The kinetics of CO

2
gasication of coal chars
Martyna Tomaszewicz

Grzegorz abojko

Grzegorz Tomaszewicz

Michalina Kotyczka-Moran ska
Received: 31 October 2012 / Accepted: 4 January 2013
Akademiai Kiado, Budapest, Hungary 2013
Abstract The gasication reactivities of three char sam-
ples derived from coals of varying ranks (Turow lignite,
Piast, and Wieczorek sub-bituminous coals) toward
CO
2
were investigated isothermally using thermogravimet-
ric analysis. Kinetic behavior was studied at temperatures of
900, 950, and 1,000 C under atmospheric pressure. Con-
ditions for the chemical-controlled regime were established
at these temperatures and pressure. In this paper, four kinetic
models were applied to describe the varying conversion rate:
volumetric model, grain model, modied volumetric model,
and random pore model. From these models, only the ran-
dom pore and the volumetric models positively corre-
sponded to nearly the entire range of experimental results.
Calculated values of activation energy for study samples
were in the range of 180250 kJ mol
-1
, which is in accor-
dance with other reported data. Moreover, the obtained
results conrmed the signicant impact of parent coal rank
on its char reactivity, offering possibilities in the approxi-
mation of coal char kinetic behavior after further more
detailed studies with a larger number of samples.
Keywords Reactivity Gasication CO
2
Kinetics
Coal char TG
List of symbols
Variables
a Empirical constant in modied volumetric model ()
A Pre-exponential factor (min
-1
)
A Ash content (wt %)
b Empirical constant in modied volumetric
model ()
C Carbon content (wt %)
E Activation energy (kJ mol
-1
)
e Porosity per unit volume of sample (cm
3
cm
-3
)
H Enthalpy (kJ mol
-1
)
k Kinetic constant (min
-1
)

k
MVM
Mean value of kinetic constant of modied
volumetric model (min
-1
)
L Pore length per unit volume of sample (cm cm
-3
)
m Mass (mg)
M Moisture content (wt %)
R Universal gas constant (kJ mol
-1
K
-1
)
R
2
Determination coefcient ()
R
0
Mean random reectance of vitrinite (%)
S Surface area per unit volume of sample
(cm
2
cm
-3
)
T Absolute temperature (K)
t Time (min)
W Structural parameter in random pore model ()
V Volatile matter content (wt %)
X Fractional conversion degree of solid ()
Subscripts
T Total
A Relates to mineral matter
C Relates to combustible matter
d Calculated by difference
max Maximal
0 Refers to initial state
Superscripts
ar As-received basis
ad Air-dried basis
d Dry basis
daf Dry and ash-free basis
M. Tomaszewicz (&) G. abojko G. Tomaszewicz
M. Kotyczka-Moranska
Institute for Chemical Processing of Coal, Zamkowa 1,
41-803 Zabrze, Poland
e-mail: mtomaszewicz@ichpw.zabrze.pl
1 3
J Therm Anal Calorim
DOI 10.1007/s10973-013-2961-2
Introduction
Carbon dioxide is regarded as a chief contributor to the
purported greenhouse gas effect that is driving global cli-
mate change. To meet emission limitations, novel tech-
nologies for fossil fuel processing must be developed and
implemented. Gasication technology, which refers to a
series of processes producing synthesis gas, i.e., H
2
and CO
from carbonaceous materials, is found to be promising for
dealing with the commercial-scale release of CO
2
[1]. Over
the past several years, the concept of polygeneration gas-
ication technology, which combines the power generation
and chemicals production from syngas, has generated a
considerable amount of attention. Recently, most of the
research has been oriented toward the increase of gasi-
cation process performance. As has been presented else-
where, the pressurized CO
2
-enriched gasication of coal is
considered a competitive alternative to conventional gasi-
cation technology [2]. The process of gasication of a
solid fuel begins with a rapid devolatilization, leaving a
char that is mainly composed of carbon and ash. The
second stage is the gasication of a nascent char; this stage
is a rate-controlling step because the reaction rate is much
lower than that of pyrolysis. The char reaction rate,
therefore, has a strong inuence on the conversion ef-
ciency that can be attained under selected process condi-
tions [3, 4]. Consequently, char reactivity is a decisive
factor in coal conversion processes and is greatly inu-
enced by the rank and characteristics of parent coal [58],
conditions during the devolatilization [4, 7], structural
evolution and morphological changes [911], and content
of inorganic matter [7, 12]. In CO
2
-enriched gasication
technology, the Boudouard reaction (1) has a critical role
due to its low reaction rate in comparison to other heter-
ogeneous gasication reactions with oxygen and steam.
C CO
2
2 CO DH 172:5 kJ mol
1
298 K
1
A detailed understanding of char reactivity toward
CO
2
and the reaction kinetics is considered essential for the
mathematical and process modeling of gasiers. A com-
prehensive kinetic model should be developed to facilitate
the application of this knowledge to practical systems.
Generally, there are numerous publications concerning the
CO
2
-gasication kinetics of chars derived from coals of
different rank and pyrolysis conditions [13, 14]. Numerous
models have been established for describing the Boudouard
reaction rate [8, 14]. Some kinetic models, such as the
volumetric and grain models, do not consider the structural
changes that solids undergo [8, 10, 15, 16]. Other models
incorporate the structural effects in addition to rates, such
as the random pore model (RPM) [1517]. The main
objective of this study was to determine the kinetic
behavior of chars derived from variously ranked coals by
means of thermogravimetric (TG) analysis. Thermogravi-
metric analysis is the most widely used technique for
analysis of gasication reaction [18]. The second objective
was to nd a suitable kinetic model to explain the variation
of char reactivity and its changes with the progress of the
CO
2
-gasication reaction. The calculations of the kinetic
parameters (e.g., activation energy and pre-exponential
factor) based on four kinetic models are the primary aim
of the study, including the comparison between results
obtained with the particular model.
The results presented herein are considered as a con-
tinuation of research on kinetics of CO
2
gasication of
solid fuels and reactivity, presented in detail elsewhere
[19, 20].
Materials and methods
For this study, three coal samples were selected: lignite
coal from Turow mine and two sub-bituminous coals
from Piast and Wieczorek mines. All mineelds are
located in Poland. Samples were characterized according to
many indices representing rank, ash content and compo-
sition, and maceral composition. The complete results are
given in Table 1.
As seen in Table 1, the samples notably differ according
to rank. The lowest degree of alteration (metamorphism) is
observed for lignite coal, Turow, followed by Piast
and Wieczorek sub-bituminous coals. Moreover, both of
the sub-bituminous coals can be distinguished by rank as
less or more metamorphosed: Piast and Wieczorek,
respectively, in Table 2.
To reduce the impact of the devolatilization conditions
on the kinetic characteristics of chars, the coal samples
were pyrolyzed in a similar manner. The coals were sub-
jected to pyrolysis in an own-designed xed-bed tubular
reactor of 75 mm internal diameter heated by an electric
furnace under inert atmosphere of nitrogen. For the dev-
olatilization, coal particles ranging from 1 to 4 mm were
chosen. The pyrolysis conditions were as follows: heating
rate of 5 K min
-1
up to 1,000 C and a 30-min holding
time. After pyrolysis, chars were cooled to ambient tem-
perature under owing nitrogen. Subsequently, char sam-
ples were ground and sieved; particle sizes less than
200 lm were selected for TG analysis.
Kinetic measurements were performed isothermally in a
Netzsch STA 409 PG Luxx thermogravimetric analyzer.
Experiments were conducted at three temperatures: 900,
950 and 1,000 C. A weighted char sample (5 mg) was
placed on an alumina crucible inside the furnace and
heated under an argon stream of 25 ml min
-1
up to
M. Tomaszewicz et al.
1 3
reaction temperature with a heating rate of 25 K min
-1
.
Once the desired temperature was reached, the isothermal
gasication reaction of the char sample was initiated by
switching on the CO
2
with a ow rate of 100 ml min
-1
.
The system recorded the weight loss by a highly sensitive
analytical balance located in a casing of apparatus with a
resolution of 10
-3
mg. Thermocouples measuring the
sample temperatures were connected to the bottom portion
of the crucible, precisely underneath the sample layer. The
TG experimental results, obtained as mass loss versus time
data, were converted according to conversion (X) versus
time proles (on ash-free basis) using Eq. (2):
X
m
0
m
m
0
m
ash
2
where m is the instantaneous mass of the sample, m
0
is the
initial mass, and m
ash
is the remaining mass, corresponding
to ash content. The apparent reaction rate was calculated as
a differential of conversion degree versus time, denoted as
dX
dt
. The calculations made with Eq. (2) are found valid
based on the assumption that no reactions of mineral matter
with CO
2
occur during gasication.
Many different models have been proposed to describe
coal char gasication reactions with CO
2
. For kinetic
analysis, four models, which assume the one-step reaction,
were selected. The change in apparent reaction rate can be
expressed as follows:
dX
dt
k T f X 3
where k is the rate constant, dependent on temperature, T, and
f(X), whichhas a structural meaningand corresponds tochosen
nth-order expressions. The kinetic constant is a function of
temperature according to Arrhenius relationship (4):
k T Aexp
E
RT

4
where A and E are pre-exponential factor and activation
energy, respectively, and T is the absolute temperature.
In this study, four nth-order kinetic models were
employed to describe the course of reaction: the volumetric
model (VM), the modied volumetric model (MVM), the
grain model (GM), and the RPM. All models provide dif-
ferent expressions for the term f(X).
The VM is the simplest model, assuming a uniform gas
diffusion within the entire particle and, in consequence,
simplies the reaction by assuming that gas is reacting with
the char in a homogenous manner [8, 15, 16, 19]. The kinetic
expression for the reaction rate is represented by Eq. (5)
dX
dt
k
VM
1 X 5
or in the integrated form by Eq. (6):
ln 1 X k
VM
t 6
The MVM was rst introduced by Kasaoka et al. [22] as
a modication of the VM. However, it assumes that the rate
Table 1 Properties of Turow, Piast, and Wieczorek parent
coals
Coal sample Turow Piast Wieczorek
Proximate analysis/wt %
M
t
ar
44.2 14.4 9.0
M
ad
3.9 4.7 2.6
AC
d
8.1 21.1 17.1
V
daf
59.14 39.10 37.82
Ultimate analysis/wt %
C
T
ad
62.3 59.3 67.8
H
T
ad
5.48 3.83 4.14
N
ad
0.61 0.91 1.16
S
T
ad
1.02 1.09 0.48
S
A
ad
0.28 0.20 0.26
S
C
ad
0.74 0.89 0.22
O
d
ad
19.17 10.27 7.38
Cl
ad
0.009 0.399 0.320
Chemical composition of ash/wt %
SiO
2
32.7 51.42 52.07
Al
2
O
3
24.5 27.03 21.77
Fe
2
O
3
11.4 7.23 9.00
CaO 4.10 2.71 5.04
MgO 6.24 3.30 4.48
TiO
2
1.86 1.04 0.73
Na
2
O 6.76 2.06 1.46
K
2
O NDA 2.40 2.27
Petrographic composition and reectance/%
Vitrinite 73 54 50
Liptinite 17 10 8
Inertinite 6 23 27
R
0
0.23 0.58 0.78
Table 2 Results of the proximate and ultimate analysis of Turow,
Piast, and Wieczorek coal chars
Char sample Turow Piast Wieczorek
Proximate analysis/wt %
M
ad
2.2 1.1 0.7
AC
d
13.7 25.4 25.8
V
daf
0.77 0.47 0.47
Ultimate analysis/wt %
C
T
ad
84.8 72.9 72.2
H
T
ad
0.28 0.32 0.34
N
ad
0.98 1.08 1.09
O
ad
2.05 0.98 0.75
The kinetics of CO
2
-gasication of coal chars
1 3
constant is changing with conversion of solid (X) as the
reaction proceeds [3, 16, 21]. The reaction rate can be
expressed by means of Eq. (7) and the change in
conversion degree with Eq. (8):
dX
dt
k
MVM
X 1 X 7
ln 1 X at
b
8
where k
MVM
(X) is the model-corresponding kinetic
constant, and a and b are empirical parameters with no
physical meaning. The rate constant k
MVM
can be
calculated using Eq. (9):
k
MVM
X a
1
b
b ln 1 X
b1
b
9
The above expression can be integrated to obtain the mean
value of the rate constant, which can be useful in obtaining the
kinetic parameters by means of Eq. (4) and comparing other
constants derived from the analysis of kinetic expressions.
The formulation for the integration is given by Eq. (10):
k
MVM

Z
1
0
k
MVM
X dX 10
The GM assumes that the reaction occurs at the external
surface of the char particle [8, 10, 15, 21, 24]. As the
reaction gradually moves inside the particle, only the ash
layer remains. At the intermediate conversion of a sample
particle, there is a shrinking core of the unreacted solid,
which diminishes with the course of the reaction. The
model is given by Eq. (11) and in an integrated form by
Eq. (12):
dX
dt
k
GM
1 X
2
3
11
3 1 1 X
1
3
h i
k
GM
t 12
The RPM which was developed by Bhatia and Perlmutter
[25] assumes that there is random overlapping of the pore
surface during the extent of the reaction [8, 1517, 2325].
Hence, the surface area available for reaction is also
changing. Those changes are expressed with the structural
parameter, W, which is characteristic for this model. The
RPM, in contrast with the VM, the MVM, and the GM, can
predict the occurrence of maximal rate in the course of the
reaction. The W parameter can be calculated according to
Eq. (13) when initial porosity, e
0
, surface area, S
0
, and pore
length, L
0
, of the solid are known:
W
4pL
0
1 e
0

S
2
0
13
Additionally, the structural parameter can be calculated
by means of maximal conversion degree of solid, X
max
, for
0
0.2
0.4
0.6
0.8
1
0 10 20 30 40 50 60
t/min.
Turw char
(a)
0
0.2
0.4
0.6
0.8
1
Piast char
(b)
0
0.2
0.4
0.6
0.8
1
0 50 100 150 200
Wieczorek char
900 C
950 C
1000 C
(c)
t/min.
X
/

X
/

X
/

900 C
950 C
1000 C
900 C
950 C
1000 C
0 50 100 150 200
t/min.
Fig. 1 Effect of temperature on conversion degree of studied char
samples: Turow (a), Piast (b), and Wieczorek (c)
0
0.2
0.4
0.6
0.8
1
0 30 60 90 120 150
X
/

Turw char
Piast char
Wieczorek char
t/min.
Fig. 2 Effect of coal rank on the carbon conversion of studied char
samples at a temperature of 950 C
M. Tomaszewicz et al.
1 3
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The kinetics of CO
2
-gasication of coal chars
1 3
which maximal reaction rate is observed. The formulation
is given by differentiation of the basic kinetic expression
(14):
dX
dt
1 X

1 Wln 1 X
p
14
After that operation, the value of W can be estimated
according to relation (15) [24]:
W
2
2 ln 1 X
max
1
15
For the evaluation of the rate constant, the integrated
form of relation (14) gives
2
W

1 Wln 1 X
p
1

k
RPM
t 16
Results and discussion
Figure 1 presents the variation of the conversion degree
with time of gasication reaction. It has been shown that
increasing the temperature leads to the shortening gasi-
cation time. This is an expected relationship due to the fact
that the Boudouard reaction is an endothermic one. The
relations presented in Fig. 1 show that the conversion
degree intensively increases from the beginning of the
reaction until a conversion degree of approximately 0.9 is
reached. Subsequently, the reaction proceeds very slowly
until complete conversion. The initial, rapid increase of
conversion can be directly related to the rapid evolution of
the surface area, which proceeds until the pores collapse.
In the case, the reaction surface is decreasing and the rate
is decreasing as well.
The effect of coal rank is shown in Fig. 2. The gure
shows the conversion degree versus time proles measured
at 950 C for the three coal chars with the parent coal rank
ranging from lignite to sub-bituminous. It can be seen that
reactivity decreases with increasing parent coal rank. The
Wieczorek sub-bituminous coal char is the least reac-
tive, whereas the Turow lignite char has a 3 times faster
reaction rate than the other chars. Similarly, small differ-
ences in rank between the Piast and Wieczorek parent
coals can also be seen in terms of their reactivity because
the gasication proles are alike.
The effect of coal rank can be associated with three
major phenomena. First, the higher reactivity observed for
low-rank chars is consistent with the higher concentration
of active sites. Second, the low-rank coal chars have higher
porosity. Hence, the probability of participation of active
sites located in micropores is also higher. Finally, low-rank
coal chars represent higher degrees of dispersion of active
components of mineral matter that are likely to catalyze the
Boudouard reaction.
Table 3 Summarized kinetic and empirical parameters for the VM, the GM, the RPM, and the MVM kinetic models for Turow, Piast, and
Wieczorek gasied at 900, 950, and 1,000 C
Sample Temp./ C VM GM RPM MVM
k
VM
/min
-1
R
2
/- k
GM
/min
-1
R
2
/- W/- k
RPM
/min
-1
R
2
/- a/- b/-

k
MVM
/min
-1
R
2
/-
Turow 900 0.0931 0.8821 0.0514 0.9989 2.87 0.0413 0.9923 0.0053 1.78 0.0823 0.9732
950 0.2146 0.9819 0.1086 0.9497 3.29 0.0885 0.9761 0.0976 1.26 0.1750 0.9941
1000 0.4630 0.9548 0.2326 0.9846 3.39 0.1829 0.9982 0.1485 1.50 0.3720 0.9957
Piast 900 0.0166 0.9497 0.0113 0.9979 3.53 0.0082 0.9996 0.0017 1.46 0.0159 0.9985
950 0.0499 0.9310 0.0277 0.9928 3.21 0.0215 0.9970 0.0197 1.19 0.0402 0.9958
1000 0.1084 0.9237 0.0605 0.9943 3.84 0.0441 0.9971 0.0253 1.39 0.0878 0.9976
Wieczorek 900 0.0128 0.9921 0.0097 0.9955 2.40 0.0078 0.9908 0.0062 1.15 0.0115 1.0000
950 0.0371 0.9657 0.0206 0.9557 2.54 0.0174 0.9807 0.0102 1.28 0.0322 0.9871
1000 0.0931 0.9586 0.0517 0.9718 4.48 0.0355 0.9818 0.0225 1.39 0.0802 0.9837
Table 4 Comparison of the kinetic parameters of the Turow, Piast, and Wieczorek coal chars obtained through analysis of the VM, the
GM, the RPM, and the MVM
Model Turow Char Piast Char Wieczorek Char
E/kJ mol
-1
A/min
-1
E/kJ mol
-1
A/min
-1
E/kJ mol
-1
A/min
-1
VM 199.14 6.87 9 10
7
233.37 4.27 9 10
8
246.44 1.22 9 10
9
GM 187.30 1.11 9 10
7
208.38 2.17 9 10
7
207.34 1.60 9 10
7
RPM 184.70 6.91 9 10
6
209.15 1.74 9 10
7
188.18 1.88 9 10
6
MVM 187.17 1.76 9 10
7
212.07 4.48 9 10
7
240.69 6.10 9 10
8
M. Tomaszewicz et al.
1 3
To study the applicability of selected kinetic models and
predict the kinetic behavior of the studied samples, the
models were tted to experimental data. The reaction rate
constants can be calculated from the slopes of the linearized
relationships expressed by Eqs. (6), (11), and (16), based on
the experimental outcomes by means of linear regression, for
the VM, the GM, and the RPM, respectively. The estimation
of the empirical parameters a and b of the MVM was per-
formed according to a non-linear curve t with the least-
squares method according to Eq. (8). The illustrated
application of the studied models used to describe the
experimental data obtained at different temperatures for
the Turow, Piast, and Wieczorek chars is shown in
Fig. 3. For these studies, the whole range of conversion was
taken into account. The analysis of the data, presented in
Fig. 3, revealed that the VMcannot be sufciently applied to
the experimental results because it does not t the data for
conversions higher than 0.95. Only for the Wieczorek char
sample gasied at 900 C, for which complete conversion
has not been reached, does the model give very good line-
arity. In the case of the GM, improved tting can be
observed. However, differences between the experimental
data and the model can be observed for higher conversion
degrees, indicating that the GM cannot be considered valid
for conversion degrees greater than 0.98. Considering the
RPM, very good linearity was observed, with pronounced
impact of surface area on reactivity for all studied coal chars
toward CO
2
. For the semi-empirical MVM, satisfactory
representation of experimental results was also observed.
The MVM represents the sigmoidal characteristic of the
-ln(1 - X) versus time relationship. Therefore, the MVM
better ts the experimental data than the VM. Small incon-
sistencies can be observed for conversion degrees higher
than 0.99, particularly for temperatures of 950 and 1,000 C.
However, this nding can be considered negligible until the
MVM covers nearly the entire range of conversion degrees.
The reaction rate constants were derived from the slopes
of the graphical representations of expressions (6), (11),
and (16) and experimental data for the VM, the GM, and
the RPM, respectively. The summarized results are listed in
y = 23952x +18.046
R =1
y = 22528x +16.225
R = 0.9992
y = 22215x +15.748
R = 0.9999
y = 22513x +16.686
R = 0.9994
3.5
3
2.5
2
1.5
1
0.5
0.00078 0.0008 0.00082 0.00084 0.00086
l
n
k
i
Reciprocal temperature/ K
1
ln k VM
ln k GM
ln k RPM
ln k MVM
(a)
y = 28070x +19.871
R = 0.9942
y = 25064x +16.892
R = 0.9997
y = 25157x +16.671
R = 0.9963
y = 25507x +17.617
R = 0.9993
5
4.5
4
3.5
3
2.5
2
0.00078 0.0008 0.00082 0.00084 0.00086
l
n
k
i
ln k VM
ln k GM
ln k RPM
ln k MVM
(b)
y = 29642x +20.922
R = 0.9997
y = 24939x +16.587
R = 0.9934
y = 22634x +14.447
R = 0.9999
y = 28950x +20.228
R = 0.9997
5
4.5
4
3.5
3
2.5
2
0.00078 0.0008 0.00082 0.00084 0.00086
l
n
k
i
ln k VM
ln k GM
ln k RPM
ln k MVM
(c)
Reciprocal temperature/ K
1
Reciprocal temperature/ K
1
Fig. 4 Arrhenius relationships obtained for the Turow (a), Piast (b),
and Wieczorek (c) coal chars
170
190
210
230
250
0 0.1 0.2 0.3 0.4
E
M
V
M
/
k
J
m
o
l

1
O/C in parent coal/
170
190
210
230
250
0 0.2 0.4 0.6 0.8 1
R
o
, random vitrinite reflectance/%
E
M
V
M
/
k
J
m
o
l

1
(a) (b)
Fig. 5 Relations between
values of activation energy
obtained using the MVM and
the atomic ratio O/C (a) and the
random vitrinite reectance R
0
(b); both quantities are
representing the rank of parent
coals
The kinetics of CO
2
-gasication of coal chars
1 3
Table 3, along with model-corresponding rate coefcients
and the RPM structural parameter, W. The values obtained
with the MVM, the estimated empirical parameters a and b,
mean kinetic rate constants for this model, and the deter-
mination coefcients are also included in Table 3.
To evaluate the kinetic parameters by means of the
Arrhenius relationship [Eq. (4)], the reciprocal relationship
between the logarithm of the rate constant and the absolute
temperature (1/T) of the reaction obtained by each model at
the studied temperature range was analyzed. The Arrhenius
plots for the Turow, Piast, and Wieczorek chars are
presented in Fig. 4. Very satisfactory ttings were found
for all samples and models as illustrated.
As seen in Fig. 4, no noticeable change in the slopes
of the Arrhenius relations was observed, proving that
increasing temperature does not shift the reaction from
chemically controlled to diffusion controlled. The slopes of
the relationships obtained for the GM and the RPM are
nearly parallel lines providing similar slopes and indicating
similar activation energy values calculated with these
models. In turn, the slopes of the Arrhenius relations for
the VM are steeper for all samples. This result could be
associated with poor tting of the models to the experi-
mental data, shown for VM in Fig. 3. Concerning the
relationship obtained for the MVM, the slope is similar to
those evaluated for the GM and the RPM in the cases of
the Turow and Piast coal chars, while for the
Wieczorek coal char, the slope is more similar to the
VM. On the basis of the slope and the intersection values,
the activation energy E and pre-exponential factor A were
obtained for all studied models, as summarized in Table 4.
The activation energies appear in a similar range as in
previous research works [3, 14, 26]. However, due to the
different slope values observed for the Arrhenius plots, the
values of A and E differ signicantly with the employed
kinetic models. The VM always gives a higher activation
energy. The activation energies estimated by the GM, the
RPM, and the MVM are in the range of 184188 and
208212 kJ mol
-1
for the Turow and Piast coal
chars, respectively. In the case of the Wieczorek coal
char, the calculated activation energy values differ signif-
icantly depending upon the model used to obtain them.
Such changes can be associated with incomplete conver-
sion observed for this sample during gasication at the
lowest temperature of 900 C, which could lead to inac-
curate or false values of kinetic rate constants. Taking into
account the rank of the Wieczorek parent coal and the
fact that the MVM is considered valid for predicting
reactivity of other samples, the activation energy value of
approximately 241 kJ mol
-1
is reliable.
To develop a comprehensive empirical kinetic model for
the char-CO
2
reaction taking into account parent coal
characteristics, the activation energies and the selected
parameters representing parent coal rank were correlated.
From the parent coal characteristics, the atomic ratio O/C
and mean random vitrinite reectance, R
o
, were chosen as
parameters expressing the alteration degree. In Fig. 5,
relations are shown between the activation energy obtained
with the MVM and the O/C ratio and between the rst and
R
o
. With increasing metamorphism degree, oxygen content
decreases and carbon content increases. As a result, the
value of the ratio between contents of these two elements
also decreases. As the O/C ratio of the parent coal rises,
the reactivity (activation energy) of the char diminishes, as
seen in Fig. 5. Likewise, in the case of vitrinite reectance,
which is high for higher-rank coals, the activation energy
increases with increasing value of this parameter. Both
relations can be expressed with simple functions, i.e.,
logarithmic and linear for atomic ratio and R
o
, respectively.
The relations described above once more conrm the
signicant impact of the parent coal rank on the reactivity
of its char. These ndings suggest that more studies should
be performed with a much larger number of samples
varying widely with their rank in order to nd a relation
which could roughly estimate the char reactivity on the
basis of the parent coal characteristics, without additional
information on the kinetic behavior during the gasication
process. Such an approach has been taken by other
researchers, and the results of correlations with petro-
graphic data [27] and the carbon content [11, 28] are
considered sufciently satisfactory.
Conclusions
A kinetic study, using TG analysis, of the CO
2
-gasication
reaction of chars derived from three coal samples of dif-
ferent ranks, one lignite and two sub-bituminous, was
performed over the temperature range of 9001,000 C at
atmospheric pressure. It was established that the char
gasication reactions were carried out under chemical
control for all temperatures studied. Furthermore, it was
observed that increases in the temperature lead to short-
ening of the gasication time due to a higher reaction rate.
This study also evaluated widely used kinetic models
(volumetric, grain, random pore, and modied volumetric)
in prediction of changes in the conversion rates during the
course of the reaction. Of the analyzed models, only the
VM can be discarded due to the poor tting of the exper-
imental data. The other models can be regarded as suitable.
A particularly satisfactory performance was given by the
RPM and the MVM, which incorporate additional param-
eters in their kinetic expressions. Kinetic rate constants and
corresponding values of activation energy and pre-expo-
nential factors were calculated. For the studied char sam-
ples, the activation energy values obtained were 180 and
M. Tomaszewicz et al.
1 3
240 kJ mol
-1
, which are in good agreement with data
reported by other researchers. Moreover, the reactivity of
the coal chars is signicantly affected by the parent coal
rank, which was shown by the activation energy and the
dependency on the atomic ratio O/C and mean random
vitrinite reectance, R
o
.
Acknowledgements The research results presented herein were
obtained during the course of the project Development of coal
gasication technology for high-efciency production of fuels and
energy, Task No. 3 of the Strategic Program for Research and
Development: Advanced energy generation technologies funded by
the Polish National Centre for Research and Development. M. Tom-
aszewicz has received a scholarship under the project Doktoris
Scholarship Programme for the Innovative Silesia, co-nanced by
the European Union in the frame of the European Social Fund.
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The kinetics of CO
2
-gasication of coal chars
1 3