Direct Methane To Methanol:
Foundations and Prospects
of the Process
Vladimir Arutyunov
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russia
The direct conversion of methane and other
light hydrocarbons to methanol (DMTM) and
other oxygenates has been a long-sought goal of
the gas industry for decades. In spite of some
experience of industrial applications in the
1930 1940s, nowadays this process remains in
the sphere of academic rather than practical in-
terest. However, some new tendencies in the
world’s gas industry rekindled interest in this
process. The monograph reviews the modern
state of knowledge in this area and discusses
some promising practical applications.
INTRODUCTION
Intense scientific research and technologi-
cal development in the field of direct conver-
sion of natural gas to chemicals has been
going on for a century. The reason for the un-
flagging interest in this problem is twofold.
On the one hand, it has been found that, un-
der certain conditions, the oxidation of even
simple hydrocarbons, such as methane, is
accompanied by a rapidly increasing com-
plexity of the system, with the formation of
a multitude of different products, from wa-
ter and carbon oxides to various carbon com-
pounds, including such complex as
fullerenes and carbon nanotubes. Therefore,
even though the oxidation of methane and
its closest homologues gave, in due time,
the main body of data underlying the mod-
ern concepts of the kinetics of gas-phase
vii
reactions, these processes even now seem so-
phisticated and inexhaustible, like the nature
itself. On the other hand, the chemical con-
version of light alkanes, the main compo-
nents of natural and associated gas, has
become one of the most important trends in
modern petro-chemistry and in a full-
fledged new industrial sector: gas chemistry.
The wide variety of products of the oxida-
tive conversion of natural gas includes
hydrogen, syngas, ethylene, other olefins, ox-
ygenates, and aromatic compounds. The
scope of the present monograph is much nar-
rower, limited to the direct conversion of nat-
ural gas to oxygen-containing compounds
(oxygenates), mainly methanol and formal-
dehyde, under predominantly homogeneous
gas-phase conditions. Nowadays, this direc-
tion revealed potentiality for new practical
applications, in particular concerning low re-
sources and remote gas fields, shale gas, and
other unconventional gas resources.
Since the predominant and most hardly
convertible component of natural and asso-
ciated gas is methane, with the main prod-
uct of the direct oxidative conversion of
methane and other light alkanes C2 C4 be-
ing methanol, the overall process of natural
gas oxidative conversion to oxygenates has
traditionally been referred to as Direct
Methane To Methanol (DMTM), a term
that will be used throughout the
viii DIRECT METHANE TO METHANOL: FOUNDATIONS AND PROSPECTS OF THE PROCESS
monograph. It covers the totality of pro-
cesses of conversion of natural gas light al-
kanes to oxygenates. In addition, the
partial oxidation of methane to methanol is
the subject of the overwhelming majority
of published academic and technological in-
vestigations on the direct gas-phase conver-
sion of alkanes to oxygenates. On the other
hand, there are only limited number publi-
cations concerning heavier hydrocarbons;
therefore, the focus will be on analysis of
methane partial oxidation to oxygenates,
with generalization to other alkanes given
separately.
As an industrial technology, DMTM has
seen a sweeping rise and subsequent
decline, mainly due to the lack of under-
standing of the underlying complex chemis-
try. However, scientific research on the
process have never stopped, as evidenced
by a large number of publications, including
very recent, cited in the monograph. Of the
most attractive features of DMTM, apart
of its technological simplicity, are a very effi-
cient internal energy self-supply by the par-
tial oxidation of the hydrocarbon itself
and the possibility of direct formation of
nonequilibrium products that cannot
be produced in significant amounts under
thermodynamically equilibrium conditions.
Current interest in DMTM is prompted by
significant changes in the gas industry,
which strongly needs low-scale technologies
capable of operating on low resources,
remote and unconventional gas fields. In
the technological niche of relatively simple
small-capacity processes, the direct partial
oxidation of natural and associated gas to
methanol is still one of the most promising
and elaborated directions. Along with fun-
damental advances in studying the mecha-
nism of the oxidation of hydrocarbons at
moderate temperatures and high pressures,
it gives a good chance to revive DMTM as
an industrial technology.
In this connection, a good deal of the
monograph is devoted to the prospects of
practical applications of DMTM and its pos-
sible future role in the gas industry. There is
a vast room for further improvements of the
process given that the interest from the in-
dustry will promote necessary efforts.
Thus, the need in alternative simple and flex-
ible low-scale Gas-to-Liquid (GTL) technol-
ogies may become a real driving force for
a DMTM refinement.
The monograph reviews the modern state
of knowledge on DMTM with emphasis on
its most evident practical applications. It
summarizes and supplements our previous
reviews [1 4] and monographs [5, 6] on
the subject, including the problem of model-
ing the homogeneouseheterogeneous oxida-
tion of light alkanes [7], as well as a number
of recent interesting but somewhat contra-
dictory experimental results. The mono-
graph covers more than 300 publications on
the high-pressure low-temperature oxida-
tion of methane and other gaseous hydrocar-
bons over a period from the beginning of the
last century up to now and offers a unique
comprehensive analysis of practically all rel-
evant experimental and theoretical data on
the DMTM process. As well it discusses the
real practical prospects of DMTM.
We believe that it will provide researchers
and engineers working in the field of gas pro-
duction and processing with necessary theo-
retical knowledge and experimental data for
development and application of new pro-
cesses involving the direct oxidation of natu-
ral gas. We hope that it will be useful for all
those who work in the field of gas processing
and gas chemistry by facilitating their efforts
in practical development and utilization of
new effective gas chemical process.
The author feels obliged to express his
deep gratitude to late Professor V.I. Vedeneev
for many years of joint work on the DMTM
process and especially its mechanism and
 DIRECT METHANE TO METHANOL: FOUNDATIONS AND PROSPECTS OF THE PROCESS ix
to late Professor O.V. Krylov for very fruitful collaboration, which has produced practi-
cooperation and discussions of the whole cally all of our recent results on DMTM.
field of hydrocarbon oxidation. The author Author thanks Dr. V.N. Smirnov for his big
is also grateful to Professor V.I. Savchenko help in preparation of English version of
and Dr. V.M. Rudakov for long-standing this monograph.