Russian Journal of Applied Chemistry, 2010, Vol. 83, No. 1, pp. 84−91.
Pleiades Publishing, Ltd., 2010.
Original Russian Text
E.N. Vinogradova, A.V. Dul’nev, V.N. Efremov, E.Z. Golosman, 2010, published in Zhurnal Prikladnoi Khimii, 2010, Vol. 83, No. 1,
AND INDUSTRIAL ORGANIC CHEMISTRY
Synthesis of Nickel–Copper–Cobalt Catalysts
for Deep Oxidation of Methane and Optimization
of Their Composition
E. N. Vinogradova, A. V. Dul’nev, V. N. Efremov, and E. Z. Golosman
NIAP-Katalizator Limited-Liability Company, Novomoskovsk, Tula oblast, Russia
Received July 29, 2009
Abstract—Possibility of fabricating catalysts based on Ni, Cu, Co, and Mn oxides by the impregnation method
was examined. The samples obtained were subjected to physicochemical analysis and their catalytic activities in
deep oxidation of methane were compared. The composition of the Ni–Cu–Co catalytic system was optimized.
The catalytic oxidation of hydrocarbons and, in
particular, methane is one of the most efficient and
cost-effective methods for purification of industrial
gases. It is preferable to perform deep oxidation, whose
technology provides conversion of a substance being
oxidized to carbon dioxide and water and precludes
formation of carbon monoxide and toxic oxygen-
containing organic substances. Compared with other
hydrocarbons, methane requires the highest temperatures
for its removal. Therefore, it has been stated  that, if the
required methane removal efﬁ ciency is provided under
certain puriﬁ cation conditions, this will be sufﬁ cient for
removing other hydrocarbons with the same efﬁ ciency.
Consequently, methane can be regarded as a key
component in gas puriﬁ cation to remove hydrocarbons.
The maximum catalytic activity in deep oxidation
of methane is characteristic of platinum-group metals
. However, their high cost and difﬁ cult availability
necessitates their replacement with nonprecious metals.
Results obtained in studies of the deep oxidation on
various oxide catalysts  convincingly demonstrate
that high activity is exhibited by transition metal oxides
having a mobile oxygen in their lattice. Boreskov studied
the catalytic activity of oxides of Period IV metals in
the methane oxidation reaction and demonstrated that
the oxygen binding energy on the catalyst surface is an
important factor determining the catalytic activity. The
highest speciﬁ c catalytic activity among transition metal
oxides is observed for Co
. Oxides of manganese,
nickel, and copper also have high catalytic activity.
However, it has been found that the activity of complex
oxide systems in oxidation of hydrocarbons exceeds that
of individual oxides [4–7]. The authors of  attributed
the increased activity of cobalt spinels in full oxidation
processes to the ease of structural transformations, which
facilitates the diffusion of oxygen to a molecule being
Development of effective catalysts for deep oxidation
of methane without use of precious metals is a difﬁ cult
task. It can only be accomplished by an integrated
approach to the corresponding studies. The severe
operation conditions of catalysts in catalytic puriﬁ cation
reactors impose stringent requirements on these catalysts.
A catalyst should have a high mechanical strength,
resistance to an oxidizing medium, high and stable
activity, and low hydraulic resistance.
The goal of this study was to develop supported
catalysts satisfying the above requirements, perform an
integrated study of processes occurring in their formation,
and examine the possibility of improving the catalytic
activity and thermal stability of the catalysts by varying
the ratio between their active components. In addition, it
was of interest to analyze the possibility of using various
supports for fabrication of puriﬁ cation catalysts.