Y.S. Mok, et al., Int. J. Sus. Dev. Plann. Vol. 8, No.

2 (2013) 186–196

PRODUCTION OF METHANE FROM CARBON MONOXIDE

AND CARBON DIOXIDE IN A PLASMA-CATALYTIC
COMBINED REACTOR SYSTEM
Y.S. MOK, E. JWA & H.W. LEE
Department of Chemical and Biological Engineering, Jeju National University, Korea.

ABSTRACT
Plasma-catalytic hydrogenation of CO and CO2 for producing methane was investigated with a catalyst-packed
dielectric barrier discharge reactor. The characteristics of methane production from CO/H2 or CO2/H2 gas
mixture were examined with bare alumina, TiO2/alumina, Ni/alumina, and Ni-TiO2/alumina under plasma and
non-plasma conditions. The results obtained with bare alumina and TiO2/alumina suggest that either plasma-
induced gas–phase reactions or photocatalytic reactions hardly contribute to the conversion of CO and CO2.
The nonthermal plasma was found to have a promotive effect on the conversion of CO and CO2 only when
nickel-loaded catalysts such as Ni/alumina and Ni-TiO2/alumina were used, implying that the nonthermal
plasma serves to promote the dissociation of carbon–oxygen bonds of CO and CO2 adsorbed on the active sites
of the catalysts, known as the slowest step of the reaction.
Keywords: catalytic hydrogenation, CO, CO2, methane, nonthermal plasma.

1 INTRODUCTION
Methane is the primary component of natural gas that is not only an important energy source but also
a valuable feedstock for the chemical industry. The catalytic conversion of carbon oxides (CO and
CO2) into methane is increasingly attracting attention, because it can provide measures for utilizing
coal-derived synthesis gas effectively and a possibility for recycling CO2 back into fuel. This is also
actuated in part by the relative abundance of coal and the need to develop a clean coal technology.
Increasing consumption – and the resultant increasing price – of natural gas are a concern. There are
several advantages associated with producing synthetic natural gas (SNG) from coal, as it could be
a major drive for energy security and diversify energy options [1]. Since coal is relatively abundant
and evenly distributed globally, as compared to petroleum and natural gas, SNG production could
also help stabilize the global energy market.
The hydrogenation of carbon oxides to produce methane is called methanation, which is one of
essential steps for SNG production, together with coal gasification step. The solid catalysts com-
monly used for methane production are based on transition metals supported on metal oxides, such
as alumina, titanium dioxide, and zeolite [2–5]. Even though the catalysts consisting of a noble
metal, such as ruthenium, rhodium or platinum [2, 6], nickel-based catalysts have been the most
widely studied because nickel is cheap and easily available and shows high activity [5, 7–9]. One of
the disadvantages of the nickel-based catalysts may be that relatively high temperatures are needed
to maintain the catalytic activity for methane production.
The catalysts can chemically be modified with support materials and additives so that they have
an enhanced low-temperature activity. Alternatively, the catalytic activity can be improved by a
physical means, such as nonthermal plasma and ultraviolet irradiation. In the literature, many studies
dealing with combined use of nonthermal plasma and solid catalysis have been reported, which
include oxidation of volatile organic compounds, degradation of halogenated carbons, steam reform-
ing of hydrocarbons, CO2 reforming of methane, etc. [10–14]. In a similar manner, nonthermal
plasma can also promote the catalytic hydrogenation of CO and CO2 into methane, as demonstrated
in a previous study, where it was shown that the plasma significantly increased the catalytic activity,

© 2013 WIT Press, [Link]

ISSN: 1743-7601 (paper format), ISSN: 1743-761X (online), [Link]
DOI: 10.2495/SDP-V8-N2-186-196
 Y.S. Mok, et al., Int. J. Sus. Dev. Plann. Vol. 8, No. 2 (2013) 187

especially at lower temperatures and pressures that the catalyst was not so active [15, 16]. In a tradi-
tional thermal catalysis, catalysts are activated by thermal energy to go over an activation barrier. By
comparison, in plasma-catalysis, catalyst is directly in contact with plasma, and reactive species,
such as energetic electrons, free radicals, excited atoms, and molecules, generated by the plasma can
activate reactant molecules either in the gas phase or on the catalyst surface, possibly leading to the
triggering of catalytic reactions at low temperatures. The bond strengths for gaseous CO and CO2 are
11 eV and 8 eV, respectively, but they get weak when adsorbed on the catalyst surface. As a result,
the energetic electrons produced by the plasma can readily break the carbon–oxygen bond of the
adsorbed carbon oxides. Once the carbon–oxygen bond is broken somehow, the adsorbed carbon is
easily hydrogenated to produce methane.
In this work, the production of methane from CO and CO2 was performed in a dielectric barrier
discharge (DBD), nonthermal plasma reactor packed with catalyst pellets at atmospheric pressure.
The effect of the plasma discharge on the conversion of CO and CO2 was comparatively examined
with four catalysts, that is, bare alumina, TiO2/alumina, Ni/alumina, and Ni-TiO2/alumina to under-
stand the role of the plasma and find out how effective the plasma-catalysis is in the production of
methane. The nickel-based catalysts used can catalyze the methanation of both CO and. CO2. The
experiments were carried out by varying reactor temperature under plasma and non-plasma condi-
tions at constant CO/H2 and CO2/H2 ratios in the feed gas.

2 THEORETICAL BACKGROUND

2.1 Reaction equilibrium

The catalytic hydrogenation of CO and CO2 proceeds fast over various transition metal catalysts
involving the following overall reactions [4]:
CO + 3H2 → CH4 + H2O (1)
CO2 + 4H2 → CH4 + 2H2O (2)
Reaction (1) represents the reverse steam reforming reaction, which also proceeds effectively over
transition metal catalysts. Thermodynamic values of relevant reactions are tabulated in Table 1 [17].

Table 1: Standard heats and Gibbs free energies at 298K.

ο ο
Reaction ΔH 298 (cal mol–1) ΔG298 (cal mol–1)
1
C(s) + O2 (g) → CO(g) −26,416 −32,781
2
C(s) + O2 (g) → CO2 (g) −94,051 −94,258

C(s) + 2H 2 (g) → CH 4 (g) −17,889 −12,140

1
H 2 (g) + O2 (g) → H 2 O(g) −57,798 −54,635
2
CO + 3H 2 → CH 4 + H 2 O −49,271 −33,994

CO 2 + 4H 2 → CH 4 + 2H 2 O −39,434 −27,152
188 Y.S. Mok, et al., Int. J. Sus. Dev. Plann. Vol. 8, No. 2 (2013)

Reactions (1) and (2) are strongly exothermic, which indicates that these reactions favor low reaction
temperatures from the chemical equilibrium point of view. It should be noted, however, that reac-
tions (1) and (2) kinetically become favorable as the temperature rises because of the activation
energy barrier.
The equilibrium constant (K) is a function of temperature and related to the Gibbs free energy
(ΔGo) and the enthalpy change of a reaction (ΔHo) as follows [17]:

ΔG ο
ln K = − (3)
RT

d ln K ΔH ο
= (4)
dT RT 2

where T is absolute temperature and R is the gas constant. Over a small temperature range, the term
ΔHo can be treated as a constant, and eqn (4) is easily integrated to give
ο
K ΔH 298 1 1
ln =− ( − ). (5)
K 298 R T 298

where the subscript ‘298’ denotes a temperature of 298K and K298 can be calculated using eqn (3)
and the data in Table 1. Once K298 is known, eqn (5) allows us to determine the equilibrium con-
stants for reactions (1) and (2) at any temperature of interest. To predict the effect of change in
temperature on equilibrium conversions of CO and CO2, following equilibrium expressions should
be considered:

PCH4 PH2O
KCO = ,for CO methanation. (6)
PCO PH32

PCH4 PH22O
KCO2 = ,for CO2 methanation. (7)
PCO2 PH42

Here, P stands for partial pressure. For the present work, the total pressure was maintained at 1.0
atm, and thus eqns (6) and (7) can also be written with respect to mole fractions.

2.2 Catalytic methanation mechanisms

The production of methane from CO and CO2 consists of several elementary reaction steps that sum
up to overall reactions (1) and (2). Previous studies that have dealt with mechanistic aspects of cata-
lytic CO conversion can be classified into two categories: carbide mechanism and CO insertion
mechanism [8, 18, 19].
The carbide mechanism explains the formation of methane with dissociative adsorption of both
carbon monoxide and hydrogen followed by stepwise hydrogenation of adsorbed carbon to produce
methane [8]:

CO + * = CO* (8)
H2 + 2* = 2H* (9)
 Y.S. Mok, et al., Int. J. Sus. Dev. Plann. Vol. 8, No. 2 (2013) 189

CO* + * = C* + O* (10)

C* + H* = CH* + * (11)

CH* + H* = CH2* + * (12)

CH2* + H* = CH3* + * (13)

CH3* + H* = CH4 + 2* (14)

The symbol (*) used in reactions (8)–(14) signifies a vacant site and chemical formulae with this
symbol refers to an adsorbed state. Meanwhile, the CO insertion mechanism assumes molecular
adsorption of CO and hydrogenation of adsorbed CO to give an oxygenated intermediate, which
further reacts with adsorbed hydrogen to form methane [18]. The important elementary steps
accounting for the CO insertion mechanism are summarized below.
CO* + H* = HCO* + * (15)

HCO* + H* = HCHO* + * (16)

HCHO* + H* = CH* + H2O* (17)

As in reactions (12)–(14), CH* is successively hydrogenated to produce methane:
+ H∗ + H∗ + H∗
CH* ⎯⎯⎯ → CH 2* ⎯⎯⎯ → CH 3* ⎯⎯⎯ → CH 4*. (18)

Sehested et al. [5] proposed a kinetic model with the dissociation of CO* as the slowest step, that
is, the rate-determining step. According to Bengaard et al. [20], the dissociation of CO* shows the
highest barrier among the elementary steps, suggesting that this reaction is the rate-determining step.
On the other hand, Alstrup [8] obtained good agreements between experimental data and kinetic
model by postulating the hydrogenation reaction between CH* and H* as the rate-determining step.
Thomson et al. [18] suggested that the rate-determining step is either the hydrogenation of CH* for
the carbide mechanism or the hydrogenation of HCO* for the CO insertion mechanism. Whatever
elementary reaction acts as the rate-determining step, nonthermal plasma may enhance the rate of
methane production, because the adsorption characteristics of the molecules excited by the plasma
should be different from those of ground-state molecules and the plasma can help dissociate adsorbed
molecules through various processes like direct electron impact. Note that the bond strength of an
adsorbed molecule is much weaker than in the gaseous state, which implies that the plasma is more
easily capable of cleaving the bond of adsorbed molecule.
As understood in reaction (2), the hydrogenation of CO2 to methane requires more hydrogen than
that of CO. Regarding the catalytic methanation mechanism, previous studies reported that CO2
adsorbs dissociatively on the catalyst surface and CO* is converted into methane via the same reac-
tion steps as in the CO methanation. The elementary reaction steps for CO2 methanation are as
follows [21]:
CO2* + * = CO* + O* (19)
CO* + * = C* + O* (20)
2CO* = C* + * + CO2 (21)
Just like the case of CO methanation, the hydrogenation of the adsorbed carbon proceeds stepwise
by reactions (11)–(14).
190 Y.S. Mok, et al., Int. J. Sus. Dev. Plann. Vol. 8, No. 2 (2013)

3 EXPERIMENTAL ANALYSIS
The experimental setup for the production of methane from CO and H2 is shown in Fig. 1. The
system consisted of four major parts: feed gas preparation, reactor, power supply, and analyzer. The
DBD reactor packed with catalyst pellets was made of a quartz tube and a concentric stainless-steel
rod acting as the discharging electrode. Details of the reactor, including its configuration and dimen-
sions, are described in our previous article [16]. The effective length of the plasma reactor was 110
mm, and the amount of catalyst pellets packed was 17 cm3 or 13.6 g. The reactor was powered by an
alternating current (AC) high voltage (operating frequency: 1 kHz). The voltage applied to the reac-
tor was changed in the range of 0–11 kV. The catalysts used in this work were prepared with alumina
ball (Sigma-Aldrich Co.) as the catalyst support, titanium dioxide (anatase TiO2, Sigma-Aldrich
Co.), and nickel nitrate (Ni(NO3)2·6H2O, Acros Organics). As well known, the anatase form of tita-
nium dioxide acts as a photocatalyst under ultraviolet light. The preparation method of the catalysts
has been described in detail in Jwa et al. [16]. The Brunauer–Emmett–Teller (BET) specific surface
areas of the catalysts were measured with a surface area analyzer (Model ASAP2010, Micromeritics).
The information on the catalysts is summarized in Table 2.
The feed gas was prepared by mixing pure hydrogen and carbon monoxide or by mixing pure
hydrogen and carbon dioxide via a set of mass flow controllers (MKS Instruments, Inc.). For the
methanation of CO, the molar ratio of H2 to CO in the feed gas was adjusted to 3 by the stoichiometry.
The methanation of CO2 was separately conducted with a H2/CO2 molar ratio of 4. The flow rate of
the feed gas was 12,000 cm3 h−1 for CO methanation, and 15,000 cm3 h−1 for CO2 methanation.
Methanation experiments were performed over the temperature range up to 320°C with an interval
of 20°C. The feed gas entered the mixing chamber where it was preheated to desired temperatures

Figure 1: Schematic diagram of the experimental apparatus for methane synthesis.

 Y.S. Mok, et al., Int. J. Sus. Dev. Plann. Vol. 8, No. 2 (2013) 191

Table 2: Information on the catalysts used.

Alumina TiO2/alumina Ni/alumina Ni-TiO2/alumina
BET surface area (m2 g−1) 195.7 168.8 138.5 116.4
Ni content (wt%) - - 10 10
TiO2 content (wt%) - 10 - 10

with a heating tape and then directed to the plasma reactor with a heating tape in which the metha-
nation of CO/CO2 proceeded. The concentrations of CO, CO2, CH4, and H2 in the effluent gas
coming out of the reactor were analyzed by a gas chromatograph (Varian Micro GC CP-4900)
equipped with an analytical column (10 m Pora Plot Q Column), using high purity helium as a
carrier gas. The voltage applied to the reactor was measured with a 1,000:1 high voltage probe
(P6015, Tektronix) and a digital oscilloscope (TDS 3032, Tektronix).

4 RESULTS AND DISCUSSION

Figures 2 and 3 present the effect of the reaction temperature on the conversions of CO and CO2
over Ni-TiO2/Al2O3 catalyst at different voltages, where the equilibrium conversions calculated
with eqns (6) and (7) are also given. The temperature was varied up to 320°C at each voltage
level of 0.0, 6.4, 8.5, and 10.3 kV. With the catalyst alone, that is, at a voltage of 0.0 kV, the
conversion of CO slowly increased with increasing the temperature from 220°C to 300°C, and
then was saturated at about 96%. As expected, there was a significant enhancement in the conver-
sion rate when high voltage was applied to the reactor, resulting in higher conversion efficiencies
at lower temperatures. Likewise, the conversion of CO2 showed a similar trend to that of CO (see
Fig. 3). When the applied voltage is high enough to create plasma, active species, such as ener-
getic electrons, ultraviolet (UV) photons, radicals, and excited molecules, are formed in the
reactor [16]. As aforementioned, these active species can promote catalytic reactions through
various channels, such as dissociation of adsorbed molecule and excitation of molecule. This
may explain the enhancement of the conversion rate under the plasma conditions. Comparing at
an identical voltage, the promotive effect of the plasma on the conversions of CO and CO2 was
more notable at higher temperatures, that is, the difference in the conversion efficiency between
with and without the plasma got wider as the temperature was increased. For instance, when the
voltage was 10.3 kV, the difference in the conversion of CO2 between with and without the
plasma was about 13% at 220°C, while it was about 50% at 260°C. The same trend was found
with the CO methanation, though the difference between with and without the plasma was
smaller. This result can partly be explained by the electron mean free path defined as the average
distance between collisions. Suppose that temperature is increased at constant pressure, the mean
free path increases by the expansion of gas. A longer mean free path enables an electron to be
accelerated more to get more energy, eventually facilitating relevant reactions. In the meantime,
the equilibrium conversions of CO and CO2 are calculated to be higher than those experimentally
obtained. It is because the methanation reactions expressed as reactions (1) and (2) are highly
exothermic and accordingly equilibrium is more favorable at low temperatures. Even if the equi-
librium conversions were so, the kinetics is favored at high temperatures due to the presence of
activation barrier.
The conversion efficiencies of CO and CO2 over three different catalysts at a temperature of
260°C are shown in Figs. 4 and 5 as a function of the applied voltage. As can be seen, there was
192 Y.S. Mok, et al., Int. J. Sus. Dev. Plann. Vol. 8, No. 2 (2013)

100

80

Conversion of CO (%)
60

40
Catalyst alone
6.4 kV
20 8.5 kV
10.3 kV
Equilibium
0
220 240 260 280 300 320
Temperature (oC)

Figure 2: Effect of reaction temperature on the conversion CO at different voltages (catalyst:

Ni-TiO2/Al2O3).

100

80
Conversion of CO2 (%)

60

40
Catalyst alone
6.4 kV
20
8.5 kV
10.3 kV
Equilibrium
0
220 240 260 280 300 320
o
Temperature ( C)

Figure 3: Effect of reaction temperature on the conversion CO2 at different voltages (catalyst:
Ni-TiO2/Al2O3).

negligible conversion of CO with either bare alumina or TiO2/alumina catalyst, regardless of the
voltage level, which implies that ultraviolet photons and gas–phase reactions formed by the plasma
do not directly contribute to the production of methane. It should be noted that TiO2 photocatalyst in
the anatase form whose band gap energy is about 3.2 eV can be activated by ultraviolet photons with
wavelengths <390 nm. The electron-impact excitation of CO emits ultraviolet light with various
wavelengths [22, 23], but the photocatalytic effect was negligible with bare alumina and TiO2/
alumina. Different from the results obtained with bare alumina and TiO2/alumina, the plasma largely
 Y.S. Mok, et al., Int. J. Sus. Dev. Plann. Vol. 8, No. 2 (2013) 193

100

80

Conversion of CO (%)
60

40
Bare alumina
TiO2/alumina
20 Ni-TiO2/alumina

0
0 2 4 6 8 10 12
Applied voltage (kV)

Figure 4: Conversion efficiencies of CO over different catalysts (temperature: 260°C).

100

Bare alumina
80 TiO2/alumina
Conversion of CO2 (%)

Ni-TiO2/alumina
60

40

20

0
0 2 4 6 8 10 12
Applied voltage (kV)

Figure 5: Conversion efficiencies of CO2 over different catalysts (temperature: 260°C).

affected the conversion of CO over nickel-loaded alumina catalyst. As the voltage was increased, the
conversion increased slowly at first and then rapidly. This enhancement suggests that the plasma can
provide some additional activation of the catalyst. Like the case of CO, the conversion of CO2 with
bare alumina and TiO2/alumina was not significant, and moreover, the CO2 converted was mostly
reduced to CO, not to methane.
In Fig. 6, the conversion efficiencies of CO and CO2 over Ni-TiO2/alumina and Ni-TiO2/alumina
that were obtained with the catalyst-alone and the plasma-catalyst are compared for a voltage of
8.5 kV and a temperature of 260°C. Either of the catalysts showed remarkable enhancements in the
conversions of CO and CO2 as a result of the plasma generation in the catalytic reactor. Unexpectedly,
194 Y.S. Mok, et al., Int. J. Sus. Dev. Plann. Vol. 8, No. 2 (2013)

(a) 100 (b) 100

Ni-TiO2/alumina
Ni-TiO2/alumina 80 Ni/alumina
80
Ni/alumina
Conversion of CO2 (%)

Conversion of CO2 (%)

60 60

40 40

20 20

0 0

Catalyst alone Plasma-catalyst Catalyst alone Plasma-catalyst

Figure 6: Comparison of conversion efficiencies between the catalyst-alone and the plasma-catalyst
cases (a) for CO methanation and (b) for CO2 methanation (temperature: 260°C; applied
voltage: 8.6 kV).

the performance of Ni-TiO2/Al2O3 catalyst was found to be inferior to that of Ni/Al2O3 catalyst for
both CO and CO2, which may be another evidence that the ultraviolet photons produced by the
plasma did not contribute to the production of methanation. According to the literature [3], noble
metals supported on titanium dioxide, such as Pt/TiO2, Rh/TiO2, and Ir/TiO2, were reported to be
effective for photo-induced dissociation of CO2, conflicting with the present study conducted with
nickel as the active metal. It is believed that the photocatalytic activity of titanium dioxide is closely
related to the nature of active metal and catalyst support. The lower performance of Ni-TiO2/Al2O3
than Ni/Al2O3 may also be attributed in part to its smaller BET specific surface area. As reported in
Table 2, the BET specific surface areas of Ni/alumina and Ni-TiO2/alumina were measured to be
138.5 and 116.4 m3/g, respectively. Even though not dealt with in detail, local heating of the catalyst
surface due to the plasma generation may have somewhat contributed to the enhancement in the
conversions of CO and CO2, because the catalysts used in this work are dielectric. To minimize such
a dielectric heating effect and make a comparison between the catalyst-alone and the plasma-catalyst
cases at an identical temperature condition, the reactor temperature was minutely controlled, and the
concentrations of relevant compounds (CO, CO2, CH4, etc.) were measured after a lapse of time long
enough to ensure that the temperature reached the same temperature as in the case of the catalyst-
alone. To sum up, the local dielectric heating effect is believed to be minor.

5 CONCLUSIONS
This work investigated the use of nonthermal plasma created in a catalyst-packed bed reactor to
convert CO and CO2 into methane in the presence of hydrogen. So as to understand the role of non-
thermal plasma in the catalytic methanation, several catalysts, including bare alumina, TiO2/alumina,
Ni/alumina and Ni-TiO2/alumina, were examined. It was found that the plasma was beneficial to the
catalytic conversion of CO and CO2 in that it shifted the optimal reaction temperature lower. The
experimental data obtained by varying the catalyst composition have shown that the enhancement in
the rate of the conversion by the plasma results from speeding up the rate-determining step, and the
contributions of gas–phase reactions and photocatalysis caused by the plasma are insignificant.
 Y.S. Mok, et al., Int. J. Sus. Dev. Plann. Vol. 8, No. 2 (2013) 195

ACKNOWLEDGMENT
This research was supported by Basic Science Research Program through the National Research
Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (Grant
number 2010-0021672).

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