Experimental Investigation of Natural Coke Steam Gasication in a

Bench-Scale Fluidized Bed: Inuences of Temperature and Oxygen

Flow Rate
Wen-guo Xiang* and Chang-sui Zhao
School of Energy and EnVironment, Southeast UniVersity, Nanjing 210096, Jiangsu, China
Ke-liang Pang
National Power Plant Combustion Engineering Research Center, Shenyang, Liaoning 110034, China
ReceiVed August 29, 2008. ReVised Manuscript ReceiVed NoVember 17, 2008
Natural coke was selected as a steam gasication feedstock in a bench-scale uidized bed (i.d. 50 mm, H
1600 mm). The impacts of the gasication temperature and the oxygen ow rate on product gas composition,
product gas yield, and gas heating value were investigated with a steam ow rate of 1050 g/h and a natural
coke ow rate of 200 g/h. Experimental results show that gasication temperature has a signicant inuence
on gasication properties. As the temperature goes up, the contents of H
2
and CO
2
in the product gas decline,
whereas the content of CO increases. As the temperature was from 850 to 1000 C, the volume fractions of
H
2
, CO, and CO
2
in the product gas changed from 63.0%, 25.0%, and 9.6% to 59.8%, 20.2%, and 18.5%,
respectively. The product gas yield increased by 4.3 times, the carbon conversion rate increased from 10.25%
to 47.76%, and the gas heating value increased from 8.87 to 9.33 MJ/m
3
. Oxygen in the oxidant reagent steam
affects the gasication properties. The product gas yield and the carbon conversion increased by 1.76 times
and 1.94 times, respectively, when the oxygen ow rate was from 0 to 0.2 L/min. But as it further increased
to 1.0 L/min, the product gas yield increased only by 1.16 times and the carbon conversion increased by 1.34
times. The effective composition in the product gas continued to decrease from 76.0% to 54.3%, and the
heating value was lowered from 9.01 to 6.35 MJ/m
3
as the oxygen ow rate was raised from 0 to 1 L/min. The
CO
2
composition increased persistently from 23.1% to 37.3%.
1. Introduction
Natural coke, a high metamorphic grade coal as a byproduct
of the coal mining process, which looks like articial coke, is
a kind of solid mineral fuel from the coal seam subjected to
magma intrusion, fast pyrolysis, and carbonization with a heating
value of 18-30 MJ/kg.
1-3
Natural coke existing in the coal
seam in the vertical and horizontal direction is generally
discarded in the gob area of coal mines, which is improvident
and causes pollution. Natural coke reserves are rich in China;
for example, the remaining geological reserves are 3 billion tons
in Shandong Province, and the total recoverable natural coke
reserves are about 1 billion tons in Huaibei, Anhui Province.
4,5
It is helpful for solving energy shortage problems to use natural
coke to generate electricity. However, natural coke was restricted
in application and research due to its hot burst, difcult ignition,
and abradability. In most cases, natural coke is discarded in
nature or is unexploited in the mine. For these reasons, the author
and co-workers
6-9
chose to use the natural coke as a gasication
material in the bench-scale uidized bed as well as to investigate
the apparent morphology, microcrystalline structure, and py-
rolysis process by SEM (scanning electron microscopy), XRD
(X-ray diffraction), and TG-FTIR (thermogravimetry Fourier
transform infrared spectrometry).
The hot burst factor of natural coke has no impact on the
gasication process due to the dramatic uidization state of bed
material in a uidized bed. At the same time, natural coke with
high abradability is suitable for gasication in the uidized bed
because the uidized bed has wider adaptability to coal type
together with the characteristic of directly utilizing the coal of
10 mm below from coal production. Natural coke will be rapidly
* To whom correspondence should be addressed. Telephone: 86-25-
83795545. E-mail: wgxiang@seu.edu.cn.
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(3) Kwiecinska, B. K.; Hamburg, G.; Vleeskens, J. M. Formation
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(8) Pang, K. L.; Zhao, C. S.; Lin, L. S.; Xiang, W. G. XRD and
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(9) Pang, K. L.; Xiang, W. G.; Zhao, C. S. Investigation on pyrolysis
characteristic of natural coke using thermogravimetric and Fourier-transform
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Energy & Fuels 2009, 23, 805810 805
10.1021/ef800724t CCC: $40.75 2009 American Chemical Society
Published on Web 01/05/2009
heated to gasication temperature by higher bed temperature.
10,11
Fluidized beds now nd wide application in coal or biomass
gasication. However, due to their high degree of solids mixing
as well as particle entrainment, a single uidized bed cannot
achieve high carbon conversion. Ocampo et al.
12
carried out
experiments to study coal char gasication characteristics at
different steam/coal and air/coal ratios and temperatures of
gasifying agent in a uidized bed. Bayarsaikhan et al.
13
studied
steam gasication of a Victorian brown coal in an atmospheric
bubbling uidized bed reactor with continuous feeding of the
coal. In the study of Chatterjee
14
gasication of a high-ash India
coal in a laboratory-scale, atmospheric uidized bed gasier
using steam and air as uidizing media was studied. The
variation of product gas composition, bed temperature, caloric
value, and carbon conversion with oxygen and steam feed was
discussed, and the experimental data were compared with the
predicted. Huang et al.
15
studied the gasication characteristics
for a sub-bituminous coal with an air-steam mixture in a
pressurized uidized bed gasier. Australian coal was gasied
at atmospheric pressure in an internally circulating uidized bed
with a draft tube by Kim et al.
16
The effects of reaction
temperature, oxygen/coal mass ratio, coal feed rate, and steam/
coal mass ratio on composition of product gas, carbon conver-
sion, cold gas efciency and gas yield, and caloric value were
determined. Similar work was done also by Kikuchi et al.,
17
Gutierrez and Watkinson,
18
and Crnomarkovic et al.
19
And more,
Cousins et al.
20
investigated the reactivity of chars formed in
uidized bed gasiers and found the char reactivity declines
rapidly during its formation as part of the pyrolysis of the coal.
The effect of pyrolysis time on char reactivity in a uidized
bed was discussed by Liu et al.,
21
and they found that a longer
pyrolysis time led to lower reactivity of a char, while this effect
leveled off as pyrolysis time increased. Guo et al.
22
investigated
the changes in char structure during the gasication of brown
coal in a uidized bed/xed bed reactor. Li et al.
23
performed
biomass gasication tests in a pilot-scale air-blown circulating
uidized bed gasier. Encinar and co-workers
24,25
carried out
isothermal experiments on steam gasication of Cynara car-
dunculus between 300 and 800 C in a xed bed and found
that particle size, nitrogen ow rate, and initial sample weight
generally did not exert any inuence, whereas temperature was
very signicant. van Dyk et al.
26
studied the effect of temper-
ature and gasication medium with the aim of optimizing
cogasication of coal and wastes for Sasol-Lurgi gasiers.
Pohorely et al.
27
investigated cogasication of 23 wt % PET
and 77 wt % brown coal in an atmospheric uidized bed gasier
of laboratory scale. The gasication agent was composed of 10
vol % O
2
in bulk of nitrogen. The inuences of experimental
conditions, such as the uidized bed and freeboard temperatures,
on major and minor gas components and tar content, as well as
features of the blended fuel gasication in comparison with the
single coal gasication, were studied. The study above inves-
tigated mostly the gasication of coal char or biomass char.
The properties of natural coke are different from those of coal
or biomass as discussed in papers.
6-9
They should be character-
ized in natural coke gasication. In this study natural coke from
Peicheng coal mine (Xuzhou, Jiangsu, China) was selected as
the gasication feedstock, and steam is used as the oxidant
reagent. The author investigated the characteristics of natural
coke steam gasication in a bench-scale uidized bed gasier.
The gasier was operated at an atmospheric pressure to
determine the effects of temperatures (850, 900, 950, and 1000
C) and oxygen ow rates (0-1.0 L/min) in the oxidant reagent
steam on the variation of the product gas composition, the
product gas yield, the gas heating value, and the carbon
conversion.
2. Experimental Section
2.1. Setup. The experimental setup is shown in Figure 1. The
setup consists of a uidized bed reactor (i.d. 50 mm, H 1600 mm),
a steam generator, a two-stage steam superheater, natural coke
feeding system, gas purication, data acquisition system, and a
temperature control section. The preheated steam enters the reactor
in the lower conically shaped part of the reactor, and natural coke
is blown to the reactor in the lower part of the reactor through
nitrogen. Temperature sensors and differential pressure indicators
were located along the gasier reactor. Additional temperature
sensors are installed to measure the temperature in the center of
the uidized bed, and the reactor is heated by electrical heaters
and is maintained at a given temperature through the control system.
Gases from the reactor pass through a small cyclone to separate
small particles. The amount of particles collected in the cyclone is
measured after each experiment. Then the gas is lead to a water
cooler where the steam vapors are condensed. A demister is installed
in case the steam vapors are not fully condensed in the cooler.
Eventually the product gas is measured by a ow meter and is
analyzed by a gas analysis unit (including CO, CO
2
, CH
4
, and H
2
).
2.2. Sample Preparation. Natural coke from Peicheng coal mine
(Xuzhou, Jiangsu, China) was used as the sample in this study.
(10) Ma, S. X.; Yang, X. Y. Study on dynamic behavior of the
combustion system of a circulating uidized bed boiler. Proc. CSEE (in
Chinese) 2006, 26, 116.
(11) Jin, Y.; Zhu, J. X.; Wang, Z. W.; Yu, Z. Q. Fluidization Engineering
Principles; Tsinghua University Press: Beijing, 2001 (in Chinese).
(12) Ocampo, A.; Arenas, E.; Chejne, F.; Espinela, J.; Londono, C.;
Aguirrea, J.; Perez, J. D. An experimental study on gasication of Colombian
coal in uidized bed. Fuel 2003, 82, 161164.
(13) Bayarsaikhan, B.; Sonoyama, N.; Hosokai, S. Inhibition of steam
gasication of char by volatiles in a uidized bed under continuous feeding
of a brown coal. Fuel 2006, 85, 340349.
(14) Chatterjee, P. K.; Datta, A. B.; Kundu, K. M. Fluidized bed
gasication of coal. Can. J. Chem. Eng. 1995, 73, 204210.
(15) Huang, J.; Fang, Y.; Chen, H.; Wang, Y. Coal gasication
characteristic in a pressurized uidized bed. Energy Fuels 2003, 17, 1474
1479.
(16) Kim, Y. J.; Lee, J. M.; Kim, S. D. Coal gasication characteristics
in an internally circulating uidized bed with draught tube. Fuel 1997, 76,
10671073.
(17) Kikuchi, K.; Suzuki, A.; Mochizuki, T.; Endo, S.; Imai, E. Ash-
agglomerating gasication of coal in a spouted bed reactor. Fuel 1985, 64,
368372.
(18) Gutierrez, L. A.; Watkinson, P. A. Fluidized-bed gasication of
some Western Canadian coals. Fuel 1982, 61, 133138.
(19) Crnomarkovic, N.; Repic, B.; Mladenovic, R.; Neskovic, O.;
Veljkovic, M. Experimental investigation of role of steam in entrained ow
coal gasication. Fuel 2007, 86, 194202.
(20) Cousins, A.; Paterson, N.; Dugwell, D. R.; Kandiyoti, R. An
investigation of the reactivity of chars formed in uidized bed gasiers:
The effect of reaction conditions and particle size on coal char reactivity.
Energy Fuels 2006, 20, 24892497.
(21) Liu, H.; Kaneko, M.; Luo, C. H.; Kato, S.; Kojima, T. Effect of
pyrolysis time on the gasication reactivity of char with CO2 at elevated
temperatures. Fuel 2004, 83, 10551061.
(22) Guo, X.; Tay, H. L.; Zhang, S.; Li, C. Z. Changes in char structure
during the gasication of a Victorian brown coal in steam and oxygen at
800 C. Energy Fuels 2008, 22, 40344038.
(23) Li, X. T.; Grace, J. R.; Lima, C. J. Biomass gasication in a
circulating uidized bed. Biomass Bioenergy 2004, 26, 171193.
(24) Encinar, J. M.; Gonzalez, J. F.; Gonzalez, J. Fixed-bed pyrolysis
of Cynara cardunculus L. Product yields and compositions. Fuel Process.
Technol. 2000, 68, 209222.
(25) Encinar, J. M.; Gonzalez, J. F.; Gonzalez, J. Steam gasication of
Cynara cardunculus L.: inuence of variables. Fuel Process. Technol. 2002,
75, 2743.
(26) van Dyk, J. C.; Keyser, M. J.; Coertzen, M. Syngas production
from South African coal sources using Sasol-Lurgi gasiers. Int. J. Coal
Geol. 2006, 65, 243253.
(27) Pohorey, M.; Vosecky, M.; Hejdova, P.; Puncochar, M.; Skoblja,
S.; Staf, M.; Vosta, J.; Koutsky, B.; Svoboda, K. Gasication of coal and
PET in uidized bed reactor. Fuel 2006, 85, 24582468.
806 Energy & Fuels, Vol. 23, 2009 Xiang et al.
The proximate and ultimate analysis results of the sample are shown
in Table 1, which reveals that the natural coke has higher carbon
content and less volatile matter with a higher heating value. The
quartz sand with an average particle size of 0.23 mm and density
of 2400 kg/m
3
was used as the bed material of the uidized bed
gasier. According to the Geldart classication, the sample particle
belongs to the B-type particle with a particle size of 100-600 m
and a density of 1400-4000 kg/m
3
. The uidization velocity is set
to 1.26 m/s, and the uidization numbers is 2.5. Steam was chosen
as the uidizing medium with a ow rate of 1050 g/h, and the
natural coke ow rate was set to 200 g/h at ambient conditions.
2.3. Experiment Schedule. Two sets of experiments, including
inuences of gasication temperatures and inuences of oxygen
ow rates, were carried out to explore the steam gasication
characteristics of the natural coke, which included product gas
compositions, gas heating value, product gas yield, and carbon
conversion. Experiments of the natural coke steam gasication under
four different temperatures, 850, 900, 950, and 1000 C were
performed. The inuences of oxygen ow rate on the gasication
properties were performed. The oxygen, mixing with steam as the
oxidant reagent, was induced to the uidized bed in the lower
conically shaped part of the gasier reactor. Six different oxygen
ow rates, 0.1, 0.2, 0.4, 0.6, 0.8, and 1.0 L/min at a temperature of
900 C were included in the experiments.
2.4. Reaction Time. Figure 2 shows the trend of product gas
composition versus the reaction time under an experiment condition
(1000 C, natural coke ow of 200 g/h, steam ow of 1050 g/h,
oxygen ow of 0.1 L/min). As can be seen, there was uctuation
in the product gas composition for the rst minutes. As the
gasication reactions go on, the uctuation was kept in a narrow
range, so the reaction time was kept for 30 min in the experiments.
3. Results and Discussion
3.1. Gasication Characteristics under Different Tem-
peratures. Steam was the uidization media and the oxidant
reagent for the experiments. The reaction temperature is one of
the most important operating variables affecting the performance
of the uidized bed natural coke gasier since the main
gasication reactions (C + H
2
O f CO + H
2
and C + CO
2
f
2CO) are endothermic. In this section, the inuences of
gasication temperature on the product gas compositions,
heating value, metric volume of product gas, and carbon
conversion of natural coke are discussed. Four temperatures,
850, 900, 950, and 1000 C, were selected to perform the
experiments.
3.1.1. Effects of Gasication Temperature on Gas Composi-
tions. The gasication temperature plays an important role in
natural coke steam gasication. The effects of the gasication
temperature on the compositions of the product gas are shown
in Figure 3. As can be seen, compositions of the product gas
are H
2
(63.0-59.8%), CH
4
(2.4-1.5%), CO (9.6-18.5%), and
CO
2
(25.0-20.2%). The effective gas (H
2
+ CO + CH
4
) has
slightly increased with the increase of temperature at a constant
value of steam/carbon ratio. In this research, the contents of H
2
and CH
4
decreased by 3.2% and 0.9% from 63.0% and 2.4%
to 59.8% and 1.5%, respectively, whereas the volume percentage
of CO increased by 8.9% from 9.6% to 18.5% for an increase
in gasication temperature from 850 to 1000 C. The volume
percentage of CO
2
decreased from 25.0% at 850 C to 20.2%
at 1000 C.
In the steam gasication of a carbonaceous material, several
reactions take place simultaneously, reactions 1-5. The extent
to which each reaction is involved depends on the operating
conditions. Reaction 2 requires high temperature, and reactions
4 and 5 require high pressure. Hence, reactions 1 and 3 are the
main reactions of interest in steam gasication when the reaction
is carried out at atmospheric pressure and temperatures above
850 C.
C+H
2
OfH
2
+CO H) +130.1 kJ/mol (1)
C+CO
2
f2CO H) +170.7 kJ/mol (2)
CO+H
2
OfCO
2
+H
2
H)-40.2 kJ/mol (3)
2CO+2H
2
fCH
4
+CO
2
H)-247.5 kJ/mol (4)
C+2H
2
fCH
4
H)-74.9 kJ/mol (5)
Reaction 1 is endothermic, H ) 130.1 kJ/mol, and reaction 3
is exothermic, H ) -40.2 kJ/mol. Therefore, an increase or
Figure 1. Experimental setup of uidized bed reactor: (1) water tank;
(2) steam boiler; (3 and 4) steam superheater; (5 and 6) electric heater;
(7) slag cans; (8) gasier body; (9) electric heater; (10) coke feeder;
(11) cyclone; (12) ash cans; (13) gas cooler; (14) dry tower; (15)
owmeter; (16) gas analyzer.
Table 1. Proximate and Ultimate Analyses of the Natural Coke
proximate analysis/% (mass, air-dry) ultimate analysis/% (mass, daf)
M A V xed carbon C H O N S
0.81 16.15 9.05 73.99 93.12 1.99 3.21 1.10 0.58
Figure 2. Product gas composition vs time.
Figure 3. Gas compositions vs operation temperature.
Natural Coke Steam Gasication Energy & Fuels, Vol. 23, 2009 807
decrease of the temperature displaces reactions 1 and 2 in
opposite directions. Consequently, the temperature is an im-
portant variable with regard to the nal composition of the gases.
The thermodynamic expectations are in good accordance with
the above experimental results. Reactions 1 and 2 are hetero-
geneous and strongly endothermic, and thus the rise in tem-
perature is conducive to a shift of equilibrium toward the right
side. Reactions 1 and 2 are accompanied by other exothermic
reaction 3, which contributes to the formation and depletion of
the above-discussed components H
2
and CO
2
.
Methane is of a higher heating value and can contribute a lot
for gas heating value. However, it can be found that CH
4
content, unlike the previously discussed trends for CO, CO
2
,
and H
2
, exhibits only weak temperature dependence, changing
the value from 2.4% at 850 C to 1.5% at 1000 C, as shown
in Figure 3. The methanation reactions 4 and 5 are exothermic
and need higher pressure. In general, the rates of carbon
oxidation by steam and carbon dioxide are of the same order
of magnitude, whereas the hydrogenation reaction (i.e., reaction
5) is several orders of magnitude slower than the steam-char
and CO
2
-char reactions.
28
Huang et al.
15
reported that the
equilibrium concentration of CH
4
should be less than 0.2% at
a temperature of 930 C in their PFB gasier experiments. In
the above experiments, a pyrolysis process and another gasica-
tion that produces activated carbons and energy-rich gaseous
products take place simultaneously. According to the thermo-
grametric analysis by Pang et al.,
9
the pyrolysis process of the
natural coke is different from that of coal with three stages of
pyrolysis. Its pyrolysis process can only be divided into two
degasication stages. The rst stage (room temperature to 550
C) is a drying degasication stage, and its decomposition
products are similar to that of coal pyrolysis, of which the
oxygenic aroma compounds are in the majority. The second
stage (550-1000 C) is a fast degasication stage, the main
stage, and its weigh loss is more than 70% of the total loss.
The decomposition gases are mainly CO
2
and CO, and less
amass double bond and treble bond, C(CH
3
)
3
and -CH(CH
3
)
2
series matter, which may form the light hydrocarbon. That
implies that the CH
4
would be mainly formed from the volatile
cracking, and the higher the temperature is, the less CH
4
is
released, as reported in the literatures.
15,16,25
3.1.2. Effect of Gasication Temperature on the Gas
Production Yield. The gasication temperatures of Peicheng
natural coke with steam were set to 850, 900, 950, and 1000
C. The changes of the gas production with the temperature
are shown in Figure 4. The gas production increases rapidly
with the increase of the gasication temperature, which shows
that gasication temperature is the main factor affecting
gasication reaction of Peicheng natural coke. The gas produc-
tion increased by 56 L/h from 80 L/h at 850 C to 136 L/h at
900 C, by 90 L/h from 900 to 950 C, and 117 L/h from 950
to 1000 C. The gas production increased by 4.3 times from 80
L/h at 850 C to 343 L/h at 1000 C. With increasing
temperature there is a major increase in the yield of gases. This
increase is due rst to the production of gases in the initial period
of pyrolysis (increasing with temperature), and second to the
cracking of tars which would also be favored by temperature,
and third to the increase in reaction rate with temperature. The
yield of gases increases sharply about 900 C. This effect has
also been observed by other workers
24,25
and seems to be due
to the existence of a rst period dominated by cracking of the
volatile matter and a second period dominated by reactions 1
and 2. In consonance with this, the conversion also increases
with temperature. The changes of the product gas components
with gasication temperature are also shown in Figure 4. With
the increase of gasication temperature, the components of
product gas increase along with the increase of the product gas
yield. The H
2
production increased signicantly from 50.4 to
205.1 L/h because of the increase of the total gas production
with the increase of gasication temperature, whereas the percent
of H
2
changed little (as shown in Figure 3) with the increase of
the total gas production.
3.1.3. Effect of Gasication Temperature on the Gas
Heating Value. From Figure 3, it can be seen that H
2
reduces
slowly and the CH
4
slightly declines, but the content of CO
increases gradually with the increase of the gasication tem-
perature. The increase of CO is large enough to offset the decline
of H
2
and CH
4
in composition so that the effective content
increases in the gas. CO
2
content decreases accordingly. The
specic changes are shown in Figure 5, where the heating value
of the gas also increases with the increase of gasication
temperature resulting from the increase of the effective com-
ponent production. The gas heating value increased by 5% from
8.87 MJ/m
3
at 850 C to 9.33 MJ/m
3
at 1000 C, while gas
heating value per hour increased by 4.5 times from 0.71 to 3.20
MJ, because of the dramatic increase of gas production with
the increase of gasication temperature.
3.1.4. Effect of the Gasication Temperature on the
Carbon ConVersion. According to the gas production, we
estimated that natural coke did not completely react with steam
in the uidized bed. Here carbon conversion rate was used to
describe the degree of gasication reaction. Carbon conversion
rate was calculated based on total inlet natural coke and outlet
product gas data at a given instant, and the gas composition
was determined by the gas chromatography at the same instant.
Carbon conversion rates of the samples were 10.25%, 17.90%,
30.13%, 47.76% at the gasication temperatures of 850, 900,
(28) Smoot, L. D.; Smith, P. J. Coal Combustion and Gasication;
Plenum Press: New York and London, 1985.
Figure 4. Gas production vs gasication temperature.
Figure 5. Gas heating value and effective composition content vs
gasication temperature.
808 Energy & Fuels, Vol. 23, 2009 Xiang et al.
950, and 1000 C (as shown in Figure 6), which indicates the
gasication temperature is the key factor impacting the carbon
conversion. In the experiments, gasication time was kept for
30 min and was relatively short. Because of low gasication
reactivity of char, char would be accumulated in the bed during
gasication, so the carbon conversion would have been higher
if the reaction time was longer.
3.2. Inuences of Oxygen Flow on Gasication Charac-
teristics. In the experiments, the natural coke ow and steam
ow were set 200 and 1050 g/h, respectively, and the gasica-
tion temperature was kept at 900 C. The oxygen ow was set
to zero as in the former experiments and then increased from
0.1 to 1 L/min in the following experiments.
3.2.1. Inuences on Gas Production and Carbon ConVer-
sion. The gas production and carbon conversion increase with
the rise of the oxygen ow, as shown in Figure 7. The gas
production increases quickly with the oxygen ow rate when
less than 0.2 L/min, and then increases slowly. When the oxygen
ow increased from 0 to 0.2 L/min, the gas production increased
1.8 times from 136 to 239 L/h. And as the oxygen ow increased
from 0.2 to 1.0 L/min, the gas production increased only by
1.2 times from 239 to 278 L/h. The carbon conversion rate
changes in line with the gas production, which increases quickly
when the oxygen ow rate is less than 0.2 L/min, and then
increases slowly with the increase of oxygen ow rate.
Because of the oxygen in the oxidant reagent, reactions 6-9
occur during the natural coke steam gasication. The reactions
are exothermic. The reaction of carbon does not stop at CO,
but any free oxygen rapidly reacts with CO in the gas phase to
produce CO
2
. For the fuel-rich uidized bed gasier, the much
slower endothermic reaction 2 may occur. Because the heat
released from the reaction between char and oxygen, reaction
1 is strengthened resulting in the increase of carbon conversion.
Because of reactions 8 and 9, CO and H
2
are consumed by the
existence of oxygen.
C+O
2
fCO
2
H)-393.8 kJ/mol (6)
C+0.5O
2
fCO H)-283.3 kJ/mol (7)
CO+0.5O
2
fCO
2
H)-110.5 kJ/mol (8)
H
2
+0.5O
2
fH
2
O(g) H)-242.0 kJ/mol (9)
The initial increase of the oxygen ow rate in the steam can
strengthen the diffusion of oxygen to the surface of solid carbon,
and more oxygen molecules are absorbed in the carbon surfaces,
so on the reaction interface natural coke particles (char) contact
with oxygen more easily and fully, and char is consumed rapidly
with increase of oxygen ow. However, when the oxygen ow
rate reaches a certain value, i.e., 0.2 mL/min in the experiments,
the reaction surfaces of carbon particles reach a saturated state.
Bulk surface diffusion reaction is converted to the pore diffusion
reaction or chemical reaction. As the oxygen ow rate increases
further, the chemical reaction is rate-determining.
28
The increase
altitude of reaction rate goes lower, so the inuences of oxygen
diffusion to the carbon particle surfaces on the gasication
reaction are almost weak and the carbon conversion tends to
change a little.
3.2.2. Inuences on the Gas Composition. With the change
of the oxygen ow in the oxidant reagent, gas composition and
gas components change, as shown in Figures 8 and 9. Methane
shows little correspondence with the oxygen ow because of
its relatively lower content. Effective gas compositions (CH
4
,
H
2
, and CO) are reduced, whereas CO
2
content increases
because of the reactions 8 and 9. Oxygen was measured
unreacted in the outlet gas when oxygen ow was further
increased because of the short resident time in the uidized bed
gasier and quick cooling in the outlet. As described in the
former section, the carbon conversion gets increased when
oxygen is added to steam as an oxidant reagent. When oxygen
was raised from 0 to 0.2 L/min at rst, the carbon conversion
increased rapidly by 1.94 times and more product gases were
generated also. Although the addition of oxygen in the oxidant
Figure 6. Carbon conversion rate vs gasication temperature.
Figure 7. Inuences of the oxygen ow rate on gas production and
carbon conversion.
Figure 8. Inuences of oxygen ow rate on gas compositions.
Figure 9. Inuences of oxygen ow rate on gas component production.
Natural Coke Steam Gasication Energy & Fuels, Vol. 23, 2009 809
steam consumes the combustible gases CO and H
2
, the CO and
H
2
yields in the product gas are increased because more effective
product gases are produced. When oxygen was raised further
from 0.2 to 1.0 L/min, the carbon conversion increased slowly
only by 1.34 times and the product gases generated slowed
down, and the CO and H
2
yields tended to decrease. At the
oxygen ow rate of 0.2 L/min, CO and H
2
productions reached
the peak.
3.2.3. Inuences on the Gas Heating Value. Because of
reactions 8 and 9, CO
2
in the product gas goes up, and effective
gases CO and H
2
go down, whereas CH
4
shows little change.
Thus, the gas heating value of the resulting gas gets decreased
as the decline of the effective gas contents, as shown in Figure
10. And the gas heating value per hour is also given in the gure.
From Figure 10, one observes that the gas heating per hour
increases at the oxygen ow rate of 0-0.2 L/min because of
the rise of CO and H
2
production, and then it declines as the
decrease of CO and H
2
production when the oxygen ow rate
is from 0.2 to 1.0 L/min. When the oxygen ow rate increases
from 0 to 0.2 L/min, the gas heating value per hour increases
1.6 times from 1.23 to 1.96 MJ because of the rapid rise in the
carbon conversion rate. The heating value per hour reaches the
highest at the oxygen ow rate of 0.2 L/min.
4. Conclusions
Experiment results of Peicheng natural coke steam gasication
show that the gasication temperature and oxygen rate are the
major factors affecting the gasication characteristics. With the
increase of gasication temperature, the contents of H
2
and CO
2
in the production gas decline, whereas the content of CO
increases. As the gasication temperature rose from 850 to 1000
C, the volume fractions of H
2
, CO, and CO
2
in the production
gas changed from 63.0%, 25.0%, and 9.6% to 59.8%, 20.2%,
and 18.5%, respectively. Production gas increased by 4.3 times,
carbon conversion rate got increased from 10.25% to 47.76%,
and the gas heating value increased from 8.87 to 9.33 MJ/m
3
.
Oxygen in the oxidant reagent steam affects the gasication
properties prominently. Product gas yield increased by 1.76
times, and carbon conversion rate increased by 1.94 times, as
the oxygen ow rate increased from 0 to 0.2 L/min. But as it
further increased to 1.0 L/min, the product gas yield increased
only by 1.16 times and carbon conversion rate increased by
1.34 times. Effective composition in the product gas continued
to decrease from 76.0% to 54.3%, and the heating value was
lowered from 9.01 to 6.35 MJ/m
3
, as the oxygen ow rate was
raised from 0 to 1 L/min. The CO
2
composition increased
persistently from 23.1% to 37.3%.
Acknowledgment. The authors express thanks to the National
Natural Science Foundation of China (90410009, 50776018) and
the Special Fund of the National Priority Basic Research of China
(2007CB210101) for providing nancial support of this project.
EF800724T
Figure 10. Inuences of oxygen ow rate on gas heating value and
effective components.
810 Energy & Fuels, Vol. 23, 2009 Xiang et al.