99

Determination of Forms o f S u l f u r i n Coal

N. F. Shimp, R. J. H e l f i n s t i n e , and J. K. Kuhn

I l l i n o i s S t a t e Geological Survey, Urbana, I L 61801

1'
INTRODUCTION
\
The need f o r low-sulfur c o a l has assumed major p r o p o r t i o n s . S h o r t a g e s of
o t h e r f o s s i l fuels, r e s t r i c t i o n s on sulfur oxide emissions, and t e c h n i c a l problems
a s s o c i a t e d with t h e u s e of h i g h - s u l f u r c o a l s i n newly proposed c o a l conversion
processes a r e c o n t r i b u t i n g t o t h e c r i s i s . I t i s now apparent not o n l y t o c o a l
s p e c i a l i s t s b u t a l s o t o o t h e r s t h a t t h e emission s t a n d a r d s and t e c h n i c a l problems
a s s o c i a t e d with h i g h s u l f u r c o n t e n t of bituminous c o a l s are c o n t r i b u t i n g g r e a t l y t o
t h e s e v e r i t y of t h e fuel s h o r t a g e s i n t h e United S t a t e s . Consequently, it i s
a p p r o p r i a t e t o d i s c u s s o l d and new methods of e v a l u a t i n g t h e s u l f u r s t a t u s of c o a l
and t o reexamine some of t h e problems a s s o c i a t e d with t h e i r a p p l i c a t i o n .
I
Free s u l f u r as such does n o t occur i n c o a l t o any s i g n i f i c a n t e x t e n t . S u l f u r
i s p r e s e n t i n c o a l i n o r g a n i c a l l y bound combinations, i n i n o r g a n i c compounds
mainly as p y r i t e (FeSp), and e s p e c i a l l y i n weathered c o a l s as msum (C&o1+.2H20)
and a s f e r r o u s sulfate (FeSOt,.TH20). I n a few c o a l s , s i g n i f i c a n t amounts of o t h e r
i n o r g a n i c s u l f a t e s and s u l f i d e s , e.g. b a r i t e (BaSOr,) and s p h a l e r i t e (ZnS), ( 1 , 2 )
which normally occur only i n t r a c e c o n c e n t r a t i o n s , may be p r e s e n t .

The t h r e e forms of s u l f u r commonly measured i n c o a l are s u l f a t e , p y r i t i c , and

organic. Although l e s s f r e q u e n t l y determined t h a n t o t a l s u l f u r , t h e y are, perhaps,
t h e most s i g n i f i c a n t i n terms o f c o a l u t i l i z a t i o n . Of t h e two predominant sulfur
forms, p y r i t i c and o r g a n i c , t h e former can b e p a r t i a l l y removed by c o n v e n t i o n a l
g r a v i t y c o a l c l e a n i n g procedures p r i o r t o combustion, b u t t h e latter cannot. The
I amount of p y r i t i c s u l f u r i n I l l i n o i s c o a l s and t h e percentages of it t h a t can be
removed with reasonable c o a l recovery (80%) were r e c e n t l y r e p o r t e d by H e l f i n s t i n e
/ e t a l . ( 3 , 4 ) . For 64 c o a l s , t h e y found t h a t t h e t o t a l sulfur removed as p y r i t e i n
l a b o r a t o r y washing s t u d i e s v a r i e d from about 1 0 t o 65%. The p y r i t i c s u l f u r t h a t
was removed with 80% c o a l recovery v a r i e d from about 10 t o 90% and averaged ab,out
60%.

Although s i g n i f i c a n t amounts of p y r i t i c s u l f u r can u s u a l l y be removed by

p h y s i c a l means, very f i n e l y d i v i d e d or framboidal p y r i t e i s n o t amenable t o r e d u c t i o n
by such treatment. For complete removal of p y r i t i c s u l f u r , a combination o f p h y s i c a l
and chemical e x t r a c t i o n methods i s u s u a l l y r e q u i r e d . Methods of t h i s t y p e are
c u r r e n t l y being developed, b u t t h e s e have n o t been employed on an i n d u s t r i a l s c a l e
(5).
S i m i l a r methods f o r t h e r e d u c t i o n of o r g a n i c s u l f u r , without d e s t r u c t i o n of t h e
c o a l molecule i t s e l f , have n o t been developed. Even if 100%of t h e p y r i t i c s u l f u r
were removed from all t h e I l l i n o i s c o a l s produced, only about 15%would meet c u r r e n t
environmental s t a n d a r d s without supplementary c o n t r o l s ( 3 , 4 ) .

Because t h e degree t o which s u l f u r can be reduced i n c o a l i s p r i m a r i l y a

f u n c t i o n of t h e forms of s u l f u r contained i n t h e c o a l , a n a l y t i c a l methods f o r t h e i r
a c c u r a t e determination a r e e s s e n t i a l . ,

ASTM FORMS OF SULFUR INVESTIGATION

Committee D-5 on Coal and Coke, of t h e 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), began a s t u d y of methods f o r t h e determination o f forms of s u l f u r
i n c o a l i n 1957. This s t u d y e v e n t u a l l y l e d t o t h e c u r r e n t Standard Method D-2492,
 100
Forms of S u l f u r i n Coal ( 6 ) . I n t h i s procedure, t o t a l s u l f u r and only two of i s
t h r e e forms - s u l f a t e and p y r i t i c -
a r e determined. The t h i r d form, o r g a n i c s u l f u r ,
i s c a l c u l a t e d by d i f f e r e n c e :
Organic S = T o t a l % ( s u l f a t e S + p y r i t i c S).

For t h i s method, it is not only e s s e n t i a l t o o b t a i n a c c u r a t e v a l u e s f o r s u l f a t e

and p y r i t i c s u l f u r forms, it i s a l s o necessary t o o b t a i n a c c u r a t e t o t a l s u l f u r values.
Any e r r o r s made i n t o t a l , p y r i t i c , o r s u l f a t e s u l f u r d e t e r m i n a t i o n s w i l l be cumulative
i n t h e organic s u l f u r c a l c u l a t i o n . U n f o r t u n a t e l y , t h e r e a r e no p u b l i s h e d methods f o r
t h e d i r e c t determination o f organic s u l f u r t h a t w i l l permit t h e sum of independently
determined values f o r t h e t h r e e forms of s u l f u r t o be checked a g a i n s t an independently
determined t o t a l s u l f u r v a l u e . This has l e d t o a number o f problems, which w i l l be
d i s c u s s e d i n more d e t a i l l a t e r .

A flow s h e e t f o r ASTM Standard Method E-2492, Forms of S u l f u r i n Coal, i s given

i n Figure 1. The method i s based on t h e d i f f e r e n t s o l u b i l i t i e s of s u l f a t e and p y r i t i c
s u l f u r i n H C 1 and HN03. S u l f a t e s u l f u r is s o l u b l e i n d i l u t e H C 1 , b o t h s u l f a t e and
p y r i t i c forms of s u l f u r a r e s o l u b l e i n H N O 3 , and o r g a n i c s u l f u r i s i n s o l u b l e i n t h e
a c i d s . P y r i t i c s u l f u r i s g e n e r a l l y determined by e x t r a c t i n g t h e c o a l r e s i d u e from
t h e s u l f a t e s u l f u r d e t e r m i n a t i o n ( F i g u r e 1 1 , although i t may a l s o be determined on a
s e p a r a t e coal sample i f c o r r e c t i o n s f o r t h e s u l f a t e s u l f u r o r i r o n are made. P y r i t e
i s oxidized by HN03 t o f e r r i c i r o n and s u l f a t e , b u t it i s t h e f e r r i c i r o n a s s o c i a t e d
with t h e p y r i t e t h a t i s u s u a l l y determined r a t h e r than t h e s u l f u r ( F i g u r e 1).
The HNO3 e x t r a c t i o n may o x i d i z e s m a l l amounts of organic m a t t e r t h a t c o n t a i n s sul-
f u r . This would b e e r r o n e o u s l y determined as p a r t of t h e p y r i t i c s u l f u r . Organic
s u l f u r i s c a l c u l a t e d by d i f f e r e n c e as p r e v i o u s l y described.

During t h e ASTM round-robin t e s t i n g of t h i s method, l a r g e amounts of d a t a were

g e n e r a t e d and subsequently compiled by Krumin ( 7 , 8 , 9 , 1 0 ) f o r Committee D-5. The re-
sults and conclusions of t h i s s t u d y a r e u n a v a i l a b l e i n published form, b u t a b r i e f
summary of i t s n a t u r e and t h e conclusions drawn a r e a s follows*.
1) Five c o a l samples c o n t a i n i n g from 1.6 t o 24% s u l f u r , each ground t o pass a
-60 mesh and -200 mesh-sieve, and analyzed by f i v e d i f f e r e n t l a b o r a t o r i e s gave
e s s e n t i a l l y t h e same r e s u l t s f o r forms of s u l f u r . Thus, t h e u s e of -60 mesh c o a l was
recommended.
2 ) Further s t u d i e s u s i n g methods o r i g i n a l l y developed by Powell and P a r r (11)
and Powell ( 1 2 ) were conducted by 24 l a b o r a t o r i e s , each a n a l y z i n g two c o a l s i n
t r i p l i c a t e and u s i n g t h e c o a l e x t r a c t i o n and method v a r i a t i o n s given i n Table I . I n
a l l c a s e s , organic s u l f u r w a s determined by d i f f e r e n c e s . R e s u l t s of t h i s study a r e
summarized i n Table I. Table I1 p r e s e n t s t h e r e s u l t s o f t h e t - t e s t of means, and
Table I11 p r e s e n t s r e s u l t s of t h e F - t e s t of v a r i a n c e s a s performed on t h e d a t a
determined by t h e v a r i o u s methods f o r s u l f a t e and p j r i t i c s u l f u r i n c o a l samples
d e s i g n a t e d S-1 and 5-2. Conclusions were drawn by Krumin ( 1 0 ) and p r e s e n t e d a t t h e
meeting o f ASTM Committee E-5, January 30, 1961:

T o t a l Sulfur-Eschka Method (ASTM 0-3177). Deviations i n t h e d a t a r e p o r t e d by

t h e v a r i o u s l a b o r a t o r i e s were w i t h i n , o r exceeded by only a small amount (0.01 t o
0 . 0 5 % ) , ASTM l i m i t s f o r maximum d e v i a t i o n s of r e s u l t s .

S u l f a t e S u l f u r (ASTM I?-2492). The r e s u l t s determined by. t h e two methods S u l f a t e

S u l f u r , Short E x t r a c t i o n and S u l f a t e Sulfur, Long E x t r a c t i o n a r e i n c l o s e agreement,
and a r e c h a r a c t e r i z e d by almost i d e n t i c a l values f o r t h e s t a n d a r d d e v i a t i o n , repeat-
a b i l i t y and r e p r o d u c i b i l i t y . The g r e a t advantages of t h e 30-minute e x t r a c t i o n
procedure over t h e 40-hour t e c h n i q u e make t h e method S u l f a t e S u l f u r , S h o r t E x t r a c t i o n
t h e more s u i t a b l e method f o r use i n t h e r o u t i n e a n a l y s i s o f c o a l .

* Permission t o summarize t h i s work was g r a n t e d by t h e Executive Committee of ASTM

Committee D-5 on Coal and Coke.
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101
TABLE I. STATISTICAL EVALUATION*
Meant Standard Repeat- Reproduc-
Experimental procedure Sample data deviation ability ibility
IC%\
\ I-,

Total Sulfur s-1 2.93 0.0945 0.0610 0.2514

s-2 2.94 0.0846 0.0928 0.2142
Sulfate Sulfur, s-1 0.08 0.0131 0.0196 0.0311
H C 1 Short E x t r a c t i o n 5-2 0.16 0.0124 0.0214 0.0322
(30 min.)
Sulfate Sulfur s-1 0.08 0.0115 0.0196 0.0339
H C 1 Long E x t r a c t i o n s-2 0.15 0.0124 0.0191 0.0316
(40 h r s . , 60' c)
P y r i t i c Sulfur, Short s-1 1.75 0.1799 0.1412 0.4412
HNO3 E x t r a c t i o n ( r e f l u x , S-2 1.62 0.1637 0.14555 0.4069
30 min.), Gravimetric
Determination
P y r i t i c S u l f u r , Long S-1. 1.74 0.1952 0.1614 0.5085
HN03 E x t r a c t i o n ( 2 4 hrs., S-2 1.59 0.1228 0.1460 0.3359
room temp. ) , Gravimetric
Determination
I P y r i t i c S u l f u r , Short S-I 1.74 0.1553 0.1198 0.4119
HNO3 E x t r a c t i o n ( r e f l u x , 5-2 1.58 0.0943 0.1213 0.2516
30 m i n . ) , T i t r i m e t r i c
Determination of I r o n
P y r i t i c S u l f u r , Long s-1 1.85 0.1027 0.0922 0.2815
HNO3 E x t r a c t i o n ( 2 4 h r s . , 5-2 1.59 0.0974 0.0998 0.2553
room temp.), T i t r i m e t r i c
Determination of I r o n
*After a t h e s i s by E. F a s i g , Jr., Engineering and Experiment S t a t i o n , Ohio S t a t e
U n i v e r s i t y , Columbus, OH.
tMois t u r e - f r e e .

TABLE 11. RESULTS OF THE T-TEST OF MEANS"

Method of Degrees of Calculated Critical value
determination Sample freedom v a l u e of t o r range of t
S u l f a t e S u l f i r , Long vs. S h o r t s-1 102 0.790 2.000 t o 1.980
Extractions s-2 10a 4.475 2.000 t o 1.980
P y r i t i c S u l f u r , Short E x t r a c t i o n , S-1 70 0.106 2.000 t o 1.980
Gravimetric VS. T i t r i m e t r i c S-2 70 1.505 2.000 t o 1.980
Determinations
P y r i t i c S u l f u r , Long E x t r a c t i o n , S-1 76 3.371 2.000 t o 1.980
Gravimetric VS. T i t r i m e t r i c S-2 72 0.007 2.000 t o 1.980
Determinations
P y r i t i c Sulfur, Short VS. b n g s-1 86 0.126 2.000 t o 1.980
E x t r a c t i o n s , Gravimetric s-2 83 0.953 2.000 t o 1.980
Determination
P y r i t i c S u l f u r , S h o r t TS.Long s-1 60 3.768 2.000
Extractions, T i t r i m e t r i c s-2 59 0.552 2.008 t o 2.000
Determination
*After a t h e s i s by E. F a s i g , Jr., Engineering Experiment S t a t i o n , Ohio S t a t e
U n i v e r s i t y , Columbus, OH.
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TABLE 111. RESULTS OF THE F-TEST OF VARIANCES*

Method of Degrees o f Freedom Calculated Critical
de termin a t i on Sample numerator denominator value of F range, F
S u l f a t e S u l f u r , Long VS. S-1 1 102 1.73 4.00 t o
Short E x t r a c t i o n s 3.92
s-2 1 100 26.97 4.00 t o
3.92
F y r i t i c S u l f u r , Long and S-1 3 146 6.87 2.68 to
Short E x t r a c t i o n s 2.60
Gravimetric and 5-2 3 142 2.96 2.68 t o
T i t r i m e t r i c Determina- 2.60
tions
*After a t h e s i s by E. F a s i g , Jr., Engineering Experiment S t a t i o n , Ohio S t a t e
U n i v e r s i t y , Columbus, OH.

F y r i t i c S u l f u r (ASTM -2492). Data determined by f o u r methods (Table l), were,

f o r a l l cases except one, i n c l o s e agreement w i t h each o t h e r and were c h a r a c t e r i z e d
by v a l u e s of s t a n d a r d d e v i a t i o n , r e p e a t a b i l i t y , and r e p r o d u c i b i l i t y , a l l of which
were very s i m i l a r . The p r e c i s i o n of t h e t i t r i m e t r i c technique w a s b e t t e r t h a n t h a t
of t h e g r a v i m e t r i c p r o c e d u r e as shown by t h e v a l u e s of s t a n d a r d d e v i a t i o n and
r e p r o d u c i b i l i t y shown i n Table I. Since t h e p r e c i s i o n and r e s u l t s o f t h e v a r i o u s
methods a r e s o s i m i l a r , t h e advantages of t h e s h o r t , 30-minute e x t r a c t i o n procedure
over t h e long, 40-hour t e c h n i q u e , and the g r e a t e r ease and speed of t h e t i t r i m e t r i c
determination i n comparison with t h e g r a v i m e t r i c procedure make t h e method P y r i t i c
S u l f u r , S h o r t E x t r a c t i o n , T i t r i m e t r i c Determination t h e most s u i t a b l e f o r use i n t h e
r o u t i n e a n a l y s i s of coal.

TOTAL SULFUR

The need f o r a c c u r a t e methods of determining t o t a l s u l f u r i n c o a l was pre-

v i o u s l y noted. The Eschka and bomb washing procedures are t h e two most commonly
used methods i n t h e United S t a t e s , both of which a r e given i n ASTM D-3177 ( 6 ) .

The Eschka procedure c o n s i s t s of thoroughly mixing c o a l w i t h Eschka mixture

( 2 p a r t s c a l c i n e d MgO and 1 p a r t anhydrous NaZC03) and ashing i t i n a muffle furnace
at 800° C. The ashed c o a l i s leached with h o t w a t e r , f i l t e r e d , and t h e s u l f u r i s
determined g r a v i m e t r i c a l l y i n t h e f i l t r a t e . This method i s r a p i d when c a r r i e d out
on l a r g e batches of samples; it i s most a c c u r a t e when used f o r c o a l s c o n t a i n i n g no
more t h a n 6 o r 7% s u l f u r .

The bomb washing procedure i s convenient f o r l a b o r a t o r i e s t h a t make f r e q u e n t

c o a l c a l o r i m e t r i c d e t e r m i n a t i o n s as d e s c r i b e d i n ASTM D-2015 ( 6 ) . After cooling and
c a r e f u l v e n t i n g , t h e bomb u s e d f o r a c a l o r i f i c determination i s thoroughly washed with
w a t e r , and t h e s u l f u r is t h e n g r a v i m e t r i c a l l y determined i n t h e bomb washings. This
method g i v e s e x c e l l e n t r e s u l t s when used f o r t h e a n a l y s i s of c o a l s c o n t a i n i n g no
more t h a n 4% s u l f u r .

A t h i r d method i n common u s e , b u t which was dropped as an ASTM s t a n d a r d i n 1974,

i s t h e peroxide bomb method ( 1 3 ) . I n t h i s method, c o a l i s fused with Na202 i n a
s p e c i a l bomb. Following d i s s o l u t i o n of t h e m e l t , s u l f u r i s u s u a l l y determined
g r a v i m e t r i c a l l y . This procedure i s e s p e c i a l l y u s e f u l f o r t h e determination of high
sulfur c o n c e n t r a t i o n s up t o 30 o r 40%. The d i f f i c u l t i e s and p r e c a u t i o n s r e q u i r e d
f o r t h e c o r r e c t u s e of t h e s e t h r e e methods have been d e s c r i b e d by S e l v i g and
F i e l d n e r ( 1 4 ) and Rees (15).

There a r e a t l e a s t t h r e e o t h e r l e s s f r e q u e n t l y used procedures: The high-

temperature combustion method ( 1 6 ) , which has been approved by ASTM Committee E-5
and w i l l probably be p u b l i s h e d i n 1975; t h e Leco o r i n d u c t i o n f u r n a c e method, which
w a s t e s t e d by ASTM Committee 2-5 with u n s a t i s f a c t o r y r e s u l t s (17); and X-ray f l u o r e s -
cence methods.

i
 103

\
The high-temperature combustion procedure i s most u s e f u l f o r t h e r a p i d (30 min.
p e r sample) d e t e r m i n a t i o n of t o t a l sulfur i n a s m a l l b a t c h o f l e s s t h a n 8 01 10
samples. Under t h e s e c o n d i t i o n s , it i s much more r a p i d t h a n t h e Eschka method;
however, when samples a r e analyzed i n l a r g e r groups (20 t o 30 samples), t h e Eschka
procedure is p r e f e r r e d over t h e high-temperature combustion method.

The high-temperature combustion method f o r determining t o t a l s u l f u r i n Coal i s

based on t h e procedure of Mott and Wilkinson (18) i n which a weighed c o a l Sample is
burned i n a t u b e f u r n a c e i n a s t r e a m o f oxygen at a temperature o f 1350' C. The Sul-
fur oxides and c h l o r i n e formed a r e absorbed i n H202 s o l u t i o n y i e l d i n g H C 1 and H2S04.
The t o t a l a c i d content i s determined by t i t r a t i o n with NaOH, and t h e amount of N a C l
r e s u l t i n g from t h e t i t r a t i o n of t h e H C 1 i s converted t o NaOH w i t h a s o l u t i o n of mer-
c u r i c oxycyanide (Hg(0H)CN). This NaOH is determined t i t r i m e t r i c a l l y and used t o
c o r r e c t t h e s u l f u r v a l u e , which i s e q u i v a l e n t t o t h e amount o f H2SO4 formed d u r i n g
combustion of t h e c o a l . The r e a c t i o n s t a k i n g p l a c e a r e as f o l l o w s :
SO2 + H202 -> H2SO4
C 1 2 + A202 -> 2HC1 + 02
N a C l + Hg(0H)CN > - HgClCN + NaOH
The method is a c c u r a t e f o r b o t h low and high sulfur c o n c e n t r a t i o n s .

F i n a l l y , X-ray f l u o r e s c e n c e h a s been used f o r determining t o t a l s u l f u r i n Coal

(19,20,21). Ruch e t al. (1)have r e c e n t l y d e s c r i b e d a method of p r e p a r i n g p r e s s e d
c o a l samples, which may b e used for t h e determination of a v a r i e t y of major, minor,
and t r a c e elements, i n c l u d i n g sulfur, i n whole coal. T h e i r s u l f u r v a l u e s f o r more
t h a n 100 c o a l s showed good agreement with t h o s e determined by t h e ASTM s t a n d a r d
Eschka procedure (Ruch, p. 1 5 ) . The economy and speed of such X-ray f l u o r e s c e n c e
methods, when used f o r m u l t i p l e determinations ( e , g . A l , S i , Ca, Mg, Fe, K , T i , P,
and S) i n t h e same prepared c o a l sample, are probably unsurpassed by any o t h e r
method. The r e l a t i v e s t a n d a r d d e v i a t i o n f o r s u l f u r , as determined by t h e X-ray
f l u o r e s c e n c e method o f Ruch e t a l . (1)i s 0.5%.

INSTRUMENTAL METHODS FOR DETERMINING PYRITIC SULFUR

The HNO3 e x t r a c t i o n of p y r i t e (FeS2) from c o a l y i e l d s a s o l u t i o n i d e a l f o r t h e

atomic absorption determination o f i r o n as a measure of p y r i t i c s u l f u r . Current
s t u d i e s of t h i s method by ASTM Committee E-5, t h e U. S. Bureau of Mines, P i t t s b u r g h ,
PA, and t h e TVA C e n t r a l Chemical L a b o r a t o r i e s , Chattanooga, TN, show good agreement
between p y r i t i c i r o n v a l u e s determined using a n atomic a b s o r p t i o n procedure w i t h t h o s e
determined by t h e t i t r i m e t r i c methods d e s c r i b e d f o r p y r i t i c i r o n i n ASTM D-2h92 ( 6 ) .
The method i s simple and r a p i d , and i t may soon r e p l a c e c u r r e n t l y s p e c i f i e d ASTM
s t a n d a r d s . Care m u s t be t a k e n t o avoid i n t e r f e r e n c e s from v a r i a b l e amounts o f
H2S04 formed when p y r i t e i s oxidized d u r i n g e x t r a c t i o n of t h e c o a l w i t h HNO3. Com-
pensation f o r t h i s m a t r i x change can b e made by adjustment of t h e sample s i z e and
a d d i t i o n o f H2SO4 t o s t a n d a r d s , by a d d i t i o n o f a flame b u f f e r such as Lac13 t o
samples and s t a n d a r d s , or both.

The determination of c r y s t a l l i n e p y r i t e i n c o a l by an X-ray d i f f r a c t i o n method

h a s been d e s c r i b e d by S c h e h l and F r i e d e l ( 2 2 ) . F i n e l y ground c o a l samples of known
p y r i t e c o n c e n t r a t i o n were used as s t a n d a r d s i n a technique t h a t takes advantage of
d i g i t a l computers f o r measurement of t h e d i f f r a c t i o n p a t t e r n s , as w e l l as f o r t h e
c a l c u l a t i o n of t h e percentage o f p y r i t e p r e s e n t i n t h e c o a l sample. Background cor-
r e c t i o n s due t o carbon a r e made and q u a n t i t a t i v e r e s u l t s achieved by comparing t h e
i n t e g r a t e d i n t e n s i t y of a given p y r i t e r e f l e c t i o n w i t h t h e i n t e g r a t e d i n t e n s i t y of a
p a r t i c u l a r r e f l e c t i o n from an i n t e r n a l s t a n d a r d ( n i c k e l ) . Acceptable p r e c i s i o n w i t h i n
c u r r e n t ASTM t o l e r a n c e s w a s obtained f o r t h e c o a l s s t u d i e d , but i n t e r f e r e n c e s from
r e f l e c t i o n s due t o aigh c o n c e n t r a t i o n s of k a o l i n i n c o a l were noted.

I/
1'
 104
CHEMICAL REDUCTION ICETHOD FOk DETERMINING PYRITIC SULFUR

Methods involving r e d u c t i o n o f p y r i t e t o H2S have a l s o been employed f o r t h e

determination of forms of s u l f u r (23,24,25). A r e d u c t i o n method ( 2 4 ) w a s r e c e n t l y
s t u d i e d by Kuhn e t a l . ( 2 6 ) . This method u s e s l i t h i u m aluminum hydride t o reduce
p y r i t i c s u l f u r t o H*S, which i s t h e n r e a c t e d w i t h CdSOt,. The H2SO4 formed from t h e
reaction
H2S + CdS04 -> H2SO4 + CdS ( p p t )
i s t i t r a t e d with s t a n d a r d b a s e . Both s u l f a t e and organic s u l f u r were determined by
ASTM D-2492 procedures ( 6 ) .

Major advantages of t h i s method a r e t h a t p y r i t i c s u l f u r can be d i r e c t l y determined

without danger of o x i d a t i o n o f t h e s u l f u r c o n t a i n i n g o r g a n i c c o n s t i t u e n t s , and t h a t
i t can b e determined w i t h o u t p r i o r removal of s u l f a t e s u l f u r . F u r t h e r , it i s extremely
u s e f u l as a n independent check on t h e accuracy of values f o r t h e forms of S u l f u r
determined by t h e ASTM o x i d a t i o n method.

ACCURACY OF FORMS OF SULFUR METHODS

Questions concerning t h e accuracy of e i t h e r o x i d a t i o n o r r e d u c t i o n methods f o r

t h e determination of forms of s u l f u r i n c o a l g e n e r a l l y stem from t h e d i f f i c u l t i e s
a s s o c i a t e d w i t h t h e incomplete e x t r a c t i o n of f i n e l y - d i s p e r s e d p y r i t e ( 2 5 , 2 7 , 2 8 , 2 9 ) .
R e s u l t s of t h e s e s t u d i e s have been a t v a r i a n c e . I n some c a s e s , f i n e g r i n d i n g o f coal
(-200 mesh) tended t o i n c r e a s e t h e amount of p y r i t e e x t r a c t e d by HN03, e s p e c i a l l y i n
h i g h rank B r i t i s h c o a l s (>85%carbon c o n t e n t ) . However, f o r U. S. c o a l s , g r i n d i n g
t o t h e u s u a l -60 mesh p a r t i c l e s i z e has been s u c c e s s f u l (7,8,9,10). Burns ( 3 0 ) a l s o
found f i n e g r i n d i n g t o b e unnecessary f o r A u s t r a l i a n c o a l s when p y r i t i c s u l f u r w a s
e x t r a c t e d from t h e c o a l r e s i d u e fo3 lowing t h e s u l f z t e s u l f u r e x t r a c t i o n rdtiler tinan
f r o m a f r e s h c o a l sample.

These and o t h e r q u e s t i o n s r e g a r d i n g t h e r e l i a b i l i t y o f d e t e r m i n a t i o n s of forms

o f s u l f u r were t h e s u b j e c t of a r e c e n t i n v e s t i g a t i o n ( 2 6 ) . For t h i s s t u d y , r e s u l t s
f r o m t h e ASTM o x i d a t i v e method were compared w i t h t h o s e of a r e d u c t i v e method ( 2 4 )
t o determine whether o r n o t e x t r a c t i o n of p y r i t e is complete, whether or not organic
matter i s s i g n i f i c a n t l y a f f e c t e d by HN03 e x t r a c t i o n , and whether or n o t organic S u l f u r
can b e o b t a i n e d e i t h e r by computation o r by Eschka determination of r e s i d u a l s u l f u r
f o l l o w i n g HNO3 e x t r a c t i o n of p y r i t i c s u l f u r . The i n f l u e n c e of c o a l p a r t i c l e s i z e s
(-60, -200, and -400 mesh) on t h e v a l u e s determined by both methods was a l s o s t u d i e d .

R e s u l t s f o r two c o a l s , which a r e r e p r e s e n t a t i v e o f t h e n i n e c o a l s s t u d i e d i n
t h i s i n v e s t i g a t i o n , a r e given i n Table I V . The p r i n c i p a l conclusions a r e summarized
as follows :
1) Coal p a r t i c l e s i z e had no s i g n i f i c a n t e f f e c t on t o t a l s u l f u r determined by
t h e Eschka method ( T a b l e I V , column f o u r ) .
2 ) X-ray f l u o r e s c e n c e v a l u e s f o r t o t a l s u l f u r agree w e l l w i t h Eschka v a l u e s
( T a b l e I V , columns f o u r and f i v e ) .
3 ) P y r i t i c s u l f u r v a l u e s determined by t h e ASTM method a r e not s i g n i f i c a n t l y
i n f l u e n c e d by c o a l p a r t i c l e s i z e ( T a b l e I V , column s e v e n ) .
41 For t h e r e d u c t i o n method, p y r i t i c s u l f u r v a l u e s i n agreement w i t h t h o s e from
t h e ASTM procedure were o b t a i n e d only when t h e c o a l was ground t o -400 mesh
( T a b l e I V , columns seven and e i g h t ) .
5) Agreement o f t o t a l i r o n i n t h e c o a l s , as determined by X-ray f l u o r e s c e n c e ,
with t h e sum of t h e i r o n determined i n t h e ASTM H C 1 and HNO3 e x t r a c t s was
e x c e l l e n t ( T a b l e I V , columns two and t h r e e ) . This i n d i c a t e s t h a t a l l of
t h e p y r i t i c i r o n ( s u l f u r ) w a s e x t r a c t e d by t h e HNO3.
6 ) I t was concluded t h a t no p y r i t i c i r o n remained i n t h e r e s i d u e s of t h e nine
c o a l s s t u d i e d a f t e r t h e y were s u b j e c t e d t o e i t h e r t h e ASTM o x i d a t i o n method
o r t h e r e d u c t i o n method ( o n -400 mesh c o a l s o n l y ) . T h e r e f o r e , organic s u l f u r
v a l u e s c a l c u l a t e d by s u b t r a c t i n g t h e sum o f s u l f a t e s u l f u r p l u s p y r i t i c
S u l f u r from t o t a l s u l f u r were deemed a c c u r a t e ( T a b l e I V , columns nine and t e n ) .
 105

\
TABLE Iv. CONCENTRATION OF I R O N AND VARIETIES OF SULFUR I N TWO ILLINOIS COAIS
Total iron Total Sulfur Sulfur
(I) (I) (%I
Sample X-ray X-ray Calculated Determined
and f luores- fluores- SOI, Pyr i t i c oruani c organic
size ASTM ence ASTM ence ASTM ASTM Reduc. ASTM LAH ASTM Reduc.
c-18067
-60 4.28 3.80 7.48 7.25 0.02 4.82 4.08 2.64 3.38 2.50 2.24
-200 4.26 4.28 7.53 7.45 0.02 4.76 4.44 2.75 3.07 2.48 2.21
-400 4.30 4.52 7.52 7.63 0.02 4.79 4.60 2.71 2.90 2.54 2.51
C-17167
-60 1.24 1.23 2.91 3.05 0.40 0.94 0.77 1.57 1.74 1-37 1-45
-200 1.29 1.31 2.95 3.09 0.39 0.92 0.88 1.75 1.68 1.26 1-25
-400 1.30 1.31 2.93 3.07 0.39 0.93 0.93 1.61 1.61 1-19 1-31

ORGANIC SULFUR

Research on t h e n a t u r e and removal of organic s u l f u r compounds from c o a l has

been e x t e n s i v e (31,32,33,34,35,36). Unfortunately, none of t h e s e i n v e s t i g a t i o n s has
l e d t o u s e f u l methods f o r determining v a r i e t i e s of organic s u l f u r i n coal. Indeed,
as previously mentioned, no methods have as y e t been developed f o r t h e d i r e c t d e t e r -
mination of t o t a l organic sulfur i n t h e presence o f i n o r g a n i c s u l f a t e s and s u l f i d e s .
When organic s u l f u r has been "determined" r a t h e r t h a n c a l c u l a t e d by d i f f e r e n c e , t h e
c o a l w a s f i r s t demineralized u s i n g methods s i m i l a r t o t h o s e d e s c r i b e d i n t h e I n t e r -
1 n a t i o n a l Standards Organization Recommended Method R-602 (371, o r by Kuhn e t a l . (26)
and Smith and B a t t s (38). In t h e s e , s u l f a t e and p y r i t i c s u l f u r a r e f i r s t removed by
a c i d d i s s o l u t i o n , o x i d a t i o n and/or r e d u c t i o n r e a c t i o n s . The t o t a l sulfur determined
i n t h e c o a l r e s i d u e i s t h e n considered t o b e organic s u l f u r . This method was found
t o be f a i r l y r e l i a b l e by Kuhn e t a l . (26), although s m a l l l o s s e s of o r g a n i c s u l f u r
were unavoidable (Table I V , columns nine through t w e l v e ) . The most a c c u r a t e r e s u l t s
f o r organic s u l f u r seemed t o be t h o s e which were c a l c u l a t e d .

An i n t e r e s t i n g new approach t o t h e purported d e t e r m i n a t i o n o f o r g a n i c s u l f u r i n

c o a l is t h a t of Hurley and White (39). They employed a X-ray f l u o r e s c e n c e method t o
f i r s t determine t o t a l s u l f u r from t h e KB l i n e i n t e n s i t y and t h e n a l i n e r a t i o tech-
I
nique t o f i n d t h e p r o p o r t i o n of s u l f a t e s u l f u r ( K B ' l i n e i n t e n s i t y ) i n t h e t o t a l s u l f u r :
%SSo, = % T o t a l S x (SKB'/SKB) x M I
where M I is t h e s l o p e of a s t a n d a r d s t r a i g h t l i n e c a l i b r a t i o n curve o f t h e r a t i o
(SKB'/SKB) vs. c o n c e n t r a t i o n . The peak s h i f t of s u l f u r KB w a s used t o determine
amounts of s u l f i d e and o r g a n i c s u l f u r : ASKB-B)
ISorg = % T o t a l S x (-
M2

I where t h e c a l i b r a t i o n c o n s t a n t s , M2 and B a r e o b t a i n e d from a s t r a i g h t l i n e c a l i b r a -

t i o n curve of t h e form Y = MX + B. I t should b e noted t h a t p y r i t i c s u l f u r i s a
c a l c u l a t e d d i f f e r e n c e f i g u r e , i e . , t h e sum o f t h e t h r e e forms of s u l f u r must e q u a l
100%. Therefore, t h e s u l f u r values a r e not independently determined.

NONPYRITIC SULFIDES

S t u d i e s have shown t h a t some c o a l s c o n t a i n s i g n i f i c a n t q u a n t i t i e s of n o n p y r i t i c

s u l f i d e (1,2), and t h a t it u s u a l l y occurs i n conjunction w i t h high z i n c c o n c e n t r a t i o n s
( u p t o 5000 ppm). I n t h e r e d u c t i o n method t h e p y r i t e (FeS2) i s f i r s t reduced t o sul-
f i d e (FeS). Any n o n p y r i t i c s u l f i d e p r e s e n t i n t h e c o a l w i l l c o n t r i b u t e t o t h e
p y r i t i c s u l f u r v a l u e when t h e chemical r e d u c t i o n o f p y r i t e i s c a r r i e d o u t p r i o r t o

J
J
f

4
 106
s u l f a t e removal*. This i s t r u e o n l y when t h e r e d u c t i o n s t e p is done f i r s t , as Some A
n o n p y r i t i c s u l f i d e is l o s t i n t h e H C 1 d i g e s t i o n f o r s u l f a t e s u l f u r (ASTM). The
ASTM method f o r p y r i t i c s u l f u r measures only t h e p y r i t i c i r o n . Consequently, a
p y r i t i c s u l f u r v a l u e determined by t h e r e d u c t i o n method t h a t i s h i g h e r t h a n one 1
determined by t h e ASTM method would be a measure of t h e amount o f n o n p y r i t i c s u l f i d e I
p r e s e n t i n t h e c o a l . I n such a c a s e , Zn c o n c e n t r a t i o n is a l s o a u s e f u l measure of
nonpyri t i c s u l f i de. i

The l o s s of n o n p y r i t i c s u l f i d e s as hydrogen s u l f i d e i n t h e h y d r o c h l o r i c a c i d
d i g e s t i o n of s u l f a t e sulfur (ASTM) would r e s u l t i n t h i s s u l f i d e ' s b e i n g determined
as n e i t h e r s u l f a t e nor p y r i t i c sulfur. The o r g a n i c s u l f u r v a l u e , c a l c u l a t e d as t h e I
d i f f e r e n c e between t h e t o t a l s u l f u r and t h e s u l f a t e + p y r i t i c s u l f u r v a l u e s , would
t h e n b e erroneously high.

ANALYSIS O F COAGRELATED MATERIALS

Coal p r e p a r a t i o n and f l o a t - s i n k s t u d i e s f r e q u e n t l y r e q u i r e t h e determination of

forms o f s u l f u r i n c o a l g r a v i t y f r a c t i o n s . Because t h e s e commonly c o n t a i n 10 t o 20%
sulfur, c a r e must b e t a k e n when applying methods developed f o r t h e a n a l y s i s of whole
c o a l t o them. H e l f i n s t i n e e t a l . ( 3 , 4 ) determined forms o f s u l f u r i n 64 I l l i n o i s
.I
c o a l s , i n t h e i r f l o a t f r a c t i o n s ( f i v e f o r each c o a l ) , and i n t h e m a t e r i a l t h a t sank 1
a t a s p e c i f i c g r a v i t y of 1.60. These d a t a were t h e n used t o c a l c u l a t e s u l f u r i n the
"raw coal" by p r o p o r t i o n a l l y combining t h e i n d i v i d u a l f l o a t - s i n k f r a c t i o n s t o give
I
v a l u e s t h a t should be e q u i v a l e n t t o values given i n t h e o r i g i n a l r a w c o a l a n a l y s i s .
I
The average d i f f e r e n c e i n p e r c e n t between analyzed r a w c o a l s u l f u r v a l u e s and those
c a l c u l a t e d from t h e i n d i v i d u a l a n a l y s e s of f l o a t - s i n k f r a c t i o n s are -0.15, -0.05, and
-0.11 f o r t o t a l sulfur, p y r i t i c s u l f u r , and o r g a n i c sulfur r e s p e c t i v e l y . Although
t h e means ( a s w e l l as t h e i r s t a n d a r d d e v i a t i o n s ) a r e small and i n d i c a t e good agree-
ment, examination o f a l l of t h e d a t a shows n o t a b l e exceptions f o r some high s u l f u r
samples. I n one c o a l , p e r c e n t d i f f e r e n c e s between analyzed and c a l c u l a t e d values
f o r t o t a l s u l f u r , p y r i t i c s u l f u r , and organic s u l f u r w e r e -0.56, -0.49, and -0.10,
r e s p e c t i v e l y . C a r e f u l resampling and a n a l y s i s has shown t h a t d i f f e r e n c e s of t h i s ,
magnitude a r e n o t due t o poor sampling o r a n a l y t i c a l t e c h n i q u e s , b u t r a t h e r t o small
e r r o r s i n the a n a l y s i s o f high s u l f u r m a t e r i a l s u s i n g t h e ASTM method of determining
forms o f s u l f u r . Such e r r o r s may b e magnified by f a c t o r s of 1 0 or 20 i n making t h e
calculations.

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1
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 107
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I
t

J
 I

108

-60 Mesh Coal

H C 1 Reflux
30 min.
Filter

iesidue

HN03 Reflux
30 min.
Filter

30% H202
NHbOH
Sulfate Iron Ppt. Filtrate
I
BaC12
Filter
-
Pyrl ic Iron Ppt.

HC1
BaS04Ppt.

-
Pyrl ic Iron Solution

Fe Titration
Weigh
(permanganate,
dichromat e)
Sulfate Sulfur

-
Pyr : ic Sulfur
1

Figure 1. Flow diagram for ASTM determination of forms

of sulfur in coal.