PRODUCTION OF METHANOL FROM METHANE AND AIR

V.Reshma Sona a, S.Vijayalakshmi b,

III year, B.Tech Chemical Engineering, ACT campus, Anna University, Chennai.
a
megarajsona@gmail.com, b vijisrinivas2209@gmail.com

ABSTRACT:

The most promising fuel of modern days, Methanol can be directly produced by
oxidizing methane using Hydrogen Peroxide. This process involves using oxygen
from air, resulting in the cheapest methanol production ever. Gold-Palladium
nanoparticles prepared using incipient wetness impregnation technique act as
catalysts here. Methyl hydro peroxide, the primary product formed is converted to
methanol at a high selectivity of 92%. This process involves mild temperatures and
high energy efficiency when compared to the current steam reforming and
methanol synthesis. This new method also avoids 100 million tons of natural gas
getting wasted each year. This way, methanol can replace petrol and diesel as the
cheap, clean and green fuel.

KEYWORDS:

Air, Gold-Palladium nano particles, Hydrogen Peroxide, Methanol,

INTRODUCTION:

Methanol also known as ‘wood alcohol’ is a revolution in chemical industry. The

annual production is 70 million tones because methanol has a number of uses. It is
considered to be the perfect solvent, a gasoline additive to increase octane number
and a chemical feedstock for the production of bio diesel and hundreds of other
chemicals. Even plastics are based on methanol. It is a light, colorless, volatile
flammable liquid of low boiling point (65°C). Methanol is the raw material for
many chemicals, formaldehyde, dimethyl terephthalate, methylamines and methyl
halides, methyl methacrylate, acetic acid, gasoline etc[1]. The existing methanol
production method is highly expensive and highly polluting. In this article, a new
method of methanol production is discussed which makes it cheaper and easier.
METHANOL – AS FUEL

Methanol is considered to be an alternate fuel for petrol and diesel. Because it does
not produce toxic exhaust and also the fuel reserves are depleting around the
world. Pure methanol is used in Formula-1 racing cars. Methanol is chiefly
produced from methane (major constituent of natural gas), which is in abundance
in nature. The chief advantage of a methanol economy is that it could be adapted to
gasoline internal combustion engines with minimum modification to the engines
and to the infrastructure that delivers and stores liquid fuel. Compared to gasoline,
methanol is more tolerant to exhaust gas recirculation, which improves fuel
efficiency of the internal combustion engines utilizing Otto cycle and spark
ignition. Using methanol as a fuel in spark-ignition engines can offer an increased
thermal efficiency and increased power output (as compared to gasoline) due to its
high octane rating and high heat of vaporization. To increase the octane number of
gasoline, methanol is added to it as an additive. Methanol, the simplest single
carbon compound can serve as the best alternative fuel for India. It is a highly
efficient fuel, can be blended with gasoline/diesel, emits lesser NOx, PM, no SOx
and can be further converted to Dimethyl ether (DME) which is a clean diesel
alternative and can be blended with LPG as well. Emissions from methanol
powered vehicles are quite less at the consumption end[2]. It can decrease the
dependency on foreign energy sources and conservation of petroleum energy
reserves of our nation[3].

CURRENT METHANOL PRODUCTION

The industrial methanol synthesis follows two steps : 1)Steam methane reforming
2)Methanol synthesis. At moderate pressures of 1 to 2 MPa (10–20 atm) and high
temperature (around 1080K), methane reacts with steam on a nickel catalyst to
produce synthesis gas. This reaction, commonly called steam-methane reforming
or SMR, is endothermic[4]. The synthesis gas is cooled and compressed before
passing to the methanol synthesis step, in which it reacts over a fixed catalyst bed
to form methanol. This is a high pressure (50 bar) catalytic conversion. The raw
methanol is purified and collected.
DRAWBACKS:

‘Steam reforming and Methanol synthesis’ is expensive and energy intensive

process. This involves high temperature and high pressure. Also, 100 million tons
of natural gas is wasted each year in this process[5]. These are flared into the
atmosphere since methane is a strong greenhouse gas (20 times stronger than
CO2)[6]. The reforming reaction takes place at high temperatures, making it slow
to start up and requiring costly high temperature materials[7].To save the most
valuable inexpensive clean burning natural gas getting wasted and to decrease the
cost of methanol, there is a need to reduce this two step process into one step
process, avoiding the production of synthesis gas which requires high pressure,
high energy, high cost and large plant size.

RESEARCHES:

For so many decades, scientists are searching for a direct one step process to
convert methane to methanol. Methane can be directly oxidized to methanol but it
poses few problems: 1) Side reactions occur – More difficult processes has to be
used to eliminate these undesired products, adding to the expense[8] 2) Process do
not take place without catalyst- search for the perfect catalyst is needed 3)
Methanol is more reactive than methane, readily forming other products 4) Poor
selectivity of methanol 5) Full combustion of methane produces CO2 instead of
methanol 6) High stability of C-H bond (435 kJ/mol) in CH4 which makes the
bond difficult to break[9].

Addition to these problems, there are certain other parameters affecting this
conversion. They are: 1) Temperature 2) Pressure 3) Methane to oxygen ratio in
the feed gas 4) Total gas flow rate (residence time) 5) Additives like ethanol 6)
Effect on reactor wall[10].

Selective oxidation of methane to methanol occurs only at low temperature. When

the yield is higher, the conversion is always lesser. This is due to the higher
activation energy needed for the reaction to occur[11]. Helton in 1991 conclude
that methanol production via a direct, single step method would be competitive
with existing methanol production methods (steam reforming of methane followed
by oxidation of synthesis gas) if it achieved a single pass methane conversion of at
least 5.5% yield with selectivity to methanol of 80%. This information is presented
here because it serves as a performance standard that any prospective direct
methanol production process must meet to be economically feasible [12]. The low
magnitude of the conversion requirement is indicative of the high expense
associated with existing methanol production methods.

NEW METHOD:

Our new method solves all these problems. Methane is oxidized using molecular
oxygen as oxidant in the presence of a very small amount of hydrogen peroxide.
This is an isotopic ally labeled oxygen derived from air. Colloidal gold-palladium
nanoparticles are used as catalysts. The controlled breakdown of H 2O2 by catalysts,
activate CH4 which incorporates molecular oxygen through a radical process. The
primary product formed here is methyl radicals breaking the C-H bonds, leading to
the selective oxidation of methane to methanol. If a stable supply of methyl
radicals can be established, this conversion is entirely feasible.

RESULTS AND DISCUSSION:

For this reaction to occur, Au-Pd nanoparticles should exist as free floating
colloids in a very weak H2O2 solution into which pressurized CH4 and O2 gas are
injected[13]. The complete set of reactions gives us an insight into this process.

Complete oxidation of methane:

CH4 + 2O2 = CO2 + 2H2O (CO2 formation is not preferred)

Partial oxidation of methane:

CH4 + 1/2O2 = CH3OH (Methanol formation is desired)

This is achieved using Au-Pd nanoparticles. Contrary to bulk gold, nanogold (3-5
nm) has high activity and high selectivity in combustion as well as partial
oxidation.
 Au- + 2CH4 + 1/2O2 = Au-(CH4) + CH3OH

Au-(CH4) + 1/2O2 = Au- + CH3OH

Adding these reactions, we get,

CH4 + 1/2O2 = CH3OH (The desired reaction)

The methyl radicals thus formed play a vital in the conversion of methanol.
Catalysts play a vital role in forming these radicals.

On discussing the results, we obtain these results:

1) Side reactions do not occur here – only methanol is formed.

2) The perfect catalyst is found – Colloidal Au-Pd nanoparticles.
3) Methanol oxidation is avoided since this reaction occurs at a very low
temperature itself.
4) This method provides 92% selectivity which is the highest ever found.
5) Selective partial oxidation occurs instead of full combustion thus CO2, a
greenhouse gas is not formed.
6) Gold catalysts break the very strong C-H bond forming methyl radicals, thus
leading to the formation of methanol.

These catalysts are formed by incipient wetness impregnation technique which is

used when the interaction between the species and the support is too weak and
used for the production of heterogeneous catalysts. This is the most common
commercial procedure for dispersing the catalytic species within the carrier. An
active metal precursor is dissolved in aqueous solution and added to catalyst
support of same pore volume[14]. Capillary action draws solution into the pores.
This is then dried and calcined to settle the metal on catalyst surface. Usually, Au-
Pd nanoparticles are always dispersed on high surface area oxide supports such as
titania. But here, ceramic support presence of Ti turns to be detrimental[15].

This new method is a low energy reaction because less energy is needed to make or
break the bonds[16]. Reactor design has the ability to limit the oxidation of
methanol. The ideal choices are Pyrex or quartz lined plasma reactor. Methanol
thus produced by this method is in an energy form which is easier to transport and
more efficient[17].

CONCLUSION:

Thus, methane can be directly converted into methanol by selective partial

oxidation. Methanol produced this way is cheap because of no synthesis gas
produced and green because of no CO2 production. Petrol reserves are depleting at
a faster rate, so we need to utilize methane of natural gas to produce methanol for
future needs. The above mentioned process is simpler in use and can be
commercialized with a better reactor design. Methanol has about half the energy
content per volume of gasoline and roughly three times that of liquid
hydrogen[18]. Further, methanol applications are expected as a matrix for storing
and transporting hydrogen. Catalysts for many commercial productions are yet to
be found. Finding the perfect catalyst in this most widely researched topic is a
major breakthrough in the fuel and chemical industry.

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