Oxidative Removal of Organo-sulfur Species via H2O2 Oxidation Catalyzed by Lacunary Keggin 11-tungstophosphates

Article abstract of DOI:10.1007/s10562-018-2433-1

Abstract: The lacunary Keggin 11-tungstophosphates were evaluated as catalysts for the oxidation of dibenzothiophene with hydrogen peroxide as oxidant in normal octane/acetonitrile biphasic system. The Na₅[PW11O₃₉Ni] exhibited good catalytic activity with the desulfurization efficiency above 99.5%. The key factors affecting the reaction, including amount of catalyst, O/S molar ratio, catalyst dosage and initial sulfur content, were investigated, whereby the favorable conditions were determined. The presence and the oxidative effect of the peroxo-heteropoly species in the oxidative reaction were determined in the contrast experiments. Moreover, the Na₅[PW11O₃₉Ni] catalyst was confirmed to have a high potential for deep desulfurization of diesel oil.

Full text of DOI:10.1007/s10562-018-2433-1

Catalysis Letters
https://doi.org/10.1007/s10562-018-2433-1
Oxidative Removal of Organo-sulfur Species via H2O2 Oxidation
Catalyzed by Lacunary Keggin 11-tungstophosphates
Han Wang1 · Rui Wang1 · Yongqiang Zhang1 · Shuaiyong Dou1 · Silchenkova Olga2 · Korchak Vladimir2
Received: 26 January 2018 / Accepted: 24 May 2018
© Springer Science+Business Media, LLC, part of Springer Nature 2018
Abstract
The lacunary Keggin 11-tungstophosphates were evaluated as catalysts for the oxidation of dibenzothiophene with hydrogen
peroxide as oxidant in normal octane/acetonitrile biphasic system. The Na5[PW11O39Ni] exhibited good catalytic activity
with the desulfurization efficiency above 99.5%. The key factors affecting the reaction, including amount of catalyst, O/S
molar ratio, catalyst dosage and initial sulfur content, were investigated, whereby the favorable conditions were determined.
The presence and the oxidative effect of the peroxo-heteropoly species in the oxidative reaction were determined in the con-
trast experiments. Moreover, the Na5[PW11O39Ni] catalyst was confirmed to have a high potential for deep desulfurization
of diesel oil.
Graphical Abstract
Keywords Lacunary Keggin anions · Oxidative desulfurization · Hydrogen peroxide · Diesel oil
* Rui Wang
wangrui@sdu.edu.cn
Extended author information available on the last page of the article
Vol.:(0123456789)
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H. Wang et al.
affecting the Keggin-type primary structure [22], transi-
tion metal-modified lacunary heteropolycompounds of the
general formula [XW11O39M]n−, where X = P or Si and
M=first row transition metals, have recently attracted con-
siderable attention [23]. In the paper, the DBT in n-octane
solution was used as simulated diesel oil. In n-octane/
acetonitrile biphasic system, with hydrogen peroxide as
oxidant, lacunary heteropolycompounds were evaluated as
catalyst for ODS with no related literature reported. Main
factors affecting the process were investigated to con-
firm optimum reaction conditions. Moreover, the contrast
experiments were conducted to determine active interme-
diates which have been reported to possess high activity
for the oxidation of many organic compounds in the pres-
ence of H2O2 [20]. And then the practical application of
catalyst was testified in real diesel oil under favourable
conditions. The good catalytic performance of lacunary
heteropolycompounds also provided a promising path-
way and foundation to the catalytic activity of supported
catalysts.
1 Introduction
The removal of the sulfur compounds in the fuel oil is
a beneficial method to reduce the total emission of SOx
in the air. Environmental specification and legal require-
ments have been well-established to promote clean fuels
in the global scope. The maximum sulfur content of fuels
was limited to 50 ppm by 2005 and 10 ppm by 2007 in
Europe Commission [1]. According to the EPA regula-
tions, the highway diesel fuel sulfur had been lessened
from 500 ppm down to 15 ppm by June 2006 in the US
[2]. More and more stringent regulation limited the sulfur
content to be about 10 ppm in diesel in many countries
by 2010.
In conventional catalytic hydrodesulfurization (HDS),
the aliphatic and acyclic thiols, sulfides and disulfides
are easily converted into H2S, while the aromatic com-
pounds with steric hindrance on the sulfur atom are dif-
ficult to be removed in hydrogenation reaction [3, 4]. The
refractory organosulfur compounds include dibenozo-
thiophene (DBT), 4-methyl-dibenzothiophene (4-MDBT)
and 4,6-dimethyl-dibenzothiophene (4,6-DMDBT) and its
derivates. In order to obtain ultra-low sulfur fuels, severe
process conditions such as higher temperature, higher
pressure and longer residence time, are required, lead-
ing to high investment and operating cost. It is extremely
desirable to develop a more energy-efficient technology.
Potential deep desulfurization processes include, but are
not limited to, adsorption [2, 5], extraction [1], oxidation
[6–16] and bioprocesses [6]. The oxidative desulfuriza-
tion (ODS), with the potential for removal of refractory
organosulfur compounds [15] and mild process conditions,
is recognized as one of the promising alternative methods
for deep desulfurization. In the ODS process, hydrogen
peroxide with the character of non-pollution and economi-
cal efficiency is used as the most common oxidant. The
heteropolycompounds (HPC), renowned as green cata-
lysts, are widely used for their effectiveness in ODS with
H2O2 [11, 13, 17–19]. The Keggin type HPA, comprised
by tetrahedral or octahedral oxygen-metal cluster, is regu-
lar hexahedron cage structure. The symmetrical structure
and the large molecule bulk determine the efficient cataly-
sis and selectivity [20]. Furthermore, in order to make
a better contact between oxidizing regent and organosul-
fur compounds, either the extracting agent incorporated
[7, 9, 10, 14] or phase transfer catalyst (PTC) [7, 11, 19]
is introduced commonly to better reaction system. And
then, the corresponding product is removed by extraction,
adsorption or distillation to improve the desulfurization
efficiency [6, 14, 21].
2 Experimental
2.1 Materials
Thiophene (C4H4S), benzothiophene (C8H6S), dibenzothio-
phene (C12H8S), 4,6-dimethly dibenzothiophene (C14H12S)
were purchased from Sigma–Aldrich and used without fur-
ther purification. Phosphotungstic acid (H3PW12O40·12H2O)
of analytical grade, was produced by National Drug &Chem-
ical Group Co. Ltd. Hydrogen peroxide (H2O2, 37 wt.%),
normal octane (C8H18, AR), acetonitrile (CH3CN, AR),
sodium carbonate (Na2CO3), sodium bicarbonate (NaHCO3)
and the transition metal sulfates (MSO4) were all commer-
cially available and used without further purification.
2.2 Preparation of Transition Metal‑Modified
Lacunary Heteropolycompounds
The lacunary heteropolycompounds catalysts used in
this paper included Na7[PW11O39], and transition metal-
modified Na5[PW11O39M], with M = Fe2+, Ni2+, Co2+
and Cu2+. The catalysts were prepared according to the
literature method [24, 25]. The lacunary heteropoly anion
[PW11O39]7− was obtained by adding the NaHCO3 solution
to H3PW12O40·12H2O aqueous solution till the pH value
up to 5.0–5.5. In order to introduce the transition metal
ion into the octahedral lacuna, the obtained solution of
[PW11O39]7− and an aqueous solution of the transition metal
salt were mixed and stirred at the molar ratio 1:1 and the
temperature in the whole reaction was controlled at 70 °C.
The Na7[PW11O39] and Na5[PW11O39M] catalysts were
Because of their thermal and chemical stability, and
the range of possibilities for their modification without
1 3

Oxidative Removal of Organo-sulfur Species via H2O2 Oxidation Catalyzed by Lacunary…
obtained by solvent evaporation and recrystallization from
water. They were dried at 70 °C before their characterization
by Avatar370 FT-IR equipment.
2.3 The Measurement of Catalyst in Simulated
Diesel Oil
The catalytic activity of lacunary Keggin 11-tungstophos-
phates was measured according to the method described in
our previous reports [17, 18], with oxidation reactions car-
ried out in acetonitrile phase. During the reactions, test sam-
ples were withdrawn from the n-octane phase of the reaction
mixture and the sulfur contents were analyzed by WK-2E
micro coulometric detector. The temperatures were set as
600 °C for stilling section, 800 °C for combustion section
and 700 °C for vaporization section.
2.4 The Measurement of Catalyst in Real Diesel Oil
Fig. 1 FT-IR spectra of the lacunary Keggin heteropolycompounds
,
[PW11O39]7−(a) and [PW11O39M]5− with M=Fe2+(b), Co2+(c),
Cu2+(d),or Ni2+(e)
A couple of real diesel oils were tested by the same proce-
dure as simulated diesel oil. Whereas, the extractant was
increased from 60 to 120 mL to deepen desulfurization reac-
tion under otherwise identical conditions. For diesel sample
A, 120 mL acetonitrile solution was added to, before ODS
reaction, while for sample B, 60 mL acetonitrile solution
was individually added to diesel before and after ODS reac-
tion. The diesel and the acetonitrile solution were separated
by funnel. Then diesel samples were analyzed for sulfur con-
tent by WK-2E micro coulometric detector.
showed a prominent band at 1080 cm− 1assigned to the ν3
vibration of the central PO4 tetrahedron. Remarkablely, in
the [PW11O39]7− anion spectrum, this band was splitted into
two components (1085–1040 cm−1), as a result of symmetry
breaking of the PO4 tetrahedron. For the [PW11O39M]5− ani-
ons, the value of the ν3 PO4 splitting, Δν, was always lower
than that of the free ligand [PW11O39]7− anion. And then,
the M cation filled the hole in the octahedral lacuna, and to
some extent restored the symmetry of the central tetrahe-
dron, owing to the interaction between M and the available
oxygen of the central PO4 group (Oa) [25]. The higher value
of Δν indicated lower interaction strength of the metal M
with the available oxygen atom of the central PO4 group
(Oa). As shown in Fig. 1, comparing the value of Δν, it can
be seen that the interaction strength decreased in the fol-
lowing order: Ni2+>Co2+>Fe2+>Cu2+. Besides, the SEM
images of the prepared catalysts are shown in Fig. 2. As
shown in Fig. 2, all the catalysts present the rough lump
structure at the micron level.
3 Results and Discussion
3.1 The Catalyst Confirmation
The compositions of the synthesized heteropolycompounds
were analyzed by Inductive Coupled Plasma Emission Spec-
trometer (ICP). As shown below, The found values were in
accordance with the calculated values.
Anal. Calcd for Na7[PW11O39]·16H2O: Na, 5.18;
W, 64.68. Found: Na, 5.23; W, 64.91. Anal. Calcd for
Na5[PW11O39Ni]·16H2O: Na, 3.66; W, 64.42; Ni, 1.87.
Found: Na, 3.76; W, 64.57; Ni, 1.91. Anal. Calcd for
Na5[PW11O39Co]·16H2O: Na, 3.66; W,64.41; Co, 1.88.
Found: Na, 3.69; W, 64.66; Co, 1.94. Anal. Calcd for
Na5[PW11O39Fe]·16H2O: Na, 3.67; W,64.47; Fe, 1.78.
Found: Na, 3.75; W, 64.81; Fe, 1.84. Anal. Calcd for
Na5[PW11O39Cu]·16H2O: Na, 3.66; W,64.32; Cu, 2.02.
Found: Na, 3.86; W, 64.52; Cu, 2.21.
3.2 Catalytic Performance in Simulated Diesel Oil
The activity of the prepared catalyst on the oxidation of the
DBT was evaluated in the n-octane/acetonitrile biphasic
system. The experimental identical conditions, which were
favorable to the keggin type acids catalyst, were adopted
with the reaction temperature as 60 °C, the initial sulfur
content as 500 ppm, the amount of catalyst as 1% of the
total mass, and the O/S molar ratio as 12. The catalysts were
pre-immersed in H2O2 solution (containing needed amount
of H2O2 with minimum water) for 5 min before fed into the
reaction mixture.
The catalysts synthesized were verified by FT-IR spec-
troscopy in Fig. 1. The four typical absorption bands which
represented Keggin structure were showed in the range
700–1100 cm− 1. The spectrum of the [PW12O40]3−anion
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H. Wang et al.
Fig. 2 SEM images of the lacunary Keggin heteropoly compounds [PW11O39]7−(a) and [PW11O39M]5−, with M=Ni2+ (b), Co2+(c), Fe2+ (d), or
Cu2+ (e)
The sulfur conversion at a reaction time of 180 min was
showed in Table 1. Due to high catalytic activity in the
H2O2 decomposition, the sulfur conversions were sharply
weakened for Na5[PW11O39Cu] and Na5[PW11O39Fe]. The
sulfur elimination of Na7[PW11O39], Na5[PW11O39Co]
and Na5[PW11O39Ni] approximated to H3PW12O40 that
was evaluated as efficient catalyst in ODS reaction, and
Na5[PW11O39Ni] was chosen for further experiments carried
out to investigate the effects of several operation factors,
including temperature, O/S molar ratio, initial sulfur con-
centration and the dosage of catalyst. Moreover, in the 5 min
pre-immersed time, the color of the mixture of H2O2 and
Na5[PW11O39M] (M = Co2+ or Ni2+) turned shallow, and
the mixture of H2O2 and Na7[PW11O39] turned from white
to pale yellow. In light of literatures reports [20, 26, 27]
and phenomena observed above, it can be inferred that the
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Oxidative Removal of Organo-sulfur Species via H2O2 Oxidation Catalyzed by Lacunary…
Table 1 Activity comparison of Keggin type catalysts on the oxida-
The increases of the catalyst dosage promoted formation
of peroxo-heteropoly compound intermediates, which pos-
sess much higher oxidation capacity than H2O2, and there-
fore accelerated the oxidation reaction. However, after a cer-
tain high catalyst dosage, higher amount of catalyst would
introduce more transition metal ions to the reaction system.
The metal ions will accelerate the decomposition of H2O2 to
H2O and O2. And the excessive catalytic decomposition of
H2O2 will reduce oxidant dosage used for sulfur oxidation,
thus declining the conversion of DBT. Hence, the favorable
catalyst dosage can be recommended as 0.5% of the total
mass.
tion of DBT
Keggin type catalysts
Sulfur
conversion
(%)
Na5 [PW11O39Fe]
Na5 [PW11O39Co]
Na5 [PW11O39Ni]
Na5 [PW11O39Cu]
Na7[PW11O39]
57.31
97.87
98.67
61.98
99.41
99.23
H3PW12O40
lacunary catalyst can react with H2O2, producing active
intermediates known as peroxo-heteropoly compound which
was testified in the further contrast experiments.
3.3.2 O/S Molar Ratio
O/S molar ratio plays a significant role in the oxidation of
DBT. As a common principle, the increase in concentration
of the H2O2 will lead to the increase of the conversion of the
DBT and the reaction rate. As the O/S molar ratio increased
from 6 to 9, the sulfur conversion resulted in a sharp increase
from 85.6 to 99.5% at the reaction time of 120 min. And
then, when the O/S molar ratio was raised from 9 to 18,
the final sulfur conversion increased slightly from 99.5 to
99.7% and a faster reaction rate can be observed (Fig. 4).
Taking account of economy and desulfurization efficiency,
the optimal O/S molar ratio was regarded as 12.
3.3 Main Factors Affecting the ODS Process
3.3.1 Catalyst Dosage
To study the effect of dosage of catalyst on the removal of
sulfur, four different values, 0.25, 0.5, 1 and 2% were taken
by varying catalyst dosages while keeping other conditions
constant. As shown in Fig. 3, with the catalyst dosage increa-
seing from 0.25 to 2% of the total mass of n-octane and
DBT, the maximum efficiencies of 99.5% can be achieved
at the 0.25 and 0.5% of the total mass and oxidation rate was
more quickly at 0.5% of that. Corresponding to 1 and 2% of
total mass, efficiencies of 98.6 and 88.0% can be obtained
at a reaction time of 180 min.
3.3.3 Reaction Temperature
As a predominant factor, reaction temperature was inves-
tigated under otherwise identical conditions as mentioned
above. The result was shown in Fig. 5. It can be observed
Fig. 3 The effect of catalyst dosage. Experimental conditions: tem-
perature, 60 °C; initial sulfur concentration, 500 ppm; O/S molar
ratio, 12
Fig. 4 The effect of O/S molar ratio. Experimental conditions: tem-
perature, 60 °C; initial sulfur concentration, 500 ppm; catalyst dos-
age, 0.5% the mass of normal octane and DBT
1 3

H. Wang et al.
marked influence on the process efficiency. From the results
in Fig. 6, within the initial sulfur content range from 150
to 500 ppm, the sulfur removal decreased in the order of
150 ppm>350 ppm>500 ppm at the reaction of 0.5 min.
This result can be attributed to the fact that with the same
amount of extractant, the lower initial sulfur content showed
higher conversion of DBT. It can be observed that the final
sulfur removals were all above 99.5%, particularly 99.9% for
initial sulfur content of 150 ppm after 120 min. These results
demonstrated that agreeable effect of deep desulfurization
has been achieved within the initial sulfur content at vari-
ous levels investigated in this paper. The reasonable initial
sulfur content of the 99.7% efficiency was recommended as
350 ppm, approximating to the 300 ppm in the real diesel
oil.
The results indicated optimized reaction conditions can
enhance ODS reaction. The favourable conditions can be
recommended with catalyst dosage as 0.5% of the total mass,
the O/S molar ratio as 12, temperature as 70 °C and the ini-
tial sulfur content as 350 ppm.
Fig. 5 The temperature dependence of the process. Experimental
conditions: initial sulfur concentration, 500 ppm; O/S molar ratio, 12;
catalyst dosage, 0.5wt.% of the total mass
that the sulfur elimination increased from 89.2 to 98.4% with
the reaction temperature increasing from 50 °C to 80 °C in
the first 5 min. In accordance with the chemical kinetics,
reaction reached an equilibrium in a shorter time at higher
temperature. As a whole, 70 °C was chosen as the suitable
condition.
3.4 The Confirmation of the Active Intermediates
and Proposed Reaction Mechanism
The catalyst with heteropoly anions can provide an efficient
oxidative reaction pathway with H2O2. Heteropoly anions
can react with H2O2, producing active intermediates known
as peroxo-heteropoly compound which facilitates the oxida-
tion of refractory organosulfur compounds [20, 26, 27]. In
order to confirm the presence and the oxidative effect of the
peroxo-heteropoly compound in the oxidative reaction with
3.3.4 Initial Sulfur Content
Another factor that should be concerned was the initial sul-
fur content. It was found that initial sulfur content had a
Fig. 7 Performance of the contrast experiments. Conditions: tempera-
ture, 70 °C; initial sulfur content, 350 ppm; O/S molar ratio, 12; cata-
lyst dosage, 0.5wt.% of total mass
Fig. 6 The effect of initial sulfur concentration. Experimental con-
ditions: temperature, 70 °C; O/S molar ratio, 12; catalyst dosage,
0.5wt.% of the total mass
1 3

Oxidative Removal of Organo-sulfur Species via H2O2 Oxidation Catalyzed by Lacunary…
Na5[PW11O39Ni] as the catalyst, contrast experiments were
carried out under the favorable identical conditions.
equilibrium in 120 and 30 min, respectively. More active
intermediates, peroxo-heteropoly species existing in the lat-
ter system may give rise to this result. The foregoing com-
parisons and analyses were responsible for the presence
and the higher oxidative activity of the peroxo-heteropoly
species.
As shown in Fig. 7, firstly, the performance comparison
between the fresh catalysts un-immersed in H2O2 and pre-
immersed in H2O2 was conducted, and the final desulfuri-
zation efficiencies were 60.7% and 99.7%, indicating that
new species formed during the interaction of H2O2 with
the Na5[PW11O39Ni], was more available for the oxidative
desulfurization reaction. The catalyst of the new species
known as peroxo-heteropoly compound can be tested in
the next two steps. Secondly, the sulfur conversion of fresh
catalyst un-immersed in H2O2 and the reused catalyst un-
immersed in H2O2 was compared, and the final desulfuriza-
tion efficiencies were 60.7 and 98.1%. This can be assigned
to a possibility that the reused catalyst was the product of
the Na5[PW11O39Ni] catalyst with H2O2. Thirdly, efficien-
cies of the reused catalyst un-immersed in H2O2 with that
pre-immersed in H2O2 were compared, and the final sulfur
conversions were 98.1 and 99.5%, and the reaction reached
The reaction product was analyzed by GC-MS. As
shown in Fig. 8, the reaction product can be determined
as DBTO2. Through the above analysis, we proposed the
reaction mechanism as follows: firstly, some of DBT in the
n-octane was extracted into MeCN phase. Then, the DBT
in the MeCN was oxidized to DBTO2 by the peroxo-heter-
opoly species produced through the reaction of H2O2 with
the Na5[PW11O39Ni]. Finally, more and more DBT was
extracted into the MeCN phase when the oxidation reaction
was in process, and oxidized to DBTO2. Due to the strong
solubility of the DBTO2 in the MeCN, the DBT in n-octane
was nearly completely removed. The proposed reaction
mechanism was shown in scheme 1.
Fig. 8 The GC-MS spectra of the reaction product in MeCN phase
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H. Wang et al.
4 Conclusion
The lacunary Keggin 11-tungstophosphates catalysts were
evaluated in ODS reaction. The catalyst Na5[PW11O39Cu]
and Na5[PW11O39Fe] were unavailable owing to the catalytic
effect in H2O2 decomposition. The remaining three cata-
lysts Na7[PW11O39], Na5[PW11O39Co] and Na5[PW11O39Ni]
exhibited high activity for the oxidation of dibenzothio-
phene, The efficiency of representative Na5[PW11O39Ni] can
be improved to 99.5% by fixing the experimental identical
conditions with catalyst dosage as 0.5% of the total mass, the
O/S molar ratio as 12, temperature as 70 °C and the initial
sulfur content as 350 ppm. Moreover, three comparisons
favored the formation of active intermediates species in the
interaction of H2O2 with Na5[PW11O39Ni] and the higher
oxidative activity which accelerated the reaction rate in ODS
process. Besides the residual sulfur content of the sample
diesel treated by Na5[PW11O39Ni] as catalyst can be reduced
to 12.6 ppm, and Na5[PW11O39Ni] was capacity for deep
desulfurization of real diesel.
H O
Na5[PW11O39Ni]
+
2
2
S
peroxo species
n-octane
MeCN
O
O
S
S
H2O
+
Scheme 1 Reaction mechanism for DBT removal
Table 2 Conversion of organo-sulfur sepcies and real diesel
Organo-sulfur sepcies / diesel samples
Sulfur
conversion
(%)
Acknowledgements Financial support from the National Natural
Science Foundation of China (20976097; 21076116) and PetroChina
Innovation Foundation (2010D-5006-0405) is gratefully acknowledged.
DBT
99.69
99.04
86.12
76.71
88.75
95.84
4.6-DMDBT
BT
TH
Compliance with Ethical Standards
Real diesel: sample A
Real diesel: sample B
Conflict of interest There are no conflicts to declare.
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Affiliations
Han Wang1 · Rui Wang1 · Yongqiang Zhang1 · Shuaiyong Dou1 · Silchenkova Olga2 · Korchak Vladimir2
1
2
School of Environmental Science and Engineering,
Shandong University, 250199 Jinan, China
Semenov Institute of Chemical Physics, Russian Academy
Sciences, Kosygina str., 4, 119991 Moscow, Russia
1 3