Journal of Natural Gas Chemistry 12(2003)81–89

Recent Progress in Direct Partial Oxidation of Methane

to Methanol
Qijian Zhang1,2 , Dehua He1∗ , Qiming Zhu1∗
1 State Key Laboratory of C1 Chemistry and Technology, Department of Chemistry, Tsinghua University, Beijing 100084, China;
2 Liaoning Institute of Technology, Jinzhou 121001, China
[Manuscript received April 03, 2003; revised May 22, 2003]

Abstract: The direct conversion of methane to methanol has attracted a great deal of attention for nearly
a century since it was first found possible in 1902, and it is still a challenging task. This review article
describes recent advancements in the direct partial oxidation of methane to methanol. The history of direct
oxidation of methane and the difficulties encountered in the partial oxidation of methane to methanol are
briefly summarized. Recently reported developments in gas-phase homogeneous oxidation, heterogeneous
catalytic oxidation and liquid phase homogeneous catalytic oxidation of methane are reviewed.
Key words: methane, methanol, catalytic partial oxidation, gas-phase homogeneous oxidation, catalyst

1. Introduction 1.1. Conversion of natural gas

Natural gas can be converted to some chemicals

Direct conversion of methane to methanol has (e.g. methanol, formaldehyde, etc.) directly or via
been attracting significant attention since it was found indirect routes utilizing syngas (CO+H2 ) as an inter-
possible in the early 20th century because of its mediate. The reactions of methane to methanol, etc.
great industrial potential for the efficient utilization by indirect routes (via syngas) or direct routes are as
of abundant natural gas reserves. Natural gas is one follows:
of the clean and effective energy resources. However, Indirect routes:
it is uneconomical to bring natural gas to market in
gas form because its density is too low for transporta- CH4 + H2 O → CO + 3H2 (1)
tion and storage, unless there are pipelines accessible.
0
In order to economize transportation, the gas can be ∆H298 = 206 kJ/mol
converted into a liquid and transported as such. Liq- CH4 + CO2 → 2CO + 2H2 (2)
uefaction of natural gas may be a choice, but the boil-
0
ing point of methane (the predominant component in ∆H298 = 247 kJ/mol
nature gas) is as low as −164 , and it requires ex-
CH4 + 1/2O2 → CO + 2H2 (3)
pensive liquid nitrogen refrigeration throughout the
0
transportation. Therefore, the most attractive alter- ∆H298 = −35 kJ/mol
native is to convert the natural gas into liquid prod-
CO + 2H2 → CH3 OH (4)
ucts such as methanol, which is a liquid under ambient
0
temperature and pressure. ∆H298 = −90.7 kJ/mol
∗ Corresponding author. Tel: (010)62772592; Fax: (010)62792122;
E-mail: hedeh@mail.tsinghua.edu.cn, dchzqm@mail.tsinghua.edu.cn
82 Qijian Zhang et al./ Journal of Natural Gas Chemistry Vol. 12 No. 2 2003

Direct routes increasingly popular, especially in the last 20 years

since the “energy crisis” in the 1970s. A technical
CH4 + 1/2O2 → CH3 OH (5) economic assessment showed that the direct process
0
for methanol production could compete with the con-
∆H298 = −128 kJ/mol
ventional indirect one in terms of production costs if
CH4 + 1/2O2 → 1/2C2 H4 + H2 O (6) an 80% selectivity of methanol could be achieved at
0
a single pass methane conversion of 10%.
∆H298 = −140 kJ/mol

CH4 + 1/4O2 → 1/2C2 H6 + 1/2H2 O (7) 2. Challenge of direct conversion of methane

0 to methanol
∆H298 = −88 kJ/mol
Conventionally, the commercialized natural gas 2.1. Brief history of direct oxidation of
conversion process is an indirect process. Natural methane to methanol
gas is first converted to syngas by steam reforming
(1-1), and then the syngas is catalytically converted The direct partial oxidation of methane to
to methanol in industry. The steam reforming of methanol was first discovered in 1902 by Bone and
methane is an energy intensive process, which requires Vheeler [3,4]. In 1932, Newitt and Haffner [5] reported
high temperature and pressure that leads to problems the formation of methanol through high-pressure oxi-
in with reactor materials, operation and maintenance. dation of methane in a static system. In 1934, Wieze-
In the process of methanol production from natural vich and Frolich [6] began to investigate the oxida-
gas via syngas, about 60%-70% of the cost of the tion of methane at high pressure in a flow system.
overall process is associated with the reforming pro- From then on, the oxidation of methane to methanol
cess [1]. In order to reduce the reforming cost, direct was always carried out in the flow system. In 1937,
routes have been attracting the attention of many re- Boomer et al. [7–9] reported the catalytic oxidation
searchers. of methane using copper as a catalyst. However, re-
search on the oxidation of methane was stagnant in
1.2. Methanol usage and production the following decades because of poor methanol selec-
tivity and the rise of the petroleum industry. In the
Methanol is one of the most important industrial 1980s, the interest in the direct conversion of methane
chemicals. Its major applications are as a solvent or to methanol was renewed by the “energy crisis” and
as an intermediate for many other chemicals that are the demand for the efficient utilization of abundant
used as fuels or fuel additives. Demand for methanol natural gas reserves. Lunsford [10] and Gesser [11]
has recently increased because it is used to produce separately reported good results in catalytic and non-
methyl tertiary butyl ether (MTBE). Methanol can catalytic oxidation of methane to methanol. The
also be blended with gasoline or used directly as reaction was extensively studied from then on, and
an automobile fuel. It has been estimated that if quite a few reviews were published [12–17]. Unfor-
methanol achieves 10% penetration into the US auto- tunately, there still has been no breakthrough, and
motive fuel market, the demand for methanol would the methanol yield is too low for commercialization.
increase 25 billion gallons per year [2]. Needless to Furthermore, good reported results have never been
say, this would greatly expand the methanol market. reproduced.
Conventionally, methanol is produced by catalytic
synthesis of syngas which is produced by steam re- 2.2. The difficulties in the partial oxidation of
forming of natural gas (reaction (1) and (4)). This methane to methanol
process suffers from the low energy efficiency and high
capital and operating cost of steam reforming. The di- The difficulty of the direct partial oxidation of
rect partial oxidation of methane to methanol (5) is methane to methanol lies in the activation of the
an exothermal reaction that is energetically more effi- methane C-H bond. The methane molecule is a
cient than the endothermic steam reforming reaction. perfect, symmetrical tetrahedron, and the four C-H
Furthermore, this more simplistic process can reduce bonds are completely uniform, making it the most sta-
the capital and operating cost. Therefore, the direct ble hydrocarbon molecule. The first dissociation en-
partial oxidation of methane to methanol has become ergy of its C-H bond is as high as 440 kJ/mol, and the
 Journal of Natural Gas Chemistry Vol. 12 No. 2 2003 83

activation and reaction of methane therefore requires be activated and oxidized.

extreme conditions. On the other hand, the required The oxidation of methane is thermodynamically
product (methanol) is much more active under the re- favored. The Gibbs free energies of the reaction at
action conditions. The dissociation energy of the H- different temperatures are given in Table 1. As the
CH2 OH bond is 393 kJ/mol, which is 47 kJ/mol less data indicate, while the formation of methanol is ther-
than the H-CH3 bond. Under the same conditions, modynamically feasible, production of carbon oxides
methanol is easier to be activated and oxidized than is even more favored. It is, therefore, necessary to
methane, leading to the deep oxidation to produce control the oxidation of methane to cease at the pro-
CO and CO2 . Additionally, the methanol molecule duction of methanol, instead of being deeply oxidized
contains an oxygen atom, which makes methanol a to the most thermodynamically favored complete ox-
polar compound (its dipole moment is 1.70 Debyes). idation product, CO2 . However, how to control the
But the methane molecule has no polarity, therefore, oxidation is a serious problem, and most of the in-
methanol is much easier to be adsorbed than methane vestigations on the partial oxidation of methane to
on the surface of catalyst or reactor metal wall and to methanol were carried out to achieve this aim.

Table 1. The gibbs free energies of reaction at different temperatures

∆ Gr /(kJ/mol)
No. Reaction
298 650 700 750 800 1000
R1 CH4 +1/2O2 → CH3 OH −111 −93 −91 −88 −86 −76
R2 CH4 +O2 → HCHO+H2 O −288 −294 −294 −295 −296 −298
R3 CH4 +1.5O2 → CO+2H2 O −544 −573 −578 −582 −586 −603
R4 CH4 +2O2 → CO2 +2H2 O −801 −800 −799 −799 −799 −798
R5 CH4 +1/2O2 → 1/2C2 H4 +H2 O −144 −147 −147 −147 −147 −147
R6 CH4 +1/4O2 → 1/2C2 H6 +1/2H2 O −80 −69 −67 −65 −63 −55
R7 CH4 +1/2O2 → CO+2H2 −86 −152 −162 −172 −182 −222
R8 CH4 +H2 O→ CO+3H2 142 60 48 36 23 −27
R9 CH4 +CO2 → 2CO+2H2 171 75 61 47 33 −23

3. Controlled direct oxidation of methane to dation reactions catalyzed by the metal surface of the
methanol reactor producing CO and CO2 . A number of other
studies have been carried out and confirmed [18–23]
The controlled partial oxidation of methane was that methanol selectivity diminishes in the presence
mainly carried out in two directions: gas phase ho- of stainless steel surfaces, which is inevitable when
mogeneous oxidation and catalytic oxidation. In the a stainless steel reactor is used. In order to mini-
paper, the two methods will be discussed separately. mize the effect of metal surface, quartz [24–30] and
Pyrex [31–39] linings have been used and improved
3.1. Gas-phase homogeneous oxidation of the methanol yield. In a quartz lined reactor, Gesser
methane et al. [11] reported greater than 80% methanol se-
lectivity at over 10% methane conversion in the gas
Under certain temperatures and pressures, meth- phase oxidation of methane, and Feng et al. [40] re-
ane can react with oxygen in the gas phase without a ported ca. 80% methanol selectivity at 12% methane
catalyst. Until now, the most promising results were conversion in a single-crystal sapphire reactor. Un-
obtained with gas phase homogeneous oxidation [16]. fortunately, these excellent results have not been re-
produced until now. A methanol selectivity of ca.
3.1.1. Effect of the reactor wall
40%–50% at methane conversions of ca. 2%–5% con-
stituted the usual reported results, and different re-
In early studies, the oxidation of methane was car-
searcher always reported different, and even opposite
ried out in a stainless steel reactor, especially when
results. In fact, the poor reproducibility is one of the
high pressures were employed because of the require-
most serious problems in the controlled partial oxida-
ment of pressure resistance. The yields of methanol
tion of methane.
obtained were very low, mainly due to the deep oxi-
84 Qijian Zhang et al./ Journal of Natural Gas Chemistry Vol. 12 No. 2 2003

There is an important problem in a quartz or HCHO was usually reported in the effluence. CH3 OH
Pyrex lined reactor, how to ensure the reaction take and HCHO were formed when the temperature in-
place essentially homogeneously in the pure gas phase. creased to nearly the transition temperature and
It is important that the reactants do not contact the passed through a maximum before decreasing as the
metal wall of the reactor under the reaction condi- temperature increased further. Recently, Zhang et al.
tions. Maybe differences in the effects of the metal [41] reported an interesting result. In a specially
wall catalytic reaction on the homogeneous reaction designed reactor, the product distribution was kept
are the main reason for the different results reported constant for a wide temperature range of ca. 40
by different researchers. In order to avoid the metal (430–470 ) when the pressure was 5.0 MPa and
wall’s influence under the reaction conditions, Zhang CH4 /O2 /N2 =10/1/1.
et al. [41] designed a reactor in which the ringed The oxidative coupling product C2 H6 was always
gap between the inner quartz line and the SS tube observed when the oxygen in the feed gas was ex-
was encapsulated by an O-ring pressed by a locking hausted. With increasing temperature, the produc-
nut. This design can efficiently avoid the catalytic tion of C2 H6 increased although its selectivity re-
effect caused by the metal wall of the reactor. A mained low.
methanol yield of ca. 7%–8% (a methanol selectiv- LΦdeng [45] and Chellappa [46] separately re-
ity of over 60% at a methane conversion of 12%–13%) ported on the production of H2 in the gas phase oxida-
was reported and could be steadily reproduced. It tion of methane, but the amount of H2 produced was
is believed that if the metal wall effect can be elimi- quite low. Zhang et al. [41] reported much more H2
nated, high methanol yields could be obtained in the production (H2 /CO=0.4–0.5) without HCHO being
gas phase partial oxidation. detected. It was supposed that HCHO decomposed
quickly to H2 and CO once it formed in the pure gas
3.1.2. Effect of Reaction conditions phase reaction.

For the gas phase homogeneous oxidation of 3.1.2.2. Pressure

methane, the only controllable reaction condition
parameters are the reaction temperature, pressure, Pressure is an important factor for the gas phase
methane/oxygen ratio in the feed and total gas flow oxidation of methane to methanol. Increasing the re-
rate (residence time). In this section, each of the pa- action pressure has been shown to shift the transition
rameters will be discussed separately, although they temperature to lower temperatures. When the pres-
are inextricably associated with each other. sure was raised from 1.0 to 3.0 MPa, the transition
temperature dropped more than 30 . However, as
3.1.2.1. Reaction temperature the pressure increased beyond 5.0 MPa, the effect of
pressure on the transition temperature becomes less
Most studies have examined the effects of temper- pronounced [42,33].
ature on the partial oxidation of methane to methanol Generally, methanol selectivity has been observed
between 300 and 500 . Little methane conversion oc- to increase with increasing pressure [18,25,34] except
curred before the reaction temperature was increased that Burch reported no smooth trend related to the
to a transition temperature, after which the oxygen effect of pressure in methanol selectivity [33]. De-
conversion sharply increased to almost 100% in a very creasing the pressure resulted in a marked increase in
narrow temperature range [41–44]. These results in- the production of CO and CO2 .
dicated that the reaction was typically operated by
a free radical mechanism. The transition tempera- 3.1.2.3. Methane/oxygen ratio (oxygen con-
ture varied depending on the other conditions, such centration) in the feed gas
as pressure, methane/oxygen ratio et al. A further
increase in reaction temperature above the transition Methane/oxygen ratio (oxygen concentration) in
temperature usually resulted in decreasing methane the feed gas is another important factor. Most studies
conversion because more CO and CO2 , the deep oxi- were carried out with a high methane /oxygen ratio in
dation products, were produced [42,33]. case of an explosion and deep oxidation. Decreasing
The products of the gas phase oxidation of the feed methane/oxygen ratio (increasing the feed
methane were mainly CH3 OH, CO, CO2 , and H2 O. oxygen concentration) generally resulted in increased
 Journal of Natural Gas Chemistry Vol. 12 No. 2 2003 85

methane conversion with a concomitant decrease in ambient conditions.

methanol selectivity [25,28,35,38,41–44]. However,
Burch et al. [33] concluded that methanol selectivity 3.1.4. Brief summary
showed little dependence on the feed methane/oxygen
ratio. However, the effect of methane/oxygen ratio on The partial oxidation of methane to methanol can
the methanol yield was not as dramatic, since yield is take place in the gas phase, homogeneously. Assuring
the product of methane conversion and methanol se- that the reaction occurs without metal wall catalysis
lectivity. is the most important factor to achieve high methanol
yields. While the feed oxygen is completed consumed,
3.1.2.4. Total gas flow rate (residence time) low temperature and high pressure favor methanol
production. However, lower methane/oxygen ratios
The effect of total gas flow rate (residence time) result in higher CO and CO2 selectivity while the
on the oxidation of methane was much less pro- methanol yield is not greatly affected because the drop
nounced. Under the conditions of fixed temperature, in methanol selectivity is mitigated by the increase in
pressure and feed methane/oxygen ratio, increasing methane conversion.
the total gas flow rate did not noticeably affect the Although the gas phase partial oxidation of
trend in methanol selectivity and yield [41]. methane to methanol can give quite good results, it is
operated by a free radical reaction mechanism, which
3.1.3. Additives (H donors and NOx ) is hard to control. Furthermore, it is almost impossi-
ble to improve the methanol selectivity and yield by
Apart from the controllable parameters discussed merely adjusting the operational parameters. There-
above, some additives were added to the reaction sys- fore, it is expected that the participation of catalysts
tem in order to decrease reaction temperature or in- could control the reaction and give better results.
crease methanol selectivity. Natural gas contains cer-
tain amounts of ethane and other higher hydrocar- 3.2. Catalytic oxidation of methane
bons, which are known to initiate the gas phase free
radical reactions at lower temperatures. It was re- The catalytic partial oxidation of methane to
ported that 5% ethane in the methane feed could methanol has been comprehensively investigated. The
lower the transition temperature by approximately examined catalysts include metals, single-metal ox-
50 [33]. If natural gas was substituted for pure ides, multi-metal oxides, zeolites and homogeneous
methane, the transition temperature could be reduced complex catalysts. Unfortunately, the catalytic re-
100 [35]. Hunter and Gesser [47] have systemat- sults reported are no better than those obtained by
ically examined the effect of sensitizers on the oxi- gas phase homogeneous reaction, and most of the
dation of methane. The sensitizers included hydro- produced oxygenates are formaldehyde other than
carbons, ethers, aldehydes, ketones, thiols, amines, methanol.
water and peroxides; most of which were able to re-
duce the MTCR (Minimum Temperature when Com- 3.2.1. Heterogeneous catalytic oxidation
plete Reaction occurred) in varying degrees. Some im-
proved formaldehyde selectivity, and some increased Catalysts based on MoO3 have been applied in
methanol selectivity. Omata [48] concluded that H2 the heterogeneous catalytic oxidation of methane and
and hydrocarbons can improve methanol selectivity extensively examined. One of the earliest report us-
because they are H-donor species. ing MoO3 based catalysts was published by Dowden
Recently, Teng et al. [49] found that when NO and Walker [50]. They developed a series of catalysts
or NO2 was introduced into methane-oxygen sys- based on MoO3 and stated that it was important that
tem as initiator, methane was able to be oxidized one oxide in the catalyst be capable of catalyzing the
to methanol and formaldehyde under ambient pres- oxidation of hydrocarbons and the other of catalyz-
sure. The results obtained were: X(CH4 )=10%, ing the hydration of alkenes in order for the catalyst
S(CH3 OH)=22%, S(HCHO)=24%. It was considered to be successful. The most active catalyst for the
that the nitrogen atom in NOx showed higher activ- production of methanol was Fe2 O3 (MoO3 )3 . Dowden
ity for the cleavage of the C-H bond than the oxygen and Walker pointed out that if the designed products
atom so as to initiate the oxidation of methane at were removed from the catalyst surface and cooled to
86 Qijian Zhang et al./ Journal of Natural Gas Chemistry Vol. 12 No. 2 2003

below 200 in less than 0.03 s, the selectivity of ing the vanadium loading resulted in the increasing
methanol could be greatly improved at low methane of the size of vanadium oxide. Larger particles pos-
conversion. sessed more active oxygen, which was responsible for
Spencer [51] has examined partial oxidation over the deep oxidation.
silica supported MoO3 catalysts. The major reac- Besides Mo and V-based oxide catalysts, many
tion products were HCHO, CO and CO2 , with only other metal oxides have also been examined [58] for
trace amounts of methanol. At low methane conver- the partial oxidation of methane, but the results
sion, selectivity to HCHO could be as high as 71%. were always unsatisfiable. The catalytic oxidation of
The effects of impurities were also examined, and it methane is also entangled by poor reproducibility.
was found that a sodium level as low as 300 ppm More recently, Hodnett et al. [59,60] assessed
had a detrimental effect on both methane conver- the limiting selectivity of active sites on oxide cat-
sion and oxygenates selectivity. In a later publication, alysts and stated that selectivity was determined by
Spencer [52] suggested that Na inhibits the oxidation the ability of the activating species to discriminate
of methane to HCHO but accelerates the further oxi- between the target bonds in reactants and the simi-
dation of HCHO to CO. lar but much weaker bonds in products. The conven-
Studies carried out by Barbaux et al. [53] on tional selective oxidation catalysts were not capable of
SiO2 supported MoO3 catalysts revealed that there selectively activating a C-H bond in a reactant in the
existed three different Mo species and distribution presence of a similar C-H bond in a product when the
regions, which were dependent on the Mo loadings. bond dissociation enthalpy of the product is weaker by
In loadings between 1wt% and 5wt%, molybdenum more than 30–40 kJ/mol. The C-H bonds in CH3 OH
strongly interacted with the support, forming silico- and HCHO are 50 and 75 kJ/mol weaker than the
molybdic acid (SMA). From 5wt%–10wt% loadings, corresponding C-H bonds in methane, respectively.
a polymolybdate species was observed to be covering Therefore, the conventional selective oxidation cat-
the SMA. At a loading of 15wt%, SMA disappeared alysts were not suitable for the partial oxidation of
and crystalline MoO3 was identified distributed over methane to methanol or formaldehyde.
the polymolybdate phase. Smith et al. [54] have There is now a new concept in catalyst design-
also investigated the nature of the surface species to control the gas phase homogeneous reaction cat-
on the MoO3 /SiO2 catalysts and identified three sur- alytically. In the homogeneous oxidation, the active
face species. Having a highly dispersed silicomolybdic oxidizing species such as OH can oxidize CH3 O and
phase, the lowest loading catalysts showed the best CH3 OH, resulting in the production of deep oxidation
catalytic performance. It was supposed that the sili- products. If some catalysts can transfer these active
comolybdic species have more terminal Mo=O sites, oxidizing free radicals into milder surface species in-
which are responsible for selective oxidation. How- stead of activating the reactant (methane), the vi-
ever, increasing the loading increased the number of olent oxidation would be greatly restrained or even
Mo-O-Mo bridging sites while decreasing the termi- avoided, and the oxidation of methane would be con-
nal Mo=O sites. It was Mo-O-Mo sites which were trolled to give higher methanol selectivity. Zhu et al.
responsible for the decrease in oxygenate production [61–63] have developed a multi-component catalyst,
and the increase in deep oxidation products. Mo-V-Cr-Bi-Ox/SiO2 , according to this concept of
Catalysts based on V2 O5 were also widely ap- catalyst design and obtained 80% methanol selec-
plied in the partial oxidation of methane. Spencer and tivity at 10% methane conversion. In Mo-V-Cr-Bi-
Pereira [55] found that on the silica supported V2 O5 Ox /SiO2 multi-component oxide catalysts, the crys-
catalyst, high selectivity of HCHO was observed at talline phase structures of the catalysts were sensitive
low methane conversion with trace methanol under to Mo, V and Bi loadings [63]. Bi could combine with
some conditions. Compared with the Mo-based cat- V and Mo to form BiVO4 and γ-Bi2 MoO6 , whereas
alysts it is showed that the V-based catalysts were Cr seemed to form a single Cr2 O3 crystalline phase in
more active. Kennedy et al. [56] have shown that the presence of Bi. Mo(VI) oxide appears to favor the
the yields of HCHO depend on the vanadium load- formation of partial oxidation products, and Cr(III)
ing, and optimum yields were achieved in the range oxide seems to enhance the conversion of methane.
1wt%-4wt%. The catalysts in their reduced state ex- The coupling of surface reaction and gas phase reac-
hibited mean vanadium oxidation states between 3 tion was supposedly responsible for the effective inhi-
and 4. Chen and Wilcox [57] suggested that increas- bition of deep oxidation and high methanol selectivity.
 Journal of Natural Gas Chemistry Vol. 12 No. 2 2003 87

3.2.2. Liquid phase homogeneous catalytic ox- dation using water as the supercritical fluid medium.
idation Unfortunately, the results were not as good as ex-
pected, and methanol yields were not greater than 1%.
There is also a great deal of interest in systems A reaction-separate reactor was designed and ap-
which could selectively activate methane at lower tem- plied to the partial oxidation of methane to methanol
peratures or preserve the selective partial oxidation by Yu et al. [71]. NO and Na2 B4 O7 were selected
products. These alternative approaches were usually as the homogeneous-heterogeneous catalysts. Cool-
in the liquid phase. Olah [64] reported the conversion ing H2 O was used to quench the reaction mixture and
of methane to methanol with >95% selectivity in liq- terminate the high temperature oxidation reaction.
uid superacidic conditions. Protonation of methanol About 20% single-pass yield of HCHO was achieved
was suggested to prevent further oxidation. In 1987, although the concentration of the produced HCHO
a two-stage process for the conversion of methane was very low because of the utilization of vapour as
to methanol and dimethyl ether was suggested [65]. an additive.
Methane was first monohalogenated through a reac- The laser stimulated surface reaction (LSSR)
tion with chlorine or bromine over either supported technique has also been applied to the partial oxida-
solid acid catalysis (e.g. SbF5 · graphite) or supported tion of methane. Zhong et al. [72] reported the results
platinum group metal catalysts (e.g. Pt/Al2 O3 ), and of this technique for the partial oxidation of methane
the resultant methyl halide was then catalytically hy- over H3 PMo12 O40 /CaF2 catalysts. The oxidation of
drolyzed to yield a mixture of methanol, dimethyl methane occurred at normal pressure and 200 , and
ether and hydrogen halide. A steady state conversion methanol was the direct product of methane oxida-
of 12%–18% was obtained producing 90% methyl bro- tion, while HCHO, CH3 OCH3 and hydrocarbons were
mide and 10% methanol/dimethyl ether, but this pro- the products of methanol continuously reacted on the
cess suffers from highly corrosive nature of reactants. solid surface.
The most exciting results ever reported were given
by Periana et al. [66]. The electrophilic displace- 3.2.4. N2 O as an oxidant
ment of methane using concentrated sulphuric acid
catalyzed by certain metal ions for the selective oxi- In the above discussions, the common oxidant is
dation of methane was developed. The required prod- molecular oxygen. The molecular oxygen in the gas
uct, methanol, was produced by hydrolysis of an in- phase might be transformed with the different oxygen
termediate methyl bisulphate species. Using mercuric species in catalysts as follows:
+e +e +2e 2−
ions as the catalyst, 43% methanol yield was achieved O2 →− O2(ad) −−→ O− 2 −−→ 2O−(ad) −−→ 2O(lattice)
when operating the reaction in a batch mode at 180 Different oxidation states possess different oxidiz-
[67]. In a later report, methanol yield was im- ing ability, which makes it very difficult to identify
proved to over 70% (81% selectivity at 90% conver- which should be responsible for the selective oxida-
sion) using a complex of platinum as the catalyst. tion and which for the combustion oxidation. The
existence of a mixture of the different oxygen species
3.2.3. Other processes also makes it difficult to control the oxidation reac-
tion. Therefore, some other oxidants have been ap-
In the above liquid phase processes, the oxida- plied in the oxidation of methane to methanol, of
tion products are all methanol derivatives that are which N2 O was the most widely studied substitute.
more stable than methanol itself. The more reason- In the early 1980s, Liu and Lunsford [10,73] reported
able methanol yields obtained demonstrated that it methanol selectivity of 84.6% at a methane conver-
is possible to achieve both methane conversion and sion of 8.1% over the MoO3 /SiO2 catalyst using N2 O
methanol selectivity if methanol can be protected as the oxidant instead of molecular oxygen. Somojai
from further oxidation. et al. [74] repeated Lunsford’s results and found that
Supercritical fluid extraction may be another V2 O5 /SiO2 was also an efficient catalyst for the oxi-
method of protecting the produced methanol to avoid dation of methane with N2 O as the oxidant, with a se-
deep oxidation, but choosing a suitable supercritical lectivity to methanol and formaldehyde of near 100%
fluid is difficult because the reaction takes place under at a conversion of approximately 0.2%. Hodnett et al.
severe conditions. Aki et al. [68], Lee et al. [69], and [75] have also observed 100% formaldehyde selectivity
Savage [70] have separately carried out methane oxi- over a 2% Mo loaded Spherosil (porous silica) or Cab-
88 Qijian Zhang et al./ Journal of Natural Gas Chemistry Vol. 12 No. 2 2003

O-Sil (fumed silica) support. ESR results confirmed 15: 375

that the active oxygen species for the N2 O selective [8] Boomer E H, Thomas V. Can J Res Sect B, 1937, 15:
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idized to CO2 [10]. 414
[10] Liu H F, Liu R S, Lunsford J H. J Am Chem Soc,
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α-oxygen, which was able to be selectively produced
[11] Gesser H D. In: Norell J R, Wada M eds. Re-
by decomposition of N2 O on a properly calcined search and development management in Pacific basin
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that the α-oxygen from N2 O could be inserted into posium held in conjunction with 1984 Chemical
the methane molecule, quantitatively, to produce Congress of Pacific Basin Societies. Honolulu, Hawaii,
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Catal Today 1998, 42: 191
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