FORMULAS FOR CALCULATING THE HEATING VALUE OF COAL AND COAL CHAR: DEVELOPMENT,

TESTS AND USES

D. M. Mason and K . Gandhi

I n s t i t u t e of Gas Technology
3424 S . S t a t e S t .
Chicago, I l l i n o i s 60616

The h e a t i n g ( c a l o r i f i c ) v a l u e of c o a l and c h a r i s of g r e a t i m p o r t a n c e i n t h e
c o n v e r s i o n of c o a l t o o t h e r u s e f u l forms of f u e l , a s w e l l a s i n i t s d i r e c t u s e .
The s i g n i f i c a n c e of t h e c o r r e l a t i o n of h e a t i n g v a l u e w i t h composition i n o r d i n a r y
f u e l usage is shown by t h e development, a s e a r l y as 1940, of some 9 d i f f e r e n t f o r -
mulas f o r c a l c u l a t i n g h e a t i n g v a l u e from t h e u l t i m a t e a n a l y s i s and 11 f o r m u l a s f o r
c a l c u l a t i n g i t from t h e proximate a n a l y s i s (1). Three a d d i t i o n a l u l t i m a t e a n a l y s i s
formulas have been proposed w i t h i n t h e last t h r e e years ( 2 , 3 , 4 ) . The c o r r e l a t i o n
i s perhaps of even g r e a t e r importance f o r t h e r a t i o n a l i z a t i o n and modeling of con-
v e r s i o n p r o c e s s e s now b e i n g developed.

Our own w o r k on t h i s problem was c a r r i e d o u t f o r a p r o j e c t on p r e p a r a t i o n of

a "Coal Conversion Systems T e c h n i c a l Data Book," s u p p o r t e d by t h e U.S. Department
of Energy and i t s p r e d e c e s s o r s .

A d a t a b a s e ( i n c l u d i n g e x p e r i m e n t a l h e a t i n g v a l u e s , u l t i m a t e a n a l y s e s and some
o t h e r p a r a m e t e r s ) was e s t a b l i s h e d , c o n s i s t i n g of 1 2 1 samples from t h e Coal Research
S e c t i o n o f Pennsylvania S t a t e U n i v e r s i t y ( 5 ) , and 681 samples a n a l y z e d by t h e Bureau
of Mines and r e p o r t e d i n v a r i o u s s t a t e and F e d e r a l government p u b l i c a t i o n s ( 6 , 7 , 8 , 9 ) .
The Penn S t a t e samples, r e p r e s e n t i n g l a r g e d e p o s i t s of coal, had been s e l e c t e d f o r
t a b u l a t i o n i n t h e Data Book ( 1 0 ) . The d a t a b a s e c o v e r s a wide range o f c o a l f i e l d s
of t h e United S t a t e s .

Four formulas were s e l e c t e d f o r t e s t . They a r e a s f o l l o w s :

Dulong (1)

Q = 145.44 C + 620.28 H + 40.5 S - 77.54 (0)

Boie (11)

Q = 151.2 C + 499.77 H + 45.0 S - 47.7 (O)+ 27.0 N

Grummel and Davis (1,121

9 = [ ~~~~~~ + 424.621 [C/3 +H -(0)/8 + s/8] 3)

Mott and Spooner ( 1 , 1 3 )

Q = 144.54 C + 610.2 H + 40.5 S - 62.46 (0) ( 0 ) 5 15%

Q = 144.54 C + 610.2 H + 40.5 S - [65.88 - -30

-(100-A)
96(0)
"---](O) (O)> 15%

235
 In t h e above, Q i s t h e g r o s s h e a t i n g v a l u e i n B t u / l b on t h e dry b a s i s and C , H ,
S , (O), N , and A a r e t h e r e s p e c t i v e c o n t e n t s o i c a r b o n , hydrogen, s u l f u r , oxygen,
n i t r o g e n , and a s h i n w e i g h t p e r c e n t , a l s o on t h e d r y b a s i s .

For a f a i r test of t h e f o r m u l a s on samples r e p r e s e n t i n g commercial c o a l we

e l i m i n a t e d samples w i t h more t h a n 30% a s h , l e a v i n g a t o t a l of 775 samples i n t h e
d a t a bank. R e s u l t s of a p p l y i n g t h e s e v e r a l formulas s e p a r a t e l y t o t h e v a r i o u s r a n k s
of c o a l and a l s o t o t h e combined ( a l l r a n k s ) d a t a are p r e s e n t e d i n T a b l e 1. The
b i a s ( a v e r a g e a l g e b r a i c d i f f e r e n c e between observed and c a l c u l a t e d v a l u e s ) and t h e
s t a n d a r d d e v i a t i o n a f t e r c o r r e c t i o n f o r t h e b i a s are t h e most s i g n i f i c a n t c r i t e r i a .
F o r most of t h e f o r m u l a s t h e r e are l a r g e d i f f e r e n c e s i n b i a s among d i f f e r e n t r a n k s
of c o a l , s o w e have c a l c u l a t e d s t a n d a r d d e v i a t i o n s f o r each r a n k a f t e r c o r r e c t i n g
f o r t h e b i a s shown f o r t h a t r a n k . The s t a n d a r d d e v i a t i o n i s a l s o g i v e n w i t h
a p p l i c a t i o n of a b i a s c o r r e c t i o n averaged o v e r a l l r a n k s . Note t h a t t h e often-used
Dulong formula h a s a s u b s t a n t i a l b i a s f o r a l l r a n k s , b u t of o p p o s i t e s i g n f o r low-
r a n k c o a l s compared w i t h bituminous and a n t h r a c i t e c o a l s . Thus t h e o v e r a l l b i a s
i s low, b u t no a d v a n t a g e is g a i n e d by i t s a p p l i c a t i o n . A l s o n o t e t h a t a l t h o u g h
r e s u l t s from t h e Boie e q u a t i o n have t h e h i g h e s t b i a s of any, a f t e r a p p l i c a t i o n of
a n o v e r a l l b i a s c o r r e c t i o n t h e r e s u l t s a r e among t h e b e s t .

I n a d d i t i o n t o c a l c u l a t i o n w i t h t h e formulas p e r s e , we a l s o c a l c u l a t e d h e a t i n g
v a l u e s by u s e of Given and Y a r z a b ' s modified P a r r e q u a t i o n f o r m i n e r a l m a t t e r c o n t e n t ,
and t h e i r c o r r e c t i o n s t o o b t a i n carbon, hydrogen, s u l f u r and oxygen on a mineral-
matter-free b a s i s (14). This c a l c u l a t i o n requires values f o r p y r i t i c s u l f u r t h a t
were n o t a v a i l a b l e f o r some of t h e samples. K e s u l t s o b t a i n e d w i t h t h e modified Mott-
Spooner e q u a t i o n s on 646 s a r i p l e s having p y r i t i c s u l f u r c o n t e n t s a r e a l s o shown i n
Table 1; r e s u l t s from o t h e r formulas were improved, b u t t h e Mott-Spooner e q u a t i o n
gave t h e b e s t r e s u l t s . D e t a i l s of t h i s c a l c u l a t i o n and f u l l r e s u l t s a r e r e p o r t e d
elsewhere (15).

The d a t a bank was a l s o s u b j e c t e d t o a l e a s t s q u a r e s r e g r e s s i o n a n a l y s i s . Carbon,

hydrogen, s u l f u r , a s h , and oxygen terms were s i g n i f i c a n t ; n i t r o g e n and c r o s s and
s q u a r e terms were n o t . To a v o i d t h e implied n e c e s s i t y of d e t e r m i n i n g n i t r o g e n , we
a d o p t e d an o x y g e n - p l u s - n i t r o g e n term. The r e s u l t i n g e q u a t i o n , which w e r e f e r t o h e r e
a s t h e Data Book E q u a t i o n , was a s f o l l o w s :

Q = 146.58 C + 568.78 H + 29.4 S - 6 . 5 8 A - 51.53 (0 + N) 5 4

When 100- C-H-S-A i s s u b s t i t u t e d f o r O+N, a n e q u i v a l e n t form is o b t a i n e d :

Q = 198.11 C + 620.31 H + 80.93 S + 44.95 A - 5153 5b )

R e s u l t s from t h i s new f o r m u l a a r e a l s o shown i n Table 1. The b i a s f o r d i f f e r e n t ranks

of c o a l r a n g e s o n l y from -45 B t u / l b on l i g n i t e t o 1 3 B t u / l b on subbituminous c o a l and
d o e s n o t show a t r e n d w i t h r a n k . The s t a n d a r d d e v i a t i o n i s s i g n i f i c a n t l y l e s s t h a n
t h o s e of t h e o t h e r unmodified f o r m u l a s , even a f t e r improving t h e s e by a b i a s c o r r e c -
tion. The new formula h a s a b o u t t h e same a c c u r a c y a s t h e Mott-Spooner w i t h modified
P a r r c o r r e c t i o n s , b u t t h e l a t t e r i s more complicated and r e q u i r e s p y r i t i c s u l f u r de-
termination.

The e f f e c t o f a s h c o n t e n t on t h e a c c u r a c y and p r e c i s i o n of t h e formula was in-

v e s t i g a t e d , w i t h t h e r e s u l t s shown i n Table 2. For t h i s t e s t , t h e formula w a s a l s o
a p p l i e d t o t h e 2 7 h i g h - a s h samples t h a t had been removed from t h e d a t a bank.

236
 T a b l e 1. TEST OF FORMULAS FOR CALCULATION OF HEATING VALUE
Standard D e v i a t i o n
Average Before After A f t e r Over-
No. o f Absolute Bias Rank B i a s all Bias**
Samples Deviation Correction Correction Correction
Btu/lb
Dulong
Anthracite 40 137 -123 157 97 146
Bituminous 406 181 -138 221 173 212
Subbituminous 130 174 127 213 170 222
Lignite 1 49 218 174 255 185 266
A l l Ranks 775 184 -15 223 - 222
Boie
__
Anthracite 40 400 -400 417 100 17 7
Bituminous 406 253 -248 279 129 129
Subbituminous 180 217 -207 249 138 146
Lignite 149 301 -298 330 138 145
A l l Ranks 775 262 -256 291 - 1 39
Grummel and Davis
Anthracite 40 107 79 134 106 165
Bituminous 406 164 -128 208 164 184
Subbituminous 180 130 46 1 68 161 185
Lignite 1 49 127 39 171 1 67 187
A l l Ranks 775 146 -44 189 - 184
Mott and Spooner
Anthracite 40 84 -56 107 91 100
Bituminous 406 160 -134 197 144 149
Subbituminous 180 113 -31 152 1 49 162
Lignite 149 124 -85 170 147 147
A l l Ranks 775 138 -96 178 - 150

Mott & Spooner,

Modified P a r r B a s i s
A l l Ranks 646 106 42 - - 132

New Formula
Anthracite 40 73 -14 93 92 93

Bituminous 406 90 10 124 1 23 124

Subbituminous 180 103 13 140 139 140

Lignite 149 96 -45 137 129 1 37

A l l Ranks 775 93 0 129 129 129

* Average observed v a l u e -average c a l c u l a t e d v a l u e

** Bias o b t a i n e d o v e r a l l r a n k s
237
 Table 2. EFFECT OF ASH CONTENT ON THE CALCULA'I'ION OF HEATING VALUE

Ash C o n t e n t , Number of Avg. Absolute Standard

W t % Samples Difference --
Bias* Deviation

0-10 394 82 6 113

10-20 320 104 -15 144
20- 30 61 112 26 141
> 30 27 155 20 211
*
Average of observed minus a v e r a g e of c a l c u l a t e d v a l u e s
The absence of s i g n i f i c a n t b i a s , h e r e and among d i f f e r e n t r a n k s of c o a l , i n d i -
cates t h a t no improvement by change i n t h e formula a p p e a r s p o s s i b l e a s l o n g a s i t
i s based on u l t i m a t e a n a l y s i s o n l v . The i n c r e a s e of t h e s t a n d a r d d e v i a t i o n w i t h
a s h c o n t e n t can b e a t t r i b u t e d t o t h e e f f e c t s of d i f f e r i n g r a t i o s of m i n e r a l m a t t e r
t o a s h , and d i f f e r i n g c o n t r i b u t i o n s of t h e m i n e r a l matter t o determined carbon and
hydrogen c o n t e n t s . A computer a n a l y s i s o f t h e d a t a i n which i t was assumed t h a t t h e
v a r i a n c e i s l i n e a r w i t h a s h c o n t e n t i n d i c a t e d t h a t t h e v a r i a n c e i n c r e a s e s by 4 / 2
( B t u / l b ) z p e r p e r c e n t o f a s h , and t h a t t h e s t a n d a r d d e v i a t i o n on a s h - f r e e samples
would be 106 B t u / l b .

I t i s of i n t e r e s t t o d e t e r m i n e whether t h e r e m a i n i n g v a r i a n c e can a c t u a l l y be
a t t r i b u t e d to t h e laboratory determinations. The l a t t e r can be e s t i m a t e d a c c o r d i n g
to -

Var (exp) = Var Q + 198.11' Var C + 62U.312 Var H

+ 80.932 Var s + 44.95' Var A 6)

where Var Q , Var C , e t c . , a r e v a r i a n c e s of t h e r e s p e c t i v e d e t e r m i n a t i o n s . Some

p r e c i s i o n d a t a have become a v a i l a b l e from t h e HYGASO program a t I G T , which can be
used for a t e s t .

Sources of v a r i a n c e of t h e e x p e r i m e n t a l d e t e r m i n a t i o n s need t o be considered f o r

t h e purpose a t hand. The h e a t i n g v a l u e and t h e a n a l y t i c a l d e t e r m i n a t i o n s (carbon,
hydrogen, s u l f u r , and a s h ) a r e a l l run o n a sample of c o a l (or c h a r ) thdL h a s been
ground f i n e r t h a n 60-mesh s i e v e s i z e . Thus, t h e v a r i a n c e from sampling of t h e c o a r s e
sample s u b m i t t e d t o t h e l a b o r a t o r y i s n o t of concern. I f t h e m o i s t u r e c o n t e n t does
n o t change d u r i n g a l l o f t h e sample w i t h d r a w a l s f o r t h e v a r i o u s d e t e r m i n a t i o n s , no
v a r i a n c e i s c o n t r i b u t e d by t h e m o i s t u r e d e t e r m i n a t i o n ; however, i f s e v e r a l days
e l a p s e between h e a t i n g v a l u e and carbon-hydrogen d e t e r m i n a t i o n s , a c o n t r i b u t i o n from
t h i s s o u r c e is l i k e l y , e i t h e r from t h e change i n m o i s t u r e o r from t h e v a r i a n c e of i t s
redetermination. V a r i a n c e c a n a l s o be c o n t r i b u t e d by day-to-day v a r i a t i o n s i n equip-
ment and o p e r a t o r ; t h u s r e d e t e r m i n a t i o n on t h e same day would n o t s e r v e t h e purpose.
I n s t e a d , o u r p r o c e d u r e c o n s i s t e d of r e s u b m i t t i n g from t i m e t o t i m e a number of ground
samples of c o a l ( i n t h e same 4-02 b o t t l e s a s o r i g i n a l l y sampled from) f o r r e d e t e r m i -
n a t i o n of m o i s t u r e , h e a t i n g v a l u e , c a r b o n , hydrogen, s u l f u r , and a s h . Each r e p o r t e d
v a l u e f o r carbon, hydrogen, a s h , and h e a t i n g v a l u e i s t h e a v e r a g e of two determi-
n a t i o n s r u n a t t h e same t i m e ; f o r s u l f u r o n l y one d e t e r m i n a t i o n i s made. Completion
o f t h e d u p l i c a t e a n a l y s i s ranged from 9 t o 46 d a y s a f t e r completion of t h e r o u t i n e
analysis. S l i g h t a v e r a g e c h a n g e s i n v a l u e s from t h e o r i g i n a l a n a l y s i s t o t h e d u p l i -
c a t e , such a s an a v e r a g e d e c r e a s e i n h e a t i n g v a l u e of 1 3 B t u / l b , o c c u r r e d ; t h e
s t a n d a r d d e v i a t i o n s were c a l c u l a t e d b o t h w i t h and w i t h o u t c o r r e c t i o n f o r t h i s b i a s .

The d u p l i c a t e d i f f e r e n c e s from t h i s program were examined f o r o u t l i e r s . Three

s u l f u r , one a s h and o n e h e a t i n g v a l u e , a l l w i t h d i f f e r e n c e s between d u p l i c a t e s
g r e a t e r than 3.8 J2 u, were d i s c a r d e d . In addition, a heating value w i t h a duplicate
d i f f e r e n c e of 2.8 J2 a , and a l s o h a v i n g a d i f f e r e n c e between observed and c a l c u l a t e d
v a l u e s of 3.5 a was a l s o d i s c a r d e d . The a n a l y s i s of t h e remaining d a t a i S pre-
s e n t e d i n Table 3.

238
 The v a r i a n c e c o n t r i b u t e d t o t h e d i f f e r e n c e between observed and c a l c u l a t e d
h e a t i n g v a l u e s by t h e v a r i a n c e of t h e e x p e r i m e n t a l d e t e r m i n a t i o n s c a n now be c a l c u -
l a t e d a c c o r d i n g t o Equation 6. The s t a n d a r d d e v i a t i o n s a f t e r b i a s c o r r e c t i o n s
(Table 3 ) y i e l d s t h e v a l u e 64 B t u / l b as t h e e x p e c t e d 0. T h i s r e p r e s e n t s 77% o f
t h e v a r i a n c e found f o r a l a r g e set of r o u t i n e HYGAS d a t a on r a w b i t u m i n o u s c o a l
d i s c u s s e d l a t e r i n t h i s p a p e r . The remainder of t h e v a r i a n c e can be a t t r i b u t e d
t o t h e e f f e c t of o u t l y i n g l a b o r a t o r y d e t e r m i n a t i o n s , and t h e e f f e c t of m i n e r a l
matter .
1 T a b l e 3. SUMMARY OF HYGAS REPEATMILITY DATA

S t a n d a r d Deviation**
No. of 'Average Before B i a s A f t e r Bias
Duplicates Value Bias* Correction Correction

Btullb
Heating Value 56 11680 13 29 27
W t %
Carbon 41 64.07 0.037 0.25 0.24
Hydrogen 41 4.52 0.028 0.051 0,051
Sultur 55 4.39 -0.011 0.084 0.086
Ash 40 16.77 0.037 0.14 0.14

* O r i g i n a l minus d u p l i c a t e
** Of r e p o r t e d v a l u e s , each t h e a v e r a g e of two d e t e r m i n a t i o n s run a t
t h e same t i m e , e x c e p t s i n g l e d e t e r m i n a t i o n s f o r s u l f u r .

TEST AND USES

Data f o r t e s t i n g of t h e new formula were s o l i c i t e d from o u t s i d e l a b o r a t o r i e s .

R e s u l t s from two l a b o r a t o r i e s p r e s e n t e d i n T a b l e 4 show good p r e c i s i o n , b u t t h e
l a r g e b i a s v a l u e s s u g g e s t t h e p r e s e n c e of s y s t e m a t i c e r r o r o r d i f f e r e n c e from t h e
original data.

R e s u l t s from a t h i r d l a b o r a t o r y i l l u s t r a t e a n i m p o r t a n t u s e of t h e formula. The

e x p e r i m e n t a l d a t a covered a p e r i o d of s e v e r a l y e a r s and were f u r n i s h e d i n t h e sequence
i n which t h e y were o b t a i n e d by t h e l a b o r a t o r y . W e e l i m i n a t e d a few samples h a v i n g
o v e r 35% a s h o r less than 3% oxygen, b e c a u s e t h e l a t t e r are l i k e l y t o b e c h a r s . On
t h e remaining d a t a , t h e s t a n d a r d d e v i a t i o n s o b t a i n e d from c o n s e c u t i v e sets of 50
samples a r e shown i n F i g u r e 1. On t h e f i r s t 650 samples t h e b i a s was 32 B t u / l b and
t h e s t a n d a r d d e v i a t i o n was 136 B t u / l b , i n good agreement w i t h r e s u l t s on t h e o r i g i n a l
d a t a bank. On subsequent samples t h e r e s u l t s i n d i c a t e a s u b s t a n t i a l d e t e r i o r a t i o n i n
laboratory precision. Thus, a c o n t r o l c h a r t of t h i s k i n d can s e r v e a s a monitor of
l a b o r a t o r y performance. Also, t h e d i f f e r e n c e between observed and c a l c u l a t e d h e a t i n g
v a l u e s on an i n d i v i d u a l sample can be used by t h e l a b o r a t o r y s u p e r v i s o r as a c r i t e r i o n
of a c c e p t a b i l i t y of t h e h e a t i n g v a l u e and carbon-hydrogen d e t e r m i n a t i o n s . The
d i f f e r e n c e is less s e n s i t i v e t o t h e s u l f u r and a s h v a l u e s .

239
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 Another i m p o r t a n t u s e of a h e a t i n g v a l u e formula i s i n computer modeling of c o a l
conversion processes. Data on h e a t i n g v a l u e and composition of samples of c o a l and
c h a r o b t a i n e d a t IGT under t h e HYGAS p i l o t p l a n t program were a n a l y z e d f o r t h i s pur-
pose. I n t h e HYGAS p r o c e s s , non-agglomerating c o a l s a r e d r i e d b u t a r e n o t o t h e r w i s e
pretreated. Bituminous c o a l s a r e p r e t r e a t e d a t t e m p e r a t u r e s of 750°F t o 800'F t o
d e s t r o y t h e i r agglomerating p r o p e r t i e s . The r e s u l t i n g p r o d u c t i s r e f e r r e d t o h e r e a s
" p r e t r e a t e d c o a l " r a t h e r t h a n "char". Samples r e f e r r e d t o as " c h a r s " a r e from later
i n t e r m e d i a t e s t a g e s o r a r e s p e n t ( r e s i d u e ) c h a r . Ash i n t h e s p e n t c h a r from t h e r u n s
on bituminous c o a l a v e r a g e d 36X, b u t ranged up t o about 85%. To augment t h e d a t a from
r u n s on subbituminous a n d l i g n i t e c o a l s , w e have added some samples taken from streams
t h a t c o n t a i n f e e d c o a l i n a d d i t i o n t o c h a r , such as t h e d u s t c o l l e c t e d by a cyclone i n
t h e r e a c t o r p r o d u c t g a s stream. R e s u l t s a r e p r e s e n t e d i n Table 5 , t o g e t h e r w i t h those
o b t a i n e d on t h e o r i g i n a l d a t a bank.

'The most i m p o r t a n t c r i t e r i o n f o r u s e of a h e a t i n g v a l u e formula i n a computer

model of a c o a l c o n v e r s i o n p r o c e s s i s t h e b i a s o r a v e r a g e d i f f e r e n c e between observed
and c a l c u l a t e d v a l u e s , b e c a u s e i t shows how c l o s e l y t h e formula r e p r e s e n t s t h e prop-
e r t i e s of t h e c o a l . On t h e 294 samples of r a w ( u n t r e a t e d ) bituminous c o a l s , t h e
c a l c u l a t e d v a l u e s a r e , o n t h e a v e r a g e , 18 B t u / l b l e s s t h a n the observed v a l u e s . T h i s
d i f f e r s by o n l y 8 B t u / l b from t h e v a l u e found on t h e 406 samples of bituminous c o a l
i n t h e o r i g i n a l d a t a bank. There i s o n l y about a 20 p e r c e n t chance t h a t t h e d i f f e r -
e n c e i s s i g n i f i c a n t ; i f s o , i t c a n be a t t r i b u t e d t o a s l i g h t l y lower a s h c o n t e n t
o b t a i n e d a t I G T , because a t IGT t h e amount of s u l f u r t r i o x i d e i n a s h is r o u t i n e l y
determined and d e d u c t e d from t h e r e p o r t e d a s h . Ash as c u s t o m a r i l y determined i s
l i k e l y t o c o n t a i n small amounts o f s u l f u r t r i o x i d e .

The s t a n d a r d d e v i a t i o n shown f o r t h e s e c o a l samples is s u b s t a n t i a l l y less than

w a s found on t h e b i t u m i n o u s c o a l s of t h e o r i g i n a l d a t a bank. The d i f f e r e n c e may be
a r e s u l t o f t h e l i m i t e d r a n g e of s o u r c e of t h e HYGAS samples: a l l were from t h e
I l l i n o i s N o . 6 seam and 95% were from a s i n g l e mine; t h e a s h c o n t e n t averaged 10.7L.
(The samples from t h e r e p e a t a b i l i t y s e t of d a t a had h i g h e r a s h , a v e r a g i n g a b o u t 17%).
On p r e t r e a t e d b i t u m i n o u s c o a l t h e c a l c u l a t e d v a l u e s a r e , o n t h e a v e r a g e , 157 B t u l l b
lower t h a n t h e observed v a l u e s . The Data Book formula i s t h u s u n s a t i s f a c t o r y f o r use
i n a computer model a p p l i e d t o t h i s m a t e r i a l ; f o r s u c h u s e a b i a s c o r r e c t i o n can be
a p p l i e d o r a formula c a n be o b t a i n e d by r e g r e s s i o n a n a l y s i s of t h e p r e t r e a t e d c o a l
d a t a . The d i f f e r e n c e i n b i a s between t h e p a r e n t and p r e t r e a t e d c o a l , 139 B t u / l b , can
b e a t t r i b u t e d t o a d i f f e r e n c e i n s t r u c t u r e ( b o n d i n g ) ; t h e formula h a s a l r e a d y taken
i n t o account d i f f e r e n c e s i n e l e m e n t a l composition. Such d i f f e r e n c e s i n s t r u c t u r e
i n c l u d e e f f e c t s of i n c o r p o r a t i o n o f oxygen i n a d i f f e r e n t form from t h a t o r d i n a r i l y
p r e s e n t . I n o t h e r p r o c e s s e s t h e d i f f e r e n c e i n b i a s may be g r e a t e r o r l e s s , depend-
i n g on p r o c e s s i n g c o n d i t i o n s s u c h as t e m p e r a t u r e and p r e s e n c e o r a b s e n c e of oxygen;
i n t h e HYGAS p r o c e s s t h e d i f f e r e n c e i s reduced t o about 40 B t u / l b a t t h e s t a g e where
t h e t e m p e r a t u r e r e a c h e s a b o u t 1200°F.
On the set o f s a m p l e s o f c h a r from b i t u m i n o u s c o a l s t h e c a l c u l a t e d v a l u e s a r e ,
on t h e a v e r a g e , o n l y 28 B t u / l b less than t h e observed v a l u e s ; t h e d i f f e r e n c e i s of
a b o u t t h e same o r d e r f o r c h a r s from subbituminous c o a l and l i g n i t e . A more a c c u r a t e
formula could be o b t a i n e d f o r t h e c h a r s from t h e bituminous c o a l , b u t t h e Data Book
f o r m u l a should b e a d e q u a t e f o r most p r a c t i c a l p u r p o s e s ; t h e a c c u r a c y s h o u l d be judged
a c c o r d i n g t o u n i t weight of c o a l f e e d r a t h e r t h a n u n i t weight of c h a r .

CONCLUSIONS

A new f i v e - t e r m f o r m u l a f o r c a l c u l a t i n g t h e h e a t i n g v a l u e of c o a l from i t s c a r -
bon, hydrogen, s u l f u r a n d a s h c o n t e n t w a s o b t a i n e d by r e g r e s s i o n a n a l y s i s of d a t a on
775 s a m p l e s of U. S. c o a l s o f a l l ranks. The s t a n d a r d d e v i a t i o n of t h e c a l c u l a t e d
v a l u e from t h e o b s e r v e d v a l u e was 129 B t u / l b , compared t o a p p a r e n t s t a n d a r d d e v i a t i o n s
r a n g i n g from 1 7 8 t o 229 B t u / l b o b t a i n e d from t h e Dulong, Boie, Grummel and Davis,
and Matt and Spooner f o r m u l a s . An a n a l y s i s of t h e v a r i a n c e of t h e d i f f e r e n c e between

242
 Table 5. TEST ON HYGAS ROUTINE SAMPLES OF THE DATA BOOK FOKMULA
FOR CALCULATION OF HEATING VALUE

Standard Deviation
No. of Before Bias A f t e r Bias
Samples Uiasd Correction Correction
\ HYGAS Data Bank Btuflb

Bituminous Coala

Raw Coal 294 18 73 71

P r e t r e a t e d Coal 572 157 174 76
Chars
F i r s t Stage H y d r o g a s i f i c a t i o n 105 58 98 79
Second S t a g e H y d r o g a s i f i c a t i o n 106 2 106 106
Spent Char 5 70 28 97 Y2
A l l Char 781 28 98 94

Subbituminous Coalb

Coal 49 -47 69 21
Chars 80 15 59 57
Mixtures of Coal and Char 66 15 55 53

Lignite'

Chars 80 34 78 77
Mixtures o f Coal and Char 44 12 88 71

O r i g i n a l Data Bank

Bituminous Coal 406 10 124 124

Subbituminous Coal 180 13 140 140
Lignite 149 -45 137 137
A l l Samples, I n c l u d i n g A n t h r a c i t e 775 0 129 129

a From I l l i n o i s No. 6 seam. About 1/8 of t h e samples were from r u n s o n hvBb

c o a l from S a l i n e County, and t h e remainder from r u n s on hvCb c o a l from C h r i s t i a n
County.

From the Rosebud Seam, Rosebud County, Montana.

From t h e Savage Mine, Richland County, Montana.

Average observed v a l u e minus a v e r a g e c a l c u l a t e d v a l u e .

243
 observed a n d c a l c u l a t e d v a l u e s o b t a i n e d w i t h t h e new formula on IGT c o a l d a t a
i n d i c a t e d t h a t a t l e a s t 77% i s c o n t r i b u t e d by t h e v a r i a n c e o f t h e e x p e r i m e n t a l d e t e r -
m i n a t i o n s ; t h e remainder c a n be a t t r i b u t e d t o t h e e f f e c t of m i n e r a l m a t t e r and out-
l y i n g experimental determinations.

A p p l i c a t i o n of t h e f o r m u l a t o c o a l o x i d a t i v e l y p r e t r e a t e d a t 750°F t o 800°F t o
d e s t r o y a g g l o m e r a t i n g p r o p e r t i e s y i e l d s a b i a s i n d i c a t i n g t h a t i t s h e a t of formation
is h i g h e r t h a n e x p e c t e d f r o m e l e m e n t a l and a s h c o m p o s i t i o n by a b o u t 140 B t u / l b ; t h i s
i s a t t r i b u t e d t o d i f f e r e n c e s i n s t r u c t u r e (bonding) of t h e p r e t r e a t e d c o a l i n comparison
to u n p r e t r e a t e d c o a l . The formula g i v e s s a t i s f a c t o r y r e s u l t s on h i g h e r temperature
HYGAS c h a r s , and, w i t h a p p l i c a t i o n of a b i a s c o r r e c t i o n , on p r e t r e a t e d c o a l

Thus, t h e formula is advantageous f o r use i n t h e compvtei- m o d e l l i n g of c o a l con-

v e r s i o n p r o c e s s e s and f o r m o n i t o r i n g test d a t a on c o a l and c h a r .

Acknowledgement

The work r e p o r t e d h e r e was conducted a s p a r t of a p r o j e c t , sponsored by t h e

U. S. Department of Energy, on p r e p a r a t i o n of a Coal Conversion Systems 'Technical
Data Book. Use of d a t a o b t a i n e d under t h e HYGAS program i s g r a t e f u l l y acknowledged.

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244
 13. Mott, R . A . , and Spooner, C. E . , "The C a l o r i f i c Value of Carbon i n C o a l , "
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245