ISSN 1070-4272, Russian Journal of Applied Chemistry, 2015, Vol. 88, No. 5, pp. 787−795. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © S.I. Abasov, Y.S. Isayeva, F.A. Babayeva, S.B. Agayeva, H.J. Ibragimov, D.B. Tagiyev, M.I. Rustamov, 2015, published in Zhurnal
Prikladnoi Khimii, 2015, Vol. 88, No. 5, pp. 744−752.
Catalytic Reactions Involving Sterically Separated Active Sites
S. I. Abasov, Y. S. Isayeva, F. A. Babayeva, S. B. Agayeva,
H. J. Ibragimov, D. B. Tagiyev, and M. I. Rustamov
Mamedaliyev Institute of Petrochemical Processes, National Academy of Sciences of Azerbaijan,
Khojaly ave, Baku, Az 1025 Azerbaijan
Received November 14, 2014
Abstract—The possibility of using mixtures of commercial catalysts bearing acid–base or redox sites for control-
ling the activity and selectivity of conversion of methanol into dimethyl ether, of these substances into desired
hydrocarbons, and of low-temperature dehydroalkylation of benzene with propane was demonstrated.
The development of processes for producing a source
of hydrocarbons and motor fuels alternative to crude oil
and based on natural gas (via syngas and methanol) and
involvement of casinghead gas components (propane,
butane) into such processes is a topical scientific
and technical problem. The flowsheet of methanol
conversion into fuels (MtSynfuels) includes steps of
methanol conversion into dimethyl ether (MtDМE) and
oleﬁ n (MtO), and also of conversion of low-molecular-
mass oleﬁ ns into motor fuels . It is known that the
MtSynfuels steps are accompanied by reactions of the
intermediates and products formed both with the reactant
and with each other. The drawback of the MtSynfuels
implementation in which MtO in combined with the
subsequent conversion of oleﬁ ns into distillate (СОD)
is the presence of excess amounts of restricted aromatic
hydrocarbons in the resulting fuel . Low conversion
of syngas into methanol in one pass over the catalyst also
restricts the development of MtSynfuels. This drawback
is eliminated by combining the methanol formation with
its irreversible conversion into dimethyl ether (DME) in
one reactor by contacting the syngas with appropriate
mechanical mixtures of catalysts or with a polyfunctional
catalyst exhibiting the required properties.
On the other hand, such passing from methanol to
DME gives rise to the problem of passing from MtO to
DМEtО and from MtSynfuels to DМEtSynfuels, and
also of controlling the M/DME ratio, because methanol is
also demanded as raw material for many other processes.
In cases when the product of one catalytic process
(primary product) is the raw material for another process
(ﬁ nal product), it becomes necessary to combine these
reactions in a common reaction space. This result can
be reached by using either mechanical mixtures of
catalysts or polyfunctional catalysts combining the
required catalytic properties. In contrast to polyfunctional
catalysts, localization of active sites of different nature on
separate components of a mechanical mixture of catalysts,
conventionally termed spatially separated sites, can allow
considerably simpler solution of the problem by choosing
appropriate commercially available catalysts.
Mechanical mixtures of catalysts are considered
by researchers, but mainly for comparison with
polyfunctional catalysts [2–6]. The possibility of
controlling the formation of final products or their
distribution by replacing components of the mechanical
mixture was not given due attention.
Here we consider the possibility of using mechanical
mixtures of catalysts for controlled conversion of
methanol and low-molecular-mass alkanes.
Experiments were performed with mechanical catalyst
mixtures (CMs) consisting of H forms of zeolites Y
and TsVK (structural analog of ZSM-5) and of a metal
oxide component. As metal oxide components we used