Fuel 79 (2000) 1145–1154

www.elsevier.com/locate/fuel

Mathematical modeling of coal char reactivity with CO2 at high pressures

and temperatures
Gui-su Liu*, A.G. Tate, G.W. Bryant, T.F. Wall
Cooperative Research Centre for Black Coal Utilization, Department of Chemical Engineering, The University of Newcastle, Callaghan, NSW 2308, Australia
Received 26 August 1999; received in revised form 22 November 1999; accepted 23 November 1999

Abstract
Literature data on the gasification of coal chars with CO2 at moderate temperatures and high pressures has been reviewed, the focus being
the factors affecting the reactivity. A model has been developed to extrapolate this reactivity data to high-temperature conditions. The
intrinsic reactivity for various chars were predicted from the moderate temperature apparent reactivity data, assuming that reaction is in
regime I, and the effects of pressure, char type and temperature on intrinsic reactivity were obtained. The apparent char reactivity was
predicted at high temperature by incorporating the intrinsic reactivity with an effectiveness factor. It is shown that both apparent and intrinsic
reaction rates at 1123 K increase continually with CO2 partial pressure. The char type has a more significant effect on the intrinsic reaction
rate than the pressure. The char surface area is an important factor in obtaining char apparent reaction rate. Gasification temperature has the
greatest influence on reactivity. The large variation in predicted intrinsic reaction rate for various chars at high temperatures is observed due
to different activation energies. The activation energy for char–CO2 gasification generally decreases as coal char rank decreases. For
char–CO2 gasification of 100 mm particles in an entrained flow coal gasification system where the gasification temperature exceeds
1700 K, the char apparent gasification rate is limited by mass transfer in porous structure of char particles. The predicted apparent reactivity
showed a reasonable agreement with experimental measurements that were obtained under high-temperature low-pressure gasification
conditions. The extrapolated high-temperature gasification kinetics can be used in modeling the performance of an entrained flow gasifier.
q 2000 Elsevier Science Ltd. All rights reserved.
Keywords: Gasification; Coal char; Intrinsic reaction rate

1. Introduction The effect of pressure on char–CO2 gasification has been

Gasification processes have been widely applied for coal
utilization [1]. Both fixed bed and fluidized bed gasifiers
have been commercialized. Recently, gasification under
elevated pressures and temperatures, for example in an
Integrated Gasification Combined Cycle (IGCC) entrained
flow gasifier, has received greater interest due to the high
conversion efficiency and low pollutant concentrations
obtained from this technology [1].
Understanding the kinetics of the gasification reaction is
essential for designing an efficient gasifier. A number of
experiments on the char reactivity at high pressure have
been carried out for a variety of coal char types using
pressurized thermogravimetry, pressurized drop-tube
furnaces or pressurized fluidized bed reactors [2–8].
* Corresponding author. Tel.: 161-2-4921-7442; fax: 161-2-4921-8692.
E-mail address: cggsl@cc.newcastle.edu.au (G.-s. Liu).
0016-2361/00/$ - see front matter q 2000 Elsevier Science Ltd. All rights reserved.
PII: S0016-236 1(99)00274-4
extensively studied [2–8]. Most of these experiments were
performed at low temperatures, which is the case for fixed
bed or fluidized bed gasification. However, there is an
absence of experimental data for high-pressure and high-
temperature gasification in the literature.
In this work, Langmuir–Hinshelwood expressions, which
were derived on the basis of adsorption and desorption
mechanisms, have been used to model the char reactivity
at pressure [2,3]. A number of Langmuir–Hinshelwood
expressions have been proposed based on CO2 gasification
experiments performed under different conditions. These
expressions can predict the apparent reactivity at low
temperatures, typically 900–1300 K. The kinetics of high-
temperature and high-pressure gasification can be modeled
by extrapolating the high-pressure low-temperature data and
considering the effects of temperature. These effects
include: (1) the effect of temperature on intrinsic reactivity;
(2) incomplete gas penetration into the char particle; (3)
surface area reduction due to graphitization [9]; and (4)
1146 G.-s. Liu et al. / Fuel 79 (2000) 1145–1154

Nomenclature
A; B; C; D intermediate parameters used in Eqs. (A2) and (A3)
Ai pre-exponential constant for ki
E activation energy (kJ mol 21)
Ei activation energy for ki (kJ mol 21)
Da macro-pore diffusivity (cm 2 s 21)
DAB binary diffusivity (cm 2 s 21)
De meso-pore diffusivity (cm 2 s 21)
Deff effective diffusivity (cm 2 s 21)
Deff;CO CO effective diffusivity coefficient (cm 2 s 21)
Deff;CO2 CO2 effective diffusivity coefficient (cm 2 s 21)
Di micro-pore diffusivity (cm 2 s 21)
Dk;a ; Dk;e ; Dk;i Knudsen diffusivity of macro-, meso- and micro-pores (cm 2 s 21)
k reaction rate constant in the nth order equation (g cm 22 s 21 atm 2n)
ki (i ˆ 1; 2, 3 and 4) reaction rate constant (i ˆ 1, g cm 22 atm; i ˆ 2; 3, atm 21; i ˆ 4; g cm 22 atm 22)
Ki (i ˆ 1; 2 and 4) transformed reaction rate constant (i ˆ 1; g cm 22 atm; i ˆ 2; atm 21; i ˆ 4; g cm 22 atm 22)
MA ; MB ; MC molecule weight of species A, B and carbon (g mol 21)
n pressure order of nth order equation
PCO CO partial pressure (atm)
PCO;0 CO partial pressure at center (atm)
PCO;S CO partial pressure at surface (atm)
PCO2 CO2 partial pressure (atm)
PCO2 ;0 CO2 partial pressure at center (atm)
PCO2 ;S CO2 partial pressure at surface (atm)
PT total pressure (atm)
r radial distance from particle center (cm)
R gas constant ( ˆ 8.314 × 10 23 kJ mol 21 K 21 ˆ 82.057 atm cm 3 mol 21 K 21)
R0 particle radius (cm)
Ra ; Re ; Ri pore radii of macro-, meso- and micro-pore, respectively (cm)
Rapp apparent reactivity (s 21)
Rin intrinsic reactivity (g cm 22 s 21)
S surface area (m 2 g 21)
S0 initial surface area (m 2 g 21)
T particle temperature (K)
V particle volume (cm 3 g 21)
Greeks
g reaction stoichiometry
1a macro-porosity
1e meso-porosity
1i micro-porosity
1T Total porosity
h effectiveness factor
sAB force constant (Å)
fM modified Thiele modulus
4 intermediate parameter
V AB collision integral

deactivation due to thermal annealing [10]. The last two effects
contribute to a reduction in reactivity for the burnt char during
the latter stages of char burnoff [10]. These are not discussed as
they are beyond the scope of the current contribution.
The purpose of this paper was to develop a model to
extrapolate the high-pressure low-temperature gasification
reactivity data to high-pressure high-temperature con-
ditions. This study will provide kinetic data for estimating
entrained flow gasifier performance and for use in modeling
of coal gasification.
 G.-s. Liu et al. / Fuel 79 (2000) 1145–1154
2. Extrapolation of reactivity data
The extrapolation of reactivity data from low temperatures
to high temperatures was conducted using the following steps:
1. derivation of the intrinsic reaction rate for various chars
from published experiments;
2. extrapolation of the intrinsic reactivity from low to high
temperature;
3. calculation of the effective diffusivity and effectiveness
factor at high temperature;
4. generation of apparent reactivity at high temperature.
Some of the steps were formulated as follows.
2.1. Intrinsic reactivity
Most char–CO2 high-pressure gasification experiments
have been performed for char particles less than 1 mm
over the temperature range of 900–1300 K. Under these
conditions gasification reactions are controlled chemical
reactions [3,4]. The intrinsic reaction rate Rin (g cm 22 s 21)
is therefore defined as the ratio of the apparent reaction rate
Rapp (s 21) to the internal surface area S (m 2 g 21) of the
particle, as given below:
Rin ˆ Rapp =S …
Several carbon–CO2 reaction mechanisms have been
proposed in the literature [5,8,11]. In recent studies, more
modern theories were proposed under atmospheric pressure
conditions [12,13], and no rate equations were provided. In
the current study, a high-pressure reaction mechanism was
used [8], for which the reaction is composed of the follow-
ing elemental reactions:
Cf 1 CO2 $ C…O† 1 CO …
C…O† ! CO …
CO 1 Cf $ C…CO† …
CO2 1 C…CO† ! 2CO 1 C…O† …
CO 1 C…CO† ! CO2 1 2Cf …
where C…O† and C…CO† denote the oxygen complexes on the
carbon surface. Furthermore, the intrinsic reaction rate
equation was derived in the form of a Langmuir–Hinshel-
wood expression as shown in Eq. (7) [5,8]:
k1 PCO2 1 k4 P2CO2
Rin ˆ …
1 1 k2 PCO2 1 k3 PCO
where k1 ; k2 ; k3 and k4 are the temperature-dependent constants
generated from the elemental reactions (2)–(7), which can be
represented in an Arrhenius-type equation, as given below:
ki ˆ Ai e2Ei =RT …
1147
The nth order intrinsic rate equation is expressed as:
Rin ˆ kPnCO2 …9†
When compared to the nth order equation, the Langmuir–
Hinshelwood expression has three important features: (a)
the intrinsic reactivity is a nonlinear function of CO2 partial
pressure, and does not use an uncertain pressure order n; (b)
it has a mechanistic basis due to the consideration of an
adsorption–desorption two-step reaction; and (c) it includes
the inhibiting effect of the product gas (CO), which may
become significant at a high CO partial pressure.
2.2. Incomplete gas penetration at high temperatures
As gasification temperature exceeds 1700 K, which is the
case for entrained flow gasification, the char–CO2 gasifi-
cation reaction is limited by gas diffusion to the porous
matrix [14]. Hence, an effectiveness factor h , which is the
ratio of the actual rate per internal surface area to the rate
attainable if no pore diffusion resistance existed, is often
used. The apparent reaction rate Rapp is then calculated by:
Rapp ˆ hRin S …10†
The effectiveness factor h , which primarily depends on
1† particle temperature and size, can be calculated by the
well-known Thiele modulus approach [15]. In this approach
an nth order equation is used. In this study, however, the
Langmuir–Hinshelwood rate expression, rather than the nth
order one, makes it difficult to calculate the effectiveness
factor due to its nonlinear differential nature. A numerical
calculation, as given in Appendix A, is therefore presented.
The pore diffusion becomes dominant as the temperature
increases. An effective diffusivity coefficient Deff at high
temperatures is significant for the calculation of the effec-
2†
tiveness factor, and is strongly dependent on the pore size
within the particle. Conventional methods for calculation of
3† Deff use a uniform pore size that can be determined by
porosity and surface area measurements [15]. However, the
4† assumption of a single pore size would result in an erroneous
result for the case of char particles with a wide range of pore
5† sizes, and hence inaccurate reactivity predictions.
Poly-pore size models, such as the bimodal model [16]
6† and the poly-modal model [17], have been developed. The
effective diffusivity Deff ; based on the poly-modal model,
has been predicted for high-temperature char oxidation
process [18]. In the poly-modal model [17] the total porosity
of the char particle is expressed as a sum of the macro-,
meso- and micro-porosity, which is written as:
1T ˆ 1a 1 1e 1 1i …11†
7†
where 1a ; 1e and 1i are denoted as the macro-, meso- and
micro-pore porosities, respectively. The effective diffusion
rate in the particle is therefore a sum of the contributions
from the micro-, meso- and macro-pores. For a given initial
micro-, meso- and macro-pore size and porosity, the effec-
8† tive diffusivity can be calculated using following equation,
 Table 1 1148
Published experimental investigation on char–CO2 gasification at high pressure

Investigation Char samples Temperature (K) Pressure (MPa) Particle diameter (mm) Surface area (m 2 g 21) Experimental method
a
Nozaki et al. [2] Yallourn sub-bituminous char 1123 0.02–2.5 500–590 282 PDTF b
Nozaki et al. [2] Baiduri sub-bituminous char 1123 0.02–2.5 500–590 278 a PDTF b
Nozaki et al. [2] Taiheiyo sub-bituminous char 1123 0.02–2.5 500–590 358 a PDTF b
Nozaki et al. [2] Hongei anthracite char 1123 0.02–2.5 500–590 115 a PDTF b
Sha et al. [3] Xiago Long Tan Lignite char 1173 0.12–3.1 420–840 682 a PFBR c
Li et al. [4] Lignite Char 1073–1223 1.96 250–420 200 g PPBR d
Blackwood et al. [5] Jarrah purified carbon 1063–1143 4.0 1200–2400 46 RR e
Boyd et al. [6] Drayton bituminous char 1138–1240 0.05–0.75 – 12 PDTF b
Adánez et al. [7] Spanish lignite char 1073–1273 2.5 100–200 211 a PFBR f
Mühlen et al. [8] German bituminuous Char 1173 , 6.0 – 100 g PTGA h
a
Values of initial surface area are calculated from the correlation S0 ˆ 218:4 × …VM=FC† 1 98:4; which is extracted from the data published in the literature.
b
Pressurized drop tube furnace.
c
Pressurized fixed bed reactor.
d
Pressurized packed bed reactor.
e
Pressurized bed.
f
Pressurized fluidized bed reactor.
g
Values of initial surface area are taken from those for the same char type given in the literature.
h
Pressurized thermogravimetrical analysis.

(16).
Intrinsic reactivity, Rin (g.cm-2.s -1) Apparent reactivity, Rapp (s -1)

1.E-11
1.E-10
1.E-09
1.E-08
1.E-05
1.E-04
1.E-03
1.E-02
121a 1e

0
0
G.-s. Liu et al. / Fuel 79 (2000) 1145–1154

1
1
2
1 21e …1 2 1a 2 1e †
1 21a …1 2 1a 2 1e †

2
…1=Da † 1 …1=De †

3
(a)

(b)
2
2
as presented in Appendix B [17]:

4
4
…1=De † 1 …1=Di †
…1=Da † 1 …1=Di †
Deff ˆ 12a Da 1 12e De 1 …1 2 1a 2 1e †2 Di

5
macro-, meso- and micro-pores, respectively.

Total pressure, Ptotal (MPa)

Total pressure, Ptotal (MPa)

6

6
7

7
…12†

[7] lignite char; —, prediction by this work using Eq. (7) and Eqs.(13)–
intrinsic reaction rate (g cm 22 s 21) of CO2 gasification. Particle tempera-

et al. [4] lignite char; O, Boyd et al. [6] bituminous char; × , Adánez et al.
trations were 100%. S, Nozaki et al. [2] sub-bituminous char; A, Nozaki et

wood et al. [5] purified carbon; 1, Mühlen et al. [8] bituminous char; –, Li
Nozaki et al. [2] anthracite char; p , Sha et al. [3] lignite char; W, Black-
tures were adjusted to 1123 K using original rate expressions; CO2 concen-
where Da ; De and Di denote the effective diffusivity for

al. [2] sub-bituminous char; K, Nozaki et al. [2] sub-bituminous char; B,

Fig. 1. Effect of total pressure on: (a) apparent reaction rate (s 21); and (b)

3. Results and discussion
3.1. Apparent and intrinsic reaction rate
Table 1 summarizes the published experimental data for
high-pressure char–CO2 gasification for a variety of coal
types under various conditions. Fig. 1(a) shows the apparent
reaction rate against total pressure at a CO2 concentration of
100%. Particle temperatures were adjusted to 1123 K using
the original rate expressions from the literature. It can be
seen that for most of coal char types the apparent reaction
rate increases as the CO2 partial pressure increases. For
purified carbon and anthracite the reaction rate increases
with CO2 pressure up to 2.5–4 MPa. It is suggested that
the pressure effect on the reaction rate varies with coal
rank, and is significant for high rank coal. This conclusion
is inconsistent with the study by Cope et al. [19] who found
that increased pressure produced greater increases in carbon
conversion as the coal rank decreased. The apparent reac-
tion rate also varies greatly with the coal char type. It gener-
ally increases by two orders of magnitude when the char
rank decreases from purified carbon to lignite coal char.
To calculate the intrinsic reaction rate of char–CO2
gasification, particle surface area is necessary, which is
absent in some original investigations. The initial surface
area of the char particle is determined by the properties of
the parent coal, and strongly depends on the devolatilization
process [20]. In order to approximate the initial surface areas a
correlation of the initial surface area with the ratio of volatile
matter to fixed carbon (VM/FC) based on experimental data
[21,22] is presented in Fig. 2. The initial surface area for
different chars was then calculated as indicated in Table 1.
The chars derived from low-rank coals with high volatile
matter contents have the highest surface areas.
1600
1400
Initial surface area, S 0(m2g-1)
1200
1000
800
600
400
200
0
0.0
Fig. 2. Correlation of initial BET surface area of char particles measured by CO2 isotherm with volatile matter (VM) and fixed carbon (FC) contents of coal. K,
Hassimoto et al. [21]; A, Adschiri et al. [22]; and —, correlation.
G.-s. Liu et al. / Fuel 79 (2000) 1145–1154 1149
Eq. (1) has been used to calculate the intrinsic reaction
rate of chars from coals of various ranks. Fig. 1(b) shows the
intrinsic reaction rate varying with total pressure at a
corrected gasification temperature of 1123 K. The effect of
CO2 pressure on intrinsic reaction rate is almost similar to
that on the apparent reaction rate. The effect of coal char
type, however, is reduced to about one order of magnitude,
indicating that the effect of char surface area on the apparent
reaction rate is significant. Smith [23] calculated the intrin-
sic reactivity for char oxidation for various chars. Large
differences were observed in the reaction rates obtained
for the chars investigated in his study due to the variation
in atomic structure for carbon, and the different levels of
catalytic and inhibiting impurities present in the particle.
The catalytic effect of CaO in low rank coal causes an
increase in the number of active sites and hence the reac-
tivity [23]. As these chars were obtained from different
studies, their preparation methods (pyrolysis conditions
and apparatus) may also have effects on their intrinsic reac-
tivity [24]. The study of Lizzio et al. [25] has mentioned that
the CO2 surface area obtained by the physical adsorption
technique does not adequately normalize the apparent reac-
tivity, which may also be the reason for the discrepancy in
intrinsic reactivity obtained in this study. However this is
beyond the scope of this study.
3.2. Extrapolation of intrinsic reaction rate to high
temperatures
Fig. 3 shows that the intrinsic reaction rate of char–CO2
gasification depends on the temperature. The calculated
intrinsic reactivity from the experimental data is shown as
points in the figure. The extrapolated intrinsic reactivity,
over the temperature range of 1300–2100 K, is expressed
S 0 = 218 . 4 × ( FC / V M ) −1 + 98 . 4
0.5 1.0 1.5 2.0 2.5 3.0
VM/FC
1150 G.-s. Liu et al. / Fuel 79 (2000) 1145–1154

1.E+00

IGCC
1.E-02 Gasifier

E1=221.2~317.7kJ/mol
1.E-04
E1=140~153.1kJ/mol
Rin (g.cm-2..s -1) 1.E-06

Fixed bed
1.E-08 or fluidized
bed

1.E-10

1.E-12

1.E-14
0.0004 0.0005 0.0006 0.0007 0.0008 0.0009 0.001
-1
1/T (k )
22 21
Fig. 3. Intrinsic reaction rate (g cm s ) of char–CO2 gasification as a function of gasification temperature. Total pressure, 2 MPa; CO2 concentration, 100%.
Points, experimental data; lines, extrapolated trends. K, – - - –, Blackwood et al. [5] purified carbon; A, – – – –, Mühlen et al. [8] bituminous char; S, - - - - - -,
Li et al. [4] lignite char; W, – - – - –, Boyd et al. [6] bituminous char; 1, – – (fine), Adánez et al. [7] lignite char. — (coarse), prediction by this work using Eq.
(7) and Eqs.(13)–(16).

as lines. A typical entrained flow gasification lies within the
two dashed vertical lines where the temperature is in the
range of 1700–2000 K. It is shown that the temperature
has a pronounced effect on the intrinsic reactivity for all
chars. For low rank lignite char, for example, as the
temperature increases from 1100 up to 2000 K, the intrinsic
reaction rate increases by approximately four orders of
magnitude. Also observed in Fig. 3 is the effect of char
types. The differences in the intrinsic reaction rate between
chars increase from an order of magnitude at a temperature
of 1100 K to four orders of magnitude at temperature of
2000 K. At the higher temperature, the intrinsic reaction
rate is approximately 1:0 × 1022 g cm22 s21 for anthracite
char, but is only 1:0 × 1026 g cm22 s21 for lignite char,
indicating a low reactivity for low rank char.
The intrinsic reactivity expressed by the Langmuir–
Hinshelwood type rate equation does not vary linearly
with temperature. For quantitative analysis, the trend lines
are approximately regarded as Arrhenius plots. The true
activation energies for these char reactions were calculated
over the whole temperature range and are provided in Table
2. The activation energies for constants k1 ; k2 ; k3 and k4 in
Eq. (7) were provided by the literature (see Table 2). It was
found that the true activation energy E for each char is only
slightly greater than E1 ; which demonstrates that the extra-
polated intrinsic reactivity is dominated by the activation
energy E1 : The activation energy E1 is also a function of
coal rank, as indicated in Table 2. Among those chars
studied, purified carbon has higher activation energy E1
(317.7 kJ mol 21) than lignite char (140.0 kJ mol 21). The
large variation for the intrinsic reaction rate observed
between chars at high temperature is attributed to the
various activation energies E of the chars. The reported
activation energy E ranges from 170 to 250 kJ mol 21 for
most char–CO2 gasification at low pressures [26–28].
These values are close to those for bituminous and lignite
chars presented in this study.
From whole source data, the averaged intrinsic reactivity
and a set of parameters k1 ; k2 ; k3 and k4 can be obtained,
with an activation energy E1 of 212 kJ mol 21. The solid

Table 2
True activation energy E and activation energies Ei of k1 ; k2 ; k3 and k4 (kJ mol 21) shown in Eq. (7) (N/A ˆ not available)

Investigation Char Sample E E1 E2 E3 E4

Blackwood et al. [5] Purified carbon 357 317.7 0 0 359.5

Boyd et al. [6] Bituminous 306.5 221.2 296.5 2227 N/A
Mühlen et al. [8] Bituminous 171 153.1 223 248.1 68.5
Adánez et al. [7] Lignite 169.5 140.0 242 260 N/A
Li et al. [4] Lignite 149.1 N/A N/A N/A N/A

1.E-01
1.E-02
Def f (cm2.s -1)
1.E-03
1.E-04
1.E-05
1.E-06
Fig. 4. Comparison of the effective diffusivity between the extrapolations from experimental results and the model predictions. K, experimental measurements
[29]; – – –-, extrapolations from experiments [29]; solid line 1, predictions using poly-modal model [17]; and solid line 2, predictions by Valix et al. [29] using
the average pore size model [15].
lines in Figs. 1(b) and 3 indicate the dependence of the
averaged intrinsic reactivity on pressure and temperature,
respectively. The Arrhenius expressions for k1 ; k2 ; k3 and
k4 in Eq. (7) are:
k1 ˆ 0:45e2212=RT …g cm22 atm21 s21 †
k2 ˆ 0:021e23=RT …atm21 †
k3 ˆ 0:038e48:1=RT …atm21 †
210 268:5=RT 22
k4 ˆ 2:03 × 10 e …g cm atm
3.3. Effective diffusivity
The overall reactivity of char particles at high tempera-
ture can be obtained with a known effective diffusivity.
There has been little information reported on the measured
effective diffusivity for bituminous chars. The experimental
effective diffusivity Deff for brown coal char was provided
by Valix et al. [29], as shown by the points in Fig. 4; the
measured activation energy of Deff was also given as
6.2 kJ mol 21. The extrapolated effective diffusivity was
obtained over a wide range of temperatures using this
activation energy, as expressed by the broken lines in Fig.
4. The predicted effective diffusivity Deff using the single
pore model [15] and the poly-modal model [17] were also
presented and are shown using the solid lines in Fig. 4. A
large variation is observed between measured and predicted
Deff at low temperatures (,700 K) which may be attributed
to pore constrictions [29]. A difference of half an order of
magnitude is also shown between the two models through-
out the whole temperature range. At low temperatures of
around 800 K, the Deff predicted using the single pore model
[15] is close to the experimentally extrapolated value, while
G.-s. Liu et al. / Fuel 79 (2000) 1145–1154 1151
1
0 1 2 3 4
1000/T(k -1)
at higher temperatures of 1400–2000 K, the Deff predicted
using the poly-modal model shows good agreement with the
extrapolated Deff : This implies that at high temperatures, the
contribution of the meso-pores as well as the macro-pores in
the particles to the effective diffusivity becomes significant.
…13† The poly-modal pore size structure of particles allows a
better understanding of the gas diffusion in the pore matrix
…14† at high temperatures.
…15†
3.4. Prediction of apparent reaction rate at high
22 21 temperatures
s † …16†
Prior to the calculation of the apparent reaction rate (s 21),
the effectiveness factors h at various temperatures were
obtained. The averaged intrinsic parameters discussed
above k1 ; k2 ; k3 and k4 were used here. In the calculation
of the effectiveness factor, a 100 mm particle was employed
and the CO2 partial pressure was taken as 2 MPa. As a
result, the calculated effectiveness factor decreases from
unity to 0.13 as the temperature increases from 1400 to
2000 K, indicating that an increase in temperature shifts
the reaction from a chemical reaction control to a pore
diffusion control. This result is in close agreement with
the investigation by Weeda [14], who reported an effective-
ness factor of 0.2 at a temperature of 2000 K with the same
particle size. In the entrained flow coal gasification system
where gasification temperature exceeds 1700 K, the char
gasification rate is likely to be limited by mass transfer in
the porous structure of char particles.
To date there has been limited experimental data for
char–CO2 gasification at both high temperature and high
pressure. To validate the model presented two experimental
measurements of CO2 gasification at high and moderate
temperatures but at low pressures were employed. The
feasibility of these demonstrations is based on two reasons:
1152 G.-s. Liu et al. / Fuel 79 (2000) 1145–1154
Fig. 5. Comparison of the apparent reaction rate of char–CO2 gasification between experimental measurements and model predictions. CO2 partial pressure,
0.1 MPa. K, experimental by Lin et al. [9]; A, experimental by Dutta et al. [30]; —, predictions for Lin et al. [9]; and – – – –, predictions for Dutta et al. [30].
(1) the model presented is suitable over a wide range of
pressures; and (2) temperature and pressure have an
independent influence on the reactivity as indicated by the
Langmuir–Hinshelwood expression.
Fig. 5 shows that the predicted apparent reactivity is in
reasonable agreement with experimental measurements for
Newlands char [9] and for Synthane char No.122 [30]. The
apparent reaction rate of Synthane char is about half an order
of magnitude higher than that of Newlands char owing to a
larger surface area. A reduction in the apparent reaction rate
occurs at high temperature due to pore diffusion, which is
observed for both cases. It is also suggested that the averaged
activation energy E1 taken as 212 kJ mol 21 is appropriate.
Further measurements of CO2 gasification reactivity
under both high-temperature and high-pressure conditions,
and a comparison between model predictions and measure-
ments will be presented in subsequent studies.
4. Conclusions
The following conclusions can be drawn from this study.
1. For low rank coal char the apparent reaction rate for
char–CO2 at 1123 K increases as the CO2 partial pressure
increases.
2. The effect of char type is more significant compared to
pressure. The apparent reaction rate at 1123 K increases
by two orders of magnitude as the coal rank decreases;
while the intrinsic reaction rate varies with coal char rank
within one order of magnitude, suggesting that char
surface area is important in obtaining char apparent
reaction rate.
3. Gasification temperature has the greatest influence on
reactivity. A large variation in predicted intrinsic reaction
rate for various chars at high temperature is observed due
to different activation energies. The activation energy for
char–CO2 gasification generally decreases as the coal
char rank decreases.
4. For char–CO2 gasification with 100 mm particles, the
calculated effectiveness factor decreases from unity to
0.13 as the gasification temperature is raised from 1400
to 2000 K, indicating that the reaction transfers from
chemical reaction limited to pore diffusion limited. In
an entrained flow coal gasification system where the
gasification temperature exceeds 1700 K, the char
gasification rate is limited by mass transfer in porous
structure of char particles.
5. An averaged activation energy E1 taken as 212 kJ mol 21
was found to be appropriate for CO2 gasification of
bituminous coal chars. The predicted apparent reactivity
showed a reasonable agreement with the experimental
measurements that were obtained under high temperature
but low-pressure gasification conditions. This suggests
that the extrapolated high-temperature gasification
kinetics can be used for the modeling of an entrained
flow gasifier.
Acknowledgements
The authors wish to acknowledge the financial support
provided by the Cooperative Research Centre for Black
Coal Utilization, which is funded in part by the Cooperative
Research Centres Program of the Commonwealth Govern-
ment of Australia. The first comparison of effective
 G.-s. Liu et al. / Fuel 79 (2000) 1145–1154 1153

diffusivity performed by Ms Valix [29] is also Appendix B. Effective diffusivity

acknowledged.
The diffusivity Da ; De and Di for macro-, meso- and
micro-pores are given by the following equations [17,18]:
Appendix A. Effectiveness factor 1 1
Da ˆ ; De ˆ and Di
1=DAB 1 1=Dk;a 1=DAB 1 1=Dk;e
For CO2 gasification reaction C 1 CO2 ! 2CO, the reac-
tion rate is expressed in a Langmuir–Hinshelwood type 12i 1
equation [5,8]: ˆ …B1†
…1 2 1a 2 1e † AB 1 1=Dk;i
2 1=D

k1 PCO2 1 k4 P2CO2 where DAB is the molecular diffusion calculated by

p
Rin ˆ …A1† DAB ˆ …0:000000266T 3=2 =…PT s2AB V AB 1=MA 1 1=MB ††, and
1 1 k2 PCO2 1 k3 PCO
the Knudsen diffusion Dk;a ; Dk;e and Dk;i are strongly depen-
dant on the macro-pore, meso-pore and micro-pore radii,
Similar to the derivation of the effectiveness factor respectively, as indicated in the following forms:
presented by Roberts et al. [31], the internal CO2 partial s s
pressure gradients along the particle radial distance is 2 8RT 2 8RT
obtained as follows: Dk;a ˆ Ra ; Dk;e ˆ Re and
3 pMA 3 pMA
s …B2†
 ( "
p f  1
dPCO2  M 2
Dk;i ˆ Ri
8RT
ˆ 2 2  B…P2CO2 2 P2CO2 ;0 † 1 C…PCO2
dr  R0  A 3 pMA
 #)1=2
 1 1 AP 
 CO2 
2 PCO2 ;0 † 1 D ln  (A2)
 1 1 APCO2 ;0  References

[1] Harris DJ, Patterson JH. Aust Inst Energy J 1995;13:22.

The effectiveness factor is then derived as: [2] Nozaki T, Adschiri T, Fujimoto K. Fuel 1992;71:213.
[3] Sha XZ, Chen YG, Cao J, Yang YM, Ren DQ. Fuel 1990;69:293.
 p !( "
3 2 1 1 APCO2 ;S
[4] Li S, Sun R. Fuel 1994;73:413.
 1
hˆ B…P2CO2 ;S 2 P2CO2 ;0 † [5] Blackwood JD, Ingeme AJ. Aust J Chem 1960;13:194.
 fM PCO2 ;S 1 2BP2CO2 ;S A [6] Boyd RK, Benyon P, Nguyen Q, Tran H, Lowe A. Final report,
Australian Coal Association Research Program (ACARP), project
 #)1=2 
 1 1 AP   C3095. Australia: Pacific Power, 1998.
 CO2 ;S  
1 C…PCO2 ;S 2 PCO2 ;0 † 1 D ln   [7] Adanez J, Miranda JL, Gavilan JM. Fuel 1985:801.
 1 1 APCO2 ;0   [8] Mühlen HJ, van Heek KH, Jüntgen H. Fuel 1985;64:591.
[9] Lin SY, Hirato M, Horio M. Energy Fuels 1994;8:598.
…A3† [10] Hurt R, Sun J-K, Lunden M. Combust Flame 1998;113:181.
[11] Gadsby J, Long FJ, Sleightholm P, Sykes KW. Proc Royal Soc
where: fM represents the modified Thiele modulus and can 1948;193:357.
[12] Kapteijn F, Meijer R, Moulijn JA. Energy Fuels 1992;6:494.
be expressed as [31]
[13] Chen SG, Yang RT, Kapteijn FK, Moulijn JA. Ind Engng Res
1993;32:2835.
!1=2 [14] Weeda M, University of Amsterdam, Amsterdam, 1995.
K1 SRT
fM ˆ R0 …A4† [15] Wheeler A. Advances in catalysis, VIII. New York: Academic Press,
VDeff;CO2 MC 1951. p. 1797.
[16] Smith IW, Tyler RJ. Fuel 1972;51:793.
[17] Wakao N, Smith JM. Ind Engng Chem Fundam 1964;3:133.
and PCO2 ;0 is a partial pressure of CO2 at the particle center, [18] Reade WC, Morris K, Hecker WC. Coal Sci Technol 1995;24:222.
which can be obtained by solving Eq. (A2) using the [19] Cope RF, Smoot LD, hedman PO. Fuel 1989;68:807.
Runga–Kutta numerical method [32]. A, B, C and D in [20] Lee CW, Jenkins RG, Schobert HH. Energy Fuels 1992;6:40.
Eqs. (A2) and (A3) are the constants expressed as A ˆ K2 ; [21] Hashimoto K, Miura K, Ueda T. Fuel 1986;65:1516.
[22] Adschiri T, Shiraha T, Kojima T, Furusawa T. Fuel 1986;65:1688.
B ˆ K4 =2K1 ; C ˆ 1 2 …K4 =K1 K1 † and D ˆ 2……1=K2 † 2 [23] Smith IW. Fuel 1978;57:409.
…K4 =K1 K22 ††; respectively. K1 ; K2 and K4 are the alternated [24] Megaritis A, Messenbock RC, Collot A-G, Zhuo Y, Dugwell DR,
reaction constants, and are defined as K1 ˆ k1 =v; K2 ˆ Kandiyoti R. Fuel 1998;77:1411.
…k2 2 k3 gDeff;CO2 =Deff;CO †=v and K4 ˆ k4 =v; and intermedi- [25] Lizzio AA, Jiang H, Radovic LR. Carbon 1990;28:7.
ate constant 4 is expressed as v ˆ 1 1 k3 …PCO;S 1 [26] Osafune K, Marsh H. Fuel 1988;67:369.
[27] Knight AT, Sergeant GD. Fuel 1982;71:879.
PCO2 ;S gDeff;CO2 =Deff;CO †; where Deff;CO2 and Deff;CO are the [28] Hampartsoumain E, Murdoch PL, Pourkashian M, Trangmar DT,
effective diffusivities of CO2 and CO in the particle, Williams A. Combust Sci Technol 1993;92:105.
respectively. [29] Valix MG, Harris DJ, Smith IW, Trimm DL. Proceedings of the 24th
1154 G.-s. Liu et al. / Fuel 79 (2000) 1145–1154

Symposium (International) on Combustion. The Combustion [31] Roberts GW, Satterfield CN. Ind Engng Chem Fundam 1965;
Institute, 1992 p. 1461. 4:123.
[30] Dutta S, Wen CY, Belt RJ. Ind Engng Chem Process Des Dev [32] Liu G-S, Tate AG, Rezaei HR, Beath AC, Wall TF. Dev Chem Engng
1977;16:20. Miner Process 1999;7:525.