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