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 in tackling
the global warming effect. Several technologies including catalytic and plasma were
proposed to improve the process involving the conversion and utilization of methane.
The direct conversion of methane to methanol in the assistance of plasma has attracted
a great deal of attention in recent years. In this reviewed paper, the usage of methanol
and concept of plasma were brief summarized. The recent advancements in direct
conversion of methane to methanol by plasma were summarized. The synthesis
methanol from methane and oxygen, methane and carbon dioxide, methane and water,
methane and nitrogen oxide by plasma were discussed in this article. Various effects of
feed gas ratio, gas flow rate, applied voltage and inert gas on the conversion and
reaction selectivity were clarified mainly on methane and oxygen system. Plasma
technology served as an unconventional catalysis will be widely used in methane
conversion to methanol.
Index Terms — Plasma applications, chemical industry, oxidation.

1 INTRODUCTION energy, particularly in space heating, automobiles, fuel cell,

OIL and natural gas, the main fossil fuels, not only remain
our major energy sources but they are also the feedstock for a
great variety of manmade materials and products that range from
gasoline and diesel oil to varied petrochemical and chemical
products, including synthetic materials, plastics, and
pharmaceuticals. As the fossil fuels continue to be significantly
depleted and will become increasingly costly, we need to search
for new sources and solutions.
The natural gas, with more than 90% consists of methane, is
becoming a new promising resource to replace the petroleum oil.
Recently, the studies related to the utilization of methane are
increasing. One of them, and could be the most challenging is
the conversion of methane to liquid chemical. There are,
however, two major reasons: 1. Most of natural gas is found in
remote areas far from the consumer markets, it is difficult to
transport and needs special pipelines. In situ process to convert
methane to liquid chemical will reduce the cost of the
transportation; 2. As the fuel cell is more preferable as the clean
electrical resources together with the safety consideration, the
liquid fuel from methane could be more promising. Many
attempts have been made to synthesize methanol from methane
[1]. Recently, studies were also carried out in producing
methanol from methane by plasma [2].
Methanol is a clean renewable fuel with a large part of useful
energy and is in great demand as an intermediate source of
Manuscript received on February 2008, in final form XX Month 2005.
electric power generation, and so on. In order to decrease the
effect of automobiles’ off-gas on air, methanol is being
recognized as a replacement for methyl tertiary butyl ether, used
as an additive in petroleum to increase the oxygen content.
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
(2)
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.
Due to the fact that the commercial methanol synthesis
process is energy intensive, it may not be economical when
the natural gas is in remote places or expensive. However, a
desirable alternative maybe the direct partial oxidation of
methane to methanol since a one-step process could
potentially reduce both capital and operating costs.
Meanwhile, an increasing number of applications and
manufacturing processes that require methanol in much
smaller quantities than refineries or methanol plants emerge,
e.g. in fuel cell applications [3]. 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.
concentric cylinders. The outer cylinder serves as ground
electrode. The inner cylinder is usually made of glass or
quartz tube and acts as the dielectric. A metal rod, made of
steel or copper, is located the inner wall of the inner cylinder
and acts as another electrode. The feed gases flow along
axially in a gas gap between the two concentric cylinders.
This type of reactor has a captive nature with a glass
dielectric that evenly distributes the “micro-discharges” and
limits their duration [6].

1.2 PLASMA AND PLASMA CHEMISTRY

Plasma can be defined as gas consisting of electrons,
highly excited atoms, ions, radicals and molecules photons
and neutral particles. One important type of plasma is the
non-thermal plasma in which the electrons have a much
higher energy than the other particles. Non-thermal plasma is
also called non-equilibrium plasma due to the difference of
temperature or kinetic energy between the electrons and the (a) Double-cylindrical tube reactor by Larkin et al. [7]
neutral particles [4].
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). DBDs have been known for more than a
century. The bulk gas temperature remains as low as room
temperature, while the electrons can reach as high as 105K in
a dielectric-barrier discharge. The gas discharge can produce
non-thermal plasma by applying a high voltage to a gas space
and inducing gas breakdowns. The gas breakdowns generate
electrons that are accelerated by an electric filed forming non-
thermal plasma. In the plasma reactor, the energetic electrons
collide with reactant molecules in the gas, resulting in
excitation, ionization, electron multiplication and the
(b) Single-Cylindrical tube reactor by Okumoto et al. [10]
formation of atoms and metastable compounds [5]. The active
atoms and metastable compounds then collide with
molecules, and reactions then happen. When the electric filed
in the discharge gap is high enough to cause breakdowns in
most gases, a large numbers 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. The basic principle
of this technique is the same as the above described. A lot of
investigations have been made to apply plasma chemical
reaction for direct methanol synthesis from methane in
combination with other gases such as O2 [6-16], CO2 [22-25],
H2O [26-28], etc.

2 METHANE OXIDATION
Various designs of plasma reactor for methane and oxygen
conversion to methanol have been proposed shown in Figure
1. A dielectric-barrier discharge (DBD) is one of the most
extensively investigated devices producing non-thermal
plasma at ambient pressure and room temperature. The
typical tubular discharge reactor is consisted of two
(c) Micro-scale DBD by Nozaki et al. [16]
Figure 1. Various designs of plasma reactor
The DBD reactor was considered as the catalytic reactor an
analog to a catalytic reactor by Larkin et al. [7] because the
DBD reactor reduced the required temperature and pressure
needed for reactions to occur within it as well as control
product selectivity just as with the catalytic reactor which was
shown in Figure 1(a). In their studies, the DBD reactor was
used to synthesis methanol from methane and oxygen.
However, methanol partially oxidized 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 investigated
experimentally and theoretically in a DBD by Zhou et al. [8].
The highest methanol yield of 3% and 2% were obtained
respectively in CH4/O2 mixtures and CH4/air mixtures.
Another type of DBD reactor was proposed by Aghamir et
al. [9] and Okumoto et al. [10]. It was shown in Figure 1(b).
Their discharge reactor consisted of a 10mm inner diameter
quartz tube, which was also served as dielectric barrier. Two
electrodes, one made of a stainless steel rod and the other
made of a 15cm long aluminum foil, formed the anode and
the cathode of the discharge. The aluminum foil was tightly
wrapped around the quartz tube, which had a 12 mm outer
diameter. The stainless steel electrode had 2 mm diameter
and was placed on the symmetric axis of the tube. Two gas
inlets located at the top and the bottom of the reactor
provided a means for the gas to flow steadily. Non-thermal
plasma was generated in this DBD reactor. C 2 hydrocarbons
and methanol were produced in their research and the
selectivity of methanol was as high as 75% when the ac
applied voltage is 16 kV. Similar principles were shown by
Okumoto et al. [10] using pulsed corona discharge with co-
axial cylindrical reactor. The inner metal electrode was a
stainless steel wire and an outer electrode of aluminum sheet
wraps around a quartz tube. The quartz tube prevented
sparking between the electrodes. The pulsed corona discharge
reactor has been used by other researchers for synthesizing
methanol from methanol and oxygen [11-15].
An interesting reactor design was also proposed by Nozaki
et al. [16] using a 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 secured in a heat
reservoir to maintain a constant reaction temperature. A high-
voltage sine wave was applied between the twisted metallic
wire and the grounded heat reservoir. The principal of
generating plasma was similar to DBD which was
characterized by a large number of filamentary micro
discharges of 1-10 ns duration. In this reactor, methanol was
the major product, whose selectivity reached 34% at 30% of
methane conversion.
Although the designs of the above four reactors were
different, they all belonged to DBD reactor. They all had large
volume excitation and the entire electrode area was effective
for discharge reactions. Moreover, the electron density in
DBD was higher than other kinds of plasma reactor. All of
these advantages were benefit for the conversion of methane.
In synthesizing methanol from methane and oxygen,
methane conversion and methanol formation were affected by
many parameters. The main parameters were the feed gas
mixing ratio, residence time, applied voltage and inert gas.
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 [17,18]
and less production of methanol. This situation is
similar when the concentration of O 2 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. [9] 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 [19]. Oppositely, it was concluded by Yao
et al. [13], and supported by Larkin et al. [7], 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 [19].
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 [7].
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 23kV, while the
later was only 15kV. 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. [12]. The similar
result was reported by Okazaki et al. [11]. A clear
profile of methanol production under different
residence times were presented in Larkin et al.
paper [7]. 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 [18]. 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 CO 2
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 [20].
The effect of supplied power will similar to the
temperature effect that higher amounts will
produce higher reactants conversion. Aghamir et
al. [9] 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 [7,19,21]. This
idea is still arguable since Okazak et al. found
that all data coincided closely for various
combinations of applied voltage and electrode
gap [11]. Below an electric field of 21.3kV/cm,
almost no methanol yield was observed.
2.4 NOBLE GAS EFFECT
In most synthesizing methanol from methane
and oxygen by plasma, the inert gas was added
to feed gas. The inert gas acted as dilution and
played an important role on reaction. Firstly, inert
gas could not only decrease the partial pressure
of source gases (methane and oxygen), but also
it changed discharge process. Secondly, the
breakdown potential of inert gas, such as He,
was lower than that of methane or oxygen on the
same condition, discharge could occur in low
applied voltage by adding inert gas to source
gases. Thirdly, population of energetic free
electrons might increase as the discharge of inert
gas; this would enhance the conversion of
methane. The detailed effect of inert gas on the
experiment was much less pronounced. It was
reported by Okumoto et al. [14] that with the
increase of dilution ratio which resulted in
decreased of the O2 partial pressure, the
methanol synthesis had a peak and then
decreased, while ethane production was
increased. They also found that when the O2
partial pressure was kept constant, the methanol
synthesis was increased with increase of the
dilution, ethane production stayed still. The
number of electron produced in one pulse was
increased at higher dilution ration. The gas
dilution analysis among different inert gases of
Ar, He, Ne and nitrogen was investigated by
Okumoto et al. [15]. 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 acted as oxidant. Because the
oxidizing ability of carbon dioxide was lower than
that of oxygen, the content of methanol in
product was very small, even in some
experiments no methanol was detected. For
instance, Jiang et al. [22] reported that syngas,
light hydrocarbons and liquid fuels could be
produced in plasma methane conversion with
carbon dioxide, there was no methanol in
products. It was reported by Zou et al. [22]
oxygenates could be produced from methane
and carbon dioxide using DBDs in the presence
of starch, a selectivity of oxygenates as high as
41% were obtained. The total oxygenates yield
was 5-26 wt %, formaldehyde, alcohols, and
acids were the main compounds. The highest
content of methanol in the product distribution of
oxygenates was only 7.1 %. Zhang et al. [24]
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 effect of concentration of
reactants (CH4+O2 and CH4+CO2 mixtures) was
studied by Rajanikanth et al. [25]. In their
studies, the maximum methanol concentration
reached 5×10-3(mol) in case of CH4+O2, but only 4×10-
3
(mol) of methanol production was observed in the case of
CH4+CO2. The fewer yields might attribute to energy required
to decompose carbon dioxide.
Since methane and carbon dioxide are the top
two greenhouse gases which can lead to global
warming, the combination of utilization of carbon
dioxide and methane will be promising in future.
More and more researchers have focused on the
methanol synthesis directly from methane and
carbon dioxide using plasmas. 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 be realized under
thermal equilibrium conditions using catalysts.
However, this conversion process was not
optimized for the system because an input
energy for methane conversion to methanol with
oxygen was used only as a trigger of this
reaction and was not stored as chemical energy
of products because of the exothermic process.
By contrast, methanol synthesis from a methane
and water-vapor mixture gas had an advantage
of being able to store the injected energy as
chemical energy of products since this reaction
takes place as an endothermic process. But this
conversion hardly finishes by thermal energy due
to increasing of Gibbs free energy via this
reaction. In order to achieve this conversion,
some researchers have undergone many
investigations on plasma methane conversion to
methanol with water vapor or water.
Methanol was successfully produced from
methane and water in a pulsed discharge plasma
reaction by Rajanikanth et al. [26]. They
designed three types of reactor: straight wire
reactor (SWR), Helical wire reactor (HWR), and
Barbed plate reactor (BPR) and found that Helical
wire and barbed plate reactors performed better
than straight wire reactor in synthesizing
methanol. Methanol was synthesized at two
different temperatures. The methanol output was
highly dependent on the state of the water in the
reactor.
Direct methanol conversion from a methanol
and water-vapor gas mixture by spark and a
glow-like discharge was investigated by Hijikata
et al. [27]. The conversion and product yield
were depended on applied high voltage time,
total pressure and ratio of gas mixture. The
maximum mol 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. [28] to
synthesize methanol from methane and water-
vapor mixture gases. In order to enhanced the
value of methanol yield, adding rare gas such as
Kr or Ar to the source gas was chosen. Methanol
yield reached the order of 1% at the water-vapor
concentration of about 50%. In our previous
investigation [29], 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 is
attractive in synthesizing methanol through
plasma.
2.7 NITROUS OXIDE (N2O)
The partial oxidation of CH4 with N2O to CH3OH
was explored in a non-thermal dielectric-barrier
discharge system under mild condition by
Matsumoto et al. [30]. The partial oxidation of
CH4 with N2O has been considered to be one of
the most selective processes in CH3OH synthesis.
In an Ar stream, about 10% of the combined
yield of CH3OH and HCHO, and 40% of the
selectivity to these products were achieved. This
value is high compared with the above
processes. However, the experiments on the
mixture of CH4+N2O are currently suspended due
to the excess production of lethal HCN gas.
3 CONCLUSIONS
The conversion of methane to methanol by plasma
technology has just been studied for a few years. This area is
attracting more and more researchers’ attention and is
flourishing. However, there are still a lot of problems needed
to be solved. The methanol yield in most experiments was
very low. Most experiments on plasma methane conversion to
methanol are based on experiences and the detailed
mechanism on synthesizing methanol has not been formed.
Only a few mechanisms were assumed in the experiments
[19, 31-32], but they are 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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