Renewable and Sustainable Energy Reviews 65 (2016) 250261

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Renewable and Sustainable Energy Reviews

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Direct conversion technologies of methane to methanol: An overview

Z. Zakaria a, S.K. Kamarudin a,b,n
a
Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia
b
Department of Chemical and Process Engineering, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia

art ic l e i nf o a b s t r a c t

Article history: The emission of greenhouse gases (GHGs) is a major air pollution issue that affects climate change across
Received 23 September 2014 the globe. Methane (CH4), behind carbon dioxide (CO2), is the second most abundant GHGs that nega-
Received in revised form tively impact the atmosphere layer. Many studies have been conducted to identify a method for reducing
31 March 2016
the concentration of methane in the atmosphere. Converting methane to alternative forms source of
Accepted 24 May 2016
energy, such as methanol, is a preferred method for methane reduction. This review aims to present an
overview of recent literature that focuses on conversion of methane to methanol, with a focus primarily
Keywords: on the manufacturing systems and processes used in this conversion. Basic descriptions are given of
GHGs several relevant technologies for converting methane to methanol and their characteristics, including
Methane
conventional catalytic processes, plasma technology, photo-catalysts, supercritical water processes,
Methanol
biological processes and other processes. All of these options are feasible for use in the conversion
Conversion of methane to methanol
process of methane to methanol.
& 2016 Published by Elsevier Ltd.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
2. Manufacturing and processing of methanol from methane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
2.1. Direct conversion of methane to methanol via conventional catalytic processes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
2.1.1. A high-temperature route based on homogeneous radical gas-phase reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
2.1.2. A low temperature catalytic route involving heterogeneous catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
2.1.3. Homogeneous catalysis in solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
2.1.4. Bio-catalysis based on enzymes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
2.2. Conversion methane to methanol via plasma technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
2.3. Conversion methane to methanol via photo-catalysts technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
2.4. Conversion methane to methanol via supercritical water technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
2.5. Conversion methane to methanol via biological process (Membrane technologies) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
3. Challenges and advancements in technologies for direct conversion of methane to methanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
3.1. Single-step oxidation of methane to methanol via conversional catalytic processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
3.1.1. Homogeneous gas-phase partial oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
3.1.2. Heterogeneous catalytic partial oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258
3.1.3. Homogeneous catalysis in solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258
3.1.4. Biocatalysis based on enzymes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258
3.2. Plasma technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258
3.3. Photocatalyst technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258
3.4. Supercritical water technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259
3.5. Biological process (Membrane technology) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259
4. Potential for expanding direct conversion of methane to methanol in industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259
5. Other possible technologies for conversion of methane to methanol. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259
6. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260

n
Corresponding author. Tel.: 60 389216422; fax: 60 389216148.
E-mail address: ctie@ukm.edu.my (S.K. Kamarudin).

http://dx.doi.org/10.1016/j.rser.2016.05.082
1364-0321/& 2016 Published by Elsevier Ltd.
 Z. Zakaria, S.K. Kamarudin / Renewable and Sustainable Energy Reviews 65 (2016) 250261 251

Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260

1. Introduction methane and anthropogenic sources of methane. Fig. 2 presents

Since the 1960s, many different human activities have required
the use of energy, especially from the burning of fossil fuels, which
produces car exhaust and industrial smoke emissions, to produce
electricity, power automobiles, heat houses, power factories, and
provide for cooking. These human activities listed above con-
tribute to the production of GHGs [13]. Fig. 1 shows the compo-
sition of GHGs produced by consumers worldwide since 1978.
All of these gases represent greenhouse gas emissions that
potentially contribute to global warming, which has a negative
impact on human life. The emission of GHGs such as carbon
dioxide, nitrous oxide, methane and chlorouorocarbons (CFCs)
has resulted in additional heat being trapped in the lower atmo-
sphere, ozone depletion, and an increase in global temperature.
According to a World Health Organization (WHO) report, the
Earth's temperature has risen approximately 0.75 C in the last one
hundred years. In effect, every quarter-century is experiencing an
increase in temperature of about 0.18 C [5], and this high rate of
global warming is adversely affecting the world's ecosystems.
A notable portion of the increase in GHG emissions is due to
methane. Methane is the simplest alkane and contains only one
carbon atom; it is a building block of most bulk organic com-
pounds on earth [6]. An advantage of methane as a fuel source is
that it is high caloric. As a main component of natural gas,
methane is used for residential heating and cooking and as a fuel
in gas turbines for generating electricity [6,7]. Due to its desirable
properties, methane is a widely consumed fuel in the chemical
industry and households alike. In general, methane emission
sources can be classied in two categories: natural sources of
the anthropogenic methane emissions from all different source
sectors while Fig. 3 shows the contribution of individual sources to
total natural methane emissions [2,711].
Aside from all the benets of methane to daily human activ-
ities, it is nonetheless classied as GHGs [2]. As shown in Fig. 1,
there has been a signicant increase in GHGs emissions into the
atmosphere since 1978, which creates an imbalance air composi-
tion resulting in climate change. Although the emission of
methane is smaller than carbon dioxide, methane has a tendency
to absorb and release infrared radiation (IR). The combined effect
of heat trapping and IR absorption will increase world temperature
on a continuous basis due to the formation of a thermal layer in
the atmosphere [8]. Therefore, methane has a 25 times larger
potential impact to trap heat than carbon dioxide on increasing
global warming and thus affecting the climate [7,8]. Another
detrimental effect of methane in the environment is that as it sinks
in the atmosphere, it reacts with hydroxyl radicals in the tropo-
sphere and chloride radicals in the stratosphere leading to an
imbalance in composition of methane [8].
Many researchers today are addressing the issue on recycling
the GHGs by converting into value added product [1,2,711].
Reddy et al. [8] presented a review on the conversion of methane
to value added product while Alvarez-Galvan et al. [12] presented
work in direct conversion of methane to fuel and chemicals. This
paper will present the direct conversion technologies of methane
to particularly to methanol.
From another angle, the worldwide energy demand is
increasing daily due to worldwide population increases. The
human population in 1750 was approximately 800 million. In

Fig. 1. Global averages of the concentrations of the greenhouse gases carbon dioxide, methane, nitrous oxide, CFCs-12 and CFCs-11 [4].
252 Z. Zakaria, S.K. Kamarudin / Renewable and Sustainable Energy Reviews 65 (2016) 250261

Fig. 2. Anthropogenic methane emissions from all different source sectors [8].

Fig. 4. Theoretical energy densities [15].

sources such as the lithium rechargeable battery. Fig. 4 clearly

illustrates the advantages of the DMFC energy density compared
with that of batteries. Kamarudin et al. [18] published an excellent
overview of several applications of DMFCs as energy sources in
portable electronic devices such as cellular phones, laptop com-
puters, and portable cameras. Recently, industrial companies such
as Panasonic, Toshiba, Hitachi, Sanyo and NEC have developed
Fig. 3. Contribution of individual sources to total natural methane emissions [10].
DMFC products. Panasonic plans to manufacture a portable power
generator that is more compact than engine-based generators and
1900, it increases to 1.6 billion. In 2005, the global population produces an output of 100 W [22]. Samsung's Advanced Institute
achieve to 6.5 billion [1,13]. A survey from the US Department of of Technology and Motorola Labs have created portable power
Energy in 2009 revealed that the consumption of electricity sources with power densities of 23 mW cm  2 and 12
increases signicantly every year and is projected to increase by 27 mW cm  2, respectively [23,24]. Hence, DMFCs offer the
44% from 2006 to 2030 [14]. Therefore, to nding alternative
advantages of high energy density, easy of charging, low weight,
energy sources are necessary to ensure that the advancement of
simplicity, rapid start-up, small-size storage and low environ-
modernity is sustainable for future generations and, simulta-
mental impact as a green energy source that is safe for consumer
neously, to solve the environmental crisis involving emissions of
use [21,24].
methane, which has become a formidable challenge. This study includes the different technologies for the direct
Additionally, methanol is a clean and renewable fuel source
conversion of methane to methanol, including conventional cata-
that contains a large amount of useful energy and is in great
lytic processes, photocatalysis technologies, plasma technologies,
demand as an intermediate source of green energy to provide
supercritical water oxidation technologies, membrane technolo-
electric energy generation via fuel cell (FC) technology applications
gies and other methods. We also summarize the advantages, dis-
[14]. FCs act as alternative sustainable power sources and offer
advantage, challenges and advancements of each technology.
high potential for distributed power generation in portable and
Based on the expected potential of this technology, this review
stationary applications as well as transportation [19]. Zakaria et al.
addresses two critical global issues involved in the reduction of
[20] described the FC as an electrochemical device that directly
methane emission as a GHG via conversion to methanol, which is a
converts fuel such as methanol into electrical energy via zero-
promising alternative source of green energy for meeting world
emission fuel combustion. Direct methanol fuel cells (DMFCs) have
demand and consumption. Fig. 5 illustrates the diversity of direct
emerged as a one type of green technology for alternative energy
conversion technologies for conversion of methane to methanol.
sources and are gaining attention among researchers. The ef-
ciency of DMFC electrical energy conversion reaches 60%; this
compares favorably with the conventional methods of generating
electrical energy, which require many conversions [21]. Compared 2. Manufacturing and processing of methanol from methane
with hydrogen, which is the pioneer fuel used in FCs, methanol
2.1. Direct conversion of methane to methanol via conventional
offers promising characteristics as a simple organic liquid with
catalytic processes
reactivity at low temperatures, efcient energy storage, and
handling that does not require a cryogenic container. In addition,
The conventional mechanism of methane to methanol direct
the volumetric energy density of methanol is 6.09 kW h kg  1,
conversion goes directly through a catalytic oxidation processes.
which is higher than the value of 3.08 kW h kg  1 for liquid
Methane can be converted to methanol in two ways: either via
hydrogen [1,20].
synthesis gas and steam reforming or directly into methanol. The
Kamarudin et al. [18] reported that the DMFC has demon-
fundamental conversion takes place by partial oxidation of
strated sustained cell performance for over 200 h of operation and
methane, as shown in Eq. (1):
did not signicantly degrade in performance until after 1002 h of
operation. DMFCs could potentially replace conventional batteries CH4 0.5O2-CH3OH H298  30.4 kcal/mol (1)
due to their high energy density compared with other energy
 Z. Zakaria, S.K. Kamarudin / Renewable and Sustainable Energy Reviews 65 (2016) 250261 253

Methane processing Conventional catalytic Homogeneous radical gas-

method: Oxidation process processes phase reactions

Plasma technologies Low temperature

heterogeneous catalysis

Conversion technologies: Photo-catalysis Homogeneous catalysis in

technologies solution

Supercritical water Bio-catalysis based on

oxidation technologies enzymes

Yielding production: Membrane technologies Fuel Cells

Methanol

Other technologies Electro-synthesis

Fig. 5. Diagram of diverse conversion pathways of methane to methanol.

The reaction can occur in both gas and liquid phases. In gas phase
oxidation, the parameters are typically as follows: 30200 bars and
200500 C with catalysts. In the liquid phase, these reactions are
implemented with the oxidization of methane by super acids. This
mechanism process was occurred by the activation of CH bonding in
the methane and subsequently it is splitting the covalent bonding
through electrophilic attack to yield e CH3. Then, oxidation reaction
yields the oxidized products of methane [2,25]. Currently, conven-
tional catalytic processes for conversion methane to methanol exist
according to:
2.1.1. A high-temperature route based on homogeneous radical gas-
phase reactions
The gas-phase reactions occur due to a free radical mechanism
at high temperature and pressure [12]. Thermodynamic and
kinetic analysis revealed that the partial oxidation of methane is
the rate-limiting step due to the formation of methyl radicals. The
initiators and sensitizers have been combined into the reaction
mixture to decrease the energy barrier of H-abstraction. Babero
et al. [26] introduced nitrogen oxide as a novel initiator in order to
promote the gas-phase reaction with methane, whereas, Tabata
et al. [27] make the comparison between the oxygen and nitrogen
oxide in order to promote gas-phase reaction with methane.
Meanwhile, the Fujimoto [28] reported that the consumption of
small quantities of hydrocarbons, such as ethane, was indicative of
a lower initiation temperature and increased selectivity and yield
of methanol.
One of importance factor that pronounced effect on the selec-
tivity of methane oxidation is control the pressure process. In the
Huels process via cold-ame burners using a pressure of 60 bars,
the conversion of methane is achieved to a selectivity of 71%
methanol and 14% formaldehyde [29]. While, Zhang et al. [31]
claimed indicate that under best conditions, i.e., temperatures of
723773 K and pressures of 3060 bars. Holmen [25] concluded
that the best conditions for the gas-phase reaction are a tem-
perature of 450500 C and a pressure of 3060 bars, with a
methanol yield reaching 3040% at 510% methane conversion.
Besides, there are several works presented on design and
modication of reactor with different wall materials to enhance
the conversion for minimize reactions on a metal surface, which
could diminish the methanol selectivity such as Arutyunov [30]
investigated on fast-ow gas-phase partial oxidation in reactors
with different wall materials (stainless steel and quartz) and
examined four parameters: pressure, methane/oxygen ratio, tem-
perature, and residence time. Zhang et al. [31] was provided a
comparatively high yield of methanol (78%, methanol and 63%
selectivity at 13% methane conversion) which set up the para-
meters over a 40 C temperature range (430470 C) at 5.0 MPa
and CH4/O2/N2 100/10/10 (ml/min, STP). They also designed a
new reactor based on the quartz-lined and stainless-steel-lined
tubular reactors and introduced the ringed gap by using a Viton O-
ring pressed as a locking nut to avoid the feed gas ow through
the ringed gap, as shown in Fig. 6. Another effort to enhance the
conversion via developing models of multiple beds gassolidsolid
reactor, such a containing of a catalyst xed bed and a second solid
that owing gas in counter-current. This reactor would tolerate
continuing lower temperatures in the adsorbent and higher levels
of adsorption because the temperature excess is removed after
each stage [32].
The high conversion of methane into methanol also was
obtained by working under non-catalytic reaction conditions. The
specic operation begins at 350 C, and the temperature is
increased to 500 C under fuel-rich mixtures with the oxidant to
minimize the extent of combustion reactions. Unfortunately, this
reaction is detrimental to controlling methanol selectivity [12].
There are also researchers examined that conversion through
under the non-catalytic gas-phase reaction accomplishment con-
verts methane from 10% to 80% [33,34].
2.1.2. A low temperature catalytic route involving heterogeneous
catalysis
The development of an active and selective catalyst is another
optional for the partial oxidation conversion of methane to
methanol because the gas-phase operation is unfavorable in terms
of controlling the selectivity of the desired yield and requiring a
254 Z. Zakaria, S.K. Kamarudin / Renewable and Sustainable Energy Reviews 65 (2016) 250261
Fig. 6. Reactor designed with Viton O-ring [31].
high operation pressure. Nevertheless, at lower pressure, i.e.,
1 atm, the selection of catalyst is very important for the yield.
Several of catalysts have concerning effort through the researcher,
such as, optimizing the catalytic performance with a slightly
reduced state by storing the isolated metal oxide on a silica sub-
strate [12]. Tabata et al. [35] proposed that the selection of O-
insertion into CH3 from the rst H-abstraction molecules of
methane by reduction of molybdenum and vanadium to their
oxides (MoO3 and V2O3). Aoki et al. [36] founded the formation a
silicomolybdic acid (SMA)-like structure on a MoO3/SiO2 catalyst
seems to drive the successive oxidation of methanol and increase
the amount of oxygenates produced during the partial oxidation of
methane due to the high catalytic activity. Reaction temperature
was kept at 873 K in an excess amount of water vapor.
Vafajoo et al. [37] optimized the catalyst through the CFD
mathematical model for the stimulated direct conversion of
methane to methanol over a V2O5/SiO2 catalyst in a Fixed-Bed
Reactor with a temperature from 450 to 500 C, a pressure range of
20120 bars and a time on stream of 3 s. The feed composition
consisted of 95% methane and 5% oxygen as the oxidizing agent.
Zhang et al. [38] prepared the lanthanum cobalt oxide impreg-
nated with different amounts of a (NH4)6Mo7O24 aqueous solution.
This perovskite-type oxide has a strong ability to activate and
diffuse oxygen. Therefore, the catalyst showed good activity in the
partial oxidation of methane. The catalytic test was carried out in a
continuous vertical-ow xed-bed reactor. Zhang et al. [39]
reported that as high as 78% methanol production was achieved
in the absence of catalysts. The reactor inertness is suitable for
obtaining good selectivity to methanol and the feed gas should be
barrier by using quartz and Pyrex glass-lined reactor. The utiliza-
tion of phthalocyanine complexes of Fe and Cu encapsulated in
zeolites X and Y as catalysts and O2/tert-butyl hydro-peroxide as
oxidants in ambient conditions successfully produces high-yield
activity (turnover number, TON above 100) and selectivity (CO2
less than 5%). A 4.9 mol% of methane conversion was achieved
with 107.2 t yield, of which 52.9 t is a methanol. These values are
among the highest for the catalytic oxidation of methane at
ambient temperature, as reported by Raja et al. [40].
Another catalyst was recognized favorable in selective oxidation of
methane to methanol is catalyst based on iron. Fe3 species
impregnated on copper iron pyrophosphate catalysts show high
reactivity for or selective oxidation of methane to methanol among
the heterogeneous catalysts. The highest single-pass yield of useful
oxygenates (1.8%) was achieved with N2O over the Cu/Fe 1:2
pyrophosphate catalyst which consists mainly of the crystalline FeIIFe
III
2 (P2O7)2 and copper-containing nano-domains [41]. Zocony Structure
Mobil Oil-5 (ZSM-5) zeolite catalysts have been exposed in this con-
version. This catalyst was modied with iron impregnation (Fe-ZSM-
5) by -oxygen pre-deposited from nitrous oxide was studied at room
temperature and placed in a specially designed one-piece quartz IR
reactor cell [42]. Another modication of ZSM catalyst was impreg-
nation with cobalt (Co-ZSM-5) for the conversion of methane until
achieved 42% and product yield methanol of 7.56% [43]. Another
approach, Co-ZSM-5 was tried to modied with Fe and Cu via a
chemical vapor impregnation method and presented high selectivity
to methanol (492% selectivity, 0.5% conversion) [44].
2.1.3. Homogeneous catalysis in solution
The conversion of methane to methanol also recognized
through the homogeneous catalysts under low temperature in
solution. Under this conditions, the catalyst activation of CH
bonds do not involve radicals, which has the potential to lead to
more selective reactions than those promoted by heterogeneous
catalysts operating at high temperatures [12]. The homogeneous
reaction kinetics of methane to methanol can achieve higher
conversion by controlling the operating parameters, such as tem-
perature, CH4/O2 ratio, OH concentration, and residence time, to
their optimum values. In the lower temperature range under
consideration, i.e., from 35 to 700 C, a temperature of 100 C was
found to be most suitable for this maximum conversion [16].
Several of catalysts have been introduced by the researcher for
this method. For examples, Shilov et al. [45] used of Pt (II) and Pt
(IV) for this conversion and they contributed in this eld since the
1970s. Since then Periana et al. [46,47] have developed several
oxidation catalysts based on Pt (II), Pd (II), and Hg (II) salts, such as
bipyrimidyl platinum (II) complex. They are proven to functiona-
lize CH bonds, which obtain a good yield of partially oxidized (Eq.
(2)).
CH4 2H2SO4-CH3OSO3 SO2 2H2O (2)
PtCl2 catalyzes the selective oxidation of methane in fuming
sulfuric acid to give methyl bisulfate in a 72% one-pass yield at 81%
selectivity based on methane. Then, methyl bisulfate is hydrolyzed
to methanol (Eq. (3)).
CH3OSO3 H2O-CH3OH H2SO4 (3)
Unfortunately, using H2SO4 as a solvent makes it difcult to
separate methanol from the solvent. It is also necessary to use
expensive corrosion-resistant materials, and regeneration of spent
H2SO4 also proves difcult. In addition, Pd (II) salts have also been
analyzed as a catalyst for the conversion of methane to methanol
products in sulfuric acid as a solvent. However, due to the reduc-
tion of Pd (II) to Pd (0) species and the slow re-oxidation of Pd (0),
this system was not as suitable as the ligated Pt (II) complexes.
Rahman et al. [48] increased the performance of the catalyst
using strong and environmental unfriendly oxidizing agents like
SO3, K2S2O8 and NaIO4. Meanwhile, Li et al. [49] reported methane
conversion is 24.9%, selectivity being up to 71.5% and methanol
yield being 17.8% by binding nano-particle gold [Au/SiO2] catalyst
and in [Bmim] Cl a ionic liquids (IL) as the solvent, triuoroacetic
acid (TFA) and triuoroacetic anhydride (TFAA) as the acidic
reagents, and K2S2O8 as the oxidant. Besides, Pd(OAc)2-p-benzo-
quinone-CO catalyst also has explored with acetic acid as a solvent
to increase the selectivity oxidation of methane. The catalytic
performance of Pd(OAc)2 catalyst obviously improved by adding p-
 Z. Zakaria, S.K. Kamarudin / Renewable and Sustainable Energy Reviews 65 (2016) 250261
benzoquinone [50]. The porous structure of zeolite catalysts based
on aluminosilicate minerals previously introduced for this tech-
nique like Fe-ZSM-5 catalysts, which are metal-containing zeolites
was investigated the kinetics of the process of partial methane
oxidation and produced the highest methanol and formaldehyde
yield until 3.16% and 4.52%, respectively [51]. Beznis et al. [52]
reported that the Co-ZSM-5 also can be used as a catalyst for direct
partial oxidation of methane due to the activity and selectivity of
cobalt. Cobalt in the ion-exchange position results in a selectivity
towards methanol by impregnating larger Co-oxide species (CoO
and Co3O4). Besides, the cuprum-containing zeolite, Cu-ZSM-5,
was applied as a catalyst for this conversion at the temperature of
100 C with more than 98% selectivity when oxygen used as oxi-
dizing agent [53].
2.1.4. Bio-catalysis based on enzymes
Methane monooxygenase (MMO) enzymes are natural catalysts
were recognized has the opportunities to accompany the direct
conversion of methane to methanol under ambient or physiolo-
gical conditions [42]. Lunsford [54] provided a major advance in
methane conversion technology through the discovery of the for-
mation of oxygenates such as methanol through methane MMO
enzymes. The enzyme activates O2 at iron centers with the aid of a
reductant known as NADH. Besides, Michalkiewicz [55] studied
partial oxidation of methane to formaldehyde and methanol with
molecular oxygen by using zeolite catalysts, i.e., Fe-ZSM-5, Fe-
NaZSM-5 catalysts and MMO enzymes. The activation of methane
over Fe-ZSM-5 is similar to methane activation in MMO inside
methanotrophic bacteria catalysis. The reaction temperature was
carried out at the atmospheric pressure at 350650 C. Higher
values of methane conversion to methanol were observed when
using Fe-HZSM-5 (31.51% for Si/Fe22) and Fe-NaZSM-5 (74% for
Si/Fe45). Furthermore, these enzymes classiable are according
two types of enzymes whether they recover methane from solu-
tion for use as an energy source or they synthesize the methanol.
First is soluble methane monooxygenase (sMMO), which is a
complex of iron found in the cytosol of some methane-
metabolizing bacteria, and second are particulate methane
monooxygenase (pMMO), which is a methanotrophic integral
protein and a complex of Cu [56]. Besides, Razumovsky et al. [57]
explored another biocatalyst based on the cell of the bacteria
Methylosinus sporium B-2121 for conversion methane to metha-
nol for biochemical formation.
2.2. Conversion methane to methanol via plasma technologies
The oxidation of methane to methanol can also be performed
under plasma conditions. Generally, plasma technology is used
under atmospheric gas pressure. Plasma is often referred to as the
fourth state of matter, and it includes several components: positive
ions, negative ions, electrons, and neutral species. Reddy et al. [8]
reported that plasma has found widespread use in many applica-
tions, including oxidative decomposition of methane. Generally,
plasma technology can be classied into thermal plasma and non-
thermal plasma. Roth [58] elaborately discusses both conditions.
Thermal plasma can be described as a gas consisting of electrons,
highly excited atoms, ions, radicals, photons, and neutral particles.
Meanwhile, non-thermal plasma (non-equilibrium plasma), also
called low-supplied power plasma, is populated by electrons that
have much higher energy than other surrounding particles. Oka-
zaki et al. [3] reported that the conversion of methane to methanol
was achieved using non-equilibrium plasma chemical reactions
under atmospheric pressure by ultra-short pulsed barrier dis-
charge in an extremely thin glass tube reactor. Direct synthesis of
methanol from methane and water vapor mixtures has been
successfully realized with exergy regeneration. Methanol yield
255
reached the order of 1% at the water-vapor concentration of
approximately 50%, and it has been proposed that the yields of
methanol and other products may be increased due to the effec-
tive dissociation of source gas molecules by adding rare gases such
as Kr or Ar to the source gas.
Various designs for plasma reactors for methane and oxygen
conversion to methanol have been proposed in order to enhance
the conversion of methane to methanol. For examples in thermal
plasma reactors, Larkin et al. [59] used the dielectric barrier dis-
charge (DBD) reactor for synthesis of methanol from methane. It
could be considered analogous to the catalytic reactor because the
DBD reactor was able to reduce the required temperature and
pressure needed for reactions to occur as well as its ability to
control the products selectivity. Nozaki et al. [60] reported a sin-
gle-step, non-catalytic, direct and selective synthesis of methanol
via methane partial oxidation at room temperature using a new
non-thermal discharge micro-reactor. This method enabled one-
pass methane conversion of 40% with a selectivity for useful
oxygenates (including methanol) of 3050%, given that micro-
plasma produces a relatively large amount of syngas with 40%
selectivity and H2/CO 1. Assuming one-step catalytic DME
synthesis as a post-discharge reaction, an overall liquid yield of
30% with 80% selectivity is feasible.
Meanwhile, Okumoto et al. [61] expands researched this con-
version using pulsed DBD plasma under room temperature and
atmospheric pressure. These experiments pay special attention to
the effect of the specic input energy (SIE), also known as the
electrical input energy per unit mass of the material gas. The
experiment shows that the highest methanol production ability
and reaction selectivity were achieved with a relatively low spe-
cic input energy of 360 J/l, based on the feed gas. Under this
optimum condition, a maximum production ability of approxi-
mately 0.65 mmol J  1 and a selectivity of 64% were obtained.
Another approach, Wang et al. [62] conducted non-catalyzed
reactions in an argon (Ar) environment with a 50 W radio-
frequency (RF) plasma system for conversion of methane to
methanol. Several parameters were studied, including the effects
of various feed compositions, CH4/O2 ratio, and plasma discharge
areas. Among the various feed compositions, including CH4/O2,
CH4/CO, CO/H2 and CH4/H2/O2 plasma systems, a higher compo-
sition of methanol was found for the CH4/O2 plasma system, where
19.1% of methane was converted with a 1.12% yield of CH3OH; the
thin plasma discharge area is suitable for large-scale production of
CH3OH. In another paper, Wang et al. [63] investigated several
parameters that affect the production of methanol from methane.
Various specic energies (power or ow variation) and CH4 and O2
feeding concentrations were examined. Tsuchiya et al. [64] studied
a low-pressure discharge without using catalysis in low-pressure
steam plasma. The experiment was conducted under different
discharge parameters, such as voltage, gas ow rate, and gas-
mixing ratio, where methane was mixed with steam at a total gas
pressure of 110 Torr. Another interesting aspect is non-thermal
plasma was integrated the reactor with addition of catalyst to
improve the activity and selectivity. Recent studied developed the
Cu doped Ni supported on the CeO2, the presence of catalysts
enhance the selectivity of methanol until 36% [65]. Besides, there
are efforts to introduce multicomponent catalyst was combined
with plasma in two different congurations, i.e., in-plasma cata-
lysis (IPC) and post-plasma catalysis (PPC) for achieving high levels
in both methane conversion and aimed methanol selectivity
through the synergetic effect of Fe2O3CuO/Al2O3 catalyst [66].
The combination of catalyst with plasma is recommending the
efciency of methane conversion [81].
256 Z. Zakaria, S.K. Kamarudin / Renewable and Sustainable Energy Reviews 65 (2016) 250261
Fig. 7. Schematic representation of band gap formation and photo catalytic processes [67].
Fig. 8. Graphical represent reaction of conversion methane to methanol via photo-
catalysts [72].
2.3. Conversion methane to methanol via photo-catalysts
technologies
The fundamental principal of the photo-catalytic process is a
photo-chemical reaction that is carried out with external energy
provided by ultraviolet light radiation that has energy equal to or
greater than the energy band gap (EBG) of a semiconductor.
Radiation strikes the semiconductor surface and generates elec-
tron (e  )Hole (h ) pairs. Several of oxidation and reduction
processes are involved in the photo-generated electron and hole.
Fig. 7 shows the general reaction of photo-catalytic schematic
reaction when using titanium oxide (TiO2) as the catalyst. TiO2
catalysts are extensively used as semiconductor photo-catalysts
and have been applied to a wide array of environmental applica-
tions [67].
Numerous photo-catalysts were deliberated via several works.
Among the candidate materials have been studied, tungsten oxide
(WO3) highest talented as photo-catalysts due to high chemical
stability in aqueous solution under acidic conditions, non-toxicity,
and moderate oxidizing power [68]. For examples, Taylor et al.
founded that the WO3 photo-catalyst doped to an electron transfer
molecule will produce a hydroxyl radicals which can react with a
methane molecule to produce a methyl radical, which eventually
produces methanol [69]. Gondal et al. [70] reported on the photo-
catalytic conversion of methane into methanol using a visible laser
which WO3 was used as the semiconductor photo-catalyst. The
investigation included different experimental parameters, such as
catalyst concentration, laser power, laser exposure time, effects of
free the radical generator (H2O2) and electron capture agent
(Fe3 ), using visible laser light.
Gondal et al. [71] expended the examined of WO3 for conver-
sion of methane to methanol through comparison with TiO2
(rutile) and NiO as semiconductor photo-catalysts. The WO3 con-
version showed the largest conversion of methane to methanol.
On the other hand, the light source of intense monochromatic
light with 355 nm laser photons, facilitated the study of complex
processes conversion via WO3 catalyst in a short time span. The
characterization techniques conrmed that Ag ions share surface
oxygen with WO3 to give Ag2O, which enhanced the absorption of
photons and the lifetime of excited states. Hence, an increase in
the yield of methanol was observed, the reaction of this conver-
sion clearly shown in Fig. 8 [72]. Recently, Villa et al. [68] introduce
the electron scavengers such as (Fe3 , Cu2 , and Ag ) and H2O2
species to the WO3 catalyst to improve the production of metha-
nol. They successfully enhance the methanol yield until 58.5%
selectivity via WO3/Fe3 catalyst. Furthermore, Lanthanum as
transection element was doped in mesoporous WO3 in order to
increase the selectivity and yield of methanol. Yield of methanol
generated over WO3/La sample is around double higher than that
of neat WO3 [73]. Another catalyst, an imp V-Containing MCM-41
catalyst would be suitable for the photo-catalytic oxidation of
methane into methanol. The catalyst was prepared with a vana-
dium oxide support on mesoporous molecular sieves (MCM-41)
with impregnation of an aqueous solution of NH4VO3 into MCM-
41. Nitric oxide (NO) was used as an oxidant for the oxidation of
methane under UV irradiation at 295 [74].
 Z. Zakaria, S.K. Kamarudin / Renewable and Sustainable Energy Reviews 65 (2016) 250261
2.4. Conversion methane to methanol via supercritical water
technologies
The supercritical water oxidation (SCWO) method is one of the
most promising options for the production of methanol. SCWO is a
process that occurs in water at elevated temperatures and pres-
sures above the thermodynamic critical point of the mixture.
Under these conditions, water becomes a uid with unique
properties that aid in the destruction of hazardous wastes like
methane. Under the supercritical uid conditions, the reaction
environment can be adjusted because the properties of water such
as viscosity and dielectric constant can be readily manipulated
between high gas-like diffusion rates and high liquid-like collision
rates by varying pressure and temperature [8]. Dixon et al. [75]
reported that methanol production can be accomplished by cata-
lytic partial oxidation over Cr2O3 in SCWO. A high concentration of
water inhibits the methane conversion and promotes the yield of
methanol because methanol oxidation correlates positively with
oxygen concentration, and the presence of a Cr2O3 catalyst can
enhance the efciency of the SCWO process by increasing the
methane conversion rate. Lee et al. [76] reported that isothermal
conditions with a laminar reactor in SCWO could be feasible for
the direct partial oxidation of methane to methanol. The highest
production of methanol was approximately 35%, with a methane
conversion of 13% at temperatures of 400410 C. Phillip et al.
[77] described that the type of reactor used along with other
factors inuence the production of methanol in SCWO. Two types
of reactors have been examined: glass-lined reactors and stainless-
steel reactors. Both of these reactors have been investigated
experimentally with several congruent parameters, and the glass-
lined reactor showed higher conversion of methane to methanol.
2.5. Conversion methane to methanol via biological process (Mem-
brane technologies)
Another method that allows the conversion of methane to
methanol via biological processes is based on membrane reactor
technology. Reddy et al. [8] reviewed the chemical reactor that
operates on the membrane. This membrane reactor is able to
perform dual functions at once. During the conversion process, the
reaction occurs inside the separation membrane of the physical
device. Thus, the membrane serves as the separator and reactor.
Membrane reactors are classied based on the type of membrane
materials, either inorganic or polymeric, and on the porosity of the
membranes, such as micro, macro, and dense. Commonly, an
inorganic membrane reactor is used instead of a polymeric
membrane due to a low tolerance to chemical and temperature
effects. Additionally, an inorganic membrane is mainly composed
of metallic or ceramic materials and has greater physiochemical
stability. Lee et al. [78] used Methylosinus trichosporium OB3b
with a high concentration of Cu2 to produce methanol by an
oxidation process. Takeguchi et al. [79] also investigated Methy-
losinus trichosporium OB3b for methanol production. Several
parameters play an important role in the optimization of the
conversion rate, including changes in cell density, temperature, pH
away from 7.0 and concentrations of sodium formate, phosphate
buffer and cyclopropanol. Duan et al. [80] reported a methane
conversion rate as high as 60%. An approximate yield of methanol
of 0.95 g/L was produced using Methylosinus trichosporium OB3b
in a biotransformation process carried out in a membrane aerated
reactor into which methane and oxygen were introduced via two
separate dense silicone tubing. The high yield of methanol pro-
duction reached over 1.12 g/L, which is 4.5-fold higher than the
highest value (0.25 g/L) previously reported.
257
3. Challenges and advancements in technologies for direct
conversion of methane to methanol
In industry, practical production of methanol from conversion
of methane is executed via a two-step process. Initially, methane
steam reforming produces synthesis gas, followed by catalytic
conversion at high pressure of synthesis gas to methanol. Because
this method incurs high capital and maintenance costs for steam
reforming plants, this technology is not applied on a smaller scale.
Energy intensive synthesis gas manufacturing consumption occurs
in operational plants at pressures between 200 and 600 psi with
process outlet temperatures in the range of 7001000 C [82].
Although the two-step process is implemented and operated in a
stable manner, it is not feasible for high efciency operation in the
new proposed system due to the strongly endothermic reaction in
the reforming process that necessities a large external energy
supply [3,37]. Therefore, the conversion of methane to methanol
via an alternative process is highly desirable to overcome this
problem. Several processes have been reported in the academic
sphere but are not yet practical for wide application in industry.
3.1. Single-step oxidation of methane to methanol via conversional
catalytic processes
Partial oxidation has attracted a sweeping increase in attention
due to the attractive feature of methane-to-methanol conversion
via direct conversion in a single-step reaction. This technology is
simple, leading to a more economical process with efcient con-
version of the internal energy of methane and to the possibility of
direct formation compared with the two-step process. However,
the major challenge is that the yield of organic oxygenates is quite
inferior in this process [83].
3.1.1. Homogeneous gas-phase partial oxidation
Direct partial oxidation of methane to methanol is highly
appealing because of its high potential for effective industrial
utilization of abundant natural gas resources. As an exothermic
reaction, the direct conversion of methane to methanol via
homogeneous gas-phase partial oxidation is a potential option for
replacement of the conventional industrial process via syngas
production by steam reforming of methane. A technical/economic
evaluation has demonstrated over 70% methanol selectivity at 8
15% methane conversion [31,32].
Two well-known drawbacks of homogeneous gas-phase partial
oxidation are the low conversion of methane per pass and rela-
tively low selectivity of methanol formation [30,40]. The problems
with this method arise from both thermodynamics and kinetics,
such as complex chain-branched kinetic processes [30]. This
method requires high pressures that exceed to 10 atm and high
temperatures of up to 1000 C to favor and activate greater
methane conversion for formation of methanol selectivity. In
reality, the methane conversion rate is still less than remarkable
[31,32,40]. The strength of the CH bond in methane is stronger
than that of methanol, which means that methanol tends to be
more reactive than methane (the CH bond strength in methanol
is 389 kJ/mol, whereas that in methane is 440 kJ/mol). For these
reasons, the foremost challenge in methane conversion is related
to selectivity rather than reactivity [25,85]. Experimental results
achieved approximately 10% conversion of methane, but the lim-
itation of methanol selectivity was quite poor because the required
product of methanol is more active than methane [32,83].
Moreover, this method operates under a free radical mechan-
ism, which is highly difcult to control and requires recycling of
unconverted methane, which limits industrial applications
[25,31,65]. Therefore, the proposed participation of a catalyst
could improve the methanol selectivity and yield. However, until
258 Z. Zakaria, S.K. Kamarudin / Renewable and Sustainable Energy Reviews 65 (2016) 250261
now, catalytic reactions have not produced yields of methanol plus
formaldehyde that are better than those of the reported gas phase
process, except for a few excellent reports [31]. Hence, research
and development are urgently needed in the area of direct con-
version to methanol in a single exothermic step with high yield
[40].
3.1.2. Heterogeneous catalytic partial oxidation
The direct methane to methanol oxidation process at low
temperature via heterogeneous catalytic partial oxidation is an
interesting alternative to the current process. If this method can
successfully convert methane, the new process could lead to a
decrease in the current market price of methanol [37]. The con-
version is conducted with lower energy consumption and at lower
temperature, practically at ambient conditions. Selective oxida-
tions at low temperature give the impression that this route might
avoid excessive formation of CO2 [38,40]. One important factor is
the need for high conversion with highly selective catalysts and
the use of silent discharge, which selectively converts methane to
methanol directly.
Unfortunately, in practice, methane conversion and methanol
selectivity in the proposed new process are less effective than
those of the homogeneous gas-phase partial oxidation method
[83]. However, the conversion ratio of methanol via catalysis is not
sufciently high to provide a new energy system and to induce
silent discharge consumed only as triggered through the input
energy for partial oxidation of methane due to an exothermic
reaction. Although numerous studies have been reported, they
were unable to satisfy the highly sophisticated energy utilization
system without recovery of heat generated efciently in the exo-
thermic reactions [3].
3.1.3. Homogeneous catalysis in solution
A low-temperature homogeneous catalyst in solution for acti-
vation of CH bonds is unnecessary in the free radical mechanism,
which is difcult to control, and the reuse of unconverted methane
could possibly promote more selective reactions than those pro-
moted by the heterogeneous catalyst method of partial oxidation
at high temperatures [12]. In addition, this green chemical process
conversion is performed under mild conditions such as silica [49].
The key problem in this method is the introduction of a catalyst
system with suitable reactivity and selectivity that also tolerates
oxidizing and protic conditions [12]. Another consideration in
catalyst identication is a suitable yield of methanol and other by-
products, such as formaldehyde [51]. Additionally, in nding the
correct solvent system for catalysts, it is quite difcult to separate
the yielded methanol and the solvent. Sulfuric acid (H2SO4) was
commonly applied as the solvent system in several studies. The
main disadvantage of H2SO4 as a solvent system is the difculty in
separating methanol product from the H2SO4. Moreover, as a
strong acid, H2SO4 has the potential to corrode applied catalysts
such as Pd(II). Practical solutions to this issue must overcome the
obstacles of corrosion-resistant materials and periodic regenera-
tion, which lead to costs that contribute to the overall cost of
production [12]. Another approach to nding suitable solvents
uses K2S2O8 and KMnO4 for conversion of methane, specically to
oxidize methane into methanol under the appropriate conditions.
Nevertheless, molecular oxygen is undoubtedly the ideal oxidant
from the viewpoints of environmental safety and raw material cost
[50]. The consumption of H2SO4 or heavy metals as catalyst sys-
tems could lead to problems of strong corrosion and serious pol-
lution. As a result, the exploration of new of green processes for
methane conversion has attracted further signicant attention
[49].
3.1.4. Biocatalysis based on enzymes
This seemingly simple reaction has remained one of the major
unanswered challenges in catalytic chemistry, the area of research
that has proposed new green processes. Using methane mono-
oxygenases (MMOs) that are classied as ammonia-oxidizing
bacteria (AOB), this conversion method is able to oxidize
methane to methanol at room temperature [42], and thus the
conversion of methane occurs. An additional advantage of using
AOB to oxidize methane to methanol via the nonspecic action of
the enzyme ammonia mono-oxygenase co-metabolism in AOB
without any net energy synthesis is that contaminants such as
moisture and CO2 do not create a limitation for biological con-
version and consumption of CO2 in gas mixtures for cell synthesis.
Although biocatalysts are a potential alternative for conversion of
methane to methanol, microorganisms are limited for industrial
consumption. Inhibition of cell growth by H2S was observed when
methane in biogas was used. In addition to the high-cost electron
donors required for conversions, the limitation of mass transfer
from gas to liquid and NH3 might inhibit the growth of micro-
organisms, including methanotrophs [86,87].
3.2. Plasma technologies
Oxidation of methane to methanol was also achieved under
plasma conditions, which offer clean destruction of hazardous
waste and no harmful emission of toxic waste such as CO2 and CO
[88]. Recently, the development of micro-reactor plasma offered
the benets of removal of heat generated by efcient methane
partial oxidation. A low temperature reaction is essential in
operation temperature because the oxygenates are condensed on
the micro-reactor wall, which realizes product separation from O2-
rich reactive plasma. Additionally, the micro-plasma reactor design
is benign, simple, and does not involve hazardous or costly
materials such as palladium, platinum, ionic liquid, or mercury,
thus rendering the process more economically attractive [60].
Unfortunately, the productivity for this conversion is lower and
is restricted by the quantity of methane that can be dissolved in
water. This approach requires the dissolution of methane in an
aqueous solution, but the solubility of methane at room tem-
perature in aqueous solution is notably low. To enhance the con-
version, the concentration of methane in water was cultivated
using methane hydrates. This process has also been studied
experimentally but did not result in breakthroughs. The processes
involved in plasma conversion are still less selective than catalytic
processes, leading to greatly complex product distributions. As a
possible approach to overcoming this problem, certain researchers
have attempted to exploit the inherent synergetic potential
between plasma-mediated reactions and heterogeneous catalysts
[25,66].
3.3. Photocatalyst technologies
Two decades later, researchers are still working on photo-
catalysis technologies for environmental applications. One recog-
nized process holds promise as a tool for allowing methane con-
version to methanol under mild conditions using an appropriate
catalyst and light. In this sense, this technique can be classied as a
green alternative for selective oxidation in a wide range of appli-
cations. The basic requirements for this method are the use of
three relatively abundant and inexpensive reactants of light, water,
and methane to produce methanol. Therefore, this process option
is highly attractive [68,70]. The performances of various photo-
catalysts have been investigated but have still not achieved the
level of selectivity required for methanol yield. The addition of
chemical additives such as H2O2 in photocatalytics has also been
reported as a source of hydroxyl radicals, which are an important
 Z. Zakaria, S.K. Kamarudin / Renewable and Sustainable Energy Reviews 65 (2016) 250261 259

intermediate that contributes to the methanol formation reaction Table 1

and improves the generation of methanol yield [68]. This potential Summary of conversion methane to methanol production.
approach to conversion of methane to methanol could not be
Type of conversion Conversion of Selectivity of Refs.
extended to the industrial sector because of the limited investi- process methane (%) methanol (%)
gation of photocatalysts and suitable reactors for this method, but
this method has gained attention from academicians for CO2 Gas-phase reaction 3040 510 [25]
conversion [89,90]. Gas-phase reaction 510 3040 [29]
Gas-phase reaction 13 60 [31]
Gas-phase reaction 13 60 [32]
3.4. Supercritical water technologies Gas-phase reaction 10 80 [33]
Gas-phase reaction 10 80 [34]
Supercritical water oxidation (SCWO), also known as hydro- Heterogeneous catalyst 8.2 11 [36]
Heterogeneous catalyst 0.661.52 93.491.9 [37]
thermal oxidation (HTO), provides a high-efciency conversion
Heterogeneous catalyst 11.6 33.2 [38]
and thermal oxidation process to treat a wide variety of hazardous Heterogeneous catalyst 50.5 [40]
and non-hazardous wastes. However, no research papers have Heterogeneous catalyst 1.3 10.1 [41]
reported applications of SCWO in methanol processing via Heterogeneous catalyst 0.5 92 [44]
methane conversion, and progress is limited. Among the possible Homogeneous catalyst 8 72 [47]
Homogeneous catalyst 24.9 17.8 [49]
factors that restrict the use of this method are a highly compli- Homogeneous catalyst 1 3.16 [51]
cated SWCO reactor engineering design, the high temperature Bio-catalysis 0.6 23 [53]
environment of the SWCO reactor and a high corrosion rate when Bio-catalysis 31.51 74 [55]
treating wastes containing halogen, such as chlorine, that do not Plasma technology 50 0.87.5 [3]
Plasma technology 40 3050 [60]
provide adequate protection against chloride attack under the
Plasma technology 64 [61]
oxidizing conditions found in SCWO systems [8,91]. Plasma technology 19.1 1.12 [62]
Plasma technology 25 20 [64]
3.5. Biological process (Membrane technology) Plasma technology 23 36 [65]
Plasma technology 46.9 1.6 [66]
Photo-catalysts 58.5 [68]
In the pursuit of an alternative method for methane to technology
methanol conversion, membrane technologies are also feasible for Photo-catalysts 50 [73]
applications due to their advantage of consumption of the mem- technology
brane, including membrane processes that can separate the Membrane technology 6 0.7 [78]
Membrane technology 20 60 [80]
methane and methanol. This alternative implies that a number of
bulky separation essentials could be replaced by a membrane
process, which does not involve a phase change to produce efciencies, slow reaction rates, and lack of economic competi-
separation. Therefore, the energy requirements for conversion will tiveness because these methods are typically highly energy
decrease, unless large amounts of energy are required to increase intensive. Oxidation of methane still suffers from poor conserva-
the pressure of the methane feed stream to drive the permeating tion and low methanol product selectivity while high selectivity
methane across the membrane, and the yield production will and yield remain desirable [70,85]. In addition, the consumption of
display notably high selectivities for the components to be sepa- oxidants such as oxygen is a key aspect for commercialization of
rated. Because low priced polymer based membranes have a low
conversion technologies. The limitations of an oxidation reaction
tolerance to, e.g., chemicals and temperature, the membrane
that occurs via oxygen are based on the spin-forbidden reaction,
method has relatively limited applicability [8,92]. However, the
i.e., molecules of methanol and methane have a singlet ground
limitations of these technologies involve incompatibilities of the
state. Thus, adequate catalysts are necessary to activate this reac-
membrane applied in conversion of methane. The high conversion
tion. However, no previous reports have noted catalysts suitable
of methane will produce a high concentration of various organic
for the industrial scale. Therefore, research and development on
compounds. Therefore, the permeability of methane might cause
this conversion are still urgently needed for the improvement of
dissolution, swelling or breakage of the membrane, which lead to
methanol production, which remains a costly alternative fuel
membrane degradation. Moreover, membranes are usually sui-
compared with other fuels [85]. Table 1 shows a summary of the
table for operation at room temperature. Therefore, reactions that
results of methane conversion and methanol selectivity and all
occur at higher temperatures might create a problem for mem-
conversions that have still not satised the requirement for
branes that cannot maintain their physical integrity under these
industrial scale use.
conditions [8,92].

4. Potential for expanding direct conversion of methane to 5. Other possible technologies for conversion of methane to
methanol in industry methanol

Complete conversion of methane to methanol at the industrial
scale was discussed previously, and generally, several require-
ments must be fullled for these academic discussions to apply.
Most importantly, the direct conversion of methane to methanol
should lead to an economic advantage over the indirect method
[70,85]. The key to single-step direct conversion is the feasibility of
replacing the existing industrial methanol production methods if
the conversion of methane can achieve at least 5.5% with 80%
methanol yield production, as described in the literature [84].
Unfortunately, direct conversion methods have yet to success-
fully reach the commercialization stage due to poor conversion
A newly developed fuel-cell-type reactor enables single-step
oxidation of methane and selective synthesis of methanol yield.
The reactor consists of a metal anode and cathode or metal oxide
catalysts. Various catalysts have been analyzed, such as various
metals (Pd, Ru, Au, and Ag) or metal oxides (V2O5, Fe2O3, CoO,
Mn2O3, MoO3, and CrO) and were impregnated on the surface of
the optimized support catalysts. The investigated operating tem-
peratures ranged from 50 C to 250 C. Among the various cata-
lysts, the consumption of the V2O5/SnO2 catalyst anode was ef-
cient during methanol production, and the selectivity reached as
high as 61.4% and 88.4% at a temperature of 100 C [93].
260 Z. Zakaria, S.K. Kamarudin / Renewable and Sustainable Energy Reviews 65 (2016) 250261
Another type of technology for conversion of methane to
methanol is electrosynthesis via gas diffusion electrodes (GDEs).
Electrosynthesis is the synthesis of chemical compounds in an
electrochemical cell. The key advantages of this method are
avoidance of possibly wasteful half-reactions and the ability to
precisely tune the required potential. The reaction that occurs at
the TiO2/RuO2/V2O5/PTFE GDE with a methane fuel feed was
designed to potentially enhance the selectivity for methanol at low
values of current density. However, one of the obstacles in this
reaction is the formation of by-products such as formic acid and
formaldehyde during oxidation of methane [94].
6. Conclusion
In this article, we discussed the potential of methane as one of
the GHGs that can be converted to methanol for use as a valuable
fuel. The increasing demands of consumption in DMFCs as an
alternative source of energy make the production of methanol
highly attractive. Therefore, we listed and discussed the various
alternative conversion methods that are feasible for conversion of
methane to methanol, including recent progress, challenges and
advances in each of the current conversion technologies and the
latest conversion technologies. Advancement in all of these tech-
nologies for conversion is eventually expected to resolve global
environmental issues and offer alternative sources of energy for
world consumption. Hence, we conclude that single-step oxida-
tion methane to methanol is a topic that will continue to attract
attention from academicians and researchers in the environmental
and energy sectors worldwide.
Acknowledgment
The authors gratefully acknowledge the nancial support given
for this work by the Universiti Kebangsaan Malaysia (UKM) under
UKM-GUP-2013-031 and FRGS/2/2013/TK06/UKM/01/1.
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