Chemistry and Technology of Fuels and Oils, Vol. 41, No.

3, 2005

REMOVAL OF SULFUR FROM HYDROTREATED DIESEL FUEL

A. Kh. Sharipov and V. R. Nigmatullin UDC 655.664.245

A simple and ecological two-stage method of removing sulfur from hydrotreated diesel fuel is described.
In the first stage, the sulfur compounds left in the fuel are oxidized by hydrogen peroxide into sulfones,
and in the second stage, the sulfones formed are extracted from the oxidation product by adsorption
with silica gel. The diesel fuel obtained with this method satisfies the new European standards for sulfur
content.

The current world market imposes stiff requirements on the quality of diesel fuels. Most European
governments have switched to use of diesel fuels that satisfy the requirements of standard EN 590 for sulfur
content: maximum of 350 ppm. EU countries must manufacture fuel with a maximum sulfur content of 50 ppm by
June 1, 2005 [1]. Stiffer requirements are being established by the EPA (Environmental Protection Agency) in
the USA [2].
Hydrotreating of diesel fuels is conducted with a feedstock space velocity of 2.5-3 h -1 at a temperature
of 343-358C, hydrogen pressure of 3.5-4 MPa, and hydrogen-containing gas:feedstock ratio of 220-350 m3 /m 3 (in
normal conditions) [3]. In these conditions, up to 90% of the sulfur is removed from the fuel. Incomparably higher
hydrogen and power consumption, development of new catalysts, etc., will be required to bring this index to 99%
according to the European standards which will soon come into force.
This is probably the reason for the heightened interest of many investigators in developing more modern
and less expensive methods of removing sulfur from fuels by oxidative reactions [4, 5]. The essence of these
studies consists of the following.
The difficulty in separating sulfur compounds from diesel cuts is due to the closeness of the polarity of
these compounds and the aromatic hydrocarbons with which they are mixed. In oxidation of sulfur compounds,
their polarity changes significantly [6], which allows easily extracting sulfoxides and sulfones, as more polar
compounds, from diesel cuts with adsorbents and polar solvents. Adsorption of sulfoxides and sulfones on silica
gel is 1000 times greater than adsorption of thiophenes and aromatic hydrocarbons [7].
For oxidation of sulfur compounds, 27-30% aqueous solutions of hydrogen peroxide are proposed. An
important advantage of this method is the absence of other products of decomposition except for water. In

____________________________________________________________________________________________________
Institute of Petrochemistry and Catalysis, Academy of Sciences of Republic of Bashkortostan and Ufa
Scientific Center of Russian Academy of Sciences. Institute of Petrochemical Refining. Translated from Khimiya
i Tekhnologiya Topliv i Masel, No. 3, pp. 42 44, May June, 2005.

0009-3092/05/41030225 2005 Springer Science+Business Media, Inc. 225

addition, improvement and development of hydrogen peroxide production was due to the prospects for using this
oxidant on the industrial scale [8].
However, this method is not profitable for treating fuels with a high sulfur content due to high hydrogen
peroxide consumption [9]. We thus investigated the oxidative method of finishing of hydrotreated diesel fuels
with a low content of sulfur compounds.
Oxidation of organosulfur compounds with hydrogen peroxide is a typical reaction of acid catalysis.
Acids polarize the OO bond in the hydrogen peroxide and accelerate the reaction by decreasing the activation
energy of the transitional state [10]. We investigated the effect of acetic and sulfuric acids and mixtures of the two
on oxidation of sulfur compounds contained in hydrotreated diesel cut. Oxidized sulfur compounds were extracted
from the oxidation product by adsorption with silica gel.
A mixture of straight-run diesel cut with catalytic and thermal gasoils (up to 30 wt. %) manufactured at
Novo-Ufimskii Oil Refinery Open Joint-Stock Company was used as feedstock After hydrotreating, the
hydrogenation product contained 482 ppm total sulfur. As studies on a Finnigan 4021 mass spectrometer (USA)
showed [11], the organosulfur compounds in the hydrogenation product were basically represented by thiophene
methyl derivatives, benzothiophene, and dibenzothiophene, as well as a small amount of derivatives of aromatic
sulfides. The total sulfur content in the treated product was determined on a MKA spectrometer from Asoma
Instruments (USA).
Selection of a method of oxidation that leaves the products of oxidation in the reaction zone for the
minimum time with effective heat and mass exchange is very important for selective oxidation of sulfur compounds
in crude oil cuts. Diesel cut sulfur compounds are oxidized into sulfones in tank equipment with mechanical
stirrers for a relatively long time.
To enhance the process, conducting the process in a column-type reactor in foam-emulsion conditions
where the oxidation rate increases due to an important increase in the phase interface is proposed in [12]. In
addition, oxidation can be conducted continuously in such a reactor.
We investigated oxidation of sulfur compounds to sulfones in hydrotreated diesel cut in foam-emulsion
conditions. Most of the laboratory setup a glass oxidative column (foam-emulsion reactor)
measuring 35 1000 mm was equipped with two serially connected reflux condensers and a heating element with
a thermoregulator.
A porous glass plate that acted as a perforated tray was soldered in the lower part of the column. Foam
was formed in blowing air through a layer of the reacting substances on this tray. The linear air flow rate in the full
section of the reactor was 0.05-0.1 m/sec.
The sulfone content in the oxidation products obtained was determined by IR spectroscopy. The
absorption band at 1320 cm -1 , caused by the stretching vibrations of a sulfone group, corresponds to these

Table 1

Composition of catalyst, g-mole per g-atom of total sulfur Sulfone content in oxidation
sulfuric acid acetic acid product, wt. %
2 0.44
1 0.46
0.15 0.13 0.49
0.2 0.13 0.5
0.15 0.25 0.51
0.2 0.25 0.53

226
 0.6
1
0.4

2
0.2
a
0
40 60 80 100 120 140
t, C

0.6
c, %
1
0.4
2
b
0.2
1.75 2 2.5 3 3.5 4
Q, g-mole/g

0.6
1
0.4
2
0.2
c
0 40 80 120 160 200

Fig. 1. Sulfone content c in oxidation product vs. temperature t (a), hydrogen peroxide
consumption q (b), and oxidation time (c) in the presence of the catalyst; 1) mixed
sulfuric and acetic acids; 2) acetic acid.

compounds in the spectra. The compounds accompanying the sulfones do not have bands in this section of the
spectrum [13].
The dependence of the sulfone content in the oxidation product on the nature and consumption of the
catalyst, hydrogen peroxide consumption, temperature, and duration of oxidation was investigated to determine
the optimum parameters of oxidation of diesel cut sulfur compounds in foam-emulsion conditions.
The activity of acid catalysts glacial acetic and concentrated sulfuric acids and mixtures of them were
compared at a temperature of 100C, oxidation time of 60 min, and hydrogen peroxide consumption of 3 g-mole per
1 g-atom of total sulfur. Consumption of acetic and sulfuric acids varied from 0.2 to 7 g-mole per 1 g-atom of total
sulfur.
It was found that the sulfone content in the oxidation product increased rapidly with an increase in acetic
and sulfuric acid consumption from 0.5 to 2 and from 0.2 to 1 g-mole per 1 g-atom of total sulfur. With a further

227
Table 2

Total sulfur content (ppm)

Sample number
in sample mixed with preceding samples
1 22 22
2 22 22
3 23 22.5
4 23 22.7
5 24 23.2
6 25 23.9
7 25 23.9
8 27 24.4
9 30 24.9
10 32 25.2
11 36 25.8
12 43 36.5
13 48 40.2
14 51 45
15 58 53
16 65 58
17 72 64

increase in acetic acid consumption, the sulfone content almost did not change. It decreased with higher sulfuric
acid consumption. The maximum sulfone content was 0.44-0.46 wt. % with both sulfuric and acetic acid.
In using a mixture of 0.25 g-mole of acetic and 0.15-0.2 g-mole sulfuric acids per 1 g-atom of total sulfur, the
yield of sulfones increased to 0.51-0.53 wt. %, which is 7-8 wt. % higher than the maximum yield in oxidation in the
presence of each of the acids individually (Table 1).
The dependence of the yield of sulfones on the oxidation temperature in the 50-140C range was investigated
for a process time of 60 min and oxidant consumption of 3 g-mole per 1 g-atom of total sulfur. In the presence of
acetic acid, this dependence was described by an extreme curve with a maximum corresponding to a yield
of 0.39 wt. % sulfones at 100C (see Fig. 1a).
At temperatures above 100C, the yield of sulfones decreased, which could be due to blowing out of the
system in conditions of foam-emulsion oxidation of acetic acid, whose boiling point is 188C. In oxidation in the
presence of a mixture of 0.2 g-mole sulfuric and 0.25 g-mole acetic acid per 1 g-atom total sulfur, a high
sulfone content was attained in the oxidation product more than 0.5 wt. % in a wide range of
temperatures from 70 to 120C.
To determine the oxidant consumption that ensures the maximum degree of conversion of sulfur compounds
into sulfones, the diesel fuel cut was oxidized at different hydrogen peroxide consumption (from 2 to 3.5 g-mole
per 1 g-atom total sulfur) in the presence of acetic acid and a mixture of acetic and sulfuric acids in the ratios
indicated above. The experiments were conducted at the optimum catalyst consumption, temperature of 100C,
and oxidation time of 60 min.
The highest yield of sulfones was attained in oxidant consumption of 3 g-mole per 1 g-atom total sulfur
(see Fig. 1b). At higher hydrogen peroxide consumption, the yield of sulfones did not increase. At the same

228
oxidant consumption, the yield of sulfones in the presence of a mixture of acetic and sulfuric acids was higher than
with acetic acid alone.
The effect of the oxidation time in the range of 10 to 150 min in the presence of mixed sulfuric and acetic
acids and acetic acid alone on the yield of sulfones (see Fig. 1c) was investigated at a temperature of 100C and
hydrogen peroxide consumption of 3 g-mole per 1 g-atom total sulfur. The highest sulfone content in the oxidation
products was attained in oxidation for 60-100 min.
The following conditions of oxidation of sulfur compounds in the hydrotreated cut into sulfones are
recommended based on the results obtained: linear air flow rate in full reactor section of 0.05-0.1 m/sec; temperature
of 100C; oxidation time of 60 min; hydrogen peroxide, acetic and sulfuric acid consumption of 3, 0.25, and
0.2 g-mole per 1 g-atom total sulfur.
Treatment of the oxidation product to remove sulfones was investigated by adsorption on ASK technical
silica gel [14]. The method is based on the much higher adsorbability of sulfones in comparison to hydrocarbons.
The silica gel was ground, the 149-74 mm fraction was taken off, sulfate ions were washed off with water,
and the silica gel was first dried at normal temperature and then for 12 h at 145-150C. Then 75 g of adsorbent
prepared in this way was placed in a glass column with an internal diameter of 15 mm and 850 ml of oxidized
feedstock was passed through it, taking off 50 ml of purified product at the bottom of the column.
The total sulfur content was determined in each sample. In addition, each sample was mixed with the
preceding samples and the total sulfur content was determined. The results of the analysis are reported
in Table 2. The total sulfur content in a mixture of the first 14 samples was les than 50 ppm, which satisfies the new
requirements in standard EN 590.

REFERENCES
1. I. V. Babich and J. A. Moulin, Fuel Proces. Techn., 82, 607-631 (2003).
2. R. L. Levy, A. S. Rappas, and S. J. Stephen Decanio, Hydrocarb. Process., 80, No. 5, 241-245 (2001).
3. A. Yu. Mupirov, E. L. Talisman, D. O. Belikov, et al., Neftepererab. Neftekhim., No. 1, 17-20 (2003).
4. US Patent No. 6 274 785, 6 402 940, 6 402 939, 6 500 219.
5. F. Zannikos, E. Lois, and S. Stournas, Fuel Proces. Techn., 42, 35-45 (1995).
6. C. W. Cumper and A. J. Vogel, J. Chem. Soc., No. 1, 3521-3526 (1959).
7. G. D. Galpern, T. S. Bobruiskaya, and E. S. Brodskii, Petroleum Institute Research [in Russian], Izd. AN
SSSR, Moscow (1959), pp. 51-57.
8. G. A. Seryshev, Chemistry and Technology of Hydrogen Peroxide [in Russian], Khimiya, Leningrad
(1984).
9. F. M Collins, A. R. Lucy, and C. Sharp, J. Molec. Catal. A: Chemical, 20, 1303-1306 (1997).
10. L. S. Levin, J. Org. Chem., 20, 1303-1306 (1955).
11. R. M. Masagutov, E. A. Kruglov, J. N. Popov, et al., in: Tenth Intern. Sympos. on the Organic Chemistry
of Sulphur, September 5-10, 1982, Univ. College of North Wales, Bangor, England (1982), pp. 129-131.
12. USSR Inventors Certificate No. 469326.
13. N. N. Anashkina and D. M. Zagryatskaya, Referativn. Sbor. TsNIITEkhima Metody Analiza Kontrolya
Proizvodstva v Khim. Promyshl., No. 4, 16-20 (1974).
14. E. N. Karaulova, G. D. Galpern, L. D. Aristova, et al., Neftekhimiya, 5, No. 5, 753-759 (1965).

229