Coal and Coal Products: Analytical Characterization Techniques

Publication Date: November 12, 1982 | doi: 10.1021/bk-1982-0205.
fw001
Coal and Coal Products:

Analytical Characterization
Techniques
In Coal and Coal Products: Analytical Characterization Techniques; Fuller, E.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
Publication Date: November 12, 1982 | doi: 10.1021/bk-1982-0205.fw001

Coal and Coal Products:
Analytical Characterization
Techniques
E. L. Fuller, Jr., EDITOR

Union Carbide Nuclear Division
Sponsored by the ACS
Divisions of Analytical,
Fuel, and Colloid
and Surface Chemistry
ACS SYMPOSIUM SERIES 205
AMERICAN CHEMICAL SOCIETY
WASHINGTON, D. C. 1982

Library of Congress Cataloging in Publication Data
Coal and coal products.
(ACS symposium series, ISSN 0097-6156; 205)
Includes bibliographies and index.
1. Coal—Analysis—Congresses.
I. Fuller, E. L. II. American Chemical Society.
Division of Analytical Chemistry. III. American
Chemical Society. Division of Fuel Chemistry. IV.
American Chemical Society. Division of Colloid and
Surface Chemistry. V. Series.
TP325.C5145 1948 622.6'22 82-18442
ISBN 0-8412-0748-8 ACSMC8 205 1-326
1982
Copyright © 1982
American Chemical Society

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PREFACE
THE INDUSTRIAL REVOLUTION was based upon efficient use of mechanical

energy for production and processing of materials. The initial source of
this energy came from the thermal energy stored in coal, but rapid advan
mentsweremade,andpetroleumsoonreplacedcoalastheprimesource
of energy to support an increased standard of living for mankind. The
world's population has increased to such a staggering extent that the
Publication Date: November 12, 1982 | doi: 10.1021/bk-1982-0205.pr001
machines that were such a luxury a century ago have now become nece
ties just to provide essential life-supporting food, clothing, and shelter.
Only a degree of "independence" and self-sufficiency can be achieved, a
each of us must work to provide services and products that are needed
by others. This increase in efficiency allows us to inhabit the earth at a
population density and state of well being far in excess of the hunter/
farmer status of the past.
However, this mode of operation strains our natural resource suppl
to varying degrees. The recent "energy crisis" serves a good purpose: it
points out that comprehensive planning and research are required to ensure
that mankind can flourish and that the raw materials are carefully and
efficiently utilized. The simple political control of one supply of energy
(crude oil in this case) from one rather small geographic region has suddenly
impacted the global market to "crisis" proportions. Systematic planning
and foresight will be required to avoid crises reminiscent of the "energy
crisis" that came about when the hardwood forests were decimated to
provide charcoal for the steel industry.
We now have adequate information, processing capabilities, techni
knowledge, and trained personnel to ensure that smooth transitions can
implemented without the tragic impact of "crisis" situations. Our sourc
of energy can be brought into play without significant impact on the
environment if proper comprehensive analysis is employed. Coal still rei
among sources of energy in terms of the amount and availability. The
generically related materials (oil shales, tar sands, lignite, peat, heavy o
etc.) further extend the importance of fossil fuels for energy bases.
This volume represents a small step toward the research and inter-
disciplinary communications required to return efficiently to our large
reservesofcoalforaprimarysourceofenergy.Eachpresentationchosen
ix

for this volume represents a significant contribution to either a specific area
of technical importance in coal processing and utilization, or a specific
application of a given method of analysis as applicable to various coals and/
or derived products.
New and/or alternate approaches to studies of the structure and
chemistry of coals and related materials will yield increased productivity
and improved environments. In our small way this treatise is our current
international effort to advance the technology we all need.
E. L. FULLER, JR.
Union Carbide Nuclear Division
Oak Ridge, TN 37830
Publication Date: November 12, 1982 | doi: 10.1021/bk-1982-0205.pr001
August 1982

1
Theoretical and Experimental Approaches

to the Carbonization of Coal and Coal Blends
MAGGI FORREST and HARRY MARSH

University of Newcastle upon Tyne, Northern Carbon Research Labs,
School of Chemistry, Newcastle upon Tyne, NE1 75U, England
Publication Date: November 12, 1982 | doi: 10.1021/bk-1982-0205.ch001
Mechanisms of carbonization of fluid systems from pitches and

coals of different origin and rank to form anisotropic cokes are
discussed. The concept of nematic liquid crystals and mesophase is
introduced. The origins of optical texture in cokes and the
chemical and physical factors which control the size and shape of
optical texture are explained. The significance of optical texture
in metallurgical cokes is analysed in terms of coke strength and
chemical reactivity. Laboratory experimental approaches include
control over carbonization procedures, the examination of polished
surfaces of resultant cokes by optical microscopy, the use of
scanning electron microscopy to monitor changes induced by thermal
treatment and gasification of cokes, as well as point-counting of
optical texture and the use of microstrength testing procedures.
Modern technological approaches to the successful use of coals of
several ranks to make metallurgical coke include blending of coals
sometimes with pitch additions. The resultant enhancement of coke
strength is explained in terms of the development of suitable
optical texture from solutions of coal in coal or of pitch in coal.
Hydrogen transfer reactions are important here. The use of breeze
additions in coal blends is commented upon.
Metallurgical coke is used in the blast furnace as an energy

source, a chemical reducing agent and to provide permeability and
support for the furnace load. To fulfil these functions and
maintain blast furnace performance the coke must maintain i t s size
within an optimum range. It must therefore be able to maintain
its mechanical strength and to withstand degradation due to gasifi-
cation in carbon dioxide, abrasion, compressive forces and thermal
shock in the furnace. Prime coking coals of volatile content
19-33% are becoming scarce in Western Europe and Japan and economic
necessity dictates the need for the development of blending
0097-6156/82/0205-0001$07.50/0
© 1982 American Chemical Society

2 COAL AND COAL PRODUCTS
procedures which make use of c o a l s of v o l a t i l e content above and

below t h i s c r i t i c a l range. The c h a r a c t e r i s t i c s of cokes from such
blends must f a l l w i t h i n s t r i n g e n t s p e c i f i c a t i o n s to m a i n t a i n b l a s t
furnace performance ( 1 ) . I t i s t h e r e f o r e necessary to combine the
r e s u l t s of fundamental research w i t h experience gained from the
past e m p i r i c a l approach to c o a l blending (£). The purpose of t h i s
paper i s to d i s c u s s recent t h e o r e t i c a l c o n s i d e r a t i o n s and e x p e r i -
mental s t u d i e s of c o a l and c o a l / p i t c h blending procedures,
g a s i f i c a t i o n and thermal treatment of m e t a l l u r g i c a l cokes and the
e f f e c t s of p i t c h coke breeze a d d i t i v e s upon coke s t r e n g t h .
The C a r b o n i z a t i o n Process
The Formation of A n i s o t r o p i c Carbon. As c o a l i s heated i t

undergoes d e p o l y m e r i z a t i o n and decomposition r e s u l t i n g i n the
e v o l u t i o n of gas and condensible vapours and leaves behind a s o l i d
r e s i d u e of high carbon content (2). The a b i l i t y of some c o a l s to
s o f t e n and become p l a s t i c upon h e a t i n g , c o a l e s c i n g to form a
coherent mass, i s the property upon which the formation of coke
depends (4). Such c o a l s are described as caking c o a l s .
Over the temperature range 623 K to 773 K, caking c o a l s begin

to s o f t e n , c o a l e s c e , s w e l l and then r e - s o l i d i f y i n t o a porous
s t r u c t u r e which, at temperatures j u s t above the r e s o l i d i f i c a t i o n
temperature, i s green coke.
I n i t i a l s o f t e n i n g of the c o a l i s due to increased thermal

a g i t a t i o n . At the same time, but independently of the p h y s i c a l
process, p y r o l y s i s begins to modify the v i s c o s i t y of the c o a l by
breakage of the chemical c r o s s - l i n k a g e s r e s p o n s i b l e f o r making
c o a l a polymeric m a t e r i a l . S w e l l i n g of the mass i s due to the
e v o l u t i o n of v o l a t i l e matter which cannot escape from the c o a l mass
and which encounters r e s i s t a n c e to i t s f l o w through macropores and
f i s s u r e s i n the c o a l C5).
R e s o l i d i f i c a t i o n of the c o a l i s due to chemical c r o s s - l i n k i n g

of molecular c o n s t i t u e n t s so c o n v e r t i n g the p l a s t i c s t a t e i n t o a
v i s c o - e l a s t i c s t a t e and f i n a l l y i n t o a b r i t t l e porous s o l i d .
S i m i l a r l y , c o a l t a r and petroleum p i t c h e s , on c a r b o n i z a t i o n ,
form a f l u i d m e l t . The v i s c o s i t y of t h i s melt i n i t i a l l y decreases
w i t h i n c r e a s i n g temperature and then increases once again as
molecular r e a c t i v i t y leads to chemical p o l y m e r i z a t i o n . Eventually
these m a t e r i a l s form the a n i s o t r o p i c g r a p h i t i z a b l e cokes.
I t i s d u r i n g the p l a s t i c ( f l u i d ) stages of c a r b o n i z a t i o n that

the most important f e a t u r e s of coke s t r u c t u r e are formed,
p a r t i c u l a r l y p o r o s i t y (6) and pore w a l l s t r u c t u r e . During the
p l a s t i c stage, the o p t i c a l l y i s o t r o p i c parent m a t e r i a l undergoes
a phase t r a n s i t i o n to an o p t i c a l l y a n i s o t r o p i c melt which f i n a l l y

1. FORREST AND MARSH Carbonization of Coal and Coal Blends 3
forms an a n i s o t r o p i c coke. The s i g n i f i c a n c e of t h i s phase

t r a n s i t i o n to coke p r o p e r t i e s i s profound, as w i l l be shown.
L i q u i d C r y s t a l s and Mesophase
Conventional L i q u i d C r y s t a l s . There e x i s t some ( g e n e r a l l y

o r g a n i c ) systems which do not pass d i r e c t l y from a s o l i d t o a
l i q u i d on h e a t i n g but do so v i a d i s t i n c t phases, c a l l e d l i q u i d
c r y s t a l s , having p r o p e r t i e s i n t e r m e d i a t e between s o l i d s and
l i q u i d s . The t r a n s i t i o n a l symmetry of a s o l i d c r y s t a l i s not
present i n l i q u i d s , a l t h o u g h dynamic l o c a l p o s i t i o n a l o r d e r i n g
( s t a t i s t i c a l o r d e r ) i s p r e s e n t , extending over 1 nm and l a s t i n g
f o r 10 to 100 molecular i n t e r a c t i o n s . I n a l i q u i d c r y s t a l phase,
however, there i s w e l l d e f i n e d order on a l e n g t h s c a l e of 10^ urn

although f l u i d p r o p e r t i e s are a l s o w e l l d e f i n e d . V i s c o s i t i e s are
measurable and of the order of 10^ to 10** Nsm~ . Conventional
l i q u i d c r y s t a l s (known s i n c e 1880) w i l l d i s s o c i a t e and r e v e r t to
normal l i q u i d s on h e a t i n g . There a r e s e v e r a l types of l i q u i d
c r y s t a l , nematics, smectics and c h o l e s t e r i c s , of which o n l y
nematics w i l l be d i s c u s s e d here ( 7 ) . Conventional nematics are
composed of r o d - l i k e molecules, p o l a r and w i t h o u t f a c i l i t y of
i n t r a - m o l e c u l a r r o t a t i o n . The long axes of these rods are a l i g n e d
about a common d i r e c t i o n i n space, the d i r e c t o r v e c t o r , n, which
i s an a x i s of r o t a t i o n a l symmetry f o r a l l macroscopic p r o p e r t i e s .
The p o s i t i o n s of the c e n t r e s of mass of the rods a r e randomly
d i s t r i b u t e d ; t h e r e i s no long range order and an X-ray d i f f r a c t i o n
p a t t e r n would show no Bragg peaks. A nematic l i q u i d c r y s t a l i s
u n i a x i a l w i t h the o p t i c a x i s along n.
L i q u i d C r y s t a l s i n Carbonaceous Systems. The f o r m a t i o n of

a n i s o t r o p i c carbon from the i s o t r o p i c melt of p i t c h or c o a l was
f i r s t a t t r i b u t e d t o the presence of a l i q u i d c r y s t a l phase by
Brooks and T a y l o r ( 8 ) . The i s o t r o p i c m e l t undergoes a p h y s i c a l
phase t r a n s i t i o n to a l a m e l l a r nematic l i q u i d c r y s t a l . There are
important d i f f e r e n c e s between the l a m e l l a r nematics a s s o c i a t e d
w i t h carbons and c o n v e n t i o n a l r o d - l i k e nematics. Their p h y s i c a l
p r o p e r t i e s are e s s e n t i a l l y i d e n t i c a l but c h e m i c a l l y they are q u i t e
d i f f e r e n t . C o n v e n t i o n a l nematics a r e c h e m i c a l l y s t a b l e w h i l e
p i t c h or c o a l l a m e l l a r nematics i n a p y r o l y s i n g system are
extremely r e a c t i v e . The important d i s t i n c t i o n of shape of
c o n s t i t u e n t molecules must a l s o be emphasised; a c o n v e n t i o n a l
nematic c o n s i s t s of long rods a l i g n e d about n w h i l e carbonaceous
mesophase i s composed of p l a t e - l i k e m o l e c u l e s . Here i t i s the
normal to the surface of the molecule (again the a x i s of symmetry)
which i s a l i g n e d p a r a l l e l to g. F u r t h e r , i n c o n v e n t i o n a l l i q u i d
c r y s t a l s the phase change from l i q u i d t o l i q u i d c r y s t a l i s brought
about by a r e d u c t i o n i n k i n e t i c energy (molecular m o b i l i t y ) by
lowering the temperature; i n the carbonaceous mesophase molecular
m o b i l i t y i s reduced to a p o i n t where i t i s f a v o u r a b l e f o r the
phase change to take p l a c e because of i n c r e a s i n g molecular weight

caused by p o l y m e r i z a t i o n a s s o c i a t e d w i t h i n c r e a s i n g heat treatment

temperature (HTT). Chemical s t u d i e s of the molecular species
present during the f l u i d phase of c a r b o n i z a t i o n suggest molecular
weights of t y p i c a l l y 2000 amu (2).
A p y r o l y s i n g system about to pass through the l i q u i d c r y s t a l

phase t r a n s i t i o n (630-700 K) comprises molecules w i t h a l a r g e
spread of molecular weights which are c o n t i n u a l l y i n t e r a c t i n g
c h e m i c a l l y and p o l y m e r i s i n g v i a c r o s s - l i n k a g e s u s i n g dehydro-
genative polymerisation r e a c t i o n s * This polymerisation creates
planar molecules c o n s i s t i n g of sheets of hexagonally l i n k e d carbon
atoms c o n t a i n i n g h o l e s , heteroatoms and f r e e e l e c t r o n s . When the
molecular s i z e reaches -1000 amu i t becomes e n e r g e t i c a l l y f a v o u r -
a b l e f o r the system to undergo a p h y s i c a l phase t r a n s i t i o n to a

l i q u i d c r y s t a l phase i n which van der Walls f o r c e s m a i n t a i n
s t a b i l i t y i n i t i a l l y . The t r a n s i t i o n i s seen i n the hot stage of
a p o l a r i z e d l i g h t microscope as the f o r m a t i o n of d r o p l e t s of
o p t i c a l l y a n i s o t r o p i c m a t e r i a l which appear as spheres of y e l l o w /
b l u e c o l o u r i n a purple i s o t r o p i c m a t r i x . Continued p y r o l y s i s
causes these d r o p l e t s to grow a t the expense of the surrounding
isotropic material.
T h i s phase t r a n s i t i o n i s i n i t i a l l y r e v e r s i b l e , as demonstrated
by Lewis (10), but as c a r b o n i z a t i o n progresses chemical c r o s s -
l i n k i n g makes i t i r r e v e r s i b l e . The l i q u i d c r y s t a l d r o p l e t s grow
and c o a l e s c e u n t i l a l l the i s o t r o p i c melt has undergone the phase
t r a n s i t i o n . This new phase i s then termed the l i q u i d c r y s t a l
mesophase, i . e . the phase intermediate between the i s o t r o p i c f l u i d
p i t c h and s o l i d semi-coke.
O p t i c a l Texture
The o p t i c a l a n i s o t r o p y of cokes g i v e s r i s e to a c h a r a c t e r i s -
t i c p a t t e r n of e x t i n c t i o n contours when a p o l i s h e d surface i s
examined by p o l a r i z e d l i g h t microscopy u s i n g crossed p o l a r s , or
r e f l e c t i o n i n t e r f e r e n c e c o l o u r s i f the p o l a r s are p a r a l l e l and a
h a l f wave p l a t e i s i n s e r t e d i n t o the o p t i c a l system (11, 12).
This c h a r a c t e r i s t i c p a t t e r n i s termed the o p t i c a l t e x t u r e of the
coke. O p t i c a l t e x t u r e i n c r e a s e s i n s i z e w i t h i n c r e a s i n g f l u i d i t y
(decreasing p l a s t i c i t y ) of the mesophase. Mesophase v i s c o s i t y
can be a f f e c t e d by parameters of c a r b o n i z a t i o n such as h e a t i n g
r a t e , HTT and soak time but the s i n g l e most important f a c t o r i s
chemical r e a c t i v i t y (13). I f r e a c t i v i t i e s are too h i g h , e a r l y
p o l y m e r i s a t i o n leads to the f o r m a t i o n of i s o t r o p i c carbon because
of randomly a l i g n e d i n t e r a c t i o n s . Low r e a c t i v i t i e s g i v e r i s e to
a low v i s c o s i t y mesophase which flows and coalesces e a s i l y . Hence
the s i z e and type of o p t i c a l t e x t u r e i s predominantly a f u n c t i o n
of the parent m a t e r i a l carbonized and may be used to c h a r a c t e r i s e
the coke. I t i s t h e r e f o r e necessary to d e f i n e p r e c i s e l y the
d i f f e r e n t types of o p t i c a l t e x t u r e seen i n cokes. A standard

nomenclature has been devised (Table I ) which ranges from v e r y

f i n e - g r a i n e d mosaics (<0.5 urn diameter) *to f l o w domain a n i s o t r o p y
(>60 urn l e n g t h , >10 urn w i d t h ) .
S i g n i f i c a n c e of O p t i c a l Texture. I n m e t a l l u r g i c a l and
foundry cokes, subject to s t r i n g e n t s p e c i f i c a t i o n s of s t r e n g t h ,
s i z e and r e a c t i v i t y , i t i s necessary to know whether the develop-
ment of a n i s o t r o p y d u r i n g the mesophase i s i n c i d e n t a l or e s s e n t i a l
to coke p r o p e r t i e s (14, 15, 16).
Strength
Coke s t r e n g t h i s i n t i m a t e l y r e l a t e d t o i t s p o r o s i t y and pore

w a l l s t r u c t u r e . During the f o r m a t i o n of the l a t t e r , l i q u i d

c r y s t a l s encounter surfaces (gaseous or s o l i d ) w i t h i n the
c a r b o n i z a t i o n system and tend to f l o w i n such a way that the
l a m e l l a r molecules a l i g n w i t h the surfaces (14). O p t i c a l m i c r o s -
copy of coke shows l a y e r s of a n i s o t r o p i c m a t e r i a l forming a
' l i n i n g ' on i n t e r n a l and e x t e r n a l s u r f a c e s . Thus a growing pore
may develop such a l i n i n g which undergoes f u r t h e r p o l y m e r i z a t i o n
to form a continuous l a m e l l a r s t r u c t u r e (17). This i s e q u i v a l e n t
to a l a r g e i n c r e a s e i n surface t e n s i o n , s e v e r e l y r e s t r i c t i n g pore
growth and preventing the formation of ' f r o t h y ' coke. S i m i l a r l y ,
an i n e r t p a r t i c l e may be encased i n a strong l a y e r of o r i e n t a t e d
l a m e l l a r molecules. These mechanisms i n c r e a s e coke s t r e n g t h .
F i s s u r e propagation through the pore w a l l m a t e r i a l of coke

i s a l s o dependent on the s i z e and o r i e n t a t i o n of a n i s o t r o p i c
components present; f i s s u r e s propagate e a s i l y through l a r g e
o p t i c a l t e x t u r e s (>60 urn) w h i l e mosaic t e x t u r e s (1 to 10 urn) tend
to act as f i s s u r e stops. Experimental v e r i f i c a t i o n of t h i s aspect
of f i s s u r e generation and propagation w i l l be d i s c u s s e d below.
Reactivity
When carbon d i o x i d e r e a c t s w i t h carbon to produce carbon

monoxide a t temperatures above 1140 K, i n the b l a s t furnace,
carbon goes i n t o ' s o l u t i o n ' i n the gas and s o l u t i o n l o s s i s s a i d
to have occurred (18). S o l u t i o n l o s s i s so termed because carbon
monoxide i n b l a s t furnace gases represents a l o s s i n r e d u c t i o n
c a p a c i t y . Reduction c a p a c i t y i s maximised w i t h zero CO i n the
e f f l u e n t gas. The r e a c t i o n reduces the impact s t r e n g t h and
a b r a s i o n r e s i s t a n c e of the coke and must be minimized. The
r e a c t i o n does not occur evenly over the coke surface but g i v e s
r i s e to p r e f e r e n t i a l g a s i f i c a t i o n f i s s u r i n g and p i t t i n g (17, 15,
20). This i s a d i r e c t consequence of the a n i s o t r o p y of coke
whereby r e a c t i o n r a t e s d i f f e r w i t h c r y s t a l l o g r a p h i c d i r e c t i o n .
Such f i s s u r i n g causes premature coke a b r a s i o n and breakage,
reducing p e r m e a b i l i t y i n the b l a s t furnace m e l t i n g zone and
i n f l u e n c i n g the s t a b i l i t y of the race-way. Formation and

Table I
Nomenclature to Describe O p t i c a l Texture

i n P o l i s h e d Surfaces of Cokes
Isotropic (I) No o p t i c a l a c t i v i t y
Very f i n e - g r a i n e d mosaics (VMF) <0.5 urn i n diameter
F i n e - g r a i n e d mosaics (Mf) <1.5 >0.5 Urn i n diameter
Medium-grained mosaics (Mm) <5.0 >1.5 urn i n diameter
Coarse-grained mosaics (Mc) <10.0 >5.0 urn i n d i a m e t e r

Supra mosaics (SM) Mosaics of a n i s o t r o p i c
carbon o r i e n t a t e d i n
the same d i r e c t i o n to
g i v e a mosaic area of
isochromatic c o l o u r .
Medium-flow a n i s o t r o p y (MFA) <30 urn i n length;

<5 urn i n w i d t h
Coarse-flow a n i s o t r o p y (CF) <60 >30 urn i n l e n g t h ;

<10 >5 ym i n w i d t h
A c i c u l a r f l o w domain a n i s o t r o p y (AFD) >60 um i n l e n g t h ;

<5 um i n w i d t h
Flow domain a n i s o t r o p y (FD) >60 um i n length;
>10 ym i n w i d t h
Small domains (SD) <60 >10 ym i n diameter
Domains, - i s o m e t r i c (D) >60 ym i n diameter
i s from b a s i c a n i s o t r o p y of l o w - v o l a t i l e
coking v i t r a i n s and a n t h r a c i t e .
D m i s by growth of mesophase from f l u i d phase.
Ribbons (R) Strands of mosaics i n s e r t e d i n t o an i s o t r o p i c t e x t u r e .

propagation of f i s s u r e s formed upon g a s i f i c a t i o n and thermal

s t r e s s i n g of the coke a r e minimized i n cokes of small o p t i c a l
t e x t u r e ( f i n e - and medium-grained mosaics; see Table I ) , as found
i n cokes from prime coking c o a l s * O v e r a l l , a n i s o t r o p i c carbon i s
l e s s r e a c t i v e than i s o t r o p i c carbon.
The presence of a l i q u i d c r y s t a l phase d u r i n g c a r b o n i z a t i o n

i s t h e r e f o r e a p r e - r e q u i s i t e f o r the f o r m a t i o n of good m e t a l l u r g i -
c a l coke.
Blending Procedures
The p r a c t i c e of c o a l b l e n d i n g i s now of c e n t r a l importance to

the coke making i n d u s t r y as s u p p l i e s of prime coking c o a l s become

depleted. Blends must c o n s i s t of c o a l s which have complementary
p r o p e r t i e s to compensate f o r t h e i r i n d i v i d u a l coking d e f i c i e n c i e s
The coking p r o p e r t i e s of the o v e r a l l blend must be s i m i l a r to
those of a s i n g l e prime coking c o a l . Coking p o t e n t i a l of a c o a l
blend i s determined by:
(a) Behaviour i n the p l a s t i c zone ( f u s i n g and pore f o r m a t i o n ) .
(b) Behaviour i n the p o s t - p l a s t i c zone ( f i s s u r e f o r m a t i o n
from d i f f e r e n t i a l c o n t r a c t i o n ) .
(c) C o m p a t i b i l i t y of the blend components.
(d) Content and s i z e d i s t r i b u t i o n of the m i n e r a l matter.
The P l a s t i c Zone. P l a s t i c zone behaviour i s q u a n t i f i e d by

determining d i l a t i o n i n a d i l a t o m e t e r (21); c o n d i t i o n s and
c o n s t r a i n t s are not the same as i n a coking oven, but r e s u l t s are
i n d i c a t i v e of the s w e l l i n g pressure developed and show i f i t i s
s u f f i c i e n t to achieve the degree of s u r f a c e c o n t a c t of p a r t i c l e s
necessary to produce adequate coalescence. I t has been shown (2)
that f o r charges to equal v o l a t i l e content, the cohesion improves
as t o t a l d i l a t i o n of the blend i n c r e a s e s to 40-50% and then
remains c o n s t a n t . The t a r g e t s p e c i f i c a t i o n f o r c o a l blends f o r
m e t a l l u r g i c a l cokes i s t h e r e f o r e a t o t a l d i l a t i o n of not l e s s
than 50%. (That of prime c o k i n g c o a l s i s -75%).
The P o s t - P l a s t i c Zone. I t i s d i f f i c u l t to q u a n t i f y blend

behaviour ( c o n t r a c t i o n and r e s u l t a n t f i s s u r i n g ) i n the p o s t - p l a s t i c
zone. There i s , however, a r e l a t i o n s h i p between the temperature
of the f i r s t peak of the c o n t r a c t i o n c o e f f i c i e n t of the coke and
v o l a t i l e matter content (2) which suggests t a r g e t s p e c i f i c a t i o n s
f o r blends of v o l a t i l e content i n the range ~20-32% and d i l a t i o n
i n the range -50-150%.
C o m p a t i b i l i t y of Blend Components. I t i s important when

b l e n d i n g c o a l s to ensure t h a t the temperature ranges over which
the i n d i v i d u a l c o a l s become p l a s t i c o v e r l a p . The g r e a t e r the
degree of o v e r l a p , the b e t t e r the f l u i d m i x i n g and chemical i n t e r -
a c t i o n of the components and the more homogeneous and cohesive the

r e s u l t a n t coke. C o m p a t i b i l i t y may be improved by c r u s h i n g the low

v o l a t i l e blend components t o <0.5 mm before mixing or by a d d i t i o n
of a b r i d g i n g c o a l of intermediate p l a s t i c zone.
M i n e r a l Matter Content. Coarse m i n e r a l matter content can

i n i t i a t e f i s s u r e formation and decrease coke s t r e n g t h and so must
be monitored during blending procedures. However, the c a r e f u l
a d d i t i o n of i n e r t m a t e r i a l can sometimes be used t o improve coke
s t r e n g t h . Coke oven breeze or petroleum coke breeze may be added
to a c o a l blend to improve the t e n s i l e s t r e n g t h of the coke (22,
23). Coke oven breeze, f i n e l y ground and added as up t o 8% of the
charge can improve the t e n s i l e s t r e n g t h of some cokes.
Petroleum coke breeze, however, g i v e s p r o g r e s s i v e i n c r e a s e s

of t e n s i l e s t r e n g t h f o r breeze a d d i t i o n s of up t o 50% i n some
blends. I n g e n e r a l , the lower the HTT of the breeze, the b e t t e r
the t e n s i l e s t r e n g t h of the coke (24). P a r t i c l e s i z e ( a f f e c t i n g
the a b i l i t y of the r e a c t i v e components t o i n c o r p o r a t e the
p a r t i c l e s ) a l s o c o n s i d e r a b l y i n f l u e n c e s coke s t r e n g t h . Increases
i n coke s t r e n g t h w i t h low percentage a d d i t i o n s and small p a r t i c l e
s i z e s a r e thought to be due t o the a c t i o n of breeze as a f i l l e r ,
i n c r e a s i n g the t h i c k n e s s of the pore w a l l m a t e r i a l of the coke
and thus i n c r e a s i n g the volume of load-bearing m a t e r i a l (24)• This
strengthening f a c t o r outweighs the weakening due t o m i c r o - f i s s u r e
generation a s s o c i a t e d w i t h non-uniformity of c o n t r a c t i o n r a t e s of
the breeze and surrounding c o a l coke.
The Use of P i t c h as a Blend A d d i t i v e . The use of p i t c h

a d d i t i v e s i n blends i s being i n c r e a s i n g l y i n v e s t i g a t e d as an
a l t e r n a t i v e t o u s i n g prime coking c o a l as one blend component.
Low v i s c o s i t y p i t c h a d d i t i v e s a r e p a r t i c u l a r l y s u c c e s s f u l when
used i n place of b r i d g i n g c o a l s to extend the temperature range
of p l a s t i c zone overlap of the d i f f e r e n t blend components.
P i t c h m a t e r i a l s f a l l i n t o two main c a t e g o r i e s ; some p i t c h

a d d i t i v e s i n c o a l blends have the a b i l i t y to modify the o p t i c a l
t e x t u r e of the r e s u l t a n t coke (and hence i t s bulk p r o p e r t i e s )
s i g n i f i c a n t l y . Small percentage a d d i t i o n s of such p i t c h e s t o poor
q u a l i t y c o a l s can s i g n i f i c a n t l y improve coking p r o p e r t i e s and
b r i n g them w i t h i n the s p e c i f i c a t i o n s f o r i n d u s t r i a l usage. Such
p i t c h e s a r e termed ' a c t i v e ' or ' s u p e r a c t i v e ' . P i t c h e s which do
not possess t h i s modifying a b i l i t y a r e termed 'passive'. Work
has been done on the modifying a b i l i t y of v a r i o u s p i t c h e s and
makes use o f the r e l a t i o n s h i p between o p t i c a l t e x t u r e and coke
p r o p e r t i e s (25). The a b i l i t y of a p i t c h to modify o p t i c a l t e x t u r e
of a blend t o g i v e a t e x t u r e c h a r a c t e r i s t i c of a good coke i s
e a s i l y monitored u s i n g techniques of o p t i c a l microscopy; o p t i c a l
t e x t u r e i s thus an i d e a l parameter f o r i n i t i a l c h a r a c t e r i z a t i o n
of blends. This work i s reported below.

Hydrogen Transfer
As chemical compositions of c o a l s and p i t c h e s are extremely

complex no exact e x p l a n a t i o n e x i s t s of d i f f e r e n c e s i n s i z e and
shape of o p t i c a l t e x t u r e of the coke i n terms of the p y r o l y s i s
chemistry of the c a r b o n i z a t i o n process (26). I t has been
suggested that the presence of naphthenic groups and aromatic r i n g
systems i n molecular c o n s t i t u e n t s promote the growth of l a r g e r
a n i s o t r o p i c areas ( o p t i c a l texture) w h i l e the presence of hetero-
atoms and f u n c t i o n a l groups promote the growth of smaller o p t i c a l
1
t e x t u r e s (27). Recently, the concept of 'hydrogen s h u t t l i n g has
been introduced i n d i s c u s s i o n s on the development of mesophase
d u r i n g c o - c a r b o n i z a t i o n of c o a l s w i t h p i t c h e s (2§, 2§). I t i s
suggested that the hydrogen may s t a b i l i z e c e r t a i n f r e e r a d i c a l s

produced during p y r o l y s i s (JO). T h i s s t a b i l i z a t i o n of the o t h e r -
wise r e a c t i v e molecules prevents e a r l y formation of s o l i d
i s o t r o p i c carbon and allows the temperature of the c a r b o n i z a t i o n
system to be increased such that v i s c o s i t y of the system i s
decreased. This i n t u r n f a c i l i t a t e s the phase t r a n s i t i o n to a
nematic l i q u i d c r y s t a l . The mesophase growth u n i t s i n c r e a s e i n
s i z e and coalesce and an a n i s o t r o p i c coke r e s u l t s ( 3 J ) . L a r s e n
and Sams (32) consider c o a l s to be good hydrogen donors and
acceptors and that only heat and the proper medium a r e necessary
to c a r r y out extensive i n t e r n a l hydrogen t r a n s f e r r e a c t i o n s .
These r e a c t i o n s produce more condensed aromatic m a t e r i a l , the
r e l e a s e d hydrogen forming a l i p h a t i c s t r u c t u r e s . I f a p i t c h i s
hydrogenated and then carbonized then the v i s c o s i t y of the meso-
phase i s s i g n i f i c a n t l y decreased (2JJ). O p t i c a l t e x t u r e i s
t h e r e f o r e increased i n s i z e . This i s probably a s s o c i a t e d w i t h
hydrogen t r a n s f e r r e a c t i o n s (hydrogen s h u t t l i n g ) i n v o l v i n g
movement of hydrogen from the p i t c h to the r a d i c a l s of the
c a r b o n i z a t i o n process. Thus, s t u d i e s of hydrogen t r a n s f e r
r e a c t i o n s involved i n c o a l l i q u e f a c t i o n and of f r e e r a d i c a l
concentrations i n c a r b o n i z i n g systems may be r e l a t e d (22). These
c o n s i d e r a t i o n s a r e r e l e v a n t both to c a r b o n i z a t i o n s of s i n g l e
p i t c h e s and, more i m p o r t a n t l y , to c o - c a r b o n i z a t i o n systems of
c o a l and p i t c h i n which the l a t t e r i s used t o up-grade the coking
a b i l i t y of the c o a l (27, 34, 31).
Experimental Techniques of the Study
O p t i c a l Microscopy and Scanning E l e c t r o n Microscopy. Cokes

are prepared f o r o p t i c a l microscopy by mounting i n r e s i n , g r i n d i n g
a f l a t surface and p o l i s h i n g w i t h p r o g r e s s i v e l y f i n e r grades of
alumina powder. These p o l i s h e d surfaces a r e then examined under
a V i c k e r s M41 p o l a r i z e d l i g h t microscope using p a r a l l e l p o l a r s
w i t h a half-wave r e t a r d e r p l a t e to g i v e r e f l e c t i o n i n t e r f e r e n c e
colours.

Coke samples to be examined by SEM are mounted on a stub

and g o l d coated to prevent charging i n the e l e c t r o n beam.
P o i n t - c o u n t i n g . O p t i c a l t e x t u r e s seen under the o p t i c a l

microscope are c l a s s i f i e d according to the d e f i n i t i o n s i n Table I
(25). M e t a l l u r g i c a l coke i s heterogeneous and o f t e n c o n t a i n s
s e v e r a l d i f f e r e n t types of o p t i c a l t e x t u r e . I n order to o b t a i n
a s t a t i s t i c a l l y r e l i a b l e d e s c r i p t i o n of o p t i c a l t e x t u r e , each
coke i s point-counted. The frequency of occurrence of each type
1
of t e x t u r e a t p o i n t s on a ' g r i d i s recorded on a S w i f t Automatic
p o i n t counter.
Strength T e s t i n g . The r e l a t i v e s t r e n g t h s of cokes are

measured u s i n g a m i c r o s t r e n g t h apparatus s u i t a b l e f o r l a b o r a t o r y
use. T h i s c o n s i s t s of two metal c y l i n d e r s c o n t a i n i n g 12 s t e e l
b a l l b e a r i n g s , ~8 mm i n diameter. The tubes are r o t a t e d a t 25
rev m i n ~ l f o r 400 r e v o l u t i o n s . The r e s u l t a n t coke p a r t i c l e s are
subjected to c a r e f u l s i e v e a n a l y s i s and are c l a s s i f i e d as three
percentages of the t o t a l weight i n s i z e groups 600 ym - 1.17 mm
( R ) , 212 - 600 ym (R ) and <212 ym ( R ) .
x 2 3
M a t e r i a l s Used i n the Study
Coals
1. Blaenhirwaun Pumpquart a n t h r a c i t e (NCB CR 101).
2. Tilmanstone v i t r a i n (NCB CR 204).
3. North Celynon Meadow V e i n (NCB CR 301a).
4. Roddymoor B a l l a r a t (NCB CR 301b).
5. S i x B e l l s (NCB CR 301a).
6. Cortonwood S i l k s t o n e (NCB CR 401).
7. Maltby Swallow Wood (NCB CR 502).
8. Manton Parkgate (NCB CR 602).
9. N a i l s t o n e Yard (NCB CR 902).
Comparison of the UK and USA c o a l r a n k i n g systems i s i n

Table I I .
Pitches
Ashland A200 petroleum p i t c h .
Ashland A170 p i t c h coke (green).
I n d u s t r i a l l y Prepared M e t a l l u r g i c a l Cokes
Spencer Works Wharf coke )
; , . .
, . _ · π ^ ncnv
; carbonized i n d u s t r i a l l y to 1350 K.
J
Clyde Ironworks coke
r T
)
Experimental Procedures of the Study
G a s i f i c a t i o n and Heat Treatment. Two p o l i s h e d s u r f a c e s of

each of the i n d u s t r i a l l y prepared m e t a l l u r g i c a l cokes l i s t e d
above were prepared and examined under the o p t i c a l microscope.

A r e p r e s e n t a t i v e area of each was chosen, photographed and i t s

p o s i t i o n r e c o r d e d . The same areas were l o c a t e d and photographed
i n the scanning e l e c t r o n microscope (SEM). The technique of
examining the same area b e f o r e and a f t e r e x p e r i m e n t a t i o n e l i m i n
ates much of the s t a t i s t i c a l v a r i a t i o n inherent i n such a
heterogeneous m a t e r i a l as m e t a l l u r g i c a l coke.
G a s i f i c a t i o n i n Carbon D i o x i d e . One sample of each coke was

g a s i f i e d i n CO2 i n a h o r i z o n t a l e l e c t r i c a l tube furnace f o r 16 h
a t 1173 Κ (900°C).
Heat Treatment. One sample of each coke was heat t r e a t e d

under argon i n a g r a p h i t e r e s i s t a n c e furnace f o r 0.5 h a t 2073 Κ
(1800°C).
The s e l e c t e d areas of a l l samples were then r e l o c a t e d and

photographed by SEM.
Breeze A d d i t i v e s . A170 p i t c h coke breeze was f u r t h e r

carbonized t o HTTs of 900 K, 1000 K, 1100 Κ and 1200 Κ a t 3 Κ
1
m i n " under N w i t h a soak time of 0.5 h.
2
The f i v e r e s u l t a n t p i t c h cokes and the c o a l s l i s t e d above

(numbers 5, 6 and 7) were ground t o s i e v e s i z e s 600 ym - 1.17 mm.
Blends of c o a l and p i t c h coke (9:1 by weight) and the s i n g l e
c o a l s were carbonized i n a h o r i z o n t a l e l e c t r i c a l tube furnace
1
under N to 1250 Κ (977°C) a t 3 K m i n " w i t h 0.5 h soak time.
2
Each coke was mounted i n r e s i n and a p o l i s h e d surface

prepared which was examined and photographed under the o p t i c a l
microscope. F r a c t u r e s u r f a c e s of each coke were examined by SEM.
Analyses of these c o a l s a r e i n Table I I I .
Strength Measurements. Each coke was ground to p a r t i c l e

s i z e s of 600 ym - 1.17 mm. 2 g of each coke was tested i n the
m i c r o s t r e n g t h apparatus and then s i e v e d .
Blending of P i t c h w i t h Coals. The c o a l s l i s t e d above (with

the e x c e p t i o n s of those numbered 5, 6 and 7) were ground to a
p a r t i c l e s i z e of <250 ym and were then mixed w i t h 25 wt % A200
p i t c h . These blends were carbonized i n a h o r i z o n t a l e l e c t r i c a l
tube furnace t o heat treatment temperatures (HTTs) of 1273 Κ
1
(1000°C) a t a heating r a t e of 5 K m i n " under N w i t h a 0.5 h 2
soak. The r e s u l t i n g cokes were mounted i n r e s i n and p o l i s h e d

s u r f a c e s prepared. The s u r f a c e s were examined o p t i c a l l y and
point-counted. The cokes from c o a l s were a l s o point-counted a f t e r
being carbonized s i n g l y under i d e n t i c a l c o n d i t i o n s f o r comparison.
Analyses of these c o a l s and of the A200 p i t c h are i n Tables

IV and V.

Table I I
Comparison of U.K. and U.S.A. coak r a n k i n g systems
U.K. U.S.A.
N.C.B. c o a l rank
100-102 Meta a n t h r a c i t e
*V.M. 2-9% Anthracite
200-206 Semi a n t h r a c i t e
V.M. 9-19.5% Low v o l a t i l e bituminous

t300-306 Medium v o l a t i l e
V.M. 19.5-32% bituminous
400-700 High v o l a t i l e
V.M. 32-44% bituminous
800-900
V.M. 32-47% Sub bituminous
* V.M. = v o l a t i l e matter content,

t Coals 304-306 heat a f f e c t e d .
Table I I I
Analyses of Coals
Material V o l a t i l e Content C H
(wt % d.a.f.) (wt % d.a.f.) (wt % d.a.f.)
Six Bells
c o a l (CR 301a) 24.1 90.0 4.7
Cortonwood S i I k s t o n e
c o a l (CR 401) 35.4 86.8 -
Maltby Swallow
Wood coal (CR 502) 37.4 86.8 -

Table IV
Analyses of V i t r a i n s
Β.S. NCB
Air-dried Coal
Dry ash-free b a s i s <(wt %)
b a s i s (wt %) Swelling Rank
Code
Vitrain M o i s t u r e Ash C H Ν S o VM
a
No. No.
Blaenhirwaun
Pump quart 0.5 93.6 3.2 1.2 0.7 1.3 4.6 Ν. A. 101
1.6
Tilmanstone 1.0 1.3 89.7 4.6 1.4 1.0 3.3 19.3 8è 204
North Celynon
Meadow V e i n 1.0 2.5 88.6 4.9 1.5 1.1 3.9 24.4 9 301a
Roddymoor
Ballarat 0.9 0.4 88.4 5.3 1.7 0.7 3.5 29.8 9 301b
Manton Main
Parkgate 8.1 1.2 82.8 5.4 1.8 1.2 8.8 35.3 4 602
Nailstone
Yard 13.2 3.6 78.2 5.2 1.5 1.1 14.0 42.5 1 902
N.A. Non-agglomerating
Table V
A n a l y s i s of Ashland A200 P i t c h
Softening RB (°C) 199 Benzene-insolubles (wt %) 35.1

V o l a t i l e matter (wt %) 35.5 Heptane-insolubles (wt %) 93.5
Sulphur (wt %) 2.9 α-resin, Q u i n o l i n e
CERCHAR Conradson i n s o l u b l e s (wt %.) 0.45
carbon (wt %) 71.6 α + 3 r e s i n s (wt %) 20.8
Asphaltenes (wt %) 58.4
Elemental a n a l y s i s (dry ash-free b a s i s ) :
Carbon Hydrogen Sulphur Nitrogen Oxygen Ash

91.7 5.0 2.9 0.1 0.3 0.1
By d i f f e r e n c e

R e s u l t s and D i s c u s s i o n
G a s i f i c a t i o n and Heat Treatment. Examination under the

o p t i c a l microscope showed the Spencer works and Clyde Ironworks
cokes to have o p t i c a l t e x t u r e s m a i n l y c o n s i s t i n g of f i n e - and
medium-grained mosaics w i t h some coarse f l o w a n i s o t r o p y and
i s o t r o p i c i n e r t m a t e r i a l . Of p a r t i c u l a r i n t e r e s t a r e the f i s s u r e s
which develop i n d i f f e r e n t types of o p t i c a l t e x t u r e and those
o c c u r r i n g a t the a n i s o t r o p i c - i n e r t i n t e r f a c e . SEM examination of
these p o l i s h e d s u r f a c e s before experimentation shows a l l of them
to be f l a t and f e a t u r e l e s s .
G a s i f i c a t i o n . O p t i c a l microscopy of the g a s i f i e d cokes was

not p o s s i b l e as t h e i r s u r f a c e s were too roughened. SEM examination

of the same areas of Spencer and Clyde cokes o r i g i n a l l y s t u d i e d by
o p t i c a l microscopy r e v e a l e d e x t e n s i v e g a s i f i c a t i o n f i s s u r i n g over
t h e i r s u r f a c e s . F i g u r e 1 i s an o p t i c a l micrograph of Spencer coke
before g a s i f i c a t i o n ; F i g u r e 2 i s a SEM micrograph of the same
area of coke s u r f a c e a f t e r g a s i f i c a t i o n i n C 0 f o r 16 h a t 1173 K.
2
Comparison of the two F i g u r e s i n d i c a t e s t h a t , i n g e n e r a l , s i z e ,

shape and o r i e n t a t i o n of the g a s i f i c a t i o n f i s s u r e s o c c u r r i n g i n
o p t i c a l l y a n i s o t r o p i c areas a r e s t r o n g l y dependent upon the
character of the o p t i c a l t e x t u r e i n which they occur ( P o s i t i o n A ) .
In r e g i o n s of medium-grained mosaics, f i s s u r e s develop which a r e
t y p i c a l l y of the same s i z e as the o p t i c a l t e x t u r e ; these f i s s u r e s
are o r i e n t a t e d p a r a l l e l t o the l a y e r planes of the a n i s o t r o p i c
carbon and tend not to c r o s s i s o c h r o m a t i c boundaries.
The bonding between the i n e r t s and surrounding a n i s o t r o p i c

m a t e r i a l appears to be a r e g i o n of weakness which g a s i f i e d
p r e f e r e n t i a l l y . Large f i s s u r e s (~5 ym wide) are found a t these
i n t e r f a c e s ( P o s i t i o n B ) . I n e r t m a t e r i a l o f t e n g a s i f i e s completely
l e a v i n g a v o i d ( P o s i t i o n £) ; t h i s may be due t o the presence of a
c a t a l y s t i n some i n o r g a n i c i n e r t s . Other i n e r t s g a s i f y u n i f o r m l y
or not a t a l l ; there i s no evidence of the p r e f e r e n t i a l g a s i f i c a -
t i o n seen i n the a n i s o t r o p i c areas.
Heat Treatment. O p t i c a l microscopy showed two changes t o

have taken p l a c e i n these cokes upon heat treatment to 2073 K.
F i r s t l y , both showed a s t r e n g t h e n i n g o f the i n t e r f e r e n c e c o l o u r s .
This e f f e c t may be caused by an i n c r e a s e i n the p e r f e c t i o n of
o r d e r i n g of the g r a p h i t i c l a y e r planes as the heat treatment
approaches g r a p h i t i z i n g temperatures. Secondly, a network of
f i s s u r e s c o u l d be seen on the coke s u r f a c e , p a r t i c u l a r l y i n the
a n i s o t r o p i c areas. These f i s s u r e s were more c l e a r l y v i s i b l e u s i n g
SEM. F i g u r e 3 i s an o p t i c a l micrograph of the Clyde coke;
F i g u r e 4 shows the same area examined by SEM a f t e r heat treatment.
Once a g a i n , comparison shows f i s s u r e s of the same s i z e and
o r i e n t a t i o n as the o p t i c a l t e x t u r e (predominantly medium-grained
mosaics) t o have developed ( P o s i t i o n D). These f i s s u r e s appear

FORREST AND MARSH Carbonization of Coal and Coal Blends
Figure 1. Optical micrograph of Spencer Wharf coke. Positions A, B, and C dis-

cussed in text.
Figure 2. SEM micrograph of Spencer Wharf coke after 16 h gasification in COt
at 1173 K. Positions A, B, and C discussed in text.

Figure 3. Optical micrograph of Clyde Ironworks coke. Positions D and Ε dis

cussed in text.
Figure 4. SEM micrograph of Clyde Ironworks coke after heat treatment to

2073 Κ under argon. Positions D and Ε discussed in text.

to be bounded by the isochromatic boundaries across which few of

them propagate. Hence a r a p i d change i n o r i e n t a t i o n o f , or
d i s c o n t i n u i t y i n , the l a y e r planes of the coke appears to act as
a f i s s u r e stop. The few l a r g e r f i s s u r e s (~30 ym χ 5 ym) which
were found i n these cokes occurred m a i n l y i n the i n f r e q u e n t areas
of coarse f l o w a n i s o t r o p y . In the absence of r a p i d changes i n
s t r u c t u r a l o r i e n t a t i o n i n t h i s type of o p t i c a l t e x t u r e the
propagation of f i s s u r e s i s p o s s i b l e to a much l a r g e r extent than
i n the r e g i o n s of smaller mosaics.
Again, the i n e r t - a n i s o t r o p i c boundary i s a r e g i o n where

f i s s u r i n g occurred ( P o s i t i o n E ) ; the i n e r t s themselves show no
surface f i s s u r i n g .
D i f f e r e n c e s i n coke behaviour i n the b l a s t furnace (not

d e t e c t a b l e by c o l d t e s t i n g p r i o r to the charging of the b l a s t
furnace) may be a t t r i b u t a b l e to d i f f e r e n c e s i n the mode of
g a s i f i c a t i o n of the coke as a r e s u l t of combined e f f e c t s of
thermal and g a s i f i c a t i o n f i s s u r i n g . These r e s u l t s i n d i c a t e that
mosaic o p t i c a l t e x t u r e s are p r e f e r a b l e to f l o w a n i s o t r o p y i n terms
of f i s s u r e containment and a l s o show that i n e r t p a r t i c l e s can a c t
as centres of f i s s u r e g e n e r a t i o n .
Breeze A d d i t i v e s . O p t i c a l microscopy of the S i x B e l l s

(CR 301a), Cortonwood (CR 401) and Maltby (CR 502) cokes w i t h the
A170 p i t c h coke breeze a d d i t i v e s shows that the breeze a d d i t i v e s
w i t h predominantly f l o w domain a n i s o t r o p y o p t i c a l texture are
e a s i l y d i s t i n g u i s h a b l e from the surrounding c o a l coke of p r e
dominantly f i n e - g r a i n e d mosaics. The e f f e c t of c a r b o n i z a t i o n to
1200 Κ upon the petroleum coke breeze i s to i n c r e a s e p r o g r e s s i v e l y
the number and s i z e of f i s s u r e s w i t h i n the breeze p a r t i c l e s .
F i g u r e s 5 and 6 are of coke from S i x B e l l s c o a l co-carbonized

w i t h green A170 p i t c h coke breeze and 1200 Κ A170 p i t c h coke breeze
r e s p e c t i v e l y . P o s i t i o n £ shows the o p t i c a l texture of the c o a l -
coke, w h i l e P o s i t i o n P^ shows that of the p i t c h coke breeze.
F i g u r e 5 shows that the green p i t c h coke i s w e l l bonded to

the surrounding c o a l coke ( P o s i t i o n s E_, F) ; there are no f i s s u r e s
at the i n t e r f a c e . F i s s u r e s w i t h i n the p i t c h coke do not propagate
across the i n t e r f a c e i n t o the c o a l coke. As the HTT of the p i t c h
coke breeze i s i n c r e a s e d , the i n t e r f a c e becomes p r o g r e s s i v e l y more
f i s s u r e d , u n t i l f o r the 1200 Κ p i t c h coke breeze (Figure 6,
P o s i t i o n s L, M) the breeze p a r t i c l e i s almost e n t i r e l y surrounded
by v o i d s . Where breeze p a r t i c l e s of HTT 1200 Κ are bonded to the
surrounding coal coke, f i s s u r e s o r i g i n a t i n g i n the breeze
propagate across the i n t e r f a c e i n t o the surrounding m a t e r i a l .
These r e s u l t s are confirmed by SEM examination of f r a c t u r e surf aces
of a l l the cokes produced and are true f o r a l l three coals used.

Figure 5. Optical micrograph showing green pitch-coke breeze in coke from Six
Bells coal. Positions C, E , F, and Ρ discussed in text.
Figure 6. Optical micrograph showing pitch-coke breeze (1200 K) in coke from

Six Bells coal. Positions C, L, M , and Ρ discussed in text.

Data from the micro s t r e n g t h measurements are given i n Tables

V I , V I I and V I I I . The higher the v a l u e s of the s i z e f r a c t i o n s R^
and R2, the stronger i s the pore w a l l m a t e r i a l of the coke. These
r e s u l t s i n d i c a t e an i n t e r e s t i n g f e a t u r e of the e f f e c t s of breeze
a d d i t i o n s upon coke s t r e n g t h . For a l l three c o a l s used i t i s true
t h a t the lower the HTT of the p i t c h coke breeze added, the stronger
the r e s u l t a n t coke. Strength decreases p r o g r e s s i v e l y w i t h
i n c r e a s i n g HTT of p i t c h coke breeze. However, comparison of the
m i c r o s t r e n g t h r e s u l t s f o r the prime coking S i x B e l l s c o a l when
carbonized s i n g l y , w i t h those f o r the same c o a l carbonized w i t h
any of the breeze a d d i t i v e s , shows the s i n g l e substance coke to be
s i g n i f i c a n t l y stronger than those cokes w i t h breeze a d d i t i v e s .
Strength of coke from the prime coking c o a l i s decreased by
a d d i t i o n of p i t c h coke breeze.
For the Cortonwood and Maltby c o a l s the s i n g l e c o a l cokes

are s i g n i f i c a n t l y weaker than those cokes w i t h breeze a d d i t i v e s ,
even 1200 Κ breeze a d d i t i v e s .
I t t h e r e f o r e appears that p i t c h coke breeze a d d i t i v e s can

enhance the coke s t r e n g t h of poorer q u a l i t y caking c o a l s and
that the p i t c h coke breezes of lower HTT (higher v o l a t i l e content)
produce the best r e s u l t s . I t should be emphasized t h a t o n l y one
v a r i a b l e (HTT of the breeze) has been i n v e s t i g a t e d here; other
v a r i a b l e s i n c l u d e s i z e and shape of the breeze p a r t i c l e s and
percentage by weight added to the c a r b o n i z a t i o n system.
Blending. The c o a l - p i t c h and c o a l - c o a l blends were analysed

i n terms of t h e i r o p t i c a l t e x t u r e by p o i n t - c o u n t i n g . Care i s
necessary to d e s c r i b e a c c u r a t e l y the type of a n i s o t r o p y seen and
f o r t h i s purpose a standard nomenclature has been devised (Table
I ) . R e s u l t s of the p o i n t - c o u n t i n g of cokes from the s i x c o a l -
p i t c h blends are shown i n Figures 7 to 10.
From these r e s u l t s i t i s evident that 25 wt % a d d i t i o n of

A200 to c o a l c a r b o n i z a t i o n s can s i g n i f i c a n t l y modify the o p t i c a l
t e x t u r e of the coke from the parent c o a l . R e s u l t s can be p l a c e d
i n 5 categories.
F i r s t l y , c o - c a r b o n i z a t i o n of a n t h r a c i t e s (CR 101) w i t h A200

g i v e s a coke showing two d i s t i n c t types of a n i s o t r o p y or phases.
One phase i s coke from the a n t h r a c i t e not m o d i f i e d by the A200
p i t c h and which shows b a s i c a n i s o t r o p y . The other phase i s coke
from the A200 p i t c h ( f l o w domain a n i s o t r o p y ) which appears to a c t
as a b i n d e r .
Secondly, f o r high rank low v o l a t i l e caking c o a l s (CR 203-

204), cokes produced w i t h 25% A200 p i t c h a l s o show two phases or
types of a n i s o t r o p y but w i t h no sharp boundary between the two.
O p t i c a l t e x t u r e p r o g r e s s i v e l y decreases i n s i z e from the f l o w

Table VI
M i c r o s t r e n g t h r e s u l t s from S i x B e l l s c o a l p l u s 10%
A170 p i t c h coke
Coke c o n s t i t u e n t s R R
3
R
l 2
(%)
S i x B e l l s Coal 3.4 68 26
S i x B e l l s + A170 (green) 2.4 57 39
Six B e l l s + A170 (900 K) 1.9 60 37
S i x B e l l s + A170 (1000 K) 1.2 55 41
S i x B e l l s + A170 (1100 K) 0.85 53 44

S i x B e l l s + A170 (1200 K) 1.0 50 49
Table V I I
M i c r o s t r e n g t h r e s u l t s from Cortonvood coal p l u s 10%
A170 p i t c h coke
Coke c o n s t i t u e n t s R
R
i 2 R
3
(%)
Cortonwood S i l k s t o n e coal 0.1 28 69
Cortonwood + A170 (green) 0.8 48 49
Cortonwood + A170 (900 K) 0.9 50 46
Cortonwood + A170 (1000 K) 0.5 47 51
Cortonwood + A170 (1100 K) 0.2 32 66
Cortonwood + A170 (1200 K) 0.2 42 57
Table V I I I
M i c r o s t r e n g t h r e s u l t s from M a l t b y coal p l u s 10%
A170 p i t c h coke
Coke c o n s t i t u e n t s R
R
l R
2 3
(%)
Maltby Swallow Wood coal 0 21 77
M a l t b y + A170 (green) 0.6 39 59
Maltby + A170 (900 K) 0.5 41 58
Maltby + A170 (1000 K) 0.3 38 60
Maltby + A170 (1100 K) 0.2 31 57
Maltby + A170 (1200 K) 0.1 32 66

100·
80-
60'
40 «
U-4
Ο
20-
lJ
G
CD
4J
G
Ο
Ο
* * ι ι ι ι ι
I Mf Mm Me CFA FD D D I Mf Mm Me CFA FD D
b b
Figure 7. Point-counting analyses of optical textures of cokes. Key: a, Blaen-

hirwaun Pumpquart vitrain (N.C.B. rank 101); and b, Blaenhirwaun Pumpquart
vitrain + 25% A200 pitch.
y 100 η
80-
ο 60-
u
u
ο
•H 40
20-
0J
D,_ I Mf Mm Me CFA FD D I Mf Mm Me CFA FD D
Figure 8. Point-counting analyses of optical textures of cokes. Key: a, Tilman-

stone vitrain (N.C.B. rank 204); and b, Tilmanstone vitrain + 25% A200 pitch.

I Mf Mm Me CFA FD D I Mf Mm Me CFA FD D
o.
Figure 9. Point-counting analyses of optical textures in cokes. Key: a, North
Celynon, Meadow Vein vitrain (N.C.B. rank 301a); and b, North Celynon,
Meadow Vein vitrain + 25% A200 pitch.
u 20-
D, I Mf Un Me CFA FD D I Mf Mm Me CFA FD D
Figure 10. Point-counting analyses of optical textures of cokes. Key: a, Roddy-

moor Ballarat vitrain (N.C.B. rank 301b); and b, Roddy moor Ballarat vitrain
+ 25% A200 pitch.

20-
I Mf Mm Me CFA FD D I Mf Mm Me CFA FD D
Figure 11. Point-counting analyses of optical textures of cokes. Key: a, Manion

Parkgate vitrain (N.C.B. rank 602); and b, Manton Parkgate vitrain + 25% A200
pitch.
100 -,
80·
60-
40-
20-
0J
I Mf Mm Me CFA FD D D, I Mf Mm Me CFA FD D
Figure 12. Point-counting analyses of optical textures of cokes. Key: a, Nail-

stone Yard vitrain (N.C.B. rank 902); and b, Nailstone Yard vitrain + 25% A200
pitch.

domain of coke from the A200 p i t c h through coarse- and f i n e - g r a i n e d

mosaics which extend about 10 ym i n t o the u n a l t e r e d domain a n i s o
tropy of the coke from the c o a l .
T h i r d l y , when A200 i s blended w i t h prime coking and medium

v o l a t i l e caking c o a l s (CR 301-501) the r e s u l t a n t coke shows an
increase i n s i z e of o p t i c a l t e x t u r e compared to that of the c o a l
coke when carbonized s i n g l y . T h i s new o p t i c a l t e x t u r e i s i n t e r
mediate i n s i z e between that of the c o a l coke and p i t c h coke.
F o u r t h l y , A200 p i t c h when co-carbonized w i t h h i g h v o l a t i l e

caking c o a l s (CR 601-701) almost completely m o d i f i e s the i s o t r o p i c
t e x t u r e of the c o a l coke to g i v e an o p t i c a l t e x t u r e predominantly
of medium-grained mosaics. A g a i n , the o p t i c a l t e x t u r e i s uniform

r a t h e r than having two phases.
F i f t h l y , the e f f e c t of A200 a d d i t i o n upon h i g h v o l a t i l e , v e r y

weakly caking and non-caking v i t r a i n s (CR 801-901) i s to reduce
the i s o t r o p i c content of the coke and to i n c r e a s e the content of
f i n e - and medium-grained mosaics.
Thus, f o r most c o a l ranks some m o d i f i c a t i o n i n the o p t i c a l

t e x t u r e i s produced by a d d i t i o n of A200 to the c a r b o n i z a t i o n
system; A200 i s an a c t i v e p i t c h . I t i s suggested t h a t the
mechanism of m o d i f i c a t i o n i s the suppression of the recombination
r e a c t i o n s of f r e e r a d i c a l s created d u r i n g c a r b o n i z a t i o n . This
suppression can be f a c i l i t a t e d by a d d i t i o n of hydrogen donors to
the c a r b o n i z a t i o n system. I t t h e r e f o r e appears that f o r p i t c h e s
such as A200 to be good m o d i f i e r s they should have the a b i l i t y to
donate hydrogen to the products of thermolysis of c o a l .
Acknowledgements
This study was c a r r i e d out w i t h f i n a n c i a l support from the

European Coal and S t e e l Community, Grant No. ECSC 7220-EB-807.
The authors a l s o acknowledge support from BCURA L t d (UK) and the
ACS which made p o s s i b l e the p r e s e n t a t i o n and p u b l i c a t i o n of t h i s
paper. The support of Mrs. Marion Poad and Mrs. P a t r i c i a M. Woo s ter
i s appreciated.
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Gesellschaft 1980, p. 13.
29. Marsh H., Neavel R.C. Fuel 1980, 59, 511.
30. Petrakis L., Grandy P.W. Fuel 1981, 60, 115.
31. Yokono T., Miyazawa K . , Obara T., Sanada Y . , Marsh H. Ext. Abs.
15th Conf. on Carbon, Philadelphia, American Carbon Society
1981, p. 134.
32. Larsen J.W., Sams T.L. Fuel 1981, 60, 272.
33. Marsh H., Mochida I., Scott E., Sherlock J . Fuel 1980, 59, 517.
34. Yokono T., Marsh H. Fuel 1981, 60, 607.
35. Lopez H., Marsh H. Ext. Abs. 15th Conf. on Carbon, Philadelphia,
American Carbon Society 1981, p. 124.
RECEIVED April 30, 1982

2
Characterization of Alkanes in Extracts of Coals,
Lignites, and Related Fuels
K. D. BARTLE
University of Leeds, Department of Physical Chemistry,
Leeds LS2, 9JT, England
D. W. JONES and H. PAKDEL

University of Bradford, School of Chemistry,
Bradford BD7, 1DP, England
1 13
The application of H and C N.M.R. spectroscopy,
gas chromatography (G.C.) and mass spectrometry
(M.S.) in the separation and identification of
alkanes extracted from fossil fuels is illustrated
with three Turkish lignites (including one
extracted by supercritical gas), coal tar and
petroleum crude. Elution of hydrocarbons from a 1
silica-gel column may be monitored byHN.M.R.
and molecular-sieve sub-fractionation into normals 13
and branched/cyclics by G.C., together with C
N.M.R. T measurements. G.C. (e.g. with a eutectic
1
packed column) can enable individual normal, iso-

prenoid and cyclic alkanes, valuable as geochemical
13
indicators, to be identified. C N.M.R. chemical
shifts are consistent with G.C.-M.S. identifications
of acyclic isoprenoids in several fuels.
Alkanes in Fossil Fuels. Sedimentary rocks, which range in

1 9
age from Recent (MO* years) to the pre-Cambrian period (^3 χ 10
years), contain the major reservoir of organic (and reactive)
carbon in the crust of the earth, deposited as fossil fuels: these
include oil shale, coal, petroleum, tar sands, natural asphalts
and natural gas. The organic matter in fossil fuels contains, in
addition to carbon, several percent each of hydrogen and oxygen;
coals and related fuels typically also include 1-5$ nitrogen and
1—10% sulphur (and small amounts of many other elements). These
complicated coal materials are thought to have been generated by
anaerobic degradation of plant and animal materials by micro
organisms in a reducing environment. From asphaltites to high-
rank coals, the carbon content increases and hydrogen content
decreases (Table I); crude oils, to which some reference will also
be made here, have higher hydrogen contents (and much lower
mineral contents) than the solid fuels.
0097-6156/82/O205-0O27$06.0O/O

Table I
Alkane Content o f Hydrocarbon Minerals and Other Sediments
Atomic H/C R a t i o % Alkanes i n

Source
o f Organic Matter Organic Matter
Recent sediments 1.7-1.9 0.8-36.9

Crude o i l s 1.5-2.0 30-1+5
O i l shales 1.3-1.6 6
Turkish asphaltites 1.3 ^-10
Bituminous c o a l s 0.5-0.7 0.U-0.7
Lignites 0.7-1.0 0.01-1.0
T u r k i s h Montan Wax 0.80 0.05
Saturated hydrocarbons amount t o 30 or k0% o f petroleum

crudes and are thus o f d i r e c t economic importance. Although the
much s m a l l e r p r o p o r t i o n s o f alkanes i n c o a l s represent very
l i t t l e d i r e c t commercial v a l u e , a knowledge o f the alkanes
e x t r a c t e d from c o a l l i q u i d s can be o f c o n s i d e r a b l e h e l p i n
determining the behaviour d u r i n g p r o c e s s i n g o f commercial f u e l
products, as w e l l as i n organic geochemical i n v e s t i g a t i o n s o f the
nature and o r i g i n o f f u e l s . The alkanes are g e n e r a l l y present as
a multi-component mixture o f (a) a c y c l i c s - n o r m a l s (predominant),
singly-branched (iso and anteiso), and m u l t i p l y branched (mainly
a c y c l i c i s o p r e n o i d s ) — and (b) c y c l i c s ( n a p h t h e n i c s ) — mono-, d i - ,
t r i - , t e t r a - , and p e n t a c y c l i c s , i n c l u d i n g isoprenoids (Table I I ) .
A n a l y t i c a l Spectroscopy and Spectrometry o f F o s s i l F u e l s .

I n v e s t i g a t i o n o f the composition and s t r u c t u r e o f f u e l s has f o r
long p r o v i d e d one o f the major f i e l d s o f i n d u s t r i a l a p p l i c a t i o n
of molecular spectroscopy (J_). More r e c e n t l y , the demand f o r
d e t a i l e d s t r u c t u r a l analyses o f f o s s i l - f u e l e x t r a c t s has been
stimulated both by i n c r e a s e d i n t e r e s t i n energy sources i n
g e n e r a l , e s p e c i a l l y t h e i r organic geochemistry and the e n v i r o n
mental consequences o f combustion, and, a l s o , f o r c o a l i n
p a r t i c u l a r , by the need f o r i n f o r m a t i o n on the chemical s t r u c t u r e
of the s t a r t i n g m a t e r i a l and o f subsequent stages o f new c o a l -
conversion processes. A wide range of s p e c t r o s c o p i c methods ( 2j ,
i n c l u d i n g n u c l e a r magnetic resonance (N.M.R.) ( i n s o l u t i o n and i n
s o l i d ) , e l e c t r o n s p i n resonance (E.S.R.), i n f r a r e d ( I . R . ) , u l t r a
v i o l e t (U.V.), X-ray and luminescence, has been a p p l i e d t o the
s t r u c t u r a l a n a l y s i s o f f o s s i l f u e l s . However, f o r m a t e r i a l s as
complex as c o a l s , p r e l i m i n a r y s u b d i v i s i o n o f e x t r a c t s i s an
e s s e n t i a l p r e - r e q u i s i t e f o r s u c c e s s f u l e x p l o i t a t i o n o f these
spectroscopic techniques (3.). Thus, when alkanes have been
i s o l a t e d , t h e i r f u r t h e r s u b - f r a c t i o n a t i o n i n t o η and branched-
c y c l i c alkanes may be achieved by 5^ m o l e c u l a r - s i e v e a d s o r p t i o n ,
a method which we g e n e r a l l y p r e f e r t o t h i o u r e a - or urea-adduction.

2. BARTLE ET AL. Characterization of Alkanes 29
TABLE II Saturated Hydrocarbons
Type Typical Carbon S t r u c t u r e Formula Group
(a) acyclic
(i) Normal n 2n+2
C H
(ii) Iso C H n 2 n + 2 Singly-

n Z n + Z
branched
Ante-iso C H 9 a 9 Singly-
n Z n + d
branched
(iii) Acyclic CH 9 9 Poly-

isoprenoid
n Ζ η
~ ά
branched
(b) cyclic
(iv) Monoterpane C^ Q
C H 0 Monocyclic
η en
(Sesquiterpene C | 5
C
n 2n-2 H
Dicyclic
(v)
(Diterpane C H « D i cJ y c l i c
η 2n-2 0
(vi) Diterpane C
n 2n-4 H Τ Η <
* ε 1 1 ( :
(vii) Sterane CH Tetracyclic

η Zn-o
0 c
(viii) Triterpane R
C
n 2 -8 H
n Pentacyclic

Gas chromatography (G.C.) by packed and c a p i l l a r y column then

enables i n d i v i d u a l normal (homologous s e r i e s ) and a c y c l i c i s o -
prenoid alkanes t o be i d e n t i f i e d from, i n the present work, c o a l
t a r s and T u r k i s h l i g n i t e , wax and a s p h a l t i t e s (and a l s o petroleum
crudes).
Over the l a s t two decades, developments i n G.C,, mass
spectrometry (M.S.), N.M.R. spectroscopy and other p h y s i c a l
techniques have a p p r e c i a b l y extended the a b i l i t y o f chemists t o
undertake d e t a i l e d analyses o f f r a c t i o n s e x t r a c t e d from c o a l and
other f o s s i l f u e l s . In t h i s paper, we survey some o f the
c h a r a c t e r i z a t i o n techniques f o r alkanes, emphasising p a r t i c u l a r l y
N.M.R. and M.S. I l l u s t r a t i o n s o f t h e i r a p p l i c a t i o n are mainly
taken from m a t e r i a l s l e s s f u l l y covered i n other p a r t s of the
Symposium, i n c l u d i n g commercial c o a l products, crude petroleum,

and T u r k i s h a s p h a l t i t e s (which have some a f f i n i t i e s with North
American t a r sands), l i g n i t e s and Montan wax.
Experimental
M a t e r i a l s and Methods o f E x t r a c t i o n . The s o l i d Montan wax

(58.8$ carbon i n dry ash-free m a t e r i a l ) was S o x h l e t - e x t r a c t e d
from T u r k i s h (Demircikoy) l i g n i t e (k) with benzene/isopropyl
a l c o h o l , and the r e s i n s andasphaltenes were removed by
Dr. E. E k i n c i ( T e c h n i c a l U n i v e r s i t y of Istanbul). A s p h a l t i t e from
the Avgamasya v e i n (Sirnak i n S i i r t Province, Turkey) was
S o x h l e t - e x t r a c t e d with chloroform and benzene/ethanol and gave
elemental a n a l y s i s C 56.8, Η 5-7, Ν 0.9, S Q.0% (5). The
E l b i s t a n (Turkish) l i g n i t e sample, i n c l u d e d f o r comparison o f 100
1
MHz H N.M.R. s p e c t r a of t o t a l organic e x t r a c t s o f f u e l s , was
e x t r a c t e d by s u p e r c r i t i c a l toluene a t 350°C, a m i l d method which
has been shown (]+,6_) t o possess advantages over Soxhlet
e x t r a c t i o n i n minimising degradation o f alkanes and s e c u r i n g
a p p r e c i a b l e and r e p r e s e n t a t i v e q u a n t i t i e s o f alkanes, v a l u a b l e as
p o t e n t i a l geochemical markers. The Rexco c o a l t a r i s a low-
temperature (750°C) c a r b o n i z a t i o n product (81.U# C d.a.f.)
obtained by the Rexco (smokeless f u e l ) process from U.K.
(Thoresby, CRC 901) c o a l ( j ) . The above v i s c o u s s t a r t i n g
m a t e r i a l s were p a r t i t i o n - s o l v e n t - e x t r a c t e d with d i s t i l l e d c h l o r o
form (or t e t r a h y d r o f u r a n f o r the s o l i d Montan wax) and
s u c c e s s i v e l y separated and e x t r a c t e d with n-hexane u n t i l aromatic
i n s o l u b l e m a t e r i a l no longer separated.
The Kuwait crude-petroleum sample, obtained from
Dr. D.F. Duckworth (B.P. L t d . ) , was d i s t i l l e d up t o 192° under
ordinary pressure t o separate o f f s t r a i g h t - r u n g a s o l i n e and
naphtha (b.p. 32-190°C). The naphtha-free degassed o i l
d i s t i l l a t e was then v a c u u m - d i s t i l l e d on a molecular s t i l l ,
s u c c e s s i v e l y a t 90° and 1.8 T o r r , 130° and 0.9 T o r r , and 130° and
0.08 T o r r . Unsaturateds were l a r g e l y removed from the s o l u t i o n
i n n-hexane by a l t e r n a t i n g separations and treatments w i t h
concentrated s u l p h u r i c a c i d .

N e u t r a l o i l s from s o l i d f u e l s and petroleum crude were

e x t r a c t e d with 10% s u l p h u r i c a c i d and 10% sodium hydroxide
solutions.
Separation and S u b - f r a c t i o n a t i o n o f Alkanes. Saturated

hydrocarbons were separated from the n e u t r a l o i l by s i l i c a - g e l
(60-120 mesh, dehydrated at 150°C f o r 5 h) chromatography i n a
1 m χ 30 mm i . d . column e l u t e d with d i s t i l l e d rc-hexane.
rc-Alkanes were separated from iso-octane s o l u t i o n s of t o t a l
alkanes by adsorption f o r one week on 5 2 molecular s i e v e
( f r e s h l y dehydrated f o r 2h h a t U00°C). Washing with i s o - o c t a n e ,
followed by Soxhlet e x t r a c t i o n , f r e e d the molecular s i e v e from
unwanted non-adsorbed compounds; π-alkanes were recovered by

desorption a f t e r r e f l u x i n g the molecular sieve f o r s e v e r a l hours
with π-hexane. For the Kuwait crude and f l u i d i z e d - b e d t a r , the
molecular-sieve treatment was preceded by urea-adduction o f
rc-alkanes and thiourea-adduction of branched-chain alkanes.
Gas Chromatography, Spectroscopy and Spectrometry. Gas

chromatography on a Pye 105 instrument with f l a m e - i o n i z a t i o n
detector was used f o r monitoring the s e p a r a t i o n o f normals from
t o t a l alkanes and f o r i d e n t i f i c a t i o n o f i n d i v i d u a l rz-alkanes.
i
With a * m x 5 m m i . d . g l a s s packed column, a 30% e u t e c t i c
mixture o f i n o r g a n i c s a l t s (5^.5 wt% KN0 , 27.3% L i N 0 and 18.2
3 3
wt% NaN03 (Analable)) supported on Chromosorb W (J+,.8) proved

quicker and more e f f e c t i v e as s t a t i o n a r y phase than organic
phases. G.C.'s were a l s o run with a 50 m χ 0.25 mm i . d . g l a s s
WC0T c a p i l l a r y column coated with 0V-101.
Gas-chromatography coupled t o mass spectrometry (G.C.-M.S.)
was c a r r i e d out on Rexco and Kuwait b r a n c h e d / c y c l i c f r a c t i o n s
with a Pye 1OU chromatograph (WC0T g l a s s - c a p i l l a r y column coated
with 0V-1) on a V a r i a n MAT hh spectrometer (with SS ihh computer)
at 70 eV i o n i z a t i o n v o l t a g e . For T u r k i s h Montan wax and
a s p h a l t i t e , G.C.-M.S. were run with the e u t e c t i c packed column on
an MS 50 spectrometer. F i e l d - d e s o r p t i o n (F.D.) M.S. f o r Kuwait
and Rexco samples were recorded on a V a r i a n CH5D spectrometer
( c a l i b r a t e d with perfluorkerosene) l i n k e d t o a V a r i a n Spectro-
system 100 data output.
X
H N.M.R. s p e c t r a o f 20% w/v s o l u t i o n s i n d e u t e r i a t e d
chloroform were recorded at 100 MHz on a JE0L MH-100 spectrometer
1 3
and 220 MHz on a V a r i a n HR-220 with T.M.S. as r e f e r e n c e . C
N.M.R. s p e c t r a were recorded at 15 MHz on a JE0L FX 60Q s p e c t r o
meter f o r a s p h a l t i t e b r a n c h e d / c y c l i c (IRFT s p e c t r a ) , a t 22.6 MHz
on a Briïker HX-90E spectrometer f o r b r a n c h e d / c y c l i c s of Kuwait
and Rexco and a s p h a l t i t e e x t r a c t , and at 25.2 MHz on a V a r i a n
XL-100 f o r Rexco b r a n c h e d / c y c l i c s (IRFT s p e c t r a ) .
I n f r a r e d (IR) s p e c t r a o f the t a r e x t r a c t and c r u d e - o i l
d i s t i l l a t e were run as KBr d i s k s on a Perkin-Elmer 257 g r a t i n g
1
spectrometer over the range 600-3500 cm"" .

A p p l i c a t i o n o f Instrumental Techniques
U l t r a v i o l e t (U.V.) and I n f r a r e d (I.R.) Spectroscopy.

1
Observation o f U.V. a b s o r p t i o n (30,000-1+5,000 cm" ) was l a r g e l y
c o n f i n e d t o confirming the absence o f unsaturateds during the
e a r l i e r e l u t i o n with n-hexane o f s a t u r a t e d hydrocarbons through
the s i l i c a g e l . For monitoring the progress o f t h i s s e p a r a t i o n ,
1
i t had some advantage over H N.M.R. i n speed and s e n s i t i v i t y t o
alkenes.
Although o v e r l a p prevents much use o f conventional I.R.
spectroscopy ( i . e . other than i n combination with G.C. (9.) i n
i d e n t i f i c a t i o n o f i n d i v i d u a l alkanes, I.R. can a i d d i f f e r e n t i a
t i o n between s a t u r a t e d and unsaturated hydrocarbons and, t o a

small extent, between c l a s s e s o f alkanes. S l i g h t d i f f e r e n c e s
- 1
i n c l u d e narrower 11+70 c m a b s o r p t i o n i n n-alkanes than branched/
1
c y c l i c s , l o s s o f n-alkane 735 cm" a b s o r p t i o n f o l l o w i n g
1
molecular-sieve treatment, and emergence o f a weak 2880 cm"
C-H band i n b r a n c h e d / c y c l i c alkanes. The I.R. spectrum o f
Montan wax (which has the s u r p r i s i n g l y high sulphur content,
mostly elemental, o f 27%) shows absorptions i n the r e g i o n
c h a r a c t e r i s t i c o f -S-S-, C-S, S=0, S=C, 0-H (presumably primary,
secondary and t e r t i a r y a l c o h o l s ) , C=0, N-H (amide I and I I ) , as
w e l l as weaker absorptions i n the s a t u r a t e d C-H r e g i o n .
^•H N.M.R. Spectroscopy. For comparing mixtures o f s a t u r a t e d

hydrocarbons from d i f f e r e n t f u e l s and f o r monitoring the e f f e c t
iveness o f s i l i c a - g e l column chromatography i n the s e p a r a t i o n o f
normal alkanes from non-normals by 100 and, e s p e c i a l l y , 220 MHz
X
H N.M.R., the emphasis i s on the c h e m i c a l - s h i f t p r o f i l e (j_0) and
peak areas r a t h e r than on s p i n - s p i n c o u p l i n g constants
(Table I I I ) . Although the 100 MHz s p e c t r a i n d i c a t e t h a t the
n-hexane-soluble p a r t o f Montan wax i n CCli* has r a t h e r s i m i l a r
hydrogen d i s t r i b u t i o n s t o the c h l o r o f o r m - s o l u b l e part,about 5k%
of Montan wax was s o l u b l e i n n-hexane; presumably the n-hexane-
i n s o l u b l e f r a c t i o n contains a l l the alkanes, as w e l l as p o l y -
c y c l i c aromatics. The s p e c t r a o f n-hexane- and chloroform-
s o l u b l e f r a c t i o n s o f T u r k i s h a s p h a l t i t e i n d i c a t e hydrogen
d i s t r i b u t i o n s o f about 7.8 and 12.2 H , 21.2 and 22.0 H , 1+6.0
A a
and 1+3.3 Hg, and 25 and 22.5% Η . γ
X
A v a i l a b i l i t y o f H N.M.R. s p e c t r a a t 220 MHz (Figure 1)
increases the c h e m i c a l - s h i f t s e p a r a t i o n and so enhances the
d i f f e r e n c e s between d i s t i n c t kinds o f hydrogen. For a l l the f u e l
e x t r a c t s examined, removal o f n-alkanes by molecular s i e v e from
the t o t a l alkanes causes small changes i n the methyl absorptions
as a r e s u l t o f changing p r o p o r t i o n s o f s p i n - s p i n t r i p l e t s (from
C# -CH -), doublets (from C# -CH-), and s i n g l e t s (from CH -Cc).
3 2 3 3
At 220 MHz, the C# r e g i o n o f the b r a n c h e d / c y c l i c Kuwait crude

3
(Figure 1(b)) i s c l o s e l y s i m i l a r t o the C# r e g i o n o f the branched/

3
c y c l i c f r a c t i o n from a U.K. low-temperature-carbonization

c l a s s i c a l coal t a r .

Table I I I
Examples o f Hydrogen D i s t r i b u t i o n i n F o s s i l - F u e l Alkane

1
E x t r a c t s Measured from 100 MHz H N.M.R. Spectra:
( i ) t o t a l - a l k a n e e x t r a c t (before n-alkane removal);
( i i ) branched-chain/cyclic e x t r a c t ( a f t e r n-alkane removal
by molecular s i e v e .
&
%
Sample
H
3,
(i) (ii) (i) (ii) (i) (ii
3h
Kuwait crude 50 1*5 16 18 37

Rexco c o a l t a r 69 53 9 15 21 32
Turkish asphaltite
(Avgamasya) 38 27 35
Turkish l i g n i t e
(Elbistan) 21 31
T u r k i s h Montan-wax hi 19 31»
Branched-chain C#2 (plus small amounts o f CH3 α t o a r i n g (10) ).

Branched-chain CH and c y c l i c CH2 hydrogens.
C#3 i n l i n e a r and branched-chains and i n c y c l i c s 3 or f u r t h e r
from r i n g .
Figure 1. Alkane regions of 220-MHz H NMR spectra of a, Montan wax total

1
alkanes; and b, Kuwait crude branched cyclics in CCl solution (shifts in ppm
h
downfield from TMS).

During e l u t i o n o f the n-hexane-soluble f r a c t i o n s o f f o s s i l

f u e l s , s a t u r a t e d alkanes, with strong resonances "between 0.5-2.0
p.p.m., may be d i s t i n g u i s h e d r e a d i l y by areas on 100 MHz s p e c t r a
from unsaturated hydrocarbons, with peaks i n the regions o f k-6
p.p.m. and 6-8 p.p.m. Thus, the change i n p r o f i l e o f alkane
resonances during e l u t i o n o f a Kuwait c r u d e - o i l d i s t i l l a t e
f r a c t i o n ( f r e e o f unsaturateds) p r o v i d e s a very e f f e c t i v e monitor
of the s e p a r a t i o n p r o c e s s . In the spectrum o f the branched/
c y c l i c alkane f r a c t i o n ( i . e . a f t e r removal o f n-alkanes) chain
methylenes absorb a t s l i g h t l y higher f i e l d than r i n g methylenes
and are a l s o sharper (because o f the f r e e r o t a t i o n o f the
m a g n e t i c a l l y equivalent hydrogens) than c y c l i c methylenes i n
f i x e d conformations ( i n which the hydrogens are not m a g n e t i c a l l y
X
e q u i v a l e n t ) . Thus the H N.M.R. spectrum o f a complex mixture
which contains both r i n g and chain hydrocarbons shows a broad
band f o r c y c l i c methylene absorption and a narrower one f o r chain
methylenes (which sharpens as the number o f methylenes i n c r e a s e s ) .
The l a t e r the e l u a t e , the h i g h e r i s the area r a t i o C#3/(C#2 + CH).
3
Successive 10 cm eluates show a steady decrease i n the propor
t i o n o f C#2 (from the combination o f normals, which are removed
f i r s t , and branched) and then a steady i n c r e a s e i n (C#2 + CH)
(6 M.3-2.0 p.p.m.), which comes from branched (CH) and c y c l i c
(C#2 C#) peak areas. Since they are mostly e l u t e d i n ^ t h e l a s t
5
few f r a c t i o n s , c y c l i c s can have t h e i r c o n c e n t r a t i o n reduced by

s i l i c a - g e l chromatography, a procedure which would favour
1 3
i d e n t i f i c a t i o n o f a c y c l i c i s o p r e n o i d s by C N.M.R. For Montan
X
wax, about o n e - t h i r d o f the alkane-peak area i n the 100 MHz H
spectrum i s Ηγ (CH3), a much higher p r o p o r t i o n than i n c o a l t a r s ;
the appearance o f the methyl r e g i o n at 220 MHz a l s o p o i n t s t o
a p p r e c i a b l e branched chains i n t h i s m a t e r i a l .
1 3 1 3
C N.M.R. Spectroscopy. As an N.M.R. n u c l e u s , C s u f f e r s
from low " r e c e p t i v i t y " (JJ_) and r e l a t i v e l y long (and d i f f e r e n t )
s p i n - l a t t i c e r e l a x a t i o n times, Τχ, but these disadvantages are
overcome by p u l s e e x c i t a t i o n and f a s t F o u r i e r t r a n s f o r m a t i o n o f
the f r e e - i n d u c t i o n decay. Advantage may thus be taken o f the
1 3
narrow w e l l - r e s o l v e d C N.M.R. l i n e s (with a much wider spread
1 1 3 1
of chemical s h i f t s than f o r H and with C - H s p i n c o u p l i n g
X
e l i m i n a t e d by noise-modulated H decoupling) from, i n p r i n c i p l e ,
a l l the c h e m i c a l l y d i s t i n c t carbon atoms i n a complex n a t u r a l -
1 3
abundance f o s s i l - f u e l e x t r a c t . Consequently, C N.M.R. has been
much used f o r petroleums and i s now i n c r e a s i n g l y a p p l i e d t o
sediments and c o a l s . For alkanes, whether s i n g l e compounds o r
1 3
mixtures, isomers may o f t e n be d i s t i n g u i s h e d by means o f C
s h i f t s and i n t e n s i t i e s , taken with s u b s t i t u e n t - s h i f t c a l c u l a t i o n s
based on a d d i t i v i t y r u l e s . Thus, i n the a c y c l i c i s o p r e n o i d
p r i s t a n e , whereas CH and C#2 resonances are not r e s o l v e d i n the
X 1 3
H spectrum, nine C resonances can be r e s o l v e d (j[2). Broad
1 1 3
band H-decoupled C s p e c t r a have p r o v i d e d c o n v i n c i n g support
f o r the i d e n t i f i c a t i o n o f s i x a c y c l i c i s o p r e n o i d s i n alkane

mixtures d e r i v e d from f l u i d i z e d - b e d low-temperature-carbonization

(Rexco) c o a l t a r and from Kuwait crude (_13j ; these assignments
are supported by recent T i measurements (see l a t e r ) . Both f o r
n-alkanes (or s t r a i g h t - s i d e - c h a i n s e c t i o n s o f branched or
s u b s t i t u t e d c y c l i c s ) and f o r a c y c l i c i s o p r e n o i d s , the c l o s e
1 3
agreement between observed C s h i f t s and those c a l c u l a t e d shows
that the a d d i t i v i t y r e l a t i o n , w e l l - t e s t e d f o r s h o r t e r - c h a i n
s i n g l e compounds (j_2), i s a l s o a p p l i c a b l e t o mixtures o f l o n g -
chain alkanes. For a c y c l i c i s o p r e n o i d s , the m a j o r i t y o f the
absorptions f o r p a r t i c u l a r carbon environments occur i n s e v e r a l
d i f f e r e n t compounds; indeed, about seventeen s h i f t s accounted f o r
a l l the resonances i n a l l i s o p r e n o i d s , as w e l l as f o r those i n
n-alkanes. For c y c l i c alkanes, on the other hand, which f i g u r e

s i g n i f i c a n t l y i n the branched-chain/cyclic f r a c t i o n s o f Kuwait
1 3
and a s p h a l t i t e , f o r example, C absorptions are d i s t r i b u t e d over
the approximate range 10-55 p.p.m. and there i s l e s s coincidence
between chemical s h i f t s o f d i f f e r e n t homologues. Thus i d e n t i f i
c a t i o n o f i n d i v i d u a l c y c l i c alkanes, i f achieved, w i l l be
unequivocal, but the resonances tend t o be broad (from overlap
of c l o s e s h i f t s ) and weak (7.).
For Rexco b r a n c h e d / c y c l i c s , g a t i n g o f the ^ - n o i s e
decoupling (so t h a t i t i s a p p l i e d only during s i g n a l a c q u i s i t i o n )
i n order that nuclear Overhauser enhancement (n.O.e.) i s
suppressed causes the i n t e n s i t i e s o f the methylene (29.85 p.p.m.)
t o decrease r e l a t i v e t o that o f the methyl (1U.15 p.p.m.).
Presumably d i f f e r e n t r e l a x a t i o n mechanisms predominate i n the two
cases (Jih) ; f o r the methylene group, r e l a x a t i o n i s mainly d i p o l a r ,
with p o s i t i v e Overhauser enhancement, whereas the methyl group
may r e l a x by s p i n - r o t a t i o n with negative Overhauser enhancement.
In q u a n t i t a t i v e measurements, the problems posed by
v a r i a b l e n.O.e. and by r a t h e r long and d i f f e r e n t s p i n - l a t t i c e
r e l a x a t i o n times, Τχ, can be l a r g e l y overcome, as with o i l
products (j_5 ), i f Τχε are reduced by the a d d i t i o n o f paramagnetic
r e l a x a t i o n agent, Cr(acac)3, t o the sample, together with the use
1 3
of gated c o u p l i n g . F o r the gated-decoupled C spectrum o f
branched/cyclic alkanes from a U.S. f l u i d i z e d - b e d c o a l t a r (FMC
COED), a d d i t i o n o f 150 mg Cr(acac)3 had greater e f f e c t on the
i s o p r e n o i d resonances than on those a t t r i b u t e d t o s t r a i g h t - c h a i n
s e c t i o n s . Problems due t o low concentration o f isoprenoids and
to broadening and overlap o f l i n e s , may s t i l l remain, o f course.
1 3
As an example o f off-resonance ^ - d e c o u p l i n g o f C s p e c t r a ,
whereby the m u l t i p l e s t r u c t u r e s due t o s p i n - s p i n c o u p l i n g t o
d i r e c t l y - b o n d e d hydrogens are r e t a i n e d but longer-range couplings
are e l i m i n a t e d , the Rexco branched-chain/cyclic f r a c t i o n spectrum
(Figure 2) contains t e n m u l t i p l e t s (with i n d i v i d u a l l i n e widths
up t o Τ Hz), i d e n t i f i e d (from s h i f t s i n the f u l l y decoupled
spectrum and from s p l i t t i n g s ) as alkane (mainly a c y c l i c - i s o -
prenoid) resonances. Quartet 1 (1U.0 p.p.m.) a r i s e s from methyl,
and t r i p l e t s 2, 3 and h (22.8, 28.5 and 29.8 p.p.m.) from methy
lene absorptions o f s t r a i g h t - c h a i n s e c t i o n s . The f a i r l y intense

J oo
N
s: -
g
Sac
lis
&s s-
"•s s
8 sf*
« §
. s:
fN —
«Ο
%>
S e

branched-chain methyl, methylene and methine carbon resonances a t

19.7 (-CH ), 2h.6 (-OT -), 28.1 (-CT ), 32.9 (-CH), 3 7 · ^ (-CH )
3 2 2 2
and 39-5 p.p.m. (-CH ) were a l s o i d e n t i f i e d with the a i d o f t h e i r

2
m u l t i p l e t p a t t e r n s i n the off-resonance spectrum.
1 3
C S p i n - l a t t i c e Relaxation-Time Measurements. Determination
1 3
of C s p i n - l a t t i c e r e l a x a t i o n times (Τχ) f o r i n d i v i d u a l carbons
of alkanes provides a d i r e c t probe o f backbone segmental motion
and o f l o c a l i s e d motion o f s i d e - c h a i n and t e r m i n a l main-chain
carbons (16,17). In a given alkane, enhanced segmental motion o f
the c h a i n causes Τ χ o f CH groups t o decrease as a f u n c t i o n o f
2
the distance from the end o f the c h a i n , and Τχ f o r a given carbon

to decrease p r o g r e s s i v e l y as the c h a i n l e n g t h i s i n c r e a s e d . Thus

Τχ i s l i k e l y t o depend on the molecular weight o f the sample, as
w e l l as on i t s v i s c o s i t y . By changing the r e o r i e n t a t i o n a l
c h a r a c t e r i s t i c s o f the nearest carbons, branching a l t e r s t h e i r
r e l a x a t i o n times, an e f f e c t which decreases with i n c r e a s i n g
numbers o f bonds away from the branching p o i n t .
Τχ measurements a t normal probe temperature were made by the
i n v e r s i o n - r e c o v e r y F o u r i e r - t r a n s f o r m (IRFT) technique on
d e u t e r i a t e d chloroform s o l u t i o n s o f p r i s t a n e ( 2 , 6 , 1 0 , l U - t e t r a -
methylpentadecane) and o f b r a n c h e d - c h a i n / c y c l i c alkanes from
Rexco c o a l t a r and a T u r k i s h a s p h a l t i t e (Avgamasya). I n v e r s i o n -
recovery t r a c e s were recorded by u s i n g 200 c y c l e s o f the 180°-
90°-PD p u l s e sequence with a p u l s e delay time (PD) o f about 20s
at a s e r i e s o f i n t e r v a l s , τ (e.g. 1,3,5s, F i g u r e 3 ) . Τ χ values
(±0.5s) (Table IV) were measured by p l o t t i n g l n ( A - A ) vs. τ , Q
where A i s the e q u i l i b r i u m amplitude i n a normal FT spectrum and

Q
A i s the amplitude i n an IRFT spectrum (Figure k).

Τχε f o r the branched-chain carbons from Rexco c o a l - t a r
alkanes are g e n e r a l l y r a t h e r lower (0.7-2.0s) than those o f the
n-alkanes (1.0-3.5s) i n the mixture. For s i n g l y branched alkanes
(e.g. 10-methylnonodecane) (YJ_) and m u l t i p l y branched alkanes
(j8.), the decrease i n t h e Τχε at (or near) t h e branch p o i n t o f
the c h a i n has been a s s o c i a t e d with a decrease i n i n t e r n a l motion.
For p r i s t a n e , our Τχε (Table IV) measured i n d e u t e r i a t e d c h l o r o
form s o l u t i o n are r a t h e r l a r g e r than, but g e n e r a l l y i n t h e same
sequence a s , those r e p o r t e d by Long et a l . (_l8.) f o r neat samples
at about the same temperature; the s h o r t e s t Τχε correspond t o the
midchain methylenes C5, C7 and C and the longe8t t o the8
(branched) methine C . Τχε a t t r i b u t e d t o re8onance i n s t r a i g h t -

2
chain s e c t i o n s are r a t h e r s h o r t e r i n Rexco and longer i n the

a s p h a l t i t e than those r e p o r t e d by B i r d s a l l e t a l . (j_9) and L y e r l a
et a l . (Jj6) i n the neat n-alkanes hexadecane, octadecane and
eicosane. Now i t i s t o be expected t h a t , i n g e n e r a l , Txs w i l l be
shorter f o r systems o f higher molecular weight and o f lower
viscosity. Since n e i t h e r the molecular weights nor t h e v i s c o s
i t i e s o f the two samples are thought t o d i f f e r a p p r e c i a b l y , one
may i n f e r t h a t some o f the c h a i n carbons i n Rexco alkanes are
f a i r l y c l o s e t o methine carbons (branch p o i n t s ) , so t h a t i n t e r n a l

oo

Table IV
1 3
C s p i n - l a t t i c e r e l a x a t i o n times, Τχ/s, o f branched-chain/cycl
f r a c t i o n o f Rexco c o a l t a r , T u r k i s h (Avgamasya) a s p h a l t i t e and
p r i s t a n e ( a l l measured i n d e u t e r i a t e d chloroform s o l u t i o n ) .
Chemical s h i f t Ti (coal t a r ) Τχ ( a s p h a l t i t e ) Example o f carbon

/ppm from TMS /s /s type***
11.U U.O Ci (phytane)

6
1*.1 3.5 5.3 CH 3
19.8 1.5 2.1 Ci7>C (phytane)

18
22.6 1.7 NM Ci(phytane)

22.7 2.0 3.9 CH3 — C ~2
2U.5 0.7 NM Ci*(phytane)

2k.9 1.3 NM Ce,i2(phytane)
26.9 1.2 2.1 (cycloalkane)
27.2 1.2 NM C12(norpristane)
28.1 2.5 7.8 C (phytane)
2
29Λ 1.5 2.U 3

CH -(CH )2-CH - 2 2
29.8 1.0 1.9 CH3-(CH )3-(ÇH ) - 2 2 n
30.2 1.0 1.2 (cycloalkane)

32.0 1.7 3.5 CH3—CH —CH2 2
32.9 1.0 2.5 Ce,io(phytane)

33.3 1.3 NM C13(norpristane)

3U.5 1.3 NM Cii*(phytane)
37.1 0.8 2.0 Ci3(pbytane)
37. U 0.7 2.0 C5 9 , 1 1 , 7 ( p h y t a n e )
39.5 1.5 NM C (phytane)
3
t S u b s c r i p t s i n d i c a t e carbon-atom numbers. NM = not measured.

COAL AND COAL PRODUCTS
ln(^-A)5
Pulse interval T/S
Figure 4. Logarithmic plots of relative signal amplitude, (A — A) vs. pulse

0
interval, τ, for determination of C spin-lattice relaxation times (T ) of three species

13
t
of carbons in Avgamasya-asphaltite alkanes. Key to 7V O, 2.2 s; Φ, 1.9 s; and

A, 2.0 s.

motions are reduced and consequently T i s are lower than i n a f r e e

n-alkane c h a i n ; f o r a s p h a l t i t e alkanes, on the other hand, c h a i n -
carbon peaks may be superimposed on those o f carbon atoms with
longer r e l a x a t i o n times.
Gas Chromatography. Whereas N.M.R. e f f e c t i v e l y senses the

f u n c t i o n a l groups present i n a mixture, d i f f e r e n c e s between
r e t e n t i o n times enable G.C. t o i d e n t i f y i n d i v i d u a l members
(provided they are moderately v o l a t i l e ) o f a homologous s e r i e s
such as the n-alkanes. P o s i t i v e i d e n t i f i c a t i o n r e q u i r e s
c a l i b r a t i o n by c o - i n j e c t i o n with authentic samples (here
n-alkanes) or c o u p l i n g o f M.S. w i t h , p r e f e r a b l y , a c a p i l l a r y G.C.
column. Although G.C. s t i c k diagrams o f n-alkane d i s t r i b u t i o n s

have been used f o r comparing e x t r a c t s from f o s s i l f u e l s , we
advocate a c y c l i c - i s o p r e n o i d - h y d r o c a r b o n d i s t r i b u t i o n s , and
p a r t i c u l a r l y t h e pristane/phytane r a t i o , as more r e l i a b l e
i n d i c a t o r s o f f o s s i l f u e l maturation (6).
G.C. was c a r r i e d out on a l l the f o s s i l - f u e l e x t r a c t s but t h e
a n a l y s i s by e u t e c t i c packed column and by c a p i l l a r y - c o l u m n (OV-1
WCOT) o f the t o t a l alkane f r a c t i o n from T u r k i s h Montax wax
i l l u s t r a t e s (h) t h e unambiguous assignment o f s e r i e s o f
n-alkanes {0ΐ2-0$ι> with odd carbon numbers predominating over
9
evens from n - C 2 upwards) and o f a c y c l i c i s o p r e n o i d s ( C 1 8 - C 2 0 :

2
n o r p r i s t a n e , p r i s t a n e and phytane); cycloalkanes were a l s o

i d e n t i f i e d by G.C.-M.S. For Avgamasya a s p h a l t i t e , the t o t a l -
alkane G.C. ( e u t e c t i c column) shows an approximately Gaussian
d i s t r i b u t i o n o f n-alkanes i n the C12-C32 range (centred on
n-Cu) with a l a r g e background peak due t o the r e l a t i v e l y high
cycloalkane content. The G.C. o f the b r a n c h e d / c y c l i c f r a c t i o n
a s s i s t e d r e t e n t i o n - t i m e c o n f i r m a t i o n o f the presence o f f i v e
a c y c l i c i s o p r e n o i d s ( C 1 5 , C i 6 , C i e , C 1 9 and C 2 0 ) i n d i c a t e d i n t h e
G.C.-M.S. From the G.C. o f t h e t o t a l - a l k a n e f r a c t i o n o f another
T u r k i s h a s p h a l t i t e ( H a r b u l i t e ) (5.), i t was p o s s i b l e t o recognise
three s e r i e s , namely n-alkanes, a c y c l i c i s o p r e n o i d s ( C 1 5 , C i 6 ,
Ci8> C 1 2 , C 2 0 K and c y c l i c i s o p r e n o i d s ( C 2 7 » C 2 9 , C 3 0 , C 3 1 and
C 3 2 ) , a l l on t h e same chromatogram. F o r the Rexco c o a l t a r ,
G.C.s o f t o t a l - a l k a n e (Figure 5(a)) and b r a n c h e d / c y c l i c alkanes
(Figure 5(b)) demonstrate t h e e f f e c t i v e n e s s o f the molecular
s i e v e i n removing n-alkanes; the remaining t r a c e o f n-alkanes
would be e l i m i n a t e d by r e f l u x i n g i n t h e molecular s i e v e f o r a
few more hours.
Gas Chromatography - Mass Spectrometry. Coupling t o a mass

spectrometer can g r e a t l y reduce t h e ambiguities i n e x t r a c t i n g
s t r u c t u r a l i n f o r m a t i o n from the small q u a n t i t i e s o f m a t e r i a l s
employed i n gas chromatography. With G.C.-M.S., a complete
mass-spectrometric a n a l y s i s can be obtained i n e s s e n t i a l l y the
time r e q u i r e d f o r an o r d i n a r y G.C. run; with computer data-
p r o c e s s i n g , each component can be analysed and t h e homogeneity
o f a s i n g l e G.C. peak can be checked by o b t a i n i n g s u c c e s s i v e mass

Figure 5. Gas chromatograms of Rexco coal-tar recorded on glass column with

eutectic salt on Chromosorb. Key: a, total alkanes; and b, branched cyclic alkanes
following molecularsieve removal of most of the n-alkanes.

s p e c t r a l scans. In t h i s way, i t has been p o s s i b l e t o e s t a b l i s h

the presence, i n alkane f r a c t i o n s from a range o f c o a l t a r s and
l i g n i t e s , o f up t o s i x a c y c l i c i s o p r e n o i d s (j_3) and a number o f
c y c l i c i s o p r e n o i d s (7.). Thus f o r the b r a n c h e d / c y c l i c alkane
f r a c t i o n from T u r k i s h Montan wax, G.C.-M.S. with a e u t e c t i c
packed column allowed i d e n t i f i c a t i o n o f 21 n-alkanes ( C i - C ) , 3 3 3
three a c y c l i c i s o p r e n o i d s ( C 1 8 - C 2 0 K and three c y c l i c alkanes

(two C 3 i t r i t e r p a n e s and one d i c y c l i c alkane) (k). Figure 6
shows the t o t a l - i o n - c u r r e n t t r a c e computer-reconstructed from the
G.C.-M.S. a n a l y s i s . The n-alkane d i s t r i b u t i o n i s d i s t i n c t i v e ,
with a marked preference o f odd over even carbon number (carbon
preference index, 1.9, as i n low-rank c o a l s ) i n the range above
C25 but with a smooth, n e a r l y Gaussian, d i s t r i b u t i o n f o r the

lower rarge (peaked at Ci6 or C 1 7 ) ; a l s o , the pristane/phytane
r a t i o i s high (1+.5), as i n sediments o f marine o r i g i n .
Field-Desorption-Mass-Spectrometry. A n a l y s i s o f G.C.-M.S.
s p e c t r a from complex mixtures such as c o a l - d e r i v e d e x t r a c t s
recorded by electron-impact (E.I.) i o n i z a t i o n spectrometers i s
o f t e n rendered d i f f i c u l t by the p r o f u s i o n o f fragment-ion peaks,
weak molecular-ion peaks and background G.C. peaks; moreover l e s s
v o l a t i l e compounds may not be sensed. F i e l d - d e s o r p t i o n (F.D.)
M.S., though not without experimental and i n t e r p r e t a t i v e problems
(fragment-ion peaks are not a v a i l a b l e t o a i d isomer e l u c i d a t i o n ) ,
permits i o n i z a t i o n (by an e l e c t r i c f i e l d ) o f h i g h e r - b o i l i n g
compounds i n v o l a t i l e under E . I . M.S. c o n d i t i o n s . For the
branched/cyclic f r a c t i o n o f Kuwait crude, F.D. M.S. enabled the
molecular-weight ranges f o r a c y c l i c and mono-, d i - , t r i - , t e t r a -
and p e n t a c y c l i c alkanes ( i n c l u d i n g C2 8» unusual i n f o s s i l f u e l s )
to be e s t a b l i s h e d . F.D. M.S. has a l s o been v a l u a b l e i n
i n d i c a t i n g the presence o f a range o f mono-, d i - and t r i c y c l i c
alkanes (some t e t r a c y c l i c s (steranes) and p e n t a c y c l i c s ( t r i t e r -
panes) had already been e s t a b l i s h e d by G.C. M.S. (7.)) i n the
b r a n c h e d / c y c l i c e x t r a c t from Rexco c o a l t a r . F.D. M.S. s p e c t r a
of C S 2 e x t r a c t s o f c o a l macérais (20) a l s o provide evidence f o r
the presence i n c o a l o f n-alkanes with η as high as 50 or 60.
Acknowledgement s
We express thanks t o Drs. E. E k i n c i and D.F. Duckworth f o r

samples, t o Dr. D. Games f o r the f i e l d - d e s o r p t i o n mass s p e c t r a ,
and t o Drs. J.E. Beynon and F.W. Wehrli and t o the PCMU Harwell
1 3
for C N.M.R. s p e c t r a .

•Ρ*
DS-58 CROSS SC«Η REPORT. RUN: D441 Montan wax SOW REPORT. RUN: D441
Eutectic colum

1 28
Figure 6. Total ion current constructed from GC MS spectra of Montan wax total-alkane frac
tion.
I
Η
Literature Cited
1. Friedel, R.A. "Spectrometry of Fuels"; Plenum, New York,
1970.
2. Speight, J.G. "Analytical Methods for Coal and Coal
Products"; Karr, C. J r . , Ed., Academic, New York, 1978;
Vol. 2; p.75.
3. Bartle, K.D.; Jones, D.W.; Pakdel, H. "Analytical Methods
for Coal and Coal Products"; Karr, C. J r . , Ed., Academic,
New York, 1978; Vol. 2; p.210.
4. Bartle, K.D.; Jones, D.W.; Pakdel, H. Separation Science
and Technology 1982, in press.
5. Bartle, K.D.; Ekinci, E . ; Frere, B.; Mulligan, M.; Sarac,
S.; Snape, C.E. Chem. Geol., in press.

6. Bartle, K.D.; Jones, D.W.; Pakdel, H.; Snape, C.E.; Calimli,
Α.; Olcay, Α.; Tugrul, T. Nature 1979, 277, 284.
7. Jones, D.W.; Pakdel, H.; Bartle, K.D. Fuel, in press.
8. Snowden, L.R.; Peake, E. Anal. Chem. 1978, 50, 379.
9. Abelson, H.I.; Gordon, J.S.; Lowenbach, W.A. "Analytical
Methods for Coal and Coal Products"; Karr, C. Jr., Ed.,
Academic, New York, 1978; Vol. 2; p.563.
10. Bartle, K.D. Rev. Pure Appl. Chem. 1972, 22, 79.
11. Harris, R.K. "N.M.R. and the Periodic Table"; Harris, R.K.;
Mann, B.E. Eds., Academic, London, 1979.
12. Lindemann, L.P.; Adams, J.Q. Anal. Chem. 1971, 43, 1245.
13. Bartle, K.D.; Jones, D.W.; Pakdel, H. "Molecular Spectro
scopy"; West, A.R., Ed., Heyden, London, 1977; p.127.
14. Abraham, R.J.; Loftus, P.L. "Proton and Carbon-13 N.M.R.
Spectroscopy"; Heyden, London, 1979.
15. Gillet, S.; Rubini, P.; Delpuech, J.I.J.; Escalier, J.-C.;
Valentin, P. Fuel, 1981, 60, 221.
16. Lyerla, J.R.; McIntyre, H.M.; Torchia, D.A. Macromolecules
1974, 7, 11.
17. Lyerla, J.R. Jr.; Horikawa, T.T. J. Phys. Chem. 1976, 80,
1106.
18. Long, R.V.; Goldstein, J.H.; Carman, C.J. Macromolecules
1978, 11, 574.
19. Birdsall, N.J.M.; Lee, A.G.; Levine, Y.K.; Metcalf, J.C.;
Partington, P.; Roberts, C.K. J.C.S. Chem. Comm. 1973, 757.
20. Drake, J.A.G.; Games, D.; Jones, D.W. unpublished
measurements.

3
Fourier Transform IR Spectroscopy

Application to the Quantitative Determination
of Functional Groups in Coal
PAUL C. PAINTER, RANDY W. SNYDER, MICHAEL STARSINIC,

MICHAEL M. COLEMAN, DEBORAH W. KUEHN, and ALAN DAVIS
Pennsylvania State University, College of Earth and Mineral Sciences,
University Park, PA 16802
Fourier transform infrared (FTIR) spectroscopy is

potentially a powerful tool for the characterization
of coal. Although the optical advantages of these
instrument compared to traditional dispersive de-
vices are important, we believe that the most sig-
nificant results can be obtained by applying sophis-
ticated data analysis programs. However, if these
programs are applied uncritically there is the real
possibility of serious error, particularly in quanti-
tative work. Consequently, in this paper we will
attempt an assessment of the application of FTIR to
the quantitative determination of functional groups,
with particular emphasis on O-H and C-H groups. We
will consider the use of programs for spectral sub-
traction, derivative spectra, curve resolving and
factor analysis.
1
In the late 1950*s and early I960 s infrared spectroscopy
was a widely used analytical tool for investigating the
structure of coal. Unfortunately, this technique was limited
in part by the problems associated with investigating highly
absorbing systems but predominantly by the overlap and super-
position of the vibrational modes characteristic of such
complex multicomponent systems. In fact, by 1973 there was
a general decline in the use of infrared spectroscopy for chemical
studies as other techinques (eg NMR) came to the fore.
This state of affairs prompted H.A. Laitinen, in an editorial in
Analytical Chemistry (1), to draw an analogy between the seven
ages of an analytical technique and Shakespeare's seven ages of
man, using infrared spectroscopy as a prime example. Senescence
and an early demise seemed assured. However, for analytical
CgWW^WmwWaiMiSRSiucal Society
Society Library
1155 16th St. N. W.
In Coal and Coal Products: Analytical
Washington, 0. C. Characterization
20036 Techniques; Fuller, E.;
techniques there i s always the p o s s i b i l i t y of r e i n c a r n a t i o n and at

the same time as L a i t i n e n ' s depressing prognosis appeared commer-
c i a l F o u r i e r transform i n f r a r e d instruments were being d e l i v e r e d
to a number of l a b o r a t o r i e s . The subsequent resurgence of i n f r a -
red spectroscopy has been remarkable and has l e d to a renewed i n -
t e r e s t i n a p p l y i n g t h i s technique to the c h a r a c t e r i z a t i o n of c o a l
structure.
A d e s c r i p t i o n of F o u r i e r transform i n f r a r e d (FTIR) instruments
together with an account of the u n d e r l y i n g theory and o p t i c a l ad-
vantages compared to conventional d i s p e r s i v e spectrometers has
been given by a number of authors (2-4). Although the improvements
i n the q u a l i t y of the s p e c t r a that can be obtained from m a t e r i a l s
such as c o a l are u s e f u l , i n our o p i n i o n the most s i g n i f i c a n t ad-
vances have been made through the use of the dedicated o n - l i n e

minicomputer that i s an i n t e g r a l p a r t of the system. Programs cap-
able of a range of manipulations, from the simple such as s p e c t r a l
s u b t r a c t i o n to the complex l i k e f a c t o r a n a l y s i s can now be r o u t i n e -
l y a p p l i e d . N a t u r a l l y , t h i s type of a n a l y s i s i s not unique to
1
FTIR and many s o p h i s t i c a t e d techniques were developed i n the I960 s
f o r use with d i g i t i z e d data obtained from d i s p e r s i v e instruments.
Nevertheless, computer methods were not r o u t i n e l y a p p l i e d and the
type of a n a l y s i s that depends on data manipulation has subsequently
become a s s o c i a t e d with FTIR.
Havelock E l l i s remarked that "What we c a l l progress i s the
exchange of one nuisance f o r another nuisance". The advent of
computerized instruments has c e r t a i n l y made r o u t i n e a number of
d i f f i c u l t s p e c t r o s c o p i c measurements. U n f o r t u n a t e l y , the s o p h i s -
t i c a t i o n of the procedures now a v a i l a b l e can r e s u l t i n erroneous
r e s u l t s or i n t e r p r e t a t i o n s i f they are not used with c a u t i o n . A
c l a s s i c example i s the use of c u r v e - r e s o l v i n g techniques. There
i s always a s u s p i c i o n that a good f i t between an observed s p e c t r a l
p r o f i l e and a number of bands can be obtained p r o v i d i n g that a
s u f f i c i e n t number of the l a t t e r are i n c l u d e d i n the a n a l y s i s .
C l e a r l y , i n such cases a p r i o r knowledge of the number of bands
and t h e i r frequency would s i g n i f i c a n t l y i n c r e a s e our confidence i n
the r e s u l t s .
In t h i s review we w i l l attempt to c r i t i c a l l y assess the
a p p l i c a t i o n of FTIR procedures to the c h a r a c t e r i z a t i o n of the
s t r u c t u r e of c o a l . To an extent much of what we have to say i s not
original. D i f f i c u l t i e s , such as those mentioned above f o r curve
r e s o l v i n g , were encountered and addressed a number of years ago.
However, with the advent of any new instrumentation there i s a
tendency to ignore segments of previous work that were obtained on
i n f e r i o r machines and i n e f f e c t spend a c o n s i d e r a b l e amount of
time and e f f o r t " r e i n v e n t i n g the wheel". A c c o r d i n g l y , we w i l l not
simply review the r e s u l t s of the FTIR s t u d i e s of c o a l published
to date, but f i r s t consider the use of c e r t a i n computer r o u t i n e s .
We w i l l then consider how such r o u t i n e s can be a p p l i e d to the
q u a n t i t a t i v e determination of s p e c i f i c f u n c t i o n a l groups i n c o a l .
Published work concerning the a n a l y s i s of mineral matter i n c o a l

3. PAINTER ET AL. Functional Group Determination Using FTIR 49
or chemical changes such as o x i d a t i o n w i l l only be considered i n

p a s s i n g , t o the extent that they i l l u s t r a t e the usefulness o f a
given procedure.
Sample P r e p a r a t i o n
When commercial FTIR instruments were f i r s t introduced the

w i d e l y touted o p t i c a l advantages of the instrument sometimes
gave the impression that one could p l a c e a b r i c k i n the sample
chamber and s t i l l o b t a i n a spectrum. The p r e p a r a t i o n o f samples
was not emphasized, but i f anything the data manipulations that
have s i n c e became r o u t i n e have made c a r e f u l and c o n s i s t e n t
sample p r e p a r a t i o n even more important, p a r t i c u l a r l y f o r q u a n t i -
t a t i v e work.
Coal samples are most c o n v e n i e n t l y prepared by d i s p e r s i o n i n
an a l k a l i h a l i d e m a t r i x , u s u a l l y KBr o r C s l . Estep e t a l (5)
examined the problems i n v o l v e d i n t h i s method o f p r e p a r a t i o n
w i t h s p e c i f i c reference t o the a n a l y s i s o f m i n e r a l matter i n c o a l .
These authors preground the m i n e r a l o r ash under i n v e s t i g a t i o n
and then simply mixed a measured weight o f the m a t e r i a l w i t h
d r i e d C s l . For optimum a b s o r p t i o n and the m i n i m i z a t i o n o f
problems a s s o c i a t e d w i t h p a r t i c l e s c a t t e r i n g i t i s necessary that
the s i z e of the sample p a r t i c l e s are l e s s than the wavelength o f
the i n f r a r e d r a d i a t i o n and t h a t they are evenly dispersed w i t h i n
the matrix. Estep e t a l (5) noted that t h i s method of sample
p r e p a r a t i o n d i d not give maximum a b s o r p t i o n , g r i n d i n g o f the C s l
was a l s o necessary. Consequently, i n work i n t h i s l a b o r a t o r y we
a l s o g r i n d the a l k a l i h a l i d e ( u s u a l l y KBr) together w i t h the
c o a l using a P e r k i n Elmer Wig-L-Bug. [For hard minerals and shale
i t i s necessary t o a l s o p r e g r i n d the samples ( 6 , 7 ) ] . The g r i n d -
ing time necessary t o achieve optimum a b s o r p t i o n w i l l vary from
l a b o r a t o r y t o l a b o r a t o r y according t o the equipment a v a i l a b l e .
An i n i t i a l g r i n d i n g study should be conducted t o determine op-
timum c o n d i t i o n s . For example, F i g u r e 1 i s a p l o t o f the i n t e g -
r a t e d a b s o r p t i o n of the aromatic C-H out-of-plane bending modes
of a v i t r i n i t e concentrate (1.3 mg o f maceral i n 300 mg KBr)
p l o t t e d as a f u n c t i o n o f g r i n d i n g time. I n r e c e n t l y acquired
equipment optimum a b s o r p t i o n was reached a f t e r g r i n d i n g f o r 30
seconds, although on o l d e r equipment approximately 20 minutes
g r i n d i n g was r e q u i r e d .
G r i n d i n g i n t o KBr i s a convenient and r e l a t i v e l y s t r a i g h t -
forward method o f sample p r e p a r a t i o n , but i t i s not without
problems. I n terms of c o a l a n a l y s i s the most severe d i f f i c u l t y
i s the u b i q u i t o u s presence of water, s i n c e the strong water
a b s o r p t i o n near 3400 cm" overlaps the c o a l bands due to OH and
NH groups. The e f f e c t of water can o f t e n be minimized by h e a t i n g
the p e l l e t s under vacuum, but i n t h i s l a b o r a t o r y we have never
succeeded i n completely e l i m i n a t i n g water a b s o r p t i o n by such
procedures. This problem was addressed some years ago by
F r i e d e l (8) who observed t h a t h e a t i n g p e l l e t s t o 175°C i s

Figure 1. Plot of the integrated absorption in the region 900-700 cm in the 1
spectrum of a coal sample vs. grinding time in KBr pellet preparation.

r e q u i r e d to completely remove water bands, which nevertheless r e -

appear upon c o o l i n g . Breger and Chandler (9) a l s o reviewed t h i s
problem and reported that they could not e l i m i n a t e the p r e s i s t e n t
3400 cm~l water absorption d e s p i t e numerous attempts at dehyd-
ration. I t was suggested that t h i s band may not only be due to
water, but a l s o hydroxyl groups s u b s t i t u t e d i n the a l k a l i h a l i d e
matrix, an i n t e r p r e t a t i o n a l s o proposed by Efcirie and Dzewczyk (10).
The problems a s s o c i a t e d with water i n a l k a l i h a l i d e pre-
parations suggest that other p r e p a r a t i v e techniques are worth
pursuing. M u l l i n g techniques were o r i g i n a l l y used i n c o a l s t u d i e s
but r e q u i r e long g r i n d i n g times. Furthermore, q u a n t i t a t i v e
s t u d i e s are d i f f i c u l t i f not impossible on the r e s u l t i n g "smears"
that are u s u a l l y used f o r a n a l y s i s .
Recently, F u l l e r and G r i f f i t h s (11) have demonstrated that

d i f f u s e r e f l e c t a n c e could be extremely u s e f u l . Photoacoustic
spectroscopy a l s o has p o t e n t i a l (12=15)· However, at t h i s time
the a p p l i c a t i o n of these techniques to the q u a n t i t a t i v e deter-
mination of f u n c t i o n a l groups i n c o a l remains to be demonstrated.
Corrections Or Adjustments To The Spectra
In order to obtain q u a n t i t a t i v e measurements of the f u n c t i o n -

a l groups present i n c o a l by FTIR i t i s necessary to f i r s t
account f o r the minerals that may be present. Solomon (16,17)
reported that c o a l s p e c t r a were c o r r e c t e d by s u b t r a c t i n g the con-
t r i b u t i o n s of k a o l i n i t e and i l l i t e and s c a l i n g the s p e c t r a to
give the absorbance f o r 1 mg of c o a l dmmf. However, i t i s o f t e n
the case that the s p e c t r a of mineral components are dominated
by c l a y s such as k a o l i n i t e and i l l i t e (18,12), but these may
c o n s t i t u t e only 20 to 30% by weight of the mineral matter
present. Furthermore, p y r i t e does not have absorption bands i n
the m i d - i n f r a r e d region used i n c o a l s t u d i e s , so that the con-
t r i b u t i o n of t h i s mineral would not be measured by simple sub-
t r a c t i o n procedures. The most accurate method f o r determining
mineral content and a d j u s t i n g the s p e c t r a to account f o r a l l the
m a t e r i a l s that may be present i s to f i r s t o b t a i n the low temper-
ature ash and then adjust the spectrum to the equivalent of 1 mg
of organic m a t e r i a l using the f r a c t i o n a l amount of ash i n the
c o a l so determined. The spectrum of t h i s ash can then be
d i r e c t l y subtracted from that of the c o a l so as to e l i m i n a t e the
bands of the mineral c o n s t i t u e n t s (19). O c c a s i o n a l l y , organic
s u l f u r and n i t r o g e n can be f i x e d as inorganic s u l f a t e and n i t r a t e
i n the ashing process, but these minerals can r e a d i l y be d e t e c t -
ed and q u a n t i t a t i v e l y measured by FTIR methods (19,20).
The second adjustment to c o a l s p e c t r a that concerns us,
s i n c e we b e l i e v e i t may lead to s p e c t r a l a r t i f a c t s , i s the
c o r r e c t i o n of the b a s e l i n e f o r s c a t t e r i n g . In h i s seminal paper
on the i n f r a r e d spectra of c o a l , Brown (21) discussed the o r i g i n
of the s l o p i n g background and concluded that s c a t t e r i n g was not
the only source. M i c r o s c o p i c examination of various KBr p e l l e t s

showed no s i g n i f i c a n t v a r i a t i o n i n average c o a l p a r t i c l e s i z e ,
but there was a general trend to higher background absorption
with i n c r e a s i n g rank. Reviewing the work of Brown and other
s i m i l a r s t u d i e s , Dryden (22) concluded that at l e a s t i n higher
rank coals part of the background can be a t t r i b u t e d to the
1
'wings of e l e c t r o n i c absorption bands extending i n t o the i n f r a -
red. The background absorption may t h e r e f o r e vary with frequency
i n a non-linear f a s h i o n . In f a c t , i f we examine the spectrum
of a v i t r i n i t e sample shown i n Figure 2, a s u b s t a n t i a l s l o p i n g
b a s e l i n e i s apparent between 3800 and about 1850 cm~l, but the
spectrum f l a t t e n s out and apparently slopes i n the opposite d i r -
e c t i o n between 1800 and 500 cm~l. This type of v a r i a t i o n i n
background i s apparently not unique to c o a l . Maddam's (23) has
pointed out that various workers have employed p a r a b o l i c

functions to f i t b a s e l i n e s . C l e a r l y , i f we s t r a i g h t e n the base-
l i n e according to the slope i n one region (e.g. between 3800 and
1850 cm 1 , as shown i n Figure 3, there w i l l be a d i s t o r t i o n i n
the remaining part of the spectrum. Solomon (16,17) used t h i s
approach and obtained spectra s i m i l a r to those reproduced here,
with the absorbance minima between 1000 and 500 cm" clearly
r a i s e d above the new ( s t r a i g h t ) b a s e l i n e . In subsequent curve
r e s o l v i n g an extremely broad band ( h a l f width approximately
200 cm ) centered near 700 cm~l was determined. This band was
t e n t a t i v e l y assigned to a carbonyl group and was stronger than
the c h a r a c t e r i s t i c C=0 s t r e t c h i n g mode near 1700 cnT^-. However,
the c h a r a c t e r i s t i c s of the 700 cm~^ band do not correspond to any
known carbonyl group frequency. We suggest that i t may be an
a r t i f a c t of the method used to s t r a i g h t e n the b a s e l i n e . The
bottom spectrum shown i n Figure 3 d i s p l a y s the r e s u l t of using
two separate s l o p i n g s t r a i g h t b a s e l i n e s , i l l u s t r a t e d i n the top
spectrum, to adjust the s p e c t r a between 3800 and 1850 cm"l and
between 1850 and 500 cm"^, r e s p e c t i v e l y . In t h i s adjusted
spectrum there i s c l e a r l y no broad (200 cm~l h a l f width) under-
l y i n g absorption centered near 700 cm"^.
I f c o a l s p e c t r a are to be curve resolved or i f spectra of
m a t e r i a l s having d i f f e r e n t backgrounds are to be a c c u r a t e l y com-
pared, i t may prove necessary to adjust the b a s e l i n e . However,
the s p e c t r a reproduced i n Figure 3 i n d i c a t e that such procedures
are more dependable i f a p p l i e d s e p a r a t e l y to s p e c i f i c l o c a l
regions of the spectrum.
Computer A p p l i c a t i o n s
The primary f u n c t i o n of the computer i n FTIR instruments i s

to perform the F o u r i e r transformation that converts an i n t e r -
ferogram to a recognizable spectrum. However, the a v a i l a b i l i t y
of an o n - l i n e mini-computer has opened the door to r o u t i n e data
manipulations. In t h i s s e c t i o n we w i l l review procedures that
have been or promise to be u s e f u l i n c o a l c h a r a c t e r i z a t i o n .
C e r t a i n data a n a l y s i s operations, such as numerical i n t e g r a t i o n

Coal OH groups
—•· — I — · — ι — · — \ — ι •—«—ι—·—ι—•—ι—•—•—»—ι—·—ι—·—ι—«—•—ι ι • •—·—ι—«—<—

3Κ00 3200 38(30 2M00 2000 1600 1200 800 1
«η»*
Figure 2. FTIR spectrum of a vitrinite concentrate.
Figure 3. FTIR spectra of vitrinite concentrate. Key: top, spectrum with estima
tion of baseline positions; middle, spectrum corrected for single, sloping straight-
line spectrum; and bottom, regions of spectrum corrected separately for back
ground.

between defined l i m i t s , are to some degree t r i v i a l and w i l l not

be discussed.
D i f f e r e n c e Methods
The a b i l i t y to s u b t r a c t one spectrum from another to o b t a i n

a d i f f e r e n c e spectrum has proved very u s e f u l i n c o a l s t u d i e s ,
p a r t i c u l a r l y the d e t e c t i o n of o x i d a t i o n products (24,25) and the
a n a l y s i s of mineral matter i n c o a l (18-20» 26). Spectra are
stored i n d i g i t a l form i n computerized systems and i t i s a r e l -
a t i v e l y s t r a i g h t forward task to m u l t i p l y these s p e c t r a by
appropriate s c a l i n g f a c t o r s and s u b t r a c t one from another. For
example, F i g u r e 4 compares the i n f r a r e d spectrum of a f r e s h c o a l
sample to that of the same sample o x i d i z e d f o r two hours at 150°C.

The only apparent d i f f e r e n c e i s the appearance of a shoulder near
1695 cm~l i n the spectrum of the o x i d i z e d sample. However, more
information can be obtained from the d i f f e r e n c e spectrum, shown
i n the same f i g u r e . The d i f f e r e n c e spectrum was obtained by
m u l t i p l y i n g the spectrum of the unoxidized c o a l by a s c a l i n g
f a c t o r ( u s u a l l y a f r a c t i o n a l number) and s u b t r a c t i n g from the
spectrum of the o x i d i z e d sample. This procedure was repeated
on a t r i a l - a n d - e r r o r b a s i s u n t i l the bands of the mineral matter
(near 1000 cnT^) were e l i m i n a t e d . The 1695 cnT^ i s r e s o l v e d as
a separate band i n the d i f f e r e n c e spectrum and a prominent new
band near 1575 cnr-*- i s now revealed. In a d d i t i o n , bands due to
a l i p h a t i c C-H v i b r a t i o n a l modes near 2900 cm ^ appear negative or
below the b a s e l i n e , i n d i c a t i n g that the f u n c t i o n a l groups r e s -
p o n s i b l e f o r these absorptions are disappearing upon o x i d a t i o n .
There are two major problems a s s o c i a t e d with t h i s procedure.
F i r s t i s the choice of bands to be e l i m i n a t e d or used as an i n -
t e r n a l standard. In the example used above bands due to mineral
matter were chosen. This could lead to e r r o r s i n that only s m a l l
q u a n t i t i e s of sample (about lmg) are used to o b t a i n a spectrum.
Consequently, any v a r i a t i o n i n mineral matter content among the
c o a l p a r t i c l e s w i l l lead to an improper choice of s c a l i n g f a c t o r .
This problem can i n p r i n c i p l e be solved by o b t a i n i n g the spectrum
of the low temperature ash (LTA) of the c o a l . This spectrum i s
then subtracted from each of the s p e c t r a of the c o a l samples.
The r e s u l t i n g d i f f e r e n c e s p e c t r a can then be adjusted to the
equivalent of 1 mg of organic m a t e r i a l by m u l t i p l y i n g by s c a l i n g
f a c t o r s c a l c u l a t e d from the weight of c o a l i n the o r i g i n a l KBr
p e l l e t s and the s c a l i n g f a c t o r determined from e l i m i n a t i o n of the
mineral bands. A l l s u b t r a c t i o n s between the s p e c t r a o x i d i z e d and
f r e s h samples can then be performed on a 1/1 weight b a s i s to
determine true d i f f e r e n c e s .
The second problem i s more general to a l l d i f f e r e n c e methods
and i n v o l v e s the c o r r e c t determination of s c a l i n g parameters.
T r i a l - a n d - e r r o r s u b t r a c t i o n s are l i m i t e d by the e s s e n t i a l l y sub-
j e c t i v e judgement of when bands have been e l i m i n a t e d . . This pro-
cedure i s tedious but reasonably accurate i f strong f a i r l y

i s o l a t e d bands can be used as an i n t e r n a l standard. I f there are

only s l i g h t d i f f e r e n c e s between the s p e c t r a of i n t e r e s t , p o t e n t i a l
e r r o r s are n a t u r a l l y much l a r g e r . Koenig and co-workers have
addressed t h i s problem with respect to the a n a l y s i s of polymers
and developed a r a t i o method (27) and l e a s t - s q u a r e s s p e c t r a l f i t -
t i n g procedures (28). These programs have yet to be a p p l i e d to
the a n a l y s i s of organic f u n c t i o n a l groups i n coal, although the
l e a s t squares method o f f e r s some p o t e n t i a l i n the a n a l y s i s of
mineral matter (25). We w i l l consider a d d i t i o n a l examples of the
use of d i f f e r e n c e methods below i n our d i s c u s s i o n of methods f o r
the determination of hydroxyl groups i n c o a l .
Factor A n a l y s i s
The a n a l y s i s of the s p e c t r a of c o a l s would be c o n s i d e r a b l y

a s s i s t e d by a knowledge of the number of p r i n c i p a l components that
c o n t r i b u t e to the spectrum. T h e o r e t i c a l l y , t h i s knowledge can be
obtained by the method of f a c t o r a n a l y s i s , described i n d e t a i l by
Malinowski and Howery (29) and adapted to FTIR by Koenig and co-
workers (30). A requirement of the method i s that the s p e c t r a
of a number of samples are a v a i l a b l e i n which the c o n c e n t r a t i o n of
the components v a r i e s from sample to sample. N a t u r a l l y , the
number of samples (or spectra) must be greater than the number of
components. I f the s p e c t r a are w r i t t e n i n matrix form so that the
absorbance values at designated frequency i n t e r v a l s are the
elements of the matrix, then the rank of t h i s matrix should be
equal to the number of components. The rank or number of com-
ponents i s u s u a l l y determined by forming an a p p r o p r i a t e square
matrix by m u l t i p l y i n g the matrix constructed from the s p e c t r a by
the transpose of i t s e l f and determining the number of non-zero
eigenvalues.
One u s e f u l a p p l i c a t i o n of t h i s method i s the determination of
the number of components i n a set of mineral mixtures ( f o r example,
a set of low temperature ash samples from a given s u i t e of c o a l s ) .
To determine the usefulness of t h i s program i n c o a l s t u d i e s we
made up a set of ten mixtures, each c o n s i s t i n g of s i x minerals.
The composition of each mixture was d i f f e r e n t . The r e s u l t s are
i l l u s t r a t e d i n F i g u r e 5, where the v a l u e of the l o g of each
eigenvalue i s p l o t t e d as a f u n c t i o n of component number as
recommended by Antoon et a l . ( 3 0 ) . C l e a r l y , there are s i x non-
zero or s i g n i f i c a n t eigenvalues i n d i c a t i n g the presence of s i x
components.
Although a knowledge of the number of major components con-
t r i b u t i n g to a set of s p e c t r a would be important i n performing an
accurate a n a l y s i s , there i s a more i n t r i g u i n g aspect to f a c t o r
analysis. I t i s t h e o r e t i c a l l y p o s s i b l e to r e c o n s t i t u t e the
s p e c t r a of the components and determine the c o n c e n t r a t i o n of each
i n a l l mixtures by the determination of the eigenvalues and eigen-
1
vectors of appropriate m a t r i c e s . This would r e q u i r e a ' t a r g e t i n g
of the eigenvectors to the s p e c t r a of mineral standards (17).

792S
ι
1
3800 700 cm'
Figure 4. FTIR study of coal oxidation. Key: A. FTIR spectrum of oxidized

PSOC 377 coal (HVA) (I h, I50°C in air); B, FTIR spectrum of fresh coal; A—B,
difference spectrum.
'rj
T~i ] ι 3 ] 3 )
ΊΖ> Ζ *i 6 8 \2 \Z
COMPONENT
Figure 5. Factor analysis of ten mineral mixtures (1700-500 cm' ) each contain
1
ing six minerals. Plot of log eigenvalue vs. component number.

This approach has been attempted some years ago i n the study of
r e a c t i o n k i n e t i c s , but at the time o n - l i n e mini-computers were not
a v a i l a b l e . The procedure i n v o l v e d o b t a i n i n g a l a b o r i o u s point-by-
point d e s c r i p t i o n of each spectrum which was then used as input to
a l a r g e computer. Consequently, the method was not a c t i v e l y pur-
sued. The use of FTIR with i t s o n - l i n e computer should t h e o r e t i -
c a l l y allow us to use t h i s approach to analyze mineral mixture,
but at t h i s time the procedure has yet to be adapted. We are
p r e s e n t l y attempting to develop a p p r o p r i a t e programs.
The a p p l i c a t i o n of f a c t o r a n a l y s i s to the determination of
mineral matter i n c o a l i s r e l a t i v e l y s t r a i g h t f o r w a r d . In p r i n -
c i p l e , t h i s technique should be of value i n the a n a l y s i s of the
organic s t r u c t u r e of c o a l samples obtained from d i f f e r e n t p o s i t -
ions i n a seam or l i q u e f a c t i o n products from a c o a l obtained as

a f u n c t i o n of d i f f e r e n t l i q u e f a c t i o n c o n d i t i o n s . However, min-
e r a l mixtures are simple i n that the s p e c t r a are a c c u r a t e l y r e -
produced by a sum of the s p e c t r a of the c o n s t i t u e n t s . There
appears to be no v i b r a t i o n a l c o u p l i n g or s i g n i f i c a n t i n t e r a c t i o n s
between the components. This i s probably not the s i t u a t i o n i n
s t u d i e s of the organic s t r u c t u r e of c o a l . Nevertheless, even i f
the complete i n f r a r e d spectrum i s too complex f o r such an
a n a l y s i s , s p e c i f i c regions c o n s i s t i n g of well-known, i s o l a t e d
modes might prove more amenable to f a c t o r a n a l y s i s . In pre-
l i m i n a r y work we have examined the out-of-plane bending modes
between 950 and 750 cm~l of 13 v i t r i n i t e concentrates. The
spectrum of one of these was shown i n F i g u r e 2, above. A l l of
these s p e c t r a have three main bands i n t h i s r e g i o n (near 850,
810 and 750 cnT^) with the suggestion of weak a d d i t i o n a l
shoulders i n c e r t a i n samples. The r e s u l t s of the f a c t o r a n a l y s i s
are i l l u s t r a t e d i n F i g u r e 6. The f i r s t eigenvalue has a
s i g n i f i c a n t non-zero v a l u e , but there i s a c o n s i d e r a b l e drop i n
magnitude to the second and t h i r d eigenvalues, followed by a
f u r t h e r drop to the other components. This type of r e s u l t i s not
easy to i n t e r p r e t . I t suggests that a l l the s p e c t r a can be r e -
produced by the spectrum of one p r i n c i p l e component. This com-
ponent would have the three bands shown i n F i g u r e 1. Minor
v a r i a t i o n s are then accounted f o r by the presence of two other
components represented by the second and t h i r d eigenvalues.
This i n t u r n i m p l i e s that the r e l a t i v e i n t e n s i t i e s of the out-
of-plane bending modes and hence the r e l a t i v e c o n c e n t r a t i o n of
aromatic hydrogen groups (lone C-H, two adjacent C-H etc) are
f a i r l y constant over the range of samples examined, although the
absolute c o n c e n t r a t i o n of aromatic hydrogen v a r i e s . Unfortunate-
l y , at t h i s p o i n t i n our s t u d i e s we are not c e r t a i n whether we
are g u i l t y of the s i n of o v e r - i n t e r p r e t i n g the data. More work
on the a p p l i c a t i o n of t h i s method i s r e q u i r e d , but i t c l e a r l y
has i n t e r e s t i n g p o t e n t i a l .

Figure 6. Factor analysis of a set of 13 macérais in the aromatic C-H out-of-

plane bending mode region (950-700 cm' ). Plot of log eigenvalue vs. component
1
number.

Derivative Spectroscopy
D e r i v a t i v e spectroscopy has been used f o r many years as a

means of enhancing the appearance of minute shoulders i n spectra
(31). The d e r i v a t i v e of d i g i t a l data can be computed by a Newton-
Gregory i n t e r p o l a t i n g polynominal (32). A p p l i c a t i o n s such as
the d e t e c t i o n of weak bands i n the i n i t i a l stages of c o a l o x i d -
a t i o n are p o t e n t i a l l y of great value. However, i n our laboratory
the major a p p l i c a t i o n of t h i s technique to c o a l s t u d i e s has been
the determination of the number of bands c o n t r i b u t i n g to a given
spectral profile. I t was mentioned i n the i n t r o d u c t i o n to t h i s
review that i n order to have confidence i n the r e s u l t s of curve-
r e s o l v i n g procedures i t i s necessary to have a p r i o r knowledge
of the number of bands i n the s p e c t r a l region of i n t e r e s t and, i f

p o s s i b l e , an estimate of the p o s i t i o n of each band and i t s width
at h a l f height. Within c e r t a i n l i m i t a t i o n s t h i s information can
be obtained from the second d e r i v a t i v e of the absorbance spectrum.
As an example of the use of t h i s method F i g u r e 7 d i s p l a y s
the r e s u l t of adding two overlapping bands of equal h a l f w i d t h and
i n t e n s i t y . Three spectra are shown i n which the two peak p o s i t i o n s
are separated by an amount equal to the h a l f w i d t h , h a l f the h a l f -
width and one t h i r d the h a l f w i d t h of the bands, r e s p e c t i v e l y .
Superimposed upon each of these s p e c t r a i s the p r o f i l e of the
second d e r i v a t i v e . The minima i n the second d e r i v a t i v e p r o f i l e
corresponds to the p o s i t i o n of bands and shoulders (23). I t can
be seen that t h i s method i s not capable of d i f f e r e n t i a t i n g between
bands separated by l e s s than h a l f t h e i r h a l f w i d t h . The f o u r t h
d e r i v a t i v e of the spectrum i s capable of a higher degree of
r e s o l u t i o n , as i l l u s t r a t e d i n F i g u r e 8. (The maxima i n the f o u r t h
d e r i v a t i v e p r o f i l e corresponds to the peak p o s i t i o n ) . However,
the s i g n a l - t o - n o i s e r a t i o degrades considerably with every
successive d i f f e r e n t i a t i o n , so that the f o u r t h d e r i v a t i v e of a
t y p i c a l c o a l spectrum i s o f t e n so noisy as to be uninterpretable.
Nevertheless, as long as these l i m i t a t i o n s are kept i n mind
d e r i v a t i v e spectroscopy can s t i l l be extremely u s e f u l . We w i l l
consider some s p e c i f i c examples below when we discuss the
a n a l y s i s of f u n c t i o n a l groups.
Curve Resolving
Coal spectra c o n s i s t of broad overlapping peaks, so that i f

we are to gain some i n s i g h t i n t o s t r u c t u r e i t would seem essen-
t i a l that attempts are made to resolve i n d i v i d u a l bands
associated with s p e c i f i c f u n c t i o n a l groups. I t i s u s u a l l y a
smiple task to obtain a good f i t between a synthesized spectrum
c o n s i s t i n g of a sum of a s u f f i c i e n t number of bands and an ob-
served s p e c t r a l p r o f i l e . However, the v a l i d i t y of the r e s u l t s are
open to question unless a number of key problems are addressed.
The f i r s t problem i s the choice of mathematical f u n c t i o n
most s u i t a b l e f o r c h a r a c t e r i z i n g the observed band shapes. In a

Figure 8. The second (F", left) and fourth (F"", right) derivatives of a spectrum
consisting of two bands separated by D = V3&X . 1/t

review of the l i t e r a t u r e Maddams (23) has pointed out that the

evidence i n favor of L o r e n t z i a n band shapes i n the s p e c t r a of
homogeneous m a t e r i a l s i s very strong. Gauss-Lorentz sum and pro
duct f u n c t i o n s have o f t e n been used, as with d i s p e r s i v e i n s t r u
ments a s h i f t from L o r e n t z i a n to Gaussian band shapes was found
with i n c r e a s i n g s l i t width. Although FTIR instruments do not have
a set of s l i t s , bandshapes can be a f f e c t e d by instrument f a c t o r s
such as the a p o d i z a t i o n f u n c t i o n used i n the F o u r i e r transform
a t i o n and by f a c t o r s a s s o c i a t e d with the m a t e r i a l under c o n s i d
e r a t i o n ; f o r example, i n t e r a c t i o n s between the c o n s t i t u e n t s of a
complex multicomponent system. Consequently, an e m p i r i c a l l y
determined bandshape would seem to o f f e r the best choice i n c o a l
s t u d i e s . Jones and co-workers (33-35) examined a number of
d i f f e r e n t bandshapes i n t h e i r i n f r a r e d s t u d i e s and expressed a

preference f o r a f u n c t i o n that i s a sum of Gaussian and Lorentz
ian bandshapes. On t h i s b a s i s we decided to u t i l i z e a s i m i l a r
f u n c t i o n i n which the Gaussian and L o r e n t z i a n c o n s t i t u e n t s that
make up a given band have equal h a l f widths and are present i n
the p r o p o r t i o n f to ( 1 - f ) ;
r 2(x-x ) ri d-f)A n m
A = fA Q exp^- 1 π 2 [ ^ - ^ ] ] + 1 + ^ - ζ ) , ^ *
where A i s the peak height, X i s the wavenumber coordinate of the

i s t n e
peak and bandwidth at h a l f height. I n i t i a l estimates
of these parameters are input to a program that f i t s the para
meters f o r a set of bands to the experimental s p e c t r a l p r o f i l e
by a l e a s t squares o p t i m i z a t i o n procedure, as described by
Fraser and Suzuki (36).
Other problems with curve r e s o l v i n g are a s s o c i a t e d with the
i n i t i a l choice of parameters as input to the type of program
o u t l i n e d above. I t i s important to have a p r i o r knowledge of the
number of bands i n the region of the spectrum that i s to be r e
solved and good i n i t i a l estimates of the peak p o s i t i o n of each
band and i t s width at h a l f height. The problems that a r i s e when
such information i s not i n i t i a l l y obtained are best i l l u s t r a t e d
by an example. T h i s w i l l be presented i n the f o l l o w i n g s e c t i o n
where we consider the a p p l i c a t i o n of FTIR to the determination of
f u n c t i o n a l groups i n c o a l .
The A p p l i c a t i o n Of FTIR To The Q u a n t i t a t i v e Determination Of

F u n c t i o n a l Groups In Coal
Because of the complexity of the i n f r a r e d s p e c t r a of coals

most q u a n t i t a t i v e s t u d i e s have been l i m i t e d to the determination
of hydroxy1 groups and a l i p h a t i c and aromatic C-H. Brown (21)
attempted to obtain a measure of the r e l a t i v e proportions of
these l a t t e r groups by measuring the r a t i o of the peak heights of
the aromatic and a l i p h a t i c C-H s t r e t c h i n g modes at 3030 and

2925 cm \ r e s p e c t i v e l y . This approach r e q u i r e s a knowledge of

the e x t i n c t i o n c o e f f i c i e n t s , e and e -, which Brown estimated
ar. al
from measurements on a number or low molecular weight model
compounds. An average value of 0.5 f o r e /e was used, a l -
a
though measured values ranged from 0.3 to ï.of In a l a t e r study
Brown and Ladner (37) a p p l i e d both i n f r a r e d and proton magnetic
resonance to the study of s o l u b l e c o a l products and proposed the
Brown-Ladner equation to determine a r o m a t i c i t i e s from i n f r a r e d
measurements. Other authors (38-40) have attempted to improve
the i n f r a r e d technique by using i n t e g r a t e d absorption measure-
ments as opposed to simple peak heights and by c o n s i d e r i n g other
regions of the spectrum, p r i n c i p a l l y the aromatic C-H out-of-
plane bending modes between 900 and 700 cm" . Although a com-
p a r i s o n with the r e s u l t s of NMR s t u d i e s i n d i c a t e d f a i r l y con-
s i s t e n t r e s u l t s f o r c e r t a i n c o a l s , there are d i s c r e p a n c i e s . For
example, Retcofsky (38) c a l i b r a t e d the C-H aromatic out-of-plane
v i b r a t i o n s of p y r i d i n e and carbon d i s u l f i d e c o a l e x t r a c t s using
the r e s u l t s of proton magnetic resonance s t u d i e s , but obtained
d i f f e r e n t curves f o r the two s e t s of e x t r a c t s . These d i f f e r e n c e s
could be due to v a r i a t i o n s i n the values of e x t i n c t i o n c o e f f i c -
i e n t s with s t r u c t u r e . However, there i s a remarkable s i m i l a r i t y
i n the s p e c t r a of c o a l s and t h e i r e x t r a c t s or l i q u e f a c t i o n
products. In a d d i t i o n , the main features of the s p e c t r a of
coals do not show s i g n i f i c a n t changes as a f u n c t i o n of rank,
v a r y i n g only i n the r e l a t i v e i n t e n s i t i e s of some features and
the appearance of prominent bands due to carbonyl groups and
c a r b o x y l i c acids i n low rank, (or o x i d i z e d ) m a t e r i a l .
(Anthracites could be considered an exception to t h i s general-
i z a t i o n because the presence of an intense background absorption
which has to be regarded as a key feature.) On the b a s i s of
t h i s s i m i l a r i t y we would i n t u i t i v e l y expect only minor
v a r i a t i o n s i n the values of the e x t i n c t i o n c o e f f i c i e n t s of the
c h a r a c t e r i s t i c C-H group frequencies. We suggest that the ob-
served v a r i a t i o n could be due to the procedures used to make
most measurements. For example, Retcofsky (38) and Durie, et a l .
(39) considered the i n t e g r a t e d absorption between 680 and
920 cm~l where there are t y p i c a l l y three major aromatic C-H out-
of-plane bending modes, near 850, 810 and 750 cm" . This
i m p l i c i t y assumes that the e x t i n c t i o n c o e f f i c i e n t s of these three
bands are the same or that the r e l a t i v e i n t e n s i t i e s of the three
bands remains unaltered from c o a l to c o a l . The l a t t e r p o s s i b i l -
i t y i s c l e a r l y not true when a range of coals from d i f f e r e n t
sources i s examined. There are s i g n i f i c a n t d i f f e r e n c e s i n the
r e l a t i v e i n t e n s i t i e s of the out-of-plane C-H modes that r e f l e c t
d i f f e r e n t degrees and types of aromatic s u b s t i t u t i o n . Con-
sequently, i t would be more accurate to define the absorbance i n
1
the range 920 to 680 cm" as the sum of ( u s u a l l y ) three compon-
ents, each with a d i s t i n c t e x t i n c t i o n c o e f f i c i e n t . Variations
i n the degree of aromatic s u b s t i t u t i o n among d i s t i n c t sample
sets (e.g. p y r i d i n e s o l u b l e or carbon d i s u l f i d e s o l u b l e m a t e r i a l )

would then r e s u l t i n d i f f e r e n t c a l i b r a t i o n curves. This problem

a l s o extends to the a l i p h a t i c C-H s t r e t c h i n g r e g i o n of the spect-
1
rum, where the bands between 3000 and 2800 cm" can be considered
as a s u p e r p o s i t i o n of CH, CH^ and CH« modes.
Recently, Solomon (16,17) has used FTIR to examine the
r e l a t i o n s h i p between c o a l s t r u c t u r e and thermal decomposition
products. In t h i s work the s p e c t r a of a number of c o a l s were
" c o r r e c t e d " i n order to account f o r p a r t i c l e s c a t t e r i n g and min-
e r a l content. Each spectrum was then f i t t e d to a s e l e c t e d s e t of
24 Gaussian bands whose i n d i v i d u a l widths and p o s i t i o n s were held
constant so that only t h e i r r e l a t i v e i n t e n s i t i e s were allowed to
vary. A q u a n t i t a t i v e measure of a l i p h a t i c and aromatic C-H
content was determined using the area under the peaks between
1 1
3000 and 2800 cm" and between 900 and 700 cm" .
The papers of Solomon are the f i r s t to r e p o r t the use of the
data handling c a p a b i l i t i e s of FTIR i n an attempt to o b t a i n
quantitative results. In s e v e r a l e a r l i e r s t u d i e s with d i s p e r s i v e
instruments, f o r example the work of Durie, e t a l . (39) and Von
Tschamler and de R u i t e r (41), s i m i l a r q u a n t i t a t i v e measurements of
a l i p h a t i c and aromatic C-H contents have been made u s i n g the i n -
tegrated i n t e n s i t y of the same peaks as Solomon (16,17). However,
there are s i g n i f i c a n t d i f f e r e n c e s i n the value of the f a c t o r , k,
r e l a t i n g to the r a t i o n of the i n t e g r a t e d areas to the correspond-
ing r a t i o of a l i p h a t i c to aromatic hydrogen, H -^/H · Solomon
determined a value of 1.06 whereas Durie, e t a?, determined
values ranging from 0.52 to 0.86. Although i t was c e r t a i n l y more
d i f f i c u l t f o r t h i s l a t t e r group to o b t a i n data with the same
degree of accuracy as can be determined with modern instrument-
a t i o n , t h e i r measurements cannot be e a s i l y dismissed. Calibration
of peak areas to hydrogen content was obtained using proton
magnetic resonance s t u d i e s on e x t r a c t s r e p r e s e n t i n g approximately
40% of the o r i g i n a l c o a l . On the b a s i s of the range of values of
k obtained, Durie, e t a l . suggested that any use of i n f r a r e d
spectroscopy to o b t a i n H^/H ^ values be t r e a t e d with c a u t i o n .
a r
Solomon (16,17) h a s u s e § a d i f f e r e n t method to o b t a i n ex-
tinction coefficients. E s s e n t i a l l y , t o t a l hydrogen content from
elemental a n a l y s i s and hydroxy1 content from measurements of the
1
area of the 0-H s t r e t c h i n g band near 3450 cm" were used i n con-
j u n c t i o n with the peak areas of a l i p h a t i c and aromatic bands to
o b t a i n a p l o t from which e x t i n c t i o n c o e f f i c i e n t s can be determined.
In p r i n c i p l e , t h i s approach appears to be sound, but there are a
number of problems. One d i f f i c u l t y , discussed above, i s general
to a l l i n f r a r e d methods that have been employed so f a r ; what
e r r o r s are introduced by summing peak areas over a number of bands,
each of which has an i n d i v i d u a l e x t i n c t i o n c o e f f i c i e n t , and
e s s e n t i a l l y averaging such c o e f f i c i e n t s f o r the t o t a l area? Other
problems i n v o l v e the c o r r e c t use of curve r e s o l v i n g techniques
and the measurement of hydroxyl groups, which we w i l l now consider
i n more d e t a i l .

The Determination Of Hydroxyl Groups In Coal By FTIR
There have been a number of attempts to measure the -OH con-

tent of c o a l by i n f r a r e d spectroscopy, e i t h e r by d i r e c t measure-
ment of the i n t e n s i t y of the 0-H band near 3450 cm (16,17,42)
or by measuring the i n t e n s i t i e s of c h a r a c t e r i s t i c bands i n t r o -
duced by chemical r e a c t i o n , e.g. a c e t y l a t i o n (43). Osawa and
Shin(42) determined a r e l a t i o n s h i p between the s p e c i f i c e x t i n c t -
1
ion c o e f f i c i e n t of the 3450 cm" absorption and the hydroxyl con-
tent, which was subsequently a p p l i e d i n FTIR s t u d i e s of c o a l by
Solomon (17,18). There are a number of problems with t h i s
approach. The e x t i n c t i o n c o e f f i c i e n t reported by Osawa and Shih
1
r e l a t e s to the peak height of the 3450 cm" band. Solomon (16)
apparently a p p l i e d t h i s c o e f f i c i e n t to the area under t h i s ab-

s o r p t i o n . Assuming the c o e f f i c i e n t was adjusted to r e f l e c t areas
r a t h e r than peak h e i g h t s , i t i s s t i l l d i f f i c u l t to see how
accurate r e s u l t s can be obtained. Not only were d i f f e r e n t methods
used to estimate the b a s e l i n e , but Solomon a p p l i e d the same
e x t i n c t i o n c o e f f i c i e n t to the summed areas of four separately
resolved^bands. Furthermore, i n p l o t s of o p t i c a l density at
3450 cm vs weight of c o a l sample (42) there i s an i n t e r c e p t at
p o s i t i v e values of o p t i c a l d e n s i t y . Osawa and Shih proposed that
1
t h i s ' r e s i d u a l absorption was due to traces of water remaining
i n the KBr d i s k , despite the care taken i n the p r e p a r a t i o n and
subsequent d r y i n g of the sample. We have discussed t h i s problem
i n the s e c t i o n concerning sample p r e p a r a t i o n . However, water
absorbed i n KBr i s not the only problem i n using the i n t e n s i t y
1
of the 3450 cm" band to q u a n t i t a t i v e l y determine the number of
OH groups. In a d d i t i o n to water absorbed by the KBr d i s k s ,
water i s bound to the c o a l i t s e l f i n a complex manner that i s
apparently a f u n c t i o n of rank. The broadening of the hydroxyl
band due to hydrogen bonding (the degree of which could vary from
c o a l to coal) and the p o s s i b l e presence of NH groups are a l s o
f a c t o r s that conspire to make the i n t e r p r e t a t i o n of q u a n t i t a t i v e
measurements suspect. F i n a l l y , i t i s not always d e s i r a b l e to heat
c o a l samples p r i o r to a n a l y s i s . Coking c o a l s , f o r example, are
e a s i l y o x i d i z e d and we have detected the formation of carbonyl
groups and l o s s of a l i p h a t i c C-H gorups at low l e v e l s of oxidation
(1 hour at 150°C) (25). Consequently, t h i s band may be u s e f u l i n
the q u a l i t a t i v e comparison of the hydroxyl group content of
d i f f e r e n t c o a l s , p r o v i d i n g that the KBr p e l l e t s are prepared i n
an i d e n t i c a l manner, but f o r q u a n t i a t t i v e measurements we should
consider other procedures.
In view of these f a c t o r s we suggest that i t w i l l u l t i m a t e l y
prove more u s e f u l to measure OH groups i n c o a l by a combination
of FTIR and chemical procedures. Durie and S t e r n h e l l (43) r e -
ported an i n f r a r e d study of a c e t y l a t e d c o a l twenty years ago.
Although some u s e f u l l i n e a r p l o t s were obtained, the method was
complicated by the overlap of the a c e t y l bands with those of the
o r i g i n a l c o a l . This made the determination of b a s e l i n e s and the

measurement of peak i n t e n s i t i e s subject to p o s s i b l e e r r o r . The

problem i s i l l u s t r a t e d i n Figure 9, which compares the i n f r a r e d
spectrum of an Arizona HVC c o a l (PSOC 312) to that of the same
sample subsequent to a c e t y l a t i o n . FTIR i s capable of s o l v i n g many
problems of t h i s type (band overlap) by simple s p e c t r a l s u b t r a c t -
ion. Figure 9 a l s o shows the d i f f e r e n c e spectrum obtained by sub-
t r a c t i n g the spectrum of the o r i g i n a l c o a l from that of the ace-
t y l a t e d product. The c h a r a c t e r i s t i c a c e t y l bands are now
r e l a t i v e l y w e l l - r e s o l v e d and i t i s a s t r a i g h t - forward task to
draw an appropriate b a s e l i n e and measure peak h e i g h t s , or even
make i n t e g r a t e d absorption measurements of, f o r example the
1370 CH^ mode. We w i l l discuss the d e t a i l s of the use of
a c e t y l a t i o n r e a c t i o n s i n conjunction with FTIR i n a separate
p u b l i c a t i o n . Here we wish to point out the p o t e n t i a l of FTIR f o r

d i s c r i m i n a t i n g between d i f f e r e n t types of OH groups i n the
o r i g i n a l c o a l , s i n c e t h i s brings us back to the s e n s i t i v e subject
of curve r e s o l v i n g .
In an i n i t i a l a n a l y s i s of the carbonyl region of the
d i f f e r e n c e spectrum shown i n Figure 9, three bands were defined
for curve f i t t i n g at the i n i t i a l estimated p o s i t i o n s of 1770, 1725
1
and 1605 cm"* . Although a 'good f i t i n l e a s t squares terms was
obtained the r e s u l t s are probably meaningless. Figure 10 shows
the d i f f e r e n c e spectrum between 1900 and 1550 cm thgether with
the three component bands determined by the program to give the
best f i t to the data. A strong, very broad band near 1725 cm~l
i s the major component and appears stronger than the band assigned
to a c e t y l a t e d phenolic-OH groups near 1765 cm . This r e s u l t
does not make sense i n terms of what i s known of the s t r u c t u r e of
coal. I t i s thought that phenolic OH groups are by f a r the major
hydroxyl component. Although a l a r g e d i f f e r e n c e i n the e x t i n c t i o n
c o e f f i c i e n t s of various types of e s t e r linkages could account
for t h i s discrepancy, i t i s f a r more l i k e l y that the curve r e -
s o l v i n g procedure i s i n s u b s t a n t i a l e r r o r . There are two
probable sources of such e r r o r . F i r s t , that we have not included
a s u f f i c i e n t number of bands i n the a n a l y s i s ; second, that the
1765 cm i s s i g n i f i c a n t l y asymmetric, as a l s o i l l u s t r a t e d
schematically i n Figure 10. These i n i t i a l e r r o r s and misconcept-
ions on our part allows us to emphasize a key p o i n t i n curve
resolving. I t i s u s u a l l y p o s s i b l e to obtain a reasonable f i t
between a synthesized spectrum c o n s i s t i n g of a sum of a
s u f f i c i e n t number of bands an observed s p e c t r a l p r o f i l e . However,
i f we are to have confidence i n the r e s u l t s i t i s d e s i r a b l e or
even e s s e n t i a l to have an i n i t i a l knowledge of the number of
bands. We reviewed one method f o r o b t a i n i n g a knowledge of the
number of bands i n a p r o f i l e above, namely d e r i v a t i v e techniques.
The a p p l i c a t i o n of t h i s method to the carbonyl region of the
d i f f e r e n c e spectrum of an a c e t y l a t e d c o a l (PSOC 272, Kentucky
No. 9, HVB coal) i s shown i n Figure 11. The spectrum and i t s
second d e r i v a t i v e are both presented i n t h i s f i g u r e . The minima
i n the second d e r i v a t i v e p r o f i l e correspond to the p o s i t i o n s of

1
·, , 1 1 1 1 ' · 1 1 1 1 1 1 « ι ' I ' ' I · ·
A
2000 1800 1600 1400 1200 1000 800 *m
Figure 9. FTIR spectra of an Arizona HVC coal. Key: top, acetylated coal; mid
dle, original coal; and bottom, difference spectrum.
1900 1800 1700 1600
Figure 10. Spectral profile of the difference spectrum shown in Figure 9 between
1900 and 1550 cm' fitted to three curves (top); and spectral profile considered
1
with an asymmetric major peak (bottom).

bands and shoulders (23). The presence of most of the bands can
be confirmed by i n s p e c t i o n of the s p e c t r a l p r o f i l e . The only
-1
questionable assignment i s of a band near 1747 cm , where the
second d e r i v a t i v e minima i s of the order of magnitude of the
noise l e v e l . However i f the d i f f e r e n c e spectrum i s c a r e f u l l y ex
amined an i n f l e c t i o n near 1747 cm can be observed. Maddams (23)
has pointed out that the value of the eye and b r a i n should not be
underestimated i n such judgements. Less s u b j e c t i v e evidence,
however, i s provided by examination of other coals where the
components have d i f f e r e n t r e l a t i v e i n t e n s i t i e s . For example, the
d i f f e r e n c e spectrum obtained from an a c e t y l a t e d l i g n i t e i s shown
i n F i g u r e 12. The presence of a band near 1740 i s c l e a r l y i n
d i c a t e d from the second d e r i v a t i v e curve shown i n the same f i g u r e .
It i s s a t i s f y i n g to observe that bands i n approximately the same

p o s i t i o n are obtained from s p e c t r a of c o a l s of d i f f e r e n t rank.
The small d i f f e r e n c e s i n frequency are to be expected i n mat
e r i a l s that vary i n chemical s t r u c t u r e .
In a d d i t i o n to p r o v i d i n g i n i t i a l values of the peak p o s i t i o n s
for the l e a s t squares refinement, the second d e r i v a t i v e curves
can be used to o b t a i n an i n i t i a l estimate of the width at h a l f
height from a measure of the d i s t a n c e between i n f l e c t i o n p o i n t s .
It i s e s s e n t i a l to have good i n i t i a l estimate of these values i f
convergence to a good (and meaningful) l e a s t squares f i t i s to
be obtained. Figure 13 and 14 show the curves resolved i n the
carbonyl region of the d i f f e r e n c e s p e c t r a of the bituminous c o a l
and l i g n i t e considered above. Figure 13 a l s o shows the e f f e c t of
d e s c r i b i n g the 1769 cm~l band as asymmetric according t o :
ln(l+2B) (Χ-Χ )/ΔΧο m 2 ( 2 )
A o exp^-ln2 g j
Where Β i s a f a c t o r which determines the degree of asymmetry, as

described by Fraser and Suzuki (36). I t can be seen that the
e f f e c t of asymmetry i s to reduce the i n t e n s i t y of the 1745 cm
band. However, i t has been emphasized that i n s t u d i e s of t h i s
f 1
type bandshapes should not be skewed unless there are a p r i o r i
grounds f o r doing so (23). Consequently, a f i t that has symmetric
bands i s to be p r e f e r r e d . T h i s aspect of the problem i s p r e s e n t l y
being checked by a study of model compounds and the r e s u l t s ,
together with evidence supporting a complete assignment of the
resolved bands, w i l l be presented i n a future p u b l i c a t i o n . It is
p e r t i n e n t to p o i n t out here, however, that the band near 1720 can
be assigned to r e s i d u a l a c e t i c a c i d , so^Jhat previous methods of
measuring OH groups, f o r example using C l a b e l l e d a c e t i c an
hydride, could be i n e r r o r . The bands near 1773, 1740 and
-1
1660 c m can be assigned to a c e t y l a t e d phenolic OH, a l k y l OH,
and > N-H groups, r e s p e c t i v e l y . A c c o r d i n g l y , t h i s p r e l i m i n a r y
work i n d i c a t e s that FTIR should not only be u s e f u l i n determining
t o t a l OH, through measurements of the i n t e n s i t y of the CH^ and

Figure 11. Difference spectrum between

1900 and 1550 cm obtained from acety
1
lated PSOC 272 coal (bottom) and sec

ond derivation of spectrum (top). 1S00 1800 1700 1600 «™*
Ί

PAINTER ET AL. Functional Group Determination Using FTIR

1773
I
Figure 14. The resolution of the differ

ence spectrum obtained from the acetyl- — ι i i
ated lignite into six bands. IS 00 1800 1700 1600

C-0 bands, but a l s o has the c l e a r p o t e n t i a l f o r d i s c r i m i n a t i n g

between types of OH groups and a l s o measuring N-H groups through
an a n a l y s i s of the C=0 s t r e t c h i n g r e g i o n , p r o v i d i n g that curve
r e s o l v i n g methods are a p p l i e d with circumspection.
The Determination Of C-H Groups
In a number of s t u d i e s attempts have been made to o b t a i n

s t r u c t u r a l information by measuring the peak heights or i n t e g r a t e d
i n t e n s i t i e s of bands assigned to aromatic and a l i p h a t i c C-H modes.
As we mentioned above, there i s some v a r i a t i o n i n values of ex-
t i n c t i o n c o e f f i c i e n t s determined by d i f f e r e n t groups (16, 21,
.22-41). We have suggested that at l e a s t i n part t h i s v a r i a b i l i t y
i s due to the methods used to obtain, data, namely measuring i n -

t e g r a t i n g i n t e n s i t i e s over an e n t i r e s p e c t r a l region thus
assuming that the e x t i n c t i o n c o e f f i c i e n t s of each band i s the
same (or that the bands maintain a constant r e l a t i v e i n t e n s i t y
from c o a l to c o a l ) . At the beginning of t h i s s e c t i o n we used the
aromatic C-H out-of-plane bending modes to i l l u s t r a t e t h i s p o i n t .
The same argument a p p l i e s to measurements i n the a l i p h a t i c C-H
s t r e t c h i n g region where i t has become conventional_Jo measure
the i n t e g r a t e d absorption between 3000 and 2800 cm as a
measure of t o t a l a l i p h a t i c C-H c o n c e n t r a t i o n . This region of the
spectrum has to be considered as the sum of c o n t r i b u t i o n s from
three components, CH, CH^ and CH^. I f the s p e c t r a l c o n t r i b u t i o n
of these groups could be separated, then not only would we have
obtained a greater i n s i g h t i n t o the s t r u c t u r e of c o a l and i t s
v a r i a t i o n with rank, but more c o n s i s t e n t a l i p h a t i c to aromatic
C-H r a t i o s might be obtained by t a k i n g i n t o account d i f f e r e n c e s
i n the e x t i n c t i o n c o e f f i c i e n t s of these groups.
In order to o b t a i n a meaningful r e s o l u t i o n of the bands i n
the C-H s t r e t c h i n g region we followed the procedures o u t l i n e d
above f o r a n a l y s i s of the carbonyl region of the d i f f e r e n c e
s p e c t r a of a c e t y l a t e d c o a l s . Figure 15 shows a s c a l e expanded
p l o t of the a l i p h a t i c C-H s t r e t c h i n g region of the spectrum of
the v i t r i n i t e concentrate considered i n Figure 2. A l s o d i s p l a y e d
i n Figure 15 i s the second d e r i v a t i v e p l o t , c l e a r l y i n d i c a t i n g
the presence of f i v e bands. With an appropriate i n i t i a l choice
of band p o s i t i o n and width at h a l f height obtained from t h i s p l o t ,
the C-H s t r e t c h i n g region can be r e s o l v e d i n t o the f i v e components
shown i n F i g u r e 16. At t h i s p o i n t i t i s tempting to make the
obvious assignment of the 2956 and 2864 cm"" modes to asymmetric
1
and symmetric CH s t r e t c h , the 2923 and 2849 cm" barujls to the
3
asymmetric and symmetric CH^ s t r e t c h and the 2891 cm band to

lone C-H groups. However, we have to consider one more l i m i t -
a t i o n to curve r e s o l v i n g methods. The i d e n t i f i c a t i o n of peaks
i n a p r o f i l e by second d e r i v a t i v e techniques w i l l obviously
depend upon the r e l a t i v e i n t e n s i t i e s of the peaks i n v o l v e d and
t h e i r s e p a r a t i o n r e l a t i v e to t h e i r h a l f widths, as discussed
previously. I f we c a r e f u l l y consider e s t a b l i s h e d group

PSMC 52
I
3000 8900 2800
Figure 15. Scale expanded aliphatic C—H stretching region of the spectrum of
a vitrinite concentrate (bottom); and second derivative of the spectrum (top).
PSMC 52
2956
3000 2900 2800

Figure 16. The resolution of the aliphatic C—H stretching region intofivebands.

frequencies i n conjunction w i t h what i s known of the s t r u c t u r e of

c o a l we have to conclude that the 2923 cm" band i s a composite
of two c o n t r i b u t i o n s , the asymmetric CH s t r e t c h i n g mode and the
?
asymmetric CH~ s t r e t c h i n g mode of methyl groups attached d i r e c t l y

to aromatic r i n g s . However, the p o s i t i o n of the symmetric CH^
s t r e t c h i n g m o d e appears to be l e s s s e n s i t i v e to l o c a l environment,
1
appearing near 2865-2875 cm" f o r methyl groups attached to a l k y l
chains or aromatic r i n g s . Consequently, i f appropriate e x t i n c t i o n
c o e f f i c i e n t s can be determined i t should prove p o s s i b l e to use the
symmetric CH« and CH^ modes to determine these groups and there_Js
then the f u r t h e r p o s s i b i l i t y of using the 2956 cm" and 2923 cm
bands to determine the d i s t r i b u t i o n of methyl groups. (The i n
t e n s i t y of 2923 cm" band would have to be considered as the sum
of the c o n t r i b u t i o n s from CH^ and CH^ groups). F i n a l l y , the

2891 cm could be a p p l i e d to the defermination of t e r t i a r y
hydrogen.
These i n i t i a l r e s u l t s i n d i c a t e that good curve r e s o l v i n g
methods are capable of a l l o w i n g a greater i n s i g h t i n t o c o a l
s t r u c t u r e through a more d e t a i l e d a n a l y s i s of the i n f r a r e d spect
rum. However, there remains the d i f f i c u l t task of o b t a i n i n g ex
t i n c t i o n c o e f f i c i e n t s . Methods used i n previous s t u d i e s , mainly
the use of model compounds and c a l i b r a t i o n by means of s o l u b l e
e x t r a c t s c h a r a c t e r i z e d by proton magnetic resonance, should prove
u s e f u l , but we wish to suggest a t h i r d method. E s s e n t i a l l y , t h i s
b u i l d s on the approach used by Von Tschamler and de R u i t e r (41)
and more r e c e n t l y by Solomon (16,17). We propose to equate the
experimentally determined elemental hydrogen to the sum of con
t r i b u t i o n s from hydrogen c o n t a i n i n g f u n c t i o n a l gorups, as
measured by the i n t e n s i t i e s of appropriate i n f r a r e d bands m u l t i
p l i e d by a conversion f a c t o r (equivalent to an e x t i n c t i o n co
e f f i c i e n t converted to weight u n i t s ) ;
Η = Σ I e
η η η
where Η i s the weight percent hydrogen content, I i s the i n n
t e n s i t y of the η band (e.g. a band assigned to CH^ groups) and

e i s a conversion f a c t o r r e l a t i n g band i n t e n s i t y to the weight
percent hydrogen percent at t h i s s p e c i f i c f u n c t i o n a l group. I f
we consider the curve r e s o l v i n g r e s u l t s discussed above, i t i s
p o s s i b l e to i d e n t i f y three bands a s s o c i a t e d with aromatic hydrogen,
three bands a s s o c i a t e d with v a r i o u s a l i p h a t i c groups (CH, CH^
and CH«) and bands i n the s p e c t r a of a c e t y l a t e d samples that can
be assigned to NH, a l k y l OH and p h e n o l i c OH. In low rank c o a l s
1
bands near 1700 cm" can be r e a d i l y assigned to COOH groups.
C l e a r l y , i f we have s u f f i c i e n t c o a l (or maceral) samples chosen so
as to cover a range of rank and hence hydrogen content, then
t h e o r e t i c a l l y the problem could be solved as a s e t of simultaneous
11
equations. In f a c t , we should be able to "over-determine the
problem by a n a l y z i n g a s u f f i c i e n t number of samples.
T h i s approach has a number of advantages. Model compounds w i l l

not be r e q u i r e d t o o b t a i n e x t i n c t i o n c o e f f i c i e n t s . If a
s u f f i c i e n t l y l a r g e data base i s used, any systematic v a r i a t i o n s
i n e x t i n c t i o n c o e f f i c i e n t s with rank and hence chemical s t r u c t u r e
should be apparent p r o v i d i n g that a method f o r determining
v a r i a t i o n s i n measured and c a l c u l a t e d (by FTIR) hydrogen i s i n -
cluded i n the procedure.
Summary And Conclusions
One of the major advantages of FTIR i n the a n a l y s i s of complex,

systems i s the ready a p p l i c a t i o n of s o p h i s t i c a t e d programs made
p o s s i b l e by the n e c e s s i t y o f an o n - l i n e mini-computer i n these
instruments. We have considered the a p p l i c a t i o n of s e l e c t e d pro-
grams and pointed out that they have t o be a p p l i e d with c o n s i d e r -

able c a u t i o n . In p a r t i c u l a r , we have attempted t o c r i t i c a l l y
assess the problems i n v o l v e d i n determining f u n c t i o n a l groups by
curve r e s o l v i n g methods. There i s a l a r g e body of work i n the
l i t e r a t u r e concerning t h i s problem and by a p p l y i n g the r e s u l t s o f
these s t u d i e s we can conclude t h a t ;
a) E m p i r i c a l l y determined bandshapes should be c a l c u l a t e d
using l e a s t squares curve f i t t i n g programs.
b) In order to have confidence i n the r e s u l t s i t i s necessary
to have a good i n i t i a l estimate of the number o f bands i n a pro-
f i l e , t h e i r frequency and width a t h a l f h e i g h t .
c) These methods should be a p p l i e d s e p a r a t e l y to s p e c i f i c
regions o f the spectrum.
We have considered the a p p l i c a t i o n of these c r i t e r i a to the
determination of OH and CH groups i n c o a l . By combining FTIR
measurements with a c e t y l a t i o n procedures i t appears f e a s i b l e not
only to measure t o t a l ( r e a c t i v e ) OH and NH content, but t o d i s -
t i n g u i s h between p h e n o l i c and a l k y l OH groups by curve r e s o l v i n g
methods. F i n a l l y , we have argued that the determination o f con-
s i s t e n t e x t i n c t i o n c o e f f i c i e n t s f o r a l i p h a t i c and aromatic C-H
bands f o r v a r i o u s c o a l samples would be f a c i l i t a t e d by the use of
curve r e s o l v i n g procedures and a determination of the r e l a t i o n -
ship between the e x t i n c t i o n c o e f f i c i e n t s o f i n d i v i d u a l components.
In previous s t u d i e s i t has been general p r a c t i c e to sum the i n -
tegrated i n t e n s i t y o f a number of bands and hence i m p l i c i t l y
assume that each mode has the same e x t i n c t i o n c o e f f i c i e n t .
Acknowledgements
The authors g r a t e f u l l y acknowledge the f i n a n c i a l support of

the Department of Energy under c o n t r a c t No. De-AC22-OP30013 and
the Penn State Cooperative Program i n Coal Research.
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1. Laitinen, H.A. Analytical Chemistry, 1973, 45(14), 2305.
2. Griffiths, P.R. Chemical Infrared Fourier Transform Spectros-
copy. John Wiley and Sons, New York (1975).

3. PAINTER Et AL. Functional Group Determination Using FTIR 75
3. Koenig, J . L . Applied Spectroscopy, 1975, 29, 293.

4. Chenery, D.H. and Sheppard, N. Applied Spectroscopy, 1978,
32, 79.
5. Estep, P.Α., Kovach, J.J. and Karr C., Jr., Anal. Chem,
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34, Aug. 1980.
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(1980) (in press).
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and Walker, P . L . , Jr., Fuel, 1978, 57, 337.
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P.L., Jr. Fuel, 1978, 57, 125.
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Fuel, 1980, 59, 282.
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Komatsu, M. and Walker, P.L. Jr., Applied Spectroscopy
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Applied Spectroscopy, 1981, 35 (1), 292.
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29. Malinowski, E.R. and Howery, D.G. "Factor Analysis in

Chemistry". Wiley Interscience, New York (1980).
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"Selected Computer Programs With Application to Infrared
Spectroscopy", Digilab Users Group Conference, 1979.
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Leach, Editor, Academic Press, New York.
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4
A p p l i c a t i o n s of F o u r i e r T r a n s f o r m I R S p e c t r o s c o p y
in F u e l Science
P. R. SOLOMON, D. G. HAMBLEN, and R. M. CARANGELO

Advanced Fuel Research, Inc., East Hartford, CT 06108
Petroleum reserves are limited and supplies are

becoming expensive and unstable. Extensive efforts
are underway in the United States and abroad to find
alternative sources for fuel and chemicals by employ-
ing coal, oil shale, tar sands, and biomass. But com-
plicated processing of these raw materials is re-
quired to deliver environmentally acceptable products
at a competitive price. It is, therefore, increas-
ingly important to obtain better characterization
of these raw materials and better understanding of
their transformation in a process.
Fourier Transform Infrared (FT-IR) Spectroscopy is one of the

most versatile techniques available for providing analytical data
on the raw materials, the process chemistry and the products.
Dispersive infrared spectroscopy has traditionally been an
important tool in fuel characterization since most organic and
mineral components absorb in the IR. Discussions of applications
to coal may be found in Lowry (1), van Krevlen (2), Friedel (3),
Brown (4), Brooks, Durie and Sternhell C5) Friedel and Retcofsky
(6) and references cited therein. But FT-IR with i t s advantages
in speed, sensitivity and data processing has added new
dimensions.
The FT-IR permits rapid routine quantitative
characterizations of solids, liquids and gases. The FT-IR's speed
(a complete spectrum can be obtained in 80 msec) provides the
possibility of following chemical transformations (such as coal
0097-6156/82/0205-0077$07.25/0

p y r o l y e i s ) as i t occurs or permits o n - l i n e a n a l y s i s of products

subject to s e p a r a t i o n techniques such as LC, GC or solvent
separation. The FT-IR provides h i g h s e n s i t i v i t y because of i t s
high s i g n a l throughput and by co-adding s p e c t r a to produce good
s i g n a l to n o i s e . This f e a t u r e permits measurement of h i g h l y
absorbing m a t e r i a l s such as c o a l or the use of difficult
techniques such as photoacoustic or diffuse reflectance
spectroscopy. The l a t t e r techniques a l l o w measurement of s o l i d s
w i t h minimal sample p r e p a r a t i o n .
Other advantages of the FT-IR are d i g i t a l storage of s p e c t r a
and the a v a i l a b i l i t y of many data a n a l y s i s r o u t i n e s which were
developed to take advantage of the computer which an FT-IR
r e q u i r e s . These r o u t i n e s permit such operations as base l i n e
c o r r e c t i o n s , smoothing, s p e c t r a l comparisons, s p e c t r a l s y n t h e s i s ,
f a c t o r a n a l y s i s , c o r r e l a t i o n techniques, s o l v e n t subtraction,
mineral subtraction, display and plotting flexibility and
programmed c o n t r o l of experiments. These techniques have proved
so u s e f u l that d i s p e r s i v e instruments are now being o f f e r e d w i t h
add-on computers.
As a r e s u l t of the above advantages of FT-IR, i n v e s t i g a t o r s
have βtarted to reexamine a p p l i c a t i o n s i n f u e l science and
technology. P a i n t e r et a l . (_7, 8) have proposed techniques f o r
q u a n t i t a t i v e l y analyzing mineral components i n c o a l s and low
temperature ash by using s u b t r a c t i o n r o u t i n e s and a quantitative
mineral l i b r a r y . P a i n t e r a l s o has used FT-IR f o r studying c o a l
o x i d a t i o n (9) and l i q u e f a c t i o n products (10, 11). Solomon has
considered the a n a l y s i s of organic constituents. Calibration
factorβ were determined f o r computing the a l i p h a t i c and aromatic
hydrogen concentrations from the i n t e g r a t e d areas under the peaks
near 2900 cm and 800 cm r e s p e c t i v e l y (12) and f o r determining
the hydroxyl concentrations from the abeorbance at 3200 cm (13).
From the aliphatic hydrogen concentration, a reasonable
determination can a l s o be made of the a l i p h a t i c and aromatic
carbon c o n c e n t r a t i o n using the Brown-Ladner r e l a t i o n (14) and an
assumed a l i p h a t i c s t o i c h i o m e t r y . A p p l i c a t i o n s of q u a n t i t a t i v e
a n a l y s i s of organic components have been a p p l i e d to c o a l proximate
a n a l y s i s (15), o i l shale y i e l d s (16), p y r o l y e i s y i e l d s (17) and
c o a l s t r u c t u r e (18). A p p l i c a t i o n s of FT-IR f o r a n a l y s i s of
p y r o l y e i s gases has been discussed by E r i c k s o n et a l (19) and by
Solomon and co-workers (20-23). The FT-IR*s rapid data
a c q u i s i t i o n s (80 m sec/scan) a l s o allows p y r o l y e i s k i n e t i c s to be
followed ( 2 0 - 2 3 ) .
F i n a l l y , the FT-IR system operates by coding the i n f r a r e d
source w i t h an amplitude modulation which i s unique to each
i n f r a r e d frequency. The d e t e c t o r i s s e n s i t i v e to the modulated
r a d i a t i o n so that unmodulated s t r a y r a d i a t i o n i s e l i m i n a t e d from
the experiment, p e r m i t t i n g the use of the FT-IR as an in-situ
detector i n many experiments. For example, an FT-IR has been used
to monitor the e v o l u t i o n of c o a l p y r o l y e i s products w i t h i n a drop
tube furnace (24) and w i t h i n an e n t r a i n e d flow r e a c t o r (25). The
l a t t e r has been operated up to 1200°C.

4. SOLOMON ET AL. Applications of FTIR in Fuel Science 79
These a p p l i c a t i o n s o f FT-IR i n f u e l science are reviewed i n

the f o l l o w i n g pages. The paper d e s c r i b e s techniques o f sample
preparation, q u a n t i t a t i v e analysis of spectra for s o l i d s , l i q u i d s
and gases and a p p l i c a t i o n s to hydrocarbon a n a l y s i s and conversion.
Apparatus
Most o f the measurementβ described i n t h i s paper were made

w i t h a N i c o l e t model 7199 F o u r i e r Transform I n f r a r e d Spectrometer
using a Globar source and a l i q u i d n i t r o g e n cooled mercury-cadmium
t e l l u r i d e d e t e c t o r . For s o l i d s and l i q u i d s , good q u a l i t y s p e c t r a
were obtained a t 4 wavenumber r e s o l u t i o n by co-adding 32 scans
w i t h the IR beam t r a n s m i t t e d through the sample r a t i o e d t o a
background o f 32 scans co-added i n the absence of the sample.

Spectra are converted to absorbance s i n c e under the c o n d i t i o n s o f
the measurement, Beer's Law i s expected to h o l d and the absorbance
i s p r o p o r t i o n a l t o sample q u a n t i t y . For gases, h i g h r e s o l u t i o n
spectra were obtained a t 0.5 wavenumberβ and r a p i d scan data were
obtained at 8 wavenumbers.
A n a l y s i s o f S o l i d Samples
P r e p a r a t i o n o f KBr P e l l e t s Q u a n t i t a t i v e FT-IR t r a n s m i s s i o n
s p e c t r a o f s o l i d s were obtained u s i n g f i n e l y ground samples
pressed i n KBr p e l l e t s . Ten t o f i f t y mg o f sample taken from a
ground (100 mesh o r f i n e r ) , w e l l mixed, r e p r e s e n t a t i v e sample were
placed i n a s t a i n l e s s s t e e l g r i n d i n g capsule, d r i e d i n vacuum f o r
s e v e r a l hours, b a c k f i l l e d w i t h dry n i t r o g e n , sealed i n the capsule
and ground. The length o f g r i n d i n g time necessary to o b t a i n
p a r t i c l e s which are s u f f i c i e n t l y f i n e ( f o r the IR r a d i a t i o n t o
penetrate) depends on the shaker, amount and c h a r a c t e r i s t i c s of
the sample and the g r i n d i n g capsule. A good r u l e t o f o l l o w i s t o
g r i n d so that f u r t h e r g r i n d i n g does not change the i n t e n s i t y of
the a b s o r p t i o n . For most samples, 20 minutes u s i n g a "Wig -L-Bug"
shaker i s s u f f i c i e n t . M a t e r i a l s l i k e t a r sands which have l a r g e
m i n e r a l g r a i n s and s o f t organic matter a r e among the most
d i f f i c u l t to handle and must be ground c o l d ( t o freeze the organic
matter)·
A small sample ( t y p i c a l l y 1.0 mg but as low as 0.25 mg f o r
h i g h carbon content c o a l s o r chars) o f t h i s f i n e l y ground dry
sample i s weighed (to _+·01 mg) i n a dry box and added to a weighed
amount (about 300 mg determined to +_ 0.1 mg) of KBr. The KBr and
c o a l are then mixed by g r i n d i n g f o r 30 seconds and pressed i n t o a
p e l l e t i n an evacuated d i e under 20,000 l b s pressure. The p e l l e t
i s then weighed and the sample weight per cm o f p e l l e t area i s
determined.
The s p e c t r a f o r a c o a l (approximately 1 mg sample i n 300 mg
KBr) prepared i n t h i s manner are shown i n F i g 1. The s p e c t r a f o r
undried p e l l e t s show the presence o f absorbed water (peaks a t
-1 1
3400cm , 1640cm and 600cm" ). The more KBr used and the longer
the mixing d u r a t i o n , the l a r g e r the water peaks.

Figure 1. FTIR spectra of a North Dakota lignite showing the effects of drying a
KBr pellet sample up to 48 hours.

Drying P e l l e t s to Remove Water The problem o f the KBr-H 0 2
bands i s discussed i n Refs. Q , 3^ 1_3 and 26). They appear only

a f t e r g r i n d i n g the KBr. To remove them, i n v e s t i g a t o r s have t r i e d
h e a t i n g the p e l l e t s w i t h v a r i a b l e success. F r i e d e l reported work
of Tschamler which suggested that the complete removal o f the
KBr-HÔ bands occurred only when the p e l l e t s were measured a t
175°C ( 3 ) . Upon c o o l i n g , the bands reappeared, although at
reduced i n t e n s i t y . Osawa and Shih d r i e d p e l l e t s f o r 2 days a t
60°C and found r e s i d u a l a b s o r p t i o n a t t r i b u t a b l e t o water (27).
Roberts reported that d r y i n g a t 100 t o 110°C diminished o r
e l i m i n a t e d the KBr-HÔ bands (28). Solomon and Carangelo achieved
good r e s u l t s by d r y i n g a t 110°C f o r 48 hours (13). For a pure KBr
p e l l e t , t h i s procedure reduced the i n t e n s i t y o f the 3400 cm" band
from .06 absorbance u n i t s i n the undried p e l l e t t o .01 absorbance

u n i t s . For c o a l , these c o n d i t i o n s are a good choice s i n c e 104° t o
110°C i s the s p e c i f i e d d r y i n g temperature f o r determining c o a l
moisture.
The e f f e c t i v e n e s s o f h e a t i n g the p e l l e t s depends on the
p e l l e t p r e p a r a t i o n procedure which i n c o r p o r a t e s the water and on
the d r y i n g c o n d i t i o n s which removes i t . I n c o n s i d e r i n g the
r e s u l t s o f Ref. (13) i t must be coneidered that the c o a l s were
f i r e t d r i e d and ground and then mixed w i t h the KBr using a 30
eecond g r i n d so that a v a i l a b l e moisture from the c o a l i s minimized
and long g r i n d i n g o f the KBr does not occur.
The r e e u l t e o f d r y i n g a c o a l p e l l e t are i l l u e t r a t e d i n
F i g . 1. The p e l l e t wae d r i e d i n vacuum at 105°C f o r 6, 12, 24,
and 48 hours. The f i g u r e shows the s p e c t r a o f the undried
pelleté, the apectra o f the pelleté d r i e d f o r 48 houre and the
d i f f e r e n c e between a l l the s p e c t r a and the 48 hour s p e c t r a . The
d i f f e r e n c e epectra enow the f o l l o w i n g f e a t u r e e : 1) There are l a r g e
water peaks i n the c o a l pelleté which are l a r g e r than i n a KBr
p e l l e t without c o a l . The s i z e o f the peak increases w i t h
decreasing c o a l rank. 2) Drying f o r 48 houre s u b s t a n t i a l l y
reducee the water absorptions a t 3450, 1640 and 600 cm" · Longer
time s and higher temperatures produce l i t t l e a d d i t i o n a l change i n
the e p e c t r a . 3) The d r y i n g a l e o reducee the peak i n t e n s i t i e s a t
1
1560 and 1360 cm" . 4) Drying producee no change i n the peak
i n t e n s i t i e s a s s o c i a t e d w i t h a l i p h a t i c o r aromatic hydrogen.
I t i e reasonable t o assume that the epectra obtained a f t e r 48
houre o f d r y i n g ( a t which p o i n t the epectra atop changing) are
"moieture f r e e " i n the eame sense that c o a l d r i e d a t 110°C u n t i l
i t etope l o o s i n g weight i e d e f i n e d to be "moieture f r e e " . The
reeidue peak i n t e n s i t y c o n t r i b u t e d by the KBr i e t y p i c a l l y leee
than 10% o f the i n t e n e i t y c o n t r i b u t e d by the c o a l (13).
1 1
B e e r e Law To v e r i f y Beer β law, eamplee o f c o a l were
prepared u s i n g approximately 0.5, 1.0 and 1.5 mg o f c o a l i n each
300 mg p e l l e t . To compare abeorbancee o f the eamplee i t i e
neceeeary t o separate the e f f e c t o f the a b s o r p t i o n from t h a t o f
s c a t t e r i n g caused by the c o a l p a r t i c l e e o r by imperfectione i n the
KBr p e l l e t . E m p i r i c a l l y , t h i s s c a t t e r i n g can be represented
reasonably w e l l by a s t r a i g h t l i n e . The appropriateness of t h i e

s t r a i g h t l i n e s c a t t e r i n g c o r r e c t i o n i s d i s c u s s e d i n (13)* To make
the s c a t t e r i n g c o r r e c t i o n , a l i n e which i s tangent to the spectrum
1
near 3800 and 2000 cm" i s s u b t r a c t e d from the spectrum over the
r e g i o n i n which the base l i n e has p o s i t i v e values of absorbance.
The s c a t t e r i n g c o r r e c t i o n was a p p l i e d to the s p e c t r a of the
c o a l considered i n F i g . 1. The c o r r e c t e d s p e c t r a have a l s o been
s c a l e d to 1 mg (DAF) per cm by m u l t i p l y i n g by
f . 100 li
—
(100 - %ASH) VT . Wp/iW^ +"W^)
where A i s the p e l l e t a r e a , W , W RBr and W are the weights i n mg

of the c o a l sample, the for and the p e l l e t , and % ASH i s the
weight percent ash determined by ASTM procedures. The r e s u l t s are

presented i n F i g . 2. The s c a l e d s p e c t r a show some minor
v a r i a t i o n s but i n general are reproduceable w i t h i n 5%. The most
n o t i c e a b l e d i f f e r e n c e s are i n the KBr-HÔ regions e s p e c i a l l y i n
the .5 mg samples which, when s c a l e d , make the KBr-HÔ more
prominent. The near e q u a l i t y of the s p e c t r a f o r the three
d i f f e r e n t sample weights i n d i c a t e s t h a t Beer's law a p p l i e s .
E a r l i e r s t u d i e s reached the same c o n c l u s i o n (27, 29 - 31).
Photoacoustic Spectroscopy A more recent measurement
technique f o r the a n a l y s i s of f u e l s , p a r t i c u l a r l y s o l i d samples,
i s the photoacoustic (PAS) measurement ( 3 2 ) . This technique
allows IR s p e c t r a of s o l i d samples to be obtained e s s e n t i a l l y
without p r e p a r a t i o n . PAS should be considered whenever p h y s i c a l
sample p r e p a r a t i o n i s d i f f i c u l t or when an a r t i f a c t of p r e p a r a t i o n
i s suspected to occur.
The photoacoustic e f f e c t i n s o l i d s i n v o l v e s a thermal
t r a n s f e r from the s o l i d sample to the surrounding gas. Energy
absorbed from the IR r a d i a t i o n by the s o l i d heats the surface of
the s o l i d , which i n t u r n c o n d u c t i v e l y heats a boundary l a y e r of
gas next to the s o l i d s u r f a c e . Thus, sound i s generated at the
frequency of the IR modulation and can be detected w i t h a
microphone. This s i g n a l can be processed i n the same way as the
modulated IR. Because of the d i f f e r e n t t r a n s f o r m a t i o n s i n the
forme of the energy, the PAS s i g n a l s are much lower than i n d i r e c t
IR a b s o r p t i o n measurements. Long data c o l l e c t i o n times a r e ,
therefore, required.
D i f f u s e R e f l e c t a n c e Spectroscopy A t h i r d technique f o r the
study of s o l i d s by FT-IR i s d i f f u s e r e f l e c t a n c e spectroscopy. The
technique which was r e c e n t l y d e s c r i b e d by F u l l e r and G r i f f i t h s ,
(33, 34) a l l o w s good q u a l i t y s p e c t r a t o be obtained on neat
powdered samples. The technique r e q u i r e s f i n e g r i n d i n g of the
samples so, i n t h i s aspect, i t i s more r e s t r i c t i v e than PAS but i s
s u b s t a n t i a l l y f a s t e r than PAS so i s a p p l i c a b l e to f o l l o w i n g
reactions. F i g . 3 compares s p e c t r a f o r a P i t t s b u r g h seam c o a l
ueing the three techniques.
D i f f u s e r e f l e c t a n c e spectroscopy i s p a r t i c u l a r l y u s e f u l i n
studying r e a c t i o n s where the KBr p e l l e t would r e s t r i c t access to
the c o a l . As an example, c o n s i d e r the exchange of deuterium for

4. SOLOMON E T A L . Applications of FTIR in Fuel Science 83

U)
Ο
UAVENUMBERS
Figure 3. Spectra of a Pittsburgh seam coal by three techniques.

hydrogen on c o a l hydroxyl groups. This exchange may be

accomplished i n a few minutes by exposing powdered c o a l t o DÔ
vapor. F i g * 4 shows the d i f f u s e r e f l e c t a n c e spectrum o f a d r i e d
f i n e l y ground c o a l powder, the spectrum o f the same powder a f t e r
exposure t o DÔ vapor and then a f t e r exposure t o room a i r . The
upper and lower s p e c t r a are almost i d e n t i c a l . The middle spectrum
shows a decrease i n the OH r e g i o n (3400 wavenumbers) and an
i n c r e a s e i n the OD r e g i o n (2600 wavenumbers). The s p e c t r a were
obtained i n about two minutes, p e r m i t t i n g the k i n e t i c s o f the
exchange t o be f o l l o w e d . Such deuterated c o a l samples have been
used t o f o l l o w the chemical r e a c t i o n s o f the h y d r o x y l groups i n
p y r o l y e i e by f o l l o w i n g the occurrence o f the deuterium i n the
products (35).
M i n e r a l A n a l y s i s and S p e c t r a l C o r r e c t i o n s The FT-IR s p e c t r a

are obtained i n d i g i t a l form so t h a t c o r r e c t i o n s f o r p a r t i c l e
s c a t t e r i n g and m i n e r a l content may be e a s i l y made. A typical
c o r r e c t i o n sequence i s i l l u s t r a t e d i n F i g . 5. The upper curve i n
F i g . 5 i s the uncorrected spectrum o f a d r i e d c o a l . I t has a
slope from 1000 t o 4000 cm due t o p a r t i c l e s c a t t e r i n g and
c o n t r i b u t i o n s from the m i n e r a l components near 3,600, 1,000 and
450 cm" . I d e n t i f i c a t i o n o f the minerals may be made by reference
to s e v e r a l previous s t u d i e s (36 - 38). The bottom spectrum i n
F i g . 5a has had the m i n e r a l peaks removed by s u b t r a c t i n g
appropriate amounts o f the reference s p e c t r a shown i n F i g . 5b t o
produce a smooth spectrum i n the r e g i o n o f the m i n e r a l peaks.
S i m i l a r procedures f o r m i n e r a l a n a l y s i s using FT-IR have r e c e n t l y
been reported by P a i n t e r e t a l . (7^, 8 ) . The spectrum a l s o has a
s t r a i g h t l i n e s c a t t e r i n g c o r r e c t i o n and has been s c a l e d t o give
the absorbance f o r 1 mg/cm^ o f dmmf c o a l .
A more accurate way o f o b t a i n i n g the m i n e r a l components i s
i l l u s t r a t e d i n F i g . 6 which i s the spectrum and m i n e r a l a n a l y s i s
for the low temperature ash o f the c o a l i n F i g . 5.
S p e c t r a l Synthesis Much previous work has been done t o
i d e n t i f y the f u n c t i o n a l groups r e s p o n s i b l e f o r the observed peaks.
Extensive references may be found i n Lowry, ( 1 ) , and van Krevelen
(2). A convenient way t o o b t a i n areas under the absorbance peaks
i s t o use a curve a n a l y s i s program t o s y n t h e s i z e the IR s p e c t r a
(12). The s y n t h e s i s i s accomplished by adding a b s o r p t i o n peaks
w i t h Gaussian o r L o r e n z i a n shapes and v a r i a b l e p o s i t i o n , w i d t h ,
and height as shown i n F i g . 7. The peaks are separated according
to the i n d e n t i f i e d f u n c t i o n a l group. I t has been determined that
most o f the f u e l r e l a t e d products which were s t u d i e d ( c o a l , t a r ,
char, o i l shale and t a r sand) could be synthesized by v a r y i n g only
the magnitudes of a set o f peaks whose widths and p o s i t i o n s were
h e l d constant. E x p e r i m e n t a l l y , the best shape f o r most o f the
peaks i s a Gaussian. The f i t s obtained f o r s i x c o a l s o f v a r y i n g
rank are i l l u s t r a t e d i n F i g . 8. The f i t s t o other products and
model compounds are shown i n F i g . 9. For a t y p i c a l s i m u l a t i o n f o r
c o a l s and chare the absolute value o f the area i n the d i f f e r e n c e
between the spectrum and the s i m u l a t i o n i s t y p i c a l l y l e s s than 3%
of the spectrum. For t a r s , r e c y c l e s o l v e n t s and o i l shales t h i s


40bo 36bo iibô iëbô 24 bo 2obo i6bo 1200
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Figure 5. Correction of coal spectrum for scattering and minerals. Key: a, correc-
tion of coal spectrum; b, determination of mineral spectrum by addition of reference
spectra.

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F/gwre 6. Synthesis of low temperature ash spectrum by addition of spectra from

mineral library.

SOLOMON ET AL. Applications of FTIR in Fuel Science
" "1
WAVENUMBERS
Figure 7. Spectral synthesis of FTIR of Pittsburgh seam coal


Figure 9. Applications of spectral synthesis to other hydrocarbons.

value i n c r e a s e s to 5% but was as h i g h as 14% i n one case. Optimum

use of such a f i t t i n g procedure r e q u i r e s a set of c a l i b r a t i o n
constants which r e l a t e s the d i s t r i b u t i o n of peaks i n the s y n t h e s i s
to the a b e o r p t i v i t i e e of f u n c t i o n a l groups i n the sample. This i s
the subject of a c o n t i n u i n g i n v e s t i g a t i o n .
The Hydroxyl C o n c e n t r a t i o n The i n f r a r e d measurement of the
h y d r o x y l c o n c e n t r a t i o n of c o a l s prepared i n KBr p e l l e t s was
discussed by Osawa and Shih (27). These authors used the
a b s o r p t i o n of the 0-H s t r e t c h at 3450 cm . Two major problems i n
making t h i s determination are the o v e r l a p of a band due to water
i n the c o a l or water absorbed i n preparing the KBr p e l l e t and
s c a t t e r i n g which a l s o a f f e c t s t h i s r e g i o n of the spectrum. To
overcome these problems Osawa and Shih d i d the f o l l o w i n g : 1)
obtained s p e c t r a of c o a l i n KBr p e l l e t s a f t e r d r y i n g the p e l l e t s

to reduce the water a b s o r p t i o n ; 2) obtained s p e c t r a at s e v e r a l
sample s i z e s and determined "specific extinction coefficients"
(more commonly c a l l e d a b s o r p t i v i t y ) from the slopes of absorbance
V8 sample s i z e and 3) used a l i n e a r base l i n e c o r r e c t i o n f o r
scattering. A p p l y i n g these techniques, they found a l i n e a r
r e l a t i o n between the a b s o r p t i v i t y at 3450 cm and the h y d r o x y l
content of the c o a l determined chemically. Many of Osawa and
Shih'β suggestions were subsequently used i n measurements made by
Solomon ( 1 2 ) . Painter and co-workers (26) have r e c e n t l y
questioned s e v e r a l aspects of these procedures. For the h y d r o x y l
determination these authors have suggested an a l t e r n a t i v e
o r g i n a l l y used by Durie and S t e r n h e l l (29), which employs
a c e t y l a t i o n of the c o a l and a n a l y s i s of the d i f f e r e n c e between
s p e c t r a of raw and a c e t y l a t e d c o a l . This procedure has advantages
i n a v o i d i n g the water problem and i n d i s t i n g u i s h i n g d i f f e r e n t
types of OH groups but i s time consuming. The determination of
hydroxyl d i r e c t l y from the absorbance i n the OH s t r e t c h r e g i o n
would be much 8imp l i e r so i t i s worthwhile to evaluate i t s
accuracy. This was done r e c e n t l y by Solomon and Carangelo (13).
The r e s u l t s are summarized below.
As seen i n the c o a l s p e c t r a the h y d r o x y l O-H s t r e t c h
absorbance appears to be a broad band s t r e t c h i n g from 3600 to 2000
cm"* . The broadness of the band has been a t t r i b u t e d to hydrogen
bonding. I t i s important to be sure that the band shape i s r e a l
and not an a r t i f a c t of the s c a t t e r i n g c o r r e c t i o n . Several
observations i n d i c a t e that the band shape i s r e a l . 1) S i m i l a r
band shapes were observed by F r i e d e l and Queiser (39) u s i n g t h i n
s e c t i o n s of c o a l which don't e x h i b i t s c a t t e r i n g and by Brown (4)
using n u j o l m u l l s . 2) S i m i l a r band shapes are a l s o observed in
non s c a t t e r i n g s p e c t r a of vacuum d i s t i l l e d c o a l t a r melted onto a
KBr blank ( 1 2 ) . 3) Spectra f o r c o a l may a l s o be obtained by
d i f f u s e r e f l e c t a n c e spectroscopy (33, 34) and by photoacoustic
spectroscopy (32) which don't r e q u i r e KBr. Spectra of a
P i t t s b u r g h seam c o a l taken u s i n g these methods are compared i n
F i g . 3. A l l three s p e c t r a show the broad hydroxyl absorbance. 4)
I t i s p o s s i b l e to change the shape of the h y d r o x y l absorbances by
a l l o w i n g the hydrogen to exchange w i t h deuterium. This can be

done by exposing the c o a l t o DÔ vapor. F i g . 4 shows the d i f f u s e

r e f l e c t i o n spectrum of a dry c o a l and the c o a l a f t e r exposure f o r
1/2 hour t o DÔ. The broad OH a b s o r p t i o n peak i s d r a s t i c a l l y
1
reduced and the 0-D peak a t 2600 cm"" appears. 5) The broad peak
i s a l s o d r a s t i c a l l y reduced by a c e t y l a t i o n (Durie and S t e r n h e l l
(29)) and by a l k y l a t i o n ( L i o t a ( 4 0 ) ) .
To v e r i f y that the broadness i n the peak i s due t o hydrogen
bonding, s p e c t r a o f a t a r sample coated on a KBr p e l l e t were
obtained a t e l e v a t e d temperatures (12). As expected f o r hydrogen
bonding, the a b s o r p t i o n f o r bonded OH groups (3200 - 2400 c m )
decreases w h i l e that f o r f r e e OH i n c r e a s e s . The change i n the
high temperature spectrum was not permanent as the room
temperature spectrum returned a f t e r c o o l i n g .
Osawa and Shih found a good l i n e a r r e l a t i o n s h i p between

specific e x t i n c t i o n c o e f f i c i e n t s and h y d r o x y l c o n c e n t r a t i o n s
determined u s i n g an a c e t y l a t i o n method. The c o r r e l a t i o n was
e s p e c i a l l y good when c o n s i d e r i n g only Japanese c o a l s . I n the work
of Solomon and Carangelo (13) the c o r r e l a t i o n was made using
samples from the Pennsylvania State U n i v e r s i t y coal bank.
Hydroxyl c o n c e n t r a t i o n s were determined c h e m i c a l l y by Yarzab,
Abdel-Baset and Given ( 4 1 ) . The c o r r e l a t i o n was determined f o r
1
the absorbance a t 3200 cm"* r a t h e r than 3450 used by Osawa and
Shih (27) t o avoid problems of r e s i d u a l KBr water l e f t after
drying. The broad OH absorbance i n c o a l has an i n t e n s i t y a t 3200
s i m i l a r t o that a t 3450 w h i l e the i n t e n s i t y due t o water i n KBr i s
c l o s e t o zero. The absorbances a t 3200 cm f o r three c o a l s are
p l o t t e d as f u n c t i o n s o f c o a l amount i n F i g . 10. The v a r i a t i o n of
absorbance i s l i n e a r i n sample amount. The slope of the l i n e
1
gives a(3200), the a b s o r p t i v i t y a t 3200 cm" i n ( a b s .
units/cm /mg). The correlation of hydroxyl content and
a b s o r p t i v i t y i s i l l u s t r a t e d i n F i g . 11.
The h y d r o x y l content computed f o r 46 c o a l s u s i n g the
c o r r e l a t i o n o f F i g . 11 i s i l l u s t r a t e d i n F i g . 12 as a f u n c t i o n o f
carbon content. The data are f o r c o a l s from the Exxon c o a l sample
bank which were analyzed r e c e n t l y . The Exxon c o a l s which were
sealed i n n i t r o g e n when prepared were analyzed immediately w i t h i n
dayβ a f t e r breaking the s e a l . Except f o r the c o a l s w i t h high
h y d r o x y l content, the Exxon c o a l s appear t o l i e i n a t i g h t band
which i s s l i g h t l y lower than the average values f o r the Penn State
coals. The r e s u l t s a r e , however, d i f f e r e n t from the chemical
determinations o f Osawa and Shih (27) and o f Blom (42).
The r e s u l t s i n d i c a t e that h y d r o x y l oxygen c o n c e n t r a t i o n s i n
c o a l can be determined by FT-IR w i t h an accuracy of about 10%
compared t o the c h e m i c a l l y determined standards. The c o n s i s t e n c y
of the chemical d e t e r m i n a t i o n o f OH should, however, be improved.
A l i p h a t i c and Aromatic Hydrogen A c a l i b r a t i o n f o r the
a l i p h a t i c peaks near 2900 cm and the aromatic peaks near 800
cm" was obtained by Solomon (12). The o b j e c t i v e was t o determine
the values o f the i n t e g r a l a b s o r p t i v i t i e e a ' ( a l ) and a'(ar) ( i n
abs. u n i t s cm /mg/cm ), which r e l a t e peak areas ( i n abs. u n i t s
cm" ) t o the corresponding hydrogen c o n c e n t r a t i o n ( i n mg/cm ),

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Figure 11. Variation of absorptivity with hydroxyl concentration. (Reproduced,

with permission, from Ref. 13.)
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CARBON (WT. % DMMF)
Figure 12. Variation of hydroxyl concentration determined by FTIR with carbon

concentration. (Reproduced, with permission, from Ref. 13.)

A ( a l ) - a'(al) H(al)
and
A (ar) » a'(ar) H(ar)
where A ( a l ) i s the area under the a l i p h a t i c peaks, A ( a r ) i s the

area under the aromatic peaks and H ( a l ) and H(ar) the a l i p h a t i c
(or hydroaromatic) and aromatic hydrogen c o n c e n t r a t i o n s i n the
sample, r e s p e c t i v e l y . The equation for total hydrogen
c o n c e n t r a t i o n H ( t o t a l ) » H ( a l ) + H(ar) + H(hydroxyl) may be
combined w i t h the above equations to y i e l d ,
A(al) L ! . 1 A(ar)
»(al) H ( t o t a l ) - H(hydroxyl)) " " a'(ar) H ( t o t a l ) - H(hydroxyl)
where H(hydroxyl) i s the percent hydrogen i n h y d r o x y l groups. If

a ' ( a l ) and a'(ar) are constant f o r a l l products than p l o t t i n g one
term i n the square b r a c k e t s a g a i n s t the other should y i e l d a
s t r a i g h t l i n e w i t h i n t e r c e p t s a ' ( a l ) and a ' ( a r ) . In Ref. (12) the
above a n a l y s i s was performed f o r a group of c o a l s and model
compounds. Peak areas were determined u s i n g a s p e c t r a l s y n t h e s i s
r o u t i n e employing 26 Gaussian peaks as d e s c r i b e d above. Hydroxyl
concentrations were determined from the i n f r a r e d s p e c t r a u s i n g the
a b s o r p t i v i t y of Osawa and Shih ( 2 7 ) . The r e s u l t s i n d i c a t e a ' ( a l )
and a'(ar) to be constant f o r most c o a l products as w e l l as many
model compounds c o n t a i n i n g aromatic r i n g s . Exceptions were long
a l i p h a t i c c h a i n model compounds, and two h i g h a l i p h a t i c c o a l s and
a low temperature t a r . For these samples, i t appears t h a t longer
a l i p h a t i c chains r e s u l t i n a higher absorbance per hydrogen atom.
The i n t e g r a l a b s o r p t i v i t i e s obtained were
a ' ( a l ) - 900 and a'(ar) - 800
The above a n a l y s i s was a p p l i e d to a wider group of c o a l s

( i n c l u d i n g 44 c o a l s from the Exxon L i b r a r y and a number of c o a l s
from the Pennsylvania S t a t e U n i v e r s i t y c o a l bank) and s e v e r a l s e t s
of c h a r s , t a r s and r e c y c l e s o l v e n t s . S e v e r a l improvements were
a l s o made i n the s p e c t r a l s y n t h e s i s r o u t i n e .
The r e s u l t s are shown i n F i g . 13. F i g . 13a compares r e s u l t s

f o r bituminous c o a l s and t h e i r chars and t a r s . For t h i s group of
m a t e r i a l s the i n t e g r a l a b s o r p t i v i t i e s , determined from the
r e g r e s s i o n a n a l y s i s are
a ' ( a l ) - 746
a'(ar) - 686
F i g . 13b c o n t a i n s r e s u l t s f o r subbituminous c o a l s and l i g n i t e s and

A(al)/(H(total) - H(hydroxyl))
Figure 13. Regression analysis to determine aromatic and aliphatic absorptivities.

Key: a, bituminous coals and products; and b, lignite and subbituminous coals and
products.

t h e i r chars. The data l i e i n a band which i s lower than f o r the

bituminous ( F i g . 13a) i n d i c a t i n g some v a r i a t i o n s i n a b s o r p t i v i t y
w i t h rank. The i n t e g r a l a b s o r p t i v i t i e s are
a ' ( a l ) « 710
and
a'(ar) « 541
The i n t e g r a l a b s o r p t i v i t i e s are lower than those p r e v i o u s l y

obtained by Solomon (12) even though the bituminous group c o n t a i n s
many of the c o a l s o r i g i n a l l y used. The major reason f o r the
d i f f e r e n c e i s v a r i a t i o n s i n the choice of component peaks to use
f o r the s p e c t r a l s y n t h e s i s . A p a r a l l e l problem i s the choice of
i n t e g r a t i o n l i m i t s and the base l i n e when d i r e c t i n t e g r a t i o n i s

used to o b t a i n peak areas. A l s o , the previous work contained o n l y
one l i g n i t e and hydrogen v a l u e s were obtained on vacuum d r i e d
samples by an elemental a n a l y z e r . These values were t y p i c a l l y
lower than those obtained by ASTM procedures. In r e a n a l y z i n g
these c o a l s the ASTM hydrogen values were used f o r c o n s i s t e n c y .
In view of the p o s s i b l e v a r i a t i o n s i n a b s o r p t i v i t y w i t h the
choice of peaks, i n t e g r a t i o n l i m i t s or base l i n e , i t i s e s s e n t i a l
to use the same methods f o r determining peak areas f o r both the
c a l i b r a t i o n of a b s o r p t i v i t i e s and the d e t e r m i n a t i o n of hydrogen
concentrations·
F i g . 14 compares values of H ( a l ) + H(ar) determined u s i n g the
i n t e g r a l a b s o r p t i v i t i e s f o r the bituminous c o a l ( a ' i a l ) - 746 and
a'(ar) » 686) and f o r the subbituminous c o a l s and l i g n i t e s ( a ' ( a l )
f
- 710 and a ( a r ) - 541 ) w i t h H ( t o t a l ) - H ( h y d r o x y l ) .
The i n t e g r a l a b s o r p t i v i t i e s f o r a l i p h a t i c and aromatic
hydrogen appear accurate f o r most c o a l s . As i n Ref. (12)
exceptions are seen f o r some m a t e r i a l s w i t h h i g h a l i p h a t i c or
hydroaromatic c o n c e n t r a t i o n s (above 4 to 5%). These i n c l u d e
a l g i n i t e c o a l s , some t a r s , o i l s h a l e s , o i l s and c o a l l i q u e f a c t i o n
recycle solvents. These compounds f a l l below the p a r i t y l i n e .
The a l i p h a t i c l i n e shapes f o r these m a t e r i a l s appears to be higher
and narrower and the a b s o r p t i v i t i e s are l a r g e r than those f o r most
of the c o a l s and chars considered above. Model compounds
containing long aliphatic chains or having extensive
hydroaromatic i t y show s i m i l a r shapes and have s i m i l a r high
a b s o r p t i v i t i e s (47).
The aromatic hydrogen values computed, u s i n g the above
a b s o r p t i v i t i e s , are i n agreement w i t h those f o r c o a l s of s i m i l a r
rank determined by van K r e v e l e n (43) and by Mazumdar, et a l . (44)
from p y r o l y s i s measurements but are l a r g e r (by about a f a c t o r of
2) than those determined by Brown (4) u s i n g IR techniques f o r the
peaks near 3100 cm.
Determination of Carbon F u n c t i o n a l Group Concentrations The
c o n c e n t r a t i o n of aromatic and a l i p h a t i c carbons may be obtained
u s i n g some simple assumptions. The s t o i c h i o m e t r y of the a l i p h a t i c
p o r t i o n of the sample can be estimated and C(ar) can be c a l c u l a t e d
using a method suggested by Brown and Ladner (14). The method
determines C(ar) by d i f f e r e n c e .

4. SOLOMON E T A L . Applications of FTIR in Fuel Science
C(ar) « C ( t o t a l ) C(al)
- C(total) (12/x) H ( a l )
Where C ( t o t a l ) i s the t o t a l carbon c o n c e n t r a t i o n and χ i s a

parameter which d e s c r i b e s the s t o i c h i o m e t r y of the a l i p h a t i c
m a t e r i a l CH . The accuracy of the method has r e c e n t l y been
A a
determined from H-NMR. For c o a l s , a v a l u e o f χ 1.8 i s
reasonable. T h i s i s based on estimates o f the a l i p h a t i c
s t o i c h i o m e t r y made by s e v e r a l i n v e s t i g a t o r s , a summary o f which
appears i n Ref. ( 1 5 ) .
Compari8ion w i t h NMR To check the accuracy o f the
d e t e r m i n a t i o n o f aromatic and a l i p h a t i c carbons, eighteen c o a l s
f o r which q u a n t i t a t i v e FT-IR data were obtained were a l s o studied
by C NMR by Bernard G e r s t e i n e t a l . , (46) a t Ames Laboratory.
The r a t i o s o f aromatic t o t o t a l carbon obtained by the two methods
are compared i n F i g . 15. There i s good agreement between r e s u l t s
of the two methods.
Model Compounds
A l i b r a r y of 156 model compounds o f i n t e r e s t i n c o a l has been

created under EPRI and DOE sponsored programs (47, 4 8 ) .
Q u a n t i t a t i v e FT-IR spectra were obtained i n d u p l i c a t e f o r each
compound. The compounds which have known molecular s t r u c t u r e were
used t o o b t a i n i n t e g r a l a b s o r p t i v i t i e s f o r f u n c t i o n a l groups of
i n t e r e s t . In working w i t h c o a l and c o a l l i q u i d s which produce
broad i n f r a r e d absorptions because o f t h e i r inhomogeneity, i t i s
p r e f e r a b l e to work w i t h i n t e g r a t e d areas r a t h e r than peak h e i g h t s .
For each compound, the i n t e g r a l a b s o r p t i v i t y a ' ( i ) i n Abs. u n i t s
cm" /(mg/cm ) was determined which r e l a t e s the i n t e g r a t e d area
A ( i ) i n absorbance u n i t s times wavenumber to the c o n c e n t r a t i o n of
the absorbing species C ( i ) i n the sample i n mg/cm by the equation
,
A(i)» a (i)C(i)
Table I summarizes the absorbing groups and the r e g i o n s o f

the spectrum considered and provides a summary o f the average
i n t e g r a l a b s o r p t i v i t i e s w i t h 90% confidence l i m i t s . A number of
conclusions may be drawn from these d a t a .
A l i p h a t i c and Aromatic Hydrogen The average integral
a b s o r p t i v i t i e s f o r H ( a l ) and H(ar) are
a»(al) » 963 + 109 and a'(ar) » 768 + 85

H(al) + H(ar) by FTIR (%)
Figure 14. Comparison of hydrogen concentrations determined chemically with

those determined by FTIR. Key: Q, subbituminous coals, lignites, and products;
and X, bituminous coals and products.
0 20 60 100
C /C - FTIR
ar
Figure 15. Comparison of FTIR and NMR results for aromatic carbon.

TABLE I ι
INTEGRATION LIMITS AND MEAN EXTINCTION COEFFICIENTS FOR ABSORBING GROUPS OF 156 MODEL COMPOUNDS
1
w
H
>
REGION TITLE BASELINE LIMITS INTEGRATION LIMITS INTEGRAL ABSORPTIVITY

Appl
1 H(al) 2600 TO 3120 2800 TO 3000 963.189 +/- 108.975

2 H(ar) 2600 TO 3120 3000 TO 3120 242.693 +/- 31.5441 δ*
3 H(ar) WAG 665 TO 925 680 TO 920 768.354 85.9592 ·>«.
•/-
+/- §*
4 N-Hx 3140 TO 3600 3140 TO 3600 7443.55 4793.54
5 O-C(al) NONE 1000 TO 1200 1078.05 •/- 266.587
6 O-C(ar) NONE 1160 TO 1320 1181.72 +/- 285.379
7 C-C a r Rng NONE 1525 TO 1700 57.9966 •/- 17.0062
8 H-C ( s t r ) 2600 TO 3120 2800 TO 3000 9876.80 +/- 6586.99
9 H2-C- s t r 2600 TO 3120 2800 TO 3000 1338.76 +/- 188.994 S'
10 H3-C- s t r 2600 TO 3120 2800 TO 3000 3524.42 +/- 1679.72
11 H3-C (wag) 1360 TO 1400 1360 TO 1400 69.6250 22.3508 R
+/- <^
12 H-O- NONE 3200 TO 3600 22797.5 +/- 3982.39
13 O-C NONE 1640 TO 1760 603.513 +/- 209.718
14 H-S- s t r
l Scienc
2500 TO 2600 2500 TO 2600 568.171

15 «N- rng NONE NONE
16 C(al)-C NONE NONE

Ν other NONE

17 NONE
18 -S- NONE NONE
102 C O A L AND COAL PRODUCTS
f
The average aromatic a b s o r p t i v i t y f o r model compounds ( a ( a r ) •
768) are higher than those d e r i v e d f o r bituminous c o a l s and
products C ( a r ) * 686) and f o r l i g n i t e and subbituminoue c o a l s and
products ( a ' ( a r ) » 541)· The comparison i s s i m i l a r f o r the
average a l i p h a t i c a b s o r p t i v i t y f o r model compounds a ' ( a l ) • 900
and those d e r i v e d f o r bituminous ( a ' ( a l ) « 746) and l i g n i t e and
subbituminoue ( a ' ( a l ) * 710) c o a l s and products. Examination of
the data show that compounds w i t h CH^ groups ( e i t h e r a l i p h a t i c or
hydroaromatic) removed from aromatic carbons have the h i g h e s t
1
i n t e g r a l a b s o r p t i v i t i e s (1060 +_ 147) i n the 2900 cm" region
compared w i t h methyl groups (753 ^ 159) or OU groups attached to
aromatic carbons (778 jf 213). The l a t t e r values are i n b e t t e r
agreement w i t h most of the c o a l s w h i l e the former agrees w i t h the

products w i t h h i g h a l i p h a t i c or hydroaromatic c o n c e n t r a t i o n s .
The 1600 cm^=- Absorption The a b s o r p t i o n at 1600 cm" is
c h a r a c t e r i s t i c of an aromatic r i n g s t r e t c h i n g mode. The average
1
a b s o r p t i v i t y of a « 7.4 f o r pure hydrocarbon species i s q u i t e low
and would not e x p l a i n the l a r g e a b s o r p t i o n i n c o a l s and c o a l
l i q u i d s . The presence of hydroxyls attached to the r i n g enhances
t h i s absorption. The average i n t e g r a l a b s o r p t i v i t y goes up to
1
a « 41.6. The l a r g e s t a b s o r p t i v i t y i s , however, obtained by the
1
combination of an attached h y d r o x y l and a n i t r o g e n i n the r i n g a
3
187. This combination a l s o produces strong a b s o r p t i o n i n the
1
r e g i o n between 2800 cm" and 2000 cm c h a r a c t e r i s t i c of a strong
hydrogen bonding s h i f t i n the OH a b s o r p t i o n d i s c u s s e d below.
Ring N i t r o g e n Compounds In the absence of h y d r o x y l s , or
other hydrogens which can bond to the n i t r o g e n , the s p e c t r a f o r
r i n g n i t r o g e n compounds are s i m i l a r to t h e i r hydrocarbon analogs.
F i g . 16 compares such a p a i r . S u b s t a n t i a l changes occur however,
when hydrogen bonding occurs. As an example, F i g . 17 compares
Napthol w i t h 4-hydroxy q u i n o l i n e . The 1600 cm absorption
becomes enormous and the f r e e 0-H a b s o r p t i o n at 3450 i s s h i f t e d to
2800 and increased i n i n t e n s i t y and w i d t h .
Hydrogen Bonding 0-H a b s o r p t i o n 2800 to 2000 cm^=- Coals and
d e r i v e d l i q u i d s produce a s u b s t a n t i a l a b s o r p t i o n below 2800 cm
which i s b e l i e v e d to be due to a s h i f t i n the O-H absorbance due
to hydrogen bonding. Examination of the model compound s p e c t r a
shows the absorptions are a l l small f o r the r e g i o n 2800 cm" to
2000 cm" except f o r 4-5 dihydroxy phenanthrene which has
neighboring OH groups and f o r compounds where hydrogen bonding to
a r i n g nitrogen i s possible (47). The average integral
a b s o r p t i v i t y f o r compounds w i t h OH but without n i t r o g e n i s a' •
1
5400. With n i t r o g e n the average i s a * 16,000. This i n t e r e s t i n g
o b s e r v a t i o n i n d i c a t e s the p o s s i b l e importance of n i t r o g e n i n
hydrogen bonding and suggests f u r t h e r study.
L i b r a r y Search Routines To a i d i n the i d e n t i f i c a t i o n of
hydrocarbons, computer programs are being developed f o r comparing
unknown s p e c t r a to l i b r a r i e s of known compounds. As an example, a
sample of 2-hexadecanol was compared to a l i b r a r y of over 100
compounds. The l i b r a r y search i d e n t i f i e d 2-hexadecanol as the

NAPHTHALENE
JjJjdjJ
QUINOLINE
.a:
fOÙO 3«ib0 28b0 22b0 16b0 1000 Too
WAVENUMBERS
Figure 16. Comparison of the FTIR spectra of naphthalene and quinoline.

(Reproduced, with permission, from Ref. 47.)
WAVENUMBERS
Figure 17. Comparison of the FTIR spectra of 4-hydroxyquinoline and

1-naphthol. (Reproduced, with permission, from Ref. 47.)

best f i t but a l s o i d e n t i f i e d the other s p e c t r a i n F i g , 18 which

have s i m i l a r i t i e s i n s t r u c t u r e to 2-hexadecanol as c l o s e f i t s .
Such r o u t i n e s work w e l l f o r pure compounds but not f o r
mixtures. To overcome the problems of i d e n t i f y i n g components of a
mixture, a d i f f e r e n t r o u t i n e was developed (47). In t h i s program,
a model compound i s compared w i t h an unknown mixture i n the
f o l l o w i n g way. The important peaks i n the known are identified
and a comparision w i t h the unknown i s made to o b t a i n a r a t i o of
the i n t e n s i t y of the peaks i n the unknown to the peaks i n the
known. I t i s assumed that the known i s i n c l u d e d as a component of
the unknown when more than 50% of the known peaks appear i n the
unknown w i t h a c o n s i s t e n t r a t i o . This r a t i o i s the percentage of
the known component.
As an example of t h i s procedure, a spectrum obtained by

mixing the s p e c t r a of 3 model compounds was used as an unknown.
The three s p e c t r a and the spectrum of the mixture are presented i n
F i g . 19. The program picked the three components as the top
choices and d i d a good job of p i c k i n g the c o n c e n t r a t i o n s .
Liquids
Q u a n t i t a t i v e A n a l y s i s Q u a n t i t a t i v e a n a l y s i s of l i q u i d s may
be obtained by using a c e l l of known thickness and determining the
sample d e n s i t y . A c e l l of 10 to 20 microns i s adequate f o r most
hydrocarbon l i q u i d s of i n t e r e s t . The c e l l width may be c a l i b r a t e d
using i n t e r f e r e n c e f r i n g e s . R e s u l t s f o r a c o a l r e c y c l e s o l v e n t
are i l l u s t r a t e d i n F i g . 20 ( p l o t t e d i n abs. units/mg per 1.33
cm ). A KBr p e l l e t was prepared f o r the same solvent f o r
comparisons, F i g . 21. The two s p e c t r a agree w i t h i n 5%. The
p e l l e t spectrum has an e x t r a peak near 3500 wavenumbers due to
water absorbed by the KBr.
LC/FT-IR L i q u i d chromatographic s e p a r a t i o n of m a t e r i a l s w i t h
FT-IR d e t e c t i o n i s a good method to c h a r a c t e r i z e heavy hydrocarbon
products. The o p t i c a l design and computational power of an FT-IR
can be u t i l i z e d i n an i n t e g r a t e d LC/FT-IR system f o r r o u t i n e
a n a l y s i s of extremely complex samples. An i n t e g r a t e d LC/FT-IR
system has been d e s c r i b e d by V i d r i n e and Mattson (49)· A simple
flow c e l l w i t h a very small i n t e r n a l volume can be used f o r
d e t e c t i o n so there i s no peak-spreading and other d e t e c t o r s can be
used simultaneously. Chromatographic f r a c t i o n s of i n t e r e s t can be
e a s i l y c o l l e c t e d f o r f u r t h e r a n a l y s i s . In o p e r a t i n g the system, a
complete FT-IR spectrum can be obtained every 100 m i l l i s e c o n d s as
the f r a c t i o n s enter the c e l l . The FT-IR s p e c t r a so obtained may
subsequently be compared w i t h a l i b r a r y of model compounds.
A p p l i c a t i o n of LC/FT-IR to c o a l l i q u i d s has been described by
Brown et a l . (50, 51).

l-EICOSENE (2*9^ ^ _ A J~"
1-EIC0SAN3L (168lJ^ j}*
(166)
-HEXADECANOL ^JL^__JVÂ^
(1*3)
8-HEXADECANOL
(1361
Ί-HEXADECANOL
(0>
2-HEXADECANOL
fOOÔ 35U0 30b0 25b0 20bO 1500 îobo

UAVFNUMBERS
Figure 18. Compounds identified in library search using 2-hexadecanol as the

unknown. (Reproduced, with permission, jrom Ref. 47.)

18.9%
ADAMANTANE
16.0%
-METHYLANTHRAI
35% POLYETHYLENE
35% PENTACENE
30% BTDA
MIXTURE t
fobo 35bô 3obo 25bo 2obo isbo iobo ibo

WAVENUMBERS
Figure 19. Compounds identified in library search using the mixed spectra of
35% polyethylene, 35% pentacene, and 30% BTDA as the unknown. (Reproduced,

4. SOLOMON ETAL. Applications of FTIR in Fuel Science 107
ο
CM
Ο
^ Ο
r
u
5 ·
Ν
Id
(Ο
oc
ο
in
en ο
ο
CM
Ο
Ο
HOI bo 36bo 32bo zebo 21 bo 2obo iebo i2bo βδδ îbo
UflVENUliBERS
F/gwre 20. Liquid cell spectrum of recycle solvent (18.9 microns). (Reproduced,

Ο
Ο
CM
ο
ο
«ς-
u
Id
CD
C
Ο
to
(DO
C s*
Ο
CM
t'obÔ 3600 32b0 zebo 2%b0 20b0 1600 1200 Ï55 ïbo
WeVENUMBEflS
Figure 27. . O r pe//ef spectrum of recycle solvent. (Reproduced, with permission,
from Ref. 47.)

Gases
Quantitative Analysis Quantitative measurements of

complicated gas mixtures may be made w i t h the FT-IR without u s i n g
chromatographic s e p a r a t i o n . An example i s the spectrum i n F i g . 22
from c o a l p y r o l y s i s gas a t 0.5 wavenumber r e s o l u t i o n . The f i g u r e
compares s p e c t r a f o r the p y r o l y s i s gas i n a room temperature c e l l
c o l l e c t e d a f t e r i n j e c t i n g c o a l i n t o a furnace at 800 and 1200°C.
The top p a i r of s p e c t r a show the r e g i o n between 3500 and 2800
1
cm" . The 1200°C spectrum shows HCN, C ^ , and CH^. The 800°
spectrum shows l e s s methane and l i t t l e HCN or but s i g n i f i c a n t
amountβ o f ethane and heavy p a r a f f i n s ( i n d i c a t e d by the broad
background). The r e g i o n between 2600 and 1900 cm shows the C 0 2
and CO. The r e g i o n between 1800 and 1200 cm shows a water ana
methane. The r e g i o n between 1200 and 500 cm shows o l e f i n s ,
a c e t y l e n e , HCN and C 0 . 2
C a l i b r a t i o n o f the FT-IR can be made u s i n g pure gases or

prepared gas m i x t u r e s . Care must be e x e r c i s e d because most o f the
gases o f i n t e r e s t show a marked increase i n absorbance w i t h
dilution. The e x p l a n a t i o n f o r t h i s e f f e c t i s that the a b s o r p t i o n
l i n e s f o r these gases are extremely sharp and f o r moderate
c o n c e n t r a t i o n s a l l the i n f r a r e d energy i s absorbed i n the l i n e
center i n a path s h o r t e r than the a b s o r p t i o n c e l l . The instrument
r e s o l u t i o n i s s u b s t a n t i a l l y broader than the l i n e w i d t h so the
l i n e s do not appear to be t r u n c a t e d . D i l u t i o n o f the gas broadens
the l i n e , reducing the absorbance a t l i n e center so that a longer
path c o n t r i b u t e s t o the a b s o r p t i v i t y , thus i n c r e a s i n g the average
absorbance. T h i s e f f e c t makes c a l i b r a t i o n o f these gases i n the
p y r o l y s i s gas mixture d i f f i c u l t . A s o l u t i o n i s t o d i l u t e the
mixture to a f i x e d pressure at which c a l i b r a t i o n s are made.
K i n e t i c Measurements The N i c o l e t 7199 has the c a p a b i l i t y t o
o b t a i n and s t o r e a complete low r e s o l u t i o n spectrum every 80 msec.
This c a p a b i l i t y may be used t o study time dependent events such as
p y r o l y s i s , polymerizations, surface adsorption, e t c . As an
example c o n s i d e r the a p p l i c a t i o n o f r a p i d FT-IR i n the study o f
c o a l p y r o l y s i s . The experimental apparatus c o n s i s t s o f a heated
g r i d p y r o l y z e r i n a l a r g e gas c e l l w i t h KBr windows to permit
i n f r a r e d a n a l y s i s . The c o a l i s evenly d i s t r i b u t e d between the
f o l d s o f a metal screen and a c u r r e n t i s passed through the screen
to heat the c o a l . Coal temperatures o f 1800°C and h e a t i n g r a t e s
i n excess o f 10,000°C/sec f o r the h i g h e r temperatures can be
achieved.
A t y p i c a l s e t o f s p e c t r a showing the e v o l u t i o n o f gases
d u r i n g a 10 sec p y r o l y s i s i s i l l u s t r a t e d i n F i g . 23. The low
r e s o l u t i o n a n a l y s i s can determine CO, CO^, hÔ, CH^, S 0 C S , 2 > 2
HCN, C H , C H,, C^H , benzene, COS, and heavy p a r a f f i n s and

2 2 2 6
olefins.
The time-temperature e v o l u t i o n f o r each species can be
determined from such scans as i n d i c a t e d i n F i g . 24 which shows the
CO y i e l d as a f u n c t i o n o f time a t s e v e r a l temperatures.

1200 C.
.illiniuml u l l
Ο
ο 600 C
3«*bo 33bo 32bo 11
s i bo'' sobo 29b0 28b0
600 C.
25bo iïEo 23bo 22bo 2 i bo 2obo Tibo
4
u
u o
ζ in
<c ·
m —
ce
D
Sg
B
9Q . ^ . . . A iJLilâ.uâqi. •i f|,ûM Jri'
l
>
, , L
l t
Γ V
1800 1700 16b0 1500 ÛD01300 12bo
1200 C.
800 C.
1200 nbo îobo 9bo ebo 7bo 6bo 5bo
WAVENUMBERS
Figure 22. High-resolution spectra of gases jrom coal pyrolyzed at 1200°C and
800°C. Spectra are obtained in a room temperature cell. (Reproduced, with permis-
sion, from Ref. 25.)


6.25 n
TIME (SECONDS)
7.50 n
TIME (SECONDS)
Figure 24. CO, yield vs. time from pyrolysis of Beulah North Dakota lignite.
Symbols are data and lines are theory using distributed rate kinetics. (Repro-
duced, with permission, from Ref. 22.)

In S i t u A n a l y s i s i n a Furnace S u c c e s s f u l i n s i t u measurement
of c o a l p y r o l y s i s have r e c e n t l y been made (24, 2 5 ) . I n one
a p p l i c a t i o n ( 2 4 ) , small samples o f c o a l were r a p i d l y i n j e c t e d i n t o
a preheated zone which i s t r a v e r s e d by the IR beam. With t h i s
apparatus s p e c t r a have been obtained f o r gases a t temperatures up
to 1000°C. I n the second a p p l i c a t i o n , a gas stream o f
predetermined composition i s heated d u r i n g t r a n s i t through a bed
of alumina c h i p s maintained a t furnace temperature. The gas
stream then enters a t e s t s e c t i o n , maintained a t the same
temperature, where c o a l i s i n t r o d u c e d through a water cooled
i n j e c t o r . A f t e r a v a r i a b l e residence time the r e a c t i n g stream
crosses t h e FT-IR beam and i s quenched i n a water cooled
c o l l e c t o r . FT-IR s p e c t r a have been obtained at temperatures up to
1200°C. The input gas stream and e f f l u e n t stream can a l s o be

analyzed by r o u t i n g the stream through an i n f r a r e d c e l l . The
s p e c t r a presented i n F i g . 22 were o f the e f f l u e n t gas i n the
external c e l l .
F i g u r e 25 shows the i n - s i t u gas a n a l y s i s . There i s an
acceptable n o i s e l e v e l and no d r a s t i c e f f e c t s from the p a r t i c l e
scattering. The analyses are f o r the c o a l i n j e c t o r at p o s i t i o n s
from 5 to 66 cm above the o p t i c a l p o r t . The species which can
e a s i l y be seen a r e CO, C 0 , H 0 , CH^, C H , C H,, and heavy
2 2 2 2 2
p a r a f f i n s . A d d i t i o n a l species c o u l a be observed through the use

of software s i g n a l enhancement technique. FT-IR s p e c t r a obtained
d i r e c t l y w i t h i n the hot furnace a l l o w s the o b s e r v a t i o n o f heavy
products such as t a r which don't appear i n the gas phase a t room
temperature and provide a means t o determine whether reactions
occur d u r i n g the quenching and sampling of the gas stream.
Temperature measurements may a l s o be obtained u s i n g i n t e n s i t y
r a t i o s o f a b s o r p t i o n l i n e s . As the temperature of a gas changes,
the p o p u l a t i o n s i n i t s higher energy l e v e l s i n c r e a s e s . This
g e n e r a l l y means the absorbance i n t e n s i t i e s became more uniform.
The e f f e c t i s i l l u s t r a t e d i n F i g . 26 which compares the hot and
c o l d CO s p e c t r a . The energy i s c l e a r l y s h i f t e d from the c e n t r a l
l i n e s toward the wings. Such a s h i f t could be used f o r
temperature measurement·
GC/FT-IR Complete GC/FT-IR systems are now a v a i l a b l e from

the major FT-IR manufacturers. The system requirements,
techniques and a p p l i c a t i o n s have r e c e n t l y been reviewed by
E r i c k s o n ( 5 2 ) . Spectra can be obtained as the components a r e
e l u t e d from the column, stored and i d e n t i f i e d u s i n g model compound
libraries.
Applications
Coal S t r u c t u r e and Thermal Decomposition The study of

thermal decomposition i s important s i n c e a l l c o a l c o n v e r s i o n
processes (combustion, liquefaction and g a s i f i c a t i o n ) are
i n i t i a t e d by t h i s step. I n a d d i t i o n , i t appears that many o f the
c o a l s t r u c t u r a l elements a r e preserved i n the heavy molecular

«iCIEG ssbo ioEo ii55 sobo îsbo iobo sbo.

WAVENUM8ERS
Figure 25. In situ FTIR spectra of pyrolysis gas in a furnace. (Reproduced, with
permission, from Ref. 25.)


weight product8 ( t a r ) r e l e a s e d i n thermal decomposition so

a n a l y s i s of the products can supply important c l u e s to the
s t r u c t u r e of the parent c o a l . FT-IR a n a l y s i s of the s o l i d
products, char and t a r , produced at s u c c e s s i v e stages of thermal
decomposition provides i n f o r m a t i o n on the changes o c c u r r i n g i n the
chemical bonds. Rapid i n f r a r e d scans taken d u r i n g the thermal
decomposition provide data on the amount, composition and r a t e of
e v o l u t i o n of l i g h t gas s p e c i e s . By comparing the r a t e of
e v o l u t i o n w i t h the r a t e of change i n the chemical bonds,a general
k i n e t i c model was developed which r e l a t e s the products of thermal
decomposition to the organic s t r u c t u r e of the parent c o a l (12, 15,
18, 21, 22).
The model uses a w i d e l y accepted view of c o a l s t r u c t u r e which
assumes a macromolecule c o n s i s t i n g of groups of fused aromatic

r i n g c l u s t e r s l i n k e d by r e l a t i v e l y weak a l i p h a t i c b r i d g e s . The
r i n g c l u s t e r s c o n t a i n heteroatoms (oxygen, s u l f u r and n i t r o g e n )
and have a v a r i e t y of attached f u n c t i o n a l groups. During thermal
decomposition, the weak l i n k s are r u p t u r e d , r e l e a s i n g the c l u s t e r s
and attached f u n c t i o n a l groups. These l a r g e molecules comprise
the c o a l t a r . In vacuum d e v o l a t i l i z a t i o n i n a t h i n heated grid,
the t a r molecules may be removed q u i c k l y from the bed and undergo
few secondary r e a c t i o n s . The evidence f o r t h i s i s the s t r i k i n g
s i m i l a r i t y between the t a r and parent c o a l which has been observed
i n elemental a n a l y s i s , FT-IR s p e c t r a and NMR s p e c t r a (12, 21,
53-55). The FT-IR s p e c t r a f o r four c o a l s and t h e i r vacuum t a r are
i l l u s t r a t e d i n F i g . 27. For bituminous c o a l s , the two m a t e r i a l s
are almost i d e n t i c a l except f o r a higher c o n c e n t r a t i o n of
a l i p h a t i c (hydroaromatic) hydrogen ( e s p e c i a l l y methyl) i n the t a r .
This e x t r a hydrogen i s presumably a b s t r a c t e d from the char to
s t a b i l i z e the f r e e r a d i c a l s i t e s formed when the b r i d g e s were
broken. S i m i l a r arguments were g i v e n f o r p y r o l y s i s of model
compounds by Wolfs et a l . ( 5 6 ) .
Since the a b s t r a c t e d hydrogen i s most l i k e l y to come from the
hydroaromatic p o r t i o n of the c o a l , i t i s reasonable to expect the
t a r y i e l d to depend on H ( a l ) . In F i g . 28, taken from Ref. ( 1 7 ) ,
the t a r y i e l d ( c i r c l e s ) i n vacuum p y r o l y s i s i s p l o t t e d a g a i n s t
H ( a l ) f o r a number of c o a l s . A l s o p l o t t e d are the y i e l d s of heavy
hydrocarbons, ( i . e . , o i l s and BTX) from h y d r o p y r o l y s i s ( s q u a r e s ) ,
(57). Indeed, there i s a strong c o r r e l a t i o n between t a r y i e l d and
H(al). The o b s e r v a t i o n t h a t the t a r i s r i c h i n methyl hydrogen
but not i n aromatic hydrogen when compared to the parent c o a l has
i m p l i c a t i o n s concerning the nature of the a l i p h a t i c l i n k a g e s . The
r e s u l t suggests that the bonds which were broken to free the r i n g
c l u s t e r s were predominantly between two a l i p h a t i c carbons, not
between an aromatic and an a l i p h a t i c .
Simultaneous w i t h the e v o l u t i o n of t a r molecules i s the
c o m p e t i t i v e c r a c k i n g of the bridge fragments, attached f u n c t i o n a l
groups and r i n g c l u s t e r s to form the l i g h t molecules of the gas.
The q u a n t i t y of each gas species depends on the f u n c t i o n a l group
d i s t r i b u t i o n i n the o r i g i n a l c o a l . At low temperatures there i s
very l i t t l e rearrangement of the aromatic r i n g s t r u c t u r e . There

PSOC 170 PSOC 212

STRETCH BENDING "I
WAVENUMBERS WAVENUMBERS
Figure 27. Comparison of FTIR spectra of coals and their vacuum distilled tars.
(Reproduced, with permission, from Ref. 12)
50
rH
Q)
30
•4 · •
U
10
2 4 6
% A l i p h a t i c Hydrogen
Figure 28. Correlation of tar yield with aliphatic (hydroaromatic) hydrogen.

Key: ·, tar yield in vacuum pyrolysis; and heavy hydrocarbon yield from
hydropyrolysis. (Reproduced, with permission, from Ref. 17.)

i s decomposition of the s u b s t i t u t e d groups and a l i p h a t i c (or

hydroaromatic) s t r u c t u r e s r e s u l t i n g i n CO., iÔ, hydrocarbon gases
and some CO r e l e a s e from the c a r b o x y l , h y d r o x y l , a l i p h a t i c and
weakly bound ether groups, r e s p e c t i v e l y . At h i g h temperature
there i s breaking and rearrangement of the aromatic r i n g s . In
t h i s process, H 2 i s r e l e a s e d from the aromatic hydrogen and HCN
and a d d i t i o n a l CO are r e l e a s e d from r i n g n i t r o g e n and tightly
bound ether linkages. The e v o l u t i o n of each species i s
c h a r a c t e r i z e d by r a t e constants which are i n s e n s i t i v e to c o a l
rank. The d i f f e r e n c e s between c o a l s are due to d i f f e r e n c e s i n the
mix of sources i n the c o a l f o r the evolved s p e c i e s .
The p y r o l y s i s chemistry may be f o l l o w e d by examining the
i n f r a r e d s p e c t r a of chars and t a r s . The s p e c t r a f o r a s e r i e s of
chars i s i l l u s t r a t e d i n F i g . 29. The chars were produced by

d e v o l a t i l i z i n g c o a l i n an e n t r a i n e d f l o w r e a c t o r at the i n d i c a t e d
temperature and r e a c t i o n d i s t a n c e . The r e s u l t s are s i m i l a r to
those observed by Brown (58) and O e l e r t (59). The r a p i d r e d u c t i o n
of the a l i p h a t i c and h y d r o x y l peaks corresponds to the h i g h r a t e
formation of t a r , hydrocarbon gases and H 0. 2 The aromatic and C-0
peaks remain to h i g h temperature. The s p e c t r a f o r t a r s produced
at v a r i o u s temperatures are i l l u s t r a t e d i n F i g . 30. The spectra
i n d i c a t e p y r o l y s i s of the t a r at h i g h temperatures. There i s a
decrease i n h y d r o x y l and a l i p h a t i c groups and an i n c r e a s e i n
aromatic hydrogen, e s p e c i a l l y the peak a s s o c i a t e d w i t h 3 and 4
adjacent hydrogens at 750 cm .
R e l a t i o n Between Coal S t r u c t u r e and Proximate A n a l y s i s F i x e d
Carbon One of the most commonly used determinations of the
thermal decomposition y i e l d has been proximate analysis v o l a t i l e
matter d e t e r m i n a t i o n i n which weight l o s s i s measured a f t e r r a p i d
h e a t i n g of the c o a l to 950°C. An e a r l y attempt to c o r r e l a t e the
"fixed carbon" r e s i d u e (FC) w i t h s t r u c t u r a l p r o p e r t i e s was
discussed by van K r e v e l e n , ( 4 3 ) . Based on experiments w i t h model
compounds i t was p r e d i c t e d t h a t the aromatic carbon f r a c t i o n
should remain i n the FC w h i l e the remainder of the c o a l should be
s p l i t o f f completely forming the v o l a t i l e matter (VM). FC should
t h e r e f o r e be roughly equal to the aromatic carbon content of the
c o a l , C ( a r ) . The c o r r e l a t i o n was v e r i f i e d f o r s e v e r a l c o a l s u s i n g
values of C(ar) determined from densimetrie c o n s t i t u t i o n a n a l y s i s .
In a recent study, measurements were made f o r a number of
1
c o a l s to v e r i f y van K r e v e l e n s c o r r e l a t i o n (15)* Values of C ( a r ) ,
computed u s i n g the Brown-Ladner r e l a t i o n w i t h v a l u e s of H ( a l )
determined by FT-IR are p l o t t e d i n F i g . 31 a g a i n s t the ASTM
determined values f o r FC. A l s o p l o t t e d are data f o r the c o a l s
reported by van K r e v e l e n . The values of C(ar) f o r s i m i l a r rank
c o a l s determined by the two methods are i n agreement. Values f o r
C(ar) show a systematic v a r i a t i o n w i t h FC but, as noted by van
K r e v e l e n , are t y p i c a l l y h i g h e r than FC. The data seem to
c o n t r a d i c t the o b s e r v a t i o n that v o l a t i l e t a r s have a p p r e c i a b l e
aromatic contents (see F i g s . 27 and 30). The reasons for this
c o r r e l a t i o n are d i s c u s s e d i n (15).

WAVENUMBERS
Figure 29. FTIR spectra of chars at successive stages in thermal decomposition.

Chars were produced in an entrainedflowreactor at 800°C, 1000°C, and 1200°C
by reaction over the indicated distances.


0 20 40 60 80 100
Fixed Carbon (FC)
Figure 31. Correlation of proximate analysis fixed carbon with aromatic carbon
C(ar). Key: +, data obtained by van Krevelen using densimetric constitution
analysis (43); and O, data obtained by Solomon using FTIR and the Brown-
Ladner relation (15). (Reproduced, with permission, from Ref. 15.)

O i l Shales Among the methods used f o r c h a r a c t e r i z i n g o i l

s h a l e , those a p p l i e d to the raw shales are most u s e f u l because
they are not i n f l u e n c e d by p o s s i b l e changes i n the organic
s t r u c t u r e produced by the e x t r a c t i o n procedure. R e c e n t l y . M a c i e l
et a l . , (60, 61) demonstrated the usefulness of the C cross
p o l a r i z a t i o n NMR technique f o r o i l shale measurements. The method
was a p p l i e d t o a number o f o i l shales to determine the r a t i o of
a l i p h a t i c to aromatic carbon. From these measurements, i t was
found that there e x i s t s an approximate r e c t i l i n e a r correlation
between the "apparent" a l i p h a t i c carbon content of the o i l shale
and the o i l y i e l d as determined by F i s c h e r assay.
In a recent study by Solomon and M i k n i s , (16) s e v e r a l raw o i l
shales from the group s t u d i e d by M a c i e l et a l . , were analyzed by
FT-IR u s i n g the same techniques employed f o r a n a l y z i n g c o a l s . The

r e s u l t s are presented i n F i g . 32. The f i g u r e shows the a l i p h a t i c
content computed i n two ways. F i r s t , i t can be determined
d i r e c t l y as the sum of H ( a l ) + C ( a l ) (squares) where H ( a l ) and
C ( a l ) are determined from FT-IR and C NMR, respectively.
Second, i t can be determined from H ( a l ) u s i n g an assumed
s t o i c h i o m e t r y of CH i . e . %C-H « 7 H ( a l ) . The agreement of the
2
two determinations of a l i p h a t i c C-H suggests that the assumed

s t o i c h i o m e t r y i s reasonable. The r e s u l t s o f F i g . 32 show t h a t the
weight percent o i l y i e l d s are only s l i g h t l y l e s s than the weight
percent a l i p h a t i c C-H. An a t t r a c t i v e e x p l a n a t i o n of the r e s u l t i s
that under c o n d i t i o n s of the F i s c h e r assay there i s almost
complete conversion of the a l i p h a t i c components but l i t t l e of the
aromatics.
Liquefaction The a b i l i t y to do q u a n t i t a t i v e s t r u c t u r a l
a n a l y s i s makes FT-IR a good t o o l f o r c o a l l i q u e f a c t i o n r e s e a r c h .
As an example, F i g . 33 compares the feedstock and the product i n a
l i q u e f a c t i o n process ( 4 7 ) . The feedstock c o n s i s t s o f 33.3% c o a l
plus 66.6% r e c y c l e s o l v e n t . The combined spectrum i s compared
w i t h the spectrum o f the product. The lowest spectrum i s the
d i f f e r e n c e between the feedstock and the product. The product i s
lower i n oxygen groups but h i g h e r i n aromatic hydrogen.
E f f e c t of Hydrode8ulfurization on Coal S t r u c t u r e Several
processes have been developed to reduce the c o n c e n t r a t i o n o f
s u l f u r i n c o a l p r i o r to i t s u t i l i z a t i o n . Besides a s s e s s i n g the
s u l f u r c l e a n i n g p o t e n t i a l of these processes, i t i s important t o
determine what changes have been made i n the o v e r a l l p r o p e r t i e s of
the c o a l .
F i g u r e 34 i l l u s t r a t e s the r e s u l t s f o r a raw and c h e m i c a l l y
cleaned c o a l ( 6 2 ) . A s u b s t a n t i a l decrease i s observed i n the
a l i p h a t i c peak (2900 cm" ) and s u b s t a n t i a l increases are observed
1
i n the carbonyl peak (1700 cm" ), the h y d r o x y l peak (3500-2400
cm ) and the ether peak (1250 cm ).
According to the p y r o l y s i s model discussed above, the changes
i n the organic s t r u c t u r e which are i n d i c a t e d i n the FT-IR s p e c t r a
w i l l r e s u l t i n s u b s t a n t i a l changes i n the d i s t r i b u t i o n of v o l a t i l e
products. A comparison o f the gas y i e l d s as determined by FT-IR
f o r a raw and t r e a t e d c o a l are shown i n F i g . 35. As expected, the

0 20 40 60 80 100
WEIGHT PERCENT ALIPHATIC CH
Figure 32. Correlation of Fischer assay oil yield with aliphatic hydrocarbon
concentration. Key: O, %CH=7H(al); and •, %CH—H(al) + C(al). (Repro-
duced, with permission, from Ref. 16.)

Figure 33. FTIR spectra of liquefaction feedstock and products. (Reproduced,


4. SOLOMON E T A L . Applications of FTIR in Fuel Science


cleaned c o a l shows reduced l e v e l s o f hydrocarbon gases, and

increased l e v e l s of oxygen c o n t a i n i n g s p e c i e s , H«0, CO and CO^.
The l e v e l of SO^ i s s h a r p l y reduced w h i l e the l e v e l of COS i s
r e l a t i v e l y unchanged. These d i f f e r e n c e s are r e l a t e d t o the change
which the treatment imposes on the sources f o r these products.
The t a r y i e l d f o r the cleaned c o a l i s a l s o reduced i n agreement
w i t h the r e l a t i o n between t a r y i e l d and a l i p h a t i c hydrogen which
was discussed above (see F i g . 28).
Acknowledgement
The authors would l i k e to acknowledge the c o n t r i b u t i o n of

s e v e r a l colleagues and t h e i r i n s t i t u t i o n s . Warren V i d r i n e o f
Nicolet Instrument C o r p o r a t i o n provided h i s a s s i s t a n c e and

l a b o r a t o r y t o o b t a i n the photoacoustic a t t e n u a t i o n and d i f f u s e
reflectance spectra. Richard Neavel and the Exxon C o r p o r a t i o n
s u p p l i e d samples from the Exxon sample bank and allowed the
p u b l i c a t i o n o f the h y d r o x y l data. P r o f e s s o r Douglas Smoot o f
Brigham Young U n i v e r s i t y s u p p l i e d the samples on which the d r y i n g
and Beer's Law s t u d i e s were performed and has allowed the use of
data obtained f o r him. Much o f the e a r l y FT-IR work was done a t
United Technologies Reserach Center under DOE Contract
ET-78-C-01-316. More recent work has been done a t Advanced F u e l
Research, I n c . under EPRI c o n t r a c t s RP 1604-2 and RP 1654-8 and
DOE Contract DE-AC01-81-FE05122. Support f o r some o f the
p y r o l y s i s / F T I R s t u d i e s was r e c e i v e d from the Grand Forks Energy
Technology Center.
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Wiley, NY. (1963)
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(1961)
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L., Jr., Fuel 57, 125 (1978)
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Cava, A. and Graff, R. Α., Fuel 60, 342 (1981)
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263 (1981)
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Chemistry Preprints 27, (to be published)
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Proceedings of the International Conference on Coal Science,
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39. Friedel, R. A. and Queiser, J. Α., Anal. Chem. 28, 22 (1956)
40. Liotta, R., Fuel 58, 724 (1979)

41. Yarzab, R. F., Abdel-Baset, Z. and Given, P. H., Geochim. et

Cosmochim., Acta, 43, 281 (1979)
42. Blom, L., Edelhausen, L. and Van Krevelen, D. W., Fuel 38, 537
(1959)
43. van Krevelen, D. W., and Schuyer, J . , Coal Science, Elsevier,
Amsterdam. (1957)
44. Mazumdar, Β. Κ., Chakrabartty, S. K. and Lahiri, Α., Fuel 41,
129 (1962)
45. Retcotsky, H. L., Schweighardt, F. K. and Hough, Μ., Chem. 49,
585 (1977)
46. Gerstein, B. C., Murphy, P. D., Ryan, L. Μ., and Solomon, P.
R., A Study of Carbon and Hydrogen Aromaticity in Coals by
High Resolution Solid State Nuclear Magnetic Resonance and
Fourier Transform IR Spectroscopy, (to be published)
47. P. R. Solomon and R. M. Carangelo, Characterization of
Wyoming Subbituminoue Coals and Liquefaction Products by
Fourier Transform Infrared Spectrometry, EPRI Final Report for
Contract #1604-2. (Sept., 1981)
48. Solomon, P. R., Monthly Topical Report, Investigation of the
Devolatilization of Coal under Combustion Conditions, Dept. of
Energy, Contract ET-78-C-01-3167. (November, 1979)
49. Vidrine, D. W. and Mattson, D. R., Applied Spectroscopy 32,
502 (1978)
50. Brown, R. S., Hausler, D. W. and Taylor, L. T.,
Anal. Chemistry 53, 197 (1981)
51. Brown, R. S., Hausler, D. W. and Taylor, L. T., Reprint
Anal. Chemistry 52, 1511 (1980)
52. Erickson, M. D., Applied Spectroscopy Reviews 15, 261 (1979)
53. Brown, J. K., Dryden, I. G. C., Dunevein, D. Η., Joy, W. Κ.,
and Pankhurst, K. S., J. Inst. Fuels 31, 259 (1958)
54. P. R. Solomon and Mereidth B. Colket, Fuel 57, 749 (1978)
55. Orning, A. A. and Greifer, B., Fuel 35, 381 (1956),
56. Wolfs, P. M. J . , van Krevelen, D. W. and Waterman, H. I., Fuel
39, 25 (1960)

57. Chen, W., La Cava, Α., and Graff, R. Α., ACS Div. of Fuel
Chemistry Preprints 24, #3, 94 (1979)
58. Brown, J. K., J. Chem. Soc., 752 (1955)
59. Oelert, Η. Η., Fuel 47, 433 (1968),
60. Maciel, G. E., Bartuska, V. J. and Miknis, F. P., Fuel 57, 505
(1978)
61. Maciel, G. E., Bartuska, V. J. and Miknis, F. P., Fuel 58, 155
(1979)
62. The samples were supplied by Sid Friedman of the Pittsburgh

Energy Technology Center.
RECEIVED September 7, 1982

5
Chemistry and Structure of Coals
Diffuse Reflectance IR Fourier Transform (DRIFT)
Spectroscopy of Air Oxidation
N. R. SMYRL and E. L. FULLER, JR.

Union Carbide Corporation, Oak Ridge Y-12 Plant, Nuclear Division,
Oak Ridge, T N 37830
Diffuse reflectance infrared Fourier transform (DRIFT)

spectroscopy has been proven to be an excellent means of charac-
terizing coals and related materials. This report is devoted to
the evaluation of the technique as a method for in situ monitoring
of the chemical structural changes wrought in reactions of coal
with fluid phases. This technique does not require a supporting
medium (matrix) which can contain chemical artifacts which
inherently serve as a barrier for access to the solid coal. The
rapid response of the Fourier transform infrared technique is
further beneficial for kinetic studies related to combustion,
liquefaction, gasification, pyrolyses, etc. Experimental equip-
ment and techniques are described for studies over wide ranges of
-5 2
pressure (10 Pa to ca 1.5 x 10 kPa) and temperature (298°K to
800°K).
Fourier transform infrared (FTIR) spectroscopy has been used

extensively in the past several years in the study of coal and its
related products (1-13). The majority of this work has been done
by transmission spectroscopy utilizing the KBr pellet technique.
In relation to coal, the method has several drawbacks including
variable H O content in the KBr, high scattering background, dif-
2
ficulty in reproducing background for accurate subtraction stu-

dies, the unknown effect of pressure in fabricating the pellet,
and the inability to perform in situ studies. Diffuse reflectance
(DR) and photoacoustic (PA) detection as infrared (IR) sampling
methods both possess the potential to alleviate most of the above
mentioned problems; although, neither of these techniques is
completely without its own pitfalls.
In the field of IR spectroscopy, DR has only recently experi-
enced a wave of renewed interest when coupled with FTIR instrumen-
tation (14-20). There are also recent reports by Hattori, et
a l , (21-24) of the design of an emissionless DR-IR grating
0097-6156/82/0205-0133$06.00/0

spectrometer along w i t h i t s a p p l i c a t i o n to c a t a l y t i c r e a c t i o n s at
e l e v a t e d temperatures and t o adsorbed s p e c i e s . We have r e c e n t l y
reported the development of a high-vacuum DR-IR sample c e l l having
a temperature c o n t r o l l e d sample stage f o r use w i t h our FTIR equip-
ment (25). The c a p a b i l i t i e s of t h i s c e l l were demonstrated by
m o n i t o r i n g the i n s i t u r e a c t i o n s of L i H and LiOH w i t h H 0 and C0 *
2 2
P h o t o a c o u s t i c d e t e c t o r s f o r use w i t h FTIR spectrometers have

been developed and are p r e s e n t l y a v a i l a b l e f o r a number of commer-
c i a l instruments. Since·PA-FTIR represents a very recent area of
i n t e r e s t , the published l i t e r a t u r e i s , t h e r e f o r e , r a t h e r l i m i t e d
(26-34)· The photoacoustic and d i f f u s e r e f l e c t a n c e methods are
complimentary and both have been shown to be a p p l i c a b l e to c o a l
a n a l y s i s (16 ,_19,29,31,34) .
Our i n t e n t i o n i n t h i s report i s to demonstrate the u t i l i t y of

d i f f u s e r e f l e c t a n c e i n f r a r e d F o u r i e r transform (DRIFT)
spectroscopy f o r c o a l a n a l y s i s , p a r t i c u l a r l y i n r e l a t i o n to moni-
t o r i n g the i n s i t u o x i d a t i o n of c o a l , and to compare i t s r e l a t i v e
m e r i t s to those of the KBr p e l l e t and PA sampling techniques.
Experimental
The DR equipment used f o r the present s t u d i e s c o n s i s t e d of a

Model DRA-SID accessory designed f o r D i g i l a b FTS-15 s i d e - f o c u s
FTIR spectrometers by H a r r i c k S c i e n t i f i c C o r p o r a t i o n . The u l t r a -
high-vacuum (UHV) DR c e l l was a modified v e r s i o n of a c e l l a l s o
developed by H a r r i c k S c i e n t i f i c . A d e t a i l e d d e s c r i p t i o n of the DR
c e l l and the accessory are given i n a previous report ( 2 5 ) .
The c o a l samples u t i l i z e d i n the present work were a sub-
bituminous c o a l and a bituminous c o a l obtained from f r e s h l y
opened mine faces i n the Wyoming Wyodak mine and Pennsylvania
Bruceton mine, r e s p e c t i v e l y . The samples were stored under argon
p r i o r to i n i t i a t i o n of any experimental work. The chemical analy-
ses f o r these p a r t i c u l a r c o a l samples are given i n Table 1. The
samples were prepared f o r the DR s t u d i e s by g r i n d i n g i n a b a l l
m i l l under an argon atmosphere to pass a 200 mesh screen.
The Wyodak sample was u t i l i z e d f o r the o x i d a t i o n s t u d i e s . A
powdered sample of t h i s c o a l was placed i n the DR c e l l i n the neat
form (no supporting matrix medium). The pressure was s l o w l y
reduced from atmospheric pressure (~ 100 kPa) to 1 Pa f o l l o w e d by
a gradual i n c r e a s e i n temperature from 27°C to 191°C i n order to
f o l l o w the d e s o r p t i o n of moisture. The sample was then heated to
393°C and o x i d i z e d i n 2.7 kPa of a i r f o r ~ 24 h r s . Spectra were
p e r i o d i c a l l y obtained throughout t h i s sequence of events.
1
The s p e c t r a were scanned at 2 cm" r e s o l u t i o n on a D i g i l a b
FTS-15C F o u r i e r transform i n f r a r e d spectrometer as the s i g n a l
average of 100 i n t e r f e r o g r a m s . A few s e l e c t e d s p e c t r a were
obtained at a higher s i g n a l to noise r a t i o by scanning f o r a
longer p e r i o d . The s p e c t r a are d i s p l a y e d i n the o r d i n a t e format
of [- l o g ( R / R ) l which i s r e f e r r e d to i n t h i s paper as r e f l e c -
s 0
tance (by analogy to absorbance i n normal t r a n s m i s s i o n work)

5. SMYRL AND FULLER DRIFT Spectroscopy of Air Oxidation 135
where Rg i s the r e f l e c t i o n of the sample and RQ i s the r e f l e c t i o n

of the r e f e r e n c e . The r e f l e c t i o n from a m i r r o r mounted at 45° i n
the DR accessory was used f o r the reference which had only the
e f f e c t of v e r t i c a l l y s h i f t i n g the o v e r a l l b a s e l i n e when compared
t o a m a t e r i a l such as KC1 f o r a reference standard. The m i r r o r
reference was p r e f e r r e d since i t could be assured that there would
be no moisture c o n t r i b u t i o n to the s p e c t r a .
R e s u l t s and Discussion
I n order to perform i n s i t u r e a c t i o n s t u d i e s and to monitor

s o r p t i o n - d e s o r p t i o n phenomena, i t i s very b e n e f i c i a l to have the
c a p a b i l i t y to view a s o l i d m a t e r i a l as a powder i n the neat form.
Both DR and PA i n f r a r e d sampling methods possess t h i s a b i l i t y .

Although DR can sometimes y i e l d h i g h l y d i s t o r t e d band s t r u c t u r e
when viewing h i g h l y c r y s t a l l i n e neat m a t e r i a l s (16,25), DR-IR
would s t i l l appear to have the edge over PA-IR f o r i n s i t u powder
r e a c t i o n s t u d i e s . The reason f o r t h i s i s the f a c t that the PA
method r e q u i r e s a d i l u e n t gas f o r sound propagation which i s
r e q u i r e d f o r d e t e c t i o n and, t h e r e f o r e , cannot be used to acquire
s p e c t r a under vacuum c o n d i t i o n s . Photoacoustic IR i s not,
however, r e s t r i c t e d to only powder samples and t h e r e i n l i e s one of
the p r i n c i p a l advantages of the PA method.
As Figure 1 demonstrates, DRIFT spectroscopy can be u t i l i z e d
f o r the a n a l y s i s of powdered c o a l without the n e c e s s i t y of d i l u
t i o n i n a supporting medium. This f i g u r e a l s o demonstrates the
a i b l i t y to f o l l o w the moisture desorptlon process as the Wyodak
m a t e r i a l i s both evacuated and heated. Curve A of Figure 1
1
e x h i b i t s a r a t h e r broad band extending from ~ 3700 cm" to 2100
1
cm" which can be a t t r i b u t e d to the 0-H s t r e t c h of H 0 and various 2
hydroxy c o n t a i n i n g c o n s t i t u e n t s i n the c o a l i n a v a r i e t y of hydro

gen bonded environments. Superimposed on t h i s broad band are the
aromatic and a l i p h a t i c C-H s t r e t c h i n g bands of the organic c o a l
c o n s t i t u e n t s . As the head space i s evacuated and the sample i s
heated, the broad 0-H band i s observed to decrease i n i n t e n s i t y
and become more s t r u c t u r e d w i t h s e v e r a l d i s t i n c t peaks being
1
r e s o l v e d a t 3540, 3390, 3290 cm" as noted i n Curves Β and C.
Curve Β i s the DRIFT spectrum at room temperature and ^ 1 Pa
pressure w h i l e Curve C i s the spectrum of the m a t e r i a l a t the same
pressure heated t o 191°C. Most of the changes occur on I n i t i a l
evacuation w i t h very l i t t l e o c c u r r i n g i n the heating stage as
noted i n Curves D and Ε which represent the r e s p e c t i v e d i f f e r e n c e
s p e c t r a (A-B) and (B-C)· (These d i f f e r e n c e s p e c t r a were obtained
by s u b t r a c t i o n of the C-H s t r e t c h i n g bands which presumes that no
v o l a t i l e organic f r a c t i o n Is l o s t i n the evacuation and heating
process.)
The major p o r t i o n of the changes appear to r e s u l t from
moisture d e s o r p t l o n . One of the problems observed i n KBr p e l l e t
t r a n s m i s s i o n work i s the u n c e r t a i n t y a s s o c i a t e d w i t h d r y i n g the

4,000 3,500 3,000 2,500 2.000

WAVE NUMBER [cm ] -1
Figure 1. DRIFT spectra of Wyodak coal. Key: A, 27°C, 100 kPa; B, 27°C,
1 Pa; C, 191°C, 1 Pa; D, difference spectrum (A — B); and E, difference spectrum
(B - C).
T a b l e 1. Chemical a n a l y s i s o f c o a l samples.
Wyodak Bruceton
Analysis Composition Composition
(wt %) (wt %)
C 72.5 82.5
H 5.45 5.5
0 (by d i f f e r e n c e ) 20.5 7.7
Ν 1.01 1.3
S 0.53 3.0
Moisture 28.9 1.6
Ash 5.98 14.3

KBr and the p o s s i b l e c o n t r i b u t i o n of the moisture from t h i s

m a t e r i a l t o the 0-H band i n the c o a l spectra (10). The p o t e n t i a l
v a l u e of DR f o r o b t a i n i n g b e t t e r understanding of the r e l a t i v e
c o n t r i b u t i o n s to the 0-H band from the water and the organic
c o n s t i t u e n t s i s apparent.
Another d e s i r a b l e c h a r a c t e r i s t i c which i s demonstrated i n the
DRIFT spectra of c o a l i s the r e l a t i v e l y f l a t b a s e l i n e s . The
advantage from t h i s p a r t i c u l a r aspect i s apparent when compared to
the r a t h e r severe s l o p i n g b a s e l i n e s which appear i n the spectra of
KBr p e l l e t s of c o a l due to l i g h t s c a t t e r i n g .
FTIR has been used s u c c e s s f u l l y i n the q u a l i t a t i v e and quan
t i t a t i v e a n a l y s i s of mineral matter i n c o a l (1,5,13). The
success of these methods r e l i e d h e a v i l y on computer s u b t r a c t i o n
techniques. Figure 2 i l l u s t r a t e s that s i m i l a r techniques may be

a p p l i c a b l e to DRIFT s p e c t r a . Curve Β i n Figure 2 represents the
DRIFT spectrum of k a o l i n , a common mineral component found i n
c o a l , d i l u t e d i n KC1 at the 2% l e v e l . The absorption c o n t r i b u
t i o n s due to k a o l i n i n the Bruceton c o a l can be removed by
s u b t r a c t i o n of Curve Β from Curve A to y i e l d Curve C. The 3390
1
cm" band of k a o l i n was used to determine the proper degree of
s u b t r a c t i o n . I t i s necessary i n t h i s case to d i l u t e the k a o l i n i n
KC1 to avoid problems a r i s i n g from specular r e f l e c t i o n . Figure 2
was included f o r i l l u s t r a t i v e purposes o n l y , and no q u a n t i t a t i v e
work has been attempted i n the present study.
P a i n t e r , e t a l , have studied c o a l o x i d a t i o n both f o r samples
obtained from v a r i o u s areas i n a v e i n e x p l o r a t i o n audit through a
h i g h v o l a t i l e coking c o a l seam(8) and i n l a b o r a t o r y studies at low
temperature (100°C) ( 9 ) . I t was concluded from t h i s work that a
v a r i e t y of carbonyl, c a r b o x y l i c a c i d , and carboxylate c o n t a i n i n g
products are formed i n the o x i d a t i o n process. Rockley and
D e v l i n ( 2 9 ) have compared the surfaces of f r e s h l y cleaved c o a l with
aged surfaces by PA-FTIR and have a l s o noted carbonyl species on
the aged surfaces which were a t t r i b u t e d to o x i d a t i o n . Our i n s i t u
s t u d i e s a t a somewhat higher temperature (393°C) e s s e n t i a l l y
p a r a l l e l the observations by P a i n t e r ' s group, although, there were
some d i f f e r e n c e s that are noted i n the f o l l o w i n g d i s c u s s i o n .
The DRIFT spectra of an e s s e n t i a l l y unoxidized s t a t e of the
Wyodak c o a l (Curve B) i s compared to that of the same sample a f t e r
1 hour of o x i d a t i o n i n 2.7 kPa of a i r at 393°C (Curve B) i n Figure
3. The most notable d i f f e r e n c e s i n these spectra are decreased
a b s o r p t i o n of the a l i p h a t i c C-H s t r e t c h i n g bands at ~ 2900
1
cm" and the appearance of a carbonyl s t r e t c h i n g band at ~ 1700
1
cm" . These features are accentuated i n the d i f f e r e n c e spectrum
(Curve C). Figures 4 and 5, which represent the s e r i e s of d i f
1 1
ference s p e c t r a f o r the 3900-2500 cm" and 2000-1200 cm" r e g i o n s ,
r e s p e c t i v e l y , measured at successive time i n t e r v a l s i n the oxida
t i o n , i l l u s t r a t e i n considerably more d e t a i l the changes which are
o c c u r r i n g . The negative peaks are i n d i c a t i v e of species or func
t i o n a l groups which are l o s t and the p o s i t i v e peaks to those which
are formed. Since the study was done i n s i t u , there was l i t t l e

4,000 3,500 3,000 2,500 2,000 1,500 1,000 500

1
WAVE NUMBER [cm" ]
Figure 2. DRIFT spectra. Key: A, Bruceton coal; B, kaolin in KCl (2.0%); and
C, difference spectrum (A - 0.7404 X B).
1
WAVE NUMBER [cm" ]
Figure 3. DRIFT spectra of Wyodak coal. Key: A, sample after ~ 24 h of oxida-

tion in 2.7 kPa of air at 393°C; B, dried unoxidized sample; and C, difference
spectrum (A — B).

3400 3Z00 30 2600

WAVENUMBERS
Figure 4. DRIFT difference spectra of in situ oxidized Wyodak coal (3990 - 2500
cm' ). Key to time elapsed: A, 1 min; B, 5 min; C, 15 min; D, 30 min; E, 45 min;
1
F, 1 h; G, 1.5 h; H, 1.75 h; I, 2 h; and J, 19.5 h.

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doubt about the proper weighting f a c t o r f o r the s u b t r a c t i o n (1:1).

Problems a s s o c i a t e d w i t h v a r i a t i o n s between samples, matrix
a f f e c t s , t r a n s p o r t , and handling, e t c . are nonexistent. The
changes due to o x i d a t i o n are evident since the mathematical d i f
ferences need not be adjusted f o r extraneous f a c t o r s .
The l o s s of a l i p h a t i c C-H f u n c t i o n a l groups i s a measure of
the degree of o x i d a t i o n as noted by the i n c r e a s i n g negative
1
f e a t u r e s at 2950, 2925, and 2865 cm" (Figure 4 ) . The l o s s of
a l i p h a t i c C-H s t r e t c h i n g i n t e n s i t y has been i n t e r p r e t e d as oxida
t i v e a t t a c k a t a l i p h a t i c s i t e s ( p r i m a r i l y methylene groups i n the
b e n z y l i c p o s i t i o n ) i n c o a l (9)· There a l s o appears to be a s l i g h t
1
l o s s i n aromatic C-H s t r e t c h i n g i n t e n s i t y at 3035 cm" w i t h oxida
t i o n . However, by comparing the spectrum of the unoxidized c o a l
t o that of the f i n a l o x i d i z e d s t a t e i n Figure 6, the a l i p h a t i c and

aromatic C-H s t r e t c h i n g bands are observed to be roughly the same
i n t e n s i t y i n the f i n a l s t a t e i n d i c a t i n g that o x i d a t i o n has had
o n l y a minor e f f e c t on the aromatic p o r t i o n of the c o a l . I t
should be noted a t t h i s point that the d i f f e r e n c e i n Curves A and
Β o f Figure 6 i s represented by Curve J i n both Figures 4 and 5.
The formation of c e r t a i n o x i d a t i o n products are noted i n the
s e r i e s of d i f f e r e n c e spectra d i s p l a y e d i n Figure 5. The complex
1 1
band s t r u c t u r e from ~ 1650 cm" to ~ 1875 cm" represents a broad
range of carbonyl species formed during o x i d a t i o n . There are a t
l e a s t four d i s t i n c t bands which can be d i s t i n g u i s h e d at v a r i o u s
stages i n the o x i d a t i o n . There i s also a band noted at lower
1
wavenumbers (1550 cm" ).
1
P a i n t e r , £t a l , assigned a band at 1575 cm" t o a carboxylate
1
s a l t . The bands observed i n the present study at 1550 cm" might
correspond to the frequency observed f o r the antisymmetric O-C-O
s t r e t c h i n g i n c e r t a i n carboxylate s a l t s (35). We would, however,
tend to discount carboxylate s a l t formation during o x i d a t i o n due
t o l a c k of m o b i l i t y of both the organic and mineral phases of the
c o a l a t these lower temperatures. At t h i s p a r t i c u l a r time we have
no s t r a i g h t f o r w a r d a l t e r n a t i v e suggestion f o r the o r i g i n of t h i s
1
band. The s l i g h t i n c r e a s i n g negative feature at 1455 cm" should
a l s o be noted. This feature i s due t o the l o s s of absorption f o r
the methylene bending band which should accompany the
corresponding l o s s of methylene C-H s t r e t c h i n g absorption as pre
v i o u s l y noted.
1
I n Figure 5 a band at 1705 cm" i s observed which appears to
predominate i n the e a r l y stages of o x i d a t i o n (note i n p a r t i c u l a r
Curve B ) . I n the low temperature o x i d a t i o n work of P a i n t e r ,
et a l ( 9 ) , i n a higher ranked c o a l , a band near t h i s v a l u e , a t t r i
buted to a r y l a l k y l ketones, predominated i n the spectra of both
the e a r l y and l a t t e r stages of o x i d a t i o n . A prominent shoulder i s
1
a l s o noted i n Curve Β of Figure 5 a t ^ 1745 cm" . This band along
1
w i t h a band observed at 1775 cm" , which i s the dominant feature
i n the l a t t e r stages of o x i d a t i o n (see Curve J ) , are perhaps due
t o a v a r i e t y of e s t e r type f u n c t i o n a l groups (9,10,35). The obser
1
v a t i o n of a prominent shoulder at ~ 1845 cm" i n Curve J might

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i n d i c a t e that the 1775-1750 cm"" r e g i o n might a l s o contain an
a b s o r p t i o n c o n t r i b u t i o n from c e r t a i n c y c l i c anhydrides attached to
aromatic or unsaturated r i n g s t r u c t u r e s (10,35). Another p o s s i b l e
e x p l a n a t i o n f o r the o r i g i n of the 1845 c n f ^ f e a t u r e i s the forma
t i o n of organic carbonates (35,36). C e r t a i n l y , the i n t e r p r e t a t i o n
of the carbonyl r e g i o n of the d i f f e r e n c e spectra i s f a r from being
s t r a i g h t f o r w a r d ; however, a general trend does appear throughout
these s p e c t r a which would i n d i c a t e a l o g i c a l p r o g r e s s i o n of oxida
t i v e productβ that might be expected from i n c r e a s i n g
r e a c t i o n (36,37). The e f f e c t i s manifest i n two aspects: (1)
enhanced a b s o r p t i o n at (2) higher wavenumbers.
Conclusion
A number of d i s t i n c t advantages over the standard KBr p e l l e t

technique has been demonstrated f o r the a n a l y s i s of c o a l using
DRIFT spectroscopy. The p r i n c i p l e advantage i s the a b i l i t y to
monitor v a r i o u s r e a c t i o n processes i n s i t u where temperature and
f l u i d phase environment can be a c c u r a t e l y c o n t r o l l e d .
S p e c i f i c a l l y , data was presented d e s c r i b i n g moisture desorptlon
and intermediate temperature a i r o x i d a t i o n of a powdered sub-
bituminous c o a l . In comparison to i t s companion method, PA-IR,
DRIFT spectroscopy would appear to be the technique of choice f o r
the study of such r e a c t i o n processes i n v o l v i n g powdered samples
s i n c e the temperature and environment of the sample are more con
v e n i e n t l y c o n t r o l l e d . A l s o PA-IR i n general r e q u i r e s longer data
a c q u i s i t i o n times than DRIFT to produce a s i m i l a r q u a l i t y S/N
r a t i o (34). No e f f o r t has been made i n t h i s report to t r e a t i n
any way the q u a n t i t a t i v e aspects which most s u r e l y at some point
must be considered. Most q u a n t i t a t i v e work i n v o l v i n g DR spectra
has u t i l i z e d the Kubelka-Munk Equation to mathematically t r e a t the
d a t a . This Equation seems to apply mainly to species i n h i g h l y
r e f l e c t i n g matrices at low d i l u t i o n . Therefore, i t remains to be
determined what treatment may be required f o r DR s p e c t r a l data
obtained from neat m a t e r i a l s such as c o a l .
I t should be emphasized that the technique has been shown to
work very w e l l i n d e f i n i n g the organic intermediates f o r a i r o x i
d a t i o n of c o a l . The progressive dehydrogenation and subsequent
oxygenation of the s o l i d substrate are quite w e l l defined; thus we
have the c a p a b i l i t y to e l u c i d a t e , i n r e a l time, the intermediate
s t a t e s ("activated s t a t e s " , "surface complexes", etc.) (38) that
e x i s t i n the c o n t r o l l e d combustion the of powder where the f i n a l
s t a t e s are carbon d i o x i d e , carbon monoxide, and water.
Future s t u d i e s w i l l evaluate the k i n e t i c s of combustion and
the r e l a t i v e c o n t r i b u t i o n of these o x i d i z e d e n t i t i e s i n the g l o b a l
analyses r e l a t e d to r e l e v a n t parameters: (1) c o a l rank, (2) par
t i c l e s i z e , (3) gas phase t r a n s p o r t , (4) c a t a l y t i c adducts, (5)
c o a l p o r o s i t y , (6) temperature, (7) pressure, e t c .

Acknowl edgment
T h i s work was c a r r i e d out at the Oak Ridge Y-12 P l a n t ,

operated f o r the U.S. Department of Energy by the Union Carbide
C o r p o r a t i o n , Nuclear D i v i s i o n , under U. S. Government Contract
W-7405-eng-26.
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P. L., Jr., Fuel, 57, 125 (1978).
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and Walker, P. L., Jr., Fuel, 57, 337 (1978).
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Gong, H., and Suhr, Ν., Fuel, 59, 364 (1980).
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5. Painter, P. C., Youtcheff, J., and Given, P. Η., Fuel, 59,
523 (1980).
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and Walker, P. L., Jr., Fuel, 58, 293 (1979).
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Komatsu, Μ., and Walker, P. L., Jr., Appl. Spectrosc., 35,
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Kuehn, D. W., and Davis, Α., Appl. Spectrosc., 35, 475
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11. Solomon, P. R., and Colket, Μ. Β., Fuel, 57, 749 (1978).
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Decomposition Products, in "Coal Structure: Advances in
Chemistry Series", Gorbaty, M. L., and Ouchi, Κ., Eds.,
American Chemical Society, Washington, D. C., Vol 192, Chap.
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(3), 104 (1980).
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21. Niwa, M., Hattori, T., Takahashi, M., Shirai, K., Watanabe,
Μ., and Murakami, Υ., Anal. Chem., 51, 46 (1979).
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RECEIVED July 15, 1982

6
Comprehensive Elemental Analysis of Coal
and Fly Ash
R. A . NADKARNI
Exxon Research and Engineering Company,
Analytical Research Laboratory, Baytown, T X 77520
All major ash elements and some trace elements are

determined in coal or fly ash by inductively
coupled plasma emission spectrometry. Parr oxygen
bomb combustion followed by ion selective electrode,
X-ray fluorescence or atomic absorption spectrom-
etric measurements are used to determine halogens,
sulfur, nitrogen, mercury, arsenic, selenium, and
phosphorus. Hydride generation-atomic absorption
spectrometry is used to determine traces of As,
Se, Sn, Sb, Te, Pb, and Bi. Spectrophotometric
determinations are used for gallium and germanium.
With the increased emphasis on the development of syn-

t h e t i c f u e l s to supplement the d e p l e t i n g n a t u r a l petroleum
resources, c o a l i s coming i n t o prominence as a v i a b l e a l t e r n a t i v e
f u e l source. Since c o a l i s a heterogeneous mixture o f many
m i n e r a l s , i t i s important to have a n a l y t i c a l methods to measure
the inorganic c o n s t i t u e n t s a c c u r a t e l y and thus to be able t o
f o l l o w t h e i r path through various stages of c o a l production and
utilization. This paper describes the approach o f Exxon's
Baytown Research and Development D i v i s i o n to a n a l y z i n g c o a l and
f l y ash samples with some e s t a b l i s h e d techniques and some newer
improvements that have been incorporated i n them. The f i r s t
paper i n t h i s s e r i e s was published by us e a r l i e r (I) emphasizing
the a n a l y s i s o f major elements.
Experimental
Sample Preparation.
F i n e l y ground ( u s u a l l y -300 mesh) c o a l samples are ashed at

750°C i n a muffle furnace to a constant weight. Alternatively,
an RF plasma low temperature asher can be used; however, the time
needed f o r ashing i s o f the order of a few days. The c o a l ash or
American Chemical
0097-651/82/0205-0l47$06.00/0
© li(HWewrMffT3tônûcal Society
In Coal and Coal Products: 16th St.Characterization
1155 Analytical N. W. Techniques; Fuller, E.;
ACS SymposiumWwfctoette. 0.Chemical
Series; American C. 2003·
Society: Washington, DC, 1982.
f l y ash thus prepared i s brought i n t o s o l u t i o n by d i s s o l v i n g i n a

mixture o f aqua r e g i a + HF i n P a r r T e f l o n bombs heated a t 110°C
f o r two hours. The d e t a i l s are d e s c r i b e d elsewhere (jO.
I n d u c t i v e l y Coupled Plasma Emission Spectrometry (ICPES).
The sample prepared by d i s s o l u t i o n i n a P a r r bomb i s

analyzed by ICPES. We use a J a r r e l l - A s h Plasma AtomComp 90-975
w i t h 90-55 spectrum s h i f t e r f o r background c o r r e c t i o n . The
d e t a i l s o f our i n s t r u m e n t a t i o n and the o p e r a t i o n have been
described elsewhere ( 2 ) .
Atomic A b s o r p t i o n Spectrophotometer (AAS).

A V a r i a n 475 spectrophotometer and M-65 vapor g e n e r a t i o n

accessory i s used f o r the d e t e r m i n a t i o n o f mercury through c o l d
vapor g e n e r a t i o n , and f o r the d e t e r m i n a t i o n o f As, Se, Sb, B i ,
Te, Sn, and Pb through hydride g e n e r a t i o n . The procedure f o r
mercury i s d e s c r i b e d elsewhere (1). In practice, after d i s -
s o l u t i o n and d i l u t i o n o f the sample i n a f i x e d volume, an a l i q u o t
of the s o l u t i o n i s taken and i s t r e a t e d w i t h enough HC1 t o proper
normality.
As d e s c r i b e d l a t e r , the s o l u t i o n s are t r e a t e d w i t h a d d i -
t i o n a l reagents and allowed t o r e a c t f o r d e s i r e d time p e r i o d s .
The s o l u t i o n i s t r a n s f e r r e d t o the M-65 hydride generator acces-
sory. The generator i s c o n t i n u o u s l y f l u s h e d w i t h n i t r o g e n gas
to c a r r y the hydrides t o the burner. On dropping a p e l l e t o f
NaBH4 i n t o the generator, gaseous metal-hydrides are immediately
produced and are swept by the n i t r o g e n gas i n t o a heated open-
ended quartz tube l o c a t e d on the burner-head i n the l i g h t path o f
the AA-475 instrument. The hydrides are decomposed i n the heated
tube w i t h hydrogen burning q u i e t l y a t both ends o f the tube.
Some p a r t i c l e s o f NaBIty are p h y s i c a l l y c a r r i e d over i n t o the
flame, which imparts a b r i g h t y e l l o w c o l o r t o the flame. The
atomized elements are measured by the AA instrument, p r e f e r a b l y
i n the peak area mode. A f t e r one measurement i s completed, the
s o l u t i o n i n the generator i s drained out, and i t i s ready f o r the
next a n a l y s i s . D e t a i l s o f t h i s method a r e p u b l i s h e d elsewhere
(3).
P a r r Oxygen Bomb.
A P a r r 1901 oxygen bomb apparatus i s used w i t h s t a i n l e s s

s t e e l combustion c a p s u l e s . Less than 1 gm o f c o a l sample i s
mixed w i t h a few drops o f white o i l i n the cup. F i v e mL o f water
i s placed i n the bottom o f the bomb. The assembled and c l o s e d
bomb i s p r e s s u r i z e d t o 30 atm o f oxygen. A f t e r a few seconds o f
combustion (<10) the bomb i s allowed t o c o o l and then c a r e f u l l y
opened. The i n s i d e w a l l s o f the bomb are washed w i t h water and
combined w i t h 5 mL water i n the bomb. I f necessary, the s o l u t i o n

6. NADKARNi Elemental Analysis of Coal and Fly Ash 149
i s f i l t e r e d , and d i l u t e d to 50 mL. A l i q u o t s of t h i s s o l u t i o n
are analyzed f o r halogens, mercury, s u l f u r , n i t r o g e n , a r s e n i c ,
and selenium by d i f f e r e n t a n a l y t i c a l techniques. D e t a i l s of
t h i s method are published elsewhere ( 4 ) .
Miscellaneous Instrumentation.
Halogens are determined by an Orion 901 ion analyzer using

94-09 f l u o r i d e , 94-17 c h l o r i d e , 94-35 bromide, or 94-53 i o d i d e
e l e c t r o d e s . These determinations can be c a r r i e d out s e q u e n t i a l l y
on 1 a l i q u o t of sample i n the order c h l o r i d e , bromide, i o d i d e ,
and f l u o r i d e . F i v e M KNO3 i s used as the i o n i z a t i o n b u f f e r f o r
the f i r s t three ions, while Orion " t o t a l i o n i c strength a d j u s t o r
b u f f e r " i s used f o r f l u o r i d e a n a l y s i s . A l l determinations are

done by the standard a d d i t i o n s technique.
C o l o r i m e t r i c measurements are c a r r i e d out using a Varian
634 UV-VIS spectrophotometer. Gallium and germanium are the only
elements determined i n t h i s f a s h i o n .
Other miscellaneous instrumentation used i n t h i s scheme of
complete c o a l a n a l y s i s i n c l u d e : P h i l l i p s PW-1212 X-ray F l u o r -
escence analyzer f o r s u l f u r , Antek-771 chemiluminescent analyzer
for n i t r o g e n , and Texas Nuclear 9500 14-MeV neutron generator
for oxygen.
Results and D i s c u s s i o n
ICPES A n a l y s i s .
We have described our b a s i c procedure f o r the "ash elements"

a n a l y s i s by ICPES e a r l i e r (1)> and we w i l l not d e s c r i b e the
d e t a i l s here. Even though our ICPES system i s equipped with 34
element channels, normally data on 20-25 elements can be obtained
with good p r e c i s i o n and accuracy i n a c o a l ash s o l u t i o n matrix.
Some a d d i t i o n a l trace elements have been determined with a com-
puter c o n t r o l l e d scanning monochromator ICPES by Floyd et a l
(5), however, our ICPES i s equipped with f i x e d array of e x i t
s l i t s on a polychromator and some t r a c e elements cannot be
determined with r e l i a b i l i t y due to a combination of t h e i r low
c o n c e n t r a t i o n i n the c o a l or f l y ash, and the background i n t e r -
ference from major elemental l i n e s i n the determination of weaker
trace element l i n e s . A t y p i c a l example of r e s u l t s obtained by
the Parr bomb d i s s o l u t i o n procedure, followed by ICPES measure-
ments, i s given i n Table I. Our r e s u l t s f o r N a t i o n a l Brueau of
Standards (NBS) Standard Coal-1632 and F l y Ash-1633 are compared
with NBS c e r t i f i e d v a l u e s , or "best" values from the l i t e r a t u r e ,
where a v a i l a b l e . The best values were obtained from over 70
papers i n the l i t e r a t u r e . The obvious o u t l i e r s were omitted i n
c a l c u l a t i n g the average v a l u e s . The agreement between our r e -
s u l t s and the "known v a l u e s " i s s a t i s f a c t o r y . The average
accuracy of our data i s ±10%, though some trace elements have

150 COAL A N D COAL PRODUCTS
Table I
Elemental A n a l y s i s of Coal and F l y Ash

by I n d u c t i v e l y Coupled Plasma Emission Spectrometry
Element, NBS-1632 Coal NBS-1633 F l y Ash

ppm Present(a) Found Present(a) Found
Al, % 1.78 1.71 12.5 12.7

Ba 342 219 2700 2100
Be 1.45 1.53 11.9 18.7
Ca, % 0.41 0.49 4.60 5.21
Co 5.78 5.5 39.3 25
Cr 20.2±5 12 131±2 104
Cu 18+2 15 128±5 142
Fe, % 0.87±0.03 0.72 6.18 5.53
K, % 0.29 0.20 1.68 1.71
Mg, % 0.16 0.12 1.55 1.30
Mn 40±3 39 493±7 483
Na 380 368 3200 3000
Ni 15±1 15.7 98+3 —
Ρ 71; 118 118 880 1004
Si, % 3.38 2.41 20.5 22.7
Ti 960 702 7200 6800
V 35±3 30 214±8 214
Zn 37±4 39 210±20 197
(a) From Nadkarni ( 1). Values with standard d e v i a t i o n s

are N.B.S. c e r t i f i e d .

l a r g e r e r r o r s . Many other standards have been analyzed by t h i s

procedure with e q u a l l y good r e s u l t s .
Parr Oxygen Bomb Procedure.
The main advantage of t h i s method i s i n determining what we

c a l l the " v o l a t i l e " elements such as halogens, s u l f u r , n i t r o g e n ,
phosphorus, a r s e n i c , and selenium. Normally these elements have
to be determined i n d i v i d u a l l y with separate sample p r e p a r a t i o n i n
each case. However, once the c o a l sample i s combusted i n a Parr
oxygen bomb, and the gases produced are trapped i n an e x t r a c t a n t
such as water or d i l u t e d Na2C03, a l l the above elements can be
determined i n the r e s u l t a n t s o l u t i o n . A l l the halogens are
determined by i o n s e l e c t i v e e l e c t r o d e s , mercury by Cold Vapor-

AAS, n i t r o g e n by Antek chemiluminescent d e t e c t o r , s u l f u r by XRF,
a r s e n i c , phosphorus and some other elements by ICPES. Our
r e s u l t s f o r NBS-1632 and 1632a c o a l s and 1571 Orchard Leaves are
given i n Table I I . We f i n d good agreement between our r e s u l t s
and the l i t e r a t u r e v a l u e s . We have seen no iodine or selenium i n
any c o a l samples we have analyzed, because of t h e i r low l e v e l s of
c o a l . The only other trace elements we found i n the combustion-
absorption s o l u t i o n s were boron and lead; however, n e i t h e r of
these elements seem to be q u a n t i t a t i v e l y recovered by t h i s
procedure.
Vapor Generation-Atomic Absorption Spectrometry.
Even though the ICPES system i s extremely s e n s i t i v e f o r

most o f the trace elements, i t i s s t i l l not p o s s i b l e to determine
s e v e r a l c r i t i c a l l y important elements such as As, Se, Sb, Pb,
e t c . i n a c o a l or f l y ash matrix. Though t h e o r e t i c a l s e n s i t i v i t y
may be impressive, the presence of large concentrations of the
matrix elements, which produce i n t e r f e r e n c e s and high background,
make the high ICPES s e n s i t i v i t y i n e f f e c t i v e . Atomic a b s o r p t i o n
spectrophotometry with a hydride generation accessory i s one
p o s s i b l e way of determining t h i s group of elements. In t h i s
mode, the elements of i n t e r e s t are converted i n t o gaseous
hydrides, which are then fed i n t o the flame, decomposed t h e r e i n ,
and the elements are determined by AAS. Mercury, which does not
form a hydride, can a l s o be determined i n t h i s same f a s h i o n by
forming gaseous elemental mercury. The d e t e c t i o n l i m i t s of
ICPES, AAS with flame, and AAS with hydride generation are com-
pared i n Table I I I (6) where i t can be c l e a r l y seen that the l a s t
mode of determination i s the best. In a d d i t i o n , the matrix i s
e l i m i n a t e d i n the hydride mode but not i n flame AAS or ICPES.

Table I I
Trace Elements Determination i n Coal Using Parr Oxygen Bomb
Method NBS-1632a NBS-1632 NBS-1571

of Coal Coal Orchard Leaves
Deter- Found Found
Element, mination Pres. (c) Près. Pres. (c)
ppm (a) (b) (N=5) (d) Found (b) (n=3)
Fluorine I SE 92 84±8 90 71 - -
Chlorine I SE 784 770 962 915 690 638
(12) ± ±
48 27
Bromine ISE 45 43 - - - -
(13)
Mercury CV-AAS 0.13 0.17 0.12 0.12 — —

± ± ±
0.03 0.02 0.02
Nitrogen, Antek 1.27 1.19 — — — —
(12) ±
0.08
Sulfur, % XRF 1.62 1.48 1.35 1.32 0.19 0.27

± ± ±
0.03 0.07 0.04
Arsenic ICPES 9.3 8.9 5.9 5.31 10±2 8.9

± ± ± ±
1 1.2 0.6 2.2
Phosphorus ICPES - 85±17 71;118 156 - -

Boron ICPES 53 22±3 40 29 - -
(12)
Lead ICPES 12.4 7±1 30±9 19 45±3 31±2

±
0.6
(a) E x p l a n a t i o n i n the text

(b) From NBS C e r t i f i c a t e of A n a l y s i s and l i t e r a t u r e values where
available
(c )Number of r e p l i c a t e analyses; ± values represent one
n
standard d e v i a t i o n from mean value

(d) From Nadkarni (1)

Table I I I (6)
D e t e c t i o n L i m i t s of D i f f e r e n t Spectroscopic Procedures
Element, ppm ICPES AAS Flame AAS Hydride
As 0.04 0.63 0.0008

Bi 0.05 0.044 0.0002
Ge 0.15 0.02 0.004
Pb 0.008 0.017 0.10
Sb 0.20 0.06 0.0005
Se 0.03 0.23 0.0018
Sn 0.30 0.15 0.0005
Te 0.08 0.044 0.0015
The s p e c t r a l p r o p e r t i e s of the hydride forming group of

elements are given i n Table IV. As i s e v i d e n t , the hydride
generation-AAS method i s extremely s e n s i t i v e with a f a i r l y large
dynamic range. This higher s e n s i t i v i t y i s obtained by using the
peak area r a t h e r than the peak height absorbance mode. Use of
e l e c t r o d e l e s s discharge lamps instead of the hollow cathode lamps
a l s o increases the s e n s i t i v i t y s e v e r a l f o l d i n the case of
a r s e n i c and selenium. In the case of other elements, the EDLs
are not that advantageous over HCLs.
Table IV
AAS Determination of Hydride Forming Elements
Wavelength Slit Sensitivity Range

Element Hydride B.P. °C nm nm ng ng
As AsH 3 -55 193.7; 1 0.2 30

197.2
Bi BiH 3 -22 233.1 0.2 0.4 60
Ge GeH 4 -88.5 265.1 1 0.05 —
Pb PbH 4
— 217.0 1 1.4 300
Sb SbH 3 -17 217.6; 0.2 0.2 30
231.2
Se H Se
2 -42 196.0 1 0.6 100
Sn SnH 4 -52 286.3 0.5 0.8 100
Te H Te
2 -4 214.3 0.5 0.5 50
Most of these hydrides are generated i n s t r o n g l y a c i d i c

s o l u t i o n with some reducing agents such as z i n c , magnesium,
t i t a n i u m t r i c h l o r i d e or sodium borohydride. The l a s t reagent i s
now almost u n i v e r s a l l y p e r f e r r e d . I t can be used as a d i l u t e
s o l u t i o n , which i s somewhat unstable, or as s o l i d p e l l e t s . Since
ng amounts of the hydride forming elements are determined, i t i s
extremely important to keep the working environment c l e a n . Ultra

pure reagents o n l y , where a v a i l a b l e , should be employed, although

sometimes we have found even these to be contaminated. Thus, an
i d e n t i c a l blank must be c a r r i e d through the e n t i r e procedure each
time. V a r i a t i o n i n the a r s e n i c content of the NaBIty p e l l e t s
from 3 ng to 90 ng per p e l l e t has been r e p o r t e d ( 7 ) . The con
c e n t r a t i o n of a c i d i n s o l u t i o n has pronounced e f f e c t on the
a b s o r p t i o n s i g n a l . No e f f e c t on absorbance of As, B i , and Sb
was observed on changing the HC1 c o n c e n t r a t i o n from 1 to 9 N.
The selenium response i s optimum i n the 2.5 to 5 Ν range of HC1
s t r e n g t h . The optimum HC1 c o n c e n t r a t i o n f o r the I^Te p r o d u c t i o n
i s between 2.5 to 3.6 N. The production of SnH4 i s markedly
dependent on the HC1 c o n c e n t r a t i o n , the optimum being 0.6 to 1 N.
Outside these l i m i t s , the absorbance dropped s h a r p l y . For the
r e s t of t h i s work 4 N HC1 s o l u t i o n s t r e n g t h was used i n the

a n a l y s i s of As, B i , Sb, and Se. O x i d a t i o n s t a t e of some elements
i s a l s o c r i t i c a l i n a n a l y s i s . Thus, a r s e n i c and antimony have
to be i n +3 form, and selenium i n +4 s t a t e . This i s achieved by
a p p r e c i a b l e amounts of c o a l m a t r i x — N a , A l , K, Ca, Mg, Fe, T i ,
P, L i , Sr, Ba, N i , Cr, S i , e t c . — w e r e found not to i n t e r f e r e
w i t h the hydride d e t e r m i n a t i o n .
Lead i s determined by hydride-AAS procedure f o l l o w i n g the
method of Fleming and Ide ( 8 ) . T a r t a r i c a c i d and l ^ C ^ O y at
pH 1.5 to 2 are used f o r optimum Pblty p r o d u c t i o n .
R e s u l t s of u s i n g the hydride-AAS method f o r two NBS standard
c o a l s and a f l y ash are summarized i n Table V. Each sample was
run on f i v e r e p l i c a t e a l i q u o t s . No bismuth was detected i n any
sample. No t e l l u r i u m was detected i n c o a l 1635. There are no
l i t e r a t u r e values a v a i l a b l e f o r e i t h e r of these c o a l s ; two
l i t e r a t u r e values a v a i l a b l e f o r t e l l u r i u m i n the f l y ash are
w i d e l y d i f f e r e n t from each other and from our v a l u e , p o i n t i n g
to the d i f f i c u l t y i n determining t h i s element by most a n a l y t i c a l
techniques. Agreement of other elements between our r e s u l t s
and the NBS values i s s a t i s f a c t o r y . The o v e r a l l p r e c i s i o n of
the r e s u l t s i s of the order of ±10%.
Spectrophotometric Determination of Ga and Ge.
The s i g n i f i c a n c e of these two elements i n c o a l or f l y ash

i s from the p o i n t of view of t h e i r recovery from c o a l ashes or
f l y ashes. The c o n c e n t r a t i o n l e v e l s of these two t e c h n o l o g i c a l l y
v a l u a b l e elements i n other m i n e r a l sources ( p r i n c i p a l l y z i n c
and aluminum ores) i s about the same l e v e l as i n c o a l or f l y
ashes (Table V I ) . Both of these elements are d i f f i c u l t to
determine by most a n a l y t i c a l techniques. We have chosen to
use two s e n s i t i v e and r e l a t i v e l y s e l e c t i v e reagents to e x t r a c t
these elements i n t o organic s o l v e n t s and then spectrophoto-
m e t r i c a l l y measure them. The flow scheme of a n a l y s i s i s given
i n Table V I I .

Table V
Determination o f Trace Elements i n Coal by

Hydride Generation-Atomic Absorption Spectrometry
Coal-1632a Coal-1635 F l y Ash-1633

Found Found Found

Present (b) Present (b) Present (b)
Element (a) (n=5) (a) (n-5) (a) (n-5.)
Arsenic 9.3±1 9.5 0.42 0.28 61±6 64±4

± ± ±
0.6 0.15 0.02
Selenium 2.6±0.7 3.1 0.9±0.3 0.79 9.4±0.5 8.8±0.5

± ±
0.2 0.07
Antimony 0.58 0.41 0.14 0.13 6.9 6.0*0.6

± ±
0.15 0.01
Tin - 8.1±1 - - 10.9 12.7±0.8
Lead 12.4 12.4 1.9 1.5 70±4 80i-10

± ± ± ±
0.6 0.4 0.2 0.2
Tellurium - 0.50 - <0.1 2.3; 0.9±0.1

+ 9.9
0.05
(a) From N.B.S. C e r t i f i c a t e o f A n a l y s i is or 1:

where a v a i l a b l e .
(b) Number of r e p l i c a t e analyses; ± values represent one
standard d e v i a t i o n from the mean value.

Table VI
Gallium and Germanium i n Coals
Material Ga, ppm Ge ? ppm
Western U.S. c o a l s 1-7 1-22

I l l i n o i s coals 1-10 1-43
Appalachian coals 3-11 6
Eastern coals 4 13
N. Dakota l i g n i t e ashes 10-50 2-7
S. A f r i c a n coals
A u s t r a l i a n coals
50
1-20 1-30
-
Indian (Assam) c o a l s - 0.06-1%

1.5%
Indian f l y ash
-
The g a l l i u m ( I I l ) - m a l a c h i t e green r e a c t i o n has to be per-
formed i n a reducing medium since the colored o x i d a t i o n product
of the dye i s a l s o e x t r a c t e d . Titanium c h l o r i d e i s used f o r t h i s
purpose. The c o l o r i s extracted i n t o the organic solvents from
1 to 9 N HC1 s o l u t i o n s ; however, the maximum e x t r a c t i o n takes
place i n the range 5 to 6.5 N HC1. The e x t r a c t i o n i s complete i n
l e s s than a minute and f u r t h e r shaking has no e f f e c t on the
maximum e x t r a c t i o n . Various complexing agents such as sodium
c i t r a t e , sodium potassium t a r t a r a t e and potassium cyanide have no
e f f e c t on the e x t r a c t i o n o f the c o l o r e d complex. Among the
organic solvents tested f o r e x t r a c t i o n behavior, CCI4 and
dichloroethane were found to have the lowest e x t r a c t i o n c a p a c i t y
for the complex, while chloroform, benzene and e t h y l acetate
were a l l found to e x t r a c t the complex q u a n t i t a t i v e l y . Chloroform
was used as the extractant i n a l l f u r t h e r work.
The maximum absorption of the colored gallium-malachite
green complex i n chloroform was found to be 623 nm. The c o l o r
once extracted was s t a b l e f o r three hours, a f t e r which the
absorption g e n e r a l l y decreased. The Beer-Lambert law i s obeyed
at l e a s t up to 0.4 ppm g a l l i u m .
Jankovsky (9) and Nadkarni et a l (10) have studied the
i n f l u e n c e o f f o r e i g n ions i n the gallium-malachite green r e a c t i o n
and e x t r a c t i o n . Only elements that can i n t e r f e r e are s i l v e r
(by formation o f AgCl); Au, Pb, Se and Te (by r e d u c t i o n to
m e t a l l i c s t a t e by T1CI3); and tungsten (by h y d r o p y r o l y s i s ) .
However, none of these elements are present i n c o a l or f l y ash
at l e v e l s more than subppm, and hence, no serious i n t e r f e r e n c e
from these elements i s expected. Copper, Mo, Sb and T l give
colored e x t r a c t s , but even i n the presence of 100 to 1000 f o l d
excess t h e i r i n f l u e n c e on the g a l l i u m determination i s small.
T i n can be t o l e r a t e d up to 50 fold* excess. Thus, f o r p r a c t i c a l
purposes o f c o a l or f l y ash a n a l y s i s , no p a r t i c u l a r i n t e r f e r e n c e
i s expected i n the g a l l i u m determination.

Table VII
A n a l y t i c a l Scheme f o r Gallium
and Germanium Determination i n Coal
Parameter Gallium Germanium
Dissolution Aqua-Regia + Aqua-Regia + HF i n a

HF i n a Parr Parr Bomb
Bomb
S o l u t i o n Treatment T1CI3 + Na*K° 8-9M i n HC1 + FeS04

T a r t r a t e + HC1
to 6N Strength
Reagent Malachite Green Pheny1fluorone
Extractant Chloroform Carbon T e t r a c h l o r i d e
Organic Phase Wash with 6N Back e x t r a c t i n t o water

Treatment HC1 + T1CI3
Wavelength 623 nm 511 nm
Linearity 0-0.3 ppm 0-1.0 ppm
Interferences None Serious None a f t e r P r e p a r a t i o n
Sensitivity 0.05 ppm 0.1 ppm
Reference ( 9 ) , (10) (11)

The most s e n s i t i v e and s e l e c t i v e method f o r the determination

of germanium appears to be a c o l o r i m e t r i c procedure based on the
r e a c t i o n o f Ge (VI) with phenylfluorone or 9-Phenyl-2,3,7-
t r i h y d r o x y - 6 - f l u o r o n e (J_l ). This reagent gives f l u o r e s c e n t red
c o l o r with Ge (IV) s o l u t i o n s . A p r i o r s e p a r a t i o n o f germanium
from other metals i n the s o l u t i o n i s necessary. The best pro-
cedure f o r t h i s i s to e x t r a c t GeCl4 i n t o immiscible organic
s o l v e n t s . GeCl4 i s q u a n t i t a t i v e l y e x t r a c t e d i n t o CCI4 at HC1
concentrations o f 8-9 M. E q u i l i b r i u m i s a t t a i n e d i n 1-2 minutes
of shaking. Germanium i s r e a d i l y recovered from the CCI4 phase
by shaking f o r 1-2 minutes with water. The only element ex-
t r a c t e d to a large extent (about 70%) i s a r s e n i c ( I I I ) . Since
small amounts o f a r s e n i c do not i n t e r f e r e with the phenylfluorone
method f o r germanium, i t s c o e x t r a c t i o n i s not a s e r i o u s matter.

The only other elements e x t r a c t e d by CCI4 at 8-9 M HC1 concen-
t r a t i o n s are: Se (IV) 0.01%, Sb (V) 0.01%, Sb ( I I I ) 0.003%, As
(V) 0.002%, Hg ( I I ) 0.003%, and Sn (IV) 0.001%. These elements
are completely recovered from the CCI4 l a y e r by washing i t with
9 M HC1. Once the germanium i s separated from other metals, i t
can be determined by the r e d c o l o r i t develops with phenyl-
fluorone. T h i s r e a c t i o n proceeds slowly i n d i l u t e (0.2-1.5 M)
HC1 s o l u t i o n s . About an hour i s needed f o r the maximum c o l o r
development. The c o l o r i s s t a b l e f o r s e v e r a l hours, but
g r a d u a l l y a f l o c c u l e n t product p r e c i p i t a t e s out overnight. There
are s e v e r a l ions which w i l l i n t e r f e r e i n t h i s r e a c t i o n by e i t h e r
developing c o l o r or o x i d i z i n g the reagent, but t h i s i s of l i t t l e
importance s i n c e the germanium w i l l have been separated from a l l
ions by CCI4 e x t r a c t i o n to i t s t e t r a c h l o r i d e p r i o r to the
phenylfluorone c o l o r development. The only element to accompany
germanium i s a r s e n i c ( i l l ) , which i s i n s e n s i t i v e to phenyl-
fluorone and does not i n t e r f e r e i n the germanium determination.
The maximum absorption o f the red germanium-phenylfluorone
complex was found to be 510-512 nm. The Beer-Lambert law i s
obeyed up to at l e a s t 1 ppm Ge. Results o f the determination
of g a l l i u m and germanium are shown i n Table V I I I . Our r e s u l t s
are mostly i n good agreement with the l i t e r a t u r e v a l u e s . The
eight l i t e r a t u r e values a v a i l a b l e f o r F l y Ash-1633 seem t o f a l l
i n t o two groups, four i n between 35-49 ppm, and the other four
between 58-77 ppm. The r e l a t i v e standard d e v i a t i o n f o r g a l l i u m
i s about 3% and f o r germanium ~3% f o r the f l y ash sample, but
-20% f o r the BCR rock sample.

Table V I I I
Spectrophotometric Determination of G a l l i u m and Germanium
Gallium, ppm Germanium, ppm

Sample Present Found(e) Present Found(e)
Coal-1632 6.8(a) 6.11 2.5(c) 2.6

Coal-1632a 8.49(b) 8.15
Coal-1635 1.05(b) 1.88
F l y Ash-1633 35-77(c) 49±0.4 (4) 25(c) 21±1 (3)
Rock BCR-1 20(d) 20±0.5(4) 1.54(d) 1.33±0.3(5)
(a) From Nadkarni (1)

(b) From NBS C e r t i f i c a t e of A n a l y s i s
(£) From l i t e r a t u r e values
(d) From Flanagan (14)
(e) Number o f r e p l i c a t e analyses i n parentheses; ± values
represent one standard d e v i a t i o n from the mean values
Conclusion
With the completion of t h i s work, we now have a n a l y t i c a l

c a p a b i l i t i e s f o r the determination of over 40 elements i n c o a l
and f l y ash. Table IX l i s t s these c a p a b i l i t i e s , and the same
data are depicted i n Figure 1 i n the p e r i o d i c t a b l e form.
Depending on the a n a l y s i s d e s i r e d , the c o a l or f l y ash a n a l y t i c a l
procedure can be v a r i e d . T r a d i t i o n a l l y , a c o a l sample i s ashed
i n a muffle furnace at 750°C f o r p r e p a r a t i o n of the ash. The
same r e s u l t with b e t t e r c o n t r o l of t r a c e element l o s s e s i s
achieved by using a low temperature RF plasma asher. The ash
from these steps i s fused with 1128407 on a C l a i s s e F l u x e r to
prepare a s o l u t i o n f o r major elements a n a l y s i s by ICPES.
A l t e r n a t i v e l y , the ash can be d i s s o l v e d i n a c i d s i n a Parr bomb
and analyzed by AAS or ICPES f o r the measurement o f a l l major
as w e l l as t r a c e metals. Other v o l a t i l e elements can be d e t e r -
mined by Parr oxygen bomb combustion and absorption of the
gaseous products i n a s o l v e n t . From t h i s s o l u t i o n , i n d i v i d u a l
elements can be determined, such as halogens by ISE, s u l f u r by
XRF, n i t r o g e n by Antek and a r s e n i c , selenium or phosphorus by
ICPES/AAS. In a d d i t i o n , a few s p e c i f i c elements are determined
d i r e c t l y , e.g. oxygen by 14-MeV NAA and mercury by Cold Vapor-
AAS. These methods, developed over the l a s t three years, are
now being a p p l i e d r o u t i n e l y f o r the a n a l y s i s of trace elements
i n s e v e r a l hundred c o a l s and s i m i l a r m a t e r i a l s each month i n
the BARD A n a l y t i c a l Resarch Laboratory.

160 COAL A N D COAL PRODUCTS
Table IX
Exxon-Baytown A n a l y t i c a l Methods
f o r Coal and F l y Ash A n a l y s i s
Detection
Limits i n
Sample Elements Sample
Technique Preparation Determined
ICPES Acid Dissolution A l , As, B, Ba, 0.1-10

or A l k a l i Fusion Be, Ca, Cd,
Co, Cr, Cu,
Fe, K, L i , Mg,
Mn, Mo, Na, N i ,
Ρ, Pb, Sb, S i ,
Sr, T i , V, Zn,
and U.*
AAS Acid Dissolution As, B i , Ge, 0.5

Hg, Pb, Sb,
- Hydride Se, Sn, and
Generation Te
Colorimetry Dissolution Ge and Ge 0.5

Extraction
INAA None Oxygen 0.01%
I SE Parr Oxygen Bomb Halogens 50

Combustion
Miscellaneous Parr Oxygen Bomb As, S, Ν, Ρ 10-1000

Combustion
*Not a l l o f the trace elements can be seen i n normal c o a l or f l y

ash samples, because of t h e i r very low concentrations and/or
matrix i n t e r f e r e n c e s .

NADKARNi Elemental Analysis of Coal and Fly Ash
(Zn - ICPES
H He
- INAA
X£3 * Cdor
Li Be L_.J · P » r r
02 Bomb
Β C Ν [0 j F Ne
1
LV. J - AAS
Να Mg Al Si! Ρ S Cl A
L._
ri
Κ Co Sc Ti V Cr Mn Fe Co Ni Cu ZnS5""(î£pS"Sê*fer Kr
Rb Sr Y ZrNb Mo Te Ru Rh Pd Ag Cd[în] Sn Sb Te 11 Xe
Cs Bo La Hf To WJRe Os Ir Pt Au[Hg|TI]Pb Bi ! Po At Rn
Fa Ra Ac
Ce Pr Nd Pm SmEu Gd Tb Dy Ho Er Tm Yb Lu
Th Pa[Û] Np Pu AmCmBk Cf Es Fm Md No Lw
Figure 1. Exxon-Baytown analytical methods for coal and fly ash analysis.

Ac know1edgemen t s
The author wishes to express h i s thanks to R. B. Williams

and R. I. Botto f o r encouragement and e n t h u s i a s t i c support.
Able t e c h n i c a l helps was provided by H. H. McQuitty, 0. Thomas,
D. M. Pond, and L. B. J e f f r e y during the development o f these
a n a l y t i c a l methods.
Literature Cited
1. Nadkarni, R. Α., Anal. Chem. 1980, 51, 929.
2. Botto, R. I., Proc. Intnat. Conf. Dev. At. Plasma
Spectrochem. Anal., Puerto Rico, 1980, In Press.
3. Nadkarni, R. Α., Anal. Chim. Acta, 1982, In Press.

4. Nadkarni, R. Α., Amer. Lab., 1981, 13-8, 22.
5. Floyd, Μ. Α., Fassel, V. Α., and D'Silva, A. P., Anal.
Chem., 1980, 52, 2168.
6. Robbins, W. B. and Caruso, J. Α., Anal. Chem., 1979, 51,
899A.
7. Knudson, E. J. and Christian, G. D., At. Abs. Newslett.,
1974, 13, 74.
8. Fleming, H. D. and Ide, R. G., Anal. Chim. Acta., 1976,
83, 67.
9. Jankovsky, J., Talanta, 1959, 2, 29.
10. Nadkarni, R. Α., Tejam, Β. M. and Haldar, B. C., Radiochem.
Radioanal. Lett., 1972, 12, 235.
11. Snadell, Ε. Β., "Colorimetric Determination of Traces of
Metals," 3rd Ed., 1959, Interscience Publishers, Inc.,
Ν. Y.
12. Failey, M. P., Anderson, D. L., Zoller, W. H., Gordon, G. E.
and Lindstrom, R. Μ., Anal. Chem., 1979, 51, 2209.
13. Gladney, E. S. and Perrin, D. R., Anal. Chem., 1979, 51,
2015.
14. Flanagan, F. J., Geochim. Cosmochim. Acta, 1973, 37, 1189.

7
Application of Inductively Coupled Plasma Atomic
Emission Spectrometry (ICP-AES) to Metal
Quantitation and Speciation in Synfuels
R. S. BROWN, D. W. HAUSLER , J. W. H E L L G E T H , and L . T . T A Y L O R

1
Virginia Polytechnic Institute and State University,

Department of Chemistry, Blacksburg, V A 24061
Metal analysis in coal derived products has

typically been a laborious, time consuming process.
Even with multielement emission techniques, typical
sample preparations involving destruction of the
sample matrix has limited sample throughput while
not allowing any subsequent speciation. The direct
analysis of coal derived products via inductively
coupled plasma atomic emission spectrometry
(ICP-AES) in organic solvents without pre-treatment
is reported. Several solvents which can be employed
with ICP are tabulated along with specific element
detection limits. Subsequent analysis by liquid
chromatography coupled with ICP detection in several
modes is described for model organometallic systems
as well as for several coal derived products as a
first step toward speciation of organically bound
metals in coal derived products.
Highly s p e c i f i c information concerning the chemical nature
and concentration of each moiety i n coal and coal conversion
products i s d e s i r a b l e i f extensive coal u t i l i z a t i o n i s t o be
achieved.(1_) Considering the high complexity and heterogeneous
nature of each sample, m u l t i p l e , i n f o r m a t i o n - s p e c i f i c ,
chromatographic-spectroscopic a n a l y t i c a l methods are r e q u i r e d . In
s o l u t i o n , where the maximum information i s achieveable the
a n a l y s i s problem i s f u r t h e r complicated by the f a c t that most
conventional s p e c t r o s c o p i c and chromatographic solvents have
l i t t l e a f f i n i t y f o r coal and coal l i q u i d s .
Within t h i s context, the q u a n t i t a t i o n and s p e c i a t i o n
of o r g a n i c a l l y bound t r a c e metals i n coal l i q u e f a c t i o n
s o l u b l e products presents a r e a l c h a l l e n g e . Quantitative
t r a c e element methods i n the s o l i d s t a t e on l i q u e f a c t i o n
1
Current address: Phillips Petroleum Company, Research and Development Labora-
tory, Bartlesville, OK 74005
0097-6156/82/0205-0163$06.25/0

products have been p r e l i m i n a r i l y e x p l o r e d . Spark source

mass spectrometry has been used to survey the d i s t r i b u t i o n and
general l e v e l of about s i x t y elements in the feed coal (West
V i r g i n i a ) and products from a s i n g l e batch of a long-term
l i q u e f a c t i o n run on the 400 l b coal/day PDU at the Pittsburgh
Energy Technology Center.(2) Atomic absorption spectrometry (AAS)
was employed f o r p r e c i s e a n a l y s i s of s p e c i f i c elements. In each
case, samples were ashed p r i o r t o a n a l y s i s to destroy the organic
m a t e r i a l . Neutron a c t i v a t i o n a n a l y s i s (NAA) has been r e c e n t l y used
t o obtain information on p o s s i b l e t r a c e element species present in
s o l i d SRC I and l i q u i d SRC II products derived from a Western
Kentucky c o a l . ( 2 » £) Although the d e t e c t i o n l i m i t s , multielement
c a p a b i l i t y and r e l a t i v e lack of matrix i n t e r f e r e n c e s make NAA an
a t t r a c t i v e a n a l y t i c a l procedure, long i r r a d i a t i o n times (10

minutes to 8 hours) and counting times (up t o 3 weeks) are major
undesirable f e a t u r e s . Furthermore, " o n - l i n e " a n a l y s i s of
separated components i s t o t a l l y i m p r a c t i c a l from a t i m e / e f f o r t
point of view.
Quantitation methods in s o l u t i o n have a l s o been minimal and
have involved e i t h e r s i n g l e element (continuous n e b u l i z a t i o n )
a n a l y s i s v i a atomic absorption spectrometry^) (AAS) or m u l t i -
element a n a l y s i s v i a i n d u c t i v e l y coupled plasma atomic emission
spectrometry (ICP-AES) both on acid digested aqueous-based
matrices.(6) These methods have not proven h i g h l y s a t i s f a c t o r y
because acTd d i g e s t i o n r i s k s the loss of v o l a t i l e elements and
i n t r o d u c e s , in some cases, a s u b s t a n t i a l blank v a l u e , r e q u i r e s a
great amount of time and labor and, in the AAS c a s e , provides f o r
only s i n g l e element determinations with mandatory background
correction. An a n a l y t i c a l method which e l i m i n a t e s the sample
preparation step and provides f o r multi-element q u a n t i t a t i v e
a n a l y s i s in the low ppm range seems h i g h l y a t t r a c t i v e f o r coal
l i q u e f a c t i o n products. In t h i s regard ICP-AES a n a l y s i s in a
p y r i d i n e matrix w i l l be reported here. For comparison, the
simultaneous determination of 15 d i f f e r e n t wear metals in
l u b r i c a t i n g o i l s d i s s o l v e d in 4-methyl-2-pentanone appears t o be
the only p r e v i o u s l y reported e f f o r t at q u a n t i t a t i o n v i a ICP-AES
in a t o t a l l y organic m a t r i x . ( 7 )
The need f o r sample d i g e s t i o n , in most of these r e p o r t s , in
order t o achieve a metal a n a l y s i s r e s u l t s in m o d i f i c a t i o n of the
chemical nature of the metals in these complex mixtures. Direct
a n a l y s i s in p y r i d i n e or any other organic solvent may allow f o r
information regarding the chemical nature of s p e c i f i c e n t i t i e s to
be e s t a b l i s h e d . Information regarding s p e c i a t i o n , however, i s not
r e a d i l y a s c e r t a i n e d . While c e r t a i n spectroscopic techniques such
as x-ray photoelectron spectroscopy and heavy metal nuclear
magnetic resonance spectrometry, are capable of y i e l d i n g
s p e c i a t i o n i n f o r m a t i o n , these methods normally r e q u i r e a
r e l a t i v e l y large concentration of i n d i v i d u a l metal s p e c i e s . A
c e r t a i n degree of success in t h i s area has been r e c e n t l y achieved.
EXAFS has been used to c h a r a c t e r i z e t i t a n i u m species in s o l i d SRC

7. BROWN ET AL. Metal Analysis Using ICP-AES 165
I and l i q u i d SRC II products and t o probe the chemical and

s t r u c t u r a l environment of vanadium in coal and coal l i q u e f a c t i o n
products,(8) Q u a n t i t a t i v e aspects of these s t u d i e s were not
considered. In the same v e i n , an extensive e x t r a c t i o n ( a c i d i c
methanol) and chromatographic procedure has been applied t o Daw
M i l l coal (92 Kg) with the r e s u l t that 17.8 mg of a mixture of
gallium complexes of homologous porphyrins (C27-C32) has been
i s o l a t e d f o r the f i r s t time. I d e n t i f i c a t i o n was based upon a
combination of s p e c t r o s c o p i c techniques.(9)
In a n t i c i p a t i o n of experiments designed t o y i e l d q u a n t i t a t i v e
s p e c i a t i o n i n f o r m a t i o n , we have r e c e n t l y e s t a b l i s h e d the
c a p a b i l i t y f o r multi-element detection in toluene and p y r i d i n e
matrices.(1Ό, 11) The development of a s i z e e x c l u s i o n
chromatographyTTCP-AES i n t e r f a c e designed to handle h i g h l y

v o l a t i l e organic solvents was reported and t e s t e d with mixtures of
model organometallies. Multi-dimensional chromatographic
f r a c t i o n s c o n t a i n i n g o r g a n i c a l l y bound metals from a SRC (Wyoming
subbituminous coal) have r e c e n t l y been isolated(12) employing t h i s
technique as a f i r s t step toward metal s p e c i a t i o n .
The present work which we b e l i e v e r e l a t e s to both
q u a n t i t a t i o n and s p e c i a t i o n w i l l (1) extend the number of solvents
and chromatographic methods which can be employed using t h i s
technique, (2) present metal detection l i m i t s in a v a r i e t y of
solvents f o r both d i r e c t a s p i r a t i o n and pumped d e l i v e r y , (3)
d i s c u s s t r a c e metal q u a n t i t a t i v e a n a l y s i s data obtained on
p y r i d i n e s o l u t i o n s of several SRC's as a f u n c t i o n of processing
c o n d i t i o n s and coal source and (4) d e s c r i b e the i s o l a t i o n of
o r g a n i c a l l y bound metal f r a c t i o n s in a SRC process s o l v e n t .
Experimental
The ICP-AES used in t h i s work was an ARL (Sunland, CA) model

137000. The LC i n t e r f a c e and instrumental parameters have been
described p r e v i o u s l y ( l O ) . An ice bath was used t o thermostat the
i n t e r f a c e with a l l s o l v e n t s . Chromatographic equipment consisted
of a Waters 6000A ( M i l f o r d , MA) pump with a Valco (50 and 200 yl
loop) i n j e c t i o n valve f o r i s o c r a t i c s e p a r a t i o n s . Columns were
purchased commercially and included a Waters μ - P o r a s i l s i l i c a
column (3.9mm χ 30cm), a Waters normal phase μ-Bondapak CN (3.9 mm
χ 30 cm) column, a Whatman Polar Amino Cyano column (4.6mm χ 75cm)
and a Waters 100 A μ-Styragel s i z e e x c l u s i o n column (3.9 mm χ 30
cm). Solvents were chromatographic grade from F i s h e r S c i e n t i f i c .
Model organometallie compounds were from "in-house" stocks or were
purchased from chemical warehouses.
Organo-metal q u a n t i t a t i o n standards in an o i l matrix were
obtained from Conostan (Ponca C i t y , 0K) at 300 ppm concentration
of each element. C a l i b r a t i o n standards in the range 0-25 ppm were
prepared on a w/w basis in p y r i d i n e . C a l i b r a t i o n curves were
generated from these standards f o r subsequent metal a n a l y s i s .
T y p i c a l root mean square (RMS) concentration e r r o r f o r t h i s curve

was -2% or b e t t e r f o r most elements. P y r i d i n e s o l u t i o n s of coal

derived material were -5-7% w/w. In order t o provide continuous
d e l i v e r y of p y r i d i n e t o the n e b u l i z e r spray chamber, a standard
l i q u i d chromatographic pump in conjunction with an i n j e c t o r
equipped with a 3 ml sample loop was employed. To avoid d i l u t i o n
of t h i s sample " p l u g " , a i r bubbles were placed in f r o n t and back
of the sample. Flow r a t e s of 0.5 ml/min were employed with s i g n a l
i n t e g r a t i o n times of 10-30 seconds. With chloroform and heptane
as s o l v e n t s , d i r e c t a s p i r a t i o n of standard s o l u t i o n s was employed
and d e t e c t i o n l i m i t s f o r a l l solvents were determined f o r each
element by c a l c u l a t i n g the concentration of analyte necessary t o
give a s i g n a l equal t o twice the standard d e v i a t i o n of the
background emission at each wavelength. It should be noted that
a l l d e t e c t i o n l i m i t s reported here are those at the i n t e r f a c e and

represent the l i m i t s f o r both t o t a l unseparated metal and
chromatographically separated and detected metal as each comes o f f
the column. We have observed f o r i n j e c t e d known amounts onto a
s i z e e x c l u s i o n column that a 10-20 f o l d increase i n d e t e c t i o n
l i m i t due t o chromatographic d i l u t i o n i s r e a l i z e d at the
interface.
Six SRC samples derived from Kentucky No. 9 c o a l were
obtained from the Southern S e r v i c e s , I n c . , W i l s o n v i l l e , AL p i l o t
plant funded by the E l e c t r i c Power Research I n s t i t u t e and the U.S.
Department of Energy and operated by C a t a l y t i c Inc. Information on
processing c o n d i t i o n s was k i n d l y supplied by Mr. B i l l Weber. A
process r e c y c l e solvent (92-03-035) o r i g i n a t i n g at the SRC-I p i l o t
plant in W i l s o n v i l l e , AL. was obtained from Mobil Research and
Development Corporation Central Research D i v i s i o n , P r i n c e t o n , NJ.
Results and Discussion
Metal A n a l y s i s of Solvent Refined C o a l s . I n i t i a l l y elemental

d e t e c t i o n l i m i t s were determined in a v a r i e t y of organic s o l v e n t s .
Chloroform and heptane were chosen because of t h e i r d e s i r a b i l i t y
as chromatographic s o l v e n t s . Toluene and p y r i d i n e were s e l e c t e d
f o r t h e i r tendency to s o l u b i l i z e coal derived products. Detection
l i m i t s f o r each metal in chloroform, toluene and heptane were
measured by d i r e c t a s p i r a t i o n using the n e b u l i z e r and spray
chamber chromatographic i n t e r f a c e described in reference ( 1 1 ) ,
while a pumped d e l i v e r y system was employed f o r p y r i d i n e .
Individual element d e t e c t i o n l i m i t s are shown in Table I f o r these
solvents along with the a n a l y t i c a l wavelengths monitored. These
represent compromise emission l i n e s f o r our polychromator system
i n order t o minimize i n t e r f e r e n c e s while maintaining reasonably
good d e t e c t i o n l i m i t s . Background l e v e l s f o r blanks although
higher than those of aqueous s o l u t i o n s showed l i t t l e i n t e r f e r e n c e
problems from organic emission. Detection l i m i t s f o r each metal
are, in g e n e r a l , s i m i l a r in each organic solvent as well as in
MIBK which has been p r e v i o u s l y i n v e s t i g a t e d . ( 7 ) An examination of
Table I i n d i c a t e s that water continues t o be The s u p e r i o r matrix

TABLE I
ELEMENTAL DETECTION LIMITS AND EMISSION LINES MONITORED IN VARIOUS SOLVENTS*
5 0 0 8 15
ELEMENT PYRIDINE* TOLUENE CHLOROFORM HEPTANE° MIBK WATER WAVELENGTH (A)
Ag 0.015 0.025 0.013 0.004 0.02 0.007 3280.7

Al 0.060 0.014 0.025 0.025 0.09 0.045 3082.2
Β 0.007 — 0.012 0.007 — — 2497.7
Ba 0.003 0.003 0.003 0.004 — 0.0013 4554.0
Ca 0.067 0.673 0.249 — 3179.3
Cd 0.004 0.005 0.003 0.005 — 0.0034 2265.0
Cr 0.011 — 0.005 0.009 — — 2677.2
Cu 0.006 0.017 0.009 0.018 0.006 0.0054 3247.5
Fe 0.009 0.070 0.006 0.008 0.04 0.0062 2599.4
Mg 0.003 0.005 0.001 0.001 0.007 0.00015 2795.5
Mn 0.002 0.002 0.001 0.001 0.01 0.0014 2576.1
Mo 0.074 — 0.025 0.043 — — 3132.6
Ni 0.038 0.034 0.026 0.096 0.1 0.015 2316.0
Pb 0.079 0.091 0.124 0.258 0.3 0.042 2203.5
Si 0.126 0.197 0.378 0.044 0.07 0.027 2881.6
Sn 0.055 0.041 0.086 0.064 0.03 0.025 1899.8
Ti 0.006 0.003 0.004 0.005 0.03 0.0038 3349.4
V 0.016 0.040 0.025 0.012 0.03 0.0075 2924.0
Zn 0.015 0.005 0.142 0.009 0.04 0.0040 2025.5

a A l l concentrations in ppm
^Pumped d e l i v e r y
c
Direct aspiration
f o r metal a n a l y s i s provided there are no other experimental

difficulties.
Detection l i m i t s v i a e i t h e r d i r e c t a s p i r a t i o n or pumped
d e l i v e r y are s i m i l a r f o r the same solvent ( t o l u e n e - p y r i d i n e ) ,
since n e b u l i z e r and spray chamber are i d e n t i c a l . P r e c i s i o n of
a n a l y s i s , however, i s c o n s i d e r a b l y improved in the l a t t e r c a s e .
This observation was most pronounced when p y r i d i n e s o l u t i o n s of
coal derived m a t e r i a l were being examined r a t h e r than s o l u t i o n s of
elemental standards. The r e l a t i v e l y high v i s c o s i t y of the
concentrated coal derived s o l u t i o n s (-5-7% w/w) no doubt leads to
i n c o n s i s t e n c y in a s p i r a t e d sample d e l i v e r y . R e l a t i v e standard
d e v i a t i o n s (RSD) were a l s o improved on going from 10 second t o 30
second i n t e g r a t i o n t i m e s . Table II compares d e t e c t i o n l i m i t s and
RSD's in p y r i d i n e employing d i r e c t a s p i r a t i o n (10 second

i n t e g r a t i o n s ) and pumped d e l i v e r y (30 second i n t e g r a t i o n s ) . The
RSD s f o r most elements were l e s s than 10% f o r the pumped
1
delivery.
The above f o r c e d flow procedure was employed t o determine
t r a c e element content in s i x a d d i t i o n a l p y r i d i n e s o l u b l e SRC's.
Each SRC d i f f e r s from another i n e i t h e r raw coal source,
conversion s e v e r i t y ( i . e . pressure-temperature), added Na£C03
content or method of residue removal. Table III o u t l i n e s the
various processing parameters and the assigned run number. The
measured elemental concentrations are l i s t e d in Table IV.
R e l a t i v e standard d e v i a t i o n s f o r each a n a l y s i s were, in g e n e r a l ,
l e s s than 10%. This of course was higher f o r elements near t h e i r
detection l i m i t . Runs #1636* and #166B ( L a f a y e t t e coal) d i f f e r
only in the amount of Na2C03 added to the b a t c h . The concentration
of each metal f o r the two runs i s remarkably s i m i l a r . Na2C03
a d d i t i o n i s supposed to i n h i b i t c o r r o s i o n . This o p e r a t i o n , no
doubt, has been e f f e c t i v e s i n c e #166B c o n s i s t e n t l y has equal or
lower metal concentrations than #163B. The decrease in Si and Fe
concentration i s most n o t a b l e . On the other hand, the s i t u a t i o n
i s d i f f e r e n t f o r Runs #210 and #220 ( F i e s c o a l ) . Few metals
(Si and Sn) show concentration decreases upon a d d i t i o n of 25 lbs
Na2C03/ b a t c h . Runs #210 and #220 were made at both higher
temperature and p r e s s u r e , however, metal content comparisons with
s i m i l a r runs (#163B, 166B) at lower temperature did not reveal any
significant trends. Runs #198 and #199 employed a more conven-
t i o n a l f i l t r a t i o n method. V a l i d comparisons would be #163B vs
#198 and #166B vs # 199. In most every case the metal concen-
t r a t i o n i s higher f o r the f i l t e r e d method (#199 vs #166B). This
was not true f o r the other pairwise comparison (#198 vs #163B).
It i s conceiveable that c o l l o i d a l mineral matter may have escaped
the f i l t e r process. For c e r t a i n of the t r a n s i t i o n metals
concentration remained e s s e n t i a l l y constant as one might suspect
i f they are t r u l y s o l u b l e o r g a n i c a l l y bound s p e c i e s . Runs #217
and #220 enables one again t o observe i f processing s e v e r i t y
i n f l u e n c e s metal content. For t h i s coal and these c o n d i t i o n s
there s u r p r i s i n g l y i s e s s e n t i a l l y no change in metal content.

TABLE II
TRACE ELEMENT ANALYSIS OF A SOLVENT REFINED COAL 3
MEASURED IN PYRIDINE AS A FUNCTION OF SAMPLE DELIVERY

Direct Aspiration Pumped D e l i v e r y

pg of element uq of element
Element g of SRC RSD g of S R C RSD
b
Ag ND 2.7 16.8
AT 325.8 6.8 152.3 1.8
Β 121.4 2.5 87.7 14.4
Ba 1.7 43.3 1.5 5.1
Ca 789.9 55.0 601.5 3.0
Cd ND - 4.4 19.3
Cr 18.5 15.3 13.3 2.1
Cu 3.0 235.0 15.2 86.9
Fe 38.4 28.3 29.9 4.5
Mg 17.9 3.9 12.6 7.1
Mn 3.1 13.1 1.1 11.9
Mo 8.8 225.6 6.0 5.8
Ni ND - 21.7 58.1
Pb ND - 59.6 11.4
Si 1074 6.3 737.6 7.3
Sn 171.5 36.2 122.5 4.5
Ti 1217.0 10.3 466.8 3.2
V 13.7 6.4 6.5 7.5
Zn 8.4 32.9 33.8 6.6
a
Wilsonville, AL, Run 199 (See Table I I I )
ND = elemental concentration i s less than ten times the

b
d e t e c t i o n l i m i t as determined in p y r i d i n e

TABLE III
PROCESSING CONDITIONS FOR KENTUCKY NO. 9 SOLVENT REFINED COAL
Severity Na?C03
e
Mine Run Number PSI/ F LB/Batch Residue Removal
Lafayette 163B 1700/825 Ο Critical Solvent Deashing
Lafayette 166B 1700/825 40 Critical Solvent Deashing
Lafayette 198 1700/825 Ο Filter
Lafayette 199 1700/825 40 Filter
FIES 210 2100/840 Critical Solvent Deashing
FIES 217 2000/785 25 Critical Solvent Deashing
FIES 220 2100/840 25 Critical Solvent Deashing

TABLE IV H
0
TRACE ELEMENT ANALYSIS OF SRC AS A FUNCTION OF SOURCE AND PROCESSING CONDITIONS** g
z
ELEMENT RUN 163B RUN 166B Run 198 RUN 210 RUN 217 RUN 220 Run X °
— M
H
>
ND ND ND ND ND 6.4 - r
Ag
Al 120.4 35.9 133.8 28.9 43.3 95.8 102.0
Β 47.4 36.3 70.3 45.9 47.9 66.3 -
Ba 0.5 ND ND ND ND 0.7 - !
Ca 134.3 133.7 65.7 85.8 133.4 82.8 73
Cd 0.2 ND 0.4 0.5 ND 0.7 -
Cr 1.3 2.2 8.9 0.2 1.3 0.7 2.8
Cu 0.7 7.2 ND ND ND ND - f
Fe 268.2 14.8 167.1 27.9 7.1 27.7 3.9 55*
Mg 10.6 4.8 9.7 1.0 5.6 3.2 -
Mn 5.0 0.2 9.2 0.7 0.3 1.4 16.6
1'
Mo ND ND ND ND ND ND -
Ni 1.1 ND ND 8.7 ND ND ND
Pb 4.0 ND 2.7 ND ND ND -
Si 270.6 6.7 8.1 11.7 ND ND - ta
Sn ND ND ND 48.0 ND ND - CO
Ti 235.9 136.0 591.0 52.7 97.2 99.3 223.0
V 6.4 5.2 9.4 5.0 4.8 11.7 6.1
Zn 15.2 7.8 10.9 4.2 3.5 1.3 ND

Concentration expressed in ug of element per gram of SRC
b
ND = Elemental concentration i s l e s s than ten times the d e t e c t i o n l i m i t as determined in pyridine
c
R e p o r t e d in Reference 9; SRC obtained from Tacoma, WA p i l o t p l a n t ; data obtained by NAA
A number of general observations can be made but not r e a d i l y

explained given the l i m i t e d h i s t o r y a v a i l a b l e on each SRC. First,
Lafayette and F i e s mines produce SRC of s i m i l a r metal content with
a few e x c e p t i o n s . Second, those metals which are expected to be
most s t r o n g l y organo-bound (mainly t r a n s i t i o n metals) do not
s i g n i f i c a n t l y change concentrations as a f u n c t i o n of these
processing parameters; whereas, " m i n e r a l - r e l a t e d " elements appear
t o f l u t u a t e with processing c o n d i t i o n s . It i s r e a d i l y apparent
that s p e c i a t i o n data i s d e s i r a b l e .
A r e l a t e d study has been r e c e n t l y reported(4, 8) on one SRC.
While the samples were drawn from a d i f f e r e n t piTot plant and the
mine source i s unknown, i t i s i n t e r e s t i n g to note that our
measured concentrations v i a ICP-AES and Weiss' concentrations v i a
NAA are comparable. The absence of data in Table IV i n d i c a t e s

that the element's concentration was not monitored by Weiss.
Metal Detection In Coal Derived Process Solvent Chromato-

graphy. ICP-AES alone w i l l not suggest s p e c i a t i o n ; however,
coupled with chromatography some knowledge of the nature of metal
species can be obtained. Size e x c l u s i o n chromatography (SEC) of a
SRC process solvent (92-03-035) with ICP-AES d e t e c t i o n has been
performed. The solvent was d i l u t e d with p y r i d i n e (1:1) and
i n j e c t e d (200 y l ) on the column. P r i o r to SEC, the process
s o l v e n t , which had a b o i l i n g range defined as i n i t i a l b o i l i n g
point ( I B P ) - 8 0 0 F , was r e - d i s t i l l e d to y i e l d 400-600 F and
e e
600-800 F c u t s .
e
Figure 1 shows s e l e c t metallograms f o r these
three d i s t i l l a t e s . At the o u t s e t , i t should be noted that
m e t a l l i c species have g e n e r a l l y not been thought to r e s i d e in
process s o l v e n t s . Since the 400-600 F and 600-800 F f r a c t i o n s were
e e
taken from the IBP-800 F d i s t i l l a t e , a d d i t i o n of the former two

e
metallograms should y i e l d the l a t t e r . Indeed, i f one looks at the

Fe 400-600 F metallogram one sees a bimodal d i s t r i b u t i o n with the
e
prominent f r a c t i o n being of smaller molecular s i z e . The 600-800 F e
Fe metallogram i s l i k e w i s e bimodal but the predominant f r a c t i o n i s

of l a r g e r molecular s i z e . The IBP-800 F Fe metallogram e x h i b i t s
e
an equal d i s t r i b u t i o n of small and large s i z e d molecules. S i m i l a r

type r e s u l t s are noted f o r Cu and Zn although Zn appears t o be
concentrated i n the lower temperature d i s t i l l a t e and the higher
temperature f r a c t i o n s u r p r i s i n g l y has the smaller s i z e Zn
compounds. One explanation f o r t h i s i s that these compounds may
be more polar and intermolecular associaton causes the higher
d i s t i l l a t i o n temperature. A d d i t i o n a l elements (Mg, Ca, T i , Cr,
Mo, Mn, Co, N i , Cd, Hg and A l ) were monitored but not detected
except f o r the t r a c e of Mn found in the IBP-800°F f r a c t i o n .
These experiments suggest (1) m e t a l l i c m a t e r i a l s are found i n
process s o l v e n t s , (2) metals are o r g a n i c a l l y bound s i n c e they have
survived both d i s t i l l a t i o n and chromatographic separation and (3)
a large number of d i f f e r e n t molecular s i z e d species c o - e x i s t . The
exact nature of these metal components remains a mystery p r i m a r i l y
because (1) the separation behavior of metal complexes v i a s i z e

IBP-800° F 600°-800° F 400°-600 F
Mn

Figure 1. Separation of process solvent 92-03-035 boiling cuts diluted 1:1 with pyridine with
specific metal detection. Conditions: 100Â μ-Styragel column; eluent, pyridine;flowrate, 0.5 mL/
min; injection, 200 μΣ.
e x c l u s i o n chromatography i s not c l e a r l y e s t a b l i s h e d , (2) adequate,

s o l u b l e models are not forthcoming and (3) SEC does not
e f f e c t i v e l y concentrate a p a r t i c u l a r metal type f o r i s o l a t i o n and
examination by other a d d i t i o n a l spectroscopic methods.
SEC-ICP-AES, i n other words, may never y i e l d d e t a i l s as to the
exact environment about the metal i o n . M u l t i p l e peaks may
represent d i f f e r e n t o x i d a t i o n s t a t e s or v a r i o u s l y i n t e r m o l e c u l a r l y
associated or solvent associated metal-containing s p e c i e s . Broad
peaks may suggest information regarding h i g h l y r e a c t i v e metal
species. C l e a r l y a b e t t e r understanding of the chromatography of
m e t a l l i c species i s needed here.
In order t o employ more s p e c i f i c , "chemical c l a s s "
separations and t o gain more d e t a i l e d s p e c i a t i o n i n f o r m a t i o n ,
normal phase chromatography of metal compounds with ICP-AES

d e t e c t i o n has been e x p l o r e d . Normal phase l i q u i d chromatography
with ICP d e t e c t i o n should provide a b e t t e r means f o r eventual
s p e c i a t i o n of o r g a n i c a l l y bound metals in coal derived products.
Its advantage l i e s in the a b i l i t y to separate compounds by
p o l a r i t y and allows use of solvents which have a reasonable
s o l u b i l i t y f o r coal derived products. Through extensive modeling
work and the f u r t h e r development of separation schemes, i t should
be p o s s i b l e t o more f u l l y understand the nature of the o r g a n i c a l l y
bound metals present in coal derived products. One drawback t o
normal phase LC i s that r e t e n t i o n and i r r e v e r s i b l e adsorption of
l a b i l e species such as c o o r d i n a t i o n complexes may occur. The
question of whether the solvent system employed i s strong enough
to remove the more polar m a t e r i a l s i s always subject t o
conjecture. Both normal phase and reverse phase gradient e l u t i o n
should solve the l a t t e r problem; whereas, the former appears t o be
most r e a d i l y approached by using r e l a t i v e l y mild i n t e r a c t i n g
reverse phase m a t e r i a l s (~Cis) with aqueous/methanol solvent
systems. Only one b r i e f report(14) has mentioned adsorption
LC-ICP-AES i n a t o t a l l y organic pfîase; t h e r e f o r e , some p r e l i m i n a r y
modeling has been performed in order t o show f e a s i b i l i t y of t h i s
approach.
Organometal 1ic systems i n c o r p o r a t i n g e i t h e r Fe or Si served
as r e p r e s e n t a t i v e model mixtures. Figure 2 i l l u s t r a t e s a simple
i s o c r a t i c separation of a mixture of s i x organo-iron compounds.
The mixture i s composed of four organometallie compounds and two
c o o r d i n a t i o n compounds (see f i g u r e 3 ) . The cyano-amino bonded
phase s i l i c a (PAC) column used was s u f f i c i e n t l y r e t e n t i v e t o allow
the employment of a good s o l u b i l i z i n g solvent (CHCI3) while also
o b t a i n i n g a reasonably good s e p a r a t i o n . While a separation v i a
p o l a r i t y i s envisioned here, nevertheless the only i o n i c compound
in the mixture, i r o n c l a t h r o c h e l a t e , (15) was not the most
retentive. I n t e r a c t i o n of the bonded pïïâse with the f r e e acetyl
groups in acetyl ferrocene and d i a c e t y l ferrocene must be
comparable to the above in that each of these compounds f l a n k s the
i o n i c chelate in r e t e n t i o n time. Fe3(C0)i2 and CpFe(C0)2l are
obviously q u i t e non-polar being neutral compounds with h i g h l y

_l I I I
2 3 4 5 6 7 8 I 2 3 4 5 6 7 8
TIMS (rain) ΎΏΈ. (rain)
Figure 2. Separation of iron model compounds with Fe and Β detection. Condi

tions: Polar amino cyano column; flow rate, 1 mL/min; eluent, CHCl /0.5% s
C H OH. Key: 1, triirondodecacarbonyl; 2, (Cp)Fe(CO) I; 3, acetyl ferrocene; 4,

t s g
iron clathro chelate; 5, diacetyl ferrocene; and 6, Fe[B(PZ)J . Iron compounds are
t
illustrated in Figure 3.

(CO^FE
CO COLL.,
O C - F E - C O
(CO)Î,FE—>FE(C0) 3
I
φ)
1
CH3
c — < /
H II ÊLÎ-CH,
R-Bf-O-N ff-0 -R
V
3
roi r£i
Ν—Ν Ν—Ν
/ \/ \
N—N

F/gwre J. Molecular structures of iron model compounds. Key: i , triirondodecacarbonyl; 2,
(Cp)Fe(CO),I; 3, acetyl ferrocene; 4, iron clathro chelate; 5, diacetyl ferrocene; and 6, Fe[B(PZ)J .9
covalent i r o n - l i g a n d bonding. The higher symmetry of the former

no doubt accounts f o r i t s e a r l i e r e l u t i o n p a t t e r n . The e a r l y
e l u t i o n of iron t e t r a k i s ( l - p y r a z o y l ) - b o r a t e (16) i s somewhat
puzzling. The uncoordinated pyrazoyl group apparently has l i t t l e
a f f i n i t y f o r the column. The high symmetry of the complex and i t s
zero charge probably operate to lower the a f f i n i t y a l s o . This
separation a l s o demonstrates the multielement c a p a b i l i t y of
ICP-AES d e t e c t i o n . The two c o o r d i n a t i o n compounds contain both Fe
and B. Upon monitoring both Fe and Β emissions, p a i r s of peaks
are observed at the same r e t e n t i o n time.
The second mixture studied was composed of several
o r g a n o - s i l i c o n compounds. Their separation was examined as a
f u n c t i o n of column packing and s o l v e n t . Optimized separations are
shown in Figure 4 f o r each column with the corresponding solvent

system employed. By using stronger r e t e n t i v e packings ( i . e .
s i l i c a ) b e t t e r solvents f o r s o l u b i l i t y ( i . e . heptane, heptane/2%
2-propanol, CHC13/5% 2-propanol) may be employed while again
achieving s u i t a b l e s e p a r a t i o n s . The general e l u t i o n pattern f o r
t h i s group of s i l i c o n compounds i s explained in terms of varying
p o l a r i t y analogous to the s i m i l a r carbon c o n t a i n i n g components.
An increase in r e t e n t i o n time i s observed from compound 1, the
e a r l i e s t e l u t i n g and hence l e a s t p o l a r , through compound 6, the
most s t r o n g l y r e t a i n e d and most p o l a r . The i n c l u s i o n of
heteroatoms accounts f o r t h i s change in p o l a r i t y . The separation
of compounds 1, 2 and 3 on PAC with non-polar heptane shows the
separation of these weakly polar components. The acetylene group
i s l e s s polar than the ether group which i s l e s s polar than the
carbonyl group. Compounds 4, 5 and 6 do not e l u t e under these
conditions. By changing t o a weaker r e t a i n i n g support (CN) and
adding a polar m o d i f i e r in small amounts to heptane (2%
2-propanol), the most polar components are now e l u t e d , however,
the e a r l y e l u t i n g weakly polar components now c o - e l u t e . The f r e e
hydrogen on the nitrogen of compound 5 makes i t more r e t e n t i v e
than the d i e t h y l groups on compound 4, while the dihydroxy groups
are most r e t e n t i v e . S i m i l a r l y , by going to the strongest
r e t a i n i n g support, s i l i c a , and a much stronger mobile phase, an
intermediate separation i s achieved with r e s o l u t i o n of four of the
s i x components. Gradient e l u t i o n should provide s i g n i f i c a n t
improvement and should allow these components to be f u l l y
separated. This w i l l be examined in f u t u r e work.
The p r e l i m i n a r y modeling work on a v a r i e t y of
chromatographically s t a b l e metal systems e s t a b l i s h e d a basis to
separate and detect metal components in the process r e c y c l e
solvent. P r e l i m i n a r y q u a n t i t a t i v e t o t a l metal a n a l y s i s showed
only small amounts of a few m e t a l s . For t h i s reason, neat
i n j e c t i o n s of the sample were performed.
Large amounts of chromium, iron and s i l i c o n species were
observed by normal phase separation with chloroform. Figure 5
shows the SEC of iron species in 400-600°F and 600-800 F b o i l i n g e
fractions. It i s i n t e r e s t i n g to note the large amount of iron

SILICA
1
CONDITIONS
Detector: Si Channel ICP-AES
PAC: 2 ml/min Heptane
CN: 1 ml/min Heptane/2% 2-propanol
Silica: 1 ml/min CHCl3/5% 2-propanol
PAC CN
ι .
0 2 4 6 8 10 1 2 3 4 5 6 7 2 3 4 5 6 7
TIME (min.) TIME (min.) TIME (min.)
Figure 4. Separation of silicon model compounds with silicon detection (Si chan
nel ICP-AES) as a function of column packing. Key to packing: left, polar amino
cyano (PAC); middle, cyano (CN); and right, silica. Key to compounds: 1, d j ^ i C s
CSi<t> ; 2, (C H ) Si(OC H ) ;
s 6 s 3, Si(OOCCH ) ; 4, 4> Si(NC H ); 5, Hexamethyl-
t g 5 g s k s g s
disilazane; and 6, <f> Si(OH) . t g

7. BROWN ET A L . Metal Analysis Using ICP-AES 179
600-800
-800
I I I I 1 1 1 1
318 4 21 5.24 6 27 7.31 8.34 9.37 10.40
RETENTION TIME
Figure 5. Separation of process solvent 92-03-035 boiling cuts with Fe detec-

tion. Conditions: column, PAC; eluent, CHCl ; flow rate, 1 mL/min; and injection,
s
200 pL.

species present in the 400-800 F f r a c t i o n as compared to the

e
higher b o i l i n g f r a c t i o n . This i n d i c a t e s that most of the iron

species are v o l a t i l e below 6 0 0 F . It should also be noted that
e
subsequent a n a l y s i s showed a very l a t e e l u t i n g F e - c o n t a i n i n g peak

in the 400-800°F f r a c t i o n .
The same two b o i l i n g f r a c t i o n s monitored simultaneously in
the chromium channel ( F i g u r e 6) showed j u s t the reverse behavior.
Chromium appears t o be concentrated in the 600-800°F f r a c t i o n
while being absent or below the d e t e c t i o n l i m i t s in the o v e r a l l
400-800°F f r a c t i o n . S i m i l a r l y , in Figure 7, s i l i c o n species are
more prevalent in the 600-800°F f r a c t i o n while appearing t o a much
smaller degree i n the 400-800°F f r a c t i o n . Other metals are e i t h e r
not present at measurable q u a n t i t i e s or they are i r r e v e r s i b l y
r e t a i n e d on the column. The low concentration of metal species in

these samples r e q u i r e d overloading of the column with organic
c o n s t i t u e n t s and t h i s accounts f o r the broadness of the observed
peaks.
It should be noted that the c o n d i t i o n s employed f o r these
separations were the same as those used f o r the separation of the
i r o n models. The absence of several metals which were observed in
SEC of the same process solvent i n d i c a t e that a l t e r n a t e
separations w i l l have to be developed.
Conclusions
Work t o present has demonstrated both the existence of

o r g a n i c a l l y bound metals in coal derived products as well as the
f e a s i b i l i t y f o r d i r e c t d e t e c t i o n and q u a n t i t a t i o n in organic
solvents by ICP-AES. Before r e l i a b l e s p e c i a t i o n can be
accomplished, b e t t e r chromatographic separations need to be
developed. These include p r e l i m i n a r y separation i n t o various
f r a c t i o n s by p o l a r i t y followed by subsequent a n a l y s i s by HPLC.
Work t o better separate a wide range of p o l a r i t i e s v i a gradient
e l u t i o n i s d e s i r a b l e . A l s o , those m a t e r i a l s which are l a b i l e
enough t o react with the normal phase packings need t o be examined
by reverse phase chromatography both i s o c r a t i c a l l y and v i a
gradient e l u t i o n . A d d i t i o n a l work on modeling of various
o r g a n i c a l l y bound metal systems needs to be accomplished
e s p e c i a l l y with those l a b i l e systems which up to now have been
d i f f i c u l t to separate except by SEC. Work to developed methods of
q u a n t i t a t i o n f o r chromatographically separated components i s
necessary. Comparison of t o t a l metal content t o separated metal
content should be made t o insure that a l l metal species have been
removed from the column. From t h i s work, the r o l e of o r g a n i c a l l y
bound metals in the SRC p r o c e s s , as well as other processes, can
be b e t t e r understood. The a b i l i t y to track metals throughout a
process as well as to i d e n t i f y p o s s i b l e species should g r e a t l y aid
i n determining the e f f e c t of s p e c i f i c metals as p o s s i b l e c a t a l y s t s
and/or poisons t o the c o n v e r s i o n .

BROWN ET AL. Metal Analysis Using ICP-AES 181
l.25mv
IBP-800
3.18 5.24 6.27 7.30 833
RETENTION TIME
Figure 6. Separation of process solvent 92-03-035 boiling cuts with Cr detec-

tion. Conditions are the same as in Figure 5.

400-600
ι 1 ι ι I ι ι —ι
2 16 3 18 420 521 6 23 7 35 847 948
RETENTION TIME
Figure 7. Separation of process solvent 92-03-035 boiling cuts with Si detec

tion. Conditions are the same as in Figure 5.

Acknowledgement - Support by the Commonwealth of V i r g i n i a ,

the Department of Energy under Grant EF-77-01-2696 and the
E l e c t r i c Power Research I n s t i t u t e i s g r a t e f u l l y appreciated.
Literature Cited
1. Gorbaty, M. L . , F. J. Wright, R. K. Lyon, R. B. Long, R. H.
Schlosberg, Z. Baset, R. Liotta, B. G. Silvernagel and D. R.
Neskora, Science, 1979, 206, 1029.
2. Lett, R. G., J. W. Adkins, R. R. DeSantis and F. R. Brown,
"Trace and Minor Element Analysis of Coal Liquefaction
Products", PETC/TR-79/3, August, 1979.
3. Filby, R. H. and S. R. Khalil, "Synthetic Fuel Technology",
Κ. E. Cowser and C. R. Richmond, eds., Ann Arbor, MI, Ann

Arbor Science, p. 102 (1980).
4. Weiss, C. S., "The Detection of Trace Element Species in
Solvent Refined Coal", Ph.D. Dissertation, Washington State
University, 1980.
5. Coleman, W. M., P. Perfetti, H. C. Dorn and L. T. Taylor,
Fuel, 1978, 57, 612 and references therein.
6. Hausler, D. W. and L. T. Taylor, Fuel, 1981, 60, 41.
7. Fassel, V. Α., C. A. Peterson, F. N. Abercrombie and R. N.
Kniseley, Anal. Chem., 1976, 48, 516.
8. Filby, R. H., D. R. Sandstrom, F. W. Lytle, R. B. Greegor, S.
R. Khalil, V. Ekambaram, C. S. Weiss and C. A. Grimm,
Proceedings DOE/NBS Workshop on "Environmental Speciation and
Monitoring Needs for Trace Metal-Containing Substances from
Energy Related Projects", F. E. Brinckman and R. H. Fish,
eds., NBS Special Publication 618, 1981, p. 21.
9. Maylotte, D. H., J. Wong, R. L. St. Peters, F. W. Lytle and
R. B. Greegor, Science, 1981, 214, 554.
10. Bonnett, R. and F. Czechowski, Phil. Trans. R. Soc. Lond. A,
1981, 300, 51.
11. Hausler, D. W. and L. T. Taylor, Anal. Chem., 1981, 53, 1227.
12. Hausler, D. W. and L. T. Taylor, Anal. Chem., 1981, 53, 1221.
13. Taylor, L. T., D. W. Hausler and A. M. Squires, Science,
1981, 213, 644.
14. Winge, R. K. Peterson, V. J. Fassel, V. A. "Inductively
Coupled Plasma-Atomic Emission Spectroscopy: Prominent
Lines", EPA-600/4-79-017, March, 1979.
15. Gast, C. H., J. C. Kraak, H. K. Poppe and F.J.M.J. Maessen,
J. Chromatoqr., 1979, 185, 549.
16. Boston, D. R. and N. J. Rose, J. Amer. Chem. Soc., 1968, 90, —
6859.
17. Trofimenko, S., J. Amer. Chem. Soc., 1968, 89, 3170.
RECEIVED May 17, 1982

8
Determination of Chlorine in Organic
Combination in the Coal Substance
J. N. CHAKRABARTI
I. S. M., Fuel and Mineral Engineering, Department of Chemistry,
Dhanbad 826004, India
Opinions vary regarding the node of combination of chlorine

in coals. Early investigators reported that only part of the
chlorine could be removed by extraction with water and suggested
that some of i t is chemically combined with the coal substance,
either as organic chlorine or as adsorbed ions. Later workers,
notably Crossley (1952), concluded that virtually the whole of the
chlorine is present as alkali chlorides, possibly with small quan-
tities of calcium and magnesium chlorides as well. Edgcombe
(1956) found that the alkali in the extracts was equivalent to
only part of the total chlorine and concluded that only half of
the chlorine could be present as alkali chlorides. He held the
view that the volatile chlorine represented that part of the total
chlorine which was not present as alkali chlorides and that i t
existed in the coal as chloride ions held on the coal substance by
an ion-exchange linkage.
The nature of chlorine in coal is of major interest in its
industrial applications. For example, combustion of high-chlorine
coal in boilers results in serious fouling by the formation of
alkali-bonded deposits. A correct measure of the chlorine as
inorganic chlorides is required in the case of coals that are to
be carbonized, since at the temperature of carbonization these
salts may react with the refractory walls, forming a glaze. This
glazed coating reduces the effective l i f e of a coke oven or of a
gas retort. This is precisely the reason why the presence of an
appreciable quantity of chlorine in a sample of coal is ordinarily
considered detrimental to the brickwork of coke ovens and gas
retorts. However, high chlorine contents in coals may not always
be prejudicial to the stability of the refractories, as an appre-
ciable percentage of i t may be in organic conbination. In the
latter case, there may be either volatilization or decomposition
or both. Halogenated organic compounds have hardly any effect on
refractories. If there is any liberation of hydrogen chloride gas
O097-6156/82/0205-O185$O6.0O/O

or simple c h l o r i n e gas due to decomposition, the r e f r a c t o r i e s may

be simply bleached. I t i s thus evident that a c o r r e c t e s t i m a t i o n
of c h l o r i n e i n organic combination i s of great s i g n i f i c a n c e .
In h i s i n v e s t i g a t i o n s on Indian c o a l s , the author proved f o r
the f i r s t time the e x i s t e n c e of c h l o r i n e i n organic combination i n
the coal substance. I t was found that i n a l l the ten coals exa-
mined, the p r o p o r t i o n of c h l o r i n e i n organic combination was
a p p r e c i a b l e and i n some cases i t s p r o p o r t i o n rose to 30-36 percent
of the t o t a l c h l o r i n e .
I t has been suggested that on an average 50% of the t o t a l
c h l o r i n e present i n coals of East Midlands C o a l f i e l d i n the U n i t e d
Kingdom (which may have t o t a l c h l o r i n e contents as high as 1%)
must be assumed to be a s s o c i a t e d w i t h organic matter, probably as
h y d r o c h l o r i d e s of p y r i d i n e bases. (Given and Yarzab, 1978.)

Work on c h l o r i n e contents of coals from I l l i n o i s Basin has
shown that a l l the c h l o r i n e present could not be accounted f o r i n
minerals present as h a l i t e (NaCl) or s y l v i t e (KC1) and t h e r e f o r e a
s u b s t a n t i a l p r o p o r t i o n i s a s s o c i a t e d w i t h the organic matter.
O u t l i n e of the Method
The c h l o r i n e i n organic combination i n c o a l i s allowed to

combine w i t h hydrogen i n the presence of n i c k e l c a t a l y s t i n a
s i l i c a combustion tube. The hydrogen c h l o r i d e gas so formed i s
combined w i t h ammonia c i r c u l a t i n g through the r e a c t i o n tube,
forming ammonium c h l o r i d e as a sublimate, which i s d i s s o l v e d out
by washing w i t h water. Any unreacted hydrogen c h l o r i d e i s
a r r e s t e d by hot barium carbonate kept at the e x i t end. The
c h l o r i d e formed i s then estimated v o l u m e t r i c a l l y .
Y& + CI" • HC1 (i)
NH 3 + HC1 • NH^Cl (ii)
2 HC1 + BaC0 3 + B a C l + H 0 + C0
2 2 2 (ill)
Apparatus and Reagents
A. Apparatus.
(a) A s i l i c a tube 55-60 cm long and 15 cm i n diameter

(b) Two s i l i c a or p o r c e l a i n boats, one f o r c o a l and the other
f o r h o l d i n g barium carobnate
(c) Three Meker burners
(d) Kipp's apparatus f o r generating hydrogen
(e) C o n i c a l f l a s k provided w i t h d e l i v e r y tube and c o n t a i n i n g
aqueous ammonia
( f ) Vacuum d e s i c c a t o r

8. CHAKRABARTi Chlorine in Organic Combination in Coal 187
B. Reagents
(a) Granualted Zinc

(b) Dilute s u l f u r i c acid
(c) S o l u t i o n of lead acetate
(d) S o l u t i o n of potassium hydroxide
(e) Aqueous ammonia
(f) Barium carbonate (pure)
(g) Acetic acid
(h) Concentrated n i t r i c a c i d
(i) S i l v e r n i t r a t e s o l u t i o n , 0.05 Ν
(j) Nitrobenzene
(k) Standard potassium thiocyanate s o l u t i o n , 0.05 Ν
(1) F e r r i c alum i n d i c a t o r , saturated s o l u t i o n i n water, suf

f i c i e n t n i t r i c a c i d being added t o remove the brown c o l o r ,
i f any
(m) 2 , 4 , 6 - T r i c h l o r o p h e n o l , A.R.
(n) Sodium c h l o r i d e , A.R.
(o) Sugar c h a r c o a l , s p e c i a l l y prepared.
Procedure and S t a n d a r d i z a t i o n
A· Procedure
The s i l i c a tube i s mounted h o r i z o n t a l l y by two clamps,

the v e r t i c a l d i s t a n c e being adjusted so as to u t i l i z e f u l l y
the h e a t i n g e f f e c t of three Meker burners. One end of the
combustion tube i s provided w i t h a cork and d e l i v e r y tube and
connected to a constant supply of pure hydrogen (e.g. Kipp's
apparatus)· The other end of the combustion tube i s kept open
v i a a c o n s t r i c t e d tube (see F i g . 1 ) .
B. S t a n d a r d i z a t i o n
F i r s t , an a r t i f i c i a l mixture of pure sodium c h l o r i d e ,

sugar c h a r c o a l and 2 , 4 , 6 - t r i c h l o r o p h e n o l i s put i n the boat.
T h i s i s introduced i n t o the tube near the end connected t o the
source of hydrogen and i s placed at a d i s t a n c e of 8 cm (see
F i g . 1 ) . A n i c k e l f o i l r o l l e d i n the form of a s p i r a l i s
placed a t a d i s t a n c e of 20 cm from the same end. Another boat
c o n t a i n i n g pure barium carbonate i s placed j u s t near the open
end of the tube. At the o u t s e t , a steady stream of pure
hydrogen, s a t u r a t e d w i t h ammonia, i s maintained through the
tube. For t h i s purpose, the gas i s bubbled s u c c e s s i v e l y
through water, s o l u t i o n s of lead a c e t a t e , potassium hydroxide,
and aqueous ammonia (not shown i n F i g . 1). The burner imme
d i a t e l y below the n i c k e l f o i l i s s t a r t e d f i r s t . When the
e x t e r i o r s u r f a c e of the tube i s red hot (temperature
700-800°C) h e a t i n g of the boat c o n t a i n i n g barium carbonate i s
s t a r t e d . The temperature of the boat c o n t a i n i n g the mixture

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s
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8. CHAKRABARTI Chlorine in Organic Combination in Coal 189
of 2 , 4 , 6 - t r i c h l o r o p h e n o l , sodium c h l o r i d e and sugar charcoal i s

r a i s e d g r a d u a l l y and the f u l l temperature e f f e c t i s allowed o n l y
a f t e r 15 minutes. Hydrogen combines w i t h c h l o r i n e l i n k e d t o
o r g a n i c compounds i n the presence of n i c k e l . This then combines
w i t h ammonia, forming ammonium c h l o r i d e , and i s deposited on the
i n n e r w a l l s of the tube between the n i c k e l c a t a l y s t and the open
end. The l e a s t traces of unreacted hydrogen c h l o r i d e are r e t a i n e d
by hot barium carbonate. The r e a c t i o n r e q u i r e s a period of 45
minutes. A f t e r the r e a c t i o n i s over, the tube i s allowed t o c o o l .
This i s then washed w i t h water to d i s s o l v e the deposited ammonium
c h l o r i d e , a f t e r withdrawing the boats and the s p i r a l . Barium c a r -
bonate i s a l s o washed i n t o the s o l u t i o n c o n t a i n i n g ammonium
c h l o r i d e . This i s then rendered a c i d i c by a c e t i c a c i d , and b o i l e d
t o expel hydrocyanic a c i d , i f any. C h l o r i n e i s estimated v o l u -

m e t r i c a l l y by Volhard's method.
T h i s method has been found to be very s u i t a b l e f o r o b t a i n i n g
a true measure of the c h l o r i n e l i n k e d to organic compounds. The
i n o r g a n i c c h l o r i d e s , however, are not a f f e c t e d by t h i s treatment.
T h i s i s v e r i f i e d a t the very outset by t a k i n g a mixture of pure
sodium c h l o r i d e , sugar charcoal and 2 , 4 , 6 - t r i c h l o r o p h e n o l i n the
boat and e s t i m a t i n g the c h l o r i n e l i b e r a t e d . As the organic com-
pound, i . e . 2 , 4 , 5 - t r i c h l o r o p h e n o l , i s l i k e l y to c o n t a i n some
moisture, i t i s d r i e d i n a vacuum d e s i c c a t o r p r i o r to being
weighed. The r e s u l t s (Table I ) show that the organic c h l o r i n e
alone i s l i b e r a t e d i n t h i s way. The marginal d i f f e r e n c e s between
the observed and c a l c u l a t e d values of c h l o r i n e are probably due to
the f a c t that the substance was not 100% pure. However, the d i f -
ferences are w i t h i n the l i m i t s of experimental e r r o r .
Having thus standardized the method f o r e s t i m a t i n g organic
c h l o r i n e , c o a l samples crushed t o pass through a 240 mes BS, or 6
mesh (64 ym) 15 s i e v e , are put i n the boat and t h e i r organic
c h l o r i n e contents determined as described f o r the s t a n d a r d i z a t i o n .
For accurate determinations of c h l o r i n e , i t i s a d v i s a b l e t o
c a r r y out a blank determination using sugar charcoal i n s t e a d of
c o a l and t o determine the c h l o r i n e c o l l e c t e d , i f any, as ammonium
c h l o r i d e and a l s o i n the barium carbonate.
TABLE I
S t a n d a r d i z a t i o n w i t h a Pure Organic Substance
Chlorine %
Experiment No. Substance Found Calculated
1 2,4,6-trichlorophenol 53.49 53.93

2 Do 53.56 53.93
3 Do (0.144g) + NaCl(0.7917g) 54.10 53.93
4 Do(0.1509g)+NaCl(1.023g) 54.09 53.93

The r e s u l t s of experiments w i t h ten coals from d i f f e r e n t l o c a l i -

t i e s are shown i n Table I I . For a comparative study, the t o t a l
c h l o r i n e content of each c o a l sample was a l s o determined by the
Eechka method.
TABLE I I
C h l o r i n e Contents of Indian Coals
Organic
Organic C h l o r i n e T o t a l Chlorine R a t i o of Chlorine
imp l e on d.a.f. Coal on d.a.f. Coal Total/Organic as % of
No. (%) (%) Chlorine Total

Chlorine
1 0.097 0.395 4.07:1 24.50

2 0.124 0.495 4.0:1 25.05
3 0.127 0.418 3.29:1 30.38
4 0.043 0.426 9.9:1 10.09
5 0.032 0.322 10.06:1 9.93
6 0.124 0.538 4.33:1 23.04
7 0.045 0.551 12.2:1 8.16
8 0.082 0.340 4.1:1 24.10
9 0.068 0.537 7.9:1 12.66
10 0.127 0.350 2.75:1 36.20
Literature Cited
1. Given, P.H.; Harzab, R.F. In "Methods for Coal and Coal Products",
Anal. Vol. II, 1978, 19-20.
RECEIVED July 14, 1982

9
Electron Probe Microanalysis
A Means of Direct Determination of Organic Sulfur in Coal
ROBERT RAYMOND, JR.

Los Alamos National Laboratory, Earth and Space Sciences Division,
Los Alamos, N M 87545
An analytical method of measuring organic

sulfur directly by use of the electron probe micro-

analyzer (EPM) avoids the uncertainty of calcu-
lating organic sulfur by difference. The EPM
enables rapid, nondestructive determination of the
organic sulfur content of individual macerals.
Thus, total organic sulfur content of a coal may be
computed by a mean modal analysis of the macerals.
Twenty-nine coals, collected from 13 states within
the contiguous USA, and ranging in rank, age, and
organic sulfur content (0.2 to 5.3 wt% dmmf) have
been analyzed. When plotting organic sulfur con-
tent of the coals vs organic sulfur content of
respective vitrinite components, the best linear
fit of the data has a correlation coefficient of
0.99, a slope of 0.98, and a y-intercept of -0.03.
Empirically, organic sulfur content of a coal
(dmmf) essentially equals organic sulfur content of
its vitrinite. Note that analyzed samples con-
tained as little as 41.9 wt% vitrinite macerals
(dmmf).
For EPM organic sulfur analysis representative
samples (-20 to -100 mesh) are potted in epoxy
pellets, polished, and carbon coated. Vitrinite
grains are identified during analysis by shape and
texture, with resulting organic sulfur contents
equivalent to those determined when using
oil-immersion, reflectance techniques for vitrinite
identification. According to t-statistics, ana-
lyzing 15 vitrinite grains achieves a maximum
variability of less than 0.20wt%in the coals that
contain less than 2.00 wt% organic sulfur. Instru-
ment time to analyze 15 grains, and therefore to
determine the organic sulfur content of a sample,
is less than 10 minutes. To test the EPM method,
0097-6156/82/0205-0191$06.00/0

we chose coals containing either no inorganic sul

fur (organic sulfur = total sulfur), or for which
ASTM organic sulfur values were corrected for
unextracted iron (which takes into account any
unextracted pyrite). These 13 samples contained up
to 2.09 wt% organic sulfur and variations between
EPM and ASTM values were less than 0.16 wt%.
As o u r need f o r e f f i c i e n t c o a l u t i l i z a t i o n i n c r e a s e s ,
i n a b i l i t y to i n t e r p r e t the occurrence and the amount o f s u l f u r i n
c o a l becomes i n c r e a s i n g l y s e r i o u s . The e f f e c t that s u l f u r has on
c o a l u t i l i z a t i o n , and on the environment i s s t a g g e r i n g . We can
t h e o r i z e that s u l f u r form and content vary w i t h i n a c o a l as a

d i r e c t r e s u l t o f the geochemistry o f precursor peatforming
environments, source areas surrounding the peats, and d i a g e n e t i c
c o n d i t i o n s o c c u r r i n g l a t e r during c o a l i f i c a t i o n . S t i l l , we have
l i t t l e knowledge about the emplacement o f s u l f u r i n peats, and o f
the t r a n s i t i o n s i t goes through during c o a l maturation. Largely
because o f t h i s l a c k o f knowledge i s our b a s i c i n a b i l i t y t o a n t i
c i p a t e and c o n t r o l the e f f e c t s o f s u l f u r during c o a l u t i l i z a t i o n .
The American S o c i e t y f o r T e s t i n g and M a t e r i a l s (ASTM) Stan
dard Test Method D2492-68 f o r s u l f u r a n a l y s i s i n c o a l s p e c i f i e s
the a n a l y t i c a l determination o f values f o r t o t a l , p y r i t i c and
sulfate sulfur. Organic s u l f u r i s c a l c u l a t e d by s u b t r a c t i n g
p y r i t i c and s u l f a t e s u l f u r from the t o t a l . The procedures a r e
aimed at p r o v i d i n g r a p i d , inexpensive, and r e p r o d u c i b l e data f o r
coal u t i l i z a t i o n . The p y r i t i c , s u l f a t e , and organic s u l f u r
contents reported by the processes adequately r e f l e c t the amount
of s u l f u r that can be removed by s i z i n g , s p e c i f i c g r a v i t y separa
t i o n , and hindered s e t t l i n g techniques. But any e r r o r i n t o t a l ,
p y r i t i c or s u l f a t e s u l f u r determination w i l l show up as an e r r o r
i n organic s u l f u r determination. Reasons f o r e r r o r i n p y r i t i c
s u l f u r determinations are reported by Edwards e t a l . (J.) and
Greer ( £ ) .
The e l e c t r o n probe microanalyzer (EPM) uses a f i n e l y focused
e l e c t r o n beam that impinges on a p o l i s h e d sample, g e n e r a l l y a t
15-20 keV, producing χ rays c h a r a c t e r i s t i c o f the elements pres
ent i n the sample. In g e n e r a l , EPM r e s u l t s are accurate and
r e p r o d u c i b l e to ±2% o f the amount present f o r most major e l e
ments. R e l a t i v e accuracy decreases with decreasing elemental
concentrations. For elemental c o n c e n t r a t i o n s o f about 1 w t i ,
r e l a t i v e accuracy should be w i t h i n ±5$. The EPM r e v o l u t i o n i z e d
p e t r o l o g y and geochemistry, but the p a u c i t y o f published papers
r e p o r t i n g i t s use i n c o a l and peat s t u d i e s shows that EPM has
been neglected i n c o a l r e s e a r c h . E l e c t r o n m i c r o a n a l y s i s o f c o a l
g e n e r a l l y has been l i m i t e d t o the scanning e l e c t r o n microscope
(SEM) with energy d i s p e r s i v e x-ray (EDX) c a p a b i l i t y . The unique
c a p a b i l i t i e s o f the EPM can provide i n f o r m a t i o n that i s i n a c c e s
s i b l e through other methods. Examples are x-ray chemical s h i f t

9. RAYMOND Electron Probe Microanalysis 193
determinations, l i g h t element d e t e c t i o n , and r e s o l u t i o n o f x-ray

l i n e s that have EDX i n t e r f e r e n c e s by wavelength d i s p e r s i v e x-ray
(WDX) techniques. Modern c o m b i n a t i o n EPM-SEM i n s t r u m e n t s
equipped with both EDX and WDX c a p a b i l i t i e s are e s p e c i a l l y power-
f u l tools for coal analysis.
EPM has important advantages over c o n v e n t i o n a l methods o f
a n a l y s i s f o r organic s u l f u r i n c o a l : a n a l y s i s by EPM i s done
d i r e c t l y , thus a v o i d i n g problems a s s o c i a t e d with calculating
organic s u l f u r content by d i f f e r e n c e ; organic s u l f u r contents o f
i n d i v i d u a l macérais can be measured i n s i t u i n a sample; and
organic s u l f u r a n a l y s i s with the EPM i s n o n - d e s t r u c t i v e and
rapid. The f o l l o w i n g shows how the EPM may be used f o r q u a n t i -
t a t i v e a n a l y s i s o f organic s u l f u r i n c o a l .
Background
I n i t i a l l y Raymond and Gooley (3.) c a l c u l a t e d the organic

s u l f u r content o f a c o a l with the EPM using a mean modal a n a l y s i s
technique. For t h i s work well-documented samples from the
Pennsylvania State u n i v e r s i t y Coal Bank were analyzed. The
samples had p r e v i o u s l y been ground to -20 mesh s i z e . Upon
r e c e i p t , the samples were s p l i t , potted i n epoxy, and made i n t o
p o l i s h e d 2.5 cm rounds, approximately 120 μ m t h i c k . The rounds
were mounted on 27x46 mm g l a s s s l i d e s , and photomicrograph
mosaics o f p o r t i o n s o f the samples were prepared at approximatley
400X m a g n i f i c a t i o n . Mosaics are necessary s i n c e the samples must
be carbon-coated f o r conduction during e l e c t r o n bombardment, and
once the samples are carbon coated, r e f l e c t a n c e l e v e l s are
obscured and i d e n t i f i c a t i o n o f a l l the v a r i o u s macérais i s
extremely d i f f i c u l t . Coal macérais present i n the mosaics were
i d e n t i f i e d by o i l - i m m e r s i o n , r e f l e c t e d l i g h t techniques. Where
p o s s i b l e , 15 examples o f each maceral type w i t h i n the s e c t i o n
were l o c a t e d . In most cases l e s s than 15 p i e c e s o f one or more
p a r t i c u l a r macérais could be found, and so fewer than 15 were
t h e r e f o r e i n c l u d e d i n the a n a l y s i s . Our EPM has a 400X m a g n i f i -
c a t i o n o p t i c a l system, and using morphology o f the v a r i o u s c o a l
g r a i n s i n c o n j u n c t i o n with the mosaics, the p o i n t s o f EPM analy-
s i s could be e x a c t l y l o c a t e d .
S t a n d a r d i z a t i o n datum f o r EPM a n a l y s i s i s determined as an
average o f seven background and matrix c o r r e c t e d i n t e n s i t i e s on a
r e c e n t l y developed petroleum coke standard (A). A f t e r each c o a l
a n a l y s i s the computer p r i n t s x-ray i n t e n s i t i e s and wt% s u l f u r as
determined by comparison with the x-ray i n t e n s i t y o f the p e t r o -
leum coke standard. X-ray i n t e n s i t y o f i r o n i s c o n t i n u a l l y moni-
tored during a n a l y s i s and any i n t e n s i t i e s i n excess o f background
l e v e l s are assummed to r e s u l t from contamination by p y r i t e , so
those r e s u l t s are r e j e c t e d . At the same time, an energy d i s p e r -
s i v e system output i s monitored f o r any elements that might sug-
gest the presence o f other s u l f i d e s or s u l f a t e m i n e r a l s . There-
f o r e our reported s u l f u r contents are most l i k e l y o r g a n i c .

Another p o s s i b i l i t y i s elemental s u l f u r , but the homogeneous

d i s t r i b u t i o n of s u l f u r throughout each maceral i s i n d i c a t i v e o f
organic r a t h e r than elemental s u l f u r .
The r e s u l t s of a sample a n a l y s i s i n c l u d e a number o f organic
s u l f u r measurements f o r a l l macérais present i n the sample. An
example of the a n a l y s i s of a high v o l a t i l e A bituminous (hvAb)
c o a l can be seen i n Table I . The mean organic s u l f u r content
(S ) f o r each maceral-type determined by EPM was m u l t i p l i e d by
the wt* o f that maceral i n the dry c o a l sample. The Pennsylvania
State U n i v e r s i t y Coal S e c t i o n determines the wtjC o f i n d i v i d u a l
macérais i n the c o a l by m u l t i p l y i n g maceral d e n s i t y by volume %
i n the c o a l . Volume % i s determined by counting 1000 p o i n t s , a
method that the Pennsylvania State U n i v e r s i t y Coal S e c t i o n has
been able to show has a r e p r o d u c i b i l i t y o f 2-3*. The s u l f u r

contents c o n t r i b u t e d to the t o t a l organic s u l f u r content o f the
c o a l by the i n d i v i d u a l macérais i s a l s o shown i n Table I . The
summation o f the c o n t r i b u t i o n s o f the i n d i v i d u a l macérais g i v e s
the t o t a l organic s u l f u r c o n c e n t r a t i o n (dry) as determined by
EPM.
To measure the v a l i d i t y o f the EPM technique c o a l s were
chosen i n which s u l f a t e s u l f u r as determined by ASTM methods
equaled zero and i n which p y r i t i c s u l f u r was minimal as d e t e r -
mined by ASTM methods and as observed by o p t i c a l microscopy.
Since i n o r g a n i c s u l f u r contents are s m a l l , any d i s c r e p a n c i e s
between EPM and ASTM organic s u l f u r contents due to i n a c c u r a t e
p y r i t e or s u l f a t e a n a l y s i s a l s o should be s m a l l . As can be seen
i n Table I I the EPM analyses very c l o s e l y approach those o f the
ASTM.
The comprehensive EPM method discussed above i s extremely
time consuming. The method r e q u i r e s point counting the sample to
determine the wt* o f the v a r i o u s macérais. An oil-immersion
photomosaic has to be prepared f o r i d e n t i f i c a t i o n o f a n a l y t i c a l
s i t e s once the sample has been placed i n the EPM. Finally,
g r e a t e r than 60 EPM analyses must be performed to determine the
organic s u l f u r content o f a s i n g l e c o a l sample. Data d e r i v e d
from a n a l y s i s o f numerous c o a l s using the comprehensive method,
Table I: Comprehensive EPM method o f organic

s u l f u r a n a l y s i s o f L. Elkhorn, KY, hvAb
c o a l ( a f t e r 3.).
MACERAL wtjt S /
UACEBAL wt* S wt* MACERXL
Vitrinite 0.61° 52.8 0.32
Pseudovitrinite 0.56 16.4 0.09
Fusinite 0.27 6.2 0.02
Semifusinite 0.44 6.2 0.03
Sporinite 0.64 6.0 0.04
Micrinite 0.59 2.8 0.02
Macrinite 0.51 0.7 (0,004)
Total S (dry) = 0.52 wt$

Table I I : ASTM/EPM comparative study

( a f t e r (3.) ; a l l contents as dry wt% )
ASTM ASTM EPM

lAHK PYRITIC S ORGANIC S ORGANIC S
U. Elkhorn #3 hvAb 0.01 0.61 0.63

Ohio #5 subC 0.01 0.92 0.94
L. Elkhorn hvAb 0.03 0.52 0.52
Hazard #7 hvAb 0.03 0.51 0.58
U. Sunnyside hvAb 0.06 0.59 0.66
B l i n d Canyon hvAb 0.13 0.33 0.41
0.18
D i e t z #3 subC 0.13 0.15
t h o u g h , p r o v i d e d us w i t h a b e t t e r and more c o n f i d e n t EPM

approach.
The comprehensive method was performed on 29 c o a l s that
represented 27 seams from 13 s t a t e s i n the contiguous USA. Rank
o f the c o a l s ranged from subbituminous C to low v o l a t i l e ; t o t a l
s u l f u r contents ranged from 0.28 t o 8.60 wtj ( d r y ) ( T a b l e I I I ) .
The organic s u l f u r contents o f the c o a l s determined by the com-
prehensive EPM method are p l o t t e d vs the organic s u l f u r content
o f r e s p e c t i v e v i t r i n i t e components ( F i g u r e 1). The best l i n e a r
fit of the data has a c o r r e l a t i o n c o e f f i c i e n t o f 0.99, a
y - i n t e r c e p t o f -0.03, and a slope o f 0.98. E m p i r i c a l l y , the
organic s u l f u r content o f a c o a l e s s e n t i a l l y equals the organic
s u l f u r content of i t s v i t r i n i t e .
Raymond (5.) showed that a general r e l a t i o n s h i p e x i s t s i n
most c o a l s with respect to organic s u l f u r contents o f the
macérais: s p o r i n i t e , r e s i n i t e Σ m i c r i n i t e , v i t r i n i t e > psuedo-
v i t r i n i t e Σ s e m i f u s i n i t e Σ m a c r i n i t e > f u s i n i t e (Table I V ) . How
then can the v i t r i n i t e organic s u l f u r content be r e p r e s e n t a t i v e
of a l l macérais present i n a c o a l sample? In most o f the 29
c o a l s discussed above (as i s the case i n most c o a l s ) the v i t r i -
n i t e macérais dominate (Table I I I and V). Thus the v i t r i n i t e
organic s u l f u r content has a major i n f l u e n c e on the organic s u l -
f u r content o f the c o a l . But what o f the c o a l s c o n t a i n i n g as
l i t t l e as 41.9 wtjt v i t r i n i t e macérais? Table VI c o n t a i n s the
wt* of the v a r i o u s macérais found i n two c o a l s and the organic
s u l f u r contents o f those macérais. As can be seen i n Table VI,
the v i t r i n i t e organic s u l f u r contents approximate the organic
s u l f u r contents determined from the weighted mean o f the other
macérais present. Therefore, as w e l l as commonly being the most
dominant maceral, the v i t r i n i t e contains an organic s u l f u r con-
tent approximately equivalent to the mean of a l l the macérais.
Two f a c t o r s make i t advantageous to measure the organic
s u l f u r content o f v i t r i n i t e i n order to f i n d the organic s u l f u r
content of a c o a l . The most obvious i s that the number o f EPM
analyses w i l l be fewer. For each o f the c o a l samples l i s t e d i n

Figure 1. Organic sulfur content of coal vs. organic sulfur content of respective
vitrinite components for coals listed in Table III (dmmf wt %). All measurements
by EPM.

VO
Table III: V a r i o u s c h a r a c t e r i s t i c s o f t h e 29 c o a l s a m p l e s o n w h i c h t h e c o m p r e h e n s i v e EPM method

was p e r f o r m e d ( T o t a l S on d r y b a s i s ; a l l o t h e r v a l u e s on dmmf b a s i s ) ,
macérais, I = i n e r t i n i t e macérais, L = l i p t i n i t e macérais, S
V = vitrinite
Mod. = o r g a n i c s u l f u r
ι
Ο
v a l u e d e t e r m i n e d b y m a c e r a l mean m o d a l a n a l y s i s , S V i t . = organic sulfur value Ο
0
d e t e r m i n e d by v i t r i n i t e a l o n e .
Rank Tot. S Seam Name State ÎV $1 *L S Mod. S„ Vit

0 ο
lvb 2.07 L. Kittanning PA 76.0 24.0 0.0 0.46 0.48

tt 3.29 U. Hartshorne OK 92.2 7.8 0.0 0.84 0.89 ο
η 6.01 U. Kittanning PA 76.4 23.5 0.1 0.74 0.78
mvb 0.82 Sewell W.VA 66.9 28.7 4.4 0.65 0.77

η 1.62 U. F r e e p o r t PA 87.6 9.1 3.3 0.48 0.52
Î
hvAb 0.46 Blind Canyon UT 88.5 9.8 1.7 0.43 0.44
η 0.54 H a z a r d #7 KY 70.9 20.1 9.0 0.74 0.77
η 0.55 L. E l k h o r n KY 75.9 17.5 6.6 0.55 0.61
η 0.62 U. E l k h o r n KY 41.9 38.9 19.2 0.67 0.73
tl 0.65 U. S u n n y s i d e UT 89.8 8.5 1.7 0.71 0.75
ft 1.96 Clintwood VA 64.5 31.2 4.3 0.81 0.88
ft 2.34 Americana ALA 68.7 24.9 5.4 1.32 1.52
ft 2.62 Pittsburgh PA 83.6 13.7 2.7 1.08 1.19
ft 2.93 Pittsburgh W.VA 75.1 20.9 4.0 2.41 2.65
ft 3.73 L. K i t t a n n i n g PA 85.0 11.8 3.2 1.07 1.14

ft 5.64 L. Clarion PA 83.9 11.0 5.1 1.28 1.23
ft 6.55 Clarion PA 72.6 16.9 10.5 1.64 1.50
Continued on next page.

TABLE I I I (continued)
Rank Tot. S Seam Name State %V ÎI %L S^ Mod. S Vit.

-2 _2
hvBb 3.39 Ohio #4 OH 75.0 17.7 7.3 2.80 2.93

tt 3.60 I l l i n o i s #2 IL 78.3 18.4 3.3 3.02 3.09
tt 4.55 Kentucky #14 KY 83.4 12.0 4.6 1.16 1.13
tt 5.85 Bevier MO 69.6 28.7 1.7 2.97 3.08
tt 7.27 Tebo MO 75.3 19.1 5.6 3.13 3.55
hvCb 2.59 I l l i n o i s #6 IL 84.7 4.4
10.9 2.26 2.28
tt 3.86 I l l i n o i s #5 IL 89.2 10.1 0.7 2.80 2.96
η 6.14 L. Cherokee ΙΑ 74.3 3.4
22.3 5.29 5.10
tt 8.60 unknown ΙΑ 89.4 9.3 1.3 4.08 4.31
subB 0.28 D i e t z #3 WY 83.8 15.6 0.6 0.19 0.21
subC 0.93 Ohio #5 OH 84.6 10.0 5.4 1.04 1.16
tt 1.78 Wildcat TX 88.8 10.0 1.2 1.50 1.59

Table IV: General r e l a t i o n s h i p between macérais and organic s u l f u r contents

f o r high and low s u l f u r c o a l s (S wt$ on dmmf b a s i s ) S = s p o r i n i t e ,
R = r e s i n i t e , Mi = m i c r i n i t e , V = v i t r i n i t e , Pv = p s e u d o v i t r i n i t e ,
Ma = m a c r i n i t e , S f = s e m i f u s i n i t e , F = f u s i n i t e ( a f t e r 5.).
Rank Coal _5L -Ha JL
lvb L. K i t t a n n i n g _ 0.48 0.36 0.30

0.57 0.39
hvAb U. Sunnyside 0.56 0.53 0.69 0.75 0.53 0.43 0.47 0.39
hvAb B l i n d Canyon 0.70 0.53 0.48 0.44 0.40 0.30 0.30 0.26
hvAb Americana 1.23 1.07 1.52 1.30 0.83 0.71 0.57
hvBb Tebo 4.07
-
4.99 3.87 3-55 2.81 1.03 0.75
subC Ohio #5 0.87 1.28 1.16 0.35
-
0.82 0.32 0.20
-

Table V: A n a l y s i s o f maceral c o n s t i t u e n t s f o r 29 c o a l s
(maceral wt* on a dmmf b a s i s )
* wtf MUSK
Vitrinite 78.5 41.9-92.2

Inertinite 17.3 7.8-38.9
Liptinite 3.7 0.0-19.2
Table V I I , Raymond et a l . (&) analyzed up to 400 v i t r i n i t e g r a i n s

for organic s u l f u r content both with and without the a i d o f
photomosaics. Using a t - s t a t i s t i c approach they c a l c u l a t e d the
number o f analyses (n) f o r each run necessary to g i v e a d e s i r e d

maximum v a r i a b i l i t y o f 10*, at the 95* confidence l e v e l , from the
true mean as defined by 100 analyses. As can be seen i n Table
VII, i n no case was i t necessary to analyze more than 14 v i t r i -
n i t e areas. The second advantage to a n a l y z i n g o n l y v i t r i n i t e i s
that Raymond et a l . (&) were able to achieve e s s e n t i a l l y i d e n -
t i c a l r e s u l t s both with and without the use o f photomosaics.
Using texture and morphology to i d e n t i f y areas o f v i t r i n i t e a f t e r
the sample had been placed i n the EPM was as s u c c e s s f u l as i d e n -
t i f y i n g the v i t r i n i t e using oil-immersion microscopy p r i o r t o
analysis. I t should be noted that only two o f the four
researches were f a m i l i a r with the EPM. T h i s , combined with the
v a r i e t y o f c o a l s chosen, supports the unbiased nature o f the t e s t
even though the sample set c o n s i s t e d o f only four c o a l s . Thus
the need f o r photomosaics i s e l i m i n a t e d .
The Rapid EPM Method

EPM a n a l y s i s f o r organic s u l f u r content can be performed
e a s i l y on -20 to -100 mesh c o a l samples. Samples need o n l y be
mounted i n epoxy and p o l i s h e d s i m i l a r to how c o a l samples are
commonly prepared f o r pétrographie examination. 15 areas w i t h i n
non-contiguous v i t r i n i t e g r a i n s are analyzed with the EPM. With-
out the need to produce a photomosaic, the organic s u l f u r content
of v i t r i n i t e , and t h e r e f o r e o f a c o a l , may be determined i n l e s s
than 10 minutes.
To t e s t the EPM method c o a l s were analyzed f o r which the
ASTM organic s u l f u r values were c o r r e c t e d f o r unextracted i r o n .
As discussed by Suhr and Given (2) such a c o r r e c t i o n would take
i n t o account the e f f e c t o f any p y r i t e that remained unextracted
f o l l o w i n g the ASTM Standard Method D2492-68. As can be seen from
the data i n Table V I I I , the EPM o r g a n i c s u l f u r contents are yery
c l o s e to those o f the c o r r e c t e d ASTM v a l u e s .
Plgovisslon
The chemistry o f a c o a l may vary g r e a t l y w i t h i n a seam, both
from the top to the bottom and t r a n s v e r s e l y throughout i t . These
v a r i a t i o n s are r e a l , and they represent d i f f e r e n t c o n d i t i o n s that

Table V I : R e l a t i o n s h i p between o r g a n i c s u l f u r contents o f v i t r i n i t e ,

remaining macérais, and whole c o a l ( a l l wt* on dmmf b a s i s ) V
= v i t r i n i t e , Pv = p s e u d o v i t r i n i t e , F = f u s i n i t e , S f = semi-
f u s i n i t e , Ma = m a c r i n i t e , Mi = m i c r i n i t e , S= s p o r i n i t e , R =
resinite.
U. Elkhorn hvAb Coal
_Ji EY Ε Si tfe Mi S &_
wt* o f sample 38.9 2.2 7.1 5.3 13.2 13-3 17.6 2.4
wt* S 0.73 0.45 0.30 0.38 0.64 0.60 0.94 1.03
ο
S V i t . =0.73 S A (wt'd x) remaining macérais = 0 . 6 7 S^ c o a l = 0.69
Ohio #4 hvBb Coal
V Pv F Sf Ma Mi S
wt* of sample 72.0 3.0 3.9 5.7 0.3 7.8 7.3

wt* S
o 2.93 2.56 0.73 1.51 0.92 2.90 3.89
S V i t . =2.93 S (wt'd x) remaining macérais = 2 . 5 0 S c o a l = 2.80

0 0 ο
Table V I I : Number o f analyses (n) necessary to g i v e a

maximum d e s i r e d v a r i a b i l i t y when a n a l y z i n g
f o r organic s u l f u r with EPM ( a f t e r £ ) .
£QAL JBAHK SULFUR wt* (drv) _π_
Tebo hvBb 7.27 13-14

Ohio #5 subC 0.93 10-12
U. Sunnyside hvAb 0.65 5-6
L. K i t t a n n i n g low v o l 2.07 7-9
Table V I I I : Coals c o n t a i n i n g p y r i t e - EPM S vs

documented ASTM S Q (ASTM data a f t e r (1);
a l l contents as dry wt*).
L. KITTANNING hvAb/hvBb COAL
ASTM EPM
SAMPLE S Q (diff.) S Q (corr.) S Q
1273 1.54 1.49 1.50

1276 2.12 2.07 2.09
1277 2.09 2.04 2.08
1279 0.55 0.44 0.60
1282 0.61 0.53 0.57
1299 1.28 1.19 1.09
occur during c o a l maturation processes. Using the EPM method,

the p o t e n t i a l e x i s t s to achieve very r a p i d , m u l t i p l e organic
s u l f u r analyses, which i n t u r n w i l l allow f o r r a p i d , d e t a i l e d
measurements o f v a r i a t i o n s i n organic s u l f u r content o c c u r r i n g
across c o a l seams. Indeed, Raymond (8) and Raymond and Davies
(9) have been able to apply the EPM method to the L. K i t t a n n i n g
c o a l seam and have been able to show how organic s u l f u r values
f o r that seam c o r r e l a t e with organic s u l f u r values f o r recent
peats deposited under s i m i l a r c o n d i t i o n s i n F l o r i d a Bay. The EPM
o f f e r s the opportunity to i n v e s t i g a t e the occurrence o f organic
s u l f u r i n c o a l , on a maceral or whole c o a l b a s i s , that h e r e t o f o r e
was shrouded i n the heterogeneity o f the sample and the com
p l e x i t y o f the a n a l y s i s .
Acknowledgments
I would l i k e to thank the Pennsylvania State U n i v e r s i t y Coal
S e c t i o n f o r the samples they provided f o r EPM a n a l y s i s , and f o r
the c o n s t i t u e n t maceral data and ASTM analyses on those samples.

I would e s p e c i a l l y l i k e t o thank Dr. Peter Given f o r p r o v i d i n g me

with s p l i t s o f the L. K i t t a n n i n g samples l i s t e d i n Table V I I I .
Over the past four years Tom Gregory, Roland Hagan, and Dave
Mann, Los Alamos N a t i o n a l Laboratory, have provided the t e c h n i c a l
a s s i s t a n c e i n sample p r e p a r a t i o n and a n a l y s i s necessary t o keep
the development o f the EPM organic s u l f u r technique on l i n e . Ron
Gooley, Los Alamos N a t i o n a l Laboratory, and Tom Davies, Exxon
Production Research, provided the s c i e n t i f i c e x p e r t i s e t o ques
t i o n v a r i o u s aspects o f the EPM procedure, and by so doing,
helped t o make the procedure that much stronger. The general
a s s i s t a n c e o f Tom Davies, Roland Hagan, and Alan A l l w a r d t , UC
Santa Cruz, i n the s t a t i s t i c a l analyses i s t r u l y a p p r e c i a t e d .
T h i s work was performed a t the Los Alamos N a t i o n a l Laboratory and
supported by the Department o f Energy under c o n t r a c t W-7405-ENG-

36.
Literature Cited
1. Edwards, A. H., Jones, J. Μ., Newcombe, W. Fuel 1964, 43,
55-62.
2. Greer, R. T. in "Scanning Electron Microscopy/1977/I," O.
Johari (ed.), ITT Research Institute, Chicago, 1977, 79-93.
3. Raymond, R., Jr.; Gooley, R. in "Scanning Electron Micros
copy /1978/I," O. Johari (ed.), SEM Inc., AMF O'Hare, IL,
1978, 93-107.
4. Harris, L. Α., Raymond, R., Jr.; Gooley, R. in "Microbeam
Analysis," D. B. Wittry (ed.), San Francisco Press, San
Francisco, 1980, 147-148.
5. Raymond, R., Jr. in "Microbeam Analysis," Ε. E. Newbury
(ed.), San Francisco Press, San Francisco, 1979, 105-110.
6. Raymond, R., Jr.; Davies, T. D.; Hagan, R. C. in "Microbeam
Analysis," D. B. Wittry (ed.), San Francisco Press, San
Francisco, 1980, 149-150.
7. Suhr, N.; Given, P. H. Fuel 1981, 60, 541-542.
8. Raymond, R., Jr. Compte Rendu of the IX Inter. Cong. of
Carb. Strat. and Geol., Urbana, IL (in press).
9. Raymond, R., Jr.; Davies, T. D. GSA Abst. with Progs., 1979,
V. 11, no. 7, p. 501.

10
Chemical Fractionation and Analysis of Organic
Compounds in Process Streams of Low Btu
Gasifier Effluents
R. L . HANSON, R. E . ROYER, J. M . BENSON, R. L . CARPENTER,
G. J . NEWTON, and R. F. HENDERSON
Lovelace Biomedical and Environmental Research Institute, Inhalation Toxicology
Research Institute, Albuquerque, N M 87185
Low Btu gas requires cleanup before it can be burned

in a turbine. Several cleanup devices have been
used on the output stream of the stirred bed gasi-
fier at the Morgantown Energy Technology Center.
Both vapor phase and particulate phase organic com-
pounds were sampled at several locations in the
cleanup process. Vapor phase samples were collected
using Tenax-GC polymer adsorbent and by condensa-
tion traps. The particulate phase organic materials
were collected on glass fiber filters placed before
the Tenax adsorbent, by condensation traps and by a
multicyclone train. Methods of chemical analysis
included: the determination of mass of total di-
chloromethane extractable materials and gas chroma-
tographable organic compunds, fractionation using
gel permeation chromatography and silica column
chromatography and analysis by gas chromatography/
mass spectrometry to identify compounds. We found
that the cleanup system preferentially removed
higher molecular weight organic compounds from the
process stream. Greater quantities of organic com-
pounds were found associated with the particulate
phase than the vapor phase in cooled and diluted
samples of the process stream. Gas chromatographic/
mass spectrometry analysis indicated the presence
of aliphatic compounds and many polynuclear aromat-
ic compounds containing oxygen, nitrogen and sulfur
heteroatoms.
Coal gasification is being developed as an alternative method

of energy production. Low Btu gasification of coal is being
evaluated for use in combined-cycle electrical generation in
which the low Btu coal gas is combusted in a gas turbine and
0097-6156/82/0205-0205$06.00/0

the hot exhaust gases sent through a steam recovery system. Low
Btu gas can also be upgraded to higher Btu gas by methanation
processes.
C u r r e n t l y a v a i l a b l e g a s i f i e r s have two major r e s t r i c t i o n s :
(A) they are only compatible with noncaking coals and hence are
unable to use the large eastern USA coal r e s e r v e s ; and (B) except
f o r Lurgi g a s i f i e r s they are l i m i t e d to low operating pressures
which r e s u l t in l i m i t e d throughput. A research and development
program at the Morgantown Energy Technology Center (METC) i s
under way t o overcome these r e s t r i c t i o n s . Program goals at METC
include development of gas cleanup systems to allow the use of
combined-cycle low Btu g a s - f i r e d t u r b i n e s .
The Lovelace Inhalation Toxicology Research I n s t i t u t e (ITRI)
has been involved with METC i n a cooperative program t o address

basic human health r i s k s associated with low Btu coal g a s i f i c a -
tion. A p o r t i o n of t h i s research involves chemical c h a r a c t e r i -
z a t i o n of organic compounds in gaseous, l i q u i d and s o l i d process
and waste streams.
Complex organic mixtures r e q u i r e chemical f r a c t i o n a t i o n p r i o r
to chemical analyses i f minor components are to be i d e n t i f i e d
(1). Chemical f r a c t i o n a t i o n methods used in t h i s study were gel
cïïromatography, acid-base neutral solvent p a r t i t i o n i n g and chrom-
atography on s i l i c a gel columns. I d e n t i f i c a t i o n of compounds
was done by gas chromatography/mass spectrometry (GC/MS). Proton
nuclear magnetic resonance (PMR) spectroscopy was used to char-
a c t e r i z e f r a c t i o n s and s u b f r a c t i o n s which were not amenable t o
GC/MS a n a l y s i s .
Experimental
The METC Low Btu Coal G a s i f i e r . The METC coal g a s i f i e r has

been described p r e v i o u s l y (2, 3 ) . B r i e f l y , i t is a pressurized
v e r s i o n of the McDowell-WelTman (Wellman-Galusha) atmospheric
pressure s t i r r e d - b e d coal g a s i f i e r (Figure 1) and d i f f e r s from
commercial fixed-bed producers in i t s smaller s i z e (1.1 m ID)
and various p r o v i s i o n s f o r s t i r r i n g the bed. Cleanup devices
c o n s i s t e d of a cyclone f o r removing large p a r t i c l e s , a humid-
i f i e r , t a r trap and Venturi scrubber f o r removal of t a r s and o i l s
and a s i d e stream f o r experimental gas cleanup with the cleaned
gas burned in a f l a r e . The experimental cleanup devices were an
e l e c t r o s t a t i c p r e c i p i t a t o r , a d i r e c t c o o l e r , Holmes-Stretford
d e s u l f u r i z e r , a l k a l i scrubber and i n d i r e c t c o o l e r .
Sample C o l l e c t i o n . Producer gas was d i l u t e d with cool dry
nitrogen by a r a d i a l l y i n j e c t e d d i l u t e r which r e s u l t e d in aerosol
formation (2). For c o l l e c t i o n of p a r t i c l e s and vapor phase ma-
t e r i a l s the d i l u t e d producer gas was passed through a glass f i b e r
f i l t e r and then through a Tenax-GC polymer adsorbent trap (4)
#
at a flow r a t e of about 12 L/min. Table I l i s t s the types o7

samples c o l l e c t e d and the p o s i t i o n s at which they were c o l l e c t e d .
In order to obtain l a r g e r amounts of condensates, a s e r i e s sam-
p l i n g t r a i n c o n s i s t i n g of four modified Greenberg-Smith impingers

10. HANSON E T A L . Organic Analysis of Process Streams 207

was used to sample undiluted gas a f t e r the c y c l o n e . Modifica-

t i o n s c o n s i s t e d of increasing c o l l e c t i n g surfaces (glass beads
or s t e e l wool) i n s i d e the main v e s s e l s , e l i m i n a t i n g the j e t and
c o l l e c t o r and adjusting sample flow to 20 L/min. Condensers were
placed in temperature-controlled baths with Number 1 at ambient
(0° to 10°C), Number 2 in an i c e water bath (approximately 0°C)
and Numbers 3 and 4 in dry i c e acetone (-77°C). Tar was obtained
from the h u m i d i f i e r t a r t r a p and with the o u t l e t water from the
Venturi scrubber decanter. Ash was obtained from the g a s i f i e r
and c y c l o n e .
Table I
Samples Col at G a s i f i e r
Position Type of Samples

Base of G a s i f i e r Âsfi
Base of Cyclone Ash
A f t e r Cyclone F i l t e r , Tenax Adsorbent,
Condenser
Base of Humidifier Tar
Base of Tar Trap Tar
A f t e r Tar Trap F i l t e r , Tenax Adsorbent
Venturi Scrubber Decanter T a r , Water
A f t e r Venturi Scrubber F i l t e r , Tenax Adsorbent
A f t e r Side Stream Cleanup F i l t e r , Tenax Adsorbent
Sample E x t r a c t i o n s . Both f i l t e r p a r t i c u l a t e samples and

Tenax adsorbent samples were e x t r a c t e d with organic solvents to
remove the adsorbed organic m a t e r i a l . Pentane was used f o r
Soxhlet e x t r a c t i o n of Tenax samples whereas dichloromethane was
used f o r u l t r a s o n i c e x t r a c t i o n of p a r t i c u l a t e f i l t e r samples ( 5 ) .
E x t r a c t s were concentrated by r o t a r y e v a p o r a t i o n . For g r a v i -
metric analyses of some of the e x t r a c t s , the concentrate from
the r o t a r y evaporator was t r a n s f e r r e d t o a small v i a l and taken
to dryness under a stream of n i t r o g e n .
Venturi scrubber o u t l e t water and the condenser samples were
solvent p a r t i t i o n e d with dichloromethane. The dichloromethane
was removed by r o t a r y evaporation followed by f i n a l drying under
a stream of n i t r o g e n .
Sample F r a c t i o n a t i o n s . Organic m a t e r i a l s were f i r s t f r a c -
tionated using a column (1 m by 1.5 cm I . D . ) f i l l e d with Sephadex
LH-20. The column i s f i r s t e l u t e d with 240 mL of tetrahydrofuran
which e l u t e s the l e a s t p o l a r and the higher molecular weight com-
pounds f i r s t followed by the more p o l a r ones. A f i n a l , very
p o l a r , f r a c t i o n i s eluted with 300 mL of methanol. Several s t a n -
dards were run t o c h a r a c t e r i z e the e l u t i o n of c l a s s e s of organic
compounds from the column as shown in Figure 2.

10. HANSON ET AL. Organic Analysis of Process Streams 209
F-2 F-»
POLYMERS
ALKANfJ
NQ2-PAHS
QRQANOMETALLIC8
PAH'S
_AMIMO-PAirS_
KETQ-PAHS
S-PAH'S
PHENOLS
AZA-ARENE8
ACIDS
SALTS
100 115 ISO 146

TETRAHYDROFURAN (ml) METHANOL (ml)
Figure 2. Elution profiles of compounds from Sephadex LH-20 column using

tetrahydrofuran (THF) as eluant. The lines for each compound indicate the volume
of THF in which the compounds eluted. Elution of compounds was monitored with
an ISCO model UA-5 absorbance monitor at 280 nm.

F r a c t i o n s 3 and 4 from the Sephadex column, which contained

p r i m a r i l y nonpolar p o l y c y c l i c aromatic compounds, were combined
and then s u b f r a c t i o n a t e d on a column of s i l i c a g e l . The s i l i c a
(Sigma Chemical C o . , 60-200 mesh type I chromatographic grade)
gel was a c t i v a t e d at 110°C f o r 1 hr and placed i n the column
(30 cm χ 2 cm I . D . ) as a s l u r r y in t o l u e n e . Combined F r a c t i o n s
3 and 4 (200 mg) were placed on the column i n 5 mL of toluene
and e l u t e d s e q u e n t i a l l y with 115 mL of toluene ( s u b f r a c t i o n A ) ,
110 mL of propanol ( S u b f r a c t i o n Β) and 300 mL of methanol (Sub-
f r a c t i o n C ) . When F r a c t i o n s 3 and 4 were s u b f r a c t i o n a t e d sepa
r a t e l y 1:1 toluenern-propanol (V:V) was used in p l a c e of propa
nol. For a f i l t e r sample F r a c t i o n s 1 and 2 were a l s o separated
on the s i l i c a gel column.

Because of i t s more p o l a r nature, F r a c t i o n 5 from the Sepha
dex column was s u b f r a c t i o n a t e d by aqueous/organic p a r t i t i o n i n g .
A 100 mg sample of F r a c t i o n 5 was d i s s o l v e d i n 20 ml of d i c h l o
romethane and extracted twice with equal volumes of IN H3PO4
and twice with equal volumes of 5% sodium carbonate.
The organic phase (neutrals/phenols) was d r i e d over sodium s u l
f a t e , reduced by r o t a r y evaporation and the remaining solvent
was removed under a stream of dry nitrogen at 50°C. The aqueous
H3PO4 (organic bases) and Na2C03 (organic acids) e x t r a c t s
were washed with hexane and then n e u t r a l i z e d with d i l u t e sodium
hydroxide or HC1 s o l u t i o n , r e s p e c t i v e l y . The bases and acids
were back extracted with dichloromethane and t r e a t e d in the same
manner as the n e u t r a l s / p h e n o l s . The aqueous phase remaining from
e x t r a c t i o n of the bases was allowed to evaporate over a period
of several days in a fume hood and the dry s a l t s were extracted
with dichloromethane to remove any organic material (water s o l
uble compounds).
Chemical A n a l y s i s . The q u a n t i t y of gas chromatographable
organic compounds were determined as described p r e v i o u s l y
(4, 5 ) . For GC/MS a n a l y s i s , a Finnigan model 4023 gas chromato-
grapïï/mass spectrometer and INCOS data system were used to ob-
t a i n 70 ev e l e c t r o n impact mass s p e c t r a of gas chromatographable
compounds. A 25 m OV-101 quartz c a p i l l a r y column was used.
C a r r i e r gas was helium with a flow v e l o c i t y of 30 cm/sec. The
temperature program was 50°C f o r two minutes and then 5° per
minute t o 270°. The f i n a l temperature was held f o r 15 minutes.
Samples were i n j e c t e d ( s p l i t l e s s i n j e c t i o n ) in 1 yL of d i c h l o -
romethane at a concentration of 2 yg per y L .
The PMR s p e c t r a were taken at 80 MHz with a Varian FT-80A
NMR spectrometer. Samples (0.5 mL) were prepared i n deutero-
chloroform at concentrations of 10-25% by weight. Tetramethyl-
s i l a n e (TMS) was used as an i n t e r n a l r e f e r e n c e . Chemical s h i f t s
(δ) are given in p a r t s per m i l l i o n from TMS. Five hundred
pulses were taken t o obtain very high s i g n a l to noise r a t i o s .
Results and Discussion
Process Stream Samples. The concentrations of organic ex-

t r a c t a b l e material in the process stream are l i s t e d in Table I I .

These r e s u l t s show that the cleanup system removed the p a r t i c u

l a t e phase organic compounds. The reconstructed ion chromatogram
from GC/MS a n a l y s i s of the samples c o l l e c t e d a f t e r the cyclone
are shown in Figure 3. The GC/MS analyses of samples i n d i c a t e d
t h a t compounds with molecular weights from about 100 to 400 d a l -
tons were present in samples c o l l e c t e d a f t e r the cyclone whereas
the cleanest gas a f t e r the d i r e c t c o o l e r had fluoranthene (MW=202)
as the l a r g e s t organic compound. The gas chromatographable p e r
centage f o r various g a s i f i e r sample e x t r a c t s and Sephadex LH-20
f r a c t i o n s of a condenser sample are given in Table I I I .
Table II
Concentrations of Organic M a t e r i a l in G a s i f i e r Process Stream
Organic E x t r a c t a b l e Material
Vapor Phase P a r t i c l e Phase
Sampling P o s i t i o n η g/m 3
g/m 3
Between Cyclone and (D 0.48 12.5

Humidifier
Between Tar Trap and (2) 0.15 - 0.64 0.83 - 3.0
Venturi Scrubber
A f t e r Venturi Scrubber (2) 0.45 - 1.17 1.34 - 2.12
A f t e r Side Stream (2) 0.12 - 0.90 0.0014 - Ο.Όθ18
Cleanup
Table III
Gas Chromatographable Percentage f o r E x t r a c t s

and F r a c t i o n s of G a s i f i e r Samples
Sample Gas Chromatographable %
Tenax F i l t e r E x t r a c t s A f t e r Cyclone 36
Tenax F i l t e r E x t r a c t s A f t e r Tar Trap 54
Tenax F i l t e r E x t r a c t s Cleaned Gas 100
Tar Trap Tar E x t r a c t s 39
Condenser Sample Obtained A f t e r Cyclone 31
Sephadex LH-20 F r a c t i o n s of Condenser
M a t e r i a l Obtained A f t e r Cyclone
Fraction 1 34
Fraction 2 27
Fraction 3 100
Fraction 4 28
Fraction 5 58
Fraction 6 20

100.0
Figure 3. Reconstructed ion chromatograms from GC/MS analysis of vapor phase

organic extractable from Tenax (upper trace) and dichloromethane extractables from
glassfiberTenaxfilter(lower trace). Samples of the raw gas collected after the
cyclone. A 25 m OV-101 quartz capillary column was used in a Finnigan model
4023 gas chromatograph mass spectrometer. Temperature program was 2 min at
50°C, 5°C/min to 270°C with 15 min at 270°C.

Since higher molecular weight organic compounds were found

a f t e r the cyclone than f u r t h e r down the process stream the con-
denser samples and a f i l t e r sample from a f t e r the cyclone were
studied f u r t h e r . Because a l l the gas chromatograms of condenser
samples i n d i c a t e d the presence of components with a wide range
of v o l a t i l i t y , a p o r t i o n of the dichloromethane sample c o l l e c t e d
at 0°C was f r a c t i o n a t e d by the Sephadex LH-20 column. The mass
d i s t r i b u t i o n of t h i s condenser sample and i t s s u b f r a c t i o n s are
given i n Table IV.
A f i l t e r sample c o l l e c t e d a f t e r the g a s i f i e r cyclone was
extracted with CH2CI2 and i t was found that 96.8 percent of
the mass on the f i l t e r was s o l u b l e . A p o r t i o n of t h i s e x t r a c t
was f r a c t i o n a t e d on the Sephadex LH-20 column. The mass d i s t r i b -
u t i o n of the Sephadex LH-20 f r a c t i o n s and s i l i c a gel s u b f r a c t i o n -

a t i o n of F r a c t i o n s 1 and 2 are given i n Table V.
The d i f f e r e n c e s i n mass d i s t r i b u t i o n f o r the Sephadex LH-20
f r a c t i o n s l i s t e d i n Table IV and Table V are due to d i f f e r e n t
modes of sample c o l l e c t i o n . The condenser sample contains con-
densable material that i s present i n the vapor phase and i s not
c o l l e c t e d by the f i l t e r even though the process stream f o r the
f i l t e r sample was d i l u t e d with n i t r o g e n .
The three s i l i c a g e l column s u b f r a c t i o n s of F r a c t i o n 1 were
analyzed by GC/MS. The toluene s u b f r a c t i o n ( A ) , which had the
m a j o r i t y of the mass, produced the reconstructed ion chromatogram
shown i n Figure 4 . This chromatogram and the mass s p e c t r a of
the peaks i n d i c a t e d the presence o f a homologous s e r i e s of a l i -
p h a t i c compounds as expected from Sephadex LH-20 F r a c t i o n 1.
These a l i p h a t i c compounds are gas chromatographable and do not
account f o r the n o n v o l a t i l e components i n the g a s i f i e r t a r sam-
ples. Most l i k e l y , higher molecular weight polynuclear aromatic
hydrocarbons eluted in Sephadex LH-20 F r a c t i o n 4 and the more
p o l a r compounds eluted i n F r a c t i o n s 5 and 6 of many of the t a r
samples c o n t r i b u t e to the non-gas chromatographable components.
Cleanup Device Samples. The percent dichloromethane
e x t r a c t a b l e s from s o l i d and l i q u i d samples c o l l e c t e d by the
g a s i f i e r cleanup devices are given i n Table V I . A p o r t i o n of
the dichloromethane e x t r a c t a b l e s from the Venturi scrubber
decanter o u t l e t water was f r a c t i o n a t e d on the Sephadex LH-20
column. The organic compounds i n t h i s sample eluted from the
column p r i m a r i l y (approximately 80%) i n F r a c t i o n 5. A p o r t i o n
of F r a c t i o n 5 was s u b f r a c t i o n a t e d i n t o a c i d i c , basic and neutral
components. This r e s u l t e d i n 15 percent of the mass recovered
in the a c i d i c s u b f r a c t i o n , 1.5 percent i n the basic s u b f r a c t i o n ,
11 percent i n the neutral s u b f r a c t i o n and the remaining 72.5
percent being water s o l u b l e . Many nitrogen heterocycles were
a l s o found i n the basic s u b f r a c t i o n by GC/MS a n a l y s i s .
The t a r phase from the Venturi scrubber decanter o u t l e t and
t h e t a r from the t a r trap were f r a c t i o n a t e d on the Sephadex LH-20
column. A much broader d i s t r i b u t i o n of the organic compounds

214 coal and coal products
Table IV
Mass D i s t r i b u t i o n of 0°C Condenser Sample
Sephadex LH-20
F r a c t i o n s and Subfractions % Mass in F r a c t i o n
Fraction 1 14
Fraction 2 6
Fraction 3 14
a. Toluene 3
11
b. Toluenern-propanol 3
c. Methanol 0.1
Fraction 4 6
a. Toluene 3
4
b. Toluenern-propanol 2
c. Methanol 0.2
Fraction 5 30
a. Acids b
4.5
b. Bases 0.3
c. Neutrals 3.3
d. Amphoterics
and Water Soluble Compounds 22
Fraction 6 30
TOTAL 100
a
S u b f r a c t i o n s obtained by e l u t i o n from a s i l i c a gel column
using t o l u e n e , toluene:n-propanol ( 1 : 1 ; V:V) and methanol.
b
S u b f r a c t i o n s obtained by a c i d , base solvent p a r t i t i o n i n g with
dichloromethane.

Table V
Mass D i s t r i b u t i o n of Dichloromethane Extract

of a Raw Gas F i l t e r Sample
Sephadex LH-20
F r a c t i o n s and Subfractions % Mass i n F r a c t i o n
Fraction 1 11
a. Toluene 6.9
b. Toluene:n-propanol 3.4
c. Methanol 0.7
Fraction 2 19
a. Toluene 8.9
b. Toluenem-propanol 9.7
0.4
c. Methanol
31
Fraction 3
10
Fraction 4
23
Fraction 5
6
Fraction 6
TOTAL 100
Table VI
Dichloromethane E x t r a c t a b l e s From G a s i f i e r
Cleanup Device Samples
Effluent % Extractable
Bottom Ash 0.01

Cyclone Ash 0.30
Tar Trap Tar (100)
Scrubber Water 0.17
Scrubber Tar (100)
from the t a r s was found than occurred f o r the dichloromethane

e x t r a c t a b l e organics from the o u t l e t scrubber water ( 6 - 9 ) . Mass
d i s t r i b u t i o n s in the LH-20 f r a c t i o n s of the Venturi scrubber de-
canter o u t l e t t a r and of the t a r trap t a r are given i n Table V I I .
Mass d i s t r i b u t i o n s f o r the t a r s from these two cleanup devices
are s i m i l a r , i n d i c a t i n g that these t a r s may be s i m i l a r i n com-
position. A p o r t i o n of F r a c t i o n 5 from the t a r trap t a r was s o l -
vent p a r t i t i o n e d i n t o a c i d s , bases, n e u t r a l s and water s o l u b l e s .
Most of mass appeared i n the neutral s u b f r a c t i o n (67%) with 9%

JL
1000 1500 2000 2500
SCAN
Figure 4. Reconstructed ion chromatogram of toluene subfraction from silica gel

column of Sephadex LH-20 fraction 1 of filter sample collected after the gasifier
cyclone. The major peaks are the aliphatic hydrocarbons in this sample.

a c i d s , 4% bases and 20% water s o l u b l e . This neutral subfraction

was found to have c a r b a z o l e , methylcarbazoles, phenanthridone
and phenols present when analyzed by GC/MS. Two of these phenols
were i d e n t i f i e d as 2-hydroxyfluorene and 9-phenanthrol.
Table VII
Mass D i s t r i b u t i o n of Sephadex LH-20 F r a c t i o n s of Tar Samples

from Venturi Scrubber Decanter O u t l e t and the Tar Trap
Sephadex LH-20 Venturi Scrubber

Fraction Decanter O u t l e t Tar Trap
(#) (Weight Percent) (Weight Percent)
1 7 11
2 12 15
3 32 29
4 22 18
5 20 21
6 7 6
A n a l y s i s of the basic s u b f r a c t i o n of F r a c t i o n 5 by GC/MS i n

dicated that i t contained a s e r i e s of aza-arenes and methylated
aza-arenes ranging i n s i z e from methylquinoline t o azapyrene as
i n d i c a t e d i n Table V I I I .
F r a c t i o n s 3 and 4 from the t a r t r a p t a r , which p r i m a r i l y con
tained p o l y c y c l i c aromatic hydrocarbons and t h e i r a l k y l a t e d d e
r i v a t i v e s , were combined and s u b f r a c t i o n a t e d on a s i l i c a gel c o l
umn. In sequential e l u t i o n , toluene e l u t e d 46 percent of the
mass ( s u b f r a c t i o n A ) , propanol e l u t e d 48 percent ( s u b f r a c t i o n Β ) ,
methanol e l u t e d 3 percent ( s u b f r a c t i o n C) and 3 percent was r e
covered by washing the s i l i c a gel with tetrahydrofuran ( s u b f r a c
t i o n D ) . The toluene s u b f r a c t i o n was found by GC/MS a n a l y s i s t o
c o n s i s t of a s e r i e s of PAH, both parent compounds and numerous
methylated d e r i v a t i v e s . In a d d i t i o n , the h e t e r o c y c l i c compound
dibenzothiophene was present as a major peak. Tentative i d e n t i
f i c a t i o n s are l i s t e d i n Table IX. Compounds whose i d e n t i f i c a t i o n s
were confirmed by GC r e t e n t i o n time comparisons with standards
are noted. Although the i d e n t i t i e s of many of the i n d i v i d u a l
PAHs have not been confirmed, i t i s c l e a r that most of the sub-
f r a c t i o n i s PAH i n nature.
For the t a r trap t a r Sephadex LH-20 F r a c t i o n s 1 and 2 and
s i l i c a gel s u b f r a c t i o n s Β and C of combined F r a c t i o n s 3 and 4
were too n o n v o l a t i l e f o r GC/MS a n a l y s i s so they were analyzed by
PMR. The s p e c t r a are shown i n Figures 5 a , 5b, 5 c , and 5d respec
tively. The various regions of the s p e c t r a were assigned by
using a system based on that of B a r t l e and Jones ( 1 0 ) . S i g n a l s
f o r various chemical s h i f t ranges were assigned as shown i n Table
X. I n t e g r a t i o n over the chemical s h i f t ranges l i s t e d gave the

Table VIII
Compounds T e n t a t i v e l y I d e n t i f i e d by GC/MS in the Basic

S u b f r a c t i o n of Sephadex LH-20 F r a c t i o n 5 of Tar Trap Tar
M.W. Number of Isomers Found
Methylquinoline 143 3
2,7-Dimethylquinoline a
157
Dimethylquinolines 157 4
Triomethylquinolines 171 7
Benzo(h)quinoline a
179
Acridine 3
179
Phenanthridine 3
179
Benzo(f)quinoline 179
Methylbenzoqui n o l i nes 193 4
Methylacridine 193 1
Methylphenanthridines 193 2
Dimethylbenzoquinolines 207 6
Azapyrene 203
a
Had same r e t e n t i o n times as standards.
Table IX
Compounds T e n t a t i v e l y I d e n t i f i e d by GC/MS in Toluene S u b f r a c t i o n

of Sephadex LH-20 F r a c t i o n 3 and 4 of Tar Trap T a r .
M.W, Number of Isomers Found
Dimethylnaphthalene 156 4
Acenaphthene 154
Trimethylnaphthalene 170 3
Fluorene a
166
Methylfluorene 180 3
Dibenzothophene a
184
Phenanthrene a
178
Anthracene 3
178
Methyldibenzothiophene 198
Methylphenanthrene 192
Dimethylphenanthrene 206
Fluoranthene 3
202
Pyrene a
202
Phenylnaphthalene 204
Methylpyrene 216
Trimethylphenanthrene 220
Benzo[a]fluorene 216
Benzo[a]pyrene a
252
a
Had same r e t e n t i o n times as standards.

Table X
The Mole Percent of D i f f e r e n t Types of Hydrogen Atoms

i n Non-Gas Chromatographable F r a c t i o n s and Subfractions
of Coal G a s i f i e r Tar as Determined by PMR
Mole Percent of Hydrogen

Fraction Fraction Subfraction Subfraction

δ range 3
Assignment 1 2 B C
0.5-1.0 CH3 γ or 11 8 1
further
from a r o
matic r i n g
1.0-2.0 CH β or
2 49 19 24 4
further
from a r o
matic r i n g
or CH3 β
to aromat
ic ring
2.0-3.3 CH, CH or 2 11 27 30 34
CH3 α t o
aromatic
ring
5.5-9.0 aromatic
and phen- 29 46 44 50
o l i c hy
drogen
3
I n parts per m i l l i o n from t e t r a m e t h y l s i l a n e .
b
S e e reference 5.

1 I '— i 4
CHEMICAL SHIFT (PPM TMS)
Figure 5. PMR spectra of tar trap tar sample. Key: A, Sephadex LH-20 fraction
1; B, Sephadex LH-20 fraction 2; C, propanol subfraction of Sephadex LH-20
fractions 3 and 4; and D, methanol subfraction of Sephadex LH-20 fractions 3
and 4.

values f o r mole percent o f the d i f f e r e n t types of hydrogen i n

F r a c t i o n s 1 and 2 and s u b f r a c t i o n s Β and C as shown.
The PMR s p e c t r a showed that m a t e r i a l i n F r a c t i o n 1 had more
a l i p h a t i c character than that i n F r a c t i o n 2, which i n d i c a t e s t h a t
some c l a s s separation occurs on Sephadex LH-20 even f o r m a t e r i a l s
which are excluded from the gel p o r e s . The increase i n mole p e r
cent of aromatic hydrogen i n F r a c t i o n 2 over F r a c t i o n 1 was ac
companied by a l a r g e r percentage of the a l i p h a t i c hydrogen being
α t o an aromatic r i n g , as would be expected. M a t e r i a l e l u t i n g
in s u b f r a c t i o n Β (from Sephadex LH-20 F r a c t i o n s 3 and 4) appeared
to be s i m i l a r t o F r a c t i o n 2 by PMR, except f o r the smaller peak
a s c r i b e d t o methyl groups β or f u r t h e r from an aromatic r i n g .
I t i s p o s s i b l e that these m a t e r i a l s were separated on the

Sephadex LH-20 column due t o s i e v i n g a c t i o n of the gel and that
the material i n s u b f r a c t i o n Β was lower i n molecular weight than
t h a t i n F r a c t i o n 2. In s u b f r a c t i o n C, n e a r l y a l l the hydrogens
were aromatic or on carbon α t o an aromatic r i n g . In a d d i t i o n ,
the s i g n a l i n the range 6 3-4 i s s i g n i f i c a n t , probably i n d i
c a t i n g the presence of hydrogens on carbon atoms s u b s t i t u t e d with
0 or Ν atoms (11). The source of the peak very near TMS in F r a c
t i o n s 1 and 2 i s not known. The peak at « 5.3 in the spectrum
of s u b f r a c t i o n Β i s r e s i d u a l CH2CI2 s o l v e n t .
Many s i m i l a r types of g a s i f i e r process e f f l u e n t s and c o a l
t a r have been studied from a v a r i e t y of coal g a s i f i e r s . The com
p o s i t i o n of organic e x t r a c t s of scrubber water p a r t i c u l a t e matter
from a high p r e s s u r e , entrained flow g a s i f i e r has been reported
(12). Glass c a p i l l a r y GC/MS was used t o separate 140 components
i n coal t a r (J3). Several l i q u i d phases f o r c o a t i n g of c a p i l l a r y
columns were evaluated i n t h i s r e s e a r c h . Coal t a r from a coking
operation was analyzed with g l a s s c a p i l l a r y GC/MS (J4). The coal
t a r was f r a c t i o n a t e d to obtain f r a c t i o n s c o n t a i n i n g acids and
phenols, bases, hydrocarbons, neutral p o l a r and aromatic compo
nents before the GC/MS analyses. Coal l i q u e f a c t i o n d i s t i l l a t e
c u t s from the SRC-II process have been studied using m i c r o b i a l
mutagenesis assays together with solvent f r a c t i o n a t i o n and GC/MS
a n a l y s i s (15). T h i s report i n d i c a t e d that h y d r o t r e a t i n g reduced
the mutagenicity of samples. Much of t h i s loss was a t t r i b u t e d
t o the conversion of three and f o u r - r i n g primary and aromatic
amines by the hydrotreatment. Work has not yet revealed the
presence of primary aromatic amines i n the mutagenic samples,
f r a c t i o n s and s u b f r a c t i o n s of g a s i f i e r m a t e r i a l s (16).
Conclusions
Results i n d i c a t e d the complex nature of organic m a t e r i a l s

associated with low Btu coal g a s i f i c a t i o n . Several c l a s s e s of
organic compounds were found, i n c l u d i n g neutral s u l f u r and n i t r o
gen h e t e r o c y c l e s , phenols, bases i n c l u d i n g aza arenes and p o l y -
c y c l i c aromatic hydrocarbons. Some organic compounds were not

gas chromatographable, so various l i q u i d chromatographic f r a c

t i o n a t i o n procedures and pH p a r t i t i o n i n g were used t o f r a c t i o n a t e
and c h a r a c t e r i z e these compounds. The PMR spectoscopy also
provided useful information about the s t r u c t u r e of the non-gas
chromatographable organic compounds.
The f o l l o w i n g conclusions can be drawn concerning the gas-
i f i e r cleanup system. The concentration of p a r t i c l e associated
organic compounds i s reduced. The cleanup system removes higher
molecular weight organic compound which are p r i m a r i l y aromatic
and a l k y l s u b s t i t u t e d aromatic compounds. D i l u t i n g and c o o l i n g
the low Btu producer gas, as would happen in f u g i t i v e r e l e a s e s ,
produces a r e s p i r a b l e a e r o s o l . I t i s mainly the heavier p o l y -
nuclear aromatic hydrocarbons that are t r a n s f e r r e d from the
vapor t o the p a r t i c l e phase by d i l u t i n g and c o o l i n g the producer

gas.
Acknowledgements
The authors acknowledge the e x c e l l e n t cooperation and a s s i s

tance received from the s t a f f of the Morgantown Energy Technology
Center. The authors thank D. Horinek, S. S i n c l a i r , and S. C r a i n
for their technical assistance. We thank our colleagues on the
ITRI sampling team f o r o b t a i n i n g samples. The review and support
of Drs. C. H. Hobbs and R. 0 . McClellan i s also acknowledged.
This research was performed under U. S. Department of Energy
Contract Number DE-AC04-76EV01013.
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of METC 42-inch Gas Producer During 1964-1977," METC/RI-
78/12, October 1978.
4. Hanson, R. L.; Royer, R. E.; Carpenter, R. L.; and Newton,
G. J., "Characterization of Potential Organic Emissions from
a Low Btu Gasifier for Coal Conversion," in Polynuclear Aro
matic Hydrocarbons, Ann Arbor Science Publishers, Inc., Ann
Arbor, MI, 1979, pp 3-19.
5. Hanson, R. L.; Carpenter, R. L.; Newton, G. J.; Rothenberg,
S. J., J. Environ. Sci. Health, Part A, 1979, 14, 223.

6. Royer, R. E.; Mitchell, C. E.; Hanson, R. L. Submitted to

Environ. Sci. Technol., 1981.
7. Hill, J. O.; Royer, R. E.; Giere, M. S.; Mitchell, C. E.
Submitted to Environ. Sci. Technol., 1981.
8. Benson, J. M.; Hill, J. O.; Mitchell, C. E.; Newton, G. J.;
Carpenter, R. L. In Press Arch. Environ. Contam. Toxicol.,
1982.
9. Benson, J. M.; Mitchell, C. E.; Royer, R. E.; Clark, C. R.;
Carpenter, R. L.; Newton, G. J. Submitted to Arch. Environ.
Contam. Toxicol., 1981.
10. Bartle, K. D.; Jones, D. W. In "Analytical Methods for Coal
and Coal Products, Vol. II"; Karr, C. Jr., Ed.; Academic
Press, New York, 1978; pp 103-160.
11. Aczel, T.; Williams R. B.; Brown, R. Α.; Pancirov, R. J. In

"Analytical Methods for Coal and Coal Products, Vol. I",
Karr, C. Jr., Ed.; Academic Press, New York, 1978; pp 499-
540.
12. Hansen, L. D.; Phillips, L. R.; Mangelson, N. F.; Lee, M.
L., Fuel 59, 323, 1980.
13. Borwitzky, H.; Schomburg, G., J. Chromatogr. 170, 99, 1979.
14. Novotny, M.; Strand, J. W.; Smith, S. L.; Wiesler, D.;
Schwende, F. J., Fuel 60, 213, 1981.
15. Wilson, B. W.; Petersen, M. R.; Pelroy, R. Α.; Cresto, J.
T., Fuel 60, 289, 1981.
16. Benson, J. M.; Hill, J. O.; Royer, R. E.; Hanson, R. L.;
Mitchell, C. E.; Newton, G. J., "Toxicological Characteriza
tion of the Process Stream and Effluents of a Low Btu Coal
Gasifer," in Proceedings of the 20th Hanford Life Sciences
Symposium, Richland, Washington, 1980, in press.

11
Solvent Analysis of Coal-Derived Products
Using Pressure Filtration
BRUCE R. UTZ, NAND K. NARAIN, HERBERT R. APPELL, and

BERNARD D. BLAUSTEIN
U.S. Department of Energy, Pittsburgh Energy Technology Center,
Pittsburgh, PA 15236
A room-temperature, pressure-filtration method for solvent

characterization of coal-derived products is described. Tetra-

hydrofuran solubility and cyclohexane solubility of coal-
-derived products were determined. A comparison of the method
was made with a room-temperature, reduced-pressure
Soxhlet-extraction method, and demonstrated that the pressure-
-filtration method can solubilize as much coal-derived product
as the special type of Soxhlet extraction. Pressure filtration
was also shown to be precise, and gave standard deviations as
low as S = 0.10% when using tetrahydrofuran and S = 0.26% when
using cyclohexane. Values of S can be slightly larger
depending on the vehicle used in the coal-vehicle slurry. A
major advantage of pressure filtration is that solvent
filtration of a sample can be completed within 15 minutes,
whereas a Soxhlet extraction can take many hours or even days.
With high-conversion coal-oil slurry, reaction products, the
solvent classification can be completed in 1 1/2 to 2 hours.
Solvent solubility is widely used to classify coal-derived

products (1,2). The most popular methods are based on some
form of Soxhlet extraction. Methods involving Soxhlet
extraction are normally time consuming; thus complete solvent
solubility classification is laborious. An alternate method,
used initially by Bertolacini et al. (3) and modified for our
use, employs pressure filtration. Pressure filtrations carried
out at room temperature have been used to classify a number of
coal-derived products obtained under a variety of liquefaction
conditions.
The purpose of this paper is to present data on pressure
filtrations as a method to classify coal-derived products, and
to show the advantages of using pressure filtrations in place
of methods employing Soxhlet extractions. The types of samples
that require special care in handling and interpretation, and
This chapter not subject to U.S. copyright.

Published, 1982, American Chemical Society.

the precision o f the p r e s s u r e - f i l t r a t i o n method a r e a l s o

discussed. No attempt i s made t o compare pressure f i l t r a t i o n
with any "standard" Soxhlet method used by various
laboratories. The comparisons between room-temperature
pressure filtrations and room-temperature continuous
e x t r a c t i o n s were made only t o determine r e l a t i v e extraction
efficiencies.
Experimental
All experiments were carried out using the

pressure-filtration apparatus (Figure 1) and the
S o x h l e t - e x t r a c t i o n apparatus ( F i g u r e 2 ) . The s o l v e n t s used f o r
t h i s study were t e t r a h y d r o f u r a n (THF) and cyclohexane. The

v e h i c l e s used were a f i l t e r e d Koppers creosote o i l (b.p.
0
250-410 C) and SRC Heavy Distillate recycle o i l (b.p.
275-540°C). The c o a l s (Table I ) used were Kentucky 9/14,
C o l o n i a l Mine (-250 t o +325 mesh); and I l l i n o i s #6, Burning
S t a r Mine (-100 mesh). Both c o a l s were vacuum d r i e d .
Pressure F i l t r a t i o n Apparatus and Procedure. The two most

important components o f the p r e s s u r e - f i l t r a t i o n apparatus a r e
r e s e r v o i r R, a Whitey 1000-mL s t a i n l e s s s t e e l sample c y l i n d e r ,
and h o l d e r F, a 100-mL M i l l i p o r e pressure f i l t e r / h o l d e r . A
weighing pan c o n t a i n i n g a M i l l i p o r e T e f l o n f i l t e r and a T e f l o n
0 - r i n g was weighed. Most f i l t r a t i o n s were done with a
10-micron t e f l o n f i l t e r , which was adequate f o r removal o f
i n s o l u b l e s o l i d s from the suspension. The lower c o l l a r #5 o f
the M i l l i p o r e f i l t r a t i o n apparatus F was unscrewed, the T e f l o n
f i l t e r and 0 - r i n g were f i t t e d i n t o p l a c e , and c o l l a r #5 was put
back on. A r e p r e s e n t a t i v e sample weighing 5-7 grams was
removed from the r e a c t i o n s l u r r y and added t o a tared Pyrex
30-mL o r 90-mL weighing b o t t l e with a ground g l a s s l i d . The
sample was then d i l u t e d with solvent and mixed by s t i r r i n g w i t h
a g l a s s rod. Approximately 30 mL o f f r e s h s o l v e n t was added t o
apparatus F t o d i l u t e the s o l u t i o n / s u s p e n s i o n d u r i n g a d d i t i o n .
The sample was then added by washing out the weighing b o t t l e ,
and the f i l t r a t i o n h o l d e r was f i l l e d t o a t o t a l volume o f
approximately 100 mL.
L i d #4 and quickconnect #3 were attached. Quickconnect #2
was disconnected and 400 mL o f solvent was added t o the
s t a i n l e s s s t e e l sample c y l i n d e r ( R ) . Quick-connect #2 was
reconnected and two-way v a l v e #1 was turned to p r e s s u r i z e the
system t o approximately 40 p s i g with n i t r o g e n . The flow r a t e ,
approximately 35-45 mL/min, was c o n t r o l l e d a t the v a l v e ,
allowing a fine stream o f f i l t r a t e t o form. Once the
e x t r a c t i o n / f i l t r a t i o n was complete (13-15 min), n i t r o g e n was
used to blow the r e s i d u e dry f o r 1-2 minutes. The v a l v e used
to pressurize the apparatus was turned o f f and the

11. υ τ ζ ET AL. Solvent Analysis Using Pressure Filtration 227
Figure 2. Reduced-pressure, room temperature Soxhlet-extraction apparatus.

Table I . Analyses o f Coal

Kentucky 9/14, I l l i n o i s #6,

C o l o n i a l Mine Burning S t a r Mine
Proximate A n a l y s i s
(Wt* $, moisture f r e e )
V o l a t i l e Matter 39.0 39.7

Fixed Carbon 51.7 48.9
Ash 9.3 11.3
Ultimate A n a l y s i s
(Wt. %, moisture f r e e )
Hydrogen 4.9 4.7

Carbon 72.1 69.8
Nitrogen 1.5 1.2
Sulfur 3.4 3.1
Oxygen (ind.) 8.8 9.9
Ash 9.3 11.3

the solvent may be l a r g e r than those obtained from a room-

temperature e x t r a c t i o n , because the solvent may be able t o d i s
solve more of the sample at higher temperatures. Since p r e s
sure f i l t r a t i o n s were conducted a t room temperature, a meaning
ful comparison o f data could best be made i f Soxhlet
e x t r a c t i o n s were a l s o conducted a t room temperature* This
r e q u i r e d Soxhlet e x t r a c t i o n a t reduced pressures ( F i g u r e 2 ) . A
Sargent-Welch "Ser Vac" pump, used with a simple manometer and
Hoke " M i l l i - M i t e " needle v a l v e , was used t o maintain pressures
n
o f 9-12 mm Hg. Trap #1 was cooled by a Neslab U C o o l "
immersion c o o l e r a t -5°C i n an ethylene g l y c o l bath. Trap #2
was cooled a t -30°C wi*h a Neslab temperature-controlled Cryo
Cool CC-80 I I i n an ethylene g l y c o l bath. The condenser, u s i n g

ethylene g l y c o l , was a t 5°C f o r cyclohexane e x t r a c t i o n s and a t
-10° t o -20°C f o r THF e x t r a c t i o n s u s i n g a Lauda K-4/R r e f r i
gerated c i r c u l a t o r . Trap #1 was a simple vapor t r a p , but t r a p
#2 was a f i l t e r i n g f l a s k t o accommodate a l a r g e r volume o f
escaping vapor due t o the v o l a t i l e nature o f s o l v e n t s . The
e x t r a c t i o n solvent was s t i r r e d and warmed i n a 1 o r 2 l i t e r
round bottomed f l a s k u s i n g a Corning Combo hot ρlate/stirrer.
The water bath was kept a t 25°-30°C
Soxhlet e x t r a c t i o n s were u s u a l l y c a r r i e d out on r e a c t i o n
s l u r r i e s weighing 100 t o 150 grams t o allow s u f f i c i e n t m a t e r i a l
f o r product i s o l a t i o n , c h a r a c t e r i z a t i o n , and mass balances.
The 100-150 g sample was d i l u t e d i n 600-700 mL o f s o l v e n t , the
suspension s t i r r e d f o r 15 minutes and then f i l t e r e d through a
p r e d r i e d c e l l u l o s e thimble. The f i l t r a t e was then pressure-
filtered through a 5-micron filter t o remove any s m a l l
p a r t i c l e s t h a t may have passed through the thimble. The
r e s i d u e was then e x t r a c t e d u n t i l the f i l t r a t e i n the Soxhlet
e x t r a c t o r was n e a r l y c o l o r l e s s (2-5 days). The thimble, with
r e s i d u e , was d r i e d i n a vacuum oven a t 100°C f o r a t l e a s t 4
hours, or u n t i l there was no f u r t h e r weight l o s s . The f i l t r a t e
was again p r e s s u r e - f i l t e r e d through a 5-micron f i l t e r , and the
weight o f f i l t e r e d s o l i d was added t o the r e s i d u e weight a f t e r
drying. As i n pressure f i l t r a t i o n , the conversion t o s o l u b l e
m a t e r i a l was based on the r e s i d u e weight and the weight o f the
c o a l i n the sample.
Measurements of P r e c i s i o n . Experiments to measure

p r e c i s i o n were done on a c o a l - o i l s l u r r y t r e a t e d a t 440°C u s i n g
e i t h e r Koppers creosote o i l o r SRC Heavy D i s t i l l a t e r e c y c l e
solvent as a v e h i c l e . The c o a l - o i l s l u r r i e s were r e a c t e d i n a
1 - l i t e r continuously s t i r r e d tank r e a c t o r (CSTR) using 25 wt %
o f I l l i n o i s #6 Coal (Burning Star Mine), 2000 p s i g hydrogen,
and a s l u r r y feed r a t e o f 524 mL/hr with Koppers creosote o i l
and 414 mL/hr with SRC HD r e c y c l e s o l v e n t . Experiments were
a l s o done on a c o a l - o i l s l u r r y t r e a t e d a t 250°C f o r 15 minutes
u s i n g Koppers creosote o i l as a v e h i c l e . Reacted coal-oil

d e p r e s s u r i z a t i o n v a l v e , on two-way v a l v e #1, was opened. Lower

c o l l a r #5 was unscrewed; the T e f l o n f i l t e r with r e s i d u e and
T e f l o n O-ring were taken out, put into their appropriate
weighing pan, and d r i e d under a vacuum a t 100°C f o r 1 hour and
then immediately weighed.
Modified Pressure Filtration Procedure. A modified

procedure t o determine cyclohexane solubility of reaction
s l u r r i e s having high to moderate s o l i d s content r e q u i r e d the
use o f some THF. A 5-7 g r e a c t i o n s l u r r y sample was d i l u t e d
with approximately 25 mL o f THF; the mixture was s t i r r e d and
t r a n s f e r r e d to the f i l t r a t i o n holder c o n t a i n i n g 30 mL o f THF,
and the normal f i l t r a t i o n procedure was c a r r i e d out. The

r e s i d u e was removed, d r i e d , and weighed.
The THF f i l t r a t e , which a l s o c o n t a i n s cyclohexane s o l u b l e
v e h i c l e , was concentrated by roto-évaporâtion t o remove the
THF, 5 mL o f THF was added back to the s l u r r y , and t h i s THF
s l u r r y was dripped i n t o 150 mL o f s t i r r e d cyclohexane. The
flask that contained the concentrated THF solution was
sonicated w i t h 10-30 mL o f cyclohexane i n order to c l e a n i t
thoroughly. Since the f i l t e r / h o l d e r has a c a p a c i t y o f 100 mL,
only two-thirds o f the 150-mL cyclohexane suspension was added.
Approximately half of the cyclohexane suspension in the
f i l t e r / h o l d e r was p r e s s u r e - f i l t e r e d t o a l l o w a d d i t i o n o f the
remaining suspension. F i v e hundred mL o f cyclohexane was then
added to r e s e r v o i r R, and the sample was pressure-filtered.
The r e s i d u e was then removed, vacuum-dried, and weighed. Since
the THF-insoluble m a t e r i a l was a l s o cyclohexane-insoluble,
combining the weight o f the THF-insoluble r e s i d u e and the
i n s o l u b l e r e s i d u e obtained from the cyclohexane filtration
a l l o w s the c a l c u l a t i o n o f a cyclohexane s o l u b i l i t y v a l u e . The
r e s u l t s from the modified procedure on one sample w i l l thus
g i v e both THF and cyclohexane s o l u b i l i t y v a l u e s . The modified
p r e s s u r e - f i l t r a t i o n procedure takes 2 t o 2 1/2 hours.
The f o l l o w i n g equation was used to c a l c u l a t e conversion o f
c o a l to s o l u b l e products:
Wt. o f c o a l i n sample - r e s i d u e wt. = , s (3)

Wt. o f maf c o a l i n sample
I t should be understood t h a t the ash value does not represent

the a c t u a l amount o f m i n e r a l matter i n c o a l and the m i n e r a l
matter i n the r e s i d u e i s probably a reacted form o f m i n e r a l
matter. These slight d i f f e r e n c e s do not significantly
i n t e r f e r e with the "% s o l u b l e s " c a l c u l a t i o n .
Reduced-Pressure, Room-Temperature Soxhlet Extraction:

Apparatus and Procedure. S o l u b i l i t y v a l u e s obtained from a
t y p i c a l Soxhlet e x t r a c t i o n conducted near the b o i l i n g p o i n t o f

s l u r r i e s were heated t o 60°C i n order t o improve mixing, and 5 -

7 g a l i q u o t s were added t o g l a s s weighing b o t t l e s having ground
glass l i d s . I n d i v i d u a l samples were then analyzed by the
pressure f i l t r a t i o n method.
R e s u l t s and D i s c u s s i o n
Three d i f f e r e n t types o f m a t e r i a l were used t o study the

p r e s s u r e - f i l t r a t i o n method. Those were 1) Kentucky 9/14 c o a l ,
2) s l u r r i e s from low-temperature r e a c t i o n s (low conversion t o
s o l u b l e products, high s o l i d s c o n t e n t ) , and 3) s l u r r i e s from
high-temperature reactions (high conversion to soluble
products, low s o l i d s c o n t e n t ) . These p a r t i c u l a r types were

chosen because the f i r s t represents a material that i s
d i f f i c u l t t o e x t r a c t ; the second, a m a t e r i a l t h a t was d i f f i c u l t
to e x t r a c t with some s o l v e n t s and more e a s i l y e x t r a c t e d with
o t h e r s ; and the t h i r d , a m a t e r i a l that can be e x t r a c t e d w i t h
most s o l v e n t s .
Extraction o f Coal; A Study o f V a r i a b l e s . Approximately

10% o f Kentucky 9/14 c o a l i s soluble i n THF, u s i n g a
reduced-pressure Soxhlet e x t r a c t i o n . When e x t r a c t i n g c o a l , the
l e n g t h o f time that the s o l v e n t i s i n c o n t a c t w i t h the c o a l i s
very important ( 4 J . The s o l v e n t must be i n contact with the
c o a l p a r t i c l e long enough t o cause s w e l l i n g ( i f p o s s i b l e ) ,
penetrate the deepest pores, and then e x t r a c t and remove those
s o l u b l e components from w i t h i n the c o a l matrix ( 5 , 6 ) . With
Soxhlet e x t r a c t i o n s the contact time i s e s s e n t i a l l y u n l i m i t e d ,
and the sample i s e x t r a c t e d f o r as long a s necessary. Contact
time i n pressure f i l t r a t i o n s can be c o n t r o l l e d by decreasing
the flow r a t e o r by u s i n g more s o l v e n t . Table I I demonstrates
the v a r i a t i o n s i n THF s o l u b i l i t y t h a t occur when e x t r a c t i n g
Kentucky 9/14 c o a l by pressure f i l t r a t i o n .
The r e s u l t s obtained by v a r y i n g the f i l t r a t i o n time
demonstrate t h a t by i n c r e a s i n g c o n t a c t time, the s o l v e n t has a
greater opportunity t o i n t e r a c t with the c o a l sample and
e x t r a c t the s o l u b l e components. As can be seen i n Table I I ,
g r e a t e r amounts o f s o l v e n t which l e a d t o longer filtration
times, and smaller sample sizes, increase the amount o f
material extracted from c o a l . In f i l t r a t i o n s where the
f i l t r a t i o n times were 13-15 minutes, we were able t o o b t a i n an
extraction value approaching the 10$ value obtained by
room-temperature, reduced-pressure Soxhlet e x t r a c t i o n .
Results for Slurries Reacted at Low

Temperatures. Reduced-pressure Soxhlet extraction o f the
low-temperature-reaction sample, using THF, continued f o r
approximately 4 days. On the other hand, pressure filtration
o f d u p l i c a t e low-temperature samples took only 13-15 minutes.

Table I I . Pressure F i l t r a t i o n o f Kentucky 9/14 Coal
Amount o f Filtration
Weight c o a l * solvent time THF s o l u b l e s
Variable (g) (mL) (min) (*)
1.837 500 1 3.4

2.060 500 1 3.4
1.001 500 1 3.8

1.001 500 1 3.5
0.501 500 1 6.4

0.502 500 1 6.2
0.937 1000 13-14 7.0

0.931 1000 12-14 7.3
0.500 1000 14-15 8.6

0.506 1000 14-15 8.3
Filtration
1.001 500 1 3.8
1.001 500 1 3.5
1.002 500 4-5 5.5

1.008 500 4-5 5.8
1.002 500 7-8 6.2

1.005 500 7-8 5.8
0.937 1000 13-14 7.0

0.931 1000 13-14 7.3
1.029 1000 14-15»» 8.3
» -250 + 325 mesh

»» Coal sonicated i n 50 mL THF f o r 10 minutes before f i l t r a t i o n

The THF s o l u b i l i t y v a l u e s ( T a b l e I I I , SCT 65 & 69) d e m o n s t r a t e

t h a t t h e e x t r a c t i o n s u s i n g t h e p r e s s u r e - f i l t r a t i o n method a r e
thorough, and t h e s o l u b i l i t y values a r e comparable to the
c o n t i n u o u s S o x h l e t - e x t r a c t i o n method. When t h e same p r o c e d u r e
was p e r f o r m e d u s i n g c y c l o h e x a n e , a l a r g e d i f f e r e n c e was s e e n
between low-temperature Soxhlet-extraction values and t h e
pressure-filtration values.
The n e g a t i v e numbers f o r s o l u b i l i t y v a l u e s shown i n T a b l e
I I I show t h a t t h e r e s i d u e w e i g h t a f t e r r e a c t i o n i s g r e a t e r t h a n
the i n i t i a l weight o f c o a l i n the sample. (See % s o l u b l e s
equation i n experimental s e c t i o n . ) T h i s a p p a r e n t anomaly c a n
be a c c o u n t e d f o r b y some o f t h e v e h i c l e b e i n g i n c o r p o r a t e d i n t o
t h e c o a l m a t r i x d u r i n g r e a c t i o n a t 250°C ( 7 - 1 0 ) . Experiments
h a v e b e e n c o n d u c t e d t h a t show t h a t d u r i n g t h e s o l u b i l i z a t i o n o f
c o a l a t l o w t e m p e r a t u r e s some o f t h e n i t r o g e n r i c h c o m p o n e n t s
of the vehicle creosote o i l are chemically incorporated within
the c o a l matrix, a n d some o f t h e v e h i c l e may b e p h y s i c a l l y
entrapped or difficult to extract because of diffusional
l i m i t a t i o n s (JJ_). Creosote oil, is completely soluble in
cyclohexane, and i t s e x t r a c t i o n from t h e p a r t i a l l y disrupted
c o a l matrix should occur r e a d i l y , unless p h y s i c a l o r chemical
i n c o r p o r a t i o n has taken p l a c e . T h u s t h e n e g a t i v e v a l u e s f o r "$
solubles" are a r e s u l t o f the incorporation o f vehicle into the
residue. The t y p i c a l filtration times using cyclohexane in
p r e s s u r e f i l t r a t i o n may n o t a l l o w f o r a t h o r o u g h e x t r a c t i o n o f
high-solids content, coal-oil slurries a n d may r e q u i r e a
modified procedure as discussed below.
R e s u l t s f o r S l u r r i e s Reacted a t High Temperatures. Coal-

o i l s l u r r i e s r e a c t e d a t h i g h t e m p e r a t u r e s , where most m a t e r i a l s
a r e i n s o l u t i o n and t h e c o a l m a t r i x h a s been degraded, does n o t
necessitate the solvent swelling o f s o l i d c o a l p a r t i c l e s . The
r e s u l t s ( T a b l e I I I , SCT-83) compare t h e e f f e c t i v e n e s s o f b o t h
s o l v e n t s u s i n g p r e s s u r e f i l t r a t i o n and S o x h l e t e x t r a c t i o n . The
p r e s s u r e - f i l t r a t i o n r e s u l t s f o r b o t h c y c l o h e x a n e a n d THF a p p e a r
to be comparable to those using the Soxhlet-extraction
procedure.
M o d i f i e d Cyclohexane Pressure F i l t r a t i o n . Cyclohexane is

not an efficient solvent when extracting material from
low-temperature reaction slurries that include significant
amounts o f u n r e a c t e d c o a l . Since t h i s s o l v e n t does n o t have
the a b i l i t y t o swell the c o a l matrix, i t must g r a d u a l l y force
i t s way i n t o t h e p o r e s o f t h e r e a c t e d c o a l m a t r i x a n d s l o w l y
e x t r a c t the cyclohexane soluble m a t e r i a l . This requires a long
contact time and p r e s s u r e filtration does not s a t i s f y this
requirement. S o x h l e t e x t r a c t i o n w i t h cyclohexane r e q u i r e d 3-4
d a y s f o r t h e f i l t r a t e t o become e s s e n t i a l l y c o l o r l e s s . When
using cyclohexane as a solvent, the d i s p a r i t y between t h e

4^
Table I I I . E x t r a c t i o n o f S l u r r i e s Reacted a t High & Low Temperatures
% Solubles
Reaction Cyclohexane
Wt. Ratio Temp. Time THF E x t r a c t i o n Extraction
Run # Coal Coal:Oil °C min. Soxhlet Pressure Soxhlet Pressure
SCT- Filtration Filtration
65 KY 9/14 1:5 250 15 18.7 18.8 -5.3 -30
69 KY 9/14 1:5 250 15 18.1 17.9 -4.3 -32

IL #6 M50 40 90.2 88.8 Ο
83 1:3 28.5 34.3

ι
I
Η
11. υτζ ET AL. Solvent Analysis Using Pressure Filtration 235
Soxhlet and the p r e s s u r e - f i l t r a t i o n e x t r a c t i o n v a l u e s obtained

with coal-derived products from low-temperature reactions
necessitated the development of an alternate
p r e s s u r e - f i l t r a t i o n procedure. I f cyclohexane cannot s w e l l and
penetrate the unreacted c o a l i n the reacted s l u r r y adequately,
then THF can be used t o s w e l l and penetrate the unreacted c o a l .
A l l the THF s o l u b l e m a t e r i a l (which i n c l u d e s the cyclohexane
soluble vehicle) can then be efficiently extracted and
separated from the unreacted c o a l matrix.
The r e s u l t s u s i n g the modified procedure are shown i n
Table IV. The p r e s s u r e - f i l t r a t i o n v a l u e s i n SCT-87 compare
w e l l with the S o x h l e t - e x t r a c t i o n v a l u e s from SCT 65 and 69. In
other experiments (SCT 91 and 95), p a r t o f the reacted s l u r r y
was used to perform solvent classification by pressure

f i l t r a t i o n and the remainder f o r s o l v e n t c l a s s i f i c a t i o n by
Soxhlet e x t r a c t i o n . Agreement o f cyclohexane s o l u b i l i t y v a l u e s
w i t h i n 3-6$ i s a c o n s i d e r a b l e improvement over the d i f f e r e n c e
of approximately 25% obtained with the standard
p r e s s u r e - f i l t r a t i o n procedure, but f u r t h e r improvements i n the
technique are being sought. The s o l u b i l i t y v a l u e s f o r the two
methods compare f a i r l y well, c o n s i d e r i n g that these "high
solids content" slurries are difficult to extract with
cyclohexane.
P r e c i s i o n o f Pressure F i l t r a t i o n . Pressure f i l t r a t i o n can

s o l u b i l i z e as much m a t e r i a l from c o a l - d e r i v e d products as a
room-temperature Soxhlet e x t r a c t i o n , but i t a l s o must be
p r e c i s e i n order t o be a v i a b l e method ( 1 , 2 ) . Measurements o f
p r e c i s i o n are shown i n Table V and were made on samples
obtained both from high-temperature reactions using either
creosote o i l or SRC HD r e c y c l e o i l as a v e h i c l e , and from
low-temperature r e a c t i o n s u s i n g c r e o s o t e o i l as a v e h i c l e . The
standard d e v i a t i o n s and r e l a t i v e standard d e v i a t i o n s from the
r e s u l t s f o r the high-temperature s l u r r y products demonstrate
t h a t the p r e s s u r e - f i l t r a t i o n method has the necessary p r e c i s i o n
t o be a v i a b l e method. Values f o r samples from low-temperature
r e a c t i o n s show that THF f i l t r a t i o n s provide the necessary
p r e c i s i o n , but the p r e c i s i o n f o r the cyclohexane f i l t r a t i o n s
should be improved.
In summary, the p r e s s u r e - f i l t r a t i o n technique i s a u s e f u l
and precise analytical tool in performing the solvent
c l a s s i f i c a t i o n o f c e r t a i n c o a l - d e r i v e d products. The method
w i l l not only g i v e meaningful r e s u l t s comparable t o continuous,
room-temperature Soxhlet e x t r a c t i o n s but, most importantly,
save many hours i n the l a b o r a t o r y . We have found i t r a p i d
enough to monitor continuous o p e r a t i o n s . With c o a l - o i l s l u r r y
reaction mixtures obtained from high-temperature
c o a l - l i q u e f a c t i o n r e a c t i o n s , the s o l v e n t c l a s s i f i c a t i o n can be
completed i n 1 1/2 t o 2 hours.

Table IV. Comparisons Using the Modified Cyclohexane Pressure

F i l t r a t i o n f o r S l u r r i e s Reacted a t Low Temperatures
M o d i f i e d cyclohexane Cyclohexane
Run # pressure f i l t r a t i o n s Soxhlet e x t r a c t i o n s
SCT (% s o l u b l e s ) (% s o l u b l e s )
65 -5.3
69 -4.3
87* -6.8
91 -5.7 -8.9
95 -9.8 -4.1
* Value based on 5 r e p l i c a t e s .
Table V. Standard D e v i a t i o n s and R e l a t i v e Standard D e v i a t i o n s

f o r Pressure F i l t r a t i o n s of C o a l - O i l S l u r r i e s
Standard D e v i a t i o n ( $ ) * /
R e l a t i v e Standard D e v i a t i o n
Vehicle THF Cyclohexane
High Creosote o i l 0.10/0.005 0.26/0.004
Temperature
Reactions SRC HD r e c y c l e 0.12/0.005 0.61/0.007
Low
Temperature Creosote o i l 0.29/0.003

1.1**/0.012
Reactions
* 5-7 R e p l i c a t e s f o r each s e t .
** Only 4 r e p l i c a t e s used.

Acknowledgement
We thank Dr. Richard T i s c h e r f o r h i s a s s i s t a n c e and

expertise. We a l s o wish t o thank Mr. Gary S t e i g e l f o r
supplying us with samples from the high-temperature continuous
reactor.
Reference i n this report t o any s p e c i f i c commercial

product, process, o r s e r v i c e i s t o f a c i l i t a t e understanding and
does not n e c e s s a r i l y imply i t s endorsement or f a v o r i n g by the
united States Department o f Energy.
Literature Cited
1. Mima, M. J.; Schultz, H.; McKinstry, W. E. "Methods for

the Determination of Benzene Insolubles, Asphaltenes, and
Oils in Coal-Derived Liquids", PERC/RI 76/6, September
1976. .
2. Schultz, H.; Mima, M. J. "Comparisons of Methods for the
Determination of Asphaltenes, Oils, and Insolubles. Part
1 - A Coal-Derived Liquid." PETC.TR-80/3, May 1980.
3. Bertolacini, R. J.; Gutberlet, L. G; Kim, D. K.; Robinson,
Κ. K. "Catalyst Development for Coal Liquefaction", EPRI
Report AF-574, November 1977.
4. Dryden, I. G. C. Fuel 1951, 30, 145-158.
5. Kiebler, M. W. "Chemistry of Coal utilization", Wiley and
Sons; New York, 1945; 715-760.
6. Marzec, Α.; Juzwa, M.; Betlej, K.; Sobkowiak, M. Fuel
Proc. Technol. 1979, 2, 35-44.
7. Grens, Ε. Α. II; Hershkowitz F.; Holten, R. R.; Shinn, J.
H.; Vermeulen T. Ind. Eng. Chem., Process. Des. Dev.
1980, 19, 396-401.
8. Wright, C. H.; Schmalzer, D. K. "Coal Liquefaction
Preheater Studies", U. S. Department of Energy Project
Reviews Meeting, Section 4, March 1979.
9. Bickel, T. C.; Stohl, F. V.; Thomas, M. G. "Coal
Liquefaction Process Research", Sandia National
Laboratories, Quarterly Report, April - June 1980.
10. Longanbach, J. R.; Droege, J. W.; Chauhan, S. P. "Short
Residence Time Coal Liquefaction", EPRI Report AF 780,
Battelle Columbus Laboratories, June 1978.
11. Utz, B. R.; Narain, N. K.; Appell, H. R. U.S. Department
of Energy, Pittsburgh Energy Technology Center, 1980,
private communications.

12
Scanning Electron Miscroscope-Based Automated
Image Analysis (SEM-AIA) and Mössbauer
Spectroscopy
Quantitative Characterization of Coal Minerals
F. E . HUGGINS, G. P. H U F F M A N , and R. J. L E E
U.S. Steel Research, Monroeville, PA 15146
Many coal-utilization problems derive from the

mineral matter in coal and require for their solution

quantitative determinations of this component. For
such determinations, we use automated image analysis
(ΑΙΑ) in the scanning electron microscope (SEM-AIA)
57
and Fe Mössbauer spectroscopy. SEM-AIA involves
measurement of the areas of typically 1024 particles
in a polished coal section and classification of each
particle into one of 29 categories on the basis of its
energy-dispersive x-ray spectrum. From such data, the
relative weight percentages of the different minerals
are derived. Mössbauer spectroscopy is used for
classifying certain iron-bearing categories that could
arise from two or more distinct minerals with identi-
cal energy-dispersive spectra. Because these
techniques are used directly on the coal, provide
information on mineral particle size, and are more
sensitive to minor constituents than other techniques,
they compare well with other techniques such as
Fourier transform infrared spectroscopy and x-ray
diffraction commonly used for quantitative coal miner-
alogies.
T h e r e i s c u r r e n t l y much i n t e r e s t i n t h e m i n e r a l m a t t e r
i n c l u d e d i n c o a l and t h e b e h a v i o r and p r o p e r t i e s o f such m a t t e r
during c o a l - u t i l i z a t i o n technologies. F o r t h e most p a r t , t h e
mineral matter has d e l e t e r i o u s e f f e c t s d u r i n g u t i l i z a t i o n , and
c o n s i d e r a b l e a t t e n t i o n must o f t e n be g i v e n t o m i n i m i z i n g p r o b -
lems a r i s i n g f r o m t h i s i n o r g a n i c , n o n c o m b u s t i b l e component i n
coal. On t h e p o s i t i v e s i d e , h o w e v e r , t h e m i n e r a l m a t t e r
appears t o have d e s i r a b l e c a t a l y t i c p r o p e r t i e s i n c e r t a i n c o a l -
c o n v e r s i o n t e c h n o l o g i e s a n d c a n be u s e d b y g e o l o g i s t s i n
exploration t o delineate c o a l - q u a l i t y trends within a c o a l
deposit. A l t h o u g h some m i n e r a l o g i c a l i n f o r m a t i o n c a n be
i n f e r r e d from standard c h e m i c a l and other a n a l y s e s o f t h e c o a l
and t h e a s h r e m a i n i n g a f t e r c o n t r o l l e d c o m b u s t i o n , a f u l l
0097-6156/82/0205-0239$06.00/0

u n d e r s t a n d i n g o f m i n e r a l - r e l a t e d phenomena i n c o a l u t i l i z a t i o n
r e q u i r e s a d e t a i l e d knowledge o f the m i n e r a l o g y o f t h e c o a l .
A number o f t e c h n i q u e s h a v e b e e n u s e d t o d e t e r m i n e m i n e r -
a l o g i e s of c o a l . As d i s c u s s e d i n a r e c e n t r e v i e w (J_), t h e m o s t
common t e c h n i q u e s a r e x - r a y d i f f r a c t i o n , i n f r a r e d s p e c t r o s c o p y ,
o p t i c a l m i c r o s c o p y , and e l e c t r o n m i c r o s c o p y . X-ray d i f f r a c t i o n
a n d i n f r a r e d s p e c t r o s c o p y c a n be c o n s i d e r e d " b u l k " methods
b e c a u s e t h e y a r e g e n e r a l l y b e s t p e r f o r m e d on t h e m i n e r a l - m a t t e r
c o n c e n t r a t e o b t a i n e d by r e m o v a l o f t h e m a c é r a i s by l o w - t e m p e r a -
t u r e a s h i n g (2). The m i c r o s c o p e methods c a n be c o n s i d e r e d
" p a r t i c u l a t e " methods b e c a u s e m i n e r a l g r a i n s i n t h e c o a l a r e
s i z e d and c l a s s i f i e d i n d i v i d u a l l y . T h e s e m i c r o s c o p e methods
a r e u s u a l l y u s e d w i t h o u t s e p a r a t i o n o f m i n e r a l s and m a c é r a i s
b e c a u s e the c o a l macérais can s e r v e as a b a c k g r o u n d m a t r i x t o
s e p a r a t e m i n e r a l p a r t i c l e s and t o p r o v i d e c o n t r a s t f o r t h e
d i m e n s i o n a l measurement o f t h e p a r t i c l e .
A l t h o u g h p a r t i c u l a t e methods a r e p o t e n t i a l l y more i n f o r m a -
t i v e t h a n b u l k methods b e c a u s e o f t h e e x t r a i n f o r m a t i o n
o b t a i n e d on p a r t i c l e s i z e , t h e i r a p p l i c a t i o n i n c o a l m i n e r a l o g y
has been r e l a t i v e l y l i m i t e d . The m a i n r e a s o n f o r t h i s h a s b e e n
t h e l a c k o f a u t o m a t i o n , as s u c h m i c r o s c o p i c m e a s u r e m e n t s a r e
t i m e - c o n s u m i n g and t e d i o u s i f s u f f i c i e n t d a t a h a v e t o be
generated manually. R e c e n t l y , however, t h e a p p l i c a t i o n o f
m i c r o c o m p u t e r s and i m a g e - a n a l y s i s s y s t e m s t o m i c r o s c o p y has
p r o g r e s s e d t o t h e e x t e n t t h a t most o f t h e o p e r a t i o n , d a t a
c o l l e c t i o n , and a n a l y s i s c a n now be done a u t o m a t i c a l l y * A
number o f r e p o r t s o f s u c h a u t o m a t e d m i c r o s c o p e t e c h n i q u e s u s e d
i n c o a l r e s e a r c h have appeared r e c e n t l y i n the l i t e r a t u r e
(2-8).
I n t h i s p a p e r we d e s c r i b e t h e u s e o f a s c a n n i n g e l e c t r o n
m i c r o s c o p e (SEM) e q u i p p e d w i t h a u t o m a t i c - i m a g e - a n a l y s i s (ΑΙΑ)
c a p a b i l i t y f o r the determination of c o a l m i n e r a l o g i e s . Because
one o f t h e m a i n l i m i t a t i o n s o f t h e SEM-AIA t e c h n i q u e i s i t s
5 7
i n a b i l i t y to d i s t i n g u i s h the v a r i o u s i r o n - b e a r i n g minerals, Fe
MiJssbauer s p e c t r o s c o p y i s u s e d t o s u p p l e m e n t d a t a f r o m SEM-AIA
with respect to iron-bearing minerals. The c o m b i n a t i o n o f
t h e s e two t e c h n i q u e s u s u a l l y p r o v i d e s a d e t a i l e d , q u a n t i t a t i v e
c h a r a c t e r i z a t i o n of the m i n e r a l s i n c o a l .
Experimental Methods
Sample P r e p a r a t i o n . Our s a m p l e - p r é p a r â t i o n p r o c e d u r e s f o r
SEM-AIA on c o a l h a v e b e e n m o d i f i e d f r o m t h o s e d e s c r i b e d e a r l i e r
{8). A p p r o x i m a t e l y 7 g o f -60 mesh c o a l i s m i x e d i n t o a s l u r r y
w i t h a b o u t 2 g o f an epoxy p l a s t i c and p r e s s e d i n a s t a i n l e s s -
s t e e l d i e t o f o r m a c y l i n d r i c a l s a m p l e p e l l e t 1.6 cm i n
d i a m e t e r and 3 t o 4 cm i n l e n g t h . A s l i c e , a p p r o x i m a t e l y 1 cm
t h i c k , i s c u t f r o m t h e p e l l e t w i t h a d i a m o n d w a f e r i n g saw a t a n

12. HUGGINS ET AL. SEM-AIA and Môssbauer Spectroscopy 241
a n g l e o f 54.7° t o t h e a x i s o f t h e c y l i n d e r . T h i s angle of cut

h a s b e e n f o u n d (9) t o m i n i m i z e b i a s t h a t m i g h t a r i s e f r o m
p o s s i b l e p r e f e r r e d o r i e n t a t i o n o f c l a y m i n e r a l s due t o c o m p r e s -
s i o n of the coal/epoxy mixture. The r e s u l t i n g o v a l - s h a p e d
p e l l e t i s p l a c e d f a c e down i n a o n e - i n c h b a k é l i t e r i n g f o r m a n d
s u r r o u n d e d by more e p o x y t o f o r m a c y l i n d r i c a l p e l l e t t h a t f i t s
c o n v e n i e n t l y i n t o an a u t o m a t i c p o l i s h i n g m a c h i n e . The
c o a l / e p o x y p e l l e t i s then ground, p a r a l l e l t o the c u t f a c e ,
w i t h g r i d s impregnated w i t h c u b i c boron n i t r i d e and f i n a l l y
p o l i s h e d w i t h 3 um and 1 um d i a m o n d p a s t e s .
The u s e o f c u b i c b o r o n n i t r i d e a n d d i a m o n d p a s t e f o r
g r i n d i n g and p o l i s h i n g m i n i m i z e s c o n t a m i n a t i o n by m a t e r i a l s
t h a t c a n be m i s t a k e n f o r m i n e r a l s i n t h e SEM a n a l y s i s . The
sample p e l l e t i s t h e n c u t p a r a l l e l t o t h e p o l i s h e d f a c e t o
r e d u c e i t s h e i g h t t o a b o u t 0.6 cm, mounted on an a l u m i n u m s t u b ,
a n d c a r b o n - c o a t e d f o r u s e i n t h e SEM.
S a m p l e - p r e p a r a t i o n p r o c e d u r e s f o r Mô'ssbauer s p e c t r o s c o p y
are r e l a t i v e l y simple. D e p e n d i n g on t h e i r o n c o n t e n t o f t h e
c o a l , 0.3 t o 1.0 g o f v e r y f i n e l y c r u s h e d (-400 mesh) c o a l i s
p l a c e d i n a p l e x i g l a s s c o m p r e s s i o n h o l d e r o f 1.3-cm-diameter.
The f i l l e d h o l d e r i s t h e n p l a c e d i n a m e t a l l i c s h i e l d w i t h a
1.3 cm d i a m e t e r o p e n i n g t h a t e n a b l e s t h e sample t o be e x p o s e d
t o t h e γ-ray beam f r o m t h e Mo'ssbauer s o u r c e . Identical proce
dures w i t h a d i f f e r e n t m e t a l l i c s h i e l d arrangement i n s i d e a
vacuum s h r o u d a r e u s e d f o r c r y o g e n i c e x p e r i m e n t s .
SEM A u t o m a t e d Image A n a l y s i s . SEM-AIA h a s b e e n u s e d i n

our l a b o r a t o r y f o r a b r o a d range o f a p p l i c a t i o n s , from c h a r a c
t e r i z a t i o n o f a i r - p o l l u t i o n samples t o measurement o f
inclusions i n steel. In t h i s paper, only i t s application to
m i n e r a l s i n c o a l w i l l be d e s c r i b e d , as more g e n e r a l d e s c r i p
t i o n s o f t h e r a n g e and p o t e n t i a l o f SEM-AIA h a v e b e e n g i v e n
elsewhere (10,11).
SEM-AIA o f c o a l u s e s two d i s t i n c t s i g n a l s e m i t t e d f r o m t h e
s a m p l e i n r e s p o n s e t o i r r a d i a t i o n by t h e 20-kV e l e c t r o n beam.
One o f t h e s e s i g n a l s i s t h e b a c k - s c a t t e r e d - e l e c t r o n (BSE)
r a d i a t i o n , which p r o v i d e s e x c e l l e n t c o n t r a s t between m i n e r a l
p a r t i c l e s and t h e b a c k g r o u n d m a t r i x o f c o a l m a c é r a i s and e p o x y
( F i g u r e 1); i t i s u s e d t o l o c a t e t h e m i n e r a l p a r t i c l e s a n d
measure t h e i r a r e a . A f o u r - c h a n n e l BSE d e t e c t i o n s y s t e m i s
used t o c o l l e c t t h i s r a d i a t i o n because i t i n c r e a s e s t h e
c o n t r a s t and s i g n a l - t o - n o i s e r a t i o a n d m i n i m i z e s g e o m e t r i c
v a r i a t i o n i n the s i g n a l . The o t h e r s i g n a l u s e d i s t h e
c h a r a c t e r i s t i c x-ray spectrum a r i s i n g from the elements i n the
mineral p a r t i c l e . T h e s e x - r a y s a r e c o l l e c t e d by means o f a n
e n e r g y - d i s p e r s i v e x - r a y s p e c t r o m e t e r and a r e u s e d t o t y p e t h e
mineral p a r t i c l e .

The SEM-AIA s y s t e m c o n s i s t s o f a n SEM (ETEC A u t o s c a n )

i n t e r f a c e d by means o f two m i n i c o m p u t e r s t o a b e a m - c o n t r o l unit
(LeMont S c i e n t i f i c ) and an e n e r g y - d i s p e r s i v e x - r a y a n a l y z e r
unit (Tracor Northern). A d i a g r a m o f t h e s y s t e m i s shown
s c h e m a t i c a l l y i n F i g u r e 2. T h e b e a m - c o n t r o l u n i t c o n s i s t s o f a
m i n i c o m p u t e r - c o n t r o l l e d d i g i t a l scan g e n e r a t o r and an a n a l o g
comparator. T h e d i g i t a l s c a n g e n e r a t o r moves t h e e l e c t r o n beam
i n a s p e c i f i c p a t t e r n through t h e f i e l d o f view t o l o c a t e p a r
t i c l e s a n d t o measure t h e i r a r e a .
To l o c a t e p a r t i c l e s , t h e beam i s s t e p p e d a c r o s s t h e s a m p l e
i n a c o a r s e g r i d p a t t e r n , w i t h t y p i c a l l y 300 χ 300 g r i d p o i n t s
c o v e r i n g the f i e l d o f view. A t each p o i n t , t h e i n t e n s i t y o f

t h e BSE r a d i a t i o n i s s a m p l e d , a n d t h e m i n i c o m p u t e r d e c i d e s
w h e t h e r t h e beam i s on o r o f f a m i n e r a l p a r t i c l e . The i n t e n
s i t y l e v e l o f t h e BSE r a d i a t i o n t h a t d i s c r i m i n a t e s b e t w e e n
m i n e r a l and background i s s e t manually a t t h e b e g i n n i n g o f each
f i e l d o f view u s i n g t h e a n a l o g comparator. Once a p a r t i c l e i s
l o c a t e d , t h e g r i d d e n s i t y i s i n c r e a s e d t o 2048 χ 2048 g r i d
p o i n t s t o i n c r e a s e t h e p r e c i s i o n o f t h e a r e a measurement o f t h e
particle. The s i z e a n d s h a p e o f t h e p a r t i c l e a r e d e t e r m i n e d
from t h e c o n t i g u o u s group o f p o i n t s above t h e a n a l o g comparator
l e v e l (11). The b e a m - c o n t r o l u n i t t h e n p o s i t i o n s t h e e l e c t r o n
beam a t t h e c e n t e r o f t h e p a r t i c l e a n d c o n t r o l o f t h e o p e r a t i o n
i s t r a n s f e r r e d t o the minicomputer i n t h e e n e r g y - d i s p e r s i v e
x-ray u n i t .
The e n e r g y - d i s p e r s i v e x - r a y s p e c t r u m o f t h e p a r t i c l e i s
c o l l e c t e d f o r two t o t h r e e s e c o n d s i n a m u l t i c h a n n e l a n a l y z e r ,
a n d t h e p e r c e n t a g e s o f x - r a y s f r o m 11 p r i n c i p a l e l e m e n t s i n
c o a l a s h (Na, Mg, A l , S i , P, S, C l , K, C a , T i , F e ) a r e s t o r e d
i n t h e m i n i c o m p u t e r memory a l o n g w i t h d i m e n s i o n a l a n d l o c a -
t i o n a l d a t a a b o u t t h e p a r t i c l e t r a n s f e r r e d f r o m t h e beam-
c o n t r o l minicomputer while t h e x-rays a r e being recorded. The
x - r a y s p e c t r u m i s c l a s s i f i e d by means o f a s o r t i n g r o u t i n e i n t o
one o f 29 c o m p o s i t i o n a l c a t e g o r i e s . C o n t r o l i s t h e n r e t u r n e d
to t h e beam-control minicomputer and t h e next p a r t i c l e i s
s o u g h t by t h e b e a m - c o n t r o l unit.
The a n a l y s i s i s t e r m i n a t e d o n c e 1023 p a r t i c l e s h a v e b e e n
l o c a t e d , measured, and c l a s s i f i e d . However, t o g e t a good
r e p r e s e n t a t i o n o f p a r t i c l e s a c r o s s a broad s i z e range, a l i m i t
i s p u t on t h e number o f p a r t i c l e s m e a s u r e d i n v a r i o u s s i z e
r a n g e s ( T a b l e I ) . The a r e a o f t h e s a m p l e s c a n n e d t o c o l l e c t
t h e r e q u i r e d number o f p a r t i c l e s i n e a c h s i z e r a n g e i s
recorded. The r a t i o (Mj) o f t h e a r e a s c a n n e d i n t h e t o p s i z e
range t o t h a t i n t h e j t h s i z e range i s used as a w e i g h t i n g
f a c t o r i n the c a l c u l a t i o n of the weight percentages o f the
different minerals. The f o r m u l a f o r t h i s c a l c u l a t i o n i s based
on t h e a r e a o f t h e p a r t i c l e s o f a g i v e n t y p e , m u l t i p l i e d by t h e
d e n s i t y o f t h e m i n e r a l and t h e f a c t o r , Mj:

Figure 1. Secondary electron image (left) and inverted backscattered electron

(BSE, right) image of a polished sample of a bituminous coal (D seam, Colorado).
The minerals are black and the maceral epoxy background is light gray in the
inverted BSE image.
DUAL DISC UNIT

MINI DIGITAL SCAN
COMPUTER GENERATOR
TTY
τ DUAL
ANALOG ELECTRON
τ DISC
COMPARATOR DETECTION
Y
UNIT
MULTI
MINI CHANNEL X-RAY
COMPUTER ANALYZER DETECTION
HIGH SPEED
PRINTER
Figure 2. Schematic diagram of the SEM-AIA system.

Table I. Size-Range C l a s s e s m SEM-AIA o f C o a l
Maximum
Lower Upper Number o f
Class Limit (um) L i m i t ( un) Particles
1 10.0 50.0 300
2 5.0 10.0 200

3 2.5 5.0 175
4 1.0 2.5 175
5 0.2 1.0 173
Table II. SEM-AIA M i n e r a l Categories
Major* Accessory** Mixed"*"
Quartz Montmorillonite Pyrite/Jarosite

Kaolinite Chlorite Silicate/Sulfur
IIlite Gypsum Silicate/Pyrite
Pyrite Jarosite Mixed s u l f a t e / s u l f i d e
Fe-rich Fe S u l f a t e Mixed Carbonate
Calcite Halite Mixed C h l o r i d e
Sylvite
Mixed S i l i c a t e s Dolomite Trace element
Ankerite
Rutile Unknown
Apatite
Sulfur 2 spare
* U s u a l l y e a c h >3 wt% o f m i n e r a l m a t t e r a n d sum o f m a j o r

categories >90 wt % .
** U s u a l l y e a c h <3 wt % o f m i n e r a l m a t t e r a n d sum o f a c c e s s o r y
categories <5 wt % .
Sum o f m i x e d categories usually <10 wt %.

5 Nij / 29 5 Nij
wi = ioo p±y^Mjy^ Aijk/y^ ^ y ^ y ^

j=l k=l / i=l j=l k=l
where Wi i s t h e w e i g h t p e r c e n t a g e o f t h e i t h m i n e r a l ,
p i i s the d e n s i t y of the i t h m i n e r a l .
N i j i s t h e number o f p a r t i c l e s o f t y p e i i n t h e j t h
s i z e range.
Aijk i s the area of the kth p a r t i c l e of type i i n the
jth size range.
T h i s p r o c e d u r e and c a l c u l a t i o n y i e l d r e s u l t s o f much b e t t e r r e -
p r o d u c i b i l i t y t h a n t h e method f o l l o w e d e a r l i e r {6) of simply
m e a s u r i n g t h e f i r s t 1000 p a r t i c l e s e n c o u n t e r e d . The d e r i v e d
r e s u l t s on w e i g h t p e r c e n t a g e s and on t h e s i z e d i s t r i b u t i o n o f
t h e d i f f e r e n t m i n e r a l s a r e s t o r e d on f l o p p y d i s k e t t e s a l o n g
w i t h t h e o r i g i n a l d a t a on t h e i n d i v i d u a l p a r t i c l e s .
A s a r e s u l t o f e x p e r i m e n t s done t o t e s t t h e a c c u r a c y and
p r e c i s i o n o f SEM-AIA f o r c o a l m i n e r a l s ( 8 ) , i t was f o u n d t h a t
p y r i t e i s o v e r e s t i m a t e d by a b o u t o n e - t h i r d b e c a u s e i t s BSE c o n -
t r a s t i s much h i g h e r t h a n t h a t o f a l l o t h e r common c o a l
m i n e r a l s t h a t h a v e v e r y s i m i l a r BSE c o n t r a s t s . The w e i g h t
p e r c e n t a g e s f r o m SEM-AIA a r e a d j u s t e d f o r t h i s o v e r e s t i m â t i o n
and a l l d a t a r e p o r t e d i n t h i s paper a r e so a d j u s t e d .
The 29 c o m p o s i t i o n a l c a t e g o r i e s u s e d i n t h e s o r t i n g r o u -
t i n e c o n s i s t o f 18 i n d i v i d u a l m i n e r a l s / 7 m i x e d c a t e g o r i e s / a
t r a c e - e l e m e n t c a t e g o r y (most i n t e n s e p e a k i n t h e e n e r g y -
d i s p e r s i v e s p e c t r u m i s n o t one o f t h e 11 e l e m e n t s l i s t e d a b o v e )
and an unknown c a t e g o r y . T h e r e a r e a l s o two s p a r e c a t e g o r i e s
a v a i l a b l e f o r s p e c i a l u s e ; f o r example/ i n c e r t a i n l i g n i t e s
f r o m M o n t a n a , b a r i t e ( B a S 0 ) was a s i g n i f i c a n t (>5 wt%)
4 acces-
s o r y m i n e r a l a n d was i n c l u d e d i n t h e a n a l y s i s by s i m p l y
r e p r o g r a m m i n g t h e s o r t i n g r o u t i n e . The c a t e g o r i e s a r e l i s t e d
i n T a b l e I I ; t h e y and t h e s o r t i n g r o u t i n e h a v e b e e n d e s c r i b e d
i n d e t a i l elsewhere ·
57
Mffssbauer S p e c t r o s c o p y .
v Fe Mo'ssbauer s p e c t r o s c o p y o f
c o a l s and c o a l d e r i v a t i v e s i s y i e l d i n g much new i n f o r m a t i o n
a b o u t t h e i r o n m i n e r a l s i n c o a l and t h e i r b e h a v i o r d u r i n g c o a l
utilization. However/ i n t h i s p a p e r , o n l y i t s u s e t o s u p p l e -
ment SEM-AIA d a t a w i l l be d e t a i l e d a n d t h e i n t e r e s t e d r e a d e r i s
r e f e r r e d t o p u b l i s h e d r e p o r t s (12-17) d e s c r i b i n g t h e t h e o r y a n d
p r a c t i c e o f Mtfssbauer s p e c t r o s c o p y a n d i t s a p p l i c a t i o n t o a
b r o a d range o f c o a l s and c o a l p r o d u c t s .

Our Mtfssbauer t e c h n i q u e s / when u s e d s i m p l y t o s u p p l e m e n t

SEM-AIA o f a c o a l # are q u i t e standard. A l l measurements a r e
c o n d u c t e d i n t r a n s m i s s i o n mode/ w i t h t h e c o a l s a m p l e u s u a l l y a t
room t e m p e r a t u r e . Spectra are not o b t a i n e d r o u t i n e l y with the
sample a t c r y o g e n i c t e m p e r a t u r e s u n l e s s t h e c o a l i s w e a t h e r e d
o r u n u s u a l i n some o t h e r r e s p e c t . I n most c o a l s t h e d i f f e r e n t
m i n e r a l s each c o n t r i b u t e a quadrupole doublet/ c o n s i s t i n g of
two s i m i l a r p e a k s , t o t h e s p e c t r u m ( F i g u r e 3/ t o p ) . However/
i f the mineral i s m a g n e t i c a l l y ordered/ a six-peak p a t t e r n w i l l
be o b s e r v e d ( F i g u r e 3/ b o t t o m ) . D i f f e r e n t Môssbauer parameters
a r e d e r i v e d f r o m t h e p e a k p o s i t i o n s i n t h e s e two-peak o r s i x -
p e a k p a t t e r n s a n d t h e i r o n - b e a r i n g p h a s e c a n t h e n be i d e n t i f i e d
from the v a l u e s of these parameters.
The d i f f e r e n t i r o n - b e a r i n g m i n e r a l s t h a t we h a v e o b s e r v e d
i n Mtfssbauer s p e c t r a o f v a r i o u s U. S. c o a l s a r e l i s t e d i n
T a b l e III, a l o n g w i t h t h e i r Mtfssbauer p a r a m e t e r s . From e x a m i n -
a t i o n of t h i s table/ i t i s q u i t e obvious t h a t there are a
number o f d i f f e r e n t m i n e r a l s t h a t c o u l d g i v e r i s e i n SEM-AIA t o
F e - r i c h x - r a y s p e c t r a ( s i d e r i t e / i r o n m e t a l / h e m a t i t e / magne-
t i t e / g o e t h i t e / o t h e r o x y h y d r o x i d e s ) o r t o Fe-S x - r a y s p e c t r a
(pyrite # marcasite/ szomolnokite # melanterite # coquimbite/
other iron s u l f a t e s ) . Thus# d i s c r i m i n a t i o n among t h e p o s s i b i l -
i t i e s f o r t h e s e SEM c a t e g o r i e s i s n e c e s s a r y and c a n be a c h i e v e d
by Mtfssbauer s p e c t r o s c o p y / a l t h o u g h i t s h o u l d be n o t e d t h a t
p y r i t e and m a r c a s i t e a r e s u f f i c i e n t l y d i f f e r e n t from s u l f a t e s
i n t e r m s o f t h e Fe:S r a t i o t h a t s e p a r a t e c a t e g o r i e s a r e i n c o r -
p o r a t e d i n t h e SEM-AIA s o r t i n g r o u t i n e . The Mo'ssbauer s p e c t r u m
i s a l s o q u i t e s e n s i t i v e t o m i n o r d e g r e e s o f w e a t h e r i n g (18) a n d
p r o v i d e s a means by w h i c h o x i d a t i o n c a n be r e a d i l y r e c o g -
nized. O x i d a t i o n u s u a l l y gives r i s e t o a wider v a r i e t y o f
m i n e r a l s i n t h e c o a l t h a n w o u l d n o r m a l l y be f o u n d . As a
r e s u l t / some m o d i f i c a t i o n o f t h e SEM-AIA o p e r a t i o n may be
needed.
Discussion
O v e r t h e l a s t two y e a r s we h a v e d e t e r m i n e d t h e m i n e r a l
m a t t e r i n a b o u t 100 c o a l s a m p l e s f r o m some 30 U. S. c o a l seams
by u s i n g t h e c o m b i n a t i o n o f SEM-AIA and Mo'ssbauer s p e c t r o s -
copy. These c o a l s have v a r i e d a c r o s s a wide rank spectrum/
f r o m Montana l i g n i t e s t o N a r r a g a n s e t t B a s i n a n t h r a c i t e s . I n
t h i s s e c t i o n t h e r e l a t i v e m e r i t s and l i m i t a t i o n s o f a p p l y i n g
t h e s e t e c h n i q u e s w i l l be i l l u s t r a t e d a n d d i s c u s s e d .
C h a r a c t e r i z a t i o n o f M i n e r a l s i n U. S. C o a l s .
A n a l y s e s a r e shown i n T a b l e IV f o r n i n e c o a l s o f d i f f e r e n t
rank. The Mô'ssbauer d a t a a r e e x p r e s s e d a s p e r c e n t a g e s o f t h e
t o t a l i r o n c o n t a i n e d i n s p e c i f i c m i n e r a l s / w h e r e a s t h e SEM d a t a
a r e e x p r e s s e d as w e i g h t p e r c e n t a g e s o f the m i n e r a l matter i n
the c o a l . T h e s e c o a l s were a l s o c h o s e n t o i l l u s t r a t e t h e

12. HUGGiNS E T A L . SEM-AIA and Mossbauer Spectroscopy 247
ι ι 1 1 1 1 1 1 1 1 r
c
-12 -8 -4 0 4 8 12
VELOCITY, mm/s
Figure 3. Room temperature Mossbauer spectra of coal samples from the Pratt
seam in Alabama (top) and from an anthracite deposit in Rhode Island (bottom).
In the top spectrum, peaks indicated arise from iron in the common coal minerals
pyrite (Ρ), clays (C), siderite (S), and jarosite (J). In the bottom spectrum, peaks indi
cated arise from iron in clays (C), and in the rare coal minerals, ankerite (A), iron
metal (I), and ferric oxide (H).
American Chemical
Society Library
1155 16th St. N. w.
Washington,
ACS Symposium Series; D. C.Society:
American Chemical 20036 Washington, DC, 1982.
Table III. L i s t o f I r o n - b e a r i n g M i n e r a l s R e c o g n i z e d i n Room-Temperature

00
Mffssbauer S p e c t r a o f U. S. C o a l s
Mo'ssbauer P a r a m e t e r s
Isomer Quadruple Magnetic
Shift Splitting Splitting
Mineral (mm/s) (mm/s) (kG) Comments on O c c u r r e n c e
Pyrite, FeS 2 0.31 0.61 V e r y common, i n most coals.
Marcasite, FeS 2 0.29 0.51 Very rarely observed;

subordinate t o p y r i t e .
Clay ( i l l i t e , chlorite) 1.12 2.65 Commoni e s p e c i a l l y i n l o w s u l f u r

S i d e r i t e , FeC0 3 1.23 1.80 CommonI a n d h i g h e r r a n k c o a l s
Clay (montmorillonite) 1.12 2.79 Rare
Jarosite, (K,Na)Fe (S0 ) (OH) 3 4 2 6 F a i r l y common, f r o m FeS 2

0.38 1.15*
oxidation.
Szomolnokite, FeS0 4 ·Η 0 2 F a i r l y common, f r o m FeS

ο
2
1.26 2.71 g
oxidation.
>
Melanterite, FeS0 ·7Η 0 H
4 2
Rare, r e s t r i c t e d t o wet" coals. α
1.27 3.18
ο

Coquimbite, Fe (S0 ) ·9Η 0
2 4 3 2
Rare %
Ankerite, Ca(Fe,Mg)(C0 ) 3 2 1.23 1.50 R a r e ; New E n g l a n d a n t h r a c i t e s
o n l y examples o f a n k e r i t e
dominant o v e r s i d e r i t e . I
Η
Table I I I (Continued)
Mo'ssbauer P a r a m e t e r s
Isomer Quadruple Magnetic
Shift Splitting Splitting
(mm/s) (mm/s) (kG) Comments on O c c u r r e n c e
Mineral
0.00 0.00 330 V e r y R a r e ; New E n g l a n d

Fe m e t a l , Fe
a n t h r a c i t e s only - from
reduction of s i d e r i t e ?
1 1
0.37 Var" 390" Common i n w e a t h e r e d coals/ from
Goethite/ orFeOOH
pyrite oxidation.
0.37 0.65 Hare; i n weathered coals.

Lepidocrocite/ γ-FeOOH
0.31 0.00 495 Rare; o x i d a t i o n product or process

Magnetite Ee 0 3 4
0.65 0.00 465 ing contaminant.
0.38 -0.10 515 Very rare; d e h y d r a t i o n o f FeOOH

Hematite/ or^^2°3
* V a r i e s somewhat (1.05 - 1.25 mm/s) depending on c o m p o s i t i o n .

** Complex s p e c t r u m
+
V a r i e s d e p e n d i n g on m a g n e t i c properties. Commonly superparamagnetic
Κ)
Ο
Table IV
M i n e r a l o g i c a l Analyses o f Selected U. S. Coals
Coal (Seam, County, S t a t e , Rank)

P u s t R o s e b u d H e r r i n No. 6 D Seam Gholson Pratt Pocahontas No. 3 No. 8 Seam " A n t h r a c i t e "
Dawson, MT Rosebud, MT , IL Gunnison, Co. Shelby, AL J e f f e r s o n , AL Wyoming, WV -, PA B r i s t o l , MA
Môssbauer Sbb HVbb LVb Anthracite Anthracite
% Fe i n p y r i t e 100 65 93 15 16 45 19 78 16
Siderite 78 79 17 20 12 9
Clay tr 5 27 58 7 41
Jarosite 16 4 7 11 4 3
Other* 19-ra tr-m 31-a
Other 4-i
SEN-ΑΙΑ, wt%
Quartz 16 24 15 8 3 7 10 9 32
Kaolinite 38 40 5 29 1 20 26 5 tr
Illite tr 1 5 1 1 32 13 29 24
Chlorite tr tr 2 1 7 tr
Montmorilloni te - -1 1 15 tr 1 tr
Mixed s i l i c a t e -2 6 25 17 7 10 20 21 10
Pyrite 4 6 27 1 5 11 2 23 3
Fe-rich 1 tr 4 37 4 3 2 2
Calcite 7+- 8 6 6 28 4 4 1 6
Ankerite 1 tr 7 tr tr tr 9
Gypsum -
1 tr- tr
Jarosite - tr -
tr -
tr tr tr tr
Fe-sulfate - 2 -1 _ tr 1 1
Rutile t r- tr tr 1 1
Apatite -1 - 1 1 tr
î
Barite -8 2 _
- _ _ _
Sil/sul tr 1 7 2 _ 1 1 >
tr
Sil/pyr 1 2 _ tr -
1 1 tr tr
Others** -4 1 4 2 4
Ό
3 1 5 1
Unknown 20+ 4 2 14 5 4 10 4 5 Ο
t r - < 0.5 wt % f o r SEM-AIA; t r - <2% of t o t a l Fe f o r Môssbauer. ?

* Minerals i n d i c a t e d a r e : ra-melanterite, a - a n k e r i t e , i - i r o n metal.
** Other mixed c a t e g o r i e s , f o r the most p a r t . r
Mostly C a - r i c h macérais (see t e x t ) .
I
π
H
12. HUGGiNS ET AL. SEM-AIA and Mossbauer Spectroscopy 251
h e t e r o g e n e o u s n a t u r e o f U. S. c o a l s i n t e r m s o f t h e v a r i a t i o n
of i n d i v i d u a l m i n e r a l s . Even m i n e r a l s t r a d i t i o n a l l y c o n s i d e r e d
a s m a j o r components o f c o a l m i n e r a l o g y ( k a o l i n i t e , i l l i t e ,
p y r i t e ) c a n be n e g l i g i b l e i n c e r t a i n c o a l s .
The Mo'ssbauer d a t a i n d i c a t e t h a t t h e F e - r i c h c a t e g o r y c a n
be e q u a t e d t o s i d e r i t e e x c e p t f o r t h e M a s s a c h u s e t t s a n t h r a c i t e ,
i n which i r o n metal a l s o s i g n i f i c a n t l y c o n t r i b u t e s t o t h i s
category. E x c e p t p o s s i b l y f o r t h e two l o w e s t r a n k c o a l s , t h e s e
n i n e c o a l s do n o t show a p p r e c i a b l e e f f e c t s o f w e a t h e r i n g a n d no
o x i d e s o r o x y h y d r o x i d e s were o b s e r v e d i n a n y Mo'ssbauer
spectrum. The p r e s e n c e o f j a r o s i t e i n t h e m a j o r i t y o f t h e s e
s a m p l e s , h o w e v e r , i n d i c a t e s t h a t some o x i d a t i o n o f p y r i t e h a s
been i n i t i a t e d . The p r e s e n c e o f s i g n i f i c a n t m e l a n t e r i t e i n t h e
Rosebud sample s u g g e s t s t h a t such o x i d a t i o n h a s p r o g r e s s e d
f u r t h e s t i n t h i s sample.
The SEM-AIA c a t e g o r i e s l i s t e d i n T a b l e I V c o n s i s t o f
15 i n d i v i d u a l m i n e r a l c a t e g o r i e s . T h i s number o f m i n e r a l s i s
a b o u t d o u b l e t h a t d e t e r m i n e d b y s t a n d a r d XRD o r I R t e c h n i q u e s ,
w h i c h a r e g e n e r a l l y l i m i t e d t o t h e d e t e r m i n a t i o n o f no more
t h a n s e v e n m a j o r m i n e r a l s (J_). T h e SEM-AIA t e c h n i q u e , t h e n , i s
more s e n s i t i v e t o m i n o r m i n e r a l components t h a n t h e s e more
t r a d i t i o n a l techniques. A l s o , i t i s c o n s i d e r a b l y more f l e x i b l e
i n t h a t a n o v e l m i n e r a l c a n be i n t r o d u c e d i n t o t h e a n a l y s i s
v e r y e a s i l y and w i t h o u t t h e need f o r c a l i b r a t i o n d a t a , u n l i k e
these other techniques.
A s c a n be s e e n i n T a b l e TV, one o f t h e m a j o r SEM-AIA

c a t e g o r i e s i n most a n a l y s e s i s t h e m i x e d s i l i c a t e c a t e g o r y .
T h i s c a t e g o r y a r i s e s f r o m two m a i n s o u r c e s : either physically
a s s o c i a t e d s i l i c a t e s , such as q u a r t z - c l a y combinations d e r i v e d
from p a r t i n g s , or mixed-layer c l a y s o f v a r i a b l e compositions
outside the compositional l i m i t s of the i n d i v i d u a l c l a y
categories (kaolinite, i l l i t e , montmorillonite, c h l o r i t e ) . For
e x a m p l e , a b o u t 30 p e r c e n t o f t h e p a r t i c l e s i n t h e m i x e d -
s i l i c a t e category o f the Massachusetts a n t h r a c i t e had composi-
t i o n s c o n s i s t e n t w i t h an i l l i t e - c h l o r i t e m i x e d - l a y e r c l a y . The
w e i g h t p e r c e n t a g e s i n t h i s c a t e g o r y c a n be f u r t h e r s u b d i v i d e d
as needed.
I t must be n o t e d h e r e t h a t XRD a n d I R t e c h n i q u e s a r e
m i n e r a l o g i c a l l y s p e c i f i c , w h e r e a s SEM-AIA i s o n l y c o m p o s i t i o n -
a l l y s p e c i f i c a n d t h e c o r r e c t n e s s o f t h e SEM-AIA m i n e r a l
a n a l y s i s d e p e n d s on t h e u n i q u e n e s s o f t h e i n d i v i d u a l m i n e r a l
compositions. F o r e x a m p l e , SEM-AIA c a n n o t d i s c r i m i n a t e b e t w e e n
p y r i t e a n d m a r c a s i t e , o r among t h e T i 0 p o l y m o r p h s , o r b e t w e e n
2
h a l l o y s i t e and k a o l i n i t e [both A l S i 0 ( O H ) ] .
2 2 5 4 However, e x c e p t
f o r t h e F e - r i c h and Fe-S c a t e g o r i e s , which a r e r e s o l v e d by
Mo'ssbauer s p e c t r o s c o p y , a l l o t h e r d u p l i c a t i o n s o f m i n e r a l
c o m p o s i t i o n s i n v o l v e m i n e r a l s t h a t a r e uncommon i n c o a l . In

g e n e r a l , t h e c o m p o s i t i o n s o f t h e common c o a l m i n e r a l s a r e
u n i q u e a n d a s u f f i c i e n t means by w h i c h t h e m i n e r a l s c a n be
identified.
T h i s l a c k o f m i n e r a l o g i c a l s p e c i f i c i t y i n SEM-AIA,
h o w e v e r , c a n be u s e d t o a d v a n t a g e when e x a m i n i n g m i n e r a l -
d e r i v e d m a t t e r i n c o k e s , c h a r s , and o t h e r p r o d u c t s o f c o a l
conversion technologies* As t h e SEM-AIA t e c h n i q u e i s i n s e n s i -
t i v e t o c r y s t a l s t r u c t u r e , i t makes no d i f f e r e n c e w h e t h e r t h e
m i n e r a l s d u r i n g c o n v e r s i o n undergo phase t r a n s f o r m a t i o n s ,
become amorphous ( e . g . , d e h y d r a t i o n o f c l a y s ) , o r e v e n m e l t , as
l o n g as t h e c o m p o s i t i o n a l f i n g e r p r i n t s r e m a i n u n a l t e r e d .
T h e r e f o r e , t h e SEM-AIA t e c h n i q u e c a n be a most u s e f u l means t o

c o r r e l a t e d i r e c t l y minerals i n the c o a l with the m i n e r a l -
d e r i v e d phases i n the conversion product. F o r e x a m p l e , we h a v e
been a b l e t o d e m o n s t r a t e ( u n p u b l i s h e d work) t h a t d u r i n g c a r b o n -
i z a t i o n , the m i n e r a l s p r i n c i p a l l y o n l y undergo decomposition
r e a c t i o n s i n v o l v i n g the l o s s of v o l a t i l e m o l e c u l e s , such as
H 0,
2 H S,
2 and C 0 .
2 T h e r e i s no e v i d e n c e f o r e x t e n s i v e r e a c t i o n
among t h e d i f f e r e n t m i n e r a l s , d e s p i t e e x p o s u r e t o t e m p e r a t u r e s
a b o v e 1000 C f o r p e r i o d s o f h o u r s d u r i n g c a r b o n i z a t i o n , b e c a u s e
e
t h e w e i g h t p e r c e n t a g e s o f t h e d i f f e r e n t SEM-AIA c o m p o s i t i o n a l
c l a s s e s a r e n o t g r e a t l y d i f f e r e n t b e t w e e n t h e c o a l s and t h e
c o k e s d e r i v e d f r o m them.
C h a r a c t e r i z a t i o n of I n o r g a n i c Elements i n Macérais* As
n o t e d a b o v e , one o f t h e a d v a n t a g e s o f SEM-AIA i s t h e f a c t t h a t
the m i n e r a l matter i s analyzed without s e p a r a t i o n from the
macérais. O c c a s i o n a l l y , however, t h e p r e s e n c e o f d i f f u s e ,
o r g a n i c a l l y bonded i n o r g a n i c elements i n t h e macérais w i l l
c o m p l i c a t e t h e a n a l y s i s . T h i s c o m p l i c a t i o n i s most s e r i o u s f o r
l i g n i t e s , the macérais of which o f t e n c o n t a i n s i g n i f i c a n t
c a l c i u m and o t h e r i n o r g a n i c e l e m e n t s . As shown i n F i g u r e 4,
t h e s i m p l e t w o - p h a s e BSE image ( m i n e r a l s and m a c e r a l / e p o x y
b a c k g r o u n d ) i n h i g h - r a n k c o a l s i s r e p l a c e d by a t h r e e - p h a s e BSE
image ( m i n e r a l s , C a - r i c h m a c é r a i s , and e p o x y ) i n l i g n i t e s .
If the p a r t i c l e / b a c k g r o u n d d i s c r i m i n a t i o n l e v e l i n the
a n a l o g c o m p a r a t o r i s s e t h i g h enough t o e x c l u d e C a - r i c h
m a c é r a i s , t h e n an a p p r e c i a b l e f r a c t i o n o f t h e i n o r g a n i c m a t t e r
i n l i g n i t e s i s e x c l u d e d f r o m t h e a n a l y s i s . I f , however, t h e
l e v e l i s s e t t o i n c l u d e t h e C a - r i c h m a c é r a i s , t h e SEM-AIA
p r o c e d u r e f i n d s t h e m a c é r a i s and v e r y l i t t l e e l s e b e c a u s e o f
t h e i r l a r g e t o t a l a r e a compared w i t h t h a t o f d i s c r e t e m i n e r -
als. Of t h e s e two p r o c e d u r e s , we p r e f e r t h e f i r s t s o t h a t t h e
d i s c r e t e m i n e r a l s a r e emphasized i n t h e a n a l y s i s . A mass-
balance c a l c u l a t i o n comparing the d i s c r e t e m i n e r a l a n a l y s i s
w i t h the c h e m i c a l a n a l y s i s of the ash w i l l then g i v e an
approximate value f o r the f r a c t i o n of i n o r g a n i c elements i n
combination with the macérais. However, as t h e i n o r g a n i c -

12. HUGGiNS ET AL. SEM-AIA and Môssbauer Spectroscopy 253
Figure 4. Inverted backscattered electron image of a polished sample of Montana

Pust seam lignite (left) and energy-dispersive x-ray spectrum of an individual
maceral (right). Note, in comparison to Figure 1, the enhanced contrast of the
macérais due to the presence of inorganic elements.

e l e m e n t c o n c e n t r a t i o n s i n t h e m a c é r a i s v a r y , some i n o r g a n i c -
r i c h m a c e r a l a r e a s a r e a l s o measured, and t h e r e f o r e s u c h
a n a l y s i s o f l i g n i t e s c a n o n l y be r e g a r d e d a s s e m i - q u a n t i t a -
tive. T h i s d i f f i c u l t y s h o u l d u l t i m a t e l y be r e s o l v e d b y
m o d i f i c a t i o n of the d i s c r i m i n a t i o n - l e v e l d e f i n i t i o n from the
p r e s e n t o v e r a l l a v e r a g e v a l u e t o one s e n s i t i v e t o l o c a l v a r i a -
tion.
F o r t h e l i g n i t e a n a l y s i s shown i n T a b l e IV, most o f t h e

m e a s u r e d i n o r g a n i c - r i c h m a c e r a l a r e a s were a s s i g n e d t o t h e
unknown c a t e g o r y , a l t h o u g h t h o s e t h a t were p a r t i c u l a r l y r i c h i n
c a l c i u m were a s s i g n e d t o t h e c a l c i t e c a t e g o r y . In t h i s l a t t e r
s i t u a t i o n , t h e v e r y low t o t a l i n t e n s i t y o f x - r a y s , a p a r a m e t e r
recorded i n the a n a l y s i s , serves t o d i s t i n g u i s h these C a - r i c h
areas from c a l c i t e . I n d e e d , v e r y l i t t l e c a l c i t e was p r e s e n t i n
this lignite.
The same p r o b l e m o f C a - r i c h m a c é r a i s h a s a l s o b e e n n o t e d
i n SEM-AIA o f s u b b i t u m i n o u s c o a l s a n d h i g h l y w e a t h e r e d b i t u m i -
n o u s c o a l s ( u n p u b l i s h e d d a t a ) , b u t t o a much l e s s s e r i o u s
degree. S i m i l a r c o m p l i c a t i o n s a r i s e when an o r g a n i c e l e m e n t ,
u s u a l l y s u l f u r or c h l o r i n e , c o n t r i b u t e s a s t r o n g background
s i g n a l t o the x-ray spectrum. For s m a l l p a r t i c l e s , e s p e c i a l l y ,
t h i s e x t r a x - r a y p e a k c a n be s u f f i c i e n t l y i n t e n s e t o c a u s e t h e
p a r t i c l e t o be a s s i g n e d t o a m i x e d o r unknown c a t e g o r y . In
T a b l e IV, f o r e x a m p l e , a s t r o n g o r g a n i c s u l f u r b a c k g r o u n d i s
r e s p o n s i b l e f o r the r e l a t i v e l y high percentage of p a r t i c l e s i n
t h e s i l i c a t e / s u l f u r c a t e g o r y f o r t h e H e r r i n No. 6 c o a l , and a
s t r o n g c h l o r i n e background i s mostly r e s p o n s i b l e f o r the l a r g e
number o f unknown p a r t i c l e s i n D-seam c o a l f r o m C o l o r a d o .
Although the presence o f C a - r i c h macérais i n l i g n i t e s and

the o c c a s i o n a l l y s t r o n g organic-element background i n other
c o a l s c o m p l i c a t e SEM-AIA, t h e i n f o r m a t i o n o b t a i n e d a b o u t t h e s e
components i s , i n i t s e l f , v e r y u s e f u l . Scanning e l e c t r o n
m i c r o s c o p y may be one o f t h e few t e c h n i q u e s t h a t e n a b l e t h e s e
d i f f u s e components t o be i n v e s t i g a t e d i n any d e t a i l .
P a r t i c l e - s i z e A n a l y s i s . A n o t h e r a d v a n t a g e t h a t SEM-AIA
o f f e r s o v e r b u l k methods i s t h e i n f o r m a t i o n t h a t c a n be
obtained r e l a t i n g t o the d i s t r i b u t i o n of p a r t i c l e s i z e .
I n d e e d , n o t o n l y a r e b u l k methods u n i n f o r m a t i v e a b o u t p a r t i c l e
s i z e , b u t c o n s i d e r a b l e p r e c a u t i o n s must be t a k e n t o e n s u r e t h a t
p a r t i c l e - s i z e e f f e c t s do n o t a d v e r s e l y a f f e c t t h e determina-
t i o n s of the minerals ( ·
An e x c e l l e n t a p p l i c a t i o n o f SEM-AIA p a r t i c l e - s i z e d a t a was
d i s c o v e r e d i n an i n v e s t i g a t i o n o f p y r i t e o x i d a t i o n a s a r e s u l t
o f a c o a l w e a t h e r i n g (18)· T a b l e V summarizes m i n e r a l o g i c a l
d a t a o b t a i n e d by SEM-AIA on a s u i t e o f f o u r s a m p l e s o f M i d d l e
Kittanning coal. T h e s e s a m p l e s were o b t a i n e d f r o m a s t r i p mine

12. HUGGiNS ET AL. SEM-AIA and Môssbauer Spectroscopy 255
T a b l e V. M i n e r a l o g i c a l Data on Samples o f
M i d d l e K i t t a n n i n g Seam by SEM-AIA
Weight P e r c e n t o f M i n e r a l M a t t e r
Mineral Unweathered Highwall Intermediate Outcrop
Quartz 3 11 13 7
Kaolinite 14 17 17 18
Illite 18 24 8 5
Mixed Silicate 9 15 11 7
Pyrite (FeS ) 2 50 24 20 9
Goethite (FeOOH) 1 4 27 51
Calcite 3 1 1 -
Others 1 1 2 2
unknown 1 2 2 2
FeOOH
; 0 2 1 4 5 7 8 5
FeOOH + F e s 2 °· ° · °- °'
b y Mtfssbauer 0.00 0.16 0.53 0.78

b e t w e e n t h e h i g h w a l l o f t h e mine a n d a n o u t c r o p . The weathered

n a t u r e o f t h e c o a l i n c r e a s e s f r o m l e f t t o r i g h t i n T a b l e V.
Mo'ssbauer d a t a c o n f i r m e d t h e i d e n t i t y o f t h e i r o n - r i c h c a t e g o r y
as g o e t h i t e ( a-FeOOH) a n d e x c e l l e n t a g r e e m e n t was f o u n d b e t w e e n
SEM-AIA a n d Mo'ssbauer t e c h n i q u e s f o r t h e g o e t h i t e / p y r i t e r a t i o ,
as shown i n T a b l e V .
D a t a on t h e d i s t r i b u t i o n o f t h e a v e r a g e d i a m e t e r o f
g o e t h i t e p a r t i c l e s over the s i z e ranges l i s t e d i n Table I a r e
shown i n F i g u r e 5 . T h e s e d a t a show t h a t t h e s l i g h t l y o x i d i z e d
h i g h w a l l sample h a s t h e h i g h e s t p e r c e n t a g e o f g o e t h i t e p a r t i -
c l e s i n t h e s m a l l e s t s i z e range. The g o e t h i t e d i s t r i b u t i o n
p r o f i l e s become l e s s s t r o n g l y b i a s e d t o w a r d s s m a l l p a r t i c l e
s i z e from the h i g h w a l l t o t h e o u t c r o p . The d i s t r i b u t i o n
p r o f i l e f o r g o e t h i t e i n t h e o u t c r o p sample, i s i n f a c t , q u i t e
similar t o that f o r p y r i t e i n the unoxidized coal.
These d a t a c o n f i r m t h a t p a r t i c l e s i z e i s an i m p o r t a n t
factor c o n t r o l l i n g the conversion of p y r i t e to goethite i n coal
undergoing atmospheric weathering. Such d a t a o n p a r t i c l e s i z e
c o u l d n o t be e a s i l y o b t a i n e d b y o t h e r m e t h o d s .
Conclusions
I n t h i s p a p e r , we h a v e d e s c r i b e d how m i n e r a l s i n c o a l c a n
be q u a n t i t a t i v e l y d e t e r m i n e d by t h e c o m b i n a t i o n o f SEM-AIA a n d
Mo'ssbauer s p e c t r o s c o p y . T h e s e t e c h n i q u e s c a n be a p p l i e d t o a l l
c o a l s , f r o m l i g n i t e t o a n t h r a c i t e , w i t h l i t t l e o r no m o d i f i c a -
tion. A l t h o u g h s u c h a p p l i c a t i o n s a r e n o t d i s c u s s e d i n any
d e t a i l h e r e , t h e s e t e c h n i q u e s c a n a l s o be a p p l i e d t o c o k e s ,
c h a r s , s o l v e n t - r e f i n e d c o a l s , and o t h e r p r o d u c t s o f c o a l
conversion.
M i n e r a l c h a r a c t e r i z a t i o n b y SEM-AIA a n d Mo'ssbauer
s p e c t r o s c o p y i s p e r h a p s l e s s s p e c i f i c t h a n b y F T I R o r XRD.
However, t h i s d i s a d v a n t a g e i s c o m p e n s a t e d b y t h e f a c t t h a t more
i n f o r m a t i o n i s o b t a i n e d b y SEM-AIA. Such added i n f o r m a t i o n
i n c l u d e s d a t a on p a r t i c l e - s i z e p a r a m e t e r s and s e m i q u a n t i t a t i v e
determinations o f i n o r g a n i c c o n s t i t u e n t s o f macérais, as w e l l
a s d a t a f o r a l a r g e r number o f m i n e r a l s i n t h e r o u t i n e
analysis. I n a d d i t i o n , a s t h e m i n e r a l s do n o t h a v e t o b e
s e p a r a t e d f r o m m a c é r a i s f o r t h e a n a l y s i s , SEM-AIA s h o u l d be
amenable f o r s t u d i e s o f m i n e r a l a s s o c i a t i o n s and p o s s i b l y f o r
mineral-maceral associations.

12. HUGGINS E T AL. SEM-AIA and Môssbauer Spectroscopy 257
CLASS LIMITS IN MICRONS
Figure 5. Distribution of particle-size parameter (average diameter of cross-

sectional area) for geothite (a-FeOOH) in samples of Middle Kittanning coal. Key:
Δ, high wall sample; O, middle sample; •, outcrop sample; and P, original pyrite
sample. See Table I for definition of class limits.

The m a t e r i a l i n t h i s p a p e r i s i n t e n d e d f o r g e n e r a l i n f o r m a t i o n
only. Any u s e o f t h i s m a t e r i a l i n r e l a t i o n t o a n y s p e c i f i c
a p p l i c a t i o n s h o u l d be based on i n d e p e n d e n t e x a m i n a t i o n and
v e r i f i c a t i o n o f i t s u n r e s t r i c t e d a v a i l a b i l i t y f o r such use, and
a d e t e r m i n a t i o n o f s u i t a b i l i t y f o r t h e a p p l i c a t i o n by p r o f e s -
sionally q u a l i f i e d personnel. No l i c e n s e u n d e r a n y U n i t e d
States Steel Corporation patents or other proprietary i n t e r e s t
i s i m p l i e d by t h e p u b l i c a t i o n o f t h i s p a p e r . Those making u s e
o f o r r e l y i n g upon t h e m a t e r i a l assume a l l r i s k s a n d l i a b i l i t y
a r i s i n g from such use o r r e l i a n c e .
Literature Cited
1. R. G. Jenkins and P. L. Walker, Jr. "Analytical Methods

for Coal and Coal Products", Vol. II; Academic Press: New
York, 1978, 265-292.
2. H. J. Gluskoter, Fuel 1965, 44, 285-291.
3. L. A. Harris, T. Rose, L. DeRoos, J. Greene, Econ. Geol.,
1976, 71, 695-697.
4. P. L. Walker, W. Spackman, P. H. Given, E. W. White,
A. Davis, R. G. Jenkins, EPRI Report AF-417, 1977.
5. P. L. Walker, W. Spackman, P. H. Given, A. Davis,
R. G. Jenkins, P. C. Painter, EPRI Report AF-832, 1978.
6. R. J. Lee, F. E. Huggins, G. P. Huffman, SEM/1978/I,
561-568.
7. A. Moza, L. G. Austin, G. G. Johnson, Jr., SEM/1979/I,
473-476.
8. F. E. Huggins, D. A. Kosmack, G. P. Huffman, R. J. Lee,
SEM/1980/I, 531-540.
9. T. Erickson, R. Wappling, J. Physique, 1978, 37(C6),
719-723.
10. R. J. Lee, R. M. Fisher, NBS Special Publication 553,
1980, 63-83.
11. R. J. Lee, J. F. Kelly, SEM/1980/I, 303-310.
12. G. P. Huffman, F. E. Huggins, Fuel, 1978, 57, 592-604.
13. F. E. Huggins, G. P. Huffman, "Analytical Methods for Coal
and Coal Products", Vol. III; Academic Press: New York,
1979, 371-423.
14. I. S. Jacobs, L. M. Levinson, H. R. Hart, Jr., J. Appl.
Phys., 1978, 49, 1775-1780.
15. P. A. Montano, "Mössbauer Spectroscopy and its Chemical
Applications"; American Chemical Society: Washington,
D. C., 1981, 135-175.
16. G. P. Huffman, F. E. Huggins, G. R. Dunmyre, Fuel, 1981,
60, 585-597.
17. C. C. Hinkley, G. V. Smith, H. Twardowska, M.
Saporoschenko, R. H. Shiley, R. A. Griffen, Fuel, 1980,
59, 161-165.
18. F. E. Huggins, G. P. Huffman, D. A. Kosmack, D.
E. Lowenhaupt, Coal Geol., 1980, 1, 75-81.

13
Analytical Instruments in the Coal Preparation
Industry
Current Status and Development Needs
LEON N. KLATT
Oak Ridge National Laboratory, Analytical Chemistry Division,
Oak Ridge, T N 37830
The expanded use of domestic coal supplies as

a substitute for imported petroleum will require

significant expansion and modernization of the coal
preparation industry. The Oak Ridge National
Laboratory has assembled a multidisciplined team to
study the needs of this industry and to undertake a
development program with the goal of improving the
efficiency and practice of coal beneficiation.
Automated on-line analytical instruments are key
elements in accomplishing this goal. On-line ash
monitors are commercially available and have been
successfully used in coal preparation plants world
wide. On-line sulfur meters, based upon prompt
neutron activation analysis have been developed.
These systems can be modified to determine ash and
calorific value. A moisture monitor, based upon
microwave attenuation can be added to the sulfur
meter. Nuclear density gauges are the only on-line
process control instruments used in coal prepara-
tion plants. World wide development activities
related to on-line analytical instruments are sum-
marized, and development needs for product quality
and process control instruments are discussed.
Coal p r e p a r a t i o n has been an important segment of the c o a l

i n d u s t r y i n the United States f o r approximately one hundred
years. Its i n i t i a l use was i n the production of high q u a l i t y
c o a l used i n the manufacture of coke. By 1965 approximately 95%
of m e t a l l u r g i c a l grade c o a l was processed through a c o a l prepara-
t i o n p l a n t . The use of cleaned c o a l as a f u e l f o r e l e c t r i c power
generation and as an i n d u s t r i a l b o i l e r f u e l i s r e l a t i v e l y recent.
Studies conducted f o r the U. S. Department of Energy (1) and the
U. S. Environmental P r o t e c t i o n Agency (2) concluded that c o a l
p r e p a r a t i o n combined with f u e l gas d e s u l f u r i z a t i o n i s the l e a s t
0097-6156/82/0205-0259$06.25/0

c o s t l y method of meeting New Source Performance Standards f o r

s u l f u r d i o x i d e emissions. The use of cleaned c o a l as a b o i l e r
f u e l should improve b o i l e r e f f i c i e n c i e s ; however, the comparative
data r e q u i r e d to q u a n t i f y the impact that cleaned c o a l has on the
performance and r e l i a b i l i t y of power p l a n t s are not a v a i l a b l e
(3).
Coal p r e p a r a t i o n can be d e f i n e d as a process or s e r i e s of
processes which reduces the m i n e r a l and p y r i t i c s u l f u r content of
run-of-the-mine c o a l . Although chemical and p h y s i c a l methods can
be used t o achieve the bénéficiâtion, past and current i n d u s t r i a l
p r a c t i c e s employ only p h y s i c a l methods, and are based upon the
d i f f e r e n c e s i n s p e c i f i c g r a v i t y between the c o a l , m i n e r a l matter,
and p y r i t i c s u l f u r . A s i m p l i f i e d block diagram of a c o a l prepa-
r a t i o n p l a n t i s shown i n Figure 1. The run-of-the-mine c o a l i s

s i z e d c l a s s i f i e d by a wet screening o p e r a t i o n . The coarse c o a l
i s cleaned i n j i g s or heavy media baths. The s m a l l e r s i z e d
m a t e r i a l i s f u r t h e r subdivided i n t o intermediate and f i n e f r a c -
t i o n s . The intermediate m a t e r i a l i s processed v i a a wide v a r i e t y
of u n i t o p e r a t i o n s , ranging from heavy media cyclones to wet
c o n c e n t r a t i n g t a b l e s . The f i n e f r a c t i o n i s u s u a l l y processed v i a
f r o t h f l o t a t i o n . Figure 2 summarizes the q u a n t i t y of clean c o a l
produced s i n c e 1940 and compares t h i s w i t h the t o t a l U.S. c o a l
production.
D i f f e r e n t c o a l deposits d i f f e r widely not only i n maceral,
s u l f u r and m i n e r a l content but a l s o d i f f e r widely i n other prop-
e r t i e s , e.g., g r i n d a b i l i t y , v o l a t i l i t y and BTU content. Signif-
i c a n t v a r i a t i o n s i n the p r o p e r t i e s of c o a l can a l s o occur w i t h i n
a deposit and w i t h i n an i n d i v i d u a l seam. As a r e s u l t , each c o a l
deposit presents to the c o a l p r e p a r a t i o n engineer and p l a n t
operator a unique set of f a c t o r s that must be considered i n the
design and o p e r a t i o n of a p r e p a r a t i o n p l a n t .
The fundamental i n f o r m a t i o n r e q u i r e d by the c o a l p r e p a r a t i o n
engineer and p l a n t operator i s summarized i n c o a l w a s h a b i l i t y
curves. Figure 3 i s an example of a w a s h a b i l i t y curve. This
data i s obtained by s u b j e c t i n g the c o a l sample to a s e r i e s of
s p e c i f i c g r a v i t y f r a c t i o n a t i o n s and a n a l y z i n g each f l o a t and s i n k
s u b f r a c t i o n f o r ash content. Other analyses, such as s u l f u r and
BTU content, are o f t e n conducted, depending on the end use of the
c o a l . W a s h a b i l i t y data f o r d i f f e r e n t p r e s e l e c t e d p a r t i c l e s i z e
f r a c t i o n s of the o r i g i n a l c o a l sample are a l s o obtained. This
l a t t e r i n f o r m a t i o n i s p a r t i c u l a r l y important to the c o a l
p r e p a r a t i o n engineer because d i f f e r e n t p r o c e s s i n g techniques and
equipment are r e q u i r e d to t r e a t d i f f e r e n t s i z e m a t e r i a l .
Analytical Instrumentation
Laboratory Instrumentation. S u c c e s s f u l o p e r a t i o n of a
modern c o a l p r e p a r a t i o n p l a n t r e q u i r e s the a v a i l a b i l i t y of a w e l l
equipped and w e l l s t a f f e d c o a l a n a l y s i s l a b o r a t o r y . This
l a b o r a t o r y must be capable of performing t e s t s to c h a r a c t e r i z e

KLATT Analytical Instruments in the Coal Industry 261
/6>
PRIMARY SCREEN
FINE COAL
C L E A N I N G CIRCUIT
28M X 0
COARSE COAL
C L E A N I N G CIRCUIT
4 X V
4
INTERMEDIATE COAL
H C L E A N I N G CIRCUIT
% X 28 M
CLEAN COAL
REFUSE
Figure 1. Simplified diagram of a modern coal preparation plant.
900
c
ο
ο 700
Ε
ζ
9 500
Ι
Ο
Ζ)
Ο
ο
CL
< 300 S
100 _L
1940 1950 1960 1970 1980
YEAR
Figure 2. Coal mine ( ) and coal preparation plant ( ) production.

Figure 3. Coal washability curves. Key: , cumulative ash; , ± 0.10

specific gravity distribution; and , yield.

13. KLATT Analytical Instruments in the Coal Industry 263
the feed c o a l , to v e r i f y product q u a l i t y , and to provide process

control information. The analyses commonly performed are
described i n standard t e s t procedures published by the American
Society f o r Testing and M a t e r i a l s (4).
On-Line Instrumentation-General C o n s i d e r a t i o n s . Rapid

response time and the a b i l i t y to sample l a r g e q u a n t i t i e s of
m a t e r i a l c o n s t i t u t e the p r i n c i p a l design c r i t e r i a f o r o n - l i n e
instruments i n the c o a l p r e p a r a t i o n i n d u s t r y . Other important
f a c t o r s i n c l u d e c o s t , r e l i a b i l i t y , and m a i n t a i n a b i l i t y ; however
these a r e common to o n - l i n e instrumentation i n any i n d u s t r y .
Rapid response i s r e q u i r e d because the residence time of m a t e r i a l
i n the process equipment v a r i e s from a few seconds to a few
minutes; average residence time i n the plant i s t y p i c a l l y l e s s

than t e n minutes. Furthermore, s i g n i f i c a n t v a r i a t i o n s i n the
composition of the run-of-the-mine c o a l f e d to the plant can
occur i n a step f u n c t i o n a l manner. The heterogenous nature o f
c o a l and the quantity of m a t e r i a l processed through a t y p i c a l
c i r c u i t w i t h i n a preparation plant r e q u i r e s a simple means of
o b t a i n i n g information r e p r e s e n t a t i v e of the process stream.
Non-invasive sampling methods are p r e f e r r e d because m a t e r i a l
handling problems are minimized.
Because of the above requirements, most of the l a b o r a t o r y
techniques used to analyze c o a l cannot be t r a n s f e r r e d to o n - l i n e
instruments. Methods which use high energy photons, gamma or
x-ray, can meet the above design c r i t e r i a , and consequently, a l l
the systems developed or under development f o r the c o a l i n d u s t r y ,
and which y i e l d elemental composition information employ
methodology which involves the measurement o f gamma or x-rays.
On-line instrumentation i n c o a l preparation plants can be
c l a s s i f i e d i n t o two broad c a t e g o r i e s , instruments that monitor a
process or m a t e r i a l parameter and instruments that monitor pro-
cess equipment s t a t u s . L i q u i d l e v e l and pressure gauges which
monitor sump l e v e l s and pump o u t l e t pressure are examples of
instruments i n the l a t t e r c l a s s i f i c a t i o n and w i l l not be
discussed i n t h i s report.
On-Line Instrumentation Used i n the Coal Preparation

Industry. Ash monitors, nuclear density gauges, and pH monitors
are the only o n - l i n e instruments c u r r e n t l y used to measure
process o r m a t e r i a l parameters i n U.S. c o a l p r e p a r a t i o n p l a n t s .
Two o n - l i n e ash monitors are commercially a v a i l a b l e , the
Sortex Ash Monitor (Gunson's Sortex Ltd., London, England) and
the KHD Analyzer (KHD Industrieanlogen, Humbolt, Weday, Federal
Republic of Germany). Both instruments use the backscatter of
h i g h energy photons to determine the ash content of the sample;
the Sortex u n i t employs ^^^Pu, which emits a 17·6 KeV x-ray,
while the KHD u n i t uses Am, which emits a 60 KeV gamma
241
ray. The Sortex Ash Monitor has been i n s t a l l e d i n eight U.S.

c o a l preparation p l a n t s ; t h i r t y a d d i t i o n a l u n i t s have been
i n s t a l l e d worldwide.

The f i r s t i n s t a l l a t i o n and use of an ash monitor i n the U.S.

was a Sortex u n i t at the Moss No. 3 P r e p a r a t i o n Plant ( C l i n c h -
f i e l d Coal Company, D i v i s i o n of P i t t s t o n Coal Group, Lebanon,
V i r g i n i a ) . The Moss No. 3 p l a n t produces three blends of m e t a l -
l u r g i c a l côal and a steam c o a l . The Sortex Ash monitor i s used
to monitor the m e t a l l u r g i c a l c o a l product, and i t s output i s used
by the p l a n t superintendent to s e l e c t the blending r a t i o s of
run-of-the mine c o a l being cleaned at the p l a n t .
When a m a t e r i a l i s exposed to x-rays or gamma r a y s , a
p o r t i o n of the r a d i a t i o n i s absorbed and a p o r t i o n i s s c a t t e r e d .
The a b s o r p t i o n process f o l l o w s an e x p o n e n t i a l r e l a t i o n s h i p
I » I exp[-u pl] (1)

0 m
where I i s the i n c i d e n t x-ray i n t e n s i t y , I the i n t e n s i t y a f t e r

Q
t r a v e r s i n g an absorber t h i c k n e s s 1, \i i s the mass a b s o r p t i o n

m
c o e f f i c i e n t , and ρ i s the d e n s i t y of the m a t e r i a l . The mass

a b s o r p t i o n c o e f f i c i e n t i n c r e a s e s approximately as the 3.5 power
of the atomic number and decreases w i t h i n c r e a s i n g photon energy.
The t o t a l s c a t t e r i n g process i s composed of e l a s t i c and i n e l a s t i c
components. The p r o b a b i l i t y f o r e l a s t i c s c a t t e r i n g of a photon
increases w i t h the square of the atomic number and decreases w i t h
i n c r e a s i n g photon energy. The p r o b a b i l i t y f o r i n e l a s t i c s c a t t e r
ing i s p r o p o r t i o n a l to the atomic number and a l s o decreases w i t h
i n c r e a s i n g photon energy. Consequently, f o r a g i v e n i n c i d e n t
photon energy, an i n c r e a s e i n ash forming elements i n the c o a l
decreases the t o t a l number of photons backseattered, and a meas
urement of the b a c k s c a t t e r i n t e n s i t y provides a measure of the
t o t a l ash forming elemental content of a c o a l sample.
A schematic drawing of the sensor system employed i n the
Sortex Ash Monitor i s shown i n F i g u r e 4. The x-rays emitted by
the 23*Spu s o u r c e i r r a d i a t e the c o a l sample and penetrate up
t o 38 mm. This r a d i a t i o n i s absorbed and s c a t t e r e d ; the f r a c t i o n
backscattered i s counted w i t h a gas p r o p o r t i o n a l counter. The
aluminum f i l t e r i s used to compensate f o r i r o n f l u o r e s c e n t
x - r a y s , which are e x c i t e d by the i n c i d e n t x-rays. The f i l t e r
p r e f e r e n t i a l l y absorbs most of the i r o n f l u o r e s c e n t x-rays (^6
KeV), and i t s t h i c k n e s s i s chosen based upon the i r o n content of
the c o a l samples. The aluminum f i l t e r a l s o compensates f o r
s u l f u r v a r i a t i o n s i n the c o a l . This occurs because a major
f r a c t i o n of s u l f u r i s present as p y r i t e and the decrease i n x-ray
b a c k s c a t t e r i n t e n s i t y due t o s u l f u r i s p a r t i a l l y o f f s e t by an
i n c r e a s e i n i r o n f l u o r e s c e n c e . Organic s u l f u r i s g e n e r a l l y
c o n s t a n t , and i t i s c o r r e c t e d f o r i n the c a l i b r a t i o n of the
instrument ( 5 ) .
F i g u r e 5 c o n t a i n s the flow diagram f o r the i n s t a l l a t i o n of
the Sortex Ash Monitor at the Moss No. 3 c o a l p r e p a r a t i o n p l a n t .
The c l e a n c o a l product i s sampled, crushed to a top s i z e of 5 mm,
and presented to the ash monitor. The discharged sample i s

Figure 4. Schematic drawing of Sortex ash monitor sensor system.

CUTTER
NOOOIb/CUT
^ ^ ^ I B R A T I N G FEEDER
HAMMER MILL
CRUSHER
ROTARY SPLITTER
REJECT |l5lb/CUT
8516/CUT
SAMPLE
COLLECTION
SURGE CONTAINER
HOPPER
12 in. S C R E W
CONVEYER
BYPASS
TO SORTEX
RR CAR A S H MONITOR
BYPASS
TO
CALIBRATION RR CAR
SAMPLE
TO RR CAR
Figure 5. Typical coal sampling system and flow path.

combined w i t h the main product stream at the r a i l r o a d car l o a d i n g

chute.
A c t u a l o p e r a t i n g data i n d i c a t e an e x c e l l e n t c o r r e l a t i o n
between the ash monitor and l a b o r a t o r y ash analyses ( 6 ) . The
observed c o r r e l a t i o n equation i s :
Ash Monitor - 0.74 (Lab Ash) +1.88 (2)
Data spanning s i x consecutive months of o p e r a t i o n showed that the

d i f f e r e n c e between the ash monitor r e s u l t s and the l a b o r a t o r y
r e s u l t s was l e s s than 1.12% ash at the 95% confidence l i m i t . The
p r e c i s i o n of the ash monitor d u r i n g the same time p e r i o d averaged
0.53% ash. The f a i l u r e to o b t a i n the i d e a l c o r r e l a t i o n probably
can be a t t r i b u t e d to a number of f a c t o r s ; however, the two meas-

urements are very d i f f e r e n t , the ash monitor provides data i n d i c -
a t i v e of the elemental composition of the m i n e r a l matter i n the
c o a l w h i l e the l a b o r a t o r y analyses y i e l d data r e f l e c t i n g the mass
of m e t a l l i c oxides derived from t h i s m i n e r a l matter.
The accuracy of the ash monitor f o r d i f f e r e n t c o a l types was
evaluated by Cammack and B a l i n t ( 5 ) . For f i f t e e n d i f f e r e n t c o a l
samples w i t h ash content ranging from 4 t o 40% ash, the accuracy
of the ash measurement a t the 95% confidence l i m i t ranged from
+ 0.3 t o + 2.2% ash; the average value f o r t h i s confidence l i m i t
was + 1.3% ash.
The moisture content of the c o a l i s a major v a r i a b l e a f f e c t -
i n g the performance of the ash monitor. I t a l t e r s the packing
c h a r a c t e r i s t i c s of the c o a l , and thereby, i n f l u e n c e s the bulk
d e n s i t y of the sample. Moisture a l s o a f f e c t s the h a n d l i n g char-
a c t e r i s t i c s of the c o a l . Cammack and B a l i n t (5) found that the
compacted c o a l bed has a minimum d e n s i t y a t 8% moisture; and f o r
moisture l e v e l s up to 7%, the maximum e r r o r i n ash a n a l y s i s was
0.5% ash. Jones and Stanley (6) found that the c o a l handling
system does not operate r e l i a b l y above 8% moisture.
The o p e r a t i n g experience a t Moss No. 3 c l e a r l y i n d i c a t e s
t h a t the Sortex Ash Monitor i s a very u s e f u l t o o l and that i t
possess s u f f i c i e n t r e l i a b i l i t y and accuracy to be s u i t a b l e f o r
c o n t r o l of p l a n t c i r c u i t r y . Through use of a c o r r e l a t i o n
equation and c a r e f u l c a l i b r a t i o n , the system should be able t o
provide the accuracy r e q u i r e d to meet the q u a l i t y c o n t r o l
requirements of the c o a l p r e p a r a t i o n i n d u s t r y .
Nuclear d e n s i t y gauges are commercially a v a i l a b l e and have
found use i n many m a t e r i a l h a n d l i n g i n d u s t r i e s . Nuclear d e n s i t y
gauges determine the d e n s i t y of m a t e r i a l by measuring the a t t e n u -
a t i o n of gamma-rays passing through the m a t e r i a l . Equation 1
provides the b a s i s f o r the measurement. The gauge c o n s i s t s of a
r a d i o a c t i v e source, u s u a l l y ^ ^ C s , a gamma-ray d e t e c t o r ,
a m p l i f i e r and a s s o c i a t e d s i g n a l p r o c e s s i n g e l e c t r o n i c s .
Nuclear d e n s i t y gauges are t y p i c a l l y used as process c o n t r o l
instruments t o monitor the d e n s i t y of water-magnetite s l u r r i e s
used i n the heavy medium c l e a n i n g c i r c u i t s . The instrument

package i s designed t o clamp onto a process p i p e . Accuracies of

+ 1-2% are r o u t i n e l y achieved. The n u c l e a r d e n s i t y gauge,
c o n f i g u r e d as a l i n e source w i t h a l i n e a r a r r a y of d e t e c t o r s and
coupled t o a tachometer, i s used as a b e l t s c a l e .
The pH process monitoring and c o n t r o l equipment i s standard
i n d u s t r i a l grade i n s t r u m e n t a t i o n and i s a v a i l a b l e from numerous
vendors. The pH measurement i s commonly made i n the f r o t h f l o t a -
t i o n c e l l s , and c a u s t i c soda or lime i s added t o the t a i l i n g s
output of the f r o t h c e l l s . This measurement i s p r i m a r i l y used t o
c o n t r o l the pH of the p l a n t process water w i t h the set p o i n t
s e l e c t e d t o y i e l d optimum performance from the f l o c c u l a n t s added
t o the s t a t i c t h i c k e n e r . C o n t r o l of the process water a c i d i t y i s
a l s o r e q u i r e d t o minimize the c o r r o s i o n of process equipment.
On-line Instrumentation A p p l i c a b l e t o the Coal P r e p a r a t i o n

Industry. Although numerous measurement concepts have been con-
s i d e r e d f o r o n - l i n e a n a l y s i s i n the c o a l p r e p a r a t i o n i n d u s t r y and
s e v e r a l of these are being evaluated i n the l a b o r a t o r y , e.g.
Môssbauer spectroscopy Ç7), x-ray d i f f r a c t i o n , and x-ray f l u o r e s -
cence, t h i s s e c t i o n w i l l d i s c u s s only those systems that have
undergone or are scheduled f o r f i e l d t e s t i n g and are a d v e r t i s e d
as a v a i l a b l e . These i n c l u d e elemental a n a l y z e r systems, a
moisture monitor, and a coal-rock-water s l u r r y meter.
Two elemental a n a l y z e r systems have been developed, the
"Continuous On-line Nuclear Assay of C o a l " , CONAC, (Science
A p p l i c a t i o n , Inc., Palo A l t o , CA) and "The Elemental A n a l y z e r "
(MDH I n d u s t r i e s , Inc., Monrovia, CA). Both of these u n i t s a r e
based upon the measurement of prompt gamma rays t h a t are emitted
from a nucleus f o l l o w i n g the capture of a neutron. This t e c h -
nique i s commonly known as prompt neutron a c t i v a t i o n a n a l y s i s ,
PNAA.
In a t y p i c a l a p p l i c a t i o n a ^ ^ C f n e t r o n source i s p o s i -
U
t i o n e d e i t h e r beneath a conveyor b e l t or on one s i d e of a g r a v i t y

f e d chute. The h i g h energy neutrons emitted by the neutron
source are t h e r m a l i z e d by the c o a l sample before undergoing cap-
t u r e by the v a r i o u s sample c o n s t i t u t e n t s . The r e s u l t i n g prompt
gamma ray spectrum provides a q u a l i t a t i v e s i g n a t u r e f o r the v a r -
ious elements, and the number of c h a r a c t e r i s t i c photons, which
depends upon the capture cross s e c t i o n and weight percent, p r o -
vides a q u a n t i t a t i v e measure of each element. Most of the emit-
ted gamma rays have energies i n excess of 0.4 MeV and r e a d i l y
penetrate the s t r u c t u r a l m a t e r i a l of the c o a l h a n d l i n g system as
w e l l as the mass of c o a l being measured. The gamma ray d e t e c t o r
i s placed o u t s i d e the c o a l h a n d l i n g system. For those a p p l i c a -
t i o n s r e q u i r i n g analyses f o r major and minor elements a h i g h
r e s o l u t i o n d e t e c t o r , such as germanium-lithium d r i f t e d d e t e c t o r ,
i s used. I f only s u l f u r and a few major elements i n c o a l a r e
d e s i r e d , a medium r e s o l u t i o n d e t e c t o r , such as a Nal (TI) c r y s t a l
i s used. A computerized multichannel a n a l y z e r i s r e q u i r e d to
process the gamma ray data. The system i s c a l i b r a t e d using known

reference samples of c o a l . The CONAC system can handle up to 50

ton/hr c o a l streams; the MDH system can handle up t o 10 ton/hr.
The CONAC system can be s u p p l i e d with the c a p a b i l i t y to
measure a s i n g l e element, e.g., s u l f u r , to perform a complete
elemental a n a l y s i s , or any intermediate l e v e l of a n a l y s i s capa-
bility. The l a r g e r systems a l s o provide an estimate of the BTU
content of the c o a l . Generally, the r e s u l t s from the CONAC s y s -
tem are more p r e c i s e than the r e s u l t s obtained from ASTM a n a l y t i -
c a l procedures (8). L i t e r a t u r e data i n d i c a t e that the accuracy
of the CONAC system surpasses that of the ASTM procedures ( 8 ) ;
however, a c a r e f u l study of i t s accuracy has not been completed,
p r i m a r i l y because of the u n a v a i l a b i l i t y of a v a r i e t y of standard
samples i n q u a n t i t i e s r e q u i r e d by the CONAC system. The heating
value of the c o a l sample i s c a l c u l a t e d from an e m p i r i c a l equation

(9) , which requires analyses f o r hydrogen, oxygen, nitrogen, and
s u l f u r . The agreement with r e s u l t s obtained by bomb caloriraetry
i s e x c e l l e n t (+ 1.2 + 0.3%). Coal samples with top s i z e s up to 8
cm per s i d e have been s u c c e s s f u l l y analyzed.
The MDH "Elemental Analyzer" performs analyses f o r s u l f u r
and the major ash forming elements; an estimate of the BTU con-
tent i s a l s o provided. Computer simulations of the systems per-
formance i n d i c a t e that s u l f u r analyses can be performed with
e r r o r s of + 2.2% and ash analyses with average e r r o r s of + 3.4%
(10) . Experimental data acquired with the system have not been
reported.
A CONAC system, " S u l f c o a l y z e r " , has been i n s t a l l e d at
D e t r o i t Edison Company's Monroe, Michigan, power s t a t i o n (11).
This plant i s a four u n i t complex rated at 3000 megawatts. The
" S u l f c o a l y z e r " cost $500,000 and w i l l be used to c o n t r o l the c o a l
blending f a c i l i t y . Operating data from t h i s i n s t a l l a t i o n are not
a v a i l a b l e . A second CONAC system w i l l be i n s t a l l e d a t the
Tennessee V a l l e y Authority, Kingston, Tennessee, steam p l a n t .
This plant i s a m u l t i - b o i l e r complex with 1600 megawatt c a p a c i t y .
The CONAC system w i l l be used i n connection with a consent agree-
ment i n v o l v i n g environmental r e g u l a t i o n s , compliance schedules,
and methods of achieving compliance f o r s u l f u r dioxide and par-
t i c u l a t e emissions. While i t seems most d e s i r a b l e to c o n t r o l
c o a l q u a l i t y at the mine or at a preparation p l a n t , the important
c o n t r o l point f o r a u t i l i t y i s at the d e l i v e r y area at the power
s t a t i o n . TVA's i n i t i a l e f f o r t w i l l concentrate on the use of the
" S u l f c o a l y z e r " to monitor c o a l as i t i s d e l i v e r e d . A CONAC
system has not been i n s t a l l e d at any c o a l preparation p l a n t .
Two i n s t a l l a t i o n s of the MDH "Elemental Analyzer" are
planned, one i n a c o a l a p p l i c a t i o n and a second u n i t i n an o i l
blending f a c i l i t y (12). The c o a l a p p l i c a t i o n i s i n the Homer
C i t y , Pennsylvania, c o a l preparation plant c u r r e n t l y under con-
struction. The analyzer system w i l l provide a feedback s i g n a l
that w i l l be used to c o n t r o l the s p e c i f i c g r a v i t y of the heavy
media c o a l c l e a n i n g operations. The i n s t a l l a t i o n was scheduled
f o r Spring, 1981. The u n i t cost $300,000.

On-line moisture monitors, which are based on i n f r a - r e d

a b s o r p t i o n , nuclear magnetic resonance, capacitance and microwave
a t t e n u a t i o n are used i n numerous process i n d u s t r i e s . The a p p l i
c a b i l i t y of these techniques to the c o a l p r e p a r a t i o n industry has
been reviewed (13,14)· The C0NAC and "Elemental Analyzer" u n i t s
use a microwave a t t e n u a t i o n method f o r the moisture measurement.
This information i s used to c o r r e c t the PNAA hydrogen assay data
i n order to c a l c u l a t e the hydrogen content of the c o a l . Kay-
Ray, Inc., ( A r l i n g t o n Heights, I l l i n o i s ) has developed an
instrument that measures the moisture content of a coke stream
and uses a combination of microwave and gamma ray a t t e n u a t i o n
measurements.
A schematic diagram of an o n - l i n e microwave moisture monitor
i s shown i n Figure 6. At a frequency of 1 GHz sample thickness

of approximately 15 cm are employed.
D i p o l e - d i p o l e i n t e r a c t i o n between molecules placed i n an
o s c i l l a t i n g e l e c t r i c f i e l d r e s u l t s i n energy being t r a n s f e r r e d
from the o s c i l l a t i n g f i e l d to the sample. This phenomenon
manifests i t s e l f as a frequency dependent d i e l e c t r i c constant and
i s a property common t o a l l m a t e r i a l s . The p h y s i c a l b a s i s of the
measurement i s expressed by Equation 3.
Ρ = P 0 exp[-2at] (3)
P i s the i n c i d e n t power, Ρ i s the t r a n s m i t t e d power, t i s the

0
sample t h i c k n e s s , and α i s the a t t e n u a t i o n f a c t o r defined by

Equation 4:
(4)
ω i s the frequency, y i s the magnetic p e r m e a b i l i t y , Σ i s

Q s
the s t a t i c component of the d i e l e c t r i c constant, and Σ ^ i s the

complex component of the d i e l e c t r i c constant, i . e . , the frequency
dependent term. Because water i s a very p o l a r molecule, r e l a t i v e
to the hydrocarbon c o n s t i t u e n t s of c o a l , i t i s r e s p o n s i b l e f o r a
s i g n i f i c a n t f r a c t i o n of the microwave a t t e n u a t i o n , i . e , tan
(Σ^/Σ )>>1, and Equation 4 reduces to
8
α * ω /μ Zjl (5)
— ο I
A t y p i c a l response curve obtained f o r an i n d i v i d u a l seam of
c o a l i s shown i n Figure 7. Two major aspects of the measurement
are contained i n t h i s response curve. F i r s t , the curve i s com
posed of two l i n e a r segments. The p o r t i o n of the curve with the
smaller slope i s due to water adsorbed on the c o a l surface, and
because of the r e s t r i c t e d motion i t s l o s s f a c t o r , a, i s l e s s than
that of f r e e water molecules. The p o r t i o n of the curve with the
l a r g e r slope i s due to the bulk water a s s o c i a t e d with the c o a l .

RECORDER
Figure 6. Schematic drawing of an on-line microwave moisture meter.

MOISTURE (%)
Figure 7. Response of microwave moisture meter for an individual seam of coal.

The band nature of the response curve i s r e l a t e d to the average

particle size. As the average p a r t i c l e s i z e decreases the g r a d i
ent of both l i n e a r segments decreases. Changes i n the bulk
d e n s i t y and the surface t o volume r a t i o , and the r e s u l t i n g change
i n the r a t i o of surface to bulk water have been p o s t u l a t e d as
r e s p o n s i b l e f o r these changes i n the slopes of the response curve
(15). From the envelope of t h i s curve and the p r e c i s i o n of the
a t t e n u a t i o n measurement, the moisture content of a known c o a l can
be measured with an u n c e r t a i n t y of + 1% water. I f the c o a l type
i s unknown the u n c e r t a i n t y i n c r e a s e s t o approximately + 2.8%
water (13).
Coal transport i n the intermediate and f i n e c o a l p r o c e s s i n g
c i r c u i t s of a c o a l p r e p a r a t i o n plant i s accomplished by means of
water-coal s l u r r i e s . C o n t r o l of the various unit operations

w i t h i n these c i r c u i t s requires a means of measuring the r e l a t i v e
masses of c o a l , rock, and water i n the feed, product and/or waste
streams. Science A p p l i c a t i o n , Inc., under contract from the
P i t t s b u r g Mining Technology Center, U. S. Department of Energy,
has developed a s l u r r y c o n c e n t r a t i o n meter (16). Although i t s
intended a p p l i c a t i o n i s i n s l u r r y haulage systems, i t i s e q u a l l y
a p p l i c a b l e i n the c o a l p r e p a r a t i o n i n d u s t r y .
Figure 8 contains a schematic drawing of the s l u r r y concen
t r a t i o n meter. The instrument package c o n s i s t s of three separate
gauges: a gamma density gauge, a neutron gauge, and a conduc
t i v i t y gauge. The gamma density gauge provides a measure of the
t o t a l mass, the neutron gauge provides a measure of the t o t a l
hydrogen, and the c o n d u c t i v i t y gauge measures the f r e e water i n
the s l u r r y . The equations r e l a t i n g the observed response of each
gauge t o the mass of each component a r e :
(a) gamma gauge
Ύ Ύ Ύ
Μ μ + Μ μ + Μ μ » -1η (Ν /ε ) (6)
ce r r ww γ γ
(b) neutron gauge
11
Μ μ* + M / + M μ = -In (Ν /ε ) (7)
ce r r ww n n
and (c) c o n d u c t i v i t y gauge
M/ w = K O w (8)
M , M , and M denote the mass ^per ûnit area of c o a l , rock,

c r w
Ύ 1
and water; μ , μ^., and μ ^ and μ , μ^, and μ ^ a r e the e f f e c t i v e
0 0
gararaa-ray and neutron mass a b s o r p t i o n c o e f f i c i e n t s , ε and ε η
are the e f f i c i e n c e s of the gamma and neutron d e t e c t i o n systems.

o and a are the c o n d u c t i v i t y of the water phase measured i n
w w
a reference c e l l and the c o n d u c t i v i t y of the s l u r r y , respec

t i v e l y ; Κ i s the c o n d u c t i v i t y c e l l constant. S o l v i n g these

SIGNAL
PROCESSOR
I
CONDUCTIVITY -IRON PIPE
GAUGE
GAMMA GAMMA
GAUGE GAUGE
JL
SLURRY
>
GAMMA
SOURCE
NEUTRON
SOURCE
iT
PVC PIPE-
Figure 8. Schematic drawing of the coal slurry concentration meter.

equations simultaneously y i e l d s the r e l a t i v e p r o p o r t i o n of c o a l ,

rock, and water i n the s l u r r y .
The s l u r r y gauge was evaluated at the Colorado School of
Mines, Research I n s t i t u t e . For s l u r r i e s i n which the p a r t i c l e
s i z e s were l e s s than 0.6 mm, the absolute d i f f e r e n c e between the
measured and a c t u a l s l u r r y composition averaged 1.7%. Slurries
c o n t a i n i n g 0 to 25% c o a l and rock were u t i l i z e d i n these t e s t s .
The p r e c i s i o n of the measurement was l i m i t e d by the counting s t a -
tistics. Response time i s one second. For s l u r r i e s c o n t a i n i n g
s o l i d p a r t i c l e s approximately o n e - t h i r d the pipe diameter, l a r g e
e r r o r s i n the measured s l u r r y composition were observed. These
e r r o r s are probably due to the i r r e g u l a r movement of the l a r g e
p a r t i c l e s . The custom designed s l u r r y c o n c e n t r a t i o n meter cost
$150,000; mass production of the meter probably w i l l reduce the

cost to $75,000 (17)»
Economic Considerations of On-Line A n a l y t i c a l Instruments
Most c o a l p r e p a r a t i o n p l a n t s use instrumentation to inform

the c o n t r o l room operator of equipment status and guide the
employees w i t h i n the plant i n the manual adjustment of the set
points on the process equipment. Many u n i t operations are not
equipped with any instrumentation and s u c c e s s f u l implementation
of these u n i t operations r e l i e s t o t a l l y upon the experience of an
employee charged with the r e s p o n s i b i l i t y of monitoring s p e c i f i c
p i e c e s of process equipment. New p l a n t s are being designed with
increased l e v e l s of automation and o n - l i n e instrumentation; how-
ever, the investment i n instruments i s only a small f r a c t i o n of
comparable investments i n other process i n d u s t r i e s . For example,
the p r o j e c t team v i s i t e d two modern c o a l p r e p a r a t i o n plants i n
the Appalachian c o a l f i e l d s which cost $75,000,000 and the t o t a l
o n - l i n e instrumentation investment was approximately $150,000.
The r a t i o of instrumentation to p l a n t investment i n the chemical
industry i s s i g n i f i c a n t l y larger.
Several f a c t o r s are r e s p o n s i b l e f o r the low investment i n
o n - l i n e instrumentation. F i r s t , c o a l r e l a t i v e to other f u e l s i s
undervalued, and as a r e s u l t the c o a l i n d u s t r y i s under c a p i t a l -
ized. Second, the c o a l i n d u s t r y has been r e l u c t a n t to t r y new
technology. However, based upon v i s i t s to s e v e r a l c o a l prepara-
t i o n p l a n t s i n the Eastern U.S., the r a t e of t e c h n o l o g i c a l change
w i t h i n the c o a l p r e p a r a t i o n i n d u s t r y i s a c c e l e r a t i n g . For exam-
p l e , computers are being used to a u t o m a t i c a l l y operate c o a l
p r e p a r a t i o n p l a n t s . T h i r d , an economic r a t i o n a l e f o r o n - l i n e
instrumentation has not been provided. F i n a l l y , only a p p r o x i -
mately o n e - t h i r d of the t o t a l c o a l mined i s cleaned, and t h i s
f
f r a c t i o n has been d e c l i n i n g since the raid 1960 s.
The economic b e n e f i t derived from the use of o n - l i n e process
c o n t r o l and q u a l i t y c o n t r o l instruments u l t i m a t e l y must be t r a n s -
l a t e d i n t o the a b i l i t y to improve product q u a l i t y , i . e . , improve
product s p e c i f i c a t i o n s and reduce v a r i a t i o n s i n product q u a l i t y .

Improved o n - l i n e instrumentation should allow the c o a l prepara-

t i o n p l a n t operator t o accomplish t h i s o b j e c t i v e through a more
e f f i c i e n t use of the raw m a t e r i a l , by producing more product
without i n c r e a s i n g plant c a p a c i t y , and by a l l o w i n g one to operate
c l o s e r to product s p e c i f i c a t i o n l i m i t s . A r e d u c t i o n i n operating
and maintenance costs should a l s o occur.
On-Line Instrumentation Development Needs
The o n - l i n e instrumentation development needs can be d i v i d e d

along the t r a d i t i o n a l l i n e s of q u a l i t y c o n t r o l and process con-
t r o l instrumentation. The i n t e r r e l a t i o n s h i p between the two and
the proposed mode of i n t e r a c t i o n are shown i n Figure 9. The
q u a l i t y c o n t r o l instruments, i n an o p e r a t i o n a l and a p r a c t i c a l
sense, are l o c a t e d outside the preparation p l a n t . As a r e s u l t of
data obtained on product q u a l i t y , the q u a l i t y c o n t r o l instrument
i n t e r a c t s with the p l a n t feed and the process c o n t r o l instrumen-
t a t i o n to optimize the use of raw m a t e r i a l c o n s i s t e n t with the
d e s i r e d product s p e c i f i c a t i o n s . This feedback loop can be auto-
matic; however, current p r a c t i c e places the p r e p a r a t i o n plant
superintendent or engineer i n the loop and the q u a l i t y c o n t r o l
measurement i n a remote l a b o r a t o r y , r e s u l t i n g i n manual c o n t r o l
scheme with a long time delay. The process c o n t r o l instrumenta-
t i o n c o n t r o l s a s i n g l e u n i t o p e r a t i o n and the instrumentation i s
unique to each u n i t operation. T h e i r set points are e s t a b l i s h e d
by the output from the q u a l i t y c o n t r o l instruments.
S e v e r a l q u a l i t y c o n t r o l devices are a v a i l a b l e and the d e v e l -
opment status has been summarized i n a previous s e c t i o n . Labora-
t o r y s t u d i e s i n d i c a t e that the p r e c i s i o n and accuracy of these
devices are adequate to meet product c e r t i f i c a t i o n needs. Field-
ing t e s t i n g of these u n i t s i n the c o a l p r e p a r a t i o n plant e n v i r o n -
ment i s r e q u i r e d to demonstrate t h e i r usefulness and economic
viability.
The development status of process c o n t r o l instrumentation
lags that of the q u a l i t y c o n t r o l instruments s i g n i f i c a n t l y .
Nuclear density gauges f u n c t i o n i n the c o a l preparation plant
environment. The s l u r r y c o n c e n t r a t i o n meter has a p p l i c a t i o n i n
the intermediate and f i n e s i z e d c o a l cleaning c i r c u i t s and needs
to be t e s t e d i n a p r e p a r a t i o n p l a n t . Other devices, such as ash
monitors to c o n t r o l the operation of heavy media baths or j i g s
are not a v a i l a b l e ; and instruments developed f o r other process
i n d u s t r i e s are not s u i t a b l e f o r use i n c o a l p r e p a r a t i o n p l a n t s .
Modeling s t u d i e s of the v a r i o u s u n i t operations are required i n
order to a s c e r t a i n the fundamental parameters required to auto-
mate the c o n t r o l of these systems. Primary process c o n t r o l
instrument needs include ash, s u l f u r , and moisture monitors;
secondary needs include an o n - l i n e w a s h a b i l i t y and ash f u s i o n
measurement·

FEED
QUALITY CONTROL
INSTRUMENTATION
j t_.
1 ^ I PROCESS CONTROL
Γ1 INSTRUMENTATION |
1 ι
I
I—^
UNIT
I OPERATION
ι
PREPARATION PLANT
Figure 9. Interrelationship between process control quality

and control on-line
instrumentation.

Acknowledgement
Research sponsored by the O f f i c e of Energy Research, U. S.
Department of Energy under Contract W-7405-eng-26 w i t h the Union
Carbide Corporation.
Literature Cited
1. "Engineering/Economic Analysis of Coal Preparation with SO 2
Cleanup Processes", ΕΡΑ-600/7-78-002, U. S. Department of

Energy, Pittsburgh, ΡΑ., 1979.
2. "Environmental Assessment of Coal Cleaning Processes:
Technology Overview", EPA-600/7-79-073e, U. S. Environmental

Protection Agency, 1979.
3. Vivenzio, Τ. Α . , "Impact of Cleaned Coal on Power Plant
Performance and Reliability", Electric Power Research
Institute, EPRI CS-1400, 1980.
4. "Gaseous Fuels; Coal and Coke; Atmospheric Analysis, Part
26", American Society for Testing and Materials,
Philadelphia, PA., 1978.
5. Cammack, P.; Balint, Α., Trans. SME, 1976, 260, 361.
6. Jones, D. W.; Stanley, F. L., "Ash Monitoring at Pittston
Moss No. 3 Plant", Coal Convention of the American Mining
Congress, St. Louis, MO, 1978.
7. Levinson, L. W., "Mossbauer Effect Spectroscopic Study of
Pyritic Sulfur in Coal", EPRI FP-1228, 1979.
8. Tassicker, O. J., "Continuous Nuclear Analyzer of Coal for
Improved Combustion Control", International Symposium on
Pulverized Coal Firing and Its Effects, University of
Newcastle, Australia, 1979.
9. Berkowitz, N., "An Introduction to Coal Technology", Academic
Press, 1979, p. 35.
10. Cekorich, Α.; Deich, H.; Harringon, T . ; Marshall, J . H. III,
"Performance of an On-line Elemental Analyzer for Coal", 2nd
International Coal Utilization Conference, Houston, TX, 1979.
11. Lagarias, J.; Irminger, P.; Dodson, W., "Nuclear Assay of
Coal, Vol. 8, Continuous Nuclear Assay of Coal: Progress
Review and Industry Applications", EPRI FP-989, January 1979.
12. Deich, Η., MDH Industries, personal communication.
13. Brown, D. R.; Gozani, T . ; Elias, E.; Bozorgmanesh, Η.,
"Nuclear Assay of Coal, Volume 4: Moisture Determination in
Coal - Survey of Electromagnetic Techniques", EPRI CS-989,
1980.
14. Fauth, G., "On-Stream Determination of Ash and Moisture
Content in West German Coal Preparation Plants", Proceedings
of the 1980 Symposium on Instrumentation and Control for
Fossil Energy Processes, Virginia Beach, VA, 1980.

15. Hall, D. Α.; Sproson, J . C . ; Gray, W. Α., J . Institute of

Fuel, 1970, 43, 350.
16. Verbinski, V. V . ; Cassapakis, C. G.; deLesdernier, D. L.;
Wang, R. C . , "Three Component Coal Slurry Sensor for Coal,
Rock, and Water Concentrations in Underground Mining
Operations", 6th International Conference on the Hydraulic
Transport of Solids in Pipes, University of Kent, United
Kingdom, 1979.
17. Orphan, V. J., Science Applications, Inc., personal
communication.


Coal as Energy in the Steel Industry
D A N P. M A N K A
1109 Lancaster Avenue, Pittsburgh, PA 15218
The iron and steel industry uses up to 20 per-

cent of the energy consumed by industry in the

United States. Coal is a major source of this
energy. Turning coal into coke has three major
advantages to the industry: coke is essential as
a source of heat in the blast furnace. One-third
of the gas generated during the coking of coal is
a source of heat for underfiring of the coke ovens
and two-thirds is used in steel reheating furnaces.
The coal-byproduct chemicals derived from the gas
are increasingly valuable. Washed metallurgical
bituminous coal is charged into the ovens. It must
have low sulfur and low silica content; it must
have proper volatile matter and expansion proper-
ties, otherwise it will stick in the ovens. Anal-
yses of the various coals charged to the ovens will
be discussed, as well as the composition of the
gases liberated during the carbonisation cycle.
Recovery of the various chemicals from the gas will
be discussed. The mixture of iron ore and lime-
stone in the blast furnace is heated by the coke to
form liquid pig iron. The gases liberated in the
blast furnaces are used in stoves to preheat the air
which is blown into the furnace to maintain combus-
tion of the coke. The liquid pig iron is refined
to liquid steel by direct reaction with oxygen in
the Basic Oxygen Furnace. Some boiler coal is used
as a source of heat in boilers to produce steam
used throughout the coke and steel plants.
The iron and steel industry uses up to 20 percent of the

energy consumed by all industry in the United States. Coal is
a major source of this energy. Converting coal Into coke serves
this steel industry in three ways.
1. Coke is essential as a source of heat and as a reactant
in the blast furnace to convert iron ore into pig iron.
0097-6156/82/0205-0281$06.00/0

2. One-third o f the gas generated d u r i n g the coking o f c o a l

i s a source o f heat f o r u n d e r f i r i n g o f the coke ovens.
3 . The remaining two-thirds o f t h e gas i s used i n the r e -
heating furnaces i n the s t e e l p l a n t .
Valuable chemicals are recovered from the gas i n the coke
p l a n t . Benaene i s used i n the production o f nylon, toluene and
xylene a r e used as s o l v e n t s and i n the making o f v a r i o u s chemi-
c a l s . Phenols recovered from t a r and the gas f i n d uses i n making
thermosetting p h e n o l i c p l a s t i e s . Ammonia i s used as f e r t i l i s e r
i n a g r i c u l t u r e . Coumarone-indene recovered from the high b o i l i n g
s o l v e n t i s used i n the r e s i n i n d u s t r y . Naphthalene recovered
from t a r i s used t o make p h t h a l i c anhydride. There a r e l i t e r a l l y
hundreds o f compounds i n the t a r and the chemicals recovered from
the coke oven gas. S e v e r a l o f these a r e i n s u f f i c i e n t l y l a r g e

concentrations t o make recovery i n pure form economically f e a s -
ible.
In the production o f coke c o a l i s heated f o r s e v e r a l hours
f
i n ovens i n the absence o f a i r a t temperatures above 1000°C t o

remove the v o l a t i l e matter i n the c o a l . C o a l must be washed with
water t o remove many i m p u r i t i e s . I t i s charged t o the ovens i n
the wet o r d r y form.
A coke oven i s constructed from high temperature, s t r o n g
b r i c k s . The oven dimensions a r e 1 5 t o 18 inches i n width, 1 5 f t .
high, and f t . i n l e n g t h . The l a r g e s t width o f 18 inches i s on
the s o - c a l l e d coke s i d e where the coke i s pushed out o f the oven
i n t o coke c a r s . Subsequently, the r e d hot coke i s cooled d i r e c t -
l y with water. The narrow, o r 1 5 i n c h width, i s on the other end
of the oven g e n e r a l l y c a l l e d the pusher s i d e where a l a r g e ram
from a pusher c a r i s guided i n t o the oven t o push out the coke.
Between the outer w a l l s o f the ovens i s an opening extending the
f u l l height and l e n g t h o f the oven which i s the f l u e . Coke oven
gas i s burned i n these f l u e s t o supply heat t o the charged c o a l .
The w a l l on one s i d e o f the oven i s heated f o r a predetermined
time and then the other w a l l i s heated f o r the same p e r i o d o f
time. I n t h i s manner, heat i s s u p p l i e d t o the c o a l t o coke the
coal uniformly.
G e n e r a l l y , there a r e 5 9 ovens t o a b a t t e r y . A l l the v o l a t i l e
l i q u i d f l o w i n g from a b a t t e r y i s c o l l e c t e d i n a separate c o l l e c t -
ing main before the l i q u i d s from a l l the b a t t e r i e s a r e mixed t o -
gether ahead o f the t a r - l i q u o r s e p a r a t i n g tanks. Some b a t t e r i e s
may c o n t a i n as many as 7 9 ovens. I n t h i s d i s c u s s i o n we w i l l con-
s i d e r a coke p l a n t c o n s i s t i n g o f f o u r b a t t e r i e s with 5 9 ovens
each and one b a t t e r y c o n t a i n i n g 7 9 ovens f o r a t o t a l o f 3 1 5 ovens.
Not every c o a l can be charged t o the ovens. The concentra-
t i o n o f a s h and s u l f u r must be considered t o make good, s t r o n g
coke. Too much s u l f u r i n the coke w i l l f i n d i t s way i n t o the
s t e e l . Some c o a l s expand when they a r e heated, while others con-
t r a c t . Some c o a l s have a high content o f v o l a t i l e matter, while
others have a low c o n c e n t r a t i o n . Therefore, blends o f v a r i o u s
c o a l mixes a r e coked i n s m a l l experimental ovens t o determine the

14. MANKA Coal as Energy in the Steel Industry 283
expansion or contraction of the coal and the physical character

istics of the final coke. If the coal expands too much, it will
be detrimental to the walls of the ovens and also cause sticking
of the coke, so that it cannot be pushed out of the ovens. Stick
ing ovens removes them from normal production, thereby lowering
the daily production of coke. The sticking ovens in many cases
have to be cooled down to facilitate removal of coke and again
must be reheated before charging with eoal. Too much contrac
tion of the coal forms an undesirable, dense coke.
Table I lists the analysis of a typical coal mixture charged
to the ovens. The lower the sulfur content, the lower the HgS
concentration in the coke oven gas that must be removed from the
gas before it is burned to meet the pollution standards set by
EPA. Note that the contracting coals expand somewhat during the
coking process before finally contracting. The expansion and eon-
traction of the various coals was determined on the individual
coals charged to the small experimental oven. The coal mixture
is determined on the quality of the final coke, whieh must meet
certain hardness, volatile matter, ash and sulfur content to be
suitable for use in the blast furnace.
The oven is charged through three openings located on top of
the oven. The oven is filled to a heighth of 12 feet with 16.2
tons. A leveling bar on the pusher machine levels the eoal in the
oven. As noted previously, a l l doors and openings on the oven are
closed so that the coal is heated in the absenee of air, otherwise
the eoal would only burn and not form coke. Oxygen analysis of
the gas exiting the oven during the 16-17 hour coking cycle is
0 . 1 # or less. A total of 695° tons of coal is charged per day,
forming 46Θ0 tons of coke per day, and 7 3 , 3 0 0 , 0 0 0 cubic feet of
coke oven gas per day.
Coke Oven Gas Flow Diagram
The flow diagram of gas is practically the same in a l l coke

plants. As more desulfuriaation processes are installed, these
will vary in location depending on the type of system being i n
stalled.
In the flow diagram in Figure 1, coke oven gas rises from the
coke oven, a, through standpipe, b, to gooseneck, c, where it is
contacted with flushing liquor (ammonia liquor). Tar and moisture
are condensed. Ammonium ehloride, and a portion of the ammonia,
fixed gases, hydrogen cyanide and hydrogen sulfide are dissolved
by the liquor. The gas, liquor and tar enter the gas collecting
main, d, which is connected to a l l the ovens of a battery. In
some cases there may be two gas collecting mains to a battery.
The gas, liquor and tar are separated in tar decanters. The tar,
f, separated from the liquor, e, flows to tar storage, g. A por
tion of the liquor, e, is pumped to the gooseneck, c, on the top
of each oven. The remainder of the liquor is pumped to the
ammonia liquor s t i l l , h, where it is contacted with live steam to
drive off free ammonia, fixed gases, hydrogen cyanide, and

to
00
4*
Table I. Analysis of Typical Coal Mixture Charged to Ovens.
% IN % VOLATILE % FIXED
MIX MATTER CARBON % ASH %S % H0 2
LOW VOLATILE 12 16.3 75.7 8.0 0.7 6.5 12.5% EXPANSION

W. VA. 13 psig PRESSURE
MID VOLATILE 15 24.7 68.4 6.9 0.89 7.5 8.0% EXPANSION

PA. 4 psig PRESSURE
HIGH VOLATILE 46 36.4 56.7 6.9 1.35 7.0 26% CONTRACTION

PA. 0.9 psig PRESSURE
BEFORE CONTRACTION
HIGH VOLATILE 27 33.6 61.4 5.0 0.64 7.4 15.5% CONTRACTION

W. VA. 2 psig PRESSURE ι
BEFORE CONTRACTION >
α
MIXTURE 31.4 62.9 5.7 1.03 6.3 10% CONTRACTION ο
1.7 psig PRESSURE g

BEFORE CONTRACTION r
I
ο
H
C/3

hydrogen s u l f i d e . As the l i q u o r flows from the f r e e s t i l l , h t o t
the f i x e d s t i l l , i , i t i s contacted with lime o r sodium hydroxide,

k, t o l i b e r a t e f r e e ammonia from ammonium c h l o r i d e . L i v e steam,
admitted a t j , flows up through the f i x e d and f r e e s t i l l s and the
ammonia, f i x e d gases, hydrogen cyanide and hydrogen s u l f i d e are
added through, 1, t o the main coke oven gas stream ahead o f the
ammonia s a t u r a t o r , r .
The coke oven gas, separated from l i q u o r and t a r i n , e, i s
cooled i n d i r e c t l y with water i n the primary c o o l e r s , m. The
f i n e t a r t h a t separates from the gas i s pumped through, n, t o the
t a r storage tank. The cooled gas i s pumped by exhausters, o, t o
the e l e c t r o s t a t i c p r e c i p i t a t o r s , p, where a d d i t i o n a l f i n e t a r i s
condensed and pumped through, q, t o the t a r storage tanks. The
gas i s contacted with a d i l u t e s o l u t i o n o f s u l f u r i c a c i d i n the

ammonia s a t u r a t o r , r , t o remove f r e e ammonia. The ammonium s u l -
f a t e - l a d e n a c i d flows through, s, t o the ammonia c r y s t a l l i z e r
(not shown) where c r y s t a l s o f ammonium s u l f a t e are separated, and
the remaining s u l f u r i c a c i d i s pumped back t o the ammonia s a t u r a -
t o r through, t .
The ammonia-free gas flows t o the f i n a l c o o l e r s , u, where
i t i s f u r t h e r cooled by d i r e c t water c o n t a c t . The water p l u s con-
densed naphthalene flows from the c o o l e r through t a r , which ab-
sorbs the naphthalene. The water i s cooled and r e c i r c u l a t e d i n t o
the f i n a l c o o l e r through, v.
The cooled gas enters the wash o i l scrubbers, w, a l s o known
as benzole scrubbers, where i t contacts wash o i l , a petroleum o i l ,
pumped i n t o the scrubbers through y. The a l i p h a t i c and aromatic
compounds a r e e x t r a c t e d from the gas by the wash o i l . The p r i n -
c i p a l components a r e benzene, toluene, xylenes, indene, and s o l -
vent, a l s o known c o l l e c t i v e l y as l i g h t o i l . The b e n z o l i z e d wash
o i l i s pumped through, x, t o the wash o i l s t i l l (not shown) where
l i v e steam s t r i p e out the l i g h t o i l compounds. The debenzolized
wash o i l i s cooled and returned t o the wash o i l scrubber. I n some
p l a n t s the l i g h t o i l i s f u r t h e r processed and f r a c t i o n a t e d i n t o
benzene, toluene, and xylenes and i n t o a h i g h - b o i l i n g s o l v e n t
f r a c t i o n . Naphthalene i s a l s o present i n the l i g h t o i l . Plants
with low volumes o f l i g h t o i l do not have f a c i l i t i e s f o r r e f i n i n g ,
t h e r e f o r e , the o i l i s s o l d t o l a r g e r e f i n e r i e s .
The gas from the wash o i l scrubbers flows through, z, t o a
gas h o l d e r which tends t o e q u a l i z e the pressure. Booster pumps
d i s t r i b u t e o n e - t h i r d o f the gas f o r u n d e r f i r i n g o f the coke ovens,
and two-thirds t o the s t e e l p l a n t where i t i s used as a f u e l i n
the many f u r n a c e s .
Determining End o f Coking Cycle By Gas A n a l y s i s
The l e n g t h o f a coking c y c l e f o r c a r b o n i z i n g o f c o a l i n an
oven i s determined from experience and the range o f the f l u e tem-
p e r a t u r e . Most coke p l a n t s a l s o have experimental coke ovens t o
determine coking c y c l e s f o r v a r i a b l e c o a l mixes and a t d i f f e r e n t
f l u e temperatures. Another method t o determine the end o f t h i s

c y c l e i s by a n a l y s i s o f the gas f l o w i n g from the oven i n t o the

standpipe. T h i s s e e t i o n w i l l d e s c r i b e t h i s approach.
A. Sampling System. The gas sample from the standpipe must be

eooled, separated from t a r and water and f i l t e r e d before i t i s
analyzed f o r Ho, 0^, N » CH/. CO, CO? and i l l u m i n a n t s .
2 f
The sampling t r a i n i n F i g u r e 2 has been used s u c c e s s f u l l y f o r

the continuous pumping o f gas t o a sample b o t t l e o r t o a gas
chromâtograph. I t i s designed t o operate f o r s e v e r a l hours so
t h a t many samples can be analyzed before there i s an accumulation
of t a r i n probe. c o r i n the s e p a r a t o r s , d.
t
Standpipe, b i s l o c a t e d on the gas discharge and on t o p o f

f
coke oven. a . Normally, there i s an opening on the s i d e o f the

standpipe where l i v e steam i s admitted t o remove accumulated t a r

i n the p i p e . T h i s opening i s i d e a l l y l o c a t e d f o r gas sampling,
s i n c e i t i s g e n e r a l l y about two t o three f e e t above the oven.
The probe, c, extending t o approximately the center o f the
standpipe. i s a 3A i n c h o r 1 i n c h heavy w a l l s t a i n l e s s s t e e l p i p e .
The end o f t h i s pipe i n the gas stream i s sealed and the other end
has a plug f o r removing accumulated t a r . A l / 4 - i n c h by a p p r o x i -
mately 3 - i n c h s l o t i s c u t along the l e n g t h o f the pipe i n the gas
stream extending from the c l o s e d end. When the probe i s i n s e r t e d
i n t o the standpipe. i t i s important t h a t the s l o t face the l l r e c -
t i o n o f gas flow. T h i s p o s i t i o n decreases the amount o f t a r
pumped i n with the sample gas. The probe i s i n s e r t e d i n t o a plug
s i m i l a r t o the one used f o r the steam l i n e and pushed through the
opening i n the standpipe u n t i l the plug s e a l s the opening. This
i n s e r t i o n should be done r a p i d l y t o prevent excessive flow o f coke
oven gas through the opening. The probe extending outside o f the
pipe and the l / t f - i n e h pipe from the probe t o the f i r s t separator,
d should be i n s u l a t e d .
f
The two s e p a r a t o r s , d, f o r c o o l i n g the gas and s e p a r a t i o n o f

t a r and water, a r e i d e n t i c a l . These a r e made from *f-ineh pipe,
10- t o 12-inch long, one and sealed and a flange with a gasket on
the t o p end. The i n l e t pipe extends approximately half-way i n t o
the s e p a r a t o r . Both separators a r e kept i n a bucket o f water, e.
The separators should be pressure t e s t e d before they are used.
The remaining p i p i n g i s l/Jf-inch copper o r s t a i n l e s s t u b i n g with
Swaglock f i t t i n g s . Although most o f the t a r i s condensed i n the
s e p a r a t o r s , the gas i s drawn through g l a s s wool i n a g l a s s tube, f ,
t o remove the l i g h t e r t a r o i l . T h i s g l a s s tube can be a g l a s s
b o t t l e normally used i n the l a b o r a t o r y t o d r y gases with d r i e r i t e .
I t has an i n l e t connection on the bottom, an o u t l e t connection near
the top, and a metal screw cap with a s e a l on the top. Tygon
t u b i n g i s used f o r the metal tube t o g l a s s connection. The gas
flows through a f i n a l f i l t e r , &, t h a t removes submicron p a r t i c l e s ,
such as the P a l l T r i n i t y " J u n i o r S i z e " E p o c e l c a r t r i d g e . The gas
i s drawn from the standpipe by a p e r i s t a l t i c pump, i . Good r e -
s u l t s a r e obtained with t h i s type o f pump u s i n g a l / 2 - o r 5 / 8 - i n c h
diameter p l a s t i c tube f o r conveying the gas. The t u b i n g i s e a s i l y

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r e p l a c e d i f i t "becomes broken o r contaminated. A vacuum gauge, h f
ahead o f the pump i s v a l u a b l e t o d e t e c t plugging o f l i n e s o r sepa-

r a t o r s . When vacuum reaches 20 inches, i t i s most probable t h a t
t a r i s accumulating i n the probe. A rod i n s e r t e d i n t o the probe
through the plug opening o f the probe w i l l g e n e r a l l y be s u f f i c i e n t
t o reopen the pipe.
Gas passes through v a l v e , k, a f t e r the pump, i , and i s d r i e d
i n tube, 1 , c o n t a i n i n g d r i e r i t e . The flow t o the sample l o o p o f
the chromâtograph i s maintained a t $0 ec per minute as i n d i c a t e d
by rotometer m. Excess sample gas i s vented t o atmosphere
through valve j .
B. C r s a t A n a l y s i s . I f a p o r t a b l e gas chroraatograph i s not

a v a i l a b l e , a gas sampling b o t t l e can be f i l l e d with the d r i e d gas
a f t e r rotometer, m. A n a l y s i s o f hydrogen, oxygen, carbon d i o x i d e ,
carbon monoxide, methane, and i l l u m i n a n t s concentrations i n the
gas can be determined on an Orsat equipped with combustion appara-
tus t o determine hydrogen and methane. However, the a n a l y s i s time
i s lengthy so t h a t the number o f analyses made near the end o f the
coking c y c l e a r e t o o l i m i t e d t o o b t a i n a true p i c t u r e o f the cok-
ing c y c l e *nd p o i n t .
C. Gas Chromatographic A n a l y s i s . The use o f a portable gas

chromât ograph l o c a t e d i n a s h e l t e r e d a r e a near the sampling system
i s the best method t o f o l l o w the course o f the coking c y c l e .
The curves i n F i g u r e 3 are based on the a n a l y t i c a l r e s u l t s
obtained on a gas chromatograph with a thermal c o n d u c t i v i t y de-
t e c t o r ( l ) . The s e p a r a t i o n column i s a l / 8 - i n c h by 1 0 - f o o t s t a i n -
l e s s s t e e l tube c o n t a i n i n g #5A molecular s i e v e and the r e f e r e n c e
column i s a l / 8 - i n c h by 6 7 - i n c h s t a i n l e s s s t e e l tube c o n t a i n i n g
Porapak Q. The o p e r a t i n g c o n d i t i o n s a r e argon flow 1 2 ec per min-
ute t o each column, 1 0 0 ma c e l l c u r r e n t , column and c e l l tempera-
t u r e i s 40°C. The chromatograph i s standardised with a gas con-
t a i n i n g 5 0 $ H , yff> ChY, 10^ CO, % CO2 and N the balance. The
2 2
standard gas i s admitted i n t o the sample l i n e ahead o f the d r i e r -

i t e i n 1 and the flow r a t e maintained through the sample l o o p the
same as f o r coke oven gas. The sample l o o p c a p a c i t y i s 0 . 5 ec
and i s dependent on the s e n s i t i v i t y o f the d e t e c t o r , u s i n g argon
as c a r r i e r gas.
I f the d e t e c t o r has i n s u f f i c i e n t s e n s i t i v i t y f o r CO and CH^,
a c a r r i e r gas c o n t a i n i n g &f> hydrogen and 92$ helium may be used
a t a c e l l c u r r e n t o f 1 5 0 ma.
Concentrations o f C 0 and i l l u m i n a n t s , as ethylene, can be
2
obtained on the Porapak column. The chromatograph must a l s o be

equipped with a sample valve f o r t h i s column and a p o l a r i t y switch
so t h a t the peaks a r e p o s i t i v e on the c h a r t paper o f the r e c o r d e r .
However, COp and i l l u m i n a n t s axe n o t necessary t o determine the
end p o i n t ; t h e r e f o r e , these can be ignored o r p e r i o d i c a l l y d e t e r -
mined by the Orsat method.

0 7 14 21 28 35 42 49 56 63 70 77 84 91 100
% OF COKING C Y C L E
Figure 3. Composition of coke oven gas during coking cycle.

D. R e s u l t s . The p l o t o f the a n a l y t i c a l r e s u l t s i n F i g u r e 3
are those f o r coking d r y c o a l f o r Ik hours a t a f l u e temperature
of 1260°C. Concentration of hydrogen approaches a maximum o f over
70# and the methane approaches the minimum o f l e s s than Ifi near
the end o f the coking c y c l e . G e n e r a l l y , coking i s continued f o r
an a d d i t i o n a l 30 minutes a f t e r these a n a l y t i c a l values are reached
and then the coke i s pushed from the oven.
S i m i l a r curves are reported (Beckman e t a l . , 1962) f o r the
c o k i n g o f wet c o a l s ( 2 ) . However, the c o k i n g c y c l e i s 18 t o 19 hours,
because a l a r g e amount o f water must be evaporated from the wet
c o a l eharged t o the ovens.
The major c o n s t i t u e n t s o f the 7 3 3 0 0 , 0 0 0 c u b i c f e e t o f coke
f
oven gas a f t e r condensation o f the t a r are shown i n Table I I .

Table Π. Composition of Deterred Coke Oven Gas.
CONSTITUENT VOLUME PERCENT
55.0
CH^ 29.0
CO 5.5
Aromatics 3.0
COg and S compounds 2.6
°2 °.9
H 2 k.O
The volume o f t a r i n t h i s p a r t i c u l a r coke p l a n t i s 5 8 , 9 0 0

gallons/day and the volume o f l i g h t o i l i s 2 2 , 3 0 0 g a l l o n s / d a y .
The l i g h t o i l contains 6 3 . 0 £ benzene, 1 3 . 0 ^ toluene, 5.69? xylene,
and 5.1# o f crude s o l v e n t . There are a l s o produced 3 3 . 5 tons/day
o f ammonium s u l f a t e and *K)0 g a l l o n s o f t a r a c i d s , which are mainly
phenols.
The coke oven gas, p r a c t i c a l l y f r e e d o f t a r , ammonia and
l i g h t o i l , i s e x t r a c t e d with monoethanolamine t o remove h^S, HCN,
and SO2 t o l e v e l s r e q u i r e d f o r a i r p o l l u t i o n abatement. One t h i r d
o f the d e s u l f u r i z e d gas i s returned t o the coke ovens as a source
o f heat f o r c a r b o n i z i n g the e o a l i n the ovens. Two-thirds o f the
gas flows t o the s t e e l p l a n t furnaces where i t i s used as the
source o f heat f o r r e h e a t i n g s t e e l products.
The coke produced i n the coke ovens i s charged t o the b l a s t
furnaces together with i r o n ore and limestone where, a t h i g h tem
peratures, the i r o n ore r e a c t s with the coke and limestone t o form

292 C O A L A N D C O A L
PRODUCTS
p i g i r o n and s l a g . The spent gases c o n t a i n i n g h^, C0 and C 0 are 9 2
used t o heat l a r g e volumes o f a i r which a r e blown i n t o the furnace

t o a i d the r e a c t i o n o f coke, limestone, and i r o n ore.
T y p i c a l charges per day i n t o a medium s i z e d b l a s t furnace a r e :
Dry Coke 1050 l b s . / t o n hot metal, a l s o

called pig iron
I r o n Ore 3200 l b s / t o n hot metal
Limestone & Dolomite 2 7 0 l b s / t o n hot metal
Wind f o r Combustion
of the Coke 5 1 , 0 0 0 t o 5^,000 c u b i c f e e t / t o n
hot metal
O i l Injection 100 l b s / t o n hot metal
Production 3000 tons hot metal/day
The 3200 l b s . o f ore per net ton o f metal c o n s i s t s of 100

l b s . B0F s l a g , I50 l b s . o f s c r a p and 2950 l b s . o f i r o n ore
pellets.
T h i s i l l u s t r a t i o n shows t h a t c o a l i s a major source o f
energy i n the s t e e l i n d u s t r y . Although the i n d u s t r y i s i n a de-
pressed s t a t e today, i t w i l l use 7 5 m i l l i o n tons o f c o a l i n 1 9 8 1 .
Literature Cited
(1) Manka, D. P., "Analytical Methods for Coal and Coal Products,"
Vol. III, edited by C. Karr, Jr., Academic Press, New York,
1979, 6--10.
(2) Beckmann, P., Simons, W., and Weskamp, W. (1962) Brennst.--
Chem. 43 (8), 24l.

15
Electron Optical and IR Spectroscopic
Investigation of Coal Carbonization
J. J. FRIEL, S. M E H T A , and D. M . FOLLWEILER

Bethlehem Steel Corporation, Homer Research Laboratories, Bethlehem, PA 18016
The chemistry of coal carbonization was

studied i n an attempt to better understand the

changes that take place as metallurgical coal
becomes plastic. Infrared spectroscopy was used
to study the transformation from coal-mesophase-
-semicoke and to relate the changes to those
observed i n the electron microscope. Spectra of
semicokes produced from three different coals at
various heat-treatment temperatures show changes
that can be related to the fluid properties of
the coals. Evidence of mesophase i n the fluid
range of temperature can be obtained from changes
in the region of the spectra assigned to aromatic
hydrogen out-of-plane bending modes. Heat-treatment
temperatures above the fluid range result in conden-
sation of the mesophase as hydrogen i s lost.
Various metallurgical coals with different coking properties

were examined i n an attempt to learn more about the carbonization
process. In our previous studies, we observed three basically
different microstructures i n different coals during heating stage
experiments i n the transmission electron microscope (1). A
Pittsburgh No. 8 coal with good coking properties readily formed
mesophase spheres that coalesced before solidification to a
semicoke (Figure 1). An I l l i n o i s No. 6 sample of similar rank
but l i t t l e fluidity exhibited only isolated small mesophase
spheres (Figure 2). A Lower Kittanning low-volatile coal formed
not only spheres but rods (Figure 3).
The purpose of the present study was to examine the coal-to-
coke transformation away from the heating stage of the electron
microscope. We carbonized samples at various heat-treatment
temperatures in a plastometer. The plastometer has the advantage
over the electron microscope hot stage not only i n that i t is the
apparatus we used i n the fluidity test but also i n that i t
minimizes thermal gradients across the sample. Semicokes thus
0097-6156/82/0205-0293$06.00/0

Figure 1. Electron micrograph of coalesced spheres in Pittsburgh No. 8 vitrinite

on the heating stage of the TEM.
Figure 2. Electron micrograph of isolated spheres in Illinois No. 6 vitrinite.

15. FRIEL ET AL. Spectroscopic Investigation of Carbonization 295
produced were examined i n the e l e c t r o n microscope and by i n f r a r e d

spectroscopy.
Studies on c o a l s t r u c t u r e and i t s decomposition products
u s i n g F o u r i e r transform i n f r a r e d spectroscopy (FTIR) were r e c e n t l y
reported by Solomon ( 2 ) . While t h i s technique produces a g r e a t e r
peak-to-background r a t i o than i s p o s s i b l e w i t h the c o n v e n t i o n a l
i n f r a r e d technique, we were s t i l l able t o o b t a i n u s e f u l informa-
t i o n w i t h the c o n v e n t i o n a l d i s p e r s i v e instrument by means o f
m u l t i p l e accummulations. P a i n t e r and Coleman a l s o used the FTIR
technique on c o a l and c a r e f u l l y assigned a b s o r p t i o n s t o s p e c i f i c
f u n c t i o n a l groups ( 3 ) . Our aim was t o study the d i f f e r e n c e s
among c o a l s of d i f f e r e n t coking p r o p e r t i e s and r e l a t e the growth
of mesophase i n these c o a l s t o the changes that take place upon
c a r b o n i z a t i o n . The p r o p e r t i e s of the c o a l s s t u d i e d a r e l i s t e d
i n Table I . Inasmuch as i n f r a r e d s p e c t r a of c o a l s o f d i f f e r e n t
rank are s i m i l a r , i t was necessary t o s e l e c t c o a l s o f markedly
d i f f e r e n t coking p r o p e r t i e s t o improve our chances o f seeing
differences.
Experimental Technique
Coal ground t o <4.75 mm was placed i n the plastometer

e q u i l i b r a t e d a t 300°C. The c o a l was then heated a t a standard
r a t e of 3°C/min t o the d e s i r e d temperature without s t i r r i n g and
allowed t o c o o l . Heat-treatment temperatures ranged i n 25°
increments between 300 and 550°C f o r the P i t t s b u r g h No. 8 c o a l ,
between 300 and 500°C f o r the I l l i n o i s No. 6 c o a l , and between
400 and 550°C f o r the Lower K i t t a n n i n g c o a l . Other samples o f
these c o a l s were subjected t o the standard Bethlehem plastometer
t e s t t o measure the temperatures of onset of f l u i d i t y , maximum
f l u i d i t y , and r e s o l i d i f i c a t i o n .
Semicokes prepared i n the plastometer were ground, and
observed as a d i s p e r s i o n i n a P h i l i p s EM300 t r a n s m i s s i o n e l e c t r o n
microscope or P h i l i p s EM400 scanning t r a n s m i s s i o n e l e c t r o n
microscope (STEM). The instruments were operated a t 100 kV, and
the STEM was employed i n both the t r a n s m i t t e d e l e c t r o n and the
secondary e l e c t r o n imaging modes. A p o r t i o n of each o f the
samples from the plastometer was reserved f o r i n f r a r e d s p e c t r a .
These s p e c t r a were taken on KBr p e l l e t s i n t o which a known amount
of c o a l o r semicoke was pressed. A spectrum was obtained from
each o f the c o a l s and from the semicokes from each heat-treatment
temperature. A l l s p e c t r a were a c q u i r e d a t room temperature.
A Perkin-Elmer Model 283B automated i n f r a r e d spectrophotometer
was used, and each sample was scanned from 301-4000 cm and
accumulated t w i c e . The r e g i o n of the spectrum c o n t a i n i n g aromatic
out-of-plane bending modes (595-900 cm ) was accumulated 25 times
f o r each sample i n order t o more c a r e f u l l y evaluate the changes
that take p l a c e i n the s u b s t i t u t e d aromatic groups. A l l o f the
s p e c t r a were normalized by the computer on the b a s i s of the
weight of sample i n the KBr p e l l e t .

Figure 3. Spheres and rods in Lower Kittanning vitrinite shown after cooling on
the heating stage of the TEM.
Table I . Some C h a r a c t e r i s t i c s of the Coals Used i n This Study
^ Volatile Fluidity^ Mesophase

Rvit matter (%) (ddpm) structure
P i t t s b u r g h No. 8 ΌΤ8? 3871 5,200 coalesced
spheres
I l l i n o i s No. 6 0.69 40.4 <10 isolated
spheres
Lower K i t t a n n i n g 1.57 19.5 <50 rods and
spheres
a « v i t r i n i t e reflectance
b - d i a l d i v i s i o n s per minute

Results
F l u i d p r o p e r t i e s o f the c o a l s are given i n Table I I . The

f l u i d ranges of temperature of the I l l i n o i s and Lower K i t t a n n i n g
c o a l s a r e l e s s than that o f the P i t t s b u r g h No. 8 c o a l . The
temperature of maximum f l u i d i t y i s highest f o r the l o w - v o l a t i l e
Lower K i t t a n n i n g c o a l and i s lowest f o r the I l l i n o i s No. 6 c o a l .
Even though the Lower K i t t a n n i n g and I l l i n o i s c o a l s have s i m i l a r
low f l u i d i t i e s , they d i f f e r s i g n i f i c a n t l y i n rank, and the
reason f o r the low f l u i d i t y may w e l l be d i f f e r e n t . The u l t i m a t e
a n a l y s i s of the c o a l s i s shown i n Table I I I .
Semicokes prepared a t v a r i o u s temperatures were examined i n
the t r a n s m i s s i o n e l e c t r o n microscope, but few f e a t u r e s could be
seen i n the lower- and higher-temperature samples. Because of

the porous and b r i t t l e nature of semicoke, i t was d i f f i c u l t t o
prepare good i o n - t h i n n e d s e c t i o n s as we d i d f o r c o a l . Therefore,
f e a t u r e s such as spheres and rods may have been destroyed d u r i n g
g r i n d i n g t o prepare the sample.
The P i t t s b u r g h No. 8 semicoke that was cooled from 400°C
contained remnant mesophase spheres, and these can be seen i n
Figure 4. This photomicrograph was taken i n the secondary
e l e c t r o n mode i n the scanning t r a n s m i s s i o n e l e c t r o n microscope.
In t h i s imaging mode, o n l y surface f e a t u r e s can be seen by
topographic c o n t r a s t . I n the t r a n s m i t t e d e l e c t r o n mode, most
of the sample was too t h i c k t o pass e l e c t r o n s , and spheres were
d i f f i c u l t t o d i s t i n g u i s h . I n the P i t t s b u r g h No. 8 sample, 400°C
i s the onset o f f l u i d i t y , and mesophase spheres were s u f f i c i e n t l y
abundant t o be observed i n the STEM (Figure 4 ) .
Figure 5 shows rod-shaped f e a t u r e s i n the 500°C Lower
K i t t a n n i n g semicoke seen i n the t r a n s m i t t e d e l e c t r o n mode.
Although 500°C i s beyond the temperature of r e s o l i d i f i c a t i o n
measured i n the plastometer, the temperatures reported f o r
l o w - f l u i d i t y c o a l s are not as meaningful as those f o r h i g h -
f l u i d i t y c o a l s . I n a d d i t i o n , f l u i d p r o p e r t i e s of many samples
of l o w - f l u i d i t y c o a l s cannot be measured i n the plastometer.
A c c o r d i n g l y , the temperatures measured f o r one sample may not
be a p p l i c a b l e t o other samples o f the same l o w - f l u i d i t y c o a l .
In the I l l i n o i s No. 6 semicokes, we were not able t o detect
remnants o f the mesophase w i t h the e l e c t r o n microscope. I n each
of the semicokes observed, fewer f e a t u r e s were found than were
p r e v i o u s l y seen on the h e a t i n g stage. This s i t u a t i o n might be
expected because o f the d i f f e r e n t sample p r e p a r a t i o n techniques.
A uniform 100 nm t h i n s e c t i o n used on the h e a t i n g stage i s b e t t e r
s u i t e d f o r examination i n the e l e c t r o n microscope than i s a f i n e
d i s p e r s i o n o f p a r t i c l e s , which may or may not have e l e c t r o n
transparent edges.
I n f r a r e d s p e c t r a of each o f the three c o a l s a r e shown i n
Figure 6. The s p e c t r a a r e s i m i l a r t o each other, w i t h s u b t l e
d i f f e r e n c e s o f t e n being masked by the o v e r a l l a b s o r p t i o n o f the
c o a l . Although we s t u d i e d c o a l s w i t h d i f f e r e n t c a r b o n i z a t i o n

Table I I . F l u i d P r o p e r t i e s from Bethlehem Plastometer Test
Initial Maximum Solidification

Coal Bonding Fluidity Point Fluidity
P i t t s b u r g h No. 8 397°C 450°C 470°C 5200 ddpm
I l l i n o i s No. 6 405 422 445 3
Lower K i t t a n n i n g 457 475 480 35
Table I I I . Chemical A n a l y s i s and Ash Content of the Coal Studies

(Wt %, Dry B a s i s )
Coal C H Ν S 0* Ash
P i t t s b u r g h No. 8 79.82 5.15 1.86 0.84 6.42 5.9
I l l i n o i s No. 6 76.74 5.24 1.51 1.15 9.06 6.3
Lower K i t t a n n i n g 85.58 4.58 1.38 0.46 1.50 6.5
* By d i f f e r e n c e

Figure 4. Secondary electron micrograph of semicoke from Pittsburgh No. 8 coal

after heating to 400°C.
Figure 5. Transmitted electron micrograph of semicoke from Lower Kittanning

coal after heating to 500°C.

p r o p e r t i e s , one must remember that these are s t i l l bituminous

c o a l s . Lowry gives many references to i n f r a r e d s p e c t r o s c o p i c
s t u d i e s of c o a l s of d i f f e r e n t rank, but marked changes are not
evident i n the i n f r a r e d spectrum (4_).
In the spectra shown i n Figure 6, d i f f e r e n c e s can be seen
p r i n c i p a l l y i n the 1000-1300 cm r e g i o n . There are a l s o d i f -
ferences i n the a r o m a t i c / a l i p h a t i c r a t i o s , but such determina-
t i o n s have been made by Solomon with more s e n s i t i v i t y than i s
p o s s i b l e with our technique ( 2 ) . The I l l i n o i s No. 6 c o a l shoys
evidence of a greater content of aromatic ethers (1200-1300 cm^ ) .
The P i t t s b u r g h No. 8 c o a l absorbs throughout the 1000-1300 cm"
range, owing t o the presence of both aromatic and a l i p h a t i c ether
groups. In t h i s r e g i o n the Lower K i t t a n n i n g sample absorbs l e a s t .
Spectra of semicokes made from P i t t s b u r g h No. 8 c o a l at

v a r i o u s temperatures are shown i n Figure 7. Increasing the heat-
treatment temperature from 300°C causes l i t t l e change i n a g i v e n
spectrum u n t i l 400°C. At t h i s temperature, corresponding t o the
onset of f l u i d i t y , the peaks become sharper. At 450°C, c o r r e s -
ponding t o maximum f l u i d i t y , the peaks become t h e i r sharpest.
Beyond the r e s o l i d i f i c a t i o n temperature of 470°C, s p e c t r a l d e f i -
n i t i o n i s l o s t , and by 525°C the spectrum i s e s s e n t i a l l y
featureless.
Spectra of semicokes from I l l i n o i s No. 6 c o a l are shown i n
Figure 8. Ether groups, and i n p a r t i c u l a r aromatic e t h e r s , are
a s i g n i f i c a n t feature of t h i s c o a l , which i s high i n oxygen.
Increasing temperature causes l i t t l e change i n t h i s s e r i e s of
spectra u n t i l 400°C. Between 400 and 425°C the s p e c t r a l peaks
become sharpest and then decrease i n the higher temperature
samples. The spectra a l s o show a probable decrease i n the
amount of aromatic ethers and probable i n c r e a s e i n the amount
of a l i p h a t i c ethers (1000-1200 cm ) with i n c r e a s i n g temperature.
The temperature of maximum f l u i d i t y of I l l i n o i s No. 6 c o a l i s not
e a s i l y measured i n the plastometer owing to i t s low f l u i d i t y .
However, i n f r a r e d evidence i n d i c a t e s that the temperature of
maximum f l u i d i t y i s probably between 400-425°C.
Spectra of semicokes from the Lower K i t t a n n i n g c o a l are
shown i n Figure 9. The spectrum with the most d i s t i n c t peaks i n
t h i s s e r i e s i s the 500°C semicoke. However, as i n the case of
the I l l i n o i s No. 6 s e r i e s , there i s not the marked improvement
i n s p e c t r a l q u a l i t y a t the temperature of maximum f l u i d i t y that
we observed i n the P i t t s b u r g h Seam s e r i e s . There i s a l s o
evidence of carbonyl groups at 1740 cm i n t h i s s e r i e s of semi-
cokes — p o s s i b l y corresponding t o e s t e r s .
The aromatic peaks between 700 and 900 cm are shown at
higher s e n s i t i v i t y i n Figure 10. The semicokes that produced
the sharpest spectrum and those from the two adjacent tempera-
tures are shown along with the untransfjrmed c o a l s . In each
s e r i e s of semicokes the peak at 750 cm , corresponding to 1,2
s u b s t i t u t i o n , reaches a maximum n j a r the onset of f l u i d i t y
temperature. The peak at 860 cm , corresponding t o h i g h l y

15. FRiEL ET AL. Spectroscopic Investigation of Carbonization 301
.s:
I
.3
S
II
11
î i
« 0 0
13
a
Si


FRIEL ET AL. Spectroscopic Investigation of Carbonization 303

ι ι ι I I I I I I
4000 2500 ,2000 1800 1600 1400 800 600 400 200
Figure 9. Spectra of semicokes prepared from Lower Kittanning coal at various

heat-treatment temperatures.

Figure 10. Spectra showing the aromatic hydrogen out-of-plane bending vibra-
tions in different coals and semicokes—25 times accumulation. Key: top row,
Pittsburgh No. 8; middle row, Lower Kittanning; and bottom row, Illinois No. 6.

s u b s t i t u t e d aromatics becomes prominent only at the next

higher temperature and then diminishes g r e a t l y at the r e -
s o l i d i f i c a t i o n temperature.
Discussion
The data gathered from these three c o a l s serve to provide

i n s i g h t i n t o the chemical changes that take place as m e t a l l u r -
g i c a l c o a l goes through i t s p l a s t i c s t a t e while transforming i n t o
semicoke. A great d e a l of the more recent work on c o a l has d e a l t
with c o a l conversion processes or a d d i t i v e s to c a r b o n i z a t i o n
r a t h e r than with the c a r b o n i z a t i o n of c o a l alone. Although the
chemical changes i n c o a l during i t s f l u i d range are s t i l l not w e l l
understood, some i n f o r m a t i o n can be d e r i v e d from observations of

the mesophase and from changes i n f u n c t i o n a l groups as i n f e r r e d
from i n f r a r e d s p e c t r a .
As a h i g h l y f l u i d c o a l such as P i t t s b u r g h No. 8 i s heated,
the c o a l s t r u c t u r e begins to break down i n t o s m a l l e r u n i t s
probably c o n s i s t i n g of 2-5 fused aromatic r i n g s along with the
a l i p h a t i c and a l i c y c l i c component. The s p e c t r a up to 400°C show
an i n c r e a s e i n the methyl and methylene bending peaks at 1380 and
1450 cm , p o s s i b l y r e s u l t i n g from the cleavage of ethylene
b r i d g i n g u n i t s as suggested by Solomon (_5). The I l l i n o i s No. 6
c o a l does not show t h i s e f f e c t . In the I l l i n o i s c o a l the i n i t i a l
breakdown, which i s c r i t i c a l to f l u i d i t y , perhaps does not occur
to the same extent as i t does i n the P i t t s b u r g h No. 8 c o a l . The
i n c r e a s e d amount of aromatic compared with a l i p h a t i c ether groups
i n the I l l i n o i s No. 6 sample may i n h i b i t breakdown of the c o a l
s t r u c t u r e . Aromatic ether l i n k a g e s are known to be strong bonds
and may be at l e a s t p a r t i a l l y r e s p o n s i b l e f o r the l a c k of f l u i d i t y
of t h i s c o a l . With i n c r e a s i n g temperature up to the onset of
f l u i d i t y , the number of ether l i n k a g e s remains almost constant.
There may be an e q u i l i b r i u m at any given time between cleavage
of e x i s t i n g ether bonds and formation of new ones by dehydration.
The small aromatic u n i t s formed by breakdown of the c o a l
s t r u c t u r e are s i m i l a r to those i n t a r , although t h e i r molecular
weight i s probably g r e a t e r . The s p e c t r a of t a r c o l l e c t e d during
the p i l o t - s c a l e c a r b o n i z a t i o n of P i t t s b u r g h No. 8 and of Lower
K i t t a n n i n g c o a l s are shown i n F i g u r e 11. I t can be seen that the
t a r s are r i c h i n aromatic compounds and are remarkably s i m i l a r to
each other i n s p i t e of the d i f f e r e n c e s i n ran^ and p r o p e r t i e s of
the c o a l s . The strongest peak i s the 750 cm v i b r a t i o n of
o r t h o - s u b s t i t u t e d aromatics. Naphthalene, anthracene, and
s i m i l a r polynuclear aromatic molecules found i n these t a r s are
the most l i k e l y c o n t r i b u t o r s to such a peak.
During the e a r l y stages of heating before the onset of
f l u i d i t y , l i t t l e change occurs i n Jhe s p e c t r a . The broad absorp-
t i o n between 2400 and and 3400 cm a s s o c i a t e d with hydrogen
bonding remains r e l a t i v e l y constant as does the ether r e g i o n
between 1000 and 1300 cm . At the temperature at which the c o a l

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becomes p l a s t i c , the peak at 750 cm becomes the s t r o n g e s t
aromatic a b s o r p t i o n and i n d i c a t e s that s m a l l o r t h o - s u b s t i t u t e d
molecules such as those i n t a r have reached t h e i r maximum
abundance. Hydrogen bonding begins to decrease at the tempera-
ture of onset of f l u i d i t y i n the P i t t s b u r g h No. 8 sample as w e l l
as i n the I l l i n o i s No. 6. Apparently at t h i s stage the aromatic
molecules are h i g h l y mobile. A l s o , a t t h i s stage the f r e e
r a d i c a l concentration i n v i t r i n i t e increases sharply (6),
probably as a r e s u l t of cleavage of C-C and/or C-O-C bonds.
F u r t h e r i n c r e a s e i n temperature causes the s m a l l aromatic
u n i t s to recombine and form aromatic s h e e t s . I t was p u z z l i n g
that i n f r a r e d s p e c t r a seem t o g i v e evidence f o r more l i g h t
aromatic molecules than the t a r y i e l d of c o a l c o u l d account f o r .
This i n c o n s i s t e n c y can be r e s o l v e d i f what occurs i s that the

l i g h t aromatics are formed and then most of them polymerize to
form sheets. The remaining l i g h t aromatic molecules that do not
polymerize are c a r r i e d o f f as t a r . The sheets can then form
l a y e r e d s t r u c t u r e s h e l d together by London d i s p e r s i o n f o r c e s ,
which i n c r e a s e w i t h i n c r e a s i n g molecular s i z e . S t r u c t u r e s such
as these are capable of d i f f r a c t i n g e l e c t r o n s and are probably
the l i q u i d - c r y s t a l l i n e mesophase seen on the hot stage of the
e l e c t r o n microscope.
At^the temperature of maximum f l u i d i t y the v i b r a t i o n at
860 cm reaches i t s maximum. This peak, which a r i s e s from
h i g h l y s u b s t i t u t e d aromatic r i n g s , i s c o n s i s t e n t w i t h a model o f
l i q u i d c r y s t a l s composed of l a y e r e d aromatic sheets w i t h lone
hydrogen atoms o n l y on the edges. The 860 cm peak becomes
s i g n i f i c a n t i n each c o a l at o n l y one temperature. I n another
P i t t s b u r g h No. 8 s a m p l j , whose f l u i d i t y was s e v e r e l y reduced by
o x i d a t i o n , the 860 cm peak d i d not become s i g n i f i c a n t at any
temperature. Hence, f l u i d i t y and mesophase are e v i d e n t l y
related.
Continued c a r b o n i z a t i o n beyond the temperature of maximum
f l u i d i t y causes r e s o l i d i f i c a t i o n . The 860 cm peak disappears
as the coalesced mesophase l o s e s more v o l a t i l e matter, mostly
hydrogen, and the aromatic sheets bond t o each o t h e r , but not
i n a w e l l - o r d e r e d f a s h i o n . I t i s l i k e l y that the hydrogen l o s t
at t h i s stage comes from the edges of the sheets, l e a v i n g f r e e
r a d i c a l s . This i n t e r p r e t a t i o n i s c o n s i s t e n t w i t h the observa-
t i o n by P e t r a k i s et a l that the maximum number of f r e e r a d i c a l s
measured by e l e c t r o n paramagnetic resonance occurs roughly
around the r e s o l i d i f i c a t i o n temperature ( 6 ) . In c l a s s i c a l
l i q u i d - c r y s t a l systems, on h e a t i n g , c r y s t a l s transform to l i q u i d
c r y s t a l s and then to an i s o t r o p i c l i q u i d , the t r a n s f o r m a t i o n s
being r e v e r s i b l e . In the carbonaceous mesophase, on the other
hand, decomposition proceeds s i m u l t a n e o u s l y w i t h the phase t r a n s -
f o r m a t i o n s , so that the r e a c t i o n s are not r e v e r s i b l e .
I n semicokes cooled from above the r e s o l i d i f i c a t i o n p o i n t ,
the i n f r a r e d s p e c t r a become l e s s i n t e n s e as e l e c t r o n i c a b s o r p t i o n

becomes s i g n i f i c a n t . Further heating o f semicokes a f t e r s o l i d i -

f i c a t i o n evolves p r i m a r i l y hydrogen.
Conclusions
From the foregoing data and previous h e a t i n g stage e x p e r i -

ments we conclude that the c a r b o n i z a t i o n of m e t a l l u r g i c a l c o a l
proceeds v i a a mesophase composed o f sheets o f aromatic r i n g s
possessing f u n c t i o n a l groups s i m i l a r t o those i n the parent c o a l .
Mesophase d i f f e r s from c o a l i n that i t has a g r e a t e r aromatic
component and i s more ordered. During c a r b o n i z a t i o n , c o a l
reaches i t s maximum f l u i d i t y as the mesophase c o a l e s c e s . As
c a r b o n i z a t i o n proceeds beyond the f l u i d range, decomposition
w i l l have occurred and a disordered semicoke w i l l form. The

p r o p e r t i e s of t h i s semicoke and o f the r e s u l t i n g coke are con-
t r o l l e d t o a l a r g e extent by what happens during the p l a s t i c
stage. Therefore, what we l e a r n about the mesophase we hope w i l l
help us achieve b e t t e r c o n t r o l o f the c a r b o n i z a t i o n process
and improve the product.
Acknowledgments
The authors g r a t e f u l l y acknowledge the a s s i s t a n c e o f

N. Marion f o r preparing the semicoke samples and W. S. S z u l b o r s k i
f o r t a k i n g the i n f r a r e d s p e c t r a .
Literature Cited
1. Friel, J. J.; Mehta, S.; Mitchell, G. D.; Karpinski, J. M.
Fuel 1980, 59, 610-616.
2. Solomon, P. R. Am. Chem. Soc. Div. Fuel Chem., Preprints
1979, 24 (2) 184.
3. Painter, P. C.; and Coleman, M. M. Am. Lab. 1980, 12, 19-29.
4. Lowry, H. H. "Chemistry of Coal Utilization (Supplementary
Volume)"; Wiley: New York, 1963; p 61-78.
5. Solomon, P. R.; personal communication.
6. Petrakis, L.; Grandy, D. W. Fuel 1981, 60, 115-119.

INDEX
A Ankerite
Môssbauer spectra 247/, 248/
AAS—See Atomic Absorption SEM-AIA analyses 244/, 250/
Spectrometry Anthracene, GC/MS identification in
Absorbance variation in FTIR 94/ toluene subfraction of Sephadex
Absorption process 264 LH-20 fractions of tar trap tar .. 218/
Absorptivities Anthracite, Rhode Island, Môssbauer
aromatic and aliphatic 97/ spectra 247/
of hydroxyl concentration, FTIR .. 95/ Antimony analyses in coal by
Acenaphthene and acridine, GC/MS hydride-atomic absorption
identification in toluene subfrac- spectrometry 155/
tion of Sephadex LH-20 fractions
Publication Date: November 12, 1982 | doi: 10.1021/bk-1982-0205.ix001
Apatite, SEM-AIA analyses 244/, 250/

of tar trap tar 218/ Appalachian coals, gallium and
Acicular flow domain anisotropy 6/ germanium content 156/
Activated states in air oxidation ... 143-144 Apparatus, pressure filtration and
Active pitches 8 Soxhlet extraction 266-231
Acyclic structure 29/ Applications of FTIR 77-127
Additives Arizona coal, FTIR spectrum 66/
breeze 11 Aromatic absorptivities 97/
pitch 8 Aromatic C - H group determination
AES—See Atomic emission
by FTIR 61-63, 71-74
spectrometry
Aromatic carbon
Aliphatic absorptivities from regres-
sion analysis 97/ FTIR vs. NMR 100/
proximate analysis fixed carbon 121/
Aliphatic hydrocarbon concentration
analysis by FTIR 61-63, 71-74 Aromatic ethers in Illinois
and degree of oxidation 141 coal semicokes 300
and Fischer assay oil yield 123/ Aromatic hydrogen, FTIR 93, 96-99
Aliphatic hydrogen concentration Aromatic hydrogen in coal gasifier
analysis by proton NMR 219/ tar by proton NMR 219/
analysis by FTIR 93, 96-99 Aromatic hydrogen out-of-plane
correlation with tar yield 117/ bending vibrations shown by
Alkali halide matrix 49-51 IR spectra 305/
Alkane content Arsenic analysis
of fossil fuels 27-43 using hydride generation-atomic
of hydrocarbon minerals 28/ absorption spectrometry 155/
Aluminum analysis using ICP-AES 150/, Ash content
153/, 160/, 167/, 169/, 171/ of Kentucky Colonial Mine and
Americana, sulfur analysis using Illinois Burning Star Mine 228/
EPM 195-202 of Pittsburgh, Illinois, and Lower
American Society for Testing and Kittanning coal 298/
Materials (ASTM) Standard of vitrains 13/
Test Method—See ASTM of Wyodak and Bruceton coal 136/
Analytical instruments, on-line, Ash monitors 263-267
economic considerations 275-277 Ashes, North Dakota lignite,
Analytical instruments in coal prep- gallium and germanium content. 156/
aration industry, overview ...259-277 Asphaltenes, Ashland A200 pitch
Analyzer, elemental, using Cali- analysis 13/
fornium-252 neutron source .268-269 Asphaltite, Turkish
Anisotropic and isotropic properties alkane content 28/
of cokes and coke blends 1-7 carbon-13 spin-lattice relaxation
Anistropy nomenclature 6/ times 39/
313

ASTM for sulfur analysis 192-194, 200 Blind Canyon, sulfur analysis
ASTM/EPM comparative study 195/ using EPM 195-202
Atomic absorption spectrometry, Bonding of Pittsburgh, Illinois, and
detection limits 153* Lower Kittanning coal 298*
Atomic absorption—hydride genera Boron analysis
tion spectrometry, trace ele using ICP-AES 167*, 169*, 171*
mental analysis 155* using Parr oxygen bomb elemental
Atomic absorption spectrophoto analysis 152*, 153*, 160*
meter (AAS) 148, 151, 153 Bottom ash, gasifier cleanup device
Atomic emission spectrometry for samples 215*
metal quantitation and Breeze additives 11
speciation 163-182 Bromide analysis 149
Atomic H/C ratio of organic matter Bromine analysis using Parr oxygen
in hydrocarbon minerals 28* bomb 152*, 153*, 160*
Australian coals, gallim and Bruceton chemical analysis 136*
germanium content 156* Btu, low, sasification 205-222
Avgamasya-asphaltite alkanes 40/

Azapyrene, GC/MS identification C
in tar trap tar 218* C NMR—See Carbon-13 NMR
13
Cadmium, detection limits and anal

Β ysis using ICP-AES ...167*, 169*, 171*
Backscattered electron (BSE) Caking coal, 2-3
radiation in SEM-AIA 241 Calcite, SEM-AIA analyses 244*,
Bale correction, FTIR 51-52 250*, 255*
Barite, SEM-AIA analyses 250* Calcium, detection limits and analysis
Barium analysis using ICP-AES 150*, by ICP-AES 150*, 153*, 160*,
153*, 160*, 167*, 169*, 171* 167*, 169*, 171*
Barium chloride formation in chlorine Californium-252 neutron source for
determination 186-190 elemental analyzer system 268-269
Beer's law in FTIR 81-83 Capacitance, on-line moisture
Benzene-insolubles in Ashland monitors 270-273
A200 pitch 13* Carbon
Benzo[a]fluorene and benzo[a]pyrene, anisotropic 2-3
GC/MS identification in toluene aromatic, C(ar), correlation of
subfraction of tar trap tar 218 proximate analysis fixed
Benzo(f)quinoline and benzo(h)- carbon 121/
quinoline, GC/MS identification aromatic, FTIR vs. NMR 100/
in the basic subfraction of Sepha- content in coal 298*
dex LH-20 fraction 5 of tar functional group concentrations,
trap tar 218* determination 94-99
Beryllium analysis in coal andflyash Kentucky Colonial Mine and Illinois
using ICP-AES 150*, 153*, 160* Burning Star Mine 228*
Bethlehem plastometer test, fluid Pittsburgh, Illinois, and Lower
properties 298* Kittanning coal 289*
Beulah North Dakota lignite, carbon Six Bells, Cortonwood Silkstone,
dioxide yield vs. time from and Maltby Swallow Wood
pyrolysis 112/ coal 12*
Bevier, sulfur analysis by EPM 198* vitrains 13*
Bituminous coal Wyodak and Bruceton coal 136*
alkane content 28* Carbon-13 NMR of coal-derived
DRIFT analysis 133-143 products and spin-lattice relaxation
FTIR 67-68,97/ time measurements 34-41
secondary electron image and Carbon dioxide
inverted backscattered elec concentration determined by
tron (BSE) image analysis .... 243/ GC 289-292
Blaenhirwaun Pumpquart 13* gasification 11
Blast furnace, typical charges per day 292 yield vs. time from pyrolysis of
Blending procedures 7-8,11-12 Beulah North Dakota lignite 121/

INDEX 315
Carbon monoxide spectrum 114/ Coal-derived products solvent

Carbonaceous system and liquid solubility analysis 225-236
crystals 3-4 Coal gasifier tar, proton NMR, mole
Carbonization process 2-3 percent of hydrogens 219*
electron optical and IR spectro- Coal-oil slurry, high conversion, and
scopic investigation 293-309 solvent solubility 229-236
gas analysis to determine length Coal ranking systems, comparison of
of coking cycle 287 U.K. and U.S 12*
Categories, SEM-AIA mineral 244* Coal structure and proximate analysis
Cesium iodide matrix 49-51 fixed carbon relation 118, 121-122
Chars, FTIR spectra during Coal tar, alkane characterization 27-43
thermal decomposition 119/ Coal-tar branched/chain alkanes,
Cherokee, sulfur analysis by EPM .... 198* Rexco, proton-decoupled
Chloride analysis 149 carbon-13 36*, 35-38
Chlorine analysis 185-190 Cobalt analysis in coal andflyash
using ICP-AES 150*, 153*, 160*
of Indian coals 190*

using Parr oxygen bomb Cokes
elemental analysis 152*, 153*, 160* nomenclature, optical texture in
Chlorite, Mossbauer and S E M - polished surfaces 6*
AIA analyses 244*, 248*, 250* optical properties 4-7
Chloroform, solvent matrix for optical and SEM micrograph of
ICP-AES 167* Spencer Wharf and Clyde
Chromatogram, reconstructed ion, Ironworks 15/, 16/
toluene subfraction from silica properties and carbonization 2-7
gel column of Sephadex strength 5, 8
LH-20 column 216/ Coke oven, construction 282
Chromatograms, reconstructed ion, Coke oven gas
from GC/MS analysis of vapor composition during coking
phase organic extractable 212/ cycle 290/, 291*
Chromatography flow diagram 283-286
gas—See GC Coking cycle, gas analysis to determine
liquid—See L C length 286-292
size exclusion, ICP-AES Coking potential of coal blends 7
detection 172-180 Colormetric procedure for the deter-
solvent, metal detection in coal- mination of germanium 158
derived process 172 Column, elution profiles of compounds
Chromium from Sephadex LH-20 209/
analysis in coal andflyash using Column, silica gel, reconstructed ion
ICP-AES 150*, 153*, 160* chromatogram of toluene
detection subfraction 216/
limits and analysis by Column packing, separation of silicon
ICP-AES 167*, 169*, 171* model compounds with silicon
separation of process solvent 181/ detection 178/
Clarion, sulfur analysis by EPM .195-202 Complex of gallium—malachite green 156
Classes size in SEM-AIA of coal 244* Composition of coke oven gas during
Classification by solvent solubility 225-236 coking cycle 290/, 291*
Cleanup device samples, dichloro- Computer applications, FTIR 52-58
methane extractables from bottom Computer programs, library search
ash, cyclone ash, tar trap tar, routines 102, 104
scrubber water, scrubber tar 21 Concentration meter, slurry 273-275
Cleanup system, M E T C low Btu Conductivity gauge for slurry
gasifier, schematic diagram 207/ concentration meter 273-275
Clintwood, sulfur analysis by Continuous on-line nuclear assay of
EPM 195-202 coal (CONAC) 268-269
Clyde Ironworks coke, optical and Copper, detection limits and analysis
SEM micrograph 15/, 16/ by ICP-AES 150*, 153*, 160*,
Coal-derived process solvent 167*, 169*, 171*
chromatography, metal Coquimbite, Mossbauer and SEM-AIA
detection 172 analyses 248*, 250*

Corrections for FTIR mineral analysis 85 Diterpane, cyclic structure 29/

Cortonwood Silkstone coal, analysis .... 12/ Dolomite, SEM-AIA analyses ...244/, 250/
Cost of elemental analyzers 269 Domains 6/
Creosote oil, pressure filtration 236/ DRIFT (diffuse reflectance IR Fourier
Cross-linking in liquid crystals 3-4 transform spectroscopy) 133-143
Crude oils, alkane content 28/ DRIFT spectra of Wyodak coal 136/,
Crystals, liquid, and mesophase 3—4 138/, 140/, 142/
Curve, coal washability 262/
Curve resolving, FTIR 59, 61
Cyclic monoterpane, diterpane, ses- Ε
quiterpane, sterane, and triter- Eastern coals, gallium and germanium
pane, structure 29/ content 156/
Cyclohexane solubility in coal-derived Economic considerations of on-line
products 225 analytical instruments 275-277
Cyclone ash, gasifier cleanup device EDX—See Energy dispersive x-ray
samples 215/
Electron image
inverted backscattered, of Pust
D seam Montana lignite and
Data analysis operations, FTIR 52-58 energy-dispersive x-ray spec
Density gauges, nuclear 267-268, 273 trum of a maceral 253/
Derivative spectroscopy, secondary, of bituminous coal 243/
FTIR 59, 60/, 68/, 72/ Electron micrograph of coalesced
Detarred coke oven gas, composition .. 291/ and isolated spheres in Illinois
Detection No. 6 vitrinite and Pittsburgh
gamma and neutron 273-275 No. 8 vitrinite 294/
ICP-AES for size exclusion Electron micrograph transmitted of
chromatography 172-180 semicoke from Lower Kittanning
iron, separation of process solvent . 179/ coal 301/
metal, in coal-derived process Electron optical IR spectroscopic
solvent chromatography 172 investigation of coal
silicon, iron, and chromium, sepa carbonization 293-309
ration of process solvent ...177-182 Electron probe microanalysis for
Detection limits direct determination of organic
ICP-AES 166 sulfur 191
spectroscopic procedures 153/ The Elemental Analyzer 268-269
Deuterium-exchanged Pittsburgh Elemental detection limits monitored
seam coal, FTIR spectra 86/ in various solvents for ICP-AES 167/
Dibenzothophene, GC/MS identifica Elkhorn, sulfur analysis by E P M .195-202
tion in toluene subfraction of Elution profiles of compounds from
tar trap tar 218/ Sephadex LH-20 column 209/
Dichloromethane extractables from Emission lines of elements in
glass fiber Tenaxfilter,recon ICP-AES 166-172
structed ion chromatograms from Energy dispersive x-ray ( E D X ) -
GC/MS analysis and mass scanning electron microscope
distribution 212/, 215/ (SEM) vs. electron probe micro
Dicyclic hydrocarbons, structure 29/ analysis for sulfur
Dietz, sulfur analysis by EPM 195-202 analysis 192-194,200
Difference methods, FTIR 54-55 Energy-dispersive x-ray spectrum of a
Difference spectrum maceral of Pust seam Montana
of acetylated lignite 68/ lignite 253/
using DRIFT 138/, 139/, 140/ EPM—-See Electron probe micro
Diffuse reflectance IR Fourier trans analysis
form spectroscopy—See DRIFT Eschka method, chlorine
Diffuse reflectance spectroscopy 82, 84-85 determination 190
Dimethylbenzoquinoline, dimethyl- Ethers, aromatic, in Illinois coal
naphthalene, dimethylphenana- semicokes 300
threne, and dimethylquinolines, Experimental apparatus for determi
GC/MS identification in tar nation of chlorine in organic
trap tar 212/, 218/ combination 188/

INDEX 317
Extinction coefficients, mean, for FTIR—

absorbing groups of 156 model Continued
compounds 101/ vs. NMR for aromatic carbon 100/
Extracts, fossil fuel, structural of solids 79-99
spectroscopic analyses 28 thermal decomposition
Exxon-Baytown analytical methods study 113, 116-118
for coal and fly ash analysis 161/ spectra
of chars during thermal
F decomposition 119/
of coals and their vacuum
Factor analysis, FTIR 55-58 distilled tars 117/
Fast Fourier transformation of the of 4-hydroxyl quinoline and
free-induction decay of coal- 1-napthol, comparison 103/
derived products 34 of lignite 80/, 83/
Ferric oxide, Mossbauer spectra .247/, 248* of liquefaction feedstock and
Field desorption MS 31,43
products 124/
Fies coal, elemental analysis using of napthalene and quinoline,
ICP-AES 168-172 comparison 103/
Filter, glassfiberTenax, reconstructed of raw vs. chemically cleaned
ion chromatograms from GC/MS coal 125/, 126/
analysis of vapor phase organic of tars from a Pittsburgh seam
extractable 212/ bituminous coal 120/
Filter sample, raw gas, mass distribu- of vitrinite concentrate 53/, 72/
tion of dichloromethane scattering and mineral correction 87/
extract 215* vs. wet chemistry 100/
Fischer assay oil yield correlation FTIR, diffuse reflectance—See DRIFT
with aliphatic hydrocarbon Fuels, fossil
concentration 123/ alkanes in 27-43
Fissure formation, coal blends 5, 7 spectroscopy 28, 29-43
Fixed carbon, proximate Functional group, aliphatic C-H,
analysis 118, 121-122 and degree of oxidation 141
Flow domain anisotropy 6* Functional group, carbon,
Fluid melts and carbonization process 2-3 determination 98-99
Fluid phases, reactions with coal 133 Functional group, quantitive deter-
Fluid properties from Bethlehem mination using FTIR 47-74
plastometer test 298* Furnace, blast, typical charges per day 292
Fluidity of Pittsburgh, Illinois, and Fusinite, organic sulfur analysis
Lower Kittanning coal 296*, 298* by E P M 194-202
Fluidized-bed coal tar, carbon-13
spectrum 35
Fluorene andfluoranthene,GC/MS G
identification in toluene subfrac-
tion of tar trap tar 218* Gallium, spectrophotometric
Fluoride analysis 149 determination 154-161
Fluorine analysis using Parr oxygen Gallium (III)—malachite green
bomb elemental reaction 156
analysis 152*, 153*, 160* Gamma density gauge for slurry
Fly ash, elemental analysis 147 concentration meter 273-275
Fossil fuels Gas analysis to determine length of
alkanes in 27-43 coking cycle 286-292
spectroscopy 28, 29-43 Gas, coke oven, composition during
Freeport, sulfur analysis by EPM .195-202 coking cycle 290/, 291*
FTIR 47-74 Gases from pyrolyzed coal, high
applications 77-127, 113 resolution spectra 110/, 111/, 114/
determination of hydroxyl groups 61—71 Gases, analysis using FTIR 109
free-induction decay 34 Gasification
of gases 109 in carbon dioxide 11
inversion recovery technique 37 and heat treatment of metallurgical
of liquids 104-108 coke 10-11, 14-17
model compounds 99-104 low Btu 205-222

318
Gasifier cleanup device samples, per Hydrogen—Continued

cent dichloromethane extract aromatic, out-of-plane bending vi-
ables from bottom ash, cyclone brations shown by IR spectra 305/
ash, tar trap tar, scrubber water, FTIR analysis 93, 96-99
and scrubber tar 212/ proton NMR analysis, mole percent 219/
Gasifier, M E T C low Btu, Hydrogen bonding O-H absorption .... 102
schematic diagram 207/ Hydrogen/carbon ratio of organic
Gauss-Lorentz sum and product func matter in hydrocarbon minerals 28/
tions, FTIR spectral analysis .... 61 Hydrogen chloride formation in
GC analysis 31, 34, 210, 289-292 chlorine determination 186-190
GC/FTIR analysis 113 Hydrogen content
GC/MS analysis of Kentucky Colonial Mine and
of coal-derived products 31, 41, 43 Illinois Burning Star Mine
of gasifier process streams 210-222 coal 228/
Gel permeation chromatography .208-218 of Pittsburgh, Illinois, and Lower
Germanium, spectrophotometric Kittanning coal 298/
determination 154-161 of Six Bells, Cottonwood Silkstone,

Gas flow diagram, coke oven 283-286 and Maltby Swallow Wood
GlassfiberTenaxfilter,reconstructed coals 12/
ion chromatograms from GC/MS using slurry concentration meter 273-275
analysis of dichloromethane of vitrains 13/
extractables 212/ of Wyodak and Bruceton coal 136/
Goethite, particle-size parameter Hydrogen distribution in fossil fuel
distribution in middle alkane extracts from proton
Kittanning coal 249/, 250/, 257/ NMR spectra 33/
Gypsum, SEM-AIA analyses 244/, 250/ Hydrogen transfer 9
Hydroxyl group determination
by FTIR 61-71, 92, 95/
4-Hydroxyl quinoline and 1-napthol,
Ή NMR—See Proton NMR comparison of the FTIR spectra 103/
Halite, SEM-AIA analyses 244/, 250/
Halogen analysis using ion analyzer .. 149
Hartshorne, sulfur analysis
using E P M 195-202 ICP-AES 148-151, 163-182
Hazard, sulfur analysis ICP-AES, detection limits for differ-
using E P M 195-202 ent spectroscopic procedures 153/
Hematite, Môssbauer and Illinois coal
SEM-AIA analyses 249/, 250/ Burning Star Mine, analysis 228/
Heptane, solvent matrix gallium and germanium content 156/
for ICP-AES 167/ IR spectra 301/, 300-307
Heptane-insolubles in Ashland No. 6 vitrinite, electron micrograph
A200 pitch 13/ of isolated spheres 294/
Heat treatment and gasification of sulfur analysis by EPM 198/
metallurgical coke 10-11, 14-17 Illite, Môssbauer and SEM-AIA
High resolution FTIR spectra of gases analyses 244/, 248/, 250/, 255/
from pyrolyzed coal 110/, 111/, 114/ Indian coals
High-conversion coal-oil slurry chlorine contents 190/
solubility 229-236 gallium and germanium content ... 156/
Hydrocarbon, aliphatic Indianflyash, gallium and germanium
correlation of Fischer assay oil content 156/
yield 123/ Inductively coupled plasma-atomic
structures 29/ emission spectrometry—See
Hydrocarbon minerals, alkane ICP-AES
content and H/C ratio of Industry
organic matter 28/ coal preparation, analytical
Hydrodesulfurization effect on coal instruments 259-277
structure 122, 124-127 steel, coal as energy 281-292
Hydrogen Inertinite macérais, sulfur analysis
aliphatic, correlation with tar yield 117/ by E P M 195-202

INDEX 319
Infrared spectroscopy—See IR Κ
Inorganic elements in macérais, Kaolin, DRIFT spectra 138/, 139/, 140/
characterization 252-254 Kentucky coal, sulfur analysis by
Instrumentation in coal preparation EPM 198*
industry 259-277 Kentucky 9/14 coal, pressure
Integration limits for absorbing groups filtration 232*
of 156 model compounds 101* Kentucky Colonial Mine, analysis 228*
Interferences in gallium and germa- Kentucky solvent refined coal pro
nium determination 157* cessing conditions 170*
Intermediate states in air Kinetic measurements of gases using
oxidation 143-144 FTIR 109
Inversion-recovery Fourier transform Kittanning, sulfur analysis by
(IRFT) technique of coal- EPM 195-202
derived products 37 Kuwait crude branched/cyclics,
Inverted backscattered electron proton NMR spectra 33*
(BSE) image of bituminous

coal 243/ L
Inverted backscattered electron (BSE)
image of Pust seam Montana Laboratory instrumentation 260, 263
lignite 253/ Lafayette coal, elemental analysis
Ion analyzer for halogen analysis 149 using ICP-AES 168-172
Ion chromatogram, reconstructed LC/FTIR 104
from GC/MS analysis 212/, 216/ LC/ICP-AES 163-182
IR absorption and on-line moisture Lead determination
monitors 270-273 using hydride-atomic absorption
IR spectroscopy 31 spectrometry 155*
of coal carbonization 293-309 using ICP-AES detection
Fourier transform—See FTIR limits 167*, 169*, 171*
Fourier transform, diffuse using Parr oxygen bomb elemental
reflectance—See DRIFT analysis 152*, 153*, 160*
spectra of Pittsburgh coal and Least squares optimization procedure,
semicokes, Illinois coal and FTIR spectral analysis 61
semicokes, and Lower Kittan- Leaves, orchard, elemental analysis . 152*
ning coal and semicokes .300-307 Lepidocrocite, Mossbauer and S E M -
Iron-57 Mossbauer spectroscopy of AIA analyses 249*, 250*
coal minerals 241, 245-252 Library search routines, computer
Iron analysis programs 102,104
in coal and fly ash using Lignite ashes, North Dakota, gallium
ICPES 150*, 153*, 160* and germanium content 156*
in clays, Mossbauer spectra ...247/, 248* Lignite
using ICP-AES 150*, 153*, 160*, alkane content 28*
167*, 169*, 171* Beulah North Dakota, carbon
Iron detection, separation of process dioxide yield vs. time from
solvent 179/ pyrolysis 112/
Iron model compounds, molecular FTIR spectra 80/, 83/, 97/
structures 176/ Pust seam Montana, inverted back-
Iron-sulfate, SEM-AIA scattered electron image 253/
analyses 244*, 250*, 255* Turkish, alkane characterization ....27-43
Isocratic separation, organometallic Linearity, gallium and germanium
systems 174, 175 determination in coal 157*
Isoprenoid, acyclic structure 29*Liptinite macérais, sulfur analysis
Isotropic properties of cokes and by EPM 195-202
coke blends Liquefaction feedstock and products,
1-7
FTIR 122, 124/
Liquid cell spectrum of recycle
solvent 107/
Liquid chromatography—See L C
Jarosite, Mossbauer spectra 247/, 248* Liquid crystals and mesophase 3-4
Jarosite, SEM-AIA analyses 244*, 250* Liquids, FTIR 104-108

Lorentzian band shapes, FTIR Metallograms 172-173

spectral analysis 61 Metallurgical coke 123
Low Btu gasification 205-222 Metallurgical coke, point-
Low temperature ash spectrum by counting 10, 21-24
addition of spectra from mineral Metallurgical cokes, Spencer Works
library 88/ Wharf coke and Clyde Iron-
Lower Kittanning coal and semicokes, works coke 10
IR spectra 300-307 M E T C low Btu gasifier and cleanup
Lower Kittanning vitrinite, spheres system, schematic diagram 207/
and rods 296/ Methods
Exxon-Baytown analytical, for coal
M and fly ash analysis 161/
Macérais Soxhlet-extraction vs. pressure-
aromatic C - H out-of-plane bend- filtration 225
ing mode, factor analysis 58/ Methylacridine, Methylbenzoquino-
line, Methyldibenzothiophene,
characterization of inorganic
elements 252-254 Methylphenanthridines, and
organic sulfur analysis by EPM 194-202 Methylquinoline, GC/MS iden-
of Pust seam Montana lignite, tification in tar trap tar 212/, 218/
energy-dispersive x-ray Micrinite, organic surfur analysis
spectrum 253/ by E P M 194-202
Magnesium analysis detection limits Micrograph—See Optical and second-
and analysis by ICP-AES .150/, 153/, ary electron (SEM) micrograph
160/, 167/, 169/, 171/ Micrograph, electron
Magnetite, Môssbauer and SEM-AIA of coalesced spheres in Pittsburgh
analyses 249/, 250/ No. 8 vitrinite 294/
Maltby Swallow Wood coal analysis .. 12/ of isolated spheres in Illinois No.
Manganese, detection limits and anal- 6 vitrinite 294/
ysis by ICP-AES 167/, 169/, 171/ of semicoke from Lower
Manton Main Parkgate 13/ Kittanning coal 301/
Marcasite, Môssbauer and SEM-AIA of semicoke from Pittsburgh No.
analyses 248/, 250/ 8 coal 299/
Mass distribution of dichloromethane Microscopy, optical 9-23
extract of a raw gas filter sample 215/ Microwave moisture meter, on-line,
Mass distribution and Microwave attenuation .270-273
of 0 ° C condenser sample of gasifier Middle Kittanning coal, particle-size
process streams 214/ parameter distribution for
of Sephadex LH-20 fractions of tar goethite 249/, 250/, 257/
samples from Venturi scrubber Middle Kittanning seam mineral
decanter outlet and the tar analysis 255/
trap 217/ Mineral characterization
Mass spectroscopy—See MS using FTIR, spectral
Mechanistic studies of air corrections 51, 55, 85
oxidation 141-144 using SEM-AIA and Môssbauer
Mean extinction coefficients for spectra 239-256
absorbing groups of 156 model Mineral content blends 8
compounds, FTIR 101/ Mineral library, synthesis of low
Melanterite, Môssbauer and S E M - temperature ash spectrum by
AIA analyses 248/, 250/ addition of spectra 88/
Mercury analysis using Parr oxygen Mineral mixtures, factor analysis 56/
bomb elemental analysis 152/, Minerals, hydrocarbon, alkane con-
153/, 160/ tent and atomic H/C ratio of
Mesophase, definition 3-4 organic matter 28/
Mesophase structure of Pittsburgh, Minicomputer, FTIR 52-58
Illinois, and Lower Kittanning Model compounds for quantitative
coal 296/ FTIR 99-104
Metal quantitation in synfuels, Moisture content
using ICP-AES 163-182 of vitrains 13/
Metallic materials in process of Wyodak and Bruceton coal 136/
solvents 172-180 Moisture meter, on-line microwave 270-273

INDEX
321
Molecular structures of iron

model compounds 176/
Ohio coal, sulfur analysis by EPM .195-202
Molybdenum, detection limits and
analysis by ICP-AES 167/, 169/, 171/ Oil, creosote, pressure filtration 236/
Monocyclic hydrocarbons, structure .. 29/ Oil shales
Monoterpane, cyclic structure 29/ alkane content 28/
Montana lignite, Pust seam, inverted characterization using FTIR 122
backscattered electron image 253/ On-line analytical instrumentation 259-277
Montmorillonite, Mossbauer and S E M - On line microwave moisture meter. 270-273
AIA analyses 244/, 248/, 250/ On-line microwave moisture
Montan wax total alkanes meter 270-273
proton NMR spectra 33/ Optical micrograph
total ion current constructed of Clyde Ironworks coke 16/
from GC/MS 44/ of pitch-coke breeze in coke from
Mosaics 6 Six Bells Coal 18/, 21/
of Spencer Wharf coke 15/
Mossbauer spectroscopy, iron-57,

Optical microscopy 9-10
of coal minerals 245-252
Optical properties of cokes 4-7
MS, field desorption 43
Orchard leaves, elemental analysis . . . 152/
Organic chlorine determination 185-190
Ν Organic sulfur analysis by EPM 191
Organometallic systems, isocratic
Nailstone Yard 13/ separation 174, 175
Napthalene and quinoline, comparison Orsat analysis 289-292
of the FTIR spectra 103/ Oven, coke, construction 282
1-Napthol and 4-hydroxyl quinoline, Overhauser enhancement 35
comparison of the FTIR spectra . 103/ Oxidation, air, studies of coal using
Nematic liquid crystals 3-4 DRIFT 133-143
Neutron gauge for slurry concen Oxidation product, detection using
tration meter 273-275 FTIR 54-56
Nickel analysis using ICP-AES Oxygen content
150/, 153/, 160/, 167/, 169/, 171/ of Kentucky Colonial Mine and
Nitrogen analysis Illinois Burning Star Mine
of Kentucky Colonial Mine and coal 228/
Illinois Burning Star Mine .... 228/ of Pittsburgh, Illinois, and Lower
using Parr oxygen bomb elemental Kittanning coal 298/
analysis 152/, 153/, 160 of vitrains 13/
of Pittsburgh, Illinois, and Lower of Wyodak and Bruceton coal 136/
Kittanning coal 298/
of vitrains 13/
of Wyodak and Bruceton coal 136/
Nitrogen compounds, ring 102
Parr oxygen bomb 148-149, 151, 152/
NMR spectroscopy
carbon-13, of coal-derived Particle size and tensile strength 8
products 34-41 Particle-size analysis by
vs. FTIR for aromatic carbon 100/ SEM-AIA 254, 256
on-line moisture meters 270-273 Passive pitches 8
proton, mole percent of hydrogens Pentacyclic hydrocarbons, structure .. 29/
in coal gasifier tar 219/ Petroleum coke breeze and tensile
spectra, proton of Montan wax strength 8
total alkanes 33/ Petroleum crude, alkane
spectra, photon of Kuwait crude characterization 27-43
branched/cyclics 33/ pH monitors 268
Nomenclature, optical texture in Phase transition, liquid crystal 4-7
polished surfaces of cokes 6/ Phenanthrene and phenanthridine,
North Ceylon Meadow Vein 13/ GC/MS identification in tar
North Dakota lignite ashes, gallium trap tar 218/
and germanium content 156/ Phenolic hydrogen in coal gasifier
Nuclear density gauges ' 267 tar by proton NMR 219/

Phenylnaphthalene, GC/MS identifi- Proton NMR 33

cation in tar trap tar 218/ spectra of Kuwait crude branched/
Phosphorus analysis using Parr cycles and Montan wax total
oxygen bomb elemental alkanes 33/
analysis 152/, 153/, 160/ mole percent of hydrogens in coal
Photoacoustic spectroscopy 82 gasifier tar 219/
Physical properties of nematic Proximate analysis fixed carbon rela-
liquid crystals 3-4 tion and coal structure .118, 121-122
Pitch, Ashland A200 10, 13/ Pseudovitrinite, organic sulfur
Pitch additives 8 analysis by EPM 194-202
Pitch and coals, blending 11 Pust seam coal, inverted backscat-
Pitch-coke breeze in coke from Six tered electron image 253/
Bells coal, optical micrograph .18/, 21/ Pyrene, GC/MS identification in
Pittsburgh coal tar trap tar 218/
electron micrograph of coalesced Pyridine, solvent matrix for
spheres in vitrinite 294/ ICP-AES 167/
FTIR spectra 85/, 86/, 89/, 120/ Pyrite

IR spectra 301/, 300-307 Môssbauer spectra 247/, 248/
SEM of semicoke from 299/ SEM-AIA analyses 244/, 250/, 255/
sulfur analysis by EPM 195-202 Pyritic sulfur analysis 194-195
Plant, coal preparation 260-262 Pyrolysis analysis 113
Plastic and post-plastic zone of blends 7 Pyrolysis of Beulah North Dakota
Point-counting, metallurgical lignite, carbon dioxide yield
coke 10,21-24 vs. time 112/
Poly-branched hydrocarbons, Pyrolyzed coal, high resolution spectra
structure 29/ of gases 110/, 111/, 114/
Porosity and coke strength 5
Post-plastic and plastic zone of
blends 7 Q
Potassium analysis in coal and fly Quality control on-line
ash using ICP-AES ...150/, 153/, 160/ instrumentation 275-277
Potassium bromide matrix 49-51 Quantitative analysis
Potassium bromide pellets, of functional groups by FTIR 47-74
preparation 79-81 of gases by FTIR 109
Potassium bromide spectrum of of liquids by FTIR 104
recycle solvent 108/ of minerals by SEM-AIA and
Powdered coal, analysis using Môssbauer spectra 239-256
DRIFT 135, 136/ of model compounds by FTIR .99-104
Pressure filtration for solvent Quartz, SEM-AIA
solubility analysis of coal-derived analyses 244/, 250/, 255/
products 225-236 Quinoline-insolubles in Ashland
Pristane, carbon-13 spin-lattice A200 pitch 13/
relaxation times 39/
Process control on-line instru-
mentation 275-277 R
Process solvents containing metallic
materials 172-182 Range for AAS determination of
Processing conditions for Kentucky hydride-forming elements 153/
solvent refined coal 170/ Ranking systems of coal, comparison
Product quality and on-line analytical of U.K. and U.S 12/
instruments 275-277 Rapid EPM method for organic
Properties sulfur content 200
coke, and carbonization 2-7 Raw vs. chemically cleaned coal,
fluid, from Bethlehem plastometer FTIR spectra 125/, 126/
test 298/ Reaction of gallium (III)-malachite
nematic liquid crystals 3-4 green 156
Proton-decoupled carbon-13 NMR of Reactions, coal with fluid phases 133
Rexco coal-tar branched/chain Reactivity of cokes and optical
alkanes 35-38 properties 5-7

INDEX 323
Reconstructed ion chromatogram— Semicoke

See Chromatogram, recon from Lower Kittanning coal, T E M 301/
structed ion from Pittsburgh No. 8 coal, SEM .. 299/
Reflectance, diffuse, IR Fourier trans from Pittsburgh, Illinois, and Lower
form spectroscopy—See DRIFT Kittanning coal IR
Regression analysis to determine spectra 301/, 300-307
aromatic and aliphatic Semifusinite, organic sulfur
absorptivities 97/ analysis by E P M 194-202
Resinite 195,201* Sensitivity
Resolution for AAS determination of hydride
of difference spectrum obtained forming elements 153*
from acetylated coal 68/, 69/ for gallium and germanium deter
of FTIR spectra 59, 61 mination in coal 157*
Rexco coal-tar Separation of process solvent 177-182
branched/chain alkanes, proton- Sephadex LH-20 fractions of tar
decoupled carbon-13 35-38 samples from Venturi scrubber

carbon-13 spin-lattice relaxation decanter outlet and tar trap,
times 39* mass distribution 217*
GC 42/ Sesquiterpane, cyclic structure 29*
Rhode Island anthracite, Mossbauer Sewell, sulfur analysis by EPM .195-202
spectra 247/ Siderite, clays, Mossbauer spectra 247/, 248*
Ribbons 6* Silicate, SEM-AIA
Ring nitrogen compounds 102 analyses 244*, 250*, 255*
Roddymoor Ballarat 13* Silicon, detection limits and analysis
Rods in Lower Kittanning vitrinite .... 296/ by ICP-AES 150*, 153*, 160*,
Rutile, SEM-AIA analyses 244*, 250* 167*, 169*, 171*
Silicon model compounds, separation
S with silicon detection as a func
tion of column packing 178/
Sample preparation for FTIR 49-51 Silver, detection limits and analysis
Saturated hydrocarbons, structures .... 29* by ICP-AES 167*, 169*, 171*
Scanning electron microscope Singly-branched hydrocarbons,
(SEM)-energy dispersive x-ray structure 29*
(EDX) vs. electron probe Six Bells coal
microanalysis for sulfur analysis 12*
analysis 192-194,200 optical micrograph of pitch-coke
Scanning electron microscopy 9-23 breeze in coke 18/, 21/
and automated image analysis Size exclusion chromatography with
(ΑΙΑ) 241-245, 250-256 ICP-AES detection 172-180
and micrographs of Clyde Iron Slit width for AAS determination of
works and Spencer Wharf hydride forming elements 153*
cokes 15/, 16/ Slurry concentration meter 273-275
Scattering and mineral correction of
Slurry, high-conversion coal-oil, and
FTIR spectrum 87/
solvent solubility 229-236
Scattering process 264
Sodium analysis in coal andflyash
Scrubber tar and scrubber water,
gasifier cleanup device samples .. 215* using ICP-AES 150*, 153*, 160*
SEC—See Size exclusion chromatography Solid sample analysis using FTIR 79-99
Second derivative spectra 60/ Solidification of Pittsburgh, Illinois,
Secondary electron image of and Lower Kittanning coal 298*
bituminous coal 243/ Solubility analysis using pressure
Secondary electron micrograph of filtration 225-236
semicoke from Pittsburgh Solvent
No. 8 coal 299/ elemental detection limits and
Selenium determination in coal by emission lines monitored
hydride generation-atomic using ICP-AES 167*
absorption spectrometry 155* process, detection of metals 172-182
SEM—See Scanning electron recycle, liquid cell and potassium
microscopy bromide spectrum 107/, 108/

Solvent chromatography and metal Spectral corrections and mineral

detection in coal-derived process 172 analysis, FTIR 85
Solvent refined coal, metal Spectral subtraction, FTIR 54-55
analysis 166-172 Spectral synthesis 85,88-92
Solvent solubility analysis using Spectrometric determination of
pressure filtration 225-236 germanium 154-161
Sorption-desorption monitoring by Spectrometry, inductively coupled
DRIFT 135-143 plasma emission (ICPES) ... 148-151
Sortex Ash Monitor sensor system .... 265/ Spectrophotometer, atomic absorp-
Source, Californium-252 neutron, tion (AAS) 148, 151, 153
for elemental analyzer system 268-269 Spectrophotometric determination
South African coals, gallium and of gallium 154-161
germanium content 156/ Spectroscopic analyses, structural, of
Soxhlet extraction, apparatus and fossil fuel extracts 28
procedure 230-231 Spectroscopy of fossil fuels 28, 29-43
Soxhlet-extraction method vs. pres- Spectroscopy
sure-filtration method 225 derivative, FTIR 59, 60/, 68/, 72/

Speciation in synfuels, ICP-AES .163-182 detection limits 153/
DRIFT, of Wyodak coal 136/, 138, diffuse reflectance 82, 84-85
140/, 142/ IR, electron optical investigation of
energy dispersive x-ray 253/ coal carbonization 293-309
FTIR Môssbauer, of coal minerals,
of carbon monoxide 114/ iron-57 241,245-252
of chars during thermal photoacoustic 82
decomposition 119/ Spencer Wharf coke, optical and
of coals and their vacuum SEM micrograph 15/
distilled tars 117/ Spheres in Lower Kittanning, Pitts-
of 4-hydroxyl quinoline and burgh No. 8, and Illinois No. 6
1-napthol, comparison 103/ vitrinite, electron micro-
of lignite 80/, 83/ graph 294/, 296/
of liquefaction feedstock and Spin-lattice relaxation time measure-
products 124/ ments, carbon-13 37-41
liquid cell, of a recycle solvent .. 107/ Sporinite, organic sulfur analysis
of naphthalene and quinoline, by E P M 194-202
comparison 103/ Steel industry, coal as energy 281-292
of a raw vs. chemically cleaned Sterane, cyclic structure 29/
coal 125/, 126/ Strength of coke 5, 8
recycle solvent, potassium Strength testing 10
bromide 108/ Structural spectroscopic analyses of
scattering and mineral correction 87/ fossil fuel extracts 28
synthesis of low temperature ash Structure
by addition of spectra from analysis using FTIR 113
mineral library 88/ mesophase, of Pittsburgh, Illinois,
of tars from a Pittsburgh seam and Lower Kittaning coal 296/
bituminous coal 120/ molecular, of iron model
of vitrinite concentrate 53/, 72/ compounds 176/
high resolution of gases from pyro- and proximate analysis fixed
lyzed coal 110/, 111/, 114/ carbon relation 118,121-122
IR for Pittsburgh, Illinois, and of saturated hydrocarbons 29/
Lower Kittanning coal and Subbituminous coal
semicokes 300-307 analysis using DRIFT 133-143
Môssbauer, Rhode Island analysis using FTIR 97/
anthracite 247/ Sulfcoalyzer, CONAC system 269
proton NMR Sulfur analysis
of Kuwait crude branched/ of Ashland A200 pitch 13/
cyclics and Montan wax of Kentucky Colonial Mine and
total alkanes 33/ Illinois Burning Star Mine 228/
of tar trap tar 220/ organic, by EPM 191-202

INDEX 325
Sulfur analysis— Tin, detection limits and analysis

Continued by ICP-AES 167/, 169/, 171/
using Parr oxygen bomb 152/, 153/, 160/ Titanium, detection limits and analysis
of Pittsburgh, Illinois, and Lower by ICP-AES 150/, 153/, 160/,
Kittanning coal 298/ 167/, 169/, 171/
SEM-AIA analyses 244/, 250/ Toluene subfraction from silica gel
of vitrains 13/ column of Sephadex LH-20
of Wyodak and Bruceton coal 136/ column, reconstructed ion
Sulfur contents chromatogram 216/
Sunnyside, sulfur analysis by EPM 195-202 Toluene, solvent matrix for
Superactive pitches 8 ICP-AES 167/
Surface complexes in air oxidation 143-144 Total ion current constructed from
Sylvite, SEM-AIA analyses 244/, 250/ GC/MS of Montan wax total
Symmetry, liquid crystals 3-4 alkane fraction 44/
Synfuels, metal quantitation and Trace element analysis
speciation using ICP-AES .163-182 of a solvent refined coal in
Synthesis of low temperature ash pyridine 167/

spectrum by addition of spectra in coal by hydride generation-
from mineral library 88/ atomic absorption
Synthesis, spectral 85, 88-92 spectrometry 155/
System Transmitted electron micrograph of
coal sampling 266/ semicoke from Lower
CONAC, solfcoanalyzer 269 Kittanning coal 301/
Sortex Ash Monitor sensor 265/ 2,4,6-Trichlorophenol in chlorine
Szomolnokite, Mossbauer and S E M - determination 187
AIA analyses 248/, 250/ Tricyclic hydrocarbons, structure 29/
Trimethylnaphthalene, trimethyl-
phenathrene, and trimethyl-
Τ quinolines, GC/MS identification
Tar of tar trap tar 218/
alkane characterization 27-43 Triterpane, cyclic structure 29/
coal gasifier, proton NMR, mole Turkish asphaltite, carbon-13 spin-
percent of hydrogens 219/ lattice relaxation times 39/
Pittsburgh seam bituminous coal, Turkish asphaltites, alkane content .... 28/
FTIR spectra 120/ Turkish lignites, alkane
Rexco, G C 42/ characterization 27-43
yield correlation with aliphatic Turkish Montan wax, alkane content.. 28/
hydrogen 117/
Tar trap tar
V
gasifier cleanup device samples 215/
mass distribution of Sephadex Vacuum distilled tars, FTIR
LH-20 fractions of tar samples spectra of coals 117/
from Venturi scrubber decan Vanadium, detection limits and anal
ter outlet 217/ ysis by ICP-AES 150/, 153/, 160/,
Tin determination in coal by hydride- 167/, 169/, 171/
atomic absorption spectrometry .. 155/ Vapor generation-atomic absorption
Tebo, sulfur analysis by EPM 198/ spectrometry 151
Tellurium determination in coal by Vapor phase organic extractable from
hydride-atomic absorption Tenax, reconstructed ion
spectrometry 155/ chromatogram 212/
Tensile strength, cokes 5, 8 Venturi scrubber decanter outlet and
Tetracyclic hydrocarbons, structure .. 29/ the tar trap, mass distribution of
Tetrahydrofuran solubility, coal- Sephadex LH-20 fraction of tar
derived products 225 samples 217/
Thermal decomposition study Viscosity and fluid melts 2
using FTIR 113, 116-118 Vitrain analysis 13/
TIC—See Total ion current Vitrinite
Tilmanstone 13/ concentrate, FTIR spectrum 53/, 72/

Vitrinite—Continued Wax
Illinois No. 6, electron micrograph Montan, total alkane fraction, total
of isolated spheres 294/ ion current constructed from
Lower Kittanning, spheres and rods 296/ GC/MS 44/
organic sulfur analysis by EPM .194-202 Turkish Montan, alkane content . . . 28/
Pittsburgh No. 8, electron micro- Western U.S. coals, gallium and
graph of coalesced spheres .... 294/ germanium content 156/
Volatile matter content Wildcat, sulfur analysis by EPM 198/
of Ashland A200 pitch 13/ Wyodak coal, DRIFT spectra .136/, 138/,
of Kentucky Colonial Mine and 140/, 142/
Illinois Burning Star Mine
coals 228/
using Parr oxygen bomb procedure 151
of Pittsburgh, Illinois, and Lower X-ray, energy dispersive ( E D X ) -
Kittanning coals 296/ scanning electron microscope
of Six Bells, Cortonwood Silkstone,
(SEM) vs. electron probe micro-

and Maltby Swallow Wood analysis for sulfur
coals 12/ analysis 192-194,200
of vitrains 13/ X-ray spectrum of a maceral, energy-
Volhard's method, chlorine dispersive, of Pust seam Montana
determination 189 lignite 253/
W
Washability, coal, curves 262/
Water as solvent matrix for ICP-AES 167/ Zinc, detection limits and analysis
Water-coal slurries 273-275 by ICP-AES 150/, 153/, 160/,
Water-magnetite slurries 273-275 167/, 169/, 171/
Wavelength for AAS determination Zone of blends, plastic and post-
of hydride-forming elements 153/ plastic 7
Jacket design by Kathleen Schaner.

Indexing and production by Anne Bigler and Florence H. Edwards.
Elements typeset by Service Composition Co., Baltimore, MD.

Printed and bound by Maple Press Co., York, PA.


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Publication Date: November 12, 1982 | doi: 10.1021/bk-1982-0205.

Coal and Coal Products:

In Coal and Coal Products: Analytical Characterization Techniques; Fuller, E.;

In Coal and Coal Products: Analytical Characterization Techniques; Fuller, E.;

E. L. Fuller, Jr., EDITOR

Sponsored by the ACS

Fuel, and Colloid

and Surface Chemistry

ACS SYMPOSIUM SERIES 205

AMERICAN CHEMICAL SOCIETY

In Coal and Coal Products: Analytical Characterization Techniques; Fuller, E.;

American Chemical Society

In Coal and Coal Products: Analytical Characterization Techniques; Fuller, E.;

M. Joan Comstock, Series Editor

David L. Allara Marvin Margoshes

Robert Baker Robert Ory

Donald D. Dollberg Leon Petrakis

Robert E. Feeney Theodore Provder

Brian M. Harney Charles N. Satterfield

W. Jeffrey Howe Dennis Schuetzle

James D. Idol, Jr. Davis L. Temple, Jr.

Herbert D. Kaesz Gunter Zweig

In Coal and Coal Products: Analytical Characterization Techniques; Fuller, E.;

In Coal and Coal Products: Analytical Characterization Techniques; Fuller, E.;

THE INDUSTRIAL REVOLUTION was based upon efficient use of mechanical

In Coal and Coal Products: Analytical Characterization Techniques; Fuller, E.;

In Coal and Coal Products: Analytical Characterization Techniques; Fuller, E.;

Theoretical and Experimental Approaches

MAGGI FORREST and HARRY MARSH

Mechanisms of carbonization of fluid systems from pitches and

Metallurgical coke is used in the blast furnace as an energy

In Coal and Coal Products: Analytical Characterization Techniques; Fuller, E.;

procedures which make use of c o a l s of v o l a t i l e content above and

The Formation of A n i s o t r o p i c Carbon. As c o a l i s heated i t

Over the temperature range 623 K to 773 K, caking c o a l s begin

I n i t i a l s o f t e n i n g of the c o a l i s due to increased thermal

R e s o l i d i f i c a t i o n of the c o a l i s due to chemical c r o s s - l i n k i n g

I t i s d u r i n g the p l a s t i c ( f l u i d ) stages of c a r b o n i z a t i o n that

In Coal and Coal Products: Analytical Characterization Techniques; Fuller, E.;

forms an a n i s o t r o p i c coke. The s i g n i f i c a n c e of t h i s phase

Conventional L i q u i d C r y s t a l s . There e x i s t some ( g e n e r a l l y

however, there i s w e l l d e f i n e d order on a l e n g t h s c a l e of 10^ urn

L i q u i d C r y s t a l s i n Carbonaceous Systems. The f o r m a t i o n of

In Coal and Coal Products: Analytical Characterization Techniques; Fuller, E.;

caused by p o l y m e r i z a t i o n a s s o c i a t e d w i t h i n c r e a s i n g heat treatment

A p y r o l y s i n g system about to pass through the l i q u i d c r y s t a l

a b l e f o r the system to undergo a p h y s i c a l phase t r a n s i t i o n to a

In Coal and Coal Products: Analytical Characterization Techniques; Fuller, E.;

nomenclature has been devised (Table I ) which ranges from v e r y

Coke s t r e n g t h i s i n t i m a t e l y r e l a t e d t o i t s p o r o s i t y and pore

w a l l s t r u c t u r e . During the f o r m a t i o n of the l a t t e r , l i q u i d

F i s s u r e propagation through the pore w a l l m a t e r i a l of coke

When carbon d i o x i d e r e a c t s w i t h carbon to produce carbon

In Coal and Coal Products: Analytical Characterization Techniques; Fuller, E.;

Nomenclature to Describe O p t i c a l Texture

Coarse-grained mosaics (Mc) <10.0 >5.0 urn i n d i a m e t e r

Medium-flow a n i s o t r o p y (MFA) <30 urn i n length;

Coarse-flow a n i s o t r o p y (CF) <60 >30 urn i n l e n g t h ;

A c i c u l a r f l o w domain a n i s o t r o p y (AFD) >60 um i n l e n g t h ;

Small domains (SD) <60 >10 ym i n diameter

Domains, - i s o m e t r i c (D) >60 ym i n diameter

In Coal and Coal Products: Analytical Characterization Techniques; Fuller, E.;

propagation of f i s s u r e s formed upon g a s i f i c a t i o n and thermal

Figure 3. Optical micrograph of Clyde Ironworks coke. Positions D and Ε dis