Pulp Bleaching - Principles and Practice

Pulp
Bleaching
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Principles
and Practice
course of conduct or concerted

Copyright
...
CarltonW.
Science and Forestry, Retired

State University of New York
Syracuse, NY, U.SA.
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222 Rosewood Drive, Danvers, MA 01923, U.S.A. (ISBN 0-89852-063-0) $1.00 +
ISBN 0-89852-063-0
TP 0102B061
Printed in the United States of America
and
Douglas W. Reeve
Library of Congress
Department of Chemical Engineering

and AppUed Chemistry,
Pulp & Paper Centre,
University of Toronto
Toronto, Ontario, Canada
AtJanta, Georgia
@ 1996
U.S.A.
All rights reserved
College of Environmental
TAPPI
;:)1996 by:
TAPPIPRESS
Technology Park/Atlanta
P.O. Box 105113
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Dence
action.
Editors
Pulp bleaching: principles

and Douglas W. Reeve
p. cm.
Cataloging-in-Publication
Data
and practice / edited by Carlton W. Dence
Includes bibliographical references.

ISBN 0-89852-063-0
I. Wood-pulp--Bleaching.
I. Dence, Carlton W. II. Reeve,
Douglas W., 1945. III. Technical Association of the Pulp and
Paper Industry.
TS1176.6.B6P85
1996
676'.12--dc20
96-4084
CIP
~
TAPPI PRF.SS
it
specific
base fee
Center,
$.50 pp.
TABLE OF CONTENTS
Section V:The Technology of Mechanical Pulp Bleaching
Acknowledgements
Preface
vii
Section I: Introduction
11:Introductionto the Principlesand Practiceof PulpBleaching
Section II: Raw Materials

111:Production of Unbleached Pulp
25
II 2: Bleaching Chemicals: Chlorine Dioxide
59
II 3: Bleaching Chemicals:
Hydrogen Peroxide,
71
Chlorine, Sodium Hydroxide,

Peroxy Acids, ..oxygen, and Ozone
Section III:The Chemistry of Bleaching

1111: ChemicalStructureOf
and Brightness
PulpComponents
Reversion
91
III 2: Reaction Principles in Pulp Bleaching
113
11I3:Chemistry of Chemical Pulp Bleaching
125
11I4:Chemistry of Mechanical Pulp Bleaching
161
III 5: Chemistry of Brightness Reversion and its Control
183
Section IV:The Technology of Chemical Pulp Bleaching

IV 1: Oxygen Delignification
213
IV 2: Chlorination
241
IV 3: Chlorine Dioxide in Delignification
261
IV 4: (Oxidative) Alkali Extraction
291
IV 5: Ozone Delignification
321
IV 6: Hydrogen Peroxide as a Delignifying Agent
347
IV 7: Enzyme Treatments of Pulp
363
IV 8: ChlorineDioxide in Bleaching Stages
379
IV 9: Hypochlorite and Hypochlorous Acid Bleaching
395
IV 10:HydrogenPeroxideBleaching
411
IV 11: Bleaching Shives and Dirt
443
Iii
V 1: Peroxide Bleaching of (Chemi)mechanical Pulps
457
V 2: Hydrosulfite (Dithionite) Bleaching
491
Section VI:Bleach Plant Operations. Equipment and Engineering

V11: Pulp Pumping and Hydraulics
513
VI 2: Mixing and Mixers
537
V13: Washing and Washers
569
V14: Towers and Reactors
597
VIS: Sensorsand ProcessControl
625
VI 6: Water Reuseand Recycle
647
Section VII:The Properties
of Bleached Pulp
VII 1: Bleached Pulp Composition and Its Determination
675
VII 2: Brightness: Basic Principles and Measurement
695
VII 3: Strength Properties and Characteristics of Bleached Chemical

and (Chemi)mechanical Pulps
717
Section
VIII: Pulp Bleaching
and The Environment
VIII1: Effluent Characteristics and Composition
749
VIII 2: Assessing the Potential Impacts of Pulping and

Bleaching Operations on the Aquatic Environment
767
VIII 3: Dioxins
and Furansin Effluent,Pulp,and SolidWaste
799
VIII 4: Bleach Plant Air Emissions
821
VIII 5: Environmental
835
Regulations
Subject Index
847
iv
Acknowledgments
As is usually the case in any major undertaking, many individuals worked behind
the scenes in a variety of capacities to help create this book. In particular, we acknowledge with thanks the efforts of those who contributed a substantial amount of
time in serving as referees for specific chapter manuscripts: Terry Adams, Terry N.
Adams Consulting; Chad Bennington, PAPRICAN; Dennis Borton, NCASI; Bruce
Fleming, Boise Cascade; Raymond Francis, SUNY College of Environmental Science
and Forestry; Maurice Hache, Morton International, Inc.; Bruno Marcoccia, Kamyr,
Inc. ;Thomas McDonough, Institute of Paper Science and Technology;Anil Mislankar,
University of Toronto; Esa Vilen, University of Toronto, and Paul Wollwage,
Weyerhaeuser Company.We also wish to express our appreciation to the many companies and institutions for the "loan" of their employees for the purpose of contributing to this book and to TAPPI PRESS for their patience and support in this project.
As editors and contributing authors we individually wish to acknowledge those
who have been involved with us on a more personal level in the production of this
book.
Doug Reeve:
First and foremost, I am very grateful to my partner in this project, Carlton Dence.
He has been his usual self: capable, energetic, insightful, meticulous, thorough, reliable, and feisty through these many, many long months.A better partner I could not
have wished for.
.
I am grateful to my colleagues at the Pulp & Paper Centre for their steady and
capable support: in particular, Mimee Cheung, David Goring, Bruce McKague, Kate
Reeve, linda Staats, Cindy Tam, Esa Vilen, and KathyWeishar.
Finally, I wish to express my heartfelt thanks to my family for their support and
encouragement and most especially to my wife, Melanie, who tolerated my occupation of the dining room well beyond the originally agreed-upon six-month period,
often with fiery forbearance.
Carlton Dence:
The scope and detail of the material found in this book required the participation
of a co-editor whose educational background and experience complemented
my
own. By providing the chemical engineering expertise and an extensive practical
knowledge of commercial bleaching operations, Doug Reeve filled that requirement
to perfection and I sincerely acknowledge his pivotal role in determining the content and quality of this book.
I am also indebted to Elizabeth Elkins and James Williamson of the Moon Memorial library staff at the SUNY College of Environmental Science and Forestry for
providing me with copies of journal articles and for corroborating reference citations. Thanks also are due Sarah Remon for her careful work in transferring the
manuscripts for my chapters to diskette. Financial support from TAPPI as reimbursement for out-of-pocket expenses incurred in connection with this book is noted
with gratitude.
In conclusion, I wish to acknowledge the efforts of my wife, Frances, whose vicarious suffering in this literary odyssey took the form of frequent manuscript-burdened trips to Sinclair Office Supply, Mail Boxes Ine. and local post offices in the
vicinity of Hendersonville, N.C. on my behalf.
I'
Pulp Bleaching
Principles and
Practice
Preface
This edition of theTAPPI Bleaching Monograph is the fourth in a series of such books
published
in 1953, 1963, and 1979, all
projects of the TAPPI Pulping Bleaching
committee.
In a radical departure from the format of
previous monographs, the contents of this
edition have been organized under eight
major headings (designated by Roman numerals) to highlight what we perceive to
be the main subject areas for any discussion of contemporary pulp bleaching. By
this device, we have sought in particular to
give subjects relating to bleach plant engineering, bleaching chemistry, and environmental issues a more distinct identity than
in the past.
As can be inferred from the title of the

book, we have sought to stress the principles undergirding the selection, design,
and implementation of a successful bleaching operation. The decision to follow this
approach was prompted by our belief that
commercial bleaching technology has progressed so rapidly and has become so multifaceted that fundamental
chemical and
engineering
principles, properly understood and applied, are critical to the ongoing quest for new and improved bleaching
techniques.
Our decision to emphasize
bleaching principles was also motivated by
a desire to encourage the use of the book
by the academic and research communities
while still retaining its traditional usefulness
to bleach plant designers, managers, and
operating personnel.
In the preface to the 1953 edition of the
TAPPI Bleaching Monograph, the editor,
Howard Rapson, took note of the "virtual
revolution in pulp bleaching" that had occurred over the preceding ten years. The
term "revolution" applies equally well to the
period since the last bleaching monograph
was published. For example, the present

monograph
documents
the continuing
trend away from the use of elemental chlorine to ECF and TCF bleaching sequences
that favor the use of chlorine dioxide, oxygen, ozone, and hydrogen peroxide. Moreover, since the previous
monograph
appeared, oxygen and peroxide have found
new and significant uses as de lignification
chemicals in alkaline extraction stages. Also
the application of enzymes in bleaching, a
subject not included in the 1979 monograph, is an integral part of this book portending continuing interest in the use of
biological systems in bleaching.
Although external factors have been
mainly responsible for shaping the content
of this book, each edition of this series, including this one, reflects to some degree
the personal viewpoints and tastes of its
editors and authors. As examples of the latter, we cite the tWo-column page format
(unique to this edition) and its red cover
which we hope will make it visible from
anywhere in a room where it is found. Who
says erstWhile and active college professors
can't be flamboyant when properly inspired?
To our regret, the planning and production of this book has taken much longer
than we expected; we first discussed the
possibility of collaborating on the project
in the summer of 1992. It seems almost inevitable that delays will occur when the
project is as large as this and when a multiauthor format is used and when many authors must find time outside of their normal
work responsibilities.
Nevertheless,
the
authors of this book ultimately fulfilled their
commitment and we are very grateful for
their efforts in making Pulp Bleaching:
Principles and Practice a reality.
Carlton Dence
Hendersonville,
NC, USA
Doug Reeve
Toronto, ON, Canada
February, 1996
vii
SEcnON I:
Introduction
Chapter 1:
Introduction to the Principles
and Practice of Pulp Bleaching
Douglas W. Reeve
Department of Chemical Engineering and
Applied Chemistry and Pulp & Paper Centre
Toronto, Ontario
1. What is bleaching? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.1 A general description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.2 Objectives and critical parameters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
7. Trends
in pulp bleaching.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
23
Chapter I I: Introduction to Principles & Practice of Pulp Bleaching
Chapter I 1:
Introduction
to the
Principles and Practice
of Pulp Bleaching
Preface
Since the first bleaching monograph in
texts
1953 (1) two other comprehensive
have been published on pulp bleaching, in
1%3 (2) and in 1979 (]). Thorough treatments of pulp bleaching also appear as
chapters in other texts (4,5) and in the annual TAPPI Bleach Plant Operations Short
Course Notes.
In this chapter, the foundation concepts
of pulp bleaching are introduced including
the objectives, economics, history, chemistry, and engineering of pulp bleaching systems. In the other chapters in this text,
these concepts are described in greater
detail, and more penetrating explanations
and fuller descriptions are provided. There
are many places in the introductory chapter where reference might have been made
to more detail elsewhere in the text. This
has not been attempted;
however, the
reader is encouraged to seek greater detail
through the use of the table of contents and
the index.
1. What is bleaching?
1.1 A general description
Bleaching is a chemical process applied
to cellulosic materials to increase their
brightness. Brightness is the reflectance of
visible light from cellulosic cloth or pulp
fibers formed into sheets. Bleaching processes are applied to cellulosic textiles,
woven articles made from conon or linen,
and cellulosic pulp, in the form of aqueous
suspensions of individual fibers separated
from wood or non-woody materials such as
straw, reed, jute, sugarcane (bagasse), and
bamboo. Bleaching increases the capacity
of paper for accepting printed or written
images and so increases its usefulness. It
also is a means of purifying pulp, thereby
extending its application, increasing its sta-
billty,and enhancing some of its properties.

Bleaching is also effective in removing unwanted particles that contaminate pulp fibers.
The absorbance of visible light by wood
pulp fibers is caused mainly by the presence of lignin, one of the principal constituents of wood. lignin in native wood is
colored slightly, and residual lignin remaining after some chemical (e.g., alkaline)
pulping processes is highly colored. In addition, lignin darkens with age. Bleaching
processes increase brightness by lignin removal or lignin decolorization. In the manufacture of chemical pulps, most of the lignin
is removed during pulping; when these
pulps are later bleached, lignin removal is
continued. In the manufacture of mechanical and (chemi)mechanical
pulps, wood is
fiberized with linle or no lignin removal,
and bleaching of these pulps takes place
solely by the decolorization of lignin.
Bleaching produces improvements other
than enhanced brightness ofthe final product. For example, lignin-removing bleaching not only increases the brightness, but
the brightness stability of the product as
well. Treatment of pulp with some bleaching chemicals is particularly effective in
bleaching contaminating particles such as
shives (incompletely
fiberized slivers of
wood). In the manufacture of pulp for reconstituted cellulose such as rayon and for
cellulose derivatives such as cellulose acetate, all wood components other than cellulose must be removed. In this situation,
bleaching is an effective purification process for removing hemicelluloses and wood
extractives as well as lignin. To achieve
some of these product improvements, it is
often necessary to bleach to high brightness. Thus, high brightness may in fact be
a secondary characteristic of the final product and not the primary benefit. It is therefore simplistic to suggest that bleaching to
lower brightness should be practiced based
on the reasoning that not all products require high brightness.
The chemicals commonly used for pulp
bleaching include oxidants (e.g., chlorine,
chlorine dioxide, oxygen, ozone, and hydrogen peroxide), alkali (namely, sodium hy-
Pulp Bleaching - Principles and Practice
droxide), and for mechanical pulp bleaching only, a reducing agent, sodium hydrosulfite (sodium dithionite). These chemicals
are mixed with pulp suspensions and the
mixture is retained at prescribed pH, temperature, and concentration conditions for
a specified time period. The bleaching reactions that occur are highly complex due
to the complexity of lignin and the wide
variety of reactive bleaching
species
present. The progress of bleaching reactions is monitored by measuring pulp lignin content, pulp brightness, and residual
chemical.
Bleaching chemicals are frequently applied sequentially with intermediate washing between treatments (stages),
because it is not possible to achieve sufficient removal or decolorization of lignin by
the action of anyone chemical in a single
treatment or stage.
To carry out these reactions, appropriate process equipment is required for mixing steam with the pulp to control the
temperature, mixing chemicals with the
pulp, pumping or otherwise conveying the
pulp, and washing the pulp after the reaction is complete. Reaction times for bleaching chemicals are generally in the range of
a few minutes to several hours, requiring
the construction of large towers (reactors)
to provide an adequate retention (t. e., reaction) time. Bleaching processes are monitored by on-line sensors and process control
algorithms devised to achieve product quality targets with efficient use of chemicals
and energy.
1.2 Objectives and critical parameters
The prinicipal objective of pulp bleaching is to achieve a high brightness with secondary objectives, for particular end uses,
being high brightness stability, high pulp
cleanliness (freedom from colored particles), and a high cellulose content. These
objectives must be achieved without compromising the strength of the final product;
cellulose degradation during bleaching can
lead to significant loss of strength in product paper sheets.
Bleaching costs must be appropriate to
the value added by the process. Variable
costs include those of chemicals, steam, and

electric power. Capital costs associated
with the bleach plant must also be taken
into consideration, namely, the initial investment cost. depreciation, and ongoing maintenance. Bleaching reactions can lead to
significant dissolution of substance from the
pulp, decreasing the yield of final product
and affecting production cost.
The use of bleaching chemicals must be
considered in the context of the health and
safety of workers and inhabitants of the
neighboring environment and in the context of responsible environmental management. Some bleaching chemicals are highly
reactive so that proper equipment design,
operations management, materials of construction, and safeguards are required. In
the manufacture of bleached kraft pulp, for
example, effluents from bleaching operations usually constitute a significant fraction
of substances whose discharge to receiving
waters is regulated according to parameters
such as BOD (Biochemical
Oxygen Demand) and color. When chlorine is used in
pulp bleaching, as it has been for manufacture of bleached chemical pulp for many
years, chlorinated organic matter is found
in the effluent. Since the late 1980s, environmental concern has led to regulation of
<;:hlorinated organic matter in effluents and
to market pressures to decrease and eliminate the use of chlorine and chlorine-containing compounds
in bleaching.
These
environmental pressures have caused dramatic changes in bleaching technology.
In summary, the critical parameters in
pulp beaching are product quality, cost,
health and safety, and the environment.
2. Brief history of bleaching
Several good accounts of the early history of bleaching appear in the literature
0, 6, 7). Cotton and linen cloth has been
bleached since ancient times. Theophrastus, 300 BC, relates a story of a ship carrying lime for bleaching being destroyed
when water accidentally infiltrated the lime
(6). Pliny, 100 AD, described the virtues of
white linen and its production by alternate
scouring with alkali from vegetable ashes
Chapter I I: Introduction
or alkaline soils (lime) followed by washing and exposure to the sun. Buttermilk or
juices of berries were used for acid treatment. This practice continued almost unchanged until 1800.
Bleaching was a serious matter in medieval times. At one point, regulations forbade the use of lime and violators paid the
ultimate penalty: "any bleacher who used
improper materials was adjudged to be
guilty of felony and to suffer death" (6).
Cloth was laid out on bleaching-greens
(grassy meadows) for exposure to sunlight;
the process was sometimes referred to as
"grassing." Thefts from bleaching-greens
were a serious problem, so a Society of
Bleachers was formed for protection against
such thefts. Thieves were sometimes executed.
In 1784 Scheele, in Sweden, discovered
chlorine and its ability to destroy vegetable
coloring matter. At that time, chlorine was
called depholgisticated
marine acid gas because it was thought to be produced by
removing phlogiston frOm muriatic acid. In
France in 1785, Berthollet discovered that
chlorine could be dissolved in a solution of
vegetable ash, potash, and gave it the name
"eau de Javelle." Several English scientists
became involved in further developments.
Davie showed that the new gas was an element and gave it the name "chlorine" from
the Greek word "chloros" meaning green.
In 1798, Charles Tennant of Glasgow found
a less expensive alternative to vegetable ash,
namely a suspension of lime, and used the
suspension to absorb chlorine gas and make
calcium hypochlorite.
This chemical became the standard bleaching agent for the
next century. At first it was used in combination with grassing and was able to dramatically decrease the time of exposure to
sunlight from many weeks to a few days.
Experiments in which chlorine gas was
added directly to water led to tragedy in
several instances; there are accounts of wellknown scientists dying immediately, or
years later, from exposure to chlorine.
Up until the second half ofthe nineteenth
century, paper was made from cotton and
linen rags. However, with the industrial
~-~-~
to Principles & Practice of Pulp Bleaching
--~
revolution
and the advance of reading
among an increasingly larger public, the
demand for papermaking fibers for printing, publishing, and commerce outstripped
the supply of rag fiber. Wood fiber, initially
obtained from groundwood pulping and
later from kraft and sulfite pulping, was increasingly used for papermaking.
The
groundwood and sulfite pulping processes
produced fiber that was weaker than rag
fiber and of moderate brightness. The soda
and then the kraft processes produced
stronger but substantially darker pulps. One
or two hypochlorite bleaching stages were
used; the hypochlorite treatment had to
be very severe to produce even moderate
increases in kraft pulp brightness.
This
proved to be very expensive and caused
considerable damage to the pulp which increased the incentive for finding a way to
bleach wood pulp without incurring fiber
damage.
It is interesting to note that throughout
this early history, the issues of bleaching
effectiveness, cost, product quality, brightness, and strength were as important to
bleachers as they are today.
In the first 30 years ofthe twentieth century, several important
bleaching techniques were developed.
One was the
multi-stage bleach plant where hypochlorite (H) was applied first, followed by an
alkaline extraction stage (E) and then by
another hypochlorite
stage, the HEH sequence.
This approach, together with
interstage
washing, greatly decreased
chemical requirements. Ways were discovered to use gaseous chlorine (C) instead of
hypochlorite, and further savings resulted
from application of the CEH bleaching sequence. Also, in the period 1900 to 1930,
new equipment was developed to make
bleaching
more efficient.
The Belmer
bleacher permitted pulp consistency to be
increased from 3 to 6%. About the same
time, high-density bleaching was developed, which enabled bleaching to be conducted at 12% consistency. These methods
led to considerable savings in steam.
Large-scale chlorine dioxide manufacruring and chlorine dioxide bleaching (D) were
first practiced in the 1940s. This led to the
development in the 1950s of the five-stage

CEDED bleaching sequence which allowed
production
of high-brightness
products
from kraft pulp with minimal loss of pulp
strength.
In the 1970s, oxygen bleaching (0) was
commercialized.
The first commercial installation
of high-consistency
oxygen
bleaching took place in South Africa in 1970.
A decade later, the use of oxygen in alkaline extraction stages was commercialized.
In the 1980s, several other important developments took place: the introduction
of high-intensity mixers for medium-consistency pulp, medium-consistency
centrifugal pumps, and on-line optical and chemical
residual sensors. Although substantial substirution of chlorine dioxide for chlorine
had been known since the mid-1960s, it
became widely accepted only at the end of
the I980s as a result of the concern about
chlorinated organic compounds
formed
during chlorine
bleaching.
Extended
delignification of pulp was commercially
demonstrated in the 198Os; this technology
had a significant impact on pulp bleaching
by decreasing the lignin content of unbleached pulps.
In the early 199Os, market activity stimulated the development
of bleaching sequences that used no chlorine to produce
bleached chemical pulps. Complete substirution of chlorine by chlorine dioxide, the
so-called ECF (elemental
chlorine-free)
bleaching process, developed rapidly, becoming the dominant bleaching technology,
first in Sweden and then in Canada. Further development

led to bleaching processes that used neither chlorine
nor
chlorine-containing
compounds
termed
TCF (totally chlorine-free).
Development
of hydrogen peroxide and ozone bleaching
technology was an essential component of
this new technology.
3. Significance of bleaching in
the paper industry
Bleaching plays an important role in the
economics of the paper industry. Global
bleached fiber capacity in 1994 was 93 million tons as shown inTable 1 (8). This tonnage is dominated by bleached chemical
pulp, in particular kraft pulp together with
a small fraction of sulfite pulp. Although
only 2.3 million tons of bleached chemithermomechanical
pulp is reported in this
table, it should be noted that a large amount
of mechanical pulp is produced for newsprint which may require only modest, partial bleaching.
An important
distinction
is made in
Table 1 between market bleached fiber and
integrated
bleached fiber. The market
bleached fiber is sold as an end product,
and this usually imposes higher quality standards in terms of brightness, cleanliness,
strength, and uniformity. In integrated mills,
the bleached fiber is sent as a suspension
directly to papermaking operations and so
does not face the more stringent market
demands. This distinction is an important
factor in bleach plant design and operation.
Table 1. Global bletwbe4ftber j1rotbIelfmt Cflptldly I" 1994 (8).

Bleached Fiber Capacity,
Millions of Tons
Market
Integrated
32.2
1.9
2.3
Kraft
Sulfite
BCTMP
42.6
4.0
Total
Annual
Growth
Rate, %
74.8
2.5
5.9
2.3
o
7.5
5
Deinked pulp
1.1
9.2
10.3
Total
37.5
55.8
93.3
BCTMP
=Bleached
chemithermomechanical
pulp.
Chapter
I 1: Introduction
to Principles
& Practice
of Pulp Bleaching
Pulp Bleaching
- Principles
and Practice
r.bk 3. Pm4IIetIoIr of bletu:be4 palp.
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~~..c::
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ket pulp
duction
spruce,
50% of
because of the relatively high proof softwood

pulp in Canada from
pine, hemlock, fir, and cedar. About
production
in the United States is
hardwoods,
properties that are in demand on the mar~ketoThere is relatively little market for unbleached kraft pulp, the bulk of production
Bleaching not only adds to the selling

price of chemical or mechanical pulp but
often creates the market. The price of
":
bleached pulp is notoriously

volatile: in late
1993, the price was very depressed
at
(US)$4OO per ton but, by late 1995, it had
~\0
going directly
into the manufacture
of
linerboard.
It is also apparent
from Table 2
~that Japan, Germany, France, and the United
~States must import
pulp to be able to
0\
achieve the production
countries
to create
a product
with
of paper and board
indicated in Table 2. Imports cannot be

\0
r-..:
0..
-;
North America, softwood dominates mar-
in these
r<"\
0..
ct
~...
U
::;
reached
mainly
(US) $1000
eucalyptus.
per ton (8,12).
Bleached fiber is used in a wide range of
calculated directly from this table because

it does not take into account recycled fiber
products including writing and publicationgrade paper, tissue and sanitary papers,
absorbent products, and board for packag-
and non-fibrous additives.
ing. Twenty-nine percent of the world pulp
Another important issue to consider in

the structure of the bleaching industry is
and paper industry production is used for

printing- and writing-grade papers, while
U
rJJ
2.4
~...;
~woods as compared with hardwoods. Softwoods contain

more lignin than do
~hardwoods and are generally more difficult
~~~"3
13.8
8.7
softwood. In Canada, the dominant hardwood species is aspen poplar; in the United
States oaks, maple, and gum predominate.
Market pulp production in Europe is dominated by the Nordic countries where pine
is the dominant softwood and birch is the
dominate hardwood. In Latin America and
Asia, production is dominated by tropical
the production
-0
0
:is
c::
~u ::J
EQ
N
""
2 (9). The
kraft pulp
Japan, Finproducers
~0..
-0
-0
-8
U
U
S
..c::
vi
0..
0\
bleached
fiber are given in Table
leading producers
of bleached
~~arethe United States, Canada,
land, and Sweden; the leading
(11)
13.8
of market pulp (mainly bleached kraft) are

~Canada,the United States, Sweden, and Brazil. In countries where market pulp is the
~dominant fraction of bleached kraft pulp
production, the proportion of bleached to
~unbleached kraft is very high, for example,
~in Canada, Portugal, Brazil, and Chile.
Bleaching is used to economic advantage
0\
CI)
~~~r<"\ I'oci
0\
-0
~0
r<"\
0\
0..
~...
...
...
~I::!
00
"'!
""
~U
~::J'"
~~~1
~vi
r<"\
~'S
0\
-E
it
2.5
Asia
United States
'"
0..
3.8
1.4
Additionalfigureson the production of

0\
~oci
u
-0
4.5
Millions ofTons
&S
1S.
4.8
Europe
~LatinAmerica
Total Pulp Production in 1993,
""
~ee ""-
...
10.7
-a
c::
'"
.....
0
c::
'"
Hardwood
North America
c::
S
Market Pulp Production in 1994,

Millions ofTons (10)
of bleached
pulp from soft-
packaging
accounts
for 38% of all paper
and
board. Newsprint, the main end product

of mechanical pulps, accounts for 14% of
production (9).
to bleach. This difference has an impact on
The demand for bleached fiber is strong
bleaching processes and equipment. Table

3 provides statistics on the production of
softwood compared with hardwood.
In
and is expected to remain so. According to

the FAO, paper production will grow from
240 million tons per year in 1991 to 440

million tons per year in 2010 (13). Much
of this growth will result from increased use
of recovered paper (from 90 to 170 million
tons per year), but the demand for virgin
wood pulp will also grow very rapidly from
150 to 260 million tons per year.
4. Pulp composition,
and terminology
properties,
4.1 Composition
The properties of pulp are the result of
the properties of its principal components
cellulose, hemicellulose, and lignin.
Cellulose, a carbohydrate, is a linear polymer of anhydroglucose and constitutes 4050% of most wood species. However, by
acid hydrolysis or a combination of oxidation and alkaline hydrolysis, the chemical
bonds in a cellulose chain can be broken.
The strength of paper is due in part to the
strength of individual cellulose chains and
in part to hydrogen bonds formed between
adjacent cellulose moleeules, within fibers,
and between fibers, which are responsible
for the strength of paper sheets. Cellulose
has a great capacity to form hydrogen bonds
and, as a result, has a great affinity for
water.
Cellulose is essentially colorless and does
not require bleaching. However, during the
bleaching of pulp fibers to decolorize other
components, cellulose degradation can occur. This can lead to cellulose fragments
being dissolved and to a lower pulp yield.
Further, if cellulose degradation is sufficiently severe, pulp strength will decrease.
Although the strength of pulp sheets is a
complex property, the degradation of cellulose during pulp bleaching can be an important factor in determining overall pulp
strength.
To determine the extent of cellulose degradation, the average length of the cellulose
molecules is determined.
To do this, the
pulp is dissolved in a cellulose solvent and
the viscosity of the solution, which is a function of cellulose average chain length, is
measured. Pulp viscosity, as this is known,
is often used as an indicator of cellulose
degradation during bleaching and to indi-
cate the strength potential of pulp sheets.

It must be noted, however, that pulp viscosity is not linearly related to strength; as
viscosity decreases, pulp strength may not
decrease until some critical viscosity value
is reached. Further, the viscosity-strength
relationship is different for different bleaching processes and wood species.
Like cellulose, hemicelluloses are carbohydrate polymers that comprise another
important component of wood and pulp.
Collectively, hemicelluloses
usually comprise 20-30% of the dry weight of wood.
Unlike cellulose, which is derived from a
single sugar, glucose, hemicelluloses consist of several five- and six-<:arbon units nonuniformly linked. Hemicelluloses are often
branched and have a much lower molecular weight than does cellulose with the result that they are susceptible to removal
during pulp processing, especially under
alkaline conditions.
Hemicelluloses
are colorless and relatively stable and therefore need not be removed during bleaching
to produce
high-brightness
pulp. However, hemicelluloses are removed during pulp processing to produce dissolving pulps for the
manufacture of rayon and other cellulosebased materials. Although the molecular
chains in hemicelluloses are much shorter
than those in cellulose and do not make the
same contribution to the strength of paper
sheets, hemicelluloses are extremely important for bonding in paper sheets. Further,
loss of hemicelluloses
during bleaching
decreases pulp yield.
lignin comprises 26-32% of typical softwoods and 20-28% of typical North American hardwoods.
It is structurally
very
different from cellulose and hemicelluloses.
It is a randomly linked, three-dimensional
polymer consisting of phenylpropane building blocks. Some of the bonds in lignin can
be hydrolyzed so that the molecular weight
can be decreased and lignin fragments dissolved, as is the case in chemical pulping.
However, not all lignin is removed during
chemical pulping, and the residual lignin is
often darker than the original lignin. In the
manufacture of bleached chemical pulps,
10
the residual lignin after pulping is oxidatively fragmented to lower the molecular
weight to a point where dissolution takes
place. In high-yield pulps, lignin bleaching
is achieved by decolorization with an oxidizing or a reducing agent. This is termed
"lignin-retaining bleaching."
lignin content must be measured during
chemical pulping and bleaching. Because
of its complex structure and relatively low
concentration in chemical pulp, lignin is difficult to measure directly and therefore relative lignin content
is measured
by a
standardized reaction of potassium permanganate with pulp. permanganate
reacts
with the lignin in pulp but not with the
carbohydrate components. In this test, the
conditions for the reaction between permanganate and pulp (pulp concentration
in the reaction mixture, permanganate
charge or concentration,
acid concentration, time, and temperature) are carefully
controlled so that a consistent, reproducible though still relative, measure of lignin
content is obtained. Several variations of
this test are available, so it is important to
know which set of standard conditions are
used. One test is referred to as the"k number" (sometimes called the "p number" or
"permanganate
number"); another test is
termed "kappa number." Conditions used
for the kappa number test are slightly more
rigorous than those for the k number test
and provide a more linear relationship between kappa number and lignin content;
Ttlble 4. ComposIIImI
aU propertks
Pulp
of different
however it requires more time. The "k number" can be approximated by multiplying
the kappa number by 0.66. Lignin content
(in weight percent) is approximated
by
multiplying the kappa number by 0.15.
Thus, an unbleached sofrwood kraft pulp
might have a kappa number of 30, which is
approximately equal to a k number of 20
and a lignin content of 4.5%.
The properties of different pulp types are
shown in Table 4. Values for the groundwood pulp reflect the relative concentrations of cellulose, hemicellulose, and lignin '
initially present in wood. Without bleaching, the pulp has a brightness of 62. However, mechanical damage occurs in the
fiberization process with the result that the
tensile and tear strengths are low. Acid
sulfite pulping provides pulp having a lower
lignin content and a significantly higher
strength than groundwood; however, the
yield is significantly lower. Acid sulfite
pulping does not decrease pulp brightness
significantly, and this type of pulp is readily
bleached to 90 brightness.
Unbleached kraft pulp at 50% yield provides a much stronger pulp sheet, although
the kraft process leads to significant darkening of the lignin and therefore to lower
brightness. Kraft pulp can be bleached to
a high brightness with high strength retention.
Another component of pulp that must
be taken into account are the extractives.
Extractives are wood chemicals that can be
removed by extraction with neutral solvents
sjmlce pulps
(14).
lignin, Brightness, Tensile

Unbleached CeUulose, Hemi
Tear
Yield,
%
CeUuloses,
%
Strength, Strength
%
%
%
kin
Groundwood
95
42
31
27
62
2.5
40
Acid sulfite, unbleached
75
55
56
71
22
17
22
6
60
63
7.5
9.5
60
70
55 (50)'
82
18
90
10
70
Kraft, unbleached
50
79
17
20
11.5
130
Kraft, bleached
,
Bleached yield
50 (47)'
82
18
90
11.5
130
Acid sulfite, bleached
Chapter
I 1: Introduction
such as acetone, ethanol, or benzene. The

extract contains substances such as turpentine, wood resin and tall oil. Most of the
extractives are removed during chemical
pulping, but some may remain in pulp in
the form of "pitch" and cause processing
problems.
to Principles
& Practice
of Pulp Bleaching
11
feed a rotary drum filter which, in turn, increases the consistency to 12-14%, (medium consistency).
To obtain higher
consistency
pulp, pressing is required;
presses produce pulp consistencies of 3045% (high consistency).
4.2 Water and pulp

Water plays many roles in pulp bleaching. It is used to transport fibers in suspension, dissolve bleaching chemicals, and
transport them to the bleach plant. Water
is also a reactant in many bleaching reactions; it dissolves reacted, fragmented pulp
components and is used to wash them from
the pulp; in the form of steam, water is used
to heat pulp.
The pulp-water relationship is compll:X
and is summarized in Table 5. If completely
dry pulp is placed in a room at normal humidity, it will take up water because of the
high affinity of cellulose for water. Thus,
"air-dried" pulp contains approximately
<)0",4,pulp fiber and 10% water. Air-dried
pulp is the commodity sold by market pulp
mills. The water in air-dry pulp is held, i.e.,
absorbed by hydrogen bonding. As more
water is added and all adsorption sites are
taken up, the capillaries in the cell walls of
pulp fibers fill and water is held by capillary forces. The total water held in the saturated cell wall, known as the water retention value, is typically 1.5-2 g water/g pulp.
In the processing of pulp suspensions,
the percentage of pulp in the total mass of
suspension is known as consistency. To
provide sufficient freedom of movement
between pulp fibers to facilitate uniform
paper sheet formation, paper machine feed
suspensions are less than 1% consistency.
Similarly, to feed a traditional rotary drum
filter and provide uniform distribution of
fibers across the filter, the feed consistency
must be reduced to 1%. Conventional centrifugal pumps are able to pump pulp suspensions of up to 3 or 4% consistency;
therefore, discharge of pulp from bleaching towers has traditionally required dilution of the slurry to 3% consistency. This
pulp suspension is further diluted to 1% to
Oven-dry
Fiber Water,
%
%
Humidity - 5% 98.6
- 50"A>90.7
- 80% 87.0
Air-dried pulp
90
Newsprint'
1.4
9.3
13
10
Press discharge
40
60
Gas-phase bleaching
(high consistency)
30
70
Pulp washer discharge

(commonly called
medium-consistency
or high-density pulp)
12
88
Bleach tower discharge
97
Pulp washer feed

(rotary drum illter)
Paper machine feed
,
99
0.5
99.5
Data for standard newsprint

at room temperature,
CPPA Technical Data Sheets 017-05.
4.3 Optical properties of pulp

Ught shining on a paper sheet is reflected, absorbed, or transmitted. At each
air-fiber interface, light can be reflected or
refracted. In the paper sheet, there is layer
upon layer of fibers and light is scattered
through this multiplicity of air-fiber interfaces. Also, microfibrils, which are very
small fiber elements, may scatter light by
diffraction. Finally, each fiber may contain
components that absorb light.
For practical purposes, a single measure
is used to incorporate all these factors in a
meaningful way. Kubelka and Munk found
that light absorbance and light scattering
can be related to a single variable, reflectance. Reflectance is a measure ofthe light
reflected from the fiber sheet. The KubelkaMunk equation, [1], correlates these terms:
12
R.,.
=1 + (k/S) - -J(k/S)'
+ 2(k/S)
[11
where:
Roo
reflectivity of an "infinite"
pile of sheets
absorption
scattering
coefficient,
m2/kg
coefficient,
m2/kg.
The optical properties of a pulp vary with

the wavelength of the incident light. Reflection and refraction are not affected by a
change in wavelength;
however, absorbance is. Therefore, reflectance, which is a
function of absorbance, varies with wavelength.
Brightness is defined as the reflectance
at 457 nm and is a physical phenomenon.
Whiteness, on the other hand, is a physiological phenomenon based on how the eye
senses the interaction of visible light with
a paper sheet. When blue dye-stuff is added
to a yellow-tinged sheet, the sheet looks
whiter but the brightness decreases.
Brightness is affected by how it is measured. The angle of incident light, the surface properties of the sheet and the degree
of beating of the sheet all have an effect on
brightness. Brightness is measured relative
to a standard surface. Standard methods
have been developed for brightness measurement.
Another important optical or visual characteristic of pulp is dirt. Dirt is defined as
any foreign matter having a marked contrasting color to the rest of the sheet and an
equivalent black area (EBA) of 0.04 mm2 or
more. The number of particles observed

by examining both sides of the sheet are
summed to give the total EBA. Dirt can be
contributed by wood [bark, resinous material, sand, grit, and shives (incompletely
fiberized fiber bundles)], by the pulping
process (carbon specks, rust, rubber) and
by external sources (plastics, grease, fly
ash). Pulp bleaching is an effective means
of eliminating some types of dirt; some
bleaching agents and bleaching sequences
are more effective than others.
5. Bleaching chemicals and

sequences
5.1 Bleaching reactions
Bleaching reactions must be evaluated in
terms of changes in the major components
of pulp. Cellulose and hemicelluloses are
the main strength contributing pulp components, and it is desirable that these components not react with the bleaching
chemicals in chemical or mechanical pulp
bleaching. In chemical pulp bleaching, the
desired affect is to degrade and dissolve the
lignin (lignin-removing
bleaching);
in
(chemi)mechanical
pulp bleaching, the desired affect is to decolorize the lignin (lignin-retaining bleaching). Another objective
in chemical pulp bleaching is to dissolve
extractives and to decolorize or eliminate
particles.
There are several ways in which reactions
of lignin with bleaching chemicals can be
evaluated. Bleaching effectiveness depends
III
III
Q)
c
OJ
.t:
Chemical applied per unit of pulp

Fig. 1. E.JTfdetIcy IJf pulp
bletUbiJfg.
Chapter I 1: Introduction to Principles & Practice of Pulp Bleaching
13
Chemical applied per unit of pulp

Fig. 2. Selectivity
In pulp
bletu:hlng.
14
condition is usually linked to production

rate and cannot be significantly changed.
One of the most important consequences
of limited bleaching effectiveness,
approaching asymptotic limits with increased
chemical applied, is the fact that multiple
applications of bleaching chemical are often required to achieve a desired result.
Thus, a combination of reactants or a sequential application of reactants is used to
achieve bleaching objectives.
Oxidants are extremely important bleaching chemicals. In chemical pulp bleaching
they oxidatively degrade lignin thereby decreasing its molecular size. In this process
carboxylic acid groups are formed which

impart increased water and alkali solubility
to the fragments.
The only oxidant currently
used in
(chemi)mechanical pulp bleaching is hydrogen peroxide. Its relatively mild action does
not fragment and dissolve lignin, but instead
decolorizes particular structures (i.e., chromophores) within the lignin'lin the pulp.
Alkali, namely sodium hydroxide, is a vital chemical in bleaching sequences. It degrades oxidized lignin by hydrolysis and
ionizes acidic and phenolic groups, thereby
facilitating the dissolution of lignin from the
pulp.
Ttlble 6. l'InrdfmIs, IUlrll",liJgesand disadvantages of bleaching cbemkals.
on the degree to which lignin can be removed or decolorized. Bleaching efficiency

can be expressed as the amount of chemical consumed per unit of lignin removed
or decolorized.
Bleaching chemicals vary
in their effectiveness and efficiency, which,
in turn, depend on wood species, pulping
process, and bleaching conditions. It is important that bleaching chemicals be selective with respect to lignin, that is, that they
react with lignin in significant preference to
reacting with the carbohydrate components
in pulp. Selectivity is manifested by the extent of carbohydrate degradation, or the decrease in cellulose-hemicellulose
yield, per
unit of lignin removed or decolorized.
For many bleaching chemicals, bleaching
efficiency decreases as more chemical is
applied, as illustrated in Fig. 1. For the delignification process shown, lignin content
reaches a lower limit asymptotically while
brightness reaches an upper limit asymptotically. These trends are characteristic of
many different bleaching agents. Similarly
(chemi)mechanical
pulp bleaching efficiency decreases as more chemical is applied and brightness limits are approached
asymptotically.
Bleaching effectiveness,
as measured by the maximum brightness
that can be achieved, is a function of the
ble~ching chemic~, pulp, :md process con.
ditions.
Bleaching selectivity is often described
by plotting pulp viscosity against chemical
applied as illustrated in Fig. 2. Comparisons of bleaching chemicals are also made

based on viscosity at a particular brightness
or viscosity at a particular degree of lignin
removal.
Selectivity is governed by the relative
reaction rate of a particular
bleaching
chemical with lignin compared with that
for other pulp components.
It is desirable
to have a high reaction rate of the bleaching chemical with lignin and extractives and
a low or negligible reaction rate of the
chemical with the carbohydrate
components. In addition, there are competing
reactions in bleaching systems which lead
to the formation of unwanted by-products
and do not produce higher brightness or
lower lignin content. For instance, bleaching chemicals may react with lignin already
dissolved. As another example, chlorate ion,
an unreactive species, is formed in the chlorine dioxide bleaching of pulp thereby decreasing bleaching efficiency. Bleaching
reaction rates and pathways are often profoundly affected by pH; in such cases, alkali or acid may be added to achieve the
optimal pH. Most bleaching reactions are
accelerated by increases in temperature,
pulp consistency, and bleaching chemical
concentration. Temperature change is the
most widely used means of controlling reaction rate and extent. Although the retention time can be changed to a modest
degree in bleaching systems, this process
Pulp
Type'
Advantages
Disadvantages
Effective,econonUc~
delignification; good
Organochlorine formation;
highly corrosive
Oxidant
Function
Chlorine
Oxidize and chlorinate

lignin
Hypochlorite
Oxidize, decolorize, and

solubilize lignin
Easy to make and use;

Low cost
Can cause loss of pulp

strength; chloroform
formation
Chlorine
dioxide
1) Oxidize, decolorize,
and solubilize lignin
2) In s~
amounts with
Cl;" protects against
cellulose degradation
Achieves high brightness

without loss of pulp
strength; good particle
bleaching
Must be made on-site;

cost; some organochlorine
formation; highly corrosive
Oxygen
Oxidize and solubilize

lignin
Low chenUcal cost;

provides chloride-free
effluent for recovery
Requires significant capi~

equipment when used in
large amounts; potenti~
loss of pulp strength
Hydrogen
peroxide
Oxidize and decolorize

lignin
Cor
M
Easy to use;
low capit~ cost
High chenUc~ cost;

poor particle bleaching;
can cause loss of pulp
strength
Ozone
Oxidize, decolorize, and

solubilize lignin
Effective; provides
chloride-free effluent for
recovery.
Must be made on-site; cost;

poor particle bleaching and
pulp strength
Reductant
Hydrosulfite
Reduce and decolorize

lignin in high-yield pulps
Easy to use;
low capit~ cost
Decomposes readily;
linUted brightness gain
~Xylanase
Ca~e
xylan
hydrolysis and aid in
Easy to use;
low capi~ cost
limited effectiveness;
cost
particle
remov~
lignin remo~
~Sodium
hydroxide
Hydrolyze chlorolignin
and solubilize lignin
Effective and econonUcal
Darkens pulp
Chelants
EDTA or
DTPA
Remove me~ ions
Improves peroxide
selectivity and efficiency
Cost
'C = chenUc~;
M = mechanic~.
Chapter I 1: Introduction
5.2 Bleaching chemicals

Table 6 summarizes the chemicals used
in pulp bleaching, their function, advantages, and disadvantages. The statements
made here are, of necessity, simplifications.
It is important to remember that the conditions of application are extremely important for achieving bleaching objectives.
Table 7 presents further information
about bleaching chemicals, in particular, the
formula and letter designation for each
chemical. The manufacturing process and
means of transport are also listed. Finally,
the form in which the chemical is used in
the bleach plant is indicated. The latter is
critical to process and equipment design.
Oxidants accept electrons and are reduced; the substances they react with give
up electrons and are oxidized. Table- 8
shows the half-reactions for oxidants commonly used in bleaching and the number
of electrons transferred per molecule. For
instance, chlorine molecules accept two
electrons and form two 1:Woride ions. The
equivalent weight is the weight of substance
required to transfer one mole of electrons,
that is, the formula weight divided by the
number of electrons transferred.
Equivalent weight can be used to compare equivalent oxidizing power. For example, only
19 kg of chlorine dioxide are required to
achieve the same transfer of electrons as 50
kg of cWorine.
Oxidizing capacity can also be expressed
in unit OXE or oxidizing equivalents (15).
An OXE is equal to one mole of electrons
transferred
during oxidative bleaching.
Therefore, an OXE of cWorine weighs 35.5
grams. As can be seen in Table 9, atypical
application of cWorine, cWorine dioxide,
or oxygen to a 30 kappa number pulp provides 1700 OXE for the first two chemicals
and 3750 OXE for oxygen. It is apparent
that oxygen is less efficient in the transfer
of its electrons than is cWorine or cWorine
dioxide. However, bleaching costs are determined by many factors besides oxidizing equivalence, namely, delignification or
bleaching efficiency, bleaching chemical
cost per unit weight, capital cost, other
chemical requirements, and environmental
costs.
15
In comparing and selecting bleaching

chemicals, other factors must also be taken
into account: selectivity and the ability of
the chemical to bleach to the desired brightness without decreasing pulp strength, particle removal efficiency, environmental
concerns, hazards to personnel and equipment, materials of construction,
stability,
and unwanted by-products.
5.3 Bleaching sequences

Single applications of chemicals have a
limited effect in brightness improvement or
in delignification.
Multi-stage application
of bleaching chemicals can provide much
greater benefits. Interstage washing, which
removes dissolved impurities, is partially
responsible for improvement in the extent
and efficiency of bleaching and,in addition,
multi-stage sequences take advantage of the
different action of each chemical and provide synergy in bleaching or delignification.
For example, consider the results of bleaching chemical pulp with (a) D, (b) DO, or (c)
DED, that is, (a) one. stage of cWorine dioxide bleaching, (b) two stages of cWorine dioxide bleaching with interstage washing
and (c) two stages of chlorine dioxide
bleaching with an intermediate
stage of
extraction with sodium hydroxide, each
stage being followed by washing.
00
bleaching provides greater final brightness
and greater efficiency of chemical usage
than does the single D stage. DED bleaching provides greater efficiency and final
brightness than does 00 bleaching.
A classic example of the synergy between
stages is the partial sequence CE, cWorination followed by extraction with sodium
hydroxide. CWorination oxidizes and fragments the lignin but, because it is carried
out under acidic conditions, only part of the
degraded lignin dissolves. The following
extraction stage is extremely effective in
removing the lignin degraded in the preceding cWorination stage. The CE partial sequence provides efficient lignin removal
because of the combined action of each of
these chemicals in the proper sequence; if
the sequence was reversed, EC; relatively
little delignification would occur.
16
- Principles
Pulp Bleaching
Table 7. Dnerlptioll
and Practice
of bletrel1i"g cbemktds.
Stage
Designation
Manufacture
Form in Bleach Plant at

Point of Application
By electrolysis of NaCi
solution; shipped as liquid
under pressure
By reaction of CI with
NaOH (or for Ca(OCI) with
Ca(OH),}; usually on site
Pressurized gas
On-site by reduction of
chlorate
By separation from air;
shipped as cryogenic liquid
or separated on-site
By reduction of oxygen via
organic intermediates;
Shipped as 50% solution
Solution, -10 g/L
On-site by silent electric

discharge in oxygen gas
By reduction of bisulfite
Pressurized
gas mixture.
up to 12% OJ in 0,
Isolated from fermentation

processes
Solution
By electrolysis of NaCi
solution; shipped as
50% solution
Solution, -10%
Name
Formula
Chlorine
CI,
Hypochlorite
NaOCI
Chlorine
dioxide
Oxygen
ClO,
0,
Hydrogen
peroxide
H,o,
Owne
O~
Hydrosulfite
Na,S,o.
Enzymes
Sodium
hydroxide
NaOH
Pressurized gas
Solution, 2-5%
Solution
Table 8. Oxldizi"g
equitJlllents
Oxidant
Formula
Weight
(g/mole)
Electrons
Transferred!
Molecule
Equivalent
Weight
(g/mole electrons
transferred)
Equivalent
to
50 kg of CI, (kg)
71
133'
2
2
35.5
66.5
94
67.35
13.5
19
32
34
4
2
8
17
II
24
48
II
Chlorine
Sodium
hypochlorite
Chlorine
dioxide
Oxygen
Hydrogen
peroxide
Ozone
of differnt
Solution, -40 g/L as

equivalent el,
bletrel1i"g agenls.
Reactions of different oxidants used in bleaching

CI2 + 2 e- ~ 2 CINaOCI + H,o + 2 e- ~ NaCi + 2 OHCl02 + 2 H,o + 5 e- ~
02 + 2 H,O + 4 e- ~
H202 + 2 H++ 2 e- ~
03 + 3 H+ + 6 e- ~
'Including NaOCIand NaClsince 2 NaOH + CI, ~
CI- + 4 OH40H2 H20

30H-
NaOCI+ NaCI+ ",0
Amount of
Chemical
-"._~---
Chapter I 1: Introduction
17
18
Table'.
Oxidizing
e'l.drllllerUs
Chemical
Applied'
(kg/metric ton
of pulp)
Chlorine
60
Chlorine
23
dioxide
Oxygen
30
'To 30 kappa unbleached
ofbleacltlng
agerUs.
Equivalent
OXEI
Weight Metric Ton
(g/mole)
of Pulp
35.5
13.5
8
1700
1700
3750
softwood
Cost and selectivity are two very important aspects of establishing the proper sequence of bleaching chemicals. Chlorine
is less expensive than chlorine dioxide, so
chlorine should be used earlier in the sequence where more lignin is present and
more chemical is required. Thus, for great.er
economy, the preferred sequence is CEO
instead of DEe. Also, chlorine is less selective than chlorine dioxide, so the former
should not be used at the end of the sequence where the lignin content is low and
the possibility of degrac:fmg carbohydrates
is greater. Thus, to achieve greater for selectivity, the preferred sequence is CEO instead of DEe.
Bleaching sequence designation is specified by TAPPI Information Sheet TIS 060621. The letter designated for each chemical
is used to describe a stage of chemical application followed by washing. Thus, CEO
refers to the application of chlorine (C) followed by washing, then sodium hydroxide
for alkaline extraction (E) followed by washing, then chlorine dioxide (D) followed by
washing. When washing is omitted between chemical applications, letters indicating the chemicals in that portion of the
sequence are enclosed in parentheses. For
instance, C(EO)D refers to the sequence
chlorine, washing, sodium hydroxide addition, oxygen addition and washing, chlorine
dioxide and washing. If the chemicals are
added simultaneously, in this case alkali
and oxygen, the sequence is designated
C(E+O)D.
Examples
of bleaching
sequences are shown in Table 10. It is noteworthy that, in chemi-mechanical
pulp
bleaching, a single application of one chemical is most common.
Table 10. 1'yJ1ka1 bleacltlng
sefJ'll!'fUS.
Sequence
Comment
CEH
Classical sequence for production semi-bleached kraft

pulp
(C+D)(EO)DED Classical market kraft pulp

sequence of the 19805
D(EO)DED
Classical ECF(elemental chlorine-free) sequence for market
kraft pulp
OZ(EO)D
First sequence using ozone for
commercial production of
kraft pulp in NorthAmerica
OQP
First commercial rCF sequence for bleached kraft
pulp
yP
Two-stagebleaching of (chemi}
mechanical pulp with hydrosulfite and peroxide
5.4 Process conditions

Process conditions govern the extent and
efficiency of bleaching reactions and also
strongly influence selectivity and, in some
cases, particle elimination. Chemical consumption during a bleaching stage is the
single most important parameter. Chemical application
is set by proportioning
chemical flow to pulp flow with adjustments being made based on information
about brightness
target levels or delignification achieved. The pH has a profound
effect on most bleaching reactions and may
be controlled by addition of alkali or acid
before or with the bleaching chemical.
The extent to which the applied chemicals are consumed depends on the kinetics
of the chemical reaction and the reaction
time. Time is specified in equipment design but is difficult to adjust because it is
linked to equipment size and production
rate. Because most bleaching reaction rates
increase with temperature, the reaction rate
and therefore the extent of reaction is most
commonly controlled by temperature adjustment. Temperature increases are constrained by economic factors because they
require the use of steam and by equipment
design because, for example, rotary drum
filters do not operate well when the
temperature of the pulp suspension is so
Table 11. TypktII process
cmrditforrsfor
bleacbing
softwood
kraft jmlp
In an OD(EO)DED sequerru.
(EO)
8
,-5
3.5
70
180
12
5
10.6
70
60
12
Chemical applied,
kg/t
30
l
CIOl
NaOH
End pH
Temperature, C
Tune, min
30
11+
95
30
12
Consistency, %
10...J
8i
~
:g
0.1-
"0
en
5
15
25
10.6
70
60
12
3
60
30
3
5
4
70
180
12
~:
~c
0.01-
0.001
0.01
0.1
10
Partial pressure, atm

Fig. 3. Solubilily
of bleacltlng
gases.
high that flashing in the drop leg occurs.

Chemical reaction rates are often increased
by increasing chemical concentration; however chemical concentration
in bleaching
is fued by the original equipment design
which fIXes pulp consistency. Once pulp
consistency is fixed, it is difficult to make
any significant changes in chemical concentration. Chlorination stages are typically
operated at 3% consistency, but most other
stages are operated at 12% consistency.
Some oxygen and ozone stages are operated at high consistency (approximately
30%).
Process conditions are therefore established by bleaching reactions, process targets, and process equipment.
Typical
process conditions for bleaching a softwood
kraft pulp in an OD(EO)DEO sequence

presented in Table 11.
are
5.5 Bleaching with gases

Several of the bleaching chemicals described above are gases that have a limited
solubility in water as shown in Fig. 3. Chlorine dioxide is the most soluble of these
gases and, when introduced into chilled
water, can be made into a 10 g/L solution,
thus providing a practical means for its transport to the bleach plant. The partial pressure of chlorine dioxide must be kept below
a specific limit to avoid its spontaneous decomposition in the gas phase. Chlorine can
also be absorbed into water, but the volume
of water or partial pressure required is too
high. As a result, chlorine gas is the most
(EO)
delignification
30%
12%
19
20

Steam
extraction
12%
Water
Fig. 6. U"it opertItWns
NaOH
dium consistency (12%), the gas must be

finely dispersed in the continuous water
phase to provide sufficient surface area for
mass transfer to take place.
6. Bleaching flowsheets
There are a number of ways in which
bleaching can be represented in flowsheets.
One example is given in Fig. 5, a block diagram showing the application of chemicals
in each of four bleaching stages. Water is
added to each bleaching stage for washing,
and in most bleaching stages steam is added
to increase the temperature. Effluent from
the oxygen stage is sent to the recovery
system of the kraft mill, but acidic and alkaline effluents from the remaining bleaching stages are discharged, usually after
passing through biological treatment systems.
CI02
CI02
NaOH
Water &
steam
O2
Water &
steam
Unbleached
pulp
EO
Effluent
to recovery
Acidic
effluent
Alkaline
effluent
Fig. 5. Biocii dl4gmm flowsbeet of cbemklll pulp bleaebl"g.
Mixer
Bleached
pulp
Reactor
Washer
Washed
pulp to
next stage
Washed
pulp from
previous
stage
02 gas
practical form for chlorine application in

bleaching.
Oxygen and ozone have very
low water solubility and must be applied
to pulp suspensions directly as gases.
Any gas mixed with a pulp suspension
must dissolve in water and diffuse to the
reaction site on the pulp fiber before reaction can occur. In such cases, a significant
engineering
challenge ;lrises, namely, to
provide sufficient surface area to facilitate
this mass transfer. This objective is made
more difficult by the relatively large gas
volumes required in comparison with the
volume of pulp suspension as shown in Fig.
4. In high-consistency designs, mass transfer from gas to fiber is facilitated by elimination of all free water; at high consistency,
all water is held within the fiber cell wall.
The gas phase is the continuous phase and
pulp fibers are dispersed within it. At me-
Water
Consistency
Mixer
000000
000000
~~~g~~~~~6~6~
o~o~ooooooooo
Chemical
Effluent
I"
pulp bletU:bI"g.
Within each of these stages, there is usually a series of unit operations as depicted
in Fig. 6. There are often several mixing
stages where steam and chemical are applied to the pulp. The mixture of chemical
and pulp suspension then passes into a reactor which provides sufficient retention
time for bleaching reactions to occur. Pulp
exiting the reactor passes through a washer
before continuing to the next stage.
1\.wide variety of equipment is available
to accomplish the unit operations in each
of the various stages used for bleaching
chemical and (chemi)mechanical
pulp.
Traditionally,
rotary drum filters have
been used as washers between bleaching
towers as illustrated in Fig. 7. Several
other examples of process equipment for
bleaching kraft pulp are shown in Figs.
8-10.
Further details on the chemistry, processes and equipment used in pulp bleaching are found in the chapters that follow.
7. Trends in pulp bleaching
In the last decade there has been an extremely rapid evolution of processes for
production of bleached pulp. Much of this
technological activity has been environmentally driven. There are several important
emerging technologies for manufacture of
bleached pulp: extended, in digester delignification; oxygen delignification; "elemental chlorine-free" (ECF) bleaching, bleaching
with chlorine dioxide, and "totally chlorine
free" (TCF) bleaching, bleaching with oxygen, ozone, and hydrogen peroxide.
Over the last decade various changes
have taken place that will influence bleaching technology for the next decade. There
have been dramatic shifts in fiber supply.
Forest utilization, particularly preservation
of old-growth forests is now much higher
on the public agenda than in the past.
Sustainability of forests is under closer scrutiny than ever before. Increasing restriction
of wood supply and increasing wood cost
must be expected over the next decade,
certainly in a number of important pulp
manufacturing regions. These factors will
require increasing emphasis on maximizing
yield in pulp manufacturing processes. In
the past ten years, extensive legislation on
recycling of paper has been enacted causing significant restructuring, in terms of fiber supply, in the newsprint industry.
In the early 199Os, markets were highly
competitive. There was an oversupply of
pulp which caused significant cutbacks in
production, low prices, and in many cases,
heavy financial losses. This situation stimulated marketing based on environmental
quality criteria. The demand for so-called
"environmentally superior" pulps, particularly those having lower quality and higher
cost, will undoubtedly
suffer in times of
tight markets.The market for the long term
will surely favor competition based on performance, cost, and other traditional criteria for industrial products.
The age and size of pulp and paper
mills is an element in the development
of
technology
that is often forgotten. The
average age of kraft mills in the United
States was twenty years (in 1994) (16).
For example, a mill started up in 1974 may
Pulp
in
(Slo~ge
nots~own)
Pulp
out
..
Fig. 7. Example
of a bleacb pltlllt jlowsbeet
::r
"0
'"
~....
......
for all OD(EO)D setJf'6ffU
uslllg rotary
drum
fJtU:Ullm filters.
a0c:
P-
o'
:;)
8
"tI
S'
,.,
:0'
'"
Ro
;y
Pr:;"
Ib
0....,
Pulp
~out
"0
1:1:1
n,.,
'"
::r
5"
rJQ
Fig. 8. Example
of a bleaeb pltlnt fiowsbeet
for an (OO)D(EO)(DN)D
lIefjllem:e using specialized
drum
washers
and diffusion
washers
(Ahlstrom
N
......
Kamyr).
N
N
~"0
,.,
~'"
e:
~Pulp
out
"tI
S'
,.,
:0"
n
'"
8"tI
(EOP)
R
r:;"
Ib
Pulp
out
Pulp
in
Fig. ,.
Examples
ofproeess efjlllpmtnrtjlowsbeets:
Deflbrator
botb using wash presses (SII'"
Upper) aflber
Inc.).
llnefor
bakb pulping
and OZfJ{PO) bleaeblng
and, Lower) a bleadnng
llnefor
tbe lIefjIIence OD(EOP)DD.
Chapter I 1: Introduction to Principles & Practice of Pulp Bleaching

have been designed as early as 1970 or
1971 and built with the technology and
equipment of the day. Many mills currently
in operation are much older. The average
production
rate of kraft pulping lines in
the United States is only 600 air-dry unbleached tonnes per day; the median is
much lower (16). (These statistics include
all kraft mills, bleached and unbleached).
Technological conversion and upgrading
for many older, smaller mills is more complex and expensive than is achieving stateof-the art technology
in large. modern
mills. In the coming decade, because of
the relatively large number of older, smaller
mills. greater resources in the form of operating and capital costs will be required
and the pace of change may be slower than
if only the upgrading of modem mills i~
considered.
Environmental issues have emerged as
crucial, strategic factors for western industrial enterprises. Environmental concern
and awareness have grown significantly and
have been globalized. There have been en-
23
vironmental campaigns on particular subjects such as industrial use of chlorine. dioxins from pulp bleaching, and old-growth
forestry.The complexity and sophistication
of environmental
criteria have increased
dramatically in the last ten years. Toxicity
testing of bleach plant effluents previously
was limited in Canada to the acute toxicity
test for rainbow trout. Now there is a very
wide array of biological response tests.
There has been a significant increase in the
scope and restrictiveness of environmental
regulations in the last decade; for example,
in 1984 dioxin and AOX were unknown
terms in the pulp and paper industry. Certainly in the next ten years more testing will
be required to meet even stricter regulations.
An important trend in bleaching technology development is the renewed effort to
devise ways to decrease discharge by recycling, concentrating. and burning effluents.
for instance by recycling kraft bleaching
effluents to the kraft black liquor system
for destruction in the recovery boiler. Com-
(ON)
24
plete elimination of kraft bleach plant effluents was originally proposed by in 19(i6
and attempted on a commercial scale in
Canada in 197684(17).There
are also currently several developmental
projects to
eliminate kraft mill bleaching effluent by
independent evaporation and burning.Two
bleached chemithermomechanical
mills in
Canada operate with no aqueous effluent;
all spent liquors are concentrated
and
burned (18). Over the next decade there will
be increasingly less material discharged
from bleaching processes as such processes
are progressively implemented.
1. Wells. S.D.. in"The Bleaching of Pulp;'TAPPI

Monograph
Series No. 10 (R.S. Hatch. Ed.)
TAPPI PRESS.Atlanta.1953.
Chap. 1.
2. Rapson.W:H. (Ed.),"The Bleaching of Pulp."
TAPPI Monograph
Series No. 27. TAPPI
PRESS. Atlanta, 1%3.
3. Singh. R.P. (Ed.), Tbe Bleaching
TAPPI PRESS.Atlanta.1979.
of Pulp.
S.A.. Pulping
Processes.
Publishers, New York, 1%5.
5. Reeve. D.W:. in Pulp and Paper Manufacture. Volume 5, Alkaline

Pulping. TAPPI
PRESS. Atlanta, 1987. pp. 391-469.
6. Higgins, S.H., A' History of Bleaching.

Longmans. Green. New York. 1924.
7. Opfermann. E. Hochberger, E.. Die Blieche
des ZelfstojJs, Bd. I and II (Bleaching of
Wood Pulp, Vol. I and II). Otto Elsner
Verlagsgesellschaft, Berlin. 1935.
8. Cockram, R.. Papermaker International
Fig. 10. Example of bleacb plant equipment

layout for
fllter wasbers (IMPCO PIllping Tecbnologies).
a D(EOP)(DN)D
sequence
using
compaction
baffle
10. Stefan,v.Pulp
R.A.. Pulp Pap. Int.
Pap. Int. 37(8):13
(1995).
11. "Canadian Pulp & Paper Capacity 1993/

19%," CPPA. Montreal, 1994.
12, Keaton. D.. Pulp Pap. 69(8):13(1995).
13. "Pulp and PaperTowards
2010 - An executive summary," Food and Agriculture
Organization of the United Nations. Rome. .
1994.
14. Rydholm. S.A., Pulping
Processes,
Interscience Publishers. New York. 1965.
p.1156.
15. Grundelius. R., "Oxidation equivalents.
OXE
References
4. Rydholm,
Interscience
58(8):38(1995).
9. Brennan. w: Pappens.
37(7):19(1995).
- an
alternative
to active
chlorine."
1991 International
Pulping Bleaching Conference Proceedings.
SPCI. Stockholm. p.
49.
16.}ohnson.
A.. Trepte. R.,Gleadow.
P.. and
Herschmiller.
D
Directions
in the
Fiberline". presented
at the Pulping Horizons Seminar.Washington,
DC. September.
1994.
17. Reeve. D.W:. Pulp
(1984).
Pap. Can. R5(2):T24
18. Evans.T
Startup of MillarWestern's
Discharge BCTMP Mill in Meadow
1992 Pulping Conference Preprints.
PRESS.Atlanta.p.1167.
Zero
Lake."
T APPI
SECTION II:
Raw Materials
Chapter 1:
Production of Unbleached Pulp
James L Minort
USDA Forest Service
Forest Products Laboratory2
Madison, Wisconsin
1. Fiber component. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
1.1 Fiber sources and characteristics. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 32
1.2 Fiber supply. . . . . . . . . . . . . .'. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 32
2. Pulping process. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
2.1 Classification of processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 33
2.2 Chemical pulping. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 35
2.3 Mechanical andchemimechanical pulping. . . . . . . . . . . . . . . . . . . . .. 41
2.4 Pulping of recycled fibers
43
3. Composition and properties of unbleached pulps . . . . . . . . . . . . . . . . ..
3.1 Chemical pulps. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
3.2 Mechanical and chemimechanical
pulps. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
3.3 Recycled fibers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
44
44
50
52
Retired as of May 1994
, The
Forest Products Laboratory is maintained in cooperation with the University ofWisconsin. This article was written and prepared by U.S. Government employees on official time,
and it is therefore in the public domain and not subject to copyright.
25
Chapter n 1: Production of Unbleached Pulp
Chapter n 1:
Production of
Unbleached Pulp
1. Fiber component
Pulp can be derived from wood fibers,
nonwood fibers, and secondary or recycled
fibers.The supply of fiber also varies, changing with availability, fiber production, and
consumption.
1.1 Fiber sources and characteristics
Fibrous material from plants, such as papyrus, wood, bark, and bamboo strips, have
been used as a source of writing materials
since the earliest civilizations. Papermaking,
the formation of paper from separated nbers, originated in China in 105 AD. Its development is credited toTs'ai-Lun, a servant
of the Imperial Court, who used flax, mulberry bark, and rags as his source of fibers.
At that time, parchment was used in Europe,
but during the Middle Ages, it was supplanted by paper made primarily from rags
and rope. The use of wood as a source of
papermaking fiber was not commercially
applied until the mid-1800s. However, because of availability, economic factors, and
technological advances, wood became the
dominant source of papermaking fiber in
North America and is presently the original
source of 99% of the pulp fiber produced
in the United States.
Wood fiber
Although virtually any wood can be
pulped by some process, certain tree species are commonly used for pulp because
of their fiber quality, ease of pulping, availability,and because they may not be as suitable for other wood products. The most
frequently
used pulpwoods
in North
America are listed in Table 1.
The advantages of wood relative to other
renewable plant fiber sources include yearround availability rather than ~a5onal harvest, relative stability when stored as logs
or chips, the ability to serve as a waste resource from other wood products opera-
27
tions such as chips and residues from

sawmilling, relatively low content of silicates and other minerals, low cost of growing, and the ability to tailor fiber types to
products because of morphological differences among tree species. Disadvantages
include long growth times, high energy
harvesting and processing demands, and,
more recently, public concern about the
impact of harvesting on forest ecosystems.
Trees are classified botanically as softwoods or evergreens, which are gymnosperms, and hardwoods or broad-leaved
deciduous trees, which are dicotyledon
angiosperms. The chemistry and anatomy
of wood varies with the tree species, but
there are gross similarities within the tWo
classifications. Softwoods, which are preferred for many pulp products because of
their long fibers, generally contain a higher
percentage of lignin (26-32% on an extractives-free basis) and a lower percentage of
hemicellulose
(14-17%) than the hardwoods, which contain 17-26% lignin and 1827% hemicellulose.The
ranges of chemical
composition in wood are shown in Table 2.
Softwood anatomy and morphology
A schematic cross-section
of pine is
shown in Fig. 1 as a representation of softwood anatomy. The main cell type is the
axially aligned tracheid (fR). Although in
botanical terminology tracheids are not
considered to be true fibers, they are the
papermaking fibers in softwoods and are
referred to as such throughout this chapter
as is common practice in the industry. Other
cell types in softwoods are the fusiform
wood ray (FWR) and wood ray (WR) cells,
and the longitudinal and epithelial parenchyma, which are the cells surrounding the
horizontal and vertical resin ducts (HRD and
VRD, respectively).
As a tree grows, the cells are produced
in concentric lamellae in the cambium layer,
which is betWeen the bark and the wood.
In the spring, when moisture is plentiful and
the tree is growing rapidly, the tracheid cell
wall is (hin (3.; /lm) ana (he hollow centCf
or lumen is relatively large (26-43 J.I.ffi).This
portion of the woody tissue is called earlywood (EW). During the summer or later in
28
Table 1. wood species
used for palpl,,&
i"
North America.
Softwood
Dominant
Secondary
Hardwood
Dominant
Secondary
Spruce, fir,
white pine
Hemlock,
tamarack
Hickory
South
Yellow pines
Cypress
Oaks, gums
Northwest
Douglas-fir,
western
hemlock
True firs,
spruce
Red alder
Lake states
Jack pine,
White pine,
red pine
Red oak,
tamarack
Birch
aspen, maple
Douglas-fir,
western hemlock, spruce,
lodgepole pine
Western red
cedar. true firs
Aspen,
cottonwood,
red alder
Hybrid
poplars
Aspen
Balsam fir
Region
United States
Northeast
Canada"
British Columbia
Oak aspen,
other poplar,
maple, birch
Prairie region
Spruce, pine
Ontario
Jack pine,
spruce
Balsam fir,
larch, red pine
Aspen, beech
Birch, maple
Quebec
Black spruce,
jack pine,
balsam fir
White spruce
Aspen,beech
Birch, maple
Maritime region
Spruce,
balsam fir
Eastern hemlock,
eastern white
pine, red pine
Aspen, birch
Beech, maple
a Reference
(1)
the growing season, the cell wall thickness

increases to 8-12 ~m and the outside diameter decreases from about 47 ~m to about
29 J.I.ffiin species such as the southern pines.
These cells form the latewood (LW). The
sequential combination
of seasonal cell
types leads to the characteristic annual ring
(AR) of trees, which is more or less distinct
in softwoods depending on the species.
In the living tree, nutrients flow through
the cells of the sapwood.The pattern of liquid conductance in wood is also important
for the penetration of chemicals in the initial stage of chemical pulping. In softwoods,
liquid is transferred from rays to tracheids
and between tracheids through tiny voids
or pits (P) in the cell wall. Usually, pits in
adjacent cells are aligned so that a passage
betWeen the lumens of the tWo cells is
formed that is blocked only by a thin pit

membrane of interceIlular
substance. In
bordered pits (BP), this membrane contains
a thickened circular portion called a torus,
which functions as a check valve to seal the
passage against a return flow of liquid.
Hardwood anatomy and morphology
Figure 2 is a schematic cross-section of
the structure of yellow poplar as a typical
hardwood. Hardwoods have a more varied
and complex ceIl arrangement than softwoods.The main structural element of hardwoods is the wood fiber (F), which is
significantly shorter than the softwood tracheid (1-2 mm compared with 3-6 rom) and
generally thinner, that is, ca. 20 ~m in diameter. Hardwoods also contain a sizable
proportion of short, large-diameter cells or
Chapter III: Production of Unbleached Pulp
Fig. 1. SebemIItk
IrtIcbelil;
sectUm of softwood. Bp, bordereII pit; P, prtmllry

J7lD, vertiul
restn dru:t; tmd WR, wood ray.
TtIble 2. Cbemklll wmpositllln

Component
Cellulose
of wood'
Hardwoods
Softwoods
42-49
41-46
O-acetyl-4-0-methyl-
gIucuronoxylan
20-30
O-acetylgalacto-
gIucomannan
Glucomannan
16-20
2-3
4-O-methylglucuro-
noarabinoxylan
Pectin materials
Arabinogalactan
GaIactoglucomannan
Starch
lignin
Ash
Trace
Trace
Trace
20-26
0.2-0.8
8-11
1
2-3
Trace
26-31
0.2-0.4
Extractives
3-8
10-25
Uronic anhydride
3-5
3-4
IPercentageof weight of extracted wood, except
extractives analyses
wall; EIlI, etlrlywood;
Lw, IIItewood;
29
30
TR,
vessels (V) through which sap is transported.Vessels may be larger in earlywood,

as in oaks and hickories,
or uniform
throughout the annual ring, as in yellow
poplar and aspen. Vessels have open ends
or a connecting grate-like tissue called a
scalarifonn plate (SC).Vessels are not desirable as papennaking fibers and special papermaking techniques
must be used to
retain the vessels in the paper matrix. If this
is not done, the vessels may be lifted from
the paper surface by ink-coated type during contact printing.This is called "picking"
and is manifested as small white specks in
the printed image.
Hardwood fibers have simple pits that are
smaller and do not contain the torus system of the softwood bordered pits.Apparently, this difference L~related to the fact
that the vessels perform the primary liquid
transport function in hardwoods.Therefore,
Fig. 2. Scbenultk
sectllln of krdwood.
AP, lIXiIIl ptlreru:bymtI; F, wood ftber; EIlI, etlrlywood;
6RB, grollltb ring bollndsry; P, pit; WR, wood ray; and SC SC41arlform plllte.
the cross-fiber liquid flow is greatly restricted in hardwoods

in contrast with
softwoods. In general, there is less differentiation in earlywood (EW) and latewood
(LW) fibers than in those of softwoods.The
annual ring (AR) is shown by the one or two
layers of termina1 parenchyma cells, which
form at the end of the growing season.
With the maturation of softwoods and
hardwoods, the parenchyma cells at the
core die. This portion of the wood is called
heartwood, and it often contains polyphenols, flavones, and other colored compounds that do not occur in the contrasting
sapwood.The imparted color usually allows
a clear, visual distinction to be made between heartwood and sapwood, depending
on the species. Heartwood compounds,
such as dihydroquercetin in Douglas-fir,may
cause problems in pulping or bleaching.
LIlI, latewood;
N'onwood fiber
The quality of nonwood fiber varies. The
strength of fibers from some bast fiber
plants, such as hemp, jute, and flax, exceeds
that of softwood fibers. In general, however,
the stalk or core fibers from cereal grains,
grasses, and other "straw" pulps are closer
to hardwood fibers in their characteristics.
Nonwood fibers are a major fiber source in
some parts of the world, notably in much
of Asia where wood resources are limited.
At present in the United States,nonwood
fibers are used primarily for specialty paper grades. Cotton fibers, in the form of rags
or cotton linters, are used in rag-content
bond paper and various specialty grades
such as onionskin, maps. charts, and blueprint papers.
Hibiscus cannabinus (kenai) is used in
Asia as a source of papennaking fiber. It has
been studied extensively as a potential fi-
Chapter II 1: Production of Unbleached Pulp
31
40
1000
(/)
Q)
c
c
0
800
600
'C
Q)
E 400
c
~200
o
1952 1962 1970 1976 1976 1986 1990 2000 2010 2020 2030 2040
Year
Sawlogs
Veneer logs
FIg. 3. U.S. f'Otl1UItt'OtJd COtfSfImption,
1952-1986,
Pulpwood
Misc.products
witb 1989 RPA btIse projections
Fuelwood
of dem4rul
to 20f0.
Data
from (4).
ber-producing
crop in the United States
because it can be grown in the South and
in areas where wood is not abundant. largescale trials have been conducted, but there
is no commercial
kenaf pulp mill in the
United States at present.
Secondary
fibers
and wood
residues
The term "secondary fibers" refers to recycled papers. Secondary fibers are categorized according
to a single industry-wide
classification
scheme that has been maintained for many years by the Institute for
Scrap Recycling
Industries
(lSRI). These
categories (of which several dozen are in
use commercially)
are aggregated into five
principal
groups that are also recognized
by industry trade associations and by the
U.S. Department
of Commerce. For statistical purposes,
these categories
are Old
Newspapers
(ONP), Old Corrugated Containers (OCC), Mixed, Pulp Substitutes, and
High-Grade
Deinking. ONP is commonly
reconverted
into newsprint
and therefore
requires bleaching. It may be used for paperboard or non-paper products that do not
require bleaching. acc are also reconverted
to their original products and do not require
bleaching.
However, some mills upgrade
OCC to bleached printing and writing papers (2,3). Mixed papers, as the name implies, contain a variety of fiber types, some
of which may be bleachable. Pulp Substitutes are clean wastepapers such as envelope cuttings, tabulating
cards, and other
converting
wastes. Although
Pulp Substitutes may include colored papers, the white
papers are used with no further bleaching.
The High-Grade Deinking category includes
coated and fine papers that are bleachable.
The rate of recycling and use of secondary fibers in the United States has increased
substantially in the 1990s.A record 26 million tons of secondary
fibers were consumed by the U.S. industry
in 1993. The
secondary fiber input represented
about
30% by weight of the final production.
In addition to recycled paper, a substantial portion of the total pulp fiber input is
obtained as wood residues, primarily from
sawmills and plywood
mills. Wood chips,
shavings, sawdust, and other residues accounted for roughly 40% of the approximately 100 million
cords of pulpwood
consumed
Mmllillly
by U.S. mills in the e:J.fly
1990s; the remaining
60% of pulpwood
consumption
was obtained almost entirely
from domestic pulpwood
harvest.
Pulp Bleaching
-Principles
and Practice
alternatives to calcium. Magnesium sulfite

has decreasing solubility above pH 5, but
sodium and ammonium sulfites are soluble
over the entire pH range.
Acid-catalyzed
hydrolysis
of the glycosidic linkages in polysaccharides
is much
more rapid than alkali-catalyzed hydrolysis.
Sulfite pulping at low pH therefore must be
carried out at a relatively low temperature
(135C) to avoid excessive polysaccharide
depolymerization.The
lower pulp strength
of acid sulfite pulps compared with those
of kraft pulps may reflect this reaction.
Other factors, such as accessibility and the
influence
of hemicelluloses,
are also involved in determining
pulp strength because the weight-average
degree
of
polymerization
(DP) of cellulose in acid
sulfite pulps is usually higher than that in
comparable kraft pulps.
A low-hemicellulose
pulp that is suitable
for producing cellulose derivatives such as
rayon or cellulose acetate can be made by a
two-stage sequence as typified by the Sivola
process. The Sivola process employs
an
acidic first stage to reduce the DP of the
hemicelluloses,
which are then dissolved
and removed in an alkaline second stage.
The reducing end groups of polysaccharide chains are oxidized to aldonic acids by
bisulfite.
Also, in alkali, the softwood
gaIactoglucomannan
is deacetylated and the
hemicellulose
then tends to redeposit on
the cellulose microfibrils.
These carbohydrate-preserving
reactions are promoted if
a mildly alkaline first stage is followed by a
more acidic stage, as occurs in the Stora
process.
Full chemical pulp production
by the
sulfite process has almost disappeared in the
United States, but it is used in Europe. Sulfite
pulps have properties that are desirable for
tissues and top-quality fine papers, and the
pulps are more easily bleached than are kraft
pulps.
Anthraquinone
may also be used in alkaline or neutral sulfite pulping to accelerate
the rate and increase pulp yield. Such processes have not been applied commercially
in the United States, but they may appear
in new procedures presently under development (see following text).
Miscellaneous chemical processes

The motivation for research on new
pulping processes has generally been to
overcome weaknesses of the kraft process
which include low yield, air pollution
concerns,
and high capital cost. Many
chemical pulping processes have been demonstrated to be technically feasible in the
laboratory. However, despite its weaknesses, the kraft process has been highly
developed. It uses inexpensive, recoverable
chemicals and produces a high quality paperrnaking pulp. These facts and the large
investment that has already been made in
kraft pulp mills makes kraft pulping a formidable competitor to new, untested processes.At present, an additional motivation
to develop a new pulping process is the
need to produce a chemical pulp that can
be bleached without the use of chlorine.
Research on new delignification processes
has been particularly intense in Germany,
which has very strict emission regulations
and which imposes heavy taxes on the discharge of cWorinated effluents.
Because of the dramatically different
chemical structures of lignin and polysaccharides, it would be expected that a highly
selective separation of these two substances
could be achieved based on solubility differences (i.e., solubility of lignin fragments
compared
with that of low molecular
weight hemicelluloses). Indeed, many of the
new pulping systems that have been proposed utilize organic solvents, and the procedures are referred to collectively
as
organosolv pulping (5). Of the various
experimental
processes
proposed,
the
ASAM, ALCELL, and ORGANOCELL processes have reached the semicommercial
stage of development.
The ASAM process uses alkaline sulfite
with the addition of anthraquinone
and
methanol. This process is not strictly an
organosolv process because the proportion
of methanol is low (15 volume percent).The
ASAM process is reported to produce hardwood pulps with kappa numbers of 8-12
and softwood pulps with kappa numbers
of 17-22 (36). Screened yields are higher
than those from the kraft process and the

pulps are generally brighter. ASAM pulps
may be bleached without chlorine using a
four-stage (OZEP) bleaching sequence.
TheALCELL process has been successful
only with hardwoods.The process involves
the use of ethanol-water mixtures at a pH
maintained by the acetic acid generated
from the wood (7). Pulping is stopped at
a higher residual lignin content than is usual
for kraft pulps, but the pulp is reported to
have an excellent
response to oxygen
bleaching, and fully bleached pulps are produced without the use of cWorine (8).
The ORGANOCEll
process utilizes a
pulping system consisting of sodium hydroxide in methanol and anthraquinone is
added as a catalyst. Hardwoods, softwoods,
and nonwood plants have been pulped.
Pulps from spruce and pine are nearly as
strong as kraft pulps, but are bleached more
easily (9). The pulps may be bleached to
80% ISO brightness without cWorine compounds by using oxygen and peroxide. A
brightness of 90-92% ISO can be reached
by the additional use of cWorine dioxide.
Two other processes have reached advanced
stages of development.
The
ACETOCELL process employs acetic acid as
the pulping reagent. Bleaching is performed
with ozone in acetic acid, followed by hydrogen peroxide, and peracetic acid (40).
The MILOX process appears to be especially
suited to hardwoods.
In this process,
performic acid is used to pulp to kappa
numbers of 3-5. The low-lignin pulps are
then bleached with hydrogen peroxide
(41).
None of the organosolv pulping processes is likely to replace the kraft process,
but they may find limited application where
the local situation is particularly favorable
for them such as locations with an abundance of low-density hardwood resource or
in areas where the kraft process may be
restricted for economic or environmental
reasons.
2.3 Mechanical and chemimechanical
pulping
Mechanical pulping, which originally was

the groundwood process utilizing a grindstone to fiberize bolts of wood, now in-
41
eludes refiner mechanical

pulping and
thermomechanical
pulping processes that
utilize disc attrition mills to fiberize wood
chips or sawdust. These processes can produce stronger pulps than groundwood
pulps but also require
more energy.
Chemimechanical
pulping methods are
those in which some chemical treatment is
applied before or during mechanical
pulping for purposes of softening the wood,
modifying pulp properties, and reducing
energy.
Groundwood pulping
Early production of groundwood pulp
involved pressing bolts of wet wood against
a wetted rotating grindstone with the axis
of the wood parallel to the axis ofthe wheel.
Improvements have been made in the composition and speed of the grinding wheel,
in methods of feeding the wood and pressing it against the stone, and in the size and
capacity of the units.The original sandstone
wheel has been replaced by mechanically
stronger, synthetic composite stones produced from fine grits of silicon carbide or
alumina embedded in a softer ceramic matrix; therefore, the harder grit particles
project from the surface of the wheel. Synthetic stones have the mechanical strength
to operate at peripheral surface speeds of
about 1200-1400 m/min.
Pulp quality depends on a number of
variables, including grinder variables - peripheral stone speed, grit size and number
per unit area, and stone surface; wood variables - species and moisture content; and
process variables - grinding pressure, pit
consistency, and temperature. The combination of moisture and raised temperature
softens the lignin.The grit diameter is about
0.2 mm, that is, about 10 times the fiber
diameter. The repeated compression-decompression action generates heat and soft.
ens the wood matrix before it reaches the
grinding surface where the loosened fibers
are carried from the wood. Temperatures
in the immediate grinding zone can be in
the 180 - 1900( range. The movement of
water and removal of pulp control and dissipate the heat, thus preventing charring of
the wood. It is advantageous to allow the
42
water temperature in the pit to rise to 70 90C to achieve a higher grinding rate,
lower energy consumption, and higher pulp
strength than are possible at lower temperatures.
Presteaming
of wood is practiced in
Europe to add moisture and to soften the
lignin. The procedure is especially advantageous with some hardwoods. In the late
1970s and early 1980s, it was demonstrated
that pressurizing the region surrounding a
stone grinder to 100-300 kPa (1-3 attn) markedly improves the strength and fiber integrity of the pulp. This process retains the
advantages of low energy consumption and
high opacity (42). Recently, the pressure has
been increased to 450 kPa, with continuing improvements
in properties. This is
called the Super Pressure Groundwood process (43).
Refiner mechanical pulping
The conventional groundwood process
requires bolts of roundwood as raw material. In the 1950s, the refiner mechanical
pulping (RMP) process was developed,
which produced a stronger pulp and utilized various supplies of wood chips, sawmill residuals, and sawdust. However, the
energy requirement of RMP is higher and
the pulp does not have the opacity of stone
groundwood pulp.The refiners are rotatingdisk attrition mills. The plates are paired
face-to-face with a small interval between
them. Either one disc rotates against a stationary disc or they both move in a
counterrotating
manner. The chips are fed
through channels near the shaft in one of
the discs and move toward the periphery
while undergoing attrition. They emerge
from the periphery as single fibers or fiber
fragments, including ribbons and fibrils that
are formed by the unraveling of the spiral
fiber walls of individual fibers.This process
is termed fibrillation. These thin, flexible
elements considerably improve the bonding properties of mechanical pulps.
Th~rm()m~chanical pulping
If chips are presteamed to 110 130C

before refining, they become malleable and
do not fracture readily under the impact of
the refiner bars. Refining can also be performed under pressure. This modification
is called thermomechanical
pulping (TMP).
If the presteaming time and temperature are
limited, higher steam pressures can be used
in the refiners without reducing the pulp
quality. The heat can then be recovered for
other uses such as paper drying At temperatures from 100C to about 150C, wet lignin softens but does not flow.When the hot
chips are fiberized in a refiner at high consistency, whole individual fibers are released; separation occurs in the S1 layer of
the cell wall, and the same ribbonlike material described for RMP is produced. The
amount of fibrillization depends on the refining conditions and is critical to the properties of the pulp. Much less fiber
fragmentation occurs in TMP pulps than in
groundwood pulps or in those produced by
RMP. The production
of TMP pulps increased dramatically after its introduction
in the early 1970s because they could be
substituted for conventional groundwood
pulps in newsprint blends to give a stronger paper. Therefore, smaller quantities of
the more expensive, lower yield chemical
pulps were required for reinforcement.
Unfortunately, the TMP process consumes
considerably more energy than does RMP.
Combinations of mechanicaland
chemical pulping
Chemicals may be added to the wood or
fiber in any of the mechanical processes to
improve strength properties, reduce mechanical energy, reduce the shive content,
or bleach the pulp. Very often there is a
trade-off in properties or benefits obtained,
and each process is optimized to minimize
costs for the particular properties desired.
Frequently, chemical treatment lowers the
yield and decreases the optical properties
of brightness, opacity, and light scattering.
Chemithermomechanical
pulping
The strength properties
of thermomechanical pulps can be increased by a mild
pretreatment with 1-6% sodium sulflte at pH
9-12.The chips are impregnated with chemicals, steamed to 130 - 170C, then refined.
The refining can be at atmospheric pressure

or pressurized, and one or two refining
stages may be employed. Alternatively, the
chemical may be added at the refiners, between refining stages, or as a post-treatment.
The pulp yield, 86-92%, is 3-5% lower than
that in TMP.
Chemirefiner mechanical pulping

Hardwoods, particularly the denser species, cannot be refined directly to produce
a satisfactory papermaking pulp. The cold
soda process, which is especially suited to
dense hardwoods, is used in Australia to
pulp eucalyptus.As the name implies, wood
chips are impregnated with sodium hydroxide solution without heating. The treated
chips are then defiberized by refining at
atmospheric pressure in one or two stages.
In North America, chemirefinermechanical
pulp (CRMP) is produced by refining chips
that have been pretreated with sodium hydroxide and sodium sulfite and heated to
effect lignin sulfonation.
Chemimechanical pulpinIJ
There are several variations of mechanical pulping with sulfite addition that may
be classified as chemimechanical
pulping
Table 4. V.II opertlllmlsfor pulpl.g
recycledftbers
(CMP). The regular CMP process for softwoods uses sodium sulfite, 12-17% on
wood, 10 - 60 min at 130 - 170C, and twostage refining at atmospheric pressure (44).
Variations include using bisulfite at lower
pH, longer pulping time, and vapor-phase
pulping. Mechanical pulps can also be upgraded by sulfonating the oversize reject
fractions obtained by screening mechanical pulps. This fraction contains long fibers
that can be chemimechanically
pulped to
produce a stronger reinforcing pulp for the
main mechanical pulp production.
Semichemical pulping
Semi chemical pulping (see Table 3) is
chemical pulping that has been terminated
at a higher yield and lignin content than full
chemical pulping.These pulps typically are
used unbleached in corrugated boxes.
2.4 Pulping of recycled fibers
Recycled fibers have previously been
pulped by one of the existing wood pulping
processes. Hence, the equipment used to
slurry wastepapers back into a pulp form is
called a repulper, or if it is understood that
recycling is being discussed,
simply a
(45).
Function
Unit operation
Removes wire from bales
Bale de-wirer
High-density
pulper
Wastepaper
consistency,
High-density
cleaners
Remove staples, heavy debris, glass
pulped to approximately
chemicals added
Coarse screens
Remove large contaminants
Fine screens
Remove spherical
Washing
Removes fine particles

ink, clays, pigment
Belt press/screw
press
Thru-flow
Thickens
15%
plastics and stickies

less than 40 1lID,fines,
stock to 30%-35% consistency
Removes hydrophobic particles greater than

40 Im I , ink specs, stickies, clay
Flotation
cleaners
43
Remove light particles, stickies
Forward-flow
cleaners
Remove nonattached
High-intensity
dispersion
Loosens ink from fiber, breaks down particles,

homogenizes pulp
ink specs
OAF clarifier
Removes sludge and fiber from process water
Bleach towers
Provide residence
stripping
time for bleaching
and color
44
Table 5. Cbnnlcfll composltl08 of ,,.bletICbed clwmkol pulps.
Pulp constituents (%)

Wood species
Pulping process
Loblolly pine (47)
Kraft
Pulp yield
Lignin
Glucan
Mannan
Xylan
50
5
6.5
4
<;
37
8.6
5.8
50
5
5
4
36
36.6
79
8
18
9
6
3% Polysulfide
Spruce (48)
7% Polysulfide
Kraft
Polysulfide
55
Acid sulfite
Aspen (49)
Beech (50)
Kraft
55
58
Acid sulfite
64
Sulfite
45
Kraft-AQ
50
ASAM'I
ASAMn
51
'A1kaline sulfite with addition of anthraquinone
3
6
73
77
11
5.5
80.1
12.8
5.3
2.2
78
1.9
87.5
1.7
9.6
10.8
3.2
1.9
1.8
53
75.5
24.5
76.7
23.3
25.7
74.3
and methanol
pulper. Repulpers may be of various designs, but the function is to re-swell the fibers and to gently break up the paper
structure with minimum damage to individual fibers. Repulping may be done at different
consistencies
and pH levels
depending on the starting material and the
desired outcome.Various chemicals such as
surfactants and bleaching agents may be
added at this stage. The major treatment of
recycled pulp is contaminant removal, including the deinking of printed papers.Various screening and cleaning techniques are
employed to remove the wide variety of
contaminants that may be present. An example of a sequence of unit operations for
pulping and cleaning recycled papers is
given inTable 4 (45).
Deinking can be particularly problematic
and, because of its importance, special processes have been developed. Historically,
two major techniques of deinking have
been used: washing and flotation.The washing process is similar to laundering where
detergents are used to wash the contaminants from the fibers. Flotation is a method
of removing hydrophobic
contaminants
such as oil-based inks. It is based on the fact
that such materials selectively cling to air
bubbles passing through the aqueous sus-
pension of the contaminated

fibers. The
ink contaminants
are removed as a dark
froth; the purified pulp emerges as a lowconsistency suspension in water.
3. Composition and properties

of unbleached pulps
Pulping affects the composition
and
properties of fibers. The following section
describes
changes in chemical
pulps,
chemimechanical
pulps, and recycled fibers. Each pulp is also described in terms
of its "bleachability"
processed
ened.
or treated
the ease with which
pulp can be bright-
3.1 Chemical pulps

Composition
In all chemical
pulping
processes,
changes occur in the chemical composition
of the fibers. Some of these changes are intentional, others are unavoidable consequences of the procedure. None of the
commercially employed chemical processes
is completely specific for lignin removal,
and significant portions of the hemicelluloses and a small amount of cellulose are dissolved during pulping (see Chap. III 1 for
details of the chemical changes). Even
within a given pulping process, changes in
50
'"
~'" 40
if 30
o
'" 20
~
:>
10
10
20
30
Kappa number
40
Fig. 8. Loss of viscosity dIIrlrtg IImft pulpirtg

bleachirtg of softwood pulp.
and CE
chemical composition depend on the conditions employed. For example, in the kraft
process, both dissolved hemicelluloses and
lignin reprecipitate onto the fibers, esp~cially if there is a decrease in alkalinity at
the end of the pulping. In wood, the xylans
in hardwoods and the glucomannans in softwoods are substituted with acetyl groups.
Saponification of these esters under alka.
line pulping conditions
leads to lessbranched structures,
which are readily
accommodated onto the surface of the linear cellulose microfibrils. The higher alkalinity in extended
pulping
serves to
minimize the reprecipitation
of lignin, but
the reprecipitation of the hemicelluloses is
also decreased. Another factor that influences the chemical composition of kraft
pulps is the use of pulping additives, such
as anthraquinone
or polysulfide, which
leads to increased pulp yields through
greater retention of the hemicelluloses.
The chemical composition of pulps from
various chemical pulping processes is given
inTable 5. More than 98"10of the pulp weight
is usually accounted for by the summation
of lignin and the five major wood sugarsglucose, mannose, xylose, galactose, and
arabinose. In summative analyses, the sugars are calculated as if they were in the polymeric (i.e., anhydro) form. Additionally,
hemicelluloses contain uronic acid units;
for example, the uronic acid content of pine
kraft pulp is about 1% (46). For many purposes, pulps may be chemically characterized by analysis for glucose, mannose, and
xylose. The glucose analysis provides an
45
estimate of cellulose after making a correction for glucomannan based on the mannose content.The xylose analysis represents
the amount of xylan. Galactose and arabinose are present primarily as substituent
groups on the major hemicellulose chains.
There are exceptions to this general rule
as,for example, in the arabinogalactan from
larch.
The exact chemical composition
of
chemical pulps is not as important in influencing the physical properties of the pulps
as are other factors such as morphological
differences. However, the lignin content is
important to bleaching and optical properties. Carbohydrate analyses provide information on pulp yields and the relative
selectivity (removal of carbohydrates compared with removal of lignin) of the pulping
process. The proportion of glucose in the
total carbohydrate analysis provides an indication of the weight percent yield of the
pulp because, as a first approximation, the
cellulose content of pulp can be considered
to be constant on a wood basis throughout
pulping, and therefore, for a given degree
of pulping, differences in yield are due to
differences in hemicellulose retention.
During delignification, the pulp fibers
become more flexible and malleable, and
on application of relatively low pressures,
delignified pulp fibers can be flattened to
form strong, well-bonded papers (Fig. 9).
Interfiber bonds consist primarily of hydrogen bonds, and the extent of bonding of a
fiber is proportional to the surface area of
the fiber in physical contact with other fibers. Although the location of hemicelluloses and their contribution to fiber strength
is not completely understood, an increased
hemicellulose content generally correlates
with increased fiber bonding.
The ash content is a low percentage of
the pulp weight, but the trace metals in pulp
can have a significant influence on bleaching. Metals may affect the bleachability of
unbleached pulps by forming colored complexes with organic pulp constituents, particularly with phenolics such as lignin.
Heavy (transition) metals also interfere with
oxygen-based bleaching agents such as oxy-
46
Pulp Bleaching
-Principles
Fig. ,. Electrort
and Practice
micrograph
of softwood
gen, hydrogen peroxide, and ozone by catalyzing their decomposition and often initiating the formation of intermediate
free
radicals such as the hydroxyl radical, which
degrade the pulp. Metals are initially present
in wood and are also introduced from the
process water and equipment. Of the common transition metals, copper and iron are
often harmful. Manganese can sometimes
show positive effects with oxidative reagents depending on conditions (51).
The results of some ash analyses performed at the Forest Products Laboratory,
USDA Forest Service (52,53) are shown in
Table 6. Ash analysis data are very dependent on local processing conditions as well
as the wood source. For example, kraft
pulps produced at the Forest Products Laboratory tend to be high in copper and low in
manganese compared with pulps from
other sources. Mills often use chelating
agents or mineral acids to reduce the heavy
metal content of pulps. Iron is particularly
difficult to remove by any means. Some resultS of pulp treatment with the chelating
agent, diethylenetriaminepentaacetic
acid
pentasodium salt (DTPA), are also shown
in Table 6.
Properties
Pulp physical properties that affect the
bleaching operation include fiber strength,
kraft /JtIJW1'.
brightness, opacity, accessibility of residual

lignin to bleaching agents, and heterogeneity.
Fiber strength
Many different physical tests can be performed on pulp and paper, and compilations of standardized
test methods are
maintained by various pulp and paper technical associations. The major test procedures used in North America are those of
the Technical Association of the Pulp and
Paper Industry (TAPPl), the Canadian Pulp
and Paper Association
(CPPA), and the
American Society forTesting and Materials
(ASTM). Other important pulp and paper
test methods used internationally are those
of the Scandinavian Pulp, Paper, and Board
Testing Committee (SCAN), the Technical
Association
of the Australian and New
Zealand Pulp and Paper Industry (APPITA),
and the International Organization for Standardization (ISO).
With the exception of viscosity, the physical testing of unbleached and bleached pulp
is usually performed in the form of a paper
sheet. Pulp viscosity is related to the degree
of polymerization of the component polymers through the Mark-Houwink equation,
[1]]
= KMa. Because cellulose. the main
structural element, has by far the highest
molecular weight and makes up most of the
weight of the pulp fibers, pulp viscosity is
47
14b1e 6. Melli' amtertl of ""lfWIted IUUlDTPA.tJWIted /JII'PS (5Z,53).
Pulp'
Spruce groundwood
Untreated
Treated
Loblolly pine groundwood
Untreated
Treated
Aspen groundwood
Untreated
Treated
Loblolly pine kraft
Untreated
Treated
Aspen kraft
Untreated
Treated
Commercial pine kraft
(untreated)
Laboratory-made
pulps, except
Metal (ppm)
Zn
K
Ca
Mg
Na
286
<60
1,530
1,240
329
270
185
<60
9
3
117
<60
572
504
111
96
1,410
238
2
2
16
4
158
<50
1,190
1,040
165
144
<50
<50
49
37
66
24
14
4
<50
<50
2,470
1,730
465
329
<50
<50
4
2
13
12
63
30
19
7
<50
<50
3,600
2,950
767
645
<50
65
73
33
Mn
Fe
Cu
85
18
11
10
2
5
105
13
46
16
29
28
3
5
30
2
18
16
20
6
as noted.
considered to be proportional to the cellulose chain length. For conventional kraft

pulps, the viscosity drops in a curvilinear
fashion with pulping (Fig. 8). Below a certain viscosity level (about 16 mPa. s), paper
strength traditionally has been considered
to decline. In recent years, the significance
of the lower limit of viscosity has been challenged in reductive alkaline pulping (54),
ozone bleaching
(55), and extended
pulping (56). In some instances, pulps having a lower viscosity have been converted
to papers of equivalent strength to those
of higher viscosity.
Usually the strength of unbleached,
bleachable-grade
kraft pulps is somewhat
higher but close to that of the final bleached
pulp. This is because a major objective of
bleaching is to eliminate pulp color with a
minimum amount of damage to the fibers.
Removal of the last few percent of lignin
does not impart any strength improvement
in the form of additional fiber flexibility, but
a slight benefit is obtained because of the
lower fiber weight (see following text).
Although numerous physical tests are

available, the "strength" of bleachable grade
fibers is frequently expressed by two tests
and the relationship between them. The
tensile strength, or variations of it, is proportional to the extent of interfiber bonding.The tearing strength is related to single
fiber strength, but it is also influenced by
the extent of bonding in the paper sheet.
When softwood kraft pulps are beaten to
increase interfiber bonding, the resultant
papers generally show an increase in tensile properties and a decrease in tearing
properties.The "strength" properties of different pulps are therefore compared by
means of a graph such as Fig. 10 (57), in
which the tensile strength of the corresponding paper sheet is plotted against the
tearing strength. Paper sheets having the
highest tear and tensile strengths are the
strongest.
Sulflte pulps are generally considered to
be weaker than kraft pulps but the strength
of alkaline sulfite pulps approaches that of
kraft pulps. Acid sulfite pulps have bond-
48
ing properties equal to those of kraft, but

their tearing properties are 10wer.The yields
of sulfite pulps in general are somewhat
higher than those of the kraft process at the
same lignin content. The properties
of
sulfite pulps can be varied by changing the
pH and by using multi-stage pulping systems. In such cases, pulp strength varies inversely with yield at the same lignin
content. This is largely a consequence
of
paper strength being based on a fixed
weight of paper; if the weight of individual
fibers is increased, the load must be borne
by fewer fibers.
Several miscellaneous chemical pulping
processes were discussed earlier in this
chapter. With kraft pulp properties as the
standard for comparison, it appears that
pulps produced in other alkaline processes
may have strength similar to that of kraft
pulps. In cases where softwoods can be
pulped by organosolv and acid processes,
the pulp properties are likely to be more
similar to those of sulfite pulps than to kraft
pulps.The acidic solvent processes may be
limited by strength considerations to the
pulping of hardwoods.
Optical properties
The main optical properties
of unbleached kraft pulps are brightness and
opacity. The brightness of these pulps is
very low (Fig. 7) and is raised to the desired level by bleaching. Opacity, which is
related to the light absorption and scattering coefficients, decreases during bleaching because of the removal of light-absorbing chromophores.
Opacity is generally
adjusted to the desired level by the addition of fillers such as clay or titanium dioxide. Unbleached
sulfite
pulps
are
significantly brighter than unbleached kraft
pulps from the same wood species.
Accessibility of lignin
On the molecular level, micropores in
wood pulp cell walls are distributed such
that polymers of increasing size are increas-
ingly excluded from interior regions of the

wall. The phenomenon is similar to that uti.
lized in solute exclusion chromatography.
In fact, the solute exclusion technique has
been utilized to measure the pore size distribution of pulps (58,59). As wood fibers
are pulped, the size of the lignin fragments
that diffuse out increases, indicating that the
size of the pore openings is increasing.
Researchers have observed that treatment of unbleached pulps with hemicellulase enzymes improves the bleachability of
the pulps (see Chap. IV 7). Removal of some
hemicelluloses
apparently improves
the
accessibility of residual lignin to chemical
bleaching agents. One explanation is that
the accessibility is restricted by xylan readsorbed on the kraft pulp during the
pulping process (60) and that the enzymes
act to remove this restriction. The issue of
whether the hemicellulose hydrolyzed by
the enzyme is re-adsorbed hemicellulose has
not been resolved, but data showing that
the cell wall pore sizes are larger after the
enzyme treatment (61) certainly suggest
that hydrolase enzymes do remove restrictions to inner cell wall penetration.
Heterogeneity
The heterogeneity
of the unbleached
pulp has a strong influence
on pulp
bleachability and, together with product
specifications, influences bleaching strategy
(62). Because of the heterogeneity of wood
and the topochemical nature of the pulping
Pt:Ocess, unbleached pulp is composed of
fibers having a distribution of lignin con.
tents. A specified average lignin content,
as determined by kappa number or K number, is the usual goal of pulping operations.
In the pulp mill, it is difficult to consistently
reach the same average value, let alone to
produce a pulp in which all fibers have the
same lignin content.
Mter the pulped chips are defibered,
knots and incompletely
delignified chip
fragments remain unfiberized. Unbleached
pulp is screened before bleaching, but even
after screening, small fiber bundles (shives)
are still present. Shives are especially
troublesome because of their relatively high
lignin content, density, and color. For these
reasons, they are not as easily bleached as
free fibers. For some products, a very low
shive content is desired. If shive removal is
an objective of bleaching, the severe treat.
49
50
20
01
~-C\J
16
100
12
15
80
(J)
"0
.5
....
CO
(J)
90
14
70
12
10
60
10
6
I3
o
o
10
20
30
Tensile
40
50
60
index, kNmlkg
70
80
Klason
lignin
%
Fig. 11. Comparlsrm
Bleachability
Bleachability
refers to the ease with
which pulps from different processes or
after different pretreatments can be brightened. The result is expressed as the final
brightness
obtainable
with a specified
bleaching sequence or by the amount of
chemical required to reach a target brightness. In this case, each laboratory selects
its own control bleach sequence as a benchmark for comparison. A general bleachability test has been proposed by which
different bleaching chemicals or different
pu1p samples can be compared (6]). The
decrease in lignin content and brightness
increase are both determined. The oxidation equivalence of various reagents is based
on their reaction with iodide.
In industrial practice, the term bleachability, when used for a given pulping process, refers to the amount
of lignin
remaining in the unbleached pulp. Therefore, application of standard delignifying
bleaching chemicals is proportional to the
residual lignin content as determined by
reaction with oxidizing agents. Test meth-
40
30
20
10
54
52
50
48
46
90
Fig. 10. Tear-tensile

,.""ges for pulps proeessetltry
varlOllS proeesses.
SB/(, semlbletu:bed
Imlft; UBS, .,,bleacbed salftte; CTMP, cbemltbermomeclla,,1ctI1
puIJ1l"g; TMP, tbermomecbt",1ctI1
puIJ1l"g; RMP, refiner mecbt",1ctI1 puIJ1l"g; au GIID, gro.lUlwood.
Reprl"ted
try perIIIlsstOff of Dr. I"grld Fi_".
ment required can lead to overbleaching of

the bulk of the pu1p. OVerbleaching leads
to pulp strength deterioration
and high
operating costs (62) (see Chap. N 11).
35
30
25
20
15
10
5
50
ods presently in common use are kappa

number (TAPPI T 236 cm-85, APPITA P 201,
CPPA G.18, ISO R 302, SCAN Cl) and permanganate number (x: Number) (TAPPI UM
251), which are based on oxidation of residuallignin with acidified permanganate,
and hypo number (TAPPI T 253 om-86 ,
CPPA G.32, ISO DIS 3260, SCAN C-29),
which is based on the reaction oflignin with
acidified hypocWorite solution. Figure 11
shows the relationship of the values obtained by these methods to the lignin content of kraft pu1ps as determined by the
Klason procedure
(TAPPI T 222 om-88 ,
ASTM D 1106, CPPA G.8 and G.9,APPITA
Pll).
Species differences affect bleachability;
for example, spruce and aspen are lightcolored woods and kraft pu1ps made from
them are brighter at the same lignin content than are kraft pulps made from Douglas-fir, pine, or oak. The non-lignin
chromophores are often found in the heartwood and belong to chemical classes such
as the flavones or polyphenolics. Examples
are dihydroquercetin
in Douglas-fir and
leucoanthocyanadins
in western hemlock.
Hardwood pulps are generally easier to
bleach than softwood pulps. Because of
their lower initial lignin content, hardwoods
of various
Hypo
Kappa
number
number
lipi"
determ/ruJttOff
can be delignified more extensively than

softwoods without damaging the fibers.
Kappa numbers of around 15 are common
for unbleached hardwood pu1ps compared
with 27-32 for conventional unbleached
softwood kraft pu1ps.
Su1fite pu1ps are very easily bleached. A
common bleaching sequence is CEH rather
than the five- or six-stage sequences used
for kraft pu1ps. It appears that su1fite pu1ps
are amenable to new, oxygen-based bleaching sequences (64,65).
In general, the bleachability of nonwood
pu1ps is similar to that of su1fite or hardwood kraft pu1ps. Bamboo pulp is more
resistant to bleaching than pu1ps from other
annual plant fibers (66). Bamboo pulps of
12-14 Knumbercan
be bleached in a CEH
or CEHH sequence to a brightness of 7678. Many other nonwood fibers can be
bleached to brightness values in the 80s
under the same conditions. CWorine dioxide is used to attain a high final brightness.
3.2
Mechanical
pulps
and chemimechanical
Because mechanical and chemirnechanical (high-yield) pu1ps have received little

or no chemical treatment during pulping,
their chemical composition is similar to that
Permanganate
number
Unbleached
pulp yield
%
methods.
of the original wood (see Table 2).The material dissolved or released during pu1p production has been identified
as lignin,
lignans, hemicellu1oses, and lipophilic extractives (67). Ash analyses of some groundwood pulps are given in Table 6. The
transition metal content of high yield pu1ps
is especially important because these metals catalyze the decomposition of hydrogen
peroxide, a bleaching agent frequently applied to high-yield pulps.
The main contributor to physical property differences between chemimechanical
and chemical pu1ps is lignin. One function
of lignin in plants is to impart stiffness and
cohesiveness to the fibers and the cell wall
components. Thus, high-lignin content fibers are stiff and tend to retain their cylindrical shape during the drying and pressing
steps in papermaking.
Compared
with
delignified pu1ps, high-yield pulp fibers do
not flatten and "conform" to each other.
Therefore, papers from high-yield pulps
have a lower degree of interfiber bonding
than those from kraft pulps. An electron
micrograph of newsprint composed of 75%
spruce groundwood and 25% spruce su1fite
pulp is shown in Fig. 12. Although the ends
of some fibers are closed because of the
action of the razor blade used for cutting,
Fig. 12. Electrmc
mlcrogrtlpb
of newspri"t
the relatively rounded and bulky shape of

the fibers should be apparent when compared with the thin flattened fibers in Fig.
9. The strength range to ~ expected from
various high-yield pulps is shown in Fig. 10
using spruce as an example (see also Chap.
VII 3).
Groundwood pulp contains a substantial
proportion (70-80 wt %) of fiber bundles,
broken fibers, and fines in addition to individual fibers.The fibers are essentially wood
and the original cell-wall lignin is intact.The
fibers are therefore stiff and bulky. Because
groundwood pulps are obtained in yields
of about 95%, their cost is relatively low.
The main direct cost other than wood is
power, which is about 49-75 kJ (11.7-17.9
kcal)/t for normal paper grades.The principal uses of paper-grade pulps are in newsprint, magazine papers including coated
publication grades, board for folding and
molded cartons, wallpapers, tissue, and
similar products. These papers have high
bulk and excellent opacity but relatively low
mechanical
strength. Groundwood
pulp
can be partially bleached with hydrogen
peroxide or sodium dithionite without significant yield loss. However, the paper,
whether bleached or unbleached, has poor
brightness stability, particularly in the presence of light, making it unsuitable for fme
papers. Where light stability is important,
cmrsUU",
of 75% sprwe
51
g1'Ollllllwooll.
the more expensive bleached chemical

pulps are nonnally used. The newer pressurized and super-pressurized groundwood
systems produce stronger pulps, the best
of which
compare
favorably
with
thermomechanical
pulps.
Thermomechanical
pulp (TMP) has a
high light-scattering coefficient although it
is lower than that of groundwood. The fibers are relatively flexible, and this imparts
good bonding and surface smoothness to
TMP papers. The increased proportion of
long fibers improves the tearing properties
of TMP over those of groundwood pulps but
the fibers in this fraction are stiff and contribute little to bonding.The strength properties of TMP are more sensitive to the
amount of fines in the sheet than are the
strength properties of groundwood pulps
(68).
pulping (CTMP)
can produce pulps having a range of properties by adjusting the processing variables,
but in general, these pulps have a greater
long-fiber fraction and a lower fines fraction than a comparable TMP.The strength
of CTMP pulp correlates with the degree
of sulfonic acid group substitution.The sulfur content is typically 2-3 g/kg. The intact
fibers of CTMP are more flexible than TMP
fibers; and, therefore, better sheet-forming
and bonding properties are obtained. The
52
Pulp Bleaching
-Principles
and Practice
mild chemical treatment also allows the

production of a long-fibere~ pulp having
fast drainage, good absorption properties,
and sufficient softness for tissue-grade pulp.
The effect of chemical treatments on pulp
brightness is variable. 10 softwood CTMP
pulps, light scattering increases with low
sulfite application, but decreases as the
sulfite charge is increased (69).10 hardwood CTMP pulps, the higher strength obtained
from
alkali
treatment
is
counterbalanced
by lower light scattering
and brightness as the alkali application is
increased (70).
The brightness of high-yield sulfite pulps
decreases, then increases as the yield decreases as shown in Fig. 7. The trend is similar to that observed for kraft pulps, except
that the brightness remains much higher
and the upturn occurs at a higher lignin
content (15-18% residual lignin). Sulfonated
lignin-containing
pulps undergo a metalcatalyzed reddening upon storage.This phenomenon
has been attributed
to the
oxidative formation of stilbene-type quinones (71).The advantages of high-yield pulps
are their high yield and economy of production. The bleaching operation is designed to preserve these attributes. This
means that high-yield pulps are treated to
remove color as selectively as possible without removing significant amounts of fiber
constituents [see Chap. III 3]. The bleaching of high-yield pulps is thereby much
more sensitive to the chromophoric
composition of the original wood than is the
bleaching of chemical pulps.
In addition, wood tends to undergo color
changes during storage (72). Most woods
become a deeper yellow or brown from
atmospheric oxygen, light, and moisture.
The action of fungi may impart blue or red
stains; brown rot fungi can demethylate and
darken lignin. Bark pigments may be introduced into the wood after it is soaked in
water or during the chipping of some
unbarked woods such as red alder.
11 R~tYdad fib~R
Composition
The major problem in any type of recycling is removal of contaminant<;.These can
vary from physically included materials such

as metals or dirt to adsorbed, absorbed, and
even chemically bonded materials. Pollutants entering the recycle stream may be
very difficult to control. For example, recycled paper streams were contaminated by
polychlorinated
biphenyls long after their
use in paper production (e.g., carbonless
papers) had stopped. Besides additional
chemical substances that mayor may not
be known, the chemical composition
of
recycled fibers ranges from that of fully
bleached pulps to essentially the composition of wood.
Physical properties
The strength properties of recycled fibers
differ from those of virgin fibers primarily
because of the structural changes that take
place in the individual fibers during the drying stage of papermaking. This difference
is manifested as greater fiber stiffness and
is more pronounced
for chemical pulps
than for mechanical pulps, which contain
stiff fibers from the outset (73). The stiffened fibers have reduced capability for interfiber bonding and therefore lower tensile
properties. For beaten bleached kraft pulps,
the tear strength increases upon recycling.
Papers made from recycled mechanical and
chemimechanical
pulps have decreased
light-scattering coefficients but increased
breaking length. Because much of the original interfiber bonding comes from fibrillation of fiber surfaces, the fines content
increases when papers are repulped, and
the fibrils are broken.
The effects of recycling are usually the
greatest after the first cycle. In laboratory
tests, where the same batch of pulp is repeatedly made into paper and recycled,
strength and optical properties tend to level
off after 3 or 4 cycles (73).
Bleachability
Certain considerations apply specifically
to the bleaching of postconsumer
waste
papers. Such papers often contain a mixture of chemimechanical
and chemical
pulps even if postconsumer
separation is
employed because paper products may contain a blend of the two pulp types. Such
Chapter II I: Production of Unbleached Pulp

mixtures are difficult to bleach homogeneously and effectively
without
overbleaching the chemical pulp component.
Unfortunately, this problem is anticipated
to increase as the extent of recycling increases and separation of different kinds of
pulp becomes more difficult. Another major consideration is whether the recycled
paper has been dyed. Other factors, such
as the printing processes and ink types used
on the paper, affect bleaching efficiency but
are less of a consideration
in choosing a
bleaching method. In practice, the efficiency of the deinking operation has a great
impact on the ensuing bleaching stage (74).
After exposure to light and varying atmospheric conditions, once-bleached papers
undergo color reversion.This is particularly
true for high-yield, lignin-<:ontaining pulps-,
but is also true to a lesser extent for fully
bleached chemical pulps.The reverted color
is considered somewhat more difficult to
bleach than the original color (75).
Because of the extreme variability in the
supply of recycled paper; each mill should
perform bleaching optimization studies for
its own supply of recycled paper. The published results of many empirical laboratory
studies provide a guide for initial process
selection. Process control is more difficult
for bleaching recycled fibers than for virgin fibers. However, sensors based on oxidation-reduction
potential
principles
appear to give satisfactory results (76).
Dyes
The bleaching of colored papers is a separate problem. Much of the color is often
removed in the deinking step, especially if
the colored inks or pigments are only physically entrapped in the fiber matrix. However, many dyes are resistant to deinking and
to mild oxidative treatments such as treatment with hydrogen peroxide. Hypochlorite and chlorine are often effective in
destroying dyestuffs, but their use may be
discontinued for environmental reasons.
More than 300,000 color agents are reportedly in use (77); fortunately, the number of dyes commonly
used in paper
applications is much smaller and dye classes
have similar chemical characteristics. It is
53
helpful to know the composition of the dye

being bleached. Dyes are commonly classified as basic, acidic, or direct (substantive).
Basic dyes, which have been used for unbleached pulps and groundwood because
of their attachment to lignin, are falling into
disfavor because of carcinogenicity
concerns. This class includes dyes such as
Rhodamine, Victoria Green, and Victoria
Blue. Acid dyes have high water solubility
and include Quinoline Yellow and Orange
II. Acid dyes require the use of size and
alum to bind them to paper.
The most frequently used dyes in the
paper industry are direct dyes, which are
similar to acid dyes but have higher molecular weights and do not require separate
bonding agents. Direct dyes are the sodium
salts of dye acids and bond to cellulose
through hydrogen bonding of separate functional groups. At least two such functional
groups per dye molecule are necessary. The
majority of the direct dyes are azo dyes. This
class also includes stilbene, phthalocyanine,
dioxazine,and some anthraquinone-,quinoline-, and thiazole-type dyes. Many direct
dyes used in papermaking can be decolorized with reductive bleaching agents.The
azo linkage is susceptible
to reduction
which frequently produces colorless products; however, many of the reduced amine
compounds have a yellowish color, which
must be destroyed by oxidative bleaching
agents.The smaller reduced direct dye molecules are more likely to affect aquatic life
and many aromatic amines are suspected
carcinogens. Therefore, their further destruction, for example, by biological treatment of the waste streams, is desirable.
Research
is in progress
to develop
nonmutagenic dye intermediates (78). If the
amines used in azo dye production are not
genotoxic, the reduction products of the
dyes are likewise non-genotoxic.
A new class of direct dyes, designed to
increase the water solubility for application
and to overcome the electronegative repulsion of cellulose, is the cationic direct dye.
In these dyes, the charged functional group
is situated apart from the chromophoric
functional center. Upon reduction of the
54
chromophoric
group, a smaller, water-insoluble fragment and a charged, watersoluble fragment may result. Some insoluble
fragments may retain a slight yellow color.
The acid anthraquinone
dyes are problematic because reduction to hydroquinones imparts a yellow or brown color, and
the dyes are easiIy reoxidized to the quinone
state. In the ionic state, hydroquinones are
more water-soluble and the dyes are then
amenable to removal by washing before
they are reoxidized to their quinone form.
Fiber-reactive
dyes that are covalently
bonded are very difficult to remove and
often contain a quinone function.
Color stripping
Because of the chemical constitution of
the common dyes, oxidative agents alone
usually cannot adequately remove color
from dyed recycled papers.Therefore, color
stripping is generally a separate operation
as part of recycled paper bleaching (Table
4). If hydrogen peroxide is used in the
pulping or deinking stage and alkali yellowing is avoided, a single subsequent reductive bleaching stage with sodium dithionite
(NaZSZ04, also called sodium hydrosulfite)
may be sufficient. A two-stage "post-bleaching" with hydrogen peroxide, followed by
dithionite or formamidine sulfinic acid (FAS,
H1NCNHS01H, also called thiourea dioxide), may be used for high brightness. Obviously, the chemicals in the two stages are
incompatible, and residual peroxide must
be washed out or destroyed before the reductive stage. Dithionite is also subject to
air oxidation. The sequence of oxidant followed by reductant is usually recommended
because the effects of reduction of chromophores are more easily reversed than are
those of oxidation (79). However, in at least
one published example (80), bleaching
with FAS followed by hydrogen peroxide
improved brightness significantly compared
to reversing the order of these operations.
The chemical classification of the Colour
Index number system (81) combined with
the known analytical reactivity of many dyes
toward dithionite has been used to estimate
the stripping characteristics of most identifiable dyes (82). Dithionite can effectively
color strip most nitroso-nitro and azo dyes.

Some dyes with higher index numbers are
also reducible with dithionite. A more recent paper from Germany describes the
bleachability of different colors using various bleaching conditions (83). The TAPPI
Pulp Bleaching Committee is presently assembling a list of dyes currently in use, their
properties,
and methods of destruction
(84).The data base is expected to be available in printed or electronic form by 1996.
Preliminary mill trials and laboratory data
indicate that many dyes can be more effectively stripped
with FAS than with
dithionite. FAS is effective at alkaline pH
levels and therefore may be a replacement
for hypochlorite. Examples of the relative
color stripping abilities of FASand dithionite
have been published (85,86). Although FAS
is more expensive than dithionite, the more
efficient reducing action of FAS makes it
cost effective in many instances.
Ozone is beginning to be applied commercially as a replacement for chlorine in
pulp bleaching (87). In an investigation of
potential bleaching agents for anticipated
mixes of secondary fiber, ozone stripped
the color from multicolored ledger (88).
Other researchers have also noted the effective color-stripping ability of ozone (8991). Another new oxidative color-stripping
agent that shows promise is peroxymonosulfate applied in the acid (Caro's acid) or
salt form (92,93).
Acknowledgment
I am indebted to John Hatton, PAPRICAN,
and Peter Ince, USDA Forest Service, for
providing some of the information fOlmd
in the text, figures, and tables comprising
this chapter.
References
1. Hatton,].
v., personal
communication.
2. Nguyen,
X. T., Shariff,
P. E, Earl, Earner,
R.J.,Prog. Pap. Recyc. 2(5):25

3. Jackson, M., Croon,
77(9):153 (1994).
(1993)
1. 1., Nardi, E, Tappi].

4. Haynes, R. W.,An Analysis
of the Timber
Situation
in the United States: 1989-2040:
A Tecbnical
Document
Supporting
tbe
1989 USDA Forest Service RPAAssessment,
General Technical Report RM-199, USDA
Forest Service, Rocky Mountain
Forest
Range Experiment Station, Fort Collins, CO,
1990.
55
19. Greenwood,
B. F., "Extended
Delignification, a Bleaching Stage?," Bleach Plant
Operations
Short Course Notes, TAPPI
PRESS, Atlanta, 1992, p. 41.
20. Cyr, M. E., Embley, D. F., Macleod,].
TapPiJ. 72(10):157
(989).
21. Dillner,
(1993).
B., Int. Papermaker
M,
56(2):35
5. Ince, P. ]., Recycling

Long-Range
Timber
Outlook
Background
Researcb
Report
1993 RPA Assessment
Update, Research
Paper FPL-RP-534, USDA Forest Service,
Forest Products Laboratory, Madison, WI,
1994.
22. Green, R. P. and Prussas,

Can. 76(9):T272 (975).
6. McGovern,].,
in Pulp
Chemical Technology
eOO., Wiley-Interscience,
Vol. 1, Chap. 3.
25. Bach, B. and Fiehn, G., Zellst. Pap. 210):3

(972).
Paper, Cbemistry
O. P. Casey, Ed.) 3rd
New York, 1980,
7. Procter, A. R., Yean, W Q., Goring,

Pulp Pap. Can. 68:T445 (967).
8. Saka, S., Thomas, R.).,
Fiber 11(2):99 (979).
Gratzl,).
D. A. I.;
S., Wood
9. Heitner, c., Bolker, H. I., Jones, H. G., Pulp

Pap. Can. 76(8):T243
(1975).
10. Rydholm,
S. A. in Pulping
Processes,
Interscience,
New York, 1965, p. 361.
11. Favis, B. D., Willis,]. M., Goring, D.A. I., J
Wood Cbern. Tecbnol. 3(1):1 (983).
12. Favis, B. D., Willis, J. M., Goring, D. A. I.,
JWood
Cbem. Tecbnol. 30):9 (983).
13. Lin,). H., Chang, H.-M., Chen, C. L., Gratzl,
). S., "The Isolation
Characterization
of
Residual lignin in Unbleached
Pine Kraft
Pulp," Canadian Wood Chemistry Symposium Proceedings, Technical Section, Canadian Pulp Paper Association, Montreal,
1979, p. 117.
14. Li, J. Macleod, J. M.,)
19(2):J85 (1993).
Pulp
Pap.
Sci.
15. Smith, A. J., Gustafson, R. R., McKean, W

T., TaPPiJ. 76(6):81 (1993).
16. Vilpponen,A.,
Gullichsen,).,
Lindholm,
A., Tappi J. 76(2):134 (1993).
C-
17. Johansson,
B., Mjoberg,].,
Sandstrom, P.,
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87(0):30
(1984)
18. Kubes, G. J., Fleming, B. I., Macleod,
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M., Bolker, H. I.,J Wood Cbem. Tecbnol.
3(3):313 (983).
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23. Pekkala, 0., Pap. Puu 64(1):735

24. Jiang,). E., Greenwood,
R., Becker, E. S.,Appita
(982).
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(992).
26. Holton, H. H.,Pulp

(977).
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27. Blain,T.].,
76(3):137
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30. Rajan, P. S., Griffin, C. W., Jameel,

H.,
Gratzl,). S., "Extending the Digester Delignification
with Anthraquinone,"
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Proceedings,
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PRESS, Atlanta, 1992, Book 3, p. 985.
31. Raymond, D. R. and Rosen,A.,AICbE
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Series 80(239):30 (1984).
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Sym54(4):52
33. Watson, P. A., Gustafson, R. R., McKean,

W T., Andrews, E. K., "Low Sulfidity and
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35. Aziz, S. and Sarkanen,

169 (1989).
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of an Existing
Kraft Pulp Mill to an ASAM Mill;' TAPPI
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PRESS, Atlanta. 1991, Book 2, p. 925.
37. Pye, E. K., TapPiJ.
38. Cronlund,
M. and Powers,).,
"Bleaching
Responses ofALCELL Organosolv Pulps using Conventional and Nonchlorine
Bleaching
Sequences,"
TAPPI
Pulping
Conference
Proceedings,
TAPPI PRESS,
Atlanta, 1991, Book 2, p. 547.
39. Schroeter,
M. C. and Dahlmann,
G.,
"ORGANOCELL
Simplifies
the Solvent
Pulping Process," TAPPI Pulping Conference Proceedings,
TAPPI PRESS, Atlanta,
1991, Book 2, p. 646.
40. Gottlieb, K., Preuss,A.W, Meckel,]., Berg,
A., "ACETOCELL Pulping of Spruce and
Chlorine-Free
Bleaching," Solvent Pulping
Symposium
Notes, TAPPI PRESS, Atlanta,
1992, p. 35.
41. Poppius-Levlin,
74(3):113
(1991).
K., Mustonen,
R., Huovila,
Pap. Puu 73(2):154
42. Evans,]. C.W,Pulp
L., TapPiJ
29. Goyal, G. c., Powers,J., Cronlund, M., "Anthraquinone

- A Simple Approach for Extended Delignification
in Conventional
Kraft Pulping,"TAPPI Pulping Conference
Proceedings, TAPPI PRESS, Atlanta, 1992,
Book 3, p. 1047.
34. Kleppe,
T.,Sundquist,].,
28. McDonough,T.J.
and Herro,].
65(9):117 (1982).
32. Ringley, M. B.,Am.

(1991).
56
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(991).
(1980).
43. lippert, G.V.,Tuominen, R., Nerg, H. ,Pulp

Pap. Can. 94(11):69 (1993).
44. Leask, R.A., in Pulp and Paper Manufacture (M.). Kocurek R.A. Leask, Eds.) 3rd
edn., McGraw-Hill, New York, 1987, Vol.
2, Chap. 8, p. 112.
45. Babb, c., Miller, R., Mclaughlin,
S., Doyle,
M., "Recycled Fiber Processing in the Year
2000," Recycling Symposium Notes,TAPPI
PRESS, Atlanta, 1993, p. 189.
46. Minor,]. L. and Sanyer,N.,
(1975) and unpublished
Tappi 58(3): 116

data.
47. Sanyer, N. and Laundrie,).

47(10):640 (964).
F., Tappi
48. Rydholm,
S. A., Pulping
Processes,
Interscience,
New York, 1965, p. 1156.
49. Springer, E. L., Tappi 54(12):2059
50. Kordsachia,
O. and
41(7):3400987).
Patt,
(1971).
R., Papier
51. Chirat, C. and Lachenal, D., "Beneficial and

Adverse Effect of Metal Ions in ZP Bleaching Sequences,'TAPPI
Pulping Conference
Proceedings, TAPPI PRESS, Atlanta, 1994,
Book 3, p. 1239.
52. Springer,
E. L. and McSweeny,
"Bleaching Groundwood
and Kraft
with Potassium Peroxymonosulfate
J. D.,
Pulps
- Comparison with Hydrogen Peroxide,"TAPPI
Pulping Conference
Proceedings,
TAPPI
PRESS, Atlanta, 1986, p. 671
53. Springer, E. L. and McSweeny,].

J. 76(8):194 (1993).
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54. Kubes, G. J., Macleod,).

M., Fleming, B.
I., Bolker, H. I., "Viscosities of Unbleached
Alkaline Pulps,'TAPPI Pulping Conference
Proceedings,
TAPPI PRESS,Atlanta,
1980,
p.31.
55. Nutt, W E., Eachus, S. W, Griggs, B. F.,
Pikulin, M.A., "Development
of an Ozone
Bleaching Process,'TAPPI
Pulping Conference Proceedings,
1992, p. 1109.
56. Elliott, R. G. and Walley, C. A., "AOX and
Dioxin Emissions Reduction at Longview
Fibre Company,"
International
Pulp
Bleaching Conference
Proceedings,
SCPI,
Stockholm,
1991, Book 3, p. 253.
57. Hoglund, H., Fredriksson,
B., Eriksson, I.,
"Chemithermo-Mechanical
Pulp;' International Mechanical Pulping Conference Pr0ceedings, SPCI, Stockholm,
1977, p. 53.
58. Stone,]. E. and Scallan, A. M., Pulp
Mag. Can. 69(6):T288
(1968).
Pap.
59. Tarkow, H., Feist, W c., Southerland,

F., For. Prod.]. 16(10):61 (966).
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60. Kantelinen,A.,
Hortling, B., Sundquist,].,
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47(4):318 (1993).
61. Yu, X., Minor,]. L., Atalla, R. H., Labbauf,
M. M., Farrell, R. L., "Effect of Hemicellulase on Unbleached
Softwood Kraft
Pulp," International
Pulp Bleaching Conference Proceedings,
Technical
Section,
Canadian
Pulp and Paper Association,
Montreal, 1994, p. 63.
62. Hamlin,M.P.,"Impact
of Unbleached
Pulp
Quality on the Bleach Plant Operations."
Bleach Plant Operations
Short Course
Notes, TAPPI PRESS, Atlanta, 1992, p. 31.
63. Wartiovaara, I. and Toikkanen,
68:630 (986).
L., Pap. Puu
64. Kruger, H. and Suss, H. U.,Pulp

85(12):109 (984).
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65. Patt, R., Hammann,

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45(Suppl):87
(1991).
0.,
66. Misra, D. K., in Pulp and Paper, Cbemistry and Cbemical Tecbnology O. P.Casey,
Ed.) 3rd edn., Wiley-Interscience,
York, 1980 Vol. 1, p. 553.
New
~--

67. Sundberg, K.,Thomton,J.,
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(1980).
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62(12):803
57
80. Heimburger,
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69. Axelson,
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R., Svensk
Papperstidn.
85(15):RI32
(1982).
83. Troemel,
104(2):74
70. Leask, R.A., in Pulp and Paper Manufacture (M.]. Kocurek R. A. Leask, Eds.) 3rd
edn., McGraw-Hill, New York, 1987, Vol.
2, Chap. 11, p. 157.
84. TAPPI
Pulp
CA#94060608.
71. Adler,
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Papperstidn.
53(11):287,
321 (1950).
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Tech '92, Course Notes, Canadian Pulp and
Paper Association, Montreal, 1992 .
72. Loms, v., in Pulp and Paper, Chemistry

and Chemical Technology (J. P.Casey, Ed.)
3rd edn., Wiley-Interscience,
New York,
1980, Vol. 1, Chap. 5.
73. Howard, R. C. and Bichard,W.,j
Sci. 18(4):JI51 (1992).
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(1990).
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75. Joachimides,
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74(1):211 (1991).
.
76. Allen,]., Tappi 45(2): 170A (1962).
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the Challenge;
Background
report for Magazine Publishers of America, Magazine Publishers
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Claxton,
(1991).
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21(7):438
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Notes,TAPPI
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(1976).
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88. Angulo,].
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Pap. Sci. 20(7):J206 (1994).
(1992).
(1991).
N.,]
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91. Kogan,]., Muguet, M., Perkins, A., "Ozone

Bleaching of Deinked Pulp,"TAPPI Recycling Symposium Notes, TAPPI PRESS,Atlanta, 1994, p. 237.
92. Kapadia,
P. c., Tessier, H. G., Langlois,
S.,
"A Non-Chlorine
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for WetStrength Destruction," 79th Annual Meeting Proceedings, Technical Section, Canadian Pulp and Paper Association, Montreal,
1993, p.A62.
93. Walsh, P. B., Hill, R.T., Dutton,
Pap. Recycl. 3(1):9 (1993).
D. B.,Frog.
SECTIONII:
Raw Materials
Chapter 2:
Bleaching Chemicals:
Chlorine Dioxide
Maurice C. Fredette
Sterling Pulp Chemicals, Ltd.
Toronto, ON
Canada
1. Properties.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
2. Process chemistry.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
61
62
3. Generation systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 62
3.1 Atmospheric processes
63
3.2 Vacuum evaporator processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 64
4. Testing.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . ..
5. Safety hazards
67
67
59
Chapter n 2: Bleaching Chemicals: Chlorine Dioxide
Chapter n 2:
Chlorine Dioxide
1. Properties
The properties
of chlorine dioxide,
shown inTable 1,influence its manufacture
and storage. Because chlorine dioxide is
unstable as a gas and can only be stored as
a solution of approximately
1% in water
[Fig. I (1)], it must be generated on-site at
the pulp mill. All production, handling, and
storage systems control the concentration
of chlorine dioxide in the gas phase.
Most processes use air or a combination
of steam dilution and vacuum to keep the
partial pressure of chlorine dioxide below
100 mm Hg (1). At this vapor pressure
and at typical process temperatures of 4070eC, the gas is stable for at least five seconds (1); in commercial
processes, the
time to convey chlorine dioxide from the
generator to the absorption water is 0.5
seconds. Once in solution, chlorine diox5eC in
ide is stable and can be kept at
the dark for several months with little
change in concentration providing the container has no gas space.
Because many mills have now replaced

chlorine gas completely with chlorine dioxide, the production system must be very
reliable and the amount of chlorine dioxide solution in storage must be sufficient
for any upsets. Today, units producing up
to 65 tons/day are operating in large softwood kraft pulp mills, though 5 ton/day
units were typical in the 1950s.
Tabk 1: Properliesof eblorlf8etlloxUle(1, 2)
Chemical Formula
CIO,
Molecular Weight:
67.45
Gas Properties:
Green, like chlorine, but darker at the same
concentrations
Pungent, irritating odor
Density 2.4 times that of air
Soluble in water, typically in a 10 g/L (1%)
solution
Decomposes to chlorine and oxygen with
noise, heat, flame, and a minor pressure wave
at low concentrations (puff)
Decomposes explosively at ~ 300 mm Hg partial pressure
Health Hazards:
0.1 ppm permissible for 8-h exposure
17* ppm definitely detectable. 45 ppm irritates eyes and nose. Wear a mouth/nose respirator.
Effects are non-cumulative
* 1 ppm per this author
20
18
16
(.)
14
12
C
o
:;:;
:c
(.)
4
2
0
20
40
60
80
100
120
Chlorine dioxide partial pressure,

solubility
of eblorlf8e
tlIoxUIe I" water.
140
mmHg
_ CI- + 3 HP
[11]
2. Process chemistry
C103' + 6 H+ + 6 e'
Chlorine dioxide is formed in either of

two ways: by reduction of chlorate ion
(CI03-) in an acidic medium
Steps must be taken to minimize this reaction by careful choice and control of reaction conditions.
The mechanism of chlorine dioxide formation has been extensively studied and is
described in detail elsewhere (3, 4). In all
mechanisms, chloride plays a crucial role
as evidenced by its presence in all chloratebased reaction media and by the trace
amounts of chlorine in the chlorine dioxide formed. No chlorine dioxide is formed
if chloride ion is not present in the reaction medium. Chloride ion is introduced
into the system by reduction of chlorate to
chloride (reaction [11)) or by addition of
chloride in the feed. Rapson (5) proposed
the following mechanism where chloride
ion is the reducing agent:
CI03'
+ 2 H++ e- -- CIO, + H,O
[1]
or by oxidation of chlorite ion (ClO;)
ClO;
-- CIO,
[2]
+ e'
The choice of reducing agent for chlorine dioxide generation from chlorate has a
great bearing on optimum reaction conditions, by-products, and economics. Production from chlorite (CIO,-) is uneconomical;
reaction [2] is reversible and chlorite is usually synthesised from chlorine dioxide.
Commercially used reducing agents for
production of chlorine dioxide from chlorate are sulfur dioxide (SO,), methanol
(CH30H), chloride ion (Cn, and hydrogen
peroxide CHP,). Their half reactions are
as follows:
SO, + 2 HP _ SO; + 4 H++ 2 eCHpH
+ HP
_ HCOOH
[3]
+ 4 H+ + 4 e- [4]
Cl- _ 1/2CI, + eH,O, _ 0, + 2 H++ 2 e-
[5]
[6]
Combining equation [1] with with equations [3]-[6] gives:

[7]
2 CI03- + S0, _ 2 CIO, + 50/+ CHpH
+ 4 H+
_ 4 CIO,
+ HCOOH
+ 3 HP
[8]
CI03-+ CI' + 2 H+ _ CIO, + Cl, + HP
[9]
2 CI03'+ HP, + 2 H+""2 CIO, + 0, + 2 HP

[10]
Fig. 1. Equilibrium
62
4 CI03-
~"iS. 10
-001
'x
8
o
'0
6
~
';::
61
The by-products formed are sulfate ion

(54=), formic acid (HCOOH), chlorine
(CI,),and oxygen (0,). The acid equivalents
required per mole of chlorine dioxide produced differ and are zero for sulfur dioxide, one for methanol, two for chloride, and
one for hydrogen peroxide. Acid consumption is also influenced by the process conditions used in particular
commercial
designs.
In all systems, a side reaction may occur,
reduction of chlorate to chloride:
HCI03 + HCI-
HCIO, + HClO
_
2 CIO, + HP
HCI03 + HClO,
[12]
HCIO + HCI-
[14]
CI, + HP
[13]
The formation of by-products, other than

those identified in equations [7] through
[10], is governed by the chlorate salt and
acid selected. In all commercial processes,
the chlorate salt used is sodium chlorate
(NaCIO) and,to date, the only acids used
have been sulfuric (H,S04) and hydrochloric (HCI); consequently, the by-products are
sodium sulfate (Na,S04) or sodium chloride
(NaCl) , Depending upon process conditions, sulfate is recovered as neutral crystalline sodium sulfate, sodium sesquisulfate
[Na3H(SO),], or is dissolved in an acidic
effluent. If hydrochloric acid is used, sodium chloride is recovered in a crystalline
form or in an internally recycled solution.
3. Generation systems
In this section, commercial chlorine dioxide generation systems are described in
a sequence which closely follows the order
of their adoption by the pulp industry. The
evolution of the technology has been dictated by the changing ability of pulp mills
to effectively utilize the by-products and
also by the need for larger and more reliable chlorine dioxide plants. Changes have
Chapter II 2: Bleaching Chemicals: Chlorine Dioxide

also been environmentally driven, for example, the elimination of by-product cWorine.
Sodium chlorate is usually received as
crystals in rail cars and is dissolved in hot
water to make a 40-45% solution. Mills
within 100 kilometers of a supplier may
receive a cWorate solution directly. Reactants are added to the generator, and gaseous cWorine dioxide is removed. CWorine
dioxide gas pressure is controlled by dilution with air,steam,and the use of vacuum;
the generated cWorine dioxide is absorbed
in chilled water to make a solution of approximately 10 g/L. Sodium cWorate rep75% of the cost of cWorine dioxide
resents
manufacture; therefore, the processes must
generate this gas in high yield. Yield is expressed as the molar percentage of the s0dium chlorate
converted
to chlorine
dioxide. With the increase in generator
63
64
sizes, there has been a corresponding

demand for increased yield which has now
reached 97% compared with 87% 40 years
ago.
However, based on equations [3] and

[11], an unwanted side reaction takes place
under low acidity conditions, leading to
considerable loss of yield:
3.1 Atmospheric
NaCI03 + 3 S02 + 3 HP -> NaCl + 3 H2S04

[16]
processes
The Mathieson (6), Solvay (7), and R2

(8, 9) processes use sulfur dioxide, methanol, and sodium chloride, respectively, as
reducing agents. All operate at atmospheric
pressure, use air to strip and dilute the cWorine dioxide, and have an overflow of spent
sulfuric acid (10-12).
In the 1950s, the
Mathieson process was dominant,followed
by the Solvay process. There are still approximately 200 Mathieson units in service
and many Solvay units as well. The
Mathieson unit is shown in Fig. 2. The overall reaction, based on equation [7], is
2 NaCI03 + S02 -> 2 CI02 + Na2S04
[15]
Vent
Chilled
water
To help avoid this problem, enough sulfuric acid is fed to the Mathieson generator
to create a 450-500 g/L acid concentration
(9-10 N H2S04)' The acid (2-2.5 tit ofC102)
overflows from the generator and must be
used for tall oil acidulation, recovered with
black liquor for makeup sulfur, or neutralized and discharged. Some unreacted s0dium cWorate also leaves the generator with
the acid; this, and the contribution of reaction [16], limits the yield to about 87%.
The Solvay process uses methanol as the
reducing agent, also in a 450- 500 g/L sulfuric acid solution. The reaction, based on
equation [8], is
4 NaCIOj + H2S04 + CHpH
2 Na2S04 + HCOOH + 3 HP
-> 4 CI02 +
[17]
Both processes above produce cWorine

dioxide solutions having low concentrations of cWorine.
The crucial role of the chloride ion in all
processes (described in Sect. 2 ohhis chapter) led to the R2 process which became
popular in the 196Os. The overall reaction,
based on equation [9] is
Cl02
absorber
C102 and Air
CI02
solution
NaCIOj+ NaCl + H2S04 -> CI02 + 1/2 Cll +

[18]
Na2S04 + HP
As in the Mathieson process, a side reaction, [19], based on equations [6] and [11],
may occur:
...
NaCIOj + 5 NaCl + 3 HlS04 -> 3 Cil +

[19]
3 HP + 3 Na2S04
QI
Cooling
water
a.
a.
";:
.....
Air
& S02
Spent
acid
Air
Fig. 2. Flowsbeet
for tbe gerrertltUm
of cblorine
tUoxUk
In tbe Matblesofl
proeess.
The R2 process produces 0.6 t of CI/t of

1 g/L of cWorine in the chloCIO with
l'
rine dioxide solution and the balance (0.5
tIt of CIO) is used to make sodium hypochloritc.
Because the R2 reaction is much faster
than the Mathieson or Solvay reaction, the
process can be carried out in one vessel
V\
instead of two. But because no in situ acid

is fonned as in the case with the Mathieson
and Solvay processes, and because more
water is needed as the result of the addition of sodium cWoride, 4.5 t of acid/t of
CIO, is required. This marked the appearance of the first restriction in matching generator selection to pulp mill operation.
Heretofore, all the waste acid was used in
the mill recovery system as makeup for sodium and sulfur losses. The acid effluent
from the R2 generators exceeded pulp mill
needs except in the southern United States
where the waste acid could be used for tall
oil acidulation, and this is where virtually
all R2 units were sold.
3.2 Vacuum evaporator
processes
In response to the need to decrease the
amount of waste acid produced, ways to
crystallize sodium sulfate from the waste
acid, or to recycle it, were studied. Evaporation and cooling of the 9 N R2 waste acid
led to crystallization. It was recognized that
an evaporator-crystallizer
could also function as a chlorine dioxide generator with
the steam and vacuum serving to control
cWorine dioxide partial pressure. This led
to the R3/SVP (see Footnotes 1 and 2) processes (13-15).
By performing
the R2
chemistry under vacuum, at higher temperatures, and with proprietary catalysts, a
suitable production rate and yield was maintained with the reaction solution acidity less
than that corresponding to 4.5 N HlSO the
4'
point below which neutral anhydrous s0dium sulfate can be crystallized and filtered.
A typical
flow sheet
is shown
in
Fig. 3.
The cWorine
by-product
of 0.6 tIt of CIO
creates 2 g/L of Cll in the chlorine dioxide

solution and the balance, 0.4 t of CI/t of
CIO, is used to produce chlorine water or
hypochlorite in a second absorption tower.
The chemistry of the process is represented
by the same equations, [18] and [19], as the
R2 process, but no waste acid is produced.
The yield is about
93%.
As pulp mills decreased sodium and sulfur losses and also increased their use of
chlorine dioxide, sodium/sulfur
by-prod-
Chapter n 2: Bleaching Chemicals: CWorine Dioxide

ucts were fonned in excess of pulp mill
needs. The use of by-product cWorine as
hypocWorite also became less attractive as
mills strived to obtain higher strength and
higher brightness pulps and eliminate chlorofonn fonnation.
These requirements led to processes using hydrocWoric acid to replace part or all
of the sulfuric acid in an R3 or SVP process
(see reaction [20]). The hydrochloric acid
can be purchased or made by burning byproduct cWorine with hydrogen (16-18)
in a hydrocWoric acid burner, or alternatively, the chlorine could be reacted with
sulfur dioxide and water to make a mixture
of hydrocWoric and sulfuric acids (see reaction [21]). This, and the partial replacement processes
halved the by-product
65
66
Pulp Bleaching
sodium sulfate and eliminated the cWorine

water or hypocWorite by-product (19-21).
Purchased
NaCIO, + HCI + 1/2 H2S04

Na2S04
+ 1/2 CI2
1/2C12 + 1/2S02 + HP
Generator
Excess
HCI + 1/2H2S04
(21)
HydrocWoric acid processes can be operated independently (R5, SVP-HCI) or integrated with an on-site cWorate plant (R6,
Lurgi, Chemetics, and Day-Kesting processes) as shown in Fig. 4 (22-26).
The
key reactions are:
(a) chlorine dioxide is made by reaction [22]
Chlorine
& air to
scrubber
& vacuum
Generator
evaporator
crystallizer
CD
"-
H2SO4
8
u
L
tank
Cl02 + 1/2
(20)
NaCI
Jltg. 4. DUlgram
of I"tegrwletl
CD
"-
-e
0
fII
.Q
c(
cblorl~
dtozUIe gerreraUorr process.
NaCIO,. + 2 HCI ~ 1/2 CI02 + CI2 + HP +

(22)
NaCi
(b) sodium cWorate is made by electrolysis
using by-product salt (from reaction [22])
NaCi + 3 HP
Filter
cake
mix
CI2
and Practice
R3H/SVP - HCI/R7/SVP-MARS Processes
Chilled
water
Filter
-Principles
NaClO, + 3 H2
(23)
(c) by-product cWorine from the generatOr

and purchased cWorine are reacted with byproduct hydrogen from the chlorate cells
to produce HCI:
1/2 Cl2 (by-product) + 1/2 CI2 (purchased) +
(24)
H2 ~ 2 HCI
(d) combining equations [22], [23] and [24]
gives the overall stoichiometry for the integrated process:
1/2C12 + 2 HP
CI02 + 2 H2
(25)
These processes produce no sodium sulfate. The integrated plants burn 0.7 t of CII
t of CI02 (reaction [24]) to make the required hydrocWoric acid and therefore contribute
to balancing
the NaOH/CI2
purchases of the mill. Integrated plants require significantly more capital and space
compared with other chlorine dioxide
plants.
I"-CD
::I:
The R8/SVP
MeOH process (27-31)
The drive to eliminate cWorine, decrease

by-product
sodium sulfate and increase efficiency
and production
rates led to the
development
of a new methanol-based
pro-
NaG109
+ reducingagent
cess. The overall reaction for the RB/SVP

MeOH process
may be represented
3 NaCIO, + 2 H2SO4 +O.80CHpH

Fig. 3. Flowsheet
for tbe gerreratton
of t:blort~
dioxide
I"
tbe R au
SW series processes.
as
~ 3 Cl02
(26)
+ Na,H(SO)2 + 2.3 ~O + 0.8 HCOOH
The stoichiometry
based on equation
(26) does not take into account the 0.03 t
of CH,OH/t of CI02 which leaves the generator unreacted in the gas phase and dissolves in the chlorine dioxide solution.
Some of the formic acid (HCOOH) reacts
further
HCOOH ~
C02
+ 2 W + 2 e-
[27]
Because formic acid has a similar vapor

pressure to that of water, most of it is
stripped from the generator. A typical 10
g/L CI02 solution contains 0.2-0.9 g/L of
CHpH, 1.7 g/L of CHOOH, 0.4 g/L of C02'
and 0.1 g/L of C12.The amount of methanol
is in inverse relationship to the operating
acidity (see below). Because the R8/SVP
Methanol processes operate at greater than
5 N acidity, sodium and sulfate are recovered as sodium sesquisulfate [Na,H(S04)2]'
This process has the advantages of virtually
eliminating cWorine by-product (0.1 gpL of
CI2 in 10 gpL of CIO~, producing 40% less
saltcake than the R3/SVP processes, and
increasing cWorine dioxide yield (97%) and
production capacity.
CWorine is not totally eliminated because
of the necessary presence of low concentrations of cWoride ion in the generator.
Should this low concentration
disappear,
the process stops producing chlorine dioxide and a white gas (cWorine + water vapor) is seen as well as a grayish-white
generator liquor; this condition is known
as a white-out. Operation at lower acidities (5-7 N) helps prevent loss of cWoride
ion but at the expense of inefficient methanol use (up to 0.2 t/t of CI02). Operation
at 8-10 N acidity leads to better methanol

use (0.15 tIt of C102) but more care is
needed, or a small amount of sodium chloride added, to prevent white-out.
Metathesis of Na3H(SO)2 produces sodium sulfate crystals and a solution containing some dissolved sodium sulfate and all
of the sulfuric acid; the liquor is returned
to the generator (32).
Na3H(SO)2 ~ Na2S04(solid) +
NaHS04 (solution)
[28]
This process decreases the amount of byproduct requiring neutralization. A second

saltcake filter and second dissolving tank
are added as part of the flowsheet shown
in Fig. 3.
Other processes
When hydrogen peroxide is used as the
reducing agent (33, 34), the overall reaction based on equation [9] is
2 NaCI03 + H202 + H2S04~ 2 CI02 + 02 +

2 HP
[29]
+ Na2S04
This process has many. desirable characteristics because it produces no by-product

chlorine and directly produces neutral sodium sulfate. Its implementation has been
severely limited by the high cost of using
hydrogen peroxide as a reducing agent.
Considerable effort is being made to develop electrochemical
processes which
split the saltcake by-product or the sodium
chlorate feed into their respective acids and
bases:
Na2S04 + 2 HP ~ 2 NaOH + H2S04
NaCI03 + HP
NaOH + HCI03
[30]
[31]
For these technologies to be successful,

the product acids need to be of sufficient
strength not to cause water balance problems in the chlorine dioxide generating systems, the operating
costs need to be
competitive
with purchased sodium hydroxide and acid, and the process cost competitive with respect to capital.
It is
predicted that, because of their high cost,
electrochemical processes will be adopted
only if environmentally driven, for example,
by restrictions placed on the disposal of
excess saltcake. Partial splitting, together
with a lowering
due to extended
bleaching, may
ing processes to
requirements.
67
in chlorine dioxide usage

delignification and oxygen
allow saltcake from existbecome balanced with mill
4. Testing
Analysis of chlorine dioxide solution and
generator liquor is required for efficient
plant operation.
Most tests for chlorate,
chlorite, chlorine, and chlorine dioxide involve the oxydation of iodide ion to iodine
which is titrated with a reducing agent such
as sodium thiosulfate or sodium arsenite
(35). pH is used to control the reaction and
differentiate the chlorine species involved:
CI2+ 21-~
20- + 12 (neutral pH)
[32]
Cl02 + 1 ~ ClO; + 1/2 12 (neutral pH) [33]
ClO; + 4 r + 4 W
pH,
- 1 N)
CI- + 2 HP (acidic
[34]
CI03- + 6 r + 6 H+ --'->CI- + 3 12+ 3 HP

(very acidic pH, 8 N)
[35]
The largest errors come from sampling

and analytical technique (36). Low concentrations of chlorine in R8/SVP-MeOH
plants require a different method because
of interference from the methanol which
leads to chlorine concentrations two to four
times higher than are actually present (37).
5. Safety hazards
Because chlorine dioxide gas is unstable
(3), it must be handled carefully and within
accepted limits. Generators are designed
to withstand chlorine dioxide puffs up to
200 mm Hg of chlorine dioxide. A puff (1)
is the name given to the decomposition of
chlorine dioxide:
2 CI02 ~ CI2 + 2 02 + heat
[36]
This name was coined to differentiate the

low speed wave of reaction [36] 1m/s)
from explosions (> 300 rn/s).
Decompositions in atmospheric generation units such as Mathieson, Solvay, or R2
create pressure sufficient to lift the explo-
68
sion hatch, releasing chlorine into the plant.

Severe decompositions in a generator have
been known to blow off piping, an entire
roof, and even to destroy the generator vessel. These severe decompositions generally
occur because of continued
feeding of
chemicals during a shutdown or because
of inadequate air stripping of the generator
before shutdown. Interlocks normally shut
down the feeds but are sometimes defeated
by unauthorized changes, bypass systems,
or leaking valves. Decomposition most often occurs during the restart when the air
removes the chlorine dioxide from solution
and creates a gas space of 25-30% CI02
090-228
mm Hg partial pressure) (11).
The safest way to avoid an explosion is to
restart with a minimum of air to the bottom spargers, 10% of normal, using 90% of
the bypassed air to sweep the generator gas
space for a period of 20 minutes.
It is important to use a vessel which is
built to withstand the overpressure and has
an appropriately sized explosion hatch to
keep the pressure under the vessel's limit
(1). Following or during a decomposition,
operators should not go near the explosion
hatch unless it is properly vented or surrounded by a protective barrier unless it can
be shown by generator liquor and gas analyses that the chlorine dioxide has been
stripped from the vessel.
High-vacuum systems such as the R series or SVP series are inherently safer because decomposition
generally does not
elevate the pressure even as high as atmospheric. Steam strips the chlorine dioxide
from the liquor more effectively than does
air. This means that less chlorine dioxide is
available for continued decomposition.
A
few exceptions to this normal mode of operation have occurred when all utilities (air,
steam, water, and power) have failed simultaneously while under full production.
In
these instances (about 10 incidents in 1000
plant-years of operation), the explosion
hatch has been lifted. Another exception
is a puff while the generator is on standby
or during refilling or dumping at atmospheric pressure.
Dilution of the liquor
with water and air purging of the gas space
help to avoid puffs under these conditions.
The maximum recommended

limit for
chlorine dioxide is 0.1 ppm for human exposure for an 8-hour period (2). Most plant
environments are normally well below 0.1
ppm when a proper ventilation system is
used. Exceptions can occur when there is
a spill of generator liquor or chlorine dioxide solution. In this event, self contained
breathing apparatus is required.
References
1. Paulet, G., and Desbrousser, S.,Archives des
Maladies Professionnelles,
de Mededne du
Travail et de Securlte Sociale (Paris) 33:59
(1972); 35:797 (1974); 31:97 (1970).
2. Haller, ].E, and Northgraves,
39:199 (Apri11955).
WW,
Tappi
3. Lenzi, E, and Rapson, WH., Pulp Pap. Mag.

Can. 63(9):T442
(1%2).
4. Hong, c., Lenzi, E, Rapson,
Chern. Eng. 45:349 (1967).
5. Rapson,W.H.,
W.H., Can.]
Tappi 39 : 554 (1956).
6. Woodside,
V., and Macleod,
Trade] 137(8):26 (1953).
K.S., Pap.
7. Ernest, EM., U.S. Pat. No. 3,058,808

16, 1%2).
8. Rapson,WH.,
Tappi 41:181 (1958).
9. Partridge,H.D.,
(1%1).
10. Atkinson,
(Oct
Rapson,WH.,
Tappi 44:698
E.S., Pulp Pap. 42:32 (1968).
11. Owen, D., "Maintenance

of Chlorine
Dioxide Generators,"
1990 TAPPI Bleach
Plant Operations
Short Course Notes,
TAPPI
PRESS, Atlanta,
p. 169.
12. Fredette,
M.C., "New ClO, Generation
Capacity" I 990TAPPI Bleach Plant Operations Short Course Notes, TAPPI PRESS,
Atlanta, p. 159.
13. Sepall, 0., and Buser. R.C., U.S. Pat. No.
3,347,628 (Oct. 17, 1%7).
14. Read, R.}., Pulp
T506 (1%7).
Pap. Mag. Can. 68(10):
15. Partridge,
H.D., Atkinson,
E.S., Schulz,
A.C., Tappi 54:1484 (1971).
16. Partridfje,
H.D., Schotpflt,
D,<;,)" :)~h\llil,
A.C., Rosen, H.]., Can. Pat. No. 969,735

(June 24, 1975).
17. Winfield,].D.,
29. 1974).
Can. Pat. No. 956.784
(Oct.

18. Swindells,
R., Yang, K., Bechberger,
E.,
"The Use of HydrocWoric
Acid for CIO,
Production,"
1984 TAPPI Pulping Conference Proceedings,
p.195.
19. Fredette, M.C. , "ERCO R7 CIO, Generator
Helps Balance Pulp Mill Chemical Supply,"
1982 TAPPI International
Pulp Bleaching
Conference
Proceedings,
TAPPI PRESS,
Atlanta, p. 77.
20. Fredette, M.C., U.S. Pat. No. 4,393,035
No. 4,393,036 (July 12,1983).
and
69
30. Fredette,
M.C., U.S. Pat. No. 4,473,540
(Sept. 25, 1984) and 4,627,%9
(Dec. 9,
1986).
31. Eka-Nobel, "Methanol-Based
SVP-Lite Reduces By-Product
Chlorine,"
Pap. Ind.
Sept.-Oct.
1990:7 (1990).
32. Szell, M., and Fredette, M.C.," The Development of the ERCO RIO Process"CPPA
Annual Meeting Proceedings, Tech. Sect.,
CPPA, Montreal, 1994, p.A211.
33. Isa, I., Yamamoto, H., Shindo, S., Shibuya,
M., Can. Pat. 1,170,019 (July 3, 1984).
21. Norell, M.G., and Wanngard,j.C.

U.S. Pat.
No. 4,678,653
(July 7, 1987); Holstrom,
U.M., Sendgren, L.M., Norell, M.,Axegard,
PA., U.S. Pat. No. 4,678,654 (July 7, 1987).
34. Sokol,j.C.,and
Conkle,j.,"Peroxide
Based
CIO, Process," CPPA Annual Meeting Pr0ceedings,
Tech. Sect. CPPA, Montreal,
1990, p. B47.
22. Hatherly,D.G.,Can.
29, 1974).
(Oct.
35. Standard
Testing Methods, Tech. Sect.,
CPPA, Montreal, Method No.]14P
Pap.
36. Fredette,M.C.,"CWorine
Dioxide Solution
Strength Losses in Storage" Spring Conference Proceedings,
Tech. Sect. CPPA,
1988, Session 3-2.
Pat. No. 956,783
23. Lohrberg, K., and Klamp,

56 (11):114 (1982).
24. Hughes,
(1980).
T.D., Pulp
G., Pulp
Pap. Can.
81(4):30
25. Day, G.A., and Fenn, E.E, U.S. Pat. No.

2,484,402 (Oct. 11, 1949).
26. Kesting, E.E., U.S. Pat. No. 2,664,341 (Dec.
29, 1953) and No. 2,731,325
(Jan. 17,
1956).
27. Fredette, M.C., "New ERCO R8 Process

Eliminates C'z, Catalyst, Some Saltcake and
Acid," 1983 TAPPI Pulping Conference
Proceedings, TAPPI PRESS,Atlanta, p. 629.
28. Fredette, M.C., "Get 50% More CIO, for
10% Captial with an ERCO R8 Process;'
1989TAPPI Bleach Plant Operation Seminar,TAPPI PRESS, Atlanta p. 151.
29. Norell, M., U.S. Pat. No. 4,770,868
13,1988).
(Sept.
37. Fredette, M.C., "R8/SVP-MeOH Efficiency

Measurement"
CPPA Annual Meeting Pr0ceedings,
1995, p. B269.
Foot Notes:
1. ERCO R3, R3H, R5, R6, R7, R8, RIO, Rll,
R12, R13 are trademarks owned by Sterling Pulp Chemicals and Sterling Canada
Ltd.
2. SVP, SVP HCI, Svp, (HCl), SVP(MARS),
SVP(MeOH) and SVP-HP are trademarks
owned by AKZO-Nobel.
~_.,
~-~
~-
-- .----
SECTION ll:
Raw Materials
Chapter 3:
Chlorine, Sodium Hydroxide, Hydrogen Peroxide,
Peroxy Acids, Oxygen, and OZone
Dennis Owen1
John
Dennis Owen and Associates

Kingston, ON, Canada
R. Anderson1
DuPont Canada Inc.

Maitland, ON, Canada
Gordon Homer3
Canadian Liquid Air Ltd.
Vancouyer, BC, Canada
1. Chlorine and sodium hydroxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
1.1 Chlorine: properties, safety, and materials
of construction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
1.2 Sodium hydroxide properties, safety, and
materials of construction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
1.3 Manufacture of chlorine and sodium hydroxide. . . . . . . . . . . . . . . . ..
1.4 Chlorine storage and handling. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
1.5 Sodium hydroxide storage and handling . . . . . . . . . . . . . . . . . . . . . . ..
73
2.Hydrogenperoxide
2.1 Properties, safety, and materials of construction. . . . . . . . . . . . . . . . ..
2.2 Manufacture of hydrogen peroxide . . . . . . . . . . . . . . . . . . . . . . . . . . ..
2.3 Storage and handling of hydrogen peroxide
77
77
78
79
73
73
74
76
77
3.Peroxyadds.
79
3.1 Properties, safety, and materials of construction. . . . . . . . . . . . . . . . .. 79
3.2 Manufacture of peroxy acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 80
3.3 Storage and handling of peroxy acids
80
4. Oxygen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .,
4.1 Properties, safety, and materials of construction. . . . . . . . . . . . . . . . ..
4.2 Manufacture of oxygen
4.3 Transportation and handling of oxygen. . . . . . . . . . . . . . . . . . . . . . . ..
81
81
82
84
5. OZone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 85
5.1 Properties, safety, and materials of construction. . . . . . . . . . . . . . . . .. 85
5.2 Ozone manufacture. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 85
ISection I, 2Sections 2 and 3; 3Sections 4 and 5

71
~--,-_.
Chapter n 3: Bleaching Chemicals: Chlorine, Sodium

Hydroxide, Peroxy Acids, Oxygen, and Ozone
Chapter n 3:
Chlorine, Sodium
Hydroxide, Hydrogen
Peroxide, Peracids,
Oxygen, and Ozone
Preface
This chapter concerns the properties, manufacture, and safe handling of the bleaching chemicals chlorine, sodium hydroxide,
hydrogen peroxide, peroxy acids, oxygen,
and ozone. Chlorine dioxide properties and
manufacture have been covered in the preceding chapter; this material has been.
placed in a separate chapter for editorial
convenience. Hydrosulfite properties and
manufacture are covered in Chap. V 2.
1. Chlorine and sodium

hydroxide
'.
1.1 Chlorine properties,
safety, and
materials of construction
liquid chlorine is amber in color and has a
saturated liquid density of 1.467 g/cm3 at Oe.
At atmospheric
pressure
it boils at
-34e. Chlorine gas is greenish-yellow and has
a saturated gas density 2.48 times greater than
air. Under standard conditions, the weight of
one volume of liquid chlorine equals the
weight of 456.5 volumes ofthe gas.
The solubility of chlorine in water is dependent on temperature as shown in Table
1 for a partial chlorine pressure of 750 mm.
Below 1000C,chlorine combines with water, forming crystalline hydrates (1).
Table 1. S61ubilily of cblorlfle gtIS,,, lHIer /II4ifferetlt tempetYllrl"S '.
Temperature
("C)
10
20
30
40
,
Chlorine
partial pressure
Solubility
(g/L)
9.65
7.29
5.80
4.77
of 750 mm.
73
Chlorine is a hazardous chemical which

can cause injury or death. No attempt
should be made to handle chlorine for any
purpose without a thorough understanding
of its properties and the hazards involved
in its use (2). Chlorine is a respiratory irritant. In sufficient concentration,
the gas
irritates the mucous membrane, respiratory
system, and skin. In extreme cases, difficulty in breathing may increase to the point
where death can occur through suffocation.
liquid chlorine causes bums to the skin and
eyes (3). For personnel safety, canister-type
masks should be available to all personnel
working in proximity to chlorine and selfcontained breathing apparatus is required
when long-term exposure to chlorine or
high chlorine concentration is a risk. Chlorine gas monitors should be placed in and
around the facility. Immediate temporary
treatment should be given to exposed individuals. Victims should be moved into a
fresh air environment and artificial respiration and oxygen administered (3-6).
Although dry chlorine (gas or liquid) does
not react with (corrode) many metals, it is
very reactive (strongly corrosive) when
moisture is present. Precautions should be
taken to keep chlorine and chlorine equipment free of moisture. Chlorine has a strong
chemical affinity for many substances and
reacts with many inorganic substances with
the evolution of heat. At elevated temperatures, chlorine gas reacts vigorously with
many metals and, at ambient temperature,
it reacts vigorously with titanium. Chlorine
gas supports combustion.
74
mate scarring. Because signs and symptoms

of irritation are frequently not evident immediately after contact with sodium hydroxide, injury may result before one realizes
that the chemical is in contact with the
body. Therefore, sodium hydroxide in any
concentration or form should be handled
with extreme care. Persons handling sodium hydroxide should always wear closefitting chemical safety goggles, a hard hat,
rubber gloves and, depending on the probability of exposure, additional clothing and
equipment (7).
The use of silicon-<:ontaining alloys is not
recommended
for equipment to be contacted with sodium hydroxide. In order of
descending corrosion resistance to 50%
sodium hydroxide solution at 55C-75"C are
Inconel, nickel Monel, cupro nickel 00-30),
chrome nickel steel (18-8), steel, and cast
iron (8). Besides the normal corrosion, a
concentrated sodium hydroxide solution at
greater than 60"C may cause stress corrosion cracking in stainless steel. The risk can
be minimized by reducing stress in the
metal.
1.3 Manufacture of chlorine and sodium hydroxide

When a direct current is passed through
a solution of sodium chloride, the products
are chlorine, hydrogen, and sodium hydroxide. The following stoichiometric equation
applies:
Cl2 + H2
[1]
The production capacity distribution for

the major different types of operating chlorine cells in the United States at this time is
77% diaphragm cell, 15% mercury cell, and
7% membrane cell. In Canada, the distribution is 82% diaphragm, 10% mercury cell,
and 8% membrane cell (9).
On-site chlor-alkali plants are installed
where merchant chlorine and sodium hydroxide are unavailable or are too expensive. Historically, on-site generation was
desirable if the chlorine and caustic (sodium
hydroxide) purchases of a mill were in stoichiometric electrochemical
balance, that
iS,l ton of chlorine per 1.128 tons of sodium hydroxide (an Electrochemical Unit,
ECU) (10). Most on-site manufacture now
involves the use of a membrane cell because
of handling problems with mercury in the
mercury cell, mercury loss to the environment, and problems associated with the
safe handling of the asbestos required for
the diaphragms (11).
Membrane cells use a cation exchange
membrane to separate the anode and cathode compartments.
Figure 1 shows a schematic diagram of a typical membrane cell.
Brine is fed into the anode compartment
where chloride ion discharge at the anode
surface leads to the formation of chlorine
gas. Sodium ions and associated water of
Anode
Membrane
Cathode
1.2 Sodium hydroxide properties,

safety, and materials of construction
Sodium hydroxide is a white solid with a
density of 2.130 g/cm3 and a melting point
of 318"C. Most pulp mills receive sodium
hydroxide as a 50"Aisolution. Sodium hydroxide is chemically active, reacting with
a wide variety of organic and inorganic
chemicals. It can react violently with water, acid, and other substances.
Concentrated sodium hydroxide causes
bums on contact with body tissues, frequently causing deep ulceration and ulti-
2 NaCl + 2 H,o + 2 Faradays

+ 2 NaOH
Saturated
brine
__ NaOH
Depleted
brine
Fig. 1. Sbettultk
aolution
4i11grt1m of typk411llelllbrrlfle
Water
of eblorlfle
cell for
""'''''f'''"
11114soill"m
by4roxitle.
Chapter II 3: Bleaching Chemicals: Chlorine, Sodium

hydration are transported through the membrane and are discharged at the cathode
surface, forming hydrogen gas. The 32-35%
sodium hydroxide solution thus formed is
entirely satisfactory for all chemical uses in
the bleach plant.
Membranes are the most critical component of the cell technology because of their
influence on energy consumption.
Membranes consist of a film of three layers:
perfluorosulfonate,
perfluorocarboxylate,
and Teflon fabric for reinforcement. A surface treatment is sometimes applied to accommodate a no-gap cell design. Through
the use of multi-layered membranes, zero
gap, and cathodic coatings, a power consumption of 2,000-2,300 kWh/ton of sodium hydroxide
has been achieved at
current densities of 2-4 kAlm2 (12).
An effective brine purification system is
essential for the efficient operation of a
chlor-alkali membrane cell. The salt supply
for a plant can be obtained by solar or
vacuum evaporation. Solar salt is generally
the least expensive, particularly for a mill
situated on a seaboard site. However, the
solar salt brine purification requirements are
greater than those for vacuum-evaporated
salt.
Typical specifications for treated brine
are given in Table 2. Decline in membrane
performance
can be caused by calcium,
magnesium, barium, iron (ferrous and ferTllbte 2. SpeclftetIUons for memlJty,ne cell feed brine.
Impurity
Unit
Amount
NaCI
Ca+Mg
Sr
Si02
I
Ba
Al
Na2S04
Fe
Ni
g/L
ppb
ppm
ppm
ppm
ppm
ppb
ppm
ppm
ppm
280-305
20
0.5
5
0.4
0.4
50
5
0.5
0.05
Hg
T.O.c.
F
ppm
ppm
ppm
0.04
1
1
75
ric), nickel, strontium, and silica in brine.

Trace amounts of calcium and magnesium
ions markedly affect both current efficiency
and cell voltage. The most important anionic impurity is sulfate; concentrations of
this anion as low as 7 g/L cause a noticeable loss in current efficiency (13-15).
Brine treatment
Brine resaturation, precipitation, absorption, clarification, and filtration account for
a significant portion of the overall chlor-alka1i production cost. Depleted brine from
the anode compartment is first acidified and
dechlorinated to recover dissolved chlorine
and prevent corrosion in other plant equipment(16). Reducing agents, sodium sulfite
or hydrogen peroxide, are used to eliminate
chlorine (17) and catalysts are used to remove the final traces of chlorine (18). Sodium carbonate and sodium hydroxide are
added to precipitate calcium and magnesium. The brine concentration is increased
by passing the depleted brin solution
through a salt bed. The sulfate in the brine
is controlled by I) precipitation as calcium
sulphate or barium sulfate, 2) low-temperature crystallization
as sodium sulfate
decahydrate (19), or 3) adsorption onto a
catalyst (20). The resaturated
brine is
passed through an activated charcoal column to remove any residual free chlorine
and then through ion exchange columns
packed with a chelating-type of resin for
removal of calcium and magnesium. Some
brines contain ammonium ions or organic
nitrogen compounds which can be converted to nitrogen trichloride (NCI3) in the
electrolyzer
and, if concentrated
in the
downstream process, may explode (21).
Ammonium ions are removed by chlorine,
producing (N2Cl) which can be removed as
a gas or by hypochlorite which produces
nitrogen.
Electrolysis
Electrolyzers for on-site chlor-a1ka1i plants
can be of the monopolar- or bipolar-type.
Membranes are replaced approximately
every five years. The titanium anodes are
coated with oxides of ruthenium, tin, and
titanium (22-24) and require recoating every five years. Cathodes are nickel or nickel-
76
clad steel and, where activated nickel surfaces are used for lower voltage, require
replacement or recoating every five years
(12).
Chlorine and hydrogen are produced in
the electrolyzer at slightly greater than atmospheric pressure. The sodium hydroxide discharged from the cathodic side of the
electrolyzer, after separation from the hydrogen, flows to a catholyte tank where it
is cooled before being recycled to the
electrolyzer. Sodium hydroxide concentration is controlled at 32-34% by recycling the
catholyte and varying the amount of deionized water used for makeup.
Hydrogen, scrubbed to remove residual
sodium hydroxide, may be used as an auxiliary fuel in the pulp mill lime kiln or
burned with chlorine to make hydrochloric acid. Care should be taken to avoid creating an explosive mixture of hydrogen,
chlorine, and oxygen (25).
Chlorine recovery
Chlorine is recovered by cooling, drying,
compression, and liquefaction. It is stored
and transported as liquid chlorine which is
ultimately vaporized to supply chlorine gas
to a chlorination stage.
Chlorine produced by the electrolyzer is
saturated with water vapor at high temperatures. The chlorine gas is first cooled but
temperatures less than 1000C(1) should be
avoided to prevent the formation of chlorine hydrate crystals. The cooled chlorine
gas then flows to sulfuric acid drying towers. The upper limit for moisture remaining after drying is 50 ppm (-48"C dew point)
(26). A sulfuric acid-sealed, liquid-ring reciprocating compressor can be used to compress the gaseous chlorine.
Single-stage
liquefaction units are not designed to liquefy more than 90-95% of the chlorine. A
three-stage reciprocating compressor is capable of producing the chlorine gas pressure required in the chlorination
stage.
About half ofthe chlorine is liquefied (27).
The gas flows directly to the chlorination
stage. Should the plant demand exceed the
gas flow, liquid chlorine is fed from the storage tank through a vaporizer. This system
requires only one liquid chlorine storage
tank (28). To minimize the adverse consequences of tank rupture, the minimum
quantity of liquid chlorine should be stored
on-site. All chlorine-contaminated
streams
should be safely vented through emergency
scrubbers (29).
1.4 Chlorine storage and handling

Chlorine supplied by merchant producers is shipped as a liquid under pressure in
a barge, tank car, tank truck, or by pipeline. All wetted parts are made of steel, constructed according to Chlorine Institute
standards and are equipped with safety devices which relieve pressure at temperatures over 165"F (74"C) at pressures above
safe operating levels.
Most of the chlorine tank cars now in service have a 55- or 90-ton capacity. All cars
are insulated and the insulation is protected
by an outer steel jacket. Tank cars are unloaded at the center of the top through a
valve arrangement which is enclosed in a
protective steel housing. Chlorine handling
systems should be designed by engineers
familiar with chlorine (30-34). The tank car
is pressurized to 20-25 psi above the minimum chlorine pressure in the car with dry
air or nitrogen. A reserve tank is placed in
the liquid chlorine line to provide 15-30
minutes' supply to facilitate changeover
from one tank car to another; expansion
tanks are required on liquid chlorine lines
to prevent excessive pressure development
between any two shut-{)ff valves.
Chlorine is vaporized and superheated
to 150"F (66"C). The vaporization is controlled by gas temperature or, in many cases,
simply by applying a constant steam pressure of 25 psi to the steam side (35). Barometric legs should be installed immediately
before chlorine injection to stock lines, hypochlorite reactors, or blowdown tanks to
eliminate aspiration of water into the dry
chlorine system during a shutdown. A blow
down system is essential for safety in handling chlorine. A tank containing sufficient
dilute soldium hydroxide or calcium hydroxide to absorb the maximum amount of
chlorine contained in any part of the chlorine system should be provided. All chlorine gas piping should slope toward the

evaporator so that any condensed chlorine
runs back; liquid chlorine lines should slope
back to the rail car to facilitate emptying of
the system.
Emergency response plans that include
the training of personnel in the use of emergency kits to seal leaking valves (36) should
be prepared for the plant, taking into consideration the estimated area affected by
potential chlorine releases (37-38).
77
approximately 60% hydrogen peroxide. Hydrogen peroxide has a slightly pungent odor
most often detected if aerosols are formed
at a nozzle during unloading or transfer.
Table 3. Properties of bydrogtm peroxiIle.
Properties
of 50"10solution in water
Specific gravity at 25C
1.19
Freezing point
-52"C
H,o, partial pressure
at 25"C
13.5 rnrn Hg
1.5 Sodium hydroxide storage and

handling
Boiling point
Most pulp mills receive sodium hydroxide as a 50% aqueous solution in tank cars,
tank trucks, barges, or pipelines. Tank cars
contain 25 or 50 tons of sodium hydroxide
at 50% concentration (50 or 100 total tons).
Sodium hydroxide tank cars are equipped
to be unloaded by pump or air pressure;
they can be unloaded from the top or bottom of the tank car or truck. The unloading area should be designed to confine and
collect any sodium hydroXide lost from the
unloading system. Because 50% sodium
hydroxide solution freezes at 16C, it is
stored in a heated tank. Storage tank areas
need to be diked because sodium hydroxide is designated as a hazardous material.
Sodium hydroxide is diluted to 5 or 25%
in a continuous dilution system as required.
The dilute sodium hydroxide storage tank
level controls the flow of dilution water to
a mixing tee and coil. The dilute sodium
hydroxide concentration can be measured
by a conductivity cell or density gauge.
Hydrogen peroxide solutions are often

stabilized with additives to ensure safe transport and to limit decomposition if the solution is diluted for on-site storage. Hydrogen
peroxide can become unstable with the
application of heat or contaminants.
Concentrated
hydrogen peroxide solutions
(>65%) can undergo self-accelerating exothermic decomposition, with oxygen gas
and steam release, which can cause a dangerous pressure increase if the space cannot be adequately
vented.
Hydrogen
peroxide can react vigorously with rust,
dust, dirt, iron, copper, brass, heavy metals
or their salts, alkalis, and certain organic
materials (especially vinyl polymers). Hydrogen peroxide is incompatible with most
flammables/combustibles as well as cyanides,
nitric acid, potassium permanganate, and
other oxidizing and reducing agents (40).
Hydrogen peroxide is an oxidant that can
be handled safely when risks are minimized
through proper system design and use of
personal protective equipment.
Hydrogen peroxide can cause severe irritation or burns of the skin, eyes, and mucous membranes. Skin exposure can lead
to bleaching of the skin and hair. The severity of burns is dependent on solution
concentration.
Permanent damage is unlikely for exposures at less than 10% concentration.
Eye contact with hydrogen
peroxide can cause severe damage resulting from ulceration of the cornea and denaturing of the protein in the ocular fluid.
Prolonged exposure or contact with solutions at greater than 5% concentration may
cause irreversible eye damage. The first-aid
treatment is to flush the exposed areas im-
2. Hydrogen peroxide
2.1 Properties, safety, and materials of
construction
Hydrogen peroxide is a clear, colorless
liquid which is available commercially as an
aqueous solution in concentrations ranging
from 30% to 70%. It is completely miscible
with water. Hydrogen peroxide can be

transported safely at concentrations up to
70%,but it is usually stored at 50%concentration. Some of the properties of hydrogen peroxide are listed in Table 3. The
freezing point of 50% peroxide is -52C and
there is a low-freezing-point eutectic at
114"C
78
Pulp Bleaching
-Principles
and Practice
mediately with large volumes of water. All

personnel working with or near hydrogen
peroxide systems should wear proper personal protective equipment which should
include splash-proof
chemical
monogoggles. Personnel opening hydrogen peroxide systems need to be aware of the
potential for system pressurization due to
the slow "normal" decomposition of hydrogen peroxide.
Although hydrogen peroxide does not
burn, contact with organic materials may
cause decomposition with the accompanying release of oxygen gas and heat which
can initiate spontaneous combustion of the
organic material. Care must be taken to
avoid contact with clothing.
Alkaline hydrogen peroxide solutions can
cause titanium corrosion under conditions
of high temperature, pH, and concentration
(i.e., >80OC, > pH 11, >3% H202 concentration). Corrosion can be inhibited by addition of calcium or magnesium salts (41).
Hydrogen peroxide systems should be made
of 304L or 316L stainless steel. Pumps and
valves should be made of 316L stainless steel
Recycle
2.2 Manufacture
of hydrogen peroxide
Most of the hydrogen peroxide used today is produced by the anthraquinone process shown in Fig. 2. This is a cyclic process
wherein a working solution containing an
alkyl anthraquinone is sequentially hydrogenated, oxidized, subjected to an extraction process, and recycled back to the
hydrogenation step.
In the hydrogenator, alkyl anthraquinone
reacts with hydrogen in the presence of a
catalyst. The resulting solution containing
hydrogenated alkyl anthraquinone is filtered
to remove the catalyst and is fed to the oxidizer. It reacts with air or oxygen to form
hydrogen peroxide and regenerate the alkyl
anthraquinone. In the extraction step,demineralized water is added to extract crude
aqueous hydrogen peroxide, leaving the
alkyl anthraquinone
working solution for
recycle to the hydrogenator.
The crude
hydrogen peroxide is purified and concentrated.
working solution
o:)Cr
I
-..;;::
-..;;::
::
R-Anthraquinone
(RAQ)
Contaminants
and storage tanks, 304L or 316L stainless

steel or 5254 aluminum.
+H2---'
CAT
~
1
H
o
:: " ::
-..;;:: R Hydrogenated
::
R-Anthraquinone
(HRAQ)
OH
Compressor
Low strength "crude" peroxide

Stabilizers are added before shipment to
minimiZe decomposition during transit and
storage. Most hydrogen peroxide solutions
are stabilized with tin and phosphate compounds and some may contain a nitrate salt
to inhibit the tendency of any chloride ions
to corrode aluminum storage equipment.
An electrolytic process for the manufacture of hydrogen peroxide has been operated on a limited commercial
basis. It
converts oxygen and water to hydrogen
peroxide in a strong alkaline solution:
0z + HP
+ 2 e- -> HOz- + OH-
[2]
This process produces a 4% hydrogen

peroxide solution with a 1.5-1.7:1 total alkalinity to hydrogen peroxide ratio. The
plant needs to be located on the site of the
end use because any further processing,
such as purification or concentration,
or
shipping of a dilute solution would be uneconomical. The electrolytic cell produces
a hydrogen peroxide sol~tion that may be
too dilute or too alkaline for certain bleaching applications, and purchased hydrogen
peroxide may be required to supplement
the on-site production.
Hydrogen peroxide manufacture by direct combination of hydrogen and oxygen
has been tested on a pilot plant scale. The
exceptional requirements for reaction containment and other safety features have limited further development.
2.3 Storage and handling of hydrogen

peroxide
Hydrogen peroxide storage and feed systems must be designed to minimize the
potential for product contamination, chemical exposure, and pressurization
due to
decomposition.
Decomposition
is highly
eXothermic and leads to the release of oxygen gas. Pressure can increase quickly
when hydrogen peroxide decomposes in a
closed system. Storage tanks must have
adequate emergency vents and drains, or
pressure relief devices must be installed,
wherever
hydrogen
peroxide
can be
trapped between closed valves. Ball valves
are recommended
for hydrogen peroxide
service; the balls should be drilled so that
79
the cavity can be vented. Caution should

be exercised when disconnecting hydrogen
peroxide lines because of the potential for
unforeseen pressurization.
Hydrogen peroxide is usually stored as a
50% aqueous solution. It is often diluted
(to approximately 5% concentration) before
application to pulp.
3. peroxy acids
3.1 properties, safety, and materials of
construction
A peroxy acid, or peracid, is an acid that
contains a perhydroxyl group ("OOR) in
place of the hydroxyl group of its parent
acid. Peroxy acids are described in more
detail in Chap. IV 10. Percarboxylic acids
(e.g., peracetic acid) are weaker acids than
their parent acids. The peroxy acids of primary commercial interest are peracetic
acid, CH COOOH, and Caro's acid, monopers.c
acid or HzSO,. Caro's acid is a
dibasic acid. The ionization constant of the
perhydroxyl proton, pKz, is much higher
than the p~ for sulfuric acid; therefore, t~e
Caro's acid anion is a much weaker aCid
than the parent acid.
The principal hazard of peroxy acids is
their corrosive nature, which causes severe
burns to skin, eyes, and body tissue. Contacted areas must be washed immediately
with large volumes of water to avoid tissue
damage.
Peracetic acid has a sharp, pungent odor.
It has a boiling point of 103C and a vapor
pressure of 20 mm Hg at 25C. Exposure
to the vapor causes lachrrmation and possibly lung damage. Long-term exposure to
peracetic acid can lead to liver damage, decreased white blood count, and lung tumors
(42). Personal protective equipment should
include a respirator in addition to splashproof goggles, rubber acid suit, and rubber
gloves. Caro's acid, peracetic acid, and
mixtures of these two peroxy acids are not
shock sensitive. However, some mixtures
of 70% hydrogen peroxide and glacial acetic acid are detonatable if present in. the staichiometric molar ratio 4-HP z:l-CH3COOH.
Mixtures of 50% hydrogen peroxide and
glacial acetic acid are not detonatable.
80
Pulp Bleaching
-Principles
and Practice
Peroxy acids decompose on heating and

oxygen gas is released as a by-product.
Decomposition is accelerated by contamination with iron, copper, chromium, and
cobalt. The most likely source of metal contamination is the sulfuric acid feedstock. An
iron content of less than 25 ppm is recommended (43).
It is advised that pumps and piping in
contact with a moving stream of peroxy
acids be lined with an appropriate
fluoropolymer (e.g., Teflon"'). The recommended material of construction for a heat
exchanger is Teflon'" for the process-exposed tubes and carbon steel or other suitable material for the heat exchanger shell.
316L stainless steel is suitable for the peroxy
acid reactor, but care must be taken to minimize contact with dilute sulfuric acid solutions. The presence of the active oxygen
from the peroxy acid (and accompanying
hydrogen peroxide) stabilizes the oxide film
on the stainless steel and inhibits corrosion.
The main precaution to be taken when using peroxy acids in stainless steel bleaching equipment is to ensure good mixing.
Unmixed peroxy acid decomposes, creating an aggressively corrosive sulfuric acid
and acetic acid mixture. Titanium corrosion
is a function of temperature and peroxy acid
concentration. Corrosion is minimal at the
temperatures and addition rates considered
reasonable for a bleaching application (44).
3.2 Manufacture of peroxy acids

Peroxy acids are not sufficiently stable
to be shipped or stored for long periods of
time (43). Transportation of certain peroxy
acids may be restricted by Transportation
of Dangerous Goods (TOG) regulations, although Sweden permits the transportation
of distilled peracetic acid under controlled
conditions. Peroxy acids are used commercially for chemical syntheses, but the scale
of consumption in a pulp bleaching application requires safe and economical generation of peroxy acids at the pulp mill site.
Peroxy acids are usually prepared from
the reaction of the parent acid with hydrogen peroxide (see Chap. IV 10). For the
preparation of peracetic acid, a strong acid
catalyst such as sulfuric acid must be added
for the reaction to attain equilibrium in a

reasonable time. Caro's acid can be prepared by the reaction of concentrated sulfuric acid and hydrogen peroxide (45).
Peroxymonosulfate
has also been used as a
source of caroate ion (46).
Highly concentrated
reactants must be
used to shift the equilibrium reaction toward the formation of peroxy acids. A reasonable conversion of hydrogen peroxide
to peroxy acids requires the use of a significant molar excess of the parent acid. Conversion is limited to approximately 45% for
Caro's acid when a ratio of 1.5 moles of93%
sulfuric acid to 1 mole of 50% hydrogen
peroxide is used. Higher conversion can
be achieved by the use of 70% hydrogen
peroxide, but there are concomitant safety
issues associated with the storage and handling of such a high-concentration
solution.
Peracetic acid is also limited to 45% conversion under typical equilibrium conditions.
The conversion of hydrogen peroxide to
peroxy acids can be increased significantly
when glacial acetic acid is added to a Caro's
acid solution (45). The resulting solution
is a mixture of Caro's acid and peracetic
acid. Conversions of 85-90% from hydrogen peroxide can be achieved using 50%
hydrogen peroxide.
'For peracetic acid, the equilibrium can
also be shifted by vacuum distillation of the
peracetic acid together with the water. A
high conversion of hydrogen peroxide can
be achieved (e.g., >90%) with a stoichiometric (i.e., 1:1) ratio of acetic acid to hydrogen peroxide
(43). This requires the
installation of a vacuum still on the mill site.
There are process hazards associated with
the distillation of acetic acid-peracetic acid
solution, related to the detonability of concentrated mixtures, that must be considered
in the design and operation of a distilled
peracetic acid system (47).
3.3 Storage and handling of peroxy

acids
Storage is limited by the stability of the
peroxy acid and the generation method.
One method involves adiabatic in-line mixing where the pulp stock acts as the heat

sink for the exothermic heats of mixing and
reaction (48). Corrosion and the peroxy
acid yield are areas of concern in this generation method.
Temperature-<:ontrolled
reactors permit
generation of a high-<:onversion peroxy acid
solution which can be assayed before application to pulp. Control of the peroxy acid
temperature provides stability sufficient to
permit storage for management
of most
maintenance and operation outages.
4. Oxygen
construction
Oxygen is a gas under normal atmospheric conditions. It is indispensable for
the maintenance of life and for combustion..
Oxygen is a colorless, odorless, tasteless gas
that is slightly heavier than air. It accounts
for 20.94% by volume ofthe air components
heavier than air. At atmospheric pressure
and temperatures below -183"C, oxygen is
a transparent
pale blue liquid, slightly
heavier than water. Some properties of
oxygen are listed Table 4 (49). Oxygen is a
highly reactive gas which combines directly
with most elements to form oxides. Certain
elements, for example, phosphorus
and
magnesium, ignite spontaneously in oxygen
(or in air); noble metals are only slowly oxidized at very high temperatures. Oxygen is
liable to react violently with organic substances.
Oxygen does not burn but vigorously
supports combustion.
In fact, many mate-
rials not normally considered combustible

bum readily in the presence of pure oxygen. Oil and grease have a unique affinity
for oxygen, often resulting in spontaneous
combustion
when they are brought together. Oxygen is shipped as a gas under
high pressure in cylinders, as a liquid at low
temperature under its own vapor pressure,
or is transported by pipeline at moderate
pressure.
Oxygen is the gas that is essential for sustaining life. Oxygen-poor atmospheres (less
than 17% O2 by volume) can cause serious
tissue damage and are capable of leading
to death by asphyxiation if the oxygen content becomes seriously low (less than 12%
by volume). It is essential to provide adequate ventilation in areas where oxygen
tends to pool in an air atmosphere, that is,
in low spots, gutters, ditches, and drains.
Neither smoking nor open flames are permitted in oxygen storage or use areas. Similarly, storage of organic and flammable
materials is not permitted in areas where
oxygen is used.
Handling or transfer operations must be
carried out on a non-<:ombustible, non-porous floor material such as cement, concrete, or paving tiles. Bitumen, asphalt, and
wood are prohibited as flooring materials.
Oil and grease should never be used on
oxygen equipment. Oil- and grease-stained
clothing should never be worn while working on oxygen-<:arrying equipment, floors
should not be oil-stained, and all equipment
should be designed and degreased for oxy-
Table 4. Cben/kal and pbyskal properties of oxygen (1).

Specific
gravity of gas at 70"F (21.1 "C) and 1 atm (Air
Density
of gas at 70"F and (21.1 "C) and 1 atm
Density
of gas at boiling point
Density
of liquid at boiling
point
Boiling point at 1 atm

Latent heat of vaporization
at boiling point
Specific heat (Cp) at 70"F (21.1"C) and 1 atm
Specific
heat (Cv) at 70"F (21.1"C)
81
and 1 atm
= 1)
1.1053
31.329 kg/m;
4.475 kg/m;
1141.0 kg/m;
-183.00"C
213 kJ/kg
0.9li kJ/kg
0.653 kJ/kg
Liquid/gas ratio (liquid at boiling point, gas at 70"F

and 1 atm) VIV)
0.001162
Solubility of gas in water

(V IV of water)
0.031
at 70"F (21.1 "C)
82
gen service. Liquid oxygen should always

be handled with correct clothing (gloves,
goggles, and safety shoes). If clothing encounters a liquid oxygen spill or is saturated
with oxygen gas,it should be well-ventilated
before being brought close to any source
of ignition.
Should an accident occur, water is the
best extinguisher
for fire. For "bums"
caused by low temperatures, the affected
area should be bathed in water or a cold
compress applied to gradually warm the
region of the injury.
Air
4.2 Manufacture
of oxygen
Air is a mixture of the following components: oxygen (21% by volume), nitrogen
(78%), argon (less than 1%) and trace quantities of carbon (350 ppm), neon (18 ppm),
helium (5 ppm), krypton (1 ppm), and xenon (0.08 ppm). Depending on the ambient air quality, other components such as
hydrocarbons,
nitrogen oxides, carbon
monoxide, hydrogen, ozone, SO x,dust, and
water may also be present.
The separation of air into its constituents

was commercialized
in 1896 by Georges
Claude with his development of an industrial cryogenic process for the liquefaction
and fractionation of air. The three industrial processes that are presently available
to separate air into some or all of its components are
Process
Year of Invention
Cryogenic distillation
1902
Adsorption
1965
Membrane separation
1975
At present, only distillation and adsorption are commercially viable for oxygen
supply to the pulp and paper industry. The
commercial cryogenic separation of air into
its component gases entails cooling air until it liquefies and the fractional distillation
of each component. Adsorptive separation
consists of passing a feed gas (air) over a
suitable adsorbent such as a zeolite molecular sieve which selectively adsorbs one or
more components of the feed gas (nitrogen),
thereby producing a gas enriched in remaining components (oxygen).
Liquid 02
Fig. 3. Plowsheet
for cryogenk
separation
of oxygen.
In the membrane separation system for

air, oxygen and water diffuse through the
membrane to the atmosphere while a dry,
concentrated
nitrogen stream is retained.
The membrane system presently cannot
produce oxygen streams of sufficient concentration for use in pulp mills. Membrane
separation is of interest, however, in the production of dry nitrogen for the pressurization of chemical systems requiring an inert
atmosphere.
Cryogenic separation
The primary output of an on-site cryogenic air separation plant is high-purity gaseous oxygen and small amounts of liquid
oxygen produced to maintain the on-site
backup supply of liquid oxygen for pulp
mills that are remote from commercial oxygen suppliers.

Air must first be purified to remove all
moisture and carbon dioxide which would
otherwise freeze during the liquefaction
process. To accomplish this - air which
has to be filtered first to remove particles
is compressed and cooled and the water
vapor is condensed and removed. The final
small amounts of moisture and carbon dioxide are removed by adsorption or refrigeration.
A flowsheet for cryogenic separation is
shown in Fig. 3 (50). Atmospheric air is
drawn though an intake filter and compressed in a multi-stage, water- cooled, centrifugal compressor.
The air is passed
through a set of reversing heat exchangers, warm and cold in series. The incoming air is cooled by heat exchange and the:
water and carbon dioxide in it are deposited on the exchanger surfaces. When the
exchangers reverse, the solid deposits sublime into the waste nitrogen stream and
are removed.
The cold, clean air flowS from the reversing exchangers to the expansion turbine
where it is further cooled to liquefaction
temperatures. The liquid is fed to a distilla-
tion unit which produces

uid oxygen.
83
the purified liq-
Separation by adsorption
Adsorption is a very simple process that
produces gaseous oxygen at purity levels
up to 95%. Because no liquid is produced,
liquid oxygen must be supplied from an outside source and stored on-site as back-up.
The process consists of a cyclic sequence
in which 1) nitrogen is absorbed by molecular sieves at high partial pressure, forming
a purified oxygen stream and 2) desorption
at low partial pressure to regenerate the molecular sieves. Several process options are
available:
1) PSA (pressure swing adsorption):Adsorption under pressure, regeneration at
atmosphere pressure
2) VSA (vacuum swing adsorption):Adsorption near atmospheric pressure, regeneration under vacuum
3) VPSA(vacuum pressure swing adsorption):
Adsorption under pressure, regeneration
under vacuum.
In the oxygen systems in use today, the
adsorbent consists of a two-bed system with
a sparger vessel or a three-bed system. The
84
three-bed system,illustrated in Fig.4,moves

successively through the three stages of
adsorption, depressurized regeneration, and
repressurization every 90 seconds. When
the adsorber in service is nearly saturated,
it is isolated from the circuit and regenerated in three stages: 1) partial equilibrium
by means of a vacuum pump to recover residual oxygen in the top section, 2) repressurization
of the following adsorber
with the residual oxygen stream from the
vacuum pump, and 3) exhaustion of nitrogen to atmosphere by the vacuum pump.
The advantages and disadvantages
of
oxygen supply alternatives are presented in
Table 5.
Transportation and handling of
oxygen
On-site production of gaseous oxygen,
coupled with the storage of liquid oxygen
for backup, presents the complete range
of handling problems associated with oxygen. All systems must be cleaned for oxygen service: degreased and dried. Because
4.3
System
Compressor
Adsorption
Separation
Product manifold
Adsorber
beds
./'...
Exhaust
Exhaust
manifold
Vacuum
pump
Note: 1) This configuration
shows
Adsorber A - oxygen production
Adsorber B - nitrogen desorption

2) Piping and valves for repressurization
Fig. 4. PI_sheet fM pressure-S1IJItlg-adsorptlmlseJl4ratUm of~.
is extremely
cold (-183"C)
care must be taken to wear appropriate

clothing when handling liquid oxygen. All
pipelines must have safety relief valves in
case liquid is trapped and pipelines must
have the correct metallurgy for low temperatures.
The following bulletins are available from
the Compressed Gas Association, Inc., 500
Fifth Ave., New York, NY 10110, and should
be viewed as required reading for personnel handling oxygen:
CGA Bulletin G4 Oxygen
CGA Bulletin G4.1 Cleaning Equipment for
Oxygen Service
CGA Bulletin G4.4 Industrial Practices for
Gaseous Oxygen Transmission and Distribution Piping Systems
CGA Bulletin P12 Safe Handling of Cryogenic liquids
CGA Bulletin P14 Accident Prevention in
Oxygen Rich and Oxygen DeficientAtmospheres.
Cryogenic
Separation
-190C
Purchased
liquid
-190C
Operating
temperature
Ambient
Maximum purity
Up to 95%
Up to 99.9%
Up to 99.9"10
Usual purity
90 or 93%
98 or 99.5%
99.5%
Pressure (psig)
Atmospheric with
additional compression
From 10 to 200
without additional
compression
Up to 225 from
vaporization
Flexibility
in operation
Startup in 10 minuteseasy start and stop
Cold start 45 minutes warm start 2 days

continuous operation
Instantaneous
startup
From 100% to 0%
From 100% to 50%
From 100% to 0%
liquid production
No
Yes
N/A
S~cific power \it
265
300
25 x 35 m
30 x 35 m
Thmdown flow
phase
phase
not shown
the liquid product
Site size
JO
Vaporization only
site (kwhft)
6x30m
~-

The following bulletins are available from
the National Fire ProtectionAssociation,470
Atlantic Ave., Boston, MA 02210
NFPA 50, Bulk Oxygen Systems
. NFPA 53, Fire Hazards in Oxygen-enriched
Atmospheres.
Metals
85
316L stainless steel

Pyrex@
Glass
Grease
Halocarbon, Crytox'"
LOX -8'"
Teflon@, Goretex@,
Gylon"VitonA",
Silicone
Joint Sealant
Seals and Gaskets
5. Ozone
5.2 Ozone manufacture
construction
Ozone is a bluish gas under normal atmospheric conditions. It is a powerful oxidizing agent, is toxic, and has a pungent
odor. Ozone exists in the atmosphere in
very low concentrations (0.025-0.045 ppm
by volume) and is a contributor to photochemical smog. It can be stored almost indefinitely at -50C but, at room temperaturer
is 50% decomposed in several days, liberating oxygen. Ozone is sparingly soluble in
water.
Ozone has a very high electronegative
oxidation potential, 2.07 .ev, second only
to that of fluorine. This high oxidation p0tential has made ozone both a good bactericide for air and water and a potent oxidiant
in chemical pulp bleaching.
Ozone is a toxic, irritating gas, with good
odor-warning properties (the odor threshold is 0.01-0.015 ppm). It is unlikely that
people people will stay in an area in which
ozone concentrations are as high as 10 ppm
because of its irritating character. Nevertheless, ozone is very toxic. Ozone should
be monitored continuously
and, should
critical levels be exceeded, the system
should be shut down. Ozone, unlike chlorine dioxide, cannot be stored and is produced only when power is applied. All
ozone relief vents should be piped to an
ozone destruction system.
All handling and safety procedures that
have been adopted for the use of oxygen
(described in the previous section) also apply to ozone. These procedures include as
a minimum, "cleaned for oxygen service,"
no smoking in the area of use, and correct
Ozone is produced on-site because it is

unstable. An ozone generating system for
a pulp mill is very site-specific and incorporates variables such as the bleaching
sequence and ozone mixing system, availability and temperature of cooling water,
power cost, availability and purity of the
oxygen feed gas, and the capability to reuse or recycle vent gas (oxygen) for other
mill processes. A process configuration for
a pulp mill is shown in Fig. 5.
m1terials
selection.
The following materials have been found

to be suitable for use in the presence of high
ozone concentrations (55):
86
Pulp Bleaching
-Principles
and Practice
Ozone is commonly produced in a corona discharge process. Ozone production

is a function of the applied voltage, electrical frequency, the physical parameters of
the dielectric, temperature, pressure, and
the geometry ofthe discharge gap. The system should maximize the power input ratio, have no sparking, and prevent ozone
decomposition after generation by providing for efficient heat removal.
The principal elements of an ozone
generator are an electrical source, a gap
bounded by the high-voltage electrode, (dielectric material) and the vessel receptacle,
(ground electrode), and a mechanism for
removing the by-product of the generation
process.
Ozone production is accomplished when
dry oxygen-<:ontaining gas is subjected to a
high voltage/high density electrical current.
The corona discharge is formed in the oxygen-filled gap when the applied voltage
exceeds the ionization potential of the dielectric material and electrons travel across
the gap, colliding with oxygen molecules.
These collisions produce oxygen atoms
which recombine with molecular oxygen
to form ozone. The dielectric material is
used to prevent arcing and provide a uniform discharge surface (Fig. 6). Recently,
the introduction
of non-glass dielectrics
having selected properties and optimized
geometries has led to a significant decrease
in energy consumption and cost and to a
significant increase in ozone concentration,
unit capacity, reliability, and operational
flexibility (52).
Most commercial systems currently in
use are horizontal, dielectric tube exchangers. Feed gas passes through the gap between the dielectric shells and the electrode
receptacle; water flows outside the tubes
to remove the heat generated by the process. The generators are self-<:ontained,
each having individual power systems and
controls to allow each to be an independent production unit.
Energy and cooling systems
Cooling in an ozone system is achieved
by a coolant circulating in the generator
shell and, if required, in the ozone liquidring compressor.
Power requirements decrease and unit production increases with
decreasing cooling water temperature. The
water flow requirements for system cooling are substantial, but the temperature rise
(3"C) is small. Depending on the temperature of cooling water available at the mill, a
chiller or cooling tower may be required.
Outer
electrode
Cooling
water
Pulp
02 gas
to recycle or
Dialectric coated
inner electrode
reuse
Fig. 5. Ozone systemsfor
pulp
bleaebillg.
Fig. 6. ScbemtJtie
diIIgrtI1II
of ozone
generwtioll
discbarge
gap.
Chapter II 3: Bleaching Chemicals: CWorine, Sodium

Ozone compression
Ozone formation in the corona discharge
determines the optimum gas pressure (usually less than one atmosphere) in the generator. To allow sufficient ozone-bearing gas
to effectively mix in a high-shear mixer, both
high-concentration
ozone feed (10%) and
compression are needed to overcome the
system back pressure and reduce the gas
volume. Compression should be carried out
isothermally to avoid ozone decomposition.
For this purpose, the liquid-ring compressor is a suitable choice. liquid- ring compressors are durable, low maintenance
machines, and the water used for compression also cools the gas. Experiments have
been carried out at high concentrations and
pressures (18% w/w concentrations and 20
bar pressures) with no explosive decompo-sition observed (51).
Ozone destruction
Because ozone is an oxidative, corrosive
gas that is harmful to hum;jJls and the environment, its destruction in vent gases is required. All gases in the system must be
collected and residual ozone concentration
reduced to less than 0.1 ppm. This can be
87
accomplished by withdrawing the vent gas

from the pulp reactor using the system pressure or a supplementary blower and passing the ozone-containing
gas through a
destruction step based on the application
of heat and/or a catalyst. The thermal system uses high temperatures (300"C) to convert ozone to oxygen through high-density
electric or fossil fuel heaters. Catalyst systems employ a manganese dioxide- or palladium-coated alumina which catalytically
converts ozone into oxygen. A low-temperature heating step (50C) is employed
to fully vaporize moisture in the inlet gas.
A hybrid unit of both thermal and catalytic
uses temperatures of 150C to reduce the
ozone concentration before reaction with
the catalyst (56). The low energy cost inherent in the catalyst system makes it an
attractive option; however, the catalysts can
be poisoned by cWorinated organics.
Ozone consumption
in commercial
pulp systems is about 95% of that applied
so that, on a continuous basis, small residual
amounts of ozone are present in the vent
gases. However, the destruction systems
must be designed to handle the full ozone
flow for short time periods and able to shut
A. Once through
Exhaust
and/or
02 usage
B.Shortloop
Exhaust
C.
Long loop
Fig. 7. AltertUltives
for oxygen
reuse in 0%_
bleaching
systems.
Ozone destr.
Exhaust
02 purificat.
02 compress.
and/or
02 usage
88
Pulp Bleaching- Principles and Practice
down ozone production in the worst case

where none of the ozone is being consumed. Care must be taken to direct the
outlet oxygen-rich stream away from personnel or equipment, and suitable automatic shutdown and alarm systems must be
provided for a destruct system failure.
the ozone pulp reaction is a function of the

pulping process, (medium- or high-consisten{.""y),ozone charge, feed gas purity, and
air entrainment in the pulp.
Vent gas recovery and recycle loops
The properties,
generation, handling,
storage, and safety concerns of sodium hydrosulfite are found in Chap. V 2 as part of
the description of hydrosulfite bleaching
technology.
In parallel with ozone generation development work, optimized oxygen-ozone systems have been developed as illustrated in
Fig. 7.
Once throueh systems are effective when
there is a sizable oxygen demand in a pulp
mill that reuses a significant portion of the
vent gas (Fig. 7A).
Short loop systems recover oxygen before the
gas mixture reacts with the pulp and avoid
the need for extensive gas cleanup but require a second carrier gas such as dry air
or nitrogen (Fig. 78). The principal methods for ozone separation are adsorption!
desorption (silica gel, molecular sieves, and
dissolving/stripping of the gases from an
aqueous medium). It is also possible to
increase ozone concentration with these
techniques. Work is continuing in this area,
including the possible use of membranes
to separate oxygen and ozone.
Lone loop systems recycle the oxygen after
reaction with the pulp. Impurities are produced from the products of reaction of
ozone with pulp (Fig. 7C). It is necessary
to reduce the concentration of these impurities in the recycle gas to a level that
ozone generators can tolerate. The steps
involved are dilution, chemical conversion,
and separation. The most recent example
is a system that incorporates a combination
of ozone and hydrocarbon destruction
(conversion) compression, purge (dilution)
and drying (separation) (57).
In current commercial practice, ozone is
delivered by long loop and once through
systems at applications of 5- IO kg per metric ton of pulp. For a 1,200 metric ton/day
pulp mill, the ozone supply therefore var-
ies from
6,000 to 12,000 kg of 100% ozone

for a 24-hour period. The oxygen feed gas
can be supplied ina 90-99.5% purity range.
The purity of the vent gas produced from
6. Sodium hydrosulfite (sodium

dithionite)
References
1. Perry, R.H. and Green,
Engineering
Handbook,
Hill, 19843.102.
D.W., Cbemical
6th edn., McGraw
2. Tbe Cblorine Manual,The

CWorine
tute Inc., Washington,
D.C., 1993.
Insti-
3. Pampblet
63, The CWorine
Washington,
D.C., 1990.
Institute
Inc.,
4. Pampblet
74,The CWorine
Washington,
D.C., 1991.
Institute
Inc.,
5. Pampblet
85, The CWorine
Washington,
D.C., 1992.
Institute
Inc.,
6. Pampblet
73,The Chlorine
Washington,
D.C., 1993.
Institute
Inc.,
7. Cbemical Safety Data Sbeel SD-9 Manufacturing Chemists Association Inc.,Washing. ton, D.C., 1968.
8. Caustic Soda Solution
Handbook,
Dow
Chemical Company, Midland, MI, 1986
9. Pampblet
10, The CWorine
Washington,
D.C., 1993.
10. Perham,
D.A.,Appita
Institute
39(5):391
Inc.,
(1986).
11. Brown,D.R.,"Current
legislative and regulatory
developments
affecting
the
chloralkali
industry," Plant Operations
Seminar,The Chlorine Institute Inc.,Washington, D.C., 1989, p. 5-1.
12. Wilson, R.D., "Advances
in design for
higher current density cells;' Plant Operations Seminar,The Chlorine Institute Jnc.,
Washington,
D.C., 1989, p. 3-1.
13. White I.f. and O'Brien, n, in Modem
Cblor-alkali Tecbnology, Elfevier Applied
Science, London, 1988, Vol. 4.
Chapter n 3: Bleaching Chemicals: CWorine, Sodium

Hydroxide, peroxy Acids, Oxygen, and Ozone
14. Ogata,Y., Kojima,T., Uchiyama, S.,Yasuda,
M., Hine, E)., Electrocbem.
Soc. 136 (1):
p. 91 (1989).
15. Keating,).T. and BeWing, K.J., in Modern
Cblor-alkali Tecbnology, Elfevier Applied
Science, London, 1988, Vol. 4.
16. O'Brien,T.E, in Modern Cblor-alkaliTecbnology, Elfevier Applied Science, London,
1988, Vol. 4.
17. Mannig, D. and Scherer, G., "Hydrogen
peroxide in the chloralkali industry;Plant
Managers Seminar, The CWorine Institute
Inc., Washington,
D.C., 1987, p. 1-1
18. Hodge,).R., Gardner, D., and Clark, R, "KCAT process for brine!water
decWorination" Plant Managers Seminar, The CWorine Institute Inc.,Washington,D.C.,
1987,
p.2.1.
19. Yohe, T.H., "Use of salt/brine evaporators
in brine fed membrane cell NaOH plants;
Plant Managers Seminar,The Chlorine Institute Inc., Washington, D.C., 1987, p. 3-1.
20. Silver, M.M., "Sodium sulphate removal;
Plant Operations Seminar Notes,The CWorine Institute Inc.,Washington,D.C.,
1992,
p.2-1.
28. Pampblet
5, The Chlorine
Washington,
D.C., 1982.
89
Institute
Inc.,
29. Pampblet
89, Edn 1, The Chlorine
D.C., 1991.
insti-
30. Pamphlet
79, Edn 1, The CWorine
D.C., 1984.
insti-
31. Pamphlet
66, Edn 1, The CWorine
tute Inc., Washington
D.C., 1979.
Insti-
32. Pampblet
49,The CWorine
Washington
D.C., 1989.
Institute
Inc.,
33. Pampblet
60,The CWorine
Washington,
D.C., 1990.
Institute
Inc.,
34. Pamphlet
6, The CWorine
Washington,
D.C., 1989.
Institute
Inc.,
35. Pamphlet
9, The CWorine
Washington,
D.C., 1987.
Institute
Inc.,
36. Pamphlet MIR-126,The

CWorine Institute
Inc., Washington,
D.C., 1977.
37. Pampblet
64,The CWorine
Washington,
D.C., 1990.
Institute
Inc.,
38. Pamphlet
65,The Chlorine
Washington,
D.C., 1988.
Institute
Inc.,
39. Pamphlet
IB/C, The Chlorine
Inc., Washington,
D.C., 1983.
Institute
21. Ypdyke, L.). and Heilala,).,"Case

histories
involving nitrogen trich1orine;
Plant Operations Workshop,
The Chlorine
Institute Inc., Washington,
D.C., 1989, p. 81.
40. Hydrogen
Peroxide
(20-60%) Material
Safety
Data Sheet, CAS# 7722-84-1,
DuPont Canada Inc., Mississauga,
ON,
1994.
22. de Nora V. and Kuhn, ).W,

Tech., 47:125(1975).
4 I. Schutz, R.W and Xiao, M., "Practical windows and inhibitors

for titanium use in
alkaline peroxide bleach solutions,"NACE
International
Corrosion
Meeting Notes,
NACE International,
Houston,
paper #
427.
Cbem.
Eng.
23. Tratari, S., Ed., Electrodes of Conductive

Metallic
Oxides,
Parts A & B, Elsvier,
Amsterdam,
1980, 1981.
24. Tilac,B.and Conway,B.E.,ModernAspeds
of Electrochemistry,
(BokrisJ.O., Conway,
B.E., White, R.E.D., Novak, M., Eds.), Plenum, New York, 1982, Vol. 14.
25. Suzuki, O. and Fukunaga,T.].,Electrochem.
Soc.jpn.
24:104(1956).
26. Watson,Wand
Updyke,).,"Corrosion
and
materials of construction
in the cWoralkali
process," Plant Operations Seminar Notes,
The CWorine Institute Inc., Washington,
D.C., 1987, p. 1.
27. Mayo, P.and Means, R, "CWorine compressors," Plant Operations Seminar Notes,The
CWorine Institute
1987, p. 26.
Inc.,Washington,
D.C.,
42. Peroxyacetic
acid (35%) Material Safety
Data Sheet, E.I. du Pont de Nemours
&
Co.,Wilmington,
DE, 1994 (based on FMC
Corporation
MSDS dated 3/9/90).
43. Amini, B., DuPont Pxa;
High Conversion Pero.xyacids, DuPont Techncial Bulletin H-57651, E.I. du Pont de Nemours
& Co., Wilmington, DE, 1994.
44. Reichert, D.L., "Corrosion
behaviour
of
hydrogenperoxide
bleaching
solutions,"
CPPA Pacific and Western Branch Annual
Meeting
Preprints,
Tech. Sect., CPPA,
Montreal,
1995.
90
45. Wang, S., Chang, H-m.,]amee1, H., Amini,

B. ,"The preparation
of peracids for bleaching," Pulping Conference
Proceedings,
TAPPI PRESS, Atlanta, 1994, p. 531.
51. Armengaud,
B., Schmid, E., Thonnelier,
).Y., Nicolas,). E, and Lang, H., Proceedings of the 1993 11 th World Ozone Congress Proceedings,
lOA, San Francisco.
46, Francis, R.C., Zhang, X-Z., Troughton,

N.A.,and Hill,RT.,"Caroate
delignification
n: enhancement
by halides," 1993 TAPPI
Pulping Conference
Proceedings,
TAPPI
PRESS, Atlanta, p. 333.
52. Wiegart,
N., 1993 Air Liquide/Ozonia
Ozone Symposium Notes, Helsingor, Denmark, available from Air Liquide, P&P/
Ozone Division, Paris.
47. Anderson,).R,Amini,
B., and Wilkinson,
W,"On-site generation and use ofperoxyacids in chemical
pulp bleaching;
81st
CPPA Annual Meeting Preprints,
Tech.
Sect., CPPA, Montreal, 1995, p. B59.
48. Seccombe,
R, Hill, R., Martens, H., and
Haakana, A., "Practical
mill experience
with the use of Caro's acid to produce
high brightnessTCF
pulps," Non CWorine
Bleaching Conference Proceedings, Miller
Freeman, San Francisco, 1994.
49. Encyclopedie
des Gaz Air Liquide, L'Air
liquid, Elsevier Scientific Publishing Company,Amsterdam,
1976, pp. 1079-1118.
50. Canadian
available
Montreal,
Liquid Air Gas Handbook,

from Canadian
Liquid Air,
Subsect.A, Sect. 2, pp. 1-5.
53. Govers, T., 1994 International

Non-Chlorine Bleaching Conference
Proceedings,
Amelia Island, Florida, paper 4-4, Miller
Freeman, Inc., San Francisco.
54. Encyclopedie
des Gaz Air Liquide, L'Air
liquid, Elsevier Scientific Publishing Company,Amsterdam,
1976, pp. 1131-1137.
55. Funk, E., Hornsey,
D., and Munro,
E,
"Espanola Ozone Pilot Plant: New Data,
Experiences,
and Completion,"
Conference Proceedings,
CPPA, Montreal, 1994.
56. Ozone Safety Measures,Workers
Compensation Board of British Columbia, ISBN 07718-9243-8.
57. W Nutt, 1993 Air liquide/Ozonia
Ozone
Symposium
Notes, He1singor, Denmark,
Air liquide, P&P/Ozone
Division, Paris.
SECTIONm:
The Chemistry of Bleaching and
Brightness Reversion
Chapter 1:
Chemical Structure
of Pulp Components
G. Gellerstedt
Royal Institute of Technology
Stockholm, Sweden
1. Stnlcture of lignin in unbleached pulps . . . . . . . . . . . . . . . . . . . . . . ..

1.1 Reactivity of lignin in wood. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
1.2 lignin in unbleached and bleached
high-yield pulps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
1.3 Chemical modification of lignin in
kraft pulping'; . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
sulfite pulping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
106
2. Carbohydrate
106
constituents
3. Extractives in pulps.
in pulps
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
4. Stnlctural changes of lignin in bleaching
91
. . . . . . . . . . . . . . . . . . . . ..
93
93
96
99
108
108
Chapter III 1: Chemical Structure of Pulp Components
Chapter m 1:
Chemical
Structure Of
Pulp Components
In pulp bleaching, all chemical reactions
involve fiber constituents that have been
chemically modified as the result of mechanical and chemical treatments of wood
material. In the following survey, an attempt
is made to describe the chemical characteristics of the pulp components, particularly lignin, in (chemi)mechanical
and
chemical pulps.
The information presented below originates from a variety of analytical methods
applied to lignin, cellulose, and hemicelluloses. Nevertheless, our present knowledge
of the chemical structure of the residuallignin in chemical pulps is far from complete.
Available analyses are better developed for
polysaccharides than fo~ lignin, but information about lignin-carbohydrate
linkages
and molecular weight distribution and their
possible change during refining or pulping
is, to a large extent, still Jacking.
1. Structure of lignin in unbleached pulps

1.1 Reactivity of lignin in wood
Native lignin is a polymer comprised of
coniferyl alcohol (softwood) or a mixture
of coniferyl and sinapyl alcohol (hardwood)
CHlOH
I
CH
II
Q
OH
p-Coumaryt
alcohol
Fig. 1. Lipi" precursors.
CHlOH
I
CH
II
~
V~
OH
Coni/eryt
alcohol
93
94
units. Small amounts of p-<:oumaryl alcohol

units are usually also incorporated in the
lignin polymer, notably in compression
wood (Fig.l).The mode of polymerization
of these alcohols in the cell wall leads to a
heterogeneous
branched and cross-linked
polymer in which the phenylpropane units
are linked by carbon-carbon and carbonoxygen bonds 0, 2). In addition, secondary reactions in the lignification process
lead to the formation of benzyl alcohol and
benzyl ether groups. Etherification of carbohydrates
with benzyl alcohol groups
leads to cross-linking between lignin and
polysaccharide
chains. The main linkages
joining the phenylpropane
units are depicted in Fig. 2.
The frequency of occurrence of the predominant types of interunit linkages in softwood and hardwood lignin is shown in
Table 1. In alkaline processes leading to lignin dissolution (e.g., kraft pulping), the
number of ether linkages connecting the
phenylpropane units is of particular importance because these are the only chemical
bonds which, on cleavage, lead to fragmentation of the lignin polymer. The values in
Table 1 indicate that,for both softwood and
hardwood lignin, ether linkages are by far
the most abundant. Efficient cleavage of
ether structures therefore constitutes one
of the most important chemical reactions
in alkaline pulping.
1,2-Diarylpropane (~1) structures can be
converted to the corresponding
stilbene
5-5
CHlOH
&
II
CH,O~
OH
Sinap~
alcohol
Fig.Z.l"'erw,,i,li_ges
ill lipi..
c
b
c
b
99
,/
,/
Chapter ill 1: Chemical Structure of Pulp Components

under mildly acidic or alkaline conditions
(Fig. 3), Stilbenes are highly reactive in oxidative (4) and other processes and, as
strong absorbers of visible light, participate
in light-induced yellowing reactions (5) .The
1,2-diarylpropane structures in native lignin
have been estimated to be approximately
7/100 phenylpropane
units (Table I).This
figure may be falsely high, however, as a
figure of approximately
2 has been indirectly obtained (6).
95
end groups are converted

to carbonyl
groups that increase both the reactivity and
light absorption characteristics of structures
containing these groups (8).
The most important functionality in lignin from a reactivity point of view is the
free phenolic hydroxyl group (Fig. 4), and,
in most chemical reactions of lignin, phenolic phenyipropane units are attacked preferentially. The phenolic hydroxyl group
content in wood has been determined using a variety of methods, and, for both softwoods
and hardwoods,
a figure of
approximately 10/1 00 phenylpropane units
has been obtained (Table 2) (9-11, if. 12).
In addition to monohydric phenols (Type
A), lignin also contains trace amounts of
catechol and hydroquinone groups (Type
B) as depicted in Fig. 4. These diphenols
are of technical importance because, as a
result of their facile conversion to the corresponding quinone structures in the presence of air (oxygen) (Fig. 5), they constitute
potential chromophore structures in native
lignin (13).
96
Pulp Bleaching
-Principles
and Practice
above 400 nm, resulting in the emission of

yellow light. Coniferaldehyde
structures
have been estimated to be approximately
4/100 phenyipropane units, three of which
are non-phenolic. As conjugated carbonyl
structures, both types are susceptible to
attack by nucleophilic species such as hydroperoxide, bisulfite, and hydroxide ions.
0i0
I
a-t
<9Y~
0
r.<
L
<D = Lignin
O:>nWeraldehyde
structure
~~A
o
1.2
lignin in unbleached
high yield pulps
and bleached
Quinone
structures
Fig. 5. CI1romopl1ore stnu:hlra
TypeA
jugated aliphatic aldehydes are present as

glyceraldehyde structures linked to the lignin polymer through carbon-carbon or carbon-oxygen
linkages. Analytical
data
indicate, however, that these structures are
present in low concentrations
(15).
The inorganic content of wood usually
is less than 0.5% by weight and, of this
amount, the predominant elements consist
of calcium, potassium, and magnesium.
From a technical point of view, however,
trace amounts of transition metals (manganese, iron, and copper) are of a greater importance since they have a detrimental
effect on the efficiency of bleaching agents
such as oxygen, hydrogen peroxide, and
ozone (16-18). In addition, ferrous/ferric
ions are known to form strong and deeply
colored complexes
with catechol-type
structures
(19). Large variations in the
amounts of transition metals in wood are
observed depending on wood species and
growth site. Values typically are in the order of 50-100 ppm of manganese, 10-20
ppm of iron, and 1 ppm or less of copper.
I"
_lifI#Jlipl".
Other types of carbonyl structures usually encountered in small amounts in native

lignins are aromatic aldehydes typlfied by
vanillin structures. It has also been suggested that substantial amounts of non-con-
Unbleached
pulps
The structural changes occurring in lignin. when wood is converted to mechanical pulp by grinding
or refining
are
apparantly small (20, 21) .The phenolic content does not change to any noticeable
extent (Table 2) nor does the relative distribution of different types of lignin sub-structures. Analysis of lignin end groups
rtlbk 1. Freqrmu;y of oecIIrmIU of /1f'OIIIlfIetII1i"""ges cmmecli"g pbenylproJItIM ,,,dts ,,,
(b) =Lignin
Linkage type
Dimer structure
~-0-4
a-0-4
~-5
~-1
Phenylpropane ~-arylether
Phenylpropane a-aryl ether
Phenylcoumaran
1,2-Diarylpropane
50
2-8
9 -1 2
7
60
7
6
7
5-5
4-0-5
Biphenyl
Diaryl ether
~-~
Lignan-like
10 -11
4
2
5
7
3
Type B
Fig. 3. ForrruIHoII
of II slilHMfrum
II ~-1 stnu:lrm!.
During the biosynthetlc process and during tree aging, the acidic environment in a
tree promotes
condensation
reactions
within or between the lignin macromolecules which lead to the formation of new
carbon-carbon
linkages between adjacent
lignin chains (7). Furthermore, some lignin
Fig.4.1'ypes ofpbnwlk stnu:hIra I" lip''',

The yellowish hue of many wood species
to a large extent can be attributed
to
coniferaldehyde
end groups in the LIgnin
(Fig. 5) (14). The light absorption of this
type of structure extends into the blue region of the visible light spectrum, that is,
(3).
lip''''
Percent of total linkages

Softwood
Hardwood

indicates, however, that a minor conversion
of 1,2-diarylpropane
(13-1) structures into
the corresponding stilbenes may take place
during refining (Fig. 3) (22), a result which
is supported by model compound experiments (23).
Tllble Z. Free pberwlic Itytlrozyl group COtItefll of
flJood, meeba,deal pulPs, a"d Isolated
IIgnlns.
Sample
Phenolic
groups!
100 phenylpropane units
Wood flour,
Wood flour,
Wood flour,
Wood flour,
TMp, spruce
CTMP,
spruce
pine
birch
aspen
spruce
Milled wood lignin,

spruce
Milled wood lignin,
sweetgum
Reference
10,13
13,12
7
10
13
12
9,11
10,11
11
11
20
12
12
When wood is impregnated with sodium

sulfite prior to refining, a bleaching effect
is usually observed. Acting as a strong nuc1eophile, the sulfite ion adds to conjugated
carbonyl structures typified by those in
coniferaldehyde
and quinone structures,
and in the process, the color contributed
by these chromophores
is eliminated to a
considerable extent (24, 25). In these and
similar reactions, sulfonic acid groups are
introduced into the lignin thus increasing
the total number of acidic (hydrophilic)
groups (Table 3). This results in brighter
pulps having physical properties different
from those of an unsulfonated mechanical
pulp.
The desired degree of sulfonation of the
lignin can be achieved by varying the
amount of sulfite and the preheating time,
temperature, and pH conditions.Therefore,
pulps with very different physical properties em be produced (26) .With high sulfite
charges and long reaction times, most of
the phenolic lignin structures become sulfonated at the benzylic position of the side
98
Pulp Bleaching
-Principles
and Practice
chain. Under these reaction conditions, several new phenolic structures, formed simultaneously by hydrolysis of alkyl-aryl ether
1inkages, undergo sulfonation with the result that degrees of sulfonation are obtained
far above that expected based on the original free phenolic hydroxyl content. It has
also been noted that, under these sulfonation conditions, lignin undergoes other
profound chemical changes, notably condensation reactions, which presumably lead
to cross-linking of the lignin network (20).
suI/_ie
Tllble 3. CIIrIJoxyI
various pulps
""" (67).
Pulp
group COtItefll of
Sulfonate,
mmol/kg
Unbleached (TMP
Bleached CTMP
Unbleached kraftb
Unbleached sulfiteb
Bleached kraft
.
b
Total
capacity' ,
mmol/kg
-~!
80-11 0
150-250
Unbleached TMP
Bleached TMP
Gellerstedt, unpublished
97
40-70
40-70
120-180
190-320
100-120
60-80
150-180
10-25
Sum of carboxyl and sulfonic

Kappa number 32
acid groups
Bleached pulps
The bleaching of high-yield pulps is usually conducted
with alkaline hydrogen
peroxide and/or sodium dithionite (hydrosulfite) under nearly neutral conditions.The
latter chemical is a reducing agent used to
produce small or moderate increases in
pulp brightness (less than 10 brightness
units). In dithionite bleaching, lignin chromophores typified by simple quinones (Fig.
5) are rapidly eliminated without any further chemical modification of the lignin
(27).
Hydrogen peroxide, on the other hand,
can be used to increase the brightness of
high-yield pulps to values of around 80%
ISO for spruce and 85% ISO for aspen. The
chemical changes occurring in lignin are
again minor and the bulk of the polymer i~
seemingly
unchanged structurally.
The
most important reaction in peroxide bleaching is the oxidative elimination of conifer-
ConiferyI
alcohol
Enol ether structure
structure
Fig. 6. ClellfJllge of~-0-4
slnU:tures
I" IIgnl"
""ri"g
allulllne
pulpi"g.

aldehyde end gr.oups. Quin.ones, when
present, are also rapidly destroyed. These
reacti.ons lead to the formati.on of acidic
groups (Table 3) and to vanillin-type structures (28). Conversi.on .of small am.ounts
.of 1,2-<1iarylpropane (~1) structures t.o stilbenes also takes place under the alkaline
bleaching c.onditi.ons (Fig. 3) (29). This reacti.on is .of particular interest because it
leads to the introducti.on .of a strong lightabs.orbing gr.oup in the bleached pulp
which in turn may have a large negative effect .on brightness stability (30). The destruction
.of chrom.oph.ore
systems in
peroxide bleaching is discussed in greater
detail in Chap. 4 .ofthis secti.on.
The structures of the remaining colorc.ontributing groups in fully bleached highyield pulps are not known with certaintY.
It has been demonstrated,
however, that
c.oniferaldehyde structures are n.ot quantitatively eliminated during technical brightening c.onditi.ons
indicating
that, f.or
example, accessibility
.of the bleaching
agent may playa role. Other residual chrom.ophores may c.onsist .ofhydroxyquinonetype structures because the latter have a low
reactivity toward hydrogen peroxide (31).
99
aIkyl-ary1ether $-0-4) structures is critically

dependent .on the availability .ofsulfide i.ons
(Fig. 6). If this requirement is not met, these
ether structures are transf.ormed int.o alkali
stable en.ol ethers which d.o not fragment
and lignin diss.olution is restricted (34).
In "normal" kraft pulping at a sulfidity of
ab.out 30%, en.ol ether structures can be
detected both during and at the end .ofthe
process indicating that, even at this sulfidity
level, the alkyl-aryl ether (fH>-4) cleavage
reactions are n.ot t.otally effective (35). Furthermore, analytical data .on the presence
.of alkyl-aryl ether (fH>-4) linkages in softwood lignins indicate that the residuallignin after kraft pulping to kappa number
near 30 still c.ontains about 15% of the .original ether linkages (Fig. 7) (36). In hardw.ood
(birch) pulps, on the other hand, the alkylaryl ether (~-4) linkages seem to be more
reactive so that at kappa numbers of approximately
17, that is, at 91% delignificati.on, n.o ether linkages can be detected
(37).
700

kraft pulping
Several types of chemical reactions taking place during alkaline pulping affect the
structure of the lignin remaining in the fibers at the end .of the process. In the f.oll.owing sections the reacti.ons and process
parameters which are believed to have a
major impact .on the structural characteristics .of lignin in unbleached kraft pulps are
reviewed.
Sulfidity effects
The imp.ortance .of the sulfidity level in
alkaline pulping is well-d.ocumented.
In
particular, a high c.oncentration of sulfide
i.ons is needed in the initial phase of pulping
.otherwise the amount of lignin present at
the tramition point Ixtween the b\llk ami
(slow) final delignification phases will be
high (32, 33).The fragmentati.on .of the lignin macromolecule, that is, the cleavage of
20
40
60
80
Delignification, % on wood
100
of ~-Q-4 strru:IIIrf!S
Fig. 7. C'-"t.e
lIS
". lip'"
fuctIott of tbe degree of dellpljktlltorll.
"
llraft Jndpt",.
Phenolic hydroxyl content
The cleavage of an alkyl-aryl ether
<IH>-4. a-0-4, or ~5) linkage in lignin leads
t.othe formati.on .ofa new phen.olic hydroxyl
end group that is i.onized under the alkaline conditi.ons prevailing in the digester.
The phenolic hydroxyl group content of the
lignin is of great importance because, except for a ornall nwnbtr of carboxyl groUP1!,
this is the .only type .offuncti.onal group conferring water (alkali) S.olubility to the lignin
in kraft pulping. During the c.ourse .of
100
Pulp Bleaching
-Principles
and Practice
pulping the phen.olic hydroxyl c.ontent .of

the residual lignin sl.owly increases but
never reaches the much higher level attained by the lignin dissolved in the pulping
liquor (Fig. 8) (38).
80
dissolved
lignin
carbon-carbon bonds. Analyses indicate that

the f.ormer type .of structure (in its ringopened form) is more abundant in the residual lignin than in the native lignin. As
stated above (see Fig. 7), the quantity of
alkyl-aryl ether (~-4)
linkages in residual
kraft lignin is also far from zero (36). In additi.on, such linkages when present in nonphen.olic and/.or c.ondensed units, are not
analyzed f.or by the methods available and
so may be present in substantial amounts.
pulp lignin
~
,
o
20
40
60
80
Delignification,% on wood
Fig. 8. P6Moik bydrozyl grotI/IS of IlpilllIS

timI oftbe UgrN of dellpljktlltorlI.
JIrIlpI",.
100
"futU:llraft
After pulping, the average number of

phenolic hydroxyl groups in the residual
lignin is about 30/100 phenylpropane units
(3~0),
c.orresponding t.o approximately
50-100 mmoles/kg of pulp, depending .on
the kappa number. At present, it is n.ot
kn.own if these values reflect true differences in the pulping process .or merely illustrate weaknesses
in the analytical
procedures. From a bleaching perspective,
it is advantage.ous for the residual lignin to
have a high free phenolic hydroxyl gr.oUP
content because these functionalities react
preferentially with oxidants such as .oxygen
and chl.orine di.oxide.
Distribution
of lignin sub-units
The comprehensive cleavage .ofalkyl-aryl
ether (fH>-4, a-0-4,and ~5) linkages in lignin during kraft pulping leads t.o a modified lignin polymer in which the relative
distributi.on of inter-unit linkages is different than that .of the starting P.olymer. In
particular, the number of carbon-carbon
linkages such as th.ose in biphenyl (5-5)
structures and the number of carbon-oxygen linkages in biphenyl ether (4-0-5) structuresincrease slightly (41,42) because they
are c.ompletely stable under the pulping
conditions. Phenylc.oumaran (~5) and 1,2diarylpropane
(~1) structures are other
examples of phenylpropane units linked by
Condensed
structures
The alkaline conditions prevailing in kraft
pulping favor a variety .of c.ondensati.on reacti.ons between lignin units and between
lignin and carb.ohydrates. Several such reacti.ons have also been identified in m.odel
compound studies (43-45). Whether c.ondensati.on reactions actually take place in
the polymeric material is, however, still a
debatable issue. Four main modes of ligninlignin condensation
reactions have been
identified on the basis of model compound
studies (43).
Table 4. c.rbtm "toms II
10 CIIrbtm "rulbytlrognl/l00 C4rbtm "toms I. Is6lt1tetlllplllS.
(Dat" btrse4 0fI ClJNMR """'ysls by tH DEPT
~.)
Type of
carbon
Aliphatic CH
Aliphatic CH2
Aliphatic CH3
Native
lignin
(MWL)
2.9
2.0
Kraft pulping to
kappa no. 3D.5
Residual
lignin
Dissolved
lignin
3.3
4.8
2.3
5.2
8.4
2.4
In the first of these, styrene- or stilbenetype structures react with a quin.one methide S.o as to form a carb.on-carbon
linkage
between two lignin side chains. This reacti.on leads t.o the f.ormation
.of methine
carbons in the lignin. However, as shown
in Table 4, the number of methine carbons
is not significantly
different in native and
kraft pulp lignins. In an.other type .of condensati.on, aromatic rings add to a quinone
methide forming a diarylmethane
structure
(Fig. 9, reacti.on A). Again, an increase in
the number of methine carb.ons W.ould result if this reacti.on occurred t.o a meaningful extent.
Chapter
III 1: Chemical
Structure
of Pulp Components
102
Pulp Bleaching
2
OCH.!
Table 5. S}lifk
peru:e.)
Typeof
carbon
l~
CtlrIHnI
atoms ,,, some Isolatetl IIg,II",. (Dtlta

btlsetl on"C
<9 =Ugnin
and Practice
types of CtlrIHnI tIItnIUI100

NMR "",'ysIs
Native
lignin
(MWL)
CH:zC)
- Principles
Aliphatic
carbonyl
structures
present
in
lignin side chains are reaction
sites for the
third suggested
type of condensation.
The
amount
of carbonyl
groups in lignin is low,
however,
(Table 5) and, despite the fact that
this reaction
accounts
for the observed
increase in methylene
groups, it is reasonable
to assume that condensation
reactions
of
this type are of minor importance.
4-
101
Carbonyl
Carboxyl
Olefinic +
aromatic Cq
Aliphatic CHx-OR
Methoxyl
Aliphatic CHx
by tbe DEn' $e-
Kraft pulpi'1% to
kappa no. .5
Residual Dissolved
lignin
lignin
0.8
0
0
2.1
0.3
1.5
39
54
39
23.6
11.2
4.9
9.5
9.1
10.4
10.1
8.9
16.0
The coupling of formaldehyde with two

adjacent aromatic rings having un substituted C-5 positions may contribute to
undesirable secondary reactions, however
(Fig. 9, reaction B). Formaldehyde is produced when terminal hydroxymethyl units
in lignin are liberated during pulping (34).
Although this reaction occurs only to a
moderate extent, it has been demonstrated
that formaldehyde is incorporated in the
dissolved lignin as pulping proceeds (46)
possibly in the form of methylene bridges
between aromatic structures. In the solid
(gel) lignin phase, however, such coupling
reactions can be assumed to be less important than similar reactions occurring in s0lution.
Recently it has been suggested that a
comprehensive formation of diarylmethane
structures takes place in the residual pulp
lignin during the course of kraft pulping
(47, 48). TI1is view has been questioned,
however, because the results provided by
the analytical method employed do not
unequivocally support this conclusion (49).
Furthermore, analysis of the dissolved low
molecular weight lignin-derived material in

kraft pulping liquor also does not support
the concept that lignin reactions involving
condensation constitute a major reaction
mode (50). Obviously, further work is
needed before the occurrence of condensation reactions in the residual lignin is conclusively established.
Reduced structures
A large number of the chemical reactions
of lignin occurring under kraft pulping conditions have been identified (51). However,
none of these indicates that reduction is a
major reaction pathway. Nevertheless,
a
variety of reduced lignin structures
are
found after kraft pulping both in the dissolved and residual lignin (Tables 4 and 5).
In reduced structures, one or more of the
side chain carbons has been converted from
an alcohol (ether) to a hydrocarbon group.
Although these structures are known to be
present in trace amounts in native lignin,
the high concentration found in kraft lignin indicate that reduction processes may
be important (ef Refs. 50, 52). In fact, the
most notable quantitative structural difference between native and kraft lignin seems
to be the number of methylene groups
formed during pulping. If these groups are
present in benzylic positions, the resulting
phenylpropane
unit becomes essentially
stable towards further degradation. Additional information about the chemistry underlying the formation of reduced structures
in kraft pulping therefore would be of great
technical interest.
Functional groups
Analysis oflignin isolated from kraft pulp
supports the view that this material is still
polymeric although it has an altered distribution of functional groups. One major
modification is the apparent conversion of
aliphatic oxygen-linked carbon atoms into
carbons linked only to other carbons and
hydrogen (fable 5). Residual kraft lignin also
contains more quaternary aromatic carbons
than native lignin, a fact consistent with the
increased amounts of phenylcoumaran
(~
5), biphenyl (5-5), and biphenyl ether (4-05) structures
found (53). Condensed

structures involving aromatic rings formed
during pulping, however, also may contribute. As stated above, residual alkyl-aryl ether
(fH>-4) linkages are much lower in kraft lignin than in native lignin, but still far from
zero.
Carbonyl groups are virtually absent in
residual kraft lignin but some carboxyl
groups are formed during pulping.The wellknown demethylation reaction resulting in
the formation of methyl mercaptan and dimethyl sulfide during kraft pulping (Fig. 10)
accounts for the decrease in methoxyl
group content and the increase in catechol
groups (41, 42, 53). Ring-conjugated structures of the type found in stilbenes (Fig. 3)
and enol ethers (Fig. 6) are present in residuallignin although in low amounts. Stilbenes are estimated to be present to the
extent of approximately 3/100 phenylpropane units (38).
Lignin-carbohydrate
linkages
The presence of chemical linkages between lignin and polysa~charides in wood
has been debated for a long time and divergent opinions about their existence still
prevail. A large amount of indirect evidence
indicates, however, that such linkages exist. The types of linkages suggested most
frequently involve benzyl ester and benzyl
ether bonds and phenyl glucosidic bonds
(54) .Treatment of wood under alkaline conditions leads to the cleavage of all types of
ester linkages, but stable ether linkages may
exist in non-phenolic units.
The reaction conditions in kraft pulping
favor the formation of new Iignin-carbohydrate
linkages.
Thus, it has been
demonstated in model compound experiments that formation of an ether linkage
between a sugar moiety and non-phenolic
(Fig. 11) (44) and phenolic lignin structures
(55) is possible when a carbohydrate hydroxyl group, acting as a nucleophile, attacks an epoxide or a quinone methide. In
other model compound studies, the formation of carbon-carbon
linkages between
quinone methides in lignin and enediol
structures arising from reducing end groups
in carbohydrates has been suggested (45).
If they occur, such reactions would have
103
104
OH
0--
=Cerbohydrate
+
a-I:!S-
(a-I:!Sa-I:!)
C0 =Lignin
PI,. 10. FortlUJtiml of melby' tMt'CIIpt."

/It.""
mBtby' s,dfltle from .rtnlUlttc metboxy'
VO"JIS ""rlfIg Inwft Jndplflr.
an important influence on the peeling of

polysaccharides in the early part of pulping,
by leading to the formation of stable lignincarbohydrate cross links.
The residual lignin in kraft pulps and the
dissolved lignin are linked to carbohydrates
as indicated by determination of the carbohydrate content and composition
in the
lignins dissolved in flow-through pulping
(56).
Thus,
increased
carbohydl".lte
con-
tents are found in dissolved lignin fractions

corresponding to the final part of the bulk
phase and to the residual delignification
CH:IOH
tt-OH
tt
(;lI
@ ~
oc:H3
CH:I
OH
OH
~~----
105
106
phase. Sugar analysis has revealed that arabinose and xylose are the predominant
structural units. Similar analysis of the lignin dissolved in an oxygen bleaching stage
has again revealed the presence of carbohydrates with xylose once again a major
component (57).
On the other hand, analyses of the residual polysaccharides in lignin isolated by
enzymatic hydrolysis of kraft pulps have
provided divergent results. In one study, the
results suggest that the residual lignin is
mainly bonded to cellulose (58) and that
these lignin-<:arbohydrate bonds to a large
extent are generated during pulping according to the reaction outlined in Fig. 11. The
results of another study in which a similar
analytical technique was used suggest, however, that the lignin-<:arbohydrate linkages
are predominantly native and bond lignin
to the hemicelluloses, that is, to glucomannan and arabinoxylan
(59). It was also
noted that the number of linkages between
each individual polysaccharide
chain and
lignin is low (about one);
Molecular weight distribution
Gel permeation chromatography
of lignin isolated by enzymatic or acid hydrolysis of kraft pulp provides molecular weight
distribution curves indicating that the apparent molecular weight of this material is
higher than that of dissolved kraft lignin (38,
60, 61). However, the differences are not
of such a magnitude, nor do other analytical data differ sufficiently, to suggest that a
completely different solubility behavior
should be expected. Nevertheless, the linkage of residual lignin in the fiber wall to
polysaccharides
by alkali-stable chemical
linkages substantially increases its molecular weight and molecular size distribution.
This, in turn, makes diffusion of lignin fragments through the pore system and out of
the fiber wall much more difficult. By applying a high temperature to facilitate the
diffusion of lignin molecules, a "leaching"
effect can be observed for both kraft and
high-yield pulps over long periods of time
(62). Consequently, the efficiency of the
pulp washing stage is of great practical importance in later bleaching reactions be-
cause that part of the residual lignin which

can be removed must be assumed to have a
chemical structure and reactivity closely
resembling that of dissolved kraft lignin. A
preferential bleaching (t.e., oxidation, chlorination) of this part of the residual lignin,
therefore, can be anticipated.
Colored structures
Kraft pulp fibers are brown because of
the formation of chromophoric groups during pulping. These groups may be present
in both lignin and carbohydrates (see below) although lignin is assumed to be the
predominant contributor. In the presence
of alkali, the absorption maxima of some
types of chromophoric groups are shifted
to higher wavelengths because of the ionization of phenolic hydroxyl groups. This
shift is accompanied by an increase in color
intensity which is retained by the pulp after pulping and washing.
Several explanations can be offered for
the facile formation of color in lignin structures.Although the exact structures of the
chromophores involved is not known with
certainty, it is reasonable to assume that
double bonds conjugated with aromatic
rings, quinones, and quinone methides play
a dominant role as color contributors.These
structures are formed during pulping directly by elimination of water and/or formaldehyde from phenolic phenylpropane
units or indirectly by oxidation of, for example, a catechol or hydroquinone. Structures of the latter type are present in trace
amounts in native lignin (53), but catechols
are also formed during pulping as a result
of the cleavage af aromatic methoxyl groups
(Fig. 10). Quinone methides may function
as oxidants in these reactions (52).
At the end of pulping, autoxidizable
structures such as catechols in the still-a}..
kaline pulp are susceptible to secondary
oxidation reactions when contacted with
air (oxygen). In the presence of transition
metal ions, these autoxidation reactions are
enhanced,butfernou~/ferncion~can

sulfite pulping
The reactivity of lignin in sulfite pulping
depends to a major degree on the pH of
the pulping liquor (63). For all types of
pulping, however, sulfonic acid groups are
introduced into the benzylic positions of the
lignin side chain (cf. Table 3). Depending
on pH, this sulfonation is more or less complete as is the dissolution of lignin. Pulping
at a low pH and temperature is the preferred
approach for making chemical pulps although conditions utilizing a high alkalinity also can be used. The degree of lignin
fragmentation
also depends on pH and
more fragmentation occurs at higher (alkaline) pH values because of the base-<:atalyzed cleavage of alkyl-aryl ether linkages.
Little is known about the structure of
residual lignin in sulfite pulps. Neutral
sulfite pulping of both softwoods and hardwoods to various pulp yields, isolation of
the residual lignin, and determination of the
distribution of interunit linkages has revealed, however, that the structure of these
lignins is very similar to that of the corresponding native lignins (64). In contrast,
analysis of an acid sulfite pulp has shown
that condensation reactions involving aromatic rings take place in the lignin (65).
Such condensation
reactions
are wellknown and may lead to cross-links between
lignin chains. Nevertheless, industrial sulfite
pulps having very low kappa numbers and
good bleachability are routinely obtained,
indicating that the structure of the residual
lignin closely resembles that of native" lig"
nin and therefore is reactive toward oxidative bleaching agents.
2. Carbohydrate constituents
pulps
in
In kraft pulping, a substantial loss of carbohydrates results from alkaline extraction

and peeling reactions in the early part of
pulping and from alkaline hydrolysis in the
later phases when the maximum pulping
temperature
is reached. In particular,
(galacto)-glucomannan
in softwoods
is
prone to undergo peeling and a severe loss
of this hemicellulose occurs (Fig. 12); on
the other hand, xylans in both softwoods
and hardwoods are more resistant. Because
of the solubility of xylan under strongly alkaline conditions, this type of hemicellulose, however, may partly dissolve at the
(Q
C
vF~H
CQ(J
OH
HO:/,
OH
Metasaccharinic
acid end group
~oo
OH
@
= Carbohydrate
chain
~so
form stable and strongly colored complexes

directly with catechol-type lignin structures
(/9).
DIssoIIIed
glucoisosaccharinic
acid
--- _._-----Chapter III 1: Chemical Structure of Pulp Components
107
108
metasaccharinic acid-type (Fig. 12) and, at

the end of kraft pulping, it may be assumed
that virtually all carbohydrate end groups
have been converted to carlJoxylic acids.
Analyses of the carboxyl group content of
unbleached kraft pulps yield values of about
60-140 mmoles!kg of pulp (67, 68). Of
these, approximately 31k5 are associated
with the residual lignin. However, the figures depend, to a great extent, on both pulp
yield and kappa number.
Less well-recognized among the carbohydrate reactions occurring during alkaline
pulping is the possible conversion of sugar
moieties to structures containing double
bonds and aromatic rings. In this connection,it has been demonstrated that,on treatment of cellulose under kraft conditions in
the presence of milled wood lignin, xylan,
or glucomannan, the brightness of the cellulose decreases considerably in all cases
(fable 6) (69). Other indirect evidence has
been obtained from studies with selected
monomeric sugars such as xylose and glucose which, on treatment with alkali, are
converted to aromatic structures (Fig. 13)
(70).
Recently, during attempts to isolate lignin from an unbleached birch kraft pulp by
acidic hydrolysis, a large quantity of material derived from carbohydrates was found
besides a lignin fraction (71). Based on the
observed reduction in the kappa number
of the hydrolyzed pulp, these results can
be interpreted as indicating that structurally modified carbohydrates contributed significantly to the kappa number reduction.
The quantitative importance of reactions of
this type is still not known, nor is their potential impact in bleaching.
~~OO
OH
0." M.ecH
9O"C,"
r:>:
o
+
0
I
OH
OH
and others
FIg. 13. E:xinnples
of fIIWIhItwINl
t:OtII/JOIIIUI8 f017llell
of gl_
in tN al""'me trelJlJJIeIJt
lose.
or :!tY-
beginning of pulping.At a later stage, when

the concentration of alkali has decreased,
the xylan may reprecipitate (66) resulting
in a redistribution of polysaccharides inthe
fiber.
The peeling reaction gives rise to stable
polysaccharide
end groups
of the
3. Extractives in pulps
Wood extractives, for the most part, are
dissolved in alkaline pulping liquor directly
by soap formation or indirectly by micelle
formation caused by the presence of ionized resin and fatty acids. In softwoods especially; which contain only small amounts
of neutral components, the amount of extractives remaining after kraft pulping is low
and approximately 0.1% for pine and 0.20.3% for spruce. Neutral components such
as sterols and sterol esters predominate, but
smaller amounts of resin and fatty acids are
also present (72).
In hardwoods (e.g., birch), on the other
hand, the extractives are comprised of large
amounts of neutral components
making
them much more difficult to remove during pulping (Fig. 14). Despite the addition
of an emulsifier, tall oil, to the kraft pulping
liquor, the remaining amount of extractives
in the unbleached pulp, is about 0.5-1.0%
but may vary widely depending on such
variables as wood species and debarking efficiency (72).
Several of the extractives in unbleached
kraft pulps contain one or more double
bonds making them extremely reactive toward bleaching agents such as elemental
chlorine (see Chap. 3). Pulps from such

bleaching sequences in all probability contain organically bound and extractable cWorine (73) (see Chap. 3).
4. Structural changes of lignin in

bleaching
Unbleached softwood kraft pulp contains
approximately 3-5% lignin corresponding to
a kappa number of 20-33; in hardwood
pulps, the residual lignin content may be
considerably lower. To a great extent, this
lignin is chemically linked to polysaccharides by alkali-stable ether bonds. Except
in the precencl': of strong acids, these ether
linkages are moderately resistant toward
acidic hydrolysis as well.
The predominant mode of lignin removal
in bleaching is through oxidation. In such
processes, acidic groups are formed which
impart increased water solubility to the lignin polymer while simultaneously inducing
cleavage of carbon-carbon and carbon-oxygen bonds. In or after each bleaching (oxidation) stage, the chemically modified lignin
is washed from the fibers again leaving a
residual lignin (74). The structure of this
lignin is changed only to a minor extent,
however, compared to the structure of lig-
Squalene
Table 6. CINmgeill brlgbtfless after ~

of
~lllllou ntb ""rlmIs tUldtti_ "".,. iraft
p,dJlillg
tXHIIUtkms
Additive
Brightness
of resulting
pulp, %
HO
80.1
None
Milled wood
lignin
Birchxylan
Spruce
(69).
glucomannan
65.6
69.5
72.2
S~osIerol
Fig. 14. Examples of extrGdi_
tN IHIrlI.)
Betu~nol
preSMt ", "tlbletu:bed bircb iraft JIIIlp (BetflliflOl orlglfllJtes exclflSively Iff
109
110
Table 7. Spmfte types of carbon atomsl100
isolatell from IIJOtHI(MWL), """leaebetl

ImIft pulp, oxygea-bleaebetllmlft
pulp, aatllmlft pulp bleaebetll.
a OD(EOP) seqtUIJIU. (PIlIp
IIg,"as were Isolatell by aeUl bydrolysls
(71); Data basetl 08 '1(; NMR a8tllysis by tbe DEPT sequerree
(75).)
Type of carbon
Aldehyde
Carboxyl
Aromatic + olefinic Cq
Aromatic + olefinic CH
Aliphatic CH-OAliphatic CH2-OMethoxyl
Aliphatic CH
Aliphatic CH2
Aliphatic CH3
carbon
atoms
MWL
Kraft Pulp
After 0
0.8
0
39
32
15
9.1
11
2.9
2.0
0
0
2.1
54
21
5.5
4.0
9.1
3.3
4.8
2.3
0
3.5
52
21
6.4
3.9
8.2
3.7
6.5
3.1
nin in the unbleached pulp (fable 7) (75).

Therefore, several bleaching stages have to
be employed to completely remove the lignin.With continued oxidation, the residual
lignin becomes progressively less reactive
because the most reactive structures,for example those with free phenolic hydroxyl
groups or with non-substituted
guaiacyl
rings, are attacked and eliminated preferentially in an earlier bleaching stage (57).
The effect of individual bleaching agents on
the structure of lignin, carbohydrates, and
extractives is discussed in detail in Chap. 3.
The present trend away from bleaching
sequences using chlorine-containing bleaching agents further increases the difficulties
encountered in obtaining a completely lignin-free,high brightness pulp because cWorine has an outstanding reactivity toward
lignin compared
to all other bleaching
agents. The further development of chlorine-free bleaching sequences for chemical
(kraft) pulps, therefore, requires a thorough
knowledge of the structure of residuallignin and how its reactivity can be changed
by various means.
After 0-0(1
OO)-EOP
0
10
47
14
9.4
5.7
5.4
2.6
7.7
3.6
Kemisk
2. Nirnz, H., Angew. Chem.
Tidskr.
56:124
80:279
(1973).
3. Sjostrom, E., Wood Chemistry: Fundamentals and Applications,

Academic
Press,
New York, 1993, p. 82.
4. Adler,
E., and H:iggroth,
Papperslidn.
53: 321 (1950).
5. Zhang, L., and Gellerstedt,
Scand., 48:490 (1994).
6. Lundquist,
Berndtson,
(1967).
S., Svensk
G., Acta
Chern.
K., Miksche, G.E., Ericsson, L,

1., Tetrahedron,
Lell. 4587
7. Larsson, S., and Miksche, G.E., Acta Chern.

Scand. 25: 647 (1971).
8. Adler, E., Marton,].,
75 (1959).
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9. Yang, J-M., and Goring,

Chern. 58: 2411 (1980).
10. Gellerstedt,
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D.A.I.,
13:
Can. j.
G., and Lindfors, E-L., Svensk

87: R115 (1984).
11. Lai,Y-Z., and Guo, X-P, Wood Sci. Technol.

25: 467 (1991).
II
valuable
criticism
of the
Gellerstedt, G., and Pettersson,

Papperstidn.
83: 314 (1980).
14. Pew,].c.,
(1971).
and Connors,W.j.,
I.,] Wood
19. Polcin,).,
and Rapson, WH., Pulp
Mag. Can. 73(1):86 (1972).
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(1')68).
0.,
18. Pan, G., Chen, C-L., Chang, H-m., Gratzl,

J.,"Modei Experiments
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Vol. 2, p. 132.
'!'hanks are due to Dr. Ants Teder of this

CSIRO,Australia,for
manuscript.
and Practice
15. Nakano,)., Ishizu, A., Hosoya, S., Kaneko,

H., Matsumoto,
Y., "Oxidation
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1982 TAPPI Research and Development
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Chem Technol. 2:231 (1982).
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- Principles
16. Manouchehri,
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12. Chang, H-M., Cowling, E.B., Brown, W.,

Adler, E., Miksche, G.E., Holzforschung
29:153 (1975).
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1.lIplas
B., Svensk
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Pap.
21. Pan,X., Lachenal, D., Lapierre, C., Monties,

B.,JWood Chem Technol. 12:135 (1992).
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Z-H.,
Matsuoka,
M., Lee, D-Y.,
M., Mokuzai
Gakkaishi
37:164 (1991).
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24. Suckling,
I.D.,
"The
Effect
of
Coniferaldehyde
Sulfonation on the Brightness
and
Absorption
Spectra
of
Pulps," 1991
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on Wood and
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Appita,
Parkville, Victoria, Australia, Vol. 1, p. 587.
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(1952).
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31. Gel!erstedt,
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Hartler,
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35. Gellerstedt,
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36. Gellerstedt,
63:315
73:571
E-L., Nord.
G., Lindfors, E-L., Lapierre,
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37. Gellerstedt, G., Lindfors, E-L., Lapierre, c.,

Robert, D., "The Reactivity
of Lignin in
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on lignocellulosics
and Pulp Proceedings,
Buchhandlung
Max Wiedebusch,
Hamburg, 1990, p. 224.
38.Yamasaki,T., Hosoya, S., Chen, C-L., Gratzl,
]., Chang, H-m., "Characterization
of Residual Lignin in Kraft Pulp;' 1981 International Symposium
on Wood and Pulping
Chemistry Proceedings, SPCI, Stockholm.,
Vol. 2, p. 34.
39. Gellerstedt, G., and Lindfors, E-L.,Svensk

, Papperstidn. 87: R115 (1984) .
40. Francis,
R.C., Lai, Y-Z., Dence,
C.W.,
Alexander,T.C., Tappif. 74(9): 219 (1991).
41. Gel!erstedt, G., and Gustafsson,
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42. Gellerstedt,
G., Gustafsson,
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Imsgard,
K.,] Wood
K., Northey,
3:87 (1988).
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Polym. Symp. 28:1195 (1976).
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Pap. Sci. 10: 12 (1984).
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44. Gierer,]., and Wannstrom,

schung 40:347 (1986).
27. Polcin,].,
(1976).
45. Fullerton, T.j., and Wilkins, A.L.,j.

Pap. Celul. 31(3):V9
28. Gellerstedt,
G., Pettersson,
I., Sundin, S.,
"Chemical Aspects of Hydrogen Peroxide
Bleaching",
1981 International
Symposium
on Wood and Pulping
ceedings,
SPCI, Stockholm,
29. Gellerstedt,
Chem.
Scand.
Chemistry
Pr0-
Vol. 2, p. 120.
G., and Agnemo,

B34:461 (1980).
c.,
87:R61
(1984).
20. Gellerstedt, G., and Gustafsson, K., 1987

International
Symposium
on Wood and
Pulping
Chemistry
Proceedings,
ATIp,
Paris, 1987, Vol. 1, p. 15.
23. Wu,
30. Castellan,A., Colombo, N., Nourmamode,

A., Zhu,j.H., Lachenal,
D." Davidson, R.S.,
Dunn, L.,] Wood Chem. Technol. 10:461
(1990).
R., Acta
S., Holzfor-
46. Araki, H., Tomimura,

Y, Terashima,
Mokuzai
Gakkaishi
26:102 (1980)
47. Chiang, Y.L., and Funaoka,
schung 42: 385 (1988).
48. Chiang, Y.L., and Funaoka,
forschung
44: 147 (1990).
Wood
N.,
.
M., Holz!orM., Holz-
--"-
Chapter III 1: Chemical StructUre of Pulp Components

49. Chan, E, Nelson, P.E, Nguyen, K.L., Wallis,
A.EA., "Chemical Transformations
of Eucalypt Wood Components
during Kraft
Delignification," 1993 Annual General Conference
Proceedings,
Appita Parkville,
Victoria, Australia, Vol. 2, p. 757.
50. Gierer, J., and lindeberg,
Scand. B34:161 (1980).
51. Gierer,}.,
(1985).
Wood
0., Acta
Set. Tecbnol.
Chem.
19:289
52. Falkehag, S.I., Marton, J., Adler, E., Adv.

Chern. Ser. 59:75 (1985).
53.
Gellerstedt,
Holzforscbung
G., and Lindfors,

38: 151 (1984).
E-L.,
54. Fengel, D., and Wegener, G., Wood. Cbemistry, Ultrastructure,

Reactions,
W. de
Gruyter, Berlin, 1983, p. 172.
55. Ohara, S., Hosoya, S., Nakano,}.,
Gakkaisbi
26:408 (1980).
Mokuzai .
56. Robert, D., Bardet, M., Gellerstedt,

G.,
Lindfors,
E-L.,] Wood Cbern. Tecbnol.
4:239 (1984).
57. Gellerstedt,
G., and lindfors,
70(6):119 (1987) .
E-L., Tappi J.
58. Iversen, T., and Wannstrom,

scbung 40:19 (1986).
S., Holz/or-
59. Minor,}. L., "Chemical linkage of Polysaccharides to Residual lignin in Pine Kraft
Pulps," 1983 International
Symposium on
Wood and Pulping Chemistry
Proceedings, }TAPPI, Tokyo, Vol. 1, p. 153.
60. Hortling, B., Ranua, M., Sundquist,}.,
Pulp Pap. Res.}. 5: 33 (1990) .
Nord.
61. Gellerstedt,
G., and lindfors, E-L., "On the
Structure
and Reactivity of Residual lignin in Kraft Pulp Fibers," 1991 International Pulp Bleaching
Conference
Proceedings,
SPCI, Stockholm, Vol. I, p. 73.
62. Favis, B.D., Willis:}.M., Goring, D.A.I.,j
Wood Cbern. Tecbnol. 3:1 (1983).
63. Gellerstedt,
537 (1976).
G., Svensk
111
PaPPerstidn.
64. Glasser, WG., and Morohoshi,

62(12):101 (1979).
79:
N., Tappi
65. Gellerstedt,
G., in Metbods
in Lignin
Chernistry
(S.Y. lin, C.W Dence, Eds.),
Springer, New York, 1992, p. 322.
66. Meller, A., Holzforscbung
19:118 (1965).
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D., Engstrand, P.,
Htun, M., in Properties 0/ Ionic Polymers.
( L. Salmen, M.
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and syntbetic
Htun, Eds.), Swedish Pulp and Paper Research
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Stockholm,
STFIMeddelande
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68. Scallan, A.M., and Grignon,}.,
PapPersttdn.
82:40 (1979).
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69. Theander,
Carbobydr.
(1988).
0., and Nelson, D.A., Adv.

Cbern. Biocbern.
46:273
70. Forsskahl,
Carbobydr.
I., Popoff, T., Theander,

Res. 48:13 (1976).
0.,
71. Gellerstedt, G., Pranda,}., lindfors, E-L.,j

Wood Cbern. Tecbnol., 14:467 (1994).
72. Assarsson, A., in Hartskornpendiurn
(I.
Croon,
Ed.),
Svenska
Pappers-och
Cellulosaingeniorsforeningen,
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no. 11, I969,p.62.
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74. Berry, R.M., and Fleming,
scbung 41:177 (1987).
B.I., Holz/or-
75. Gellerstedt,
G., lindfors, E-L., Pettersson,
M., Sjoholm, E., Robert, D., "Chemical Aspects of Chlorine Dioxide as a Bleaching
Agent," 1991 International
Symposium on
Proceedings, Appita, Parkville, Victoria, Australia,
Vol. 1, p. 331.
----
SECTION m:

Chapter 2:
Reaction Principles in Pulp Bleaching
Carlton W. Dence
Professor Emeritus
College of Environmental Science and Forestry,
Syracuse, NY
1. General considerations
. . . . . .. .
. . . .. . . . . . . . .. . .. .. . ..
2. Classificationof bleachingreaction types. .. .. .. . . . ...

3. Reactive sites for attack of bleaching
4. General
reactions
in pulp
agents
. ... .. ... ..
115
115
. 115
bleaching
118
4.1 Electrophilic
substitution
and oxidation of
aromatic structures.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 118
4.2 Addition
reactions
of olefinic
strucrures
. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 120
4.3 Free radical-initiated

cleavage of orthoquinonoid
rings. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 120
4.4 Coupling
of lignin free radicals
121
4.5 Homolytic rearrangement

of initially formed
free radicals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
4.6 Free radical abstraction
of hydrogen
atoms
...
124
4.7 Addition of nucleophiles

to carbonyl
and conjugated
carbonyl groups. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
113
Chapter III 2: Reaction Principles in Pulp Bleaching
ChapterID 2:
Reaction Principles
in Pulp Bleaching
A precise and comprehensive description
of every chemical transformation
taking
place during pulp bleaching is not available.
lbis deficiency, in part, is attributable to the
large number and complexity of the bleaching systems currently in use. Bleaching system complexity is expressed not only by
the number of chemicals involved and the
sequence in which they are applied, but
because an individual bleaching chemical
may give rise to additional, intermediate reactive species throughout the course of the
bleaching treatment.
An additional handicap encountered in
attempting to characterize the principal
chemical transformations occurring during
bleaching is the lack of a clear understanding of the structure of the components that
constitute various unbleached pulps, particularly lignin. As was indicated in the previous chapter, information
about the
structure of lignin in unbleached
pulps
ranges from good to incomplete depending on the type of pulping process used and
on the process conditions. Moreover, with
each successive stage in a multi-stage bleaching sequence, the structural features of the
residual lignin become increasingly less distinct until a point is eventually reached
where it is no longer possible to correlate
structural changes in the lignin with the
bleaching response of the pulp.
In an attempt to address the problems
outlined above, Gierer (1-4) has developed
a concept in which the complex chemical
reactions observed in pulp bleaching are
classified according to common mechanistic types. Using this approach, the fundamental similarities and differences inherent
in the action of various bleaching agents are
highlighted. Because this concept provides
a useful background for the discussion of
the chemistry of individual bleaching stages
in the following chapters, it has been
adopted as the basis for the organization
and discussion
chapter.
115
of material covered in this
2. Classification
of bleaching
reaction types
116
Table 1. Reactive
Reactive
species
In the general concept developed by

Gierer, bleaching reactions may be classified mechanistically as electrophilic or nucleophilic. Typically, electrophilic reactions
initiate lignin-degrading
bleaching processes and involve cations (in acidic media)
and radicals (in acidic, neutral, or alkaline
media) generated from commonly used
bleaching chemicals. These species function mainly as oxidants, preferentially attacking electron-rich phenolic and ethylenic
structures in lignin.
Initial nucleophilic reactions occur typically in lignin-retaining bleaching. These
reactions take place primarily in alkaline
media and involve anions and, to a much
lesser extent, radicals. In an initial step,
these reactions are essentially reductive and
involve carbonyl- and conjugated carbonylcontaining structures. Nucleophilic reactions also occur in lignin-degrading
processes where they follow and complement the initial attack of an electrophile.
The electrophiles,
radicals, and nucleophiles present in commercial pulp bleaching systems are listed in Table I.
cbemlcal
species
I. blHcbl.g.
Name
Type
E'orN'
Function in
Cl+
ct.
octCIO,
cWoronium ion"
cWorine radical
hypochlorite ion
cWorine dioxide
cation
radical
anion
radical
E
E
N
E
pH range
initial reaction
1. Present during bleaching with cWorine, hypocWorite,
and cWorine dioxide
oxidant
oxidant
reductant
oxidant
acidic
acidic
alkaline
acidic
2. Present during bleaching with oxygen, hydrogen peroxide, and ozone
.00.
00"
HOO.
HOOHO.
OH+
+000-
oxygen
superoxide
anion radical
hydroperoxide
radical
hydroperoxide
anion
hydroxyl radical
hydroxonium ion
ozone
3. Present during hydrosulfite

SO,"
3. Reactive sites for attack of

bleaching agents
The chemistry of bleaching is concerned
mainly with the response of lignin to the
action of various bleaching agents because
successful bleaching requires that lignin be
removed from the pulp or modified in situ.
The principal sites for the attack of electrophilic species on lignin are shown for the
upper two softwood (guaiacyl) lignin units
in Fig. IA. In theory, sites ortho and para
to the hydroxyl and alkoxyl substituents on
the aromatic ring should be preferentially
attacked by electrophiles. In practice,however, the preferred sites of attack in nonconjugated and non-condensed lignin units
are the positions para to the hydroxyl and
alkoxyl substituents (t.e., the 1- and 6-positions) and ortho to the hydroxyl substitu-
HS03-
sulfur dioxide
radical anion
bisulfite anion
diradical
radical
anion
oxidant
all
oxidant
alkaline/neutral
radical
oxidant
acidic
anion
radical
cation
cation
N
E
E
E
reductant
oxidant
oxidant
oxidant
alkaline
all
acidic
acidic
reductant
reductant
all
acidic
(dithionite)
radical
anion
anion
bleaching
N
N
4. Present during all alkaline treatments

OH,
b
hydroxide ion
anion
alkaline
E = Electrophile; N = Nucleophile
Derived
from Clz or HOel
ent (i.e., the 3- and 5-positions).

This
anomoly may be traced to electronic and
steric effects. In ring-conjugated ethylenic
units (upper right-hand structure in Fig. lA),
the karbon
atom represents an additional
reactive site for electrophilic attack.
The preferred sites for attack of nucleophiles on lignin are shown by the two bot-
tom structures in Fig. IA. In this instance,

nucleophiles typically attack electron-deficient carbonyl carbon atoms and carbon atoms conjugated
to carbonyl groups as
shown in the figure for qUinone methide

(left) and extended quinone methide (right)
units. This same principle may be used to
identify reactive sites in 0- and p-quinones,
--
117
118
(Non-<:onjugated
units)
(Ring.oonjugated
4. General reactions in pulp

bleaching
that are specific to a single bleaching

cal are discussed
in Chap. III 3.
A relatively large number of reaction

types have been identified as contributing
to the overall effect produced when pulps
are bleached (3,4). Because a comprehensive and detailed discussion of each and
every one of these processes is outside of
the scope of this book, a few examples of
what are judged to be the more significant
reaction types have been arbitrarily singled
out for illustration and comment. Reactions
4.1 Electrophilic substitution and

oxidation of aromatic structures
chemi-
The reactions of cationic bleaching species with the residual lignin in chemical
pulps are among the most important and
well-documented of all bleaching reactions.
The general sequence shown in Fig. 2 is
comprised of three distinct pathways: electrophilic substitution at an unsubstituted
ring carbon, electrophilic substitution of the
units)
+X
Sites of Attack by Electrophiles
-CI
-C-R
_c-
.~-~--
Main Attack
--
Minor Attack
'~-~OCH3
+H:10
--_
(Non-conjugated
units)
(Ring-<:onjugated
units)
~/
:~~OH
.2H'"
-ROO
.2H'"
-ROO
Sites of Attack by Nucleophiles

Fig. 1.
ReJlCU"e sites in lignin
(A) tmil CIIr/Iobydrtde
(8) ,,,dls.
AtliIptedfrom
H-zO
:~~oo
~o
o
Gierer (1-4).
R=H.alk~.oraryi
stilbene quinones, and vinylogous stilbene

quinone:>.
Although attack of bleaching chemicals
on the carbohydrate components of pulp
is almost always unintentional, in practice
these side reactions are unavoidable and

have the potential for causing deterioration
of pulp strength and yield. The sites in cellulose monomer units prone to attack by
electrophiles are shown in Fig. lB.
/
luther electrophtlic
attack by cations
Fig.2. Reaetimrsof a_tic
X=CI.HO
polymerization
through attack
strrwtures in lignin with cationk speeies (:J).
andlor degradation
by nucleophiles

l-carbon with displacement of a benzyl alcohol side chain, and dealkylation. All of
these transformations proceed through a
complex to three distinct cyclohexadienoyl
intermediates.
Electrophilic substitution is illustrated in
Fig. 2 by an attack of a cationic species (X+)
on the 6-carbon of the aromatic ring (Pathway A).
Additional substitution may take place at
other electron-deficient
ring sites to a degree depending on the type and availability
of the cationic species and the incidence
of competing reactions. The effect of the
introduced ring substituent on lignin solubility depends on the hydrophilicity of the
attacking cationic species; for example,
chloro substituents have an adverse effect
on water solubility; hydroxyl groups have
the opposite effect.
The occurrence of electrophilic substitution at the I-position carbon (Pathway B,
Fig. 2) is contingent on the susceptibility
of the side chain to displacement.
Resonance stabilization
of the displaced
cationoid side chain appears to facilitate its
release (5). Benzyl alcohol groups ably
meet this requirement because, in this instance, the displaced side chain is readily
stabilized by the loss of a proton and the
creation of an aldehyde group. Because side
chain displacement leads to the rupture of
a lignin unit, it is of potential importance
as a Iignin-degrading reaction in pulp bleaching. The significance of its contribution to
lignin degradation
during bleaching depends, to a large degree, on the survival of
119
suitably substituted lignin side chains in the

pulping process.
The dealkylation reactions outlined in
Fig. 2 (C Pathways) lead to the conversion
of aromatic to o-quinonoid moieties. When
the R substituent in the figure is a lignin
residue, the overall process involves the
splitting of an interunitary lignin linkage,
that is, the lignin is degraded.
O-quinones are colored, reactive compounds that typically undergo carbonyl and
conjugated
carbonyl (Michael) addition
reactions with nucleophiles
besides cycloaddition, redox, and rearrangement
reactions (6). In aqueous media, especially
under alkaline conditions, o-quinones exhibit general instability and a pronounced
tendency to undergo self-decomposition
reactions (7). O-quinones are generally
short-lived in the reaction environment of
most commercial bleaching stages.
Catechols (l,2-dihydroxybenzenes)
are
reduction products of o-quinones. In aqueous media, their formation from o-quinone
intermediates,
based on the results of a
study by Simson et aI. (7), can be accounted
for by the sequence shown in Fig. 3.
In this sequence, the trihydroxybenzene,
B, formed by Michael addition of water to
the o-quinone ring system, serves as a reductant for residual starting quinone, A, in the
formation of catechol C. O-quinones and
catechols are readily introconverted and often appear jointly as members of a redox
system. When present as constituent units
of residual lignin in pulp, catechol structures
impart enhanced water and alkali solubility.
120

to the degradation of lignin, the physical
properties and chemical reactivity of the
modified lignin may be significantly altered.
Ethylenic groups are also attacked by reactive bleaching species other than those indicated in Fig. 4. These reactions
are
described in Sect. 3 dealing with the chemistry of individual bleaching agents.
4.2 Addition reactions of olefinic structures

As indicated in Sect. I, ethylenic groups
are often present in the lignin component
of pulp as parts of larger structural types,
for example, stilbenes and vinyl aryl ethers.
As electron-rich entities, these groups react
initially with cationic bleaching species in
a manner analogous to that described for
phenolic nuclei (Fig. 2). A general sequence
for the addition reaction is outlined in Fig.
4. Following the formation of a 1t-complex,
a carbonium
or oxonium ion is formed
which is attacked by weak nucleophiles,
yo, in the system to yield vicinal disubstitution products. Although, as portrayed in
Fig.4,addition reactions do not directly lead
4.3 Free radical-initiated
cleavage of
ortho-quinonoid
rings
As noted by Gierer (3), cationic bleaching species are unable to oxidatively cleave
aromatic rings or o-quinonoid intermediates. Instead, ring rupture is proposed to
occur following the coupling of an initially
formed phenoxyl radical (upper sequence)
X-C-R
~I
.....
-.:
..
/(fOCH,
,
.'
OH ]
/0+[
.#'
()cH3
[
,........0 OH]
C-R
II
/~
[
+:;/
>v
!
,........0
OH]
+X~
A
/~ o
A
~ *
+
Fig. 3. FomullUm of utecbols.frmn o-fJfIl_.
.-
"'"
OH
X-C-R
I
CH
.'
+ C-R
>(1
+Y'
0
H, lv, Olv
X=C1, H)
Y =a, H)
Fig. 4. AdllilUm
or Alk
~/~~
,........0
[ OHJ
retlCliollSof ring-conj"gllted etbylenic groups
.#'
.'
,........0
wit" clltionic species
(3).
()cH3
[O~J
R = Alkyor
Aryl
121
122
or cationic radicals (lower sequence) with

a reactant radical as shown in Fig. 5. The
initial products of the ring opening are
muconic acid (2,+hexadienedioic
acid) esters. The formation type of structures is
noteworthy because they contribute enhanced water and alkali solubility to lignin
residues of which they are a part. Moreover, subsequent hydrolysis of the alkyl or
aryl (R) ester groups (see Fig. 5), as in all
likelihood occurs in an alkaline extraction
stage, leads to cleavage of an interunitary
lignin linkage. Muconic acid derivatives are
also subject to further oxidative fragmentation reactions by bleaching chemicals such
as oxygen, ozone, and cWorine dioxide (2).
x.
OI-r
4.4 Coupling of lignin free radicals
.~"'
HO
.~
RO0
+
HClO
HelO or H2o
x= 00,..
or H2O
0, OH or OOH
Ftg. 5. Proposetl setpm8CfISfor tbe free rtUlklll.t,d.

Hated CleaVilgeof orlbo.q,drunroUl rirrgs (3).
Evidence for the coupling of lignin free

radicals during pulp bleaching has been provided almost exclusively by lignin model
compound studies. However, the oxidative
coupling of phenol-derived radicals in other
reaction environments
is a well.documented process (see, e.g., ref. 8). A5 depicted in Fig. 6, the actual coupling is
preceded by what amounts to the abstraction of a hydrogen atom from a phenolic
hydroxyl group by a reactant free radical to
form a phenoxyl radical (A). A cyclohexadienonyl
radical mesomer
(B) of the
phenoxyl radical then couples with a different or identical free radical to form, in
the example shown in Fig. 6, a biphenyl
compound (C). To the extent that it occurs
in lignin-degrading bleaching, the coupling
of lignin radicals may negate the desirable
effect of competing lignin-degrading reactions.
A
Ftg. 6. Free radkilis
coupUrrg of pberrol-derltJf!d
rtUlkills.
--C-R
I
H~OH
...
"
'...
OCH,
0+
x = CI.O. CI. OH. OOH

Ftg. 8. Proposetl reRCUorr sequences for Irydrogerr
atom abstractWrr from ligrrtrrs (A) and car.
bohydrates (8) (3,4).
-<;:-R
4.5 Homolytic rearrangement

tially formed free radicals
of ini-
As illustrated by the sequences in Fig. 7,

initially formed cation and hydroxylcyclohexadienonyl radicals are postulated as undergoing a rearrangement
in which the
bond between the a and 15camon atoms of
the side chain is homolyticaUy cleaved (3).
This reaction scheme is based on the observed response of lignin model com.
pounds. particularly those having benzylic
R = Aryl or Araxy!
Ftg. 7.
Proposed sequerrces for tbe spumrrg

C IX. C borrd (3).
of the
alcohol groups, to various r~:1~tM\ti':1di~:iI~.

The relevance of this reaction mode as a
lignin-degrading process in pulp bleaching
has yet to be confirmed.
- TYPE
124
123
4.6 Free radical abstraction of

hydrogen atoms
STRUCTURES
Hydrogen atom abstraction from both lignin and carbohydrates by free radicals has
been postulated (2). For lignin, the hydrogen atom may be directly and preferentially
removed from the alpha (i.e., benzyl) carbon atom of the side chain as illustrated in
Fig. SA (3,9). In this process, a benzylic
hydroxyl group is converted (i.e., oxidized)
to an a-keto group. Alternatively, an a-keto
group may arise following abstraction of a
hydrogen atom from the benzyl carbon of
a cationic radical or cydohexadienonyl
radical (3). The a-keto group activates the side
chain in reactions with nudeophiles in later
bleaching stages.
The mechanism by which secondary alcohol groups in glucopyranose
units are
transformed to keto groups is illustrated in
Fig. SB. The introduction of keto groups
into hemicellulose and cellulose chain units
makes them susceptible to S-elimination
(t.e.,"peeling") reactions which often translate into losses in pulp yield and fiber
strength.
Comparison of the proposed sequences
for lignin and carbohydrate units illustrates
a parallelism that frequently is duplicated
in other pulping and bleaching reactions as
well 0,3, 10, 11). That both lignins and carbohydrates react competitively with reactant free radicals bears on the issue of
selectivity in lignin-degrading bleaching reactions. This important topic is dealt with
specifically in Chap. III 3.
..
x = 0: (unconjugated)
X
= 1:
= 2: quinonemethides
=3: extended
conjugated
carbonyl
carbonyls
groups
in side
chain
quinonemethides
8 - TYPE STRUCTURES
4.7
Addition
carbonyl
carbonyl
X = 1: para-quinones
X = 2: stilbenequinones
X = 3: vinylogous
stilbenequinones
N-=nucleophile
Fig. I). Gerlerdl sequences
for the a"'ilion
of nueteopblles
to CIlriJonyl MUI conjugated
cariJonyl structures
(4).
to
This reaction mode is applicable as an

initial step in lignin-retaining bleaching and
as a secondary step in lignin-degrading
bleaching. A general sequence for the reaction of nudeophiles
with conjugated and
non-conjugated
carbonyl structures
is
shown in Fig. 9. In the bleaching of mechanical pulps, the reactive structures are
typically conjugated carbonyl groups such
as are found in coniferaldehyde and quinonoid structures.
References
1. Gierer,].,
Hol:iforschung
2. Gierer,].,
Wood Set. Technol.
36(2):43
(1982).
20:1 (1986).
3. Gierer,].,Holzforschung
44(5):387
(1990).
4. Gierer,J.,Hol:iforschung
44(6):395
(1990).
5. Sarkanen,
K.Y., and Dence,
Chern. 25:715 (1960).
6. Horspool,
(1%9).
WH.,
Quart.
C.W,J
Rev.
Org.
23(2):204
7. Simson, B.,Ayers,]., Schwab, G., Galley. M.,

Dence, c., Tappi 61(7):41 (1978).
8. Gierer,].,
Wood Set. Technol.
20:1 (1986).
9. 'Harkin, J.M., in Oxidative

Coupling
of
Phenols (W.1. Taylor, A.R. Battersby, Eds.),
Marcel Dekker, New York, 1967, pp. 300312.
10. Ek, M., Gierer, J., Jansbro,
schung 43(6):391 (1989).
11. Gierer,
(1980).
X = 0: ortho-quinones
of nucleophiles
and conjugated
groups
J., Wood
K., Holzfor-
Sci. Technol.
14:241
SECTIONm:
Chapter 3:
Chemistry of
Chemical Pulp Bleaching
Carlton W. Dence
Professor Emeritus
Syracuse, NY
1. Introduction
.......
2. Reactions of lignin with bleaching
agents and aJkaJi. . . . . . . . . . . . . . . .
. 127
127
2.1 Chlorine
2.2 Chlorine dioxide.
....
"
............................................
"
2.3 Sodium hydroxide in alkaline extraction. . . . . . . . . . . . . . . . . . . . . . . . . . .
"
2.4 Molecular oxygen. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
127
2.5 Ozone
144
3. Reactions of carbohydrates
with bleaching
132
138
141
agents and aIka1i. . . . . . . . . . . .. 148

149
3.1 Reactions at acetal (glycosidic) sites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

"
3.2 Reactions at non-acetal sites. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
150
3.3 Selectivity in bleaching reactions
152
4. Reactions of extractives
with bleaching
. . . . . . . . . . . . . . . . . . . . . ..
agents . . . . . . . . . . . . . . . . . . . . . . .. 153
125
Chapter III 3: Chemistry of Chemical Pulp Bleaching
127
128
Chapter m 3:
Chemistry
of Chemical
Pulp Bleaching
1. Introduction
Multi-stage bleaching sequences are customarily divided into delignification and
bleaching segments. In a typical delignification sequence, the bulk of the residual
lignin in a chemical pulp is degraded and
solubilized by a single oxidant or combination of oxidants such as chlorine, chlorine
dioxide, oxygen, hydrogen peroxide, and
ozone in conjunction with joint or sequential alkali (NaOH) treatments.
Oxidative
processes invariably lead to the formation
of acidic groups (carboxylic, phenolic and
enolic) that lend enhanced water and alkali
solubility to the lignin fragments to which
they are attached.
Depending
on the
bleaching chemical and. the residual lignin
content of the pulp, some bleaching may
accompany delignification.
In the bleaching segment of a multi-stage
bleaching sequence, oxidants such as chlorine dioxide, sodium hypochlorite, and hydrogen peroxide are used to remove the
remainder of chromophore systems initially
present in the lignin and those formed
in preceding
pulping and prebleaching
treatments.
Because at this juncture of a
multi-stage
bleaching
sequence
the
concentration
of non-carbonhydrate
material in the pulp is relatively low, it is essential that the bleaching (oxidizing) agent
selectively eliminate chromophore residues
while leaving the carbohydrate components
relatively intact to preserve pulp strength
and yield.
Any attempt to describe delignification
and bleaching phenomena by a set of welldefined chemical reactions is of necessity
limited by the meager amount of information available dealing with the structure of
lignin in unbleached pulps or in partially
delignified or bleached pulps. The situation
is further complicated by the fact that most
of the oxidant systems used to delignify or
bleach pulp consist of mixtures of active

species each of which is a potential contributor to the bleaching process. These obstacles have necessitated
the ensuing
descriptions of the chemistry of the different bleaching chemicals being restricted to
the initial treatment of unbleached pulps
with oxidant and alkali because only in
pulps of this type is the structure of the residual lignin known with any reasonable
degree of certainty (see Chap. m 1).
Although the main emphasis in this chapter is on the chemistry of delignification in
bleaching, discussion of the reactions of
carbohydrates and extractives with various
oxidizing agents and alkali is included
below in cases where the outcome of a
bleaching treatment is affected by their
occurrence.
2. Reactions of lignin with

bleaching agents and alkali
2.1 Chlorine
Reaction species in the chlorine-water system
The principal active chemicals in an aqueous chlorine solution are elemental chlorine
and hypochlorous acid. In bleaching, the
relative amounts of these chemicals are
determined mainly by the elemental chlorine and hydrogen ion concentrations
in
accordance with the equilibrium relationship.
Cl, + HP
+->
HOCl + W + Cl
tion pH enhances the delignification of softwood kraft pulp by increasing the proportion of elemental chlorine (2).
Other reactive species that may play a
role in chlorination are chlorine radicals (3)
and dichlorine monoxide (4). The proposed minor involvement of chlorine radicals in bleaching is based on the detection
of a dimeric coupling product after the chlorination of guaiacol (5) and on the effect of
known radical scavengers such as chlorine
dioxide and sulfamic acid in controlling the
viscosity loss (6) proposed to result from
attack of chlorine radicals on cellulose (7).
Dichlorine monoxide is formed by the
dehydration of hypochlorous acid (4):
2 HOCI
+->
qo
[2]
HP
The involvement of this reactive compound

in pulp chlorination has not been demonstrated.
In their reactions with lignin and other
pulp constituents, elemental chlorine and
hypochlorous acid function as electrophiles
(8 and Table I in Chap. m 2). The initial
reacting
species in this instance
is a
chloronium ion (Cl+) formed by the heterolytic cleavage of the Cl-CI bond in elemen-
tal chlorine and the O-CI bond in the conjugate acid of hypochlorous acid:
HOCI + W +-> HpCl ~ HP
[1]
Under typical pulp chlorination conditions.

elemental chlorine and hypochlorous acid
are present initially in approximately equal
amounts (1). As the chlorination proceeds,
the pH decreases because of the formation
of hydrochloric and organic acids. As a result, the [Cl,]/[HOC1] ratio increases in accordance with the equilibrium expressed
by equation [1].
Although the reactions of chlorine and
hypochlorous acid with lignin are qualitatively similar, their relative contributions to
the overall reaction comprising the chlorination process may vary significantly depending on the reaction conditions. For
example, a decrease in the initial chlorina-
+ CI+ [3]
Substitution reactions
Hydroxyl- and alkoxy-activated aromatic
nuclei in lignin undergo rapid and extensive substitution by chlorine. Thus, in the
chlorination of a softwood kraft pulp, substitution of nearly 2 CI/C9 unit has been
observed after only five minutes' reaction
(9). Most, if not all, of this chlorine uptake
can be attributed to aromatic substitution.
:ru~ reaction is portrayed mechanistically
III FIg. lA. The number and location of ar0matic chloro substituents in chlorinated lignin depend on the amount of chlorine
applied and the number and type of substituent groups initially present.
Uncondensed guaiacyl nuclei in softwood lignin
have three unsubstituted sites available for
chlorine substitution; syringyl nuclei, typical of hardwood lignin, have but two. An
additional chloro substituent can be introduced into each of the foregoing ring types
by electrophilic displacement of a suitably
substituted side chain (see below). Under
conventional chlorination conditions, chlo-
-w
H. Alkyl, Aryl
=
R1 = H or rest of lignin molecule
W.
~~
/yoc~
/0
R,
Fig.1. ReactUmsequem:esfor aromstk sabstl",tlon and side chal" displacement Irycbloronillm Ums.
129
130
rine uptake by aromatic substitution in the
range 1.5-3.0 CVC9 units has been reported
for softwood kraft pulps (11-13). Chlorine
uptake by lignin becomes increasingly restricted with each successive introduction
of a chlorine atom because of the deactivating effect of the electron-withdrawing
chloro substituents on aromatic substitution
reactions (9).
The relative reactivity
of the three
unsubstituted
ring sites in uncondensed
guaiacyl units during chlorination is determined by the combined and overlapping
o,p-directing effects of the hydroxyl and
alkoxyl substituents.
Steric hindrance by
the side chain and alkoxyl substituents also
may have an effect in detennining the preferred site(s) for chlorine substitUtion (9).
The results of studies of the chlorination
behavior of guaiacyl-type lignin model compounds (14-16) and softwood lignin (13,
14) indicate an order of preference for ring
monosubstitution
of 6>5>2 (see Fig. 1 for
ring numbering system).ln syringyl nuclei,
the 2- and 6-positions are equally activated
by the two para methoxyl groups with the
result that monosubstitution
may occur
with equal ease at either site.
The solubility of chlorinated lignin in
water is decreased by the substitution of
(hydrophobic)
chloro substituents on the
aromatic ring. However, to the extent that
these substituents are replaced by hydroxyl
groups in following alkali (NaOH) treatments, both alkali and water solubility of
the lignin may be enhanced (see Sect. 2.3).
The formation of chloroaromatic structures
during the chlorination of lignin has great
environmental significance because the observed toxicity and mutagenicity displayed
by a large number of compounds identified
in spent chlorination effluent can, in part,
be attributed to such groups (Chap.VIllI).
Aromatic substitution of lignin also occurs by electrophilic displacement of the
side chain by chlorine as illustrated by sequence B in Fig. 1 (15,17). Although the
substitution reactions shown in the figure
occur simultaneously, reaction A has been
estimated to occur at about 10 times the
rate of reaction B (17). Side chain displace-
ment takes place to a meaningful extent

only when the a-carbon of the side chain is
suitably substituted, for example, by a hydroxyl group (14, 15, 17-20). Thus, phydroxybenzyl alcohol units in lignin are
especially subject to electrophilic displacement reactions.
Because they lead to modification of the
functional groups attached to the benzyl (a)
carbon atom in the 1ignin side chain, kraft
and sulfite pulping processes have a major
influence in determining the extent to which
side chain displacement occurs in chlorination. Typically, the benzyl alcohol content
of lignin is reduced following kraft and sulfite
pulping. However, some of these groups
apparently survive and participate in side
chain displacement reactions as evidenced
by the detection of compounds in pulp chlorination effluent in which the carbon atom
to which the side chain was initially linked
is occupied by a chlorine atom (21).
The displacement of a lignin side chain
during chlorination is significant in bleaching because, in contrast to electrophilic substitution of chlorine at unsubstituted sites,
it represents a process in which aromatic
substitution is accompanied by rupture of
a lignin structural unit. Side chain displacement reactions may have important environmental implications because it has been
proposed (22, 23) that dibenzodioxin and
dibenzofuran structures, initially formed in
lignin biosynthesis, undergo aromatic chlorine substitution and are released from the
lignin network by side chain displacement
reactions.
Addition reactions
Organochlorine structures are also proposed to arise by the addition of chlorine
to olefinic structures in lignin. Ethylenic
groups are present in native lignin as phydroxylcinnamyl alcohol and p-hydroxylcinnamaldehyde
end units (24). During
kraft pulping, these groups are eliminated
and new ring-conjugated ethylenic groups
are introduced as part of styryl ether (2527) and stilbenoid structures (26-28). In
sulfite pulping, some ring-conjugated ethylenic groups reportedly survive the sulfonation conditions (29-31).
As was the case with aromatic substitution, the initial step in the addition of chlorine to olefinic groups is an attack of a
chloronium ion on an electron-rich carbon
as pictured in Fig. 2(3). The resulting intermediate undergoes attack by a weak nucleophile such as chloride ion or water forming
a vicinal dichloro unit or a chlorohydrin,
respectively. The formation of a chlorohydrin from ring-conjugated
ethylenic
structures has the effect of introducing a
hydroxyl group on the a-position of the side
chain, making the side chain susceptible to
displacement by chlorine (Rg. 1, sequence
B).
Although chlorine addition is invariably
included in lists of the types of reactions
occurring when chlorine reacts with lignin,
there is almost no direct evidence that such
reactions have any relevancy in the chlorination of pulp. However, in a recent study,
a chlorohydrin was reported to be formed
from an intermediate chloro-o-quinone in
the aqueous chlorination
of trichloromethylcatechol (32). The effect of chlorine
addition reactions on the solubilization
of lignin during pulp chlorination is, in all
probability, minimal because the number of

available ethylenic groups is small. A portion of whatever aliphatic-bound chlorine
is formed during chlorination is removed
in succeeding treatments with alkali in basecatalyzed e1imination and substitution reactions (Sect. 2.3).
Cleavage of alkyl aryl ethers (dealkylation)
The guaiacyl and syringyl nuclei of lignin characteristically contain one and two
methoxyl groups, respectively; other alkyl
aryl ether groups that may be present are
those in which the alkyl group is the side
chain of an adjacent phenylpropane
unit.
During chlorination in aqueous media, the
methoxyl groups in lignin model compounds (14, 16, 19,20,33,34)
and in lignin (9, 11, 33, 35-37) are rapidly and
extensively cleaved as evidenced by the
large amounts of methanol found in the
product mixtures and the lower methoxyl
content of the chlorinated pulp. lignin
model compound studies (19,34,38)
have
also demonstrated that isopropyl aryl ethers
are equally susceptible to cleavage during
chlorination.
C-R
II
HC
'
_0
Y:[ ]
ocH3
o OH
Fig. 2. RetJCtlOfl seiJllenees for IUldItIon of elenumtal

ylenlc groups (3).
cblorlfU! or hypocblorous
arid to ring-conjugated
etb-
--------------.~---
131
132
R = Alkyl
Ct. = Chlorine atoms at
unspecified ring sites
Catechol
unit
/~
o
+7
Q-Ouinone
Unri
Degradation
products
Muconlc acid
Unri
Fig. 3. RetU:U018S6q_es
for cleavllge of IIIIlyI aryl etllers (.tdllylatftm)
benzoq,"_
Irrterrrretlllltes by cblorlflt! In IItJfIJfISffIt!tlitl.
IIU tbe oxIiltIt"'"
of 0-
A proposed mechanism for the cleavage

of alkyl aryl ethers is shown in Fig. 3. The
sequence is initiated by attack of a chloronium ion or polarized chlorine molecule
on the ether oxygen to form an oxonium
ion (A). Decomposition of this ion by water leads to the formation of a hypochlorous aryl ester (B) and release of methanol
in the example shown. The final step is pictured as consisting of alternative pathways
that account for the observed formation of
o-quinone (16, 19) or catechol (9,15,20)
structures. The main difference in these tWo
pathways is that the step leading to the for-
quinones are potentially interconvertible in

pulp chlorination systems: catechols may
be oxidized to o-quinones by chlorine or
dissolved oxygen (air) and o-quinones may
be reduced by hydrogen donors such as
appropriately substituted catechols.
The cleavage of methoxyl groups by chlorine increases the water solubility of lignin
and especially its alkaIi solubility when the
reaction leads to the formation of a phenolic
hydroxyl group. Under the same conditions, cleavage of ether bonds typified by
those in g.()-4 structural units is far more
important
in its favorable
impact on
matiM of a catechol is essentially a hydrolysis catalyzed by chlorine; the reaction giving

rise to an o-quinone is an oxidation step.
As shown in the figure, catechols and 0-
deHgnification
because it leads to the
splitting of a lignin interunitary bond. Because some B-aryl ether structures are
present in the residual lignin in kraft (26)
Pulp Bleaching
- Principles
and Practice
and sulfite (39) pulps, their rupture may

account for a portion of the lignin dissolved
when these pulps are chlorinated.
DeaIkylation is pH-dependent and occurs
to an increasingly greater extent as the cWorination pH is lowered. For example, the
amount of methanol recovered after cWorination of a softwood lignosulfonate
decreased about 4-fold when the pH was
lowered from 9 to less than 1 (33). Another
factor that gives evidence of controlling the
extent to which dealkylation occurs in cWorination is steric hindrance. This effect was
indicated by the results of a lignin model
compound study in which aromatic chloro
substituents, positioned ortho to methoxyl
and isopropoxyl substituents, were found
to severely retard the cleavage of these
groups when chlorinated (34). Because a
direct relationship has been found between
dealkylation (specifically, demethylation)
and delignification of a softwood kraft pulp
by chlorine (9), sterlc hindrance may be
viewed as indirectly having an adverse effect on delignification
by retarding the
cleavage of alkyl aryl ethers.
Oxidation reactions
The incidence of oxidation reactions is
indicated by the identification of low molecular weight carboxylic acids (35, 40-42)
and other compounds (4345) in the chlorination effluent, by the carboxyl content
of the effluent solids (37), and by spectroscopic (JR, 'H NMR,I3C NMR) analysis (37)
of the aformentioned solids. Kraft lignin
that is not solubilized during chlorination
is also oxidized as indicated by its increased
carboxyl content (11). Further, oxidative
degradation of aromatic rings in lignin is suggested by the systematic decrease in ar0matic structures
in softwood kraft and
bisulfite pulps following the addition of increasingly higher amounts of chlorine (11).
Reaction sequences giving rise to the
wide array of structures represented by the
compounds identified in cWorination effluent have not been characterized in most
instances. Presumably, the sequence shown
in Fig. 3 is an accurate depiction of the overall sequence of oxidation reactions which
occur during chlorination. The formation

of o-benzoquinone
intermediates
is welldocumented
by lignin model compound
studies (16, 19) and supported by the detection of tetrachloro-o-benzoquinone
in
chlorination effluent (46), but the reactions
accounting for the subsequent degradation
of these rings have received relatively little
attention.
The conversion of cWorine-substituted 0benzoquinones to muconic acid-type structures is a logical step in the oxidative
breakdown sequence (Fig. 3), but support
for this transformation is limited (16, 37)
and alternative pathways have been suggested (32, 47). Gierer (8) has pointed out
that oxidative cleavage of aromatic nuclei
either directly or by way of o-benzoquinone
intermediates cannot occur by the action
of a cationic species such as CI' but instead
requires attack by a radical species, possibly .OCI. The involvement of hypochlorous acid in the oxidative degradation of
aromatic rings is suggested by the finding
that the amounts of aromatic products and
oxalic acid in the effluent of a chlorinated
softwood kraft pulp decrease significantly
when the initial pH of the cWorination mixture is artificially lowered to 0.5 to decrease
the proportion of hypocWorous acid relative to that of elemental chlorine (11).
2.2 Chlorine dioxide
In this section, the chemistry of chlorine
dioxide bleaching is of necessity restricted
to those reactions occurring in the delignification portion of a multi-stage bleaching sequence where the lignin content of
the unbleached pulp is relatively high and
the structural features of the residual lignin
are known to some extent.
Reactive species in aqueous chlorine
dioxide systems
CWorine dioxide is a free radical and a
powerful oxidant which, on undergoing
reduction to chloride ion, releases five oxidation equivalents/mole:
ClO, + 2 H,o
+ 5 e- ~ CI" + 4 OR"
[4]
When used to delignify pulp under acidic

conditions, chlorine dioxide is reduced by
"--~
~_._-

lignin to chlorous acid, HCIO" and hypochlorous acid, HOCI, in a series of stepwise reactions (48). Chlorous acid (or
chlorite, depending on the pH of the bleaching liquor) is essentially unreactive toward
lignin (48); hypochlorous acid (or elemental chlorine), on the other hand, is a reactive chlorine dioxide reduction product
which can function as an oxidizing agent
or react in ways that lead to the formation
of chlorine-substituted
organic products as
described in Sect. 2.1. Also, the reactive
free radical species, chlorine monoxide
(Cia.), has been postulated as arising from
a two-electron reduction of chlorine dioxide by lignin (48).
The inorganic chlorine species formed
in the reduction of chlorine dioxide by lignin may interact with one another or aecompose in a variety of ways. For example,
chlorous acid and hypochlorous acid can
interact to regenerate chlorine dioxide (51):
2 HCI02 + HCIO --.202 +2 HP + H' + 0- [5]
In a reaction that is pH-dependent
(52),
chlorite reacts with hypochlorous acid to
form chlorate (53):
HClO + CI02- --> CI03' + H' + a-
[6]
Chlorate is an inactive species in chlorine

dioxide delignification (54) and hence its
formation represents a loss of active chemical. Finally, molecular oxygen has been
proposed to arise from the decomposition
of chlorite (51), chlorine monoxide (55),
and chlorine dioxide (54, 56). Under the
prevai1ing acidic conditions of chlorine dioxide bleaching, molecular oxygen is not
an active bleaching agent.
Reactions of chlorine dioxide with lignin
Chlorine dioxide is an electrophile (fable
1, Chap.lll 2) and as such preferentially attacks electron-rich lignin sites typified by
phenolic and non-phenolic rings and ringconjugated ethylenic groups. Based almost
exclusively on the results of model compound studies, the two principal types of
reactions that occur when chlorine dioxide is used as a delignifying agent can be
classified as oxidation and aromatic chlo-
133
134
rine substitution. These reactions are discussed below as they apply individually to
phenolic and non-phenolic units and ringconjugated ethylenic groups.
Phenolic units
Several of the proposed sequences for the
overall reaction of phenolic lignin units with
chlorine dioxide are outlined in Fig. 4 (3,
49, 57-59). The initial reaction in all instances is the formation of the phenoxy radical (IA) and its mesomeric radical forms
(lB-ID) by a one-electron oxidation. The
coupling of these various radicals with additional chlorine dioxide leads to the formation of chlorous acid esters (Fig. 4,
lIB-lID). On decomposition, the latter structures are convened to o-benzoquinones or
the corresponding catechols (49, 57, 60),
p-benzoquinones
(49, 59, 61, 62), and
muconic acid mono methyl esters (38, 49,
57) or their lactonized forms (49, 57, 59,
62) with release of chlorous acid or hypochlorous acid in one- or two-electron oxidation reactions.
The conversion of guaiacyl nuclei to
muconic acid monomethyl esters and their
cyclicized (i.e., lactonized) forms (Fig. 4,
IIIBI) is an important degradation reaction
in chlorine dioxide bleaching because it
leads to increased water and alkali solubility of the residual lignin. Muconic acid
structures and their corresponding lactones
are also subject to funher oxidation reactions in which dicarboxylic acid fragments
are formed (63-65).
The most prominent reaction of those
shown in Fig. 4 is oxidative demethylation
(57,59). The prevalence of this reaction is
indicated by the high yields of methanol
found in the reaction mixtures following
treatment of lignin model compounds (59)
and lignin (37, 62) with chlorine dioxide.
The initial product of oxidative demethylation is an o-benzoquinone derivative (Fig.
4, lIB). The latter is not convened to a
muconic acid derivative by chlorine dioxide, but instead undergoes dimerization and
polymerization reactions (57) that have a
retarding effect on delignification.
Conversely, funher oxidation and degradation
of o-quinonoid units through the proposed
_A
R=HorSldeChain
.-~~
Biphen)i
Structures
OH I
+clO'l-
/~ o
HCIO,
IB
/~o lIB
'I -
+H,o
+H,o
_
HOCI(CI.)
Lactone
esters
+H,o
-HCIO,
HCI02
CHpH
Side chain oxidation

and coupling
products
Condensation and
reduction products
Fig. 4. SeqrInIen for tile retIdimI of chlorine dioxide with pbettolk
(57) attack of chlorite ions or chlorine dioxide on the ethylenic

groups in the
quinone ring should promote lignin degradation.
The postulated formation of p-benzoquinone structures (Fig. 4, IICl) by the oxidation of lignin with chlorine dioxide is
rings In lignin (57).
restricted by the requirement that benzyl

alcohol groups be present in the side chain.
Because the number of such groups is significantly reduced during puJping, the probability of any meaningful lignin degradation
occurring by this route is low. Alternatively,
an alkyl substituent
at the alpha (i.e.,

benzyl) side chain position may be oxidized
by chlorine dioxide to a benzyl alcohol or
a-carbonyl group as described elsewhere
(57) in greater detail.
The reactions of the ortho-radical (lD)
(Fig. 4) with chlorine dioxide have not been
as thoroughly documented as those of the
other mesomeric radicals. From a model
compound study (57), evidence has been
obtained indicating that free radicals typified by ID may couple with one another to
fonn biphenyl structures. Although such
reactions impede lignin solubilization, the
effect may be partially or totally offset by
subsequent rupture and degradation of the
coupled phenolic rings. In the other reaction of radicailD shown in Fig. 4, a quinol
chlorous ester (lID) is fonned and then converted to an oxirane structure, lID!. Under the existing acidic conditions,
the
oxirane ring presumably is hydrolyzed to
the corresponding glycol (66).
Chlorine dioxide oxidation of lignin and
lignin model compourtds invariably is accompanied by chlorination reactions. These
reactions can be traced to hypochlorous
acid (in equilibrium with elemental chlorine) fonned from the partial reduction of
chlorine dioxide by an organic substrate as
illustrated in Fig. 4 (hydrolysis of chlorous
ester lIB). In the chlorine dioxide treatment
of lignin model compounds, chloroaromatic
compounds
are detected indicating that
aromatic substitution competes favorably
with oxidative ring cleavage and other reactions. With model compounds as substrate, chlorine substitution has been found
to occur to the extent of about one atom!
phenolic ring (38, 57, 60, 62-65). The uptake of chlorine by lignin in kraft pulp in a
chlorine dioxide delignification treatment
is of the same order of magnitude (37).
In principle, elemental chlorine or hypochlorous
acid, fonned in the chlorine
dioxide oxidation of lignin models or lignin, can undergo other typical reactions, for
example, dealkylation, as is described in
Sect. 2.1. Although some evidence has been
obtained indicating that chlorine-promoted
demethylation takes place during the chlo-
135
136
rine dioxide oxidation of lignin models,

most demethylation
observed in this instance is ascribed to the effect of chlorine
dioxide (59).
Despite the reported finding that hypochlorous acid is generated in yields of 5060% when chlorine dioxide reacts with
lignin model compounds
(59), chlorine
uptake by model compounds (60) and lignin (37) in chlorine dioxide treatments is
nevertheless far less than that occurring
when chlorine is the sole reactant. This finding is the basis for the partial replacement
of chlorine by chlorine dioxide, a practice
commonly employed in commercial bleaching to reduce the fonnation of chlorinated
toxic and mutagenic compounds.
Non-phenolic units
Chlorine dioxide reacts with non-phenolic units as well as with phenolic units
although at a greatly reduced rate (57, 59,
67). Sequences outlining several of the
identified reaction pathways are shown in
Fig. 5. In contrast to the initial fonnation
of phenoxy radicals postulated to occur
when chlorine dioxide reacts with phenolic
structures, non-phenolic nuclei are first converted to the mesomeric radical cations lA,
m, and IC in acidic media as shown in the
figure. Addition of chlorine dioxide to radical cations lA and m (Fig. 5) followed by
hydrolysis of the resulting chlorous esters
leads ultimately to the fonnation of a pbenzoquinone,
IlIA (57, 69, 63) and a
muconic acid di-ester, IIIB (57, 59, 63, 67)
or lactone (59). It is noteworthy that the
same types of compounds are fonned when
chlorine dioxide reacts with phenolic structures.
Abstraction of a hydrogen atom from a
benzyl carbon yields, after loss of a proton,
an a-keto group in the example shown in
Fig. 5. Ca-C. cleavage by rearrangement of
cation radicailD leads finally to the fonnation of an aromatic aldehyde, IIID (Fig. 5).
Although side chain fragmentation would
be expected to enhance lignin degradation,
its impact on chlorine dioxide ddignification treatments has not been demonstrated. Other types of products fonned in
the reactions of chlorine dioxide with non-
R,==
R,
Side chain
Alkyl or aryl
Aryl
of
aroxyl
lCIO,
,I- ,==()
==,~
.- YOCH,
'-R~OCH'
/O+
R
IB
I'"
.- TOCH,
IC
R/O
ID
["t']!
[+]1"
-C-R,
R
000
COH
"'"
t>-
..-
~0cH,
,Q,
RP
/0
R,
.-
j'-HCIO
- CH,OH
-w
cf
/~
OCH,
000
.-' '
/0+
R,
lIB
IIA
HC-OH
[,
- HCIO
nated by hypochlorous acid (in equilibrium

with elemental chlorine) generated through
reduction of chlorine dioxide (57, 63, 67).
As indicated by lignin model studies, the
substitution level in these

again is about one chlorine
ring (57, 63, 67) for typical
oxidant. If the chlorinated
OCH,
/0
R,
["'
-w
phenolic lignin model compounds

are
recorded elsewhere (38, 57, 59,63,64,67).
As was noted previously for the reactions
of chlorine dioxide with phenolic structures, etherified phenolic rings are chlori-
IIC
lID
["'
instances once
atom/aromatic
applications of
ring is then oxi-
oy chlorine dioxide, {he chlorine mar

appear as a substituent of an oxidized product, for example, a muconic acid derivative
(63).
dized
Chapter
m 3: Chemistry
Based on product analysis, the dominant

process in the reaction of both phenolic and
non-phenolic structures with chlorine dioxide is demethylation as evidenced by the
recovery of methanol from the product
mixtures (59). The methanol arises from
the hydrolysis of methyl aryl ether groups
(e.g., structure IrA in Fig. 5) and the hydrolysis of muconic acid methyl esters. Competing sequences leading to the formation
of p-benzoquinones
and muconic acid esters (or lactone esters) are relatively more
important when phenolic structures are
oxidized by chlorine dioxide (59).
As stated at the outset of this subsection,
the results of lignin model compound studies reveal that phenolic rings are far more
reactive toward chlorine dioxide than th~ir
non-phenolic counterparts
(57, 59, 67).
This implies that, under technical bleaching conditions,
chlorine dioxide reacts
mainly, if not solely, with phenolic units in
the residual lignin. However, it is conceivable that non-phenolic muts may indirectly
react with chlorin: dioxide following their
conversion to phenolic units by the action
of hypochlorous acid or elemental chlorine
formed by the reduction of chlorine dioxide (59).
Ring-conjugated ethylenic groups
Besides phenolic and non-phenolic rings,
the other principal electron-rich sites in lignin are ring-conjugated double bonds such
as are present in p-hydroxycinnamaldehyde
and p-hydroxycinnamyl
alcohol units in
native lignin (24) and in styryl aryl ether
(25-27) and stilbenoid (26-28) structures
in chemically modified lignin. The initial
attack of chlorine dioxide on an olefinic
double bond leads to the formation of an
epoxide and elimination of a hypochlorite
radical as shown in the right-hand column
of Fig. 6 (3, 48, 55). The reactions of the
epoxide that follow are pH-dependent: at
pH 2, acid-catalyzed hydrolysis of the ring
occurs and a diol, IV,is formed, but at pH 6
the ring is relatively stable (68).
The hypochlorite radical released in the
epoxidation reaction oxidizes chlorine dioxide to chlorate and is reduced to hypochlorous acid or elemental chlorine:
of Chemical
Pulp Bleaching
137
138
H, aryl, or araxyl
ij
..,
80
80
60
60
ij E
.~ '"
~E-o
e <Ii
"'<z:
0"';:;~c: 40
o <Ii
:E-o.U
'0 20
"#
0
/~~
/0
Hi
/0
40
80
60
Cl02 Substitution, %
40
a.-.g
.~
~.c
20
E:'::
00
..( ,0
C'
0
100
to the formation of an a-chloro ketone, VI

(68,69). Similar to aromatic chlorine substitution, these addition reactions of chlorine or hypochlorous acid, by leading to the
formation of organically bound chlorine, are
undesirable from an environmental viewpoint and have little, if any, impact on lignin degradation. Cleavage of the ethylenic
double bond, which would be expected to
have a favorable effect on lignin degradation, appears to occur to only a minor extent (68).
V
CI02
a-C-R
I
/~~
/0
20
'g
=>1:1
~-0'"
e
Fig. 7. Effeet of chlorhre dioxide Sllbstihllfml on

tbe fOrmlltion of chlorotlromatic products
(NlNJe A) ami arotlltltk riIIg degrtUl4tion
(CUNJeB) in tbe reaction of creostJl with chlorine-chlorine dioxide mixtures.
a-C-R
I
/~
100
100
C-R
VI
Fig. 6. Seqrmu:e for tbe reaction of chlorhre dioxIde with ri.g-conjugated etbylenic groups
(3,68,69).
.ClO + CIO, + H,O + ClO;- + HOCI + H+
Either of these two chlorinating
agents
[7]
may,
in turn, add to the ethylenic

group to form
(in the case of hypochlorous
acid), the
chlorohydrin,
V, shown in the left-hand column of Fig. 6 (68,69).
Oxidation
of V leads
Reactions of chlorine-chlorine dioxide combinations with lignin

When chlorine and chlorine dioxide are
initially present as co-reactants, as is commonly the situation in the initial bleaching
stage, the individual reactions of these two
species with lignin and its degradation products overlap with the result that the overall
bleaching process is too complex to be adequately described by a manageable number of reaction sequences. At best, a few
meaningful parameters can be singled out
to provide an indication of how variations
in the chlorine-chlorine dioxide ratio influence the course of the overall delignification
reaction.
The effect of chlorine dioxide substitution on the degradation and chlorine uptake of a phenolic lignin model compound,
creosol, is shown in Fig. 7. Plot A shows
that the chlorine content of recovered aromatic products decreases progressively as
the fraction of chlorine dioxide in the chlorine-chlorine dioxide mixture increases.

This trend is in agreement with the claim
that chlorine dioxide itself is not an effective chlorinating agent (59). Plot B reveals
that maximum degradation of the phenolic
model occurs when 100% chlorine is applied. However, beyond 50% chlorine dioxide substitution,
ring degradation
increases with increasing substitution.
The trend of decreasing
organically
bound chlorine with increasing chlorine
dioxide substitution in the first stage bleaching of a softwood kraft pulp is illustrated
by the plots in Fig.8 (70). In the same figure, the increase in methoxyl content provides evidence that less degradation of the
aromatic ring in lignin occurs with increasing chlorine dioxide. Increasing chlorine
dioxide substitution also has the effect of
decreasing the number of chlorinated compounds found in the effluent and the number of chloro substituents attached to them
(70).
2.3 Sodium hydroxide in alkaline extraction

Sodium hydroxide is both a strong base
and nucleophile and these properties are
demonstrated in its diverse reactions with
the residual lignin in prebleached
pulps.
Some of these reactions have been thoroughly studied and documented while others have been proposed on the basis of the
predicted behavior of a particular structure
in alkaline media.
c:
'"
o
..c
o
o
]
E
Z=>
o
o
20
40
60
CI02 Sulmitution,
80
100
Fig. 8. Effect of cbiorllle dioxide substitution

on tbe
chlorine an4 metboxyl contents of lipi.
(M. w'>1(00) in tbe bleachi.g effJuent (70).
Chapter ill 3: Chemistry of Chemical Pulp Bleaching

Neutralization of acidic groups
The most important reaction of sodium
hydroxide with the residual lignin during
the extraction stage of a multi-stage bleaching sequence is the conversion of partially
degraded acidic fragments to their corresponding anionic fonns (i.e., neutralization).
The principal effect in such reactions is the
accompanying increase in the solubiliry of
the lignin fragments to which the acidic
groups are attached.
Typical acidic groups in native and oxidized lignin and their neutralization with
alkali (i.e., sodium hydroxide) are shown
in Fig. 9. Carboxylic acid groups arise
mainly from the oxidative rupture and later
fragmentation of aromatic rings in the initial bleaching stage as is described in Sects.
2.1,2.2,2.4,
and 2.5. A spectrometric iIIvestigation of a high molecular weight lignin-derived material recovered from the
effluent of a chlorinated and alkaIi-extracted
kraft pulp has provided ~ldence suggesting that the carboxyl groups are attached
to saturated carbons and to a-substituted
or ethylenic carbons
(37, 70, 71).
RCOOH
Carboxylic
(R
=
Aryl
or
Carboxylate
acid
anion
Alkyl)
\
Phenol
C-QH
II
He
Phenolate
C-O-
HO-
He
I
Enol
f).
Enolate anion
NeuIrfllizllHoll
tioruIl
+ H2O
II
Fig.
anion
grtnI/JS
of lignill-tIerlreti
i. prebk4ebetl
addle jilrreJItIlps.
Besides the phenolic groups initially

present in unbleached pulps, more such
structures are formed in the first bleaching
stage especially when the bleaching agent
is chlorine. Phenols of the catechol-type
139
(i.e., 1,2-dihydroxybenzenes)
appear to be
dominant in the extraction effluent of a
chlorinated pulp but, in the corresponding
effluents of oxygen- and chlorine dioxidepretreated pulps, the guaiacyl-type prevails
(70).
Enol groups arise from carbonyl groups
adjacent to carbon atoms containing an ahydrogen. Although this structural requirement is met by lignin in unbleached and
prebleached pulps, the contribution of enol
groups to lignin solubilization in alkaline
treatments has not been established.
Base-catalyzed
hydrolysis of organically
bound chlorine
A large fraction (ca. 60-70"10for kraft pulp)
of the organically bound chlorine in chlorinated pulp is removed in the ensuing extraction stage (72-74). In a study of the
base-<:atalyzed hydrolysis of aromatic and
aliphatic chlorine-substituted
lignin model
compounds under simulated alkaline extraction conditions, loss of chlorine invariably
was found to occur although to widely varying extents (75). Chlorine bound to aliphatic structures, for example to the lignin
side chain and to aromatic ring oxidation
products
such as o-benzoquinone
and
muconic acid derivatives, is extensively
removed. Although less susceptible to alkaline hydrolysis than the foregoing structure-types, even chloroaromatic derivatives,
particularly phenolic moieties, sustain a significant loss of chlorine on treatment with
alkali.
The removal of chlorine from lignin during the initial alkali extraction stage may be
described mechanistically as a nucleophilic
displacement reaction in which a chlorine
atom is replaced by a hydroxyl group. Two
types of displacement reactions are illustrated by the sequences in Fig. 10 (3). As
shown in the right-hand sequence, chlorine
attached to a side chain may be displaced
through attack of a neighboring alkoxide
group to form an oxirane and, ultimately, a
glycol structure. In the left-hand sequence,
the end-product of chlorine replacement
from an o-quinonoid unit displacement may
be viewed as a vinylogous enolate ion
(Fig. 9, bottom sequence). In each of the
140
~
~
-C-CI
I
HOC-
HO-
-H+!
+ HO-
-c-o
-o-c-
"
.--""-
0-
Joc
I
-OOH
1~
O~
.--yo
0Fig. 10. Sequ1u:es for tH lHrse-catillyze4 elimitUlo
titm of Mg..leally bormII cblorltle (3).
sequences outlined in Fig. 10, replacement

of a hydrophobic chlorine atom by a hydrophilic hydroxyl group has a favorable influence on the water and alkali solubility of
the lignin structure.
Condensation reactions
Lignin-derived
structures that appear
most vulnerable to base-<:atalyzed condensation reactions during the alkaline extraction st!ige !ire 0- :md p-ben:zoquinones
generated in the initial bleaching stage. Depending on the number and type of ring
substituents, quinones display varying de-
grees of instability in aqueous media. When

generated under acidic conditions, quinones are relatively stable but with increasing
pH they give evidence of becoming increasingly unstable (76). Under the initially highpH conditions
prevailing in an alkaline
extraction stage, quinone decomposition
may be expected to accelerate greatly (76).
Quinone decomposition in alkali usually is
accompanied by darkening or "browning"
of the substrate be it a prebleached pulp or
solution of a simple quinone.
Although the decomposition of relatively
simple 0- and p-benzoquinones
in aqueous
alkali has not been studied in any great detail, a few characteristic structural changes
appear to occur in virtually all instances.
These include condensation
in which biphenyl linkages are formed (76,77), a decrease in the number of carbonyl groups
(76), and an increase in the number ofphenolic hydroxyl groups (76-78). For 0- and
p-benzoquinones, the formation of catechol
and hydroquinone structures, respectively,
is indicated.
A sequence accounting for the observed
structural
changes occurring
when a
benzoquinone,
typified by methoxy-pbenzoquinone,
reacts with alkali is proposed in Fig. 11. Key elements in the
sequence are a Michael-type addition of a
hydroxide ion to the quinone ring and an
attack of the carbanion, B, on the enone
system of the starting quinone,A. The resulting polyphenolic dimer may be partially
oxidized by air (oxygen) to a quinone-substituted polyphenolic unit, C. A similar sequence can be devised to account for the
reactions of an o-benzoquinone derivative
with alkali.
When occurring in an alkaline extraction
stage, condensation reactions of the type
portrayed in Fig. 11 would be expected to
adversely affect lignin solubilization
although the effect would be at least partially
offset by the formation of phenolic hydroxyl
groups which would be converted to the
more soluble phenol:ue
iOil in :l1K:lli (Fig.

9, middle sequence). Brightness loss associated with the formation of condensed
quinone-substituted
di- or triphenolic struc-
141
142
OH
HO
H
---A
O2
- e, H~
HOO-
pKa
tl
4.8
OCH3
- e, H~ HOOH - e. H+.
HO' + -OH - e. H+. 2 H20
I.
H+ + -00'
tl
10.5
tl
11.3
I.
I.
W + -OOH
W + -0'
Fig.12. ReadltJespedes furmetll" tbe stepwise reduction of oxygen (80).

conceivably can arise by redox disproportionation reactions that involve only inorganic species.
Transition
HOOH + HOo- -Metals) 0, +
HO. + HO[8]
HOO' + HO. -- 0, + H,o

M" + 0,' + H,O -- HOO- + HO- +
M"+l
[9]
[10]
(M=transition metal)
C
Fig. 11. Seqrumce for tbe j'ormstion
wltb aliI/IIi.
of eondenseJl structures
tures undoubtedly would be recovered in

an ensuing treattnent with a strong oxidizing agent such as chlorine dioxide, sodium
hypochlorite, or ozone.
Base-catalyzed rearrangement of o-quinonoid structures
In principle, o-benzoquinone structures
formed from lignin in the initial bleaching
stage may undergo a benzylic acid rearrangement in alkali leading to the formation
of a cyclopentadiene
a-hydroxycarboxylic
acid derivative (right-hand sequence in Fig.
8, Chap. 1114) (79). The formation of a carboxyl.substituted
ring would enhance the
alkali solubility of lignin fragments containing such units. However, it should be emphasized that the occurrence of this type
of rearrangement
has not been demonstrated for o-quinonoid
structures introduced into a lignin network.
Z.4 Molecular oxygen

Reactive species in oxygen bleaching systems
Molecular oxygen. a diradical in its
ground state, is an electrophile which at.
I" tbe reaction of metboxy-p-benzoqulnone

.
tacks electron-rich sites in lignin typified by

phenolic nuclei and enolic hydroxyl groups.
Oxygen is a relatively weak (and therefore
selective) oxidizing agent (80). Therefore,
to ensure that the reactions of lignin with
oxygen proceed at a reasonable rate, it is
necessary to first activate the lignin by add.
ing alkali to convert the phenolic and enolic
hydroxyl groups to their more reactive phenolate and enolate ion forms.
In the process of autoxidizing lignin,
oxygen undergoes a stepwise reduction by
way of a series of one-electron transfer reactions which lead to the formation of a
superoxide ion radical, 0,' (81-83), a hydroperoxide anion, HOO' (80, 84, 85),and
a hydroxyl radical, HO. (86) or its ionized
form, 0,", depending on the reaction pH
(80,84) as is shown in Fig. 12 (69, 80, 84,
85). These oxygen-derived species have significant roles in the overall degradation of
lignin in oxygen prebleaching treatments
as is described in the following section. In
addition to their formation in the reduction
of oxygen by lignin, these reactive species
The remaining active species in oxygen

delignification systems is the hydroxide ion,
HO-, which, besides functioning as a base,
is believed to participate in nucleophilic
displacement reactions.
Reactions of oxygen with phenolic
structures
As was the situation with chlorine dioxide oxidation, an understanding of the reo
actions of oxygen with lignin during
prebleaching
has been achieved largely
through model compound
studies. Although the reactions that delineate the overall degradation of lignin are multifold and
complicated by a pH-dependency, most in.
vestigators (3, 10, 83, 84, 87-90) are in
agreement that the steps outlined below are
pivotal in the delignification sequence.
The initial step in this sequence is the
formation of a phenoxy radical through
electron transfer from a phenoxide ion to
molecular oxygen (Fig. 13). In the process,
a superoxide ion radical, 0,', is formed. In
the following step, the mesomeric forms of
the phenoxyl radical react with oxysen orl
more probably, with a superoxide ion radical (81) forming a hydroperoxide
radical
or, as is shown in the figure, an organic
hydroperoxide anion. This anion attacks a
carbonyl carbon or a vinylogous carbon in

an intramolecular
nucleophilic
reaction
forming a dioxetane structure. Rearrangement of this cyclic peroxide leads to the
formation of oxirane structures (A), formation of muconic acid derivatives (B), and
rupture of the Ca-C. bond with formation
of a a-keto structures (C) as shown in the
figure. As an alternative to oxirane formation, p-hexadienoyl
hydroperoxides
may
fragment with elimination of the side chain
and formation
of a methoxy-p-benzoquinone derivative (83, 85, 91). The validity of these sequences in the bleaching of
kraft pulp is supported by the observed
decrease in phenolic hydroxyl content (92,
93) and increase in carboxyl content (92)
of the residual lignin and by the detection
of low molecular weight carboxylic acids
(94-96) and methanol (94) in the bleaching effluent.
The organic hydroperoxides
formed in
the oxygenation step in all likelihood give
rise to hydrogen peroxide and hydroxyl
radicals as illustrated in Fig. 14. Other reactions proposed for the predicted formation of hydrogen
peroxide
are listed
elsewhere (3, 80, 85). Under the prevailing alkaline conditions of oxygen delignification, hydrogen peroxide is converted
(i.e., ionized) to a hydroperoxide
anion
which, as a strong nucleophile, attacks unsaturated structures and oxirane rings (3,
80, 89,93). The brightness improvement
accompanying oxygen delignification has
been credited to the bleaching effect of hydroperoxide ions (80). Hydroxyl radicals
oriBinate from the homolytic splitti"8 of the
oxygen-oxygen
bond in hydroperoxide
units through thermal and transition metalinduced reactions (80, 97) (Fig. 14). The
rate of hydroxyl radical formation during
143
R = H.alkyl,arylor aroxyl
..-y~
0-o~
Alphatic
degradation
products
including methanol and

arlxn'yti aid~ (ee)
Fig. 13. Sequeru:esfor lbe a,,'oxIdalkm

carbonyl structures (3).
.II
ofpbellolk
"
IIpl"
Mn+1 + HO' +,'n
"

R
I
C-R
-c
144
C
,,"Ils 10 oxIrrme (A), tmICOIIk add (B), aIId
II(
,
YOCH3
,'00
,x
YOCH3
o
R = Side chain
M Trans~ion metal
=
Fig.14.1'nIgmeItIiIIIoretIdknISof IIpIII-tlmved bydroperoxtdesleadl""o lbeformation ofperbydroxyl

alltom aIIdbydroxyl rtIIlkals.
oxygen delignification has been estimated
to be 0.6 J.UI1ol"'L') min. (86). In contrast
to molecular oxygen, the hydroxyl radical
is a very strong electrophile and therefore
may react preferentially with phenoxide
ions in the phenoxyl radical generation step
(Fig. 13) and with other organic structures
(including carbohydrates) in the system (80,
97-99). During oxygen delignification, both
hydroperoxide ions and hydroxyl radicals
contribute to the further breakdown of partially oxidized lignin to water- and alkalisoluble fragments (89).
Based on the results of studies with lignin (J 00) and lignin model compounds (90,
93,95,96,
101-103),free radical coupling
(t. e., condensation) reactions are very likely
to occur during oxygen delignification. The
negative effect of such reactions on lignin
solubilization would be moderated by the
ensuing rupture of the phenolic rings constituting biphenyl-like condensation products (91,104). The observed lower rate of
lignin compound degradation under oxygen
delignification conditions in the presence
of transition metals (93) possibly may be
attributed to an enhanced formation of
phenoxy radicals and later coupling of their
mesomeric forms.
(Fig. 15). Rearrangement

of this cyclic
dialkyl peroxide leads to side chain cleavage. Based on results of a model compound
study (106), this type of reaction is restricted to etherified phenolic units. Although side chain fragmentation could be
an important
contributor
to lignin
delignification in oxygen delignification in
this particular instance, the low concentration of a-<:arbonyl groups in residual kraft
lignin (Chap. III 1) militates against such a
possibility.
Reactions of oxygen with ring-conjugated
Reactivespecies in ozone bleaching systems
carbonyl groups
Ring-<:onjugated carbonyl structures in
lignin react with oxygen under alkaline conditions in a series of steps (Fig. 15) which
lead ultimately to the cleavage of the Co-C.
bond in the side chain (3, 89, 105, 106).
Key steps in the sequence include the formation of a hydroperoxide anion followed
by the intramolecular attack of this nucleophile on the carbonyl carbon atom to form
a four-membered (dioxetane) ring structure
Relative reactivity of kraft lignin structural

types toward oxygen
The reactivity of the various types of
structural units in residual lignin toward
oxygen under typical bleaching conditions
is strongly influenced by the substituent
groups attached to the phenolic nuclei and
ring-<:onjugated ethylenic groups. Thus,
catechol units are far more reactive than
guaiacyl- or p-hydroxyphenyl-type
structures (93) and syringyl nuclei are more reactive than guaiacyl nuclei (95). Stilbenes
are more reactive toward oxygen than
vinyl ethers which, in turn, are more reactive than B-aryl ethers (107).
2.5 Ozone
Ozone is a triatomic, non-linear allotrope
of molecular oxygen that can be viewed as
a resonance
hybrid of four mesomeric
forms:
~O,
/0",
_ _

_
/0,
+ /0,
'!'he dipole character 01 these mesomers

suggests that ozone may react as an
electrophile or nucleophile. However, in
its reactions with electron-rich structures
c=o
+OH-
OCH,
CfI~
.--
/0
02
OCH3
/0
Fig. 15. Seqrumcefor
= H. alkyl.
tbe retldlon
aryl
+ 02' -> 22 ('02,singletoxygen)
OCH,
.--
HOO-(02')
+ 02
H04. + H04. -+ H202 + 20,
O=C-R +
O
~C=O
OCH,
/0
6 ~
OCH3
OCH3 ~
--H20,.-0
/ 0[OH] 0
.--""'- 0
o
/
-lOH]0-0
:;n
:;n
+H 0
+H 0
CH,H.--
with CIIrlxmyl-eonj"gatetl
[11]
+ HO. (12)
[14]
[15]
In the above decomposition sequence, the

initial step (Equation [11 D is slow and ratedetermining; the propagation and termination steps (including several not shown)
are, by contrast, rapid. Hydroxyl and hydroperoxyl radicals, besides being chain carriers in the overall decomposition, are also
potential participants in lignin degradation
reactions. However, hydroxyl radicals have
been detected in the ozonation of a lignin
model compound (114) and found not to
contribute significantly to its degradation.
strllctrlres
OCH3
0
/ 0[OH] 0
OCH,
/0
C-R
II
o
or aroxyl
[13]
-+
~C-O-
/0
ofoxygen
0, + HO- -+ 02' + HOO.
HO;
Cf1- cf1-
in lignin, it is generally agreed that ozone

reacts as an electrophile (Table 1, Chap. III
2), the positively charged terminal oxygen
atoms being the attacking sites (3, 8, 10,
84, 108). Ozone is a powerful oxidant and,
of the reactive oxygen-containing
species
encountered
in bleaching, is surpassed in
oxidizing power only by the hydroxyl radical (108, 109).
Ozone is inherently unstable in aqueous
solutions where its decomposition
rate is
markedly enhanced by an increase in pH
(80, 84, 108, 110). The. overall decomposition can be represented as a free radical
process leading to the formation of oxygen,
hydroxyl and perhydroxyl (or superoxide
anion) radicals, and hydrogen peroxide (80,
108, 112, 113):
03
O-C-R
~C=O
1-
.--
O-C-R
c=o
146
Lignin
JC-R
He-R
145
(3).
Ozone decomposition is also initiated by

trace amounts of transition metals (80,110,
111), especially cobalt (11) and iron (11)
(110, 111). A sequence for the transition
metal-catalyzed decomposition of ozone has
been proposed by Brolin et al. (115). The
sensitivity of ozone toward decomposition
by transition metals is substantially greater
than that observed for oxygen and hydrogen peroxide (80) and indicates a need for
the prior removal of such metals in ozone
delignification processes to lessen the risk
of radical-induced degradation of carbohydrates (80).
Alternative
sources of hydroxyl and
perhydroxyl
radicals, molecular oxygen
(singlet oxygen), and hydrogen peroxide
are the ozonides, hydrotrioxides, and hydroperoxides
formed in the reactions of
ozone with organic substrates in homolytic
and heterolytic processes (80, 84, 116). Sequences illustrating their formation are presented in the following section.
The decomposition of ozone to molecular oxygen represents
loss of oxidizing
power because, under rypical (t.e., acidic)
ozonation conditions, oxygen is not an effective oxidizing agent.
Reactions of ozone with lignin model compounds
Based on model compound studies, several distinct types of ozone reactions have
been identified (3,10,80,84,108).
Among
the transformations having the greatest potential bearing on lignin degradation are
those leading to the rupture of aromatic
rings and the cleavage of ethylenic and ether
bonds (3). In keeping with its dominating
electrophilic characteristics, ozone prefer-
R=ArorOAr
R
aryl or aroxyl
Fig. 16. Sequeru:esfor tbe ozOIUIIItm of a_tic

(3, 10).
entially attacks electron-rich sites in lignin

rypified by aromatic rings and ring-conjugated ethylenic groups.
The initial electrophilic attack of ozone
on an aromatic ring leads to the formation
of an ozonide through a 1,3-cycloaddition
reaction (Fig. 16, sequence A). Following
hydrolysis of the ozonide, the aromatic ring
is cleaved and a muconic acid derivative is
formed (117-120). After hydrolysis of either or both of the ester groups, lactone
formation may occur (114,121,122).
The
hydrogen peroxide that is released when
the ozonide decomposes can undergo decomposition
to hydroxyl
(114) and
hydroperoxy
radicals both of which are
strong oxidizing species. Ring rupture is
generally observed to occur between the
carbon
atoms
bearing
the oxygen
functionalities, but ring rupture at other
sites has been observed (117, 118). The
muconic acid esters and their lactonized
forms may be further degraded by ozone
(117,118,123-125).
With reference to sequence A in Fig. 16, it is important to note
that ring rupture of non-phenolic as well as
phenolic nuclei takes place in contrast to
an oxygen de lignification system where
only phenolic rings are degraded.
Ethylenic groups, typified by those
present in kraft lignin in the form of styryl
rings (A) and ring-eonj"gatel
etbylenk gt'OIIPs (B)
aryl ethers and stilbenes, are readily degraded by ozone (3,119). In the sequence
outlined in Fig. 16B, the initially formed
ozonide, a 1,2,3-trioxolane,
decomposes
and is reformed into 1,2, 4-trioxolane (secondary ozonide). On hydrolysis of the latter, the ethylenic double bond is ruptured
and the ethylenic carbons are converted to
carboxyl groups.
Alkyl aryl ethers, represented by B-aryl
ethers in lignin, undergo ozone-induced
cleavage (118). Cleavage of the ether linkage can result from attack of ozone at the
alkyl or aryl end of the linkage. In the first
instance, ozone initially attacks the B-hydrogen-carbon bond and a 1,~ipolar insertion
reaction leads to formation of a hydrotrioxide (Fig. 17, right-hand sequence).
Following the loss of a hydroperoxide radical,
Ca-C. cleavage occurs and the ester fragment is ultimately converted to creosol.
Electrophilic attack of ozone on the aryl
component ofthe B-aryllinkage leads to the
cleavage of the aryl-oxygen bond and formation of a diol with accompanying release
of the B ring as an o-quinone (Fig. 17, left.
hand sequence).
E1ch of the sequences outlined in Fi~s_

16 and 17 represents a reaction mode having the potential for degrading and solubilizing lignin during ozone bleaching.
In
Chapter m 3: Chemistry of Chemical Pulp Bleaching
-02
- CH30H
1-000.
HC +
'~_'
/~o
0
/0
H20
1
r3
<>-0
I
Threo
Isomer
~/
y
. .))
.-y~
CH3
1+ H.<'
t - CH3COOH
.~OH
Fig. 17. SefJllellUs
for tbe OZOJUItUm of tllfryl tlryl ether ",dls
(18).
147
148
practice, lignin degradation is most likely

achieved through the combined effect of
the ozonation reaction modes listed above
and others described elsewhere (3, 10,
108). The relative contributions of the various types of ozone reactions to the degradation of lignin depend on the type and
abundance of reactive structures in the lignin. For example, a comparison of the relative reaction rates of different types of lignin
structures toward ozone indicated the following decreasing order of reactivity (119):
stilbenes > styrenes> phenolic structures
> muconic acid intermediates
(from the
opening of aromatic rings) > non-phenolic
structures
aromatic aldehydes (from the
cleavage of ring-conjugated
ethylenic
groups). Substituent groups attached to the
lignin skeleton also have a major influence
on the reactivity of lignin during ozone
bleaching.
In accordance
with the electrophilic
characteristics of ozone, electron-donating
substituents increase the reactivity of aromatic rings toward this oxidant and electron-attracting
substituents
have the
opposite effect (117). Thus, the reactivity
of phenol toward ozone is enhanced by the
addition of increasing numbers of methoxyl
substltuents (108). When present as phenolic ring substituents
in diaryl ether-,
diphenylmethane- and diphenyl ether-type
lignin structures, aryl, benzyl, and aroxyl
groups enhance the reactivity toward ozone
in the order stated (119). Carbonyl groups,
on the other hand, are electron-attracting
and when conjugated with aromatic nuclei,
greatly reduce the reactivity of such structures toward ozone (119, 121, 122). On
conversion of ring-conjugated carbonyls to
benzyl alcohol groups, which are electrondonating, reactivity toward ozone is once
again increased (122).
Reactions of ozone with lignin
The structural changes occurring when
lignin is ozonated are consistent with those
expected based on the documented reactions of lignin model compounds under
similar conditions. For ozonated kraft lignin, these structural changes are manifested
principally by a decrease in aromatic ring
content (126-128) and an increase in the

number of free and esterified unsaturated
carboxylic acids and carboxylic esters ( 117,
126-128). The methoxyl content of the lignin decreases and methanol is found in the
reaction mixture (127). Methanol can arise
from direct oxidative dealkylation of methoxyl groups as shown in Fig. 17 (left-hand
sequence) or by the oxidative breakdown
of muconic acid methyl ester intermediates
(127). The increase in carbonyl groups observed during the ozonation of kraft lignin
(126) possibly can be ascribed to the cleavage of ring-conjugated ethylenic groups as
shown in Fig. 16(B) or the cleavage of aromatic rings at sites other than those carrying oxygen-containing
functional groups.
Molecular weight determinations
reveal
that the lignin macromolecule is not significantly degraded during ozonation (127,
128). However, treatment of ozonated lignin with alkali reportedly leads to a decrease
in molecular weight (126). This decrease
may be ascribed to the saponification of
ester groups derived from what were originally B-aryl ether groups (Fig. 17, right-hand
sequence). A proposed structural representation of ozonized softwood lignin embodying the reaction principles described above
is presented
in Fig. 18 (129).
Before
ozonation the two fragments shown in the
figure were joined through a S-O-4 linkage
involving units A and B.
3. Reactions of carbohydrates
with bleaching agents and
alkali
Although the chemistry of pulp bleaching mainly involves the reactions of lignin
with bleaching chemicals, carbohydrates
nevertheless undergo concurrent transformations during bleaching that often have
an important bearing on the strength properties and yield of the resulting pulp. The
impact of these reactions becomes increasingly more significant as the lignin content
of the pulp decreases. The reactive sites
for attack by electrophilic bl~d1ing s~ecies
on carbohydrates
are shown in Fig. 1(B)
(Chap. III 2); nucleophilic sites in carbohydrates include acetal (glycosidic) linkages,
--'-'----
149
dence indicating that the acetal bond in

cellulose is ruptured in chlorination and
ozone bleaching stages. In the upper sequence in Fig. 19, the attacking electrophile
in chlorination treatments is a chlorine radical 030-132) formed by abstraction of a
hydrogen atom from an organic compound
(33):
o
o I?O
11 C
0Me
'"
H.z9/0'CH
1
I
HC-CH
I
1
He,
CH:2
RH + CI2
O-OMe
K,F
HCOH
o=c
HCOH
~
6
tiOCt\>
HC
HC-O
MeO-:
~
B
H'
o=c,
OMe
C-OMe
C II
II 0
0
CH,OH
I
HCOH
II
C-OMe:o
W
I
o lI'o-C-HC
o
I'
HOCK,
"
O-W
o
d'
OMe
OH
Fig. 18. Structurtll representllllon

flJfHNllIgnhl ftwgmen#.
of OZOlUlted soft.
reducing end-groups and enone structures

formed initially by attack of an electrophilic
bleaching species. The reactions of carbohydrates with bleaching chemicals may be
conveniently
classified
according
to
whether they occur at acetal sites or else.
where.
3.1 Reactions at acetal (glycosidic) sites

Studies on carbohydrate model compounds and cellulose have provided evi.
GI-f2OHo
GI-f2OHO
R
'0
+CI.
-HCI
D
OH
R. + CI. + HCl
CI2
.R-\OH-CI.
OH
<;:H"OH0
0,
-ROH R
R-,OH
a
+2H.o
OH
IOH
X ~
Cellulose
Fig. 19. Proposed
GH.oHo
R
\
O
OH
-02
R
H
~
OH '0
0
residues
seqaeru:es
for tbe dlred
0
C
+0,
4:r
H20
-ROH
co-o-o'")
[16]
In a free radical chain process, the chlorine

radical abstracts a hydrogen atom the C-l
atom of the glycoside forming an organic
radical (A) which then reacts with elemental chlorine to regenerate chlorine radicals
(Equation [16]) and form a chlorinated
anhydroglucose
unit (B). In an ensuing
hydrolysis step, the acetal linkage is directly
cleaved and an aldonic acid end group (D)
is ultimately formed (Fig. 19). Alternatively,
cleavage of the acetal linkage may be described by an ionic mechanism in which a
reducing end group or a gluconolactone (D)
is formed (34).
The free radical mechanism is supported by the finding that acetal bond cleavage is decreased by the
inclusion of radical scavengers such as chlorine dioxide, oxygen, and sulfamic acid
035,136).
However, the failure of radical
scavengers to eliminate completely cleavage of the acetal linkage lends credence to
the possibility that an ionic mechanism may
also be operative (30).
In the ozonation of carbohydrate model
compounds and cellulose, the dominant
reactions in the initial phase are ionic and
-C-CH,OH
,
A'"
II C
IF~?
o""y ~
cleavage
R, OH
0
COOH
OH
of glycoslilk
IIniages
In cell"lose
cblorlne and ozone.
150
Pulp Bleaching
- Principles
and Practice
involve a direct attack on the acetal linkage

(137, 138). A typical sequence is illustrated
in the lower sequence in Fig. 19 where the
anomeric C-H bond is attacked by ozone
and a hydrotrioxide (E) is formed by a 1,3dipolar addition mechanism. The hydrotrioxide undergoes
fragmentation
to the
lactone (D) with release of oxygen which
may be in the singlet form (38). Alternatively, the cleavage of the glycosidic bond
has been pictured as an attack of ozone on
the bridging oxygen atom in an ozone-catalyzed mechanism 037,138).
Irrespective
of the mechanism of acetal cleavage, that
this process occurs during the chlorination
and ozonation of pulp is of extreme importance because it signifies a decrease in the
D.P.of cellulose which often translates into
a loss in pulp strength.
Oxidation
- Alkoxy
of alcohol
Oxygen reportedly does not react directly

with the acetal linkages in cellulose under
alkali-oxygen bleaching conditions (139)
and chlorine dioxide is essentially unreactive toward carbohydrates when typical
bleaching conditions are used (40).
Neither acidic nor alkaline hydrolysis of the
acetal linkage contributes significantly to
the depolymerization of cellulose under the
pH and temperature conditions normally
used in commercial bleaching processes.
3.2 Reactions at non-acetal sites

Oxidation of hydroxyl groups
One of the several reactions in this category having an important bearing on the
outcome of pulp bleaching is the oxidation
of primary and secondary hydroxyl groups.
The oxidants in these reactions are generally believed to be free radicals formed in
groups
elimination
+
(C)
1-"
Oxidation
of Ketol B
ROH
~t' 0
-----

the decomposition of the bleaching chemicals or during reactions of the bleaching
chemicals with pulp constituents (80, 84,
130, 138, 139, 141) although some evidence has been reported indicating the involvement of ionic species in the oxidation
(130, 142). The origin of chlorine radicals
has already been described (Equation [16 D.
In addition, hypochlorous acid present in
the chlorination mixture may give rise to
hydroxyl radicals (130):
R. + HOCI
->
RCI + HO.
[17]
In hypochlorite bleaching, a hypochlorite

ion and hypochlorous acid may engage in a
redox reaction in which hypochlorite and
chlorine radicals are formed:
HOCI + on
-> CIO. + Cl. + HO-
[18]
The particular electrophile or combination

of electrophiles (radicals or cations) responsible for initiating the oxidation of alcohol
groups in polysaccharides during chlorination is not known with certainty.
Reactions accounting for the formation
of hydroxyl radicals in oxygen and ozone
bleaching are described in Sections 2.4 and
2.5; hydroxyl radicals have been detected
in oxygen, ozone, and peroxide bleaching
treatments (115, 143). Hydroperoxy radicals generated in oxygen and ozone bleaching processes probably do not participate
in the oxidation of primary and secondary
alcohol groups, but may oxidize reducing
end groups in carbohydrates (138). The
oxidation of a secondary alcohol group in
cellulose by a hydroxyl radical is illustrated
by the top sequence in Fig. 20 (144). The
sequence is initiated by abstraction of a hydrogen atom from a hydroxyl-substituted
carbon (in this instance, C-2). An ensuing
attack by molecular
oxygen or other
electrophiles (e.g., chlorine, hypochlorite,
hydroxyl, or hydroperoxide radicals) on the
hydroxyalkyl radical (A) leads ultimately to
the formation of the ketol (B). This sequence may also be used to rationalize the
formation of 3-keto and 6-aldehydo groups.
B-Alkoxy Elimination: Cleavage of Polysaccharide Chains

Ketols formed by the oxidation of
polysaccharide alcohol groups readily un-
151
dergo alkali-induced B-aIkoxy elimination

reactions (84, 139, 141, 145-147). When
applied to cellulose, as is the case in the
middle sequence shown in Fig. 20, B-elimination leads to chain rupture that is manifested as a decrease in pulp viscosity and
frequently by a loss of pulp strength. The
role of carbonyl groups in the viscosity loss
is indicated by the finding that their removal
by reduction with sodium borohydride before reaction with alkali greatly decreases
the extent of viscosity loss (128,142). Carbonyl groups introduced at the 3- and 6-carbons by reactions sequences paralleling
those outlined in Fig. 20 also activate glycosidic linkages toward alkaline cleavage by
B-alkoxy elimination reactions. Oxidation
of alcohol groups in polysaccharides and
ensuing B-aIkoxy elimination reactions may
occur successively in a single bleaching
stage where alkaline conditions exist, that
is, in oxygen, peroxide, and hypochlorite
bleaching. For bleaching agents normally
applied under acidic conditions (chlorine,
chlorine dioxide, and ozone), the B-elimination reaction can occur in the following
alkaline extraction stage.
The oxidation of ketol (B) in Fig. 20 competes favorably with B-elimination with the
result that keto groups at both the 2- and 3carbons are introduced
almost simultaneously (139). The diketo unit, (D), can
be further oxidized to a dicarboxylic acid,
(E), by nucleophilic reagents such as hypochlorite and hydroperoxide ions (3, 84,
139,141,148).
Althoughdepolymerization
does not directly result from this process,
the glycosidic linkages in the modified unit
become sensitized to cleavage by acid hydrolysis (139,148). The diketo unit may also
be converted
to a carboxyl-containing
furanosidic structure, (F), by the action of
alkali in a benzylic acid rearrangement reaction (80, 131, 139, 148). In Fig. 20, the
eliminated alkoxy group, (C), is, in effect. a
degraded cellulose chain. Because the chain
fragment has a terminal reducing unit, it is
susceptible to oxidation and step-wise depolymerization
(i.e., "peeling") reactions
under the appropriate alkaline bleaching
conditions (149-152).
152
R-C-OH
II
R-
O-O-Q-H
.-----------.------..----------------------.------.--.-----.--------.--------.----------------.-------.----.-----..--COOH
/
B
-1-
H
(f)
o
It
HCOH
'c
I
-C=O
I
-C-
(9)
Step-wise
depolymerization
COOH
I
HC-QH
I
-C-
Fig. 21. O%id4tkm
of carlJol1yllrtlte
redtIdIIg
end groups
Oxidation of reducing end groups

Oxidation of the aldehyde form of a terminal polysaccharide unit to a carboxylic
acid by chlorine (chlorine cation), hypochlorite ion, and ozone is illustrated by
reactions (a), (b), and (c) in Fig. 21(A). In
contrast to these relatively straightforward
reactions, the oxidation of reducing end
groups to carboxyl groups in an oxygen-alkali system occurs indirectly and involves a
complex set of reactions (Fig. 21 (B)) (141).
The pivotal step in the sequence, (d), is the
formation and subsequent oxygenation of
a carbanion adjacent to the carbonyl group.
The resulting hydroperoxide anion attacks
the carbonyl group forming a dioxetane ring
which then fragments yielding formic acid
and the next lower aldonic acid (Fig. 21,
reaction (e)). Elimination of the hydroperoxide anion in reaction (f) leads to the formation of a 1,2-dicarbonyl structure which
with bleaching
chemicals.
is transformed to the corresponding aldonic

acid in a benzilic acid rearrangement, (g).
The dicarbonyl group can disproportionate
(h) to formic acid and the next lower aldose which, together with the reducing end
group of the starting polysaccharide chain,
can undergo competing step-wise depolymerization
("peeling")
reactions.
The
higher yields of oxygen-bleached pulps suggest that the formation of end group-stabilizing carboxyl groups competes well with
the peeling reactions which are mainly responsible for yield loss (141).
3.3 Selectivity in bleaching reactions
Selectivity in bleaching can be defined
as the relative reactivity of a particular reactive species toward the lignin and carbohydrate
components
of pulp in a
competitive situation. The competing initial reactions are believed to consist of the

addition of an electrophile (cationoid or free
radical species) to an aromatic ring or olefinic structures in lignin and the abstraction
of a hydrogen atom from carbohydrates,
usually by a hydroxyl radical arising from
the decomposition
of a hydroperoxide
group or ozone (132).
The bleaching agents currently in use
commercially generally fulfill the requirements of selectivity with respect to lignin
and chromophore removal. The degree of
selectivity may vary, however, depending
on the bleaching agent, its stability under
the reaction conditions, and the structural
characteristics of the residual lignin. As an
example, the initial rates in the reactions of
chlorine (130, 154) and ozone (115, 119,
138) with lignin model compounds are several orders of magnitude greater than those
found using carbohydrate models. This disparity is, most probably, the result of strong
electrophilic chlorine and ozone species
being initially available to react with the
electron-rich sites in the lignin models. In
contrast, carbohydrates
react relatively
slowly with hydroxyl or other radicals
formed in secondary decomposition
processes.
Hydroxyl radicals, formed during oxygen, ozone, and hydrogen peroxide bleaching, react not only with carbohydrates, but
with lignin as well (80, 83, 97, 132). Using model compounds as substrates, the
relative reactivities of lignin and carbohydrates toward hydroxyl radicals, generated
by radiolytic methods, have been determined (97). The rate constants for the initial reactions of hydroxyl radicals with these
models are listed in Table 1. The selectivity
factor for these reactions is the ratio of the
rate constants for the reaction of lignin and
r""e
1. Rille COItSI.,," for lbe retldkms

pouruls (83, 97,154).
Compound
Veratrylglycerol-B-guaiacyl
carbohydrate models with hydroxyl radicals

which, using the values in the table, can be
calculated to be about 5-6. This range of
values indicates that the initial addition of
hydroxyl radicals to the aromatic ring of the
lignin models occurred at about 5-6 times
the rate of hydrogen atom abstraction from
the carbohydrate models.
The selectivity factor increased approximately 2o-fold when the lignin and carbohydrate models listed in Table 1 were
exposed to hydroxyl radicals in the presence of magnesium salts at a pH approaching 11 (83). This increase was attributed
to the retarding effect of magnesium on the
abstraction of hydrogen atoms from the carbohydrate models (154). Also, selectivity
was found to decrease in acidic solutions
and increase in alkaline solutions (83). In
the ozone bleaching of kraft pulp, selectivity, as indicated by viscosity, has been found
to increase with increasing consistency and
acidity and with the addition of a chelating
agent such as sodium pyrophosphate (115).
These trends were linked to the formation
of hydroxyl radicals in decomposition reactions and their reactions with the carbohydrate constituents of the pulp.
4. Reactions of extractives with

bleaching agents
Because of their low concentration
in
unbleached pulp, extractives playa relatively minor role in determining the outcome of bleaching. The effect of extractives
in bleaching is most evident in chlorination
where chlorinated extractives reportedly
contribute to pitch problems (particularly
those encountered with hardwood pulps)
(155, 156), promote the thermal yellowing of pulps (157-159), and add to the toxicity load of the CE effluent (160,161).
of bydl'O:ltJI rtJdkllls
IIIItb lip'"
tIrUl Ctlrbobydrtlle
Rate constant, M.I, S.I
Veratrylglycol
1.5 X 1010
ether
153
1.7 X 1010
Methyl B-D-glucopyranoside
3.2 X 10'
Methyl B-D-xylopyranoside
2.6x
10'
model
rom-
154
Pulp Bleaching
-Principles
and Practice
OH
A'V~
>=<
B
o
2 -!!oH
9Q:...
CIO:!, 00-
!
CIO:!
/''1''-
.......
2,;;c=o
+ C1:1 (HOCI)
OH
~
Fig. 22, Reaclkms
of "leaebi"g
.g"""
11II1"elbyl""k
Extractives having the greatest influence

on bleaching appear to be those containing ethylenic groups, namely, unsaturated
fatry acids, fatty acid esters, and resin acids. During chlorination, chlorine and hypochlorous acid add to ethylenic groups
forming dich1oro and ch1orohydrin moieties
as shown in Fig. 22 (pathways AI and~,
resp.) (155, 161, 163). The mechanisms
of these reactions are outlined in Fig. 2. The
addition of chlorine atoms to the ethylenic
groups has the effect of making the extractive molecules of which they are a part more
hydrophobic and therefore less easily dispersed and removed from the pulp during
bleaching.
The formation of chlorinated extractives
can, in part, be prevented by prior removal
of the ethylenic double bonds by reaction
with oxidants such as chlorine dioxide,
hypochlorite, and alkaline hydroperoxide.
These reactions with ethylenic groups give
rise to what appears to be a common intermediate, an epoxide or oxirane structure
(Fig. 22) (3, 68, 162, 164). On further re-
grtn'ps
,,, exIrtu:UfJf!:S.
action with chlorine dioxide, the epoxide

ring is ruptured and tWO fragments, each
containing a carbonyl group, are formed
(Pathway C). The chlorine or hypochlorous acid generated in this free radical reaction may, in turn, undergo addition reactions
with unconsumed
ethylenic groups as
shown in pathways A, andAz' The ability of
chlorine dioxide to eliminate ethylenic
groups in extractives is shown by its effectiveness in reducing the resin content of
softwood and hardwood sulfite pulps (165,
166).
Sodium hypochlorite degrades unsaturated fatty acids and fatty acid esters such as
oleic acid and triolein presumably by nucleophilic attack of hypochlorite ion on the
ethylenic group (162). As was the situation with chlorine dioxide, one major degradation pathway appears to include the
formation of an oxirane ring (Fig. 22). Further oxidation of this ring structure leads
ultimately to the formation of carboxylic
acid fragments by way of aldehyde intermediates (Fig. 22, pathway D). Some chlori-

nation of the ethylenic group also occurs
as evidenced by the formation of chlorohydrin and chloroketone structures (162).
In alkaline media, the epoxide (oxirane)
intermediate
can be converted to a diol
through nucleophilic attack by a hydroxide ion (Fig. 22, pathway E). Thus, when
oleic acid and triolein are oxidized with alkaline hydrogen peroxide, hydroxyl and
epoxide groups are introduced (162). Oxygen bleaching, when used in conjunction
with other bleaching stages, reportedly
(167) is able to effect a reduction in the
resin content of sulfite pulps. However, the
specific reactions of oxygen with resins
under these conditions apparently have not
been studied.
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68(9):339
Pappersttdn.
}., Svensk
(1965).
159. Croon, I., Dillen, S., Olsson,J-E.,

Pappersttdn.
69(5):139 (1966).
Svensk
160. Leach,JM.,
and Thakore,A.N.,
ter Technol. 9:787 (1977).
Prog. Wa-
161. Holmbom,
B., and Lehtinen,
Puu 62:673 (1980).
K.}., Pap
162. Leopold,
42(3):218
B., and
(1959).
Mutton,
D.N.,
Tappi
163. Sjostrom, E., in Wood Chemistry: Fundamentals

and Applications,
Academic
Press, New York, 1981, p. 163.
164. Lindgren,
(1974).
B.O.,
Papier
165. Rapson, W.H., Pulp

57(10:147 (1956).
28(lOA):V9
Pap. Mag.
Can.
166. Croon, I., and Dillen, S., Tappi 51 (5):97 A

(1968).
167. Lom,
and
Ed.),
York,
v., in Pulp and Paper: Chemistry

Chemical
Technology
a.p. Casey,
300 edn., Wiley-lnterscience,
New
Vol. I, p. 693.
SECTIONill:
Chapter 4:
Chemistry of
Mechanical Pulp Bleaching
Carlton W. Dence
Professor Emeritus
Syracuse, NY
1. Chromophores
in unbleached
1.1 Coniferaldehye-type
(cheml)mechanical
structures.
1.2 Ortho- and para-quinonoid

1.3 Quinone
units.
1.5 Stabilized
complexes.
free radicals.
.........
163
164
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
164
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
164
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
164
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
164
methideintermediates
1.4 Metal-catechol
pulps.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
of hydrogen peroxide bleaching.

. . . . .. . . . . . . . . . . . . . . . . . .. 166
"
2.1 Reactive species in alkaline hydrogen peroxide bleaching
systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 166
2. Chemistry
2.2 Chromophore changes in the reactions of lignin with

hydroperoxide ion
167
2.3 Reactions of alkaline hydrogen peroxide with carbohydrates

and extractives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 175
3. Chemistry
of dithionite
(hydrosulfite)
bleaching.
. . . . . . . . . . . . . . . . . . . . . ..
176
3.1 Reactive species in sodium dithionite bleaching systems. . . . . . . . . . . . . . ., 176

3.2 Reactions of sodium dithionite with chromophore
systems in 1ignin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 177
161
Chapter ill 4: Chemistry of Mechanical Pulp Bleaching
Chapter m 4:
Chemistry
of Mechanical
Pulp Bleaching
Carbonyl group
163
Ethylenic group
164
Pulp Bleaching
-Principles
and Practice
J:
N
I
1. Chromophores in unbleached
(chemi)mechanical pulps
The objective in the bleaching of (chemi)mechanical pulps is to selectively remove
color-contributing groups (chromophores)
while simultaneously preserving pulp yield.
In current practice, this involves mainly the
use of bleaching agents such as hydrogen
peroxide and sodium dithionite (sodium
hydrosulfite).
Notwithstanding
the enormous importance of chromophore
structures in dictating the ultimate extent to
which (chemi)mechanical
pulps can be
bleached, the origin and identity of the entire array of color-contributing structures in
these pulps remain to be'.convincingly established in many instances.
The color of wood itself is variable, exhibiting dependence
on such factors as
plant species, growing conditions, composition, and microbiological breakdown (1).
On storage, wood may become further discolored through the influence of air, heat,
light, and fungal activity. In the refining
and grinding operations used to produce
(chemi)mechanical
pulps, the combination
of mechanical action, heat, added chemicals, and transition metals may also contribute to discoloration (2). Although every
principal component of wood -lignin,cellulose, hemiceUuloses, and extractives
has the potential for contributing to the
overall color of wood (3), lignin is generally singled out as the constituent having
the greatest direct influence on the color
of wood (2, 4-6). Because wood components are largely retained in the production
of (chemi)mechanical
pulps, lignin or
chemically modified lignin is also regarded
as the principal color source in unbleached

high-yield pulps (4).
The basic chromophore
units in lignin
are carbonyl and ethylenic groups and aro-
J:
N
+
Aromatic ring
Fig.1. &uk slrrlet.rtd eleme1lts

i" U",i" emmopboresys'-.
matic rings (Fig. 1). When present as single
or multiple non-conjugated groups, these
basic units do not impart color to the parent structure; however, a sufficient number
of basic chromophore units, linked conjugatively,give rise to chromophore systems that
confer color. Several such systems are illustrated in Fig. 2. It should be emphasized
that the presence in (chemi)mechanical
pulps of the different chromophore systems
listed in the figure has not been confirmed
in many instances.
Further, there is no
consensus concerning the relative contributions of the different proposed chromophore systems to the overall color of
high-yield pulps. These defects may be ascribed to the low concentrations
of chromophore groups in lignin and the lack of
analytical methods of sufficient sensitivity
and selectivity to detect and measure them.
The absorption maxima shown for the
chromophore
systems in Fig. 2 are those
reported for relatively simple monomeric
and dimeric chromophore
prototypes.
When the same structures form part of a
lignin macromolecule,
their absorption
maxima and peak intensities are, in all likelihood, altered by the electronic and steric
effects of substituent groups attached to
protOtype structural units. In some instances, this effect may lead to the displacement of the absorption maximum of the
unit from the near-UV to the visible spectral region (400-800 nm); that is, the material containing this particular unit becomes
colored.
J:
N
I
J:
N
+
J:
I
9J:
+
J:
N
I
J:
+
'"
J:
N
I
J:
N
+
-{)-oj
\

1.1 Coniferaldehyde-type
structures
The occurrence of coniferaldehyde-type

structures in softwood lignin is well-documented (7). Although the absorption maximum of coniferaldehyde itself, 0 in Fig. 2),
is located at about 340 nm in the near-UV
region, the tail of the peak extends into the
visible absorption region thus accounting
for its characteristic color. Moreover, it has
been suggested (8) that, when coniferaldehyde is incorporated into a cellulose matrix during the biogenesis process, its tail
absorbance is displaced to higher wavelengths and intensified. Imsgard et at. (9)
have estimated that coniferaldehyde units
account for 10-20% of the total light absorption of softwood lignin at 457 nm.
.
1.2 Ortho- and para-quinonoid
units
The suggested presence of 0- and pquinonoid units OIA and IlIA in Fig. 2) in
wood and unbleached (chemi)mechanical
pulps has been attributed
to oxidative
demethylation Ooss of methoxyl groups) (1,
JO) and side chain displacement (8) reactions, respectively.
These reactions are
mediated by phenol oxidases during lignin
biosynthesis. Alternatively, 0- and p-quinonoid structures may arise by hydrolysis of 0and p-ketals formed during this process (11,
12). Exposure of wood and (chemi)mechanical pulps to visible light (13) and
fungal degradation of wood occurring during storage (10) may provide additional 0quinone
structures.
Because simple,
unsubstituted 0- and p-quinones are inherently unstable in the presence of moisture
and heat, their proposed presence in a lignin or lignocellulose matrix implies that
they become stabilized through linkage to
adjoining structural units. Typically, quinonoid units in lignin are detected and estimated
indirectly,
that is, following
conversion to more stable structures. The
contribution
of o-quinonoid units to the
absorbance of lignin at 457 nm has been
estimated to be 30-65% (9).
1.3 Quinone methide intermediates

Quinone methides are intermediates in
the dehydrogenative polymerization of lig-
165
nin precursors (14). As shown in Fig. 2,

relatively simple p-quinone methides such
as IVAabsorb well outside the visible spectal
region. This fact and the susceptibility of
quinone methides to attack by nucleophiles
present in the biosynthesis reaction medium makes them unlikely candidates as
significant color sources in lignin. Conversely, o-quinone methide structures (yA
in Fig. 2) derived from diphenylmethanetype lignin units, absorb in the visible region and reportedly are relatively stable in
aqueous media (15). These qualifications
notwithstanding,
the proposed contribution to the color of native lignin by structures of this type is not unequivocally
supported by confirmatory evidence.
1.4 Metal-catechol
complexes
Another proposed source of color in lignin is metal chelate complexes of catechol
groups (1). The presence of catechol groups
in native lignin has been demonstrated using a variety of analytical approaches, the
most convincing of which consists of the
ethylation of milled wood lignin (MWL) followed by sequential permanganate and peroxide oxidation
treatments
(16). The
presence of catechol units in the original
lignin is confirmed by the detection of 1,2diethoxy-substituted
aromatic carboxylic
acid derivatives (16).
The structure of a ferrous iron-catechol
complex may be represented as shown in
Fig. 3. The absorption maxima of a variety
of model catechols with ferrous iron appear
in the 550-580 nm range (9). Calculations
based on the average molar absorptivity
value for such complexes indicate a catechol content for spruce MWL of about 1%
(9).
1.5 Stabilized free radicals
Stabilized free radicals also have been
suggested as contributing
to the color
of lignin in wood (1). In such instances,
radicals are postulated as arising from postbiogenesis processes such as autoxidation,
irradiation by UV and visible light, transition metal-catalyzed oxidation, enzymatic
and fungal attack, and mechanical action
166
(18,19). One of the most likely reaction

sites is the phenolic hydroxyl group which
is converted by one-electron oxidation processes to the corresponding phenoxy radical as illustrated in Fig. 4. An absorption
maximum of approximately
400 nm has
been reported (20) for this radical in an
aqueous alkaline solution. Through resonance stabilization and as the result of being trapped within the lignocellulose
matrix, phenoxy or other radicals, especially those derived from syringyl moieties
(21), conceivably may exist in sufficiently
high (steady state) concentrations to contribute significantly to the color of lignin.
finer (22). The resulting p,p'-dihydroxystilbene can then be autoxidized to the

corresponding
stilbenequinone, VIA, as illustrated in Fig. 2.
Lignin
--9=,
OH
1-
+2
Fig.3. Structurtd ~
cateebol complex.
(H\
'l
of IIferrtnlSlron-
1.6 Leucochromophores
Leucochromophores
comprise a class of
structures that, although nominally colorless, are readily converted to chromophore
systems through dehydration or dehydrogenation reactions as illustrated in Fig. 2.
Transformations of this type have the potential for significantly affecting pulp brightness. For example, the ease with which
hydroquinone (1m) and catechol (lIm) derivatives are oxidized to their chromophore
counterparts is a distinct disadvantage in
reductive bleaching where brightness gains
may be partially offset by successive re-conversion by air oxidation of the leuco (colorless) form to the quinonoid (colored)
form.
Inclusion of the stilbenequinone, VIB, in
the group of leucochromophores
is based
on the finding that structures of this type
are formed when diarylmethane-type lignin
model dimers are subjected to mechanical
action in a ceramic ball mill or a disc re-
1
Resonance-stabilized
radicals
Fig. 4. 6e1wral retU:tltm seqrunu:e for pberwxy
c4l f0rm4tKm
I.. lip''',
rtUU-
2. Chemistry of hydrogen peroxide bleaching

2.1 Reactive species in alkaline hydrogen peroxide bleaching systems
The principal reactive species in peroxide bleaching sytems is the hydroperoxide
ion (HOO) formed by the addition of alkali
to hydrogen peroxide:
HOOH + HO
HOO- + H20
[1]
This ion is a strong nudeophile, exceeding the nucleophilic reactivity of the hy-

droxide ion by approximately
200-fold
(2],24). The purported major role of the
perhydroxyl
ion in the bleaching
of
(chemi)mechanical
pulps is based on the
observed relationship between brightness
and pH as illustrated in Fig. 5 (25,26). In
this figure, brightness response is shown
to improve with increasing pH up to 12,
presumably as a result of a parallel increase
in hydroperoxide ion concentration. At pH
values above 12, brightness decreases most
likely because of offsetting chromophore
formation arising directly or indirectly from
alkali-induced reactions.
10.0
10.5
11.0
11.5
Initial pH
Fig. 5. RelilllmlsJtlp belrtleert i.i""1

brlgbt.ess
i. tbe peroxide
12.0
12.5
JIll ad flul
bletlcbi.g of
sJ'fIU TMP (25).
Under bleaching conditions, hydrogen

peroxide is partially decomposed to molecular oxygen, an electrophile, in a process having the overall stoichiometry
2 HOOH -> O2 + 2 HP
[2]
Alkali-induced peroxide decomposition has

been the subject of numerous studies from
which several distinct mechanistic interpretations have been made (27). Relatively recent studies lend credence to the conclusion
that, under bleaching conditions, the essential element of any proposed peroxide decomposition sequence is a transition metal
catalysis step (27-30) such as is included
in the following series of reactions (27):
M + HOOH -> M+ + HO. + HO-
[3]
02~ + HO. -> O2 + HO-
167
168
[6]
tions have been identified and classified

largely from studies with lignin model compounds. Although information gaps still
persist, it nevertheless is possible to discern
repetitive trends that are relevant for interpreting bleaching phenomena at the molecular level. In broad outline, the various
reactions can be classified according to
whether they lead to chromophore elimination or formation. In the complex set of
reactions that determine the outcome of
peroxide bleaching, both types may be
viewed as occurring competitively and sequentially from the outset although at different rates. Thus, in any given time frame,
the resulting brightness gain or loss is an
expression of the extent to which one type
of reaction outweighs the other.
(M = Transition metal ion)

Transition metals, typically Cu, Mn, and
Fe, are present as impurities in bleaching
chemicals (26,33), process water, and unbleached pulp (34).
AlkaIi-induced peroxide decomposition
is accompanied
by the formation of hydroxyl radicals (.OH) and superoxide anion radicals (02~) as shown in Equations [3]
and [4] (27.30,31,35).
These radicals also
may be generated during peroxide bleaching by molecular oxygen-initiated reactions
of lignin and carbohydrates. The hydroxyl
radical is an exceptionally strong electrophile and oxidant that is capable of reacting with both lignin and carbohydrates
(]6-38). Conversely, the superoxide anion
radical is a strong nucleophile in aprotic
solvents with moderate reducing properties
(36). Its possible role in pulp bleaching
has not been explored to the same degree
as that of hydroxyl radicals, but its involvement in the oxygenation of cyclohexdienyl
radical intermediates
has been proposed
(39) and is illustrated in Fig. 10 (left-hand
column).
Recent evidence suggests that free radical species may have a significant and positive effect on the bleaching of (chemi)mechanical pulps with alkaline hydrogen
peroxide (]1,36). Based on an analysis of
a kinetic expression describing peroxide
bleaching, Hobbs andAbbot (26) have suggested that pulp bleaching may consist of
two parallel processes: a reaction involving
the direct participation of hydroperoxide
ions in bleaching and a reaction in which
free radical species participate
in chromophore elimination. Irrespective of the
exact function of the different nucleophiles
and electrophiles present in a typical peroxide bleaching system (Table 1), the wide
range of possibilities contributes to making
the overall process extremely complex.
2.2 Chromophore changes in the reaction~ of lignin with hydroperoxide

ion
The reactions of lignin with alkaline hydrogen peroxide under bleaching condi-
Chromophore
elimination
reactions
The reactions of side chain enone structures with hydroperoxide ions are outlined
in Fig. 6. Coniferaldehyde
units (A) are
present in softwood lignin to the extent of
4-5/100 phenylpropane
units (4]). Enone
structures of the type represented by B in
the figure are not initially present in native
lignin but may be formed from phenacyl-<xaryl ether units on treatment with alkali
(44) alone or by hydrogen peroxide in alkali (45,46). The initial step in the reactions of these two enones, a conjugate
addition of hydroperoxide ion, is formally
a reduction process (47). Succeeding rearrangement and oxidation reactions lead to
the rupture of the n-S bond in the side chain
and formation of aromatic aldehydes for Atype structures (48,49) and aromatic carboxylic acids for B-type structures (45,46).
In the process,
the conjugated
chromophore systems of enone types A and B
(Fig. 6) are interrupted with the result that
the absorption maximum of each is shifted
from the near-visible to the UV spectral region, that is, "bleaching" occurs.
The aromatic aldehydes formed by reaction of contferAldehyde.type strUCt\IJ.'rS(A)
with alkaline hydrogen peroxide may, in
turn, be converted to p-benzoquinonoidtype chromophores by the Dakin reaction
as described below. The formation of phenolic end groups in the reaction of B-type
enones with hydroperoxide ions (Fig. 6) also
has important implications with respect to
the generation of new chromophore systems.
0- and p-quinonoid rings are comprised
of dual enone elements which offer multiple sites for attack by hydroperoxide ions
as illustrated, in part, by the sequences in
Fig. 7. The common feature of all these sequences is the destruction
of the chromophoric
systems terminating
in the
formation of carboxylic acids (50-54). Relatively simple carboxylic acids have, in fact,
been detected in the effluents from peroxide-bleached mechanical pulps (52,53).
When the quinonoid rings are condensed,
that is, linked to adjacent lignin units by
carbon-carbon or stable ether bonds, carboxylic acid fragments remain attached to
the lignin network as evidenced by its increased carboxyl content (51,55). Besides
carboxylic acids, methanol invariably is
formed from methoxyl-substituted phenolic
and p-quinonoid rings during the reaction
of lignin (52,53,55) and lignin model compounds (46, 50, 51, 52, 56, 57) with hydroperoxide ions.
Hydroxide ions, the other major nucleophile present initially in alkaline peroxide
bleaching system (Table 1), in principle may
attack enone units in quinonoid structures
in a manner analogous to the much stronger hydroperoxide ions. As an example, the
conjugate addition of a hydroxide ion to an
o-quinonoid ring is outlined in the left.hand
sequence of Fig. 8. The hydroxylated catechol dianion formed (41) is a leucochromophore (see Fig. 2) and is readily reoxidized
to a hydroxyquinone
structure by molecular oxygen, hydroxyl radicals, or specific
metals in the appropriate valence state as
described below in Subsect. 2.2. In the
right-hand sequence in Fig. 8, attack of a
hydroxide ion on the carbonyl group of an
o-benzoquinonoid
ring is pictured as giving risc (Q a ring contr.lctlon by a benzylic
acid-type rearrangement with accompanying
partial destruction of the chromophore system (41).
Chapter III 4: Chemistry of Mechanical Pulp Bleaching
169
170
Conjugate
addition
HCOO+
l-~'
1
~oo
roo
~-o-
~o
. ,
~~HO<r
"
./
~-HO
OCH;,
~~o
0-
./
/0~
l-w
HCOO+
ROH
+
I
Carboxylic acid
fragments
coo-
/~./
--~:
~~o
o
0-
HOD-
HO
IH~
~1-=
1
GartJoxyllC
Carboxytic
Fig.6. ElIml1Ul1lonof _
oxide lOllS(41.42).
acid
fragments
sUIechain cbromo'/Jbore smu:"'res IryreflCtltmwltb Irydroper-
Fig. 7. ElIml1Ult1tm
of 0- find p-qrdrunwlll
cbromopbore
IIdd
fragments
Carboxytic acid
fragments
systems
Iry refIClIon wltb Irydroperoxlde
Ions ( 41).

f'f!flCtive species ,,,,.
Table 1. Ozygetl.etmta''''"g
t"'lly preSet/t or generated I" bydrogetl
peroxtde "leacbing systems
Electrophiles
Nucleophiles
0/-0,-)
HO-
HOO'
HO'
0,'
Finally, the removal of quinone methide.

type chromophore systems is illustrated by
the sequences in Fig. 9. In the left.hand
sequence, the conjugate addition of hydroperoxide ion to the methide group is followed by rearrangement
to an oxirane
(epoxide) intermediate which, in turn, is
transformed
to a p-quinonoid structure.
This chromophore may be degraded to colorless fragments as shown previously in Fig.
7. In the right-hand sequence in Fig. 9, conjugate addition of a perhydroxide ion to a
stilbene quinone unit, which may be viewed
as a diquinone methide,and rearrangemenr
to a dioxetane intermediate ultimately yields
an aromatic aldehyde. Structures of this
type may then be converted by the Dakin
reaction (see below) to a p-quinonoid derivatives that are degraded to colorless fragments in further oxidation reactions as
illustrated above. The examples shown in
Fig. 9, chromophore
elimination involves
cleavage of a C,-a or Ca-C. bond; as applied
to the same type of units in a lignin network, this reaction represents the splitting
of the lignin chain and the possibility of increased solubility.
Chromophore-forming
reactions
In addition to the isolated chromophores
and conjugated
chromophores
initially
present in lignin, others may be formed
during peroxide bleaching by the action of
reactive oxygen species initially present
(HO' and HOO") or those generated in the
course of bleaching (e.g., 02 and HO.). A
few illustrative examples are outlined in
Figs. 10 and 11. The left-hand sequence in
Fig. 10 represents the so-called Dakin-like
reaction. In this reaction, p-hydroxybenzyl
171
alcohol groups are converted ultimately to

p-quinonoid
chromophores
(39,45,52,
56,58-60) by oxygenation of a free radical
intermediate (39, 45,59, 68). Salient features of the reaction are phenoxide radical
formation initiated by molecular oxygen
(30,39,41,50,
59), hydroxyl radicals (30,
47,50,61,62)
or transition metals in their
higher oxidation states (30, 50,61,63 -65),
addition of a superoxide anion radical (OJ)
or molecular oxygen (.02,) to a mesomeric
form of a cyclohexadienoyl radical, and rearrangement of the resulting alkylhydroperoxide ion.
172
l~
-- \::0
~
Stilbenequinone-type
~f~l,
o
1
Fig. 8. Eltml",,1ttm
of fJIIltIOfUJitl cbromopbof'f!
Kms.
tems by f'f!tICIUm wit" bydroxtde
sys-
The Dakin reaction is outlined in the

middle section of Fig. 10. This reaction is
applicable to 0- and p-hydroxyphenacyl
structures and leads ultimately to the formation of methoxy-substituted
hydroquinones for lignin-like structures (48, 49,
52,56, 59,66). The principal steps in the
Fig. ,. EllmttltltUm of fJIIl_tbide

byd~
Kms (39,41).
arut sttlbetle fJII'-
cbromopbof'f! systems by f'f!aditm wit"
~--
~~~b_
#
" ~0- C>CI'\
173
#
"
~,HO..orM+
HOO1
~~-
!{
~"
"
~C>CI'\
~C>CI'\
j-HO-
j
J/OH
~-
--9-000
"
C>CI'\
~,
b=a
~,
I I
"
1-~
"
~C>CI'\
~
~II
C>CI'\
HO-
--~-"'-l~
~--~~
l-oow
OH
Reduction
(Proton donor)
~,HO.,orM+
Oxidation
"
~C>CI'\
--~
0
Fig. 10. FomJIItkm of'l,dtUmOiIl cbronwpbore arulleru:ocbrrnrropbore systems by reactiorr witb diff-t
ffucleopbiles arul electropbiles.
174
sequence are a nucleophilic attack of a hydroperoxide ion on the -carbonyl group

and a following series of rearrangements of
the hydroperoxide adduct leading finally to
the formation of a methoxyhydroquinone
structure. Detection of methoxyhydroquinone itself in the effluent of a peroxidebleachedTMP (67) indicates the relevancy
of this reaction in the bleaching process.
Methoxyhydroquinones
are the leuco
(colorless) forms of the corresponding pbenzoquinones into which they are readily
converted by an one of several one-electron
transfer oxidants, for example, molecular
oxygen (45), present in the bleaching system (Fig. 10). In aqueous alkaline media,
the quinone may be reconverted (t.e., reduced) to the hydroquinone
(colorless)
form (68) to complete the redox cycle as
illustrated in the figure. In an analogous
series of reactions, catechol units can be
oxidized to their o-benzoquinone counterparts as shown in the right-hand sequence
of Fig. 10. The latter structure, in turn, may
be reduced to catechol units in the presence of suitable proton donors (69).
It is important to note that the Dakin and
Dakin-like reactions are restricted to phenolic units and that, in both instances, the
side chain is displaced from the aromatic
ring.
The formation of chromophore systems
by base-catalyzed elirnination reactions is
illustrated by the two sequences in Fig. 11.
In each instance, the alkalinity and temperature of a conventional peroxide bleaching
system is sufficient to cause the reactions
to occur. In the left-hand sequence, the
1,3-ketol unit comprising the side chain is
dehydrated under the prevailing alkaline
conditions to a pheny1-conjugated enone
chromophore system (45,46). In the righthand sequence of the figure, a 1,2-diarylpropane unit undergoes loss of water or
formaldehyde and a proton to produce a
stilbene-type
structure
(70,71).
This
leucochromophore
can then be oxidized to
a stilbene quinone-type chromophore
as
shown in the figure.
With the foregoing as a basis, the peroxide bleaching of (chemi)mechanical
pulps
may be said to consist of the partial or total

destruction of chromophore
systems initially present in the lignin and the formation of new chromophore structures. With
this concept as a foundation, the typical
bleaching rate plot (see Fig. 13, Chap. V 1)
can be interpreted as follows: the rapid initial brightness increase may be assigned
principally to the removal of the original
chromophore
systems; the phase exhibiting a reduced bleaching rate may reflect the
offsetting effect of chromophore
creation
(49,50,52, 64, 65, 72, 73). The structural
characteristics of the chromophore systems
formed during peroxide bleaching are of
particular interest because of their presumed influence in determining the upper
limits to which (chemi)mechanical
pulps
can be realistically bleached.
In all probability, the types of chromophore structures formed from lignin
during peroxide bleaching are similar or are
closely related to those pictured in Fig. 10.
Although, in general, quinonoid structures
are readily degraded to colorless fragments
by hydroperoxide
ions, typified by biphenyl (a, b, c), ~-5 (d), and diaryl ether (e)
units (Fig. 12) linked to methoxy-pbenzoquinone
groups (R) formed during
bleaching are reportedly unreactive (74).
If, in fact, degradation-resistant
quinonoid
or related chromophore systems are present
during pulp bleaching, their practical effect
would be to increase the amount of peroxide required to reach a given brightness
level (64,65).
2.3 Reactions of alkaline hydrogen

peroxide with carbohydrates and
extractives
Unlike the reactions of alkaline hydrogen
peroxide with lignin, the participation of
carbohydrates and extractives in peroxide
bleaching has received only limited attention as would be expected from their generally recognIzed
mInor effect on the
brightness
of most (chemi)mechanical
pulps. Nevertheless, the reactions of alkaline peroxide and its decomposition prod-

R
= H,
Aryl,
175
<;:HzOH
b-R1
/~
It'
l-~-
Fig. 11. FfJt'JllllUon of sIIIe chai.

elimiaaUon
reaetWas.
Stilbenequinone
chromophoresystem
arrtl slilbeae
'1'11-
clmnrwpllore
systems
ucts with these two pulp components have

a potential bearing on such other considerations as paper strength and quality, heat
and light reversion,
paper
machine
runnability, and effluent management (55)
and therefore are discussed briefly below.
Carbohydrates
in (chemi)mechanical
pulps are subject to attack by nucleophiles
(HOO- and HO-) initially present in the
bleaching system and active oxygen species
formed from peroxide decomposition.
For
example, hydroperoxide
ions can oxidize
polysaccharide end units to aldonic acids
(76) thereby helping to reduce cellulose
degradation by alkali-promoted peeling reactions; hydroxide ions can effect the release of acetic acid by deacetylation
of
galactoglucomannans
in the hemicelluloses
in TMP (55) and groundwood (53). Also,
acidic hemicelluloses (t.e., those containing
uronic acid units) dissolve in the alkaline
bleaching solution (55) where they may enhance the demand for cationic polymers
used in papermaking systems. The extensive degradation of carbohydrates in groundwood (53,77)
and a cellulose
model
compound (78) by alkaline hydrogen peroxide has been reported. Such processes
undoubtedly are initiated by peroxide decomposition products such as superoxide
anion (79) and hydroxyl (60) radicals.
The fate of extractives during peroxide
bleaching is governed by their ability to dissolve or disperse in the alkaline medium
(55,77). The loss (t.e. degradation) of free
fatty acids from spruce groundwood during peroxide bleaching reportedly is restricted to a small proportion
of the
unsaturated type (77). Triglycerides and
steryl esters are also unresponsive to alkaline peroxide, but conjugated resin acids,
lignans and bark-derived stilbenes are extensively oxidized (77). For those extractives removed
from the pulp during
bleaching, descriptions of the reactions and
reactive oxygen species involved are, with
or Alkyl
R1 AryIoxy
Conjugetedenone
chramophoreaystem
176
very
fry base-eatJJlyzeti
few exceptions,
unavail1ble.
One such
exception is abietic acid and similar resin

acids having conjugated double bonds. On
treatment with alkaline peroxide, abietic
acid is converted to a complex mixture of

oxo and hydroxyabietic acids (55,77) by
reactions most likely initiated by hydroxyl
radicals arising from peroxide decomposition. The modification and degradation of
resin and fatty acids in peroxide bleaching
has environmental significance because of
their toxicity to fish (81).
Oxidanl
(b)
(e)
(eJ
Fig. 12. Sfldflres resistteatto degnulatkm frybydro/J6f'fdIk Was arrtI tbe deeompositkm
protlru:1s.
3. Chemistry of dithionite (hydrosulfite) bleaching

3.1 Reactive species in sodium
dithionite bleaching systems
The principal reducing species in dithionite
bleaching is thought to be a sulfur dioxide
radical ion (82) formed by dissociation of
the dithionite ion (83,84):
[7]
In addition, possible electron exchange
between sulfur dioxide radical ions may give

rise to sulfur dioxide and sulfur dioxide
dianions (sulfoxylate) ions, both of which
are reducing species (84).
2 502'
502 + 5022-
[8]
As a reductant in pulp bleaching dithionite

ion is converted to bisulfite ion in a reaction having the following overall stoichiometry:
520l- + 2 H20
2 HS03- + 2 W + 2 e- [9]
Under bleaching
conditions,
sodium
dithionite is unstable, particularly in the
presence of oxygen, and undergoes oxidation and auto-oxidation-reduction
reactions
leading to the formation of complex mixtures of inorganic species that includ~
sulfite, sulfate, thiosulfate, and polythionate
ions (85-87). These decomposition
reactions are described in greater detail in Chap.
V 2. Apart from bisulfite ions which have
found limited use in the bleaching
of
groundwood and disc refiner pulps (88),
dithionite decomposition
products other
than sulfur dioxide appear to have no
demonstratable
role in chromophore
removal.
3.2 Reactions of sodium dithionite

with chromophore systems in
lignin
The reactions of sodium dithionite with the
chromophore
systems in (chemi)mechanical pulps have not been as systematically
and comprehensively
studied as those involving alkaline hydrogen peroxide. Moreover, of the relatively few studies that have
been reported, most have limited their experimental approach to UV and IR spectroscopy in attempting to identify chromophore
systems susceptible
to reduction
by
dithionite. Thus, relatively few definitive
statements on the response of individual
chromophore systems to dithionite under
typical bleaching conditions can be made
with much assurance.
However. there is general agreement that
relatively simple (uncondensed)
0- and pquinonoid structures can be reduced by
177
dithionite to their corresponding colorless

(leucochromophore)
catechol and hydroquinone forms (84, 89-94). The left-hand
sequence in Fig. 13, proposed by Gierer
(82), illustrates the reduction
of an 0benzoquinonoid
unit to a catechol dianion
by a sulfur dioxide radical ion. The reduction of a p-benzoquinonoid
structure presumably
proceeds
by an analogous
sequence. As was the case for hydroperoxide ions, condensed quinonoid structures
are reported to resist reduction by dithionite
ions (74).
The foregoing reduction reactions are
proposed to occur by a one-electron transfer mechanism.
An alternative pathway
consists of a nucleophilic addition of a sulfur dioxide dianion (sulfoxylate ion) to the
carbonyl carbon atom as the first step in a
series of steps leading ultimately to the same
products obtained with sulfur dioxide radical anion as reductant (95). The reduced
structures are leucochromophores
and, as
such, are subject to. reoxidation to their
quinonoid forms by oxygen (air).
Sulfur dioxide and bisulfite ions, products
of dithionite reduction and decomposition
reactions, are also reported to have the capability of decolorizing simple quinonoid
units (89, 90). The extent to which such
species participate in dithionite bleaching
is not known.
Another cbromophore system that is generally believed to respond favorably to
dithionite
is that
represented
by
coniferaldehyde-type
structures (91-93).
The removal of such groups in dithionite
bleaching can be rationalized in a variety of
ways, several of which are shown in the
right-hand section of Fig. 13. In pathways
A and B, the dithionite ion serves as a reductant for the aldehyde group and as an
adduct in a nucleophilic conjugate addition
reaction, respectively (95); in pathways C
and D, by-product bisulfite ions react with
the conjugated system to form mono- and
disulfonates (96). Reactions such as C and
D may occur before bleaching as part ofthe
chemical modifications occurring during
178
H
R-C=~-CH.10H
A
H
AC=C-a-tO
H
HS03-
Fig. 13. Bllmllultlol8

arullnMllftte
of f/IIi-imu.
arul COIIifemltlebyde-type
chemimechanical
pulping (97-99). In all
four examples shown in the figure, the reactions lead to the partial reduction of the
chromophore system and the displacement
of absorption maxima from the visible region to the near-UV spectral region.
Under pulp bleaching conditions, a-aryl
ketone-type structures are generally unresponsive toward reduction by dithionite
(90,91,93).
At higher temperatures and
in mixed solvent systems, aliphatic and aromatic aldehydes and ketones are reported
cbromoJlbores
H
R-C-~-CHO
I
saz-
H
R-C=C-C-H
H
OH
I
I
S03OH
H
R-C-CHz-C-H
S03-
I
I
503-
by retlCtioII IlIitb ditbUmite
to undergo significant conversions to primary and secondary alcohols (100, 101).

Similarly, ethylenic groups conjugated with
an aromatic ring, typified, for example, by
coniferyl alcohol. appear to be unreactive
toward dithionite
(91, 93). However,
bisulfite ions have been found to add to ethylenic groups in compounds
such as
isoeugenol and chalcone (90). Studies of
the reactions of dithionite with other individual chromophore systems in lignin have
not been reported.
~-
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SECfION ill:
Chapter 5:
Chemistry of Brightness Reversion
and Its Control
Cyril Heitner
The Pulp and Paper
Research Institute of Canada
Point Claire, Quebec
1. Introduction.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
2. Experimental
methods for determining
yellowing.
. . . . . . . . . . . . . . . . . . . . . ..
2.1 Optical measurements
185
185
185
2.2 Aging tests. . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 186

3. Thermal yellowing.
. . . . . . . . . . . . . . . . . . . .. . . . . . . .. . . . . . ... .. . . . .. . . . . ..
3.1 Effect of wood species

3.2 Effect of pulping.
186
187
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 188
3.3 Effect of bleaching

188
3.4 Effect of metal ions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 190
4. light-Induced
yellowing..
. . . . . ... . . . .. .. . . . . . . . . . . . . . . .. . . . . .. . . . . . . ..
4.1 Chromophoreformation
4.2 Role of oxygen in light-induced yellowing.
190
190
. . . . . . . . . . . . . . . . . . . . . . . . . .. 1%
4.3 Mechanism of the light-induced yellowing process . . . . . . . . . . . . . . . . . . . .. 197

4.4 Inhibition of light-induced yellowing. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
5.Summary
209
183
Chapter ill 5: Chemistry of Bdghtness Reversion and its Control
Chapter m 5:
Chemistry of
and its Control
1. Introduction
Ugnin-containing pulps, thermomechanical (TMP) and chemithermomechanical
(CTMP), are used primarily for the production of newsprint, advertising inserts, directory paper, and some catalogue papers
all short-life products. These pulps can be
bleached to an ISO bdghtness level of about
80% using two alkaline hydrogen peroxide
stages or an alkaline hydrogen peroxide
stage followed by a sodium dithionite stage._
At this brightness level, these pulps can be
used in furnishes for the manufacture of
business forms, copy and reprographic papers, tablet and writing papers, and highgrade publication
papers for books, all
long-life uses. However, papers made from
bleached TMP and CTMP turn yellow during use, a property which restricts their use
to short-life papers. It has been suggested
(1) that, if the time taken for light-induced
yellowing of these papers could be increased by 3-36 months, the potential market for bleached TMP and CTMP would be
expanded by 0.6-2.2 million tons per year.
If the tendency to yellow, termed brightness reversion,
could be prevented,
bleachedTMP and CTMP could be included
in furnishes used to manufacture
highbrightness papers (2).
Brightness reversion may be classified
according to the following two processes:
1) Thermal, oxidative discoloration caused by

long-term storage of paper at ambient temperature
2) Photochemical, oxidative discoloration
caused by exposure of paper to daylight
2. Experimental methods for

determining yellowing
2.1 Optical measurements
Both thermal and light-induced yellowing can be measured by the decrease in
185
brightness. However, direct correlation of

the brightness decrease with chromophore
concentration
can be misleading because
brightness is not a linear function of chromophore concentration.
For example,
fewer chromophores are required to cause
a 3-point brightness decrease from an initial value of 80 than from an initial value of
60.
At a given wavelength, the reflectance
CR. at 457 nm is brightness) of an opaque
sheet of paper (i.e., at infinite thickness),
R. is related to k/s, the ratio of the specific
abSorption (k) to the specific scattering (s),
by the Kubelka-Munk equation.
k/s
(l-Rj/2R.
[1]
If the specific scattering, s, remains constant

during thermal or light-induced yellowing,
k/s can be used as a measure of the amount
of chromophores produced in the pulp. In
1945 Giertz (3) proposed the concept of
post color number, P.c. number, defined
according to the following equation.
P.c. number
= 100{(k/S)attt<a_(k/S)bdo",_}
[2]
Thus, the P.c. number calculated from the

change in k/s was found to be directly proportional to the chromophores formed during thermal- or light-induced yellowing.
For the optical parameters derived from
the Kubelka-Munk equations to be valid, the
sample must be optically uniform. That is,
the distribution of chromophores
in the
direction of the incident light must be uniform. Thermally yellowed paper fulfills this
requirement because the temperature and
ambient atmosphere are equalized throughout the thickness of the sheet. However,
the chromophores
in paper yellowed
through exposure to IN light are not uniformly distributed throughout the thickness
of the paper sheet. Because the intensity
of incident light decreases with increasing
penetration into a sheet of moderate-to-high
basis weight, the concentration
of chromophores formed is greatest at and near the
surface and decreases with increasing
depth. Irradiation ofvery thin paper sheets
having a basis weight of 10 glm2 produces
186
a sheet with a uniform distribution
of chro-
mophores throughout its thickness as indicated by identical reflectance values on

both sides (4).This sampling method is required to accurately determine the chromophores formed during light-induced
yellowing.
2.2 Aging tests
The propensity of Iignin-containing pulps
to yellow during aging in the dark or during exposure to light containing IN radiation can be measured under ambient or
accelerated conditions. Thermal discoloration is accelerated by a combination of high
temperature
and humidity; light-induced
yellowing is accelerated by high-intensity
light sources or by light sources rich in IN
light.
The use of high temperature and relative
humidity to accelerate the thermal reactions
leading to yellowing is fraught with uncertainty regarding the correlation of accelerated yellowing results with those obtained
under ambient conditions. The rate of yellowing of newsprint at 9<>"Cand 100% R.H.
has been found to be a linear function of
oxygen concentration (5). However, even
at zero oxygen concentration a finite rate
of yellowing,attributed
to the elevated temperature was observed in this study. Also,
the relative importance of oxygen in the
overall deterioration of paper (yellowing
and mechanical strength) decreases with deceasing temperature (6). These results suggest that accelerated thermal aging not only
increases the rates of reactions occurring
under ambient conditions, but also initiates
color-forming reactions that occur only at
elevated temperatures. Therefore, accelerated thermal yellowing at temperatures of
80-1OOC may lead to uncertain conclusions
about
the extent
to which
paper yellows in the dark at room temperature.
The use of IN-rich light to accelerate
light-induced yellowing can produce results
comparable to those obtained under ambient conditions (i.e., under natural or artificial daylight),
provided
the emission
spectrum of the IN light source has a similar wavelength range and light intensity distribution as the IN region of the ambient
light.
3. Thermal yellowing
Thermal yellowing of lignin-containing
paper is caused by storage in the dark under warm and moist conditions, for example, during paper roll storage in the
manufacturer's or customer's warehouse or
during storage in an office filing cabinet.
Excessive yellowing due to thermal reversion often causes the brightness of the
paper to decrease below contracted specifications leading to increased costs to the
16
Jack pine
heartwood
14
....
Q)
.c
E
:]
c:
10
0
(5
0
en
0
a..
12
Jack pine
sapwood
~Westernhemlock
heartwood
Western hemlock
sapwood
1
2
~Peroxidecharge, % on pulp
Fig.1. YelWwlllgof peroxiIle-blellCbedJtU:1I

JllIIeand westem bemlocllsapwoodand heartwood (10).
~_._--_.
Chapter III 5: Chemistry of Brightness Reversion and its Control
187
188
manufacturer in the form of penalties. Also,

thermal yellowing decreases the useable
lifetime of documents containing historical
data.
groundwood to the level of that of black

spruce groundwood (9).
nrbk I. l!ffed ofsJlla 0II1be t6enruIl ~
(ItKJ'C, (}'JI.R.H.) of m1HmiaI1
3.1 Effect of wood species

The results (Table 1) of a study on the
brightness stability of stone groundwood
and refiner mechanical pulps from eight
eastern Canadian wood species indicate that
furnish content has a significant effect on
brightness after accelerated thermal aging
(7). Cedar mechanical pulps were the most
stable to heat (105"C, 0% R.H.) of the softwoods studied. White spruce, balsam fir,
and black spruce had about the same heat
stability and were less stable than cedar.
Larch and jack pine had the lowest heat stability; birch and poplar were found to to
have similar stability. The thermal stability
of a softwood species native to British
Columbia,
western
hemlock
(tsuga
beteropbylla), has been compared to that
of black spruce (picea mariana), an eastern Canadian softwood (8). The western
hemlock pulp yellowed to a much greater
extent than black spruce pulp after accelerated aging at 105"C for 18 h. Dithionite
bleaching had very little effect on the extent of thermal yellowing of these samples.
However, peroxide bleaching decreased the
extent of yellowing
western
hemlock
Species
/JIIlp (7).
Thermal reversion
(&em' m2/kg)
Softwood
Cedar
Balsam fir
Black spruce
White spruce
Larch
Jack pine
0.6i1.0
0.9:1:0.3
1.110.1
1.210.1
2.010.5
2.510.6
Hardwood
Birch
Poplar
1.310.8
1.210.2
The region in the tree from which the

fiber originates can have a large effect on
thermal yellowing for some wood species.
Figure 1 shows that the heartwood of jack
pine (pinus bankstana) yellows more than
jack pine sapwood or western hemlock
(Tsuga beteropbylla) sapwood and heartwood (10). Bleaching with up to a 2%
charge of alkaline peroxide did not significantly change the degree of yellowing as
measured by the P.C. number.
3.2 Effect of pulping

The effect of pulping process on thermal yellowing depends on the method of
aging. When accelerated aging conditions
(100"C,O% R.H., 24 h) are used, both unchelated and chelated unbleached SGW and
RMP orTMP undergo thermal yellowing to
the same extent as seen in Fig. 2 (8, 11).
However, Fig. 3 shows that, under ambient
aging conditions (23C, 50% R.H.), unchelated and chelated thermomechanical pulps
yellow to a slightly greater extent than does
SGW (11). Similarly, chelated TMP also yellows more than chelated SGW
Treatment of chips with sodium sulfite
followed by disc refining produces pulp
which yellows to a greater extent after ambient (11) or accelerated aging (11, 12)
than does pulp made from untreated chips.
pulp (CTMP) produced from lightly sulfonated chips, yellows
in the dark at a higher rate than does
thermomechanical
pulp (TMP) (12). Highyield sulfite (HYS) pulp, produced at 80%
yield, yellows to a greater extent under both
accelerated and ambient conditions as seen
in Figs. 2 and 3 (11). Chelation has only a
small etkct on the thermal yellowing ofHYS
pulp.
The propensity for pulp produced from
sulfonated chips to yellow during aging in
the dark may be associated with the forma-
30
o Unchelated
100C,
tion of catechols by reduction of <>-quinone

groups native to lignin or formed by
demethylation of the guaiacyl groups during pulping as shown in Scheme 1 (13-16).
Catechols then undergo autoxidation
to
colored quinones and hydroxyquinones
(17).
3.3 Effect of bleaching
lignin-retaining bleaching of mechanical
pulp has a significant efkct on the yellowing associated with the thermal aging of lignin-containing
(mechanical,
CMP and
CTMP) pulps. Any lignin-retaining bleaching - reductive bleaching with sodium
dithionite or oxidative bleaching with alkaline peroxide - increases the extent of yellowing during aging in the dark (7, 18, 19).
Under ambient aging conditions, dithionitebleached mechanical pulps yellow to the
greatest extent as seen in Fig. 4. The yellowing of mechanical pulps bleached with
alkaline peroxide is less than that of dithionite-bleached pulps but greater than that
of unbleached pulps (7, 18, 19). This result is consistent with the fact that peroxide oxidizes colored quinonoid structures
to colorless non-reactive products while
dithionite reduces yellow quinones to colorless hydroquinones
which are readily
oxidized to quinones under ambient conditions (20). This observation also explains
70
III Chelated
o Unchelated
ED Chelated
23C, 50% R.H.
60
0% R.H.
C>
.:JI!. 20
N"
E
,::.
It)
:2 10
<1
C>
50
.:JI!.
N" 40
J<1
~30
20
10
o
SGW
TMP
HYB
TMP or RMP
SGW
Pulp type
Fig. 1. Yell_Ing of stone gt'OfIn4uJood (SGW), t~kal
under 4IXBlertdell aging corulttlorts (11).
HYS
Pulp type
JIIIlp (TMP), IIIUlblgb yklil S8lfth! (HYS)
Fig. 3. Yelloll1lng of stone ~
(SGW), tbermomeclHmkal
ruuler "",blent agingcorulttltnrs(11).
jIIIlp (TMP), IIIUlblgb ylelil S8lftte (HYS)
Chapter ill 5: Chemistry of Brightness Reversion and its Control
189
190

15
Unbleached
1.5% Peroxide
...
~
5% Peroxide
20C, 65% R.H.
c:::
Ambient
conditions
OH
~ 10
E
::J
~
6-
1 % Dithionite
...
o
"0
o
-IoI)
a.
Sebeme1.
the lower extent of yellowing of peroxidebleached HYS pulp compared with that of
unbleached HYSpulp.
results than those obtained under ambient

aging conditions. Figure 5 shows that the
rate of thermal yellowing is highest for
dithionite-bleached mechanical pulp during
aging under ambient conditions (200C and
65% R.H.); unbleached
and peroxidebleached pulps each yellowed at the same,
but considerably lower, rate (18). As seen
in Figs. 6 and 7, accelerated aging at 85C,
95% RH. and at 105OC, 0% RH. increases
the yellowing rate of peroxide-bleached
pulps with so that their P.c. number is about
the same or greater than that of dithionitebleached pulps (18). However, under these
drastic conditions, yellowing reactions that
Unbleached and peroxide-bleached

mechanical pulp (brightness, 78%), aged between book pages, both yellowed to the
same extent (21). The difference in yellowing resulting from ambient aging in an
open atmosphere and aging between book
pages indicates how sensitive thermal yellowing is to the environment of the paper
sheet being studied.
The thermal yellowing of bleached mechanical pulps under accelerated aging conditions (e.g., 85C and 95% RH. to l00"C
and 0% RH.) produces somewhat different
60
50
C)
.:.:.
-C\I
o Unbleached
Peroxide-
bleached
23C, 50% R.H.
Dithionite-
bleached
40
E 30
~II)
v 20
.:.:.
<I
10
0
SGW
TMP
HYS
Pulp type
Fig.4. Yellowlllgof ~-
IlUbkmUe-bletIcbetl
SWlle~
(SGW),tbermtnrleelHm,"1
pulp
(TMP),
blgb-yNlIl s"lflte
""" (HYS) "ruler tlf!lerwIetI IIgllIg WIIIlIHmu (7, 18 ,19). No"'"
IIf)/dltlble
"""for tbe yellowlllg of tUtlmmite-bletlcbell HYSpulp.
tWe
100
200
Aging time, h
FI,. 5. Yellowlll' tYIIa of~-bktIdHNI

tUHmu
(18).
"""
300
400
tUtlmmite-bletlcbetlmedll..,"l p.lp """'lIIfIlMnt
do not occur or are very slow at ambient

temperatures and humidity become significant.
3.4 Effect of metal ions

The ferric ion (Fe<) is the most detrimental transition metal ion affecting the color
and thermal yellowing of lignin-<:ontaining
pulp (22). It has been observed to cause
an immediate drop of 3 points in the brightness of western Canadian pulp and 2 points
in the brightness of eastern Canadian pulp
and can accelerate brightness reversion
(22). Increased Fe3+content increases the
P.c. number of unbleached and peroxidebleached SGW resulting from accelerated
aging at 85C and 95% R.H. (23).
Dithionite-bleached SGW;to which no Fe3+
has been added has a high P.C. number of
60 (23) and Fe3+ addition appears to have
very little additional effect on the thermal
yellowing of pulp bleached with this chemical. Lead, Pb2+, cuprous, Cu 2+,manganous,
Mn 2+,or zinc, Zn 2+ions had no detectable
effect on pulp thermal brightness reversion.
Chelation of all unbleached lignin-<:ontaining pulps (SGW; RMP,TMP and HYS)
decreased the extent of yellowing after accelerated aging at lOOOCand 0% R.H. (8,
11) and after aging under ambient conditions at 23C and 50% R.H. (8) as seen in
Figs. 2 and 3. These results suggest that Fe3+
roII-
does play a role in the thermal reactions

leading to brightness reversion.
4. Light-induced yellowing
Photochemical reversion or light-induced
yellowing of lignin-<:ontaining paper can
lead to brightness decrease of more than
30 points in a short time (6-8 months).
Under identical conditions, light-induced
yellowing of bleached kraft pulp (i.e., a lignin-free pulp) causes only about 3-points
loss in brightness. As a result, kraft pulp is
used in the manufacture of produ<.:ts where
long life is important.
Early studies led to the conclusion that
thermal- and light-induced yellowing are
attributable to chemical changes in the lignin,specifically the oxidative demethylation
of aromatic methoxyl groups (24-28). Further progress in elucidating the yellowing
reaction pathway was hampered by lack of
knowledge about the structure of lignin.
4.1 Chromophore formation

Ught-induced reversion of unbleached mechanical pulps
light-induced brightness reversion of lignin-containing papers was initially measured as the difference between the initial
and final reflectance (i.e., brightness) at a
single wavelength. More detailed informa-
-~~
191
192

100
12
Unbleached
....
....
CD
1 % Dithionite
-+-
1.5% Peroxide
.......
.c
E
:J
C
....
o
(5
o
1i)
;:R.
-+-
'S;
:g
Q)
:;:::
Q)
....
Q)
o
a..
>
..as
Q)
a:
85C, 95% R.H.
20
60
50
30
40
Aging time, h
~tbIOldlfl-blMellM mee/NmlulIn''p "".,.
..
tion about the reaction pathways leading

to yellowing can be obtained from the UVvisible spectra of lignin-containing paper
measured before and after brightness reversion. Claesson et aI. (29) carried out the
earliest studies on the effect of near-UV irradiation on the UV-visible reflectance spectra of high-yield spruce bisulfite liner pulp
and newsprint.
In this work, the relative
reflectivity [Eq. 3] was plotted against wavelength in the 300600 nm range as seen in
Figs.8 and 9 (29).
85
80
75
Relative reflectivity
R(irradiated)lR(initial)
250
x 100
20
....
Q)
-+-
.a
350
400
450
500
550
Wavelength,
nm
600
650
300
350
400
600
650
125
[3]
(R=Reflectance)
The relative reflectivity of bisulfite liner after brightness reversion decreased to a

broad minimum at wavelengths between
450 and 500 nm as shown in Fig. 8. The
effect of UV irradiation of newsprint and
wood on their relative reflectivity is different from that of high-yield bisulfite liner.
The relative reflectivity of these materials,
Unbleached
~
1.5% Peroxide
300
tIfIlfIrwIfIfl
25
:J
c
~90
70
10
JIll. 6. fflilowllll tWla of ~iIIfIGebM

(B5"C, 9j'YolUl.) eOIIIIltimrs (I8).
95
5% Peroxide
1 % Dithionite
i-
~120
'S; 115
..0
Q)
110
:;:::
Q) ~105
..>
as 100
Q)
a:
95
90
-+-
250
5% Peroxide
.......
450
500
Wavelength,
nm
550
15
....
'0
0
UJ
0
a..
10
5
Fig.7.
100C, 0% R.H.
10
20
30
40
Accelerated aging time, h
Yellowlllg ",ta of peroxUIe-61Me1lM

(100 .c, O%R.H.) COII4itimts (I8).
..
~tblolllte-iIIfIGebM
m1HI1IIul
90
JIfIIp "ruler
tIfIlfIratetl
shown in Fig. 9, increases at about 360 nm

and decreases at about 430 nm (27, 29);
that is, photobleaching
occurs at 360 nm
and brightness reversion occurs at 430 nm.
The reflectance
changes observed
by
Claesson et al. (29) and Leary (27) are attributable to changes in light absorption
caused by chromophores
fonned during
exposure of the paper to UV light.
These results raise the critical question
about the structure of chromophores that
cause brightness reversion at wavelengths

> 400 nm and that are photobleached
at
360 nm. Both Claesson and Leary observed
an increase in the reflectance of newsprint
irradiated at 350 nm. This increase can be
attributed to photooxidative cleavage ofthe
coniferaldehyde
carbon-carbon
double
bond in newsprint lignin (see Scheme 2),
which causes the absorption maximum to
shift from 350 to 280 nm. Claesson found
no such reflectance increase after high-yield

0
C)
~(:;j-
194
Pulp Bleaching
-20
I
I
I
I
I
CL
-40
~I-
;r
/'"'"
'-/
\
\
~-60
t>
;r
,t, I
/
I
-Principles
and Practice
40
/,...,--
CL
193
I
I
C)
Na2S03 Charge,
% on wood
-1
---
~
.......
C\I
20
'.L
<I
-80
350
400
Wavelength,
300
250
450
nm
500
550
260
340
420
500
Wavelength, nm
580
Fig. 11. Effect of ~

IitM Oft lbe ebtmp 1ft lIgblllbsorptlml coe./ftdetll (MI) of blMebetl TMP. Tbe
tJIIlws Jltlf'elllbeus iIefto~ btnIrs oflrrruUlllUm lime. (31,34).
I"
bisulfite add to the carbon-carbon double

bond of coniferaldehyde (Scheme 3), causing the absorption maximum to shift from
350 to about 280 nm and light absorption
to decrease ( increased reflectance) at 350
nm (Fig. 10) (31). Therefore, irradiation of
bisulfite liner with UV light did not increase
the reflectance
at 350 nm because the
coniferaldehyde
unit had previously reacted with bisulfite.
Leary (32) proposed that an o-quinone
Hc o
is the yellow product formed in the photooxidation of lignin in paper based on the
O=CH-CHoO observed demethylation of lignin during
,_
the light-induced yellowing of newsprint.
VOMe
Evidence for the formation of o-quinones
during the UV irradiation of lignin models
O-lignin
has been provided by Un and Kringstad
(28). They observed that the reduction
of II cmdfertdllebytle lIgdifference spectrum of vanillin treated with
bisulfite liner was irradiated with UV light

(29). This difference in response of highyield bisulfite liner and newsprint to irradiation with UV light may be traced to the
reaction of bisulfite with the coniferaldehyde group in lignin as reported
by
Gellerstedt (30). Sodium sulfite and sodium
O-lignin
Scheme 2. Pbo/~
","."".
sodium periodate and that of vanillin irradiated with near-UV light are nearly identical, suggesting that photooxidation
of
vanillin produces a quinone similar to that
known to be formed by sodium periodate
oxidation.
Solid state 31p NMR spectroscopy of mechanical pulp derivatized with trimethyl
phosphite has provided more direct evidence for the formation of o-quinones in
light-induced brightness reversion (33).
When applied to refiner mechanical pulp
(RMP), this derivatization treatment led to
a decrease in the specific absorption at 457
nm before and after UV irradiation (fable
2), indicating that trimethyl phosphite had
reacted with chromophores in unirradiated
and irradiated pulp resposible for most of
the color. The chemical shift in the solid
Q
"'"
OMe
O-Lignin
Scheme 3. AJl411Umof sodl_
.""
(30).
O-Lignin
O-Lignin
bls8lflte 10 tbe CIIrlHmyl-crmJ.glltM etbylenk
Sample
Untreated
4. RHcIIorI
49
Trimethyl phosphitetreated RMP

Irradiated
13
186
RMP
Irradiated and trimethyl

phosphite-treated
RMP
~o
~o
o_rl__OMe
O_P.
/~o
MeO
MeO/'-OMe
31p NMR CHEMICAL
SHIFT, -45 ppm
Scheme
RMP
6'"
(MeOhP
O-Lignin
group 'It II COftifemlllebytle
Specific
Absorption at
457 nm (cm2/g)
Lignin
Lignin
O~
state 31p NMR of pulp "labelled" with

trimethyl phosphite (-11 ppm) was consistent with the formation of the cyclic phosphate triesters from o-quinones as shown
in Scheme 4.
oftrimetbyl
pbopbIIe
wllb 11fto-tl'IItU1IWId
31 P NMR CHEMICAL
SHIFT, 11 ppm
lIpl"
.""
(33).
42
Chapter m 5: Chemistry of Brightness Reversion and its Control
195
1%
40
Untreated
C)
20
-20
.::t:.
.....
C\I
C)
E -40
.::t:.
.....
C\I
-60
E -20
~
<! -40
TMP brightness
Unbleached
-80
Bleached
57"k
C=O
in BTMP
I
77%
/"
NaBH4-reduced
'/
-60
-100
320 - 330 nm
-80
250
300
350
400
Wavelength,
Fig. 12.f/t of~
C=Ofrom
irradiation
550
250
300
coe.fllcie18t (i(tl).j,_)
ofTMP (31).
IN light. Similar changes in the absorption

spectrum have been observed after IN irradiation of bleached CTMP except that the
extent of light-induced brightness reversion
of these pulps at 420 nm is about 30% less
than that ofTMP (31). Another striking
change in absorption caused by the IN irradiation of bleached TMP and CTMP occurs at 330 nm (31, 34, 35) and is shown
forTMP in Fig. 11. After treatment of photochemically yellowed bleached TMP with
sodium borohydride, the specific absorption above 400 nm is reduced to the original value
(t.e.,
MI:
= 0)
as seen
in Fig. 13
(35). Also, the absorption maximum at 330

nm, attributable
to aromatic ketones in
lignin (37, 38), decreases to a minimum
because chromophores produced by IN irradiation and those initially present in the
pulp are reduced. These results indicate
that, in addition to o-quinones, aromatic
o;
HC=O
H""",oOH,-OOHI
,
OMe
Q-Lignin
350
400
450
500
550
600
Wavelength, nm
nm
blMd1hlg 018tile d1tItIt.!'" Ilgbt"'-"Plfml
Light-induced reversion of bleached pulps

Figure 11 shows the effect of near-lN irradiation on the light absorption of peroxide- bleachedTMP (31, 34). The shoulder
at 420 nm is consistent with results obtained
for unbleached mechanical pulp. However,
in the 320-350 nm range, the specific absorption increases because of the formation
of aromatic carbonyl groups (35). In contrast, the light-induced brightness reversion
of newsprint made from unbleached stone
groundwood is accompanied by an increase
in light absorption at about 420 nm and a
decrease in light absorption at 350 nm (27,
29). As stated earlier, the photobleaching
of unbleached mechanical pulps observed
at 350 nm has been attributed to oxidation
of the conikraldehyde
group in lignin. The
light absorption of peroxide-bleached TMP
at 350 nm increases instead of decreasing
after exposure to IN light because, during
bleaching,
alkaline hydrogen peroxide
cleaves the carbon-carbon double bond of
the coniferaldehyde group in lignin (36) as
illustrated in Scheme 5. Cleavage of the
coniferaldehyde
carbon-carbon
double
bond is accompanied by a large decrease
in the light absorption oITMP at 350 nm as
shown in Fig. 12 (31).
Light absorption at wavelengths greater
than 400 nm is responsible for the yellow
color of lignin-containing paper exposed to
500
450
H
HOCH2C=O
OMe
carbonyl groups are produced during the

irradiation of bleached TMP and CfMP.
4.2 Role of oxygen in light-induced yellowing

Van denAkker et aL (26) and Leary (27)
have found that oxygen affects the light-induced yellowing of wood fiber. However,
these researchers observed differences in
the effect of atmospheric oxygen on lightinduced yellowing. Van den Akker et al.
(26) found that for a given IN irradiation
of groundwood pulp, the brightness loss
was 6.8 points in nitrogen and 10.1 points
in air. Leary (27), however, found that irradiation of newsprint in a vacuum or in the
presence of nitrogen or carbon dioxide did
not cause any significant yellowing after
irradiation of up to 500 hours. The yellowing in an nitrogen atmosphere observed by
Van denAkker may be attributed to incomplete removal of oxygen from the wood fiber or to the formation of chromophores
through reaction pathways not involving
oxygen.
Un and Kringstad (28) confirmed Leary's
results by irradiating a solution of milled
wood
O-Lignin
Scheme 5. ReMUoIt of" bytltvperoxlde IUIImt wltb

etbylelllc IHnuIhi COJIIf_lilebyM
tWbu:1fmI 018tbe cbtmge hi IIgbt absorplfml coe.fllcie18t (MI) of}letYJ#Fig. 13.Ejft of so4I8m ~
Ide-bletu:bed, pbotoyellouJeil TMP (35).
(36).
lignin
(MWL)
in methyl
cellosolvel
water. Under vacuum, this solution produced no color; but, when opened to air
and irradiated, it produced the same amount
of color as a similar solution of milled wood

lignin initially irradiated in air. The effect
of oxygen on the light-induced yellowing
of newsprint is further illustrated by its accompanying effect on methoxyl content.
Leary found that the methoxyl content of
newsprint irradiated in a vacuum decreased
by only 0.1 %,but the same irradiation in air
reduced the methoxyl content by 0.4%
(27).
It has been proposed that singlet oxygen,
formed by energy transfer from the triplet
excited state, abstracts a hydrogen atom
from phenolic hydroxyl groups to produce
the phenoxy free radical, the precursor of
the chromophore
contributing to yellowing (39). However, this reaction does not
appear to occur during the light-induced
yellowing of paper. Exposure of lignin-rich
paper containing mechanical pulp to singlet oxygen does not cause yellowing (40,
41). Indeed, a slight bleaching is observed.
The limited permeability of oxygen into
the fiber wall has been demonstrated (42).
In that study, the quenching of triplet excited states by oxygen was used as a test to
determine if oxygen uniformly penetrates
paper fibm.~e ~ts

indieak that roomtemperature phosphorescence of CTMP
was reduced but not eliminated as the air
pressure was increased from 0 to 760 torr.
--
Chapter m 5: Chemistry of Brightness Reversion and its Control
--s$l _ -Q
~
ROO.
OMe
198
. . hU
Ligmn
197
ooR
'.:::::-
OMe
II
(1)
+ RooH+ MeOH
0
(2)
RO-
H or alkyl
L = Lignin
Sebeme
hv
6. O$Id4tknr
of II pI1etwxy
rtUlktll
to
O-lfIIlrumoid
IIpm
by pnwty
."It
rtUlktIls
""
..
RH + 02
L=Lignin
.
ROO-
ROO- + RH
Rhv or!!.
-CZ
Mn+
RO _
+ HO
RO -
+ -OH +M(n+1)+
Sebeme 7. '/'be tWdiofI Sl!IpU!fffor tbe tUIIoxItl4IIfJt!jomuIIUm of ~I
4.3 Mechanism of the light-induced

yellowing process
Formation of phenoxy free radicals
The initially formed o-quinonoid strUctures believed to contribute to light-induced
yellowing as illustrated in Scheme 6 (43)
are formed by the reaction of peroxyl radicals, ~roduced by the reaction of light.gen.
erated alkyl free radicals with oxygen as
seen in Scheme 7. The following five reaction pathways (illustrated in Schemes 8 and
(3)
OMe
+ ROOH
_
M = Transition metal
Had oxygen been able to completely penetrate the fiber wall, phosphorescence
should have been fully quenched. Therefore, some photochemical
reactions may
occur in pulp fiber in the absence of oxygen.
In a study of the reaction of guaiacoxy
free radicals with ambient oxygen (43), it
has been found that the formation of yellow chromophores
from phenols occurs
only in the presence of carbon-centered free
radicals, molecular oxygen, and phenoxy
free radicals.
LO~L
= Photo-excited structure
R = H or alkyl
SebertIe8. FomuItW8of ~
rtUlIt:Mstlmnlgb direct tIIUIlrullrectllgbt-Irulltcedhomolytic elHvage of II
pbetwlk by""-,yl grotIJI.
HOO - + R -
R- + 02
ROOH
OH
(43).
*0
9) account
tIIUI1I~1
for the formation
rtUlktlls.
of the phenoxy
free radical:
1. Direct absorption of light by phenolic chromophores
(Scheme 8, reaction 1) (44)
2. Abstraction
of a hydrogen atom from the
phenolic hydroxyl group (Scheme 8, reaction 2)
3. Abstraction
of a phenolic hydrogen atom
by a triplet excited state carbonyl group
(Scheme 8, reaction 3)
4. Cleavage of the g.Q..4 aryl ether bond of
the singlet and triplet excited state of the
phenacyl aryl ether group (Scheme 9, reaction 1)
5. Abstraction
of a benzylic hydrogen atom
to form a ketyl free-radical followed by the
facile cleavage of the s-o-4 aryl ether bond
(Scheme 9, reaction 2).
Phenolic
units as chromophore
precursors
The role of the phenolic hydroxyl group

in photoyellowing
has been convincingly
demonstrated by the pioneering work of

Singh (45) and Leary (27) in which replacement of the phenolic hydroxyl hydrogen
atom by a methyl or acetyl group was found
to decrease the light-induced yellowing of

newsprint. The extent of yellowing can be
decreased by 15 to 20% (27, 34) after methylation of unbleached
and peroxidebleached TMP. However, methylation does
not affect the rate of yellowing (34, 44).
Similar effects have been reported by Gierer
and Lin (46) after they first methylated
milled wood lignin with diazomethane.
Yellowing was inhibited but, as with newsprint, was not completely prevented.
Phenolic groups in lignin absorb UV light
at wavelengths > 300 nm to produce a
phenoxy free radical that in turn produces
yellow chromophores as shown by reaction
I in Scheme 8. Although monomeric
phenols have very low light absorption
above 300 nm, conjugated phenols absorb
a moderate amount of UV light in the 300330 nm range (47). For example, conjugated biphenyl-type lignin model phenols,
adsorbed on cellulose paper, yellow when
exposed to UV light at wavelength > 300
nm (47). Biphenyl structures are initially
present in lignin and have been proposed
to arise from the reaction of light-induced
phenoxy free radical with neighboring ar0matic groups (48).
Recently, it has been shown that mechanical pulping can give rise to a precursor of light-induced yellow chromophores
(49): Lignin contains at least 18 phenylcoumaran units per 100 phenylpropane
units (49,50) 11\ddisc refining of pulp

samples impregnated with phenylcoumaran
models produces
the corresponding
diguaiacylstilbene compounds (49). When
absorbed on cellulose paper, the latter

compounds undergo rapid light-induced
yellowing (47). Non-phenolic
stilbenes
photoyellow less than phenolic stilbenes.
Phenoxy radicals can also be formed by
abstraction of a hydrogen atom from a phenolic hydroxyl group by hydroxyl or alkoxyl
radicals as illustrated
in reaction
2 of
Scheme 8. These latter radicals may arise
by light-, heat-, or metal-induced homolytic
cleavage of hydroperoxide
structures
formed in autoxidation reactions or by the
coupling of previously generated alkyl radicals with molecular oxygen (Scheme 7).
The effect of oxygen removal, carbonyl
group reduction, and phenolic hydroxyl
group alkylation or acetylation in lowering
the rate and extent of light-induced yellowing has been explained by Leary (27),
Kringstad and Lin (28, 51), and Gierer and
Lin (46) and is shown as reaction 3 in
Scheme 8, which is thought to proceed by
initial excitation
of the carbonyl chromophore and intersystem crossing to the
triplet state. The triplet excited state carbonyl abstracts hydrogen from a neighboring phenolic hydroxyl group to produce a
ketyl-phenoxy
free radical system. The
phenoxy free radical is then oxidized to
chromophore structures.
Evidence for the mechanism involving
abstraction of a hydrogen atom from the
phenolic hydroxyl group was first obtained
by Kringstad and I.in (51) prim1i'ily thMu~
experiments with the appropriate
lignin
models. ESR spectra, attributed to the appropriate phenoxy free radical, were ob-
199
200
duced yellowing shown by reaction 3 in

Scheme 8.
Non-phenolic (etherified) units as color precursors
MeO
MeO
MeO
The failure of etherification or esterification of the phenolic groups in lignin to totally inhibit
light-induced
yellowing
ultimately led to the identification of two
additional pathways involving non-phenolic
guaiacyl propane-s-0-4 aryl ether structures
containing a<arbonyl and benzyl alcohol
groups (reactions 1 and 2 in Scheme 9) that
account for most of the light-induced color
formation.
MeO
M~J?
~M~
MeO
'60
MeO
MeO
4
Fig.14. Up'" __I
~M~
J9l"2
flew- (46).
served
when solutions
containing
a
non-phenolic
aromatic aldehyde (3,4,5trimethoxybenzaldehyde
or veratraldehyde)
and a phenolic compound (syringyl alcohol, vanillyl alcohol, catechol, or phenol itself) were irradiated with near-W light.
Separate irradiation of the aldehydes or
phenols did not produce any free radicals
or yellowing. The inability ofthese phenols
to absorb W light at the wavelengths used
in this experiment (jOO-4OO nm) suggests
that phenoxy free radicals produced by the
abstraction
of hydrogen from phenolic
groups by photo-excited
carbonyl struc-
tures may play an important part in the lightinduced yellowing of lignin. Brunow and
Sivonen (52) have obtained similar results
using a phenolic lignin model compound,
ethyl guaiacyl carbinol. This compound did
not undergo oxidation when irradiated with
near-UV light until p-methoxyacetophenone, a triplet sensitizer, was added to
the solution. When the molar ratio of pmethoxyacetophenone
to ethyl guaiacyl
carbinol was increased from 0 to 0.32, the
rate of photooxidation
of this benzyl alcohol also increased. The above results are
consistent with the mechanism of light-in-
8-0-4 structures
containing
a-carbonyl
groups
Gierer and liD (46) have shown that the
non-phenolic
phenacyl-a-O-aryl
ethers,
a-guaiacoxyacetoveratrone
[1], a-guaiacoxy3,4-dimethoxypropiophenone
[~], and
a-guaiacoxy-B-hydroxy-3,
4-dimethoxypropiophenone
[3.] (Fig. 14), are rapidly
discolored after irradiation with near-W
light. Irradiation of these lignin models
produced
the corresponding
ketones,
(acetoveratrone and dimethoxypropiophenone) and ketols,(a-hydroxyacetoveratrone
and a-hydroxydimethoxypropiophenone)
from 1 and ~ and, in all cases, guaiacol. The
formation of these products can be explained by the light-induced cleavage of the
B-aryl ether bond to produce a phenacylphenoxy free radical pair, as shown in reaction 1, Scheme 9. Guaiacol and the aketone are produced through hydrogen
atom abstraction
by the guaiacoxy and
phenacyl free radicals; the ketols are formed
by reaction of the phenacyl free radical with
ambient oxygen. The corresponding structural isomers, B-keto-a-O-aryl ether [1] or
a-keto-yO-aryl ether [2], shown in Fig. 14,
are unaffected by irradiation with near-W
light. The formation of guaiacol, ketones,
and ketols as monomeric products of lightinduced cleavage of the a-aryl ether bond
of phenacyl-a-O-aryl ethers in solution and
!ldsorbed on cellulose have been confirmed
byVanucci and co-workers (53).
Because light-induced cleavage of the aaryl ether bond of the phenacyl aryl ether
moiety of lignin is a pathway to paper yellowing, it is essential to understand the effects of chemical and physical environment
on the extent of bond cleavage and the relationship of bond cleavage and yellowing.
The effect of protic as against aprotic solvents on the photochemistry
of the
phenacyl aryl ether bond has been determined using a-guaiacoxyacetoveratrone
as
a model. The cleavage of the phenacyl aryl
ether bond occurred through both the singlet and excited states of the carbonyl chromophore (54-58). In aprotic media the
triplet excited state of the phenacyl aryl
ether is unreactive; only the singlet excited
state undergoes aryl ether cleavage (54-56).
Aryl ether cleavage occurs in a protic environment through both singlet and triplet
excited states (54-56). This result is significant because the fiber wall in wood and
pulp, which is composed of cellulose,hemicellulose, and lignin, is highly protic.
8-0-4 structures containing benzyl alcohol
groups
Sequential reduction and alkylation of
TMP (59) and peroxide-bleachedTMP
(35)
effectively lowers the light-induced yellowing of these pulps. However, photostabilization is incomplete and only temporary
so that, with continuing
irradiation,
photoyellowing ultimately occurs (35). Although the forgoing results confirm the
roles of aromatic carbonyl and phenolic
hydroxyl groups in the initial stages of lightinduced yellowing, they also indicate that
other structures may contribute to yellowing as part of another reaction pathway.
One such possibility is illustrated by reaction 2 in Scheme 9.
The steps in this reaction sequence consist of the formation of a peroxyl free
radical from the combination of a carboncentered lignin free radical and oxygen, a
typical first stage in the oxidative degradation of polymeric materials (see Scheme 7).
The peroxyl radical then abstracts a benzylic hydrogen atom from a guaiacylglycerol-i?raryl ether forming a ketyl free
radical and the hydroperoxide.
The ketyl
free radical is converted to an aromatic ketone with accompanying elimination of a
201
202
(2)
~L
OMe
ROO-
/~OMe
OL
. =Excited state
L = Lignin
Scbeme 9. JIormIlUort of~

rtIIllads tbrougb IIgbt-t'""'-l
fl-0-4 etber ""tts (35, (1).
phenoxy free radical. This reaction pathway accounts for the light-induced formation of aromatic carbonyl groups that cause
an increase in specific absorption at 330 nm
for both unmodified, bleached TMP and
sodium borohydride-reduced,
bleached
TMP (31, 35). Also, analysis of mechanical
pulp photodegradation
products indicates
the formation
of 3-hydroxypropioguaiacone, an expected product of f?rO.4-aryl
ether cleavage (60). The proposed formation of ketyl free radicals by abstraction of
a hydrogen atom from a benzylic alcohol
group followed by f?rO.4-aryl ether bond
cleavage is further supported by results
obtained by Scaiano (61) showing that the
t-butoxy free radical generated by the photolysis of t-butyl peroxide abstracts the
benzylic hydrogen atom of l-phenyl-2phenoxyglycol
to produce the ketyl free
radical which in tUrn undergoes B-aryl ether
cleavage yielding acetophenone
and phe-
- Principles
and Practice
lignin, a one order of magnitUde decrease.

Because the carbonyl content of lignin is
only about 400 J.UDoVg, cleavage of the
phenacyl aryl ether bonds cannot account
for such a large loss of f?rO.4-linked guaiacyl
units.
In summary, three concurrent chemical
changes in the composition
of lignin in
photo-yellowed
bleached TMP lend credence to validity the proposed mechanism:
(1) A net increase in aromatic carbonyl
groups: this is observed during the lightinduced yellowing of untreated, bleached
TMP, sodium borohydride-reduced,
bleached TMp, and reduced and methylated bleachedTMP (31, 35).
(2) An increase in phenolic hydroxyl content:
although phenolic hydroxyl groups are
oxidized during yellowing, a three-fold increase in phenolic hydroxyl groups is
found on UV irradiated bleachedTMP that
was reduced and methylated (35).
(3) Near-UV irradiation of bleached TMP for
24 hours decreases the S-O 4-linked
guaiacyl groups by an order of magnitude
(62).
CH20H ,
H?-0-1
Pulp Bleaching
bomolytk
cleilfJllgeoftbefl CoOIKnul In tbe
nol through the enol and phenoxy free

radical.
Evidence for the light-induced degradation of 8-O-4-guaiacyl ether bonds is provided by the effect of UV irradiation on the
phenolic hydroxyl content of reduced and
methylated bleached TMP. UV irradiation
of methylated bleachedTMP for thirty hours
increased the phenolic hydroxyl content
from about 0.58% to 2. 13%.The same irradiation of methylated and reduced bleached
TMP increased the phenolic hydroxyl content from 0.66% to 1.59% (35). This is consistent with the cleavage of B-O-4 ether
bonds to release phenolic groups.
Further evidence for the cleavage of B0-4-aryl ether bonds in lignin units containing a benzylic alcohol group is provided by
the results of Pan et al (62). It\di~1tin.g
that irradiation of bleached TMP for 24
hours lowered the content of B-O-4-linked
guaiacyl units from 1003 to 149 J.UDoVgof
Formation of o-quinonoid structures

Quinonoid structUres have been proposed as comprising the colored products
formed during the initial stages of light-induced yellowing (32). This proposal has
been confirmed both by the analysis of
products formed in model compound photolysis (30) and solid state 31pNMR of phosphorous labelled lignin-containing
pulp
fibers that were previously irradiated (33,
63). However, there has been no definitive research on the mechanism
of 0quinone formation. Initially, the formation
of o-quinone structUres was represented
through the oxidative demethylation
of
phenoxy free radicals by molecular oxygen
(27) as the ground state triplet or by the
excited state singlet (39). Recently, however, it has been shown that the exposure
of mechanical pulp handsheets to a stream
of singlet oxygen does not yellow the sheet
(40, 41). Also, the introduction of ground
state triplet oxygen into a solution containing guaiacoxy free radicals has no effect
(43). It is therefore unlikely that either of
these oxygen species participates

in 0quinone formation. However, combining
a alkyl free radical with molecular oxygen
and the guaiacoxy free radical does immediately produce color (43). This color is
attributed to the formation of o-quinonoid
groups formed by a reaction of peroxyl free
radicals with a phenoxy free radical as seen
in Scheme 6.
4.4 Inhibition of light-induced yellowing

The diverse approaches available for controlling the light-induced yellowing of paper have been outlined by Leary (64). The
following review summarizes the degree of
success achieved when paper is subjected
to specific types of stabilizing treatments.
Modification of functional groups in lignin
The first efforts to inhibit photochemical yellowing of lignin-containing
paper
were based on the belief that the dominant
reaction pathways leading to chromophore
structUres were reactions 1-3 in Scheme 8,
and reaction 1 in Scheme 9. The approaches
used to inhibit these reactions were modification of lignin by etherification or esterification of the phenolic hydroxyl groups,
reduction of the aromatic carbonyl groups,
combined etherification
of phenolic hydroxyl and reduction of aromatic carbonyl
groups, and hydrogenation of vinyl groups.
Etherification and esterification the phenolic hydroxyl groups:
The objective of early research was to
stabilize newsprint to UV irradiation by
masking (t.e., blocking) phenolic hydroxyl
groups with alkyl or acyl groups. Singh (45)
and Andrews and Singh (65),and Leary (27)
were the first to observe the effects of
etherification and esterification of phenolic
hydroxyl groups on the rate and extent of
light-induced yellowing of newsprint. Methylation and acetylation decreased the extent of yellowing but did not appreciably
affect its rate. Andrews and Singh (65)
claimed that unbleached
and bleached
stone groundwood
pulps, methylated with
dimethyl sulfate or benzoylated with benzoyl chloride had a lower degree of lightinduced yellowing
after one hour of

near-UV irradiation than did the corresponding unmodified pulps. Similar results were
obtained by Francis et al. (66) and Schmidt
and Heitner (34) for benzoylation and alkylation of spruce TMP.
Conventional alkylation or acylation (t. e.,
blocking) of phenolic groups in lignin does
not completely eliminate the light-induced
yellowing of (chemi)mechanical
pulp because new phenolic groups are formed during exposure to near-UV light (see Scheme
9). In this connection, Castellan et al. (67)
have found that etherification or esterification of bleached CfMP in the presence of
cationic phase-transfer catalysts leads to significant decreases in the degree of light-induced yellowing compared to the same
treatments without the phase-transfer catalyst. However, the improved photostability
of these pulps was accompanied by a catastrophic decrease in interfiber bonding and
lower paper strength. Apparently, phase
transfer catalysts increase the reactivity of
the alkylating and estefing agents so that
they also react with cellulosic hydroxyl
groups that contribute to interfiber bonding. If cellulosic hydroxyl groups are
etherified or etherified by phase-transfer
catalysis, then it is reasonable to assume that
other non-phenolic hydroxyl groups, such
as primary and secondary (benzyl) alcohol
groups are also alkylated or acylated. Such
reactions would retard the cleavage of the
8-O-4-aryl bond of guaiacylglycerol-B-aryl
ethers (Scheme 9, reaction 2), thereby explaining why phase-transfer
catalysis of
methylation or acetylation is more efficient
in inhibiting light-induced yellowing than
the non-cataIyzed treatment. In this connection, others have shown that the lightinduced yellowing of lignin-containing
paper can be completely inhibited by acetylation with acetic anhydride without adversely affecting its strength (68). In this
case, acetic anhydride acetylates both phenolic and benzylic hydroxyl groups in lignin, so that the formation of phenoxy free
is prevented.
Reduction of aromatic carbonyl groups:
Carbonyl groups were recognized at the
early stages of research on light-induced
r.ulic'Als
203
yellowing as being likely participants in the

reactions leading to the formation of chromophore structures. Reaction 3 in Scheme
8 and reaction 1 in Scheme 9 involve carbonyl excited states. Therefore, reduction
of carbonyl groups with, for example, s0dium borohydride should lessen light-induced yellowing by eliminating both of
these reactions. The reduction of carbonyl
groups in unbleached mechanical pulps
does in fact appear to be successful in lowering the rate of yellowing (27, 59). For
example, treatment of newsprint with s0dium borohydride increased the time for
complete yellowing from 500 to 1200 hours
(27). On the other hand, the rate of lightinduced yellowing of peroxide-bleached
TMP reduced with sodium borohydride was
the same as that of unreduced bleachedTMP
(31, 66, 69). Apparently, light-induced yellowing of bleached TMP can occur without
the participation of carbonyl groups.
Hydrogenation of vinyl groups:
Un and Kringstad (28) have demonstrated that sodium borohydride reduction
followed by heterogeneous catalytic hydrogenation prevents the light-induced yellowing of methyl cellosolve solutions of milled
wood lignin. In contrast, Castellan et al.
(67) have found that sodium borohydridereduced milled wood lignin (MWL), hydrogenated over a Pd/C catalyst, yellowed
significantly after near-UV irradiation in a
hydroxypropylcellulose
film. This disagreement may be caused by one or a combination of factors including differences in the
reaction media, light sources, and wood
species. Castellan et al. (67) did find that
catalytic hydrogenation of MWL, bleached
with hydrogen peroxide and reduced with
sodium borohydride, decreased the extent
of yellowing.
Successful
hydrogenation
of vinylic
groups in solid materials such as TMP requires a homogeneous catalyst. However,
hydrogenation
of vinyl groups with a
soluble (RhCI(pPh3)) or a heterogeneous
(PdJC) catalyst does not dimhUsh l!ght-Induced yellowing (59); hydroboration and
reaction with diimide are equally ineffective in these particular situations (59). Cata-
204
lytic hydrogenation,
hydroboration
with
diborane,or reduction with diimide may not
have completely
eliminated the vinylic
double bonds in the pulp fiber.
Sequential reduction of carbonyl groups
and etherification of phenolic hydroxyl
groups.
That both carbonyl and phenolic hydroxyl groups may play a direct role in lightinduced yellowing has led to the strategy
of preventing light-induced yellowing by
sequentially reducing carbonyl groups and
etherifying phenols in lignin. Tschimer and
Dence (59) found that sodium borohydride
reduction of spruce TMP followed by complete alkylation with dimethyl sulfate, propylene oxide, or diazomethane completely
prevented light-induced yellowing for up to
2 hours. This series of treatments has been
proposed as two segments of a three-stage
process designed to inhibit light-induced
yellowing (70). The three-stage treatment
is composed of reduction with sodium borohydride followed by hydroxypropylation
(i.e., etherification) with propylene oxide.
The treated sheet is then coated with a fluorescent inorganic material.
Paper thus
treated shows a decrease in the extent of
light-induced yellowing after an undisclosed
time of exposure to near-UV light.
Although a combination of etherification
of phenolic hydroxyl and reduction of carbonyl groups delays yellowing for up to 2
hours no information is available on the
effect'of long-term exposure of treated paper to UV light. Figure 15 shows the effect
of reduction and methylation of bleached
TMP on the change in specific absorption
at 420 nm (35). Reduction and methylation delays yellowing for 1.5 hours, results
that are similar to those of Tschimer and
Dence (59). However, after 1.5 hours of
near-UV irradiation, yellowing, as measured
by ~420' increases at about the same rate
as that for untreated paper. As illustrated
by reaction 2 in Scheme 8, cleavage of the
B-O-4-aryl ether bond in the guaiacylglycero\-P.-ary\ ether lignin. unit produces
phenoxy free radicals which in turn are
oxidized to colored chromophores.
This
means that reduction of carbonyl groups
and etherification
of phenolic hydroxyl
groups in lignin only delay yellowing for a
short time or until phenoxy radicals are
formed in the ether cleavage reaction. Successfullong-term inhibition of light-induced
yellowing requires a method that prevents
cleavage of the B-04-aryl ether bond and
oxidation of the resulting phenoxy free
radical.
Addition of Inhibitors
listed in the following sections are various types of paper additives that affect the
degree and rate of yellowing caused by exposure of paper to near-UV light.
UV Absorbers
mtraviolet absorbers, that is, compounds
that absorb UV light and dissipate the light
energy by a non-yellowing mechanism,have
been used extensively to prevent the lightinduced degradation of a wide variety of
polymers. It was recognized at the start of
research on this subject that compounds of
this type, decrease light-induced yellowing,
when added to a paper surface.
The effect of UV-absorbing additives on
the light-induced yellowing of groundwoodbased paper was first reported by Nolan
(71). In this study, sheets treated with
Eastman Ultraviolet Sensitizer required
twice the amount of UV exposure as untreated sheets to undergo a given brightness
decrease.
Hydroxybenzophenones
have been
widely used as UV light absorbers (72). This
type of compound absorbs UV light and
forms an o-quinonemethide
which dissipates the light energy
as heat by
tautomerizing
to the starting material as
shown in Scheme 10. Kringstad (73) has
found that the addition of 2-2'-dihydroxy-4methoxybenzophenone
or 2,2',4,4'tetrahydroxybenzophenone
to bleached
groundwood-based
paper decreases lightinduced yellowing.
Similar results have
been obtained by Gellerstedt et al. (74)
using 2,4-dihydroxybenzophenone
and by
Fomier de Violet et al (75) who used a series of 2-hydroxybenzophenones.
However,
achievement of 93% stability requires more
than a 4% charge ofUV absorber,an amount
too large and expensive for commercial use.
------
Chapter 11I5: Chemistry of Brightness Reversion and its Control

cal and convert
structure.
205
free radicals. Ascorbates, thiols, and
bic acid alone
thioethers all stabilize lignin in paper by

quenching peroxyl and alkoxyl free radicals,
species that oxidize the phenoxy free radi-
bic acid to bleached aspen CTMP increases

the specific absorption from 0.85 to 1.41
mZ;kg, but the addition of sodium sulfite
Polymeric inhibitors
Polyethylene glycol has been used to prevent light-induced yellowing of wood surfaces and paper (76, 77). Its effectiveness
in inhibiting light-induced
yellowing increases as its degree of polymerization increases from 2 to 90 (78). Although the
mechanism of polyethylene glycol inhibition of light-induced yellowing is not well
understood, it has been suggested that it
inhibits yellowing by excluding air from the
paper fibers (77).
Polyvinylpyrrolidone
(I>VP), used to improve the whiteness and gloss in paper coatings, as an additive in inks to prevent paper
slippage, and to improve the dimensional
stability of wood, also reduces light-induced
yellowing (79). The monomer, n-vinyl-2pyrrolidone,
and the lowest molecular
weight (molar mass 104) PVP are the most
efficient. It is has been proposed (79) that
the phenolic hydroxyl forms strong hydrogen bonds with the amide group ofPVP and
prevents
its oxidation
by alkoxyl and
peroxyl free radicals.
(Fig.
-Principles
17). Addition of a~or.
and Practice
50
.
Free radical scavengers

All five light-induced yellowing pathways
illustrated earlier in Schemes 8 and 9, involve a series of free radical reactions leading to a phenoxy free radical (27, 28, 35,
46, 61). Also, as illustrated in Scheme 6,
the phenoxy free radical reacts with peroxyl
radicals to form chromophore
structures
(43). The most successful methods for inhibiting light-induced yellowing of lignincontaining papers are those that scavenge
of
Pulp Bleaching
it to an o-quinonoid
Ascorbic acid and ascorbates

The inhibition oflight-induced yellowing
of lignin-containing papers by ascorbic acid
and sodium ascorbate was first reported 25
years ago (73). The ability of ascorbates to
inhibit light-induced yellowing may be understood by considering the relationship of
this biological antioxidant to (X-tocopherol.
Niki et al. (80) observed that an (X-tocopherol radical, generated by an alkoxyl radical, rapidly disappeared when mixed with
ascorbic acid, suggesting that ascorbic acid
reduces the phenoxy radical of (X-tocopherol. Similarly, ascorbic acid reduces
phenoxy radicals in Iignin-containing paper
produced by exposure to near-UV light.
BleachedTMP irradiated with near-UV light
exhibits a large ESR signal attributed to a
phenoxy radical which decreases after the
addition of ascorbic acid (81). The ESR signal attributed to phenoxy radicals was replaced by a new persistent signal assigned
to the ascorbyl radical.
When applied to a paper surface, ascorbic acid inhibits light-induced yellowing for
a finite time, (1-2 h) after irradiation with
near-UV light (34). With longer irradiation,
yellowing proceeds at the same rate as that
for the untreated paper (34, 75) as shown
in Fig. 16. This limitation has been attributed in part to photooxidation of the ascorbic acid. Besides undergoing air oxidation,
ascorbic acid is oxidized by photochemically produced peroxyl radicals, superoxide radical anions, and singlet oxygen (82,
83). If ascorbic acid is to be an effective
inhibitor of light-induced yellowing, its usefullifetime must be significantly increased.
Agnemo (84) has studied the effect of
bleached aspen CfMP treatment with ascorbic acid and sodium sulfite. From this work
it appears that, relative to the initial specific absorption, sodium sulfite and ascorbic acid addition
to paper decreases
light-induced yellowing no more than ascor-
Sebeme 10. Ligbt-ttUl.eeli t..tomertztltto"

Z-byi/lYJxy~.
206
40
!if
N"
E
<5
C\I
Untreated
Reduced + methylated
Methylated + reduced
30
20
<!
10
o
0.1
10
100
time, h
Irradiation
Fig. 15. Bffect of metbylatttm

atUl SOIII_ IJorobyllrltle retbu:ttorr Oft ebromopbore
IIgbt tmulItIttorr
of jIerrMiIe-bktIcbetl
61iu:1l S/Jf'1KoeTMP (35).
and ascorbic acid does not increase initial

light absorption. It appears that the function of sodium sulfite is to prevent the initial yellowing caused by the addition of
ascorbic acid (85).
J?
..
RSH
qSR
/1
HO
OH
II
(B)
RSH+
Qri"g
R"
0
"-
,/
R
II
_uv
Forsskahl (78) showed that thiols are one

of the more effective inhibitors of light-induced yellowing. In an intensive study on
the effect of impregnating
groundwood
paper with thiols, thioethers, and their derivatives, Cole et al. (87, 88) found that
when added to lignin-containing paper, thiols had both a bleaching
and photostabilization
effect. For example,
the
addition
of glycol dimercaptoacetate
(CHzCH/OOCCHzSH))
to peroxidebleached
cottonwood
CMP and thioglycerol
(HOCHzCH(OH)CHzSH)
to
peroxide-bleached
loblolly pine TMP increases brightness by 3.5 (88) and 5 (89)
percentage points, respectively.
A similar
Thiols
Aromatic thiols such as mercaptobenzothiazoles,
mercaptobenzimidazole,
Snaphthyl thiol, and alkyl thiols such as
dodecylmercaptan,
have been used effectively as stabilizers for a wide variety of
polymers (86). The fll"Stthiols used to inhibit light-induced yellowing of lignin -containing papers was sodium thiopropionate
(65). In a preliminary study, Janson and
(A)
~o
ftJf7l/lltttm
III
C=CH-C-R
Scheme 11. MIeHeI-type IIIIdIttorr oftbtols to"" o-q,d_
...
II
R-S-C-CH-C-R "'
I.
R
(A) atUl a.~-.ffStIhrf'tlte4lletOftes
(B).
207
208
45
3
C)
~
C\J
35
--
C!
N-
~25
s:::
c\I
:; 15
~<I
o Untreated
.D
CO
o
;;:::
0.01
0.1
1
Irradiation time, h
ng. 16.E.I1eet
of IISeOrlJkIICUIIlMlUort 011t:itrrnIuJp/Ior
blMll Sj1rIIeeTMP (34).
10
4rIrhIg _UV
100
IIgbt I~
. Ascorbic acid
'0Q)
. Na2S03
a.
. Ascorbic acid + Na2S03
en
-5
tmM-blMdJetl
o
+a.
...
of/')
o
o
of JIn'
group. Thus, bleached cottonwood CMF,

treated with glycol dimercaptoacetate,does
not loose brightness after five days' irradiation but glycol dimercaptopropionate,
(CH2CH2(OOCCHFH2SH)
loses about 6
brightness points. Molecular dimensions
are also important in the inhibition of yellowing: Polyethylene glycol dimercaptoacetate does not inhibit the light-induced
yellowing of bleached cottonwood CMP but
the monomeric
analogue, glycol dimercaptoacetate, is a very efficient inhibitor of
yellowing (88).
Solid-state ESR and CIDEP spectroscopy
have provided insight into the mode of inhibition by aromatic thiols (81). Near-TN
irradiation of unbleached and peroxidebleached TMP impregnated with aromatic
thiols causes a rapid increase in the formation thiol radicals. The time-resolved CIDEP
spectrum, however, shows a symmetric
broad band characteristic of the polarized
phenoxy radical. This result suggests that
aromatic thiols quench triplet-generated
phenoxy radicals in a secondary thermal
process.
Thioethers
Unlike
its
structural
analogue,
thioglycerol,
S-methyl-I-thioglycerol,
(CH3SCH2CH(OH)CH,oH), does not bleach
mechanical pulp but retains the ability to
4
Irradiation
6
time, h
Fig. 17. Bf/eet of IISeOrlJk lICUIiJU SOlUImt IIIIlftU lUIdlUort 011ebromopbore

ItTtIIIliIIItnI
bleaching effect has been observed by

Fornier de Violet et al. (75). Kutney (89)
has found that certain dithiols and mercapto
acids were effective bleaching agents for
mechanical pulps. This bleaching effect has
been attributed to Michael-type addition of
the thiOl to a, 8 -unsaturated ketones and
quinones as illustrated in Scheme 11. In
support
of this suggestion,
Lee and
Sumimoto have isolated Michael-type addition products from 3,4-dimethoxystilbenep-quinone
following irradiation
in the
presence of thioglycerol (90).
Besides their bleaching effect, glycol
dimercaptoacetate
and thioglycerol inhibit
light-induced yellowing oflignin-<:ontaining
papers (75, 87). It appears that the ability
of thiols to inhibit light-induced yellowing
is associated with their propensity to bleach
ultra high-yield pulps. The effectiveness of
thiol inhibitors depends on their molecular structure and size. For example, esters
of thiocarboxylic acids are better inhibitors
of light-induced yellowing than are their
carboxylic acid analogues (75, 87, 88). The
effectiveness of thiocarboxylate esters depends on the location of the thiol group in
the molecule relative to that of the carboxylate group: Thiol groups alpha to the carboxylate group are far more effective in
inhibiting yellowing than the same thiol
group located beta to the carboxylate
of~-b'MCIJM
fortlUltiOll
10
""rmg
18e"r-UV IIgbt
IISJHm TMP (70).
inhibit light-induced yellowing (87). It is

believed that the methylene hydrogens alpha to the electron-donating sulfide group
in S-methyl-I-thioglycerol
are readily abstracted by peroxyl radicals. Thioethers of
thiocarboxylic
acids, such as methylthioacetic acid, in which the sulfide group
is alpha to the carboxylic acid group are
effective inhibitors oflight-induced yellowing (75). When the sulfide group is situated beta to the carboxylic acid group, as
in dilauryl thiopropionate,
the thioether
does not inhibit yellowing (87). These results can be explained by assuming the
quenching of oxygen-based free radicals
with activated methylene hydrogen atoms.
The electron-donating sulfide group and the
electron-withdrawing carboxylic acid group
combine to enhance the hydrogen donor
character of thiocarboxylic acids and thus
promote free radical quenching.
Dienes
Cyclic dienes can act as quenchers of
photo-excited
aromatic ketones and residual quinones in mechanical and ultra
high-yield pulps. Several cyclic dienes,
I-methoxy-l ,3-<:yclohexadiene, I-methoxy1,4-cyclohexadiene,
1,4-dihydro-2-methylbenzoic acid and 2,4-hexadienoic
acid
inhibit light-induced yellowing to some degree (91). There appears to be a correla-
tion between the structure and effectiveness of diene inhibitors.

Trans,trans-2,4hexadien-l-ol
appears to be the most
effective inhibitor of all the dienes tested
thus far. However, the use of these dienes
to inhibit light-induced
yellowing has a
major disadvantage: their application
to
paper made from bleached CTMP accelerates thermal yellowing.
Formates and aldehydes
.Formates represent another type of hydrogen-donating group believed to be an
inhibitor of light-induced yellowing (92).
Sodium formate, together with a trace
amount (80 ppm) of Cu++or 0.1 % ascorbic
acid, decreases light-induced yellowing by
67% and 50%, respectively. Ascorbic acid
and Cu++are added to quench the superoxide radical anion which plays an active role
in the formation of chromophores.
Aliphatic aldehydes reduce p-quinones to
hydroquinones during irradiation with nearTN light (93). The application of acetaldehyde and propionaldehyde
to stone
groundwood and TMP partially bleached
with hydrogen peroxide both increases
their brightness and prevents yellowing.
Because the objective in applymg InlUbltors
to lignin-<:ontaining paper is to stabilize
brightness, the photo-bleaching effect may
be undesirable.
Irradiation
of partially

bleached mechanical pulps in the presence
of n-butyraldehyde
maintains brightness
levels constant for up to 30 hours but the
pulps are not bleached. The differences in
the photoreactivity of these aldehydes may
be structure-related.
5. Summary
The aging of lignin-containing pulps in
the dark is very likely caused in part by the
autoxidation of hydroquinonoid groups in
lignin. This explanation accounts for the
higher brightness reversion of dithionitebleached mechanical pulps compared with
unbleached or peroxide-bleached
pulps.
Dithionite
bleaching
occurs primarily
through the reduction of quinoid groups to
hydroquinones
(8) which are susceptible
to autoxidation leading to brightness reversion (17).
Thermal yellowing of peroxide-bleached
pulps during aging under ambient conditions, or after less than 16 hours of accelerated aging, occurs to a lesser degree than
that of dithionite-bleached
pulps. Peroxide bleaching oxidizes quinone groups to
carboxylic acids and lactones (20) which
contribute only slightly to thermal yellowing. The lower thermal yellowing of peroxide-bleached pulps compared with that
observed for dithionite-bleached pulps may
be attributed to the low amount of residual
hydroquinones in peroxide-bleached
pulps
available to undergo autoxidation to colored
quinones.
Treatment of pulps with chelating agents,
ethylenediaminetettaacetic
acid (EDTA) or
diethylenetriaminepentaacetic
acid (DTPA),
decreases thermal yellowing. This result
suggests that the presence of transition
metals promotes thermal yellowing. In particular, the presence of femc (Fe3+) ions
appears to promote the thermal yellowing
of unbleached
and peroxide-bleached
pulps. Apparently, dithionite-bleached
pulps have an abundance of easily oxidizable groups, (i.e., catechols) with the result
that Fe3+-cata1yzed autoxidation contributes
only minimally to the overall thermal yellowing of dithionite-bleached
pulps.
209
Cumulative research results show that

the light-induced yellowing of mechanical
and ultra high-yield pulps occurs by photooxidation of lignin in the fiber wall. The
phenoxy free radical, believed to be the
precursor
of o-quinonoid
structures
resposible for light-induced yellowing, participates in yellowing through at least five
reaction pathways.
1) Absorption ofUV light by conjugated phenolic groups
2) Abstraction of a phenolic hydrogen atom
by oxygen-based free radicals
3) Abstraction of a hydrogen atom from the
neighboring phenolic hydroxyl group by a
photo-excited aromatic carbonyl (triplet
excited state)
4) Cleavage of non-phenolic phenacyl-a-oaryl ethers
5) Abstraction of benzylic hydrogen by oxy~~ootainingfreeradic~mch~pero~
and alkoxyl to produce ketyl free-radicals
that undergo facile J3-0-4-aryl ether cleavage to phenoxy radicals and the corresponding guaiacyl-l.propanone.
Although there h~ been much progress
both in elucidating the reaction pathways
leading to yellowing of bleached mechanical and ultra high-yield pulps and in identifying the colored chromophores,
more
information is needed about the keyoxidation step in which phenoxy free radicals
are converted to quinones.
Four approaches have been used in attempting to inhibit light-induced yellowing
of lignin-containing paper:
1) Chemical modificatioo of lignin by alkylation or acylation of the phenolic hydroxyl
group
2) Reduction of aromatic carbonyl group and
hydrogenation of the vinylic C=C
3) Blocking near-UV light with UV-absorbing
compounds
4) Quenching of peroxyl and alkoxy free radicals with a hydrogen donating compound
Chemical modification only partially prevents yellowing because about 70% of the
light-induced yellowing of paper proceeds
through
homolytic
cleavage
of the
guaiacylglycerol-E-0-4-guaiacyl
ether.
210
Blocking the UV light interrupts the photochemical process at the first ~

and cleavage of the B-O-4-aryI ether bond does not
take place. However, ~ stated earlier, these
UV blocking agents are too costly to be applied commercia11y. Ascorbic acid, thiols,
thioethers, formates, dienes, and aldehydes
used to quench the peroxyl and alkoxy free
radicals do not prevent photodegradation
of the lignin macromolecule through cleavage of the g.o.4.aryl ether bond.
The stability of lignin-containing paper
to near-UV light might be improved if free
radical quenchers were combined with
compounds that prevent cleavage of the &0-4-aryl ether bond. Detailed knowledge
of the mechanism governing the inhibition
of light-induced yellowing by various reagents is essential if an economical method
to maintain pulp brightness and whiteness
is to be developed.
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83. Kwon, B.-M., Foote, e.S., Khan,
AmCbem.
Soc. 111:1854 (1989).
S.I., )
84. Agnemo,A.R.,
International
Patent Application PCT/SE91/00798,
Publication
No.
WO 92/09745 Oune 11,1992).
85. Ragauskas, A.J., Cellul.
28(3):265 (1994).
Chem.
Tecbnol.
86. Stepek, j. and Daoust,

H., Additives
Plastics; Springer, New York, 1983.
87. Cole, B.j.W and Sarkanen,
72'117 (1987).
for
K.V., Tappi]
88. Cole, B.j.W, Sarkanen, K.V., Hooper, j.E.,

"Sulfur-Containing
Pulp Brightness Stabilizers; Fourth International
Symposium
on Wood and Pulping Chemistry Proceedings,ATIP, Paris, 1987, Vol. 1, p. 321.
89. Kutney,
(1986).
G.W.j.
90. Lee,
D.Y.
Holzforscbung
(1991).
91. Ragauskas,A.J.,
Pulp
and
Pap. Sci.12(4).:J129
Sumimoto,
45 (Supplement):15
Tappi]
76(12):153
M.,
(1993).
78. janson, j. and Forsskahl, I., Nord. Pulp

Pap. Res.] 4 (3):197 (1989).
92.. Francis, R.e., Dence, CW, ,Alexander,TC

U. S. Pat. No. 5,080,754 Oan. 14, 1992).
79. Ratto, M., Forssk:\hl, I., janson,

1.., Tappt] 76 (6).-67 (1993).
93. Hirashima, H. and Sumimoto,

77(1):146 (1993).
J.. Vtikari,
M., Tappi]
SECTIONIV:
The Technology of
Chapter 1:
Thomas J. McDonough
Institute of Paper Science and Technology, Inc.
Atlanta, Georgia
1. Introduction
1.1 History
1.2 Process overview .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.3 Advantages and dissadvantages of oxygen
delignification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
215
216
216
217
2. Fundamental aspects of oxygen deUIV'Jflcation

217
2.1 Chemistry
218
2.2 Rates of reaction"and mass transfer. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
2.3 Heat effects, chemical consumption,
and reaction products.
226
3. Processes and equipment
. . . . . . .. . . . .. .. . .. . . .. .. . . . .. .. . . . .. . . . . . . ... 227
3.1 Medium-<:onsistencyprocesses
227
3.2 High-<:onsistency processes
229
3.3. Comparison of medium- and high-<:onsistency
systems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
4. Process variables. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
4.1 Time and temperature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2 Alkali charge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3 Oxygen pressure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.4 Consistency
232
232
233
233
234
5. Effects on mill operation.

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 234
5.1 Pulp washing before and after the oxygen
stage
234
5.2 Screening
5.3 Implications for the recovery system.
236
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
6. Pulp quality . .. . . .. . . . . . . .. . . .. . .. . . . . . . . . . . . .. . . . . .. . . .. . .. . . . . . . ...
213
237
Chapter IV 1: Oxygen Delignification
Chapter IV 1:
Oxygen
DeHgnification
1. Introduction
Oxygen delignification can be defined as
the use of oxygen and aIkaIi to remove a
substantial fraction of the lignin in unbleached pulp. The process is usually conducted under pressure, and delignification
is normally in the range of 35-50%. Oxygen
is usually applied to kraft wood pulps but
can also be used for sulfite, secondary fiber, nonwood, and other pulp types. In this
chapter, oxygen bleaching is considered
to be synonymous with oxygen deligni- .
fication.
The main benefits of oxygen bleaching
are environmental.They derive from the fact
that both the chemicals applied to the pulp
and the materials removed from the pulp
are compatible with the kraft chemical recovery system. This enables the recycling
of oxygen-stage effluent to the recovery
system by way of the brown stock washers, decreasing the potential environmental impact of the bleach plant.The decrease
is roughly proportional to the amount of
delignification achieved in the oxygen stage.
This applies not only to chlorinated organic
by-products, but also to other environmental parameters associated with bleach plant
effluents, including BOD, COD, and color.
The decrease in color, however, is larger
than expected on the basis of the lignin removed in the oxygen stage.
The industrial application
of oxygen
bleaching has expanded very rapidly in recent years.The first commercial system was
not started up until 1970 and total world
capadtyin 1980 was only about 10,000 tons
per day. By 1992 the number of operating
systetns stood at 155, with a total capacity
of about 85,000 tons per day, as illustrated
in Fig. 1 (1). Furthermore, this rapid growth
is likely to continue. As trends away from
the use of chlorine and chlorine-containing
compounds intensify, both technical and
economic considerations will mandate the
use of oxygen. Ozone, for example, though
it possesses certain advantages over oxygen,
will probably see application only in conjunction with oxygen. Oxygen will be used
to predelignify pulp to the point where the
necessary ozone charge becomes small
enough to be economical and selective.
1.1 History
The gestation period of commercial oxygen bleaching was a long one. It began in
1867 with the patenting of an "Improvement in Bleaching of Paper Pulp" by Joy and
140
~120
c:
~100
"C
ni
0
0
0.....
80
-:0
II
Single-stage systems
Two-stage systems
60
~40
'u
CtS
Co
CtS
c;)
20
0
1970
Fig. 1. WorUwUIe
prodlletlorl
1975
alJNldty
1980
of oxypn-tiBllpifled
215
1985
pulp.
1990
1995
216
NaOH
Steam
O2
Vent
gases
Wash
water
Pulp to
further
bleaching
Filtrate to
washing unbleached
pulp (recovery system)
Campbell (2) that involved passing heated

air through an agitated pulp suspension. In
a 1915 patent (3), Mueller advanced the
state of the art by providing for pressurized
operation and addition of an "alkaline earth
metal hydrate." Harris (4) and Marshall and
Sankey (5) disclosed further improvements
in 1954. During the period from 1956 to
1960, Nikitin andAkim (6) made a series of
contributions stemming from their interest
in combining the delignification and viscosity control steps of dissolving pulp manufacture. In 1960 and 1%1, Grangaard and
Saunders (7) patented additional improvements aimed at making the process more
commercially feasible.
Despite these advances, oxygen delignification remained uncommercialized.
The
main reason was that, under conditions
necessary to achieve appreciable
delignification, cellulose was attacked and degraded, leading to sharp decreases in pulp
viscosity and strength. This obstacle was finally removed when Robert and co-workers (8) discovered that addition of small
amounts of magnesium salts sharply decreased the damage suffered by the polysaccharide components
of the pulp during
oxygen bleaching. The remaining obstacle
to commercialization, providing for the high
mass transfer rates made necessary by the
low solubility of oxygen in water, was soon
overcome, and the first commercial system

was started up in South Africa in 1970 (9).
1.2 Process overview
Figure 2 shows a simplified oxygen delignification stage flowsheet. In a typical embodiment of the process, unbleached pulp
discharged from the repulper of the last
brown stock washer passes to a steam mixer
and then to a feed tank. Alkali, usually so. dium hydroxide or oxidized white liquor,
is added to the pulp at the base of the feed
tank and mixed with the pulp by the discharge pump.The pulp then goes to one or
more medium consistency, high-shear mixers where oxygen gas is added together
with additional steam. The mixers disperse
the oxygen in the pulp, which then passes
to an upflow pressurized reactor. After a
retention time of about one hour, the pulp
is blown to a gas separator mounted on a
blow tank. Product gases and unreacted
oxygen are vented, and the pulp enters the
first of two washing stages, perhaps a wash
press followed by a rotary drum washer.The
use of two washing stages at this point reflects the importance of complete removal
of material dissolved in the oxygen stage.
This is necessary to take advantage of the
environmental benefits ofthe oxygen stage
by capturing the lignin and other material
dissolved here and returning it to the mill

recovery system. Any dissolved material that
escapes to the following bleaching stages
becomes part of the effluent of those stages
and is a potential environmental liability.
In addition to the medium (1 ()..14%) consistency-type systems, high (2()"28%) consistency systems are common, though few
new ones are being installed. The main distinguishing characteristic of the high-consistency system is the presence
of a
dewatering device to produce high consistency and a down flow reactor. Both types
of systems are considered in more detail in
a later section of this chapter.
1.3 Advantages and disadvantages

oxygen delignification
of
The chief advantages of oxygen bleaching are related to its beneficial effects on
environmental parameters, although there
are also some operating cost advantages.
Its chief disadvantages are capital costs and
increased demand on the mill recovery
system.
The most obvious beneficial effect of installing an oxygen pre-delignification stage

in a cWorine compound-based bleach plant
is a decreased need for oxidizing chemical
in the de lignifying part of the bleaching
sequence. If this is cWorine or cWorine dioxide, there is a corresponding decrease in
chlorinated
organic byproducts
in the
bleach plant effluent (as measured by adsorbable organic halide, AOX). When the
de lignification stage oxidant is cWorine dioxide, the effect is smaller because cWorine dioxide generates much less AOX, but
the chemical cost saving is greater. In either case, the oxygen stage leads to a major
decrease in biochemical oxygen demand
(BOD), chemical oxygen demand (COD),
and color.
Lower chemical cost results from the
decreased requirement for delignifying oxidizing chemical (cWorine, cWorine dioxide,
or ozone, for example), because oxygen is
less expensive, and oxidized white liquor
usually provides the necessary alkali for the
oxygen stage at low cost. Further savings
result from a decrease in the cWorine dioxide charge needed for final bleaching stages.
Both decreases in chlorine dioxide require-
ment translate
into the additional
217
advantage
of allowing a smaller cWorine dioxide generator to be used. Additional savings result

from a decrease in the caustic (i.e. sodium
hydroxide) required in the first extraction
stage.
Of the disadvantages, capital cost is the
most apparent. In 1987, in the course of
one economic comparison of bleaching
alternatives (10), the cost of a medium-consistency oxygen delignification
system
was estimated to be $14.1 million. More
recently, it has been estimated that the installed cost of such a system with two postoxygen washing stages is in the range $1326 million, depending on equipment selection and site (11). A further drawback is
the possibility of overloading systems in the
chemical recovery area ofthe mill.The use
of oxidized white liquor as an alkali source
requires additional causticizing. Recycling
of oxygen-stage solids to the recovery system increases recovery boiler loading and
water, added as steam and with chemicals,
increases evaporator loading (12).An additional disadvantage is the tendency of oxygen bleaching to be nonselective at higher
degrees of delignification.This is not a problem if a suitable carbohydrate protector is
used and the degree of delignification is
not too high, that is, not more than about
50%. Also included under the heading of
disadvantages are increased steam costs,
higher maintenance costs, and an increase
in overall process complexity.
2. Fundamental aspects of
Before considering equipment configurations and process variable effects in oxygen bleaching, it is worthwhile to review a
number of its fundamental aspects. This
provides a logical framework for understanding the design and behavior of the
process, and for predicting the effects of
changes in hardware or mode of operation.
The basic aspects of oxygen bleaching can
be organized under the headings of chemistry and process fundamentals. Important
chemical considerations include the chemistry of oxygen, reactions of lignin and carbohydrates, and the related concepts of
218
Pulp Bleaching
- Principles
and Practice
selectivity and protectors. Features of the

process to be considered are rates of chemical reaction and mass transfer, heat effects,
chemical
consumption,
and reaction
products.
2.1 Chemistry
Several reviews of the chemistry of oxygen delignification that have appeared in
the literature may be consulted for more detailed information. Gratz1 (13) has reviewed
the inorganic chemistry of dissolved oxygen and the various radicals and other species derived
from it. Singh (14) has
presented a comprehensive overview of the
chemistry of the various radical species
likely to play a role in oxygen bleaching.
Reactions of lignin, inferred from the results
of model compound studies, have been the
focus of reviews by Gierer and lmsgard (15)
and Gratz1 (16).A more general review by
Gierer (17) also discusses relevant lignin reactions. Carbohydrate reactions are the subject of papers by Theander
(18) and
Sjostrom (19). All three topics have been
reviewed by Robert and de Choudens (20),
Hise (21), and Gratz! (22).
Oxygen chemistry
Oxygen is an unusual molecule in that
its normal Oowest energy) configuration is
the trlplet state. It contains two electrons
+8,- H+. HOO
.
+8,- H+. HOOH +8, H+. HOH + .OH +8.- H+~ 2 HOH
1l
11
4.8
11.8
11.9
11
II
II
pKa
H+ + o~
Flg.3. SleJniMe
that, because of their parallel spin, are unpaired. Each of these electrons therefore has
an affinity for other electrons of opposite
spin. In other words, oxygen is a free radical. Although less reactive than other free
radicals, it shares their tendency to react
with appropriate substrates at regions of
high electron density. The result is the initial step in a four-step process in which
oxygen is reduced to water and the substrate is oxidized. Figure 3 illustrates the
process. The product of the first step is a
negatively charged ion, called the superoxide anion, 0z"' which can combine with a
hydrogen ion to form the hydroperoxy radical HOO~ However, because this radical is
a weak acid (PK.=4.8), the anion remains
uncombined under the alkaline conditions
of oxygen bleaching.
Both the superoxide
anion and the
hydroperoxy radical have higher oxidation
potential (affinity for electrons) than their
parent oxygen. In principle, therefore, each
can readily acquire another electron to
form, respectively, the peroxide dianion,
ot, and the hydroperoxide
anion, HOO-.
In reality, the dianion is probably not sufficiently stable to form in appreciable
amounts. The hydroperoxide
anion is the
dissociated form of hydrogen peroxide.
Because hydrogen peroxide is a weak acid
(PK. = 11.8), both it and its anion are present
~ofoqgM.
H+ + .OOH
II
H++ 0:
Chapter IV I: Oxygen Delignification
Initiation
ROo + 02.
(1)
R. + H02
(2)
R02
(3)
R02H + R.
(4)
ROR
(5)
Propagation
Termination
PIg.4. Steps'n tbe m/Mnism of ~
ROo + R.
219
220
Lignin reactions
Two general approaches have been used
to learn about the mechanisms of lignin
removal during oxygen bleaching: Model
compound studies beginning in the 1960s
(23) and continuing up to the time of writing (24) have provided considerable insight.
More recently, studies of the effects of the
process on structural features of both residual and dissolved lignins have led to increased understanding of the chemical and
physical aspects of the mechanism (25).
The review articles already mentioned are
a good source of information on these studies.A brief summary of the major findings
is presented here.
Free phenolic hydroxyl groups playa key

role.When ionized by addition of alkali, they
furnish the high electron density that is
needed to initiate reaction with the relatively weakly oxidizing molecular oxygen.
This, together with the weakly acidic nature of phenolic hydroxyl groups, explains
why strongly alkaline conditions are needed
to achieve appreciable de lignification rates.
The initial step is conversion of the ionized
phenolic group to a phenoxy radical by the
loss of a single electron to a suitable acceptor; this may be molecular oxygen (which
is thereby transformed to the superoxide
radical anion) or one of the many other radical species present. The resulting phenoxy
blueblng.
-L
I
in appreciable
amounts under oxygen
bleaching conditions.
The third step in the stepwise reduction
of oxygen occurs whe11, hydrogen peroxide accepts an electron to form a hydroxide ion and a hydroxyl radical, HO.. The
hydroxyl
radical is also a weak acid
(PK,,=11.9) that exists in equilibrium with
its anion, -0.. Finally, the hydroxyl radical
can acquire another electron to form hydroxide ion or water. The occurrence of
hydroxyl radicals in this process is particularly significant because they are extremely
reactive and indiscriminate, attacking cellulose as well as lignin.A final point worth
noting about Fig. 3 is that a variety of reactions may occur between the species shown
(13).ln some of these, entirely new species are formed, such as the hydrotrioxy
radical, HOOO., and singlet oxygen, 102'
The complex oxidation processes that
occur in the oxygen bleaching reactor include radical chain reactions involving a
variety of organic species derived from both
lignin and carbohydrates. Figure 4 shows
likely initiation, propagation, and termination steps. Oxygen in its normal state is a
weak oxidizing agent, so it is necessary to
promote its reaction either by raising the
temperature or by providing a reactive substrate. In oxygen bleaching, the substrate
is activated by providing alkaline conditions
to ionize free phenolic hydroxyl groups in

the residual lignin. The resulting anionic
sites are electron-rich and therefore vulnerable to attack by oxygen. An electron is abstracted, fortning superoxide anion and a
phenoxy radical (Fig. 4, reaction I). An alternate pathway for initiation of the radical
chain reaction is abstraction of a hydrogen
atom from an unionized phenolic group or
other functional group to give the corresponding organic radical (Fig. 4, reaction
2). Propagation of the chain reaction occurs
by reactions such as the one between oxygen and an organic radical to form a peroxy
radical which, in turn, may abstract a hydrogen atom to regenerate a new organic
radical (reactions 3 and 4). The chain is terminated by coupling reactions.
An added complication, and one of great
significance, is the involvement of trace
quantities of transition metals, acting as
catalysts for peroxide decomposition. This
catalytic decomposition
forms hydroxyl
radicals, the indiscriminately reactive species that are believed to be the source of
much of the damage to cellulose that occurs during oxygen bleaching. Conse-
quently, m~Mgement
of tree tt'!l.ngttion
metals concentration
is an important consideration in achieving selectivity in oxygen
bleaching.
R=H,OAr,Ar,orAIk
.'
.~
'('~,
o
-L
=1:/
7 ..;1)
.
r~'
-Y-R
~.
7):
I
-Y-R
7;X:
0-
0CH0
221
222
I
-Y-R
".;;::
09
HO
._~
oci
I
-Y-R
/~
.
0..,,0
--90
- ,~
0-
...~
I
O=:Co-R
.--9-0-
Fig.6. RetU:tknIsoflfllermetlWe~.
radical is a resonance hybrid of structures
in which the odd electron formally resides
at the phenolic oxygen, at one of several
different carbon atoms in the aromatic ring,
or at the S-carbon atom of the side chain.
All of these positions are therefore potential sites for the next step of the reaction,
conversion to a hydroperoxide. The other
reactant can be molecular oxygen, the superoxide anion radical, or the hydroperoxy
radical. Figure 5 illustrates these steps.
In the alkaline environment of the oxygen bleaching process, the hydroperoxide
intermediate
exists, in pan, as the corresponding anion, which can subsequently
undergo an intramolecular nucleophilic reaction at an adjacent site. This may be the
carbonyl carbon of the quinone methide, a
ring carbon conjugated with it, or an adjacent side chain carbon, depending on the
location of the hydroperoxy function.These
reactions, illustrated in Fig. 6, lead to the
I
-Y-R
Fig. 7. RelldlOfU of byIIroJlet'WtUk IIIt-uu.tes
-OO---Y-R
o 0"
I
-Y-R
fOnnation of oxirane, muconic acid, and carbonyl structures. The last corresponds to
breakage of a bond joining two lignin monomeric units and therefOre leads to lignin
fragmentation. The others correspond to
introduction of hydrophilic groups, impaning polar character. Both types of reactions
may be expected to enhance the solubility
of the lignin in the alkaline medium.
Pathways are also available for similar
reactions of unionized hydroperoxides,
and for conversion of the hydroperoxides
to onho- and para-quinones. The resulting
quinones are susceptible to nucleophilic
attack by the hydrogen peroxide anion.
Figure 7 illustrates these routes. These reactions lead to opening of the quinone ring,
and the formation of muconic acid and
other acidic structures that ionize and impan solubility to the lignin. Hydrogen peroxide is present as a result of oxygen
to form mlU:Of8kIIdds ,,,uI'l"lIrones.
reduction, as described above, and decomposition or hydrolysis of organic hydroperoxide intermediates.

The phenoxy radicals formed at an early
stage of the process are, in principle, capable of undergoing coupling reactions to
form new carbon-carbon bonds between
lignin units. These condensation reactions
are obviously undesirable because they increase the molecular size of the lignin and
thereby decrease its solubility. Funhermore,
the condensed units are resistant to nmher
reaction. Because of the restricted mobility
of the phenoxy radicals in lignin, however,
it is unlikely that these reactions occur extensively during oxygen bleaching, although there is some evidence for their
occurrence (26).
Residual lignin may contain many types
of structural units that have free phenolic
hydroxyl groups, all of which are subject
to the reaction types depicted in Figs. 6 and
7. However, not all react at the same rate,
and some may react so slowly as to be considered stable.The relative rates of the various possible reactions have been the subject
of a series of studies by Ljunggren and
Johansson (27). Cenain structures known
to be present in appreciable amounts in
kraft residual lignin are very reactive. That
these include catechols, stilbenes, and enol
ethers, shows that additional phenolic hydroxyl groups and unsaturation in the side
chain are both structural features that enhance reactivity. A methoxyl substituent in
the aromatic ring also increases the reaction rate. On the other hand, a carbonyl
group in the a-position of the side chain or
an interunit linkage at the 5-position of the
aromatic ring decreases the rate.
Studies employing pulp or lignin instead
of model compounds have, to a large extent, confirmed the conclusions drawn from
the model studies. Gellerstedt and co-workers (28) investigated the structure of the
lignin in oxygen-bleached
pulp and concluded that oxygen bleaching
reduces
the content of free phenolic units. In contrast, the lignin remaining in the pulp
after oxygen bleaching was enriched in
biphenyl-type condensed structures and
p-hydroxyphenyl-type
lignin units. Both
observations are consistent with the results
of earlier model studies. In a later study
(29), it was confIrmed that the number of
phenolic hydroxyl groups in the pulp lignin decreased and the number of carboxylic acid groups increased.
Pulp lignin
structural studies have also shown that
diphenylmethane-type
condensed
structures are panicularly resistant to oxygen
bleaching.
A fInal point concerning the chemistry
of lignin reactions during oxygen bleaching concerns the role of covalent linkages
between lignin and one or more of the car-
223
224
bohydrate components of the fiber wall.

This topic has been studied byTaneda and
co-workers (30), who found that a Iignincarbohydrate complex extracted from pulp
after oxygen delignification contained about
half of the residual lignin, and that it was
extensively degraded. They concluded that
cleavage of a bond between xylan and lignin would allow more extensive oxygen
delignification.
Carbohydrate reactions
Carbohydrates are attacked during the
course of oxygen delignification to a greater
extent than during chlorination and alkali
extraction. For this reason, delignification
is usually limited to removal of no more than
about half of the lignin in the pulp entering
the oxygen stage.
Reactions that degrade cellulose can be
divided into two categories: random chain
cleavage, which may occur at any point
along the chainlike molecule, and endwise
"peeling; by which units on the end of the
chain are attacked and successively removed (3 1). Although both types may occur during oxygen bleaching, random chain
cleavage is the more significant.
Traces of metals that are unavoidably
present in unbleached pulps (32) promote
random chain cleavage. Transition metals
such as iron, manganese, and copper are
particularly troublesome. They catalyze the
formation of reactive, oxygen-based radicals, such as hydroxyl radicals, that randomly attack the cellulose chain, ultimately
leading to chain breakage at the point of
attack. The associated decrease in the average length of the cellulose chains manifests
itself as a decrease in pulp viscosity and, if
allowed to proceed far enough, as a decrease in pulp strength.
As illustrated in Fig. 8 (22), the initial step
in the chain cleavage process involves oxidation of a hydroxyl group to a carbonyl
group. The ionized enol form of the resulting carbonyl-containing
unit then undergoes a beta-elimination reaction, breaking
the glycosidic linkage joining the affected
unit to the rest of the cellulose chain. The
initially formed carbonyl-containing
unit
does not necessarily have to react as de-
C~H
1T
OH
R1-<P ~-
O'
0-R2
scribed above to break the cellulose chain.

A competing reaction occurs when oxygen
attacks its ionized keto form, forming a cyclic carboxylic acid or an open-chain structure containing two carboxylic acid groups.
In neither case is the cellulose chain broken. Figure 9 (22) illustrates these reactions.
The reaction that causes yield loss in alkaline media, the peeling reaction, is usually of less Importance in oxygen bleaching
than random chain cleavage. For an end unit
to be susceptible to removal by the peeling
reaction, it must contain a carbonyl group.
Because occurrence of the reaction leaves
behind a new end unit containing a carbonyl group (a "reducing end group"), the process is self propagating
and can, in
principle, continue until all the cellulose dissolved. This is prevented by the occurrence
of a competing reaction termed the stopping reaction that converts the end unit to
one that does not contain a carbonyl group.
In the oxygen bleaching of kraft pulp,

yield loss is generally not a serious problem, for two reasons: Kraft pulps, because
of their long previous exposure to strongly
alkaline conditions in the digester, contain
very few end units that have not already
been converted to the stable form by the
stopping reaction. The other reason is that
oxygen itself converts reducing end groups
to the stable oxidized form (32). However,
peeling can become a problem if random
chain cleavage is excessive because every
chain breakage creates two new chain ends,
one of which is a reducing end group.
Selectivity and protectors
Selectivity can be loosely defined as the
ratio of attack on lignin to attack on carbohydrate. It is affected by the choice of process conditions and by the presence of pulp
contaminants. Of the factors governing selectivity in oxygen bleaching, one of the
most Important is the transition metal content of the pulp, because these metals catalyze the generation
of harmful radical
species. Most pulps contain appreciable
quantities of iron, copper, and manganese,
all of which have this effect. One approach
for dealing with transition metals is to remove them by acid washing before the oxygen stage; another is to add compounds to
the pulp that inhibit carbohydrate degradation. These compounds are called carbohydrate protectors.
The protector of greatest commercial
Importance is the magnesium ion. The discovery of its effectiveness in 1963 by Robert and co-workers (8) provided a great
Impetus for the development
of oxygen
bleaching.
Since then a considerable
number of compounds have been found
effective, but none is as economical
as
magnesium sulfate or its heptahydrate,
Epsom salt. It is normally applied at levels
as low as 0.05-0. 1% Mg+2on oven dry pulp.
It is believed to function by precipitating
as magnesium hydroxide, which adsorbs
the metal ions, making them unavailable for
catalysis of peroxide decomposition
(33)
or by forming complexes with them (34).
Figure 10 (35) illustrates the effectiveness
of magnesium in preserving pulp viscosity
Chapter IV I: Oxygen Delignification

and is typical of selectivities
obtained
bleaching
of softwood
kraft pulp.
in the
MgS04
(moleslton
pulp)
,
,,
eo
40
20
,.i
'
".""
"
o~
10
20
Kappa number
Fig. 10. Effect of IUIIlIIUm of _pes/Nm

sekclllllty.
30
Ion 011
It is apparent from the nonlinear nature

of the curves in Fig. 10 that selectivity does
not remain constant as the kappa number
of the pulp is decreased to progressively
lower levels. However, selectivity usually
remains nearly constant until about 50% of
the lignin has been removed from the pulp
after which it deteriorates. In virtually all
of the existing pulping systems, the target
degree of delignification
is 60% or less.
When delignification is no greater than 4550%, the resulting
pulp may be fully
bleached to give a final product of strength
equivalent to that of the corresponding
conventionally bleached pulp, although its
viscosity is usually slightly lower.
Selectivity may be different for different
process types and is affected by process
variables, as is more fully discussed later in
this chapter. The fundamental reasons for
these effects are probably related to the
multiplicity of reactive oxygen-containing
species
present
and their different
reactivities with the variety of lignin and carbohydrate structures available to them. Hydroxyl radicals, which are among the least
selective of the reactive species present,
have been specifically studied from this
viewpoint by measuring their reaction rates
with compounds representative
of lignin
and carbohydrate structures (36). The ratio of the lignin rate constant to that for
carbohydrate was observed to lie betWeen
5 and 6. Hydrogen peroxide addition can
enhance selectivity (37) presumably be-
225
cause it favorably affects the composition

of the reactive species mixture present.
Carryover of black liquor from the brown
stock washers into the oxygen stage adversely affects selectivity (38).
Selectivity improvement by nitrogen dioxide pretreatment is a development worth
noting. Pioneered byYethon (39), this process has been intensively studied and developed by Samuelson and co-workers (40,
41). Treatment of unbleached kraft pulp
with nitrogen dioxide in the presence of
oxygen makes a following oxygen stage
more selective and efficient,even when the
oxygen stage conditons are mild. lignin
removal in the oxygen stage can be as high
as 80%, considerably enhancing pollution
abatement benefits. The mechanism ofthe
effect may involve acceleration of lignin
fragmentation because of nitration of lignin
monomeric units. Such nitrated units are
more readily separated from their neighboring units by cleavage of the intermediate
ether linkages (42). Another likely factor
is oxidative fragmentation
of lignin by
nitrogen dioxide (43, 44). The process
(Prenox8) reached the pilot plant stage (45)
but has not been commercialized. Among
the questions raised in assessing its viability are problems that may result from the
necessary recycling of effluent from the
acidic nitrogen dioxide stage to the kraft
chemical recovery system. These include
metals build-up and increased gaseous nitrogen oxide emissions. Other pretreatments shown to favorably affect oxygen
stage selectivity (46) include chlorine,
chlorine dioxide, and acidic hydrogen
peroxide.
2.2 Reaction and mass transfer rates
The rate of oxygen bleaching and its dependence on process variables are factors
that determine the design and size of the
equipment and the optimal choice of process conditions. In describing and predicting the rate of the overall process, it is
important to distinguish betWeen physical
and chemical phenomena, either of which
may determine the rate under a given set
of conditions. Physical factors govern the
movement of the reacting species within
226
the pulp mass (mass transfer), while chemical factors govern the rate at which the pulp
and bleaching chemicals react with one
another once they are in contact (chemical
kinetics).
Mass transfer
Mass transfer is an important consideration because most oxygen bleaching stages
are three-phase systems. Oxygen must cross
the gas-liquid interface, diffuse through the
liquid film surrounding the fiber, and finally
diffuse into the fiber wall before reacting.
Depending on the conditions, the rate of
oxygen transport can limit the rate of the
overall process because of the inherent
slowness of the diffusion phenomena involved (47).
The mass transfer problem is aggravated
by the low solubility of oxygen in aqueous
sodium hydroxide (48, 49). Typically, 24
times as much oxygen is consumed during
bleaching at 15% consistency as can be
present in the liquid phase at anyone time
and, at 27% consistency, 50 times as much.
Obviously, a viable process must facilitate
the transfer of oxygen into and through the
liquid phase.This can be done by ensuring
that the partial pressure of oxygen in the
gas phase and the gas-liquid interfacial area
are both sufficiently large.
Kinetics
Several studies have examined the rate
dependence of delignification and carbohydrate degradation reactions on reactant concentrations and temperature (50, 51).The
lignin in the pulp appears to be of tWo different types that differ with respect to the
ease of their removal by oxygen. The first
type is removed within about the first 10
minutes in a rapid initial phase. Removal
ofthe second type proceeds at a rate that is
proportional to the amount oflignin remaining at any given time. This means that the
lignin content can be reduced to any desired level by allowing the reaction to continue for a sufficiently long time. In practice,
the extent of reaction is limited by the availability of aIkali.The rates of removal of both
types of lignin increase with increases in
alkali concentration,
oxygen partial pressure and temperature.
Depending on reactor type and conditions, the delignification rate may be determined by the intrinsic chemical reaction
rate or by the rate of mass transfer of oxygen or alkali to the fiber. In the limiting case,
where mixing is so good that oxygen and
alkali are equally available to all fibers, the
rate is equal to that of the chemical reaction. Empirical models are available for predicting this rate and can be used to evaluate
mixing in a given reactor (52). They indicate that high-shear mixers are capable of
achieving very good mixing of alkali and
oxygen with pulp at medium consistency.
2.3
Heat effects, chemical consumption, and reaction products

The requirements
for application
and
release of heat, chemical requirements, and
types of reaction products formed have significant implications for the design and
operation of oxygen bleaching systems.
Heat effects
At reasonable alkali levels, temperatures
should be in the range 85-115C, so providing the required amount of heat in a steam
mixer and recycling hot filtrate must therefore be considered, especially in mediumand low-consistency processes.The heat of
reaction is appreciable (53) and its removal
may be a problem in high-consistency, high
kappa-drop systems. According to one estimate, the heat of reaction is 2400 kJ/kg of
material dissolved; another places it at
12,000
- 14,000
kJ per metric
ton for each
unit of kappa number reduction
(11).
Chemical consumption
The stoichiometry of oxygen bleaching
is such that, for each unit of kappa number
decrease, about 0.13% NaOH (o.d. pulp
basis) is required for softwoods and about
0.16% for hardwoods (54). In high-consistency systems, alkali consumptions in this
range are realized in mill-scale bleaching.
Medium-consistency
systems tend to consume slightly more alkali because the alkali
concentration is lower at a given charge in
these systems. The alkali is usually supplied
in the form of oxidized white liquor, which
can often be made available at lower cost

than purchased
sodium hydroxide. Unoxidized white liquor can be used (38), but
there may be adverse effects on selectivity
and rate (55). If unoxidized white liquor is
used, oxygen consumption
increases significantly.
Oxygen consumption is normally about
0.14% per unit of kappa number decrease
for softwoods and 0.16% for hardwoods.
Oxygen consumption in high-consistency
systems is slightly higher than in mediumconsistency systems because of losses due
to reactor venting and entrainment with the
pulp leaving the reactor.
Reaction products
Reaction products include organic acids
and carbon dioxide, small amounts of
carbon monoxide, and traces of methanol. Because the last two products are
combustible, it is necessary to control their
concentrations in the gas phase ofhigh-consistency reactors. This can be accomplished
by continuously bleeding gas from the reactor or circulating it through a catalytic
converter.
TIIbk 1. 1)pIt:41 ojIertIH", Au rvIIIpS for ~
3.1 Medium-consistency
processes
As a1ready mentioned, the low water solubility of oxygen makes it necessary to 1)
have a very large amount of water present
Ilelipi,/bl1orl
of softrJD4 IIfwft jI8Ip.
Medium Consistency
High Consistency
10-14
25-28
Retention time, min.
50-60
30
Initial temperature, C
85-105
1()()'1l5
lnIet pressure, kPa
7()().800
415-600
Outlet pressure, kPa
450-550
415-600
Delignification, %
40-45
45-55
Low press. steam cons., kg/t
4().1l 0
30-50
Med. press. steam cons., kg/t
40-1BO
75-175
Power consumption, kwh/t
35-45
40-50
Alkali consumption,
18-28
18-23
20-24
15-24
kg/t
228
3. Processes
and equipment
The factors discussed above influence
equipment
design for oxygen delignification. In particular, the relevant reaction
kinetics determine the size of the reactor;
mass transfer considerations determine the
configuration of the reactor and the provisions for efficiently contacting the pulp with
oxygen. The factor that most clearly distinguishes the available process types is pulp
consistency, but most systems being installed currently are of the medium-consistency type. High-consistency
systems
constituted the majority of those installed
during the first fifteen years of commercial
oxygen bleaching, beginning in 1970. Both
types have advantages and continue to be
available, and a few high-consistency
systems have been installed recently. Typical
operating data ranges for the two types are
given inTable 1 (54,56).
Consistency, %
Oxygen consumption, kg/t
227
Oxygen
blowtank
to dissolve all the oxygen needed for delignification, or 2) use a smaller amount of
water and provide conditions that facilitate
continual replacement of the dissolved oxygen by oxygen from the gas phase.This generally means providing
a very large
interfacial area between the liquid and gas
phases. One way of doing this is to dewater the pulp to high (20-27%) consistency
and fluff it to separate the fibers before
bleaching to create a dispersion of fibers in
a continuous
gas phase. When oxygen
bleaching was first introduced, this was the
only feasible method. Operating at medium
consistency was not feasible because of the
unavailability of equipment for intimately
mixing a very large volume of gas with the
pulp suspension (57). This problem was
solved when medium-consistency
mixing
technology became available in the late
1970s. The new high-shear mixing devices
make it possible to efficiently disperse oxygen as very small bubbles in 10-14% consistency pulp. After the oxygen is dispersed,
the pulp is tr.lnSferred to a reactor, where
the delignification reaction is allowed to
continue. The dispersion is relatively stable
and the buoyancy imparted by the trapped
oxygen eliminates any tendency for bed

compaction. An advantage of this approach
is that no special dewatering equipment is
needed before the oxygen stage.
Processes operating in the 10-14% consistency range have been described by,
among others, Kamyr (58, 59), Impco (60),
Sunds Defibrator
(61,62),
and Rauma
Repola (63). A typical system is represented
by the fIowsheet in Fig. 11 (54). Partia1Iy
washed brown stock is fed to a washer and
washed with illtrate from the post-oxygen
washer. The pulp from the washer is
charged with caustic (NaOH) or oxidized
white liquor, preheated in a low-pressure
steam mixer, and fed to the high-shear,
medium-consistency
mixer by a medium
consistency pump. Oxygen is added directly to the mixer from which the mixture
of pulp, alkali, and oxygen gas passes to the
bottom of the upfIow reactor which, in
some designs, is equipped with a rotary distributor to prevent channeling and in others is simply conical in shape. In either case,
the reactor is designed with a higher aspect
ratio than is typical of other types of bleaching towers to minimize the likelihood of
channeling. Channeling tendency increases

if the consistency decreases below 10%.
Post-oxygen washer filtrate is used for stock
dilution at the top of the tower to facilitate
discharge, which is mechanically assisted.
The stock is blown to a blow tank through
a separator, which allows entrained product gases, steam, and residual oxygen to be
released.
In one example (60), the reactor is 2.75
m in diameter and 27.9 m high and is designed for 45 minutes'retention
at a production rate of 320 tons per day. Although
smaller than most, this system is typical in
other respects. The reactor is designed to
operate at a pressure of 420 kPa and is constructed of 316L clad stainless steel. At the
top of the reactor, the stock is diluted to
10% consistency before being moved ,1:0ward a central discharge housing by a r0tating plow-type discharger. It is then blown
to a vertical pipe on top of the blow tank
that is equipped with an induced draft fan
to purge the tank of entrained gases. Stock
from the blow tank passes to a pressure
washer, where it is washed with filtrate from
the screened pulp washer. The washed
stock is diluted, screened, and sent to the
screened pulp washer, where it is further
washed. From there it goes to a multi-stage
bleach plant. In operation, this system has
allowed bleach plant production to be increased from 320 to 410 tons/day with no
change in pulp strength and with improved
final brightness and brightness stability.
To maximize environmental benefits and
cost savings, it is normally desirable to remove as much lignin in the oxygen stage as
possible, usually 40-60"A.,without adversely
affecting pulp qualIty. Achieving these levels in practice is often difficult, however,
particularly in medium-consistency systems.
Limitations on the degree to which all of
the oxygen added can be dispersed as sufficiently small bubbles and coalescence of
bubbles may contribute to a slowing of the
reaction as the pulp progresses upward
through the reactor. Attempts to increase
delignification by increasing the oxygen
charge may be counterproductive;
the gasdispersing ability of the mixer decreases and
channeling becomes more likely as the volu-
229
230
Pulp Bleaching
-Principles
and Practice
feeder or thick-stock pump, which maintains a seal against the reactor pressure. At
the bottom of the reactor, the pulp is diluted
to 5% consistency with recycled oxygenstage filtrate. Discharge is accomplished by
a rotating conical screw and agitating arms.
The system is exemplified by those in
operation
at Eddy Forest Products
in
Espanola, Ontario (67), and at the Franklin,
Virginia, mill of Union Camp Corporation
(68). Figure 13 (54) is a generic flowsheet
of the process. Washed unbleached pulp is
dewatered to a consistency of about 30%
in a twin-roll press. Alkali, usually in the
form of oxidized white liquor, and steam
are added and the pulp is transferred to the
reactor by a thick-stock pump or plug screw
feeder. Steam is added at the top of the reactor to maintain the desired temperature.
Upon entering the reactor, the pulp passes
through a fluffing mechanism and falls onto
the bed. A nuclear gauge senses the bed
level, which is controlled by changing the
flow rate of the leaving pulp suspension.
Oxygen is added at the top or bottom of
the reactor to maintain the desired partial
pressure. A small gas phase stream is con-
metric fraction of gas in the pulp suspension is increased.

These considerations have led to the development of two-stage, medium-consistency systems (64). They differ from the
single-stage systems only by the addition of
a mixer and a second reactor between the
first reactor and the blow tank, and often
require no addition of oxygen or alkali between stages. The first reactor may be
smaller than the second.
Although normally designed for pressurized operation, medium consistency systems incorporating open towers are also
being used (63). These are sometimes referred to as hydrostatic systems because the
only pressure supplied is the hydrostatic
head represented by the pulp column in the
reactor. Hydrostatic systems are normally
found in sulfite mills, but are also capable
of delignifying kraft pulps, especially hardwoods, to modest degrees (about 30%).
3.2 High-consistency
processes
One approach to solving the three-phase
mass transfer problem is to remove most of
the free liquid phase. This has the two-fold
effect of providing a large gas-liquid interfacial area and reducing the thickness of the
liquid layer through which oxygen must
diffuse to reach the fiber. Also, the amount
of recycled, potentially oxidizable dissolved
organic material in the reactor is reduced,
as is the amount of water that must be
heated to the reaction temperature.
For these reasons, many of the existing
commercial installations operate at high
consistency. Two general types are available: one originally matketed by Kamyr as
the Sapoxal process and the other by MoDoChemetics and Impco as the MoDo-CIL system. The two are similar, the only major
difference being in the design of the reactor itself.
The MoDo-CIL process (65,66) uses a
vertical cylindrical reactor designed to contain a continuous pulp bed at a consistency
of about 27% (Fig. 12). Keeping the consistency at or slightly above this value prevents
bed compaction, which would otherwise
reduce the free volume needed to serve as
an oxygen reservoir. Feeding is by a screw
Fig. n.
MoDo-CH
rwwltw.
Vent
Post oxygen
washer
Steam
Post oxygen
filtrate
FIG

tinuously bled from the reactor to remove
inert gases and combustible reaction products.
The possibility of ignition of combustible
gases is rendered insignificant by taking
simple precautions. Concentrations of carbon monoxide, methanol, hydrocarbons,
and other volatiles in the reactor are monitored and care is taken to ensure that volatile additives (i.e., some defoamers) do not
enter the reactor with the pulp. The usual
safety devices include an automatic relief
valve, rupture discs, and temperature-controlled quench showers. The concentration
of combustible gases is controlled by maintaining a continuous bleed stream. In some
installations, the bleed stream is routed
through a catalytic system for destruction
of combustibles, allowing it to be returned
to the reactor to reduce oxygen consumption.
The Sapoxal reactor (9, 69, 70, 71) is similar to the MoDo-CIL reactor, but operates
at sOmewhat lower consistencies (17-25%),
for which the reactor is specially designed.
As Fig. 14 shows, the reactor contains a series of trays arranged one above the other.
Each tray is divided into twelve compartments by radial walls and each has a cutout
that coincides with the cross section of the
compartments.The
trays, but not the walls,
rotate with the result that each compartment is emptied into the one below once
per revolution. It is therefore possible to
vary the retention time of the pulp by varying the rotation speed and, within limits,
to keep it independent of the production
rate. Bed compaction, which tends to become more pronounced as the consistency
is decreased, is avoided because the bed
depth is never greater than the distance
between trays.
Advantages claimed for operating at the
lower consistencies that this arrangement
permits are low bed combustibility and a
lowering of the temperature rise associated
with the reaction exotherm. Other advantages claimed for the trAy.type reactor are
better control of retention time resulting
from the absence of channeling and a more
uniform gaseous atmosphere.
Oxygen reactor
FIg.14. Bottom stKmofrHetor
J1rocas.
Bottom
231
section
ruMfor
StIJNW
3.3 Comparison of medium- and highconsistency

systems
Both medium- and high-consistency oxygen delignification systems should be considered for any new installation. Their
relative merits have been evaluated by several authors (10, 54, 56, 64, 72, 73).
The trend in new installations is strongly
toward the medium-consistency
process.
Prior to 1983, virtually all installations were
of the high-consistency type, but since 1983
virtually all have been medium-consistency.
According to a 1987 review, for example,
of 19 new systems started up or slated for
startup in the period 1985-1989, all but one
were medium-consistency.
As of 1993,
medium-consistency systems accounted for
82% of installed capacity. Among the reasons that may be cited for this trend are
lower capital costs, greater ease of stock
handling with medium-consistency
mixing
and pumping technology, and improved
selectivity in the presence of appreciable
amounts of black liquor solids. On the other
232
hand, chemical consumption is higher than

in the high-consistency
systems and the
extent of de lignification tends to be lower.
The high-consistency system still has its
proponents, as evidenced by the fact that
700,000 annual tons of high-consistency
capacity was scheduled for startup in 1991
(56). Those favoring the high-consistency
process claim that the advantages of the
medium-consistency
approach are overstated. The investment difference is mainly
the result of a simpler feeding system for
medium-consistency
and elimination of a
press upstream of the reactor. However, to
maintain the same level of preoxygen washing, the medium-consistency
system requires an extra washer to replace the press,
lessening the advantage. Laboratory data
indicate no difference in selectivity at the
same level of magnesium addition (74).
High-consistency
systems often provide
substantially more delignification and the
chemical consumption difference may be
significant. In summary, both process types
should be considered for any new installation.
manifestation of the kinetics ofthe component chemical reactions and mass-transfer

processes. Kinetic studies such as those of
aim andTeder (50) therefore provide a useful framework for rationalizing and predicting these effects.
4.1 Time and temperature

At fixed alkali concentration,
the decrease of kappa number with time exhibits
two distinct stages, both of which are firstorder rate processes.There is an initial rapid
kappa number drop followed by a slower
one. This is interpreted as being caused by
the presence of two types of lignin that differ in ease of removal. The two delignification stages are directly paralleled by two
corresponding cellulose depolymerization
stages.
A consequence of the first-order nature
of the delignification process is that, given
enough alkali, the kappa number continues
to drop indefinitely. This is in contrast to
the normal observation that the process
appears to stop when a limiting kappa number is reached, as shown in Fig. 15 (75).
The latter behavior results when the alkali
charge is exhausted. Figure 15 also shows
that delignification is considerably accelerated by temperature increases; the point
4. Process variables
The response of an oxygen bleaching
system to changes in process variables is a
40
....
CD
.c
. Original pulp
o Temperature
85C
. Temperature 100C
V Temperature 115C
t!. Temperature 130C
30
~
c:
as
2: 20
as
~
10
1
Reaction
2
time, h
~-_._--

of alkali exhaustion is reached much more
rapidly at 130C than 85C.
As Fig. 10 shows, the parallel between
delignification and carbohydrate degradation rates leads to a good correlation between viscosity and kappa number. This
relationship tends to be moderately independent of process variables although
selectivity does suffer if the temperature is
increased beyond about 120C or if all of
the alkali is consumed.
4.2 Alkali charge

Increasing the alkali concentration by
increasing the alkali charge at constant consistency substantially
accelerates
both
delignification and cellulose degradation.
Figures 16 and 17 (74) illustrate this relationship.
4.3 Oxygen pressure
Beyond a minimum value of about 4 atm,
the effect of oxygen pressure is generally
small in comparison to the effects of alkali
Consistency 825% 07%
30
Temperature
110eC
pp02 0.68 MPa
1% NaOH
25
.D
20
15
as
0.
0.
3.5% NaOH
10
15
80
60
30
Time,m
011
Fig. 16. Effeel:l of lime, .0..11 eJHnre,
~
"*
tkllpljklltiolt
of IIlWftwooillnwft
JItIlp.
~
234
Pulp Bleaching
-Principles
and Practice
charge and temperature. On the other hand,

the kinetic studies already referred to show
that oxygen pressure has an appreciable
effect on the observed reaction rates at constant alkali concentration.
The apparent
departure of observed behavior from theoretical predictions is ascribable to the fact
that,for economic reasons, alkali is normally
present in limited amounts. In the absence
of an excess of alkali, increases in oxygen
pressure have relatively little effect.
4.4 Consistency
Despite its far-reaching equipment and
process implications, the effect of consistency at fixed alkali charge is relatively small.
Lowering the consistency leads to a moderate slowing down of both the delignification and carbohydrate
degradation
reactions as a result of the associated decrease in alkali concentration.
5. Effectson mill operation
2.5% NaOH
233
/uIJIPtI---'"
1M
The effects of installing an oxygen

delignification stage extend far beyond the
bleach plant. The operation and, in some
cases, even the design of other equipment
is affected in significant ways that must be
considered
before the change is made.
The areas affected include screening, brown
stock washing, chemical and heat recovery,
1100
Consistency 825% 07%
Temperature 11oec
Pp02 0.68 MPa
1% NaOH
45
2.5% NaOH
3.5% NaOH
25% consistency
IJ
'C
;Eo 1000'0
o
o
15
30
20
900U
en
40
60
I
15
I
20
Time,m
Fig. 18. Bffeel:l ofbliu:lI
121
44
Bleck
Iiquo<
Numberof
Addition
Recirculations
Kgs DSIBOMT 0 1 2 3
UJ
'5O
80
COfISlMMeY011vlscosUy I" tbe o.YFig. 17. Bffeel:l of lime, ill/mil clMrge,

"*
,en tkllpiftclltltm
of IIlWftwooillnwft
JItIlp.
121
25
5
oxygen stage
If an oxygen stage is to be used for
predelignification, it is most logically integrated into the brown stock washing system. Good upstream washing is essential,
because black liquor solids consume oxygen and may adversely affect selectivity.
Good downstream washing is necessary to
fully realize the pollution abatement potential of the stage. Oxygen-stage washer ftltrate is used as wash liquor in the brown
stock system and therefore finds its way
back to the recovery system. Oxygen-stage
washer losses enter the chlorination stage
and become unrecoverable.
The effects of pre- and post-oxygen washing efficiency have been the subject of several studies (56, 64, 76, 77). The dissolved
solids entering the oxygen stage arise from
two different sources, the digester and the
oxygen stage, and the effects of each are
dependent on the consistency of the oxygen stage. Oxygen-stage solids find their way
back into the oxygen stage because it is part
of a closed countercurrent washing system.
This is necessary to capitalize on the environmental benefits obtainable by prevent-
ti:s
~
60
5.1 Pulp washing before and after the
C)
~
M-
UJ 40
E 35
;Eo
'0
o
~ 30
:>
downstream bleaching, stock preparation,

and wastewater treatment.
Ilq80r
tit 25% conslsteney.
ClJrtyooer
"""
8444
V'f"'''
IJI2lIiI.
I
25
Kappa
number
dlssolved
IWlltls reclmlllllUm
011 oxygen-stllge
selectivity
235
1200
C)
'C
1100
'w
8rn
Block liquor
of
Recirculalions
-.
KgsDS.9OMT 0 1 2
20
64"-
'>
Z
() 1000
40
V".
eo
en
[J~.
100
OC)8
4-?
15
20
..,
~-' _
}nIlp).
Fig.If). Effects of bhlci llqrwr ~

10%COfISisIetrt;y
(so~""/I
200
30
sol,. rw:Ircllt.tW. 011ttypff-slllge.lectinty
50% delignification
C)
~
;;;-
25
Kappa number
III
[J
160
'C
:Z 120
.Q
~ 80
'w
o
urn
:> 40
Z
(S
0
en
Pulp
<:ons-.cy
10%
25%
20
40
COD
Fig. ZOoVIsrosUy loss
"",."""."k
in liquor
to el6stlre (so~
ing discharge of oxygen stage solids to the

environment, directly or by way of the conventional part of the bleach plant. Filtrate
from post-oxygen washing, used to wash
the pulp, partially displaces black liquor
from the pulp before it enters the oxygen
stage. Highly efficient post-oxygen washing
is desirable from the environmental standpoint but results in maximum recycle of
oxygen-stage solids. The desirability of efficient pre-oxygen washing is determined by
the effect of high solids carryover into the
oxygen stage, which is therefore of interest.
after
.o
WlOl8drculatlon
With r&eircu8ation
[J WIO 18dn:ulation
.__Iion
60
O2 (gIl)
80
lnwft JIfIlp).
Greenwood (64) has reported data obtained by the laboratory bleaching of softwood kraft pulp at 25% consistency in the
presence of systematically varied amounts
of dissolved solids (Fig. 18). At each level
of black liquor addition, the oxygen-stage
was repeated four times. In each experiment, a fresh sample of pulp was diluted
with filtrate from the previous experiment,
simulating oxygen stage solids recirculation,
and fresh black liquor was added, simulating carryover from the brown stock washers. Apparently,
in the absence
of
236
recirculation
of oxygen-stage
solids,
carryover of as much as 60 kg/t black liquor
solids has no effect on selectivity. On the
other hand, combinations of the two types
of dissolved solids, as would occur in practice, have a detrimental effect.
Experiments of the same type at 10%
consistency provided the data shown in Fig.
19. In this case, combinations of recirculated solids with up to 40 kg/t black liquor
solids were tolerated without loss of selectivity, but higher levels had a detrimental
effect. The higher tolerance of the mediumconsistency system for dissolved solids suggests that the important parameter is their
concentration in the liquor, not the ratio of
their dry weight to the dry pulp weight. To
test this possibility, liquors were removed
from the pulps after the oxygen stage in experiments conducted at both consistencies,
with and without recirculation, at different
levels of black liquor carryover. Figure 20
shows the results of determinations of their
chemical oxygen demand (COD), a surrogate for total organic dissolved solids concentration, plotted against the viscosity loss
in excess of that observed when fully
washed pulp was bleached. A definite relationship is apparent, despite scatter in the
data, which suggests that viscosity loss is
incurred when the COD concentration is
higher than about 20 g/L.
Greenwood (64) has performed calculations to demonstrate the practical implication of these phenomena,
namely that
highly efficient washing after the oxygen
stage, essential for environmental reasons,
requires an increase in the efficiency of the
brown stock washing system before the
oxygen stage to keep the COD levels in the
oxygen stage below that at which viscosity
is affected. In the ideal case, represented
by perfectly efficient brown stock washing,
the dissolved solids entering the oxygen
stage consist only of recirculated oxygen
stage solids. This emphasizes the importance of good washing before oxygen
bleaching. Greenwood's calculations demonstrate the desirability of three washing
stages before, and an additional three washing stages after, the oxygen stage.
The current practice in high-consistency

systems is to employ two washers (or indigester washing and one washer) before
the press (54). In medium-consistency
systems these are augmented by an additional
washer to replace the press. Two washers
are often employed after the oxygen stage,
but some systems have three.
5.2 Screening
Placing the oxygen stage in the brown
stock washing area makes it necessary to
close the screen room water circuit to avoid
the loss of oxygen-stage solids. The resulting potential for foaming problems normally
dictates the use of pressure screens.
The screen room may be located before
or after the oxygen stage. Most mills screen
the pulp before oxygen bleaching, but there
are many examples of the screen room being located after the oxygen stage. Important factors to consider in locating the
screen room are effects on cleanliness, heat
balance, and capital costs. Leaving the knots
in the pulp during medium-consistency
oxygen bleaching creates the risk of breaking them up in the mixer, thereby making
them more difficult to remove later. Otherwise, there does not appear to be a major
effect of screen room location on pulp
cleanliness. Because screen room deckers
typically do not operate well above 80C,
locating the screen room before the oxygen stage necessitates cooling of the oxygen stage filtrate before using it on the
screen room washer, increasing overall
steam consumption (64).
5.3 Implications
system
for the recovery
Recycling of organic material dissolved

in the oxygen stage to the recovery furnace
typically increases the load on the furnace
by 3% for softwoods and 2% for hardwoods.
A further increase of about 1% results from
improved recovery of black liquor solids
which can be credited to the additional
washing stages. The increase in steam generation is somewhat less because of the
lower heating value of oxidized solids (54).
If pure sodium hydroxide were used as

alkali in the oxygen stage, the amount
added, together with the chlorine dioxide
generator spent acid, would probably exceed the requirement for sodium makeup
to the liquor system. For this reason, and
because it is usually less expensive than
purchased caustic, oxidized white liquor is
usually used as a partial or sole alkali source.
If white liquor were used to satisfy the total alkali requirements of the oxygen stage,
an increase of about 5% in the capacity of
the causticizing and lime reburning systems
would be needed.
The additional water added with the alkali and as direct steam in the oxygen stage
leads to additional evaporator steam requirements of about 4% when high-consistency
systems are used. The corresponding figure for medium-consistency
systems Is
higher, perhaps as much as 10%, because
of the higher steam usage in medium-consistency reactors. Alternatively, washing
capacity can be added to allow a corresponding decrease in the dilution factor.
6. Pulp quality
The strength equivalence of conventionally bleached pulps and pulps that have
been oxygen delignified to an extent of
about 50% before conventional bleaching
iswell-documented(66,78,
79). Although
the viscosity of the oxygen bleached pulps
may be lower (as much as 4 mFa-s on the
TAPPI T230 scale), their tear factor at a
given tensile strength is generally the same
as that of conventiona11y bleached pulps.
The effects of oxygen bleaching on pulp
cleanliness, pitch, brightness stability, and
refining energy requirements are at least
neutral and in some cases slightly beneficial. The effect on cleanliness may be indirect inasmuch
as oxygen bleaching
is
usually followed by short bleaching sequences consisting of high concentration
chlorine dioxide stages, which are known
to improve pulp cleanliness. Refining energy requirements have been observed to
decrease upon installation of an oxygen
stage (79).
237
l.}ohnson,A.P.,Pulp
Pap. 67(3):103
2. Joy, W.e. and Campbell,}.,

66,353(July 2, 1867).
(1993).
U.S. Pat. No.
3. Mueller, R., U.S. Pat. (1915); d. Liebergott,

N.,NTRI (Pretoria) Symp.Forest Prods. Res.
Int., Proc. Vol. 2, Paper No. 7-1 (April 2226, 1985).
u.s. Pat. No. 2,673,148
(1954).
5. Marshall, H.B., and Sankey, e.A., U.S. Pat.

No. 2,686,120 (1954).
6. Nikitin,
V.M., and Akim, G.L., Trudy.
Lentngr. Lesotekbn.Akad.
75:144 (1956);
80:77 (1958); 85:3 (1960); Bum. Prom.
35:5 (1960).
7. Grangaard, D.H. and Saunders, G.H., U.S.
Pat. No. 2,926,114
(1960); Can. Pat. No.
611,503
(1960); Can. Pat. No. 632,280
(1961).
8. Robert, A., Traynard, P., Martin-Borret,
0.,
Fr. Pat. No. 1,387,853 (1963); Robert, A.,
Rerolle, P.,Viallet,A., Martin-Borret, O.,ATIP
Rev. 18(4):151 (1%4); Robert, A., Vtallet,
A., Rerolle, P., Andreolety, }.-P., ATIP Rev.
20(5):2071966).
9. Rowlandson,
G., Tappt 54(6):962
(1971).
10. Arhippainen,
B. and Malinen, R., "Cost
Competitiveness
of Oxygen Bleaching,"
1987Tappi International
Oxygen Delignification Conference
Proceedings,
TAPPI
11. Greenwood,
B.E and Hallenbeck,
Private communications,
1995.
M.R.,
12. Kamyr, Inc., Glens Falls, N.Y., U.S.A., "Oxygen Delignification,"

Technical Bulletin
No. KGD1801-WNI087.
13. Gratzl,}.S.,
Papter
46(10A):Vl
(1992).
14. Singh, A., "Phenoxyl- and Oxy- Radicals

and their Role in Oxygen Delignification,"
1987Tappi International Oxygen Delignification Conference
Proceedings,
TAPPI
PRESS, Atlanta, p.111.
15, Gierer,}. and Imsgard,
sttdn. 80:510 (1977).
16. Gratzl,}.S.,
Pulp Bleaching
-Principles
20. Robert,A. and de Choudens,

36(6-7):332 (1982).
References
4. Harris,G.e.,
238
Papier
E, Svensk
41(3):120
Papper-
(1987).
17. Gierer,}.,
Wood Set. Tecbnol.
20:1 (1986).
18. Theander,
0., in Cbemtstry
of Deltgnt-
ftcaUon
witb Oxygen, Ozone and Peroxtdes, Uni, Tokyo, 1980, p. 43.
19. Sjostrom, E., in Cbemistry

of Deltgnificatton wttb Oxygen, Ozone and Peroxides, Uni, Tokyo, 1980, p. 61.
and Practice
e.,.Al1P
Rev
21.Hise,R.G.,"A
Critical Review of the Chemistry and Technology
of Oxygen-Alkaline
Delignification," Department
ofWood and
Paper Science, North Carolina State University, Raleigh, 1983, pp. 6-17.
22. Gratzl,}.S., "Reactions of Polysaccharides
and Lignins in Bleaching with Oxygen and
Related
Species,"
1990 Tappi Oxygen
Delignification
Symposium Notes, TAPPI
23. Kratzl, K., Gratzl, }., Claus,
Chern. Series 59:157 (1966).
P., Adv.
in
24. Gierer,}., "The Reactions of Lignins with

Oxygen-Containing
Species," Seventh International
Symposium
on Wood and
Pulping Chemistry
Proceedings,
CTAPI,
Beijing, 1993, Vol. 1, p. 301.
25. Gellerstedt, G. and Lindfors,
Structure and Reactivity of
nin in Kraft Pulp Fibers,"
Pulp Bleaching Conference
Stockholm,
1991, Vol. 1, p.
E.-1., "On The

Residual LigInternational
Notes, SPCI,
73.
26. Hagstrom-Nasi, e. and Sjostrom, E.J Wood

Chern. Tecbnol. 8(3):299 (1988).
27.}ohansson,
E. and Ljunggren, S., "The Reactivity of Lignin Model Compounds
and
the Influence of Metal Ions During Bleaching with Oxygen and Hydrogen Peroxide,"
Seventh
International
Symposium
on
Wood and Pulping
Chemistry
Notes,
CTAPI, Beijing, 1993, Vol. 1, p. 180.
28. Gellerstedt,
E.-1., Nord.
(1986).
G., Gustafsson,
K., Lindfors,
Pulp Paper Res.]
1(3):14
29. Gellerstedt, G. and Lindfors, E.-1., Tappt]

70(6):119 (1987).
30. Taneda, H., Iwase, Y, Matsukura, M., "Heterogeneity
of the Residual
Lignin in
Oxygen Delignified Kraft Pulp," Seventh
International
Symposium
on Wood and
Pulping Chemistry Notes, CTAPI, Beijing,
1993, Vol. 1, p. 318.
31. Sjostrom, E., Pap. Puu 63(6-7):438
(1981).
32. Samuelson,
Pappersttdn.
33. Robert,A.
(1971).
O. and Stolpe, L., Svensk

72:662 (1969).
and Vtallet,A. , ATIP Rev. 25:237
34. Gilbert,A.E,
Pavlovova,
Tappt 56(6):95 (1973).

T., Holzforscbung
37. Parthasarathy,
YR., Sundaram,
YS.M,
}ameel, H., Gratz!, }.S., Klein, R., "Hydrogen
Peroxide-Reinforced
Oxygen
Delignification of Southern (Loblolly) Pine
Kraft Pulp and Short-Sequence
Bleaching,"
1989 Tappi Pulping Conference
Proceedings,TAPPI PRESS, Atlanta, p. 539.
38. Colodette,}.L.,
Campos,A.S., Gomide,}.1.,
"Attempts
to use White Liquor as the
Source of Alkali in the Oxygen
Delignification
of Eucalypt Kraft Pulp," 1990
Tappi Oxygen Delignification
Symposium
Notes, TAPPI PRESS, Atlanta, p. 145.
39.Yethon,A.E.,
5, 1980).
40.
35. Berry, R.M., "Oxygen Delignification,'Tech

'91 Kraft Pulp Bleaching Course, Tech.
Sect., CPPA, Montreal, 1991, p. 10-1.
Can. Pat. No. 1,070,909
(Feb.
Abrahamsson,
K., Lowendahl,
L.,
Samuelson,
0., Svensk
Pappersttdn.
84(12):RI52
(1981).
41. Samuelson, O. and Sjoberg, L.,.J Pulp Pap.

Set. 9(1):TR21 (1983).
42. Walding,}. and Lindeberg, 0., "Faster Alkaline Hydrolysis of Aryl Ether Bonds in
Nitrated Lignin," 1987 International
Symposium on Wood and Pulping Chemistry
Preprints,ATIP,
Paris, Book 2, p. 267.
43. Ohi, H. and McDonough,
T.}., Mokuzat
Gakkatsbt
38(6):570 (1992).
44. Ohi, H. and McDonough,
T.}., Mokuzat
Gakkatsbi
38(7):707 (1992).
45. Lindqvist, B., Marklund, A., Lindstrom, L.,
Norden, S., "Nitrogen
Dioxide
Preoxidation before Oxygen Delignification
-A
process for the Future?" International
Pulp
Bleaching
Conference
Preprints,
Tech.
Sect., CPPA, Montreal, 1985, p. 221.
46. Fossum, G. and Marldund, A., "Pretreatment of Kraft Pulp is the Key to Easy Final
Bleaching," 1988Tappi International
Pulp
Bleaching
Conference
Preprints,
TAPPI
47. Hsu, c.1. and Hsieh,}.S.,
( 1985).
TapptJ.
68(6):92
48. Broden, A. and Simonson,

R., Svensk
Pappersttdn.
82(16):487
(1979).
49.Akim,
E., Rapson, WH.,
}ansbo, K., Reitberger,

43(6):391 (1989).
G.L., Pap. Puu, 63(4a):291
50. Olm, 1. and Teder, A., Tappt

(1979).
(1981).
62(12):43
51. Evans, }.E., Venkatesh,

Y, Gratzl, }.S.,
Chang, H.-M., Tappt 62(6):37 (1979).

52. Hsu, c.L. and Hsieh,
34(1): 116 (1988).
J.S., AICbB
J.
53. Hillstrom, R., Jamieson, A., lindqvist, B.,

Smedman,
L., Svensk Pappersttdn.
80(6):167 (1977).
54. Tench, L. and Harper, S., "Oxygen
ing Practices
and Benefits
-An
G.B.,
57. Reeve, D.W and Earl, P.E,Tappt J 69(7):84

(1986).
S., Tappt
59. Kawase, T., "Operational

Experience of
Medium Consistency Oxygen Delignification at Sendai Mill," 1987Tappi International Oxygen Delignification Conference
Proceedings,TAPPI
Oxygen Bleaching System at Skutskar Mill,

Sweden," 1978 Tappi Oxygen, Ozone and
Peroxide Bleaching Seminar Notes,TAPPI
PRESS,Atlanta,
70. David, E., Cannone

Carles,].,
Durand,
M.D., Pulp Paper Int. 18:47(1976).
71.
56. Miller, W, Shackford, L.D., Minami, S.,

"Oxygen, Peroxide and Ozone Process
and Equipment," Non-CWorine Bleaching
Conference Proceedings, Miller-Freeman,
Atlanta, 1993, 'futorial Paper No.5.
60. Enz, S.M. and Emmerling,

70(6):105 (1987).
68. Smith, K.E., Pulp Pap. 56(10):90 (1982).

69. Svensson,J.E., "Experiences of the Sapoxal
Overview,"
55. Leader, J.P., Lim, H.H.K., Byrom,

AppttaJ.39(6):451
(1986).
58. Kleppe, P.]. and Storebraten,

68(7):68 (1985).
67. Munro, EC., Pulp Pap. Can. 88(7):34

(1987).
Bleach-
1987Tappi International Oxygen Delignification Conference Proceedings, TAPPI

PRESS,Atlanta, p. I.
p. 245.
EA., Tappt J.
61. Annergren, G. and Nasman, L., "Medium

Consistency Oxygen Bleaching -An Alternative to High Consistency
Oxygen
Bleaching?" International Pulp Bleaching
Conference
Proceedings,
Tech. Sect.,
CPPA, Montreal, 1979, p.99.
62. Kalish,]. ,Pulp Paper Int. 28(6):49 (1986).
63. Thtsuishi, H., Hatano, T., lwai, T., Kovasin,
K., "Practical Experiences of Medium Consistency
Oxygen
Delignification
by
Rauma-Repola and Sumitomo Heavy Industries," 1987Tappi International Oxygen
DeIignification
TAPPI PRESS,Atlanta, p. 209.
64. Greenwood, B.E, "Oxygen Delignification
Stage Design and Performance -A Kamyr
Perspective," 1990Tappi Bleach Plant Operations Shott Course Notes,TAPPI PRESS,
Atlanta, p. 63.
65. Jamieson, A., Noreus, S., Pettersson,
Tappt 54(11):1903 (1971).
B.,
66. Jamieson,A.G. and Smedman, L.A., Tappt

57(5):134 (1974).
239
Coetzee,
75(6):T223
B., Pulp
(1974).
72. Idner, K.,"Oxygen
- High
Pap.
Bleaching
Mag.
Can.
of Kraft Pulp
Consistency vs. Medium Consis-
tency," 1987 Tappi International

Oxygen
Delignification
Conference
Proceedings,
73. lindstrom,
L.-A., "Oxygen Stage Design
and Performance," 1990Tappi Bleach Plant
Operations
74. Liebergott, N., van Lierop,B.,Teodorescu,
G., Kubes, G.J., "Comparison
Between
Low and High Consistency
Oxygen
Delignification
of Kraft Pulps," 1985 Tappi
Pulping Conference
Proceedings,
TAPPI
75. Harder,
N., Norrstrom,
H., Rydin, S.,
Svensk Pappersttdn.
73(21):6%
(1970).
76. SSVL (Swedish Forest Industry Foundation
for Water andAir Protection, Environmental Care Project), Technical
Summary,
1974, p. 75.
77. Magnotta, v.L. and Courchene,
C.E., "Process Effects of Entrained Black liquor and
Oxygen Stage Filtrate Solids on Oxygen
Delignification,"
1982 Tappi Pulping Conference
Proceedings,
TAPPI PRESS,
Atlanta, p. 309.
78. Jamieson, A., "The Strength
of Oxygen
Bleached
Pulps," Report
of Mo och
Domsjo Study, Sunds Defibrator/MoDoChemeticsAB,
ca. 1979.
79. Munro, EC., "Integrating
an Oxygen Stage
into a Bleached
Kraft Mill," 1985 Tappi
Seminar Notes,
IMPI
PRESS,AtIanta,
p. 61.
SECfION IV:
The Technology of
Chapter 2:
Chlorination
Ronnie Rise
Westvaco Corporation
Covington, Vlfginia
1. Introduction.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
2. Role of chlorine
as adellgnifyingagent.
244
3. Chlorination chemistry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
'.'
3.1 Chlorine-water equilibrium
.......................
3.2 Reactions of chlorine with lignin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3 Reactions of chlorine with carbohydrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.4 Reaction kinetics
4. Impact of chlorination
4.1
4.2
4.3
4.4
4.5
243
process variables
245
245
246
247
247
248
Chlorine charge
Temperature and time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Consistency
pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Chlorine dioxide substitution. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
249
250
251
251
251
5. Process equipment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
5.1 Stock dilution. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . .
5.2 Blending and consistency control
5.3 Chemical injection and dispersion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.4 Mixing. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
252
253
253
253
254
6. Process control.
254
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
7. Effect of chlorination
and dirt removal
8. Environmental
on shives
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
aspects of chlorination.
255
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 255
741
Chapter IV 2: Chlorination
Chapter IV 2:
Chlorination
1. Introduction
In the early 19005, practical means were
developed for handling liquid chlorine. This
was a key step leading to the use of chlorine as the first delignification stage after
pulping. Previously, hypochlorite was used
to continue the delignification
process.
Chlorine came to be preferred because of
its lower cost and improved selectivity for
reaction with lignin compared with cellulosic materials. At present, the use of chlorine for bleaching is decreasing rapidly. Its
decline can be attributed to concerns about
the formation of chlorinated organic compounds - mainly fragments of degraded
lignin as by-products of the delignification
process. Government regulations and market pressures in the early 1990s have led to
the virtuaI elimination of molecular chlorine for bleaching in Sweden, Finland, and,
to a large extent, Canada, as well. Proposed
legislation will effectively eliminate the use
of molecular chlorine in the United States
for the bleaching of kraft pulp by the year
2000 if not sooner.
243
The chlorination stage has traditionally

been the "workhorse" of the post-pulping
processing steps in the manufacture
of
bleached pulps. As illustrated in Fig. 1, the
chlorination and following alkaline extraction stages together can selectively remove
75-90".4,of the lignin remaining in the fiber
after pulping. It can be safely stated that
no other chemical can achieve this performance as economically.
Another benefit of the chlorination stage
is that metals are effectively solubilized and
removed from the pulp. This is a result of
the low pH levels normally employed in this
stage. Some of these metals can interfere
with the performance of later bleaching
stages and can cause or enhance brightness
reversion in the final bleached pulp.
The amount of chlorine required for
bleaching conventional softwood kraft pulp
may be as high as 10% on pulp, or 100 kg
per metric ton of pulp. More typically, usage is 4-6% for softwood and 2-4% for hardwood.
A schematic drawing of a typical lowconsistency chlorination stage is shown in
Fig.2. Unbleached pulp is diluted at the
bottom of the storage tower, passes to a
blend chest to even out consistency variations, and then to the chlorine addition
.....
\I)
.I
c:
='
as
a.
a.
as
~
Fig. 1. Uplll
~s.
_,,1
lIS IIuUaItM by TuIpptI""mber III ClUT'MttnUIpossIble.futrwe JIIII"*,,..
",,,g
244
point(s), chemical addition and mixing

points, a retention tower, and a washing
stage.
The purpose of this chapter is (1) to review the role of the chlorination stage in
the preparation of conventional bleached
kraft pulp, (2) to discuss what is known
about the reaction mechanisms and kinetics, and (3) to provide the basic information required for an understanding
of
chlorination
systems and the principles
governing their sound operation.
2. Role of chlorine as a
delignifying agent
The chlorination and first alkaline extraction stages generally are viewed collectively
as a continuation of the delignification process that began in the digester in contrast
to later bleaching stages which mainly serve
to bleach the pulp. Lignin removal is more
selective in the chlorination and extraction
stages than in the pulping process. Wood
chips contain 2().30% 1ignin on a dry-weight
basis depending on the species. Pulping to
a bleachable grade removes over 90% of the
original lignin, but, because portions of the
cellulose and hemicellulose are dissolved
d111'ingpulping, lignin still comprises about
4-5% of the dry weight of unbleached pulp.
Chlorination, combined with an ensuing
alkaline extraction stage, removes 75-90%
.of the lignin remaining in unbleached kraft
~,ul~!I. The lignin remaining in the fibers
after chlorination and extraction, usually
leSiSthan 1.5% by weight, can be removed
or decolorized in one or more bleaching
stages. Various aspects of chlorine bleaching are well covered in the literature (1-7).
More selective and expensive chemicals
must be used to preserve pulp yield and
strength as the lignin content of the pulp is
further decreased. Therefore, the importance of the chlorination stage is emphasized by the fact that inadequate
chlorination leads to hlgh chemical demand
in later bleaching stages. Excessive or
poorly controUed chlorination may result
in unsatisfactory pulp quality and yield loss.
Equally important of late, the formation of
highly chlorinated by-products such as chlorinated dioxins, may increase as chlorine
consumed increases.
Another important function of the chlorination stage is to smooth out variations in
unbleached kappa number and to insulate
the remaining bleaching stages from any
black liquor carryover which may accompany the pulp after the brown stock washing and screening operations. In this regard,
chlorine has been a nearly ideal first-stage
bleaching agent following pulping.
Chlorine may be described as a very"user
friendly" bleaching agent compared with
other well-known chemicals. For example,
chlorine reacts with pulp rapidly and selectively over a broad range of pH values, over
a wide range of temperatures, and at low,
medium, or high consistency. Because of
the high reaction rate, in-line sensors can
be used effectively to obtain real-time information for controlling the process with
a short feedback loop. Chlorine is also effective in bleaching "dirt" and shives (fiber
bundles) (see Section 11 in this Chapter).
Drawbacks in using chlorine include the

formation of chlorinated organic by-products; formation of chloride ions, which
renders the filtrate corrosive toward conventional carbon and stainless steel; and a
complicated handling and delivery system.
The presence of railroad tank car quantities of liquid chlorine at a mill site also represents a potential hazard.
It is useful to understand some basic aspects of chlorination stage chemistry to
understand and predict the effects of modifications on the process. The search for alternative bleaching chemicals also can be
guided by detailed knowledge of how chlorine reacts with pulp components.
3.1 Chlorine-water
equilibrium
Chlorine is partially soluble in water and
exists in various molecular forms, governed
by the pH of the system. Molecular chlorine (Cl) and hypochlorous acid (HOCl) are
in equilibrium, with approximately equal
amounts present at pH 2.0 at 25C:
~
HOCI + HCl
[I]
Both hypochlorous and hydrochloric acids (on the right side ofEq. 2.1) dissociate
in water to release a hydrogen ion (H+).
Hydrochloric acid is completely dissociated
at the normal chlorination stage pH levels,
but hypochlorous acid is only slightly dissociated according to the equation below:
HOCl ~
W + ocr
[2]
The concentrations of these chlorine species can be calculated based on the law of
mass action:
K, = [HOC;h[~+]
2
[OCI"] [W]
1(,=
[HOC1]
[CI"]
- 3.94 x IQ4
at 25C [3](8)
[4)(9)
= 5 .6 x W" at 25C
where Kl and Kz are the equilibrium constants for these reversible reactions (8, 9).
From these known relationships, predictions can be made on how changes in process variables affect the distribution
of
246
romolecules into small enough fragments

to be soluble in the acidic C-stage filtrate,
or serve to modify the lignin so that it becomes soluble in the following alkaline extraction stage. The last two reactions types,
substitution and addition, lead to the formation of chlorinated organics.
The chlorination-stage
pH decreases
typically to 2.0 or lower as the reactions proceed, because of the formation of hydrochloric acid and organic acids. In some
mills, part of the acidic C-stage washer filtrate is recycled for dilution of unbleached
pulp, and this helps to keep the pH below
2.0.
20
b80
0
.,,60
I:
as
HOCI
0'''40
~0
20
400
0
J:
6O~
80
CI2
100
023456789
3. Chlorination chemistry
Cl2 + HP
100
pH
FIg.3. 1)e t:OIIIJIOSUItm

of till 0.01N.,.,. IOlllliorlllS"j'ruIdIotI of pH
-Principles
245
dllo-
reactive species in the chlorine-water system and therefore affect the reactions that
occur in the chlorination stage. Operating
the C stage at a lower consistency, for example, causes the equilibrium to shift to the
right in [I]. A similar effect is observed as
the temperature is increased and the system becomes enriched in hypochlorous
acid relative to molecular chlorine.
Probably the most important process
variable controlling the form of chlorine
present in the C stage is pH. It is clear from
[I] and [2] that an increase in hydrogen ion
concentration forces the equilibrium to the
left which facilitates reactions involving
molecular chlorine. Increasing the pH (decreased hydrogen ion concentration) shifts
the equilibrium to the right and enhances
the formation of hypochlorous acid and finally hypochlorite ions [I] and [2]. This
effect is illustrated in Fig. 3 (10). As the
temperature is increased, and the system
becomes enriched in hypochlorous
acid
relative to molecular chlorine.
The type of reactive species present in
the chlorination stage is significant because
hypochlorous acid reacts with pulp components by different mechanisms than does
chlorine.
Hypochlorous
acid reacts less
selectively with lignin than chlorine and loss
of pulp quality and yield may result from
attack on carbohydrates.
Reactions of hypochlorous acid with lignin are mainly oxidative, but reactions with chlorine involve
oxidation, substitution, and addition. All of
these reactions contribute directly or indirectly to the breakdown of the lignin !mC-
Pulp Bleaching
and Practice
does not proceed in a step-wise manner for
the system as a whole: even under the relatively homogeneous reaction conditions existing when model compounds are treated
with chlorine, the reaction mixture often
contains unsubstituted as well as polychlorinated phenolic materials.
It was noted earlier that the main function of chlorination stages is to continue the
removal of lignin from unbleached pulp in
a more selective manner than is possible
during pulping. Oxidation, substitution,
and addition reactions with various reactive
species in the chlorine-water system lead
to the breakdown and removal of most of
the residual lignin from the cellulose matrix. These reactions are described in detail in Chapter III 3. Some lignin is dissolved
in the acidic chlorination filtrate as was
noted earlier. The dissolved lignin consists
of relatively low molecular weight carboxylic acid-containing
organic compounds.
Various chlorine-containing
compounds
such as phenols and fatty and resin acids
also are dissolved in this ftltrate (13, 14).
lignin not dissolved in the acidic C-stage
nevertheless is modified extensively by re-
3.2 Reactions of chlorine with lignin

Model compound studies have provided
critical information for gaining an understanding of the reactions that occur in the
chlorination stage. These studies have been
reviewed and summarized in earlier publications (1, II, 12). Figure 4 illustrates the
major reactions of chlorine with lignin
model compounds based on these studies.
One interesting observation provided by
these extensive model studies is that substitution of chlorine on the phenolic ring
~:}
I
A
~ }
H-C! oR
Ugni'(
-LVdn
/A
~. 8q.
~nln
I
,C.
H 0
-lJg~
~}
I
COOH
~
o (O-Benmquinone
=Aromatic sub8tltutlon
= Electrophlllc
= Oxidation
displacement
C
Clx= Chlorine substltuent(s) at
unspecified ring slte{s)
derIv8tIve)
Ox.
Red .
1
CIx~
DiC8rt1oxy1lc
hgmen18
~OH
OH (C8techoI
deriv8tllre)
FIg.4. 1)e rt!fIetWruof cblorllw IIIIIb ~fllive
"grd" ftwgmeat.
"
8Cid
actions with chlorine (15). Oxidation reactions destroy aromatic ring structures,
generating
hydrophilic
carboxylic acid
groups (Fig. 4). Substitution and addition
reactions lead to the incorporation of chlorine atoms into the structure
of the
residual lignin. In the following alkaline extraction stage, much of the chlorine-substituted lignin is solubilized and removed by
alkaline hydrolysis reactions, a topic discussed in greater detail in Section 4. Studies have shown that some organically bound
chlorine remains with the pulp and cannot
be removed with organic or inorganic solvents (16).
In theory, conditions in the C stage can
be manipulated to favor substitution or oxidation reactions but, in practice, only a few
mills change chlorination-stage variables in
this stage for this express purpose. It has
been shown, for example, that formation
of highly chlorinated phenolic and chlorinated dioxin and furans (products of substitution
reactions)
can be decreased
dramatically by operating the chlorination
stage at a higher pH and splitting the total
charge of chlorine among multiple addition
points (17, 18). The effects of other selected process variables on these chlorine
reactions are listed below:
Change in Bleaching
Conditions and
Putp Cofi\POSition
Effect on
Bleaching
Reaction
Higher temperature
More oxidation
Longer reaction time
More oxidation
Higher pH
More oxidation
Higher chlorine
concentration
More substitution
Higher lignin content
More substitution
More condensed
More oxidation
lignin
Methanol, one of many chlorination byproducts, arises mainly, if not exclusively,

from an oxidative of methoxyl groups from
phenolic rings in the lignin structure (19).
Yields in excess of 70% of the theoretical
amount (based on methoxyl group content)
have been re1\Orted
(20).
Van Heiningen
and co-workers have used the generation

of methanol to study the kinetics and mechanisms of chlorination of pulp (20-22).
247
3.3 Reactions of chlorine with

carbohydrates
Reactions of molecular chlorine with
cellulose and hemicelluloses
are much
slower than those with lignin as indicated
by the substantial reduction in kappa number observed with only a moderate accompanying loss in viscosity. This high degree
of selectivity explains, in part, the widespread acceptance of chlorine as a primary
bleaching chemical for almost 100 years.
Cellulose chains can be broken by oxidation reactions involving hypochlorous acid
or chlorine and also by attack of chlorine
radicals. Carbonyl groups are generated
which render the carbohydrate chain susceptible to cleavage in later alkaline extraction stages.
Studies involving simple
carbohydrates and cellulose have helped to
identify the general reaction types which
lead to formation of both carbonyl and carboxylic acid groups. These reactions have
been reviewed elsewhere (1, 9; Chap. m
3). It generally is accepted that both ionic
and free radical mechanisms are involved
in the chlorination of pulp: ionic reactions
predotninate with lignin and radical reactions predotninate with carbohydrates. lignin acts as an effective radical scavenger
and, by virtue of favorable reaction kinetics, protects carbohydrates from oxidation
reactions. This protecting effect diminishes
as the lignin content decreases. Chlorine
dioxide often is added to help protect
against radical attack as is discussed more
fully below. Other materials, for example,
sulfamic acid, also have been shown to be
effective protectors.
3.4 Reaction kinetics

Chlorine consumption in suspensions of
unbleached pulp is extremely rapid, and lignin removal is correspondingly
rapid as
shown in Fig. 5 (23). In the presence of
excess chlorine, two-thirds of the lignin in
a kraft pulp can be solubilized within 4 seconds and 85% in 30 seconds. lignin removal
approaches an asymptotic litnit at longer
reaction times. Numerous attempts have
been made to explain the observation that
248
Pulp Bleaching
-Principles
and Practice
4. Chlorination process variables

Several process variables can affect the
outcome
of the chlorination
1. Amount
of chlorine
stage:
applied
and consumed
2. Initial kappa number
3. Reaction
time
4. Chlorine
concentration
5. Temperature
o
o
12
16 20 24 28
Time, S
32
36
40
44
6. pH
7. Pulp consistency
8. Degree of chlorine dioxide substitution.
Fig.5. 1lJIIe
remorHIll. tile mUUI s~
of"""
of1nwft }HIIp eblorllUllitm.
some of the residual lignin is resistant to
removal by chlorination and extraction (2427).
In one study (25), for example, a 2minute chlorination (denoted CRin Fig. 6)
was followed by alkali extraction, a second
2-minute chlorination and extraction, and
finally a third chlorination and extraction.
The CE K number was reduced substantially
each time, but the repeated chlorinations
and extractions
failed to completely
delignify this softwood pulp. Thus, some
of the lignin remaining after kraft pulping
is highly resistant to removal by chlorine
and alkali alone (25).
Practically, the bleach plant operator has

only a few of these variables available for
control on a daily basis. The amount of chlorine applied is the main operator controlled
variable.
Both temperature and pH are established
by water recycle practices. The amount of
chlorine applied and extent of black liquor
in carryover both affect pH in the C stage.
Retention time is fixed by equipment limitations and pulp production rates but may
be varied to some extent by changing pulp
consistency. Incoming pulp kappa number
traditionally was set based on pulp yield,
effluent characteristics, recovery considerations, or other concerns. Beginning in the
late 1980s, pressures to meet emissions
30
...
aCE
c CAECE
25
l>.CAECAECE
CA : 2 min., 5.74% CI2 on o.d. pulp
CD
.Q 20
::J
c:
as 15
a.
a.
as 10
~W
: t min., 5.74% CI2 on o.d. pulp
()
5
0
0
10
20
40
30
50
Time, min
Fig. 6. Effects
of re}letded
eblorllUllitm
tmd extraetiorl
08 IIg1".
removal,
lIS measured
IIap/JII
.umber.
4.1 Chlorine charge

The amount of chlorine consumed is
more important in determining pulp quality and extent of delignification than the
amount of chlorine applied. Because most,
if not all, mills in North America have lowered the use of molecular chlorine in response to environmental concerns, chlorine
applied is now, in most cases, virtually
equivalent to chlorine consumed.
As chlorine consumption increases, pulp
brightness in the C stage increases, and the
quantity of lignin remaining after the E stage
(measured by permanganate consumption,
as "CE K number") decreases. A good correlation of the chlorination progress exists
between these two measures (Fig. 7), making it possible to use brightness sensors for
short-term feedback control of chlorine
addition.
The incoming kappa number varies in any
mill situation as does the. level of carryover
of black liquor with the unbleached pulp.
Traditionally, an important function of the
C-stage has been to smooth out this variability so that the rest of the bleach sequence
operates economically. In the non-chlorine
bleach sequences of the future, this role may
be played by an oxygen, ozone, or chlorine
dioxide "first" stage.
One way to express the relationship between chlorine applied and incoming kappa
number is as a "molecular chlorine multiple"
(28). This term is defined as the chlorine
5.5
Molecular
chlorine
4.5
24
22
35
40
Fig. B. Bffrd of nnble4cbell Jnlip 1IIIJIP4

on
tbe IJrlgbmas of cblori..tM Jnltp (_Ieen1M'cblorine _ltIple:
0.18).
ffi
"
CEHDED
0.15
0.20
Kappa factor
0.25
cblorine IlJlPlka-
0.32
C-stage brightness
%GE
A significant economic benefit can be

achieved by selecting an appropriate molecular chlorine multiple as shown in Fig.
10 (34). The shape of these curves is governed by the relative costs of different
bleaching chemicals and chlorine is one of
the least expensive. Another trend shown
in this graph is that, as bleach sequences
become shorter, the economic minimum
favors using more chlorine.
Therefore,
trends toward shorter sequences and lower
chlorine multiples increase costs for two
reasons.
Although environmentally driven process
modifications have made over-chlorination
much less likely, it must be noted that degradation of cellulose may result if the chlorine charge is too high. The data in Fig. I I
8
<Q
as 25
Q.
E
'iii
0
(J
20
:>
w
5'
15
0.22
11
~~3QC
o 40.C
. 50.C
rn
0.24
[J 60C
Il 70.C
V BO.C
5
5
0.16
22
24
26
28
30
C-stage brightness,
32
34
Fig. 7. The re14timlsblp betrrem C stage IJrlgbmas

and CE "I("
,""nber,
Ing of a softwood
In tbB 14bomtory
ImIft Jnllp.
36
20
40
60
80
100
120
bleaeb-
Fig. 9. Effect of liqruJr carryover on moleentar cblorine mnmple

required to obtain a constant
C-stage Jnllp IJrlgbtness.
6
7
8
9
CI2 applied, % on pulp
I
I
I
I
0.160 0.192 0.224 0.256
Kappa factor
COD, Ibiton of pulp
OJ.
4.2 Temperature
and Time
Chlorination stages may be conducted at
various temperatures ranging from ambient
to 70C. As is shown in Fig.ll, viscosity
loss is independent of temperature; for the
most part, given sufficient reaction time, the
extent oflignin removal also is independent
of C-stage temperature. However, temperature does affect reaction rate. Increased
efforts to close the system and conserve
water have led to the recycle of chlorination and chlorine dioxide stage filtrate and
use of paper machine or similar process
waters instead of fresh water for dilution of
unbleached pulp. The result of such filtrate
recycle is an increase in C-stage temperature. The use of recycled filtrate may be
limited by the material of construction
in
pumps, piping, and unbleached pulp storage chests. As is discussed later, it is important to maintain a constant temperature in
this stage to facilitate control strategies and
reduce variability in the post-extraction K
30
::;;
2.5
were generated by allowing pulp to react

to zero residual chemical after increasing
amounts of chlorine were added together
with a small amount of chlorine dioxide to
help preserve viscosity. Viscosity loss has
been shown to be independent of temperature but proportional to chlorine consumption (35).
IIonsfor MrloIISbleaebhlg~.
26
30
25
Kappa number
Fig. 10. IIetnrmItks of optirnhitlf
28
20
0.10
0.2
'3
u
CI>
0 0.18
,-....... /
30
15
:2
u
(,)3.5
[5]
32
W
CJ
~0
u;
In
..
C
E
C>
'C
.Q
..
C>
as
7ij
'C
0
A number of studies (29-31) have indicated that a molecular chlorine multiple of

0.15-0.17 or less is sufficient to avoid formation of chlorinated dioxin and furans as
trace by-products.
Although the molecular chlorine multiple
concept does take into account changes in
the incoming kappa number, it has been
shown that using a constant molecular chlorine multiple does not result in a uniform C
stage pulp brightness or CE K number (Fig.
8) (32). Variable levels of black liquor
carryover with unbleached pulp also affect
the required chlorine multiple (Fig. 9) (33).
0.3
'3 0.28
E
.. 0.26
C
multiple
Cl2 applied, % on pulp

Kappa number
..
15.
250
charge, expressed as percent on pulp,

divided by the unbleached pulp kappa
number:
regulations created pressure to decrease the

unbleached pulp kappa number.
~
W
249
Fig.
11.
Bffect
of cblorine
charge on Jnllp vIscostty.
10
I
I
0.288 0.320
number. Knowledge of expected temperatures is critical in choosing sites for mounting on-line brightness and residual chlorine
sensors.
Most chlorine is consumed within the
first few minutes of reaction, even at room
temperature.
Most delignification occurs
in this same period as was noted earlier.
Even so, allowing extra time for the slower
phase of the chlorination reactions to be
completed significantly improves the economics for attaining a high final brightness.
Pulp quality, as measured by pulp viscosity,
does not suffer as retention time increases
(36). Additional retention time also provides flexibility for handling upset conditions and production rate changes.
4.3 Consistency
Most pulp chlorination stages are conducted at relatively low (2.5-4.0"16) consistency. Several mills now operate mediumconsistency
(8-15%) chlorination
stages,
utilizing recently develQped medium-consistency pumping and mixing equipment.
There are limitations in the volume of gas
that can be mixed into a medium-consistency slurry (37, 38). Laboratory studies
have shown some benefits in selectivity and
efficiency of delignification accruing from
medium-consistency
chlorination (39,40).
However, because of the higher concentration of chlorine, more chlorinated organics
would be expected to be generated at medium consistency (17,41). The operation
of in-line sensors may also be adversely affected by changing from low to medium
consistency.
4.4 pH
The pH of the pulp suspension influences chlorination reactions by controlling
the relative amounts of chlorine or hypochlorous acid present as discussed previously. Organic acids and hydrochloric acid
are generated as by-products as chlorine
reacts with lignin causing the pH to drop
as the chlorination proceeds. The bleach
plant operator can control the pH in only a
few ways. Recycle of chlorination washer
(or chlorine dioxide washer) filtrate for
major or minor dilution of unbleached pulp
251
252
32
co
30
28
(fJ
a,
~24
~..~20
:> 16
22
18
o
o(fJ
234
567
End pH in the first stage
'S;
W
U
I'll. 12. 1JfIeel 01 cillorllllllitnl JIll 011fII8co8IIy .per

~
will lower the pH. In some cases, paper

machine white water is used for such dilution and buffering components
may be
present that affect the pH.
It has been demonstrated in laboratory
studies (42) that a lower pH favors reaction of chlorine with lignin (Fig. 12). When
relatively little chlorine is applied, such as
to oxygen-delignified
hardwood,
pulp
filtrate recycle may be necessary to obtain
a sufficiently low pH. This practice has an
added advantage itl that any carryover of
organics with the unbleached pulp may be
eliminated by reaction with residual chlorine in the recycled filtrate.
4.5 Chlorine dioxide substitution
It is well known that small amounts of
chlorine dioxide added to the chlorination
stage will protect pulp viscosity. This is an
important consideration in some mills, particularly for market pulp producers. A 1988
EPA survey showed that many mills in the
United States did not require chlorine dioxide substitution
to meet pulp quality
targets (43). Environmentally driven modifications in the early 1990s have led to significant increases
in chlorine dioxide
substitution for all NorthAmerican mills.
Chlorine dioxide also is an effective oxidant for lignin and can replace part of the
chlorine charge in the first stage. Because
of the higher unit cost of chlorine dioxide
and the fact that it must be generated onsite, its use in this manner has found limo
ited acceptance until relatively recently.
Many studies have been published
dealing with the substitution of chlorine
points
26
Q..
E
'ii)
12
Optimum
CIO2 addition-
30%
14
30C
10
I 1/ I I"
10 5 I
300
..-
60 3020
Seconds before
5. Process equipment
Chlorinatlon equipment varies considerably at different mills, but many of the system components are common. The diagram
in Fig. 1 shows the following components:
Brown stock pulp dilution
Blending and consistency control
Chemical injection and dispersion
Sensors and control

Reaction
mechanisms
vessels for retention
Pulp washing.
Seconds
60
300
after.......
Timing of chlorine dioxide addition
dioxide for chlorine to achieve viscosity protection and delignification. The impact of
chlorine dioxide substitution on environmental parameters has also been reported
in recent years (44). The timing of chlorine dioxide addition relative to that of chlorine is an important consideration for pulp
quallty as shown in Fig. 13. When used in
relatively small quantities in softwood kraft
pulp bleaching, chlorine dioxide should be
added with or slightly after the chlorine
(45). Chlorine dioxide may be entirely consumed if added too far ahead of the chlorine, resulting in poor viscosity protection.
Similar curves have been developed for
hardwood (46).
Mixing
5 10 2030
Chlorine added
5.1 Stock dilution

Following brown stock washing and
screening, pulp usually is stored at medium
consistency before bleaching to decouple
the pulping and bleaching operations. Water is added at the base of the storage tank
to dilute the pulp for pumping. The volume of water used for dilution can be con.
siderable, particularly when, for example,
pulp is stored at medium consistency (12%)
and the C-stage is operated at low consistency (3%). In this case, a mill producing
1000 metric tons per day would add 0.27
cubic meter per second (4340 gal/min) of
dilution water.
This water can be recycled chlorinationor chlorine dioxide-stage filtrate, fresh water, paper machine or pulp dryer white
water, or other process streams. There are
many operational considerations, depending on the choice of dilution water:
Corrosion due to incompatible materials of
construction
Chlorine demand of dissolved organics in the
dilution water
Formation of highly chlorinated by.products
from recycle of chlorinated organics
C-stage pH, temperature
Overall mill water usage
Waste treatment plant hydraulic capacity,
--Chapter IV 2: Chlorination
Fillers, clays, other additives which that may
interfere with optical sensors
Inorganic compounds which buffer pH and
create scale or deposits
The choice of the dilution water source
must involve these and perhaps other considerations. For low-consistency chlorination stages, the C-stage water balance is the
highest volume filtrate/effluent
system in
the bleach plant. A purge from this system
to the wastewater treatment plant is required because corrosiveness due to the
presence of chloride ions and the low pH
preclude countercurrent
use of this filtrate
for screening or brown stock washing.
5.2 Blending and consistency control
Stock is diluted to a fixed consistency in
the 2.5-4.0% range and pumped out ofstOrage to an agitated blend chest. This step
helps smooth out fluctuations in the lignin
content of the unbleached pulp and consistency.
Elimination of short-term variations in
these two variables facilitates control of
chemical addition and improves the uniformity of chlorinated pulp. This procedure
has taken on added significance with the
recent concerns raised about formation of
chlorinated organics that can occur in cases
of excess chlorine application. Dilution is
generally controlled at two points: out of
storage (major dilution) and out of the blend
chest (minor dilution).
5.3 Chemical injection and dispersion
The goal is to treat each fiber in the pulp
suspension
uniformly with the proper
chemical charge. Injection techniques and
mixing devices are used to disperse the
chlorine gas because more chlorine is generally required than can practically be dissolved in the water, throughout the slurry.
In low consistency applications, this goal
generally is achieved by dispersing the gas
in water in the form of small bubbles using
venturi devices or static mixers. High-shear
mixers are used in low- and medium-consistency chlorination systems, because of
the importance of good mixing for lowering the formation of chlorinated by-products (39). The effects of water temperature
253
on chlorine gas dispersion have been studied in the laboratory (47). Hot water was
shown to facilitate coalescence of small
bubbles into larger ones in less than 0.25
second. These findings have practical significance for the design of chlorine injection systems: the chlorine gas dispersion
should be formed and injected into the
slurry with as little "dead time" in the pipeline as possible and should be mixed with
the pulp slurry immediately following injection.
Maintaining an adequate water flow to
the dispersion device has also been shown
to be important. At least 60 kg of water per
kg of chlorine is required to form a stable
dispersion and prevent plug flow (47).
Adding chlorine gas without prior dispersion can be practiced on low- or mediumconsistency
systems when high-shear
mechanical mixers are used. Because no
injection water is used, check valves are recommended to prevent plugging chlorine
addition ports by pulp during interruptions
in the chlorine flow.
Chlorine dioxide solution should be
added together with the chlorine dispersion, upstream or downstream depending
on chlorine dioxide substitution (Fig. 13).
Because chlorine dioxide is added as a solution, the mixing requirements are less rigorous and static mixers are often used.
5.4 Mixing
Diffusion of chlorine in pulp slurries has
been shown to be slow relative to the rate
of reaction of chlorine with pulp (47).
Good mixing is therefore important to avoid
pockets of over-chlorinated and under-chlorinated pulp. Proper performance of in-line
sensors depends on uniform mixing of
chemicals with pulp. Symptoms of poor
mixing may include dirty pulp (shives, bark
particles) after the chlorination stage, loss
of pulp viscosity, and varying levels of residual chemicals in the washer vat. Local
over-chlorination may result in formation of
highly chlorinated by-products even at relatively low chlorine dosages.
Several general types of mixers currently
are used in chlorination stages, each having advantages and disadvantages.
254
In-line static mixers are also used in low

consistency chlorination stages. A 1982
survey found that these mixers dominated
NorthAmerican bleach plants (48). In this
equipment, mixing elements are built into
a special section of the stock line to repeatedly subdivide the flow and induce turbulence and radial mixing. One advantage
provided by this type of mixer is that it does
not require much space because it is part
of the stock line. Because there are no
moving parts, maintenance and operating
costs are low. A potential disadvantage is
that these mixers must be sized properly
to perform well. Changes in production
rate may cause problems with inadequate
mixing at low flow rates and high pressure
drops at high flow rates.
"High-shear" mechanical mixers also are
used to disperse chlorine. These mixers,
introduced in the early 19808, operate with
low/medium consistency stock. Chlorine
gas can be injected directly without prior
dispersion in water, and some results indicate improved performance compared to
static mixers. These mixers are relatively
insensitive to production
rate changes.
Depending on the manufacturer, the pressure drop across these devices may be
slightly negative (pumping action) or 1(}'15
psi positive. Low-consistency stock can be
pumped through some of these mixers even
when the motor is off. The rotating elements operate at 6O(}.1500 rpm which implies high maintenance
requirements
compared with static mixers.
6. Process control
The objective of a chlorination stage control strategy is to produce a uniform pulp
exiting the C-stage washer regardless of incoming pulp variations in kappa number,
black liquor carryover, consistency, temperature, or flow rate. In part, this implies
maintaining a constant ratio of chlorine
consumed (not applied) to mass flow of lignin through the pipe line. In practice, this
goal can be achieved by good feedback control of chemical addition based on in-line
sensor measurements of the degree of chlorination at a point downstream. Sensors can
detect variations in pulp brightness (reflec-
tance), temperature, pH, and level of residual chemical(s). Control room personnel and the computer control system can
then use this information, together with
consistency
and flow measurements,
to
adjust chemical flows in response to detected variations. Sensors can be located a
short distance after chlorine/chlorine
dioxide addition points, after the retention
tower, in the washer vat, or in all of these
locations (49).
Another technique for controlling chemical addition to the C stage is to measure Cstage washer pulp brightness and extracted
pulp K number. These tests are still widely
used today as a longer term set point to
adjust pre-tower sensor set points. Other
manual tests that are commonly performed
are chlorine residual in the washer vat and
vat pH.
Reflectance of light by the chlorinated
pulp slurry is an indication of lignin content. Several optical sensors use this principle to estimate the degree of chlorination
by illuminating the flowing stock at a specified wavelength.
As noted earlier, paper
machine additives such as titanium dioxide
can give false indications of delignification
progress by increasing the reflectance of the
stock slurry. Aiso, the relationship between
chlorinated pulp brightness and post-extraction K number shown in Fig. 7 changes with
changes in chlorine dioxide substitution
level. Practically, this means that brightness
setpoints must be adjusted or sensors must
be tuned as the degree of substitution
changes.
Two basic types of sensors are used to
measure chemical residuals (49): one is
based on measuring the "ORP" (oxidationreduction potential) and the other type depends on polarography. The signal from a
polarographic sensor indicates the voltage
required to reduce chlorine at an electrode
which is directly proportional
to the residual chlorine concentration. The ORP sensor measures the potential
difference
between a platinum and reference electrode
immersed in the solution. The signal is
markedly non-linear, however, and rises
sharply as the chlorine residual increases
from zero but levels off at higher residuals.
7. Effect of chlorination on
shives and dirt removal
The chlorination stage has played an important role in the bleaching of coarse particles derived from the woody starting
material, for example fiber bundles (shives),
bark specks, and particles from ground up
knots. Bleaching has relatively little impact
on other extraneous particles, such as sand,
pitch particles, and rust that may be present.
Removal of these materials, collectively
known as "dirt; is an important goal of
bleaching, in addition to brightness development. The presence of dirt in the final
paper or board products can cause a variety of quality defects. A significant observation is that particle reduction during
bleaching is a statistical operation; ev~n
though the percent reduction may be acceptably large, when more particles enter
the bleach plant, more leave the bleaching
operation intact (50, 51).
According to extensive laboratory studies conducted by AxegaId and co-workers,
bleaching eliminates most of the shives,
leaving the bark and knot particles and inorganic materials relatively enriched among
the remaining particles. Given that the relative rate of chlorine bleaching of dirt particles is much lower than that for fibers,
several principles have been proposed for
improving the cleanliness of the final pulp
(52). These include maintaining high concentrations of chlorine and operating the
chlorination stage at lower temperatures to
ensure a chemical residual for a longer period of time. These same principles apply
to chlorine
dioxide and hypochlorite
bleaching, but not to oxygen and ozone
bleaching. In these latter cases, the kinetics of bleaching particles and fibers are similar so that little can be done by way of
process modification to enhance dirt removal dirt.
Even with partial chlorine dioxide substitution, higher chlorine charges lead to
improved dirt bleaching (50). Clearly,with
the trend toward decreasing use of chlorine
for bleaching, it becomes increasingly advantageous to take steps to prevent dirt
particles from entering the bleach plant.
255
256
These steps could include improved chip

quality (fewer oversize, over-thick chips),
better liquor penetration
in the pulping
process, improved debarking, and greater
efficiency in brown stock screening.
Removal of shives and dirt is covered in
more detail in Chap. IV 11.
8.
Environmental
aspects of
chlorination
Lignin represents about 4.5% of the dry
weight of unbleached softwood kraft pulp
at 30 kappa number. Perfectly selective
delignification would therefore lead to a
4.5% yield loss across the bleach plant.
Actual values are estimated at about 7%, or
70 kg/ton of unbleached pulp, depending
on the bleaching process and the final
brightness target. Because most of the residuallignin is degraded and removed in the
chlorination and extraction stages, the chlorination-stage filtrate is a major contributor
of organic loading to the bleach plant effluent stream. Because, in most cases, chlorination is conducted at low consistency, the
volume of filtrate in the overall water balance is large in comparison
with other
bleaching stages operated at medium consistency unless recycled filtrate is used for
dilution. In most existing bleach plants, a
large purge to the waste treattnent plant is
required because of the corrosiveness of
chlorination filtrate. The degree of recycle
of this filtrate plays an important role in determining the temperature and pH of the
chlorination stage and affects the quantity
and type of chlorinated organics that are
formed.
The lignin remaining in the fiber after
pulping still contains aromatic structures,
but differs from "native" lignin in that it
contains more carbon-carbon inter-unit linkages and fewer labile inter-unit ether linkages (53). Reactions in the chlorination
stage lead to substantial depolymerization
oflignin; carboxylic acid groups are formed
and chlorine atoms are introduced.
Most
of the aromatic rings are destroyed by oxidative cleavage reactions. Some of the degraded material is dissolved and removed
in the acidic chlorination stage filtrate, but
t
5%
Mw< 1000
30%
Mw < 25000
C-stage
Jlig.14.
Mo'-"'"
mgllt
E-stage
MstrlIndimt of ",.,erllIl 4isMJlfletl
most of the degraded lignin and carbohydrate fragments are solubilized in the following hot alkaline extraction stage. It has
been estimated that of the 70 kg/ton that is
removed during bleaching:
about 50 kg
originates from lignin, 19 kg from carbohydrates, and 1 kg from extractives (54).
About 90% of the chlorine used for
bleaching is converted to chloride ion,
which contributes to salinity and corrosivity
but has no harmful effect on the receiving
streams at the concentrations encountered.
The balance, about 10%,is bound to organic
molecules or high molecular weight material. The organically bound fraction is measured asAOX (adsorbable organic halogen).
AOX is used world-wide as a basis for estimating the discharge of chlorinated organics, and has in some cases been used in
establishing effluent discharge limits for
pulp bleaching operations. Details on the
significance of this sum parameter for characterizing effluents are covered in Chap.
Vlll, Sects.I and 2.
Dence andAnnergren initially compiled
much of the relevant information that has
been generated regarding the chemical
composition
of the chlorination
filtrate
(55). Kringstad and Lindstrom provided an
update in 1984 on the nature and identity
of compounds in the C- and E-stage filtrates
(56). Through the use of membrane separation techniques, it has been shown that
about 70% of the organically bound chlorine in the chlorination
stage filtrate is
present as high molecular weight material
If blMdmIg stIIges.
C
"'
"""
(greater that about 1000 g/mole, based on

a polymer standard). The remaining 30"AJ
of the weight of material passes through the
1000 molecular weight cut-off membrane.
In contrast, about 95% of the organically
bound chlorine in the E-stage filtrate is in
the high molecular weight fraction (Fig. 14)
(57).
In the low molecular weight fraction,
various classes of monomeric compounds
have been identified including carboxylic
acids, carbohydrates (present as oligomeric
fragments), neutrals (including methanol,
chloroform, and acetone), and chlorinated
phenols. Some of these compounds contribute to the observed toxicity of the untreated
chlorination stage filtrate. This topic is discussed in greater detail in Chap. VIII, Sects.
1-3.
Material comprising the high molecular
weight fraction is considered to be of less
significance from a biological standpoint
because this material is too large to pass
through cell wall membranes.
Nevertheless, the material is environmentally significant because it contains chromophoric
structures that interfere with the passage
of light through the receiving water. The
high molecular weight fraction consists primarily of chlorine-substituted
polycarboxylic acid polymers originating from
oxidative degradation of the aromatic ring
system in the residual lignin. The aromatic
nuclei content has been shown in several
studies to be low (58-61).
Degraded material from the chlorination

stage represents a biological oxygen demand (BOD) for the wastewater treatment
system and contributes to the dark color of
the effluent as noted above. The chlorination stage ffitrate is Initially light straw-colored but darkens with time and also as the
pH is increased following mixing with other
waste streams.
The relative amounts of some of the more
prominent materials in chlorination ffitrate
are noted in Table 1 (62). Methanol,which
arises from demethylation
of methoxyl
groups by chlorine, is by far the most abundant single component (20, 21). This compound is easily degraded in biological
treatment systems.
Component
Amount
kg/ton bleached pulp
Methanol
4.6
Formic Acid
1.2
Acetic Acid
0.1
Non-volatile acids
0.3
Carbohydrates'
0.4
Chlorophenols
2.3 x 10'3
'present as polymers
Some organically bound chlorine remains
with the pulp and cannot be removed even
by exhaustive extraction with water or organic solvents (16). The ecological significance of this type of organically bound
chlorine has been compared with that of
polyvinyl chloride (PVC), a common plastic, in which the chlorine is part of the structure of the polymer itself and quite inert.
Chloroform is one of the volatile by-products of pulp chlorination which is proposed
for regulation in bleach plant ffitrates in the
United States. A number of structures found
in pulp can react with chlorine to yield chloroform, including carbohydrates and lignin
(63). Although chloroform is found in largest amounts in hypochlorite
bleaching
stages, it is also detected in C, E, and D
stages (14,64-67). The source of the chlo-
257
roform in D stages may be from chlorine in

the chlorine dioxide solution but may also
arise from reactions with the intermediately
formed hypochlorous acid (63). Factors
affecting the formation of chloroform in the
chlorination stages have been studied and
reported recently (68).
Under certain conditions, chlorinated
dioxin and furans, most notably 2,3,7,8tetrachlorodibenzo-JHlioxin
(2378- TCDD)
and 2,3,7 ,8-tetrachlorodibenzofuran
(2378TCDF) may also be formed in the chlorination stage. These compounds are detected
in only trace amounts but are highly stable
and persistent in the environment and are
classified as extremely toxic. Detection of
the foregoing compounds in bleaching effluent has prompted the development of
new technology to prevent their inadvertent formation. This subject is covered in
more detail in Chap.VIll 3.
References
1. Dence, C.W and Annergren, G. E., in Tbe
Bleaching
of Pulp (R. P. Singh, Ed.) 300
eOO.,TAPPI PRESS,Atlanta, 1979, Chap. 3.
2. Loras,V., in Pulp and Paper Chemistry and
Chemical Technology Q. P. Casey, Ed.) 3rd
eOO., Wtley, New York, 1980, Vol. I, p. 670.
3. Smook, G.A., Handbook for Pulp & Paper
Technologists
(M.}. Kocurek, Ed.), TAPPI
PRESS,Atlanta,
1982, p. 160.
4. Singh, R. P., Handbook
of Pulp and Paper
Technology, 2nd eOO., Reinhold, New York,
1970, p. 249.
258
11. Dence, C.W, in Ugnins: Occurrence, Formatton, Structure,

and Reactions,
(K. V.
Sarkenen and C. H. Ludwig, Eds.) WileyInterscience,
New York, 1971, p. 373.
12. Gess,}.
M. and Dence,
54(7):1114 (1971).
C. W., Tappi
31. Berry, R. M., Pulp Pap. Can. 90(8):T279

(1989).
14. Kringstad,
K. P. and Lindstrom,
K.,
Environ. Set. Tech. 18(8):236A (1984).
32. Hise, R. G., "Chlorination

of Pulp," 1992
Tappi Bleach Plant Operations
Short
Course Notes,TAPPI PRESS,Atlanta, p. 69.
15. Kempf, A. W. and

53(5):864 (1970).
Dence,
C. W., Tappi
16. Reeve, D. W and Weishar, K. M.,]

Paper Sci. 16(4):}118 (1990).
17. Hise, R. G., TapPiJ.
72(12):121
Pulp
(1989).
(1992).
19. Van Buren,}. B. and Dence,

53(12):2246
(1970).
C. W, Tappi
21. Van Heiningen, A. R. P.,j Pulp

16(3):}83 (1990).
38. Reeve, D. W, Pu, C. M.,Ashinowo,

Pap. 59(3): 172 (1985).
Pap. Set.
22. Ni, Y., Kubes, G.}., van Heiningen,

A.,
"Demethylation
Kinetics of Kraft Pulp
Chlorination;
1989Tappi Pulping Conference Proceedings,
Book 1, p. 23.
23. Russell, N.A., Tappi 49(9):418
(1966).
B.
6. Rydholm,
Intersdence,
26. Berry, R. M., and Fleming,

69(3):226 (1987).
9. Kraft, E, The Pulping

of Wood, (R. G.
MacDonald,
Ed.), 2nd edn.,McGraw
Hill,
New York, 1969, p. 629.
10. Rydholm,
S. A., pulptng
Processes,
Interscience,
New York, 1965, p. 921.
R., Pulp
36. Reeve, D. W, "Chlorination

Stage Conditions," CPPA Annual Meeting Preprints,
Tech. Sect., CPPA, Montreal,
1992, p.
139A.
25. Berry,
R. M. and
Fleming,
HolzfiJrschung
41(3):177 (1987).
S. A., pulping
Processes,
New York, 1965, p. 916.
35. Histed,}. A. and Vega Canovas,

Pap. Can. 88(1):T22 (1987).
20. Van Heiningen,A.

R. P., "The Characteristics of Pulp Demethylation
During Chlorine Dioxide
Bleaching,"
1991 Tappi
Pulping Conference
Proceedings,
TAPPI
PRESS,Atlanta, Book 2, P 657.
Tappi
8. Rydholm,
Interscience,
33. Streisel, R. c., Hise, R. G., BilIs,A. M., "The

Effect of Brownstock Washing on Bleach
Plant Effluents," 1991 Thppi Brown Stock
Washing
Short Course
Notes, TAPPI
PRESS, Atlanta, Section 20.
34. Annergren, G., lindblad, P.-0., Norden, S.,
Svensk Pappersttdn.
90(12):29 (1987).
18. Hise, R. G., Tappi j 75(2):57
5. Parsons,}. 1., Handbook

of Pulp and Paper Technology, (K.W Britt, Ed.) 1st eOO.,
Reinhold, New York, 1964, p. 267.
7. Kraft, E, The Pulping

of Wood, (R. G.
MacDonald, Ed.), 2nd eOO., McGraw Hill,
New York, 1969, p. 629.
30. Kringstad, K. P., Fleming, B. I., Voss, R. H.,

Luthe, C. E., 1988Tappi International
Pulp
Bleaching Conference Proceedings,TAPPI
13. Voss, R. H., Wearing,}. T., Mortimer, R. D.,

Kovacs, T., Wong,A., Pap. Puu 62(12):809
(1980).
24. Pugliese, S. C. and McDonough,T.}.,

j 72(3);159 (1989).
S. A., pulping
Processes
New York, 1965, p. 916.
29. Axegard,P., 1988Tappi International

Pulp
27. Grangaard.
I.,
B.I., Pap. Puu
D. H., Tappi 39(5):270
(1956).
28. "Molecular Chlorine Multiple" has been

proposed for use by the Tappi Bleaching
Committee.
Related terms still in common use include "Chlorine Factor" (synonymous) and "Kappa Factor." The latter
is more accurately called" Active Chlorine

Multiple" because it includes chlorine and
chlorine dioxide, expressed as % equivalent chlorine on pulp, divided by kappa
number.
37. Bennington,P.}.,
Tappij.
76(7);77
(1993).
T., Pulp
39. Reeve, D. W, Earl, P. E, Gullichsen,}.,

Pu,
C. M., Magued, A., Rapson, W H., Pulp
Pap. Can. 89(6):T202
(1988).
40. Tibbling, P.,"Medium Consistency
Chlorination: Studies in a High Intensity laboratory Mixer," 1988 Tappi International
Proceedings,
41. Berry, R. M., Fleming, B. I., Voss, R. H.,
Luthe, C. E., Wrist, P. E., Pulp Pap. Can.
89(12):151 (1988).
42. Rapson, W H., Tappi 61(10):97
(1978).
43. US EPA Document,"Summary

ofTechnologies for the Control and Reduction of Chlorinated
Organics
from the Bleached
Chemical Pulping Subcategories
of the
Pulp and Paper Industry," draft dated April
27, 1990.
44. Pryke, D. c., "The Impact of Chlorine Dioxide Delignification
on Pulp Manufacturing and Effluent Characteristics
at Grande
Prairie,Alberta;
Non Chlorine Bleaching
Miller Freeman,
Inc., San Francisco, 1993, Paper #11.
45.
du Manoir,]. R., Trans. Tech. Sect. CPPA

6(2):TR25 (1980).
46.
Macas, T. S. and
tion Strategy:
Kraft Softwood
ing Preprints,
Montreal, 1985,
Gowan, G. A., "ChlorinaKraft Hardwood

versus
Pulp," CPPAAnnual MeetTech.
Sect. (CPPA),
Book A, p. 205.
47. Reeve, D.W, Pu, C. M., Oshinowo,T.,

Pap. 59(3):172 (1985).
48. Reeve,
tion
D. W and Davis,].
Practice
in North
Pulp
c., "Chlorina-
America
Part
I:
Process Conditions, Chlorine Dispersion,

and Mixing," 1982 Tappi Pulping Conference Proceedings,
p.347.
49. Baker,]., "Bleach Plant Dual Sensor Control," 1991 Tappi Bleach Plant Operations
Short Course Notes,TAPPI PRESS,Atlanta,
p.205.
259
57. lindstrOm, K., Nordin,]., Osterberg,

E, in
Advances
in tbe Identification
and
Analysis of Organic PoUutants in Water,
(L. H. Keith, Ed.) Ann Arbor Science,Ann
Arbor, MI, 1981.
58. Hardell, H.-L. and de Sousa,
Papperstidn.
80:110 (1977).
E, Svensk.
59. Hardell, H.-L. and de Sousa,

Papperstidn.8O:201
(1977).
F., Svensk.
60. Lindstrom,
Holzforscbung
K.
and
Osterberg,
39(3):149 (1985).
F.,
61. Erickson, M. and Dence, C. W, Svensk.

Papperstidn.
74:316 (1976).
62. Hardell, H.-L. and Lindgren, B. 0., SSVL
Project No.7, "Chloride in the Recovery
System," Report No. 21, Stockholm, 1976.
63. Hrutfiord,
73(6):219
B. E and Negri, A. R., Tappi ].

(1990).
50. Axegard,
P., Lindblad,
P.-D., Popke, I.,
Puukko, M., "The Matrix for Softwood
Pulp Quality and Effluent
Kraft Pulp
Load," 1991 Tappi Bleach Plant Operations
Short Course Notes,TAPPI PRESS,Atlanta,
p.21.
64. NCASI Technical Bulletin 515, "Results of

Laboratory
Studies of Bleaching Parameters Affecting Chloroform
Production
from Kraft Pulps; National Council of the
Paper Industry for Air and Stream Improvement, New York, 1987.
51. Annergren, G. E. and Lindblad, P.0., Tappi

59(11):95 (1976).
65. NCASI Technical Bulletin 558, "Results of

Field Measurement
of Chloroform Formation and Release from Pulp Bleaching;
National Council of the Paper Industry for
Air and Stream lmprovement,
New York,
1988.
52. Axegard,
P. and Bergnor,
Shives and Dirt
E., "Bleaching
- An Overview,"
1991
Tappi Bleach Plant Operations

Short
Course Notes, TAPPI PRESS,Atlanta, p. 31.
53. Marton,]., in Lignins:Occummce,
Formation, Structure,
and Reactions,
(K. V.
Sarkenen and C. H. Ludwig, Eds.), WdeyInterscience,
1971, p. 639.
54. Annergren,
G.E., unpublished
results.
55. Dence, C. W, in The Bleacbing

of Pulp,
(R. P. Singh, Ed.), 3rd edn., TAPPI PRESS,
Atlanta, 1979, pp. 69-71.
56. Kringstad,
K. P. and Lindstrom,
K.,
Environ. Sd. Technol. 18(8):236A (1984).
66. Dallons, V. J., Hoy, D. R., Messmer, R. A.,

Crawford, R.]., TapPiJ. 73(6):91 (1990).
67. Crawford, R.]., Dallons, V. J., Jain, A. K.,
Jett, S.W, TapPiJ 74(4):159 (1991).
68. DaIIons, V. ]. and Crawford, R. J., "Chloroform Formation in Bleaching;
1990Tappi
Pulping Conference
Proceedings,
TAPPI
SECTIONIV:
The Technology of
Chapter 3:
Chlorine Dioxide in Delignification
Douglas W. Reeve
and Applied Chemistry
Pulp & Paper Centre
Toronto, Ontario, Canada
1. Introduction
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
2. DeUgnificationchemistryandkinetics
2.1 Definitions.. . . . . . . . . . . . . . . . '. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2 Reactions during chlorine dioxide delignification
.....
2.3 Delignification kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3. ~tlonefEkiency..
...
3.1 Degree ofsubstinItion and mode of addition.
3.2 Alkali required for extraction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3 Brightness development. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.4 Chlorate formation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4. Process flowsheet and delignification conditions . . . . . . . . . . . . . . . . . . . . . . ..
4.1 Flowsheets and equipment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2 Chemical charge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4. 3 Timing of chlorine dioxide addition.
4.4 Time and temperature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.5 pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.6 Chloride ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.7 Consistency
4.8 Carryover from brown stock washing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
263
263
263
264
265
266
266
268
269
271
273
273
273
274
275
276
278
278
5. Pulp quality .. .. .. .. . .. .. .. .. .. .. . .. .. .. . .. .. .. .. . .. .. .. . .. .. .. ..
5.1 Brightness stability. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.2 VIScosity and strength. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3 Cleanliness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.4 Extractives and organochlorine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.5 Dioxins in pulp. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6. Effluent properties. . . . . . . . . .. . . . . . . . .. .. . . . . . .. . . . . . . . .. . .. . . .. . . . . ..
278
278
279
280
281
282
282
6.1 Dioxins
278
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
6.2 AOX and EOX . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282

6,3 Chlorophcnols
6.4 Biological
6.5 Other
7.
Economic
and other
effects.
parameters:
factors.
organochlorine
compound5
..... .......,....
. . ~61
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
color, chlorate,
BOD, COD.
. . . . . . . . . . . . . . . . . . . . . . . . . 286
.................................................
261
286
"
Chapter IV 3: Chlorine Dioxide in Delignification
Chapter IV 3:
Chlorine
Dioxide in
Delignification
1. Introduction
"Euchlorine," a mixture of chlorine dioxide and chlorine generated from the reduction of potassium chlorate by hydrochloric
acid, was first described by Davy in 1811
who noted that it destroyed the color of
vegetable dyes (1). Watt and Burgess patented the bleaching of soda wood pulp with
chlorine, euchlorine, and sodium hydroxide in 1854 (2). In the 1920s,Schmidt and
co-workers demonstrated that chlorine.dioxide does not react with carbohydrates
(3). In the 1930s, the Mathieson Chemical
Corp. introduced a process for bleaching
in which sodium chlorite was added to a
pulp suspension and ~ous
chlorine was
added to "activate" the. chlorite, that is, to
generate chlorine dioxide. The first industrial processes for continuous generation
and use of chlorine dioxide for pulp bleaching began in 1946 with almost simultaneous, though independent, developments
in Canada and Sweden (4, 5). In one early
application, chlorine dioxide was used as
the sole bleaching agent, replacing chlorine
for delignification and, in later stages for
bleaching, to facilitate resin removal and for
the preparation of pure alpha cellulose from
sulfite pulp (6).
However, from 1946 on into the 1980s,
chlorine dioxide was not used extensively
for delignification but was mainly used for
bleaching in the final stages. Chlorine dioxide was more expensive than chlorine or
calcium hypochlorite, but it enabled production of high brightness kraft pulp without loss of pulp strength. Indeed, it was
these advances in pulp bleaching technology and chlorine dioxide generation which
stimulated the growth ofthe bleached kraft
industry.
Industrial use of chlorine dioxide to replace chlorine was at first only a means of
protecting the strength of the pulp; 5-10%
263
of the chlorine was replaced with equivalent chlorine dioxide (7). However,in 1963
it was reported that substantial substitution
of chlorine by chlorine dioxide resulted in
a synergistic effect so that delignification
efficiency was greatly improved (6). Further improvement was achieved when the
chlorine dioxide and chlorine were added
sequentially, chlorine dioxide first, with 50%
substitution having the greatest efficiency
(8). This technique did not gain wide acceptance until the late 1980s when environmental
concerns
about chlorinated
dioxins and other chlorinated organic materialled the industry to decrease chlorine
use and adopt substantial, and later complete, replacement with chlorine dioxide.
In this chapter, the subjects discussed are:
process chemistry, flowsheets, and variables; pulp qualities such as brightness,
strength, and cleanliness; dioxins in pulp
and effluent; effluent qualities such as organochlorine content, toxicity, and color;
and finally, economics. There have been several reviews on chlorine dioxide delignification in which these issues are discussed
(9-14).
2. Delignification chemistry and

kinetics
2.1 Definitions
Chlorine dioxide is an oxidant which
accepts five electrons per molecule in being reduced to chloride ion:
CI02 + 4 W + 5 e- --+ CI- + 2 HP
[1]
The molecular weight of chlorine dioxide

is 67.5 and so its equivalent weight is 13.5
(67.5 + 5). Chlorine accepts two electrons
when reduced to chloride ion, has a molecular weight of 71, and so has an equivalent weight of 35.5 (71 + 2):
CI2 + 2 e- --+ 2 Cl"
264
CI02 Bleaching Reactions

Oxidation
states
5
C103-
CI02
_
--
C102:
1
2
8 9 10
J
L_-t~HCIO
3--.
Cb ~l~
CI- .,--4
-1
6 4 5 7
Organochlorine
of chlorine dioxide is equal to 2.63 weight

units of "equivalent chlorine." Chlorine dioxide substitution, expressed as a percent,
is also a very common unit and is based on
equivalent chlorine.
Equivalent chlorine
applied on pulp is sometimes expressed as
"kappa factor," also known as (equivalent
or active) chlorine multiple:
chlorine + chlorine dioxide appliedl
as % equivalent chlorine on pulp
[3]
fkappal funbleached PulP
x
Lfactor
Lkappa
number
As an example, a 25 kappa pulp treated with

chlorine and chlorine dioxide corresponding to a kappa factor of 0.20 at 50";6substitution would be treated with:
25 x 0.20
[2]
Therefore, in substituting chlorine dioxide

for chlorine to provide equivalent electron
transfer, one weight unit of chlorine dioxide can replace for 2.63 weight units (35.5
+ 13.5) of chlorine.
"Equivalent chlorine," also known as active chlorine, is a common unit of oxidant
in bleaching technology; one weight unit
Pulp Reactions
"\.0 X0."\0 =
and
5.0 x 0.50
/ 2.63
5.0";6equivalent chlorine
on pulp
50 kg equivalent chlorine per
metric ton of pulp
100 Ib equivalent chlorine
per short ton of pulp which
would be made up of
2."j% chlorine on pulp
= 0.95%
chlorine
on pulp.
dioxide
2.2 Reactions occurring during chlorine

dioxide delignification
Chlorine dioxide is reduced through a
series of steps involving several intertnediates before chloride ion is produced. Hypochlorous acid (HOCl) and chlorine (CI2)
are among these intertnediates, and their
presence can lead to the fortnation of chlorinated organic matter. Another undesirable
by-product is chlorate ion (CIO;) which is
not reactive and so its formation' means loss
of bleaching efficiency.
Figure 1 illustrates the changes in oxidation state and reaction pathways of the reactive intermediates
during chlorine
dioxide bleaching of pulp (15). Chlorine
dioxide reacts with pulp, transferring, in the
process, one electron to produce chlorite
ion (CI02") by reaction {I} (Fig. 1). Chlorite ion does not react directly with pulp.
Chlorine dioxide also reacts with pulp 12}
to fortn HOCl, which is, in part, converted
to CI2by hydrolysis 13}. Hypochlorous acid
and chlorine react with pulp producing
chloride ion and chlorinated organic matter {4 to 7}. Chlorine reacts with chlorite
to regenerate chlorine dioxide {l0}, while
hypochlorous acid reacts with chlorite to
265
.'
100
....
<1J
E
~"
'x
0 . (D+C)E
l::,. .... DE
<1J
7 .J:J
E
::::I
6 c:
::.!
::::I 60
en
c:
20
4
-----
~::.!
5
4
50C
0
40
80
120
160
tlloxlM
IJIItl eblorllrs. liellg,dftclllimI
of sojlrrJootlltrwft
40

of cblorltre
::::I
~'l::,. r-:P-~ __ .,cr-~{j

"'x
Do
0 20
l::,.--"'D--------
...
<1J
7 .J:J
6 c:
c: 40
8
E
....
Fig. 2. TIle Nte
. CE
<1J
...
::::I 60
en
c:
0
U
....
c: 40
JIll
~~9
'* 80
,,'
DE
.........-.-.-JIIl
100
(D+C)E19
'*
,,' 80
266
/JfIlJIllt
80
120
upc.
Fig. 3. TIle Nte of eblorltre tlloxlM IJIItlcblorlM liellpljfctrllml
form cWorate ion (00,) 18} (16). Under

acidic conditions, cWorite decomposes to
cWorine dioxide and cWoride ion 19} (16).
The pathways described above and the
mechanisms of reaction. of cWorine dioxide with lignin and with other pulp constituents are discussed in depth in Chap. m
3 (125).
Much of the literature on cWorine dioxide delignification concerns manipulation
of conditions to influence the reactions iIlustrated in Fig. 1; for example, to decrease
cWorate formation and thereby increase
efficiency or to decrease cWorine formation
so as to decrease organocWorine formation.
2.3 Delignification kinetics

The earliest
studies of the rate of
delignification using cWorine dioxide,alone
and in combination
with cWorine, were
reported by Hatton in 1966 (17). The results for treatment of softwood kraft pulp
having a 19.5 permanganate number (kappa
number of approximately 30) are shown in
Figs. 2 and 3. The same amount of equivalent cWorine was applied for each case (approximately 0.18 kappa factor). As is typical
of such studies, after the cWorine dioxide/
cWorine treatment, the pulp is treated with
alkali in an extraction stage and the extent
of delignification is measured after the extraction stage. The initial rate of consump-
tion of oxidant and the rate of delignification are extremely high. Even at the
relatively low temperature of lOoC, 90% of
the cWorine and 60% of the cWorine dioxide are consumed in only ten minutes (Fig.
2), while at 500c virtually all of either chemical is consumed in ten minutes (Fig. 3). At
l00c, the rate is low enough so that cWorine can be observed to react faster than
cWorine dioxide; both the rate and extent
of delignification with cWorine dioxide are
significantly less. At 500C, the rates of cWorine dioxide consumption
and delignifi.
.
cation are indistinguishabl e fro m th oseo f
cWorine; a SO/50 mixture of cWorine and
cWorine dioxide (D+C) reacts almost as rapidly as cWorine.
Extensive kinetic studies by Germgard
show that the rate of delignification with
cWorine dioxide is fifth order with respect
to kappa number (18):
-!.!K
dt
= k [CIO 2]05 [H+102 [Cn03
K5
This is an empirical, rather than mechanistic, kinetic expression which represents

a large number of simultaneous and sequential reactions between cWorine dioxide and
lignin. The activation energy is in the range
52 to 66lQ'/mole, t.e., the rate doubles for
each rise in temperature of l00c. From the
equation it is apparent that the rate can also
be increased by increasing the cWorine dioxide concentration, by increasing the cWoride ion concentration, and by decreasing
the hydrogen ion concentration. This equation applies to conventional and "modified"
unbleached kraft pulps. Oxygen-delignified
pulps react more slowly and to a lesser extent as shown in Fig. 4 (19).
When both cWorine and cWorine dioxide are present, the rate of delignification
can be expressed by (20):
= k [CIO 2]" [CI2]mK5

-QK
dt
[4)
of softwootlltrwft pulp at 5OOC.
The activation energy is 56 kj/mole.

Where mixtures of cWorine and chlorine
dioxide are used, cWorine disappears proportionately faster than does cWorine dioxide (21).
3. Delignification efficiency
3.1 Degree of substitution and mode
of addition
Although the use of mixtures of cWorine
dioxide and cWorine to bleach pulp had
been described in the literature on numerous occasions (2, 22, 23), it was not until
1963 that it was shown that when cWorine
dioxide was substituted
for chlorine
delignification efficiency increased signi:
ficantly (6). This was confirmed in other
20
[5]
[l
-0,
where
= 0.5 for unbleached kraft and 0.0 for

oxygen-delignified
determined
an alkaline extraction stage.
after
to K 4,
where Kois the initial kappa numbe;),

dependent on the type of pulp and
temperature)
k = rate constant (influenced by the type

of pulp, the bleaching temperature,
and the extraction stage conditions)
{)
Oxygen bleached
n...
k = rate constant (proponional
where
= bleaching time
K =pulp kappa number
160
pulps
m= 0.5 for [C~] < 1.0 mmolelL, and 0.0

for [C~) > 1.0 mmolelL.
_ _
Kappa
number
[l" - - {] 22.4
unbl;'ched
23.8
o
o
1
Time, hr
Fig. 4. TIle hrrpIIcIof oxygen jWetretltment ore cbwriM tlloxllie lieUplftcatiore

of softf/Jood
Itrwft pulp.
267
268
Pulp Bleaching. Principles and Practice
9
17 Kappa birch kraft
(CD)E /:,.
(D+C)E
~E 4
c:
"
29.8 Kappa unbleached pulp
Kappa factor
(DC)E
~7
0.15
"
c:
Q. 6
'"
Q.
'"
~w
21 Kappanumbersoftwood kraft
o
o
20
FIg. 5. MoMs
40
60
CIO, Substitution,
o
80
of IIIIIlIIimI of dllorI8e MtmM

11M
$OJIw1oo4I1twft JIIIlp.
dllorlIIe ~
100
'"
20
40
60
CIO, Substitution,
80
FIg. 7. MoM of IIIIIlIIimI of d1IorI8e MtmM

dllorI8e
etnIIlmuIHtnu
~S
100
11M
. "'rei nft JIIIlp.
8
19 Kappa oxygen
delignified
softwood
kraft
11 Kappa oxygen delignified eucalyptus
20
40
60
CIO, Substitution,
Fig. ,.
TIle effect of c6lorl8e
MtmM
IIIJtINI ftu:lor
chlorine dioxide as are unbleached kraft

pulps. The equations below permit calculation of the chlorine dioxide required:
o
for unbleached
o
o
20
FIg. 6. MoMs
40
.60
CIO, Substitution,
of IlMltimI
of dllorI8e
100
'"
MtmM
11M
-oqgn-bllplJW
cIJlorI8e~
soJlw1oo4 nft
80
JIIIlp.
reports (17,24,25,26).
Further, it was discovered that when the chlorine dioxide and
chlorine were added to the pulp sequentially, the chlorine dioxide first, the benefit
was even greater (8). Maximum delignification efficiency was achieved when the fraction of chlorine dioxide was between 40
and 60% (8, 27-29). When chlorine was
added first, delignification efficiency was
worse. This is illustrated in Fig. 5 for softwood kraft pulp (30), in Fig. 6 for oxygendelignified softwood kraft pulp (31), in Fig.
7 for birch kraft pulp (32), and in Fig. 8 for
oxygen-delignified
eucalyptus kraft pulp
(33). In the case of oxygen-delignified softwood pulp, birch pulp, and most dramatically, for oxygen-delignified
eucalyptus
pulp, the final kappa number is higher for
100"16chlorine dioxide compared to 100%
chlorine, illustrating the relative difficulty
in delignifying these pulps with chlorine
dioxide. In going from softwood to hardwood and from unbleached kraft to oxygen-
20
40
60
CIa, Substitution,
80
100
Fig. 8. lIoMs of IIIIIlIIimI of c6lorl8e MtmM 11M

dllorI8e ~
-oqgn-b,lpi/W
naIlYftI8snft JIIIlp.
delignified pulp, the free phenolic content

of pulp decreases thereby increasing the
difficulty of delignification with chlorine
dioxide alone.
Figure 9 shows the benefit of 40-60%
chlorine dioxide substitution in the (DC)
sequential mode (34). For example, to
reach an extracted kappa number of 6.0, a
kappa factor 0.20 (60 kg of equivalent chlorine per metric ton of pulp) is required at
10% chlorine dioxide substitution but only
0.17 (50 kg) is required at 40"A>chlorine dioxide.
A useful approach for quantifying the
efficiency of delignification has been used
extensively by Germg:ird. Chlorine dioxide delignification of kraft unbleached and
oxygen-delignified pulps are compared in
Fig. 10 where the chlorine dioxide consumed per metric ton of pulp is plotted
against kappa number decrease achieved
(35).
As mentioned
earlier, oxygenbleached pulps are not as responsive to
~ CIO,
kraft pulp
= k [H+]-o"'ln
(KjK)
and for oxygen-delignified

~ ClO,
= k [W]-o
[6]
kraft pulp
(K-os - Ko-oS)
[7]
where
~ CIO,
=ClO,
consumption
to reach target
kappa number, K
k = a constant (influenced by pH, [Cn, the
type of pulp, and the extraction stage
conditions)
Ko= kappa number of the starting pulp
K
= kappa
number
of the treated
pulp
af-
ter alkaline extraction.

It was found that, if the chloride ion concentration is lower than 58 mg/L, the chlorine dioxide requirement doubles. pH had
no influence between 1.2 and 3, but at pH
greater than 3 the chlorine dioxide requirement increased. Several variables had no
effect on delignification efficiency; temperature from 25 to 6O"C, chlorine dioxide concentration from 1 to 5 mmolelL and pulp
consistency from 0.4 to 10%.
A study of the delignification efficiency
of chlorine dioxide/chlorine
mixtures
showed very similar behavior with respect
'"
011soJlw1oo4nft
80
100
/J8lp Ullpfte4Htm.
to temperature, pulp and chemical concentration, chloride ion concentration, and the
responses of oxygen-delignified
and unbleached pulp. With a 50/50 mixture, pH
had no influence between 1.5 and 2 but, at
pH greater than 2, the chemical requirement increased (36).
3.2 Alkali required for extraction

Sodium hydroxide is required in the extraction stage to solubilize lignin made susceptible to alkali in the previous stage.
Sodium hydroxide acts in a number of ways:
to neutralize acid carryover from the first
stage; to hydrolyze chlorine bound to the
pulp, which creates new phenolic groups;
and to neutralize phenolic and other acidic
groups in the pulp, which leads to ionization and increased water solubility of lignin fragments as described in more detail
in the chapter on extraction (125). When
chlorine dioxide replaces chlorine, less hydrochloric acid is produced in the first stage
and there are fewer phenolic groups and
less organically bound chlorine in the pulp.
In addition, depending on the way in which
the chlorine dioxide is used, less equivalent
chlorine may be needed in the first stage
and less sodium hydroxide
again is
required.
Estimates of the sodium hydroxide required have been reported by several authors for softwood pulps (25, 26, 28, 37,
CII
270
0.6
Oxygendeligni/iedsoftwoodkraft
~30
269
95
Kappa 35
0
~...
"2't
Eu 0.4
C.-~c
0-"
~uU
Ig~",,0.2
1f 20
E
C
8 10
90
(D+qEDED
"*
~S
z]>
~Q;
0
0
10
20
Kappa number reduction
30
20
60
40
CIO, 5ubstitution,%
80
85
-e--
.-e_e-e-e-e-.
after
aging --e_e
80
100
75
Fig. 12. Pro ,.",. soMam l1ytIro:xItIe t:OIIS8IIfM lit tbe

ulrYllItm
sItIge follmlll"g
tlellpljktltlmt
","b eombIIIIIUoIIs of eblorirle dIo:xIiIe tIrId
eblorlu.
5
:;00C 4
o
55
"* 3
"2'
E
~
C
ou
I
a
z'"
o
"*
80
30
100
Fig.11. WI_11y4rozIM ~
lit tIJeuIrYIIItm st.ge follmlllag tlellpljietlllqa ","b
eombl".tloru of eblorl"e dioxide ."d
eblorlu.
38) and hardwood pulps (26). Figure 11
shows sodium hydroxide consumed in the
extraction stage, for three softwood kraft
pulps (28). Figure 12 indicates the sodium
hydroxide consumed per equivalent chlorine consumed in the first stage, as a function of chlorine dioxide substitution, for
both softwoods and hardwoods (26). As
an example, in the delignification of softwood kraft pulp having a 30 kappa number,increasing the percent chlorine dioxide
in the first stage from 10 to 50 to 100 would
decrease the sodium hydroxide required
(not including acid carryover in the filtrate)
from 2.4 to 1.8 to 1.2% on pulp (24 to 18 to
12 kg per metric ton of pulp).
3.3
Brightness
development
Brightness development actually begins

during delignification with combinations of
chlorine and chlorine dioxide. As shown
in Fig. 13, brightness, after alkaline extrac-
60
40
Substitution,
80
100
45
i>
as 35
40
60
CI02 Substitution,
20
Fig. 14. fte brlgbtua ofJnllPufler three tIrIdfive sltlges ofbletu:Wag of sojlwJood lmIfI
pulp
","b eblorirle tIrId eblorirle dIo:xIiIe.
50
S40
20
Cia,
70
34.8
15
.10
Kappa number
Fig. 13. fte post-t:#flStie-uIrYItIort

brlgblrless
of
JIIIlps .fIn' tlellpljletllltm
U1IIfbI",,""tb
tUnu of eblorirle dIo:xIiIe tIrId eblorlu.
tion, increases with degree of delignification

with the exception of the initial phases of
chlorine-only delignification; the brightness
increase is greater with increasing degree
of chlorine dioxide substitution
(39).
Equimolar concentrations of chlorine dioxide and chlorine were used for the (D+C)E
case.
The discussion of delignification in the
previous section is predicated on the assumption that the kappa number is a true
measure of progress toward fully bleached
pulp and, in particular, that it is an accurate
measure of the amount of bleaching agent
required in later stages. It has been argued
that, because chlorine dioxide oxidizes (and
bleaches) lignin to a greater degree than
does chlorine, an oxidative permanganate
test, for example, kappa number, gives a
false measure of lignin content. However,
it has been clearly shown that the post-extraction kappa number is linearly correlated
with chlorine dioxide required in later

stages to achieve the desired final brightness for a wide range of degree of substitution (4043). TI1is subject is discussed in
greater detail in the chapter on chlorine
dioxide bleaching (125).
The synergistic effect of chlorine dioxide
in combination with chlorine in the first
stage is apparent from the brightness reached
in later stages. Figure 14 shows the brightness advantage gained, before and after thermal aging, in the third and fifth stages of a
(D+C)EDED sequence when mixtures,O+C,
are used in the first stage (44). Figure 15
shows the even more dramatic advantage
obtained when sequential treatment, DC, is
used in the first stage of a (DC) ElI sequence
as compared to mixtures (8).
Assessment of the impact of chlorine dioxide use in delignification on the achievement of high brightness is complicated by
the variety of chemicals and sequences used
and the range of conditions applied that can
be used for bleaching partially delignified
pulp and by the diversity of criteria available by which to judge a bleaching sequence. Germg3.r'd and co-workers have
optimized (DC)EDED sequences by adjusting the kappa factor in the first stage to give
the lowest overall equivalent chlorine use.
The results are given in Table 1 for several
pulps (4043, 45). The minimum overall
chemical requirement is achieved with 3050% chlorine dioxide substitution. Optimization for lowest chemical cost was also
studied and was usually close to the optimal conditions for lowest overall equivalent
chlorine. For unbleached softwood pulp,
the lowest chemical cost was at 30% chlorine dioxide substitution.
Increasing substitution to 70-90% required a significant
increase in chemical and led to a significant
increase in cost. The results of a similiar
study on optimization
of (OC)(E+O)O
bleaching of oxygen-delignified eucalyptus
are summarized inTable 2 (33).
To decrease the cost at 70-90% chlorine
dioxide substitution,
for bleaching softwood kraft, consistency was increased from
3-8%, chloride ion was added, and the interval between 0 and C was increased from
2 to 4 minutes; a 5% decrease in cost was
reported (40). These changes in process
conditions had no influence on costs at 3050",,(,chlorine dioxide.
Another optimization study, for (OC)E
(HO) bleaching to 86 ISO brightness,found
minimum costs at 30% substitution independent of kappa factor in the range 0.20 to
0.27 (46). At 90% substitution the lowest
cost was at 0.20-0.24 kappa factor; costs
increased at 0.27 kappa factor. At 50% chlorine dioxide for the same sequence bleaching to 90 ISO brightness,
cost was
minImized at 0.16-0.18 (47).

Tllble 1. optImIzetI (DC)EDED6lMe1mtf ollmlft /NIlp 10 ~
271
272
ISO MI,,,,-.

8
80
ClO, in first bleaching

stage, % of total
equivalent chlorine
Optimal charge in
first bleaching stage,
kappa factor
Kappa number
after extraction
Total equivalent chlorine

to reach 90% ISO brightness, kappa factor
A. 29.8 Kappa number softwood (40)

10.
0.20
30
50
70
90
0.20
0.18
0.17
0.14
6.4
4.8
5.1
5.6
8.7
B. 26.8 Kappa number softwood from modified continuous cooking (41)

10.
0.18
5.9
30
50
70
90
0.17
0.17
0.17
0.14
6.1
4.9
5.8
8.1
0.29
0.27
0.25
0.28
0.30
0.17
0.17
0.17
0.16
0.16
4.3
4.1
3.7
4.4
5.4
40
60
CI~ Substitution, %
100
80
10
10
30
Chlorine dioxide applied, kwtonne
FI,. 17. C61ort1tfJ.for'mH
m, ~
frmrt e61or1u
.,...
tI'-Itle
lrfJ"'-Ia.ftnm4lt1
VGrl-
OIlS sllulla.
0.28
1.0
0.27
0.25
0.28
0.31
o
:to.8
*-
C. 18.2 Kappa number oXygen-delignified softwood (45)

10'
30
50
70
90
10
0.27
0.26
0.26
0.27
0.31
Pulp
J'
"i' 0.6
E
..2 0.4
S
~
0.1
U
Optical and
residual
sensor
10
40
60
Cia, Substitution, %
80
100
Mix
tank
Chlorination
tower
PI,. 16. C61on11e

m I. .IIpiJbtiort
01
..,
tll./fernt e6wsojlrlJoHI""""
Inwft
""p
rl1N-e61or1u~
IIIItIItImtmotles.
FI,. 18. FlmDs6efJllor
Iow-etnlSlsIf!fU:J
(DC) .11181.
By changing the process, particularly the

mode of chlorine/chlorine dioxide addition,
pH, chloride ion concentration,
and consistency, chlorate formation can be decreased.
Chlorate formation decreases
oxidizing chemical available for delignification; however, there are other factors that
also contribute to delignification efficiency.
When chlorine dioxide is added first in
sequential treatment, (DC), the chlorate
formed is decreased compared to mixtures

or to (CD), in part accounting for the increased efficiency of this sequential treatment. Figure 16 illustrates this statement
(30); similiar results have been reported by
others (42, 50-52). In a (DC) treatment,in
the interval before chlorine addition, chlorite undergoes acidic decomposition to give
chlorine dioxide and chloride but no chlorate (16). Conversely, in a (CD) treatment,
./b1Um.
D. 17.2 Kappa number birch (42)

10'
30
50
70
90
0.37
0.35
0.34
0.36
0.42
0.24
0.17
0.17
0.24
0.24
E. 16.0 Kappa number eucalyptus (43)

10'
30
50
70
90
0.29
0.24
0.26
0.28
0.32
0.17
0.17
0.15
0.15
0.20
'Sequence (C+D)EDED
Some mills using only chlorine dioxide
in the first stage have had difficulty in reaching high brightness (90 ISO); the addition
of peroxide to the second extraction stage
has helped to overcome
this problem
(48, 49).
TIIbk
2. optImIzetI
(DC)(B+O)D
CIO, in first bleaching

stage, % of total equivalent chlorine
6lMe1mtf
0112.0
bpJJtI
tI_'-
Optimal charge in first

bleaching stage, kappa
stage, kappa factor
0xyffJtI-6IfJGC6fJtI_lyptus
""p
3.4 Chlorate formation
10"
30
0.15
0.15
0.22
0.21
M described in Sect. 2.2, the chlorate ion

formed when chlorine dioxide is used in
bleaching represents a loss of active bleaching chemical. Chlorate is formed by reaction of chlorite ion with hypochlorous acid.
50
70
~
OJ7
0.17
QB
O,~l
0.25
Q~
'Sequence (C+D)EDED
(33).
Total equivalent chlorine

to reach 90",{,ISO brightness kappa factor
Chapter IV 3: CWorine Dioxide in Delignification

hypocWorous add is present when chlorite
is formed by the reduction of chlorine dioxide and this leads to chlorate formation.
CWorate formed is a function of chlorine
dioxide applied. All the data for (DC) treatment from the reports dted above have
been plotted in Fig. 17. Although chlorate
formation is strongly affected by process
conditions, it can be seen that cWorate formation, expressed as a percentage of chlorine dioxide consumed, is approximately
20% on a weight basis (13% on a mole basis). The percentage cWorate formation is
higher for chlorine dioxide bleaching stages
as discussed in Chap. IV 8 (105).
4. Process flowsheets and

conditions
4.1 Flowsheets and equipment
At this time, most delignification stages
using chlorine dioxide in combination with
chlorine or alone are modified chlorination
stages. Unbleached pulp is diluted to a low
consistency, typically 34%, and chlorine
dioxide solution is added using a mixer; the
mixed suspension passes into an upflow
tower and then to a washer. When chlorine is also added and it is added after the
chlorine dioxide, there are two mixers separated by a section of pipe, or a modest flowthrough tank, to provide retention time.
The flowsheet
must provide suitable
process conditions for effective chlorine
dioxide delignification.
Typically, those
conditions fall in the following ranges:
Total chemical
charge:
0.15-0.25
kappa factor
Chlorine dioxide
charge:
25-100% of the
total
Temperature:
30-60C
nil up to 5 min.
Time between
D and C:
Total time:
20-60 min.
End pH:
1.5-3
Consistency:
3-4%
Reports of mill implementation

of chlorine dioxide delignification provide many
273
examples of flowsheets. In a 1967, trial in

which hardwood pulp was delignified with
chlorine dioxide/chlorine
mixtures, chlorine dioxide was added to the dispersion
of chlorine gas in water immediately downstream of the chlorine disperser (53). In a
1973 report on sequential (DC) treatment
of softwood, one mill employed a 9-minute,
10% consistency retention tower for the
chlorine dioxide reaction, a dilution step,
and chlorine addition followed by a 60minute, 3.5% consistency tower; a second
mill employed two in-line mixers separated
by a 3-minute section of pipeline followed
by a 45-minute tower, all at 3.5% consistency (54). Several recent mill reports provide other examples of low consistency
flowsheets (55-57) and another report of
successful mill trials provides five examples
of process flowsheets, an example of which
is given in Fig. 18 (58, 59). This flowsheet
is appropriate for 30-700A,substitution with
a small portion of the cWorine dioxide (5l00A,)being added with the cWorine to pre-
vent viscosity loss. . Medium-consistency

(10-15%) cWorine dioxide delignification is
not widely practiced at present but is being adopted more widely. An example of a
medium-consistency flowsheet is shown in
Fig. 19 (58).
4.2 Chemical
charge
The issue of how much chemical to add

in a delignification stage using chlorine dioxide has already been discussed, to a certain extent, in Sect. 3 on delignification
effidency.
Germgard has shown that, as
delignification is extended, the incremental chemical charge required to achieve an
incremental kappa number decrease becomes greater, that is, delignification effidency decreases (see Fig. 10).
This effect can also be seen by plotting
extracted kappa number against chemical
consumed as shown in Fig. 20 (60). The
softwood pulp used had a kappa number
of 26; (C+D) was at 15% substitution and
(DC) was at 50% substitution.
As more
chemical is applied, the curve flattens,
that is, the chemical becomes less and less
effective and delignification effidency de-
274
Pulp Bleaching
-Principles
and Practice
10
Chlorine
gas
Pulp
26 kappa softwood kraft
.~
~~:::--~:
t
Pulpto
tower
DE
(C~+D,JE
MC
pump
CIO,
Optical and
residual
sensor
JIIg.If). ~tftn'mftiam~(DC)de.
IIpljlaltlml.
creases. There is merit in limiting the charge
of chemical to the range in which it is most
effident, that is, an amount corresponding
to the steep part of the curve. As the cWorine dioxide in the first stage increases
above 500A"the curve flattens at a higher
extracted kappa number. Optimal chemical charge must be determined in the context of the overall bleach plant as discussed
in Section 3.3.
4.3 Timing of chlorine dioxide addition
Chlorine dioxide, added in advance of
the cWorine, reacts with the pulp before
cWorine is added and is more effident than
when cWorine and chlorine dioxide mixtures are used. The logical extension of this
finding is therefore that delignification effidency is maximized when all the chlorine
dioxide is consumed before the chlorine is
added. The time required for complete reaction of the cWorine dioxide is a function
of temperature,
consistency, and kappa
factor.
Early laboratory wode:, by Hatton (8), on
the timing of sequential delignification was
done only at 200C with hand mixing and
chlorine dioxide was limited to 50% substitution. It was found that a 3-minute chlorine dioxide
reaction
time at this
temperature was insuffident to give maximum benefit; 5 minutes gave greater
delignification and higher brightness (8).
Hatton also used a 5-minute chlorine dioxide reaction time at 200C; delignification
was not increased at 10 minutes and, in fact,
was poorer at 15 minutes' reaction (27).
O-{D"C.,JE
0.20 kappa factor
4
Chemical consumed,
Fig. 20. DellgrdJ'ktlUmt
cblorlu.
wltb
6
% equiv. CI, on pulp
cblorine
dWxUle
"""
With effident laboratory mixing, incorporating a stirred tank reactor at low consistency, it was shown that at 300C and with
30% substitution, 30 seconds was suffident
to obtain almost maximum delignification
(61). However, in the same study, it was
shown that if 60 seconds or more were
used, pulp viscosity suffered because all the
cWorine dioxide had disappeared before it
could be useful in protecting
the pulp
against cWorine. Further discussion of this
topic is found in Chap. III 2 on chlorination (125). To avoid viscosity loss, where
the combination of time, temperature, and
amount of added chlorine dioxide lead to
complete consumption of protective chlorine dioxide,it is recommended that a small
amount of chlorine dioxide (5-10% of the
total charge of equivalent chlorine) be
added with the chlorine. In another study,
it was found that 60 seconds was required
to obtain maximum delignification at 400C
18
D(C+D)
Delignification
. 2 min between
D and (C+D)
10
. D fully reacted before C + D
20
40
Clo,
60
Substitution,
80
100
')(,
Fig. 21. Tbe effed of cblorlu dw:dlle subtitrltklll

.rultbe "me to _me
tbe cblorlu diox.
ide 011(DC) deUpljlaltlml.
CI02 in first
stage, % of
total equivalent
chlorine
275
Temperature, C
20
35
50
Tune to 95% consumption, minutes

10
30
70
aDelignification
14
11
11
conditions:
kappa
8
6
5
factor 0.155; consistency
for 30-50% substitution (62). In the same

study it was found that when the consistency was increased to 10%, the chlorine
dioxide reaction time required for maximum delignification decreased to 20 se~onds for the same conditions.
Increased delignification results if the
chlorine dioxide is completely consumed
before the chlorine is added. This is clearly
shown in Fig. 21 for delignification of 31
kappa number softwood kraft pulp at 300c
with a kappa factor of 0.19 (47). The high
delignification efficiency is mainly due to
the high efficiency of that phase of sequential delignification occurring immediately
after chlorine is added (63).

Tune and temperature are critical factors
in determining the extent of consumption
of chemical in delignification using chlorine
dioxide. If the time is too short or the temperature too low, the chemical applied is
not totally consumed and residual chemical remains at the end of the stage. Usually
the principal objective of the chlorine dioxide/chlorine
delignification stage is to
achieve a particular degree of delignification
by consumption of a specified amount of
chemical.
Most of the discussion in this
section concerns this objective; however,
it is important to note that if residual is consumed too rapidly shive removal in this
stage may be adversely affected.
The rate of deligniflcation controls the
consumption rate as discussed earlier in the
section on kinetics. A higher delignification
rate occurs with pulp having a higher kappa
5
4
2
1.5%
number, with application of a higher concentration of chlorine dioxide and chlorine,

at higher temperature, and with chlorine
dioxide/chlorine
mixtures in the range 3060% chlorine dioxide as compared to chlorine or chlorine dioxide alone. For each
lOoC increase in temperature,
the delignification rate doubles.
In many cases, mills delignifying with
chlorine dioxide, with or without chlorine,
have fixed volume towers built originally
for low consistency chlorination. The retention time available in such a stage would
typically have been designed for 30-60 minutes, but, with production rate increases
over and above design as is often the case
in mills, the retention time is much lower
in operation than originally designed. If a
longer retention time is required, a slight
increase can be achieved by increasing consistency although this strategy is very much
limited by the "pumpability" of the pulp.
The principal means of overcoming limitations in retention time is to increase the temperature. As shown in Table 3, the time
required to achieve 95% consumption
of
chemical decreases rapidly as temperature
is increased (64).
Temperature is controlled by regulating
the temperature
of the incoming
unbleached pulp, usually by adjusting wash
water temperature in the last stage of brown
stock washing. In modem mills, no dilution water other than recycled first-stage
flttrate is used for dilution of the pulp leading into the delignification stage. However,
where other sources of water are used, temperature control is possible by adjusting the
276
Pulp Bleaching
-Principles
and Practice
temperature of the dilution water. Some

delignification stages are subjected to wide
fluctuations in temperature due to seasonal
variations which provide large changes in
the raw water temperature. In Canada, the
raw water temperature may change from 2
or 3C in the winter to 20 or 25C in the
summer. Chlorine dioxide solution is typically applied at 5-lOoC and is added to the
system in sufficient volume to decrease the
temperature several degrees. To offset this
negative effect on temperature,
heat exchangers may be used to heat the chlorine
dioxide solution.
Controversy exists about the impact of
higher temperature on delignification efficiency. A thorough study by Germgard
(35), discussed previously in the section on
delignification efficiency, showed the absence of a temperature effect on delignification of unbleached softwood kraft and
oxygen-de lignified softwood kraft using
chlorine dioxide alone or a 50/50 mixture
of chlorine dioxide and chlorine (9). Another study failed to demonstrate any effect
on delignification efficiency for substitution
in the 30-70% range when the temperature
was increased from 20 to 50C at a 0.20
kappa factor (64). However, this same
study showed that, when the kappa factor
was 0.155, delignification
efficiency decreased as the temperature increased. In
yet another study, it was found that delignification with mixtures of chlorine and
1IIbk 4. Effect o/~
mft jHltp.
D-stage
temperature, C
chlorine dioxide at 5()-6(}oA,substitution was

significantly less effective at 60C than at
30C (61).
Another example of decreased efficiency
as chlorine dioxide delignification temperature increases is shown in Table 4 (65). It
should be noted that the time to reach zero
residual for a 100% chlorine dioxide treatment is much greater than the time given
in Table 3 for sequential addition of chlorine dioxide and chlorine.
There is no evidence that temperature
alteration has any impact on the quality of
pulp produced by chlorine dioxide delignification. As a final note, neither pulp viscosity nor kappa number is adversely
affected by extending the retention time
well beyond the time needed to exhaust the
residual in either chlorine dioxide (66) or
chlorine delignification (67).
4.5 pH
pH has a significant impact on most
bleaching stages. There is some controversy
about the optimal pH for chlorine dioxide
delignification.
Rapson studied the effect
of pH on chlorine dioxide/chlorine
stages
and found that delignification was slightly
influenced by pH with delignification being greatest, as evidenced by the kappa
number after extraction, near an end pH of
2 for both chlorine dioxide alone and a 70/
30 chlorine dioxide/chlorine
mixture (68).
The kappa number after the extraction stage
OftelJlorlIIedioxide dellplftetlliml e./ftderleyfor" 31.0 luIpJMsoJt-04

Extracted kappa number
Tune to zero
residual, min
(EO)
(EP)'
5.8
5.5
6.4
6.2
Kappa factor 0.190

30
40
50
60
Kappa factor 0.155
180
82
34
19
7.0
6.8
7.9
7.6
5.9
6.1
6.7
6.8
30
60
155
16
8.3
9.6
7.5
8.2
'0.5 % HP2 on pulp

3.5
_
3.0
12
4.6 Chloride ion

10
8]
E
6
"
:;;
Q.
Q.
'* 0.5
o
5
pH in D stage
Fig. 22. De IffI/HId of JIll 011tlellp'.fktlt"m
.,."" cbIurl1Ie
~
278
End pH in the range 2-4 has no affect on

pulp viscosity (70, 72).
14
.!j-Q.
" 5:E
u c:
0 2.5
CIi
"t:J
cra .5
(5 2.0
.!j~"5
..Qc 1.5
CIi
--"u!:
~ 'S 1.0
"t:JCT
Q,)
"in
&!
277
increased slightly as the pH increased to 4

and then increased dramatically with further increase in pH. However, delignification efficiency was not directly related
to the formation of non-reactive oxidant
(CI03- and CIO;) as shown in Fig. 22 for
chlorine dioxide alone. At a pH below 2,
sodium chlorate formation was significant
but thereafter decreased sharply up to pH
4. Above pH 4,chlorite formation increased
very dramatically. The minimum chemical
loss in the form of chlorate and chlorite occurred at a pH between 3 and 4, in an identical manner to that found to occur in
chlorine dioxide bleaching. However, this
minimum did not correspond precisely with
the optimal pH for delignification which
was 2.
Several studies by various authors have
shown chlorine dioxide delignification to
be insensitive to pH from an end pH ofless
than 2 to an end pH of 4,for 28 kappa pine
kraft pulp and 17 kappa oxygen-delignified
pine kraft pulp (69),33
kappa number
softwood kraft (66), 16 kappa number eucalyptus (43), 13.8 kappa number oxygendelignified eucalyptus pulp (70), and 24
kappa number southern pine 01).
Two studies reported the optimal pH to
be in the range of approximately 3-4. In
one study, treatment of oxygen-delignified
a4
jomItItitm
of35/u1pJ111
__
9
of dllorl~
a4
dllmwle
SDftrDootllmlft
JHIlp.
kraft pulp of 22.4 kappa number with chlorine dioxide indicated a steadily decreasing
DED brightness with decreasing initial pH
in the first D stage from 8.3 "natural pH" to
1.5; this range corresponded to end pH values ranging from approximately 2.5-4 to 1.5
respectively (72). Another study provided
supporting evidence indicating that the
maximum delignification efficiency and DE
brightness occurred at a pH slightly below
4, a value consistent with the minimum loss
of chemical in the form of chlorate and chlorite (73).
The kinetics of chlorine dioxide/chlorine
delignification are affected by pH in a manner complicated by the chloride ion concentration. With chlorine dioxide alone,
increasing the pH from 2 leads to a steady
increase in delignification rate. In the presence of 0.1 M sodium chloride (5.8 g/L),
the delignification rate is higher at all pH
levels but a distinct minimum appears at pH
3 (18). When mixtures of chlorine dioxide
and chlorine are used, the delignification
rate is again lowest at low chloride ion concentration but increases substantially with
increasing chloride ion concentrations
up
to 0.50 M at all pH levels. The delignification
rate decreases from pH 2 to pH
in the
" from
absence of chloride ion but increases
pH 2 to pH 4 in the presence of chloride
ion (20).
Given the number of reactions in which

chloride ion takes part as shown in Fig. I,
it is not surprising that chloride ion concentration has a significant influence on
delignification kinetics and efficiency. In
the chloride ion concentration range 0.020.5 M, delignification
efficiency
is
unchanged but, when the chloride ion concentration is less than 0.001 M, delignification efficiency is decreased by almost
50% (35). In another study it was found
that only 0.01 M chloride was required in a
chlorine dioxide delignification
stage to
increase final brightness
in a D(EO)D
bleaching sequence by 1% ISO. Separate
studies on the delignification of hardwood
pulp using chlorine dioxide revealed that
addition of chloride ion decreased the
kappa number after extraction and decreased chlorate formation (43, 66).
4.7 Consistency
In the 1970s, delignification studies of
high-consistency
pulp (>35%) using gaseous chlorine dioxide and chlorine showed
that an increase in consistency led to a dramatic increase in delignification efficiency
(74). However, another early study provided evidence showing that increasing the
pulp consistency from 0.4%-10% in delignification of oxygen-prebleached
softwood
kraft pulp with chlorine dioxide had no
impact on delignification efficiency (35).
Independent
studies of hardwood pulps
have shown the significant benefit resulting from an increase in consistency from
low (3-4%) to medium (1(}14%) in delignification efficiency for eucalyptus (33, 43),
aspen (66), and oxygen-delignified
kraft
pulp of kappa 13.1 (72). Another report
provides numerous examples of superior
delignification obtained at medium consistency as compared to low consistency for
sequential treatment of oxygen-delignified
kraft pulp with 10,30, and 50% chlorine
dioxide substitution (62).
Recent studies show that increases in
consistency from low to medium to high
increase delignification efficiency of 30-35

kappa softwood kraft and decreases chlorate formation (75). This is explained by
reaction pathways and reaction intermediates which provide a sound theoretical basis for these empirical observations.
4.8 Carryover of dissolved organic

material
It is well-known that residual dissolved
organic maner retained by unbleached or,
oxygen-delignified pulp because of incomplete washing, consumes bleaching chemical in a chlorination
stage. However,
relatively linle information has been published for the case where chlorine dioxide
or chlorine dioxide/chlorine
is used in the
first stage. An early report of mill trials provides evidence of the increased chemical
consumption that may result from carryover
(54).
Carryover can be determined by total
organic carbon (fOe) measurement or by
oxidant consumption, for example, permanganate consumed per volume of illtrate.The
traditional measurement, "saltcake losses;
based on sodium or conductivity measurement, is not appropriate in systems employing illtrate recycle. Recycled illtrate from
the chlorine dioxide/chlorine stage can also
consume chemical in a closed system. Per
unit of organic carbon, extraction stage illtrate consumes more chemical than does
recycled first stage illtrate and black liquor
consumes more chemical than does extraction stage illtrate (76). Oxygen and 100%
chlorine dioxide delignification both decrease the chemical consumed by illtrate
carryover in illtrate recycle systems using
little water (77).
5. Pulp quality
5.1 Brightness stability
Bleached pulp darkens with age. This
"brightness
reversion" is a function of
chemical structures in the pulp. It is possible to accelerate aging by elevating the
temperature and, for light-sensitive structures, by exposing the pulp to light. Until
recently, there has been no standard procedure for measurement of brightness stabil-
Chapter N 3: Chlorine Dioxide in Delignification

40
5
w
U 35
'ifci
'"
-: 30
6-
~
.~ 25
5
20
o
20
40
60
ClO, Substitution. ')(,
Fig.23. 1IoeImJNIdofcblorlu ~
- so~
80
100
-/I JnIlJI
"'-11].
ity, that is, for accelerated aging; a range of

temperatures, exposure times, and humidities have been used. Although mechanical
pulps are light sensitive, accelerated aging
of chemical pulps is principally accomplished by increasing the temperature.
The use of chlorine dioxide in place of
chlorine for delignification
has been reported to increase brightness stability. It
has been well-known for many years that
substantial replacement of chlorine by chlorine dioxide increases the brightness stability of sulfite pulp (25). This finding has been
confirmed more recently both in the laboratory (78) and on a mill scale (79). Poor
brightness stability has been shown to be
directly related to the high extractives content of chlorine-bleached sulfite pulp. A significant decrease in extractives content can
be achieved when chlorine dioxide replaces
chlorine (80). Similarly, hardwood pulps
have been found to be more stable when a
high degree of chlorine dioxide substitution
is used in the bleaching of mixed Canadian
hardwood species (25, 26, 78) and birch
(42). Once again, a decrease in extractives
Ttlble5. hIfl-
of cbltJrlu ~
1125
1135
1115
of cblorl_ ~
and Practice
sUsllhItItm ~ tilestrefIgtbof so~
ing chemicals attack the cellulose fraction

in pulp, the cellulose degree of polymerization may decrease and with it viscosity.
Beyond a critical point a decrease in viscosity leads to a decrease in sheet strength.
Because chlorine dioxide is known to be
less damaging to cellulose than chlorine,
increasing substitution of chlorine dioxide
for chlorine logically should reduce degradation of the cellulose. A comparison of
pulp strength data, particularly those in
early studies, is complicated by the lack of
standard testing procedures. It is now generally accepted that strength comparisons
can best be made by comparing
tear
strength at a given tensile strength.
Data listed in Table 6 show that, although
oxygen delignification leads to a lower tear
at a given tensile, chlorine dioxide substitution in the 1009Q"Ai
range has no influence
on tear (82). It should also be noted that
oxygen delignification increases the beating time requlred to achieve a given tensile
strength, but chlorine dioxide substitution
has no effect (82). Other laboratory ,studies have shown that 1009Q"Ai
chlorine dioxide substitution has no effect on strength,
that is, on tear at a given tensile (31, 83).
Two mill studies have shown that significant increases in tear occur at a given ten-
of so~
1nW/IJnllp bleacbed ",

"
Starting Pulp
(oxygen-delignified)
16.0
10.7
Viscosity, dm3fkg
10
50
90
-Principles
5.2 Viscosity and pulp strength

Pulp viscosity increases dramatically with
only 5-10% chlorine dioxide substitution
and then decreases slightly as percent substitution increases further at a fixed chemical charge (Fig. 23) (25). The decrease
experienced
in the mid-range of percent
substitution is likely related to the greater
delignification achieved and the comparatively lower post-extraction kappa number
that results. Pulp viscosity is also sensitive
to the mode of addition of chlorine dioxide
and chlorine. Addition of chlorine dioxide
in advance of chlorine gives the highest viscosity at a given kappa number (31). On
the other hand, the viscosity of fully
bleached pulp has been found to be unchanged as chlorine dioxide substitution
increases from 10 to 50 to 90% as shown in
Table 5 (82).
The relationship between viscosity and
strength is complex as discussed in other
chapters of this book (125). When bleach-
Starting Pulp
(unbleached)
33.3
Pulp Bleaching
Ttlble6. r-fl-
SllbstUrllloll~ tile "'-II]
Kappa number:
280
content is associated with this increase in

brightness stability.
For softwood pulps the situation is less
clear. Several authors have claimed that
softwood pulps are more heat stable when
delignified with more chlorine dioxide and
less chlorine (6, 25, 81). However, there
are also data which show that the brightness stability of softwood pulp does not
change with increasing chlorine dioxide
substitution
(32, 51, 78). Even though
there is some doubt arising from the lack
of a standard test method for reversion, it is
likely that chlorine dioxide substitution has
little impact on brightness stability of softwood pulps (12).
(C+D)EDEDset[fImU.
00,,%
279
920
935
950
740
745
745
-/I Jnllpbleacbed",
(C+D)EDEDset[fImU.
ClO" %
Kappa number:
Starting Pulp
(unbleached)
33.3
"
Starting Pulp
( oxygen-delignified)
16.0
Tear index,Nm'/kg
10.7
at tensile index 90 kNm/kg
10
14.6
13.4
11.0
50
90
13.4
13.0
11.5
13.4
13.3
11.5
Beating revolutions to tensile index 90 kNm/kg

IO
900
2000
2500
50
90
1000
2000
2300
1000
2000
2400
sile with increasing chlorine dioxide

substitution. An increase in substitution
from 10% to 30,40, or 50% increased the
tear strength of softwood kraft pulp by
10% (55). Increasing the chlorine dioxide

substitution from 30 to 100 % and decreasing the chlorination factor led to a similar
increase in tear at a given tensile index for
an oxygen-delignified softwood kraft pulp
(84).
5.3 Cleanliness
Removal of contaminating
particles is
an important function of bleaching. A rate
equation for particle removal during chlorine dioxide delignification is given below
(85):
-d(partlcles)
= k [ClO,]07
[particles]l
dt
where
= shives,
particles
k
knots, and bark

constant
(varies according to particle).
= rate
The particle concentration decreases linearly with time, and so this is a first-order
equation. This is distinctly different from
the concentration of1ignin which decreases
very rapidly initially and then more slowly.
Thus, particle removal is favored by prolonged retention at a given concentration
of chlorine dioxide. The Arrhenius activation energy for chlorine dioxide reaction
with paniclc~, jj :t j kJ/mol ({J5), compares to a value of 60 kJ/mol for reaction
with lignin as measured by kappa number
decrease. Thus, lower temperature
in a

chlorine dioxide delignification stage decreases the rate of delignification and the
rate of chlorine dioxide disappearance
while the rate of particle elimination is
reduced to a much lesser degree. Lower
temperatures therefore favor particle elimination.
Particle removal in bleaching is dependent on many factors, the most important
of which may be the extent of bleaching in
a particular stage or sequence. The first
chemical applied in a bleaching stage is
consumed mainly by lignin rather than by
particles and so extended bleaching with
greater addition of chemical leads to improved particle elimination.
Further, particles may not be immediately eliminated
in a particular stage but may be made more
susceptible to removal in a later stage. Chlorine dioxide alone has been found in severallaboratory studies to be highly effective
in removing particles (85, 86). As shown
in Fig. 24, chlorine dioxide alone is uniformly superior to chlorine; alone in the first
stage of a five-stage sequence over a range
of targeted values. In Fig. 25, a similar result is seen for a given consumption
of
bleaching chemical. Figure 24 shows that
mixtures of chlorine dioxide and chlorine
are not as effective as chlorine dioxide by
itself. Another study showed that 30, 50,
and 70% substitution was decidedly inferior
for wood dirt removal compared with 10
and 90% substitution (46). To complement
information in the literature about the effectiveness of combinations of chlorine and
chlorine dioxide in removing particles,
281
several recent mill studies have shown that

no change in pulp cleanliness occurs when
chlorine dioxide substitution is altered over
a wide range (13, 55-57).
5.4 Extractives and organochlorine
It has long been known that the bleaching of pulp having a high extractives content (e.g., sulfite softwood or kraft birch)
with chlorine dioxide rather than chlorine
leads to decreases in the extractives content of the final product. Indeed, the bleaching of sulfite pulp to produce a dissolving
grade with low extractive content was one
of the first uses of chlorine dioxide in commercial bleaching.
The substantial impact of chlorine dioxide substitution on extractives in sulfite pulp
has been reported frequently (25, 79, 80,
87). An increase in chlorine dioxide substitution from 0 to 100% decreased the extractives content of a sulfite pulp by 50%
(from 1.5% on pulp to 0.75% on pulp) after
CEDED bleaching (25). The extractives
content of fully bleached birch kraft pulp
decreased from 0.5 to 0.4% on increasing
the chlorine dioxide. substitution from 0 to
100",1,and the chlorine content of the extractives decreased from 25% to approximately 1% (42).
The organochlorine content of pulp can
be subdivided into water extractable and
carbon adsorbable (AOX), solvent extractable, and inextractable fractions (88, 89).
Substitution of chlorine dioxide for chlorine
decreases the organochlorine
content in
pulp (80) as shown inTable 7 (90).
400
400
Substitution.
o
0
jb
Substitution,
o
0
.. SO
70
300
300
. 90
o 100
~c:
-"<Ii 200
:i5
.in
CEDED
:>
100
.o 100
90
lJ
oc:
<Ii 200
"'"
:i5
.in
:>
.. 50
70
100
o
o
75
80
85
Brightness, % ISO
Fig. 24. '111eImpad of clllorl_

dloxiile
on dirt bleaclling
capability
against briglltness.
90
Sllbstitutton
measured
70
80
90
100
110
Chemical consumed. kg equiv. CI, /tonne
Fig. 25. 1'be Impact of cI1lorl_ diOJdde Sllbstitutton

on dirt bleacblng capability measured
against cllemkal etmSfImption.
282
5.5 Dioxins in pulp

Following the discovery, in the mid1980s, of the formation of chlorinated dioxins and furans during pulp bleaching,
extensive research was undertaken to discover means of avoiding their formation.
This subject is covered in considerable detail in the chapter on dioxins (Chap.VIII 3)
(125). Substitution of chlorine dioxide for
chlorine was found to have a profound affect on dioxin formation. As chlorine was
replaced by chlorine dioxide and the chlorine (CIZ>multiple was reduced to below
approximately 0.15, the formation of 2, 3,
7, 8-tetrachlorodibenzo-p-dioxin
(TCDD)
and its furan analog (TCDF) was eliminated
(91). Similar studies have shown that a combination of low kappa factor and high percent substitution can be used to maintain
the application of chlorine below the threshold which leads to TCDD formation (92).
Numerous recent mill studies of dioxin
control techniques have been reported. In
one such study involving the bleaching of
softwood kraft in an O(DC)(EO)HD sequence, chlorine dioxide substitution was
increased incrementally until, at 52% substitution, TCDD and TCDF became non-detectable in the pulp (55). In another mill
study,TCDD andTCDF became non-detectable at 85% substitution (57).
6. Effluent properties
6.1 Dioxins
Substitution of chlorine dioxide for chlorine has a profound affect on the formation
of chlorinated dioxins as is discussed in
more detail in Chap. VII 3 (125). It was
established in 1989 that increasett chlorine
dioxide substitution is one means by which
the formation of chlorinated dioxins and
furans can be reduced; at substitution
greater than 50-70%, TCDF and TCDD are
no longer detectable in pulp (91-93).
Because of their very low concentration
and limited solubility in bleaching effluent,
chlorinated dioxins and furans are difficult
to detect and measure with the result that
little information
about them has been forthcoming from laboratory
studies. However,
several mill studies have shown that,as chlo-
Table 7. Effeel of Increased clllorl_ dloxiile sullstitution 018tbe org_IIlorlne

content of
fully bleacbed commerdill pulps.
Organochlorine,
Total
mg/kg
Nonextractable
Birch kraft
O(C+D)(EO)DED
OD(EO)DED
650
120
250
100
Softwood kraft
O(C+D)(EO)D(E+P)D
OD(EOP)D(E+P)D
270
110
230
100
rine dioxide substitution increases, TCDD

and TCDF concentrations
in the effluent
decrease. Non-detectable concentrations
have been achieved at several different chlorine dioxide substitution levels: 57% (55),
85% (57), and 70% (94). Another study
showed that, as chlorine dioxide substitution increased to 100%, the concentration
of dioxins and furans decreased to less than
5 mgTEQ per kg in whitefish fillets (95).
6.2 AOX and EOX
The first measurement of the impact of
chlorine dioxide substitution on formation
of chlorinated organic material was made
by Rapson in 1966: 6% of the chlorine (CI)
charged was found as organochlorine. This
figure decreased to zero at 70% substitution
(25). In 1983 Germg:ird showed that it was
possible to estimate the organochlorine
formed by multiplying the amount of chlorine (CI) in all the chlorine bleaching agents
used in a sequence by a factor (96).
Numerous reports indicate that, as chlorine dioxide is substituted for chlorine, the
amount of chlorinated organic matter in the
effluent decreases. In earlier publications,
chlorinated organic matter was measured
asTOCI (total organochlorine)
(34). However, this method is not as accurate and
much more complex than theAOX (adsorbable organic halogen) technique. Early research showed TOCI to be much less than
AOX (91), but a more recent comparison
showed contrary results (97).
&
283
200
Kappa no.
Unbl.
30.0
o (E+O)
23.5
t>. (E+O+ P) 20.5
00
16.6
284
6.3 Chlorophenols
150
<11
t::
t::
S
0.,100
x'
o SW
Lab
0"
o HW, Lab
10
100
20
30
CI. k&'tpulp
ClO, Substitution, %
FIg. 26. TIle reWlmtsItIJI
of AOX Jonrtft
bkbi.,toe~
tN (DC)""p.
~(a)..
40
o
o
0
I.
(DC)E
I.
Axegaro showed that AOX decreases as

chlorine dioxide substitution increases and
varies linearly with the elemental chloriIle
(Cl) used in the first stage as shown in Fig.
26 (91). In these experiments, the pulp
kappa number was 20 and kappa factor was
0.18. AOX can be calculated by multiplying the elemental chlorine applied by a filetor of 0.13. This factor ~es
between 0.07
and 0.13 for laboratory-bleached softwoods
(96, 98) but has been found to be lower in
mill practice (99). In laboratory studies on
hardwoods, the factor has been found to
be much lower (0.04-0.05) (100). liebergott
also found a linear decrease in effluentAOX
accompanied increasing chlorine dioxide
substitution as shown in Fig. 27 (97, 101).
At very high levels of substitution, AOX was
lower than anticipated based on the linear
relationship observed at lower substitution
levels. There are many other studies of the
impact of chlorine dioxide substitution on
AOX formation (71, 75, B3, 102-107).
When only chlorine dioxide is used in
bleaching, the amount ofAOX formed is low
and can be further decreased by modifying
several process variables.
A mill trial
showed that, at 100% substitution, a softwood kraft pulp (post-oxygen kappa number 20) bleached
in a D(E+O)DED
sequence produced 0.65 kg of AOX/ADt
(56). AOX has been shown to decrease lineM\.y with 1'QSt-Oxygen k1~1Y.l number in the
16to 10 range for softwood kraft pulp from
an extended delignification batch process
(lOB). Another important factor inAOX for-
20
40
&0
CIO, Substitution, %
80
100
Fi,. 27.AOX~irf(DC)E~tlSlI.frMc'
tin of .MIH4:Nl
soJtfllool "rIIJt pip
lrNtMMIal
bJI/M """.,.,
IS
0.8
i<110.6
Ii:
"<11
0.4
.S
x
~ 0.2
o
0.1
0.12
0.14
0.1& _0.18 0.2
Kapp~ tartar
0.22
Fi,. 2'.
mation is the kappa factor. As shown in Fig.

28, total sequenceAOX formation decreases
with decreasing kappa factor in Do (10B).
EOX (extractable organic halogen) is a
parameter that includes all chlorinated organic compounds which can be extracted
from bleach plant effluent with an organic
solvent. EOX is also referred to as EOCI
(extractable organochlorine).
The chlorinated organic compounds of greatest concern are those which are lipophilic, that is,
those which are sparingly soluble in water
and highly soluble in fatty tissue such as
found in fish. EOX and EOCl are tests which
depend on the isolation of a fraction of chlorinated organic compounds that are only
slightly soluble in water. EOX comprises
less than 1-2% of the AOX in bleach plant
effluent; the amount of chlorinated organic
matter that is extracted depends to a major extent on the solvent used. Generally,
o
~
50
0.24
infi~ 0 ~~
D(EO)IJ(EOP)D 61MeW"g
Fig. 28. AOXfortrllltilm
I"
of 1311t1ppt1..-Hr
GXYIfI"-llelig,dfld
Super B4tcIr softwootl.
3
4
5
&
AOX, kgltonne pulp
BOX tIS IIfnctiorc
of AOXfor
6lNdn.,
9
ef-
fl.-b.
only a small fraction of the EOX is highly

lipophilic.
Extraction with ether gives EOX values
of 300-500 grams per ton of pulp for 10"10
chlorine dioxide substitution and less than
100 gran3s per ton of pulp at 90% substitution (31, 34). However, as a polar solvent,
ether extracts many compounds that are not
lipophilic. It is generally recognized that
non-polar solvents such as cyclohexane and
heptane provide EOX values which are
more meaningful. In two separate laboratory studies, a distinct relationship between
EOX andAOX has been demonstrated as is
illustrated in Fig. 29 (heptane EOX: (9B);
cyclohexane EOX: (91). Results from a mill
trial show cyclohexane EOX values for 60%
chlorine dioxide substitution in the range
5-20 grams per ton. These values decrease
by approximately 50% when substitution is
increased to 100% (56).
Lipophilic
chlorinated
organic substances, which have a potential to bio-accumulate, represent a small fraction of EOX.
Substances with an octanol-water partition
coefficient of greater than 105 Oog Kow= 5)
are generally thought of as being compounds of concern.
Chlorinated organic
substances with a log Kowgreater than 5.7
have been isolated from bleach plant effluent. At 0% chlorine dioxide substitution,
200 mg of equivalent trichlorobenzene
per metric ton of pulp was found, but when
the level of chlorine dioxide substitution exceeded 40%, only 5 mg of equivalent
trichlorobenzene
per metric ton of pulp
was found (109).
and other organo-
chlorine compounds
Several types of chlorophenolic
compounds are generated when chlorine dioxide is used in combination with chlorine to
de1ignify pulp. Formation is strongly dependent on the amount of molecular chlorine
(C~ used; some compounds, particularly
those which are highly chlorinated, are not
formed when chlorine dioxide alone is
used. Chlorine-substituted
phenolic compounds,
that is, catechols,
guaiacols,
vanillins, and syringols are formed from the
lignin remaining after pulping and may have
from one to five chlorine atoms per aromatic ring. The most abundant ring type is
guaiacol
(Fig. 30, Rl = OCH3;
~ = ~ = H).
Increased degree of chlorine substitution

leads to increased toxicity and a tendency
for bioaccumulation so that polychlorinated
aromatic compounds are of greater threat
to the environment.
When chlorine dioxide is substituted for
chlorine, the total amount of chlorinated
phenols formed increases to a maximum at
50% substitution and then decreases rapidly
to near zero at 100% substitution (31, 110,
111,124). This characteristic maximum is
decreased or vanishes if the order of chemical addition is changed from DC to CD (52)
or if the chemical charge is adjusted to provide a constant
kappa number after a
(DC)E sequence (106, 112). The maximum
OH
Phenol
Catechol
Guaiacol
Syrlnvol
Vanillin
Rs
H
H
H
H
CHO
EI,. 30. StruelufYIl types I. eblo,.," tkrlvlltives

ebloriM-tlIoxUk l!jJJ_t.
I"
- 0- .4,5 dichloro -8~

3,4,5trichloro .~.
E6
."
~5
"8 4
.~
'" 3
~
(;
_0
2
:E
U 1
,
'
,,
,,
. 0...
4,5,6trichloro
tetrachloro
,,
o
o
20
40
60
80
CIa.,Substitution,%
100
FI8. 31. CbloroguiM:ol J-IIott

lIS 8 jinIctImI of
cblorltle 4umM SfIbsIU8U-.
at 50% substitution is mainly the result of

dramatic increases in the amount of monoand dichloro compounds formed: at 90%
substitution the amounts of tri- and tetrasubstituted compounds steadily decrease ~o
near zero (52, 91,104,109).
These trends
are illustrated in Fig. 31 for the formation
of chloroguaicols
(109). The type and
amount of chlorinated
phenolic
compounds formed are also strongly dependent
on mixing (113) and kaPpa factor.
When chlorine dioxide alone is used,
trio, tetra- and penta-chlorinated
phenolic
compounds
are non-detectable
(116).
When unbleached softwood kraft pulp at
26 kappa number was bleached to 90
brightness with the sequence D(E+O)DED,
only dichlorocatechol
was found in the effluent (114). A compilation
of twelve
months of effluent data for a mill bleaching
30 kappa softwood kraft pulp to 90 brightness with a D(EOP) DED sequence showed
non-detectable trio, tetra-, and penta-chlorinated phenolic compounds at 0.1 parts per
billion (95). There are numerous other examples of mills using chlorine dioxide alone
and recording non-detectable highly chlorinated phenolics (115).
A lower unbleached kappa number, such
as can be achieved by oxygen delignification or extended delignification, was not
necessary to eliminate highly chlorinated
phenolics (115).
Chloroform formation decreases linearly
with increasing substitution of chlorine dioxide for chlorine with one study recording less than 10 glodt being formed when
chlorine dioxide alone was used (117).
285
286
Pulp Bleaching
- Principles
and Practice
Again, as with chlorophenolic

formation,
the critical factor is the amount of chlorine
used. It has also been shown that poor
mixing increases chloroform
formation
(112). In another study, it was reported
that less than 1 g of chloroform/odt
is
formed at chlorine dioxide substitution
greater than 75% (91).
Very little literature is available on the
formation of any other chlorinated compounds resulting from chlorine dioxide use
in delignification.
It has been found that,
as chlorine dioxide substitution increases,
the amounts of chloroacetic acid (31) and
tetrachlorofuranone
formed (104) decrease. The concentration
of chlorine in
high molecular weight material decreases
as chlorine dioxide substitution increases
(see Chap.Vl111) (125).
initially non-toxic, or close to the detection

limit, particularly after secondary treatment.
In addition, there are other significant
sources of toxicity from kraft mills which
complicate test results. Nonetheless, the
results of ecosystem studies consistently
indicate that increased chlorine dioxide
substitution is one means of decreasing
overall effects (98).
The many reported studies of the environmental impact of 100% chlorine dioxide bleaching sequences have been critically
reviewed by Solomon et at. (122), who concluded that:
mills bleaching with chlorine dioxide (100% substitution)
and
employing secondary treatment and with
dilution typical of North American mills,
present insignificant risk to the environment from organochlorine compounds."
6.4 Biological effects

Prior to approximately
1985, measurement of the biological effects was generally
limited to acute toxicity and mutagenicity
tests. Several reviews and laboratory studies of that time concluded that acute toxicity tended to decrease as chlorine dioxide
was substituted for chlorine in the delignification of pulp (10-12, 118). Later, acute
toxicity to rainbow trout was found to decrease to zero with increasing chlorine dioxide substitution up to 90% in laboratory
bleaching (101). Decreased acute toxicity
to Ceriodaphnia and minnows was dependent on the manner of addition of chlorine
and chlorine dioxide (52).
Laboratory studies have also shown that
effluents from chlorination stages are mutagenic and that chlorine dioxide substitution diminishes mutagenicity (11, 12, 118120). Mutagenicity disappears very rapidly
when acidic chlorination effluents are neutralized.
Many mill studies on the effects of substantial chlorine dioxide substitution include acute toxicity measurements (55, 56,
83) and other biological tests (121). However, the results are often inconclusive
about the effect of chlorine dioxide substitution because the effluents for the base
case (0"10chlorine dioxide substitution) are
6.5 Other parameters:
color, chlorate,
BOD, and COD

Chlorine dioxide substitution decreases
effluent color in proportion to the percent
substitution; one estimate is that a 1% decrease in color occurs for each 2% increase
in percent substitution (11, 12). There are
many sources of information about color
removal from laboratory (26, 31, 101, 105)
and mill studies (56, 94, 95).
Chlorate ion is a by-product of chlorine
dioxide delignification as was stated earlier
in this chapter in the discussion of delignification efficiency. Chlorate ion has been
linked to toxic effects on brown algae at
one mill in Sweden. Chlorate is eliminated
readily by the action of anaerobic bacteria
in unaerated parts of biological treatment
systems or by treatment of effluent with
sulfur dioxide.
As reported
in a the review
by
McDonough et al., BOD (Biochemical Oxygen Demand) decreases very slightly with
chlorine dioxide substitution (11, 12); a
more recent study reported
that BOD
changes very little up to 90% substitution
and then declines slightly thereafter (101).
Effluent COD (Chemical Oxygen Demand) decreases approximately
10% as
chlorine dioxide substitution increases from
0-100% although there is considerable

ter in the data (11, 12, 101).
scat-
7. Economicfactors
The greatest economic consideration in
the use of chlorine dioxide in delignification is the chemical cost. The relatively high
cost of bleaching chemicals is basically a
function of percent chlorine dioxide and
the price ratio of chlorine dioxide and chlorine as illustrated in Fig. 32 (31). This is
typical of many similar studies in which the
lowest cost is obtained in the range of 3050% substitution with the cost being rela.
tively insensitive over this range. As 100%
substitution is approached, the chemical
cost increases sharply.
The cost of increasing chlorine dioxide
substitution has been estimated from the
results in numerous mill trials. In 1%7, a
trial on a hardwood kraft pulp indicated that
increasing chlorine dioxide substitution to
about 50% does not influence cost (53). A
study made in 1973 showed that, at 25%
substitution, chemical costs were decreased
by 10% in one mill but were unchanged in
another (54). More recent mill studies and
mill surveys have examined 100% chlorine
dioxide substitution and have reported a
significant increase in bleaching chemical
cost (48, 49,56, 57).
Another factor, sometimes discussed in
connection with chlorine dioxide substitution economics, is pulp yield. This question was thoroughly
examined
by
McDonough in a 1985 review where it was
concluded that, based on literature published up to that time, chlorine dioxide
160 27 Kappa softwood
150
140
"*
Tt
u 130
.~ 120
~
110
100
90
20
40
60
80
ClO, Substitution, %
Fig. 32. Ftletors 8ffectlllg

ide SflbstttflU-.
100
tbe cost of cblorlM tUoz-

substitution had no effect on pulp yield
(11,12).
Another
aspect of the economics,
broadly speaking, of bleaching chemical
usage is the extent to which the pulp manufacturing industry adopts a particular chemical. Substantial usage of chlorine dioxide
in the first deIignification stage was limited
to 7 out of 51 bleach plants in Canada as
late as 1987, but by 1994 virtually all bleach
plants in Canada used at least 30% chlorine
dioxide in the first stage and a delignification stage using 100% chlorine dioxide accounted
for over half of the total
production of bleached kraft pulp (123).
Acknowledgments
Sterling Pulp Chemicals has provided financial support for chlorine dioxide bleaching research to the University of Toronto.
Paul Earl and Ulf Germgird reviewed this
chapter and provided helpful comments.
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a Combination
of
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M. Eng. Thesis, Dept. of
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of Toronto, Toronto, 1994.
50. Bergnor,
lindgren,
(1987).
E., Germgard,
U., Kolar, J.]',
B.O., CeUul. Chern. Tech. 21: 307
51. Axegard, P., "CIO, Substitution

Reduces
the Load of TOCI; 1987 Tappi Pulping
Conference
Proceedings,
TAPPI PRESS,
Atlanta, p.l05.
52. Liebergott, N., van Lierop, B., Kovacs, T.,
Nolin, A., Tappi J 73(10):207
(1990).
53. Wawer, A. and Scribner
Mag. Can. 68(12):T646
H.C., Pulp
0%7).
Pap.
54. Edblad, B.A., Becker, E.S., Nicholson,

R.,
Thomas,
P.R., Pulp Pap. Mag. Can.
74(3):68 (1973).
55. Munro, EC., Chandrasekaran,
S., Cook,
C.R., Pryke, D.C., Tappt J 73(5):123
(1990).
56. WlI.son, R., Swaney,]., Pryke, D.C., Luthe,
C.E., O'Connor,
B.I., Pulp Pap. Can.
93(10):35 (992).
57. Johnson, D.C., Conkle,].,
Hashimoto,
Minday, M., TapPiJ 76(3):89 (993).
S.,
58. Pryke, D.C., Tappi J 72(6):143 (1989).

59. Pryke, D.C., "Chlorine Dioxide Substitution: Mill Experience;
1992 Tappi Bleach
Plant Operation
Short Course, TAPPI
60. Reeve, D. W, unpublished
Report
Vniversity of Toronto, 1991.
61. du Manoir, }.R., CPPA
6(2):TR25 (1980).
'/rans.
C43,
Tech. Sect.
62. Tibbling, P., "Medium Consistency

Chlorination: Studies in a High Intensity laboratory Mixer" ,1988Tappi International
Pulp
Bleaching
Conference
Proceedings,
63. Germgard, V., Teder,A., Tormund,
Puu 65(4):264 (l9~3).
64. Virkola,
N.-E. and
62(12):35 (979).
65. Histed,
1994.
].A., personal
Kiiskila,
D., Pap.
E., Tappi
communication,

66. Reeve, D.W: and Weishar,
74(6):164 (991).
K.M., Tappi
67. Reeve, D.W: "Chlorination

Stage Conditions," 70th Annual Meeting, Tech. Sect.,
CPPA, Montreal, 1984, p.AI39.
68. Rapson, W:H. and Anderson,
61(10):97 (978).
69. Wartiovaara,
(982).
1., Pap.
C.B., Tappi
Puu
64(0):581
U., Apptta
71. Basta,J.,Andersson,
L., Blom, c., Forsstt
m, A., W ne, G., Johansson,
N.-G., "New
and Improved
Possibilities
in DI00
Bleaching," 1992 Tappi Pulping Conference Proceedings,
TAPPI PRESS, AItanta,
p.547.
R.W: and Wrathall,
S.H., Appita
45(5):3360992).
.
73. Basta, J., Andersson,
1., Blom, C.,
Holtinger, L., Hook,}., Appita 45(1):29
(1992).
74. Liebergott, N., Pulp Pap. Mag. Can.
720):109 (971).
75. Reeve, D.W:,Weishar, K.M., li. L.,"Process
Modifications to I>ecrease Organochlorine
Formation During Chlorine Dioxide Delignification", 1994 Tappi International
Tech. Sect., CPPA, Montreal, p.283.
76. Reeve, D.W:, Anderson, C.B., Rapson,
W:H.,Pulp Pap. Can. 81(6):Tl42 (980).
77. Maples, G., Ambady, R., Caron, J. R.,
Stratton,S.,VegaCanovas,R"BFR-A
New
Process Toward Bleach Plant Closure," International Pulp Bleaching Conference
Proceedings, Tech. Sect., CPPA, Montreal,
1994, p.253.
78. Kutney, G.W:, Macas, T.S., Donnini, G.P.,
Pulp Pap. Can. 86(5):Tl35 (985).
79. Grundelius, R, Mitchell, K.A., Rankin,}.P.,
Pulp Pap. Can. 92(4):T87 (991).
80. Howard, E.}. and Histed, }.A., Tappi J
47(1):653 (964).
81. Fergus, B.}., Tappi 56(1):1140973).
82. Fossum, G. and Marklund, A., Tappi J
71(1):79
83. Axeg:ird,
84. Basta,
P., Svensk
(980).
(1988).
P., TapptJ
69(10):54
J., Andersson,
(1986).
1., Blom, c.,

forsstrom, A. ,Wane, G.,Johansson,
N.-G.,
"New and Improved Possibilities in Dloo
TAPPI PRESS, AItanta,
p.547.
Papperstidn.
86. Annergren, G.E. and lindblad,

59(11):95 (1976).
88. Reeve, D.W:, Weishar,

Sd. 16(4):JI18 (990).
P.O., Tappi
K.M.,J
Pulp
74(2):123
Pap.
P., Pulp
(991).
Pap. Can. 9O(5):Tl83
92. Berry, R.M., Fleming,

B.I., Voss, R.H.,
Luthe, C.E., Wrist, P.E., Pulp Pap. Can.
9O(8):T279 (989).
93. Axegaro, P. and Renberg,
19(1-6):661 (989).
L., Cbemosphere
94. Pryke, D.C., Winter,

P., Bouree,
G.R.,
Mickowski, c.,PulP Pap. Can. 95(6):T230
(1994).
95. Pryke, D.C., Swanson,
S.M., KIoepperSams, P.J., Bouree; G.R., Owens,}.W:, "The
Impact
of Chlorine
Dioxide
Delignification on Pulp Manufacruring
and Effluent Characteristics
at Grande Prairie: Effluent Quality Improvements
and Ecosystem Responses," International
Non-Chlorine Bleaching Conference
Proceedings,
Miller Freeman, San Francisco, 1994.
96. Germg:ird, U. and Larsson,
65(4):287(1983).
S., Pap. Puu
97. liebergott,
N., van lierop, B., Nolin, A.,
Faubert, M., Laflamme,J., "Modifying the
Bleaching Process to Decrease AOX Formation," 76th Annual Meeting,Tech.
Sect.,
CPPA, Montreal 1990, p.B229.
98. Earl, P.F. and Reeve,
72(0):183
(989).
D.W.,
99. Sangster,
1971.
communication,
M.C., private
100. Earl, P.E, private
communication,

115. Anon.. NCASI 1994 Report.
Tappi
104. McFarlane, P.N.,AlIison, R.W:, Clark, T.A.,

Mackie, K.L., Water Sd. Tech. 24(3/4):55
(1991).
105. Allison, R.W:, McFarlane,
P.N., Clarke,
T.A.,Appita
43(4):289 (1990).
106. Berry, R.M. and Luthe, C.E.,]
Set., 18(6):JI97 (1992).
90. Annergren, G., Osterberg, E, lindblad, P.,

"Chlorinated
Organic Matter in Bleached
Kraft Pulp -Effect of Important
Process
Variables," 1990Tappi Pulping Conference
Proceedings,TAPPI
PRESS,Atlanta, p.185.
91. Axeg:ird,
(989).
290
103. Basta,}., Holtinger, L., Hook,}., Lundgren,

P., TapptJ 73(4):155 (990).
87. Granum, E, Hasvold, K., Loras, v., Soteland,

N.,] Pulp Pap. Sd. 10(3):]25 (984).
89. Reeve, D.W:, TapPiJ
70. Asplund,
C. and Germgard,
44(2):950991).
72. Allison,
85. Axegard,
83(0):284
289
1994.
101. liebergott,
N., van lierop, B., Nolin, A..
Faubert, M., Laflamme,}., Pulp Pap. Can.
92(3):T70 (991).
102, Histed,]., and Vega Canovas, ft.."Dccrea~
ing the Usage of Chlorine and Caustic in
p.85.
Pulp Pap.
107. Allison, R.W:, McFarlane, P.N.,Judd, M.C.,

Pap. Puu 75(4):234 (993).
lOB. Boman, R., Dahl, M., Lindstrom,
L.-A.,
Norden, S., "Pulps Produced in Extended
Super
Batch
Cooks
Show
Good
Bleachability," 1991 Tappi International
109. Annergren, G., Carlsson, G., Norrby, M.,
"Spent liquors for Bleaching of Softwood
Kraft Pulps. Effect of Chlorination
Variables on the Content of lipophilic
Chlorinated Organic Matter with Low Molecular Mass; EUCEPA Symposium Proceedings, EUCEPA, Paris, 1986, p.65.
110. Voss, R.H., Wearing,}.T., Mortimer, R.D.,
Kovacs,T.,Wong,A., Pap. Puu 62(12):809
(980).
Ill.
Voss, R.H., Wearing, }.T., Wong, A., Tappi

64(3):167 (981).
112.Earl,
P.F. and Reeve,
730):179
(990).
D.W.,
Tappt
113. Earl, P.P. and Reeve,

73(1): 179 (990).
D.W.,
Tappi
114. Morgan,}., Thakore, A., Krauza, K., "Mill

Scale Evaluation
of Pulp Chlorination
Systems," 1991 Tappi International
Pulp
Bleaching
Conference
Proceedings,
TAPPI PRESS,Atlanta, p.271.
116. O'Connor,
B.I., Kovacs, T.G., Voss, RH.,
Martel, P.o., van Lierop, B., Pulp Pap.
Can. 95(3):T99 (1994).
117. Crawford, R}., Dallons,V.}. ,Jain,A. K.,Jett,
S.w., TapptJ 74(4):159 (1991).
118. Donnini,
(1983).
119. Eriksson,
K.,Svensk
G.P., Pulp Pap. Can. 84(3):T55

K.-E., Kolar, M.-C., Kringstad,
Pappersttdn.
82(4):95 (1979).
120. Nazar, M.A. and Rapson, W.H., Pulp Pap.

Can. 81(8):Tl91
(1980).
121. Hall, T. and Haley, R.K., "The Use of
Chronic Bioassays in Characterizing
Effluent Quality Changes in a Mill Conversion to Increased Chlorine Dioxide Substitution;
International
Pulp Bleaching
Conference
Proceedings,
Tech. Sect.,
CPPA, Montreal, 1994, p.1l5.
122. Solomon, K., Bergmann, H., Huggett, R,
Mackay, D., McKague, B.,"A Review and
Assessment of the Ecological RisksAssociated with the Use of Chlorine Dioxide
for the Bleaching of Pulp," International
Tech. Sect., CPPA, Montreal, 1994, p.145.
123. Pryke, D.C.,"A Survey of Chlorine Dioxide Substitution
in Canada," prepared for
the Bleaching
Committee,
Tech. Sect.,
CPPA, Montreal,June,
1994.
124. Voss, R.H., Wearing,
Pap. Can. 82(2):T65
}.T., Wong, A., Pulp

(981).
125. Dence, C. and Reeve,D.W: (Eds.), in "Pulp

Bleaching
and Practice;
- Principles
TAPPI PRESS, Atlanta, in press, 1996.
SECOON IV:
The Technology of
Chapter 4:
(Oxidative) Alkaline Extraction
Richard Berry
Pulp and Paper Research Institute of Canada
Pointe Claire, Quebec
1. Introduction.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
1.1 Development of alkali use in bleaching.
2. Role of extractlon in bleaching. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
2.1 Solubilization and reactivation of lignin
2.2 Alkali-consuming reactions
',' . , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
2.3 Lignin dissociation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
3. Factors affecting aIkaJi consumption.
................................
"
3.1 Carryover
3.2 Addition of oxygen and peroxide. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
3.3 Substitution of chlorine with chlorine dioxide. . . . . . . . . . . . . . . . . . . . . . ..
4. Effect of extraction on extractives and carbohydrates.
.................
"
5. Effect of extraction on reversion.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
6.First extraction stage
6.1 Kinetics
6.2 Chemical concentration (charge and consistency) . . . . . . . . . . . . . . . . . . . ..
6.3 Consistency. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
6.4 Temperature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
6.5 Time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
6.6 Pulp type . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
6.7 First-stage oxidant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
7. Oxidant-reinforced
extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
7.1 Development of oxidant addition. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
7.2 Oxygen
,
7.3 Peroxide
8. Seomd extraction stage . . .. . . .. .. .. . . .. . .. . .. .. . . . .. . . . . . . . . .. .. . . . ..
8.1 Kinetics
8.2 Chemical concentration (charge and consistency) . . . . . . . . . . . . . . . . . . . ..
8.3 Tune. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
8.4 Temperature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
8.5 Rapid extraction
8.6 Added oxidants
9. Other aIkalles. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
? 1 Chlorine-tO"5Odium hydroxide ratio
9.2 On-site sodium hydroxide generation
9.3 Conversion of chlorine to chlorine dioxide. . . . . . . . . . . . . . . . . . . . . . .,
9.4 Alternative alkali sources. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ." . . . . . . ..
9.5 Papricycle process. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .,
291
293
293
293
293
296
296
297
297
297
297
297
298
299
299
302
303
304
305
305
305
305
305
306
310
312
312
313
313
313
313
314
314
j 14
314
315
315
315
Chapter IV 4: (Oxidative) Alkaline Extraction
Chapter IV 4:
(Oxidative)
Alkaline Extraction
1. Introduction
1.1 Development of alkali use in
bleaching
The use of a1kali has remained one of the
few constants in the evolution of pulp
bleaching. However, the way a1kali has been
used has changed significantly since the first
recorded alkaline bleaching stage using
potassium hypochlorite for bleaching textile fabrics was described in 1789 (I). In
the intervening 200 years, a1kali has been
used to achieve several objectives in the
bleaching process. In the first application
cited, a1kali was used to provide an optimum reaction pH for the hypochlorite and
simultaneously to provide the conditions
under which the reaction products could
be hydrolyzed and solubilized. It was later
recognized that chlorine is more effective
under acidic conditions and so the oxidation step, chlorination (C),and the hydrolysis/ solubilization step, extraction (E), were
separated. This led to the development of
multiple-stage bleaching processes, such as
CEH and CEDED, where the oxidation and
hydrolysis steps are separated. In modem
bleaching, the distinction between an alkaline oxidizing stage and an extraction stage
is blurred by the now routine addition of
oxidants to the latter stage. A distinction
can be made between the two by considering that a stage having a final pH higher than
TtJlJle1. RetJeIIon coruIltitms for ~
IIIssoI""
293
10.5 following an acidic oxidizing stage can

be properly considered an extraction stage.
Although most of the sodium hydroxide
used in bleaching today is applied to softwood or hardwood kraft pulps in sequences
such as (DC)(EO)DED, more sophisticated
alkaline extraction techniques (2) are still
used on acid sulfite pulps.The a1kali charge.
temperature, and retention time of the extraction stage determines
the degree of
hemicellulose removal and the a-cellulose
yield in these extraction techniques (fable
1). Products ranging from hemicelluloserich glassine and greaseproof papers to the
hemicellulose-poor dissolving pulps may be
generated. Dissolving pulps are used as an
a-cellulose source for polymeric chemical
products such as cellulose nitrate, cellulose
acetate, and rayon. These techniques, although of only historical interest to a large
segment of today's industry, have provided
a valuable understanding of the action of
sodium hydroxide on the carbohydrate fraction of the pulp, an understanding which
is relevant today when considering the accumulated effects created by the highly alkaline steps ofTCF (totally chlorine free)
bleaching processes.
2. Roleof extraction in bleaching

2.1 Solubilization and reactivation of
lignin
For bleached kraft pulp producers, the
role of extraction is to remove the lignin
made potentially soluble by the previous
acidic oxidizing stage and to reactivate the
pulp to further oxidation. Directly after
pulping, the combination of a single acid
oxidizing stage (until recently chlorination)
prIIps.from cll10rlrutlell SfIIftIe Jnllps (1).
a-Cellulose,
%
NaOH,
% on o.d. pulp
Tune,
min
Temp.,
C
Consistency,
%
89-90
0.5-2
120
50-SO
10
<]0-93.5
2-6
45-150
80-125
10-22
93.5-96
6-15
15-240
95-145
10-22
>96
to
30-60
30-40
294
-Principles
Pulp Bleaching
and Practice
30
~
Q)
J:j
25 -
20
E
::J
Rapid phase
/'
c:
15-
a.
CO
~
10
W
c..>
Slow phase
5-
..
,
I
10
20
30
I
40
50
Time, min
Rg.l.
CII_gell,
CE lIIIJIIItt amber
IIIUII/:b1orlfUllttm
and an extraction stage removes over 90%

of the remaining lignin (Fig. 1). Most of this
delignification can be achieved with a 2minute chlorination. If the chlorination reaction time with excess chlorine
is
extended from 45 minutes to 7 days, the
CE kappa number is further decreased only
to a small extent (3). Some lignin remains
in the pulp despite the presence of excess
oxidant. By extracting the chlorinated pulp
with a1kali, the pulp can then be further
bleached with, for example, chlorine dioxide. Again, there is a limit to the degree of
lignin removal that further oxidation can
achieve and another extraction step is often required to reactivate the pulp for a final oxidation stage.
Several hypotheses have been put forward to explain the role of extraction in
reactivating the pulp. One proposal is that
a chloro-lignin layer forms in the fiber walls,
and that this layer constitutes a barrier to
further chlorination by limiting the motion
of the chlorine front through the fiber matrix (4). According to this hypothesis, the
role of extraction is to remove the physical
barrier and allow the exposure of unreacted
lignin
to further
oxidation.
This theory,
however, requires that an unreacted core

be observed in the center of the fiber wall
which has been shown not to exist (3). A
it_forti
softwood
Inwft p,IIp (/ulpptl..umber;
28.8)(3).
modification of the foregoing hypothesis

(5) attempts to overcome this difficulty by
proposing that chi oro lignin layers form
around lignin which is distributed heterogeneously in the fiber wall. Chlorine, therefore, could access the whole fiber wall at a
macro level but not at a micro leveL However, the lignin that remains in the pulp after extraction contains substantial amounts
of chlorine suggesting that all lignin in the
pulp, at both the macro and micro level,
has been fully chlorinated (3).
A second hypothesis is that the lignin that
remains is bonded to carbohydrate and that
acidic oxidants other than chlorine are required to break these bonds (6). It seems
likely that these bonds exist but, as similar
kinetics are exhibited by other oxidants, it
is unlikely that these bonds cause the observed need for alternation of acid oxidation with alkaline extraction.
A third hypothesis is that oxidation cannot continue further because of chemical
deactivation of the remaining lignin. Acidic
oxidation leads to modification of the molecular structure of lignin and creation of
blocking groups which prevent further oxidation but which are broken down under
alkaline conditions (Figs. 2 and 3) (3,7).The
role of alkaline extraction, according to this
hypothesis, is to generate new active groups
on the remaining lignin structures that al-
295
296
o
II
C-OH
CI-b-O-Ug.
CI.
H
Blocking
-Principles
Group
2.2 Alkali-consuming
Ug.
Ltg.
"*"
C, C):~ H
Cl...... ....c....~~b
~O
CI.
HOOCH.
~OH
Lig.
C, J~
~~C
Blocldng Group
Lig.
"*"
HOOCH.
loll
Ltg.
"*"~o
CI
C~
-------
"*"
CI 0
OCH.
OR
~C1z
Ho'H
Blocking Group
Lig.
H
b~OH
H
CI/ 'C
OCH.
OR
BlocktlgGroup
Pig. Z. Prop0se4
frmutlml
o
II
C-OH
I
CI-C-o-Ug.
I
C-oH
II
o
!'IaCL C...C~ H
cv
H b~o
fio
blocih8g
01....'"'
NIIOH
Blocking
groups
(3, 7).
NaCI
+ Na2C03
HO-Llg
HaCI
+ Ha2C03
Activated Lignin
NIIOH
~
NaCI
+ Na2C03
+ Activated Lignin
CI
OR
Furta Oxidation
~Productl
reactions
In the fina1 ana1ysis, it is likely that both

removal of organic material and chemical
reactivation of the 1ignin structure have significant roles in alkaline extraction. The removal of organic material ensures minimum
chemical consumption in the subsequent
oxidizing stage and chemical reactivation
ensures renewed rapid initial reaction in the
subsequent stage. Quantification of caustic
(NaOH) consumed in various ways has been
determined by doing a sodium balance on
the extraction stage (9) (Fig. 4). A 33 kappa
softwood kraft pulp was chlorinated with
6% chlorine on o.d. pulp and extracted with
variable charges of sodium hydroxide. At a
charge of 3% NaOH on o.d. pulp, 30% of
the sodium hydroxide was consumed in
forming sodium salts of soluble carboxylic
or phenolic organic acids, 30% in forming
sodium chloride, and 30% in forming s0dium carbonate.
Sodium chloride formation during caustic (NaOH) extraction of thoroughly washed
pulp that was is caused by hydrolysis of organically bound chlorine in the pulp. Most
aliphatic organically bound chlorine and
heavily chlorinated aromatic compounds
are susceptible to alkaline nucleophilic substitution reactions (Fig. 3). Sodium carbonate formation
is caused
by another
hydrolysis reaction which occurs with activated carboxylic acids (Fig. 3).All these reactions activate the remaining lignin to
funher oxidation.
A funber small amount of the sodium hydroxide is consumed in forming sodium
salts of insoluble organic acids which remain with the pulp. These insoluble acids,
particularly if phenolic in nature, probably
represent a portion of the reactivated structures. Some residual sodium hydroxide also
is present to ensure a sufficiently high pH
for full extraction of the pulp.
2.3 Lignin dissociation
The solubilization of the oxidized material is largely caused by the greater water
solubility of the sodium salts of otherwise
insoluble organic acids. However, the alkaline environment also decreases the degree
of association of lignin molecules and decreases their hydrodynamic volume which,
in turn, increases their ease of removal from
the fiber wall.
Ug.
LIII.
CI
Group
N80H
and Practice
low reaction with the oxidizing agent used

in the next stage. These models have been
developed by evaluating extraction after
chlorination but could equally apply to extraction after a chlorine dioxide stage (8).
FUItIMr OIdd8lon
Produclo
b-OH
Pulp Bleaching
Ct
CI
NeOH
OCH1
NaCI
+
CI
*
OR
OH
OCH1
234
NaOH charge, % on o.d. pulp

I
PIg.4. Whmr HIturcelor ,. ~
ezIrtIetlml.fter eblorl""tImIol50ftwootllmlftpulp (hIpptI
.IImber, 33.4) lIS.j'rnretWtI 01'. sodtllm by4rw1de elHwge(9).
297
50
a.
:;
a.
40
~30
0"'"
c:
Precipitable
~Fraction
~20
Z
0
10
....I
11<
*_
0
0
Fraction
7
~~.
10 11 12
pH
298
Pulp Bleaching
-Principles
and Practice
stage. Fatty and resin acids are saponified

(sodium salts are fonned and the acids solubilized) (13) and polysaccharides can be degraded
and solubilized
(14-18).
In
particular, hemicelluloses can be removed
under certain extraction conditions (Sect.
1). Oxidation, before and during extraction,
stabilizes the carbohydrates against yield
loss by the peeling reaction (19). Oxidation, however, can introduce
carbonyl
groups into the carbohydrate
structure
which allow rearrangements to occur in the
presence of sodium hydroxide (Fig. 7) (2022). These rearrangements
lead to chain
cleavage and decreased chain length, which
is observed as a decrease in pulp viscosity.
In most circumstances, the degree of viscosity change is too small to affect the
strength of the paper made from bleached
pulp. However, one method of eliminating
most of this viscosity loss is to use a reductant such as sodium borohydride (23). It is
also possible to stabilize carbohydrates by
oxidizing the carbonyl groups to carboxylic acids with a selective oxidant such as
sodium chlorite (23). Neither of these
methods is practised on a commercial scale.
5. Effect of extraction on reversion

The removal of carbonyl groups by the
action of alkali, although causing viscosity
loss, decreases brightness reversion (Table
2)(24).
Table 2. Effect of" SOIUl e:!drtldloll slilge"" brigbtness reversUm (24).
Evidence for association of lignin molecules during a1kali extraction is provided

by the amount of the lignin dissolved in the
extraction stage that is precipitable when
the pH is decreased to 2 (Fig. 5) (1 0). This
progressive association, or precipitation, is
the reverse of the progressive dissociation,
or dissolution of lignin, occurring in the
chlorinated fiber during extraction.
3. Factors affecting alkali consumption

3.1 Carryover
All of the reactions occurring in extraction are affected by carryover from the previous stage. Any organic material not
removed by washing can participate in s0dium hydroxide-<:onsuming reactions while
carryover of hydrochloric acid and carbon
dioxide increases the amounts of sodium
chloride and sodium carbonate produced
by neutralization with sodium hydroxide in
the extraction stage.
3.2 Addition of oxygen and peroxide

Analysis of the sodium balance also allows the effect of changing the degree of
oxidation to be determined. The introduction of oxygen or hydrogen peroxide into
the extraction stage increases the amount
of carbonate that is produced and also decreases the amount of residual sodium hy-
droxide.This increase in carbonate is caused

by an increase in the degree of lignin oxidation and an increase in the concurrent
formation of carboxylic acids.
3.3 Substitution of chlorine with

chlorine dioxide
The replacement of chlorine with chlorine dioxide in the first bleaching stage also
changes the amounts of sodium salts of organic acids, sodium chloride, and sodium
carbonate fonned in the extraction stage
(Fig. 6). It is well recognized
that the
amount of sodium hydroxide required in
extraction is decreased by chlorine dioxide
substitution (11). Most of this decrease in
sodium hydroxide consumption is achieved
through the decrease in the amount of s0dium chloride produced in the extraction
stage. However, with the increased oxidation caused by chlorine dioxide substitution, greater lignin removal occurs in the
washing step before extraction (12); therefore, there is less organic acid to neutralize
in the pulp and to be decarboxylated and
converted to sodium carbonate in the extraction stage.
CEHD control
81.3
83.1
82.7
82.7
30
30
60
Extraction
Extraction
Unbleached pulp:softwood
Water soak: 48C
Extraction: 48OC, 10.5 pH
Thermal Reversion,
% ISO Brightness
ISO Brightness,
%
pulp
Water soak
4.6
4.3
3.3
3.1
kraft
3.5
3
Residual
sodium hydroxide
2.5
2
1.5
0.5
Sodium chloride
o
o
4. fffett of extrilttion on extractives and carbohydrates

The other pulp components are also affected by the alkalinity of the extraction
Time,
min
Treatment
00
00
100
Chlorine dioxide substitution, %

Fig. 6. JJfft
of.flrst
stlJge eblorllHl tlItmtIe
Sllbstltrltltm
Off sodI.m
11Me:drtletltmof MlftfIJOOtllnwft
jnIlp (1uIppa".mber, 29.5).
balmlee
ill
OXYgert-rel"forced
""
"1,,,,-
299
300
- Principles
Pulp Bleaching
and Practice
20
(1~~ ~~
~~~
0 0
HO
011
IKIfIoC
HO
IKIfIoC
011
HO
000
I
IKIfIoC
-~~-
CD
.0 15
E
::J
c:
CO
0.. 10
011
0..
+OH13
HO
~W
()
~~--
-0=---
o
o
0
8
IKIfIoC
011
~
0
000
I
S
IKIfIoC
O
.
011
H:zO.
0
IKIfIoC
FIg.8. IlIJUof CEUJ1IM""",... ~

JIfIlp(UJ1IM"""""
+OHS
2!}.5)(25).
00
~
Time,h
.t . CONSt""t
~
100
1~
1~
UmCOtfeet8lrrJtUm
for. softwoolllmJft
18
16
Chlorine charge
....
CD
FIg.7. ~ofOJdlUzM~
'-I'sgto
6. First extraction stage

6.1 Kinetics
The previous section has shown that the
extraction stage is a process that involves
multiple chemical reactions. Some of these
occur easily and rapidly; others require
more vigorous conditions.The physical processes of sodium hydroxide diffusion into
the fiber and sodium salts out of the fiber
also have to be considered. Of the oxidized
lignin reactions occurring with sodium hydroxide, neutralization reactions occur instantaneously.
The second most rapid
reactions are those leading to chlorine hydrolysis which generate sodium chloride;
finally, the slowest reactions are carboxylic
acid elimination reactions that generate s0dium carbonate (9). Based on this analysis,
it is the conditions allowing full generation
of sodium carbonate that are required for
an effective alkaline extraction stage. The
overall reaction rate in the extraction stage
is determined by the temperature, as dictated by the Arrhenius equation, and by the
concentration
ofthe active chemical (25).
There are, however, other limitations on the
process, and these are determined by the
economics of providing a given tempera-
dM", t:1MHge""""'g""'*-~
.0
14
E
::J
c: 12
CO
0..
0.. 10
CO
~W
8
()
(15).
ture, a suitable retention time, and a requisite chemical charge.

In low-consistency kinetic experiments
in which the hydroxide ion is kept constant
(25), the CE kappa number is shown to decrease in two phases (Fig. 8). There is an
initial rapid reaction phase which is completed in 10 minutes and a slower reaction
phase which continues even after long
reaction times. For 4 or 5 hours, the decrease
in kappa number is exponential and, beyond
this, the kappa number decreases according to a zero order reaction (25). In the
rapid phase, the reaction is affected most
by the incoming C-Stage kappa number (Fig.
9), pH (Fig. 10), and temperature (Fig. 11)
(25).The slow second phase of reaction is
far less dependent upon these variables than
the fast phase of the reaction. This conclusion is drawn from the almost parallel decreases in the kappa numbers of the pulp
samples beyond a 100minute reaction time
in Figs. 9-11. The conclusion drawn from
these observations is that there are two different mechanisms working in the extraction
process; one mechanism is operative during
the rapid phase of the extraction and the
other during the later phase of extraction.
O.15'Kappa number
O.20'Kappa number
O.25'Kappa number
6
4
FIg.!}. JlJIteof ~
.rlsg
10
20
30
40
Time, min
50
60
70
", tbe UJ1IM""",... of. ImJftJIfIlpblebetI wltb tIlfJ-t

emwetltm., t:OIIStat IIqrwr """"sUy (25).
"""'*These observations have been summarized (25) in the form of a mathematical

equation in which the kinetics are described
as two first-order reactions with respect to
kappa number:
dK/dt = -~.[OH-]oz.K,-- k;[OH-]005.K, [1]

where K = kappa number after extraction
= K,- + K,
K,-= the lignin removed in the fast

reaction
=K.-K.
o ,
Ko = kappa number before extraction
K,= the li~ removed in the slow

reaction
eblorlu mulUples
intercept
=the
extrapolation
kf
=
=
of the reverse
of the linear
slow phase with the Y-axis.
the fast reaction rate constant
Af.e('390001R1)
= 1.5
min.1.mol-oz
at 6O"C
k, = the slow reaction rate constant

A, .e(:zooolR1)
= 0.005 min.l.mol-o.05 at 60C
Af = Frequency factor in the Arrhenius
equation for the fast reaction
A, Frequency factor in the
Arrhenius equation for the
slow reaction.
=
=
Chapter
IV 4: (Oxidative)
Alkaline Extraction
301
302
14
12
13
...
....
~12
CD
.c
10
~11
c:
c 8
as
a.
a.
6
::I
~10
0.
as
~W
()
9
8..1
J2
04~.
-...........
w
()
4
10
20
30
40
Time,
Rg. 10. 1J.ffect
ol,,'IMlI,,'ty
""ted
softwood
011tbe me 01 bpJM _her
Inwft pulp
50
60
70
min
tlecretue ariftg
"lIulil.
(25).
extrtldlort
14
12
::I
c:
as
10
0.
0.
as
8J
w'-.
~------
~W
()
6
30
01" cblorlftllted
dK;dt
= -kfI.[OH-j02.K,-~'[COtjLO.K.
[2]
dK/dt
= -kd.[OHY01.K, - k,2.[COtjo.oo;.K, [3]
where
10
20
30
40
50
Time, min
60
Rg. 11. 1J.ffect01 temperatrwe 011tile me 01 bpJM ""mber tlecretue 48rl"g tIlIMll.
utetl softwood Inwft pulp (25).
This work shows that conditions in the first

10 minutes of extraction are critical and that
high temperature and high alkalinity during this phase of extraction provide the best
extraction. It suggests also that an increase
in alkali concentration
resulting from an
increase in consistency improves the degree
of de lignification achieved in the rapid
phase of reaction.
One factor not included in this evaluation, but which affects the later phase of
reaction more than the earlier phase of reaction, is the concentration of organic material in the spent liquor (Fig. 12) (25).
These results strongly suggest that the slow
kfl = the fasthydroxide reaction rate constant
70
2.1
=
exIrtIctUm 0111eblorl-
reaction phase is dominated by a diffusion

process much like alkaline leaching which
can be used after kraft pulping (26).Alkaline leaching changes the degree of association of the lignin molecules, which in
turn decreases their apparent molecular
weight and increases their rate of diffusion
from the fiber. Diffusion processes are less
influenced by temperature than are chemical processes but are largely affected by the
concentration gradient from the inside to
the outside of the fiber.
Two other kinetic studies have been
made (27, 28). Each demonstrates the significance of the hydroxide concentration,
40
50
!tJInIllqIwr011tbeme 01bpJM
-'Inwft pulp (25).
softwood
but the more recent study (28) also takes

into account the effect of carbonate and is
considered in more detail here.
Using the same nomenclature as in Equation [1j:
...
<D
20
60
Time, min
R,. 12. Effect
01tIllMI.
16
..c
10
01" eblorl-
kf2
= the
=1
k" =
k'2 =
0'
arl",,,,IMl.
tions are an order of magnitude lower than

those of the hydroxide reactions. Extraction with carbonate, therefore, would require more time or a higher temperature to
compensate for the lower reaction rates.
These kinetic equations allow a theoretical understanding of the effects of chemical concentration (which includes the effect
of consistency), temperature, and time.This
understanding, when coupled with practical constraints, yields the optimum operating conditions.
'e(-~9000IR1)
fast carbonate
reaction
rate constant
ij6.e(-4I4001R1)
the slowhydroxidereactionrate constant

e<-2OOOIR1)
the slow carbonate

0.05.e(-20001R1)
reaction rate constant
This analysis allows more precise modelling of the extraction stage and predicts the
performance of the extraction stage when
all the sodium hydroxide in the extraction
stage is consumed and only carbonate remains to continue the extraction process.
This analysis also allows the prediction of
results when sodium carbonate alone is
used as the extractant (28). In particular,
the rate constants for the carbonate reac-
6.2
Chemical concentration
(charge
and consistency)
The kinetic analyses show that, although
the hydroxide concentration
has a much
larger effect on the fast phase than on the
slow phase of extraction, both phases benefit from a high concentration
of sodium
hydroxide. There is, however, a practical
constraint on how much sodium hydroxide can be applied. A balance is achieved
between the amount of sodium hydroxide
used and the amount of oxidant required
in the following stage. Figure 13 shows that,
with increasing sodium hydroxide charge,
the CE kappa number decreases to an asymptotic limit which is lowered as more
oxidant is applied in the first stage of bleaching (29, 30). In a first stage in which only
303
20
c:
0
:;::; 18
0
as
... 16
)(
Q)
...
Q)
1ij
...
Q)
.D
14
Kappa
factor
12
10
E
::] 8
c:
as 6
0.
0. 4
as
~2
0
JIIg.13. E.fIeeto/s0M88
~
In"IIftJnIlp (IuIppII-.6er,
234
5
6
NaOH, % on o.d. pulp
dNIrp '"t6e.extrwetloll
31.')} (29).
cWorine is used, the optimum charge of

sodium hydroxide to the extraction stage
has been suggested to be Q.6 times the cWorine added to the cWorination stage (31).
As already explained and illustrated in Fig.
6, substitution
of cWorine with cWorine
dioxide allows the sodium hydroxide
charge to be decreased which changes the
relationship between the oxidant and caustic (NaOH) charge. In practice, the optimum charge is the amount required to give
a final minimum pH of 10.5 at the end of
the retention time. This measurement
is
most frequently made in the dilution zone
of the extraction tower. Some mills, however, measure pH in the E-stage washer vat.
A pH of 10.5 indicates the near total consumption of sodium hydroxide and is a consequence of the alkalinity associated with
the sodium carbonate formed during the
extraction.
Using final pH as a control of the sodium
hydroxide application allows the bleach
plant operator to respond effectively to the
several variables that affect the required
charge of alkali: changes in the kappa number of the pulp entering the bleach plant
which in turn affects the oxidant and alkali
requirements; changes in cWorine dioxide
substitution;
addition of oxidants to the
extraction stage; and carryover of acidity
slllp 011tile CE1u1pp111I1IIII6er

01 II sofl-otl
from the bleaching first stage. The time delay in such a control feedback loop is large,
corresponding to the retention time of the
stage but, because the degree of change in
the caustic charge caused by variations in
normal operation is small, this control system functions adequately. The extraction
stage control system can be refined to include a feed forward signal from the cWorination stage control system (30). In this
strategy, the caustic charge is ratioed to the
oxidant addition. When this approach is
combined with final pH control, both shon
and long period variations can be managed.
6.3 Consistency
In practice, bleaching at higher consistencies decreases the amount of steam required
to achieve
a given reaction
temperature and also decreases the retention time which determines the size of the
bleaching tower. Bleaching at lower consistencies generally allows better mixing
which in turn ensures more uniform and
complete reaction.
Theoretical considerations can also be
incorporated into the determination of optimum consistency. The kinetic analysis
shows that increasing the alkali concentration by increasing the consistency improves
the degree of delignification achieved in the
304
Pulp Bleaching
- Principles
and Practice
rapid reaction phase. However, if diffusion

is a key mechanism in the later extraction
phase, a low consistency would then be
advantageous during this phase. These results present a contradiction which calls for
a different recommendation
regarding consistency depending on the extraction phase
being considered. When these theoretical
conjectures are superimposed on the practical considerations, then medium consistency (8-1ZOA,)
is the preferred choice for mill
systems (29). At this consistency, most of
the benefit of high alkali concentration is
obtained (Fig. 14). Concurrently, a balance
is found between the capital cost ofthe required tower and the cost of obtaining
higher consistencies, and between the operating cost, in terms of steam, of attaining
a given temperature (Table 3) (29) and the
disadvantages resulting from less uniform
mixing. Concern over mixing, however, has
been almost eliminated with the advent of
high-intensity
mixers which have been
widely installed in first extraction stages to
allow the use of oxygen.
6.4 Temperature
The extraction rate increases with temperature.The kinetic analysis shows that the
rates of the fast-phase reactions with both
hydroxide and carbonate ions are increased
to a greater extent by increasing temp-
Table 3. Effect oltl!lftjlerlllurt! ;md consistency 011

strllm reqrdremmts (29).
Temp.,
cC
Consistency,
%
Steam,'
kg/t
40
400
760
1334
667
400
266
10
10
10
40
60
80
60
60
60
60
3
6
10
15
C stage: 6.8% Cl, on o.d. pulp, 3.5% consistency, 20C, 60 minutes

E stage:4% NaOH on o.d. pulp, 60 minutes
. Assuming
the temperature of chlorinated
and washed
pulp is 38C.
erature than those of the slow-phase reactions.Again, practical considerations determine the eventual configuration
of the
system. The temperature in an extraction
stage without oxygen carried out in a conventional downflow tower cannot exceed
95C. Temperatures higher than 95C are
achievable in retention vessels built to withstand pressure but, even in extraction systems that include
both oxygen
and
peroxide, a temperature of 95C is rarely
exceeded in present bleach plant configu-
8.5
8
...
Q)
.D 7.5
E
::]
c:
7
as
0.
0.
as 6.5
~w
U
6
Time, min
15
5.5
2
6
8
Consistency,
10
%
12
14
16

rations. The cost of attaining higher temperatures generally does not justify any
chemical savings that might be achieved by
increased extraction in a given retention
time or a saving in capital cost associated
with a smaller retention tower (29).A balance of practical factors usually establishes
the extraction temperature between 60 and
80C.
6.5 Time
The kinetic analysis shows that the extraction rate is determined by the concenttation of active chemicals and temperature.
The time available for exttaction is determined by retention tower size and mill production
rate. Most extraction
towers
provide a retention time of between 60 and
90 minutes which tends to be shortened as
mills exceed the nominal production rate.
The towers are usually downflow in design
which allows the retention time to be varied. The time is always sufficient to allow
the fast-phase reactions to occur and allows
some time for the slow-phase reactions.The
kinetics described in Figs. 8-12 were developed by keeping the concentration of s0dium hydroxide constant throughout the
exttaction. With a single application of sodium hydroxide, the concenttation
of s0dium hydroxide falls throughout the stage,
and only the time required to allow complete consumption of the sodium hydroxide is necessary.
Literature
data (31)
indicate that the time required is about 60
minutes.
6.6 Pulp type

The conditions of the exttaction stage
that are effective for kraft softwood furnishes are also effective for kraft hardwoods
and for sulfite pulps. For conventional papermaking pulps, the control sttategy of
targeting a final pH of 10.5 in the extraction stage ensures the correct alkali charge.
6.7 First-stage oxidant
Chlorine and chlorine dioxide are the
dominant acidic oxidants used in the first
stage; the effect of changes in chlorine dioxide substitution on extraction have already been described. However, ozone is
305
also now being used in several mill installations (32).As with the other oxidants, extraction of ozone-treated pulps improves
the efficiency of a sequence in which ozone
is used by decreasing the kappa number and
improving the further bleachability (33,
34). Some advantage may be obtained by
eliminating the wash step between highconsistency ozone (Z) stages and the following E stages; peroxides, carried over
from the ozone stage, become active in the
alkaline environment
of the extraction
stage.At medium consistency, however, the
amount of acid in the carryover substantially
increases the caustic (NaOH) requirement
of the extraction stage.
7. Oxidant-reinforced
extraction
7.1 Development
of oxidant addition
Before 1980, oxidants were used sparingly in the extraction stage. Sodium hypochlorite and hydrogen peroxide were
added to overcome specific problems such
as shortfalls in the availability of chlorine
dioxide, the need to produce a very high
brightness grade, or the need to decrease
the color of the extraction stage effluent.
Since 1980 there has been a rapid implementation of oxygen reinforcement in the
alkaline exttaction stage.
The potential of using less expensive
oxygen in oxygen-reinforced alkaline exttaction to replace more expensive chlorine di-
oxide in the D1 stage was recognized before

1980 (35), but an easy and economical
method of industrial implementation was
not available until the introduction of medium-consistency
high-intensity
mixers
(36). Since that time, other reasons for using oxygen and peroxide in extraction
stages have arisen, for example: 1) to decrease the molecular chlorine multiple used
in the first bleaching stage to decrease the
formation of chlorinated dioxins and furans;
2) to decrease the concentrations of chlorinated phenolic compounds and adsorbable
organic halogen (AOX) in the effluent; and
3) to decrease the concentration of organically bound halogen (OX) in pulp. These
environmental
pressures
have led to
306
Pulp Bleaching
-Principles
and Practice
16
c:
0
:u
x
a>
14
Chlorinated and washed pulp
~12
....
a> 10
1ij
....
a>
.c
E
~c:
as
a.
a.
as
x:
I(E~)I
8
6
4
2
0
1
2
3
4
NaOH charge, % on o.d. pulp
ng. 15. E./fectof fr1P"-mtljtm:tNllll1ull_ ~

Inwft}1tllp
1h
""'_
(IIIpJM nlllber,
", plltntbesa
0tI tbe IuIjJJM___
vIseosIty of" softrNNl
32; tJIseosIty, 2BmP"os; chlorllllltell with 6.M>"""

Cl,
0.1% CIO on PUlP).
IIt'e 0.5% CED IIIseoslty of tbe pulp II.ftn' extrtu:tlon """
'ti ",p"os (J3).
sequences where most of the bleaching

work is done in oxidative exttaction stages
(37-40) and where the initial acidic-oxidant
stage can be considered a lignin activator.
At the limit of this scenario, the use of nitrogen dioxide (41), chlorine, chlorine dioxide, or ozone (42) before oxygen
delignification can confer on the oxygen
delignification process some of the characteristics of a fortified exttaction stage.
7.2 Oxygen
Oxygen-reinforced
alkaline extraction
decreases the kappa number of the pulp
compared with a non-oxidative exttaction
without affecting pulp viscosity to any significant degree (Fig. 15) (43). This lack of
reaction with the carbohydrates in the pulp
is also confirmed by evaluation of pulp
strength (43). Most frequently, the decreased kappa number is used to decrease
the amount of the more expensive oxidant,
chlorine dioxide, used in the following stage
(fable 4) (30, 43). Under constant extraction conditions, the magnitude of this kappa
number decrease is determined
by the
amount of oxidation occurring in the previous stage as measured by the incoming
kappa number. Applying chlorine at a low
active chlorine multiple in the first bleaching stage allows a greater benefit to be ob-
tained from the oxygen applied in the exttaction stage than when chlorine dioxide
is applied at a high active chlorine multiple
(44). In some cases, the degree of oxidation of the first stage pulp can be so high,
for example when using ozone, that a negligible benefit is obtained from the application of oxygen (45) .These results show that
not only the stage but the sequence needs
to be optimized to ensure the maximum
benefit from the use of the lowest cost
chemical. In general, both softwood and
hardwood furnishes and pulps produced by
the kraft and sulfite processes all respond
well to the application of oxygen in the
extraction stage (fable 5) (43).
Thekappanumberdecreaseob~Nedin
oxygen-reinforced alkaline extraction does
not accurately represent a corresponding
Ttlble4. Chlorltle IIlonu Sllvltlgs 'Itrough usltlg
oxygetl- or JH!t"fJXlU-mtiforcetl "lI"dltle
extrtlctton (30).
Stage
(EO)
(EP)
Cost of Oxidant,
$ per metric ton of pulp
5 kg 02 in E1
saves
0.75
3 kg C102 in D.
3.00
1.5 kg Hz02 in E2
saves
3 kg CI02 in D.
1.65
3.00
Net saving
2.25
Net saving
1.35

Tllbk 5. ~""""fUIIIIber~by"
.pp11allUmof.. ~-rri1Ifon:l
IIne~(43).
Pulp
Type
"",..
Post
Post
&kappa (EO}kappa
1st
Stage
Softwood
kraft
C90+D10
D7OC30
5.8
4.6
3.4
3.3
Hardwood
kraft
C90+D10
D7OC30
3.4
2.7
2.2
2.1
Softwood
sulfite
C90+DI0
2.6
1.2
Unbleached
Softwood
Hardwood
Softwood
pulps:
kraft; kappa
number,
kraft; kappa
sulfite;
kappa
C stage: 0.22 x kappa

3.0% consistency
33.9
number,
17.7
number,
30.5
number;
20 min at sooC;
E stage: 0.12 x kappa number; 60 min at 60C;

10% consistency
(EO) stage: 60 min at 60C; 10% consistency;
0,
gauge pressure,
0.14 MPa applied for 10 min
decrease in the lignin content of the extracted pulp because the remaining lignin
is more oxidized and therefore consumes
less potassium permanganate in the kappa
number test than a conventionally extracted
pulp (Fig. 16) (9). However, kappa number is still the critical indicator of the chlo-
307
cine dioxide consumption required in the

ensuing D stage to achieve a particular
brightness (Fig. 17) (12).The reactions occurring with oxygen in this stage have not
been studied, but it is likely that phenolic
structures liberated in the extraction process are the point of attack for the oxygen
as discussed in earlier chapters.
Pressure and time-at-pressure distinguish
the oxygen-reinforced
alkaline extraction
stage from oxygen delignification.The minimum conditions necessary to obtain most
of the kappa number decrease are an oxygen pressure of O.14 MPa held for 3 minutes (Fig. 18). For mills equipped with an
upflow extraction tower, these conditions
can be easily achieved; the head of pulp in
the tower provides the necessary pressure
over the requisite retention time. However,
because the majority of mills in North
America use downflow towers, an upflow
pre-retention tube is required to provide the
necessary pressure and time.
When pressurization is provided by the
head of pulp in the tower, the pressure decreases as the pulp progresses through the
tower. If the starting gauge pressure at the
bottom of the tower is 0.14 MPa and attnospheric at the top, then 10 minutes' retention is required to obtain the same results
308
Pulp Bleaching
-Principles
and Practice
50
(C90+D10)EDED
[J
cD
"C
'x
(D3OC70)EDED
<>
(D5OCSO)EDED
40
Q)
(D7OC30)modEDED
.~
(D70C30)convEDED
.
.
30
~~
(..)E
(D9OC10)modEDED
--
"C
Q)
rn
c:
o
U
(D9OC10)convEDED
20
10
2
4
567
8
E-stage kappa number
Q) 6
.D
E
:J
c: 5
as
a.
a.
as 4
27.0
"C
Q)
as
10
Pressure02
I-....~ PSIG MPa
10 0.07
~(211.8)
~2b 20
0.14
~50 0.50
(27.2)
~UJ
o 1 2 3 4 5 6 7 B 9 10
60
02 treatment time from beginning of stage, min
2
0.4
0.6
0.8
1.2
1.4
1.6
1.8
Total lignin. % on o.d. pulp

Fig. 16. RellltWnsbtp betwetm aJ1/Hl..mber
.forced ,"aline extr'tlcUmu (9).
KlIIstm lipi.
"'"'
t:tmIe8i i. CMI_Uo1uIl
~-ret..
"'"'
that are obtained when a gauge pressure of

0.14 MPa is applied constantly over 3 minutes (Fig. 19) (46).This time can be shortened significantly by increasing the pressure
at the bottom of the tower; for example, at
0.35 MPa, a retention time of only S minutes is required. In some installations, however, the retention time may be too short
to provide the necessary pressure and time-
at-pressure conditions. In these installations

a flow restriction valve may be placed a~
the outlet of the upflow tower to ensure
that the minimum required pressure exists
at the top of the tower.
Pressure application is the first factor in
ensuring good oxygen-reinforced
alkaline
extraction. The second is good mixing.
Oxygen is a sparingly soluble gas and must
309
co
a.. 0.4
~cD
....
::J
en 0.3
en
Q)
"..................
\',
....
c..
Q)
0) 0.2
::J
CO
0)
c:
Q) 0.1
0)
>.
x
0
\ \ .".
\'
g-J.................
. :
I
\:
\:
oftbe
..
~:
\~~,
:'
\
Kappa number
shown in circles.
..................
' , ........
o
Fig. If). ComptIrlstm
............
..........
.\
I
I
\:
':\
",
..
..........
....
.........
"\
.........
........
............
2
3
4
5
6
7
8
9
Oxygen treatment time, min
effect ofgrw4lullly
Mctwsmg
the tMYfM Jna$8refrom
10
0.35 MP. tMYfM Jna$8re
to .tmospberk ad tbe effect of tlUd"tldttUrg. wutllflt Jna$8re of 0.14 MP. lit VlJrWusm,refl
Ire"",,",t times. Tbe reSJIltiltg1uIJIPII bers lire cIrr:W Tbe Iiotmlilfle reJIrWefItstbe expected
to tbllt obtllifled Iry~g
. wutll"t
Ire"",,",t (5 ",.tes) rel/fdred to glfJII. result t:OIIIJNII'fIble
Jna$8re of 0.14MP. _ 3 ",I""tes (46).
be well distributed throughout the pulp
mass for uniform reaction to occur. The
advent of high-intensity mixers allowed the
successful application of (EO) (36). Other
less expensive mixer designs (for example,
static mixers) may be used, (47, 48) but
the decreased rate of reaction of pulp with
oxygen because of poorer gas distribution
must be compensated for by using higher
pressure and extending the reaction time
at pressure. This type of installation represents an option for those mills using upflow
extraction towers.
Most of the operating conditions in oxygen-reinforced alkaline extraction are similar to those of conventional extraction.Time
and temperature are generally in the same
ranges. The kinetic models described earlier in Equations [1] to [3] are still relevant
in the context of oxygen-reinforced alkaline
extraction.
It is perhaps significant that
there is a correspondence between the time
required for pressurization in (EO) and the
time span of the rapid phase described in
the model. This correlation suppons the
conclusion that the rapid phase is the period during extraction when most of the
chemical reactions occur with the pulp.
-Principles
and Practice
7.3 Peroxide
.............
Pulp Bleaching
trained in the pulp, pulp washing becomes

more difficult. Ensuring full reaction without excess gas entrainment may be one of
the benefits of good oxygen-addition control.
c~.....
\~\ "\,
\ \
310
One operating
condition
that does
change is the sodium hydroxide charge
which, for oxygen-reinforced
extraction,
must be 0.5% on pulp higher than in conventional extraction if the stage is controlled
to the same final pH (9). The reason for
this increase, as stated earlier, is the increased formation of sodium carbonate occurring during oxygen-reinforced
alkaline
extraction.
The oxygen charge applied is commonly
0.5% on pulp, most of which is consumed.
Generally, the amount required is determined by the point at which no further
benefit is obtained in terms of kappa number reduction or cWorine dioxide savings.
Some analyses of the residual gases have
been made (49); however, mills do not routinely measure the oxygen content of the
off gases. For the limited amount of oxygen added, it is judged not worthwhile to
control the oxygen addition more closely.
Although some carbon monoxide and hydrocarbons are produced in oxygen-reinforced alkaline extraction
stages, the
concentrations
are not high enough to cre.
ate an explosion or fire hazard (50).
One negative aspect of oxygen-alkali extraction is that when residual gas is en-
Peroxide use in the extraction stages of

multi-stage bleaching has a long history. In
the past, peroxide cost has generally militated against its widespread use, but this is
no longer true. In Scandinavia, even when
(EO) technology was available, peroxide
instead of oxygen was the preferred chemical for use in the first extraction stage, partly
because of the capital costs associated with
implementing oxygen-reinforced
alkaline
extraction (51). Today, with the need to
minimize the use of cWorine-containing
oxidants in the bleaching sequence, both
oxygen and peroxide are used extensively
in the first extraction stage. Because peroxide bleaching is dealt with extensively in
Chap. V 1, only peroxide addition to oxygen-reinforced
alkaline extraction is described here.
Peroxide addition to the first extraction
stage can be used to decrease the amount
of cWorine-containing oxidant in the first
bleaching stage. When concerns about
cWorinated dioxins and furans arose, and
in the absence of the necessary cWorine dioxide generator capacity to provide for the
alternative strategy of increasing the cWorine dioxide substitution, this approach allowed some mills to promptly decrease the
fIrst-stage cWorine multiple (52). Alternatively, by applying peroxide in either or both
of the extraction stages, chlorine dioxide
could be made available to increase the
degree of cWorine dioxide substitution in
the first bleaching stage (53).
As in oxygen-reinforced alkaIine extraction, the effect of the oxidant, in this case
peroxide or both peroxide and oxygen, is
superimposed on the effect of the alkali on
the pulp. Figure 20 shows the change occurring in the extracted kappa number
when different oxidants or combination of
oxidants are applied to a softwood kraft
pulp (54). There is much debate, and no
definitive answer,about how to achieve the
maximum bleaching effect from the peroxide addition, particularly when oxygen is
also being applied to the extraction step.
One configuration commonly being used is
shown in Fig. 21 (39). However, it is difficult to obtain the full value from the peroxide in an (EOP) stage. If the full value of
the oxygen is obtained,llitrate-peroxide
reactions tend to dominate. If, on the other
hand, the full value of the peroxide is ob-
0.26
~ 0.24
c..
:;:::::
'3 0.22
~
.;::
o
0.2
:c
0.18
o
~ 0.16
13
<C 0.14
0.12
2
2.5
3.5
4.5
CE kappa number
FIg. 10. XiIpJM".mber
bludmtg of. so~
1Id1lerJeII1rylIIidI"g combl""tIorrs of oxIdimts to tbe exhYlctWrr st.ge ,,, tbe

1mIft /1fIlp (54).
311
312

the following chlorine dioxide stage (58):
8. Second extraction stage

8.1 Kinetics
Caustic (NaOH)
Retention
tube
(EOP)
bleach
tower
Oxygen
Pulp to
E-stage
washer
Thickstock
pump
= kE2.[HO'Jo.t.to.3.e.f/RT
k02
The same principles used to assess the

first extraction stage also apply to the second extraction stage (58). However, the
second extraction stage is not a delignifying
stage, instead it activates the pulp to further oxidation and, in particular, allows the
amount of oxidant in the following stage to
be decreased (Fig. 23). The effect of the
extraction stage has been described in terms
of how it affects the rate constant <kr,;) of
[4]
where
~=
the E"stage
reaction
rate constant
= the Eistage reaction time in minutes
= the
E2'stage reaction
= the
apparent
activation
temperature
energy
stage reaction
in "K
of the E 2
= 15 k]lmot.
95
Hydrogen peroxide
90
Fig. 21. 'J'ypIaI1lrulustrlill COIIflprtltltmftn' tbe II/IPlktltWrtof~

exlrtldttm sttlge (3').
ill... ~-retnfim:e4
.IWiIIe
~0
iii
(/)
85
Q)
c::
62
..c:
C)
.;::
D
#.
c::
o
60
'U
as
'U
58 ~
~Qj 3.6
75
~70
Q)
~...Q)
56
65
0.05
!jto
rJ)
rJ)
.c
80
54
3.2
c::
as
a.
a.
as
~
2.8
0.1
0.2
0.3
0.4
0.5
EC)
52
15
50
tion stage (55) or in high density stot1ge

(56) w-here reactions with pulp instead of
with filtrate are maximized.
The effect of peroxide charge on the CE
0.2
0.25
dioxide, mmol/g
0.3
e%trtu:tkm st.ge on tbe chlorine dioxUle demlmd In tbe flul

hleaching (0 or OED) of. softwood Imlft pulp prebleacbetl using.n O(C+D)Esequence (58).
91
0.6
E-stage
NaOH,
mmoVL
~1
90
0
89
iii
(/)
Peroxide, % on o.d. pulp
tained, the lower cost chemical, oxygen, is

not used effectively. For these reasons, before the environmental constraints created
the need to maximize bleaching with
oxygen and peroxide, peroxide was more
frequently applied during the second extrac-
0.15
chlorine
Fig.23. Effectof 11ftIntn'lrledillle s-u
o(/)
brightness In.n ~-retnfim:e4

Fig. 22. Effect of~
cbIIrge on C(EOP)1uIppIImnnber
"""
eztrllCtKnt stllge (3').
0.1
Consumed
IIlU"ne
kappa number and pulp brightness after

extraction is shown in Fig. 22 (39).A good
relationship exists between the kappa number of the pulp after extraction whether
peroxide, oxygen, or neither is used and
the amount of chlorine dioxide required in
the foU()wing stage (Fig.l7) (11).TlJj~ rrlJ'
tionship allows comparative costs of different bleaching strategies to be determined
(Table 4) (30, 57).
Q)
c:: 88
..c:
.~ 87
D
0 86
en
85
84
0.02
Fig. 24. Effect of .UIIIlI
0.025
0.03
0.035
0.04
Consumed chlorine dioxide, mmol/g
cmu:nJtrtltItm
In tbe second extrtlctw..
chlorinedtoxftleCOlJSllmptton
(58).
0.045
st.ge on tbe D 1-st.ge flul
brightness
.nd
Chapter
IV 4: (Oxidative)
Alkaline Extraction
313
314
Pulp Bleaching
92
and Practice
93
92
~90
~0
iii
II)
Q)
c: 88
iii
II)
Q)
E-stage
c:
time,min
sC)
=.
.;::
.D
0
-Principles
sC)
=.
.120
86
-;::
.D
0
. 60
~o 30
o 0
84
20
40
60
D-stage
Fig. 25. Effect of t'I'J'-"-
tI_
I" tile ~
~tIoft
80
retention
100
120
140
SI4ge OftDz-Sl4geft",,, brlgl1lJ1ess(58).
the reaction time in the O2 stage, but the

asymptotic limit, or brightness threshold,
is lowered by shortening the E2-stage reaction time.
8.2 Chemical concentration
8.4 Temperature
(charge
Lowering the temperature in the E2stage

has an effect similar to that produced by
shortening
the reaction time (Fig. 26).
Lower D,stage brightness can be overcome
to some degree by extending the D,stage
reaction time but, again, the asymptotic
limit, or brightness threshold, is lowered by
decreasing the E2-5tage reaction temperature.
The shorter the extraction time in the Ez

stage, the greater the demand made on the
8.5 Rapid extraction

Irrespective of these principles, mills can
arrive at a position of using two chlorine
dioxide stages without an intermediate extraction stage. For example, a mill needing
to eliminate the use of sodium hypochlorite in a CEHD sequence for environmental
reasons may replace the H stage with a 0
stage. For these mills, the benefit of an
intermediate extraction can be partially obtained by using a rapid extraction (neutralization) step (59, 60).The rapid extraction
D stage (Fig. 25). As the extraction time is

shortened, the brightness obtained in a
given time in the O2 stage is lowered. Some
compensation can be made by increasing
can be done by adding alkali to the bottom

of the D.-stage tower (On)' The disadvantages of such an approach are the need to
neutralize the acidity in the filtrate from the
8.3 Time
89
88
86
0
20
40
time, min
This kinetic equation shows that the caustic (NaOH) concentration, time, and temperature in the E2stage each affect the rate
of bleaching achieved in the O2 stage.
and consistency)
Figure 24 (58) shows that the alkali concentration used in the E2 stage determines
the brightness obtainable in the O2 stage
and determines the amount of chlorine dioxide required to provide this brightness.
In the extreme case, if no alkali is used in
the second extraction stage, the final brightness will be significantly lower (two points
in this example) than when a proper alkali
charge is used.
E,stage alkali charge is controlled by pH.
The charge is much lower than that of the
first extraction stage, typically 0.5% NaOH
on pulp (30), because of the decreased
amount of alkali-consuming
material remaining in the pulp after the previous oxidation stage.
90
~87
82
0
91
80
60
D-stage
Fig. 26. Effect of~
1ft tile ~
8.6 Added oxidants

As is often done in the first extraction
stage, oxidants also may be added in the
second extraction stage. Generally, the addition of oxygen is not considered worthwhile because of the lack of return on the
capital investment; however, peroxide addition can be effective (62).The peroxideto-chlorine dioxide substitution ratio in this
case is more favorable than that encountered in the first extraction because peroxide reacts with pulp instead of with the
filtrate (Table 4).
9. Other alkalies
hydroxide
120
140
emwetloft sItIge Oft tile Dz-sI4ge jltuIl brlgl1lJ1ess (58).
D. stage and the potential for hypochlorite

formation which can cause loss of pulp viscosity. However, well-controlled operation
to low chemical residual before alkali addition can eliminate the latter problem and
higher brightness at lower cost can be
achieved than in the original CEDD process.
Applying On also can be useful when washer
breakdowns occur and it becomes necessary to bypass a stage (61).
9.1 Chlorine-to-sodium
100
time, min
ratio
Most alkaline chemicals have been evaluated for use in bleaching (63), but sodium
hydroxide is the alkali of choice because of
low cost, high solution concentration, high
water solubility, and the solubility of the

resulting sodium salts.
One of the challenges, however, that may
arise through increased concern about chlorine chemicals and particularly chlorine itself, is the increase in the cost of sodium
hydroxide (64-66). Chlorine and sodium
hydroxide are produced in an electrochemical cell in the weight ratio of 1.1 units of
sodium hydroxide to 1 unit of chlorine. A
mill can use these chemicals most economically when the consumption balance is
in this ratio. However, with increasing chlorine dioxide substitution levels or elimination of all chlorine, "out-of-balance" sodium
hydroxide is required. Several strategies
have been proposed to address this concern.
9.2
On-site sodium hydroxide

generation
The first approach involves the development of alternative
sodium hydroxide
sources. Induded in this group is the generation of caustic from: 1) sodium carbonate by a conventional
recausticization
process (67); 2) sodium sulfide by reaction
with copper oxide in theAtby process (68,
69); and 3) any salt by electrochemical salt
splitting (70, 71), a process which is incorporated into the Sterling R9 and R12 chlorine dioxide generating systems (72, 73).

c: 20
;;0
--
Sodium carbonate
-+-
I!!
X 15
...
CD
316
Sodium silicate
Chemical in
E-Stage
CE
Kappa No.
NaOH
Na2C03
NaHC03
HP
4.6
7.0
9.1
11.9
WMe liquor
Sodium sulfide
10
Sodium
~Xide
.c
E
~c:
5
as
0.
0.
as
~0
Unbleached
C stage:5.6%
and Practice
c:
0
Alkali addition, % on o.d. pulp

ng. 27. BJfeet of tISItIltllff-t
",,,,,,,. ", t. extrtIetUnl.,.,. 011

t. CEIIIJIIHI-'-
Of50ftrtItHM
X
CD
ImIft
JlJ4IJ1(IuIpJNI tUIIIIber, 32.6) (63).
9.3 Conversion of chlorine to chlorine

dioxide
The second approach involves eliminating the out-of-balance caustic by increasing
the use of chlorine in the generation of chlo-
rine dioxide. In the integrated chlorine dioxide process (74), chlorine is burnt with
hydrogen to produce hydrochloric acid
which is then used as the reducing agent in
the generator.
alkali sources
The third approach is to use an alternative alkali source. Some alkali replacements
that have been considered are sodium silicate (63), sodium sulfide (75),oxidizedand
unoxidized white liquor (76, 77), sodium
carbonate
(78), and calcium hydroxide
(23). The comparative efficiency of these
different alkalies is shown in Fig. 27. None
of these alkali sources is as efficient as s0dium hydroxide on a weight basis but, by
increasing the charge and time and temperature of reaction, sodium carbonate, for example, can be made to give comparable
results (fable 6). There are also concerns
with scaling and reactions with added oxidants with some of these alternative alkali
sources.
9.5 Papricycle process

Another alkali source which can be included in the final category is extraction-
...
CD
1ij
...
CD
Strategy
Increase
time by 2 h
Increase
temp. by 20"C
Capital Cost,
$ million
Operating
Cost', $/ton
0.41 - 0.81
- 4.00
Na.c03
Na-Organics
NaHC03
NaCI
% as NaOH on o.d. pulp

0.96
0.95
0.51
0.46
0.92
0.79
0.74
1.78
1.88
pulp:black
spruce kraft; kappa number, 28.0
02 on o.d. pulp; 45 min at 25C; 3.5% consistency
E stage: 3.1% as NaOH
02468
9.4 Alternative
-Principles
Pulp Bleaching
Calcium hydroxide
(J
CD
...
CD
1ij
315
.c
E
on o.d. pulp
(except
in the last experiment);
10% consistency.
14
~12
10
Na2C03
NaOH
~c:
as
0.
0.
90 min at 70C;
N~C03
NaOH
~4
2.50
'Cost of replacement of hydroxide with carbonate in extraction if carbonate is $180/t,

hydroxide is $380/t, and steam is $7.9/6J
stage filtrate (79-82). Earlier, it was shown
that the E-stage filtrate contains sodium carbonate, which is likely formed by the reaction of labile carboxylic acid structures with
sodium hydroxide. Sodium carbonate, as
shown in Fig. 28, can be used as an extractant but is less efficient than sodium hydroxide. Differences in the amounts of reaction
products arising from the use of different
alkalies are shown in Table 7 (80). Combinations of sodium carbonate and sodium
hydroxide are no more efficient, to a first
approximation, than if the amount of sodium hydroxide used in the mixture were
used alone (Fig. 29). The reason for this is
that sodium bicarbonate and carbon dioxide, which are the reaction products in the
oxidized pulp/sodium carbonate reactions,
react with sodium hydroxide regenerating
sodium carbonate. In a sodium carbonate/
c:
0
2
3
Charge, % on o.d. pulp
16
~14
...
X 12
CD
...
NaOH+Ca(OH)2
CD
1ij 10
...
CD 8
.c
c:
as
0.
0.
NaOH+N~C03
~6
'"NaOH
4
~2
0
Alkali addition, % on o.d. pulp

Pl,. 2'. ~
ejJfdnrey of~
CllrlHnMle (63).
ofllOtll_lty4rtdM wltb CIIlci_ bytlroxUe."" sodl_
317
NaOH Charge,
% on o.d. Pulp
CE
Kappa No.
D,
3.0
2.0
1.0
5.4
6.1
9.0
81.0
76.7
56.5
84.6
Conventional
Recycle
(with no wash)
3.0
2.0
1.0
5.5
5.8
8.4
81.4
76.6
60.7
89.6
87.9
85.5
Recycle
Followed by washing
(Papricycle)
3.0
2.0
1.0
5.1
5.3
5.8
82.2
81.7
79.6
89.9
89.6
88.7
No recycle
pulp:black
ISO Brightness. %
D2
89.5
spruce kraft; kappa number, 27.5
Sewer
C stage: 5.5% CI, on o.d. pulp; 45 min at 25C;"3.5% consistency

Papricycle:5 mL of extraction
effluent' per gram of chlorinated
pulp; 5 min at 60C; 10% consistency
E stage: 90 min at 70C; 10% consistency

D, stage: 1% ao,
and 0.55% NaOH on o.d. pulp; 3 h at 60C; 10% consistency

stage:
1%
NaOH
on o.d. pulp; 1 h at 60C; 10% consistency
E2
D, stage: 0.5% ao,
The extraction
with 3% NaOH

ST-5
Hot water
ST-6
Type of E,
Effluent Recycle
Unbleached
318
on o.d.'pulp; 3 h at 60C; 10% consistency
effluent used
on o.d. pulp.
for recycling
was produced
by extracting
the same chlorinated
pulp
Fig. 30. FIonbeet
'-;
Sewer
of t#le PlIJWkyele pt'of:es$ implemer8ted at w~
Kimtloops mill (
Iv. IlItISber', 1:,
ST,UIIltMdI)(79).
'
exchange with the cooler acid-oxidized

pulp. Costs associated with the process are
for the operation and maintenance
of a
washer and for the alternative neutralization
of effluent which requires a larger addition
of lime mud.
7. Ni, Y, Kubes, G.}., Van Heiningen,A.R.p.,]

Pulp Pap. Set. 16(1):13 (1990).
8. Ni, Y., "A Fundamental
Study of CWorine
Dioxide Bleaching
of Kraft Pulp," Ph.D
Thesis, McGill University, Montreal, 1992.
9. Berry, R.M. and Fleming,
Sci. 11(6):176 (1985).
sodium hydroxide mixed reaction medium,

there is a set of positive reactions:
Chlorinated pulp + NaOH
NaCI + Na2COj
Na organics +
[5]
Chlorinated pulp + Na2COJ

NaO + NaHCOj
Na organics +
[6]
Chlorinated pulp + NaHCOj

+ NaCI + C02
Na organics
[7]
and a set of negative reactions:

NaHCOj + NaOH
C02 + NaOH
Na2COj + HP
NaHCOj
[8]
[9]
This combination of positive and negative

reactions causes a normal recycle of extraction filtrate onto an acid-oxidized pulp to
be ineffective for decreasing the amount of
sodium hydroxide required. However, a
wash between the addition of the extraction-stage filtrate and the addition of sodium
hydroxide removes any sodium bicarbonate or carbon dioxide and allows use of the
residual alkalinity in the filtrate to reduce
the caustic charge required (fable 8). This
process requires an extra washing step.The
cost depends on whether an extra washer
is available, as is the case in a six-stage sequence where the hypochlorite stage has
been removed, or if a new washer has to
be purchased. One of the simplest process
designs is shown in Fig. 30. In this case
only two pipe lines were added to an existing installation. The process is now being
used with differing degrees of implementation complexity in twelve bleach plants in
Canadian mills. The process can also provide further savings by decreasing
the
amount of chlorine
dioXide
required in the
following stage because organic carryover

is decreased and by decreasing the steam
requirement because of the greater heat
References
1. Larsen, L.H. and Partridge, H. deV., in The
Bleacbtng
of Pulp (R.P. Singh, Ed.) TAPPI
PRESS,Atlanta,
1979, p. 101.
2. Wayman, M., in Tbe Bleacbtng
of Pulp
(WH. Rapson, Ed.)TAPPI PRESS, New York,
1963, p. 67.
3. Berry, R.M. and
scbung 41(3):177
Fleming,
(987).
4. Karter, E.M. and Bobalek,

(11):18820971).
B.I., HolzforE.G., Tappt
54
5. Pugliese
III, S.c. and McDonough,
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18. Polcin,].,
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19. Richtzenhain,
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57:363 (1954).
20. Ranby, B.G. and Immergut,

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21. Richards,
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22. Corbett,WM.
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62:865 (1959).
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24. Singh, R.P. and Atkinson,

E.S., in Tbe
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25. Axegaro, P. Svensk
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"A Numerical Simulation of the First Extraction
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and Rate;
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28. Saltin, G. and Edwards, L.,"Advanced Technologies for Mill Close up: a Model for the
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29.Van Lierop, B., Liebergott, N.,Teodorescu,
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31. Massey, WM., Jr. and Nay, M.]., "Alkaline
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33. Lindholm,
(1992).
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7(2):95 (1992).
35. Kempf, A.W. and
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319
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Nasman, L. E., Tappi ] 67(6):58 (1984).
37. Van Lierop, B., Liebergott,N.,
Faubert,M.,
"ECF Bleaching
with Very Low ClO,
Charges,"
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38. Klein, R.]., Strunk,WG.,Vegega,A.M.,
"Low
Kappa Factor Bleaching
A Low capital
Strategy to achieve EPA Guidelines;
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39. Althouse,E.
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40. Meng,T., Owins,R.,

66(5):38 (1984).
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41. Samuelson, 0., Swedish

Oan.4,1982).
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42. Lachenal, D. and de Choudens, c., "High

Efficiency Oxygen and Peroxide Delignification,"
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R.,
51. Andersson,
L., Hook, J., Basta, J., Wallin,
S., Holtinger, L., "The Use of Hydrogen
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52. Reid, D.W., Billmark, G.G., Sutton,
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53. Robitaille,
89(12):167
M.A.,
(1988).
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54. Carmichael,
] 69(11):90
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(1986).
C,J.,
Can.
E. B., Tappi
55. Rapson, WH., Magued, A., Reeve, D.W,J

Pulp Pap. set. 9( 4):TR95 (1983).
56. Owins, R., Strunk, W G., Meng, T. Y., Pulp
Pap. Can. 86(9):79 (1985).
57. Althouse, E.B.,Anderson, K.L., Houle, L.L.,
Trebilcock,J,W,Jain,
D.K., "Hydrogen Peroxide Addition to an (EO) Stage. (EOP)
Technology:
Part 1; 72nd CPPA Annual
Meeting Proceedings,
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58. Axegaro, P., Jansson, U., Teder, A.,j
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43. van Lierop, B., Liebergott, N., Kubes, G.].,

Tappi] 69(12):75 (1986).
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the Caustic Chlorine Balance in a Bleached
Kraft Pulp Mill; CPPA Pacific and Western Branch Meeting Proceedings,
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44. Berry, R.M. and Fleming, BJ.,)

set. 12(5):152 (1986).
60. Histed,
(1984).
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45. Berry, R.M., Barclay, H., Prins,]., Sacciadis,

G., Skothos, A., Ayala, V., Magnotta,
V.,
Breed, D., Rounsaville,].,
Shackford,
L.,
"Medium
Consistency
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with
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with Laboratory Bleaching; International
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46. van Lierop, B., Liebergott, N., Teodorescu,
G., Kubes, G.].,) Pulp Pap. Sci. 12(5):133
(1986).
47.Ducey,M.J.,Pulp
48. Kuryllowicz,
(1984).
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K., Pulp
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(1984).
37(6):22
49. Cirucci,]. E, "(EO) Optimization

by Vent
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85(6): 114
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(1991).
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] Pulp Pap. Sci. 8(1):TR5 (1982).
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and Pulp Mill Chemical
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Reality - Softwood Bleaching: Chemical
Balances, Costs, and Environmental
Impacts," CPPA Pacific and Western Branch
Montreal, 1990.
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66. Fleming, B.I. ,"Chlorine and Caustic in Pulp

Bleaching:
Future Trends," 2nd World
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Institute, Washington,
D.C, 1990.
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M.-O.,
5(5):65 (1988).
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Pap. Res.] 3(4):191 (1988).
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] Pulp Pap. Sci. 20(2):39 (1994).
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72. Fredette, M.C., "Chlorine Dioxide Generators for Chemical

Balance", Kraft Pulp
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73. Stockburger,
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76(3):99
(1993).
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Proceedings, TAPPI PRESS, Atlanta, p. 167.
75. Richter,
G.A., Tappi 38(3):129
(1955).
76. Rapson, WH., Pulp Pap. Can. 66(5):T295

(1965).
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78. Kress, O. and Davis, R.L., Paper

94(11):34 (1932).
81(1):24
Trade]
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so. Berry, R.M. and Fleming,
Sci. 14(5):121 (1988).
81. Berry, R.M. and Fleming,
43(6):426 (1990).
82. Berry, RM. and Fleming,
Sei. 15(5): 165 (1989).
BJ.,)
Pulp Pap.
B.I., Appita.]
B.I.,)
Pulp Pap.
SEcnON IV:
The Technology of
Chapter 5:
Ozone Delignification
B.
van Uerop
Paprican
A. Skothos
Noranda Technology Centre
N. Uebergott
liebergott &Associates Consulting Inc.
Laval,Quebec
1. Introduction.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 323
2. Fundamental aspects of ozone bleaching. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 323

2.1 Ozone reactions with lignin and cellulose . . . . . . . . . . . . . . . . . . . . . . . . . .. 323
2.2 Expression of ozone effectiveness and selectivity . . . . . . . . . . . . . . . . . . . . . 325
3. Process conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
3.1 Mass transfer of ozone to pulp fiber. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
3.2 Pulp consistency. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
3.3 Effect of pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
3.4 Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
3.5 Additives
3.6 Alkaline extraction after ozone stages
325
326
326
328
329
329
331
4. Role of ozone in a bleaching sequence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 332

4.1 Ozone delignification as a replacement for chlorination . . . . . . . . . . . . . . .. 332
4.2 Placement of ozone in a bleaching sequence . . . . . . . . . . . . . . . . . . . . . . . ., 333
5. Process equipment.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
5.1 High-consistency ozonation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
5.2 MediU1IKonsistency ozonation
5.3 Low-consistency ozonation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
5.4 Materials of construction
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
6.Carryover
336
336
337
338
339
to the ozone stage. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 339
7.t:nvironmentalconsideratlons
310
321
Chapter IV 5: Ozone Delignification
Chapter
IV 5:
Ozone
Delignification
1. Introduction
Ozone is a powerful oxidizing agent
which reacts readily with most organic
materials, including lignocelluloses. Its oxidizing potential (+2.07 electron volts) is
exceeded by that of only a few compounds,
among them fluorine, atomic oxygen, and
perhydroxyl radicals (1). Ozone is used in
commercial oxidation processes to bleach
textiles, waxes, and starches, and to disinfect air and water (1). Although ozone itself is highly reactive, its application)s
restricted because it is generated in low
concentrations
diluted with a carrier gas,
usually oxygen or, less commonly, air. The
reactivity of ozone, therefore, is not only
defined by its own properties but also by
those of the carrier gas: The main impediment in ozone utilization is its low solubility in water (0.98 g of Oil of water at room
temperature
and atmospheric
pressure).
This limits its reactivity in aqueous systems
where ozone must transfer from the gas
phase into water to react. The mass transfer of ozone into the liquid phase, and hence
to the reactive site, can be improved by increasing the concentration of ozone in the
carrier gas and by compressing the gas mixture.The early generators produced only 4%
ozone by weight in an oxygen-ozone mixture, but generators are now being designed
to produce concentrations
of 12-14% by
weight (2, 3). Although ozone generators
are limited to operating pressures of about
2 atm, auxiliary compressors can achieve
10 atm.
Ozone is toxic in small amounts, but its
odor can be detected at only 0.01-0.015
ppm. The accepted maximum allowable
concentration
for a daily 8-hour exposure
is 0.1 ppm (4).
A patent tracing the application of ozone
in the bleaching of fibrous substances used
to make paper was issued in 1889 (5); the
process conditions best suited for ozone
323
bleaching of chemical pulps were identified

by Brabender et aI. in 1949 (6). Considerable research during the 1960s and 19705
dealt with the bleaching capabilities of
ozone, but commercial application was delayed because of poorer pulp quality and
higher production costs than were being
obtained with existing chlorine-based technology (7-JO).
Interest in ozone in the 19905 as a replacement for chlorine in pulp bleaching
has been accelerated by the progression
toward minimizing discharges of chlorinated compounds and by market demands
forTCF pulps. As a result, ozone bleaching
has evolved from pilot plant operations (2,
11-16) to commercial installations (15, 1720) which numbered 13 in 1995 (3).
Ozone is less selective toward lignin than
are chlorine and chlorine dioxide and low
charges are required to prevent strength
loss. Unwanted reactions with cellulose
leading to a deterioration in pulp quality
occur when large doses are applied (21-27).
A highly selective ozone treatment remains
elusive despite the intensive efforts directed
toward elucidating
the mechanisms
of
ozone and carbohydrate reactions and the
conditions required to minimize these reactions. A number of references describe
the mechanisms of the reactions of ozone
with pulp and define the best conditions
for ozone bleaching systems (7-10, 12, 26).
This chapter describes ozone-pulp reactions, process conditions, the role of ozone
in a bleaching sequence, and ozone bleaching equipment. A description of ozone-lignin and ozone-cellulose reactions is found
in Chap. ill 3.
2. Fundamental aspects of
ozone bleaching
2.1 Ozone reactions with lignin and
cellulose
The strongly electrophilic character of
ozone promotes its reaction with functional
groups in the lignin remaining after pulping
and other deligniflcation
processes (see
Chap. ill 3). Aliphatic double bonds conjugated to the aromatic rings in stilbene, styrene, and enol ether structures react with
324
. Carboxylicacid
. Total hydroxyl group
o Phenolic hydroxyl group
. Methyl ester
o
Fig.1. F8fI(;tiouigrtJfIp~
30
60
Time of ozone treatment,
",/nwft IIpl" tlftn _
ozone to form epoxides or ozonides which,

on further reaction, form carbonyl groups
and hydrogen peroxide
(28). Another
mode of ozone reaction is insertion of an
oxygen atom into carbon-hydrogen bonds
in alcohol-, aldehyde-, and ether-type structures, resulting in fragmentation of the residual lignin. Studies with lignin model
compounds show that ozone reacts with
the aromatic rings in lignin to form muconic
acid derivatives and other compounds containing carboxylic acid groups (29). The
formation of various functional groups in
lignin during the course of an ozone treatment is indicative of the structural changes
occurring in the lignin macromolecule.
Most of the phenolic groups in lignin are
oxidized and a large number of carboxylic
acid groups are introduced especially at the
beginning of the reaction, forming a hydrophilic polymer that is soluble in water under neutral conditions (Fig. 1) (29). In fact,
ozone appears to be more efficient than
chlorine dioxide, hydrogen peroxide and
dimethyldioxirane
in inducing the formation of carboxylic acids and eliminating
condensed phenolic structures in solventextracted residual kraft lignin (30).
In pulp, the potential for fragmentation
and solubilization of lignin by these reactions with ozone is thought to exceed that
of the other agents currently used in pulp
90
min
tretlIrMrII
titJIll7 (29).
bleaching (31). Ozone itself is approximately 1<f' times more reactive toward lignin than toward carbohydrates (32), but the
by-products from these reactions react more
readily with carbohydrates
(33-35). Two
such intermediates are hydroxyl (HO.) and
perhydroxyl (HOO.) radicals formed by direct decomposition
of ozone in water or
indirectly by the reaction of ozone with an
organic substrate
(26, 32, 36-39). The
strongly electrophilic hydroxyl radical, in
particular, has been shown in model compound studies to attack lignin structures
only 5-6 times faster than carbohydrate
structures (35). The susceptibility of carbohydrates to react with ozone-reaction byproducts
restricts
the de lignification
capabilities of ozone in a pulp bleaching
process.
Most of these studies, as with others
aimed at gaining an understanding
of the
chemistry underlying
the ozonation
of
wood pulps, were performed on model
compounds instead of on pulp. Linking
these findings with ozone-pulp reactions
where the pulp substrate is highly variable,
presents contradictions. Because of the vigorous reaction of ozone and lignin, and because of the slightly greater reactivity of the
hydroxyl radical with lignin than with carbohydrates, it can be speculated that highlignin pulps are less likely to sustain a

viscosity loss than are low-lignin pulps (40).
Carbohydrates appear to be vulnerable to
attack during ozone treatment regardless of
the amount oflignin in a chemical pulp (4144). More selective lignin removal takes
place when an oxygen stage precedes the
ozone stage (41, 43, 45, 46).
Carbohydrate degradation results from
the fonnation of functional groups such as
carbonyl and carboxyl structures (45).The
reaction of carbohydrates with the hydroxyl
radical involves the removal of carbonbound hydrogen atoms, resulting in the formation of hydroxyalkyl radicals which are
then converted after reaction with oxygen
to the corresponding
carbonyl structures
(35) .The carbonyl groups produced on the
polysaccharide chain in a highly oxidizing
environment under acidic conditions later
induce chain cleavage when the polysaccharide is exposed to an alkaline environment
such as is present in alkaline extraction and
peroxide stages and in the cuene viscosity
test (35, 40, 45). Reduction of ozonated
pulp with a strong reducing agent such as
sodium borohydride converts the aIkaIi-sensitive carbonyl groups to alkali-stable hydroxyl
groups
thus preventing
the
alkali-induced chaIn cleavage (47, 48). Although sodium borohydride treatment of
pulp prevents viscosity loss, the amount
required (up to 2% on pulp) does not make
it a cost-effective option in a commercial
operation (35, 44, 47).
Another approach to prevent the hydroxyl radical-carbohydrate
reactions is to
use radical scavengers such as methanol and
acetic acid to destroy the hydroxyl radicals
as they are fonned.This is discussed in Section 3.6.
2.2 Expression of ozone effectiveness

and selectivity
The response of pulp to an ozone treatment is characterized by the amount of lignin removal (as measured by the kappa
number), and carbohydrate degradation (as
measured by pulp strength or, less desirably
but more conveniently, by viscosity). These
two parameters are critical in detennining
if the amount of ozone required to remove
325
lignin will compromise pulp quality.

Because ozone reactivity is influenced by
many external treatment conditions, it is
useful to express kappa number and viscosity values in relation to each other to simplify comparisons.
The two terms used to express the response of pulp to ozone are the effectiveness of ozone in delignification
and its
selectivity. The effectiveness is measured
as the kappa number decrease per unit of
ozone consumed which is an indicator of
lignin removal; selectivity is measured as the
kappa number decrease per unit of viscosity decrease where viscosity is an indicator
of carbohydrate degradation (26, 49-51).
The reactivity of ozone, expressed as the
amount of ozone consumed as a function
of the ozone applied, is dependent on the
design of the ozone-pulp mixer. The effectiveness, reactivity, and selectivity of ozonepulp treatments
at varying consistency
levels are shown in Table 1.
A drawback of the viscosity test as a selectivity rating is that the correlation between
pulp viscosity
and strength
properties of ozone-treated pulps differs
from that of chIorine-treated pulps. Depending on the reaction conditions and the treatment history of the pulp, ozone-treated
pulps can have much lower viscosity values than pulps bleached with chlorinebased sequences
to the same strength.
Therefore, the viscosity at which strength
deterioration occurs must be assessed for
each pulp and each set of operating conditions.
3. Process conditions
In ozone delignification, the main process variables that influence the ozone-pulp
reactions, pulp properties, and commercial
viability are pulp consistency, ozone charge,
pH, time, temperature, chemical additives,
effect of metal ions, carryover of residual
dissolved organic matter to the ozone stage,
and pulp treatment before an ozone stage.
It is crucial to identify the conditions that
induce rapid and efficient transfer of ozone
to the appropriate fiber constituents and
thereby enhance ozone-lignin reactions in
326
Pulp Bleaching
-Principles
Ttlble 1. EJfti_S$,
selecti"'ty
pine Inwft Jnllp' (49).
and Practice
tItUl reaetivlty
0lozone
I"
tbe blHcbtng
01 tm oxygn-dellgnlftetl
Pro.Perties after ZE
Z-stage
Con-
sistency (%)
3
(% consumed)
Ozonation
Yield
(%)
Kappa
No. (K)
Viscosity(V)
(mPa.s)
rvul14M
re&POnse
Reactivity" Effectiveness Selectivity

(%)
(dKlkg OJ (dKldV)
89
1.8
0.74
88
1.4
0.69
30
0.35
0.5
98.9
98.3
'5.5
4.5
13.3
11.2
0.29
0.49
0.85
98.5
97.8
97.8
6.3
3.8
2.4
13.6
11.4
10.4
59
55
57
1.9
1.6
1.1
0.67
0.77
0.83
0.25
97.0
7.0
16.8
0.51
97.7
3.9
13.2
0.73
95.4
1.9
11.6
'Kappa number, 11.7; viscosity, 21.7 mPa.s
b% reactivity
ozone consumed/ozone applied x 100
56
58
55
1.9
1.5
1.3
0.96
0.92
0.97
1.5
pulp, instead of ozone decomposition

actions.
re-
3.1 Mass transfer of ozone to pulp

fiber
The transfer of ozone to the active site in
the fiber takes place by convection in the
gaseous or liquid phase in which moist fibers are dispersed, dissolution in the water
layer surrounding the individual fibers and,
finally, diffusion to the reaction site. A
model of the mass transfer of ozone to the
fiber, first proposed by Osawa and Schuerch
(52) (Fig. 2) has been quantified
by
Bouchard et al. (53). Although ozone is a
strong oxidant and reacts rapidly with the
fiber constituents, its reactivity is inhibited
by its low solubility in water compared with
that of other bleaching agents (54). Ozone,
however, is generated in low concentrations
d,
Ozone
(gas)
Fiber
as an Oxygen/ozone gas mixture and its solubility in water is a function of its partial
pressure (2). The low solubility of ozone
in water and the large gas volume required
in bleaching processes restricts the physical transfer of ozone through the water layer
to the pulp fiber. Increasing the ozone concentration and gas pressure not only improves its solubility but also lowers the
volume of gas charged to the pulp. The
accessibility of the fiber to ozone has been
considered the rate-detennining step in the
ozone-fiber reaction instead of the reaction
between ozone and the fiber itself (52,53,
55).
To achieve effective mass transfer between the gas phase and the liquid phase,
ozone bleaching processes are designed for
high transfer rate. Dispersion of the gas in
the fiber suspension is a key component and
the process design is dictated by the amount
of water in the fiber suspension, that is, pulp
consistency.
Other variables, such as pH
and temperature, figure prominently in facilitating ozone solubility in the water surrounding the fiber and the reaction itself.
3.2 Pulp consistency

Much of the early worlc: on ozone
Mobile
Immobile
Water
Water
Fig.2. MIISShYmIIlM'jn'rJu$S In ozone bt"tlebtng
(5Z).
bleach-
ing focused on low (0.;-3%) and high (3040%) consistency because of limitations in
pulp mixing equipment. In low-consistency
bleaching, vigorous stirring of very dilute

pulp suspensions with conventional mixers facilitates the transport of ozone to the
reaction site by convection across the mobile water layer (d,) and by diffusion across
the immobile water layer (d,) immediately
surrounding the fiber (Fig. 2) (52, 53). At
low consistency, the immobile water layer
is of maximum thickness. Diffusion across
is the rate-determining step because convective transport across d, is faster (52).
As the consistency is increased from low
3.5%) to medium (about 10",,(,),the mobile layer is progressively eliminated leaving only the immobile layer. Water layer
thickness now becomes the rate-determining step. Fluidization of a fiber suspension,
made possible by recent medium-consistency mixing technology, effectually sets the
d,layer in motion (48, 56, 57) and changes
the environment so that ozone can be transported by convection instead of the more
sluggish diffusion process. Therefore, medium-consistency
ozone reactions require
high-intensity mixing systems.
In the high-consistency
(HC) range
(>25%), most of the water is stored within
the fiber and only a thin immobile water
layer envelopes the fiber, thus decreasing
considerably the diffusion path length of
ozone to the fiber. Maximum exposure of
the fiber surface to the ozone-containing gas
phase is achieved by finely shredding or
"fluffing" the pulp to separate fiber aggregates to the greatest extent possible before
contacting the fiber with ozone gas. Ozone
gas can diffuse quickly through the diminished immobile water layer; consequently,
relatively mild agitation is sufficient in HC
ozone bleacWng to facilitate the transport
of ozone to the fiber surface. One drawback: of a hlgh-consistency process is that
the ozone reacts with the surface of the fiber flocs and may be consumed before it
reaches the interior of a large fiber floc (55).
Pulp dispersed as single fibers or small fiber aggregates helps to assure a more even
distribution of ozone within the fibers (18,
52, 57-59).
White et al. (60) have identified four potential rate-determining steps in a hlgh-consistency
process
for contacting
the
327
ozone-containing
bulk gas with reactive
sites in the fiber (See also Chap. VI 4): 1)
transfer of ozone from the bulk gas phase
to the floc surface,2) transfer of ozone from
the floc surface to the fiber surface, 3) transfer of ozone from the fiber surface to the
reaction site, and 4) chemical reaction. The
essential components
of reactor design
which enhance these steps include pulp
consistency approacWng fiber saturation
point to decrease the water surrounding the
fiber, small-sized flocs adequately fluffed for
bleaching uniformity, and efficient pulp
agitation to ensure intimate contact of pulp
with ozone gas (60).
Laboratory comparisons of high- and lowconsistency ozonation indicate that higher
pulp viscosity and strength are obtained at
low consistency
(25, 49), especially as
delignification increases (Fig. 3) (25). The
heterogenous nature of high -consistency reactions may cause localized overexposure
of fibers to ozone and create zones of a low
lignin content, making the carbohydrates
vulnerable to attack:by ozone with the result that pulps of inferior strength are produced. Interest in low consistency
as a
viable commercial technology has dwindled
because of the large volumes of fresh water required (57).
Reports of selectivity differences between medium- and hlgh-consistency systems are less conclusive;
evidence
is
available which shows no change in
strength properties (2, 59,61, 62),greater
selectivity at high consistency (49, 58), or
greater selectivity at medium consistency
(62). The weakness of these comparisons
in selectivity differences may be due to an
effect of the pulp-ozone mixing apparatus
used at the different consistencies instead
of a direct consequence of consistency (2).
Viscosity is often used as a criterion of
selectivity, but its measurement
is influenced by the treatment history of the pulp
and may not necessarily correlate with the
strength of pulp bleached at different consistencies and made by different processes
(2, 49). The tearlbreaking length plots of
data from medium-consistency
pilot plant
ozonation and hlgh-consistency laboratory
328
Pulp Bleaching
-Principles
and Practice
tests show a lack: of strength deterioration

at the 11 km breaking length point even
though the corresponding viscosity varies
(Fig. 4) (2).There is an indication in Berry's
data (2) of limited strength penalty at viscosity values below 12 mPa.s which may
be exacerbated in the following bleaching
stages. Although the ozonation and following extraction stage may not affect pulp
strength at high (19) or medium consistency (63), the strength profile needs to be
evaluated within the context of the entire
totally chlorine-free (rCF) or elemental chlorine-free (ECF) sequence.
3.3 Effect of pH
The most efficient de lignification for
ozone bleaching occurs near pH 2 (Fig. 5).
The pH effect has been established in several studies (8, 9, 12, 26, 46, 58, 64-67),
confirming that lowering pH from neutral
enhances delignification.
The viscosity
shows only a slight improvement (Fig. 5),
or none at all (41, 46, 58) depending on
the treatment before the ozonation. The
combined effect of delignification and viscosity, however, results in an overall selectivity advantage at low pH. ThIs effect has
been demonstrated for hlgh- (8, 12, 41, 46,
24
Kappa
number
4.9
3.0
6.3
3.4
22
~20
C\I
E 18
Z
E 16
ViscOSity
(dm3/kg)
1120
695
735
580
xQ) 14
'C
.5 12
...
as
Q) 10
I8
6
40
Fig. J. ""Ip
JnIl/I (25).
'-,
60
80
100
Tensile
index, Nmlg
strMgtll j1roJIerHa IIfm' /otv- tm4 I1Igb-amslstertcy OZOfNtrHtrrm8I of IIJII- irIIft
22
20
CI
E
Z
E
X
Q)
'C
.5
...
as
Q)
I-
AIIMO
AlterOZE
~18
MC Z. pilot
plant
16
HC Z. laboralOry
14
% 03 Kappa Viscosity.
inZ no. mPa-9
- 16.9 21.6
.0.35
11.3
~0.53 10.1
. 0.30 11.0
.. 1.00 3.4
17.0
15.7
18.4
11.6
12
10
8
6
4
8
Breaking
, strMgt6 j1roJIerHa lifter ,.",_tl'OO4irIIft JnIl/I (2).
Fig. 4. PrIIJI
10
12
14
length, km
IIrrdI1Igb-emrsIstertcy OZOfNtrHtrrm8I of II soft-

58, 64-(6), medium- (58, 67) and low- (41,
46) consistency ozone bleaching conditions.
It has been proposed that in high-consistency ozone bleaching, an acid treatment
and a subsequent
pressing step remove
transition metal ions from pulp thus decreasing ozone decomposition (58) or carbohydrate
degradation
(68, 69). The
presence of metal ions in pulp, particularly
Cu2+ and Fe2+,has been shown to be instrumental in degrading carbohydrates, thereby
compromising pulp quality (68, 69). Improved ozone bleaching at low pH has also
been attributed to low concentration of hydroxide ions which catalyze the decomposition of ozone in water and lead to the
formation
of unselective
hydroxyl and
perhydroxyl radicals (70, 71).
Bouchard et aI. (53) have derived equations to link the ozone-lignin reactions at
low pH to the increased solubility of ozone
in the water layer surrounding the fiber, thus
enhancing the diffusion of ozone through
the immobile water layer and subsequent
delignification. The reaction of ozone with
low- and medium-consistency
pulp is pH
dependent regardless of the acid (sulfuric,
nitric, oxalic or S02 water) used to lower
the pH (53, 65, 72).
3.4 Temperature
Ozone reactions proceed rapidly even at
low temperatures. Generally, the most efficient delignification
and best selectivity
occur at 25-30C for high- (8,58,68) or medium- (73,58) consistency ozonation, al-
~..
~
3.5 Additives
Considerable research effort has been
directed toward identifying an additive or
pulp treatment capable of preventing ozone
from reacting with the carbohydrate fraction of pulp and thus promoting its reaction with lignin. This goal is linked to several
approaches. One is to restrict the physical
availability of ozone to the carbohydrate
fraction (55,76-78). Another approach is
based on suppressing the formation or scavenging activity of secondary reactive species, such as hydroxyl radicals, considered
20
~ 19
~
18
a
0; 6
.c
E
::>
c:
though some results indicate that temperatures as low as OC offer the best selectivity
(55,74,75).
At high temperatures, delignification efficiency decreases (8,58,61,73), mostly as
a result of accelerated ozone decomposition
(45,68). Figure 6 shows that an ozone treatment at 20C offers an advantage of lower
kappa number and less viscosity loss
compared to the treatment at 60C (58),
indicating the desirability of low ozonation
temperatures.
Most bleaching stages are operated at elevated temperatures. Oxygen and peroxide
stages are more effective at temperatures
approaching or even exceeding 100C. Because an ozone stage requires much lower
temperatures, steps must be taken to cool
the pulp before it enters the stage. Therefore, when incorporating an ozone stage in
a bleaching process, the temperature prome of the sequence and the implications
for energy consumption are important considerations.
III
<is
W 8
329
117
e!i
2
4
6
.~
16
III
og
:>
1.5
Ozone, % on O.D. pulp
15
1.5
2
Ozone,
% on O.D. pulp
Fig. 5. Effect of pH 0fI hppa ,,,,,,,her IIU IJiseosiIy ill tbe OZOM treatmerIt of""
rrood "raft pulp (8).
oxygerr-tkUgnified
soft-
330
Pulp Bleaching
-Principles
and Practice
950
5.5
N
o
Z-stage temperature, C
.60
.40
020
4.5
~
0;
.c
c:
Z-stage, C
-20
~:
:3'900
E
N
a
0; 850
4
3.5
1ij
~800
g
c.
..
~ 2.5
:>
750
0.4
0.5
0.6
Ozone consumption
0.7
0.8
in Z, % on O.D. pulp
0.9
2.5
Fig. 6. 1jfft of t~
OfITuIJI/M1I8Ml1er1lllll1Jiseosi1y i" metH_
pi_ AS.4MoxygM-tkllg,dfW
jnIlp (58).
to be responsible for cellulose degradation

(78,79). Elimination of metal ions before
an ozone treatment (68,69,71,80) and increased ozone stability (78) or solubility
(53) in organic solvents and in acids at low
pH are also claimed to improve selectivity.
The improvement in ozone delignification purported to result from the addition
of acetic acid (68,77,78,81, 82),fortnic acid
(78, 82, 83), and oxalic acid (65,78, 82)
remains contradictory, especially considering the excess of acid required to detect an
advantage over sulphuric acid (65,77). In
general, the particular acid used to ensure
efficient delignification is not as important
as maintaining a pH of less than 3 during
ozonation (53).
Some organic additives, specifically
methanol (42,76,83), urea-methanol (76),
and dimethylformamide (76) help to retain
viscosity to varying degrees during an ozone
treatment, but the quantities required exceed practical limitations. For example,
Jacobsen et al. (42) have reported that 50%
replacement
of water by methanol increased the viscosity of a softwood kraft
pulp by only 100 viscosity units (dm3fkg).
Methanol has received attention because of
its reported ability to act as a radical scavenger (84), thereby preventing free radical
species from contacting the carbohydrate
fraction. Ni et aL (37), however, have reported a viscosity increase of only 2-3 mPa.s
units when a kraft pulp acidified to pH 1.8
with sulphuric acid was impregnated with
a 5% methanol solution before ozonation.
3
3.5
Kappa number
etmSistlm9
4
4.5
after OZ
OZOM blMcW"g of II
Magnesium compounds, which are used

effectively as cellulose protectors during
oxygen delignification fail to protect cellulose during ozone delignification (76). The
addition of small amounts of iron and copper salts (37, 69, 76) increases cellulose
degradation slightly. The presence of cobalt (C02+) and iron (pe2+ and Fe3+)enhances
ozone decomposition in sulphuric acid at
pH 3, but considerably less so than in acetic acid at pH 3 (71).
Transition metals must be removed before a peroxide stage, but whether this is
necessary before an ozone stage remains
unclear. Some authors claim that ozonation
at medium consistency
is insensitive to
metal ions (24, 37,85). The improved effect of operating an ozone stage after an
acid wash (80, 81) or after chelation with
EDTA (38) or DTPA (68) has been attributed to the removal of metal ions_ A detailed investigation aimed at isolating the
effects of process variables and metal ions
in pulp is necessary to clarify their effect
on ozonolysis reactions.
A xylanase treatment (I.e., enzyme) designated as X, provides a brightness increase
of 2-4 points when it precedes an ozone
stage in OXZP (86), XQP(ZE)P (24), and
OXZED (87) bleaching sequences.
The
observed lack of viscosity improvement indicates that the preceding xylanase treatment does not suppress
carbohydrate
degradation in the ozone stage.
Combining an ozone and chlorine dioxide in a single stage to form the (DZ) (3,

Tule 2. eo-m.l
/JIu Ittwft pIIlJt' bletriN"
(% on pulp')
Kappa
Number
no prior
treatment
2.25
2.25
1.3
1.3
16.9
4.9
2.7
0.5
3.0
0.7
1045
1120
645
630
695
675
Z-mge
Sequence
0
(CD)(EO)
OZ
OZD
OZE
OZED
332
.. OZ, OZE, om IIfI4 OZEDsequences (Z5).
Viscosity (dm' Ig)
03Applied in
331
NaBH.
reducedd
775
680
675
Tear index (mNm'/g) at
ISO
tensile index eNmllz) of
Brightness
70
90
(%)
35.2
42.4
70.2
88.1
58.8
84.1
14.2
15.5
14.0
13.0
14.8
14.0
10.2
12.1
10.3
9.5
10.5
10.3
'Unbleached kappa number, 34.0; viscosity, 1280 dm'/kg

bZ-stage: 1% consistency, pH 3; E stage, 2% NaOH, 70C, 60 miD; D, 1.0% CIO ,,70C 180 miD , 10%
consistency
'
'All charges are expressed as % on pulp, oven-dry basis
"Pulp reduced with 3% NaBH. for 24 hr at 2% consistency before viscosity test
31, 88-90) or the (ZD) (3, 91) configuration is proving to be an attractive solution
to decrease the chiorine dioxide requirement and, subsequently, AOX formation.
Several mills have incorporated this stage
in their ECF bleaching sequence (3). Dillner
and TibbIing (88) has shown that 6 kg of
ozone applied 5-20 seconds after chiorine
dioxide at pH 4 in a medium-consistency
(DZ) stage of the (DZ)(EOP)D(ED)
sequence replaced 9.7 kg of chlorine dioxide
in the D(EOP)D(ED) sequence.Whether the
(DZ) or (ZD) combination has a synergistic
effect on delignification is unclear.
3.6 Alkaline extraction after ozone

stages
There are conflicting reports about the
merits of extracting a pulp with alkali after
an ozone stage. The general consensus is
that an alkali extraction stage decreases the
kappa number of an ozone-delignified pulp
by about 1.5-5 units and is beneficial to the
bleaching process by reducing the need for
the application of more costly bleaching
chemicals in later oxidizing stages (9, 27,
39, 59, 92-98). The effect of alkali extraction on viscosity and strength is, however,
a subject of controversy. Numerous reports
have provided data showing that the high
alkalinity of the viscosity test contributes
to a viscosity decrease in which the values
are lower than those attributable only to the
ozone stage. TI1is effect is eliminated by

treating ozonated pulp with sodium borohydride as a separate stage (27, 39, 69, 96,
99, 100) or as part ofthe following extraction stage (96). The high charges of borohydride required (as much as 5%) (39),
combined with the long retention time (up
to 24 hours) (92), cast doubt on the commercial viability of this approach.
The response of Z-treated pulp to alkaline and non-alkaline conditions can be
evaluated in ZD and ZED sequences in
which the D stage is conducted at a pH of
less than 4. Comparisons of strength properties after Z, ZE, ZD, and ZED sequences
indicate that the negative viscosity effects
arising from alkaline extraction are not necessarily reflected in the strength properties
of the pulp (25).These results are summarized in Table 2. Unlike after the D stage in
an OZED sequence, a borohydride
treatment preceding a viscosity measurement of
the Z- and the D-stage pulps in an OZD sequence increases the viscosity value. However, pulp strength, as measured by the tear
index (mNm'/g) extrapolated at 90 Nm/g
tensile index, is lower after an OZD sequence than after an OZED sequence, despIte the borohydnde-reduced
vIscosIty
levels of each pulp being the same. Without a borohydride treatment, the viscosity
after OZD is lower than that after OZED. A
Pulp Source
Kappa number
Viscosity, rnPa.s
Sequence
Western Canadian Softwood Kraft
Black Spruce Kraft
33.3 (19.0 after 0)

28.6 (22.3 after 0)
42.0 (29.7 after 0)
OZD
OZED
30.6 (15.1 after 0)

OZP
0.5
1.0
1.0
03, % in Z'
NaOH, % in E'
CIO" % in D'
% in pa
HP"
Kappa number
OZEP
0.5
1.5
2.0
6.8
5.7
6.8
5.8
ISO Brightness, %
DorP
83.4
89.2
76.1
85.1
Viscosity, rnPa.s
ZorZE
DorP
18.9
16.7
17.2
15.4
23.4
21.6
24.8
22.8
ZorZE
-z stage: 40 % consistency;
ambient temperature;
2.5 end pH; E, D and P stages,
E: 60 or 70C, 90 min; P: 10 min, 80C; D stage, 180 min, 70C.
viscosity measurement after a borohydride

treatment therefore may not give a more
accurate indication of the strength profile.
Also, an alkaline treatment does not necessarily cause strength deterioration of ozonetreated pulp.
Because the comparisons in Table 2 are
for pulps having the same kappa number
entering the D stage, the ISO brightness after OZD bleaching (88.1 %) is higher than
that after OZED bleaching (84.1%) as a result of the brightness of the OZ pulp (70.2%)
being higher than that of the OZE pulp
(58.8%). Comparison at a constant kappa
number after the Z stage indicates that, after an OZED sequence, the brightness is
89.2% but only 83.4% after an OZD seq~oce~wle~.G~taandEckert~~
have postulated that, not only does the removal of chromophores by the extraction
stage improve the response to chlorine dioxide, but the alkali also improves the accessibility
and uniformity
of the pulp
following chlorine dioxide treatment. Inclusion of an extraction stage between the
Z and P stages in the OZEP sequence also
improves the brightness compared with
10% consistency;
that obtained in the OZP sequence ~able

3) (9,24).
Elimination of the washing step between
the Z and E stages decreases the kappa numberby 1 point (9, J01);however,additional
alkali is required to achieve a pH adequate
for an extraction stage.
4. Role of ozone in a bleaching

sequence
4.1
Ozone delignification
as a replace-
ment for chlorination

The main role advocated for ozone in a
bleaching sequence is that of a replacement
for chlorine (or chlorine dioxide) as a
delignification agent. A chlorination and
extraction sequence (CE or DE) decreases
the kappa number of a softwood kraft pulp
from 30 to 5 with relative ease, without
adversely
affecting
viscosity
(Fig. 7).
Achieving this level of delignification with
ozone is difficult unless a high charge is used
or the pulp entering the ozone stage has a
low lignin content. To achieve a low lignin
content, some form of delignification process is required, either extended pulping
or oxygen delignification. An illustration of
333
334
Pulp Bleaching
-Principles
and Practice
40
35
(/)
cis
30
a...
;i'0
0
0
(/)
:>
25
PO)
20
15
10
5
0
15
10
20
25
30
35
Kappa number
Fig. 7. ~IecUlJity
of"
bigb-cmrsIsteru:y
oz_
COfIIIeIIIIoul (D+C)E trNIrrIe18I (34).

"
the effect of an ozone treatment applied to

a kraft pulp and its oxygen-de1ignified counterpart is shown in Fig. 8. An ozone charge
of 1.4% on a softwood kraft pulp having a
kappa number of 22.4 entering the Z stage
is required to produce a pUlp of kappa number 10.9 (43). A kappa number of 5 is
achieved in an ozone stage with a 1.2%
ozone application provided the entering
pulp has a kappa number of 15.8. Half of
this ozone charge is required when the pulp
entering the ozone stage is first delignified
to a kappa number of 11.7 in an oxygen
stage. Apart from being a costly approach.
the relatively high ozone doses required to
delignify kraft pulp from a kappa number
Q)
of 30 to as low as 5. which is suitable for a

pulp destined for further bleaching. invariably impair fiber quality. Consequently. it
is preferable
to include
an oxygen
delignification stage before an ozone stage
to minimize the amount of ozone usage required to reach a given kappa number (41,
43.99). Replacement of cWorine or cWorine dioxide in the first bleaching stage
therefore requires both oxygen and ozone
delignification stages.
4.2 Placement of ozone in a bleaching

sequence
Ozone is currently being applied in both
elemental cWorine-free (ECF) and total cWo-
rine-free (fCF) processes (fable 4). Considerable variation in the sequence configuration is apparent.
Medium-consistency
ozone stages are included in 9 out of the 13
installations reported in 1995. An example
of how an ozone stage is integrated into a
TCF bleaching sequence is shown in Fig. 9.
In all commercial sequences, the ozone
stage is placed after an oxygen delignification treatment.
Some sequences are
arranged with an ozone stage even later in
the sequence, following a peroxide stage.
Final brightening is accomplished with peroxide (fCF). cWorine dioxide (ECF), or
both. Chelation is appropriately situated
in the sequence to improve the bleaching
efficiency of the ozone or peroxide stage.
25
25
89.9
90
0>
1;;20
'"
N
iD
(/)
CD 70
Initial
Initial
Krait pulp 22.4
10
c
as
Q.
51- 5
~
77.9
~80
uj
ti 15
~
Krait pulp 22.4
After 0
15.8
After 0
AlterO
0.5
1.5
Ozone charge. % on 0.0. pulp

Fig. 8. Effect of ""ryt..g oz_
oxygen tkUpijle4timt
The implications of where the ozone stage

is positioned within a bleaching sequence
have been studied extensively (10). The
OZ sequence is preferred over ZO because
a given kappa number can be achieved with
less ozone consumption and viscosity loss
(102).
Earlier studies have shown that a multistage ozone treatment requires 20-50"/0 less
ozone than does a single stage, provided a
washing step is placed between the ozone
stages (74,78,103). The improved delignification of the multi-stage system was attributed to the intermediary
removal of
degraded lignin products which, when generated in a single-stage treatment, consume
part of the ozone. A sequence that includes
15.8
11.7
AlterO
0.5
11.7
1.5
c:
.s=
C)
60
'C:
.c
0
P2
Z
P2
P1
P1
P1
50
~40
83.9
P2
Ozone charge, % on 0.0. pulp
pulps witb 111IIIflJitbollt

cIMrge Oft tlH IuIppa ..mnber 111IIIvisrosity of
""'ft
(43).
OQPP
FII. 10. Brlgbtrum of uo.tt-H
OZQPP
Inwft JIIII/Jbktrebetl flJitb oxygen, oz_,
OQPZP
111III
~
(110).
Tok 4. 0z0M
335
blMelml6 ,lIStIIlilltUms'.
Company
Process
Z-Stage
Sequence
Consistency
Ozone
Process
Supplier
Owne
Generator
Manufacturer
LenzingAG
Hwdb sulfite
MCC
(EOP)ZP
Kvaerner
Schmidding
Union Camp
Franklin, VA, USA
Swdb kraft ECF
HCC
OZ(EO)D
Soods
Ozonia
SOdraCell
Monsteras,
Sweden
Swd and hwd

rCF kraft
Lenzing, Austria
MC
OQZP
MC
O(DZ)(EOP)D(EP)D
01JQ(EOP)P
Kvaemer
Ozonia
MC
OQPW
OQPZP
AhlstromKamyr
Ozonia
Kvaemer
rrailigaz
Stora Billerud
Skogha1l,
Sweden
MoDo
Husum,
Sweden
WJSafurest
Pietarsaari,
Swd and hwd
Finland
ECF,rCF kraft
Swd ECF,
rCF kraft
Hwd ECF,
rCF kraft
Metsii-Botnia
Kaskinen,
Swd and hwd

ECF, rCF kraft
Finland
Peterson Seffle
Siiffle, Sweden
Sulfite
Swd and hwd
rCF kraft
Swd and hwd
ECF kraft
Recycled
fiber
Swd kraft
rCF
SCA Ostrand
rinui, Sweden
SAPPI
Ngodwana, SA
Ponderosa~rs
Memphis,
Metsii-Rauma
Rauma, Finland
Consolidated Papers
Wisconsin Rapids
Swd and hwd

rCF kraft
WI,USA
O(ZD)(EO)(ZD)(EP)D
MC'
OQ1JQ(EOp)ZP
O(ZD)(EOP)(ZD)(EP)D
MC
OQZlQ(EOP)ZP
AhlstromKamyr
rrailigaz
Schmidding
AhlstromKamyr
Ozonia
MC
ZEP
Kvaemer
Schmidding
HC
OPZEP
Ozoma
HC
O(W)(EO)D
MC
ZPZP
MC
OZPZP
Soods
AnOOtz
Sunds
AhlstromKamyr
AhlstromKamyr
Schmidding
HC
OZEDD
Sunds
Ozonia
Ozoma
Ozonia
List compiled in 1995
Hwd
= hardwood;
MC = medium
Swd
= softwood
consistency;
HC
= high
consistency
ozone in several positions, for example

OZEZP and OPZEZ, can provide an 88-89
brightness pulp (104), but a final Z stage
causes the bleached pulp to undergo considerable brightness reversion, unlike a pulp
bleached in a sequence consisting of a peroxide stage at the end of the sequence
(102).
Although ozone is commonly applied as
part of an OZEP sequence (8,9,15), moving the Z stage toward the end of the sequence increases brightness and decreases
the ozone requirement
in the bleaching
process (24, 47, 102, 105-109). Earl (105)

and Soteland (111) have reported that insertion of the ozone stage between two peroxide stages "reactivates. the pulp so that
it responds better to the second peroxide
stage. This is illustrated by a comparison of
OQPp, OZQPP, and OQPZP sequences (Fig.
10) which yielded kraft pulps having brightness values of 77.9%, 83.9%, and 89.9%,
respectively (110). An evaluation of the
delignification and brightness progression
within the stages of each sequence indicates
that a peroxide stage de lignifies and espe-
336
Pulp Bleaching
-Principles
and Practice
.. IIrlfImras ofllOfttr004
T"bk 5. KiIJIPII
."""- blMeW", TCF~
lnwft"uJl'
COItpi
III'.'", (1',1!',flll1lll sIIIgtIS(110).
Kappa
number
Brightness,
% OSO)
OZ
OQP
9.9
7.1
46.7
71.1
OQPP
OZQP
OQPZ
OZQPP
OQPZP
5.9
3.6
2.7
77.9
77.5
77.6
2.8
nde
83.9
89.9
Sequence
'Kappa number after 0, 15.0

bZ: 0.5%
10% consistency
OJ'
'Q: EDTA chelation at pH 6
"p: 2.5% H,o, (0.9-1.9% consumed), final pH 11
'nd: not determined
cially bleaches an oxygen-delignified kraft

pulp more extensively than does an ozone
stage (fable 5). The extent of brightening
and lignin removal (as measured by kappa
number) depends on the placement of
ozone and peroxide in a sequence. The
OQPP, OZQP, and OQPZ sequences produce pulps having identical brightness
(77.5-77.9%) but with markedly different
kappa numbers: 5.9 after OQPp, 3.6 after
OZQP, and 2.7 after OQPZ (Table 5).
Malinen et al. (61) have compared OQZPZP
and OQPZP sequences in which a 0.55%
ozone charge was split between the two
ozone stages in the first sequence; in this
instance, the OQPZP sequence produced a
pulp having a slightly superior brightness
and viscosity.
The combination of ozone and cWorine
dioxide sequentially in a single stage as a
(ZD) or (DZ) configuration early or later in
a sequence, is emerging in several mills (])
(fable 4).
5. Process equipment
Process equipment for ozone delignification of pulp is designed to achieve the
desired degree of delignification
and to
maximize selectivity and pulp uniformity
while minimizing ozone usage. The process
of ozone bleaching of pulp comprises several fundamental steps: pulp washing to
minimize carryover of organic material to
the ozone stage, pulp pretreatment for acidi.

fication, ozone-fiber contact and reaction,
separation of residual ozone gas and pulp,
and washing of dissolved organic matter
from the pulp.
In a high- or a medium-consistency
process, the residual gas from the ozone/pulp
reactor is treated to destroy any remaining
ozone. The gas, mainly oxygen, can be recycled back for use in ozone generation or
diverted for use in other parts of the mill.
Residual gas can be recycled back to the
ozone generator only if it is freed of any
contaminants that may be detrimental to the
ozone generator. Residual ozone can be
destroyed thermally or catalytically. Hydrocarbons are removed by catalytic oxidation
to carbon dioxide and, finally, the gas is
dried to achieve the low dew point essential for ozone generation.
Ozone-pulp mixing is the most critical
unit operation
because selectivity
and
complete ozone consumption depend on
ozone-fiber contact. Equipment for ozone
bleaching has been developed and tested
on pilot and commercial scales at high(12,18,19,112), medium- (2,14,16,17,113)
and low- (16,114) consistency levels. The
first commercial ozone stage was installed
at Lenzing AG,Austria, with a medium-consistency Z stage in an (EOP)ZP sequence
(17). In North America, the first ozone
bleaching stage was started up as a highconsistency
process by Union Camp at
Franklin, Virginia, as part of an OZ(EO)D
sequence (18).
ozonation
High-consistency ozone bleaching occurs
in a gas-phase reactor when the pulp fibers
are dispersed
in an ozone/oxygen
gas
phase. Ozone gas can be supplied at low
concentration
and pressure. An example
of a high-consistency ozone bleaching stage
is depicted in Fig. 11.
Pulp preparation
for high-consistency
ozone bleaching consists of thorough washing to reduce the carryover of organic
material into the Z stage,acidification ofthe
pulp to pH 2-3 at low consistency, thickening to the high-consistency range (30-40%),
and fluffing. Lowering the pulp consistency

Feeder
Pulp in
337
338
Pulp Bleaching
- Principles
and Practice
(EO) filtrate
Flutter
Preheater
Chilled
water in
Scrubber
r:
1Liiiiii]}
Pulp to
(EO) stage
;:
Pulp in
at medium
consistency
~
1
Discharger
jlJ-~
L1iJ
Exhaust
Destructor
II
I
19
Pulp out
'-I
Acid
Ozone
reactor
Pump
Pump
Filtrateto!
O-stagewasher
Fig.
11. Flowsbeetfor
!
m
Wgb-coruisteru:y 0_
Z filtrate
mm
bletIebhtg systMrt
m..........
-..
Ozonein
(lhIw.
CimIp
Corp.)
(112).
1
I
Compressor
with dilution water during acidification also

serves to reduce the pulp temperature.
During the pressing step, transition metal
cations are removed together with the effluent. At the press flischarge, the pulp mat
is shredded and fluffed so that the pulp floes
are decreased in size to increase the gassolid interfacial specific surface area.
Two reactor designs have been proposed
to provide good contact between ozone and
pulp fibers: a vertical static bed-type reactor (57) and a horizontal dynamic reactor
(60).A narrow pulp residence time distribution approaching plug flow is required
for uniform treatment of pulp with ozone
to prevent under- or overbleaching which
leads to pulp strength loss.
In the bed-type reactor, ozone is usually
added at the fluffer co-currently with the
pulp flow. The fiber floes are exposed to
the ozone-rich gas phase as they fall to the
bottom of the reactor and form a bed. The
retention time is in the order of minutes.
At the bottom of the vessel the pulp is diluted, neutralized, and pumped to the next
processing step.
The horizontal dynamic reactor improves

the ozone-pulp fiber contact and narrows
the pulp residence time distribution which
leads to improved uniformity (60). A specially designed paddle conveyor reactor disperses the pulp flocs into the gas phase
while conveying the pulp forward. Ozone
is added counter-currently to the pulp flow.
ozonation
Recent developments in ozone generation and in bleach plant equipment design
have made medium-consistency
ozone
delignification a commercial reality (15. 17,
20). Medium-consistency
processes for
ozone bleaching have, so far, predominated
in mill-scale installations because of lower
capital cost and ease of implementation
compared with high-consistency processes
(Table 4).
The main processing steps in mediumconsistency ozone bleaching, as shown in
Fig. 12, are acidification of pulp, transfer of
pulp under pressure to a high-intensity
mixer, compression of ozone gas, mixing
of ozone gas with the pulp suspension, back
Fig. 12. J1IorIJsbeetformdI_-~
0%_ bleJu;W.g syst_ (Abhtrom-~
pressure control at the reactor to maintain

high pressure, separation of the gas from
the pulp, destruction of any residual ozone
gas, and pulp washing. A liquid-ring compressor is used to compress the ozone/oxygen gas to a pressure of 7-12 atm.
Increasing the partial pressure of ozone
in the ozone/oxygen gas mixture, which facilitates treatment of pulp with the required
amount of ozone, is done in two ways: by
compressing the gas to reduce the volume
(48, 115) and by increasing the ozone concentration (2,3). Ozone generators routinely produce ozone at 12% concentration,
decreasing substantially the volume of gas
to be mixed with pulp in ozone bleaching
stages (2, 3).
High-intensity mixers, originally designed
to mix a fluidized suspension of pulp with
oxygen gas, have proved adequate for low
ozone charses in a medium-consistency
stage (2, 15,20,58). These mixers are limited by the amount of gas that can be sufficiently dispersed and mixed effectively with
pulp (62,63). Pilot-scale investigations of
I,".) (116).
mixing efficiency at various phase ratios,

that is, the ratio of gas phase volume to pulp
suspension volume, indicate that mixing
efficiency decreases at a phase ratio greater
than 0.43 (63). At these phase ratios, the
gas bubbles become too large to be dispersed by the mixer into micro-bubbles. As
the ozone concentration
increases, however, more ozone can be charged to the pulp
at a given pressure. Two mixers in series
provide a further improvement in ozone
consumption at a given charge (116).
5.3 Low-consistency
ozonation
Before the development of medium-consistency bleaching technology, the low-consistency approach was investigated (16,
114). At low consistency, the ozone gas
must be dissolved in water before it can
react with the pulp fiber. The low solubility of ozone and the large volumes of water
required to achieve the desired ozone
charge make low-consistency
ozone processes unattractive for commercial implementation.
(3). Generally, the metallurgy

recommended for wetted parts of the fiber line
and ozone gas is 316 stainless steel (3, 117119). Piping connections should be welded
or flanged with fluorocarbon gaskets. Overall, the ozone bleaching process causes less
corrosion problems than does chlorine and
chlorine dioxide bleaching.
The VAl process, which was piloted at

the OZF facilities in Gratkorn,Austria (16),
makes use of a high-concentration
aqueous
ozone solution prepared by stripping ozone
from the oxygen carrier gas by recycling
bleaching filtrate to an absorption column
under high pressure (-7 atm). Using this
approach, wet oxygen from the absorption
column can be dried and recycled back to
the ozone generator. The ozone concentration in the gas is increased by recycling a
portion of the aqueous ozone solution back
to an expansion tank. The ozone gas evolves
from the solution and increases the concentration of the gas entering the absorption
column. The aqueous ozone solution is
added to medium-consistency
pulp under
pressure. Depending on the concentratioQ
of the ozone solution and the desired ozone
charge on pulp, the pulp consistency drops
to 1-5%. Major drawbacks in this process
are carryover organic material in the filtrate
which reacts with the ozone and the increasing temperature of the filtrate recycled
to the absorption column. (With increasing temperature, ozone solubility in the filtrate decreases.)
6. Carryover to the ozone stage

The use of ozone technology in a bleaching sequence offers more possibilities than
does chlorine-based technology for recycling the filtrates rather than discharging
them to a receiving stream. This approach
serves to decrease the water usage and effluent discharge which is the essence of
systems closure. The waste materials in the
filtrates contribute to carryover in the pulp
suspension, which affects the bleaching
process.The sources of waste in the filtrates
are carried forward with the pulp suspension from the preceding stage into the
ozone stage or carried back from the ozone
stage itself and used for tower dilution, consistency adjustment, or washing.
As COD (chemical
oxygen demand)
carryover from an oxygen stage increases,
so does the ozone consumption per unit
decrease in kappa number (63, 120), as indicated in Fig.H. Published results on the
5.4 Materials of construction

Information on the corrosive effect of
ozone gas at high concentrations is limited
1
3.5
c:
o
'5.
EO.as 2.5
~o.
II) as 2
c:.>o:
8~
C')~ 1.5
O"M
.!:!0
~CI
&!.>o:
0.
en
Fig.
13.
EjJeet
10
COD carryover from oxygen stage,

kg! O. D. metric ton of pulp
of CtI1TJOfJ6f"frmrt oxygm
340
TIIbk 6. Effl'"'" f'II'lUy of')(1'J(,

I1rl,6'-lnwft
In", (112).
Effluent Loading
kg/ODTP"
Bleaching Sequence
kg/ADTBP"
Color
BOD
COD
0.25
0.8
0.6
0
15
12
12
6
10
6
6
3
33
17
14
12
1.7
2.4
1.6
0.3
0
53
69
57
35
27
13
16
15
13
12
52
35
34
32
30
Hardwood kraft"
D,oo(EO)DED
O(D50+C~O)DED
0(070 +C~O)DED
OZ(EO)PY
Softwood kraft"
D,oo(EO)DED
0(050 +C~O)DED
0(070 +C~O)DED
OD,oo(EO)DED
OZ(EO)PY
'Air-dry metric ton of bleached
"Oven-dry metric ton of pulp
'Unbleached
"Unbleached
pulp
kappa number, 15.8

kappa number, 30.6
effect of COD carryover on ozone bleaching show a high degree of variability (57).
For example, a COD carryover of 10 kg/ton
of pulp from the oxygen stage was reported
to increase the specific ozone consumption
by 20% (113), 47% (59), and as much as
100",1,(63).
Ozone bleaching is more sensitive to
carryover from an oxygen stage than to
carryback from Z-stage filtrate (59). Carryback from the Z stage has been shown to
improve selectivity (113, 120).
The effect of the carryover to the ozone
stage is less sensitive at high than at medium consistency because six times more
water is removed from the pulp ozonated
at high consistency (18, 59,121).
7. Environmental considerations
0.5
339
sliJge 011 speclJk
corurImJJtIorI
12
(63).
14
An advantage of using an ozone stage in

a sequence is that, contrary to bleaching
with chlorine chemicals, its filtrate can be
recycled to existing chemical recovery processes. However, because many mills are
limited in their recovery capacity, processing this filtrate may not be possible. There-
fore, the properties of effluents from an

ozone bleaching stage need to be characterized.
The properties of ECF and TCF bleaching effluents are summarized in Table 6.
Effluent from the oxygen stage is excluded
because it is sent to the recovery process.
OD1OO(EO)DEDand OZ(EO)PY bleaching of
softwood kraft pulp produce effluents with
similar BOD (biological oxygen demand)
and COD characteristics (122). Bleaching
processes containing an ozone stage generated effluents having 25% less color than
did effluents from ECF sequences. Comparable results have been obtained for a hardwood kraft pulp (122).
The relative merits of ECF and TCF
bleaching on toxicological properties of effluents are inconsistent
(123).
For example, biotests conducted
in the same
laboratory showed that chronic effects of
effluents from TCF bleaching could be
greater than (Flg.14) (J 24) or less that CP
effluents (123). Collectively, the results indicate that effluents from ECF or TCF
bleaching have the potential to cause bio-
Chapter N 5: Ozone Delignification
0
.n
C\I
S:2
100
Stage
C12:C102
80
(C+D)
(DC)
90:10
50:50
0:100
~D
341
60
40
16. Schwarzl,
K., "Pulp Bleaching
Using
Ozone,"Workshop
on Emerging Pulping
and BleachingTechnologies
Proceedings,
North Carolina State University. Raleigh,
NC, 1991.
32. Gierer,}., and Zhang, Y, "The Role of Hydroxyl Radicals in Ozone Bleaching Processes," Seventh International
Symposium
of Wood and Pulping Chemistry
Notes,
CTAPI, Beijing, 1993, p.951.
17. Peter,W, "First Experience With Mill-Scale

Ozone Bleaching," Non-Chlorine
Proceedings,
Miller Freeman, San Francisco, 1993, Session 22.
33. Balousek, P.}., McDonough,T.}.,

McKelvey,
R.D.,Johnson,
D.C., Svensk Papperstidn.
84(9) R49 (1981).
18. Nutt, W.E., Griggs, B.F, Eachus, S.W.,

PikuIin,M.A., TapPiJ 76(3):115 (1993).
20
0
342
19. Gotlieb,
P.M., Nutt, W.E., Miller, S.R.,
Macas,TS., TapPiJ 77(6):117 (1994).
(DC)E
DE
Bleaching
logical effects only at high concentrations

not likely encountered in'receiving waters.
The advances being made with systems closure, however, may make these contradictions inconsequential.
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62. Greenwood,
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R.,
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Miller Freeman, San Francisco, 1992, Session V.
63. Funk, E., Dekourt,
T., Vilpponen,
A.,
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Victoria, Austra1ia, 1993, p.217.
64. Hosokawa,].,
Kimura,Y,]apan
Kobayashi,
T., Kubo, T.,
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65. Lindholm,
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23:307 (1989).
66. Wang,
D.L.K. and
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67. Sreeram, C., Sundaram,V.S.M., Jameel, H.,

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68. Al1ison, R.W, "Effects of Temperature
and
Chemical Pretreatment
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69. Chirat, C. and Lachenal,
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Pulp
Pap.
70. Parthasarathy,
V.R. and Peterson,
R.S.,
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and Transition Metals on the Rate Kinetics of Ozone
Decomposition,"
1990 TAPPI Oxygen
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71. Pan, G., Chen, C., Chang, H., GratzI, ].S.,
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Peter,
W., Pap.
!.,jaPuu
92. Lindholm,
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C.-A.,
(1990).
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Set.
93. Lindholm, C.-A., Nord. Pulp

7(2):95 (1992).
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94. Lindholm,
(1992).
C.-A., Pap. Puu
74(3):224
75. Kobayashi, T., Hosokawa,

K., Kubo, T.,
Matuo,
R., Kimura,
Y., Japan
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31(12):S07 (1977).
95. Lindholm,
(1992).
C.-A., Pap.
74(9):738
76. Kamishima, H., Fujii, T., Akamatsu,

pan Tappt 31(9):664 (1977).
96. Lindholm,
19(3):JI08
!.,ja-
77. Brolin, A, Gierer, J., Zhang, Y, Wood Sci.

Technol. 27:115 (1993).
78. Mbachu,
64(1):67
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(1981).
79. Zhang, Y., Kang, G., Ni, Y, van Heiningen,

A.R.P., "Degradation
of Carbohydrate
Model Compounds
During Ozone Treatment," Workshop
on Lignocellosics
and
Pulp, The Royal Institute of Technology
and STFI, Stockholm,
1994, p.112.
SO. Bergnor, E., Ek, M., Johansson,
E., "The
Role of Metal Ions inTCF-bleaching,'Workshop on Lignocellosics
and Pulp, The
Royal Institute of Technology
and STFI,
Stockholm,
1994, p.284.
81. Lachenal, D. and Bokstrom,
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82. Xu, J., Cogo, E., Briois, L., Duprat,

S.,
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83. Al1ison, R.W, Appita
84. Reitberger,T.and
42:351 (1988).
36(1):42
(1982).
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85. Henricson,
K. and Lindholm,
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C.-A., Pap.
86. Yang, J.L. , Sacon, V.M., Law, S.E., Eriksson,

K.-E., Tappi] 76(7):91 (1993).
87. Brown,]., Cheek, M.C., Jameel, H., Joyce,
T., Tappt] 77(11):105 (1994).
88. Dillner, B. and Tibbling, P. "Use of Ozone
at Medium Consistency for Fully Bleached
Pulp. Process Concept and Effluent Characteristics."
International
Pulp Bleaching
Conference,
Vol. 2, SPCI, Stockholm,
1991, p.59.
89. Tsai, T.Y, U.S. Pat. No. 4,959,124
25, 1990).
(Sept.
C.-A.,
(1993).
J.
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Set.
97. Liebergon,N.,
van Lierop,B.,Garner,B.C.,
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98. Sundin,]., and Hartler, N., Nord. Pulp Pap.
Res.] 9(3):140 (1994).
99. Hartler, N., Granlund,V., Sundin,].,ThbekLindbolm,A., "Ozone Bleaching of Chemical Pulps," International
Pulp Bleaching
Conference
Proceedings,
Vol. 2, SPCI,
Stockholm,
1991, p.75.
100. Kordsachia,
0., Oltmann,
D.L.K., Patt, R., Wochenbl.
7:251 (1990).
E., Wang,
Papierfabr.
101. Liebergott,
N., "Peroxyacids
used in
Bleaching Sequences," 1995 TAPPI Workshop on Emerging Pulping and Bleaching Technologies,
Section 3-1.
102. Lachenal, D. and Nguyen-Thi, N.B., "TCF
Bleaching - Which Sequence to Choose?,"
1993 TAPPI Pulping Conference Proceedings, TAPPI PRESS,Atlanta, p.799.
103. Rothenberg,
Johnsonbaugh,
(1975).
S., Robinson,
D.H.,
D.K., Tappi 58(8):182
104. Phillips, R.B., Kempf,A.W,

Eckert, R.C..
U.S. Pat. No. 4,372,812
(Feb. 8, 1983).
105. Earl, P.E and Nguyen, X.T., "High Brightness Chlorine-free
Bleaching Without
Oxygen Delignification;
International
Non-Ghlorine Bleaching Conference Pr0ceedings, Miller Freeman, San Francisco,
1993, Session 3-2.
106. Dillner, B. and Tibbling,P.,
"Isothermal
Cooking to Low Kappa Numbers Facilitates TCF Bleaching to Full Brightness,"
90. Lachenal, D. and Muguet, M., Nord. Pulp

Pap. Res.], 7(1):25 (1992).
International
Non-Chlorine
Bleaching
Conference Proceedings, Miller Freeman,
91. Larsson, P., and Samuelson, 0., Nord. Pulp

Pap. Res.], 5(4):180 (1990).
San Francisco, 1993, Session 3-7.
345
107. Dillner, B. and Tibbling, P.,"Optimum Use

of Peroxide and Ozone inTCF Bleaching;
International
Proceedings,Tech.
Sect., CPPA, Montreal,
1994, p.319.
116. Henricson,
K., "MC Ozone Bleaching:
Machinery
and Pulp Reactor; International Non-Chlorine
Bleaching Conference Proceedings,
Miller Freeman, San
Francisco, 1994, Session 4-1.
108. Dahllof, H. ,"Medium Consistency Ozone

Bleaching, an Established Technology in
Mill Scale; International
Non-Chlorine
Bleaching
Conference
Proceedings,
Miller Freeman, San Francisco, 1994, Session 4-2.
117. Byrd, M.V. and Knoernschild,

J 75(5):101 (1992).
109. Stromberg, B. and Szopinski, R.,"Pressurized Hydrogen

Peroxide Bleaching for
Improved TCF Bleaching;
International
Tech. Sect.,CPPA,Montreal,
1994,p.199.
110. van lierop, B., Berry, R., Roy, B., "High
Brightness Bleaching of Softwood Kraft
Pulps with Oxygen, Ozone and Peroxide; 82nd Annual Meeting, Tech. Sect.
CPPA, Montreal, 1996, p.A247.
111. Soteland,
(1978).
N., Norsk
Skogtnd.
32(9): 199
112. Nutt, WE., "One Year's Experience

of
High Consistency
Ozone Bleaching" ,Air
Liquide/Ozonia
Ozone
Symposium
Notes,Air liquid, Paris, 1993.
113. Munro, E, "Espanola Ozone Pilot Plant
Results, Delignification
and Pulp Quality,
Hardwood
and Softwood;
Air liquide/
Ozonia Ozone Symposium
Notes, Air
liquid, Paris, 1993.
114. Bentvelzen,].M.,
Bogart, S.L., Gupta, M.
K., McKean,
W.T., Meredith,
M.D.,
Torregrossa, L.O., U.S. Pat. No. 4,216,054
(Aug. 5, 1980).
115. Sixta, H., Gotzinger,
G., Hog/inger, A.,
Hendel, P., Riicld, W, Peter, W, Kurz, E,
SchrittWieser,
A., Schneeweisz,
M. U.S.
Pat. No. 5,346,588 (Sept. 13, 1994).
K.]., Tappi
118. Bardsley, D.E.,"Compatable

Meta1lurgies
for Today's New Bleach Washing Processes; Eighth International
Symposium
on Corrosion
in the Pulp and Paper industry Notes, STFl and Swedish Corrosion Institute, Stockholm, 1995, p. 75.
119. Klarin,A. and Pehkonen,A., "Materials in
Ozone Bleaching;
Eighth International
Symposium on Corrosion in the Pulp and
Paper Industry Notes, STFI and Swedish
Corrosion Institute, Stockholm, 1995, p.
96.
120. Halinen, E., lindholm.,
C.-A., Gullichsen,
]., Henricson,
K., "Effect of Dissolved
Organic Material From Various Sources
on the Efficiency and Selectivity of MC
Ozone Bleaching;
International
Pulp
Bleaching Conference Proceedings,Tech.
Sect., CPPA, Montreal, 1994, p.l.
121. Neubauer, G., Kappel, J., Brauer, P., "Pr0cess Parameters of the High Consistency
Ozone Stage; International
Pulp Bleaching Conference Poster Proceedings,Tech.
Sect., CPPA, Montreal, 1994, p.41.
122.liebergott,
N., van lierop, B., Fleming,
B., Pulp Pap. Can. 94(11):T344
(1993).
123. Kovacs, T.G., Tana,].,
Lehtinen,
K.-].,
Sangfars, O.,"A Comparison
of the Environmental Quality of Elemental ChlorineFree (ECF) and Totally Chlorine-Free
(TCF) Hardwood Bleach Plant Effluents;
International
Non-Chlorine
Bleaching
San Francisco, 1995, Session 5-3.
124. O'Connor,
B.I., Kovacs, T.G., Voss, R.H.,
Martel, P.H., van Lierop, B., Pulp Pap.
Can. 95(3):47 (1994).
SECfION IV:
The Technology of
Chapter 6:
Hydrogen Peroxide
as a Delignifying Agent
D. Lachenal
CfP
Grenoble, France
1. The dual role of hydrogen peroxide in
delignifying and bleaching . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . .. . . .. . .. 349
2. Hydrogen
peroxide
delignification
Processes
. . . . . . . . . . . . . . . . . . . . . . . . . .. 351
3. Variables in hydrogen peroxide delignHication

3.1 Metals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
3.2 Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
"
3.3Time ..
"~'
3.4 Chemical charge. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
3.5 Consistency
4. Modified peroxide
delignification
treatments
353
353
355
355
355
356
. . . . . . . . . . . . . . . . . . . . . . . . . .. 356
5. Process equipment and Oowsheets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 357

6. Process control
7. Characteristics
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
of peroxide
delignHied pulp.
8.En~nmentdf.actors
358
. . . . . . . . . . . . . . . . . . . . . . . .. 358
359
347
Chapter IV 6: Hydrogen Peroxide as a Delignifying Agent
Chapter IV 6:
Hydrogen Peroxide
as a Delignifying
Agent
1. The dual role of hydrogen
peroxide in delignifying and
bleaching
Alkaline hydrogen peroxide is widely
used in the pulp industry to bleach ligninrich pulps to brightness levels of 80-83% ISO
without any substantial dissolution of lignin. The bleaching effect of hydrogen peroxide has been attributed to its ability to
react with various colored carbonyl-containing structures in lignin. Its use in chemical
pulp bleaching has long been limited to the
final stages to improve not only brightness
but also brightness stability (1). The commercial use of hydrogen peroxide as a
delignifying agent for kraft pulp was reported in the late 19705 (2). More recently,
some Swedish, Spanish, and Canadian mills
(3, 4) started the commercial production
of bleached kraft pulps using sequences
containing at least one extensive peroxide
delignification stage. A similar development
has been observed in the sulfite pulp industry, especially in Germany (5). The advantages of delignification
with hydrogen
peroxide are low investment cost and the
accompanying strong bleaching effect.
The action of alkaline peroxide as a
bleaching agent has been explained through
the reactions of the hydroperoxide anion,
HO~, formed in an alkaline medium according to the equilibrium:
HP2
+ OH- +-+ HO;
where the pKa
= 11.6
+ HP
[1]
at 25C.
This anion is believed to be the principal active species involved in the elimination of chromophores in lignin structures,
particularly conjugated ca.rbonyl structures

that are prone to react with the hydroperoxide anion (6) (See also Chap. 1lI 4, section 2.2.1.) The bleaching of mechanical
349
pulp by hydrogen peroxide has been essentially explained by this mechanism even
though it has been claImed recently that
peroxide decomposition products such as
the hydroxyl and superoxide anion radicals
('OH and 0>" respectively) may participate
in the bleaching mechanism, at least to a
small extent (7) .Whatever their form, these
bleaching reactions proceed with only minor amounts of material being dissolved and
cannot explain the delignification observed
with hydrogen peroxide in the processes
described below. It has been shown that,
under alkaline conditions, hydrogen peroxide is unable to attack phenols of the type
present in lignin (B).This finding was confirmed recently in a study on the modification of the lignin in a mechanical pulp
during peroxide bleaching (9,10). No degradation of the phenolic rings was observed.
These considerations indicate that no significant degradation of the residual lignin
in kraft pulp by hydrogen peroxide should
be expected. Indeed, there is no apparent
reason why residuailignin would be more
reactive than the original lignin. On the contrary,residual kraft lignin is more condensed
(11) and does not contain easily cleavable
ether bonds. Despite this, delignification
does in fact take place when a kraft pulp is
treated with alkaline hydrogen peroxide
(12). A temperature of 90C is usually required to produce a substantial decrease in
kappa number. Higher temperatures (e.g.,
110C) lead to increased delignification,
comparable to that occurring in a conventional oxygen delignification process (13),
Studies on the behavior of lignin in kraft
pulp during hydrogen peroxide delignification at 90C indicate that some depolymerization
of lignin occurs (11) and
carboxyl groups are created (11,14).
A comparison of peroxide and conventional oxygen bleaching shows that the
brightness is higher (13,15) and the resulting viscosity is lower for a peroxidebleached pulp than for a corresponding
oxygen.IJleached mt't pulp of the EIlC li~nin content; that is, the selectivity is lower
for peroxide delignification. The selectivities of chlorine, oxygen, and hydrogen
350
Pulp Bleaching
-Principles
and Practice
1600
40
Fe
Mn
'",
/0
:&1400 CE
o
(0)
b 30
u;S>
..20
~
:a
a;
"
~1200
'E
~/
1000
5
10
15
20
Kappa number
25
30
o'"
~"
a:
8DTPA
added
10
0.285
0.150
0.213
0.285
Metal ion concentration,
mM
Fig.2. lJ:tmIposItItmof by4rogM ~

IIb_
IIIUl~e
of trwutltm
Itms (M") (17).
peroxide are compared in Fig. 1 for a softwood kraft pulp (9).
The decomposition
products of hydrogen peroxide in alkaline media are thought
to cause the oxidation of lignin structures
which leads to the introduction of hydrophilic (carboxyl) groups, the cleavage of
some interunit bonds and, eventually, the
dissolution of lignin (12,16,17). Alkaline
hydrogen peroxide decomposes
to hydroxyl radicals and superoxide anions in the
presence as well as in the absence of transition metals (17):
H202 + H02 0;
+ .OH
.OH + 0>, + H20
+ 02 + OM"
M(n+I)++ 'OH + OHH202 + Mn+ +

HO; + M(n+,)+ + Mn+ + 02: + H+
The radicals formed may react further with
each other or hydrogen peroxide and give
rise to oxygen and water as the final products. Some transition metals accelerate peroxide decomposition (Fig. 2). Formation of
hydroxyl radicals can also result from the
thermal homolysis of hydrogen peroxide.
This decomposition pathway is substantial
at a temperature above 100C.
The contribution of peroxide decomposition products to lignin degradation is supported by several studies which clearly
show a close relationship between the rate
of oxidation of lignin model compounds
and the rate of decomposition of hydrogen
peroxide (17). As an example, oxidation
,,, tile
_t,d
of some phenolic models was found to be

maximum at pH 11.5 where the decomposition of hydrogen peroxide is also near its
maximum. The primary reaction of residual
lignin with hydroxyl radicals is believed to
be the formation of phenoxy radicals from
phenolate ions by one-electron abstraction.
Hydroxyl radicals and oxygen are known
to give rise to such a reaction. On the contrary, it has been shown that superoxide
ions do not react with phenolate ions (17).
Superoxide ions can, however, react with
the phenoxy radical intermediate to form
an organic hydroperoxide which is subsequently degraded to low molecular weight
compounds (1B). Similarly, oxygen also reacts with phenoxy radicals. The observed
bleaching effect is most likely a result of the
action of undecomposed hydroperoxide anions on carbonykontaining
chromophores.
Cellulose may undergo depolymerization
by reaction with hydroxyl radicals (19). If
transition metals are present in the cellulose matrix, formation of hydroxyl radicals
may take place in close enough proximity
to the cellulose chains to react with them.
In oxygen bleaching, peroxides are formed
during the reaction of oxygen with lignin
and therefore the hydroxyl radicals are generated at or near a lignin site. This difference may explain why the selectivity is less
in hydrogen peroxide delignification than
in oxygen delignification (Fig. I). Moreover,
a higher yield of hydroxyl radicals in peroxide delignification may also be expected
because of the higher peroxide charge (20).
351
352
Pulp Bleaching
-Principles
and Practice
To evaporation plant
and recovery plant
Sequence
Pulp type
PC ED ED
Hardwood and softwood

and soda AQ
OPDED
PPDED
Op,OPP'
OPD
PDp,PDPD
PHDH
PCHH
(PO) (PO)
(EOP) P
PPacP
OPZ
OPZP
(EOP) Z P
Reference
Softwood
kraft
Softwood
kraft
Softwood
and hardwood
Hardwood
kraft
Softwood
sulfite
Softwood
sulfite
Softwood
sulfite
kraft
Softwood
and hardwood
Softwood
sulfite
Hardwood
kraft
Hardwood
2,12,42
13,18,29,30
Softwood
Softwood
kraft
39
4,57
9
24
5,25
5
31
52
58
9
59
52
kraft
sulfite
kraft
and softwood
sulfite
AQ, anthraquinone;
Pac, peracid; Z, ozone
. Semi-bleached
(70-80% ISO for softwood and 75-85% ISO for hardwood)
b
Low-brightness pulp (50.60 % ISO)
To summarize, in the bleaching of chemical

pulp hydrogen peroxide may function as:
1. A true bleachiDi aRent. Because its specific
and efficient action on carbonyl and conjugated carbonyl groups, the hydroperoxide anion can destroy many of the chromophore groups present in pulp, including those created by the other reagents
applied in previous bleaching stages. Chlorine, chlorine dioxide, and oxygen are
known to form quinone groups (21-23).
To eliminate such structures hydrogen peroxide is added in an alkaline extraction
stage or at the end of the bleaching sequence.A temperature of 50 to 70C is sufficient for this purpose.
2. A deli2nifyinll a2ent. At a temperature
higher than 80C, hydrogen peroxide starts
to have a marked effect on unbleached lignin or oxygen-bleached lignin. Several options are available for introducing hydrogen peroxide in the bleaching process,
among them the application of hydrogen
peroxide after oxygen bleaching. An OP
sequence offers the advantage of extending the chlorine-free part of a bleaching
process at a relatively moderate investment

cost. Simultaneous
addition of oxygen and
peroxide
is an alternative,
although
less
efficient for brightness
development
(9).
As indicated
previously,
peroxide
delignification theoretically
can replace oxygen
delignification.
However, oxygen is more
cost effective for the same degree of delignification. This is why this last option is
currently restricted to the prebleaching
of
some sulfite pulps. Indeed, the easily solubilized lignin in sulfite pulps responds particularly well to hydrogen peroxide delignification (5, 24-27). Several bleaching sequences, including hydrogen peroxide delignification, that have been proposed
for
commercial
use are listed in Table 1.
2. Hydrogen peroxide delignification processes

Three hydrogen peroxide delignification
proce55e5 havebeen de5Cribed.In the fir5t,
the peroxide is applied directly to the unbleached pulp.This process has been implemented on kraft pulp at Cellulose des
Ardennes in Belgium since 1979under the
,.------...
and recovery boiler
_~ l-_-:_~
:Brownstock:
washing ,
:
J
.------.
I
: Pulping :
:I Pulping :,
L:
:-~~~~!~t=k:
washing
-...
~--
: Stage:
O2 +
NaOH
'--+--'
:Washing 1
I
---'
r-------...
I
I
: Bleaching:
I
L
I
J
FI,.3. ~toftlle~~.lIpijbIIoII (MI_J prot:ns.

commercial name MINOX (for mini - QXygen) (2). The peroxide stage is integrated
into brown stock washing in a way similar
to that for an oxygen bleaching stage (Fig.
3). Low charges of hydrogen peroxide and
sodium hydroxide (NaOH) are used (less
than 0.5% on pulp) which explains why delignification is limited to 20%.
The second process is characterized by
a first step that alters the trace metal profile of the pulp by pretreatment
with a
complexing agent (Q stage) and by a second step in which the alkaline hydrogen
peroxide bleaching solution is applied (2830). Commercialized
under the name of
UGNOX (for lignin oxidation), this process
has so far been used to complement oxygen bleaching. The hydrogen peroxide and
sodium hydroxide charges are generally
high (up to 3-4% on pulp for HP ) and
delignification can be as high as 5o%.This
process theoretically can be integrated with
oxygen bleaching into brown stock washing. However, the acidic nature of the effluent from the sequestering stage and its
relatively high metal content introduces a
Water
Water
difficulty that has not yet been overcome.

The flowsheet for this process is shown in
Fig. 4.
The third process uses both oxygen and
hydrogen peroxide to provide a hydrogen
peroxide-reinforced
(J1).When hydrogen peroxide is added in
a conventional oxygen bleaching process,
delignification is extended.This effect is substantial even for peroxide additions as low
as 0.2 -0.5% (31). The viscosity is increased
because of the lower alkali charge and the
lower temperature required in the process
353
the rate of peroxide decomposition

influence the extent of delignification
cellulose degradation.
also
and
and recovery boiler
: Pulping
:
iuTuJ
t____..
:Brown stock:
washing
'
,-------...
: Bleaching:
I
I
I
I
J
Fig.5. FIort1sbHtoftlle~osygM-~
peroxIik dellg,dJbtloft
process.
(32).A kappa number reduction of 60% is

easily achieved in an oxygen stage reinforced by hydrogen peroxide. The schematic flowsheet presented in Fig. 5 is the
same as that of an oxygen delignification
process. For practical reasons, hydrogen
peroxide is added before oxygen injection.
No commercial implementation of this process has been described so far. Addition of
hydrogen peroxide in a non-pressurized
(E+O)-type of delignification is possible if a
full-fledged oxygen delignification system
is not available.The (E+O+P) stage may lead
to a 30-35% kappa number reduction when
0.5% HP2 is added (4, 33, 34).The (E+O+P)
stage is even more attractive when applied
to sulfite pulps (35).
3. Variables in hydrogen peroxide delignification

As noted previously hydrogen peroxide
delignification results partly at least from
the oxidation of lignin by the decomposition products of the hydroperoxide anion,
H02~Therefore, the parameters that affect
3.1 Metals
Decomposition
of hydrogen peroxide
under alkaIine conditions is greatly influenced by the presence of specific inorganic
substances that act as catalysts or stabilizers. Among the catalysts, transition metals
such as Fe, Cu, and Mn have been studied
extensively (28, 36, 37). On the other hand,
magnesium salts and sodium silicate are
well-known peroxide stabilizers According
to some studies, the key to optimum hydrogen peroxide delignification is to control the metal profile in the pulp before
hydrogen peroxide treatment in such a way
that the concentration of transition metals
is as low as possible and that of alkalineearth metals (essentially Mg) is sufficient (28).
In other studies (3637), it has been
shown that not all transition metals are detrimental. For instance, addition of manganese has been found to be effective in
retarding carbohydrate degradation (36).
Although the ideal metal profile is not
known, a beneficial effect is observed when
a pretreatment
with a chelating agent is
used. For example ethylenediaminetetraacetic acid (EDTA) is best used at pH 5-7, as
shown in Figs. 6 and 7 (28). Other preferred
conditions in the pretreatment are 90C for
60 minutes at a consistency
of 10%. A
charge of 2 kg EDTA per ton of pulp is sufficient. After EDTA pretreatment, not only
is hydrogen peroxide delignification
improved, but bleaching is enhanced and cellulose degradation is less. At the same time,
peroxide consumption
is lower (9). It is
probable that other complexing agents applied under similar or different conditions
lead to the same improvements.Thus,DTPA
in the presence of sodium sulfite provides
about the same benefits (38)Acid pretreatment with sulfur dioxide or sulfuric acid
improves peroxide delignification (11, 39,
40) but not to the same extent
as
complexing agents (41).
Therefore, it appears essential to limit the
effect of metal catalysts even though
delignification involves the decomposition
354
Pulp Bleaching
- Principles
and Practice
70
400
E
Q.
Q.
Ci
~
200
en
~60
:Z
CD
C
-,5O
'C
m
11
pH
11
11
11
pH
80
E
Q.
Q.
c:
~40
o
1
11
pH
5
pH
20
950
C>
E
Q.
~925
E
'0
': 10
CD
LL
. , .EDTA
~900
o
>875
pretreated
o
1
I
7
850
I
11
pH
Plf. 6. Ejfed of JIll 018tile ~
7
pH
of-Ws
rIIIIrMtM .. ED1'A-JlretrMtM
sojlrt1ootl
"' prdJts (18).
nft
j
c:
products of hydrogen peroxide. This suggests that the radicals and oxygen have to
be formed slowly to actively participate in
delignification process without any detrimental effect on cellulose.
The effect of stabilizers on delignification
has been investigated.
Sodium silicate,
organophosphonates,
and polylactones do
not lead to any significant improvement
when added in a peroxide stage (5,12,39,
42).Although addition of magnesium sulfate does not seem to improve delignification either, its effect on cellulose
degradation is favorable (4, 13).
~E 15
.,::>
c
N
<&
:I:
10
5
1
.-
.
5
pH
EDTA
pretreated
11
Fig. 7. Iff/ed of JIll I.. tile perozIM dellpljletlUorl

of .rIIre4IeIllIfIII ED1'A.pretreated softrwotl
nft jIrIlps (28).
Chapter IV 6: Hydrogen Peroxide as a DeIignifying Agent
355
-.e.
::i
~Z
20
40
60
Time. m
80
100
0.5
120
1.0
1.5
H202. %
4
Fig. B. Rille of B,O, eo

Plto.. I.. peroztlle
."pljktiltofl
(OP ~)
(9). CoUtf)(f'C,
t:OfISlsUfIt:y,
:rr.NIIOB, 1.6%
tWfIs :
1O'X.
BP. 0fIJIfIlp.
OzygefI-l'rNIMsoft-Jll
JIfIlJIoflulJ!lM-IB.O tI8Il brlgiltflas 31%
'FlfItIlluIpptI--'(lifter 120 11II...): 12.1
it11U1l6.5
(EDTA
~Z
0.5
1.0
1.5
H202. %
On.ce the peroxide stage has been successfully stabilized with optimal pretreatment, the reaction time should be as long
as practically possible. Figure 8 shows that
oxide charge, there exists an optimum s0dium hydroxide charge. At sodium hydroxide charges above the optimum,
the
effectiveness of hydrogen peroxide is reduced and brightness reversion is observed
(41).The trend is similar for softwood kraft
pulps although the adverse effect of high
alkalinity is not always observed (42).Therefore, there is no incentive for increasing the
sodium hydroxide charge beyond an optimum level. This level is a function of the
hydrogen peroxide charge and has been
estimated from previous studies (fable 2).
::i
FIfItII brlgbtrtess (lifter 120

: 45% tI8Il
""".)
54% (EDTAJlr8trNbrtMl).
3.3 Time
-.e.
Jlr81ret11rf8erat)
3.2 Temperature
Hydrogen peroxide 'decomposition
is
strongly influenced by temperature. Thermal decomposition
occurs by homolytic
cleavage of the peroxide bond. Temperatures as high as 120C have been used in
peroxide de1ignification (I3, 43). However,
it has been shown that a decrease in temperature from 120C to 100C improves
pulp quality without affecting lignin dissolution. Again, it seems that too rapid peroxide decomposition
(which occurs at
120C) has a detrimental effect on selectivity. A temperature of 90C represents a good
compromise because the rate of delignification is still relatively high and cellulose
depolymerization does not take place to any
appreciable extent provided a complexing
pretreatment is used (41,42). Furthermore,
no pressurized
equipment
is needed.
Higher temperatures may be used, for instance, when hydrogen peroxide is added
in an oxygen delignification stage (31).
356
0fI1uIpptI
Fig.,. If/fed of BP, tI8IlNtIOII~
...""- tI8Il ""81_ DP I. lbe perozUe
.'iptjktllWfl of IIbtIt*JootIlmfftJI8lJI(a22, DP 15(0) (11)
bktlt:betl UJIIHI
--'t:OfISlsUfIt:y.
CoIuIItiou
: Btl'C,
1'beoJIM.-
120""'"
2O'X.
0/1"- t:OfIIlI-
tIou for 3O'X.tI8Il 45% .'ipt./futHm.
H202' % on Pulp
1
1.5
2
3
4
NaOH, % on Pulp
Operating
90C, 2 h, 1(}"15%
consistency
3.5 Consistency
Increases
the longer the hydrogen peroxide is allowed

to react, the more it is beneficially consumed. Satisfactory results can be achieved
in 120 minutes at 90C (4, 9,41,42).
3.4 Chemical charge
The effect of sodium hydroxide (NaOH)
and hydrogen
peroxide
charge
on
delignification is shown by the curves in
Fig. 9 which represent the change of kappa
number and cellulose DP with varying sodium hydroxide and hydrogen peroxide
dosages for a hardwood kraft pulp.The plots
show that kappa number reduction is maximum at the highest applications of sodium
hydroxide and peroxide. However, if the
peroxide charge is kept constant, the kappa
number generally decreases as the sodium
hydroxide amount increases although this
effect is not observed at the highest sodium
hydroxide dosages (I 2).Thus, for each per-
conditions:
2-2.5
2-3
2-3
2.5 - 3.5
3-4
in consistency
from
1 OOAi
to 25%
have a positive effect on the extent of peroxide delignification (41, 42).Trials at higher
consistency (30%) have shown a further
improvement
in peroxide delignification
(41). Whether high consistency should be
used, however, is questionable considering
the higher investment cost required to dewater the pulp. In most mills performing
hydrogen peroxide delignification, the consistency is about 10%.
4. Modified peroxide
delignification treatments
In some cases, peroxide delignification
has been carried out under nonconventiona! conditions at laboratory, pilot, or full
scale. For example, delignification
using
hydrogen peroxide and oxygen under acidic
conditions has been investigated (44).The
mechanism of delignification is completely
different from that previously described for
reactions in alkaline media. In acidic me-
dia, the reaction involves an initial electrophilic attack of a hydroxonium

cation,
(OH+) and subsequent oxidation of the hydroxylated lignin by oxygen or hydrogen
peroxide (45, 46). Compared with alkaline
peroxide treatments, there is less delignification and a greater viscosity drop which is
further increased if the pulp is later subjected to an alkaline stage (44). This process has been proposed for sulfite pulps and
as a pretreatment before the oxygen or alkaline hydrogen peroxide de1ignification of
kraft pulps (45,47). Activation ofacidic hydrogen peroxide by sodium molybdate has
been described (48).
Another example of a modified process
is the use of magnesium hydroxide to provide an alkaline medium for peroxide delignification. This modification
makes it
possible to recycle the effluent back to the
recovery furnace of a magnefite mill (25,
26, 49).When magnesium oxide (MgO) is
dissolved in water, a pH of only 9-9.5 is obtained. Consequently, much higher temperatures must be applied to achieve the
same degree of delignification as with sodium hydroxide. A temperature
range of
11(}'120C is required which implies the use
of pressurized equipment. Under these conditions, the combined use of hydrogen peroxide and oxygen represents an attractive
alternative.
The desire to improve the efficiency of
peroxide delignification has been the stimulus for a number of studies. For example, if
peroxide delignification is initiated by the
attack of the peroxide decomposition products on the phenolic groups in residual lignin, one way to enhance the process would
be to increase the number of these phenolic
groups. The validity of this supposition has
been clearly demonstrated in experiments
in which kraft pulp was demethylated by
potassium triphenoxide
to produce new
phenolic hydroxyl groups or methylated by
dimethyl sulfate to eliminate phenolic
groups (50). Demethylation enhanced peroxide delignification, while methylation of
phenolic hydroxyl groups retarded peroxide delignification. In another study, kraft
pulp was pretreated with small amounts of
chlorine. This step resulted in a dramatic
-~~_.

improvement in the efficiency and, more
importantly, the selectivity of the following
peroxide treatment as illustrated by the values in Table 3 (43). One effect of chlorine
in this process may be to create new phenolic hydroxyl groups in the lignin macromolecules. Nitrogen dioxide has a similar
effect (51). These results confirm the importance of phenolic hydroxyl groups in
hydrogen peroxide delignification and open
the way for the discovery of more efficient
peroxide-based delignification processes.
Table 3. EfJt of. cblorlM JWeIrNlrrtMl Oft_lee1i",1y I. IN JIer'OXIiletlellpljietltlml
of.
pulp (KlIpp. No. 30, DP
HNfIJOOIl
""'/I
1600) (43).
% on pulp
0Z'
Kappa no.
19.5
14.6
Cellulose
1065
1300
Conditions:
DP
12.01410
1% HPz, 120C, 1.5 h, 12%

consistency
Activation of hydrogen peroxide is another possibility for enhancing delignification. As mentioned previously, some
transition metals likely act as activators in
peroxide delignification treatments. Other
substances have also led to positive results,
at least in some cases. Among them, cyanamide, (NHzCN) was found to enhance the
peroxide delignification of sulfite pulps substantially without negatively affecting the
cellulose (52-54).
357
problem indicate that titanium is not corroded under conditions existing in alkaline
peroxide bleaching (55). A conventional
downflow extraction tower can be used
without any modification. However, the
desired retention time is generally greater
than that of a regular extraction stage which
may require the use of two towers in series.As a general rule, the peroxide should
be introduced at a point as distant as possible from where other chemicals (e.g.,
sodium hydroxide)
and live steam are
added. Inadequate mixing may lead to unproductive
peroxide decomposition
in
pockets of extremely high alkalinity or temperature. Several peroxide
application
points are indicated in Fig. 10.A good application point is the throat of an MC pump.
Peroxide addition in a mixer just before the
bleaching tower is another possibility. The
use of a high-shear mixer is not required
because hydrogen peroxide is very easily
mixed with pulp. However, chemical consumption may be reduced by instantaneous
and thorough mixing. Although not recommended, the addition of peroxide can be
made following washing. In this approach,
hydrogen peroxide and sodium hydroxide
are sprayed onto the mat exiting the decker.
The two chemicals must be added separately because of the poor stability of hydrogen peroxide
in sodium hydroxide
solutions.
5. Processequipment and
flowsheets
The process flowsheet of a typical hydrogen peroxide delignification is given in Fig.
10. A peroxide stage can be carried out in
whatever alkaline peroxide-compatible
equipment is available. Alkaline peroxide
is normally incompatible with carbon steel
and titanium. This is of particular concern
where existing chlorine dioxide stages are
being considered for replacement by peroxide in non-d11orine bleaching sequences.
However, actual mill operating experience
has shown that alkaline hydrogen peroxide
has only a moderate effect on titanium
equipment elements. Recent studies of this
358
chelating agent, EDTA. The major change

required is the regulation of the pH of the
pulp prior to this stage by sulfuric acid addition. The E, tower may be used for the
peroxide stage. In some cases, a second extraction tower may be used to extend the
delignification.
In this case, it has been
found advantageous to split the hydrogen
peroxide between the two stages.A further
advantage of operating two successive P
stages is that the hydrogen peroxide residual
from the second stage, which is generally
higher than that of the first stage, can be
recycled to the first stage, reducing the
chemical requirement for the sequence (41).
Figure 11 shows the process flowsheet
for combined
hydrogen
peroxide
- oxy-
gen delignification.As stated above, hydrogen peroxide is introduced immediately

after washing or at the high-shear mixer. It
has been suggested that hydrogen peroxide is best used when added after oxygen.
However, this last option is difficult to perform in a pressurized oxygen system. It
nevertheless is possible if the oxygen stage
is of the (EO)-type.
7. Characteristics
of peroxidedelignified pulp
Implementation
of peroxide delignification in kraft pulp mills is still too recent
for much published data on pulp yield, pulp
quality, and cost to have accumulated. From
laboratory studies there is evidence that
peroxide-<:ontaining sequences give higher
pulp yields. A comparison
Fig. 11. Proens fl-sbHt

of mHI"..-COIfSisIet8cy
(HP, + 0,) tlellpljietltlml.
6. Process control
Because
For mills in which the peroxide delignification process is combined with a metal
complexing stage, few bleach plant modifications are required (30). The C tower can
be used for the pretreatment
with the
chemical reaction can proceed with the

current dosage and how fast the peroxide
is being consumed. Combined, the two sensors effectively prevent excessive or insufficient peroxide from being applied. At the
same time, compensations
for changes in
the process conditions can be made. Measurement of residual peroxide can be made
before or after the tower.
The pH of the metal complexing or Q
stage is critical for its effective operation.
The pH should therefore be monitored constantly and the acidification liquor flow
controlled. If the acidification is being carried out in a retention chest where mixing
is not ideal, the pH should be measured in
the exit pipe.
of the high cost of hydrogen
per-
oxide and the large quantities

usually
needed for delignification, a peroxide stage
requires more accurate control than do
other bleaching stages. A reliable feedback
control of brightness is achievable using an
optical in-line analyzer alone. However, a
dual sensor strategy is often preferable (56).
A brightness sensor reveals how far the reaction has progressed; a residual chemical
sensor indicates how much further the
of APPDED
(A
acid pretreatment) and CEDED sequences

showed a 2% difference in yield loss during
bleaching in favor oftheAPPDED sequence
(39). No similar data exist for the OQPDED
sequence. As indicated by some preliminary work, an OQP bleaching sequence
does not provide a better yield than a
(CD)(EO)D sequence (4). As to brightness
stability, some comparisons between APp,
CEH,APPDED, and CEDED sequences can
be made. Although CEH-bleached pulps are
brighter, they are less stable than APPbleached pulps under storage at 105C.The
same trend is observed for fully bleached
pulps, but the difference is less marked
(39).
For semibleached pulps (APP- and CEHtreated),
the differences
in strength
properties are not significant (39). DEDEDbleached pulps appear to be stronger than
APPDED pulps. In this case, however, no
complexing stage precedes the peroxide
stage. The introduction of a Q stage ahead
of the peroxide stages should minimize the

strength differences. According to mill data,
OQP-prebleached softwood kraft pulps, after full bleaching, have strength characteristics quite comparable
to those of
conventionally bleached pulps (30) despite
the lower viscosity of OQP-treated pulp (4).
OQP- or OQPP-bleached market pulps are
currently being produced at various brightness levels. It has been shown that some,
despite being of only moderate brightness
(7().8()% ISO), are very clean with respect
to both shives and dirt. These pulps may
possess other properties which need to be
evaluated in long-term tests.
Considering the difference in cost between the two chemicals, hydrogen peroxide delignification
cannot compete with
oxygen delignification. However, hydrogen
peroxide may be the reagent of choice to
extend the chlorine-free part of a bleaching sequence as much as possible in a separate stage following the oxygen stage, or in
combination
with oxygen in one single
stage. At current prices, the use of hydrogen peroxide leads to
substantial cost
penalty which is difficult to justify were it
not compensated for by market advantages
provided by a significant reduction in the
amount of absOrbable organic halide (AOX)
formed.
8. Environmental
factors
Because peroxide bleaching is a chlorinefree process, the resulting effluent can theoretically be burnt after it is recycled back
to the brown stock washer.This strategy has
been followed on a mill scale for many years
(2). As a consequence, a potential reduction in pollution load can be achieved which
is roughly proportional to the kappa number drop during the peroxide stage. As an
example, it has been shown that, if the
CEDED sequence is replaced by APPDED
(50% delignification after APP) and the effluents from the peroxide stages are recycled, reductions of over 90% in color, 40%
in BOD, and 65% in TOC can be obtained
(39). Compared
with oxygen delignification, peroxide delignification appears to
provide better color abatement because of
the specific action of hydrogen peroxide on
chromophores.
359
The AOX issue has been the major incentive for the development of hydrogen peroxide delignification as a complement to
oxygen delignification.As indicated above,
it is possible to achieve a 50% further kappa
number reduction using about 25-30 kg
HP/t
of pulp provided that the oxygenpredelignified softwood kraft pulp is given
a proper chelating pretreatment.
Pulp
treated in this way can be easily bleached
to a full brightness in three stages without
molecular chlorine, while generating substantially less than 0.5 kg AOXlt of pulp in
the total mill effluent (30). The development of extended pulping has made it possible to reach a brightness higher than 80%
with both hardwood and softwood kraft
pulps using the totally chlorine-free OQPP
sequence in which noAOX is formed (57).
The ultimate goal in such sequences is to
bum the effluent. One intermediate step
would be to use the alkaline effluents for
brown stock washing and to dispose of effluent from the acidic Q-stage. However, an
effluent consisting of sequestered transition
metals and excess sequestrant may not be
environmentally
acceptable. The Q-stage
effluent could be concentrated and burnt.
If the effluent was burnt in the recovery
boiler, the metals would be carried forward
to the green liquor clarifier where they
would precipitate. A modem kraft pulp mill
must dispose of about 10 to 30 tons of metal
residues annually which would have to be
passivated if used for landfill (41). Another
problem arising from burning the Q stage
effluent might be the sequestrant itself.The
sequestrants proposed to date are EDTA and
DTPA, and the burning of such nitrogencontaining compounds is likely to generate
NOx although the extent of this problem is
unknown. The best choice of sequestrant
is one which, on combustion, yields only
carbon dioxide, water, and sodium for recovery (41). Another solution to the transition metal problem is to inactivate the
metals and to leave them in the puIp (41).
This area has yet to be studied extensively.
The effluents from Q and P stages of the
OQP sequence have been tested for toxic-
360
ity to daphnia and found to be non-toxic,

provided the residual peroxide in the peroxide stage effluent is destroyed, for example, by acidification with sulfur dioxide
(4). These effluents are also very low in
color. Biodegradation of peroxide stage effluent has been studied (5) and no particular problems were encountered.
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(17):494 (1980).
52. Siiss, H.U. and Nimmerfroh,

N.E, "Peroxide bleaching Technology
Review," 1993
Workshop on Emerging Pulping and Chlorine-Free BleachingTechnologies
Proceedings, Dept of Wood and Pdper Science,
North Carolina State University, Raleigh,N.C.
53. Granger, M., Desmurs, M.]., Stefan, M.D.,
French
Pat. No. 2,560,898
(March 6,
1984).
54. Sturm,W:,
(1990).
Wocbenbl.Papteifabr.(10):423
55. MacDiarmid,].A.
and Reichert, D.L., "Corrosion and Materials Engineering Considerations in Hydrogen Peroxide Bleaching,"
Symposium on
Corrosion in the Pulp and Pdper Industry
Notes, TAPPI PRESS,Atlanta, p.97.
56. Makkonen,
H. and Paakkonen,
Trade] 166 (4):31 (1982).
57. Pearson,].,
(1992).
Pulp
Pap. Int.,
T., Paper
34 (3):50
58. Hebel, G. and Kruger, H., U.S. Pdt. No.3,

867,246
(Feb. 18, 1975).
59. Lachenal,
D., "The Pulping
and Bleaching
Process of the Future," 1993 Workshop on
Emerging Pulping and Chlorine-Free

Bleaching
Technologies
Proceedings,
Dept. of Wood and Pdper Science, North
Carolina State University, Raleigh, N.C.
SECTIONIV:
The Technology of
Chapter 7:
Enzyme Treatments of Pulp
Roberta L Farrell
Biotech division of C1ariant Corporation
Lexington, MA, USA
and
University ofWaikato
Depanrnent of Biological Sciences
Hamilton, New Zealand
Uisa Viikari
VIT Technical Research Centre of Finland
Espoo, Finland
David Senior
ICI Canada Inc
Mississauga, Ontario
1. Introduction
. . . . . . . . . . . . . . . . . . .. . .. . . . . . . . . .. . . . . . .. . .. .. . ..
365
2. Initial studies on the use of enzymes In bleaching. . . . . . . . . . . . . . . . . . . . . . .. 365

2.1 Bleaching with ligninases and laccases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 365
2.2 Bleaching with xylanases. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 366
3. Proposed
mechanism
of enzyme action
366
4. Hemicellulose-degrading
enzymes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 367
4.1 Enzyme sources. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 367
4.2 Enzyme activity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 368
S. Process aspects of enzyme treatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 368
5.1 Effects of enzyme treatments in multi-stage
bleaching sequences. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 368
5.2 Environmental effect of enzyme treatments. . . . . . . . . . . . . . . . . . . . . . . . . . . 371
6. Enzyme treatments In the bleach plant. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
6.1 Process flowsheets
6.2 Economic factors in xylanase treatments. . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.3 Effect of conditions external to the bleach plant
6.4 Benefits in bleach plant operations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
7. ~tureprospects
"
363
,.,
372
372
373
374
375
375
Chapter IV 7: Enzyme Treatments of Pulp
Chapter IV 7:
Enzyme Treatments
of Pulp
1. Introduction
The traditional, effective approach of
using chlorine-containing
chemicals as
bleaching agents has been challenged, first
by environmental groups and then by consumers. In response to these pressures, alternative bleaching technologies have been
developed to partially or completely replace
these chemicals, particularly elemental chlorine (Cl). Enzymatic processes have been
developed
as one of these alternative
bleaching technologies.
The primary goal of chemical pulp
bleaching is to remove lignin from the pulp
while retaining the carbohydrates
in the
pulp. Two different approaches using enzymes have been followed since the early
1980s to accomplish this goal, but only one
has led to a successful commercial mill-scale
process. The main focus of this chapter is
to discuss the use of such enzymes, called
hemicellulases (specifically xylanases) for
enhancing the chemical removal of lignin
in multi-stage bleaching sequences. This
process, sometimes termed "bleach boosting" (1), has been successfully used in pulp
mills throughout the world. An alternative
approach, direct delignification, using enzymes called ligninases or laccases which
act directly on lignin, is still in the exploratory stage and awaits possible future commercialization.
Environmental, customer, and regulatory
concerns have favored the investigation of
enzymes in bleaching because they are
readily biodegradable and do not contribute to organochlorine formation.
Enzymes are catalysts of highly specific
reactions.
In their capacity as catalysts,
enzymes are not consumed and only a small
amount is required to bring about a particular reaction. Enzymes consist mainly of carbon, oxygen, hydrogen, and nitrogen and
are classified as proteins, molecules made
by living organisms. Enzymes are often
365
366
Pulp Bleaching
-Principles
and Practice
named by adding the suffix "-ase" to the

name of a specific substrate upon which
they catalyze certain reactions. For example, a cellulase catalyzes the hydrolysis
of cellulose, and a xylanase catalyzes the
hydrolysis of xylan. That enzymes catalyze
only very specific reactions has made them
particular1y relevant to the pulp and paper
industry. For example, xylanases catalyze
hydrolysis of xylans but not of cellulose.
Enzymes are manufactured by fermentation, the large-scale growth of microorganisms. After growth, the enzymes
are
collected and separated from the microorganism source by various separation methods. The enzymes are delivered typically in
a concentrated liquid form which is stable
and safe to handle and which does not contain any living organism.
Enzymes used in bleaching are marketed
by several suppliers. The beneficial effects
of enzymes in bleaching depend on the
bleach sequence used, the residual lignin
content of the pulp, the final target brightness, and environmental concerns of the
mills. The main goals in the enzyme-aided
bleaching of pulps have been directed toward reducing the consumption of chlorine
chemicals in the bleaching process and lowering the adsorbable organic halogen (AOX)
content of the effluents. Enzyme treatments
have been successfully used in conventional
chlorine-containing
sequences, such as (CI
D) E D E D, in ECF (elemental chlorine-free)
sequences, in TCF (totally chlorine-free)
sequences, and also in sequences where
oxygen, peroxide, and ozone are used.
ment of unbleached kraft pulp with the

white-rot fungus, Pbanerocbaete
cbrysosporium, leads to a significant drop in
kappa number (4). However, pulp bleaching with this fungus is not commercially
feasible because the organism requires more
than five days' incubation with the pulp to
achieve significant delignification.
Research activity using enzymes produced by Basidiomycetes for the laboratory
bleaching of pulp followed the discovery
of lignin peroxidases
(initially called
ligninases) (5-8). It was later reported,
however, that different mixtures of lignin
peroxidases
and manganese-dependent
peroxidases did not consistently delignify
unbleached kraft pulp, although lignin-containing materials appeared to be released
into the effluent as evidenced by absorption spectroscopy (9).
Besides lignin and manganese-dependent
peroxidases, a prevalent enzyme in many
white-rot fungi is laccase; an enzyme which
catalyzes the synthesis of lignin in growing
plants (10). Laboratory results have shown
that treatment of unbleached
northern
softwood kraft pulp with laccase in the presence of a dye, 2,2' -azinobis- (3-ethylbenzthiazoline-6-sulfonate)
(ABTS), causes more
than a 25% drop in kappa number, indicating direct delignification (11). This work
has not been applied outside of the laboratory, but the use of laccase in combination
with an aromatic molecule mediator and
oxygen has achieved significant reduction
in the kappa number of unbleached kraft
pulp (12).
2. Initial studies on the use of

enzymes in bleaching
2.2 Bleaching with xylanases

In 1987, Finnish researchers proposed
the novel idea of using enzymes from the
group called endo-beta-xylanases
(xylanases) for treating unbleached kraft pulps
(13, 14). Previous non-bleaching uses of
endo-beta-xylanases had been reported in
the early 1970s (15, 16) and included the
removal of hemicelluloses from chemical
pulps to produce dissolving pulps (17). The
effects of xylanases on bleaching have also
been reported by several other groups (1820).
2.1 Bleachingwith ligninases and

laccases
Initial studies on the use of enzymes in
bleaching were performed with the goal of
imitating the wood-decaying action of fungi
in nature. The largest group of fungi that
degrade wood are the Basidiomycetes
(2)
and the best-studied are those which decay
wood specifically by degrading lignin and
bleaching the wood (3). Laboratory treat-
These initial reports prompted investigations by many academic laboratories and

industrial groups on the effect of different
xylanases in bleaching. Patent applications
in the area of enzyme bleaching have been
madefrequently
starting in 1988 (21). The
first mill trials were conducted in 1988 (22).
literature reviews covering the development of enzymes for bleaching are available
(23,24).
3. Proposed mechanism of
enzyme action
Hemicelluloses are polysaccharides associated with cellulose and lignin in plants.
The two most common hemicelluloses are
xylans and mannans. Not only do the relative amounts of these two polysaccharides
vary in hardwoods and softwoods, but their
chemical composition as well (25).
Extensive modification of hemicelluloses
takes place during pulping processes. During the initial heating period in kraft
pulping, when the alkali concentration
is
comparatively high, the xylan is partially
depolymerized and stripped of substituents
such as acetyl and arabinosyl groups. As
pulping proceeds, the a1kali concentration
decreases and degraded, short-chain xylans
precipitate in a more or less crystalline form
on the surface of cellulose microfibrils (26).
Overall, xylan constitutes over 90% of the
hemicelluloses in hardwood kraft pulp and
50% in softwood pulp. Because of the
reprecipitation, hemicelluloses are concentrated on the fiber surfaces of microfibrils
although a part remains at its originallocation in the fibers.
One of the predominating hypotheses for
the mechanism
of xylanase activity in
bleaching is that these enzymes catalyze the
hydrolysis of reprecipitated
xylan on the
surface of the pulp fibers making the lignin
fragments in and on the fiber easier to
remove in the following bleaching and
alkaline extraction stages (27,28). This hypothesis is not supported by the results of
experiments in which pulp was delignified
under high alkalinity conditions which precluded xylan deposition. In that situation,
xylanase treatment lead to a reduction in
Optimum
pH'
Optimum
Temp. ("C)'
Supplier
Product
Trade Name
Primalco
Ciba-Geigy
(collaboration with Genencor
International Inc., U.K.)
Ecopulp'"
Irgazyme to'"
Irgazyme 40'"
4-7.5
6-7
7-8.5
55
60
50-70
ICI
(collaboration with Primalco)
Ecopulp
4-7.5
55
5.0-7.7
5.2-7.8
~
7-8
45-57
40-62
55
55
3-5.5
7-10
40-55
50-70
50-80
40-65
45-65
X-200'"
Iogen
Pulpzyme
Novo-Nordisk
HA
'"
Pulpzyme HB'"
Pulpzyme HC'"
CartazymeHS'"
Sandoz
Cartazyme ps'"
~e
sa'"
3-5.5
Solvay
Xy1anase 18000'"
Zeneca
Ecozyme'"
'Optimum
conditions
not directly comparable
the amount of chemical required to reach a

final brightness equivalent to that obtained
for a conventional pulp in which the xylan
was reprecipitated on the pulp surface (29).
Another hypothesis is that xylanases, by
catalyzing the depolymerization of xylan in
the cell walls allow entrapped lignin to diffuse more easlly out of the fiber (30).
A large part of softwood glucomannan,
the other major hemicellulose in wood, is
also dissolved in alkali but, because of its
instability, it is rapidly and completely degraded at 130C. Therefore, the amount of
glucomannan relative to that of xylan is the
same or lower in chemical pulp than in the
original wood for both hardwood and softwood. The glucomannan remaining in the
fibers, however, is resistant to dissolution
and degradation (31).
By the mid-l990s only initial studies have
been conducted to understand the mechanisms for the action of mannanases
on
chemical pulps.
4. Hemicellulos@-d@grading
enzymes
The two main enzymes which depolymerize the hemicellulose backbone are
6-8.5
6-9
because
367
tests were done independently
endo-l,4-g-D-xylanase
(EC 3.2.1.8) and
endo-l,4-g.D-mannanase
(EC 3.2.1.78), referred to generally
as xylanases
and
mannanases, respectively. Xylanases and
mannanases are produced by many species
of bacteria and fungi. Xylanases, the enzymes applied in commercial bleaching, are
available from several different sources.The
most thoroughly studied bacteria sources
include several Bactllus species and actinomycetes such as Tbermonospora fusca; the
most weU-studied fungal sources include
Tricboderma
sp., Aspergtllus
sp., and
Aureobasidium
pullulans.
Mannanases
have been studied in several laboratories (3133) and are available for commercial use.
4.1 Enzyme sources

Commercial enzyme preparations
are
comprised
mainly of the endo-l,4-g-D
xylanases. Contaminating enzymes can effect pulp quality. For example, by catalyzing
the hydrolysis of cellulose, ceUulases have
a deleterious
effect on pulp yield and
strength. Table 1 lists the predominant
xylanases available on the market in 1995.
Most of the currently marketed xylanases
have different molecular structures, and,for
368
this reason, often have correspondingly different properties. Typically, the properties
which vary among different xylanases are
related to stability, the number of catalytic
cycles occurring per enzyme unit, which
determines dosage, and the pH and temperature range required for activity.
As reported in Table I, enzymes are catalytically active over a specified pH and temperature range. Most of these enzymes are
active at neutral pH, although some function under alkaline or acidic conditions. In
mill operations, the pH of the pulp is typically adjusted with acid (usually sulfuric
acid) to a range suitable for the selected
enzyme to function.
4.2 Enzyme activity

Commercial enzymes are added to pulp
according to their catalytic activity.The catalytic activity of each xylanase, expressed in
activity units, is determined by suppliers
through calibration with xylose standards.
Activity units are defined as micromoles of
reducing sugar (xylose) produced
per
minute or moles of reducing sugar produced per second (katals) under prescribed
standard conditions. In commercial bleaching, the amount of enzyme product applied
to a pulp is based on the xylanase concentration in the particular product.
Commercial enzymes are generally stable
at ambient temperature for 6 months. Most
suppliers recommend
that during prolonged storage, the product be refrigerated
to preserve its optimum activity.
5. Process aspects of enzyme

treatments
Xylanase bleaching, from here forward
referred to as enzyme bleaching, is wellsuited for use in the bleach plant for the
following reasons:
1. Xylanases react selectively with xylan.
2. Xylanase treatment allows higher brightness ceilings to be reached with some
pulps.
3. Xylanase treatment allows bleaching sequences to be used which produce effluents containing reduced amounts of
organochlorine compounds.
4. Xylanase treatment is implemented

in
modem integrated bleach plants without
extensive capital investment.
5.1 Effects of enzyme treatments in

multi-stage bleaching sequences
Originally, the main goal in enzyme-aided
bleaching was to decrease chlorine consumption in conventional
bleaching sequences (13, 14). By the mid-l990s, mill
practice may encompass a xylanase treatment of an unbleached
or oxygende lignified kraft pulp destined for ECF or
TCF pulp production. Table 2 lists representative bleaching sequences that include
a xylanase treatment. The impact of enzyme
treatments on various parameters is discussed below.
Ttlblf!2. BIHe""'g~COIII"'''mg''xy'Ir'HImeIIt.
Conventional
ECF
TCF
XCEDED
X(CD)EDED
XDED
OXDED
OX(CD)ED
X(EOP)D(EOP)D
X(EP)P
ZX(EP)
XZ(EP)
OXQPZP
OXZP
OX(EP)ZP
OXDP
Effect of enzyme treatment
on kappa
number
Two aspects of the effect of enzyme treatments on kappa number are important to
bear in mind: First, the effect of the starting kappa number on the overall benefit
derived from enzyme use and second, after
enzyme use, the significance of kappa number in terms of the amount of chemical required to bleach a particular pulp.
The magnitude of the effect of enzymatic
treatments depends on the pulping process
and starting kappa number. In general, the
greater the residual lignin content of the
pulp,(i.e., the higherthe initial kappa number), the greater the effect ofaxylanase
treatment in bleaching sequences.
An example of this trend has been shown
by laboratory
experiments
in which
xylanase treatments were performed on
different softwood kraft pulps made by eX-

tended delignification (EXT pulps) having
kappa numbers varying between 26.8 and
13.1 and oxygen-delignified softwood kraft
pulps (OX pulps) whose kappa numbers
ranged from 26.9 to 6.4 (34). The results
indicated that higher amounts of lignin with
higher average molecular weight were extracted by alkali after xylanase treatment of
conventional and extended pulping kraft
pulps having higher starting kappa numbers
than from xylanase-treated
pulps having
lower starting kappa numbers. The amount
of lignin extracted from an EXT pulp compared with that from an OX pulp with the
same kappa number was also clearly different with more lignin being extracted from
the former. Therefore, the pulping process
and starting kappa number affected the
quantity of lignin eventually removed from.
the pulp after xylanase treatment and alkali
extraction.
The chlorine multiple (kappa factor) required for pulps which had first received a
xylanase treatment was found to be 75-80%
of the chlorine multiple required for conventional, non-enzyme-treated
northern
hardwood kraft pulps (35). In this study,
enzyme-treated
and conventionally
bleached pulps were found to have approximately the same kappa number (1.85-2.0)
after the CE stages. Based on the kappa
number, each pulp should have contained
about the same amount of residual lignin.
However, the enzyme-treated pulps had a
final brightness 6-10 points above those of
the conventionally treated pulps (35). In
the sequence X(E+O+P)D(E+O+P)D (1.2%
total chlorine dioxide), used to bleach
mixed hardwood kraft pulp (starting kappa
number 13.5), the final ISO brightness of
the xylanase-treated pulp was 89.6 while
that of the non-xylanase-treated
(control)
pulp was 83.S.
An explanation for the effect of xylanase
treatment on kappa number has not been
established. It has been postulated that the
chlorine multiple and CE kappa number of
pulps receiving an enzyme treatment differ
from those found in control pulps for the
following reasons (36):
1. Xylanases effect the removal of specific lignin structures, leaving a residual lignin in
369
the pulp which may be more responsive

to permanganate oxidation than the re- .
siduallignin in conventional pulps. Thus,
the quantities of lignin represented by
kappa numbers of between 1.85 and 2.0
in conventional and enzyme-treated pulps
may not be identical but actually lower in
the enzyme-treated pulp. lignin in the enzyme-treated pulps may respond better to
oxidation by permanganate; the enzymetreated pulp samples, which contain less
lignin, are bleached to a higher brightness
than conventionally bleached pulp.
This explanation may account for the residual chemical commonly observed after
the first stage of a bleaching sequence preceded by a xylanase treatment but which
is not observed when the enzyme treatment is omitted.
2.The lignin contents of the enzyme-treated
and conventional pulps are identical, but
proportionately more lignin is removed
from the fiber surface receiving the enzyme
treatment, resulting in a higher final pulp
brightness.
Regardless of the mechanism of enzyme
bleaching, the kapp.a number continues to
be an often unreliable indicator of Klason
lignin content, and does not indicate structural differences in the lignin which may
become manifest in the following bleaching stages.
Effect of xylanase treatment on bleaching
chemical requirements
Xylanase-treated pulps do not respond to
bleaching chemicals in the same manner as
untreated pulps. Significantly less chlorine
is needed to bleach enzyme-treated pulps
than is indicated by kappa number alone.
Moreover, enzyme-treated pulps are significantly brighter than untreated
pulps
bleached to an equivalent CE kappa number.
Frequently used bleaching sequences following a xylanase treatment employ reduced amounts of chlorine and chlorine
dioxide. The reduction in chlorine-containing chemicals resulting from the use of
xylanases when bleaching to the same or
higher final brightness has been primarily
responsible for the rapid commercialization
of xylanases in the paper industry. The reduction in chlorine-containing
chemicals
has important implications not only for the
370
environment,
but also for some mills
through cost savings or increased pulp production capacity through expansion of the
chlorine dioxide generator capacity.
Enzo-Gutzeit was first to patent a process
for the reduction of chlorine bleaching
chemicals through use ofaxylanase
treatment (21).The introduction of an enzyme
treatment before a D<)OC1oE
sequence had
the effect of reducingAOX from 1.0 to 0.6
kg/ton of pulp and the COD from 55 to 40
kg/ton of pulp.
Xylanase-treated pulps respond to varying chlorine dioxide substitution differently
than do untreated pulps (37). The traditional untreated pulp shows a concave
curve when total chlorine charge (% on
pulp) is plotted against chlorine dioxide
substitution and the characteristic
minimum charge requirement corresponds to
40% substitution
(38). Xylanase-treated
hardwood pulps bleached at 10% chlorine
dioxide substitution levels surprisingly require less total chlorine than at other substitution levels. A possible explanation for
this effect may be the sensitivity ofxylanasetreated pulps to the addition of chlorine and
chlorine dioxide.
Although savings in chemicals are also
obtained when enzyme treatments precede
the multi-stage bleaching of hardwood kraft
pulps, the economic benefit is larger for
softwood. Undoubtedly this is because the
lignin content of softwood pulps ls higher
and therefore they benefit more than hardwood pulps from delignification-promoting
enzymatic treatments.
du Manoir and Dubelsten
(39) have
shown that kraft pulp can be more effectively delignified and bleached in sequences
that include an oxygen delignification step
and a xylanase treatment.This combination
allows bleaching to be performed with
lower amounts of chlorine-containing
bleaching agents or in the absence of elemental chlorine (in an ECF sequence). Preferred processes consisting of oxygen and
xylanase treatments include an OXC/OED
or OXDP sequence. The results in Table 3
show the favorable effect on final bright-
ness ofaxylanase
treatment after oxygen
delignification of northern hardwood kraft
pulp (22). In addition, the kappa number
was reduced by about 60",.(,following oxygen delignification and xylanase treatments.
The chemical charges applied to the oxygen-delignified and xylanase-treated pulp
in the subsequent C/O, E,and D stages were
significantly less than those required to
reach the same or even higher final brightness using a C/OEDED, OC/OED, or XCI
CED sequence.
Tultl 3. IIl/tlCt of O:JrYIIIIItkllpiflctltwII
tlrut tI
trntrrumt 011softwood lnwft Jnllp
xy"""propertks.
Treatment
None
(unbleached
pulp)
0
X
OX
OX(C+D)ED
Kappa
Number
Viscosity Brightness
(% ISO)
(mFa's)
14.1
8.3
10.8
49.1
5.3
26.6
55.9
25.7
90.5
34.3
Xylanase can be used in TCF sequences

to reduce the application of other non-chlorine bleaching agents. Ledoux et at. (40)
used a xylanase in TCF sequences containing an ozone stage. Results for hardwood
kraft pulps indicated ISO brightness values
in the 88%+ range, higher DP values, and
reduced ozone applications. Similar brightness and DP values were obtained for all
bleaches such as XOQPZP, OXQPZP, and
OQPXZP. Moving the X stage closer to the
Z stage appeared to lower the ozone charge
required to reach the same final brightness.
Eriksson and co-workers (41, 42) have
conducted studies on combined enzymeozone treatments, referred to as the En
Zone~ process. They demonstrated
that
xylanase treatments enhance the brightness
of ozone-treated pulps and reduce oxidative damage to the cellulose fibers. Examples cited include eucalyptus pulp fully
bleached to an ISO brightness of 90% in a
OXZP sequence using 0.8% (w/w) ozone
Bleaching
sequence
371
CWorine
% on Pulp
CWorine Dioxide
%on Pulp
Brightness
%
Yield
%
91.9:t0.7
(1)
(CD)(EO)DED
2.6
0.5
88.8
(2)
(CDXEOP)D(EOP)D
2.6
88.8
(3)
X(EOP)D(EOP)D
0.0
0.3
1.1
89.0
92.2:t1.2
(4)
(EOP)D(EOP)D
0.0
1.8
87.4
93.7:t1.0
(5)
X(EO)D(EOP)D
0.0
0.9
86.3
(6)
(EO)D(EOP)D
0.0
2.2
87.0
'Unbleached
on pulp.
bleached
quences
ozone to
kappa number:
372
Pulp to
final
bleaching
14.5
Pine kraft and superbatch pulps,

using OX(EP)ZP and X(EP)ZP serespectively,
needed 0.8-1.0%
reach 85-90% brightness.
Effect of xylanase treatment on bleached

pulp yield and physical properties
The effect of xylanase on the final yield
of fully bleached pulp is not fully understood. Too much applied 'xylanase leads to
a decreased yield because of hemicellulose
loss. Yield losses associated with early trials can be attributed to the presence of cellulase which is no longer a contaminant in
xylanase products. Yield losses may also
occur if excessive amounts of xylanase are
applied for long periods of time.
The yields of enzyme-treated hardwood
kraft pulp bleached in ECF and chlorinecontaining sequences (35), shown in Table
4,indicate that the yield of hardwood kraft
pulp bleached to the same brightness in an
ECF sequence preceded by a xylanase treatment X(EOP)D(EOP)D is about the same as
that obtained
using a conventional
sequence (CD)(EO)DED. A typical bleaching sequence for northern hardwood kraft
pulp using 2.6% equivalent chlorine, in the
sequence (CDXEO)DED, gave 88.8% final
brightness with a yield of 91.9:t0.7%. An
enzyme treatment followed by a (EOP)D
(EOP)D sequence, with 1.1 % chlorine dioxide used in the D-stages, gave a final
brightness
of 90.0% and a yield of
92.2:tl.2%.Therefore,
enzymatic treatment
of unbleached
kraft pulp, which is later
bleached in a chlorine-free sequence, gives
essentially equivalent final brightness and

yield as did the conventional chlorine-containing bleach sequences.
Extensive testing of xylanase-treated
pulps indicates that such pulps need equivalent or sometimes slightly more energy to
refine to the same freeness than do pulps
bleached in chlorine-containing
bleaching
sequences. At the same freeness, both types
of pulp show equivalent sheet strength. In
one mill trial, extensive testing of pulp quality parameters
demonstrated
that the
xylanase-treated pulp was of the same, if
not better, quality as typical (t.e., untreated)
pulp produced at the mill (43).
Results from another mill study in which
xylanase was used indicated that the average pulp viscosity was not significantly altered and that the handsheet
strength
properties and the beatability of enzymetreated pulp (tear and tensile) were equal
to those obtained during the control period
(44). The zero-span breaking length of the
pulps was also not markedly changed by the
xylanase treatment.
5.2 Environmental effect of enzyme

treatments
Effluent properties, namely AOX, COD,
and color, are improved indirectly through
the use of xylanase treatment which promotes lignin removal and allows lower
amounts of chlorine-containing
chemicals
to be used.
In sequences employing 90% chlorine
dioxide substitution and an alkaline extraction after the enzyme treatment, AOX was
reduced to 0.6 kg per ton of pulp and COD

to 40 kg per ton pulp compared with noenzyme treatment sequences where AOX
and COD were, respectively, 1 and 55 kg
per ton of pulp (45).
A laboratory study of oxygen-delignified
softwood kraft pulp bleached using the ECF
sequence,
XD(EOP)D, was conducted to
determine the impact ofxylanase treatment
on effluent quality based on the chemical
required to reach 85% ISO brightness starting with pulps having different kappa factors (46). The use ofthe enzyme stage in
this study led to the replacement of nearly
5 kg of chlorine dioxide per ton of pulp.As
anticipated, the total amount of AOX generated decreased with decreasing kappa
factor.
6. Enzymetreatments in the
bleach plant
As indicated above, the use of enzymes
can reduce bleaching chemical requirements and preserve or enhance pulp quality while maintaining equivalent yield at
comparable final brightness. Before introducing an enzyme treatment in the bleach
plant, it is useful to address the following
questions:
1. What is the driving force for enzyme usage (environmental, reduction of bleach-
ing chemical, cost,AOX reduction, chlorine dioxide generator bottleneck, dioxin

concerns)?
2. Where are the preferred
application
points for enzyme?
3. How can the pulp be monitored to maintain the proper pH?
4. How will enzyme effectiveness be monitored?
S. What are the "criteria for success" and
the benefits required to justify enzyme
use?
6.1 Process flowsheets
Figures 1 and 2 show schematics of the
typical equipment and flow configuration
for pH control and enzyme treatment of
unbleached kraft pulp in conventional and
TCF bleaching sequences.
The application of xylanase to a pulp
under mill conditions is relatively straightforward: usually only a pump is needed to
deliver, at a flow rate of about 1 liter per
minute, the enzyme solution to the pulp
slurry before it enters the high-density storage tower. When enzyme is added to unbleached kraft pulp, it may also be necessary
to adjust the pH level to a range compatible with the enzyme activity, usually between 4 and 9. Some enzymes also can be
readily added in conjunction with a chela-
373
374
Pulp Bleaching
Ttlble 5. DeserlptUm
Pulp to
final
bleaching
Fig. 2. SebelluUk
oflyJtlall
Mzyme
tm4 iIdd .Mi,,,,,
tion (Q) stage at a pH of approximately 4 to

4.5 or immediately following an ozone stage
at pH 3.5.
Acidification of unbleached kraft pulp to
a pH range appropriate for enzyme activity
can be achieved with various acids; typically, sulfuric acid is used in most mills although C-stage filtrate or chlorine dioxide
generator waste acid may also be used.
Aqueous sulfur dioxide has been used successfully in mills to acidify pulp before a
xylanase treatment, but its use is not recommended because of its high corrosivity
and potential for consuming chlorine dioxide in later bleaching steps if it is not adequately washed from the pulp. Caution
must be taken at pH levels below 5 to ensure that the acidity selected is compatible
with the metallurgy and the high-density
storage tower lining and grouting.
Enzyme dispersion, as determined
by
tracer tests, ls significantly better with a
shower bar than with other addition systems. Enzymes typically are mixed with
water before being added to the repulper
side of the brown stock decker by a shower
bar. The pulp is allowed to react with the
enzyme in the high-density storage tank for
at least two hours before being conveyed
to the next stage of the bleach sequence.
-.11$
and Practice
of mill trIIIls witb enzymes.
Mill
Trial
Enzyme
Pulp
Bleaching
Sequence
Pulpzyme HB
Hardwood
OX
Albazyme 10
Softwoods
XD(E+O+P)DED
Cartazyme HS
Eucalyptus
X(E+O+P)D(E+P)D
logen Xylanase
Unknown
X(DCXE+O)DED
Ecopulp
Softwood
(MCCb)
XD(E+O)D(E+P)D
Result
18%decrease
in bleaching
chemical usage
ACM' decreased
by 28.3%;
15%decrease
inCIO,
Brightness
increase of 5-7 pts
23% decrease in
equivalent chlorine
ACMdecreased
by 26%;
16%decrease in
CIO, usage
Reference
50
48
43
49
'ACM -Active chlorine multiple

bMCC Modified continuous pulping
I. TCF seqwru:e.
Effective enzyme and acid addition systems

can:
1. Control pulp pH to an acceptable
range
"
2. Proportionately
pulp
tm4
-Principles
apply enzyme
to the
3. Adequately mix the enzyme with the pulp

4. Monitor process variables important to
enzyme performance (pH, temperature,
and acid addition)
5. Respond quickly to mill upsets to ensure
the xylanase treatment proceeds without
interruption.
6.2 Economic factors in xylanase

treatments
Estimates for the 1995 capital cost of
enzyme delivery and pH adjustment vary
from (US) $10,000 to (US) $100,000. For
mills that already have existing equipment
for adjusting pH to minimize pitch problents, the capital cost is lower.
Enzymes are sold as concentrated liquids
and the amount required per metric ton of
pulp is small (- 0.1 L).The cost of enzyme
per ton of pulp is variable and depends on
the dosage required and supplier. In 1995,
a target price of about (US) $3.50 per metric ton of pulp could generally be assumed,
(US) $3500/day for a 1000 ton/day mill.
A calculation of savings in other bleaching chemicals can be made as follows: for

a 1000 ton/day mill bleaching softwood
kraft pulp of 26 kappa number using an ECF
sequence, a reduction of approximately 5
kg CI0,lton of pulp might be achieved.
Assuming a chlorine dioxide cost of (US)
$0.70 per kg, an estimated (US) $3500/day
can be saved in chlorine dioxide costs.
Additional savings in alkali (caustic soda)
can also be expected. Reduced peroxide
requirements arising from enzyme use can
also reduce overall bleach costs.
6.3
Effect of conditions
bleach plant
external
to the
Mill operations external to the bleach

plant can influence the overall effect of
enzymes in bleaching (47). Two of the more
significant influences are described below.
1. Chip Furnish: Among chip furnishes, the
most important distinction is between
hardwood and softwood because hemicellulose content and structure in each
are different. Most mill activity has been
focused on softwood use because of its
higher chemical requirements in bleaching. In general, hardwood hemicelluloses are more responsive to xylanase enzyme action than are those in softwood.
The percent savings in bleaching chemicals is therefore greater for hardwood

than for softwood but the overall economic benefit is less.
Among hardwood pulp species there is
considerable variation in the benefit received from enzyme treatment. For example, after conventional kraft pulping
to kappa number 15, aspen shows 30%
less and oak and eucalyptus shows 30%
more response to enzymes than most
other hardwood species. Among softwood pulp species, less variation in response to enzyme treatment is observed.
2. Digester Operation: Digester operation
can affect the content and structure of
the hemicelluloses in a pulp which, in
tum, affect the response of the pulp enzyme action. Kraft pulping under severe
conditions, such as those used in the
conventional pulping of softwoods to
kappa numbers less than 23, remove
much of the hemicellulose which is accessible to the enzyme. On the other
hand, MCC- or oxygen-delignified pulps
having low unbleached kappa numbers,
respond well to enzyme treatment (J 1).
MCC- and oxygen-delignified pulps contain hemicellulose
structures that are
similar to those in conventional, highkappa number pulps. Enzyme treatment
benefits have been achieved in mills us-

ing conventional,
MCC, and oxygen
delignification systems. Mill experience
has shown that the addition of anthraquinone during kraft pulping tends
to preserve hemicellulose content and
produce pulps which also respond well
to enzyme treatment.
3. Unbleached Kraft Pulp Washing: Mill experience has shown that day-to-day variation in the extent of brown stock washing has little impact on enzyme performance.
6.4 Benefits in bleach plant operations
Table 5 summarizes the published results
of mill trials in which xylanase has been
used. Collectively, these findings confirm
the previously observed benefits of xylanase
in reducing bleaching chemical requirements and improving brightness.
In mill trials,results were reported on the
brightness gain at each stage of the bleach
sequence (48).The gains in ISO brightness
for pulp bleached using- the enzyme-preceded ECF sequence (X(E+O+P)D(E+P)P),
after each stage, compared with a no enzyme-treatment,
ECF sequence, were not
equivalent and ranged from a 4- point to
12.2-point brightness gain with enzyme
compared with the no-enzyme treatment sequence and imply again that the residual
lignin after xylanase treatment may be different from the residual lignin in pulp
bleached by conventional bleach stages.
Not all xylanase mill trials have been fully
successful, though such findings are not
often reported in the literature. If the enzyme or acid is not well-mixed with the pulp
or if the pH and temperature fall outside of
the optimum range for the enzyme during
a considerable part of its residence time on
pulp, the bleaching effect will be diminished. In mill trial E (fable 5),lithium tracer
studies revealed that tower channeling effectively reduced the retention time (49).
This problem was corrected by raising
tower levels to the degree necessary to ensure adequate retention. Also, several reports of acid-related corrosion damage
provided a clear indication that metallurgy
requirements must be considered.
375
7. Future prospects
Pulp and paper mills are presently facing
formidable regulatory pressure to reduce
the discharge of chIoIDQrganic substances
(as represented byAOX) and other wastes.
The industry is assessing various technol~
gies to identify means for achieving less than
0.2 kg ofAOX/ton of pulp in effluents. This
target is achievable using extended pulping,
oxygen delignification, pulping additives
(i.e., anthraquinone),
and ECF bleaching;
however, older mills are faced with meeting the targets without the advantages of
capital funding to install this equipment.
Mill data suggest that xylanases may be an
important factor in helping such mills meet
the AOX discharge limits.
The eventual significance of enzyme
bleaching in the pulp and paper industry
remains to be detertnined.The
technology
is relatively new and the mechanisms of
enzyme action are not fully understood.The
commercial xylanases currently available
offer the advantages of reduced bleaching
chemical requirements'for
high brightness
pulp, relatively low cost, ease of application, and great selectivity. Researchers continue to isolate new xylanases and to
investigate the effect of other hemicellulases and ligninolytic enzymes such as lignin peroxidase, laccase, and manganesedependent peroxidase on pulp bleaching.
References
1. Pedersen, L., Elm, D.D., Nissen, A.M.,
Choma, P.P.,"Bleach Boosting of Kraft Pulp
Using Alkaline Hemicellulases," International Chlorine-Free Bleaching Conference,
Stockhoim Proceedings, 1991, Vol. 2, p.
107.
2. Eriksson, K.-E., Blanchette, R.A.,Ander, P.,
in Microbial and Enzymatic Degradatiotl
of Wood and Wood Components
(T. E.
Timell, Ed.) Springer-Verlag, Heidelberg,
1990, Chap. 2.
3. Kirk,T. K. and Cowling, E. B., in The ChemistryofsolidWood.(R.M.Rowell,Ed.)
Adv.
Chern. Ser. 207, American Chemical Society, Washington, D.C., 984, pp. 455-487.
376
4. Yang, H. H., Effland, M., Kirk, T K., Biotech.

Bioeng. 22:65 (1980).
16. Paice, M. G., Bernier, R. Jr., Jurasek,

Biotechnol.
Bioeng. 32:235 (1988).
5. Gold, M. H., Glenn,].

K., Mayfield, M. B.,
Morgan, M.A., Kutsuki, H., in Recent Advances
in Lignin
Biodegradation
Research (T.Higuchi, H.-mChang,
T.KKirk,
Eds.) Uni, Tokyo 1983, p. 219.
17. Clark, TA., McDonald, A.G., Senior, D.].,

Mayers, P.R. in Biotechnology
in Pulp and
Paper Manufacture
(T.K. Kirk and H-m.
Chang, Eds.), Buttersworth-Heinemann
Boston 1989, pp. 153-167.
'
6. Tien, M. and Kirk, TK., Science

(1983).
18. Boutelje, S., Eriksson,

H., Svensk Papperstidn
221:661
7. Shimada, M. and Higuchi, T, in Recent

Advances
in Lignin Biodegradation
Research, (T. Higuchi, H.-m. Chang.,T K. Kirk,
Eds.) Uni, Tokyo, 1983, p. 195.
8. Kirk, T K. and Farrell, R. L., Annu.
Microbiol., 41:465 (1987).
Rev. of
9. Farrell, R. L., "Kraft Pulp Bleaching with

Ugninolytic
Enzymes,"Third
International
Conference
on Biotechnology
in the Pulp
and Paper Industry
Proceedings,
STFI,
Stockhoim,
1986, p. 86.
10. Shimada, M., Fushiki, H., Higuchi, T, Phytochemistry
11:2247 (1972).
11. Bourbonnais,
R., Paice, M. G., Reid, I. D.,
"lignin Oxidation and Pulp Delignification
by Laccase of Trametes versicolor in the
Presence ofABTS," Fifth International
Conference on Biotechnology
in the Pulp and
Paper Industry Proceedings,
Kyoto, 1992,
p. 181.
12. Call, H. P. and Miicke, I., "State of the Art
of Enzyme Bleaching and Disclosure of a
Breakthrough
Process," Paper presented
at Non-chlorine
Bleaching
Conference
Proceedings,
1994.
13,Vtikari, L., Ranua, M., Kantelinen,A.,
Unko,
M., Sundquist,]., Third International
Notes,ATIP, Paris, 1987, p. 151.
14. Kantelinen,A.,
Ranua, M. Ratto, M., Viikari,
L., Sundquist,]., Unko, M., "Hemicellulases
and Their Potential
Role in Bleaching,"
Pulp Bleaching
Conference
Proceedings,
TAPPI PRESS,
Atlanta, p. 1.
15. Chauvet,].
M., Comtat,].,
Noe, P., "Assistance in bleaching of ncverilricd
pulp by
the use ofxylanases, consequence
on pulp
propetties,"
International
Symposium on
Wood and Pulping
Chemistry
Notes,
ATIP, Paris,
1987,
p. 325.
L.,
K-E., Hallmark,
74:32 (1972).
B.
19. Sinner, M., Paramesivaran,

N., Dietrichs,
H. H., Liese, W. Holzforschung
27:36
(1973).
20. Paice, M.G., Jurasek, L.,
Tech. 4(2):187 (1984).
21. Salkinoja-Salonen,M.
M.,PatApplication
14, 1988).
Wood
Chem.
,Vaheri, M., Koljonen,

No.FI881192
(March
22. Lavielle, P., Koljonen,

M., Piioinen,
P.,
Koponen, R., Reid, D., Frederiksson,
R.,
"Three Large Scale Uses of Xylanases in
Kraft Pulp Bleaching," Proceedings,
SPCI,
Bologna, 1992 p. 203.
23. Senior,
66:111
D. J., Hamilton,
(1992).
J.
Pulp
Pap.
24. Viikari, L., Kantelinen,A.,

Unko, M., FEMS
Microbial. Rev. 13(2-3):335 (1994).
25. Sjostrom, E., Wood Chemistry Fundamentals and Applications,
2nd edn., Academic Press, San Diego, 1993.
26. Eriksson, 0., Goring, D.A.I., Lindgren,
B.O., Wood Set. Technol. 14:267 (1980).
27. Viikari, L., Kantelinen,A.,
Buchert,].,
Puls,
]., Appl. Microbiol. Biotechnol.
41 (1): 124
(1994).
28. Kantelinen,
A., Sundquist,].,
Linko, M.,
Viikari, L., "The Role of Reprecipitated
Xylan in the Enzymatic Bleaching of Kraft
Pulp;' Sixth International
Symposium
on
Wood and Pulping
Chemistry
Notes,
APPITA, Parkville,
Victoria,
Australia,
1991, Vol. 1, p. 493.
29. Chang, H.-m., and Farrell, R. L., Sixth International Conference on Biotechnology
in the Pulp and Paper Industry Proceedings,Technische
Universitat,Vienna,
1995.
30. Pake, M.G., Gurnagul,
N., Page, D.H.,
Jurasek, L., Enzyme
Microbiol.
Technol.
14:272 (1992).
--...--Chapter IV 7: Enzyme Treatments of Pulp

31. Clark, T.A., Steward,
D., Bruce, M.E.,
McDonald, A.G., Singh, A.D., Senior, D.}.,
Appita 44:389 (1991).
32. Stalbrand, H., Siika-Aho, M., Tenkanan, M.,
Viikari, 1., J Biotechnol.
20(3): 229
(1993).
41. Yang, }.L., Cates, D.H., Sacon, V.M., Law,

S.E., Eriksson,K.-E.-L.,"Bleaching
of Kraft
Pulps with Enzyme and Oxygen-based
Chemicals," 1993 TAPPI Pulping Conference Ptoceedings,
p. 1033.
42.Yang,}.L.,
33. Biely, P., and Farrell, R. L., Sixth International Conference on Biotechnology
in the
Pulp and Paper Industry
Proceedings,
Technische
Universitat, Vienna, 1995.
34. Suurnakki, A., Kantelinen, A. Buchert,}.,
Vrikari, L. Tappi J 77(11): 1 II (1994).
35. Skerker, P.S., Farrell, R.L., Chang, H-m.,
"Chlorine
Free
Bleaching
with
CartazyrneTM HS Treatment," International
Ptoceedings,
SPCI, EUCEPA, Tech. Sect., CPPA, TAPPI,
Stockholm,
1991, vol. 2, p. 93.
36. Farrell, R.L., Skerker, P. S. in Xylans and
Xylanases,
O. Visser,
Ed.) Elsevier,
Amsterdam,
1992, p. 315.
37. du Manoir,}.R., Hamilton,}.,
Senior, D.}.,
Bernier, }.E., Moser, L.E., Dubelsten,
P.,
"Biobleaehing
of KraffPulps
wtth CeUulase-Free Xylanase,"
International
Pulp
Ptoceedings,
SPCI,
EUCEPA, Tech.
Sect.,
CPPA, TAPPI,
Stockholm,
1991, Vol. 2, p. 123.
38. Senior, D.}., Hamilton,}.,
"Xylanase Treatment for the Bleaching of Softwood Kraft
Pulps:The Effect of CWorine Dioxide Substitution," 1992TAPPI Pulping Conference
Ptoceedings,
39. du Manoir,}. R., Dubelsten,
P., U. S. Pat.
No. 5,179,021 Qanuary 12, 1993).
40. Ledoux, P., Detroz, R., de Buyl, E., Shetty,
)., Troughton,
N., Presley, }. R., "Use
of Bacterial Xylanase in Chlorine
Free
Bleaching Sequences," 1993 TAPPI Pulping
Conference
Proceedings,
TAPPI PRESS,
Atlanta, p. 1057.
377
Lou, G., Eriksson,
K.-E. L., Tappi
J 75:95 (1992).
43. Luers, M., "Biobleaching
at Skeena Cellulose," 1993 TAPPI Pulping Conference Pr0ceedings, TAPPI PRESS,Atlanta, p. 12.
44. Scott, B.P., Young, E, Paice, M.G.,
Pap. Can. 94(3):75
(1993).
Pulp
45. Senior, D., Hamilton,).,

"Use of Xylanase
to Decrease the Formation ofAOX in Kraft
Pulp
Bleaching,"
J Pulp Pap. Set.
18(5):165 (1992).
46. Vegega, A.M., Elm, D.D., Strunk, W.G.,
Choma,P.P.,
Sezgi,A.,"Low Kappa Factor
Bleaching of Oxygen Delignified Softwood
Kraft Pulp," 1993 TAPPI Pulping Conference Proceedings,
p. 1049.
47.Tolan,}.S.,"Using
Enzymes in Pulp Bleaching," CPPA Bleaching Course Manual,Tech.
Sect., CPPA, Montieal, 1993.
48. Turner,}.
c., Skerker, P.S., Burns, B.).,
Howard,}.C.,Alonso,
M.A., Andres,). L.,
TapptJ 75:83 (1992).
49.)ean, P., Hamilton,), Senior, D.}., Pulp Pap.
Can. 95:126 (1994).
50. Vaheri, M., Miiki, K, Jokela, v., Kitunen,
v., Salkinoja-Salonen,
M., "Bleaching
of
Kraft Pulp Without Formation of Dioxins."
Ninth International
Symposium on CWorinated Dioxins and Related Compounds
Notes, NCASI, Corvallis, OR/Environrnent
Onario, Rexford, Ont., 1989.
-------._-
SEcnON IV:
The Technology of
Chapter 8:
Chlorine Dioxide in
Bleaching Stages
Douglas W. Reeve
and Applied Chemistry
and the Pulp & Paper Centre
Toronto, Ontario
1. Introduction.
......................................................
381
"
2. Chemistry and kinetics

2.1 Chemistry
2.2 Kinetics
381
381
382
3. Process tlowsheets and conditions . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . ..

3.1 FIowsheets, equipment, and bleaching sequences. . . . . . . . . . . . . . . . . . . . . .
3.2 Chemical charge and residual. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3 pH
3.4 Time and temperature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.5 Consistency
3.6 Influence of chlorine and chloride ion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.7 Washing and carryover. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
383
383
385
388
390
391
391
392
4.E~eerbmgconsiderations
4.1 Mixing
4.2 Chlorine dioxide solution heating
392
392
393
5. Pulp quality
.. .. .. .. .. . .. .. .. .. .. .. .. .. .. . .. . .. .. .. .. .. .
6. Environmental factors
" " " " " ".
393
393
379
Chapter IV 8: CWorine Dioxide in Bleaching Stages
Chapter IV 8:
Chlorine Dioxide
in Bleaching Stages
381
2. Chemistry and kinetics

2.1 Chemistry
portant chemicals used for bleaching chemical pulp because it reacts readily with lignin
and does not react to any significant extent
with carbohydrates.
It can be used to
achieve high brightness and is also extremely effective in bleaching particles.
Chlorine dioxide bleaching has been essential to the manufacture of strong, stable,
clean, high-brightness kraft pulp. Economical means of manufacture and use of chlorine dioxide were developed in the 1940s.
This technology
was essential for the
growth of the bleached kraft pulp industry.
Until very recently, all mills manufacturing
bleached kraft pulp of brightness greater
than 80 had to use chlorine dioxide.
An interesting survey' of chlorine dioxide bleaching in North America was published by Rapson in 1958 (1). Chlorine
dioxide stages in operation grew from 1 in
1946 to 9 in 1953, and to 43 in 1957; 60%
of the mills employed only one stage of
chlorine dioxide in the bleach plant and
40'>,1,
used two stages; 74% of chlorine dioxide bleaching stages were in kraft mills and
20% were in sulfite mills; 58% of the chlorine dioxide generators were Mathieson and
34% were Solvay generators.
From that
time, chlorine dioxide bleaching stages
grew to be universal in kraft mi1ls producing bleached market-grade kraft pulp. There
are a number of comprehensive references
on chlorine dioxide bleaching beginning in
1953 (2-6).
In this chapter, the use of chlorine dioxide to brighten pulp in the latter stages of
bleaching sequences is discussed, including
chemistry and kinetics, process flow sheets
and process conditions,
bleaching
se-
Chlorine dioxide gas is unstable; when

the concentration in the gas phase exceeds
100 mm Hg partial pressure, it spontaneously decomposes to chlorine and oxygen,
sometimes explosively. Chlorine dioxide is
therefore generated at the pulp mill site,
absorbed into chilled water to form a dilute solution, generally 8-12 grams per liter at 5-1O"C. Depending on the generator
process, some chlorine may be present in
the solution. When cool chlorine dioxide
solution is added to hot pulp, chlorine dioxide vapor can be released. To prevent
such release, chlorine dioxide bleaching
towers are designed to provide a significant
hydrostatic head at the point of chemical
addition which maintains sufficient pressure to keep the chlorine dioxide in solution until it reacts with pulp. Chlorine
dioxide bleaching towers are therefore
upflow towers or upflow-downflow towers.
Chlorine dioxide reacts with lignin fragments responsible for light absorption in the
visible region. The chemistry of these reactions is discussed in detail in Chap. III 3.
Some lignin fragments remain in the pulp
and some are dissolved. Chlorine dioxide
reacts only to a minor extent with carbohydrates; aldehyde groups are oxidized to carboxyl groups.
As shown in Fig. 1 of Chap. IV 3, when
chlorine dioxide reacts with pulp, a number of intermediates containing chlorine are
formed before chloride ion, the ultimate
reaction product, is produced. The first step
is the formation of chlorite ion (CIO;).
Chlorite ion then reacts with the pulp forming hypochlorous acid (HCIO) which in turn
reacts with the pulp to form chloride ion
(Ct"). Hypochlorous acid can form chlorinated organic structures by reaction with
pulp. It is important to note,as is discussed
in more detail later in Chap. IV 3, that chlorite ion does not react when the pH is above
quences, engineering considerations, pulp
4 and, therefore, the bleaching potential of
quality and, finally, environmental factors.

It is important to note that the use of chlorine dioxide as a delignification agent has
been described in Chap. IV 3.
the chemical added is lost. Further, the intermediates formed by reaction with the
pulp react with one another to form chlorate ion (CI03'). Chlorate ion does not react
1. Introduction
CWorine dioxide is one of the most im-
382
with the pulp and also represents a loss of

bleaching potential. Further information on
the intermediates and reaction mechanisms
in chlorine dioxide bleaching can be found
in Chap. IV 4 and Chap. III 3 (7-12).
CL
],
0.15
--E0
""
pH 2
CWorate Formed
(mole % of Cl02 added)
pH
pH 3
E 0.10
11'
E
.E
S 0.05
oi!
:2
u
0.10
0.2
0.3
0.4
ClO, consumed, mmoll g pulp
38
28
17
(Ref. 17)
28
15
(Ref. 19)
Formation of chlorate ion decreases the

efficiency of chlorine dioxide bleaching
(13-17). Chlorate formation is proportional
to chlorine dioxide consumption
and
strongly dependent on the bleaching pH as
is illustrated in Table 1 (15, 17). Low-<:onsistency,constant-pH experiments have also
demonstrated these characteristics as is illustrated in Fig. 1 (16). Chlorate formation
is unaffected by temperature and chlorine
in chlorine dioxide solutions (13). Most
chlorate formation takes place in the first
15 minutes of the bleaching reaction (13).
If 20% chlorine dioxide is converted to chlorate, 2.5 kg of chlorate ion will be formed
for each 10 kg of chlorine dioxide added
per metric ton of pulp. Chlorate is also
formed when chlorine dioxide is used in
delignification as discussed in Chap. IV 3.
In delignification stages, less than 20% of
chlorine dioxide is converted to chlorate.
It has been found that carbon monoxide
is formed during chlorine dioxide bleaching (18, 19). This led to a fatality in 1980
when a workman entered a chlorine dioxide tower to make repairs (18); up to 7%
carbon monoxide was found in the gas at
the top of the chlorine dioxide towers studied. An extensive study of the chemistry of
carbon monoxide formation has also been
reported (/9).
When chlorine dioxide oxidizes pulp,
organic acids are formed. These acids and
hydrochloric acid (from and chloride ion)
0.5
formed from the chlorine dioxide, lead to a

decrease in pH. To counter this decrease
and to establish optimal pH conditions, sodium hydroxide may be added.
2.2 Kinetics
The kinetics of pulp bleaching with
chlorine dioxide have been thoroughly described (20). The light absorption coefficient of pulp (k457)is directly proportional
to the concentration
of chromophores
in
the pulp and is related to pulp brightness
and light-scattering
coefficients
by the
Kubelka-Munk equation (see Chap. VII 2).
Figure 2 shows the rate of decrease in
k457
for pulps prebleached using different sequences (20). These experiments
were
conducted at low pulp consistency and at
constant chlorine dioxide concentration
and pH. The kinetic expression for the
elimination of chromophores
is given below:
-dkm = k[Cl02]05[H+lo.3 (k457-k457~)3 [1]
dt
where
k457
= the
light absorption
coefficient
at
457 nm
(k457)~
= km
for the unremovable
chromophores
This equation describes the elimination of
chromophores as being very fast initially but
slowing as the absorption
coefficient
(brightness) limit is approached. This equa-
Chapter IV 8: Chlorine Dioxide in Bleaching Stages
383
384

CIO,
20
Vapor
to
scrubber
NaOH
54
10
Steam
Water
67
11
::; 1.0
;;
..z
82
"#
JCD
CI02
aH
89
CEHDE
0.1
Pulp
in
stage
Pulp
out
94
Effluent
Reaction time, h
Fig.2. RIlle 01eltrmtwJl#lm'e

ellmlutltnl IIIeb~
tion also shows that an increase in chlorine
dioxide concentration increases the rate of
chromophore
elimination as does a decrease in the hydrogen ion concentration
(increasing pH). The activation energy (E)
has been found to be approximately 60 Jij/
mol, indicating that the rate of reaction approximately doubles with each lOoC temperature increase.
0.3
0'30-
E
c:
o
4Io:dM blMd1illgo/}lrelrNlM so.flrroo4itw/l jIfIlJIs.

cations which is extremely useful for predicting changes in conditions and circumstances (21).
1WIle2. ~
IIIg.
Pulp
Pretreatment
CEHH
(DC)E
(DC)EDE
O(C+D)E
O(C+D)EDE
0.2
01eblorllte 4Io:dM blHeb-
n'
a'
0.072
0.058
0.078 (km)o
0.042
0.010 (km)o
1.6
1.0
2.3
1.3
2.0
Iii!
o'"
Note: (km)o = the initial value of km
THE UPFLOW-DOWNFLOW TOWER
a and n are constants in the expression:

a ---1d{QQJ
dkm
(km)"
Vents to
scrubber
0.1
i3
cycled from use at some other location and

the effluent is in turn reused for washing
the pulp at some stage upstream. Vapor
emitted from the stage is sent to a scrubber
for removal of chlorine dioxide.
The process flowsheet and equipment
for chlorine dioxide bleaching are straightforward as is illustrated in Fig. 5 (22). Pulp
leaving the washer of the previous bleaching stage contains sodium hydroxide, often
added in the repulper of the washer, and
then typically falls into a steam mixer to

increase and control the temperature. Pulp
from the steam mixer is pumped through a
chemical mixer, where chlorine dioxide
solution is added, and then into the tower.
Pulp exiting the tower proceeds
to a
washer. It is noteworthy that the chlorine
dioxide solution is added after the pulp suspension has been pressurized and that pressure is maintained on this mixture by the
hydrostatic head of the upflow tower.
There are, of course, many variations of
this flowsheet.
In most modem installations, traditional thick-stock, positive-<lisplacement pumps have been replaced by
fluidizing, medium-consistency
pumps.
Chlorine dioxide solution can be added in
the turbulent zone on the discharge side of
this type of pump and effective mixing is
achieved without a separate mixer. In installations where the temperature
of the
pulp entering the stage is sufficiently high,
the steam mixer may not be required. In
place of the upflow-<lownflow tower illustrated in Fig. 5, upflow towers may be used
(22). For further discussion of these options, the chapters on bleaching equipment
may be consulted.
The position of a chlorine dioxide stage
in a bleaching sequence varies, but because
0
o
10
15
20
NaOH
Wash
water
-ACk. m2/kg
Fig. 3. Wed
01 eblorllte 4Io:dM t:OIISImIptlml 0fI
tbe
tM ell"d""tImI
01 elmnrro/lllores
I"
IHau:ImIg o/preIrNIM
so.flrroo4lm1ft In'',,.
These kinetic experiments

have been
used to determine the chlorine dioxide consumption required to achieve a particular
degree of bleaching (i.e., elimination of
chromophores)
as is represented in Fig. 3
andTable 2 (21). This information has been
used to create a mathematical model for
chloriDe dioxide bleaching and its appli-
3. Process flowsheets and

bleaching conditions
3.1 Flowsheets, equipment,
bleaching
and
sequences
A generalized flow sheet for a chlorine

dioxide bleaching stage is shown in Fig. 4.
Pulp usually enters and exits the stage at
medium consistency, typically 10-16%;
chlorine dioxide, sodium hydroxide, steam,
and water are required, and an effluent is
produced.
Usua1Jy the wash water is re-
Pulp
out

Ttlble 3.
/i3uImpIes
of eblorl1le
tUoziM
94
bletlebhtg
~.
92
Single CI02 Stage

Pre-1980
CElID
CEHED
CEHDP
385
Post-l990
(DC)(E+O)D
O(DC)(E+O)D
OD(E+O)D
OZ(E+O)D
Two CI02 Stages

CmIDED
(DC)EDED
CEDED
DEDED
D(E+O)DED
OD(E+O)DED
OD(E+O)(DN)D
OD(E+O+P)(DN)D
of the high selectivity of chlorine dioxide

and its relatively high cost, chlorine dioxide stages are most commonly used at, or
near, the end of bleaching sequences. Examples of pre-1980 bleaching sequences are
given in Table 3. Sequences with only a
single stage may have been limited to 8085 brightness depending on the properties
of the unbleached pulp. Marlcet kraft pulp
sequences generally consisted of two chlorine dioxide stages separated by an intermediate alkaline extraction stage.
Since 1980 there has been an extremely
rapid development of bleaching technology
which has led to a great variety of bleaching sequences in which chlorine dioxide
bleaching stages are included. Some examples of post-I990 bleaching sequences
are listed in Table 3. Optional features include oxygen delignification, a high degree
of chlorine dioxide substitution for chlorine, a chlorine dioxide delignification
stage, ozone delignification, and oxygenenriched alkaline extraction.
If sufficient
lignin is removed in the stages before chlorine dioxide bleaching, then 90 brightness
can be achieved in a single stage. It must
also be remembered that the lignin content
of unbleached pulp produced after 1990
may be significantly lower because of extended delignification technology.
For production of bleached kraft marlcet
pulp, two chlorine dioxide stages are still
CEDED
90
88
'*
~86
.s 84
..c
00 82
~80
80
75
70
W
o 65
*::60
~ 55
CEDED
cm
50
as 4S
40
35
78
76
o
386
0.25 0.50 0.75 1.00 1.25 1.50 2.00

Cia, applied in the third stage, % on pulp
0.2
0.4
0.6
0.8
1.0
1.2
Cia, applied in the final stage, % on pulp
Fig. 6. lfIIect of IN S:OtUIeblorlw tUoziM slllge

(DJ Oft IN brigb,,",ss of (I so~
ImIft
JIrIIJIbletlebetll" (I CEDED~.
common. These chlorine dioxide stages are

usually separated by an extraction stage or
a neutralization step designated N. Neutralization involves adding sodium hydroxide
to the dilution zone at the end of the first
chlorine dioxide tower. This step provides
most of the benefit of the intermediate alkaline extraction stage. With the replacement of chlorination
stages by chlorine
dioxide delignification stages, stage numbering has become confused. The chlorine
dioxide delignification stage is sometimes
designated Do' for example, DOEDJED2'
3.2. Chemical charge and residual
When chlorine
dioxide is added to
bleached pulp, initially the brightness increases rapidly with increasing chlorine dioxide charge, then the rate of brightness
gain decreases until some asymptotic brightness limit is reached. This effect is illustrated
in Fig. 6 for a final D stage and in Fig. 7 for
a DJ stage (4,5). Despite increased chemical application
effective (23).
40
6"
..,
c:
<II
35
92%ISO
'. c: 30
og
c:.....
'~6
25
Qo
u~
aJ 20
E
i;1
c:
15
S
"!
{?
50
75
25
% Cia, consumed in the D, stage
100
Fig. B. Effect of eblorlw lllonM tIIstrlInItIo8 beIN D, tIt8tID, slilges of (I CIIDI!Dse'f.etlee

Otl Ibe 101,,, eblorltle IIloxllle
eotJS8mptUM by (I so~
ImIft JIrIIJI.
Normally the pulp is washed after the D

and E2 stages. However, it has been sho~
that even without interstage washing, a
(DED) sequence produces higher brightness pulp with significant chemical savings
compared with a single D stage (24).
Oxygen enrichment of the first alkaline
extraction stage produces brighter pulp in
that stage and in the following D and D
stages. Figure 9 illustrates the ~pact
of
oxygen enrichment on the development of
brightness in the D, and D2 stages (25).
Considerable work has been done on the
use of the E-stage kappa number to predict
pulp bleachabllity in the following chlorine
dioxide stages. It has been argued that, as
chlorine dioxide substitution increases the
lignin residual in the pulp is more oxi<Ilzed
and therefore is not accurately characterized by kappa number measurement. How-
100
..- E,D.
-E,D,
'D,
~110
'D,
.."
in the D I stage, it is not pos-
sible to increase
brightness
further.
However, when the DJ stage is followed by
an alkaline extraction treatment and a second chlorine dioxide stage, an additional
brightness gain can be achieved as shown
in Fig. 7.
Another way of describing this effect is
illustrated in Fig. S (23), To achieve a particular brightness, optimal use of chlorine
dioxide is obtained when 20-30% of the
selected amount is applied in a second (D)
stage. If only one stage is used (t.e., 100%

of the chlorine dioxide is consumed in the
D, stage), much more chemical is required.
A thorough analysis of the conditions req~red for an effective E2 stage provides
gwdance for bleach plant operations (23).
Increasing the Eistage temperature
from
40-80C provides a small increase in D
brightness; increasing the E -stage alkalin~
ity from pH 7 to 12linearIy in~reases brightness after Dr Relatively little time (5-10
minutes) is required for the E2 stage to be
1A!i
iii)
DIC-OE
40
DIC-E
20
10
20
30
40
50
dO, applied, kg I metric IOn pulp

JIIg.,.
IJfIeei0foxyga
irwft JIrIIJI.
errrlebmerJt
hi lbe E, slilge of (I CIIDIJD ~
Oft IN fir,,"
brlgbtrfess
of (I so~
387
388
2.00
12
fiN' B..........
90 ISO
.9-1.50o &.
c: .
1:i
1.00-
1:!'>
Q~
u
0.50:is
o
,
I
2
Fig. 10. Cliwrlu ~

,..,lretIllllbe
blueW
III. (D+C)BDI!D~.
10
Chlorine Dioxide Increase,

(kg/unit increase in kappa
number after the first
extraction stage)
1.9
Eucalyptus (32)
3.4
Birch (33)
4.5
:r
Q.
Figure 10 shows that the total amount of

chlorine dioxide required to bleach to 90
brightness is linearly related to the E, kappa
number (30). Thus, the slope of each line
indicates the amount of cWorine dioxide
required per unit of kappa number increase
(see Table 4). It is evident that 0) different
wood types exhibit different degrees of
bleachability, (2) varying cWorine dioxide
substitution in the "cWorination" stage from
NaOH added.
onpulp
"
t
0.4
0.0
I
3
4
5
Post E, kappa num~
DI!D *Ja
Softwood (28 - 31)

(including conventional
and modified pulping and
oxygen delignification)
/I
, ,,
,, ,
ever, the results of many different studies

have shown clearly that cWorine dioxide
substitution in the first stage over the 1090% range has no impact on bleachability
.
(26-33).
Pulp (Reference)
, , , , , Etalyptus
,
, 5oltwood
, ,, , ,
,,
,
,
, ,, , , , , , ,
, ,
~ j
Ii
, Birch "
I
7
I
6
o 10
60
120
1110
Reaction time, min
16 tIdIIne jO'1(,ISO brlfblr8ess for Mrlo8s ",."ft JIfIlps
10-90".4 has no effect on bleachability, and

(3) the bleachability of softwood kraft pulp
from conventional and modified pulping
processes and from oxygen delignification
is the same.
Further information on the bleachability
of eucalyptus kraft pulp in various modified
bleaching sequences is available elsewhere
(32, 33).
AJ; illustrated in Fig. II, increasing the
brightness target to 91 increases the slope
somewhat and increases the cWorine dioxide required by 1 kg per metric ton of pulp
(34). Decreasing the brightness target to
89 decreases the slope and chemical consumption similarly.
CWorine dioxide stages are usually operated to maintain a cWorine dioxide residual
Q.
01..
~20
'j 15
~
'i'5. ~ 10
~~
8j
4
Post
Fig. 11.
of
5 6
7 8
[, kappa number
9 10
IJrlgblr8ess IIIrgeI Oft lbe

JI"'"requlmlllllbe
"'JI-DED sltlges
eb/qrirH!
"'-IM
for softof. fD+C)BDI!Dblefu:blllg ~
fIJOOll ",."ft
JIfIlps.
at the end of the stage to prevent a darkening of the pulp corresponding to approximately 2 brightness units. Maintaining a
certain concentration level of cWorine dioxide throughout the bleaching stage provides a continuing
driving force for
brightness increase and, more importantly,
for particle bleaching as is discussed in
Chap. IV 11. However, minimizing the residual is desirable for decreasing washer
corrosion, emission of cWorine dioxide into
the air, and complications in systems closure. An analysls of low residual cWorine
dioxide bleaching shows that this approach
is more economical and produces higherquality pulp (36).
CWorine dioxide residual is usually measured at the washer vat following a cWorine dioxide stage and typically is in the
range 10-50 mg ClOIL (10-50 ppm). A 10
mg aOIL residual in the vat corresponds
to 1 kg of cWorine dioxide per metric ton
of pulp.
Some mills add "anti-<:Wor" at the end of
a cWorine dioxide tower to minimize the
negative effects of large concentrations of
residual cWorine dioxide. The "anticWor"
reacts with the chlorine
dioxide
and elimi-
nates it. Sulfur dioxide dissolved in water

has been used extensively for this purpose
in the past. More commonly, sodium hy-
droxide is added at the end of the tower to

increase the pH to 6-7, converting residual
cWorine dioxide to sodium cWorite which
is non-volatile and much less corrosive than
cWorine dioxide.
-1.0
~5
0
NaOH.
05
1~
15
2.0
% on pulp
Fig. 13. pH COfIIroI III cbWrlfH! d'-IM

blefu:lnng
sltlges by tIlliUIWt8of IIdII or .Iull.
3.3 pH
When cWorine dioxide reacts with pulp,
organic and hydrocWoric acids are formed
and the pH decreases. The rate of pH decrease is extremely high with most of the
change occurring in the first 10 minutes of
reaction as is illustrated in Fig. 12 (37).
Sodium hydroxide is added to the pulp be-
Chapter
IV 8: Chlorine
Dioxide
in Bleaching
Stages
389
1.0
..
1.4
'0
~.!!:1.2
!fs.
c
'C
0 0
1.0
:e II!
~80
1
Iii
0.8
75
15 'C
t~
70
3
End
4
pH
in
5
the
Fig. 14. Effecl of eM pH in . D, slIIge 018 I1rlgbmess
Dt
1.2
1.0
~
u
~ 0.8
~
0.6
5
~ 0.4
~
0.1
z
o
'I
:;
6
pH
Fig. 15. SodhIm byIlro:ritle fWI'Ilrwl to aebkve.

tieulllr eM pH III IID, stage.
14
~ 6
c:f 4
2
I .
3.0
4.0
D,
tower
5.0
terminal
6.0
pH
Fig. 16. Effect of eM pH ill . D, sItIg6 018 UirJes ill

1M JnIlp .fter 1M D, sIiIge.
10
jJtIr-
3.5-4 for the time remaining in the stage.

Less chlorate is formed, and the savings in
chlorine dioxide can be as great as 24%.
stage
tmtl ebWrlte
fore addition of chlorine dioxide to increase

the starting and final pH as is illustrated in
Fig. 13 (37).
Early studies showe4 that maximum
brightness was achieved over a broad pH
range centered at pH 6. However, in these
studies, buffer solutions were used so that
the pH was constant (38). A more appropriate simulation of the falling pH during a
chlorine dioxide bleaching stage showed
the optimal end pH to be in the range 3.5
to 4 (14, 35). Figure 14 shows that maximum brightness is obtained in this range as
a consequence of a minimum loss of active
bleaching chemical (35). Chlorate formation decreases and chlorite formation increases with increasing
pH. Although
chlorite reacts with pulp when the pH is
"l
?d
Practice
0.2
11
- Principles and
. .
12
~>Q; 10
":fj
0.5 .!! ..
~';
0.4 6
Pulp Bleaching
22
20
1: 18
16
8
1.8
85
390
tmtl eblorwte
j'ormIItWrI.
low ( < 4), it has been clearly shown that, as

the pH increases above 4, its reactivity with
pulp drops very rapidly. At a pH greater
than 5, chlorite is stable in pulp suspensions, and therefore its potential for bleaching is not realized (38). Some mechanistic
studies have attempted to explain the importance of pH in chlorine dioxide bleaching (12).
The amount of sodium hydroxide required to achieve a particular end pH is
shown in Fig. 15 (15). For solutions consisting only of chlorine dioxide, approximately 0.6% sodium hydroxide on pulp
should be added for each 1% chlorine dioxide applied to the pulp. Chlorine dioxide
solutions containing chlorine require more
sodium hydroxide. It should be noted that
only a small amount of sodium hydroxide
is required to increase the end pH from 4
to 7. There is, therefore, significant danger
in exceeding the target pH when it is set at
4. Further, as can be seen from Fig. 16,
when the pH rises above 4, there is a tendency for the shive removal capacity of the
stage to decrease sharply (39).
A two-step process has been proposed
for increasing the efficiency of chlorine
dioxide ble2l'htng st2ges (40). In the ftr~[
step of chlorine dioxide bleaching, the pulp
is held for 5-15 minutes at an end pH of
6-7.5. The mixture is then acidified to pH

When the reaction time of a chlorine dioxide bleaching stage is increased, more
chlorine dioxide is consumed (t.e., its concentration decreases) and pulp brightness
increases. The pH drops very rapidly at the
beginning of the stage as is illustrated in Fig.
17 (21). The data points are taken from
experiments, and the lines originate from a
mathematical simulation based on kinetic
studies (20).
The traditional design of chlorine dioxide stages in a CEDED sequence provides
threehours of retention time in each chlorine dioxide stage. In an upflow-downflow

tower, the upflow leg has 30 minutes' retention and the remaining 2.5 hours is allocated to the downflow tower. Some towers
have been constructed with up to 5 hours'
retention time, while others have as little
as 90 minutes' retention time because of
production increases beyond the designed
capacity. In upflow towers, the retention
time is fixed; in downflow towers, some
variation is possible to accommodate short
shutdowns.
It is desirable under normal
circumstances to operate chlorine dioxide
towers with the maximum practical retention time to facilitate elimination of bleachable particles.
The temperature in a chlorine dioxide
stage is typically 70"C. As discussed earlier,
the rates of bleaching and chlorine dioxide
consumption are increased or decreased by
increasing or decreasing the temperature.
For instance, at a given chlorine dioxide
charge, increasing
the temperature
increases the brightness and lowers the residual. It is desirable to retain a chlorine
dioxide residual throughout the stage to
facilitate brightness increase and, particularly, shive removal. The temperature of the
stage is adjusted by adjusting the flow rate
of steam
to the steam
mixer
to achieve
60
6
..J
......
(5
650
~
~
4
(\j
70 u)
I1J
Q)
c:
75 '5
.;;::
o 2
J:
a.
80m
90
60
120
Bleaching
Fig. 17.
qfI
of"-
ness.
of. eblorllae d'-IM
time,
180
min
b1eaebillg stage 011pH, ebillrine tlio:dM COIISIItIIpIUm,IIntll1rlgbt.

100
391
noted that when the consistency is low, the

retention time in a tower is shorter at a given
80
production rate. For instance, a decrease
\-i
c:
in consistency from 12 to 10% increases the
E
60
S
volumetric flow rate by 20% and decreases
E
the effective retention time by 20%, that is,
:>
40
E
from ISO to 144 minutes. For this reason
"c:
~20
and because lower consistency
means
greater steam requirement
for heating,
higher consistency is desirable. The upper
0
30
20
0
10
consistency
limit is usually dictated by
Chlorine dioxide, kg/ tonne pulp
pumping constraints. The addition of chll>n,. 18. JlI___ ~
rwJ8hwlfor IfHWo rine dioxide solution decreases consistency;
C4JflSlml/ltItm01 dI~
~
III. elllofor instance, with addition of 10 kg chll>rille ~
blMeill"l sItIfe.
rine dioxide per metric ton of pulp at 10 g/
L, pulp consistency decreases from 12 to
desired residual, usually in the range 10- 30
10.7%.
mg/L (1-3 kg/metric ton of pulp). The
As discussed in Chap. IV 4, chlorine dimathematical model referred to earlier was
oxide has been shown to be very efficient
used to calculate the minimum temperature
at consistencies
in the 30-40% range.
required to achieve zero residual with
However, operation in this range requires a
changing chlorine dioxide charge as is ilvery high capital investment and is not praclustrated in Fig. 18 (21). To obtain this reticed.
sult, the initial and final brightness were
varied while consistency, production rate,
3.6 Influence of chlorine and chloride
and retention time were fixed.
ion
The upper temperature limit in chlorine
Several
studies have been made on the
dioxide stages is usually fixed by the practieffect of chlorine on chlorine dioxide
callimitations of feeding steam into a steam
bleaching (15, 41, 42). Chlorine may be
mixer. When the mixer is operated beyond
present in chlorine dioxide solutions from
its capacity, steam blows back into the
certain types of generators, namely, R2 and
washer repulper. In some systems, 9O"C
R3/SVP. The chlorine dioxide generated
can be achieved. Addition of chlorine dimay be accompanied by up to 25% of its
oxide solution, which is typically at 5-1 O"C,
weight in chlorine. For instance, a 10 g/L
decreases the temperature of the pulp in
chlorine dioxide solution may contain 2.5
the tower. For instance, when a 10 g/L chll>g/L chlorine. In this solution, 9",,(,of the
rine dioxide solution at 5"C is added to 12%
oxidizing equivalents are provided by chll>consistency pulp at 7O"C at the rate of 10
rine. Generally, the above studies have
kg chlorine dioxide per metric ton of pulp,
shown no significant impact of such conthe temperature drops from 70C to 67C.
centrations of chlorine on bleaching effi3.5 Consistency
ciency with the exception of situations
where there is very high carryover of exChlorine dioxide bleaching is normally
traction-stage filtrate into the chlorine diconducted
at medium consistency.
The
oxide bleaching stage. No change in pulp
consistency is determined by the water redegradation has been observed. The oximoval capability of the washer preceding
dizing power of chlorine is utilized as efthe chlorine dioxide stage; overloaded
fectively as if it were chlorine dioxide (15).
washers may deliver as low as 9",,(,consistency, but some washers deliver 16% or
As discussed
earlier, when chlorine is
present in the chlorine dioxide solution,
more. Consistency over this range has a
more sodium hydroxide may be required
negligible effect on reaction chemistry or
to control pH.
bleaching efficiency. However, it should be
392
Pulp Bleaching
-Principles
and Practice
As discussed in connection with chlorine

dioxide delignification in Chap. IV 3, the
addition of chloride ion can influence chll>rine dioxide reactions. Addition of 2 g IL
sodium chloride leads to a significant (2
points) brightness gain and lower chlorate
formation (14).
3.7 Washing and carryover
Washing after the extraction stage preceding the chlorine dioxide stage influences
the carryover of extraction-stage
filtrate.
Filtrate that is not removed from the pulp
contains dissolved lignin fragments which
compete for the chlorine dioxide with lignin still remaining in the pulp, causing increased chemical consumption
or lower
brightness. This is particularly problematic
in closed systems where low water use is
required. Carryover can be measured by
permanganate consumption, as in a modified K number or kappa number test (15),
or by light absorbance, for instance at 278
nm (43). Kinetic studies and development
of a mathematical model allow prediction
of the impact of carryover on chlorine dioxide bleaching (43). Addition of oxygen
or peroxide to extraction stages decreases
the filtrate absorbance by decolorizing the
dissolved lignin but does not significantly
alter the concentration of dissolved lignin
in the filtrate as measured by absorbance
(43).
1
""
models (48). The degree of

by the variation
coeffi-
cient (sIX). Perfect mixing has a variation

coefficient
of zero. As shown in Fig. 19, for
5
10
15
2(
00, applied, kg / metric ton pulp
Fig. 1'). Efft 01 mlxlag ~./JfdMey 011eblorl_ 111O#IM resIilul I". eblorl_ llloxUe bletleb-
'''g st.ge.
40
Fig. 10.lffft
10
15
CIO, applied. kg / metric ton pulp
01 mlzl..,
. eblorl_ ~
~./JfdMey 011brlglllrrns
bletleblrtg
st.ge.
I"
100
~
-110
is quantified
s/'i.
o
4.1 Mixing
mixing
0,,"
:> 2
4. Engineering considerations
mathematical
40"
~;;
.~
.11:
"'60
..c
';;
There have been a number of studies

made on the influence of high-intensity
mixing on the efficiency of chlorine dioxide bleaching stages (44-48). Laboratory
and field studies have consistently shown
that failure to properly distribute chlorine
dioxide throughout the pulp suspension
leads to high chemical consumption and
low brightness and, in many instances, poor
particle bleaching. The influence of mixing is very well illustrated by the use of
60"
:::6
0
.~
t4
~ 40
20
CIO, applied,
10
15
kgl metric ton pulp
Fig. 11.lfffeet
01 mlxlag ~./JfdMey 011sblve rmrolJld
. eblorl_
llloxUe 6lMebl..,
slilge.
I"
a given chlorine dioxide charge, the residual

chlorine dioxide decreases as mixing improves, assuming all other variables are held
constant (48). Figure 20 shows that, as
mixing improves, a higher brightness is
achieved for a given chemical charge or, to
achieve a given brightness, less chemical is
required (48). The situation is somewhat
2(
Chapter IV 8: CWorine Dioxide in Bleaching Stages

more complex where particle bleaching is
concerned. As illustrated in Fig. 21, when
there is a relatively high cWorine dioxide
charge, particles
are more effectively
bleached as mixing Improves (48). However, when the cWorine dioxide charge is
relatively low, good mixing rapidly depletes
the supply of available cWorine dioxide and
particle elimination is actually worse. To
compensate for this change in the rate of
chlorine dioxide consumption,
the temperature should be decreased to maintain
the cWorine dioxide residual for the entire
stage. The subject of mixing is covered in
detail in Chap. V 2.
4.2 Chlorine dioxide solution heating
With increasing cWorine dioxide use in
pulp bleaching, it has become more apparent that there is a cost associated with heating the large volume of chilled chlorine
dioxide solution to the bleaching stage temperature. For instance, if cWorine dioxide
is applied to pulp at the rate of 10 kg per
metric ton of pulp in a 10' g/L solution, then
the cWorine dioxide solution contains one
metric ton of water per metric ton of pulp.
Heat exchangers can be used to raise the
temperature of a cWorine dioxide solution.
Extraction-stage filtrate is used as a heat
source on the shell side of a heat exchanger
having titanium tubes. The heated solution
must be kept under pressure to prevent
cWorine dioxide vapor from forming and
suitable safety precautions and interlocks
must be designed into the system (49).
5. Pulp quality
CWorine dioxide provides pulp of high
brightness and low brightness reversion and
is extremely effective in particle elimination. Chlorine dioxide does not react extensively with carbohydrates although some
oxidation of cellulose does take place (50).
In addition, if the cWorine dioxide stage is
very acidic, some acidic hydrolysis of cellulose can take place. Although viscosity loss
in cWorine dioxide bleaching stages is usually very low, under aggressive conditions,
such as pH 2, at temperatures greater than
80"C, or when the chlorine concentration
equals that of cWorine dioxide, some carbohydrate degradation can take place.
6. Environmental
393
factors
Some chlorinated
organic matter is
formed during cWorine dioxide bleaching
stages. AOX in the amount of about 0.1 kg!
metric ton pulp in the combined D, and D2
stages has been reported (15, 51). AOX
from these stages may increase if the lignin
content of the entering pulp increases.
Chlorine dioxide emission from chlorine
dioxide-stage towers and washers can also
occur. Emission rates and control strategies
are described in Chap.VIlI 4.
Acknowledgments
Sterling Pulp Chemicals
has provided
financial support for cWorine dioxide bleaching research to the University
of Toronto.
References
1. Rapson, W H., Pulp Pap. 32(1):46
(1958).
2. Casciani,].,Pap.Tradej
(1953).
136(10):21
3. Harrison, WD., in The Bleaching

of Pulp,
Monograph No. 10 (R.S. Hatch, Ed.), TAPPI
PRESS, New York, 1953, pp. 119-135.
4. Rapson, W H., in Tbe Bleaching
of Pulp,
Monograph
No. 27 (W.H. Rapson, Ed.),
TAPPI
PRESS, New York,
1963,pp.13O-179.
5 Rapson, W.H. and Strumila, G.B., in The

Bleaching
of Pulp (R.P. Singh, Ed.), TAPPI
PRESS, Atlanta, 1979, pp. 113-157.
6. Rydholm,
S.A., in Pulping
Processes,
Interscience,
New York, 1%5, pp. 972-991.
7. Soila, R., Lehtikoski,
0., Virkola, N.-E.,
Svensk Pappersttdn.
65(17):632(1%2).
8. Lindgren,
B.O.,
82(5):126(1984).
9. D'Aveni,
Tecbnol.
Svensk
A. and Robert,
16:77(1982).
10. Wartiovaara,
(1982).
Papperstidn.
A., Cellul.
I., Pap. Puu
11. D' Aveni, A. and Renaud,

Chim. Fr. 6:1038 (1985).
12. Wartiovaara,
I., Tappij
Chern.
64(11):680
M., Bull.
Soc.
69(2):82(1986).
13. Nilsson,
T. and Sjostrom,
L., Svensk
Papperstidn.
77(17):643
(1974).
14. ~pson,
WHo and AndersM, CB.,
Trans. Tech Sect. 3(2):TR52

15. Reeve, D.W. and Rapson,WH.,
Can. 82(12):T426
(1981).
CPP.4
(1977).
Pulp Pap.
394
16. Germgaro, U.,Teder,A.,Tormund,

Puu 63(3):127 (1981).
D., Pap.
17. Bergnor,
E., Ge, rmgard
D., Kolar, ).J.,
lindgren, B.O., Cellul. Chern. Technol. 21:
307 (1987).
18. Van der Merwe,AJ.W,VlIjoen,
FJ.,Thom,
B.D. Lourens, G.]., Tappi 63(8):94 (1980).
19. Kutney, G.W and Mallais, M.M., Svensk
Pappersttdn.
86(12):RI35
(1983).
20. Teder, A. and Tormund, D., CPPA Trans.
Tech. Sect. 3(2):TR41 (1977).
21. Teder,A. and Tormund, D., "Mathematical
Model for CWorine Dioxide Bleaching and
ItsApplications;
AlChE Symposium Series
No. 200, Vol. 76, 1980, p. 133.
22. Reeve, D.W, in Pulp and Paper Manufacture,
Vol. 5 - Alkaltne
Pulping
(T.M.
Grace, E.W Malcolm, MJ. Kocurek, Eds.),
3rd eOO. JointTextbook
Committee of the
Paper Industry,
CPPA (Montreal)
and
TAPPI (Atlanta), 1989, pp. 390469.
23. Axegaro, P., Jansson, U., Teder, A.,j
Pap. Sci. 10(1):JI (1984).
Pulp
24. Histed,J.A.andVega
Canovas,R.,"Decreasing the Dsage of CWorine and Caustic in
Bleaching; 1989TAPPI Pulping Conference
25. Carre, G., Nasman,
L., Annergren,
G.,
lindstrom,
L.-A., "Oxygen Alkali Extraction,A Versatile Tool Towards a Simplified
Bleaching Technique;
1982 TAPPI International Pulp Bleaching Conference
26. Axegard,P.,"Effect
ofCl02-Substitution
on
Bleaching
Efficiency and Formation
of
Organically Bound CWorine; 1984 TAPPI
Pulping Conference
Proceedings,
TAPPI
27. Germgard,
D. and Karlsson,
Puu 66(11):627 (1984).
R.-M., Pap.
28. Germgird,
D. and Karlsson,
Puu 67(11):655 (1985).
R.-M., Pap.
29. Germgaro, D. and Karlsson, R.-M., Svensk

Pappersttdn.
88(15):RI33
(1985).
30. Germgaro, D. and Lundqvist,
43(1):63 (1990).
M., Appita
31. Germgaro, D. and Karlsson, R.-M., Nord.

j Pulp Pap. Res. 3(4):166 (1988).
32. Germgard,
D. and Vannfalt,
43(4):305 (1990).
c., Appita
33. Asplund,
44(2):95
D., Appita
34. Axegard,
C. and Germgard,
(1991).
P., "ClO.-Substitution
Reduces
the Load of TOCl," 1987 TAPPI Pulping

Conference
Proceedings,
TAPPI PRESS,
Atlanta, p. 105.
35. Rapson, WH. and Strumila, G.B., in Tbe
Bleaching of Pulp (R.P. Singh, Ed.), T APPI
PRESS,Atlanta,
1979, p. 133.
36. Annergren, G.E., Hiiggkvist,].E.
Lindblad,
P.O.,] Pulp Pap. Set. 13(1):)9 (1987).
37. Wartiovaara, I. ,Pap. Puu 64(9):534 (1982).
38. Rapson, W H., Tappi 39(5):284 (1956).
39. Pattyson,
G., Rae, R.G., Reeve,
D.W.,
Rapson,WH.,
(1981).
40. Seger, G.E.,Jameel, H., Chang, H.-M., Tappi
j 75(7):174 (1992).
41. Rapson, WH. and Anderson,
40(5):307 (1957).
C.B., Tappi
42. Macas, T.S. and Evans, T.D.,]

Set. 13(3):JI06 (1987).
Pulp
Pap.
43. Parming, A.M., Bergnor, E., Backlund, B.,

"A Kinetic Study of the Reactions Between
Dissolved Organic Substance and CWorine
Dioxide;
Pulp
44. Torregrossa,
L.O., "Effect of Mixing Efficiency on Chlorine Dioxide Bleaching,"
Proceedings,TAPPI PRESS,Atlanta, p. 635.
45. Pattyson, G.W., "Kamyr MC. Mixer for
CWorine Dioxide Mixing at Great Lakes
Forest Products, Thunder
Bay, Ontario;
70th Annual Meeting
Preprints,
Tech.
Sect., CPPA, 1984, p.A63.
46. Kolmodin,
H., Svensk
87(18):8 (1984).
Pappersttdn.
47. Bergnor, E., Backlund, B., Teder, A., "The

Benefits of Better Mixing; 1985 TAPPI International
Pulp Bleaching
Conference
Proceedings,
TAPPI
PRESS,
Atlanta, p. 233.
48. Backlund, B. and Parming,A.M.,"A
Kinetic
Srudy of Inhomogeneities
in Bleaching",
1985 International
p.155.
49. Atkinson,
(1980).
E.S., Pulp
50. Teder, A. and Tormund,

(12):59 (1979).
Pap.
54(10):152
D., Tappi
51. Basta, j., Andersson, t,
6I
Blom, C.,
Holtinger, L., Hook, J., Appita 45(1):29

(1992).
SECTIONIV:
The Technology of Chemical Pulp Bleaching
Chapter 9:
Hypochlorite and Hypochlorous Acid Bleaching
J.A. Histed
LF. Sandel Jr.
Jack Histed Consulting Ltd.

L'Original, Ontario.
International Paper Company

Natchez, MS
M.M. Hurst
Quantum Technologies
Twinsburg, OH
Inc.
1. Introduction
... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 397
1.1 History of hypochlorite bleaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 397
1.2 Evolution of hypochlorite bleaching
397
1.3 Modification of bleaching conditions in
response to changing control methods
397
2. Process variables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 398
2.1 Chemical charge. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 398
2.2Time
399
2.3 Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 399
2.4 Consistency
,.,
399
2.5 pH . . . . . . . . . . . '. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 399
2.6 Conditions affecting viscosity loss. . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . 400
3.Reaction kinetics. . . . . . . . . . . . . . . . . . . . . . , . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 400
3.1 Kinetics equations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 400
3.2 Effect oftemperature
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 401
3.3 Effect of consistency. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 401
3.4 Effect of pH. . . . . . . . . . . . . , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 402
4. Process equipment . , . . . , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 402
'
4.1 Flowsheet of hypochlorite
stage
402
4.2 Effect of bleaching temperature on equipment design . . . . . . . . . . . . . . . . . . . 403
4.3 Use of towers or flow-through tubes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403
5. Particle b
h1ng with hypochlorite.
. . . . . . . . . . . . . . . . . . . . , . . . . . . . . . . . . .. 403
6. Hypochlorite bleaching ofdJssolving pulp. ... .. . . .. . . ... . . ... . . . .. . . . ... 403
7. Washing of hypochlorite-bleached
pulp .. . .. .. . . .. . . . .. .. .. .. . . . .. . .
404
8. Modern process control.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 404
8.1 Sensors. . . . . . . . . . . . '. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
8.2 Sensor location. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
8.3 Response of optical sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405
8.4 pH sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405
9. ~nomlcconskieratlons
406
10.EJ1vDnDnmmentdas~
...
407
11. Chlorine monoxide bleachIng of pulp . . . . ... .. .. ... . . . ... . . . . . . . . . .. .. 407
11.1 Background
407
11.2 Effect of pH. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 408
11.3 Process conditions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409
11.4 Bleaching responses. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409
11.5 Environmental aspects. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409
11.6 Hypochlorous acid generation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 410
395
Chapter IV 9: Hypochlorite and Hypochlorous Acid Bleaching
Chapter IV 9:
Hypochlorite and
Hypochlorous
Acid
Bleaching
1. Introduction
1.1 History of hypochlorite
bleaching
Following the discovery ofJavelle water
(chlorine dissolved in caustic soda) in 1789
and bleach powder (calcium hypochlorite)
in 1799, hypochlorite
was the preferred
bleaching agent for cloth and wood pulp to
1946 when chlorine dioxide became commercially available. Because bleach powder
could be made in dry form and shipped long
distances in wooden kegs, it was the preferred bleaching agent and became the standard oxidant against which the oxidizing
power of all other bleaching agents was
measured.
Hypochlorite stages are in the process of
being phased out of commercial bleach
plants for environmental reasons including
the perceived hazard of hypochlorite as a
chlorine compound and the documented
role of these chemicals in the formation of
chloroform during pulp bleaching.
1.2 Evolution of hypochlorite
bleaching
Initially, soda and sulfite pulps were
bleached at 3%-4% consistency in a series
of vertical tanks. In 1895 the Bellmer brothers in Germany introduced a new type of
bleacher which operated at 7% consistency.
TIlls was a horizontal oval tub divided into
compartments
by two interior walls. Pulp
flowed from the outer compartment to a
pumping element which returned the pulp
to the central compartment (1). Bleach was
added into the circulating pulp until the
desired brightness was reached in a single
stage.
During World War I, a need developed
for large quannties ofhighly purified sulflte
wood pulp for nitrocellulose production.
This pulp was prepared using a three stage
HEH process with inter-stage washing.Wlth
397
the commercial introduction of the chlorination stage in 1930, hypochlorite lost its
position as the sole oxidizing agent in pulp
bleaching and became part of a multi-stage
CH or CEH sequence capable of producing
high brightness (about 88 ISO) sulfite pulps
having improved strength and brightness
stability.
Only a few kraft mi1ls produced bleached
pulp before the advent of chlorine dioxide
in 1946. These mills used multi-stage sequences such as CEHEH to produce pulp
of about 82 ISO brightness. One variation
of this sequence
was a hypochlorite
prebleach which preceded chlorination,
(HC), with no interstage wash. The advantage of this modification was that the total
dose of chlorine chemicals was split thus
decreasing the amount of chlorine gas that
had to be dispersed in the slurry by the rudimentary mixing equipment available at
that time. Another variation of the sequence
was the inclusion of small amounts of hypochlorite in the high-pH second extraction
stage (E+H).
After becoming available in 1946, chlorine dioxide received rapid commercial
acceptance
by the kraft industry which
was then able to compete with companies
producing high brightness sulfite pulps.
Sequences such as CEHD and CEHED came
into use for bleaching pulp to 82-85 ISO
brightness and a CEHDED sequence was
used to produce pulps of 90+ ISO brightness.
1.3 Modification of bleaching conditions in response to changing

control methods
Control of the initially used low-consistency batch processes was achieved by adding the chemiqlls to the circulating pulp as
required. When the desired brightness was
reached, the batch was discharged and
washed free of residual chemical. The temperature of the hypochlorite stage was normally a few degrees above ambient summer
water temperature, that is, 30-3;oC. However, for dissolving pulps where hypochlorite was used to control solution viscosity
of the pulp, temperatures in the range of
398

25
,,-,
20
~0
15
:>.
0
c:
Q)
::J 10
c:r
\./
\
\
I
I
I
68C
\
I
I
I
I
~u...
5
0
52
56
60
Brightness,
50-60"<: were used to consume the higher

chemical dosages in a reasonable time.
When medium-consistency
(10-12%)
downflow continuous towers came into
use, only one opportunity was available to
add chemical. Low temperature was important because, in the event of an overdose
of bleach, most was discharged as residual
and washed from the pulp instead of causing severe viscosity and strength losses.
Chemical addition was based on hourly
brightness
measurement
and residual
chemical analysis performed on pulp leaving the 9O-minute retention bleach tower.
When upset conditions occurred in the digester or chlorination stage, this method led
to wide variations in hypochlorite
stage
brightness and viscosity.
In the early 19705, many mi1ls used optical sensors for on-line feedback control of
the chlorination stage. Early attempts to
control the hypochlorite
stage with this
type of sensor were not successful because,
with the sensor located on the stock line
between the thick-stock pump and the
tower, there was very little optical response
to changes In chemical addition on a 2- to
3-minute feedback loop at about 40C.
However, when the bleaching temperature
was later raised to 8O"C, the same sensor
64
68
72
% Elrepho
gave a very strong signal (2). Devoe (3)

showed that, by increasing the hypochlorite stage temperature
from 35-68C, a
much narrower final range of brightness
could be obtained (Fig. 1). Improved brightness control at high temperature leads to a
higher average viscosity
of the fuHy
bleached pulp and to lower chlorine dioxide requirements in later stages (2). However, it is necessary to lower the target
brightness of pulp exiting the hypochlorite
stage washer to take into account the alkaline reversion that occurs when the hypochlorite
charge is exhausted
(2,3).
On-line hypochlorite stage control at high
temperature has made possible the implementation
of countercurrent
washing
through the hypochlorite stage, a procedure
previously developed by Histed on a laboratory scale (4,5).
2. Process variables
2.1 Chemical charge
The chemical charge required to achieve
a given hypochlorite stage brightness is di-
rectly proportionll
to the kappa number
of the extraction-stage pulp (6). The relationship between hypochlorite consumed

and (EO)-stage kappa number can be
399
,j
"'cO
oo .
>
:::::J C\I
0)'5
:t::CT
0)
J:~
0
o
o
2
10
Fig. 2. JJfft of(BO)-6IiIge #uIJIJM__

011tbe -.t
1mQt jIfIlJI to tlllfernt brlgbtrNss '-Is.
mathematically
where H= hypochlorite
B
K
=
=
hypochlorite
ofilypodlWrite
COIUIIIIId hi bletu:bhJg IJllOftrrood
by the equation:
= 14.7113-0.4196(B)-
and Practice
2) pH
(EO) -stage kappa number
expressed
-Principles
2.6 Conditions affecting viscosity loss

The viscosity loss that occurs during hypochlorite bleaching is affected by many
variables:
1) Hypochlorite charge
Co
>:r:
Pulp Bleaching
The pH of the stage is normally determined by mixing caustic with the hypochlorite immediately before the point of addition
of chemical to the pulp. pH can be controlled using a feedback loop from in-line
pH probes located between the thick-stock
pump and the tower. Alternatively, a liquor
extractor may be used to provide a liquid
sample for an external pH probe.
0)
E
400
0.778500
+ 0.OO2873(Bi
+ 0.0163(BxK)
[1]
consumed, % on pulp
brightness
after an S02 (antichlor)
treatment
kappa number ofthe (EO)-stage pulp.
The relationship has a correlation coefficient r' of 0.996. A similar relationship can
be derived for E-stage pulp.
Figure 2, generated from the above equation, shows the linear relationship between
(EO)-stage kappa number and hypochlorite
consumed in reachIng brightness values between 65 and 80.
2.2 Time
A hypochlorite stage can be as shon as 8
minutes at 8O"C or as long as 90 minutes at
the more conventional 35"C.Mills that have
converted from a low-temperature to a hightemperature hypochlorite stage incorporating a 9O-minute retention downflow tower
can decrease the retention time by lowering the operating level in the tower.
2.3 Temperature
Temperature in the hypochlorite stage
may be as low as 3O"C for a conventional
9O-minute stage or as high as 8O"Cfor a stage
having an on-line feedback control system.
2.4 Consistency
The hypochlorite stage normally is operated at a consistency only slightly lower than
the discharge consistency of pulp from the
extraction-stage washer. This general principle takes into account dilution due to the
chemical charge, condensed steam, and any
seal-water leakage. Consistency may be limited on the high side by limitations of the
thick-stock pump. The consistency
may
range from 9-14%. However, at 14%, there
is a risk of non-uniform mixing because the
stock directly in contact with the chemical
at the point of application may adsorb more
than its share of chemical.
2.5pH
The initial pH at the point of pulp-bleaching liquor contact is usually 11 or higher to
maintain a final pH of 9.5 or,preferably,10.
The risk of viscosity loss is less at the higher
pH; below pH 9.0 the viscosity loss for a
given hypochlorite addition may be severe
(7).
3) Kappa number and viscosity of the

unbleached pulp
4) Chlorination-stage kappa factor
5) Kappa number of the E-stage pulp
6) Hypochlorite-stage brightness.
The viscosity of all pulps decreases with
increasing amounts of hypochlorite consumed and increasing final brightness.
However, high kappa number, high viscosity unbleached pulp has a higher viscosity
at a given brightness than a low kappa number,low viscosity pulp. Kraft pulps, chlorinated at a 0.13 or lower kappa factor, have
high CE kappa numbers requiring high hypochlorite consumption to reach a specified brightness. These pulps undergo a
severe viscosity loss when bleached to 70
brightness. In comparison, pulps chlorinated at kappa factors in the range 0.160.20 sustain minimum viscosity loss at 70
brightness.The viscosity loss becomes more
severe when the brightness exceeds 70.
These brightness
values are for pulps
treated with a sulfur dioxide antichlor.
Brightness levels without the addition of an
antichlor may be 4-6 points lower if alkaline reversion has occurred.
3. Reaction kinetics
l1 Kinetic equations
Histed and co-workers (6) have carried
out kinetic studies in a stirred tank reactor
in which kraft pulp was bleached with hy-
pochlorite at varying temperatures and consistencies. The results of this work showed
that the rate of disappearance of hypochlorite is governed by two kinetically distinct
mechanisms:
1) At high hypochlorite concentration (i.e.,
at the beginning of the reaction), the reac,
tion is zero order.
2) At low hypochlorite concentration (i.e., at
the end of the reaction), the reaction is
first order.
The rate equation for the consumption
of hypochlorite in this situation is:
-dfNaOCIl
dt
= -k1 fNaOCIl
[2]
1+k2[NaOCI]
Where k, and k, are the rate constants for

the reaction occurring by the two mechanisms.
Axegard (8) has also studied the stoichiometry and kinetics
of hypochlorite
bleaching as they relate to the decrease in
chromophores, carbohydrate degradation,
and removal of particles. His findings indicate that the rate of chromophore removal
is characterized by a very fast initial reaction followed by a progressively slower reaction. It was concluded that the rate and
stoichiometry
of hypochlorite
bleaching
can be described by the differential equations, [3] and [4], shown below.
The hypochlorite stage is best described
by an apparent reaction order of 3.5 with
respect to the remaining chromophores.
The concentration of chromophores in the
pulp was approximated by the light absorption coefficient, k, determined at 457 nm.
Temperature has a large effect on the rate
of chromophore removal but the effect of
alkalinity is small in the pOH range of 3-5.
This means that the bleaching rate increases
slightly with decreasing pH.
The effect of these variables can be expressed mathematically by the equation:
-dkm
= k,'
[ClO,]06 . [OR].() 1.
km3'
[3]
(it
The stoichiometry of chromophore
removal is not affected by the temperature or
alkalinity, but the concentration
of hypochlorite has a significant effect.The lower

the concentration
of hypochIorite
ions, the
lower the quantity of chemicals consumed

in bleaching to a given k4~7value. In mathematical form, the stoichiometry
is described by the equation:
-d rocr!
kz'---L..
dk457
km11
[4]
The exponent, 11,which varies between 1.0

and 1.3, and the rate constant,k, depend
on the type of pulp and the bleaching conditions.
When the concentration of hypochlorite
ions and the alkalinity are kept constant,
cellulose degradation is directly proportional to the reaction time and independent
ofthe initial lignin content of the pulp (8).
This means that, with respect to carbohy:
drate degradation, the reaction order is zero.
Carbohydrate
degradation
at a given
brightness is less when bleaching is performed at low temperature, low hypochlorite concentration, and high pH. Maximum
pulp cleanliness is obtained using low temperature and a high concentration
of hypochlorite.These
results indicate that a hot
hypochlorite stage leads to low viscosity
and cleanliness. However, these conclusions
are not borne out in commercial practice
where the much lower brightness variation,
~Q.
E"5
~
c::
8~
(I)
~
o
401
402
resulting from on-line optical control, is

reflected
in pulp quality by a higher
monthly-average
pulp viscosity which is
not accompanied by an increase in shive
content (2,3).
-oQ.
(1)_
E
:JQ.:J 0.8
II) c::
c:: 0
~ 0.6
8(l)U
3.2 Effect of temperature

Temperature has a large effect on the rate
of chromophore removal. Axegaro showed
that the effect of temperature on the rate
of hypochlorite bleaching is best described
by an Arrhenius activation energy of 77 :t
5k]/mole (8). The rate of hypochlorite consumption is also strongly affected by temperature
as shown
in Fig.3 where
hypochlorite consumption is plotted against
the log oftime (6).
3.3 Effect of consistency

Consistency has a very strong effect on
reaction rate as shown by Fig.4. Of the 1.0%
hypochlorite applied at 3.0% consistency,
approximately 0.2% is consumed within the
first 3 minutes; at 12% consistency, over
0.9% is consumed in the same time.A comparison of Figs. 3 and 4 shows that increasing the consistency from 3-12% has a much
larger effect on reaction rate than does increasing the temperature from 50-93"<: (6).
~>
.Q'S 0.4
.c::c:r
g (I) 0.2
g;?f.
J:
o
3%
E-stage kappa no., 3.3

Hypocholorite
applied,
Temperature,
10
1.0 % on pulp
50C
100
1000
Time, min
FI,. 4. E/fect of cmuIsIftu:y Oft tile rwU of bypoeblorlt~ t:OIISfIIII/Itk i.. tile bluebl..,
PMlp.
3.4 Effect of pH
The rate of chromophore removal increases slightly with decreasing pH but the
rate of cellulose degradation increases significantly with decreasing pH (8).
4 Process equipment
4.1 Flowsheet of hypochlorite
stage
In a conventional low-temperature
hypochlorite stage, the hypochlorite and alkali are normally added at the re-pulper of
the E-stage washer. The pulp is then dis-
of tI so,ftrtitHMTwtIft
charged vertically downward to a steam

mixer (Fig.5). The steam mixer should be
of the double-shaft design because singleshaft steam mixers do not mix chemicals
efficiently. From the steam mixer, the pulp
drops down a chute into the thick-stock
pump (Fig.5) and thence to the top of a
medium-consistency
downflow tower by
way of a stock line that normally has a 2- to
4-minute retention. The bleached pulp is
discharged from the bottom of the tower
to the H-stage washer.
NaOCI
NaOH
0.8
~
0
D-- --------
U 0.6
Pulp
Sen8Ol'8
1. Temperature
2. pH
3. Brightness
.->-
:c 50.4
(I)
e-?f. 0.2
J:
E-stage kappa no., 3.3

Hypocholorite
applied, 1.0 % on pulp
Consistency,
3.00/0
o
1
10
100
1000
Pump
Time, min
Fig. 3. Effect of temJHmltrtre on the f'tIt~ of typocblorlte _mptItm
PM'p.
I.. the bletu:bl..g of tI softrrooil TwtIft
Pulp

4.2
Effect of bleaching temperature on

equipment design
When the hypochlorite stage is operated
at high temperature, the conventional design may be modified to include an on-line
control system (Fig.5).Because the temperature of the sheet leaving the exttaction-stage
washer is much higher than that from a lowtemperature hypochlorite stage, it is important to move the point of chemical addition
to the throat of the double-shaft steam mixer
to minimize non-uniform bleaching prior to
pulp mixing (2).The a1kali (NaOH) for pH
adjustment
should be added to the hypochlorite solution after their respective
flow meters but before the chemical is
added to the mixer. Multiple injection ports
are desirable to help ensure that the chemicals are distributed uniformly throughout
the pulp.
In-line pH and optical control are essential at high temperature because consumption of any excess chemical may have an
adverse effect on pulp vi5cosity. The optical signal can be enhanced by using it in
conjunction with a polarographic-type
residual chemical sensor. The pH and optical
control sensors are mounted 1- to 3- minutes downstream from the point of chemical addition.
In mills having medium-consistency centrifugal stock pumps, the chemicals may be
added at the feed to the pump. Thorough
initial mixing is essential because there is
no opportunity for diffusion of the chemicals before reaction is almost complete (see
Chap. VI 2). The plots in Fig. 4 show that
the reaction at 50"C and 12% consistency is
more than 90% complete in 3 minutes. As
expected, the bleaching rate is much higher
at 8O"C.
4.3 Use of towers or flow-through tubes
Towers are required for a low-temperature hypochlorite stage but can also be used
in a high-temperature
stage. However, at
high temperatures (70-8O"C), an 8-minute
retention flow-through tube is more than
adequate for complete consumption of the
hypochlorite (2).The feedback control sensors are mounted on the vertical upflow
portion of the tube if possible.
403
At high temperatures, the pulp reaches

its maximum brightness when the bleach
residual disappears. Alkaline reversion then
occurs which can lower the brightness at
the washer by 5 or 6 points although it has
no effect on later chlorine dioxide consumption (2).
5. Particle bleaching with

hypochlorite
In a series of bleaches of hardwood kraft
pulps that had been substantially fortified
with resin shives and resin fibers,
a
(CD)EHED sequence performed as well as
a (CD)EDED sequence with respect to shive
removal when the pulps were bleached to
75 brightness in the H stage (6). A 3O"C
hypochlorite stage gave slightly better shive
removal than an 8O"C stage.
Particle removal increases with increasing brightness after a particular brightness
level is reached (8). This trend reflects the
different kinetic behavioral patterns for
chromophore and shive removal. Chlorine
dioxide is a more efficient chemical for
shive removal than hypochlorite
when
bleaching to high brightness. A detailed
discussion of the effect of bleaching on particle removal is found in Sect. 11 of this
chapter.
6. Hypochlorite bleaching of
dissolving pulp
Hypochlorite
stages are normally required in the manufacture of dissolving
pulps for the viscose process. Hypochlorite is used to control cellulose degradation
to achieve a desired viscosity level and to
further purify the pulp by oxidizing and
solubilizing non-cellulosic components.
Control of the hypochlorite stage bleaching conditions must be maintained to produce a pulp of uniform viscosity and
reactivity. This goal is best accomplished
with a carefully defined bleaching strategy
using state-<>f-the-art process control technology. Typically, only one hypochlorite
stage is required for viscosity control, and
it is normally located after the first alkaline
extraction stage.
The major variables in effective control
of the process are pH, consistency, tempera-
404
ture, and hypochlorite application. One effective strategy is to operate at fixed consistency and temperature and at a fixed pH
above 10. The viscosity reduction is then
controlled by varying the hypochlorite application.
Overbleaching may occur if the pH is
below the optimum, if an excessive dosage
of hypochlorite is applied, or if the temperature significantly exceeds the preselected
maximum. In each case, the rates of bleaching and viscosity loss are both significantly
increased. Overbleaching is evidenced by
a decrease in viscosity and alpha-cellulose
levels.
pH is ordinarily the most important variable in hypochlorite bleaching. For control
purposes, it is normally kept above 10.0
because the degradation reactions leading
to viscosity decrease become much faster
and less controllable as the pH decreases.A
higher pH favors a lower and more controllable bleaching rate. The pH of the hypochlorite stage also affects the aging of the
a1kali cellulose in the viscose process.
The first steps in the viscose process are
mercerization of the pulp with caustic soda
(NaOH) followed by pressing to a constant
cellulose-to-caustic
ratio. The cellulose is
then shredded and aged at constant temperature in the presence of oxygen. During the
aging step, the cellulose depolymerizes at a
rate governed by the carbonyl content of
the cellulose. Because carbonyl formation
during hypochlorite bleaching is low above
pH 10 but increases significantly as the pH
decreases to 7.0 (9), the aging rate is greatly
dependent on hypochlorite stage pH.Variation in hypochlorite
stage pH probably
accounts for much of the variability in solution viscosity in the viscose process.
7. Washing of hypochloritebleached pulp

The primary function of washers is to
remove reaction products and colored material that could consume bleach chemical in a succeeding
bleach stage. In a
conventional bleach plant equlpped with
drum washers, the washers have a secondary function of conveying the pulp from one
stage to the next.
When the kappa number of the pulp leaving the first extraction stage washer is 4.5
or lower and when good washing is provided on the first extraction stage washer
to minimize lignin carryover, a washing step
between the hypochlorite stage and chlorine dioxide stage is not required. Indeed,
the carryover of alkaline salts of weak organic acids formed in the hypochlorite stage
is beneficial because these materials act to
control pH in the following chlorine dioxide stage. This alkali source maintains the
D-stage pH in the optimum range and minimizes viscosity and strength loss in a strong
final chlorine dioxide stage (10).
8. Modern process control

8.1 Sensors
A high-temperature
hypochlorite stage
requires on-line feedback control of the
hypochlorite and a1kali additions. Alkali addition is controlled by a pH sensor, hypochlorite addition is controlled solely by
a signal from an optical sensor or by a combined signal from a pair of sensors which
make both optical and residual chemical
measurements. The latter signal is referred
to as "compensated brightness." For maximum sensitivity, the optical signal should
be measured at approximately 420 nm because this is the wavelength at which the
maximum change in the reflectance of the
pulp occurs during hypochlorite bleaching.
8.2 Sensor location
Ideally, pH and optical sensors are located
side by side at a site approximately
1.5-3
minutes downstream
from the point of
chemical addition. If a compensated brightness signal is used, the residual chemical
sensor must be located in close proximity
to the optical sensor. Factors influencing
sensor location are:
(l)Target brightness (affects chemical consumption)
(2)Temperature
(affects reaction rate)
(3) Range of tonnage rate variation (affects
retention time).
When optical control alone is used, it is
desirable to position the sensor at a point
405
406
80
70
60
c 50
OJ
'00
a; 40
a;
88
en
U)
A
Hypochlorite
:;::: 30
Final
pH
10.6
10.5
10.6
11.3
applied, % on pulp
A
0.45
B
0.7
C
1.03
D
1.03
20
10
0
0
10
15
20
CD
C
Rnal
brightness, % ISO
58
71.2
76.7
74.7
25
30
.s::.
Fig. 6. Effecl of byJJoeblmittJ elHnp,Ji"'" JIll, tIIUIre'-lkm

so.ftrti004 ImIft Jnllp blu:'-l tll8ff'C tIIUI:1.2%~.
where nearly all of the change in optical

response occurs at the lowest production
rate. Figure 6 shows typical optical responses for a kraft pulp bleached with hy.
The principles for on-line hypochlorite

stage control and sensor location can be illustrated using Fig.6. However, in a mill situation, actual retention
times at 12%
consistency are much shorter for the reasons discussed in Subsect. 3.3.
It is important to select a retention time
which gives good separation of signals for
various chemical charges and for final
brightness. In Fig. 6, this occurs at about 5
minutes for curves A, B, and C at a final pH
ofabout 10.5. Since curves B and C increase
with time, changes in production rate require a change of setpoint if an optical signal is the sole means of control
for
hypochlorite
addition. Curve A passes
through a maximum at the point where all
of the residual hypochlorite is consumed.
Beyond this point alkaline reversion occurs.
It is important, therefore, to properly locate
the sensors so that the optical signal is recorded before the hypochlorite
is exhausted.
The bottom curve shows alkaline reversion starting to occur at about 6 minutes,
the point where the hypochlorite is all consumed.
11IM OIIlbe oplit:4l sigul
86
OJ
'C
m
35
84
1.5
2.5
3.5
4.5
Chemical consumed, % on pulp equiv. CI2
Retention time, min
pochlorite (6).
90
~~0
(.)
a.
0
92
i. lbe bktu:lmlg of tI
8.3 Response of optical sensors

In Fig. 6, the very sharp increase in optical response in the first 2 minutes of reaction is a visual demonstration of the kinetics
discussed in Subsect. 3.1: a very fast initial
reaction followed by a slower reaction after 2 minutes up to completion
of the
bleach.
Curves C and D in Fig. 6 illustrate the
effect of pH on optical response. Curve C,
corresponding
to a pulp bleached under
conditions where the final pH was a normal 10.6, has a much higher optical signal
than a pulp bleached under conditions
where the final pH was high (11.3). It is
therefore evident that, to reliably monitor
the progress of a bleach, good control of
the pH is required when a feedback optical
control system is used.
8.4 pH sensors
At least two types of in-line pH sensors
are available. One type, which does not
have a bubble in the glass electrode, can be
mounted in any orientation. Glass electrodes having bubbles must be mounted
slanting downward. Electrodes should not
be mounted on the bottom of horizontal
pipes, where extraneous metal fragments
can shear them off or on pipe elbows where
turbulent flow can abrade them and shorten
their life. Ideally, pH sensors are located in
Fig. 7. Brlgbtrlas
resJHnIU of (W)E .'lgrdftetl
sIIIga oftbe (W)E(DIEID)
tIIUI (W)E(HID)
so.ftrti004 ImIft Jnllps

Sl!tJIIi!fI"S.
a pipe that remains full during shutdowns

so that the electrodes do not dry out. The
pipe should also have a sample port near
the electrode for calibration purposes. Some
residual chemical
sensor probes are
equipped with liquor extractors which conveya liquid sample to an external pH probe.
9. Economicconsiderations
In general, to be cost effective, hypochlorite should be less expensive than chlorine
dioxide on an oxidizing equivalent basis.
Figure 7 shows that, on an equivalent chlorine basis, the (DIEID) stage pulps of a simplified (CD)E(DIEID) sequence have higher
brightness and a higher brightness ceiling
than the same extraction
stage pulps
bleached by the (CD)E(HID) sequence. This
is true for pulps chlorinated at 0.157 or 0.22
kappa factor. Therefore, the (CD)E(DIEID)
sequence is more cost effective than the
(CD)E(HID) sequence unless the chlorine
dioxide generator produces by-product hypochIorite which would require disposal.
Figure 8 shows that pulp bleached in a
(CD)E(DIEID) sequence has better brightness stability than that bleached
in a
(CD)E(H/D) sequence. However, if the
grade of pulp being produced requires low
viscosity, or rapid strength development
during beating, the hypochlorite sequence
would be favored.
bletlt:'-l
,.
lbe (DIEID) tIIUI (HID)
Some mills use lime bleach (calcium hypochlorite) because lime is a less expensive
alkali than sodium hydroxide. However, use
of a calcium base may be disadvantageous
for a variety of reasons. When sodium hydroxide is added for pH control, lime is precipitated onto the fiber. Lime carryover into
a following chlorine dioxide stage may lead
to low brightness because of the high pH.
Also, lime bleach cannot be used in countercurrent washing because of problems
associated with lime scale formation.
The use of a hypochlorite stage necessitates the inclusion of an additional wash
before the D, stage in a CEHDED sequence.
A 1978 survey of Canadian mills (11)
showed that six-stage bleacheries used an
average of 6.8 kg of CIO /metric ton of pulp
compared with 17.7 kg ofCIO/metric
ton
of pulp used by five-stage CEDED bleacheries. This difference in chlorine dioxide
consumption cannot be explained by the
10 kg of Cljtonne of pulp normally used in
the hypochlorite
stage. Poor extractionstage washing is suspect as the cause of
much of the high chlorine dioxide consumption in the D, stage of the CEDED sequence. Most bleachery washers remove
only 85% of the solids generated in the extraction stage. This amount increases to 97%
removal after two stages. The waste of chlorine dioxide in the D, stage was confirmed
Chapter IV 9: HypocWorite and HypocWorous Acid Bleaching
0
0
407
C>
':
CC

88
90
~~88
86
~
c:
1:
C)
82
22
80
20 '(jj
0
u
I/)
80
18 :>
78
76
78
84
86
88
Initial brightness,
90
92
a.
u
;i.
82
':
III
"1. B.Rellllimublp be'sojhtItJN itwft ~
24
w
~
cf?84
u)
cii
c: 86
'en
as
...
Q) 84
=as
I/)
I/)
Q)
c:
408
16
2.0
3.0
% ISO
4.0
5.0
6.0
pH
tbe IIIUW.. T-ZfiOfftIe1'tM""'lbl8tJss'" tbe blHd1i"l of(CD)H.'ipiftetl

,,, (1JIlVD) (HID).,.~.
"'"'
after some six-stage bleacheries used the H

stage as a water soak and second wash. In
this example, the carryover of EI dissolved
solids into the DI stage d(ove the cWorine
dioxide application to the asymptotic limit.
The uppermost curve in Fig. 7 illustrates
the asymptotic approach of brightness to
its maximum value with increasing chemical application.
A hypocWorite stage can be used to control the beating properties of bleached kraft
pulps (6). Less refining energy is requln:d
to achieve a given freeness when a hypochlorite stage is part of the bleaching
sequence. This is a particularly attractive
feature for paper mills lacking sufficient
refining capacity.
A normal hypocWorite stage in a bleach
sequence has no adverse effect on the yield
of fully bleached pulp. However, yield may
decrease if severe cellulose degradation
occurs as a result of bleaching in the 6-8
pH range.
10. Environmental aspects

The United States government became
concerned about cWoroform in the environment following its detection in cWorinated
drinking water (12). This finding led ulti.
mately to the identification of chloroform
in bleach plant effluents (13). In 1985 the
Environmental Protection Agency reported
that pulp bleaching was the single largest

source of chloroform emission to the atmosphere in the United States (14). Primarily
because of cWoroform formation, the hypocWorite stage is gradua1ly being phased
out of pulp mills in the United States.
The hypocWorite stage is by far the largest source of cWoroform in a multi-stage
bleaching sequence, accounting for 5-15
times the total amount produced by the C,E,
and D stages (15). HypocWorite consumption is the dominant factor affecting the
amount of cWoroform produced in the hypochlorite stage (15). CWoroform formation
is a1sO indirectly a function of the kappa
number of the pulp entering the hypochlorite stage (16) because the CE kappa number usually determines
the size of the
hypocWorite charge.
For a specified hypocWorite charge,hardwoods produce much less chloroform than
do softwoods (15). An investigation of the
mechanism of cWoroform formation (17)
has led to the conclusion that most of the
chloroform is derived from aromatic ring
carbon atoms in residual lignin.
11.Chlorinemonoxidebleaching
of pulp
11.1 Background
Chlorine monoxide (CIP) is a reddish
yellow gas which was first synthesized in
1834 by the French chemist Belard. A comprehensive review of the chemistry of this
compound has been published (18).
Uebergott and Bolker (19, 20) used chlorine monoxide to delignify unbleached kraft
pulp in the first stage of a high<onsistency
bleaching sequence. Chlorine monoxide,
2%, was applied to the pulp at 30",1,consistency in a I-minute treatment. The resultant pulp had a lower kappa number (4.3
compared with 7.6) than pulp delignified
in a conventional chlorination stage (5.9",(,
Clz on pulp at low consistency). By bleaching at high consistency, it was a1sOpossible
to replace cWorine dioxide with chlorine
monoxide in the latter stages of a multi-stage
bleach sequence and produce pulp of comparable brightness and strength.The bleaching characteristics
of chlorine monoxide
have also been studied by Christiansen and
Friedt (21).
Hypochlorous
acid (HOCI) is the hydrated form of cWorine monoxide. It is also
formed in the cWorine-water or hypochlorite-water systems by pH adjustment. In
such systems, hypochlorous
acid is the
dominant species present between pH 3
and S. Hypochlorous acid is a very powerful oxidizing agent with a standard reduction potential of 1.63 volts. However, it has
generally been considered to be destructive
of cellulose and therefore has been avoided

in pulp bleaching (22).The destructive action .of hypochlorous acid can be curbed
by the use of additives that inhibit the degradation reactions. In some cases, where a
low pH in the hypochlorite stage has been
deliberately used to increase the reaction
rate, sulfamic acid is added to prevent excessive cellulose degradation (23). MonoxL,a patented mixture of hypochlorous acid
and one or more of several nltrogen additives (24), has been used in several bleach
plants (25-27).
11.2 Effect of pH
The pH of the hypochlorous acid bleaching stage is the most critical process variable affecting pulp and effluent properties.
The pH at the end of a hypochlorous acid
bleaching stage should be between 3 and
5. In this pH range hypochlorous acid is the
dominant species and pulp brightness and
viscosity are maximumized. Figure 9 illustrates the brightness and viscosity response
of kraft pulp to hypochlorous acid in conjunction with a nitrogen additive over a pH
range of 2-6.The plots indicate that. below
pH 3, the brightness and viscosity of the
pulp decrease significantly. At pH values
higher than approximately 4.5, brightness
begins to decrease.

84
0
82
~80
en
78
en
Q)
409
~~~24
22
20
(C+D)(E+O) H
a.
76
18
~u
72
+ 70
~w
68
CJ
66
64
16
:g
c:
~~? 74
.;::
.r::.
C)
~+O)M
a:!
14
~12
10
0.8
1.0
1.2
1.4
1.6
1.8
Chemical charged, % equiv. CI2 on pulp

Fig. 10.ComJMrlstm of tbe tlfft of H muI M sl4ps 018
fl"'"
softwood In'fIft pulp.

Generally, the conditions
used in hypochlorous
acid and chlorine dioxide
bleaching stages are similar. Bleaching-stage
temperatures can be varied between 50 and
70DC and reaction times between 1 and 4
hours. It is desirable to maintain a small residual (50-100 ppm) of hypochlorous acid
at the end of the bleaching stage and the
temperature or time should be adjusted to
obtain this residual. Satisfactory bleaching
results have been attained using pulp consistencies between 3 and 12%.
11.4 Bleaching responses
Substitution of a combined mixture of
hypochlorous acid and a nitrogen-containing additive for chlorine dioxide in the D,
stage involves replacing the chlorine dioxide with an equivalent amount (on a weight
basis) of hypochlorous acid.The brightness
and viscosity
of a pulp bleached
in
a(C+D)(E+O)MED
sequence
(where M
stands for Monox-L) is comparable to that
obtained using a(C+D)(E+O)DED sequence
(28).
Substitution of hypochlorous acid and a
viscosity protector (M stage) for hypochlorite can produce pulp having a higher
brightness and viscosity. Figure 10 shows
a comparison of the brightness of a soft-
IJrlgblrJess
I" tbe mulU-stflgtl blHebl"g
410
Pulp Bleaching
-Principles
and Practice
ing the pH of the hypochlorous acid stage

below 5, chloroform formation is minimized; 40-80"10reduction of chloroform can
be achieved by substituting hypochlorous
acid for hypochlorite (28).
11. Boughner, R.T., "Chlorine Dioxide Bleaching and Manufacture

- 1978," Rpt.issued
by CPPA Tech. Sect. Alkaline
Pulping
Committee,
1979.
11.6 Hypochlorous
acid generation
Hypochlorous acid is not stable and has
to be generated at the mill site. The raw
materials are water, alkali, and chlorine.
When Monox-L is used, a nitrogen-containing viscosity protector is also added. The
materials of construction for the hypochlorous acid generator must be such that they
can tolerate the acidic (pH 4.5), strongly
oxidizing medium. Such materials include
titanium, Hastalloy, and some plastics.
13. NCASI, Tech. Bulletin No.298, National

Council of the Paper Industry for Air and
Stream Improvement,
New York, 1977.
11.5 Environmental
aspects
Hypochlorous acid bleaching has significant environmental advantages over chlorine or hypochlorite bleaching.To maintain
these advantages, the pH of the hypochlorous acid stage should be between 3.0 and
4.5. If the pH decreases much below 3, the
fraction of chlorine (Clz) present in the system increases (see Chap. IV 2, Fig. 3). Chlorine undergoes substitution reactions with
lignin more extensively than does hypochlorous acid which reacts oxidatively. As a result, the quantity of chlorinated organic
compounds increases dramatically in lower
3.5) pH regions. As evidence of this, mill
data have shown that tetrachlorodioxin
is
non-detectable when hypochlorous acid is
used as a bleaching agent and that AOX levels can be reduced by 30-60% compared to
when chlorine is used (27).
Chloroform formation is also heavily influenced by pH and is enhanced under
alkaline bleaching conditions. By maintain-
References
1. Hatch, R.S., The History
of Bleaching,
Monograph
No. 27, (WH. Rapson, Ed.),
TAPPI PRESS,Atlanta, 1963, pp. 1-7.
2. Milne, P.T.,"High Temperature
Short Retention Hypochlorite
Bleaching; International
Pulp Bleaching
Conference,
Preprints,
Tech Sect. CPPA, 1979. Montreal, p. 189.
3. Devoe, P.,"Crofton's Experience with High
Temperature
Hypochlorite
Bleaching", intern. Pulp Bleaching Conference Preprints,
Tech Sect. CPPA, 1979, Montreal, p.185.
4. Histed, J.A. and Nicolle,
EM.A., CPAR
Project Report 47-4,(copies
available from
Environment Canada library, Place Vincent
Massey, 251 St. Joseph
Blvd. Hull QC
Canada KIA OH3), 1974, pp. 3-20.
5. Histed, J.A. and
59(3):75 (1976).
6. Histed,J.A.,
Inc.
private
7. Rapson,WH.,
Nicolle,
EM.A.,
file courtesy
Tappi 39(5):284
Tappi
of Avenor
(1956).
8. Axegard,
P. and Tormund,
D., Svensk
Papperstidn.
88(3):R36 (1985).
9. Rapson, WH., Anderson,
Tappi 41(8):422 (1958).
C.B., King, G.F.,
10. Histed,
(Dec.9,
No. 4,238,281
J.A., U.S. Pat.

1980).
Exam.
23(2):
14. U.S. EPA Report No. EPA-450/3-85-026,

Environmental
Protection
Agency, Washington DC, 1985.
15. Crawford,
R.]., Stryker, M.N., Jett, S.W.,
Carpenter,
W.L., Fisher, R.P., Jain, A.K.,
Tappi] 70(11):123 (1987).
16. Dallons, Y.J., Hoy, D.R., Messner,
R.A.,
Crawford, R.]., Tappij. 73(6):91 (1990).
17. Hrutfiord,
73(6):219
of fI
wood kraft pulp bleached in (C+D)(E+O)M

and(C+D)(E+O)H
sequences. At a given
charge level, the hypochlorous
acidbleached pulp is approximately
6 points
brighter and the viscosity is 4 units higher
compared
with hypochlorite
bleached
pulp.
12. Rook,]., Water Treatment

234 (1974).
B.F. and Negri, A.R., Tappi]

(1990).
18. Renard, J.J. and Bolker, H.I., Chern.

76(4):487 (1976).
Rev.
19. liebergott,
N. and Bolker, H.I., U.S. Pat.
No. 3,619,359 (Nov.9, 1971).
20. Bolker, H.I. and liebergott,
N., Pulp
Mag. Can. 73(11):T332
(1972).
Pap.
21. Christiansen,
C.B. and Friedt, R.D., Paper
Trade] 159(19):44 (1975).
22. Larson, L.E. in Handbook
of Pulp and Paper Technology @ritt, K.W,Ed.) 2nd eOO.
Reinhold, New York, 1970, p.272.
23. Larson, L.E., U.S. Pat. No. 3,177,111
6, 1954).
(April
24. Yant, R.E., Wolfe, A.L., Hurst, M.M., U.S.

Pat. No. 4,740,212 (April 26, 1988).
25. Hurst, M.M., Korhonen,
R., Vakeva, K.,
Yant, R.E., Pulp Pap. Can. 93(11):T311
(1992).
26. Yant, R.E. and Hurst,
74(4):165 (1991).
M.M.,
Tappi]
27. Klykken, P.G. and Hurst, M.M., "Molecular Chlorine Free Bleaching with MonoxL," 1991 TAPPI Pulping Conference
28. Yant, R., Smeds, U., Hyvarinen,
H., 76th
Annual Meeting Proceedings,
Tech. Section, CPPA, Montreal, 1990, p. 315.
SECfION IV:
The Technology of
Chapter 10:
Hydrogen Peroxide Bleaching
J. Ross
Anderson
DuPont Canada Inc.

Maitland, Ontario
Canada KOE lPO
B. Amini
E.I. DuPont de Nemours & Co.
Wilmington, Delaware
U.S.A. 19898
1. Introduction.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
413

. . . . . . .. . . . . . .. . . ..
2.1 Reactions of hydrogen peroxide with lignin
under alkaline conditions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2 Hydrogen peroxide decompostion reactions. . . . . . . . . . . . . . . . . . . . . . . . . .
2.3 Kinetics and stoichiometry of hydrogen peroxide bleaching. . . . . . . . . . . . . .
415
415
416
3. Factors affecting brightness in hydrogen peroxide bleaching. . . . . . . . . . . . ..

3.1 Bleaching conditions.
3.2 Wood type (hardwood and softwood) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3 Kappanumberofunbleachedpuip
3.4 Carryover
..............
3.5 Hydrogen peroxide decomposition and its control. . . . . . . . . . . . . . . . . . . . .
417
417
421
422
422
424
4. Typical hydrogen peroxide bleaching sequence applications

4.1 "Conventional"
4.2 ECF . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3 TCF . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
428
428
429
429
5. Pulp
5.1
5.2
5.3
414
quality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 430
Brightness stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 430
Strength
431
Cleanliness
431
6. Process Oowsheets
7. Environmental
8. Economics
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
considerations
of hydrogen
432
434
peroxide bleaching.
. . . . . . . . . . . . . . . . . . . . . . . . . . .. 434
9. Activators and hydrogen peroxice.cJerived bleaching
agents.
. . . . . . . . . . . . ..
435
9.1 Hydrogen peroxide activators. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 435

9.2 Hydrogen peroxide-derived bleaching agents
435
411
Chapter IV 10: Hydrogen Peroxide Bleaching
Chapter IV 10:
Hydrogen Peroxide
Bleaching
1. Introduction
The use of hydrogen peroxide ("peroxide") as a wood pulp bleaching agent has
been well documented since its introduction for mechanical pulp bleaching in 1940.
The literature dealing with the early development of hydrogen peroxide bleaching has
been comprehensively reviewed by Beeman
and Reichert (1) and later by Holladay and
Solari (2). The more recent review of hydrogen peroxide bleaching by Andrews and
Singh (3) includes examples of its applif,;ation to chemical pulps.
Before the widespread use of cWorine
dioxide, a typical use of hydrogen peroxide was in short bleaching sequences, of the
type CEHP, for producing brightness levels
in the range of 75-85% ISO. The introduction of cWorine dioxide led to the division
of old multi-stage processes and the development of many short sequences. The addition of a final hydrogen peroxide stage in
such a sequence contributes to a gain in
brightness and brightness stability while
preserving high viscosity and pulp strength.
Similar benefits are seen with the substitution of hydrogen peroxide for sodium hypocWorite.
The proliferation in the late 19508 and
1960s of five- and six-stage bleach plants
using cWorine dioxide in multiple bleaching stages led to a general shift to high
brightness (>89% ISO) and high-strength
market chemical pulps. Hydrogen peroxide
was used in the final bleaching stages to
achieve higher brightness P-<)2% ISO) and
improved brightness stability for specialty
pulps (4). Over the years, the versatility and
relative ease of use of peroxide has led to
applications that overcome the inherent
limitations of existing bleach plant equipment and chemicals. A typical application
of peroxide involves reinforcement of an
alkaline extraction stage, which transforms
it from a simple extraction or washing stage
413
into an oxidative delignification or bleaching stage (see Chaps. IV 4 and IV 6).

The growth in the use of hydrogen peroxide in chemical pulp bleaching since the
late 1980s is attributable largely to environmental constraints in the operation of
the bleach plant. The Pulp and Paper Research Institute of Canada (pAPRICAN) has
identified kappa factor reduction as one
means of e1iminating the formation of"dioxin", specifically 2,3,7,8-tetrachlorodibenzo-p-dioxin
(2,3,7,8-TCDD)
and
decreasing the formation of adsorbable organic halogens (AOX) (5-7).
Use of hydrogen peroxide to reinforce
the oxidative extraction stage (see Chap. IV
4) enables the preceding cWorination stage
to be operated at a lower kappa factor. Although this is primarily a demonstration of
the delignification capability of hydrogen
peroxide, the pulp and effluent from the
extraction stage are also bleached (7,8).The
increase in brightness and lower kappa
number of the pulp leaving the extraction
stage allow the redistribution of part of the
cWorine dioxide from the bleaching (brightening) stages to the cWorination stage.This
leads to an increase in the cWorine dioxide
substitution level and/or elimination of cWorine in the cWorination stage (7,8).A typical sequence for this purpose is (D,D+C)
(E+O+P)DPD.
For elimination of dioxin, approximately
70"A, of the cWorine must be replaced by
cWorine dioxide in the chlorination stage
(D+C). Therefore, many mills installed additional cWorine dioxide capacity in the
mid-1980s to reach this substitution level.
A developing market for ECF pulp, bleached
without the use of cWorine in its elemental
form, Cl2, now finds many of these mills
again having insufficient cWorine dioxide
capacity to convert to an ECF process. In
such cases, hydrogen peroxide can be used
to decrease the total cWorine dioxide requirement of the mill and enable it to maintain its pulp production
rate when
operating an ECF process. Some softwood
kraft pulp mills, particularly those employing oxygen delignification, experience a
decrease in brightness ceiling when they
414
convert to ECF bleaching. Hydrogen peroxide reinforcement

of extraction stages
may allow such mills to regain their fmal
brightness target and decrease their chemical bleaching costs (8,9). Typical modern
ECF bleaching sequences are D(E+O+P)
DPD and OD(E+O+PX(D+E)/D).
As market niches for totally cWorine-free
(TCF) pulps and low AOX pulps have developed, interest has shifted to non-cl1lorine
chemicals including hydrogen peroxide. An
integral part of allTCF chemical pulp bleaching sequences is the use of a peroxide
bleaching stage or stages. Initially, sulfite
TCF pulps were introduced at brightness
levels in the low 80s. However, technical
advances since that time period have led to
the production of fully bleached sulfite, as
well as kraft pulps, having brightness targets approaching 9O"A,ISO.
The initial kraftTCF bleaching sequences
mimicked the bleached
chemithermomechanical pulp bleaching concepts of
metals management and multiple peroxide
bleaching stages. Because the final brightness is a function of the lignin content of
the pulp, most mills have invested in extended delignification and/or an oxygen
delignification stage to lower the kappa
number of the pulp entering the bleaching
stage (10,11). They have also focused on
effective screening and washing operations.
Typical early kraftTCF bleaching sequences
were of the type OQE+O+P)PP).
More
recent mill experience has shown that other
non-cWorine bleaching agents can also be
used to further delignify the pulp and thus
achieve a higher brightness. Ozone, for example, is now used at both high and medium consistency on a commercial scale.
Hydrogen peroxide can also be used as a
starting chemical for the production
of
peroxy acids. The peroxy acids, which have
a higher oxidation potential than hydrogen
peroxide, are capable of selectively oxidizing lignin (12). Peroxy acids can increase
the TCF pulp brightness threshold by 3-4
points when applied at the start of a kraft
TCF bleaching sequence (13), They are also
being investigated as a means of activating
oxygen stages and hydrogen peroxide
bleaching stages (14,15).
When peroxide is used to reinforce an

extraction stage, the process conditions are
relatively mild and decomposition is not a
major factor. However, when peroxide is
used as the primary bleaching and delignification reagent, it is usually necessary to
operate the peroxide stage at higher temperatures (> 100C) and under pressure (see
Chapt. VI 6). Under these conditions, the
tWo competing reactions (pulp bleaching
and peroxide decomposition) must be managed. Because transition metals catalyze the
decomposition of hydrogen peroxide, this
undesirable reaction must be minimized by
reducing the metal content of the pulp.
Specially designed pressurized hydrogen
peroxide stages, (PO), have been installed
in commercial operations and have resulted
in improved bleaching response at lower
hydrogen peroxide consumption (16, 17).
Commercial
sequences,
combining
an
ozone stage and the (PO) stage, have taken
the form OZQ(PO). The (PO) stage has also
been incorporated into ECF bleaching sequences.
Advances in of hydrogen
peroxide
bleaching technology have been critical to
the development oITCF-bleached chemical
pulps.The improved performance and efficiency of these technologies, however, are
also applicable to ECF sequences. In addition, further development in the use' of activators and stabilizers
for hydrogen
peroxide should allow better control of its
reaction kinetics during bleaching. This,
coupled with improvements in the design
of hydrogen peroxide bleaching stages, can
ultimately be incorporated into an effluentfree chemical pulp bleaching concept.

Most studies on the chemistry of hydrogen peroxide bleaching have been confined
to the reactions of hydrogen peroxide with
the lignin under alkaline conditions. These
studies have been carried
out with
(chemi)mechanical
pulps or with lignin
model compounds. In such instances, the
main concern has been in establishing how
...~,
~-

hydrogen peroxide selectively removes the
chromophore groups that contribute to the
color of the pulp without concurrently attacking the lignin and reducing pulp yield.
Several reactions that illustrate this process
are described in Chap. III 4. This concept
contrasts with the objectives in the hydrogen peroxide bleaching of chemical pulps
where the emphasis is on the combined
removal of the residual lignin and bleaching the pulp.
The chemistry of (chemi)mechanical
pulp bleaching is relatively simple because
the lignin is mostly unchanged after the
peroxide treatment. The color<ontributing
structures (chromophores)
of mechanical
pulps are well-known and only one or two
hydrogen peroxide stages are used to bleach
this type of pulp to its target brightness.
Chemical pulping, on the other hand, leads
to extensive modification ofthe lignin and
a variety of new structures are formed (see
Chap. III 1). These reactions of lignin with
hydrogen peroxide have not been as thoroughly investigated, and the chemistry of
hydrogen peroxide reactions with pulp is
further complicated by decomposition of
peroxide into oxygen<ontaining
free radicals such as hydroxyl (RO') and superoxide ion (02;)(18,19).
These radicals can
also participate
in de lignification
and
bleaching (20).
2.1 Reactions of hydrogen peroxide

with lignin under alkaline conditions
Hydrogen peroxide, under alkaline conditions, as it is normally used, reacts with
the hydroxyl
ion (HO) to yield the
perhydroxyl anion (ROO-):
HPz
+ HO- ->
HOO.
+ HP
[1]
This anion is a strong nucleophile and is

primarily responsible for the bleaching effect of alkaline hydrogen peroxide.
There are two competing reactions in hydrogen peroxide bleaching:The first leads
to a brightness increase while a second parallel reaction leads to the decomposition of
hydrogen peroxide into water and oxygen.
415
Hydrogen peroxide bleaching reactions are

discussed in Chap. III 4.
2.2
Hydrogen
peroxide
416
HO' + HOO- -> 02; + HP
[3]
02; + HP2 -> 02 + HO' + OH-
[4]
decomposition
reactions
Hydrogen peroxide decomposition
is
catalyzed by metais normally present in the
bleaching solution and pulp. Martin (21)
established that hydrogen peroxide decomposition, as well as the bleaching reaction,
is first order with respect to hydrogen peroxide concentration. Tests also showed that
hydrogen peroxide consumption increases
as the pH is increased from 9 to 12; this
was attributed to an enhanced reaction of
hydrogen peroxide with the pulp.Although
the rate of hydrogen peroxide decomposition also increases with the increasing pH,
decomposition can be minimized by addition of stabilizers.
To utilize alkaline hydrogen peroxide as
an effective lignin-retainin bleaching agent,
precautions should be taken to minimize
peroxide decomposition. Some decomposition products, however, may be necessary
for delignification and bleaching of kraft
pulps with hydrogen peroxide (18 and
Chapt IV 6). In conventional bleaching sequences, decomposition of hydrogen peroxide can be controlled by:
Using mild alkaline bleaching conditions
Stabilizing the hydrogen peroxide (by the
addition of magnesium sulfate and s0dium silicate)
Removing transition metals from the pulp
(by pretreatment with an acid or chelating agent).
Despite these measures, Gellerstedt et al.
(22) showed that hydrogen peroxide decomposition will occur to some extent.The
principal decomposition products studied
are hydroxyl radicals, HO', and, to a lesser
extent, superoxide
anion radicals, 02;
(23,24). The generation of hydroxyl radicals occurs primarily by the transition metal
(M) ion<atalyzed decomposition of hydrogen peroxide (23,24):
Alkali-induced cleavage of hydrogen peroxide has also been described (23,24).

The hydroxyl radical is the most powerful one-electron oxidant in an aqueous s0lution (23) and has a standard oxidation
potential of 2.32V in neutral media. Because
the half-life of hydroxyl radicals is very
short, reactions tend to occur near the generation site.The proximity of the site of radical generation to potential chromophores
may increase the likelihood for the occurrence of reactions leading to chromophore
destruction. The effectiveness of radical
species in increasing pulp brightness is influenced by whether peroxide decomposition occurs predominantly in solution or on
the fiber. Hobbs and Abbot (20) have found
that manganese is bound almost exclusively
to the lignin portion of the pulp and have
proposed that radical species resulting from
decomposition of hydrogen peroxide attack
only the lignin and do not cause cellulose
degradation. Their study also showed that
hydroxyl radicals brighten the pulp in hydrogen peroxide bleaching while superoxide anion radicals depolymerize cellulose.
Phenolic units in lignin can react with
hydroxyl radicals; the reaction is accelerated by the presence of transition metals.
Hydroxyl radicals are also believed to react
by electrophilic addition to the aromatic
rings of lignin (23). It has also been postulated that radical species play a more significant role in pulp bleaching at higher
pulp consistencies (20).
Although hydroxyl radicals can degrade
carbohydrates,
they react preferentially
with the phenolic units (25) that are plentiful in the residual lignin ofkraft pulps. This
tendency depends on the kraft pulp bleaching stage and the ratio of lignin to the carbohydrates
in the pulp. Free radical
reactions may contribute positively to pulp
delignification and bleaching but it is important to control the decomposition of

hydrogen peroxide to minimize pulp degradation and improve the efficiency of the
bleaching
process.
Gellerstedt
and
Pettersson (26) have shown that efficient
control of transition metals in chemical
pulps and control of pH and temperature
conditions make it possible to use hydroge~ peroxide to substantially increase pulp
bnghtness and remove a major portion of
~e re~iduallignin without decreasing pulp
VISCOSity to an unacceptable
level.
2.3 Kinetics and stoichiometry
of
hydrogen peroxide bleaching

In a hydrogen peroxide bleaching stage,
the elimination of chromophores
in pulp
can be modeled according to the Arrhenius
rate law for chemical reactions (27). Assumi~g that the perhydroxyl anion is the prinCipal active species in the elimination of
chromophores (19), the rate of destruction
of chromophores is given by the following
equation (27):
-dNdlron,ldt = OK exp(-E IR1) [HOO- ] Ndvom
0'
[5]
where Neh = chromophore concentration

in the pulp at a given time,
[HOO-]
=perhydroxyl
anion concen
, tration,
= gas constant,
Ko = rate constant,
T = absolute temperature,
E, = activation energy, and
D = transfer coefficient from liquid
to pulp phase.
According
to this model, the highest
rate
of brightness
increase is obtained with
1) The highest practical
temperature.
Temperature is limited by the homolytic cleavage. of hydrogen
peroxide into hydroxyl
radicals (approximately
130C)(28).
2) A high concentration
of perhydroxyl
anion. This is affected by the amount of hydrogen peroxide applied, the alkali charge
(for convcr~iQn of peroxide
to the
pe~hydroxyl
anion), and the rate of peroXide decomposition.The
optimum alkali
charge is not necessarily the highest practical charge but pH must be sufficiently
~--~---_....--

high to ensure that the rate of formation
of perhydroxyl anions is not the rate limiting step. An excessively high pH, however, may result in alkali-induced decomposition of peroxide, or increase its rate
of decomposition
through transition
metakatalyzed reactions. High pulp consistency contributes to higher effective
bleaching concentrations and an increased
likelihood of chromophore elimination.
3) Unimpeded transport in liquid phase.
When the temperature is raised above the
boiling point of the bleaching liquor, vapor bubbles can form at the interface between the liquid phase and the pulp surface. This phenomenon interferes with
the transport of bleaching reagents to the
pulp (27). Increasing the pressure increases the boiling point which prevents
the formation of gas bubbles. The net result should be maintenance of the transfer coefficient, D, at a high level. To date,
the value of D has not been determined
and the role of other surface-active technologies that could further improve the
transfer of active bleaChing species to the
fiber surface has not been investigated.
In bleaching pulp with hydrogen peroxide, the peroxide is consumed in two parallel reactions:
pulp brightening
and
decomposition.
Decomposition, which decreases the perhydroxyl anion concentration, can be controlled to some extent by
minimizing the concentration of transition
metals and by addition of peroxide stabilizers. Stabilizers can sequester (i.e., deactivate) the metals that catalyze hydrogen
peroxide decomposition.
The exponential
expression
of the
Arrhenius equation predicts that: the larger
the activation energy, Ea' the more sensitive
the reaction rate will be to temperature
changes. When there are two competing
reactions, raising the temperature will accelerate the reaction that has a higher activation energy to a greater extent than the
one with a lower activation energy. Although the activation energies of pulp
bleaching and peroxide decomposition are
not known, it may be assumed that the
activation energy of the transition metalcatalyzed decomposition is much lower because it occurs readily under moderate
417
reaction conditions. Therefore, an increase

in temperature should enhance the bleaching reaction to a greater extent than the decomposition of peroxide.These conclusions
are confirmed by recent experience that has
shown significantly improved brightness
response by operating a peroxide stage at
high temperature and pressure (16,17,28).
In this case, the difference in activation
energy between the bleaching and decomposition reactions is exploited to improve
the net efficiency of a hydrogen peroxide
bleaching stage.
The effect of temperature on the bleaching rate for an oxygen.oelignified softwood
kraft pulp, kappa number 6, is shown in
Fig. 1; the effect of hydrogen peroxide
charge on the bleaching rate of a hardwood
kraft pulp is shown in Fig. 2.
418
Pulp Bleaching
Hydrogen peroxide charge

To the extent that the hydrogen peroxide is effectively consumed, an increase in
hydrogen peroxide charge leads to higher
pulp brightness.
The brightness
gain
achieved with peroxide application also
depends on factors such as metal removal,
liquor carryover, pH, temperature, and retention time. These factors are discussed
in more detail later in the chapter.
The uses of hydrogen peroxide can range
from its application as an oxidizing reagent
added to reinforce an existing extraction
stage to those to which peroxide is employed as the principal bleaching reagent.
The optimum hydrogen peroxide charge is
determined to a large extent by the objectives of the application. Reinforcement of
the extraction stage with peroxide is done
to reduce the initial chlorination
stage
charge or to reduce the chlorine dioxide
charge in a later bleaching stage. For fully
bleached pulps, an extraction stage can also
be reinforced with peroxide to achieve a
slight increase in final pulp brightness or
to decrease brightness reversion. A peroxide bleach stage, P, is normally used to re-
and Practice
H202 charge:
90
88
0
86
~84
~0
82
en
I/J
Q) 80
c:
-C)
35 kg/metric
ton
Consistency: 10-12%
78
.r:
.;::
76
CD 74
72
70
4
Retention
time,
10
Fig.1. FJ/t of terrrpmlhlre OIl lbe rille of bletleblflg of till ~

No.6) blelleW
wllb 6ytIrogenpnvzide
(17).
3. Factors affecting brightness in

hydrogen peroxide bleaching
3.1 Bleaching conditions
-Principles
delignifW
softwood ImIft }mlp (/uJpJM
90
H202 kg/metric ton
40
30
o
C/)
85
20
rft.
en
I/J
Q)
.E
C)
.;::
Temperature: 90C
80
11 %
ConsistencYi
.r:
CD
75
ft
6
Retention
10
time,
FIg.2. JJffeel
of ~
ciNll'p OIl tH rille of blelleblflg of till ~.del""ifW
(IuIpJM No. 11) blelleW with 6ytIrogen ~
(32).
placetraditional bleaching stages in mills

usingTCF or ECF bleaching sequences.
Peroxide is norrnally applied using existing equipment under prevailing process
conditions. Charges of 0.25-0. 75% on ovendry pulp are typical for CE+O+P) stage applications
and the hydrogen peroxide
charge in the second extrnction stage (E+P)
in normally limited to 0.05-0.2% on pulp.
By limiting the peroxide charge in the (E+P)
stage, any negative impact that peroxide
12
14
IMrdttIootllmlft
}mlp
may have on pulp viscosity is minimized (9).

For an CE+O+P) stage, a hydrogen peroxide charge in excess of 1% on pulp can be
used when the kappa factor of the first
chlorine dioxide stage is less than 0.13.
Temperature
and pH, however, must be
increased in this case to increase the reaction rate and to effectively consume the
higher hydrogen peroxide charge. Control
of pH in the initial chlorine dioxide stage is
an important aspect of this application (30).
__ _'___~_'_'__'___n_____

In many applications, there is a practical
minimum in the amount of hydrogen peroxide that must be added to obtain the
desired results. In some cases, dissolved organics or transition metal ions present in
the pulp stock:, or solution, may consume
the bulk of the added hydrogen peroxide.
If this occurs, the pulp may not be bleached
appreciably.
Improved pulp preparation
can increase the efficiency of the hydrogen
peroxide application and thus decrease the
peroxide charge required.
Hydrogen peroxide bleaching stages
were initially developed for the production
of TCF pulps and because brightness development is limited by the peroxide reaction
kinetics, mills have attempted to increase
retention time,process temperature, or the
peroxide charge. The amount of hydrogen
peroxide added to aTCF process is normally
dictated by economics. In a well-run TCF
sequence, the hydrogen peroxide is approximately 80",(,consumed (27). The residual from a strong hydrogen peroxide
bleaching stage may be put to benefidal use
in washing step of a preceding stage. Increasing the hydrogen peroxide charge can
increase the bleaching reaction rate and
produce incrementally higher brightness.
Typical hydrogen peroxide charges range
from 1.5% to 4.5% in one or multiple application points. For a single application stage,
the practical limit for the peroxide charge
is approximately 2.5% on pulp.
The excessively high hydrogen peroxide
charges required to produce high brightness TCF pulps with existing bleaching
equipment provides an incentive for installing the more specialized hydrogen peroxide bleaching stages. Instead of spending
capital for large towers that simply provide
increased retention time, mills are installing high-temperature, pressurized hydrogen
peroxide stages for improving the efficiency
of the hydrogen peroxide application. The
hydrogen peroxide charge is typically 1.52.5% on pulp, and these stages are capable
of bleaching and deUgnifying the pulp.
Therefore, they can be viewed as replacement for traditional bleaching stages in 'conventional" or ECF bleaching sequences.
Time and temperature

When a hydrogen peroxide
is refitted
into an existing
bleach
419
420
Pulp Bleaching
-Principles
OffIH brlgbmess of II tWrlbenr softwood ltrIIft Inllp blelleHII
Tllbk 1. Effect of P, I~
(O+P)Q(E+O+P)P(JI+P)P
application
and Practice
setpIBfIU.
Mill results
(E+O+P)
PI
0.6
2.5-3.0
14-17
4-10
65-77
plant, time
and temperature are normally the two parameters that are difficult to change. This
is because water flow and heat transfer generally limit the change in pulp temperature
from one stage to the next and the tower
size determines the pulp residence time for
a given production rate. When the temperature is below the optimum value of about
90C (atmospheric
towers), the performance of a hydrogen peroxide bleaching
stage is often disappointing. Table 1 shows
the brightness results for a TCF sequence
in a mill producing an oxygen-delignified
softwood kraft pulp using conventional
bleaching equipment.
For reinforcement of an existing extraction stage, process conditions in most pulp
mills are generally adequate to effectively
utilize the added hydrogen peroxide. To
obtain the maximum effect from oxygen
and added peroxide, however, the oxidative extraction stages are currently being
designed to operate at temperatures
of
90C or higher and at pressures exceeding
75 psig (31).
To prolong the retention
time and
achieve a higher brightness, several bleaching towers can be combined in a single stage
(32). Figures 1 and 2 show, however, that
the brightness increase is modest even after an extended (> 10 hours) retention time
(17,32). Figure 1 also shows the impact of
temperature on brightness response.
For an atmospheric pressure peroxide
stage, 90C is normally the maximum operating temperature (10, 19,33,34). Even at
90C, however, the time required to attain
the desired brightness may be longer than
most mills can achieve in their existing towers and it may be economically difficult to
justify building additional towers. The retention time to reach a target brightness can
be dramatically shortened, however, by increasing the temperature of the peroxide
stage. The plots in Fig. 1 show that for an
oxygen-de lignified softwood
pulp, an
equivalent brightness is achieved in only 2
hours at 110C compared with 6 hours at
90C (17). Other workers have presented
(O+P)Q
Stage:
",0" %
0.5
19-20
60-65
<120
40
Kappa no.
Temperature, C
Tune, min
Brightness, % ISO
45-48
uboratory
P, Temperature, C
(E+P)
65
i"
""
0.6
P,
2.;
66-69
72-79
evaluation"
P, Brightness, % ISO
77
88
77b
77.6
80.0
82.3
"Mill PI-stage pulp sampled and (E+P)P2 evaluated in laboratory

b
(E+P) replaced
by 0.5% PxaTM (mixed
peracid
solution),
as %
",0,
85
0
~80
~0
en
en
Q) 75
c::
.C)
c
'C::
III 70
65
10
Hydrogen
Fig. 3. lJJTecIof IIpressrn1w

JnIIp
(IMpJM
no.
12.5)
peroziM
20
30
peroxide charge,
Off IH me of bletwbi",
40
kg/metric ton
of II" o:rygen-tieUpiftetl
softwood In'IIft
(17).
similar results (11, 16, 27, 29). These findings are the basis for the design of pressurized hydrogen peroxide stages.
The application of pressure is an engineering device to maintain control of a hightemperature stage and avoid boiling. The
benefits can be higher brightness and decreased hydrogen peroxide charge (17)
(Fig. 3). Some researchers have reported
brightness improvement when oxygen, instead of nitrogen, is used to provide the in-
creased pressure; others have reported little

difference in results based on the method
of pressurization (17, 27). The maximum
temperature of a hydrogen peroxide stage
should be below 130C to avoid the homolytic cleavage of the oxygen-oxygen
bond in hydrogen peroxide (27). A properly conditioned kraft pulp can be bleached
to high brightness (88% ISO) in as little as 2
hours when this temperature limit is approached (25).
Chapter IV 10: Hydrogen
Peroxide Bleaching
421
422
Pulp Bleaching - Principles
65
Conditions:
Cf)
8 kg H202/metric
ton, 82C, 12 min at 30 psig

60 min at atm. press.
<f.
en
II)
Q)
c:
'5
.;::
.t:I
Q)
C)
co
0
SQ
~0
ui
II)
60
Q)
c:
.C)
l:
.;::
CD
II)
I
H202 Change,
85
84
83
82
81
80
79
kg/metric
40
o
ton
20
78
Kappa number of oxygen-delignified
(PO) stage: 100C, 2 h
77
76
fL
o
~
and Practice
pulp: 9
75
55
10.8
11.0
11.2
(EOP)
ng. 4. ReWUmsblp behtJeM flul
pulp (/ItIJ1p8110.
2')).
-stage
pH hi 1m (EOP) 81.ge
pH
The pK, for formation of perhydroxyl
anion is 11.6 at 25C. Equation 6 predicts
that: when the applied hydrogen peroxide
is 50% dissociated ( [HOO-]
[HP2] ), pH
and pK, will be equal. When the pH is de.
creased to 10.6, the hydrogen peroxide will
be only 10% dissociated to perhydroxyl
anion according
to Eq. 6. Because the
perhydroxyl anion concentration is essen.
tial to brightness development, it is not surprising that as pH decreases, brightness also
decreases as shown in Fig. 4. In a peroxide
bleaching stage, alkalinity must be optimized to balance
the formation
of
perhydroxyl anions with the formation of
colored compounds attributable to alkali
darkening (10). The previous history of the
pulp may also govern the optimum pH. For
example, softwood kraft pulps tolerate a
wide range of alkalinity, when the P stage
is preceded by a vigorous chelation stage
(10). This effect is shown below in Fig. II.
Consistency also has an impact in determining the optimum alka1inity level. At medium consistency (9-12%), depending on
other process parameters, the optimum
molar ratio of caustic soda (sodium hydrox.
ide) to hydrogen peroxide is approximately
1:1. In high-<:onsistency (20-30%) bleaching, the best results are obtained at a so-
"""
10
11.4
final pH
brlgblJlas hllbe bletrcblttg of IIOjI1IJootl
""'fl
= pK, +
20
25
Pulp consistency,
dium hydroxide to hydrogen peroxide

lar ratio of only 0.25 (35).
pH
15
log
[HOO']
mo-
[6]
IHPz]
When short retention times are used in a

peroxide stage, the alkali charge must be
increased to achieve the same brightness.
However, if the temperature is increased,
the alkali charge must be decreased to obtain optimum bleaching results (35).
Consistency
As stated earlier, an increase in pulp consistency can lead to improved bleaching
performance in a hydrogen peroxide stage
(35). This is seen in Fig. 5 (and in Fig. 7)
for a pressurized hydrogen peroxide bleaching stage. The wash presses needed to operate a high-<:onsistency bleach plant may
provide an opportunity for interstage removal of metals. Alternatively, the press illtrate can be recycled to recover the value
of the residual hydrogen peroxide.
3.2 Wood type (hardwood
softwood)
and
When a conventional
chlorine bleaching
sequence for kraft pulp is converted to an
ECF sequence, many mills find that total
chemical charge for bleaching is higher than
ng..s.
30
Effeel of pulp ~
OIIlbe brlgblJlas of"" oxygn-tleliplfletIlIOjI1IJootl
9) bletu:bedhl" pre!l88rl%etl~81"ge
(17).
expected based on kappa number of the

pulp entering the first chlorine dioxide
stage. This is especially true for hardwood
pulps or when softwood pulp is oxygen.
delignified. This phenomenon
may be related to an increase in the pH of the initial
chlorine dioxide stage and is often corrected by maintaining the pH below 3.
However, addition of hydrogen peroxide
may be required to reduce the demand for
chlorine dioxide, especially for the higher
lignin content softwood pulps.
When peroxide is used to reinforce an
extraction stage, the process is usually controlled to a target extracted kappa number
or brightness. There is little difference in
the hydrogen peroxide charge required for
bleaching hardwoods or softwoods. The
typical lower lignin content of hardwood
pulps, however, does allow operation of the
chlorination stage at a lower kappa factor
than would normally be used for softwood
pulps.
The brightness of a peroxide-bleached
pulp depends primarily on the structure of
the residual lignin and the lignin content of
the pulp entering the peroxide stage (10).
In the TCF bleaching of kraft and sulfite
pulps, at an equivalent hydrogen peroxide
charge, brightness is typically highest for
sulfite pulps followed in order by hardwood
35
%
""'ft
pulp (/ItIJ1p8No.
and softwood kraft pulps. To achieve the

highest possible brightness for TCF pulps,
mills often attempt to overcome the shortcomings of their equipment and process
conditions by applying high charges of hydrogen peroxide.
3.3 Kappa number of unbleached pulp

For hardwood iffid softwood kraft pulps
and for sulfite pulps the brightness obtained
in a hydrogen peroxide stage is inversely
proportional to the kappa number of the
incoming pulp. The relationship is essentially linear (Fig. 6) and is independent
of
the delignification process used to produce
the pulp entering the bleaching stage (10,
11). Further evidence of the beneficial effect of a low initial kappa number, on the
final brightness of a peroxide-bleached pulp
is shown in Fig. 7 (17).
3.4 Carryover
Carryover of liquor containing dissolved
organic fragments usually increases consumption of hydrogen peroxide. The peroxide is expected to have free access to the
dissolved organic fragments in the bleaching liquor, but its access to the lignin residue of the pulp (which is bound to the
carbohydrate)
is somewhat
restricted.
Therefore, it is expected that peroxide is
423
90
Postage: 25 kg H202"metric ton, 90C, 4h
85
10% consistency
85
424
-09-
0
~80
ui
IJ)
75
-c:
70
0)
'C
IJ)
QP
.s:::.
0)
. (EOP)QP
'C
.Q
CD
0)
tU
. D(EOP)QP
h. A(EOP)QP
(where, A= dioxirane)
o A(EOP)QP
o O(ZE)QP
65
fIO. 14.8) blaeW
10 12 14 16 18 20 22 24
softwood"""/I Jnllp (/uIpJM
Post-oxygen
kappa number
5.7
o
~
5.7
80
12.5
15
CD
c:
.s:::.
.g'
IJ)
70
- - - -
25% consistency
12%consistency
Postage: 90C, 4h
60
f
2
3
4
Hydrogen peroxide charge, kg/metric ton
011flul brlgblrfnsof... ~efI-tkUpifted

FIg.7. Bff1of O-slllge".,. __
(/uIpJM110.6)bWd1M "'... 0fJI'
(17).
partly consumed in oxidation reactions with
the organic compounds of the liquor. These
reactions do not lead to an increase in pulp
brightness but may reduce the color of the
bleach plant effluent. Although this may
be desirable, it is usually not the reason for
applying the hydrogen peroxide.
In a conventional bleaching process, the
residual chlorine from the chlorination stage
enters the following alkaline extraction
stage and reacts with the sodium hydrox-
35 kg H202/metric
ton, 90C,
4 h, pH 11-12
10
12
Q-stage pH
brIgbtrrns of... ozygm.uUplfted

(10).
lit -'it-slllge
~
90
-09ui
IJ)
Postage:
55
__OIIlbe
fIIIIb~
IJ)
Pre-QP kappa number

FIg.6. BJ/ed oflrIIIW ".,.
65
ci..
60
024
75
CD
c:
..OOP
CD
.s:::.
ui
IJ)
~Legend:
FIg.8. EJ/ed offJ-~

pH 011tile
brIgbtrtas of /UIozygm-tkUpiftM
fl"'"I. fJI'~
10.3) bWd1M ItIitb~
(38).
ide carryover. Conversely, because the
carryover of residual peroxy acids or hydrogen peroxide from a peroxy acid stage appears to activate hydrogen peroxide (15),
an interstage wash is neither needed nor
recommended.
In TCF bleaching, the effectiveness of the
bleaching process also depends greatly on
the efficiency of bleach plant washers. For
TCF sequences, the performance
of a P
stage can be improved by minimizing the
carryover (from the pulping process) of alkali and materials that contribute to the
chemical oxygen demand (COD). Postage
performance can also be improved by reducing the amount of dissolved lignin and
metals (from recycled bleach plant effluents) that enter the P stage.
softwoodltrwftJnllp
ide to form sodium hypochlorite.

When
hydrogen peroxide is added to the extraction stage, it reacts with both the chlorine
and hypochlorite. These reactions consume
part of the peroxide that would otherwise
be available for pulp bleaching. Carryover
of chlorine dioxide from a previous stage
can also consume hydrogen peroxide and
increase the peroxide demand. Therefore,
an efficient wash stage becween the cwo
stages is needed to minimiZe chlorine diox-
3.5 Hydrogen peroxide decomposition

and its control
Metal removal: chelation and acid washing
A primary objective of a hydrogen peroxide bleaching stage is to achieve the highest brightness and lowest kappa number
using the least amount of hydrogen peroxide. It is also desirable to achieve the target
kappa reduction with minimum viscosity
loss. Achieving these objectives invariably
requires an optimal metal profile (11, 27,
29, 32, 34, 3(40). Some transition metals
softwood
"""/1
Jnllp (/uIpJM110:
(e.g., manganese, copper, and iron) catalyze

hydrogen peroxide decomposition and contribute to the formation of hydroxyl radicals, HO., and superoxide anion radicals,
O2'. The presence oflow concentrations of
these radical species may actually be necessary for hydrogen peroxide bleaching to
proceed (26). However, a high concentration of such radicals leads to poor selectivity and decreased bleaching. Some research
has indicated that among the metal catalysts,
Mn2+does not decompose hydrogen peroxide by a radical mechanism. Therefore, it is
suggested that it cannot contribute to the
formation of hydroxyl radicals (41). However, other research indicates that bleaching in a hydrogen peroxide stage (pulp
brightness and strength) improves as the
manganese level in the pulp is decreased
(39).
Alkaline earth (e.g., magnesium
and
calcium) compounds and sodium silicate
appear to hinder hydrogen peroxide decomposition (42). These compounds may form
a complex with the transition metals that
catalyze the decomposition of peroxide and
lower their catalytic activity. However, the
exact mechanism of the stabilization is not
well understood. Two methods for achieving an appropriate metal profile have shown
successful results: I) metal chelation at pH
+7 followed by a washing or liquor removal

Ttlble 2. Effect of cbeltltltm (fJ sItJge) 011_till
COIIIetItof Stlftrrood hft
Metal Content,
Before chelation
After chelation
aQ-stage conditions:
't:I
Fe
Cu
300
11
47
0.6
500-1000
120-280
6-8
<5
0.1.Q.2
Initial metal
68
<fl.
en 66
en
Q)
c::
&
levels
(ppm)
Mn
70
Mg
220
Ca 2300
Na 2900
CD
No DTPA
in Postage
62
Postage: 25 kg H202/metric
ton, 90C. 4h
60
20
Legend:
Sodium
-0Mn: ppm x 3.5

- /1- Mg: ppm
- -Q - Ca: ppm/10
___
Na: ppm/4.3
~uo.~100
25
hydroxide
30
in P-stage,
Fig.10.1Ufect ofD'lPAIIIIMtItm IlIIIfJsIiIge 011tbeftul
kg/metric
50
brightness ofa softwootllnYlft p.lp (lI4ppa tW.32.5)
75
Postage: 25 kg H202/metric
ton, 90C, 4 h
o
0
~
2
Acid treatment
en
en
Stlftrrood InYIft
Q)
c::
~
01
'C
P.lp (37).
stage (38) and 2) an acid treatment at pH

<3 followed by washing and treatment with
magnesium salts to replenish the magnesium ions lost in the washing stage (39). A
chelation pretreatment step, conducted at
pH 4-7 for 30-60 minutes at 6O-90C, has
been shown to provide a metal profile leading to optimum brightness in a following
hydrogen peroxide stage (38) (Fig. 8).
Chelants are polydentate
ligand molecules, which bind metal cations between
donor atoms. The bonding between the
chelant and metal ions ranges from ionic to
essentially covalent. The chelants used primarily in the pulp industry are the sodium
salts of ethylenediaminetetraacetic
acid
(EDTA) and diethylenetriaminepentaacetic
acid (DTPA). Table 2 shows an example of
a typical metal proflle for a pulps treated
The plots in Fig. 9 show that significant removal of magnesium, calcium, and sodium
ions can occur in an acid wash-stage together with the manganese (37).
Pulps exhibit ion exchange properties
because they contain weakly acidic groups.
Neither chelation nor an acid wash removes
all of the transition metals. Iron is particularly difficult to remove because
it has an
affinity for phenolic
groups in lignin and
can also exist as a counter-ion to carboxylic acid groups in the pulp. Such acid groups
also bind many other transition
and alkaline earth metals (37). This may explain
why acid pretreatment
is less effective than
chelation. In a peroxide bleaching stage,
the metals bound to the pulp may be released and reduce the effectiveness of the
with EDTA (36).

An acid pretreatment
chelation in removing
0.2% DTPA to the pulp may be required as

part of the Postage bleach liquor makeup to
is less selective than

transition metal ions.
bleadUng reaction. The addition of 0.1-
tie up the released
70
EDTA in Q,
% on pulp
A
1.2
65
0.6
60
0.2
<fl.
pH
Fig.9. Effectof tIdd prelretllrrlerlt pH 011tbe remorJal of _1tIIs from an oxyfen-ikUgnlftetl
ton
bluebell III an 0fJP sequerree (10).
g!
:;:::~
.!!! 0
0
oen
1:
0164
pulp, 9OC, 1 h, pH 5-7
250
't:ICD
C\JCD
O-!!!..
'0 E 150
-0.
co. _
~~g
Mn
'C
..0
~:g
c CD
~CD_:?200
.!!11ij
.!!!...

70
1400
0.2% EDT A on oven-dry
426
p.lps.
ppm
Mg
Ca
425
metal ions. DTPA is used
..0
a..
o
o
55
50
. ----.
OP
45
15
20
Sodium
hydroxide
25
in P-stage,
30
kg/metric
ton
Fig. 11. Effect ofEIJTA IIIIMtItm ", a fJ sIiIge 011tbe ftul

bluebell
I. an 0fJP SMJIIMU (10).
brighmess
often because it is more effective at higher

pH than EDTA (Fig. 10). The benefits of
DTPA addition include a small brightness
gain, higher hydrogen peroxide residual at
the end of the bleach stage, and tolerance
for a wider alkalinity range (Fig. 11).
Commercial chelant/stabilizer
formulations have been introduced for Postage applications and have been demonstrated to
lead to an improved brightness gain and a
higher hydrogen peroxide residual (45).
Combining two or more metal management

treatments can also lead to improved Postage
efficiency. For example, an acid wash at
pH <2 followed by the addition of a 0.10.2% diethylenetriamine-penta(methylenephosphonic)
acid (DTMPA) leads to a
better Postage efficiency than the application of other common chelating agents
(46). The addition of sulfur dioxide or sodium bisulfite in an acid pretreatment stage
further enhances the removal of metals and
of a StlftwootIhft
P.lp
(lappa
110.32.5)

bleaching performance
stage (46).
in a following
427
Studies have shown that a Mg/Mn ratio

of over 30 is needed for effective hydrogen
peroxide bleaching under normal temperature conditions (~90C). When the hydrogen peroxide stage is conducted at a higher
temperature (e.g., 120C) and under high
pressure, the Mg/Mn ratio must be even
higher (> I 00). In addition, the manganese
level must be less than 2 ppm to achieve
the benefits of the accelerated pulp bleaching reactions (47).
A chlorination stage, operated at pH 3,
provides adequate metal removal for a following hydrogen peroxide-reinforced
oxidative extraction stage and, generally, in an
ECF process the (E+O+P) stage conditions
are not ~ere enough to warrant the addition of chelants or magnesium (48). inclusion of 0.0~.2% magnesium sulfate in an
(E+O+P)-stage can, however, minimize viscosity loss (6,9,48) and may be required if
the extraction stage is operated under severe conditions or if there is an unusually
high level of metals in the wood furnish.
Although a high dose of magnesium in a
hydrogen peroxide stage suppresses the decomposition reaction, which is desirable,
it may also suppress the bleaching reaction
which is undesirable (10, 37).
Sodium silicate is an essential component
of the bleaching liquor in the peroxide
Magnesium sulfate (Epsom salt) and sodium

silicate addition
The non-selective removal of metals in
an acid-wash stage produces a pulp that
upon bleaching with hydrogen peroxide,
has a lower brightness and viscosity. The
peroxide residual is also lower as a result
of the removal of magnesium ion in the acid
wash step. Magnesium, usually as magnesium sulfate (MgSO 4)' can be re-applied to
the pulp to restore the appropriate metal
profile (27, 36-39). Figure 12 shows ~eral of the benefits that have been discussed
(39):
1) The addition of a chelation stage after the
acidic ozone stage can lead to a significant reduction in hydrogen peroxide consumption (compare QZQP and QZP).
2) The addition of magnesium,as magnesium
sulfate, to the P stage (P) produces an
even more dramatic improvement in both
brightness and hydrogen peroxide consumption (compare QZP' and QZP).
3) Both chelation and acid-wash pretreatments are effective when provision is
made to restore the magnesium/manganese (Mg/Mn) balance.
94
92
o
~
90
#.
88
iii'
I/)
Q)
c:
86
azp
Z-stage: 0.5% 03, pH 2
Postage: gooc
82
pO-stage: gooC, includes Mg addition

80
Hydrogen
Fig. 12. IUfects of ebe'-t
10
15
peroxide
20
25
consumption,
30
35
40
kg/metric
IIMUImr 011tbe brlgblrlns of."
""""mbletWbetll" ~
ImIft I"dp (i4pJMno.
""" B)
Pulp Bleaching
t:fnII/Iosedofoz_"""~
ton
meygen-tieliplftM
I16j'trtJoot1
stllge5(39).
-Principles
and Practice
90
0
0
u)
80
~H202added to (E+O)
~",,/
~70
I/)
Q)
60
50
c:
C)
.t:
CD
,/
40
P '"
'"
~/
(E+O)
Stages
Rg. 13. Effectof~

~.
peroxide
IIMUImrm." (E+O)stage011brlgblrlns
consumption
in bleach sequence
bleaching of chemithermomechanical
pulps
(CfMP). Similar to magnesium, the silicate
complexes the transition metals through
oxygen or hydroxyl bridges (43,44). The
formation of the complex changes the catalytic activity of the transition metal and its
ability to decompose the hydrogen peroxide (36). Despite a previous chelation or
acid-wash stage, metals may be released
from the pulp during hydrogen peroxide
bleaching and addition of silicate to the
bleaching liquor can decrease the negative
impact of these metals on bleaching performance. This benefit is particularly apparent in high-consistency
hydrogen
peroxide stages (11, 35,49). Forexample,
the addition of 2% silicate in a high-consistency stage has been found to decrease the
hydrogen
azap
"5> 84
.t:
CD
428
(91 % corn-
pared with 100%), increase the brightness

(89.5% ISO against 87.3% ISO), and improve
the viscosity [820 DP ("'15.8 mPaos) compared with 810 DP ("'15.3 mPaos)] (43).
The benefits obtained are in addition to
those gained by using magnesium (0.5% on
pulp) and DTMPA (0.1 % on pulp) as a stabilization system. In Europe, silicate is also
used in the hydrogen peroxide bleaching
Or sulfite pulp but lcrAftmills in North
America have been reluctant to add silicate
to their bleaching processes. The potential
for scale deposition on process equipment
'"
tbe _
of etldl stllp I" IID(E+O)DED
appears to be the main obstacle for the use

of silicate in of kraft pulp bleaching.
4. Typicalhydrogen peroxide
bleaching sequences
4.1 .Conventional.
Hydrogen peroxide is generally applied
as a reinforcing chemical in an existing extraction stage. The combined delignification and bleaching effects of hydrogen
peroxide allow the kappa factor for addition of chlorine and chlorine dioxide to be
reduced and thereby decrease their consumption. Peroxide addition in an extraction stage may also help a mill achieve
environmental objectives (lower AOX) and
maintain pulp production capability when
the mill's chlorine dioxide capacity is limited (8, 9). Some mills may make changes
in their process conditions to optimize the
peroxide-reinforced extraction stage as previously described. In most cases, however,
because the applied peroxide charges are
low and performance
expectations
are
modest (often, to overcome a specific sequence constraint), the mills are inclined
to accept whatever benefits they can get
without incul'1'iJ1g additioMl ~rocess optimization costs.
The primary objective of a reinforced
extraction (E+O+P) stage is to improve lig-
0
.c.
c.
429
92
91
~90
iIi
89
::!!
0
ui
88
(/)
Q)
-c::
.c.
OJ
.;::
.c
DO
W
U
H202 charge: 2 kg/!
87
86
85
84
80
82
84
86
88
90
CEO brightness, % Elrepho

p age to II CEllD~
obltlilted ~ atltlilirm of II
Fig.14. BrlgbtruJSSglli.
softwood iIrIIftJnllp (50).
. ft'""
92
i. tbe bktu:bi.g of"
nin removal which permits a reduction in

the total active chlorine charge in the initial chlorination stage (see Chap. IV 6). An
application in the secon<1,extraction stage
counteracts the alkali darkening typical of
this stage. This may allow a lower brightness control target in the D 1 stage which
would lead to a decrease in the chlorine
dioxide requirement (Fig. 13) (9). Hydrogen peroxide is also applied in a final bleaching stage to replace a sodium hypochlorite
stage or to provide higher brightness and
brightness stability in a short bleaching sequence (Fig. 14) (50).
Steep bleaching, that is, allowing hydrogen peroxide to react with the pulp under
ambient conditions over a prolonged time
period (>7 days while the pulp is stored external to a bleaching tower) is still practiced
at some locations (51).
traction stages has allowed many mills to

maintain pulp production capacity and pulp
quality. The use of hydrogen peroxide in
ECF applications can be economical but the
benefit must be determined on a mill-bymill basis. There is also often an opportunity for process optimization, as previously
described, when a mill is converted to an
ECF bleaching sequence.
Hydrogen peroxide can be used as a primary bleaching agent in sequences
designed to decrease AOX formation
by
eliminating the first chlorine dioxide stage
(32). Sequences such as QPD(E+P)D can
be used, but the operating costs are high.
Other technologies that use stronger oxidants such as ozone or peroxy acids in place
of hydrogen peroxide may significantly reduce the bleaching costs 05,53,54).
4.2 ECF
ECF bleaching sequences currently dominate the production of bleached kraft market pulp in Canada and Scandinavia (52).
A typical ECF bleaching
sequence
is
D(E+O+P)DD.The conversion of sequences
from "conventional" to ECF often is hampered by limitations in cWorine dioxide
generating
capacity and by bleaching
equipment capacity and configuration. Hydrogen peroxide reinforcement of the ex-
The concept of a metal management pretreatment followed by an alkaline peroxide

stage was the basis for the first commercial
TCF chemical pulp bleaching sequences
(32). Typically, these sequences are variations of a Q(PP) sequence. The advantage
of this sequence is that it can be implemented in an existing bleach plant without
major capital investment. The brightness
obtained depends on the incoming kappa
number (0) and the flexibility for incor-
4.3 rCF
430
5. Pulp quality
porating effective metals management

stages. Multiple peroxide stages can also
be combined to increase the retention time
of an alkaline peroxide stage and thereby
achieve higher brightness (32). In the past,
this strategy has been utilized for sulfite
pulps or when pulp production volume did
not justify the investment in other delignification technologies (55). For sulfite pulps,
the brightness can approach 90% ISO for
hydrogen peroxide charges of less than
3-4% .
Hydrogen peroxide is the primary chemical responsible for bleaching in TCF chemical pulps. It has been shown that brightness
and brightness stability are optimum when
hydrogen peroxide is applied at the end of
a sequence that includes an ozone stage.
Sequences such as Ozp, OZEP,OZ(E+O+P)P,
and o(QZ)Q(P+O) can be used to produce
acceptable market-grade softwood pulps
provided strength degradation in the final
P stage can be managed (33). Peroxy acids
have been evaluated as activators for improved brightness response in a final hydrogen peroxide stage 04, 15).TCF sequences
can take the form OZ(E+O+P)PaP
or
OQ(E+P+O)PaP where Pa is a peroxy acid
such as Caro's acid, peracetic acid, or a mixture of the two.
85
5.1 Brightness
stability
Carbonyl groups are known to be responsible for photo sensitizing heat-induced (56)
and photochemically- induced (57) brightness reversion of bleached pulps. Hydrogen
peroxide is effective in eliminating carbonyl groups (33) and a final P stage leads to
excellent brightness stability in TCF sequences even when the bleached pulp has
a relatively high residual lignin content. For
example, the brightness reversion was only
2-3 points for samples of softwood and hardwood sulfite pulps (kappa numbers, 2-4)
that W8re bleached in TCF sequences (49).
The initial brightness range for the pulps
was 81-88% ISO and the reversion was measured at 100C for 2 hours using the standard TAPPI heat-aging test. The reversion
was 3.5-4 points after a 3-<iaylight-induced
yellowing test. Results for softwood kraft
pulps were similar. Figure 15 shows the
comparative brightness reversion of pulps
bleached in OZP and OPZ sequences after
exposure to heat at 105C (33).
The primary benefit of a peroxide application in the final stage of a conventional
bleaching sequence such as (CIDXE+O)DP,
is brightness stability. Reversion for a fully
Z-stage: aprox 0.6% 03, pH 2.5, 10 min, 3.5% consistency

Postage: 15 kg H20:!-'metric ton, SOC, 2 h, 10% consistency
80
0
~::!! 75
0
ui
(/)
Q)
c:: 70
.c.
OJ
.;::
II)
65
60
12
24
36
Heat exposure
Pi,. 15. 'l'bemuIl
slllbilily
tnMOQPZ~
of...
oxygert-."piftetl
(33).
48
60
72
time, h
softtllOOd iIrIIft JnIlp (bppa
tIO. 17.8) blebetI
i. OQZP

bleached (90% ISO) pulp, prepared using a
sequence with a final P stage, can be limited to 1-2 points compared with 3-4 points
in a sequence without a final P stage (58).
When hydrogen peroxide is applied to reinforce the oxidative extraction stage of an
ECF sequence, the brightness reversion can
also be slightly improved (8).
5.2 Pulp strength
The strength properties of a conventional
(D,D+C)(E+O+P)D(E+P)D
pulp are not
changed by the addition of hydrogen peroxide to the extraction stages (7). Softwood TCF pulps, bleached
to high
brightness using hydrogen peroxide, can approach the brightness levels obtained in ECF
bleaching. For such pulps, however, many
researchers report a 5-10% lower tear index
at the same tensile index compared to oxygen-delignified
ECF pulps (16, 27, 39).
When other non-chlorine bleaching agents,
such as ozone or peroxy acids, are utilized,
the TCF and ECF pulps that are obtained
are roughl:f equivalent in strength (13, 17,
39, 59-61). Figure 16 shows the tear-tensile relationship for MCC oxygen-delignified
softwood kraft pulps bleached to 90% ISO
brightness
in TCF (OAZQP) and ECF
(OD(E+O)DD) sequences.
431
432
Pulp Bleaching
-Principles
and Practice
5.3 Cleanliness
6. Process flowsheets
High-performance
TCF bleaching sequences presuppose
effective screening
and washing. The low kappa numbers required for achieving a high final brightness
ensure a low shive content in the incoming
pulp. Therefore, pulp cleanliness is not an
issue in most pulp mills that have an established TCF pulp bleaching process. Hydrogen peroxide is not as effective as chlorine
dioxide for bleaching shives and dirt. Mills
attempting to produce TCF pulp through
the application of high charges of hydrogen peroxide, but without having made the
investment in adequate pulp preparation,
do not achieve the expected pulp brightness and cleanliness.
When hydrogen peroxide is used to reinforce the oxidative extraction stage in an
ECF sequence for the purpose of reducing
the kappa factor, attention must be given
to adjusting the conditions of the chlorine
dioxide stages to maintain pulp cleanliness
(9). Although some of shive removal may
take place in the (E+O+P) stage, it is important to reduce the pH in the Dl stage
for shive control. The chlorine dioxide
charge in the first stage may also have to be
increased to completely remove shives.
The process flowsheet of a typical hydrogen peroxide-reinforcement

application in
an oxidative extraction stage is shown in
Chap. IV 6. Figure 17(a,b,c) shows three
process flowsheets that have been used
successfully for refittingTCF sequences into
existing bleach plants (32).The sequences
in Fig. 17 were designed to maximize pulp
retention time in the alkaline hydrogen peroxide bleaching towers and make the most
efficient use of the residual hydrogen peroxide through counter-current filtrate flo~
Figure 18 shows an example of a TCF sequence using advanced
non-chlorine
delignification
technology and washing!
pressing. The flowsheet in Fig. 19 shows a
pressurized hydrogen peroxide (PO) stage
in greater detail (28). Retention time and

heat transfer capability usually determine
which configuration has the potential to
produce a TCF pulp having the desired
quality.
The addition point for hydrogen peroxide should be isolated from the injection
points of other chemicals such as sodium
hydroxide or live steam.This is particularly
relevant for high-temperature
P stages. It is
also crucial that hydrogen peroxide be
mixed well with the pulp, because inadequate mixing may result in hydrogen peroxide decomposition
in pockets
of
extremely high alkalinity or temperature.
The release of oxygen during decomposition can cause the pulp density in the P
stage to be lower than normal and the
(a)
Q
20
Z-stage: 0.5"1003, pH 2
PO-stage: 30 kg H:p~metric ton
includes Mg addition
0>
C\I
Z
E
15
(b)
xCD
"C
.S
....
10
<U
CD
~5
60
80
100
Tensile index, Nm/g
Fig. 16. Tellr-tenslle reWUmsbip for 11IIoxypII.tIe"g,dftetl

~.
:ro~
120
(c)
ImIft "",p bluebetl
", IICF111MTCF
Fig. 17. Prwas flonbHl6
ft1r TCFbluebirJg seqrmrces sullilble for refittl"g I"to exlstl"g bleaeb pl",,16 (32).
433
EOP
PO
ZQ
towers may have to be operated at a lower

volume to prevent stock overflows. Thi~,
however, may only be an issue at process
shutdowns when the stock can "bloat" (62).
The refitting of hydrogen
peroxide
bleaching stages into existing bleach plants
and the use of multiple towers for prolonged P stage retention. time usually requires the use of a stage designed primarily
for chlorine dioxide application. Some mills
have reported grout damage or disappearance, and deterioration of tile lining, espe-
cially at the tile edges (32). A potential exists for titanium corrosion at sufficiently
high temperature, pH, and peroxide charge.
Effective inhibitor species for preventing
titanium corrosion include calcium, magnesium, and silicates (63,64).
Brightness control in a hydrogen peroxide bleaching stage may be difficult if the
lignin content of the pulp varies over a wide
range. Most processes can be controlled by
maintaining a uniform low kappa number
for the incoming pulp. Brightness thresh-
Degassing
Standpipe
MC-pump
Fig. 19. Processflowsbeetfor
Diffuser
washer
MC-pump
a pressurized
Pulp Bleaching
-Principles
and Practice
olds can be gradually increased as mills gain

experience in minimizing their kappa number variations. Control initiatives can also
be directed upstream to include furnish
selection by species and age, chip sorting,
and the use of the new alkaline pulping
technologies.
A TCF process may be difficult to control at the beginning of a production run
but after 4-6 days the sequence eventually
acquires a high degree ofstability (65). A
method for in-process metals analysis and'
real-time control would be of immense benefit in the operation of a TCF kraft pulp
bleaching sequence.
NaOH
EDTA
434
JIf!rtdile (PO) stage at 10% COffSistency
(Kvaemer)(28).
7. Environmental considerations
The main environmental consideration
associated with peroxide bleaching is the
role of this oxidant in facilitating the recycle
of bleach plant effluents to the recovery
cycle. Effiuent recycling can help to reduce
water use in a mill and may ultimately lead
to elimination of effluent discharge to waterways. Other considerations, such as the
drive to eliminate dioxin and reduce AOX,
have led to the concept of ECF bleaching.
Such sequences use a low kappa factor in
the initial chlorination stages (5,6,9). The
benefits of an ECF process, with inclusion
of hydrogen peroxide, are lower AOX in the
bleaching effluent and, more particularly,
lower AOX in the pulp (10,65). When a
mill's capacity to produce chlorine dioxide
is limited, the use of hydrogen peroxide may
allow the mill to convert to an ECF process
and yet maintain its pulp quality and production rate (7,8).
Hydrogen peroxide reinforcement of the
oxidative extraction stage can be used to
decrease the color of mill effluent (9). Hydrogen peroxide has also been used to control odor by treatment of reducible sulfur
compounds in the mill effluent.
The major incentive for the development
of TCF bleaching sequences has been the
elimination of AOX. Reduction of AOX may
be required by regulation, due largely to the
public's concerns about the Impact of chlorine on the environment even though there
is little evidence indicating that chlorine

compounds are a major source of effluent
toxicity (66). Moreover, the effluents from
TCF bleaching of kraft pulp processes may
not be any less toxic than those from chlorine-containing bleaching sequences (65).
There are also reports that effluents containing a high hydrogen peroxide residual
can cause biological treatment system dormancy (65). This phenomenon
can be
avoided if the residual hydrogen peroxide
in effluents is eliminated by "souring" with
sulfur dioxide or sodium bisulfite. The fate
of the metal-chelate complexes in pulp mill
effluent and the potential for the buildup
of toxic metals in the food chain is another
open issue. In some jurisdictions, there has
been discussion of restricting in the use of
certain chelating agents.
8. Economics of hydrogen
oxide bleaching
per-
The economics of a hydrogen peroxide

bleaching sequence are related closely to
the circumstances of a given mill. These
factors include equipment
and performance, sequence configuration, operator effectiveness, chemical costs, and furnish.
The capital cost for investing in new technology can be a major hurdle to overcome,
and often the existing technology at a mill
is related to previous environmental regulatory requirements As a result of these past
regulations, mills in various regions around
the globe have taken divergent technology
paths, and this may affect their ability to
economically invest in new technology.
Generally, peroxide reinforcement of an
extraction stage in an ECF sequence can
decrease bleaching cost and allow a higher
pulp production rate (9). A hydrogen peroxide-based TCF sequence, on the other
hand, has a significantly higher chemical
cost than an ECF (control) sequence (9).
Some mills may be able to negotiate a premium forTCF pulp to offset the increased
production cost (65). It has been also reported that new TCF bleaching sequences
can be built and operated more inexpensively than new ECF installations (67,68).
9. Activators and hydrogen

peroxide-derived bleaching
agents
9.1 Hydrogen
peroxide
activators
Activators, such as nitrilamine (cyanamide), which

modify the hydrogen
peroxide reaction have recently been investigated. Nitrilamine reportedly increases
the brightness threshold of a P stage by 2-3
points and also increases peroxide residuals (45,69). This may allow the use oflower
peroxide
charges or the attainment
of
higher brightness pulps. The amino-imino
peracid anion [Eq. 7J is a
H202 + H2NCN -+ H2N~
= NH
OOH
[7J
strong nudeophile
that .reacts selectively
with chromophores
and lignin to increase
pulp brightness. The nitrilamine is consumed in the bleaching reaction and converted to urea.
The use of tungstate and molybdate catalysts to activate acidic hydrogen peroxide
in bleaching reactions has also been investigated aO). Similarly, transition metal-substituted polyoxometalate duster ions have
been proposed
primarily
for use as
delignifying agents. Polyoxometalate cluster ions are inorganic analogs of the organic
platfonns known to control the activity of
transition metals in enzymes that selectively
catalyze the oxidation of lignin (71).
Application of a silicon-tungsten-manganese-based
cluster ion to an oxygendelignified softwood kraft pulp at 125C for
2 hours decreases the kappa number from
35 to 5 and produces only a small reduction in viscosity (from 34 to 27 cP) (71).
The polyoxometalate cluster can be re-oxidized, after reaction with the lignin, for recycle and reuse. Air and hydrogen peroxide
have been used to re-oxidize the catalyst.
To be viable economically, the industrial
application
of these polyoxometalate
435
clusters would undoubtedly require an extremely high recovery of the polyoxometalate catalyst.
Heteropolyoxometalates,
which can be
produced from relatively inexpensive reagents, have also been proposed as catalysts
for delignification of pulps (72). They are
added directly to the P stage to improve the
effectiveness of the peroxide application.
For example, the addition of a polymeric
silicoperoxomolybdate
leads to significant
improvements in delignification in a peroxide stage and improves brightness development in the following stages (72).
The formation of carbonyl groups, which
the perhydroxyl anion effectively attacks,
may be considered a form of activation. It
has been shown that a peroxy acid pretreatment enhances the performance of a following hydrogen peroxide bleaching stage.
The effect surpasses the simple finding of a
decrease in kappa number or the carryover
of residual hydrogen peroxide from such a
stage to a subsequent
peroxide
stage
(15,59). The mechanism for this performance enhancement has not yet been determined.
9.2
Hydrogen
bleaching
peroxide-derived
agents
Introduction and chemistry of reactions

A peroxy acid, or peracid, is an acid that
contains a perhydroxyl group rOOR) in
place of the hydroxyl group of its parent
acid:
II
R - C - OH
Carboxylic acid
II
R-C-OOH
Percarboxylic acid
For Peracetic acid,
R
II
HO-S-OH
II
Sulfuric acid
=CH3
II
HO - S
II
OOH
PeroxymonosuHuric
acid
Caro's acid
436
Pulp Bleaching
-Principles
and Practice
rllbk 3. ~JIoInUMlsof~
(59).
Oxidation Potential
(e', V)
03 + 2 H+ + 2 e- -+ 02 + H20
H202 + 2 H+ + 2 e- -+ 2 H20
HCI02 + 3 H" + 4 e" -+ C.- + 2 HzO
HOCl + H" + 2 e" -+ C.- + HzO
HSOs- + 2 H+ + 2 e" -+ HSO;
+ H20
Cl2 + 2 e' -+ 2 Cl"

CI02 + H" + e- -+ HCI02
2.07
1.78
1.56
1.49
1.44
1.36
1.15
CH3C03H + 2 H" + 2 e- -+ CH3C02H + HzO
1.06
ClO' + HzO + 2 e- -+ Cl- + 2 OH'
0.90
0.87
0.78
0.40
HOO' + HP
+ 2 e' -+ 30H-
CI02' + 2H20 + 4 e' -+ C.- + 4 OH02 + 2 H20 + 4 e- -+ 4 OH-
In solution, percarboxylic acids are more

volatile than carboxylic acids and are also
weaker acids than their parent acids. Generally, the pK. of a percarboxylic acid is 3-4
units higher than that of its corresponding
parent acid (73). Caro's acid, H2SOS' is a
dibasic acid in which the protons are attached to the oxygen of the hydroxyl group
and the perhydroxyl group. The Caro's acid
anion, HSOs"' is a considerably weaker acid
than HS04", the anion of sulfuric acid (74).
Hydrogen peroxide is a relatively weak
oxidizing agent and this limits its use in
applications where a strong oxidizing agent
is required.
Percarboxylic
acids (e.g.,
peracetic acid) and Caro's acid are powerful oxidizing agents. Table 3 lists the oxidation potential of peracetic acid and Caro's
acid together with that of other oxidants.
Because the removal of lignin involves oxidation to form alkaline soluble fragments,
peroxy acids are of interest as potential nonchlorine bleaching agents (75). Their high
oxidation potential allows them to be used
In bleaching reactions under more moderate conditions than those required for hydrogen peroxide.
It has been shown that peracetic acid is
capable of hydroxylating the aromatic ring
of a phenolic compound to form a hydroquinone (12). Hydroquinones are readily
oxidized to quinones which then undergo
ring opening to yield muconic, maleic, and

fumaric acid derivatives of the starting phenolic compound
(12). Hydroxylation
of
phenolic compounds, epoxidation of olefinic bonds, and the Baeyer-Villiger oxidation of ketones all involve oxidation of
functional groups that are normally present
in lignin. Lignin-containing pulps therefore
should be susceptible to oxidation with
peroxy acids and consequently there is interest in using the compounds to delignify
and bleach chemical pulps (75).
The largest commercial use of peroxy
acids is for chemical syntheses, especially
for the epoxidation of olefins and the oxidation of cydohexanone.
Peroxy acids are
also used commercially In laundry bleaching (75). The use of peracetic acid as a
de lignifying agent was initially investigated by Poljak in 1948 as a method for
preparing holocellulose from wood (76).
Other studies confirmed that peracetic acid
is highly selective in the removal of lignin
from wood (77). The effect of pH (in the
range 3-9), temperature (in the range 5085C), and consistency on delignification
and properties of kraft pulps treated with
peracetic acid were investigated by Bailey
and Dence (78). At pH 7-9, the reduction
in kappa number of pulps oxidized with
peracetic acid was essentially equivalent to
the kappa number of similar pulp samples

oxidized with an equimolar quantity of chlorine.Within a pH range of 5-9, reaction temperature
and pulp consistency
had a
minimal impact on pulp strength. Pulp viscosity and strength, however, did decrease
with increasing
temperature
when
peracetic acid treatment was carried out at
pH 3.
Peracetic acid has also been evaluated as
a bleaching agent for mechanical pulps at
neutral pH (79). IDtraviolet and infrared
spectroscopy
of mechanical
pulps,
bleached at pH 7-8,haveshown that bleaching results primarily from modification of
the side chain groups of lignin (a,B-unsaturated aldehydes, conjugated double bonds,
and a-carbonyl groups). Oxidation of the
phenolic rings is normally minimal in this
pH range (80).
The drawback in the use of peroxy acids, particularly in the pulp and paper industry, is their high manufacturing cost and
the fact that they are g~nerally not sufficiently stable to be shipped or stored for
long periods of time (71). These obstacles
can be overcome if a safe and economical
process can be developed for producing
peroxy acids at the pulp mill site. The onsite generation of peroxy acids is discussed
in Chap. n 3.
Function
Application of peroxy acids in chemical pulp

bleaching
The applications of peroxy acids and
laboratory data comparing their performance have been reviewed by Uebergon
(15). Thble 4 provides a summary of peroxy
acid use in a bleaching sequence.
The relative effectiveness of the various
peroxy acids in bleaching has been compared (15), but more study is warranted.
The following benefits have been demonstrated for the use of peroxy acids in TCF
chemical pulp bleaching sequences (59):
1) Higher
3-4 points increase with replacebrightness ment of hydrogen peroxide (2.5%
tbresbold on pulp) by peroxy acid (0.5% on
pulp based on the hydrogen peroxide used in peroxy acid preparation)
2) Higher
viscosity
and
strength:
viscosity and strength comparable to ECF control (conventional TCF sequence showed a
3) Lower
cost:
total chemical bleaching requirement is decreased because of improved bleaching efficiency
5-10"10strength
agent
agent
The bleaching
performance
of peroxy acids has been evaluated in pulp mill trials and
the results have duplicated
the laboratory
findings (13,59).
Wood (pulping processes such as Milox'")(81); Pulp (replacement

or reinforcement
in an initial chlorination
stage)(13, 14,59,82,83);
reinforcement
of an (EOp) stage
(15) or an ozone stage (82)
Activation of lignin before or between
83-85)
oxygen stages (15,
Activation of hydrogen peroxide stage together with oxygen under acidic or mildly alkaline conditions (15,59)
Activation of a following hydrogen peroxide bleaching stage
(15, 59, 82, 83)
Bleaching agent in later
oxidizing stages
In ECF bleaching as a replacement

or hypochlorite stage (14, 15,82)
In ECF bleaching
438
Pulp Bleaching
-Principles
and Practice
of dioxiranes in chemical pulp

bleaching
Dimethyldioxirane (DMD), which can be
formed in situ by the reaction ofCaro's acid
with acetone Eq. (8], has been demonstrated to be a very selective delignification
agent (88):
Application
[8]
The acetone acts essentially as a catalyst
and is regenerated following the oxidation
of the pulp with DMD. Elucidation of the
pulp reaction mechanisms remains a subject of research activity. The practical application of this technology depends on the
extraction and recovery of acetone from the
bleaching effluent. In any commercial use
of DMD, the Caro's acid would likely be
produced on site as a product of reaction
of sulfuric acid with hydrogen peroxide.
loss)
Application
Delignification
Activation
437
for a chlorine
dioxide
to reinforce a chlorine dioxide stage (15)
In TCF bleaching to replace a hydrogen peroxide

15,48,59,61,82,86,87)
stage (14,
References
1. Beeman, L.A. and Reichert,
J.S., in The
Bleaching of Pulp,TAPPI PRESS, New York,
1953, p. 210.
2. Holladay,P.C.and
Solari,R.]., in The Bleaching of Pulp (W.H. Rapson, Ed.), TAPPI
PRESS, New York, 1%3, p. ISO.
3. Andrews,
D.H. and Singh, R.P., in The
Bleaching
of Pulp (R.P. Singh, Ed.), TAPPI
PRESS,Atlanta, 1979, p. 211.
4. Robitaille, M.A., "Hydrogen Peroxide - A
Versatile Bleaching Agent," 74th CPPA Annual Meeting Preprints, Tech. Sect., CPPA,
5. Berry, R.M. Fleming, RI., Voss, R.H., Luthe,
C.E.,Wrist, P.E., Pulp Pap. Can. 9O(8):T279
(1989).
6. Liebergott,
N., van Uerop, B., Nolin, A.,
Faubert, M., Laflamme,].,
"Modifying the
Bleaching Process to DecreaseAOX Formation," 76th CPPAAnnual Meeting Preprints,
Tech. Sect., CPPA, Montreal, 1990, p. B229.
7. Reid, D.W, BiIlmark, G.G., Sutton, c.].,

TapPiJ 74(7):99 (1991).
8. Young, J., Start, G., Lazorek,]., "Utilization

of an Eop Stage During 100% Cl02 Bleaching at Weldwood Hinton, CPPA Pacific and
Western BranchAnnual
Meeting Preprints,
Tech. Sect., CPPA, Montreal, 1992, section
4A, Paper No.3.
9. Anderson,].R.,"Hydrogen
Peroxide Use in
Chemical
Pulp Bleaching,"
1992 TAPPI
Short Course
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73. Klenk, H., Cotz, P. H., Siegmeier, R., Mays,
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79.
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442
Pulp Bleaching
-Principles
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83. Anderson,
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86. Devenyns,].,
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87. Devenyns,J.,Troughton,
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SECfION IV:
The Technology of
Chapter 11:
Bleaching Shives and Dirt
Peter Axegird
and
EUsabeth Bergnor Gidnert
Swedish Pulp and Paper Research Institute
P.O. Box 5604
50114 86 Stockholm, Sweden
1. Background
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 445
2. PartlcIemmeasuremment...
3. RelatIonship
445
between cIeanllness
and brightness.
4. Effect of particle origin and size on bleachabiHty

5. Patterns for the degradatIon
durlngbIeaching
6. InteractIon
7. Extended
of particles
448
between different bleaching

delIgnificatIon
stages . . . . . . . . . . . . . . . . . . . . . . . . .. 450
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 450
8. ~ndelIgnificatIon
9. ChlorinatIon.
. . . . . . . . . . . . . . . . . . . . . .. 445
. . . . . . . . . . . . . . . . . . . . . . .. 445
..,
450
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 451
10. Elemmental chlorine-free
(ECF) bleaching
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 452
11. Totally chlorine-free (TCF) bleaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 453

11.1 Bleaching with ozone. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 453
11.2 Bleaching with hydrogen peroxide. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 453
12. Mixing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 454
13. Approaches
for Immprovlng cIeanllness
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 454
443
Chapter IV 11: Bleaching Shives and Dirt
445
2. Particle measurement
Table 1. Metbods fur JMrlkle
Chapter IV 11:
Bleaching Shives
and Dirt
The wide range of methods available for

particle measurement are summarized in
Table 1.
1. Background
3. Relationship between cleanliness and brightness
Cleanliness is a very important quality

parameter of a bleached chemical pulp.The
cleanliness level at a particular brightness
is the result of the competition for bleaching chemicals between dissolved organic
substances, pulp fibers, and wood particles.
There are three main sources of dirt contamination: the wood, process problems,
and external origins, for example, plastics.
More than half of the impurities found in
pulp originate from the wood (I).The cleanliness of bleached pulp is affected by coarse
particles derived from the cellular tissue of
the tree and by extraneous particles. The
former group consists of shives (fiber
bundles),knots,and
balk specks, which can
be eliminated during bleaching but less easily when the pulp fibers are bleached. The
latter group consists of pitch, fungus hyphae,rust stains,lime,and
sand (2), which
can be bleached only to a small extent, if at
all, and are not discussed in this paper.
The main purpose of bleaching kraft pulp
to full brightness is to produce a white,
strong, clean, and stable pulp that is suitable for high-quality grades of printing paper. It is natural to stress brightness and
cleanliness
while properties
such as
strength are often given a lower priority.
However, for most purposes, cleanliness is
more critical than brightness and the advantages of bleaching to very high brightness
are therefore not always evident. The reason for bleaching to a very high brightness
is that this indirectly guarantees an acceptable cleanliness or that customer demands
are not always necessarily related to the end
product demands.
For many paper grades, a significantly
lower bleached pulp brightness can be accepted if the cleanliness is sufficient. A lack
of cleanliness can lead to a number of problems such as dark dots, fish-eyes, gravure
speckle, perforations, and uneven coating
in the paper mill or final product.
446
Comment
Method
In unbleached paper-grade kraft pulps,

shives dominate and the content of bark,
knots, and other particles is very low. In
bleached pulps, the situation is different.
The shives are eliminated to a large extent
......
" " '\
8-150
c:
::0
o
Average and 95%

confidence limits
'\
~ 100
is
'\
'\
"
50
......
--
o
85
87
89
Brightness,9/,
Fig. 1. Effect of tUrI 011In1gbtness
91
93
95
SCAN
fur"
t:tntrmet'C1iII
plM ImIft pulp bletU:betl'n ~

"
'ng cblorlM-conI,,'n'ng
cbemkills
fIS-
(Z).
Most common
method
TAPPI Test Method
C) Determination
of particle
elimination during bleaching
after the addition of larger
amounts of particles to the
pulp before bleaching
(3)
D) light microscope
examination
of
single particle before and after
bleaching
(4)
E) Determination
of particles
bleaching
of size distribution
before
F) IN microscopic
lignin gradients
(5)
and after
determination
after bleaching
G) Continuous
monitoring
contaminants
of
(6)
of
1) on paper strip
Detects only visible dirt

and does not differentiate
between different types
of contaminants
H) Determination
of type and
structure of residual particles
(scanning electron microscopy,
(1)
(7)
2) in pulp suspension
3) by on-line plastic
dectector
4. Effect of particle origin and

size on bleachability
200
of pulp
T 213 om-85
The concentration
of shives and other
bleachable particles decreases significantly
during bleaching. However, a large reduction in the number of particles does not
necessarily yield a clean pulp because particle elimination is a statistical operation.
This means that an increase in the number
of particles entering the bleach plant leads
to an increase in the number of particles
exiting the bleach plant.
For a given bleaching sequence, a typical relationship exists between cleanliness
and brightness as shown by the example
shown in Fig. 1. Cleanliness improves with
increasing brightness up to a critical brightness above which it changes only slightly.
The critical brightness is often higher than
the brightness needed for a particular paper. Bleaching in the pulp mill is often targeted to the critical brightness to obtain a
sufficlently clean pulp.
Reference
A) Pulp screening
B) Visual inspection
250 ......
tlU!lJS#remenI.
Plastic specks as small as

0.3 nun detected by prototype high-speed camera
(1)
(8)
SEM)
and there is a relative enrichment of particles, knots, bark (mostly stone cell aggregates from spruce), and inorganic material.
A small quantity of knot particles and stone
cell aggregates in an unbleached kraft pulp
may become the predominant residual particles in a pulp bleached to high brightness.
Furthermore,
particles
evident in the
bleached pulp cannot be observed in the
unbleached pulp: pitch, pollen, and insect
fragments (9, JO).
To determine the relative bleachability of
different particles during bleaching, welldefmed kraft pulped particles have been
bleached in a CEDED sequence (9,lO).The
relative bleachability of different particles

during bleaching is shown in Table 2.
The particles most difficult to eliminate
during bleaching are large stone cell aggregates from old birch bark (Fig. 2) and, to a
slightly less degree, stone cell aggregates
from the inner bark of spruce. Note that
the stone cells from the birch inner bark
are almost spherical (11, 12). Stone cell
aggregates are generally more difficult to
eliminate during bleaching than knot particles (Fig. 3). Knot particles can be divided
into two groups: those containing compression wood fibers and those lacking compression wood fibers.
Fig.3.
SeIJImIrtg eltrrnr
mlemgrwpb
oJ" blMebetl
#mot JItIrlIek
447
(11,13).
448
Pulp Bleaching
Low
b1eachability
Birch stone cell aggregates

Spruce stone cell aggregates
Softwood knots
Pine outer bark
Softwood shives
Spruce inner and outer bark

High
bleachability
Birch inner bark

Birch outer bark
Of these two groups, knots containing

compression wood fibers are the more difficult to eliminate during bleaching. Both
types of knots are more difficult to eliminate during bleaching than shives (Fig. 4).
Bark particles from the pine outer bark are
almost as easy to eliminate as shives.
Other bark particles (such as those from
spruce and birch) that are free ofiarge stone
cell aggregates are very easy to eliminate
during bleaching. The results show that it
is advisable to avoid the use of poorly
barked spruce and the unintentional addi-
and Practice
tion of poorly barked birch and to prevent

knot particles from entering the bleach
plant. A 1arge proportion of knot<ontaining chips show up in the coarse screenings
because they are largely found in overthick
and overlarge chips.
If particles of different size are bleached
with chlorine dioxide, particle elimination
is adversely affected by increased particle
thickness (Fig. 5). The critical dimension
for the elimination of particles (shives,
knots, and bark) during bleaching is the
thickness, not the length or width, since
diffusion of chlorine dioxide in the particle
is probably the rate<ontrolling step.
The reaction time in Fig. 5 is defined as
the time required to make the particles visually acceptable as being fully bleached.
50
1IIb1e 2. ReWire bletJdMbUlty oj ll1mldes oj tit/Jernt orlglll blMebetl hi" CI!DED~

(9,10).
-Principles
Knots,
compression
wood
.....
. .
0.5
o
0.1
0.2
OJ
0.4
05
Thickness,mm
0.0
0.7
Fig. 5. Effect oj JItIrlIek tl1kaess 0fI tN time refIIIlm to blMeb sbI_

#mots wtb cblorl1re tlIonM (13).
"""
In these experiments, the pH, temperature,

and concentration of chlorine dioxide were
kept constant (13).
5. Patterns for the degradation

of particles during bleaching
The degradation
of particles during
bleaching occurs by the three different patterns shown in Fig. 6: 1) surface peeling of
fibers when knots consisting of compression wood are bleached with chlorine dioxide (PathA), 2) rapid partial degradation
at the point of fiber liberation during oxygen delignification (Path B), or 3) fragmentation to a number of smaller particles when
shives and bark particles are bleached with
chlorine dioxide (Path C).
Fragmentation increases the rate of particle removal in succeeding bleaching stages
because smaller particles are eliminated
more easily than larger ones. By a proper
mechanical treatment with sufficiently high
shear forces, Path A can be shifted to Path
C (14).
When particles are bleached with ozone,
extensive delignification occurs at the surface (Fig. 7) (15), but the lignin content of
the inner region of the particle is the same
as before bleaching.
The rate<ontrolling step when there is a
surface reaction (Paths A and C) seems to
be diffusion of chemicals within the par-
Chapter IV II: Bleaching Shives and Dirt
449
Partially bleached
ticles.The rate-controlling step when there

is no gradient (Path B) probably is a chemical reaction.
Cleanliness at a specified kappa number
or brightness is the result of two parallel
reactions: bleaching of pulp and bleaching
of particles. Any chemical that can bleach
fibers also has at least some ability to eliminate particles. A typical relationship
between cleanliness
and degree of pulp
bleaching is shown in Fig. 8 for a final chlorine dioxide bleaching stage. The curve is
similar to that found for chlorine, hypochlorite,and oxygen bleaching stages.The curve
is relatively fiat until a particular critical
brightness is reached. Further bleaching
greatly improves the elimination of particles
but fiber bleaching is only marginally affected. From this finding, it can be con0.3
cluded that a sequence with many stages

affords poorer cleanliness than a shorter
sequence.
The relative rates of pulp bleaching and
particle elimination determine pulp cleanliness. Cleanliness is improved if the rate of
pulp bleaching is reduced in relation to the
rate of particle elimination. Because particle bleaching seems to be a diffusion-controlled reaction and the bleaching of fibers
is controlled to a greater degree by the
chemical reaction, it is possible to improve
cleanliness in a particular bleaching stage
by varying the temperature, concentration
of bleaching chemicals, and pH. How this
can be done is briefly discussed below.
For most bleaching
chemicals, pulp
cleanliness is improved by an increase in
chemical concentration and a decrease in
450
1j
~ 01
j
20
10
:~
E
*'
iIJ'
>
.~
.;;;
""
7. Extended delignification
New pulping processes make it possible
to prolong delignification during pulping
(Chap. II I).The result is greater selectivity
with respect to delignification and a much
smaller formation of rejects (Fig. II) (19,
20). In Super Batch pulping, the depth of
delignification in a shive at a given kappa
number has been shown to be about I mm
deeper than in a shive pulped conventionally (19).
8. Oxygen delignification
In laboratory studies, it has been found
that, when an oxygen stage is included in a
bleaching sequence, cleanliness at a particular final brightness may decrease or increase
50
20
..:
'"
10
120min
80 60
40"C
5
0.2
0.2
I
93
92
0.5
I
1
2
k457. m2/kg
I
10
I
0.5
2
k.,,, m'lkg
20
10
67 61 76
64
54
Calculated brightness. % ISO
67
6Z
Fig. 8. Effect of _I'''ttg

sblves Offbrightness afIer a flul eblorlffe dloxUle stllge (16).
Flg.!J.
Effect of
sIJIvM Off brightness
brightness.
20
)4
64
76
Calculated
Fig 7. Estl",.tetlllgnlll
~
III IIff 0%_tkllgnlfted }HIrtkle IU IIJuctIoft of cross-stkm tUstllru:efrom tbe }HIrlkle SJlrftree (15).
Pulp cleanliness after bleaching is the

result of the combined effects of a number
of individual bleaching stages. It would be
advantageous if the final cleanliness were
the sum of particle elimination in each stage
of a particular bleaching sequence. Unfortunately this is not generally the case because particle elimination in any particular
stage varies with bleaching conditions and
the extent of the bleaching in each stage.
0.1
0.3
6. Interaction between different bleaching stages
0.1
0.2
Cross-sectiondistance, mm
and Practice
100
-<
-Principles
temperature as has been demonstrated in

hypochlorite, chlorine, and chlorine dioxide bleaching (9,10,16,17). Exam\>les of the
benefits occurring from a decrease in temperature and an increase in chemical concentration on cleanliness are found in Figs.
9 and 10, respectively, for a final CDI) chlorine dioxide bleaching stage.
pH is another important variable in chlorine dioxide stages. Cleanliness is increased
by a decrease in pH (14,18). Drawbacks
resulting from a decrease in pH are increased chemical consumption
and decreased pulp viscosity.
Oxygen bleaching seems to be one exception to the rule that elimination of particles is diffusion-controlled. This anomaly
is indicated by a uniform lignin content, as
measured by UV absorbance, in oxygenbleached shives which is not observed in
ozone and chlorine dioxide bleaching. On
the other hand, oxygen and ozone bleaching have the same activation energy in the
bleaching of both pulp and particles and a
similar rate equation for the bleaching of
pulp and particles. Therefore, the possibility of improving cleanliness at a given kappa
number by varying the bleaching conditions
in oxygen and ozone bleaching appears
unlikely.
100
"#. 50
~-
E
c:
c
NO.2
'"
@)
Pulp Bleaching
% ISO
for tiff O(C+D )E-hletM:bed
-"""g
tUozIde blellCbIttg
at fllll'Ylflg temperIIlflres tIffd times (9,16).
softtrood
Inwft pulp afin'
chlorlffe
'5000
100
;f.
50
t,oooo
.f
~..
CII
10
.~
c::
'2
.
a:
!5000
OEIJED
1
0.5
2
m2&g
k057'
87
Fig. 10. Efft ofllrlglltruss OJI

4tonM
blMelliltg fllUII~""'"
".".g
s/1IH$ft!r
__trYItimIS-
10
ng. 13. Bfed
20
64
% ISO
54
O(C+D)IJ-6lHeIIH sofl-M
Ittwft pIIq"'fterell/qrlfUJ
of eIIIorIINtUoxIikfor tlIfferl8g U-
(9,16).
9. Chlorination
Annergren and lindblad (2) have studied the effect of C-stage conditions
on clean-
liness after a CEDED sequence.

They
showed that an increased chlorine charge
improved cleanliness at a specified final
brightness. Similar results have also been
published by Histed and Canovas and by
Rapson et al. who used varying chlorine
dioxide substitution
levels (10, 23, 24).
Their results indicate that a risk for decreased cleanliness exists when the "low
chlorine multiple technique" is used for environmental
reasons. Annergren
and
lindblad (2) also showed that the use of
'00
,..
...
,.
40
etdtmJ hteb (S8JWrJltIteII)(B) Ittwft p.lpt",

ofsofhrootl (19).
SllbstttJllUnl
(2).
more chlorine dioxide in OED final bleaching improved cleanliness. They concluded
that an alternative to hlgh chlorine charge
in the first bleaching stage is to bleach at
economically
optimized conditions to a
higher brightness, mainly by increasing the
chlorine dioxide charge in the final bleaching. In any event, the choice is dictated by
local economic considerations.
10. Elemental chlorine-free (ECF)

bleaching
Substantial substitution of chlorine dioxide in the first bleaching stage improves
cleanliness if a mixture of chlorine and chlorine dioxide is used (2, 3, 10,23, 24).When
sequential bleaching is employed at 25%
100
50
~
10
E
'"'"
t,oooo
8
f
'5000
1
0.1
Fig.11. CompdrlsonofnJedforrlUltton In_timull Well (A) .fIIl e:deruletl ."",Ift-
for WIorwtory
Ittwft JnIlI fllUII IItIryIIIg
'c
'iij
20
0.0
... <
JI
tltonM
... SCAN
chlorine dioxide substitution, a deterioration in cleanliness has been reported by

Annergren and lindblad, while a DEDED
sequence produced a very clean pulp (Fig.
13) (2). The improvement obtained with
increased chlorine dioxide substitution
when bleaching with a chlorine/chlorine
dioxide mixture probably results from an
improved rate of particle removal in chlorine dioxide final bleaching. The negative
effect of sequential bleaching at 25% substitution may be attributed to the improved
bleachability of the fibers which decreases
the chlorine dioxide consumption
in the
final bleaching. Because of the decreased
chemical charge, the driving force for particle removal in the final bleaching is also
decreased.
Introduction of the medium consistency
(MC) technique in the first stage increases
bleaching chemical concentration with the
result that the cleanliness of the pulp is improved.
Final bleaching in a single D-stage provides much better cleanliness than a OED
sequence (Fig. 14). The reason is that the
selectivity for particle removal increases
with increasing brightness in a given stage.
It, however, would be very uneconomical
to bleach with CED to a high brightness
rather than with CEDED because of the high
~- 20
'5000
2.0
0.'
of s/1IH$ OJIlIrlgillrlns
clllorIIN
82
76
CalcuIaIBd blighb_.
(21). This behavior reflects the combined

effects of a less intensive final bleaching
than is used in the absence of an oxygen
stage and particle elimination in the oxygen stage. When comparing these laboratory results with industrial experience, it
must be remembered, bowever, that industrial oxygen delignification employs a mechanical treatment which probably has a
positive effect on particle removal.
A pronounced
improvement in cleanliness is obtained after final bleaching if
deligniflcation in the oxygen stage is extended to very low kappa numbers. This
situation is possible with the PRENOX'"
system (Fig. 12) (22).
1'0
6IHd1M sofl-M
92
"
1IIigI8I88.
0.2
452
451
0.2
0.5
10
20
k4571m2Jkg
1\)
7'
80
..
90
.,
93
92
87
82
Calculated
ng. 14. IJffed of~l.g

D or DIJD(16).
64
76
brightness,
54
%150
dtlfIfISOJIlIrlglltfless of _ (O(C+D)IJD).blHellM mft pilip .fter blMe""'g wltll
chemical consumption in the three-stage

sequence. However, the introduction of
oxygen- ancl/or hydrogen peroxide-reinforced alkaline extraction improves the economics of the short sequence
(25).
Although the reinforcement may negatively
impact cleanliness after a particular sequence, a C(E+O)D sequence provides a
much cleaner pulp than a CEDED sequence
(25) because of the higher chemical concentration in C and D stages. Contradictory
results on the effect of reinforced alkaline
extraction on cleanliness have been reported by van Lierop et al.(26). They
claimed that the shive count after bleaching was 3MO% lower than after a sequence
without (EO).The peg-type stirring mechanism that was used to simulate the (ED)
stage eventually could have partially degraded the particles.
Figure 15 contains a summary of how
different variables influence the relationship
between cleanliness and brightness. The
development of the relationship between
cleanliness and brightness is indicated by
an area which shows a normal range of
variation, and the limiting curves are examples of typical extreme relationships.
The length of the arrows indicates the
relative importance of the different variables: lower kappa number of unbleached
pulp, decreased equivalent active chlorine
multiple in the first bleaching stage, and an
increased share of D in the first bleaching
stage (27).
Brightness
Fig. 15. Effect ofb~
IJIIrl4bIes011tbe ,."WioIIship behtJetm dellalifIBss llrut brlgbtflBss
(27).
453
11. Totally chlorine-free (TCF)

bleaching
Because of market conditions, a demand
for totally chlorine-free bleached pulp has
arisen. Instead of chlorine and chlorine dioxide, bleaching chemicals such as hydrogen peroxide and ozone are used, often
combined with extended deIignification in
the pulping process. However, very few
studies have been reported on how these
new bleaching agents affect the cleanliness
of kraft pulps.
11.1 Bleaching with ozone
Ozone followed by alkaline extraction
(ZE) has been shown (28) to be a very poor
bleaching agent for the elimination of particles compared with chlorine and chlorine
dioxide (CE or DE). The problem is that
ozone is very reactive with pulp fibers and
therefore very inefficient for particle bleaching if the comparison is made at a specified
kappa number. However, after DED bleaching, the cleanliness of an ozone-bleached
pulp may still be satisfactory (15).A high
E, kappa number and, thus, a very high
chlorine dioxide demand in the final bleaching explains the good cleanliness obtained
using a ZEDED sequence.
11.2 Bleaching with hydrogen
peroxide
Annergren
and Hagglund (29) have
found that lignin-preserving bleaching of
TMP with hydrogen peroxide has only a limited effect on the concentration of shives
and dirt specks. On the other hand, the visibility of these impurities is substantially
decreased because of the lessened fiberparticle contrast resulting from extended
hy~nperoxide~e~hing.
When kraft pulps are bleached with hydrogen peroxide, an EDTA pretreatment
is
very important otherwise transition metals
decompose the hydrogen peroxide to radical species that cause a fiber strength decrease (30).
An EDTA pretreatment
is also very important for pulp cleanliness, especially if the
chips contain knots. Knot-containing chips
have much higher manganese content than
conventional chips (Table 3) (31).
454
Pulp Bleaching
-Principles
and Practice
Tllble 3. Met'" COfIteatof cltlps (mgIIrg)(31).
o 0
[J OZ
... OO(EO)IJED
20000
Knot-free chips
Knot-containing
chips
Ca
Na
Fe
Mn
690
32
32
10
3070
1.0
13
390
Norden and Germgard (32) have found

that the cleanliness of a pulp bleached with
oxygen, ozone, and hydrogen peroxide is
comparable with that for a chlorine~ioxide bleached pulp (Fig. 16). These results
are contradictory to those of Ow and Singh
(33) and DaSilva (34) who claimed that
bleaching in a sequence using ozone and
peroxide has a negative impact on cleanliness.
Moldenius (35) has reported that hydrogen peroxide combined with extended
cooking is very effective and that the cleanliness ofTCF-bleached pulps is better than
that of chlorine- and chlorine dioxidebleached pulps.
The superiority of hydrogen peroxide in
improving cleanliness is expected because
modem bleaching with hydrogen peroxide
is characterized by long retention times,
high concentrations of hydrogen peroxide,
and slow fiber bleaching. The combination
of extended kraft pulping and present~y
bleaching with hydrogen peroxide therefore can be expected to provide a very clean
pulp.
12. Mixing
High-shear mixers are attractive from an
economic point of view. It is well established that, in most cases, they lead to a reduced chlorine dioxide requirement which
in turn makes it possible to lower the
bleaching temperature (36, 37).
The effect of mixing on cleanliness is not
straightforward. In a study based on a computer simulation of the Dl stage, it was concluded that more efficient mixing decreases
cleanliness at a specified brightness and
temperature (Fig. 17) (38). If the temperature is decreased, the effect is less and, at a
sufficiently low temperature, and in the
presence of a relatively high chemical residual, cleanliness is improved.
. OZP
o
~
00
m
ro
~%ISO
Fig. 16. Effects of shives 011 brlgbtfIBss
W-blucbetl pulps (32).
for ECF- llrut
Improved mixing, which may be used for

bleaching to higher brightness in a D 1 stage
(or any other stage) without consuming
more chlorine dioxide, also improves cleanliness. This principle has been verified for
chlorination by Reeve et al. (39). Improved
mixing in a D, or chlorination stage also
makes it possible to save chemicals in other
stages bleached to the same final brightness.
This can lead to increased or decreased
cleanliness. A saving in hypochlorite or a
reinforcement chemical most likely would
increase cleanliness, but a saving of chemicals in the chlorine or the chlorine dioxide
stages would have the opposite effect.
100
80
60
.c
""
" 40
.n;
E
20
o
40
50
60
70
Brightness, % ISO
80
Fig. 17. Effect of mlxhlg Oft tbe ,."IIItimIsbip behtJetm

resitIIItIl shives llrut brlgl1tflBss. 171e mixiag
eJJfd-cy
is reportetl tIS tbe coejJfdeat
of
IJllrl4Iitm sIR, lllbert! s is tbe sttllUltlrtl devitI.
tiort of tbe cl1lorlfIB tlioxitk cHrge llrut x is
(38).
tbe -IC/
c"""'"
13. Approach@s for improving

cleanliness
When impurities are encountered in the
final pulp, the identity of the particle type

should be determined. Precautions should
be taken to ensure that no foreign bodies
or particles, such as plastic and sand, reach
the pulping equipment. Particles that are
difficult to bleach should not enter the
bleach plant.
Reduced chip thickness, improved alkali
treatment
and impregnation
during
pulping, and separation of coarse rejects
followed by repulping reduce the particle
content
entering
the bleach
plant.
Delignification to low kappa numbers in
kraft pulping leads to a much smaller formation of rejects.
Bleaching in short bleaching sequences
provides much better cleanliness
than
bleaching in long sequences. A high bleaching chemical concentration, a high chemical charge, and a low reaction temperature,
improve pulp cleanliness. It is important
never to exhaust chemicals before the pulp
leaves the bleaching tower. Bleaching to
higher brightness favors the cleanliness of
the pulp.
13. AxegArd, P., Svensk

345 (1980).
Pappersttdn.
1. Robitaille, M.A., "Policing Dirt and Plastic

Contamination,"
1991 TAPPI Bleach Plant
Operations
2. Annergren,
G.E. and Lindblad,
59(11):95 (1976).
3. Axegard, P., Svensk
284 (1980).
P.O., Tappi
Pappersttdn.
4. Axegard, P. and Teder, A., Pulp

78(9):T196
(1977).
5. Hill,). and Haglund,
(1975).
83(10):
Pap. Can.
H., Tappi 58(10):120
6. Axegard,
P. and Jonsson,
V.,
Pappersttdn.
82(10):310
(1979).
7. Karlsson, H., STFI Sweden,
results, 1993.
8. Treiber,
E., unpublished
9. Axegard, P., Svensk

398 (1980).
Svensk
unpublished
results,
Pappersttdn.
1973.
83(14):
10. Bruun, H., Henricson, K., Kroriliif, T., Pap.

Puu 10(3):126 (1983).
11. Axegaro, P. and Teder, A,. Pulp Pap. Can.
78(9):T200
(1977).
12. AxegArd, P., Svensk
449 (1978).
Papperstidn.
81(14):
83(12):
i56
30. GeUerstedt, G. and Pettersson,

I.,J U"'bod
Chem. Technol 2(3):231 (1982).
14. AxegArd, P. and Teder,A.,Trans.Tech.

Sect.
Can. Pulp Pap. Assoc. 6(2):48 (1980).
31. Sahlberg, V., STFI, Sweden,

results, 1993.
15. Germgard,
Pappersttdn.
32. Norden,
S. and Germgard,
V., Svensk
Papperstidn.
96(2):26 (1993).
V. and Sjagren, B., Svensk

88(15):RI27
(1985).
16. AxegArd, P. and Teder,A., Trans. Tech. Sect.

Can. Pulp Pap. Assoc. 6(3):73 (1980).
17. Axegard,
P. and Tormund,
D., Svensk
Pappersttdn.
88(3):R36 (1985).
18. pattyson,
G., Rae, R.G., Reeve, D.W.,
Rapson, WH., Pulp Pap. Can. 82(6):T212
(1981).
19. Kovasin, K. and Tikka, P., "Superbatch
Cooking Results in Superlow Kappa Numbers,"International
Conference: New Available Techniques
and Current Trends Proceedings, SPCI, Stockholm,
1992, p. 71.
20. Hjort,A.,"Effects
on pulp and paper properties from Iso-thermal
cooking (lTe) and
black liquor impregnation
in a continuous
digester,"
International
Non-Chlorine
Freeman, San Francisco, 1994.
21. AxegArd, P., Pap.Puu
References
455
6(11):723
(1979).
22. Lindqvist,
B., Marklund,
L.A., Norden, S.,] Pulp
(1986).
A., Lindstram,
Pap. Set. 12(6)
23. Histed, ).A. and Canovas,
R.V., "Optimum
CWorination Stage Conditions
Part I
and II," International

Pulp Bleaching Conference,
Preprints,
Tech. Sect., CPPA,
Montreal, 1985, p. 127.
24. Rapson, WH., Anderson, B., Reeve, D.W;
Pulp Pap. Can. 78(6):T137 (1977).
25. Lindstram,
L.A, Norden,
Tappi 64(6):91 (1981).
S., Carre,
G.,
26. van Lierop, B., Liebergott, N.,TeOOorescu,

G., Kubes, G.).,). Pulp Pap. Sci. 12(5):}133
(1986).
27. Annergren,
G.E., "Environmental
Harmonization of High Quality Bleached Kraft
Pulp Production
a High Tech Development," EUCEPA Conference
Proceedings,
SPCI, Stockholm,
1990, p.66.
28. Germgard,
68(4):307
29. Annergren,
V, and Sjagren,
(1986).
B., Pap. Puu
G.E. and Hagglund,
T.A., "Ef-
fect of Peroxide
Bleaching on Dirt and
Shives in TMP," International
Mechanical
Conference
Preprints, Tech. Sect, CPPA,
Montreal, 1979, p.145.
unpublished
33. Ow, S.K. and Singh, R.P., "Advances

in
Ozone Bleaching Part II, Bleaching of Softwood Kraft Pulps with Oxygen and Ozone
Combination,"
1984 TAPPI Oxygen Delignification
Symp. Notes, TAPPI PRESS,
Atlanta, p.43.
34. Claudio DaSilva, E., "Aracruz Celulose SA
Mill in Brazil: CWorine-Free Pulp Production Experience," International
Non-cWorine Bleaching Conference
Proceedings,
35. Moldenius,S.,"Mill-scale
operation ofTEF
Bleaching at SOOra's Monsteras Mill, Sweden," International
Non-Chlorine
Proceedings,
36. Sinn,S.,PulpPap.
58(6):1190984).
37. Kolmodin,
H., Svensk
87(18): 8 (1984).
Papperstidn.
38. Backlund, 8. and Parming,A.M., "A Kinetic

Study of Inhomogeneities
in Bleaching,"
International
Preprints,
1985, p.155.
39. Reeve, D.W, Earl, P.R, Gullichsen,].,
Pu,
C.M., Magued,A., Rapson, WH., Pulp Pap.
Can. 89(6):T202 (1988).
SECTION V:
The Technology of
Chapter 1:
Peroxide Bleaching of
(Chemi)mechanical Pulps
J.R. Presley and R.T. Hill
Solvay Interox
Houston, TX
1. Introduction.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 459
2. Peroxide bleaching
2.1 Composition
2.2 Stability
solutions.
. . . ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 459
459
460
3. General description
of peroxide bleaching
4. Peroxide bleaching
chemistry.
processes
. . . . . . . . . . . . . . . . . . . .. 460
. . . .. . . . . . . . . . . . .. . . . . . . . . . .. . .. . . . . . . .. 461
5. Factors affecting brightness response in peroxide bleaching

5.1 Initial color (brightness) of wood and unbleached pulp . . . . . . . . . . . . . . . . .
5.2 Effect of the pulping process on initial
brighmess and bleachability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3 Metal impurities
5.4 Process variables. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.5 Peroxide bleaching of recycled fiber ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6. Effect of peroxide bleaching on physical properties . . . . . . . . . . . . . . . . . . . . ..
461
462
7. Bleach plant design and operation

7.1 Flowsheets for peroxide bleaching processes
7.2 Bleach plant process description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
7.3 Guidelines for bleach plant selection. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
477
478
480
484
462
463
468
474
477
8. Non-conventional
peroxide bleaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 485
8.1 Refiner bleaching. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 485
8.2 Alkaline peroxide chemithermomechanical
pulping. . . . . . . . . . . . . . . . . . . . 485
9. Heat- and Ught-stability of peroxide-bleached
pulps
. . . . . . . . . . . . . . . .. 487
9.1 Factors affecting light and heat reversion.
487
9.2 Strategies for controlling reversion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 488
10. Environmental
impact.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 488
457
Chapter VI: Peroxide Bleaching of (Chemi)mechanical
Pulps
459
Chapter V 1:
Peroxide Bleaching
of (Chemi)mechanical
Pulps
In this chapter, the use of peroxide in

bleaching is confined to its applications in
(chemi)mechanical
pulp bleaching and in
the processing (including bleaching) of secondary (recycled) fibers.
1. Introduction
2.1. Composition
Hydrogen peroxide can dissociate through
ionization or radical reaction mechanisms
as shown by the examples listed in Table 1.
2. Peroxide bleaching solutions
Hydrogen peroxide is a versatile and

widely used oxidative bleaching agent in the
pulp and paper industry. In chemical pulp
bleaching, hydrogen peroxide is used to
reinforce a1kali extraction stages and reduce
the kappa factor required to achieve good
delignification in the first stage, or to reduce
the total applied chiorine dioxide in the final D stages (see Chap.IV).As a final stage
or in the bleached high density storage
chest, peroxide is a good brightening agent
and can provide increased brightness stability (reduced reversion) (see Chap.IV).
Hydrogen peroxide is the most widely
used oxidative
bleaching
agent in
(chemi)mechanical
pulp bleaching. In this
application, it is particu1arly useful in situations where high brightness is desired or
where the grade-mix produced requires increased flexibility in the bleach plant. Hydrogen peroxide is also used in secondary
fiber operations as a brightness preserver
during pulping and flotation, and as a
bleaching agent in the post-bleaching
of
deinked stock.
TIIbk l.lIytItvprI perodtIe 4issoeIIItitnJ1"HdioIIs.

HP2 +-+HOO' + 0+
HP2 -+ HO- + 00+
HP2 -+ HOO. + H.
OH' !t 0+
0>, (superoxide anion radical) + HP
[IJ
[2J
[3J
HP2 -+ 20H.
[4J
(hydroxyl radical)
The perhydroxyl anion, HOO-, is generally

accepted as the active bleaching species in
alkaline hydrogen peroxide systems. Although the anion is normally present in
equilibrium with undissociated hydrogen
peroxide (Eq. 1), the formation of the anion can be regulated by increasing or decreasing the pH (Eq. 5) and temperature
(Fig. 1).
HP2 + OH- -+ OOH- + HP
[5J
The addition of an alkali source (usually
sodium hydroxide) to a peroxide solution
-N
0
C\I
;;.
+
1.0
0.8
g.....
0.6
460
forces the equilibrium in Eq. 5 to the right,

producing the desired anion. For example,
at pH 10.5, less than 10% of the total peroxide is present as perhydroxyl anion while
at pH 12.5, the peroxide is 95% dissociated
(1). The formation of perhydroxyl ion is
also enhanced by increasing the temperature of the system as shown by the plots in
Fig. 1.
Other reactive species in an alkaline peroxide bleaching system include molecular
oxygen (0) and oxygen<ontaining radicals
such as the hydroxyl radical, (80.) and superoxide anion (2') formed in peroxide decomposition reactions and by autoxidation
of the lignin during bleaching.
2.2 Stability
Hydrogen peroxide readily decomposes
under bleaching conditions according to the
overall reaction
[6J
Although the decomposition process is often viewed as a base<atalyzed reaction having the overall form,
HP2
+ HOO' -+ 02 + HO- + HP
[7J
results reponed by Colodette et al. (3) indicate that peroxide decomposition can be
more accurately described as a transition
metal<atalyzed process whose main reactions are illustrated by the sequence shown
in Table 2.
The transition metal-induced decomposition of hydrogen peroxide during bleaching is generally believed to be undesirable
because it leads to a loss of perhydroxyl ion,
a species believed to react with and eliminate chromophores of the type present in
(chemi)mechanicals pulps (see Chap. III 4).
For this reason, control of the transition
metals responsible for peroxide decomposition is an imp on ant goal in peroxide

bleaching (see Sect. 5.3). On the other hand,
there is experimental suppon (4) for the
view that a controlled release of hydroxyl
and superoxide
ion radicals by metal-induced decomposition
may have a positive
effect on brightness in the bleaching of
(chemi)mechanical
pulps.
3. General description of peroxide bleaching processes

The bleaching of (chemi)mechanlcal
pulps with hydrogen peroxide is usually
carried out by intimately mixing an alkaline
peroxide bleaching solution (commonly
referred to as bleach liquor) with the pulp.
The components
of alkaline peroxide
bleach liquor are hydrogen peroxide, caustic soda, sodium silicate (41 Be), water, and
(sometimes) Epsom salts. The mixture of
pulp and liquor is then held in a bleaching
tower for 0.5-4 or more hours. The temperature of the mixture commonly ranges
from 140 to 180F (60 to 77C).
After exiting the tower, the pulp pH is
lowered to prevent alkaline reversion and
sent to the paper machine or to dryers
when produced as a market pulp. In some
operations, the residual peroxide is decomposed.This step occurs automatically when
sulfur dioxide is used for pH adjustment
before the fmal processing step.
Several factors influence bleaching performance: consistency, retention time, temperature, total alkalinity level, pretreatment,
bleach liquor stability, furnish type, and
even the preceding pulping process. Many
of these factors are interrelated and are discussed in several of the following sections
of this chapter.
'J: 0.4
0
Q.
~
m
0.2
H202
HOO'
0
8
Fig. I. HlTeet ofpll 011tile ~
10
11
pH
of #JytIroga perodtIe (1).
12
13
14
Mn+ -+
M(n+l)+
M(n+l)+
+ HO'
+. OH'
+ OH.
-+ Mn+ + HlO + 0>,
M(n+l)+
0>,
+ 2' -+ 02 + Mn+
+ HO. -+ 02 + HO'
(M
= transition
[8J
[9J
[IOJ
[llJ
metal ion)
4. Peroxide bleaching chemistry

The reactions involved in the hydrogen
peroxide bleaching of (chemi)mechanical
pulps are discussed in greater detail in Chap.
III 4. A brief review of the subject is included here.
As stated previously, the perhydroxyl
anion (HOO-) is genera1ly accepted as being the principal active species in peroxide
bleaching.This anion is a strong nucleophile
which, during bleaching, converts electronrich chromophores typified by , p -unsaturated aldehydes and ketones, and phenolic
ring-conjugated
ethylenic
or carbonyl
groups to their non-chromophoric
counterparts. The reactions of lignin with peroxide are not reversible
and lead to the
permanent removal of most of the chromophoric groups present in the lignin m~lecule.An example of a nucleophilic attack
of a perhydroxyl anion on a lignin chromophore during hydrogen peroxide bleaching is shown in Fig. 2. The phenolic and
non-phenolic units comprising lignin are
not directly attacked by the perhydroxyl
anion itself so that the lignin is not destroyed
or modified sufficiently to appreciably increase its solubility. As a result, bleaching
occurs without a significant impact on yield.
In conjunction with the elimination of
certain chromophore groups during bleaching, competing reactions involving hydroxyl
and perhydroxyl ions lead to the formation
of new chromophore systems as is detailed
in Chap. III 4. These newly created chromophores may partially offset the bright-
Pulps
461
ness gains resulting from chromophore

elimination reactions.
Besides the contributions of ionic species in the elimination and creation of chromophore systems in peroxide bleaching,
there is mounting evidence that oxygencontaining free radicals, arising from metalinduced peroxide decomposition, may have
an active role in determining the outcome
of peroxide bleaching. For example, hydroxyl radicals, in the proper amount, have
been reported (4) to have a positive effect
on mechanical pulp brightness. When acting in conjunction with hydroxyl radicals,
superoxide anion radicals also appear to
have an active role in peroxide bleaching
of mechanical
pulps (5). It should be
pointed out that these two radicals can
attack and degrade phenolic and non-phenolic groups. Therefore, high concentrations of these radicals should be avoided to
maximize pulp yield.
5. Factors affecting brightness

response in peroxide bleaching
The raw material in (chemi)mechanical
pulping is, almost without exception,
wood. At present, (chemi)mechanical pulps
are made from a large variety of both softwoods and hardwoods, all of which have
different responses in peroxide bleaching.
As a further complication, the pulping process itself can have a significant impact on
the bleachability of the pulp.
462
5.1 Initial color (brightness) of wood

and unbleached
pulp
The initial brightness
and potential
brightness response of any (chemi)mechanical pulp is highly dependent
on the
wood species from which it is made. Many
of the wood species used to make (chemi)mechanical pulp are light in color and relatively easy to bleach. These include
softwoods such as spruce, fir, and pine as
well as hardwoods such as aspen, other
poplar-type species, and birch. The wide
range of brightness
values found after
thermomechanical
pulping of a variety of
softwoods is shown by the data in Table 3.
Generally, a higher initial (unbleached)
brightness implies a higher bleached brightness when equivalent amounts of bleaching chemical are applied (6). This is also
shown in Fig.3, where pulps produced from
the same wood but by different processes
were bleached over a range of peroxide
applications.
5.2 Effect of the pulping process on

initial brightness and bleachability
(Chemi)mechanical
pulping refers to a
wide variety of processes, but the major
(chemi)mechanical
pulping processes employ grinders or refiners to separate the
wood fibers.The major (chemi)mechanical
pulping processes are briefly described
below (see also Chap. n 1).
Table 3. l!1IblMcbetll1rlgbmess
Wood Species
Eastern larch
Balsam fir
Lodgepole
pine
Eastern hemlock
57.3
61.1
White pine
Red pine
5.2.1 Groundwood
and
pressurized ground-
wood
Groundwood pulping processes employ
pulp stones which are covered with an abrasive grit. Debarked whole logs, cut to a uniform length, typically about four feet, are
pressed against the revolving stone and individual fibers and fiber bundles are peeled
away. Although the grit does not cut the
wood as this would produce an excess of
debris (shorter fibers and fines), grinder
pulps nonetheless do have higher levels of
debris than do refined pulps. This is not a
totally undesirable characteristic of groundwood pulps because the high debris helps
contribute to making a smoother, more
opaque sheet, particularly when hardwoods
SGW
PGW
TMP
80
59.4
59.5
41.6
54.5
56.7
45.2
Black spruce
Jack pine
85
of so.flviotM 1MP (7).
Unbleached TMP
Brightness, %150
75
~~70
en
HCOO.
I/J
Q)
-c:
Bleaching
65
60C, 180 min,

20% consistency
C)
.;:: 60
conditions:
3% silicate
.s::.
55
50
0
234
H202,
Flg.3. hlfl-
ofp,dfrl"g}tl'flass
% on pulp
ONbrlgbltlus tlevelojlttltml ofspntu
(cbemi)mecbtmklll
jItIlps (8).

are the wood source (See Chap. VII 3).
Stone grinding is performed at atmospheric temperatures and pressures. It is the
oldest form of (chemi)mechanical
pulping
and was first practiced commercially in the
1850s. The product, stone groundwood
(SGW), is typically referred to as groundwood. Pressurized grinding is practiced, as
its name implies, at pressures above atmospheric, thus permitting the grinder to operate at higher temperatures. The higher
temperature provides additional softening
of the lignin, and the fibers are more easily
separated. Pressurized groundwood (PGW)
pulps therefore have higher long fiber fractions and lower debris contents than do
stone groundwood pulps. Both stone and
pressurized
groundwood
pulps typically
respond better to bleaching than do refuier
(chemi)mechanical
pulps (RMP, TMP,
CfMP).
5.2.2 Refiner pulping processes
Refiner pulping processes typically consist of two or more disc refining stages.The
refiners are equipped with either two
counter-rotating
discs or one rotating disc
and one stationary disc. A suspension of
wood chips (in water) is fed into the center of the refiner and propelled outward by
centrifugal force through the refining zone.
Although the exact mechanism of fiber
separation is not known, it has been proposed that, as the chips pass through the
refiner, they are repeatedly compressed and
relaxed.This compression-relaxation
action
imparts energy to the chip and causes the
bonds holding the individual fibers together
to rupture, producing pulp (9). A large
amount of steam is also generated during
the pulping process, and it has been speculated that it may play a major role in the
(chemi)mechanical
separation of the fiber
(10).
There are several variations of refiner
pulping processes. The simplest is refiner
mechanical pulping, which was first practiced commercially in the 1950s. In this
process, raw wood chips are refined at atmospheric
pressure to produce a pulp
(RMP) having a higher long-fiber fraction
than groundwood.Therefore,
RMPs are typi-
Pulps
463
cally stronger and bulkier than groundwood

pulps. The heat generated during pulping,
however, does tend to darken RMP so that
it typically has a lower brightness [darkerJ
and is less bleachable than groundwood
pulp.
Thermomechanical
pulping differs from
refiner (chemi)mechanical
pulping in that
the chips are preheated to a temperature
of 120-1350 C and refined under pressure
in the primary refiner. Preheating softens
the wood chip so that the resulting pulp
has a higher long-fiber fraction and is slightly
stronger than refiner mechanical
pulp
(RMP). The unbleached brightness is also
slightly higher than that of RMp, although
TMPs are still not as bright or bleachable as
groundwood made from the same wood
species.
pulping employs both chemical and thermal pretreatments of wood chips. In sulfite-based
pulping, the chips
are presteamed and then impregnated with
sodium sulfite. The . sulfite reacts with the

lignin to soften the chip and provides a
modest amount of bleaching. Chemithermomechanical pulp (CTMP) has a higher longfiber fraction than TMP and tends to be
stronger, brighter, and of lower opacity. It
also tends to be more bleachable than RMP
orTMP produced from the same wood.
The relative bleachability
of (chemi)mechanical pulps made from the same
wood species tends to be as follows:
GW > PGW > CfMP > TMP > RMP

5.3.1 Metal sources in peroxide bleaching
systems
The main source of metal ion contamination in (chemi)mechanical pulp bleaching is the pulp itself. Trees (plants in general)
assimilate metal ions and nutrients present

in the soil in which they are grown (11).
The amounts and types of metal ions
present depend on the species and growing location. Trees grown on the mineralrich soils in Ontario and Quebec (the
Canadian shield formation) have a different
464
metal ion content than do trees grown in

the Pacific Northwest. Coniferous trees
(e.g., hemlock) tend to have a higher metal
content than do hardwoods such as aspen.
The metal ion contents of four pulp samples
are listed in Table 4. Besides their effect on
bleach response and their deleterious effect
on hydrogen peroxide stability, metals in
pulp can form colored complexes with lignin macromolecules (12).
Also of concern is metal contamination
from the chemicais used to make bleach liquor. Iron is a contaminant
in technical
grade sodium hydroxide or in bulk sodium
silicate. Other non-wood sources of metal
contamination in the pulp include process
water and processing equipment (through
wear and chemical attack).
1iIbk 4. 'J'yJIIad-W
etmImt of tIJOOII
sJIks (13).
Wood Species
Metal Content,
Iron Manganese
Hemlock, western
Hemlock, eastern
Aspen, midwest
Spruce, eastern
115
20
55
17
105
110
4
136
ppm
Copper
14
1
5
1
5.3.2 Control of hydrogen peroxide decom.

position
As described in the section on peroxide
decomposition (Sect. 2.2, eqns. [8J and [9]),
metais, particularly transition metals, act
as catalytic decomposition agents when in
contact with hydrogen peroxide. The most
common metals routinely encountered in
the peroxide bleaching of (chemi)mechanical pulps, in order of decreasing decomposition activity, are manganese,
iron,
copper, chromium, and nickel. Of these, the
most active decomposition element is manganese. Other transition metais (e.g., cobalt)
also cause peroxide decomposition but are
usually not present in the pulp or bleaching chemicals
in amounts
significant
enough to have an appreciable effect.
The first step in successful hydrogen peroxide bleaching is to minimize the occurrence of catalytic decomposition.
Two
approaches, commonly used together, are
used to achieve this goal: pretreatment of

the pulp before bleaching and stabilization
of the bleach liquor before addition to the
pulp. Bleach liquor stabilization is covered
in detail in a later section.
5.3.2.1 Pretreatment of (chemi)mechanical
pulps with organic chelants
The purpose of pretreating (chemi)mechanical pulps is to complex and wash out
most of the transition metals present in the
pulp before the addition of bleach liquor.
Pretreatment is commonly carried out using an organic chelant which forms a
organo-metallic
complex with the free
metal. Typically, the pentasodium
salt of
diethylenetriaminepentaacetic
acid
(Na5DTPA) is used in this role. Na,DTPA
fortnS a very strong complex with manganese, the most active of the peroxide decomposition agents. The pretreatment
is
usually carried out at low consistency
(e.g. ,3-5%) at a pH of 4.0-6.0, after refining
or grinding (e.g., in a latency chest following refining).The amount ofDTPA added is
usually in the range of 1 to 6 kg/ton of pulp
and is added on an "as received" basis. Before being bleached, the pulp is thickened
to moderate or medium consistency ).1 0%)
on a decker or disc filter or to high consistency (20-35%) on a belt (twin wire) press
or twin roll press. This thickening step is
important
because the chelated (complexed) metals are washed from the pulp
in the process. When a thickening step before bleaching is not possible, the addition
of the chelant still decreases the amount of
peroxide decomposition which occurs during bleaching, though not as significantly.
The addition of organic stabilizers to bleach
liquors is discussed in a later section.
There are two easily measured parameters to detertnine the effect of a pretreatment and define the optimum application.
These are brightness and hydrogen peroxide consumption, which is determined by
measuring the residual peroxide on the
pulp at the discharge point of the bleach
tower. In the example shown in Fig. 4, the
effect of a DTPA pretreatment on CTMP 1
was to increase brightness by at least 4
points and reduce peroxide consumption

by 35%. This reduction
in peroxide
con-
sumption
can be important
in situations
where bleach liquor is reclaimed at the end
of the bleaching treatment and recycled to
a previous bleaching stage.The response of
the PGW sample to pretreatment was much
less pronounced, suggesting the need to determine if pretreatment
was necessary in
this case. Figure 4 also provides an example
of a pulp (CfMP 2) where DTPA pretreatment had no significant effect on brightness
response or peroxide
consumption.
In the
Pulps
465
case of CfMP 2, no pretreatment is recommended.

It should be noted that aluminum,
although not usually considered a peroxide
decomposition
cata1yst, can affect the chelation of other metals, notably manganese.
This effect is usually seen where aluminum
concentrations
in the process stream reach
500 ppm or more, although an effect on
pretreatment
requirements
has been seen
at levels as low as 100 ppm.This occurs as
a result of the preferential chelation of alu-
78
466
Pulp Bleaching Principles and Practice

73.0
o
-a.
Q) 72.0
....
iIi
cfl 71.0
en
(/)
Bleaching conditions:
2% H202, 1.4% NaOH
3% silicate
68aC. 120 min.
20% consistency
Q)
c:
E 70.0
OJ
.;::
III
69.0
0.0
76
0.6
0.8
1.0
1.2
DTPA, % on pulp
PGW
~74
Fig.5. Effectof DTPA tU/dltimt

taining a bigb al"",l,",m
~0
en 72
III
Q)
c:
.E 70
OJ
.;::
CD
68
0
0.2
0.4
DTP A, % on pulp
0.6
0.8
0.6
0.8
100
c..
a.
as 90
0
~0
80
r::
0
70
EE
60
CTMP1
:J
III
c:
0
()
50
C\I
40
0
C\I
:I:
CTMP2
30
0
0.2
0.4
DTP A, % on pulp
Spruce:
CTMP:
60C. 120 min.

15% consistency
3% H202.
Fig. 4. Effect of DTPA pretreatment

ofsjmu:e
0.4
Cl'MP (8).
1.5% NaOH.
2% silicate
OIl brlgbtllt!ss
development
PGW:
2% H202. 2.5% NaOH,
3% silicate
and peroxide
OOtISUmptitm
In the bleaebing
OIl the brlgbmas
respmue of a peroxide
bleached SOfItbent }rill/! TMP con-
content (8).
minum over manganese in the pH range 4.0

to 6.0 (normal pretreatment pH). It is a concern in mills which pulp resinous woods
and use alum for pitch control or when
paper machine whitewater (aluminum-rich
where alum is being used for pH control) is
recycled back to the bleach plant. Under
these conditions. both the use of alum in
pulping and the recycle of paper machine
white water should be minimized to reduce
the aluminum loading in the bleach plant.
Figure 5 shows the effect of high aluminum
content on bleach response. The pulp
sample contained 630 ppmAl, 59 ppm Mo,
1.7 ppm Cu, and 34 ppm Fe. The bleach
response curve in Fig. 5 indicates that even
after a pretreatment
consisting of 1.2%
DTPA the bleaching response is still not
optimized. It also suggests that a further improvement may result with even greater
DTPA applications.
In this case, a metal
management strategy focuses on the alum
usage and encompassing both the pulp and
paper mills is necessary to ensure a successful pretreatment
and efficient hydrogen
peroxide bleaching stage.
5.U.2 Stabilization of peroxide bleach

liquor with sodium silicate
The second approach to minimizing catalytic peroxide decomposition is bleach Ii-
quor stabilization.This is routinely done by

adding sodium silicate (41 Be), hereafter
referred to as "silicate; to the alkaline peroxide bleach liquor. Silicate is a cost-effective stabilizer
for alkaline
peroxide
bleaching and produces two strong benefits: it significantly reduces peroxide decomposition occurring during bleaching,
and it improves the internal stability of the
bleach liquor solution itself. Silicate applications in modem (chemi)mechanical
pulp
bleach plants are routinely 3% or less on
pulp. In cases where closed water loops
promote silicate buildup or where scaling
problems lead to downtime for equipment
de-scaling. applications of 1-2% are common. With good pretreatment or for pulps
having low levels of metal contamination
(e.g., aspen), the level of silicate required
for good bleaching can sometimes be reduced even further. The effect of consistency
on metal and bleach
liquor
concentrations is discussed in later sections.
In systems where silicate use is not practical (e.g., in refiner bleaching), other means
of stabilization must be employed.The most
common non-silicate alternative for bleach
liquor stabilization is an organic stabilizer,
notably organo-phosphonates.
Organophosphonates
are preferred over aminocarboxylic acid derivatives such as DTPA,
Pulps
467
20
c
16
'c
:J
14
CI)
CI)
Q)
12
~OJ
.;::
III
-Principles
and Practice
For a given set of bleaching conditions

and furnish, there is a threshold beyond
which increased peroxide dosage has a
minimal effect on brightness. This observation is consistent with industry experience
with many types of bleaching chemicals.
5.4.1 Peroxide charge

Brightness response in the peroxide
bleaching of (chemi)mechanical
pulp is directly related to peroxide application. As
shown in Fig. 8, increased peroxide dosage
leads to increased brightness. Response to
increased peroxide application is dictated,
in part, by bleaching conditions such as initial pH, time, temperature, consistency, and
furnish type. The impact of each of these
conditions on peroxide bleaching performance is discussed in the following subsections.
CI)
Pulp Bleaching
5.4 Process variables

Chelated
Unchelated
18
'(ij
OJ
468
10
8
6
0.0
0.5
1.0
1.5
2.0
2.5
3.0
35
Total alkali, % on pulp
30
c
'(ij
whose use is favored in pretreatment applications.The use of organic stabilizers is not,
however, common beca,use of both performance limitations and economics: It is difficult to fmd a more cost-effective stabilizer
than silicate.
5.3.2.2.1 Mechanism of sodium silicate stabilization in the peroxide bleach
ing of (chemi)mechanical pulp
Several theories about the role of silicate
in the peroxide
bleaching of (chemi)mechanical
pulp have been suggested.
These roles include silicate acting as a peroxide stabilizer, metal ion sequestrant, buffering agent, and metal surface passivator.
For stabilization, metal sequestration and
metal surface passivation are two important
silicate functions. Indications of silicate activity as a sequestrant or metal complexing
agent have been reported (15). Experience
has also shown that, even with inclusion of
a pretreatment
to eliminate some of the
metals, the addition of silicate to the bleach
liquor leads to a higher brightness for the
same peroxide application.This is illustrated
in Fig. 6 where the bleaching response at
varing silicate applications for chelated and
unchelated groundwood pulp is shown.
Peroxide residual is also increased by silicate addition (15), suggesting that peroxide decomposition
is reduced, probably
through metal control. There is also evidence indicating that the amount of silicate
applied should be increased with higher
peroxide applications (14) as illustrated in
Fig. 7 (B). The brightness response at varying silicate addition levels is somewhat flat
at low peroxide applications 1%). At intertnediate peroxide applications (3-5%),
the brightness response levels off at 3% silicate addition and, at elevated peroxide application levels (8%), the addition of high
sillcate charges further improves the brightness response.
The inclusion of silicate also allows the
use of some types of mild steel equipment
in peroxide bleaching. Mild steel is not normally used in peroxide service and any
equipment used for bleach liquor storage
or transport of bleach liquor must be made
of compatible materials such as stainless
steel or aluminum. Silicate, however, coats
equipment surfaces, presenting a non-reactive surface for the alkaline peroxide bleach
liquor to contact. This allows the safe and
efficient use of mild steel equipment such
as stock mixers and pumps.
5.4.2 Total alkalinity (pH)

After peroxide stabilization concerns are
addressed, the most important relationship
for the proper control of alkaline peroxide
(chemi)mechanical
pulp bleaching is that
between peroxide and alkalinity. H the alkali charge is too low, inefficient bleaching
is likely to result; too high an alkali charge
CI
CI)
25
'c
:J
20
0-
CI)
CI)
CD 15
C
CI
-;::
CD
[}.-
---<J
/1
/1
~10
/1
5
0
Silicate,
Fig.7. AJfeetofso4hml sU~
UMIimI OIIlJrlg"'-
% on pulp
It'bI tit Mff-t
UMlimIlevela (8).
85
80
0
5!2
0
TMP
75
~70
u)
CI)
Q)
65
3%silicate
~SO.C. 180 min,
CI 60
'i:
CD
20% consistency
55
50
o
Fig.8. Hjfeetof I1yt/t'ogM
~
234567
H202' % pulp
tl/lPlktIIImI011tile IJrlg"'of" sprvee (el1eml}mlHmkt" lnllp (8).

may lead to pulp darkening or yellowing.
In a conventional
peroxide bleaching
System, the pH of the pulp slurry immediately after bleach liquor addition is routinely
in the 10.5 to 11.2 range. If the initial pH is
too high, the rate of peroxide decomposition may exceed the rate of the bleaching
reaction, thereby reducing brightness response.If the initial pH is too low, the lower
perhydroxyl anion concentration impedes
brightness development. At a lower pH, an
extended retention time or higher temperature may be required to obtain the same
brightness response. For any given peroxide application to a particular pulp, an optimum alkali charge is required to achieve
the maximum brightness gain. This phenomenon is illustrated in Fig. 9.
Total alkalinity is the sum of all sources
of alkali in the bleach liquor, expressed as
sodium hydroxide. In most cases, sodium
hydroxide and. sodium silicate (41 oDe) are
the sole contributors to the total alkalinity.
In a bleach liquor where the alkali sources
are sodium hydroxide and sodium silicate,
the following calculation may be used to
determine the total alkali application:
= % NaOH
% Total Alkali
+ [0.115
x %
NazSi03 (applied as a 41"BC solution)] [12]

A useful way of expressing
the relationship
Pulps
469
between peroxide and total alkalinity (I'.A.)

is the T.A./Hpz ratio. As mentioned previously, an optimum alkalinity exists for maximum brightness gain for a given peroxide
application. This optimum can also be expressed as an optimum T.A/HzOz ratio as is
shown in Fig. 10.
The optimum T.A./HzOz ratio decreases
as the hydrogen peroxide charge increases.
This is partially explained by the alkali demand from the wood acids present in the
pulp. Because this value is constant, it is
more significant at low peroxide applications than at high peroxide applications.
This observation is confirmed in two-stage
peroxide bleach plants where theTA./HzO z
ratio is significantly lower in the second
stage. Pulp entering the second stage is neutral or slightly alkaline (7.0-8.0) before
bleach liquor addition. This contrasts with
the moderately acid pH of the unbleached
pulp entering the first stage (4.5-5.5) before chemical addition. Temperature and
retention time also affect the optimumT.A./
HzOz ratio. This effect is discussed in detail
in subsect. 5.4.4.
Hydrogen peroxide and alkali residuals
are also affected by the T.A./HzOz ratio.
Hydrogen peroxide residual, previously
mentioned in connection with the amount
of peroxide consumed
in bleaching, is
defined
as the amount
of peroxide
470
unconsumed at the end of the bleaching

stage as determined by analysis of a ftltrate
sample at the discharge of the bleach tower.
Residual total alkalinity is similarly determined, usually by titration with acid to pH
7.When theT.A./HzOz ratio is optimized to
provide the maximum brightness response,
brightness development and the decrease
in residual peroxide should mirror each
other. This relationship is illustrated in Fig.
11 and is sometimes referred to as "balanced
bleaching."
Historically, the rule-of-thumb in the per-
oxide bleaching of (chemi)mechanical

pulps has been to maintain a residual peroxide level at the end of the bleach of approximately 10"16of the original application.
This value was appropriate for peroxide
applications of less than 2.5% in bleach
plants having no bleach liquor recycle capability.In modem high-consistency bleach
plants, where higher peroxide applications
(3-6% in a singie stage) are used, it is very
difficult to consume sufficient peroxide to
reduce peroxide residuals below 25% of the
applied amount without resorting to very
80
Bleaching
~~0
conditions:
3% silicate
60C, 180 min, 18% consistency
u)
70
II)
CD
c:
.s:::.
01
'1::
ID
60
1.0
1.5
(NaOH + 0.115 Na2Si03)/H202
Fig.10. /"fl-
o/T.AAlP, rtIIIo018IJrlgblrlessI" tbeperoxIiIe bl_bl",

72
70
0
.s:::. 68
70
W
0
u) 68
II)
CD
c:
.s:::.
01
'1::
ID
,,
u) 62
II)
CD 60
c:
E 58
0.9% H202, 5% silicate
66
65
0.5
Fig. I}. Effect 0/ ,,11uI1I ebllrge O18lJrlgblrless
1.0
1.5
2.0
NaOH, % on pulp
resptmse
m tbe peroxIiIe
60
2.25%
NaOH
50
3% silicate
70C, 14% consistency
40
30
~01
.;: 56
ID
54
32C, 6h, 5% consistency
0.0
80 0..
a.
70
~~2.5%H202,
90 "C
.9,!
,,
W 64
,,~I
,,
,,
67
CD
.... 66
2.5
bletu:bI",
3.0
0/ SOfIIbem pille TMP (8).
TMP(8).
100
-----
--~---------------
, ,.......:=J
I
,I
a.
,
,,
~69
0/ ~
20
10
lIS
'0
0
(ij
:I
"C
'w
N
0
N
:I:
Time, h
Fig. 11. Rellltlmlsblp
beIwJeerJ IJrlgblrless
pille JlMlp (8).
tlerJeloJmltlflt
,,"" resUhull peroxuIe
I"
tbe bletu:bI",
0/ Soutberrt

long retention times. Therefore, in such
cases, residual peroxide levels are commonly in the range of 30",1,or more of the
applied amount. Aside from the desire to
have a control point during long retention
(3 hours or more) times, the implementation of two-stage bleaching with recycle was
driven by the desire to reclaim this high
peroxide residual so as to make high-application peroxide bleaching more economical. For example, a 30% residual from a 5.0",1,
H202 application amounts to 1.5% H202 on
pulp, an amount which can be profitably
applied to another bleaching stage.
Besides alkalinity and stabilization, three
other factors affect hydrogen peroxide
bleaching response: consistency, time, and
temperature.
Although the effect of each
on the bleaching response can be considered separately, one or more of these variables may be fixed by the pulp mill design.
This may coincidentally force the other two
variables into certain ranges to produce a
specific end result (e.g., brightness
response). In the following discussion, the
effects of each variable are first described,
witholit regard for the effect of the others.
Following this, the interactions between the
other two variables are then described.
5.4.3 Consistency
The effect of consistency on hydrogen
peroxide
bleaching response has been
Pulps
471
documented (16,17). Hydrogen peroxide

bleaching can be carried out over a wide
consistency range, from as low as 4% to as
high as 35%. Historically, the limitations on
bleaching at high consistency have been
equipment related: no efficient, commercially available dewatering systems or highconsistency mixers existed before the last
ten or fifteen years. Following the appearance of commercial mixing and dewatering equipment capable of functioning in the
higher-consistency
range, most modern
bleach plants elected to operate at medium
consistency or higher. Tw<Hitage peroxide
bleaching often incorporates both a medium-consistency (15%) stage and high-consistency (25-35%) stage to allow maximum
liquor recycle.The effect of consistency on
bleaching response is illustrated in Fig. 12
for the peroxide bleaching of a northern
spruce groundwood at three different consistencies. It is clear that, at low consistency,
not only does the groundwood
require
more peroxide to achieve the same brightness, but that there is a definite "ceiling"
for the brightness response which cannot
be exceeded by further peroxide addition.
The slope of the response curves for the
two higher-consistency pulps indicates that
further brightness gains can be achieved.
However, from the shape of the curves it is
clear that an upper brightness limit will also
Consistency
472
eventually be reached under these conditions.

Common bleaching responses for highconsistency
(18%+) peroxide bleaching
stages are:
1% HP2
8-10 points
2% HP2
14-16 points
3% HP2
18-20 points
A continuous increase in bleaching response occurs as consistency is increased

up to the 40% level (18). Above this level,
pulp handling and homogeneous chemical
mixing limitations exceed the capabilities
of commercially available equipment. The
effect on brightness of increasing the consistency from 15% to 30% is illustrated in
Fig. 12. For this pulp, an increase of slightly
more than 1% ISO was obtained after a 10%
increase in consistency.
Several theories for the effect of consistency on bleaching have been advanced (19).
Common themes in these theories include the
effect that increased consistency has on the
concentration of bleaching chemicals around
pulp fibers, and mass transfer phenomena involving the mobility rates of decomposition
agents such as transition metals (14,15,17).
The most significant of these effects is that of
concentration. As reported by Ali et al. (14),
increasing the bleaching consistency from 4%
to 20% increases peroxide concentration by
a factor of 6.
Moldenius and SjOgren (19) have developed an empirical kinetic model for the
peroxide bleaching of Scandinavian spruce:
= -k
dC/dt
[HPzror]067[ORj023Ck2.2
[13]
where
~
o
C.
= light
absorption
coefficient
at
457 nm, m2/kg

t
= bleaching
[HPzror]
64
of COIISuteru:y 011 brlgbltlns
I"
tbe peroxIile
bletU:bl"g
= [HP2]
= sum
+ [OOR]
of undissociated
peroxide, mole/L
H202, % on pulp
Fig. 12. EDed
time, min
and dissociated
[OH'] = hydroxide ion concentration,mole/L

of spruee grourulUJOOd
(8).
= kinetic
rate constant.
This equation clearly shows the importance

of peroxide concentration and the relationship between peroxide and total alkalinity
(OR).The apparent high reaction order for
C (chromophore concentration) is consist~nt for a set of chromphores
having a
widely varying susceptibility to peroxide
bleaching.
5.4.4 Time and temperature
Of the variables affecting the brightness
response of (chemi)mechanical
pulp, time
and temperature are the most closely related. Under routine bleaching conditions
at high consistency, time and temperature
can be interchanged. An increase in bleaching temperature can compensate for a reduction in retention time up to a point.
Conversely, if bleaching temperatures
are
held below 140F (60C), extending the
retention time often produces the same
brightness response. There are limitations
to this "exchange; however. For example,
when a TMP is bleached at different temperatures under optimized total alkalinity
conditions, two effects are immediately
apparent (Fig. 13)
1) At higher temperatures, brightness development is rapid, reaching a maximum
in 30 minutes or less.
2) Although brightness
development
is
more rapid at higher temperatures, fmal
brightness is less than that achieved with
the same chemical charge at a lower temperature.
The rapid decrease in brightness observed
for the high-temperature (95C) bleach is a
result of the peroxide being totally consumed. This occurs because, at the higher
temperatures, the reaction rates of both the
bleaching and decomposition reactions are
increased. Under these conditions, effective
transition metal control is imperative to
minimize peroxide decomposition. Because
of the increased rate of the bleaching reaction, it is also necessary to make the appropriate adjustments in retention time: at
160F (71 C), the retention time required
for full brightness development may be on
the order of two or more hours; at 195,
Chapter VI:
Peroxide Bleaching of (Chemi)mechanical
5.5 Peroxide bleaching of recycled fiber

Peroxide is also used in the bleaching of
recycled fiber of both mechanical
and
chemical pulp origins.The peroxide bleaching response and bleaching conditions asSOciated with recycled fiber are sufficiently
dIfferent from virgin pulps to require description below.
80
!:Q
473
includes alkalinity levels which, as mentioned previously, vary to some extent with
time and temperature.
200F (90-93C), full brightness development may be achieved in 30 minutes, with

95+% of the increase occurring within the
first 10-15 minutes. Therefore, where
bleaching is restricted to high-temperature
conditions, good pretreatment, adequate
bleach liquor stabilization, and a relatively
short retention time are important.
A convenient rule-of-thumb guide for selecting the proper peroxide bleaching conditions is shown in Fig. 14. This figure
Pulps
45C
5.1
75
65C
4.8
70
85C
4.5
474
Pulp Bleaching
-Principles
and Practice
5.5.1 Peroxide bleaching of groundwood

(mechanical pulp)-containing
deinked pulp
In general, the same types of bleaching
chemicals are used to bleach recycled
groundwood-containing
deinked pulps as
are used to bleach virgin (chemi)mechanical
pulps. like virgin mechanical pulps, chlorine bleaching compounds darken recycled
groundwood furnishes and decrease yield.
As a result, it is necessary to use the same
lignin-preserving
bleaching chemicals to
bleach recycled fiber as are used to bleach
virgin fiber. Consequently, hydrogen peroxide is widely used to bleach recycled mechanical
pulps, often referred
to as
65
iii
(/)
CD
c:
60
.C)
c:
.;::
II)
55
5.5.2 Peroxide applied to the pulper

Alkaline pulping with hydrogen peroxide is perfortned in both medium- and lowconsistency
pulpers. The pulper pH is
usually adjusted to between 10.0 and 10.5
with caustic soda (sodium hydroxide) and
DTPA or sodium silicate is added to stabilize the hydrogen peroxide. In some cases,
a soap or surfactant is added to aid in ink
White water makeup + surfactant
Bleachin
Ii uor
~Total
groundwood-containing
pulps by deinkers.
In addition, peroxide is very versatile for
these applications because it can be used
in the pulper, in a tower as a dedicated post
bleach, or in a disperser operated under
alkaline conditions.
alkali,
% on pulp
4% H202. 5% silicate
30% consistency
To cleaning,
screening,
deinking,
and bleaching
50
o
Pi,. 13.~ eJfeetofl~
(8).
30
60
90
120 150
Time, min
011tIIe"*
ofbrlflllrless
180
210
240
MleIoJmretrl for. jIero%iM-blHeW
Low temperature
Medium temperature
(1408-175F; 6o-79C)
. Medium alkali
Medium retention
time (2-3 h)
(95'-120F;
35-44C)
. Med. - high alkali
Long retention
time (4-6 h)
\ /
.
.
.
Dump/soak
chest
SJWrIceTMP
Fig. 15. ~I
for jIero%iM IUItIItImI to IN pulpet:
70
0.4%, DTPA, 2.5% silicate
65
43C. 8% consistency
!:Q
~0
iii
(/) 60
CD
c:
.C)
c:
.;:: 55
II)
High temperature
(ZocrZ10F;S3-S6G)
Low alkali
Ntweefl time, tempertllrlre,
.""
0.5
Short retention
Pig. 14. ReWUmsllip
50
time (5-20 min)
.lWiIIUy.
H202.
1.0
% on pulp
Pi,. 16. Brlglllrless response to jIero%iM applW i.. IN pulpet' of. 70130 ONPIOMGdelnJr slid
(8).
Chapter V I: Peroxide Bleaching of (Chemi)mechanical

removal but, in other instances, the alkalinity of the pulper is sufficient to ensure good
ink separation from the fiber. A flowsheet
of the process is shown in Fig. 15.
Peroxide is commonly applied to groundwood-containing
furnishes in the pulper.
An application of 0.3-1.0% increases the
post-flotation brightness of blends of old
newsprint (ONP) and old magazines (OMG)
by 3 to 7 brightness units, depending on
pulper conditions (see Fig. 16). Much the
same brightness gain can be attained with
100% ONP, and the addition of peroxide to
the pulper helps to level out the brightness
swings of ONP furnishes which have yellowed (suffered reversion) from age or storage conditions (tN-induced reversion from
outdoor storage, heat-induced
reversion
from outdoor collection boxes during the
late spring and summer).
5.5.3 Hydrogen peroxide applied as a post
bleaching stage
Post bleaching of recycled fiber in a tower
or chest is very similar to bleaching virgin
pulp. The same basic principles concerning the effects of alkalinity, temperature,
retention
time, and consistency (as discussed above) still apply. There are, however, a few notable exceptions. The most
important of these is that potential brightness gains of recycled fiber may be lower
than for similar virgin fiber because the fiber has been through the papermaking process
and
possibly
bleached.
On
groundwood or wood-free pulps, applications of 0.5-1.5% peroxide may achieve
brightness gains of only 2-5 units. Gains of
12-14 points are possible with peroxide
applications as high as 4.0% on pulp.
rule 5 ~
H202'
%
unbleached
I
4
~,..
TAl
~ 02
0.8
0.8
3
j
0.35% DTPA pretreatment,

17% consistency
Samples pretreated
with 0.35% DTPA
Bleach conditions:
17% consistency, 71 C
475
The limiting factor in the brightness response of recycled mechanical pulps is ink
removal: even under optimum bleaching
conditions
and with a fresh (under 6months-old) furnish, if the ink is not thor.oughly removed, it can mask brightness
gained in bleaching.An example of bleaching response
in a post-de inking tower
bleaching application based on laboratory
bleaching data is given in Table 5.
Another difference between recycled and
virgin pulps is the alkalinity demand in the
peroxide stage. The alkalinity demand of
recycled fiber is much lower than that of
virgin pulp because most of the wood acids in the fiber were neutralized or removed
when the fiber was first processed into paper. Consequently, the ratio of total a1kaIi
to peroxide necessary for efficient bleaching of recycled fiber is lower than that for
virgin pulps. This is critical to groundwood
pulps which can alkaline-darken if all the
peroxide is consumed before the end of the
bleaching stage.
As in the peroxide bleaching of virgin
mechanical pulps, metals control is essential for effective peroxide perfonnance.This
can be very difficult because of the diversity of fiber sources and contamination from
trash and dirt (ink, particles, soil, tramp
metal) that often finds its way into bales of
waste paper. Aluminum may also buildup
in the pulp mill water loop because the
alum or sodium aluminate that deposited
on the paper during the papennaking process is freed from the fiber during
repulping. The aluminum itself does not
decompose peroxide in the bleaching stage
but, in high concentrations, it can complex
m-r(post-b~
Silicate,
%
Pulps
II[IJIlIeIdImI
(8).
Bleaching
Time, m
Brightness,
% Hunter
120
...49. 5
59.6
60
63.3
476

65
0
~60
Unbleached brightness: 51.9% ISO Furnish: 100% ONP

IZJ Hydrosulflte stage
131 Peroxide stage
Peroxide: 1% silicate 70.C, 120 min, 15% cons
Hydroeulflte: 0.75% hydrosulflte, 45.C,
60 min, 4% cons.
~0
qj
(/)
Q)
c:
-C) 55
J::
':
50
0.5 (0.50)
H202
Fig. 17. Dro-sIIJp ~lfUe
and
0.75 (0.55)
(NaOH),
lllaebi..,
% on pulp
of ImIIIetllOO'11. ONPsttJdr (8).
with most or all of any chelant added before the stage. This leaves transition metals
which can decompose
the peroxide,
uncomplexed.
Peroxide stages are often incorporated
into sequences with sodium hydrosulfite or
formidiline-sulfinic acid (FAS). This is especially the case for post-bleaching wood-free
deinked stock. The peroxide stage almost
always precedes the hydrosulfite or FAS
stage and can be economical
if higher
brightness levels are required or if residual
color is present on the fiber. The peroxide
stage provides an initial brightness increase,
while the hydrosulfite or FASstage destroys
the color or gives an additional brightness
increment (Fig. 17).
5.5.4 Peroxide applied in a disperser
Kneader and disc-type dispersers, operated under alkaline conditions, are another
application point for hydrogen peroxide.
The disperser is an excellent mixer and the
high temperature and consistency, up to
90C and 30%, are well-suited for peroxide
bleaching. The disperser can function in
place of the traditional high-consistency
mixer, and the pulp exits the disperser directly into a bleach tower. Even if the additional retention after dispersion is short,
peroxide bleaching in the disperser can
produce a significant brightness increase.
The alkaline peroxide bleaches the pulp
1.0(0.60)
and, in instances where a flotation stage

follows dispersion, increases the efficiency
of the post-flotation stage (20).
5.5.5 Peroxide bleaching of wood.free recycled pulps
Peroxide is also used to bleach wood-free
recycled waste, especially post-consumer
office waste. The acceptable level of groundwood content in some of these furnishes
has risen to as high as 15%.When bleached
with hypochlorite or chlorine (traditional
wood-free deink pulp bleaching chemicals),
these pulps turn yellow because the groundwood content causes darkening.
Wood-free pulps were once almost exclusively bleached with hypochlorite, either
alone or in sequences with chlorine.These
compounds are still in widespread use although, with the mounting pressure to reduce or eliminate
their use, other
alternatives such as peroxide, hydrosulfite,
fonnimidinesulfinic
acid (FAS), and ozone
have appeared. Peroxide can be used effectively to bleach wood-free pulps in a single
stage or as a part of sequences composed
of chlorine, hypochlorite,
or any of the latter-mentioned
chlorine-free
compounds.
Wood-free furnishes are not as commonly
pulped with peroxide, and the brightness

lift after flotation is usually not as great as
for a groundwood-containing
furnish. Although pulper conditions are generally too

mild to effectively bleach wood-free furnishes, some bleaching can be accomplished by an application of peroxide in the
pulper. Higher temperature, consistency, or
alkalinity is usually required to achieve effective bleaching of wood-free furnishes
with peroxide.
6. Effect of peroxide bleaching

on physical properties
During peroxide bleaching, the physical
properties of the pulp are affected in many
ways.The extractives (resin) content of the
pulp is substantially reduced and cleanliness
is improved. Peroxide bleaching improves
the beating properties of (chemi)mechanical pulps and produces less stiff fibers with
improved bonding properties. As a result,
peroxide
bleached
pulps
produce
smoother, higher tensile strength papers
than unbleached pulps (see Chap. VII 3).
On the debit side, peroxide bleaching lowers the opacity of high-yield pulps. Opacity
losses increase as brightrtess increases and
may be as high as 10%.
Hyperalkali peroxide bleaching (HAPB)
is a peroxide bleaching stage specifically
designed to enhance the physical properties of a pulp. Large alkali charges are used
in the bleaching stage and enough peroxide is applied to furnish a modest bright-
Pulps
477
ness gain or prevent alkali darkening. HAPB

can substantially enhance the physical properties of (chemi)mechanical
pulps when
conducted at very high pH (> 11.5). Such
treatments are reported to improve tensile,
tear, and burst strength. Although the exact reasons for the improvement are not
fully understood, Moldenius (21) has suggested that the high pH increases the rate
of hydrogen peroxide decomposition
and
generates radical species that are responsible for the physical property enhancement. Another theory is that the sodium
hydroxide in the alkaline peroxide bleach
liquor swells the fiber walls and enhances
the ability of the fibers to conform and bond
to one another during sheetmaldng (22,23).
7. Bleachplant design and

operation
The following sections address bleach
plant design and selection and contain descriptions of the various components currently commercially available; flowsheets
are included to illustrate several common
bleach plant configurations. Bleach plant
flowsheets are presented first, followed by
a discussion of process steps, components,
and criteria for bleach plant selection.
DTPA
478
7.1 Flowsheets for peroxide bleaching

processes
7.1.1 Single-stage medium-consistency
bleach plant
Before brightness targets for (chemi)mechanical pulps exceeded 75% ISO, the
typical peroxide bleach plant was the medium consistency, single-stage peroxide
bleach plant (see Fig. 18). Most of these
mills use a decker or disc filter as a thickening device before adding chemicals to the
pulp. The pulp is pretreated as follows:
DTPA is added in the feed chest for the
thickener where conditions include agitation and at least 15 minutes' retention time
at temperatures ranging from at least 105
to 130F (40 to 54C). If the retention time
is sufficient, DTPA may be added to the suction side of the stock pump feeding the
decker. The pretreatment is completed by
removal of the filtrate (containing
the
complexed metals) on the thickener ahead
of the bleach tower. Bleach liquor is generally made up in a cascade mixing system
and applied to the pulp using a peg or
paddle mixer. The pulp is held in a tower
for at least two hours though retention in
excess of this time is also common. In general, a peroxide residual of 5-10% of the
amount applied is desired. Most systems
include a sulfur dioxide sour, either in
preparation
for a following hydrosulfite
stage or to prevent reversion. Fewer mills
currently operate medium-consistency per-
oxide bleaching stages because of their

brightness gain limitations and the operating expense associated with the use of
lower-efficiency bleaching conditions. However, there are some circumstances where
medium-consistency
systems can deliver
the required brightness. In these situations,
a mill does not need to invest in a more capital-intensive,high-consistency
bleach plant
as is further discussed in sect. 7.4.
7.1.2 Single-stage high-consistency bleach
plant
The demand for higher brightness
(chemi)mechanical
pulp was the incentive
for the development
of the single-stage,
high-consistency
bleach plant (Fig. 19).
farly systems used twin-wire presses orscrew presses for thickening.These are still
in modem bleach plants, although the twinroll press is now also an option. The size of
available mixing equipment (throughput)
was the limiting factor in determining the
production capacity of the early high-consistency bleach plants.Today, however, highconsistency mixers are available with a
through-put in excess of 300 tons/day. As
with medium-consistency
bleaching, pulp
is usually pretreated with DTPA before the
thickening step, often in the latency chest,
where the treatment conditions include
agitation, temperatures in the 140-165 F
(60 -74C) range, and a retention of at least
15 minutes. Following thickening, bleach
liquor, either from a cascade mixer or in-
Washer
Bleaching
Unbleached
pulp
(H20,
Twin wire
press
liquor
NaOH,
Na2Si03'
H202)
28% BD
peroxide
tower
H.D.
storage
10%BD
Bleach tower
10-15% cons.
12Q-170F
2-4 h
Bleached
Dilution
8%BD
pulp
4.5% BD
Fig. 18. Flowsheet
for st.gle
stage, medl.",
etmslstnu:y,
jIet'rdIk
blueb
plll.t.
4%BD
To paper machine
Chapter VI: Peroxide Bleaching of (Cheml)mechanical

line system, is added to the pulp by means
of a barrel-type compression mixer or a
fluffer-type mixer.The pulp is then retained
in a tower for 1-3 hours, with 1.5-2 hours
being the most common retention time.The
pulp may be diluted to aid in its discharge
from the tower or removed from the tower
bottom by screw conveyors. Upon discharge, the pulp is soured with sulfur dioxide or, if the residual peroxide is to be
recycled, with sulfuric acid (other means
of adjusting the pH may also be used, e.g.,
carbonic acid).1f liquor recycle is desired,
a second thickening stage is added after the
tower to reclaim peroxide-rich filtrate for
recycling. The high-consistency
(chemi)
Pulps
479
mechanical
pulp bleach plant offers a
greater range of brightness response and a
much more efficient bleaching environment
than does a medium-consistency
bleach
plant (see Sect. 7.3).
7.1.3 Two-stage medium-high consistency
bleach plant (with recycle)
The most prevalent (cheml)mechanical
pulp bleach plant configuration for achieving high brightnesses is shown in the flow
sheet in Fig. 20. The first stage is run at
medium consistency to permit the uti1ization of the highest volume of recycled (recovered) filtrate (further discussion see
Sect. 7.3).
Fresh bleaching chemicals

Screw
press
I
CD
"0
II:
480
7.1.4 1\No-stage peroxide - hydrosulfite

bleach plant
Another option in two-stage (chemi)mechanical bleaching is the peroxide/hydrosulfite bleach plant as shown in Fig. 21.
Hydrosulfite bleaching is covered in some
detail in Chap. V 2. Further discussion of
criteria for (cheml)mechanical bleach plant
selection is provided in Subsect. 7.3
7.2 Bleach plant process
description
7.2.1 Bleach liquor makeup

Hydrogen peroxide is a clear, colorless
liquid, commercially avaiIable in aqueous
solutions of varying concentration,
although in the pulp and paper industry it is
generally stored at 50% concentration
for
safety reasons. Because it is an oxidizing
agent, some special care is required in its
storage and handling and in determining its
compatibility with equipment. Safety and
handling information and advice on equipment installation can be obtained from any
of the commercial hydrogen peroxide suppliers. Some physical characteristics of hydrogen peroxide are provided in Table 6.
Hydrogen peroxide is, of course, only
one component of peroxide bleach liquor.
As mentioned earlier, sodium silicate and
sodium hydroxide or some other alkali
source are typically included in peroxide
bleach liquors. To obtain the maximum

bleaching efficiency, these chemicals must
be premixed in a bleach liquor makeup system before addition to the pulp.
rok 6. P#1yskIIljIrOJImIn olllytlrogn peroxIM.
H,02 content (ByWeight)
Active oxygen, weight %
Freezing point, C
of
50%
23.5
70%
32.9
-52
-63-40
40
Boiling point,
c (76Omm Hg)
of
Density, g/mL (20C)
Ib/gal (68F)
114
237
1.20
9.98
Bleach liquor makeup systems have undergone changes over the past decade.
There has been a movement away from the
traditional cascade makeup systems as described by Andrews in his 1968 survey of
existing (chemi)mechanical
pulp bleaching
technology
(24). Although the cascade
mixer (see Fig. 22) still has utility in bleach
liquor makeup systems, it is not always the
makeup system of choice. In state-of-the-art
(chemi)mechanical
pulp bleach plants, the
cascade mixer has given way to in-line (see
Fig. 23) and/or combination makeup systems. This is largely because bleach plants
have shifted to continuous liquor makeup
Water
Bleached
pulp
4%
cons.
Utilization
t
Fig. 21. FlofllSbut lor II two-stllge peroxIM-byIlf'OSfllftte b~
Na2S04
JmH:eSS.
Fig. 22. CMetItk __-tip
systMI.
125
258
1.29
10.75
Pulps
481
To
process
NaOH solution
~
Fig. 23. 1.-11_ blMeb llfrwr
"""fI/J
Static mixers
sysm..
to avoid loss of flexibility during graae

changes. In mills with hard process water,
scaling occurs in the cascade mixer and may
cause a loss of line diameter in the bleach
liquor lines connecting the mixer to the
process. Some mills have moved the peroxide addition point closer to the mixer
(25) to reduce this problem; others have
gone to the extent of adding the sodium
hydroxide/silicate
and hydrogen peroxide
solutions separately to the chemical mixer.
At high consistency, this is acceptable only
if there is sufficient mixing to produce a
homogeneous discharge.
7.2.1.1 Hazards associated with in-line mix
ing systems
Although cascade mixers have the drawbacks mentioned above, they may offer an
advantage compared with in-line mixing
systems with regard to safety considerations
in the design and operation of the bleach
liquor makeup system. The major safety
consideration
involved in bleach liquor
makeup is the prevention of concentrated
hydrogen peroxide solutions coming in
contact with concentrated sodium hydroxide solutions in an environment
lacking
adequate venting. A vigorous reaction that
takes place when 50",.{,hydrogen peroxide
is mixed with ;0% sodium hydroxide. The
subsequent large volumes of gas and steam
evolved requires that special precautions be
taken to ensure that irrterlocks shut down
the flow of both the hydrogen peraxtde and

sodium hydroxide to the bleach ltquor
makeup unit in the even of an interruption in dtlution water flow. A cascade
mixer's open top design offers an easy escape route for evolved gas and steam. Although all peroxide storage and handling
systems and peroxide-containing
bleach liquor storage and handling systems should
be vented to attnosphere or include in-line
pressure relief valves, such venting is inadequate to handle the potentially high volumes of gas and steam that may result from
mixing the concentrated chemicals. Lack of
sufficient venting may result in line ruptures
or pressure bursts in the bleach liquor handling system. It therefore is essential that
proper care be exercised in interlocking inline systems so that the opportunity for such
a reaction is minimized.
7.2.1.2 Peroxide bleach liquor stabilization
during storage
Historically, when bleach liquor was
made in batch quantities of 5,000-10,000
gallons and stored up to 24 hours,sufficient
silicate was routinely added to provide applications of 5-7% (dry pulp basis) when
the pulp and bleach liquor were mixed.
Addition of MgSO 4 . 7HP (Epsom salt) in a
concentration
of 0.42 Ibs/lOO gal or 0.5
g/l (translating to approximately 0.05% on
pulp) to the liquor also improved peroxide
bleach liquor stability during storage. How-
482
ever, because peroxide is destabilized by the

addition of alkali, this approach is not the
most efficient, particularly if moderately
concentrated bleach liquors are required to
achieve peroxide applications in excess of
3.0% on pulp. Storage tanks and transfer
systems also provide an additional opportunity for scaling which in turn can lead to
bleach liquor decomposition because the
scale formed often contains transition metals in the scale matrix that can act as catalytic decomposition agents.
7.2.1.3 Continuous makeup compared to
small batch systems
The advantage of continuous makeup
over small batch systems is the quick response it provides to bleaching demand
changes. When the incoming brightness
fluctuates, it is possible to continuously
adjust the bleach liquor in an attempt to
compensate for the variations. Also, there
is no lag time involved in grade changes:
bleach liquor can be adjusted to the appropriate concentration for the next grade immediately. The advantage of a small batch
system lies in the area of security: If chemical deliveries are somewhat undependable
or if there are no installed back-ups for the
equipment used in transferring the bleach
liquor components, a batch system offers a
time period for corrective action. The continuous makeup system is employed in most
modem bleach plants.
7.2.2 Pretreatment and thickening
In most (chemi)mechanical
pulp bleach
plants, pretreatment
of the pulp with a
chelant is performed before the thickening
step preceding the peroxide bleaching
tower (or the first tower in a multi-stage
bleach plant). Probably the most common
location for chelant addition is in the latency
chest after refining or, for stone groundwood, in the chest immediately after the
grinder pit.
The following thickening
step, on a
decker, disc filter, or press, is of extreme
importance because it permits the extraction or removal of complexed transition
metals. The choice of thickening device
depends in large measure on the desired

bleaching consistency
in the following
bleaching stage: Deckers and disc filters are
generally used in low-to-medium-consistency situations; twin-wire, screw, or twinroll presses are generally employed
in
high-consistency bleaching operations. As
stated in the previous discussions of metal
removal and control (Subsect. 5.3), even
complexed or chelated metals can catalyze
the decomposition of peroxide in a bleaching stage, so efficient metal removal is necessary to optimize peroxide bleach plant
performance.
7.2.3 Mixing of bleach liquor with pulp
Following the thickening stage, bleach
liquor, whether recycled, fresh, or a combination of the two, is added to the pulp at
a mixer. Once again, consistency has the
greatest influence on choice of equipment:
Peg or paddle mixers may be sufficient to
mix medium- or low-consistency pulp slurries; high-shear mixers are needed for highconsistency applications.
An approximate measurement of mixing
efficiency can be obtained by spraying a
sample of pulp from the mixer discharge
with Universal indicator (pH) solution.The
uniformity of color is a good qualitative
measure of how well the chemicals are being mixed into the pulp.
7.2.4 Transport of pulp to the bleach tower
When the pulp being transported in the
bleach plant is of medium or low consistency, a thick-stock or clove rotor pump
generally serves the purpose. If the pulp has
a consistency above approximately 15%, it
may be necessary to use rotolifts and screw
conveyors to move the pulp from stage to
stage.
7.2.5 Monitoring and control
In the modem bleach plant, monitoring
and control is the key to process optimization (see Chap. VI 5). Production
rate,
chemical flow, pulp temperature and pH,
brightness (incoming and outgoing), and in
some cases, chemical residuals are monitored and fed into a Distributive ~ontrol
~ystem, together with motor loads, water

flows, and other pertinent production information. The following parameters (discussed in Subsect. 5.4) are of greatest
importance in optimizing a peroxide bleach
plant: chemical application, bleach tower
temperature, production rate, pulp pH, and
incoming and outgoing brightness. When
the bleaching sequence consists of two or
more stages and recycled liquor is involved
in a bleaching stage, peroxide and alkali
content of the recycle liquor are also important.
Operating experience with a given pulp
should allow the development of application guidelines regarding bleach liquor
makeup and the amount of chemical required to reach a target brightness. Once
these values are determined, it is possible
to optimize the TA (total alkalinity)/H202
ratio (see Subsect. 5.4.2).At this point, the
monitoring of pH, temperature, and residual
chemicals should allow the bleach plant
operator to maintain the brightness targets
associated with the pulp grade in production.
In two-stage peroxide bleach plants with
recycle, the most significant control parameters are the chemical charge to the first
tower and the brightness of the pulp entering the second tower. In both cases, process stability is the desired characteristic.
Control of the final brightness and chemical applications
in the second peroxide
bleaching stage require a stable incoming
brightness. To ensure a stable pulp brightness exiting the first peroxide bleaching
stage, the incoming pulp brightness and
chemical content of the recycled liquor
must be monitored.
The following strategy should be employed:
On startup, the recycle liquor is weak but
gradually
increases
in concentration.
Therefore, fresh liquor must be added to
the stage to produce the desired exit brightness.
Care must be taken to monitor and control this transition to a steady-state condition by decreasing
the fresh liquor
application in the first stage until the chemical content in the recycled liquor becomes
Pulps
483
484
constant. When a steady state is reached,

any further optimization of the second stage
must be accompanied by further monitoring of the recycled liquor to ensure that the
residual chemical content
from the first
stage remains stable. This procedure also
minimizes offgrade and transition pulp during grade changes.
Maintaining a stable first bleaching stage
avoids introducing a cyclical variation in the
first stage final brightness. This is usually
caused by decreasing the peroxide application in the second stage without regard
to the impact on the chemical content of
the recycle liquor. When the second-stage
peroxide applications are reduced, the peroxide content of the recycled liquor is similarly reduced. If this loss is not made up by
the addition of fresh chemical to the first
stage, brightness loss occurs in the first
stage.The normal operator response to this
brightness loss is to compensate for it by
overbleaching in the second stage, thereby
increasing the concentration of chemicals
in the recycled liquor and initiating a sinusoidal variation that may take several hours
to eliminate.
In adjusting the chemical application in
two-stage bleach plant with or without recycled liquor, silicate addition may not be
necessary in the second bleaching stage.
hydrogen
peroxide
from the mill's
whitewater system. Other chemicals commonly used to acidify peroxide bleached
pulp include sulfuric acid and sodium
bisulfite; however, sulfuric acid does not
destroy residual hydrogen peroxide.
7.2.6 Neutralization of peroxide-bleached

pulp
Because hydrogen peroxide bleaching is
performed under alkaline conditions, it is
often necessary to adjust the bleached pulp
to a pH of 5-8 before sending it to the pulp
dryer or paper machine. Historically, sulfur
dioxide, which forms sulfurous acid when
scrubbed into water, is preferred for this
purpose because it is both a strong add and
a reducing agent. Addition of sulfur dioxide therefore reduces the pH level of the
pulp to an acceptable value for the pulp
dryer or paper machine and destroys the
peroxide remaining after the bleaching
stage. This latter function is panicularly
important when a reductive bleach stage,
such as one employing sodium hydrosulfite
or sodium borohydride, follows the peroxide stage or when it is important to remove
Brightness
Gain
Required,
Points ISO
gain required. The other main species-related impact is the metals content of the
pulp which, in some cases, may require a
special removal or stabilization treatment.
Several common bleach plant configurations in conjunction with the usual brightness gain produced are shown in Table 7.
In general, if the brightness gain desired
exceeds 12-15 points or if the peroxide
application required to produce the desired
gain exceeds 2.5%, then bleach liquor recycling and/or two-stage systems should be
considered
to optimize bleaching economics. It is also possible to perform twostage bleaching without two conventional
towers, for example, by using refiner
bleaching or alkaline peroxide chemithermomechanical pulping system as a first stage
(see below). It should also be recognized
that the recycling of bleach liquor around a
single stage can lead to significant savings
in bleaching chemicals.
7.3 Guidelines for bleach plant selection

Bleach plant selection in (chemi)mechanical pulp bleaching, whether for a retrofit, rebuild, or new (greenfield) operation,
is dependent on four major concerns: the
brightness gain and physical properties required,available capital, available space, and
the wood species to be processed. Of primary concern are the brightness gain and
physical properties required. When these
parameters are defined, selection of the
bleach plant configuration
is usually reduced to one or two options which are often funher limited by the availability of
capital. Space limitations are usually not an
issue in a green-field operation but can be a
constraint where a retrofit or rebuild operation is concerned. In most cases, the
greatest impact of wood species is on
bleachablity
and/or unbleached
(raw)
brightness and is dictated by the brightness
1IIbk 7. C~
01_
Number
of
Stages
bIMdI"""
8. Non-conventional peroxide
bleaching
8.1 Refiner bleaching
Peroxide bleaching can be conducted
etnIftprYltllnrs.
Consistency,
%
Recycle
Wood
Type
Advantagesl
Disadvantages
8-10
10-15
No
HWD or
SWD
Minimum capital costs,

somewhat higher chemical costs per unit of
brightness gain
10-16
10-15
No
HWD,
easy
Minimum capital costs,

higher chemical costs per
unit of brightness gain
8-20
18-25
No
SWD
Moderate chemical costs,

higher capital costs
8-20
18-25
Yes
HWD or
SWD
Reduced chemical costs

per unit of brightness
gain, higher capital costs
15,30
Yes
HWD or
SWD
Lower chemical cost per

unit of brightness gain,
higher capital cost
l;-~O
HWD =hardwood,
SWD =softwood

during refining by adding a1'1alkaline peroxide bleach liquor to the chips or pulp
immediately before the primary or secondary refiner (see Fig. 24). Alternately, the liquor may be added with the refiner eye
water (water added to the "eye" of the refiner to facilitate the refining of the pulp).
The refiner mixes the liquor into the pulp
and generates the heat necessary to drive
the bleaching
reaction. Temperatures
reached in the refiner are, in fact, high
enough (>100 0c) so that it is not necessary to employ a bleach tower to provide
additional retention time. As a result, a peroxide bleach plant Is not required.
There is, of course, some trade-off in
bleaching effidency in refiner bleaching.
Transition metal contaminants cannot be
removed before adding the peroxide bleaCh
liquor, although it may be possible to add a
chelant in a preceding impregnation or refining stage. Furthermore, sodium silicate
cannot be added as a component of the
peroxide bleach liquor because of the risk
of scale formation on the refiner plates.
These factors, coupled with the high operating temperature in the refiner, limit the
potential brightness gains achievable by this
technology.
RefIner bleaching lends itself to mills
having an occasional need for higher brightness pulps. The process is easy to operate
Pulps
485
Pulp Bleaching - Prindples and Practice
486
on an intermittent
(campaign) basis and
requires only a peroxide bleach liquor
makeup and delivery system.
8.2 Alkaline peroxide
chemithermo-
mechanical pulping
Alkaline peroxide chemithermomechanical pulping offers an opportunity to obtain not only a chemithermomechanical
pulp having a higher brightness, but also a
pulp with enhanced physical properties.
The process is flexible enough to be used
in a variety of applications. For example,
alkaline peroxide chemithermomechanical
pulping can be installed in a greenfIeld mill
for the production of market BCTMP. Alternatively, it can be used to upgrade the physical properties of a lower-grade newsprint
TMP, relieving brightness limitations or improving the strength characteristics of the
paper sheet to reduce kraft usage. In either
case, this process can be implemented without the same capital constraints of a conventional
two-stage
bleach plant. An
additional benefIt of the process is the potential for energy reduction resulting from
refIning alkaline impregnated
chips. The
basic process involves impregnation with
an alkaline peroxide bleach liquor in one
or more steps, followed by refining, atmospheric or pressurized. The number of impregnation steps used depends on the final
Chip washing
and
presteaming
Impregnation
Refining
Screening Bleaching
(Single- or (atmospheric)
and
two-stage)
(Single- or cleaning
two-stage)
H202
H202
+
bleaching
NaOH
liquor
DTPA
Rg.
25.
FlmlJsbeet.fur
t.
",.,.
jJerrJzIM cbemitberr1unrrbtmktll
brightness and pulp quality desired. Different variations of the alkaline peroxide
pulping process
may be referred to as alkaline peroxide
pulping, alkaline peroxide
mechanical
pulping and bleached chemithermomechanical pulping. An outline of the process is shown in Fig. 25.
lf the goal is fiber development and only
a moderate (8-10% ISO) brightness increase,
a one- or two-stage impregnation process, in
which low levels of chemicals are applied,
should be evaluated. The results of a moderate two-stage impregnation
on hemlock!
lodgepole pine chips followed by two stages
/1fIIpirtg
process.
of atmospheric refining are shown inThble 8.

A brightness increase of approximately
13 points ISO was achieved along with 7%
decrease in bulk and a 32% decrease in shive
content. In addition, the alkaline peroxide
CTMP required 300-350 kWh/oven-dried
metric tons less energy to refine to the same
freeness (26).
lf a market-type (chemi)mechanical
pulp
brightness
and quality is desired, then
higher applications of chemicals and at least
two impregnation stages are required. The
properties of a black spruce BCTMP and a
black spruce alkaline peroxide CTMP are
compared
in Table
9.
Pulp
1IIbkB. ~o/,,~jJrllJlbkllcW"'''IrIJo-slllge''''''''.~cbMrlt~
~1JIIrtg
ro
H202
bleaching
liquor
process (26).
Furnish: 53% Hemlock! 47% Lodgepole Pine
H202
bleaching
liquor
49.9
Opacity, %
96.6
Freeness, CSF
Bulk, cm3 / g
110
Burst index, mN.m2 / g
3.05
2.1
Tear index, kPa.m2/ g

Tensile index, N.m / g
41.6
Stretch, %
2.I4
T.E.A.,] / m2
32.4
10.2
Pulmac shives, %
Fig. 24. FIoIlJsbeet 1M' reft-
bletreW"g.
Control
Brightness, %ISO
1.5%
HP2'
1.7% NaOH,
1.92
2.5% Na2Si03,
0.5% DTPA, 0.3% MgSO;7HP
APaMP
62.8
88.7
114
2.85
2.0
9.4
42.9
2.30
36.3
1.3
Tule,. ~ofIN~of'-efUl
,,",6'bIM:I:
~
palps
ebe"dmeeblllliall
(AP CTMP 11IMBCTMP) (17).
8CfMP
AP CfMP
80
80
245
244
Burst index, mN.m'fg
3.4
3.2
Tear index, kPa.m'fg
9.9
9.7
Tensile index, N.m'fg
57
56
Scattering
m'/kg
47
50
0.6
0.1
Brightness,
Freeness,
Shives, %
%ISO
CSF
coefficient,
The alkaline peroxide CfMP has equivalent

strength and brightness, a higher light scattering coefficient, and lower shives than
does sulfite CfMP bleached to an equivalent brightness.This suggests that there may
be no need for a bleach plant, and would
significantly reduce the capital required for
a green-field operation (27).
9. Heat- and light-stability of

peroxide-bleached pulps
Color reversion is caused by both heat
and light. Photoyellowing is initiated by the
UV excitation of ring-conjugated carbonyl
and ethylenic groups present in the lignin.
This leads to the formation of free radicals
which abstract hydrogen atoms attached to
phenolic
hydroxyl and benzyl alcohol
groups forming, respectively, phenoxy and
ketyl radicals (28). Phenoxyl radicals are
ultimately converted to quinonoid structures which impart color to the pulp. Heat
reversion has been postulated as occurring
through autoxidation of hydroquinonoid
groups in lignin to their quinonoid counterparts (29).
9.1 Factors affecting light and heat

reversion
Metals, particularly iron, also contribute
to color reversion. In the presence of mois-
Pulps
487
hydroxyl groups generating phenoxy radicals which are the precursors of quinonoid
structures
(4,28). Chelation
improves
brightness stability if the complexed metals are washed from the pulp following the
reaction.The chelation and wash stages that
normally precede bleaching therefore serve
to improve color stability.
Peroxide bleaching irreversibly removes
some of the chromophore
systems from
pulp thus reducing the potential for color
reversion. In practice, however, peroxide
bleaching produces, as well as destroys, lignin species that are prone to revert. As a
result, bleaching may have little net effect
on light stability (30). Bleached and unbleached groundwood papers suffer substantial brightness losses even after short
exposure to sunlight. For this reason, highyield pulps, some of which can be economically bleached to mid-80 brightness levels,
are generally unsuitable as a sole furnish for
high-quality papers which traditionally are
made from chemical pulps.
Peroxide-bleached
(chemi)mechanical
pulps are generally more resistant to color
reversion than are similar pulps bleached
with reducing agents because many reduced chromophores
(leucochromophores) are easily re-oxidized in air to their
colored form.
9.2 Strategies for controlling reversion
To date, the most effective means of controlling the reversion of papers made from
high-yield pulps is through the use of fillers
and coatings. Fillers reduce the fiber content in the sheet whIle increasing the visible light-scattering properties of the sheet
(31). Coatings prevent damaging UV light
from contacting the fiber and/or mask the
yellowed fiber (32). Calcium carbonate, titanium dioxide, and bentonite clays are effective for reducing the light-induced
reversion of high-yield pulps.
ture and oxygen, they produce hydroxyl
10. Environmental impact

Although there are none of the chlori-
radicals (OH) by way of a Fenton-type reaction (30). As stated above, hydroxyl radicals abstract hydrogen atoms from phenolic
nated or suifonated by-products associated

with chlorine or sulfur compounds, peroxide bleaching of (chemi)mechanical
pulps
488
nevertheless makes a large contribution to

the BOD level of the bleach plant effluent.
As reported by Dinsmore (33), BOD loading can be as high as 50-75 kg/metric ton in
effluent from a bleached CfMP mill. The
BOD level is directly related to the amount
of alkali applied to the pulp and is therefore higher for higher brightness applications. Material contributing to the high BOD
is composed primarily of extracted organics and cellulosic and hemicellulosic materials solubilized during bleaching. Besides
the BOD loading, some extracted resin acids can be toxic and may require extended
treatment as, for example, in an anaerobic
or activated sludge process (33,34).
Treatment approaches for bleach plant
effluent vary because the effluent toxicity
may require a combination of anaerobic and
aerobic treatments as in the situation for a
mill bleaching sulfite-based chemithermomechanical pulp, or simply an aerobic treatment pond and associated holding lagoon
as in the case for a stone groundwood
bleach plant. Probably the most versatile
and robust system (with respect to performing through process upsets and loading
swings) is a combination of activated sludge
treatment followed by aeration (34,35).
Before the addition of a peroxide bleaching stage to an existing, non-bleaching
(chemi)mechanical
pulp mill, an environmental impact assessment of the proposed
bleach plant should be evaluated and appropriate changes should be made in the
existing treatment systems to compensate
for the increased BOD loading and potential increase in effluent toxicity.
The alternative
strategy for (chemi)mechanical pulp mills that bleach with peroxide is the "zero liquid effluent" approach
(36). To date, this approach has been successfully implemented at two NorthAmerican mills producing market BCfMP. The
treatment involves filtration, careful monitoring of dissolved components, and distillation.
It requires
that the mill have
si6fillicant water retention (sto1ase) capability. The solid waste by-product that remains is currently disposed of in a land-fill.
The "zero liquid effluent" approach may be
attractive to mills in areas where water discharge regulations are very restrictive.
References
1. Martin, D.H., Tappi 40(2): 65 (1957).
2. Gierer,J.,
Wood Set Technol.
20:1 (1986).
3. Colodette,
J.L., Rothc:nberg,
S., Dence,
C.W,] Pulp Pap. Set. 14(6):JI26
(988).
4. Gierer, J., Jansbo, K., Yang, K., Yoon, B.-H.,
Reitberger,
T., J Wood Chem. Technol.
13:561 (1993).
5. Gierer,J.,Yang,
E., Reitberger,T.,
"The role
of superoxide
anion radicals
(0 .;<:) in
delignification," Seventh Internatioo:..
Proceedings,
CTAPI, Beijing, 1993, p.240.
6. Dodson,
M.G., Bohn, W.L., Meyrant,
P.,
Kouk. R.S., "Impact of sulfonation
level on
hydrogen peroxide bleaching response of
hardwood and softwood high-yield pulps,"
Pulping Conference
Proceedings,
TAPPI
press,Atlanta,
1987, p. 479.
7. Leask, R.A. and Kocurek, M.J., Pulp and
Paper Manufacture,
Vol. 2 Mechanical
Pulping, TAPPVCPPAJointTextbook
Committee,
TAPPI press,
Atlanta,
CPPA,
Montreal, 1987, p. 149.
8. Unpublished
ton, TX.
results, Solvay Interox,
Hous-
9. Pearson, A.J. , "Towards a unified theory of

mechanical
pulping
and refining," 1983
TAPPI International
Mechanical
Pulping
Conference
Proceedings,
TAPPI PRESS,
Atlanta, p.131
10. Newman, B.G., Stationwala,
M.I., Atack,
D., "Analysis of steam flow in disc refining," International
Mechanical
Pulping
Conference
Proceedings,
EUCEPA, Paris,
1965, p. 213.
11. Young, RE. and Guinn, Y.P., Tappi 49(5):
190 (1966).
12. Falkehag, S.I., Marton,J.,Adler,
Cbem. Ser. 59: 75 (1966)
E., Advan.
13. Hart, J.R., Modern Mechanical

Pulping
In Tbe Pulp and Paper Industry
(K.L.
Patrick,Ed.),
Miller Freeman,
San Francisco, 1989, p.189.
14. Ali,T., McArthur,
Whiting,
D., Stott, D., Fairbank,
M.,
p.,J Pulp Pap. ~d. 12(6) 1996.
15. Ali,T., McArthur, D., Stott, D., Fairbank M

Whiting, P.,"The role of silicate in pe;ox:

ide brightening
of mechanical pulp: 2.The
effects of time and temperature;
73rd
Annual Meeting
Reprints,
Tech. Sect.,
16. Moldenius,S.,
R116 (1982).
Svensk
30. Eisenhauer, H.R.,J Water PoUut. Control

Fed. 36(9):1116
(1964).
Pappersttn.85(15):
18. Sbaschnigg, J., Kappel,].,

Petschauer,
E,
"Peroxide high<onsistency
bleaching for
groundwood
and TMP," APPITA Conference Proceedings,Australia,
1988.
19. Moldenius,
S., and Sjogren, B., J Wood
Cbem. Tecbnol. (4):447 (1982).
20. Renders, A. and Hoyos, M., "Disperger
Bleaching with Hydrogen Peroxide:A Tool
for Brightening
Recycled
Fiber", 1993
Proceedings,
TAPPI PRESS,Atlanta,p.1017.
21. Moldenius,
S., J Pulp Pap. Set. 10(11):
Jl72 (1984).
22. Neale, ER., Pearson, A.). Somerville,].L.,
APPITA Tech. Assoc. Proceedings
4:134
(1950).
N. Scallan, A., Tappt
24. Andrews, D.H., "The brightening

of mechanical pulps - A survey of existing technology; 54th Annual Meeting Technical
Section CPPA,Tech. Sect., CPPA, Montreal,
1968.
25. ReferenceAbitibi description from bleach
plant paper -1985 Quebec Int. Pulp
Bleaching.
26. Sabourin, M.J, and Presley, J.R., "Low
chemical
slkaline
peroxide
TMP
489
29. Gellerstedt,
G. and Petersson, B., Svensk
PappersUdn.
83(11):314
(1980).
17. SjOgren, 8., Engstrand, P., Htun, M. "Some

aspects
of high consistency
peroxide
bleaching affecting process efficiency and
pulp properties;
International
Mechanical Pulping
Conference
Proceedings,
EUCEPA, Paris, 1993, p.409.
23. Katz, S. Liebergott,

14(7): 97 (1981).
Pulps
means of upgrading newsprint mills; 1992

TAPPI Pulping Conference Proceedings,
TAPPI PRESS,Atlanta, p.1l35.
27. Sferrazza, M.). and Bohn, WL., "Alkaline
peroxide mechanical pulping, the pulp of
the 1990's," ABTCP Pulp and Paper Conference Proceedings, Sao Paulo, Brazil,
1989.
ZB.Leary, G.].,] fulP fap. Set. 20(6):]1;4
(1994).
31. Casey, J.P., Pulp and Paper Cbemistry

and Cbemtcal Tecbnology, Vol.III, Wiley,
New York, 1981, p.1524.
32. Bristow, ].A.and Kolseth, P., Paper Structure and Properues, Marcel Dekker, New
York, p. 203.
33. Dinsmore,
(1987).
N., Pulp
Pap.
34. Servizi,].A and Gordon,

Can. 87(11):42 (1986).
61(10):139
R.W, Pulp Pap.
35. Rankin, A., Maclean,

B., Irvine, G.A.,
Stevens, G., "Pilot studies of activated
sludge at Quesnel River Pulp; CPPA Technical Section Spring Conference,
Preprints, Tech. Sect., CPPA, Montreal, 1992.
36. Evans,T. "Start-up of Millar Western's zero
discharge BCTMP mill in Meadow Lake;
1992 TAPP1 Pulping Conference Proceedings, TAPPI PRESS, Atlanta, p.1167.
SECTION V:
The Technology of
Chapter 2:
Hydrosulfite (Dithionite) Bleaching
Michael E. Ellis
Hoechst Celanese Corporation
Charlotte, North Carolina
1. Introduction.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 493
2. Chemistry of hydrosulflte bleaching. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 493

2.1 Composition of hydrosulfite bleach solutions
494
2.2 Stability of hydrosulfite bleach solutions
. . . . . . 495
3. Factors affecting brightness response in hydrosu1fite bleaching . . . . . . . . . ..
3.1 Process conditions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2 Mixing efficiency
3.3 Air (oxygen) entrainment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4. Effect of hydrosulflte
bleaching on pulp properties.
495
495
499
500
500
. . . . . . . . . . . . . . . . . . . . .. 501
5. Commerdal hydrosulflte bleaching operatIons . . . . . . . . . . . . . . . . . . . . . . . . ..

5.1 Propertiesofsodiumhydrosulfite
5.2 Composition of typical hydrosulfite bleaching fonnulations . . . . . . . . . . . . . .
5.3 Hydrosulfite bleaching systems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
501
501
502
504
6. Application of hydrosulflte to secondary

(recycled) ftbers
. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 509
6.1 Bleaching of deinked pulps. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 509
6.2 Color stripping. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 510
7. Typical bleaching
results for representative
pulp types
510
8. Safety and environmental

aspects of sodium hydrosu1fite bleaching . . . . . . .. 510
8.1 Chemicals in bleaching solutions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 510
8.2 Bleaching reaction products. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 511
9. Future trends in hydrosuUite
bleaching.
. . . .. . . . . . . . . .. .. . .. . .. . .. .. . ...
491
511
Chapter V 2: Hydrosulfite (Dithionite) Bleaching
Chapter V 2:
Hydrosulfite
(Dithionite) Bleaching
1. Introduction
As used in this chapter, the term "hydrosulfite" refers to sodium hydrosulfite or,
more correctly,
to sodium dithionite
(Na2S20~) because this compound is a salt
of dithionous acid. Because the name "hydrosulfite" is found more frequently in the
context of commercial pulp bleaching, it is
used preferentially throughout this chapter.
The recommended
pulp bleaching stage
designation for sodium hydrosulfite is Y.
The use of hydrosulfite as a bleachittg
agent in the pulp and paper industry began
with its addition to groundwood
pulps.
Following the development
of thermomechanical pulping processes, hydro sulfite
was used to bleach thermomechanical
pulp
(fMP) and became the bleaching agent of
choice for all (chemi)mechanical
pulps,
especially in situations where a brightness
increase of 4-14 points was required. The
use of hydrosulfite in pulp bleaching grew
significantly as more TMP was produced to
meet the growing demands for newsprint.
Paper destined for news applications was
bleached to significantly higher brightness
levels as new printing practices (especially
color printing) were developed.
Mechanical pulps, by nature of their processing, contain all the components initially
present in wood and therefore are classified as high-yield pulps. This means that
most of the cellulose and hemicellulose,
together with lignin and smaller amounts
of lower molecular weight organic and inorganic material, remain in the unbleached
pulp. Carbohydrates are essentially colorless; lignin, the other main component of
wood, contains
chromophoric
groups
which impart color to the pulp. In contrast to the bleaching of chemical pulps, a
purification
process in which residual
chemically modified lignin and other materials are removed from the cellulose fiber
at the expense of decreased pulp yield, the
493
objective in chemimechanical and mechanical pulping is to selectively eliminate colorcontributing groups while maintaining pulp
yield.
Many factors affect chromophore formation in mechanical pulps: wood species and
age, storage conditions after cutting, and
exposure to light and oxygen all play a role.
The pulping process itself provides an excellent environment for newly created fiber surfaces to interact with metals and
other chemicals. Groundwood pulping is
known to produce relatively high-brightness pulp. With the onset of thermomechanical
pulping, unbleached
pulp
brightness decreased. It is now generally
understood that the two most significant
causes of this brightness decrease are elevated stock temperature and retention of
metals in the pulp.
The following sections include a detailed
discussion of the factors influencing the
brightness response of (chemi)mechanical
pulps to hydrosulfite, various aspects of
commercial hydrosulfite bleaching including the handling of hydro sulfite in solid and
solution forms, the various modes of its
application to pulp and its effect on the
brightness of different types of pulp and
recycled paper. The chapter concludes with
an analysis of the future directions hydrosulfite bleaching are likely to take.
2. Chemistry of hydrosulfite
bleaching
Sodium hydrosulfite is classified as a lignin-retaining bleaching agent, that is, it selectively
converts
color-contributing
structures (chromophores) in pulp to their
corresponding colorless Oeuco) forms without simultaneously degrading and solubilizing the 1ignin where the color-<:ontributing
structures are concentrated. In contrast to
alkaline hydrogen peroxide, which is an oxidative bleaching agent, hydrosulfite functions as a reducing agent in pulp bleaching.
Hydrosulfite characteristically reacts with
lignin or lignin-derlved carbonyi-<:onjugated
structures typified by those found in orthoand para-quinones, quinone methides, and
the side chain of coniferaldehyde units. The
494
Pulp Bleaching
-Principles
and Practice
0\ J
II
C-~ "
-W
"""
(Direct Red 81)
0\
S~H
C-N
N= N
-0-
&"
OH
0II
J
"'
S03H
"""
__
-.
S~H
'-
&"
~
N-~
~H
'-
v
H-("("'(H
(Dihydrazo
Intermediate)
OH
I
N-N -V
&"
~S~H
N-~~
&"
(Amine Fragments)
Fig. 1. l'roJIO$M ~
ftw tile rMtIdImt of" direct dy~ (DIrect Dye 81) IlIitb sodl_
reduction of these structures with hydrosulfite involves an electron-transfer reaction

in which sulfur dioxide radical anion attacks
a particular chromophore system and converts it to a structure that no longer confers visible light-absorption properties on
the whole structure. This reaction is illustrated in Chap. ill 4, Fig. 18, for an o-quinonoid unit.
Commercial hydrosulfite bleaching solutions often contain sodium bisulfite as an
impurity or as a result of its formation during hydrosulfite decomposition (see following section). Bisulfite ions can react with
a-, ~unsaturated aldehydes such as those
present in the side chain of a coniferaldehyde unit, forming mono- and disulfonates
in which
all or a part of the chro-
mophore system is eliminated (t.e., decolorized or bleached) as shown by reactions

C and D in Fig. lB, Chap. ill 4.
Hydrosulfite can also reduce azo groups
to hydrazo groups or amines. When these
groups are present as constituents of dyes
bydrostIlftt~.
in recycled paper, their reduction interrupts

the conjugation in the chromophore system
with the result that the dye color is partially
or totally eliminated as is illustrated
in
Fig. I for a typical paper dye, Direct Red
81. The process, referred to as color stripping, is more fully discussed in Chap. II 1.
The chemistry of hydrosulfite bleaching
is described in greater detail in Chap. III 4.
2.1
Composition
solutions
of hydrosulfite
bleach
The principal active (reducing) species

in a hydrosulfite bleaching system is the
dithionite anion,Sp;.
This ion is believed
to dissociate into a sulfur dioxide radical
ion through homolytic splitting of the weak
sulfur-sulfur bond (1,2):
[IJ
This radical ion may give rise to sulfur
dioxide and a sulfoxylate dianion, both of
which are reducing agents (2):

2 S02' ---+
S02
SO;>
[2]
Other
sulfur-containing
compounds
present in hydrosulfite bleaching solutions
are introduced
as minor impurities
during
the synthesis of hydrosulfite
or are formed
from the hydrosulfite
during bleaching:
Pulp + Na2S20. + H20 ---+
BleachedPulp
2 NaHS03
495
2.2 Stability of hydrosulfite bleaching

solutions
I. Exclude air from the pulp during mixing

and bleaching.
In sealed containers, sodium hydrosulfite

powder blends are stable over long periods
of time. Aqueous solutions of hydrosulfite
are relatively unstable and, in the presence
of air, decompose to sodium bisulfite and
sodium bisulfate:
2. Mix the hydrosulfite and pulp thoroughly.
[3]
NaHS03
or by decomposition:
496
+ NaHSO.
(8]
3. Control the ratio of the bleach addition

to the pulp stock flow (adjust accordingly
for pulp consistency changes).
4. Provide suitable retention
proper pH conditions.
The normal ranges of operating conditions

are:
(4]
application
Temperature
Retention
[9]
2 Fe2+ + 2 HS03- + 2,0+
[6]
Of the suIfur-containing by-products initially present or formed during bleaching,

only the bisulfite ion appears to have any
direct bleaching effect (see previous sect.).
Hydrosulfite bleaching solutions, made
commercially by the reduction of sodium
bisulfite with sodium borohydride, contain
sodium borate (NaBO) as a by-product:
NaBH. + 8 NaHS03 ---+

4 Na2Sp. + NaB02 + 6 HP
2-20Ib.ofpwp~on
(1% by wt)
HydrosWfite
In the absence of air, sodium hydrosulfite

can decompose to sodium thiosulfate and
sodium bisulfite:
[7]
This compound may have a buffering effect on the bleaching pH but does not participate in bleaching reactions.
Hydrosulfite bleaching solutions usually
contain additives such as anti-oxidants, pH
buffers, chelants/sequestrants (for metal
control), and alkali to obtain the optimum
pH level required for a particular bleaching
application. Although these additives have
no direct role in eliminating color-contributing (chromophore) groups in the pulp
during bleaching they are essential for maximizing the bleaching efficiency of hydrosulfite.
Although the aerobic decomposition of

sodium hydrosulfite occurs in a relatively
short time, the anaerobic decomposition
begins only after several days. The latter
reaction is governed by pH and temperature. Solutions that are maintained at low
temperatures (-7"C) and at an alkaline pH
00-12.5) remain stable for many days.
For efficient bleaching reactions, (2] and
(3] must be minimized. Suppression of the
oxidation reaction requires carefW control
of mill systems. Care is needed to ensure
that air is not introduced into the pulp, particu1arly in or near the bleaching stage. Pr0prietary hydrosulfite
blends have been
formulated to suppress the anaerobic decomposition reaction.
3. Factors affecting brightness

response in hydrosulfite
bleaching
Sodium hydrosulfite is a strong
reducing
agent and must be used in a manner which
allows for complete
reaction with all materials capable of being reduced.
Each variable or operating parameter produces a
measurable result. Collectively, they can

help to produce brightness gains of 4-14
points. The following operating guidelines
help ensure maximum brightness increases.
time and
40-100'C (higher
in pressurized refiners)
30-60 mIn
time
pH
4.5-6.5
Consistency
3-30 %
These variables are all interdependent;

for example, elevating the temperature allows the retention time to be reduced, increasing mixing at the point of addition
pertnits reduction of the retention time,
and an increase in pulp consistency allows
the use of a lower retention time. A detailed
discussion of the individual effects of the
different variables on brightness continues
below.
Chemical charge
The amount of sodium hydrosulfite or
hydrosulfite-contalning
bleaching solution
added to a pulp stock varies from mill to
mill, from wood species to wood species,
and according to type of equipment used.
Generally, 0.1 to 1.0% or 2 to 20 pounds of
bleach per ton of pulp is used. (It should
be noted that a 1% addition refers to a
weight percent addition
based on the
weight of chemicals added per weight of
oven- dry pulp. Therefore, a I % addition
corresponds to adding 20 pounds of chemical to 2,000 pounds of oven dry pulp. This
is more commonly referred to as 20 Ibs/ton
in most North American mills.) As seen in
Fig. 2, there is a limit (ceiling) to the brightness gain that can be achieved by increasing the amount of hydro sulfite applied to a
particular pulp. In the example shown, the
upper limit is about 10 points. Once the
brightness plateau is reached, any excess
hydrosulfite may decompose
to sodium
thiosulfate and sodium bisulfite (see reaction 151 in the previous section).
Temperature
The ideal temperature range for bleaching mechanical pulps with hydrosulfite is
45-6O"C. The temperature range commonly
used to bleach pulp at 3-5% consistency in
12
c:
10
'co
CI
UJ
c:
'0
a.
UJ
UJ
Q)
c:
~CI
'C
Temperature: 60C
Consistency: 3.3%
pH: 5.9
4
2
m
0
0
ng.2. Ilrl&""'- ~
0.2
0.4 0.6 0.8 0.10 1.2

Hydrosulfite, % on pulp
1.4
ofTMP blMeW ntb IIIIryI., IIm088tsof IIydronlftte (3).
1.6
497
plete hydrosulfite consumption. With this

in mind, most mills design their bleaching
towers to accommodate a 30-minute retention time. An increase in temperature and
good mixing may overcome the need for
an extended retention time.
an upflow tower is 55-6O"C. As expected,

an increase in bleaching temperature increases the bleaching rate and also leads to
a higher final brightness (Fig. 3). Although
these results suggest the advisability of
bleaching at still higher temperatures, it has
been found that brightness reversion also
is accelerated at higher temperatures.
Another factor limiting the use of higher
temperatures in bleaching is mixing. Refiner bleaching techniques have eliminated
some of these problems. Although the survival of hydrosulfite at temperatures near
l00"C (as occurs in primary and secondary
pressurized
refmers) seems doubtful, in
practice high turbulence in the refining
zone ensures that the pulp and bleaching
chemical react rapidly with the result that
only a relatively small amount of hydrosulfite is decomposed.
Pulp pH
The relationship between pH and the stability of hydrosulfite solutions is well recognized: Lowering the pH leads to a
decrease in hydrosulfite stability; for example, at pH levels < 4, immediate decomposition occurs. Conversely, when the pH
is increased to near 11, hydro sulfite solutions are stable for weeks, provided the temperature remains low and contact with air
is minimized.
Although sodium hydrosulfite has a much
higher reduction potential in alkaline media than in acidic media, mill experience
has confirmed that higher brightness levels are achieved when hydrosulfite bleaching is performed
under mildly acidic
conditions (pH 4.5-6.5). However, hydrosulfite bleaching also can be successfully
conducted under slightly alkaline conditions provided additional bleaching chemical is added to offset the apparent negative
effect of alkali darkening at the higher pH(6).
Retention time
The optimum retention time for hydrosulfite bleaching is 30.60 minutes. As shown
by the plot in Fig. 4, most bleaching typically occurs within the first 10-15 minutes
following hydrosulfite addition. However,
to fully utilize the reductive capacity of the
bleaching agent, sufficient additional retention time must be provided to allow com-
498
Pulp Bleaching
-Principles
c:
'(ii
C>
!/)
c:
'0
0..
!/)
Hydrosulfite:
Temperature:
Consistency:
pH: 5.5
!/)
CD
c:
.c:
C>
.;::
c:
'(ii
C)
!/)
o
o
c:
'0
0..
,/
c::
.t;j
C>
J9
c::
'0
0..
!/)
!/)
CD
".""
".
/' ,.,','
,I,,"
C>
'C:
on brigbtness
tlellelopmertt
pH= 6.0
pH=5.0
pH=4.0
."
0.2
Hydrosulfite,
of ,,,""'1/,,11,
bytlroSfllftte (4).
Consistency:
pH: 5.0
Consistency:
Temperature:
4%
60C
0.4
0.6
0.8
% on pulp
0.6
m tbe blellebl"g
of _them
JIll Oft brightness tlellelopment I" tbe bletU:blng of _them
pine TMP wltb
4%
0.8
Fig. 3. E.I1t of temperature
Stllftte (3).
-',-'
I,,'/"
I""
c::
Fig.5. E.I1t
0.4
0.2
70
time, min
_-".,,,._.>..,'
.,'
".".,,,,,,'"".",."
0
0
60
50
a:I
40
50C
/ ,,' "
I ,I'
1',1'
,I,"
,
/,,'
!/)
!/)
CD
c:
.c:
C)
.;::
./ ,,,'
"
",,'-
30
10
.---------------------.
./''/
20
Retention
./,- 60C
,./
10
Fig. 4. E.I1t of retention tbne on brigbtness tlellelopment I" tbe bletU:blngof smahem pine TMPflJUb bytlroSfllftte (4)
-----------.
0.5%
60C
4%
a:I
m
8
and Practice
pine
TMP wltb bytlro-
The pH of the pulp mixture decreases

during hydro sulfite bleaching as a result of
pulp bleaching and decomposition
reactions. As shown in Fig. 5, decreasing the
pH in the 4-6 range leads to decreased pulp
brightness.
This may be because hydrosulfite decomposition
is enhanced under
conditions of increasing acidity. For this
reason, commercial hydrosulfite blends
containing buffers are available to ensure
that the appropriate pH is uniformly main-
tained throughout the pulp over the course

of bleaching. If pH buffers are not included
with the hydrosulfite solution, they must
be added separately.
Consistency
Within the 2-5% range, consistency
has a
minimal effect on pulp bleachability. However, when bleaching is performed

at a
medium-consistency level (6-10%), a brightness gain 1 or 2 points higher than that cor-
499
500
12
c:
'(ij
C>
II)
"E
'0
a.
8
7
10
10% consistency
J::
C>
'C:
m
II)
c:
'0
a.
Temperature: 60C
pH: 5.5
II)
II)
Q)
"
,,
,,,
J::
C>
'C:
m
"
0.2
0.4
0.6
0.8
Hydrosulfite,
011 brl,,,,-
1.0
1.2
TMP bytIro.
""'"
Goodmixing
II)
c:
'0
a.
--- --
c:
J::
C>
'C:
m
""
-- --
"
,I"
"
0.2
0.4
Hydrosulfite,
FI,.7.If/feetof~
Temperature: 60C
Consistency: 4%
pH: 5.5
"
/"
FI,. 8. Blfeetof ."",i1IM
0.2
0.4
0.6
",,. 011brl,,,,-
~loJtrt-I'.
-1fUe (4).
discussed
_-------------------
,,/'--,
II)
II)
Q)
,,"
tion is increased.
Mixing principles and
technology, as they apply to bleaching, are
10
effldaey
~1fUe(4).
011brlt"'-
leveloJtrt-l
responding to low-consistency
bleaching
can be obtained over a wide range of by.
drosu1fite applications (Fig. 6). The benefit accruing
from higher-consistency
hydrosulfite bleaching offers mills the option of reaching the same brightness in less
time with smaller bleaching towers.
3.2 Mixing efficiency

Goo<Imixing of pulp and bleach chemical is an important requirement for hydro-
0.8
0.6
% on pulp
ill.
of~
pirie TMP
""t"
sulfite bleaching as, in fact, it is in all bleach.

ing processes. Proper mixing helps to ensure uniform bleaching and efficient use of
bleaching chemical. Although mixing effi.
ciency is difficult to quantify, the effect of
good and poor mixing, as indicated by the
difference in bleaching response, may be
signiflcant in hydrosuUite bleaching as the
plots in Fig. 7 demonstrate.
In this case,
the effect of mixing on brightness increases
in significance as the hydrosulfite applica.
in detail
...-----------_.
/,'
12
c:
1.4
of 6tnIII1erw pirie
tN W-:"""
_---------
,/,'-,
% on pulp
leveloJtrt-ll.
air
-- "."' ,.
'(ij
C>
Without
c:
,,
Fig.6. B.Jft of ~
-file (4)
'(ij
C>
CD
c:
c:
//---/_.
II)
II)
_---
#'------------------------
in Chap.VI
2.
Hydrosulfite bleaching solutions are usual1y introduced through the suction side of
a stock pump in which the impeller serves
as a mixing device. Pump malfunctioning,
often indicated by noise and vibration, may
imply that poor mixing is occurring.
In
such instances, a brightness loss may be
observed. This problem can be resolved by
the institution of a preventative pump main.
tenance program.
Some mills use in.line mixers following
the addition of the bleaching solution. In
this case, there is concern that dewatering
may actual1y negate anticipated gains from
their use. The recommended solution is to
use a pump which is designed to accom.
modate the addition of chemicals into the
pulp. Such a pump would fluidize the pulp
and enhance the dispersion of the added
chemical introduced into it.
3.3 Air (oxygen) entrainment

As indicated in Sect. 2, oxygen has a det.
rimental effect on brightness in bydrosulfite
bleaching because it reacts with and con.
sumes the bleaching chemical. In addition,
oxygen can react with the reduced chromophores in the pulp and re-convert (re.
oxidize) them to their corresponding
tN "luc6lltg
of_tlJer.
0.8
pirie TMP
""t"
IIytlr'O.
colored forms thereby lowering the bright.

ness. The plots in Fig. 8 indicate that this
brightness loss can be as much as 2 points.
Because the amount of air entrained in
pulp increases with increasing consistency,
the adverse effect of air entrainment can
be offset to some extent by bleaching at
lower consistency
levels. Although the
theory is unproven to date, lower bleaching temperatures may have a negative ef.
fect on brightness because the resulting
increased solubility of oxygen in the bleach.
ing solution leading to increased hydrosulfite decomposition.
The oxidized form of some metals in pulp
can lead to a decreased bleaching response
by catalyzing the decomposition
reaction
[6) of the hydrosulfite and the re-oxidation
(brightness reversion) of bleached pulp.
Iron and manganese are generally viewed
as the worst offenders in each instance (7.
9). Analysis of thermo mechanical pulping
systems has shown that as much as 10 ppm
iron and 150 ppm manganese can be contributed by the wood. One of the most
manageable sources of iron contamination
is the alum used for pitch or deposit control. Iron is present in varying concentrations throughout the ra11geof commercial1y
available alum products. When attempting
to maximize brightness, it is advisable to
501
66
64
o
~
62
............
......
---- ......
~
Ethylenediaminetetraacetic
'::::.---------------- ---
?f.
U;
rJ)
Q)
60
c:
.C)
c:
'C
CD
acid
------- ~"'.......
Diethylenetriaminepentaacetic
-------acid
.............
...
58
Sodium
tripolyphosphate
56
100
200
300
Iron added,
Fig.,. EffIof lUff-I ebe"",,,gagerttstml1rlgllhtnS

.
~ofi"",
(9).
use only low iron-containing or iron-free
alum. Iron in its reduced state does not affect brightness. However, when deposited
on a paper sheet, ferrous iron is subject to
oxidation. When this occurs, the resulting
black form of iron oxides reduces brightness significantly.
Most commercial hydrosulfite blends and
some liquld formulations contain sufficient
amounts of chelating agents to control the
adverse effect of small amounts of iron,
copper, manganese, aluminum, and chromiumonbrightne~.Howeve~whenmetal
contamination is especially high or when a
mill uses hydrosulfite generated on-site, the
application of additional amounts of chelating agents may be required. The effect of
different chelating agents on brightness response in hydrosulfite bleaching is illustrated in Fig. 9.
Normally, 0.1 to 1.0",6(2-6 lb. per ton of
pulp) of chelant perton of pulp provides
adequate control. Ethylenediaminetetraacetic acid (EDTA) is generally used in a pH
range below 7.0. Sodium tripolyphosphates
also control metals and are viewed more as
sequestering
agents than as chelants.
Diethylenetriaminepentaacetic
acid roTPA)
is used in alkaline systems. It should be
noted that excessive amounts of chelating
agent may adversely affect brightness.
500
400
ppm on pulp
~
of _Ibent
~u
TMP
CtnI"'''''''g
fMJryiIIg
Regardless of the choice of chelating

agent, once metals enter the system it is best
to reduce them to their non-colored state,
complex them with a chelating or sequestering agent, and remove them from the
pulp before it is sent to the paper machine.
The most satisfactory way of dealing with
metal contamination
is to exclude them
from the process.
4, Effect of hydrosulfite
properties
502
it forms a dihydrate that reacts almost instantaneously with oxygen. The solubility
of sodium hydrosulfite in water is about 18%
at 20"C. A 1% solution of commercial sodium hydrosulfite has a pH of 6.5 +/- 1.
Sodium hydrosulfite can decompose when
exposed to air, moisture, heat, or oxidizing
agents. Its decomposition produces both
heat and oxygen; the heat generated can
be sufficient to cause a fire.
Solutions of sodium hydrosulfite are clear
liquids at varying concentration levels. For
long-term stability purposes, the liquid
products are cooled to about 7"C, stabilized
with alkali, and maintained in an oxygenfree environment.
The aerobic and anaerobi~ecomposition of hydrosulfite solutions is described
by reactions [8] and [9] (Sect. 2.2). Although the aerobic decomposition
of sodium hydrosulfite occurs in a relatively short
time, anaerobic decomposition begins only

after several days. The latter reaction is governed by pH and temperature. Hydrosulfite
solutions, maintained at low temperatures
(-7"<:) and at an alkaline pH (l()'12.5), remain stable for many days.
For efficient bleaching, reactions [2] and
[3] must be minimized. Suppression of the
oxidation reaction requires careful control
of mill systems. Care is needed to ensure
that air is not introduced to the pulp, particularly in or near the bleaching stage. Pr0prietary blends have been formulated to
suppress the anaerobic decomposition
reaction.
5.2 Composition of typica1-hydrosulfite

bleaching formulations
Reductive bleaching with hydrosulfite
has grown over the years because of its
ease of handling and low cost. Sodium
3'_
I~ICI
on pulp
quick
2'
dloconnecl
GIll.
"'s.>
In general, the following can be stated

regarding the effect of hydro sulfite bleaching on pulps: Ugnin and lignin containing
compounds are bleached (whitened) but
not removed, there is little effect on hemicelluloses, extractives are bleached or removed, the degree of polymerization
of
cellulose is essentially unchanged, and the
amounts of shives and fiber bundles are
decreased (10). To date, little has been reported in the literature about pulp strength
as it relates to pulp bleaching with sodium
hydrosulfite.
2XIK:
3X2 -
5, Commercial hydrosulfite
bleaching operations
1*
5.1 Properties of sodium hydrosulfite

Sodium hydrosulfite is a free-flowing,
white crystalline solid. When moistened,
2.truck
unloedlng
lJnloedll1!J""-'"P
Fig.10.St:bemIIIkIUagrwM
for ~
"-"
ptlmpo
aU slorwgeof
l1y4msulfltesol.1imI
at" mill sile.
Toproceso

hydrosulfite is supplied to the industry in a
number of different fOnDs. It can be purchased as a liquid or powder or made onsite from the addition of sulfur dioxide or
sodium bisulfite solution to caustic soda
(sodium hydroxide) and sodium borohydride.
When delivered as a solution, hydrosulfite is pumped from the delivery tank
truck into a storage tank at the mill (Fig.
10). A typical installation uses a 37,85460,566 L (l0,OOO-16,OOO gallon) insulated
fiberglass-reinforced
plastic tank equipped
with a nitrogen padding system to keep
exposure to air at a minimum. Depending
on usage rates, refrigeration on the storage
tank may be necessary. If approximately
three truck loads per week (56,781 liters
or 15,000 gallons) are used refrigeration wilt
most probably not be needed. The newly
arriving material (supplied at 7"C) assists
in maintaining
a suitable storage temperature.
503
When delivered as a powder in 113 kg

or 1000 kg (250 or 4,400 Ib) returnable
containers, the sodium hydrosulfite product is dissolved in water and added directly
to the pulp slurry (Fig. 11).
On-site generation of hydrosulfite is accomplished
through the use of a skidmounted reaction unit into which is added
sulfur dioxide or sodium bisulfite solution,
caustic soda (sodium hydroxide), and s0dium borohydride (Fig. 12).
If sodium bisulfite solution is used, sulfuric acid is also added to neutralize excess
sodium hydroxide in the borohydride solution (reaction [10)). 10 this case, the added
caustic soda is added only for post pH adjustment of the resulting sodium hydrosulfite solution.
NaBH. + 3.2 NaOH + 8 NaHS03 + 1.6
H2SO. -+ 4 Na2Sp.
+ NaB02 + 6 H20
[10]
504
In alternative procedure (reaction [II)),

sodium hydroxide is used for both the generation of sodium hydrosulfite and for postpH adjustment of the manufactured hydrosulfite solution.
NaBH. + 3.2 NaOH + 8 S02 + 4.8 NaOH
-+
NaBH. + 8 NaHS03 -+
4 Na2Sp. + NaB02 + 6 HP
[11]
The borohydride is supplied as a solution

containing 12% sodium borohydride, 40%
sodium hydroxide, and 48% water. Regardless of which of the above reactions [10 and
11] is used, the reaction of sodium bisulfite
and sodium borohydride produces sodium
hydrosulfite and the by-product, sodium
borate. Hydrogen gas is also produced by
a simultaneous
competing
hydrolysis
reaction:
NaBH. + 2 HP
-+ NaB02 + H2 (gas) [12]
The sodium borate remains in the hydrosulfite solution, but the hydrogen gas must
be carefully vented to the atmosphere.
5.3 Hydrosulfite bleaching systems

The choice of hydrosulfite bleach addition point(s) depends on the amount of
brightness gain required. On average, a mill
can expect the following results:
Points
Brightness
Gain
Addition Point
4-6
8-10
2-6
9-14
Refiner (single-stage)
Tower (single-stage)
Stock chest (single-stage)
Refiner and Tower (two-stage)
Refiner bleaching
A process for bleaching lignocellulose
material (pulp) with a reducing bleaching
agent in multi-stage refiners was patented
Sodium
borohydrlde
solution
BIn
BIn
Vent
Water
'" Oeuas
IXlJ
Sodllm
blsumt.
To
t
t
)(()(IJI
lank
(jJ
t
t
Static mixer
Sulfuric
acid
I
L
I
I
I
I
J
1L
Caustic
soda
solution
DlnoMng
tank
i
'
L
~
lie
,nrr
pHI
pll".'
Fig. 11. Sebem4tk
tUtlgrwm of II maUap
systtlm
for
soM_
~lftle
bktldmtg
sol.tItms.
Fig. 11. Seberrrstk tUtlgrwm of OIl-sUe bytlros,Ilflle
Demand from process
gnreraU18g sysltlm.
To storaaelProcess
in 1969 by Crown Zellerbach Corpora-
(11)
tion.
The addition of sodium hydrosulfite
bleaching products into the refining zone
of a TMP refiner was commercially undertaken in North America in the early 1970s
by Bowater Corporation to increase pulp
brightness. With respect to the bleaching
effect of hydrosulfite, the following factors
are critical: pulp temperature, pH, alkalinity, bleaching chemical charge, and effective chelation (12).
Refiner bleaching provides mills with the
opportunity to obtain incremental brightness gains without having to rely on a singlestage hydrosulfite addition step to attain the
brightness objective. In refiner bleaching,
50-95% of the total brightness gain required
is typically obtained.
Refiner bleaching,
combined with a following second-stage
bleach treatment in an upflow tower, can
provide the desired brightness at reduced
cost under more easily controlled bleaching condition than does tower bleaching
alone. An operator needs only to reduce
hydrosulfite addition in the tower to reach
the target brightness.
Hydrosulfite
505
Operationally, all that is required for the

implementation
of an on-ref mer hydrosulfite bleaching treatment is extension of
the bleach solution line (including addition
of suitable control valves) to the dilution
water line at the refiner (Fig. 13). Bleach
dosage can be controlled automatically or
by manual adjustment.
Sodium hydrosulfite addition to pulp in
aTMP refiner is successful because it allows
several very important bleaching conditions
to be accentuated.
First, the temperature
in a refiner zone is very high, forcing the
bleaching reactions to completion
in a
shorter time. Second, the design of the refiner itself represents one of the best pulp
mixing environments in a mill. Even though
the residence time of the pulp in the refiner is short, the mixing intensity is extremely high thus ensuring a uniform
distribution of bleaching chemical in the
pulp fibers. Coupled with the high bleaching chemical-to-fiber ratio created in the
high-consistency
refining zone, refiner
bleaching has proven to be a very effective
initial treatment in combination with further hydrosulfite bleaching in a TMP mill.
506
The addition of excessively high amounts

of hydrosulfite bleaching solution to the
refiner should be avoided. Because of the
high temperature in the refining zone, excess hydrosulfite may decompose to sodium
bisulfite or sodium sulfate which can undergo thermal decomposition
to gaseous
sulfur dioxide. Specially formulated hydrosulfite blends are available to alleviate this
problem.
A portion of the brightness gained in
refiner bleaching may be lost in ensuing
pulp processing steps because of reversion.
However, by paying proper attention to the
factors that cause reversion (metals, oxygen, heat), a 4- to 6-point brightness gain
can be maintained.
Tower bleaching
Hydrosulfite bleaching in towers evolved
from the need for a defined amount of retention time following the addition of
bleaching chemical to the pulp. The bleaching solution is added to the pulp on the discharge side of a medium-consistency pump
(the point where maximum fluidization of
the pulp occurs) or on the suction side of a
Unbleached
stock
storage
Bleaching
Solution
centrifugal
stock pump preceding
an
upflow bleaching tower (Fig. 14). The pulp
moves through the upflow tower in a plugflow condition and is not mixed or aerated.
The tower is sized according to the consistency of the pulp used and the time required
to complete the bleaching reaction. Most
towers are tile-lined and provide a retention
time of 30 to 40 minutes. Brightness gains
from the use of hydrosulfite in tower bleaching typically range from 8 to 10 points.
Stock chest bleaching
Bleaching in a stock chest is similar to
tower bleaching but the bleaching response
is not as favorable. Stock storage chests do
not possess the upflow character of bleaching towers; therefore, it is not possible to
properly regulate the retention time or to
ensure that the bleaching chemicals react
uniformly with the pulp. Because of their
design characteristics, pulp storage chests
usually do not prevent air from contacting
the pulp. As a result, air entrained in the
pulp can consume any unreacted hydrosulfite and cause oxidative brightness reversion of the pulp. Hydrosulfite bleaching
Steam
Upflow
tower
Temperature
r:::J
o confrol
I
1-2 houre
retention
time
Pulp
I
PrInwy
SecondBry
Ratio
control
Ter1I8y
Level
control
Refiners
.......
Latency Chest
Fig. 13. Flowsheet
for refiner
bletu:btng
wltb bytlrrJSIIlflte.
nleached stoc~
to
Level
chest
Fig. 14. Flowsbeet
for bytlrosfIlflte
blellCbtng
paper
In an upflow
tower.
machine
507
solution is introduced into the stock chest

in much the same manner as in a bleaching
tower (see Fig. 14). Brightness increases
of from 2 to 6 points are typical.
finer bleaching is followed by tower bleaching as outlined in the process fIowsheet

shown in Fig. 15, a combined brightness
increase of 14 points is obtainable (Fig. 16).
Sequential refiner and tower bleaching

As stated in Sect. 5.3.1, a 4- to 6-point
brightness increase can be achieved by hydrosulfite bleaching in a refiner. When re-
Sequential peroxide-hydrosulfrte bleaching

Sequential oxidative-reductive bleaching
(i.e., peroxide-hydrosulfite)
is used byTMP
mills to obtain large brightness increases
gl
508
Pulp Bleaching
- Principles
and Practice
(15-25 points) at lower total bleaching cost

compared with that for single-stage peroxide bleaching (Fig. 17). It is the preferred
method for obtaining a brightness gain
which surpasses the limit achieved with
single- or multiple-stage hydrosulfite additions (13).
The fIowsheet for a sequential peroxidehydrosulfite bleaching sequence is shown

in Fig. 18. The two-stage sequence consists
of the following steps:
1) A first-stage peroxide bleach performed
under conditions described in Chap. V 1
25
r ,--........
c
'Cij 20
C>
UJ
---
Pulp
--1-'
C
'0Q.
UJ
UJ
Q)
C
..._ CIw8t
hydrosulfite addition:
10
"
.-,
Fig.17. Brlgblrlns ~
1
2
Hydrogen peroxide, % on pulp
of,."
blHdJed I.." two-Stllp ~-bydrosulftte
system (5).
Up.Iow
,,-Pulp 10
Blond
O.1_8-~~~:-_.
"""".......................
15
.J::.
C>
.;::
II)
Second-stage
BIo8ch
Tower
Cho8I
16
14
C
'Cij
C> 12
UJ
C
'0Q.
UJ
UJ
Q)
C
C>
'C
II)
Refiner
10
S
6
,.-- - -- --
---------
addition
1%
FeraKIde
Bleac:hlng
System
-----------------------------.
"""""'0.5%
::',/,
R_
will
appropriate
resldU81
neulnllzatlon
4
2
0
0.2
Hydrosulfite
Fig. 16. Brlgblrlns resptmse of_them

bydrosulftte (5).
0.4
applied
0.6
0.8
in tower, % on pulp
pille TMPblellCbl..g I.. seqrumUtlI reft_-upjl_
Hydrosulfite
Bleach Solution
tower system tdtb
Pulp to
Paper
Machine
Blind Chili
509
2) Reduction (neutralization) of residual peroxide with sulfur dioxide or sodium

bisulfite
3) Adjustment of pH, as required, to a level
suitable for optimal hydrosulfite bleaching
4) Application of a second-stage hydrosulfite
treatment in an upflow tower
both requirements are met by the addition

of a single, inexpensive chemical, sulfurous
acid.
Care must be exercised when storing and
handling peroxide and hydrosulfites. These
two chemicals are not compatible: peroxide is an oxidizing agent and hydrosulfite is
a reducing agent. (14)
Because peroxide bleaching is terminated before the peroxide is totally consumed, the residual
oxidant
is first
destroyed so that it does not consume hydrosulfite in the following stage. Sulfurous
acid (82S03)' formed by dissolving sulfur
dioxide in water, or sodium bisulfite
(NaHSO,) is generally used for this purpose.
The neutralizing
agent is automatically
added as called for by in-line pH sensors.
Sulfurous acid both reduces residual peroxide and lowers the pH from the alkaline levels used for peroxide bleaching to the
slightly acidic levels required for optimized
hydrosulfite bleaching. .If sulfuric acid is
added to make this pH adjustment, as is
sometimes done, a separate reducing agent
must be added to destroy the residual peroxide. Although the addition of these two
chemicals may achieve the desired effect,
this approach is more costly than when
'0
a.
U)
U)
Q)
c:
ofslllgle-color}Hl/ler
StI1IIJIles to sodium
35.3
83.4
92.2
94.6
-13.4
-0.8
46.2
2.5
Blue
None
Hydrosulfite
75.0
82.0
83.1
93.4
-4.6
-2.1
-10.6
1.6
6. Application of hydrosulfite to
secondary (recycled)fibers
Red
None
Hydrosulfite
42.5
84.7
73.3
94.6
32.3
0.0
3.2
1.6
Sodium hydrosulfite plays two roles in

the processing of secondary fibers and
deinked pulps. First, because of its high
reducing potential, sodium hydrosulfite is
an excellent additive for the removal of
color introduced into the pulp in the form
of dyes or other coloring agents (see Fig.
19). Second, deinked pulps containing mechanical pulps can be bleached with sodium
hydrosulfite to regain brightness which may
have been lost through reversion.
Green
None
Hydrosulfite
51.6
68.5
81.3
93.7
-22.3
-6.0
7.8
13.0
6.1 Bleaching of deinked pulps

Bleaching conditions for deinked pulps
are very similar to those used for TMP except that the pH is considerably higher. TMP
bleaching is usual1y performed at pH 4.56.0; Deinked pulps are bleached at pH 5.57.5.
50C
3.5%
Color
Chemical
Yellow
'CIELAB or STARLAB values
L. = Yaxis
a*= Xaxis
b. =
Z axis
6.2 Color stripping

When color removal is the goal, operators of deinking mills are advised to consider the use of hydrosulfite to strip dyes.
Many dye colors are eliminated more effectively by sodium hydrosulfite than by an
oxident
If the furnish contains mainly chemical
fibers such as a mixed office waste furnish,
decoloration
occurs under conditions
slightly different from those used for a furnish containing mostly mechanical fibers.
Higher temperatures, 8Q-l00"C, and a pH
of7.0 and higher improve the dye-stripping
efficiency of sodium hydrosulfite. The textile industry successfully uses large quantities of hydrosulfite in a higher pH range
(9.5-11.5) to reduce dyes.
Table 1 shows the bleaching
and
decoloration responses of single-color paper samples to sodium hydrosulfite using
1% addition of sodium hydrosulfite at 4%
consistency, pH 7.0, 80"C, and a 6O-minute
retention time.
.L:
C)
7. Typicalhydrosulfite bleaching
responses for representative
pulp types
'C:
CD
0
0.2
0.4
Hydrosutfite,
Fig. 19. Brlgbmess
resptmse
of dellIied
old -sJIrlllt
(4).
None
Hydrosulfite
Temperature:
Consistency:
pH: 6.5
bydrosuljite
a.'
-c:
Table 1. Resptmse
L"'
'6
C)
U)
Brightness
(% ISO)
c:
'(ij
510
0.6
0.8
1.0
% on pulp
(ONP) pulp
bletlCbed wltb bydrosuljite
(3).
Wood species vary greatly from region

to region. They contain different levels of
metals, may be cut at different ages of
growth, and may be subjected to different

handling practices. All these conditions affect unbleached brightness and, therefore,
final brightness. It is difficult to assign typical brightness response values to groundwood or mechanical pulps without regard
to their history.
Nevertheless, the information in Table 2 provides as approximate
indication of the differences in response of
different (chemi)mechanical
pulps and secondary fibers to hydrosulfite bleaching.
8. Safety and environmental

aspects of sodium hydrosulfite bleaching
8.1 Chemicals in hydrosulfite
bleaching
solutions
Powder forms of sodium hydrosulfite are

classified by the United States Department
of Transportation as being spontaneously
combustible.
Sodium hydrosulfite
is a
strong reducing agent and care must be
exercised to ensure that it does not contact
oxidizing agents, acids, or water. Depending on their pH, solutions of sodium hydrosulfite mayor may not be classified as
corrosive. When delivered to the mill in
solution form, these products are slightly
alkaline; when prepared as a solution from
the powder form, these solutions are near
neutral to slightly acidic,
Pulp Description
TMP
Spruce
Aspen
Douglas-fir
Hemlock
Balsam
Pine
Hardwoods
+++
+++
+
++
+++
+++
++
Northern
Western
Cottonwood
Pine
Spruce
Hemlock
Northeast
Northwest
SprucelFir
?
++
+++
+++
++
++b
++b
Secondary Fiber
Mechanical Pulp-Containing
Mechanical Pulp-Fn:e
Northern
Western
Southern
Groundwood
CTMP
Other
Bleaching Response
Southern
Kenaf
511
++
+
+
Brightness points gain: + 3-5;++ 4-7; +++

~10
Information provided by Morton International, Inc.
512
free kraft pulp demonstrated that (under o~

timized conditions) as many as 7 points of
brightness can be gained(6).
The use of secondary fiber will continue
to grow until availability or market conditions limit its use. This will lead to incn:ased
use of sodium hydrosulfite. Addition of hydrosulfite to pulp will not only be in bleach
towers but will encompass din:ct addition
into dispersion units, and other new equi~
ment designed
to ease the burden of
deinking on washers and flotation cells.
Sodium hydrosulfite will even be applied
to n:cycled corrugated for some form of
decoloring so that the base sheet will have
a more uniform appearance making coating operations mon: consistent from batch
to batch and from mill to mill.
References
1. Cotton, EA. and Wi1kinson, G., Adt'anced
Inorganic
Chemistry,
4th edn. WileyInterscience,
New York, 1980, p.535.
2. Atkins, P.W., Horsfield,A.,
8.2 Bleaching reaction products

Proposed United States and worldwide
environmental
regulations are currently
being designed to limit air and water pollutants including, but not limited to, chloroform, adsorbable organic halides (AOX ),
dioxin, and furans. In contrast to kraft
bleaching, (chemi)mechanical
pulp bleaching with sodium hydro sulfite does not generate chloro-organic compounds and other
pollutants.
Biological oxygen demand
(BOD) and chemical oxygen demand (COD)
incn:ases caused by lignin decomposition
an: not seen because sodium hydrosulfite
modifies but does not degrade or solubilize
lignin in its pulp bleaching process.
9. Future trends in hydrosulfite

bleaching
Because of its ease of use and n:latively
low cost, sodium hydrosulfite should continue to be the chemical of choice in mechanical pulp bleaching and in secondary
fiber bleaching and decoloring.
With the continuing need for chlorinefree bleaching systems and mon: environmentally compatible
processes, sodium
hydrosulfite may find a new application in
the bleaching of kraft pulp. Work has already begun in this an:a and severallaboratory, pilot plant, and even mills trials have
been completed.
The resulting pulp will
almost certainly have different physical
properties,
including the possibility of
gn:ater stn:ngth and a lower lignin content.
Laboratory bleaching of a totally chlorine-
M.R.C.,
3. Ellis, M.E.. "Deinking

of Secondary
Fibers,"Seminar
Proceedings,
Western
Michigan University, Kalamazoo, MI. 1990,
p.277.
4. Fluet, A., "The Brightening
of Mechanical
Pulp with Sodium Hydrosulfite;TECH
'94,
CPPA Mechanical
Pulping Course Notes,
Tech. Sect., CPPA, Montreal, 1992, p. 1.
5. Unpublished
results,
Corp., Charlotte, NC.
Hoechst
Celanese
6. Ducharme,
N.R. and Nye, J.E, "Optimum
Conditions
for Bleaching Totally Chlorine
Fn:e Kraft Pulps with Hydrosulfite;
1993
Proceedings,
7. Hart, R., Pulp Pap.
8. Hart, R., Tappi
9. Ganguli,
When hydrosulfite is prepared on-site

from sodium borohydride
and sodium
bisulfite and sulfuric acid or sulfur dioxide
and sodium hydroxide (caustic soda), can:
must be taken in handling these chemicals.
Sodium borohydride is supplied as a solution containing 12% sodium borohydride,
40% sodium hydroxide, and 48% water. This
solution is highly alkaline and should not
be allowed to contact the skin. Sulfur dioxide is a Class B poison and must be
handled accordingly.
As with all chemicals, the appropriate
Material Safety Data Sheet (MSDS) should be
consulted befon: working with the material.
Symons,
J Chern. Soc. 1%4:5220.
55:138
(1981).
64 (3):43 (1981).
K.K., Pulp Pap.
54:108
(1980).
10. Voelker,M.H.,The
Bleaching of Pulp CR.P.
p.342.
11. West, W B., US Pat. No. 3,467,574
16, 1%9).
(Sept.
12. Ellis, M. E., "Pulp Bleaching

with Sodium
Hydrosulfite
in a TMP Refiner System:Important Parameters,
1989TAPPI Pulping
Conference
Proceedings,
TAPPI PRESS,
Atlanta, p. 191.
13. Ellis, M.E., Pulp Pap. 61:129
(1987).
14. Kise, M.A., The Bleaching

of Pulp CR.P.
pp. 255-273.
SECfION VI:
Bleach Plant Operations,
Equipment and Engineering
Chapter 1:
Pulp Pumping and Hydraulics
Jeffrey lindsay
Institute of Paper Science and Technology
Atlanta, GA
(Currently at Kimberly-Clark Corp., Neenah,WI)
Johan
Gullichsen
Department of Forest Products Technology
Helsinki University of Technology
Espoo, Finland
1. Overview of pumping
needs and trends . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . .. 515
2. Pulp suspension behavior. . . . . .., . .. . . . . . . . . . .. . . . . . . . . . . .. . . . . . . . . . .. 515

2.1 Low-consistency flows. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 515
.2.2 Medium-consistency flows. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 516
3.Basicpumpingconcepm
518
3.1 Centrifugal pumps. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 518
3.2 Positive-displacement pumps
520
4. Pumping of pulp
4.1 Low-consistency pulp. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2 Medium-consistency centrifugal pumps. . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
.....
4.4 Design of medium-consistency systems
for design of pumping
and piping systems . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
5.1 Power requirements and pipe size
5.2 Sizing pumps. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3 Materials for pumps and pipes
5.4 Pressure measurement. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.5 Partial flow. . . . . . . . . . . . . . : . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.6 Elbows, valves, flanges, supports. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.7 Pump drive trains. . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.8 Seals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.9 Potential of sealless pumps. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.10 Filtrate air. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
S.11
5.12
5.13
5.14
Maintenance
........................................
Control and stability issues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Startup. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Flow metering. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
513
521
521
522
526
528
529
530
530
530
530
531
531
531
532
532
532
532
533
533
534
Chapter VI I: Pulp Pumping and Hydraulics
Chapter VI 1:
Pulp Pumping
and Hydraulics
1. Overview of pumping needs
and trends
No other non-Newtonian fluid is pumped
in larger volumes than wood fiber suspensions,and yet these suspensions remain one
of the least understood industrial flows. In
the past, pulp operations at low-consistency
(less than 6%) were commonplace. In the
bleach plant, chemical addition and mixing,
pulp discharge from storage towers, and dilution and washing historically were done
at low-consistency. Conventional centrifugal pumping strategies were usually adequate.Where pulps of higber consistencies
had to be pumped, positive displacement
pumps were the standard, but significant
pumping at elevated conSistencies was generally avoided.
Now, however, there are strong incentives to operate at higher-consistency
wherever
possible. The advantages
of
higher-consistency
include lower energy
costs to pump and heat water, less capital
equipment when diluting and thickening
operations are eliminated, more compact
equipment and facilities, chemical savings
when less diluting water is present during
bleach addition, and decreased effluent
volume (a major environmental
and economic consideration).
Since the late 19505, many bleaching and
transfer systems have employed mediumto high-consistency (10-18%) pumping to
decrease water use, energy use, and pulp
storage space. These "thick stock" systems
accept the various sized lumps of wet stock
and air and displace them into a pipe for
mixing, heating, bleaching, refining, or
transport to storage. In the past decade, a
need has developed to process the higherconsistency pulps at pressures up to 1.4
MPa (200 psi) and with significantly less air
content as newer bleaching processes replace cWorine bleaching.
515
Recently, significant gains have been

made in pumps for medium-consistency
pulp slurries, but feedback from the industry suggests that even greater gains are
needed. It also appears that a fundamental
understanding of medium- and high-consistency flows does not yet exist to adequately
guide equipment development.
While medium-consistency
technology
will grow in importance, low-consistency
pumping operations will continue to be significant. Both processes are discussed below. The behavior of pulp suspensions
relevant to pumping and pipelines is first
reviewed, and pumping strategies are then
discussed.
2. Pulp suspension behavior

2.1 Low-consistency
flows
The unique characteristics of pulp suspensions in pipe flow have been reported
by many authors (1-9), and will only be
touched upon here. The ability of fibers to
entangle and form a network dominates the
physics of pulp suspension flow. The fibrous network causes high head losses at
low velocities,sometimes
leads to plugging
especially in contracting channels or
small passages, and entrains air bubbles.The
behavior of the pulp suspension depends
strongly on consistency
and flow rate
within a given pipe. Loosely following
Duffy et al. (2), several common effects are
discussed in terms of Fig. 1, which is a typicallogarithmic head loss-velocity curve for
a low-consistency pulp suspension. In the
region fromA to B, plug flow of the fibrous
Pulpcurve
516
Pulp Bleaching
-Principles
network occurs. Near or slightly beyond B,

at a higher velocity, a clear annulus of water with laminar flow may form around the
plug; the annulus tends to be thin, typically
less than a fiber length. (In some short-fibered or mechanical pulps, the maximum
at point B may be suppressed.) Near C, turbulence in the annulus is apparent, and the
fibers still form a plug in the center. The
plug is increasingly disrupted and begins
to shrink at some point between
C
andE.
At point D, the pressure drop in the suspension is the same as in pure water at the
same liquid velocity. This marks the onset
of drag reduction for, at higher velocities,
the friction losses are less than for pure
water in spite of the higher apparent viscosity of the suspension.The point of maximum drag reduction occurs at point E.
Increases in velocity continue to disrupt the
plug until the flow is fully turbulent, perhaps at point E Drag reduction still occurs
although the degree of drag reduction tends
to decrease as velocity increases further.
Details of the head loss curve for pulp suspensions can vary widely depending on fiber properties, slurry concentration,
and
even configuration of the flow loop used
in the measurements.
The behavior of a pulp suspension is
closely related to the network strength of
the flocs. A useful parameter is 'td,the wall
shear stress at the point where the pulp frictionallosses and the water frictional losses
are equal (point D in Fig. I). This factor is a
measure of the stress required to disrupt
the network. Moller (10) found that different sets of data for a given pulp type can be
collapsed onto a single curve if the data are
plotted in terms of a dimensionless pressure loss term,
(~)D
c
I
I
I
I Water curve
(turbulent
flow)
Log velocity
Fig. 1. ~of'-"IossCllroesftwWtllertmil
II /IfIlp SfU/IeIISUm.
and Practice
[1]
4'td
compared
with a dimensionless
( Y'PZI1 )
velocity tenn,
average velocity, p is the liquid density, and

Jl is the viscosity.
Methods for estimating friction losses and
for optimizing pipeline design are welldescribed
in several recent references
(J 1-16). Pumping operations in the bleach
plant tend to fall in the range of regimes A
to B, though flows in static mixers or in
centrifugal pump impeller zones may be in
the C to E regime.
Details of flow behavior are related to
characteristics
of the pulp fibers themselves, meaning that flow properties vary
with species (especially between hardwoods and softwoods), pulping method
(e.g., kraft compared
with mechanical
pulping), the degree of refining, and the
bleaching process (if any).
In designing a hydraulic system using a
centrifugal pump, data are rarely available
for the exact pulp-type and flow conditions
to be used. Typically, friction data for a similar pulp-type are used (similar origin, similar pulp processing and treatment), and
correction terms are used to account for
differences in temperarure,refming,consisteney, f1l1er, and other factors. Published
data are usually obtained for flow in long,
straight runs of pipe, but the actual application includes elbows, valves, and other
departures from fully developed flow conditions. There is a lack of basic data on the
effects of these perturbations, and general
rules used to estimate their effect on pressure loss may be significantly in error. For
example, elbows increase the pressure drop
in Newtonian fluids; but, in some cases of
pulp flow, elbows may decrease the pressure drop by disrupting part of the plug
when plug flow is occurring. In general,
predictions of pressure losses and power
requirements in the pulp flow systems in a
bleach plant may be in error by 25% or
more. The calculations made by various
vendors may offer widely different predictions about the power and even pump size
required for a system.
1/6
[2]
't3dD
where .1PIL is the pressure drop per unit

distance, D is the pipe diameter, V is the
flows
The frictional resistance of pulp flowing

at a given velocity increases strongly with
consistency. In the medium-consistency
range (8-18%), the strength of the fibrous

NPSH
=Z + (h, -h..) -(ht, + h)
[4]
where Z is static head in the suction line h

is the pressure above the li q uid level 'vp
h ' i~
the vapor pressure of the liquid, hIs is the
friction loss in the suction line, and hi is the
head loss at the pump inlet, all expressed
in equivalent height of fluid. This value
must be greater than the pump manufacturer's specified net positive suction head
required (NPSHR) or, for positive displacement pumps, the net positive inlet pressure
required (NPIPR). NPSHR is a function of
the pump type, pump speed, and the fluid
properties.
If the NPSH is less than the
NPSHR when a pure fluid is pumped, cavitation occurs in the pump, lowering the
pump capacity, possibly damaging the
pump, and causing excessive vibration'in
the pipeline. For air-containing stock (dissolved air as well as air bubbles), cavitation
in the classic sense (sudden vapor collapse
creating shock waves) is reduced or may
not occur (23). Instead,-Iarge air and vapor
bubbles fill the impeller and cause flow reduction or air binding. The presence of air
greatly affects the NPSHR. Manufacturer recommendations are typically based on trials
with pure water and may not apply well to
pulp suspensions.
NPSHR is determined empirically by the
manufacturer. The Hydraulic Institute has
established useful standards for the determination of NPSHR (24). Operating above
the NPSHR typically does not mean that
cavitation is completely absent: it may take
2-20 times the head given by the NPSHR
to completely suppress cavitation bubbles,
but the degree of cavitation occurring for
heads above the NPSHR is usually harmless
and does not reduce the available pump
head by more than 5% (25). However, for
some high-energy pumps, maximum cavitation damage may occur at suction heads
of two to three times the NPSHR.
Performance curves
Performance
curves for centrifugal
pumps can show the relationships between
pump capacity and efficiency, horsepower,
NPSHR, and other factors. Performance
curves are typically determined for a spe-
519
cific pump speed, impeller diameter and

width, and fluid viscosity. Typical performance curves for one pump speed are
shown in Fig. 5.A given piping system also
has a characteristic
curve of head loss
against flow rate.This system curve can only
be modified by changing system head loss
(adjusting valves) or by changing the consistency within the system (e.g., by dilution). The intersection of the system head
loss curve with the pump head curve gives
the flow rate and head loss through the system. Pump suppliers may provide performance curves that show the effect of
impeller size and pump speed to assist in
the choice of pump operating conditions.
520
Flow rate
RI.5. '/)JIIaIlmfIrl./ilpl JHItIIP~~.
Centrifugal pumps tend to be inexpensive, reliable, and easily repaired. They are
the mainstay of most processes
in the
chemical process industries, including the
pulp and paper industry.
Centrifugal pumps cannot perform well
when large amounts of gas are in the system unless some strategy is applied to remove the gas. likewise, startup requires that
the pump be primed with liquid to create
suction to pull in fluid into the impeller.
Self-priming pumps, which must be IDled
with fluid before the first operation, are
available.
-Principles
and Practice

Positive-displacementpumps mechanically open a volume to suction, increase the
volume to take in flow, seal off the volume,
then displace it to the discharge. Pressure
is created as a system response to the motion of the discharged flow and any static
head on the discharge.
Two types of positive-displacement
pumps have been used in pulp handling.
The reciprocating plunger pump was used
for many years for pulp up to 6% consistency. These pumps have valves and were
thus limited to low-consistency application
where valve plugging was less likely. The
other type, rotary positive-displacement
(a)
'U
as
Q)
Pulp Bleaching
pumps, are still widely used. These include

lobe, gear, single-screw, and two-screw
types. Figure 6 shows examples of twinscrew and gear pumps that can be used for
pumping medium-consistency
pulp. Standards and definitions for rotary positive displacement pumps have been provided by
the Hydraulic Institute (26).
Positive displacement pumps can operate with an open suction (no head of stock
at the inlet) or with a suction head. Normally, pumps are run at a fixed speed or
volumetric displacement rate slightly above
the average rate of flow from the source to
allow for normal fluctuations. The self-priming action of the pump displaces whatever

50
E
~20
~ 10
o
o
8 10 12 14
Consistency,
%
16
18
20
Fig. Z. '1'ypkiI1 ,,'r C08tM1s of pulp.
network imparts a high-yield stress to the

pulp and allows large volumes of air to be
entrained (17). The high-flow resistance
and the increased air content prohibit the
use of conventional centrifugal pumps f9r
medium-<:onsistency flow. Figure 2 shows
typical results for volumetric air content as
a function of consistency. Not only does air
fill the eye of the impeller and cause loss of
pumping action with a conventional centrifugal design, but the aJ1-lowers the stock
density so much that feeding stock into the
pump becomes a severe problem. A feed
chute with medium-<:onsistency stock can
bridge or jam under the simultaneous conditions of high network strength and low
density, especially above 14% consistency.
A major breakthrough in handling medium-<:onsistency suspensions was achieved
when Gullichsen and Harkonen (18) discovered that these suspensions can "fluidize" at high shear rates, behaving almost like
water.This is demonstrated in Fig. 3, which
shows data from a rotational shear tester. It
was found that the disruptive shear stress
at which fluidization occurs was a simple
function of consistency, and no obvious
change in mechanisms occurs as consistency increased.
This work laid the
foundation
for centrifugal
pumping of
medium-<:onsistency suspensions (19,20)
which is described below.
Friction calculations in general are done
in the same way as for low-<:onsistency. For
example, some pump manufacturers rely on
a modified form of the Bodenheimer equation (21) which can also be used for lowconsistency flow:
H
= 482
F, F2 F3 C2.33 1""5
. Complete turbulence
D-13
[3]
where H = friction loss (m water/lOO m

pipe), C is consistency (% BD), P is the production rate (admt/d), and D is pipe diameter (mm), and F"F2,and F3 are correction
factors for pulp type, pH, arid temperature,
respectively. This equation applies to pulp
which has been deaerated by vacuum.
Aerated low-<:onsistency pulp may have
higher friction losses, but medium-<:onsistency pulp that contains air may have substantially lower friction losses.
..:..
0)
~
cD
::3
517
518
3. Basic pumping concepts

A wide variety of pump types can be
found in bleach plants. We will concern
ourselves primarily with centrifugal and
positive displacement pumps, which are the
typical pump types used for pulp. Detailed
descriptions of pump components, hydraulic system design, and pump standards are
given in several excellent sources, including publications of the Hydraulic Institute
(24-26), Slurry Transport Using Centrifugal Pumps by Wilson et al. (34), and
Garay's PumpApplicatton
Desk Book (22).
3.1 Centrifugal
pumps
Centrifugal pumps are the most common

example of kinetic pumps, in which kinetic
energy imparted to the fluid in the pump is
partially converted to pressure. In typical
centrifugal
pumps, a rotating impeller
brings fluid to high velocity. The fluid is directed into a spiral volute with a constantly
increasing cross-sectional area (see Fig. 4).
The volute is shaped to produce a uniform
fluid velocity as it moves around the casing
and to gradually decelerate the fluid as it
leaves the pump. The decrease in velocity
as the fluid enters the discharge line converts kinetic energy into pressure. Diffuser
vanes may be added between the impeller
and the outer casing to help decelerate the
fluid and increase the efficiency of converting velocity to pressure.
Impeller design is critical for pump performance. The major categories include
open and closed (or shrouded) impellers.
eO
t-
1000
Revolutions, rpm
2000
Fig. 4. Cross uetIlm of" emIrl/rIgtIl pump showing
Fig. 3. RolfillotuIl
SNflr tWfI for metUllm-corasislettcy
pulp
(18).
Irwpeller
In IN ClUIng.
The open impeller consists of raised vanes

on a plate. The closed impeller has vanes
through two plates; the fluid must enter the
closed impeller through an open eye on the
suction side and pass through the rotating
assembly. Closed impellers are most common for they generally have higher efficiency and are less subject to cavitation
problems. However, closed impellers are
more subject to plugging problems and may
not be reliable for pulp suspensions. Open
impellers can be made with small clearances
between the casing and the impeller, an
essential feature for good efficiency, but lose
efficiency rapidly as the clearances increase
from wear. Clearances in closed impellers
also increase because of wear, but efficiency
decreases only weakly. For high head, large
impellers are desired.To operate efficiently
at the specified head, a smaller sized or cut
impeller is needed. A variety of impellers
may be available for a single pump casing
to allow the user to operate efficiently under a variety of conditions.
Net positive suction head
The radial acceleration of the flow in an
impeller leads to low pressure at the impeller eye and high pressure at the outer casing of the pump. The low-pressure region
can fall below the vapor pressure of the
fluid, leading to the formation of vapor
bubbles, or cavitation. These bubbles can
suddenly collapse as they pass to higher
pressure regions, and the sudden collapse
can induce intense localized shock waves
that may erode and pit a metal surface. Cavitation in pumps is a common cause of pump
failure and is a complex problem with a
variety of causes.
Many cavitation problems can be avoided
if the fluid head in the suction line is high
enough that the low-pressure zone near the
eye of the impeller never drops below the
vapor pressure of the fluid. Net positive suction head (NPSH) (or,for positive displacement pumps, net positive inlet pressure,
NPIP. following the usage of the Hydraulic
Institute) is the difference between the absolute fluid head at the inlet of the pump
and the vapor pressure of the fluid (expressed in terms of head of liquid):
Chapter VI 1: Pulp Pumping and Hydraulics
523
524
(a)
The operation of medium-consistency

centrifugal pumps is typically based on high
shear forces in the inlet throat to reach a
fluid-like state in the pulp (see Fig. 3),
coupled with separation of gas entrained
in the suspension. The typical mediumconsistency pump has five functional zones
(see Fig. 7):
A. A shear zone where the fiber network is
broken down and the suspension shows
fluid-like behavior
B. The gas separation zone where air or other
gases are separated from the stock by centrifugal forces
C. The pumping zone where impeller vanes
pump the stock towards the discharge
D. A fiber return zone where fibers entrained
in the separated gas are returned to the.
pump discharge
E. The degassing zone where separated and
purified gas is removed to the degassing
unit.
Many of the differences between various
medium-consistency
pumps on the market
lie in the way gas is separated from the pulp
and in the way the pulp is brought to the
impeller. Four commercial examples are
shown in Fig. 8.
Goulds medium-consistency
pump removes air through balance holes in the impeller shroud. A dynamic vane on the back
of the impeller is part of the secondary separation strategy to separate fibers and air. The
air may be connected to a vacuum line or
to the atmosphere, depending on pumping
conditions. As with the Ahlstrom design,
an inducer is used to break up the fiber net-
Fig. 7. Impeller -furll

typkIIl rentrlfuglll pump
usedfur medl"m-consisteney pulp.
work entering the suction line. A consistency range of up to 16% is claimed.

A former Sunds Defibrator pump (the
CMB series) for medium-consistency
pulp
features a centrifugal pump preceded by a
screw feeder that is designed to oversupply the pump with pulp. As a result, there
is overpressure in the pump housing inlet
which forces a return flow of pulp through
openings along the center of the feeder.
This return flow removes some air from the
pulp, making a separate air removal system
unnecessary. The manufacturer
claims a
pulp consistency range of up to 12%.
A new pump design, developed jointly
by Sunds Defibrator and ABS Pumps, does
away with inducers and screw feeders before the impeller, placing the impeller directly against the face of the supply vessel.
This is achieved with a modified impeller
that offers a large open area for stable flow
and provides for direct air removal. like
most centrifugal pumps for medium-consistency pulp, a vacuum system is included
for air removal though it may not be necessary under stable operating conditions.
Operating guidelines
Fiber network properties vary. It is important to establish the impeller's minimum
rotation speed to bring stock of given consistency to a fluid-like state. The critical impeller speed may vary as stock properties
change. The fiber suspension rapidly resumes its network character upon leaving
the pump volute, and returns to the plug
flow regime.
The large volumes of gas present in typical medium-consistency
pulp can defeat
centrifugal pumping unless proper degassing is performed. Without degassing, gas
may accumulate in the rotational center
until the pump housing is filled with gas.
Because the pressure rise across the impeller is proportional to the density of the fluid,
a gas-filled impeller generates negligible
pumping power and pulp flow ceases. A
suitable discharge gas flow must be maintained. This is achieved by creating a positive pressure differential between the pump
inlet and the degassing line. No vacuum
devices are needed if the suction side head
(b)
(c)
(d)
FIg. 8. FtnwtX1lllrlln'l:W
3500, (c) C8mmt
"""-consIsteney
S
Defilnwtor
rentrlfuglll
pump
pumps:
(eM Series),
(II)AblstromMC"
(d) ellrller
S"W
pump, (b) GmllIls Model

De.fi1wlltor CMB serres.

pulp enters the suction. Usually a feeder is
used (integral with the pump or a separate
unit) to ensure that pulp reaches the suction entrance of the pump rotor.
The NPIP (net positive inlet pressure)
for a positive displacement pump can become important when a steam mixer is used
before the pump, especially at temperatures
over 80C. Steam bubbles in the stock may
cavitate (collapsing violently) as the stock
moves toward the high-pressure end of the
pump.
Inlet flow variations to a pump operating at fIXed speed require that the pump
handles a varying amount of air in open
suction mode. This is readily done if the
overcapacity
remains around 10-25%. If
operated at much higher overcapacity to
handle a larger range of flow rates, tlie
pump is compressing and expelling large
amounts of air and suffers from poor performance due to air slip (compressed air
escaping through pump clearances, decreasing the discharge head).
Rotary positive displacement pumps tend
to be self-priming. They are well-suited to
highly viscous flows. They tend to have high
efficiency, leading to lower energy costs.
Air content and cavitation is often less a concern than in centrifugal pumps, but NPSHR
ratings are usually more difficult to establish for rotary pumps, making cavitation
problems sometimes difficult to predict.
Open-feed pumps, such as gear pumps and
screw pumps for medium-<:onsistency pulp,
may have no suction head requirements.
Positive-displacement
pumps can run
easily with simple, fixed-speed drives and
without vacuum systems or related control
equipment.
pumps usually
have large pumping cavities which permit
them to handle a large number of solids and
foreign objects. However, objects larger
than the cavity which resist breakup may
jam the pump, causing stoppage. If stoppage occurs, the pump can often be reversed to allow removal of the offending
object, and no serious damage to the pump
may occur.
Several possible disadvantages to positivedisplacement pumps must also be consid-
521
ered. Positive-displacement
pumps tend to
be more expensive than centrifugal pumps.
The cost may be higher by 50% or more for
a given application. The higher purchase
cost must be weighed against the lower
costs achieved by higher efficiency, less
peripheral equipment, and simpler operation.
If a positive-displacement
pump is damaged by foreign objects or other problems,
repairs can be expensive (on the order of
$30,000 for a typical pulp pump) because
of the precise machining and small tolerances required. In some pumps, small
changes in clearances caused by wear may
significantly decrease pump performance
so maintenance tends to be more frequent
than for centrifugal pumps. Actual service
needs vary widely depending on the type
of pump, the application, and the preventative maintenance program.
4. Pumping
of pulp
4.1 Low-consistency
pulp
Flow disturbances before the pump inlet such as elbows or bends increase the
likelihood of cavitation and increase the
true NPSHR beyond the manufacturer's recommendation. Poor layout of the inlet piping to a pump is a common problem in the
pulp and paper industries, contributing to
the widespread occurrence of pump cavitation. Careful consideration of inlet pressure requirements is essential to designing
a good pumping system. In designing a
pump system, the highest possible pulp
temperature that might be encountered in
the line should be used in calculating the
vapor pressure for NPSH estimations.
Horo and Niskanen (27) found that
NPSHR values or centrifugal pumps were
often not reliable for pulp suspensions because the head required to avoid cavitation
did not follow the expected trend as fluid
temperature was changed. They found that
a higher suction head is needed for pulp
than for water and that the additional head
required increases with consistency. Users
of centrifugal pumps for stock should inquire how the NPSHR value was determined: If it was determined in water flow,
522
additional head may be needed for pulp

flow. A common problem with mediumconsistency pumps is that an increase in
consistency leads to a drop in pulp density
that may lower the available suction head
in a standpipe enough to cause cavitation.
A useful concept in failure analysis of
pumps caused by cavitation is suction specific speed, a parameter that describes inlet conditions
for geometrically
similar
pumps (28).
Operating at excessively high speed is a
well-known cause of cavitation. Less known
is the danger of operating at too Iowa speed
or at too Iowa flow rate. In this case, the
flow pattern in the pump changes: Instead
of regular stream lines leading from the inlet to the outlet, recirculation zones occur
having eddies of fluid spinning inside the
pump.The flow separation that occurs may
lead to damaging cavitation and loud noise
in the pump. Cavitation damage can then
occur even when the suction head available
is well above the NPSHR.A review of several aspects of this problem is presented in
(29). Furthermore, the thrust on the shaft
and bearings are much different than at normal speed, leading to an imbalance of forces
that can cause premature bearing failure.
To increase the NPSH of a system, several strategies can be considered (22). Solutions involving changes to the pump
include:
Using an oversized pump for applications
with "small" head requirements. (Highhead pumps operating at flow rates well
below the intended range are subject to
cavitation and excessive shaft stresses, as
discussed above.)
Using a double suction impeller design
to reduce the NPSHR by roughly 25% at a
given speed and flow rate.
Use of a low-speed pump. (However,
these tend to be less efficient and more
expensive than higher speed pumps.)
Increasing the size of the impeller eye to
reduce the velocities in the impeller inlet. (There is a danger of operating at too
Iowa velocity if the eye is oversized; in
this case ,internal recirculation can occur
which lowers efficiency and shortens
pump life.)
Adding an inducer to the impeller

Using a multi-stage pump
Adding a small booster pump to increase
the head in the suction line to the main
pump
NPSHR can also be increased by modifying
the flow to the pump. Strategies include:
Raising the head in the suction line, typically by raising the fluid level in the tank
before the pump. This is often easiest solution.
Cooling the liquid, often with a heat exchanger or injection of cold water.
Proper approach flow into the pump is
critical for long life and good operation. This
is one of the most abused aspects of hydraulic design in paper mills. A straight run into
the suction side of the pump is preferred.
Valves or other fittings should be avoided
near the suction side of most pumps because they contribute to cavitation.
Users should insist that NPSH specifications for pumps have been properly obtained. Standards for testing have been
defined by the Hydraulic Institute (24-26).
Air can enter the flow into a pump
through leaks, packings, and through vortices that extend into tanks when liquid levels are low. Venting is sometimes needed to
allow accumulated air to be removed. For
centrifugal pumps, air content below 3%
poses few problems, but 7% or greater may
require a self-priming pump.
4.2
Medium-consistency
pumps
centrifugal
Design principles
The advent of modern medium-<:onsistency technology for the bleach plant came
with the development
of Kamyr's Me'''
pump (now made by Ahlstrom) which combined pulp fluidization,
degassing, and
pumping in a single-shaft tower discharge
unit. Gullichsen et al. (18,19) have outlined
the path taken to achieve this goal. The
manufacturer's
current MC"" pumps are
claimed to operate at consistencies up to
16%. Other centrifugal pumps for mediumconsistency
pulp are now marketed by
Goulds Pumps and Sunds Defibrator. These
pumps are described below.

is sufficiently high. This is often not the
case, so many pump installations include a
vacuum pump. This can be externally installed or built into the pump back end on
the same shaft. Fibers escape if the applied
pressure difference is kept too high. Stable
operation is reached when applied pressure
differentials are in the range of 1-2 meters
of water. The vacuum system should be interlocked with the pump drive.
Once the pump is properly tuned, up to
16% consistency can be pumped. However,
if there are significant changes in the incoming pulp (especially a change in consistency), the degassing
system of some
pumps may be out of tune, resulting in inadequate gas removal or excessive fiber
flow into the gas line. To avoid manual ~tuning, some mills simplify pump operation
by disconnecting the degassing system and
running at a lower-consistency (say, 9-10%).
Some new degassing systems offer improved stability of operation above 12%
consistency.
Pulp flow out of the pump can be controlled by regulating the pump's rotation
speed with the limitation that the speed be
above the minimum required for network
disruption. Many instalIations use throttling
for flow control. The choice of control valve
is important: Ball sector or v-sector ball
valves are preferred to guarantee stable operation. Full bore ball valves or disc valves
may provide unstable operation. The control valve should be mounted as close as
possible to the pump discharge and have
the same free diameter as the pump discharge.
Centrifugal pumps for medium-consistency pulp generally require few repairs
largely because they are designed to have
large enough clearances to tolerate foreign
materials that might be introduced with the
pulp. They are generally built of stainIess
steel or titanium and can be mounted with
the shaft horizontal or, for tower discharge,
vertical.
The flow velocity in medium-consistency
pipelines is typically near 0.2 m/s. In some
cases, this is not enough to avoid stick/slip
motion or pulsations in the flow, and op-
525
eration at higher velocities (say, 0.5 m/s) can

result in improved performance.
Centrifugal medium-consistency
pump
efficiencies
currently lie in the 35-45%
range, well below that of positive-displacement pumps. Manufacturers
are actively
working on improvements to lower operating costs. In some cases, energy lost because of low pump efficiency may be small
compared to extra energy required for heating diluted stock in the bleach plant.
Standpipes for pulp flow to centrifugal
pumps are an important aspect of mediumconsistency technology. New designs feature large columns (near 1 m diameter) with
an inverse taper (the standpipe widens toward the ground) to prevent bridging and
plugging. Dilution lines are present in the
event the degassing system fails or other
problems occur. It is important that the
proper level of pulp be maintained in the
standpipe. A common design head is 3 m.
The level in the standpipe is usually controlled with a control valve downstream of
the centrifugal medium-consistency pump.
Chemicals can be mixed into the pulp in
the standpipe and fully mixed as the pulp
passes through the pump. In some cases,
this mixing strategy can eliminate the need
for a mixer downstream.
The shear rate in the impeller zone of a
typical medium-consistency
centrifugal
pump exceeds, by orders of magnitude, that
required to break down the fiber network.
This means that the pump itself can be used
as a mixer with some limitations. For example, one manufacturer reports that approximately
three-fourths
of their
medium-consistency
pumps in bleach
plants are used for mixing. Reagents such
as sodium hydroxide and sodium hypocWorite that react slowly with pulp can be injected successfully in the pump inlet while
chemicals such as hydrogen peroxide, sodium hydrosulfite, and sulfuric acid have to
be injected through a special nozzle located
on the inlet throat. Chemicals with a high
partial pressure such as chlorine dioxide
must be injected through 'a nozzle located
on the pump volute to avoid gas escape
through the degassing system. Other cases
526
Pulp Bleaching
-Principles
require separate mixers suitable

medium-consistency
regime.
4.3 Positive-displacement
and Practice
for the
pumps
pumps for medium-consistency have predominantly been
of two types, rotary screw pumps and gear
pumps. Most rotary screw or progressing
cavity pumps for medium-consistency pulp
are twin-screw pumps, but single-rotor progressive cavity pumps are also found in
some installations.
Twin-screw pumps
Twin-screw pumps carry fluid in the
spaces between screw threads. The fluid
moves axially as the threads rotate and mesh
inside a closely fitting housing.The required
pressure gain occurs as the volume between
the threads progressively decreases because
of an axial increase in shaft diameter or an
increase in thread thickness. The decreasing volume pressurizes the fluid.The major
producer of twin-screw pumps for mediumconsistency pulp has been Warren Pumps.
Figure 6a shows an example of such a
pump. Twin-screw pumps were the most
common means for pumping thick stock
before the development of centrifugal medium-consistency pumps in the 1980s and
are still widely used.
Perhaps the main advantage claimed for
twin-screw pumps over centrifugal medium-consistency
pumps is the ability to
handle higher ranges of pulp consistency.
Current technology permits pumping stock
up to 18% in consistency, according to
manufacturer claims, and pumps that will
handle up to 25% consistency are planned
for the near future. Typical week-to-week
variations in pulp consistency do not have
a dramatic effect on pump performance.A
significant benefit for the bleach plant is the
high flow uniformity possible with twinscrew pumps.
Other potential advantages of twin-screw
pumps for medium-consistency
include
lower energy costs and the ability to handle
high gas content in the incoming stock.
Unlike the centrifugal medium-consistency
pump, positive displacement pumps do not
depend on high shear to create fluid-like
behavior in the stock, a process that requires substantial power. This accounts for
part of the energy savings with positive displacement pumps. Because degassing ofthe
stock is not needed, a vacuum pump and
the associated control equipment need not
be purchased with the pump. However,
for some bleaching processes (especially hydrosulfite bleaching), the presence of air is
harmful, so degassing may be needed in any
case. If the pulp is pumped with some air
content, further energy savings may be
achieved because of the friction-lowering
effect of air in medium-consistency
pulp
(30). Apparently, the air acts as a lubricant
between the pulp and the pipe wall, lowering friction. At 14% consistency, for example, the energy savings due to decreased
pipe friction may be on the order of 50%
compared to pumping degassed pulp. One
mechanism that may be important in achieving this friction reduction is the relatively
long dwell time the pulp suspension has in
the twin-screw pump. The shear in the
pump folds in and disperses the air in the
pulp. Much of the air is removed from the
pump by an air bleed valve, but a portion is
still present in the discharged pulp. If the
air is not well dispersed, slug flow and large
pulsations can occur.
Capital costs for twin-screw pumps are
40-100% higher than medium-consistency
centrifugal pumps. Although the pulp is
usually free of harmful foreign objects in
the bleach plant, there may be high maintenance costs if damage occurs. (Foreign
objects that might cause problems are usually the result of poor maintenance; for example, damaged repulper blades that are
not replaced can eventually fail and enter a
pump, or damaged screen straps from a
washer drum may break off and fall into the
pulp.)
Positive displacement pumps tend to do
much less mixing of the pulp than do centrifugal pumps, which is not necessarily a
disadvantage unless the chemical mixing
systems of the bleach line are marginal.
The design of the feed system for a positive displacement
pump is important. If
proper guidelines are not followed, bridg-

ing of the pulp in a feed chute may occur,
especially above 14% consistency. The feed
line should have straight, vertical walls, no
obstructions, and the diameter should be
dimensioned so that the friction loss per
foot in the chute is less than static head per
foot of pulp.
Single-screw pumps
Similar in principle to twin-screw pumps,
single-rotor or eccentric-screw pumps are
progressive
cavity pumps in which the
moving cavities are formed between a r0tor having a single external helical thread
and the stator, which has a double internal
helical thread. The rotor is made from hard
metal (e.g., stainless steel, titanium, or other
alloys); the stator is an elastomeric material
bound to a metal housing. Though singlerotor pumps are not commonly used for
mediurn-consistency
pulp, such use is increasing in North America. Robbins and
Meyers, Inc., is a major manufacturer
of
single-rotor pumps (Moyno"" pumps) for
mediurn-consistency pulp. The pumps have
a claimed range of 6-16% consistency.
As with twin-screw pumps, low pulp
shear and low energy use are possible advantages for single-rotor pumps. Low cost
of installation is another claimed advantage
over centrifugal pumps. Single-rotor medium-consistency
pumps feature openthroat positive auger feed that does not
require air removal from the stock. Heads
up to 1 MFa (150 psig) can be generated.
The elastomeric stators are available in
various formulations for specific pulping
and bleaching conditions. In bleaching operations, bleach chemicals can sometimes
be added at the auger feed or in a section
between the feed and the stator.
Gear pumps
Gear pumps depend on the relative
movement between rotating elements and
the pump housing. Fluid is trapped in
spaces between gear teeth and moved from
the inlet to the outlet. Pressurization
is
achieved by a progressively
decreasing
pumping volume as the fluid approaches
the outlet.The primary manufacturer of gear
pumps for medium-consistency
pulp is
527
Ingersoll-Rand which produces a dual-gear

pump and a single-gear pump that intermeshes with a screw to drive the pulp (see
Fig.6b). The latter system (termed CloveRotorTM) can manage consistencies up to
35%. At high-consistency the pulp cannot
be pumped long distances because of the
high pressure drop, the danger of plugging
and the risk of intense vibrations. However,
the pump is used to feed some high-consistency processes and storage tanks. Most
gear pump installations in bleach plants are
for medium-consistency
operation (some
users give a limit of roughly 14% for "typical" operations such as feeding the top of a
tower
from ground
level). Oxygen
delignification
and bleaching stages are
common candidates for this pump.
Besides a broad consistency range, these
pumps offer other potential advantages. No
discharge control valve or other control
equipment is required, no priming is necessary, degassing systems are not needed,
efficiency is high, and friction losses in the
pulp are claimed to be 5-10% lower than
when pumped by centrifugal pumps because of a friction-lowering effect from the
air in the pulp. The difference in pulp-gas
mixing may account for the different degrees of friction reduction obtained by the
gear and twin-screw pumps, and the latter
is capable of greater friction reduction in
many cases. There also tend to be fewer
problems with pulp feed to the pump, perhaps because of the mechanical vibration
of the feed system induced by the pump
itself.
Although the gear pump for medium-consistency pulp has been a long-used device,
it is inherently subject to flow pulsations
as the gears sweep through the casing.
These pulsations induce a stick/slip motion
in the pipeline where the cycle of acceleration/deceleration
increases the normal friction losses. Air content can be a problem
because the air is not well dispersed in the
pulp during its brief passage through the
pump. Slug flow can occur, leading to large
pulsations in the line. In medium-consistency flow, the pulsations can be severe
enough to cause hammering that can cup-
528
ture steel piping. Some gear pump users

report the need to dilute the stock below
10% consistency to avoid pulsations. By reducing the air content, avoiding steam mixing just before the pump, and controlling
pulp properties,
steady operation
with
medium-consistency
pulp above 10% is
possible.
4.4 Design of medium-consistency

systems
Medium-consistency pumps can be used
in many applications (see Fig. 9).The most
common applications are pumping from a
dropleg and tower discharge. For tower discharge, a scraper is often needed in the
tower bottom (as shown in Fig. 9), but this
is not mandatory. No tower scrapers are
required if one can accept that some pulp
is left in the tower on emptying. Mediumconsistency pumps can be used to feed several stock lines, one by one or several lines
simultaneously as shown in Fig. 9.The latter case requires that the flow splitter be
equipped with a rotating device to break
down the fiber network before flow splitting. Medium-consistency pumping can be
used for long-distance transportation (several hundred meters) by installing pumps
in series. Only the first pump in the chain
needs degassing.
Delivery of medium-consistency
pulp
into a pump deserves special attention.
Centrifugal pumps require a certain head
of pulp over the pump inlet to establish
flow, but open suction pumps must have a
feeder to physically move the material into
the pumping rotor. In designing the feed
system to a pump, the relation between
stock density and frictional head losses in
the chute must be considered. As consistency increases, the density of the stock
decreases and the network strength and
wall friction increase, making bridging and
other feed problems more likely. Figure lOa
shows the suction head available per foot
in a vertical column of pulp; Fig. lOb shows
the frictional he1d loss for 18% consistency
pulp in a rectangular feed chute (50 cm x
85 cm) as a function of flow rate (31).
Above 500 tpd, the frictional losses in the
Fig. 9. Use of nmU.",-etmSistertey
dertsltySlortlp t_
]I1ImJlsfor blgb-
disekrge (Ahlstrom).
chute would exceed the head because of

gravity. In this case, bridging may occur in
the chute or the flow rate may become erratic. A feed screw or agitator in the feeder
may then be necessary.
a)
:B
~
(b)
0.8
~0.8
0
to
.,...
'(0
>
as -.E 0 .6
-00
as C\I
~ 0.4
c::
o
. 0.6
000
~::I
529
~0.4
:CE
as
Q)
I
0.2
U)
0.2
0
10
12
14
16
Consistency,
18
%
20
500
1000
ADT per day
1500
Fig. 10. Rel4timlsbips be,..,.

sru;tImI betuI ad betulloss lit tbe feNt clnlte for medi"m-crnuistetu:y flow;
(.) Allldlllble sru;tImI betuI per _ter of stoell /IS..frurditm of COIISIstnlCy;(b) Frktkm4liosses
lit tbe
cInIte for 18% stoe" /IS. ftmdlml of flow ~e (31).
Stock velocity plays an important role in

the stability of a hydraulic system. For typical pipelines, velocities of 0.15-0.5 mls are
generally preferred. At velocities below 0.15
mis, there may be partial separation of the
phases (water, air, and fibers) which, in
some cases, can lead to pipeline pulsations,
plugging of valves, or nonuniform flow.
In practice,
pipelines
with mediumconsistency centrifugal pumps tend to run
in the range of 0.15-0.3 mis, lines fed by
positive displacement pumps may run up
to 0.5 mls.
Flow stability is essential for mixing and
refining. Better stability is achieved with
higher velocity. For stable flow at mediumconsistency, the flow velocity from the
pump should be at least 2 mls.The velocity
should be even further increased just before the flow enters a refiner. For mixers
and refiners, the distance from the pump
should be kept under 10 m if possible. If
the line must be longer, the velocity should
be maintained at 0.3 to 0.6 mls for most of
the distance, then increased in an abrupt
step (through a reduction in pipe diameter)
to a velocity of at least 2 mls to stabilize the
flow (31).
Although pipelines for medium-consistency stock should be kept as short as possible to avoid pulsations and to conserve
energy, long transfer lines can be operated
with little pulsation if the flow velocity is

maintained in the 0.15-0.6 mls range. If the
flow velocity becomes low 0.15 mls) and
if there are perturbations such as a series of
valves and elbows downstream of a long,
straight run, large pulsations may take place.
These pulsations stem from the combination of a compressible
air-laden volume
which alternately compresses and expands
as it approaches and passes zones of increased flow resistance (obstacles). Pumps
that remove much of the air, such as centrifugal pumps or twin-screw pumps, decrease the likelihood of pulsations.
5. General considerations for design

of pumping and piping systems
An excellent discussion of design considerations for slurry pumps in general is offered by Wilson et al. (32). Guidelines for
centrifugal stock pumps are found inTAPPI
Technical Information Sheet 0420-10 (33).
5.1 Power requirements
and pipe size
Many pump systems have been overdesigned because of uncertainties

about
pulp friction. Improved data for practical
fiber suspension flows are needed.There is
a great need for laboratory tests that could
be used to accurately predict the flow properties of a pulp. Currently, no set of tests is
entirely adequate.
530
Pulp Bleaching
-Principles
and Practice
One of the major problems is that the

data used for design are based on measurements in ideal piping systems with long,
straight runs, but the piping systems in typical mills are a maze of elbows, valves, and
joints. For example, in designing the pumping system for a bleach plant, one paper
company recently reported that various sets
of correlations for pressure drop were as
much as 200% in error and most of the error was due to the pressure drop in elbows.
There is a serious need to better understand
pulp flow in elbows and other nonideal
flow geometries.
Pressure drop predictions
for typical
medium-consistency operation are generally
reasonably accurate. For example, correlations for medium-consistency
transport using twin-screw pumps have been verified
over a 35-year period and typically predict
pressure drop within 10% if a small to moderate amount of air is present and if the velocity is at least 0.15 mls.
It is important to know the full range of
pulp consistency that a pump will encounter during normal operation as well as the
range of flow rates and the range of discharge head. The pump should be able to
handle the most extreme requirements to
be imposed on it without being overburdened. Sudden decreases in pulp consistency also must be considered because a
lower consistency may let the pump surge
to a flow rate high enough to overstress
it (34).
5.2 Selection of pump size

Because energy and capital equipment
costs have become more important considerations in selecting a pump, purchasers
now increasingly seek the smallest, most energy-efficient pump that can meet specifications. At the same time, existing mills
often seek to operate their equipment beyond the original specifications
which
sometimes leads to pumps being operated
beyond the best efficiency point in a region
where cavitation damage, erosion, and excessive shaft stresses may occur. The result
is shortened pump life. It is wise to anticipate the possibility of future flow increases
in a system and to carefully consider the

economic trade-offs between pump size,
operating costs, and pump life in off-design
flows.
Optimum performance of a pump occurs
at only one point on the three-dimensional
surface plot of kinetic head as a function of
speed and flow rate. Users should not overemphasize pump efficiency at the expense
of pump lifetime and overall performance
across the expected range of pumping conditions.
5.3 Materials for pumps and pipes

In the bleach plant, stainless steel alloys
are the dominant materials of construction
for modern pumps. Cast iron casings are
still common. Modern impellers are no
longer bronze or iron but are overwhelmingly stainless steel. Rubber or polymer linings, which may break off with wear, are
less used. When bleaching chemicals are
injected directly into the pump, special
materials are often needed. For chlorine
dioxide injection, titanium is often specified. If chlorine is injected into a pump
(not common), or if high residual chlorine
passes through a pump, Hastelloy or other
chlorine-resistance
alloys are needed; titanium is not recommended. In medium-consistency pumps for ozone bleaching, 317
stainless steel is preferred. For oxygen treatments, stainless steel is usually adequate.
Although fiberglass has proven useful in
some low-consistency pipelines, pulsations
in medium-consistency
flow may lead to
rupture, especially at elbows. High-strength
piping (stainless steel or titanium) is usually used for elbows.
5.4 Pressure measurement

Pressure measurement is recommended
in both the suction line and the discharge
line. Previously, Boudon gauges were used,
but electric pressure transducers are now
recommended.
Ring-type tapping points
should be located no closer than one pipe
diameter past the pump discharge. Unes
connecting tapping points to a transducer
should have valving to permit backflushing
with water.
5.5 Partial flow

In the design of hydraulic systems, pump
performance
at the best efficiency point
(B.E.P.) is often the main factor considered.
However, temporary swings and long-term
modifications often leads to off-design flow
conditions that shorten pump life. It is important to plan for reduced flow conditions
especially when oversized pumps are used.
Pump damage at low flow is a common
problem and is much different than the
problems that occur at high flow or with
low NPSH.
Bypass loops that recirculate part of the
flow are a common means of operating at
low flow without damage to the pump.The
temperature rise in the pump is the key factor to consider in determining the amo~t
of recirculation (Garay, p. 107). Garay discusses several options for recirculating flow
control (p. 128 ff.).
Low NPSHR pumps (especially those
with large impeller eyes) may experience
low-frequency pulsations (8Hz or less) under low-flow conditions with internal recirculation in the impeller eye. Impeller vane
inlet angles at low flow do not correspond
well to the flow, leading to flow separation
on the back of impeller vanes which in turn
can cause cavitation. This problem is not
easily detected by head loss as is normal
cavitation from inadequate NPSH.
5.6 Elbows, valves, flanges, supports

Control valves are commonly required on
the discharge side of centrifugal mediumconsistency
pumps to regulate the flow
rate. Valves or other fittings should be
avoided near the suction side of most
pumps because they contribute to cavitation.
Medium-<:onsistency process and transfer lines are normally sized for low flow
velocity and are therefore large in diameter.
These lines, when full, have great weight
yet usually have small structural stiffness
(pipes are typically Schedule 10 to Schedule 40) .'I'his requires special care with pipe
supports. A further problem is the large
thermal expansion that can occur when the
pipes are heated from room temperature
531
to process temperature, causing large forces

and moments on pump flanges. Therefore,
discharge lines should be rigidly supported
near the pump. Poor piping support or
simple fulcrum-type support near the pump
is the primary factor requiring pump maintenance for medium-<:onsistency applications.
Pulsations in medium-<:onsistency flows
is a common problem, especially at or above
14% consistency. Pipelines should be firmly
anchored, instead of supported by hangers,
and bends or elbows should be supported
with thrust blocks to prevent deflection. In
medium-<:onsistency pipelines, more stable
operation has been experienced with 90"
elbows as opposed to 45 elbows (35).
5.7 Pump drive trains

The power demand of a pump is given by
Power
= Q6P
- 11
[5]
where Q is the volumetric flow rate of the

pulp suspension (m3/s), M is the pressure
gain across the pump, and is the fractional
pump efficiency. 6P can be expressed in
terms of the hydraulic head in height of
suspension:
[6]
where p, is the suspension density,g is gravitational acceleration, and H is the hydraulic head in units of length.
For many pumps, the pressure gain delivered decreases as the flow rate is increased, often resulting in a maximum
pump power at some flow rate.
Direct drives for slurry pumps are not
common. Generally, drives for pulp pumps
operate at a fixed high speed (e.g., 1750
rpm) with a speed reducer and coupling
connected to the pump. Gears and V-belts
can be used to adjust shaft speed.
Variable-speed drives allow great flexibility in mitt operation but are less eMdent
and more expensive than fixed-speed motors. However, they can provide large cost
savings for mills that frequently vary ton-
532
Pulp Bleaching
-Principles
and Practice
nage rates or consistency. Variable-frequency drives should be considered for

mills that use many storage tanks because
the tanks allow substantial flexibility in operation which usually means that flow rates
and consistencies through a given pump are
likely to vary frequently.Variable-frequency
drives are also of great value during startup
because the ability to gradually increase
flows and pressures decreases the likelihood of water hammer and increases the
life of the pump by decreasing startup
stresses.
Shaft couplings should be chosen to permit pump operation even when shaft misalignment occurs and to allow impeller
clearance to be adjusted as wear occurs.
Base plates are important in maintaining
pump alignment. The plate must be able to
resist high torque and vibrations.When high
pump loads are required, a stress analysis
of the pumps and pipes may be needed. A
well-grouted baseplate and properly supported pipe are essential to good operation.
If an expansion joint is used to decouple
piping forces and moments on the pump
discharge, it must have tie rods set to prevent piping pressure load from overloading
the pump flange.
For medium-<:onsistency pumps, double

mechanical seals are the standard. These
are required for the vacuum air-removal system to function properly. Double mechanical seals are commonly used in applications
where a pump may run dry. They prevent
leakage from the pump and prevent dilution of the stock. Chlorine dioxide bleaching stages
increasingly
use double
mechanical seals to stop leakage contributing to effluent.
Split-seal technology has become relatively popular in the pulp and paper industry because the seals are easy to install.
Cartridge seals are also finding increased acceptance.
Useful guidelines for meeting environmental regulations with mechanical seals
are given in Ref. (37). Specific guidelines
for the pulp and paper industry are published byTAPPI (38).
5.8 Seals
5.10 Filtrate air

Filtrate lines from washers in bleach
plants should have large retention tanks to
allow good removal of air. Entrained air in
the filtrate can lead to severe damage in following stock pumps. Air in the stock also
reduces filtration efficiency and lowers
washing capacity. New pump and filter systems have been developed in recent years
to remove air from filtrate lines.
5.9 Potential of sealless pumps

A variety of sealless pumps, such as magnetic pumps, offer complete protection
against leakage and dilution. High expense
and the inability to run dry are disadvantages of these systems, but they are finding
applications for chemical delivery systems.
Although most stock pumps in Europe

use mechanical seals, packing dominates in
North America. One representative
of a
major pump supplier noted that 95% of the
low-consistency
pumps sold by it use
packings rather than seals. However, the
trend is clearly away from packings and toward mechanical seals. This trend is driven
primarily by environmental
concerns.
Packings increase water use and result in
more effluent though they are simple and
inexpensive. A conversion to mechanical
seals may be necessary for many applications, not only to reduce water consumption, but also to prevent pollution from
leaks. Expeller-type seals are used in some
5.11 Maintenance
Pumps used in the pulp and paper industry have some of the highest mean time between failures of all available industrial
pumps, permitting continuous operation
for many months. However, failures still oc-
~ul~ 1~~lic1tions where dilution is undesirable; however, these are associated with
efficiency losses typically on the order of
3% (36).
poorly. It is advisable to keep a spare rotating assembly for every pump to ensure that
pump failures result in minimal down time.
cur, especi1lly
when the I'urnl' i~Of'ef'Jrell
Chapter VII: Pulp Pumping and Hydraulics

Pumps can be damaged in many ways:
by flow too far below or above the best efficiency point, too low a suction head,
improper startup, and sudden changes in
consistency. Regular inspection and maintenance is vital. Visual inspection of pump
parts is important: the observations should
be recorded to permit analysis of changes
and trends. Impeller inlets, blade surfaces,
and corners between vanes and shroud
should be checked as should the pump
shaft. Photographs are a useful tool.A mirror may help provide access to the back of
vanes. Inspections may be spaced with intervals of a few months to a year, but inspections should be held after the first
startup and after significant changes in operating conditions.
More sophisticated inspection tools may
be applied for critical applications if desired.
These tools include hydrophones for signal
analysis and accelerometers
for vibration
signature analysis.
'.
Operating conditions should be recorded

regularly: these include consistency, temperature, pH, pulp type, chemical concentrations, speed, flow rate, discharge head,
and suction head. For critical pumps, these
data should be evaluated jointly with the
manufacturer.
Regular inspection and troubleshooting
of mechanical seals is especially important.
Only 5% of these precision devices achieve
their expected lifetime; most fail early because of improper operation and poor maintenance (39).
In all cases, a proactive policy of regular
maintenance
and inspection to prevent
pump damage is recommended instead of
troubleshooting once problems set in.
5.12 Control and stability issues
For controlling flow rate, past strategy
has typically called for control valves to
throttle the flow being pumped by constantspeed motors. A modem trend, especially
outside North America, is to use variablespeed drives instead of control valves. This
may be economic when the pump power
exceeds 25 kW
533
pumps do not require regulation and must not be regulated
by a valve.
The principles of pump control and stability are presented in the Pump Handbook
of Karassik et ai. (40).
5.13 Start-up
For pumps with heated fluids, it is wise
to warm up a pump before startup to prevent misalignments or high stresses due to
strong thermal gradients. Garay (p. 124)
advises that all parts of a pump should be
held within 25C of each other. Pumping
hot fluids (fluids hotter than the pump by
35C or more) with a cold or partially
warmed-up pump may damage the pump
severely.
Water hammer can occur during pump
startup, and needs to be carefully considered. When a surge of fluid forcefully impacts an empty elbow or valve, a shock
wave can be generated that can damage the
pipeline, even rupturing
components.
When a pump is turned off, pulp may drain,
resulting in evacuated regions that can contribute to hammering. A solution is to gradually increase the flow on startup, beginning
with closed discharge valves that are slowly
opened manually or by installing automatic
ramping valves on discharge piping. (positive-displacement pumps must not have discharge valves.) Variable-speed
drives, if
available, can be used to ramp the start-up
velocity.
5.14 Flow metering
Magnetic-flux meters, or simply magmeters, are generally preferred for measurement of flow rates in pulp suspensions and
other slurries. These meters do not interfere with the flow, offer high accuracy (0.5%
of full scale is commonly claimed), and can
remain accurate over a wide range of consistencies (low- and medium-<:onsistency
flows).The reading from magmeters is proportional to the velocity of the conductive
fluid (water) passing through a magnetic
field; it does not directly measure the mass
or liquid volumetric flow rate. If there is a
significant amount of gas in the flow, the
534
flow rate obtained from the meter is inflated

because the velocity ofthe pulp suspension
at a given mass flow must increase as the
volume fraction of liquid in the pipe is decreased (void volume is increased).
Magnetic flow meters should be of a lowfrequency impulse type which is less sensitive to entrained gas in the suspension. Recommended magnetic flowmeter location is
on a straight pipe as close as possible to
the pump discharge and before the control
valve where suspension velocity is still high.
Magmeters are susceptible to stray electric
fields and must be properly grounded.
illtrasonic flowmeters are often used for
low-consistency
flows. The most commonly employed are Doppler meters and
transit-time meters. Doppler meters measure the frequency shift of an ultrasonic signal imparted
by the moving fluid to
determine
fluid velocity.
Transit-time
meters determine fluid velocity by the difference in the time of flight for ultrasonic
signals traveling upstream and downstream.
Doppler meters require particulates
or
bubbles in a flow to scatter the signal and
impart a Doppler shift to an ultrasonic signal and can work well in dilute pulp suspensions (0.1-4% may be general good
range, with measurements at higher consistencies possible depending on the instrument and the pipe).With proper calibration
for a particular pulp, Doppler meters may
have accuracy near 1%.Transit-time meters
are capable of high accuracy with little calibration but are unlikely to succeed at consistencies above about 2% because of signal
attenuation (41). If many gas bubbles are
present, the transit-time meter is likely to
fail at even lower-<:onsistency.
Both types of ultrasonic meters are available as fixed installations and portable
clamp-on units. Clamp-on units may have
less accuracy because they can be influenced by defects and variations in pipe
properties and variation in the installation
but are useful in auditing flow systems.
Acknowledgment
Many individuals and companies provided assistance for this chapter. Special
thanks are due to Elliot Blackwell and Ray
Barufaldi of Warren Pumps; Bruce Conner
of Goulds Pumps; Frank Steffes and Paul
Flickinger
of Sunds Defibrator;
Jeff
Rounsaville
of Ingersoll-Rand;
Kaj
Henricson of Ahlstrom Machinery; Mike
Chervenic of ABS Pumps; Elton Krogel of
Durametallic Seals; Dave Evans of Peak Instruments; John O'Brien of Controlotron;
Tom McDonough of IPST;Thomas Hagler,
Jr., and G. R.Addie of Georgia Iron Works;
Geoff Duffy of the University of Auckland;
Ben Thorpe of James River; and Karol
Kocourek of James River.
References
1. Lee, P.F.W. and Duffy,
22(4):750 (1976).
G.G.,
AIChE
J.
2. Duffy, G.G., Titchener,

A.L., Lee, P.F.W.,
Moller, K.,Apptta
29(5):363 (1976).
3. Mih, Wand
(1%7).
Parker,].,
Tappt
50(5):237
4. Daily, J.W and Bugliarello.

44(12):881 (1%1).
G., Tappt
5. Daily, ].W. and Bugliarello,

44(7):497 (1961).
G., Tappt
6. Norman,
B.G., Moller, K., Ek, R., Duffy,
G.G., "Hydrodynamics
of Papermaking
Fibers in Water Suspension,"Transactions
of
the Fundamental
Research Symposium
at
Oxford. BPBIF, London, 1977, p. 195.
7. Kerekes, R.J and Gamer, R.G., Trans. Tech.
Sect., CPPA 8(3):TR53 (1982).
8. Lee, P.F., "Predicting
Local Velocities
and
Pressure Gradients in Thrbulent Fiber Suspensions,"
International
Symposium
on
Papermachine
Headboxes,
McGill Univ.,
Montreal. 1979, p.36.
9. Moller, K.and Sullivan,
57(3):165 (1974).
M.].O.,
Tappt
10. Moller, K., Tappt 59(8): 111 (1976).
11. IMPI TIS41().I;, "Optimum Consistency

for Pumping Pulp,"TAPPI PRESS,Atlanta.
1993.

12. TAPPITIS 410-14,"Generalized
Method for
Determining
the Pipe Friction Loss of
Flowing Pulp Suspensions,"TAPPI
PRESS,
Atlanta, 1993.
13. TAPPI TIS 410-412,"Pipe Friction Pressure
Loss of Pulp Suspensions:
literature
Review and Evaluation of Data and Design
Methods,"TAPPI
PRESS,Atlanta, 1993.
14. Duffy, G.G.,APPITA
42(5) 358 (989).
28. Rayner, R.E., Chem.

(993).
29. Schiavello,
(992).
30. Longdill,
41(6):456
535
Eng. Prog. 89(3):79
B., Chern. Eng. Frog. 88(11):35

G.R. and
(988).
Duffy, G.G., Apptta
31. Blackwell, E., Warren Pumps, Warren, MA,

personal communication.
15. Laskey,H.L., TapptJ 71 (6):790988),see

also a correction
in Tappt J 71 (9):135
(988).
32. Wilson, K.e.,Addie,

G.R., Clift, R., Slurry
Transport
Using Centrifugal
Pumps,
Elsevier Applied Science, London, 1992.
16. Higgins,
65(3):131
33. TIS 0420-10 "Horizontal End Suction Centrifugal Stock Pumps," TAPPI PRESS, At-
B.G. and Wahren,

(982).
D., Tappt
17. Dosch, J.8., Singh, K.M., Stenuf, T. J., "Air

Content of Medium and High-consistency
Pulp Slurries," 1986 TAPPI Engineering
Conference
Proceedings,
TAPPI PRESSJ
Atlanta, p. 721.
18. Gullichsen,
J. and Harkonen,
64(6):69 (981).
E., Tappt
19. Toivo, N.; Frey, S.;jorma, T.;"Method and

Apparatus
for Pumping
Fibre Suspensions," U.S. Pat.4,435,122
(March 6,1984).
20. Gullichsen, J., Harkonen,
Tappt 64(9):1130981).
21. Bodenheimer,
32(9):420%9).
E., Niskanen,
V.B., South.
Pulp
T.,
Pap.,
22. Garay, P.N. ,PumpAppltcatton

Desk Book,
Fairmont Press, lilburn, GA, 1990.
23. Pyotsia,J.
(990).
and Palo, T., Tappi J 73(4):271
24. "Centrifugal Pump Test Standards,"m

1.6,
Hydraulic Institute, Parsippany, NY, 1993.
25. "Centrifugal
Pump Standards,"m
1.1-1.5,
Hydraulic Institute, Parsippany, NY, 1993.
26. "Rotary Pump Standards," m 3.1-3.5, Hydraulic Institute, Parsippany, NY, 1993.
27. Horo, K. and Niskanen,T.,
(978).
Tappi 61(1):67
1anta' 1988.
34. Homer,
E, PaPier
33(3):93
35. Barafaldi, R., personal
(979).
communication.
36. Wilson, K.e. , Addie, G.R., Clift, R., op. cit.,

p.187.
37. "Guidelines for Meeting Emission Regulations for Rotating Machinery
with Mechanical Seals," STLE Special Publication
SP-30, Seals Technical Subcommittee,
S0ciety ofTribologists
and Lubrication Engineers, Park Ridge, IL, 1990.
38. Bosar, G.J. and Krogel, E.T., "Mechanical
Seals: Guidelines for the Pulp and Paper
Industry," 2nd edn., Mechanical Seals Task
Group, Maintenance
and Mechanical
Engineering
Committee,
TAPPI PRESS, Atlanta, 1993.
39. Bosar, G.J. and Krogel,
62(3):155 (1989).
E.T., Pulp
Pap.
40. Karassik, I.J., Krutzsch, We., Fraser, WH.,

McGrawMessina, J.P. , Pump Handbook,
Hill, New York, 1986.
41.lindsaY,J.D.,"Evaluation
of Portable Ultrasonic Flowmeters
in Pulp Suspension
Flow," 1994 TAPPI Engineering
p.743.
SECTION VI:

Chapter 2:
Mixing and Mixers
C.P J. Bennington
and
Pulp and Paper Centre
The University of British Columbia
Vancouver, B.C. V6T lZ4 Canada
1. Introduction.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 539
2. General principles.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 539
2.1 Goals of mixing and mixing scales
. . . . . . . . . . . . . . . . . . .. 539
2.2 Pulp suspension rheology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 540
2.3 Mixing gases intI) pilip suspensions
542
3. Mixing in pulp bleaching
3.1 Mixing quality.
3.2
Mass transfer,
3.3 Mass transfer
544
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 544
reaction
rate, and mixing
after mixing
rate.
. . . . . . . . . . . . . . . . . . . . . . . . . . 544
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 545
4. Mixersusedforpulpbleachlng
4.1 Low-<:onsistency mixers
4.2 Medium-<:onsistency mixers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3 High-<:onsistency mixers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5. Mixing Practice.
546
546
549
554
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 554
5.1 Equipment use in mills
. . . . . . 554
5.2 Mixing assessment.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 557
5.3 Estimates
quality.
of mixing
5.4 Mixing rate in industrial

5.5 Mixing in the laboratory
5.6 Economics
of improved
5.7 Troubleshooting.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 561
mixers
562
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 563
mixing.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 563
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 564
537
Chapter VI 2: Mixing and Mixers
Chapter VI 2:
Mixing
and Mixers
1. Introduction
Good mixing is a critical requirement for
effective pulp bleaching.This principle has
been demonstrated in many mills and laboratories where more efficient mixing has
been observed to reduce chemical consumption and improve pulp quality (1-13).
Together, these benefits provide an important economic incentive for achieving good
mixing in bleaching operations.
A discussion of mixing theory and principles can be found in several books (1"423). The fundamentals of mixing in pulp
bleaching operations have been reviewed
by Bennington et ai. (24); a description of
older pulp mixing equipment is available
in an book chapter coauthored by Perkins
and Doane (25) and pulp agitation has been
discussed by Yackel (26).
Many types of mixers have been used in
pulp bleaching applications over the years.
Mixer design has progressed as a result of
practical experience and with increasing
knowledge of mixing principles and pulp
rheology. In addition, as bleaching processes have evolved, so have bleaching
chemical
mixers. For example, the increased use of gaseous chemicals in bleaching has necessitated
development
of
efficient gas-pulp mixers. This chapter reviews these developments as well as the
current technology and understanding of
mixing in delignification and bleaching operations.
2. General principles
2.1 Goals of mixing and mixing scales
The objective of any mixing process is
to commingle two materials to produce a
uniform distribution of one in the other. For
pulp bleaching, exposure of each fiber to
the correct amount of bleaching chemical
must be ensured. To achieve a well-mixed
state, nonuniformities must be eliminated.
539
540
These may be of varying scales, as illustrated

in Fig. lea) which portrays a hypothetical
longitudinal concentration profile in pipe
flow. The concentration
variations span a
wide range of sizes - from distances which
are large with respect to the pipe diameter
down to distances of about a fiber diameter or less.
Tllbk

1: MixI"g
St:llles
I" In"p
blHcbl"g.
Mixing
Dimension
Scale
Designation
Approximate
Size (mm)
Large
Macroscale
>10
Small
Fiber-scale
0.05 - 10
Very small
Microscale
< 0.05
Mixing Achieved
Primarily by
Bulk motion
Laminar and turbulent
shear, diffusion
Diffusion aided by
small-scale fluid motion
Concentration
(8)
Small-acala
mixing by local ahear and diffusion
(b)
Fig. 1. Process flOflJS Htle etmt:tmlrtltUm
flru:llulof St:llles or tItstUms IHI SJMfI . spec""""
(.). B.IIII "0110"

I."ees .s sbow" I" (_k)
fJllriIIell",lutes
IIIrge-St:IIk
tUms wblk Weill sl1ellr II1Id tlljf'llslqtl ell",,smIIIl-SCIIk (ftber-_k
II1Id ",leroseIIk)
""'e
(b).
fJllrilltUms
lIS sIHntnt
I"
Nonuniformity scales may be defined in

a number of ways. One useful basis is the
distance of relative motion required to even
out concentration variations. As illustrated
in Fig. I (b), large-scale or macroscale variations require backflow or bulk movement
of fluid over relatively large distances for
homogenization. Macroscale distances can
span sizes ranging from 10 mID to a pipe
diameter or larger. Small-scale variations can
be removed by shear - IOeID rel1tive fluid

movement induced by velocity gradients or
turbulence,
and by diffusion
- molecular
movement induced by concentration gra-
dients. Because fiber suspensions are discontinuous over small distances, it is useful
to define two small scales of mixing: a fiber-scale to represent nonuniformities having a size comparable to fibers and flocs,
and a microscale to represent nonuniformities approaching the molecular level. Although uniformity on the latter scale is
attained by molecular diffusion, it is aided
by clump breaking and stretching (produced by relative fluid movement) which
greatly increases the surface area available
for diffusion. Table 1 summarizes these mixing scales.
The nonuniformities to be removed by a
mixer can be considered the "mixing load."
They may originate in flows external to the
mixer, for example, as flow or concentration fluctuations in the incoming pulp and
chemical streams, or they may be imposed
by the mixing geometry. This latter case is
illustrated in Fig. 2 by two configurations
for chemical addition to a mixer. A scale of
nonuniformity is introduced in both cases
at the point of chemical addition by the distance over which the added material must
be transported to contact and mix with all
of the pulp stream. In the second configuration [Fig. 2(b)] ,the distance is smaller and
therefore imposes a smaller "load" on the
mixer. Consequently, less mixing is required
to attain a desired level of uniformity. It is
important
to recognize
that, although
nonuniformities entering a mixer are caused
by external factors, the mixing load imposed by the positioning of the chemical
addition point is controllable by the designer. Mixing can often be improved by
lowering the mixing load instead of increasing mixer capacity.
2.2 Pulp suspension
rheology
Mixing is produced by creating relative

motion within the pulp suspension. This
requirement makes mixing in pulp bleaching uniquely difficult because of the complex rheology of pulp suspensions.
Chemical Addition
Pulp
MIXER
(8)
Chemical Addition
Mixer
(b)
Fig. 2. Ntm-U"iformUies
III' I04tl
tbllt COIfIrIhte
1,,1rfHlMcetl
to tbe ",ix-
lbe
__ I"
ronlaetetl. Tbe
wbleb lbe""'feed slre._

.re
",ixI"g 100000Imposetl ~ ronflprwtton
(.)
Is l.rger tH" IHII",posed ~ ronflpr.tton
(b).

characteristics
Pulp suspensions are continuous fiber
networks which possess structure
and
strength resulting from interaction between
neighboring fibers. In suspensions having
consistencies greater than 0.5%, cohesive
strength occurs from mechanical forces
caused by the bending and hooking of fibers (27). As the consistency of the suspension increases, the number of fiber/fiber
interactions
increases which in turn increases network strength. However, the distribution of fibers within the network is
never uniform, and loeal mass concentrations of fibers give rise to floes within the
suspension. Because network strength depends on the number of fiber contacts, floes
have a higher strength than the surrounding suspension.Therefore,floes
are not only
regions of higher mass concentration, but
are also regions of greater strength in the
suspension. As a consequence, floes may
behave as independent entities in a flowing suspension.
.
At low consistencies (0-4%), the fibers
and floes are suspended in abundant free
water. These suspensions can be pumped
and mixed with relative ease. As the suspension concentration
increases into the
medium-consistency
range (8-16%), the
greater number of interfiber contacts substantially increases both network and floc
strength. The character of the suspension
changes from one of mass concentrations
(floes) of fibers in water to one of wet fiber
aggregates surrounded by gas. The volume
of entrained air in medium-consistency
suspensions may exceed 10% (28). The gas
content can be dramatically increased if
gases are intentionally added to the suspension.
At high consistency (20-40%), the suspension becomes a network of damp fiber
aggregates surrounded by gas. The void ratio in this range is sufficiently great that the
network is a permeable medium having a
much lower resistance to gas flow in the
inter-floc spaces than in the intra-floc passages. Thus, fiber floes in this consistency
range present an "aerodynamic specific surface" to a flowing gas substantially less than
Pulp network
541
the specific surface of an individual fiber,

approximately 15-60 m2Jkg compared with
approximately 350-1000 m2Jkg (29).Thus,
although a gas readily flows through the suspension, there may be little contact between the gas and most fibers unless the
floes are broken up in some manner.
Fiber network strength
To produce flow in a mixer and to expose fibers to a chemical at an addition
point, sufficient stress must be applied to
rupture the fiber network as well as the
floes within it. Therefore, pulp network
strength is an important factor in the design of mixing equipment.
Network
strength depends strongly upon suspension
concentration as shown by many investigators (27, 30-33).
In recent work, Bennington et al. (33)
measured the network strength of a number of pulp suspensions over the wide range
of consistency (0.4-50%) and void fraction
(0-90%) encountered in pulp delignification
and bleaching processes. Using a cylindrical shear-tester with profiled rotors to impose shear within the network instead of
at the network-solid interface, it was found
that
ty
=7.7
32 (I-X)3.4
X 105 C m....
A06
[1]
where t is the yield stress of the network

in Pascals C is the mass concentration and
c~ntent of the suspension both
X the
dpressed
as fractions, and A is the fiber
aspect ratio. (Terms and expressions are
defined in the Glossary at the end of the
chapter.)
Turbulence in fiber suspensions

The initiation of motion in a pulp suspension first oecurs at the weak zones of
the suspension, that is, between floes. As
the applied shear is increased, the relative
motion between floes increases and floes
themselves are ruptured. Further increases
in shear cause more intense movement and
eventually turbulent flow. Thus, pulp suspensions display a range of fluid-like behavior, extending from motion of floes relative
to one another to motion of individual fibers relative to one another. Energy is dis-
';42
Pulp Bleaching
- Principles
and Practice
sipated during these flows and therefore

power must be supplied continually to
maintain motion. Indeed, because energy
dissipation oecurs through small-scale fluid
motion, the power dissipation per unit volume,E,can be used to characterize the level
of small-scale motion and thus the degree
of fluid-like behavior created within a suspension.
The creation of turbulence within a suspension is often referred to as "fluidization."
The power dissipation required to fluidize
a suspension has been estimated (34) and
measured by a number of investigators (3538). Bennington (36) found that for a widegap configuration
E
= 7.5
X 103 Cm25
[2]
where Cmis given in percent. Equation [2]

is valid over a consistency range of 1.0 to
12%. Achievement of a fluidized state is one
design criterion for medium-consistency
"fluidizing" pumps (39) and medium-consistency mixers (40).
2.3 Mixing gases into pulp suspensions
As increased use is made of gaseous
bleaching chemicals, efficient means of
Table 1. s8SJ1erlSlmt et1IfIJIOSUIoIIlff
blMcItIffl
contacting the gas and fibers are needed.

Two issues are important: creation of a homogeneous mixture with ample interfacial
area for mass transfer. and maintenance of
a stable three-phase suspension for a suitable period.
Table 2 lists typical suspension compositions for a number of bleaching operations.
The gas fraction and suspension consistency
determine the suspension rheology as described previously. These factors, coupled
with the net bleaching reaction rate, dictate the contacting method appropriate for
each situation.
At high consistencies,little
free water is
present in the suspension because approximately 1.5 kilograms of water is absorbed
in the fiber wall for each kilogram of fiber
in suspension (4 J). Additional water is also
located within the fiber lumen depending
on the degree of fiber collapse. At 20% consistency, for example, no more than 2.5 kg
of water per kilogram of fiber resides outside the fiber. This decreases to 0.8 kg/kg
as the suspension consistency is increased
to 30%.This water forms a liquid film around
the fibers and may represent a mass transfer limitation for the bleaching reaction
operatltms.
Bleaching Stage
Qperating Conditions
Suspension
Pressure Temp.
Consistency
kPa
C
%
(Absolute)
Cm'
Air content of kraft pulp [28]
10
101
25
15
101
25
20
101
25
Chlorination of kraft pulp
(7.2% equivalent chlorine on pulp)
C~
3
Cwo
12
12
C,J)""
Oxygen delignification
12
(2.2% 02 on pulp)
30
Oxidative extraction
(0.5% 02 on pulp)
(E+O)
12
Gas Void Fraction of Suspension

Before
After
Dissolution
Saturation
of Chemical
of Water'
0.04-0.10
0.10-0.30
0.30 - 0.50
350
350
3';0
30
50
50
0.18
0.49
0.33
0
0
0
750
7';0
100
100
0.26
0.49
0.26
0.48
450
70
0.11
0.10
700
10
0.6j
0.84
0.62
1100
40
0.23
0.50
0.22
0.49
Ozone bleaching
(1.0%
0;
on pulp,
7"(0
q in OJ 10
30
(0.5% 03 on pulp, 12% 03 in 0,)

'All water is assumed
available
10
30
to dissolve
the gas phase.
0.84
543
544
phase mixtures can be created under turbulent conditions as illustrated in Fig. 3(a)
(45). Here it is difficult to identify the gaseous phase although small pockets of gas
can be seen moving in the flow. Increasing
the gas phase above that which can be
handled by the mixer leads to phase separation and poorer contact between the gas
and suspension as shown in Fig. 3(b).
Energy input is required to create interfacial area and maintain a mixed state.Thus,
the quality and extent of mixing depends
on the rate and duration of energy input.
As gas is added to a pulp suspension, the
power that can be applied by a mixer decreases as shown in Fig. 4. In this figure,
the ratio of the power drawn under gassed
conditions (P) to that drawn by water under ungassed' conditions (po..J is plotted
against the gas void fraction for a laboratory mixer operated in batch mode. The
graph shows a rapid decrease in energy input to medium consistency suspensions
with increasing gas content. The upper gas
handling ability of a mixer is dictated by
geometry and is approximately 13% by volume (0.13 gas fraction) in this case (45). In
industrial settings, maximum gas void volumes of around 30% have been reponed
(46-48).
(42). At high consistencies, the mixing

strategy is to fluff the pulp to expose fiber
surface which is then contacted with the
gaseous phase (43,44).
At medium consistencies, more water is
present in the suspension but,for low-solubility gases, a gas phase is still present. In
this situation, it is important to develop interfacial area to facilitate contact between
the gas and the suspension. This objective
is usually accomplished by creating turbulence within the suspension. The vast density difference between the gas and pulp
fibers makes mixer design difficult. Although rotary motion is often used to
achieve mixing, this same motion also separates the gas phase from the suspension.
When gases are mixed into medium-consistency suspensions, homogeneous tmee-
..1.0
D-
e 0.5
c;;
plpBllIIe~",
0.4
0.6
Gas fraction, Xg
0.8
1.0
ps fIII:t-
poeIu!t
(11IIUuted
by lbe
(b)
movIllg wIIb the SIISJIefISItm flow.
"rrow)
A C = 12'J(,SIISJIefISItmwltb X = 0.20 sbows
pbase segreg"Uon tbllt IImlls moment"m

transfer to tbe buill of tbe SIISJIefISItm'
The
contact
action.
phase
to jn'fH/IIetlon
""'e
of 477 tidily. Tbe ps tUltUtIon" rwte eorresporuIs
IJOItlftwetlon
ofll-3%
t:OIIf/NItWbk
to
COIIto"
f!eIIttoul
~-rellI.foreM
e3drtletlon.
IlIg Into metll8m-DOllSlstertey

1mift JnIlp SfISbIIIeb 0JIn'tdM liIburtItory
pensunrs flSlllg
(,,)
wIIb X
A C " 1(1%
mlJtn:
Note tbe"gu
3.2 Mass transfer, reaction rate, and

mixing rate
The overallbleachingrate for a panicu-
1.') meters
3. Mixing in pulp bleaching

0.2
O.lj.
Flg..s. PbotOfNllb of /JbtI# ~
=14.1
Pig.j. mgb-BP-I ri4eo l-.ges ~
linear function of the applied chemical. At

some point in the reaction, proponionally
larger amounts of chemical are consumed
in producing an incremental gain in the
degree of bleaching. At the same time, undesirable degradation reactions may occur
with the carbohydrates
remaining in the
pulp.
When mixing is not uniform, some regions of the pulp receive chemical in excess of that required, some of which may
be consumed in the less desirable side reactions. Other regions receive insufficient
chemical and the pulp, shives, and other
bleachable panicles may not be adequately
bleached. In this situation, the net effect is
that additional chemical is required to attain a desired degree of bleaching and a pulp
of less than-optimal-strength
is produced.
The above discussion illustrates the effect of the post-mixer mixture quality on
pulp bleaching. However, the rate at which
this mixing quality is achieved may also be
important. When the rate of mixing is low
compared with the effective chemical reaction rate, the deleterious effects discussed
above occur even if acceptable mixing quality is eventually achieved.
IlIg lit 23.s01/m11l118tk jM em

" lIiImeter
.. =12
=14
. =16
""
exiting a mixer is difficult. The gas phase

readily separates in the decaying turbulence
following mixing as shown in Fig. 5 (49).
The photograph
was taken immediately
downstream of the control valve after addition of nitrogen using a sintered metal
sparger. The gas void volume was 11.3%,
equivalent to that found in oxidative extraction stages. Although gas segregation has
been found to be rapid following mixing in
pilot-scale facilities, the formation of a "fiber foam" in industrial applications may
help to stabilize the suspension (50).
dm/m.strNm
of the mIIIrVl V4lve follollJlrsg gtIS
sl1IIerN metlll sptIt'ger. Tbe
tUltUtIon flSlllg
vIewIrsg wlruImIJ " Is ').2 em III tiUlmeter. Afully
blellebM lnwft pulp lIt C
WIIS flow-
Cm.'"
0=6
C =8
.6. = 10
required duration oCgas-suspenslon

is determined by the bleaching reMaintenance of a well-mixed threestate in a pulp suspension
after
3.1 Mixing quality

Bleaching involves multiple simultaneous
chemical reactions with lignin and carbohydrate components
in the pulp. Consequently, both the quality and rate of mixing
affect bleaching efficiency.
Bleaching reactions follow a common
trend: a very rapid initial reaction is followed by a declining rate period in which
the reaction rate levels off. Although the
extent of reaction is determined by the
quantity of chemical consumed, it is not a
tar system is a function of the rates of chemical reaction, mass transfer resistances, and
mixing. In the general case of a three-phase
(gas-water-fiber) reacting system, a number
of mass transfer steps are involved in the
bleaching process. However, one step often controls the reaction rate, and this controlling step must be determined for each
system. Bleaching reactions are complex
and the net bleaching rate may change during the course of reaction or be different in
different pieces of equipment. For example,
the rate-limiting step in pulp chlorination
has been reponed as being chemical reaction (51-54), diffusion through the liquid
film ~urrounding the fiber1l (JJ),and diffusion through the fiber wall (56,57).
Mixer design should take mass transfer
resistances into account. For example, if
diffusion to the center of a floc has been

determined to be the rate limiting step, a
mixer designed to disperse flocs would increase the effective bleaching rate by decreasing the key mass transfer resistance.
The rate at which the bleaching chemical and pulp fibers are brought together also
influences the overall reaction rate. Bleaching chemical must be supplied to the reaction site as fast as it is consumed otherwise
bulk transport becomes the rate-limiting
step. The impact of mixing on a chemical
reaction can be assessed by comparing the
relative rates of mixing and chemical reaction. By defining two characteristic times:
one characteristic of the mixing process,
tm,and the other characteristic of the chemical reaction, t" three cases of interest
emerge:
1. Mixing occurs much faster than the effective reaction rate, 1:/1: 1: Here mixing
has achieved homoge;eity before chemical reaction has proceeded to any extent.
The overall bleaching rate therefore is governed solely by the effective reaction rate
and a further increase in mixing rate would
not improve pulp bleaching.
2. Mixing and reaction proceed at approximately the same rate, 1:/1: =1: In this case,
both mixing and reactio~ kinetics determine the rate and quality of bleaching.
3. Reaction occurs much faster than mixing,
1:/1: <<1: Here mixing is slow compared
t~ the effective reaction rate. Consequently, the efficiency of pulp bleaching is
determined by the rate at which mixing
proceeds as well as the quality of the final
mixture.The effect of slow mixing on pulp
quality is identical to that of obtaining a
poor final mixture quality.
To compare mixing and reaction times,
they must be determined independently of
each other. This requirement is not trivial
as they are often intimately linked.The characteristic reaction time, t, should be measured under conditions where mixing does
not hinder reaction. Reasonable estimates
may be obtained using laboratory data obtained under well-mixed conditions. For
example, flfst-order rate constants, k, can
be fit to the initial (rapid) portion of kinetic
data reported in the literature. In this case,
545
the reaction half-lifetime (ln2lk) can be used

to estimate t .
Mixing oc~urs simultaneously over many
scales, any of which can inhibit bleaching
reactions. Macroscale mixing rates can be
estimated
using bulk blending
times.
Microscale mixing rates can be estimated
based on turbulence theory and the rheology of the suspensions.
A number of
mathematical expressions can be used depending on the mechanism creating the
mixing (16,22). In many cases, the rate of
energy dissipation enters into the calculation and mixing rate is found to increase
with increasing energy expenditure.
546
(a)
ment mixing on a fiber-scale may be important.

In passage through pipes and retention
towers, the liquid (aqueous) phase flows
at a greater rate than the solid (fiber) phase
(60). This rate difference
is most pronounced for low-consistency suspensions
(Cm < 3%) which have abundant free water
in suspension. In these situations the relative flow enhances mass transfer between
the chemical and the fiber.
At higher mass concentrations,
relative
flow between liquid and fiber does not occur in flow situations. However, by imposing a differential flow between the fibers
and the chemical containing liquid in medium-consistency suspensions (C
to to
12%), the bleaching reaction rat~ can be
accelerated (55).This concept was used by
Kamyr in the design of the displacement
bleaching tower (61,62).
(b)
3.3 Mass transfer after mixing

Bleaching reactions continue after mixing has ceased because of the short mixer
residence time compared with the longer
period required for bleaching reactions. In
addition, because mixture quality is seldom
perfect following mixing, diffusional processes play an important role in achieving
uniformity in the suspension.
Given sufficient time, diffusion eventually produces a uniform mixture. Paterson
and Kerekes (58) measured the distance a
reacting front of chlorine moved through
an unbleached pulp suspension as a function of time. Over a I-hour period, the
chemical advanced 3-5 mm through a 3%
consistency
suspension
and 1-2 mm
through a 12% suspension. Wong and Reeve
(59) found that the fibers obstructed diffusion and that diffusivity decreased linearly
with increasing fiber void fraction. A diffusion front is shown as a function of time in
Fig. 6. Here a non-reacting chemical is imaged as it diffuses through a 3% suspension
(36).The initial sphere of chemical grows
in radius from I to 6 mm in 38 minutes.
The decreasing diffusional distance ass0ciated with increasing consistency implies
that better mixing is required as bleaching
consistency increases. Chemical reaction
increases the diffusion rate but also depletes
the reacting chemical. Therefore, the initial
size of the unmixed regions determines if
it is possible to achieve uniformity in the
suspension. Indeed, depending on the ini-
4. Mixersused for pulp bleaching

The rheology
of pulp suspensions,
bleaching chemistry and kinetics, and mass
transfer resistances govern the design of
mixers used in bleaching applications.
Mixer design has continued to evolve with
the changing needs of bleaching processes.
In this section, these developments are examined with attention focused on the hydrodynamic
principles
of each class of
mixer and the ability of each mixer to
achieve macroscale, fiber-scale, and microscale mixing of pulp suspensions.
(c)
F'g. 6. l_ges sbormfl tII./fuItm 0111_-rHetlIIg

IrtIar IlmnIlb IIInwft JnIlp SIISJIftUImt ole
j%. lire 'rugn ~
ob,.'lIBtIlISI1Ig NMI
(Ntu:letlr
Mtlpetk~)
, ,,'"
_ tuJotIIlMIISIoIIIIlslka (2-3
"""
11M")
IlmnIgb I. CMtM
SJlberk4llydiffus"""
01"'"
trtu:er. lire IrtIar /IHr5 flIbire I.
'"I
'"
'_1ft, lllbik I. urt lI~tIS II~ InIbbles
trrIpJJetllllllblll
SfIS/IeIIsIotI.lIre ermtllhler
boItIIIII I. /'8lp"'" Is spberleIIllI"" 40
tllllmeler. l_ges nuuIe lifter (II) 38, """
(b) 82
'"
(e) 660
""".
"""
tial degree of segregation and chemical concentrations, diffusion distances may be limited to fractions
of a millimeter. This
indicates that flocs should be disrupted in
the flow-through mixers and that assess-
4.1 low consistency mixers

Continuous stirred tanks (CSTs)
The CST is widely employed in pulp mixing and blending operations. In the past,
these vessels were commonly used for lowconsistency pulp chlorination. Today, the
agitators and circulators used in bleaching
residence towers create actively mixed regions that can be considered CSTs (Fig. 7).
The impellers produce bulk movement of
fluid by a pumping action and turbulence
in the wake of rotating blades. The size of
the mixed region is determined by the shear
produced by the impeller and the yield
stress of the pulp suspension.
547
548
must occur at all points within the vessel.

This requires that the shear stress created
by the impeller(s) be sufficient to ruptttre
the fiber network even in remote zones of
the vessel. The tendency to form stagnant
zones increases with increasing suspension
consistency (36,63,64). Second, there must
be adequate residence time in the mixer in
relation to the flow rate and scale of
nonuniformities to be removed (65-68).
Mixing at the fiber-scale is achieved by
fluid shear and turbulence. In a CST, the
shear level varies over a wide range and can
be quantified using the local power dissipation (16,69-71). For Newtonian fluids,
the power of distribution in a conventional
CST is shown in Fig. 9 (70). Here the CST
FIg. 7. TmI1ermixers t:I'WIU/I _

motItm
sIm''''r
11Ch~mical
In
of supasitm
Impeller
tip zone
Fig. ,. SIIe/IrtUstrilnltlon ,.. . CSTIs re"'tell to loul

tbrougbIIIIrle&
JIOfIIertUssIp/ItIon
""'y
_I. """ TIleCST""",11e
tI,vIdetI
tbe
""t
"'~ zorres ,.. aeeruII..g order of sbe/Ir:
11IIotlwee
hili, tmpeller,
Bulk
flow
tmpeller tip.
"""
is divided into three zones in ascending order of shear: the bulk, impeller, and impeller tip. Power dissipation in the impeller
tip zone (accounting for only 0.5% of the
vessel volume) is fifty times that of the
mean.The significance ofthis for pulp mixing may be illustrated by examining the av-
High
shear
.. erage power used for agitation of a 4%

consistency kraft pulp suspension, 1-2 HPI
1000 use (200-400 W/m3) (72). Based on
of...
Pulp
out
to tlMt of /I CST.
Bulk flow in a conventional CST is the

recirculating flow pattern illustrated in Fig.
8. Elements of the pulp suspension spend
differing times in the mixer and therefore,
on recirculating, meet different parts of the
incoming flow. Through this process of
backmixing,large-sca1e nonuniformities are
eliminated. Thus, good macroscale mixing
has two key requirements. First, movement
Fig. 8. Rototlon
Pulp
in
tmpeller
"'rge-set"e
reclt'CfI"""'g
sel /15 well /15 sbe/Ir
"""
fIJIIIIe of rototl..g I1l1Uies.
,.. . CST JtrrHltIees

motion ,.. tbe rJeSturlnlleru:e ,.. tbe
the power distribution given in Fig. 9, the

power dissipation in the region immediately
around the impeller (the impeller tip zone)
is 1.0 - 2.0 x 104WIm3, a value close to that

measured by Gullichsen et al. (35) for "fluidization" of a 4% suspension. Other regions
in the vessel have dissipation rates much
lower than this value. Therefore, the most
intense suspension motion and fiber-scale
mixing occur only in the impeller tip region.
The amount of shear imposed on a portion of a pulp suspension depends on the
number of times it is circulated through the
impeller tip zone. Therefore, because a CST
has a distribution of residence times, not
all of the suspension is subjected to the
same fiber-scale mixing.This nonuniformity
of residence time and circuit history leads
to both the principal advantage and disadvantage of a CST: it produces both macroscale and fiber-scale mixing but, by virtue
of producing the former, it cannot produce
a uniform level of the latter. This is a shortcoming in bleaching because each fiber
should be uniformly contacted with the
bleaching
Dynamic
reagent.
mixers
To achieve more uniform fiber-scale

ing, CSTs were modified
to subject
mixpulp
suspensions to more uniform and higher

levels of shear and turbulence.As illustrated
in Fig. 10, this is achieved by forcing the
suspension and chemical to flow through
the high-intensity impeller tip zone. Other
mixer designs use a series of stirred regions
partitioned by baffles within one vessel.
Increased fiber-scale miXing can also be
achieved by reducing or eliminating the
low-shear zones of bulk motion in the vessel by reducing the mixer volume and increasing the average energy dissipation.This
trend has been continued as high-shear mixers (developed
operations) are used in low consistency
applications. In all cases, fiber-scale mixing
is improved, but only at the expense of
macroscale mixing.
Static mixers
Static mixers consist of a series of stationary mixing elements positioned in a section
of piping. There are many proprietary designs for these mixers but all achieve fluid
mixing by dividing and recombining the
flow (cutting and turning), by generating
turbulence in the flow, or by a combination of these two mechanisms
(73,74).

(a)
plug flow. Moreover, mixing quality is

linked to the flow velocity and therefore to
the production rate of the bleach plant. Consequently, static mixers must be correctly
sized to ensure proper mixing for all
planned operating conditions.
Static mixers are generally chosen for use
only with low~onsistency pulp suspensions
(75). They are also used in a few mediumconsistency applications with appropriate
means of chemical addition to minimize
the mixing load (76). However, they cannot generate the intense shear required to
create turbulent motion within medium
consistency suspensions and must rely on
cutting and turning to mix.
Fig. 11. Sl4tk~ekmMts--'forJn"p",UIflg.

(tI) Knies, (b) IComtIx, tmd (e) Koeb SMF.
Figure 11 shows some of the flow element

designs used for mixing pulp suspensions.
The key feature of static mixers is that the
entire flow is subjected to a similar degree
of shear. This ensures that all the flow receives the same level of fiber-scale mixing.
The mixing energy is extracted from the
mean flow and leads to a significant pressure drop through the mixing part of the
pipeline.
Static mixers are usually sized for a flow
velocity which places them in the turbulent flow regime. Although this ensures
good small-scale mixing, large macroscale
variations are not eliminated because the
suspension passes through the mixer in
549
';50
(a)
mixers
Peg mixers
Mixing in medium-consistency
pulp suspensions has conventionally been achieved
by peg mixers. These are tubular vessels
having one or two shafts, with attached
pegs, that rotate between stationary elements attached to the mixer casing as
shown in Fig. 12. As pulp is conveyed
through the mixer, the rotating bars shear
the suspension against the stationary elements. This shearing action creates transport through the suspension and exposes
new fiber surface. Chemicals may be added
ahead of the mixer (as in the Ingersoll Rand
mixer) or distributed
inside the mixer
through appropriately
located injection
ports (as in the Dorr-Oliver steam mixer).
Peg mixers have also been used, to a limited extent, in gas-mixing applications. In
the "swept area" mixer shown in Fig. 13
(77), the design aim is to achieve a target
value of area swept out by the rotating pegs.
In so doing, a given area of fiber surface
per metric ton of pulp is exposed. The
swept area required for different applications has been determined in pilot-scale
studies and found to depend on the bleaching chemical used (50).
(b)
Steam inlet nozzles

Fig. 12. Peg ",furs.
(tI) Iflgersoll-Rmul
(tAPPI Mmrogrwpb 17, 1963).
Cblorine
dloxUk
High-shear mixers
tational speeds across narrow gaps through

which the pulp suspension flows as illustrated in Fig. 14.Although there are design
differences among the high-shear mixers,
they all attempt to fluidize the suspension
in the mixer working zone. The high shear
rate ensures floc disruption and good fiberscale mixing. It also leads to high power
dissipation per unit volume. Small mixing
zones keep power use to acceptable values,
although the size and power requirements
In high-shear (high-intensity)
mixers,
chemicals and pulp are mixed during passage through zones of intense shear. The
high shear is created by imposing high TO-
of these mixers have always been a concern

(76). Recently, two mixers, the Ahlstrom
Ahlmix and SundsT, were introduced.These
have smaller mixing zones and require less
mixer,
(b) Dorr-Ollfltl1' double
shaft
slHm
mixer
installed horsepower than previous designs.

However, in all high-shear mixers the small
mixing zone leads to extremely short residence times which preclude macroscale
mixing. Thus, macroscale nonuniformities
in the flow of chemical or pulp to the mixer
must be eliminated upstream by other
means.
The maintenance of a fluidized state during mixing operations subjects pulps to
mechanical treattnent and alters their physical properties (35,78,79). Studies indicate
that fluidization beats and induces curl and
microcompression
in the fibers. However,
the treatment
received
from passage
551
';52
Pulp inlet
Pulp Bleaching
-Principles
and Practice
Chemical in
~
(a)
Chern.
Fig. 13. Beloit
PUlp out
IV-Series srtJePt llrea mixer.
through a number of bleaching stages' alters pulp properties only very slightly (the
changes in tear, tensile, burst, and freeness
are less than 5-10%). Consequently, the
pulp appears only slightly pre-beaten. In
laboratory batch operntions, the energy
exposure is generally substantially higher
and may need to be considered when evaluating the outcome of bleaching. '
Gas contacting is also carried out with
high-shear mixers. In this situation, the volume of gas to be mixed with the pulp is
usually the limiting factor. For the Ahlstrom

Ah!mix, maximum gas fractions of approximately 30% have been recommended
(46,80). Because the entrained air content
of industrial pulp suspensions
may approach this value (Table 2), it is recommended that it be reduced before addition
of gaseous chemicals.This reduction can be
accomplished using the degassing ability of
centrifugal medium-consistency
pumps.
The high-shear mixers used for pulp
bleaching are illustrated in Fig. 15. It should
(b)
Pulp in
Pulp out
<:).
Pulp out
(c)
Chemicalin
Mixingpin
.-
Rotor
mbIy
Pulp in
Fig. 14. J"tense sbetlr .forr:es lire _tM

", blgb-sbetlr mixers. Sbetlr Is gertertJted by impost"g blgb rollltUmiI/ speeds tIC1'OSS
tttlrrotIl gtIJIStbrougb wbkb tbe Jnlip suspettslott flows.
(d)
Fig. 15. High-s"'"
m:izers: (II) AIIIstrom All/mix, (6) Ahlstrom Me Jnlmp (c) Be/oit-Rtlutrltl R Series F
. dJ
J"get'SOlI-RmuI
Hi-SbetIr.
'
""
553
554
Pulp Bleaching
-Principles
and Practice
Pulp out
(t)
Pulp in
(g)
be noted that the Ahlstrom pump is included in this figure. The decaying turbulence produced in fluidizing pumps is often
utilized for mixing purposes.
Mixing in pipe contractions and expansions
Thrbulence can occur wherever a fluid
is subjected to intense power dissipation.
For example, turbulence may oecur during
flow through centrifuga1 pumps or in the
wake of any flow element that causes
boundary layer separation (e.g., partially
closed valves or sudden expansions in process lines). These are flows of decaying turbulence because the power dissipation
required to maintain the turbulent flow is
not sustained. Fluid motion in a pulp suspension diminishes very quickly in decaying turbulence.
For example,
at 3%
consistency, cessation of inter-fiber motion
leads to refloeculation approximately 0.005
second after the turbulence maximum is
attained (27). This refloeculation time decreases dramatically as the consistency is
increased.
Despite the rapid loss of mixing action
in decaying turbulence, it can be used for
mixing in the low- and medium-<:onsistency
ranges. For example, in oxygen-reinforced
extraction, oxygen bubbles from a sintered
metal sparger are mixed into the discharge
flow from a Kamyr MC pump just before
passage through an orifice plate and control valve with good results (81). Indeed,
Cirucci et aI. (82) conclude that this method
permits oxygen to be mixed into mediumconsistency pulp as efficiently as with highshear mixing. While decaying turbulence
from the medium-<:onsistency pump is a key
factor in this mixing, the shear and turbulence induced by the orifice plate and pipe
expansion contribute to the good mixing.
mixers
Pulp suspensions at high mass concentrations have very little free water present.
Mixing can be achieved by creating surface
area within the suspension to facilitate con-
tIlct betWeen fibers and bleaching chemi.
Fig.
15. High-shear
mixers:
(e)
Kamyr
MC, (j)
S,,1UIs
SM arul
(g) S,,1UIs
T.
cal or by subjecting the suspension to cycles

of compression, relaxation, and shear to
distribute chemical through the suspension.
Fluffers and shredders create surface area

by passing the fiber suspension through narrow apertures over which strong shearing
forces act to disperse fiber floes. The A.B.
Nilsen disc mixer and Andritz Sprout-Bauer
HCM are examples. As shown in Fig. 16,
the suspension is passed between a stationary and rotating plate on which raised knobs
intermesh to shear the suspension. The
plate gap can be adjusted to increase or
decrease the shear level which alters both
the mixing action and the energy expended
in mixing. Aqueous chemicals are added
ahead of the mixer to take advantage of distributive mixing within the unit. Gaseous
chemicals can be added directly to the mixing zone or contacted in a separate reactor
once the fiber surface area has been created.
Repeated compression and decompression cycles can be used to distribute aqueous chemicals throughout high-<:onsistency
pulp suspensions.
The Sunds Rotomixer
and Kamyr MDR (Fig. 17) use a kneading
action of shear and repeated compression!
decompression cycles to move the chemical between floes and neighboring regions
within a suspension.
The mixers discussed above, together
with their advantages and disadvantages in
pulp bleaching operations, are summarized
in Table 3.
5. Mixing practice
5.1 Equipment use in mills
In the 1970s static mixers replaced CST
and dynamic mixers in low-<:onsistency operations; medium-<:onsistency
operations
relied on peg mixers (25). In the early and
mid-1980s, replacement of existing C- and
D- stage mixers with high-shear mixers proceeded rapidly in a quest for chemical savings and increased product quality (13).
High-shear mixers are now common in
medium-consistency
operations. In lowconsistency operations, static mixers continue to be widely used. However, a wide
range of mixing equipment is found in mills.
Mixer installation is highly site-specific and
a wide range of configurations are possible
as illustrated by Pryke (75).
:,
..
!"
..~
i,.
~1
!i
~l
~~ii
"c
it
-6'
:i'
r!~..
~!
~Ir
z
CD
I
... ca
C')
n ~~.
~~CD
nCD
C')
CD
1:"[
~l~
C')
-:r
it.....
_.CD
~3
n.
It
0-.I:
os
tI
:;;
CD 0
AI
~:::
~:
c?1
_c
[
:::~.
Ci1
!!.
i':..
~!-
~VI
VI
VI
Table 3: Mixers lISeJlfor pulp bletu:bI"g.

Consistency,
Mixer
type
CST
Low
( l.()
.Various
configurations
and
residence times
Comments
%
High
(20-40)
Medium
(8-16)
. In-tower mixers
Backmixing is generally good provided the CST is properly designed

and short circuiting avoided.
Potential for cavern formation due to the suspension yield stress.
Nonuniform fiber-scale mixing.
Mixing efficiency drops as pulp consistency increases.
In-tower mixers
STATIC
.Widely used
. Some applications
Employs laminar and/or
turbulent
mixing.
All flow receives uniform treatment.

Mixer must be properly sized for the expected flow. TIlis is usually
based on a critical velocity. Increased flow increases pressure drop.
Turndown ratio can be small.
Many proprietary units available.
DYNAMIC
Agitated vessels
.Various
.Short residence times
CSTs reduced in size to achieve better fiber-scale mixing.

Backmixing traded for increased and more uniform turbulence
shear.
configurations
Peg mixers
High-shear
Intense short duration
mixing of pulp
.
.
Single and double shaft
High power input with

short residence
times
.
.
Fluffers/Shredders
Kneaders
PIPE
CONTRACTIONS
and EXPANSIONS
. Decaying turbulence .
generated by flow
through valves.
Turbulence
created
pump discharge and

flow through valves.
Expose fiber
surface area
Squeeze liquid
from floes
in MC
Widely used for steam heating.

Multiple injection ports.
Uttle or no macroscale mixing. Residence
All flow treated equally.
Imposed shear independent
of production
...
.
.
times as low as 0.05 s.

rate.
Refiner-like devices with raised knobs to shred pulp.

Repeated
cycles of compression
and
and decompression.
Wake turbulence can be used for mixing.

Relative motion and turbulence decay decreases rapidly in
downstream tlow. Decay time decreases as pulp consistency
increases.
557
Pulp Bleaching
-Principles
and Practice
mixing quality. If the results are poorer than

expected when compared to known wellmixed cases, the mixing may be considered to be poor. However,factors other than
mixing affect product quality and direct
methods for assessing mixing quality are
desirable.
(a)
..
Pulp in
(b)
"In
Che!1'iC81
Fig.17. Hlgb-eonsIstem:ym~
558
Pulp
out
TheKIImyrMDR(II)II1IdS"rulsRotomlxer (b).
Changes in mixer design and insta1lation

configuration continue as the needs of the
bleaching process evolve and as more is
learned about mixing. The Ahlstrom Ah1mix
and Sunds T mixers consume less power
than previous high-shear mixers, raising the
question about what constitutes the minimum power requirement
necessary to
achieve good mixing in different bleaching
situations. Gas contacting is becoming increasingly important as ozone bleaching
technology develops. What mixing strategies provide adequately mixing of high gas
volumes into medium-consistency
suspensions? and how long must the mixed state
be maintained? These are questions which
will be answered as experience is gained

from current and future insta1lations. The
acquisition of information will be facilitated
by assessing the mixing quality produced
by operating industrial mixers.
5.2 Mixing assessment
As in other industrial processes, the assessment of mixing quality in pulp bleaching operations is a difficult task. The most
common methods are indirect ones based
on measurement of product quality at the
end of the process. In pulp bleaching, for
example, residual chemical content, pulp
brightness, pulp cleanliness, and pulp viscosity are commonly used as indicators of
Macroscale mixing assessment

Macroscale mixing can be measured using two approaches. The first uses the residence time distribution to determine the
ability of a mixer to attenuate incoming
process fluctuations and identify short circuiting and dead zones within the mixer
(65,66,83). The second uses the spatial distribution of a tracer to quantify the homogeneity of the mixture produced. In most
cases, an inert tracer is used (5,6,84,85) although radioactive tracers can be used
(86,87). Because sampling is often a problem in the mill, some investigators have
used the temperature proftle around the
mixer discharge pipe to identify macroscale
variations where an initial temperature difference exists between the pulp and added
chemical (5,7,88).
Mixing is often quantified using statistical parameters such as the mixing index,
M, dermed by
I
~
M = sIX
.
L~=1
(Xi
n-l
- X)2
[~
x
where s is the standard deviation of the
measured quantity and x is its mean value.
Other indices have also been used.
Torregrossa (5) used the concept of "charge
deviation," which assumes a rectangular
distribution of chemical in the suspension,
to quantify mixing. For a given mixing quality, the charge deviation reported is smaller
than the value of M.
Before comparing the results of different
studies, the sample volume used in determining the mixing index should be known.
Figure 18 shows a set of test results in which
M was determined as a function of sample
size and mixing time in a batcb-operated
laboratory mixer (89). This figure shows
that sample size affects the value of the
mixing index measured. Therefore, sample
volume should be taken into account when

comparing different mixers and, in part,
may account for the large discrepancy in
axial and radial mixing indices reported by
Kuoppamaki (86).
o
:!;
0.1
"'"
'0
5
C>
c:
'x
:E
8
9m.min
0=2
0=5
6.= 10
. =20
0.01
10
Sample
100
size, cm3
Fig. 18. M~"g lrulex metlS"red lIS II

of
SIImple size IIrIdm~"g lime """';110"
I" II bIIteb opeNded lIIborIItory mixer.
Regardless of the sample size or the mixing index used, the literature reports large
differences in macroscale mixing quality as
shown in Table 4. This table shows that
macroscale mixing varies within a particular mixer group and that mixing can be significantly improved by using high-shear
mixers in place of static, peg, and tower
mixers. This observation seems to contradict the earlier statement that high-shear
mixers do not achieve macroscale mixing.
However, the improved macroscale mixing
occurs because of the reduction in mixing
load resulting from improved chemical addition, akin to that illustrated in Figs. 2(a)
and 2(b). Direct evidence for this view has
been provided by Breed (85) who demonstrated that the macroscale mixing efficiency of an Ingersoll-Rand Hi-Shear mixer
could be substantially improved by optimizing the point of chemical addition.
Fiber-scale mixing assessment
At the fiber-scale, 0.05-10 mm, a number of techniques have been used to measure mixing quality. Paterson and Kerekes
(90) developed a method to assess fiberscale mixing using a micro-sampling technique. The test was developed
for
chlorinated pulp suspensions at low consistencies and consists of removing a series
Chapter
VI 2: Mixing and Mixers
559
560
Pulp Bleaching
Ttlble 5: 111t'_ml
-Principles
of fiber-sult'
and Practice
mLnllB """Illy.
Intensity
e::
Goo .9
e::
~...
IU
~~.'W; u .5
e::lUco
0'0
u IU u
~E 'sIU
"Oe::.c:
IU 0 U
..
IU
.!:S
~5
IU e::
. ~.e::
. .9
Q.~
0'0
o os
Z-e
~~~-g
e::
~IU
8'-'0'0
p.,g...!:!
g
.'O].Q
00 8
p., '0
'sIU
~",.c:
e::u
0....
:;jO
:8
os e::
~. ~.9
...
os
u
::i;.9
Mill and Mixer Type
5
e-
-&1\
~t
.!:S
CO
~~~:;~
g.~
'.c:
'0....,
~~rIJ
4J oo~
~p.,~'E
~8e:: 0 .'8 0
'Oosc;
..'"
IU
'<1'
'0
B
55 ....
::i;'O
Low consistency suspensions (92,93):

Good laboratory mixing
Poor laboratory mixing
Mill A
static
MillB
two chamber CST
'0IU
IU
p.,
IU
IU
p.,
static
CST and static
e::
'0
.~
.;:
p.,
MillE!
MillE2
CST
two static
0.12
0.Q7
MiUF
MillG
~~Mill
H
Mill I
two static. one mechanical

static
two static mixers
static
0.12
0.14
0.55
0.36
..
os
~@.c:
~IU os
~.
0.13
0.16
MillC
Mill D
=p., 't
IU
'0
'~1
. u
.5
~ ~U
'<1'
t-0 0
'O/)u
'<1'
~e::!
:g~
0-
::i;
..IU u
IU
p.,
.!:S ::i;
~...
IU
.!:S
l!
:;:
I!
~5
..IU
::i;
:g~
00
.=
'0
'"
8~
00
0'"
0
'"
0
0
v
- ~.:::
0
~.
0$
~os
u
..
-'-5"8
~.. ~"'~~
IU-B
IU
IU
~~'C:
~e::1U,Q
_CIJ
N
~\0
N
:;
IU
.c:
'"
~CIJ .
0
8 '<1'
~0 0
'"
0 '"
0
IU
IU
.!:S u
5 ::i;
..
..
.!:S
IU
::i;
~;0coco
.=
'8 '6!
~vo
'
'<1' '<1'
..u
1U::i; "!!f
' !;. '6

~005 "3
&~ F .5
CIJ
i]
-N
fc
~i:;-IU
.=
~vo J~
.!
lUlU,...,
o.~
~5- 8
N
~~'-"
'<1'
8.....
'"
'"
-
II
::i;
:;:ri::
~~'8
~~.c:U
;:3
t~iI
U
::i;
U
os
z
U
;:3
'<1'
N
cis
..
~G-
I
..,.
IU
.c:
'0
'0IU
'0
~e::
I~
II
II
.~
~'"
'"
::t:
..
~~0
~;0
.~
.....
G-
<:!
...
o.
..0
..!I
~'8
.5
~~~~~a
'IU
-cis
~p.,;:3
U
;:3
'"
~~os
0.10'
0.13'
of 5-jlL samples spaced at 2-mm intervals

from the aqueous phase of the suspension
following mixing. The residual cWorine in
each sample was measured and the data
were used to determine the intensity of seg-
Individual flocs were removed from the

suspension fOllowing mixing and the dye
within each floc was extracted and measured.The measurements were normalized
based on floc mass and used to compute I,.
regation within the suspension: I, (90,91).

~~Note
that M = "<n-I) / n where n is the
I"
sample size. For n =
Francis and Kerekes found that fiber-scale

mixing quality improved with increasing
~The results
50, I, M.
==
of mill measurements
tained by Paterson
and Kerekes
Teodorescu
and Liebergott
(93)
ob-
(92) and
are sum-
energy expenditure
as expected.
However,
as shown in Table 5, the measured
segregation values were higher than those found
previously
for the low-consistency
suspen-
marized in Table 5. Most mills report I, val-
sions.This finding shows the increasing dif-
ues in the range
ficulty
.....
..~~<:!
.~
o.
~~C
~:;
~'"
'"
0.27 - 0.45
~'"
~~~R
p.,~ ~~00p.,
- 0.11
- 0.22
- 0.24
- 0.83
- 0.58
'0IU
'"
p.,
~~~..
e::
~~'0
~IU
t-.....
0.00
0.00
0.00
0.23
0.09
'Mixing Index, M.
.!:S
E5
~..;0 ~.8~
0.00 . 0.30
1.15
1.48
0.48
900 rpm
:E ..
0.09 - 0.18
0.03 - 0.11
0.25
0.14
High-consistency suspensions:
Kamyr MDR (Frotapulper) (94)
Hobart lab mixer (94)
30 s mixing
60 s mixing
240 s mixing
~laboratory high-shear (105) 1800 rpm
00
IU
~p.,
ON
$
0
0.12-0.14
0.00 - 0.23
IU6
0.09
Medium-consistency suspensions (104):

Medium-consistency valve
.~
-;'2
::10
0'.;:
I,
Range of Results
0.0
0.67
'
0
e::
..IU .g
'"
of Segregation,
Average
,Q
~'3
00
~E
:8
~~~:;E
0.07-0.16
which
may be
considered typical values. However, sub~~stantially

higher values were identified in
two mills where
pected.
poor mixing
was sus-
Francis and Kerekes (94) used a tracer

dye to measure
fiber-scale
mixing
in high-
consistency pulp suspensions. The dye was

added to the suspension at the mixer inlet.
of creating
fiber-scale
uniformity
as
~suspensionconsistency is increased.
Microscale mixing assessment
Chemical reactions are affected by mixing at the microscale level. The turbulence
experienced during reaction can determine

the overall
rate at which
reaction
proceeds
and, where competing reactions occur, the

distribution of the reaction products (22).

The effects of microscale mixing in fiber
suspensions
have been investigated
by
Bennington and Bourne (95) and Bennington
and Thangavel (96). They used mixing-sensitive chemical reactions to measure the
local energy dissipation rate in low-consistency pulp and model fiber suspensions.
Their results showed that the existence of
a fiber network at consistencies as low as
0.5% reduced the turbulence when compared with water alone (96). It is postulated
that the continued disruption of the fiber
network dissipates energy at fiber contact
points. This sink removes energy from the
turbulence cascade which never shows up
as small-scale fluid deformations leading to
better mixing.
5.3 Estimates of mixing quality
The difficulty of measuring mixing quality in pulp suspensions has encouraged the
use of indirect methods for comparing mixers. Indices based on power and energy use
are logical choices. Ene..gy creates mixing
on all scales: it is needed for creation of bulk
flow within the mixer, the rupture of flocs
within the suspension, and the generation
of turbulence.
Mixing power dissipation
Power dissipation is an indicator of the
intensity of relative motion created within
the fluid. Bourne (97) states that "all devices operated at the same power per unit
volume will generate the same rate of
micromixing." This statement, of course,
assumes
uniform
energy dissipation
throughout the mixer. While uniform dissipation may be approached in the mixing
zone in high-shear mixers, it is not achieved
in all mixers, such as the CSTs mentioned
earlier. Thus, the distribution
of power
throughout the suspension is as important
as its total. It should be noted that enormous power may be used to mix and remix
a restricted region of the mixer while other
regions are left unchanged.With the understanding that it must be well distributed,
power dissipation is a useful parameter to
estimate the rate of small-scale mixing. Typical values of power dissipation in common
pulp mixers are given in Table 6.
561
The usefulness of power dissipation as a

parameter can be illustrated by several examples. First, one can estimate the ability
of a mixer to create turbulence within a
suspension. Second, power dissipation affords a rough indication of the rate of mixing achieved by a mixer. On the basis of
data given in Table 6, medium-consistency
mixers designed to fluidize the suspension
all generate approximately the same rate of
small-scale mixing.
Mixing energy expenditure
Power dissipation over time yields energy
dissipation. The energy expended in mixing per unit mass of suspension provides
an indication of the amount of relative motion and therefore of the total mixing that
has occurred. Often, it is the only parameter readily available to estimate mixer performance. Typical energy expenditures for
pulp mixers are included in Table 6.
Several observations may be made using
these data. First, the energy expended in
mixing increases with suspension consistency and reflects the increased difficulty
in creating motion as suspension consistency increases. Second, the energy for
manual laboratory mixing (based on temperature rise) and laboratory high-shear
mixing is about an order of magnitude
greater than the energy expended in mill
mixers at the same consistencies. This difference may account, in part, for the fuct
that laboratory bleaching is often better
than that achieved in the mill. Third, the
energy input for mill medium-consistency
mixers (with the exception of the Ahlmix
and SundsT) ranges from 8 to 43 MJ/t over
a consistency range of 9 to 16%.Although
some of this difference is related to suspension consistency and differing mixer efficiencies, the lowest energy for each mixer
type is approximately the same, about 11
MJ/t pulp. This comparison is remarkable
because mixing times vary over three orders of magnitude in these mixers.
In comparing the energy expended in
mixing, it should be noted that equal energy expenditure does not necessarily imply equal mixing quality. For example, a
mixer operating at a high rate of power
562
Pulp Bleaching
-Principles
and Practice
Tuk~~m-~m~u~m~~~~M~
Mixer
Laboratory mixers
Hand mixing
High-shear (37)
Quantum mixer
(256 g pulp, 2600 rpm)
Fluffer
Hobart (94)
Industrial mixers
Stirred tank (CST)
Agitation vessels
Static
Static
(Komax)
Peg
In Tower, Radial (5)
Ahlstrom, AhImix (106)
Beloit-Rauma, R-Series
Ingersoll-Rand, Hi-Shear
Kamyr MC
Soods SM
SundsT-25
Kamyr MC pump
(pilot plant) (49)
Valve and pipe expansion
(pilot plant)(49)
Power Dissipation
(W1m3)
Energy
(M]lt)
2xlO'
5 x 10'
1.8 x 10.
4.5 x 10'
1.1 x 1()6
2.2 x 1()6
1.2- 1.6 X 105
7.7 x 10'
120
90
180
63
160
310
50 - 200
II -86
Consistency
(Cm,%)
Residence
Time (s)
3
10
10
5
10
15
25-40
28
180
180
10
10
10
10
40 - 200
30 - 240
2-3
4
2-3
10
10 -12
8 - 12
8-20
10
9-16
9 -14
9 -14
18 (max)
150- 400
3-5
4
10-12
8
0.03 - 0.2
2-4
-.05
0.2-0.9
0.025 - 0.05
0.05 - 0.2
8-11
0.3 - 0.5
4-5xl()6
13 - 18
8 - 11
0.3 - 0.4
1 - 3 x 1()6
9 - 11
600
2 - 4 X 10'
3 X 10'
5-9
1 X 105
8 - 11 X 10'
1.7 X 105
1-6xl()6
4 x 1()6
4
11- 15
13
2-6
13- 28
8 - 15
14 - 43
9 -18
3-6
5.5
6-12
4 - II
5
x 107
x 1()6
X 107
X 107
ABNiIson
20-35
3-6x
Andritz Sprout-Bauer HCM
25 - 50
3 - 7 X 107
Kamyr MDR (Frotapulper)
Sunds Rotomixer ROA
(94)
26 - 27
25 45
107
8.6 - 17 x 10'
60-90
22 - 65
400 - 700
70 110
'To convert to horsepower days per metric ton multiply by 0.0155. Unless indicated otherwise, the data
for this table were obtained from reference (24). estimated through consultation with equipment suppliers, or measured directly.
dissipation for a short period of time may

be more effective than a mixer having a
lower rate of power dissipation for a longer
period of time. This possibility is particularly likely for filst reactions where mixing
rate is important. However, when used with
caution, the energy expended in mixing per
unit mass of pulp is a useful parameter for
comparing and characterizing alternative
mixers.
5.4 Mixing rate in industrial mixers

Mixing rate varies depending on the scale
of mixing concerned. For bulk blending
(macroscale mixing) of a medium-consistency suspension in a laboratory high-shear

mixer, mixing time has been measured
as 1.5 s (36). For industrial
mixers,
Bennington et ai. (24) estimated macroscale mixing times using the mixer residence time and assumed a first-order
process. On this basis, estimates of relative
mixing/reaction times, t/tm, were made for
a number of bleaching reactions in common
pulp mixers. These results showed that the
ability of high-shear mixers to more rapidly
achieve macroscale homogeneity may account for some of the benefits derived from

these mixers in pulp chlorination applications.
Mixing rate can also be expressed as the
rate at which energy is converted to smallscale fluid motion in the suspension. For
Newtonian fluids, a characteristic mixing
time is the mean lifetime of the most active
turbulent eddies, expressed by
[4]
t = 12.7;/ Q.l/E)
where E is the energy dissipation per unit

volume and J.1is the viscosity of the fluid
(22). Using the measured energy dissipation rates listed in Table 6 and a correlation
for the apparent viscosity of a pulp suspension given by Bennington (36), t is 0.02 s
for a 10% consistency suspension in a typical high-shear mixer. In a CST operating ilt
3% consistency,
= 0.4
s but varies
locally
throughout the mixer. Taking again the example of pulp chlorination and using t as
t , in both cases t It 1 and mixing rate
at this scale will ~ot mcontrol the outcome
of bleaching.
5.5 Mixing in the laboratory

A number of investigators
have conducted laboratory studies on the effect of
mixing intensity and duration on bleaching.
Liebergott et al. (98) found that increased
agitation, beyond that required to initially
disperse the reactant throughout the suspension, was not beneficial in low-consistency chlorination.
However, prolonged
gentle agitation was found to reduce shives.
Hsu and Hsieh (99) found that for mediumconsistency oxygen bleaching, continuous
agitation (without fluidization) produced
better results than fluidization for a shorter
period. And Hurst (100) found that highintensity mixing had little effect on the outcome of ozone bleaching over the range of
conditions studied.These seemingly contradictory fmdings can be understood by examining each separately using the concepts
developed in this chapter.
For low-consistency
chlorination,
the
relative rate of mixing is higher than that of
chemical
reaction. Once uniformity
is
achieved, further agitation has no benefit.
The shives, however, do benefit from con-
563
tinued agitation even though the net reaction rate is lower for shives than for pulp.
Shives are isolated regions of great chemical demand within the suspension; they
deplete the chemical supply in their vicinity and diffusion alone cannot meet the demand. Continued
mixing maintains
a
uniform chlorine concentration throughout
the suspension which aids shive removal
without affecting pulp quality.
In medium-consistency
oxygen bleaching, there is a need to maintain a homogeneous gas-fiber mixture for the duration of
the reaction. Premature cessation of mixing leads to phase segregation, loss of contact between the oxygen and the pulp, and
reported poor bleaching. In this case, prolonged gentle agitation improves bleaching.
Finally, ozonation is a rapid reaction. In
this case, once mixing of sufficient intensity (rate) and duration are supplied, increased mixing does not improve bleaching.
Mixing also plays a role in the outcome
of bleaching reactions where multiple products may be formed. Earl (37) measured the
formation of AOX during laboratory chlorination using manual and high-intensity mixing. He found that the formation of AOX
was reduced when high intensity mixing
was used. This may be attributed to the increased rate and/or quality of mixing produced by the high-shear mixer.
Although laboratory studies provide indications of what may be expected in mill
situations, laboratory mixing generally uses
more energy and consequently
achieves
better mixing than in the mill. Studies made
under conditions closer to that experienced
in the mill are needed to confirm the relationships indicated above.
5.6 Economicsof improved mixing

In 1990 a CPPAsurvey examined the
benefits of high-intensity mixing in the chlorine and chlorine dioxide stages (13).The
report surveyed mills which had replaced
existing mixers with high-shear mixers.
Reported chemical savings varied and averaged 7 - 8 kg Cl/t for the C stage and 2.0 2.4 kg Clq/t for the 0 stage. However,
individual savings were found to vary over
564
Pulp Bleaching
-Principles
and Practice
a much wider range (2.5 -17 kg CI/t for

the C stage and 1 - 3.4 kg CIO,l t in the 0
stage).
The benefits of improved mixing can be
predicted using laboratory data and computer simulations (5,101.102).
Only the
bleaching response under ideal conditions,
the distribution of chemical within the suspension, and the current and anticipated
mixing quality need be known. This procedure is illustrated in Fig. 19. Here the bleaching response for one particular pulp was
determined under well-mixed conditions
(M 0) in the laboratory. Choosing the distribution of the chemical within the suspension allows calculation of the bleaching
response as a function of mixing quality. In
preparing Fig. 19, a Gaussian distribution
of chemical has been assumed which is in
agreement
with mill measurements
(93,103).
This figure can be used to estimate the
mixing quality in the mill. If, for example,
the mill required 7% active chlorine to produce an extracted pulp of 4.8 kappa, the
mixing
quality
can be reported
as M
=0.30.
This is the approach used by Torregrossa

(5). Evaluation of various operating strategies can also be made using these curves.
For example,
improving
mixing
to M
ing on the mixer, suspension consistency,

and bleaching chemistry, assessment
of
mixing at the macroscaie mayor may not
be appropriate in a given situation.The technique should be validated by comparing
tracer results with pulp quality data (e.g..
the kappa number) obtained in the mill.This
allows the predictive power of the technique to be established for the individual
case.
5.7 Troubleshooting
Mixing is an intimate part of the bleaching process. Consequently a "mixing" p'roblem may be caused by any number of factors
of which mixing in the mixer may be one.
Mixing quality can be estimated using product quality benchmarks or directly measured using tracers. The latter approach
unequivocally confirms the extent that mixing quality deviates from expected values.
The mixing load before the mixer should
be minimized. Pulp and chemical flows
should be uniform within the backmixing
capability of the mixer. A problem with
consistency control ahead of a mixer, for
example, may lead to a mixing problem that
has nothing to do with the mixer. Process
=0.10
would allow the same bleaching result to

be achieved using only 5.7% active chlorine,
an estimated saving of 13 kg/to Other strategies could include maintaining the same
chemical charge while reducing the extracted kappa number. The same procedure
may be used to estimate other bleaching
variables (strength, shives, brightness) provided suitable experimental data exist (101).
Note that little benefit is predicted by reducing the mixing index below 0.1.
To confirm the reliability of the technique, mixing quality should be measured
independently.
Backlund et al. (103) recommend using an inert tracer for this purpose and found that a 200 ml sample size
gave adequate results. Their tests showed
little difference in mixing quality determined using sub samples taken from the
larger sample. However, as shown in Fig.
18 this may not always be the case. Depend-
14
12
~10
CD
D
E
OJ
c:
to
a.
a.
to
8
M
0.60
0.50
0.40
0.30
02(J010
~6
o
357
Active chlorine charge. %

Fig.19. Delipifk4titm lIS 1I.fu1lt:tiOllof chemiC/II
cbtlrgefor D+Cbletlcbhtg of IIsoftwood pulp.
Tbe effect of mixing fJlltllity is giVrtI using

tbe mixing }HImmeterM.
565
changes may also be interpreted as mixing

problems. A production rate change is perhaps the most obvious example. Mixers are
normally designed to operate over a range
of conditions and operation outside this
range may produce inferior mixing. Mixers, of course, can cause problems. Mixer
internals can wear and decrease mixer performance.This problem may be caused by
improper specification of the mixer metallurgy or a change in bleaching chemistry

that accelerates corrosion. In a mechanical
mixer, this may appear as a decrease in
power consumed by the mixer. It is not
unknown for static mixer elements to "disappear" betWeen inspections. In this case,
a measurement
of the pressure
drop
across the mixer would confirm
the
problem.
Acknowledgments
References
1. Schlumberger,
(1%1).
The following individuals are acknowledged

for their contribution
of figures in this chapter:
Ron Weetman, lightnin
Tony Fandetti,Ahlstrom
Process Equipment Inc.
Lew Shackford, Ingersoll-Rand
Brian Greenwood, Kamyr Inc.
Nancy Kuran, Chemineer, Inc.
Jukka Perala, Sunds Defibrator, Inc.
Richard Carlson, Komax Systems, Ine.
Istvan Forster,Anthon
B. Nilsen EngineeringAS
Chris 150m, Koch Engineering Co.
Franz Resch,Adritz Sprout-Bauer Inc.
Keith Barratt, Beloit Corporation
Glossary of terms and symbols

A
Cm
d
I
Fiber aspect ration (lid), [-]

Mass concentration of fibers, [-]
Fiber diameter, [m]
Scale of segregation, [-]
First-order reaction rate constant, [I/s]
I
Fiber length, [m]
M Mixing index, six, [-]
p. Power drawn when gas is present, [W]
P u.w Power drawn in water when gas is not
present, [W]
s
Standard deviation
V Sample volume, [m3]
X Mean value
X. Void fraction, [-]
E Energy dissipation per unit volume,
[W/m3]
Mixing
time, Is]
em
~ Apparent viscosity of fiber suspension,
[Pa.s]
't
Mean lifetime of turbulent eddy, [s]
1:m Characteristic mixing time, Is]

1:, Characteristic bleaching reaction time, Is]
1:, Suspension yield stress, [N/ml]
566
13. Berry, R.M., Pulp

(1990).
Pap. Can. 91(4):T151
14. Uhl, v.w: and Gray, ].B. (Eds.). Mixing:

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Y., "A Kinetic
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54. Berry, RM., and Fleming, B.I., "Why Does

Chlorination
and Extraction
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570
SECTIONVI:
Chapter 3:
Washing and Washers
Authors
P.A. Turner, LH. Allen, S.L Allen,

S. Clarke, R.W. Cunnington, E. Dylke,
C. Hastings, T. Picaro, N.A. Poirier,
R.C. Reid-Bicknell'
1. Introduction
571
2. Fundamentals
of pulp washing.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 571
2.1 Dilution/extraction
and displacement
washing.
. . . . . . . . . . . . . . . . . . . . . . . 571
2.2 Washer performance
parameters
'. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 572
3. Washing equipment
3.1
3.2
3.3
3.4
3.5
3.6
3.7
.............
Vacuum drum washers.
.......
Pressure washers.
............
Wash presses.
...............
Atmospheric
diffusers.
...... ..
Pressure diffusers
............
Comparison
of washer efficiencies.
Proper sampling around a washer
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575
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578
579
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582
582
4. Brown stock and post-oxygen

delignHication
washing
. . . . . . . . . . . . . . . . . . . 582
4.1 Selection of oxygen delignification
washing equipment
. . . . . . . . . . . . . . . . . 584
5. Washing in the bleach plant
5.1 First washer. . . . . . . . . . . . . . . .
5.2 Second washer . . . . . . . . . . . . .
5.3 Washers used later in the bleach
5.4 Washing in an ozone or peroxide
6. Control
of bleach
washers.
..............
..............
plant. . . . . . . . .
bleaching stage.
and pitch
9. Defoamers
and drainage
10. Washing
bleached
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585
585
585
585
585
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7. Material selection
for bleach washers.
...
7.1 Oxygen delignification
washers.
.....
7.2 Chlorine/chlorine
dioxide washers
7.3 Alkaline extraction
washers.
........
7.4 Hypochlorite
washers.
.............
7.5 Hydrogen peroxide washers.
........
7.6 Electrochemical
protection
for stainless
7.7 Manufacturing
considerations.
8. ExtractIves
....
....
....
...
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 586
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 587
587
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 588
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 588
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 588
steel equipment
. . . . . . . . . . . . . . . . 588
588
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 589
aids
mechanical
591
and high-yield
'See authors' affiliations next page.
569
pulps
. . . . . . . . . . . . . . . . . . . . 592
contributed
text to this chapter
in the following
P.A.Turner:
LH. Allen:
S.L Allen:
S. Clarke:
R.W. Cunningham:
Lead author, Washing
E. Dylke:
C. Hastings:
T. Picaro:
N.A. Poirier:
R.C.Reid-Bickne~
Brown stock and post-oxygen
equipment,
Extractives
and pitch
Defoamers
and drainage
Material
Washing
washing,
selection
areas:
Control
of bleach
aids
for bleach
washers
equipment,
Brown stock
Bleach plant washing
and post-oxygen
delignification
washing
and high-yield
pulps
Bleach plant washing

Washing
bleached
Fundamentals
mechanical
of pulp washing
Bleach plant washing.
washers
de lignification
Chapter VI 3: Washing and Washers
Chapter VI 3:
Washing
and Washers
havior of
defoamers
followed
bleached
pulps.
571
Washing in a conventional bleach plant

has not received the same amount of attention, historically, as washing in the brown
stock area. The need to wash pulp adequately between
bleaching
stages is
becoming increasingly important, however,
because of environmental pressures to decrease the discharge of bleach plant effluents and to change bleaching technologies.
This chapter is divided into several sections, starting with a discussion of pulp
washing principles and definitions and an
introduction to the types of washing equipment found in the bleach plant. Washing
in the brown stock and post-oxygen delignification areas is then covered briefly because carryover from these areas has a direct
impact on bleach plant operations and because broad commonalities exist between
all washing areas within a mill. Bleach plant
washing itself is then discussed, and a discussion of the potential for automatic process control
to improve operation
is
presented. A review of material selection
for bleach plant washers follows. The be-
The primary objective of all pulp washing operations is to remove soluble organic
and inorganic materials. Dissolved material carried with the pulp to delignification
and bleaching stages can be deleterious by
impairing the delignification or bleaching
and by consuming costly bleaching chemicals with the result that the end product
may be a pulp with lower brightness or
lower strength.
It is necessary for the reader to possess a
basic understanding of the principles and
definitions of pulp washing before equipment design, operation, and optimization
can be discussed. Parts of the section which
follows are taken from a paper by Crotogino
etal. (1).
2.1 Dilution/extraction
and displacement washing
Dilution/extraction and displacement
washing are the two basic operations that
take place when pulp is washed (Figs.1 and
2, respectively). All pulp washing equipment described in this chapter performs
Clean
pulp
\ !
...
...
... "
...
"
Dirty
. water
...
Mix
Fig. 1. Sebem4tk dUlgrtlm of dtl"tltntlexlrlletton
Drain
wabt"g.
Clean
water
Clean
pulp
,-:f
2. Fundamentals of pulp washing
Clean
water
extractives and pitch and use of

and drainage aids are discussed
by a closing section on washing
mechanical and other high-yield
1. Introduction
Dirty
pulp
572
Press
I '
,--,,"1,
I
Dirty
pulp
Fig.2. Sebem4tk dl."..",. of dts/J'-t
I_~::_,,_~-~_~?~
wabt"g.
one or both or these basic operations. Commercial washers that depend on dilution!
extraction alone include presses for washing chemical pulp and screw presses and
twin-wire presses for washing (chemi)mechanical pulp. Washers that use a combination
of dilution/extraction
and
displacement washing include pressure and
atmospheric
diffusion washers, vacuum
drum filters, wash presses, and pressure
washers such as the Compaction Baffle Filter (CBF) and the Drum Displacement (DD)
Washer.
In dilution/extraction
washing, an unwashed pulp slurry is diluted and thoroughly mixed with clean wash water or
weaker wash liquor and then thickened by
filtering or pressing (Fig. 1). The washing
efficiency depends primarily on the consistency to which the pulp is diluted and thickened. The amount of soluble organic and
inorganic material remaining in the thickened pulp can be easily calculated if it is
assumed that the solute is split in the same
proportions as the liquor although deviations from this simple picture of dilution!
extraction washing can be caused by incomplete mixing. Efficiency also depends on
the extent to which solute has been sorbed
onto the fibers and the time required for
solute to diffuse out of the fibers (1).
''''''1'-'
I_';'_~_-=--~--'-
DIrty
water
In displacement washing, the liquor in a
pulp mat is displaced in a piston-like fashion with weaker wash liquor or clean water (Fig. 2). Mixing at the interface between
the wash liquor and the liquor being displaced should be minimized to achieve ideal
displacement washing. If no mixing takes
place, it is possible to remove all of the solute by displacing one volume of the liquor
in the pulp pad. In practice, thorough washing cannot be achieved using the principle
of displacement
washing alone because
there is always some mixing at the interface between the liquor in the pulp and the
wash liquor and because some solute is
trapped within the fibers. Variables such
as displacement velocity, pulp pad thickness, pulp pad consistency, and temperature have been shown to have an effect on
displacement washing efficiency (2-7).
2.2 Washer performance parameters

The efficiency of a pulp washing system
is judged by how much of the solute present
in the washer feed is removed from the pulp
and the amount of wash water required. A
number of schemes and nomenclatures
have been developed to express the performance of washers and washing systems.
Definitions of washing terms are presented
in Table 1 in reference to the generalized
washing module defined in Fig. 3 (8).
Filtrate
573
Wash water
574
Table 1: Deft,dtlml of 1II1IlI"'",terms.
Tenn and Description
_ V.. YI
~Vz,Yz
Lo,Xo
Washer
L., X1_
p
Fonnula'
Dilution Factor, DF
liquor leaving with

wash liquor
washed pulp
enterinl!
washed pulp
DF =V,-L,
Wash Liquor Ratio, R

Unwashed
Washed pulp
pulp
filtrate stream, metric tons of liquor/oven dry (o.d.) metric ton of washed pulp
pulp stream, metric tons of liquor/o.d. metric ton of washed pulp
Yt, Y,=
concentration
of dissolved solids in pulp stream, kg of dissolved solids/metric ton of liquor
concentration
of dissolved solids in liquor stream, kg dissolved solids/metric ton of liquor.
Fig. 3. ScbemiIIk
Weight Liquor Ratio, W

filtrate liquor leaving
liquor entering with unwashed pulp
W=VtlLo
WashYie1d,Y
tliIIgrtIm of IIIIIlI""'g motlrIle.
Table 1 lists the three most common Rarameters used to describe the amount of
wash water used and the efficiency of solute removal in pulp washing operations. Of
these, dilution factor (DF) is the only one
that is defined in tenns of the weight of pulp
being washed. DF represents the amount
of water that is added during washing over
and above the volume of water in the pulp
pad and provides an indication of the evaporator load attributable to brown stock and
post-oxygen washing and the effluent volume from open washing stages in the bleach
plant. For displacement
washing, a DF
equal to zero implies that the liquor in the
pulp pad was displaced by an equal amount
of wash liquor. When pulp is washed with
less water than the amount leaving with the
pulp, the dilution factor is negative.
The wash liquor ratio (R) is defined with
reference to the liquor leaving with the
pulp. R equals V 2 IL, which is the ratio of
shower water applied ' on the washer to the
flow of filtrate leaving the washer with the
washed pulp. For displacement washing,
an R equal to 1 implies that the liquor in
the pulp pad was displaced by an equal
amount of wash liquor. The weight liquor
ratio (W) relates the filtrate flow rate to the
liquor entering the washers with the pulp.
Rand Ware approximately
equal when
there is no change in pulp consistency
through a washer.
Table 1 lists the two ratios commonly
used to describe the amount of solute re-
R =V/Lt
wash liquor entering

liquor leaving with washed pulp
moved from pulp during washing. Implicit

in the definition of the wash yield (Y) is the
assumption that no solute enters the washer
with the wash liquor. On the other hand,
the displacement ratio (DR) accounts for
solute entering with the wash water. It does
this by calculating an efficiency based on
the premise that pulp cannot be washed
any cleaner than the wash water.
Any combination of parameters describing the quantity of wash liquor used and
the quantity of solute removed can be used
to characterize the performance of a washer
or a washing system. However, it is not
possible to compare the efficiencies of two
different washing systems using DF,R,Y, or
DR unless both systems operate with the
same feed and discharge consistencies. The
modified Norden efficiency factor CE,) and
the equivalent displacement ratio (EDR) can
be used to compare the efficiency of different washers when the washers being evaluated share the same value for one of the
wash-liquor usage parameters.
The Norden efficiency factor (8) is derived by comparing the performance of a
given washing system to that of a hypothetical system of ideal countercurrent
mixing
stages in series. It is defined as the number
of these ideal stages required to achieve the
same depatting stream flows and concentrations as in the actual washing system or
single washer. When a washing system has
n washers in series, its efficiency can be
determined by summing the Norden effi-
dissolved solids removed
~dissolved solids entering

Displacement
= 1- !b
Loxo =
Loxo
Ratio, DR
reduction of dissolved solids

maximal reduction of dissolved solids possible
DR
Modified Norden Efficiency Factor, EM
Number of ideal counter current mixing stages

equivalent to a washer or washing system.
EqulvalentDisplacementRatio,EDR
Est=
log (1+
(1
- EDR)
and ICF =
XI
y,
x" -
log !:Y(Xo - Yt )
L, x, -y,
where
Displacement ratio for standard inlet consistencyof 1% and discharge consistency of 12%
= Xo -
- Cst
where Lst = 100Cst
~)
= (1
- DR)
DCF
(DCF)
(ICF)
100 C
7.33 (C~
99 (Ll + DF)
LI (99 + DF) - L. (99 - L,) (1 - DR)
:VI,VZ = filtrate stream, metric tons of liquor/oven dried (o.d.) metric ton of washed pulp;
pulp stream, metric tons of liquor/o.d. metric ton of washed pulp;
Lo' Lt
concentration
of dissolved solids in pulp stream, kg of dissolved solids/metric ton of liquor;
XO,x\
concentration
of dissolved solids in liquor stream, kg dissolved solids/metric ton of liquor.
Y1,Y,
=
=
ciency factors for the individual washing

stages (1). This is of interest in brown stock
or post-oxygen delignification washing. Because constant discharge consistency is frequently not the case, a modified Norden
efficiency factor CE,) (9) has been developed which is not dependent on the inlet
or discharge consistency.
The equivalent displacement ratio (EDR)
(10), like
Est' is a performance parameter
that is independent
of the inlet and discharge consistencies.
It expresses washer
performance
in terms of a hypothetical
washer operating at 12% discharge consistency that has the same dilution factor as
the actual washer. Loss from the hypothetical washer must be the same as that from
the actual washer. Loss in this case is dermed as the difference between the weight
of dissolved solids leaving with the washed
pulp stream and the weight of dissolved
solids entering with the wash liquor.
Both E and EDR are useful tools for comparing th~ performance of washers or wash-
Efficiency Factor,
E"
Vacuum drum filter
1.2 - 2.5
0.58 - 0.77
Decker/rewasher"
Compaction baffle filter
0.9 - 1.5
0.50 - 0.58
4.5-4.6
0.80 - 0.85
Drum displacer washer
6.5-8.3
0.95 - 0.98
Rotation
Face wire
~,
/.,
/"
3.0-3.7
0.76 - 0.90
Two-stage atmospheric
diffuser
5.9 - 7.4
0.92 - 0.96
0.87- 0.92
~.
pipes
Fig. 4. CfIt."",., dUIgrtmI of lNICII"mtlrum /lltIS'- (lflgn'SOll.IlJuul).
4.5-6.0
~\,~..
Internal
Pressure diffuser
for service
~ Worm drive
..;i~
Drop leg
'""" Valve
/?""7'J
Trunnion
"- Drum
One-stage atmospheric
diffuser
Values were calculated
0.83 - 0.86
Wash press'
576
Corrugated
Equivalent Displacement
Ratio,EDR
Modified Norden
Equipment Description
575
in an unbleached
softwood
kraft line, using total dissolved
solids as the
basis. Dilution factor 3. (Infonnation courtesy SandweU Inc. and H.A. Simons Consultants Ltd.).
bA decker/rewasher is a simple vacuum decker, or thickener, that bas been converted to a washer by the
addition of shower bars. It functions much like a vacuum drum filter except that the consistency of pulp
leaving the drum is generally lower.
,
Values of E. for wash presses are very low because solute removal is achieved mostly in the final
dewatering step.
ing systems (Table 2). EDR is easier to understand because it is directly related to the
fraction of solute removed; E ,on the other
hand, expresses performan;e
in terms of
an equivalent number oftheoretica1 stages.
One advantage ofE" over EDR is that the E..
for the overa1l wash system can be easily
calculated from the E.. values of the indio
vidual stages.
3. Washing equipment
The five most common types of washers
used in oxygen delignification systems and
in bleach plant operations are described in
this section in the following order: vacuum
drum washers, pressure washers, wash
presses, atmospheric diffusers,and pressure
diffusers.
It is important to emphasize that wash.
ing equipment
should be selected only
when its design specifications meet the requirements for a particular operation. The
capital and installation costs of washing
equipment are important when consider.
ing a purchase, although several factors can
outweigh the importance of capital cost
(fable 3). Typical loading factors, operat.
ing consistencies, and drum dimensions of
vacuum drum washers, pressure washers,

and wash presses are listed in Table 4.
.leetltm oflllUbl..g
tlHlt'''flT""k 3. FtICIOrS
BtJI"pmnd.
.
.
Intended service
.
.
.
.
Washer Type
Loading Factor"
(admt/d/m')
Vacuum drum
washer
GasFree filter (GFF)
Compaction baffle
filter (CBP)
Drum displacement
(DD) washer
Wash press
8.0.8.5
< 12
-30
Consistency
Feed
Discharge
(% a.d.)
(% a.d.)
Drum Dimensions
Diameter x Length
(m x m)
1.0-1.3
16-18
4.1 x 9.1
0.5 - 2.0
14 -17
4.0 x 7.0
3.5 . 4.0
13 -15
3.0 x 4.0
< 15
3.0 - 5.0 or
10.0 - 12.0
12 - 15
4.0 x 6.0
< 27
3.5 - 4.0
28- 35
1.2 x 5.0
(x 2 rolls)
25
Capital cost
Operating
Operational
Down-time
routine
Availability
.
.
.
ease of the equipment

and mechanical
necessary
accessibility
for routine
and non-
maintenance
of spare
parts
Building space necessary

the system
Energy consumption
and factory
support
to accommodate
of the equipment
Compatibility with other washing

within the mill
'Design values for a modern greenfield softwood kraft mill producing 1000 admt of pulp/day. (H.A. Simons
Consultants Ltd. and SandweU Inc.).
"Loading factor is defined as the drum loading capacity in admt of pulp/day/square meter of drum surface
area.
systems
3.1 Vacuum drum washers

The rotary vacuum drum washer or filter (Fig. 4) has been the type used most
commonly for browstock and bleach plant
washing (1,12) and is still the washer type
selected for many applications. Operation
of these units can be divided into several
steps. Pulp is diluted to low consistency
with recirculated filtrate from the filtrate

tank. The slurry enters the vat at an optimal consistency of between 1.0 and 1.25 %
for softwood and 1.1 and 1.5 % for hardwood when the washer operates at design
capacity. Vat consistencies are higher in
overloaded equipment to increase capacity
because the limitation associated with this
type of filter is governed by the fiItrate handling capacity of the system. A wire-covered drum, typica1ly 4.1 meters in diameter
by 9.1 meters in length for a 1000 admt/d
mill (fable 4), rotates in a vat and a pulp
mat forms on its surface. The mat is partially dewatered with the aid of a vacuum
created inside the drum as filtrate flows
down the drop-leg to the ftltrate tank. On
the upper part of the drum, where the mat

is not immersed in the vat, shower wash
water is applied to displace dissolved sol.
ids from the pulp. Further dewatering takes
place before the mat is removed from the
drum.
Pulp consistency leaving a vacuum drum
washer can be as low as 8% if the washer is
overloaded or if air entrainment is a problem, or as high as 18% when the washer
performs optimally. Louvered surfaces such
as the Coru-dek (Fig. 5) have been installed
successfully on washer drums to improve
mat dewatering.
A doctor blade lifts the
washed mat off the drum, assisted by air or
water jets. The discharged pulp pad is broken up by a screw conveyor and the pulp
577
578
1.8
Airlift take-off
Hood pr_ure
throttle back
to blower _a...-
~u
01
=..
0.6
E
..
~ 0.4
"S.
..
is Dol
0.0
4
Fig. 6. Gaerwl
~
0
1
DUution Factor
rflltllHnrsblp
betllJen
tUl"Utm
flU:-
__
tur"""~rwIIofortl"""'"
tJ/IC'fYIIIlm (H.A. Simorrs
ConsrllltItIls
U41.).
Division
Grid
Fig. 5. C"t-tlllItry tlItIgrtI'" sllflwlng Co",-."

slrtu:Utm (Ingersoll-Rilnd).
COII-
drops through a chute to the next piece of

equipment.
Filtrate removed from the pulp travels
down a 30- to 35-foot long drop-leg (12) and
is deaerated in the filtrate tank. The dropleg and filtrate tank must be designed with
the correct geometry to avoid air ingress
and separation in the drop-leg because more
than 25% of the volume flowing down the
drop-leg is air (12). The filtrate tank is designed to separate air from the filtrate. Filtrate is then recirculated as dilution water
for pulp entering the washer or can be used

as shower water for the previous washer.
Sheet dryness and shower water flow
rate and distribution affect washing efficiency. A general relationship has been
observed between dilution factor and displacement ratio in mill operation (Fig. 6).
An increasing amount of wash water must
be applied for every incremental gain in
cleanliness (13).
Ahlstrom Kamyr markets the GasFree Filter (GFF), a modified vacuum drum washer
(Fig. 7). The feature that makes the GFF
unique is that air is separated from the flltrate using a specifically designed rotary
valve. Filtrate travels down the drop-leg and
air is vented back to the hood to minimize
Fig. 8. lH4grt1'" of CornptICUtm BtI.tfIe Filter (CBF) (Ingersoll-RtInd).
..
1. Cake forming
2. Flat washing
3. Second washing
4. Cake discharging
..
FIltrate /'
no. 2 out
Fig. 9. Sebem4t1c
Washed
pulp
Unwashed
pulp
Filtrate
Fig. 7. C"t-tlwtly
tlItIgrwm of GtIsFree Filter (GFF) (ilblstrom
KiImyr Inc.).
FIltrate
no. 1 out
Pulp out
tlItIgrwm of Drum IHspltU:er (DO) IlItISber (ilblstrom
air emissions from the washer. This increases the efficiency of the drop-leg and
provides a higher mat discharge consistency.
3.2 Pressure washers

Recent washer installationshave been
the Ingersoll-Rand
Compaction
Baffle Filter
KiImyr Inc.).
(CBF) (Fig. 8) or the Ahlstrom Kamyr Drum

Displacement (DO) Washer (Fig. 9). Operation of both is described in this chapter.
Generally, gas emissions from a pressure
washer are lower than those from a vacuum
drum washer because the former are sealed.
The possibility of filtrate flashing in the
drop-leg limits the upper operating tempera-

ture in a vacuum drum washer but this
maximum temperature can be exceeded in
a pressure washer, because of the absence
of a drop-leg.
Compaction Baffle Filter (CBF)
The CBF is becoming popular in brown
stock and oxygen delignification systems as
well as in new or modernized bleach plants
because of its compact size, high feed consistency (Table 4), and high washing efficiency. A pulp slurry is fed to the vat of a
CBF at 3-5% consistency
and a mat is
formed on the surface of the rotating drum.
High feed consistency allows the CBF to
operate at much higher loading per surface
area than a conventional drum washer and
reduces the volume of filtrate removed from
the pulp to one-quarter of that for a conventional drum washer. This allows piping,
pumps, and tanks to be sized much smaller
for a given design capacity.
A baffle separates the feed section ofthe
vat from the wash liquor pond. An initial
pressing of the pulp by the baffle increases
the consistency to 20% and forces liquor
and dissolved solids from the pulp. The mat
then enters the wash liquor pond and washing is carried out at 10% consistency. The
mat is discharged from the CBp,typically at
13-15% consistency.
A sealed hood over the washing pond
provides the driving force for filtrate displacement. The hood is pressurized by a
low-pressure
blower which recirculates
vapor from the filtrate tank. Pressurized
operation eliminates the need for a dropleg and allows the CBF to be installed at
any elevation. Pond washing eliminates the
foam generated by spray-type showers and
minimizes air entrainment.
Drum displacement (DO) washer
The DD washer is a pressurized, multistage, drum washer consisting of a mat formation zone, two to four washing zones,
and a discharge zone. A two-stage unit can
be selected for post-oxygen delignification
washing applications and a three- to fourstage unit can be selected for brown stock
washing applications. The washer drum is
typically 4.0 meters in diameter by 6.0
579
580
meters in length for a 1000 admt/d mill

(Table 4).
The drum is surrounded
by a casing
which is separated into sections by sealing
bars that run along the length ofthe drum.
Pulp enters the forming zone at 3-5 % consistency or at 10-12 % consistency, depend-
Hood
Doctor
ing on the design chosen, and forms an

approximately 10-12 % consistency mat on
the drum. The drum passes stationary sealing bars as it rotates. These sealing bars
create a separate stationary wash pond for
each washing stage. The wash zones remain
stationary as the pulp mat rotates through
them.
Fully flooded displacement washing occurs as wash water flows countercurrently
from one washing compartment
to the
next, and no interstage filtrate tanks are required. Pulp rotating past the final wash
zone enters a vacuum zone where mat consistency is raised to approximately 15% by
a vacuum pump. Filtrate removed from the
pulp is returned to the previous washing
zone and fresh water is added to the final
washing stage.
HydrauUc
Moton
Filtrate
Oul
Fig. 10. ScbeIruItk
of IIItISb J1ress (Sliruts De.fibrtltor).
baffles. Wash liquor is then added in the

displacement zone and extracted through
small perforations in the rolls. Filtrate leaves
Wnh
through the openings at the end of the rolls
lOall
and is discharged through outlets in the
bottom of the vat to a small tank. An exhaust fan is used to remove vapors from the
enclosed hood and shredder-conveyer.
Mter displacement
washing, the pulp is
ItJdflullc pressed in the roll nip to 30-35% consiscyll.der
tency. One of the rolls is adjustable to set
the nip. Pulp leaving the nip is discharged
to an overhead shredder-conveyer.
3.3 Wash presses

The wash press (Fig. 10) is mainly a dilution/extraction
washer. It is designed to
carry out the operations of thickening, displacement washing, and pressing in a continuous sequence. The benefits of using a
wash press over a vacuum drum washer in
a given application are similar to the benefits of using a CBF.The consistency of pulp
discharged from a wash press is much
higher than that for the other washers described, which explains its high efficiency
(Table 2).
The Displacement Press offered by Sunds
Defibrator is composed of two synchronous, counter-rotating rolls that operate in
a pressurized vat. Typical dimensions of
each roll are 1.2 meters in diameter by 5.0
meters in length for a 1000 admt/d mill
(Table 4). Pulp enters the vat, at a consistency of 3-5%, through dual inlets on opposite sides of the machine. A pulp sheet
at 10% consistency is formed in the dewatering zone between the rolls and tapered
tile"..".
Slott
oil
51ock1.
3.4 Atmospheric
diffusers
The atmospheric diffuser (Fig. 11) is essentially a displacement washer. It can be
installed as a single-stage washer in the
bleach plant or as a single- or two-stage unit
for washing brown stock or oxygen-delignifled pulp. A medium-consistency
storage
tank is often located below the washer
when the washer is used in the brown stock
area. The diffuser is mounted on the top of
a bleach tower when used as a bleach
washer (Fig. 11).
A two-stage diffuser is typically 16 meters
high (elevation difference between pulp
inlet and wash water inlet, including cone
section) and 6 meters in diameter at the
Fig. 12. Cu'-"fIHIJ' fJlew of 11II"Imospberk

(Ahlstrom KAmyr lrre.).
dt/ftlser
base for a 1000 admt/d mill. Pulp residence

time in an atmospheric diffuser is about 15
minutes for a two-stage diffuser.
Equally spaced concentric screen rings
are arranged about a common vertical axis
inside the diffuser tank for each washing
stage (Fig. 12). Each ring is comprised of
two perforated plates about 5 centimeters
apart that form a hollow interior channel
for filtrate to flow through. Pulp travels
upward between the concentric rings and
wash water is introduced into the pulp
through distributors located in the annuli.
Filtrate is forced to flow through the pulp
to the screens where it is extracted.
Filtrate flow is countercurrent between stages
in a multi-stage diffuser.
The entire screen assembly undergoes a
regular, vertical stroking cycle to remove
pulp from the surface of the screens and
prevent plugging. The upstroke speed is
adjusted so as to be slightly greater than the
pulp flow rate through the diffuser. The
diffuser is held at the top of its stroke for
581
approximately
5 seconds and is then
downstroked
rapidly in approximately
1
second.
The advantages of an atmospheric diffuser for washing bleached pulp include low
energy requirements because the pulp is
not diluted and rethickened. Space requirements are minimized because the diffusers
are normally located above a high-density
storage tower or a bleach tower. The diffuser is totally enclosed, minimizing the potential for air entrainment in the pulp.
The entire screen assembly undergoes a
regular, vertical stroking cycle to remove
pulp from the surface of the screens and
prevent plugging. The upstroke speed is
adjusted so as to be slightly greater than the
pulp flow rate through the diffuser. The
diffuser is held at the top of its stroke for
approximately
5 seconds and is then
downstroked
rapidly in approximately
1
second.
The advantages of an atmospheric diffuser for washing bleached pulp include low
energy requirements because the pulp is
not diluted and rethickened. Space requirements are minimized because the diffusers
are normally located above a high-density
storage tower or a bleach tower. The diffuser is totally enclosed, minimizing the potential for air entrainment in the pulp.
3.5 Pressure diffusers
The pressure diffuser (Fig. 13) is a displacement washer. It is built to operate at
digester pressure and is most commonly
positioned directly after a digester or an
tower. This is a
pump-through device and the pulp is discharged with sufficient pressure to flow to
the next operation. A unit for a 1000 admt/d
mill is 3 meters in diameter and 18 meters
high. The complete system, including a filtrate tank, occupies a floor space of 4.5
meters by 12 meters. Pulp residence time
in the diffuser is about 3 minutes.
Pulp at medium consistency is fed to the
bottom inlet of the pressure diffuser. The
pulp passes up through the annulus between the wash baffles on the outer shell
582

and an inner cylindrical screen (Fig. 14) and
forms a uniform bed of pulp approximately
2.4 centimeters thick. A pressure diffuser
operates optimally at 10-11 % consistency.
Wash liquor is introduced through baffles
and is forced to flow through the pulp,
through the inner cylindrical screen, and
into a central collection chamber. The wash
distribution baffles assure a uniform flow
of wash f1ltrate around the entire annulus.
The pulp is transported evenly in all parts
of the pressure diffuser by the upward
movement of the screen. As in an atmospheric diffuser. the screen is moved periodically in the direction opposing the flow
of the pulp to remove pulp from the screen
and prevent plugging.
Fig. 13. cu'-"w"y dl"p'"m of pressure

(Ahlstrom KiImyr lrre.).
diffuser
3.6 Comparison of washer efficiencies

Several equipment vendors have developed in-house washer performance parameters.
Caution must be exercised
in
comparing these efficiencies because seemingly similar parameters can be defined
differently. An understanding of the assumptions implicit in the definition of various
parameters can also help interpret this information.
For example, the modified
Norden efficiency factor calculated for a
values for
wash press is low relative to
E"
other types of washers, yet a wash press
----
"' ---
Pulp
w nozzle
Screen
--,
supportcytlnder
Fig. 14. CaI-"fIHIJ'dUlgrtmI
of pressure
tU/ftIser
cross-set:lltm
(Ahlstrom
KAmyr lrre.).

actually offers excellent solute removal because of the thickening achieved as reflected by high EDR values (fable 2).
With this in mind, typical modified
Norden efficiency factors and equivalent
displacement ratios are presented for the
various types of equipment discussed in this
chapter (fable 2). These values are intended
to be used only as a guide. The Estand EDR
values were calculated using dissolved solids as a basis and are typical for service in
brown stock or oxygen de lignification
washing. No data are available for bleach
plant washers.
The term solute is used throughout this
section for simplicity. It refers to any soluble
species found in wash liquor streams including total dissolved solids, dissolved organics or inorganics, and dissolved lignin "Or
sodium compounds in the brown stock and
post-oxygen delignification washing areas.
In the bleach plant, the list of soluble species can be extended to include cWoride
ion.
It is important to know which solute variable was used to calculate washer performance parameters before attempting to
interpret results. For example, an alkaline
extraction stage vacuum drum washer in a
bleach plant was found to have a DR of O.54
based on conductivity measurements and a
DR of 0.83 when total dissolved solids values were used (information courtesy of
Ingersoll-Rand).
3.7 Proper sampling around a washer

Careful planning and sample collection
are required to determine performance parameters in a washer operation.
Process
streams should be sampled only when the
process is operating smoothly and after
major disturbances have passed through the
system. All samples should be collected simultaneously to eliminate problems created
by unsteady operating conditions.
Obtaining pulp samples from a vacuum
drum filter can present special problems
because cleanliness and consistency can
vary significantly across the length of the
drum (Table 5) (11). Samples of washed
pulp should be collected from several
equally spaced locations across the drum
583
and composited to ensure that a representative sample is obtained. The top and bottom of the mat and the quantity of pulp from
each location should be weighted equally
in the final composite. likewise, samples
should be collected and composited along
the length of a washer vat.
Tllbte5. YIIriIIItmrs ~
/HIlpwruistmrey
'"
crnullletlfJlty
.'Off' tbe l""tb of .
.""
fJIICfI_ tltw,. fIIIISber.
Sample location
on the drum
Left
Mid-left
Center
Mid-right
Right
,
Consistency
(%)
10.74
10.40
11.65
10.87
11.50
Conductivity'
(mS/cm at 25C)
0.88
1.09
0.87
1.33
1.00
Conductivity was measured on filtrate squeezed

from the pulp mat.
Simple material balances based on water, fiber, and solute concentrations can be
calculated using washer data as a validity
check on the sampling program. All calculations should balance when sampling is
conducted during a period of stable operation. The accuracy of flow meters should
be verified because the calibration of these
instruments can change.
4. Brown stock and post-oxygen delignification washIng

Sodium losses, reported as saltcake (kg
NazSO/odmt pulp) or soda (kg Nap/odt
pulp), have been used to evaluate brown
stock and oxygen delignification washer
performance. Losses are estimated by measuring the conductivity of mtrate squeezed
from washed pulp. Losses can also be measured using atomic absorption spectrophotometry on the filtrate, but this method is
slow and laborious.
However, sodium loss is not a good indication of the dissolved organic material carried over to the bleach plant. It has been
suggested that the concentration
of total
black liquor solids (BLS) in filtrate is the only
true variable that can be used to measure
carryover when comparing washing efficiencies between different mills or differ-
584
ent types of equipment. In cWorine-based

bleaching sequences, BLS carryover to the
first bleaching stage can consume approximately 0.4-0.5 kg equivalent cWorine/kg of
total dissolved solids carryover (information
courtesy Ingersoll-Rand).
Others propose that the chemical oxygen demand (COD) of filtrate carried with
pulp from the washing area is a better measure of washer performance (14) because
it provides a direct indication of the concentration of dissolved organic material in
the mtrate, of increased chemical consumption in the first stages of bleaching, and of
increased levels of contaminant loading in
bleach plant effluents.
COD, BLS, and
saltcake concentrations
are not related directly because the ratio of dissolved organics to inorganics in mtrate streams may vary
significantly from mill to mill (14).
The ability of a washer to remove dissolved organic material from pulp can be
improved by increasing the residence time
before or in the washer. This retention time
allows the COD-causing compounds to diffuse out of the pulp fibers and facilitates
their removal by washing (14). To reduce
the COD-carryover to the first bleaching
stage, some mills take advantage of the residence time in the unbleached high-<lensity
storage tower to leach organic matter from
the pulp fibers and follow the tower leaching with an open wash stage before bleaching. Increases in temperature and pH can
increase the rate of diffusion of dissolved
organic material from pulp fibers (14).
For a mill using an oxygen delignification
stage, consideration should be given not
only to the amount ofBLS entering the stage
but also to the composition of the BLS in
terms of raw black liquor solids (RBLS) and
oxidized solids (OS) (15). RBLS are dissolved solids carried forward from the digester and pre-oxygen washers; OS are
dissolved solids discharged from the oxygen delignification stage carried with the
mtrate through the washing lines.
Black liquor solids (BLS) carryover increases the consumption
of oxygen and
sodium hydroxide in the oxygen delignification stage. Optimum performance is
obtained in an oxygen delignification stage

when OS carryover is limited to 150 kg dissolved solids/odmt and RBLS carryover is
limited to 45 kg dissolved solids/odmt for a
total BLS carryover of 195 kg dissolved solids/odmt (15). When BLS carryover is
higher, delignification can be retarded and
pulp strength properties can be adversely
affected. RBLS and OS values must be calculated manually because there is no
method for measuring the split between
oxidized and unoxidized black liquor solids during operation.
A number of washing systems have been
designed surrounding an oxygen delignification stage to ensure good selectivity by
limiting raw black liquor solids (RBLS)
carryover well below the suggested value,
especially in systems that are designed to
achieve high levels of delignification such
as high-consistency systems. At the same
time, modern post-oxygen washing systems
are being designed and operated to provide
less than 10 kg BLS/odmt carryover to the
bleach plant.
4.1 Selection of oxygen delignification

washing equipment
Washingis an important feature of any
oxygen de lignification system (16) and several types of equipment are now being used
for post-oxygen washing. Their common
feature is that they efficiently remove solute, measured as BLS or chemical oxygen
demand (COD), from pulp before it enters
the bleach plant. A COD concentration of
less than 10 kg/admt in pulp leaving the last
post-oxygen washer is important for current
chlorine dioxide bleaching technology to
ensure low levels ofAOX in pulp mill effluent. A concentration
lower than 10 kg
COD/admt is a critical requirement for totally cWorine-free (fCF) sequences.
Wash presses, pressure washers, and
pressure and atmospheric diffusion washers are the most common types of equipment being used for post-oxygen washing.
Modern washing systems require only two
stages of washing to decrease COD concentrations to less than 5 kg/admt in washed
pulp. In some mills, an additional open

stage of washing is provided in which some
f1Itrate is sewered following the second
post-oxygen washer. 111is additional stage,
usually a traditional vacuum drum washer,
can decrease COD in pulp by an additional
50%.
5. Washing in the bleach plant

Washers following individual bleaching
stages have typically been vacuum drum filters. Their performance in removing soluble
organic and inorganic material has not been
well documented. This is changing as mills
strive to decrease water consumption and
use bleaching sequences that require better washer performance.
The first two
bleaching stages are arguably the most important because they remove most of the
dissolved lignin and inorganic material from
the pulp.
5.1 First washer
The first washer follows a (C+D)-, (DC)-,
or D-stage tower in a conventional bleach
plant. 111iswasher, in combination with the
washer following the first extraction stage,
must remove 80-90% ofthe lignin from the
pulp entering the bleach plant. The firststage washer removes hydrochloric
acid
(12) and dissolved lignin and carbohydrates
generated from the reaction of chlorinebased chemicals with lignin. Carryover of
filtrate in pulp leaving the first washer can
increase alkali (NaOH) consumption in the
following extraction stage and lead to poor
lignin removal and decreased final pulp
brightness.
Sodium hydroxide used in the first extraction tower is generally added to the discharge of the first washer. The requirement
for fresh alkali is minimized by using the
alkaline filtrate as the final wash water applied in the first washing stage. Another
function of the first-stage washer is to increase the stock consistency for the following extraction stage.
5.2 Second washer

Effective washing is required after the
first extraction tower to minimize chemical requirements and achieve pulp bright-
585
ness targets in the following bleaching

stages. Washing with D ,- or D 2-stage filtrates
is an effective means of lowering the pH of
the pulp in preparation for the following
bleaching stage.
5.3 Washers used later in the bleach

plant
Although less important than the first
two bleaching stage washers, a chorine dioxide washer removes small amounts of
hydrochloric
and organic acids and dissolved lignin from the pulp to minimize
chemical application in the following stage.
It has been demonstrated that it is possible
to manufacture fully bleached sofrwood
kraft pulp without the use of a washer following the first D-stage in a DC(E+OXDED)
sequence (17). A final D-stage washer is
importanttominimizethecarryoverofco~
rosive material to the pulp dryer or paper
machine and to minimize brightness reversion of pulp in storage towers.
5.4 Washing in an ozone or peroxide

bleaching stage
Only minimal dissolved solids carryover
can be tolerated for effectIve delignification
in totally chlorine-free (rCF) bleaching sequences that use ozone (18). Ozone is extremely reactive toward dissolved organic
solids and their presence can reduce the
efficiency of the bleaching stage, resulting
in increased chemical consumption.
This
is particularly important in medium-consistency systems because ozone is applied at
a 6-14% concentration in a carrier gas and
its maximum application can be limited by
an inability to mix large volumes of gas into
the pulp and to de-gas the pulp after it exits the reactor.
6. Control of bleach washers

Application of automatic process control
to optimize water and energy consumption
is generally very rudimentary
in bleach
plants. There is currently little perceived
need to advance the level of automatic process control of wash flows. Modern secondary treatment facilities are expected to
handle the volumes of water produced during periods when the pulp is overwashed
and additional bleaching chemicals can be
586
applied to compensate for periods when

the pulp is underwashed.
Low-level control loops are required for
washers to operate. These loops include
control of stock flow rates and consistencies feeding the washers, washer vat levels
and drum speed, and filtrate pH. Improved
automatic control of filtrate tank levels and
shower water flow rates has been applied
successfully to eliminate the common problem of setpoint overshoots and tank level
and shower flow oscillations (19-21). Interactions between tanks can be decoupIed
using a cascaded, feedforward control strategy in cases where countercurrent
washing is practised.
Advanced control strategies will be necessary for successful operation of bleach
plant washers in the future. Recent advances in the area of brown stock washer
control (22-26) are beginning to appear in
the literature, and these advances can be
applied to bleach plant washers. Automatic
feedforward control strategies can be used
to maintain a constant dilution factor
(20,21). Production rate can be monitored
using stock flow, and consistency sensors
and shower water flow rates are manipulated accordingly.
The impetus to decrease the amount of
effluent from both conventional
and elemental chlorine free (ECF) bleach sequences will remain a prime motivation for
applying automatic process control strategies to bleach plant washers. The need to
control carryover of residual hydrogen peroxide in effluent from peroxide bleach
stages will also be a motivating force because significant peroxide residuals can be
toxic to microorganisms in secondary treatment plants.
Several recent papers have expressed the
need for a method to measure, on-line, the
the quality of filtrate carried by washed pulp
leaving a drum washer (24,26). Studies are
required to determine optimal sensor locations. New residual chemical sensors are
required to monitor the performance of different bleach plant washing stages. An online COD sensor, currently not available,
would be valuable for measuring carryover
in brown stock and post-oxygen deligni-
fication washing. Feedback control strategies used in brown stock washing (24,26)
would be simple to apply in bleach plant
washers if the required sensor existed. The
carryover of a specific contaminant from
the washing stage can be monitored using
the appropriate sensor and shower water
rates can be manipulated automatically to
maintain the cleanliness of the pulp at a
predetermined
setpoint.
Washer operation can be improved only
marginally at mills where bleach plant washers are overloaded because shower water
flow rates cannot be increased to the degree necessary. Periods of overwashing can
possibly be eliminated, however, which can
lead to reduced water consumption in the
pulp mill.
7. Material selection for bleach

washers
Corrosion of bleach plant pulp washers
and associated equipment
is principally
controlled by the concentration of residual
oxidant in bleach plant filtrates. For example, in the case of C- or D-stage wash. ers, when residual chlorine or chlorine
dioxide in the filtrate contacts the washer
drum surface, reduction to chloride can
occur through either of two reactions:
[1]
CI02+ 2 H20 +5 e-
Cl- + 4 OH-
Corrosion of washer metal provides

electrons in the reaction:
[2]
the
[3]
Even short duration exposure to high residual oxidant levels can cause severe corrosion, especially in acidic stages. Generally,
other environmental
parameters such as
pH, temperature, and chloride ion concentration are less important.
Major advances have occurred in the
development of materials of construction
for washers over the last twenty years. This
has been a result of changing conditions in
the bleach plant. The introduction of wash
water recycling and widespread use of chlorine dioxide gradually led to washer condi-

tions that were too corrosive for the then
standard 317L (3% molybdenum) stainless
steel washer drums. As a result, austenitic
stainless alloys containing more than 6% molybdenum, such as 254 SMO, have become
widely used (27-31). Titanium, fiberglassreinforced plastics (FRP-<:oated),and monolithic FRP washers
were also widely
introduced.
More recently, a new generation of duplex stainless steels has been introduced by alloy suppliers. These alloys
maintain or exceed the corrosion resistance
of comparable austenitic alloys and have
mechanical strengths close to that of carbon steel (32). However, experience has
been limited with them to date.
The optimum choice of material for
washer construction
depends
on the
washer stage and specific operating conditions within a mill (Table 6). A cost
effective material in one mill may be inappropriate in another. The following sections
outline some of the considerations for selection of materials for use in each bleaching stage and specific concerns that affect
the corrosion resistance of metallic and nonmetallic washers.
7.1 Oxygen delignification washers

The majority of post~xygen stage washing and pulp handling equipment is constructed
of 316L stainless steel. This
material has performed well,and today 316L
Tule 6. BlHeb plat
-.sbI.g
slllges
Alloy
Duplex (e.g., 2205)

Titanium
FRP
is the standard material of construction in

all known post~xygen washers. Corrosion
testing has shown that while carbon steel
is unsuitable, 316L and higher stainless
steels such as 254 SMO perform well (33).
7.2 Chlorine/chlorine dioxide washers

Many mills have turned to higher chlorine dioxide substitution to reduce AOX
emissions. This change makes the C+D
washer environment more corrosive. Stainless steels such as 904L, which often performed adequately
in the past, suffer
corrosion as more chlorine dioxide is substituted for elemental chlorine. FRP washers, which were adequate for use at low
chlorine dioxide substitutions, may be attacked when chlorine dioxide substitution
increases to over 50% (34). Nickel-base alloys such as Hastelloy C-276 have also been
found to be susceptible to general corrosion when high chlorine dioxide residuals
are present and the pH is greater than 3
(35).
Alloys that contain more than 6% molybdenum are now commonly used in washer
fabrication for service in oxidizing environments such as those in chlorine dioxide
stages. These alloys have sufficient resistance to the pitting and crevice corrosion
that are predominant in the oxidizing Dstage environment.
Titanium is an excellent material for D-stage equipment.
tbe .IWys tlMt _ ty/Ikdlly 5/IIflM.
0
P
P
P
D+C
NR
NR
B
P
P
P
NR
P
B
P
B
316L
3171
904L
6% Mo alloy
(e.g., 254 SMO)
"'"'
587
Bleach Plant Washing Stage

D
H
E
P
NR
B
peroxide
P
NR
P
P
P
B
P
P
P
P
P
P
NR
P
B
P
NR
P
P
P
B
P
P
NR
B
P = Premium material: Material resists corrosion even when exposed to aggressive bleach filtrates.
E.,
P
P
P
P
P
P
B
B = Budget material: Material resists corrosion in many applications but may corrode prematurely when
exposed to agressive filtrates.
NR
= Not
recommended:
Material
may experience
rapid degradation.
';88
7.3 Alkaline extraction washers

The alkaline environment in most E-stage
washers generally prevents chloride pitting
and crevice corrosion.
However, crevice
corrosion can occur where face-wire retaining bands contact the washer surface.Washers are therefore constructed from low-alloy
stainless steels such as 316L which has some
resistance to localized corrosion.
Many
mills now add oxygen, hydrogen peroxide,
or both to the E-stage. This creates a more
oxidizing environment and may require the
use of more resistant alloys such as 3171.
7.4 Hypochlorite
washers
H-stage bleaching and washing is carried
out at high pH and is therefore less likely to
cause pitting or crevice corrosion. However, the oxidative environment
in hypochlorite bleaching requires the use of
317L (31).
7.5 Hydrogen peroxide washers
Peroxide bleaching is performed under
alkaline conditions. Hydrogen peroxide is
not a sufficiently strong oxidizing agent to
cause pitting of stainless steels so 316L or
317L can be specified for this service. In
existing mills, Postage bleaching trials or
short duration production runs of TCF pulps
are often carried out in D-stage equipment
(36). Caution must be exercised when performing peroxide bleaching with titanium
equipment because titanium is susceptible
to corrosion when in contact with alkaline
hydrogen peroxide. Keeping the peroxide
residual low and the pH less than 10.5 can
prevent rapid, general corrosion of titanium.
The relatively high temperature ofP-stage
bleaching (approximately 90C) may be too
high for FRP components. If the surface of
an FRP washer has been attacked by chlorine dioxide to the extent that the reinforcing glass fibers are exposed and that washer
is then put into service in an alkaline extraction stage (E or P), alkali will attack the
glass and further degrade the washer.
7.6 Electrochemical
protection
for
stainless steel equipment
To improve the resistance of a C+D- or
D- stage washer made from a lower alloy
such as 317L or 904L, electrochemical

protection such as Papritection@ may be used
to increase washer life. Electrochemical
protection works by using an electrical circuit to provide an alternative source of electrons for the reduction
of the residual
oxidant (cf. equations [IJ to [3]), thereby
protecting the washer from corrosion. In
practice, it has been found that an electrochemically protected 317L washer performs
as well as an unprotected
254 SMO alloy
washer. Long-term corrosion monitoring
has shown that even alloys that contain
more than 6% molybdenum
can benefit
from electrochemical protection (37).
7.7 Manufacturing considerations

Fiberglass-reinforced plastics (FRP)
FRP has been used as a covering over
carbon steel or stainless steel even when
the underlying steel is pitted. However,
edges and holes in the coating are common
sites for accelerated crevice corrosion. In
such cases, it has proven beneficial to apply electrochemical protection. Monolithic
(solid) FRP washers have performed effectively in chlorination stages and at low-tomoderate (-50%) substitutions of chlorine
dioxide. Higher levels of chlorine dioxide
substitution and 100% chlorine dioxide may
be too aggressive for many FRP resins (34).
The degree of chemical attack can be reduced by ensuring that the resins are fully
cured. The degree of cure can be determined by measuring the residual styrene
content of the resin, by differential scanning calorimetry, or by Barcol hardness testing (38). Resistance to chlorine dioxide is
also improved by the use of halogenated
resins (39).
Surface cleaning of stainless steels
Stainless steels depend on a thin, tenacious protective layer - the passive layerfor their resistance to corrosion. Therefore,
it is important that the film surface be uniform. It is also important that there be no
embedded iron left on the surface when the
equipment is put into service. An optimal
surface condition is assured when all embedded iron from fabrication and handling
and all heat tint and weld spatter are re-

moved after fabrication (40,41). Pickling
with a mixture of 10% nitric and 3% hydrofluoric acids at 60C for 10 minutes is the
best surface preparation method. Pickling
should be the last stage of manufacture for
stainless steel bleach plant equipment.
Welding
317L and 904L austenitic stainless steels
usually can be welded with matching filler
without reducing the corrosion resistance
of the weldment. When alloys containing
more than 6% molybdenum are welded with
matching filler or no filler (autogenous
weld), poor mixing of the melted metal can
result in corrosion at the weldment.
To
overcome this problem, these alloys should
be welded with .over-matching" weld fillers, that is, weld fillers having superior corrosion resistance to the base material (27).
For operations conducted below pH 3, the
nickel-base alloys Inconel112 or Hastelloy
C-276 can be used as weld fillers. For chlorine dioxide
operation
above pH 3,
Hastelloy G-30 may be better (35).
8. Extractives
and pitch
The behavior of extractives

in pulp
bleaching and washing has been elucidated
mainIy during the past two decades (42-47).
Although they comprise a relatively small
fraction (usually 1-5%) of the weight of
wood, the organic solvent extractables can
cause losses in productivity and product
quality through what are commonly referred to as pitch problems (48-50).
The extractives in wood are made up of
a complex mixture of hundreds of different chemicals including glycerides, fatty and
resin acids, terpenes, steryl esters, high
molecular weight phenols, and alcohols.
During kraft pulping, the glycerides, fatty
and resin acids, and most of the steryl esters are saponified to water-soluble soaps
(sodium salts of fatty and resin acids). Some
extractives are dispersed into the process
liquid and the balance remains on the surfaces of the fibers and inside parenchyma
cells (51). During the washing of unbleached aIkaline chemical pulps, the colloidal or emulsified extractives and soluble
soaps are largely washed from the pulp
589
(43).This helps avoid pitch problems later,

in the bleach plant or on the pulp dryer or
paper machine.
In bleaching, the key to understanding
the ability of extractives to be washed from
the pulp is their physical distribution which
in turn is predominantly affected by pH. For
a kraft pulp at high pH, dissolved soaps and
dispersed extractives are present in the process liquid, and the rest of the extractives
are on the surfaces of the pulp fibers and
inside parenchyma cells. When the pH of
this pulp is decreased to below 6, the dissolved soaps are converted to their protonated (free acid) furms (52) and form a very
fine suspension of particles of fatty and resin
acids. Further decrease in pH to below 3
leads to a destabilization of the dispersed
extractives and soap particles so that they
precipitate onto the pulp fibers and fines
(44,45) .This means that the C-stage washer
is relatively ineffective at removing soaps
and dispersed extractives because they are
adsorbed on the pulp fibers. However, the
soap particles and dispersed extractives
repeptize (i.e., redisperse) into suspension
when the pH is increased and, above pH 6,
the soaps become soluble (52). Therefore,
E stages provide excellent opportunities for
extractives removal (44).
Extractives removal (deresination) in E
stages can be improved by the addition of a
pitch dispersant in the E-stage tower and
by increasing the a1kaIi (NaOH) charge and
the temperature. The physical state of the
extractives at different stages of a multi-stage
kraft bleaching sequence are summarized
inTable 7 (44).
Although oxygen delignification was not
employed in the mill referred to in Table 7,
experience
suggests that little chemical
change in the extractives occurs during an
oxygen stage. Post-oxygen washing can
therefure be considered,from an extractives
point of view, to be an extension of brown
stock washing.
In kraft mills, if the unbleached pulp has
been thoroughly washed (saltcake losses
less than 6.5 kg Na,SO/t for hardwoods or
less than 10 kg Na,SO/t for softwoods),
590
Pulp Bleaching
Table 7: EffectitJ_
Washer
Location
-Principles
and Practice
of flllISbi"g on extrlletives removal.

Physical Distribution
of Extractives
Extractives
Removal
in Washing
in Mill
On fiber surfaces (moderate
Dispersed (large amounts)
Dissolved (large amounts)
(C+D) Stage
On fiber surfaces (large amounts)

Very little dispersed
No dissolved soaps
Not effective when pH < 3
E, Stage
On fiber surfaces (moderate amounts)

Dispersed (large amounts)
Dissolved soaps (large amounts)
Very effective
D, Stage
amounts)
Very effective
Unbleached pulp
screen room
Very effective
On fiber surfaces (sometimes a little

more than in E )
Dispersed (if pH < 3, very little;
if pH > 3, can be appreciable)
No dissolved soaps
E, Stage
On fiber surfaces (usually a little less

than in E)
Dispersed (usually less than in E,)
Dissolved soaps (usually less than in E,)
D, Stage
On fiber surfaces (usually slightly more

than in E)
Dispersed (variable amounts) if pH > 3
No dissolved soaps
there is usually very little or no pitch deposition in the bleach plant. There are, however, several factors which can lead to
deposit problems.
The use of defoamers at any point in the
bleachery should be avoided because they
can form deposits (46,54).A high application (greater than 1.5 kg/t) of defoamer to
the knotters, brown stock washers or, especially, to the brown stock screen room
or o-stage washers can similarly cause deposits in the bleach plant. This problem
may be exacerbated if most of the defuamer
is added at the brown stock decker or postoxygen washers.
Kraft mills using hard water may experience scale deposition on the E-stage washers. There is evidence that this kind of
deposition can be accelerated by the presence of residual defoamerin the stock (53).
Talc has proven to be a useful additive for
sorbing defuamer residues (54,55). In addition, it acts as a de-tackifier to suppress
formation
of deposits
on equipment
(54,56). Soft water such as stripped evapo-
Effective when
3 < pH < 6
Very effective
Effective when 3 < pH < 6

rator condensate, if available, can be used

on E-stage washers to avoid the formation
of hard water soaps (e.g., calcium salts of
fatty acids).
A recent cause of pitch deposition in kraft
bleach plants has arisen from the use of
higher degrees of chlorine dioxide substitution for chlorine in the first bleaching
stage when the pH in this stage is permitted to increase above 3. In some cases
where no pH control has been used, the
pH may rise to as high as 5 or 6. If the white
liquor clarification has been poor (greater
than 200 ppm suspended solids), calcium
carbonate particles entrained in the unbleached pulp can survive the first bleaching stage and co-deposit with extractives,
defoamer,and hard water soaps on the firststage washer and, especially, the E1-stage
washer. Over time, such deposition
can
cause blinding of the washer face wire and
necessitate a costly cleanup. The solution
to this problem is to add acid (e.g., sulfuric)
to the first bleaching stage to lower the pH
to a value around 3. At this pH, the calcium

carbonate particles dissolve and the calcium
is discharged
with the effluent. Better
delignification efficiency is also obtained at
the lower pH. Aside from this aspect, the
substitution of chlorine with chlorine dioxide does not appear to affect the propensity for pitch deposition in kraft mills.
In the bleaching of both kraft and sulfite
pulps, chlorination of extractives leads to
the addition of two atoms of chlorine across
each double bond in unsaturated molecules.
Chlorine dioxide bleaching, on the other
hand, leads to the addition of a chlorine
atom and a hydroxyl group to the carbon
atoms on either side of double bonds. The
result, for both kraft and sulfite pulps, is an
increase in the molecular weight of extractives and a considerable increase (e.g.,4Q%
in chlorinated kraft) in the extractives content of the pulp (44).
In sulfite pulps, chlorination leads to a
very sticky resin which tends to deposit on
surfaces in the bleach plant. Substitution of
chlorine dioxide for cWorine in the first
bleaching stage is a documented
way to
decrease such problems in bleaching sulfite
pulps (47,57). In kraft pulps, much of the
extractable material is saponified and dissolved in the digester, resulting in a much
lower extractives content in the unbleached
pulp. As a result, chlorination does not noticeably affect the tendency for extractives
to deposit on a kraft pulp; similarly, chlorine dioxide substitution has no effect.
In conclusion, it is evident that good
washing, especially of the unbleached pulp
and after the E stages, is essential to control pitch problems in the bleach plant.
Washing is the most effective tool a pulp
mill operator has for removing extractives,
soluble soaps, calcium carbonate, and residual defoamer from the pulp. When this
is done well, no deposits form and therefore no quality problems can arise by their
sloughing off and contaminating
the fInished pulp.
9. Defoamers and drainage aids

In pulp washing, good equipment design
and maintenance
are the most effective
ways of minimizing problems arising from
591
air in the stock. However, any foam and

entrained air that remain despite these
measures can be controlled chemically. Defoamers and drainage aids are often interchangeable terms for the same products
because most formulations that control visible foam also control the entrained air
bubbles that hinder washing (58).
All defoamers and drainage aids that contain mineral or silicone oil can cause deposition of defoamer or dirt on equipment or
machine clothing, dirt in the product, and
deterioration of sheet properties. Excessive
use of these materials should be avoided,
and they should be added early enough in
the process so that they can be removed
from the stock in the final washing stages.
Defoamers and drainage aids should be used
sparingly (less than 1.5 kg/t), only in the
first stages of brown stock washing, and
never in the bleach plant. Within these limits, brown stock defoamers can be added
at the knotters, to the shower water, in the
filtrate tank, in the stock feed line to a
washer or at any other appropriate point in
the fIrst washing stages.
It is difficult to predict defoamer effIciency from laboratory tests. Manufacturers
of silicone defoamers report that emulsifIed
silicone defoamers are more effective in the
laboratory than oil-based defoamers (with
oil as the bulk phase) at both breaking and
inhibiting the formation of black liquor surface foam (59,60). However, an independent comparison of brown stock defoamers
(61) suggested that, although water-based
defoamers (containing emulsifIed silicone
or mineral oil) are slightly better than oilbased defoamers at breaking surface foam,
the latter are better at inhibiting the formation. Similar results for oil-based defoamers
have been reported in a study by a manufacturer of water-extended defoamers (water-inoOil emulsions) (62).
Evaluation of drainage aids is largely empirical. Drainage and addition can be controlled based on measurement of entrained
air in the process ftItrate. Some on-line
monitoring equipment is available commercially (63). The optimum amount of entrained air that can be tolerated, usually
592
2-8"10 by volume, must be determined

each situation.
for
Types of defoamers
There are several types of specially formulated defoamers on the market that are
well-suited to the high pH, high temperature conditions of brown stock washing.
Oil-based, water-extended, water-based, and
water-based/oil-free
defoamers, as well as
new defoamers
and drainage aids, are
briefly discussed below.
Oil-based defoamers consist of amide
wax and hydrophobic silica particles suspended in mineral oil and have traditionally been the most effective. The deposition
of oil and wax which can occur (64) may
lead to inferior paper properties (e.g. ,lower
strength, cleanliness, and printability) if the
defoamer is carried over into the paper mill.
The use of some low-quality oils has been
linked to formation of chlorinated dioxins
and furans (65). This problem has now
been eliminated by the use of oils free of
the precursors of these compounds (66).
Oil-based defoamers are the industry standard against which other types of defoamers and drainage aids are compared.
Water-extended defoamers are oil-based
defoamers in which some oil is replaced
with emulsifIed water, resulting in a lower
unit cost. This translates into savings only
when the effectiveness is the same as that
of the oil-based defoamers. Although it has
been claimed that water-extended defoamers lead to decreased deposition and paper
deterioration, there are few supporting data
available.
Water-based/oil-free defoamers are aqueous emulsions of concentrated
oil-based
defoamers with a lower unit cost compared
to oil-based defoamers. Again, there are few
data to support the claim that these defoamers lead to reduced deposition and deterioration of paper properties,
and savings
occur only if the efficiency is equal to that
of oil-based defoamers.
Water-based/oil-free
defoamers
are
emulsifiable silicone oils, or silicone-inwater emulsions and may contain hydrophobic silica. Deposition of silicone oil may
occur (67), leading to inferior paper properties if the deposit is carried over"into the
paper mill. Silicone-containing defoamers
are more expensive than oil-based products
and have a variable cost effectiveness. Originally, these were better drainage aids than
defoamers, but newer formulations
are
claimed to be equal or superior to oil-hased
products for foam control. The performance of silicone-containing
defoamers
may be optimal in combination with oilbased defoamers. Some new defoamers and
drainage aids containing neither mineral oil,
silicone oil, silica, or amide waxes (67,68)
have undergone limited testing. Paper machine defoamers and drainage aids are ineffective at high temperature and pH.
10. Washing bleached mechanical and high-yield pulps

It is often desirable to wash bleached
mechanical and high-yield pulps to remove
soluble residues that can interfere with operations downstream of the bleach plant.
Adequate washing is becoming more important as mills move to decrease effluent volume. Also, increased
recirculation
of
process water contributes to increased concentrations of detrimental contaminants in
process streams.
The build-up of silicates, added to control hydrogen peroxide decomposition, can
also have a detrimental effect. Calcium and
magnesium are desorbed from pulp by peroxide chemicals during peroxide bleaching
(69), and calcium and magnesium silicate
residues have been found on the fiber
surface.
Alkaline bleaching conditions increase
resin and fatty acid dissolution, and these
materials can adversely affect papermaking
if carried to the paper machine (70). Alkaline conditions also cause the release of
anionic substances, referred to as anionic
trash, which increase consumption of cationic polymers at the paper machine (71)"
Adequate washing after peroxide bleaching is valuable in operations where hydrosulfite bleaching
follows a peroxide
bleaching stage because residual peroxide
consumes hydrosulftte (see Chap. VI 2).
593
594
Pulp Inlet
~
FIg. 16./Hilgram
+
Pulp Outtet
Fig. 15. Cut-away diagram 01-
Vacuum drum washers
press (HymtU:/I1"",e).
One of the earliest devices for washing

mechanical pulp was the vacuum drum
washer. These washers are still in service
in older mechanical pulp mills, but their
popularity is limited today because the of
the slow drainage characteristics
of mechanical pulps. Several washers must be
employed in series, and countercurrent
filtrate flow is used to achieve satisfactory
results. Low discharge consistencies, compared with those obtained with other
washer types, are achieved using vacuum
drum washers.
Screw presses
The screw press consists of a threaded
screw or shaft that rotates inside a fixed
screen basket (Fig. 15). A half-basket surrounding the inlet of the press allows initial drainage to occur. The rotating screw
compresses and dewaters the pulp, while
simultaneously moving the pulp forward.
The screw can be plated with hardened
steel to avoid abrasion problems caused by
high-&scharge consistencies.
The screw press is best suited to pulps
with good drainage properties.
Screw
presses can accommodate feed consist en-
cies as high as 10"10although 4% consistency

is more typical. Most screw presses can
deliver thickened pulp between 30 and 40%
consistency. The presses have high production rates based on screen areas and are
compact compared with other types of
washing equipment.
The development of medium-<:onsistency
(Me) pumps has made it possible to feed
MC pulp directly from a bleach tower to a
screw press without dilution. Screw presses
are generally used for two-stage bleaching
sequences because of their high-<:onsistency discharge. They can supply high-<:onsistency pulp to later refining steps.
The two types of industrial screw presses
used are the standard screw press and the
displacement
washing screw press. The
standard screw press washes pulp by a
thickening action alone and unwanted dissolved compounds leave the pulp with the
pressate. The retention of colloidal resin
particles in the dewatered pulp is low in
comparison with other types of filtration
equipment (72,73). However, improved
removal of colloidal particles is achieved at
the cost of increased loss of fines. The displacement washing screw press is similar
0111III11wire JII"eSS (A1uIrlb: SprotIt-Btuler).
to the standard unit but has a wash zone in

the screw channel. Wash water is injected
into the pulp through the screw shaft and
forced through the pulp by hydraulic
pressure.
Twin-wire press
The twin-wire press dewaters pulp in
three separate sections (Fig. 16). Gentle
dewatering occurs as pulp is fed between
two moving wires in the wedge section.
Practical feed consistency varies between
References
1. Crotogino, R.H., Poirier, N.A., Trinh, D.T,
Tappi J 70(6):95 (1987).
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79(4): 123
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Douglas, WJM.,] Pulp Pap. Sci. 15(1):)28
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22(7):481
I % and 5%. The pulp passes from the wedge

section to the S-roll section and then to the
press section where a variety of nips are
applied. Pressure is gradually increased to
dewater the pulp to discharge consistencies
as high as 35%.
The twin-wire press can handle a wide
range of pulp freeness and can be used to
wash pulps that are difficult to dewater.
Dilution and displacement washing can be
combined in the twin-wire press.
11. Turner, P.A. and Livingstone,

L., "Brown
stock Washer Control Part III: Unique
Method to Monitor the Cleanliness
of
Washed Pulp Directly," CPPAJoint Pacific
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12. Shackford,
L., 1992 TAPPI Bleach Plant
Operations
13. Lundqvist,
(1985).
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14. Stromberg, C.B., "Washing for Low Bleach

Chemical
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1990 TAPPI
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TAPPI
15. Miller, W)., Shackford,
L.D., Jiang,
Genco, J., Tappi J. 74(2): 117 (1991).
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(1983).
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18. Tibling, P. and Dillner, B., "TCF Bleaching
Can Be Carried Out With Different Bleaching System," 25th EUCEPA Conference
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EUCEPA, Paris, 1993, p.65.
19. Harris, T.]. and McGregor,
33(9):1481
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].R, AIChB J,
20. Throer, P.A. and Allison, B.]., "Brown stock

Washer Control Part n: Filtrate Tank Level
Control," CPPA Tech. Sect. Annual Meeting Proceedings,
Montreal, 1992, p.BI09.
21. Wigsten,
A.L., "Conductivity-based
Shower Water Control In Brown stock
Washing," 1988 TAPPI Pulping Conference
Proceedings,
TAPPI PRESS,Atlanta, p.l.
22. Sande, WE., Oestreich,
M.A., Poplasky,
M.S.,Stewart,J.R,
TapPiJ 71(3):93 (1988).
23. Bender,G.,
71(12):115
Rochard,
(1988).
24. Han,Y.and
(1988).
Edwards,L.,
L., Dorn,W,
TapPiJ.
TapPiJ. 6(71):101
595
Steels" 1992 TAPPI Seventh International

Symposium On Corrosion in the Pulp and
Paper Industry Proceedings,TAPPI
PRESS,
Atlanta, p.361.
33. Bardsley, D.E., "Compatible
Metallurgies
for Today's new Bleach Washing
Processes" 1995 TAPPI Eighth International
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PRESS,
Atlanta, p.75.
34. Bergman, G., "Corrosion
Resistance
Of
Glass-Fibre Reinforced
Plastics (GRP) In
CWorine Dioxide Environments,"
1986
TAPPI Fifth International
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Corrosion in the Pulp and Paper Industry
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35. Wensley, A.D., Reid, D.e., Brown, D.,
Christie, D., "Corrosion of Stainless Alloys
in a Chlorine
Dioxide
Bleached
Pulp
Washer," 1991 TAPPI Engineering Conference Proceedings,
p.499.
25. Nase, T and Sjoberg, K-E., Pulp Pap. Can.

90(9):108 (1989).
36. Clarke, S.]., and Singbeil, D., Pulp

Can. 95 (8):T 417 (1994).
26. Thmer, P.A., Roche, A.A., McDonald,].D.,

van Heiningen,
A.R.t'., Pulp Pap. Can.
94(9):T227
(1993).
37. Singbeil, D., and Munro, I., "Papritection@

for Bleach Plants of the 90's," CPPA Technical Section Pacific Coast and Western
Branches Spring Conference Proceedings,
1990, Tech. Sect., CPPA Montreal, 1990.
27. Gamer,
(1981).
A., Pulp
Pap. Can.,
82(12):109
28. Sedricks,].A., Corrosion of Stainless

Publ. EIectrochem.
Soc. Pennington
1979, p.70.
Steels
N.].,
29. Metals Handbook (9th edn.),Vol. 13, Corrosion, ASM International,

Metals Park,
OR, 1987, p.119O.
30. Bardsley, D.E., "The Effect Of Chlorine
Dioxide Substitution
On Various Metals
Specifically For Mixer Applications," 1992
TAPPI Seventh International
Symposium
On Corrosion in the Pulp and Paper Industry Proceedings,TAPPI
PRESS,Atlanta,
p.59.
31. Ththill, A.H., "TAPPI Phase n Corrosion
Test Program-Part I. Resistance Of 26 Candidate Materials To Aggressive C,D & H
Stage Bleach Plant Environments,"
1983
TAPPI Fourth International
Symposium on
Corrosion in the Pulp and Paper Industry
Proceedings,TAPPI
PRESS ,Atlanta , p.133.
32. Nordstrom,].,
Rung, B., Olsson,J., "Utilizing the Corrosion Resistance and the Mechanical
Strength
of Duplex Stainless
38. Bishop,
(1992).
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Pulp
Pap. Can.
Pap.
93(6):62
39. Bishop, TN. and Cowley,T., "Corrosion

Resistant
Fibreglass
Reinforced
Plastic
Composites For CWorine Dioxide Environments - Initial Report," 1992 TAPPI Engineering Conference
Proceedings,
TAPPI
40. Coates, G., Materials
(8):61 (1990).
Performance
29
41. Christie, D.W, "Effect of Post-Weld Cleaning On Corrosion

Resistance Of AusteniticAnd Duplex Stainless Steel Weldments
In Bleach Plant Service," 1992 TAPPI Seventh International
Symposium on Corrosion in the Pulp and Paper Industry Pr0ceedings, TAPPI PRESS,Atlanta, p.87.
42. Bjorklund,].M.,
Back, E.L.,Thfvesson,
"A Review of Kraft Pulp Deresination
Pitch Problems," Eighth Fundamental
M.I.,
and
Re-
search Symposium Preprims, Oxford,

1985.
43. Allen, L.H. and Maine, e.]., Pulp Pap. Can.
79(4):T152 (1978).
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Pulp Bleaching
-Principles
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44. Allen, L.H. and Lapointe. c.L.. Pulp Pap.

Can. 88(12):T483
(1987).
45. Allen, L.H. and Lapointe,
c.L.,].
Chern. Technol. 8(2):289 (1988).
Wood
46. Dunlop-jones,
N. and Allen, L.H.,j
Pap. Sri. 15(6):J235 (1989).
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49. Allen. L.H., TapPiJ.

50. Back, E., Svensk
(1960).
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63(2):81
Papperstidn.
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of
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--..----
SECTIONVI:
Chapter 4:
Towers and Reactors
David E. White
Union Camp Corporation
Princeton, NJ
Rune Larsson
Sunds Defibrator AB
Sundsvall, Sweden
1. Introduction
2. General
599
principles
and fundamental
2.1 Mass transfer

2.2 Physical
2.3 Process
considerations.
and reactor
2.4 Rheology
kinetics
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 601
. . . . . . . . . . . . . . . . 601
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 603
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 603
criteria
for reactors.
4.1 Tower reactors.

4.3 High-<:onsistency
4.4 Displacement
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 604
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 604
4.2 Medium-<:onsistency,
high-intensity
contacting
bleaching
mixer/reactors.
reactors.
towers.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 609
609
- examples.
(low-<:onsistency)
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 610
for pulp bleaching
5.1 Upflow
towers
610
5.2 Upflow or upflow-downflow

towers
(medium-<:onsistency
D and (EO) stages)
5.3 Upflow or downflow
(medium-<:onsistency
5.4 Downflow
towers
5.5 Medium-<:onsistency,
5.6 High-<:onsistency
6. Case study.
7. Troubleshooting.
. . . . . . . . . . . . . . . . . . . . . 608
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 608
4.5 Tray reactors

5. Reactors
599
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 599
considerations
of pulp suspensions
3. Contactors.
4. Design
and chemical
considerations
towers
E and P stages)
(high-<:onsistency)
high-intensity
contacting
reactors.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 610
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 611
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 612
mixer/reactors.
. . . . . . . . . . . . . . . . . . . . . 614
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 616
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 617
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 619
597
Chapter VI 4: Towers and Reactors
Chapter VI 4:
Towers
and Reactors
1. Introduction
Industrial chemical processes are designed to economically produce a desired
product from a variety of starting materials
through a succession of treatment steps as
shown in Fig. I (1). In pulp bleaching, this
overall process concept involves I) mixing:
the initial physical treatment, designed to
prepare the pulp for the chemical reaction
step, including dilution, temperature adjustment, and mixing of pulp and bleaching
chemicals; 2) reaction in a bleaching tower,
contactor, or other type of reactor; and 3)
washing, an additional physical treatment
step to obtain the final product from a
bleaching stage. Mixing and washing operations are covered in Chaps. VI 2 and
VI 3; bleaching reactor design engineering
is discussed in this chapter.
The overall objective of the pulp bleaching reactor is to delignify or bleach the pulp
in a particular stage, with minimum operating cost and maximum selectivity. Additional requirements,
depending
on the
position of the treatment in the bleach sequence, may include adding enough bleaching chemical
to react with incoming
contaminants
(bark, shives) and with dissolved carryover and carryback solids.
To design a reactor to accomplish these
objectives, the thermodynamics
(heat liberated or absorbed; maximum possible extent of reaction) and chemical kinetics (rate
of reaction) must be evaluated (1-5). These
analyses generally require detailed labora-
Raw
Materials
599
tory and pilot plant evaluations to understand the fundamental physical and chemical principles which are especially relevant
to pulp bleaching where the reactions are
heterogeneous
(two or three phases are
present). These evaluations allow the correct reactor to be identified and designed,
resulting in maximuni product quality and
optimal capital and operating economics.
In this chapter, the principles and design
concepts used for low-, medium-, and highconsistency delignification and bleaching
reactors for kraft pulps are reviewed in Sect.
2. Section 3 contains a discussion
of
contactors used in pulp bleaching. Tower
and reactor types and design criteria are reviewed in Sect. 4; reactor examples are provided in Sect. 5. A case study is detailed in
Sect. 6 as an example of how fundamental
principles are applied in reactor specification and design. Finally, troubleshooting
approaches for reactor evaluation are reviewed in Sect. 7.
2. General principles and fundamental considerations

2.1 Mass transfer and chemical
kinetics
The goal of bleaching reaction engineering is to achieve results on a commercial
scale (e.g., 1000 air dry metric tons per day)
at least equivalent to those obtained in the
laboratory. Optimal reactor design requires
an understanding
of the physical and
chemical processes which must occur for
a specific pulp bleaching treatment to be
successful; it must also take into account
differences which scale-up introduces (Sect.
2.3 below).
Delignification and bleaching reactions
are heterogeneous two- or three- phase re-
Chemical
treatment
steps
Physical
treatment Products
steps
Recycle
Fig. 1. Scbemllllc rej1reseff1ll11off of typkIIl
cbemklll
process,
reprlfftJobft
Wiley & Sons, JffC. by permlssttm
(1).
600
.............
.' .
(1)/
.......
fi fi
J .fII'
. e...
fi'......
".
fi
Pulp floes
'. '.
'.
From
(1) Bulk gas phase
@ Surface of floc
@) Surface of fiber
@ Chemical reaction
.......
Fiber cross section
To
Surface of the floc
Surface of fiber inside floc
Reaction site
Fig. Z. Scbem411c "/Jf'esetlltlllott of mas transfer 1111II

cbemklll processes Iff blgb-conslslerrcy oz_
Iffg (6).
actions in which: 1) the gaseous or dissolved

bleaching chemical is transported to the reaction sites on or within the solid pulp fibers in multiple mass transport processes
occurring in series (e.g., Fig. 2) (6),2) the
intrinsic chemical reaction(s) then occur on
or within the solid pulp fibers, and 3) the
soluble reaction products diffuse away.
The overall bleaching reaction rate may
be controlled by the chemical reaction,
mass transfer, or by both intrinsic kinetics
and mass transfer when the rates are similar. The relative rates of the mass transfer
and chemical processes must be determined so that the rate-limiting step(s) can
be identified. This leads to the design of a
reactor or reactor-tower combination having maximum reaction rate and selectivity,
resulting in maximum product quality with
minimum reactor size and operating cost.
The rate-controlling
step(s) are influenced by (1) the effectiveness of mixing of
the bleaching agent with the pulp, (2) consistency, which determines the amount of
liquid available to absorb the bleaching
chemical and the size of the extrafiber diffusion path, and (3) the phase, solubility,
bled-
and reaction properties of the bleaching

agent.
To determine
rate-controlling
steps,
analysis is made of relative mixing times
compared with reaction times, as has been
done for chlorine, chlorine dioxide, and
oxygen (7), Chap. VI 2. Chlorine has the
highest intrinsic rate, followed by chlorine
dioxide and oxygen. Chlorination is totally
diffusion-controlled
unless performed in a
high-intensity mixer, in which case it is reaction-rate-controlled. The relative slowness
of the oxygen reaction rate, relative to the
mass transfer times, means that the overall
reaction rate for oxygen can be determined
partially by the (slow) intrinsic kinetics,
indicating that higher temperature is important as a means of increasing the reaction
rate.
In high-consistency
ozone bleaching,
characteristic
mass transfer or reaction
times calculated for each step have shown
that the overall reaction is mass transfercontrolled in view of the very fast intrinsic kinetics. This has led to the identification
of effective fluffing and mixing! dispersion!
contacting of gas with pulp as requirements
for uniform and efficient reaction (6). (See

Case Study, Sect. 6.)
2.2 Physical considerations
Pulp is provided to a bleaching stage in
an aqueous suspension and is reacted with
the bleaching chemical(s) in the presence
of water. Accordingly, regardless of pulp
consistency, the bleaching chemicals at
some point must be dissolved in water before reaction. Stock consistency, the solubility of the bleaching
agent, and the
contacting scheme determine the extent to
which the bleaching agent can be dissolved
when applied to the pulp.
For example, chlorine is dissolved readily
in a 3% consistency pulp suspension and
pulp chlorination stages typically have been
conducted at low consistency (2.5-4.0%)
with the tower under only the hydrostatic
pressure head. Under these conditions, the
ratio of gas to pulp suspension is relatively
low resulting in the absence of dissolved
gas after the water is saturated (8). Oxidative extraction at 12% consistency has a similar initial gas:pulp ratio as 3% chlorination
but, because of the low solubility of oxygen in water, this ratio does not change in
the (EO) stage during the mixing operation.
Therefore, an oxygen gas phase persists after the mixer and up into the upflow leg
requiring a specific length-to-diameter (II
D) ratio to keep the oxygen evenly dispersed in the pulp suspension for maximum
contact and reaction (8).
processing involving a gas-phase reactant such as oxygen or ozone, reactor design strategy is
based on use of mixers to provide intensive mixing and efficient dispersaVdissolution of fine gas bubbles into the stock
suspension at high gas partial pressure. The
high-intensity shear field takes the suspension into the turbulent regime where it behaves as a turbulent liquid and provides a
stable gas-pulp suspension with high interfacial surface area for efficient gas transfer
throuBh the liquid film into the fiber where
reaction occurs (7, 9). For oxygen delignification the ensuing tower must be able to
maintain a stable pulp suspension and pro-
601
vide sufficient residence time to achieve

the required level of delignification.
For
efficient mixing and stability of the dispersion, an upper limit exists for the maximum
charge of gas to the mixer at about 35% of
the total volume of the pulp and gas slurry;
above this level, the gas volume fraction is
so great that gas coalescence occurs, decreasing mass transfer (Fig. 3) (10, 11). As
a result, increased pressure and multiple
mixer-reactor stages in series are used.
0.6
05
'0%_
5O'C.7.5%0,'"<>:.
Balm
0.4
.,
CD
o'"
0.3
--
f! 0.2
""
~;:, 0.1
'5
>
oo
0.'
0.2
0.4
0.5
Ozone, % on pulp
Rg. j. GfUrJOl_ III 0_

blMdn.g
~
5IIIbIIUy (11).
0.6
0.7
IIIIIlIIIIIU of
In high-consistency operations, uniform

mixing of the pulp fibers with delignifying
or bleaching agents is also very important.
This has been demonstrated for alkali distribution in oxygen delignification and for
gas:pulp contact in ozone bleaching (6,12).
(See Case Study, Sect. 6.)
2.3 Process and reactor considerations
The bleaching reactor can be defined and
scaled-up once the variables including consistency, chemical type and charge, inlet pH,
type of contacting, temperature, pressure,
and residence time have been specified.
Reactor conditions also depend on the
wood species, bleaching sequence, extent
of washing, and other factors.
Chemistry
Delignification and bleaching reactions
initially proceed very rapidly and then slow
down as the bleaching agent is consumed.
Reactions of bleaching chemicals with lig-
nin proceed asymptotically toward a limit

as more chemical is applied; reactions with
cellulose tend to be linear, resulting in a
selectivity penalty at higher application lev-
602
Pulp Bleaching
-Principles
and Practice
eIs (13). For these reasons, more than one

reaction stage is required for an optimal
delignification and bleaching sequence.
Consistency
Consistency determines
the amount of
water available for gas dissolution and affects the concentration of chemical in s0lution. Traditionally, bleach plants have
operated the bleaching stages at 12% consistency because this consistency was produced by the rotary drum washer in the
previous stage. The exception was chlorination which, as discussed above, was run
at 3% consistency to provide enough water
for complete dissolution of the chlorine gas.
More recently, innovations in reactor design
and equipment and a better understanding
of bleaching chemistry have allowed reactor consistency to be specified over a wider
range to maximize stage performance.
centration or gas solubility which, in turn,

is a function of pressure and temperature.
Pressure is also important if the intrinsic
kinetic reaction is at least partially controlling and if the rate expression includes a
concentration term in the gaseous reactant.
pH
The pH is very important for all bleaching processes because it profoundly influences reaction chemistry and therefore
affects efficiency, selectivity, and bleached
pulp cleanliness. Accordingly, pH has a direct impact on the chemical application
system and on reactor specifications. The
pH at the end of a stage is often used as the
target, for example in E and D stages, or it
can be fixed on the inlet side alone, as in
ozone bleaching. The pH also affects fiber
swelling.
Temperature
Temperature affects reactor design because of its effect on reaction rate and selectivity. Temperature is important in both
diffusion-limited and kinetically controlled
bleaching reactions because it affects both
diffusivity
and chemical
kinetics
in
Arrhenius-type rate expressions. Because
the activation energy is significantly higher
for chemical reactions than for diffusion,
kinetically controlled reactions are more
sensitive to the effect of temperature on
overall reaction rate. In addition, the usual
inverse relationship between temperature
and gas solubility must be taken into account in design (Chap. I). The process thermodynamIcs (heat liberated or absorbed)
must be taken into account so the proper
strategy for temperature control can be identified. For most bleaching reactions, the
amount of heat liberated is not significant
relative to the mass of the water present.
Retention time
The retention time (how large the reactor or tower must be from the point of pulp
and chemical mixing to the point of pulp
dilution following the bleaching reactor)
depends on the reaction kinetics, production rate, effective reactor volume, consistency, and, when there is a continuous gas
phase in the reactor, the degree of packing
(14). Stagnant regions within the reactor
can cause nonuniform residence time and
over- or under-bleaching.
Residence time
can be on the order of less than 1-2 minutes in ozone bleaching and up to hours in
chlorine dioxide bleaching.
Reactor design for variable retention time
is also important for optimal chemical use
and product quality. Variable retention time
can accommodate changes in production
rate and in feedstock properties (lignin content, variation in carryover or carryback
solids, seasonal temperature variation, startup, and wood species).
Pressure
Pressure affects reactor design because
it affects gas solubility and therefore the
amount of gas which can be contacted and
reacted with the pulp in a single mixertower at a particular reaction rate. The initial dissolution step and the diffusion rate
are functions of the bulk liquid phase con-
Reactor surface: volume ratio

Scale-up from the laboratory or pilot
plant to commercial size leads to a lower
reactor surface:volume ratio in the larger
unit. This can lead to different bleaching
results on scale-up and therefore needs to
be taken into account in design; for example, a surface-catalyzed decomposition

reaction is more significant on a laboratory
scale than on a commercial scale.
Interfacial surface area
Mass transfer-limited reactions are a function of the interfacial surface area, for example,gas bubble area in gas-liquid systems
and pulp floc surface area in high-consistency systems. Contactor scale-up must
ensure equivalency of interfacial surface
area or take into account differences which
might occur in larger units.
2.4 Rheology of pulp suspensions
An understanding of the rheological behavior of pulp suspensions is important in
several key areas of bleaching reactor design. These areas include flow proffie development
in pipeline-type
reactors,
medium-consistency
pumping, high-intensity mixer specification for optimal stock
dispersion
and gas contacting,
upflow
tower sizing at any consistency to avoid
channeling, and design for uniform introduction and stock discharge from a tower.
The friction loss curVe of a pulp suspension, for example, in the medium-consistency range, deviates significantly from
water at low shear and exhibits a behavior
similar to that of a Bingham fluid (Chap.VI
1). A Bingham fluid does not start flowing
until a characteristic yield stress is exceeded
and its flow is characterized by a central
core in plug flow and an outer, annular region undergoing shear. The shape of the
velocity proffie and the amount of material
in plug flow in the central core can be calculated (15). This understanding is essential in designing upflow legs and towers for
sufficient residence time as well as for
proper sampling to assess degree of reaction.
When the velocity is high enough that
the shear field exceeds the disruptive shear
stress, the pulp suspension flow approaches
"Newtonian" behavior and the pulp assumes the properties of the liquid phase (9,
16, 17) (Chap.VI 1). This basic mechanism
for fiber network disruption exists over a
consistency range of less than 1% to greater
than 15% (9). This principle played a key
role in the design of medium-consistency
pumps and mixers.
603
3. Contactors
Efficient chemical mixing and contact
with the pulp are essential at any consistency with gaseous or liquid bleaching
agents. Inefficient mixing can lead to overor under-bleaching, compromising chemical efficiency and the ability to meet pulp
quality targets (strength, kappa or brightness, and dirt) (18). Mixers are discussed
in detail in Chap. VI 2.
Chemical mixing before the tower or reactor can be done in a static or high-intensity mixer -depending
on mixing
requirements which are a function of the
bleaching agent phase consistency, and the
degree of mass transfer control of the chemical system. Medium-consistency pumps are
sometimes used to mix chemicals, and can
lead to capital savings at the expense oflimited flexibility in controlling mixing parameters. liquids such as caustic soda (NaOH)
solutions can be added into the fluidized
zone on the suction side of a pump; moderate amounts of gases can be added using
a porous sintered metal sparger built into
the discharge shear plate (19). (Pulp suspension properties and pumping are discussed in Chap. VI 1.)
Addition of a gas phase bleaching agent
to low- or medium-consistency
stock requires very effective mixing to provide
uniform solubilization and dispersion of fine
gas bubbles in the stock to establish a stable,
dispersed gas-water-pulp mixture. Mediumconsistency, high-intensity mixers - a relatively recent development
operated
within the proper gas-suspension volume
ratio range are very effective for dispersing
gas into pulp suspensions at 8-18% consistency. Medium-consistency
chlorination,
oxygen delignification, and ozone bleaching are examples of processes based on the
use of such mixers (Chap. VI 2).
Keys to the design of high-intensity mixers are an efficient means to initially disrupt
the continuous gas phase to create high interfacial surface area, efficient distribution
of the gas into the pulp suspension, high
energy input in the mixing zone, and a small
mixing volume to minimize overall energy
consumption (20). The incoming pulp sus-
604
pension can be fluidized by the motion of

rotor wings against stationary ribs; chemicals injected through radial inlet nozzles are
mixed with the stock (19). Sunds'SM
Mixer introduces gaseous chemicals into
the middle of the pulp stream and then
forces the mixture through fine slots to induce turbulence and enhance mixing.
In higher-temperature
applications,
steam mixers are used to heat high- or medium-consistency
stock prior to its being
sent to the tower or reactor. Steam mixers
are generally single- or double-shaft horizontal peg mixers equipped with multiple
steam inlets (21).
In high-consistency processes, comminution or fluffing of the pulp leads to increased
gas-pulp interfacial surface area and decreased mass transfer resistance. One type
of fluffer consists of a vertical toothed screw
to shred the pulp and convey it to a rotating pin cage to further break up pulp
clumps before the pulp drops into the reactor below (10).
4. Design criteria for reactors

4.1 Tower reactors
General tower design
criteria
Tower reactors are the most common

bleaching reactors. The development
of
continuous bleaching stages in the 1930s
was marked by the use of upflow towers at
low consistency and downflow towers at
medium consistency (14). Modem tower
design is aimed at achieving a given residence time to complete the bleaching reaction and plug flow to obtain maximum
bleaching uniformity. The reactor interior
volume is determined by the required residence time and ranges from about 1-3 minutes for medium-consistency
ozone
bleaching to 15-30 minutes in chlorination
and hypochlorite bleaching and from 3 to
5 hours in final chlorine dioxide and peroxide bleaching. Additional allowance must
be made for the dilution zone in downflow
towers and for the top scraper in upflow
towers (21). General design criteria for
tower reactors at different consistencies
have been previously described (21,22).
The tower IjD (length/diameter)

ratio is
designed to ensure the critical minimum
stock velocity necessary to minimize channeling and pulsing and maintain plug flow
(22). For plug flow the velocity must be
high enough for the stock plug to start to
disintegrate around the outside edge ofthe
plug near the wall with enough shearing
occurring to initiate creation of a dewatered
zone. Bodenheimer established curves and
algorithms based on mill experience to predict the critical minimum velocity (22).
Types of tower reactors
Tower
reactors
can be upflow,
downflow, or a combination of both types
(Figs. 4-6) (3). Upflow reactors are used
in both low- and medium-consistency
reaction bleaching stages and are particularly
advantageous where the hydrostatic pressure is used to increase gas solubility (Sects.
5.1 and 5.2 below). Upflow towers or retention tubes are also widely used to provide additional residence time following
high-intensity mixing in medium-consistency oxygen and ozone delignification/
bleaching operations.
Compared
with downflow
towers,
upflow towers are less complicated to operate, having one less stock pump and no
dilution zone or level to control because
they work by way of overflow. As a result,
the effective tower volume for an upflow
tower is nearly 100%. Upflow towers can
discharge without dilution, an advantage
when combining two bleaching stages without intermediate washing, for example, an
upflow followed by a downflow tower
(4). The main limiting factor in upflow
towers with regard to consistency is the frictional resistance of the pulp as it is transported to and through the tower. Upflow
towers have a fIXed retention time at a
given throughput and are susceptible to
channeling at larger diameters, even when
a pulp distributor is present in the bottom.
In stages using an upflow tower, the pulp
leaves the washer of the preceding stage,
may be heated in a steam mixer, and passes
through a pump and, in some cases, a
chemical mixer, to the bottom ofthe tower.
The tower inlet contains an agitator or ro-
605
Chemical
Pulp
out
Pulp
in
Fig. 4. Seberrullt4: 41i1grwm ofUP~
IofHr
(13).
Chemical
606
Pulp Bleaching
-Principles
and Practice
packing in the tower is 1()()% because the

pulp suspension occupies the entire volume. At higher consistency, void spaces are
present and in the tower a bulk density prome exists which is a function of pulp type,
temperature, and chemicals used.
The advantages of downflow towers include variable retention time decoupled
from production rate, ease of pumpout during shutdowns,
improved mixing, and
longer retention time in the dilution zone
when a neutralizing agent, for example,
sulfur dioxide or alkali, is added at the base
of a chlorine dioxide tower (21). Downflow
towers allow the use of higher consistency
than upflow towers and are used in highconsistency bleaching (14).
The historic disadvantage of downflow
towers is their tendency to plug at consistencies approaching 20%. The risk of plug
formation in a downflow tower is greatest
at 20-25% consistency,coincident
with the
disappearance of free water (14). Other
problems include level control and the tendency of the cooler dilution zone to migrate
upward irregularly, prematurely stopping
the bleaching reaction (14). Improved sensors and more efficient agitation at the
tower base have significantly improved the
operability of downflow towers.
An upflow.<Jownflow tower combination
is used to provide both hydrostatic head and
variable retention time, as, for example, in

oxygen-enriched
extraction and chlorine
dioxide bleaching (Sect. 5.2 below).
Tower
inlet and discharge requirements
Inlet devices improve distribution, prevent channeling, and facilitate plug flow of
the stock in the tower, leading to closer
control of residence time and improved
uniformity. In an upflow tower, an agitator
will be used for low-consistency bleaching
(e.g., in chlorination).
In a larger diameter
medium-consistency
upflow tower, a rotating stock distributor is used at the tower
base to promote uniform pulp feed across
the cross-section of the tower. A distributor may also be used to add chemical at a
point of relatively high shear, but distributors are inefficient mixers compared with
modem high-intensity mixers.
In upflow tower discharge, scrapers are
used to facilitate flow and to allow better
control of reactor residence time (Fig. 7).
Scraper blades on rotating arms feed the
pulp to the sides of the bleach tower. In
wet discharge, the pulp is collected in a
chute with dilution water introduced at the
top of the chute. The tower may also have
a dry discharge, that is, with no dilution, in
which pulp, directed by a rotor to the edge
of the tower, is collected and transported
around the periphery to a chute.
Pulp
out
Fig. 5. ~
41i1grwmof tlortnIjImtJ IofHr (13).
tating distributor to facilitate plug flow. The

pulp passes up the tower where it may be
discharged without dilution with the assistance of a concentric or eccentric scraper
(21). The pulp overflows the tower and is
diluted on its way to the washer vat.
Downflow towers are used, especially in
North America, in medium-consistency
stages that do not require a hydrostatic head
for gas dissolution. The pulp is heated in a
steam mixer and dropped directly into the

tower or pumped to the top of the tower.
Agitators at the bottom of the tower provide a turbulent zone where the pulp is diluted to 3-5% and discharged uniformly.
The effective
tower volume
in a
downflow tower is about 75-80% because
of the volume lost in the dilution zone and
in the top cone of pulp (14). Up to about
10-12% consistency, the degree of pulp
Pulp
out
Fig.
6.
Seberrullt4:
4IiIgrwm
ofupflOllJ-tloumflOllJ
tower
(13).
607
608
Pulp Bleaching
-Principles
and Practice
a)
---__.
:~:J
I--
:=..~
t.-Dilution
-===-
':-~~=--"---T+r---
---
Pulp
Non diluting: inlet and outlet consistency
= 8-13%;
Diluting: inlet consistency
13-25%: outlet consistency
b)
JII,.B BoIIom mwpers for "'fICf1IISIstaey
8-1j'Jf.; OIl"",,,:
4.2 Medium-consistency, high-intensity mixer/reactors
~-----
Pulp
FIt. 7. Topmwpersjor flJlfI- '-~
(S"'DejUmllfJr,")
Ilry "",,,
to 12%emulstnu:y b) 'l'mHr6aWJIerto ~
Discharge design for a high- or mediumconsistency downflow tower must provide
for even pulp flow out of the tower to a
low- or medium-consistency transfer pump.
downflow towers,
the wall friction is generally too low to disrupt the fiber network, allowing stagnant
pulp to collect on the reactor walls near
the discharge unless discharge is designed
properly (16). Conical or hemispherical
bottom designs with rake or scraper-type
bottom dischargers are used (e.g., in high-
'l'mHr6aWJlertotUsebM,UJfJtIn"".
to 1001B'Yoemulstnu:y.
""
and medium-consistency
downflow towers) to improve circulation and facilitate
even discharge without channeling to a
medium-consistency
pump (Fig. 8). Dilution can be carried out using a diluting
scraper or a series of pressure-actuated
nozzles to induce internal circulation, break
up and dilute the underside of the pulp
plug, and ensure uniform transition to a
lower consistency (21). Circulators inside
the tanks or reactors are also used for mixing in the dilution zone. The height of the
dilution zone can be regulated using an in-
max
lliselNnre (AblstrorrtKiImyr).NmI-tUlfIIi"t: ,,,let tIIUl_tlet
'- Cf1IISIstaey
,tIlet
terface detector (21). High-consistency

tower discharge can be accomplished using an agitator in the tower base to facilitate discharge followed by dilution of the
pulp to 5-10% consistency in one or two
discharge screws.
= 13%
The development of high-intensity mixing technology to intimately mix pulp with

a gaseous bleaching agent opened up the
entire field of medium-consistency
delignification and bleaching. The high-intensity
mixer leads to effective gas dissolution because a high gas-pulp interfacial surface area
is generated at high shear levels and to pulp
network disruption in conjunction
with
increased gas solubility stemming from
higher pressures. The first high-intensity
mixer application was in chlorination and
since then pressurized high-intensity mixing technology has been broadly developed
and commercialized in other areas including oxygen delignification,ozone bleaching,
oxidative extraction,
chlorine dioxide
bleaching, and oxygen-pressurized
peroxide bleaching (Sect. 5.5 below) (23).
= 13-25%, 08tlet
etnUIstmey
= 13%_.
Following mixing, the pulp is transferred

to a pressurized upflow reactor or retention tube where reaction continues as the
small gas bubbles dissolve. By proper selection of the reactor UD ratio, use of the
proper gas volume ratio, and operation in
the correct consistency range, the dispersion is relatively stable.
contacting reactors
Reactors have been developed with internal contactors or other means to facilitate exposure of the pulp to the bleaching
agent for improved reaction unifOrmity. For
example, in high-consistency ozone bleaching, a horizontal well-mixed reactor operating close to ideal plug flow and equipped
with shaft-mounted paddles has been developed and commercialized. This reactor
design was adopted following a detailed
analysis of the rate-limiting steps, and after
extensive laboratory and pilot work demonstrated that downflow tower reactors had
unacceptable levels of brightness variation
because of non-uniform gas-pulp contact.
Another reactor design approach is based
on the reaction of pulp with ozone in a
609
Pulp In
Pulp Out
(CD)(EO)
WulUalace
Dlapla"emenl
Tower
PI,. ,. 'nro-s,.
KiImyr)
1l1sJl'-'
wee
Wi"ine
Pump
61Hd11ag1_
(D1)(EJ)
WulUalace
Dlapla"emenl
Tower
wee
Wi"inc
Pump
~ Relentlon
Tower with
Diffuaer
If..bine
III 11nw-w-r (QJ)-(IJO)-D-I!-D

61MdJ"..,
5. Reactors for pulp bleaching examples

5.1 Upflow towers (low-consistency)
Chlorination is carried out using a relatively straightforward
tower design based
on upflow. The hydrostatic head of the
tower maintains pressure on the system to
increase chlorine solubility (Fig. 10) (13,
21). Agitators in the tower bottom distribute the incoming stock uniformly over the
tower cross section to prevent channeling
and facilitate plug flow. The tower provides
sufficient residence time for the slower reactions to proceed, and typical retention
W~
Slorace
Tank
610
PuJp Out
(Ahlstrom
(28).
fluffer, the reaction being completed afterward in a tower (24, 25). This development
was in part based on studies showing the
impact of fluffing on bleaching performance.
4.4 Displacement bleaching towers

Rapson (26) showed that displacement
of bleaching chemicals through a pulp mat
led to a large increase in reaction rate compared with that in conventional bleaching
towers. The rate increase was caused by a
large increase in the mass transfer rate resulting from continuous exposure of the fiber surfaces
to highly concentrated
bleaching chemicals and more rapid mass
transfer of the reaction products from the
fibers (27).
Displacement bleaching was commercialIzed by Kamyr AB which used its diffuser
washer concept as a means of displacing
spent bleaching solution with the fresh
bleaching solution of the next stage. The
first full-scale installation was brought into
operation at Temple Eastex in 1975; four
diffuser washers were used in succession
in one tower following a conventional lowconsistency chlorination stage. More recent
designs abandoned the incorporation
of
several bleaching stages within one tower
for several reasons including lack of residence time control, stringent metallurgy
requirements, higher chemical consump-
tion, and the inability to fully utilize the

high-intensity
mixer approach for pulpchemical contacting. This led to the use of
a separate tower fur the final D-Stage to provide longer residence time fur higher brightness and dirt removal (13). Examples of
single-tower displacement bleaching are the
incorporation of two stages within a single
tower preceded by a high-intensity mixer
(e.g. ,(CD) (EO) in Fig. 9) and use of a more
conventional
single tower with diffuser
washing at the top of the tower and medium-consistency
mixing between
the
stages (28, 29). (Diffuser washers are discussed in Chap.V13.)
4.5 Tray reactors
The first commercial high-consistency
(25-30%) oxygen delignification process
was installed in 1970 at the South African
Pulp and Paper Industry's Enstra mill. The
Sapoxal (Kamyr) reactor was a downflow
tower with internal rotating trays (compared with a filled vessel). The advantages
claimed were improved gas-solid mixing
and contacting, adaptability to varying retention time (by varying the speed of rotation), and less bed compaction because bed
height was set by tray-to-tray distance (30).
However, this reactor design was significantly more complex and expensive than a
standard downflow tower and was not
widely accepted.
times are in the range of 30-60 minutes.

The dimensions of chlorination towers vary
according to the retention time, consistency, and tonnage; for a 1000 air dried
metric ton per day (admtpd) production
rate and a 45-minute retention time, the dimensions are 5.5 m in diameter by 38 m
high at 3.5% consistency.
In the overall chlorination process, pulp
stock, previously diluted to 3-5% consistency at the storage tower base, is transported successively
to a blend chest,
mixers, the bleaching tower, and the washer
vat. The chlorine gas is dispersed in water
in the form of smal1 bubbles using venturi
devices or static mixers and this dispersion
is added to the pulp (31). During the mixing step, it is important to avoid entrainment of air in the stock because
air
compromises chlorine-pulp mixing and may
lead to channeling in the tower (21). Highintensity mixers have been shown to decrease bleach chemical consumption (32).
Chlorination is characterized by a fast initial reaction (on the order of seconds) between chlorine and lignin and a slower
second reaction
which gradually
approaches an asymptotic limit (on the order
of minutes) (31). Efficient chlorination requires good initial mixing of the gas dispersion with the pulp suspension to increase
the interphase mass transfer rate, avoid
pockets of over- or under-chlorinated pulp,
and avoid bubble coalescence which can
cause corrosion and tower channeling problems (33). When good mixing is provided,
the overa1l reaction rate in pulp chlorination probably is controlled by the chemical
reaction rate (7, 34-36) although a mechanism suggesting that diffusion transport of
chlorine within the cell waIl is rate-limiting
has been proposed (37).
5.2 Upflow or upflow-downflow
ers (medium-consistency
towD- and
(EO)-stages)
Medium-consistency
chlorine dioxide stages
As was the case for chlorination,
upflow
or upflow-downflow
towers are used in
chlorine
dioxide
stages to maintain
hydrostatic pressure head at the point of
chemical
addition.
Chlorine
dioxide

delignification requires a significantly longer
retention time than chlorine delignification
because of the lower chlorine dioxide reaction rate. A typical upflow leg provides
about 30-60 minutes of residence time, and
the downflow tower the remaining 2.5-4.5
hours of residence time. Typical dimensions
for 1000 admtpd are 3.6 m diameter and 32
m high for the upflow leg and 7.0 m diameter and 34 m high for the downflow tower.
The first upflow-downflow
chlorine dioxide tower, installed in 1952,took advantage
of the invention in the 19405 of the thickstock pump which allowed use of a combination of steam mixer, thick-stock pump,
and chemical mixer to combine the pulp
with a water solution of chlorine dioxide
under pressure (21). Upflow chlorine dioxide towers have retention times of 3':5
hours.
Overall chlorine dioxide kinetics for
medium-consistency
delignification
and
bleaching involve a rapid initial reaction
followed by a rate decrease with increasing reaction time (38, 39). Assuming efficient mixing of the chlorine
dioxide
solution with the pulp slurry, the reaction
of chlorine dioxide with pulp is considered
to be reaction-rate controlled (Chap. VI 2).
Reactor design requires effective chemical
mixing, suitable control of pH and temperature, and a plug flow tower to provide the
amount of residence time needed to complete delignification/bleaching
and to decrease dirt.
To improve mixing, high-intensity mixers are used for chlorine dioxide addition,
giving rise to more homogeneous bleaching in the following upflow tower which
in turn leads to decreased chemical demand
or a higher final brightness at a given chlorine dioxide application (18, 40). When
improved mixing is utilized, the bleaching
stage conditions must be reoptimized for
time, temperature, chemical residual, and
brightness target. Shive removal efficiency
may decrease if improved mixing is used to
decrease bleaching chemical application or
reaction time (41, 42). Additional discussion of operating strategy in chlorine dioxide bleaching is provided in Chap. IV 8.
611
Medium-c:onsistency oxygen-enriched
extraction stages
Oxygen-enriched
extraction (EO) was
commercialized in Sweden in 1980 following the introduction of medium-consistency
(8-16%) high-intensity
mixers (43). An
(EO) stage employs conditions similar to
those of conventional a1kali extraction with
the exception of three additional process
variables: oxygen addition rate, oxygen
pressure, and time at pressure (44). An
additional requirement is an upflow tower
or an upflow retention
leg ahead of a
downflow tower to provide the hydrostatic
head. This increased pressure keeps the
oxygen, which has a relatively low solubility in aqueous alkaline solution, at a higher
concentration
and keeps the undissolved
oxygen bubbles small (45). Typical upflow
preretention tube conditions for (EO) include a relatively short retention time requirement of 15 minutes or less (44, 46).
For a 1000 admtpd production rate, the
upflow tube dimensions would be 2.2 m in
diameter x 21 m high.
The (EO) upflow tube can be pressurized using a back-pressure valve to allow
additional oxygen to be charged at a higher
temperature, for example, at a pressure of
0.3-0.4 MPa at the top of the upflow leg
and a temperature of 85-90C (10, 47).
The pressurized upflow leg can lead to additional delignification or can be used to
compensate for a short upflow leg height
in a retrofit. Oxygen is added to a highintensity mixer or through a sparger inunediately after a medium-consistency
pump.
An (EO) stage can also be conducted in a
displacement bleach plant (45).
5.3 Upflow or downflow towers (medium-consistency
E and P stages)
Medium-c:onsistency alkaline extraction

An upflow or downflow tower can be
used for medium-consistency
(12%) caustic extraction. Classic alkaline extraction
stages dating back to the 19305 used medium consistency which, when compared
with low consistency, permitted the use of
higher a1kali concentrations, less steam, and
smaller towers while still facilitating diffu-
612
Pulp Bleaching
-Principles
and Practice
sion and contact of a1kali with lignin (48).

Typical alkali extraction stages use a steam
mixer and high-density
pump.
Alkali
(NaOH) is usually added to the repulper
ahead of the steam mixer. Typical conditions are 10-16% consistency, 60- 70C, pH
10.5-11, and 60-120 minutes' tower retention time (21). For a 2-hour retention time
in an E stage operated at a production rate
of 1000 tons per day, a downflow tower is
6.5 m in diameter and 26 m high including
2.5-3 m for the bottom dilution zone.
Alkaline extraction is perfonned by adding sodium hydroxide to achieve a sufficiently high end pH to solubilize lignin
through ionization of acidic groups. The
reaction has been treated as chemical kinetic-controlled (with two parallel reactions
representing rapid and slow removal of lignin), assuming that there is effective initial
a1kali-pulp mixing and that intrafiber diffusion of lignin is not rate-limiting (35). As a
result, an alkaline extraction stage requires
good initial mixing, temperature and final
pH control, and adequate residence time
in the tower for the extraction to occur.
For many years, reactions occurring in
alkaline extraction-type
stages were enhanced with hypochlorite.
Work in the
1960s with hydrogen peroxide (EP) and,
in the late 19705, with oxygen (EO;see Sect.
5.2 above) further established that oxidizing chemicals could be added to provide
the benefit of higher final brightness at a
given bleach chemical charge or reduced
chemical consumption and a lower viscosity decrease (43). The minimum capital
approach is to add the oxidant before the E
tower as, for example, in an (EP) stage; the
required amounts of hydrogen peroxide and
sodium hydroxide are premixed with dilution and added to the pulp in a chemical
mixer (49).
Medium-consistency
hydrogen
peroxide
stages
Hydrogen peroxide bleaching can be
conducted
in a separate downflow
or
upflow tower or in a high-density pulp storage tank although use of a separate tower
favors improved control of retention time,
temperature,
pH, and consistency
(50).
P stages are carried out in alkaline extraction stage towers at temperatures

above
70C, an initial pH of about 11, and a residence time of from one to several hours; a
peroxide residual must be present at the
end of the reaction to prevent alkali darkening (51). Final pH, residual chemical, and
metal control (by means of magnesium sulfate and sodium silicate addition) are important process considerations
and a
separate chelation stage may be inserted
before the peroxide stage to selectively remove transition metals (52-54).
5.4 Downflow
towers
(high-c:onsistency)
High-consistency oxygen stages

High-consistency
processes were first
commercialized in 1970 prior to the development of medium-consistency
high-intensity mixers. The early focus in high-consistency reactor design was oxygen delignification. However, the process was not
commercialized until the discovery of viscosity-protecting additives in 1963 (55).
Compared with medium-consistency
bleaching, the diffusional resistances at high
consistency are less, therefore eliminating
specialized mixing requirements. Reactor
design criteria include efficient reaction of
both a1kali and oxygen in a three-phase system in which a rate-limiting step is diffusion of dissolved oxygen through the water
phase. In oxygen delignification at high
consistency, 50 times more oxygen is consumed overall than can be present in the
liquid phase at anyone time because ofthe
limited solubility of oxygen in aqueous sodium hydroxide and the relatively small
amount of water available. Also, the oxygen diffusion rate in the aqueous phase is
relatively low. Accordingly, reactor design
must create a high gas-solid interfacial surface area to facilitate oxygen mass transfer
(30, 56). Reactor design must also allow
for sufficient tower residence time because
oxygen bleaching is characterized
by an
initia1Iy rapid reaction followed by a slower
reaction (57).
The process, initia1Iy commercialized by
MoDo and CIL, with the aid of equipment
supplied by Sunds (now Sunds Defibrator)

and IMPCO, included use of a dewatering
press to raise the consistency to about 2832%, spraying of alkali or oxidized white
liquor onto the fiber mat exiting the press,
heating of the pulp in a steam mixer, and
transfer of the pulp to the downflow reactor through a thick-stock pump or a plug
screw feeder equipped with a gas seal to
hold reactor pressure (Fig. 11) (58). The
pulp is fluffed as it enters the top of the
reactor and then drops into a vertical
downflow reactor having a continuous pulp
bed with no trays and with oxygen provided
under pressure. The tower is designed to
facilitate gas/solid-type contacting and reaction.
At the bottom of the reactor, the pulp is
diluted before being blown to a blow tank.
A rotary discharge is utilized to direct the
pulp toward the blow line (10). Consistency is limited on the high side to about
32-33% by the need to control the increase
in pulp reaction temperature caused by the
exothermic heat of reaction. On the low
side, consistency must be above about 25-
614

Pulp In
26% to avoid bed compaction produced by

dewatering which compromises mass transfer and oxygen availability (30). For a 1,000
admtpd production rate and thirty minutes'
retention time, the reactor dimensions are
4.8 m in diameter x 13.3 m high.
A recent modification of the conventional
high-consistency process involves treating
the washed brown stock at low consistency
with alkali to improve fiber contact with
the alkali before dewatering and reaction
(12). Higher levels of delignification were
reported without pulp viscosity penalty.
This modification requires no change in
tower design, but good filtrate management
is important to minimize alkali use.
High-consistency ozone stages
The commercialization
of high-consistency oxygen de1ignification led to research
in the 19705 and 1980s aimed at extending
the dewatering and fluffing technology to
ozone bleaching. Compared with oxygen,
the key differences in high-consistency
ozone bleaching are lower pH, inclusion of
Twln-roll
Press
Clove-Rotor
613
..
Pump
02 Reactor
Discharger
Dftuted
stock
out
Peroside
Reactor
P-Stale
W..her Filtrate
Flg.12. Hlgb~
JIetWdM bletU:WrlgretU:tor
(S._
DejUmllor).
a chelation step, higher consistency (3545%), lower operating pressure (slightly

above atmospheric), and shorter reactor
retention time (about 60 s). Compared with
low- or medium-consistency
ozone bleaching, high-consistency ozone bleaching has
the advantages of a higher reaction rate (because the ozone is absorbed into a thinner,
immobile water layer on the fiber surface)
and lack of a physical upper limit on ozone
application. The amount of applied ozone
is a function of the properties of the pulp
entering the stage, the desired degree of
kappa number reduction in the stage, reactor type, and reaction conditions (59).
The initial step involves discharge of the
pulp from the washer of the previous stage
into a tank where the stock is chelated and
acidified to the target pH. The pulp is then
fed to a dewatering press, a thick-stock
pump or plug screw feeder conveyor, and
a pulp fluffer. In one case, a downflow bedtype reactor is used with co-current gas flow
and a pulp-gas disengagement zone at the
bottom where the diluted pulp is pumped

out (10). Pilot plant work utilizing different experimental approaches has been done
at several facilities (6, 60-62). Recent pilot work identified brightness uniformity
problems arising from the downflow bed
design which led to the use of a new reactor!contactor.
High-consistency peroxide stages
High consistency
(25-30%) has been
evaluated for hydrogen peroxide bleaching
as a means for achieving a higher final
brightness at a given chemical charge (14,
25, 63). Larger amounts of (or different)
stabilizers are required for high-consistency
peroxide bleaching than for bleaching at
medium consistency. A high-consistency
peroxide stage configuration may include
a dewatering press, a screw conveyor for
alkali and steam addition, a chemical mixer
for peroxide addition, a downflow tower, a
tank, and a washer (Fig. 12).
5.5 Medium-consistency, high-intensity mixer/reactors

Medium-consistency oxygen stages
The development of pressurized highintensity mixing was the recent key innovation leading to commercialization
of
medium-consistency oxygen delignification
in 1980. The process uses medium-consistency stock pumping technology to feed
pulp directly from the brown stock system
to the pressurized
high-intensity
mixer
where alkali, high pressure steam, and oxygen are efficiently combined before entry
into the upflow tower (Fig. 13). Recently
developed pumps and high-intensity mixers have fluidizer designs capable of operating up to about 15% consistency.
The pressurized high-intensity
mixertower concept is suited for the oxygen
delignification reaction which has the following characteristics: (1) the overall kinetics can be described by an initially fast
reaction lasting about 10 minutes and a second reaction which is proportional to the
concentration of residual lignin assuming
the availability of alkali and oxygen (Chap.
IV 1), (2) the rate is a function of the degree of mixing and is controlled by chemi-
..
615
after mixing are so numerous that gas coalescence and tower channeling occur (10).
To drive the reaction, medium-consistency
oxygen delignification is normally designed
for pressurized operation (0.5-0.6 MFa).
After the mixer, the tower provides sufficient residence time (45-60 minutes) to
achieve delignification in the 40-45% range,
above which selectivity deteriorates (64).
To prevent channeling and maintain plug
flow, pulp consistency in the tower must
be above 10%; a rotating distributor is used
in the inlet and the tower has a relatively
high aspect ratio (10) (Fig. 13). (Typical
tower dimensions for a 1000 admtpd production rate are 4.5 m in diameter by 24 m
high.) The stability of the pulp-gas dispersion is also aided by the buoyancy imparted
by the trapped oxygen which reduces the
likelihood of bed compaction. At the top
of the reactor, a fully submerged rotating
scraper- type discharger prevents plugging
and channeling
and directs the pulp
through a blow valve to the blow line and
the blow tank where the pressure is relieved.
More demanding operations
for example, those involving a larger kappa number reduction, softwood delignification, or
higher entering dissolved solids levels
may lead to oxygen depletion. Efficient prewashing minimizes black liquor carryover,
which can otherwise cause cellulose degradation and consume oxygen and alkali,
and allows higher delignification levels to
be achieved (20).
Multiple stages are required to reach the
same degree of delignification as that obtained in high-conslstency operation. This
is a result of the lower reaction rate in medium-consistency
bleaching caused by
lower alkali concentration at a given charge
and possibly by mass transfer constraints
leading to localized oxygen limitations (30,
65). To increase the total oxygen charge,
two mixer/reactor units may be used in series followed by a single blow tank (Fig. 14).
The first stage (tower or retention tube)
typically has a shorter residence time (about
10- 20 minutes) and the second, a residence
time of about 45 minutes (66).
FIg.13. Me"'
(KJJamIer
eo.stste.ey
P81p18,
o:ryle8 reactor
TeeIntologIes).
cal reaction kinetics or by the rate of mass

transfer of oxygen or alkali to the fiber (30,
56), (3) the rate is affected by the relatively
low solubility of oxygen in aqueous sodium
hydroxide and the need to mix a relatively
large volume of gas with the pulp with the
result that part of the oxygen remains in
the gas phase during the reaction (8, 30).
In the medium-consistency
high-intensity
mixer, there is an upper limit for the maximum oxygen charge per stage. Above a
critical gas:suspension
ratio, gas bubbles
616
Medium-consistency
ozone stages
A related process concept is used for
medium-consistency ozone bleaching. Pulp
(acidified and, in some cases, chelated) at
10-14% consistency is pumped to a highintensity mixer where the compressed gaseous bleaching
agent (ozone/oxygen
mixture) is added and where high pressure
and relatively high ozone feed concentration are used to decrease gas volume and
increase gas solubility. The ozone/pulp suspension is then fed into an upflow tower
where the reaction is completed (11, 67).
Discharge is through a pressure control
valve to a gas/pulp separator.
As was the case in oxygen delignification,
pilot studies have demonstrated that effective mixing and reaction take place as long
as the gas:pulp suspension volume ratio is
below a certain critical level (68, 69). An
increase in suspension gas volume led to a
decrease in applied power, indicating a reduction in mixing efficiency, bubble coalescence, poorer mass transfer, and an
increasingly unstable suspension flow following the high-intensity mixer and in the
ensuing upflow tube (11,70) (Fig. 3). Compared with oxygen delignification, the overall reaction time in orone bleaching is much
shorter. The upflow tower where the reaction is completed has a retention time no
higher than 1-3 minutes (11,67, 71) (Fig.
15). Laboratory studies showed that most
of the bleaching occurs within and immediately after the high-intensity mixer (reten-
tion times in industrial mixers are less than

one second). This was confirmed by 1) a
rapid decrease in kappa number and a high
initial rate of ozone consumption and 2)
little additional delignification in the following pressurized upflow tube even though
ozone concentration continued to decrease
(72, 73).
Another difference in ozone and oxygen
delignification is that ozone is supplied by
commercial ozone generators at a weight
concentration limited to approximately 12%
ozone in oxygen. The restrictions for ozone
concentration,and
on the gas:pulp volume
ratio, limit ozone applications in a single
mixer-reactor unit to about 4-5 kg ozonel
ton of pulp (at 150 psig or 1.1 MPa) and
10% by weight ozone (Fig. 3). Medium-consistency ozone delignification processes requiring higher applications
for a higher
kappa number reduction must use high-intensity mixers in series followed by a single
reaction tower or successive mixer-tower
units (74).
5.6 High-c:onsistency
contacting reactors
The first commercial high-consistency
ozone bleaching reactor is based on a
paddle-conveyor reactor design operating
close to ideal plug flow and is discussed in
the case study (Sect. 6).
An alternative reactor design for highconsistency ozone bleaching involves passage of the pulp and ozone into a
fluffer-blower from which the mixture is
transferred to a downflow tower to complete the reaction (24, 25). In a pilot plant
study, about 60% of the ozone consumption
and at least half of the kappa number reduction occurred in the fluffer with remaining reaction occurring in the tower (24, 25).
6. Case study
The attractiveness of ozone bleaching
from an environmental standpoint led to
intensive experimental work to quantify the
benefits and to identify the proper reactor
design for the process. Early on, ozone
bleaching was investigated at low consistency because of process simplicity and the
availability of larger amounts of water for
ozone dissolution (75, 76). In this work,
the need for suitable contacting to minimize
the mass transfer limitation was recogmzed.
Use was made of static mixers (laboratory
scale) and a pilot-scale reactor consisting
of a vertical, agitated upflow tower, a
hydrocyclone, in which ozone was introduced through an interniil porous tube, and
617
a high-pressure mixer/tower reactor (7679). However, drawbacks in the process

included (1) gas/pulp contacting difficulties
attributable to the high gas:water ratio (because ozone is supplied at 6-12 % by weight
in oxygen or at even lower concentrations
in air), (2) a relatively low reaction rate resulting from the low solubility of ozone in
water, (3) higher ozone consumption attributable to higher ozone decomposition rates
at the higher water:fiber ratio, and (4) large
volume recycle water requirements making
mill close-up more difficult (76).
Alternatively, pilot ozone bleaching at
medium consistency using a pressurized
high-intensity
mixer approach
demonstrated that effective contacting and reaction could be achieved (68, 69). However,
restrictions in the gas:pulp volume ratio and
ozone concentration
limited ozone application, a key issue when ozone bleaching
is used for "bulk delignification" (80).
Work at Union Camp with high-consistency ozone bleaching was initially con-
Scrubber
,,
618
ducted on a pilot scale following an approach similar to that used in high-consistency oxygen delignification. This consisted
of a combination of dewatering, fluffing,
and reaction in a downflow tower designed
for co<urrent
ozone feed. However, the
downflow bed design was found to lead to
brightness nonuniformity in the fast-reacting ozone system because of variation in
bed density and uneven gas flow down the
reactor (6). This led to uncertainties, not
only on the pilot scale, but also in reactor
scale-up.
As a result, a fundamental analysis was
made of the rate-limiting steps in high-consistency ozone bleaching. Characteristic
times were calculated for each mass transfer and chemical reaction step necessary to
accomplish ozone bleaching (Table 1). This
analysis showed that all three mass transfer steps - bulk gas phase mass transfer,
diffusion through the floc, and diffusion
through the water layer and the fiber wall
are important in determining the overall
c.. Out
PIltnte
In
tl'8te
Ou
o
o
Pulp out
Pulp
'"
0'16111!
111
7 1't %
150 PSIG
...Medlum Consistency
Ozone Reactor
Out
reaction rate (Fig. 2) (6). The chemical

reaction of ozone with lignin was at least
100 times faster than the other three steps
and was not limiting. This analysis identified the three requirements key to optimal
high-consistency ozone bleaching reactor
design:
1. Fluffing of the high-consistency pulp. fluffing must result in uniform, small floes (measured using aerodynamic specific surface
(81) to increase gas-solid interfacial specific surface area and reaction rate.
2. Efficient pulp agitation. The pulp floes
must be brought into contact with the
ozone, and this requires effective, uniform
mixing/contact maintained over the total
reactor residence time.
3. Optimal pulp consistency. Consistency is
optimally above 35%, that is, above the fiber saturation point where the fiber matrix is swollen and saturated with water.
At higher pulp consistency, the ozone has
less water to diffuse through before reacting (24, 80). This leads to a higher reaction rate and decreased ozone requirement.
- Pulp
In

rule 1. CIHmIt:In'U1k_lNrIsfrr..
cHrrriaJlrHdlorl
Mass Transfer Step
2. Floc penetration
3. Diffusion through
and into fiber
4. Chemical
ill blfb-t:OIISIstftey0%_ "'-:Imtg
"-
Characteristic
1. External mass transfer (from bulk

gas phase to surface of floc)
(diffusion into floc)
619
time (s,/
(6).
Affected by
2-5
1-4
PIiIp agitation
1-3
Consistency
Fluffing
water layer (if any)
reaction with lignin
'Tune fur pulp to consume

by weight.
< 0.01
0.1% ozone on fiber assuming
Based on this understanding, the decision

was made to develop a high-consistency
process incorporating efficient fluffing and
a mixed reactor and, accordingly, a pilot
plant was constructed. Extensive experimental work led to development of a horizontal, well-mixed
reactor with shaftmounted paddles which operates close to
ideal plug flow (Fig. 16) (6, 80, 82, 83). In
this process, high-consistency pulp enters
the reactor in a highly fluffed state for maximum contacting with me countercurrentflowing gas.The uniquely designed paddles
continuously lift, disperse, and suspend the
fiber in the gas space, where the pulp reacts with the ozone, while conveying the
fiber forward. The specific paddle design
was arrived at using both image analysis (to
quantify pulp dispersion) and lithium tracer
techniques (to define pulp residence time
distribution and degree of plug flow) (6).
Following the pilot work, the reactor was
scaled-up in 1992 (Union Camp, Franklin,
Virginia) as the first commercial high-consistency ozone bleaching process.
7. Troubleshooting
A satisfactory, predictive reaction model
for a bleaching stage cannot only facilitate
design, but can also be a significant aid in
reactor troubleshooting.
As an example, a
model for oxygen delignification kinetics
has been incorporated into a complete oxygen-stage model which can be extended for
stage optimization
and control (57).
lithium (6, 18) or radioactive tracer methods are commonly used in troubleshooting
reactor performance to characterize both
mean residence time and the range or van-
a bulk phase ozone concentration
of 4%
ability of residence time in bleaching reactors. Radioactive tracer data, analyzed in

terms of a dwell time distribution, showed
that operation closely approximated true
plug flow for low-consistency upflow towers and most medium-consistency
towers
-upflow, upflow/downflow,or
downflow
with a bottom dilution zone (84). Chemical and radioactive tracer techniques used
with the same tower were compared for
low-consistency
upflow chlorination and
upflow hypochlorite bleaching (14). Both techniques indicated a similar mean residence time, but the
radioactive technique showed more skewness probably because of the sensitivity of
the method.
Proper placement and use of samplers
and sensors is essential for both routine
monitoring
and control of a bleaching
stage. Key parameters such as kappa number, brightness, viscosity, pH, temperature,
pressure, and bleaching chemical concentration can then be monitored fur analysis
of reactor performance. Samplers must be
designed fur the safe withdrawal of a representative sample from the pipeline or reactor under ambient or pressurized conditions
and are essential fur proper monitoring and
control of the stage.
Safety must be a priority in bleach plant
reactor design and operation. In the design
phase, a hazard and operability (HAZOP)
study should be carried out fur identification and analysis of potential hazards and
operating problems in reactor operation
(85). Reactor/tower design should include
safety features S\Ich as use of overpressure
protection devices, for example, pressure
620
relief valves and rupture discs, temperature

profile monitoring and control, to avoid
locally overheated zones and to activate
showers, if necessary, to quench exothermic heat of reaction.
Additional safety measures are taken depending on the specific process. The properties and hazards of the specific bleaching
chemicals must be taken into account (13,
50, 86). In high-consistency oxygen delignification, concentrations
of combustible
gases such as carbon monoxide and methanol need to be monitored and controlled
using a bleed stream to control accumulation of combustible gases. Also, care must
be taken to ensure that combustible additives (e.g., defuamers) do not enter the reactor with the pulp (30). In P stages,
hydrogen peroxide is applied to the pulp
in 5-10% concentrations
to minimize the
safety hazard in the event of a leak (87).
References
I. Levenspiel, 0., Chemical
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-~------
621
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Consistency BleachingTechnology
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45. Kortelainen,
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Bellmer GmbH, Niefern, 1992, pp. 81-82.
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Enriched Alkaline Extraction;
Operations
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31. Hise, R. G., "Chlorination

of Pulp; 1991
TAPPI Bleach Plant Operations
Short
Course, TAPPI PRESS, Atlanta, p. 105.
32. Petterson, B., lindstrom,
L.A.. Sundin, M.,
"Bleaching
is Improved
by Efficient
Mixing in the Chlorination
Stage; 71st
Technical Section, CPPA Annual Meeting
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1985, p.A105.
33. Reeve, D. W:, Pu, C M. Oshinowo,
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34. Ni, Y., Kubes, G.}. Van Heiningen,A.

J Pulp Pap. Set. 16(1):}13 (1990).
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Pap. Set.
36. Ni,Y., Kubes, G.).,Van Heiningen,A.

J Pulp Pap. Sct. 21(1):}30 (1995).
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J 72(3):159 (1989).
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Tappi
38. Teder, A. and Tormund, D., CPPA Trans.

Tech. Sect. 3(2):TR41 (1977).
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Tech. Sect. 6(2):TR31
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(1980).
40. Kolmodin,
H., Svensk
87(18):8 (1984).
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).,
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47. Fredstrom, C, Idner, K., Hastings, C, "Current State-of-the-Art

of EO, EP, and EPO
Technologies;
1992 Non-chlorine
Proceedings,
Miller Freeman, Inc., San Francisco.
48. Massey, w: M. and Nay, M.)., "Alkaline Extraction Chemistry and ProcessVariables;
1984 TAPPI Bleach Plant Operations Seminar Notes, TAPPI PRESS, Atlanta, p. 27.
49. Trebilcock,).
W., "Hydrogen
Peroxide
Bleaching;
1984 TAPPI Bleach Plant Operations
Seminar Notes, TAPPI PRESS,
Atlanta, p. 75.
50. Anderson,).
R., "Hydrogen Peroxide Use
for Improved
Environmental
Performance; 1991 TAPPI Bleach Plant Operations Short Course Notes, TAPPI PRESS,
Atlanta, p. 149.
51. Kutney, G. and T. Evans, Svensk
stidn. 88(6):R78 (1985).
Pulp Bleaching
papper-
52. Basta,)., Holtinger, L., Lundgren, P., Fasten, H., "Reducing Levels of AOX. Part 3.
Lowering
of Kappa No. Prior to CIO,
Bleaching,"
1991 International
Pulp
Bleaching Conference Proceedings,Swedish Association
of Pulp and Paper Engineers, Stockholm, Sweden, Vol. 3, p. 23.
53. Basta, j., Andersson,
L., Hermansson,
W,
"UGNOX and Complementary
Combinations; 1992 Non-<:hIorine Bleaching Conference Proceedings,
Miller Freeman, San
Francisco.
-Principles
and Practice
54. Van Lierop, B., Liebergott, N., Faubert, M.

G.,"Using Oxygen and Peroxide to Bleach
Kraft Pulps; Technical Section, CPPA Conference Proceedings,
Tech. Sect., CPPA,
Montreal, 1993, p. 881.
66. Kondo,
S., "Two Stage
MC-Oxygen
Delignification
Process and Operating Experiences;
Pan-Pacific
Pulp and Paper
Technology
Conference
Proceedings,
Tokyo, 1992,p.23.
55. Robert, A., Traynard, P., Martin-Barret,

French Pat. No. 1,387,853 (1%3).
67. Peter,W:,"First ExperienceWith

Mill Scale
Ozone Bleaching,"
1993 Non-Chlorine
Freeman, Inc., San Francisco.
0.,
56. Hsu, C L. and Hsieh,). S., Tappi J 68(6):92

(1985).
57. Myers,
27. Gullichsen,).,
in Tbe Bleaching
of Pulp
(R. P. Singh, Ed.) 3rd edn., TAPPI PRESS,
Atlanta, 1979,Chap.
10.
30. McDonough,
T. }., "Oxygen
Delignification; 1991 TAPPI Bleach Plant Operations Short Course, TAPPI PRESS,Atlanta,
p.57.
622
M. R. and
72(9):215
Edwards,
L. L., Tappi
(1989).
58. Miller,W:,"ProcessTechnology,Machinery,
Advantages and Disadvantages;
1992 NonChlorine Bleaching Conference
Proceedings, Miller Freeman, Inc., San Francisco.
59. Ali, 0., Eachus, S. W:, Seiter, D. E, "Use of
Ozone for Bulk Lignin Removal: Effect of
Feedstock Quality; ESPRA Spring Meeting,
Invited Papers, Empire State Paper Research Institute,
Syracuse,
New York,
1993, p. 25.
60. Liebergott, N. and van lierop, B. ,"The Use
of Ozone in Bleaching and Brightening
Wood Pulps. Part I. Chemical Pulps; 1978
TAPPI Oxygen,
Ozone, and Peroxide
Pulping and Bleaching Seminar Proceedings, TAPPI PRESS, Atlanta, p. 90.
61. Norden,
S. and Simonson,
0., "Ozone
Bleaching of Sulfite Pulp
A Pilot Plant
Study; Proceedings
of World Pulp and Paper Week - New Available Technologies,
SPCI, Stockholm,
1984, p. 118.
62. Patt, R., Kordsachia,

0., Wang,
Papier 42(10A):VI4
(1988).
L.-K.,
68. Dillner,
B. and
74(9):720 (1992).
Peter,
w.,
Pap.
Puu
69. Szopinski,
R. and Stromberg,
B., "High
Brightness
Using Totally Chlorine
Free
(TCF) Bleaching Sequences,"
1993 NonChlorine Bleaching Conference
Proceedings, Miller Freeman, San Francisco.
70. Bennington,
(1993).
C P. )., Tappi
J 76(7):77
71. Greenwood,
B. F. and Szopinski,
R.,
"Ozone
Bleaching
Technology
'92,"
1992 Non-<:hIorine Bleaching Conference
Proceedings,
Miller Freeman,
Inc., San
Francisco.
72. Oltmann,
E., Gause, E., Kordsachia,
Patt, R., Papier 46(7):341 (1992).
0.,
73. Sixta, H., GOtzinger, G., Schrittwieser,

Hendel, P., Papier 45(10):610
(1991).
A.,
74. Dillner, B. and Tibbling, P., "Isothermal

Cooking to Low Kappa Numbers
Facilitates TCF Bleaching to Full Brightness,"
1993 Non-Chlorine Bleaching Conference
Proceedings,
Miller Freeman, San Francisco.
75. Hruschka,
A., Wochenbl.Papierfabr.
114(17):681 (1986).
63. Perala,). and Germgard, U., "The Building

Blocks of the Ftberline forTotaIIy ChlorineFree Kraft Pulping; 79th Technical Section, CPPA Annual Meeting Proceedings,
1993, p.
A281.
76. lindholm, C-A, "Some Effects ofTreatment

Consistency in Ozone Bleaching;International Pulp Bleaching
Conference
Proceedings, Swedish Association of Pulp and
Paper Engineers,
Stockholm,
Sweden,
1991, p. 1.
64. Miller, w: ). and Dixon, S. A., "Medium

Consistency
Systems: Design, Operation,
and Performance; 1991 TAPPI Bleach Plant Operations Short Course Notes, TAPPI PRESS,
Atlanta, p. 87.
77. Meredith, M. D., "Rationale for Low Consistency

Ozone Bleaching,"
Paper Presented at the 1991 AIChE National Meeting, November
17-22,1991.
65. Greenwood, B. E, "Oxygen Delignification

Stage Design and Performance
-A Kamyr
Perspective,"
Operations
78. Schwarz!, K., Vitan, A., Sinner, M., Dtsch.

Papierwirtsch.,
2:T14 (1992).
79. Funk, E., De1court,
T., Vilpponen,
A.,
Munro, E C, "Espanola Ozone Bleaching
Pilot Plant :Progress Update,"APPITA Conference, APPITA, Parkville, Victoria, Australia, 1993, p. 217.

BO. Nutt, W. E., Griggs, B. F., Eachus, S. W.
PikuIin, M.A., TappiJ 76(3):115 (1993).
81. Gamer, R. G. and Kerekes, R.}., Trans.
Tech. Sect. CPPA 4(3):TR 82 (1978).
82. Pikulin, M. A., Gandek, T. P., White, D. E.,
Joseph,}.
c., "High Consistency
Ozone
Bleaching: Commercial
Implementation,"
1993 Non-Chlorine
Bleaching
Miller Freeman, San
Francisco.
83. Trimble, D. S., Harris, W c., Reeves, S. E.,
McMahon, S. E., Thurman, R. G., "Environmental Benefits of Ozone-Based
Bleaching," EUCEPA International
Environmental Symposium
Proceedings,
EUCEPA,
Paris, 1993, p. 185.
84. Gullichsen,}., Mannisto, H., Westerberg, E.
N., Pulp Pap. Mag. Can. 68(l1):T555
(1967).
85. Fail, P.}.,Appita
43(1):14
(1990).
86. Rogers, H. G., and Kinsley, G. R., in The

Bleaching
edn., TAPPI PRESS, Atlanta, 1979, Chap.
24.
87. Anderson
R., "Peroxide
Delignification
and Bleaching,"
1992 Non-Chlorine
Bleaching
Conference
Proceedings,
Miller Freeman, San Francisco.
623
SECl'IONVI:
Chapter 5:
Sensors and Process Control
J. Willems
ValmetAutomation (USA) Inc.
Norcross, Georgia
M. Williamson
Freelance technical writer
Thornhill, Ontario
1. Introduction
627
2. In-line process and quality measurements.

.............................
2.1 Pulp brightness. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2 Residual chemical. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3 Kappa number: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4 pH measurement. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . .
2.5 Chlorine dioxide solution concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.6 Flow and consistency. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
627
630
630
632
632
633
634
3. De1ignIficationandbleachlngcontrol
3.1 Traditional C-stage control. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2 DC- and D-stage control
3.3 Oxygen-stage control
3.4 Brightening D-stage control
3.5 Peroxide-stage control
4. Optimization
ofcontrolloop
performance.
634
. 634
636
637
638
639
. . . . . . . . . . . . . . . . . . . . . . . . . . . . 639
5. Advanced control: fuzzy logic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 642

6. Shive
analysis
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 642
625
Chapter VI 5: Sensors and Process Control
Chapter VI 5:
Sensors and
Process Control
627
rine is now being substantially or totally

replaced by chlorine dioxide. Pilip consistencies in the bleaching process are higher,
as are process temperatures. The pH in the
DC stage has changed and may be more
variable than before. These changes are in
addition to the traditional problems associated with variations in the lignin content
of incoming unbleached fiber, variations in
fiber species, and variations in dissolved
chemical carryover from the brown stock
washers.
The development of pu1p quality in a fiber line depends on the reactions of bleaching chemicals
with lignin. Chemical
reactants are applied at a certain ratio to
the fiber production rate, subject to incoming lignin content of the fiber and the degree of delignification
and bleaching
required.The amount of delignification and
bleaching that can be achieved in anyone
stage depends on those factors which
affect the chemical reaction rate and the
residence time in each stage. Process conditions are usually unique to each mill and
may be optimized to maximize production,
minimize bleaching costs, minimize environmental impact or, in many cases, to accommodate
the limitations
or unique
characteristics of the existing equipment or
the fiber supply. Figure 1 illustrates how
both delignification and bleaching proceed
1. Introduction
Chemical pu1p bleaching is an extension
of the fiber delignification process started
in the digester. As an integral part of the fiber production line, bleaching is a continuation of the delignification process which
is comprised of sequential steps or stages.
Besides further delignification, unit operations in the bleach plant lead to the development of pulp quality as expressed by
brightness and cleanliness.When operating
conditions are properly managed, pu1p fiber degradation and the formation of environmentally
harmful by-products
are
minimized. For the pu1p manufacturer, it has
become a challenge to maintain pu1p or
paper quality targets and to decrease the
environmental impact of bleach plant emissions in balance with bleaching costs.
Environmental concerns and the pressure to increase production rates have created major changes
in the chemical
processes used in delignification and bleaching, the types and amounts of chemicals
applied, and the process conditions under
which chemical reactions take place. Chlo-
80
0
0
~~60
u)
II)
CD
-c:
40
In
20
1% lignin
28% lignin
.s::.
C>
'L:
------~,'
,,-,,' ~', ......

..........
\5% lignin
Digester G
E
Delignification
Fig. 1. Delipl/ktUlon
qrumce.
tUUl brigbtness
developmerll
D
profile
E
0
Bleaching
of softwootl
lnYIft pulp
blellCbed I.. (I CEDED $e-
628
through

a fiber line. In the initial stages,
lig-
nin removal is the goal; in later stages,

bleaching or brightening is the goal.
In making the transition to environmentally friendly pu1p production, many process conditions have changed, affecting the
rates of de lignification
and bleaching
reactions. The dynamics of the bleaching
process, which are well understood in traditional chlorine bleaching, have changed.
Reactions progress at different rates. The
challenge for the process control engineer
or process manager is to understand exactly
how the dynamics have changed and how
process measurements, fiber quality measurements, and control strategies can be
effectively applied in these new situations.
It is also important to understand that, because mass flow processes are comprised
of many unit operations,
bleaching sequences are subject to short-term mass flow
variations which can originate in many different locations and, if not effectively reduced, can propagate through the entire
bleaching process. Because there is a significant time delay through the process,
correcting variations earlier rather than
later is preferable. For the most effective
control, an update of product quality or
reaction rate after a few minutes is better
than an update after an hour because input
pu1p conditions may have changed within
the latter period. When the bleaching process is controlled using manual techniques
and is based on final quality measurements
that are hours old, there is a tendency to
add too little or too much chemical, thereby
destabilizing the process with the resu1t that
pu1p quality or process costs are adversely
affected.
In-line measurements of product quality
and process conditions update in seconds
or minutes, compared with updates every
hour or so in the case of manual tests. Besides in-line measurements, there are useful automated laboratory measurements
which reduce update times to a few minutes and provide a more responsive indication of process conditions.
It is also important for the control engineer or process manager to understand that
no two bleach plants are identical in design,

production constraints, or raw material inputs. Different process equipment is configured in different ways and is operated
under different conditions.
Process measurements and controls are tools which can
be selected and configured to meet the specific needs of each mill. Also, it is important for the engineer or technician to realize
that the dynamics of a bleaching process
are unique to that process.To achieve control with the least amount of variability, the
control loop tuning parameters, those factors which define a control loop's response
to a process change or upset, must be selected with those unique dynamics in mind.
2. In-line process and quality

measurements
As fiber moves through the bleach plant,
reactive chemicals are applied in proportion to the pu1p mass flow or production
rate. To monitor and regu1ate this chemical/ pu1p flow ratio, the flow of chemical
in aqueous solution or in gas phase is compared with and controlled with respect to
a measure of dry fiber flow, which is the
product of total flow and consistency. To
achieve the correct chemical/pulp flow ratio, the flow of reactive chemicals must be
measured. Besides measuring the total flow
of aqueous solution, sensors are used to
measure the concentration
of chlorine dioxide, monitor and control chemical addition, and provide feedback control of the
chlorine dioxide generator.
To achieve the right degree of delignification or bleaching without over-<:onsuming expensive chemicals and to avoid pu1p
viscosity loss, the initial chemical ratio
charge must be modu1ated based on the
indicated incoming demand for chemical,
the initial chemical reaction rate, and target pulp properties after the stage.
Consistent with the control philosophy
that earlier instead of later control is better
in the bleach plant, process and fiber quality measurement sensors are usually situated
before each bleaching stage. A list of important in-line bleach plant measurements
is compiled in Table 1. In-line kappa mea-

Tulel.
630
ImJH1t1tmIl,,-IIM~.
Measurement
Process Reaction Inference
Pulp brightness
Quality development
Reaction progress
Chemical residual
Kappa number
Temperature
50
Reaction progress
Chemical demand
0
CD
(..)
Input lignin content

Delignification across stage
x flow
dioxide concentration
surements record lignin content and infer

chemical demand. Shortly after chemical addition, pulp brightness and residual chemical sensors indicate the degree of chemical
reaction and, through predictive algorithms,
control the following stage pulp quality to
target levels. As a long-term feedback, the
same sensors may be engineered for aftertower measurements of the same variables.
Reeve and Weishar (1) have noted the
effects of consistency and temperature on
reaction rates in DC stages. For a 10 increase in temperature,
the reaction rate
doubles. As consistency increases, the reaction rate and reaction efficiency increases
and the kappa number after extraction decreases.When consistency and temperature
are increased to accelerate the reaction rate,
the process dynamics are changed significantly. For stable control-loop performance,
the altered process dynamics must be considered and control tuning parameters
changed appropriately.
In both acidic stages (DC, D) and alkaline stages (E, EOP), pH monitoring and control is important for process stabilization.
The reactivity of chlorine dioxide and chlorine dioxide/chlorine
mixtures is influenced by pH (1) because chlorine dioxide
bleaching solutions are composed of active
species whose reactivity is pH-dependent.
In the extraction stage, the correct pH is
essential for operation of the stage; therefore, pH is used to control the addition of
alkali.
Mass flow rate of fiber

Mass flow rate of chlorine
....--.........
'.
I
I"
CD 20
:;::
CD
a:
10
Equilibrium of reactive species

Alkali (NaOH) charge
Consistency
~40
"
,,'
c: 30
as
I
(..)
Reaction rate
pH
Chlorine
629
,,'
,
:'.....
:',
I
I
...,"'<
,'/
/
/
...~'
" --
"...
'...:- ,"
'-'
.........
~~~~
'
2ndD
1st D
,-.... ,
~~~~~
...............
'.
1st E
C stage
Brown
stock
0
dioxide
All in-line sensors are exposed to very

corrosive chemicals, wide temperature
variations, and mechanical vibrations. Sensors must be designed and manufactured
to ensure reliable, accurate, and stable operation.
400
600
800
Wavelength,
n,.2.
Re.fkcttmu
CfltWS of."bletlt:bM
1000
1200
nm
MUlJMrtUllly bl/lllebed""/l
pnlps.
2.1 Pulp brightness

In-line reflectance
measurements
are
used to follow changes in pulp brightness
in a bleaching stage, often after chemical
addition and a suitable reaction time or after the stage. Figure 2 shows the spectral
response of partially bleached kraft pulp
after one or more bleaching stages. Besides
causing
an increase
in the overall
reflectivity, bleaching shifts the color of the
pulp from reddish-brown to bluish-white.
Brightness sensors must have the capability of measuring the appropriate
wavelengths to provide the maximum sensitivity
in each bleaching stage.
In on-line brightness sensors, visible light,
directed along a fiber optic cable, shines
on the pulp as it flows past a transparent
sensor window. In one design, a broad-spectrum light source illuminates the pulp and
the reflectance is analyzed by monochromatic filters of defined color and bandwidth
(Fig. 3). In another design, light of a specific wavelength is generated by a lightemitting diode (LED) and the reflectance
characteristics of the illuminated pulp are
analyzed. Brightness sensors usually also
include a capability for simultaneously measuring process temperature.
Experience has indicated that,after chlorine dioxide addition in D stages, a solid residue may build up on the probe windows
when oxygen has been included in the previous extraction stage.To eliminate residue
buildup in such cases, the sensor may be
situated before the chlorine dioxide addition point and used to measure the incoming brightness level which in turn can be
used to control the chlorine dioxide flow.
Ultrasonic cleaning of the window also
solves this problem (4).
2.2 Residual chemical

Residual chemical sensors measure the
concentration
of a variety of different
chemicals by electrochemical means. Two
different designs are used:
1. The amperometric or polarographic sensor measures the current associated with
an electrochemical reaction with residual
oxidants or reductants. This type of sensor is suitable for many bleach plant applications because it can measure a wide
variety of chemicals, both oxidizing and
reducing, at low residual concentrations
and at the much higher levels found immediately after chemical addition.
2. The ORP (oxidation-reduction potential)

sensor measures a voltage gradient
caused by electrochemical potential between a platinum and a reference electrode.This type of sensor is suited for low
concentrations
of residual chemicals
found at the end of a bleaching stage.
A diagram of an in-line polarographic residual chemical sensor and the operating
princIple is shown in Fig. 4,A and B.Three
electrodes are in contact with the pulp. A
set potential (voltage) is applied to the measurement electrode with respect to the reference electrode. Electrochemical reaction
of the oxidizing or reducing chemicals occurs on the surface of the measurement
631
electrode. The rea(:tion causes a change in

the set potential. By controlling the current
between the measurement electrode and
the current electrode, the set potential is
maintained. The magnitude of the current
is proportional
to the concentration
of
chemical in the solution. As an integral part
of the measurement, the probe temperature
is monitored and used to correct the sensor reading.
Additional electrodes may be added to
measure several chemicals simultaneously.
In chlorine dioxide bleaching, this capability is important because chlorine dioxide
and an intermediate product, chlorite, may
co-exist in equilibrium. Chlorite concentra-
(c)
(a)
Light
Detector for
source reflected light
Electrical
connections
.',},
Fibre
optics
Electrodes
,. ,
.I
_'
~'_
'
"
..~;~,;,'--:VC:1~~;~_,~~~'~.1~2\\;""
'
'-:':p~if> s~~~,nsion':-"
Current flow
proportional
to chemical
concentration
Potential
set for species
to be measured
2;.\;~5<\',,~;:; }/<,.,~;';:,-->:-~p'uipsuspe_nsio~:/,
- \,'
",-
,',
- '. '.
',-,-
632
tion is often greater at a higher pH.The sum

of chlorine dioxide and chlorite indicates
the total oxidizing chemical available to
bleach the pulp.
In many cases, the measurement
electrodes may incur buildup of deposits. Electronic electrode cleaning is available to
ensure long-term measurement stability (4).
2.3 Kappa number
In the early stages of a bleaching sequence,fibers are delignified and the brightness increase is not significant.
Many
bleaching sequences now incorporate oxygen delignification stages which extend the
pulping process, significantly decreasing
the lignin content ofthe pulp entering the
first bleaching stage. In many cases, lignin
content (as represented by kappa number)
is halved. In these early stages, an in-line
kappa number analysis is useful for controlling the degree of delignification by adjusting the chemical charge to accommodate
changes in the lignin content of the incoming pulp.
Kappa analyzers automatically sample
pulp from the process.The sample is diluted
and transported by water pressure to a central unit which screens, washes, and dilutes
the sample to an accurately controlled consistency. To ensure that a precisely known
amount of fiber is measured, one commercial unit prepares two samples at different
Reference electrode
reading (4). Depending on the analyzer configuration, sample preparation and measuring sequences require from 2-8 minutes per
analysis.
Kappa number measurement is based on
lignin's characteristic absorption of ultraviolet (UV) light at specific wavelengths.
Figure 5 illustrates the operating principle
in which the absorption and scattering of
UV light is measured simultaneously. Another measurement corrects for any variation in the light source intensity.
Some kappa analyzers also measure relative fiber length. This is a useful measurement in mills whose fiber lines alternate
between hardwood and softwood grades.
This measurement is used to automatically
adjust the calibration of the sensor for hardwood or softwood fibers. Also, the chemical charge may be adjusted specifically for
each fiber type as it enters the delignification and bleaching process.The detection of fiber size transitions may aid bleach
plant operators in delivering the right fiber
to the correct storage towers, with a minimum of transition-quality pulp.
One analyzer also measures dissolved lignin in the pulp suspension as an indication
of carryover from the brown stock washers (3,5). This carryover lignin consumes
chemical which otherwise could delignify
or bleach the pulp. Because this carryover
Pulp suspension
Measurement
cell
Measurement
electrode
Current electrode
consistencies and calculates an average
Light
source
Kappa
number
Fig.4. (II) Detlllle4scbenurlk of IUIln-lIfU! ~I-.

IN'IlIdple, llrut (e) In-lme brlgbtfless -.
(b) tbe "lUIerlytng tUItJ1er'OmetrU:

ffU!lJSflremnat

consumes chemical within a few seconds
after mixing, brightness and residual chemical sensors also detect this effect. Dissolved
lignin measurement can be useful for monitoring and controlling washing efficiency.
633
A pH measurement must be temperaturecompensated for two reasons: First, the instrument is temperature-dependent.
This
effect is pre-determined
by the manufacturer and is programmed into the sensor's
electronics. Second, the process pH is temperature-dependent
as well. For instance,
preceding an E+O tower, a WOC increase
in process temperature causes a downward
shift in pH of about 0.2 unit. An uncompensated control algorithm would incorrectly add more alkali, wasting valuable
chemical. Controls therefore should have
the capability of temperature compensation
(6).
2.4 pH measurement
pH is an electrochemical
measurement
of acidity or alkalinity. There are many instances in a bleach plant where pH-related
disturbances can be created by inadequate
or unstable pulp washing or by poor regulation of dilution filtrates of differing pH
added to the pulp stream entering a bleaching stage. pH is a logarithmic measurement;
therefore, a pulp slurry at pH 3.0 has ten
times less acidity than one at pH 2.0. Because DC or D stages are operated at a
higher pH than are traditional chlorination
stages, the pH level is more susceptible to
instabilities caused by variations in dilution
water flow. In extraction stages, pH is a
function of alkali charge. Some mills may
operate
at a high pl:I to maximize
delignification but at the risk of wasting
chemical if the pH is not well regulated.
Figure 6 shows the measuring elements
of a pH probe. pH probes can be mounted
in the process stream or used to measure a
fiber-free solution sample supplied by an
automated sampling device. Newer installations favor a ball valve installation which
allows for periodic flushing or maintenance
of the sensor. This flushing sequence can
be automated.
2.5 Chlorine dioxide solution concentration

Chlorine dioxide concentration sensors
apply a combination of two principles in
measuring the concentration
of chlorine
dioxide and chlorine in solution. Figure 7
illustrates measuring the concentration of
chlorine dioxide by measuring the transmission of light though a bleaching liquor
sample flowing through a measurement
cell. The same sample flows through another cell where chlorine is measured electrochemically
with a multi-electrode
polarographic
system as described
in
Subsect. 2.2. This sensor can be installed
in the chlorine dioxide production plant
after the absorption tower or after the chlorine dioxide storage tank in the bleach
Light source
Optical
windows
634
plant. The concentration

of bleaching
chemical applied in each stage must be determined to ensure application of the correct chemical charge to the pulp mass flow.
2.6 Flow and consistency

Because oflong residence times and low
velocities, the fiber flow in a bleach plant
tends to exhibit plug flow characteristics.
This characteristic
becomes more pronounced as consistency increases. Mixing
is minimal in plug flow so short-term mass
flow variations tend to pass, without dampening, through the process. These shortterm variations in mass flow may show up
as short-term quality variations at the end
of the process.
Flow meters in the bleach plant are used
to monitor and control the flow of pulp
stock and bleaching chemicals. Most flow
meters are of the magnetic flow-tube type.
Gaseous chlorine flow is measured as a pre~
sure drop across an orifice plate.
Consistency meters are coupled with
flow meters to measure dry fiber mass flow
rate. Consistency is controlled by adjusting
dilution. Consistency can be inferred by
measuring shear force exerted by the flowing pulp on in-line blades or rotary wheels
or more recently by microwave transmi~
sion sensors. The latter technique has better repeatability,
requires only a single
calibration for all fiber lengths, and measures consistency in a normal range from
1% to 16% although it is possible to measure consistency up to 30%. In some cases,
pulp consistency can be inferred by measuring the pulp suspension density with
nuclear transmission sensors.
3. Delignification and bleaching

control
C102
solution
flow
3.1 Traditional C-stage control

Bleaching stages that use only chlorine
Transmitted
Fig. 7. Sebemttlk of" cblorltfe dioxUle COtfUtIlrtltkm $-'
light to detector
are now extremely rare. In many cases, however, the proven control strategies developed for the chlorination process can be
successfully implemented in modernized
stages, where chlorine dioxide has partially
replaced chlorine, by using different tun-
Potting Epoxy
AgJAgCI
Reference
Element
Dowel (4)
Wooden
Plug (3-4)
KCIS8turated
Autornlltlc
Temperature
Compensator
pH
Me8surament
Electrode
Epoxy
Berrlers
18rge
Wood or
Teflon
Junction
ing parameters which reflect different rates

of chemical reaction and quality development. It is useful to review the rationale
behind the development and implementation of process measurement and control
strategies for chlorination stages.
Since the early 1980s, many chlorine
stages have been controlled using dual sensors. In chlorination stages, brightness and
residual chemical sensors are installed in the
pulp line shortly after the injection of chlorine. Figure 8 shows the sensor locations
and control scheme, and Fig. 9 shows how
brightness and residual chemical measurements change as chlorination progresses.
The brightness development curve is a mirror image of the residual chemical curve.
Changes in chemical demand caused by
incoming kappa number variations and reaction rate variations resulting from temperature and flow changes influence the
brightness and residual sensors in opposite
635
Chemical
Pulp
.....
suspension
In-line
mixer
Fig. B. SeberIuItk of IJrlg""-s
sl..
111I4ralilul
Bleaching
tower
dlMlleIIl Sf!IIIIorSIllflSlJYlU.g tlul__
amtroll.
C or DC
"
Over-chlorination
II!
Q)
Target brightness
'C
II)
Under-chlorination
Iii
::>
"C
'0Q)
Target
residual a:
Time
Incoming
kappa number
Fig.'. Brlg""-s"rut ralilul d1M8IeIIl

~
ways. When
controlling
operators
brightness
- - - -Low
. ----- -- High
CfI1'fIfISP"c orDCs..
either sensor alone is used for

the exit conditions of the tower,
have to regularly change the
targets and the control cycles
between over-chlorination
and under.{:hlorination. By mathematically combining and
weighting the measurements
from each
sensor, the control operates to a single tar-
get termed "compensated brightness."

When properly tuned, the compensated
brightness target need not be adjusted even
for variations in incoming kappa number,
production
rate, and temperature.The dual
sensor system provides optimum control
over tower exit conditions, thereby minimizing chemical consumption.The achieve-
636
ment of uniform after-tower pulp quality is

affected by chemical demand which may
change with wood species and with anatomical differences (e.g., summer wood
compared with winter wood). To reduce
these long-term variations and augment the
predictive control provided by compensated brightness, after-tower measurements
of brightness and residual chemical are
sometimes recommended.
Pulp can be delignified only to a limited
extent in anyone stage. Excess chemical
addition results in waste and fiber degradation. An additional residual sensor at the
tower exit monitors
excess levels of
unreacted chemical and can be used to limit
this waste.
3.2 DC-and D-stage control

With partial substitution of chlorine by
chlorine dioxide, the bleaching process
dynamics are altered. For medium levels of
chlorine dioxide substitution (60-70%), a
DC stage may be effectively controlled in
much the same way as a C stage. Chlorine
dioxide reacts in a different way with lignin than does chlorine, hence there are
important differences in the rate for brightness development and chemical consumption. When substitution
level increases,
usually simultaneously
other process
changes, like higher consistencies and temperatures come along. Oxygen delignification before bleaching may halve the kappa
number. All these factors influence the rate
of chemical reaction and the dynamics of
the control 100p.1\ming parameters and
measurement weighting factors that are appropriate for C-stage control are not appropriate for the altered process dynamics.
Therefore, when converting to partial or
total chlorine substitution, a thorough review of process dynamics and control loop
tuning is warranted.
For 100% chlorine dioxide substitution
(Dloo), the process dynamics are very different. At the traditional dual sensor measurement location (i.e., after the chemical
mixer) chlorine dioxide produces a higher
brightness and less delignification than does
chlorine. Also, at this location, very little

change in brightness occurs as chemical
dosage is changed.The brightness measurement therefore tends to reflect change in
input brightness instead of chemical reaction progress. In dual sensor control, much
more weighting must be put on residual
chemical measurement. The D 100 stage is
therefore a good candidate for kappa number input measurement and advanced multivariable control strategies.
The pH of chlorine dioxide stages is
higher and more variable than the pH of Cstages, therefore pH control takes on added
importance for the Dloo stage. In some
cases, stabilizing the brown stock washers
and avoiding dissolved chemical carryover
provides a sufficiently stable pH. Some mills
have chosen to control pH by the addition
of acid before the chemical mixer. The pH
of the incoming stock and the filtrate water used for dilution may be significantly
different; to achieve the most stable control of both pH and consistency, loop interactions should be evaluated.
With addition of oxygen and peroxide to
the first extraction stage, more variables are
introduced to the delignification process.
The use of post-extraction kappa number
as an indicator of DE or (DC)E performance
is less trustworthy than it is in traditional
CE sequences. To reach final pulp brightness targets, some facilities have adopted
measurement of kappa number and brightness immediately after the D or (DC) stage.
3.3 Oxygen-stage
control
In the oxygen delignification stage, the

chemicals delignify, but do not bleach, the
pulp. The in-line kappa analyzer is the most
appropriate sensor for control of the degree
of delignification and the stabilization of the
lignin content of pulp exiting the oxygen
stage.
Figure 10 shows the kappa analyzer sampling points and a design for oxygen delignification control. Oxidized white liquor
and oxygen are added to pulp separately.
The prescribed reactant charge is adjusted
according to production
rate, incoming
kappa number, and reaction temperature.
Feedforward control predicts the post-delignification kappa number; the after-stage

kappa measurement provides a long-term
feedback. The after-stage kappa measurement
also provides feedforward measurement
oflignin content to the first bleaching stage.
3.4 Brightening D-stage control

Even if the DC stage is well-controlled,
the kappa number after the E stage may vary
because of the variable reactivity of the pulp
with extraction-stage additives such as oxygen and peroxide. Stable pH control in the
EOP stage is desirable but not always achievable.
The role of D stages is to remove some
of the relatively small amount of residual
lignin and, most importantly, to fully bleach
the pulp. Besides the measurement of itiitial brightness and residual chemical after a
suitable reaction time, pH measurement and

control are important for achieving the
maximum brightness development in each
stage and, in some cases, maximum pulp
cleanliness.
Figure 11 shows the configuration of a
typical D-stage control strategy with dual
sensor control before the bleaching tower
and sulfur dioxide treatment of residual
chlorine dioxide after the tower. Sintllar to
the delignification stage, variations in brightness measurement occurring shortly after
chemical mixing can be attributed to variations in the incoming pulp brightness.
The brightness development
curves do
not change significantly when different
amounts of chemicals are charged. To detect variations in incoming brightness, the
sensor, therefore, may be positioned before
the mixer.
Oxidized
white liquor
f (kappa. temp)
I
637
638
S02
water
C102
Solution
Pulp
f (alkali, pH)
If (stockflow,Cs)~
Fig.11.SdImuIIkof ..,._
blMd1l. amtrol,,, bright.l. DsltJge.

"
70
II)
:3
c:
60
..c:
C)
'C
.D
~
50
c:
Q)
en
40
Kappa
analyzer
10.2
10.4
10.6
10.8
11.2
11.0
pH
Fig. 10. ScbemtJtk
st"ge.
sbowI"g
luI/JJNI
"""'per
StJmpll"gpoi"ts
"rut amtrol
deslp
for tilt oxygM
dellpljictJlImI
Fig. 12. Relilu-shtp
belwJenl brigbblns
develOJImMI
"rut pH I"
peroxide
"
sltlge.
11.4
639
The residual chemical sensor is installed

after the chemical reaction has progressed
to a suitable extent and both chlorine dioxide and chlorite are likely to be present. It
is important at this point that both of these
reactive species are measured by the sensor and the sum of the two measurements
be used to indicate total active chemical.
To minimize brightness reversion and
equipment corrosion after tower bleaching,
the chlorine dioxide residual may be eliminated by reaction with sulfur dioxide water. The polarographic residual sensor can
measure both excess chlorine dioxide and
sulfur dioxide. The residual is sometimes
controlled to a slight excess of sulfur dioxide, ensuring complete reaction and a stable
pH.
cause the concentration

of perhydroxyl
anion is strongly affected by pH, measurement is extremely important for successfully
controlling peroxide bleaching (4). Figure
12 shows that brightness development after an 8-minute reaction is influenced by
pH; Fig. 13 shows that, after 2 hours, brightness development is at a maximum value at
a particular sodium hydroxide concentration. Brightness development and the pH
level at which it occurs are also influenced
by the concentration of added sodium silicate. Besides using a pH-compensated
re:
sidual chemical measurement, successful
peroxide bleaching control involves modeling the empirical relationships existing
between brightness development and peroxide equilibrium chemistry.
3.5 Peroxide-stage
control
Hydrogen peroxide is used to bleach
(chemi)mechanical
pulps. The dual-sensor
control used in chemical pulp bleaching has
been used in hydrogen peroxide bleaching
stages. Under alkaline bleaching conditions,
peroxide dissociates into water and the
perhydroxyl anion (HOO-).To measure reaction progress the residual chemical sensor must be designed to measure this ion
which is an active bleaching species. Be-
4. Optimizationof control loop

performance
The chemical reactions in a fiber line
depend on adding the correct amount of
reactive chemical to the fiber under the
most favorable reaction conditions. As fiber is transported through the bleaching
process, it is thickened and diluted several
times. Process waters of varying chemical
composition are recycled back to earlier
stages. Although the fiber line is a continu-
640
Pulp Bleaching
-Principles
and Practice
against time, shows this effect. The other
quadrants illustrate the power spectrum
analysis, the cumulative spectrum analysis,
and the auto-correlation analysis of the flow
measurement. These analyses indicate the
dominant frequencies of the variation, the
contribution of various frequencies to the
overall variation and the degree of data randomness. The mechanical problem illustrated here must be corrected to achieve
better control of chlorine dioxide flow and
pulp quality. Many problems with instrument location, process measurement, control strategy design, and control tuning can
be determined using PC-based diagnostic
tools (12).
For optimum control loop tuning which
leads to minimum process variability, the
process dynamics must be assessed using
open-loop bump tests. A bump test is conducted by making a small change in the
setpoint of the controlled variable and observing the corresponding
change of the
controlled variable to the new setpoint over
a period of time. Several bump tests, evaluated under different process conditions,
should be performed. By fitting one of sev-
ous process, production

rates must be
changed as smoothly as possible and intermediate storage vessels therefore must
smooth the transitions
by absorbing
changes in flow rate. There are manyopportunities for a bleaching process to become unstable. If not properly attenuated,
these disturbances can propagate through
the entire process, adversely affecting the
quality and uniformity of the final product.
Before any optimum control loop tuning
may be attempted, the variability sources
must be identified. Using time series analysis techniques, variability may be characterized and quantified. The observation and
mathematical analysis of real-time data may
reveal instrumentation and actuator performance problems (12). Figure 14 shows a
typical cycling pattern caused by valve
stiction. Stiction is a resistance to movement
caused by excessive friction in the valve
mechanism. In the example shown, a chlorine dioxide flow control valve cycles between two positions without the smooth
transition which is required for stable control. The upper left quadrant of Fig. 14,
where chlorine dioxide flow is plotted
Time Series
Sodium
silicate, on pulp
15
14
13
c
12
"cu
OJ 11
en 10
en
Q)
9
c
..c
8
C> 7
";;::
CD 6
Power Spectrum
48.14
2.601
46.73
1.9SO
~
45.33
CJ
43.92
1.300
0.6SO
0.000
42.52
o
256
512
768
1024
1024
769
Mean = 46.1088 2Sig = 4.103 (8%)

Auto Correlation
Cumulative Spectrum
0.5
75
::;:
Q. 0.0
CJ
Consistency:
;J.
Fig. 13. Effect ofsotllum
slilute
tUltIltIon on brllbtness
In tbe pet'fdde
bleacblng
50
25
-0.5
-to
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
% NaOH
0.0
10.0
20.0
30.0
40.0
SO.O
S
ofmecbanlul
pulp.
256
100
1.0
3%
Peroxide:
Time:
Temp:
513
S/cycle
PlI. 14. Ex..pk
of cblurl_
tIIoxUk j'lortJ cycling CIIuseti ~ v"lve stktlon.
769
513
S/cycle
258

era! possible control models to the observed
response, the loop time constant (lambda)
may be determined. Subject to the process
type, its observed dynamic response, the
actuator type, and the controller type, the
appropriate tuning parameters may be calculated. The desired end result is a robust
control which minimizes variability under
a variety of process conditions and production rates.
Figure 15 shows a brightness and residual
chemical control configuration
for a DC
stage and illustrates how open loop bump
tests may be used to evaluate process response and to diagnose problems with sensor location and control strategy (10). In
this example, the initial charge of chlorine
dioxide is applied at the first static mixer.at
6()<>A,
substitution. The remaining 10% chlorine dioxide and chlorine are applied 35
seconds later at the second static mixer.
A brightness sensor is situated 20 seconds
after the second mixer, and a residual chemi-
641
cal sensor is positioned to record I minute

later. A compensated brightness controller
adjusts all three chemical flows by means
of ratio stations which provide the correct
level of chlorine dioxide substitution. Open
loop bump tests comparing actual readings
to target levels are shown below the control schematic.
By visually evaluating the length of time
required for the brightness measurement to
stabilize, the bump tests show that steadystate compensated brightness is not reached
until about 2.5 minutes after the chlorine
flow or the second chlorine dioxide flow
targets (FC2,FC3) are changed. The first
problem is sensor location. Because of the
I-minute delay between sensors, the process dynamics are unnecessarily complex,
combining two flrst-order processes having
different delay times between the point of
chemical addition and the process measurement.The second problem is that the compensated brightness control adjusts the first
642
chlorine dioxide addition, adding another

35-second delay and further complicating
the response. For the illustrated process, the
closed loop time constant (lambda) is 2.25
minutes. The cut-off frequency is 14 minutes per cycle. Process variation below this
frequency cannot be reduced.
If allowed by the dynamics of the chemical reaction, the residual chemical sensor
should be relocated to the same position as
the brightness sensor, thereby equalizing
the time delay after mixing. Also, the first
chlorine addition should be regulated to a
ratio of production rate and not modulated
according to short-term brightness or residual chemical chemical. In this modified
design, the effective loop dynamics include
20 seconds of deadtime and a process time
constant of 10 seconds. A deadtime-compensated controller therefore may be tuned
to achieve a 30-second closed loop time
constant and a loop cut-off frequency at
about 3.5 minutes per cycle. This is 4.5
times better than that achieved with the
previous design.
5. Advanced control: fuzzy logic

Sample
Una
T
.C.
TOWER
Brown stock
3000 USGPM
25 K.NO
MIXER
Ie
130"F
OPEN
LOOP BUMP
FC1 SP
200---+1
350
TEST
5%
II.BRT=6%
--
FC2 SP
or
FC3 SP
II.CT=4%
II.BRT=6%
II.CT= 4%
30
60
90
120
150
180
TIME,s
Fig.15. IIlllSlrtJtUmoftbe flU of open-loop Inmtptnts to n,"""e
control.
tbe dyrumtks of ~H
brlgbtuss
Fiber production line processes are often complex and many interdependent variables influence the outcome. Responses are
usually non-linear and may depend on operating points such as production rate. Many
different "rules-of-thumb" and operating
experience are incorporated into the "art"
of producing high-quality pulp, and some
uncertainties are associated with how the
end result varies with different input conditions.
The decrease in kappa number accompanying chemical pulping and the development of brightness
and delignification
during bleaching are two notable examples
of processes which are good candidates for
fuzzy logic control. Fuzzy logic control incorporates "rules of thumb" and the longterm practical experience of operators and
process engineers
into the controller
design.
Fuzzy logic does not override basic dosage control but modifies it by introducing a
set of IF-THEN commands. "IF" represents

a process condition that must be met;
"THEN" represents the control action to be
taken. Fuzzy logic control has been applied
to DIDO-stage control. In this application.
the following variables are included:
- Incoming kappa number, in-line
measurement
- Brightness after chemical addition
Chemical residual after chemical addition
Temperature
- Production
rate (residence time)

- pH
- (EO) kappa number.
The configuration of a controller which
is comprised of separate fuzzy logic controllers is shown in Fig. 16. The fmal control is based on the average of the value pairs
for kappa control and process status and
for fuzzy brightness control and process
status. The controller compares the on-line
E+O kappa value to the setpoint and calculates the necessary corrections
for both
kappa and fuzzy brightness setpoints. Before process command signals are implemented, various alarms serve to protect
process safety and to limit control action if
there is excessive uncertainty.
Initial fuzzy logic control results from a
Finnish mill appear promising(ll).
E+O
kappa number and brightness variations
have been reduced substantially, and pulp
viscosity has been improved. Figure 17
compares the results of compensated kappa
factor control using fuzzy logic to compensated brightness control in a Dl00 stage.
The incoming kappa number variation is
about the same for both control evaluation
periods. D2 brightness and EO kappa number variations are much lower when fuzzy
logic control is used instead of compensated
brightness control.
6. Shive analysis
Dtptnding on 'hip 5ize uniformity and
pulping conditions, the bleach plant may
receive pulp containing a variable fraction
of "shives; which are visible, dark fiber
643
644
Fuzzy main control

Fuzzy
Fuzzy
feedback
Fuzzy
kappa brightness
control
Iprocesslstatus
Pulp
sample
(EO) kappa target
Rotating
screen
-, -
,~_,
\
-'
-.
Fibers
out
Unbleached
pulp
Residual
sensor
Brightness sensor
6
Softwood Mill Experience
5
4
:::e
0
'>
0
I-en
I!I
Incoming
kappa STDV
Suspension
Flow
EOK
STDV
~D2 brightness
STDV
2
Laser
Diode
Linear
camera
o
Compensated
brightness
Fig. 17. ComptIrlMm of ~
bletU:b/I"'"t.
3.2mm
Fuzzy
logic
brlgbtrNss ad /tizzy Iogk OOftlrols III tIN Dl00-mge
of. Inwft }nI1/I

bundles (see Chap. VI 5 and IV 2). Even in
pwpsofconsuntkappanwnbe~iliesruve
fraction may vary as a reswt of non-uniform
pwping.
Theoretically, sruves are any fiber bundle
larger man a single fiber. Their size characteristics and nwnbers may be defined by
screening a pwp sample under controlled
conditions. Sruve fractions retained by a
screen of defined slit size are weighed, and
ilieir relative nwnbers are expressed as a
percentage of ilie pulp sample. In one commercial shive analysis instrwnent ilie sequencing of sample dilution, screening,
washing, and collection is automated so that
a sample reading may be obtained within 5
minutes. Figure 18 illustrates one step in
ilie automated sequence of trus instrwnel1t
in wruch ilie screened sample is discharged
into ilie collection basket.
In anoilier laboratory instrwnent, shown
in Fig. 19, an automatically prepared pwp
slurry is classified by image analysis. The
slurry passes through a glass cell wruch is
illuminated by a laser beam. The outlines
of fibers and sruves are projected onto a linear camera wruch consists of an array of
many photo-sensitive detectors.The outputs
of iliese detectors are analyzed by microprocessors to construct a composite image
of ilie fibers and sruves. The processor
calcwates and displays ilie fiber and sruve
image characteristics, their lengili distribution, and the sruve fraction. An in-line version of this shive analysis sensor is also
available.
645
References
I. Reeve, D.W. and Weishar, K.M., TapptJ.74
(6):164 (1991).
2. Farrand,N.A.,"Bleach
Plant Sensors;
1990
TAPPI Bleach Plant Operations,
Short
Course Notes,TAPPl PRESS,Atlanta, p.205.
3. Hansson, A. and Kubelnieks
E., "The STFl
OPTIKappa - new tool fur On-Line Measurements
of Dissolved
Lignin:
STFI,
Stockholm,
1990.
4. VaimetAutomation
ture and personal
Inc., unpublished
communications.
5. ABB Inc., unpublished

sonal communications.
literature
6. TBI-Bailey Inc., unpublished

personal communications.
literaand per-
literature
and
7. Cowan, WE, Pulp Pap. 64(6):107(1990).

8. Sunds Defribrator
ture.
9. Young,)., Weldwood
communications.
10. The Entech
Inc., unpublished
litera-
Canada Inc., personal
Report, Vol. 1,(4),
1989.
11. Hood, K.T. and Willems, )., "Advances in

ECF Bleaching;
China Paper 95 Conference Proceedings,
Beijing, TAPPI PRESS,
1995.
12. Bialkowski,
WL.,"Bleach
Plant Process
Control; 1991 TAPPI Bleach Plant Operations Short Course Notes, TAPPI PRESS,
Atlanta, p. 189.
648
SECTIONVI:
CHAFfER VI:
Section 6: Water Reuse and Recycle
(Continued)
Chapter 6:
Water Reuse and Recycle
Jack Histed
Jack Histed Consulting Ltd.
L'Orignai Ontario, Canada
6. Countercurrent
6.1
Nell McCubbin
N. McCubbin Consultants Inc.
Foster, Quebec, Canada
Peter L Gleadow
systems.
6.2
Split-flow
6.3
Jump-stage
6.4
Process
6.5
1bree-washer
washing.
countercurrent
washing.
countercurrent
1. Introduction.
. . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
1.1 Historical review. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.2 Typical water usage for various washing sequences. . . . . . . . . . . . . . . . . . . . .
1.3 Effect of discharge volume on pollution load. . . . . . . . . . . . . . . . . . . . . . . . . .
1.4 Effect of discharge volume on effluent treatment facilities . . . . . . . . . . . . . . .
649
650
650
651
651
2. Reasons for restricting water use. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..

2.1 Water balance in a bleach plant
2.2 Economy in process heating. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3 Effluent treatment costs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4 Raw water supply limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.5 Limitations due to low flows in receiving streams . . . . . . . . . . . . . . . . . . . . .
.
.
.
.
651
652
653
653
654
654
3. Engineering approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
3.1 Need for rigorous mass balances
3.2 Tools available for calculating mass balances. . . . . . . . . . . . . . . . . . . . . . . . . .
3.3 Design of bleach plant towers
3.4 Control of washer showers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.5 Effect of washer discharge consistency on wash ratio
654
654
655
656
657
657
4. Princlplesofcountercurrentsystems
657
4.1 Wash ratio. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 657
4.2 Countercurrent flow component. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 657
5. Faaors affecting water reuse . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
5.1 Washer design and loadings. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.2 Seal tank design. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3 Most critical washers in the system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.4 Number of washers in the system
5.5 Effects of residual chemicals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . , . . . . . . . .
658
658
658
659
659
660
5.6 Temperature limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 660
(continued next page)
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 662
washing.
water use in a modem

bleach
660
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 660
plant
bleach
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 662
plant
662
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 666
7. Filtrate reuse
H.A. Simons Ltd.

Vancouver, BC, Canada
647
wasbing
Direct countercurrent
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
Chlorine/chlorine
dioxide
7.2
Extraction
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 666
7.3
Peroxide
or (EP) stages.
7.4
Chlorine
dioxide
7.5
Bleach screen
room and paper
7.6
Wire-cleaning
showers.
7.7
Seal tank connections.
stages.
delignification
stage
666
7.1
. 666
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 666
bleaching
stages.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 666
mill filtrates.
. . . . . . . . . . . . . . . . . . . . . . . . . . 666
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 668
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 668
8. Improvement of exJsting and future systems for water reuse . . . . . . . . . . . . .. 668

8.1 Opportunities to decrease water use in existing bleach plants . . . . . . . . . . . . 668
8.2 Improvement of future water reuse systems
. . . . . . . . . . . . . . . . . . 669
9. Water
9.1
9.2
9.3
9.4
reuse In non-chlorlne sequences ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..

Industry approach. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Extended delignification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Oxygen delignification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Ozone stage. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
670
670
670
670
671
10. Water reuse in closed cycle operation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 671

10.1 Toward closed cycle operation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 671
Chapter VI 6: Water Reuse and Recycle
Chapter VI 6:
Water Reuse
and Recycle
water usages ofless than 40 m3/adt of pulp.

Table 2 presents bleachery and total mill
effluent flows for Newer Mills"Oate 1980s
"
design), for state-of-the-art mills (1991 design), and for "Possible Future" configurations.
1. Introduction
Tule 2. MIll effl_tjltwJs
Water conservation has ecological merit

in its own right and can significantly decrease investment costs for water supply
and effluent treatment facilities. Consideration of the water supply source and the
aquatic impact of effluent discharges are
major considerations in the location or expansion of pulp production facilities. The
economies of many of the proposed technologies for increasing kraft mill chemical
closure are contingent on decreased water
usage.
Water use and effluent discharge from the
pulp and paper industry have been decreasing steadily over the last 50 years. Table 1
shows the trend toward decreased water
consumption in the United States from 1959
to 1988 based on information compiled by
NCASI (1). The results have been averaged
from reported consumption figures and include all types of pulp and paper producing facilities. For bleached kraft pulp mills,
the mean water use in 1988 was 103 m3/
adt of pulp compared with the 1977 level
of 132 m3/adt (1).
TIIbk 1. Aven8ge IoliJllHIer
JItIJMrlrubatry.
:Ygr
1959
1969
1975
1979
1985
1988
IISe I. tbe palp .rut
m3/adt of pulJ)
240
156
III
96
79
72
Bleaching typically contributes 50-70% of

the total mill effluent flow.
Newer bleached kraft pulp mills use ap-
proximately
649
75 m' of water/adt
of f)ulf), of
which about 20 m3/adt may bypass the effluent treatment system as clean water. The
most recent mill designs call for anticipated
Newer
Mi
Bleach plant
-Acid sewer
-Alkaline sewer
Total mill
~
21.1
10.0
72.0
(m'/1IlltojpalP) (2).
Current
D.Qign
Possible
~
10.5
10.6
35.5
10.5
0.1
14.8
Water is used in bleaching

1. To convey, heat, or cool pulp stock
2. As a medium in which delignification or
bleaching reactions occur
3. To enable separation, through washing, of
bleaching reaction products and reactants
from pulp
4. To dissolve organic and inorganic tnaterials, acids, catalysts, alkalis, and protectors.
Washing separates dissolved materials
from pulp through displacement or dilution
and thickening.The requirement and importance of washing is determined by the effect of dissolved materials on later bleaching
stages (chemical consumption, bleaching effectiveness, scaling, and equipment corrosion). These effects vary with bleaching
stage (ozone, peroxide, chlorination, extraction, chlorine dioxide), and its position in
the bleaching sequence (e.g., first, second,
or third chlorine dioxide stage), intensity
of bleaching (degree of previous delignification and chemical charges applied), and
process configuration.
Process configuration considerations in
washing can include the filtrate recycle arrangement (effect of filtrate carryover and
carryback)
and the positive effects of
reaction products in later stages. These
positive effects include, for example, phenomena associated with simplified bleaching in which reaction products provide a
f)rotective effect in a later stage (3), and in
the Ultim-o process (4), in which AOX can
be destroyed in an ensuing high- temperature (95C) (EO) stage.
650
Pulp Bleaching
-Principles
and Practice
1.1 Historical review

Pulp bleaching to high brightness was
first carried out in sulfite mills. Because
sulfite pulp was normally pulped to a low
kappa number, there was not a large amount
of impurities to be removed during the
bleaching process. Fresh water was used
for all washer showers, for controlling the
level in the seal tanks, for wire-cleaning
showers, and sometimes for tower and vat
dilution. Overflows from seal tanks were
sewered directly.
Because the large amount of fresh water
make-up added at each bleach stage created
a dilution wash, thorough washing was
achieved on small washers with a combination of this dilution washing and displacement washing. This type of washing was
transferred to the early kraft mill bleach
plants where the washers were typically
much smaller than the brown stock washers and had much smaller seal tanks.
As the size of pulp mills increased without a corresponding increase in the size of
the fresh water source or the receiving
stream, it became necessary to improve the
efficiency of bleach plant washing. The introduction of high-temperature
chlorine
dioxide stages to replace low-temperature
hypochlorite stages made it necessary to
conserve energy by minimizing the dilution
washing and improving displacement washing.The energy crisis in the mid-1970s was
a strong incentive for implementation
of
countercurrent
washing (5).
The conversion to countercurrent washing revealed many equipment limitations in
older bleach plants. Those plants with very
small seal tanks found that the washer vats
overflowed when fresh dilution water was
removed from the seal tanks.There was insufficient time for removal of the large volume of air in the filtrates entering the seal
tanks and air was no longer being flushed
to sewer by fresh water make-up. Corrosion
of 317 stainless steel washers became a serious problem and new alloys had to be in.
troduced to resist the acidity and high
chloride levels in some of the filtrate
streams.
1.2 Typical water
usage for various
washing sequences
The effluent discharge from a modern,
filter-type bleach plant in the 1990s is about
25-40 rn-'/t of pulp. The decrease has been
achieved primarily by water recirculation
together with some form of countercurrent
washing.
There are many approaches to the countercurrent use of water in today's bleach
plants, but most can be described by one,
or a combination of, the following terms:
1. ~,
where water is used once only and
all water applied to each stage is discharged
to sewer except for the relatively small volume carried forward with the pulp
2. Internal circulation, which makes use of
filtrate for tower and vat dilution and perhaps for wire cleaning and doctor showers
3. Jump-sta~e countercurrent
in which filtrate from later stages is used as wash water in two or more previous stages in the
bleach plant
4. Split-flow countercurrent, where filtrate is
used for some showers in previous stages
5. Direct countercurrent,in which the whole
shower water flow for each washer is
taken from the filtrate of the succeeding
washer.
These water usage schemes are discussed
in detail below. Typical water usage and
hence effluent discharge for the foregoing
processes applied to a typical (DC)(EO)DED
bleach plant is as follows:
Effluent Dischartle
(rn3/adt of pulp)
Theoretical
M:1Yi!
Filtrate System
Open
450
450
Internal circulation
within stages
Jump-stage
countercurrent
Split-flow
countercurrent
Split-flow-jump-stage
countercurrent
Direct countercurrent
55
55
23-25
30-40
23-25
30-40
11-15
13-15
12-25
15-25
Bleach plants using diffusion washers on

the tops of the towers can often achieve
lower effluent
flows, and a modern
D(EO)DD bleach plant may use only 15-20
m3 of water/adt of pulp.
1.3 Effect of discharge volume on pollution load

There is a common misconception that
decreasing the volume of pulp mill effluent automatically protects the environment.
In general, the environmental benefits of
decreased effluent flow are minor. There
are many reports of bleach plant modernization projects where effluent flow was decreased substantially and the discharges of
BOD, color, dioxin, or other pollutants were
also decreased. However, these pollutant
loading reductions were the result of process changes which were instituted simultaneously with the decrease in discharged
water.
Pollutants in bleaching effluent are primarily present as dissolved material. This is
true whether they are measured by generic
parameters such as BOD, COD, or AOX, or
as specific compounds
such as tricWorophenol. The volume of water discharged
has no effect on the quantities of soluble
material discharged from the bleach plant
although it can have an impact on the effluent discharged from the effluent treatment system. The only exception
is
suspended solids which are a minor environmental issue in a bleachery.
1.4 Effect of discharge volume on

effluent treatment facilities
The volume of effluent discharged can
have a significant effect on some aspects of
design and performance
of the effluent
treatment plant but little or no effect on
others_ V1rtUally all mills use an aerated stabilization basin (ASB) or some variation of
the activated sludge treatment
process
(AST). These two processes respond differently to flow variations.The following comments assume that the plant is not grossly
overloaded and that decreases in effluent
flows are within the ranges likely to be encountered in practice.
Decreased effluent flow from the bleach
plant increases the hydraulic retention time
of an ASB. However, it has no significant
effect on the concentration and characteristics of the treated effluent because the key
effluent parameter influencing the performance oftheASB is the BOD 10ad.The most
651
efficientASBs operate with long-term average discharge concentrations

of about 50
mg/L suspended solids (fSS) and 20 mg/L
BOD. In practice, it is difficult to achieve
lower concentrations with this type of treatment, and these concentrations
remain
more or less constant as effluent flow is decreased. In these cases, lowering effluent
flow has a positive effect on effluent quality (6), the effect being roughly proportional to the degree of flow reduction.
For an AST system, the increase in hydraulic retention time in the aeration vessels is unlikely to have any effect on BOD
removal. In the AST process, it is essential
that the biosolids formed during aeration
settle effectively in the secondary clarifiers.
If the clarifier performance is marginal, a
decrease in effluent flow can lead to a
marked improvement
in removal of suspended solids, BOD, and all other biodegradable substances in the effluent. It is
well-known that dioxins and furans accompany the suspended solids in the effluent
stream so that improved recovery of suspended solids leads to the transfer these
substances from the effluent to the recovered sludge.
The most efficient ASTs operate with
long-term average discharge concentrations
of about 20 mg/L TSS and 20 mg/L BOD.
The situation is analogous to the highly efficient ASBs discussed above so that, in
these cases, lowering effluent flow has a
positive effect on the mass of pollutants discharged.
If a mill has, or is considering, the use of
a physicochemical
treatment to decrease
effluent color or to comply with exceptionally stringent regulatory requirements,
a
decreased effluent flow can lead to a substantial decrease in costs.
652
Pulp Bleaching
and Practice
Avoidance of capital costs for increasing

capacity of water supply system
Decreased operating costs for raw water
treatment
Part of a long-term plan to eliminate effluent discharges entirely.
are normally many "non-process. streams

such as cooling water, seal water, and washdown hose water. These non-process
streams normally leave by way of the process sewers and so contribute to the bleaching effluent volume. In some mills, these
streams are segregated and recovered for
reuse or they bypass the treatment system.
Most bleach plant flowsheets omit non-process water, at least in the principal flow diagrams. An essential part of any successful
water conservation campaign is a detailed
flowsheet showing all points of entry to the
process, including the non-process stream.
Process water streams and non-process
water streams may include those shown in
Fig. 1, together with the routes by which
water exits the bleach plant.
In the past, many of the above-mentioned
water inputs would have been insignificant
relative to the total water flow into and out
2.1 Water balance in a bleach plant

It may seem unnecessary to state that all
water entering a bleach plant must leave,
but this apparently obvious fact is often forgotten. It is not a simple task to identify all
points of entry when calculating the water
balance around a bleach plant and is even
more difficult to determine the flows. It is
common to find that many of the points
where water enters the process are omitted from design flowsheets, particularly in
older mills.
Water that enters the stock or IDtrate
streams and dilutes the pulp is generally
termed "process. water. In addition, there
INTAKES
Water In pulp
Ctean-up
Pulpwashing._
Cooling water to hydraulic drives
Wlre-cleanlng showars
Watar with chamicaJs
Dilution!of (Me) pumps
CondonsaI8 from dInIcI~
Injection
Laa"-Ihrough
nonnaJIyclosed _
_
Hydraulic and steam
on washafs
Hose water to lower washer vat conslstancy
Water Inlata!of wash-up or start-up IeIIopen
Diluttonwater to faciNtata_1pmonI ~
ExcaaaIva maka-up to .eal tanks to avoid ..,,-
Cooling watar for jackets
hoses
SaaI-water on shafts of pumps and agitators

Cooling to hydraulic units on diffusion washers
Hooas !of tamponuy
Outft0W8
. WIth bleached
pulp
. For reu88 etsewhere.
such as the woodroom
Acid saaI tank overflows (Iha .acId sewer")
. Alkaline 8881 tank overflows

. Ov.-from
washers,
(the -alkaline sewer")
leaks, and seal water all
leave by Iha floor drsins'

.(norm8Itt floordraIn8
Fig.1.
W.m''''''"
on bearings
Seals on some types of washer drums
BLEACH
PLANT
2. Reasons for restricting

water use
The incentives for decreasing water use in
mills include:
Hcatconservation
Lower effluent flow
Conservation of a limited resource (t.e.,
water)
-Principles
sepat8Ie fromthe 8boW two MWerS)
DfII.fI-,..6lMcb pltllll.
cooling of faulty bearings
-- - ------
of the bleach plant. However, because the

major water inputs are being progressively
decreased by new designs and through the
updating of older plants, these sources have
become increasingly significant.
2.2 Economy in process heating
Most of the process water entering a
bleach plant effectively dilutes the pulp,
increasing the mass of water that has to be
heated to maintain the pulp at a temperature appropriate to each bleaching stage.
Although some of the heat may be "free" in
that it is recovered from evaporator surface
condensers or other equipment requiring
cooling, the last heat added is almost always
in the form of live steam so that any decrease in steam demand is reflected in lower
fuel consumption in a boiler.
Figure 2 shows the steam consumption
for a mill bleaching 750 odt of kraft pulp
per day under typical conditions when a series of water conservation
measures is
implemented. The data were generated by
a GEMS computer model, but the other process simulation software mentioned below,
or any rigorous calculation method, affords
the same results. The model allows virtually any variable to be manipulated and the
effect of steam consumption or other operating conditions that depend on mass and
energy balances to be determined. In this
case, the wash ratio (ratio of wash water

mass applied to the water mass carried forward from the washer with the pulp discharge) was lowered to practical minimum
values; wire showers were converted to
high-pressurelIow-volume
operation and,
for the lowest flows, the second extraction
washer was eliminated.
The maximum
steam consumption
shown (1063 kg/t of pulp) corresponds to
a cost of about (Can.)$4.25/t of pulp at a
typical mid-l990s steam cost of (Can.)$4/
1000 kg.The minimum steam consumption
for the case studied saves approximately
(Can.) $2.6O/t of pulp. This is modest but
not insignificant relative to bleaching chemical costs which are typically about (Can.)
$40-50/t of pulp.
2.3 Effluent treatment costs

Effluent treatment costs increase with
increasing effluent volume.
Approximate costs for water and effluent treatment facilities can be calculated
using equations [1] and [2]. Incremental
costs associated with a change in the capacity of the system can be estimated using equations [3] and [4] which describe
the slope of the resulting cost-flow rate
curves (7,8). Equations [1-4] are valid for
December 1991 Canadian dollars.
1,100
1,050
c..
1,000
:;
c.. 950
:c
900
800
850
.::.:.
E
m
en
750
700
650
600
15
Fig. z. Effeet of eJJlrmu ml",,",
20
25
30
35
Effluent, m3/t unbl. pulp
011stell", COfISIImptimI.
653
40
45
654
Pulp Bleaching
Water treatment
-Principles
and Practice
cost (Can$)
[1]
0.63
= 200,OOOCflowrate, Us)
Effluent treatment
500,000
(flow
cost (Can$)
rate,
Us)
[2]
0.63
Change in supply cost (Can$/Us)

126,OOOCflow rate, US).o37
[3]
Change in treatment cost (Can$/Us)

US).o.37
= 315,OOOCflow rate,
[4]
The incremental cost equation is useful

for evaluating any capital cost savings attributable to decreased water consumption.
For example, a 10 Us reduction in the required capacity of both the water supply
and effluent treatment systems having a
design capacity of 1000 Us would save approximately (Can.) $342,000. This saving
could result, for example, by specifying an
indirect contact condenser compared with
a direct contact condenser in the chlorine
dioxide plant and by providing piping to
recover the cooling water [at a capital cost
of typically less than (Can.) $100,000].
In equation [1], water treatment includes
clarification, lime softening and ffitration,
and mill and river water pumps. Effluent
treatment (eq.[2]) includes primary and
secondary clarification, activated sludge
secondary treatment, and all sludge-handling equipment. Formulae are indicative
only and are accurate to about :t 30% for
flows between 100 Us and 2400 Us. Care
should be taken when applying these cost
equations because a number of site and sitespecific design factors must be included.
However, if the mill already exists and the
flow is decreased, there would be no capital saving. However, most of the operating
saving could be realized, decreasing total
mill costs by about (Can.)$I/t of pulp.
If this same mill were expanding production, it would probably be more economical to decrease the effluent flow,including
that from the bleach plant, than to expand
the water supply and the hydraulic capacity of the effluent treatment system. It is
often possible to double production in an
older mill without increasing effluent flow.
Site-specific engineering studies, including
detailed mass and energy balances, are nec-
essary to determine the optimum combination of water conservation measures and

increased capacity of water treatment systems.
2.4 Raw water supply limitations

The available water supply may be constrained by the capacity of the raw water
treatment system, regulatory constraints on
withdrawal, or by physical limitations on
wells or small rivers. These constraints can
be seasonal, requiring storage dams to be
built. Wherever capital expenditure, new
permits, or production curtailment is a possibility, it is always worthwhile to determine
the technical and economical advantages of
taking steps to decrease water usage. Opportunities for water conservation exist in
most bleach plants.
The most economically attractive situations occur when expansion of mill capacity is sought and the cost of improving the
raw water system can be avoided. A condition under which an environmental
approval permit is often issued is that the total
water use and effluent flow remain unchanged.
2.5 Limitations due to low flows in receiving streams

A number of mills, mostly in the United
States, discharge their effluent to watercourses that have seasonal low flows, forcing the mill to store effluent for up to six
months and discharge only when the receiving stream is high. Mills in South Africa and
Thailand use effluent for irrigation in response to low receiving water flows or competing downstream agricultural uses.These
mill are innovators in adopting minimum
water usage and optimum bleaching technology (9-12).
3. Engineering approach
3.1 Need for rigorous mass balances
Whether for designing a new bleach plant
or optimizing an operating system, a rigorous mass balance is an essential tool if the
best results are to be achieved. In the past,
it was common to rely simply on various
open-loop design calculations using numer-
--~--

ous simplifications to minimize the time
required for calculation. However, as mill
processes become increasingly complex
and include more closed loops, serious design errors are likely to result if all aspects
of the mass and energy balance are not
quantified. Many designers in the past ignored flows as large as the wire cleaning
showers when calculating balances, but this
is inappropriate today.
3.2 Tools available for calculating mass

balances
Hand calculations and spreadsheets
Water systems are often very complex,
and they typically entail a great amount of
recycling, particularly in new mills or in
miIIs that have been modernized. Because
of the sheer number of streams involved,
hand calculations are of limited use. To calculate a mass and energy balance, iterative
solutions are required. With one or two
loops, hand calculations are workable but,
with multiple intersecting and nested loops,
a computer solver is necessary.
Spreadsheet programs are relatively inexpensive, easy to use, and readily available
in most mills. Because most mill engineers
are familiar with the use of spreadsheets,
the user can begin immediately without
having to spend additional time learning a
new program.
However, even though
spreadsheets are easy to use, large programs
can be difficult to follow when checking
the logic. Troubleshooting can also be diffi.
cult, as can making changes in the program.
The spreadsheet does not make any calcu.
lations automatically and the user has to
correctly enter all calculations from first
principles. Calculation errors can be introduced into the program and go undetected.
For highly complex systems, spreadsheets
may have difficulty coping with the iterations necessary to achieve a balance and do
not offer any information regarding model
convergence unless programmed to do so.
If only a small area in the mill is involved,
if Ii simf)lified water balance unquestionably
meets the needs, or if only a few scenarios
need to be to examined, a spreadsheet program may prove sufficient.
655
Beyond the use of spreadsheets for single

or smaller systems, their use for developing water balance models is not recommended. However, as tools to assist with
documentation and store data, they can be
invaluable.
Steady-state simulation
Ideally, a steady-state computer simulation package should be used to model a
detailed water system. These simulation
packages all have some sort of predefined
components such as mixers, splitters, separators, and heat exchangers and automatically do the necessary calculations. A model
is created using the simulator's keyword library. Sufficient data must be specified to
satisfy the degrees-of-freedom of all the units
or blocks in the model. The simulator package then performs all of the material and
energy calculations, often referencing builtin physical property tables. Verification of
the model is easier than for spreadsheets
because there is no need to verify heat and
mass conservation.When a few conventions
regarding style are developed and followed,
the models are virtually self-documenting
and can easily be passed from user to user.
Consultants find these tools to be particularly valuable because models developed on
previous projects can be rapidly modified
for other miIIs.
Two basic solving techniques are used
by steady-state simulators: Some simulators
use the sequential method which is similar
to the way hand calculations and spreadsheets perform. This method is easy to follow and debug; however, large programs,
such as water balances, can be difficult to
solve. Simultaneous solvers manage larger
problems with greater ease; however, they
can be more difficult to debug. With simultaneous solvers, input or output constraints
can be set as appropriate when specifying
equations to define the model.
There are many steady-state simulator
packages available including MASSBAL,
GEMS, FIowCalc,MAPPS, and ASPEN. Some
of these packages have been tailored especially for the pulp and paper industry; others are oriented to the oil and gas, food and
beverage, and chemical industries. Any of
656
the above can be used to produce heat and

mass balances for water systems.These programs can be used to calculate rigorous
steady-state bleach plant balances in pipeby-pipe detail and display the results in tabular form in a conventional
CAD-drawn
fIowsheet or a simulator package fIowsheet
(with CADSIM).
Dynamic simulation
Ideally, a plant-wide steady-state material
and energy balance model should be developed as the concluding step in the first
phase of a water reduction program. Reduction opportunities
can then be examined using this model. Once it has been
determined that an opportunity exists for
decreasing water consumption to a satisfactory level, it may be appropriate to develop a dynamic model of a given system.
Here, the need for simulation depends on
solving some sort of time-sensitive problem
not addressed by the simpler steady-state
model. For example, if a new warm water
system is required, then a dynamic model
can assist in sizing the tanks and providing
the control strategy.
Before embarking on a dynamic simulation of the mill water system, the engineer
should have a clear understanding of the
specific dynamic problem that must be
solved. Dynamic simulation requires much
more data input than steady-state simulation, and it is often particuIarly difficult to
obtain time-related data in a mill environment. If a solution for a specific dynamic
problem is required or If a general balance
is all that is required, then steady-state simulation is a simpler and more effective tool.
Most dynamic simulation software packages use a sequential solving method (e.g.,
Dynamic GEMS, DESIGNER, PAPDYN,
DYSCO and IDEAS) and these should have
sufficient accuracy for water system design
and control. MASSBAL3 is a dynamic simulation package that can perform regular
MASSBAL2 steady-state simulations.
Simulation software Is developing rapidly
with respect to both ease of use and technical capability. Current process simulation
is discussed extensively by Syberg andWtld
(13) who cover all software current at the
time of their writing. More recent developments include Simon's IDEAS andWinGEMS
(the Window's version of PCGEMS) (14).
3.3 Design of bleach plant towers

There are three types of bleach plant towers in use tOday: upflow, downflow, and
upflow-downflow. Upfiow-downfIow towers have a significant retention time designed into the upflow portion to permit
consumption of oxygen in an (EO) stage or
of a large portion of the applied chlorine
dioxide in a D stage.
Bleach plants using upflow towers exclusively have positive displacement throughout (i.e., the tonnage rate at all washers is
the same), a desirable property in a countercurrent washing system.The selection of
washer-type (vacuum, pressure, wash press,
or atmospheric diffuser) affects the ease of
start-up in such a bleach plant. This is important because start-ups of the whole plant
must occur when one stage is shut down.
To avoid having to start up the entire
bleach plant when one stage is shut down,
many plants have been designed with
downflow or a combination of downfIow
and upflow-downfIow
towers in the E and
D stages.With such a design, if all the equipment is in good condition, this type of
bleach plant can be operated for long periods under plug-flow conditions. However,
under upset conditions, when some washers may be operating at different production rates or not operating
at all, it is
impossible to run a tight countercurrent
washing system using conventional control
and conventionally sized filtrate seal tanks.
For plug flow to occur, constant tower
levels must be maintained and the dilution
zone discharge must be of constant consistency. Poor agitation in the dilution zone
or poor control of the filtrate flow for tower
dilution can cause cyclical changes of tonnage rate at the washer and interfere with
washing efficiency in a tight water reuse
system.
During upset conditions
in a countercurrent system, washers operating at higher
than feed-to-the-bleach
tonnage rates re-

quire fresh water makeup; washers operating at lower rates spill ffitrates from their
seal tanks.
3.4 Control of washer showers

A 1995 survey (15) of 30 bleach plants
revealed that 24 plants had fixed shower
flow rates and flow rate changes were made
on an individual basis. Only four of the
bleach plants varied shower flow with production rate; one plant varied the flow rate
to achieve a target displacement ratio and
another varied shower flow rate as a function of ffitrate tank level and evaporator
load.
Of the 30 bleach plants, 10 did not monitor washer performance.The most common
method of evaluating washer performance
was to monitor the chemical demand in tiie
following stage. Another method in common use was measurement of washer discharge consistency.
3.5 Effect of washer discharge consistency on wash ratio

For efficient washing, it is desirable to
malntain the maximum discharge consistency while maintaining a good wash ratio.
For example, if the discharge consistency
decreases at a constant shower flow, more
of the wash water remains in the sheet
thereby decreasing the wash ratio and the
washing efficiency.
4. Principles of countercurrent
systems
4.1 Wash ratio
Laboratory work has shown that it is
important to maintain wash ratios above
1.15:1 at the chlorination and extraction
washers to prevent excessive chemical consumption in the stage following directly
thereafter.
Examples are presented
in
Table 3.
However, varying the wash ratio at the
H, D}, and E2 washers from 1.3:1 to 0.5:1
had only minor effects on the chemical consumption in the following stage. It is evident that, with respect
to chemical
consumption, the critical washers are those
for the chlorination
and first extraction
657
stages. The final washer in the bleach plant

prevents bleaching chemicals from being
carried to the dryer or paper machine
where they can cause corrosion.
TIIbk3. lfIfm ofllJlUbrYIIio_~
_",p-
tfmI mlbe
H SIiIgeS of II (CD)EHDED
E,"""
bIut:bI18g SNJIInIU (16-18)".
Washer
Chlorination
Wash
Ratio
1.25:1
3.0",1,NaOH on
pulp in E, stage
1.15:1
3.3
1.00:1
4.7
II
..
"
"
1.30: 1
" " " "

1.45 %<:~on
pulp in H stage
1.15: 1
1.60
1.00:1
. Direct countercurrent
Chemical
Consumed
"
2.40 '
washing system used.
A wash ratio of 1.3:1 or higher is preferred at the E, stage washer. Low ratios
(e.g.,0.5:1) can be tolerated at the H,D"
and E2washers if water is added to the seal
tanks to ensure a countercurrent
flow and
provide sufficient wash water at the firstand second-stage
washers. Without this
countercurrent flow through the seal tanks,
the spent chemicals and reaction products
build up to very high levels until a steady
state is reached where impurities are removed from the system with the fully
bleached pulp.
4.2 Countercurrent flow component

For dissolved solids to work their way
forward in a countercurrent
washing system, there must be a countercurrent
flow
component. That is, the wash ratio should
be greater than 1.0:1. Using the E.-stage
washer as an example and D. ffitrate as the
shower water, at a 1.0: 1 wash ratio the D.
ffitrate theoretically will displace all of the
E}solids from the sheet into the E, seal tank.
All of the D} ffitrate, applied as shower water,is returned to the D, stage with the sheet
and the D, dissolved solids build up to a
very high level in the D, stage.
However, if the wash ratio is 1.3:1, the
additional wash water (0.3 of the 1.3) works
658
Pulp Bleaching
-Principles
and Practice
its way forward in the system. This is analogous to a person moving forward by taking
13 steps forward and 10 steps backward.
The lower the countercurrent
component,
the longer it takes the wash water to move
forward in the system and the higher the
build-up of dissolved solids within a stage.
In the theoretical example, when the
wash ratio is less than 1.0:1 some ofthe E}
stage dissolved solids are transported from
the E} washer into the D I stage and consume additional chlorine dioxide.
The second way ffitrates can work forward in the washing system is through the
overflows of seal tanks. For example, when
the D I seal tank overflows
into the (DC) seal
tank, any extra water added with chemicals

and any seal water
entering
the D 1 stage and
not used there for tower or vat dilution or

for shower water on the E} washer overflows into the (DC) seal tank.This provides
a very important purge of dissolved solids
from the system, especially if the wash ratio is low.
In the 1995 survey (15) of 30 bleach
plants, 21 had interconnected
seal tanks
with acidic-stage seal tank ffitrate overflowing from D2 to D. to the chlorination stage
and thence to the acid sewer. The E2 seal
tanks overflow to E}and then are discharged
to the alkaline sewer.
5. Factors affecting water reuse

5.1 Washer design and loadings
When the water reuse chapter of The
BleacbingofPulp
(19) was written in 1979,
bleach plant washers were mostly of the
vacuum drum ffiter-type. However, some
bleacheries
were equipped with atmospheric diffusion washers installed on the
tops of bleach towers.Today there is a wider
selection of washer types available. These
include various makes of pressure washers,
some of which have the capability for multistage washing. There are also washing
presses available (20) that can raise consistency above 30% for gas-phase bleaching
stages.
Typical design loading factors (i.e., the
tonnes of pulp/m2 of washer surface area
required to achieve good washing) for various washer-types are shown in Table 4 for
comparison purposes. Values significantly
above these numbers may result in poor
washing efficiency.
Ttlble 4. TypktII
WtISbrr 10000118gftlelors (2).
Washer1YPe
Loadin~ Factor
Vacuum drum (old)
< 7.5 adt/d/m2
Vacuum drum (new)
< 9.7 adt/d/m2
Wash press
< 27 adt/d/m'
21-27 adt/d/m'
Compaction-baffle
ffiter
More detailed information

found in Chap. VI 3.
on washers
is
5.2 Seal tank design

The seal tank performs several functions.
It is a reservoir for filtrates required for
tower and vat dilution and for filtrates
pumped to the showers of previous wash
stages. But its most important function is
to remove air from the ffitrate. Some seal
tanks are designed to remove air by centrifugal force so that the air migrates to the
vortex. Another type uses a large rectangular tile tank in which the incoming ffitrate
flows over a weir to the top of a stilling
chamber. This chamber must be large
enough so that the bubble rise is faster than
the downward movement caused by the ffitrate pumps located at the bottom of the
chamber.
Wash water must flow around bubbles
in the sheet similar to the way it flows
around fibers. The smaller the bubble size
for a given amount of air, the greater the
total surface area and the greater the resistance to flow. In an extreme case, the air
volume may be equal to the volume and
surface area of fiber in the sheet and the
washer operates as though it were at twice
its design load.
Many mills have experienced problems
with countercurrent washing because of air
in the sheet resulting from design deficiencies in the seal tanks. Centrifugal seal tanks
must be small enough in diameter to develop adequate centrifugal force and must
have means to prevent the vortex from entering the ftltrate pumps.The area-to-height

ratio of stilling tanks must be adequate to
provide for bubble rise. A manufacturer's
guarantees for washer performance are liable to be of limited value unless the supplier also endorses the seal tank design
because the latter can have a major effect
on washer performance.
5.3 Most critical washers in the system
Delignification stages require efficient
washing because most of the lignin is removed from the pulp at these points. For
example, in a (CD)(EO)D sequence, inefficient chlorination washing carries acid into
the extraction stage and increases the alkali
consumption.
Inefficient extraction stage
washing carries colored matter into the
first chlorine dioxide stage which can increase the bleaching chemical requirement
to reach a specified brightness. For example, Fig. 3 shows that, at 82 brightness,
well-washed kraft softwood
pulp (100%
efficiency) consumed 0.3% chlorine dioxide on pulp compared with 0.7% consumed
at 83% washing efficiency (21). A well-functioning single-stage washer has a washing
efficiency of about 85%. (See also Chap. IV
9, subsection 9.)
5.4 Number of washers in the system

The minimum number of washers in a
countercurrent washing system is three.
659
This is also the optimum number for keeping the flows in balance. Washing is essential after the chlorination, extraction, and
final bleaching stages. Provided the kappa
number of the extraction-stage pulp is less
than 4.0 and the extraction-stage washer is
operating at 85% efficiency, there is no need
to wash after intermediate H,D" or Ez stages
(3,17,22,23),
When the kappa number after the El
stage is high or the Et washer is inefficient,
a wash after the third stage in the sequence
saves chemical in the final stage but is not
essential for pulp quality (21,23).
In five- or six-stage conventional bleach
plants, the prime use of the H,
Dl' or Ez
washers has been to convey the pulp to the
next bleaching stage (24).There is no need
for these washers when the stages are carried out in tubes instead
of towers
(16,17,23).
Elimination of a washer has the following benefits:
a) Decreased electrical and maintenance costs
b) Decreased water uSage due to seal leakage
and wire cleaning showers
c) Simplified seal tank connections
d) Simplified countercurrent washing system
e) Higher strength bleached pulp if there is
no wash preceding the ftnal chlorine dioxide stage (3)
85
0
80
~75
~0
iii
UJ
70
CD 65
t:
.s:::.
C)
(CD)(EO) bleached,
2.7 kappa number
softwood kraft pulp
60
-;::
II)
55
50
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
CI02 consumed in D stage, % on pulp
Fig. 3.IUJed of lIJiU"'ng e.ffldnu:y 011tbe D-s"'p
blelldJlrtg of. jHIr1"'"y tkllplfted
softrr004 mft
pulp.
660
5.5 Effects of residual chemicals

Good pH control is an essential component of every bleach stage. The acidic or
alkaline filtrates used in a countercurrent
washing system can have adverse effects on
the ability to control pH. For example, if
alkali (NaOH) is normally used to control
the pH of pulp entering a D, stage, it is essential that the pulp discharged from the E,
washer never be so alkaline that sodium
hydroxide
cannot be used for control. If
this occurs, off-brightness pulp results because most of the chlorine dioxide applied
is converted to chlorite in a pH range where
chlorite reacts very slowly if at alI.This leads
to a low brightness and high chemical residual at the end of the stage.
Another problem occurs if residual peroxide in a peroxide-reinforced
Ez stage is
carried into a D stage and reacts with chlorine dioxide to form chlorite, causing the
chlorine dioxide to lose one-fifth of its oxidation capacity. Similarly, if sulfur dioxide
is used as an antichlor to destroy residual
chlorine dioxide in a Dz stage, the amount
should be controlled so that no residual is
carried onto a washer feeding into a D stage
where it can destroy part of the chlorine
dioxide.
5.6 Temperature
limitations
It is difficult to alternate hot and cold
stages in a countercurrent washing system.
Preferably, all of the stages are operated at
nearly the same temperature except for the
chlorination
stage. Temperatures
above
50C in the chlorination stage,(CD),(DC),
or D (where D denotes 100% CIO z substitution), can lead to inefficient delignification
(21)At low kappa factor levels in (CD) chlorination, high temperature can lead to nonuniform
delignification
because
of
inadequate mixing. This problem occurs
in bleach plants using in-line static mixers
where mixing takes from 5 to 10 seconds.
At high kappa factor levels, viscosity loss
can occur when chlorine bubbles enter the
tower where they dissolve producing an
over concentration in contact with some
of the pulp in the absence of a corresponding over concentration of chlorine dioxide.
6. Countercurrent washing
systems
Surveys (25,26) of NorthAmerican kraft
mill bleach plants in 1971 and 1976 showed
that there were three basic types of countercurrent washing systems operating in
conventional
bleach plants: direct, splitflow, and jump-stage countercurrent
as described below. The 1990s have produced
countercurrent
washing systems that combine features from the direct and split-flow
systems. The flowsheets for these systems
show the wash water flows to the showers
as well as the flows of excess water through
the seal tanks to the acid and alkaline sewers. Chlorination filtrate is also shown as
being added to the stock between the
decker and chlorination washer for highdensity dilution, consistency regulation,and
as injection water for cases where chlorine
gas is still in use. The flowsheets omit the
recirculation for tower and vat dilution. No
attempt has been made to distinguish between cold, warm, or hot fresh water and
machine white water used for the showers.
6.1 Direct countercurrent washing

The principle of the direct countercurrent washing system, shown in Fig.4, is to
use fresh water or white water for the Dz
washer showers. The filtrate entering the
seal tanks consists of spent bleaching liquor
and the part of the wash water representing the countercurrent
flow component.
This filtrate is used as shower water for the
Ez washer.
Because all but the small countercurrent
component of flow leaves the Ez washer
with the sheet, most of the D z filtrate is returned to the Dz stage. Similarly, Ez filtrates
are used on the D, washer and Dl filtrates,
on the (EO) washer. Only part of the (EO)
filtrate can be used on the top showers of
the (DC) washer because, if (EO) filtrate is
drawn into the (DC) seal tank, severe foaming prevents sheet formation on the washer
drum (25). Fresh water is therefore used
for the bottom showers of the (DC) washer.
In c1osed-cyc1e operation, the fresh water
can be replaced by excess D, seal tank filtrate using fresh water makeup as required
661
662
to maintain the desired wash ratio. The seal

tank connections
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should
be D 1 to D. to (DC)
and E2 to E,. This arrangement

avoids
flowback of E. illtrate into the D. seal tank
which can occur with direct countercurrent
seal tank interconnections
(27) .The foamcausing tendency of E. illtrate, when it is
carried into the chlorination-stage seal tank,
is not a problem in an OD(EOP)D sequence
(28).
The main advantage of the direct countercurrent system, compared with the splitflow or jump-stage systems, is that it uses
less fresh shower water as described in Section 1.2 above. However, it also has disadvantages:
a) The (EO)-stage illtrate, used for the top
showers of the (DC) washer, reenters the
(EO) stage and causes a build-up of highly
colored matter which leads to an increase
in the amount of bleach-consuming chromophores entering the D. stage. Color (t.e.,
chromophore) build-up can also increase
peroxide consumption in an (EOp) stage.
b) Calcium and other ions are precipitated on
the pulp in the (DC) washer when the pulp
is made alkaline by addition of (EO) illtrate
(29).
c) Precipitated metals are carried with the
(EOP)-stage pulp into the D. stage where
they dissolve and are reprecipitated in the
E2or (Ep) stage (30).
6.2 Split-flow countercurrent washing
The split-flow system is the most complicated of the three. As shown in Fig. 5,
this system uses fresh water or paper machine white water on what is the equivalent of two washers.The principle is to use
wash water of similar pH to that of the stage
which the pulp is exiting on the bottom
showers and wash water similar in pH to
that used in the stage the pulp is entering
on the top showers. To maintain a given
wash ratio, this system requires a more sophisticated system to control shower water volumes.
With split-flow operation, pulp entering
the D2 stage is always acidic so that alkali
(NaOH) is used for pH control. However,
depending on the wash ratio and the relative alkalinity and acidity of the bottom and
top showers of the (EO)-stage washer, the

pulp can be acidic or alkaline and pose a
pH control problem in the D. stage if it is
not always the same. This can lead to offbrightness pulp when the pulp entering the
D, stage becomes too alkaline. The pH-adjusting chemical must always be the same:
acid or alkali.
6.3
Jump-stage countercurrent
washing
A flowsheet for the jump-stage system is
shown in Fig. 6. As with split-flow, the
amount of fresh or white water used is the
equivalent of that of all the showers on two
washers. In its favor, jump-stage washing is
a much less complex system to operate than
the systems described above. However, it
consumes more acid or alkali for pH control because acid D2 illtrate is carried with
the pulp into the E2 stage and acid D, illtrate is carried into the (EO) stage. Similarly,
alkaline E2-stage illtrate is carried into the
D, stage where acid must be used for pH
control. Failure to do this leads to a high
pH in the D, stage and high residual chlorite levels in the D, illtrate being applied to
the (DC) washer. In the (DC) washer, the
chlorite can be converted to chlorine dioxide in an acid environment, causing severe
corrosion when the materials and construction of the washer and auxiliary equipment
are not suitable for such service. The high
pH also leads to low brightness and high
bleaching chemical cost.
6.4
Process water use in a modern

bleach plant
Figure 7 shows the wash water flows for
a modern, medium-consistency,
fourwasher bleach plant using fresh or paper
machine white water equivalent to that
used for two washers.This flow-sheet combines some of the features of the direct and
split-flow systems.
White water is used on the lower showers of the final washer so that a significant
portion of it is carried countercurrent
to
sewer; hot water is used on the top showers and leaves the washer in the pulp mat.
The final D-stage filtrate is applied directly
countercurrent
on the (DIN) washer
Cold, warm or hot water, or machine
(DC)
(EO)
Cold, warm or hot water, or machine
(EO)
Fig.6.FIOflIsbeet for
JIImp-stage
cOIIntert:llmmt
white water
WtISbIng.
white water
Chapter
CD
iii
:=
'5
:x:
(I)
VI 6: Water Reuse and Recycle
665
...
(I)
c:
:2 iii
u :=
IG
E $
.S;
D.....
,52
-..:
::::::
ci
....
'"
0
r-:
.....
ci
0
0
r-:
u'i
C\!
....
....
0
u'i
.....
ci
....
....
t\I
ci
C?
....
(')
0
r-:
~CL
0
"'"
ci
(I)...
.5 (I)
""
~~:I
..i
~en
m
<Ci
It)
(where
N represents
-Principles
and Practice
a neutralization
stage).
6.5 Three-washer bleach plant

In countercurrent
washing, the threewasher bleach plant is the easiest to operate when attempting to maintain a flow
balance. Currently there are more than 30
three-stage bleach plants in operation in the
United States and one five-stage, threewasher bleach plant.
~Figure 8 shows a countercurrent
washing system for a three-washer bleach plant.
Pulp machine white water is added at the
bottom shower of the third washer so that
most of it works its way countercurrent
to
sewer. Hot water is added at the top shower
and is carried from the washer in the sheet.
Acidic filtrate from the third washer is used
on all first-washer showers. Thus, calcium
and other metals dissolved in the first stage
are more likely to be washed from the sheet
~thereby avoiding metal-induced peroxide
"'"
c::i
~C?
Pulp Bleaching
~Pulpentering the final D stage is acidic or

~neutral and requires sodium hydroxide addition for pH control. The alkaline (DIN)
filtrate is used in a split-flow fashion on the
~bottom showers of the (EOP) washer and
on the top showers of the D washer. That
is, the bottom shower water is similar in
pH to the pulp leaving the (EOP) stage, and
the pH of the top shower water applied to
the D washer is similar to that in the stage
the pulp is entering.
:2
:;a. 3:
666
0
r-:
IX!
....
....
0
u'i
decomposition
in the (EOP)
7. Filtrate reuse
~7.1 Chlorine/chlorine
i!
-cCD
'0 :=
(I)
en
0
r-:
:::
...
~IX!
~0
'" 0IG
U Z
stage.
delignification stage
dioxide-consuming
colored
7.3 Peroxide or (EP) stages

If there is residual peroxide in filtrate leaving an (EP) stage, care should be taken to
prevent this chemical from being carried
countercurrentiy to a chlorine dioxide stage
where it can react with chlorine dioxide to
produce chlorite and decrease the oxidizing capacity of the former by one-fifth. (EP)stage filtrate can be safely used on the top
showers of the chlorination-stage washer

and on the bottom showers of the (EO)stage washer.
Chlorine
dioxide
The D i and D,-stage
bleaching
filtrates
sta~es
contain
very
little dissolved colored material and can be
In low-consistency
chlorination
systems,
filtrate is usually recycled for dilution at the
reused in their
ways as shown
bottom of the high-density storage tower

~forconsistency regulation and, if gaseous
chlorine is used, for chlorine injection.This
~recycle increases the temperature and de-
should be taken to avoid contact of low-pH

filtrates containing residual chlorine dioxide with 3 I 7 or lower grades of stainless
steel.
creases the pH in the chlorination stage.
7.2 Extractionstages
Ie;;
chlorine
material is carried with the pulp into the

D, stage.
(EO)-stage filtrate recycle should be one
of the last steps undertaken for decreasing
the volume of effluent discharged from the
bleach plant and should be implemented
only if the (EO)-stage washer has a low
carryover of dissolved colored material in
the sheet being discharged. Even then, softwood pulps have a significantly increased
chemical demand in the DI stage (31,32).
This is less of a problem with hardwood
pulps because much less delignification
occurs in the EI stage.
The E,-stage filtrate contains very little
dissolved colored material and consumes
minimal amounts of chlorine dioxide.Therefore, this filtrate can be reused in its entirety.
In TCF bleaching, (EOP) filtrate is used
for brown stock washing.
7.4
dioxide
]
t:
r(
more
entirety in several different

in Figs. 4-8. However, care
showers on the (DC) washer increases the
7.5 Bleach screen room and paper mill

filtrates
Screen room and paper mill filtrate,
termed "white water," is used for dilution
concentration of dissolved colored matter

in the (EO) filtrate. Therefore, for a given
washing efficiency at the (EO)-stage washer,
of pulp at the bottom of the bleached pulp

storage tower. Provided that it does not
contain clay, dyes, or other impurities, this
Recycle of (EO)-stage filtrate to the top
...
~:=
0
:I:
667
Q)
Co
.~
'3
~c..
0
cD
0
,...:
"'"
~:::::
oq;:
....
....
0
-i
(\I
c::i
Q)...
Q)
.5:
7.7 Seal tank connections
~c::i
~II
ari
.!I
,...:
co
,...:
(\I
~l
I"--
M
....
).."
...
~Q)
~t
J
'0
en
ari
It
II:!
~0
,...:
cD
....
E-
r
i
:II
~]
N
and Practice
Fresh water, at about the operating temperature of the washer, is usually used for
wire-cleaning showers. To conserve water,
many mills use the wire-cleaning showers
on an intermittent basis. The need for wire
cleaning is decreased if an air doctor is used.
There is an increasing use of bleaching illtrates for wire-cleaning showers.
]!~
en
-Principles
7.6 Wire-cleaning showers
~":
c::i
....
Pulp Bleaching
illtrate can also be used as shower water

for bleach plant washers. Where all of the
showers for the equivalent of two washers
are fresh water or white water (split-flow
and jump-stage), it is preferable to use fresh
water on the last washer and white water
on the preceding washers. This results in
the white water being purged to sewer and
decreases corrosion of the paper machine.
However, in mills producing alkaline paper,
calcium carbonate in the white water may
cause scaling in alkaline bleaching stages.
Particularly serious scaling results if calcium
comes into contact with oxalate which may
be formed in ozone or oxygen stages.
~~c:
:c
as
668
:I:
0
as
U z
j...
Examples of washer seal tank connections were cited above in Subsect. 6. Overflows from downstream bleaching stages
contain much cleaner water than do the seal
tanks to which they are connected. It is
desirable to use the cleanest water for vat
and tower dilution.To do this, the overflow
should be connected to the suction side of
a filtrate pump instead of flowing directly
into the seal tank.
8. Improvement of existing and

future systems for water
reuse
A 1995 survey (15) of 30 bleach plants
showed that more than half were operating over design capacity. Of these, four were
from 31 % to 51% over capacity and four
were more than 51 % over capacity.
..
~Oi;;
8.1 Opportunities to decrease water

use in existing bleach plants
The principle way to decrease process
water use in the bleach plant is to decrease
fresh water dilution and inilltration while

preserving washing efficiency through better displacement. Ideally, there should be
positive wash ratios with no seal tank overflows and no fresh water introduction except for that required for washing showers
on the final two stages. If positive wash
ratios cannot be maintained through the
washer showers, then a seal tank overflow
is required to maintain the countercurrent
filtrate flow. Seal tank overflow should follow filtrate use: D2 overflow to D, to (DC)
to acid sewer and E2 to (EO) to alkaline
sewer.
In searching for filtrate recycle opportunities, the principle "like goes with like"
applies. For example, when pulp is going
to an (EO) stage, (EO) filtrate can be used
for dilution. Similarly, for the other stages,
if the washer showers allow two different
illtrates to be used for washing, the top or
back shower can use illtrate from the following stage as it leaves with the pulp.
Conventional wisdom is to avoid penetration through the sheet of illtrate from the
following stage. Breakthrough
does not
occur as long as the back shower flow remains below 0.7 wash ratio. That is, at 12%
discharge consistency and a total shower
water flow of 10.3 m3 (1.4 wash ratio), the
back shower water could be about 4-5 m3
without any significant breakthrough. This
is the jump-stage split-flow countercurrent
washing arrangement used in many new
mills. If some breakthrough can be tolerated, a more aggressive approach toward
full countercurrent
recycle can be taken.
Full countercurrent
recycle is not generally recommended as it may increase chemical consumption and provide traps for acidand alkali-insoluble materials in the (DC)
and (EO) stages (t.e., pitch and calcium, respectively).
For all washing stages, improving the discharge consistency off the washer improves
pulp washing. Discharge consistency decreases for older and overloaded washers.
The most common operating problems on
vacuum drum washers are low operating
vacuum, improper application
of wash

water, high washer speed, low discharge
consistency,
inadequately
or unevenly
washed pulp, and pulp that is difficult to
discharge from the washer. Perrault (33) has
provided a systematic method for investigating washer problems.
Several methods for improving washing
and decreasing water consumption in existing older bleach plants are listed below
inTable 5.
There are significant opponunities
to
develop effective bleach washing control
strategies and devices. It should be noted
that ffitrate recycle can be complicated by
material of construction
considerations.
Filtrates may need to be neutralized
or
treated with an antichlor such as sulfur dioxide. For example, it is not advisable to
use (DC) ffitrate for HD tower dilution unless the HD tower dilution zone is built of
acid-resistant material. This requires that
both the grout and tiles be acid resistant
for use in a tile-lined tower.
rllble 5. M_lo
Im/Jnnie_In.,
8.2 Improvement
of future water re-
use systems
Plug flow bleach plants designed for on-line
process control
The advantages of bleach plants designed
for plug flow include having the same tonnage rate throughout the bleach plant and
a lower overall water consumption. However, to date they have suffered from designs which fail to take into consideration
the requirements for sensor location that
provide state-of-the"an feedback process
control. If there is a feed forward component to the process control system, an accurate measure of tonnage rate is essential.
Elimination of unneeded washers
Washing is not essential after H, D or E,
l'
stages as has been demonstrated in over 14
bleach plants using the (CD)(EOXHID)
sequence and two using the (DCXEOXD/
E;/D:Z>sequence (3,23,34). The bracketed
H, D., and E, stages may be carried out in
tIIUltIecretIM_ter ~
Action
Benefit
a) Install new washer drums with anti-rewet
decking
Increased
consistency
Improved
wash water distribution
c) Change end valves and adjust seal clearances
Improved
vacuum
d) Use filtrates, intermittent

wire cleaning
Decreased
effluent
e) Use illtrates for washer repulper or MC standpipe

dilution if washer discharge consistency is too high
to pump
Decreased
hot water and effluent
Decreased
water consumption
Improved
washing efficiency
b) Install improved
Replace
type of wash shower
hot or fresh
flow, or air doctor for
shower
water
with
white
water
g) Replace constant
ratio control
flow showers
with wash
h) Install level control on washer seal tanks
Fewer spills to sewer
i) Improve brown stock washing
Decreased
j) Convert first bleach stage to medium
Large decrease
consistency
chemical
consumption
in effluent volume
k) Reuse filtrate from an open wash ahead of the

bleach plant in the brownstock area
Decreased
effluent to sewer
I) Recover filtrate spiUs for HD tower dilution

or screening
Decreased
effluent volume
m) Use new wire/fabric
Improved
types for washer drum
n) Balance shower flows

0) Operate
at higher-than-design
vat consistencies
669
drainage
Improve washing
and extraction
Higher discharge
consistency
670
Pulp Bleaching
-Principles
and Practice
shon-retention
bleach tubes (3,23). Another sequence that is becoming widely
used is (Dt/N)D, where sodium hydroxide
is added to the dilution
zone of the D I tower.
With fewer washers, it is easier to keep

washer countercurrent flows in balance and
less water is required for wire-cleaning
showers and for maintaining seal tank levels.
Use of two-stage washers or two washing
stages
Multi-stage pressure washers are in use
for brownstock that could also be used in
the bleach plant to decrease chetnical consumption and water usage as well as to decrease bleach plant chetnical carryover to
the pulp machine (22). Figure 3 shows the
high cWorine dioxide consumption due to
carryover of colored material from a singlestage washer operating at 83% washing efficiency. Using two washing
stages,
efficiency is increased to 97%.TWs increase
leads to a significant saving of cWorine dioxide (21,22,35).At least one new bleach
plant has installed two washing stages after
an (EOP) stage (36) and several older, sixstage, bleach plants have modified the hypocWorite-stage washer to accommodate a
second wash after the (EO) stage.
A spare, single-stage washer can be insened in the process stream between the
(DC) washer and the (EO) tower and used
as a Papricycle
washer
(37). In the
Papricycle process, spent (EO)-stage ffitrate
is mixed with pulp leaving the (DC) washer.
A rapid reaction occurs which solubilizes
about two-thirds the amount of lignin removed in a conventional E stage (21).This
lignin is washed out on the Papricycle
washer. Therefore, there is less lignin in the
pulp entering the (EO) stage and less color
is generated in this stage (21).This reduction should also lead to lower use of peroxide in a peroxide-reinforced (EOP) stage. An
added benefit is a saving of about one-third
of the sodium hydroxide needed for the
(EO) stage.
Hot water supply
Decreases in water usage and changes in
countercurrent
washing have dramatically
decreased the need for direct steam in the

bleach plant. The hot water supplied to
showers should be produced by recovery
of secondary heat and not by the use of
fresh steam.
Many mills have a warm water system
operating at approximately 40C and a hot
water system at 50C.When bleaching stage
temperatures are 70C or higher, secondary heat should be used to heat the hot
water to these temperatures so that it can
replace primary steam heat.
9. Water reuse in non-chlorine

sequences
9.1 Industry approach
Chlorine
became
the pre-eminent
delignification chetnical because it attacks
both the phenolic and phenolic ether units
in the lignin structure; oxygen, cWorine
dioxide, and peroxide attack only the phenolic nuclei. Ozone (12) and dimethyldioxirane (38) are among the few newer
bleaching chetnicals that can also attack the
etherified phenolic units, but these chetnicals are more expensive and difficult to use
than cWorine.
Because of environmental considerations
and cost, the industry approach is to maximize delignification before bleaching chemicals are applied using approaches such as
extended delignification (39).
9.2 Extended delignification

Modifications of the pulping process (40)
make it possible to delignify kraft pulp to
kappa number 20 or lower instead of the
usual 30. This increases the amount of lignin dissolved in the digester and decreases
the delignification taking place in the bleach
plant. If extended pulping is used in combination with additions such as polysulfide
(PS) and anthraquinone
(AQ), the brown
stock kappa number can be further decreased from 20 to 12 (39).
9.3 Oxygen delignification

The oxygen stage is capable of effecting
a 40-60% delignification
of unbleached
pulp (41,42).There should be at least two
Chapter Vl6: Water Reuse and Recycle

washing stages after the oxygen stage. The
first-stage filtrate is used as shower water
for the last brown stock washer. The countercurrent component is carried forward
with the kraft black liquor to the recovery
system; most of the oxygen filtrate is carried with the pulp back to the oxygen stage.
In a survey (15) of30 bleach plants, 10
had an oxygen delignification stage. Eight
of these had fully countercurrent
recycle
back to the brownstock
washers. One
bleach plant planned to implement recycle,
and one sewered post-oxygen filtrate because of evaporator and recovery boiler
limitations. One of the 10 had only a single
drum for post-oxygen washing, six had two
washers, and three had three washers.
The survey also revealed that a variety !3f
washer combinations
and washer types
were used for post-oxygen washing. These
included wash presses, drum washers, atmospheric diffusers, pressure diffusers, and
compaction baffle filters.
9.4 Ozone stage

If an ozone stage is used, the filtrate from
both the ozone stage and the following extraction stage can be recycled to the recovery boiler as practiced in one mill (12) .This
results in very low water consumption and
effluent discharge.
When a mill continues delignification/
bleaching beyond the ozone stage by use
of hydrogen peroxide before chlorine dioxide, it is possible in principle to recover the
peroxide filtrate by using it to wash pulp
countercurrently
to the recovery boiler.
However, in this scenario the filtrate volume exceeds the volume required for
brown stock washing.
Not all mills that have installed ozone or
hydrogen peroxide delignification/bleaching stages currently recover the effluents
although all have announced their intention
to do so. Most of the dozen ozone bleaching systems presently in operation have less
than two year's experience so that new information about the feasibility and the
limitations involved in the recyclIng of such
bleach plant effluent can be expected to
become available.
671
10. Water reuse in closed cycle
operation
10.1 Toward closed cycle operation
There is public demand to eliminate effluents and the U.S. Environmental ProtectionAgency is required by law to eliminate
effluent in any industry where it is technically and economically feasible. Although
the issue of closed-cycle
operation
of
bleached kraft mills is complex, there is little
doubt but that the bleached kraft mills of
the future will approach closed-<:ycle operation and that any action that decreases
effluent flow will assist in attaining this
objective. Whenever new equipment
is
purchased, the quantity of water required
to operate the system in which it is installed
should be carefully considered.
The dissolving-grade
sulfite mills at
Domsjo in Sweden and Lenzing in Austria
reportedly recycle all bleach plant effluent
to chemical recovery boilers, eliminating
discharges to sewer (43).
In the late 1970s, the first attempt at
closed-<:ycle operation of a (DC)EDED sequence bleached kraft mill was made at
Thunder Bay, Ontario, using the RapsonReeve process (27,44,45). Problems were
encountered with corrosion in the salt removal process equipment and in the superheaters in the recovery boiler.
Other problems contributed to high chlorine and chlorine dioxide consumption in
the bleach plant and to high chloride load
in the salt-removal process. These included
poor brown stock washing and consumption of chlorination chemicals by recycled
chlorination filtrate (27). Poor air removal
in the E, seal tank led to air in the E, washer
vat.This contributed to poor E,'stage washing and increased chlorine dioxide consumption
in the Dt-stage. The D,-stage
chlorine dioxide consumption was also adversely affected by the use of in-lIne mixers
in that stage (46).These were later shown
to be inefficient and were replaced by a
high-shear mixer (47).
At present another attempt at closedcycle operation is undergoing mill-scale
tests (28).This mill is using an OD(EOP)D
sequence to bleach southern pine pulp.
672
Pulp Bleaching
-Principles
and Practice
There have been intensive investigations

of the technical feasibility of designing and
operating a bleached kraft mill without discharging any effluent. This implies that all
bleach plant wash water and other waste
streams be used to wash pulp and then recycled to the recovery boilers. Three major mill design consultants have reported
(48-50) that they consider zero effluent to
be technically feasible and that the cost of
constructing and operating a greenfield zero
effluent mill is similar to the cost for constructing a mill using recent conventional
technology.
All three consultants concluded that the
best approach to zero effluent was to eliminate the use of chlorine compounds in the
bleach plant and to recycle all bleaching
effluents to the recovery cycle. However,
because the effluent volume from the tightest bleachery water reuse system exceeds
the volume required for brownstock washing, it may be necessary to evaporate and
burn some of the bleachery effluent separately. The volume of excess bleaching filtrate can be significantly decreased by the
use of wash presses in the bleach plant (20).
The mill design of a fourth consultant
(51) shows small bleeds to sewer to purge
the system. For existing mills, it was shown
in one study (49) that it would be economically beneficial to eliminate gaseous chlorine and hypochlorite to minimize chlorine
input and to evaporate and incinerate the
bleach plant wastes separately.
References
1. Miner,R. and Unwin,}., "Progress in reducing water use in waste water loads in the
U.S. paper industry;
National Council of
the Paper Industry for Air and Stream Improvement,
New York, Technical Bulletin
No.603, 1991.
2. Carter, D.N. and Gleadow, PL., Water Use
RedUdton
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Montreal
1994,
5. Hisey, R.W., Amer.

(1969).
(Dee
Pap.
Ind.
51(9):43
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}., Bergmen, E., Owen, D., "Best Available
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Design and Economics for Cbemical Engineers, 3rd edn., McGraw-Hill, New York,
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McGraw-Hili,
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to
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(1976).
and Andre, G., Tappi
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78(3)TR23
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G.G.,Jr., Tbe
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3. Histed, J.A., U.S. Pat. NoA,238,281
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1992TAPPI Environmental Conference
Proceedings,TAPPl
PRESS,Atlanta,
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Pulping Conference
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TAPPI

21. Histed, }.A.,
Avenor, Inc.
private
file
courtesy
of
22. Histed, }.A. and Vega Canovas, R., "Decreasing the Usage of Chlorine and Caustic in Bleaching,"
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Conference
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TAPPI PRESS,
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38. Lee, C.L., Hunt, K., Murray, RW,

76(11):137
(1993).
39. McDonough,
(1995).
T.}.,
Tappt
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Tappt j
J 78(3):55
23. Vega Canovas, R. and Histed, }.A., Pulp

Pap. Can. 93(4):T94
(1992).
40. Elliot, R.G. and Walley, C.A., "AOX and Dioxin Emissions Reduction
at Longview
Fiber Company,"
International
Pulp
Proceedings,
SPCI,
Stockholm, p. 253.
24. Yankowski,A.A.,
41. Idner, K., Tappij
Tappi 55(6):937
(1972).
71(2):47
(1988).
25. Histed,].A. and Nicolle, F.M.A., Pulp Pap.

Mag. Can. 74(12):T 386 (1973).
42. Griggs, B.F., Eachus, S.W., Joseph,

Pulp Pap. Can. 95(9):T51 (1994).
26. Histed,].A., CPAR Projeet Report 47-6, En.

vironment
Canada library, Place Vmcent
Massey, 351 St. Joseph Blvd., Hull, KIA
OH3.
43. Nordberg, c., ffiiggstrom, S., Berglund, S.,

Hultman, B., "High Quality Sulfite Pulp,
Low Environmental
Impact," 1991 International Pulp Bleaching Conference
Proceedings, SPCI, Stockholm, Vol. 3, p. 135.
27. Pattyson,G.W.,
Rapson,w'H.,
(1981).
44. Reeve, D.W., Pulp

(1977).
Pap. Can. 78(3):T50
45. Reeve,D.W,
(1984).
Pap. Can. 85(2):T24
Rae,R.G.,
Reeve,D.W.,
28. Maples,
G., Ambady,
R., Caron, J.R.,
Stratton, S., Vega Canovas, R, Tappt j
77(11):71 (1994).
29. Nicolle, F.M.A. and Histed,].A.,Pulp
Can. 76(9):T253 (1975).
Pap.
30. HistedJ.A.
and Nicolle,F.M.A.,
CPAR
Project Report 47-4, Environment
Canada
library, Place Vmcent Massey, 351 St. Joseph Blvd.,Hull, KIA OH3.
31. Wartiovaara,
T167 (1980).
I., Pulp
Pap. Can. 81(7):
32. Forbes, D.R, "Countercurrent

Washing at
Scott Maritimes
Pulp Ltd.," paper presented at the Atlantic branch, Tech. Sect.
CPPA, Montreal,1976.
33. Perrault,R.R,"Upgrading
the Performance
of Bleach Plant Washers,"
1992 TAPPI
Pulping Conference
Proceedings,
TAPPI
34. Renard, }.}., Phillips,
R.B., Janeel, H.,
Rudie,A.W,
Tapptj 64(8):51 (1981).
35. Histed, JA. and Vega Canovas, R.E., Can.
Pat. No. 1,230,205 (Dec.15, 1987).
36. Young,}.,
Pulp Pap. 67(6):125
37. Berry, RM. and Fleming,

Set. 14(5):)124 (1988).
(1993).
B.I.,jPulp
Pap.
46. Steven,
(1976).
Pulp
F., Pulp
Pap. Can. 77(11)
}.c.,
28
47. Pattyson, G.W, "The Kamyr MC Mixer for

Chlorine Dioxide Mixing at Great Lakes
Forest Products Ltd.," Presented
at CPPA
Midwest Branch Members' Night,April8,
Lakehead
University,
Thunder
Bay,
Ontario, 1983. (unpublished).
48. Herschmiller,
D., Hastings, c., Gleadow,
P.,"From ECF/fCF to closed cycle operation; The Missing links" Asian Paper-94,
World Trade Center,Singapore,Miller-Freeman, San Francisco, 1994.
49. Evans, T., Sweet, W, Manolescu,
D., "Applying Proven Technology
to Eliminate
Kraft Bleach Plant Effluents," Annual Mtg.
Proceedings,Tech.
1994, p. B237.
50. Albert, R,"Worldwide
Survey, State-of-theArt TCF Bleaching," Non-chlorine
Proceedings,
51. Brunner,
76(7):65
F.L. and Pulliam,

(1993).
T.L., Tappi j
SEcnON VB:
The Properties of Bleached Pulp
Chapter 1:
Bleached Pulp Composition
and Its Determination
Jaana SjOstrom and
Anders Brolin
Stora Corporate Research
Satfle, Sweden
1. Introduction
677
2. Carbohydrate characteristics and their measurement.

. . . . . . . . . . . . . . . . . . . 677
2.1 Molecular weight and molecular weight distribution
679
2.2 Determination of cellulose and hemicellulose content. . . . . . . . . . . . . . . . . . . 681
:J. Ugnin and functional groups of 1ignin and po1ysaccharides
..............
3.1 Residual lignin in bleached pulp
3.2 Phenolic hydroxyl groups in lignin
3.3 Strong and weak acidic groups. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.4 Carboxyl groups in uronic acids. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
683
683
684
684
685
4.
686
ExtraneousmaterlaJs...'
4.1
4.2
4.3
4.4
'
'
'
"
Organic extractives. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Dirt specks, pitch deposits, and stickies
Chlorinated compounds. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5. Spectrometric
analysis and multivariate
data analysis
675
686
689
689
689
. . . . . . . . . . . . . . . . . . . . 690
Chapter vn 1: Bleached Pulp Composition and Its Determination
Chapter VII 1:
Bleached Pulp
Composition and Its
Determination
1. Introduction
Bleaching gives rise to changes in the
pa~~pro~~androemic~ro~
position of fibers. Although the influence
of chemic~ composition on the physic~
pro~rties of pulp fibers cannot,in all cases,
be fully explained, it is recognized that
measurement of manges in the roemic~
composition
of pulps occurring during
bleaming is useful in process control and
necessary in development
work. For instance, the major concern in running and
developing modem bleaming sequences is
to maintain pulp viscosity, that is, to avoid
reduction of cellulose molecular weight
and fiber strength (Table 1). Low fiber
strength limits the maximum attainable
pulp strength, but an increase in pulp hemicellulose content lowers the beating requirement
for a specific
pulp/paper
strength (1).
To minimize the use of expensive bleaching roemicals and reduce blearo plant emissions, pulping is extended to remove as
much lignin as possible before bleaming.
Because bleaching may only chemically
modify the lignin without removing it, as is
especi~ly the case when bleaching meroanic~ pulps, lignin reactions induced by
light and heat may affect paper quality
(Table 1). A high lignin content provid~
fiber stiffness which in some applications
is as important as high brightness. IT the
brightness stability ofblearoed fibers is critic~,information about example phenolic hydroxyl groups in lignin, whiro are largely
responsible for yellowing, can be ~uable.
A roemic~ change caused by bleaching
and which accounts for sevem effects on
papermaking properties can be measured
:IS ch:mges in the amount and distribution
of acidic groups on fibers (fable 1). The
mainly positive effects on papermaking of
these groups arise from their cation ex-
mange
capacity
677
678
and ability to retain cationic
polymers used, for instance, as retention

aids. Mainly negative effects on papermaking are contributed by extraneous materi~s (Table 1). These are usually dissolved or
dispersed in the paper mamine white water until they lose their solubility or colloi~ stability, for instance, because of the
presence of me~ cations such as c~cium
(Table 1), and deposit onto the paper mamine or the paper. Extraneous materials
and me~s can ~ be regarded as impuriti~ in paper gra~ intended for use in some
packaging materWs and hygienic products.
Furthermore, the ca~c
effect of me~s
on the oxidation of lignin and certain extraneous materi~s may be important in the
yellowing of pa~r.
The ~ of this roapter is to review the
methods used to. determine the chemic~
composition of pulp. The main part of the
chapter describes conventio~
wet roemiconsisting of sample pretreatc~ ~
ment by dissolution,
acid treatment,
combustion, incineration or extraction and
~
intrumen~
~is.The
discussi~n is
focused on the restrictions and benefits associated with different methods. Examples
are included to illustrate the changes in pulp
composition arising from bleaching. Subsection 5 describes a new approaro to roemic~ roaracterization
of pulp, that is, the use
of multivariate data ~sis
to extract more
information from raw ~c~
data from
rapid instrumen~
techniques that do not
require lengthy sample pretreatments.
2. Carbohydrate characteristics
and their measurement
The fiber strength of undegraded lignocellulosic mate~ is genemly proportio~
to the a-cellulose content; that is, the tensile load on the fiber is borne by the cellulose fraction, but hemicelluloses and lignin
are to distribute the load among the fibrils.
Pulp fiber strength is affected by the molecular weight of the cellulose roains comprising the fibers (24). The sites of native
irregularities or mechanical damage, e.g.,
chipping, hot blow disroarge from digesters, and high-shear mixing. are more acces-
e'" eu
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Chapter VII I: Bleached Pulp Composition and Its Determination

sible in the swollen state than the crystalline regions and are thus at greater risk for
chemical attack. This chemical attack leads
to the degradation of cellulose chains and
loss in fiber strength.
The relationship between fiber strength
and cellulose degree of polymerization (DP)
for different pulps has been examined by
several authors (4, 5). It has been demonstrated that the nature of cellulose degradation controls the extent of fiber strength
reduction
(4). Until low DP levels are
reached, homogeneous
depolymerization
does not seem to impair strength as much
as heterogeneous Oocalized) depolymerization which reduces fiber strength drastically.
A reduction in cellulose DP resulting from
homogeneous
degradation as occurs, f~r
example, during vapor phase acid hydrolysis of kraft or sulfite pulp is less detrimental to pulp strength than an equal drop in
DP resulting from a heterogenous
attack
(e.g., by treattnent of unbleached low-yield
kraft pulp with cellulase) or by liquid-phase
acid hydrolysis (e.g., during acid bleaching
stages or intermediate
stages of sulfite
pulping) (4, 6). Pulps that have undergone
heterogeneous attack are sensitive to extensive beating.
Depolymerization during pulp bleaching
occurs primarily in the chlorination, oxygen, ozone, and peroxide stages and, to a
lesser degree, if the pH is too low in the
chlorine dioxide stage (6).Acld hydrolysis
and oxidation with chlorine-based bleaching agents tend to occur in the amorphous
areas of the cellulose and do not penetrate
the crystalline areas. Oxygen and ozone are
thought to react by a free radical mechanism a-9).These
free radical reactions are
probably restricted to surfaces near the site
of their generation (t.e. near the fiber surface) because of their short lifetime.
2.1 Molecular weight and molecular

weight distribution
Staudinger developed a relation between
viscosity and molecular weight for chain
molecules which was later modified by
other researchers to the more general equation:
[1'\J = Km
MQ
679
[1J
where
M is the number average (M.), length average ~,or
weight average (M~ molecular
weight or the corresponding average degree
of polymerization (DPn' DP, or DP~.
'
Km is the S<Kalled Staudinger constant and
a is a variable which decreases with increasing molecular weight.
Kmand a vary according to the method used
and the measurement performed and are
dependent on the structure of the polymer.
This effect becomes evident at DP > 1000,
that is for high molecular weight cellulose
(10).
As a general rule-of-thumb, low viscosity
implies low pulp strength but high viscosity does not necessarily indicate a high pulp
strength. The fiber strength represented by
the rewetted zero-span tensile index (Fig I
a) has been shown to decrease almost linearly with the viscosity of the pulp. The
strength is reduced to the same extent
irrespective of whether the viscosity loss
occurred during kraft pulping, oxygen delignification, or bleaching with different chemicals. Tear index at constant tensile index
drops rapidly at intrinsic viscosities below
approximately 750 drn31kg (Fig 1 b).
Ozone-bleached
pulps tend to have
higher strength than is suggested by their
viscosity.This may be explained by the carbonyl groups introduced in the cellulose
chain during bleaching and which distort
the viscosity value. During viscosity measurement in, for example, cupriethylenediarnine (CED) under the prevailing strongly
alkaline conditions, degradation of the cellulose chains by (klirnination may occur.
To avoid this problem it has been recommended
that
carbonyl
groups
be
removed by reduction with sodium borohydride prior to making viscosity measurements (11).
The viscosity of a polydisperse polymer
generally is affected mainly by the high
molecular weight fraction of the sample
which implies that viscosity measurements
are especially useful for samples having a
PulP Bleaching - Principles and Practice
680
~140
Z
~'"130
~
'iij
c:
S 120
c:
IIIe8chIng 88qU8llce
o OC(EP)D(EP)D
. OQ(Z,O)(OP)
. OQ(Paa,O)(OP)
~
e
110
'"
500
600
700
800
900
1000
Viscosity, dm3/kg
15
0
.!2'
'"ZE 14
E
x 13
'0
'"
.5
; 12
Bl88chlng MqU8I1C8
o OC(EP)D(EP)D
. OQ(Z,O)(OP)
~. OQ(Paa,O)(OP)
b
11
500
800
700
800
900
1000
Viscosity, dm3/kg
Fi8. 1. upper: 17Ief'f1~

be'-M
"""'- PRt'nJe1tMzero-", tMSIk
-rh16
(5).
~"lItJftrtJootllnwft
~I""- I1Ist:osUy
F18.1. r-:
17Ief'f1~
be'tMr
I""., tMSIk
85 NIIII.J,,11IIIJOftrtJootllnwft
pip
Sample Type:
I""- (5).
IlIstmIIy
Sample Prqmation
and Derivatization
Sample Work-up
Swelling in water
Solvent exchange
DMAC + DMACI
UCI
narrow molecular weight distribution. Because the low molecular weight tail fractions significantly affect fiber strength,
information obtained from viscosity measurements becomes less relevant as the
polydispersity increases (2). It is therefore
imperative to have information on the molecular weight distribution to complement
the average molecular weight data provided
by the viscosity measurement. Application
of size exclusion chromatography (SEC) to
the analysis of underivatized cellulose therefore is valuable, and much effort has been
devoted to devise methods suitable for
pulps (Table 2).
Size exclusion chromatography
The main reasons for the slow development of SEC methods for the characterization of chemical pulps include, on one
hand, the problems involved in dissolving
cellulose samples and, on the other hand,
the lack of column packing materials
compatible with cellulose solvents (12, 13).
The most extensively studied cellulose
solvent for SEC is N,N-dirnethylacetarnidelithium chloride (DMAC-UCl). The main
Separation and
Chromatographic
Detection
and
Reference
Calibration
Conditions
Spruce sulfite
pulp, bin:h
kraft pulp
SEC, StyragelTTol
columns,
0.5%
RI (refractive
index) detector
(2)
ua in N,Ndimethylacetamide as eluent
Beech cfis.
solving pulp
Dissolution in cadoxen
(300 g ethylenediamine,
L water; 5.5 % Cd; 0.2
(15)
HEMA gels:
Exclusion limits
2'1()6,S'10'
and 3'10' Dalton.
cadoxen:water
M NaOH)
(1:1) as eluent.
Bleached
pine bisulfite,
dissolving pulp,
Swelling in pyridine
or DMSO, carbaniIation
with pheny\isocyanate
Precipitation of
cellulose tricarbaniIatesin
Polystyrene-i>ased
SEC packings,
tetrahydrofuran
uv, RI or low
angle laser light
prehydro\ysis
in pyridine
MeOH (pyridine)
or EtOH (DMSO),
washing, and
as eluent
(LALLS)
kraft pulp
or DMSO
drying
scattering
detector
(12, 16 - 18)
Chapter VIII: Bleached Pulp Composition and Its Determination

drawback of this solvent is that most cellulosic materials are dissolved only upon refluxing with DMAC under degradation of
the polymer molecules (14).The ease and
rate of dissolution are influenced by the molecular weight of the polymer itself and its
degree of crystallinity (2).A gentler, but less
efficient,
dissolution
is achieved
by
preswelling the pulp sample in water; however, not all pulps can be dissolved completely, especially
high-DP pulps, for
example, softwood kraft pulps (Table 2).
Another drawback arising from the use
DMAC as solvent and eluent in SEC is the
short lifetime of chromatographic columns
exposed to it (12).
Cellulose solvents used typically in
viscosimetry (cadoxen and iron sodium tartrate, FeTNa) have been investigated for
their suitability in the determination of MW
distribution by SEC (15). As in viscosity
measurements, the high pH of these solvents is a disadvantage due to the risk for
jX:limination reactions.
Because known cellulose solvents are not
suitable for chromatography, the molecular
weight distribution (MWD) analysis of cellulose is normally carried out on derivatives
which are soluble in the solvents currently
used in SEC (16). The advantages of using
cellulose tricarbanilates for MWD determinations are derivative stability (18), a simple
procedure
for achieving
complete
trisubstitution,
and insignificant (if any)
cellulose degradation during derivatization.
Some low molecular
by-products
are
formed during the carbanilation reaction
which, if not removed, interfere with the
MWD determination. Care must be taken
therefore to ensure that all of the sample
dissolves and reacts during derivatization
and is quantitatively precipitated during the
purification step (18).
Calibration
requirement
in viscosity
and SEC
measurements
Because viscosity measurements and SEC
combined with IN or RI detection are secondary methods, they need to be calibrated
to obtain absolute DP or MW values. Calibration is accomplished by the use of welldefined standards whose molecular weight
681
has been determined by primary methods

based on osmotic pressure, light scattering,
or ultracentrifuge sedimentation rate measurements. In SEC, where the separation is
based on hydrodynamic volume rather than
on molecular weight, correct results are
obtained only if the standards have the same
molecular structure as the sample (t.e. linear polymers). Polar substituents increase
the hydrodynamic volume which may lead
to overestimation of the molecular weight
of hemicelluloses. Measurement reproducibility may suffer because of the instability
of the high molecular weight standards. To
overcome these difficulties in SEC, detection by laser light scattering has been recommended
for direct measurement
of
molecular weight (12,18).
2.2 Determination
of cellulose
and
hemicellulose
content
Cellulose is the main pulp constituent
and, because of its chemical and physical
properties and its supramolecular structure,
the principal contributor to pulp strength
and other properties. Hemicelluloses affect
pulp strength properties by contributing to
bond strength and bonded area (19). In
general wood analysis, also applicable to
pulp, lignin is removed by treatment with
elemental chlorine or sodium chlorite under conditions that minimize chemical attack on the polysaccarides. The product
obtained after removal of lignin is extracted
with aqueous alkaline solutions to separate
the insoluble cellulose from the soluble
hemicelluloses. Hemicelluloses are precipitated from the alkaline solutions by acidification and by addition of organic solvents
(20). The cellulose fraction obtained by
such procedures is often contaminated by
residual lignin and polyoses while the hemicellulose fraction may contain low molecular weight cellulose.
Another approach used for measuring the
cellulose and hemicellulose content of pulp,
as well as the molecular composition, is to
determine the monomeric sugar units ari1r
ing from degradation of the polysaccharides.
Traditionally,
degradation
is
accomplished by acid hydrolysis, that is, by
682
Pulp Bleaching
-Principles
and Practice
acid-catalyzed cleavage of the glycosidic

bonds and addition of water to the anhydrosugar units to yield monomeric sugars.
Acid hydrolysis
Complete hydrolysis of crystalline cellulose requires severe conditions and lengthy
procedures. The usual methods include
impregnation and swelling of the sample
with 72% sulfuric acid followed by dilution
and refluxing for 2-5 hours or treatment in
an autoclave as described by Saeman (21,
22). Alternatively, pulps are dissolved in
concentrated
(lOO"A.)trifluoroacetic
acid
(TFA) and the solution is refluxed after dilution (23). The advantage ofTFA over sulfuric acid is its volatility: TFA can be
removed by evaporation, but sulfuric acid
must be neutralized. Both hydrolysis procedures cause. severe degradation of the
monomeric sugars, and it is necessary that
losses of individual sugars be determined
and corrected
before calculating
sugar
yields.
Analysis of sugars
Comprehensive reviews of sugar analysis are found in the literature. The methods
usually used in wood chemistry are com-
piled in Table 3. Following the appearance

of the review by Churms (24), promising
methods utilizing capillary electrophoresis
were devised (Table 3). Regardless of the
method chosen for the analysis of sugars,
response factors must be determined for
each sugar throughout the analytical procedure,
including
the pretreatment,
derivatization, separation, and detection
steps.
Analysis of polysaccharides in pulp by pyrolysis gas chromatography
It has been shown recently that pyrolysis gas chromatography (Py-GC) represents
an alternative to acid hydrolysis and analysis of monomeric sugars in pulps (31). A
pulp sample is rapidly pyrolyzed, that is,
degraded thermally in an inert atmosphere,
and the resulting products are separated by
gas chromatography. If the acidic groups in
the pulp are in their hydrogen or calcium
form, the prevailing pyrolysis mechanism
is transglycosidation leading to the formation of specific anhydrosugars.
Quantification of polysaccharides
The amount of polysaccharides
tained by multiplying the amount
is obof hex-
Separation
Technique
Pretreatment
Derivatization
of Hydrolysate
Procedure
Column
Detection
GC
Neutra1ization,
drying
Add pyridine and

HMDS/TMCS(2/1),
to form
trimethylsilyl ethers
Fuse<kilica
capillary with
nonpolar
liquid phase
FID
(25,26)
GC
Neutralization,
drying, reduction
to alditols with
KBH, or NaBH,
Acetylate with
acetic anhydride/
catalyst, extract
the alditol acetates
into organic solvent
Fused-silica
capillary column
with polar
liquid phase
FID
(22)
HPLC
Neutra1ization,
concentration,
clean-up
Polymer-based
cation exhange
column at
75-85 C
RI
(refreactive
index)
(27)
Ion
chromatography
pH adjustment
with NaOH
solution
Dionex HPIC-AS6
PAD(pulsed
amperometric)
(28)
IN of borate
complex,
(29, 30)
anion exchange
column
Capillary
electro-
No derivatization
phoresis
pyridine to form
N-2-pyridyl-
or add amino-
gIycamines
Silica capillary
column
indirect lN,
lNof
derivative
Reference
Chapter vn 1: Bleached Pulp Composition and Its Determination

oses by a factor of 0.9 and the amount of
pentoses by a factor of O.88.The amount of
cellulose is obtained as the difference between the total amount of anhydroglucose
in the pulp sample and the amount of
anhydroglucose
originating from hemicelluloses. The amount of anhydroglucose
originating from hemicelluloses can be estimated as the amount of anhydromannose
divided by a predetermined
factor whose
value depends on the wood species (20).
3. Lignin and functional groups

of lignin and polysaccharides
Lignin and carbonyl groups normally
show strong absorbance of electromagnetic
radiation in specific wavelength
bands
which facilitates their in situ identification
by spectrometric techniques such as ultraviolet (UV), near infrared (NIR), mid-infrared (lR), and fluorescence
spectrometry.
This property is especially valuable because
isolation procedures, which are normally
tedious and may introduce
structural
changes to the analyte, can be avoided.
Spectrometric methods need calibration by
traditional wet chemical methods or by
model substances to provide absolute quantitative results. In Fig. 2, a difference spectrum obtained by subtracting
the FfIR
spectrum of unbleached spruce TMP from

the spectrum of peroxide-bleached
TMP
demonstrates the effect of peroxide bleaching on the chemical composition of the pulp
and illustrates the usefulness of a simple
evaluation of spectrometric data for detecting changes in the relative composition of
mechanical pulps especially. The negative
bands at 1736 cm-I and at 1240 cm-' indicate loss of acetyl groups in bleaching.The
negative lignin bands at approximately
1510 cm-' and the positive band at 1062
cm-' indicate an increased carbohydrate/lignin ratio. Dissolved galactoglucomannans
in TMP suspensions are known to precipitate onto fibers during peroxide bleaching
after undergoing deacetylation
and thus
compensate for the yield loss in bleaching;
lignin-like substances are dissolved and
partly degraded during alkaline peroxide
bleaching (32).
3.1 Residual lignin in bleached pulp
Methods for the determination of lignin
in wood and pulp have been thoroughly
reviewed and discussed (33).The residual
lignin in bleached pulps is of great importance because it has been proven to be a
major contributor to thermally and lightinduced yellowing of paper. The residual
1240
1736
co
'iij
In
'E
In
c:
~
I-
4000
2000
Wavelength, cm-1
Fig.2. Dlffereace spectrum of~-6/eacHtl"M
683
"rJbleacHtl TMP.
450
684
lignin content of bleached chemical pulps

is normally 1% or less making the classical
gravimetric analytical methods used for
unbleached pulp, for example, Klason lignin, virtually useless for accurate determination of lignin content.
Because of the lack of reliable wet-chemical methods for determining
low 1%)
concentrations of lignin, it is not feasible to
calibrate spectrometric methods for accurate quantification
of lignin in bleached
chemical pulps. Moreover, modification of
the lignin structure
occurring
during
bleaching, for example, ring opening reactions during chlorine dioxide, ozone, or
oxygen delignification, reduces the absorbance corresponding to the aromatic ring
frequency normally used for lignin determination in unbleached pulp. As a result,
methods based on absorbance of electromagnetic radiation by aromatic rings would
indicate, in such cases, delignification even
though ring opening does not necessarily
imply lignin removal.
Modification of lignin during pulping and
bleaching also makes the relevance of classical methods for wet-chemical
analyses
(e.g., kappa number) questionable. Because
kappa number is primarily not a function
of lignin content but a measure of the oxidation state of the pulp, the use of oxidizing chemicals in bleaching may lead to
underestimation
of the actual residuallignin content.
3.2 Phenolic hydroxyl groups in lignin
Oxidation of phenolic lignin units to
quinone structures contributes significantly
to the photoyellowing of lignin-rich pulps
(34). Phenolic hydroxyl groups in lignin are
determined preferably by methods involving aminolysis of acetylated phenolic compounds with pyrrolidine
followed by
measurement of l-acetylpyrrolidine (35) or
by periodate oxidation of guaiacyl compounds to o-quinones and measurement of
the methanol released (36). Both methods
have been applied for in situ analysis of softwood kraft pulps and for unbleached and
peroxide-bleached hardwood and softwood
(chemi)mechanical
pulps (37). The methods cannot be used for routine analysis be-
cause they include chemical reactions

which take several days to complete as well
as chromatographic
measurement
of a
highly volatile reaction product which is
difficult to quantify in low concentrations
in complicated matrices.
3.3 Strong and weak acidic groups
Unbleached and bleached pulps contain
acidic groups which, in their ionized forms,
retain metal cations (38, 39).The concentration of acidic groups, their degree of dissociation, and the valency of the metal ions
influence fiber swelling (40, 41) which in
turn affect such papermaking concerns as
beating, drainage resistance, drying, and
cationic resin retention (1). Lindstrom and
Carlsson (42) have shown that homification
of bleached pulp fibers during drying, that
is, loss in swelling capacity and loss of plasticity attributable to structural changes in
the cell wall, can be reduced by introducing carboxyl groups to bleached kraft pulp
fibers and drying the fibers in their ionized
(especially Na.) form.
The total acidic group content of pulps
is measured by direct acid-base titration of
a pulp suspension or by determining the
extent to which pulps can be ion-exchanged
to a particular cation form. These methods
have been reviewed and compared for use
in the analysis of sulfite pulps (43), and
conductometric
titrimetry
was recommended for its simplicity. Both methods allow differentiation between strong acids,
that is, sulfonic acid groups in lignin and
some carboxylic acids, and weak carboxylic acid groups. Carboxylic acid groups are
present in pulp in uronic acid-containing
hemicelluloses and in lignin. Chlorine dioxide and ozone bleaching treatments reduce the amount of carboxylic acid groups
in hemicelluloses
(44); conversely, the
amount of carboxylic acid groups in the
residual lignin increases in ozone and peroxide bleaching (45). Peroxide-bleached
TCF pulps therefore normally contain more
carboxyl groups than do ECF pulps (Table
4). Because the carboxylic acid contents of
the ozone-bleached TCF pulps lie between
those of the peroxide-bleached
TCF pulps
Chapter vn 1: Bleached Pulp Composition and Its Detennination
Pulp
No.
Pulp;
Bleaching
Sequence
Brightness
(% ISO)
la'
Softwood
Ib'
Softwood kraft,
C/O Ell DED
2a
Softwood
2b
Softwood
Weak
Acids',
(mmol/kg)
0.190
18
80
0.190
17
28
96
0.172
35
88
kraft";
90.6
kraft";
TCF
3a
Softwood kraft";
D(EOP)DED
3b
Softwood
SO.l
5.0
97
0.176
10
64
88.3
0.5
94
0.171
31
84.4
1.7
95
0.172
45
96
0.263
12
65
94
0.238
13
104
0.260
10
76
88
0.183
13
81
kraft";
A(ZQ)(EOP)
Birch kraft";
D(EP)(D,E+P)D
88.9
4b
Birch
81.8
6.8
Birch kraft;TCF
(ozone)
89.2
2.8
6a
Eucalyptus
kraft";TCF
kraft";
ECF
6b
Strong
Acids',
(mmol/kg)
Total
HemicelV
Total
Carbohydrates, % Carbohydrates
32
kraft
D(EOP)D(EP)D
4a
Kappa
Number
685
Eucalyptus
90.7
kraft";
TCF
6
Softwood sulfite; P
Softwood sulfite;
OQP
85.8
86.4
5.1
90
0.181
11
114
15.0
90
0.164
36
82
87.4
4.8
94
0.126
17
52
'Pulps a and b were produced in the same mill.

"Oxygen delignification prlOt to bleaching
'Determined by conductometric titration (43)
and the ECF-bleached pulps (cf. pulps 2a,

2b, 3b and 4a, 4b, 5 in Table 2), it appears
that the formation of new carboxyl groups
in the ozone stage occurs to a lesser extent
than their degradation.
3.4 Carboxyl groups in uronic acids
Specific determination
of the carboxyl
groups in uronic acids may be of value to
establish if the carboxylic
groups in a
bleached pulp are initially present in the
polysaccharides or are introduced in the lignin during oxidative bleaching.
The total amount of carboxylic
acid
groups in uronic acids can be determined
by decarboxylation followed by measurement of the carbon dioxide released (46)
or by colorimetry (47). Application of these
rapid methods to pulps bleached with modem oxidative sequences needs to be evaluated to exclude
interferences
from
compounds having decarboxylation
rates
similar to those of uronic acids or from compounds forming colored reaction products
with the colorimetric reagents. A more reliable, but much more tedious, approach for
quantifying the carboxyl groups in uronic
acids is to analyze entire uronic acid residues as such. Individual uronic acid units
and carbohydrate composition usually cannot be determined simultaneously because
the glycosidic bond between a uronic acid
residue and a neutral sugar unit is resistant
to acid hydrolysis. Also, uronic acids are
probably degraded to a large extent during
hydrolysis with concentrated
acids. Re-
686
Pulp Bleaching
-Principles
and Practice
cently it has been emphasized

that the
~-elimination
product
of 4-0-methylglucuronic acid, hexenuronic acid, is especially sensitive toward acid hydrolysis (44,
48). To avoid contact with concentrated
acid, hemicelluloses containing uronic acid
units should be isolated from the pulp by
extraction with aqueous alkali or solubilized
by partial hydrolysis using specific enzymes
and analyzed separately.
Three principal methods are available for
the specific analysis of galacturonic and glucuronic acids present in the water and alkali-soluble carbohydrates of pulp: (1) The
hemicelluloses are hydrolyzed under mild
conditions with dilute trifluoroacetic acid
or specific enzymes. The resulting dimeric
aldobiouronic
acids and trimeric aldotriouronic acids are separated from the
hydrolyzate by ion exchange, the uronic
acid units are reduced, and the resulting
neutral disaccharides and trisaccharides are
hydrolyzed (49). Galacturonic
and 4-0methylglucuronic acids are analyzed as galactose and 4-0-methylglucose;
(2) The
carboxyl groups in hemicelluloses are reduced with deuterium borohydride,
the
polysaccharides
are hydrolyzed, and the
deuterated neutral monosaccharides,
representing the uronic acids in the original
polysaccharide, are analyzed by selected ion
monitoring
mass spectrometry
(50);
(3) The hemicelluloses
are subjected t6
methanolysis, a reaction which is efficient
in cleaving the bond between the uronic
acid unit and the neutral sugar unit (51).
The resulting methyl glycosides, representing the neutral anhydrosugars, and the methyl glycosides of uronic acid methyl esters,
representing the anhydro uronic acids, are
determined.
4. Extraneous
materials
4.1 Organic extractives

Organic extractives in pulp, that is, substances which can be extracted with an
organic solvent, consist mainly of native
wood extractives, extractives modified in
pulping and bleaching, and residual process
chemicals such as defoaming agents. End
use determines the concentration and type
of materials which can be tolerated in a

pulp. Unsaturated fatty acids and their esters, for instance, are easily oxidized to volatile, off-flavor compounds (52), and pulps
intended for food wrapping papers should
therefore be virtually free of native wood
extractives. Resin acids, present in softwood, can be oxidized by air to form contact allergens (53) and therefore should be
washed from pulps intended for use in hygienic products. Another incentive for the
chemical characterization of the extractable
materials is to identify wood extractives or
impurities which tend to deposit on the
paper machine or converting equipment.
Examples of such compounds are fatty acids, which precipitate as calcium soaps in
neutral or acidic media, and fatty acid
amides present in defoaming agents (54).
The extractives and impurity contents of
pulps are usually determined gravimetrically. The weight and composition of the
extract are highly dependent on the extraction procedure. The composition of the residue is not only determined by the wood
species used as raw material and the extraction technique but to an even greater degree by pulping and bleaching processes.
Extraction
Extraneous
materials are usually extracted from pulp with an organic solvent,
for example, acetone, ethanol, benzene, or
dichloromethane
in a Soxhlet apparatus or
a Soxtec apparatus (55). In the future, acetone will probably be the most common
solvent for extractions because the use of
aromatic and chlorinated solvents will be
restricted for health and environmental reasons. The weight of the acetone extract is
usually higher than that of a dichloromethane extract of the same pulp (56, 57).
For efficient extraction of fatty and resin
acids with acetone, it is important to acidify
the pulp to pH below 3 before the extraction to convert the acids from an insoluble
metal soap form to a soluble, free-acid form
(57).
The use of organic solvents can be minimized by supercritical fluid extraction.The
most commonly used solvent is supercritical
carbon dioxide. Only minor amounts of
Chapter VIII: Bleached Pulp Composition and Its Determination

organic solvents are used as supercritical
fluid modifiers and to collect the extract.
In a recent study, the supercritical carbon
dioxide extraction of an unbleached pine
kraft pulp has been compared to a Soxhlet
extraction with dicWoromethane
and acetone, (56). The yield of free fatty acids,
esterified fatty acids, resin acids, and sterols was highest with supercritical extraction. A further advantage of supercritical
extraction is the relatively short time required for the step.
Characterization of the extract
The first approach to extract characterization is usually IR-spectroscopy.The Fl1R
spectrum of peroxide-bleached
CTMP is
dominated by absorption bands attributable
to unsaturated fatty acid esters (carbonyl-at
1742 cm-~ ester at 1153 cm-I, carbon chains
at 724 cm-], double bonds at 3009 cm-I)
which are the main lipophilic extractives
in wood. The band at 1515 em-I (Fig. 3) indicates that the extract contains lignin-like
substances not regarded as resin components.
A universal chromatographic
approach
to obtain information about the complexity of a material is to analyze a sample by
size exclusion chromatography (SEC). The
components
are separated primarily by
687
molecular size and detected with the universal refractive index detector. The SEC
chromatograms in Fig. 4 reveal that the composition of cWorine dioxide-bleached pulp
extractives is different from that of unbleached pulp extractives. The upper chromatogram in Fig. 4 shows the presence of
the three groups of components
usually
present in unbleached sulfate pulp: steryl
esters, sterols and fatty acids, and resin acids. The lower chromatogram of cWorine
dioxide-bleached
pulp suggests that the
molecular volume of the extractives increases during bleaching, possibly because
of polymerization and oxidation. The chromatogram further shows that only a part of
the extract can be related to the groups
present in unbleached pulp and wood.
Chromatographic separation techniques
The group separation obtained by SEC
can be complemented
by other methods.
Thin layer chromatography on silica gel has
been used for analytical and preparative
fractionation of wood extractives in spruce,
pine, and birch (58; 59). Universal detection by spraying with aqueous sulfuric acid
and heating can be combined with densitometric scanning to obtain setniquantitative results. Specific detection with a UV
scanner affords chromatograms similar to
688
)(
en
1: Steryl esters
2: Fatty acids and sterols
3: Resin acids
."5
en
>
13
-a:~en
~
Fig. 4. Size e3tClulmc elmnrultogrtlffU

softrlJOO4 lmIft ptllp.
intemal
standard
20
22
24 Time, m-..
Increasing molecular volume
of tbe extrtlets
of ..bletlt:11M
tm4 ECF-bktu:11M
I.a
18:1
Q)
CJ)
~c:
0
a.
CJ)
sojtrtJ004 lmIft ptllp
l.a.-amide
I.a
16:0
u:
f.a 22:0
l.a24:0
~f.a
8:0
I.a
26:0
15
25
20
Retention
time,
<f.
Co
'iij
UJ
'E
UJ
c:
~
I-
those obtained by column liquid chromatography, but only UV-absorbing

compounds are detected.
Supercritical fluid chromatography
is a
new technique for the group separation of
wood extractives in pulp (56). Compatibility with flame ionization detection is an
advantage; however, optimum separation
may require organic modifiers which pre-
3009
1153
1742
4000
Fig. 3. FI1R spec"."", of tbe _toree
2000
Wavelength,
450
cm-1
extrtlet of tI sJIrII CTMPptlip.
clude the use of flame ionization detection

(60).
Recent improvements in gas chromatographic injection systems have allowed si-
multaneous quantitative analysis of all major wood extractive groups in silylated extracts (51). The technique has been applied
to the analysis of white water from unbleached and peroxide-bleached
TMP suspensions.Analysis oflow concentrations of
specific low molecular weight compounds,
such as individual fatty acids, resin acids,
or defoaming agents is usually done by capillary gas chromatography using conditions
optimized for the specific compounds of
interest (Fig. 5).
Chapter vn I: Bleached Pulp Composition and Its Determination

4.2 Dirt specks, pitch deposits, and
stickies
The analytical group separation techniques outlined above are suitable for the
characterization of specks and deposits that
can be dissolved in organic solvents. Combinations of several techniques are usually
needed because of the chemical complexity of deposits. Approaches to analytical
quantitative and semi-quantitative
procedures for various types of deposits are described in the literature (54, 61). In many
cases, qualitative information can be obtained rapidly by pyrolysis gas chromatography (62). This technique is especially
well-suited for the analysis of plastic impurities.
4.3 Chlorinated compounds
The total amount of cWorine in a solid
sample is traditionally determined by combustion of the sample, absorption of the
hydrogen cWoride from the combustion
gases, and determination
of cWoride ion
(63). Combustion is carried out, for example, in a Schoniger flask or an oxygen
bomb (64); cWoride is titrated with silver
nitrate,measured with an ion-selective electrode, or determined by ion chromatography. The entire procedure
can also be
carried out automatically utilizing a tube
furnace connected to a microcoulometric
titration unit. The latter equipment is usually used for the determination
of AOX in
effluents.
Direct procedures
developed for the
measurement of organically bound cWorine
in pulps include removal of chloride by
washing with potassium nitrate solution
(64, 65). Losses of organically bound cWorine during the washing can be avoided by
mixing the pulp with activated carbon (65).
The cWorine content of the washed pulp is
determined as total cWorine and denoted
as organic cWorine. The lower determination limit is approximately 20 mg/kg (20 g/
metric ton) of pulp.
The tot1l.
organochlorine in pulp is often
divided into the sub-fractions "extractable

with water." "extractable with organic solvent," and "unextractable"
(63). Further
689
characterization
of these sub-fractions is
difficult because the chlorinated
compounds are not readily distinguishable by
the techniques commonly used for characterization of pulps and extracts as a whole
(66).
Identification of cWorinated compounds
in extracts requires the use of special mass
spectroscopic
techniques. McKague and
Reeve were able to identify cWorinated linoleic acid derivatives and cWorination
products of prenols by negative ion methane desorption chemical ionization mass
spectrometry
of the extracts
of fully
bleached pulps but were unable to quantify the identified
compounds
(67).
Quantitative analysis of targeted trace compounds, for example, chlorinated phenolics, is feasible by selected ion monitoring
mass spectrometry (68).
4.4 Metals
Oxygen, hydrogen peroxide, and especially ozone bleaching are sensitive to transition metals. TWs is because of the ability
of these metals to induce the homolytic
cleavage of hydrogen peroxide and organic
hydroperoxides formed during bleaching to
yield hydroxyl radicals that in turn are capable of oxidizing and cleaving polysaccharide chains (see other chapters of this
book).To maintain pulp viscosity It is therefore vital to measure and control the metal
profile of a pulp during bleaching.
The metal profile (in the form of counter
ions attached to acidic groups) also influences papermaking
properties
as mentioned above in Subsect. 3.3. Variations in
papermaking properties therefore may be
attributable to variations in the composition
of the mill's water supply or to the retention of sodium ions by the pulp during the
pulping process (38).
Analysis of metals in pulp consists of destruction of organic material to dissolve the
metals and instrumental analysis of the resulting metal ions in aqueous solution. The
organic materials are usually destroyed by
incineration followed by dissolution of the
residue in hydrocWoric acid or by wet digestion with nitric acid in an autoclave or a
690
microwave oven (69, 70). Incineration is

not recommended
if the elements to be
analyzed are volatile or can form volatile
cWorides by interaction with the sample
matrix as is the case with lead and zinc (71).
Losses due to incineration may also be attributed to reduction of metal ions to their
metallic form, leading to poor recovery of
the element in the hydrocWoric acid solution. TWs risk should be considered when
cadmium or copper are to be analyzed.The
major problems that may arise with wet digestion methods, for example, coprecipitation of the element to be determined
with a precipitate formed in the digestion
vessel or adsorption of the element onto
the digestion vessel, seldom need be accounted for when pulps are digested in
Teflon"'-<:oated vessels with nitric acid (71,
72). The metal ions in the resulting aqueous solution are usually determined
by
flame atomic absorption spectrophotometry or by plasma emission spectroscopy.
Determination of ppm or sub-ppm concentrations of metals in acid-washed bleached
chemical pulps requires use of the graphite furnace atomic absorption technique.
Recent improvements in imaging microprobe secondary ion mass spectrometry
(SIMS), which provide high spatial resolution and high sensitivity, have allowed
direct mapping of metals in various morphological regions of wood fibers (73), as
well as on the surface of peroxide-bleached
groundwood pulp (74). Application of this
technique to the characterization
of mechanical pulp fibers might clarify the role
of metals in bleaching, brighmess reversion,
or the formation of off-odor compounds.
5. Spectrometric analysis and

multivariate data analysis
The need for rapid and improved characterization of pulps and for methods which
entalliess risk of sample modification than
isolation and work-up during classical analytical procedures has enhanced interest in
the application of non-invasive spectrometric techniques to bleached chemical pulps.
Over the years several different techniques have been used to characterize pulp
in solid state,for example,UV (75, 76),midand near-IR (77), NMR (78, 79), and Raman
(80, 81) spectrometry. Recently, multidimensional fluorescence
(MDF) has been
suggested as a potential tool in the quantitative determination of low concentrations
of lignin in pulp (82). Vibrational modes
which are weakly active in one technique
are generally detected as strong bands in
another technique with the result that techniques such as Raman and IR spectrometry
(or NMR and ESR) provide complementary
information.
Signals from these spectrometric
methods have been widely used in research to
qualitatively demonstrate structural changes
occurring during various types of pulp treatment. However, it is difficult to extract
quantitative information from specific wavelength bands without considering matrix
effects leading to overlapping bands. Furthermore, the signal at one frequency seldom originates from one specific chemical
constituent, that is, it is more common that
information from several components overlap making peak assignment impossible.To
interprete data correctly and to facilitate
quantification, special methods are required
to handle co-variation.
Methods that apply to restrictions caused
by co-variation are generally termed multivariate data analysis (MVDA) methods and
have been discussed by Martens and Naess
(83). In these methods, a factor extraction
procedure is applied to reduce the number
of variables and to render the variables orthogonal, that is, to fulfill the requirements
for a subsequent regression calculation to
relate the signals to the analytical information sought. The use of techniques such as
PCA (principal component analysis) and PU;
(partial
least squares
projection
to latent
components) may also permit reconstruction of "pure component

spectra" from
their so-<:alled loading vectors. Thus, variations in pulp properties induced by process
or raw material variations frequently can be
given a chemical and/or physical interpretation. This may provide completely new
information on pulp properties. Application of MVDA in combination with spectros-

copy on characterization of chemical pulps
has been reported by several authors (78,
79,84,85).
One particularly useful feature of multivariate analysis is that results from an
unlimited number of traditional characterization techniques can be correlated simultaneously
to signals
from different
spectrometric (or other instrumental) techniques. This provides a way of using a number of well-characterized
samples to build
a model which, together with the particular instrumental technique (one or more at
a time), can be used to rapidly predict the
chemical and physical properties of a new
sample (84, 86, 87).
References
1. Voelker,
M.H., in Tbe Bleacbing
of
Pulp(R.P. Singb, Ed.)3rd edn. ,TAPPI PRESS,

Atlanta, 1979, pp. 337-356.
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33. Dence, C. in Metbods in Lignin Cbemistry (S.Y Lin and C.W. Dence,
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1992, Chap 2.
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36. Lai,Y-Z.,Guo,X.P.,Situ,W.J.Wood
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Millen, M.A., Tappi 37(8):336 (1954).
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American Chemical Society, Washington,
D,C., 1979, p. 145.
6. Fahey, M.D., "How Bleaching Can Change

Pulp Strength;
Operations
24. Churms,
(1990).
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P.K., Henry, R.}.,

Res. 113(2):291
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25. Bethge, P.O., Holmstrom,

c., Juhlin,S.,
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69(3):60 (1966).
26. Paez, M., Martinez-Castro,
I. Sanz,].,
Olano, A., Garcia-Raso, A., Saura-caIixto,
F., Cbromatograpbia
23(1):43 (1987).
7. Lindgren,
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PappersUdn.
81(15):485 (1987).
27. Kaar, W:E., Cool, L.G., Merriman,

Brink, D.L.,) Wood Chem. Tecbnol
447 (1991).
8. Brolin, A., Gierer, J., Zhang, Y, Wood

Technol. 27(2):115 (1993).
28. Penersen,R.C.andSchwandt,Y.H.J,Wood
Cbem. Technol. 11(4):495 (1991).
9. Basch,
Polym.
A., Wasserman,
Sd. 12(6):1143
T., Lewin,
(1979).
Sd.
M:,)
10. Schurz,
I., in Die
Cbemie
der
Pflanzenzellwand
(E. Treiber,
Ed.),
Springer, Heidelberg,
1957, p 360.
11. Hartler,
N., Lindstrom,
E.-B., Tubek-
lindblom,
A., Cellul. Chern. Techno/.
387 (1987).
12. Rantanen, T, Farm, P., Sundquist,}.,
Puu 68(9):634 (1986).
21:
Pap.
500:555
M.M.,
11(4):
29. Hoffstener-Kuhn,
S., Pailus,A., Gassmann,
E.Widmer, H.M.,Anal. Chem. 63(15): 1541
(1991).
30. Honda, S., lwase, S., Makino, A. Fujiwara,
S.,Anal. Biocbem.
176(1):72 (1989).
31. Kleen, M. and Gellerstedt,
Pyrolysis 19:139 (1991).
32. Holmbom,
Eckerman,
(10A):VI6
G.JAnaI.ApPI.
B., Ekman, R., Sjoholm,

c., Thornton,}.,
Papier
(1991).
51. Holmbom,
B. and Orsa, E,"Methods
for
Analysis of Dissolved and Colloidal Wood
Components
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Process Waters and Effluents; International
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22. Blakeney, A.B., Harris,

Stone. B.A., Caroohydr.
(1983).
5. Flink,}. and Norborg, K.,"Bleaching-QuaIity and Environmental

Aspects; Third European Workshop on lignocellulosics
and
Pulp, Swedish Pulp and Paper Research
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1994, p. 125.
34. Tschirner,U.
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15. Teodorovic, M., Danhelka,].,Majdanac,L.,

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Lloyd, L.L., Warner,
F.P., Cellul. Cbem.
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pp. 164167.
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38. Scallan, A.M. and Grignon,].,

Papperstidn.
82(2):40 (1979)
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39. Ampulski, R.S., Nord. Pulp Pap. Res.].

(1):38 (1989).
40. Lindstrom,
T. and Carlsson,
G., Svensk
PappersUdn.
85(15):RI4
(1982).
41. Lindstrom,
T and Kolman, M., Svensk
PappersUdn.
85(3):RI40
(1982).
42. Lindstrom,
T. and Carlsson,
G., Svensk
PappersUdn.
85(15):RI46
(1982b).
43. Katz, S., Beatson,
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R.P., Scallan, A.M.,

87(6):R48 (1984).
44. Buchert, J., Teleman, A., Harjunpaa,

Y.,
Tenkanen, M., Viikari, L., Vuorinen, T., "Effect of Cooking and Bleaching on the Surface Chemistry of Conventional Pine Kraft
Pulp," Third European
Workshop
on
Lignocellulosics
and Pulp, Swedish Pulp
and Paper Research Institute, Stockholm,
1994, p. 16.
45. Lachenal, D., Femandes,}.C.,
Froment, P.,
"Characterization
of Residual Lignin during Bleaching,"Third
European Workshop
on Lignocellulosics
and Pulp, Swedish
Pulp and Paper Research
Institute,
Stockholm,
1994, p. 81.
46. Bylund, M. and Donetzhuber,
A., Svensk.
PappersUdn.
71(15):505
(1968).
54. Dorris, G.M., Douek, M. ,Allen,

Pulp Pap. Sd. 9(1):TRI (1983).
L.H..]
55. Halvarsson,
H. and Hult, 0., Tappi)
(10):105 (1983).
66
56. Bjorklund
Jansson.
M., Alvarado,
E,
Bergqvist,A.-K.,
Dahlman, 0., "Analysis of
Pulp Extractives with Off-line Supercritical
Fluid Extraction
(SFE) and Supercritical
Fluid Chromatography
(SFC); International Symposium on Wood and Pulping
Chemistry
Proceedings,
CTAPI, Beijing,
1993, Vol. II, p.795.
57. SCAN-cM 49:93 "Pulps-Determination
of
acetone-soluble
matter," Scandinavian
Pulp, Paper and Board Testing Committee,
Stockholm,
1993.
58. Holmbom,B.andAvela,E.,ActaAcadAbo,
Ser. B. 31(16) (1971).
59. Ekman,
(1979).
R. Acta Acad. Abo,
Ser B 39(4)
60. Lee, M.L. and Markides, K.E. (Eds.). Analytical Supercrltical

fluid Chromatography and Extraction,
Chromatography
Conferences,
Inc., Provo, Utah, 1990,
p.98.
47. Dische, Z., in Metbods in Carbohydrate

Cbemistry(R.L Whistler and M.L.Wolfrom,
Eds.)Academic
PreSS, New York, 1962,Vol
1, Section V, pp. 497-501.
61. Sjostrom,}.
and Holmbom,
70(2):151 (1988).
48. Lindberg, B., LOnngren,J,.Thompson}.L.,

Carbohydrate
Res. 28(2):351 (1973).
63. Reeve,D.W. andWeishar,

Sci. 16(4):J118 (1990).
49. Maekawa,
64. Stevens, BJ., Sell, L.O., Easty, D.B., Tappi

]. 72(7): 181 (1989).
E. and Koshijima,
T, Mokuzat
GakkatsfJt j4(4): j;9 (1988).

R.,
45
53. Karlberg,
A.T.:Contact
Allergy
to
Colophony.
Chemical
Identifications
of
Allergens, SensiUzaUon
Experiments
and
Clinical
Experiences,
Doctoral Thesis,
Karolinska Institutet, Stockholm, Sweden,
1988.
50. Quintero, E., Ishida, K., Gordon, G.,

Geesey, G.,JMicrobiol.Metbods 9(4): 309
(1989).
B., Pap. Puu
62. Dunlop-jones,
N. and Allen, L.H., Tappi]
71(2):109 (1988).
K.M.J.Pulp
Pap.
65 . Cordes-Tolle, M., Geller,A.N.. Baumgarten.

H.L., Papier 44(10A):VI8
(1990).

66. McKague A.B. and Reeve, D.W.,]
Pap. Sd., 17(4):}I15 (l99Ia).
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67. McKague, A.B. and Reeve, D.W., Nord.

Pulp Pap. Res.] 6(1):35 (l99Ib).
68. Sequeira,
A.}.
Chromatogr.Sd.
and Taylor,
L.T.,
29(8):351 (1991).
69. SCAN-CM 38R:95, "Pulp, papers

and
boards-Determination
of calcium, magnesium, iron, manganese
and copper,"
Scandinavian
Pulp, Paper and Board Testing Committee,
Stockholm, (1995).
70. SCAN-CM 54:95 "Pulps-Cadmium
and
lead," Scandinavian Pulp, Paper and Board
Testing Committee,
Stockholm, (1995).
71. Gorsuch,TT,
Tbe Destruction
of Organic
Matter, Pergamon
Press, Oxford, 1970,
pp. 19-39.
72. Kotz, 1., Kaiser, G., Tschopel, P., Tolg, G.,
Z. Anal. Chem. 260(3): 207 (1972).
73. Bailey,}.H.E. and Reeve, D.W.,] Pulp Pap.
Sd. 20(3):}83 (1994).
74. Saastamoinen,
S., Likonen,}.,
Neimo, 1.,
Paulapuro, H., Stenius, P., Pap. Puu 76(12):74 (1994).
75. Forsskahl,
I. and }anson,}.,
Pap. Res.]. 6(3):118 (1991).
Nord.
Pulp
76. Schmidt,}.A. and Heitner, C, "Use of UVVISible Diffuse Reflectance

Spectroscopy
for Chromophore
Research
on Wood
Fobres: A Review," 1993 TAPPI Pulping
Conference,
TAPPI PRESS, Atlanta, Book
2, p. 533.
77. Donkin,
Southern
M.}. and Garpatt,

D.C.F., Pap.
Africa 9(5):70 (1989).
78. Wallbacks, L.,Pulp Characterization

Using spectroscopy
and multivariate
data
analysis. Ph.D. thesis, University ofUmea,
Umea, Sweden, 1991.
693
79. Lennholm, H.,Investigations

of Cellulose
Polymorphs
byI3C-CP/MAs NMR Spectroscopy and Chemometrics,
Ph.D. thesis,
Royal Institute of Technology, Stockholm,
Sweden, 1994.
80. Weinstock, LA. ,Atalla, R.H.,Agarwal, U.P.,
Minor, }.L., Spectrochim.
Acta 49A(5/6):
819 (1993).
81. Weinstock,
LA., Minor, }.L., Reiner, R.S.,
Agarwall, U.P.,Atalla, R.H.,"FT Raman and
UV Visible Spectroscopic
Studies of a
Highly Selective Polyoxometa1ate
Bleaching System," 1993 TAPPI Pulping Conference Proceedings,
Book 2, p. 519.
82. Oldham,
P.B., Wang, I., Conners,
TE.,
Schultz,TP., "Rapid Secondary Analysis of
Lignin: A review of NIR and FTIR and a
Preliminary
Investigation
of Multidimensional Fluorescence
Spectroscopy,"
1993
Proceedings,
83. Martens, H. and Naess, T, Multivariate
Calibration,
Wiley, New York, 1989.
84. Wallbiicks, 1., "Characterization
of Chemical Pulps using Spectroscopy,
Fibre Dimensions and Multivariate Data Analysis,"
International
Symposium
on Wood and
Pulping Chemistry
Proceedings,
CTAPI,
Beijing, 1993, Vol. II, p. 802.
85. Ek, M., Some Aspects on the Mechanism
of Photoyellowing
of High-yield
Pulps,
Ph.D. thesis, Royal Institute ofTechnology,
Stockholm, Sweden, 1992.
86. Backa,S. and Brolin,A.,
(1991).
Tappt]
74(5):218
87. Gellerstedt, G. and }osefsson, T, "The Use

ofFT-Spectroscopy
and Chemometrics
for
the Analysis of Wood Conponents,"Third
European Workshop on Ugnocellulosics
and Pulp, Extended
Abstract,
Swedish
Pulp and Paper
Research
Institute,
Stockholm,
1994, p. 179.
SECTION VB:

Chapter 2:
Brightness: Basic Principles
and Measurement
Byron Jordan
Pointe-Claire, PQ
1. Introduction
697
2. Meaning and interpretation

of brightness
2.1 Brightness as an optical property. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2 Brightness and chromophore concentration. . . . . . . . . . . . . . . . . . . . . . . . .
2.3 The role of light scattering in brightness. . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4 Upper brightness limit in bleaching
2.5 Fluorescence and brightness. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.6 Whiteness and brightness
2.7 Color removal. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . .
697
698
699
701
702
703
704
704
3. Brightness measurement
3.1 Brightnesswavelength
3.2 Instrument geometries.
705
705
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 707
4. Sample preparation
712
Glossary of optical terms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 713
695
Chapter VII 2: Brightness: Basic Principles and Measurement
Chapter VB 2:
Brightness: Basic
Principles and
Measurement
1. Introduction
Brightness indicates the level of success
in a bleaching operation. Bleaching chemically reduces the concentration of lightabsorbing
constituents
so that paper
reflects more light. Improved reflectance
is both the purpose of bleaching and the
means of monitoring its progress. Brightness, as a particular kind of reflectance,
belongs to a family of measurements based
on the interaction of light with paper.
Light interacts with paper or pulp sheets
in various ways: it may pass through, be absorbed and converted into heat, be absorbed and released again as lower energy
fluorescent light, reflect from the first surface encountered
as in gloss, or diffuse
through the paper to exit eventually from
one side or the other. Only light that actually penetrates the sheet can experience
absorption and influence the paper's color
in general and brightness
in particular.
Gloss, a mirror-like first-surface reflectance,
provides the papermaker with a valuable
index of surface roughness but complicates
brightness measurement.
Another optical
interaction
that complicates
brightness
measurement is fluorescence. Fluorescent
additives in paper absorb invisible ultraviolet light and replace it with visible blue light
that enhances brightness. Once light penetrates the paper sheet, it has the opportunity to reflect from fiber surfaces, scatter
from fines or filler, or be absorbed by fiber
wall constituents. If the likelihood of scattering is much greater than the likelihood
of absorption, most of the light will eventually exit from the illuminated side of the
sheet. Light that diffuses out from the illuminated side of the paper is designated dif.
fusely reflected light. The term "diffuse
reflectance" is used because the direction
of the exiting light beam has become more
697
random and is independent of the angle of

illumination.
Diffuse reflectance
can be combined
with another optical measurement, opacity, to determine the separate contributions
of scattering and absorption to reflectance.
Opacity is the ratio of diffuse reflectance
measured on a single sheet of paper backed
by a black material to that measured with
the sheet backed by a white material. Opacity tells the papermaker if a paper sheet can
mask black printing on the page behind it
(1).
Because some readers interested
in
bleaching may be unfamiliar with the terminology describing optical interactions
and optical properties, a glossary of optical
terms can be found at the end of this
chapter.
2. Meaning and interpretation

of brightness
"Brightness" is a precisely defined measurement of the reflectance of visible blue
light from a pad of pulp sheets or an opaque
stack of paper or paperboard (2). Brightness was initially designed to monitor the
effectiveness of bleaching.
Unbleached
paper or board appears
brown because blue light is absorbed by
chemical
constituents
called "chromophores." Bleached paper has a lighter
or whiter hue because it reflects more blue
light than it did before bleaching. Bleaching increases the amount of blue light reflected by the paper by chemically lowering
the concentration of chromophores absorbing that light. In terms of product performance, bleaching success is measured by
the improvement
in reflectance
and, in
terms of the process chemistry, is indicated
by the reduced concentration
of chromophores in the paper or pulp sheet.
Over sixty years ago a group of TAPPI
members met to design a reflectance measurement to monitor bleaching effectiveness. They chose an existing optical setup
and found a commercial Wrattan ftlter that

passed blue light. A calibration procedure
was agreed upon and an industry standard
was written.The measurement was termed
698
Diffuse surface
reflectance
Gloss
------
~L
I
(a)
(b)
Diffuse internal
reflectance
Diffuse internal
transmittance
~ \~
,1/
(c)
"brightness." Over the next decade, brightness began to be specified in contracts and
regulations. By 1950, brightness measurement had become commonplace for paper
as well as pulp and remains so to this day.
It is still the only reflectance measurement
performed at some mills. Because brightness had been designed only as a tool to
monitor bleaching, its broader use as an
index of paper whiteness has led to some
inevitable confusion and controversy.
2.1 Brightness as an optical property

Brightness is a particular variety of reflectance and is related to the other optical properties of paper or pulp pads. When
a light ray encounters an interface, such as
a window surface or pulp fiber surface,
some of the light enters the material and
some reflects mirror-like from the surface.
All light rays entering a paper sheet must
pass through such a surface before they can
experience absorption inside the material.
The fiber surfaces present regions called
"facets" that are mostly aligned with the
plane of the sheet in a glossy paper (3). The
mirror-like reflectance is termed "gloss" and
is illustrated in Fig.la. If the facets are more
randomly oriented, the individual reflections disperse in many directions as shown
in Fig. Ib (diffuse surface reflectance)(4).
Although it typically contributes only about
2% of the total diffuse reflectance, even the
blackest dye component of ink cannot drive

the diffuse reflectance below the value of
the surface diffuse reflectance. Ink printed
on glossy paper may appear blacker than
ink on a matte paper because the surface
reflectance goes over the reader's shoulder
as gloss and does not meet the reader's eye.
Once the light ray penetrates the first surface of the paper, it diffuses inside the sheet
until it is absorbed or emerges as diffuse
reflectance (Fig. I c) or diffuse transmittance
(Fig. Id). Color is imparted to the paper
when the material selectively absorbs some
wavelengths of light from the diffuse reflectance or diffuse transmittance.
Brightness
illumination
~ted
~I
Diffuse illumination
~/~
I
Fig. 2. Sebertullic flprr

Illustrating
diffuse illumination.
collimated
and

is a form of diffuse reflectance, at a particular wavelength, tuned to the absorption of
light by chromophores
mainly present in
lignin. The reflectance of a paper sheet is
slightly different if the light is collimated
(t.e. the rays are all aligned in the same direction) or diffuse as illustrated in Fig. 2.
Separate measurement standards apply to
these two illumination modes (5). Because
light can often penetrate a single sheet of
paper, diffuse reflectance from a sheet also
depends upon the reflectance of the backing. H the paper is backed by a black body,
the reflectance is denoted R.. and if backed
by a white surface, it is denoted R., as illustrated in Fig. 3. H the sheet is backed by
enough additional sheets of the same material that the pad transmits no light, the difRoo
699
fuse reflectance is termed the "intrinsic reflectance

factor" and designated as R~ .
Brightness is measured as the diffuse intrinsic reflectance factor. The ratio of R.. to R~
is termed the "paper backing opacity" and
indicates how well a sheet of paper can
mask printing on its reverse side (1). The
absorption
that lowers brightness
also
makes the sheet more opaque.
2.2 Brightness and chromophore concentration

The reduction in chromophore concentration is not proportional to the change in
brightness but can be calculated easily from
the brightness. It takes very little colorant
to reduce the reflectance of a very bright
paper. Figure 4 shows the form of the re-
Ro
700
flectance loss (brightness) as a function of

chromophore
concentration.
From a
bleaching point of view, it is more instructive to think of brightness increase as a function of chromophore
removal. Figure 5
shows brightness as a function of the chromophore fraction removed from a pulp having an initial brightness of 20"/0.In this case,
the brightness increases rapidly as the last
chromophore
remnants are removed. In
Figure 6, brightness is shown as a logarithmic function of the remaining chromophore
concentration. When only 1% of the chromophore concentration
remains (a logarithm of -2), the brightness exceeds 83%;
100
90
80
70
iii
(/)
60
-~
50
40
"5
d5
Black backing
when half of that remnant is removed, the

brightness exceeds 87%.
Light falling on a pad of paper may be
absorbed and remain inside the sheet, pass
through the sheet, or reflect back out
through the surface it entered. If the pad is
sufficiently thick that no light can pass
through it, light is absorbed or reflected.
Once it enters a pad of paper, light may diffuse as far as necessary to be absorbed. The
likelihood of light diffusing back to the entrance surface and reflecting out depends
on the number of opportunities
the light
has to scatter and change direction before
it is absorbed. Within a tiny increment of
30
20
10
White backing
o
Opaque pad of
the same paper
Fig. J. SebetMtk
~
iii
(/)
Q)
c:
II4grtIm
of
1I.Il-'
sbed
INdh8gs
Oft IIgbt reflt#nu:e.
Fig. 5. ReWlmlslnp
betrl1eer8 brlgbmess
100
90
80
90
60
30
0.4
0.6
of chromophores
IIIUI cbromopbore
0.8
removed
remoIIIIl.
80
70
C>
.;::
tbe e.llt
0.2
Fraction
100
50
.s::.
sIItnring
(/)
(/)
-~
40
"5
d5
70
60
50
40
30
20
20
10
o
10
o
o
0.2
0.4
0.6
0.8
1.0
1.2
k/s (Proportional to chromophore concentration)
Fig.4. RelMlmrsbipbetrl1eer8
brlgbmess au ebromojJboreetnU:MtrYItimte~
~ (ItIs).
0.5
-log(Fraction
Fig. 6. Relatlmrsblp betrl1eer8 brlgbmess
1.5
chromophore
IIIUI tbe logtlrltbm
remaining)
of ebromopbore
removal.
Chapter vn 2: Brightness: Basic Principles and Measurement

diffusion path, the likelihood of absorption
is termed Uk"and the likelihood of changing direction is termed Us";the reflectance
of an opaque pad is a function of the ratio,
(kIs). The relationship between absorption
and reflectance is governed by the KubelkaMunk equations (6-9):
(k\=(1-[B/l00])2
sl
2(B/1 (0)
[1]
and
[2]
where B is the brightness in percent. The
absorption coefficient, k, is proportional to
the chromophore concentration (~13) aJ:.ld
the scattering coefficient, s, is determined
by the fiber dimensions and the degree of
interfiber bonding. Because bleaching has
relatively little influence on the scattering
coefficient, k/s can be expressed as follows:
step. For example, if the ratio of (kIs) values before and after bleaching is 0.4, then
60% of the chromophores
entering that
bleaching step have been removed.
When reflectance at other wavelengths
is substituted for brightness, k and s are
functions of the wavelength. When more
than one chromophore
contributes to the
brightness, the absorption coefficient is the
average of the constituent absorption coefficients weighted by the respective chromophore concentrations. Recent work (14)
suggests an alteration of the Kubelka-Munk
equations that merely reduces the k value
by half, but this has no effect on the interpretation used here.
[3]
where c is the chromophore concentration
and q is a proportionality constant. IT the
brightness is measured before and after a
bleaching step and the corresponding
(kIs) values are calculated, the ratio of these
(kIs) values is equal to the fraction of the
chromophores
surviving that bleaching
2.3 The role of light scattering

brightness
Light ray dispersal by scattering
~?-/p,\"
diagtYlm
illustrating
ligbt ray dhperstIl
in
When a board is sawn, the sawdust appears whiter than the board. Similarly, the
more wood meal is ground, the lighter it
appears or, if colored glass is powdered, the
powder appears much whiter than the glass
because finer powder offers more opportunity for light to scatter. Chemically, the
sawdust is the same as the board, but the
ground material is brighter.
Because the brightness or intrinsic reflectance factor at another wavelength is only
a function of the ratio (kIs), a pulp with
20"10more scattering can also contain a 20%
higher chromophore
concentration
and
Light ray dispersal by multiple reflectance
Fig. 7. Sebemstic
701
",,,ltillie reflectam:e .1Id scattering.
702
exhibit the same reflectance. For example,

a mechanical pulp may contain twice the
concentration of chromophores as a chemical pulp having the same brightness because mechanical pulps often display twice
the amount of scattering as a chemical pulp.
The scattering coefficient indicates the
likelihood that an optical discontinuity will
cause light to change direction within some
increment of its diffusion path. A bonded
interface between fibers is not a discontinuity and does not reflect the light (15).
True scattering redistributes
collimated
light in a wide range of angles in a single
step as illustrated in Figure 7. Filler, tiny
voids, surface asperities, and some fines are
smaller than the wavelength of visible light
and scatter light readily. In pulp sheets, the
optical discontinuity encountered is more
often the gently curved mirror-like surface
of a fiber-tOoair interface. These facets are
several microns wide and reflect light
specularly like a mirror, but a collimated
beam of light can be dispersed into random
orientation quickly by multiple reflectance
from a random hall- of- mirrors inside the
paper. Multiple reflectance and scattering
both disperse collimated light and both
enter Kubelka-Munk theory in the same
manner. The main difference is that the
wavelength
dependence
of scattering
comes from interference effects in true scattering and from the index of refraction in
the case of multiple reflectance. Lepoutre
et al. (16) have discussed true scattering
from voids in paper; Scallan (17, 18) and
Olf (1~21) have modeled multiple reflectance from layers of discrete fibers. Neither scattering nor reflectance occurs when
fibers are bonded to themselves or other
fibers (15). light can reflect from the internal surface of uncollapsed lumen or from
unbonded external fiber surface (18). Fiber possibilities can be combined in the
following equation (22):
(2<onap~ -RBA)
s <X fiber thickness
[4]
where 'collapse" is the fraction of lumen

surface dosed by internal bonding and the
relative bonded area. RBAis the fraction of
external fiber surface made transparent by
interfiber bonding. The scattering coefficient is determined by the fiber thickness

and by the degree of sheet consolidation.
The thickness of chemical pulp fibers is
determined by the wood species and the
pulp yield; the thickness of mechanical pulp
fibers is a function of energy input and
pulping conditions. Beating softens fibers
and increases bonding. As the bonding increases, the change in scattering coefficient
causes a brightness loss.
2.4. Upper brightness limit in bleaching
Middleton and Scallan (23) have found
that most fully bleached kraft pulps have a
residual absorption coefficient ranging from
0.2 m2fkg to 0.1 m2/kg and a value of 0.15
m2fkg is consistent with the reflectance of
a variety of pulps. Although this range is
narrow in absolute terms, an absorption
coefficient of 0.1 m2fkg corresponds to only
half the chromophore
concentration
represented by the 0.2 m2fkg upper limit value.
Assuming that all lignin chromophores have
been removed, this residual absorption can
be attributed to carbohydrates. Jordan and
Popson (24) have found the same minimum
absorption coefficient in newsprints measured at a wavelength of 1000 nm where
light absorption by lignin chromophores
is insignificant.
Given that fully bleached kraft pulps
reach about the same absorption coefficient
minimum, Middleton and Scallan (23) have
argued that the scattering coefficient, determined by the wood species, controls the
reflectance value. ITa constant level of collapse and bonding is assumed, SI can be
defined as the scattering coefficient of a
pulp having a 1.0 lJ.II1-thickfiber wall and
the brightness can be calculated from the
following equations:
s=-
SI
~icmn."
[5]
where t is the fiber wall thickness in microns. At small values of (k!s), the equation for reflectance as a function of (k!s)
can be approximated as follows:
B = 100"10(I-V 2~jn)
[6]
[7]
where k_ is the minimum k value of 0.15
m2 /kg. This equation reduces approximately to
Bow<= 100% - (8%) V t.mcro..
[8]
It should not be inferred from this equation

that the non-fluorescent brightness of fully
bleached spruce kraft pulp can never exceed 92%. The equation suggests only that
if a Eucalyptus globulus fiber having a cell
wall thickness ofO.9111D could be bleached
to a 92.5% brightness, then a Douglas-fir
fiber having a thickness of I. 5 I11Dwould
not be expected to be bleached to a brightness in excess of 90. This illustrates how
light scattering can limit the brightness attained by chromophore removal.
2.5. Fluorescence and brightness
Brightness
is an index of bleaching
progress because the chromophore concentration determines the absorption of light
which, in turn, reduces the reflectance.
Any light other than diffuse reflectance that
enters the detector of a brightness meter
confuses the intended relationship between
bleaching progress and recorded brightness. This extraneous light may be stray
light, gloss, or fluorescence.
Reflectance
is defined and calibrated as a ratio of the
intensity of the light flux reflecting diffusely
from the paper surface to the flux incident
on that paper surface. The scale is based
on the diffuse reflectance of a matte highiy
reflecting nonfluorescent reference material. Colorimeters used in standard brightness measurements exclude stray light and
most gloss, but fluorescence is a separate
issue.
Fluorescence
is a natural process in
which light is absorbed briefly by a molecule and re-emitted at a slightly lower energy (longer wavelength). When ultraviolet
light in the incident beam merely reflects
from the paper surface, it is excluded from
the detector by a filter or monochromator
that transmits only a specified range of blue
light (25). When that ultraviolet light is
703
demoted by a fluorescent process and exits the paper as visible blue light, it passes
through the brightness filter and is detected
as bonus brightness.
Fluorescence
may
come from at least four sources: I)An optical brightening agent may be deliberately
added to the paper to enhance the brightness reading and to make the paper appear
whiter; 2) Inclusion of fluorescent paper
in the furnish of recycled pulp may transfer
an unplanned fluorescence to recycled paper; 3) In some cases, the bleaching of
nonfluorescent recycled paper can produce
fluorescent entities (26, 27); 4) A very low
level of fluorescence is naturally present in
paper (28,29).
TAPPI's official brightness test method
(2) defines a fluorescence factor and describes its measurement. The International
Standards Organization (ISO) and the Technieal Section of the Canadian Pulp and Paper Association have written standards for
brightness measurement that exclude fluorescent papers from the scope of the standard (30, 31) The ISO reintroduces
fluorescence in a standard for whiteness
instead of brightness (32). Both theTAPPI
and ISO methods rely on a filter to absorb
nearly all incident illumination having a
wavelength
lower than 420 nm. TAPPI
brightness or ISO whiteness is measured
first with the shott wavelengths included
and then with them excluded.
Care is
needed in calibration because light with
wavelengths between 390 nm and 420 nm
is detected in the brightness measurement
and insertion of a 420 nm high-pass filter
removes that light. Separate calibrations are
needed in which ultraviolet light is included
and excluded. Use of a 390-nm high-pass
filter might be preferred except that the
fluorescent whitening agents used in paper
are also excited by some blue light as well
as ultraviolet light.
Fluorescence often increases the brightness or whiteness by 10% or more with the
result that the apparent brightness may
exceed 100%. The fluorescent "bonus" to
the reflectance increases in proportion to
the amount of ultraviolet light in the illumination. The TAPPI Official Brightness Test
704
Pulp Bleaching
-Principles
and Practice
Method (2) prescribes a filtered incandescent lamp. The International Commission

on illumination (aE) standard illuminant "A"
or "C" contains about the same proportion
of ultraviolet light as a quartz halogen lamp,
but the CIE DM illuminant simulates an average daylight and contains much more ultraviolet light. Xenon lamps are often used
to simulate the CIE DMilluminant,and they
must be strongly filtered in the ultraviolet
to bring the fluorescent excitation down
to the level of an "A"source. The fluorescent component of ISO whiteness is measured with a simulated CIE DM source, and
the bonus from fluorescence
is much
greater.
Because brightness is used in the marketplace as a value attribute for paper as
well as for pulp, it is tempting to measure
the brightness of fluorescent paper using
as much ultraviolet light as possible to "bring
the numbers up" and maximize the advantage of the fluorescent whitening agent.
This practice can distort the apparent value
of the paper if the customer's end-use environment does not excite as much fluorescence as the colorimeter
used in the
measurement.
In particular, the relative
visual whiteness ranking of competing papers is not the same outdoors as indoors.
The TAPPI Optical Properties Committee
has tested this statement by visually ranking fluorescent papers in many office environments (33). Colorimeters measuring
brightness or whiteness with quartz tungsten lamps ranked the papers in close agreement with that of a panel of judges, but
colorimeters
using simulated D6Sagreed
poorly with these indoor assessments.
2.6. Whiteness and brightness
The term "brightness" is an unfortunate
misnomer. When undyed pulp is bleached
to higher brightness, it does look lighter but
the relationship between brightness and
perceived lightness does not apply to colored papers. lightness and whiteness are
colorimetric factors and perceived color
depends upon the relative amounts of red,
green, and blue light the eye detects. The
average eye as defined by the CIE Standard
Observer (34) can be approximated in a
colorimeter using the "tristimulus" values

X (red), Y (green), and Z (blue). The X, Y,
and Z values vary independently and define
a three-dimensional color space (35). The
perception of "lightness" depends upon the
green (Y) sensation that spans the entire
visible spectrum but peaks midway between 500 om and 600 nm. Because the
blue reflectance (Z or brightness) is generally independent
of the green (Y) reflectance, brightness
and lightness
are
essentially independent. In the special case
of undyed paper, the green reflectance is
always at least as great as the blue reflectance, so a higher brightness
implies a
higher tristimulus Y value. Some specifications include the tristimulus Y value (also
termed "luminous reflectance") as a separate lightness index (36).
Even if the luminous reflectance
(Y)
measures the relevant wavelength range, it
still does not have an intensity scale that
matches perception. The CIE L* value, calculated from the cube root ofY provides a
more relevant intensity scale:
L'
= 116
yl/3
16
[9]
L*is a useful index of lightness for gray and

colored specimens, but near-white papers
appear whiter when they have blue tint. A
CIE committee
has experimented
with
equations that matched this bias. A CIE
whiteness was defined (32, 33, 37-42) in
terms of the color coordinates. When the
whiteness of a highly fluorescent
white
paper is measured under conditions that
excite as much fluorescence as a CIE D 65
iIIuminant, the fluorescent
intensity not
only enhances the reflectance but often
exaggerates it in the blue portion of the
spectrum. The whiteness benefits from the
extra intensity and the blue tint.
2.7. Color removal
Bleaching is a form of chemical treatment
aimed at the removal of color in natural or
undyed pulps. Chemical treatment is also
used to decolorize dyes in recycled paper.
Much of this color is outside the blue part
of the spectrum spanned by brightness;
therefore, several combinations
of color
coefficients have been proposed to measure

net color removal (43). As noted in Subsect.
2.2, (k/s) is proportional
to the chromophore concentration.
When (k/s) is
measured as a function of wavelength, this
spectrum contains peaks associated with
the individual chromophores.
The disappearance of these peaks is an index of color
removal with stronger quantitative ties to
the accompanying chemical changes.
Brightness is also used to indicate the
darkening induced by residual ink in recycled paper or pulp pads. When the brightness is above 50"16,the relationship between
ink concentration and reflectance is curvilinear enough to warrant converting brightness to (kIs) values. This analysis is even
more effective ifbrightness is replaced with
a reflectance measured at about 950 nm in
the near infrared (24). At this wavelength,
the contribution
from the lignin chromophores is insignificant and the ink contributes most of the absorption.
3. Brightness measurement
3.1 Brightnesswaveiength
TAPPI and 150 brightness
The wavelength distribution was originally defined by a commercially avaIlable
Wratten filter. The central wavelength is
457 nm and the filter transmittance
is
greater than 50% from 440 nm to 480 nm
as shown inTable 1. Because a fluorescence
measurement is included in the same test
method, the relative intensity of incident
light in the ultraviolet spectrum is also specified. Table 1 can be taken as a specification
to be matched by a gelatin filter or it can be
used directly as a weighting function to calculate brightness from a reflectance spectrum. The 5-nm interval is sufficient
resolution for most paper spectra, but it suffers in comparison to the CIE colorimetric
functions (35). In common colorimetric
practice, reflectance is measured at 2-nm
intervals, multiplied by tabulated weighting
functions at the same wavelength intervals,
and integrated by simple summation. If the
reflectometer
records data at 10-nm or
larger intervals, then implicit interpolation
is used for the integration (44,45). Unfortunately, the choice of integration algorithm
705
706
TIIbk 1. SJIIrtIl mgbts of ImgblJlessIIfIIltrlsti_IllS Zfruletions.

Wavelength
Microns
0.395
0.400
0.405
0.410
0.415
0.420
0.425
0.430
0.435
0.440
0.445
0.450
0.455
0.460
0.465
0.470
0.475
0.480
0.485
0.490
0.495
0.500
0.505
0.510
0.515
0.520
0.525
0.530
0.535
0.540
0.545
0.550
0.555
0.560
0.565
0.570
0.575
0.580
0.585
0.590
0.595
0.600
OJ~)j
0.610
0.615
0.620
Brightness
%
0
0
0
1
2.9
6.7
12.1
18.2
25.8
34.5
44.9
57.6
70
82.5
94.1
100
99.9
88.7
72.5
53.1
34
20.3
11.1
11.1
5.6
2.2
0.3
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Tristimulus
Z
2.03
3.81
6.18
11.64
20.83
36.22
58.30
77.74
91.05
98.02
100.01
99.42
97.85
93.65
85.73
72.24
58.45
45.61
34.57
26.10
19.82
15.26
11.91
8.88
6.27
4.39
3.21
2.37
1.67
1.14
0.75
0.49
0.32
0.22
0.15
0.12
0.10
0.10
0.08
0.06
0.06
0.04
O.Oj
0.02
0.01
0.01
100
90
80
EC!
Z and Brightness Functions
70
60
-0-0-
'ii)
3: 50
Brightness
Tristimulus z
.~ 40
Cij 30
CD
a:
20
10
o
o
0.1
0.2
0.3
0.4
0.5
Wavelength, 11Mmeters
can make a meaningful systematic difference and has been discussed within the ISO
with respect to ISO brightness.
The first instrument used for ISO brightness measurement was the Zeiss Elrepho,
and the combined effect of its detector, integrating sphere, lamp, and filter was a
weighting function having a central wavelength of 457 nm but which did not match
the details of the function in Table 1. The
SCAN brightness standard (46, 47) used the
Elrepho distribution as the new norm, but
the Technical Section of the CPPA, and later
the ISO,accepted the Elrepho as an approximation to the norm defined byTable 1. This
created some confusion as newer filter-type
colorimeters and abridged spectrophotometers having a choice of norms came into
use. All ofthis led to a call by some to abandon the brightness function and substitute
the better-defined CIE tristimulus Z measurement (48,49).
Brightness and the tristimulus Z value
Brightness is specific to the paper industry, but tristimulus colorimetry is applied
more widely. Brightness and the blue (Z)
colorimetric value sense the same part of
the spectrum as shown in Fig. 8. The Z function is better-defined
and better-studied
because of its nearly universal application
in colorimetry. At one point a decade ago,
it was proposed within the ISO to generate
0.6
0.7
standards for Z reflectance and brightness

to be run in parallel to determine if usage
shifted to the Z value. Although the ISO
did not act on this beyond the committee
level (48), the Technical
Section of the
CPPA did generate a parallel standard using
Z (49), but the popularity of Z has yet to
materialize.
Brightness and Z are not entirely redundant. The difference can be seen, when
attempts are made to calculate brightness
from Z. To do this, an arbitrary but realistic
reflectance curve R(I) is taken and represented by a Taylor's series polynomial
around the wavelength 457 nm:
[10]
where the coefficient
an =
1 do
R(I..)
n. WI.
'''''n
an is given by
[11]
Although an infinite order polynomial such

as this should represent the reflectance
curve perfectly, a quadratic or cubic polynomial should more than suffice for this
demonstration.
The reflectance is multiplied by the brightness function F(I) inTable
1 and integrated:
B
= fdA.F(I..)R(I..)
[12]

B
=L a" JdA.F(A.)RQ.-457Y'
[13]
Here the integral term is simply the nth

moment of the brightness function F(l) calculated around the wavelength 457 om.
Both functions are normalized to read 100%
for a perfect reflector and the wavelength
is expressed relative to 0.457 J.UI1for better
convergence.
The nth moment of the
brightness function can be termed MoBand
the corresponding moment of the z(l) function, M; , because
Z =L a"M~
[14]
and
B=Z+Ln=o a,,(M: -M~
[15]
Table 2 shows the first few terms of the difference in moments. In practice, the fiist
few terms can be written
B
Z + bl x slope + bl x curvature
[16]
'"
where the b coefficients are constants.
When the brightness and Z values are compared for newsprints (50), where the slopes
and curvatures of the R(l) curves are nearly
identical, the two color indices are highly
correlated. In a bleaching sequence, however reflectance increases with the extent
of bleaching and the slope of the reflectance curve becomes progressively less
steep. Therefore, the relationship between
brightness and Z varies with bleaching level.
3.2 Instrument geometries

TAPPI brightness (directional illumination)
The International Commission on illumination defines two main families of colorimeters or reflectometers
(35): The first
shines incident light at an angle of 45 to
T8ble 2. Dlf/ernce
la ..o..eats
trlstiItI8111S Z IIrUl brighlJlas
bdftleea tbe
jrutdImts.
Difference
Brightness
x 100
x 100
x 100
First
0.01605
.{).34118
0.35723
Second
0.om4
0.06933
.0.03398
Third
.{).00015
0.00041
.{).00056
Fourth
0.00005
0.00015
.{).00010
.M2mm1
707
the specimen surface and views at 0" (norma! or perpendicular to the surface). The
second instrument type diffuses the light
around the white inner surface of a spherical cavity and allows this diffuse light to fall
at all angles onto a specimen placed at an
aperture in the sphere. The light is detected
normal to the surface (0") or nearly normal
(8") to the surface. ISO brightness uses only
the integrating sphere geometry in Standard
2470. Although TAPPI has official test methods using both geometries (T 525 uses an
integrating sphere and T 452 uses directional illumination), the term "TAPPI brightness" usually refers to the directional
brightness.
Description of the geometry
As shown in Fig. 9, the light from an incandescent bulb is directed onto the paper
at 45 to the surface with a cone of illumination having a half angle 11.5 and viewing is within one-half a degree of the
perpendicular
direction with a half angle
of 22.5. The dimensions are such that light
from the rim of the 9.53 mm diameter
specimen aperture Is not viewed by the
detector. The dimensions, and particularly
the haIf.angie defined inTest MethodT 452
for brightness,
are specified much more
precisely than in the corresponding method
T 524 for colorimetry.
Brightness scale and calibration
It is important to distinguish between
relative rejlectam:e, absolute dtffuse reflectance, and absolute directional reflectance.
Barium sulfate powder may reflect about
99% of all the diffuse visible light falling on
it. This number corresponds to absolute
dtffuse reflectam:e and can be compared
with the reflectance of a fictitious "perfectly
reflecting diffuser" that reflects all diffuse
light. The perfect diffuser is also said to be
"Lambertian" in that it reflects light at all
angles with equal likelihood. Barium sulfate is not perfectly Lambertian and reflects
about 2% more light at mid-angles around
45 than it does for glancing angles or even
angles near normal (51). The reflectance
of the material for 45 illumination compared with the reflectance of a perfect dif-
708
fuser at the same angle is the absolute directional reflectance.

Because it is not
Lambertian and reflects more light in the
medium angles than at extreme angles,
barium sulfate can have an absolute directional reflectance of about 101% without
violating the laws of physics. If a scale is
defined in which the reflectance of a particular material is declared to be 100%, the
scale is termed "relative refleclam:e." Directional TAPPI brightness was originally
defined with a relative scale based on magnesium oxide. When the long-term stability of this chemical
became suspect,
absolute reflectance was adopted as a check
on the measurements based on this scale.
The original test method also set up a calibration system operated by the Institute of
Paper Chemistry (now the Institute of Paper Science and Technology). Calibrations
are also now provided by the Technidyne
Corporation forTAPPI brightness.
Sources of systematic error
The crn specifications for this directional
illumination geometry (35) allow the instrument maker greater freedom and, in the
three decades between introduction
of
T 452 andT 524, a variety of configurations
were applied to the measurement of paper
color. However, reflectometers with different illumination or detection cones may
differ significantly in the reflectance measured (52). Suppose, for example, that the
illumination cone includes light ranging in
incidence angle from 40" to 50" and that

the increase in reflectance from 40" to 45
is less than the increase from 45 to 50".
The effective reflectance
angle is then
greater than 45 and increases with the illumination cone. Because the framers of the
brightness method (T 452) were in a better
position to specify the geometric
constraints than those framing the colorimetry
method (T 524) were three decades later, it
should be easier to obtain agreement among
colorimeters configured to the more specific brightness
method (T 452) than
among general colorimeters (T 524).
TAPPI Method T 452 specifies that the
light enters the paper at 45 and is observed
normal to the surface and not the opposite.
A century ago, Helmholtz demonstrated
that the angles of illumination and detection could be interchanged without changing the reflectance provided the entering
and exiting beams had the same polarization. Over the years, the stipulation about
polarization was forgotten and the illumination and detection angles were interchanged confidently
until Clarke (53)
challenged the practice. In the worst case,
where the entering and exiting beams are
set to opposite linear polarization, even the
reflectance of a matte pressing of barium
sulfate powder differs by about 8% between
the "forward" and "reversed" configuration.
Although colorimeters
are not designed
with this kind of polarization reversal, the
Detector
Filters
Paper
Fig.'. SckmMie tlMgtwmillllStrtltillgtbe ill_IutUm
_.
system fIHtl to __
"'m:HOIu" (TAPl'1)bright-
Chapter vn 2: Brightness: Basic Principles and Measurement

mirrors and optical elements in most instruments introduce a partial po1arization of the
light beam. Only a little partial polarization
is needed to cause a commercially significant systematic error in brightness (54).
Another source of systematic error is the
so-called translucency
effect (55). The
brightness method requires that one measure a pad of paper thick enough to be
opaque. If the specimen has low opacity, a
very thick stack of sheets may be required.
In this case, light from the leading edge of
the incident beam moves closer to the center of the aperture as it penetrates the specimen, casting a shadow of the beam edge
into the depths of the specimen pad. Unless much more paper surfilce is illuminated
than is detected, some of this shadow appears in the detection cone. The apparent
reflectance loss disappears when the paper
is more opaque.
The aperture specified in Method 452
exposes less than 1 cm2 of the paper surface to the detector. This is an order of
magnitude less surface than is sampled in a
single ISO brightness measurement.
If the
paper surface is mottled, many measurements oITAPPI brightness must be recorded
to average out these surface nonuniformities.
If the specimen fluoresces, then the relative intensity of ultraviolet light at different
wavelengths
must begin and remain in
agreement with the tabulated values in the
test method.
Any combination of detector and amplifier can be subject to some "photometric
nonlinearity." When the light incident on a
detector is precisely doubled, the detected
signal must also double. This property is
termed "photometric
linearity" (56, 57).
The test method requires that linearity remain within 0.1%.
The spectral sensitivity inTable 1 applies
to the combined effect of the detector sensitivity, the lamp spectrum, and filter transmittance (if a filter is used).
ISO brightness (integrating sphere)
The geometry of TAPPI brightness corresponds to reading paper with a lamp behind the the shoulder, but the geometry of
ISO brightness corresponds to reading with
709
indirect lighting in a white room. As illustrated in Fig. 10, light is forced to diffuse
about inside a spherical white cavity before
it impinges on the paper specimen. light
fal1son the paper from nearly all angles. ISO
brightness is the standard form of brightness measurement in Europe and Canada
and much of the world.
Description of the geometry
The ISO brightness geometry is specified
in ISO Standards 2469 and 2470 and is more
restrictive than the CIE requirements for
reflectometers
employing
integrating
spheres. The diameter of the measuring
aperture is 30 mm to allow adequate sampling of the paper surface; the sphere diameter is 150 mm, but the total area of all
apertures must cover less than 10"16of the
sphere surface. The paper is viewed normal (perpendicular)
to its surface. Presently, colorimeters having smaller spheres,
or those viewing 8 from the normal are excluded from the standard.
The detector aperture is surrounded by
a black portion of the sphere surface that
subtends a half angle of 15.5 as measured
from the specimen surface. This region is
called a "gloss trap" and is either painted
matte black or can be an aperture in the
sphere opening to the black interior of the
instrument. The aperture form of gloss trap
is more popular in instruments excluded
from the ISO brightness standard because
they view 8 from the normal (47). The
purpose of the gloss trap is to exclude
specular (mirror-like) gloss reflectance from
the measurement.
When the gloss trap is
working well, the colorimeter
registers
nearly zero reflectance when a good mirror is placed at the specimen position. In
practice, 2% to 4% reflectance has been
observed (58) indicating that gloss exclusion is good but far from perfect. Agreement among colorimeters from different
manufacturers would improve if gloss traps
were absent or were identical (59), but
gloss exclusion is needed for several reasons: Creation of a glossier surface in a
brightness pad should not be a substitute
for more effective bleaching. Under usual
viewing conditions, specularly reflected
710
Pulp Bleaching
-Principles
and Practice
light does not reach a reader's eyes so

glossier paper does not look brighter. When
the brightness meter detects much of the
gloss, the assigned brightness is inconsistent with the relative perceived quality of
the product. Also, the Kubelka-Munk analysis assumes that gloss is excluded. Lastly,
directionalTAPPI brightness excludes gloss
and ISO brightness should share this attribute.
Despite the advantages of gloss exclusion, after the gloss trap provision became
part of the ISO brightness standard mills
were slow to install the traps in their meters
because the trap caused the brightness
value to decrease by as much as 2%. Even
after the market expectations adjusted to
the scale change, the last mills to change
enjoyed a temporary competitive advantage.
The gloss trap also changes
the
instrument's
response to fluorescence.
Malthouse and Popson (42) have pointed
out that the gloss trap enhances fluorescence excitation.
A slightly fluorescent
paper that loses about 1% brightness from
the loss of the gloss intensity regains that
loss from the gloss trap's fluorescence enhancement. A highly fluorescent paper may
read almost I % higher after the introduction of a gloss trap (42). Because gloss traps
differ in their effectiveness for gloss exclu-
Fig. 10.Sebem411e IlMgrwm IllflStrt1118gtllelll"mIIrtItItm
sion, they also differ in fluorescence

enhancement.
The concern about "Helmholtz reciprocity," mentioned with respect to the directional brightness, does not apply to this
geometry. Perpendicular illumination and
diffuse viewing can be substituted for the
standard configuration with more confidence than in the case of directional brightness.
Reflectance scale and calibration system
Although absolute reflectance was used
to support the relative magnesium oxide
scale for directional brightness, the ISO
chose to change the reflectance scale itself
to absolute reflectance (60-64). When this
was implemented, the indicated brightness
values on all paper products decreased to
98% of their initial value. For example, an
80% brightness dropped to 78. 5%. This
caused some confusion at the time because
national standards were not converted to
the ISO scale simultaneously.
10 principle, any competent laboratory
can determine its own absolute reflectance,
but great care is required with the result
that the measurement is usually made in
national standards laboratories such as NIST
(USA), NRCC (Canada), and PTB (Germany). These three are mentioned because
they have agreed to maintain a consensus
system used to __
diffuse (ISO) brlgbmess.

value for absolute reflectance to be used in
conjunction with ISO Standard 2469. These
three standardizing laboratories determine
the absolute reflectance of some uniform,
matte, white, opaque materials and use
these to calibrate master colorimeters at
designated authorized laboratories including CI'P in France, sm in Sweden, KCL in
Finland, and PAPRICAN in Canada. Although the standardizing laboratories each
use a different absolute reflectance apparatus that also differs from the standard ISO
geometry, the master colorimeters at the
authorized laboratories must conform to the
geometric and spectral requirements ofISO
Standard 2469. Any scale adjustments to
the specifics of the ISO measuring conditions are made in the careful process .of
transferring calibration to the master colorimeters at the authorized laboratories.
Calibration transfer from the authorized
laboratories to the mills is then between like
instruments.
Sources of systematic error
The effect of different gloss traps is discussed above. As with directional brightness, photometric
linearity must remain
within tolerance.
Although it is a challenge to match the
tabulated spectral sensitivity function in the
directional brightness using the lamp spectrum, detector sensitivity, and filter function, the ISO brightness meter includes an
additional complication,
the sphere efficiency function. If the sphere lining has a
reflectance of r(l), the efficiency function,
Q(l), is defined as follows:
Q(t..)= P(t..)
I-p(/..)
P(t..)
Q(A.) =
I-p(t..)
[17]
[18]
If r(l) changes from 0.99 (99"10)to 0.98, Q

changes by a factor of two from about 100
to about 50. Q again decreases by a factor
of two as r decreases from 0.95 to 0.9 or
again between 0.9 and 0.8. Spheres coated
with pressed and sintered PTFE (poly-
71 I
tetrafluoroethylene)
maintain stable high
reflectance from visible wavelengths well
into the ultraviolet region. The more common barium sulfate paint, however, has a
reflectance that smoothly drops from about
0.99 for green light to about 0.80 well into
the ultraviolet region depending upon its
age. If the sphere yellows with age, the
effective wavelength of the spectrum-exciting fluorescence
is substantially altered.
Reflectometers
using integrating spheres
can correct for this sphere error by measuring the light intensity on the sphere wall
with one detector and dividing this into the
intensity registered from the specimen. The
correction is more complete if done wavelength by wavelength instead of with the
intensities
transmitted
by broad filters
where major sphere yellowing can bias the
effective filter function. The integral of a
ratio is not the same as the ratio of integrals
is shown below:
rdA.
Q(t..)F(t..)R(t..)
Q(t..)
'*
JdA. Q(t..)F(t..)R(t..)
Jdt.. Q(t..)F(t..)
[19]
The left side of this inequality corresponds

to the wavelength by wavelength correction for the sphere function followed by
integration with a weighting function (filter function) F(l). The right side corresponds to the ratio of reflected fluxes
through filter functions.
An intercomparison of colorimeters conforming to the requirements of ISO 2469
using a variety of papers indicated several
sources of disagreement (65). Differences
in calibration explained a small part of the
variance as did photometric linearity. When
colorimeters have different spectral bias,
they agree better in measurements made on
white or gray papers than for measurements
made on papers with higher (dR/dl) in the
relevant spectral range. This contributed a
significant fraction of the variance. Lastly,
colorimeters disagreed more in measurements made on fluorescent papers than in
measurements
made on non-fluorescent
papers because of differences in the ultraviolet content of the illuminating systems.
712
Differences between TAPPI (45/0) and ISO

brightness
(d/O)
Differences inTAPPI and ISO brightness can

be summarized as follows:
I) ISO brightness is axially symmetric, but
TAPPI brightness is sensitive to differences
in machine direction and cross direction.
Differences of about 3% are common.
2) ISO brightness ignores most of the gloss;
TAPPI brightness excludes nearly all the
gloss.
3) ISO brightness is based on absolute diffuse
reflectance; TAPPI brightness is based on
relative directional reflectance.
4) TAPPIbrightness measures the reflectance
at a single illumination angle (45); ISO
brightness includes all but the gloss-exeluded angles at an effective illumination
angle of 60" from the normal.
If there were no gloss or z-directional
gradient of scattering or absorbing power
from fines or residual ink, then in principle
the difference between TAPPI brightness
and ISO brightness would be a fixed function of reflectance
level (66) and the
reflectivity would resemble a photometric
linearity curve. That is, the difference between ISO brightness andTAPPI brightness
would be solely a function of reflectance
level. If the difference between ISO brightness and TAPPI brightness depended only
on the test instruments, one instrument
could be calibrated against another with
confidence.
In reality, the difference depends too much on surface structure, internal sheet structure, and fluorescence.
Popson (5) has compared reflectometers
from the same manufacturer conforming to
the TAPPI and ISO standards. Among both
non-fluorescent and highly fluorescent papers, he found the TAPPI brightness could
be as much as 0.3% lower or 1.5% higher
than the ISO brightness. The directional
values were significantly higher for a nonfluorescent-coated
offset, a fluorescent-uncoated offset, and unbleached kraft board.
In the ISO geometry, it is very important
that the paper be situated in the plane of

the measuring aperture. When the paper
is lowered even a mi1limeter away from the
measuring aperture, the reflectance de-
creases significantly. This sensitivity to paper positioning makes this measurement

much less forgiving of web oscillation on a
paper machine. The directional brightness
geometry is preferred for on-line detection.
Whatever geometry is used for brightness
measurements on a paper specimen must
take note of the fact that a single sheet of
paper is not opaque.
4. Sample preparation
Machine-made paper needs no special
sample preparation for brightness measurement except to ensure that the paper stack
is sufficiently thick to be opaque. The concern in preparing pulp for brightness measurement is to form a sheet in a way that
does not introduce measurement complications.
Some sample preparation steps complicate the measurement (67). The measurement is more representative of the pulp if
the sheet is uniform from top to bottom and
across the top. Slowly draining pulps can
form density gradients in fines or residual
ink from top to bottom. Swirling of the
slurry during drainage often results in nonuniform brightness across the sheet surface.
Drying without restraint permits shrinkage
together with crinkling of the sheet surface.
When the crinkled pad does not lie flush
against the aperture
of an integrating
sphere, it cannot be properly measured. If
the pH of the slurry is not appropriate for
the pulp components or the product enduse, the pulp may discolor. or filler may
coagulate and become less effective. Mechanical pulps or unbleached kraft pulp can
lighten by one or two brightness units per
pH unit change produced by souring. Souring is appropriate if the paper is manufactured under acidic conditions. Otherwise,
souring increases the discrepancy between
the brightness of the pulp pad and the
brightness of machine-made paper.
Standard practice in Canada calls for making a 4-g pad in the stainless steel deckle of
a standard sheet mold followed by restrained drying. The relatively fast drainage
lessens the sidedness of the sheet, but whatever sidedness is present is measured and
noted. The pulp is diluted in the sheet mold

with water at pH 6.5-7.0, and no attempt
is made to neutralize or sour the slurry although the pH is noted (68).
Following the ISO standard practice (69),
the slurry is soured to a pH of between 4.0
and 5.5 and pads weighing 2-g each are
formed in a Buchner funnel. The pads are
dried without restraint. If the sensitivity of
brightness to pH is great enough to make
souring worthwhile, the pH range specified above is too wide to ensure adequate
reproducibility. The backing IDter used in
the Buchner funnel prevents measurement
of sidedness. At the 1995 plenary session
of Isorrc6,
it was agreed to broaden IS
practice to include the standard stainless
steel sheet mold; the use of chelating agent
713
(Ie) An index of light

Absol:ption coefficient
absorption.
When multiplied by the basis
weight, it indicates the light attenuation per
unit path length.
Absolute diffuse reflectance
Reflectance measured with diffuse illumination (integrating
sphere), diffuse detection, or both in which
100% corresponds
to the reflectance
of a
perfectly reflecting diffuser.
Absolute directional reflectance
Reflectance
measured with single angles of illumination
and detection,such
as 45 illumination and
in which the 100% corre0 detection,
sponds to the reflectance
of a perfectly reflecting diffuser.
QE
International
Commission
on mumination (the initials come from Commission
International
de L' Eclairage), an international group of optical experts.
Color (colour)
A sensation
associated with
the sight of light in particular wavelength
ranges.
Colorimetrv
A process of objective measurement that corresponds
to the sensation of
color under
specified
viewing
conditions.
Collimated lilZht Light rays all aligned

same direction.
in the
was discontinued, but souring was maintained.

Practice within TAPPI permits a choice
of the Buchner funnel <T218) or sheet mold
method <T 272). In the Buchner funnel
method, the slurry is soured with acetic acid
to a pH within 0.1 unit of 5.0. A stack of 3g pads is placed between a glossy plate and
a pair of blotters and pressed to 350 kPa.
The backing IDter is peeled off and the pads
are dried under restraint in drying rings. The
sheet machine procedure <T 272) also provides restraint-dried 3-g pads but without
souring or pH adjustment.
These examples illustrate the variety of
sheet preparation procedures in use today.
A TAPPI committee task force is currently
reviewing the pH issue and related issues.
llluminant
An officially tabulated spectrum
of energy emitted from a physical source
like the diffuse light from the north sky or
the light from an incandescent
lamp. The
illuminant function is used for colorimetric calibrations.
Chromo!,hore
A chemical entity that absorbs
light at a specific frequency.
Intrinsic Reflectance Factor (Reo) Reflectance

from a sufficiently thick stack of paper or
pulp sheets that the addition of another
sheet to the bottom of the stack does not
change the reading.
Glossary of optical terms

Absol:ption of light Light intensity is attenuated by its conversion
into other forms of
energy.
714
A substance, usually dye or pigment,

that imparts color to materials.
Diffuse lilZht An ensemble of light rays, each

pointing in a different direction.
Diffuse reflectance
Reflectance
in which the
incident or reflected light is diffuse. It may
employ an integrating sphere or may simply sample the reflected light far from the
specular direction.
( surface) Light rays reflect
Diffuse reflectance
diffusely from the first surface encountered
without ever entering the material.
Ih't. An additive that reacts with a substance
like paper to bond chromophores
to the
substance chemically.
Fluorescence
High-energy
light is absorbed
and released as lower energy light. If the
higher-energy
light is invisible ultraviolet
light, and the released light is visible, this
process may enhance the brightness
and
whiteness.
Specular
reflectance
from the first sur-
face of the paper encountered by the light.

It indicates the smoothness of the paper
5urfa(;t,
Gloss trap A darkened portion of an integrating sphere designed to reduce the influence of gloss in a reflectance measurement.
Index of refraction
The ratio of the speed of
light in a vacuum to the speed of light in
the material.
When light encounters
an
interface between
regions with different
indices of refraction, the light may scatter
or refract.
Infrared lilZht Light with slightly too little
energy to be visible; light with a wavelength greater than 770 om.
Int~tinsz
s!,here Light reflecting repeatedly
from a white coating inside a hollow sphere
illuminates
paper situated at an aperture
of the sphere with light impinging equally
from all directions.
Lambertion illumination
Incident light from
all directions above the sheet with equal
likelihood.
Luminous reflectance
factor The intrinsic reflectance factor of light with a spectral distribution corresponding
to the sensitivity
of the eye. Tristimulus Y reflectance.
An index of how much light diffuses

all the way through the paper and back
again. Expressed as a ratio of the reflectance of a sheet of paper over a black backing to the reflectance
over a light backing,
it relates to how well a page can mask printing from the other side.
Scatterinsz of lilZht Light passing through

a
material changes direction so as to become
less collimated without any attenuation
of
the total light intensity.
(s) An index of light
Scatterin~ coefficient
scattering.
When multiplied
by the basis
weight, it indicates the likelihood of light
changing direction in a unit distance along
its path.
Source
A physical object that emits
Lamps and the sun are sources.
light.
Transmittance
The fraction of incident light
intensity that diffuses all the way through
a sheet.
Tristimulus functions The eye processes
red,
green, and blue light in separate sensory
channels, so the perception
of any color
can be factored into a combination
of these
three basic "stimuli." The average detection
efficiency of each channel per wavelength
is called its tristimulus function x(A.), Y(A.),
or zQ..).
Tristimulus
values The reflectances
of red
light 00, green light 00, or blue light (Z)
with the spectral distributions
of the corresponding
tristimulus functions.
Ultraviolet light Higher-energy
light with a
wavelength somewhat shorter than 400 om
that is invisible.
Wavelen~
The distance light travels during
one full oscillation
of its electric vector.
Light scatters
strongly
from structural
discontinuities
that are one-quarter
wavelength wide. Wavelength
is inversely proportional to the light energy.
Whiteness A colorimetric index that takes into
account the human bias for blue-whites
over pink-whites.
It applies only at very
high reflectance.
References
Refraction The path of light bends when the

light moves from one region to another
region if the regions have different indices
of refraction.
1. TAPPI Official Test Method T 519 om-91

"Diffuse opacity of paper (diG paper backing),"TAPPITest Methods 1994-1995,TAPPI
PRESS (1994).
Relative reflectance
A reflectance
scale in
which 100% corresponds
to the reflectance
of a reference material such as barium sul-
2. TAPPI Official Test Method T 452 om-92

"Brightness of pulp, paper, and paperboard
(directional reflectance
at 457 nm);TAPPI
Test Methods
1994-1995,
TAPPI PRESS
fate.
Specular reflectance Mirror-like reflectance.
If the incident light is collimated, the reflected light will be equally collimated.
(1994).
3. Barkas, WW, Proc. Pbys. Soc. 51(2):274
(1939).

4. Stenius,
(1953).
A., Svensk.
Papperstidn.
56: 607
5. Popson, S.J. ,"Diffuse vs.Directional

Brightness Measurement;
Technical
Bull. 101,
Technidyne
Corporation,
New Albany ,IN.
6. Kubelka, P. and Munk,
12:593 ( 1931).
7. Kubelka,
E, Z., Tech. Phys.
P.,] Opt. Soc.Am.
8. Steele, EA., Paper

(1935).
38: 448 (1951).
Trade]
10. Steele,
(1937).
F.A., Paper
Trade]
54:663
104: TSI57
11. Duncan, D.R.,j Oil and Colour

Ists'Assoc.
32: 2% (1949).
12. Harrison,
w: D., Paper
Trade]
Cbem-
105:TS39
(1937).
13. Nolan, P.,Paper Trade]
105:TS42 (1937).
14. Loyalka, S. K., and Riggs, C. A., Appl.

Spectrosc. 49(8): 1107 (1995).
15. Ingmanson,
w: 1. and Thode,
42(1):83 (1959).
E.E, Tappi
16. Lepoutre, P., Pauler, N.,Alince, B., Rigdahl,

M.,] Pulp Pap. Set. 15 (5):JI83
(1989).
17. Scallan, A.M. and Borch,].,
583 (1972).
18. Scallan,A.M.,]
(1988).
Tappi
55(4):
Pulp Paper Set. 11(3):J8O
19. Olt, H. G.,] Opt. Soc. Am. A8:1620
(1988).
20. Olt, H. G., Tappi]
72(7):
21. Olt, H. G., Tappi]
72(5): 222 (1989).
159 (1989).
22. Scott, W.E., Dearth, 1.R., Jordan, B., .Optical properties

of paper",
in Pulp and
Paper Manufacture,
3rd edn, V. 9: Mill
control & control systems;Qualtty
& testing, environmental,
corrosion, electrical
(M. Kouris, Ed.), TAPPI PRESS, Atlanta,
1992, Chap. VI.
23. Middleton,
S. and Scallan, A.M., Nord.
Pulp Pap. Res.] 7(1):22 (1992).
24. Jordan, B.D. and Popson,
Set. 20(6): JI61 (1994).
25. Bonham,
(1 'J86).
26. Dubreuil, M., Prog.In

% (1994).
27. Lafreniere,
S.]., ] Pulp Pap.
J.S., Color Res. Appl.
11(3):223
Paper Recycl. 3(2):
S., Dessureault,
M., Devic, M., "Bleaching

processes
for
ONP/OMG,
MOW, SWL, and UB/OMG
deinkOO pulps; 1993 TAPPI Pulping Conference Proceedings,TAPPI
PRESS, Atlanta,
Book 3, p. 885.
28. Olmstead,]. and Gray, D.G.J, Pbotocbem.
Pbotobiol. A73: 59 (1993).
29. Zhu,].H.
and Gray, D.G., A73: 67 (1993).
30. Technical
Section, CPPA Standard
E-l,
"Brightness
of pulp, paper and paperboard; CPPA, Montreal.
l00(37):TSI51
9. Stenius, A., Svensk. Papperstidn.

(1951) and 54: 701 (1951).
715
31. International
Standards Organization Standard 2470, "Pulp and paper: Diffuse blue
reflectance
factor (ISO Brightness);
ISO
Control Secretariat, Geneva.
32. International
Standards
Organization
Document
ISO. CD 11475, ISO Control
Secretariat, Geneva.
33. Jordan, B.D. and O'Neill,
74(5): 93 (1991).
34. Commission Internationale

de l'Eclairage:
Standard CIE 002, Colorimetric
Observers, Pub. No. CIE S 002, 1st OOn., Bureau
Central de 1a CIE, P.O. Box 169, A -1033
Vienna, Austria, 1986.
de I'Eclairage:
Colorimetry,
2nd edn., Pub. No. 15.2,
Bureau Central de 1a CIE, P.O. Box 169,A
-1033 Vienna, Austria. 1986.
36. Technical
minous
Montreal.
37. Bristow,
(1994).
Section CPPA Standard

reflectance
factor;
].A., Color
38. Stenius,A.S.,j
Res. Appl.
Color Appear.
40. Gantz, E. and

20:1395(1981).
Griesser,
41. Parkes, D., Tappi]
1:8 (1972).
(1976).
R., Appl.
72(9):95
Opt.
(1989).
42. Malthouse,
D.D. and Popson,
48(1):95(1995).
43. Doshi, M. R.,Progress
107 (May 1995)
E.7P."LuCPPA,
19(6):475
39. Gantz, E., Appl. Opt. 159:2039
S.].,Apptta
in Paper Recycling:
44. American Society for the Testing of Materials Standard ASTM E308-95 , ASTM Standards on Color and Appearance
Measurement,4th
edn.,ASTM,
1916 Race Street,
Philadelphia,
1995.
45. Bristow,].
S., Dubreuil,
M.A., Tappi
A., Tappi]
46. SCAN Standard
78(12):45
P3, "Pulps,
(1995).
paper
and
716
Pulp Bleaching
-Principles
and Practice
boards -ISO brightness."

47. Bristow,].A.,
Tappi]
59. Budde,W:,Color
77(5):174
(1994).
48. ISO Document

Iso-ms 7856, "Paper and
board Determination
of diffuse Z reflectance factor of fluorescent
white materials(Z-brightness),"ISO
Control Secretariat,
Geneva.
49. Technical
Section CPPA Standard EP.6,
"Blue reflectance
(Rz) of pulp, paper, and
paperboard;
CPPA, Montreal.
50. Weiss, G. and Bruce, A., Pulp Pap. Can.
83(2):T50 (1982).
51. Eagan, W:G. and Hilgeman,
15(7): 1845 (1976).
T., Appl. Opt.
52. Johnson, N.1. and Stephenson,

H.E, "The
influence of geometric tolerances on 45/
0" and 0"/45 colorimetric measurement,"
Commission on
20'" Session, International
Illumination
Proceedings,
Amsterdam,
Bureau Central de la CIE, P.O. Box 169,A1033 Vienna, Austria, 1983.
53. Clarke, G.J.]. and Perry, D.]., Ligbting
& Tecb. 17(1):1 (1985).
54. Robertson,
(1972).
A.R., Appl.
Res.
Opt. 11(9):1936
55. Judd, D. B., and Wyszecki, G., Color in

Business, Science, and Industry, 2nd eOO.,
Wiley, New York, 1%3, pp 102-103.
56. Budde, W:, Physical Detectors
Radiation,
Academic
Press,
1983.
57. Berns, R. S. and Petersen,
Appl. 13(4): 243 (1988).
58. Jordan, B.D., O'Neill,
N.A., Bain, R.W.,
16(4):JI28(1990).
of OpUcal
New York,
K.H., Color Res.
M.A., Sommerville,
Pulp
Pap. Set.
Res.Appl.
5(2):73 (1980).
60. Budde, w: and Chapman, S. M., "Measurement of brightness and opacity according
to ISO standards,"
Transactions
2: 61
(1975).
61. Budde, w: and Dodd, ex.,
Farbe 19:94
(1970).
62. Budde, W. and Chapman, S. M., Pulp Pap.
Mag. Can. 69(7):T206
(1968).
de I'Eclairage:
Technical report No. 44, "Absolute methods for reflection
measurements"
1979.
Bureau Central de 1a CIE, P.O. Box 169,A1033 Vienna, Austria, 1979.
64. Erb, w: and Budde,
4(3):113 (1979).
W:, Color
65. Jordan, B.D. and O'Neill,

Sci. 14(5):J113
(1988).
M.,j
Res. Appl.
Pulp Pap.
66. Silvy,]., "Blancheur, opacite, couleur: Les

proprieties
optiques
des pates et des
papiers 1a nouvelle normalisation,"
Doc.
PCI Ecole
Francaise
de Papeterie,
Grenoble,
IRFIP SE 11048 (1978).
67. Jousimaa, T., "KCL Y256-1: The effect of
sheet forming conditions
on brightness;
ISO Document
ISOTC 6/SC 5 N 749, ISO
Control Secretariat, Geneva, 1995.
68. Technical
Section
CPPA Standard
C5,
"Forming handsheets
for optical tests of
pulp (British sheet machine
method);
CPPA, Montreal.
69. ISO
Standard
3688,
"Pulps
- Preparation
of laboratory
sheets for the measurement
of diffuse blue reflectance
factor (ISO
Brightness);
ISO Control
Secretariat,
Geneva.
SECTIONVB:
Chapter 3:
Strength Properties and
Characteristics of Bleached Chemical
and (Chemi}mechanical Pulps
G.E. Annergren
SCA ResearchAB
Sundsvall, Sweden
1. Introduction
1.1 General considerations.
. . . . . . .. .. . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . .
1.2 Principles underlying strength teSt measurements. . . . . . . . . . . . . . . . . . . . . .
1.3 General effect of bleaching on papennakiog properties. . . . . . . . . . . . . . . . . .
2. Factors affecting the mechaoical properties of chemical pulp fibers . . . . . . . .
2.1 Fiber dimensions
2.2 Fiber damage. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3 Cellulose content. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4 Degradation of cellulose and hemicelluloses
2.5 Drying . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3. Factors affecting the mechanical
properties
of chemical pulp fiber
4. Factors
properties
of (chemi) mechanical
affecting the mechanical

pulpfiberousmaterla1
719
719
722
723
723
725
725
726
726
727
..... .... 728

730
4.1 Principles
730
4.2 Test methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 730
4.3 Interpretation oftest results
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 732
5. Mechaoical properties ofb1eached
pulps in standard paper networks
6. Relevance of a standard
(chemi)mechaoical
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 735
test for commercial
papennakiog
736
7. Effect of d.iffereot bleaching agents on the strength

properties of d.iffereot pulps. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 738
7.1 Bleached
7.2 Bleached
7.3 Bleached
8. Future trends
kraft pulps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
sulfite pulps. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
(chemi)mechanical pulps. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
in pulp strength testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
717
738
743
744
745
Chapter
VII 3: Strength Properties and Characteristics

of Bleached
Chemical and (Chemi)mechanical
Pulps
Chapter VB 3:
Strength Properties
and Characteristics of
Bleached Chemical and
(Chemi)mechanical
Pulps
1. Introduction
1.1 General considerations
Bleached chemical pulps are used for different types of products, but mainly for paper products (fable 1). The most important
product, particularly for hardwood pulp, is
so called wood-free printing and writi(1g
paper (paper with less than 10% mechanical pulp) often tenned fine paper (1). Softwood pulps are also used for reinforcement
in wood-containing
printing paper (mechanical pulp-containing paper),newsprint,
and magazine papers. Board and tissue are
other important products made from both
softwood and hardwood pulps. Their use
in markedly strong paper products, such as
higb-quality sack, is limited. The requlre-
Paper or Board
Printing and writing paper
Wood-free
Wood- containing
Newsprint
Tissue
719
ments for different pulps vary depending

on final product, and the conditions of the
converting process making the judgment
about the suitability of an individual pulp
for a particular end use vary significantly
from case to case.
Bleached mechanical pulps are mainly
used in wood-containing printing papers.
They are chosen for applications where
good opacity, good printing surface, and
high bulk (at a sufficiently high strength
leveO are required. Bleached (chemi)mechanical pulps from softwoods are used in
paper board, mostly in a middle layer, and
in hygienic products,such as tissue and fluff
cores in diapers, where ability to absorb liquid and bulk are important requirements.
Bleached (chemi)mechanical
pulps from
hardwoods are mostly used in furnishes for
manufacturing
various types of printing
papers.
To achieve the required quality of the final product, several different kinds of properties must be satisfied (fable 2): strength
of various types, bulk, optical quality, hydrophobicity or ability to absorb water and
other liquids, surface structure (for printing), and homogeneity. Some of these pa-
Pulp Type
Contribution
Softwood kraft
Hardwood kraft
Softwood sulfite
Hardwood sulfite
Reinforcement
Opacity, formation
Reinforcement Opacity'
Filler pulp
Softwood kraft
Mechanicalb
Reinforcement
Opacity, printability
Softwood kraft
Mechanical pulp
Various chemical
pulps
CfMp<
Reinforcement
Bleaching in case of dark wood
Softness, absorption
Absorption,
to Paper Furnish
r,,6k

1. Propmies
paper
Softwood kraft
Strength
Container
boxboard
board and boxboard
Chemical pulps
Appearance, surface strength,

printability
Bulk, stiffness
COIIlrlbatN
by tlI./fnnt
Softwood Pulp
Hardwood Pulp
Strength
Runnability
Formation
Opacity
COtfI/HnIeIIts I.. tbe /HIJIn' ftmt/s6.
Mechanical Pulp
Opacity
per properties are conflicting, for example

bulk and tensile strength. Thus, paper quality depends ultimately on how well these
properties can be balanced to satisfy the
quality profile which the market demands.
The property which is critical, and hence
should be given priority in the pulp evaluation, may therefore vary depending on the
type of paper product. Strength is not necessarily critical but is given high priority in
most paper products because it provides
flexibility by allowing inclusion of increased
amounts of inexpensive but weak components in the furnish and, when necessary,
by facilitating changes in the quality profile
of the paper to emphasize properties other
than strength. In other words, strength has
a commercial value (together with brightness) which is to a large extent reflected
by the market prices of pulps.
Another complication in the assessment
of pulp quality is that present-day paper mill
furnishes usually contain more than one

component, different types of fibers, fillers,
and chemicals. This implies that each component has a more or less specialized role
to fulfill. For instance, short fibers, such as
are present in hardwood chemical pulps
and most mechanical pulps, are not used
for strength but for the improvement of formation, optical properties,
and surface
Forming Section
pulp
,
pulp.
Press
Section
1
"Free. Vacuum
Drainage Drainage
Dominating component.
Fig.1. ~
Chemicals
Retention
Hydrophobicity
Strength
Brightness
smoothness, although strength is also desirable. Long fibers, on the other hand, often have a purely strength-contributing
function which is also associated with the
diffuse concept of runnability (i.e., the ability to run the paper machine or printing
press smoothly, without breaks). In this
case, good strength is often used to minimize the long-fiber content of the furnish
to decrease costs or to improve other papennaking properties of the furnish. These
concepts also apply to the production of
wood-containing printing papers.
Mechanical pulps consist of a mixture of
long fibers and fiber fragments (2). Fiber
fragments (i.e. ,fines) play an important role
in bonding, light scattering, and surface
smoothness. The more or less undamaged
fibers help to form the backbone of the
paper sheet. The bleached mechanical
pulps are used together with reinforcing
softwood chemical pulps in printing paper
where the ability to interact and create the
required bonding in the fiber network is of
major importance.
The runnability of a pulp in a paper mill
has become increasingly important as the
demands for productivity and efficiency
have increased in paper mills. Improvements in paper machine technology have
eliminated some problems but, at the same
Headbox
. General purpose pulp, not particularly specialized.

b
Fillers
Opacity
Bulk
Surface and pore
structure for
printability
Surface
smoothness
bulk
Packaging
CTMP'; mechanical
720
tlIa"..". of. JNIJIn'1tUIdII_system.
Dryer
1
Paper
Chapter VII 3: Strength Properties and Characteristics of Bleached

Chemical and (Chemi)mechanical Pulps
TlIbk
3.
FIIdors
tlffeclitlg
I'IIIUIIIIJI1Uy.
Beating (refining)
objectives:
Development
of fiber flexibility
and tensile strength
Reasonably
Minimum
Retention
Impurity
721
low energy
for good formation
requirement
fiber damage
and formation
deposition
Drainage on the
paper machine:
(e.g., pitch)
Free drainage
Vacuum drainage
Drainage in presses
Balanced adhesion to press rolls; uncritical

Wet strength: initial wet strength, rewetted
Drying response of wet web
time, demands for still higher production

levels and increased paper machine speed
have introduced new problems and have
changed the character of runnability problems to some extent.
As illustrated by Table 3, several different factors affect the runnability of a pulp
[see also (3)). The refining response determines how well the required fiber flexibility can be developed without serious effects
on the drainage properties including free
and vacuum drainage on the wire section
of the paper machine and drainage in the
press section (see Fig. 1).
Good retention of fiber fragments and
filler particles is also important when the
fibers settle on the wire and form a paper
web. Electrical charges of the fibers affect
retention and the use of retention aids.
Large amounts of fines created in refining
increase the surface area of the fiber material. As a result, added chemicals may be
adsorbed to a greater extent on the surface
of fines than on the fiber, thereby reducing
their effect. Because good retention may
lead to flocculation and poor formation, a
balancing of the conditions is necessary.
The removal of water in the press section is impottant both for the consolidation
ofthe paper sheet and in drying.A balanced
release of the web from the press roll after
the press nip (with sufficiently strong adhesion to the press roll for an undisturbed
release from the press felt but not so strong
that the following release from the press
release of paper
strength
web
roll is disturbed) affects the operation and

may be particularly critical for never-dried
bleached pulps in fine paper. Good wet
strength is needed for safe passage of the
wet web through open draws in the paper
machine. Important issues in drying are
removal of water and shrinkage during drying which is restricted to a varying extent
by speed differences in the paper machine.
The deterioration
of strength
after
rewetting of dried paper in size presses or
coating machines is another runnability
problem. Hydrophobicity and rate of water penetration into the fiber network dominate, but wet-fiber network strength is also
important. Long-fiber material provides an
advantage in this case.
Based on the above discussion, the following important issues are dealt with in
the succeeding sections of this chapter:
1. Chemical pulp fiber propetties as determined both by the morphological characteristics of the fiber source and pulp mill
processes, mainly pulping;
2. Properties ofthe complex fibrous material
and fines which comprise
(chemi)mechanical pulps;
3. Determination of the mechanical properties of pulp fibers in network structures that
mimic those found in commercial papers;
4. Relevance of strength test results in com.
mercial papermaking;
5. Effect of different bleaching chemicals on
the strength properties of kraft, sulfite, and
(chemi)mechanical pulps.
722
1.2 Principles underlying strength test

measurements
Chemical pulps have a strength potential suitable for papermaking,
but the
strength has to be developed through refining (beating), a mechanical treatment
carried out in the paper mill. This is in contrast to the practice followed in mechanical pulp production where the desired fiber
characteristics are achieved during pulping.
Thus, for strength test measurements,
chemical pulps must be beaten in the laboratory under conditions which mayor may
not resemble those existing in the paper
mill; typical mechanical pulp samples, on
the other hand, can be tested in the laboratory without prior refining/beating in the
laboratory. In most cases, laboratory beating provides a higher strength, approaching that corresponding to the potential of
the fiber material. A complete characterization of pulp strength in relation to other
mechanical properties, such as tear and tensile strengths, should therefore include both
the strength potential of the fiber material
after laboratory beating and the possibility
of reaching this potential through refining
in the mill (4). In other words, results of
strength tests should reflect the ability of
the pulp to withstand unfavorable refining
conditions without serious strength deterioration. Standard beating (refining) prac-
tice varies considerably in different mills and

may therefore lead to different strength results, making a test for strength potential
alone appear misleading even though it is
in fact a fundamental fiber property.
Refining develops strength and improves
sheet formation and surface properties; it
also produces negative effects such as impaired drainage properties, decreased bulk
(not always disadvantageous) and decreased
dimensional
stability due to increased
hygroexpansivity (5, 6). It is therefore necessary to control the refining to optimize
the property proffie of the refined furnish.
An interaction exists between beating and
pressing in the paper machine, making it
possible to develop strength and bulk in
different ways.
The testing of mechanical pulps is simplified by the fact that no laboratory beating is required before the test sheets are
prepared.
On the other hand, the large
share of fines, which are required
for
bonding and light scattering, must be retained in the sheet so as to produce fully
representative
sheet properties.
Special
procedures
using white water recirculation during laboratory sheet making have
been developed in certain cases to ensure satisfactory
fines retention
(7).
However, standard testing procedures,
which do not prescribe water recircula-
Standard Laboratory Sheet Making
eommercItIl~.g.
"""
Commercial Papermaking
One fiber component
Multkomponent
Homogeneous and mild beating
More or less heterogeneous and usually

more intense refining (beating)
Poorer retention
Good retention of fines but non-uniform

distribution in z direction
TlIbk 4. Di./fernt:a ,. sItIfrMmlltllJorwlmyslMetmUlrtg
Extremely
formation
of fines
good random
sheet
paper furnish
Oriented sheet with pronounced

direction and cross direction
machine
Standardized, fairly low grammage

(which agrees with mill practice
in some cases, for instance in the
case of mechanical pulp in woodcontaining printing papers)
Large variation
Mild pressing
High press impulse, drying at higher

temperature
and drying
in grammage
Chapter

of Bleached
Pulps
tion, are satisfactory for process control

purposes.
As it applies to sheet formation and consolidation
on the paper machine, the
strength potential of the fiber material compared with the strength actually obtained
under mill conditions is less easily defined.
The type of laboratory sheet used for standard testing of papermaking
properties
undoubtedly represents an idealized form
of papermaking characterized by extremely
good formation, random structure, and
good homogeneity which promote strength
(8, 9). However, the less ideal mill sheet
can better satisfy other properties: strength
in a specified direction as a consequence
of the oriented structure obtained on a paper machine
and surface smoothness
achieved through restrained drying and calendering~ Furthermore, the usuallaboratory testing methods do not take into
consideration any interaction between different kinds of fibers in the furnish and the
possible effects of fillers and other chemicals, including those used for siZing.
1.3 General effect of bleaching on papermaking
properties
The complete characterization

of the
papermaking properties of both chemical
and mechanical pulps is a complex and difficult task. It is, however, less difficult to
establish the effect of bleaching on the papermaking properties of a chemical pulp
because the papermaking properties are
largely determined by wood characteristics
and pulping conditions under the proper
bleaching conditions.
The main quality
objective in the conventional bleaching of
chemical pulps with chiorine-containing
chemicals is therefore to remove as much
lignin as possible and to decrease the color
of the remaining lignin while simultaneously preserving
those papermaking
characteristics which do not depend on lignin. The strength characteristics of sulfite
pulps may, however, be affected by strong
alkaline stages in a bleaching sequence;
alkaline treatment leads to a reduction in
the hemicellulose
content which in turn
723
affects beating behavior and strength development (JO).

In keeping the present trend toward minimizing the effluent load in bleached pulp
production,
an increasing share of the
delignification in kraft pulping and bleaching is borne by extended pulping and oxygen de lignification
(J 1). The balance
between these processes can influence the
chemical composition of the pulp and therefore the papermaking
properties significantly. Pulping affords a less selective
delignification than bleaching, particularly
below a certain lignin content; further
pulping beyond this critical residual lignin
content leads to a considerably decreased
hemicellulose
content and a relative increase in cellulose content (J 2-14). The use
of alkaline peroxide as a final bleaching

chemical is less effective as a delignification
agent but efficient in color removal, producing bleached pulp fibers having a higher
proportion
of residual lignin and an increased electrical charge than lignin-removing bleaching agents. Both beating behavior
and strength may be affected by these
changes which contribute, directly or indirectly, to the potential effect of bleaching
on the papermaking properties of bleached
pulps.
The primary aim in the bleaching of mechanical pulps for use in printing papers is
to brighten the pulp without changing significantly its desired high bulk and high
light-scattering characteristics.
The main
problem, therefore, is to ensure that these
properties do not change significantly during bleaching. A lignin-preserving bleaching process serves this purpose. A similar
quality problem occurs for chemimechanical pulps; here the main pulp characteristics are determined before bleaching but
brightness, hydrophilicity and, to some extent, fiber flexibility are enhanced during
bleaching.
724
1) Fibrous form of wood cells and their dimensions;

2) General fiber wall structure (fibril arrangement) and inherent wall defects, mainly
pores;
3) Mechanical damage (sustained in pulp mill
processes) which may be later aggravated
by chemical attack and cannot be compensated for by refining;
4) Mechanical damage, such as microcompressions, kinks, and curls, which can be
offset by proper refining;
5) Dissolution of wood components during
pulping and bleaching with an accompanying decrease in lignin content and an
increase in the relative concentration of
cellulose, the main load-bearing component of the fiber;
6) Degradation of the load-bearing carbohydrates;
7) Changes in the supermolecular structure
of ordered (crystalline) and disordered
(amorphous) material; and
8) Drying.
Wood consists of fibers having widely
different properties even when they are
present in a seemingly homogeneous pulp-
wood assortment.
Mill processes
may
contribute to fiber heterogeneity through
nonuniform operating conditions.
Fiber
heterogeneity is sometimes considered to
have an adverse effect on papermaking
properties. This view is probably correct
when an unintended
heterogeneity
becomes too large. However, the fact that
paper mills successfully mix different kinds
of pulps to create the required paper properties demonstrates that fiber homogeneity
is not necessarily disadvantageous.
Because of the inherent heterogeneity of
pulp, mean values, confidence intervals,
distribution curves, and extreme values are
required for a comprehensive characterization of fiber properties. In general, mechanical properties can be related to mean
values. Flocculation and poor formation are
caused primarily by extremely long fibers.
Extremely coarse fibers contribute to an uneven paper surface with poor printing properties and unsatisfactory softness. Several
of the factors affecting the strength properties of bleached chemical pulps are listed
in Table S.
Factor
Effect on Mechanical
Weighted average fiber length and fiber

distribution
Determines the effective load-bearing length

of fibers in a loaded network and the ability to
distribute stress; may be demonstrated by short
span tests
Fiber coarseness, fiber weight per unit

length
Affects conformability and specific fiber surface

with the exception of fibers having an abnormal
combination of fiber cross section
Fiber defects, naturally occurring as well

as those introduced in the mill
To some extent observable under the microscope; a quantitative determination of their effect
011papennaking strength properties requires an
imitating papennaking test
Cellulose content
Cellulose fibrils are the main load-bearing components: the relationship between ordered (crystalline) and less ordered cellulose determines stiffness
and elasticity of the fibrils
Hemicellulose
Promotes beatability and bonding between

in the paper sheet
content
2. Mechanical properties of
chemical pulp fibers
Degradation
The mechanical properties of chemical

pulp fibers are determined by a combination of factors (J 5-21):
Residual lignin content

(usually very low)
of load-bearing carbohydrates
Properties
Main effects are detectable
fibers
by viscosity measuresolvents
ments on pulp dissolved in cellulose
Usually very small effect, except possibly properties related to fiber surface. At higher concentration, some influence on beating response.
Chapter
vn 3: Strength Properties and Characteristics

of Bleached
Pulps
725
2.1 Fiber dimensions
2.2 Fiber damage
By dictating the general structure of the

fiber network in paper, fiber dimensions
have a dominating influence on the papermaking properties of pulps. Variations in
fiber dimesions are almost entirely dependent on the properties of the fibers in the
wood supplied to the mill. Long fibers facilitate the anchoring of fibers in the network. This role is more important in poorly
bonded fiber networks but is relatively unimportant in strongly bonded fiber networks (22). Long fibers flocculate more
readily than do short fibers and may impair
paper formation.
Moderately long fibers
offer the best alternative for both strength
and formation. Mill pulps have shorter fibers than the corresponding
laboratory
pulps because of fiber damage occurring
during pulp mill processing (23).
Fiber coarseness, another important fiber characteristic, is determined by fiber
diameter and fiber wall thickness.
Low
coarseness implies more fibers per unit
weight, a larger total specific surface, and
usually better conformability in papermaking (22).
The amount and characteristics of summerwood fibers in softwood pulps are of
great importance in determining the mean
coarseness level and therefore the prospects
for forming dense paper sheets which are
promoted by a low coarseness. Coarse summerwood fibers contribute to surface irregularities
which are important,
for
instance, in printing papers. Compression
wood fiber is another fiber type which does
not conform well in paper (24).
Hardwood fibers are less heterogeneous
than softwood fibers, but the high percentage of parenchymatous cells and vessel elements in hardwood pulps contributes to
their heterogeneity. When on a paper surface, vessel elements may be harmful because they are less well-bonded and may
loosen, for instance, during a coating operation, where the effect would be to disrupt the coating layer (25). Otherwise, the
main structural feature of hardwood pulps
is their short length and lower coarse fiber
content.
Fibers are damaged mechanically in different ways in the pulp manufacturing processes with the result that pulp mill fibers
contain more kinks and cell wall dislocations than do fibers in corresponding laboratory pulps (22, 82). Fibrous material is
obviously quite sensitive to mechanical
loads, both high-shear forces, for instance
in medium-consistency
high-shear mixers,
which give a kind of beating effect (83, 84)
and loads on fibers whose motion is restricted, as, for example, in soft chips during pulping or free fibers present at such a
high consistency that a rigid network is
formed, as is the case in medium- or highconsistency operations.
Severe damage, sometimes visible as
kinked fibers with sharply acute bends, as
cell wall fractures and, in more severe cases,
as cut fibers, irreversibly affects papermaking strength.
Strength effects are often
measured as so-called "strength delivery" in
the form of tear strength at a reasonably
high tensile index after standard laboratory
beating in comparison with the corresponding values for an undamaged pulp obtained
from the same kind of process (i.e., a mild
laboratory process) (26, 85). Less pronounced damage, conspicuous as curl, less
severe kinks, or micro-compressions
in the
fibers, is reversible and can be restored by
homogeneous, mild laboratory beating but
not under less ideal mill beating conditions
where strength development
is retarded
(27, 28).
Mechanical damage leading to dislocations in the fiber wall exposes cell wall
material to intensified chemical attack. This
may lead to strong localized weakening of
the fiber wall. A typical example is the
mechanical damage occurring during chipping which greatly impairs the strength of
acid sulfite pulps. Kraft pulping, on the
other hand, is affected only to a small extent by fiber damage during chipping (29,
30). This difference in the effects of acid
and alkaline conditions in pulping suggests
that the risk of harmful combinations of
mechanical damage and chemical attack is
726

16
C)
_ E15
Jfz
C\i'014
EO
~ -;
CI)13
xCI) -g
12
"tJ ..S CI)

(ij ~ 11
CI) c:
I- ~ 10
1ii
9
40
42
Fig. Z. THI' 11UIu lIS .. f8f1d1or1
44
46
Total yield % of wood
of to,," yield
greater at a low pH. On the other hand,

alkaline conditions, particularly at high temperature and a low lignin content,make the
fibers very susceptible to mechanical action
(31).
2.3 Cellulose content
Cellulose is the backbone of the fiber wall
and the main contributor to fiber strength.
Up to a certain level, an increased cellulose
content can be expected to increase the
overall strength of the fibrous material (32).
However, the mainly crystalline cellulose
lacks elasticity and requires softening to
withstand beating forces without harmful
effects, particularly during intense refining
(high specific edge load) when used to develop, for example, tensile strength. A certain amount of hemicelluloses is required
for sufficient softening of the fiber wall
during refining and sheet forming. However, too much hemicellulose
leads to
brittleness after drying of the sheet. Thus,
cellulose content has an optimum value and
should not be permitted to become too high
as is the case for softwoods pulped to a very
low residuailignin content. This principle
also applies to hardwood pulps where the
need for good bonding is great because of
their high short fiber content. Hemicelluloses also have a role in bonding.
48
50
on WOOtlfor InYIft pulp.
Figure 2 illustrates the effect of decreased

pulp yield on strength properties (33). The
trend shown in the figure is consistent with
the fact that low-yield pulps contain more
cellulose and fibers per unit weight of pulp
(34, 35). The yield differences were obtained through modifications of the pulping
process. A similar effect of decreased pulp
yield is obtained through extended pulping,
but it is outweighed by carbohydrate degradation at low kappa numbers (36).
2.4
Degradation
of cellulose
and hem i- .
celluloses
Degradation of cellulose and hemicellulose chains to fragments is an important
consequence of both pulping and bleaching. Degradation is determined by measurement of the viscosity of a solution of the
pulp, usually in a cupriethylenediamine
(CED) solution (37). The method is based
on the fact that the viscosity of a solution
containing linear polymers depends on the
chain length, that is the degree of polymerization (DP). Cuprammonium
hydroxide
and cadoxen (a cadmium complex) have
also been used as pulp solvents (37). In all
cases, dissolution of the pulp takes place in
an alkaline medium. Viscosity testing is of
great importance in process and quality
control, particularly in the bleach plant,
Chapter

of Bleached
Pulps
Tule 6. EJlt of tlrymg 011tile pI1ysie41JII'fJPntIa of II 6lMd1M ~
Density
(kgIm3)
Wet pulp
Dried pulp
PFt beating,
640
42.5
592
30.8
handsheet
made
so.ftrr004 krwft jnIlp (13).
Beaten Pulp' (drainage resistance SR45)
Unbeaten Pulp
Tensile
index
(kNm/kg)
727
Tensile
Tear
light
Air
Beater
index
index
scattering resistance,
R'volu- Density
ions
(kgIm3) (kNm/kg) (Nm2/kg) (m2/kg) (log Gurley)
8390
8825
according
838
106
7.9
13.2
2.57
813
98.5
8.4
14.9
2.16
to SCAN-C 26:76.
because carbohydrate degradation beyond

a certain level critically affects pulp strength
(38). This subject is further discussed below.
The supermolecular structure of the carbohydrates in pulp also may be of importance because the relationship berween
crystalline and amorphous material determines the fiber property profile. However,
even though little is known about the importance of this issue, efforts have been
made to correlate differences in mechanical properties with the different crystalline
forms of cellulose (39). It has also been
suggested (40) that an increase i.ft the order of the more or less amorphous components, both cellulose and hemicelluloses,
may be related to the differences in mechanical properties
displayed by pulps
made by similar processes.
2.5 Drying
Drying has a strong influence on fiber
properties (32, 41-43) ,as illustrated inTable
6; it decreases swelling ability and makes
fiber conformability
more difficult to
achieve. In principle, mild beating should
offset adverse drying effects. However, in
practice, refining is not mild enough to allow the strength development to occur in
the same manner as that for never-dried
pulp. Thus, never-dried pulp is preferred
when strong papers are required. Fine paper is an exception because,in this instance,
the required balance berween strength and
opacity (light scattering of the fibrous material) can more easily be attained with previously dried pulp.
Recycled fibers are conventional fibers
which have been refined and dried in one
or more cycles. Contamination
with, for
728
Pulp Bleaching
1::
Q)
Q.
Mechanical and chemimechanical pulps

include a variety of fibrous materials
adapted to different end uses. The general
character of a mechanical pulp is that of a
predominantly short-fibered material while
chemimechanical
softwood pulps usually
can be characterized as being long-fibered
pulps. Pulp properties are determined in
the pulp mill through proper selection of
wood species, possible thermal or chemical pretreatment,
mode of mechanical
defibration, and further mechanical treatment of the liberated fibers to produce fibers, fines, and only small amounts of shives
(1). Pulp screening and reject refining play
important roles in arriving at the desired
pulp composition.
The types of fibrous material in mechanical pulps are listed in Table 7. The hetero-
:
0
C
0
+:
::]
.c
.;::
20
.~
Q)
0
0>
c:
as -10
.c
()
0:
geneity of the fibrous material makes it difficult to distinctly characterize this material.
A Bauer-McNett fractionation using for instance 16-,30-.50-, and 200-mesh screens
can give a general view of the characteristics of different mechanical pulps as illustrated in Fig. 4 where the distribution
berween >30 mesh, 30- 200 mesh, and >200
mesh fractions are shown (45). The +16,
+30, +50, +200, and the -200 fractions correspond, respectively, to shives, coarse fibers, finer fibrous material having good
papermaking potential, and shives.
3. Factorsaffecting the mechanical properties of chemicalpulp

fiber
30
0
~Q. 10
and Practice
example, dyes and inks and mixtures of different types of fibers and fillers also characterizes this material. The dominating
changes in the fibers are caused by degradation during refining and decreased swelling capacity of the fibers caused by drying.
The effect on papermaking properties of
repeated drying cycles is illustrated in Fig.
3 (44).
100
II)
Q)
-Principles
50
Tule 7. 1)pa of ftlmnls ""'mllu

Jnllps.
I.. mN"",,Il
Shives
Fiber bundles
Fiber fraction
Coarse, stiff, long fibers,

ribbon-like lamellae, fibrils, fiber
wall fragments and broken fibers
Fines
Parenchyma cells, very short

fibers, portions of lamellae from
the secondary wall, primary wall
and middle lamella fragments
Because of their size and poor ability to

form bonds with the fibers, shives are detrimental and should be removed to whatever extent possible, particularly from pulps
intended for use in high-quality printing
papers (46). The fiber fractions consist of
coarse, stiff fibers having a low specific sur-
Mesh
<200
30-200
II)
is
>30
-20
0
-30
2
Number of drying cycles

Fig. 3. CbII..ge I.. sheet properties ""rt..g re}1eIItM IIryI..g of II .tn
blellellell InYIftJnIlp (44).
98.5
97.5
97.0
95.0
56.5
46.5
Yield,%
Fig. 4. 1yp1al11l1strllnltttm of ftImnIs ",.,erltIlIlSeIiI..
leI!eu (1IIUIerMcNettclllSslj'laltWrl) (45).
_spri..t
jIImlsbes correspomll..g to IIIff_t
)'lelll

face ~d a low-bonding ~pacity and of ribbon-hke lamellae, fibrtls, fiber-wall fragments, and broken fibers having a fairly
~rge spec~c surfac.e area and a relatively
high-bonding capaCtty (1). Coarse long-fibers, particularly those from thick-walled
summerwood
cells, may adversely affect
surface smoothness. Fines consist of parenchyma cells, very short fibers, portions of
secondary wall lamella, primary wall fragments, and middle lamellae. These components are important for bonding and light
scattering. They also contribute to the creation of a smooth surface suitable for printing and a capillary structure which controls
the absorption of printing inks.
A freeness test is used to provide a general characterization
of mechanical puIP1'.
For a more in-depth characterization
measurement of fiber length, fiber le~
distribution, and surface area (for instance
freeness of a middle fiber fraction in a Bauer:
McNett fractionation) have been suggested
(47, 48). Collectively these measurements
.
c:m. be use d to exp Iam differences between
similar types of pulps. However, differ-
.
.
. between
ences In mec h ~c al properties
pulps made by different processes have yet
729
contrast, excessive amounts of pitch on the

fiber surface can impede bonding (46,50).
The presence of unchanged lignin in the
fiber wall confers on the fibers a woody
character which is reflected as rigidity in
forming the paper network and. as resistance toward changes in fiber structure
during drying (1). This factor makes it difficult to attain suitable strength but contributes positively to properties such as bulk
and opacity through increased light scattering. For many purposes, particularly for
printing papers, high light scattering, high
bulk, and good surface properties are at
least as important as good strength. The
primary aim in bleaching, therefore, is to
brigh~en ~he pulp wi~hout significantly
changmg Its .paJ?erm~ng character. That
means that lignm, for Instance, should be
bri~htened
without incurring
changes
whic~ measurably decrease and increase
swellin~ such as caused by rigidity. The introductlon of charged groups, indirectly
.. ~roUgh
s~ ~ation in hydrosulfite ~Ieachmg an d OD da !Ion to carboxyl groups m peroxide bleaching (51), should be minimized .
.
On the other ha n d ,mcrease d swe lling
and improved bonding may be of interest

for other end uses ,ac
if the y can be hi eve d
without too great a loss of fiber rigidity and

to be ex Pl'alne d b y stan dard stre ngth tests.
The chemical composition of the fiber
bulk in the paper. However, in such instances, replacement with chemimechans~rfac~ varies dep~nding o~ whether fiber
~Iberatton occurs m the mtddle lamella or
ical pulps is a better choice because they
(49). Both lignin and carcan provide better bonding and strength
In the fiber
bohydrate regions can be found on the fiwithout the assistance of fines while still
ber su~a~es.
Carbo~ydrat~s
provide a
preserving a reasonably high bulk (52). In
hy~philic
surface which facilitates the forthis case, further modification of lignin in a
matton of bonds between fibers during the
lignin-preserving bleaching treatment may
consolidation
of the paper network.
In
also be desirable.
Tule B.S,.".rd _lboIIs far Iw ~
tUUIInti., of blllulsbeets.
Method
Measurement
TAPPI
Scan
CPPA
Disintegration for testing

Beating
Beater with bedplate
PFI mill method
T2050m-88
T 205 om-88
T 200 om -89
T 248 cm -85
C 18:65
C 18:65
C 25:76
C 24:67
ClOP
Drainage properties
Handsheet formation for physical
testing of pulps
Strength properties
T 221 om -93
C 19:65
CI
C2
C7
730
bleached chemical pulp fibers
in standard paper networks
4.1 Principles
The papermaking properties of a pulp
depend on how pulp fibers behave in the
papermaking process and how they influence mechanical and other paper properties. To a considerable extent, the answer
to this question can be predicted from measurable fiber properties; however, the quantitative effect of such important phenomena
as mechanical
damage and structural
changes in the fiber wall on the papermaking properties carmot be easily determined
by direct measurements on the fibers. Furthermore, there is a difference between the
general behavior of fibers and their behavior in a dense network such as is present in
paper.
In the laboratory testing of papermaking
properties, the procedures that are used
attempt to imitate industrial papermaking
which consists of several different unit operations (Table 8). In any test method, the
procedure has to be carefully standardized.
Because papermaking practice varies considerably among paper mills, the test
method must involve a compromise
in
which the goal is to obtain internally repeatable and, if possible also, externally reproducible results. This means that laboratory
tests do not closely mimic common industrial operations and that they should be
considered only as an indicator of fiber behavior in a standardized network of a type
which can be found in paper, but not necessarily in a particular paper. In such instance, results are relevant for papermaking
but need to be translated to become directly
applicable to a particular paper mill situation.
4.2 Test methods
Sheet formation procedures that mimic
the formation of paper in the papermaking
process involve the following steps:
I) Disintegration of the sample;
T 205 om-88
T 220 om-88
C 26:76
C 28:76
C4
DI2
2) Beating at low or medium consistency in

different types of laboratory beaters;
3) Sampling of beaten stock at suitable intervals;

4) Disintegration;
5) Handsheet preparation at low consistency
in which fonnation is more or less random;
6) Couching;
7) Pressing in two different sets with exchange of water-absorbing blotting papers;
8) Restrained drying against a smooth plate
or drying with a shrinkage limited by the
movement of surrounding blotting papers;
9) Conditioning under standardized temperature and humidity conditions; and
10) Testing of the conditioned handsheets.
The many steps comprising the test procedures require a considerable amount of
lfianual effort, with the result that high precision is called for and scatter of the results
becomes an important issue to be dealt
with, for instance, through replication of
the test. Efforts have been made to automate test procedures (53).
The test results are usually reported in
the form of beater curves. Typically, a beater
curve consists of a zero-minute or unbeaten
strength point and a series of five points
corresponding to beaten pulp sampled at
approximately equal freeness intervals during the beater run. The test results are plotted against beating work expressed as time,
number of revolutions or freeness/drainage
resistance
(e.g., Canadian standard
or
Schopper-Riegler). The results can then be
interpolated at different levels of beating
work or freeness depending on the kind of
a comparison desired. The interpolation
eliminates part of the scatter but leaves a
considerable atnount to be dealt with in the
evaluation.
Test methods are distinguished by the
mode of beating and the fundamental structure of the handsheets. Laboratory beaters
usually act fairly homogeneously on the fibers and produce a large amount of internal fibrillation (54, 55). This is in contrast
to what is experienced in many mills where
the treatment of individualfibers is much

more heterogenous and, to a large extent,
produces external fibrillation and fines
through fiber cutting. Sheet structure is
strongly affected by the drying mode. The
Chapter

of Bleached
Pulps
loss of some fines in the sheet-forming process should be noted. Despite differences
in the standard methods, pulps are usually
ranked in a similar order. Some pulps need
more beating to develop optimal sheet
strength; sheet-forming methods which produce denser sheets for a given degree of
beating tend to favor these pulps, but the
deviation in ranking seems to be small.
Handsheet tests usually consist of density, tensile index (and/or burst index which
usually is correlated to tensile index), tear
index, and light-scattering coefficient measurements. Characteristic
values are obtained for the pulp tested.
Other tests
731
which are more sensitive to the fine structure of the sheets, for example porosity and
surface structure, require a more sophisticated sheet-forming procedure to give reliable results.
Examples of beater curves are shown in
Fig. 5 for a normal Scandinavian softwood
kraft pulp and a eucalypt kraft pulp of medium strength.
Over the years, different "standard" methods have been used, making it difficult to
compare test results from diverse pulp
sources unless results from well-characterized pulps are included. Strength test results have also been reported differently:
60
Property
Pair
Tensile index
Effect Measured
Tensile strength
beating time!beater
40
30
o Drainage resistance, SA
. s, light-scattering
/;. CSF x 0.05
o Density x 0.05
20
10
coati.
. Tensile index x 0.5

[J Tear index x 3
0
0
2000
4000
6000
8000 10000 12000
Tensile index - density

Teat index
tensile index
Possible variations
Light-scattering
SA
Tensile index
Density
s
40
30
o Drainage resistance, SA
Tear index
20
o Density x 0.05
. Tensile index x 0.5
[J Tear index x 3
10
. s, light-scattering
0
0
2000
4000
6000
8000
coati.
10000 12000
Baater revolutions
Fig. 5. &!ater
CflMJeSfor
1nwft pulps (B).
ty/IkIIl
COIIIIIIeI'ritIlly
bte.ebetl
ScIIIuUtUlvIsn
sojlwJood
IHIrtlwootl
"""
(elWidypt)
during
beating
coefficient
in beating
behavior,
paper bulk
Strength primarily related to effective load-bearing

fiber length at low tensile (low degree of bonding) and to fiber strength at high tensile index
tensile index
Surface area, tensile strength
tensile strength as breaking length or tensile index (about ten times the breaking
length) and tear strength as tear factor or
tear index (about one-tenth of the tear factor).
The purpose of the test methods is to

investigate the beating response of the fibrous material in a pulp, the strength potential
and light scattering.
Other
properties may also be of interest, but their
reliable measurement may be impossible
because they require a more precise control of the sheet structure. For example,
fines distribution, which is difficult to reproduce in simple laboratory tests, affects
porosity and dimensional stability.
Beater curves constitute the basis for
evaluation of pulp strength. For comparing pulp, the beating response of different
pulps
the strength properties at 300 mL
may
CSF (Canadian Standard Freeness)
be used (or 45 Schopper-Riegler drainage
resistance, which corresponds to a somewhat higher degree of beating). Many pulps
show a maximum tensile strength development at 300 mL freeness. Testing at 500
mL CSF (or 25 Schopper-Riegler drainage
resistance) may be more suitable for evaluating the response of a pulp to mill processIng but provides less reliable information
about the strength potential of the fibers.
Freeness (or Schopper-Riegler drainage
resistance) is expected to be related to the
drainage behavior of the beaten furnish on
a paper machine, but different kinds of fibers show somewhat dissimilar relationships. Moreover, the pattern of strength
development during beating may differ de-
Hardwood (eucalypt) kraft pulp

50
development
revolutions
4.3 Interpretation of test results
50
60
732
development
pending on the type of beater used. For a

more informative evaluation, the relationship between pairs of important properties
are used (fable 9).
Drainage properties, which are very important in the papermaking process, limit
the opportunity
for developing strength
through beating. The relationship between
tensile index and freeness!Schopper-Riegler
drainage resistance, shown by the beater
curve, give guidance as to how much the
pulp can be beaten without creating difficult drainage problems on the paper machine. However, because the relationship
may not be the same for different beaters
and different types of fibers, it should be
used cautiously.
Both tensile index and density are indirect measures of fiber conformability and
can be expected to develop in a parallel
manner during beating in standardized testing (56, 57). A decrease in tensile strength
level at a specified density is indicative of
an unfavorable initial fiber configuration
and/or a poor beating behavior; the latter
is particularly serious when it occurs in mild
laboratory beating. The relationship between tear index and tensile index is suitable for fiber strength
evaluations
of
softwood pulps. To a large extent, these
properties develop as reflected images of
each other during beating (Fig. 5) and together can provide an indication of the general strength which is independent of the
degree of beating (Fig. 6). In contrast, for
hardwood pulps, the tear index often peaks
in the laner stages of beating (Fig. 5). Hardwood pulp tear-tensile strength relationships should be evaluated with this fact in
mind.
Chapter
....
as
Q)
I-
30
25
20
15
10
5
733

of Bleached
Pulps
Batch,
indirect,
Douglas Fir
Batch,
direct steaming,
Black Spruce
Continuous,
Jack Pine
...~
",
-25% '........
10
12
14
Breaking
Fig. 6. CtmIptIrlsoII of ItHIr-tnslle
relilttmublp
lIIOOIlirflft rmbIetu:bed pulps (58).
14
10
12
14
km
(sollilll_)
soft-
A link between the kind of fiber strength

evaluation described above and tests of intrinsic fiber strength is the wet zenHipan
tensile test (53, 60, 61). There are, however,factors other than fiber strength which
affect the wet zero-span tensile strength
test. Curl, crimp, and micro-compression
change the stress-strain characteristics
of
fibers and initially produce a lower zerospan tensile strength. Homogeneous, mild
beating increases the tensile strength to a
level which more nearly corresponds to the
actual fiber strength and is higher than is
indicated by the initial zero-span test. However, in mill beating, a low zero-span tensile strength often indicates a less favorable
behavior (28).
To a great extent, the position of the more
or less linear relationship between light
scattering and tensile index (Fig. 7) repre-
60
~A...
-N
E 50
......
....................
A 66
:s::
Q)
0(.) 40
CI
c:
.;::
Q) 30
:t:
<tI
(.)
I1J 20
----
Hardwood
Softwood
1500
B1
xQ)
"C
.S:
~I1J 1000
c:
Q)
-x
x
73
78
"'-n.
100"...102
500
00
o
500
700
Intrinisic
~158
A Conventional
bleaching of
unbleached pulp
10
~
ization (DP). When the cellulose OP becomes too low, paper strength is affected.
However, the effect of cellulose OP is superimposed on the effects of other variables
such as fiber type, mechanical fiber damage, and cellulose content which may give
rise to uncertainty.
Viscosity measurements are affected by
carbonyl groups in the pulp which contribute to falsely low-viscosity results. Reduction of the pulp with borohydride prior to
the test eliminates this problem which, in
most cases, is too small to justify taking this
step. An exception may be ozonated pulp
although, even in this situation the problem is usually eliminated when the ozone
treatment is followed by an alkaline (e.g.,
peroxide) stage.
With the introduction of major changes
in bleaching technology, different relationships between strength and pulp viscosity
may be expected. By analogy with the effect of pulping pH on damaged chips having obvious fiber wall dislocations, chlorine
dioxide bleaching at low pH and high tem-
....
<tI
Q)
+----. 215
~
sents the specific surface area of dried fibers (62, 88). An unfavorable development
of tensile strength during beating can, how.
ever, produce a deviation from the normal
relationship. It should also be noted that,
in the competition for fiber surface, differences in the increase of bonding surface
area and loss of light-scattering surface area
may appear when the sheet is formed differently. This is particularly obvious for mill
sheets.
Laboratory tests for evaluating papermaking properties
are time-consuming
and
unsuitable for direct process and quality
control in the pulp mill. Several investigations (38, 63-66) have shown that there is
a strong correlation between the mechanical properties of bleached pulp and pulp
viscosity in conventional bleaching. In mills
that maintain good control of the wood raw
material and pulping conditions, viscosity
variations reflect most pulp quality variations (66).
Pulp viscosity is an indirect measure of
cellulose chain length or degree of polymer-
I"'"
b:".:-"
CI
~
.S:
..,
100"-_
::i
12
for ",111 (1iIIsbM IItUls) flM J1Ilot pltItIt
The tear index -tensile index relationship

depends on fiber bonding and fiber length
at low degrees of sheet consolidation and
on fiber strength at high degrees (86, 87).
When tear-tensile curves parallel one another for pulps of different strength, the
differentiation of strength levels is uncomplicated and evident. An example of this
are cases where cell wall fracrures lead to a
decrease in the sheet strength also at a low
degree of bonding (58, 59). In other cases
where strength
differences
for pulps
bleached in different ways exist, the relationships diverge from a common level at a
low degree of bonding (i.e., a low degree.
of beating). Pulp with lower strength may
undergo a less drastic, but more widely distributed, weakening of the fibers which first
becomes significant at a high level of bonding or responds poorly to beating.
CI
10
length,
734
100
1~
Tensile index, kNm/kg

Fig. 7. Llgbt Setltterl8g-tnslle
relotUmsbtp for tlIfferetll btmlttIooIl tIfIIl softlllOOll bleflebe4 Inwft tIUIrlIet pulps
beflten to 25-45 SR draifUlge reststflru:e (B). Fiber COdrsetUISS (",gIfmr) is IndU:ilted for etICb pulp.
900
viscosity,
o Conventional
bleaching of
oxygen-delignified
pulp
1100
dm3/kg
0 Acid hydrolysis
of bleached pulp.
OfJet'tIllstrMgtb (teMltUlu x tnslle Index) tIfIIl httrlask IIiseosUy for softFig. 8. Relilttmublp be'IIIOOIlInwft pulps flfter tlIfferetll trefltmmts (64). BetltlflgllltlS cmulrIeted lICCM'diflgto SCAN-C 18:65;
sbHt-furmirlg,
cbenrktIl c~).
tIS Jtreserlbed,.
SGtN-C 25:76(64).
(B1-B7 deJwtes
dtjJeretlt
bletlCbt"g
sequnlees
find

perature has been shown to give a less advantageous strength-pulp viscosity relationship than does normal (higher pH) chlorine
dioxide bleaching as shown in Fig. 8 (64).
Moreover, in a predominantly
alkaline
bleaching sequence, overall strength may
suffer even less from this kind of local reduction in fiber strength with the result that
the general reduction of cellulose DP in fibers becomes predominant. In this case, a
more favorable relationship between pulp
strength and viscosity would be expected.
In any case, strength should be DP-dependent in all cases: a gradual decline of the
strength occurs when the DP decreases and
the decrease is less at a high DP level and
greater below a critical DP level.
bleached (chemi)mechanical
pulps in standard paper
networks
The
papermaking
properties
of
(chemi)mechanical
pulps are determined
through use of the same standards for sheet
making and testing as for chemical pulps.
However, the wood bolts or chips, with or
without pretreatment,
have already been
ground or refined to the target freeness in
the pulp mill, thereby eliminating the need
for additional laboratory beating. On the
other hand, for the purpose of studying the
characteristics of the pulp mill equipment
or a special type of process, it may be desirable to vary the mechanical energy input
in the mill to obtain pulp at different freeness levels.
The presence of fines in mechanical
pulps is a significant issue in pulp testing
because fines retention in normal sheetmaking is not particularly high, at least not
in cases where standard tests specify a low
basis weight. White water recirculation has
been used to increase the fines retention to
a high level, an important goal, for instance,
in bonding studies (67). Otherwise, white
water recirculation is a complication and
usually is avoided when only a relative scale
is required for comparing pulps.
Control of the fines content is also essential in the sampling of mechanical pulps
735
in paper mill systems. Because of the low

fines retention on the paper machine, white
water used for dilution may contain a considerable amount of fines which may contribute to the fines content of a pulp sample
should the sampling be done at an unsuitable site in the mill.
Interpretation
of the properties
of a
chemical pulp sheet can be simplified by
taking into consideration fiber strength and
the bonded area. The properties of a mechanical pulp sheet depend on the structure of a network containing
different
particle types and on bonding which is restricted by the low plasticity of the fibrous
material and can be expected to vary depending on the chemical nature of the different surfaces comprising the material.
Fiber strength is not as significant for mechanical pulps as for chemical pulps. The
creation of new surface area is, on the other
hand, relatively more important because it
improves most properties including tensile
strength, light scattering, and, to some extent, tear strength (68).
Normally, the evaluation of (chemi)mechanical pulps consists of obtaining a
property profile at the prevailing freeness
level. Different types of mechanical and
chemimechanical pulps have different profiles. A meaningful comparison must then
consider a normalization of the properties
to similar critical property levels by mixing
the mechanical pulp with the required
amount
of reinforcing
chemical
or
semichemical
pulp. In such cases, the
amount of reinforcement pulp added is an
important factor in determining the papermaking characteristics of the mechanical
pulp. The normalization can be made hypothetically using pulp diagrams of the type
shown in Fig. 9 (45) or experimentally
where more accurate comparisons are desired.
Figure 9 also shows how strength properties and light-scattering coefficient develop when the mechanical energy and,
therefore, the freeness level is changed. The
most significant question regarding the effect of bleaching on mechanical pulps is
whether bleaching preserves the character
736

C;
80
~70
60
==
CD 50
0
0
01 40
c:
'C
CD 30
0
I/J
.,!.
.s=
01
::i
~20
10
0
0
10
20 30 40 50 60 70
Tensile index (kNm/kg)
80
90
20
01
~C\I 15
E
Z
CD 10
".5
lIS
"CD
~Arrowindicating
effect of refining
0
0
10
20
30
Tensile
40
index
50
60
70
80
90
(kNm/kg)
Fig..9A(UPJWr):
blllliolublp be'lIgbt-sadtm.g coejJfdnlt tmtl telUile ilUlD:for diffet'ftlt ebemiCIIl
tmtl (,.",,~
JIII".,.fttrM 10tUlf-'j'twtIa&l_ls
(45).
,..,. tmtl telUile ilUlD:fordiff-'
ebemiCIIltmtl (ebemi)mlHuliCIIl
Fig. (w-r): blllliolublp be''B
JIII/JIs,.fttrM 10 tUjfnnI
Jr-leffls
",."ft
TMP.."---_#all""',
,."" SBK
_ibletlcbed
JnIl"
(45). GIJ'l) I"f1II'U/IroDdJIIII" RMP
CI'MP
=cbemU~iCIIl
JIIII,.
of the original pulp type or changes it in

direction more typical of chemimechanical
pulps. The introduction of a high concentration of carboxyl groups into pulps during bleaching provides such a change (69).
As is also seen in the figure, chemimechanical pulps have strength and optical property
relationships
which vary
between those of mechanical pulps and
semichemical and chemical pulps, the zone
locations depending
on the amount of
chemical treatment received during pulping
and bleaching.
=,.ftMr mecbaiCIIl
JIIII"UBS=afli1ktlcbetlsalftte
6. Relevance of a standard test

for commercial papermaking
The standard papermaking
testing of
bleached chemical pulps in the laboratory
primarily emphasizes strength, usually expressed as tear strength at a given tensile
index. This preference is consistent with
the fact that one ofthe main distinguishing
effect:! of chemical pulp bleaching i~ a dc.
terioration of pulp strength. Strength is also
a primary concern when bleached softwood pulp is used as a reinforcement pulp
as is usually the case in printing papers. As
Chapter

of Bleached
Pulps
illustrated in Fig. 10, printing paper furnishes consist of three types of components: a dominating, more or less shortfibered pulp ( a mechanical pulp or a chemical hardwood pulp), filler, and a reinforcing long-fibered
softwood
pulp. The
amount of reinforcement pulp, usually the
most expensive component, depends on
how well it fulfills its reinforcing role.
The reinforcing effect is determined by
the manner in which the different fibers
long, more or less flexible softwood chemical pulp fibers and less flexible mechanical
pulp fibers of different length or short, flexible hardwood chemical fibers
and the
filler interact synergistically (70). Fiber
length plays an important role in the reinforcing effect, at least within the reasonable
limits determined by the ability of the lopg
fibers to provide good formation.
Fiber
length is particularly important for imparting strength to the wet web in the paper
machine and to dry paper sheets having a
low degree of bonding. Fiber strength is
important in the dry paper, particularly for
sheets having a high degree of bonding.
Good fiber strength is also required when
contending with harsh beating conditions.
The development of tear strength during
bleaching illustrates what may happed to
fiber strength when it is measured on a wellbonded sheet. However, tear index as such
is not a completely reliable measure of the
reinforcing potential of a pulp because it
tends to favor pulps with coarse fibers, at
least at a low- or medium-tensile index level.
737
The reinforcing effect is best obtained

with fibers having a high fiber length!
coarseness
ratio (70). Low coarseness
means that more fibers per unit weight of
pulp are available to offset the superior reinforcing effect a long, but coarse, individual fiber provides. This is in accordance
with the general behavior of reinforcing fibers in composite materials. Because fiber
length usually varies much less than coarseness, a low-<:oarseness pulp is normally favored in this situation although it does not
contribute high tear strength at a low- or
medium-tensile index level.
In wood-containing
printing papers,
bonding between the reinforcing chemical
fibers and the mechanical fibrous material
is an important concern. At a low chemical
pulp content, bonding related to reinforcement exists mainly only between chemical
fibers and mechanical fiber material (70).
Because of differences in behavior during
consolidation ofthe sheet and drying, difficulties are encountered in obtaining good
bonding between the two types of fiber
material.
Chemical fibers having good
confurmability should contribute to the formation of reasonably stable bonds. This
conformability
can be achieved through
beating or simply through the use of low
coarseness fiber material.
At chemical pulp contents above 25
30%, bonding between chemical fibers can
be expected, and this enhances the desired
reinforcing effect. Reinforcement is only
one aspect of the quality profile; in other
Filler
Reinforcement
pulp
Mechanical
short-fiber
pulp or
chemical pulp
FIg. 10. TentIJ1'YtlI4grwm for tM rumrtIIl mlJt of ~

I" SlIpnY:tIletUkred (SC), Ught mght COtIIett
(LWC), ,,,,"FIIII! p.per(FP) (H).11Iet:Of'lU!rS oftM trlimgltinpreUftt
100% oftMt:tJIIf/1mIe8I sbornt.
738
respects, the mechanical pulp has a dominating influence on paper properties.

Reinforcement pulp is very important in
papermaking but, because of the high percentage of mechanical pulp in the furnish,
the properties of this pulp dominate those
of the furnish. Because bleached mechanical pulps are used primarily for high quality papers, the absence of shives and
particles, which adversely affect surface
smoothness, is a top priority consideration
(1). Shives in mechanical pulps are hard
and stiff, which makes it difficult for them
to fit into the fiber network in paper webs
and, therefore, may imitate breaks of paper
webs. Drainage properties are somewhat
difficult to properly assess by means of freeness measurements because the (chemi}
mechanical pulps have poor free drainage
but very good vacuum drainage (72, 73).
Otherwise, the standard tests meet the requirement for a normal evaluation of the
pulp, particularly because no laboratory
beating is required.
Fine paper is made from a variety of fiber furnishes comprising all types of fully
bleached pulps. The use ofshort-fiber hardwood pulps is increasing and ranges from
strong pulps to so-<:alIed filler pulps whose
main role is to contribute opacity and bulk.
Long-fiber reinforcement
pulps are used
primarily for runnability purposes and are
added in amounts which vary depending
on the paper grammage. The optical properties are controlled to a large extent by the
inclusion of filler, which is an inexpensive
component and therefore should be used
to whatever extent is practicable. The use
of dried pulp offers advantages, namely,
improved runnability, facilitated balancing
of the paper properties, and lower hygroinstability. Starch is added to improve
strength.
Given this complex situation, it is often
difficult to identify the individual effects of
alternative pulps present as components in
a paper furnish. For furnish compositions
which more than meet strength requirements, it may even be difficult to distinguish
between two pulps differing, for instance,
in strength potential. However, when the
composition of the furnish is adjusted to

conform more exactly to the strength requirements, it becomes obvious that less
reinforcement pulp, which has the potential for contributing a high tensile strength
without causing excessive drainage resistance, is needed.
Moreover, a stronger
short-fiber pulp can accommodate a higher
filler content better than a filler pulp, provided that the correspondingly lower bulk
does not create a problem. In both cases,
strength can be utilized to make the furnish
less expensive.
However, consistency with respect to
papermaking properties appears to be more
important because uninterrupted
paper
production with good control of paper mill
variables is the best guarantee of high-quality frne paper. The conclusion is therefore
that papermaking tests are also relevant for
frne paper even though the primary aim is
not always strength. Tissue is another product for which product property predictability and runnability of the pulp on the paper
machine are critically dependent on pulp
quality (74). Softness is another important
quality characteristic.
It therefore is important to understand
that papermaking depends on a combination of many different factors. Thus, when
the effects on paper quality of fiber raw
material and pulp mill processes are superimposed, the effects of the paper mill processes may outweigh those of the fiber raw
material, making it difficult to isolate the
effect of a single fiber property on the property profile of a paper.
7. Effectof different bleaching

agents on the strength properties of different pulps
7.1 Bleached
kraft pulps
Pulps bleached in conventional sequences

(including ECFsequences)
The mechanical properties of conventionally bleached softwood kraft pulps are
controlled by the fiber morphology, mechanical fiber damage, and carbohydrate
degradation.
Conventional
multi-stage
bleaching chemicals delignify selectively,

Tllble10. SImfII/I 11M
~JIt'OP1ies
of blMeW so~
tII./f-' IIIseosIIy'-IS' (B).
Intrinsic
VISCosity
(dm3/kg)
TAPPI
Viscosity"
cps.
Beater
revolutions
Inwft JnlIJI(UpptI -'-1IJIPrwt.
Density
(kg/m3)
Tensile
Index
(kNm/kg)
105
Tear
Index
(Nm2/kg)
739
25) ",
lightscattering
Coeff.
(m2/kg)
Conventional multi-stage bleaching

1000
850
25.5
17.4
9000
7800
825
830
700
11.7
6500
820
99
9.3
8.7
13.5
14.5
89
7.7
16.6
TCF multi-stage bleaching with oxygen, ozone, and peroxide

800
700
I
15.2
11.7
7125
6200
835
830
99.5
92
Pulp Bleaching
8.9
8.2
14.6
15.9
-Principles
and Practice
Jnllps muI" softwood InwftJnllp COfIlJftIIIqully

TIIbIe11.1'yJIIeMslrMgtb w"fId of commMCItIIlHmlwood
~(13).
Pulp
Drainage
Resistance,
SR
Beating
Time,
min.
Density
(kgIm3)
Tensile
Index
(kNm/kg)
Tear
Index
(Nm'/kg)
Lightscattering
coeff.
(m'/kg)
Fiber
Coarseness
(mg/km)
Strong"
birch kraft
25
45
21
44
687
780
65.0
82.0
8.2
7.5
31.2
26.2
102
Soft<
birch kraft
25
45
13
33
645
28
53.3
70.0
7.3
7.1
34.0
29.3
100
Strong
25
45
23
50
601
711
52.8
76.1
7.3
7.6
38.6
31.8
78
25
45
24.5
55
576
647
45.9
71.3
7.3
8.1
41.0
34.7
73
25
45
15
41
576
647
32.1
52.6
55.0
46. 5
66
25
45
16
40
565
660
28.3
43.8
4.3
'U
4.1
4.3
40.5
35.0
98
Soft U.S.
25
southern
45
hardwood kraft
23
44
556
630
43.0
61.0
7.8
8.1
37.0
34.0
100
Scandinavian
25
softwood kraft 45
39.5
70
685
754
91.6
101
11.0
9.9
23.3
20.7
158
eucalypt kraft
PFI beating, handsheets prepared according to SCAN-C26:76, drainage resistance 45 SR;

original data interpolated to the different viscosity levels; 95% confidence limits within
~%
bTAPPI methodT-230
740
Strong
eucalypt kraft
Filler
eucalypt kraft
om-89.
Beech sulfite
producing
pulps having a carbohydrate
composition which varies only slightly with
the bleach sequence and the applied chemical (elemental chlorine, hypochlorite, and
chlorine dioxide) under reasonably wellcontrolled
conditions.
Provided
the
pulping process is not extended too long
(kappa number~ 25), its effect on the carbohydrate composition is small enough to
make variations in pulping conditions of
minor importance. Therefore, conventionally bleached softwood kraft pulps are primarily characterized
by their intrinsic
viscosity (13, 66). Introduction of an alkaline oxygen delignification stage and a corresponding
reduction
of the chemical
charge in the following bleaching stages do
not significantly change the relationship
between
strength properties
and pulp
viscosity.
Table 10 shows the difference in properties of a softwood kraft pulp bleached to
different viscosity levels after PFl beating
to a drainage resistance of 45 Schopper
Riegler (about 260 mL CSF) when a pulp
has been bleached to different viscosity levels by different bleaching sequences (conventional
5- to 7-stage sequences
with
elemental chlorine or chlorine dioxide as a
prebleaching chemical and one sequence
consisting
of an introductory
oxygen
delignification
stage).
Variations in pulping conditions are more

important for hardwoods and add to the
above mentioned factors affecting the mechanical properties of bleached kraft pulps.
High alkalinity during normal pulping or extended delignification significantly decrease
the yield and the hemicellulose content of
the pulp. The short hardwood pulp fibers
need good bonding to develop paper
strength for which the hemicellulose plays
an.important role. In practice, these variations in pulping conditions have been the
primary cause for quality differences between strong pulps and filler pulps
(fable 11).
Carbohydrate degradation has a similar
effect on hardwood pulp strength properties as it does for softwood pulps; however,
when differences in carbohydrate degradation are combined with differences in critical pulping conditions, a characterization
of pulp strength through viscosity measurements may be misleading. Pulping at a high
alkalinity followed by a mild bleaching
(hardwood pulps are usually easy to bleach)
may produce a pulp having a high viscosity
but a mediocre strength because of its low
hemicellulose
content, lfowcvtr,low pulp
viscosity, coinciding
with and partially
caused by extended pulping, may give rise
to extremely low strength compared with
the potential of the fiber raw material and
Valley beating, handsheet preparation performed according to SCAN-C 24:67.

b Pulps bleached with chlorine-contalning chemicals, no oxygen delignification.
'The terms strong and soft are used mainly to describe bleached sulfite pulp. The market bas hardwood
pulps varying from those with very good strength ("strong pulps') to filler pulps with very little strength.
"Soft pulps' are those which have somewhat higher strength than the filler pulps but are inferior to the
strong pulps.They are usually pulped to a lower yield than the strong pulps.
may jpve the impression that viscosity is

even more important for hardwood pulps
than for softwood pulps.
In principle, the introduction of oxygen
delignification
and chlorine
dioxide
prebleaching
in elemental chlorine-free
(ECF) bleaching does not significantly
change the relationship between strength
and the intrinsic viscosity of pulp. Nevertheless, mechanical damage incurred by the
fibers in the new bleaching equipment and
incorrect pH levels in chlorine dioxide
stages at relatively high temperatures,
in
some cases, may decrease strength below
the expected level as indicated by pulp viscosity. Furthermore,efforts
directed toward
providing a very low effluent load through
increased delignification with oxygen may
lead to low pulp viscosity levels and a correspondingly low pulp strength.
Pulps bleached in TeF Sequences
The commercialization of extended kraft
pulping leading to low kappa number softwood pulps, and totally chlorine-free (fCF)
bleaching for the production
of semibleached or fully bleached pulp types have
made the evaluation of strength properties
more complicated. Substantial increases in
residual lignin content and in the amount
of charged groups, which promote swelling, increased cellulose content,particularly
in the case where wood is pulped to very
low kappa numbers, and low pulp viscosity are among the present-day factors affecting pulp quality. Decreased carbohydrate
yield and hemicellulose content, brought
Chapter
VII 3: Strength Propenies

and Characteristics
of Bleached
Pulps
about by severe peroxide-stage conditions

or enzyme-assisted delignification, may also
be imponant but probably only at critically
low hemicellulose contents. As a counterbalance to the negative effects of the new
technologies (extended pulping and TCF
bleaching), systems have been introduced
for reducing mechanical damage to the fibers in the digester (75).
The combination
of pulping to a low
kappa number
and a strong oxygen
delignification leads to a low pulp yield with
effects on the papennaking properties as
described above.
As discussed earlier, the relative increase
in cellulose content resulting from extended
pulping contributes higher pulp strength
which, however, cannot always be utilized
because of increasing difficulties in refining/beating stemming from the accompanying decrease in hemicellulose content.
Therefore, there is an optimal degree of
delignification
in pulping which varies
somewhat with the pulping method. A varying degree of carbohydrate
degradation
contributes to this variation.
TCF bleaching to semibleached
pulp
brightness levels can provide a reasonably
high pulp viscosity and a guaranteed corresponding1y high strength. When the bleaching sequence includes only oJtygen and
alkaline peroxide stages, the pulp has moderately high residual lignin content and an
increased concentration of charged groups
which can be expected to promote swelling and offset the negative effect of the residuallignin on beating. As shown in Table
12, more rapid strength development can
then be obtained during the beating operation.
TCF bleaching to high brightness is also
based primarily on the use of alkaline peroxide following an oxygen stage. Because
of the limited de1ignifying ability of peroxide, however, it is necessary to delignify the
pulp to a low residual lignin level before
the final peroxide
stage. This can be
achieved through 1) modified pulping to a
low kappa number and yield and a high
cellulose content arising from a severe oxygen delignification or 2) modified pulping
to an intermediate kappa number, oxygen
delignification, and a multi-stage bleaching
process in which peroxide (with or without additives), ozone (or organic and inorganic peracids), and possibly oxygen have
a role. Other chemicals currently being
studied in the laboratory and/or in mill trials such as peracids, polyoxometalates,
laccase5 combined with mediators, and dimethyl dioxirane eventua11y may be used
commercia11y to enhance pulp strength.
J1roJ1eI1Idof. softwood lnwft /J8lp b1Mebeil,,, . OflP~
lIIbu 12. ~
(13).
741
("Upox. JIt'OCeSS)
Drainage resistance 45 SR
Pulp
Description
Beater
Revolutions
Density
(kgIm3)
Tensile
Index
(kNm/kg)
Tear
Light-scattering
Index
Coefficient
(Nm2Jkg)
(m2Jkg)
Tear Index
at Tensile
Index 100
D(EOP)D(E+P)Dbrightness -90,
kappa number 0.5.
intrinsic viscosity
870 dm3!kg
8000
828
102
9.1
13.7
9.3
OQP-brightness -SO.
kappa number 6.5.
intrinsic viscosity
855 dm3!kg
6550
818
101
9.1
13.3
9.2
OQf-brighmc5S ~60,
)no
7.9)
13.8
7.9
kappa number 5,
intrinsic viscosity
730 dm3!kg
PFI beating. handsheets preparation performed according to SCAN-C 26:76
742
Pulp Bleaching
Tabu 13. P~g
-Principles
and Practice
JI1'OIIerlId of hIIOsoftwood ImIft /lIps bUael1ed
,,, different S4IfJfU!tICes

(76 ).
Brightness
(%)
Coarseness
(mg/m)
Beater
Revolutions
Tear
Index
(mNm'/g)
Density
(g/cm')
Ughtscattering
Coefficient
(m'fkg)
88.3
0.217
1469
13.7
0.71
20.2
79.6
88.7
0.219
0.208
1271
1208
13.9
14.2
0.71
0.69
20.6
21.8
89.1
79.4
0.220
0.220
1093
1152
13.4
13.3
0.73
0.73
19.7
19.7
89.4
0.214
939
15.1
0.71
20.7
Oxygen-delignified
Softwood pulp A
Multi-stage
TCF"
Peroxide-bleached
TCF
ECF
Oxygen-delignified
Softwood pulp B
TCF"
TCF
ECF
Values calculated to correspond to tensile index 70 Nm/g.

b Averages for several bleaches with oxygen. ozone, and peroxide in multi-stage sequences
(88+ % ISO brigbtness).
,
Bleached with peroxide to about 80% ISO brigbtness. Viscosity 660-730 dm'!kg.
d VlSOCsity 800-830 dm' !kg.
In the former case (1), there is a risk that

extremely low pulp viscosity might result
which may be panially offset by a low
strength loss arising from mechanical action
occurring in the pulping process. However,
the high cellulose content of a pulp made
in an extended pulping process may have
an adverse effect on the strength development during refining/beating. The residual
lignin content at the conclusion of bleaching is higher than that in conventionally
bleached pulps and depends on the lignin
content of the pulp entering the final peroxide stage.
In the second case (a multi-stage bleaching process), the extent of carbohydrate
degradation detennines the papermaking
properties. A low viscosity affords a lower
strength as shown by the values inTable 13
(76). On the other hand, a superior balance between pulping and the bleaching
sequence gives rise to a bleached pulp
chemical composition
similar to that of
conventionally
bleached pulp. With a controlled carbohydrate
degradation, papermaking properties
close to those of
conventionally bleached pulps can be obtained (Table 10).
The relationship between strength and

Intrinsic viscosity indicates thatTCF bleaching or bleaching with only small amounts
of chlorine chemicals In combination with
TCF bleach1ng chemicals is better than conventional bleaching (77, 78), possibly because of less local chemical attack at
damaged sites on the fiber wall as is discussed in the preceding section. When
evaluating strength differences, it should be
borne In mind that they may be small or
insignificant In the beginning of beating but
thereafter Increase during beating as illustrated In Fig. 11 (13). The figure also shows
that the scatter In single measurement data
obtained from conventional strength test
methods can be considerable.
Hardwoods are easier to pulp and to
bleach than softwoods. TCF bleaching can
therefore be applied to hardwood pulp production with less risk of Incurring quality
problems. Final bleaching with peroxide
alone produces pulp with high kappa numbers even after bleaching to a high brightness. Bleaching sequences that include
ozone or other strong delignifying agents
are required to reduce bleached pulp kappa
number to a low level. The significance of
the kappa number on the mechanical prop-
Chapter
743

of Bleached
Pulps
10
C)
~
C\f
E
z
X
Q)
"tJ
.!:
....
as
Q)
. ECF reference sequence

.. TCF sequence 1
o TCF sequence 2
I7
90
Tensile
80
index,
erties of the pulp, however, is smaIl compared to the effects of other variables, particularly those affecting pulping.
7.2 Bleached sulfite pulps

The strength properties of different, conventionally bleached sulfite pulps cover a
great range, from those of strong softwood
sulfite pulps in that they are similar, t()those
of the strongest hardwood kraft pulps although their wet strength is superior, to
those of typical filler pulps exemplified by
hardwood sulfite pulps. Table 14 shows

typical strength values for pulps produced
by different sulfite processes. The table
shows that bisulfite pulp at kappa number
40 has the best strength potential; but at
extended delignification to kappa number
25, there is a risk of considerably lower pulp
strength similar to that of acid sulfite pulp.
Two-stage acid sulfite pulping with a neutral or slightly alkaline first stage can be used
to produce pulp in high yield but with lower
strength. Two-stage sulfite pulping is of
r""le 14. l'tIperrIuI/II.g jn'oJJe11Ies' of M./ferMI MWd bletu:W'

(13,79).
Kappa No.
Unb!. Pulp
Pulp
Yield % of Wood
Unb!.
Bleached
110
100
kNmlkg
IIOjhtJooIlnlflt#J JIIIIps tm4
Beating
TIlDe
(min)
Breaking
Length
(kID')
Tear
Factor
"
Density
(g/cm')
Inwft JIIIIp
Opacity
25
52.4
48.9
50
7.3
89
0.74
0.745
Two-stage acid
sulfite, moderate
hemicellulose
stabilization,
extended delig.
10
52.7
50.8
45
6.9
77
0.74
0.72
Bisulfite
25
40
52.3
54.9
48.8
49.4
60
55
7.5
8.6
90
87
0.74
0.74
0.75
0.725
32
49.2
46.0
88
11.0
115
0.74
0.71
Beaten
in a Valley
and Practice
r"",.u.
I!./ft of~
blHebl", ore.
beater.
(pH in the peroxide
treatment)
(Amount
groups)
of charged
% ISO
Tensile stiffness
p/IyskIIIproperHa of N~
59.4
28.8
3.4
105
351
index
Scott Bond, JIm'

Density, kg/mJ
Tear index, Nm/kg
Tensile energy
light
7.3 Bleached (chemi)mechanical

pulps
Bleaching can seek to preserve papermaking properties, including maintainance
of a suitable balance between strength and
light scattering, or to improve strength, in
which case good light scattering is sacrificed. Peroxide bleaching at low pH (starting pH of about 10.5-11.5) affects mainly
chromophore elimination, whereas peroxide bleaching at high pH (a starting pH
above 12) additionally introduces a considerable amount of carboxyl groups through
oxidation by oxygen-containing radical species. Carboxyl groups promote swelling,
fiber bonding, and paper strength. Table
15 illustrates the effects of these two pH
conditions on strength properties (69, 71,
81).
Chemimechanical
softwood pulps are
recognized
mainly for their superior
strength, therefore making further strength
improvement during bleaching a desirable
objective. For hardwood chemimechanical
pulps, a balance between strength and light
scattering nevertheless may be important;
it is achieved by adjusting the process conditions used in chip pretreatment
and
bleaching. Of particular interest is aspen
CTMP bleached to an ISO brightness of
about 85%. This pulp is used when opacity
and good surface properties in high-quality
printing papers are required.
Conventional hydrosulfite bleaching has
very little effect on the mechanical properties of (chemi)mechanical
pulps because of
Unbleached
TMP
Tensile index, kNm/kg
CEDEDsequence.
Old SCA standard.
-Principles
particular interest for pulping to very low

kappa numbers because the pretreatment
increases
the selectivity
of the final
delignification. The final pulp yield and, to
a degree, the papermaking properties can
be controlled by adjustment of the pH in
the pretreatment stage. A general characteristic of the different sulfite pulps is the
low beating energy required.
Bleaching can affect the mechanical
properties of sulfite pulps through carbohydrate degradation
and carbohydrate
(hemicellulose) dissolution (40). The hemicelluloses in sulfite pulps are not stabilized
against alkali as they are in kraft pulps.
Carbohydrate dissolution is promoted by
severe conditions in alkaline extraction,
oxygen delignification, and high-temperature peroxide stages. To a degree, hemicellulose dissolution tends to increase overall
strength somewhat but also increases the
beating requirements.
Efforts to minimize the effluent load
have, as for kraft pulps, led to the use of
extended pulping in sulfite processes.
In
such cases, the acid sulfite process is preferred (79, 80). The lower strength of acid
sulfite pulps can be attributed mainly to acid
attack at sites in the fiber waIl receiving
compression damage during chipping (30).
Extended pulping tends to aggravate this
problem, making the production of strong
pulps more difficult. Improved strength,
however, may be obtained through better
control of the chipping conditions.
Brightness,
Kraft
Pulp Bleaching
Property
Acid sulfite
744
scattering
absorption
coefficient,
index,J!kg
m'!kg
8.2
385
45.3
SJWIIUTMP(69, 81).
Peroxide
Low
Low
71.5
- bleached
TMP
High
High
31.3
3.6
115
382
71.3
34.6
3.8
139
452
8.2
415
45.0
8.0
510
40.1
Chapter
vn 3: Strength Properties and Characteristics

of Bleached
Pulps
the reducing (t.e. , non-degradatative) action

of the chemical. A product of hydrosulfite
bleaching and decomposition
is sodium
sulfite (see Chap. III, Sect. 4, Subsect. 3.1).
This chemical can react with coniferaldehyde-type structures in lignin forming sulfonic acid derivatives (see Chap. III, Sect.
4, Fig. 13). These latter groups, which are
more likely to be formed when a high
charge of hydro sulfite is applied to the pulp,
may significantly decrease the light-scattering coefficient (3). A lower scattering coefficient may make bleaching to the normal
hydro sulfite bleaching
ceiling more
difficult.
8. Future trends in pulp

strength testing
Characterization of bleached pulp properties, in practice, is based mainly on traditional methods having only an empirical
connection to fundamental strength parameters.
One reason for this is that any
changes made in test methods would make
the extensive, previously aquired knowledge obsolete and of little value for future
use. In many cases, it is possible to relate
measurable fiber properties, such as are
obtainable from commonly used test methods, to the characteristics of simple paper
structures.
However, because of the increasing complexiry of papermaking, it is
becoming increasingly difficult to assess the
influence of individual pulps on the paper
properties. This is partly because of an inadequate description of fiber properties,
partiy due to lack of effective models to
describe the interaction between furnish
components in paper. Wet end chemistry
and fiber distribution in the paper sheet are
other factors which make the pulp qualiry
assessment difficult. The test methods that
are used are time-i:onsurning and not sufficiently accurate for application to single
tests.
An interesting development, which may
revolutionize fiber characterization, is the
use of image analysis for optical measurements of the dimensions and shape of pulp
745
fibers in a dilute suspension. A wealth of

information can be obtained by such an
analysis but a crucial problem is to make
operational
use of it. Ultimately, image
analysis, in the case of high resolution spectrometric measurements, using near infrared (NIR) or UV light may provide detailed
chemical information about individual fibers.
Zero-span and short-span tensile tests are
being used to characterize fiber strength
and strength-bearing fiber length. The tests
also are affected
by curl, kinks, and
microcompressions
which decreases the
breaking load but increases the breaking
elongation. A careful analysis of the stressstrain relationship should increase the precision. Moreover, fiber strength analysis has
to take into account changes occurring
during beating which introduces the issue
of how to beat in a relevant way. Further
development in beatabiliry testing is pro~
ably one of the most important future needs
in strength testing.
The development of useful models indicating how fibers perform in papers are
progressing partly by the application of
empirical methods. However, the simultaneous trend toward more sophisticated
p!permaking makes it increasingly difficult
to apply them for the characterization
of
an individual pulp. In a way, this may well
be regarded as a sign of the decreasing importance of individual pulp properties in
modem papers.
The characterization of pulps has been
and is highly strength-oriented.
However,
pitch problems or problems relating to dimensional stabiliry, for example, are often
more important than strength insufficiency.
Therefore, there is a need for a holistic view
of papermaking properties which would
require the development of more stringent
test methods than are presently available.
It would also be necessary to develop relevant laboratory methods for assessing
runnabiliry of pulps in paper mills which
in turn would require a better knowledge
of what factors are critical in the papermaking process.
746
References
17. Clark,].
1. Nordman, L., in Pulp and Paper Manufacture, Volume 2, Mechanical

Pulping (R.A.
Leask, Ed.) 3rd edn., Joint Textbook Committee of the Paper Industry, TAPPVCPPA,
Atlanta, Montreal, 1987, pp. 275-282.
18. Bridge, N.K. and Homer, R]., Paper

Ind. 18(12):37 (1977).
2. Forgacs,
(1 %3).
O.L., Pulp
Pap. Can. 64(C):T89
3. Seth, R.S., Barbe, M.C., Williams, ].C.R.,

Page, DR, Tappt 65(3):135 (1982).
4. Clark, ].d'A, Pulp Technology
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San
Fransisco, 1985, pp. 356-407.
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Pulp Technology
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19. Paavilainen,
(1990).
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72(5):
Tech.
S 16
L., Pap. PItU 74(9-10):689
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23. Macleod, ].M., Cyr, M., Embley,

age, P.].J. Pulp Pap. Set. 13(3):J87
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(1981)
25. Colley,].,
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Preprints,
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13. Annergren,
G.E., unpublished
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14. Backstrom,
M, "Nagra synpunkter
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26. Macleod,
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P., Tabert,
J.M., Pulp
J., Apptta
Pap. Can. 87(1):76
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28. Mohlin, U.-B. and Alfredsson,
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S.A., Pulptng
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30. Bausch,
H. and Hartler,
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Pappersttdn.
63:79 (1960); Harlter
N.
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2a nordiska
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63(5): 143
38. Rydholm,
S.A., Pulping
Processes,
Interscience
Publishers, New York, 1%5,
pp. 970-971.
39. Lennholm, H., "Investigations
of Cellulose
PoIymorphs
by 13C-CP/MAS-NMR Spectroscopy
and Chemometrics;
Ph.D. Thesis, Royal
Institute
of Technology,
Stockholm,I994.
40. Rydholm,
S.A., Pulping
Processes,
Interscience
Publishers, New York, 1%5,
pp. 1155 - 1163.
41. McKee, R.C., Paper Trade],
155(21):34
(1971).
42. Nordman,
L., Hirvonen,
P., Levlin, J.-E.,
Ebeling, K., Papter 34(6):219 (1980).
43. Karenlampi,
(1992).
P., Pap.
Puu
74(8):650
44. Howard, R. C. and Biehard, W, "The basic

effects of recycling on pulp properties;
1st Research Forum on Recycling Proceedings, CPPA, Montreal, 1991, p. 81.
45. Hoglund, H., Fredriksson,
B., Eriksson, I.,
"Chemothermo-mechanical
pulp in newsprint furnishes;
1977 International
Mechanical Pulp Conference
Proceedings,
EUCEPA, Helsinki, Finland, 5:53.
46. Fahey, M., in Pulp and Paper Manufacture ,Volume
2, Mecbantcal
Pulptng
(R.A.Leask Ed.) 3rd edn.,Joint
Textbook
Committee
of the Paper Industry, TAPPI/
CPPA, Atlanta, Montreal,
1987, pp.252271.
47. Forgacs,
(1 %3).
0.1., Pulp Pap. Can. 64(C):T89
48. Mannstrom,
49. Franzen,
(1986).
B., Tappt 55(4):551
R., Nord. Pulp
51. Zhang,Y., SjOgren, B., Engstrand, P., Htun,

M., ] Wood Cbem. Tecbnol.
14(1):83
(1994).
52. Leask, R.A., in Pulp and Paper Manufacture, Volume 2, Mecbantcal Pulping (R.A.
Leask Ed.) 3rd edn. ,Joint Textbook Committee of the Paper Industry,TAPPI/CPPA,
Atlanta, Montreal, 1987, pp. 107-128.
53. Cowan, WE, Tappt]
Papperstidn.
(1972).
Pap. Res.]
50. Brandal, J. and Lindheim, A., Pulp

Mag. Can. 67(1O):T431 (1966).
1(3):4
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747
77:10(1994)
748
70. Levlin,).-E., Pap. Puu 73(6):512 (1991).

71. Engstrand, P., Htun, M., Jonsson, V.,
Pettersson, R., SjOgren, B., Zackrison, H.,
"Peroxidblekning
av mekanisk och
kemimekanisk
massa
vid
hog
massakoncentration;
Final report, sm,
Stockholm,
March 1988 (in Swedish).
72. Britt, K.W and Vnbehend,

68(4):104 (1985).
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80. Hultman, B. and Hillstrom,

R., "Domsjo
suphite mill- environmental
protection by
the development
and use of new technology; EVCEPA Symposium
Proceedings,
Helsinki, 1986, p. 75.
81. Engstrand,
P., Sjogren, B., Olander,
K.,
Htun, M., "Significance
of carboxylic
groups for the physical properties
of mechanical pulp fibers; 6th International
Appita,
Parkville,
Victoria,Australia,
1991, Vol, I, p. 75.
54. Kibblewhite,
(1972).
R.P., Pap. Puu
54(11):709
73. Britt, K.W, Vnbehend,J.E.,

Tappt] 69(7):76 (1986).
55. Kibblewhite,
(1972).
R.P., Appita
26(3):196
74. Lott, EH. and Pascher,

H., Wocbenbl.
Papterfabr. 100(6):188 (1972).
82. Hartler,
N., Nord.
10(1):4 (1995).
75. itkka, P.O., MacLeod,J.M.,

Tappt] 74(1):137 (1991).
83. Bennington,
c.P.J. and Seth, R.S., in Fundamentals
of Papermaktng:Transactions
of the Ntnth Fundamental
Researcb Sympostum held at Cambridge (C.E Baker and
V.W Punton, Eds.) Mechanical
Engineering Publiehations
Ltd., London, 1989, p.
87.
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77(6):158
(1994).
58. Macleod, J.M., and Pelletier, 1.J., Spring

Conference
of CPPA Proceedtngs,
Tech.
Sect., CPPA, Montrea1, 1987, p. 1.
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70(11):47
J.M., and Pelletier,

(1987).
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61. Gurnagul, N. and Page, D.H., Tappi J

72(12):164
(1989).
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San
Fransisco, 1985, pp. 720-721.
63. Croon, I. and Dillen, S., Tappi
(1%8).
51(5):97A
64. Bergnor, E. and Genberg, K., SSVL project

Miljo 93, Final report Miljo 93, SSVL, 1991,
p. 228, (in Swedish). Available from AFIPK AD, Box 8309,5-10420
Stockholm.
65. Annergren, G., Backlund, S., Hagglund,T.A., Lindblad, P., Przegl. Papier. 28(10): 239
pp. 3~7,
339, 341, 343, 345, 347, 349
(1972) (in polish).
66. Annergren,
G., "Technical
aspects
of
pulping chemistry; Wood Chemistry Conference
Proceedings,
SPCI, Stockholm,
1980, Vol. n, p.3.
67. Nordman,
29(7):274
1. and
(1975).
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J.-E., Papter
68. Olander, K., Htun, M., Gren,

Pap. Set. 20(11):J338 (1994).
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Pulp
69. Zhang,Y., Sjogren, B., Engstrand, P., Htun,

M., J Wood Cbem. Tecbnol.
14(1): 83
(1994).
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R.,
Kovasin, K.K.,
76. Ma1inen, R., Rantanen, T., Rautonen,

R.,
Toikkanen,
1., "TCF Bleaching
to high
brightness
bleaching sequences and pulp
properties;
International
Pulp Bleaching
Conference
Proceedings,
Tech. Sect.,
77. Nutt, WE., Griggs, B.E, Eachus, S.W,

PikuIin, M.A., Tappt] 76(3):115 (1993).
78. Gottlieb,
P.M., Nutt, W.E., Miller, S.R.,
Macas,T.S., Tappt] 77(6):117 (1994).
79. Annergren, G., Rydholm, S., Vardheim,
Svensk Papperstidn.
66(1):1 (1%3).
S.,
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Paper.
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84. Seth, R.S., Francis, D.W., Bennington,

c.P.J., Apptta]
46(1):54 (1993).
85. Hakanen, A. and Hartler, N., Pap. Puu

77(5):339
(1995).
86. McKenzie,A.W,Appita
87. Page, D.H., Tappt]
42(3):215
77(3):201
(1989).
(1994).
88. Middleton,
S.R. and Scallan, A.M., Nord.
Pulp Pap. Res.] 7(1):22 (1992).
SECTION vm:
Pulp Bleaching and The Environment
Chapter 1:
Emuent Characteristics
and Composition
A. B. McKague
Pulp & Paper Centre
Toronto, Canada
G. Carlberg
The Norwegian Pulp and Paper
Research Institute
Oslo, Norway
1. Introduction
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 751
2. General characteristics of bleach plant eftluent . . . . . . . . . . . . . . . . . . . . . . . . .

2.1 BOD
2.2 TOC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,,' . . . . . . . . . . . . . . . . . . . . . . . .
2.3 COD.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4 Color . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.5 AOX . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.6 EOX . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.7 Molecular weight distribution of effluent components
751
751
752
752
752
753
754
754
3. Chemical characteristics of eftluent components.

. . . . . . . . . . . . . . . . . . . . . . . 759
3.1 Characteristics of the high molecular weight material . . . . . . . . . . . . . . . . . . . 759
3.2 Compounds reponed in bleach plant effluent. . . . . . . . . . . . . . . . . . . . . . . . . 760
Chapter VIII I: Effluent Characteristics and Composition
Chaptervm
1:
Emuent characteristics
and composition
1. Introduction
Describing the characteristics and composition of bleach plant effluent is like trying to hit a moving target whose speed is
increasing exponentially. Five to ten years
ago it was possible to categorize bleaching
as conventional or modified in the sense
that "modified" meant some chlorine dioxide substitution was employed or that oxygen delignification
preceded what was
essentially conventional bleaching. Reflecting the environmental and matket pressures
to eliminate cWorine from the bleaching
process, bleaching is now classified according to the use of cWorine-containing bleaching agents. Thus, processes that do not use
molecular cWorine are referred to as elemental chlorine-free (ECF), and those that
do not use any chlorine-containing
bleaching agents are referred to as totally chlorinefree (fCF). The rapid changes which have
recently occurred have led to the appearance of a large number of publications in
which the general effluent characteristics
are reported, particularly the amount of adsorbable organic halogen (AOX), but little
is known about effluent composition in
terms of individual compounds.
In this
chapter, an attempt is made to provide a
description of bleachery effluents, recognizing that in focusing our sights on this
target, it is moving rapidly.
2. General characteristics of
bleach plant effluent
To describe bleach plant effluent in a
systematic manner, a classification system
is needed for the different types of bleaching processes. In view of the current emphasis on decreasing
the quantities of
cWorinated organic compounds
formed
during bleaching
and the anticipated
growth of TCF bleaching, effluents have
been classified as conventional (up to IO"/"
cWorine dioxide substitution), ECF,andTCE
75 I
This very simple classification system is not

meant to ignore the different levels of chlorine dioxide substitution that can be used,
but rather to be in tune with the trend in
bleaching technology. Two reviews have
been published previously which describe
the effect of cWorine dioxide substitution
on the characteristics of bleach plant effluent (1, 2). It is apparent from these reviews
that a high degree of cWorine dioxide substitution may be needed before any significant effect in a given parameter is observed,
and that any effect is much more apparent
when systematic variations are performed
within the same study, rather than when
results from different studies are compared.
In this chapter, important changes resulting from substitution by chlorine dioxide,
oxygen delignification,
decreases in the
kappa number of the unbleached pulp, and
incorporation of ozone into ECF bleaching
are reviewed.
It is not possible to systematically discuss
the effects of all the variations possible for
given bleaching sequences, for example, the
effects of e:lodifying or eliminating certain
washing steps (3, 4), split additions of chlorine and chlorine dioxide (5, 6), or enzyme
pretreatment (7,8) as these are studies in
themselves and beyond the scope of this
chapter. However, where these variations
are important, for instance in the formation
of AOX and certain types of organic compounds, they are included. It should also
be mentioned that levels of the parameters
used to characterize bleach plant effluent
can no longer be related to levels in final
mill discharge. The degree of bleach plant
closure increases as chlorine-containing
bleaching agents are removed from the process. Complete closure of mills employing
TCF processes
may be possible in the
future.
2.1 BOD
BOD (Biochemical Oxygen Demand) is
a measure of the oxygen required for the
biochemical degradation of organic material in water or effluent, The BOD of bleach
plant effluent depends on the kappa number and extent of washing of the unbleached pulp because both the residual
752
Pulp Bleaching
-Principles
and Practice
lignin and black liquor components

are
solublized during bleaching. Typical BOD
levels in effluents from the kraft bleaching
of softwood pulp are shown in Table I.
CWorine dioxide substitution has little effect on BOD until the level of substitution
is almost 100%. For example, an NCASI review (2) found that BOD decreased 20-30"/"
at 90-100% substitution.
In both conventional and chlorine dioxide-substituted
bleaching, the introduction of an oxygen
prebleaching step can reduce BOD up to
70"/" (2, 9, 11-17). In TCF bleaching, effluent loadings of 26-861b (12-39 kg)/t of pulp
have been reported (8, 12, 13). BOD levels
of effluents from hardwood bleaching are
normally lower than those from softwood
bleaching because the kappa number of the
unbleached pulp is normally 10wer.The effect of cWorine dioxide substitution on the
BOD of hardwood effluents is not clear from
the available literature. Replacement
of
chlorine dioxide by ozone in the first stage
of ECF bleaching is reported to lower BOD
dramatically because less than 10% of the
dissolved organic material is discharged
(18).
2.2 TOC
TOC (fotal Organic Carbon) is a measure
of the carbon in all organic compounds,
both oxidizable and non-oxidizable, in water or effluent. TOC has been determined
for a large number of conventional bleaching effluents (fable 2). limited data are available to show the effect of chlorine dioxide
substitution; however, the results of a previous survey indicated there is no significant difference in theTOC levels (1). The
TOC of hardwood effluents appears to be
similar to that of softwoods and is also un-
affected by chlorine dioxide substitution.

Inasmuch as recent studies reported a 35%
decrease in TOC at 100% cWorine dioxide
substitution 09,20). the effect on TOC is
still not clear. In another study (14), a 63%
reduction in the kappa number of an unbleached pulp by oxygen prebleaching led
to a decrease of 52 and 75% Toe in the Cand E-stage liquors from conventional
bleaching and 42 and 86% in the D- and Estage liquors from 100% cWorine dioxide
bleaching, respectively. No data were found
forTCF effluent.
2.3 COD
COD (Chemical Oxygen Demand) is a
measure of the oxygen consumed in the
chemical oxidation of organic material in
water or effluent, by a strong chemical oxidant. As with BOD, the COD of bleach plant
effluent depends on the kappa number of
the unbleached pulp.Typicallevels of COD
for conventional
bleaching of softwood
kraft pulp are shown in Table 3. COD levels of hardwood pulp effluent are substantially lower. As discussed in a previous
review (1), COD decreases with increasing
cWorine dioxide substitution as would be
expected since the products of chlorine dioxide bleaching are at a higher oxidation
level than those from chlorine bleaching.
A decrease in 20-25% of the COD occurs
at 100% chlorine dioxide substitution
(1,13,16,22). Oxygen delignification lowers COD values in proportion to the reduction in kappa number (typically 40-50%).
The COD of effluent from TCF pulp is 662951b (30-134 kg)/t (8, 12,23).
2.4 Color
Effluent from the first two stages of conventional bleaching of softwoods and hard-
Type of bleaching
C(D) stage
IbIt (kg/t)
E stage
Iblt (kg/t)
Total bleach
Iblt (kg/t)
Conventional
9-22(4-10)
4 - 18 (2 - 8)
22.24 (10 - 20)
ECF
14 (6.5)
11 (4.8)
18.35 (8 - 16)
26 - 86 (12 - 39)
TCF
'Kappa number: 30 . 35
Chapter VIll 1: Effiuent Characteristics and Composition
753
Tule 2. roc of softwood lnwft pull' bluebhJg efflllelll (9,10,14,19 -11).
754
T4ble 5. '/'yJIIaIlAOX
MlfleSjor
lnwft pulp'
bletlebi"g
Type of bleaching
C(D) stage
Ibit (kglt)
E stage
Ibit (kgIt)
Total bleach
Ibit (kglt)
Type of bleaching
Cb(D) stage
Ibit (kgIt)
Conventional
7-29(3-13)
70 - 75 (32 - 34)
44 - 53 (20 - 24)
4.0 - 9.2 (1.8 - 4.2)
ECF
9- 48 (4 - 22)
36 - 37 (16 - I7)
Conventional
16 -18 a.3 - 8.3)
ECF
0.9 - 1.3 (0.4 - 0.6)
'Kappa number: 26 - 38
Tule
lnwft}nlll'
bluebhJgejJllIeIII
C(D) stage
Ibit (kglt)
Type of bleaching
(6,9,13,Z8,3Z
- 34).
E stage
Ib/t (kglt)
Total bleach
Ibit (kglt)
5.3 - 6.6 (2.4 - 3.0)

0.7 - 0.9 (0.3 - 0.4)
8.1-15
(3.7 - 6.8)
- 1.7)
2.0 - 3.7(0.9
'Kappa number 19 - 34.

bChlorine multiple 0.21 - 0.47.
TCF
TtIble 3. COD of softwood
effl_t
- 57(21
Conventional
46
ECF
48 (22)
- 17,n - Z5).
(8,9,tZ,13,15
E stage
Ibit (kglt)
- 26)
68
- 119
(31-
54)
lnwft JnIlJI' bleaebi"g
Cb(D) stage
effl_t
(Z9,30,3Z,38
E stage
136 - 161 (62 -73)
66 - 295 (30 -134)
ECF
'Kappa number:
- 41).
Total bleach
Ib/t (kg/t)
0.018 - 0.15 (0.008 - 0.07)
Conventional'
75 - 123 (34 - 60)
TCF
softwood
Type of bleaching
Total bleach
Ibit (kglt)
117 (53)
6. EOX IJtdfleSfor
0.002 - 0.022 (0.0009

16
- 0.01)
- 26
"Chlorine multiple: 0.16 - 0.28

'Up to 18%CIa,
'Kappa number: 30 - 37
Tule 4. Color of softwood lnwft pull' bleaebi"g effl_t
(8,9,13
- 16,ZZ
- Z4).
Type of bleaching
C(D) stage
Ibit (kgIt)
Estage
Ibit (kgIt)
Conventional
42 - 119 (19 - 54)

51 (23)
282 - 546 (128 - 248)

150 (68)
ECF
TCF
Total bleach
Ibit (kglt)
486
- 939
(221
- 427)
57 - 330 (26 -150)

59 - 343 (27 - 157)
'Kappa number: 25 45
woods typically contains over 90% of the

total bleach plant effluent color and the Estage alone, 7<Hro% (26, 27). Color levels
are shown in Table 4. Effluent color decreases with increasing chlorine dioxide
substitution (1,2). Thus, an NCASI review
(2) found that a 5<Hro% decrease in color
occurs at 90-100% substitution.
Oxygen
prebleaching decreases the color of bleaching effluent 63-80".1. (14.17), while replacement of chlorine dioxide by ozone in the
first stage of ECF bleaching is reported to
lower color dramatically (18).
cause of recent environmental and market

pressures to eliminate chlorine from bleaching, the fonnation ofAOX during bleaching
is a subject which has been studied exhaustively.
A variety of studies have shown that lignin in pulp is the source of AOX in bleach
plant effluent. Thus, prebleaching
steps
such as extended delignification and oxygen pretreatment,
which decrease the
kappa number of the incoming pulp, decrease AOX correspondingly. For the purpose of this review, no distinction is made
among the variou5 method5 u5Cd for the

2.5 AOX
AOX (Adsorbable Organic Halogen) is an
approximate measure of the chlorinated
organic material in water or effluent. Be-
determination of chlorinated organic material in effluent. Thus, TOCl, AOX, and results from other combustion methods are
all considered equivalent.
Typical AOX levels in bleach plant effluent are shown in Table 5. Chlorine dioxide
substitution results in a virtual linear decrease in AOX in both conventionally
bleached and oxygen prebleached
pulps
(6,9,13,28,29).A
small amount of AOX is
present in effluents from 100% substitution
because, during the reaction of chlorine
dioxide with pulp lignin, a small amount of
hypochlorous acid is generated which reacts with lignin to fonn chlorinated material. The fonnation of AOX is complicated
and dependent on the chlorine multiple
(30) and mode of addition of chlorine and
chlorine dioxide (31).A low chlorine multiple and split addition give effluent containing less AOX. As expected, effluents
from TCF bleaching contain negligible
amounts of AOX. Enzyme pretreatment is
reported (7) to decrease the amount of
bleaching agent required, and to reduce
AOX accordingly.
2.6 EOX
EOX is the tenn used for Extractable Organic Halogen. Since the very non-polar
solvents used for extraction, namely, hex:me, heptane, and cyclohexane, extract only
a small portion of the extractable material,
the tenn is used here to mean that portion
of extractable organic halogen which has a
potential to bioaccumulate. A compound
that has an octanol-water partition coefficient K.>w> 1000 (t.e., log

> 3) has a
K"",
bioconcentration
factor (ratio of the concentration in a biotic phase to that in water) of about 50 (35), a level considered
reasonable by some groups for defining
bioaccumulation potential (36). Non-polar
hydrocarbon solvents give a better estimate
of the amount of material having a log Kotw
> 3 than more polar solvents such as ether,
but there is no standard procedure for measuring EOX. In this chapter, hexane, heptane, and cyclohexane
are considered
equivalent in tenns of extraction efficiency
(37).
EOX levels in bleach plant effluents are
not well documented.
Reported
levels
shown in Table 6 should be considered only
approximate
because some analytical
procedures include steps to remove chlorofonn, which makes a significant contribution to EOX (38). It is evident from these
and other studies (28) that EOX decreases
with increasing chlorine dioxide substitution and oxygen prebleaching (17,29).
2.7 Molecular weight distribution of

effluent components
The two
lar weight
material in
tration and
main methods used for molecudetennination

of the organic
bleachery effluents are ultrafilsize exclusion chromatography
Chapter VllI 1: Effluent Characteristics and Composition

(SEC). Ultrafiltration
membranes
have
pores which allow passage of molecules
smaller than the pores. By passing the effluent through a series of membranes of
decreasing molecular weight cutoff (e.g.,
25,000, 10,000, and 1,000 Daltons), the
organic matter can be separated into distinct nominal molecular weight fractions.
Size exclusion chromatography gives information about the molecular weight distribution of the organic matter. The smaller
a molecule is (t.e., the lower its molecular
weight), the more readily it can diffuse into
and out of the pores of the column packing
material and thus the more slowly it elutes
from the column. The separation can be
performed at high or low pressure and in
water or organic solvents. Both numberaverage molecular weight (Mn) and weightaverage molecular weight (Mw) can be
determined by SEe.
Bleaching produces a complex mixture
of molecules characterized by differences
in size, geometry, and polarity. Difficulties
in the molecular weight determination may
result from adsorption on membranes and
gels, ionic interactions, and intermolecular
associations (4247). The extent of adsorption in SEC is dependent both on the nature of the gel and the solvent employed
(42, 44). Ionic interactions are attributable
to the polyelectrolytic nature of dissociated
lignin in aqueous alkaline solutions (46).
The effect of intermolecular association in
SEC of lignins has been discussed
by
Sarkanen et al. (47). It has been suggested
that hydrogen bonding, hydrophobic interactions, and long-range van derWaals forces
lead to association (48-50), giving a higher
apparent molecular weight. The use of
strongly polar mobile phases, such as dimethyl sulfoxide
(DMSO) and dimethyl
formam ide (DMF), in the presence
of
lithium halide salts may eliminate association effects (42,45,47,51,52).
These solvents form hydrogen bonds with the sample
molecules and solvate them completely.
Tetrahydrofuran (fHF) can break down the
association dimers often formed in solutions
of carboxylic acids without leading to extensive solvation (47). Another way to di-
755
minish the adsorption

and association
caused by hydroxyl groups is to remove
them by derivatization. Acetylation (52),
methylation (53), and silylation (52) have
been used for this purpose. Derivatization
can also increase the solubility of the lignin
breakdown products. Although Ekman and
lindberg (53) did not find significant differences in the SEC elution profiles of methylated and underivatized lignin, Pellinen
and Salkinoja-Salonen (52) found that acetylation and silylation usually increased the
observed average molecular weights.
The molecular weight in SEC is determined by comparison with standards of
known molecular weight. A combination
of low molecular weight model compounds
and high molecular weight compounds, in
most cases polystyrene sulfonate and polystyrene standards, are often used. That
these standards may differ from the investigated compounds in size, geometry, and
polarity obviously affects the results; however, no ideal standards are available.
In additon to ultrafiltration
and SEC,
methods such as vapor phase osmometry
and dialysis have been used for molecular
weight investigations of bleaching effluent
(54-56).
The results of molecular weight determinations are described below. The influence
of different bleaching sequences, differences between ultrafiltration and SEC results, and the influence
of biological
treatment are also discussed.
Early investigations
of the molecular
weight distribution of organochlorine compounds in bleached kraft mill effluent were
performed by ultrafiltration.
The results
obtained by lindstrom and Osterberg are
shown in Fig. 1 (57,58).
It can be seen that the chlorination and
alkaline extraction stage effluents differ
greatly in the molecular weight distribution
of their chlorinated organic matter. The alkaline extraction stage contains a higher
proportion of high molecular weight chlorinated matter than the chlorination stage.
The relative distribution is also dependent
on the bleaching sequence. Lindstrom and
Osterberg compared the effluents from
756

5%
55%
50%
"--Chlorination stage
CJ
CJ
~
Extraction
stage
MW<1000
1000< MW<10,000
1000<MW<25,000
MW> 25,000
Fig. 1. MoIec8,.,. mgbt
ojcblorllUlteti tlllltn141 In bleacbl.g ejJlrmll (57,58).
three kraft softwood pulp prebleaching sequences: CE, OCE, and DE. In the acidic
effluents, about 65-70",,(,of the organochlorine material (as TOCl) was found in the
high molecular weight fraction (M>I000)
of the C and OC liquors. When chlorine
dioxide (0) was used in the first stage, only
45% ofthe organically bound chlorine was
found in the high molecular weight fraction.
In the alkaline extraction liquors, 90-95%
of the organically bound chlorine was found
in the high molecular weight fraction for
all three bleaching sequences. In the alkaline extraction liquors of the CE and OCE
sequences, 5~5% of the organically bound
chlorine was found in the highest molecular weight fraction (M>25000). The alkaline extraction liquor from the DE sequence
was only ultrafiltered at a relative molecular weight limit of M>I000. Pfister and
Sjostrom (59,60) and Hardell and de Sousa
(61,62) had previously found a lower proponion of high molecular weight material
using similar experimental
conditions.
Pfister and Sjostrom (59,60) and O'Connor
et al. (32) found that oxygen prebleaching
increased the proponion of material in the
M<I000 fraction ofthe alkaline extraction
liquor and combined chlorination and extraction effluents.
Combining
samples from different
bleaching stages or upward adjustment of
the pH leads to mineralization and dechlorination which may change the molecular
weight distribution
(63,64).
Recently,
McKague and Reeve (65-67) have provided
some clarification of the reactions taking
place during the alkaline treatment. They
reacted lignin model compounds sequentially with chlorine or chlorine dioxide and
sodium hydroxide.
After the oxidation
stage, muconic acid esters, lactones, and
quinones were formed (see also Brage et
al. Holzforschung
45:23(1991);
ibid.
45:147(1991);
Ni et al. J. Wood Chem.
Technol. 14:243(1994)).
During the alkaline treatment, the quinone rings were
opened and some organically bound chlorine was displaced. Similarly, the lactones
were convened
to muconic acids. These
reactions increase the polarity of the material and, with it, its ability to associate.
Sameshima et al. (56) used cellophane
membranes for dialysis of bleachery effluents. The nominal molecular weight cutoff
was not stated. In the chlorination liquor,
nearly all (95%) of the organic matter (TOC)
was found in the low molecular weight fraction. Two experiments were performed on
the alkaline extraction stage effluent. After
a single 24-hr dialysis, 65% of the TOC was
found in the high molecular weight fraction.
After excessive and repetitive dialysis, only
32% of the TOC remained in the high mo-
Chapter vrn 1: Effluent Characteristics and Composition

lecular weight fraction. The numerical values of average molecular weight of the high
molecular weight retentates as measured by
vapor pressure osmometry were about
3100 and 7000 for the two experiments.
S:igfors and Stark (68) used SEC to investigate the proportion
of high molecular
weight material in acidic and alkaline
bleaching effluents from four mills pulping
hardwood and softwood mixtures. The
amount of high molecular weight material
(M> 1(00), as measured by UV absorption,
was found to be 65-75% in the a1ka1ine effluent and 20",(,in the acid-stage effluent.
Only minor differences were found in the
chromatograms of effluents from the different mills. Pellinen and SaIkinoja-Salonen
(69) analyzed the a1ka1ine extraction effluent from the OCE bleaching of softwoQd
pulp using three different SEC systems. The
number-average molecular weight ranged
from 1600 to 2000 and the weight-average
molecular weight from 2700 to 4900.
The organic material in bleaching effluent from hardwood kraft pulps has a lower
molecular weight than the material in the
softwood effluents (70,71). One example
of the difference in molecular weight distribution using aqueous SEC is shown in Fig.
2. The difference was attributed to differences in the degree of chlorination and in
757
the chemical structure of the respective

residuallignins.
Effluents from modem mills using different delignification techniques such as extended pulping and ECF bleaching (AOX
less than 0.5 kg/t) have been characterized
with respect to molecular weight distribution (40,71). The results indicate that, regardless
of bleaching
sequence,
the
molecular weight distribution in the spent
bleaching liquor follows a curve similar to
the one shown in Fig. 2. About 50% or more
of the organically bound chlorine in the effluents is found in the high molecular
weight fraction (M> 1(00).
Ultrafiltration results have been reported
both for organic matter (TOC or COD) and
organically bound chlorine (AOX orTOCl),
while the SEC results are reported as UVabsorbing components, thus making comparison of the two difficult. Previously,
relatively larger proportions of high molecular weight compounds were found by ultrafiltration
than by SEC. Jokela and
SaIkinoja-Salonen (54) recently reported
results from a molecular weight-distribution
investigation of organic halogens in both
softwood and hardwood kraft pulp bleaching effluents. The molecular weight distribution was studied
by aqueous
and
non-aqueous SEC and ultrafiltration. Using
758
Pulp Bleaching
-Principles
ultrafiltration, they found that 55% of the

AOX was low molecular weight 1000);
however, using non-aqueous SEC, over 85%
of the chlorinated material in the same
bleaching effluent was found in the low
molecular weight fraction. These results
were confirmed by vapor phase osmometry.
A higher molecular-weight
peak was obtained with aqueous SEC than by nonaqueous SEC using TIfF as an eluent, (950
and 350 g/mol, respectively).
The difference was attributed to decreased intermolecular association of lignin fragments in
TIfF. It was also found that the proportion
of effluent material retained by ultrafiltration with a nominal molecular weight cutoff of 10,000 decreased
by 75% upon
l()()'fold dilution with distilled water. The
explanation for this effect was that the halogenated components occur as micellar
aggregates which break up at very low concentration. Dahlman et al. (40) suggest that
these observations may be largely the result of a "washing effect" and improved ultrafiltration
following
dilution of the
effluent. They argue that formation of micellar aggregates is less likely because of the
highly oxidized and hydrophilic nature of
the material. Furthermore, Dahlman et al.
obtained fractionation
results similar to
those reported by Jokela and SalkinojaTlIble 7. MolecalM
mg61
tllstrl1nU#oll
eJP8MI.
Kraftmill effluents
Softwood
_ _ _ Hardwood
and Practice
of orgawally
Salonen using an effective (tangential flow)

ultrafiltration followed by sequential batch
diafiltration without dilution. Roy-Arcand
and Archibald (55) performed molecular
weight distribution determinations
with
various dilutions of spent bleach liquors and
found no significant distribution
differences.
Secondary treatment reduces the concentration of AOX in bleaching effluents. By
combining aerobic and anaerobic treatments, up to 65% of the AOX may be removed. All classes of organochlorine
compounds are removed during this treatment (72,73). The removal efficiency is
higher for low molecular weight compounds. As a consequence, the relative size
distribution of the materials remaining is
shifted toward the high molecular weight
region. Jokela et al. (74) isolated a fraction of the organohalogens virtually recalcitrant to biotreatment.
This fraction was
the least-chlorinated and was obtained from
the fraction which was insoluble in THF but
adsorbable on active carbon.
Some of the molecular weight distribution results are summarized in Table 7. The
table contains results for the distribution of
both organically bound chlorine and organic matter. Generally, chlorine dioxide
substitution and oxygen prebleaching appear to increase the proportion
of low
boa""
c610rlrul tIruI orgtlMk
Type of Bleaching
CID Stage
E Stage
Total Bleach
% of Effluent Solids Having a MW > 1000 daltons
Conventional
65-70
35-40
20
ECF
45
45
90-95
85-90
Fig. 2. Apparettl
molecular
10'
10'
Molecular weight (polystrene sulphonate)
weig61 distrlbullott
of orga,,'c
rtUIIerltIl
I"
bleached
ltraft mill eJPuenl
(71).
TCF
I"
blHCbittg
Ref.
57,58
59
68
65-75
70
32
45
54
57,58
90-95
80
40-50
10'
mtIIter
59
40
55
32
40-45
75
30-40
75
Chapter VIII 1: Effluent Characteristics and Composition
Bleaching
Sequence
C/Cl
C/O
Functional
Methoxyl
Acidic liquor
CE
1.2
0.22
OCE
8.5
1.1
DE
45
1.2
CE
14
OCE
20
DE
118
759
Groups (mmoVg Organic Material)

Carboxyl'
Hydroxyl
3.5
5.2
0.35
4.9
4.7
0.74
8.7
2.9
1.3
0.58
1.2
0.39
1.7
0.94
3.4
4.2 - 4.5
3.4
4.2
5.8
0.8
Alkaline liQ.uor
Kraft li2llin
,
Determined
molecular
effluent.
by potentiometric
weight
3.7
7.5
titration
material
in bleaching
3. Chemical characteristics of
effluent components
Bleach plant effluent contains an extremely complex mixture of chemical components. Because most of the material has
a molecular weight> 1000, its exact chemical structure is unknown. General structural
features are known, however, and are described in the following section. An enormous amount of work has been done on
material having a molecular weight < 1000
as this is the molecular weight range which
causes most biological effects and is more
amenable to analysis. Over 400 individual
compounds have now been reported, but
it is interesting that this list does not contain any compounds in the 500-1000 molecular weight range. This is the range
where dimeric-to-tetrameric 1ignin degradation products or lignin-carbohydrate
compounds should be found.The identification
of compounds
in this molecular weight
range could provide extremely valuable information about the types of chemicalIinkages present in the high molecular weight
material.
l1
5.
4.3
Characteristics of the high

molecular weight material
During the first bleaching stage, lignin

goes through structural changes leading to
the formation of a chlorinated, degraded,

and extensively oxidized material. In the
reaction with chlorine, aromatic structures
in the residual 1ignin in the pulp are chlorinated and oxidized to quinones (76). The
reaction with chlorine leads to a substantia1loss of methoxyl groups (76). In reactions with chlorine dioxide, the methoxyls
may become part of methyl esters groups
(76) which are saponified in the ensuing
alkaline extraction stage to muconic acids.
lindstrom and Osterberg characterized
the high molecular weight material from
three kraft softwood pulp preble aching sequences, and the results are summarized in
Table 8 (57,58).
.As shown in Table 8, chlorine dioxide
prebleaching gives the highest carbon-tochlorine ratios and in the E-stage filtrate, the
highest carbon-to-oxygen ratios. Chlorine
dioxide also affords the highest carboxyl
and methoxyl, and the lowest hydroxyl
group concentrations.
For comparison, the
methoxyl, carboxyl, and total hydroxyl
group content of softwood kraft lignin
(77,78) is also shown in Table 8. The dramatic changes in the lignin structure occurring during bleaching are evident from the
difference between the content of these
groups in the kraft lignin and the high molecular weight material in the bleaching effluent. Gellerstedt and lindfors (79) have
shown that dissolved lignin always contains
760
Pulp Bleaching
-Principles
and Practice
a higher proportion of oxidized groups at a

given kappa number than residual lignin.
This is in accordance with the fact that dissolved lignin is more exposed to the bleaching chemicals.
In an experiment
with
softwood kraft pulp, dissolved lignin was
found to contain about twice the number
of carboxyl groups after oxygen bleaching
as the residual1ignin in the unbleached pulp
(79).
In recent investigations, Dahlman et al.
(40,75) characterized the high molecular
weight material in effluents from modern
bleaching sequences (ECF and TCF) which
contained low discharges of AOX. The results are summarized in Table 9. In one of
the studies (75), the effects of bleaching
on the high molecular weight material in
softwood and hanlwood effluent were compared. By comparing the influence on the
functional groups of the lignin, it was concluded that the hardwood-derived
materials studied were more degraded than the
softwood-derived materials.
The low AOX discharge is also reflected
in the low chlorine content and high carbon-to-chlorine ratio. Both samples had a
low methoxyl group content and high carboxylic acid group content compared with
unoxidized kraft lignin. The carboxyl acid
group content was, however, lower than
previously found in an investigation of effluents from bleaching sequences using
about 30"/0chlorine substitution (71). This
was unexpected in view of the strong oxidizing capacity of chlorine dioxide and is
contradictory
to the results shown to in
Thble 8.
Oxidative degradation studies (40,75)
indicate that the major part of the residual
Table f). Cbal'fldmmtUm
errt (40,75).
phenolic structural units in the samples

described in Table 9 were unchlorinated but
a minor part (10% for the conventional
pulping sample and about 1-1.5% for the
extended
pulping sample) was monochlorinated. Only trace amounts of dichlorinated aromatic degradation products were
identified. The results also showed that
guaiacyl units dominated the residual phenolic structures as expected. In addition,
p-hydroxyphenyl,
catechol, and syringyl
units were shown to be present.
BC NMR spectroscopy, both solid state
and solution, has been used to characterize
the high molecular weight material in
bleach plant effluent (40, 71). Because of
the complexity of the spectra, no detailed
stmctural information was obtained. The
spectra, however, do permit some general
conclusions to be drawn about the stmcture of the high molecular weight material.
The spectra indicate a low content of phenolic lignin-derived stmctures; furthermore ,
the intensity of signals from methoxyl carbons is low. The dominating signals in the
unsaturated carbon region indicate the presence of olefinic carbons instead of aromatic
carbons in phenolic units. The spectra also
indicate that large amounts of aliphatic carbons connected to oxygen, and saturated
hydrocarbon structures are present. Furthermore, the NMR spectra confirm that the
high molecular weight materials contain
numerous carboxyl groups. Recent studies indicate that some muconic acid stmctures are probably present (65-67).
3.2 Compounds reported in bleach

plant effluent
Over 300 compounds have been reported in bleaching
ofblgb mol_1II1' welgbt tIUIterltll (>1000)
effluent
(80,81).
Re-
I" bletU:bed softwood Imlft JlUlp t'fflu-
Pulping
Process
Bleaching
Process
AOX
(kg ptp)
Conventional
OD(EOP)OOP)D
0.53
1.4
94
1.7
2.8
40
Extended
OD(EO)D(EP)D
0.]9
0.51
260
1.2
2.3
40
n.d.
<0.] >]200
1.2
3.6
7'5
OQP
Cl
%
C/Cl
Functional Groups
(mmoU)
Methoxyl Carboxyl
Ref.
Chapter VIII 1: Effluent Characteristics and Composition

cently, a number of new compounds have
been
reported,
namely,
isomers
of
chlorocymenes
and chlorocymenenes
(82,83), chlorinated monoterpenes
(84),
isomers of chlorothiophenes
(85-87),2,5dichloro-3,6-dihydroxybenzo-l
,+quinone
(chloranilic acid) and the corresponding
hydroquinone
(88), 2,3,4,4-tetrachloro-3hydroxybutanoic
acid (89), dichloroacetonitrile and trichloromethanesulphonyl
chloride (86), chlororetenes (90), isomers
of polychlorodibenzo-p-dioxin
and polychlorodibenzofuran
(91) (see Chap. 3
Section VIII), 2,3,7,8- and 3,4,6,7-tetrachlorodibenzothiophene
(92), chlorinated
furanones (93-95), additional isomers of
chlorophenols, aldehydes and ketones (96,
97), chlorinated veratroles (98), 4-chloC93-hydroxy-2H-pyran-2-one (99), trichlorodibenzothiophenes,
tri- and tetrachlorothianthrenes (100), chlorofluorenes
(101), and
hexadienedioic
acid monomethyl
ester
(102).
Because of the large number of compounds reported, it is not possible to provide a list complete with structures and
quantities. However,ofthe 456 compounds
now reported, 330 are chlorinated and 126
unchlorinated. The different types of chlorinated compounds reported are summarized in Table 10. Important examples of
each group are shown in Fig. 3.
Most of the chlorinated compounds reported were identified in effluents from
conventional chlorine bleaching. Levels of
chlorinated compounds drop by a factor of
about lOin ECF bleaching, and there is a
change in the relative proportions of some
types of compounds. For example, the total amount of chlorophenols decreases from
> 100 g/t of pulp in conventional bleaching effluent to 1-10 g/t in ECF effluent, and
the wide spectrum of chlorophenols found
in conventional chlorine bleaching effluent
changes to one dominated by 6-chlorovanillin in ECF effluent (6, 13, 28, 103). A
acid
~.~
a
3.4.5- Tnchloroguaiacol
;Yro>
222- Trichloroethanol
6-Chlorovanillin
"
1.1.Dichlorodimethyt
Chloroform
xx
oyya
al#o~a
sulfone
Type of Chlorinated
eomptnmdsformed
in bleaebtng.
Number Reported
Compound
Acids, esters, anhydrides,
furanones,
2.3.7.8- Telrachlorodibenzo-p.dioxin
Aldehydes
and ketones
75
25
20
Hydrocarbons
Alcohols
Dioxins and furans
Miscellaneous
Total
few compounds, for example, 1, l-dichlorodimethyl sulfone, do not appear to be markedly affected
by the change
from
conventional
to ECF bleaching (32,89).
Only trace quantities of a few polychlorinated (> 2 chlorine atoms) compounds are
found in ECF effluent. The level of chloroform drops from > 300 g/t of pulp in conventional bleaching effluent to < 10 g/t in
ECF effluent (104). As stated in the introduction, individual compounds have not
been identified in TCF effluent.
Process
for
4. Cook, R.A., "A Bleaching
Mlnimising AOX Discharges," 1992 TAPPI
Environmental
Conference
Proceedings,
TAPPI PRESS, Atlanta, p.l 055.
5. Hise, R.G., Streisel, R.C., Bills, A.M., "The
Effect of Brownstock Washing, Split Addition of Chlorine, and pH Control in the CStage on Formation
of AOX and Chlorophenols
during Bleaching,"
1992 TAPPI
Environmental
Conference
Proceedings,

Fig. 3. Examples
of various
types of eblorluted
eom}HnInds formed
in bleael1tng.
77
52
66
pyrones
Phenols and phenol ethers
3. Allison, WA., McFarlane, P.N., Judd, M.C.,

Pap. Puu 75:234 (1993).
.y CHO
Tule 10. TyJ1esof eblorluted
2. NCASI,Effects of Chlorine Dioxide Substitution on Bleach Plant Effluent BOD and

Color, National Council of the Paper Industry for Air and Stream Improvement,
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York, Tech. Bull. No. 630, 1992.
3-ChI0r0-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone
II
~CHSC~
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du Manoir, JR., Donnini, G.P., Pulp Pap.
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c,~k
CI3CCOOH
762
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761
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Kuokkanen, T. and Koistinen,J.,

sPhere 19:727 (1989).
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Martel, P.H., van lierop, B. Pulp Pap.
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Bleach Plant Effluent;
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Rantio,T.,
(1992).
84.
Hall,
E.R.,
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9O(11):T421
Fraser,
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L-A., Pulp
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48.
Lindberg,J.J.,
Stuthridge, T.R., Wilkins, A.L., Langdon,

A.G., Mackie,
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Carlberg,
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Kirk, T.K., Brown, W., Cowling,

Biopolymers
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552:265 (1991).
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and Salkinoja - Salonen,
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l, Carlberg, G.E., Greibrook,T.,
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56(11):72 (1973).
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Tappi
McCubbin, N., Edde, H. , Barnes, E., Folke,

J., Bergman, E., Owen, D., Best Available
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tbe Ontario Pulp and Paper Industry,
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Axegird,
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Marwah,
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75(7):167
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Lindstrom,
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Colour Removal Tecbnology in tbe Pulp
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26.
33.
Earl, P.F. and Reeve,

72(10):183 (1989).
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Pap. Can. 81(12):T367
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Chemicals;
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C<HJperation
and Development,
Paris,
(1981).
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27.
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Compatible
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Haglind, I., Morek, R., de
Sousa, E, Stromberg, L., "Chemical Composition of Effluents from Chlorine Di.
oxide-Bleaching
of Kraft Pulps before and
after Secondary
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du
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34:80 (1980).
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37:1 (1955).
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20(2):49 (1988).
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E, Svensk
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B., Wat. Sei.

M., )
Morek, R., Reimann, A., Dahlman,

0.,
"Characterization
of High Molecular
Weight Organic Materials in Modern Softwood and Hardwood Ble-.lched Kraft Mill
Effluents;
1991 SEPA Conference
on
Environmental
Fate and Effects
of
Bleached Pulp Mill Effluents, Swedish
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4031, Stockholm,
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Bryant, C.W and Amy, G.L., Wat. Set.

Tecbnol. 21(4/5):231
(1989).
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Remberger,
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Gellerstedt, G., lindfors, E.-L., Pettersson,

M., Sjoholm, E., Robert, D., "Chemical
Aspects on Chlorine Dioxide as a BleachingAgent for Chemical Pulps," 1991 6th
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Smith, T.}., Wearne, R.H., Wallis,A.EA.,

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Smith, T.}., Wearne, R.H., Wallis, A.EA.,

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Mickowski,
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Lahtiperii, M., Lammi, R., Chemosphere
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Jett, S.w., Tappi] 74:159 (1991).
SECTIONvm:
Chapter 2:
Assessing the Potential Impacts
of Pulping and Bleaching Operations
on the Aquatic Environment
J. william Owens
The Procter & Gamble Company
Cincinnati, Ohio
Karl-Johan
Lehtinen
Finnish Environmental Research Group
EspOO, Finland
1. Introduction
.......................................... 3
2. Chemical and physical characterization

eft1uentsandreceivingenvironments
of
4
3. Biological
characterization
of effluents
and receiving environments
4
3.1 Single-species acute and short-term
toxicity tests. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.2
Extended laboratory exposures using

single species
3.3 Mesocosms and experimental streams

12
3.4 Field studies. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4. Expected trends and future research
Glossary.
needs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
767
Chapter
VITI 2: Assessing
the Potential
Chapter vm 2:
Assessing the potential
impacts of pulping and
bleaching operations
on the aquatic
environment
1. Introduction
In recent years, the discharge of bleaching effluents into aquatic receiving environments has been the focus of intense
scientific and regulatory scrutiny. Observations prompting this scrutiny include the
long-range dispersal of bleach plant compounds in Canadian rivers (1) and in the
Gulf of Bothnia (2), the mutagenic activity
of untreated effluents from bleach plants
using elemental chlorine (3,4), the detection of 2,3,7 ,8-tetrachlorodibenzo-p-dioxin
(rCDD) in effluents from bleach plants using chlorine gas (5,6), and the adverse environmental effects of bleached kraft mill
effluent (BKME) discharges lacking biological treatment (7,8). In reaction to such observations, environmental
concerns have
been focused almost exclusively on chlorinated organics, often measured as absorbable organic halogen (AOX) (9). As a result,
the paper industry has sharply reducedAOX
emissions and has eliminated persistent,
polychlorinated materials through chlorine
dioxide (CIO) substitution for elemental
chlorine (10). Simultaneously, the industry has begun to develop bleaching sequences whose stages employ no chlorine
compounds, that is, sequences that are totaIly chlorine-free (rCF).
The aquatic environmental
impacts of
pulp and paper effluents have been the subject of previous reviews by McLeay (11) and
Owens (12). In the 1950-60s, pulp mills
were associated with sometimes devastating effects on receiving waters caused by
the discharge of excessive amounts of suspended solids and organic matter. Historically, the observed adverse impacts have
been attributed to three possible causes: (a)
gross habitat alteration, (b) organic enrich-
Impacts
on the Aquatic
Environment
769
ment and eutrophication

effects, and (c)
chemical toxicity. Owens (12) has summarized examples from the literature of these
impacts in Finland,Sweden,Canada,Bri~
ain, and the United States. These reviews
indicated that environmental
impacts at
mills sites have been sharply reduced with
process modifications aimed at decreasing
the discharge of suspended solids through
fiber recovery and primary clarification and
by decreasing organic discharges using
measures such as dry debarking, screening
room closure, spill control, and external
biological effluent treatment (11,12). Both
reviews included examples of sites where
the receiving environments recovered following process improvements and the installation of external treatment.
Both
reviews also emphasized that the assessment of potential
toxicity impacts of
pulping and bleaching on the aquatic environment is a difficult task.
Pulping and bleaching effluents are
chemically complex and contain many components capable of causing environmental
impacts, such as organic loads, which can
lead to oxygen depletion, nutrients which
can cause eutrophication,
suspended solids which can smother bottom-living or
benthic organisms, color, and a wide spectrum of potentially toxic chemical substances. Process factors that contribute to
the effluent's chemical complexity are (a)
wood furnish (e.g., species-specific variation
in extractives composition),
(b) pulping
process chemistry, (c) degree of closure,
spill control, sewer design, and handling of
condensates, (d) added process chemicals,
(e) the organic load entering the bleach
plant (degree of delignification
or unbleached kappa number and black liquor
carryover), (f) the type and efficiency of
effluent treatment, and (g) operation variability, upsets, and process swings). Thus,
substantial variation exists from site to site,
and no two mills have identical effluents.
Contributions from pulping and bleaching
operations cannot be separated under field
conditions and, even in the laboratory, there
is sometimes carryover of pulping liquor
components into the bleaching process.
770
There are also site-specific physical and

environmental features such as water quality parameters, temperature, stream flow
velocities and sediment loads in rivers, thermoclines in lakes, and salinity in estuaries
which determine the species present and
shape the responses of biological organisms
to effluent discharges. In field studies at
mill discharge sites, habitats and other site
factors must be carefully examined, including seasonal and year-to-year variations.
Combined with site specific factors, neither
adverse effect nor lack of impact can be
widely generalized without a detailed understanding of causality. An environmental assessment
at a mill site must
discriminate between alternative causes
such as organic enrichment and chemical
toxicity within the site-specific circumstances. Otherwise, inappropriate conclusions may be made, leading to incorrect
remediation steps.
This chapter updates the reviews of
McLeay and Owens and emphasizes (a)
those data which can be used to compare
the environmental
effects of different
bleaching process technologies and (b) test
systems and measurements useful for the
environmental characterization of effluents.
Biological terms are defined and explained
in the Glossary at the end of the chapter.
have been developed to reduce chlorate

concentrations
in effluents below those
causing biological effects (15,16). Chelating agents, used to sequester metal ions
such as manganese in TCF bleaching stages
using ozone and hydrogen peroxide, can
potentially solubilize transition metals from
sediments and increase their bioavailability.
In field situations, analyses, as outlined
under the headings of receiving water, sediment, and biota in Table 1, address two primary issues: the transport
and fate of
mill-generated compounds and the exposure of biota to these compounds.
The
transport and exposure routes depend upon
the chemical character of a substance. Water-soluble substances are transported in the
water column and enter higher aquatic organisms through their gills. More hydrophobic substances partition from the water
column to water-borne dissolved carbon
(i.e., dissolved organic material), suspended
sediments,
and deposited
sediments.
Aquatic organisms
are then exposed
through the gut by ingesting sediments or
organisms lower on the food chain. Metabolism and excretion of substances depend on both the particular chemical's
characteristics and structure as well as the
metabolic
capability
of the exposed
organism.
2. Chemical
and physical characterization
of effluents and
receiving environments
3. Biological characterizationof
effluents and receiving environments
Chemical and physical characterization

of an effluent includes the measurement of
both sum parameters and individual substances. The relevant sum parameters and
individual compounds are noted and discussed in Table I together with the environmental information
and perspective
derived from them. The increasing use of
chlorine dioxide increases the potential for
chlorate formation; elevated chlorate levels
can be toxic to certain types of algae, particularly brown algae such as the bladder
WrdCk in the Baltic Sea. Threshold effect
concentrations
for chlorate toxicity have
been identified and validated in field studies (13,14). Effluent treatment processes
Biological characterization is a relevant

approach for defining the occurrence and
extent of environmental impacts on aquatic
organisms. There are a number of different
types of impacts, and these can occur simultaneously, hence, the plural is used. In
this chapter, biological characterization
is
divided into four organizational
levels:
community, population, whole-organism
measurements, and within-organism
measurements. A community is a closely interacting group of species such as organisms
living on or in (he bottom sediment ((he
benthic community) or the near shore areas of water bodies (the littoral community).
A population is the group of individuals
Chapter
VIII 2: Assessing
Tllbk 1. CIHmtktU ~
Measurement
the Potential
of bktwW..,
orTest (units)
Inorganic Parameters
pH, Color/Turbidity (Pt units), Nitrogen and
Total Phosphorus (g/ton and kg/day) Transition metals (grams or mil1igrams per day),
Chlorate (g/ton and kg/day)
Organtc Cbaracterlsttcs
Extractable Organic Chlorine (EOX)
(g/ton and kg/day)
(g/ton
tI.ffIrIMIs 11II4rwm"""
Environment
771
fINIIers.
(fest)
The BOD reflects the combination of process and effluent treatment efficiency (kg/ton) and the overall size of the point source
(tons/day); TSS reflects the suspended solids load in the effluent; AOX reflects the organic material removed in the bleach
plant, the substitution of chlorine gas with chlorine dioxide or
other bleaching agents, and the treatment efficiency.
Aquatic communities are affected by pH; light transmission affects photosynthesis; nitrogen and particularly phosphorus determine enrichment and algal growth; transition metals can be
highly toxic; chlorate can be toxic to certain highly sensitive
algae.
Bioaccumulation is based on the partitioning of a material from
water into lipid. Lipophilic components win be contained within
EOX.There are no standard, established protocols for EOX measurements.
Wetgbt Organtcs
Resin and Fatty Acids and Chlorinated Resin and Fatty

Acids
on the Aquatic
Rationale for Measurement
Sum Parameters
Biochemical Oxygen Demand (BOD), Total
Suspended Solids (I'SS),Absorbable Organic
Chlorine (AOX) (kg/ton and tons/day)
Low Molecular
Impacts
and kg/day),
Chlorophenolics
- mono-
through tetrachloro (g/ton and kg/day),TCDD and

TCDF (picograms per ton or nanograms per day)
Htgb molecular
wetgbt
Organics
Quantity ( kg/ton and tons/day) and
Elemental Ratio (Clo/a)
These materials reflect the tree species pulped (resin and fatty
acids), the chlorine multiple or indicated by the degree of chlorine substitUtion by chlorophenols with di-, trio,and tetra-substitUtion, and the efficiency of effluent treatment.
High molecular weight oxidized Ugnin fragments isolated using
membrane filtration analysis compose the bulk of material discharged after biological treatment of effluent. The elemental
ratio relates to the rate of chlorine used in the bleach plant.
Receivtng Waters
BOD,COD,andAOX (jJg/L) pH, Dissolved Oxygen, Color and Twbidity (Pt units) and Secchi
disk (em), Nitrogen and Phosphorus (mg/L),
chlorate (JJg/L), Resin Acids and Chlorinated
Resin Acids, and Chlorinated Phenolics (jJg/L)
Used to track effluent dilution and background levels. BOD may

be used to test dissolved oxygen models in receiving waters.
Expected "natural" background of AOX is I().20 microgram/L.
To determine if conditions are sufficient to support a normal
ecosystem, including oxygen, light availability for organisms to
carry out photosynthesis, nitrogen, and phosphorus and determine whether ecosystem is oligotrophic, mesotrophic, or
eutrophic. Resin acids and chlorophenols may be used to track
the effluent plume.
772
Pulp Bleaching
-Principles
and Practice
from a single species which inhabit the site.

Communities and populations comprise the
ultimate biological indicators of adverse
effects considered to be meaningful and to
require remediation.
The third and the
fourth organizational levels are,respectively,
whole-organism
or individual measurements such as weight and length and withinorganism measurements
(which may be
further subdivided into organ, tissue, cellular, subcellular, and molecular).
Changes
occurring at these lower organizational levels are not fatal and are referred to as sublethal. The use and interpretation of many
whole- and within-organism
endpoints
(biomarkers) are currently the subject of
intense study and debate among ecotoxicologists. In the context of this chapter, an
endpoint is defined as a measured change
in a biological parameter.
Because endpoints at the lower levels of biological organization may not be connected or linked
with meaningful changes at higher organizationallevels, the relevance and meaning
of endpoints at lower levels are currently
uncertain and their application may be questionable. In this chapter, these measure.
ment categories
are discussed
in four
separate exposure settings: laboratory short-
EPA Studies at
HeavIly Improved Industrial
Effluent SItea
term toxicity tests, extended single species

laboratory exposures, extended experimental stream or mesocosm tests with several
aquatic species, and field studies at mill
sites.
3.1 Single-species acute and shortterm toxicity tests

The principal objective of a laboratory
toxicity test is to predtct the potential of an
effluent to have an adverse environmental
effect. As such, regulatory agencies have
stressed the use of standardized toxicity
tests as regulatory parameters. In addition,
toxicity tests may be used for other purposes such as evaluation of mill process
streams as possible sources of effluent toxicity and the potential for process changes
to reduce effluent toxicity. A toxicity test
exposes a selected organism to a series of
effluent concentrations for a specified time
after which a relevant endpoint such as
mortality, growth, or reproduction is measured. The test result is usually expressed
as a median concentration at which an effect is noted. For acute lethality tests, toxicity is usually expressed as the effluent
concentration where 50% mortality occurs
in the test organism (LC,); for subchronic
Trinity River Study

in the
Dallas, Texas area
North Carolina
Study of Industrial
and Municipal Discharges
Sedtments
Loss on Ignition (%)
Sediment Oxygen Demand
Transition Metals (ppm or ppb)
Extractable Organic Chlorine (EOX) (ppm)
Resin Acids, Chlorinated Resin Acids and
Chlorinated Phenolics (Ppb)
TCDD andTCDF (ppt)
The organic content of sediments is related to their capacity to

bind hydrophohic molecules. The oxygen consumption capacity impacts those organisms living on and within the sediments
or eggs and early life forms deposited and batching in sediments.
Track background levels, possible mill sources, and other anthropogenic sources of transition metals.
Suspended sediment acts as rapid vector for dispersal and entry
of hydrophobic compounds into the food web.
Trace transport and fate of mill effluent compounds and natural
background levels.
Trace environmentally persistent hydrophobic compounds produced by mill.
Btota
Resin Acids, Chlorophenolics, and EOX
(ppb in bile)
TCDD and TCDF (ppt in lipid or fillet)
Bile bas highest chlorophenolic and resin acid levels of aU fish

tissues; it must be hydrolyzed prior to assay to remove glucuronide groups. EOX is measure of exposure, but some natur.ll
background levels are observed.
FIlter-feeding insects and monucs are often the entry point into
food chain as these compounds are bound to suspended sediments. TCDD and TCDF are found in lipid and should be reported on a lipid adjusted basis. The lipid level in egg may
determine larval mortality in fish species.
.
D
o
~
Tests predict impact observed

Tests do not predict impact observed
(false negative)
Tests do not predict impact not observed

Tests predict impact not observed
(false positive)
FI,. 1. RtllWtl11ly ofltlborwtory Sllbelmmk toxldly test tft1Ills I.. predktt..,

tI.ffIrIMIs.
tbe ImjNIets ofllUblstrltll
Chapter
vrn 2: Assessing
the Potential
tests, the effluent concentration is reported

where the measured biological response,
such as growth or reproduction,
reaches
half of its maximum change from the control value (EC~. For subchronic tests, the
inhibition concentration, where a response
reaches 25% of the maximum or IC25,is a
more sensitive endpoint. The test validity
is assessed using established criteria for
"healthy" control organisms to avoid false
positives.
For further background,
the
reader is referred to three sources: the review by McLeay, which contains a detailed
discussion of a broad range of various laboratory toxicity tests and test results designed specifically for mill effluents (1);
Fundamentals
of Aquattc Toxicology, particularly the chapters on acute toxicity, ~
life-stage tests, chronic toxicity tests, and
statistical treatment (7); and a review of
statistical treatment procedures for laboratory toxicity tests (18).
The United States Environmental Protection Agency (EPA) has developed and promulgated, as regulatory tools, single-species
freshwater toxicity tests using fathead minnows (PimePbales promelas), water fleas
(Cerlodapbnia dubia),and the green algae
(Selenastrum
capricornutum)
(9). Validated studies have been carried out by the
EPA (20) and state agencies (21) (see Fig.
1). However, the results indicate that singlespecies tests usually, but not always, predict major effects
on communities
inhabiting the receiving waters. It is noteworthy that these studies were conducted
largely at heavily impacted sites. The corollary large-scale testing of unimpacted sites
to truly understand the predictive error of
laboratory toxicity tests has not been done.
Examples of further oversights in most
present regulatory single-species tests are
omission of exposure routes for toxic substances such as food sources, sediment
contact and ingestion, potential environmental transformation of effluent components, and critical endpoints such as fish
reproduction.
The EPA has also initiated development
of laboratory toxicity tests for saltwater and
estuarine species. These tests show that mill
Impacts
on the Aquatic
Environment
773
effluents prevent fertilization of Pacific

Coast echinoderms at relatively low doses
(sometimes <1% effluent concentration).
The effect has been traced to reactive aldehyde groups in a high molecular weight fraction (presumably oxidized lignin) that can
be effectively eliminated by treatment with
reducing agents such as metabisulfite (2224). In addition, toxicity tests are being
developed for contaminated sediments using the reproduction and the early life-stage
endpoints of in-sediment dwelling organisms (25).
Single-species tests have been used to
assess and compare different pulp mill processes (26-28). Biologically treated discharges have passed laboratory toxicity
tests, indicating that major impacts on receiving waters are not expected from these
effluents. Differences were not observed
between mills engaged only in pulping and
mills in which bleaching was performed
(29,30). The test results suggest that oxygen delignification, combined with biological treatment, may be beneficial, because
little toxicity was observed even in undiluted, 100% effluent from mills employing
this process stage and biological treatment
(29). However, the baseline for comparison was effluents from older mills whose
design and process control technologies are
not the same as those of more modem mills.
Single-species toxicity test results have
not shown any correlation with effluent
AOX levels (31,32) (Figs. 2 and 3). Differences were observed between biologically
treated and untreated effluents (32) but not
between effluents from mills having only
pulping operations (unbleached) and from
mills incorporating
a bleaching process
(31,32). The result is not surprising because
AOX is composed
primarily of watersoluble, high molecular weight material
(> 1000 daltons).
Only low molecular
weight material readily enters organisms,
and only extractable organic chlorine (EOX
the
hydrophobic
or fatty
portion
of AOX)
should have the potential to bioaccumulate.

Effluents have been separated or fractionated into low molecular weight AOX or EOX
fractions, but these still did not correlate
774
Pulp Bleaching
-Principles
and Practice
with toxicity (32). These results support

the contention of the Canadian federal government that AOX is not a valid predictor
of environmental impact.
Initial comparisons of ECF and TCF effluents have been made in Canada using
single-species tests. Acute lethality results
from tests employing Cerlodapbnia were
equivalent
for ECF and TCF and, in
subchronic tests with the same organism,
ECF effluents from mills with and without
oxygen delignification stages were less toxic
than those from mills with TCF bleaching
operations (Fig. 2). The results of acute lethality tests using fathead minnows were
also equivalent and, in subchronic tests, ECF
effluent from an oxygen delignification mill
had the lowest overall toxicity (33). However, the limited data are insufficient to determine if ECF or TCF sequences
are
superior. As stated earlier, extrapolations
should not be made from single mills to the
industry as a whole. When biologically
treated effluents from unbleached
and
bleached kraft mills were compared, no differences in toxicity based on AOX were
observed (Fig. 3) (31).
In summary, single-species toxicity tests
are used as rapid and inexpensive predictors of major impacts, but these tests should
not be viewed as infallible predictors. More
importantly, these tests have not yet been
shown to have any predictive capability for
4>
sublethal impacts at the whole- and withinorganism levels in field studies.

3.2
~~
. Unbleached
pulp
. Bleached pulp
iE.!!!
~o
m_
4> c:
~ 5E
III
0.1
.
. .
.
~ 20
...J
us-
... -.
~100
~~
80
=m
.,~
!j
exposures
A summary of extended laboratory experiments on bleached kraft mill effluent

(BKME) is compiled in Table 2. These experiments have not been coordinated, so
that the tested species, test system in which
exposure occurred, and measured endpoints vary between experiments. In addition, the mill process and effluent treatment
were not always clearly identified and, in
most circumstances, the effluent was not
well-characterized
chemically. Tests employing organisms other than fish species
such as algae and the many invertebrate
species found in aquatic environments are
very limited.
Long-term survival and growth of fish
from eggs, larvae, and fry have been measured using extended exposure to effluents
in laboratory systems. These life-stages are
presumed to be more sensitive in comparison to adults. The primary difference observed was between untreated or partially
biologically treated effluents and efficiently
treated effluents (11). Untreated or partially treated effluents (34-37) affected
mortality and growth in some cases at effluent concentrations
below 2%. Treated
:6.2
c: c:
.2 c: 60
e'E
c~
g.2! 40
00;
Uu.
E-
Extended laboratory
ing single species
1
10
EffluentAOX,mg/L
Fig. 2. Jiffed of bletldlell ;m4 rmbletldlelllmlft

cltnnrie toddIy Ie8I (31).
mill e./ll_ts
1mffltbetUI mi_
100
larva hi sirtgle-spedes
Chapter
VITI 2: Assessing
58
Impacts
on the Aquatic
Environment
775
10.0
u';;
the Potential
5.0
-60
eu
g-J!!
... c: 1.0
as 0
'2"0; 0.5
~.~
as
<D
.
o to.,. ...
.
~~
~.~g 0.1
o
.
.
. .
1
2
3
AOX, kg/metric
KraitMiHEffluent
o Unbleached and treated
. Bleached and treated
to Unbleached and untreated
Bleachedand untreated
4
5
ton of pulp
FIg.3. Weet ojlnoiogklllly trNtN"

"tIIrwItN 6ktu:1Mtl.. """ktu:IMtllnwft fIIlII~1fIuat&011
~IJld"
t" shtgk-spectes elmntk ttmdty tests (32).
effluents had minimal effects at concentrations as high as 30% provided dissolved
oxygen levels were sufficient (3841).
Fish reproduction in BKME from a bleaching sequence in which a chlorination stage
was included has been evaluated. In Sweden, the test organism was the viviparous
blenny (Zoarces vtvparus) (35) and,in the
United States, the fathead minnow (41).
Blenny egg numbers decreased when the
fish were exposed to untreated effluent
concentrations
of below 0.5%. Fathead
minnows were exposed to biologically
treated BKME during fulllife-cycle studies.
Effects were observed at treated effluent
concentrations
of 6% for egg production,
10"/0 for larval growth, 32% for larval survival, and 56% for egg hatchability. Chemical characterization of the effluent to which
blenny were exposed was limited, and process descriptions such as organic and s0dium carryover from the unbleached pulp
washers to the bleach plant and chemical
usage in the bleach plant were not provided.
In contrast, almost all effluent samples used
during the fathead minnow tests were characterized, and the pulping and bleaching
processes were described. Thus, effluent
comparisons cannot be made to gain an
underst:mding of potential causes forthe

different observations.
Whole-organism morphological changes
(t.e., changes in appearance or form) have
been measured in several extended exposures. In Sweden, morphology and cartilage chemistry have been examined in
fourhom sculpin (Myoxocephalus quadrlcomts), bleak (Albumus
albumus),
and
perch (Perea fluvtattlts)
(42). Minor
changes occurred in several of the 13 bone,
cartilage, and other parameters studied in
all the kraft mill effluents tested. The number of parameters that significantly changed
in these experiments are enclosed in parentheses for each effluent tested with sculpin
and bleak, respectively:
untreated,
unbleached kraft hardwood (8 and 4), untreated, CI/CI02 (52/48) bleached kraft
softwood (9 and 7), untreated chlorine dioxide-bleached kraft hardwood (6 and 3),
and elemental chlorine-bleached kraft softwood with biological treatment (2 and 1).
Thus, the effects of exposure to unbleached
effluent were similar to those observed in
bleaching effluents and the severity of the
effect tended to decrease following biological treatment and chlorine dioxide substitution
(42).
In North America,
no
morphological effects were noted in full lifecycle studies with fathead minnows (41)
or extended exposures in chinook salmon
fry (Oncorhynchus
tshawytscha) (43).
Histopathology provides a means to determine structural changes and lesions in
body tissues, such as liver and kidney, under microscopic examination.
Exposures
776
Chapter
VIII 2: Assessing
the Potential
to untreated BKME produced external fin

necrosis (death of tissue) and epithelial erosion in rainbow trout (Oncorhynchus
mykiss) after 2o-day exposures in 2% effluent concentrations.
However, no histologicallesions were observed in any internal
organs after 6O-day exposures in 4% effluent concentrations
(44).
Biologically
treated BKME did not cause changes in the
external or internal tissues of fathead minnows at effluent concentrations
over 30%
(45). Minor histological alternations were
noted in chinook salmon fry, suggesting
evidence for stress (enlarged nuclei in the
anterior kidney) and bacterial kidney disease (areas of liver necrosis in some individuals) (43).
Fish physiology and biochemical measurements are often termed biomarkers.
Theoretically,
biomarkers
are sensitive
warning signals of stressors (chemical or
other changes in the environment)
and
should provide quantifiable measures in the
early phase of an organism's response to
natural or anthropogenic stressors. However, although physiological and biochemical tests have been applied on several
occasions, few biomarkers have been demonstrated to provide legitimate warning signals (46). In Sweden, several biomarkers
have been studied in extended laboratory
exposures to BKME using fourhorn sculpin.
Both untreated hardwood and softwood
effluents from mills with and without
bleaching
operations
were evaluated
(47,48). Acute and subchronic laboratory
single-species tests of these effluents indicated that they were toxic at concentrations
below 10%. Sublethal biomarker effects
were observed at effluent concentrations
of 0.3% and lower in several measurements
after 3-month exposures.
Detoxification
responses
in fish are
among the most commonly
measured
biomarkers in the past decade. Detoxification or removal of chemical substances from
the body is broadly divided into a Phase I
proccoo, convcroion of the parent com.

pound to a more polar metabolite such as
introduction of a hydroxyl group on an aromatic ring, and a Phase II process, the cou-
Impacts
on the Aquatic
Environment
777
piing of highly soluble carriers such as a

sulfate, glucuronic acid, or glutathione to
the parent or its metabolite to aid in excretion in feces or urine. The Phase I process
is conducted with a large family of proteins
termed mixed function oxidases (MFOs).
The most studied MFO in fish in conjunction with mill effluent exposures is measured by the spectral
changes when
removing
an ethyl group
from 7ethoxyresorufin
(7-ethoxyresorufin
0deethylase or EROD assay). An alternative
test is to directly assay the protein using
antibodies. In the MFO family nomenclature scheme, the protein is called P4501A.
P450lA is an inducible protein Oevels increase when certain chemicals exceed a
threshold concentration).
Therefore, although P450lA induction can indicate
exposure to certain chemicals, any consequence of induction in fish remains speculative. In the laboratory, EROD or P450lA
induction has been observed in several experiments with rainbow trout (32) and
fourhorn sculpin (47,48). Although the
original hypothesis was that chlorinated
materials were the inducers, later work has
also provided evidence for moderate EROD
induction in laboratory exposures withTCF
effluents (32).
In summary, extended laboratory experiments have been conducted using different
test species, endpoints, and mill effluents.
The results indicate that biological treatment of mill effluents reduces the lowest
observed effect concentration
(LOEC) by
approximately
an order of magnitude or
more. The majority oftests have been conducted on effluents from "conventional"
processes, that is, processes involving no
extended
delignification
or oxygen
delignification and bleaching with elemental chlorine. As noted previously, chemical
characterization
and process descriptions
from these experiments
are often inadequate to gain any understanding
of any
relationship between the chemicals in the
eIDuems and the observed effects. There
has also not been a systematic exploration
of modem pulping processes (extended
pulping and oxygen delignification)
or
778
Pulp Bleaching
-Principles
and Practice
bleaching processes (ECF andTCF).To make

systematic comparisons, the development
of standardized chemical analyses and biological protocols using a single species (e.g.,
the fathead minnow) are needed to compare effluents from different processes in
widely dispersed sites. The utilization of
sensitive endpoints such as reproduction,
larval development and growth, and sexual
development,are recommended for systematic comparisons.
3.3 Mesocosms and experimental

streams
Extended exposures of whole aquatic
communities to mill effluents have been
conducted in Sweden and Finland using
mesocosms and in the United States using
experimental streams. Mesocosms are large
pools that mimic near shoreline communities; experimental streams are artificial channels with alternating riffles and pools to
mimic freshwater stream communities. The
advantage of using mesocosms and experimental streams is to expose a variety of interacting organisms to mill effluent for an
extended period of time. These systems also
incorporate dietary exposure of organisms
to mil1-generated substance because no food
supplements are provided and organisms
must forage in the exposed environments.
Therefore, these systems have greater relevance and predictive capabilities than do
laboratory exposures. In addition, wholeorganism and within-organism responses to
mill effluents have been evaluated in these
test systems to incorporate both reproductive testing and also other sensitive measurements.
Mesocosm systems have been employed
in Sweden and Finland for the last decade
to compare effluents from mills with different pulping, bleaching, and effluent treatment processes. A brackish water Baltic
littoral (shoreline) community, which relies
on the bladder wrack (Fucus vestculosus)
for primary production (organic material
produced from sunlight ~ the foundation
for the food web) and spawning/nursery
habitat, was exposed to different effluents
(0.05 to I % concentrations)
for about six
months.
Measurements
included
the
growth, biomass, and organism number of
the bladder wrack, the invertebrates associated with the bladder wrack, invertebrates
found in the sediments, growth of sticklebacks in the original mesocosms and, in
adjacent pools, rainbow trout biomarkers.
The BKME having the greatest impact was
that from a pre-I 980 conventional mill characterized by high washing carryover, high
elemental chlorine
application, and no
biological effluent treatment.
The other
tested effluents included those from mills
with a wide range of characteristics including both unbleached and bleached softwood and hardwood
kraft furnishes.
However, most mills used little or no biological treatment (49-52). The processes
and the wide range of corresponding
biological results are summarized in Table 3.
Fish mortality was observed with threespined stickleback (Gasterosteus
aculeatus) exposed to untreated, conventional
BKME. Growth, parasite frequency, and
histopathological
endpoints (particularly
liver vacuolization) in sticklebacks were affected by several effluents even at doses of
less than 0.1 %, including the unbleached
effluent. Several biomarkers in rainbow
trout exposed to the softwood BKME were
changed to a statistically significant degree,
including up to six-fold EROD induction.
The effluent displaying the fewest and least
severe effects was that from a mill using an
oxygen delignification stage and lOO"A,chlorine dioxide substitution in the bleach plant
but lacking biological effluent treatment.
Effluent AOX levels in mesocosms did
not consistently correlate with environmental impacts. Unbleached effluent effects
were similar to those of BKME at AOX levels below 2 kg/metric ton (see Fig. 4), and
low AOX hardwood effluents were more
toxic than softwood effluents having higher
AOX levels (51,52). The biological results
were, in several instances, related to high
chlorate levels in the effluent. In other
Ca5CS, organisms living on and in the sediments were affected. The results suggest
that multiple differences in mill operations,
furnish, and process equipment
make
Chapter
VIII 2: Assessing
the Potential
Impacts
on the Aquatic
I'-
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~~~C\C\~
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~~~~~~'"'~~~""'OO"'~~N
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~~.<::
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.B~::I
~'-'~:E:~!!;t]
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t:~~
~<.>
~~'~I
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0<\
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t~0"1C1O<.g
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~..t::~::S
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~""~
e!="o~
"':~&.6,,_u'<::[Q
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~<.i!tc~!ta~
.c
(ij
0
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0
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o
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:c
DB
Effluent type
11Unbleached softwood kraft

o Bleached softwood kraft
{3.
~'"
@
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8
Bleached
(effluent
hardwood
diluted
kraft
- fold)
1 000
0
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AOX, kg/metric
~~tJ1;'~!io~
'"
!,,
~e1;-
"
~~~~~~~i.s~B~.9~"~
~~~ou",!iI,.s.s~,-"c~
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I.e
c:f C e
.,~ e :s!13 ~-5u
,g"~'201:;
~0:S"
-~u5~~~'O"B
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fJ
- ~J!!
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~~~~tJ
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~~@'~j~~.
...._":I
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~~~~;;~M~::~-~~
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&."B-"=
i!
U
Environment
RI. 4. Ctlrrelilttml ofbloloflad

effl_ts
(51, 5Z).
e./f:l& ", -_
direct mill-to-mill process comparisons difficult. Most of the mesocosm studies involved single experiments.
Because
year-to-year variability in the control data
has been observed to be almost as large as
differences between within-year control
and exposed mesocosms (51), the use of
replicate systems would have been beneficial to improve the resolution between
effluents.
The experimental
stream studies performed in the United States used two conventional softwood BKMEs
32 kappa
brownstock, extensive biological effluent
treatment). The streams modelled freshwater situations using rainbow trout in cold
water streams
and largemouth
bass
(Micropterous salmotdes), bluegi1i sunfish
(Lepomts macrocbtrus), and golden shiners (Notemtgonus
crysoleucus) in warm
water streams. Experiments have been continued for over a decade with exposures
ranging from 9 months up to 3.5 years
(48,53-57). AOX concentrations were approximately 2 kg/metric ton of pulp during the original experiments
conducted
before 1989. Tests involving .experimental
stre:l11l systems were conducted with du-
(-
plicate control streams and duplicate

exposed streams for each effluent concentration tested.
ton of pulp
wttbAOX 1erJe1&
I. bIMeW tlflillIIIble4eW
1nwft mI"
Impacts on benthic macroinvertebrates

and fish species were minimal at treated
effluent concentrations of up to 4% in cold
water streams and 10% in warm water
streams (53,55-57). Benthic organism biomass in the streams exposed to effluents
was higher, especially that of ruter-feeding
organisms (55-57). Chlorophyll from periphyton (algae) decreased with water depth
in relation to color levels and heterotrophic
organisms replaced primary producers

(59,60). Fish mortality was not affected and
fish growth and biomass were slightly
higher in the effluent-exposed streams.
Histopathological
examination
of ap.
proximately twenty fish tissues from effluent-exposed streams was normal, including
liver tissue where changes had been seen
in mesocosm studies. Observed lesions
were related to naturally occurring parasitic
infections and were equivalent in fish from
both control and effluent-exposed streams
(48,53-57). Fish sexual development was
normal starting with their introduction as
juveniles through adult spawning in cold
water streams with 1.5% effluent and warm
water streams with 5% effluent. In the cold
water streams, rainbow trout fertilization
rates were apparently lower in the effluentexposed streams although development of
fertilized eggs appeared to be normal (55).
Chaptervm
2: Assessing the Potential Impacts on the Aquatic Environment
Biomarker experiments
performed on
fish in experimental streams show that both
EROD and P450lA induction occurred at
high (70%) chlorine dioxide substitution in
largemouth
bass and channel
catfish
(Ictalurus punctatus) (these tests were not
run on chlorination-stage
effluents). The
fish were exposed to 4 and 8% effluent concentrations continuously for 260 days followed by 30 days of depuration in streams
without effluent (58). Induction rapidly
declined during the depuration phase, suggesting that compounds with extended haIflives such asTCDD are not the only inducers
in these effluents. No significant induction
of EROD activity was observed in preliminary experiments in streams containing up
to 12% effluent from a process further modified by oxygen delignification and 100%
chlorine dioxide substitution. The results
of other biomarker measurements, such as
hematocrit, leucocrit, and liver somatic index, were not significantly different for
control fish and fish exposed to chlorination-stage effluents (53).
The controlled
exposure
of fish in
mesocosms and experimental streams deals
largely with BKME and data relating to mechanical pulp, CTMp, or bleached sulfite
pulp effluents are limited. Single-species
toxicity tests performed simultaneously indicated that the experimental stream effluents were not toxic under acute and
subchronic conditions. The experimental
stream exposures using biologically treated
effluents had little or no effect on most
freshwater species at effluent concentrations in the 4-6% range (53,55,57). In contrast, the mesocosm
data indicate that
effluents from some mills may alter community and population structures even at
0.1% concentrations.
These extended exposure results reinforce the need for sitespecific limits on total organic discharges
by in-process and effluent treatment steps
and good process control and indicate the
potential usefulness of chlorine dioxide
substitution
and, possibly, oxygen delignification in reducing toxicity. However,
as in all biological tests, the toxicity of nonchlorinated and chlorinated materials is integrated and the effects attributable
to
particular individual compounds

be distinguishable.
781
782
Pulp Bleaching
and Practice
,-,
"0
...
=
'S
c::
o
.~
may not
3.4 Field studies

Field studies integrate the responses of
individual ecosystems
and the species
within them to mill effluents based on a
particular mill's individual engineering and
operating characteristics. Thus, field study
results should be considered potentially
unique until the findings have been reproduced at other sites. Pulp mills have a significant history of association with adverse
receiving water impacts in the field. The
large-scale discharge of organic material and
fiber from many pulp mills before 1970 was
the primary cause for the observed environmental impacts (11,12).
However, a
combination of reduced discharges resulting from improved process and sewer designs, improved operating control, and
biological treatment have sharply reduced
the observed incidence of major impacts.
In most cases, recent field studies, with
certain exceptions, have focused on wholeand within-organism effects of effluents on
fish. Effects in some cases have been severe, but these effects have not been observed at other mills despite intense effons
to establish a connection. This implies that
the task of identifying the causes and the
solutions of problems at certain mill sites is
difficult and reinforces the need for caution
when generalizing the findings to other sites
until studies are completed there. The field
studies that are relevant to this chapter are
summarized in Table 4.
Benthic community data
Benthic individuals are relatively stationary and in contact with sediments (which
tend to accumulate
hydrophobic
substances). Historically, benthic communities
have been the most useful for identifying
organic and fiber impacts (12). Benthic
data are available for some recently studied
BKME field sites such as Norrsundet (Sweden), Jackfish Bay (Canada), Monstecls
(Sweden), Grande Prairie (Canada), and
Flint River (United States). Major studies of
fish populations have been conducted at
several of these sites so the benthic data
are imponant to understand the potential
-Principles
='"
~o
U
Chapter
VITI 2: Assessing
the Potential
Impacts
on the Aquatic
Environment
783
784
Pulp Bleaching
-Principles
and Practice
causes of the fish observations.

For each
site, a basic process history is provided in
Table 5.
At Norrsundet, progressive data sets from
the mid-1970s (ref 61, section 10),1984
(62), and 1989 (63) show that extensive
degradation of the benthic and algal communities occurred. In the 1970s anoxic fiber mats gradually receded, and only a
strong organic enrichment and eutrophication gradient was observed in the late 1980s.
At }ackfish Bay, benthic impacts increased
between 1969 and 1985 when mill expansion led to an increase in the discharge load,
organic enrichment, and mercury and bunker oil which contaminated sediments (64).
At Monsteras, there were no obvious organic enrichment
impacts. In the early
1980s, chlorate toxicity affected the bladder wrack and many associated organisms
but the site had substantially recovered by
1990 (65). At the Grande Prairie mill,pollution-sensitive benthic species were still
present below the biologically treated discharge after nearly twenty years of mill operation (66). At Flint River, benthic,
bacterial, diatom, and fish populations
showed no adverse effects from mill operations (67). Therefore, based on benthic
data, alterations and possible adverse effects
in fish populations would be suspected at
Norrsundet and }ackfish Bay. For perspective, a variety of university, regulatory, and
private benthic and fish studies have been
performed below the discharge sites of both
bleached and unbleached mills in North
America and these have been summarized
(68). Where biological treatment was installed, adverse benthic impacts were not
commonly observed in benthic studies by
the late 1970s and early 1980s (68).
Fish population data
Fish population endpoints have included
the presence and distribution of fish species and the growth and the mortality rates
of particular species. Changes in the number and distribution of fish species is pre:!umptivc evidence for a change in feeding
habitat usually caused by organic and nutrient enrichment. In addition, changes in
spawning habitat may occur which reduce
populations. Changes in growth and mortality rates within populations contribute

more definitive data for identifying adverse
effects. At Norrsundet, significant changes
in the distribution and numbers of fish have
been observed for perch (Perea jluviatilis),
roach (RutilllS rutilus), ruffe (Gym noeepbalus eeruna), and other species. At
Monsteras, ruffe populations
increased
slightly, but no changes were observed in
perch or other species (65). At Grande Prairie, fish population densities and species
diversity were slightly higher at exposed
sites than at reference sites (71,72). At
Norrsundet, higher growth rates were observed for exposed
perch and roach
(70,73), and mortality rates were higher in
exposed perch than for unexposed perch
at a reference site (74). At Grande Prairie,
growth rates of longnose sucker (Catostomus eatostomus) and mountain whitefish
(Prosopium williamsom)
were similar to
those found at reference sites, but mortality rates in fish exposed to effluent were
slightly higher. At }ackfish Bay,white sucker
(Catostomus eommersoni)
growth rates
were lower than those of the same fish species at the reference sites. A population agedistribution analysis indicated the presence
of a greater proportion of older individuals
(75). An observation unique to Norrsundet
was the absence of fish within 1-2 km of
the mill discharge (69,70). On the other
hand, fish have been captured in or near
the effluent plume at Grande Prairie (72),
}ackfish Bay (75), LaTuque (76), and at
Espanola (78) (see Table 5 for mill description). Once more, a summary of fish population data and species distributions
indicated that few adverse effects were seen
in NorthAmerica by the late 1970s and early
1980s for mills using biological treatment
(68).
Whole-organism
parameters
At the whole-organism level, commonly
studied field endpoints include condition
factor, external gross pathology, and parasite infection rates. Condition factor is a
measure of ratio of the weight of the fish to
its length. Condition factor varies directly
with food intake and inversely with the
Chapter vm 2: Assessing the Potential Impacts on the Aquatic Environment
Ttlble 5. Process.ruI sUe ~

Site
of ",iIls
",'-e -lor
Description of Operation
f"U
785
stUIes IHlve bees coruItIde4.
Norrsundet (Sweden)
50% unbleached softwood kraft and 50% bleached softwood kraft until 1983; after
1983 l00"Aibleached production; conventional pulping; oxygen delignification beginning in 1983; chlorine dioxide substitution rising to 100% in the late 19805; no
biological treatment until 1994; discharge into very shallow estuary of Bothnian
Bay,dilution provided by pumping into effluent mixing basin
]ackfish Bay (Canada)
Softwood kraft furnish; conventional pulping and bleaching technology; no biological treatment until 1990; discharge into small creek flowing into isolated bay on
northern shore of Uke Superior
Monsteras (Sweden)
Primarily softwood furnish; extended deIignification pulping, oxygen delignification,

1()()%chlorine dioxide substitution; efficient biological treatment in aerated stabilization basin, and discharge dilution conducted through a submerged diffuser into
Baltic Sea; previous impacts in shallow bay attributable to chlorate toxicity on Fucus algae
Grande Prairie (Canada)
Softwood kraft furnish; conventional pulping and bleaching until 1990 when chlorine dioxide substitution was raised to 100%; hypochlorite stage also removed in
this period; efficient biological treatment in aerated stabilization basin; discharge
into Wapiti River with low dilution during winter ice cover
Flint River (USA)
Softwood kraft furnish; conventional pulping and oxygen delignification since start
up; 70% chlorine dioxide substitution during study and now l00"Aisubstitution;
and efficient biological treatment in aerated stabiIization basin. There is a 9O-day
holding capacity to control in-stream effluent concentration during low flows. The
discharge is via a submerged diffuser into a warm-water stream
LaThque (Canada)
Softwood kraft furnish, conventional pulping and bleaching; discharge untreated;

during first study the effluent AOX was 8-10 kg{ton of pulp. SI. Maurice River
receives effluent and is dammed immediately above the mill and 1()() km downstream, isolating fish population
Espanola (Canada)
Mixed softwood and hardwood kraft furnish; conventional pulping and oxygen
delignification; 50% CIOz substitution; and efficient biological treatment with AOX
levels < 1 kg/ton; discharge into Spanish River
expenditure of energy, especially for reproduction. Condition factors were higher for
fish at bleached kraft mill sites, including
perch at Norrsundet (70), white suckers at
LaThque (76),andjackfish
Bay (75,77),and
longnose suckers at Grande Prairie at the
site nearest the mill (71,72). Some associations have been found between condition
factor and food supply (72), lower growth
rates at jackfish Bay were associated with
empty stomachs and stomachs containing
less nourishing prey (77). At Norrsundet,
fin erosion in perch and ruffe and bone
deformities in pike (Esox lucius) were observed in 1984-85 (69,79). Changes in external pathology have not been observed
at other sites, including the untreated, high
AOX effluent at the LaThque site (65,72,
78). A possible exception for this generalization were gashes observed on the sides
of lake whitefish (Coregonus clupeafonnis)
at jackfish Bay (80). Fish parasite infestation rates were not elevated at BKME field
sites (65,72,75,76)
except at Norrsundet
where perch and ruffe parasite frequencies
were normal, but roach gill parasite numbers were increased (81).
Wrthin-organism parameters
Within-organism parameters include various biomarkers: histopathology of body tissues, liver size, hematology
and serum
chemistry, and reproductive
parameters
such as gonad size. Care is needed when
using this diverse array of measurements to
select those measures that represent important evidence of fish health. In this chapter, the histopathology
of tissues and
especially the measurement of fish reproductive parameters are emphasized. Other
biomarker endpoints may be of questionable value unless care has been taken to
786
confirm the association between these observations and the presence of chemical
contaminants or more meaningful biological measurements. Many of these measurements vary significantly
depending
on
habitat, food supply, and other field conditions so careful selection of reference sites
is necessary and the data should be compared with results of other studies before
the implications of adverse effects are deduced .
Histopathology
of liver, gill, kidney,
spleen, heart, muscle, and gonad from
white sucker captured near the Espanola
mill and of liver, gill, kidney, spleen, and
gonad of longnose sucker, and mountain
whitefish at Grande Prairie indicated that
effiuent-exposed fish were normal (78,82).
Detailed histopathology has not been conducted at other sites although ateric ovaries (where eggs were not released and
resorption of the eggs was underway) were
noted in limited
samples
taken at
Norrsundet (70).
Liver size or liver somatic index (LSI) was
reported in several studies. The liver is a
central organ for metabolism, detoxification, and energy maintenance. Changes in
ISI are usually non-specific because changes
in lipid or glycogen levels, water content
of liver cells, and other parameters may affect liver size, casting doubt about the significance of any such change. Some studies
have led to speculation that an increase in
the quantity of detoxification enzymes may
cause increased liver size. However, it is
unlikely that P4501A induction is related to
liver size because the quantity of this protein system is very small in the liver. Increased LSI values were observed in perch
at Norrsundet
(8), in several species at
jackfish Bay (77), in white sucker at
LaThque (76) and Espanola (78), and in
longnose sucker at Grande Prairie (82).
Few efforts were made to determine the
possible cause of any LSI increase. Near
the Grande Prairie mill, longnose suckers
having higher LSI had a parallel increase in
liver lipid content which was associated
with increased somatic condition factor and
more abundant food supplies (72,82).
Thus, in this case, there was no evidence

that the LSI change was an indication of an
adverse effect. In addition, LSI changes
were not universal or consistent: the LS1was
not increased in spawning individuals at
jackfish Bay (77), perch at Montseras (65)
and mountain whitefish at Grande Prairie
(72,82).
Several serum chemistry and hematological (red and white blood cell) measurements of exposed fish were statistically
different at Norrsundet when compared to
those at reference sites (8). However, these
observations were not reproduced when
the measurements were repeated at other
BKME mill sites (65,76,78,82,84).
The most frequently used reproductive
measurement in field studies is the determination of gonad size relative to whole fish
body weight or gonad somatic index (GSI).
Gonad size is generally related to reproductive capacity, but it fluctuates during the
annual sexual cycle so that the reproductive status of the fish must be precisely
known to interpret these data. Decreased
GSI has been observed at Norrsundet (8,70)
and at jackfish Bay (75,77,83,84).
GSIs
were similar for BKME-exposed and reference fish at Monsteras (65), LaThque (76),
Espanola (78), and Grande Prairie (71,72).
In addition to GSI values, other reproductive and recruitment data have been gathered at several BKME sites because a set of
related measurements
is desirable when
defining critical endpoints such as reproduction. At Norrsundet, egg production
rates of successfully spawned perch were
similar to those of reference adults. Eggs
successfully hatched, but nearly 1()()% larval mortality was observed (70). Young-ofthe-year for all species were absent within
1 km of the Norrsundet discharge, roach
and ruffe young-of-the-year were abundant
2-3 km from the discharge, and perch
young-of-the-year were found at a distance
of 4-5 km, indicating a difference in exposure or species sensitivity to chemicals or
environmental condItions. (61)). No eftects
on young-of-the-year from various species
were observed near the Monsteras (65) and
Grande Prairie (72) discharges. The age-to-
Chapter vm 2: Assessing the Potential Impacts on the Aquatic Environment

sexual-maturity was lower for white suckers at}ackfish Bay (75) but was unchanged
for both longnose suckers and mountain
whitefish at Grande Prairie (72). External
tubercle development of suckers, a male
secondary sexual characteristic, was minimal at }ackfish Bay (75) and normal at
Grande Prairie (72). White suckers at
}ackfish Bay were apparently capable of
spawning because egg fertilization, egg
hatchability, and sperm counts were normal (85). The total number of eggs per female (fecundity) and egg diameter were
lower in exposed white suckers at }ackfish
Bay (75,77) but unchanged in longnose
suckers at Grande Prairie (72).
More sophisticated analyses used to estimate the reproductive fitness of fish include
the determination of circulating levels of sex
steroids and the pituitary hormones which
directly control steroid production. The sex
steroids that have been measured are estradiol (female), ll-ketotestosterone
(male),
testosterone
(a steroid common to both
sexes in fish), and 17, 20S-dihydroxypregnenone (17 ,20-DHP), which appears to
control spawning (71,75-78,80-82,84,86).
Fish go through a progressive sequence of
gonad development (increasing size/Weight
with gamete development)
followed by
spawning activity controlled by circulating
steroids. Therefore, the reproductive stage
of sampled individuals must be precisely
known to determine if abnormal changes
in hormone levels have occurred. In addition, hormone level variations can occur
between reference and exposed sites because of temperature and water quality differences, a factor that further complicates
interpretation
in field settings. At }ackfish
Bay, males and females of three species
(white suckers, lake whitefish, and lake
trout (Salveltnus namaycusb
had sharply
decreased levels of circulating sex steroids
(75,77,83). At La1Uque, no significant effects were observed at the discharge site in
males or females, although their testosterone [eve[:! were [ower 100 kIn downstream
(76). Male testosterone
levels in white
suckers were similar upstream and downstream from the discharge at Espanola (78).
787
At Grande Prairie, no differences in the estrogen and testosterone levels of males or

females exposed were observed. The 17,20DHP level, which rises and falls sharply
during spawning, possibly was different at
Grande Prairie. Analyses of gonad size and
histology indicated that the exposed individuals were not captured during active
spawning when 17,20-DHP levels undergo
a sharp increase. Thus, it was uncertain if
any actual difference in steroid content existed (82). Additional field work has identified the actual spawning
site and
confirmed that 17,20-DHP levels in suckers
were not affected by effluent exposure. A
recent survey of ten mills in Ontario showed
that depression of sex steroids in fish varied from site to site and occurred at mills
producing both bleached and unbleached
pulp (86), indicating the lack of a direct
association
of these compounds
with
bleaching.
EROD or P4501A induction has been
observed at numerous BKME mills in both
feral (8,32,40,53-55,75-78,82-84,86-88)
and caged fish (89-91). As background, the
degree of induction may vary between species, and the females of some species have
reduced induction
before and during
spawning. Based on comparison with reference populations, induction at mill sites
was not observed at Monsteras (65) and the
W1llamette River in Oregon (92), but increased 2- to Hold in fish in the vicinty of
several Swedish mills (93),5- to 8-fold in
white suckers at }ackfish Bay (75),8- to 10fold in perch at Norrsundet (8), and up to
30-fold in mountain whitefish at Grande
Prairie (87). EROD or P4501A induction
of up to 5-fold has also been observed in
feral perch and caged rainbow trout at an
unbleached sulfite mill (94) and in feral
white suckers at a mechanical pulp mill site
(86). The chemical character and transport
of the dominant inducers may be site-specific. At }ackfish Bay, induction in white
suckers decreased rapidly during a mill shutdown ((jj) implicating a watcf1Olublc, rapidly metabolized substance(s) as the cause.
At Espanola, EROD levels rose rapidly in
unfed, caged white suckers that were not
788
in contact with sediment (92), implicating

water-soluble substances and not sediment
or food chain-associated
materials as the
cause of induction. In contrast, at Grande
Prairie, the high level of induction in mountain whitefish has been associated with
measured
levels of TCDD and TCDF
(tetrachlorodibenzofuran)
in body tissues
(86) which appear to be related to accumulation from food (95).
The important question is whether EROD
induction is associated with any adverse
biological effects. At }ackfish Bay, no association was found between EROD induction
and reproductive
effects including decreases in sex steroid levels (77,80,86) once
at Grande Prairie, where EROD induction
was highest, induction was not associated
with any adverse effects in population,
whole-organism, and within-organism measurements (72,82,87). Therefore, the available evidence strongly suggests that EROD
induction is related to exposure of fish to
pulp mill effluents but not to any adverse
effects caused by the effluent.
In summary, field studies show a wide
variation in the extent and degree of wholeand within-organism
responses of fish at
BKME sites. Fish responses have been ass0ciated with the presence and intensity
(Norrsundet and }ackfish Bay) or absence
(Monstecis and Grande Prairie) of benthic
community degradation. The dramatic effects seen at Norrsundet, evidenced by differences
in community,
population,
whole-and within-organism responses, appear to be unique in their breadth and severity for modern mills, although they
would not have been considered so at mills
before the introduction of biological treatment. In addition to the long history of
severe degradation at this site, the study was
conducted during a difficult start-up of a
major expansion that included installation
of new washers and screens, introduction
of an oxygen delignification stage, and installation of new bleach plant lines, but no
in~taIlation of cfflucnt tftaUIlcm for tlle mill
or the adjacent sawmill. During this period,
there were black liquor spills and sharp decreases in dissolved oxygen levels in receiv-
ing waters (see Figs. 5.2 and 5.4 in ref 96).

Although researchers clearly acknowledged
the impact of organic enrichment
and
eutrophication in the study(69, 70), the results have been widely communicated
as
showing a relationship between adverse
effects and AOX.
In follow-up studies at Norrsundet. the
condition of the benthic community has
continued to improve (97): no further incidents of fin erosion or malformations have
occurred since 1984 (98), fish population
effects continue to decrease although fish
still avoid the area near the discharge (99),
perch gonad size and age-to-maturity were
normal in 1992 (99), and various biomarker
responses
in perch
have improved
(93,100). It should be noted that the chlorine multiple did not change at Norrsundet
between 1984 and 1988 when increased
chlorine dioxide substitution began in the
latter year (101). In contrast, the Espanola,
Monsteras, and Grande Prairie mill studies
were performed on treated effluent discharges during periods of high chlorine dioxide substitution
(50-70%) and under
conditions of apparent process stability.
It is important to recognize that the effect of exposure to chlorinated materials
was not significantly different based on fish
body burdens at Norrsundet and Grande
Prairie. TCDDrrCDF levels were higher at
Grande Prairie than at Norrsundet (95,102),
but bile chlorophenol levels were comparable as shown inTable 6 (103,104). Where
available, data from Canadian and Finnish
mills are also included in Table 6, and these
data again indicate that exposure to chlorinated materials at Norrsundet was not unusual. Thus, chlorinated materials do not
appear to be largely responsible for the findings at Norrsundet compared to other sites,
and the Norrsundet data and conclusions
based on them should not be generalized.
As the conversion to ECF and TCF bleaching processes proceeds, researchers must
better define actual fish exposure, mill operaring condirions,
sirc habitar md hydrol.
ogy, and the historical
impacts on the
receiving waters to avoid drawing possibly
unwarranted conclusions. Although data on
Chapter
VIII 2: Assessing
the Potential
Impacts
on the Aquatic
Environment
789
790
the environmental impact of ECF effluents

are now available, no comparable field data
are currently available for TCF bleaching
processes. However,TCF bleaching usually
requires relatively low kappa number pulps,
extensive washing, and careful plant control. This indicates that, in theory, TCF mill
environmental effects would at least be no
more unfavorable than those observed at
ECF mills.
4. Expected
~... ~
...
e e
trends
and future
research
needs
The available data on pulp and paper mill
effluents indicate that environmental protection first requires the limiting of organic,
nutrient, and suspended solids loadings.
These loadings can be controlled using both
in-plant controls and efficient effluent treatment. Secondly, production of persistent
and bioaccumulative cWorinated materials
in the bleach plant can be addressed by replacement of elemental cWorine with cWorine dioxide.
In the future, continued
technical improvements in delignification
such as extended kraft pulping, ozone
delignification, and associated processes
will allow further reduction in mill loads
per ton of pulp. Unfavorable economics
may prevent older, established mills from
retrofitting extensively with newer technology. This problem may be compounded
by limits to mill expansion caused by limitations in the available wood supply. Increasing mill closure by recovery and
evaporation/incineration
of waste streams
may be practiced with decreasing water
used per ton of pulp. This may ultimately
be limited to mills that can afford to retrofit
with these technologies and whose customers are willing to pay the added capital and
production costs.
Environmental assessment of pulping and
bleaching effluents will continue and will
remain a multi-discipiinary effort. Several
measurement systems ranging from laboratory single-species tests to complex, multiyear field :itudie:i can be employed with
increasing confidence. The inherent complexity and expense of environmental testing and monitoring suggest the need for a
tiered approach in which the results from

initial tiers are used to identify the appropriate design and direction for subsequent
tiers. The initial tier should seek to ascertain if any adverse effects have occurred at
the community and population levels and
if organic or nutrient enrichment are likely.
In cases where adverse effects are found to
be severe, further studies should possibly
await remediation because the use of wholeand within-<>rganism parameters may not be
practicable under these conditions.
Chemical characterization of the effluent,
receiving waters, sediments, and organisms
can be used to indicate the potential for an
effluent to contribute to organic and nutrient enrichment, to assess environmental
transport, and to assess the effects of exposure of target organisms to mill effluent.
Where stream flow variations exist, dilution
and sediment transport variations require
seasonal sampling efforts to quantify the
range of conditions. Future analytical issues
include the chemical and biological characterization ofTCF processes, the improvement of detection limits for chlorinated
compounds whose concentrations
are reduced by ECF processes, and the analyses
of natural plant compounds, such as sterols,
in mill effluents.
Some of the frequently used single-species toxicity tests are losing their relevance.
Improving operational control, continued
mill closure, reduced brown stock kappa
number, and the growing universality of
biological treatment are steadily reducing
effluent toxicity previously observed in the
current tests. In fact, many current BKMEs
show no acute or subchronic toxicity in
these tests at 1()()% effluent concentration
(29). Because mostTCF processes involve
similar process and operating conditions,
the resulting effluents would be expected
to exhibit little toxicity in single-species
tests. However, the trend to substantially
reduce water usage toward mill closure may
increase chemical concentrations
in efflu-
ents and be a source for positive toxicity

results. In addition, the sea urchin fertilization and bivalve toxicity tests appear to be
very sensitive (22-24).
Chapter
vm 2: Assessing
the Potential
Extended exposures, such as full-life

cycle tests, will continue to have relevance,
especially where reproductive
fitness is
measured and can be linked to the health
of fish populations.
In addition, comparison of process improvements and identification of EROD inducers are needed, both
of which will require extended exposure
testing. The side-by-side capabilities of
mesocosms when attempting to compare
different effluents is especially important.
In 1993 the Swedish and the Finnish paper
industries made a major effort to compare
the effects of untreated and biologically
treated ECF andTCF effluents when present
in mesocosms. No substantial differences
were found betweenTCF (ozone) and ECF
(100"10chlorine dioxide) bleaching effluen~
005,106).
In field studies, a careful understanding
of exposure and background conditions is
necessary to ensure proper interpretation
of data. Chemical and biological measurements can quantify effluent exposure and
the effects of that exposure on aquatic communities. However, the sampling program
requires careful spatial and temporal coordination (samples taken at the right places
at the right times) to integrate these data
into a comprehensive exposure and effects
assessment.
To properly interpret field
study results, habitat assessment and a review of other factors such as fishing pressure should be included as well as an
evaluation of seasonal and year-to-year variabilities at the study site. Differences in fish
populations occurring because of habitat
changes between exposed and reference
sites has made the data interpretation more
difficult in several studies. These difficulties included river hydrology and variation
in food resources at Grande Prairie (72),
the effect of water temperature on sexual
maturity at Espanola (78), and, at Jackfish
Bay, differences in food resources and fishing pressures at the effluent-exposed
and
reference sites (07).
Numerous differences in fish, originally attributed to effluent discharge at LaTuque, may be ascribed
to habitat and nutrient gradients as indicated by a comparison with results obtained
Impacts
on the Aquatic
Environment
791
at more carefully chosen reference sites in

the nearby Gatineau River (08). Additional
surveys at multiple bleached
and unbleached mill sites in Ontario have shown
a wide variation in impacts in the occurrence and magnitude of effects which are
not associated with effluent toxicity in
single-species tests, receiving water AOX,
or a bleaching process 009, 110).
The applicability of whole- and withinorganism measurements to environmental
assessments remains, on the whole, unproven. Major disturbances in these parameters have been seen in areas where
environmental degradation is apparent at
the community and the population levels.
However, specific measurements, such as
EROD or P4501A induction and circulating
levels of sex steroids, have proven useful.
P4501A induction has been correlated with
exposure to mill effluents but not to adverse
environmental effects (86,87). Circulating
steroids have shown a spectrum of responses to mill effluent exposures at the
within-organism
level but have not been
associated with population-level
effects
(82,86). The cause of the decreases in steroid levels has not been clarified, but
decreased levels of steroid-synthesis stimulating gonadotrophin
and biosynthesis in
the gonads are associated with decreased
steroid levels (86,111). One possible explanation, an increased steroid catabolism
from P4501A induction, has not been confirmed when directly tested (82,86).
Available field data from mills that are
properly sited, under operational control,
and have efficient biological treatment (e.g.,
the Espanola, Grande Prairie, Flint River, and
Monsteras mills) show that both fish and
benthic populations appear to be healthy.
Thus, data collected from sites with historical degradation or loose operating controV
start-up problems
such as the one at
Norrsundet should not then be generalized
to include other sites. The endpoints on
which to focus future investigational efforts
appear to be reproduction and early lifestage measurements.
Current processes
that are well-operated and produce welltreated effluents having concentration
of
792
<10% do not appear to effect reproductive

success at the population level. However,
subtle to major effects have been observed
on individual level sex steroids at effluent
concentrations
of < I % at some bleached
and unbleached mill sites. Given the complexity of the effluents, receiving waters,
and species behavior, the identification of
responsible
compounds
may await extended laboratory exposures and the fractionation of mill effluents into chemically
identifiable compounds.
Nevertheless,
available data, reinforced by the recent tenmill survey In Ontario (10), indicate responses in steroid levels ranging from apparently severe at Jackfish Bay to none at
Grande Prairie. Again, generalizations about
the environmental
effects of pulping or
bleaching processes are currently unwarranted.
The pulp and paper industry is under
intense environmental scrutiny at the same
time It is undergoing major, capital-intensive process changes. A high level of interest exists in defining the environmental
benefits of process options such as ECF and
TCF bleaching. This interest will encourage comparative studies to be conducted
under controlled conditions when laboratory exposures, mesocosm, and experimental stream tests are performed and under
natural conditions at field sites. Given the
complexity of the effluents, chemical analyses alone are Inadequate to assess these process options and the biological response of
aquatic organisms and communities will
have to be measured. Increasing requests
from regulatory agencies for monitoring
data relating to the aquatic communities
below pulping and bleaching discharges are
anticipated as a means of determining the
environmental
impact of ECF and TCF
bleaching as well as other process options.
This is not a straightforward request. The
rate at which aquatic communities respond
to process changes in pulping, bleaching,
or in otl1cr mill operations :md during which
sediments lose persistent substances may
be relatively low (possibly years). As a result, long-term monitoring programs aimed
at addressing these questions will likely be

required. Given the recent marketing campaigns for various bleaching processes such
as TCF, there is a pressing need to develop
a significant environmental data base using
standardized tests to support the very limited data presented in these marketing campaigns.
References
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Water Pol/ut. Res.
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B., Hakanson,
L.,
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Board, Soma, Sweden,
1988.
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M.L., Water
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Chapter
VIII 2: Assessing
the Potential
Glossary
Impacts
on the Aquatic
Environment
797
Anoxic - Characterized
by the absence of oxygen, a condition
which is lethal to most
organisms except for certain bacteria. Sediments become anoxic when the bacterial
degradation
of organic matter, such as a
deposited mat of cellulose fiber, consumes
the available oxygen.
Ateric - A histological
condition where eggs
in the ovary have not been released under
spawning conditions
and the eggs are being metabolized
(resorbed).
Benthic - Indicating the bottom or sediments
of aquatic environments
such as those organisms which inhabit the surface of the
sediments or dwell within the sediments.
Biomarker - A within-organism
physiological
and biochemical measurement
which theoretically provides a sensitive warning !lignal of external stressors (chemical or other
changes in the environment).
Presumably
biomarkers
provide quantifiable
measures
in the early phase of an organism's response
to natural or anthropogenic
stressors. That
is, biomarker changes occur and provide a
signal before irreversible
adverse changes
occur.
Condition Factor - The ratio of the weight of
fish to its length. The ratio is greater for
heavier individuals which have more lipid
(fat) or more muscle content.
There is a
presumption
that this indicates excess energy which can be stored as fat either because of increased food supplies, alteration
in energy expenditure
for growth, or alternation in energy expenditure
for reproduction.
Gonad Somatic Index (GSI) The ratio of the

weight of the gonad (ovary or testicle) to
the total body weight.
During the reproductive cycle of most aquatic organisms,
there is a rise in the GSI as the eggs or
spenn develop and then a sharp drop with
spawning. The weight of the gonad is presumed to be indicative of the total egg and
sperm produced; therefore, GSI is a reproduction
indicator.
Hematocrit -The iron content of the red blood
cells. A low hematocrit is synonymous with
an anemic condition.
Heterotrophic
- Organisms which derive their
energy and carbon from organic materials
in their environment.
This is in contrast to
that found in primary production
where
an organism derives energy from sunlight
(photosynthesis)
and produces its own organic material by fixing carbon dioxide.
Hypoxia - A condition
in which decreased
oxygen levels in organisms cause adverse
effects.
Inducer - A compound
or condition
which
stimulates or increases the production
or
synthesis of an enzyme.
In the case of
P4501A, the inducer binds to the Ah receptor inside certain cells which then stimulates the DNA to synthesize
a template
(called messenger
RNA) used to produce
the protein.
Leucocrit - A rough measure of the numbers
of white blood cells in the serum. The number rises during an infection and is lower
when the organism's
immune system is
prevented from responding
to infection.
Depuration -A process by which an organism

decreases the concentration of a contaminant in its body. In experimental conditions, this is achieved by moving the organism to an uncontaminated setting. The
kinetics of contaminant decrease are of interest.
liver Somatic Index (LSI) The ratio of the

weight of the liver to the total body weight.
A number of conditions may increase this
ratio. The liver increases its metabolic activity in response to numerous
stimuli. It
is also a dynamic storage depot for glycogen and fat so that the ratio rises and falls
with changes in these energy stores.
Eutrophication - The excessive growth of algae and plants caused by an excess of nutrients, usually phosphorus. This classically
leads to an excess of organic matter which
decreases the oxygen levels of lakes because oxygen-consuming microbcs con-
Mesocosm -An experimental

pool of sufficient
size to contain sediment and water to simulate an aquatic community. The mesocosms
used in experiments
with pulp mill effluents are described
by drawings in references 49 and 50.
sume the organic
matter.
(continued)
798
Glossary
(continued)
Osmoregulation
- Regulation of osmotic pressure in the body of a living organism. Fish
in freshwater environments
must maintain
a higher concentration
of vital ions, such
as potassium, sodium, and chloride, inside
their bodies than exists in an aquatic environment. They must maintain this concentration gradient of ions across their gills
while preventing
an influx of water to dilute the ions (an osmotic gradient).
This
regulation of water and ions across the gills
(osmoregulation)
is achieved by chemical
pumps in the gill membranes.
Tubercle - A visible external growth of the
skin. Often, these growths are found in
one sex at a certain stage of the reproductive cycle, such as the male sucker, and are
used to estimate the reproductive
status or
strength ofthe reproductive
response.
Under microscopic
Vacuolization
of liver
examination
(histology), the liver cells appear to have smaIl voids in the cell structure or a spongy appearance
(vacuoles).
This observation may be due to several reasons ranging from deposition of starch granules for energy storage to oxidation stress
damage from peroxisomal
proUferation.
SECTIONvm:
Pulp Bleaching and the Environment
Chapter 3:
Dioxins and Furans in Effiuents,
Pulp, and Solid Waste
Richard Berry
1. Introduction.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 801
1.1 Definition of terms, nomenclature conventions,

and physical properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 801
1.2 Toxicity of dioxins.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 801
1.3 Reaction mechanisms for dioxin formation.

1.4 Historyofincreasingpublicawareness
2. Formation
. . . . . . . . . . . . . . . . . . . . . . . . . . 804
807
In pulp and paper processes
807
2.1 History
807
2.2 Chlorination stage pulp and filtrate. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 807

2.3 Mineral oil defoamers
808
2.4 Dioxin precursors in the environment
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 808
2.5 Wood . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 809

2.6 Pulping processes
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 809
2.7 Combustion of wood products.

2.8 Atmospheric contaminants
3. Strategies for redudng
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 810
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 811
dioxin formation
812
3.1 Reduced application of chlorine in the C stage
812
3.2 Split addition of chlorine in the C stage and increased pH . . . . . . . . . . . . . . . . 814

3.3 Useofpurifieddefoamers
815
3.4 Knot removal. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 815

3.5 Steam stripping of brown stock
3.6 Control of polychlorophenol
3.7 Avoidance of chloride-containing

4. Governmental
standards
816
(PolyCP) in chip supply . . . . . . . . . . . . . . . . . . . 816

hog fuel. . . . . . . . . . . . . . . . . . . . . . . . . . . . 816
for dioxin dI8cbarge
5. SampUng and measurement

5.1 Samplingprecautions
. . . . . . . . . . . . . . . . . . . . . . . . . . 816
.........................................
8] 7
817
5.2 Outline of dioxin measurement steps. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 817

6. Fate of dioxins In the environment.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 817
799
Chapter VIll 3: Dioxins and Furans in Effluents, Pulp, and Solid Waste
Chapter vm 3:
Dioxins and Furans
in Effiuent, Pulp, and
Solid Waste
1.2 Toxicity of dioxins

Despite the large number of congeners
in the family, only 17 are generally considered toxic, and these are the congeners chlorinated at the 2-,3-,7-, and S- positions of the
structure. The degree of toxicity of the
2,3,7,S-substituted
congeners varies with
the precise structure and is greatest for the
2,3,7,S-substituted
tetrachlorodibenzo-pdioxin (2,3,7,S-TCDD). Evaluations of the
comparative toxicities of these 17 structures
have led to the development
of several
scales of toxicity equivalent factors in which
2,3,7,S-TCDD is given a value of one (2).
Of these scales, the International Toxicity
Factor scale is the one which has gradually
gained acceptance in most countries (Table
2) (3). The development of an all-encompassing comparative toxicity scale is not
simple because the response to, for example, 2,3,7,8- TCDD has been documented
as changing with the test organism used and
the method of delivery (Table 3); guinea
pigs are 5000 times more susceptible than
hamsters to the toxic effect of 2,3,7,8- TCDD
(4). The mechanism by which dioxins exhibit toxicity is under continuing study, but
there is evidence that dioxins bind strongly
with the aryl hydrocarbon receptor in the
cell. This complex can then be transported
into the cell nucleus after coupling with a
translocating protein (5) .The different con-
1. Introduction
1.1 Definition of terms, nomenclature
conventions, and physical properties
Dioxin is properly the shortened name
for dibenzo-p-dioxin. However dioxin is also
the common name given to the members
of a family of tricyclic chiorinated aromatic
compounds (Fig. 1) which comprises 75
polychiorinated dibenzo-p-dioxins (PCDDs)
and generally includes 135 polychiorinated
dibenzofurans (PCDFs). Each member (CORgener) of the family belongs to a homologue
group which is defmed by the degree of
chiorination.
Tule 1. Pbyskal properties of2,3,7,S-TaJD
(1).
802
Table2. 1'ImdIy .'Vtlltmtsfaetors
TCDD
TCDD
PeCDD
PeCDD
HxCDD
HxCDD
HxCDD
HxCDD
HpCDD
HpCDD
OCDD
2,3,7,8Other
1,2,3,7,8Other
1,2,3,4,7,81,2,3,6,7,81,2,3,7,8,9Other
1,2,3,4,6,7,8-
Other
Tule
3. ~
tozIdty ofTCDD'" e~l
Atoms of Chlorine
1
2
3
4
5
6
7
8
Total
Fig. 1. Strwetures of Ml1M%o-p.~,.
lUlled molllk tIIUltile ~
polyeblorltulted dlbnzofu,.",.
6
Dioxin Isomers
2
10
14
22
14
10
2
1
75
0.1
0
0.5
0.05
0
0.1
0.1
0.1
0.1
0
0.01
0.01
0
0.001
tmI"",1s Is tISrl4l1UNl 011tile IHIsIsof tile ID... tile dose ('"
Species
~me
IDw~~)
Oral
Oral
Oral
Dermal
Intraperitoneal
Oral
Oral
Oral
Oral
Intraperitoneal
Oral
Oral
Oral
Oral
Intraperitoneal
0.6
2.1
115
275
152-500
<70
22
45-500
<150
120
30-300
>100
1,000
1,157
3,000
Hamster (male, female)

Hamster (male, female)
Dlbenzofuran
Dlbenzo-p-dloxln
I-TEF
TCDF
TCDF
PeCDF
PeCDF
PeCDF
HxCDF
HXCDF
HxCDF
HxCDF
HxCDF
HpCDF
HpCDF
HpCDF
OCDF
mleroftwms}In' frllogrwmof booiymgllt) tbat frills balf of IItest group (4).
7~~3
run
1,2,3,4,6,7,81,2,3,4,7.8,9-
7~~3
0.2:t 0.2
570
7.2 x 10.10
6.8
310
2,3,7,8Other
1,2,3,7,82,3,4,7,8Other
1,2,3,4,7,81,2,3,6,7,82,3,4,6,7,81,2,3,7,8,9Other
1
0
0.5
0
0.1
0.1
0.1
0
0.01
0
0.001
Other
8~2
Solubility
In Water, ppb
In Benzene, ppb
Vapor Pressure, torr
Log Kow
Furan
Congeners
I-TEF
8~O~2
322
303-305
(3).
Dioxin
Congeners
Guinea pig (male)

Guinea pig (female)
Rabbit (male, female)
Monkey (female)
Rat (male)
Rat (female)
Mouse (male)
Mouse (male)
Dog (male)
Dog (female)
Frog
Mol.Wt.
M.P., C
A maximum,
801
4
Furan laomers
4
16
28
38
28
16
4
1
135
IIU dlbnzofurrm, tile ,.fIfIIbmJ8g system

to IderttIfy tile el11orl.
--'
of OOfIpurs I,. Mell polyelllorl""ted Ml1M%o-p-dton,.
(PCDD)tIIUl
(PCDF)l1omo~
group.
gener toxicities by this model are therefore

an outcome of the degree to which a particular dioxin binds to the aryl hydrocarbon
receptor. The cause of the species dependence is less clear but, from this model,
likely arises from some change in binding
or transportation efficiency.
~me of the toXic effeCtS observed in the
laboratory studies are blood chemistry
changes, liver damage, skin disorders, and
lung lesions (6). 2,3,7,8-TCDD has also be
shown to be an animal carcinogen causing

several different tumor types at a number
of sites within the body including the liver
and thyroid (7).
Despite the results oflaboratory studies,
the effect of general or even severe exposure of organisms, including man, to dioxins seems to eont~dict the finding that
organisms are extremely sensitive to dioxins. This contradiction may be a result of
the tendency of dioxins to bond strongly
Chapter VIII 3: Dioxins and Furans in Eftluents, Pulp, and Solid Waste
803
804
3,500
COMBUSTION
3,000
0..
':
c
Carbon
+ Hydrogen
+ Oxygen
+ Chlorine
Heet..
CI <y0Y'lr
hO~
2,500
0 2,000
CI
CONDENSATION
~...
-c
1,500
:i~(6~
CD
0
c 1,000
0
U
500
CI N80
P5 H6 H7 08
T4
Remarks
Workers
Exposed
Location
of Accident
1949
250
Monsanto plant
in Nitro,WV
122 cases of chloracne being studied; 32 deaths

v.', 46.4 expected; no excess deaths from malignant neoplasms or circulatory disease
1953
75
BASF plant
in Ludwigshafen
55 cases of chloracne, 42 severe; 17 deaths V., 11

to 25 expected (4 gastro-intestinal cancers and
2 oat-ceiliung cancers); most common injuries
were impaired senses and liver damage
1956
Rhone-Poulenc
plant in Grenoble
17 cases of chloracne, also elevated lipid and

cholesterol levels in the blood
1963
106
NV Philips
plant inAmsterdam
44 chloracne cases (42 severe), of whom 21

also had internal damage or central-nervol15system disturbances; 8 deaths (6 possible my0cardial infarctions); some symptoms of fatigue
1964
61
Dow Chemical plant

in Midland, M1
49 cases of chloracne; 4 V.,7.8 expected deaths;

3 cancer deaths v., 1.5 expected, 1 a soft-tissue
sarcoma
1965-1969
78
Continuing leaks
in Spolana plant
near Prague
78 cases of chloracne; 5 deaths; many of the 50

workers studied for more than 10 years have
hypertension, elevated blood levels of lipid and
cholesterol, prediabetes; significant amounts of
severe liver and neurologic damage
Rh6ne-Poulenc
plant in Grenoble
21 chloracne
cases
Coalite & Chemical

plant in Derbyshire
79 chloracne
thrombosis
cases; 1 death from coronary
1966
1968
90
1976
156b
'v
verified.
= total
lcmesa plant
in Seveso, Italy
exposure
of 37,000
residents
Workers are being studied along with exposed

townspeople; more than 500 residents treated
for presumed toxic symptoms; 134 confirmed
chloracne cases; overall mortality rate normal
in nearby
communities
O=
~
CI
t)
~
CI
CI
1,2,3,6,8,9-HexBChlorodlbenzo..p-dloxln
CHLORINATION
o=:t)
"-~II86IIe.
tIHm800 fIIOf'tnsIMw 6wII ~

to
TIIbk 4. HIstory of 1__1rW ~
", IIJIIkb tolll'
of"""'"811Mby tbe AIwrka MMkIIl AssoeUIt/(m
"
sipljbtlt
_ts
of TCDD.DtItII
""-'
(9).
"" " s""'"
Date
CI
P5 H6 H7 08
PCDFs
PCDDs
FI,. 2.lHM1I~"
CI
Hepl8chlorlnllted Predloxln
T4
C~
C1
DBD
FI,. 3. G-.l
O= t)
C1
CI
CI
~1C1
2,3,7,8-
TCDD
of PCDDtIItiIPCDF
j'ormtIIIqt8.
to surfaces, which may hinder transfer to

the body. Further, the hydrophobicity
of
chlorinated dioxins makes them fat rather
than water soluble, limiting their dispersion
in the blood stream. Most animals have a
level of dioxins in their fatty tissues which
mirrors their general environmental exposure to dioxins (Fig. 2) (8). Some relevant
data for the physical properties of 2,3,7,8TCDD are given inTable 1 (1).
There have been circumstances where
humans have been exposed to dioxins at
levels potentially higher than those that
have been evaluated in laboratory animals
and much higher than the degree of exposure that has been estimated to cause an
increase in the risk of cancer (Table 4). The
observed effects were similar after each
exposure and were found to be temporary
(Table 4). The major common effect was
chloracne (9). Some examples of risk specific doses as calculated by different individuals, organizations,
and regulatory
agencies are given inTable 5 (10).
1.3 Reaction mechanisms for dioxin

formation
Dioxinoriginatesfrom manysources as
an unwanted trace contaminant (Table 6).
The dioxins from these sources can be considered as arising by three main mechanisms: combination
of chlorine radicals
with hydrocarbon structures at high temperature (11), condensation of chlorinated
sodium phenolate structures (12), and electrophilic substitution
by chlorine of an
unchlorinated
precursor compound (13,
14) (Fig. 3).
Chlorinated
dioxins can also be destroyed during combustion. The conditions
in combustion, in particular, are critical in
determining the amount and type of each
dioxin congener that is emitted into the environment (15).
Because dioxin fonnation is very depen.
dent upon the conditions that exist in the
particular dioxin-forming process, it is difficult to obtain an accurate evaluation of the
relative amounts produced by each source.
Several attempts have been made to produce a ranking, and one example is given
in Table 6 (16). Some of the most revealing
data in determining the general contribution from major sources are the results from
a comfY.lrison of industrial, suburban, and
rural sites (Fig. 4) (17).
These results show that dioxins are
largely a result of human and particularly
Chapter vm 3: Dioxins and Furans in Efiluents, Pulp, and Solid Waste
805
806
Tule 5. lbuImplesof rlslIsJIIfteloses.. refloses~

byilfdillitlul sdMIIsIs,6dMIifte
orgtlfllztlllmrs," repWory a~for
2.3,7,S-TCIJD
(10).
Risk/Specific Dose
2,3,7,8-TCDD
Source
Sielkin
CDC
EPA
FDA
FRG
LMS
M-K-V
MLE
NRC
CANADA
pg
PCIJF-..Is
t,erunwte4 yearly lit CatI4a.from
Forest fires
Municipal waste incineration
Sewage sludge incineration
Firewood combustion
Wood preserving waste water
Chlorophenol prod., air emissions'
Wood preserving waste disposal
Residential heating
Coal-fired utility boilers
1,000
o
T4
Motor vehicles
Cigarette smoke
IlI./fere81 _IUS
c:
o
:;:;
.1
c:
Q)
P5 H6 H7 08
PCDDs
of tIM PCDIJs ..
PCDFs fourut
1400-3300
1800
1500-6500
3
4
1000
600
600
>300
700
5
6
7
8
9
ZOO
10
11
T4
P5
H6
H7 08
PCDFs
In soils at frulllstrltll,
suburbtln,
"rut ,.",.,,1 sties.
100
80
()
60
o
c:
'xo 40
is
~
:;:;
20
Soil - SE England
Sediment
- Lake
Sediment Lake Siskiwit
Huron
0
1800
1850
1900
1950
2000
Year
1
550-21700
Note chlorophenol no longer produced in Canada.
(16).
FI,. 4. ComptIrlstm
a:I
Q)
a:
250-13700
900
>500
900
300
Industrial
2,000
Rank
58700
Urban
f:SJ
()
PCDF
g/year
'E
Q)
Center for Disease Control, U.S. Public Health Service

U.S. Environmental Protection Agency
U.S. Food and Drug Administration
Federal Republic of Germany
linear multistage model
Moolgavkar, Knudson, Venzon
Maximum likelihood estimate
National Research Council, Canada
Health and Welfare Canada (and) the Province of Ontario, Canada
PCDD
=picograrn.
'lllble 6. Estimate of PCDD..
o Rural
c:
.2
0.006
0.007
0.03
0.06
0.07
0.6
1.0
2.4
4.0
10.0
26.0
(MLE)
Rural, Urban and Industrial Soils
: 3,000
pg'/kg/day
EPA(LMS)
California
CDC
FDA
NRC Canada
M-K-VModel
FRG
NY State
Netherlands
Canada
4,000
FIf. 5. HIsIory of "'-lIt
UJIosItImt lit
"'U-t
loetItIorIs.
industria1 activity. Contributions from natural sources, however, cannot be ruled out.
Although attempts have been made to make
correlations (18), it is difficult to specify a
particular human activity beyond increased
combustion-related
activities. Also rural
contamination, if consistent, represents a
very large accumulation because the total
is the product of the concentration found
and the area contaminated. Historical data
on the concentrations
of dioxins in soil
samples also help to identify the contribu-
tion from non-industrial and industrial

sources (19).
Figure 5 shows results from a number of
studies made in different locations where
contamination
was considered to be the
consequence
of long-range atmospheric
transport. The data indicate that there has
been an acceleration of dioxin emissions
during the twentieth century but that the
period when an increase occurs is site specific.The results indicate that it is the onset
of industrial activity in an area which cre-
Chapter vm 3: Dioxins and Furans in Effluents, Pulp, and Solid Waste

ates a higher level of contamination. These
results also show that there was a consistent non-industrial production of dioxins
which produced a significant background
concentration.
1.4 History
of increasing
public aware-
ness
Table 4 (9) shows that there has been a
recognition of human health effects from
industrial exposure to dioxins since 1949,
when it was first understood that chloracne
was specifically associated with exposure
to the chemical. General public awareness
of concerns over dioxin exposure was awakened by the industrial accident at the
Icmesa-Givaudian plant near Seveso, Italy,
in 1976 (20). It was further heightened by
the evacuation of the contaminated areaS
atTunes Beach, Missouri, in 1983 where oil
mixed with sludge waste contaminated
with 2,3,7,8- TCDD from a hexachlorophene
plant was used for dust control on local
roads and recreational areas in 1971 (21).
These events led to concern by Vietnam
veterans about the effects of their exposure
to the defo1iantAgent Orange which possibly contained 2,3,7,8-TCDD (22).The concerns arising from these events led to an
evaluation by the U.S. Environmental ProtectionAgency (EPA) of the degree of dioxins exposure
at sites where it might
reasonably be considered that higher than
background
levels of dioxins would be
found. In 1985, a seven-tier study, known
as the National Dioxin Study, was initiated
to evaluate locations having different levels of contamination; the seventh tier of the
study involved an examination of the background level of contamination (23).
2. Formation in pulp and paper

processes
2.1 History
It was the studies associated with the
background level evaluation described in
Subsect. 1.4 that led to the finding that chlorimlted diOxins could be an unwanted by-
product
of pulp and paper processes.
Elevated levels of dioxins were found in fish

caught in the Androscoggin River (Maine)
807
and Rainy River (Ontario-Minnesota). The

common factor was that pulp mills were
located near these rivers. Ironically, a study
had been made on the Rainy River before
this one showing that there was no dioxin
contamination at the parts per billion level.
Improvements
in analytical techniques,
which allowed analysis at the parts per trillion level, led to the new finding that pulp
mills could be a source of dioxins. Results
from researchers
in several countries
showed the generality of the contamination
(24-26). The pulp and paper industry responded by determining
how general a
phenomenon
the contamination
was by
participating in several analytical studies; in
the United States, an in-depth study of five
mills (27) was supplemented
by a much
wider survey of all 104 bleached chemical
pulp mills (28) while, in Canada, an equivalent study was done of all 47 chemical pulp
mills (29,30).
These studies confirmed that some industry operating practices led to dioxin formation. The studies also showed, however,
that several mills did not produce dioxins.
Variations in the results gave some indication as to the cause of the dioxin contamination.
Today, careful control of certain key aspects of the pulp and paper process ensures
that dioxins normally cannot be detected
with the best available analytical techniques. However, before the major modifications were made to operating procedures,
it is now known that dioxins were being
generated in different parts of the process
by each of the major mechanisms described
in Subsect. 1.3.
2.2 Chlorination
stage pulp and filtrate
The major source of dioxins in the pulp
and paper industry was the bleaching process in which chlorine was used as the
chemical of choice. When analyses were
made of samples collected throughout the
pulp manufacturing process (31-33), it was
found that the C stage was generally the bt
point where dioxins appeared. This pulp
had the largest concentration
of dioxins,
and the 2,3,7,8-TCDD, 2,3,7,8-TCDF and
808
120
100
a.
80
c
0
-a.
~60
-c
CD
(,)
c
0
40
U 20
0
T4 P5 H6 H7 08
T4 P5 H6 H7 08
PCDDs
Fig. 6. 1h
typWl
SjIIrrIm
IIuIIaIH",
PCDFs
blMeb p",,,,-genertIIetI
1,2,7,8-TCDF
congeners
were always
present (Fig. 6). Of the bleaching filtrates,
the E-stage filtrate was found to have the
highest concentration of dioxins.This rmding led to speculation
that chlorinated
phenols generated in the chlorination stage
but carried over into the extraction stage,
had condensed to form dioxins by the same
mechanism as that occurring in trichlorophenol production (34). However, the particular chlorinated phenols generated in the
C stage, when condensed,
should have
given a very different congener distribution
than the one observed; the actual profile
was the same as that found in the C-stage
pulp. It was therefore concluded that the C
stage was the point of formation and that
the elevated level of dioxins in the E-stage
filtrate was a consequence of their removal
from the pulp in soap micelles or on fines
(35).The dioxins associated with the fines
accumulate in the sludge from both the primary and secondary treatment (36).
The very distinct pattern of formation,
together with the observed approximate 3
to 2 ratio of 2,3,7,8-TCDF to 1,2,7,8-TCDF,
provided a clue to the mechanism of generation because the congeners found were
also those which were predominantly
formed when unchlorinated aromatic precursors, with the basic dibenzo-p-dioxin
(OBD) and dibenzofuran (OBF) structure,
were chlorinated (37). The understanding
2,3,7,8-TCDF
tUoxhts.
of mechanism allowed strategies for preventing formation to be formulated (31-33,

3840).
2.3 Mineral oil defoamers
The unchlorinated dioxin precursors are
ubiquitous in the environment, but are particularly prevalent in certain mineral oils;
the amount present is determined by the
cut taken from the petroleum fractionating
column and can be reduced by a secondary treatment such as hydro refining (41).
These mineral oils are part of the defoamer
formulations used by the pulp and paper
industry and were a major source of precursors (42).
2.4 Dioxin precursors in the environment
Dioxin precursors can also become part
of a pulp through simple adsorption from
the ambient environment (37). The precursors have a much higher vapor pressure
than the chlorinated product and can transfer easily through polyethylene (which can
make it difficult to do accurate experimental work). The unchlorinated precursor concentration
in pulp, which is orders of
magnitude higher than the chlorinated dioxins concentration, equilibrates with its
environment (e.g., pulp). This concentration of DBD in pulp under equilibrium conditions is often two onlers of magnitude less
than the concentration
of DBE However,
Chapter VIII 3: Dioxins and Furans in Effluents, Pulp, and Solid Waste
the concentrations
of 2,3,7,8-TCDD and
2,3,7,8-TCDF under the bleaching conditions that cause dioxin fonnation are often
only one order of magnitude different. The
reason for this discrepancy is that DBD reacts faster than DBF with chlorine (37).
Dioxins can also be fonned from alkylated precursors which are present in the
environment
at higher levels than the
unalkylated precursors. The alkyl group,
however, does not undergo electrophilic
substitution very easily therefore; the formation of unalkylated chlorinated dioxins
from alkylated precursors during bleaching
occurs only slowly (43).
2.5 Wood
Another source of dioxin precursors is
the wood itself. In particular, compression
wood contains higher concentrations
of
precursors than normal growth wood. Compression wood also contains higher levels
of coumaryl-type
lignin which may be a
source of these DBD- and DBF-Iike precursors. The concentrations of dioxins fonned
in laboratory pulping and bleaching of compression wood in the furnish has been
found to be greater than from similar treatment of nonnal wood (44,45).
Debate has continued on the predominant mechanism of fonnation of chlorinated
dioxins in bleaching. Some authors have
809
810
Pulp Bleaching
1.2
a.
Co
c:
.Q
i
....
0.8
-cQ):
0.6
c:
()0
0.4
(.)
0.2
0
Fig. 8. Possible
spectrum
of PCDDs
g 2,000
o
1,000
T4 P5 H6 H7 08
PCDDs
spectrum
a""
PCDFs lukati"g
Q)
'"
C.
E
<tI 0.8
'"
.5
c
0
~0.6
Q)
'E
0
c 0.4
0
0
'0Q)
.!!1
10
E
0
effluent
contamination
of PCDDs
a""
PCDFs i""kllli"g
T4 P5 H6 H7 08
PCDFs
PolyCP-contaminateti
chips.
from fly-ash.
lZJ Unbleached kraft

~ Groundwood
DTMP
~ CTMP
0.2
T4
P5
H6
P5 H6 H7 08
H7
IUstrlInItion
fmuul
for samples
tion of the dioxin. A typical distribution

spectrum for this type of dioxin contamination is shown in Fig. 7 (49).
It has now been found that the above
mechanism of fonnation can also operate
in thennomechanical
pulping when the
chips are contaminated with a PoIyCP formulation; the heat and pressure in the refiner appear to be sufficiently high to cause
tricyclic ring closure (50).
:0:;
n!
.::. 3,000
cQ)
Fig. 7. Possible
PCDFs
PCDDs
Fig. ,. Tbe bomolope
4,000
T4 P5 H6 H7 08
PCDFs
PCDDs
: 5,000
()
H6 H7 08
P5
T4
6,000
and Practice
1.4
contended that oxidative condensation of

chlorophenols
could occur under C-stage
conditions either to fonn the unchlorinated
or partially chlorinated
precursor
(46).
However, more recent work has shown that
this does not occur to any observable extent (47).
2.6 Pulping processes
In a Canadian mill survey (48), it was
shown that many west coast miIls had elevated concentrations
of the hexachlorodioxin homologue, particularly the 1,2,4,6,
7,9-, 1,2,4,6,8,9-, 1,2,3,6,7,9-, 1,2,3,6,8,9-,
1,2,3,6,7,8-, and 1,2,3,7,8,9-congeners;
the
amounts of hepta- and octachlorodioxin
homologue were also often elevated. It was
found that these dioxins were generated by
condensation
of chlorinated
predioxins
(Reaction 2; Fig. 3) in the pulping process
(49). These chlorinated
pre dioxins are
present in the polychlorophenol
(poIyCP)
preparations
used for anti-sapstain treatment of lumber products. Therefore, chips
produced as the by-product of saw mill
operations and sent to the pulp mill could
be contaminated with chlorinated predioxins. The particular congener distribution
observed is very dependent on the PoIyCP
formulation
and probably the pulping
conditions because there are competing reactions which cause fonnation and destruc
-Principles
It is important to note that, if the polyCP

fonnulation contained only the single-ring
chlorophenol, then no dioxins would be
generated in the pulping process; it is nec-
contamitltltetl
by tbe everydlly
environment.
essary to have the predioxin present so that

the probability of tricyclic ring closure is
high (49).
2.7 Combustionof wood products

Combustion can also be a source of contamination (51), for example, in pulp mills
where chloride-laden hog fuel (> 0.1 % NaCl
on wood) is burnt as a means of decreasing
the need for land fill and as a source of low
pressure steam. Dioxins, because of their
affinity for surfaces, tend to adsorb on the
ash from these processes. A typical spectrum of this type of contamination is shown
in Fig. 8. If a wet scrubber is present on
Chapter VDI 3: Dioxins and Furans in Eftluents, Pulp, and Solid Waste
Bleached Kraft
Unbleached Kraft
811
812
However, as can also be seen from

Fig. II, dioxin levels in household dust are
orders of magnitude higher than that in any
pulp and paper product.
ND
0.02
3. Strategies for reducing dioxin

formation
Newsprint
Deinked Pulp
As there are several mechanisms

by
which dioxins are generated, there are also
several strategies that have been implemented to produce products, sludges, and
effluents that are dioxin-free (58).
0.19
TCF Bleached Kraft
0.35
Recycled Linerboard
2.5
o
0.5
1
Toxic Equivalents,
FIg. 10. CmrtptJrlsmI of PCDDIFcmtItm8l_ts,
prot/Ircts.
_millS
1.5
2
2.5
pg 2378-TCDD/g
toxk eq.dvtllnlts,
3.1 Reduced application of chlorine in

the C stage
3
of dlff-t
j"dp IIIIIl}ItIJIn'
Plastic Packaging
Clothes Dryer Lint
Vacuum Cleaner Dust
Room Air Filter
83.7
Car Air Filter
167.4
House Furnace Filter
Preventing dioxin formation in the bleach

plant has been achieved mainly by decreasing the amount of chlorine used in the first
bleaching stage (59-61). It is not necessary
to eJiminate the use of chlorine. In the early
evaluations, the formation of TCDD and
TCDF became measurable only when a
molecular chlorine multiple of 0.16 was
used (Fig. 12). In the initial rapid phase of
reaction in the chlorination stage, chlorine
is consumed by the lignin in the pulp more
quickly than it reacts with precursor compounds and, therefore, at chlorine multiples
lower than 0.16, there is no excess of chlorine available to continue the progressive
chlorination of TCDD andTCDF precursors.
Beyond a chlorine multiple of 0.16, the re-
o
50
100
150
200
Toxic Equivalents, pg 2378-TCDD/g
Fig. 11. CmrtptJrlsmIof PCDDIFcmtItm8luats, _millS
f1fInydtrynmrormumt.
these boilers, the scrubbing water becomes
contaminated with dioxins and these dioxins can be partially transferred to the mill
effluent (52).
toxk N]IIII1IIkrm,of Ym}Jles IIIMnfrrnn tH
The fina1 source of dioxin contamination

in the pulp and paper sector is the ambient
environment (53-56). The homologue distribution in this type of contamination (Fig.
9) is dominated by the higher dioxins. It
(57). Dust, which has a very high surface

area, probably becomes contaminated from
general combustion sources. For this reason, paper made from a pulp produced. for
example, by a sequence using no chlorine
or chlorine dioxide may become contaminated during its life cycle even though it
was originally dioxin-free. This phenomenon Is amplified when a material is recycled (55,56). In particular, the recycling
has recently been shown that exposed materials can become contaminated with dioxin through the entrapment of dust, which
contains high concentrations
of dioxins
of old corrugated containers can lead to

products and effluents which have a relatively high dioxins concentration
as measured byTEQs (Fig. 10).
2.8 Atmospheric contaminants
35
0.
a.
maining lignin consumes chlorine more

slowly and an excess of chlorine provides a
chlorine concentration
which drives the
dioxin-forming reaction for a longer period
oftime.
Figure 12 also shows that kappa number,
over the range commonly found before
bleaching, has no significant effect on the
progression of dioxin formation. However,
the role of kappa number in determining
the appearance of a measurable dioxin concentration is not clear. It has been suggested
(62, 63) that a higher kappa number pulp,
or one that has an effectively higher kappa
number because of liquor carryover, will
cause the formation of higher concentrations of TCDD and TCDF because of the
higher chlorine charge required at a given
kappa factor. However, changes in the
amount of the dioxins formed appears to
be small over the range of kappa numbers
commonly found before bleaching (38).
There is some indication that hardwood
pulps can be bleached with higher molecular chlorine multiples than softwood pulps
without generating PCDDs and PCDFs (48).
This result may be a consequence of a different chlorine concentration
profile during the bleaching process. Sulfite pulps do
not appear to generate PCDDs and PCDFs
at all in the range of bleaching conditions
normally used (48). No explanation has
Kappa
37.7
30
ci 25
33.1
a.
.~
0
0
U
I-,
28.1
.
25.9
"'5
20
15
10
~.....0
5
~C\I
0
0
0.1
Active
FIg. 12. 1'bt! clHulp
I.. 2,3, 7,B-TCDD jorrIMtUm
0.2
Chlorine
wltb cblorine
0.3
0.4
Multiple
m"lHpll!
IIIIIl rtJltb "..bll!tU:Hd
IIIf/I1M .."mber.
813
100
o.
c:
0
+:: 80
::J
Non-measurable
dioxin
40
15
20
0
0
0.05
0.1
0.15
Active chlorine
Pig.13. CtnI4ItknIsollldlve cblorllw _ltiple
(FilIM _rUts, 2,3,7,S-TCDD-mle,
mill
11411I; elrr:les,
lllbortItory
0.25
0.2
0.3
TCDPlomI4Ho1t
(38).
C-stage: 0.21 x kappa number (% CI, on o.d. pulp); 50C for 30 min; 3.5% consistency.
,
ND = not detected, detection limit given in brackets.
multiple
II1Iilcblorlu ~
SllbslUrlHoIttlMtform 2,3,7,S-TCDD
8".ftIW 1IIiI1'Urs.2,3,7,S-TCDD__tYlble;
If'U'"'s,
11411I).
8
C+D
-a.a.
011 TCDD _
Concentration in Chlorinated Pulp, ppt

2378-TCDD
2378-TCDF
0.5
ND(2)'
4
1.0
ND(l)'
20
1.0
ND(2)'
32
2.0
10
89
3.0
11
345
3.5
10
234
5.0
8
135
5.0
10
344
Unbleached pulp;Western hemlock kraft pulp; kappa number, 25.9.
::J 60
en
(I)
and Practice
Consistency, %
~..c
c:
'1::
.Q
.c
0
-Principles
Pulp Bleaching
Table 7. Effect 01 amsIsteMy
:::.!!
(I)
"'C
'x
0
814
C/D
ci
0
0 4
lcb
r-:
D/C
.
.
M 2
N
.
10
been proposed for this finding, but it may

be that a sufficiently high chlorine concentration is never available for PCDD and
PCDF formation in this easily bleached furnish or that dioxin precursors are sulfonated
during pulping and are solubilized or rendered unable to form the unsulfonated
PCDD and PCDFs.
The use of peroxide in the extraction
stage or higher charges of chlorine dioxide
in the dioxide stages allows an active chlorine multiple ofO.I6to be used in the chlo-
60
%
70
tile live eblorllw _ltlple
Is 11II-
rination stage (64). However, many mills

prefer to bleach with a higher active chlorine multiple in the chlorination
stage
which can be done by substituting chlorine
with chlorine dioxide (31-33,3840).
Figure 13 (38) shows the conditions of
active chlorine multiple and chlorine dioxide substitution that will lead to dioxin formation and those that will not; the line
separating the two sets of conditions was
calculated for the simultaneous addition of
chlorine and chlorine dioxide. As long as
WOC!- + W + C!-
35
30
2,3,7,8 25
TCDD, 20
ppt
15
10
5
35
30
2s2,3,7,S TCDD,
20
ppt
15
02040-
Chlorine 60Dioxide
80Substitution.
%
100-
[1]
The effect of decreasing consistency (the

addition of H20) is to drive this equilibrium
to the right and to decrease the concentration of the chloronium ion. This lowered
concentration in turn decreases the amount
of dioxin formed (Table 7) (38). Lowered
hydrogen ion (or chloride) concentration
also forces the equilibrium to the right and
Split addition of chlorine in the C

stage and increased pH
Dioxin-forming reactions occur through
the interaction of the hydrated chloronium
20
30
40
50
Chlorine Dioxide Substitution,
Fig. 14. 2,3.7.S-TCDD form4IIott by tUD-t

mo4es 01 a4tUtImJ ID_
J8Stetl to give a OOfISttmt CEIIiIJ1PdIt8mber.
CI+CI-+ HP
3.2
0
o
ion (CI+) with dioxin precursors. The concentration of this ion for a given charge of
chlorine is dependent upon elemental chlorine, chloride and hydrogen ion (pH) concentrations,and temperature because of the
chemical equilibrium
formed by dissolution of chlorine in water:
the comparison is made at constant kappa

number after extraction, there is no difference in dioxin formation caused by changes
in mode of addition (Fig. 14); it can be concluded that the chlorine dioxide-first mode
of addition is preferable because of the
lower chemical charge required (65,66).
The effect of active chlorine multiple, chlorine dioxide substitution level and precursor concentration can be summarized in a
three-<limensional plot of the data (Fig. 15)
(38).
10
5
.....
0.16
0.12
Fig. 15. Effect 01 precursor COfIttmt. lIlJe cbloritUI multiple,

2,3, 7,S-TCDDlormaHolt.
0.2
'0.24
....
0.28
Active Chlorine
Multiple
and cblorine dioxide substitution
level 011
TtIbk 8. hlcrNrill/f"
pH '-ers
bkllebed}1roMcl (38).
NaOH
Applied,%
on o.d. pulp
0.0
0.1
0.5
1.0
2.0
3.5
5.0
7.0
10.0
tbe _",
C-stage pH
Initial
8.2
8.5
8.3
8.9
11.0
11.1
11.5
Final
1.5
1.6
1.6
1.6
2.3
2.0
2.3
6.3
11.3
815
o/TCDD IIIUITaJF /ortMtl brIt /liso /If/eets tbe tpIIIltty 0/ tbe
CE
Kappa
No.
3.5
3.2
3.1
3.0
2.9
2.9
3.1
4.5
8.1
Cuene
Vise.,
mPd.s
15.6
12.3
12.1
11.3
10.2
11.2
8.5
10.1
14.5
Cone. in C-stage
pulp, ppt
2378-TCDD
2376-TCDF
15
15
15
12
11
6
2
ND(1)'
ND(1)'
456
482
461
383
347
165
23
10
5
Unbleached pulp: Western hemlock kraft pulp; kappa number, 25.9.

C-stage: 0.24 x kappa number (% Cl, on o.d. pulp); 50C for 30 min; 3.5% consistency.
.NO=
not detected, detection limit given in brackets.
decreases dioxin formation (fable 8) (38).

Finally, higher temperature
theoretically
also drives the reaction to the right although
the effect is too small to be statistically significant.
These principles have been incorporated
into a method of preventing dioxin formation which uses normal charges of chlorine
but no chlorine dioxide. By splitting the
total chlorine
application
into smaller
charges and adding them sequentially (split
addition) (36), the peak concentration of
chlorine can be kept lower than when it is
added in a single charge; chlorine concentration can also be decreased by lowering
the hydrogen ion concentration (increasing
the pH).A combination of these measures
provides a practical method of preventing
dioxin formation during bleaching (67).
3.3 Use of purified defoamers
DBD and DBF was to ensure that any defoamer used in the brown stock or bleach
plant areas was produced with an oil base
that was first treated to remove dioxin precursors or with a water base (42). Because
water-based defoamers do not work as well
as oil-based defoamers in brown stock applications, the simple expedient of substituting one product with another was found
not to be the solution. Instead, using a
hydrorefined oil base proved to be necessary. Oil-derived contamination
was also
found to occur, for example, from kerosene
(used to prevent chips freezing in chip
trucks), lubricating
oils and creosotetreated, wood-lined channels. It has been
determined that the dioxin formed by the
Canadian pulp and paper industry was decreased by approximately half through using purified defoamers (48).
One route by which dioxins are formed

is through the reaction of chlorine with
DBD and DBF or precursor compounds that
have the basic DBD and DBF structures, for
example, alkylated DBD and DBE A considerable reduction in pulp dioxin content
can be achieved at a specific molecular chlorine multiple through removal of these precursors (37).
One of the most quickly found methods
for preventing contamination of pulp with
3.4 Knot removal

The remaining precursor sources are the
tree itself and the ambient environment.
As previously mentioned, compression
wood has a high concentration of precursors (44,45). Efficient knot removal and the
assignment of knots to ~ ~dfill t"Jther than
to a refining system for recovery of fiber
can help in decreasing
this precursor
source.
816
Pulp Bleaching
-Principles
and Practice
Because contamination through the ambient environment is impossible to prevent,

some amount of the precursors will always
be carried forward into bleaching as part
of the brown stock.
3.5 Steam stripping of brown stock

The precursor concentration that finally
comes into contact with chlorine can be
decreased by steam stripping the brown
stock before bleaching (38). Although it has
not been introduced as a separate process,
steam stripping is an inherent part of highconsistency
processes where volatile components are constantly purged from the reactor to prevent
an explosion hazard. Steam stripping can
also be achieved through blowing the
brown stock at a temperature
at which
steam is driven from the pulp. This effect
of steam stripping presumably was responsible for some of the early contradictions
regarding the role of oxygen delignification
(32, 33, 36, 40) in preventing dioxin formation. If oxygen delignification is done in
a way to cause steam stripping, it is observed to reduce dioxin formation. However, this benefit is also obtained when
nitrogen rather than oxygen is used (38).
The decreases in kappa number, and corresponding decrease in chlorine concentration for a given chlorine multiple appear to
have a limited effect on the final dioxin
level.
Although the precursors with the basic
DBF structure appear to be fully removable
from the pulp, this is not the case for all precursors with the basic DBD structure (68).
Some DBD-like precursors
are probably
wood-derived and attached to the lignin in
the pulp. That these precursors have the
basic DBD structure is indicated by the very
characteristic generation of a congener distribution dominated by 2,3,7,8-TCDD.
Although not directly plotted in Figure
14, the precursor concentration
will determine the concentration of dioxin gener:Ued :it :my set of chlorination conditions
and can affect the boundary line between
conditions that cause and do not cause dioxin formation.
3.6 Control of polychlorophenol

(PolyCP) in chip supply
Another pathway by which dioxins can
be generated is through the pulping of
PolyCP-contaminated
chips (49, 50, 69).
Because there is no process change that can
easily be made to prevent dioxin formation
in this instance, it is necessary to ensure
that the chips entering the mill are free of
PolyCP-treated chips.Through education of
the chip supplier, spot inspection of the
chips in incoming trucks, and a system of
penalties, chip supplies are now generally
free from PolyCP contamination. Ironically,
some mills observe the characteristic homologue distribution of dioxins generated
through PolyCP formation although PoIyCP
is not found in the chip supply. The reason
for this anomaly may be that the sensitivity
of the dioxin test is far greater than that of
the PolyCP test (50).
3.7 Avoidance of chloride-containing

hog fuel
Dioxinsare alsogeneratedthroughcombustion of chloride-laden hog fuel at the mill
site. Strategies to overcome this problem
are to discontinue using hog fuel containing large amounts of chloride and to increase the temperature and retention time
in the hog fuel boiler (5/, 52).
4. Governmental standards for

dioxin discharge
There is considerable imperative to ensure that traces of dioxins are removed so
as to comply with governmental regulations
in certain jurisdictions
(70, 7/). For example, the Canadian federal government
has required that 2,3,7,8-TCDD
be decreased in the total mill effluent to the level
of quantitation which has been determined
to be 15 ppq; the regulated 2,3,7,8-TCDF
limit is 50 ppq. The Canadian government
also requires the chip supply to be free from
PolyCP and any defoamer used in the process to have a DBD ievelless than 10 ppb
and a DBF level less than 40 ppb.These regulations, which became effective in January
1994, require that concentrations
of dioxins in the final discharge be monitored
Chapter VIll 3: Dioxins and Furans in Effluents, Pulp, and Solid Waste
monthly until compliance is shown and
thereafter monitored at progressively longer
intervals.
The results of annual mill testing surveys
(48, 71) shows that dioxin levels have decreased by 98% since 1988 when the first
survey was made and will decrease still further as all mills complete the modifications
required to achieve full compliance. Even
with these efforts, a small residual dioxin
level will persist because of contamination
from the ambient environment which affects all materials, not just bleached chemical pulps.
Canada is the only country which presently has a national standard for dioxin discharges from the pulp and paper industry,
but there are several states in the United
States that have also required mills, by regulation, to ensure that dioxins are not discharged. Recently proposed EPAregulations
may provide an equivalent national standard
for dioxin discharges for the U.S. pulp and
paper industry (71). (See Chap.VIII 5.)
5. Sampling and measurement

(72)
Measurement of dioxins provides an extreme test of an analyst's skill and of the
equipment used. The analysis determines
the concentration of dioxins at the limits
of quantitation and detection at a level of
parts per trillion, quadrillion, and quintillion, depending on the matrix being evaluated. There are few laboratories
in the
world which can work consistently at the
high standards necessary, particularly as a
heavily contaminated
sample can change
the ambient concentrations of dioxins in a
laboratory.
5.1 Sampling precautions
It is also necessary to take considerable
care with the sampling process to avoid
contamination. Because of the high levels
of dioxins in dust, every surface coming into
contact with the sample has to be specially
prepared. Glass rather than plastic is used
in sample containers because of the microporosity of plastic. Sample bottles generally
have three parts: a glass container, a tightly
817
closing lid, and a liner. The bottles and any

other glassware used in the analytical process are cleaned by first conventional washing, followed by sequential rinsing with a
group of solvents.
5.2 Outline of dioxin measurement

steps
At the sampling site, surgical rubber
gloves are used in handling the sample
bottles. Pulp, effluent, and sludge are the
most frequently taken samples. About 40 g
o.d. of pulp, 2 liters of effluent, and 2 liters
of sludge are required
for duplicate
analyses.
Laboratory preparation including isolation, cleanup, and quality control is complex and exacting. Pulp is air dried, ground
in a Wiley mill, and Soxhlet-extracted
for
18 hours using a suitable solvent, e.g.,
acetone-toluene. Sludges are generally dried
and then extracted with toluene.
Procedures vary but involve the steps of
spiking with a sample-preparation recovery
standard, extraction, concentration,
separation by column chromatography, spiking
with an analysis recovery standard, further
concentration, and final analysis through gas
chromatographic separation and mass spectrometric identification.
Environment Canada has estimated the
variability in this last step by evaluating the
level of quantitation (LOQ). The estimate
was achieved by a study using 10 commercial, industrial, and governmental
laboratories analyzing 8 replicate
samples
containing low and near-detection-limit levels of2,3,7,8TCDD and 2,3,7,8-TCDE With
the definition of the LOQ as 10 times the
standard deviation, the concentration value
for2,3,7,8-TCDD and 2,3,7,8-TCDFwas established as 15 ppq in pulp mill effluents.
6. Fate of dioxins in the

environment
Dioxins are very stable compounds, but
there are conditions under which they are
degraded. Photodegradation
of PCDD/Fs
occurs naturally, but it appears that the rate
is very much dependent on the specific
environment (73). It has been shown that
818
concentrations
of ItCDD and HxCDD in
water decrease (half lives of 0.94 and 2.5
days respectively) through environmental
photolysis and that TCDD photo-decomposes in the vapor phase. However, it is
necessary for the molecule to be exposed
to light which is unlikely to occur in all circumstances.
Several artificial methods of eliminating
dioxins have been studied particularly in relation to the cleanup efforts made at Seveso
(74). To date, thermal destruction is the
most effective method of eliminating dioxins. The extent of destruction is a function
of time, temperature, and oxygen concentration.Temperatures
in excess of715"C for
1 second can eliminate 99",.(,of the dioxins
(75).
Photolysis by UV light can be accelerated
by the addition of chemicals, for example,
ethyl oleate/xylene, and high energy radiation such as gamma rays can be used with
solvents, for example, ethanol, to cause
dechlorination of dioxin molecules (76).
Another method consists of the direct
application
of a highly active oxidant.
Ozone can destroy dioxins after they are
extracted into an inert solvent. For example,
dioxins are degraded after being extracted
into carbon tetrachloride and then exposed
to a high concentration of ozone (77).
Another active oxidant is a mixture of
peroxide and polyethylene glycol (PEG).
Using a mixture of PEG 6000, K,CO} and
Nap, at 85C, 99.9% ofTCDD dissolved in
n-decane is destroyed in 3h.At 500C, using
the same mixture, all theTCDD is destroyed
in 3 h (75).
References
1. Crummet, W, 1988 CPPA Bleaching
mitteeTechnical
Session Proceedings,
Tech. Sect., Montreal, Chap.1.
2. Milby,
TH.,
Miller,
TL.,
Forrester,
ComCPPA
TL.,
Occup. Med. 27:351 (1985).

3. Ahlborg, U.G., in Organo Halogen Compounds in Human Milk and Related Hazards, Report on a WHO consultation. WHO
iegiotW Office
for EUf01)e
IPCICHE
SO 11
m 05, 1985.
4. Kociba, R.]. and Cabey, 0., Cbemospbere
14(617):649 (1985).
5. Poland,A. and Kende,A., in Origins of Human Cancer (H.H. Hiatt, ].D. Watson, ].A.
Winston, Eds.) Cold Spring Harbor, New
York, 1977, p. 847.
6. Poland, A. and Knutson,].,
Pharmacol.
Toxicol. 22:516
Annu.
(1982).
Rev.
7. Kociba,
R.]., Keyes, D.G., Beyer, J.E.,
Carreon, R.M., Wade, e.E., Dittenber,
D.,
Kalnins, R., Frauson, L., Park, e.N., Bernard,
S., Hummel, R., Humiston,
e.G., Tuxicol.
Appl. Pharmacol.
46:279 (1978).
8. Schecter, A., Ryan, J.]., Girtitz, G., in Chlorinated Dioxins
and Dibenzofurans
in
l'Prspective (e. Rappe, G. Choudhary,
L.H.
Keith, Eds.) Lewis Publishers,
Chelsea,
Michigan, 1986, Chap. 4.
9. Tschirley,
254(2):29
F.H.,
(1986).
Scientific
American

Protection
Agency, "A Cancer Risk-Specific Dose Estimate for 2,3,7,8-TCDD,"
EPA 600/6-88007, Office of Health and Environmental
Assessment, Washington,
D.c., 1988.
11. Choudhry,
G.G. and Hutzinger, 0., Current ToPics in Environmental
and
Toxilogical
Chemistry,
Vol. 4: Mechanistic Aspects of Thermal Formation
of Halogenated
Organic Compounds
1ncluding Polychlorinated
Dibenzo-p-dioxins,
Gordon and Breach Science Publishers,
New York, 1983, p194.
12. Dryden,
F.E., Ensley, H.E., Rossi, R.].,
Westbrook, E.)., "Dioxins: Volume III. Assessment
of Dioxin-Forming
Chemical
Processes," EPA 600/2-80-158,
Office of
Water Regulations and Standards,Washington, D.e., 1980.
13. Gray, A.P., Dipinto, Y.M., Solomon,
Org. Chem. 41(14):2428
(1976).
1.]., J
14. Gray,A.P., Cepa, S.P., Solomon, 1.].,Aniline,

0., J Org. Chem. 41(14):2435
(1976).
15. Lustenhouwer,].WA.,
Otie, K., Hutzinger
0., Cbemospbere
9(7-8):501 (1980).
16. Sheffield, A., "PCDDIPCDF: Sources and
releases," EPS Report 5/HA/2 Environment
Canada, Ottawa, Ontario, 1985.
17. Birmingham,
9):807 (1990).
B., Chemosphere
18. Hites, R.A. and Czuczwa,J.M.,
in tbe Environment
20(7in Dioxins
(Kamrin, M.A.,
Rodgers, P.W, Eds.) Hemisphere

Publishers, Washington,
1985, Chap. 7.
19. Kieller, L.-O, Jones K.e., Johnston,
A.E.,
Rappe,
C,. Environ.
Sci. Technol.,
25(9):1619
(1991).
20. Pocchiari, E, de Domencio,A.,

Silvano, V,
Viviano,
G., Zapponi,
G., Ecotoxicol.
Environ. Safety 4:282 (1980).
21. Stehr, P.A., Stein, G., Webb, K., Schramm,
W, FaIk, H., Sampson, E., in Chlorinated
Dioxins and Dibenzofurans
in Perspective (c. Rappe, G. Choudhary, L.H. Keith,
Eds.) Lewis Publishers, Chelsea, Michigan,
1986, Chap. 5.
22. Herbicides
in War: Tbe Long-Term Ecological and Human Consequences
(A.H.
Westing, Ed.) Taylor and Francis, London,
1984.
Protection
Agency, "The national dioxin study, Tiers,
3,5,6 and 7; EPA 440/4-87.003,
Office of
Water Regulations and Standards,Washington, D.C., 1987.
24. Amendola,
G.A., Barna, D., Blosser, R'.,
LaFleur,
L., McBride,
A., Thomas,
E,
Tiernan, T., Whittemore,
R., Chemosphere
18(1.Q):1181 (1989).
25. Clement, R.E.,Tashiro, c., Suter, S., Reiner,
E., Hollinger,
D., Chemosphere
18(16):1189 (1989).
26. Swanson, S.E., Rappe, c., Kringstad, K.P.,
Malmstrom,).,
Chemosphere
17(4):681
(1988).
Protection
AgencylPaper
Industry Cooperative
Dioxin Screening Study, NCASI. Tech. Bull.
No. 545, National Council (of the Paper
Industry) for Air and Stream Improvement,
New York, 1988.
Protection
Agency/Paper
Industry
Cooperative
Dioxin
Study: The
104-Mill
Study,
Whittemore,
R. c., NCASI Tech. Bull. No.
590, National Council (of the Paper industry) for Air and Stream Improvement,
New
York, 1990.
29. The CPPA National Dioxin Characterization of Canadian
Bleached
Chemical
Pulping, CPPA Final Report, CPPA Tech.
Sect., Montreal, 1991.
30. Chung,A., Halliburton, D., Van Donkelaar,
A., Chemosphere
20(10-12):1739
(1990).
31. Swanson,
Kringstad,
S.E., Rappe, c., Malmstrom,J.,

K., Chemosphere
17(4):681
(19S8).
32. De Sousa, F., Kolar, M-C., Kringstad, K.P.,
Swanson, S.E., Rappe, c., Glas, B., Tappi
72(4):147
819
(1989).
33. Kringstad, K.P.,Johansson,

L., Kolar, M-C.,
de Sousa, F.,Swanson,S.E., Glas, 8. ,Rappe,
c., TapPiJ 72(6):163 (1989).
34. Sarkanen, K.V and Goyal, G., "Review of
potential chemical processes resulting in
the formation of polycWorinated
dioxins
and dibenzofurans
in the bleaching
of
pulps;
Pulp
35. Whittemore,
R. C. and Dallons, V, "intensive study of the formation
and distribution of 2,3,7,8-TCDD
[tetracWorodibenzodioxin]
and 2,3,7,8-TCDF
[tetracWorodibenzofuran]
during the bleaching
of kraft pulps; NCASI Tech. Bull. no. 591,
National Council (of the Paper Industry)
for Air and Stream Improvement,
New
York,I990.
36. Rappe, c., Swanson, S., Glas, 8., Kringstad,
K.P., De Sousa, F.,Johansson,
L.,Abe, Z.,
Pulp Pap. Can. 90(8):42 (1989).
37. Voss, R. H., Luthe, C. E., Fleming, B. I.,
Berry, R. M.,Allen, L. H., Pulp Pap. Can.
89(12):151
(1988).
38. Berry, R. M., Fleming, B. I., Voss, R. H.,
Luthe, C. E., Wrist, P.E., Pulp Pap. Can.
90(8):48 (1989).
39. Axegaro,
(1989).
P., Pulp
(1991).
42. Allen, L. H., Berry, R. M., Fleming, B. I.,

Luthe, C. E., Voss, R. H., Chemosphere
19(1.Q):741 (1989).
43. Berry, R. M., Luthe, C. E., Voss, R. H.,
Fleming, B. I., "Curtailing
dioxin formation: ramifications
for chemical
pulp
bleaching,"
Ninth International
Symposium on CWorinated Dioxins and Related
Compounds
Proceedings,
Environment
Ontario, Toronto, 1989, PLP 05.
44. Hrutfiord, B. F. and Negri, A. R., Chemosphere 25(1-2):53 (1992).
4'. Ifrutliord,
75(8):129
D. E and Negri, A. R., Tappt

(1992).
-Principles
and Practice
of formation of cWoro-organics in cWorine

bleaching of softwood kraft pulp," International Pulp Bleaching Conference
Proceedings, Stockholm,
1991, Vol. I, p.103.
47. Luthe, C.E.,
Chemosphere
Berry, R.M., Voss,

28(10):1883
(1994).
R.H.,
48. Luthe, C.E., Wrist, P.E., Berry, R.M., Pulp

Pap. Can. 93(9):40 (1992).
49. Luthe, C.E., Berry, R.M., Voss, R.H., Tappi
J 76(3):63 (1993).
50. Luthe, C.E., Voss, R.H., Berry,
Chemosphere
30(4):661 (1995).
R.M.,
51. Someshwar,A.
V, Jain,A. K., Whittemore,
R. c., lafleur, L. E., Gillespie, w,J., Chemosphere 20(10-12):1715
(1990).
52. Luthe, C.E. and Prahacs, S.,Pulp Pap. Can.
94(8):T227 (1993).
53. Rappe, C., Glas, B., Kjeller, L.-o., Kulp,
S.E., deWit, c., Melin, A., Chemosphere
20:1701 (1990).
54. Rappe,C.,Glas,B.,Wiberg,K.,"Solved
and
remaining PCDD and PCDF problems in
the pulp and paper industry," Short Papers
from the Tenth International
Symposium
on CWorinated Dioxins and Related Compounds,
Eco-Informa
Press, Bayreuth,
Germany, 1990, Vol. 3, p. 287.
55. Shariff, A. and Nguyen,
Can. 93(9):29 (1992).
X.T., Pulp
Pap.
56. Nguyen, X.T. and Shariff, A., Jean, M.,j

Pulp Pap. Sci. (1993).
58. Berry, R.M., Luthe, C.E., Voss, R.H., Wrist,

P.E., Axegard, P., Gellerstedt, G., Lindblad,
P.-0., Popke, I., Pulp Pap. Can. 92(6):43
(1991).
L., Chemosphere
41. Hiralall, R., Pap. S.Afr. 11(6):45
Pulp Bleaching
57. Berry, R.M., Luthe, C.E., Voss, R.H.,

Environ. Sci. Technol. 27(6):1164 (1993).
Pap. Can. 90(5):T183
40. Axegard, P., Renberg,

19(1.Q):661 (1989).
820
46. Marwah, N., Rajan, P.S., Joyce, T.W, Chen,

C.-L, Gratzl, J.S., "Chemistry
and kinetics
59. Rempel, W, Pryke, D. c., Ouchi, M. D.,

"Mill trials of substantial
substitution
of
chlorine dioxide for cWorine.(3). medium
consistency;
CPPA Spring Conference
Preprints,
CPPA Tech. Sect., Montreal,
1989, Session 1, Paper no. 4.
60. Grundelius, R., Mitchell, K.A., Rankin,J.
P., Pulp Pap. Can. 92(4):43 (1991).
61. Munro, F. C.,AppitaJ
62. Hise,R.and
(1990).
Hintz,H.L.,
43(6):421
TappiJ
(1990).
73(1):185
63. LaFleur, L. E., Brunck, B., McDonough,

T.)., Ramage, K., Gillespie, W J., Malcolm,
E., Cbemosphere
20(10-12): 1731 (1990).
64. Reid, D. W., Billmark, G. G., Sutton,
TapPiJ 74(7):99 (1991).
C. J.
65. Berry, R.M. and C.E. Luthe,j

Sci. 18(6):JI97 (1992).
Pap.
Pulp
66. Berry, R.M. and C.E. Luthe,

47(4):315 (1994).
67. Hise, R. G.,Streisel,R.
75(2):
Apptta
c., BiIls,A. M., Tappi
57 (1992).
68. Lafleur, L., Brunck, B., McDonough,

Ramage, K., Gillespie, W, Malcolm,
Chemosphere
20(10-12):1731
(1990).
T.,
E..
69. McKee,
P., Burt, A., McCurvin,
D.,
Hollinger, D., Ciement, R., Sutherland, D.,
Neaves, W, Cbemosphere
20(10-12): 1679
(1990).
70. CEPA Pulp and Paper Mill Effluent CWorinated Dioxins and Furans Regulations.
Canada Gazette Part II, Vol. 126, No. 11,
1992, P 1940.
Protection
Agency, 40 CFR Partrs 63 and 430, "Effluent Limits Guidelines, Pretreatment
Standards, and New Source Performance
Standards: Pulp, Paper and Paperboard
Category; National Emission Standards
for
Hazardous Air Pollutants for Soource Category: Pulp and Paper Production;
Proposed Rule," Federal Register, Vol. 58, No.
241, P 66078,1993.
72. "Reference Method for the Determination
of Polychlorinated
Dibenzo-p-dioxins
(PCDDs) and Polychlorinated
Dibenzofurans (PCDFs) in pulp and paper mill effluents," EPS Report 1/RM/19, Environment Canada, Ottawa, Ontario, 1992.
73. Kieatiwong, S., Nguyen, L.V, Hebert, VR.,
Hackett,
M., Miller, G.C., Miille, M.J.,
Mitzel,
R., Environ.
Sci. Technol.
24(10):1575
(1990).
74. Friesen, K.J., Muir, D.C.G.,Webster, G.R.8.,
Environ. Set. Technol. 24(11): 1739 (1990).
75. Fortunati, G.U., in Chlorinated
Dioxins
and Dibenzofurans
in Perspective
(C.
Rappe, G. Choudhary,
L.H. Keith, Eds.)
Lewis Publishers,
Chelsea,
Michigan,
1986, Chap. 37.
76. Miller, H., Marklund, S., Bjerle, I., Rappe,
c., Chemosphere
18(7-8):1485 (1989).
77. Liberti,
A., Brocco,
D., Allegrini,
I.,
Cecinato,
A., Possanzini,
M., Sci. Total
Environ.
10:97 (1978).
SECTIONvm:
Chapter 4:
Bleach Plant Air Emissions
A.K.Jain
National Council for
Air & Stream Improvement,
(NCASI)
Gainesville, FL
Inc.
1. Introduction
823
2. Emission of gaseous bleaching
chemicals
823
2.1 Chlorine and chlorine dioxide eniissions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 823

2.2 Ozone emissions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 824
3. Emissions
of organic compounds
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 824
3.1 Generation and emission ofchlorofonn
824
3.2 Formation and emission of methanol from bleach plants. . . . . . . . . . . . . . . . . 826

3.3 Generation and emission of carbon monoxide.
3.4 Emissions of other volatile organic compounds
. . . . . . . . . . . . . . . . . . . . . . . . 829
. . . . . . . . . . . . . . . . . . . . . . . . 830
4. Control of chlorine and chlorine dioxide

emissions from bleach plants
830
4.1 Scrubbing media used in chlorine and chlorine dioxide scrubbers.

4.2 Scrubber process control parameters and monitoring.
821
. . . . . . . . 830
. . . . . . . . . . . . . . . . . . 833
Chapter
Chapter vm 4:
823
This chapter provides information on

bleach plant emissions and technologies
currently used for controlling the discharge
of chlorine and chlorine dioxide from
bleach plant vent gases.
Bleach Plant
Air Emissions
1. Introduction
CWorine and cWorine dioxide are gases
used in significant quantities in bleach
plants and, as a result, bleach plants contain several vents which have the potential
for releasing gaseous cWorine and cWorine
dioxide. If oxygen or ozone is used in the
bleach plant, it would also be expected to
be present in the vent gases. Of these, only
cWorine, cWorine dioxide, and ozone emissions are of environmental significance. In
addition to the gases employed for pulp
bleaching, a number of volatile organic compounds such as cWoroform, methanol, acetaldehyde, and methyl ethyl ketone are
either produced during pulp bleaching or
are present in the liquid streams which are
introduced into the bleach plant and so are
also likely to be present in bleach plant vent
gases.
2. Emissionof gaseous bleaching chemicals

2.1 Chlorine and chlorine dioxide
emissions
When cWorine and/or cWorine dioxide
are used for pulp bleaching, the vent gases
from the cWorination- and cWorine dioxide-stage towers, washers, and ffitrate tanks
contain these gases. Emissions of cWorine
and cWorine dioxide from bleach plant
vents, as presented in Tables 1 and 2, vary
considerably between and within bleach
plants (1).These data are for emissions prior
to any scrubber or other emission control
device. The extremely high levels of cWorine and cWorine dioxide measured on a
few occasions occurred during process
upsets and do not represent normal operation.
824
Pulp Bleaching
- Principles
and Practice
A number of process variables have been

shown to correlate with cWorine and chlorine dioxide emissions from various bleach
plant sources. CWorine emissions from a
chlorination
tower are expected
to be
strongly dependent upon the residual cWorine content of the pulp suspensions exiting the tower. An indirect measure of the
residual cWorine content of C-stage pulp is
the washer vat residual cWorine or total
oxidant, although these variables are also
affected by the cWorine content of the vat
dilution water. C-tower cWorine emissions
increase with increasing cWorine vat residuals (1). Similarly, cWorine dioxide losses to
the atmosphere from D-tOwer and D-stage
seal tank vents increase with increasing
cWorine dioxide application (1).
2.2 Ozone emissions

At bleach plants where ozone is employed as a bleaching chemical, ozone may
be present in the tower vent gas. However,
vent gases from the ozone stage must pass
through an ozone destructor, and so no significant ozone emissions are expected from
the ozone stage.
3. Emissionsof organic compounds

Table 1. Cblorlae
_1ssIorIs
fram
blelleb Pi"",
fJMts prior
to sawbber.
Chlorine Emissions (kg/air dried

metric ton of pulp)
Bleach Plant
Sequence
Process
Furnish
C(EO)HP
(C+D)(EO)D(EP)D
CEHD
(CD)(EO)HHD
C(EO)H
CEH
CHDED
(C+D)(EO)D
(DC)(EO)DED
(C+D)OD
K-Kraft
S - Sulfite
HW - Hardwood
SW - Softwood
Minimum
Maximum
Average
HW
0.00
0.23
0.07
SW/HW
0.02
0.14
0.08
SW/HW
0.38
5.21
2.56
SW/HW
0.01
1.71
0.41
S
S
K
K
K
K
SW/HW
SW/HW
SW/HW
SW
SW
HW
0.00
0.24
0.13
0.01
0.04
0.17
0.004
1.06
0.72
0.04
0.06
5.13
0.003
0.63
0.33
0.02
0.05
2.00
3.1 Generation and emission of chloroform

The formation of cWoroform when lignin is treated
with alkaline
chlorine
(t.e., hy-
pocWorite) has been known for many years.

Harris et al. (2) reported that this chloroform formation was the result of the classical haloform
reaction.
In this case,
hypochlorite reacts with methyl ketone to
form tricWoroketones
which undergo hydrolysis to form cWoroform.
Hrutfiord and Negri (3) have reviewed
the chemistry of cWoroform formation in
bleach plants. In the chlorination stage, a
number of low- and high-molecular-weight
chlorinated organics are produced; some of
these chlorinated
compounds,
such as
cWoroacetic acids, contain terminal carbons
with three cWorine atoms and can undergo
hydrolysis under acid conditions to produce
chloroform. Because this hydrolysis is slow
at the temperatures
prevailing in bleach
plants, only a small amount of chloroform
is produced in the cWorination stage. However, in the alkaline extraction stage, many
of these cWorinated compounds undergo
rapid hydrolysis to produce chloroform.
Consequently, significantly more chloroform is produced in the extraction stage
following the cWorination stage than in the
chlorination stage itself. Similarly, raising the
pH of cWorination stage filtrate leads to the
formation of chloroform (4).
Chloroform generation from hypochlorite
Studies have shown that chloroform formation in the hypochlorite stage of bleach-
Chlorine Emissions (kgIair dried

metric ton of pulp)
Bleach Plant
Sequence
Furnish
Minimum
Maximum
Average
SW/HW
SW/HW
0.32
0.61
0.50
0.03
0.09
C(EO)HHD
0.05
SW/HW
0.04
0.98
0.32
CHDED
(C+D)(EO)D
SW/HW
0.02
0.09
0.05
SW
0.08
0.29
0.19
(DC)(EO)DED
SW
0.64
1.21
0.86
(DCXm)D
HW
0.61
12.75
2.65
(C+D)(EO)D(EP)D
CEHD
K-Kraft
HW - Hardwood
SW - Softwood
Process
Chapter VIll 4: Bleach Plant Air Emissions
E- 0.4
::>
c..
.;:
Ii
...
t:.
100%
o
0.3
1]
.1
0.1
.. ..
~t
t:.
0.20 Kappa factor

0.25 Kappa fartor
t:.
...
..
0
0
~8
~]
0.15 Kappa factor
...
...
41
......
.2:0
o
o
E~
42-5 0.2
e i8
E
-c
CO;
Cot:
..
o..~
826
Chlorine dioxide substitution

28%
37%
46%
71%
15%
D
825
L>.
g...
.. u
... ..
~.!!
. ... .
...
1~::I
E
0.15 Kappa factor

oxygen.delignified
o
0.20 Kappa facior
oxygen-delignified
o
0.25 Kappa factor
oxygen-delignified
1
...
"
0.2
0.1
Chlorine
CHCI3,
kg/admt
of pulp
K x (-0.023 + 0.0247 H"5 + 0.00832 R) [1]

where K is the kappa number of pulp entering the hypochlorite stage, His hypochIorite charge in kg active chlorine/admt
of
pulp, and R is hypochlorite residual in kg/
admt of pulp.
At some mills, sodium hypochlorite is
made from chlorine produced in the chlorine dioxide generator or when tank cars
containing chlorine are flushed through an
alkaline (i.e., NaOH) scrubber. If this alkali,
which contains hypochlorite, is used in the
extraction stage, additional chloroform is
produced. Tests carried out at one mill
showed that the amount of chloroform produced in the extraction stage because of
hypochlorite addition ranged from 0.05 to
0.4
40
60
80
Chlorine
dioxide
substitution.
100
factor
Fig. 1. Relatlunsltlp belwee1l eblorlrul ftldor tm4 elliorojorrrl fOf'llfllliml (1IdIl_

elliorojorrrl releae tUlJrlSleIl).
10.5 tm4l1llmllne _
ing is a function of the kappa number of

pulp entering
the stage, hypochlorite
charge, and hypochlorite residual (5). Chloroform generation in the range of 0.12 to
1.2 kg/air dried metric ton (admt) of pulp
has been reported for the hypochlorite
stage (5).The following equation has been
reported to best represent the relationship
between chloroform formation and process
variables (5):
0.3
20
SIIffIJIles_/dyzell
", pH
0.4 kg/admt of pulp and increased with the

amount of hypochlorite used (5).
Chloroform generation in hypochlorite-free
bleach plants
Elimination of hypochlorite brings about
a significant decrease in the amount of chloroform generated in the bleach plant. The
amount of chloroform generated in hypochlorite-free
bleach plants has been
found to range from less than 0.02 to 0.29
kg/admt of pulp (6).As discussed earlier,
chlorination of pulp leads to the formation
of chloroform or chloroform precursors
which are carried to the extraction stage.
Chloroform precursors undergo rapid hydrolysis under the alkaline conditions of the
extraction
stage to form chloroform.
Among the factors identified as affecting
bleach plant chloroform formation are chlorine application per unit of lignin content
(e.g., kappa number) of the pulp (i.e., the
chlorine factor), chlorination stage temperature, and order of chlorine and chlorine dioxide application.
Studies (6) have shown that decreasing
the chlorine factor, usually through an increase in the degree of chlorine dioxide
substitution,
leads to a decrease in the
amount of chloroform and chloroform pre-
Fig. 2. Melllmwi
OOfI/ml of ftllrtlles
from
C lI"tI E slllges
cursors produced in the C and E stages of

the bleach plant (Fig. 1). At bleach plants
practicing 100",-6chlorine dioxide substitution, chloroform generation was found to
be less than 0.01 kg/oven dried metric ton
(odmt) of unbleached pulp (7). Laboratory
and field studies have shown that raising
the temperature in the chlorination stage
leads to an increase in chloroform formation in the C and E stages (B). The addition
of chlorine dioxide to the brownstock prior
to chlorine led to higher chloroform generation than when chlorine was added first
or when chlorine and chlorine dioxide were
added simultaneously (6).
Studies
have shown
that oxygen
de lignification does not have a significant
impact on chloroform formation in the chlorination and extraction stages (7,B).This is
consistent with the earlier findings that
chloroform generation is a function of the
chlorine factor and not the amount of chlorine applied. Although oxygen delignification has the potential to decrease the
amount of chl()rine/chlorine
dioxide applied in the first stage, it does not necessarily lead to a lower chlorine factor. However,
to the extent oxygen delignification permits
the chlorine factor to be reduced, it decreases chloroform formation.
I"
IIIe bleaelll"g
of pine
llraft pulp.
Chloroform has a very high vapor pressure. Consequently, a significant fraction of

the chloroform produced in the bleach
plant leaves with bleach plant vent gases.
Studies (9) have shown that the fraction of
chloroform leaving with vent gases averaged 58% of the chloroform produced, and,
on average, only 42% of the chloroform was
found in the sewer. It has been estimated
that almost 90% of the chloroform present
in the liquid effluent volatilizes during biological treatment of the effluent and transfer to the effluent outfall (9).
3.2 Formation and emission of methanol from bleach plants

The reaction of chlorine and chlorine
dioxide with lignin gives rise to the formation of methanol (1O-13).When kraft pulp
from black spruce at a kappa number of
28.7 was bleached at 100% chlorine dioxide substitution, 1.4 kg methanoVodmt of
unbleached pulp was generated (14). It has
been reported that, for both softwoods and
hardwoods, methanol formation decreases
gradually with chlorine dioxide substitution
up to 70% and then deceases sharply when
100% chlorine dioxide substitution is practiced (15). The study also showed that oxy-
Chapter VIII 4: Bleach Plant Air Emissions
827
828
~~Q.
"S
Q.
0
~O'"
or-.
tit .0
o
c:: V)
Q.
0.15 Kappa factor
"5
Q.
oS: 5
t!
.J<I.
U
01!
c:~
~.2~
~"
6-
'"
.
'"
..
g
'"
0.1 5 Kappa facto,

oxygen-delignifoed
.5
1,
.J<I.
"0
0
80
100
Chlorine dioxide substitution, %

Rg. 3. MetlMfIOl COfItefll01jtl"""es from C IIIUII!stages i" tbe blHdmlg
0\ 00 r<;
~~0
N
unbleached
pulp, shower
water
used on washers, and chlorine dioxide
S<>-
lution from chlorine dioxide generators

using methanol as a reducing compound.
~~Up
to 3.8 kg of methanoVodmt
of pulp can
~beintroduced into the bleach plant with

~thepulp, shower water, and chlorine diox-
ide solution (16). In chlorine dioxide gen-
from bleach plants is that the methanol content of the effluents increases with chlorine
dioxide substitution up to 70% and then
decreases slightly for 100% substitution
(Figs. 2 and 3 (15)).
Methanol has a high solubility in water,
and the vapor pressure of methanol in
methanol-water
solutions is low. Conse~~~~quently,
most of the methanol in bleach
plants remains in the effluent. The results
of methanol
tests on various process
streams and vent gases carried out at 13
bleach plants are summarized in Table 3
(16). The data show that methanol emis~sions increased with increasing amounts of
total methanol in the bleach plant and were
higher from bleach plants which utilized
vacuum drum washers and consequently
"'.~E.c
u ""
. ~'"
c:: '" 0
aJ"'.!j
",CQ
.5
\()
chlorine dioxide absorption tower. Methanol concentrations up to 1.1 g/L have been
measured in the chlorine dioxide solutions
Bleach plants generally use white water

containing up to 5 mg/L methano'l or fresh
water containing no methanol on washer
from full scale systems
showers.Table
net effect
on the total methanol content of effluents
3 shows
that, in some bleach
plants, significant amounts of methanol can

be expected to be generated.
\()
-~1t
~CQ
~I'- r<;
N
r<;
r<;
N
r<; r<;
~~N
N .,;
~~~~"".
~N
~or-.
or-.
~~or-.or-. or-.
N N
N 0
0
tJ
.c
'"
~~~I'0
00
00
~~~0
Q.
..
0
~N
~0\
~~N
C
0
~~"O
c
.2
ON$
_.~?f.
U!i;
.c::0
V)
~0
or-.
or-.
0 or-.
~~
or-. r<;
or-.
~or-.
00
Q.
'3 'in "S
-e J '0Q.
<5
0
'O~
g ;
~0
0\
or-. or-.
o 0 0
~r<; r<;
f.~'8
00
~;:::
0 0
~~8 0
0
ji"'8"O
o
~~8
C::"'"O~
~-:;
3~=7~
or-.
'""
'-'
~r<;
N I'0
N
r<;
<5 0 .g
~.sCrl
CQ'" 0
~;;
!1
!s
!s !s
..:,
~'St '"
]u -~ti~E
~'"
~~~~~-g~.~"O
_",B.c
!s !s !s !s X ~!s
B~2S~a
z~~~!:
EEEC::ji
.@sggo
. ...
1
!
'"
t'~
0
..
0
.~Hi
~'s
~-"I
.!
had higher vent gas flow rates compared

to those which employed pressure or diffu-
erators that use methanol as the reducing

agent, methanol may be carried into the
(16).The
0\
'0c
~.c
ti'"
~::!1
011Hlr4lDoo4",.ft pip.
sion washers (16). The major sources of

methanol in the bleach plant are the pulp
stream and chlorine dioxide solution.
of using these chlorine dioxide generators
"O. Q.,
~..c_
~~'5
~;
~plant with
"<1' '::S
...
0
6-
gen-delignified kraft pulps produced less

methanol than kraft pulps not undergoing
oxygen delignification and that decreasing
the kappa factor reduced the amount of
methanol generated very slightly. However,
the benefit of lower methanol formation
from oxygen delignified pulps may be lost
when the amount of methanol generated
in the oxygen delignification
reactor is
taken into consideration.
In addition to being generated in the
~bleach plant, methanol can enter the bleach
~\0
""
'1'
"S
Q.
0.25 Kappa fadO'

oxygen-delignified
60
'b.
40
or-. !::;
0.20 Kappa faclD'
"
E
20
00
N
r-. r<; 'D
""
ti C
7!rJ.!! ":
~=Q., -
~~o><ySen-delignifoed
~~~
':!:
0.25 Kappa factor
6-
""
~&a'8
0.20 Kappa faero,
..
'"
C!~e
0\
~0
:oot'~ '"
.c
.:!3
...
U
U
~'-'
-<
'-' ~~-< ::!1 -.

::!1
'-'
Z'-'
ob
I:i:j
~~~~~~~'
~~~~~~~~~~~~~"'C::C::0:E
~"
8(g!s
Chapter vm 4: Bleach Plant Air Emissions
equation is 0.89. Figure 4 shows that good

agreement exists between measured and
predicted bleach plant methanol emission
rates.
The following equation best represents

the relationship
between uncontrolled
bleach plant methanol emissions and the
process data in Table 3:
Methanol, kg/odmt of pulp =
0.01127M + 0.OOOO34V
- 0.0135
3.3 Generation and emission of carbon

monoxide
Kutney et al. (17) have published laboratory data on carbon monoxide formation
during pulp bleaching. Their results, summarized inTable 4, show significant carbon
monoxide formation occurring in the C and
[2J
where M is the amount of total methanol in

the bleach plant in kg/odmt of pulp and V
is the bleach plant vent gas flow rate in dry
standard cubic meter (DSM)/odmt of pulp.
The coefficient of correlation (r) for this
ClO2
Substitution,
%
C Stage
om
10
829
E Stage
. D Stage
E Stage
D Stage
Total
0.07
0.24
0.0
0.04
0.36
0.02
0.07
0.20
0.0
0.05
0.34
30
0.04
0.09
0.18
0.0
0.03
0.34
50
0.10
0.07
0.19
0.0
0.02
0.38
70
0.18'
0.25
0.09
0.18
0.0
0.04
0.49
0.08'
0.20"
0.0
0.04
0.57
100
'Average of 50 and 100% runs

bAverageall above runs
0.2
.' -
, ",,(SW)
. ',
N(SW)
..l~
:KfHW)
/IiI(I'IW)
",...
Tabu 5. Yolatlu orp8k

bUMb pltltUs.
rom/JOfUUlnttissImufrom
g/odmt of
Unbleached Kraft Pulp
Compound
Softwood
Hardwood
Acetaldehyde
4.2
1.4
Acetone
3.7
1.8
Acrolein'
0.2
0.038
Benzene
0.11
0.05
1.0
<0.85
0.11
0.03
46
65
1,2-Dichloroethane
0.28
<0.19
1,2-Dichloroethylene
0.17
0.11
Dimethyl disulfide
3.8
<1.4
2.4
0.60
Carbon tetrachloride
Chlorobenzene
Chloroform
Dimethyl sulfide'
Formaldehyde
<5.5
0.43
n-Hexane
0.06
0.01
Methanol
130
47
Methyl isobutyl ketone
0.11
0.06
Methyl ethyl ketone
0.46
0.27
Methyl mercaptan'
6.0
0.50
Methylene chloride
0.80
0.21
Styrene
0.14
0.07
Terpenes
12
2.3
0.90
0.13
THC (Method 25A)b
.
j(Sw)
1,2,4-Trichlorobenzene
C(l~W)
0.1
Actual methanol emissions
(kglodmt unbleached kraft pulp)
D stages: 0.35 kg/admt of unbleached pulp

for CEDED and 0.56 for DEDED. Bleach
plant surveys have shown a carbon monoxide emissions range offrom 0.02 to 0.80
kg/admt of unbleached pulp, with an average value of 0.40 (18).
Toluene
C(SW)
0.05
Tetrachloroethylene
A~H,W) E(~W)
.
A(~W)
830
0.15
0.2
75
34
0.11
0.03
2.0
0.65
1,1, I-Trichloroethane
0.22
<0.15
1,1,2-Trichloroethane
0.21
<0.19
Trichloroethylene
0.40
0.18
m,p-Xylene
0.12
0.02
o-Xylrnc
0.10
0.03
'Unexpected
bReference
and unconfirmed
(19)
by GC/MSD.
3.4 Emissions of other volatile organic

compounds
In addition to the compounds discussed
above, bleach plant emissions contain very
small quantities of acetone, acetaldehyde,
formaldehyde, and methyl ethyl ketone. At
a few mills, trace quantities
of methyl
isobutyl ketone, methylene
chloride,
tetrachloroethylene,
and 1,2,4-trichlorobenzene have also been identified in bleach
plant vent gases. The average amounts of
these and other volatile organic compounds
found in bleach plant vent gases after chlorine/chlorine dioxide scrubbers at six softwood and six hardwood bleach plants are
tabulated inTable 5 (16).These data show
that methanol and chloroform constitute
most of the volatile organic emissions from
bleach plants.
4. Control of chlorine and chlorine dioxide emissions from

bleach plants
Most bleach plants are equipped with
scrubbers to control chlorine and chlorine
dioxide emissions from process vents. Although many different types of scrubbers
are available for this purpose, the most
widely used are packed towers. A packed
tower consists of a hollow tower packed to
a certain height with commercially avaiIable
packing elements. The scrubbing solution
is introduced at the top ofthe packing and
trickles down through the packing. The gas
stream to be cleaned flows upward through
the packing, and contaminants are absorbed
in the scrubbing solution. Packed tower
scrubbers can achieve very high removal
efficiencies: commonly 70-90% and often
in excess of 99"10.
4.1 Scrubbing media used in chlorine

and chlorine dioxide scrubbers
Avariety of media are used for scrubbing
chlorine and chlorine dioxide in bleach
plants, including chilled water, sodium hydroxide (NaOH) solution, bleach plant extraction-stage filtrate, gaseous sulfur dioxide
(502) and S02 water, kraft process white liquor which contains sodium hydroxide and
sodium sulfide (Na2S), kraft process weak
wash, which is a weak white liquor solu-
Chapter
Inlet Chlorine Dioxide

Concentration
Chlorine
55-76
28- 52
78-87
30-66
44-72
9-59
20-65
160 - 540
35-87
90-640
78-94
43 - 120
67-95
110 - 220
>99
1- 310
>99
250 440
840 - 1600
290 - 670
4
5
tion, and sodium hydrosulfide

(NaHS),
which is used as the makeup pulping chemical at many kraft mills.
Chilled water
CWorine dioxide is very soluble in chillc;d
water. Consequently, a number of cWorine/
cWorine dioxide scrubbing systems utilize
a cold water scrubbing stage to recover
cWorine dioxide from the vent gases. Although the solubility of cWorine in chilled
water is not as high as that of cWorine dioxide, chilled water scrubbers are also capable of removing some vent gas cWorine.
A packed scrubber facility using chilled
water reportedly (1) removed over 97% of
the bleach plant vent gas cWorine dioxide
which was present in the inlet gas in the
concentration
range of 6,000 to 24,000
parts per million (ppm). The liquid-to-gas
mole ratio in this scrubber was, however,
well over 50. This scrubber also removed
63-93% of the cWorine from the vent gas.
The concentrations
of cWorine in the inlet
gas ranged from 1700 to 6000 ppm. The
spent scrubbing solution was used in the
cWorine dioxide bleaching stage.
Sodium hydroxide solution
Sodium hydroxide reacts rapidly with
chlorine
to form sodium hypochlorite
which is an effective scrubbing agent for
cWorine. CWorine dioxide is hydrolyzed in
alkaline solutions to cWorite (CI02-) and
cWorate (CI03-) according to the following
rtictiuo;
2 CI02 + 2 NaOH -> NaCI02 + NaCIOJ
+ H,o
Inlet Chlorine
Concentration
Chlorine Removal
Efficiency Range, %
Range, ppm
Dioxide Removal
Efficiency Range, %
831
Range, ppm
Mill
[3]
The above reaction is comprised of two

slow reactions followed by disproportionation (20). Consequently, to be effective,
an a1kaIine (NaOH) scrubber for cWorine
dioxide should have a long residence time.
A large excess of alkali in the scrubbing solution also helps.
Tests at two mills to determine the effectiveness of alkali scrubbers in scrubbing
vent gas cWorine and cWorine dioxide have
shown that, in one case, where the inlet
cWorine concentration ranged from 700 to
1600 ppm and no cWorine dioxide was
present, the caustic scrubber was effective
in removing more than 99"A.of the cWorine
in all of the tests (1). In the other instance
where the cWorine dioxide concentration
during the tests ranged from 200 to 700
ppm and the cWorine concentration ranged
from 14 to 50 ppm, the scrubber removed
greater than 99% of the cWorine dioxide and
cWorine (1).
Although these results show that alkali
was very effective in scrubbing cWorine and
cWorine dioxide from bleach plant vent
gases, the high removal efficiencies were
observed under conditions in which the
amount of alkali present in the scrubbing
solution was 30-80 times the required
amount, and the liquid-to-gas ratio was
greater than 55.
Bleach plant extraction stage filtrate
Bleach plant extraction stage filtrates are
attractive for scrubbing cWorine and cWorine dioxide because: 1) they are a1kaIine
and contain organic material that can be
oxidized by cWorine and cWorine dioxide;
2) on reaction with cWorine and cWorine
dioxide their color is reduced, thus reduc-
832
Pulp Bleaching
-Principles
and Practice
ing total bleach plant color load; and 3) they

are available at no cost. However, if chlorine is present in the gases being scrubbed,
chloroform can be formed in the scrubber.
The results of tests with extraction stage
ffitrate as the scrubbing medium at a number of mills are summarized in Table 6 (1).
An examination of the data in Table 6 shows
that except for mill 5, cWorine dioxide and
cWorine scrubbing efficiencies varied significantly both within each scrubber and
between scrubbers. Some of the differences
in scrubber performance were attributable
to equipment design differences. However,
the most significant factor found to affect
the cWorine dioxide scrubbing efficiency
was the total oxidant loading/extraction
ffitrate flow (1). No such correlation was
found for cWorine, suggesting that factors
other than oxidant loading may also playa
significant role in cWorine scrubbing.
Sulfur dioxide
Sulfur dioxide reacts with cWorine dioxide and cWorine to form hydrocWoric and
sulfuric acids. Aqueous sulfur dioxide solutions and gaseous sulfur dioxide in the gas
phase are both used for controlling cWorine dioxide and cWorine emissions from
bleach plants. Tests conducted at one mill
showed that control devices, which included gas phase sulfer dioxide reaction followed by alkali scrubbing, removed 22-60'>10
of the cWorine dioxide and 31-62% of the
cWorine entering the control device (1). In
these tests, cWorine dioxide and cWorine
inlet concentration
ranges were 49-184
ppm and 7-24 ppm, respectively.
TIIbk 7. Re6fIlls of PMfm
tests ...,
"'"""""
Inlet Chlorine
Dioxide
__
White liquor or weak wash

CWorine dioxide reacts rapidly with sulfides (S") and is reduced to chlorite (CI02-)
and cWoride (Cn. In these reactions the
sulfides are oxidized to elemental sulfur,
thiosulfate (SPJ=)' and sulfate (S0:). The
extent and the rate at which the reactions
between chlorine, cWorine dioxide, and
sulfur compounds proceed depend upon
component concentrations,
pH, temperature, and residence time, and are not well
documented. It is worth noting, however,
that during field studies of chlorine and
chlorine dioxide scrubbers which utilize
white liquor, little elemental sulfur has been
observed in scrubber overflow except
when acid conditions prevailed. This suggests that reactions in which elemental sulfur is formed are not favored in alkaline
solutions. Because sulfur formation can result in scrubber plugging, conditions favoring its formation in scrubbers should be
avoided.
The results of scrubber evaluation tests
at six mills using either weak wash or white
liquor are summarized in Table 7 (1). In
these tests, the cWorine concentration
in
the scrubber exit gas was below the detection limit for all the runs. Chlorine dioxide
scrubbing efficiency was not as high at two
of the installations.
Sodium hydrosulfide
Sodium hydrosulfide (NaHS) solutions
react rapidly with chlorine and chlorine
dioxide. Tests at one mill (1) showed that
the sodium hydrosulfide scrubber removed
74 to >99"10of cWorine dioxide and 75-99%
IIJIISbor IIJblte IIqrIor tIS II sendIbI.., sol"l1mI.
Chlorine
Dioxide
Removal
Inlet Chlorine
Concentration
Range, ppm
Efficiency Range, %
Chlorine
Removal
Mill
Scrubbing
Fluid
Range, ppm
Efficiency Range, %
Weak wash
96-150
87-93
2-15
>80->97
Weak wash
25-120
>99
260-810
>99
Weak wash
330-610
>99
28-540
>99
White liquor
130-1400
>99
9-130
>89->99
White liquor
80-480
>99
67-520
>99
White liquor
440-820
62->99
<0.5-24
>96->98
Concentration
Chapter VID 4: Bleach Plant Air Emissions

of cWorine. The inlet cWorine dioxide and
chlorine concentrations
in these tests
ranged from 29 to 130 ppm and from 3 to
47 ppm, respectively.
4.2 Scrubber process control parameters and monitoring

Bleach plant cWorine dioxide and cW~
rine scrubber effluents other than chilled
water are not recycled back to the chemical recovery process. Consequently, mills
which utilize any chemical other than oncethrough alkali, which is used in the extraction stages, or extraction- stage filtrates in
bleach plant scrubbers need to minimize
the chemicals required in the scrubber and
still maintain high chlorine dioxide and
cWorine removal efficiencies. A number of
mills control the rate of chemical addition
to the scrubber by monitoring the pH or
the oxidation reduction potential (ORP) of
the scrubber effluent stream.
Because most of the scrubbing solutions
used for chlorine dioxide and chlorine
scrubbing are alkaline, a. number of mills
monitor and control the scrubber effluent
pH to optimize the scrubbing medium
make-up rate. Alkaline conditions are required to ensure that cWorine absorbed in
the scrubber is retained and not stripped.
Scrubbers using sodium hydrosulfide white
liquor or weak wash can release hydrogen
sulfide if the scrubber pH is allowed to become too low (pH <8.5) or if too much
excess sulfide is present in the scrubbing
solution. Field tests have also shown that
elemental sulfur is present in the effluent
streams of a white liquor scrubber when
the pH of the scrubbing solution is allowed
to drop below 7.
High pH, however, does not ensure that
a scrubber always operates efficiently. In
scrubbing solutions containing compounds
such as sulfides, hydrosulfides, bisulfites,
and organics which react rapidly with cW~
rine and cWorine dioxide, the rates of mass
transfer of cWorine and chlorine dioxide
into the scrubbing solution are enhanced
due to the high reaction rates. In the absence of such chemicals, alkaline solutions
alone are less effective in scrubbing cW~
rine and chlorine dioxide. For any given
833
system, it is desirable to conduct tests at

various scrubber effluent pH values to select the optimum.
Because cWorine dioxide and cWorine
are strong oxidizing agents, most scrubbing
solutions used for cWorine dioxide and cW~
rine removal contain reducing compounds
which can be oxidized by cWorine dioxide
and cWorine. The availability of the reducing compound in the scrubbing solution can
be assessed by monitoring the oxidationreduction potential (ORP) of the scrubber
effluent. In a solution containing an excess
of reducing chemicals, the ORP is negative.
It should be recognized, however, that the
ORP of a solution is also a function of its pH.
1. Jain, A. and K. Dallons, Y.)., "Bleach Plant

Chlorine and Chlorine Dioxide Emissions
and Their Control; National Council of the
Paper Industry for Air and Stream Improvement Technical Bulletin No. 616, National
Stream Improvement
for Air and Stream
Improvement,
Inc. (National Council ofthe
Paper Industry for Air and Stream Improvement), New York, 1991.
3. Hrutfiord, B.E and Negri,A.R.,

(6):219 (1990).
Pulp Bleaching
-Principles
and Practice
7. Crawford, R.]. and Dallons,Y.). ,"CWoroform

Formation
in Bleaching,"
1990 TAPPI
Pulping Conference
Proceedings,
TAPPI
8. Crawford, R,J., Dallons, Y.)., Jain,A.K., Jen,
S.W, "Chloroform
Generation
at Bleach
Plants with High Chlorine Dioxide Substitution and/or Oxygen Delignification,"
Conference
Proceedings, TAPPI PRESS, Atlanta, Book I,
p.305.
9. National Council of the Paper Industry
Chemical Specific Information
for SARA
Section 313 Form R Reporting,
National
Stream Improvement,
Gainesville, FL, 1994.
10. Sarkanen, K.Y. and Strauss, R.W, Tappi 44
(7):459 (1%1).
References
2. Harris, E., Sherrard, E., Mitchell,

Chern. Soc. 56:889 (1934).
834
R.,JArn.
TapptJ
73
4. Crawford, R,J. and Stryker, M.N., "Factors

Affecting Chloroform Generation in Bleaching," 1988 TAPPI Environmental
Conference Proceedings,TAPPI
PRESS, Atlanta, p.
185.
5. Fisher, R.P., Crawford, R.)., Dallons, v.)., "Results of Field Measurements
of Chloroform
Formation and Release from Pulp Bleaching," NCASI Technical
Bulletin No. 558,
Air and Stream Improvement,
New York,
1988.
6. Crawford, R.). and Dallons,V.). ,"Chloroform
Generation
at Bleach Plants with Low Molecular Chlorine Usage or Split Chlorination," NCASI Technical
Bulletin No. 605,
Air and Stream Improvement,
New York,
1991.
11. Van Buren,).B. and Dence, C.W, Tappi 50

(11):553 (1%7).
12. Van Buren,).B. and Dence,
(12):2246 (1970).
C.W, Tappi 53
13. Dence, C.W, Gupta, H.K., Sarkanen,

Tappt 45 (1):29 (1%2).
K.Y.,
14. Ni, Y., Kubes, G.)., Van Heiningen, A.R.P.,

"The Characteristics
of Pulp Demethylation During Chlorine Dioxide Bleaching;
15. Crawford, R.]. and Jain, AX, "Laboratory

Studies of Methanol,Acetone,
and Methyl
Ethyl Ketone Generation
from Kraft Pulp
Bleaching," NCASI Technical Bulletin No.
666, National Council of the Paper Industry for Air and Stream Improvement,
New
York, 1994.
16. Jain, A.K., Crawford,
R.J., Dillard, D.S.,
Rovell-Rixx, D.C., "Volatile Organic Emissions from Pulp Paper Mill Sources, Part V
- Kraft Mill Bleach Plants - V (A) Study Report and V (B) Appendices;
NCASI Technical Bulletin No. 679, National Council
of the Paper Industry for Air and Stream
Improvement,
New York, 1994.
17. Kutney, G.W, Mallais, M., du Manoir,).R.,
Pulp Pap. Can. (Including Journal of Pulp
and Paper Science) 84 (6):TR43 (1983).
18. Results of field tests to be published.
19.40
CFR
Methods,
Part 6O,Appendix
A Reference
Method
25A "Determination
of
Total Gaseous Organic Concentration Using a Flame Ionization Analyzer; Office of

the Federal Register, Nationa1Archives and
Records Administration as a Special Edition of the Federal Register, U. S. Government Printing Office,Washington, DC, p.
942, 1989.
20. Masschelein,W)., Chlorine Dioxide,Ann
Arbor Science Publishers, Ann Arbor,
MI, 1979.
SECI10N vm:
Chapter ;:
Environmental Regulations
Douglas c. Pryke
Erin, Ontario
Reid A. Miner
National Council for Air and Stream Improvement
New York, NY
John Pinkerton
National Council for Air and Stream Improvement
New York, NY
1. Introduction
2. Canadian
reguJations
837
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 837
2.1 Fisheries act
837
2.2 Canadian Environmental ProtectionAct
(CEPA) . . . . . . . . . . .. . . . . . . . . . . . . 838
2.3 Canadian provincial regulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 838

3. United States reguJations
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 839
3.1 Introduction: water regulations.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 839
3.2 Water quality-based permit limits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 839

3.3 Current technology-based limitations guidelines
for wastewaters.
840
3.4 Proposed technology-based permit limitations

guidelines for wastewaters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 841
3.5 Current regulations on emissions to air from
pulp bleaching
842
3.6 Proposed regulations for emissions to air from

pulp bleaching
842
3.7 Annual chemical release reporting requirements.

4. SwedJsh and Finnish reguJations
. . . . . . . . . . . . . . . . . . . . . . 843
844
4.1 Sweden
844
4.2 Finland
845
ChapterVllI
Chapter vm 5:
Environmental
Regulations
1. Introduction
Since 1985, new environmental regulations for bleached chemical pulp, paper, and
paperboard mills, particularly those employing the kraft pulping process, have been developed and implemented in most of the
major pulp and paper producing regions of
the world. Historically, environmental regulations limited the discharge of the group
parameters, biochemical oxygen demand
(BOD) and total suspended solids (TSS), and
required fmal effluent to pass acute and
chronic toxicity tests. The newer reguI:itions, while providing more stringent limitations on these traditional parameters, also
limit the discharge of a new set of parameters such as 2,3,7,8-tetrachlorodibenzo-pdioxin (2,3,7,8- TCDD), 2,3, 7,8-tetrachlorodibenzofuran (2,3,7,8- TCDF), chlorinated
organic compounds
as measured by the
group parameter adsorbable organic halogen (AOX), polychlorinated
phenols, chloroform, chemical oxygen demand (COD),
and effluent color.
The incentive for the development
of
these regulations can be traced to two important events. The first was the discovery,
in 1985, that dioxin (2,3,7,8-TCDD
and
2,3,7,8- TCDF)was an inadvertent by-product of the bleaching processes used at the
time (1,2). The second was the release of
studies, known as the Environment/Cellulose I Project (3,4). and SSVL 85 (6), of the
ecological consequences
of the discharge
of waste water from kraft pulp mills to the
Baltic Sea. These studies were interpreted
as suggesting a link between chlorinated
organic matter and environmental effects.
As the results of these studies became
widely known, two parallel initiatives arose.
One was the response of the international
pulp and paper industry which began an
unprecedented
research and development
effort to create processes to eliminate the
formation and discharge of dioxin. The
other was the dramatic increase in pressure
5: Environmental Regulations
837
from non-governmental
environmental organizations and an increasingly concerned
public on government to enact regulations
and on industry to change their bleaching
technology. In response to such pressure,
governments in most of the major pulp producing regions of the world began to develop regulatory
policies to limit the
discharge of chlorinated
organic compounds from bleached chemical pulp, paper, and paperboard mills.
In some jurisdictions, reports assessing
the magnitude and impact of discharges of
chlorinated organic compounds were prepared and effluent limitations were developed. Because most regulatory policies and
effluent limitations are based on the concepts of "Best Available Technology (BAT)"
and "Economic Achievability," additional
studies were undertaken to assess technology options and the economic consequences
of national or regional implementation
of
effluent limitations. From 1987 through
1993 a large number of environmental, tech-
nology, and economic studies were undertaken. Regulatory policies for today and the
near future are based on such studies
(5-28).
2. Canadian regulations
Regulations affecting the pulp and paper
industry in Canada are promulgated under
two acts of the national parliament: 1) The
Fisheries Act, and 2)The Canadian Environmental Protection Act (CEPA).
2.1 Fisheries act
Revisions to the Pulp and Paper Effluent
Regulations under the Fisheries Act were
issued in May 1992 and require compliance
by December 31, 1995 (29).These regulations authorize the discharge of limited
quantities of deleterious substances: acutely
lethal effluent, BOD, and TSS.
The limitations for BOD and TSS are daily
maxima and monthly averages per unit of
pulp and or paper production using a 90th
percentile
reference
discharge rate as
shown in Table 1. The limitations for acutely
lethal effluent require the final mill effluent at 100% concentration to pass a 96-hour
LC 50 static bioassay using rainbow trout
838
as the test species. In addition, for monitoring purposes only, a similar bioassay is
required for Daphnia magna. These tests
must be run monthly.
Table 1. CtnuulUm pulp arut paper elfllletll
films for trellled flrud elfl_t.
Parameter
BOD', kg/air-dried
TSS', kg/air-dried
Acute
tonne
tonne
regula-
Monthly
limit
Daily
Maximum
7.5
12.5
11.25
18.75
lethality
Rainbow
trout
Daphnia
magna
lation defines "measurable concentration of

2,3,7,8-TCDD"
as "a concentration
of
2,3,7,8- TCDD that is greater than the level
of quantification as defmed in the Reference
Method" which is currently 15 parts per
quadrillion (29,31). Although the level of
quantification for 2,3,7,8- TCDF is 15 parts
per quadrillion, the measurable concentration has been set at 50 parts per quadrillion (Table 2) (29,31).
Table 2. ClnuuUalt pulp tIrul paper elfl_t
limits
lor cblorlltated dloxiltS arut I"NItS I" a
treatedfl,ud elfl_t.
LC 50 ~100%
Monitor
monthly
'Biochemical oxygen demand

Total suspended solids
In addition, each discharger must perform an Environmental Effects Monitoring

Study (EEM) every three years (30). The
principal components of the EEM study are
effluent characterization, receiving environment characterization,
fish surveys, and
benthic surveys.
2.2 Canadian Environmental
Protection
Act (CEPA)
Based on a study of dioxins in 1992,regulations under CEPA were promulgated to
control the formation and discharge of
2,3,7,8- TCDD and 2,3,7,8- TCDF from Canadian pulp and paper mills that operate
chlorine-consuming bleach plants (15,29).
The regulations define "chlorine bleaching
plant" as a plant in a mill where pulp is
bleached by chlorine or chlorine dioxide.
Each qualifying mill must comply with the
CEPA regulations. The CEPA Pulp and Paper Mill Defoamer and Wood Chip Regulations limit the use of defoamers to those
containing 40 ppb or less by weight of
dibenzofuran, 10 ppb or less by weight of
dibenzo-p-dioxin,
and prohibits the mill
use of wood chips that have been made
from wood treated with pentachlorophenol. The CEPA Pulp and Paper Mill Effluent
Chlorinated Dioxins and Purans Regulations
prohibit the release of final effluent that
contains any measurable concentration of
2,3,7,8-TCDD or 2,3,7,8-TCDE The regu-
Compound
limit
2,3,7,8-TCDD
< 15 parts/quadrillion
2,3,7,8-TCDF
< 50 parts/quadrillion
Canada, in contrast to other nations and

in contrast to many of its provinces, does
not have a regulation limiting the discharge
of chlorinated organic compounds as measured by the group parameter, AOX. This
decision was based in part on the findings
of the CEPA assessment of "Effluents from
Pulp Mills Using Bleaching" which concluded thatAOX did not provide an estimate
of environmental toxicity, persistence, or
bioaccumulation (18, 32).
2.3 Canadian provincial regulations

Canada produces bleached chemical
pulp in 7 of its 10 provinces, and in most of
these provinces mills are subject to provincial as well as federal regulations. The provincial regulations have limitations on the
conventional
parameters, BOD, TSS, and
acute toxicity which, in some cases, are
more stringent than the federal requirements. More importantly from a bleaching
perspective and in contrast to the federal
regulations, most provinces have limitations
on the discharge of chlorinated
organic
compounds as measured by the group parameter, AOX.
The province of Quebec has AOX limits
for both softwood and hardwood which
become progressively more stringent over
time (Table 3) (33) .The province of Ontario
has similar AOX limits and also has limitations on chloroform emissions (Table 4)
Chapter VIII 5: Environmental Regulations
839
Ttlbk 3. QrIUecpilip a4 /MJH!rmill limits for AOX

trMINl e.8lfIMI.
"' fl"'"
AOX', kg/air-&ied tonne
Hardwood
Softwood
Daily
30-day
Daily
30-day
Existing
January
October
January
mills
1.5
1.5
1.0
1.5
1.0
0.8
1, 1994
I, 1995
1,2001
2.5
2.0
0.8
New millb
0.30
0.25
0.25
'Adsorbable organic halogen
"New mill is one whose construction was completed on or after October 22,1992.
(34). In addition, the government of Ontario
has a goal of "zero AOX" by 2002 and requires each mill to periodically submit "AOX
Elitnination Reports"(34).The
province of
Alberta has site-specific regulations for each
mill that are embodied in a five-year operating license.AOX limitations are included'
and range from 0.5 to 1.5 kg/air-dried ton
of pulp.
1'tIbk 4. OJrliIrlopIllp"rut /MJH!rmlllllmltsfor AOX
e.8l_t.
"IUt chloroform /" fl""'lrMtM
Parameter
limit (Average)
Monthly
Daily
Chloroform, kg/air-dried tonne

AOX, kg/air-&ied
January 1,1996
January 1,2000
0.002
0.004
1.5
0.8
2.0
1.0
tonne
The province of British Columbia regulations are as follows:

"... every pertnittee that operates a pulp
mill or pulp and paper mill which uses chlorine or chlorine compounds to bleach pulp
shall:
a) meet a discharge limit of a monthly average of 1.5 kg of AOXI ADt on or before December 31, 1995, and
b) eliminate AOX produced in the bleaching
process on or before December 31,2002"
(35).
2.5
2.5
1.0
0.30
Pollutant Discharge Elimination System

(NPDES). NPDES permits are usually issued
for a five-year period. The United States Environmental Protection Agency (EPA) can
issue NPDES pertnits directly or it can delegate pertnitting authority to states. In states
with NPDES pertnitting authority, pertnitting and enforcement programs must be at
least as restrictive as the EPA's.
Most, but not all, states with pulp and
paper production now have NPDES pertnitting authority. In those states without such
authority, dischargers may be issued pertnits
from both the state and national governments. Even in states with NPDES pertnitting authority, it is common for the EPA to
review the provisions of proposed stateissued pertnits for pulp and paper tnills (and
other "major" facilities) to ensure consistency with national laws and regulations.
The limitations in mill discharge pertnits
can be water quality-based or technologybased.Water quality-based limits reflect an
agency's analysis of what is required to protect water quality; technology-based
limits
represent
the EPA's assessment
of the
capabilities of production and treatment
technologies to tninimize discharges irrespective of environmental quality considerations. The more restrictive of the two
types of limits is used in the discharge
pertnit.
3. United States regulations
3.2 Water quality-based

permit limits
When warranted by available toxicity
3.1 Introduction: water regulations

In the United States, wastewater discharge limitations are contained in discharge pertnits written under the National
data, the I:PA i~~ue~water quality criteria

for specific chemicals, classes of chemicals,
or water quality parameters. These criteria
represent the EPA's estimate of "safe" con-
840
centrations in the recehing water. A variety of criteria are derived to protect aquatic
organisms, consumers of aquatic organisms,
and drinkers of surface water from both
acute and chronic health effects. States may
adopt the EPA's criteria or develop criteria
that are tailored to the conditions in the
state. State-developed criteria may be more
or less restrictive than the EPA's, provided
the latter accepts the rationale behind their
development.
The EPA has developed criteria or water
quality guidance for approximately
190
chetnicals or classes of chetnicals (36).The
criteria that have had the greatest impact
on U.S. pulp and paper mills are those for
dissolved oxygen. Water quality-based permit litnits on nutrients are also relatively
common. There are also, however, national
criteria for a number of chlorinated chetnicals of special interest at facilities where
pulp is bleached with chlorine-based
bleaching agents. Table 5 contains some of
the national water quality criteria (or updated guidelines) for those chlorinated
chetnica1s named in bleached chetnical pulp
mill discharge pertnits reviewed by the National Council for Air and Stream Improvement (NCASl).
The EPA also works with state agencies
to add water quality-based bioassay provisions to discharge permits. It is common
for permits to require periodic (often quarterly) bioassays,particularly

the EPA's 7 -day
fathead minnow survival and growth test
and its seven-day Cerlodaphnta
survival
and reproduction test (37) (see Chap. VIII
2 on biological testing). Marine and estuarine dischargers are increasingly being required to perform bioassays employing
marine organisms (38). In almost all cases,
to be judged in compliance with pertnit
conditions, bioassay results must pass a predetermined threshold based upon the available dilution in the receiving water.
NPDES permit limitations are derived
from water quality criteria using models that
account for the dispersion and environmental fate of substances in the receiving water. The EPAprovides guidance on methods
for deriving water quality based-permit
limitations in "Technical Support Document
for Water Quality-Based Permit Utnits for
Toxics" (39).
3.3 Current technology-based

limitations guidelines for wastewaters
National law establishes a performance
level that must be met by all pulp, paper,
and paperboard mills.The EPAdetermines
this performance level based upon an evaluation of the capabilities of available production and waste treatment technologies.
Current technology-based BOD and TSS
rtlbk 5. SelectM tHter qrutllty crlterlIIfor chlorl""ted cbemkals specified I" U. S. blucbed pilip mill dIscNrge permits.
Fresh Water
Chronic
Toxicity
Criteria
Q1g/L)
Chemical
1.240'
Chloroform
2-Chlorophenol
Human Health
Criteria
- Based
Upon
Consumption of
Fish and Water
Q1g/L)
0.19/5.7b
180"
2,4-Dichlorophenol
365'
3090 / 93"
<0.00001'
0.000000013
Hexachlorobenzene
3.68'
0.00072
2,4,6- Trichlorophenol
970'
1.2
2,3,7,8-TCDD
Jinsufficient data to develop criteria; value

shown is lowest observed effect level.
"Recalculated values using IRIS as of 9/90
,
Proposed
Chaptervm
guidelines for existing sources represent the
outcome of the EPA's mid- to Iate-1970s
assessment of the capabilities of the Best
Practicable
Technology
(BPT). In most
cases, these limits were derived from the
performance of mills utilizing efficient biological wastewater treatment.
The law allows the EPAto establish guidelines for BOD and TSS that are more restrictive than BPT guidelines if the Agency can
demonstrate that the cost of the changes is
reasonab1e.These more restrictive BOD and
TSS guidelines are termed Best Conventional Technology (BCT) guidelines. The
pulp and paper industry's BCT guidelines
are currently identical to BPT guidelines.
The BPT/BCT guidelines
for bleached
chemical pulp mills are listed in Table 6.The
limits are given in kg per kkg (metric ton)'
of product (usually air-dried). The national
guidelines for new sources (New Source
Performance Standards or NSPS) are lower.
T4ble6. CfIfTMIpltlelilrn for IIOIJIIIUlTSS Msebargedfrum ~
bietreW Inwft}nIlp
",Ills.
Mnimnm
Category
Market
kraft
8.05
Kraft
paperboard
7.1
Kraft fine
paper
5.5
.
b
Modest
Averal!e k~
BOD"
Monthly Dally
additional
15.45
13.65
10.6
allowance
utilizing wet debarking,

fumes
See footnote to Table I
TSSb
Monthly Dally
16.4
12.9
11.9
available
30.4
24.0
22.15
for mi1Is
chip washing, or log
A list of chemicals identified in the law

as "toxic pollutants" and a variety of other
chemicals and parameters termed "nonconventional
pollutants" (e.g., chemical
oxygen demand and color) can be regulated
by the EPA to levels representing
the
Agency's assessment of the capabilities of
the Be5thvailabl(;Ttdmolo~
fconomically
Achievable (i.e., BAT guidelines). The only
chemicals currently covered by BAT guidelines for bleached chemical pulp mills are
5: Environmental Regulations
841
2,4,5-trichlorophenol
and pentachlorophenol. Companies can comply with the guidelines by monitoring effluent quality or by
certifying that these chemicals are not
present in the biocides used in the mill.Virtually all companies have complied by certification.
3.4 Proposed technology-based

permit limitations guidelines for
wastewaters
On December 17, 1993, the EPA proposed revised effluent limitations and pretreatment guidelines for all pulp, paper, and
paperboard mills and maximum achievable
control technology (MACT) air pollution
regulations for process sources at chemical
pulp mills (40). For purposes of its new effluent guidelines, the EPA consolidated the
industry into just 12 subcategories
compared to over 30 in the current guidelines.
The EPAbased the proposed BPT guidelines
for BOD and TSS on the average of the performance of the best 50",4,of mills in each
subcategory. The proposed limits are, therefore, far lower than those in Table 6.
The EPA proposed New Source Performance Standards (NSPS) that were, for the
most part, based upon the performance of
the best existing mill in each subcategory.
Specific chemicals may be regulated by
the EPA under BAT guidelines. For bleached
papergrade kraft mills, the EPA proposed
limits at the bleach plant for 2,3,7,8- TCDD,
2,3,7,8-TCDF,
twelve chlorophenolics
(tri-, tetra-, and penta- substituted), chloroform, and several other volatile chemicals.
The proposed guidelines would require
that most of these chemicals (chloroform
being one notable exception) be "non-detect" at the analytical minimum levels established by the EPA for the corresponding
analytical method.
The EPA also proposed a number of
guidelines for "non-conventional"
pollutants. Specifically,adsorhable organic halide
(AOX) limits were proposed for final efflu-
ents from bleached kraft and bleached

sulfite pulp mills. Guidelines for chemical
oxygen demand (COD) were proposed for
all kraft, sulfite, and semichemical
pulp
842
mills except dissolving sulfite pulp mills. In

addition, guidelines for fmal effluent color
(in platinum color units) were proposed for
bleached paper-grade kraft mills.All of the
non-conventional
pollutants, including
AOX, would be monitored daily.
The specific limits proposed by the EPA
for bleached paper-grade kraft mills were
based on the Agency's assessment of the
capabilities of its chosen BAT technologies
which were oxygen or extended delignification, complete substitution of chlorine
with chlorine dioxide and biological treatment. The EPA, however, is considering
changing the technology basis for its BAT
regulations
from oxygen or extended
delignification
to conventional
delignification. This change would lead to AOX
limits considerably higher than those in the
original proposal.
In most cases, proposed NSPSs for toxics
and nonconventionals were the same as the
corresponding
BAT guidelines. A notable
exception was the bleached paper-grade
kraft subcategory where NSPSs were based
on extended delignification
and oxygen
delignification followed by complete substitution with chlorine dioxide. EPA is expected to promulgate final regulations in
1996.
3.5 Current regulations on emissions

to air from pulp bleaching
The United States has an elaborate national air pollution control regulatory program. In many respects, its structure is
similar to that for water pollution. The
United States EPA has established healthbased and welfare-based ambient air quality criteria for six compounds:
ozone,
carbon monoxide, sulfur dioxide, nitrogen
dioxide, particulate matter, and lead. In
many instances, source-specific limits contained in air pollution permits have been
developed to ensure that these ambient criteria are met. National technology-based
standards also exist for a number of sources
of emissions common in pulp and paper
mills, large boilers and recovery furnaces
for instance. There are, however, no promulgated national standards specific to
bleach plant-related emissions.
In many cases, the states have developed

regulatory programs addressing some of the
chemicals emitted from pulp bleaching
operations. Chlorine,chlorine
dioxide,and
chloroform, for instance, are addressed in
a number of state and local regulatory programs. Most state programs are based on
the concept of an acceptable ambient concentration of a given compound at the fence
line of an industrial facility. Acceptable
ambient concentrations
are usually determined from established workplace limits
with adjustments for continuous exposure
and safety factors. Dispersion models are
employed to relate ambient concentrations
to emissions.
While most of the various state and local
agency programs are somewhat similar in
basic approach, there are marked differences in program details. The differences
arise in (a) lists of chemicals included in the
programs, (b) acceptable ambient levels of
identical compounds, (c) dispersion modeling techniques,
(d) methodology
for
determining acceptable ambient concentrations of known or suspected carcinogens,
(e) level of control of emissions required,
and (f) consideration of "background" ambient concentrations.
3.6
Proposed
regulations
for emissions
to air from bleached pulp mills

On December 17,1993, in combination
with the proposed wastewater regulations
discussed earlier, the EPA proposed maximum achievable
control
technology
(MACT) regulations for pulping, bleaching,
and wastewater handling, collection, and
treatment
system emission sources at
chemical wood pulp mills (40). Chemical
pulp mills addressed by the proposal include kraft, sulfite, soda, and semichemical
processes.
The proposed standards (referred to as MACT,or maximum achievable
control technology, emission standards)
would apply to all of these mill types. Although the EPA has the option to set differ-
ent standards for the various types of

pulping operations, it chose not to do so in
the proposal. However, the EPA requested
additional information which would justify

different emission standards for different
types of pulping operations.
MACf emission standards apply to both
existing and new sources. A new source is
one on which construction
begins after
December 17, 1993. All other sources are
existing sources. Standards for new sources
are to be based on "the emission control
that is achieved in practice by the best controlled similar source, as determined by the
Administrator."
Standards for existing
sources are to be based on the EPA's assessment of "the average emission limitation
achieved by the best performing 12% of the
existing sources (for which the Administrator has emissions information)." Emission
standards for the existing sources may be
less stringent than those for new sources.
The United States Congress specifically
listed 189 compounds
as "hazardous air
pollutants." Of that list, the EPA has identified chlorine, chloroform, methanol, methyl
ethyl ketone (MEK), hydrochloric acid, acrolein, acetaldehyde, and formaldehyde as
being the compounds of most significance
for chemical pulp mills. The EPA is considering MACT limitations on bleach plant
emissions of chlorine,chlorine
dioxide,and
chloroform. Scrubbing has been identified
as an appropriate control technology for
chlorine and chlorine dioxide. Chloroform
would be controlled through elimination of
hypochlorite bleaching and substitution of
chlorine dioxide for chlorine where these
process changes were found by the EPA to
be consistent with product quality requirements.
3.7 Annual chemical release reporting

requirements
Section 313 of Title III in the Superfund
Amendments
and Reauthorization Act of
1986 (SARA) requires many industrial manufacturing facilities to annually report estimated releases to the environment
and
off-site transfers for treatment, storage, or
disposal of over 300 individual chemicals.
The reports, submitted on the EPA's"Form
R," were first required for the 1987 calendar year. In the EPA's view, this annual reporting has become a powerful tool for
843
obtaining voluntary reductions in chemical

releases from industrial facilities.
All Form R submissions are available to
the public. The EPA has encouraged state
and local regulatory agencies, as well as
community groups, to access the reported
information.
Computer-based
access is
readily available because all Form R reports
are entered into a computer database. The
EPA publishes annual reports which summarize the Form R submissions.
The estimated releases and transfers reported on Form R have many limitations,
the most significant being that the majority
of the estimates are not based on measurement data. Although more measurements
of releases of Section 313 compounds are
being made, the available information is still
limited. For pulp and paper mills, atmospheric emissions and discharges to receiving waters from wastewater
treatment
systems are often based on the use of estimating information compiled by NCASI.
Atmospheric releases of chlorine, chlorine dioxide, and chloroform reported on
Form R by pulp and paper companies are
largely associated with pulp bleaching operations. NCASI has published summaries
of Form R submissions from the latest forest products industry for the years 1987
through 1993. The reported releases to air
of chlorine, chlorine dioxide, and chloroform from bleached chemical pulp mills are
shown in Table 7. Reported atmospheric
releases are approximately ten times those
reported in wastewater.
The figures in Table 7 suggest emissions
of chlorine, chlorine dioxide, and chloroform from pulp bleaching operations are
declining. Possible reasons for these declines are (a) installation or upgrading of
chlorine/chlorine
dioxide scrubbing systems, (b) reduced or more effective chlorine use in the chlorination
stage, (c)
reduced hypochlorite use, (d) use of measurement data in lieu of engineering judgment for emissions estimates, and (e) use
of updated chlorine and chlorine dioxide
emission factors for uncontrolled emissions
by mills lacking measurement
data (the
chlorine and chlorine dioxide uncontrollable emission factors were revised in 1989).
844
Pulp Bleaching
-Principles
of chlorlrN, chlorine dioxide, 11IM cbloroform
TtIbk 7. ReportN"'" t'f!'cbemlaJl
and Practice
from
U"tled
Slales
bleaebetl
}nIlp mills.
Chemical
and Year
kgx
1<J6
Average
Emission Rate
Median
Emission Rate
(kg! ADTBP')
(kg! ADTBP' )
Number
of Mills
Reporting
0.335
0.175
104
Chlorine
1987
9.4
1988
8.9
0.32
0.15
103
1989
4.9
0.175
0.075
105
1990
3.0
0.105
0.05
106
1991
2.0
0.07
0.03
108
1992
1.5
0.05
0.02
107
1993
0.6
0.02
0.004
107
Chlorine dioxide
1987
5.9
0.23
0.15
82
1988
6.0
0.235
0.15
84
85
1989
3.3
0.135
0.075
1990
2.5
0.09
0.05
88
1991
1.8
0.065
0.04
92
1992
1.4
0.05
0.G3
92
1993
0.7
0.025
0.015
88
1987
9.5
0.4
0.35
83
1988
9.1
0.35
0.3
92
1989
9.5
0.35
0.3
101
1990
8.8
0.3
0.25
103
1991
7.4
0.25
0.225
102
1992
6.9
0.25
0.175
98
1993
5.4
0.22
0.135
90
Chloroform
.Air-dried ton bleached
pulp
Regardless of these complicating factors,

it is dear that significant reductions have
been made over the 1987 to 1993 period.
Considering only the 1989 to 1993 figures
for chlorine and chlorine dioxide, the reported numbers suggest that these reductions exceeded 80%. For chloroform, the
1991 figures show about a 20% decrease in
emissions from 1990; reductions since 1987
exceed 40%.
4. Swedish and Finnish regulations

4.1 Sweden
In 1987, the Swedish Environmental Protection Agency develQped iI1l "Action Plan
for Marine Pollution" (41). The plan asserted that the discharge of stable organic
substances was a threat to the environment.
Remedial strategies were developed with
Chapter vm 5: Environmental Regulations

the goal of eliminating such discharges.The
pulp and paper industry was recognized as
the largest source of chlorinated organic
compounds and the first substances targeted for immediate attention were those
substances which produce serious toxic
effects and can accumulate
in the food
chain. The action plan proposed that within
15 years "closed system" bleaching techniques would be used. In the interim, a timetable of ever more stringent discharge limits
was proposed as shown in Table 8 (42).
ment set a target for decreasing the specific

loading of chlorinated organic compounds
so that the annual national mean should not
exceed 1.4 kg/ADt of bleached pulp. In
addition, the methods to reduce the discharges were to be such that the "toxic dioxin loading due to pulp bleaching
is
practically eIiminated" (45).The policy also
set targets for biochemical oxygen demand,
chemical oxygen demand, and phosphorous loadings as shown inTable 10 (46).
TtIbIe 10.
Tule 8. ..tor limits~
by'. StHMsbErm-
rtJIf1IIeIII4lProIllo8~,
Year
'--
1Ig/1IIr-tlrletl
o/j1IIlp,--.l
tlvertIp.
Softwood
Hardwood
1992
2.0
1.0
1995
0.5
2000
0.5
0.3
2010
0.1
0.1
'See
footnote
to Table 3.
As each pulp mill permit is renewed, the

Swedish Environmental Protection Board
presents its proposed limits to the Franchise
Board for approval. The individual mill also
presents its proposed limits. Ultimately, the
Franchise Board issues a license to the mill
in question.
Bleaching technology
has developed
more rapidly than the initial timetable contemplated by the Swedish EPA.As shown
in Table 9, limits being proposed in 1995
were originally contemplated for the year
2010 (43,44).
Tule f). Dlseb4rge limilsfor..tox IIIfilroo I'roJIosM
by the StHMsb Erml'Oll1lleflltll Prot:1itm
~,lIg/tlir-tlrlM '-- o/pIIlp,_'

IlVeNge.
1995
AOX'
COD"
0.1-0.2
10-15
'See footnote to Table 3.

Chemical oxygen demand
4.2 Finland
In 1989 the Finnish government developed objectives for water protection to be
achieved by 1995. Specifically, the govern-
845
1995
'See
I!JJl-t~oItjeeHws~
by
the FI-ub Mirfistry 0/ the Erml'fMmerll,
IIg/tlir-tlrlft imine 0/ pilip.
AOX'
BOD7b
1.4
2-4
footnote
CODe Phosphorous
65
0.06
to Table 3.
See footnote to Table 1.

e
See footnote to Table 9.
The specific methods to be used and the

actual licensed loading at each site are determined through the decisions of the Water Court.
References
1. The National Dioxin Study, Tiers 3, 5, 6,
and 7, U.S. Environmental
Protection
Agency, Office of Water Regulations and
Standards, U.S. Government Printing Office,Washington, D.C., USA,1987, EPA440/
4-87-003.
2. Amendola, G.A., Barna, D., Blosser, R.,
lafleur, L., McBride,A., Thomas, E,TIernan,
T.,Whitemore, R.,"The occurrence and fate
ofPCDDs and PCDFs in five bleached kraft
pulp and paper mills; Seventh International Symposium on Chlorinated Dioxins
and Related Compounds Proceedings,
1987.
3. Sodergren, A., Ed., Biological Effects of
Bleached Pulp Mill Effluents, National
Swedish Environmental Protection Board,
Report 3558, Solna, Sweden, 1989.
4. SOdergren, A., Ed., Bleached Pulp Mill Ef
fluents: CompostUon, Fate and Effects in
the BalUc Sea, National Swedish Environmental Protection Board Report 4047,
Solna, Sweden, 1992.
846
5. "Environmentally
Harmonized
Production
of Bleached Pulp; SSVL Project Final Report, Stockholm, Sweden, 1982.
6. "Production
of Bleached
Pulp," SSVL-85
Project Final Report, Stockholm, Sweden,
1986.
7. Janssson,
B., Alsberg, T., Bergman,
A.,
Renberg,
L., Reuterg:irdh,
L., "Persistent
organic compounds
in the marine environment: background document for the action
plan for marine pollution;
National Swedish Environmental
Protection Board Report
3395, Solna, Sweden, 1987.
8. "Environmental
Priorities for the Finnish
and Swedish Pulp and Paper Industri. ,"National Swedish Environmental
Protection
Board Report 3443, Solna, Sweden, 1988.
9. Sinclair, WF., Controlling
PolluUon from
Canadian Pulp and Paper Manufacturers:
A Federal
Perspective,
Environment
Canada, Conservation
and Protection,
Environmental
Protection,
Ottawa, Ontario,
Canada,1988.
10. Bonsor, N., McCubbin, N., Sprauge, J.B.,
Kraft Mill Effluents in Ontario, Environment Ontario, Toronto, Ontario, Canada,
1988.
11. Reduction
of Chlo7'O-Qrganic Discharge
in the Nordic Pulp Industry, Nordic Council of Ministers
Environment
Report
1989:6E, Copenhagen,
Denmark, 1989.
12. Fandry, C.B., Johannes, R.E., Nelson, P.J.,
"Pulp Mills: Modern Technology
and Environmental
Protection;
Report to Senator the Hon. John Button, Minister for
Industry, Technology
and Commerce,
Commonwealth
of Australia, 1989.
13. Controlling the Discharge of Chlorinated
Organic Substances from the Canadian
Pulp and Paper Industry,
Environment
Canada, Ottawa, Ontario, Canada, 1990.
14. "Summary ofTechnologies
for the Control
and Reduction
of Chlorinated
Organics
from the Bleached Chemical Pulping Subcategories
of the Pulp and Paper industry," U.S. Environmental
Protection
Agency, Office of Water Regulations
and
Starndards, Office of Water Enforcement
:md Permits,U
.S.
fice, Washington,
Government
D.C., 1990.
Printing Of-
15. Priorlty Substances

List Assessment
Report No.1: Polychlorinated
Dibenzodioxins
and Polychlorinated
Dibenzofurans,Canadian
Environmental
Protection Act Environment
Canada and Health
and Welfare Canada, Ottawa, Ontario,
1990.
16. Stromberg,
L.M., Lehtinen,
K-J. P.,
Annergren, G.E. ,"Bleached chemical pulp
production
- ranking of process alternatives according to the environmental
impact of discharged
effluents,"
1990
EUCEPA
Conference
Proceedings,
Stockholm, Sweden.
17. "Sixth Biennial Report on Great Lakes
Water Quality; International
Joint Commission, Washington,
D.C., 1991.
18. "Priority Substances
List Assessment
Report No.2: Effluents from Pulp Mills Using Bleaching," Canadian Environmental
Protection Act, Environment
19. Canada
1991.
20.
Gazette,
Part l, December
14,
Best Available Technology for the Ontario

"
Pulp and Paper Industry," Water Resources
Branch, Ontario Ministry of the Environment, Toronto, Ontario, Canada, 1992.
21. "MISA Economic Assessment:

Potential
Water Pollution Abatement
Programs for
Ontario Pulp and Paper Mills; Ontario
Ministry of the Environment,
Toronto,
Ontario, Canada, 1992.
22. "The Development
Document
for the Effluent Limits Regulation for the MISA Pulp
and Paper
Sector," Water Resources
Branch, Ontario Ministry of the Environment, Toronto, Ontario, Canada, 1992.
23. McKinnon, L.,AOX as a Regulatory
Parameter: CharacterlzaUon,
Toxicity, and
Environmental
Fate of AOX from
Bleached Kraft Pulp Mill Effluents, Industrial Waste and Hazardous Contaminants
Branch, Environmental
Protection
Division,British Columbia Ministry of Environment, Lands and Parks, Victoria,
B.C.,
Canada, 1992.
24. "Assessment of Industry Costs to Meet British Columbia's
New AOX Regulations;
British Columbia Ministry of Environment,
Lands and Parks and Ministry of Economic
Development,
Small Business and Trade,
Victoria, B.C., Canada, 1992.
847
25. "Pollution PreventionTechnologies

for the
U.S. Pulp and Paper Industry draft report,"
Office of Pollution Prevention andToxics,
U.S. Environmental
Protection
Agency,
U.S. Government
Printing Office,Washington, D.C., 1992.
36. "Quality Criteria for Water, U.S. Environmental Protection Agency," Office ofWater, Washington,
D.C., 1992.
26. "Regulatory
Impact Assessment
of Pr0posed Effluent Guidelines and NESHAP fur
the Pulp," Paper, and Paperboard
Industry, Office of Science and Technology, U.S.
Environmental
Protection
Agency, U.S.
Government
Printing Office,Washington,
D.C., 1993.
edn.," U.S. Environmental

Protection
Agency, Environmental
Monitoring
and
Support Laboratory, Cincinnati, OH, 1989,
EPN600/4-89/001.
27. "Development
Document
for Proposed
Effluent limitations,
Guidelines and Standards fur the Pulp, Paper and Paperboard
Point Source Category," U.S. Environmental Protection
Agency, Office of Water,
U.S. Government Printing Office,Washing.
ton, D.C., 1993.
28. "Seventh Biennial Report on Great Lakes
Water Quality," International
Joint Commission, Washington,
D.C., 1993.
29. Canada
Gazette
Pari II, Vol. 126, No. 11.
30. "Aquatic
Effects Monitoring
Requirements," Environment
Canada, EPS 1/RM/
18, Ottawa, Ontario, Canada, 1992.
31. "Reference Method fur the Determination
of Polychlorinated
Dibenzo-para-dioxins
(PCDDs) and Polychlorinated
Dibenzofurans (PCDFs) in Pulp and Paper Mill Effluents," Environment
Canada, EPS 1/RM/
19, Ottawa, Ontario, Canada, 1992.
32. Carey,].H.,Hodson,
p,y', Munkittrick, K.R.,
Servos,M.R.,Recent
Canadian Studies on
the Physiological
Effects of Pulp Mill Effluent
on Fish, Environment
33. Gazette Offidelle du Quebec,
Vol. 124, No. 43, 1992.
October
7,
34. "Regulation Made Under the Environmental ProtectionAct:

Effluent Monitoring and
- Pulp
Effluent
limits
Province
Canada,
of Ontario,
1993.
and
Paper
Toronto,
Sector,"
Ontario,
35. "Amendmentto
B.C. Reg.470/90, the Pulp
Mill and Pulp and Paper Mill liquid EffIuentControIReguiation,"ProvinceofBri~
ish Columbia, Ministry of Environment,
lmds,
1992.
and Parks, Victoria,
B.C. Canada,
37. "Short-Term Methods fur Estimating the

Chronic Toxicity of Effluents and Receiving Waters
to Freshwater
Organisms
- 2nd
38. "Short-Term Methods fur Estimating the

Chronic Toxicity of Effluents and Receiving Waters to Marine and Estuarine Organisms," U.S. Environmental
Protection
Agency, Environmental
Monitoring
and
Support Laboratory, Cincinnati, OH, 1988,
EPN600/4-87/028.
39. "Technical Support Document
fur Water
Quality-based
Toxics Control," U.S. Environmental
Protection
Agency, Office of
Water, U.S. Government
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Washington,
D.C., 1991, EPN505/2-90/
001.
40. Federal Register 58 (241): 66078-66216.
December
17,1993.
41. "Action Plan for Marine Pollution," Swedish National Environmental
Protection
Board, Stockholm, Sweden. 1987.
42. Folke, J., Mannisti),
E., Lehtinen,
K-].,
McCubbin, N., Chlorine Dioxide In Pulp
Bleaching,
Duoplan Oy, European
Environmental
Research Group, Prepared fur
CEFIC,European
Chemical Industry Council, Chlorate Sector Group, Bruxelles, Belgium, 1993.
43. LOvblad, R., Presentation
to the EDF Paper Task Force, SOdra Cell AD, Varo, Sweden, 1994.
44. Lagergren, S., Swedish Environmental
Protection Agency, Solna, Sweden, personal
communication,
1995.
45. Decision taken by the Ministry of the Environment of Finland, 22 June 1989 on the
Reduction
of Discharges
of Chlorinated
Organic Compounds
from the Pulp and
Paper Industry, Finnish Ministry of the
Environment,
Helsinki, Finland.
46. Hynninen,
pulp and
P, and Pryke, D.C., "Finnish

paper mill activated
sludge
plants: operating experience

and designing for the future," Pulp Pap. Can. 94
(10):T325 (1993).
Subject Index
849
Absorbable organic halogen (AOX)

217,256,282-284,305,359,365,370,
371-372, 375, 393, 409, 413, 429, 434,
563,584,649,689,753,754,757,758,
760, 771, 773, 774, 778, 780, 782, 785,
788,791,838,839,845
Aceta1c1ehyde 208, 823, 830, 843
Acetic add, chIoroacetic adds
41,147,257,325,330,366,713,824
ACETOCEU..Process 41
Acetylation, acylation 197,198,
202-203,209,682,755
Addie groups, structures (see also
under carboxylic, phenolic hydroxyl,
and sulfonic acid groups) 585, 677, 678
Determination in pulp 684-686
Add treatment 224,330,336,353,415,
424,425,426,427,428,515,517,519,
523
Activated sludge treatment (AST)
488,651,779,799
Activation energy 37-38, 266, 280,
312,383,401,416,417,450
Aerated stabllization
651,776, 779, 785
basin (ASB)
Air entrainment 500, 502, 506, 517,

523,527,532,541,551,576,579,581,
591-592, 610, 658
A.LCELLProcess 41
Aldonic adds, aIdono1actones
149, 152, 176
38, 40,
AJkaIi (see also sodium hydroxide) 3, 14,

127,129,139,140,148,167,216,226,
233,29~295,31+318,467,475,613
AJkaIi darkening 140, 398, 403, 405,
421,429,469,475,477,497
AJkaIine extraction 106, 139, 140,217,
244,247,265,268,299,300,331-332,
~66,'6?,'65, 3??,i07,i13,i17,i18,
423,427,430,611~12,
744, 759,824,829
Pulp Bleaching
-Principles
and Practice
SUBJECT INDEX
A
850
AlkaIkonsuming reactions 138-140,

298
Alrernative alkali sources 315-318
Effect on carbohydrates and
extractives 297-299
Factors affecting alkali consumption
297
Filtrate reuse 317,666
Flowsheet for peroxide added in
oxygen-reinforced extraction stage 311
Oxidant-reinforced 297,305-306,453,
637,638
<>xygen-reinforced 298,306-310,385,
386,392,399,428,453,542,544,670
Oxygen- and peroxide-reinforced
310-311,385,418,419,420,421,
427,428,431,433,437,453,670
Peroxide-Reinforced 310-311, 314,
392,413,414,417,418,419,420,
422,431,434,453,660,666,813
Rapid extraction 31~3I4
Reaction variables 302-305,313
Reaction kinetics, reaction rate
2~302,304,305,309,312~13
Role in multi-stage bleaching
sequences 29~297
Alkylation, methylation 93,197-198,
200,202,203,204,206,209,356
Anthraquinone, anthraquinone
~~34,39,4O,45,
78,375,670
Anti-chlor 388, 399, 400, 660, 669
Aquatic test organisms 285,286,360,
773,774,775,776,777,778,779,780,
782,783,785,786,787,789,837,838,
840
Aromatic aldehydes and ketones 96,
99, 107, 122, 124, 135, 136, 142, 144,
145, 146, 148, 169, 171, 172, 175, 178,
193,195,196,199,200,201,761
ASAM Process
41,44
Ascorbic: add,
208,210
ascorbates
205-206, 207,
Autoxidation
105, 141, 143, 165, 166,
188,198,209,487
Beating, beating energy 12,280,371,

407,677,678,679,684,702,721,722,
723, 724, 725, 727, 730, 731, 732, 733,
737, 739, 741, 742, 743, 744
Benthk: communities
770,780,781,
783, 784, 785, 788, 791
Biological cbaracterlzation
of eJIluents
and receiving environments
Single-species acute and short-term
toxicity tests 772-774
Extended single-species
exposure 77+778
laboratory
Mcsocosms and experimental

778-780
streams
Field studies 780-790

Future trends and research needs 790792
Bio1ogk:a1 oxygen demand (BOD) 215,
217,257,286,340,359,488,511,651,
751-752,771,837,838,839,841,845
Biological treatment
of etDuents
(see Bleaching effluent)
Biomarkers,
endpoints
772,773, 774,
777, 778, 779, 781, 783, 784, 785, 788,
791, 797
Biphenyl structures
52,94,96,121,
134, 135, 140, 141, 142, 198
Black liquor
B1eachability
pulp)
solids 58~584
(see under Unbleached
Bleached ~p
Chemical composition 10, 684, 685,
742
End uses 719
tight and heat stability 3, 53,188,189,
190, 191,237,278-279,298,316,
349,358,406,429,430,487,506,585
~uction
6,7,8,215,287
Strength properties 49, 150,216,237,
280,328,331,358,371,431,437,
584, 727,739, 740, 741, 742, 743,744
Strength testing principles
Bleaching
Chemicals M, 1+16
723
Critical parameters 4
Efficiency 12-13, 16,247,264,305,
356,389,419,479,544,602,650
Flowsheets 19-20,2-23
Gaseous chemicals 17-18
General description M
History of ~
Kinetically controlled reactions 326,
327,544,602,610,611,612,61~15
Objectives 4
Process conditions 17-18
Unit operations 20
Reaction rates, kinetics 54+545, 546,
600
Selectivity 13, 16, 17, 127, 152-153,
217,22+225,243,247,349-350,355,
357,385,415,436,738
Sequences 16-17
Trends 20-24
Bleaching eftluent (&trate)
19
Biological characterization 770-790
Biological treatment, treatment costs
19,53,257,359,434,65~54,
755,
758,769,773,77+775,777,778,
779,780,781,784,785,790,826,
842
Chemical characterization,
characteristics 759-762,770-771,775,
790,838
Chlorination stage 129,132,246,250,
251,252,255,256,257,285-286,
289,373,660,666,671,755,756,
807,826,824,827
CE 153, 759
Chlorine/chlorine
dioxide stage 278,
585,660,752,753,754,755,758
Chlorine dioxide stage 251,252,282285,314,600,662,666,669,756
Color 340, 752-753
Compounds detected in 760-762
DE 756, 759
Discharge volume 19,649,651,710,
773,781,784,786,837
Effect on aquatic organisms 770,775,
776, 780, 781, 779, 780, 781, 782783, 784, 785, 786, 787, 788, 789
Elemental chlorine-free
(ECF) 340341, 752, 753, 754, 758, 761, 762,
774, 790, 791
Extraction
stage (E, EO, EOp) 256,
278,296,302,317,305,315,391,
Subject Index
393,413,660,660,662,666,668,
ISO (Integrating sphere) 703, 7~711,

712
Kubclka-Munk relationships 185, 382.
701
Ught absorption, light absorption
coefficient 12,48, 167, 185, 193, 194,
195,196,382,384,632,701,702
Ught scanering, light scattering
coefficient 12,48,74,185,487,632,
701-702,703, 720 722,723,727,
729,731,732,733,735,739,740,
741,742,744
752, 753, 754, 755, 756, 758, 759,

807,
826,
827,
831.s32
Factors affecting reuse: (recycling)

65S660
General characteristics 751-759
Molecular weight (MW) and MW
distribution of dissolved material (see
under Molecular weight and
molecular weight distribution)
OCE 756, 759
Oxygcn-stagc 234, 235,671
Ozonc-stagc
Measurement, meters (reflectometers)

705-712
Preparation of sheets for measurement
712-713
Relationship to chromophore
concentration 6~ 701, 704-705
Relationship to whiteness 705
Reversion or heat and light stability
(see also Yellowing) 34,51,53,95,
99,298,335,413,497,506,677
Sensors 249,251
TAPPI(directional illumination) 703,
707-709, 712
Upper limit ("ceiling") 174, 368, 382,
385,413,472,496,702-703.745
Wavelength 705-707
339, 340, 671
~Jdd~stagc
421,432,479,480,
614,616
Reuse (recycling) 226,250,251,255,
258,278,384,434,478.479,666,
670672
Screen room 236,666,668
Totally chlorine-free (1'CF) 340-341,
666, 752, 753, 774, 777, 790. 791
ToJddty 23, 129, 135, 153, 176,256,
285,340-341,~361,434,488,678,
769,770,772-778,781,782,784,
785,790,791,837,838,839
Bleach plant closure (see Closed cycle
bleaching)
B~ht__R towers (seeTowcrs)
BreakIng Icngth (see Tensile strength)
Brightness (cUffuse Intrinsic
ref1cctance factor) 3, 12, 107, 174,
186.26~271,272,281,311,312,313,
314.317,332.334.385,386,387,389,
390,392,406,418,420,421,422,423.
426.427,428,429,430,445,449,450,
451.453,462,464,465,466,468,469,
470,472,473,474,476.483,484,486,
501.508,509,627,629,630,635,636,
637,638,639.659,697-713,742
Comparison with tristimulus Z factor

706707
Compensated 404, 634, 635, 640,
641,642
Definition and interpretation of697~99
Effect of cleanliness on 445
Effect of light scanering on 701-702
Error sources In measurement 708-709,
711,71Z
Fluorescence effect on 703-704
Gloss effect on 7~710
851
Brown stock 228,373,813

Burst factor (Index) 477, 727, 731
c
Calclum.compounds, ions
39, 75, 78,

316,407,424,425,433,590,591,592,
662,677,686
Carbohydrates
105, 106, 107, 117, 122,
148.150,151,153,167,176,247,256,
257,263,381,493,585
Content
Conversion
In pulp 685
to aromatic
structures
during pulping 107

Degradation dcpolymerization
37,40,
117,145,151,152.176,224,233,
234.298,325,329,330,353,366,
726, 727, 739, 742

Determination In pulp 681 -683 (see
also under Cellulose and
Hemicelluloses)
Molecular weight, Dp, and molecular
weight distribution 280, 370
852
Pulp Bleaching
- Principles
and Practice
Peeling reactions 103, 106. 107, 124.

151,152,176.223,224,247.258
Protectors 217,224,252,330
Reactions with bleaching agents 122,
245,148-152.232-233
Carbon monoxide
620, 82~30, 842
227,231,309,382,
Carbonyl groups 76, 116, 123, 124,

128. 135, 136, 138, 139, 143, 144. 145,
150, 151, 152, 163, 168, 169, 195, 196,
197,198,199,200,201,202,203,204,
206,221,222,223,224,247.298,324,
325,351,381,404.430,435,436,437,
461,487,493,494,679,683,734
Carboxyl groups, structures 14,102,

103, 107, 109, 132, 139. 141, 146, 148,
151,154,168,170,172,222,224,246,
247.255.256,257,296,297,315,324,
325,350.381,435-436,684,736,744,
755, 760
Carryover 225. 234, 235, 236, 248, 249,
251,254,268,269,297,303,305,336,
33~340,391,404.407,422,423,424,
435, 583. 584, 585. 586. 615, 632. 637,
769,670,775,778,812
Catechol groups, c:atechols 95,96, 103,
105, 107, 119, 130, 131, 133, 139. 140,
164. 168, 173, 174. 177, 178, 188, 189,
222,246,285,349,775,789
Catechol-metal complexes 96, 105,
165. 166
CeIluIases 367, 371,679
CE K number 249. 250, 254
CcIIuloee 12, 13.44, 124, 128. 149, 150,
151,163,244,247,280,323,330,350,
354,356,365,367,370,393,493,501,
601,677,680,723
Content In wood and pulp 4,9,723,
724. 726, 734, 740
Crystallinity 724, 726, 727
Dcpolymcrization 4,9, 13, 150, 151,
216,219,223-224,232,233,244,
280. 330, 350, 354, 355, 401, 402,
403,407,408,416,679,726-727,734
Determination of content In pulp
681-683
Molecular weight (MW),MW
distribution. DP 8, 37, 40, 677, 678.
679,681,735
Properties 9
Solvents 679,680,681
Structure 9, 117
Cell wall, fiber wall 11, 19, 27-28, 35,
37,42,48,50,93,226,294,296,477,
542,544,610.684,702,703,724,725,
728, 729, 733, 742
Chcladng agents, scquestrants 14, 46.
153,209,350,352,353,354,358.359,
373,415,425,426,428,434,453,464,
465,466,467,478,486,495,501,770
Chelation treatments 188,190,330,
334,352,353,354,355,357,358,359,
372,421,424,424,427.428,453,~
466,479,482,487
Chemical recovery 215, 216-217, 234,
237,352,353,356,671.672,833
(Chemi)m
h nl pulp, pulping 34,
43,163,167,174,177,188,206,425,
463,493,572.684,719,728,744
Composition 728-729
Chcmirc6ncr pulping 43
Chcmithcrmom
h tca1 pulp
(CI'MP), pulping 6, 34, 42-43, 49, 51,
52,97, 185, 188, 195, 196. 203, 205,
428,463.511,687,736,810
Physical properties
51-52,486
Chcmithcrmom~h
pulping 485-487
Chlorate
ion
L-aI alkaline
13,62.63,64,65,66,67,
133,137,264,265,271,272,273,277,
278,286,381,382,389,390,392,770,
771,778,782,783,785,831
Chloride ion 62,63,64,79,
130, 132,
245,253,256,264,265,268,272.277,
278,381,391,392,583.689,832
Chlorination,
chlorination
stage
234 ,
276,278,303,413,451-452,542,544,
563,604,606,610,635,769,775,777,
778,807,814.829,831
Chemistry
127-128,245-246,295
Chlorine dioJddc substitution 251-
252.253,254,255
Effect
on
pulp
cleanliness
255
Environmental effects255-257
Subject Index
Process control 244, 249, 254, 303

Process equipment 252-254
Process variables 248-252
Reaction kinetics 247-248, 600
Schematic representation 244
Chlorine 3, 62, 63, 64, 66, 67,108,130,
135,136,138,149,150,153,217,225,
266,267,270,305,306,351,391,830,
831,832,833
Emissions 823-824,830,831,843,844
Manutacture 15,37,74-76,827
Properties 18, 73
Reactions with lignin, carbohydrates,
and extractives 127-132,154,246-247,
591,610,759
Radical 128, 149, 151
Safety precautions 73
Storage and handling 76-77,245
Chlorine dioxide 50, 100, 116, 121,
127,128,132,138,141,149,217,225,
247,250,264,266,267,268,269,272,
351,372,413,525,760,830,831,832,
843, 844
Analysis of solutions 67
Decomposition 61,67-68
Emissions 381, 392, .823-824,843,844
Generation systems 62-67
Health hazards 61
Manutacture (generation)15, 314, 372,
381,391,827
Properties 18,61
Reactions with lignin and extractives
133-138, 154,759
Safety and handling precautions
67-68, 393
Sensors 633-634
Chlorine dioxide b
hl...g 13, 255,
312,313,314,334,404,437,448,563,
604,608,684,829
Bleaching sequences 384-385
Engineering considerations 292-293
Environmental factors 393
Filtrate reuse (recycle) 250,384,666
Process chemistry 381-382
Process flowsheets 383, 384
Pulp quality 393
Reaction kinetics 382-383
853
Chlorine dioxide cleUplflcation

313,
385,610-611,829
AIIa1i requirements 268-269
Brightness development 269-271
Chemical addition mode 266, 270,
271,272,274,285,754,813,825
Economic factors 286-287
Efficiency 266-273, 276, 278, 389
Equipment 273
Filtrate reuse (recycle) 666
Process flowsheets 272,274
Process variables 252, 273-278
Pulp quality 278-282
Reaction kinetics 265-266, 600, 611
Substitution of chlorine dioxide fur

chlorine
84, 132, 252, 266-268, 270,
271,272,274,275,279,280,281,
282,283,284,285,286,287,297,
298,303,310,314,370,386,387,
413,452,542,591,636,751,752,
754, 758, 775, 778, 779, 781, 785,
788,825,827,828,829,842,843
Chlorine monoxide radical
(hypochlorite radical) 132,133,137,
151,407,408
Chlorine factor 280, 825
Chlorine multiple 249, 250, 264, 369,
754,812,813,814
Chlorodioxins
(see Dioxins)
Chlorodibenzofurans
(see Dioxins)
CbIoroaromatk: structures, compounds

129,135,138,139,284,759,760
Chloroform. 256,257,285, 397,407,
409,410,761,823,824-826,830,837,
842,838,839,840,843,844
Chloronfum ion 116,128, 130, 131,
152,814
Cbloroorpnk
structures, compounds
4,129,130,133,138,139,215,217,
243,245,251,253,265,268,281,283,
284,365,368,375,381,393,689,755,
756,758,769,837,845
Content in fully bleached puips 282
Determination of chlorine in 689
Chlorophenols 246,256,257,284,285,
689,761,771,788,789,808,809,816,
840
854
Pulp Bleaching
-Principles
and Practice
Chlorous acid, chlorite ion 62, 67,

133,134,263,264,272,277,298,381,
388,389,631,638,660,662,831,832,
666
Chromophores 49, 95, 96, 97, 105,
163-164,166,168-170,171,174,175,
178,192,194,197-]98,332,350,382383,400,401,402,416,417,460,487,
494,697,700,701,705
Cleanliness 236, 237, 255, 280, 431,
477,583,603,678
Closed cycle bleaching 24, 37, 235,
660,671-672
Cobalt (see Metals)
13(:NMR spectroscopy 100,109,132,
760, 762
Color 4, 30, 34, 36, 53, 54,97, 105, 163,
196,215,217,286,305,359,371,423,
434,494,662,698,769,771,837,842
Color stripping 54,494,510
Condensation reactions, condensed
structnres 95,97,99-102, 106, 134,
14~141, 144, 177,222,324,804,809
Coniferyl alcohol, conifery1 alcohol
groups93,98,129,137,178
Conifera1dehycle, conJfera1dehycie
groups 95-96,97-98,129,137,164,165,
168,169,177, 178, 192-193, 195,461,
493, 745
Contacton (see under Mixers and
Towers)
Coumaryl (p-hydroxyphenyl)
structnres 93,95, 144,222
Counterc:un'eDt washing (see under
Washing)
o
Dakin reaction, DaIdn-Uke reaction
168, 171, 173, 174
DeaIkyIation 52, 103, 118, 119, 1~132,
133,137,148,165,189,190,196,202,
257,356,683,686
Deckers 236, 357, 373, 478, 482, 590
Defoamers (see also underWasbing)
231,590,620,686,808,815,838
Deinked pulp (see Recycled fiber)

Degassing (see under Pumping and
Hydraulics)
DiaJkyl peroxides (dioxetanes)
142,
143, 144, 145, 152, 170, 171, 172, 222
Dialysis 755, 756

Dichloromonoxicle,
dichloromonoxicle bleaching 128,
407-408
Dienes 208-210
Diffusion and penetration 19,35,37,
105,226,299,253,301,304,327,367,
448,539,540,544,545,563,584,600,
612,618,619
Dimethyldioxirane
324, 423, 438, 670,
741
Dioxins
Amounts in pulp and paper products
808,809,810,811,815
Degradation in environment 817, 818
Formation reactions 804, 806-807
Government standards for discharge
816-817
Physical properties 801
Reduction strategies 812-816
Sampling and measurement 817
Sources of formation in pulp and
paper processes 807-812
Toxicity 801-804
Dioxiranes
(see Dimethyldioxirane)
Dirt specks (see Particles)

Disc mter 464, 478, 482
Dispersers (see Kneaders and Mixers)
Displacement bleaching 609
Dissolving pulp 3,34,281,293,397,
403-404
Dithlonite (hydrosulfide) 77,494
Drainage aids (see also under Washing)
591-592
Drainage, drainage resistance 684,
721,727,730,731,732,733,738,739,
740
DTPA (diethylenetetraminepentaacetic
acid)(see Chelating agents)
Subject Index
Dyes, Inks 44, 53-54, 494, 509, 705, 728,
729
E
EDTA (ethyleu
i..rninetetraacetic
add) (see Chelating agents)
Eft1uents (see Bleaching eIDuents)
Electron spin resonance (ESR)
spectroscopy 198, 205, 207
Electrophiles,
e1ectropbllic reactions
115, 116, 117, 118-119, 128, 133, 144,

145,146,148,151,167,171,324,416
Electropbllic
dispJacement
128, 129, 130
118, 119,
Elemental chlorine.free (ECF)

b--"hing,
ECF-b1eached pulps 109,
328, 34O,365,368,370,371,372,37~,
375,413,414,419,427,429,431,434,
437, 452-453, 586,684,685,740, 742,
743, 751, 752, 753, 754, 757, 758, 760,
761, 762, 790, 792
Emissions 578, 627, 677, 823-833,

842-844
Control of chlorine and chlorine
dioxide 830-833
Gaseous bleaching chemicals 823-824,
829-830, 842, 844
Volatile organic compounds 824-830,
838
Environmental regulations 4,243,434
Canada 816-817,837-839
Finland and Sweden 844-845
United States 817, 839-844
Enzone process 370
Enzyme-alded b
hing330, 354, 365377, 741
Effect on bleaching chemical
requirements 369-371
855
Sequences comprised of enzyme

treatment 368,371,374
Enzymes 14, 15,48, 365, 372, 373, 374,
375,435,686,741
Activity 368
Suppliers 367-368
BOD induction
777, 778, 781, 782,
783, 787, 788, 791
Etben, ether struc:tures 94,96,100,

103, 145, 148
a- and ~ Aryl 94, 96, 98, 99, 100, 103,
104, 106, 131, 144, 146, 147, 148,
197,200,201,202,203,204,209,210
Oxiranes (epoxides) 103, 104, 134,
137, 139, 140, 142, 143, 154, 155,
169,172,221,222,324
Vinyl aryl 98, 100, 120, 129, 137, 144,
146,148,222,323
EthyIenk: (olefinic) groups 102,109,
116, 120, 129, 130, 133, 134, 138, 145,
146,148,154,163,178,195,323.436,
437,461,487,591
Extended dt'lignifiotion
37-38, 39,
243,285,332,368-369,375.414,450,
454,487,591,723,726,739.740,741,
742, 743, 744, 753, 757, 763, 777. 790,
842
Extractable organic halogens (EOX)
108,282,283,284,754,771,773,789
Extraction (seeAlkaUne extraction)
Extractives 3,10,30,108,153-154.176,
246,256.279,281,298,589-591,677,
686,769.771
Characterization 687
Content in wood. pulp 29, 108, 279,
281,477
Determination in wood, pulp 29, 108,
687~8
Fractionation 687~
Removal from pulp 12, ~7
Effect on kappa number 368-369

Effect on pulp properties 330,371
Environmental
Fiber networks (suspensions) 327,

515,523,525,547,561,603,607,720,
721, 725, 729, 735, 738
Characteristics 541
Mechanism
effects 371-372
of enzyme action 366-367
Process flowsheets
372-373
Fatty acids (see Extr.lctives)
856
Pulp Bleaching
-Principles
and Practice
Composition in different bleaching

operations 542
Floes, floculation 327.337,540.541,
545,546,550,554,556,560,561,
600,618.619.721,724,725
Flow velocity 515-517, 525, 528. 529,
530,533,549
Rheology 54~542, 545, 546, 603
Strength 46-48,516-517,528,547,729
Swelling 602,678,684,727,728,729,
740, 744
Turbulence in 541-542,545,548
Fiber(s)
Bonding 47,50,52,477,678,701,702,
720, 722, 726, 728, 729, 733, 737,
744
Characterization, characteristics
462-463,687,728-729,745
Coarseness 724,725,733,737,740,
742
Conformabllity 50,477,724.727,732
~8C
721,725-726,734,738,740,
741, 742
Dimensions 632,701,724, 725, 729.
733, 737, 745
DryIng 684, 724, 727-728, 729, 734
Flexibility 45, 47, 50, 51, 723, 737. 477
Morphology 724, 725, 728, 729, 738
Rigidity (stiffness) 50,52,67,678
Strength 45,677,678,679,735,737,
739
Surface 45,51,327,369,540,543,549,
554,589,590,600,658,679,698,
719, 720, 724, 725, 729, 734, 735,
738, 747
Swelling 477,678,684, 728, 729
Fiber
supply
(see Wood supply)
Filler pulp 719, 738, 737, 739, 740, 743

Fillers 48, 254, 488,666,697,720,
728, 738
723,
Flltra1l: tanks 573. 579, 586, 591,823

Fines 51, 52, 463, 593.697,720,721.
722,728,730,731,735,808
Flow meters (see under Pumping and
Hydriulics)
Flufting, f1uffers 228, 230, 327, 336,
337,554,555,562,609,600,604,613,
616,617,618
Fluorescence (see under Brightness)
Formaldehyde 37,95, 101, 102, 105,
174,830,843
Formamidine
sulfinic add 54, 476, 477
Formic acid, formates 62,66, 152, 169,

208,210,257,330
Freeness 729,730,731,732,735,738
Free radicals 116, 121. 122, 124, 128,
132. 134, 136, 143, 149, 165-166, 167.
197,200,201,202,205,209,247,453,
679, 744
Free radical coupling
135,144,198,222
121, 128, 134,
Free radical scavengers 128,149,

205-209,250,247,263,325,330,408,
409,410
Furans (see Dioxins)
G
Gel permeation
(GPC) 105
chromatography
Gloss (see under Brightness)

Glucorn..nn..n. (see HemiceUuloses)
Gonad somatic index 786, 797
Groundwood, groundwood 'Pulping
10,34,37,41-42,47,49,50,105.176,
177,187,189,190,196.462,463,493,
511,690,736,810
Guaiacyl units 93, 109, 115, 128, 129,
130,133,139,144,760
H
Heat reversion (see under Yellowing)
Hemice1lulases (see Xylanascs)
Hemice1luloses (see also Carbohydrates)
3,9,12.29,39.40,44.45,48,106,107,
124,163,176,221,244,247,293,298,
365, 366, 367, 374, 375, 493, 677, 678,
683,684,726,727,744
Analysis 681-683
Content in wood and pulp 9,27,366,
374,375,723,724,739,740,741
Subject Index
Properties 9
Structure 374
IH NMR spectroscopy
132
203-204, 209
Hydrogen ion concentration (pH)

13, 106, 127, 132, 142, 167,245,251,
272,276-277,297,328-329,354,358,
381,382,383,388-390,399400,404,
405,408,421,450,497-498,509,584,
590,627,629,632-633,638,662,713,
735,744,814,815,833
Hydrogen peroxide 3, 14,46,50,51,
54,62,67,75,96,97,99,116,127,142,
145,163,165,195,221,225,297,304,
305,349,352,353,365,525,679,818
.
Activation, activators 356,357,414,
424,430,435,437
Decomposition, decomposition
reactions 77, 142, 167, 176,219,224,
319,349,350,353,355,415416,417,
420,424,432,453,461,464,473,477
Manufacture 15,78-79
Properties 77-78,480
Reactions with lignin 168-174, 415
Reactions with carbohydrates,
extractives 174-176,461
Safety precautions 77-78
Storage and handling 79,481-482
Hydrogen peroxide b,..,...hing (see
Peroxide bleaching)
Hydrogen peroxide b
hing solutions
Composition 166-167
Makeup systems for 478, 480481
Metal-catalyzcd decomposition 167,
414,666
Recycle 478,479,480,482,483,484
Stability, stabilization 414,481-482
Hydrogen peroxide dplqp.ifV;:ation
413, 744
Environmental factors 359-360
Flowsheets 352,353,357, 358
Modified treatments 356-357
Process control 358
Processes 351-353
Hydroxonium
HydroperoxyI.
radicals 116,142,144,
145,146,151,197,200,205,209,210,
218,219,324,329
radicals
and Practice
CE 248, 269, 294, 299, 300, 302, 303,

304,306,307,310,311,315,316,
317,369,400,407,815
219
C(EO) 307, 308

C(EOp) 311
(DC)E, (D+C)E, (CD)E 265,267,269,
564
DE 265, 266, 276, 277, 387
E(O) 276, 307, 398-399, 642, 645
EP 276
ion 116
p-Hydroxybenzyl
alcohol
129, 171, 199, 200
p-Hydroxyphenacyl
200
Hypochlorite
Hydroquinone
structures,
hydroquinones
54,95,105,140,164,
171,174,208,209,436,487
4,
Hydrosu1fite
blrM'hing
185, 187, 188,
190,475,480,484,526,592,729,744,
745
Brightness response for dlffcrent pulps
510
Dcinked pulps 509-510
Effect on pulp properties 501
Factors influencing brightness
response 495-501
Future trends 511-512
Process control 505, 506
Process fIowshccts 505,506,507,508
Process variables 495499
Reactions with chromophores
177-178,
493494
Safety and environmental factors 510-
511
-Principles
Hydroxyl radica146,
116, 141, 142,144,
145, 146, 151, 153, 167, 168, 171, 173,
176, 219, 223, 225, 324, 329, 349, 350,
415,416,424,459,460,461,487,689
Hydroperoxide
(pcrhydroxyl)
anion
96,116, 141, 144, 152, 154, 166-167, 168,
171, 172, 176, 195, 218, 349, 351, 415,
416, 417, 421, 459, 460, 461, 469, 639,
640
Single-stage systems 504-507

Two-stage systems 507-509
Pulp Bleaching
Hydroxide
ion 96, 116, 142, 155, 160,
168, 171, 176,219,301-302,461
Hydrolysis
Acid-catalyzcd 9,40, 105, 109, 135,
150,151,393,679,682,686
Basc-catalyzcd 9,40,97,99,100,103,
105,106,121,139,150,295,296,
299,325,759,824,825
HydrosuIftte
(dithionite),
hydrosuIfite
b1PAtohing solutions
51,54,97,163,177,178,505,525,592
Active bleaching species 176-177,
494-495
Composition 494-495, 502-504
Handling and storage 502-503
Manufacture 15, 503-504
Properties 501-502
Stability 177,495,497,498,500,526
858
Hydrotrioxy
Pulp properties 358-359

Sequences 351, 359
Hydrochloric add 62,65,76, 127,245,

246,251,268,315,382,388,585,843
Hydrogenation
857
groups
groups
97,
171,197,
(see Sodium hypochlorite)
Hypochlorite
bleaching
151, 255, 257,
313,317,397-407,437,476,650,604,
824,825,843
Environmental effects 407
Process control 398,399,401,404-406
Processflowsheet402
Reaction kinetics 400-401
Sequences 17,50, 397,403,406,407
Hypochlorite
Hypochlorous
add 127,128,130,132,
133,135,136,137,138,151,154,245,
257,264,271,381,408,410,754
Bleaching 407-410
Generation 410
I
Impellers (see Pumps and Mixing)
132,687,
Inks (see under dyes)
K
Kappa factor 250, 264, 268, 270, 276,
283,285,369,826
Kappa number 10, 48, 50, 232, 233,
243,264,267,269,274,279,280,283,
307, 308, 311, 329, 333, 353, 354, 355,
359, 368, 386, 392, 398-399, 422-423,
629,635
C-stage 299
number
analyzer
Ketyl free radical

209,487
Kneaders
632, 636, 637,
197, 198,200,201,
476, 550, 556
Knots (see Particles)

Kraft process, kraft pulp 6, 10,34,3538,97, 102-103, 109, 131-132,282,305,
307,349,351,366,369,370,371,387,
719, 726, 736, 740, 743
Pulp composition 44, 47
Kubelka-Munk
relationships
under Brightness)
(see
radica1132
Infrared (IR) spectroscopy

690, 745
Kappa
642
Laccases (see Enzymes)

Leucochromophores
146,166,168,
174,177,487,493
Ught absorption, light absorption
coeft1dent (see under Brightness)
Ught interactions with paper 11, 697,
698
Ught scattering, light scattering
coefficient (see under Brightness)
Ugnin 3,9,12,16-17,33,34,50,100,
115,119,122,127,135,138,153,163,
177,188,197,198,216,218,220,244,
246,248,257,294,306,323,349,350,
351,365,416,436,446,461,493,585,
601,678,683,697,699,727,729,759,
760
Chemical modification of during
bleaching 97, 108-109,684
Chemical modification of during
pulping 97,99-106, 106, 184,684
Content in wood and pulps 9-10, 12,
Subject Index
34,36,37,49,269,307,422,450,
627,632,677,724,741
Determination in wood and pulp 50
Determination in bleached pulp 683684
Effect of sulfidity on degradation 99
Hardwood 93,128
Interunit linkages 94, 106
~99,
100,102,103,105,
144, 148,
349, 758
IJnkage with carbohydrates 37,93,
103-105, 108, 223, 294,759
Milled wood lignin (MWL) 97,107,
109,165,196,198,203
Model compounds 122, 129, 130, 133,
135, 137, 138, 139, 145, 153, 166,
168,193,198,199,350,414
Modification of functional groups 93,
97, 102, 103, 106, 124, 165, 197-198,
200, 201, 202-204
Soflnwood 93, 128, 129, 165,246
Sttucture, functional groups 9,93-95,
96,422,~5
'ig1'inues
(see Enzymes)
Ugnosulfonates,
lign08u1fonic
97,106,132,193,684
Ugnox process 352,741
acids
Pe~xide
Mesoc:osms
stage 78,357,433,467
778-781, 791
Metals, metal ions 45, 46, 105, 166,

173,190,198,223,243,330,352,421,
424,425,426,427,463-464,466,475,
482,484,500,677,678,684,690
Content in wood and pulp 47,454,484
Determination in pulp 689-690
Effect in bleaching 427,428,46>466,
501,689
Sources in bleaching systems 46
Transition 41,45,96,142,145,146,163,
166,171,197,219,224,329,350,353,
354,355,415,417,419,424,425,427,
428,453,460,464,472,473,
5~501.
770, 771
Methano144, 62, 63, 64, 66,130,131,
132, 133, 136, 137, 140, 142, 143, 147,
148,168,197,227,247,256,325,330,
620,684,823,826-829,843
Methoxyl (alkyl-aryl ether), alkoxyl
groups 102, 103, 105, 109, 129, 130,
138,148,165,167,190,196,222,247,
759, 760
Methyl
ethyl ketone
823, 830, 843
Milox process
41,437
Uver somatic index (ISO 783, 786, 797
Minox
351-352
Mixed function oxidases 777
Magnesium compounds, ions 39, 75,

78, 153, 216, 224, 225, 330, 353,354,
356,424,425,427,428,431,432,592
Magnesium
sulfate heptahydrate
(Epsom salt) 224, 354, 415, 427, 460, 480
Maopnese (see under Metals)
Mannaneses 367
Mass transfer ofb
hi"'g ("bemiNds
19,216,218,22>226,227,326,54+
546, 5994jOl,603, 609, 612, 615,618,
619,625
Materials of construction 16, 373, 410,
525,527,530,5~589,669
Alkaline extraction stage 73-74
Chlorination stage 73,245
Chlorination-chIorine dioxide stage
'67,'88
Oxygen stage 81-82,229.530
Ozone stage 339
859
process
Mixers 216, 468, 556, 603-604

Continuous stirred tank 546-548,556, 563
Dynamic 548, 554, 556
Flutfers, fluffing (see also under
flutfers, fluffing) 543, 554, 556
High-consistency 479, 55+555, 557
High-shear 87,216,226,228,253,254,
272,304,305,309,337,338,358,482,
548,549,554,556,557,558,559,561,
562,563,603,608,609,611,614,615.
616,617,671,677,725
Peg (paddle) 453,478, 482, 549-550,
554,556,558,561
Shredders 554,556
Static 253,254,272,481,504,516,
548-549,554,556,558,561
Steam (see also Peg mixers) 46,216,
226,228,384,390,391,402,403,477,
521,528,550,604,605,611,612
Tower 547, 559
860
Pulp Bleaching
-PrInciples
and Practice
Mixing 251,253,304,336,454,525,
54+554, 600
Assessment 557-561
Efficiency 392, 454, 482, 499-500, 559
Energy (Power) consumption 543,544,
547, 550, 557, 561-562
Fluidization (see also Fluidization under
Ptmnp~327,338,542,548,550,563
Fluid shear in 541, 546, 547, 548, 549,
551, 554
Gas contacting 542-544,549,551,557,
601
General principles 539-544
Index 558, 564
Laboratory-scale 563
Power dissipation in 541-542,543,544,
545,547,548,550,561-562
Quality 544, 557, 561-562, 563, 564
Rate 5#545,
562-563
Scales of 539-540, 546, 547, 558-561
Thrbulence 541-542,543,545,546,
547,548,554,556,561,604
Molecular weight, molecular
weight
distribution
105, 148,256,301,591,
679-681,75+758
Monox-L
(see Free radical scavengers)
MOXY process
39
Muc:onic: acids, muc:onk: acid lactones

121, 131, 132, 133, 134, 135, 136, 137,
143,146,148,221,222,246,324,436,
756, 759, 760
Multivariate
data analysis
Mutagens, mutagenk:ity
677, 690-691
129, 135, 285,
286, 769
N
Nitrilamine (Cf'ln..ftlid~) 357, 435
Nitrogen dioxide 225,306,357,842
Nonwood fiber 30-31, 39, 50
Nucleophiles, nucleophilk: reactions
116, 117,118, 120, 123, 124, 130, 138,
142, 144, 151, 165, 167, 168, 171, 176,
221,295,296,415,435,461
Nucleophilk: displacement 139-140,
142,296
o
Octanol-water
284, 754
partition
coefficient
Opacity 42, 48,51,477,

697, 699, 719,
720, 727, 738, 743, 744
Organophosphonates
agents)
Organ08Olv
pulping
(see Chelating
40-41
Oxidation,
O1l:,di7.Jng agents 3, 14, 100.
105,116,119,122,124,127,131,133,
134,137,141,145,146,150,165,217,
219,223,245,246,303,305,350,358,
382,408,413,414,416,417,423,429,
436,438,493,509,612,679,684,760,
818
Oxidation-reduction
53,254,436,630,833
potential
(ORP)
Oxidized white liquor 217.226,227,

228,230,237,250,617,636,638
OxicUzing equivalents
agents 15, 16, 132
ofb
hi"'g
Oxygen 3, 45, 62, 96, 100, 116, 121, 133,

145,149,167,171,196,197,202,205,
220,226,249,297,304,305,351,365,
420,432,679
Activation 414
Chemistry 218-219
Manufacture 15,82-84
Properties 18-19,81,226,308
Reactions with lignin and
carbohydrates
141-144,151,220-224
Safety precautions 81-82
Singlet 145, 219
Stepwise reduction of 142,218
Transportation and handling 81,8+85
Oxygen deUg1'ifVoadon 50, 105, 109,
142,151,153,155,227,266,269,270,
285,306,309,332,333,352,355,359,
370,375,414,437,448,450-451,527,
530,542,563,584,589,601,608,612613,61+615,616,620,636,670-671,
679, 723,734, 740, 741, 743, 752, 753,
756,758,773,777,778,781842,827
Effect on puip quality 237
Filtrate reuse In 226,228, 230, 234,
235,250
Heat effects 218,226
High-consistcncy 229-231
Subject Index
Medium-consistency
227-229
Oxygen and alka1i consumption 226-227
Processes and equipment 227-232
Process flowsheets 216, 228. 230
Process variables 232-234,417-428
Reaction kinetics 226, 232,600,612, 619
Reactors 227,228.229,230,231,237.
612-613,614-615
Relationship to other mill operations 234
Selectivity 219, 224-225, 227, 232, 233,
234,235,236,615
Typical operating data 227
OZone 3, 46, 54,96, 116, 121, 141, 149,

150,152,153.215.217,249,303,365,
414,429,431.679,818
Decomposition
145, 329, 617
Destruction 87-88, 336
Emissions 824, 842
Manuf.u:ture (generation) 85-87,323,
336,338,339
Properties 18-19,85,323,326
Reactions with lignin model compounds
145-149
Reactions with lignin and carbohydrates
148.149. 150, 151,32~325
OZone b~h'nB
(m-UI"'ftcation)
151,153,303,370,385.414,427,437,
453,542,557,563,670,671.679,684,
734, 741, 742, 790
Additives 329-331
Alkali extraction in following stage 331332
Environmental factors 340-341,752
Filtrate reuse 339, 340
Location in multi-stage sequences
33B36
Materials of construction 339
Process conditions 325-332
Process equipment 336-339
Process flowsheets 334,337,338
Reaction kinetics 327
Reactors 61~14. 616-617
Selectivity and effectiveness 323, 324.
325-326,327,329,333,336.340
Sequences 330, 331,332, 334,335,336
p
p4S01 induction
786.787.791
777, 779, 781, 784,
861
Paprk:ycle process 315-318,670

Particles 42, 48, 52, 244, 253, 275, 359,
401,445,521,563,643,645-646,668,
728,729,738,745,815
Content reduction 454-455
Measurement of 446, 689
Types 445
Particle bleaching 3, 12, 16, 48, 255,
281,445-455,501,544
Approaches for improving cleanliness
454-455
Chlorination stage 244,451-452
Chlorine dioxide stage 280-281,381,
389-390,392,393,448,449,450,454
Degradation patterns during 448-450
ECFsequences 452-453
Effect of particle size and origin on
bleachability 445-448
Hypochlorite stage 403
Oxygen delignification stage 450-451
Peroxide stage 487
TCF sequences 453-454
Peracetic add (see Peroxy acids)
Perhyd.roxyI ions (see Hydroperoxide
ion)
Perhydroxyl, peroxyI radicals (see
Hydroperoxyl radicals)
Perrnllnpnllte
number 10,48, 50, 265,
266,269,392
Peroxidases
366,375
of mechanical
Peroxide b~h'"'B
pulps 153.334,604,612,614,684,741
Chemistry 414
Economic factors 434
Effect on pulp quality 430-431
Factors affecting brightness 417-428
Filtrate reuse in 666
Kinetics and stoichlometry 416-427
Process flowsheets 432-434
Typical bleaching sequences 428-430
Peroxide b
h'"'B (brightening) of
(chemi)mecbanica1 pulp 97, 153, 185,
187,414,45~54.50'-50Q,592,614,
639,683,684,687,688,690,744
Bleach plant configurations 484
862
Pulp Bleaching
-Principles
and Practice
Chemical consumption In 465

Effect on pulp properties 477
Factors affecting brightness response
461-477
General description 460
Hyperalkall 477
Kinetic models 472
Monitoring and control 483
Oxygen-pressurized
414,420,422,430,
433,608
Process flowsheets 474,477,478,479,
485,486
Recycled fiber 54, 474-477
Refiner bleaching 485
Selection guide for proper conditions
484-485
Single- and two-stage 478-480
Typical bleaching responses 472
Peroxy adds, per8dds
41,197.200,
205,209,230,414.435,436,437.741
Chemical pulp bleaching with 437-438
Effect on materials of construction 80
Manufacture 80
Properties 79-80
Safety hazards 79-80
Storage and handling 80-81
Peroxymonosulfurk:
add (Caro's
add) 54, 50, 430, 435, 436, 438
pH (see Hydrogen ion concentration)
Phenolic hydroxyl
groups 14,95,97,
99-100, 131, 140, 141. 142, 166, 168.
196,197,198,201,202,209,220.222,
268,356,357,425,678,684.777
Determination of in pulp 684
Phenolic, non-phenolic
nuclei 103,
120, 133, 134, 135, 137, 141, 142, 143,
144,146,148,200.307,324,416,436,
437,670.760,762
Phenolate
ions 105, 139, 140, 142, 144,
219,220,296.350,461
Phenoxy radicals 121, 133, 135, 142,
144.166,171,196,197,198,199,201,
~O~,~Oj,Z01,Z05,Z~.Zl~,j50.4B7
13pNMR spectroscopy 194,222
Polysulfide pulping 34, 38-39, 45, 670
Physical properties of pulp (see

Strength properties)
Pitch (see Extractives)
Polyethylene glycol (PEG) 205, 818
PolyoxometaJates 435, 741
Polymers, polymerization 93,100,
118,165,206,256,257,293,324,592.
679,681,755,757
Polysaccharides (see Carbohydrates)
Polyvinylpyrrolidone
205
Post-color (PC) number (see under
Yellowing)
Prenox process 225
Presses 11,30,614
Screw 478, 482, 572, 593-594
Twin-role 230, 464, 478, 482, 579-580,
613
Twin-wire 464,478,482,572,594
Process control 4, 399, 400, 404-406,
669,677,833
Control loop tuning 586,629,636
Chlorination stage 635-636
Chlorine dioxide, chlorine dloxidechlorine delignification stages 636-637
Chlorine dioxide bleachlng stage 638-639
Fuzzy logic 642,644-645
In-line process and quality
measurements 628-634
Open loop bump test 640, 641
Optimization of control loop
performance 640.644
Oxygen stage 637-638
Peroxide stage 639-640
Pulp flow, pulp suspension viscosity
(see Pumping)
Pulping 33-44
Miscellaneous chemical processes 40-41
Process classification 33-34
Selectivity in 37, 450, 723, 738, 744
Pulp suspensions (see also Fiber
networks) 515-517,540-544,547,548,
549,551,554,558,560
Pulpwoods of North America 28
Pulp-water relationships
11
Subject Index
Pumping and Hydraulics 38
Basic concepts 51~521
Cavitation 518,519,521,522,531
Degassing, deaeration 517,522,523,525,
526527,528,529,551,585,617,658
Flow metering,flow meters 403,533-534,
583,634
Flow velocity 515,516,517,521,525,
528,529
Fluidization of puip suspensions 517,
522,523
Frictional losses 516,517,526,527,
528,529
General design considerations 529-534
Low-conslstency puip 517,521-522,
544
Medium-conslstency systems 274,515,
517,520,554
Mixing during 525,554
Net positive inlet pressure (NPIP) 518,
521
Net positive inlet pressure requirement
(NPIPR) 519
Net positive suction head (NPSH) 518,

521,522
Net pressure suction head requirement
(NPSHR) 519, 521, 522
Partial flow 531

Pressure measurement 530
Pulp suspension behavior 515-518
Pumps 50, 468
Centrifugal medium consistency 11,
357,384,403,433,506,515,516,
517, 51~519. 521, 522-526, 529, 531.
544,593,603,609,611
Drive chains 531 -532
Effidency 521,525
Fittings and supports 516,531
Gear 520, 527-528
bnpellers 517,518,519,522,523,525,
546-547,548
Maintenance 521, 532-533
Performance curves 519
Open feed 521
Positive displacement 383,515,520521,526-528,529,533
Scala ;3~
Single-screw 527
Size selection 530
Suction 528
863
Thick-stock 230,311,384,398.399,
400,402,482.515,526.611.613,614
Twin-screw 520, 526-527, 529, 530
864
Pulp Bleaching
-Principles
and Practice
Repulping (see Pulping under Recycled

fibers)
Size exclusion chromatography

(SEC)
680-681,687~8,754,
755, 757,758
Resin adds (see Extractives)
Sodium borate 495, 504

Sodium borohydride 151,201,202,
204,298,325,331,484,495,496,504,
511,679,682,734
Runnabllity and factors affecting 176,

720-721,738
Quinone methides
98, 100, 101, 103,
105, 116, 117. 123, 143, 164, 165. 171,
172,204,220,221,493
0- and p-quinonoid
units, quinones
54,96,97.99.105,116,118,119,120121, 130. 131, 132, 133, 134. 135, 137,
139,140,141,142,146,147,164,165,
168, 170, 171, 172, 173, 176, 177, 178,
188,189,193,194,197.202,206.208,
209,221.222,246,351,436,493,494,
684, 756, 759
R
Reactors (see Towers and Reactors)
Recycled (secondary) fiber, recyding
6,31,32.43-44,512,703,704,727-728,
811
BleachabiHty,brightness response 52-53,
474,475,476
Color stripping 54
Composition 52
Deinking 44
Dyes 53-54, 704
Hydrosulfite bleaching of deinked fiber
476,509-510
Peroxide bleaching of deinked fiber 474
Physical properties of 52
Pulping 43-44
Reduction, reducing agents 54,62,63,
64,67,75,97,102,116,119,134,141,
142,177,189,195,202,203-204,206,
209,298,484,493,494,502,504,509
Refiner bl(opching 497, 504-506, 507
Refiner mechanical pulp (aMP),
pulping 14, 34, 42, 49.177,187,194,
463,497,736
RefinIng, refiners 97, 166,237,407,
485,497,505,507,516,721,722,726,
728, 742
Reflectance (see Brightness)

Reinforcement
736, 737, 738
pulp 719,720,735,
Scale, scaling 407, 428, 466, 481, 485,

590,649,668
Scanning electron microscopy (SEM)
50-51.446,447,448
Scrubbing, scrobbers 76,384,617,810,
823,825,830-833,843
Seal tanks, seal tank design 650,657,
65~59,66O,662,668,671,824
Semichemical pulping, semichemical
pulps 34, 43, 735, 736
~
4,251,254,358.402,403,404406,619,586.628,643
Chlorine 633-634
Chlorine dioxide solution 633-634
Consistency 586, 629. 634
Dual 358, 634, 635, 636, 637, 639
Optical (for brightness and kappa
number) 251,254,272,274,358,
398,403.4O4,4O5,62~29,630,
632.637,642
pH 358, 403, 404, 405-406, 629,
632-633
Polarographic (for residual chemical)
254,403.404,630,638
Redox (for chemical residual) 254,630
Stock flow 586, 634
Shives (see Particles)
Shive analysis, shive analyzer 643,
645-646
Short-term tensile test 745
showers, shower water (see also under
Washing) 576, 577, 579, 586, 591,650,
653,655,657,660,662,666,669,670,
671,827
Shredding, shredders 327, 404, 554,
555,556,604
Sivola process 34, 40
Sodium carbonate 296,297,298,299,

302,303,309,314,315.316
Sodium chlorate (see Chlorate)
Sodium formate (see Formic acid and
Formates)
Sodium hydrosulfite, sodium
dithionite (see Hydrosulfite, Dithionite)
Sodium hydroxide 14,35,38, 39, 138,
226,227,228,237,268,269,293,296,
297,302,303.305,306,309,312,314,
315,316,352,355,356,357,383,384,
385,388,389,423,426,460,469,476,
503,504,511,525,585,606,612,831
Manufacture 15,74-76,314
Properties 73-74
Storage and handling 77
Sodium hypochlorite 16, 64, 65, 75,
127,141,151,152,154,245,305,313,
314,315,413,423,429,433,525,824825,831
Sodium molybdate 356, 435
Sodium pyrophosphate,
sodium
tripolyphosphate
153, 501
Sodium silicate 315,353,354,415,424,
427,428,460,464,466-467,480,481,
483,485,612,639,640
Sodium sulfate, sulfate ion 36, 62, 66,
67,75,583,589,832
Sodium suIftde 35, 36, 38, 39, 99, 103,
104,315,832-833
Sodium sulfite, sodium bisulfite 42,
43,97,116,176, 177, 178, 188, 189,
193,205,208,253,426,494,495,503,
504,509,745,773
Sodium tungstate 435
Steryl esters (see Extractives)
Stilbene quinones 52,117,164,166,
171, 172, 175,207
Subject Index
Stilbenes 93-94, 97, 100, 103, 117, 120,
129, 137, 144, 146, 148, 149, 166, 174,
175,176,198,222,323
Stock chest bJ
hing 5()6.507
Stone cell aggregates 446-447
Stora process 34,40
Strength (mechanical) properties of
bleached pulps (see also Strength
properties under Bleached pulps) 16,
730-735
Chemical pulps 659, 679, 730-735
(Chemi)mechanical pulps 477,735-736
Effect of (Chemi)mechanical pulp
bleaching 744-745
Effect of kraft pulp bleaching 738-743
Effect of sulfite pulp bleaching 743-744
Factors affecting 186,723-728
Relationship to viscosity 734-735,739,
740, 742
Relevance of standard tests in
commercial papermakinq 736-738
Strength property pairs 732-735,736
Strength property measurements
Future trends 75
Interpretation ottest results 732-735,
736
Standard testing procedures, tests 729,
730-732
Under1ying principles 722-723
Sugars, sugar analysis 45,105,107,
368,682
Sulfamic add 128, 149, 247, 682
Sulfite pulp, sulfite pulping 6,10,34,
35,3941,49,50,97,132,154,187,188,
189,190,279,293,305,307,351,353,
357,422,428,430,719,726,736,740,
743-744, 812
Sulfonic add groups, sulfonation 43,
51,97,106,177,178,494,684,723,
729, 745, 813
Determination of in pulp 684
Sulfoxylate ion 177, 494
Sulfur 34, 832, 833
Sulfur dioxide, sulfur dioxide-water
39,62,63,65,116,176,177,353,373,
388,400,426,460,477,478,479,484,
865
494,503,506,509,606,637,638,639,
660,669,832,842
Sulfur dioxide anion radical 116, 176,
178,494
Sulfuric add (see also Sulfate ion) 63,
64,65,67,80,330,353,358,373,435,
477,484,504,511,525,682
Superoxide anion radica1116, 141,
142,145,167,171,176,205,218,219,
220,349,415,416,424,459,460
S~ts
474,475
Suspended solids (see Total suspended
solids,TSS) 651
Syringyl units 93, 128, 129, 130, 144,
166, 760
T
Tear strength (tear index, tear factor)
47,48,49,52,237,280,328,371,431,
477,486,487,551,679,720,727,731,
732,739,740,741,743
Tear-tensile relationship 49,328,431,
679, 732, 733, 736, 743
Tensile strength (tensile index,
breaking length) 47,49,52,205,206,
208,237,280,327,371,431,477,486,
487,551,679,720,727,731,732,733,
739,740,741,743
Thermomechanical
pulp (TMP) 34,
42,49,51,97,185,187,188,189,190,
195,462,463,511,736,744,810
Thk~.-ning, thickeners (see also
Presses) 593, 594
Thioethers
207-208
Thiols 206-207, 210

Thiourea dioxide (see Formamidine
sulfinic acid)
Total organic carbon (TOe) 278,359,
752, 753, 756, 757
Total organic chlorine (YOCI) 282,
753, 756, 757
Total suspended solids (TSS) 651,769,
770,771,837,838,839
Totally chlorine-free (YCF) bleaching
TCF-bleached pulp 328, 334, 336, 340,
866
Pulp Bleaching
-Principles
and Practice
365,370,372,373,419,422,424,42~
430,431,432,437,510-511,584,585,
684,685,739,740-743,751,752,753,
754, 758, 760, 790, 792
Towers and Reactors 216,217,230,

231,244,303,305,307,311,313,337,
338,357,375,385,403,419,432,433,
453-454,475,477,483,497,506,507,
509,581
AIka1Ineextraction 6u612
Chlorination 610
Chlorine dioxide 610-611
Contacting reactors 558, 559,608-609,
616-617
Contactors (see also Mixers) 603-604
Design criteria 327,600,604-609,656657
Displacement bleaching 546, 609
Downflow towers 217,304,305,398,
402,604,605,607,608,611,612~14
General design principles and
considerations 5~3
lnIet and discharge requirements for
towers ~
Mixer/reactors (see also Mixers) 608,
61+616
Oxygen-reinforced a1kaI1neextraction
towers 611,670
Peroxide towers 612,614
Safety considerations 61~20
Tray reactors 231,609
Troubleshooting 61~20
Upflow towers 216,308,309,381,384,
505,506,507,604-608,610-612,617
Upflow-downflow towers 381,384,600,
606,610-611
Toxicity (see Bleaching effluents)
Tristimulus values 510,704,706,707
U
Ultim-o process 649
Ultrafiltration 755, 757, 758
Unbleached chemical pulps 7
Bleachability 4~50
Chemical composition 10, 36, 38, 39,
40,~,50,244,255
Heterogeneity 48-49
lignin accessibility In 48
Optical properties of 36, 37, 41,48

Strength (mechanical) properties 45.
46-49
Unbleached
mechanical
and
chemimechanical
pulps
Bleachability 97, 463
Chemical composition 29
Optical properties of 37, 51-52
Strength (mechanical) properties
50-51,726,728-729,733,744
Uronic acid, uronic acid anydrides
45,684,685,686
Determination of 685-686
49,
29,
v
Vapor pressure
758
osmometry
Vent gases 823,824,826,827,829,
755, 757,
830
Viscosity 13, 36-37, 45,46-47, 223, 224225,233,234,235.236,237,250,251,

252,253,278,279,298,314,325,327328,329,330,331,333,349,352,354,
393,398,399,400,403,404,408,409,
410,427,428,435,437,612,613,626,
660,680,734,739,740
Relationship to paper strength 9,325,
679,680,734-735,742
Relationship to polymer weight and DP
37,46,298,679,726,734
Solvents used in determination 679,
681,720,827
W
216,229,244,477,659,668,
823
AIka1Ineextraction (including oxidantreinforced) 402,404,407,585,587,
588,590,662,666
Atmospheric diffusers 21,575,580581,584,609,650,671
Brown stock 228,359,586,627,632,
637,671
Chlorination-stage 254, 311, 660
Chlorine/chlorine dioxide-stage 587,
660, 662, 666
Chlorine dioxide-stage 660, 666
Discharge consistency 399,593,657,
668
1Vashers
Subject Index
Drum displacement 11,20,21,575,
576,579
Elimination of unneeded 659,669-670
Factors affecting selection of 575
H~orit~tage
398,402,588
Loading factors 576, 678
Manufacturing and design considerations
588-589
Material selections for different
bleaching stages 586-587
Oxygen-stage 587,590
Peroxide-stage 588
Pressure 23, 229, 572, 575, 578-579,
584,658,670
Pressure diffusion 433,572.581-582,
585,650,671,828
Three-washer bleach plant 666-667
Vacuum drum filter 216, 572, 575-578,
.
579, 583, 585, 586, 593,658, 668,
827,828
Wash presses 22, 572, 575, 576, 579580,582,584,658,671,828

Washing 36,310,392
Bleached high-yield pulp 592-594
Brown stock 234, 244, 252, 253, 275,
352,353,375,573,574,575,586,
589,650,666,668,669,671
Control 585-586
Countercurrent flow component 657-658
Defoamers and drainage aids 590,591-592
Dilution/extraction 571-572,650
Direct countercurrent 660-662
Displacement 571-572, 573, 579, 580,
581,593,650
Efficiency (performance parameters):
dilution factor, displacement ratio,
equlvalent displacement factor,Norden
efficiency factor, wash liquor ratio,
wash yield 105, 234, 572-575, 577,
579,582-583,632,653,657,659,668,
669
Equipment and equipment selection
575-583
First and second bleaching stages 585,
671
Improvement procedures 668-670
Jump-stage countercurrent 662,664,
6(j5
Jump-stage split-flow 665,668
Mechanical pulp 592-594
867
Ozone and peroxide stages 585

Pitch and extractives removal 587
Post-oXygen delignification 228,234,
235,236,511,573,574,580,583,
584,579,586,587,588,589,671
Second chlorine dioxide stage 587
Split flow countercurrent 662, 663, 665
Wash ratio (see also Efficiency under
Washing) 657, 662, 668
Water
Balance in bleach plant 652
Conservation measures in bleaching
668-670
Consumption by United States pulp
and paper industry 649
Mass balance in bleach plant, mass
balance calculation 654-656
Restricted use advantages in bleaching
651-654
Use in different washing sequences 650
Water (filtrate) reuse (see also under
Bleaching effluent) 649-672
Closed cycle operation 671-672
Factors affecting 658-660
Improved systems for 668-671
Non-d1lorine bleaching sequences
671-672
Whiteness 12,698, 703, 704
White Hquor 237, 315, 590,636,638,
831,832
White water 250,251,252,466,474,
506,660,661,662,663,664,665,666,
668,669,677,688
Wood
Anatomy and morphology 27-31,635,
724
Ash, ash content 29, 96
Chemical composition 29, 244
Chipping, chips 27,31,35,255,434,
454,455,463,677,734,744,809,
838
Combustion 810-811
Compression 446,447,448,725,809
Consumption 31
Residues 27,31,33
Species used for pulping in North
America 28, 31
Supply 32, 33
868
Pulp Bleaching
-Principles
and Practice
x
Xy)an (see Hemicelluloses)
xy1anases 48, 365, 366, 367, 368, 369,
370, 371, 372, 3?3, 375
Y
Yellowing (reversion) 406,417,469,
500,506,509,575
Aging tests 186,430
Effect of bleaching on 188-189
Effect of metal ions 190
Effect of pulping 188
Effect of oxygen 19&197
Effect ofwood species 187
Inhibition of 202-209
Light-induced 186, 1~209, 475, 487,
683
Mechanism of 197-202
Optical measurement of 185-186, 190191
Post-<:olor (PC) number 185, 186, 188,
189, 190, 191
Relative reflectivity 191-192
Thermal (heat-induced) 153, 185, 186190,209,298,475,683
z
Zero-span tensile test 371,679,680,
733, 745

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Pulp bleaching: principles

and practice / edited by Carlton W. Dence

Includes bibliographical references.

Section V:The Technology of Mechanical Pulp Bleaching

Section II: Raw Materials

II 2: Bleaching Chemicals: Chlorine Dioxide

Chlorine, Sodium Hydroxide,

Section III:The Chemistry of Bleaching

III 2: Reaction Principles in Pulp Bleaching

11I3:Chemistry of Chemical Pulp Bleaching

11I4:Chemistry of Mechanical Pulp Bleaching

III 5: Chemistry of Brightness Reversion and its Control

Section IV:The Technology of Chemical Pulp Bleaching

IV 3: Chlorine Dioxide in Delignification

IV 4: (Oxidative) Alkali Extraction

IV 6: Hydrogen Peroxide as a Delignifying Agent

IV 7: Enzyme Treatments of Pulp

IV 8: ChlorineDioxide in Bleaching Stages

IV 9: Hypochlorite and Hypochlorous Acid Bleaching

IV 11: Bleaching Shives and Dirt

V 1: Peroxide Bleaching of (Chemi)mechanical Pulps

V 2: Hydrosulfite (Dithionite) Bleaching

Section VI:Bleach Plant Operations. Equipment and Engineering

VI 2: Mixing and Mixers

V13: Washing and Washers

V14: Towers and Reactors

VIS: Sensorsand ProcessControl

VI 6: Water Reuseand Recycle

Section VII:The Properties

VII 1: Bleached Pulp Composition and Its Determination

VII 2: Brightness: Basic Principles and Measurement

VII 3: Strength Properties and Characteristics of Bleached Chemical

VIII: Pulp Bleaching

and The Environment

VIII1: Effluent Characteristics and Composition

VIII 2: Assessing the Potential Impacts of Pulping and

and Furansin Effluent,Pulp,and SolidWaste

VIII 4: Bleach Plant Air Emissions

As can be inferred from the title of the

was published. For example, the present

Chapter I I: Introduction to Principles & Practice of Pulp Bleaching

billty,and enhancing some of its properties.

Pulp Bleaching - Principles and Practice

costs include those of chemicals, steam, and

to Principles & Practice of Pulp Bleaching

Pulp Bleaching - Principles and Practice

development in the 1950s of the five-stage

first in Sweden and then in Canada. Further development

Table 1. Global bletwbe4ftber j1rotbIelfmt Cflptldly I" 1994 (8).

r.bk 3. Pm4IIetIoIr of bletu:be4 palp.

because of the relatively high proof softwood

Bleaching not only adds to the selling

bleached pulp is notoriously

achieve the production

of paper and board

indicated in Table 2. Imports cannot be

North America, softwood dominates mar-