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A thermodynamic analysis of methanation reactions of carbon oxides for the
production of synthetic natural gas
Jiajian Gao,ab Yingli Wang,a Yuan Ping,a Dacheng Hu,a Guangwen Xu,a Fangna Gu*a and Fabing Su*a
Received 24th August 2011, Accepted 7th December 2011
DOI: 10.1039/c2ra00632d
Published on 30 January 2012. Downloaded on 9/17/2023 6:23:17 AM.

Synthetic natural gas (SNG) can be obtained via methanation of synthesis gas (syngas). Many
thermodynamic reaction details involved in this process are not yet fully understood. In this paper, a
comprehensive thermodynamic analysis of reactions occurring in the methanation of carbon oxides
(CO and CO2) is conducted using the Gibbs free energy minimization method. The equilibrium
constants of eight reactions involved in the methanation reactions were calculated at different
temperatures. The effects of temperature, pressure, ratio of H2/CO (and H2/CO2), and the addition of
other compounds (H2O, O2, CH4, and C2H4) in the feed gas (syngas) on the conversion of CO and
CO2, CH4 selectivity and yield, as well as carbon deposition, were carefully investigated. In addition,
experimental data obtained on commercial Ni-based catalysts for CO methanation and three cases
adopted from the literature were compared with the thermodynamic calculations. It is found that low
temperature, high pressure, and a large H2/CO (and H2/CO2) ratio are favourable for the
methanation reactions. Adding steam into the feed gas could alleviate the carbon deposition to a large
extent. Trace amounts of O2 in syngas is unfavourable for SNG generation although it can lower
carbon deposition. Additional CH4 in the feed gas almost has no influence on the CO conversion and
CH4 yield, but it leads to the increase of carbon formed. Introduction of a small amount of C2H4, a
representative of hydrocarbons in syngas, results in low CH4 yield and serious carbon deposition
although it does not affect CO conversion. CO is relatively easy to hydrogenated compared to CO2 at
the same reaction conditions. The comparison of thermodynamic calculations with experimental
results demonstrated that the Gibbs free energy minimization method is significantly effective for
understanding the reactions occurring in methanation and helpful for the development of catalysts
and processes for the production of SNG.

1. Introduction fuel cell and ammonia synthesis industry, methanation can also
be used for the removal of trace CO from H2-rich stream to
Recently, because of the increasing demand for natural gas and prevent catalyst poisoning.6,7 The catalysts and processes for
the reduction of greenhouse gases,1,2 interests have focused on methanation have been intensively explored and summarized in
the production of synthetic natural gas (SNG), which is the reviews.1,8–11
suggested as an important future energy carrier. The conven- Experimental results showed that the methanation reactions of
tional route for SNG production is based on the gasification of carbon oxides were sensitive to the many factors such as
coal or biomass to synthetic gas (syngas). After gas cleaning and temperature, pressure, composition of reactants (syngas).2,12,13
conditioning, the syngas containing H2, CO, CO2, H2O, CH4, Simultaneous methanation of CO and CO2 is frequently
and hydrocarbons3,4 can be converted to SNG by catalytic encountered in a coexistent system14,15 and there is a competitive
hydrogenation of carbon oxides (CO and/or CO2), otherwise reaction between CO and CO2 methanation.6,16 As we know, the
known as methanation. At the moment, there are at least 15 syngas obtained through gasification of coal and biomass
coal-to-SNG plants proposed in the U.S., which are in different inevitably includes high hydrocarbons such as C2H6, C2H4,
stages of development,5 and more than 20 coal-to-SNG plants and C2H2, and methanation of syngas involves many side-
are in construction and proposed in China because of China’s reactions that could result in complex by-products, which bring
abundant coal and poor natural gas. On the other hand, in the about a negative effect on the methanation process. The carbon
deposition always occurs on the surface of catalysts during
a
State Key Laboratory of Multiphase Complex Systems, Institute of methanation,17 resulting in the quick deactivation of catalysts,
Process Engineering, Chinese Academy of Sciences, Beijing, China. and this is one of the most serious problems in industry. It is
E-mail: [email protected] (F.Gu); [email protected] (F.Su);
Fax: +86-10-82544851; Tel: +86-10-82544850 reported that adding steam to the reactants could suppress
b
Graduate University of Chinese Academy of Sciences, Beijing, China carbon deposition.1 In the methanation industry, the recycling of

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product gas containing water and CH4 is essential in the 2. Methodology

adiabatic fixed-bed methanation process in order to cut down
reaction heat. For an example, in TREMPTM technology 2.1. Thermodynamic analysis
developed by Haldor Topsøe (Denmark), product gas recycle As we know, equilibrium composition of a reaction system can
is used to control the temperature in the first methanation be calculated using either equilibrium constants or the Gibbs free
reactor with a feed ratio of (H2–CO2)/(CO + CO2) # 3.18 energy minimization method. Since the former approach uses
Therefore, methanation is a very complicated process for the individual equilibrium constants of reactions exactly involved in
production of SNG. Although several methanation processes methanation and it is difficult to obtain the exact knowledge of
have been developed based on coal and biomass including the these reactions, the former may be not ideal for the methanation
Lurgi process,19 TREMPTM technology,18 Davy process,20 and process. The latter is based on the principle that the total Gibbs
HICOM process,21 fewer studies have been reported on the energy of the system has its minimum value at chemical
thermodynamic analysis, which is very helpful in predicting and equilibrium, in which, individual equilibrium constants, espe-
understanding the methanation process. cially for multiple reactions in one system, are not considered. If
Thermodynamics is useful in the evaluation of processes all the species in a reaction system including reactants and
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occurring in such a complex reaction system. Thermodynamic products are given, the distribution of the products under a
equilibrium calculations of complex chemical systems based on minimum free energy can be established by using a general
the Gibbs free energy minimization can give answers to mathematical technique without knowing the chemistry of the
numerous questions, including the type of thermodynamically reactions. This method also can be used for condensed species,27
stable reaction products produced, together with their selectivity non-reacting species as well as reacting species.28 Therefore, the
and yield, whether a chemical reaction proceeds endothermically Gibbs free energy minimization method is widely used to
or exothermically, the impact of reaction parameters like perform thermodynamic analysis29–31 and should be more
temperature, pressure, or reactant ratios, and whether observed suitable for the present work because the methanation process
reaction temperatures are thermodynamically determined. By involves complex species and reactions. Here, the software
comparing the calculations with experimental results, the CHEMCAD was used for carrying out the calculation, and
identification of kinetic hindrances, i.e. thermodynamically meanwhile, the Soave–Redlich–Kwong method was employed as
allowed but somehow suppressed chemical reactions, should be the equation of state to determine fugacity in the calculation.
helpful in understanding the methanation process. It is noted The total Gibbs free energy GT of the system is given as:
that some thermodynamic analysis of methanation reactions has X
m X
m X fi
been done recently. Greyson and co-workers calculated the GT ~ ni mi ~ ni mH
i zRT ni ln (1)
i~1 i~1
PH
thermodynamics equilibrium compositions for CO methanation
system only for three reactions (CO + 3H2 « CH4 + H2O, CO +
H2O « CO2 + H2, 2CO « C + CO2).22 Anderson and co-
Introducing Lagrange multipliers for species i, subject to mass
workers studied the thermodynamics of the hydrogenation of
balance constraints:
carbon oxides for the production of hydrocarbons and
oxygenated organic molecules and found that it involves X
k

methane production slightly.23,24 Beuls25 and Ocampo26 con- mi z lj aji ~0 (2)

j~0
ducted a thermodynamic calculation of CO2 methanation based
on the developed catalyst under given reaction conditions.
However, thermodynamic analysis as above is less comprehen- Where l is the Lagrange multiplier, aji is the number of atoms
sive and it would be of interest to have a deeper understanding of of element j in species i. Therefore combining eqn (1) and (2)
the on-going reactions in the absence of any hindrances caused yields:
by kinetics, transport phenomena, or hydrodynamics.
  Xk
Herein, we systematically conducted a thermodynamic analy- fi
mH
i zRT ln zRT lj aji ~0 (3)
sis of CO and/or CO2 methanation by using the total Gibbs free PH j~0
energy minimization method. The effects of various initial
reactant compositions, temperature, and pressure on the
conversion of carbon oxides, CH4 selectivity and yield, and For the condensed species:
carbon deposition were investigated. The effects of compounds
such as H2O, O2, CH4, and C2H4 in syngas were also considered. X
k
mH
i zRT lj aji ~0 (4)
We also compared the thermodynamic calculation with the j~0
experimental results obtained over two commercial methanation
catalysts. In addition, three cases with different feed gas
compositions adapted from the literature were also calculated In the CHEMCAD software, as a result of the manipulations
to verify our simulation. To our knowledge, no such systematic involved, a system of linear simultaneous equations is obtained
thermodynamic analysis has been made for CO and/or CO2 as many unknowns. When solved, the system yields a new
methanation reactions based on Gibbs free energy minimization composition that represents a new approximation of the
method yet. Our results would give a useful guidance for the composition which gives minimum free energy. The procedure
development of the methanation process. is repeated until the calculated and prior compositions are

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Table 1 Possible reactions involved in the methanation of carbon oxides8,28

Reaction no. Reaction formula DH298 K (kJ mol21) Reaction type

R1 CO + 3H2 « CH4 + H2O 2206.1 CO methanation

R2 CO2 + 4H2 « CH4 + 2H2O 2165.0 CO2 methanation
R3 2CO + 2H2 « CH4 + CO2 2247.3 inversed methane CO2 reforming
R4 2CO « C + CO2 2172.4 Boudouard reaction
R5 CO + H2O « CO2 + H2 241.2 water-gas shift
R6 CH4 « 2H2 + C 74.8 methane cracking
R7 CO + H2 « C + H2O 2131.3 carbon monoxide reduction
R8 CO2 + 2H2 « C + 2H2O 290.1 carbon dioxide reduction
R9 nCO + (2n+1)H2 « CnH2n+2 + nH2O — —
R10 nCO + 2nH2 « CnH2n + nH2O — —

identical. At this point, the free energy of the system is at a the measurement within the temperature range 200–600 uC.
minimum. Firstly, 200 mg of each catalyst (20–40 mesh) was mixed with
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As a theoretical study, catalyst, reaction kinetics, and the 1.0 g quartz sand (20–40 mesh) and placed in the reactor. The
transport process are not considered here. However, the results thermocouple was directly inserted into the catalyst bed to
from the thermodynamic analysis could be used as a benchmark measure the actual reaction temperature. Prior to the reaction,
to compare with the experiment results. Here, possible reactions catalysts were reduced by H2 with a flow rate of 50 mL min21 at
involved in the methanation of carbon oxides are given in Table 1 450 uC for 2 h. Feed gas with a molar ratio of H2/CO/N2 = x/1/1
for the calculation.8,28 Our calculation was conducted based on (x = 1, 3, and 5) controlled with the mass flowmeters was
the gaseous compounds containing H2, O2, N2, CO, CO2, CH4, introduced into the reactor at a weight hourly space velocity
H2O, C2H4 (as a typical representative of high hydrocarbons), and (WHSV) of 30 000 mL h21 g21. The reaction temperature
solid carbon. Other oxygen-containing compounds such as was controlled by the heat controller with a heating rate of
methanol, methanoic acid, acetic acid and other high hydro- 5 uC min21. After one hour of steady-state operation at a set
carbons are not considered here because of their trace amounts in temperature, the outlet product gas stream was cooled down and
the equilibrium mixture gas. Carbon (C), hydrogen (H) and analysed online using a MicroGC (3000A, Agilent).
oxygen (O) atoms are used for the elemental mass balance. CO
and CO2 conversion, CH4 selectivity and yield, and carbon yield 3. Results and discussion
are defined in Table 2. It should be noted that the molar flow rate
of solid carbon used in the definition can be obtained through 3.1. The equilibrium constants of reactions involved in methanation
calculation by the Gibbs free energy minimization method in Fig. 1 shows the equilibrium constants (K) of the first eight
accordance with other gaseous compounds.27 possible reactions (see Table 1) occurring in the methanation
process as a function of temperature. K is calculated below by
2.2. Experimental procedure the van’t Hoff equation:
For a comparison with the thermodynamic calculation, CO d ln K H Dr Hm
H
methanation was carried out on two commercial nickel-based ~ 2
(5)
dT RT
catalysts marked as C1 (N112, NiO 67 wt%, JGC Catalyst and
Chemicals Ltd., Japan) and C2 (HT-1, NiO 57 wt%, LiaoNing
HaiTai SCI-TECH Development CO., LTD, China). Two fixed It can be seen that all exothermic reactions are suppressed as
bed reactors made of a quartz tube (at 1 atm) and stainless steel temperature is increased except for the endothermic methane
(at high pressures) both with a diameter of 10 mm were used in cracking reaction (R6). R1, R2, R3, R4, and R7 play a key role

Table 2 Definition of CO and CO2 conversion, CH4 selectivity and yield, and carbon yielda
Entry Definition

CO conversion FCO,in {FCO,out

XCO (%)~ |100
FCO,in
CO2 conversion FCO2 ,in {FCO2 ,out
XCO2 (%)~ |100
FCO2 ,in
CH4 selectivity (CO methanation system) CO FCH4 ,out
SCH (%)~ |100
4
FCH4 ,out zFCO2 ,out zFC,out
CH4 selectivity (CO2 methanation system) CO2 FCH4 ,out
SCH (%)~ |100
4
FCH4 ,out zFCO,out zFC,out
CH4 yield FCH ,out
YCH4 (%)~ P 4 |100
Ni Fi,in
i
Carbon yield FC,out
YC (%)~ P |100
Ni Fi,in
i
a
Herein, i indicate all species that contain carbon (CO, CO2, CH4, and C2H4) at inlet. Ni is the number of carbon atom of species i.

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deposition of carbon, which is in accordance with the early

reports.22–24 With an increase in temperature, the mole fraction
of CH4 decreases, whereas the unreacted CO, H2, CO2, and
deposited carbon increase simultaneously. The carbon deposi-
tion occurs when the temperature is higher than 450 uC. This is
because the Boudouard reaction (R4) occurs easier than CO
methanation (R1) above this temperature due to its higher
equilibrium constant as shown in Fig. 1. In short, the reaction
temperature for CO methanation should be controlled at a low
temperature to avoid carbon deposition for the primary screen-
ing of methanation catalysts although it is not recommended for
industry to adopt such operation parameters.

3.2.2. Effects of pressure and temperature. Fig. 3 shows the

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effects of pressure and temperature on CO methanation

performance (H2/CO = 3). It can be seen that in Fig. 3a, a high
Fig. 1 The calculated K values of the reactions involved in methanation. pressure leads to a higher CO conversion at the same reaction
temperature because CO methanation is a volume reducing
in the methanation reaction system due to their high equilibrium reaction. On the other hand, a much higher pressure (100 atm)
constants in the temperature range 200–500 uC. Consumption of does not result in a much higher CO conversion below 700 uC
CO via R1, R3, R4, and R5 reactions can bring about nearly compared with that at 30 atm. As we know, high operation
complete conversion of CO because of the high K values of these pressure and temperature in chemical industry are not economic-
reactions at low temperature. In contrast, CO2 is difficult to ally recommended. At the same reaction pressure, a lower
completely convert because the reactions R3, R4, and R5 temperature results in higher CO conversion because of the
produce it. In addition, it can be deduced that carbon deposition exothermic reaction of CO methanation (R1). However, this
mainly comes from the Boudouard reaction (R4) because its K is requires sufficiently high active catalysts at the lower tempera-
much larger than R6, R7, and R8. Lastly, all these reactions may ture, which is the challenge for developing catalysts.
simultaneously happen in the methanation process leading to a Fig. 3b shows the change in CH4 selectivity with temperature
significant effect on the product composition. at different pressures. It is seen that high CH4 selectivity can be
obtained at a pressure more than 1 atm and at a relatively low
3.2. CO methanation temperature. This is because CO is partially converted to by-
products such as CO2 and solid carbon via a reversed methane
3.2.1. CO methanation at 1 atm. For primary screening of CO2 reforming reaction (R3) and Boudouard reaction (R4)
methanation catalysts in the laboratory, CO methanation is respectively at low pressure and high temperature (Fig. 1). Thus,
always conducted at atmospheric pressure. Fig. 2 shows the
typical product fraction at equilibrium calculated via the Gibbs
free energy minimization method at 1 atm. The feed gas consists
of H2 and CO with a stoichiometric H2/CO ratio of 3. It can be
seen that the products mainly contain CH4 and H2O with lesser
CO2 by-product at a low temperature (200–300 uC) without

Fig. 3 Effects of pressure and temperature on CO conversion (a), CH4

Fig. 2 Product composition of CO methanation at equilibrium. selectivity (b), CH4 yield (c), and carbon yield (d).

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CH4 selectivity can be improved markedly by increasing pressure

from 1 to 30 atm, and further increasing pressure (100 atm)
would not lead to conspicuous improvement. This may be the
reason why the operation pressure less than 100 atm (normally
20–30 atm) was selected for TREMPTM technology.18 Fig. 3c
shows the variation in CH4 yield with the temperature at
different pressures. The curves are obtained by integrating data
in Fig. 3a with that in Fig. 3b. A CH4 yield near 100% was
observed at temperatures lower than 250 uC at 1 atm or higher
pressures. Thus, high pressure and low temperature will promote
CO methanation.
Fig. 3d reveals the variation in deposited carbon yield with the
temperature at different pressures. It is seen that at 1 atm, carbon
is generated in the temperature range 400–800 uC and reaches a
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maximum (22 mol% of yield) at about 600 uC. Further increasing

pressure to 10 atm, less carbon amount is found in the
temperature range 650–800 uC and the maximum (1.8 mol% of
yield) is achieved at around 725 uC. When pressure is more than
15 atm, deposited carbon is not observed. Thus, the high
pressure could substantially alleviate the carbon deposition. It is
known that carbon deposition originates from multiple reac-
tions, including the Boudouard reaction (R4), methane cracking Fig. 4 Effect of H2/CO ratio on CO conversion (a), CH4 selectivity (b),
(R6), CO reduction (R7), and CO2 reduction (R8) (see Table 1). CH4 yield (c), and carbon yield (d).
Since K of R4 is higher than that of R1 in the temperature range
of 450–600 uC at 1 atm (see Fig. 1), R4 will take place more easily
than R1 leading to carbon deposition that is mainly from CO ratios, especially at high reaction temperatures. When the H2/CO
disproportionation. However, when the reaction temperature ratio is lowered to 1 and below, CH4 selectivity reaches only to
exceeds about 600 uC, at which the maximum amount of carbon about 20% either at 1atm or 30 atm, indicating that CO is mostly
yield is obtained, carbon deposition may occur due to R6 (see converted to non-SNG products through side reactions (see
Fig. 1). Considering the relatively low concentration of CH4 at Table 1) considering the high CO conversion (see Fig. 4a).
above 600 uC, R6 may bring about less carbon deposition at this Fig. 4c shows the CH4 yield at different H2/CO ratios and
stage. However, the reversed reactions of R7 and R8 may different pressures. It is found that a large ratio, high pressure,
become dominant and consume much of the deposited carbon and low temperature are helpful for CH4 yield. Fig. 4d shows the
beyond 600 uC. As a result, total deposited carbon decreases yield of carbon deposited at different H2/CO ratios. We can find
when the temperature exceeds about 600 uC. Therefore, the that the low ratio of 1 leads to high carbon yield (50–70 mol%) at
carbon yield curves in Fig. 3d shows firstly an increase and then both 1 and 30 atm. In contrast, the deposited carbon is not
a decrease in value and it eventually decreases to a negligible observed at the ratios of 5 (1 atm) and 3 (30 atm) because CO is
value at around 800 uC. Moreover, because a higher pressure mostly converted to CH4 via R1 and CO2 via R3, respectively. It
favours R1 and R6 more than it does for R4, R7 and R8, the is known that R3 and R4 can easily take place at a H2/CO ratio
carbon yield gradually becomes lesser and the carbon deposition smaller than 3. As a result, the improvement in CH4 selectivity is
shifts to a higher temperature range with an increase of pressure. tiny even at a pressure of 30 atm as compared to that at 1 atm.
Finally there is no carbon deposition found at more than 15 atm. Thus, to obtain a relatively high CH4 yield, H2/CO ratio should
Thus, in CO methanation, low temperature and high pressure not be lower than 3, which is consistent with that of TREMPTM
values are highly recommended. technology.18

3.2.3. Effect of H2/CO ratio. Since syngas has a variable ratio 3.2.4. Effect of H2O. Industrial experience showed that adding
of H2/CO, according to the stoichiometric ratio of R1, H2/CO is water steam into reactants could avoid carbon formation to a
required to be at around 3, which is normally controlled through large extent on the methanation catalysts.1 Fig. 5 shows the
water-gas shift reaction (R5).1 However, it is very hard to tune effect of adding steam into the feed gas at 1 and 30 atm. Fig. 5a
this value to be exactly 3 in the methanation industry. Thus, it is indicates that additional steam with different ratios leads to a
necessary to know the influence of this ratio on the methanation slight decrease in CO conversion at the high temperature (1 atm
process. Fig. 4a exhibits the effect of different H2/CO ratios at and 30 atm) since steam is one of the reaction products inhibiting
different pressures on CO conversion. It can be seen that the CO CO methanation (R1) to some extent according to Le Chatelier’s
conversion is not obviously changed at different H2/CO ratios (1, principle.
3, and 5). At 30 atm, a higher ratio seems to be beneficial Similarly, Fig. 5b shows that the introduction of steam results
towards CO conversion. Fig. 4b reveals the CH4 selectivity at in a small difference in CH4 selectivity, in which, small decreases
different H2/CO ratios. It can be seen that a higher H2/CO ratio with an increase of steam ratio can be found at 30 atm and at a
leads to a higher CH4 selectivity at both 1 and 30 atm. Reaction temperature more than 500 uC. Accordingly, Fig. 5c shows the
at high pressure also results in high CH4 selectivity at different effect of adding steam on the CH4 yield. The trend is similar to

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Fig. 5 Effect of water steam added into the feed gas on CO conversion Fig. 6 Effect of O2 contained in the feed gas on CO conversion (a), CH4
(a), CH4 selectivity (b), CH4 yield (c), and carbon yield (d). selectivity (b), CH4 yield (c), and carbon yield (d).

that in Fig. 5a and 5b. Fig. 5d reveals the effect of steam on the necessary to completely remove the O2 in feed gas for the
carbon yield at 1 atm. It can be seen that additional steam methanation process.
remarkably reduces the carbon deposition at 1 atm especially at
high temperatures although the temperature at which maximum 3.2.6. Effect of CH4. Syngas often contains a certain amount
carbon yield is obtained is not changed. When steam ratio of CH4.1,3,4 On the other hand, recycling the methanation gas
reaches to 0.5, there is no carbon formed. This is because adding product containing CH4 and H2O is usually employed to dilute
water would inhibit R7 and R8 significantly. Therefore, adding a the feed gas to control the reaction temperature in the industrial
small amount of water into the CO methanation system could methanation process such as the Lurgi process,33 TREMPTM
reduce carbon deposition. This is in agreement with the technology,18 and HICOM process.21 Thus, it is necessary to
HICOM21 and RMP32 methanation processes, in which excess understand the effect of CH4 on the methanation reaction as
steam is required for the first methanation reactor in order to shown in Fig. 7. Fig. 7a, 7b, and 7c show the effect of CH4 when
avoid carbon deposition. In addition, we did not do the it is introduced into the feed gas on the CO conversion, CH4
calculation at 30 atm because at this pressure, there is no carbon selectivity, and CH4 yield, respectively. It can be seen that
deposition even without adding steam regarding above Fig. 3d additional CH4 with different ratios does not lead to a large
and 4d. difference in conversion, selectivity and yield at both 1 and
30 atm. Accordingly, a high yield of CH4 still can be achieved at
3.2.5. Effect of O2. It is known that trace amount of O2 in the low temperature and high pressure even with high CH4 ratios
syngas is inevitable in the gasification process. At the present, (H2/CO/CH4 = 3/1/5) as shown in Fig. 7c. However, Fig. 7d
there is no report on the effect of O2 on methanation. Fig. 6 shows that deposited carbon yield sharply increases with a high
depicts the effect of O2 introduced into the feed gas on CO ratio of CH4 above 400 uC at both 1 and 30 atm mainly due to
methanation. Fig. 6a shows the O2 effect on CO conversion, the methane cracking reaction (R6), which occurs at high
from which, it can be seen that CO conversion decreases slightly temperature (Fig. 1). In brief, to get a high CH4 yield and a low
with an O2 increase at both 1 and 30 atm, owing to the reactions carbon yield, as well as optimized the energy efficiency, a large
of H2 and CO with O2, especially at high temperatures, recycling of the product gas is not suggested, and CH4 in the feed
respectively. Fig. 6b shows the effect of O2 on CH4 selectivity, gas should be controlled at a low level. The recycle ratio of
suggesting that O2 could lead to the obvious decline of CH4 product gas would be controlled in an appropriate range, for
selectivity in the whole temperature range because CO is partially example, 0.5–3.0 for the methanation process. This may explain
oxygenated to CO2. As a result, CH4 yield decreases with an O2 why the TREMPTM technology is dedicated to decreasing the
increase in reactants as shown in Fig. 6c. However, as shown in recycle ratio.18
Fig. 6d, the introduction of O2 can lead to a large reduction of
deposited carbon at 1 atm because of the reaction of O2 with 3.2.7. Effect of trace C2H4. It is also known that the presence
carbon to form CO2, especially at the ratio of H2/CO/O2 = 3/1/ of gaseous hydrocarbon compounds in syngas, such as C2H6,
0.5. Similarly, again at 30 atm, no carbon deposition occurs at C2H4, and C2H2, drastically raises the risk for carbon deposi-
high temperature. Therefore, considering the CH4 yield, it is tion.1 Fig. 8 shows the effect of C2H4 introduced into the feed

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Fig. 9 Product fraction of CO2 methanation at equilibrium.

also accounted for the drop in CH4 selectivity and yield.28

Fig. 8d shows the effect of C2H4 on carbon yield. It can be seen
that the carbon deposition rapidly increases with the increase in
C2H4 ratio, especially at 1 atm. Similarly, at 30 atm, the carbon
yield shows the same trend although there is a large reduction in
Fig. 7 Effect of CH4 introduced into the feed gas on CO conversion (a), the total amount of carbon yield. Therefore, purification of
CH4 selectivity (b), CH4 yield (c), and carbon yield (d). hydrocarbon compounds in syngas is strictly required to
diminish carbon formation on catalysts to ensure long contin-
gas on CO methanation at different ratios and pressures. Here, uous operation of the methanation process.
C2H4 represents a typical example of hydrocarbon compounds in
syngas. It can be seen that in Fig. 8a CO conversion is almost not 3.3. CO2 methanation
influenced by C2H4 because it has no effect on the reactions of
3.3.1. CO2 methanation at 1 atm. CO2 methanation as a
R1, R3, and R4 which are not related to C2H4. However, CH4
particularly promising technique for reducing CO2 emissions and
selectivity in Fig. 8b and CH4 yield in Fig. 8c are substantially
producing energy carrier or chemical has been widely studied in
reduced with the increase of C2H4 at either 1 or 30 atm. This is
recent years.34–36 In addition, syngas also contains a large
because C2H4 will compete with CO to react with H2 and enable
amount of CO2. However, few studies were attempted on the
the Boudouard reaction (R4) to occur more easily. In addition,
thermodynamic analysis in CO2 methanation. Fig. 9 shows the
pyrolysis of C2H4 at high temperature to form carbon may have
typical product fraction of CO2 methanation at equilibrium
calculated via the Gibbs free energy minimization method at
1 atm. The feed gas contains H2 and CO2 with a stoichiometric
H2/CO2 molar ratio of 4. It can be seen that the products are
mainly CH4 and H2O at a relative low temperature (200–250 uC).
Elevating the temperature above 450 uC results in the increase in
the CO by-product, due to reversed water gas shift reaction: CO2
+ H2AH2O + CO, and meanwhile, unreacted CO2 and H2 also
increase, along with a decrease in the CH4 product. Since CO2
methanation is also a strongly exothermic reaction, increasing
temperature is unfavourable for this reaction. However, when
the temperature exceeds about 550 uC, the mole fraction of CO2
reaches its maximum and then decreases because the reversed
water gas shift reaction dominates. The calculation also reveals
that no significant carbon deposition is generated under our
condition. Thermodynamically, the CO2 methanation reaction
may be assumed to take place via the following reactions
proposed by Jung-Nam Park and co-workers:36
CO2 + H2 + 3H2 « H2O + CO + 3H2 = H2O + CO + 3H2 «
H2O + CH4 + H2O
Accordingly, CO2 methanation can be seen as a series of
reactions involving firstly the reversed water-gas shift reaction
followed by CO methanation in the presence of steam with H2/
Fig. 8 Effect of C2H4 introduced into the feed gas on CO conversion CO/H2O ratio of 3/1/1. As discussed in section 3.2.4, adding steam
(a), CH4 selectivity (b), CH4 yield (c), and carbon yield (d). into CO methanation system can suppress carbon formation

2364 | RSC Adv., 2012, 2, 2358–2368 This journal is ß The Royal Society of Chemistry 2012
Published on 30 January 2012. Downloaded on 9/17/2023 6:23:17 AM. View Article Online

Fig. 10 Effects of pressure and temperature on CO2 methanation: (a) Fig. 11 Effect of different H2/CO2 ratios on CO2 methanation: (a) CO2
CO2 conversion, (b) CH4 selectivity, and (c) CH4 yield. conversion, (b) CH4 selectivity, (c) CH4 yield, and (d) carbon yield.

which may explain why no significant carbon deposition is found in promote CO2 methanation, which is similar to that predicted by
CO2 methanation. Similarly, compared with CO methanation, CO2 the calculation for CO methanation (see Fig. 3c). Furthermore, it
methanation is also favourable in thermodynamics. In order to should be mentioned that no carbon generation is found under
obtain a high CH4 yield at 1 atm, the reaction temperature should our simulation conditions (not shown here). This is because
not exceed 300 uC. However, the eight-electron reduction of CO2 to during the CO2 methanation, water is formed that can suppress
CH4 by hydrogen is difficult to achieve because of significant the carbon deposition as mentioned above.
kinetic barriers.37 Thus, a much more active catalyst is needed to
hydrogenate CO2 to CH4 especially at the low temperature. 3.3.3. Effect of H2/CO2 ratio. Fig. 11 describes the effect of
different H2/CO2 ratios on CO2 methanation. It can be seen that
3.3.2. Effects of pressure and temperature. Fig. 10 shows the CO2 conversion in Fig. 11a and CH4 selectivity in Fig. 11b are
effects of pressure and temperature on CO2 methanation. remarkably affected by H2/CO2 ratio. High H2/CO2 ratio
Fig. 10a shows the effect on CO2 conversion. It can be seen generally leads to high CO2 conversion and CH4 selectivity at
that the CO2 conversion decreases with increasing temperature both 1 and 30 atm. When H2/CO2 is equal to 2, CO2 conversion of
and increases with the pressure, at temperatures below 600 uC, only about 50–70% can be obtained at either 1 atm or 30 atm, and
similar to the trend of CO methanation as shown in Fig. 3a. This maximum CH4 selectivity of 73% and 88% is achieved at 1 atm
is because CO2 methanation is also a volume reducing and and 30 atm, respectively. Fig. 11c shows the effect on CH4 yield.
exothermic reaction. When CO2 methanation takes place at When the H2/CO2 ratio is 2, CH4 yield is as low as about 40% at
1 atm and beyond 600 uC, the CO2 conversion gradually 1 atm and 45% at 30 atm, respectively, and CH4 yield can be
increases, different from what is seen in CO methanation as enhanced markedly by increasing H2/CO2 ratio at the same
shown in Fig. 3a. This is mainly because the reversed reaction of conditions. Fig. 11d shows the carbon yield. When H2/CO2 ratio is
R5 dominates above 600 uC and consumes CO2. Fig. 10b shows 2, abundant carbon deposition (up to 50%) is found below 500 uC
the effect on CH4 selectivity. It is observed that the trend with at both 1 and 30 atm. When H2/CO2 ratio is equal to or more than
variations in the pressure and temperature is similar to CO 4 (the curve at the ratio of 6 is not shown here), carbon deposition
methanation (see Fig. 3b). It should be noted that our is not found. Thus, in order to obtain a high CH4 yield and avoid
calculation result at 1atm is in accordance with Beuls’s25 and carbon deposition, H2/CO2 ratio should not be lower than 4 even
Ocampo’s26 simulations for CO2 methanation, and also in good at 30 atm. Conclusively, low temperature, high pressure, and
agreement with the experimental results of Du and co-workers proper H2/CO2 ratio is required for optimized CO2 methanation.
based on Ni/MCM-41 catalysts for CO2 methanation.38
Comparing Fig. 10a with Fig. 3a, we find that CO2 is more 3.3.4. Effect of H2O. Fig. 12 gives the effect of adding steam into
difficult than CO to be methanized at the same temperature and the feed gas (H2/CO2/H2O = 3/1/x, x = 0, 0.2, and 0.5, here x = 0
pressure although the CH4 selectivity below 500 uC in the CO2 means that no additional H2O is added). It is seen that at 1 and
methanation system is relatively higher than that in CO 30 atm, the addition of steam leads to a little decrease in CO2
methanation. Fig. 10c shows effect of temperature and pressure conversion (Fig. 12a), and no significant difference in CH4
on the CH4 yield. Low temperature and high pressure also selectivity (Fig. 12b) and CH4 yield (Fig. 12c). This is mainly

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 View Article Online

CO conversion is much higher than that of CO2 in most

situations, especially below 600 uC, indicating that CO is much
easier to be hydrogenated than CO2 as discussed above.
However, when the temperature increases further, the CO2
conversion increases, whereas the CO conversion drops sharply
owing to the occurrence of the reversed water gas shift reaction:
CO2 + H2AH2O + CO. As a result, CO even shows a negative
conversion above 650 uC. Fig. 13b shows the effect on CH4 yield.
It can be seen that a high CH4 yield can be achieved at low
temperature and high pressure. Since it is difficult to determine
the carbon oxide source of CH4 from either CO or CO2, the CH4
selectivity is not given here. Moreover, it should be noted that no
carbon deposition is observed under the simulation conditions
(not shown here), suggesting that the water generated from CO2
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methanation may have inhibited the carbon formation not only

in CO2 methanation as observed above but also in CO
methanation. This is different from CO methanation alone.

3.5. Comparison of thermodynamic calculation with the

experimental results for CO methanation
For comparison with the thermodynamic calculations, CO
Fig. 12 Effect of additional steam in the feed gas on CO2 methanation: methanation was carried out on two commercial Ni-based
(a) CO2 conversion, (b) CH4 selectivity, and (c) CH4 yield.
catalysts C1 (NiO 67 wt%) and C2 (NiO 57 wt%). Fig. 14 shows
the comparison of the thermodynamic calculations (marked as
because H2O is one of the products in CO2 methanation reaction cal) with the experimental results for CO methanation at different
and slightly inhibits the production of CH4 as discussed in section H2/CO/N2 ratios. It can be seen in Fig. 14a that CO conversion at
3.2.4. In addition, no carbon deposition is found with additional different ratios is generally in accordance with the calculated ones
steam introduced into CO2 methanation system (figure not shown). except for the results at H2/CO/N2 ratio of 1/1/1, but this gap at
low temperature is present possibly because catalysts C1 and C2
3.4. Simultaneous methanation of CO and CO2 are not active enough at low temperature or are without adequate
Since carbon oxides with both CO and CO2 always coexist in H2. CH4 selectivity is shown in Fig. 14b. CH4 selectivity exceeds
syngas, simultaneous methanation of carbon oxides would be the calculated value to some extent at the H2/CO/N2 ratio of 1/1/1.
often encountered. Thus, it is necessary to know their co- According to simulation results (Fig. 4d), when H2/CO/N2 ratio is
methanation situation. Fig. 13 presents the effects of pressure
and temperature on the co-methanation of both carbon oxides.
Here, in order to simplify the calculation, the feed gas with a CO/
CO2/H2 ratio of 1/1/7 for reactions R1 and R2 is employed for
thermodynamic analysis. Fig. 13a shows the effect of tempera-
ture and pressure on the conversion of carbon oxides, in which, it
can be seen that low temperature and high pressure lead to high
conversion of both CO and CO2, and the conversion curve
profiles for CO and CO2 are similar to that of their respective
methanation as shown in Fig. 3a and Fig. 10a. In addition, the

Fig. 14 Comparison of thermodynamic calculation with the experi-

Fig. 13 Effects of pressure and temperature on co-methanation of mental results for CO methanation with different H2/CO/N2 ratios: (a)
carbon oxides: (a) conversion and (b) CH4 yield. CO conversion, (b) CH4 selectivity, and (c) CH4 yield.

2366 | RSC Adv., 2012, 2, 2358–2368 This journal is ß The Royal Society of Chemistry 2012
 View Article Online

possibly because the catalyst used here is not active enough, which
is a big challenge for methanation at low temperatures. However,
above 350 uC, the two catalysts show high activity for CO
conversion, which is highly consistent with the calculation values
at different pressures. Fig. 15b gives the CH4 selectivity on the two
catalysts. The experimental selectivity below 450 uC at 1 atm is
reasonably smaller than that of the calculation, but above 450 uC,
the selectivity is much higher. This may be because the actual
pressure in the reactor may have inevitably increased at 1 atm due
to the inherent system pressure drop as mentioned above. In
addition, the temperature gradient distribution also causes an
error in the catalyst bed temperature recorded, resulting in a
further gap between experimentation and calculation. Moreover,
other factors such as the reactants transport process may also have
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affected CH4 selectivity. In contrast, at 10 atm and 30 atm, the

selectivity obtained on the commercial catalysts is in a good
agreement with calculated ones. Fig. 15c shows the comparison of
the CH4 yields. It can be seen that experimental results are
generally in accordance with the calculated ones at different
pressures. The result also indicates that the calculation here, which
has considered the effects of temperature and pressure, agrees well
Fig. 15 Comparison of experimental results with calculated ones at
with the experimental data.
different pressures: (a) CO conversion, (b) CH4 selectivity, and (c) CH4
yield. 3.6. Case study
For further verification of the effectiveness of our calculation,
1/1/1, a majority of CO is converted to carbon. However, we can
three cases adopted from the literature were studied here. Table 3
roughly deduce that carbon deposition is not so serious at these
compiles the calculated results together with the experiment data
two commercial catalysts according to carbon element conserva-
reported. The feed gas in these cases contains H2, CO, CO2, CH4,
tion during the experiment although we can not directly measure
H2O, and N2(Ar) with a typical composition. Case 1 is selected
the amount of carbon deposition at each reaction temperature,
from reactor 1 of the ADAM I process, which was developed by
which results in an increase of CH4 selectivity. From another point
British Gas Corporation in March 1979,39 in which the water–
of view, we can know that reactions involving carbon deposition
gas shift and methanation reactions are combined. Case 2 and
do not reach equilibrium under this reaction condition mainly
Case 3 come from the reactors 1 and 2 of a previous experimental
because of catalyst, transport process or kinetics. Besides, the work,40 respectively. It should be mentioned that the volume
actual pressure in the reactor is normally larger than 1 atm due to fraction in the references is converted to mole fraction for a fair
the reactor system pressure, thus leading to the enhancement of comparison. It is clearly seen that the product compositions
CH4 selectivity as discussed above. In contrast, at H2/CO/N2 ratio calculated (marked as Outcal) surprisingly approach closely to
of 5/1/1, CH4 selectivity can not reach equilibrium value, those reported, for example, the outlet CH4 fraction in case 1 is
suggesting that these two catalysts should be used at a proper 37.44% for reported and 38.02% for calculated, and in case 3 it is
H2/CO ratio. CH4 yield in Fig. 14c is obtained by integrating data 10.20% for reported and 10.48% for calculated, suggesting that
in Fig. 14a with that in Fig. 14b. These results suggest that the the Gibbs free energy minimization method is an ideal tool for
effect of H2/CO ratio predicted by our calculation generally agrees thermodynamic analysis of the methanation process.
with that of our experimental results.
Fig. 15 shows the experimental results together with the
4. Conclusions
calculated ones obtained using the H2/CO/N2 ratio of 3/1/1 at
different pressures. It can be seen in Fig. 15a that below 350 uC, In summary, we have made a detailed thermodynamic equili-
the CO conversion is much lower than that of the calculation brium analysis of the methanation reactions of carbon oxides

Table 3 Calculative results for syngas methanation together with the experiment data reported in the literature
Case 1 Case 2 Case 3
Entry
In Out Outcal In Out Outcal In Out Outcal

T/uC 300 604 604 398 729 729 325 590 590
P (atm) 27.2 27.1 27.1 30.0 30.0 30.0 30.0 30.0 30.0
H2 36.88 20.96 19.90 25.64 20.60 19.92 20.6 10.42 9.72
CO 4.28 1.17 1.10 18.61 8.40 8.03 8.40 2.21 2.02
CO2 6.13 4.46 4.28 14.74 23.30 23.58 23.30 27.74 27.84
CH4 28.12 37.44 38.02 0.048 4.94 5.29 4.94 10.20 10.48
H2O 19.19 29.82 30.59 40.23 41.96 42.38 41.96 48.56 49.06
N2(Ar) 5.41 6.15 6.10 0.72 0.79 0.80 0.79 0.86 0.87

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 View Article Online

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2368 | RSC Adv., 2012, 2, 2358–2368 This journal is ß The Royal Society of Chemistry 2012