1070-4272/01/7407-1137$25.00C2001 MAIK [Nauka/Interperiodica]
Russian Journal of Applied Chemistry, Vol. 74, No. 7, 2001, pp. 1137!1140. Translated from Zhurnal Prikladnoi Khimii, Vol. 74, No. 7,
2001, pp. 1107!1110.
Original Russian Text Copyright + 2001 by Lur’e, Milova, Storozheva, Kurets, Shmidt.
Effect of Composition of Al!Co!Mo Catalyst on Its
Desulfurizing, Deasphalting, and Demineralizing Activity
in Hydrofining of Oil Residues
M. A. Lur’e, L. P. Milova, L. N. Storozheva, I. Z. Kurets, and F. K. Shmidt
Irkutsk State University, Irkutsk, Russia
Boreskov Institute of Catalysis, Siberian Division, Russian Academy of Sciences, Novosibirsk, Russia
Received March 22, 2001
Abstract-Effect of the composition of Al!Co!Mo catalysts on their desulfurizing, deasphalting, and demin-
eralizing activities in hydrofining of black oil and interrelation of these activities with coking and deactivation
of the catalyst are studied.
Study of physicochemical and catalytic character-
istics of catalysts for hydrofining of heavy oil cuts is
important in view of growing spread of this process.
Thus, in the United States the annual output capacity
of heavy cut hydrofining installations in refineries
increased by 33 million tons in the period from 1980
to 1996 [1, 2]. This tendency is initiated primarily
by steadily increasing atmospheric pollution with SO
(about 160 million tons of SO
is annually released all
over the world to the atmosphere as a result of black
oil and coal combustion), so that the steadily growing
demand for environmentally clean motor fuels should
be satisfied by hydrofining of heavy cuts.
In this connection optimization of the composition
of catalysts is one of the most important problem.
Here we report on the effect of the concentration of
the active component of the Al3Co3Mo catalyst on its
desulfurizing, deasphalting, and demineralizing activi-
ties and formation of condensation products (CPs)
on the catalyst surface in hydrofining of black oil
produced from West-Siberian crude oil.
In experiments we used samples with various con-
centrations of the active components and phase com-
positions. The g-Al
support for the catalysts was
prepared by the nitrate method. The catalysts of fixed
composition were prepared by impregnation of the
support calcined at 550oC with solutions of ammoni-
um paramolybdate and cobalt nitrate. The resulting
catalyst mass was air-dried for 24 h, dried at 60370oC
under an IR lamp with intermittent stirring, and in
an oven at 120oC for 4 h. The dried samples were
then calcined in air for 6 h at a fixed temperature from
the range 4503550oC.
The samples thus obtained varied not only in the
Mo and Co concentrations, but also in the relative
content of crystallized Co and Al molybdates and the
degree of their crystallinity. The phase composition
was varied as in [3, 4] using data on the effects of the
sequence of application of Mo and Co to Al
the mode of oxidative thermal treatment of the cata-
lyst mass. The Co/Mo atomic ratio in the samples was
0.40+0.03. The phase composition of the catalysts
was studied by X-ray diffraction analysis on a
DRON-1.5 diffractometer (CuK
monochromator for reflected beam). In data process-
ing we used the external reference method. As refer-
ence mixtures we used g-Al
, and g-Al
The catalyst activity was tested in a high-pressure
flow-through (no recycling) setup. Prior to testing the
samples were sulfidized at 400oC. The testing time
was 243110 h, temperature 3803420oC, pressure
10 MPa, and hydrogen consumption at normal condi-
tions 1000 nl l
. The experimental space velocity
of black oil across the catalyst bed provided the desul-
furization level of 25335%.
In special-purpose experiments we demonstrated
that there is no external-diffusion hindrance of the
process under the experimental conditions. Further-
more, at a grain size of 0.4 mm internal-diffusion
hindrance is not manifested also, which allows an
adequate estimation of the effect of the chemical
composition of the catalyst on its activity.