ISSN 1070-4272, Russian Journal of Applied Chemistry, 2015, Vol. 88, No. 3, pp. 449−457. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © S.A. Antonov, N.N. Tomina, N.M. Maximov, A.A. Pimerzin, M.V. Babintseva, I.I. Zanozina, 2015, published in Zhurnal Prikladnoi Khimii,
2015, Vol. 88, No. 3, pp. 444−452.
AND ION EXCHANGE PROCESSES
Chemical Transformations of Components of Rafﬁ nates
from Selective Reﬁ ning of Sulfurous Crude Oils
in the Process of Hydrotreating in Production
of Base Oils of API Group II
S. A. Antonov
, N. N. Tomina
, N. M. Maximov
, A. A. Pimerzin
M. V. Babintseva
, and I. I. Zanozina
United Research and Development Center, Leninskii pr. 55, k. 1, Moscow, 119333 Russia
Samara State Technical University, Molodogvardeiskaya ul. 244, Samara, 443100 Russia
Middle Volga Research Institute of Oil Reﬁ ning, promzona a/ya 71, Novokuibyshevsk, Samara oblast, 446200 Russia
Received April 4, 2015
Abstract–Variation of the chemical composition and properties of rafﬁ nates from selective reﬁ ning of sulfurous
crude oils in the course of hydroﬁ ning in the presence of a zinc-modiﬁ ed catalyst was studied. In hydroﬁ ning of the
rafﬁ nate obtained at the N-methylpyrrolidone : distillate weight ratio of 1.2 : 1 at 360°С, “light” aromatic hydrocar-
= 1.4900–1.5100) start to undergo hydrogenation with the formation of high-index parafﬁ n–naphthene
hydrocarbons. At the same temperature, tetra-, penta-, and hexacyclic naphthenes undergo active hydrodecycli-
zation with the formation of high-index mono-, bi-, and tricyclic structures. From the hydrogenizates obtained
at 360 and 380°С, after dewaxing, base oil samples were obtained with the sulfur content of 0.020–0.024 wt %,
content of saturated compounds of 91.2–91.4 wt %, and viscosity index of 88–91, meeting the requirements of API
group II. There are prospects for further improving the quality of the hydrogenizates by varying the hydroﬁ ning
process parameters (decreasing the space velocity to 0.5–0.75 h
, increasing the hydrogen circulation factor).
Today Russia gradually passes to the production
and consumption of fuels of Euro-4 and Euro-5 classes.
With such fuels, the sulfur content of the motor oil
becomes an important factor. This is caused by the fact
that the vaporizable fraction of the base oil burns out
in the engine with the formation of environmentally
harmful sulfur oxides SO
. Therefore, in accordance
with the modern requirements, the sulfur content of
the base oil should be reduced to 0.03 wt %. The API
classiﬁ cation of base oils is commonly accepted in the
world practice. Along with restrictions of the sulfur
content, requirements are also imposed upon the content
of saturated (parafﬁ n–naphthene) hydrocarbons and
viscosity index. When passing to Euro-4 and -5 fuels,
it is necessary to use in oil production base stocks of
API groups II and III .
In Russia, the total production volume of base oils of
groups II and III does not exceed 1% of the total volume of
oil production , which is insufﬁ cient for passing to fuels
of Euro grades. It should be noted that many producers
have potential for the production of high-quality oils.
Available hydroﬁ ning installations allow hydroﬁ ning to
be performed at a pressure of up to 5.0 MPa.
Data on chemical transformations of oil fractions
of sulfurous crude oils, in particular, of rafﬁ nates from
selective reﬁ ning with N-methylpyrrolidone (N-MP), in
the presence of modern hydroﬁ ning catalysts are few.
Therefore, it is topical to study chemical transformations
that separate groups of hydrocarbons present in rafﬁ nates
from selective refining undergo in the course of
hydroﬁ ning to obtain low-sulfur high-index base oils of
API group II.