S1
ISSN 0965-5441, Petroleum Chemistry, 2019, Vol. 59, Suppl. 1, pp. S1–S20. © Pleiades Publishing, Ltd., 2019.
New Approaches to the Design of Nickel, Cobalt,
and Nickel–Cobalt Catalysts for Partial Oxidation
and Dry Reforming of Methane to Synthesis Gas
I. I. Moiseev
a, b, c
, A. S. Loktev
a, b, c,
*
,
**, O. A. Shlyakhtin
d
, G. N. Mazo
d
, and A. G. Dedov
a, b, c
a
Gubkin Russian State University of Oil and Gas (National Research University), Moscow, 119071 Russia
b
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, 119991 Russia
c
Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, 119071 Russia
d
Moscow State University, Moscow, 119991 Russia
*e-mail: genchem@gubkin.ru
**e-mail: al57@rambler.ru
Received August 7, 2019; revised August 25, 2019; accepted September 6, 2019
Abstract—New approaches to the formation of active, selective, and stable Ni, Co, and Ni–Co catalysts for
partial oxidation and dry reforming of methane into synthesis gas (a mixture of hydrogen and carbon mon-
oxide) are considered.
Keywords: synthesis gas, partial oxidation of methane, dry reforming of methane, nickel, cobalt, perovskite-
like oxides, mesoporous materials, zeolites, magnesium–aluminum hydrotalcite
DOI: 10.1134/S0965544119130115
INTRODUCTION
The selective catalytic reforming of methane to
synthesis gas (syngas) is a key stage in the production
of a variety of petrochemicals and alternative fuel
components from natural gas [1–11]. According to
experts, it is the syngas manufacturing process that
drives about 70% of costs in the chain of production of
petrochemicals from methane. Any improvement in
the syngas production process is a desirable task.
Teams of leading world and Russian research centers
are permanently working on its solution.
The main industrial process for producing synthe-
sis gas—steam methane reforming—is highly endo-
thermic and, as a result, energy-consuming. The
resulting syngas with a ratio of H
2
/CO = 3 cannot be
directly used for the production of petrochemicals. A
more convenient composition of the synthesis gas is
achieved in the processes of methane dry reforming—
(H
2
/CO = 1) or partial oxidation—(H
2
/CO = 2). The
latter process is also less energy consuming due to exo-
thermicity.
The embodiment of the process of dry reforming of
methane (DRM) has attracted increasing attention of
researchers around the world, since two main green-
house gases carbon-dioxide and methane- are utilized
in this process. This, in turn, contributes to solving the
problem of global warming. In addition, the DRM
process is considered as a promising way to obtain pet-
rochemical products from the renewable feedstock
biogas [12].
However, the realization of partial oxidation and
dry reforming of methane into the industry is largely
hampered by the lack of appropriate stable and selec-
tive catalysts. The implemented process of partial oxi-
dation of methane (POM) proceeds as a noncatalytic
reaction above 1100°C [1–3].
Known POM and DRM catalysts contain active
sites formed by Group VIII metals, mainly nickel [1–
11]. Numerous data on the use of catalysts based on
platinum group metals are mainly of theoretical inter-
est due to their high cost. At the same time, nickel cat-
alysts are capable of catalyzing the formation of carbo-
naceous deposits (especially during the DRM process)
and, in addition, are prone to strong interaction with
the support, which can cause the formation of com-
pounds that are inactive in catalysis. To overcome
these drawbacks, catalysts are often promoted with
platinum group metals, which significantly increase
their cost. In some cases, it is possible to increase the
stability of nickel catalysts by doping with cobalt or
other nonprecious metals; however, their activity is
often reduced.
A significant number of research papers and review
articles are published annually on the search for new
approaches to the design of active, selective, and stable
POM and DRM catalysts of various natures. In this