Russian Journal of Applied Chemistry, 2013, Vol. 86, No. 1, pp. 27−31.
Pleiades Publishing, Ltd., 2013.
Original Russian Text © Yu.M. Komarov, A.A. Il’in, N.N. Smirnov, A.P. Il’in, D.B. Babaikin, 2013, published in Zhurnal Prikladnoi Khimii, 2013, Vol. 86,
No. 1, pp. 31−35.
Effect of Alkali Metal Oxides on the Selectivity
of Carbon Monoxide Conversion to Give Hydrogen
on Copper-Containing Catalysts
Yu. M. Komarov, A. A. Il’in, N. N. Smirnov, A. P. Il’in, and D. B. Babaikin
Ivanovo State University of Chemical Technology, Ivanovo, Russia
Received July 12, 2012
Abstract—Possibility of synthesizing aluminum–zinc–copper catalysts by mechanochemical activation of metallic
copper and zinc with ammonium carbonate, followed by introduction of γ-Al
and promoter additives (potas-
sium, rubidium, and cesium carbonates), hydrothermal treatment, and calcination is demonstrated. The effect of
the promoter additives and preparation conditions was studied. The activity and selectivity of the samples in the
reaction of steam conversion of CO was examined. The composition of by-products formed in the course of a test
reaction was determined.
The development of chemical industries is character-
ized by a wide use of catalysts that favor an increase in
the production volume, improve the quality of products,
and make it possible to substantially diminish their cost.
Methods used to prepare catalyst masses should be as
simple as possible, satisfy certain economical and eco-
logical requirements, and provide safe labor conditions.
In manufacture of ammonia, the stage of low-tem-
perature conversion of carbon monoxide with steam
to give hydrogen is performed on copper-containing
catalysts . The existing methods for their fabrication
employ a complex multistage scheme for preparation
of raw components and the catalyst itself, need a gross
material and energy expenditure, and produce a large
amount of wastewater and efﬂ uent gases requiring ad-
ditional puriﬁ cation.
The available published data fail to provide unam-
biguous information about copper compounds preced-
ing the active and stable state of the catalyst in operation
conditions. However, numerous researchers believe that
one of the main conditions for synthesis of a high-ac-
tivity catalyst is the maximum homogenization of com-
ponents of a catalytic formulation. It is assumed that
clusters of copper ions are distributed in a matrix of zinc
oxide crystals whose structure is distorted by impurity
anions. In this case, formation of mixed copper-zinc hy-
droxo carbonates, with copper distributed in octahedral
voids of hydroxy packages, in early stages of fabrication
makes it possible to obtain mixed Cu–Zn oxides upon
calcination [2, 3]. Mechanochemical activation (MCA)
is one of the most efﬁ cient synthesis procedures, which
can markedly raise the rate of the chemical interaction
in a heterogeneous system.
Because the existing methods for fabrication of
copper-containing catalysts are based on precipitation
processes, we demonstrate in this study that the mecha-
nochemical synthesis can be used to synthesize an alu-
minum–zinc–copper catalyst that compares well with
analogs fabricated by the conventional methods. For
this purpose, it is necessary to study in detail the phase
composition of intermediate chemical compounds,
which will enable a directed synthesis of a particular
structure of the active component. Also, a number of
side reactions yielding methanol, acetaldehyde, ethanol,
etc. occur in addition to the main reaction on catalysts
for CO conversion [4, 5]. Presence of these compounds
in the conversion gas is undesirable because it impairs