1.

Introduction
The removal of sulfur compounds from diesel oil is
necessary for the reduction of NOx and particulate con-
tents in the emission from diesel engines. New legis-
lation in Japan and Europe will limit the sulfur content
to a maximum of 50 ppm by 2005. Alkylated diben-
zothiophenes substituted at the 4 and/or 6 positions in
diesel oil are difficult to be removed by the convention-
al hydrodesulfurization method because of their steric
hindrance
1),2)
. Therefore, a new method for removing
these hindered dibenzothiophenes is needed.
Oxidative desulfurization is one of the best methods
because hindered dibenzothiophenes in diesel oil are
oxidized effectively with peroxy-acids
3),4)
, H2O2
5)
and t-
BuOCl
6)
, or by photooxidation
7),8)
, and the oxidation
products are easily removed from the diesel oil by
extraction and adsorption. We recently found that the
hindered dibenzothiophenes were oxidized smoothly
with H2O2 in the presence of 12-tungstophosphoric acid
(TPA) in a hydrocarbon/acetonitrile (MeCN) biphasic
system and that the sulfur content of a diesel oil was
effectively reduced
9)
. To further develop this oxida-
tion system, we have used immobilized TPA on a
strongly basic anion exchange resin as the catalyst.
Here we report that the immobilized TPA catalyzes
the oxidation of dibenzothiophenes in the presence of
H2O2 (Scheme 1) and is effective for the oxidative
desulfurization of diesel oil in the diesel oil/MeCN
biphasic system.
2. Experimental
2. 1. Preparation of Immobilized TPA Catalyst
Amberlyst A-26 (AER) used as an anion exchange
resin was obtained from Organo Corp. The ion
exchange capacity of AER is 3.8 meq/g dry resin. To
prepare the immobilized TPA on AER (TPA/AER), an
AER (0.5 g dry resin) suspension in an aqueous TPA
solution (100 ml) was stirred at room temperature for
24 h. Then, the resin was filtered off, washed with
distilled water and MeCN, and stored in MeCN.
TPA/AER-1, TPA/AER-2, TPA/AER-3, and TPA/AER-
4 were the immobilized catalysts prepared with 1, 2, 4,
J. Jpn. Petrol. Inst., Vol. 46, No. 6, 2003
Journal of the Japan Petroleum Institute, 46, (6), 379382 (2003) 379
Immobilized Tungstophosphoric Acid-catalyzed Oxidative
Desulfurization of Diesel Oil with Hydrogen Peroxide
Kazumasa YAZU*, Takeshi FURUYA, and Keiji MIKI
Institute for Energy Utilization, National Institute of Advanced Industrial Science and Technology,
AIST Tsukuba West, 16-1 Onogawa, Tsukuba, Ibaraki 305-8569, JAPAN
(Received May 13, 2003)
An immobilized 12-tungstophosphoric acid on an anion exchange resin (TPA/AER) catalyzes the oxidation of
dibenzothiophene and 4,6-dimethyldibenzothiophene with H2O2 in acetonitrile (MeCN) to give the corresponding
sulfones as the major product. The oxidation rates increased with increasing amounts of H2O2 and TPA/AER.
TPA/AER is reusable since the catalytic activity was not reduced even during the fifth cycle of use. TPA/AER
acts as a catalyst for the oxidation of dibenzothiophenes in an octane/MeCN biphasic system as well. The major
oxidation products were also the sulfones, which were mainly distributed in the MeCN phase. In TPA/AER-cat-
alyzed oxidative desulfurization of diesel oil containing 330 ppm sulfur, the reduction of the sulfur content was
enhanced with increasing amounts of immobilized TPA per unit weight of AER and the sulfur content was
reduced to below 50 ppm. The sulfur content was further decreased by solvent extraction with MeCN.
Keywords
Immobilized catalyst, Tungstophosphoric acid, Hydrogen peroxide, Dibenzothiophene,
Oxidative desulfurization, Diesel oil
[Research Note]
* To whom correspondence should be addressed.
* E-mail: yazu-k@aist.go.jp
Scheme 1
and 8 mM (1 M = 1 moldm
3
) TPA aqueous solution,
respectively. The amount of TPA retained on AER
was calculated from the decrease in the amount of TPA
estimated from tungsten analyses by inductively cou-
pled plasma (ICP) spectrometry using Thermo Jarrell
Ash IRIS/AP. The values for TPA/AER-1, TPA/
AER-2, TPA/AER-3, and TPA/AER-4 were 0.16, 0.29,
0.49, and 0.66 mmol/g dry resin, respectively.
2. 2. Oxidation of Dibenzothiophenes in MeCN
TPA/AER (or AER) was added to 50 ml of a MeCN
solution of dibenzothiophene (1a) (0.25 mmol) or 4,6-
dimethyldibenzothiophene (1b) (0.25 mmol) and kept
at 60C with stirring, and then the required amount of
35% aqueous H2O2 was added. High performance liq-
uid chromatography (HPLC) analysis for the oxidation
of 1a or 1b was conducted as reported previously
10)
.
Consumption of H2O2 was followed by iodometry.
Experiments for the reuse of TPA/AER were carried
out as follows. TPA/AER-3 (0.12 mmol/0.25 g dry
resin) was added to 50 ml of a MeCN solution of 1a
(0.25 mmol) and kept at 60C with stirring, and then 2
ml of 35% aqueous H2O2 (23.2 mmol) was added.
The oxidation was similarly monitored with HPLC.
After 1.5 h, the catalyst was filtered off, washed with
MeCN three times, and stored in MeCN. The catalyst
was then used in the next run. This procedure was
repeated as required.
2. 3. Oxidation of Dibenzothiophenes in an Organic
Biphasic System
TPA/AER-3 (0.12 mmol/0.25 g dry resin) was added
to 50 ml of an octane solution of 1a (0.25 mmol) or 1b
(0.25 mmol) and 50 ml of MeCN. The mixture was
kept at 60C and 2 ml of 35% aqueous H2O2 (23.2
mmol) was added. The decay of 1a or 1b was mea-
sured as described above.
2. 4. Oxidative Desulfurization of Diesel Oil
Hydrodesulfurized diesel oil was supplied by Japan
Energy Corp. The sulfur content was 330 ppm.
TPA/AER (0.25 g dry resin) was added to 25 ml of the
diesel oil, 25 ml of hexane and 50 ml of MeCN. The
MeCN phase formed the upper layer without hexane
since the densities of the diesel oil, hexane and MeCN
are 0.83, 0.65 and 0.78, respectively. The biphasic
mixture was kept at 60C and 2 ml of 35% aqueous
H2O2 (23.2 mmol) was added. The oil phase was sep-
arated, washed with water, and dehydrated with CaCl2
and the sulfur content was measured as reported previ-
ously
10)
after evaporation of hexane.
3. Results and Discussion
3. 1. Immobilized TPA-catalyzed Oxidation of
Dibenzothiophenes in MeCN
The results of TPA/AER-catalyzed oxidation of
dibenzothiophenes in MeCN are summarized in Table
1. The oxidation of 1a proceeded rapidly in the pres-
ence of TPA/AER to give the corresponding sulfoxide
and sulfone (2a) as the major products (e.g., 2a was
formed in 90 mol% yield at 1 h under the conditions of
entry 7). On the other hand, no oxidation was
observed when intact AER was used (entry 2). The
amount of immobilized TPA per unit weight of AER
was TPA/AER-1 < TPA/AER-2 < TPA/AER-3 < TPA/
AER-4 (entries 1, 3-5). The increase in the immobi-
lized TPA had little effect on the oxidation under the
conditions employed. The difference in the conver-
sion after 1 h was important since complete oxidation is
essential for the oxidative desulfurization. Therefore,
an increase in the immobilized TPA would be useful
for the oxidation. This was consistent with the results
for the oxidative desulfurization of diesel oil.
The oxidation rates increased with higher amounts of
H2O2 (entries 1, 6, 7) and immobilized catalyst (entries
1, 8, 9), but an increase in the immobilized catalyst was
not effective for complete oxidation. Oxidation to the
sulfone needs two moles of H2O2 per one mole of
dibenzothiophene (Scheme 1). Excess H2O2 was
necessary in this oxidation system since most H2O2 was
consumed by non-reactive decomposition; 84% of the
added H2O2 was consumed during 1 h oxidation but
380
J. Jpn. Petrol. Inst., Vol. 46, No. 6, 2003
Table 1 Immobilized TPA-catalyzed Oxidation of 5 mM (1 M = 1 moldm
3
) Dibenzothiophenes with H2O2 in MeCN at 60C
Entry Substrate TPA/AER [mmol/g dry resin]
35 wt% H2O2
Conversion [mol%]
[ml] 0.5 h 1 h 2 h
1 1a TPA/AER-3 (0.12/0.25) 1.0 70 93 99
2 AER (0/0.25) 1.0 0 0 0
3 TPA/AER-1 (0.04/0.25) 1.0 63 88 94
4 TPA/AER-2 (0.07/0.25) 1.0 71 93 98
5 TPA/AER-4 (0.17/0.25) 1.0 70 94 100
6 TPA/AER-3 (0.12/0.25) 0.5 57 79 88
7 TPA/AER-3 (0.12/0.25) 2.0 88 100 100
8 TPA/AER-3 (0.04/0.08) 1.0 34 65 92
9 TPA/AER-3 (0.24/0.50) 1.0 87 98 99
10 1b TPA/AER-3 (0.12/0.25) 1.0 48 77 92
11 TPA/AER-3 (0.12/0.25) 2.0 78 100 100
only about 2% of the consumed H2O2 was used for the
oxidation of 1a under the conditions of entry 7. The
consumption of H2O2 should be minimized by the
improvement of the catalytic activity since more than
80% of the consumed H2O2 was utilized for the oxida-
tion of 1a in a homogeneous TPA catalyzed reaction.
4,6-Dimethyldibenzothiophene (1b), one of the most
unreactive sulfur compounds during hydrodesulfuriza-
tion
1),2)
, was also oxidized effectively to the correspond-
ing sulfoxide and sulfone (2b); the yield of 2b was 86
mol% at 1 h under the conditions of entry 11.
However, the rate of oxidation of 1b was a little slower
than that of 1a in this oxidation system (entries 1, 7, 10,
11). This difference in oxidation rates may result
from the difference in the accessibilities of 1a and 1b to
the active sites of TPA/AER because the two substrates
were oxidized at a similar rate in homogeneous TPA-
catalyzed oxidations. TPA/AER is reusable, since
recovery can be easily achieved by simple filtration and
the catalytic activity was not reduced even after the
fifth cycle of use; the extents of the conversion after 0.5
h and 1 h oxidation were 92 mol% and 100 mol%,
respectively, in the fifth run (see entry 7 in Table 1).
Consequently, these results indicate that TPA/AER can
act effectively as a catalyst for the oxidation of diben-
zothiophenes with H2O2 in MeCN.
3. 2. Immobilized TPA-catalyzed Oxidation of
Dibenzothiophenes in an Organic Biphasic
System
Oxidation of dibenzothiophenes was investigated in
the presence of TPA/AER in an organic biphasic sys-
tem using octane as the model for the diesel oils.
Figure 1 shows that 54% of 1a was transferred into
the MeCN phase from the octane phase prior to oxida-
tion and the concentration of 1a in octane phase
decreased as 1a was oxidized in the MeCN phase
(Scheme 2). Compared with 1a, a lesser amount
(36%) of 1b was transferred into the MeCN phase from
the octane phase prior to oxidation due to the substitu-
tion with methyl groups. The oxidation of 1b pro-
ceeded similarly, but more slowly than that of 1a.
This may be ascribed to the lower reactivity of 1b
(Table 1) and the lower partition constant in the
MeCN phase. In addition, the rates of TPA/AER-cat-
alyzed oxidation of 1a and 1b were much smaller than
those observed in the TPA-catalyzed reactions
9)
.
Accordingly, improvement of the catalytic activity is
necessary for application to the oxidative desulfuriza-
tion of diesel oil. The design of AER may be effec-
tive for the improvement; the molecular weights of the
support polymers influence the catalytic activities of
the supported heteropoly oxometalates
11)
. The major
oxidation products were the sulfones, as observed in
MeCN. This biphasic system would be useful for
desulfurization of diesel oil since the sulfones are much
more soluble in MeCN than in octane due to their
polarity: 2a and 2b partition 99% and 96%, respective-
ly, into the MeCN phase.
3. 3. Immobilized TPA-catalyzed Oxidative Desul-
furization of Diesel Oil
TPA/AER was applied to the oxidative desulfuriza-
tion of diesel oil containing 330 ppm sulfur. A small
reduction in sulfur content (ca. 60 ppm) was observed
prior to the oxidation (Fig. 2) since the organic sulfur
compounds in diesel oil were extracted with MeCN.
There was little decrease in the sulfur content in the
absence of TPA/AER. In contrast, the sulfur content
was reduced with time in the presence of TPA/AER
and the reduction was enhanced by increasing the
amount of immobilized TPA per unit weight of AER.
After 5 h of oxidation, the sulfur content was reduced
to 43 ppm with TPA/AER-4 and to 97 ppm with TPA/
AER-1. These results indicate that TPA/AER-cat-
alyzed oxidation is applicable to the oxidative desulfur-
ization of diesel oil. Since a small amount of oxidized
sulfur compounds still remained in the oil phase, addi-
tional solvent extraction was effective for further
reduction of the sulfur content in the oil: the sulfur con-
381
J. Jpn. Petrol. Inst., Vol. 46, No. 6, 2003
Fig. 1 Removal of 1a () or 1b () in Octane during Oxida-
tion with Hydrogen Peroxide and TPA/AER at 60C in
an Octane/MeCN Biphasic System
Scheme 2
tent was decreased to 21 ppm by the treatment of the
oxidized diesel oil containing 43 ppm sulfur with an
equal volume of MeCN.
4. Conclusion
TPA/AER catalyzed the oxidation of dibenzothio-
phenes with H2O2 not only in MeCN but also in an
organic biphasic system. The immobilized catalyst
was useful for the oxidative desulfurization of diesel oil
in the diesel oil/MeCN biphasic system. The applica-
tion of TPA/AER would simplify oxidative desulfuriza-
tion, although the catalytic activity requires further
improvement.
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382
J. Jpn. Petrol. Inst., Vol. 46, No. 6, 2003
, TPA/AER-1; , TPA/AER-2; , TPA/AER-3; , TPA/
AER-4; , no TPA/AER.
Fig. 2 Oxidative Desulfurization of Diesel Oil Induced by
Hydrogen Peroxide and TPA/AER at 60C in a Light
Oil/MeCN Biphasic System

305-8569 16-1

MeCN
12-TPA/AERH2O2
4,6-

H2O2 TPA/AER
TPA/AER 5

TPA/AER /MeCN

MeCN TPA/AER 330 ppm

AER TPA
50 ppm
MeCN