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Fuel Processing Technology, 3 (1980) 39--53 39

Elsevier Scientific Publishing Company, Amsterdam -- Printed in The Netherlands

ESTIMATING THERMODYNAMIC PROPERTIES OF COAL, CHAR, TAR


AND ASH

W. EISERMANN, P. JOHNSON and W.L. CONGER


Department of Chemical Engineering, University of Kentucky, Lexington, Kentucky 40506
(U.S.A.)
(Received February 12th, 1979; accepted June 15th, 1979)

ABSTRACT

Methods for predicting the specific heat, enthalpy, and entropy of coal, char, tar and ash
as a function of temperature and material composition are presented. The standard entropy
of coal is approximated by comparing the behavior of the standard entropies of a number
of aliphatic and aromatic hydrocarbons as a function of the variables H](C + N), O/(C + N),
N/(C + N), and S/(C + N), where the variables are the atomic fractions of the respective ele-
ments. The standard entropy of a bituminous coal was found to be about 20 k J/ k m o l carbon K
and of the char to be about 10 k J /k m o l carbon K. Estimates of the enthalpy difference
between 273 K and temperatures above 273 K deviated from published data by about 8.49%
for chars and 8.55% for coals on the average. Maximum deviations of 18:3% and 17.6% re-
spectively were found.

INTRODUCTION

Evaluation of the thermodynamic properties of coal and coal products is im-


portant in the development and analysis of such coal related processes as
gasification, liquefaction, briquetting, and carbonization. Specifically, the
evaluation of the enthalpy and entropy of these compounds is essential for per-
forming first and second law analyses.
Although several studies have been made on the specific heat, enthalpy, and
entropy of coal and coal products [ 1,2,3], the temperature and composition
ranges covered have not always been large enough for practical application.
Also, there is very little information on the standard enthalpy and entropy of
these materials, especially in terms of varying composition, which is critical in
the determination of accurate absolute enthalpy and entropy values.
This paper presents a method for evaluating the specific heat, enthalpy, and
entropy of coal, char, tar and ash. Results for several of these materials are pre-
sented and discussed. Where necessary units have been changed to conform
with the SI system.
40

SPECIFIC H E A T O F COAL, CHAR, T A R A N D A S H

Specific heat o f coal, char and ash

The approach used in evaluating the specific heat of coal and the char re-
maining after the devolatilization of coal is similar to that developed b y Kirov
[4]. In his approach, Kirov t o o k the specific heat of coal to be the summation
of the specific heats, weighted by the respective mass fractions, of the com-
ponents: moisture; primary volatile matter (evolved at relatively low tempera-
ture); secondary volatile matter (evolved at higher temperatures); ash-free
fixed carbon; and ash. The specific heats of the components were found to be
adequately correlated as functions of temperature and volatile matter. The
temperature range covered is from 273 to 1373 K and thus includes the
regime in which gasification occurs.
In evaluating the specific heat of coal, the temperature at which devolatiliza-
tion of the coal begins is an important parameter. This temperature is
evaluated using the correlation developed b y Gregory and Littlejohn [ 5 ]:
267.4
T1 = + 273.15 (1)
W~0.2s55
O
where T1 = devolatilization temperature (K) and WV = original mass fraction
of volatiles in original dry, ash-free coal. The amount of volatiles in the coal or
char above the temperature T1 can be determined b y substituting the higher
temperature for T~ in eqn. (1) and solving for W,~.
The evaluation of the original fraction of volatile matter in the coal or char,
based on the ultimate analysis, is made using the following expression [6] :

Wv = 0 . 4 0 4
[ 28.9 +3.46
( 1 - --C'
0 )oC-' -1
] (2)

where H', C', O' = weight percents, respectively, of hydrogen, carbon, and
oxygen in the original coal, on a dry, ash-free basis, and where W~r is as de-
fined above.
Once the fraction of original volatile matter has been evaluated, the fraction
of fixed carbon in the coal on a dry, ash-free basis can be found b y subtracting
the volatile matter fraction from unity. The specific heat of fixed carbon
(using Kirov's [4] form) is expressed as
CF = - 0 . 2 1 8 + 3.807 10 - 3 T - 1.758 10 -6 T 2 (3)

where CF = specific heat (kJ/kg fixed carbon K) and T = temperature (K).


Knowing the total volatile matter fraction on a dry, ash-free basis, the
primary and secondary volatile matter fractions can be determined. Primary
volatile matter is taken to be the a m o u n t in excess of 10% on the dry, ash-free
basis. Its specific heat [4] is
41

Cv, = 0.728 + 3.391 X 10 - 3 T (4)


where CV, = specific heat (kJ/kg primary volatile matter K) and T = tempera-
ture (K).
Secondary volatile matter is taken to be 10% if the total volatile matter con-
tent is greater than 10%, and equals the total volatile matter content if the
amount is less than or equal to 10%. Its specific heat [4] is
CV2 = 2.273 + 2.554 X 10 - 3 T (5)

where CV~ = specific heat (kJ/kg secondary volatile matter K) and T is given
inK.
The specific heat of coal on a dry, ash-free basis can thus be evaluated as
follows:
Cp = FCF + V1Cv, + V2Cv~ (6)
where Cp = specific heat of coal (kJ/kg coal, dry ash-free K) and F, VI, V2 =
mass fractions, dry, ash-free basis, respectively, of fixed carbon, primary
volatile matter, and secondary volatile matter.
The specific heat of char, on a dry, ash-free basis, is also calculated by the
above procedure. The difference between the specific heats of the t w o sub-
stances is determined mainly b y their different compositions. The coal has a
higher volatile matter content than its resulting char, which causes a difference
in the values of F, VI and V2, used in the above specific heat equations.
The specific heat [4] of the ash in a coal or char is expressed as
CA = 0.594 + 5.86 X 10 - 4 T (7)
where CA = specific heat (kJ/kg ash K) and T = temperature (K).
The specific heat required for raising the temperature of, and vaporizing,
the moisture in the coal or char can be treated as a drying problem, with the
moisture vaporizing at a temperature corresponding to the system conditions.

Specific heat of tar

The specific heat of the tar produced in the gasification of coal can be
evaluated using the correlation developed b y Hyman and Kay [7] :
1
CT = - ~ (4.94 X 10 -3 T) (8)

where CT = specific heat (kJ/kg tar K), D -- specific gravity at 289 K/289 K
and T = temperature (K).
Using a typical specific gravity value of 1.17 [8] the equation can be rear-
ranged to give:
CT = 4.22 10 - 3 T (9)
42

This function is in excellent agreement with the measured but incomplete


values f o u n d in another literature source [9].

E N T H A L P Y OF COAL, CHAR, T A R A N D A S H

There are several methods presented in t he literature for evaluating the


standard enthalpy of coal, char, tar, and ash [2,10]. The m e t h o d chosen in
this r e p o r t is presented in this section.

Standard enthalpy of ash

Typical limits of the range o f composition of ash f r o m coals from the


United States are shown in Table 1 [11]. An average composition for ash was
obtained by taking the average o f the ext rem e limits of each corresponding
c o m p o n e n t presented in Table 1, once the averages had been normalized to a
100% distribution. T he results are shown in Table 1, which also presents the
molecular weight and standard enthalpy at 298 K for each c o m p o n e n t [ 1 2 ] .
A standard enthalpy for ash can be c o m p u t e d by summing up the products o f
the normalized weight per cent and enthalpy for each of the individual com-
ponents. This calculation results in an enthalpy of ash as - 9 4 0 . 9 MJ/kmol ash,
and an average molecular weight of 76.0 kg ash/kmol ash.

TABLE 1

Typical limits of ash analyses of coals from the United States plus normalized compositions
and corresponding molecular weights, enthalpies and entropies

Constituent Range W e i g h t Mol. wt. H S


(%) (%) (MJ/kmol) (kJ/kmol K)
(298 K) (298 K)

Silica, SiO2 20--60 38 60 -911.3 41.9


Aluminium oxide, A1203 10--35 22 102 -1674.4 51.1
Ferric oxide, F%O 3 5--35 19 160 -825.9 90.0
Calcium oxide, CaO 1--20 10 56 -634.6 39.8
Magnesium oxide, MgO 0.3--4 2 40 -601.5 26.8
Titanium oxide, TiO2 0.5--2.5 1 80 -945.2 50.2
Alkalies, Na20 + K20 1--4 2 62 -418.2 72.9
Sulfur trioxide, SO3 0.1--12 6 80 -437.9 132.7

Standard enthalpy of coal and char

The standard ent hal py of coal and char is taken to be equal to the differ-
ence between the heat of com bus t i on of the coal or char a n d the heat of com-
bustion of its constituents. A schematic o f a coal or char energy balance is pre-
sented in Fig. 1. There is disagreement in the literature on what oxidation
products (and their respective states) should be chosen in the combustion of
coal [2,10]. As can be seen in the schematic, the com bust i on of the coal con-
43

C
S02
Cool I/2 H20 -- Products
or Char
Constituents N2

Fig. 1. Schematic of coal or char energy balance.

stituents is assumed to result in the formation of CO2 (g), SO2 (g), N2 (g) and
H20(1). Using these compounds, an energy balance on the coal or char gives:

o o o o I o
& H = ~c(H~o= - HC) + ~s(Hso 2 - HS) + ~H( 2 HH20 - H~I) +
1 o o
+ ~N(~ HN2 - H ~ ) - ~O~
" H O ~o -- ~ O H O. (I0)

wh.ere
A H = heat of combustion (kJ/s)
~C, ~S, ~}H, 7}N,~/O = molar flow rate of respective coal or char constituent
(kmol/s)
Ha, S~, S~, S~, S~) = molar enthalpy of respective coal or char constituent
(kJ/kmol)
H~o~ = molar enthalpy of CO2 (g) at 298 K, -393693.3 kJ/kmol
H ~ O = = molar enthalpy of SO~ (g) at 298 K, -296954.8 kJ/kmol
Ho~2O = molar enthalpy of H 2 0 (I) at 298 K, -286518.3 kJ/kmol
HN~ = molar enthalpy of N2 (g) at 298 K, 0 kJ/kmol
Ho2 ~- molar enthalpy of 02 (g) at 298 K, 0 kJ/kmol
(It should be noted that the values used as the molar enthalpies of the above com.
ponents are based on the assumption that the heats of formation of all the ele-
ments are taken to be zero. This is similar to the approach used in references
such as the J A N A F tables [13]).
A general expression for the standard enthalpy of coal or char on a moisture
and ash-free basis is defined as:

h = +,sHs
o + HH{I + + (11)

where H = standard enthalpy (kJ/s) and the other variables are as defined above.
Substitution of eqn. (11) into eqn. (10) gives

o * o ~S o
~/o = - A H + ~cHco2 + ~sHso2 + --2 HH20 (12)

The heat of combustion of coal or char, &H , as a function of ultimate


44

analysis, is evaluated using the expression developed by IGT [ 14] :

A~o= i 152190~H + 9 8 7 6 6 .
sum 1
61
--3- +PH
sum 2
- is
8 (13)

where ~H, PC, UO, US = mass flow rate of respective coal or char constituent
(kg/s), sum 1 = summation of flow rates of C, H, O, N, S in coal or char (kg/s),
and sum 2 ~ summation of flow rates of C, H, O, N, S, ash and moisture in
coal or char (kg/s). Once the heat of combustion of the coal or char has been
determined from eqn. (13), the standard enthalpy of the coal or char at 298 K
can be evaluated using eqn. (12).

Standard enthalpy o f tar

The standard enthalpy of tar is calculated using the same procedure as out-
lined in the previous section for coal and char, with one exception. A constant
value for the heat of combustion of the tar is used in eqn. (12) instead of the
value calculated using eqn. (13). Tar produced from two widely different coals
(a Pittsburgh seam and a Wyodak seam) have been given a heat content value
of 130,000 BTU per gallon [15]. Using the specific gravity value of 1.17 pre-
sented previously, the heat of combustion of tar at 298 K is found to be equal
to 30,980 kJ/kg tar.

E N T R O P Y OF COAL, CHAR, T A R A N D ASH

Once the specific heats have been determined, as outlined previously, the
problem of evaluating the entropy of coal, char, tar, or ash is reduced to find-
ing one value of the e n t r o p y at any temperature, and then using this value to
recalculate the entropy at standard conditions (the standard entropy).

Standard entropy o f ash

Using the distribution of ash constituents and their respective entropies at


298 K presented in Table 1, a standard entropy for ash is calculated and found
to be equal to 54.0 k J / k m o l ash K.

Standard entropy of coal, char and tar

There is very little literature information on the entropy of coal. The thesis
of Lin [12] presents a value of approximately 17 k J / k m o l carbon K at 298 K
as the standard entropy of coal. Evaluating the standard entropy of coal via a
Gibbs function calculation proves to be impossible, because no equilibrium
state including coal in equilibrium with other species, such as gases, is known
45
to exist. It has been shown that the devolatilization of coal is n o t an equi-
librium decomposition, with one of the indications being that the decomposi-
tion process can proceed b y itself, even if very slowly [16]. Also, a real equi-
librium condition would allow for the devolatilization of coal to proceed in
both directions, which would imply that coal could be produced from
products of devolatilization (gases, char and tar), which definitely has n o t
been observed.
It has been shown b y several authors that the hydrocarbon structure of coal
is a combination of b o t h aliphatic and aromatic structures [8,17,18]. Based
on this information, the approach decided u p o n for evaluating the standard
entropy of coal was to observe the behavior of the standard entropy of various
solid hydrocarbons, both aliphatic and aromatic in structure. A list of the
solid hydrocarbons studied with their respective standard entropies is shown
in Table 2 [19]. The standard e n t r o p y of these hydrocarbons was evaluated as
a function of the following variables: H/(C + N), OT(C + N), N / ( C + N), and
S/(C + N), where H, C, N, O and S are the fractions of hydrogen, carbon,
nitrogen, oxygen and sulfur in the hydrocarbon, respectively, on an atomic
basis. In the development of a standard entropy function, a weighting distribu-
tion was used, which was based On the structure of the various hydrocarbons,
the hydrocarbons with ,structures more similar to coal receiving more weight
in terms of contributing to the function. This is in agreement with several coal
structure models presented in the literature [6,16].
The form of the function used, with the resulting coefficients found b y
regression analysis is as follows:

S = a, + a 2 exp (.-a3(H/C + N ) ) + a4
(o) + as

(14)
where, S = standard e n t r o p y (kJ/kmol carbon K), al = 37.1653, a2 =
- 3 1 . 4 7 6 7 , a3 = 0.564682, a4 = 20.1145, as = 54.3111 and a6 = 44.6712,
Values of the standard entropy of the c o m p o u n d s in Table 2 as predicted
b y eqn. (14) are plotted against actual values in Fig. 2. Very close agreement
is found except for some molecules containing large amounts of nitrogen.
Since such large quantities of nitrogen are n o t typical of coal, it is felt that
eqn. (14) adequately predicts standard entropies of molecules with hydro-
carbon structures similar to coal.
Eqn. (14) results in a value for the standard e n t r o p y of coal of approximate-
ly 20 k J / k m o l carbon K, and a standard entropy of char of approximately
10 k J / k m o l carbon K, based on representative values for the function variables.
Another estimation of the standard entropy of coal and char was made b y
extrapolating the specific heat values obtained b y the m e t h o d outlined from
298 K down to 0 K, and then evaluating the integral
298

f C--2P d T
T
0
46
TABLE 2

Standard entropies at 298 K for various solid hydrocarbons

Name Formula S Plotting symbol


(kJ/kmol carbon K)

Graphite C 5.743 A
Naphthalene C~oH8 16.7 B
Penta-methyl benzene CloH1, 26.0 C
2-methyl naphthalene C~IH:o 20.0 D
Diphenyl C~2Hlo 17.2 E
Hexa-methyl benzene C~2H:8 25.8 F
Anthracene C14H~o 14.8 G
Phenanthrene C~4H~o 15.1 H
1,2-diphenylethene C~4H~2 17.9 I
Octadecane C~8H38 27.6 J
Eicosane C20H42 27.9 K
Tetracosane C24H50 27.1 L
Pentacosane C2sHs2 26.8 M
Dotriacontane C32H,, 26.6 N
Tritriacontane C33H,8 26.6 O
Oxalic acid C2H204 60.0 P
Lactic acid C3H, O 3 47.4 Q
Maleic acid C4K404 40.0 R
Succinic acid C4HeO4 44.0 S
Phenol CeH~O 23.7 T
Benzoic acid C7H602 23.9 U
Hydroxybenzoic acid C7H603 25.3 V
Phthalic acid anhydride CsH403 22.0 W
Phthalic acid CsHeO4 26.0 X
Diphenylether C~2H~00 19.5 Y
Dibenzyl ethene CleH~202 19.9 Z
Dibenzyl ethane C16H1402 20.3
Dicyanodiamide C2H4N4 64.65
Melamine C3H6N, 49.7 ~,
Adenin CsHsN 5 30.2
2-cyanopyridine C~H4N2 53.75 e
Diphenylamine C~2H~IN 23.5 ~"
Benzothiaphene CsH~S 22.14
Alloxan C4H204N2 46.65 e
Hypoxanthine CsH4ON4 29.12
Xanthine C~H402N4 32.22
Hippuric acid C~H~O3N 26.59 k

A s c h e m a t i c o f the specific heat in the low t e m p e r a t u r e region is s h o w n in


Fig. 3. T h e values f o r the s t a n d a r d e n t r o p y o f coal were e s t i m a t e d using the
above m e t h o d . T h e first evaluation was m a d e using line 1 in Fig. 3 as the ap-
p r o x i m a t i o n o f the b e h a v i o r o f the specific heat in t h e region f r o m 0 K to
2 9 8 K. E v a l u a t i o n o f the a b o v e integral using this line resulted in a value f o r
the s t a n d a r d e n t r o p y o f coal o f 29.0 k J / k m o l c a r b o n K. The s e c o n d evaluation
was a conservative calculation using a straight line t o p r e d i c t the specific h e a t
behavior. This resulted in a value o f 23.0 k J / k m o l c a r b o n K. B o t h o f these
47

60

5O
es/a

4O

3o
J~, 0
20
~ For Identification of Symbols
See Table 2

I0

i I i I ] [
0o I0 20 30 40 50 60 T, K 298
S Predicted

Fig. 2. Predicted and actual values of the standard entropy of various organic molecules.
Fig. 3. Extrapolated values of specific heat.

values are comparable to the values which would be obtained using eqn. (14).
A similar calculation was made for the standard entropy of char using the
line for the specific heat of coal with zero original volatile matter c o n t e n t and
the extrapolation of this line, which is labeled number 3 in Fig. 3. The value
obtained from this calculation was 13.0 kJ/kmol carbon K, which also agrees
with the result obtained using eqn. (14).
It should be pointed out t h a t for this m e t h o d of approximating the
standard e n t r o p y to be valid, it is required t h a t there be no change in the struc-
ture of the coal or any major deviations from the proposed specific heat
behavior, especially at very low temperatures, as this will have a large effect on
the evaluation of the standard e n t r o p y integral. Actual measurements of the
specific heat of coal from 0 K to 298 K would be a possible solution to clear-
ing up this issue. Specific heat data for a temperature range above 298 K are
given by Lloyd [20] ; data below 298 K were n o t available.
The standard e n t r o p y of tar is also calculated using eqn. (14). The composi-
tion (on a dry, ash-free basis) of a tar produced in the gasification of an
]]linois No. 6 coal is presented in Table 3. Using this composition, evaluation

TABLE 3
Analysis of tar from an Illinois No. 6 coal -- moisture and ash-free basis

Constituent Wt. %

C 83.4
H 6.6
O 6.3
N 1.1
S 2.6
TABLE 4 00

S u m m a r y o f p r e d i c t i v e e q u a t i o n s f o r t h e t h e r m o d y n a m i c p r o p e r t i e s of coal, c h a r , t a r a n d ash. (See n o m e n c l a t u r e s e c t i o n f o r d e f i n i t i o n o f s y m b o l s a n d


units)
Substance Specific h e a t Ref Enthalpy Ref. Entropy Ref.
General
Coal* Cp = FC F + VICVI + V2Cv2 4 H=/~ +fCpdT
or S=S +f? dT
char
by parts
o 4e~t
C F = - 0 . 2 1 8 + 3 . 8 0 7 X 10 - 3 T 4 /~o = _~d4o + ~ C H C O2
- 1 . 7 5 8 X 10 - 6 T 2
o ~H o
+ ~SHSO2 4- ~ - - HH20
+a~ ~+N "\C+NI
= r 152190.0~H 6]
CV] = 0.728 + 3.391 X 10 - 3 T 4 ~H L ~ + 98766. 14
CV2 = 2 . 2 7 3 + 2 . 5 5 4 X 10 - 3 T 4
;c 7 o - ;s
-- + DH
3 8

stun 2

Tar C T = 4 . 2 2 X 10 - 3 T 7,8 H = "14 +f CTdT S=S +f? dT

o " o ,it,It, It~t


~o = _AHo + ~CHCO~+ ~sHso2 S = a 1 4- a 2 e x p 3 ~-N

+ ~H o
-~ HH20

AH = 30,980 kJ/kg tar 15

CA
Ash CA = 0.594 + 5.86 X 10 - 4 T 4 HfH +f CAdT S=S+ --T-'- d T
H e = - 9 4 0 . 9 M J / k m o l ash 12 S = 54.0 k J / k m o l K

* F o r coal a n d c h a r all v a l u e s a r e o n a w a t e r - f r e e basra.


* * D e v e l o p e d in this p a p e r .
49

of eqn. (14) results in a representative value of 20.798 kJ/kmol carbon K as


the standard entropy of tar.
The values obtained for the st~andard entropy of coal using the methods out-
lined are somewhat higher than the values observed in the literature. It is felt
that this is due to the fact that the methods developed here take into ac-
count the dependence of the standard entropy on composition, as is evident
from eqn. (14). This is considered to be an important fact, if the behavior of
solid hydrocarbons is to be used as means for evaluating the standard entropy
of coal.
In general, it is felt that values for the standard entropy of coal and coal
products remain somewhat uncertain at this point.

CONCLUSIONS

The equations recommended for prediction of the specific heat, enthalpy,


and entropy of coal, char, tar and ash are given in Table 4. Fig. 4 is a com-
parison of data for chars of three coals [1] on ( l i t - H273) with that predicted
using the enthalpy equations developed here. Excellent agreement is obtained.
Maximum percent deviations of the predicted values from experimental values
was found to be 18.3% with an average of 8.49% overall. Fig. 5 shows the ef-
fect of temperature on (HT - H273) for the same chars of these three coals
with solid lines resulting from the equations developed here. Fig. 6 completes
the analysis showing the predicted entropy as a function of temperature for
the chars.

Q S. Arcot Lignite--~ !
1.2 o Elkol Subbituminous-)~,~
SW Bituminous
o
l.o 1.0
c J
/
oe /- o
0.8

,R
= /-
~ 06 =o 0.6
o~ 'D (J
9o
-x
0.4 G4

,% ,~ ~ID~ S W Bituminous
z 0.2 z O.2
/ o Elkol Subbituminous
o(~ 0 S. Arcot Lignite

I 1 L I t 0 I
0.2 0.4 0.6 (~8 1.0 200 400 600 800 I000 1200
HT-Hz73, ~ (Calculated) T,K

Fig. 4. Comparison o f literature data and predicted values o f H T - H 2 v e for three different
chars.

Fig. 5. The e f f e c t o f temperatures on H T - H2~ 3 for the chars o f the three different coals.
50

4.0

S. Arcot L i g n i f e ~ , ~

Elkol Subbituminou o 0.3


3.0

5~

5 inou$
's

i
Z
c~ 2 0 ~o.2

/
z~oe
10 ~O.J
i Efkol Subbituminous
i.- o Sandow Lignite
O S. Arcat Lignite
n Grimes Lighite
O _ _ L [ _ I J-- I 0 I I I
200 400 600 800 I000 1200 QI 0.2 0.3

T,K H T -H273, MJ/kg Cool ( C a l c u l a t e d )

Fig. 6. Prediction o f the e f f e c t o f temperature on the e n t r o p y o f the chars o f three


different coals.

Fig. 7. Comparison o f literature data and predicted values o f H T - H273 for four different
coals.

3.0 S. Arcot L i g n i t e - - ~
Elkol S u b b i f u m i n o u s ~ /

Sandow L i g n i t e /

EIkol Subbituminous~/
c o Sondow Lignite
0.2 ~ 2.0
"5
o=

~' O.t

1:

I /" I 1.0 " { [ 1 I I


200 300 400 200 300 400 500 600 700
T,K T,K

Fig. 8. The e f f e c t o f temperature o n H T - H273 for three different coals.

Fig. 9. Prediction o f the e f f e c t o f temperature o n the e n t r o p y o f four different coals.


51

6.0

~_ 4.0

2.0

- 1.0

-3.0

-5,0

-7,0 I I I I I
200 400 600 800 [000 1200
T,K

Fig. 10. Enthalpy and entropy vs. temperature of a tar produced in the gasification of an
Illinois No. 6 coal.

Figs. 7, 8 and 9 repeat these comparisons and predictions, for several coals.
The agreement between the data and the predicted values is a b o u t the same as
with the chars. The maximum deviation on Fig. 7 was a b o u t 17.6% with an
average deviation of 8.55%. It is felt that the expressions adequately predict
the enthalpy of coals for most calculation purposes. The apparent differences
between predicted values and the data axe most probably due to some water
still present in the coals when the data were taken. The predicted values are on
a water-free basis. The S. Arcot coal is n o t shown on Fig. 8 while it is included
in Figs. 7 and 9 because it very closely approximates the data for the Elkol
Subbituminous coal and inclusion in Fig. 8 only added unnecessary clutter.
Fig. 10 shows the predicted behavior of the enthalpy and entropy of a tar
produced from an Illinois No. 6 coal. Due to lack of data no direct com-
parison with published results can be made of enthalpy and entropy of tars.
The equations in Table 4 are felt to adequately express the behavior of the
specific heat, enthalpy, and entropy of coal, char, tar, and ash with varying
temperature and material composition.

NOMENCLATURE

a l , a : , a3, coefficients in standard entropy function


a4, as, a6
C fraction of carbon in coal, char or tar on an atomic basis
C' mass fraction of carbon in coal, char or tar
CA specific heat of ash (kJ/kg ash K)
CF specific heat of fixed carbon in coal or char (kJ/k_g fixed carbon K)
Cp specific heat of coal or char (dry, ash-free basis) (kJ/kg K)
52

CT specific heat of tar (kJ/kg tar K)


CVI specific heat of primary volatile matter in coal or char (kJ/kg
primary volatile matter K)
Cv 2 specific heat of secondary volatile matter in coal or char (kJ/kg
secondary volatile matter K)
D specific gravity of tar at 289 K/289 K
F mass fraction of fixed carbon in coal or char on dry, ash-free basis
H fraction of hydrogen in coal, char or tar on an atomic basis
.H' mass fraction o f hydrogen in coal, char or tar
H standard enthalpy of coal, char or tar (kJ/s)
AH heat of combustion of coal or char (kJ/s)
H5 molar enthalpy of carbon in coal or char (kJ/kmol)
HCO2 molar enthalpy of CO2 (g) at 298 K (kJ/kmol)
Hfi molar enthalpy of hydrogen in coal or char (kJ/kmol)
H~I20 molar enthalpy of H20 (1) at 298 K (kJ/kmol)
Hh molar enthalpy of nitrogen in coal or char (kJ/kmol)
Hh, molar enthalpy of N2 (g) at 298 K (kJ/kmol)
molar enthalpy of oxygen in coal or char (kJ/kmol)
molar enthalpy of O2 (g) at 298 K (kJ/kmol)
molar enthalpy of sulfur in coal or char (kJ/kmol)
N fraction of nitrogen in coal, char or tar on an atomic basis
N' mass fraction of nitrogen in coal, char or tar
O fraction of oxygen in coal, char or tar on an atomic basis
O' mass fraction of oxygen in coal, char or tar
S fraction of sulfur in coal, char or tar on an atomic basis
S' mass fraction of sulfur in coal, char or tar
T temperature (K)
TI devolatilization temperature of coal (K)
V, mass fraction of primary volatile matter in coal or char on dry,
ash-free basis
y~ mass fraction of secondary volatile matter in coal or char on dry,
ash-free basis
original mass fraction of volatile matter in original drY, ash-free
coal
~C mass flow rate of carbon in coal or char (kg/s)
/~.H mass flow rate of hydrogen in coal or char (kg/s)
/~.N mass flow rate of nitrogen in coal or char (kg/s)
~.o mass flow rate of oxygen in coal or char (kg/s)
~.s mass flow rate of sulfur in coal or char (kg/s)
~c molar flow rate of carbon in coal or char (kmol/s)
~H molar flow rate of hydrogen in coal or char (kmol/s)
~.N molar flow rate of nitrogen in coal or char (kmol/s)
~.o molar flow rate of oxygen in coal or char (kmol/s)
77S molar flow rate of sulfur in coal or char (kmol/s)
sum 1 summation of flow rates of C, H, O, N, S in coal or char (kg/s)
sum 2 summation of flow rates of C, H, O, N, S, ash and moisture in
coal or char (kg/s)
53

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