Russian Journal of Applied Chemistry, 2013, Vol. 86, No. 5, pp. 733−738.
Pleiades Publishing, Ltd., 2013.
Original Russian Text © D.B. Tagiev, S.B. Agaeva, S.I. Abasov, R.V. Starikov, A.A. Imanova, N.S. Asadov, F.M. Nasirova, 2013, published in Zhurnal
Prikladnoi Khimii, 2013, Vol. 86, No. 5, pp. 786−791.
Conjugate Conversion of Methanol and n-Butane
on Zinc–Zirconium Catalysts
D. B. Tagiev, S. B. Agaeva, S. I. Abasov, R. V. Starikov, A. A. Imanova,
N. S. Asadov, and F. M. Nasirova
Mamedaliev Institute of Petrochemical Processes, National Academy of Sciences of Azerbaijan, Baku, Azerbaijan
Received July 12, 2012
Abstract—Conversion of n-butane, methanol, and their mixture on ZSM-5 zeolite catalysts containing zinc and/
or zirconium was studied, and ways were found to control the yield and ratio of major reaction products: С
isoalkanes, and arenes. The schemes of formation of these products were suggested.
It is known that methanol is considered as key inter-
mediate in production of hydrocarbons from raw materials
other than oil. There are about 80 plants in the world,
and there are prospects for an increase in the total output
to 55 mln tons annually, with various applications of
methanol . At the same time, in oil-extracting regions,
utilization of casing-head gases remains a topical prob-
lem, because the major fraction of these gases, as well as
hydrocarbon gases from oil reﬁ neries, do not ﬁ nd proper
use for production of valuable chemical products [2, 3].
Numerous studies have been published in the past decade
on utilization of these gases on high-silica ZSM-5 zeolite
modiﬁ ed with various metals [4–6]. At the same time, one
of possible routes of processing of casing-head gases is
their joint conversion with methanol into various oleﬁ ns
and arenes on ZSM-5 zeolite catalysts. It was shown in
 that, when performing the process in the presence of
methanol, the activation temperature of С
and the catalytic activity of НZSM-5 zeolite with respect
to alkenes and arenes can increase. However, such studies
are insufﬁ ciently systematized. In particular, they do not
allow taking into account the effect of zirconium and zinc,
which are widely used in aromatization of lower alkanes,
on the reactivity of gaseous hydrocarbons (e.g., n-butane)
in their joint conversion with methanol.
Such processing of lower alkanes can be one of
promising routes to lower alkenes, arenes, and motor
fuel components. However, the selectivity of conjugate
transformations of methanol with such alkanes remains
to be studied.
Here we report on a comparative study of the trans-
formations of methanol, n-butane, and their mixture on
ZSM-5 zeolite catalysts modiﬁ ed with zinc and/or zirco-
nium and discuss the possibility of varying the process
selectivity with respect to various reaction products.
Experiments were performed with catalysts prepared
by modiﬁ cation of the initial HZSM-5 zeolite with zinc
and/or zirconium and with the initial HZSM-5 zeolite with
the silica-to-alumina ratio of 64. The active components
were applied onto the zeolite by impregnation with solu-
tions with the preset concentrations of ZrO(NO
O, followed by evaporation, drying
for 24 h at room temperature, and mixing with the binder,
. The catalyst synthesis was completed with forming
(granulation) followed by heat treatment at 120, 350, and
500°С for 4 h. The sample containing both components
was prepared similarly. First we applied the zinc salt, and