Chemistry and Technology of Fuels and Oils, Vol. 44, No.

1, 2008

OXIDATIVE DESULFURIZATION OF LUBE OIL DISTILLATES

V. R. Nigmatullin, R. R. Mukhametova, and I. R. Nigmatullin

The problem of manufacturing low-sulfur oils has become much more acute with the increase in refining of
medium-sulfur crudes. The difficulties in obtaining lube oils with a low sulfur content are due to the restricted
selection of feedstock, changes in its composition, and especially the lack of hydrotreating in the refinery.
The method of selective treatment of lube oil distillates with selective solvents would allow eliminating
undesirable aromatic, resinous, and organosulfur compounds and obtaining raffinate of the desired
quality [1]. However, this method is only effective in treating oil distillates from low-sulfur crudes.
Sulfides and thiophenes basically remain in the raffinate. According to the published data, their content
significantly affects the performance properties of the oils. Sulfides in minimal (0.01-0.03 wt. %) amounts play the
role of antioxidants, but their effect is decreased when polycyclic and sulfur-containing aromatic compounds are
simultaneously present in the oils.
This is due to formation of associates which have no inhibiting power. Sulfides in large quantities decrease
the thermochemical stability (formation of a solid phase at high temperature) and intensify corrosion [2].
The low efficiency of selective treatment is due to the close polarity of the sulfur compounds and the
hydrocarbons mixed with them [3].
As recent studies have shown, solving the problem of producing low-sulfur lube oils from medium- and
high-sulfur crudes consists of developing primarily new manufacturing processes based on oxidation reactions.
The proposed method of treating oil distillates obtained from medium- and high-sulfur crudes is based on
oxidation of organosulfur compounds into sulfoxides and sulfones and separating the latter together with
undesirable components (aromatics and resins) from the hydrocarbons by extraction with a selective solvent.
In the first stage, the sulfides contained in the oil cuts are oxidized into sulfoxides with an aqueous
solution of hydrogen peroxide and they are in turn oxidized with formation of a small amount (0.1-0.3 wt. %) of
sulfones. In the second stage, the sulfoxides and sulfones formed are extracted from the oxidation product by
extraction with a selective solvent.
____________________________________________________________________________________________________
RB Petrochemical Refining Institute GUP. Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 1,
pp. 10 11, January February, 2008.
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0009-3092/08/44010010 2008 Springer Science+Business Media, Inc.

The polarity of the sulfur-containing compounds changes sharply as a result of oxidation, and this allows
separating sulfides and thiophenes in the form of sulfoxides and sulfones, together with other undesirable
components, from the hydrocarbon part of the feedstock. The oxidation product obtained contains more polar
organosulfur compounds that primarily pass into the extract phase in selective treatment. The total sulfur content
in the raffinate decreases significantly.
To increase the degree of oxidation of sulfides, the process (with the method in [4]) was conducted in the
presence of a catalyst formic acid.
As an example, let us examine the results of treating III oil cut with N-methylpyrrolidone with the proposed
method (see Table 1). Oxidation was conducted with an aqueous solution of hydrogen peroxide in the presence of
0.03 wt. % formic acid in feedstock. The organic (oxidation product) and aqueous phases formed were separated
by standing for 30 min at 60C.
The feedstock III oil cut and its oxidation product was extracted with N-methylpyrrolidone
according to the three-stage scheme of Nash and Hunter in three extractors: at 52, 57, and 62C in the first case
and at 54, 59, and 64C in the second case.
As Table 1 shows, the total sulfur content in the raffinate obtained by extraction of previously oxidized
feedstock was 2-3 times lower than in the raffinate obtained from the initial feedstock with the same ratio of
feedstock to solvent.
These results indicate the effectiveness of preliminary oxidation in treating oil distillate to remove
organosulfur compounds.
The proposed technology can be an alternative to hydrotreating. However, in contrast to hydrotreating,
it is conducted without hydrogen, at atmospheric pressure, and at a maximum temperature of 70C. A unit for
selective treatment with N-methylpyrrolidone must be supplemented by an oxidation-settling block and a block for
regenerating the catalyst from aqueous solution. The diagram of such a unit is shown in Fig. 1.
Oxidation of oil-cut sulfides is a heterogeneous reaction between two immiscible liquids. For this reason,
in addition to the temperature and nature of the catalyst, the surface area of the contacting phases has a large
effect on the oxidation rate.
A reactor with a stirrer is proposed as the basic unit in the oxidation block and a settling tank is suggested
for removing the organic layer from the aqueous layer. The aqueous layer, which consists of 70% water
and 30% formic acid, goes to the catalyst regeneration block, which is an azeotropic rectification tower. The
regenerated acid is then recycled in the process.
When this process is included in the manufacturing scheme of active oil refineries, the selectivity of the
process increases significantly and the feedstock refining conditions become milder. Takeoff of oil of the required
quality remains at the level corresponding to refining of low-sulfur cuts.
Table 1
Raffinate
Indexes

sample 1

sample 2

oxidation product
of sample 2
of III oil cut

III oil cut

III oil cut

Ratio of feedstock to solvent

1:6

1:4

1:4

Yield of raffinate, wt. %

15.5

36.8

31.5

Refractive index at 50C

1.4841

1.4495

1.4480

6.85

6.11

6.01

888

830.7

831

1.38

0.24

0.4

0.12

Viscosity at 50C, mm /sec

Density at 20C, kg/m

Total sulfur content, wt. %

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Fig. 1. Diagram of the selective treatment unit: 1) formic acid regeneration block;
2) reactor with mixer; 3) settling tank; 4) extraction column; 5, 6) blocks for regeneration
of solvent from raffinate and extract solutions; I) regenerated formic acid; II) water;
III) fresh formic acid; IV) oil cut; V) aqueous solution of hydrogen peroxide; VI) reaction
mixture; VII) aqueous layer; VIII) oxidation product; IX) solvent; X) raffinate; XI) extract.

The proposed process is characterized by high efficiency and low operating costs. The cost of introducing
the oxidation block is incommensurably small in comparison to the cost of constructing a hydrotreating unit.
REFERENCES
1.
N. I. Chernozhukov, Crude Oil Refining and Gas Processing Technology [in Russian], Part 3, Khimiya,
2.

Moscow (1978).
Ya. B. Chertkov, Nonhydrocarbon Compounds in Petroleum Products [in Russian], Khimiya, Moscow

3.

(1964).
A. Kh. Sharipov and V. R. Nigmatullin, Khim. Tekhnol. Topl. Masel, No. 1, 38-40 (2006).

4.

A. Kh. Sharipov, R. M. Masagutov, Z. A. Suleimanov, et al., Neftekhimiya, 29, No. 4, 551 (1989).

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