A review on direct methane conversion to methanol by

dielectric barrier discharge

Antonius Indarto
Korea Institute of Science & Technology
PO BOX 131 Cheongryang
Seoul, South Korea

ABSTRACT
The topic on conversion and utilization of methane were important issues to tackle the
issue of the global warming. Several technologies including plasma-based process were
proposed to improve the process involving the conversion and utilization of methane.
The direct conversion of methane to methanol in the presence of energetic species, i.e.
ion, radical, electron, and excited molecules, has attracted many experts’ attention in
recent years. In this reviewed paper, the concepts and the applications of plasma to
synthesize methanol from methane were brief summarized. The recent advancements
in direct conversion of methane were summarized. The synthesis methanol from
methane and oxygen, methane and carbon dioxide, methane and water, methane and
nitrogen oxide by plasma were discussed as well. Various parameters of feed gas ratio,
gas flow rate, applied voltage and inert gas on the conversion and reaction selectivity
were also discussed but mainly on the methane-oxygen system.
Index Terms — Plasma applications, chemical industry, oxidation.

1 INTRODUCTION Methanol, a well-known clean renewable fuel, is in great

OIL and natural gas, not only our remain major energy
Manuscript received on February 2008, in final form XX Month 2005.
sources but also the feedstock for various man-made materials
and products, range from gasoline and diesel oil to many
different petrochemical and chemical products, including
synthetic materials, plastics, and pharmaceuticals. As the
crude liquid oil continues to be depleted significantly and will
become costly, the solution and/or the invention of new
sources are necessary.
The natural gas, with more than 90% consists of methane,
is becoming a new promising resource to replace petroleum
oil. Recently, the studies related to the utilization of methane
demand as an intermediate source of energy of our daily life,
for example: space heating, automobiles, fuel cell, and
electric power generation. In the transportation sector,
methanol has been recognized as an environmental
friendliness-replacement for methyl tertiary butyl ether
(MTBE), used as an additive in petroleum in order to
increase the oxygen content of reactants. Therefore, methanol
could prove to be a principal fuel for the 21st century.
1.1 INDUSTRIAL METHANOL SYNTHESIS
Nowadays, methanol is manufactured by a two-step
method, which means that, to begin with, synthesis gas
(syngas) is produced from methane,
CH4 + H2O  CO + 3H2 ΔHo = 206 kJ/mol (1)
CH4 + ½O2  CO + 2H2 ΔH = -36 kJ/mol
o

are increasing. One of them, and could be the most (2)

challenging, is the conversion of methane to liquid chemicals.
There are, however, two major reasons: 1. Most of natural gas
was found in remote areas and far from the consumer
markets. It brings a difficulty to transport it which required
long pipelines system. In situ process to convert methane to
liquid chemical could reduce the cost. 2. These days, some
new energy converter processes, e.g. fuel cell, are preferable
as a clean electrical resource together with its safety
consideration. The production of liquid fuel from methane
could play an important pivot point and be more promising in
the future. Many attempts have been done to synthesize
methanol from methane [1]. Recently, some studies are still
carried out in producing methanol from methane by plasma
[2-5]. Mostly, the investigations were focused on finding the
best catalyst to improve the yields of methanol.
then, methanol synthesis from syngas. This process is
called indirect routes.
CO + 2H2  CH3OH ΔHo = -90.6 kJ/mol (3)
CO2 + 3H2  CH3OH + H2O ΔHo = -49.5 kJ/mol (4)
CO + H2O  CO2 + H2 ΔHo = -41.2 kJ/mol (5)
As the first reaction is highly endothermic, the process
suffers from high cost and thermal insufficiencies. The
second process is an exothermic reaction and needs copper
as catalyst. The synthesis reactor is typically operated at
the condition of high temperature and high pressure to
achieve high yields of methanol. On the other hand, this
environment tends to shorter the lifetime of the catalyst
due to sintering of the active metal on the surface of the
catalyst. the most investigated devices for producing non-thermal
Due to the fact that the commercial methanol synthesis plasma at ambient pressure and room temperature. The
process is energy intensive, it may not be more economic typical tubular discharge reactor is consisted of two
when the natural gas could be utilized directly. However, a concentric cylinders. The outer cylinder functions as
ground electrode and the inner cylinder, usually made from
desirable alternative maybe the direct partial oxidation of
glass or quartz tube, serves as the dielectric. A steel or
methane to methanol since a one-step process could
copper metal rod is located inside the inner cylinder and
potentially reduce both capital and operational costs. performs as another electrode. When plasma was turned
Meanwhile, an increasing number of applications and on, the micro-discharges could appear on the surface of the
manufacturing processes that require methanol in much inside electrode with very short lifetime [10].
smaller quantities or methanol mobile-plans, e.g. fuel cell
applications [6], would deliver a strong message about the
importance of methanol-based process in the future.
Compare to hydrogen-based processes, methanol fuel is
safer and easier to handle. A comprehensive review of this
comparison has been done by Olah [7]. Developing new
techniques and processes of direct conversion of methane
to methanol is becoming a challenging research subject.
Among other methods and techniques, non-thermal plasma
chemical process is one of the most promising technologies
in synthesizing methanol.

1.2 PLASMA AND PLASMA CHEMISTRY (a) Double-cylindrical tube reactor by Larkin et al. [11]
Plasma can be defined as gas consisting of electrons,
highly excited atoms, ions, radicals, photons, and neutral
particles. Non-thermal plasma, classified as low-supplied
power plasma, is populated by electrons that have much
higher energy than the other surrounding particles. Non-
thermal plasma is also called non-equilibrium plasma due
to the difference between ion and electron temperature or
because the velocity concentration of energetic species did
not follow a Maxwell-Boltzmann distribution [8].
The non-thermal plasma can be generated and
maintained by electrical discharge such as corona
discharges, pulse discharge, microwave discharge and
dielectric-barrier discharge (DBD). DBD has been known (b) Single-Cylindrical tube reactor by Okumoto et al. [14]
for more than a century. The bulk gas temperature remains
as low as room temperature, while the electrons can reach
as c.a. 105 K. Usually, the discharges are produced by
supplying high voltages (10-20 kV) to the electrodes and
the gas between the two electrodes will reach the phase-
transition point between ground-state and excited-state
levels. Inside the plasma reactor, energetic electrons can
collide with reactants in many modes: excitation,
ionization, electron multiplication, fragmentation into
atoms, and metastable compounds [9]. When the electric
field in the discharge gap is high enough to cause, a large
number of micro-discharges can be observed.
Recently, the use of non-thermal plasmas has been
proposed as a new technology for methanol synthesis at
ambient pressure and room temperature. Many
investigations have been devoted to apply plasma chemical (c) Micro-scale DBD by Nozaki et al. [20]
reaction for direct methanol synthesis from methane in
combination with other gases, such as O2 [10-20], CO2 [26- Figure 1. Various designs of plasma reactor
29], and H2O [30-32].
The DBD reactor could be considered as the catalytic
2 METHANE OXIDATION reactor analog to a catalytic reaction following the idea of
Various designs of plasma reactor for methane and Larkin et al. [11]. It is because the DBD reactor was able to
oxygen conversion to methanol have been proposed shown reduce the required temperature and pressure needed for
in Figure 1. Dielectric-barrier discharge (DBD) is one of reactions to occur as well as its ability to control the
products selectivity. The proposed reactor is shown in
Figure 1(a). In their studies, the DBD reactor was used to
synthesis methanol from methane and oxygen. However,
methanol, oxidized partially from methane, could further
react to form other oxygenates such as formic acid,
formaldehyde, and methyl formate. The partial oxidation
of methane to methanol with oxygen or air was also
investigated experimentally and theoretically by Zhou et al.
[12]. The highest methanol yields of 3% and 2% were
obtained in CH4/O2 and CH4/air mixtures, respectively.
Another type of DBD reactor was proposed
independently by Aghamir et al. [13] and Okumoto et al.
[14]. The general scheme of the reactor is presented in
Figure 1(b). The discharge reactor consisted of a 10 mm
inner of diameter quartz tube, which was also served as
dielectric barrier. Two electrodes i.e. a stainless steel rod
and a 15 cm long aluminum foil, formed as a pair of anode
and cathode of the discharge. The aluminum foil was
tightly wrapped around the quartz tube, which had outer
diameter of 12 mm. The stainless steel electrode was
placed on the symmetric axis inside the tube. Two gas
inlets located at the top and the bottom of the reactor were
provided as an inlet of the reactants and an outlet of
products. C2 hydrocarbons and methanol were produced
mainly and the selectivity of methanol reached c.a. 75%
when the alternating current (AC) voltage was 16 kV. A
similar experimental set-up was used by Okumoto et al.
[14] with different type of plasma, pulsed corona
discharge. The inner metal electrode was a stainless steel
wire and an outer electrode of aluminum sheet wrapped
around a quartz tube. The quartz tube could prevent the
‘sparking’ between two electrodes. The pulsed corona
discharge reactor has been also used by other researchers
for synthesizing methanol from methane and oxygen [15-
19].
An interesting reactor design was also proposed by
Nozaki et al. [20], so-called micro-plasma reactor, shown
in Figure 1(c). It consisted of a pyrex thin glass tube and a
twisted metallic wire inside the tube. The reactor was
placed in a heat reservoir to maintain a constant reaction
temperature. High sinusoidal-voltage was connected to the
twisted metallic wire and the grounded-heat reservoir. The
principal of generating plasma was similar to the DBD
which was characterized by a numerous numbers of
filamentary micro discharges. In this experiment, methanol
was the major product, whose selectivity reached 34% at
30% of methane conversion.
Different designs of the above three-type reactors could
lead to the different strength of electrical field and
energetic species distributions. These advantages could be
the benefit of the conversion of methane using plasma.
Apart from the reactor set-up choices, methane
conversion and methanol formation were still affected by
many parameters. The main parameters were the feed gas
mixing ratio, residence time, applied voltage and inert gas.
These parameters have to be managed in order to achieve
the optimum production of methanol.
2.1 CH4 TO O2 RATIO
The ratio of methane to oxygen in the feed
gas plays an important role to produce a good
selectivity of methanol. Similar to the thermal-
based process, O2-rich condition will drive the
reaction to the perfectly oxidation reaction
where the products will be dominated by CO2
[21,22] and less production of methanol. This
situation is similar when the concentration of
O2 in the feed is low, the lack of oxygen will
inhibit the synthesis of methanol and methyl
coupling will be the major pathway. Aghamir et
al. [13] reported that the existence of oxygen
in gas mixture leaded to the production of
methanol and with the increasing of the ratio
O2/CH4, the selectivity of methanol first
increased rapidly, then decreased. The
optimum ratio of methane to oxygen was
reported to be 4:1 which result methanol
selectivity of 12% in catalyst-free process [23].
Oppositely, it was concluded by Yao et al. [17],
and supported by Larkin et al. [11], that
oxygen concentration could not influence the
methane conversion rate and methanol
selectivity, but high oxygen concentration
resulted in the increase of CO and CO2
formation. Moreover, the reported methanol
production by plasma method was higher than
that resulted by thermal process in all ranges
of methane to oxygen ratios [23].
Following the different above ideas, it was
strongly concluded that the methanol
production is also affected by other variables.
Larkin et al pointed that at longer residence
time, the produced methanol will be consumed
to the formation of organic acids and
formaldehyde [11]. The difference of reactor
used in the experiment and supplied powers
could also be the reason of different results.
For example, the applied voltage of former
reactor was 23 kV, while the later was only 15
kV. The amount of methane activated was
mainly influenced by the discharge
characteristics, but the rates of oxidation of
•CH3, •CH2, and •CH to CO and CO2 were
depended on oxygen concentrations.
2.2 RESIDENCE TIME
Under the conditions of fixed temperature,
pressure, and methane/oxygen feed ratio,
increasing the total gas flow rate could
increase the methanol concentration in the
products reported by Okumoto et al. [16]. The
similar result was reported by Okazaki et al.
[15]. A clear profile of methanol production
under different residence times were
presented in Larkin et al. paper [11]. They
reported that when the residence time <2.5 s,
the methanol selectivity was initially the
dominant products among other organics
liquids then decreased gradually on longer
residence time. It means that methanol
scavenging reaction was occurred just after
methanol formed by plasma reaction. The
methanol will be decomposed to form other
oxygenates such as formic acid, methyl
formate.
By different way of the presentation,
Indarto’s work shows that the CO2
concentration was higher at longer residence
times [22]. In the conclusion, they mentioned
that longer residence time will drive the
plasma reactions into perfect oxidation
reaction by giving more chance to oxygen to
react with molecules. As CO2 is
thermodynamically stable molecule, the
pathways of CO2 synthesis are preferable.
However, the shorter residence time or faster
feed to the reactor will definitely reduce the
conversion of methane and affect to the
lowering the yields of methanol.
2.3 APPLIED VOLTAGE
Voltage and power are the intrinsic property
of electrical generator used to generate
plasma. Many studies have examined the
effects of different wave power, e.g.
alternating current (AC), direct current (DC),
mono-pulse, bi-pulse, etc., or different power
strengths on methane conversion to methanol
by plasma. Song et al. showed that different
wave forms will result different products
distribution quantitatively [24]. The effect of
supplied power will similar to the temperature
effect that higher amounts will produce higher
reactants conversion. Aghamir et al. [13]
reported that the conversion of methane
increased with an increase in applied voltage
and increasing the applied voltage had almost
no effect on the product selectivity in without
oxygen and helium.
In general, many papers mentioned that
there is an optimum point of supplied power to
the reactor for methanol production [11,23,25].
This idea is still arguable since Okazak et al.
found that all data coincided closely for
various combinations of applied voltage and
electrode gap [15]. Below an electric field of
21.3kV/cm, almost no methanol production
was observed.
2.4 NOBLE GAS EFFECT
In most researches of methanol synthesis
from methane and oxygen by plasma, noble
gas, e.g. helium, neon, argon, was added to
feed gas to help the performance of the
process. The noble gas could act as inert gas
dilution and play an important role on the
reactions. First, noble gas was not only
decreasing the partial pressure of reactants,
but also it could change the density of the
discharge species in the plasma-zone. Second,
the breakdown potential of inert gas, such as
helium and argon, was lower than that of
methane or oxygen at the same condition. It
means that the plasma could be initiated in
low supplied voltage. Third, the population of
energetic free electrons might increase at
higher concentrations of noble gas. Moreover,
this would enhance the conversion of
methane. The detailed effect of inert gas in the
experiment was much less pronounced. First
report by Okumoto et al. [18] mentioned that
with the increment of dilution ratio of noble
gas, resulted the decrease of the O2 partial
pressure, the methanol synthesis could
reached the maximum point before it
decreased for further more addition. The
ethane production, however, was increased
linearly. They also found that when the O2
partial pressure was kept constant, the
methanol synthesis increased in higher noble
gas concentrations and ethane production was
constant. The number of electrons produced in
a full pulse wave was increased at higher
dilution ratios. More detailed analysis among
different noble gases of helium, neon, argon,
and nitrogen was presented in the second
paper of Okumoto et al. [19]. Their research
revealed that for the dilution with these inert
gases, the production of liquid products
showed almost the same. Only in the case of
using nitrogen as the dilution gas, the
maximum value of the production ability was
low compared to other rare gases, but the
same tendencies of enhancement of
production with the dilution rate were
obtained.
2.5 CARBON DIOXIDE (CO2)
Experimental investigations on plasma
methane conversion in the presence of carbon
dioxide using dielectric barrier discharges have
been conducted. Similar to oxygen, carbon
dioxide also functioned as oxidant. As the
oxidizing ability of carbon dioxide was lower
than that of oxygen, the produced methanol
was very small, even in some experiments no
methanol was detected. For instance, Jiang et
al. [26] reported that synthesis gas, light
hydrocarbons, and liquid fuels could be
produced but there was no methanol in
products. Further report by Zou et al. [27]
mentioned that oxygenates species could be
produced from methane and carbon dioxide
using DBDs in the presence of starch and the
obtained selectivity of oxygenates was c.a.
41%. The total oxygenates yield was 5-26 %,
and formaldehyde, alcohols, and acids were
detected as the main compounds. The highest
concentration of methanol among the
oxygenates was only 7.1 %. Almost similar
results was presented by Zhang et al. [28] who
reported that acetic acid was the primary
product in the condensate with the highest
selectivity of 5.2 % at 66.8 % of methane in
the feed. However, the highest selectivity of
methanol was only 1.1 %. The comparison
reactants study of CH4+O2 and CH4+CO2
mixtures was performed by Rajanikanth et al.
[29]. In their studies, the maximum methanol
concentration reached 5×10-3 mol in case of CH4+O2
and only 4×10-3 mol of methanol was produced in the case
of CH4+CO2. A fewer methanol yields may attribute to
higher energy required to decompose carbon dioxide.
Since methane and carbon dioxide are the
main two greenhouse gases which can lead to
global warming, the utilization of carbon
dioxide and methane will be promising in
future. However, the co-feed of carbon dioxide
induces a more complex product during
plasma methane conversion. Except for
methanol, other oxygenates such as formic
acid can also be generated.
2.6 WATER (H2O)
Methanol conversion from a gas mixture of
methanol and oxygen could only be realized
under thermal equilibrium conditions using
catalysts. By contrast, methanol synthesis from
a methane and water-vapor mixture gas has an
endothermic energy balance which could be an
advantage process by enabling the energy to
be conserved. But this reaction has an obstacle
on the thermal-based process as the Gibbs
energy (ΔG) is also raising. In order to realize
the reactions, some researchers have
undergone many trials on the plasma
environment to avoid the above problem.
Methanol was successfully produced from
methane and water in pulsed discharge
plasma by Rajanikanth et al. [30]. They
designed three types of reactor: straight wire
reactor (SWR), helical wire reactor (HWR), and
Barbed plate reactor (BPR), and found that
HWR and BPR performed better than SWR for
synthesizing methanol. Methanol could be
synthesized at two different temperatures and
strongly dependent on the presence of water
in the reactor.
Direct methanol synthesis from methane
and water-vapor gas mixture by spark and
glow-like discharge was investigated by
Hijikata et al. [31]. The methane conversion
and products yield were strongly depending on
the applied voltage, total pressure, and ratio of
gas mixture. The maximum fraction of
methanol produced from methane and water-
vapor by spark and glow-like discharge were
0.5 % and 0.7 %, respectively. A newly
developed ultra-short pulsed barrier in an
extremely thin glass tube reactor was used by
Okazaki et al. [32] to synthesize methanol from
methane and water-vapor mixture gases. In
order to enhance the production of methanol,
the addition of rare gas, such as Kr or Ar, to the
reactants was recommended. Methanol yield
reached ~ 1% at the water-vapor concentration
of about 50%. In our previous investigation
[33], direct synthesis methanol from methane
and water vapor mixture was successfully
enhanced in a concentric cylinder with a rod
steel electrode and an outer electrode of
copper foil around a quartz glass tube.
In the process of synthesizing methanol
from methane and water vapor using plasma,
no oxidant, such as oxygen or carbon dioxide,
is added which can avoid over-oxidation of
methane. Moreover, water, as co-feed
reactant, is very cheap and abundant. This
process could be attractive in this sense.
2.7 ALTERNATIVE PARAMETERS
There are many ideas have been proposed to
boost the small production of methanol. The
additional of unusual additive gasses, i.e. N2O,
has been explored by Matsumoto et al. [34].
The process has been considered to be one of
the most selective processes for methanol
synthesis. In the presence of argon, the yield
of methanol and HCHO was about 10%, and
40% of converted methane transformed to
production of those two products. This value
was significantly higher compared to the
results of the previous processes. However, the
experiments are currently suspended as it
suffers from a drawback by the production of
toxic side gas HCN.
The most promising way in plasma-chemical
process of methanol synthesis is by the
addition of catalyst. Many works have been
done and some are still in progress [2-5]. Liu et
al. and others mentioned that the catalyst
acted well in the presence of plasma although
the temperature of bulk gas was low for
methane conversion [35-37]. However, only
few researches were devoted for finding the
best catalyst for methanol synthesis. Indarto et
al. mentioned that the catalytic plasma
process was actually ‘mimic’ the conventional
ways of methanol synthesis by forming
synthesis gas in the first step of non-catalytic
plasma process [2]. Later on, the presence of
some catalysts, such as Cu/Zn/Al [2] or
yttrium-stabilized zirconia (CZA) [3,4], could
help the formation of methanol following the
reaction 3-5. However, this idea is still
arguable since there is no real analytical
research on the detailed mechanisms.
3 CONCLUSIONS
The conversion of methane to methanol by plasma
technology has been studied for a few years. This research
area has been attracting many experts to put efforts to
realize this idea. However, there are still many problems
needed to be solved which means a large space for further
researches. The methanol yield in most experiments was
very low. Most experiments on plasma methane conversion
to methanol were based on the experiences while the
detailed mechanism on it has not been well performed yet.
Only a few mechanisms were proposed [23, 38-40] and
still needed to be improved. In order to increase the
methanol yield and methanol selectivity, the combination
of plasma with catalyst may be a good choice.
ACKNOWLEDGMENT
This study was funded by the Korea Institute of Science
of Technology under the program of the National Research
Laboratory project of the Korea Ministry of Science and
Technology. The author thanks to the BK 21 program of
the Korea University and the Università degli studi di
Torino for the generous supports.
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