Fuel Vol. 77, No. 15, pp.

18311839, 1998
1998 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
0016-2361/98 $19.00+0.00

PII: S0016-2361(98)00123-9

Reactivity of coal gasification with

steam and CO 2
Alejandro Molina and Fanor Mondragon*
Chemistry Department, University of Antioquia, A.A. 1226, Medelln, Colombia
(Received 14 March 1997; revised 12 February 1998; accepted 30 July 1998)

A description of the main parameters affecting char gasification, as well as an evaluation of the kinetic models
used for describing the char gasification reaction, are presented. By reviewing literature on char gasification
reactivity it is shown that of all the parameters involved in char gasification, the thermal history of the char, the
pore structure and the coal chemical composition are those which present the most different results. The
examination of reactive models indicates that their use depends mainly on their purpose in use. 1998 Elsevier
Science Ltd. All rights reserved
(Keywords: coal; gasification; models)

Nomenclature
a

r
Rc
RCO dx=dtlt 0
Ru

parameter for Dutta and Wen model in eqn (31),

empiric constant for homogeneous model in eqns (33)
and (34)
constants for Gavalas pore random model in eqns (26)
and (27)
active surface area (m 2/g)
empiric constant for homogeneous model in eqns (33)
and (34)
concentration of gaseous reactant A (mol n lt n) in
eqn (21)
concentration of gaseous reactant (mol lt 1) in
eqn (32)
relative reactive factor in eqn (30)
kinetic reaction constant (s 1)
rate constant in eqn (47)
rate constant for surface reaction (m 2 lt n mol n s 1)
in eqn (21)
kinetic constant (s 1) in eqn (30)
pore length at t 0
non-reactive core model parameter in the unification
theory model
generalized m
reaction order in eqn (21)
rate constants in reaction (44) and (41)
normalized gasification rate (g g 1 s 1) in eqn (6);
pore radius (m) in eqns (22) and (24)
gasification rate (g g 1 s 1)
rate constant for a particular experiment in eqn (41)
initial reaction rate in eqn (37)
unified constant for gasification rate in eqn (40)

So
S (x)
t
t 1/2
V o(r)
W
Wo
x
a
b

surface area at t 0 (m 2/g)

surface area (m 2/g)in eqn (35)
time (s)
half time of gasification reaction (s)
pore volume distribution (m 2/g)
mass (d.a.f.) of char at time t (g)
initial mass of the char
char conversion
Johnsons kinetic parameter
empiric parameter in eqn (31)

A o and A 1
ASA
b
Cn
Cg
f1
k
k1
Ks
kt
Lo
m

m
n
q 1, q 1 and q 2
r

* Corresponding author.

o
n
t K sC nS ot/1- o
t
Q
w 4pL o(1- o)/S2o
w

coal porosity at t 0
empiric constant for eqn (31)
dimensionless time in eqns (19) and (20)
dimensionless time in eqns (36), (38) and (39)
coal moisture holding capacity (g H 2O/g dry solid)
structural parameter in eqns (19), (20) and (39)
unified w

INTRODUCTION
Coal gasification has emerged as a clean and effective way
for the production of gas which can be used for power or
heat generation or as a synthesis precursor. A good
understanding of the char reactivity makes it possible to
improve gasifier design and efficiency.
A distinction of the factors affecting char gasification can
be made according to whether they are only related to the
intrinsic chemical characteristics of the char, or if they can
be related to the physical structure of the coal or to the
environment in which it goes through chemical reactions
(combustion or gasification). In this way, the first are said to
represent the char reactivity and the second are related to the
respective reaction rates. Once the kinetic parameters (or
constants) are determined for a given coal, the respective
reaction rates can be computed taking into account several
factors, such as: temperature, pressure, composition of the
atmosphere surrounding thecoalorcarbonaceousparticles,etc.
This paper attempts to review both, the different
parameters affecting char reactivity and the influence of
some factors affecting the gasification reaction rates. It also
includes a summary of the most important kinetic models
proposed for char gasification, as well as the effectiveness of
these models on the prediction of char reactivity.
GASIFICATION REACTIONS
Coal gasification is a two step process: pyrolysis and char
gasification. The first step, pyrolysis, involves the evolution

Fuel 1998 Volume 77 Number 15 1831

Reactivity of coal gasification with steam and CO 2: A. Molina and F. Mondragon

Figure 1 CO 2 char gasification 800C; Cerrejon coal23

of compounds of low molecular weight, at temperatures

between 300 and 500C. These compounds are mainly tars
and non-condensable gases.
Normally, pyrolysis residue or char represents from 55 to
70% of original coal. At the usual temperatures of
combustion and gasification processes, the char gasification
reactions are slower than the pyrolysis ones. Therefore, only
those elements affecting char gasification reactions are
considered in the present study.
During char gasification, the following main reactions
may be considered1. A more detailed list of independent
chemical reactions can be found in a recent book2.
C CO2 2CO DH 159:7 kJ mol 1

(1)

C H2 O CO H2 DH 118:9 kJ mol 1

(2)

C O2 CO2 DH 405:9 kJ mol 1

(3)

CO H2 O CO2 H2 DH 40:9 kJ mol

C 2H2 CH4 DH 87:4 kJ mol 1

(4)

(6)

where r is the normalized gasification rate, t is time, W is the

char mass at time t (d.a.f.), x is char conversion,
x

Wo W
Wo

(7)

and W o is the initial mass of char, and

r

1 dW dx

Wo dt
dt

(8)

In this case r is considered as the gasification rate. It should

be stated that although the most used expression is eqn (6),
some authors35 use eqn (8) as well.
TYPICAL RESULTS IN COAL GASIFICATION
When considering the reactivity of coal gasification, the
behaviour of the conversion versus time (x versus t) and that
of the reaction rate versus conversion (r versus x or r versus
x) are studied when char is reacting with CO 2 or H 2O at
temperatures between 800 and 1200C.

Relationship between steam gasification rate and %C in coal25

1832 Fuel 1998 Volume 77 Number 15

1 dW
1 dx

W dt
1 x dt

(5)

Reactions (1) and (2) are endothermic, and can be considered as the most important in a gasification process. Oxidation reaction (3) provides the energy needed for the
promotion of reactions (1) and (2). The shift reaction (4)
occurs mainly at high steam concentrations, while reaction
(5) is more important at high pressures.

Figure 2

As gasification proceeds, the char loses mass. The burnout rate is used to determine the gasification reactivity.
There are two ways in which the gasification rate can be
considered:

Reactivity of coal gasification with steam and CO 2: A. Molina and F. Mondragon

Figure 3 Relationship between CO 2 gasification rate and the %C in coal25

In general, the curves of conversion against time show a

similar shape, regardless of coal type and experimental
conditions 620. The curve is almost a straight line up to
x 0.75.
On the other hand, there is no agreement regarding the
variation of the gasification rate with conversion. Some
authors3,7,17,18,21,22 have found a maximum rate for conversions between 20 and 60%, as can be seen in Figure 1 for a
Colombian coal23, Cerrejon (82% C). Others12,24 found a
linear decrease of gasification rate as reaction advances.
Finally, some studies10,11,13,15 regarding coal reactivity
during gasification, do not consider gasification rate
variation with conversion and only report the gasification
rate at a specific value of conversion.

Therefore, by making the pyrolysis temperature equal to the

gasification temperature, laboratory work will become more
representative of industrial reactor work.
Chin et al.12 and Goyal et al.14 also considered that
pyrolysis and gasification temperatures should be the same
when coal reactivity is to be determined. Goyal et al. carried
out a gasification of chars taken from a pilot U-GAS
(fluidized bed) bituminous coal gasifier. The chars were first
gasified at 980C. The authors found that the experimental
kinetic constant (0.045 min 1) was lower than the theoretical value (0.0774 min 1). However, when the same chars
were gasified at 1038C, experimental and theoretical
constants matched very well. This meansas the authors
suggestthat pyrolysis in the pilot U-gas gasifier occurs at
1038C.

FACTORS AFFECTING THE REACTIVITY OF COAL

Pore structure
It could be thought that pore structure is a physical factor
which would be better related to the gasification rate than to
the reactivity. Nevertheless, the relationship between char
porosity and active sites concentration, as will be shown,
suggests that pore structure should be related to char
reactivity.
The reaction rate of the char changes with conversion
(Figure 2). Normally, this change would be related to
changes in pore structure during reaction, but there is no
unanimous approach. Adanez and de Diego13 did not find
any variation in surface area as reaction advances. On the
other hand, Adshiri et al.24 considered that the gasification
rate is proportional to the surface area during gasification.
However, the most common result is that surface area
presents a maximum value, as does the reaction rate, for
conversions between 20 and 60% (Figure 4).
There is no consensus either concerning the pore diameter
where gasification reaction takes place. Dutta et al.3, Chi
and Perlmutter17, Gavalas18 and Bhatia and Perlmutter21
found that the main contribution to the surface reaction area
is made by the micropores. This overrides the effect of the
macropores since the surface area originated by the latter is
insignificant. In other words, the surface area occupied by
is 10 m 2 g 1, while that occupied by pores
pores above 30 A

below 20 A is more than 25 m 2 g 1 3.

On the other hand, Hurt et al.27 found that gasification
occurs mainly outside the micropores, that is, on the
macropores surface. They maintain that this is not due to
diffusion restrictions, since chars with a larger pore
diameter do not have higher reactivity. They propose

Coal reactivity is affected by different variables which

involve the coal properties that can not just be related to coal
physical structure or to process parameters. An attempt to
describe the influence of these variables in coal reactivity is
given in the following sections.
Coal rank
Coal reactivity decreases as coal rank increases. Miura
et al.25 found (Figure 2) that the gasification reactivity data
of chars prepared from 68 different coals by different
authors, were very scattered for low rank coals (%C 80),
but the reactivity was higher than that obtained for higher
rank coals. When carbon content was more than 80%,
reactivity data were less scattered, but decreased as rank
increased. For the CO 2 reaction, the same behaviour was
found (Figure 3).
Thermal history of the char (pyrolysis)
Several factors concerning the pyrolysis may affect the
reactivity, such as, the volatile content, the temperature at
which coal is pyrolysed26, the extension of the pyrolysis, the
heating rate and the gas atmosphere at which the pyrolysis
occurs25.
Due to this strong influence of pyrolysis in gasification, it
is usedwhen determining coal reactivityto pyrolyze
coal at the same temperature as it will be gasified. Adanez
and de Diego13 stated that although there is a theoretical
mistake when kinetic constants are determined in compounds of different heat-treatments, pyrolysis occurs at the
same temperature of gasification in an industrial gasifier.

Fuel 1998 Volume 77 Number 15 1833

Reactivity of coal gasification with steam and CO 2: A. Molina and F. Mondragon

Figure 4 Surface area variation during char gasification

instead that there is a higher concentration of active sites in

macropores than in micropores. Macropores might appear in
crystallite edges or sites in contact with catalytic active
inorganic impurities, while micropores would be composed
of basal planes, which are less reactive.
The above result is based on the fact that subbituminous
coals, heat-treated up to 1200C, showed a decrease in
reactive surface area from 510 down to 4 m 2 g 1, while
gasification rate was only reduced by a factor of about 4.
During gasification, surface area increases from 4 up to
250 m 2 g 1, while char reaction rate always decreases.
Clemens et al.28 showed that it is possible to achieve the
same reaction rate of untreated coal by adding a fraction
(25%) of the calcium of untreated coal to acid washed coals
which go through steam gasification (900C). According to
them, this could be explained by the difference between the
reactivity of micropores and macropores.
Although the relationship between reaction rate and
surface area has been widely studied3,7,12,16,19,20,29,30 there
is no general agreement. Chin et al.12 and Adshiri et al.24
state that reaction rate is proportional to surface area.
However, most of the studies3,7,16,19,29,30 found that surface
area and reaction rate are not proportional. Proportionality is
rather found between reaction rate and other parameters
such as ASA16,24 (Active Surface Area) or Q16,19 (coal
moisture holding capacity). ASA is related to the amount of
oxygen chemisorbed by coal, and Q with the total micropore
volume25. Parameters like ASA and Q are apparently more
related to the number of active sites on coal surfaces, rather
than to the total surface area. This is in accordance with new
theories of gasification reaction.
Chemical structure of coal
The influence of chemical structure of coal in gasification
reactivity has not been as thoroughly studied as other coal

1834 Fuel 1998 Volume 77 Number 15

properties. Most of the attempts to find a relationship

between reactivity and chemical structure have ended in
numeric expressions relating fixed carbon, moisture holding
capacity and reactivity7,20. In fact Martinez et al.31, working
with lignite coals of different chemical compositionone
oxygen rich with low aliphatic hydrogen content, and
another aliphatic hydrogen rich with low oxygen content
concluded that chemical composition has no influence on
the air gasification rate, since both coals had almost the
same reactivity. No further relation has been found in the
reviewed papers.
However, studies of the gasification reaction mechanism
are still being made. From the molecular point of view, it is
necessary to consider the role of active sites when the
reactivity of carbonaceous materials is studied. In the case
of carbon gasification with molecular oxygen, several
authors3235 have suggested the existence of oxygen on
the basal plane of aromatic structures during gasification
reactions. This oxygen is considered an additional oxygen
source in gasification reactions. Theoretical calculations
based on molecular orbital theory suggest that when oxygen
is placed in the basal plane, the CC bond strength of the
bridging atoms can be reduced by 30%. That means that
the reactivity of carbonaceous material will also depend on
the capability of trapping oxygen in the basal plane.
Chen and Yang35 showed that a potassium atom, forming
a phenolate in coal structure will not reduce the bonding
strength of CC bridging atoms, but will reduce the net
charge of the bridging C atom, and consequently the
possibilities of trapping an oxygen atom in the basal plane
will increase, thereby increasing reactivity.
Based on the existence of this oxygen, different
mechanisms have been proposed for CO, CO 2 production
in noncatalytic and catalytic reactions, as shown in Figure 5.
This figure shows that CO 2 production implies the

Reactivity of coal gasification with steam and CO 2: A. Molina and F. Mondragon

Figure 5 Proposed mechanism for CO and CO 2 production during carbon gasification33

Table 1 Incidence of reactive gases concentration in char gasification14; P 7.8 atm, T 1310.9 K
Gasification rate (min 1)

Reactive gas composition (%)

H2

H 2O

CO

CO 2

50

50

0.106

50

50

0.061

30

50.3

11.5

8.2

0.047

simultaneous cleavage of three bonds, and the formation of

another CO. Although this reaction occurs at high
temperatures, this event has little chance of success.
FACTORS AFFECTING REACTION RATES
In contrast to reactivity, some factors that are solely related
to the physical structure of coal or to the conditions in which
reactions take place are said to affect the reaction rate.
Reactive gases concentration
Char gasification reaction is considered a first order
reaction, both for CO 2 and steam, when working at
pressures below atmospheric pressure3,7,12,14. For pressures
above atmospheric, the reaction order approaches zero.
Shufen and Ruizhang8 found that for lignite coals at
1.6 MPa, reaction orders were 0.26, 0.34 and 0.50 for steam,
CO 2 and H 2, respectively. On the other hand, Goyal et al.14
showed that there is no steam pressure dependence in a
range of 0.72.8 MPa when gasifying bituminous coals.
This contradiction can be explained since the more reactive
lignites may be more affected by steam pressure than the
less reactive bituminous coals.
Another factor to be considered regarding reactive gases
concentration is the inhibition by H 2 and CO. Some
studies14,20,36 have shown a retarding effect when CO and
H 2 are produced. Table 1 shows the inhibitory behaviour of
H 2 and CO. The gasification rate decreases almost 42%
when H 2 concentration is the same as that of H 2O. At the
same time, a further decrease is observed when CO and CO 2
are added to the reactive gas.
This inhibitive phenomenon has been extensively
explained by LangmuirHinshelwood relations11,20. The
proposed mechanism is:
C CO2 C(O) CO
C(O) CO

(9)
(10)

The main characteristic of this mechanism is the inhibition

made by the CO produced which will shift reaction 9 to the
left.
However, recently Moulijn and Kapteijn34 considered
that the inhibitory mechanism does not fully explain the

N2

reduction of gasification rate by H 2. Experimentally they

found that gasification reaction stops almost completely
when hydrogen concentration is more than 50%. This
suggests that H 2 is part of two different mechanisms during
gasification, a reversible reaction which agrees with the
LangmuirHinshelwood kinetics, and an irreversible reaction which leads to the deactivation of the active sites. The
proposed mechanism is:
Cf H2 O C(O) H2

(11)

Cf H2 CF H2 (Inhibition)

(12)

2Cf H2 2C H (Deactivation)

(13)

C(O) CO Cf

(14)

Pressure
Although the incidence of the partial pressure of the
reactive gases in the char gasification rate has been
exhaustively studied3,7,1214,17,20,36, there is a dearth in the
open literature concerning the influence of the total system
pressure.
Schmal et al.15 found that total pressure affects gas
composition during steam coal gasification at 8501000C
in a fluidized bed. High pressures do not alter the system H 2
concentration to any extentfrom 61% at 0.1 MPa, to 58%
at 1.0 MPabut it increases methane concentration from
1.1% (0.1 MPa) to 2.0% (1.0 MPa). The CO/CO 2 ratio also
decreases for higher pressures.
In the same research, it was found that the gasification
rate increases with total pressure and its effect is more
marked in the low pressure region. For example, the
reactivity doubles its value when pressure is raised from 0.1
to 0.5 MPa. However, pressure values above 1 MPa do not
produce a significant increase in gasification rate.
Sample size
When char reactivity is studied, laboratory experiments
are generally done in such a way that diffusive restrictions
can be avoided. The analysis is done by plotting char
conversion against time for different particle sizes. Diffusion restrictions should be considered when burn-off curves
begin to level off for larger particles. This means that

Fuel 1998 Volume 77 Number 15 1835

Reactivity of coal gasification with steam and CO 2: A. Molina and F. Mondragon

particle size should be small enough so that no difference

can be found in reactivity if a smaller particle is used for
reactivity studies.
The particle size where diffusion restrictions can be
neglected depends on coal type. Kovacik et al.10 found
diffusion restrictions for subbituminous and bituminous
coals at 900C and particle size above 105 74 mm. On
the other hand, Matsui et al.11 did not find diffusion
restrictions when working with subbituminous 710-mm coal
particles. Chin et al.12 worked with coal particles up to
1000 mm, without finding any diffusion effect.
Such differences have made every research team change
the particle size in order to find the experimental conditions
where diffusion restriction can be neglected.

REACTION MODELS FOR CHAR GASIFICATION

REACTION
Different models have been proposed to describe the char
gasification reaction. Models which do not consider coal
structural changes during reaction are the most simple. The
homogeneous model, and unreacted core model are
examples of this type of models.
Homogeneous model13
This model reduces the heterogeneous gassolid reaction
of coal gasification to an homogeneous reaction by
assuming that the gas is reacting with char in all possible
places, both outside and inside the particle surface. Reaction
rate expressions are:
x 1 exp( kt)

(15)

dx
k(1 x)
(16)
dt
where k is the kinetics reaction constant and x is the conversion.
Non-reacted core model37
Reacting char particles are considered as spherical grains
whose radius decreases as the gasification reaction
advances. If chemical reaction is the controlling step,
reactivity expressions are:
x 1 (1 kt)

(17)

dx
3k(1 x)2=3
(18)
dt
where k is the kinetics reaction constant.
Random pore models, in contrast, do consider physical
structural changes during the gasification reaction.
Random pore model (1980)
Bhatia and Perlmutter21 and Gavalas18 found that a
random pore model can be applied to coal gasification
reaction. Bhatia and Perlmutter considered the random
overlapping of pores surfaces, which reduced the area
available for reaction. The equations of this model are:



wt
(19)
x 1 exp t 1
4
p
dx
(1 x) [1 w ln(1 x)]
dt

1836 Fuel 1998 Volume 77 Number 15

(20)

with
t

Ks C n So t
1 o

(21)

where S o is the surface area at t 0,

Z
Vo(r)
dr
(22)
So
0
r
V o(r) is the pore volume distribution (m 2/g) determined by
CO 2 at 273 K,
w

4pLo (1 o )
S2o

(23)

is a structural parameter, L o is the pore length at t 0,

Z
1
Vo (r)
dr
(24)
Lo
p 0 r2
and o is the coal porosity at t 0,
Z
1 X
V (r)dr
(25)
o
p 0 o
S o, L o and o represent the surface area, length and total
volume of a system which is made by the random overlapping of cylindrical surfaces whose size distribution is
V o(r).
Gavalas18 also considered the random pore overlapping
in the char reaction. But unlike Bhatia and Perlmutter, he
assumed the shape of pores as cylindrical, straight and
infinitely long capillaries. He used a single density
function for calculating the number of overlappings, the
length of pores, and the change of volume and area during
reaction.
By this treatment, he obtained the following relations:
(26)
x 1 exp[ 2pt(Ao t 2A1 )]
q
dx
4p(1 x) A21 Ao ln(1=1 x)
(27)
dt
where A o and A 1 are empirical constants.
It should be noted that the above model considers
equations similar to those of Bhatia and Perlmutter.
x 1 exp[cte1 t(1 cte2 t)]

(28)

p
dx
(1 x) 1 cte1 ln(1=1 x)
(29)
dt
The main difference is the way for finding the constants.
A third group of authors3,57,14,24,38 considered that none
of the theoretical models, either structural or nonstructural,
describes experimental results in an acceptable way. They
proposed semiempirical models as follows.
The Johnson model14
According to this model:
dx
f k (1 x)2=3 exp( ax2 )
(30)
dt 1 t
where f 1 is the relative reactive factor, which depends on
char type and heat-treatment temperature; k t is a kinetic
constant, which depends on partial pressures of reacting
gases; ax 2 represents the relative influence of the effective
surface area, which decreases with conversion. If a 0, the
Johnson model becomes the same as the non-reacting core
model; if a 1, the model can be represented by the homogeneous model for conversions below 0.75.

Reactivity of coal gasification with steam and CO 2: A. Molina and F. Mondragon

The Dutta and Wen model3

Dutta introduces a new factor a into the rate expression.
This a is defined as the ratio between the available pore
surface area per unit weight at any stage of conversion and
the initial pore surface area per unit weight.
(31)
a 1 100xnb exp( bx)
Here, n and b are constants which depend on each char. The
rate expression for this model is therefore:
dx
akCg (1 x)
(32)
dt
which is the same equation as that for a homogeneous reaction (16), except the new factor a has been included.
Modified volumetric model (1985)6,7,9,39
This model was developed by Kasaoka et al. and it
modifies the equation of the homogeneous model, adding a
new parameter, the time power (b):
x 1 exp( atb )

(33)

dx
a1=b b(1 x)[ ln(1 x)]b 1=b
(34)
dt
where a and b are empirical constants.
This model applies a reaction order (b) to the homogeneous model. It seems that by applying this order, the
homogeneous model expressions get closer to random pore
models, in which a two-order polynomial is the power of the
time (eqn (28)).
24

The Adshiri and Furusawa model

These researchers considered that the homogeneous
model is enough for high porosity (0.5) chars. They
include the value of the surface area, and by semiempirical
experiments conclude that:
dx
S(x) k k(1 x)
(35)
dt
where S(x) is the surface area.
Unification theory model40
This model is based on the fact that when conversion (x)
is plotted against dimensionless time t t/t 1/2 where t 1/2 is
the half-life time for chargas reactionirregardless of
temperatures, pressures, gasifying agents and coals, all the
experimental plots can be described by only one curve for
conversions 0.7.
The equation which this model considers is based on the
non-reactive core model (order m for gas):
x 1 [1 RCO (1 m)t]1=1 m

(36)

dx
RCO (1 x)m
(37)
dt
and on the Bhatia and Perlmutter21 random pore model, but
modified for x 0.5 and t t 1/2:
The unification equation for the unreactive core model
(parameter m) is:
(38)
x 1 [1 {1 (1=2)1 m }t]1=1 m
The unification equation for random pore model (parameter
w) is:
x 1 exp[ p(t pwt2 =4)]
p

(1 w ln 2)
w=2

1=2

(39a)
(39b)

By adjusting experimental x versus t information, it is

and w w which will
possible to find values of m m
unify any gasification. The authors use experimental data
from 110 gasification experiments and found the following
0.5 and w w 2.7.
values m m
They also supposed that the gasification rate is only a
function of conversion, hence a unified constant for
gasification rate can be defined as:
Z1
Ru dx=dt

(dx=dt)dx Z1

(dx=dt)dx
Z1
0
dx

(40)

and the rate constant for a particular experiment would be:

Rc (dx=dt)

Z1
0

(dx=dt)dx

(41)

Finally:
t1=2 Rc Ru

(42)

By eqn (42), it is possible to compute the gasification rate

for a particular experiment just by knowing the half-life
time, and the unified constant for gasification rate, R u.
Raghunathan and Yang40 found that by applying eqn (40)
to data from six different laboratories, coals, temperatures
and gasifying agents, that 0.366 R u 0.393, and they
assume R u 0.38. Hence:
Rc 0:38=t1=2

(43)

and the previous equation allows one to find the constant for
the gasification rate, just by knowing the half-life time for
each experiment.
Recent developed model38
A relatively recent approach to the modeling of chargas
reaction kinetics was made by Liliedahl and Sjostrom38.
Their model is based on the following gasification
mechanism:
q1

C C

(44)

q1

q2

H2 O, CO2 , CO and=or H2

gas

(45)

where q 1 and q 2 are rate constants, C denote a free char and

C * an active site. From this mechanism and considering a
non-steady-state model the following equations are derived:
x cosh(kk1 ) exp( kt)

(46)

x (1 kk1 t) exp[ k(k1 1)t]

(47)

where k and k 1 are kinetic constants which depend on the

nature and pressure of the gasifying agent. The first equation
would be representative of gasification rates which decrease
with conversion, whereas the second one would be related to
increasing gasification rates. Although good agreement is
claimed between the reactivities predicted by eqns (46)
and (47) and actual results for a CO 2 gasification at 770
800C, the position of when each equation should be used
was not addressed.
Other empirical models
Another approach is the use of completely empirical
models for the prediction of char reactivity during
gasification. In this case a two-order polynomial is used to

Fuel 1998 Volume 77 Number 15 1837

Reactivity of coal gasification with steam and CO 2: A. Molina and F. Mondragon

describe gasification reaction, e.g. the Mahajan model

(1978) and the parabolic model5.
VALIDITY OF KINETICS MODELS
The efficiency of kinetic models in predicting the coal
reaction rate during gasification depends mainly on the type
of coal, the purpose of char reactivity evaluation, and the
experimental conditions.
If the main intention for studying coal reactivity is just to
describe the relation between time and conversion, homogeneous and non-reactive core models are preferred (as can
be seen in Table 2). This is because of its mathematical
simplicity, and the conversion-time behaviour is well
described by these models. Usually in these studies the
change of kinetic parameter constants with conversion is not
considered and char reactivity is found for a specific
conversion figure. This is the case in Refs 2,14,11,24. All of
these use either the homogeneous or non-reactive core
model for determining the reaction rates. Souza-Santos41
included a correction to account for the coal reactivity based
on the volatile content. In addition, he states that by a simple
evaluation of the residues of a coal boiler or gasifier, it is
possible to decide whether a non-reactive core model
(relatively large char particles in ash) or a homogeneous
model (small and cracked particles) is better.
However, when all factors affecting reactivity are
considered, the non-reactive core model or the homogeneous model fail to precisely describe the changes in
reaction rates with conversion. On the other hand, these
models are useful for approximate computations. Of course,
when available for a specific coal, semi-empirical and
random pore models are preferable (Table 2). These models
can describe a maximum in reaction rate and hence
experimental information. Nevertheless, they are not
frequently used since they have a more complex mathematical structure, and since there is not a big difference in the
way these models describe conversion-time behaviour, in
comparison to the homogeneous and non-reactive core
models.
Sometimes the purpose of a study is to compare the
reactivity of different coals, as in catalyst investigations. If
this is the case, the modified volumetric model6,7,9,39 and
unification theory40 are mostly used.
Table 2 Use of kinetic models for prediction of coal gasification
reactivity
Purpose of research
x versus t

dx/dt versus x

Kinetics constant

Model

Table 2 shows a summary of the implementation of

different models in the determination of coal reactivity. It
can be seen, as previously explained, that the model used
depends mainly on the purpose of the research.
CONCLUSIONS
The influence of coal rank, reactive gas concentration,
system pressure and sample size in char reactivity and
gasification rate, has been widely studied and there is an
agreement among different authors. However, the incidence
of factors, such as thermal history of char, pore structure and
coal chemical composition, on char reactivity and gasification rate, is not so well defined and there still remain some
contradictions in the literature.
There is no mathematical model that can describe exactly
both conversion behaviour against time, and rate variation
with conversion and consequently, the model selection
depends on the purpose of the reactivity determination.
ACKNOWLEDGEMENTS
The authors thank Colciencias, Ecocarbon and University of
Antioquia for supporting the project 48-06-192-95, and
Professor Marcio de Souza-Santos, IPT-Brazil, for kind
review of the draft and useful suggestions. A. M. would like
to thank Colciencias and Universidad de Antioquia for the
Jovenes Investigadores grant.

REFERENCES
1
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References

11

Homogeneous
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Non-reactive core
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Dutta et al.
Random pore model
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7,8,10,13,24

Homogeneous
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12

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