Chapter 15

METHANOL PRODUCTION FROM NATURAL

GAS
Assessment ofCOl utilization in natural gas reforming

Angeliki A. Lemonidou, Julia Valla and Iacopos A. Vasalos

CPER! - Dep t. Chemical Engineering Aristotele "Univ. of Thessaloniki " PO Box 1517,
54006 University City Thessaloniki - Greece
lemonido@eng.auth.gr

1. INTRODUCTION

Carbon dioxide (C0 2) is widely recognized as a major greenhouse gas

contributing to global warming. This greenhouse gas is produced in large
quantities worldwide by the heavy industry, such as steel production,
chemical and petrochemical manufacturing, cement production etc.,
including power generation from fossil fuel. In the past decades, the
continuous and rapid development of such industries has caused
considerable concern. Awakening to the CO2-mediated global warming
problem has led to several international forums on c1imate change called by
the United Nations. As a result all developed countries are called to regulate
the COz emissions in order to eliminate the long term risk associated with
elimate change. Such a stipulation may adversely affect the development of
a large number of industries in the near future. [I, 2]
To mitigate the global warming problem, the removal of CO2 from the
industrial flue gases seems to be necessary. Carbon dioxide recovered from
flue gases can be sequestered in oceans or spent gas and oil wells in an
attempt to mitigate atmospheric CO2 increase. [3,4] An alternative and more
effective way is the recovered gas to be used for the production of
chemicals, fuels and other useful products. The motivation for the
production of chemieals lies in the fact that CO2 is a cheap, totally renewable
feedstock that can be used for the synthesis of materials like polymers and
the synthesis of intermediates and chemieals via new routes that are

379
M. Aresta (ed.), Carbon Dioxide Recovery and Utilization , 379-394.
© 2003 Kluwer Academie Publishers.
380 Angeliki A. Lemonidou et al.

competitive with the current established methods. [5] Even though the
impact of chemical utilization of CO 2 on the global carbon balance is small,
by no means can it be considered insignificant. However, the utilization of
CO2 as a feedstock for fuels and chemieals has to fulfill economie, technical
and environmental prerequisites in order to be feasible. [4]
One of the most promising and feasible routes for the use of CO 2 is the
synthesis of methanol. Methanol, a commodity chemical with agiobal
demand of around 36 MMT in 2000 is commercially manufactured via
indirect route based on natural gas. [6] It is actually used as a chemical
feedstock, mainly for the manufacturing of formaldehyde and methyl tert-
butyl ether (MTBE), a gasoline octane booster. The demand for MTBE is
dec1ining steadily due to environmental concerns . However, a much larger
potential for the methanol market is in the fuels sector. The conversion of
remote natural gas into easily transportable methanol is achallenge for the
gas industry. According to the Shell Briefing Service an annual demand of
2000MMT of gas for transportation is foreseen, as well as another
4000MMT of coal equivalent for power generation. [7] Stimulated research
efforts over the last few years have been directed towards the application of
methanol as a fuel for fuel cells. The methanol reforming system is an
attractive option for on board hydrogen generation at low temperature with
very promising results. [8]
Methanol is produced commercially from synthesis gas (CO + H2) via the
following basic reaction over zinc/copper based catalyst:

2Hz + CO ~ CH 30H (MI= -91 kJ/mol) (1)

The overall methanol synthesis is exothermic and equilibrium limited,

being favored by low temperature and high pressure. Commercial reactors
are fixed bed, operating in the range of230 to 270°C and 50 to 100 atm. [6]
The mixture of H2 and CO (syngas) is industrially produced by steam
reforming of natural gas, a mature and most established process, over Ni
based catalysts . [9] The main stoichiometrie equation that describes the
steam reforming of methane is:

C~ + H20 !:+ CO + 3H2 (MI = 206.3 kJ/mol) (2)

The water gas shift reaction is always active In methane reforming

environment:

CO + HzO !:+ CO z + Hz (MI = -41 kJ/mol) (3)