Professional Documents
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INTRODUCTION
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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 .
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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 .
TOTAL SULFUR
i
103
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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.
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CHEMICAL REDUCTION ICETHOD FOk DETERMINING PYRITIC SULFUR
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
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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
NONPYRITIC SULFIDES
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.
REFERENCES
I
t
J
I
108
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