ISSN 09655441, Petroleum Chemistry, 2014, Vol. 54, No. 1, pp. 51–57. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © E.B. Krivtsov, A.K. Golovko, 2014, published in Neftekhimiya, 2014, Vol. 54, No. 1, pp. 52–58.
The Kinetics of Oxidative Desulfurization of Diesel Fraction
with a Hydrogen Peroxide–Formic Acid Mixture
E. B. Krivtsov and A. K. Golovko
Institute of Petroleum Chemistry, Siberian Branch, Russian Academy of Sciences, Akademicheskii pr. 3, Tomsk, 634055 Russia
email: john@ipc.tsc.ru
Received May 13, 2013
Abstract—The dependence of the oxidation rate of sulfur compounds on duration, oxidation temperature,
and amount of the introducing oxidizer has been demonstrated with the straightrun diesel with a high initial
sulfur content. The data for the oxidation rates of benzo and dibenzothiophene homologues depending on
the amount and the position of alkyl substituents in them during competing oxidation reactions of different
diesel components have been obtained. The effective rate constants have been calculated for the oxidation
reactions of the sulfur compounds during the oxidative desulfurization. The mechanism of the interaction of
diesel sulfur compounds with the oxidant is proposed.
Keywords: diesel fraction, sulfurcontaining compounds, oxidative desulfurization, rate constant
DOI: 10.1134/S0965544114010083
Gasoline, diesel, and nonvehicle fuels comprise
75–80% of the total amount of oil distillation prod
ucts. A continuous rise in the proportion of sulfur and
highsulfur crude oils arriving at refineries and tight
ening environmental requirements to quality of the
product fuels make resolving the problem of deep de
sulfurization of commercial petroleum products an
urgent task. In Europe it is allowed to use motor fuels
with a sulfur content no more than 0.005% since 2005
and up to 0.001 wt % since January 2009 [1]. The
EURO3 standard (sulfur content is no more than
0.035 wt %) came in force in Russia since January
2009 and EURO4 (0.005 wt % sulfur), since January
2010 [2].
aration methods, since their properties significantly
differ from those of petroleum hydrocarbons. Further
more, the process is more costeffective because
cheaper oxidants, such as air oxygen, hydrogen perox
ide, and organic peroxides, are used [11–16].
The purpose of the present work was to establish
the kinetic relations of the composition of diesel sulfur
compounds during oxidative desulfurization (combi
nation of oxidation by a hydrogen peroxide–formic
acid mixture with the subsequent adsorption removal
of the oxidized sulfur compounds) involving competi
tive oxidation reactions of different diesel compo
nents.
The main industrial process used currently for
removal of sulfur is catalytic hydrodesulfurization.
This method allows up to 90% of sulfur to be extracted
from petroleum products. Bringing the degreed of de
sulfurization to 97–99% (EU and US standards) will
require an increase in the capital and operational costs
of production lowsulfur fuel. The increase of the
motor fuel production costs is mainly determined by
an increase in the hydrogen partial pressure in the sys
tem and a decrease of the unit throughput. These fac
tors explain the urgency of search for new, nontradi
tional processes for sulfur removal during petroleum
refining [3, 4]. One of these processes is oxidative de
sulfurization [5–10]. Oxidative desulfurization can be
run at room temperature and atmospheric pressure,
conditions that allows the process costs to be substan
tially decreased. Sulfur compounds during desulfur
ization are oxidized to sulfones and sulfoxides, which
are subsequently easy to remove by conventional sep
EXPERIMENTAL
The object of study was the straightrun diesel frac
tion 200–360°С from the Ryazan refinery (GOST
(State Standard) 217799) with a high total sulfur (St)
content of 1.19% (GOST R 418592002) including
sulfide sulfur of 0.30 wt %. The group type composi
tion of sulfur compounds and hydrocarbons (HCs) of
this fraction are presented in Tables 1 and 2.
The concept scheme of oxidation of the diesel frac
tion, adsorption separation, and product analysis is
given below.
The oxidation of the diesel fraction with hydrogen
peroxide (37 wt %, GOST 17788, medical grade,
available from Lega, Dzerzhinsk) and formic acid
(85 wt %, GOST 584873 or (runs 1–3) chemically
pure grade, Germany) was carried out according to the
procedure detailed in [17, 18] at 35°C with varying the
process time from 30 min to 8 h, in a reactor at a stir
51
52
KRIVTSOV, GOLOVKO
Table 1. Group type composition of sulfur compounds of
the diesel fraction
Sulfur
compounds
Sulfur content
in sulfur compounds, wt %
Sulfides
Thiophenes
Including:
Benzothiophenes
Dibenzothiophenes
0.26
0.93
0.63
0.30
Table 2. Hydrocarbon type composition of the diesel frac
tion
Hydrocarbons
Content, wt %
Saturated
Monoaromatic
Biaromatic
Triaromatic
53.4
28.7
8.2
7.9
ring rate of 2100 rpm, and varying the total sulfur to
hydrogen peroxide molar ratio from 1 : 1 to 1 : 20; the
Н2О2 : HCOOH molar ratio was 3 : 4. The degree and
the rate of the oxidation of sulfur compounds in this
heterogeneous system (mixture of hydrogen peroxide
and formic acid solutions with the diesel fraction)
mainly depend on degree of its homogenization.
Fraction
Oxidation by H2O2 + HCOOH mixture
Removal of oxidation
products by adsorption on SiO2
Refined fraction
Oxidation products
Adsorption on Al2O3
Saturated HCs Monoarenes Biarenes Triarenes
Scheme of the experiment.
The polar products of oxidation were removed
by adsorption on silica gel of the ASKG brand
(GOST 395676, Sorbis, Moscow) at a sample to sor
bent mass ratio of 3 : 1. The flow rate of the solution
subjected to separation through the sorbent bed was
0.2 cm3/min. The sample residues were washed off the
silica gel with nhexane; in this case, the polar com
pounds formed by oxidation are quite strongly
retained on the adsorbent surface, thereby making
them easy to separate from the hydrocarbon portion.
The hydrocarbon type composition of the initial
distillate and its oxidative desulfurization products was
determined using liquid–adsorption chromatography
on activated aluminum oxide of Brockman activity
grade II (STO (Company Standard) 12452011 proce
dure, FR (Federal Register) no. 1.31.2011.10349), by
eluting the fractions of saturated, mono, and biaro
matic hydrocarbons (HCs) with nhexane; triaromatic
HCs, with a hexane + benzene mixture (3 : 1 by vol
ume); and resins, with a 1 : 1 ethanol–benzene mix
ture (by volume). The separation of different HC
classes was monitored by measuring the electronic
absorption spectra of eluate taken on a UNICO 2804
spectrometer. The losses during the solvent distillation
off the eluates did not exceed 2.5 wt %.
The individual composition of different hydrocar
bons was determined by gas–liquid chromatography
on a Kristall2000M chromatograph (25 m × 0.22 mm
fused silica capillary column with SE54 stationary
phase, helium was a gas carrier, is flameionization
detector). The saturated and aromatic hydrocarbon
fractions were analyzed in linear temperature pro
gramming mode from 80 to 290°С at heating rates of
15 and 2°C/min, respectively. The sulfur compounds
(SC) were determined using a linear temperature rise
from 50 to 290°С at a rate of 4°C/min.
RESULTS AND DISCUSSION
It is known that saturated compounds (alkanes,
isoalkanes, naphthenes) are the most stable during
oxidation. Among aromatic hydrocarbons, the stabil
ity to oxidation falls in the order: monoaromatic >
biaromatic > triaromatic > polyaromatic. The analysis
of the HC type composition of the initial diesel frac
tion and its oxidative desulfurization products showed
that the oxidation of the diesel fraction with the mix
ture of hydrogen peroxide and formic acid leads to sig
nificant changes (Table 3). For example, the incre
ment in the amount of saturated HCs is up to 23.3 wt %,
with the oxidation time of 4 h or longer (followed by
adsorption purification) having almost no effect on
the hydrocarbon type composition of the products.
The change in the type composition is caused by the
removal of the oxidation products of aromatic hydro
carbons and sulfur compounds during the adsorption
purification. The higher degree of removal of monoar
omatic hydrocarbons relative to the bi and triaro
matic ones is due to their content in the fraction,
which is higher by an order of magnitude . The oxida
tion of triaromatic compounds is more efficient at the
initial stage, than biaromatic ones, but the total con
tent of these HCs levels off during longtime (more
than 4 h) oxidation with the mixture of hydrogen per
oxide and formic acid and differs only by 0.4 wt %.
Figure 1 shows the change in the sulfur content of
the oxidative desulfurization products. During the first
PETROLEUM CHEMISTRY
Vol. 54
No. 1
2014
THE KINETICS OF OXIDATIVE DESULFURIZATION OF DIESEL FRACTION
53
Table 3. Hydrocarbon type composition of oxidative desulfurization products depending on the time of oxidation with the
H2O2/HCOOH mixture (oxidation temperature 35°C)
Oxidation time, min
Hydrocarbon
content, wt %
initial
fraction
30
60
120
180
240
300
360
55.24
44.76
64.73
35.27
69.75
30.25
73.75
26.25
75.97
24.03
78.07
21.93
78.26
21.74
78.50
21.50
28.74
8.16
7.86
24.11
6.19
4.97
21.48
5.37
3.40
18.94
4.57
2.74
17.83
3.71
2.49
17.22
2.57
2.13
17.14
2.52
2.07
17.05
2.43
2.02
Σ Saturated
Σ Aromatic
Including:
monoaromatic
biaromatic
triaromatic
half hour of the oxidation of the diesel fraction with
the Н2О2–НСООН mixture, as much as 84 rel. % of
sulfur is removed. An increase in the oxidation time to
6 h allows more than 12 rel. % of sulfur to be addition
ally removed.
The change in the amount of sulfur compounds in
the samples obtained was calculated from chromato
graphic analysis data (Table 4). Benzothiophene (BT)
and its methylated derivatives (С1BT) were not
detected in the fraction. According to the data
obtained, sulfur in all the samples occurs mostly in
thiophene structures, with the concentration of BT
homologues being higher or almost the same as that of
dibenzothiophene (DBT) homologues. The sulfur
content in the BT homologues of the initial diesel frac
tion is 0.63 wt %, whereas that in DBT and its homo
logues does not exceed 0.30 wt %; the rest of the sulfur
occurs in organic sulfides (0.26 wt %). The group type
composition of sulfur compounds in the products of
oxidative desulfurization (for 6 h) substantially alters:
sulfides almost completely disappear (their content
drops to 0.0182 wt %), the ratio of BT and DBT
homologues changes, and products of oxidation of
sulfur compounds appear.
Table 5 shows the degrees removal of different
groups of sulfur compounds during the oxidative de
sulfurization of the diesel fraction. It is seen that
the efficiency of removal of the BT and DBT homo
logue falls with the increasing number and size of alkyl
substituents. The relatively low degree of removal of
С3BT is explained by their initially high content in
the diesel fraction. It is likely that under these condi
tions the oxidation with the hydrogen peroxide–for
mic acid mixture proceeds to a significant extent not
through the straightforward formation of performic
acid, unlike the case described in [19, 20]. In the
absence of compounds that facilitate phase transfer of
the interacting components (similar to those described
in [21, 22]), the following scheme is the most proba
ble: formic acid partially dissolves in the diesel frac
tion, and an aromatic compound (hydrocarbon or sul
fur compound) is protonated then. The intermediate
product (charge transfer complex) due to its polarity is
pushed to the aqueous solution/diesel fraction inter
face, at which it is oxidized by a hydrogen peroxide
molecule:
HCOOH
HCOO–
+
S
S
••
The sulfur atom containing the lone electron pair
on the 3p sublevel is the most convenient protonation
site. An increase in number or size of the alkyl substit
uents substantially hinders the protonation of an aro
matic compound, thus, affects the rate of its oxidation.
However, compounds containing substituents in the 4
and 4,6positions (dibenzothiophene homologues are
Vol. 54
No. 1
S
O
H
PETROLEUM CHEMISTRY
+H2O2
–H2O + HCOOH
2014
the most hardtoremove by hydrotreating) are almost
completely removed using the hydrogen peroxide–
formic acid mixture (Table 4).
To determine the kinetic parameters of the oxida
tive desulfurization of the diesel fraction, a formalized
kinetic model was proposed as detailed in [23] (Fig. 2).
54
KRIVTSOV, GOLOVKO
Table 4. Sulfur content in different types of sulfur compounds depending on the time of oxidation by H2O2/HCOOH
Sulfur content in sulfur compounds, wt %
Oxidation time, min
Initial fraction
30
60
120
180
240
300
360
ΣC2BT
ΣC3BT
ΣC4BT
DBT
ΣC1DBT
ΣC2DBT
0.0983
0.0136
0.0048
0.0032
0.0023
0.0011
0.0010
0.0008
0.3417
0.0348
0.0195
0.0151
0.0134
0.0117
0.0110
0.0106
0.1906
0.0326
0.0314
0.0283
0.0206
0.0151
0.0074
0.0028
0.0518
0.0069
0.0048
0.0035
0.0016
0.0010
0.0003
0.0003
0.1375
0.0115
0.0075
0.0063
0.0032
0.0030
0.0010
0.0012
0.1063
0.0227
0.0140
0.0123
0.0096
0.0083
0.0041
0.0025
Table 5. Degree of removal of sulfur compounds by oxidative desulfurization
Removal degree, rel. %
Oxidation time, min
ΣC2BT
ΣC3BT
ΣC4BT
DBT
ΣC1DBT
ΣC2DBT
30
86.2
64.6
66.8
93.0
88.3
76.9
180
97.7
86.4
79.0
98.4
96.7
90.2
360
99.2
89.2
97.1
99.7
98.8
97.5
For this model, it was assumed that the oxidation
reactions are parallel and not autocatalytic. In addi
tion, it was accepted that the oxidation of 1 mole of a
sulfur compound or aromatic hydrocarbon requires no
more than 1 mole of oxidant (i.e., sulfur compounds
are oxidized to the corresponding sulfones). Accord
ing to published data, the oxidation of sulfones to the
S content of products, wt %
1.2 1.190
1.0
0.8
0.6
0.4
0.194
0.2
0
0.125 0.091
0.087 0.067 0.060
0.047
1
2
5
3
4
Oxidation time, h
6
0.046
7
Fig. 1. Decrease in the sulfur content of the oxidative de
sulfurization products of the diesel fraction (oxidation by
H2O2–HCOOH mixture) with time.
8
sulfoxides occurs at significantly lower rates; there
fore, the pseudofirstorder rate law for the oxidation
reactions of sulfur compounds was accepted in further
calculations. Testing the reaction order by the graphi
cal method (plotting ln(cS) versus oxidation time)
showed the time dependence to be linear, suggesting
that the firstorder rate equation can be used for fur
ther calculations (in agreement with published data
[24, 25]). Since the oxidant concentration is taken in a
substantial excess, the effective rate constant which
includes the oxidant concentration was calculated.
The constants were calculated by the equation for the
⎛c ⎞
firstorder reaction k ef = 1 ln ⎜ S 0 ⎟ , where cS is the ini
t ⎝ cS ⎠
tial concentration of a sulfur compound of a particular
type and cS is the concentration of the sulfur com
pound at a time t.
The results of calculation of the oxidation rate con
stants for the groups of BT and DBT homologues are
presented in Fig. 3. It is seen that the effective oxida
tion rate constants for the oxidation by the Н2О2–
НСООН system decreases as the number of the alkyl
substituents in the benzo and dibenzothiophene
homologues increases. This is a consequence of
enhancement of steric hindrances around the sulfur
atom electron pairs with the increasing number of the
alkyl substituents. It was found that the most heavily
substituted BT (ΣС4BT) and DBT (ΣС2DBT)
homologues have the least values of their oxidation
rate constants.
PETROLEUM CHEMISTRY
Vol. 54
No. 1
2014
THE KINETICS OF OXIDATIVE DESULFURIZATION OF DIESEL FRACTION
Diesel fuel components:
ΣС2DBT
Excess oxidant
Monoaromatic hydrocarbons
k1
Biaromatic hydrocarbons
k2
Triaromatic hydrocarbons
k3
0.38
ΣС1DBT
0.58
0.50
DBT
Sulfides
BT and its homologues
DBT and its homologues
ΣС4BT
Oxidation
products
k4
k6
0.54
ΣС2BT
0.56
0.1
0.2
0.3
0.4
0.5
0.6
Fig. 3. Effective rate constants of oxidation of SC groups
by mixture of hydrogen peroxide–formic acid.
The values of the effective oxidation rate constants
obtained for the homologues of sulfur compounds
(Fig. 3) are lower than the relevant values reported in
[20, 26]. For example, de Filippis et al. [26] presented
the oxidation rate constants for sulfur compounds as
obtained in model experiments, the oxidation of one
or several individual sulfur compounds in an organic
solvent (saturated hydrocarbons are most frequently
used in order to exclude the oxidation reactions of the
solvent proper). The values of the effective oxidation
rate constants calculated in this work reflect the rate of
oxidation of the benzo and dibenzothiophene homo
logue groups present in the initial diesel fraction. In
this case, as has been mentioned above, the oxidation
reactions of all groups of sulfur compounds present in
the feedstock (sulfides, BT and DBT homologues)
proceed simultaneously and the oxidant is partially
consumed for oxidation of aromatic hydrocarbons,
which also leads to a decrease in the rates of oxidation
of the sulfur compounds.
Figures 4a and 4b present the values of the effective
oxidation rate constants for the of С1 and С2DBT
homologues identified (names of isomers are given on
the ordinate in the order of increasing retention time
of the compounds). The alkyl substituents in the
dibenzothiophene homologues exhibit two effects that
influence the oxidation rate in opposite manners, the
steric effect when the substituents attached in the
immediate vicinity of the lone electron pairs of sulfur
atom screen them from attacking by electrophilic par
ticles, thereby decreasing the oxidation rate, and the
positive inductive effect (+I), which extends over the
C–Cbond chain and leads to an increase of the elec
tron density in the conjugated aromatic system,
thereby facilitating electrophilic addition reactions.
Vol. 54
ΣС3BT
Effective rate constants, s–1
Fig. 2. Formalized kinetic model for the oxidation process
of components of the diesel fraction.
PETROLEUM CHEMISTRY
0.38
0
k5
55
No. 1
2014
The influence of the position of the methyl substit
uent (Fig. 4a) on rate constants of oxidation of meth
yldibenzothiophene (MDBT) homologues was
revealed. There are all four possible MDBT isomers in
the diesel fraction, although the isomers bearing the
methyl group in the 2 and 3positions are chromato
graphically unresolved. The oxidation of 4MDBT in
which the methyl group is in the closest position to the
lone electron pair of the sulfur atom, creating the
greatest steric hindrances, proceeds at the highest rate.
This is an indication of the significant predominance
of the +Ieffect over the steric hindrance created by
the methyl group. The oxidation rate constant of total
(2+3)MDBT isomers is slightly lower, since the influ
ence of the +Ieffect weakens. The least value of
the oxidation rate constant is for 1MDBT: there no
+Ieffect, since the influence of the inductive effect is
negligible along the chain of more than four bonds.
The steric effect of the methyl group (despite the
greatest distance from the sulfur atom) leads to the fact
that the value of the oxidation rate constant is smaller
for 1MDBT (0.47 s–1) than for DBT (0.50 s–1).
2Ethyldibenzothiophene has the highest oxida
tion rate constant (Fig. 4b). The rate constant of
4ethylDBT oxidation is almost two times below that
of DBT. The steric effect of the ethyl group in the
4position dominates over its +Ieffect (in contrast to
the methyl group). The position of the methyl groups
in the DMDBT isomers has a significant effect on
the oxidation rate constants. 2,4DMDBT and
4,6DMDBT are oxidized faster than DBT
(keff = 0.58 s–1). There is the concerted orientation of
the +Ieffect of the methyl groups in the former iso
mer, which leads to an increase of the electron density
in the conjugated aromatic system and facilitates
interaction with electrophilic particles. The combined
positive inductive effect of the methyl groups in
4,6DMDBT dominates over the steric hindrances to
the electrophilic attack at the lone electron pair of the
56
KRIVTSOV, GOLOVKO
(а)
1MDBT
(2 + 3)MDBT
4ETDBT
0
(b)
1.7/1.9/3.4DMDBT
1.3DMDBT
1.4/1.6/1.8DMDBT
2.7/2.8/3.7DMDBT
2.6/3.6DMDBT
2.4DMDBT
0.47
2ETDBT
0.63
4.6DMDBT
0.66
4ETDBT
0.1 0.2 0.3 0.4 0.5 0.6 0.7
0
Effective rate constants, s–1
0.26
0.26
0.47
0.24
0.38
0.58
0.80
0.58
0.43
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Effective rate constants, s–1
Fig. 4. Effective rate constants of oxidation of BT and DBT homologues by the hydrogen peroxide–formic acid mixture:
(a) methyldibenzothiophene (MDBT), (b) dimethyl and ethyldibenzothiophene (DMDBT and ETDBT).
sulfur atom, as in the case of 4MDBT. However, the
rate constant of 4,6DMDBT is below that of
4MDBT because of the enhanced hindrance of the
sulfur atom (by the second methyl group). The rate of
oxidation of the other identified DMDBT isomers is
lower than that of DBT. Note that the isomers con
taining one of the methyl groups in the 4 or 6posi
tion are characterized by higher values of the effective
oxidation rate constants.
In the oxidation of sulfur compounds, the value of
kef substantially depends on the hindrance of the sulfur
lone electron pair by alkyl substituents. Relatively low
effective rate constants for oxidation by the Н2О2–
НСООН system are due to the fact that the reaction
occurs predominantly through the protonation step in
which the polar transition state is formed, not through
the formation of performic acid as described in [20].
It is known [1, 3] that the presence of alkyl substit
uents at the 4 and 4,6positions in methyl and di
methyldibenzothiophenes, respectively, leads to a sig
nificant decrease in the rates of hydrodesulfurization
of these compounds. This is due to the quite close
location of the alkyl groups, which sterically hinder
the coordination of the DBT molecule through the
lone electron pair of the sulfur atom to the catalyst
active site. The +Ieffect plays the significant role in
the oxidative desulfurization—the closer the alkyl
substituent to the sulfur atom, the stronger the effect.
The interplay of the +Ieffect and steric hindrances
due to the alkyl group size determines the reactivity of
DBT homologues in their oxidative desulfurization. In
many cases, it is in the 4 or 4,6positions that the
presence of alkyl substituents enhances the reactivity
of a DBT homologue.
Thus, the oxidation of the diesel fraction with a
high total sulfur content (1.19 wt %) with the mixture
of hydrogen peroxide and formic acid (35°С, 8 h) fol
lowed by the adsorption of the oxidation products
allows the degree of desulfurization of 96 rel. % to be
achieved. The sulfur compounds and, in part, aro
matic hydrocarbons are predominantly oxidized, with
the degree of removal of benzo and dibenzothiophene
derivatives decreasing as the number of their substitu
ent groups decreases. In terms of the proposed formal
ized mechanism and the kinetic model of transforma
tion of the diesel fraction components during the oxi
dative desulfurization, the kinetic parameters of
oxidation have been calculated. The differences in the
reactivity of sulfur compounds depending on the
degree of their substitution and the position of alkyl
radicals have been revealed. It has been shown that
the stability of the diesel sulfur compounds in oxida
tion by the Н2О2–НСООН mixture falls in the order:
С2DBT = С4BT > DBT > С3BT > С2BT >
С1DBT.
REFERENCES
1. S. Eijsbouts, A. A. Battiston, and G. C. van Leerdam,
Catal. Today 130, 361 (2008).
2. M. I. Levinbuk, S. D. Netesanov, A. A. Lebedev, et al.,
Pet. Chem. 47, 230 (2007).
3. I. V. Babich and J. A. Moulijn, Fuel 82, 607 (2003).
4. R. Javadli and A. de Klerk, Appl. Pet. Res. 1 (1–4), 3
(2012).
5. A. Kh. Sharipov and V. R. Nigmatullin, Pet. Chem. 45,
371 (2005).
6. A. V. Anisimov and A. V. Tarakanova, Ross. Khim. Zh.
7 (4), 32 (2008).
7. B. Pawelec, R. M. Navarro, J. M. CamposMartin, and
L. G. Fierro, Catal. Sci. Technol. 1, 23 (2011).
8. A. M. Aitani, M. F. Ali, and H. H. AlAli, Pet. Sci.
Technol. 18, 537 (2000).
9. J. M. CamposMartin, M. C. CapelSanchez, P. Perez
Presas, and J. L. G. Fierro, J. Chem. Technol. Biotech
nol. 85, 879 (2010).
10. J. Zongxuan, L. Hongyinga, Z. Yongna, and L. Can,
Chin. J. Catal. 32, 707 (2011).
11. E. V. Rakhmanov, D. Tszinyuan, O. A. Fedorova, et al.,
Khim. Tekhnol., No. 1, 31 (2011).
12. Fa Tang Li, Ying Liu, and Zhimin Sun, Energy Fuels
24, 4285 (2010).
PETROLEUM CHEMISTRY
Vol. 54
No. 1
2014
THE KINETICS OF OXIDATIVE DESULFURIZATION OF DIESEL FRACTION
13. Ngo Yeung Chan, TingYang Lin, and Teh Fu Yen,
Energy Fuels 22, 3326 (2008).
14. S. Otsuki, T. Nonaka, and N. Takashima, Energy Fuels
14, 1232 (2000).
15. A. A. Kazakov and G. V. Tarakanov, Neftepererab.
Neftekhim., No. 4, 8 (2012).
16. M. S. Mullakaev, D. F. Asylbaev, G. B. Veksler, and
D. A. Baranov, Oborud. Tekhnol. Neftegaz. Komple
ksa, No. 4, 38 (2010).
17. Yu Guoxian, Lu Shangxiang, Chen Hui, and Zhu.
Zhongnan, Energy Fuels 19, 447 (2005).
18. E. B. Krivtsov and A. K. Golovko, Khim. Interesakh
Ustoich. Razvit., No. 1, 89 (2009).
19. P. de Filippis and N. Verdone, Ind. Eng. Chem. Res. 48,
1372 (2009).
PETROLEUM CHEMISTRY
Vol. 54
No. 1
2014
57
20. P. de Filippis, M. Scarsella, and N. Verdone, Ind. Eng.
Chem. Res. 49, 4594 (2010).
21. Dishun Zhao, Hongwei Ren, Jianlong Wang, et al.,
Energy Fuels 21, 2543 (2007).
22. A. di Giuseppe, M. Crucianelli, F. de Angelis, et al.,
Appl. Catal. B: Environ. 89, 239 (2009).
23. E. B. Krivtsov, Candidate’s Dissertation in Chemistry
(Tomsk, 2011) [in Russian].
24. E. TorresGarcia, A. Galano, and G. RodriguezGat
torno, J. Catal. 282, 201 (2011).
25. Wenshuai Zhua, Guopeng Zhub, Huaming Li, et al.,
J. Mol. Catal. A: Chem. 347, 8 (2011).
26. P. de Filippis, L. Giuseppe, M. Scarsella, and N. Ver
done, Ind. Eng. Chem. Res. 50 (18), 10452 (2011).
Translated by K. Aleksanyan