i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 4 5 1 3 e4 5 2 3

Available online at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/he

Kinetic model and prediction for coal hydrogasification

Linbo Yan, Boshu He*, Xiaohui Pei, Xusheng Li, Chaojun Wang, Huaxin Liang
School of Mechanical, Electronic and Control Engineering, Beijing Jiaotong University, Beijing 100044, China

article info abstract

Article history: Coal hydrogasification is a key component of zero emission coal (ZEC) power generation
Received 13 November 2012 system which discharges little CO2 and other pollutants at a thermal efficiency close to
Received in revised form 70%. In addition, coal hydrogasification itself has many advantages. A hydrogasification
15 January 2013 kinetic model including ten homogeneous reactions and four heterogeneous reactions is
Accepted 18 January 2013 established in this work and is validated against experiment data available in literatures.
Available online 21 February 2013 The validated model is then used to predict the effects of different reaction conditions
including the reaction temperature T, the reaction pressure pt, the H2/coal mass ratio U and
Keywords: the reaction time t on coal hydrogasification properties. The results indicate that coal
Hydrogasification hydrogasification is facilitated by the increased pt and t. When T is not higher than 1273 K,
Pyrolysis the gasification process is promoted with T increment. Increasing U can promote the coal
Kinetic model hydrogasification process on the whole. When U is larger than 0.5, however, the coal
Zero emission coal conversion ratio (xcoal) will slightly decrease with U increment.
Prediction Copyright ª 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

1. Introduction technology and has attracted more and more attention

Although many new clean energy sources are now under
development and some have been used commercially, coal is
still expected to be the dominant fuel in the future since it is
abundant and widely distributed on the earth [1]. However,
coal is the dirtiest fuel and traditional coal based power gen-
eration not only has low efficiency but also emits large amount
of pollutants including NOx, SOx, CO2, fine particles, heavy
metals and other trace elements [2]. Coal gasification tech-
nology which has a long history is one way of clean coal
utilization. Coal gasification technical typically includes Tex-
aco, E-gas, Shell and Prenflo etc. Coal gasifiers also have many
different categories such as fixed bed, fluidized bed, entrained
flow bed etc. Moreover, coal gasification products are distinct
from each other, e.g. hydrogen, syngas and liquid fuel etc.
Hydrogasification of coal is a relatively new gasification
recently for its unique advantages. For example, the hydro-
gasification process is exothermic and thus no additional en-
ergy source is required; the direct product of hydrogasification
is methane so no additional methanator is required; the
hydrogasification process has high thermal efficiency reaching
into 80%; there is no requirement for catalyst [3]. Based on the
coal hydrogasification technology, the zero emission coal
(ZEC) concept proposed by Zero Emission Coal Alliance (ZECA)
and Los Alamos National Laboratory (LANL) is considered to be
a promising coal based power generation system for its po-
tential advantages [4e6]. First, it’s highly efficient. High heat-
ing value (HHV) for carbon is 393.5 kJ/mol and low heating
value (LHV) for H2 is 241.8 kJ/mol. Supposing the efficiency of
SOFC is 50%, the electricity generated from this system is then
241.8 kJ. Thus the whole system efficiency can be 61.4%. If part
of the exhausted heat which is mainly the sensible heat of CO2

* Corresponding author. Tel.: þ86 10 5168 8542; fax: þ86 10 5168 8404.
E-mail addresses: 09116329@bjtu.edu.cn (L. Yan), hebs@bjtu.edu.cn (B. He).
0360-3199/$ e see front matter Copyright ª 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ijhydene.2013.01.133
4514 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 4 5 1 3 e4 5 2 3

Nomenclature R14 reaction rate of R14, mol/s

Ri net reaction rate of species i, mol/s
Parameters Ri,r reaction rate of i in reaction r, mol/s
c population of char bridges t reaction time, s
dp particle diameter, cm T reaction temperature, K
f coal conversion ratio after pyrolysis xcoal coal conversion ratio
g1 gas generated in one path xchar char conversion ratio
g2 gas generated in the other path Y ash thickness coefficient
I total number of species yj mass fraction of species j
k reaction rate constant YiC calculated mole fraction of species i
kdash ash film diffusion constant YiE experiment mole fractions of species i
kdiff gas film diffusion constant
Subscripts
ks surface reaction rate constant
a moles of C in coal
Keq equilibrium constant
b moles of H in coal
mchar mass of char, g
c moles of O in coal
mcharl mass of char left, g
d moles of N in coal
mcoal mass of input coal, g
e moles of S in coal
mcinchar mass of C contained in char, g
l element H, O, N or S
mcingas mass of C contained in MECC, g
mointar mass of O contained in tar, g Greek symbols
mcintar mass of C contained in tar, g 3 ash layer voidage
mcincoal mass of C contained in coal, g F mechanism factor
mcr residual mass of char, g rg gas density, kg/m3
mgr residual mass of light gas, g £ population of labile bridges
mlp mass of MECC, g £* population of reactive bridges
mgas mass of light gas, g d population of side chains
mlr residual mass of each element l, g
Abbreviations
mlincoal mass of element l in coal, g
CPD chemical percolation devolatilization
mlinchar mass of element l in char, g
FCM fixed-core model
mlinCH4 mass of element l in CH4, g
FDM fractal dimension model
mlinC2 H6 mass of element l in C2H6, g
HHV high heating value
mlinCO mass of element l in CO, g
IGT Institute of Gas Technology
mlinCO2 mass of element l in CO2, g
LANL Los Alamos National Laboratory
Mj molecular weight of species j, g/mol
LHV low heating value
NR number of reactions
MECC CH4, C2H6, CO and CO2
pep* effective partial pressure, atm
RPM random pore model
pi partial pressure of species i, Pa
SCM shrinking-core model
pt total pressure, atm
ZEC zero emission coal
q ratio of constants
ZECA Zero Emission Coal Alliance
Rs reaction rate of R1eR4, g/cm2 s
R5eR13 reaction rate of R5eR13, mol/m3 s

generated in the decarbonater and the SOFC exhaust is
recovered, the whole system efficiency can be improved fur-
ther. Second, coal hydrogasification is auto thermal because
the carbon methanation is an exothermic reaction, so no
additional heat source is required. Third, gasification and ref-
ormation are processed in two different vessels. Thus, there is
no risk that CaO will be ash contaminated. Fourth, the carbo-
nation and reformation process are taking place in the same
vessel simultaneously so the extent of the reform reaction can
be extended. Fifth, CO2, sulfur and chlorine discharge of this
system is almost zero. Most of CO2 can be captured in the
reformer; sulfur and chlorine will be eliminated in the
cleaners. Although some research [7e9] has been done on coal
pyrolysis and gasification, models mathematically describing
the coal hydrogasification kinetics are rarely found. Some
meaningful results about coal hydrogasification obtained by
former researchers are of great reference value, but the kinetic
mechanisms of coal hydrogasification are still not fully un-
derstood up to now [10e14]. In order to further study the coal
hydrogasification process, a basic zero-dimensional kinetic
model based on the former researches is set up in this work.
The model is validated against experiment data from litera-
tures including coal gasification in oxygen and steam domi-
nant atmosphere and hydrogen dominant atmosphere,
respectively. After validation, the effects of different reaction
conditions on the coal hydrogasification properties are pre-
dicted and analyzed. In addition, the model can be further
used in computational fluid dynamic software via proper
interface such as the user defined function to deeply research
the coal hydrogasification properties in a specific gasifier.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 4 5 1 3 e4 5 2 3 4515

composition of the inlet gasification agent are treated as input

2. Kinetic model for coal hydrogasification parameters and the gasification results depend on all those
boundary conditions.
2.1. General description of this model
2.2. Model for coal hydropyrolysis
The model consists of coal pyrolysis process and the subse-
quent gasification reactions which involves four heteroge-
Several investigators over the years, working both together
neous reactions and ten homogeneous reactions. There are
and independently, have proposed numerous mechanisms
totally five elements (C, H, O, N, S) and eleven species (char,
and kinetic models for the coal pyrolysis, such as the constant
CO, CO2, CH4, H2H6, C6H6, H2, H2O, H2S, N2, O2) in this model.
rate devolatilization law [17], the devolatilization model of
The model is based on the following assumptions and the
single kinetic rate [18], the devolatilization model of two
whole gasification process is illustrated with Fig. 1.
competing rates [19,20], the devolatilization model of chemi-
cal percolation devolatilization (CPD) [21] and so on. Some
1) All the reactions take place in a zero-dimensional reactor,
experiments on the hydropyrolysis of coal have been reported
namely all the species are assumed to be mixed homoge-
[7,8] but mathematical models specially for coal hydro-
neously and the distribution of the coal particles is also
pyrolysis are rarely found. Researchers from the institute of
homogeneous. The coal grains are of uniform diameter.
gas technology (IGT) once developed a coal hydrogasification
2) The pyrolysis process is prior to the gasification process.
kinetic model including the coal hydropyrolysis process. The
Volatiles and char are firstly prepared through rapid
model can properly predict the hydropyrolysis and hydro-
pyrolysis. Then the homogeneous and heterogeneous
gasification process. However, the coal composition analysis
reactions take place. If the char composition is known, the
considered in the model is not common and it cannot predict
volatile composition can be estimated by an empirical
precisely the evolution of an individual species. Moreover,
model [15]. If not, the volatile composition can be estimated
only elements of C, H and O are considered [11,12]. The CPD
with the method developed in this work.
model is finally selected in this work to predict the coal
3) The final temperature of char is the same as the ambient
pyrolysis process for it is not dependent on the empirical
gas temperature.
correlations and can predict well the effects of temperature,
4) Gaseous products from coal pyrolysis consist of volatiles
pressure and heating rate on the coal pyrolysis. Although it is
and tar. The volatiles are composed of CH4, CO, CO2, H2O,
not specially developed for coal hydropyrolysis, it is believed
H2S, N2 and H2 and tar is considered as C14H10 [16].
that the CPD model can predict the coal hydropyrolysis
process reasonably because it has been found that hydro-
All the gasification reactions are coupled and simulta-
gasification undergoes the same initial devolatilization and
neous. The net reaction rate of a species is the sum over all
primary reaction processes as that of the thermal pyrolysis
reactions and is calculated with Eq. (1).
through experimental research [22].
X
NR
Ri ¼ Ri;r (1) 2.3. Description of CPD model
r¼1

where the subscript i denotes the ith species; Ri is the net re- CPD model describes the devolatilization behavior of rapidly
action rate of species i; Ri,r is the reaction rate of species i in heated coal based on the chemical structure of the parent
reaction r; NR denotes the total number of reactions. Then the coal. In this model, coal is visualized as a macromolecular
generation or consumption of each species is calculated by array consisting of clusters, bridges, side chains, and loops, as
integrating the net reaction rate with respect to time. All the illustrated in Fig. 2. The clusters consist of fused aromatic and
model independent parameters including reaction pressure,
temperature, coal type and inlet coal flow rate, flow rate and CH3
R
OH
Reactions
Light gas: CO,CO2,
between
CH4,H2,H2O,H2S,N2 R O
light gases
Side Chain
Bridges CH2
CH2
+H2 CH2
CH4,C2H6 CH3
Heavy CH2 CH2
hydrocarbons: +H2O
COAL tar/metaplast
CO,H2
+O2
CO,H2

+H2
CH4,H2O,H2S,N2 LOOP
R COOH
+H2O
Char(consists of CO,H2,H2S,N2
C,H, O, N, S) +O2 CO,CO2,H2O,H2S,N2
Aromatic Clusters
+CO2
CO,H2O,H2,H2S,N2
PYROLYSIS PROCESS GASIFICATION PROCESS R

Fig. 1 e The general coal hydrogasification process. Fig. 2 e Chemical structures identified in the CPD model.
4516 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 4 5 1 3 e4 5 2 3
heteroaromatic rings of various sizes and types and are con-
nected by a variety of chemical bridges. Some of the bridges
are labile and broken easily during pyrolysis while some of
them are stable. The side chains are those who attach to the
aromatic clusters such as aliphatic (eCHn) and carbonyl
(eCO2) etc. [23].
In CPD, modeling the cleavage of the bridges and the gen-
eration of light gas, char, and tar precursors is considered to be
analogous to the chemical reaction scheme and can be
depicted in Fig. 3. The variable £ denotes the original popula-
tion of labile bridges which will become the set of reactive
bridges £* upon heating. Two competing paths are available
for the reactive bridges. In one path, the bridges cleave and
form two side chains, d. The side chain may detach and form
light gas, g1. As bridges between neighboring aromatic clusters
are cleaved, a certain fraction of the coal detach from the coal
lattice and become heavy-molecular-weight tar precursors
that form the metaplast. The metaplast can either vaporize to
form tar or reattach to the coal lattice. In the other path, the
reactive bridges react and become a char bridge, c, and an
associated light gas, g2, is released. The reaction rates are
governed by the following equations. The ratio rate constants,
q, is set as 0.9 based on experiments [24].
d£
¼ kb £
dt
dc £ mcr ¼ mchar  mcinchar
¼ kb
dt qþ1
 
dd £
¼ 2rkb  kg d
dt qþ1
dg1
¼ kg d
dt
dg2 dc
¼2
dt dt
Before the CPD model is run, a serious of chemical structure
parameters is required. The input parameters are strongly
related to the coal type and details can be found in literatures
[21,23,24]. The results of CPD model consist of three compo-
nents including mass fractions of char, gaseous tar and light
gas. The compositions of the three components are however
not predicted. The composition of light gas is very complex
and varies from different coals and different pyrolysis condi-
tions. In this work, the light gas composition is predicted
based on the concept provided by David [15]. If the original
David’s model is used, many input parameters would be
required, e.g. the composition of char and the constants
predicting the yields of CH4, C2H6, CO and CO2 (methane,
ethylene, carbon monoxide and carbon dioxide, MECC) etc.
Fig. 3 e The pyrolysis scheme in the CPD model.
If these parameters can be obtained either from literatures or
experiments, the original model can then be used directly. If
not, a modified method based on the original David’s model is
developed in this work to roughly predict the light gas species
compositions for a unit mass of coal. The modified David
model includes the following five steps.
First, the constants predicting the yields of MECC are
required. They are supposed to be obtained from experiments.
If no experiment data are available, empirical value can be
assigned based on the element balance with the penalty that
the volatile composition cannot be predicted accurately.
Slight effects of the constants on the final gasification results
are detected because the reactions of gaseous species are very
close to the chemical equilibrium before they leave the
gasifier.
Second, the mass of C contained in char, mcinchar, can be
calculated supposing tar is a giant molecule composed of C
and H [25]. It can be obtained by subtracting the mass of C
contained in MECC, mcingas, and tar, mcintar, from that in the
original coal, mcincoal, as shown by Eq. (7).
mcinchar ¼ mcincoal  mcingas  mcintar (7)
Third, the residual mass of char, mcr, and light gas, mgr, can
then be calculated. mcr can be calculated by subtracting the
(2) mass of C contained in char from the mass of char, mchar,
predicted by the CPD model, as Eq. (8) shows.
(8)
(3)
mgr can be calculated by subtracting the mass of MECC
predicted before, mlp, from the mass of light gas, mgas, got by
(4) the CPD model, as shown by Eq. (9).
mgr ¼ mgas  mlp (9)
(5)
The residual mass of each element l (l denotes H, O, N and S),
mlr, can then be calculated from the element mass balance
calculation, as shown by Eq. (10).
(6)
mlr ¼ mlincoal  mlintar  mlinCH4  mlinC2 H6  mlinCO  mlinCO2 (10)
Fourth, the mass of l contained in char, mlinchar, can be
calculated supposing they are proportional to the mass ratio
of the residual char to the total residual char and light gas,
namely, they can be calculated with Eq. (11).
mcr
mlinchar ¼ mlr (11)
mcr þ mgr
Fifth, the species composition of the light gas can be
calculated based on element mass balance. The mass of S
contained in H2S can be calculated by msincoal  msinchar and
the mass of H2S can then be obtained. The mass of O con-
tained in H2O can be calculated by moincoal  moinchar  moingas
and the mass of H2O can then be calculated. Then the mass of
H2 can be calculated based on H mass balance. The mass of N2
can be calculated by mnincoal  mninchar. Thus, the species
composition of the light gas can therefore be obtained.
2.4. The gasification model
To develop a gasification model, the dominant reactions taking
place during the gasification process should be known firstly.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 4 5 1 3 e4 5 2 3 4517

After pyrolysis, the feed coal has been decomposed into char,
tar and light gas. So the gasification includes the reactions of
char, tar and light gas on the whole. Reactions of char are
heterogeneous while those of tar and light gas are homoge-
neous. Fourteen reactions including 4 heterogeneous reactions
and 10 homogeneous reactions which are typical for the coal
gasification process are considered in this work. More than one
reaction rate correlation has been developed by different re-
searchers for each of the reactions. Those correlations are
compared with each other and finally a set of correlations for
the 14 reactions is established in this work. The heterogeneous
reactions are R1eR4. R1 is the reaction of char with oxygen [26].
 
kdash ¼ kdiff 3
2:5
(14)
where, 3 is the voidage in the ash layer and is assumed to be
a constant value of 0.75 or 0.5 as reported [26,27]. In this work,
the value of 0.75 is assigned to 3 .
Detailed kinetic correlations for the heterogeneous
reactions of R1eR4 are listed in Table 1. In Table 1, T is the
reaction temperature in K; pt is the total pressure in atm; dp is
the particle diameter in cm; pi is the partial pressure of con-
stituent species i in Pa; Keq is the equilibrium constant; f is the
mechanism factor governing the yield of CO and CO2 of R1 and
can be calculated with Eq. (15) preliminarily.

8
< ð2Z þ 2Þ=ðZ þ
 2Þ for dp 
 0:005 cm
f ¼ ð2Z þ 2Þ  Z dp  0:005 =0:095=ðZ þ 2Þ for 0:005 cm < dp  0:1 cm (15)
:
1:0 for dp > 0:1 cm

   
a c b e 1 where, Z is determined with Eq. (16).
Ca Hb Oc Nd Se þ  þ  O2 /2 1  aCO
f 2 4 2 f
    Z ¼ 2500expð6249=TÞ (16)
2 b d
þ  1 aCO2 þ  e H2 OðgÞ þ eH2 S þ N2 (R1)
f 2 2 Reactions R5eR14 listed in Table 2 are CO combustion, H2
combustion, CH4 combustion, wateregas shift reaction, CH4
R2 is the reaction of char with steam [26]. reformation reaction, oxidization of tar, wateretar shift
  reaction, reaction of tar with H2, C2H6 combustion and C2H6
b d
Ca Hb Oc Nd Se þðacÞH2 OðgÞ/aCOþ acþ e H2 þeH2 Sþ N2 reformation reaction, respectively. Detailed kinetic correla-
2 2
tions for the homogeneous reactions, R5eR14, are also listed
(R2)
in Table 2. In Table 2, R5eR13 are the reaction rates in mol/
R3 is the reaction of char with carbon dioxide [26]. (m3 s); R14 is the reaction rate of R14 in mol/s; rg is the gas
  density; ytar is the mass fraction of tar; yj is the mass fraction
b d
Ca Hb Oc Nd Se þaCO2 /2aCOþcH2 OðgÞþ ec H2 þeH2 Sþ N2 of gaseous species j; Mj is the molecular weight of the gaseous
2 2
species j; nC2 H6 is the amount of substance of C2H6.
(R3) Many mathematical models have been developed by in-
R4 is the reaction of char with hydrogen [26]. vestigators to predict the evolution of the effective reaction
surface area of the solid particles. The fixed-core model (FCM)
 
b d assumes the reaction surface to be at fixed diameter and co-
Ca Hb Oc Nd Se þ 2a þ c þ e  H2 /aCH4 þ cH2 OðgÞ þ eH2 S þ N2
2 2 incides with the original surface area [34]. The shrinking-core
(R4) model (SCM) allows for the reduction in the char core radius as
conversion proceeds and the reaction occurs at the surface of
For the heterogeneous reactions, a general correlation to the inner shrinking core [26]. The fractal dimension model
determine the reaction rate can be written as Eq. (12) [26,27]. (FDM), which is based on the shrinking-core model, allows for
the irregular surface shape of char particles [35]. The random
ðp  p Þ
Rs ¼   (12) pore model (RPM) allows for arbitrary pore size distributions in
1 1 1Y 1
þ þ 2 the reacting solid [36]. In this work, RPM which is believed
kdiff kdash Y Y ks
more accurate is used along with the charegas heterogeneous
where, Rs is the reaction rate in g/(cm2 s); Y is the parameter reaction kinetic correlations. In RPM, the evolution of the
reflecting the thickness of ash layer and can be calculated internal surface area during char conversion is expressed as
from Eq. (13); kdiff is the gas film diffusion constant; kdash is the Eq. (17).
ash film diffusion constant and can be calculated from Eq. (14); qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
S
ks is the surface reaction rate constant; pep* is the effective ¼ ð1  xchar Þ 1  jlnð1  xchar Þ (17)
S0
partial pressure in atm.
where S0 denotes the initial internal reactive area; S denotes
1=3
Y ¼ ½ð1  xcoal Þ=ð1  f Þ (13) the reactive area at any time during the reaction; xchar denotes
where, f is the coal conversion ratio based on original dry coal the char conversion ratio; J is the structure parameter for
when pyrolysis is finished; xcoal is the coal conversion ratio a particular char particle.
based on original dry coal at any time after pyrolysis is There are totally 11 constituent species and 14 reactions in
completed. the model set up in this work. Thus, a 14  11 matrix can be
4518 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 4 5 1 3 e4 5 2 3

Table 1 e Kinetic correlations for the heterogeneous reactions.

Kinetic parameters for R1 [26,27] Kinetic parameters for R3 [26,27]

ks ¼ 8710exp(17,967/T ) ks ¼ 247exp(21,060/T )
  1:75  0:75
4:26 T T
kdiff ¼ 0:2924 =ðpt dp Þ kdiff ¼ 7:45  104 =ðpt dp Þ
T 1800 2000
 
p i  p i ¼ pO 2 pi  pi ¼ pCO2

Kinetic parameters for R2 [26,27] Kinetic parameters for R4 [26,27]

ks ¼ 247exp(21,060/T ) ks ¼ 0.12exp(17,921/T )
 0:75  0:75
T T
kdiff ¼ 1:0  103 =ðpt dp Þ kdiff ¼ 1:33  103 =ðpt dp Þ
2000 2000
0:175
Keq ¼ exp[17,644  30,260/(1.8T )] Keq ¼ exp½18; 400=ð1:8TÞ
34; 713
pH pCO pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
pi  pi ¼ pH2 O  2 pi  pi ¼ pH2  pCH4 =Keq
Keq

built to reflect the net increment of each species during the

reaction as shown in Fig. 4. With the above correlations, 3. Model validation
a program for coal gasification is written based on Cþþ codes.
The differential equation set is calculated with the Merson To verify the stability and accuracy of the model set up in this
Variational Step algorithm [37]. work, eight sets (IeVIII) of experimental data in literatures

Table 2 e Kinetic correlations for the homogeneous reactions.

Reactions Kinetic correlations Ref.
p
2 p  [28]
CO O2
CO þ 0.5O2 / CO2 (R5) R5 ¼ k5
RT RT
k5 ¼ 2.4602  1012exp(21137/T þ 24.74414)T3
 2   [28]
pH2 pO2
H2 þ 0.5O2 / H2O( g) (R6) R6 ¼ k6
RT RT
k6 ¼ k5/0.35
 0:2  1:3 [29]
pCH4 pO2
CH4 þ 2O2 / CO2 þ 2H2O( g) (R7) R7 ¼ k7  1000
1000RT 1000RT
k7 ¼ 2.119  1011exp(2.027  105/(RT ))
p
p  
pCO2
 
pH2
CO H2 O
CO þ H2O( g) / CO2 þ H2 (R8) R8 ¼ k81  k82
RT RT RT RT
k81 ¼ 2.75  103exp(8.36  104/(RT )) [30]
Keq8 ¼ 2.65  102exp(3956/T ) [31]
k82 ¼ k81/Keq8
   p
p 3
pCH4 pH2 O CO H2
CH4 þ H2O( g) / CO þ 3H2 (R9) R9 ¼ k91  k92
RT RT RT RT
k91 ¼ 312exp(2  104/RT ) [28]
Keq9 ¼ 6.7125  1024exp(27,020/T )(RT )2 [31]
k92 ¼ k91/Keq9
   1:25 [25]
pC14 H10 0:5 pO2
C14H10 þ 7O2 / 14CO þ 5H2 (R10) R10 ¼ k10  1000
1000RT 1000RT
k10 ¼ 2.0  1011exp(1.256  105/RT )
  
pC14 H10 pH2 O [25]
C14H10 þ 14H2O( g) / 14COþ19H2 (R11) R11 ¼ k11  1000
RT RT
k11 ¼ 312exp(1.256  105/RT )
R12 ¼ 1.7  104exp(98409.38/RT )3 0rgytar [32]
C14H10 þ 19.5H2 / 7CH4 þ 3.5C2H6(R12) 30 ¼ 0.3
pt X9
rg ¼ ð y =M Þ1
RT j¼1 j j
   1:65 [29]
pC2 H6 0:1 pO2
C2H6 þ 3.5O2 / 2CO2 þ 3H2O( g) (R13) R13 ¼ k13  1000
1000RT 1000RT
k13 ¼ 6.186  109exp(1.256  105/RT )
R14 ¼ k14 nC2 H6 [33]
C2H6 þ 2H2O( g) / 2CO þ 5H2 (R14) k14 ¼ 312exp(30,000/1.987T )
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 4 5 1 3 e4 5 2 3 4519

⎛ ⎞
⎜ −1 −1 −1 −1 0 0 0 0 0 0
0 ⎟ 0 0 0
⎛ dchar ⎞
⎜ ⎟ ⎜ dt ⎟
⎜ ⎟ ⎜ ⎟
⎜ 0 0 0 0 0 0 0 0 0 0 0 −1 −1 −1 ⎟ ⎜ dC14 H10 ⎟
⎜ ⎟ ⎜ dt ⎟
⎜ ⎟ ⎛ R1 ⎞ ⎜ ⎟
⎜ 0 0 0 a 0 0 −1 0 −1 0 0 7 0 0 ⎟ ⎜ R 2 ⎟ ⎜ dCH 4 ⎟
⎜ ⎟ ⎜ ⎟ ⎜ dt ⎟
⎜ ⎟ ⎜ R3 ⎟ ⎜ ⎟
⎜ 0 0 0 0 0 0 0 0 0 0 0 3.5 −1 −1 ⎟ ⎜ ⎟ ⎜ dC2 H 6 ⎟
R4 ⎟
⎜ ⎟⎜ ⎜ dt ⎟
⎜ 1 ⎟ ⎜ R 5 ⎟ ⎜ dCO ⎟
⎜ 2(1 − ) a a 2a 0 −1 0 0 −1 1 1 4 1 4 0 0 2 ⎟ ⎜ ⎟ ⎜ ⎟
⎜ φ ⎟ ⎜ R 6 ⎟ ⎜ dt ⎟
⎜ 2 ⎟ ⎜ R 7 ⎟ ⎜ dCO ⎟
⎜ ( − 1) a 0 −a 0 1 0 1 1 0 0 0 0 2 0 ⎟⎜ ⎟=⎜ 2
⎟
⎜ φ ⎟ ⎜ R8 ⎟ ⎜ dt ⎟
⎜ ⎟ ⎜ R 9 ⎟ ⎜ dH 2 S ⎟
⎜ e e e e 0 0 0 0 0 0 0 0 0 0 ⎟⎜ ⎟ ⎜ ⎟
⎜ ⎟ ⎜ R10 ⎟ ⎜ dt ⎟
⎜ d d d d ⎟⎜ ⎟ ⎜ dN ⎟
0 ⎟ ⎜ R11 ⎟ ⎜
2
⎜ 0 0 0 0 0 0 0 0 0 ⎟
⎜ 2 2 2 2 ⎟ ⎜ R12 ⎟ ⎜ dt ⎟
⎜ b b b ⎟⎜ ⎟ ⎜ dH 2 ⎟
⎜ 0 a−c+ −e −e−c −( 2a + c + e − ) 0 −1 0 1 3 5 1 9 − 19 .5 0 5 ⎟ ⎜ R13 ⎟ ⎜ dt ⎟
⎜ 2 2 2 ⎟ ⎜⎝ R14 ⎟⎠ ⎜ ⎟
⎜ b ⎟ ⎜ dH 2 O ⎟
⎜ −e −(a − c) c c 0 1 2 −1 −1 0 0 0 3 −2 ⎟ ⎜ dt ⎟
⎜ 2 ⎟ ⎜ ⎟
⎜ a c b e ⎟ ⎜ dO2 ⎟
⎜⎜ −( − + − ) ⎜ ⎟
0 0 0 −0.5 −0.5 −2 0 0 −7 0 0 −3.5 0 ⎟⎟ ⎝ dt ⎠
⎝ φ 2 4 2 ⎠

Fig. 4 e Species net increment matrix.

[31,38] are used to do the validation. The overall objects of the
work in the two literatures [31,38] are to generate exper-
imental data required to verify the corresponding chemical
reaction mechanisms. Exps. IeIV [31] are the experiments on
coal gasification in the steam and oxygen dominant atmo-
sphere for different coals under different reaction conditions.
The residence time of these reactions are several seconds and
usually not less than 4 s [28]. Exps. VeVIII [38] are the exper-
iments on coal flash hydrogasification in hydrogen dominant
atmosphere for different coals under different reaction con-
ditions. In the experiments implemented in literature [38], the
whole reactor was divided into four parts including the pre-
burner where the fast reaction of oxygen and excessive
hydrogen took place, the steam generator where water and
additional hydrogen were injected, the main burner where
additional oxygen was injected and reacted with excessive
hydrogen and the hydrogasifier where coal and nitrogen were
injected and the coal hydrogasification reactions took place.
Reaction in the first three parts, the preburner, the steam
generator and the main burner, is the fast combustion of
hydrogen, thanks to which the gasification agents (surplus
hydrogen and water generated) are prepared. In the hydro-
gasifier, surplus hydrogen along with water obtained from
hydrogen combustion mixes and reacts with coal and nitro-
gen injected. So the real coal hydrogasification took place in
the last part of the whole reactor, the hydrogasifier. The mean
particle diameter is set as 60 mm based on the literatures.
Boundary conditions of Exps. IeIV are listed in Table 3.
Boundary conditions of Exps. VeVIII are listed in Table 4.
Comparisons of the calculated results and the experiment
data are listed in Table 5. The steam gasification of coal has
nearly reached chemical equilibrium while the coal hydro-
gasification processes have not yet [31,38].
The square sum of errors, Error shown in Table 5, is defined
by Eq. (18) [28,31,33].
X
I
 2
Error ¼ YiC  YiE (18)
i¼1
where I is the total number of constituent species; YiC and YiE
are the calculated and experimental mole fractions of species
i, respectively. The calculation results of the model set up in
this work, shown in Table 5, are found agreeing well with the
experimental data except for the mole fractions of CO and CO2
for the coal hydrogasification processes. This is because the
fluid dynamics and the heat and mass transfer are ignored,
which would affect the detailed kinetic processes of coal
hydrogasification that are still far from chemical equilibrium
since the overall conversions of coal are around 0.6 for Exps.
VeVIII, respectively. However, it doesn’t matter for the coal
hydrogasification process since CO and CO2 are not the staples
and the yields of them are very little.

Table 3 e Boundary conditions of Exps. IeIV [31].

Exp. Gas/coal mass ratio pt T Coal analysis (d)

O2/coal H2O/coal N2/coal C H O N S Ash

I 0.8 0.08 0.13 23.81 1574 69.6 5.3 10.0 1.3 3.9 10.0
II 0.86 0.5 0.017 40.30 e 69.6 5.3 10.0 1.3 3.9 10.0
III 0.87 0.61 0.003 40.30 1317 66.8 5.0 7.3 1.7 4.2 15.0
IV 1.41 0.16 6.22 1.00 e 73.1 4.9 7.9 1.3 2.1 10.6
4520 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 4 5 1 3 e4 5 2 3

Table 4 e Boundary conditions of Exps. VeVIII [38].

Exp. Gas/coal mass ratio pt t Coal analysis (ar)

H2/coal H2O/coal N2/coal C H O N S M Ash

V 0.374 0.524 0.104 69.07 4.91 73.23 5.15 7.83 1.52 3.21 0.99 8.08
VI 0.358 0.539 0.105 69.07 4.72 72.98 5.20 8.13 1.49 3.08 0.77 8.19
VII 0.291 1.053 0.105 69.07 4.58 72.92 4.99 8.72 1.47 3.08 0.43 8.39
VIII 0.261 1.610 0.105 69.07 4.88 73.11 5.14 8.26 1.46 2.96 0.78 8.29

decreases with T increment. This is because the char metha-

4. Coal hydrogasification prediction
After being verified, the model can then be used to predict the
effects of the reaction pressure pt, the reaction temperature T,
the H2/coal mass ratio U and the reaction time t on the evo-
lution of major constituent species of coal hydrogasification
products and the coal conversion ratio (xcoal). Illinois No. 6 coal
used in Exps. I and II as listed in Table 3 is chosen for the
prediction calculation. The reaction condition for the baseline
case is set as pt of 7 MPa, T of 1273 K and U of 0.3. The uni-
variate analysis method is then used to investigate the effects
of each reaction parameter on the coal hydrogasification
properties when the other parameters are kept coincident
with those of the baseline case. Effects of T, pt and U on the
evolution of xcoal defined by Eq. (19) are depicted in
Fig. 5(a)e(c). Effects of T, pt and U on the evolution of CH4 mole
fraction are depicted in Fig. 6(a)e(c). Effects of T, pt and U on
the evolution of the H2 mole fraction are depicted in
Fig. 7(a)e(c).
mcharl
xcoal ¼ 1 
mcoal
where mcharl denotes the mass of char left in the dry ash-free
basis and mcoal denotes the mass of input coal in the dry ash-
free basis.
Fig. 5(a) shows that when T is not higher than 1273 K, xcoal
increases with T increment; when T is higher than 1273 K, xcoal
nation, R4, is an exothermic reaction. The chemical equilib-
rium constant will decrease with T increment based on the Le
Chatelier’s principle. When T is not higher than 1273 K, the
equilibrium constant is relatively large so increasing T will
increase the net reaction rate and will thereafter promote the
reaction process. But, when T is higher than 1273 K, the re-
action will be greatly restricted by the chemical equilibrium
constant. Thus the net reaction rate will be lowered and the
coal conversion will be consequently reduced [39]. Fig. 5(b)
shows that increasing pt can greatly increase xcoal. This is
because increasing pt can obviously increase the partial
pressure of H2, which promotes the char methanation pro-
cess. Fig. 5(c) shows that increasing U will increase xcoal on the
whole. When U is 0.1, the partial pressure of H2 is low while
the partial pressures of other gaseous constituent species,
such as CH4 and CO from the coal pyrolysis, are relatively
high, which is not beneficial to the char methanation process.
When U is higher than 0.1, the partial pressure of H2 becomes
higher while those of CH4 and CO become lower. Thus, the
coal hydrogasification process will be promoted. When U is
(19) high enough, the partial pressure of H2 will increase slightly
with U increment while the partial pressures of H2O and
CO2 will decrease sharply, which will restrain the coal
conversion.
Fig. 6(a) shows that increasing T will increase the CH4 mole
fraction on the whole. But, when T is higher than 1273 K, CH4
mole fraction will decrease with T increment. This is because

Table 5 e Comparisons of the calculation results and the experimental data.

Species CH4 H2 H2O CO CO2 N2 H2S Conversion Error

I Exp. [31] 0.08 30.3 e 61.5 1.4 5.38 1.25 e 2.685

Cal. 0.079 29.6 2.17 60.02 1.44 5.43 1.28 0.989
II Exp. [31] 0.3 29.8 17.1 41 10.2 0.8 1.1 e 0.91
Cal. 0.28 30.2 16.4 40.6 10.5 0.9 1.1 0.996
III Exp. [31] 0.4 29.6 20 35.4 12.8 0.63 1.1 e 0.792
Cal. 0.39 29.3 20.6 34.9 13.1 0.62 1.14 0.987
IV Exp. [31] 0.19 3.37 6.69 10.43 7.70 71.37 0.21 e 0.383
Cal. 0.00 3.18 7.18 10.32 7.56 71.56 0.21 0.913
V Exp. [38] 11.904 69.593 14.877 0.874 0.107 1.915 0.347 0.456 2.187
Cal. 12.078 68.295 15.395 0.426 0.091 1.965 0.351 0.437
VI Exp. [38] 15.573 65.141 15.017 1.716 0.153 1.996 0.372 0.595 1.754
Cal. 15.415 63.86 15.193 1.55 0.309 2.066 0.371 0.573
VII Exp. [38] 14.72 52.35 27.37 2.54 0.58 2.02 0.39 0.604 2.559
Cal. 14.13 52.05 26.06 2.65 1.20 2.06 0.42 0.607
VIII Exp. [38] 10.35 44.58 40.92 1.02 0.35 1.83 0.34 0.428 2.31
Cal. 10.59 43.60 40.07 1.04 1.09 1.91 0.38 0.462
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 4 5 1 3 e4 5 2 3 4521

(a) 0 .8 0 (a)
0 .2 4
0 .7 5 T=1273 T=1323 T=1273 T=1323
0 .2 2
0 .7 0 T=1373
0 .2 0 T=1373
Over all coal conversion

0 .6 5
0 .1 8

CH4 mole fraction

0 .6 0
T=1173 T=1223 0 .1 6
0 .5 5
0 .1 4
0 .5 0
0 .1 2
0 .4 5
0 .1 0
0 .4 0
0 .0 8
T=1073 T=1123
0 .3 5 T=1123
T=1073 T=1173 T=1223
0 .0 6
0 .3 0
0 1 2 3 4 5 6 7 8 9 10 11 0 1 2 3 4 5 6 7 8 9 10 11
Reaction time (s) Reaction time (s)
Effects of T (K) on coal conversion Effects of T (K) on the CH4 mole fraction
(b) 0 .9 0 (b)0 .3 5
0 .8 5 pt=9 pt=11 pt=1 pt=3 pt=5 pt=7

0 .8 0 pt=13 0 .3 0 pt=9 pt=11

Over all coal conversion

0 .7 5 pt=13

CH4 mole fraction

0 .2 5
0 .7 0

0 .6 5
0 .2 0
0 .6 0 pt=5 pt=7

0 .5 5 0 .1 5

0 .5 0 pt=1 pt=3
0 .1 0
0 .4 5

0 .4 0
0 1 2 3 4 5 6 7 8 9 10 11 0 .0 5
0 1 2 3 4 5 6 7 8 9 10 11
Reaction time (s) Reaction time (s)
Effects of pt (MPa) on coal conversion Effects of pt (MPa) on CH4 mole fraction
(c) 0 .8 5 (c)0 .3 0
U=0.5 U=0.6 U=0.7
0 .8 0 U=0.5
0 .2 5
0 .7 5 U=0.6
Over all coal conversion

CH4 mole fraction

0 .7 0
U=0.7 0 .2 0

0 .6 5
0 .1 5

0 .6 0
U=0.1 U=0.2
0 .1 0
0 .5 5
U=0.3 U=0.4
0 .5 0 0 .0 5

U=0.1 U=0.2 U=0.3 U=0.4

0 .4 5
0 1 2 3 4 5 6 7 8 9 10 11 0 .0 0
0 1 2 3 4 5 6 7 8 9 10 11
Reaction time (s) Reaction time (s)
Effects of U on coal conversion Effects of U on CH4 mole fraction
Fig. 5 e Effects of T (K), pt (MPa) and U on the coal Fig. 6 e Effects of T (K), pt (MPa) and U on the CH4 mole
conversion. fraction.

the char methanation is an exothermic reaction. When T is Fig. 7(a) shows that increasing T can reduce H2 mole fraction
higher than 1273 K, the net CH4 formation rate will be lowered. on the whole. When T is higher than 1273 K, H2 mole fraction
Fig. 6(b) shows that CH4 mole fraction increases obviously will increase with T. This is also due to the exothermic char
with pt increment. This is because H2 partial pressure in- methanation reaction. Fig. 7(b) shows that H2 mole fraction
creases with pt, which will promote the char methanation decreases obviously with pt increment. This is because H2
reaction. Fig. 6(c) shows that CH4 mole fraction decreases with partial pressure increases obviously with pt, which promotes
U. This is because the char methanation reaction rate is the coal hydrogasification reaction. Fig. 7(c) shows that H2 mole
relatively slow and the reaction is still far from chemical fraction increases obviously with U. This is because the char
equilibrium. Thus, the coal hydrogasification products will be methanation reaction rate is small and increasing U can only
diluted by the unreacted H2. slightly increase the H2 partial pressure when U is large.
4522 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 4 5 1 3 e4 5 2 3

further used in the computational fluid dynamic software

(a)0 .9 0
to study the coal hydrogasification properties in a specified
T=1073 T=1123 T=1173 T=1223
gasifier.
0 .8 5 2) Increasing pt and t can extend the coal hydrogasification
extent. When pt is 13 MPa, t is 10 s and other parameters are
H2 mole fraction

0 .8 0
kept coincident with those of the baseline case, the coal
conversion is nearly 0.9, CH4 mole fraction is about 0.32 and
H2 mole fraction is about 0.6.
0 .7 5
3) When the other parameters are kept coincident with those
of the baseline case, increasing T can promote the coal
0 .7 0
hydrogasification process when it is not higher than 1273 K.
T=1273 T=1323 T=1373
When T is higher than 1273 K, however, increasing T will
0 .6 5 restrain the gasification process.
0 1 2 3 4 5 6 7 8 9 10 11
Reaction time (s) 4) When the other parameters are kept coincident with those
Effects of T (K) on H2 mole fraction of the baseline case, increasing U will promote the coal
hydrogasification on the whole. When U is larger than 0.2,
(b)0 .9 0 the coal hydrogasification increases slightly with U. When U
is larger than 0.5, the coal conversion ratio slightly decreases
0 .8 5
with U. CH4 mole fraction also decreases with U increment.
0 .8 0
H2 mole fraction

0 .7 5

Acknowledgments
0 .7 0

pt=1
0 .6 5
The authors gratefully acknowledge financial supports from
pt=3 pt=5 the National Natural Science Foundation of China (NSFC,
0 .6 0 50876008) and the Fundamental Research Funds for the
pt=7 pt=9 pt=11 pt=13
Central Universities (2013YJS078) for this work.
0 .5 5
0 1 2 3 4 5 6 7 8 9 10 11
Reaction time (s)
Effects of pt (MPa) on H2 mole fraction references
(c)0 .9 5
U=0.1 U=0.2 U=0.3
0 .9 0
[1] International Energy Outlook 2010. Washington, DC: U.S.
0 .8 5 Energy Information Administration. 2011 Sep. Contract No.:
DOE/EIA-0484, http://me.queensu.ca/Courses/430/
H2 mole fraction

0 .8 0
InternationalEnergyOutlook-summaryonly.pdf; 2011.
0 .7 5 [2] Franco A, Diaz AR. The future challenges for “clean coal
0 .7 0 technologies”: joining efficiency increase and pollutant
emission control. Energy 2009;34:348e54.
0 .6 5
[3] Steinberg M. Process for conversion of coal to substitute
0 .6 0 natural gas (SNG). Contract No.: HCEI-8-05-001r2, http://
www.hceco.com/HCEI805001.pdf; August 2005.
0 .5 5 U=0.4 U=0.5 U=0.6 U=0.7
[4] He BS, Li MY, Wang X, Zhu L, Wang LL, Xue JW, et al.
0 .5 0 Chemical kinetics-based analysis for utilities of ZEC power
0 1 2 3 4 5 6 7 8 9 10 11
Reaction time (s) generation system. Int J Hydrogen Energy 2008;33:4673e80.
[5] Yan LB, He BS, Ma LL, Pei XH, Wang CJ, Li XS. Integrated
Effects of U on H2 mole fraction characteristics and performance of zero emission coal
system. Int J Hydrogen Energy 2012;37:9669e76.
Fig. 7 e Effects of T (K), pt (MPa) and U on the H2 mole fraction.
[6] Ziock HJ, Lackner KS, Harrison DP. Zero emission coal power,
a new concept. Los Alamos, New Mexico: Los Alamos
National Laboratory. Contract No.: LA-UR-01-2214, http://
5. Conclusions www.netl.doe.gov/publications/proceedings/01/carbon_seq/
2b2.pdf; 2001.
A coal hydrogasification kinetic model is set up in this work. [7] Lee SH, Lee JG, Kim JH, Choi YC. Hydrogasification
characteristics of bituminous coals in an entrained-flow
The model is validated against experimental data available
hydrogasifiers. Fuel 2006;85:803e6.
from literatures and then used to predict the effects of T, pt, U [8] Xu WC, Matsuoka K, Akiho H, Kumagai M, Tomita A. High
and t on the evolution of the major coal hydrogasification pressure hydropyrolysis of coals by using a continuous free-
products. Summing up the aforementioned expressions and fall reactor. Fuel 2003;82:677e85.
analysis, the conclusions can be drawn as follows. [9] Chem JS, Hayhurst AN. Fluidised bed studies of: (i) Reaction-
fronts inside a coal particle during its pyrolysis or
1) The coal hydrogasification model set up in this work is devolatilisation, (ii) The combustion of carbon in various coal
validated and proved to be reliable. The model can be chars. Combust Flame 2012;159:367e75.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 4 5 1 3 e4 5 2 3
[10] Epstein M, Chen TP, Ghaly MA. An analysis of coal
hydrogasification processes. San Francisco (CA): Bechtel
Corporation (US). Contract No.: EF77A012565. URL: http://
www.osti.gov/bridge/purl.cover.jsp?purl¼/6074682-KtEPFx/
6074682.pdf; 1978 Aug.
[11] Hippo EJ, Johnson JL. Modeling of initial stage
hydrogasification of various ranked coals. Chicago: Institute
of Gas Technology (US). Report No.: CONF7809025, http://
www.osti.gov/bridge/purl.cover.jsp?purl¼/6074682-KtEPFx/
6074682.pdf; 1978 Jan.
[12] Johnson JL. Kinetics of initial coal hydrogasification stages.
Chicago: Institute of Gas Technology (US). Report No.:
CONF770301P2, http://web.anl.gov/PCS/acsfuel/preprint%
20archive/Files/22_2_NEW%20ORLEANS_03-77_0017.pdf;
1977 Jan.
[13] Sakellaropoulos GP, Skodras G, Kaldis SP, Stavropoulos GG,
Kokorotsikos PS. Modeling of hydrogasification of a single
lignite char particle. Prepr Pap Am Chem Soc Div Fuel Chem
1978;32:176e85.
[14] Blackwood JD, McCarthy DJ. The mechanism of hydrogenation
of coal to methane. Aust J Chem 1966;19:797e813.
[15] David M. Mathematical models of the thermal
decomposition of coal. Fuel 1983;62:534e9.
[16] Biagini E, Masoni L, Pannocchia G, Tognotti L. Development
of gasifier models for hydrogen production optimization. In:
AIDIC conference series. p. 45e54, http://www.aidic.it/
icheap9/webpapers/439Biagini.pdf; 2009 Sep.
[17] Baum MM, Street PJ. Predicting the combustion behaviour of
coal particles. Combust Sci Technol 1971;3:231e43.
[18] Badzioch S, Hawksley PGW. Kinetics of thermal
decomposition of pulverized coal particles. Ind Eng Chem
Proc Des Dev 1970;9:521e30.
[19] Kobayashi H, Howard JB, Sarofim AF. Coal devolatilization at
high temperatures. In: 16th symposium (international) on
combustion; 1976. p. 411e25.
[20] Higuera FJ. Numerical simulation of the devolatilization of
a moving coal particle. Combust Flame 2009;156:1023e34.
[21] Grant DM, Pugmire RJ, Fletcher TH, Kerstein AR. Chemical
percolation model of coal devolatilization using percolation
lattice statistics. Energy Fuels 1989;3:175e86.
[22] Zhang A, Kaiho M, Yasuda H, Zabat M, Nakano K, Yamada O.
Fundamental studies on hydrogasification of Taiheiyou coal.
Energy 2005;30:2243e50.
[23] Fletcher TH, Kerstein AR, Pugmire RJ, Grant DM. Chemical
percolation model for devolatilization: 2. Temperature and
heating rate effects on product yields. Energy Fuels 1990;4(1):
54e60.
4523
[24] Fletcher TH, Kerstein AR. Chemical percolation model for
devolatilization: 3. Direct use of 13C NMR data to predict
effects of coal type. Energy Fuels 1992;6(4):414e31.
[25] Kumar M, Zhang C, Monaghan RFD, Singer SL, Ghoniem AF.
CFD simulation of entrained flow gasification with improved
devolatilization and char consumption submodels. In:
IMECE2009: ASME 2009 international mechanical
engineering congress and exposition, 2009 Nov 13e19. Lake
Buena Vista, Florida; 2009. p. 383e95.
[26] Wen CY, Chaung TZ. Entrainment coal gasification
modelling. Ind Eng Chem Proc Des Dev 1979;18:684e94.
[27] Liu XJ, Zhang WR, Park TJ. Modelling coal gasification in an
entrained flow gasifier. Combust Theor Model 2001;5:595e608.
[28] Wu XC, Wang QH, Luo ZY, Fang MX, Cen KF. Modelling on
effects of operation parameters on entrained flow coal
gasification (I): model established and validation. J Zhejiang
Univ (Eng Sci) 2004;38:1363e5 [in Chinese].
[29] FLUENT6.3-User’s guide. Fluent Inc.; 2006.
[30] Wu YX, Zhang JS, Yue GX, Lv JF. Analysis of dominating
process between mixing and reactions in a Texaco coal
gasifier. J Combust Sci Technol 2009;15:287e92 [in Chinese].
[31] Watkinson AP, Lucas JP, Lim CJ. A prediction of performance
of commercial coal gasifiers. Fuel 1991;70(4):519e27.
[32] Goyal A. Mathematical modelling of entrained-flow coal
gasification reactors [Ph.D.]. Chicago, IL: Illinois Institute of
Technology; 1980.
[33] Li Z, Wang TJ, Han ZM, Zheng HT, Ni WD. Study on
mathematical models of Texaco gasifier modelling. Power
Eng 2001;21:1161e5 [in Chinese].
[34] Brown BW, Smoot LD, Smith PJ, Hedman PO. Measurement
and prediction of entrained-flow gasification processes.
AIChE J 1988;34:435e46.
[35] Borgwart RH. Calcination kinetics and surface area of
dispersed limestone particles. AIChE J 1985;31:103e11.
[36] Bhatia SK, Perlmutter DD. A random pore model for fluid-
solid reactions: 1. Isothermal, kinetic control. AIChE J 1980;
26:379e86.
[37] He Y. Common computer numerical algorithm and
programming. Beijing: Posts and Telecom Press; 2003 [in
Chinese].
[38] Falk AY, Schuman MD, Kahn DR. Advancement of flash
hydrogasification: Task VIII-performance testing. Topical
Report. Morgantown Energy Technology Center. Contract
No.: DE-AC21e78ET10328., http://www.osti.gov/bridge/purl.
cover.jsp?purl¼/5377768 -SKAxm4/5377768.pdf; 1986 Jun.
[39] Missen RW, Mims CA, Saville BA. Chemical reaction engineering
and kinetics. New York: John Wiley & Sons, Inc; 1999.