10 High-Temperature Interactions among Minerals Occurring in Coal Donald L . Biggs and Curtis G . Lindsay
1
Ames Laboratory, Iowa State Mining and Mineral Resources Research Institute, and
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Department of Earth Sciences, Iowa State University, Ames,IA50011
Minerals known to be present in the low temperature ash extracted from coals were heated in a microscope heating stage from 25° to about 1400°C. Mineral types were arranged in homogeneous fields where two fields shared a linear boundary or three fields were in contact at a point. Because of the known reactivity of calcite and pyrite, all specimens contained this pair. Clay minerals, kaolinite, illite and montmorillonite were used as the third component. Reaction temperature between calcite and pyrite is lowered by the presence of clays. Iron was observed to migrate into the clay domain after the formation of pyrrhotite from pyrite and oldhamite was observed forming between the domain of lime formed from calcite and the pyrrhotite.
M i n e r a l i m p u r i t i e s i n c o a l a r e known t o be p r i m a r y c o n t r i b u t o r s t o the s l a g g i n g and f o u l i n g o f u t i l i t y b o i l e r s , f l y a s h and bottom a s h p r o d u c t i o n as w e l l as a t m o s p h e r i c p o l l u t i o n . They a l s o produce u n d e s i r a b l e e f f e c t s i n some p a r t s o f hydrogénation p r o c e s s e s such as l i q u i f a c t i o n and g a s i f i c a t i o n ( 1 , 2 , 3 ) . D e s p i t e a l o n g h i s t o r y o f i n v e s t i g a t i o n prompted by t h e s e o b s e r v a t i o n s , many q u e s t i o n s remain unanswered. Simple e m p i r i c a l r e l a t i o n s h i p s between f u s i o n temperature o f the f u r n a c e d e p o s i t s and t h e m i n e r a l o g y o f c o a l s have been p r o p o s e d (4,5,6). More r e c e n t l y attempts have c o n c e n t r a t e d on a p h y s i c o c h e m i c a l view o f t h e problem comparing a s h f u s i o n temperatures w i t h phase r e l a t i o n s i n three-component c h e m i c a l systems ( 7 , 8 ) . This method o f a t t a c k has y i e l d e d some s i g n i f i c a n t r e s u l t s , b u t a t l e a s t some r e s e a r c h e r s (8) have q u e s t i o n e d t h i s approach, which i s based 1
Current address: Department of Geologic Sciences, Virginia Polytechnic Institute, Blacksburg, VA 24061. 0097-6156/ 86/ 0301 -0128S06.00/ 0 © 1986 American Chemical Society
Vorres; Mineral Matter and Ash in Coal ACS Symposium Series; American Chemical Society: Washington, DC, 1986.
10.
BIGGS A N D LINDSAY
High-Temperature
Interactions
among
129
Minerals
on t h e assumption t h a t these p r o c e s s e s o c c u r under c o n d i t i o n s o f equilibrium. The aim o f t h e r e s e a r c h d e s c r i b e d here i s t o o b s e r v e i n t e r a c t i o n s between m i n e r a l s known t o o c c u r i n c o a l s i n t h e most d i r e c t f a s h i o n p o s s i b l e and i n t h e s i m p l e s t c o n d i t i o n s c o n s i s t e n t w i t h causing the r e a c t i o n s to occur. I t i s considered that observation o f s i m p l e m i x t u r e s o f m i n e r a l s o b s e r v e d t o e n t e r i n t o r e a c t i o n may make p o s s i b l e a b e t t e r a c c o u n t i n g o f t h e p r o c e s s e s by which s l a g and f o u l i n g d e p o s i t s form i n f u r n a c e s .
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Experimental
Methods
I s o l a t i o n and I d e n t i f i c a t i o n o f C o a l M i n e r a l s . Two c o a l samples, c o l l e c t e d from d i f f e r e n t c o a l b a s i n s i n t h e U n i t e d S t a t e s (see T a b l e I ) , were s u b j e c t e d t o low-temperature a s h i n g as d e s c r i b e d by Gluskoter (9). T h i s process avoids d e s t r u c t i o n of the m i n e r a l s while o x i d i z i n g the o r g a n i c p o r t i o n o f the c o a l . T h i s ashing procedure o c c u r s a t a much lower temperature than t h a t o f 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) method i t i s g i v e n t h e name o f "lowtemperature a s h i n g and g e n e r a l l y a b b r e v i a t e d LTA. I n f o r m a t i o n o f a m i n e r a l c o n c e n t r a t e by LTA, a few changes a r e a n t i c i p a t e d ; some c l a y s a r e r e v e r s i b l y d e h y d r a t e d , and h y d r a t e d s u r f a c e s a r e reduced t o t h e hemihydrate form ( f o r i n s t a n c e gypsum i s c o n v e r t e d t o b a s s a n i t e ) . Because these changes a r e known i n advance, due a l l o w a n c e c a n be made f o r them. 11
Table I.
Seam: Locality:
C o a l Samples, L o c a l i t i e s o f O r i g i n , and A n a l y s e s ( a l l samples run-of-mine)
I l l i n o i s #6 S t . C l a i r County, I l l i n o i s
Analysis:
9 mesh χ 0 Raw
M o i s t u r e (%): Ash, ASTM (%): P y r i t i c S u l f u r (%): T o t a l S u l f u r (%): H e a t i n g Value ( B T U / l b . ) : Seam: Locality:
5.31 32.86 2.46 4.57 9,039
9 χ 32 mesh Float 5.44 7.10 0.76 4.57 13,248
9 χ 32 mesh Sink 2.55 68.05 5.08 5.94 3,574
Upper F r e e p o r t Grant County, West V i r g i n i a
Analysis :
M o i s t u r e (%): Ash, ASTM (%): P y r i t i c S u l f u r (%): T o t a l S u l f u r (%): H e a t i n g Value ( B T U / l b . ) :
9 mesh χ 0 Raw 0.30 35.90 1.58 2.18 9,695
9 χ 32 mesh Float 0.68 7.26 0.27 1.06 13,365
9 χ 32 mesh Sink 0.93 72.10 2.62 3.00 3,086
Vorres; Mineral Matter and Ash in Coal ACS Symposium Series; American Chemical Society: Washington, DC, 1986.
130
M I N E R A L M A T T E R A N D A S H IN C O A L
M i n e r a l c o n s t i t u e n t s o f t h e LTA c o n c e n t r a t e s were i d e n t i f i e d by x-ray d i f f r a c t i o n techniques. I l l i t e , k a o l i n i t e , q u a r t z and p y r i t e a r e u b i q u i t o u s i n t h e m i n e r a l s u i t e s ; c a l c i t e o c c u r s i n most c o n c e n trates. Many o t h e r m i n e r a l s have been i d e n t i f i e d i n c o a l s b u t were not o b s e r v e d i n t h e s e specimens. Heating-Stage M i c r o s c o p i c Observations. F o l l o w i n g the c h a r a c t e r i z a t i o n o f the m i n e r a l s u i t e s by x - r a y d i f f r a c t i o n t e c h n i q u e s , each LTA c o n c e n t r a t e was heated i n a h e a t i n g s t a g e mounted on a m i c r o s c o p e f i t t e d f o r observation i n v e r t i c a l l y incident l i g h t . Concentrates examined i n t h i s way and t h e p r o d u c t phases a r e found i n T a b l e I I .
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Table I I .
LTA Samples and H e a t i n g
LTA Sample Upper F r e e p o r t raw
max (°C) 560 1410
Products
Phases I d e n t i f i e d quartz, i l l i t e , pyrrhotite quartz, m u l l i t e a
Upper F r e e p o r t
1.40 f l o a t
1031 1250
quartz^ quartz^
Upper F r e e p o r t
1.40 s i n k
635 1150
quartz, i l l i t e , pyrrhotite quartz, pyrrhotite, i l l i t e
Illinois
#6 raw
880
Illinois
#6 1.40 f l o a t
625 1370
Illinois
#6 1.40 s i n k
920 1334
d
quartz, i l l i t e , oldhamite(?)
0
pyrrhotite,
quartz, i l l i t e , pyrrhotite, troilite(?) quartz, pyrrhotite quartz, i l l i t e , pyrrhotite, oldhamite quartz, p y r r h o t i t e , oldhamite
XRD peaks o c c u r r e d a t t h e c o r r e c t d i f f r a c t i o n a n g l e s f o r m u l l i t e but were too weak t o p e r m i t a c c u r a t e i n t e n s i t y comparisons. The o v e r a l l p a t t e r n was s i m i l a r t o t h e one f o r t h e i l l i t e k a o l i n i t e p a i r h e a t e d t o 1410°C, except t h a t s t r o n g e r peaks f o r q u a r t z were found i n the LTA XRD p a t t e r n . Peaks were d e t e c t e d a t some o f t h e d i f f r a c t i o n a n g l e s f o r i l l i t e , but t h e i n t e n s i t i e s were n o t comparable w i t h s t a n d a r d p a t t e r n s ; i t i s p o s s i b l e t h a t t h e s e were r e l i c t peaks o f i l l i t e as i t began t o alter. Another sample o f I l l i n o i s #6 raw LTA was heated t o 1421°C; i t formed a h a r d , d a r k - c o l o r e d g l a s s a t about 1400°C; t h i s m a t e r i a l c o u l d n o t be removed from the h e a t i n g - s t a g e c r u c i b l e .
Vorres; Mineral Matter and Ash in Coal ACS Symposium Series; American Chemical Society: Washington, DC, 1986.
10.
BIGGS A N D LINDSAY
High-Temperature
Interactions
among
Minerals
131
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The h e a t i n g s t a g e i s l i m i t e d to i n e r t atmosphere o r vacuum operation. T h e r e f o r e , r e a c t i o n s s e n s i t i v e to a t m o s p h e r i c c o n d i t i o n s , such as p a r t i a l p r e s s u r e o f oxygen, cannot be s t u d i e d . Furthermore, the e x t r e m e l y s m a l l p a r t i c l e s i z e of the sample r e s u l t e d i n i n a b i l i t y to observe changes o c c u r r i n g below the mount s u r f a c e and t o r e s o l v e the s p e c i f i c m i n e r a l s e n t e r i n g i n t o a r e a c t i o n a t any p o i n t i n the run. These d i f f i c u l t i e s were a d d r e s s e d by o b t a i n i n g samples o f the m i n e r a l s i d e n t i f i e d i n the LTA c o n c e n t r a t e b e f o r e h e a t i n g , g r i n d i n g them t o a p p r o x i m a t e l y the same s i z e c o n s i s t as the c o n c e n t r a t e , and mounting them i n s e p a r a t e domains i n the h e a t i n g s t a g e c r u c i b l e . The geometry of these mounts i s shown i n F i g . 1.
Experiments
w i t h Known M i n e r a l s
Experiments w i t h I n d i v i d u a l M i n e r a l s . S i n g l e m i n e r a l mounts i n the h e a t i n g - s t a g e c r u c i b l e y i e l d e d the expected p r o d u c t s , t h a t i s , p y r i t e y i e l d e d p y r r h o t i t e and t r o i l i t e , c a l c i t e gave l i m e and c a r b o n d i o x i d e , and c l a y s r e a c t e d under h i g h temperature c o n d i t i o n s t o y i e l d a s i l i c a t e glass. Experiments w i t h P a i r s and T r i p l e t s o f Known M i n e r a l s . In these e x p e r i m e n t s , known m i n e r a l s were ground and p l a c e d i n the h e a t i n g s t a g e c r u c i b l e i n s e p a r a t e domains as p a i r s or t r i p l e t s o f m i n e r a l s . The p a i r s and t r i p l e t s were heated and the b e h a v i o r a t t h e i r bounda r i e s observed. T a b l e I I I l i s t s the m i n e r a l s used i n p a i r mounts and the r e a c t i o n p r o d u c t s o b t a i n e d by h e a t i n g . Because the most r e a c t i v e phases found i n the experiments w i t h p a i r s o f m i n e r a l s were c l a y s , c a l c i t e , and p y r i t e , t h e s e were p r e p a r e d i n t r i p l e t mounts. In t r i a l s u s i n g e i t h e r m o n t m o r i l l o n i t e or i l l i t e w i t h c a l c i t e and p y r i t e , a l i q u i d formed a t the mutual boundary o f the l a t t e r p a i r a t 600-650°C. P y r i t e and c a l c i t e had, of c o u r s e , p r e v i o u s l y r e a c t e d and t h i s l i q u i d t h e r e f o r e o c c u r r e d between the p r o d u c t phases p y r r h o t i t e and l i m e . Subsequent x - r a y a n a l y s i s showed the p r e s e n c e o f p y r r h o t i t e , l i m e , and o l d h a m i t e . In b o t h i n s t a n c e s , the temperature o f t h i s r e a c t i o n was lower than t h a t o b t a i n e d i n the p a i r mount o f c a l c i t e and p y r i t e , 1140°C. When k a o l i n i t e was i n the mount w i t h c a l c i t e and p y r i t e , the same r e a c t i o n o c c u r r e d a t 750-760°C. Though the mechanism by w h i c h the c l a y s reduce the r e a c t i o n temperature i s not y e t u n d e r s t o o d , the d i f f e r e n c e s i n r e a c t i o n temperature w i t h and w i t h o u t c l a y i s considered s i g n i f i c a n t . The most o b v i o u s change i n the c l a y s themselves d u r i n g t h e s e experiments was a d a r k e n i n g b e g i n n i n g w i t h p y r i t e d e c o m p o s i t i o n . T h i s was more marked i n the case o f i l l i t e and m o n t m o r i l l o n i t e . I t i s c o n s i d e r e d t h a t i n a l l t h e s e c a s e s , the c l a y m i n e r a l s t r u c t u r e was d e s t r o y e d and p o s s i b l y formed a s i l i c a t e g l a s s , much l i k e those found i n f u r n a c e s l a g s but h a v i n g , perhaps, l e s s oxygen.
Vorres; Mineral Matter and Ash in Coal ACS Symposium Series; American Chemical Society: Washington, DC, 1986.
M I N E R A L M A T T E R A N D A S H IN C O A L
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132
Figure
1.
Geometric arrangement o f m i n e r a l p a i r s and t r i p l e t s used i n the h e a t i n g s t a g e e x p e r i m e n t s and s u p p o r t i n g e x p e r i ments. I n a l l t r i p l e t mounts, p o s i t i o n 3 was o c c u p i e d by a clay mineral.
Vorres; Mineral Matter and Ash in Coal ACS Symposium Series; American Chemical Society: Washington, DC, 1986.
10.
BIGGS A N D LINDSAY
Table I I I .
High-Temperature
among
133
Minerals
M i n e r a l P a i r s and H e a t i n g P r o d u c t s
Mineral Pair Calcite-illite Calcite-kaolinite Calcite-montmorillonite Calcite-pyrite
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Interactions
Calcite-quartz Illite-kaolinite Illite-montmorillonite Illite-montmorillonite Illite-pyrite Illite-quartz Kaolinite-montmorillonite Kaolinite-pyrite Kaolinite-quartz Montmorillonite-pyrite Montmorillonite-quartz Pyrite-quartz
max (°C) 1310 1322 1285 1253 1467 1410 662 1212 1519 1450 1403 1445 1220 1053 1492 1571
Products I d e n t i f i e d l i m e (CaO) l i m e (CaO) (indeterminate)* lime, pyrrhotite ( F _ S ) , o l d h a m i t e (CaS) q u a r t z ( S i 0 ) , l i m e (CaO) mullite ( A l ^ i o O ^ ) ( i n d e te rminate;b (indeterminate) p y r r h o t i t e , t r o i l i t e (FeS) quartz mullite (poorly-crystalline) mullite quartz ^ (indeterminate) quartz quartz e i
x
2
Only those p r o d u c t s a r e l i s t e d which c o u l d be p o s i t i v e l y i d e n t i f i e d by XRD; no attempt i s made here t o deduce the c o m p o s i t i o n o f amorphous p r o d u c t s . XRD p a t t e r n s f o r t h e s e h e a t i n g p r o d u c t s d i d not match any s t a n d a r d p a t t e r n c l o s e l y ; attempts t o match w i t h computer r o u t i n e s produced r e s u l t s o f low r e l i a b i l i t y . " P o o r l y c r y s t a l l i n e " means t h a t d i f f r a c t i o n maxima were found c o r r e s p o n d i n g t o the i n d i c a t e d phase, but peaks were not sharp d i d not have the c o r r e c t r e l a t i v e i n t e n s i t i e s i n a l l c a s e s .
and
Supporting Experiments. To examine the e f f e c t o f o x i d i z i n g and r e d u c i n g atmosphere on t h e s e m a t e r i a l s , g r a p h i t e c r u c i b l e s 10mm i n d i a m e t e r and 2mm deep were packed i n the manner d e s c r i b e d above and h e a t e d i n a f u r n a c e f i t t e d t o p e r m i t i n t r o d u c t i o n o f s p e c i f i e d gases d u r i n g h e a t i n g . A f t e r h e a t i n g , the samples were examined by 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 y and energy d i s p e r s i v e x - r a y s p e c t r o s copy (SEM/EDS) ( F i g u r e 2 ) . Samples t r e a t e d i n t h i s way are l i s t e d i n T a b l e IV. In a l l t h e s e c a s e s where p y r i t e was used w i t h a c l a y , i r o n was found t o have m i g r a t e d from the i r o n s u l f i d e i n t o r e g i o n t h a t was originally clay. E l e m e n t a l mapping showed the p r e s e n c e o f i r o n t o have c o m p l e t e l y pervaded the r e g i o n f o r m e r l y o c c u p i e d by c l a y . In a l l mounts c o n t a i n i n g c a l c i t e and p y r i t e , the c a l c i u m and s u l f u r peaks were p r e s e n t i n the r e g i o n o r i g i n a l l y o c c u p i e d by c a l c i t e and sometimes found i n the r e g i o n t h a t had been p y r i t e - f i l l e d .
Vorres; Mineral Matter and Ash in Coal ACS Symposium Series; American Chemical Society: Washington, DC, 1986.
134
MINERAL
MATTER
A N D A S H IN C O A L
α 500 Pyritef
All
] pKaolinite
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3 Ο Ο
0.000
5.000 10.000 15.000 ENERGY (KEV)
20.000
Al 500
Pyrite
Kaolinite
ζ ο ο
0.000
I500h
1000
5.000
C
10.000 15.000 ENERGY (KEV)
20.000
Pyrite ^J>)
Kaolinite
Fe
-
CD h-
I
500
Ο
Al | i
S i
"0.000
F i g u r e 2.
5.000
Γ,
1
1
•
ι
10.000 15.000 ENERGY (KEV)
ι 20.000
E n e r g y - d i s p e r s i v e s p e c t r a from a p y r i t e - k a o l i n i t e mount h e a t e d to 1200°C. L o c a t i o n s o f the s p e c t r a w i t h r e s p e c t to the sample are i n d i c a t e d by the s m a l l squares i n the circles.
Vorres; Mineral Matter and Ash in Coal ACS Symposium Series; American Chemical Society: Washington, DC, 1986.
BIGGS A N D LINDSAY
High-Temperature
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1500 V
Interactions
among
Minerals
|Fe Pyrite
Koolinite
£ 1000 ζ Z> Ο
ο 500 Ι
0.000
1000 h
5.000
10.000 15.000 ENERGY (KEV)
20.000
e
Fe Pyrite
3 Ο
Kaolinite
500
Fe
0.000
5.000
10.000
15.000
20.000
ENERGY ( K E V ) Figure
2.
Continued.
Vorres; Mineral Matter and Ash in Coal ACS Symposium Series; American Chemical Society: Washington, DC, 1986.
136
M I N E R A L M A T T E R A N D A S H IN C O A L
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T a b l e IV.
Subjects of Supporting
Assemblage Calcite-kaolinite Calcite-quartz Pyrite-quartz Pyrite-quartz Pyrite-calcite Pyrite-kaolinite Pyrite-kaolinite Pyrite-montmorillonite Pyrite-montmorillonite Py.-calc.-kao. Py.-cale.-mont. Py.-cale.-mont. Note:
Atmosphere inert inert oxidizing reducing reducing oxidizing reducing inert reducing reducing inert reducing
Experiments Τ
(°C) 1400 1400 1200 1200 1200 1200 1200 800 800 1200 800 800
Duration 60 60 30 30 30 30 30 15 15 30 15 15
(min)
The i n d i c a t e d temperature was the s t e a d y - s t a t e temperature f o r the t r i a l . The i n d i c a t e d d u r a t i o n was the p e r i o d o f time f o r which t h a t s t e a d y - s t a t e temperature was m a i n t a i n e d .
D i s c u s s i o n and C o n c l u s i o n s I t i s apparent t h a t the phenomena d e s c r i b e d here a r e not complete p r o c e s s e s t e r m i n a t i n g i n e q u i l i b r i u m assemblages. The times o f r e a c t i o n are too s h o r t f o r many o f the p r o d u c t s o f s i l i c a t e s such as c l a y s and q u a r t z t o come to thermodynamic e q u i l i b r i u m a t the new temperature. That t h i s i s i n d e e d the case i n o p e r a t i o n of powerp l a n t b o i l e r s i s o b v i o u s from the c o n s i d e r a t i o n o f the amount o f g l a s s found i n f u r n a c e s l a g s and f l y - a s h . I l l i t e and m o n t m o r i l l o n i t e a r e s i m i l a r i n s t r u c t u r e and d i f f e r s l i g h t l y from k a o l i n i t e i n t h i s r e g a r d . The f i r s t two a r e composed of two s i l i c o n - o x y g e n l a y e r s p e r o c t a h e d r a l l a y e r c o n t a i n i n g i r o n , magnesium and aluminum and i n k a o l i n i t e the r a t i o o f t e t r a h e d r a l and o c t a h e d r a l l a y e r s i s 1. In c l a y s t h e r m a l m o d i f i c a t i o n o c c u r s a t lower temperature t h a n s i l i c a because the bonds formed between the A l , Fe, and Mg atoms and oxygen a r e weaker than the S i - 0 bonds. C l a y s , t h e r e f o r e , a r e e x p e c t e d to be more r e a c t i v e than the s i l i c a crystals. There i s e v i d e n c e of d r a s t i c s t r u c t u r a l m o d i f i c a t i o n s , i f not v i t r i f i c a t i o n , i n the c l a y m i n e r a l domains d u r i n g t h e r m a l t r e a t ment and t h a t i r o n e n t e r s the r e g i o n . F u r t h e r i n q u i r i e s are i n p r o g r e s s t o answer t h e s e q u e s t i o n s . C a l c i t e appears l a r g e l y i n e r t a t temperatures a p p r o a c h i n g 600°C i n the p r e s e n c e of some o f the c l a y m i n e r a l s and i n e r t u n t i l about 900°C i n t h e i r absence. The cause o f t h i s f l u x i n g i s not w e l l under s t o o d a t t h i s time, but i n v e s t i g a t i o n s a r e p l a n n e d t o e x p l a i n t h i s behavior. At whatever temperature, the r e a c t i o n o b s e r v e d i s the d e c o m p o s i t i o n o f c a l c i t e to l i m e (CaO) and c a r b o n d i o x i d e . The e x t e n t to which c a r b o n d i o x i d e i n f l u e n c e s f u r t h e r r e a c t i o n i s n o t known but must be c o n s i d e r e d as an i m p o r t a n t s t e p i n a complete explanation. L i k e c a l c i t e , p y r i t e i s q u i t e r e a c t i v e and i t s t h e r m a l b e h a v i o r i s i n f l u e n c e d by the p r e s e n c e o f c l a y m i n e r a l s . The i n i t i a l r e a c t i o n temperature o f p y r i t e a l o n e o r i n the p r e s e n c e o f c a l c i t e a l o n e i s to
Vorres; Mineral Matter and Ash in Coal ACS Symposium Series; American Chemical Society: Washington, DC, 1986.
10.
BIGGS A N D LINDSAY
High-Temperattire
Interactions
among Minerals
137
produce p y r r h o t i t e , ( F e ^ ^ S ) and t r o i l i t e ( F e S ) . The l o s s o f s u l f u r i s o b v i o u s and c o n t i n u e s over an a p p r e c i a b l e temperature range. The most i m p o r t a n t r e a c t i o n p r o d u c t s a r e those o f t h e i r o n enrichment o f t h e c l a y m i n e r a l r e s i d u e s , p r o b a b l y a p r e c u r s o r o f t h e i r o n o x i d e and g l a s s m i x t u r e s commonly o b s e r v e d i n s l a g s and f l y a s h e s , and t h e f o r m a t i o n o f t h e s u l f i d e o f c a l c i u m , o l d h a m i t e . Oldhamite i s o b s e r v e d i n a l l experiments where c a l c i t e and p y r i t e i n t e r a c t , whereas a n h y d r i t e i s o b s e r v e d o n l y where they have r e a c t e d i n t h e p r e s e n c e o f an o x y g e n - r i c h atmosphere. T h i s behavior suggests t h a t o l d h a m i t e , formed i n t h e r e d u c i n g p a r t o f a f l a m e , i s a n e c e s sary p r e c u r s o r t o the formation o f a n h y d r i t e .
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Acknowledgments T h i s m a t e r i a l i s based, i n p a r t , on work s u p p o r t e d by t h e U.S. Bureau o f Mines, Department o f t h e I n t e r i o r , under Grant No. Gl106002. Any o p i n i o n s , f i n d i n g s , and c o n c l u s i o n s o r recommendations e x p r e s s e d i n t h i s p u b l i c a t i o n a r e those o f t h e a u t h o r s and do n o t n e c e s s a r i l y r e f l e c t t h e views o f t h e U.S. Bureau o f Mines, Department of t h e I n t e r i o r . Work on o t h e r p a r t s o f t h i s p u b l i c a t i o n was performed i n Ames L a b o r a t o r y and was s u p p o r t e d by t h e A s s i s t a n t S e c r e t a r y o f F o s s i l Energy, D i v i s i o n o f C o a l U t i l i z a t i o n t h r o u g h t h e P i t t s b u r g h Energy Technology C e n t e r , C o a l P r e p a r a t i o n Branch. Ames L a b o r a t o r y i s o p e r a t e d f o r t h e U.S. Department o f Energy by Iowa S t a t e U n i v e r s i t y under C o n t r a c t W-7405-Eng-82.
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RECEIVED June 13, 1985
Vorres; Mineral Matter and Ash in Coal ACS Symposium Series; American Chemical Society: Washington, DC, 1986.