Oxidative Desulfurization Using Polyoxometalates

C. Komintarachat and W. Trakarnpruk*

Petrochemistry and Polymer Science, Faculty of Science, Chulalongkorn UniVersity, Bangkok 10330, Thailand

Oxidative desulfurization of model compounds (benzothiophene, dibenzothiophene, 4,6-dimethyldibenzothiophene) with hydrogen peroxide/acetic acid using polyoxometalates as catalysts has been studied. The
tetrabutylammonium salts of [W6O19]2-, [V(VW11)O40]4-, [PVW11O40]4-, and [PV2Mo10O40]4- were prepared,
and their activities were compared with (VO)2P2O7. The experimental results show that the highest active
catalyst is [V(VW11)O40]4-. The method was also used for the treatment of gas oil. The combination of solvent
extraction and alumina adsorption can efficiently separate sulfone products. The resulting oil contained less
than 0.055% sulfur, and this corresponds to 90 % removal.
Introduction
Sulfur compounds in fuels are a major source of pollution.
Sulfur containing compounds such as thiophenes can poison
catalysts used to remove the residue of hydrocarbons and
nitrogen oxides derived from combustion reactions. The requirement to produce diesel fuels with very low levels of sulfur has
stimulated much work in the area of hydrodesulfurization
(HDS). This usually requires high temperatures and the presence
of hydrogen. Oxidative desulfurization (ODS), an alternative
or complementary technology to HDS for deep desulfurization,
has several advantages such as mild reaction conditions (ambient
pressure and relative low temperatures), high selectivity, and
the potential for desulfurization of sterically hindered sulfur
compounds. Benzothiophene and dibenzothiophenes are hardly
oxidized. ODS generally consists of two processes: the first
step is oxidation, and the following step is the removal of
oxidized compounds. Different oxidizing agents were used, such
as H2O2 in combination with acetic acid, formic acid,1 NO2,2
ozone,3 and t-butyl-hydroperoxide.4 Phosphotungstic acid5 and
polyoxometalates/hydrogen peroxide were found to increase the
conversion of DBT to sulfone.6 The Keggin ion, PV2Mo10O405-,
was found to be a very active and selective oxidation catalyst.
The oxidation reactivities of the thioethers in the polyoxometalate/peroxide system do not correlate with their redox potentials,
where steric effects play a significant role. A European patent
claims a method of removing organic sulfur compounds from
liquid oil using oxidizing agents, followed by distillation, and
solvent extraction or adsorption.7
The aim of the present work was to carry out a comparative
study of the benzothiophene and dibenzothiophene (model
compounds) oxidations using a series of polyoxometalates as
catalyst precursors. Hydrogen peroxide was chosen as an oxidant
as it does not adversely affect the product or cause environmental problems. Additionally, results on the chemical oxidation
and extraction of organosulfur compounds from gas oil are
presented.
Experimental Procedures
Materials and Apparatus. Phosphotungstic acid hydrate
(99%), dibenzothiophene (C12H8S, DBT, 98%), 4,6-dmethyldibenzothiophene (C14H12S, 4,6-DMDBT, 97%), and benzothiophene (C12H8S, BT 98%) were purchased from Fluka. Gas
* Author to whom correspondence should be addressed. E-mail:
wtrakarnpruk@yahoo.com.

oil (density at 15 C, 0.8565 g/mL, 0.575 wt % sulfur) was

supplied from the Thai Oil Company. Hydrogen peroxide (30
wt % H2O2, Fluka) was used as an oxidant. DMSO, DMF, and
acetonitrile were used as solvents. The silica gel and aluminum
oxide adsorbent were Merck Silica Gel 60. IR spectra were
measured using an infrared spectrophotometer Nicolet FT-IR
Impact 410 on KBr disks.
The XRD patterns of catalysts were obtained on Rigaku,
DMAX 2002 Ultima Plus X-ray powder diffractometer equipped
with a monochromator and a Cu-target X-ray tube (40 kV, 30
mA) and angles of 2 ranged from 2 to 60. UV-vis spectra
were recorded on Milton Roy Spectronic 3000 Array. The sulfur
content of original and treated oils was determined using a
SISONS X-ray fluorescence spectrometer ARL 8410 (ASTM
D4294 method), whose limitation of sulfur detection is 5 wt
ppm. The test method is based on the ASTM D-4294 standards.
Model compounds and oil samples were analyzed with a gas
chromatograph (Shimadzu GC-14B equipped with a flame
ionization detector and a 30 m (0.25 mm i.d., 0.25 m film
thickness) capillary column).
Preparation of Polyoxometalates. Polyoxometalates were
synthesized using the following procedures.
(A) Polyoxotungstate Complex, [W6O19]2-.8 A 3.3 g
quantity of sodium tungstate dihydrate (Na2WO42H2O) was
dissolved in 250 mL of deionized water, followed by the
addition of 250 mL of acetonitrile. After the addition of 1.5
mL of 10 M hydrochloric acid, 3 g of tetrabutylammonium
bromide (n-Bu4NBr) was added to precipitate a white salt, which
was filtered off and washed with deionized water and ethanol.
The crude salt was further purified by recrystallization from a
mixture of an acetonitrile/ethanol solution (3:1 v/v).
(B) 11-Tungstovanadate, [V(VW11)O40]4-.9 To a solution
of 4.9 g of sodium tungstate dihydrate (Na2WO42H2O) and
1.7 g of ammonium m-vanadate (NH4VO3) in 45 mL of warm
water was added 50 mL of acetonitrile. A total of 27 mL of 9
M perchloric acid was added with vigorous stirring. The
resultant orange solution was heated at 70 C for 24 h, and
after cooling to room temperature, the precipitate was filtered
off. To the filtrate was added 3 g of tetrabutylammonium
bromide to precipitate an orange salt. The salt was filtered and
washed with deionized water and ethanol and air-dried. It was
recrystallized from a mixture of an acetonitrile/ethanol solution
(3:1 v/v).
(C) 11-Tungsto-1-vanadophosphate, [PVW11O40]4-.10 A 0.4
g quantity of sodium dihydrogen orthophosphate (NaH2PO4
2H2O) was added to a 400 mL aqueous solution of 8.2 g of

Table 1. Characterization of Catalysts

catalyst
[W6O19]2[V(VW11)O40]4[PVW11O40]4[PV2Mo10O40]4(VO)2P2O7

mp (C)

max (nm)

FT-IR (cm-1)

XRD (2, deg)

168-170
332-335
235-238
178-182
332-335

275
265
261
308
267

979, 889, 813, 586

967, 894, 777, 518
1095, 1071, 963, 890
1075, 1057, 941, 873
1246, 1135, 1081, 962

8.9, 9.5, 10.8,14.0, 25.9

6.6, 7.0, 8.0, 8.5, 29.9
6.6, 7.6, 12.1, 23.5, 29.9
6.7, 7.7, 12.1, 23.5, 30.0
23.0, 28.4, 29.9

sodium tungstate dihydrate (Na2WO42H2O), followed by the

addition of concentrated nitric acid. After stirring, 5 mL of
aqueous solution containing 0.2 g of ammonium m-vanadate
(NH4VO3) and 0.2 g of sodium hydroxide was added, and then
the mixed solution was refluxed for 24 h. After cooling to room
temperature, the precipitate was filtered off. To the filtrate was
added 3 g of tetrabutylammonium bromide to precipitate a
yellow salt. The salt was filtered and washed with deionized
water and ethanol and dried. It was recrystallized from acetonitrile.
(D) Molybdophosphate Complex, [PV2Mo10O40]4-.11 A 0.5
g quantity of ammonium m-vanadate (NH4VO3) was dissolved
in 10 mL of 1 M sodium hydroxide. This solution was added
to a solution of 6.0 g of sodium molybdate (Na2MoO42H2O)
and 0.4 g of sodium dihydrogen orthophosphate (NaH2PO4
2H2O). Concentrated nitric acid was slowly added until the
solution had a pH of 4.0. The brown solution was refluxed for
24 h. After cooling to room temperature, 3.5 g of tetrabutylammonium bromide was added to precipitate an orange salt.
The salt was isolated, washed with water and ethanol, and airdried. It was recrystallized from acetonitrile/ethanol (1:1 v/v).
(E) Vanadyl Pyrophosphate, (VO)2P2O7.12 A 3.0 g quantity
of vanadium oxide (V2O5) was refluxed in a mixture of
2-butanol (18 mL) and benzyl alcohol (12 mL) for 14 h followed
by the addition of 85% phosphoric acid (H3PO4) (P/V ratio of
1.1) and refluxed for a further 6 h to form a light green
precipitate, which was filtered off, dried, and calcined in air at
400 C for 4 h.
Typical Pprocedure for the Oxidation. Model Sulfur
Compounds. Model sulfur compounds (benzothiophene, BT;
dibenzothiophene, DBT; or 4,6-dimethyldibenzothiophene, 4,6DMDBT) in the amount of 0.1 mmol, which dissolved in 5 mL
of hexane, were added to the catalyst and a 30% solution of
hydrogen peroxide (as an oxidant). It was stirred for 3 h at 60
C. After that, 5 mL of extraction solvent was added to the
mixture and stirred for 10 min. The biphasic mixture was
separated by decantation. After being dried over anhydrous
sodium sulfate, a 1 mL sample was withdrawn and worked-up,
added to an internal standard, and subjected to GC analysis.
The GC program started at 100 C for 2 min, and the
temperature was raised to 290 C at 8 C/min and was held for
10 min.
Gas Oil. The mixture of 50 mL of gas oil (containing 0.575
wt % sulfur), catalyst (0.18 mmol), hydrogen peroxide, and
acetic acid (hydrogen peroxide/acetic acid molar ratio of 1) was
stirred at 60 C for 5 h. The oil was extracted with acetonitrile
3 times (total volume 50 mL) and passed through a glass column
(1 25 cm) containing 10 g of alumina to remove oxidized
sulfur. The oxidized oil was washed with water and dried over
anhydrous sodium sulfate. The concentration of the remaining
sulfur compounds was determined by XRF.
Results and Discussion
Characterization of Catalysts. The FT-IR, UV-vis spectroscopy, XRD analyses, and the melting temperatures of the
prepared catalysts are collected in Table 1.

Table 2. Oxidation of DBT Using [W6O19]2-a

DBT/ oxidant/
entry catalyst DBT
1
2
3
4
5
6
7
8
9b
10b

100
100
100
50
25
100
100
100
100
25

5
5
5
5
5
10
20
5
5
20

extraction
solvent
EtOH/H2O2
MeCN
DMSO
DMSO
DMSO
DMSO
DMSO
DMF
DMF
DMF

conversion
DBT in
%
extraction solvent %
50
56
58
78
83
80
86
61
70
93

22
28
20
18
9
11
7
0
0
0

a Conditions: DBT 0.1 mmol, catalyst 0.01 mmol, hexane 5 mL,

temperature 60 C, reaction time 3 h, extraction solvent 5 mL. b Added
acetic acid (1 equiv to oxidant).

The absorption of the tetrabutylammonium salts of polyoxometalates in acetonitrile were measured, which showed a
maximum at about 260 nm.13 The IR spectra showed four
characteristic bands at around 1070-1080 cm-1, (P-O); 967976 cm-1, (M-Oterminal); 875-894 cm-1, (M-O-M, octahedral
corner-sharing); and 810-813 cm-1 (M-O-M, octahedral
edge-sharing).13
Oxidation of Model Compounds. Dibenzothiophene (DBT)
was selected as a sulfur compound representative of those
present in gas oils. Oxidation of DBT was performed with a
[W6O19]2- catalyst to study the effect of different extraction
solvents, as well as the amounts of catalyst and oxidant; the
results are tabulated in Table 2.
After oxidation, the gas chromatographic analysis shows
remaining dibenzothiophene and dibenzothiophene sulfone as
the only product. The oxidation reaction was monitored with
time (0-3 h), and sulfone was still the only product detected.
Generally, the oxidation of sulfur compounds is considered to
be a consecutive reaction (i.e., sulfur-containing compoundss
sulfoxides and sulfones). Therefore, in this study, no sulfoxide
was detected, and the sulfoxide formation was considered to
dominate the reaction rate.
From Table 2, comparing among several solvents tested, it
was found that DMSO and DMF yielded a higher % conversion
than MeCN or EtOH/H2O2. This agrees well with that reported.14
The disadvantage of the former two solvents is that they have
a high boiling point at 300 C, which is close to the boiling
point of the sulfone. Acetonitrile (MeCN) has a relatively low
boiling point (82 C) and is easily separated from the sulfone
by distillation. It is known that an aprotic solvent, like DMF,
and MeCN enhance water and hydrogen peroxide dissociations
to obtain OH- and HO2-, respectively. The perhydroxyl ion
(HO2-) is quite stable and interacts with the hydroxyl groups
formed during water dissociation to produce the superoxide
radical O2-.
It should be noted that when using DMF as an extraction
solvent, no DBT was detected in this solvent phase. Therefore,
it is suitable for the complete separation between substrate and
sulfone product.
The percent conversion increases when the amount of oxidant
and catalyst is increased. The addition of acetic acid enhanced
the conversion. The reaction proceeds via oxidation by peracetic

Table 3. Oxidation of DBT Using Different Catalystsa

entry

catalyst

DBT/catalyst

oxidant/DBT

conversion %

1
2
3
4
5
6
7
8
9
10

]2-

100
25
100
25
100
25
100
25
100
25

5
20
5
20
5
20
5
20
5
20

70
91
74
94
62
90
64
85
28
40

[W6O19
[W6O19]2[V(VW11)O40]4[V(VW11)O40]4[PVW11O40]4[PVW11O40]4[PV2Mo10O40]4[PV2Mo10O40]4(VO)2P2O7
(VO)2P2O7

Figure 1. Pseudo-first-order oxidation of BT at 50-70 C using

[V(VW11)O40]4-.

a Condition: DBT 0.1 mmol, hexane 5 mL, extraction solvent DMF 5

mL, [AcOH]/[H2O2] ) 1, temperature 60 C, reaction time 3 h.

Table 4. Oxidation of Different Sulfur Compoundsa

Table 5. Rate Constants at Different Temperaturesa

substrates

conversion %

BT

entry

catalyst

DBT

4,6-DMDBT

BT

1
2
3
4
5

[W6O19]2[V(VW11)O40]4[PVW11O40]4[PV2Mo10O40]4(VO)2P2O7

87
99
88
86
50

74
80
70
70
39

50
55
40
42
20

a Condition: substrate 0.1 mmol, hexane 5 mL, extraction solvent DMF

5 mL, substrate/catalyst ) 100, oxidant/substrate ) 30, [AcOH]/[H2O2] )
1, temperature 60 C, reaction time 5 h.

acid, which was formed in situ from a mixture of hydrogen

peroxide and acetic acid.
To compare the reactivity between the different catalysts, the
oxidation of DBT was carried out under the same reaction
conditions. The results are shown in Table 3. The oxidation
reactivity order of the catalyst in the presence of acetic acid
is [V(VW11)O40]4- > [W6O19]2- [PVW11O40]4- > [PV2Mo10O40]4- > (VO)2P2O7.
Comparison of the Oxidation Reactivity of the Sulfur
Compounds. To investigate the difference of reactivity between
the different sulfur compounds, the oxidation of three model
sulfur compounds (DBT, 4,6-DMDBT, and BT) was carried
out under the same reaction condition. The results are shown
in Table 4.
The oxidation reactivity decreased in the order of DBT >
4,6-DMDBT > BT. BT exhibited the lowest reactivity, and this
was attributed to the significantly lower electron density on the
sulfur atom on BT. For DBT and 4,6-DMDBT, the difference
in the electron density on the sulfur is very small (5.756 and
5.760, respectively), calculated by the semiempirical MO
method.15 Therefore, reactivity was governed by the steric
hindrance of the methyl groups, which become an obstacle for
the approach of the sulfur atom to the catalytic active species.
The results obtained in this work correspond to that reported
for a formic acid/H2O2 system.16
In the oxidation of sulfur compounds, the formation of
corresponding sulfones can be explained as follows: the sulfur
compound reacts with peracetic acid, which resulted from a
combination of H2O2 and acetic acid. In the presence of a
catalyst, the mechanism involved a metal-peroxo intermediate
formed by the reaction of the catalyst with the oxidant. This
intermediate was detected by NMR.17 In this work, it was found
that polyoxometalate containing vanadium has the highest
reactivity, and this corresponds to the reported results on the
effect of substituted transition metal in the polyoxometalate
compounds.18 The substitution of Mo(VI) with V(V) would
result in the generation of more reactive lattice oxygen associated with the Mo-O-V species.
Kinetics. Since H2O2 was present in large excess, the reaction
data were fitted to a first-order rate equation. The rate constant

DBT
4,6-DMDBT

reaction
temperature (C)

rate
constants (min-1)

correlation
factor R2

50
60
70
50
60
70
50
60
70

0.0057
0.0103
0.0223
0.0109
0.0171
0.0344
0.0061
0.0152
0.0223

0.9845
0.9916
0.9856
0.9971
0.9897
0.9801
0.9870
0.9820
0.9925

a Condition: substrate 0.01 M, [V(VW )O ]4- 1.25 10-4 M, oxidant

11
40
1.0 M. substrate/catalyst molar ratio ) 80, oxidant/substrate molar ratio )
100, hexane 5 mL, extraction solvent DMF 5 mL, [AcOH]/[H2O2] ) 1.

Table 6. Apparent Activation Energies for Oxidation of Sulfur

Compounds
substrates

Ea (kJ/mol)

correlation factor R2

BT
DBT
4,6-DMDBT

62.73
52.83
57.35

0.9849
0.9943
0.9963

(k) and reaction time (t) can be described using the following
equation: ln(Ct/Co) ) -kt, where k ) A exp(-Ea/RT). A is
the preexponential factor, Ea is the apparent activation energy,
and R and T are the gas constant and reaction temperature (K),
respectively. A plot of ln(Ct/Co) versus reaction time (t)
displayed a linear relationship that confirmed the pseudo-firstorder reaction kinetics, as shown in Figure 1. The rate constants
(k) were determined and collected in Table 5.
A plot of ln k versus 1/T allows us to calculate the activation
energy Ea (slope ) -Ea/R). The apparent activation energies
are listed in Table 6.
The apparent activation energy of pseudo-first-order reaction
for BT, 4,6-DMDBT, and DBT were determined to be 62.73,
57.35, and 52.83 kJ/mol, respectively. It should be noted that
the apparent activation energy obtained from this work is in
good agreement with those reported. For the polyoxometalate/
H2O2 system, the apparent activation energy of 4,6-DMDBT
and DBT were 57.41 and 53.8 kJ/mol, respectively.16
Oxidative Desulfurization of Gas Oil. To investigate
whether the oxidative desulfurization system is effective for
diesel fuels, the oxidative desulfurization of a commercial gas
oil (containing 0.575 wt % of sulfur) was carried out. It was
previously reported that the most effective solvent for the
removal of the sulfone product was DMF, but oil recovery was
low.19 In regards to oil recovery, acetronitrile is better than
DMF.20 Therefore, in this work, acetonitrile was chosen as an
extraction solvent. The oxidative reaction was followed by the
adsorption of oxidized product using alumina as an adsorbent.
The results are shown in Table 7.
Acetonitrile has a relatively low boiling point and can be
easily separated by distillation, and it can be reused for further
extraction. Sulfone is more polar and is likely to bond strongly

Table 7. Oxidative Desulfurization of Gas Oila

entry

catalyst

sulfur content
remained (wt %)

1
2
3
4
5

[W6O19]2[V(VW11)O40]4[PVW11O40]4[PV2Mo10O40]4(VO)2P2O7

0.142
0.055
0.098
0.129
0.208

conversion
%

recovery
of oil (%)

75
90
83
78
64

87
87
86
87
86

a Condition: gas oil (0.575 wt % S) 50 mL, catalyst 0.18 mmol,

extraction solvent acetonitrile 50 mL, Al2O3 10 g, substrate/catalyst molar
ratio ) 50, oxidant/substrate molar ratio ) 100, [AcOH]/[H2O2] ) 1, temp
60 C, time 5 h.

to an alumina adsorbent without decomposition of H2O2 taking

place.21 From the results obtained in this work, it was
demonstrated that the catalyst can catalyze the oxidation reaction
in 5 h and can reduce the sulfur content of diesel oil from 0.575
wt % S to 0.055 wt % S. For comparison, it should be mentioned
that in the oxidation of straight run light gas oil (1.35 wt % S)
in a hydrogen peroxide/formic acid system, the removal of sulfur
was 99% in 46 h.19
Conclusions
A desulfurization process of light oil using hydrogen peroxide
and a catalyst has been investigated. It was found that the
oxidation reaction proceeds very rapidly and selectively to give
the corresponding sulfones under mild conditions. The oxidation
with solvent extraction and alumina adsorption to further remove
the oxidized product reduces the sulfur content of oil successfully up to 90%, from 0.575 wt % S to 0.055 wt % S.
Acknowledgment
The authors are grateful for the financial support from the
Graduate School, Chulalongkorn University.
Literature Cited
(1) Rappas, A. S.; Nero, V. P.; DeCanio, S. J. Process for removing
low amounts of organic sulfur from hydrocarbon fuels. United States Patent
6,406,616, 2002.
(2) Tam, P. S.; Kittrel, J. R.; Eldridge, J. W. Desulfurization of fuel oil
by oxidation and extraction. 1. Enhancement of extraction oil yield. Ind.
Eng. Chem. Res. 1990, 29, 321.
(3) Otsuki, S.; Nonaka, T.; Qian, W.; Ishihara, A.; Kabe, T. Oxidative
desulfurization of middle distillate using ozone. Sekiyu Gakkaishi 1999,
42, 315.
(4) Koch, T. A.; Krause, K. R.; Manzer, L. E.; Mehdizadeh, M.; Odom,
J. M.; Senupta, S. K. Environmental challenges facing the chemical industry.
New J. Chem. 1996, 20, 163.
(5) (a) Yazu, K.; Yamamoto, Y.; Furuya, T.; Miki, K.; Ukeawa, K.
Oxidation of dibenzothiophenes in an organic biphasic system and its
application to oxidative desulfurization of light oil. Energy Fuels 2001,
15, 1535. (b) Yazu, K.; Furuya, T.; Miki, K.; Ukegawa, K. Tungstophos-

phoric acid-catalyzed oxidative desulfurization of light oil with hydrogen

peroxide in a light oil/acetic acid biphasic system. Chem. Lett. 2003, 32,
920.
(6) Collins, F. M.; Lucy, A. R.; Sharp, C. Oxidative desulphurization
of oils via hydrogen peroxide and heteropolyanion catalysis. J. Mol. Catal.,
A 1997, 117, 397.
(7) Funakoshi, T.; Aida, T. Solvent effects during oxidation-extraction
desulfurization process of aromatic sulfur compounds from fuels. European
Patent 0565324A1, 1993.
(8) Himeno, S.; Yoshihara, M.; Maekawa, M. Formation of voltammetrically active isopolyoxotungstate complexes in aqueous CH3CN media.
Inorg. Chim. Acta 2000, 298, 165.
(9) Himeno, S.; Takamoto, M.; Higuchi, A.; Maekawa, M. Preparation
and voltammetric characterization of keggin-type tungstovanadate [VW12O40]3and [V(VW11)O40]4- Complexes. Inorg. Chim. Acta 2004, 57, 87.
(10) Ueda, T.; Komatsu, M.; Hojo, M. Spectroscopic and voltammetric
studies on the formation of Keggin type V(V)-substituted tungstoarsenate(V) and phosphate(V) complexes in aqueous and aqueous-organic solutions.
Inorg. Chim. Acta 2003, 344, 77.
(11) Himeno, S.; Ishiro, N. A voltammetric study on the formation of
V(V) and V(IV) substituted molybdophosphate(V) complexes in aqueous
solution. J. Electroanal. Chem. 1998, 451, 203.
(12) Pillai, U. R.; Sahle-Demessie, E.; Varma, R. S. Alternative routes
for catalyst preparation: use of ultrasound and microwave irradiation for
the vanadium phosphorus oxide catalyst and their activity for hydrocarbon
oxidation. Appl. Catal., A 2003, 252, 1.
(13) Himeno, S.; Takamoto, M.; Ueda, T. Synthesis, characterization,
and voltammetric study of a Keggin-type [PWO]3- complex. J. Electroanal.
Chem. 1999, 456, 129.
(14) Otsuki, S.; Nonaka, T.; Takashima, N.; Qian, W.; Ishihara, A.; Imai,
T.; Kabe, T. Oxidative desulfurization of light gas oil and vacuum gas oil
by oxidation and solvent extraction. Energy Fuels 2000, 14, 1232.
(15) Wang, X.; Xu, L.; Chen, X.; Ji, W.; Qijie, T.; Chen, Y. Novel
modifications in preparing vanadium phosphorus oxides and their applications for partial oxidation of n-butane. J. Mol. Catal., A 2003, 206, 261.
(16) Te, M.; Fairbride, C.; Ring, Z. Oxidation reactivities of dibenzothiophenes in polyoxometalate/H2O2 and formic acid/H2O2 systems. Appl.
Catal., A 2001, 219, 267.
(17) Kala Raj, N. K.; Ramaswamy, A. V.; Manikandan, P. Oxidation
of norbornene over vanadium-substituted phosphomolybdic acid catalysts
and spectroscopic investigations. J. Mol. Catal., A 2005, 227, 37.
(18) Liu, Y.; Murata, K.; Inaba, M. Liquid-phase oxidation of benzene
to phenol by molecular oxygen over transition metal substituted polyoxometalate compounds. Catal. Commun. 2005, 6, 679.
(19) Zannikos, E.; Lous, E.; Stournas, S. Desulfurization of petroleum
fractions by oxidation and solvent extraction. Fuel Proc. Technol. 1995,
42, 35-45.
(20) Murata, S.; Murata, K.; Kidena, K.; Nomura, M. A novel oxidative
desulfurization system for diesel fuels with molecular oxygen in the presence
of cobalt catalysts and aldehydes. Energy Fuels 2004, 18, 116.
(21) Shiraishi, Y.; Hara, H.; Hirai, T.; Komasawa, I. A deep desulfurization process for light oil by photosensitized oxidation using a triplet
photosensitizer and hydrogen peroxide in an oil/water two-phase liquidliquid extraction system. Ind. Eng. Chem. Res. 1999, 38, 1589.

ReceiVed for reView October 28, 2005

ReVised manuscript receiVed January 23, 2006
Accepted January 26, 2006