Article

pubs.acs.org/IECR

Development of a Kinetic Model for Industrial Entrained Flow Coal

Gasifiers
Feng Qian,*,† Xiangdong Kong,† Hui Cheng,† Wenli Du,† and Weimin Zhong*,‡
†
Key Laboratory of Advanced Control and Optimization for Chemical Processes, Ministry of Education, and ‡Automation Institute,
East China University of Science and Technology, Shanghai 200237, China

ABSTRACT: The characteristics of the industrial Texaco entrained flow coal gasifier are numerically studied in this paper. A
kinetic model is proposed by dividing the gasifier into two zones to obtain the temperature and product concentration
distribution along the reactor. These two zones are the pyrolysis−combustion zone and the reduction zone. The pyrolysis−
combustion zone is modeled using the stoichiometry method. A detailed investigation was carried out on the gasification reaction
rates in the reduction zone. The particle swarm optimization technique is introduced in this paper to address the lack of
heterogeneous reaction kinetic parameters based on the random pore model for the specific feed Shenfu coal, and the huge
deviation of the industrial product gas composition from the theoretical composition at equilibrium state. With the evaluated
optimum kinetic parameters, robust agreement is achieved between the model outputs and the industrial data. Moreover, a
sensitivity analysis related to the O2-to-coal ratio and coal slurry concentration was carried out in light of the proposed model.

1. INTRODUCTION The current study proposes a model for an industrial Texaco

Coal gasification technology is being developed worldwide for a
more efficient and clean use of coal with substantially reduced
carbon dioxide and pollutant gas emissions.1 Entrainment flow
coal gasification is regarded as a practical coal-utilizing
technology due to its advantages of high carbon conversion
with short residence time and fossil fuel versatility. Synthetic
gas (syngas) is the major product of coal gasification, and is
primarily a mixture of hydrogen and carbon monoxide. Syngas
is a very flexible intermediate product that can be used either as
fuel for electricity generation or as a raw material for synthetic
fuel production.
A viable model can provide a better understanding of gasifier
characteristics and the complicated reaction phenomena in the
reactor under high temperature and pressure. Many efforts have
been devoted toward developing gasifier models through
thermodynamic equilibrium modeling and the kinetic modeling
approach. The pure equilibrium approach assumes the
reactions in the gasifier reach a thermodynamic equilibrium
state.2−6 Therefore, a closer prediction is easy to implement
and provide when the reaction temperature is sufficiently high.
Although equilibrium models are used in the preliminary study
of process fundamentals, they pose difficulties in being adapted
for process analyses and optimization procedures. Compared
with equilibrium models, kinetic models are more accurate and
could give more detailed information of the gasification
processes. However, the use of kinetic models is more difficult
and time-consuming in terms of coming up with a solution.7−12
In addition, kinetic gasification models are generally established
for specific gasifiers and types of feed. The kinetic parameters
derived from the literature are not applicable for different coal
or gasifier types. Several studies were reported on reaction
kinetic rate determination for pyrolysis and gasification
processes using the parameter fitting approach.13−15 Research-
ers adopted different optimization methods to minimize errors
between model results and experimental results in the search
for optimal parameters for specific reacting conditions.
down-flow entrained bed gasifier with a water quench section
designed to treat up to 500 tons of coal per day as water slurry
type. The gasifier is divided into two zones: (1) pyrolysis−
combustion zone and (2) reduction zone. Detailed kinetic
behaviors of pyrolysis and combustion reactions involved in the
pyrolysis−combustion zone are not considered. The products
of the pyrolysis−combustion zone are calculated using the
stoichiometry method by assuming that all the volatiles are
released and that the gasification agent oxygen is combusted
completely. Beneath the pyrolysis−combustion zone is the
reduction zone, where the char gasification reactions occur. The
occurring reactions are regarded as the key procedures for
reactor modeling. The random pore model (RPM)16,17 is
utilized to depict the behavior of the heterogeneous char
gasification reactions. Due to the differences of coal types and
gasification circumstances, using the parameters derived from
the literature will give mismatched results for the industrial
process as aforementioned. This disparity necessitates the
estimation of optimum kinetic parameters to model the specific
commercial gasifier and Shenfu coal feed precisely. Recently,
numerous efforts have been made to estimate the parameters
using intelligent methods.18−22 In this article, industrial data
and calculated values are compared, and optimum kinetic
parameters are estimated using the standard particle swarm
optimization (PSO) technique.23 This paper aims to develop a
simplified one-dimensional industrial gasifier model that
emphasizes the reaction behaviors in the reduction zone and
to determine the corresponding optimal parameters. Sensitivity
analysis is conducted to investigate the effects of the oxygen-to-
Received: January 13, 2012
Revised: October 8, 2012
Accepted: January 10, 2013
Published: January 10, 2013

© 2013 American Chemical Society 1819 dx.doi.org/10.1021/ie301630x | Ind. Eng. Chem. Res. 2013, 52, 1819−1828
Industrial & Engineering Chemistry Research
coal ratio (ROC) and coal slurry concentration on gasifier
performance.
2. PROCESS DESCRIPTION
The Texaco gasifier runs at an elevated pressure. The coal
slurry is atomized by a high-speed pure oxygen spray into the
gasifier from the jets. The small coal slurry particles are rapidly
accelerated, heated for a short period of time by flame, and then
transported along the gasifier. Then, the particles are dried
before being subjected to pyrolysis, combustion, and char
gasification to generate syngas. Separating the actual process
into pyrolysis−combustion and reduction zones can simplify
the model and improve accuracy.24 Figure 1 shows the sketch
Figure 1. Scheme of the physical model of the gasifier along with
possible reactions.
of the physical model of the gasifier along with possible
reactions in both zones. The pyrolysis−combustion zone is at
the top of the gasifier, where pyrolysis and combustion
reactions proceed. Pyrolysis is an extremely complex process
due to the large number of chemical and physical trans-
formations that occur rapidly and simultaneously.25 Pyrolysis
can be simplified by eq 1:
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Article
coal → α1CH4 + α2 H 2 + α3CO + α4CO2 + α5H 2O
+ α6char + α7 H 2S + α8 N2 + α9ash (1)
where αi is the number of moles of a species after
devolatilization.
The combustible pyrolysis products, such as CO, H2, and
CH4, quickly react with the oxidant, and a large amount of heat
is produced to heat coal rapidly to the pyrolysis temperature
simultaneously. The extent to which the oxidant is completely
or only partially depleted depends on the amount of volatile
products produced and of oxygen. Generally, an overall excess
of oxygen is needed to consume the volatile products
completely. Therefore, the product char can react with the
remaining oxygen to produce CO/CO2. Only eq 2 is
considered in the char combustion process in this paper to
simplify the solid−gas combustion reactions. The combustible
gas CO in turn reacts in the gas phase with oxygen to produce
CO2 and more heat. Once the temperature in the pyrolysis−
combustion zone exceeds 2000 K, the pyrolysis and
combustion reactions occur very quickly and can be
instantaneous. Therefore, the detailed kinetics of pyrolysis
and combustion can be neglected under these circumstances.
The char combustion reaction is as follows:
C(s) + 0.5O2 → CO (2)
Beneath the pyrolysis−combustion zone is the reduction
zone, where CO2 and H2O are reduced. The borderline is
assumed to be at the location where the oxygen is exhausted.
The gasification process in the reduction zone is key for syngas
production in a gasifier. This region has three main
heterogeneous reactions, namely, char−steam gasification,
char−carbon dioxide, and char−hydrogen, and two homoge-
neous reactions, namely, the water gas shift reaction (WGS)
and the methane steam reforming reaction (as shown in Figure
1). The possible products of the reduction zone are assumed to
be CO, CO2, H2, CH4, H2S, and N2. H2S and N2 are assumed
to be the final products for elemental sulfur and nitrogen in the
reducing gasification system based on the trace amounts of
sulfide and nitride in the products.
3. GASIFICATION REACTION KINETICS IN THE
REDUCTION ZONE
The slowest reactions in gasification that govern the overall
conversion rate are the heterogeneous reactions with char.26
However, obtaining the gasification rate is difficult due to the
combination of different mechanisms, such as mass transfer,
chemical reaction, and heat transfer. A great deal of research has
been carried out on the development of char gasification
reaction rate models.27−31 Still, the reaction rate expressions
adopted in the one-dimensional gasifier models rarely consider
the mass transfer rates. The expressions of the overall reaction
rates should consider the mass transfer among the gas phase,
char particles, and the intrinsic kinetics. The final reaction rate
of each heterogeneous reaction is calculated by32 the following:
R i ,dR i ,k
Ri =
R i ,d + R i ,k (3)
where Ri is the final reaction rate of the ith reaction, Ri,d is the
bulk diffusion rate, and Ri,k is the apparent chemical reaction
rate, which includes the effects of pore diffusion and the
intrinsic reactivity of char. The value of Ri,d is given as follows:
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Industrial & Engineering Chemistry Research
[(Ts + Tg)/2]0.75
R i ,d = Ci Pi
dp (4)
where Ci is the diffusion coefficient of the ith reactant, Ci = 3 ×
10−12 s K−0.7532, Ts is the absolute temperature of the particle,
Tg is the absolute temperature of the bulk gas phase, dp is the
particle diameter (in meters), and Pi is the partial pressure of
the ith reactant (in pascals).
The random pore model (RPM) is utilized to express
intrinsic heterogeneous reaction kinetics. The RPM is known to
be the most flexible in modeling the char gasification reactions
as it can represent the behavior of the char gasification process
that shows a maximum rate at certain conversion levels proved
by experiments.28 Liu et al.33 found that the RPM gives a
reasonable prediction of the char gasification rate in the
entrained flow coal gasifiers. The RPM model can be described
as34 follows:
dx ⎛ E ⎞
= A 0, i exp⎜ i ⎟(1 − x) 1 − ψi ln(1 − x) P n
dt ⎝ RTs ⎠ (5)
where x is the carbon conversion of each particle, ψi is the pore
surface parameter, i represents the different heterogeneous
reactions, A0,i is the frequency factor, Ei is the activation energy,
R is the gas constant, n is the reaction order, and Ts is the solid
particle temperature.
The intrinsic chemical reaction rate Ri,k can be obtained from
eq 5 based on stoichiometry. The particle diameter dp emerging
in eq 4 depends on char conversion and decreases along the
reactor length:
⎛ d p ⎞3
⎜⎜ ⎟⎟ = 1 − x + ε
⎝ d p,0 ⎠ (6)
where dp,0 is the initialized particle diameter. The constant ε in
eq 6 is assumed to be 1 × 10−4 to ensure convergence stability
with a minimum value of dp.
In addition to the three heterogeneous reactions mentioned
above, two homogeneous ones are considered, namely, the
WGS reaction and the methane steam reforming reaction
depicted in Figure 1. The two reactions attain equilibrium at
higher temperatures.10,11 Equilibria for the WGS reaction and
the methane steam reforming reaction are given in ref 35.
However, industrial measurements show that the water gas shift
reaction is not at equilibrium in the commercial gasifier; i.e., the
value of (yH2yCO2)/(yCOyH2O) for a real gasification system
differs from the equilibrium constant. Two fixed values are used
in the current work to account for the deviations from the
theoretical equilibrium constants of the WGS reaction and the
methane steam reforming reaction derived from ref 19 (Cf, the
corrective factor). These values help in dealing with the
predicted compositions in the actual process. The corrected
equilibrium constants can be obtained according to eq 7.
K = Cf K * (7)
where K is the final equilibrium constant for the homogeneous
reactions in this work, and K* is the theoretical equilibrium
constant from ref 35. Cf is practical to compensate for the
deviation from the theoretical equilibrium.
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4. MATHEMATICAL MODEL
The process of gasification is isobaric. The pyrolysis−
combustion zone immediately following the inlet of an
entrainment gasifier is similar to a stirred tank reactor. The
reduction zone is directly adjacent to the pyrolysis−combustion
zone; thus, the vortex pattern rapidly dissipates, and plug flow
can be assumed. The cell-in-series approach is employed to
represent the hydrodynamics in the reduction zone. The size of
the pyrolysis−combustion zone and the number of compart-
ments in series are determined assuming a temperature profile
based on the reference data for a similar reactor.10,12,36
Accordingly, the pyrolysis−combustion zone is assumed to be
completely mixed and is taken to account for about 1/20 of the
effective reactor size. Many experiments have been conducted
to study the effect of the compartment number on the model
predictions. In the present work, dividing the reduction zone
into 50 compartments is found to be the most suitable.
4.1. Model of the Pyrolysis−Combustion Zone. Due to
the high temperature of nearly 2000 K, the simulation of the
pyrolysis and combustion processes is instantaneously and
simultaneously considered. Reaction kinetics is not involved in
this study.
First, the composition of products after pyrolysis can be
calculated by atomic equilibrium equations in light of ultimate
element analysis and proximate analysis of the coal, i.e., the
conservation equations for atomic C, H, O, N, S, and ash. The
ratio of moles of CO and CO2 is assumed to be inversely
related to their molecular mass to close the equations. The
moles of the products after pyrolysis can be obtained by solving
the equations.
Second, when the combustible gases are completely burnt,
the amount of residual oxygen can be calculated from the mass
balance and stoichiometry:
n r‐O2 = nO2 − 2α1 − 0.5α2 − 0.5α3
(8)
where nr‑O2 is the number of moles of the residual oxygen when
the volatile parts have been completely burnt, and nO2 is the
number of moles of the oxygen fed into the gasifier. About 50%
of the excess oxygen reacts with char to form char monoxide.
Subsequently, char monoxide reacts with balanced 50% of
oxygen to generate CO2. The amount of CO as the
intermediate product can be expressed by eq 9:
nCO = n r‐O2 (9)
where nCO is the number of moles of CO.
Third, except for the inert gases H2S and N2, the products of
the pyrolysis−combustion zone can be obtained from eqs
10−12:
nC = α6 − n r‐O2 (10)
nCO2 = α1 + α3 + α4 + n r‐O2 (11)
n H2O = 2α1 + α2 + α5 (12)
where nC, nCO2, and nH2O indicate the number of moles of char,
CO2, and H2O, respectively.
Finally, the temperature calculations of gas and solid at the
exit of the pyrolysis−combustion zone are expressed by eqs 13
and 14.
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Industrial & Engineering Chemistry Research Article

solid phase heat balance gas phase heat balance

(WC
s p ,sTs)z p − b − (WC
s p ,sTs)0
∑ (WgmCp,gmTg)z +Δz − ∑ (WgmCp,gmTg)z
m m
= (AcAz p − b)[eFσ(Tg 4 − Ts 4) + hc p − b(Tg − Ts)] = −(AcAΔz)[eFσ(Tg − Ts 4) + hc(Tg − Ts)]
4

+ 0.5nCOΔHgs‐CO
(13)
gas phase heat balance
∑ (WgmCp,gmTg)z p − b − ∑ (WgmCp,gmTg)0
m m
= −(AcAz p − b)[eFσ(Tg − Ts 4) + hc p − b(Tg − Ts)]
4 Stokes’ law is applied for the solid flow in the gasifier, which
+ (2α1ΔHg1 + 0.5α2ΔHg2 + 0.5α3ΔHg3
+ 0.5nCOΔHg1)(1 − Hg‐loss) (14)
In eqs 13 and 14, Wg is the gas flow rate, Ac is the contact
area between the gas and the solid per unit volume of the
reactor, zp−b is the pyrolysis−combustion zone size; hcp−b is the
convection and conduction heat transfer coefficient in the
pyrolysis−combustion zone, m is the mth component of the gas
phase, and Hg‑loss is the heat loss in the pyrolysis−combustion
zone consisting of heat consumed by pyrolysis, drying, and heat
transport from the gas to the reactor. The viewing factor, F, for
radiation heat transfer between gas and coal particles, and the
emissivity, e, are assumed to be 1.0 and 0.9, respectively.
4.2. Model of the Reduction Zone. The reduction zone is
divided into compartments where the local variables (hydro-
dynamic, kinetic, and thermodynamic variables) are evaluated.
Compartments are solved sequentially with the output of the
Nth compartment considered as the input for the (N + 1)th
one.
The mass balances for solid particles and gas are illustrated in
eqs 15 and 16.
solid phase mass balance
3 The char reaction rate greatly depends on the coal type and
dWs
= −∑ ri /vs
dz i (15)
gas phase mass balance
2
Wgm , z +Δz − Wgm , z = AΔz∑ vm , jrj + ΔR sg
j (16)
In eqs 15 and 16, Δz is the cell size, ΔRsg indicates the gas
components produced by the solid−gas reactions in the current
cell, and i and j are the reactions in the solid and gas phases,
respectively.
The energy balances in the reduction zone can be described
by eqs 17 and 18.
solid phase heat balance
d(WC
s p ,sTs)
= AcA[eFσ(Tg 4 − Ts 4) + hc(Tg − Ts)]
dz
3
+ ∑ (−ΔHi)ri/vs
i (17)
1822
2
+ aA∑ ( −ΔHj)rj − Hloss,g‐w Δz
j (18)
In eqs 17 and 18, hc is the convection and conduction heat
transfer coefficient and Hloss,g‑w is the heat exchange per unit
area of the reactor wall, which is assumed to be constant.
is due to the small solid particle size and the low Reynolds
number obtained by eq 19. The gas flow rate is calculated using
the global mass balance of the produced gas during the
calculation process. The coal gasifier model can be established
by combining those for combustion−pyrolysis and the
reduction zone:
|vg − vs|
Rep = ρg d p
μg (19)
where Rep is the Reynolds number of the dimensionless
particle.
5. OPTIMIZATION OF THE HETEROGENEOUS
REACTION KINETIC PARAMETERS
Parameter estimation is critical in modeling. The gasification
reaction in the reduction zone is the rate-determining step in
the coal gasification process and the most important factor in
evaluating gasifier performance.31,34 The mass and energy
balance equations in the reduction zone can be solved only
after the parameters associated with them are obtained.
Determining the intrinsic kinetic parameters is critical in
establishing the gasification model. In this study, the kinetic
parameters for the three heterogeneous reactions and the Cf
values for the two homogeneous reactions need to be
estimated.
gasification circumstances. Most studies about the RPM are
based on experiments under atmospheric pressure or with a
packed bed reactor at specific conditions. Thus, the kinetic
parameters obtained in the literature cannot express the natural
behavior of the heterogeneous reaction in the industrial
process. However, determination of the optimal reaction rate
parameters is difficult due to the nonlinearity of the models.
Therefore, the PSO technique is used to optimize the kinetic
parameters of the char gasification reactions. The PSO
technique performs robustly for systems that have large
parameter spaces containing many local optima, especially
when no obvious starting value exists for the optimization
problems.23,37
The PSO method is a population-based search algorithm. In
this method, each individual, often called a particle, represents a
candidate solution in the feasible space of the optimization
problem. Each particle is characterized by its position and
current velocity. The fitness function or the objective function
is introduced to assess the quality of the particle location, and
this process is called fitness evaluation. Each particle flies
through the search space with an adaptable velocity that is
dynamically modified by combining the best position found so
far by itself, namely, pbest, and the best position found by any
dx.doi.org/10.1021/ie301630x | Ind. Eng. Chem. Res. 2013, 52, 1819−1828
Industrial & Engineering Chemistry Research Article

member of the particle’s topological neighborhood, namely, 6. RESULTS AND DISCUSSION

gbest, with several random perturbations. The cognitive The industrial data are taken from a Texaco down-flow
acceleration factor determines the magnitude of the random entrained bed gasifier that is designed to treat up to 500 tons of
forces in the degree of pbest, whereas the social acceleration coal per day as water slurry type, at an operating pressure of 4.0
factor determines the magnitude of the random forces in the MPa, and with an exit temperature between 1400 and 1700 K.
degree of gbest. These learning strategies are known to belong The industrial data were gathered by averaging the measure-
to the flying experience. This process is repeated until a user- ments in 1 min. The obtained data went through steady-state
defined stopping criterion is reached. identification and gross error detection to eliminate noise-
The PSO is briefly described as follows:23 containing data. The typical Shenfu coal with an average
1. Initialization. Create a population array of particles with particle diameter of 80 μm is used in the gasifier as feed.
random positions and velocities in the search space. Proximate and ultimate analyses of the Shenfu coal are given in
2. Main Loop. Table 1.
(a) For each particle i, evaluate the desired optimization
fitness yi at current position xi. Table 1. Properties of Shenfu Coal
(b) Compare each particle’s fitness evaluation with the best
function result so far, which is called pbesti. If yi is better, then proximate anal. of coal
(dry basis, wt %) ultimate anal. of coal (dry basis, wt %)
update pbesti to the current value, and make pi equal to the
current location xi. fixed
carbon volatile ash C H O N S ash
(c) Identify the particle in the neighborhood with the best
58.9 33.9 7.2 74.56 5.31 11.48 0.99 0.46 7.2
success so far, and then assign its index to the variable g.
(d) Update the velocity vi and position xi of the particle
according to the following equation: 6.1. Optimization Results. The standard PSO technique is
used to obtain the optimum model parameters based on the
vi⃗ ← ωvi⃗ + c1r1(pi ⃗ − xi⃗ ) + c 2r2(gi⃗ − xi⃗ ) data set collected from the industrial gasification process. In this
(20) model, the parameters of Ψ, A0, E, and Cf need to be estimated.
xi⃗ ← xi⃗ + vi⃗ However, the RPM has the same structural parameter Ψ for the
same coal with different gases. In the experiments, the
where ω is the inertia weight factor, c1 and c2 are the cognitive parameters for PSO algorithm are settled as follows: the initial
and social acceleration factors, respectively, and r1 and r2 are the population size N = 50, the maximum iteration number G =
random numbers uniformly distributed in the range [0,1]. 100, the inertia weight factor ω = 0.729, and the cognitive and
3. Cycle. Repeat from step 2 until a certain termination social acceleration factors c1 and c2 are both set at 1.494. Other
criterion is met. parameters involved in the experiments are chosen empirically.
Fitting the model to industrial data involves searching for the The calculated optimum kinetic parameters of the heteroge-
kinetic parameters that minimize the error criterion, which is neous reactions based on the RPM in the reduction zone are
generally the sum of squared differences between the outputs listed in Table 2.
calculated by the proposed model and those from the industrial
measurements. The deviations considered here as the objective Table 2. Calculated Char Gasification Reaction Kinetic
function are given by Parameters for Shenfu Coal by PSO
parameter reaction estd value 95% confidence limit
⎡m ⎛ j ⎛ T j − T j ⎞2
Ci ,sim − Cij,ind ⎞
l 2
⎢ Ψ − 12 0.11
f = ∑ ⎢∑ ⎜⎜ ⎟⎟ + ⎜ g,sim j g,ind ⎟
j ⎜ ⎟ A0,1 C + H2O 1.26 × 107 4.12 × 105
j=1 ⎣ i=1 ⎝ C i ,ind ⎠ ⎝ Tg,ind ⎠ E1 (kJ/mol) 226.08 7.32
2.03 × 105 5.483 × 103
⎞2 ⎤
A0,2 C + CO2
⎛Xj j
char,sim − Xchar,ind ⎥ E2 (kJ/mol) 169.03 5.88
+ ⎜⎜ j
⎟⎟
⎥ A0,3 C + H2 1.22 × 103 94.3
⎝ Xchar,ind ⎠⎦ (21) E3 (kJ/mol) 166.87 3.1
Cf1 CO + H2O 1.11 0.05
where f is the objective function, i is the ith dry product gas Cf2 CH4 + H2O 0.76 0.12
component (available in the industrial measurements, including
CO, CO2, CH4, and H2), j is the data point, and Ci is the The optimized kinetic parameters are then applied to
volume fraction of component i. simulate the industrial gasifier under different operating
Gas composition is measured online by a gas chromato- conditions, and the output component concentrations are
graphic analyzer at the exit of the water scrubber, and the obtained. Detailed information of the operating conditions for
carbon conversion is calculated from the carbon residue these runs is given in Table 3. The current study compares the
analysis conducted by an analyst from the plant. The cooling calculated CO, H2, and CO2 mole fractions on a dry basis and
rate in the quench coolers is very high (around 30 000 K/s). carbon conversion using the present model with optimized
The temperature in the quench cooler is sufficiently low to stop kinetic parameters, as well as that with the parameters from ref
the kinetics of the water gas shift reaction. Operational 34 due to a lack of RPM parameters for the Shenfu coal and
experience suggests that very little to no reaction occurs in from industrial data. The parity plots are shown in Figures 2−5.
the quench cooler and scrubber. Therefore, the gas Figures 2−4 show the distributions of CO, CO2, and H2 in the
composition measured at the exit of the water scrubber is product syngas, in which y1CO, y1CO2, and y1H2 denote the volume
approximately equal to that at the exit of the gasifier. fractions of CO, CO2, and H2 based on the optimized kinetic
1823 dx.doi.org/10.1021/ie301630x | Ind. Eng. Chem. Res. 2013, 52, 1819−1828
Industrial & Engineering Chemistry Research Article

Table 3. Experiment Conditions of the Texaco High

Pressure Gasifier
slurry feed rate slurry concn O2 flow rate
case (m3/h) (wt %) (Nm3/h)
run 1 31.14 57.6 15 028.75
run 2 30.82 58.8 15 119.04
run 3 31.02 59.2 15 214.66
run 4 29.36 61.7 15 106.51
run 5 30.98 62.0 15 891.96
run 6 30.63 61.6 15 716.53
run 7 30.55 59.0 15 003.69
run 8 28.76 58.2 14 197.59
run 9 28.23 57.9 14 133.98
run 10 27.99 58.4 14 210.19
run 11 27.17 58.5 13 942.81
run 12 27.95 60.1 14 684.71
run 13 27.84 59.5 14 236.02 Figure 4. Comparison of industrial volume fractions of H2 with model
run 14 29.14 60.2 14 971.66 predictions.

Figure 5. Comparison of industrial carbon conversions with model

Figure 2. Comparison of industrial volume fractions of CO with
model predictions.
Figure 3. Comparison of industrial volume fractions of CO2 with
model predictions.
parameters, respectively, and y2CO, y2CO2, and y2H2 denote the
model predictions with the parameters derived from ref 34,
respectively. Figure 5 shows the carbon conversion distribution,
whereby Conversion1 denotes the calculated carbon conversion
1824
predictions.
based on the optimized kinetic parameters and Conversion2
denotes the calculated carbon conversion based on the kinetic
parameters derived from ref 34.
The predictions of the present model show a close fit with
the real volume fractions of CO, H2, and CO2, and carbon
conversion. For the volume fractions of the product gas, the
maximum relative error between the calculated one and the
industrial measurement is about 6.3%. For the carbon
conversion, the relative error is less than 1.1%. Therefore, the
present model with its optimum kinetic parameters listed in
Table 2 is reliable, given the operating conditions of this study.
Figures 6 and 7 show the model predictions in the form of
temperature profiles, carbon conversion profile, and species
concentration profiles along the axis distance of the gasifier at a
specified condition. The gasifier is operated at 4.0 MPa, with a
coal slurry flow rate of 28.8 m3/h, a slurry concentration of
60%, and an oxygen flow rate of 14 619 Nm3/h.
Figure 6 shows the temperature profiles for solid and gas and
the carbon conversion profile. Two peaks are observed in the
temperature profiles of the solid and gas. These maximum
points are associated with the point at which the oxygen is
completely consumed and combustion reactions end. As long
as oxygen exists in the bulk gas, a significant temperature
difference will be observed between the coal particles and the
bulk gas. After oxygen depletion, the temperatures decrease
dx.doi.org/10.1021/ie301630x | Ind. Eng. Chem. Res. 2013, 52, 1819−1828
Industrial & Engineering Chemistry Research
Figure 6. Calculated temperature profiles and carbon conversion
profile at a specified condition.
Figure 7. Calculated product gas composition profiles (wet basis) at a
specified condition.
along the reduction zone, and the difference between the solid
and gas temperatures drops. This drop in temperature is due to
char gasification reactions, which are endothermic reactions
that become predominant in the reduction region.
The changes in gas composition over the reactor length are
illustrated in Figure 7. In the pyrolysis−combustion zone, any
methane, hydrogen, or carbon monoxide produced is
immediately consumed in the gas phase. In the initial
combustion period, the concentrations of steam and carbon
dioxide increase and show maxima after the oxygen is
exhausted, whereas the concentrations of CO, hydrogen, and
methane decrease to zero. Only when the oxygen concentration
falls to zero do hydrogen and CO appear in the bulk gas.
Subsequently, CO and hydrogen formation occur, and the
concentrations of both increase along the length of the
reduction zone. Meanwhile, the concentrations of steam and
CO2 decrease toward the exit of the reactor.
6.2. Effect of O2-to-Coal Ratio. The effects of feed oxygen
on gasifier performance are studied using the proposed model
at 4.0 MPa, with a coal slurry flow rate of 28.8 m3/h and a coal
slurry concentration of 60%. In Figure 8a, the carbon
conversion and the gasification temperature are plotted as a
function of the ROC. With increase in the ROC, the
gasification temperature rises, and the reaction rates in the
1825
Article
Figure 8. Effect of the ROC on (a) temperature and carbon
conversion and (b) product gas compositions.
gasifier become faster. A higher temperature accelerates char
gas reactions. Hence, the carbon conversion approaches unity.
The product gas composition fraction of each component
and the efficient syngas yield at various ROCs are shown in
Figure 8b. As the ROC increases, the CO composition
considerably increases whereas H2 rapidly decreases. The
reason is that a higher operating temperature makes the water
shift reaction move to the direction where more CO is
generated and suppresses H2 generation. Moreover, the
composition of the syngas has a maximum value when the
ROC is around 0.99. At this point, an increase of CO
composition and a decrease of H2 composition balance and
create an optimization point. Simulation results show a
decreasing trend for CO2 when the ROC is less than 0.99.
Trends will be reversed if the ROC is higher than 0.99 as a
result of the increase in oxygen supply.
6.3. Effect of Slurry Concentration. The effects of the
coal slurry concentration ranging from 56 to 68% on
gasification performance are likewise investigated. In previous
literature,10−12,36 analyses on slurry concentration were carried
out at a fixed ROC. However, the change of the coal slurry
concentration causes the amount of supplied oxygen to vary
with it at a fixed ROC. Therefore, the effect of coal slurry
concentration is examined through three cases shown in Table
4.
dx.doi.org/10.1021/ie301630x | Ind. Eng. Chem. Res. 2013, 52, 1819−1828
Industrial & Engineering Chemistry Research Article

Table 4. Three Methods To Change the Slurry

Concentration
case number
1 2 3
coal slurry constant changing with coal constant
flow rate slurry
concentration
O2 feed constant constant changing with coal
flow rate slurry
concentration
ROC changing with coal constant constant
slurry
concentration

Figures 9, 10, and 11 show the effects of the coal slurry

concentration on the carbon conversions, gasification temper-

Figure 10. Effect of coal slurry concentration on (a) temperature and

carbon conversion and (b) product gas composition for case 2.

the slurry concentration. In both cases 2 and 3, the simulation

Figure 9. Effect of coal slurry concentration on (a) temperature and
carbon conversion and (b) product gas composition for case 1.
atures, and product gas compositions for these three cases,
respectively. In Figure 9 for case 1, with the increase of slurry
concentration, the gasification temperature and carbon
conversion decrease simultaneously. The reason is that the
ROC decreases as the coal slurry concentration increases when
the input O2 flow rate and coal slurry rate remain constant. In
this condition, the average temperature in the reactor decreases
and consequently reduces the char gasification reaction rates.
The composition of CO increases significantly, whereas that of
CO2 decreases. In addition, H2 changes slightly with respect to
1826
results show similar performances, which can be observed in
Figures 10 and 11. The gasification temperature slightly rises,
whereas the carbon conversion remains unchanged due to the
decrease of heat needed for slurry water evaporation. In both
cases, the mole fraction of CO increases. However, the mole
fraction of H2 exhibits the opposite trend due to the
compromise between the increasing temperature and the
exothermic water gas shift reaction. Based on all three cases,
the increase of coal slurry concentration improves the efficient
gas yield. However, the carbon conversion decreases in case 1.
The amount of dry coal treated in the industrial process is fixed.
Thus, the method described in case 2 can provide a better
performance for optimization.
7. CONCLUSION
By dividing the gasifier into pyrolysis−combustion and
reduction zones, this work proposes a new model for an
industrial Texaco entrained flow coal gasifier. A standard PSO
technique is applied to estimate the reaction parameters in the
reduction zone. The temperature profiles in the solid and gas
phases over the gasifier length, as well as the carbon conversion
and the product concentrations, are obtained. The present
model can properly predict the behavior of the industrial
entrainment coal gasifier to improve process performance. On
the basis of the proposed model, a sensitivity analysis related to
dx.doi.org/10.1021/ie301630x | Ind. Eng. Chem. Res. 2013, 52, 1819−1828
Industrial & Engineering Chemistry Research Article

for Outstanding Young Scholars (61222303), and the Shanghai

Leading Academic Discipline Project (B504).

■ NOTATION
A0 = pre-exponential index
At = cross-sectional area of reactor (cm2)
Ac = contact area between the gas and the solid per unit
volume of reactor (m2/m3)
Cj = diffusion coefficient of the jth rate (K−1)
Cf = corrective factor
Cp,g, Cp,s = specific heats of gas and solid, respectively (J/
kg·K)
c1, c2 = cognitive and social acceleration factors, respectively
Di, Do = inside and outer gasifier diameters, respectively
(cm)
dp = particle size (m)
E = activation energy (kJ/mol)
e = emissivity of gas
ΔH = enthalpy of the reaction (J/mol)
Hloss = heat loss
hcp−b = convection heat transfer coefficient in the pyrolysis−
combustion zone (J/m2·K)
Hg‑loss = heat loss in the pyrolysis−combustion zone
Hloss,g‑w = heat exchange per unit area of reactor wall (J/m·s)
hc = convection and conduction heat transfer (J/m2·K)
K = equilibrium constant
n = number of moles (mol/s)
P = pressure (Pa)
R = gas constant (J/mol·K)
Ri = net rate of generation or consumption of species i due
to chemical reactions (mol/m3·s)
r1, r2 = random numbers
t = time (s)
Figure 11. Effect of coal slurry concentration on (a) temperature and Tg = gas-phase temperature (K)
carbon conversion and (b) product gas composition for case 3. Ts = solid-phase temperature (K)
u = velocity (m/s)
the practical operating variables, such as the ROC and coal Wg = gas flow rate (mol/s)
slurry concentration, is carried out. The increase of the ROC Ws = solid flow rate (mol/s)
significantly increases carbon conversion and the temperature x = carbon conversion
of the reactor. For a given slurry concentration, an optimal y = volume fraction
ROC that maximizes the efficient gas yield exists. Furthermore, z = height (m)
the effects of coal slurry concentration are analyzed three ways. zp−b = height of the pyrolysis−combustion zone (m)
With the increase of coal slurry concentrations, the Greek Symbols
composition of the efficient gas in the product gases increases, α = constant
and the CO concentration sharply increases. Keeping the ROC αi = mole fraction of ith species after devolatilization
constant offers an advantage of changing the coal slurry μ = kinetic viscosity (kg/m·s)
concentration in the industrial processes. In addition, the slurry ρ = density (kg/m3)
concentration should be large enough to enhance the yield of σ = Stefan−Boltzmann constant (J/m2·s·K4)
the effective compositions in the product gas. Ψ = structural parameter

■ AUTHOR INFORMATION
Corresponding Author
ω = inertia weight factor
Subscripts
d = diffusion
*E-mail: fqian@ecust.edu.cn (F.Q.); wmzhong@ecust.edu.cn g = gas
(W.Z.). Tel.: 86-21-64252060 (F.Q.); 86-21-64251250 (W.Z.). i = ith reaction
Notes j = jth reaction
The authors declare no competing financial interest. k = intrinsic

■ ACKNOWLEDGMENTS
This work is supported by the Major State Basic Research ■
m = mth component

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