Article

pubs.acs.org/EF

Experimental and Modeling Study of Char Gasication with Mixtures

of CO2 and H2O
Chao Chen, Sen Zhang, Kai Xu, Guangqian Luo, and Hong Yao*
State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan, Hubei 430074, Peoples
Republic of China

ABSTRACT: Six chars, such as four coal chars of varying rank and two chars derived from acid-washed coals, were prepared by
fast pyrolysis using a drop-tube furnace at 1323 K to study the gasication reaction mechanism when both CO2 and H2O were
present using a thermogravimetric analyzer and a uidized-bed reactor at the atmospheric condition at 11731273 K. It was
found that the char gasication rate in the mixtures of CO2 and H2O was obviously lower than the sum of the two rates of the
char individually reacting with CO2 or H2O but higher than the rate of each individual reaction. CO2 and H2O competed for the
same active sites on the surface of char. The charH2O reaction was independent of the charCO2 reaction, while the char
CO2 reaction was inhibited by the charH2O reaction. With the increase of the coal rank and temperature, the inhibition
decreased. On the basis of the results, a new mechanism was suggested to describe the competition between the CO2 adsorption
and the H2O adsorption. Moreover, a detailed mathematical model based on the derived mechanism was used to predict the
performance of an axisymmetric, entrained-ow gasier. Comparisons between values predicted by the model and experimental
study of the literature had shown good agreement.

1. INTRODUCTION The mechanisms are also known as an oxygen-exchange

Gasication of coal oers several advantages; e.g., various types
of coals ranging from lignite to anthracite can be used, and
dierent syngas and byproducts can be obtained depending
upon the operating conditions. Various types of reactors, such
as xed (moving) bed, uidized bed, entrained bed, and molten
bath, may be used along with autothermal or allothermal heat
arrangements.1 Understanding the gasication reaction mech-
anism and reactivity is essential in relation to gasier design,
operation, and troubleshooting.2,3
Most published gasication reactivity investigations studied
char gasication with a single CO2 or H2O.25 The surface
reaction rate, especially the eect of gas partial pressures on
that, has been successfully modeled using the Langmuir
Hinshelwood (LH) equation.6 The traditional LH rate
equation can work well when the gas partial pressure is low.7
The mechanisms of the charCO2 reaction and charH2O
reaction have been considered to be essentially the same as the
following:
k1
C( ) + CO2 CO + C(O)
k 1 (1)
k2
C(O) CO + C( ) (2)
and
k3
C( ) + H 2O
H 2 + C(O)
k 3 (3)
k4
C(O) CO + C( ) (4)
A CO2 or H2O molecule is adsorbed at a carbon active site,
releasing carbon monoxide or hydrogen and forming an
oxidized surface complex. Then, the carbonoxygen complex
subsequently produces a molecule of CO and a new active site.
mechanism.
However, the mechanism of char gasication with the
mixtures of CO2 and H2O is not clear. According to published
results, a few possible surface reaction mechanisms were
proposed. Some people proposed that charH2O and char
CO2 reactions occurred at the separate active sites. The
relationship between the CO2 adsorption and H2O adsorption
was independent, and the gasication rate in mixtures was the
sum of each individual gasication rate.810
On the other hand, other researchers found that the
gasication rates in the mixtures were lower than the sum of
each individual gasication rate and proposed that charH2O
and charCO2 reactions occurred at the same active sites.1114
The active sites for both the charCO2 and charH2O
reactions were the edge sites, and the basal plane carbon atoms
were usually less reactive.7 However, there is no consensus on
the competition between CO2 adsorption and H2O adsorption.
Muhlen et al.11 proposed that the relationship between the CO2
adsorption and H2O adsorption was parallel. The adsorption
step was coupling. The CO2 adsorption had inuence on the
H2O adsorption, and the H2O adsorption also had inuence on
the CO2 adsorption. The gasication rate in mixtures was the
coupled form of CO2 adsorption and H2O adsorption.
However, Roberts and Harris13,15 proposed that the relation-
ship between the CO2 adsorption and H2O adsorption was
competitive. CO2 could be adsorbed preferentially at the active
sites. Adsorption of H2O was blocked by pre-adsorbed CO2.
Special Issue: 5th Sino-Australian Symposium on Advanced Coal and
Biomass Utilisation Technologies
Received: September 30, 2015
Revised: December 11, 2015
Published: December 11, 2015

2015 American Chemical Society 1628 DOI: 10.1021/acs.energyfuels.5b02294

Energy Fuels 2016, 30, 16281635
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Therefore, the charCO2 reaction was independent of the Table 1. Properties of the Coals Used for Char Generation
charH2O reaction, while the charH2O reaction was inhibited
coal CF SH PDS YQ
by charCO2 reaction.
Furthermore, Umemoto et al.16 also found that the Proximate Analysis
gasication rates in the mixtures were lower than the sum of moisture (%, ad) 4.47 4.90 4.31 3.14
each individual gasication rate. However, the study proposed ash (%, ad) 15.34 7.11 35.15 16.57
that both the separate active sites and the same active sites volatile matter (%, ad) 37.14 32.55 28.51 11.95
coexisted during char gasication in the mixtures of CO2 and xed carbon (%, ad) 43.05 55.44 32.03 68.35
H2O. CO2 gasication and H2O gasication could share active Ultimate Analysis (%, daf)
sites partially. carbon 70.56 76.93 73.77 90.45
The survey above indicates that the main dierences among hydrogen 6.85 4.47 5.52 3.46
these mechanisms on char gasication with mixtures of CO2 oxygen (by dierence) 19.60 14.68 13.68 3.64
and H2O are the relationship between the active sites for the nitrogen 1.01 0.92 1.22 1.26
charCO2 reaction and those for the charH2O reaction and sulfur 1.98 3.00 5.81 1.20
the competition between the CO2 adsorption and the H2O Analysis of Ash (%)
adsorption. Previous work by the authors17 had found that SiO2 46.66 29.17 58.38 49.90
gasication rates of the chars prepared by a lignite in the Al2O3 15.94 14.18 28.75 34.36
mixtures were obviously lower than each individual gasication Fe2O3 10.52 9.50 3.02 3.14
rate at 1273 K. However, the charH2O reaction was CaO 7.30 25.57 2.26 2.84
independent of the charCO2 reaction, while the charCO2 K2O 0.82 0.39 1.21 0.98
reaction was inhibited by the charH2O reaction. To better Na2O 0.83 2.19 1.16 1.16
understand the conditions applicable to various mechanisms, MgO 2.65 1.13 1.67 1.24
more experiments are needed to verify which mechanism is MnO 0.26 0.33 0.05 0.02
more suitable under certain conditions. In particular, the eects P2O5 0.52 0.68 0.82 0.75
of coal type and temperature on the char gasication with TiO2 0.42 0.46 0.82 1.00
mixtures of CO2 and H2O are needed to be understood, SO3 13.44 16.07 1.60 4.30
because the rank of parent coal is an important factor aecting
the char active sites and the temperature is an important factor
aecting the adsorption rate.18 Two chars derived from acid-
H2O at atmospheric pressure were measured using a vertical TGA.
washed coals have also been determined in this paper, avoiding The reactor diameter of the TGA was 70 mm. Each experiment used 3
the eect of the catalyst on the reaction mechanism. To study NL/min of gas mixture and 300 mg of char sample. The conditions
the competition between the CO2 adsorption and the H2O could ensure that the gasication rates were not aected by the gas
adsorption, the char gasication under dierent gas partial ow rate, weight of sample, and particle size. The ow rates of CO2
pressure conditions at dierent temperatures has been and N2 were controlled by the mass ow meters. The ow rate of H2O
investigated. was controlled by a peristaltic pump (0.8 mL/min of liquid water
provides 1 NL/min of vapor). Specic gasication rates10,13 were
2. EXPERIMENTAL SECTION calculated from the mass versus time proles using eq 5
Because the char reactivity is generally proportional to the active sites
1 dX
and the active sites for charCO2 and charH2O reactions in the r= (g s1 g 1)
mixtures were dicult to measure directly, most researchers usually 1 X dt (5)
study the relationship between the active sites for the charCO2
reaction and those for the charH2O reaction by the measurement of where X is the char conversion at reaction time t. The kinetic
the gasication rate. In this study, a common experimental reactor of parameters and adsorption and desorption rates were derived by the
the thermogravimetric analyzer (TGA) was used to measure the rates LH rate equation.
by changes of the char weight. The condition approximated a 2.3. Fluidized-Bed Gasication Experiment. The experimental
commercial moving bed gasier, but it was dierent from that in a conditions in the FBR were designed to inhibit the uid dynamics on
uidized bed or entrained ow gasier.6 Thus, a uidized-bed reactor the intrinsic reaction kinetics. The reactor is a one-stage uidized bed
(FBR) was also used to measure the rates by evolved gas analysis, with 40 mm diameter and 120 mm height, as shown in Figure 1, which
strengthening the collision frequency between the gas and the solid. is similar to the study by Xie et al.20 The Al2O3 particles with a size of
2.1. Char Preparation. Four coals were used in this work with 74106 m were used as the uidization medium. The critical
sizes of 106180 m. They range from lignite to anthracite. The uidization velocities of the two type of particles were closed, avoiding
properties of the pulverized coals are presented in Table 1. With the the separation of particles in the bed. A total of 600 mL/min of gas
increase of the coal rank, the volatile content and oxygen content mixture and 60 mg of char sample were used for each experiment to
decrease. To study the eect of mineral matter on the char gasication, ensure a high excess gasifying agent ratio, to reduce the diusion
two coals were subjected to acid washing to remove the inorganic resistance between the emulsion phase and bubble phase.
matter. About 5 g of coal sample was mixed with 48% concentrated The char sample was injected into the uidization medium at the
hydrouoric acid for 24 h at room temperature, then treated with 6 N holding temperature in one shot within 2 s to cause the fast mixing,
hydrochloric acid, and kept for 12 h at 333 K. At last, the sample was heating, and reaction. The evolved gas was then passed through
washed with excess demineralized water. Most of the ash could be concentrated sulfuric acid to remove vapor, and the dried gas was
removed by the demineralization process.19 analyzed by an online gas analyzer. CO2, CO, CH4, and CnHm were
Four raw coals and two acid washed coals (AW-SH and AW-PDS) measured by a non-dispersive infrared (NDIR) method with an
were used to prepare the chars. The pyrolysis was carried out in a accuracy of 0.1%. H2 was measured by an electrochemical detector
drop-tube furnace at atmosphere pressure under a N2 atmosphere at with an accuracy of 0.4%, and O 2 was measured by an
1323 K, with a high heating rate. electrochemical detector with an accuracy of 0.2%. The gasication
2.2. Reaction Rate Measurements in the TGA. The rates of the rates could be obtained through the production rate of evolved gas
char gasication with CO2 or in H2O and the mixtures of CO2 and based on the mass balance calculations.

1629 DOI: 10.1021/acs.energyfuels.5b02294

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Figure 1. Schematic diagram of the one-stage FBR.
3. RESULTS AND DISCUSSION
3.1. Eect of Coal Types on the Char Gasication with
CO2, H2O, and Their Mixture. Char conversion curves during
gasication in the TGA were obtained by the direct measure of
weight changes in the controlled gasication atmosphere. The
typical results of SH char and AW-SH char conversion are
shown in Figure 2 in 1/3 atm CO2, 1/3 atm H2O, and their
mixture of 1/3 atm CO2 and 1/3 atm H2O. These data were all
presented at 1273 K. The reaction time was shorter for the
charmixture reaction than for the charH2O reaction and
much shorter than that for the charCO2 reaction. Conversion
Figure 2. (a) SH char and (b) AW-SH char conversion curves reacting
in the TGA and the FBR at 1273 K in 1/3 atm CO2, 1/3 atm H2O, and
their mixture of 1/3 atm CO2 and 1/3 atm H2O.
1630
Article
curves of other chars have the same trend, which are not shown
here. Specic reaction rates at the char conversion of 50% for
the six chars reacting in all atmospheres investigated in the
TGA are all shown in Table 2. With the increase of the coal
rank, the gasication rate decreased under the same conditions.
The gasication rate of raw coal char was faster than that of
acid-washed coal char. The charH2O reaction rate was higher
than the charCO2 reaction rate in the same gasication agent
partial pressure. Because the experiments were carried out at a
lower pressure, the reaction rate was controlled by the
adsorption step. It meant than H2O might be more easily
absorbed on the surface of char than CO2. The CO2 gasication
rate of CF char was about 10 times higher than that of YQ char,
while the H2O gasication rate of CF char was about 2 times
higher than that of YQ char in the TGA. The coal rank had
greater impact on the charCO2 reaction than on the char
H2O reaction. The charmixture reaction rates were a little
higher than the individual charH2O reaction rate but lower
than the sum of each individual reaction rate for all chars.
Figures 3 and 4 show the variations of the production rates of
syngas in dierent atmospheres during SH char and AW-SH
char gasication in the FBR. Char conversion curves in the FBR
can be obtained, which are also shown in Figure 2, by the
following equations:17
nC = 0.5(nCO + n H2) (6)
t t
m = MC 0 nC dt = 0.5MC 0 (nCO + n H2) dt
(7)
t
m 0.5MC (nCO + n H2) dt
0
X= =
m 0.5MC (nCO + n H2) dt
0 (8)
where nC is the conversion rate of carbon (mol/min), nCO and
nH2 are the production rates of carbon monoxide and hydrogen
(mol/min), respectively, m is the weight conversion of carbon
(g), and MC is the molecular weight of carbon (g/mol). The
xed carbon content of 60 mg of SH char particles was about
53.18 mg, and that of 60 mg AW-SH char particles was 60 mg
in theory. The weight conversion of SH char during the FBR
gasication was 53.61, 53.40, and 51.84 mg, respectively, by eq
7, under dierent gasication conditions. The weight
conversion of AW-SH char during the FBR gasication was
about 58.31, 59.11, and 58.94 mg, respectively. The results
showed that the two quartz frits had a good eect on the gas
solid separation, and the mass balance for the one-stage FBR
was good to the kinetics tests.
The obtained specic gasication rates are shown in Table 2.
The results of equilibrium calculation are also shown in Figures
3 and 4 on the basis of the assumption that the gas reaction was
local instantaneous equilibrium. It was found that the
experimental syngas production rates were very close to the
results of equilibrium calculation. It means that the water-gas
shift reaction always tends to the equilibrium in the FBR. Thus,
the compositions of syngas were very dierent between the
charH2O and charmixture gasications, even if the gas-
ication rate of the charmixture reaction was a little higher
than that of the charH2O reaction. The charH2O reaction
produced more hydrogen, while the charmixture reaction
produced more carbon monoxide as a result of the high
concentration of CO2.
DOI: 10.1021/acs.energyfuels.5b02294
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Table 2. Specic Reaction Rates at the Char Conversion of 50% for the Six Chars Reacting in All Atmospheres Investigated in
the TGA and the FBR
specic gasication rate (103, g s1 g1)
reactor partial pressure CF SH PDS YQ AW-SH AW-PDS
1
TGA /3 atm CO2 1.93 1.66 1.33 0.190 1.11 1.02
2
/3 atm CO2 3.33 2.30 1.84 0.264 1.51 1.42
1 atm CO2 4.00 2.79 2.15 0.327 1.80 1.76
1
/5 atm H2O 2.46 2.10 2.42 1.03 2.34 2.05
1
/3 atm H2O 3.25 3.17 3.26 1.46 3.08 2.72
2
/3 atm H2O 4.78 4.93 5.18 2.38 4.46 4.39
1
/3 atm H2O + 1/3 atm CO2 4.04 4.14 3.91 1.59 3.56 3.39
1
/3 atm H2O + 2/3 atm CO2 4.63 4.59 4.16 1.65 3.73 3.59
1
FBR /3 atm CO2 10.9 10.2 7.37 0.587 5.15 3.69
1
/3 atm H2O 16.3 14.7 13.9 3.22 12.4 8.79
1
/3 atm H2O + 1/3 atm CO2 22.8 20.1 17.7 3.80 15.1 10.5

The rate of char gasication in the FBR was about 35 times
higher than that in the TGA at the same atmosphere because of
the better collision between the char and the gasication agents,
increasing the frequency factor in chemical kinetics. The
changes in the reactor seemed to have a similar eect on the
charCO2, charH2O, and charmixture reactions. The
gasication rates in mixtures were also lower than the sum of
each individual gasication rate for all chars in the FBR, just like
in the TGA.
3.2. H2O Inhibition of the CharCO2 Reaction. As
shown in Table 2, charmixture reaction rates are obviously
higher than each individual reaction rate but lower than the
sum of the two rates of the char individually reacting with CO2
and H2O. At the xed partial pressure of H2O, the char
gasication rate increased with the increase of the CO2 partial
pressure. It indicated that the charH2O and charCO2
reactions might compete for the same active sites on the
surface of char.
Figure 5 shows the variation of rmix (charmixture reaction
rate in the TGA) with rCO2 (charCO2 reaction rate in the
TGA), indicating a good linear relationship between the two
rates for all of the gasication cases at the xed partial pressure
of H2O. Therefore, linear regression can be employed to derive
the correlation coecients, and the results are shown in Table
3. The regressed coecients of rH2O were all close to 1, while
those of rCO2 were all lower than 1. This might be due to the
bond energy of HO of H2O being lower than that of CO of
CO2, and the chemical adsorption of H2O on the surface of the
char was preferential. The coecient of rCO2 decreased with the
increase of the coal rank because the lower H2O adsorption rate
of high-rank char decreased the H2O inhibition of the char
CO2 reaction.
The raw coal charmixture reaction and acid-washed coal
charmixture reaction had a similar mechanism. It might be
due to the mineral matter having no impact on the chemical
bond of the gas molecule. The competition between the CO2
adsorption and the H2O adsorption was mainly aected by the
gas properties.
The rate expression shown in Table 3 for char gasication in
the mixture of CO2 and H2O derived from the TGA
experiments can also well represent the char gasication
process in the FBR, even if there is better contact between char
and gasication agents in the FBR. The coupling mode between
the gas and solid phase might had little impact on the
1631
competition between the CO2 adsorption and the H2O
adsorption
3.3. Eect of the Temperature on the Char Gas-
ication with CO2, H2O, and Their Mixture. Figures 6 and 7
show the conversion of SH char in 1/3 atm CO2, 1/3 atm H2O,
and their mixture at 1173, 1223, and 1273 K. With the increase
of the temperature, the coal reaction rate increased rapidly. The
charmixture reaction rate was always obviously lower than the
sum of the two rates of the char individually reacting with CO2
and H2O at dierent temperatures. On the experimental
hypothesis that the charH2O reaction was independent of the
charCO2 reaction, while the charCO2 reaction was inhibited
by the charH2O reaction, the coecient of rH2O was 1 and the
coecient of rCO2 could be obtained by calculation, as shown in
the Figures 6 and 7. The obtained coecient of rCO2 increased
with the increase of the temperature. It indicated that the
inhibition decreased with the increase of the temperature
3.4. Possible Rate Equation of the CharMixture
Reaction. It was found that charH2O and charCO2
reactions might not occur at the completely separate active
sites for all of the investigated chars. Thus, a new possible rate
equation of the charmixture reaction can be proposed
assuming that CO2 and H2O compete for the same active
sites, and H2O can be adsorbed preferentially at the active sites.
CO2 does not signicantly retard the rate of the charH2O
reaction. The empty sites for H2O adsoprtion are not aected
by CO2. The rate of H2O adsorption should be proportional to
the empty sites. Considering the retardation eect of H2 on the
charH2O reaction, the steady-state reaction equation (overall
reaction rate is equal to the adsorption and desorption step
rates) based on the LH mechanism can be expressed
k 3(1 H2O)PH2O k 3H2OPH2 = k4H2O (9)
rH2Omix = k4H2O = rH2O (10)
where H2O is the fractional coverage of H2O at the active sites
and rH2Omix is the rate of H2O gasication in the mixture.
However, adsorption of CO2 is blocked by pre-adsorbed
H2O; therefore, the rate of the charCO2 reaction is reduced
by the presence of H2O. The empty sites for CO2 adsorption
are aected by pre-adsorbed H2O. Considering the retardation
eect of CO on the charCO2 reaction, the steady-state
reaction equation can be expressed
DOI: 10.1021/acs.energyfuels.5b02294
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Figure 3. Variations of production rates during SH char gasication in
the FBR at 1273 K in (a) 1/3 atm CO2, (b) 1/3 atm H2O, and (c) their
mixture of 1/3 atm CO2 and 1/3 atm H2O. ( and ) Equilibrium
calculation results of evolved gas.
k1(1 H2O CO2)PCO2 k 1CO2PCO = k 2CO2 (11)
k 3PH2O
rCO2mix = k 2CO2 = 1 rCO
k4 + k 3PH2 + k 3PH2O 2
(12)
where CO2 is the fractional coverage of CO2 at the active sites
and rCO2mix is the rate of CO2 gasication in the mixture.
Thus, a combined rate expression of eq 13 can be derived to
calculate the charmixture reaction rate. H2O inhibition of the
charCO2 reaction is aect by the partial pressure of H2 and
H2O and the adsorption and desorption rates of the charH2O
reaction. With the increase of PH2O and the decrease of PH2, the
coecient of rCO2 decreases and the inhibition increases.
Article
Figure 4. Variations of production rates during AW-SH char
gasication in the FBR at 1273 K in (a) 1/3 atm CO2, (b) 1/3 atm
H2O, and (c) their mixture of 1/3 atm CO2 and 1/3 atm H2O. ( and
) Equilibrium results of evolved gas.
Because of the slower H2O adsorption rate k3 of high-rank coal
char, the inhibition decreases with the increase of the raw coal
rank. Because of the lower active energy of k3 lower than k4, the
ratio of k3/k4, the inhibition decreases with the increase of the
temperature in the regime of adsorption control. These
conclusions are consistent with the experimental results.
rmix = rCO2mix + rH2Omix
(k 3/k4)PH2O
= 1 rCO + rH O
1 + (k 3/k4)PH2 + (k 3/k4)PH2O 2 2
(13)
Figure 8 shows the comparison of experimental rates of the
charmixture reaction and calculated rates using eq 13. The
derived rate equation is appropriate to predict the char
1632 DOI: 10.1021/acs.energyfuels.5b02294
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Figure 5. Linear relationship between rmix (char gasication rate with

the mixture of CO2 and H2O in the TGA) and rCO2 (individual char
gasication rate with CO2 in the TGA).

Table 3. Linear Fit Equation between rmix (Char Gasication

Rate with the Mixture of CO2 and H2O in the TGA) and rCO2
(Individual Char Gasication Rate with CO2 in the TGA)
char partial pressure reaction rate equation
1
CF /3 atm H2O rmix = 0.414rCO2 + 1.000rH2O
1
/3 atm H2O + 1/3 atm CO2
1
/3 atm H2O + 2/3 atm CO2
1
SH /3 atm H2O rmix = 0.611rCO2 + 1.001rH2O
1
/3 atm H2O + 1/3 atm CO2
1
/3 atm H2O + 2/3 atm CO2
1
PDS /3 atm H2O rmix = 0.489rCO2 + 1.000rH2O
1
/3 atm H2O + 1/3 atm CO2
1
/3 atm H2O + 2/3 atm CO2
1
YQ /3 atm H2O rmix = 0.713rCO2 + 1.000rH2O
1
/3 atm H2O + 1/3 atm CO2
1
/3 atm H2O + 2/3 atm CO2
1
AW-SH /3 atm H2O rmix = 0.431rCO2 + 1.000rH2O
1
/3 atm H2O + 1/3 atm CO2
1
/3 atm H2O + 2/3 atm CO2
1
AW-PDS /3 atm H2O rmix = 0.621rCO2 + 1.003rH2O
1
/3 atm H2O + 1/3 atm CO2
1
/3 atm H2O + 2/3 atm CO2

gasication rates with the mixtures in both the TGA and the
FBR.
4. SIMULATION MODELING
4.1. Model Description. A number of models have been
developed to simulate the coal gasication process, many of
them using simple reaction kinetics. The aim of this paper is to
report the development gasier model using the derived char
mixture reaction mechanism based on the LH equation. A
laboratory-scale, axisymmetric, entrained-ow gasier at Brigh-
ham Yong Unversity (BYU) was simulated. Brown et al.21 had
given detailed experimental methods and test conditions.
The one-dimensional steady calculation was used in the
numerical simulation of gasication. The temperature and gas
compositions were assumed to be uniformly dispersed across
the reactor and only change along the reactor. Gas turbulence
was neglected. The model includes the following components:
particle heating, devolatilization, char combustion, char gas-
ication, gas reaction and equilibrium, internal and external
diusion, and heat balance between the wall, gas, and particles.
1633
Figure 6. SH char conversion curves reacting in the TGA in 1/3 atm
CO2, 1/3 atm H2O, and their mixture of 1/3 atm CO2 and 1/3 atm
H2O, at (a) 1173 K, (b) 1223 K, and (c) 1273 K.
These model components can be found in the paper by Liu and
Niksa.12 The original gasication model was provided by Liu
and Niksa12 and was not repeated here.
4.2. Modeling Results. As shown in Figure 9, the predicted
gas species in the axial direction agree reasonably well with the
experimental tests. The euent gas property composition (dry
and inert free basis) of the modeling result was 49.7% CO,
26.0% H2, 24.1% CO2, and 0.0025% CH4 compared to the
experimental result of 51.1% CO, 24.7% H2, 23.6% CO2, and
0.3% CH4. The carbon conversion of the modeling result was
81.2% compared to the experimental result of 82%. The exit gas
temperature of the modeling result was 1344 K, which is also
close to the experimental result of about 1350 K. The mean
deviations between the modeling result and the experimental
result were less than 2%. The results indicated that the derived
DOI: 10.1021/acs.energyfuels.5b02294
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Figure 7. SH char conversion curves reacting in the FBR in 1/3 atm
CO2, 1/3 atm H2O, and their mixture of 1/3 atm CO2 and 1/3 atm
H2O, at (a) 1173 K, (b) 1223 K, and (c) 1273 K.
Figure 8. Comparison of experimental rates of the charmixture
reaction and calculated rates using eq 13.
1634
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Figure 9. Modeling predictions and experimental data at the reactor
centerline.
charmixture rate equation based on the LH equation gave a
reasonable prediction.
Figure 10 shows the sensitivity analysis of dierent char
mixture rate equations on the char conversion. The results
showed that the deviation of predicated carbon conversion was
about 3% and the gas components were similar because the gas
component was mainly controlled by the local instantaneous
equilibrium. The results indicated that the simplied kinetic
equations in the gasication simulation were also acceptable,
because gasication was generally carried out at a high
temperature and the inhibition of the charH2O reaction and
the charCO2 reaction was not strong.
5. CONCLUSION
Four chars produced by four raw coals range from lignite
through bituminous to anthracite and two chars produced by
two acid-washed coals were used to investigate the mechanism
of the char gasication reaction mechanism with mixtures of
DOI: 10.1021/acs.energyfuels.5b02294
Energy Fuels 2016, 30, 16281635
Energy & Fuels
Figure 10. Sensitivity analysis of dierent charmixture rate equations
on the coal conversion.
CO2 and H2O using both the TGA and the FBR. It was found
that CO2 and H2O competed for the same active sites and H2O
could be adsorbed preferentially at the active sites. The char
H2O reaction was independent of the charCO2 reaction,
while the charCO2 reaction was inhibited by preferentially
adsorbed H2O. With the increase of the coal rank and
temperature, the inhibition decreased. A new possible
mechanism equation was proposed, which was appropriate to
predict the charmixture reaction rates. Future work will focus
on the eect of the pressure on the inhibition between the CO2
adsorption and H2O adsorption and using the derived
mechanism to simulate some three-dimensional gasiers at
elevated temperatures and pressures.
AUTHOR INFORMATION
Corresponding Author
*Telephone/Fax: +86-27-87545526. E-mail: hyao@mail.hust.
edu.cn.
Notes
The authors declare no competing nancial interest.
ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation (51476065), the International Science & Technol-
ogy Cooperation Program of China (2015DFA60410), and the
National Major Scientic Instruments Development Project of
China (2011YQ120039). The authors also thank Dr. Liu Gui-
Su for the initial development of the gasication model and the
Analytical and Testing Center of Huazhong University of
Science and Technology for providing the facilities for the
experimental measurements.
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DOI: 10.1021/acs.energyfuels.5b02294
Energy Fuels 2016, 30, 16281635