Journal of the Air Pollution Control Association

ISSN: 0002-2470 (Print) (Online) Journal homepage: https://www.tandfonline.com/loi/uawm16

Black Liquor Oxidation as a Method for Reducing

Air Pollution from Sulfate Pulping

E. R. Hendrickson Ph.D. & C. I. Harding Ph.D.

To cite this article: E. R. Hendrickson Ph.D. & C. I. Harding Ph.D. (1964) Black Liquor Oxidation
as a Method for Reducing Air Pollution from Sulfate Pulping, Journal of the Air Pollution Control
Association, 14:12, 487-490, DOI: 10.1080/00022470.1964.10468320

To link to this article: https://doi.org/10.1080/00022470.1964.10468320

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E. R. HENDRICKSON, PhD,
Professor
and C. I. HARDING, Ph.D.,
Assistant Research Professor,
Air Pollution Research Laboratory,
University of Florida,
Gainesville
Black Liquor Oxidation as a
Method for Reducing Air Pollution
from Sulfate Pulping*
This paper will discuss the sources of odorous air pollutants from sulfate pulping op-
erations. One of the major sources is the recovery furnace. Odors from this source
can be reduced considerably by oxidation of the black liquor prior to evaporation and
burning. The procedure has been used with considerable success in the northwestern
and northeastern parts of the United States. Unfortunately, the majority of sulfate pulp
production occurs in areas where southern pine is the basic raw material. For several
reasons the black liquor resulting from southern pine operations presents problems
when the usual oxidation procedures are used. Although not as effective as normal
black liquor oxidation strong black liquor can be oxidized without too much difficulty.
Various procedures for oxidation of black liquor will be discussed. Results of stack
sampling in U. S. pulp mills with and without the oxidation unit in operation will be
reported.

N learly all of the paper produced

in the United States today is derived
from wood as the raw material. The
cellulosic components of the wood may
be prepared for paper making by several
chemical processes including sulfite,
soda, and sulfate or kraft. Since the
kraft process can be used to produce
pulp from a variety of wood species and
since the pulp thus produced can be
used for making a variety of paper
products ranging from brown wrapping
paper to white writing paper to "dis-
solving cellulose," it has developed into
the most popular pulping process in the
United States. At present more than
17 million tons of paper pulp are pro-
duced in this country each year by this
process. This represents considerably
more than half of the total wood pulp
produced chemically in the United
States.
The sulfate process is so named be-
cause the makeup chemical is added
mainly in the form of salt cake or so-
dium sulfate. It is more popularly
known as the kraft process from the
German word for strong < which is in-
dicative of the strength of the paper
kraft pulping and chemical recovery.
The active chemicals in the white liquor
used for pulping are sodium sulfide,
sodium hydrosulfide, and sodium hy-
droxide. When the cooking liquor and
wood chips are combined in the digester
under high temperature and pressure
the active chemicals dissolve away the
the noncellulosic parts of the wood and
free the bundles of cellulose fibers. A
variety of organic and inorganic com-
pounds is formed and accumulates in
the black liquor. Some of the com-
pounds are combined with sulfur. The
spent cooking liquor is separated from
the wood pulp to complete the kraft
pulping cycle. This spent cooking liq-
uor is now known as black liquor and
an essential part of the economic balance
of the kraft process is recovery of the
cooking chemicals and heat from the
black liquor. In general, this is accom-
plished by condensing the black liquor
in multiple-effect and direct-heat evap-
orators before burning it in a recovery
furnace. The numbers shown on Fig-
ure 1 represent losses of gaseous sulfur
compounds from the various processes.
These figures represent losses in pounds
of compounds per ton of pulp produced.
As much as 100 pounds of such losses
per ton of pulp may occur if no special
procedures are used to prevent them.
A variety of compounds containing
sulfur is to be found in the black liquor,
including mercaptides, sulfides, and
disulfides. These compounds contrib-
ute to the characteristic odor of black liq-
Kraft Pulping
Multiple Effect
Evaporators

produced from the pulp. The kraft

process has been described in detail in
i I
I Soap Skimming
several publications including a pre-
vious one from this laboratory.1- 2 For
the purpose of this paper the discussion
of the process itself will be limited to a Smelt
Dissolving
schematic diagram shown in Fig. 1. Tank

It will be noted that there are two

essential elements to the process:
Black Liquor Green Liquor White Liquor
or Smelt

* Presented at the 57th Annual Meeting

Shamrock-Hilton Hotel, June 20-21, 1964,
Houston, Texas. Fig. 1. Flow diagram for kraft pulping and recovery process.

December 1964 / Volume 14, No. 12 487


Fig. 2 Scheme for incineration of noncondens-
able gases from digester and blow tank.
uor and when they are released contrib-
ute to the typical odors associated with
kraft pulping. The concentration of
the various constituents in the black
liquor varies from mill to mill and
within a given mill from time to time
depending on several variables including
operating conditions, the type of wood
being pulped, and the type of pulp being
produced. In practically all instances,
however, the sulfur compounds men-
tioned above are present in some con-
centration.
When the black liquor enters the
multiple-effect evaporators some of the
sodium sulfide is hydrolized and may
be lost as hydrogen sulfide gas. Under
similar conditions mercaptides may
hydrolize to form methyl mercaptan.
Methyl mercaptan, hydrogen sulfide,
and methyl sulfide may all be released
in the multiple-effect evaporator simply
because of their low vapor pressure.
It will be noted that the multiple-effect
evaporators are the second largest
source of gaseous sulfur losses in the
process.
In nearly all mills the black liquor is
further concentrated by passing it
through direct-heat evaporators heated
by flue gases from the recovery furnace.
Theoretically, carbon dioxide in the
flue gases results in the formation of
hydrogen sulfide from sodium sulfide
according to the following reaction:
Na2S + CO2 + H2O -^ Na2CO3 + H2S
The hydrogen sulfide released from this
source frequently shows up in the com-
bined stack gases from the recovery
furnace. Actually the recovery fur-
nace is the largest source of gaseous
sulfur losses in the mill. Hydrogen
sulfide and sulfur dioxide plus traces of
mercaptans and disulfide arise from this
source.
Several methods have been proposed
for reducing gaseous sulfur losses from
pulp mills and converting odorous sulfur
compounds to less obnoxious ones. One
or more of these methods may be em-
ployed at a given mill. One procedure
involves the use of wet scrubbers on the
stack gases from the recovery furnace.
Venturi-type scrubbers are most fre-
quently used for this purpose with
water, caustic, or black liquor serving
as the liquid phase. Recent field in-
488
vestigations by this laboratory reveal
excellent reduction of SO2, H2S, and
RSH using black liquor for scrubbing
Another procedure oxidizes the non-
condensable gases from the digester and
blow tank. The oxidation may be
accomplished by mixing with bleach
plant effluent or by burning. Several
west coast mills have installed equip-
ment to incinerate the odorous gases.3
One of the most recent installations is
shown in Fig. 2.4 Special precautions
must be taken to insure proper dilution
with air and to reduce explosion haz-
ards. The procedure which is possibly
most effective in reducing gaseous sulfur
losses from evaporators and the re-
covery furnace is black liquor oxida-
tion. If the sulfur compounds in the
black liquor are oxidized they are less
volatile and hence are less likely to be
released under the processing condi-
tions. It is estimated that sulfur losses
from the recovery furnace can be de-
creased as much as 95% and losses from
multiple-effect evaporators reduced sig-
nificantly by appropriate oxidation of
the black liquor.5
Most workers today recognize that
M. G. Schmitt about 1938 reported the
original work which embodied the
present concept of black liquor oxida-
tion. A complete report of Schmitt's
work was never published, but Collins
discussed the work in a recent paper.5
Since Schmitt's original work a few
groups of researchers in Sweden,
Canada, and the United States have
advanced the storehouse of knowledge
with respect to black liquor oxidation.
Some of the earliest work was done in
Sweden in the late 1920's.6 This re-
sulted in a system which performed as
a nonfoaming aerator and evaporator
but not actually as an oxidation unit.
The first commercial oxidation unit was
based on the work of Bergstrom and
Trobeck.5 Much of the knowledge
until very recently has been based on
the work of these two researchers in
Sweden. Groups of workers in the
United States and Canada 7~13 fur-
ther developed the processes and added
to our knowledge of it.
The original theory of black liquor
oxidation proposed by Trobeck14 is
shown by the following two equations:
2Na2S + 20o + H,0 ->
Na2S2O3 + 2NaOH
and
Na2S2O3 + 2NaOH + 202 -+
2Na2SO4 + H2O
Fones and Sapp15 in studying the oxida-
tion of weak black liquor at digester
conditions with pure oxygen felt that
oxidation proceeded as shown in Fig.
3. A sulfur balance on their data
does not account for all sulfur in the
reaction. They indicated that at 100
to 120 pounds per square inch the sul-
fide was oxidized to thiosulfate which
Fig. 3. Fate of sulfur compounds during oxida-
tion at 100-120 psi pressure using pure
oxygen.
in turn was oxidized to sulfate. Under
the conditions existing in the evapora-
tors and the furnace neither the thio-
sulfate nor the sulfate result in the
emission of gaseous sulfur compounds.
The effect of black liquor oxidation on
mercaptans is controversial. Some
workers report that oxidation takes
place and others that it does not. More
recent work at the Air Pollution Re-
search Laboratory at the University of
Florida12 where black liquor was oxi-
dized with pure oxygen at atmospheric
pressure and between 60°C and 90°C
indicates that the oxidation proceeds
according to the following two reactions:
4NaHS + O2 -*- 2Na2S2 + 2H2O
and
2NaHS + 202 -> Na2S2O3 + H2O
Ricca12 also found that no increase in
sulfate occurred in his experiments.
Typical results are shown in Fig. 4. A
lack of sulfate buildup may be accounted
for by differences in black liquor.
The identification of the polysulfide ac-
counts for nearly all of the sulfur in the
reaction. It was further found that
at temperatures below 60°C there was
a tendency to produce elemental sulfur
in small quantities. With the presence
of sodium hydroxide in the black liquor,
however, the elemental sulfur event-
ually reacted to form sodium sulfide
and sodium thiosulfate. In theory
then, the oxidation of black liquor prior
to its concentration in multiple-effect
evaporators results in the formation of
more stable sulfur compounds which
will not be released under existing con-
ditions of temperature and pressure.
Furthermore, the release of hydrogen
sulfide from the recovery furnace will
be reduced although the production of
sulfur dioxide may increase slightly as
compared with the burning of non-
oxidized liquor. The theory is borne
out in practice. The results of black
liquor oxidation on recovery stack
emissions is shown in Table I. The
data illustrate not only the dramatic
reductions which can result from this
process change but also the great varia-
tions in emissions which can be ex-
pected from one mill to another. Sev-
eral mills have reported that less dif-
ficulty is experienced in burning oxi-
Journal of the Air Pollution Control Association
 Table I
Without With
.—BLO—.
H2S SO2 H2S SO2
ppm ppm ppm ppm
52
Mill A 508 369 426
MillB 1560 2 95 9 „.—•
dized liquor than in burning nonoxidized
liquor.
From the point of view of the public
and of the air pollution control agencies
the reduction in concentration of mal-
odors from the evaporators and from
the recovery furnace is the most im-
portant result of black liquor oxidation.
Unfortunately, many times odor con-
trol is judged on an all or nothing basis.
The public generally is concerned more
with the presence or absence of odors
than their intensity. There are other
benefits that accrue to the producers
from black liquor oxidation. Tro-
beck14 originally pointed out that evap-
orator corrosion occurred by the re-
action between hydrogen sulfide and
oxygen to produce sulfuric acid. It
should follow therefore that the reduc-
tion of hydrogen sulfide concentration
in the liquor should reduce the amount
of corrosion in the evaporators. By
reducing the concentration of mal-
odorous compounds in the condensate
from the evaporator it makes possible
the reuse of this water in many parts
of the mill with a subsequent reduction
in water usage and a savings in heat.
When black liquor is oxidized the con-
servation of sulfur results in higher sul-
fidity of the cooking liquor. This has
the advantage of making possible the
use of other makeup chemicals which
may be cheaper, and reduced lime re-
quirements for causticizing. There are
also some savings to be realized from
a lower power requirement due to more
efficient heat transfer in an oxidized
liquor system.
There are some disadvantages to
black liquor oxidation; mainly in the
cost of constructing, maintaining, and
operating the black liquor oxidation
system. In some instances it has been
reported that the savings in chemicals
does not recover this investment. In
a few instances scaling was noticed in
the evaporators when using oxidized
liquor.
In the United States the majority of
sulfate pulp production occurs in the
southeastern states and in the north-
west. In the northwest the character-
istics of the wood pulped are somewhat
different from that in other regions.
The first black liquor oxidation units
in this country were installed in north-
western mills and at present 15 to 20
mills in that region conduct black liquor
oxidation as an integral part of their
process. In practically all instances
December 1964 / Volume 14, No. 12
Oxygen Actively ^ _ _ _ _ _ _ _ _ — •
Absorbed
" without the production of foam pro-
1
-__^
0 20 40 60 80
Fig. 4. Fate of sulfur compounds during static
oxidation with pure oxygen at 75°C and atmos-
pheric pressure.
these mills oxidize the liquor prior to
the evaporators. Black liquor oxida-
tion units take three general forms:
packed towers, thin film oxidizers, and
porous plate aerators. These various
types of units have the advantages and
disadvantages well known to chemical
engineers. Air is used as the source of
oxygen and except in those places where
pine is pulped no excessive foam is
produced.
As one moves eastward across the
country more and more severe foam
problems are found until they reach
their peak in the pine pulped in the
southeast. Southern pine has a large
concentration of fats and resin. The
alkaline pulping liquor converts these
into sodium soaps with a high foam
potential. The procedures used in
northwestern mills for oxidation of
black liquor have been tried with modi-
fication in several southeastern mills.
The stable foam which is produced
during the oxidation has resulted in
abandonment of these procedures. Col-
lins16 developed a system for oxidizing
the black liquor resulting from the
pulping of southern pine. His system
involved the removal of as much soap
as possible in a foaming type tower.
Other attempts have been made to oxi-
dize weak black liquor in southern mills
with pure oxygen.12 At the present
time the economics of a pure oxygen
system are not good. Following some
initial investigations using pure oxygen,
Hawkins17 began experimenting with
the oxidation of black liquor after
evaporation. He worked on liquor with
40 to 50% solids. He found that better
than 98% of the sulfide in the liquor
could be oxidized with less production
of foam. What foam is produced can
be controlled with the use of fuel oil or
mechanical foam breakers. Since the
initial installation of a strong black
liquor oxidation unit at the Champion
Paper Company in Texas, one other
southern mill has installed such units
and others are contemplated. This
mode of black liquor oxidation has been
necessary in order to avoid the severe
foam problems with southern black
liquor. It has the obvious disadvan-
tage that there is no reduction in the
amount of malodorous compounds re-
Sodium Thiosulfo
leased from the evaporators. Sulfur
losses from the recovery furnace, how-
ever, are reduced by this procedure.
Landry18 attempted the oxidation of
weak black liquor from southern mills
utilizing a falling film type oxidizer.
Sodium Sulfote
He felt that the liquor could be oxidized
Sodium Polysulfide
f Sodium Sulfide
vided the loading rate was kept low.
100 120 140 160 With a loading rate of 10 pounds of so-
dium sulfide per thousand square feet
per hour he obtained 100 per cent oxi-
dation of the sulfides. When this was
increased to a loading rate of 50 the
oxidation was reduced to 28%. Landry
felt that the rates investigated where no
foam was produced were too low to be
feasible.
Surveys have been conducted on
several northwestern mills utilizing
weak black liquor oxidation and several
southeastern mills utilizing strong black
liquor oxidation to attempt to compare
the two procedures. Unfortunately,
the data have not been obtained in the
same manner nor on the same basis and
thus makes comparisons difficult. It
has been reported that sulfur savings of
about 32 pounds per ton of pulp have
been realized from strong black liquor
oxidation as compared with an average
of 43 pounds per ton of pulp for weak
black liquor oxidation. In both proc-
esses the reduction of gaseous sulfur
emissions from the recoverv stacks has
Fig. 5. Hydrogen sulfide emission from a kraft
recovery furnace with increasing load.
ranged from 80 to 95%. Figures of
this type, however, do not give the com-
plete picture. The discharge of hydro-
gen sulfide from a recovery furnace, for
example, depends on a number of factors
including composition of the liquor
feed, the rate of liquor feed, combustion
conditions in the furnace, amount of
excess air admitted to the furnace, and
percentage of design load at which the
furnace is operated. It is known, for
example, that the hydrogen sulfide con-
centration in the off gases from a fur-
nace operated at greater than 100% of
design capacity increases nearly ex-
ponentially. Recent field work by
this laboratory produced the results
shown in Fig. 5. It is to be noted that
the data are limited and confined to
one furnace. The shape of the curve,
however, approximates that given by
489
Wright19. Wright stated that the in-
creasing H2S losses at higher loadings
resulted from, a cutback in secondary
air in an attempt to prevent overheating
of an overloaded furnace. The losses
indicated in Fig. 5 occurred with no
reduction of secondary air. A reduction
of this nature would tend to increase
the loss of H2S. Thus the apparent
effectiveness of black liquor oxidation
would be considerably greater from an
overloaded furnace than for one oper-
ating at design capacity.
Oxidation of kraft black liquor is one
of the most effective ways of reducing
the loss of gaseous sulfur compounds
from the sulfate pulping process. The
design and installation of oxidation
units is mainly a problem for individual
mills since processes found satisfactory
at one location may not be applicable
to another. This is particularly true
for pulp mills in the southeast. Al-
though the problems of oxidizing black
liquor from southern pine have been
solved to some extent by strong black
liquor oxidation, the maximum bene-
fits cannot be achieved by this process.
The Air Pollution Research Laboratory
at the University of Florida has re-
cently completed some new work on
weak black liquor oxidation. The new
process provides sufficient financial re-
turns from recovery of salable products
to justify elaborate foam breaking
equipment and make weak black liquor
oxidation economically attractive.
This work will be reported in the
following paper.
Summary
Several methods have been proposed
for reducing gaseous sulfur losses from
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490
pulp mills and converting odorous com-
pounds to less obnoxious ones. One
or more of these methods may be em-
ployed at a given mill. One of the
procedures involves the use of wet
scrubbers following the primary collec-
tion device on the stack gases from the
recovery furnace. Another procedure
oxidizes the non-condensable gases from
the digester and blow tank. Oxidation
of kraft black liquor prior to burning in
the recovery furnace is one of the most
effective ways of reducing the loss of
gaseous sulfur compounds from the sul-
fate pulping processes. Reduction of
gaseous sulfur emissions from the re-
covery stacks may range up to 80 to
95%. The theory, practice, and prob-
lems of black liquor oxidation are de-
scribed in the paper. Unfortunately,
black liquor oxidation processes found
satisfactory at one location may not be
applicable to another and thus the proc-
ess must be tailored to the individual
installation.
REFERENCES
1. J. N. Stephenson, Ed., Pulp and
Paper Manufacture—Volume I, Prep-
aration and Treatment of Wood Pulp,
McGraw-Hill, New York (1950).
2. E. R. Hendrickson, C. G. Walker and
V. D. Chapnerkar, "Identification of
Non-sulfur Compounds in Stack Gases
from Pulp Mills," American In-
dustrial Hygiene Association J., 24:
pp. 121-126 (March-April 1963).
3. G. G. DeHaas, and G. A. Hansen,
"The Abatement of Kraft Pulp Mill
Odors by Burning," TAPPI, 38:
pp. 732-738 (December 1955).
4. A. A. Coleman, "The Combustion of
Noncondensable Blow and Relief
Gases in the Lime Kiln," TAPPI,
41: pp. 166A (October 1958).
5. T. T. Collins, Jr., "The Oxidation of
Sulfate Black Liquor," A review of the
literature in two parts: Paper Trade
Journal, 136: pp. 19-24 (March 27,
SCOTT RESEARCH
LABORATORIES, INC.
MOTOR VEHICLE POLLUTION
CONTROL DEVICE TESTING
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Photochemistry, combustion, corrosion,
surface chemistry, fuel and lube additives,
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GASES & GAS MIXTURES
For instrument calibration
P. O. BOX 66, PERKASIE, PA. 18944
215-249-3526
P.O. BOX 2416,
SAN BERNARDINO, CALIF. 92406
714-TURNER 7-2571
1963); and Paper Trade Journal,
136: pp. 37-40 (March 20, 1963).
6. T. T. Collins, Jr., "The Oxidation of
Sulfate Black Liquor," Paper Trade
Journal, 131: pp. 30-38 (October 12,
1950).
7. H. W. Bialkowsky, and G. G. DeHaas,
"Stabilization of Douglas Fir Kraft
Black Liquor," Paper Mill News,
74: pp. 14-22 (September 1,1951).
8. C. L. Tomlinson, and J. M. Ferguson,
"Odor Abatement in an Alkaline
Pulp Mill," Pulp and Paper Magazine
(Canada), 57: pp. 119-122 (December
1956).
9. F. E. Murray, "The Kinetics of
Oxidation of Kraft Weak Black
Liquor," TAPPI, 42: pp. 761-766
(September 1959).
10. R. H. Wright, "British Columbia
Research Council Discovers Method
to Reduce Kraft Mill Odors," Paper
Trade Journal, 134: pp. 14 (January
11, 1954).
11. R. H. Wright, "Kinetics of the Ox-
idation of Sulfate Black Liquor,"
TAPPI, 35: pp. 276-280 (June 1952).
12. P. M. Ricca, "A Study in the Ox-
idation of Kraft Black Liquor,"
(Unpublished Ph.D. dissertation, Uni-
versity of Florida, February 1962).
13. J. E. Landry, "Black Liquor Oxidation
Practice and Development—A Critical
Review," TAPPI, 46: pp. 766-772
(December 1963).
14. K. G. Trobeck, "Some Data on the
Oxidation of Black Liquor," Paper
Trade Journal, 135: pp. 27-31 (July
4, 1952).
15. R. E. Fones, and J. E. Sapp, "Ox-
idation of Kraft Black Liquor with
Pure Oxygen," TAPPI, 43: pp.
369-373 (April 1960).
16. T. T. Collins, Jr., U. S. Patent, 2,999,-
044 (September 5, 1961).
17. G. Hawkins, "Black Liquor Oxidation
at Champion's Texas Mill Has
Unusual Twist," Paper Trade Journal,
146: pp. 38-39 (March 5,1962).
18. J. E. Landry, "A Study in the Ox-
idation of Kraft Black Liquor,"
(Unpublished M.S. thesis, Louisiana
State University, August, 1963).
19. R. H. Wright, "New Work in Kraft
Mill Odor Control," / . of the Air
Poll. Control Assoc, 13: pp. 101-104
(March 1963).
JACKSON & MORELAND
DIVISION OF UNITED
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