CONVERSION OF METHANE TO GASOLINE RANGE

HYDROCARBONS VIA OXIDATIVE COUPLING.

Methane is the major constituent of natural gas and also of biogas. World reserves of
natural gas are constantly being upgraded and more and more natural gas is currently being
discovered than oil. Because of the problems associated with transportation of a very large
volume of gas, most of the natural gas produced along with oil, particularly, at remote places,
and the methane produced in petroleum refining and petrochemical process are flared and
hence wasted. Both methane and CO2 are green house gases, responsible for global warming.
Hence, in future the flaring of natural gas produced during the oil production and methane
produced in the petroleum refining and petrochemical processes would not be allowed and
hence the methane or natural gas is to be converted to useful value-added and easily
transportable product like liquid hydrocarbons of gasoline range.
Natural Gas (comprising of methane) is an abundant fossil fuel resource. Recent
estimates places worldwide Natural Gas reserves at about 35x10^14 standard cubic feet
which is equivalent to 657 billion barrels of oil. Methane is the most stable and symmetric
organic molecule consisting of four C–H covalence bonds with bond energy of 435 kJ/mol.
Accordingly, the effective activation and direct conversion of methane are also a great
challenge in the science of catalysis.
A number of strategies are being explored and developed for the conversion of
methane to more useful chemicals and fuels. These include steam and carbon dioxide
reforming or partial oxidation of methane to form carbon monoxide and hydrogen, followed
by Fischer-Tropsch chemistry, direct oxidation of methane to methanol and formaldehyde,
oxidative coupling of methane to ethylene and direct conversion to aromatics and
hydrogen in the absence of oxygen . However, most of those processes occurred at high
temperature and suffered from severe catalyst deactivation because High temperature
operation for the direct methane conversion led to poor economics associated with a low
yield of the desired hydrocarbon products. This is because the products formed may be
readily oxidized under the conditions required to activate methane, thus limiting selectivity.
Zeolites such as ZSM-5 have been found to be active for low temperature conversion to
more valuable hydrocarbons with and without oxidants.
 The heterogeneously catalyzed oxidative coupling of methane (OCM) seems to be
one of the most promising routes to convert methane directly from the natural gas into
ethylene which is a feed stock for chemical industry and/or by oligomerization of ethylene
into transportation fuels. Two factors handicap commercialization of this process.

1. C2 selectivity and yield are two low.

2. Technological novelty in uncertainty for scale up.

The concerned process involves converting methane to hydrocarbons having at least

2 carbon atoms by bringing it in contact to either a reducible metal sulphide (which can be
regenerated by oxidation) or with the help of a basic catalyst. Reactions of methane with
metal sulphide is carried out under the reaction temperature of 400-1000 degree Celsius and
a pressure of 0.1-30 atmospheres, the contact between the two being provided by either a
fixed bed or a fluidised bed. The metal sulphide is regenerated by an oxidation process such
as H2S to elemental S via the Claus process.
In case of basic catalyst methyl radicals combine to form ethyl radicals which on
oxidative dehydrogenation give ethylene. Higher range hydrocarbons can be converted to
gasoline range products via oligomerisation/cyclisation or dehydrocyclisation process in
presence of catalyst. A coupling reaction involves the joining of two hydrocarbon fragments
with the aid of a metal containing catalyst, in this case we carry out an oxidation
process(zeolite catalyst) to complete the coupling under the conditions specified above,
giving rise to a range of products from ethane and butane to aromatics like benzene or xylene.
The methane can also be converted or oxidised to methanol which is further converted to
gasoline range through the MTG(methanol to gasoline) process.
Thereby, I intend to carry out the aforesaid process on the laboratory scale and take
note of the reaction conditions and the expense involved, so that it can be implemented on a
larger scale to meet the current demands. Therefore, we can conclude that gasoline, a major
energy source, needs to be produced from alternate sources such as natural gas as the
naturally occurring crude is fast depleting.