Front. Energy Power Eng.
China 2009, 3(3): 369–372
DOI 10.1007/s11708-009-0044-7
RESEARCH ARTICLE
Zhe WANG, Jinning YANG, Zheng LI, Yong XIANG
Syngas composition study
© Higher Education Press and Springer-Verlag 2009
Abstract The syngas composition characteristic was
investigated in the real slurry-feed gasifier using a detailed
gas phase reaction mechanism. The results show that the
time for syngas to reach equilibrium is much shorter than
the residence time for slurry feed entrained-flow gasifiers,
indicating a gas phase species partial equilibrium state.
Further calculation shows that the four major species, CO,
CO2, H2, and H2O, are in equilibrium via the reaction
CO þ H2 O () CO2 þH2 . Suggestions are provided for
future modeling and model validation.
Keywords gasification, syngas composition, simulation
1 Introduction
Integrated gasification combined cycle (IGCC) is gaining
more and more attention as one of the cleanest coal
technologies. However, the low availability of IGCC is a
bottleneck for successfully commercializing the technol-
ogy [1] partially due to the current ineffective control
method. Currently, signals such as the appearance of the
collected slag and the concentration of CH4 are utilized as
feed back signals for temperature control. In real applica-
tion, however, the concentration of CH4 is not reliable
enough to control the gasifier temperature since this is a
down-stream measurement, which does not reflect the
gasification operation condition accurately.
Modeling is a powerful tool to obtain a more detailed
and deeper understanding of the gasifier dynamic perfor-
mance and to help design a more reliable measurement
method for temperature control. In equilibrium models [2–
4], minimum Gibbs free energy was used to calculate the
equilibrium state species concentration. The reaction rates
among the involved species were assumed to be fast
Received December 4, 2008; accepted March 31, 2009
✉
Zhe WANG, Jinning YANG, Zheng LI ( ), Yong XIANG
The State Key Lab of Power Systems, Department of Thermal
Engineering, Tsinghua-BP Clean Energy Center, Tsinghua University,
Beijing 100084, China
E-mail: lz-dte@tsinghua.edu.cn
enough to reach an equilibrium state before exiting the
gasifier. In kinetic models [5–13], gasifier performance
was studied by calculating the reaction rate of the
heterogeneous and homogenous reactions inside the
gasifier. In the model of Li et al. [5, 6], in which five
heterogeneous and six homogenous reactions were
considered, a cell model concept was utilized to divide
the Texaco gasifier into a series of cells to calculate the
mass and energy balance for each cell. More complicated
CFD modeling work included momentum, mass, and
energy conservation of the solid and gas phase species
together with the turbulence calculations [7–13]. In these
models, too much attention was paid to the flow structure
and concentration distribution inside the gasifier. There-
fore, the reaction mechanisms were simplified, which
might lead to inaccuracy in the final syngas compositions.
A detailed reaction mechanism is thus needed to study the
gasification process.
2 Basic research approach
Due to the incomplete understanding of surface chemistry,
currently, no clear heterogeneous reaction mechanism for
gasification is available. However, it is possible to
decouple the gas phase reactions from the heterogeneous
reactions. As described by Perkins and Sahajwalla [14],
coal gasification process can be divided into wet zone, dry
zone, and gas film zone. In the wet zone, there is no
reaction, and thus, only heat transfer needs to be
calculated. The kinetics of gas combustion and gasification
are mostly concentrated in the dry zone. In the dry zone,
the volatile composition in the coal is devolatilized from
the coal and in the second stage of the reaction are the
reactions between the solid carbon, O2, and H2O, which
produces CO and H2 and releases chemical energy to
maintain the high gasifier temperature. In the gas film zone,
gas phase reactions dominate the process. Previous
modeling work [6–13] has already shown that the carbon
conversion ratio remains almost constant after the mixture
enters the last stage (gas film zone) of the gasifier.
Therefore, it is possible to study the gas film zone reactions
370 Front. Energy Power Eng. China 2009, 3(3): 369–372
using only a gas phase reaction mechanism, which is
further supported by the fact that at this stage, the unburnt
coal is almost completely covered with ash, isolating the
particle from the surrounding gases.
For a slurry feed entrained-flow gasifier, the typical
syngas is comprised of CO (35%–45%), CO2 (10%–15%),
H2 (27%–30%), H2O (15%–25%), and H2S and COS
(0.2%–1%). For a dry feed, the typical syngas is comprised
mainly of CO (60%–65%). Considering that the amount of
COS and H2S is very small, it is assumed in the present
work that after the main reaction zone (the dry zone), the
concentration of COS and H2S does not change too much.
Thus, the well-accepted C–H–O–N reaction mechanism
(GRI MECH III, the mechanism of Li et al. [15]) was
chosen to study the syngas transitional performance in the
gasifier. It needs to be pointed out that although the present
work is directed at slurry-feed entrained-flow gasifiers, the
methodology is applicable to other types of gasifiers.
Inside the gasifier, there are two limiting conditions:
gases pass through the gasifier without any recirculation or
mixing; and the gases inside the gasifier are well stirred.
The real situation is between these two extremes. In the
present work, commercially available Chemkin software
was used to investigate the syngas composition, with a
closed-homogenous reactor (CHR) model to simulate the
first condition and a perfectly stirred reactor (PSR) model
to simulate the second.
3 Syngas dynamic performance
The syngas from Tampa IGCC power plant was chosen as
the baseline for analyses. The syngas composition is listed
in Table 1. As described above, the concentrations of COS
and H2S were assumed to remain constant during the
calculations.
Calculations were made to study the transient perfor-
mance if the selected syngas were put back into the gasifier
operating at 2560 kPa and 1588.15 K. In Fig. 1, the solid
lines are CHR calculation results and the dotted lines are
PSR calculation results (residence time: 1 s). It is seen that
the solid and dotted lines overlap, showing that in a real
entrained-flow gasifier, there is no difference between the
two extreme conditions. Because of this, only CHR
calculations were performed in most of the analyses. As
shown, the time it takes for the gas phase species to reach a
quasi-equilibrium state is about 0.04 s (defined as equili-
bration time in the present work), which is much shorter
Table 1 Tampa IGCC power plant syngas composition (mole fraction)
CO H2 H2O
0.347102 0.279211 0.196819
Ar N2 H2 S
–3 –2 –3
5.036
10 2.5797
10 6.794
10
than the residence time of a typical gasifier (generally a few
seconds). Although the present calculation is aimed at the
gas film zone, it needs to be pointed out that in a real
gasification process, the gas phase species start to react
with each other from the beginning of the gasification
process. Furthermore, the existence of radical species such
as O, OH, and H inside the high-temperature gasifier
accelerates the reactions, so the equilibrating process could
be even shorter, as shown in Fig. 1. Both GRI MECH III
and Li's reaction mechanisms were applied in the present
calculations, and little difference was found between the
results, further verifying the applicability of these reaction
mechanisms. Checking the NH3 and CH4 concentration
change, it was found that the equilibration time for NH3 is
about 1 second, indicating a quasi-equilibrium state. In
addition, the CH4 concentration differs from its original
value by about three times. Since most of the CH4 was
produced outside the gasifier, the downstream-measured
CH4 concentration would naturally not be reliable as a
feedback signal for controlling purposes. The baseline
syngas compositions are measured values, and the final
concentration in Fig. 1 can be regarded as the real value
inside the gasifier. It is seen that there is a difference
between the measured value and the actual value,
suggesting that there is a composition shift during the
measurement process due to the temperature and pressure
drop. Currently, the measured syngas composition is
regarded as a standard to validate the model results. The
results presented in Fig. 1 clearly show that this is
arguable, and the measure value needs modification for
validation.
The effect of the initial syngas composition on the
equilibration time was also investigated. Two series’ of
calculations were performed to study the effects of the
initial syngas compositions. One simulated conditions with
the same carbon conversion ratio while the other simulated
conditions with a slight change in carbon conversion
ratios.
The first series simulated the conditions with same
carbon conversion ratio by keeping the C, H, and O
concentrations constant (Fig. 2). Under this condition,
there are different ratios of CO2/CO with the same C, H,
and O concentrations, which may result from different
heterogeneous reactions. As shown, even if the initial
concentration differs from each other (H2, for example),
the time to reach equilibrium is the same (0.04 s), and the
final composition of the syngas is the same. These results
indicate that the ratio of CO2 and CO generated from the
CO2 CH4
–4
0.137503 1.61
10
COS NH3 O2
–5 –3
9.66
10 1.476
10 3.00
10–6
 Zhe WANG et al. Syngas composition 371

Fig. 3 CHR results for the syngas to reach equilibrium from

Fig. 1 CHR and PSR results for the syngas to reach equilibrium different carbon conversion ratio
in real condition ( p = 2560 kPa, T = 1588.15 K)
heterogeneous reaction mechanism to obtain the correct
carbon conversion ratio and a correct set of gas phase
reaction mechanism to finalize the syngas compositions.
To obtain a clear picture of the equilibration time of the
syngas under different temperatures and pressures, several
series of calculations were performed. As the temperature
or the pressure increase (Fig. 4), the equilibration time for
the syngas becomes shorter, reflecting the fact that the
overall gas phase reaction rate increases with temperature
and pressure. As shown, the temperature is the most
important parameter affecting the equilibration time. For
Texaco entrained-flow gasifier, the working pressure is
between 30 and 5000 kPa, and the working temperature is
above 1573 K. Under this condition, the equilibration time
for the syngas is always below 0.1 s. This implies that the
Fig. 2 CHR result for the syngas to reach equilibrium from
different initial conditions (H2 mole fraction)
initial heterogeneous reactions produced syngas has
enough time to reach a quasi-equilibrium state since the
typical residence time of an entrained-flow reaction is
reaction between oxygen and carbon may not be as
about a few seconds. Figure 4 also indicates that in
important for slurry-feed entrained flow gasifier modeling
entrained-flow gasifier modeling, an accurate set of gas
as regarded by previous researchers [5–13] since the
composition will be equilibrated to the same value very
quickly.
The second series simulated the gasification process
with different carbon conversion ratios (Fig. 3). Under this
condition, the H, O, and N atomic concentrations were kept
constant while changing the carbon concentration in gas
phase species. As shown, even as the carbon conversion
ratio changes, which may result from a change in coal
particle-size or flow structure, the syngas reaches equili-
brium within the same time (0.04 s). Since there is more
carbon in the syngas, the final CO concentrations have
different values.
These two series of calculations clearly show that the gas
phase reactions modulate the final syngas composition to a
quasi-equilibrium state very quickly (some minor species
such NH3, H2S may not be in equilibrium). These
Fig. 4 Equilibration time under different temperatures and
results suggest that for gasifier modeling and simulation,
pressures (p = 100, 500, 1000, 2000, 2500, 3000, 3500, 4000,
there are two important issues that require attention: a 4500, and 5000 kPa for different lines)
372 Front. Energy Power Eng. China 2009, 3(3): 369–372
phase reactions determines the overall quality of the model
for syngas concentration. Moreover, the coal-gas reaction
mainly determines the carbon conversion ratio. Thermo-
dynamic calculations are accurate enough for entrained-
flow gasifier modeling if a proper carbon conversion ratio
can be calculated. The result can also be applied to other
types of gasifiers. For example, for fluidized bed gasifiers,
the equilibration time is larger than 1 s, as shown in Fig. 4,
indicating that under this condition, the gas phase is not
equilibrated. Also, there may be tar generated during the
coal gasification process inside the fluidized-bed gasifier,
which needs more time to decompose. It would not be
proper to establish a thermodynamic model based on
minimum free Gibbs energy for this kind of gasifier.
The main gas species of syngas from a Texaco entrained-
flow gasifier are CO, H2, CO2, and H2O. The shift reaction,
CO þ H2 O () CO2 þ H2
connects these major species together. If the gas phase
species reach a quasi-equilibrium state, the shift reaction
should also be in an equilibrium state, which can be
confirmed by applying the equilibrium constant of the shift
reaction,
pCO2
pH2
Kp ¼
pCO
pH2 O
to the final syngas compositions. It was found that the shift
reaction is absolutely equilibrated over a broad temperature
range. Together with the previous conclusion, it strongly
suggests that in entrained-flow gasifier modeling, the
bidirectional shift reaction should be taken into account.
4 Conclusion carriage
Using detailed gas phase reaction mechanisms, the
dynamic performance of syngas inside an entrained-flow
gasifier was studied. The results show that the gas phase
species reach a quasi-equilibrium state in a very short time,
mainly due to the shift reaction. The results also suggest
that for entrained flow gasifier modeling and simulation,
carbon conversion ratio and the shift reaction almost
completely determines the major syngas compositions and
that the measured syngas composition used to validate
modeling work may be arguable.
Acknowledgements The work was sponsored by the National Basic
Research Program of China (No. 2005CB221207).
References
1. Maustad O. An overview of coal based integrated gasification
combined cycle (IGCC) technology. 2005, http://lfee.mit.edu/
public/LFEE_2005-002_WP5.pdf
2. Ruggiero M, Manfrida G. An equilibrium model for biomass
gasification processes. Renewable Energy, 1999, 16(1–4): 1106–
1109
3. Chern S M, Wallawender W P, Fan L T. Equilibrium modeling of a
downdraft gasifier. 1. overall gasifier. Chemical Engineering
Communications, 1991, 108(1): 243–265
4. Li X, Grace J, Watkinson A, et al. Equilibrium modeling of
gasification: a free energy minimization approach and its application
to a circulating fluidized bed coal gasifier. Fuel, 2001, 80(2): 195–
207
5. Li Z, Wang T, Han Z, et al. Study of mathematical model for Texaco
gaifier (I)–Modeling. Power Engineering, 2001, 21(2): 1316–1319
6. Li Z, Wang T, Han Z, et al. Study of mathematical model for Texaco
gaifier (II)–Calculation and analysis. Power Engineering, 2001, 21
(4): 1161–1168
7. Ruprecht P, Schafer W, Wallace P. A computer model of entrained
coal gasification. Fuel, 1988, 67(6): 739–742
8. Chen C, Horio M, Kojima T., Numerical simulation of entrained
flow coal gasifiers. Part I: Modeling of coal gasification in an
entrained flow gasifier. Chemical Engineering Science, 2000, 55(8):
3861–3874
9. Chen C, Horio M, Kojima T. Numerical simulation of entrained
flow coal gasifiers. Part II: Effects of operating conditions on gasifier
performance. Chemical Engineering Science, 2000, 55(8): 3875–
3883
10. Chen C, Horio M, Kojima T. Use of numerical modeling in the
design and scale-up of entrained flow coal gasifiers. Fuel, 2001, 80
(10): 1513–1523
11. Choi Y, Li X, Park T, et al. Numerical study on the coal gasification
characteristics in an entrained flow coal gasifier. Fuel, 2001, 80(15):
2193–2201
12. Cho H. A numerical study on parametric sensitivity of the flow
characteristics on pulverized coal gasification. International Journal
Energy Research, 2000, 24(6): 511–523
13. Vicente W, Ochoa S, Aguillon J, et al. An Eulerian model for the
simulation of an entrained flow coal gasifier. Applied Thermal
Engineering, 2003, 23(15): 1993–2008
14. Perkins G, Sahajwalla V. A mathematical model for the chemical
reaction of a semi-infinite block of coal underground coal
gasification. Energy & Fuels, 2005, 19(4): 1679–1692
15. Li J, Zhao Z, Kazakov A, et al. A comprehensive kinetic mechanism
for CO, CH2O, and CH3OH combustion. International Journal of
Chemical Kinetics, 2007, 39(3): 109–136