This article was downloaded by: [University of Sussex Library]

On: 11 February 2015, At: 11:25

Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered
office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK

Petroleum Science and Technology

Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/lpet20

The Deep Oxidative Desulfurization

of Fuels Catalyzed by Surfactant-type
Octamolybdate in Acidic Ionic Liquids
a b b b c
J. Ge , Y. Zhou , Y. Yang & M. Xue
a
School of Earth Science and Environmental Engineering , Anhui
University of Science and Technology , Huainan , China
b
School of Chemistry and Chemical Engineering , Southeast
University , Jiang Ning Region , Nanjing , China
c
Biochemical and Environmental Engineering College , Nanjing
Xiaozhuang University , Nanjing , China
Published online: 20 Nov 2013.
Click for updates

To cite this article: J. Ge , Y. Zhou , Y. Yang & M. Xue (2014) The Deep Oxidative Desulfurization of
Fuels Catalyzed by Surfactant-type Octamolybdate in Acidic Ionic Liquids, Petroleum Science and
Technology, 32:1, 116-123, DOI: 10.1080/10916466.2011.580304

To link to this article: http://dx.doi.org/10.1080/10916466.2011.580304

PLEASE SCROLL DOWN FOR ARTICLE

Taylor & Francis makes every effort to ensure the accuracy of all the information (the
“Content”) contained in the publications on our platform. However, Taylor & Francis,
our agents, and our licensors make no representations or warranties whatsoever as to
the accuracy, completeness, or suitability for any purpose of the Content. Any opinions
and views expressed in this publication are the opinions and views of the authors,
and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content
should not be relied upon and should be independently verified with primary sources
of information. Taylor and Francis shall not be liable for any losses, actions, claims,
proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or
howsoever caused arising directly or indirectly in connection with, in relation to or arising
out of the use of the Content.

This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,
systematic supply, or distribution in any form to anyone is expressly forbidden. Terms &
 Conditions of access and use can be found at http://www.tandfonline.com/page/terms-
and-conditions
Downloaded by [University of Sussex Library] at 11:25 11 February 2015
 Petroleum Science and Technology, 32:116–123, 2014
Copyright 
C Taylor & Francis Group, LLC
ISSN: 1091-6466 print / 1532-2459 online
DOI: 10.1080/10916466.2011.580304

The Deep Oxidative Desulfurization of Fuels Catalyzed by

Surfactant-type Octamolybdate in Acidic Ionic Liquids

J. Ge,1,2 Y. Zhou,2 Y. Yang,2 and M. Xue3

1
Downloaded by [University of Sussex Library] at 11:25 11 February 2015

School of Earth Science and Environmental Engineering, Anhui University of Science

and Technology, Huainan, China
2
School of Chemistry and Chemical Engineering, Southeast University, Jiang Ning Region,
Nanjing, China
3
Biochemical and Environmental Engineering College, Nanjing Xiaozhuang University,
Nanjing, China

Four surfactant-type octamolybdates were synthesized, characterized, and then used as effective catalysts
associated with H2 O2 as oxidant in the acidic ionic liquid, which has been found suitable for deep removal
of organic sulfur in fuels. Under the favorable conditions, the sulfur removal could reach almost 100%,
which was much better than desulfurization performance by the simple extraction with acidic ionic
liquid. Moreover, this acidic ionic liquid can be recycled six times by distillation without obviously
decrease in activity. Meanwhile, the mechanism of oxidation desulfurization was also elaborated.
Keywords: acidic ionic liquid, catalytic oxidation, desulfurization, hydrogen peroxide, octamolybdate

1. INTRODUCTION

Over the past few years, new strict environmental regulations are being imposed on oil refineries to
reduce sulfur level for liquid hydrocarbon fuels (Alonso et al., 2008). For example, many developed
countries have mandated a reduction in fuels sulfur level to 10 ppm by 2009 (Babich and Moulijn,
2003). To meet the requirements of more and more stringent legislations (Wang et al., 2010), the
traditional sulfur compound removing method is catalytic hydrodesulfurization (HDS) has encoun-
tered a great challenge and need a substantial improvement for both selectivity and reactivity of
the catalyst used. Therefore, the development of alternative deep desulfurization processes, such as
adsorption, extraction oxidation, and bioprocesses, is desired. Catalytic oxidation combined with
extraction using ionic liquid has been reported recently. In these processes, with H2 O2 as oxidant,
ionic liquids served as extractants, and additional catalyst was added, such as peroxotungsten com-
plex (Lo et al., 2003), Na2 MoO4 ·2H2 O (Zhu et al., 2008), and phosphotungstic acid (Li et al., 2009).
Lu et al. (2007) and Zhao et al. (2007) first used acidic ionic liquid and H2 O2 in the desulfurization
field. But the experiment had to be carried out in two phases (Jiang et al., 2008) and with large
amount of ionic liquids. In very recent years, octamolybdate catalysts were successfully applied in
the selective oxidation of various sulfides to sulfoxides with H2 O2 as oxidant under mild reaction

Address correspondence to Yuming Zhou, School of Chemistry and Chemical Engineering, Southeast University, Jiang
Ning Region, Nanjing 211189, PR China. E-mail: ymzhou@seu.edu.cn

116
 DESULFURIZATION BY SURFACTANT-TYPE OCTAMOLYBDATE 117

conditions (Yang et al., 2009). However, we found that octamolybdate as a catalyst for desulfuriza-
tion reaction was rarely investigated in contemporary chemistry field. For these reasons, in this work,
we introduced a series of surfactant-type octamolybdate catalysts into catalytic oxidative extractive
desulfurization system (Zhu et al., 2007). It was found that the sulfur removal could reach almost
100%.

2. EXPERIMENTAL

2.1 Instrumentations
Downloaded by [University of Sussex Library] at 11:25 11 February 2015

Infrared (FT-IR) spectra of all the catalysts (KBr pellets) were recorded on Tensor 27 (BrukerT27)
equipment, while ultraviolet-visible light (UV-Vis) spectra were obtained using a Model Shimadzu
UV-2201 spectrophotometer (Shimadzu Corporation, Japan); TG/DSC was done on STA-449C
Jupiter (NETZSCH Corporation, Germany); elementary (C, H, and N) analyses were performed using
CHN-O-Rapid (Heraeus Corporation); the content of Mo was measured by gravimetric determination
(GD) in a muffle furnace burning at 800◦ C for 0.5 h.

2.2 Preparation of Tetra-(tetraalkylammonium) octamolybdate

All the octamolybdates were synthesized and purified according to the procedures reported in the
literature with a little modified (Yang et al., 2009).

2.3 Preparation of Acidic Ionic Liquids

The acidic ionic liquids were synthesized and purified according to the method reported by Fei et al.
(2004).

2.4 General Procedure of Oxidation of Model Oils

The catalytic oxidative desulfurization experiments of the model oil were carried out in a 50 mL
round-bottomed flask. The required amounts of acidic ionic liquid, catalyst, model oil (1000 ppm
sulfur as DBT in normal n-octane), and H2 O2 were added to the flask in turns and stirred vigorously
in oil bath at reaction temperature. After the reaction, the model oil was withdrawn and analyzed by
gas chromatography with tetradecane as internal standard, coupled with a flame ionization detector
(GC-FID). AC5 capillary column (30 m × 0.53 mm inner diameter × 1.0 μm film thickness) was
used for separation.

3. RESULTS AND DISCUSSION

3.1 Characterization of Catalysts

3.1.1 Catalysts confirmation

Through elementary (C, H, and N) analysis and GD method, the found values of C, H, N, and
Mo content of catalysts. Compared with the calculated values, the molar ratios of C, H, N, and Mo
were confirmed to agree with the desired ratios.
 118 J. GE ET AL.

TABLE 1
Data of IR and UV-Vis

Entry Q4 [Mo8 O26 ] FT-IR, cm−1 UV-Vis, nm

1 [(C4 H9 )4 N+] 952 916 858 802 665 552 206

2 [(C12 H25 )N+(CH3 )3 ] 952 915 858 801 664 552 211
3 [(C14 H29 )N+(CH3 )3 ] 952 915 858 801 664 554 209
4 [(C16 H33 )N+(CH3 )3 ] 952 905 854 805 662 559 210

3.1.2 The FT-IR and UV-vis spectra of catalysts

Downloaded by [University of Sussex Library] at 11:25 11 February 2015

The FT-IR and UV-Vis spectroscopy of the catalysts are shown in Table 1. The FT-IR and UV-Vis
spectra of catalysts were proved to be the structure of [Mo8 O26 ]4− and in good agreement with the
results reported previously (Klemperer and Shum, 1976).

3.1.3 TG-DSC analysis of catalysts

TG-DSC of [(C4 H9 )4 N] 4 [Mo8 O26 ] under nitrogen showed that the catalyst did not have crystalline
water and coordinated water, because there was no mass loss and no endothermic peak under 100◦ C.
After 300◦ C there were two mass loss on the TG curve, which might have contributed to the
decomposition of organic cations of catalysts. The endothermic peaks on the DSC curve emerged
from 320◦ C to 360◦ C and from 380◦ C to 410◦ C, respectively. Until about 700◦ C, there was no
more mass loss. The final reminder was molybdic oxide. The other compounds TG–DSC curves of
tetra-(tetraalkylammonium) octamolybdate were shown a similar decomposition process (Figure 1).

3.2 Desulfurization Catalyzed by Tetra-(tetraalkylammonium) octamolybdate

3.2.1 Influence of different reaction systems

Table 2 shows four kinds of different desulfurization systems. When using acidic ionic liquid
(CH2 )3 SO3 HMIm]BF4 solely as the extractant for removing DBT-containing model oil, the sulfur

FIGURE 1 TG–DSC of catalysts.

 DESULFURIZATION BY SURFACTANT-TYPE OCTAMOLYBDATE 119

TABLE 2
Sulfur Removal of Different Desulfurization Systems

Catalyst Sulfur Removal of Different Desulfurization Systems, %

Entry Q4 Mo8 O26 Catalyst + H2 O2 IL + Catalyst + H2 O2 IL + H2 O2 IL

1 [(C4 H9 )4 N]+ 33.8 94.6 33.8

2 [(C12 H25 )N(CH3 )3 ]+ 86.8 98.3
3 [(C14 H29 )N(CH3 )3 ]+ 71.6 88.7
4 [(C16 H33 )N(CH3 )3 ]+ 99 77.2
16.4
Downloaded by [University of Sussex Library] at 11:25 11 February 2015

Conditions: n (DBT)/n (catalyst) = 100, Catalyst = [(C12 H25 )N+(CH3 )3 ]4 [Mo8 O26 ], n (H2 O2 )/n (DBT) = 4, V (model
oil ) = 5 mL, V ([(CH2 )3 SO3 HMIm]BF4 ) = 1 mL, T = 70◦ C, t = 3 h.

removal only reached 16.4%, with addition of H2 O2 in [(CH2 )3 SO3 HMIm]BF4 the sulfur removal
increased to 33.8%. On the other hand, when the catalyst, H2 O2 , and acidic ionic liquid were
employed together, the removal of DBT increased sharply. However, In this experiment, three
catalysts with long alkyl chains ([C14 H29 N+(CH3 )3 ]4 Mo8 O26 , [(C12 H25 )N+(CH3 )3 ]4 Mo8 O26 , and
[C16 H33 N+(CH3 )3 ]4 Mo8 O26 exhibited high catalytic activity without acidic ionic liquid, The results
obtained in this work identical to that described for the emulsion droplet system (Gao et al., 2006).
However, after addition of acidic liquid in the desulfurization system, this phenomenon lay in that
long alkyl chain catalyst distribute in acidic ionic liquid evenly and the stability of emulsion droplets
were break, leading to low sulfur removal. Moreover, as the length of the alkyl chain of catalyst
increased, the sulfur removal decreased (He et al., 2008). The reactivity order of the catalyst was
[C12 H25 N (CH3 )3 N] +> [C14 H29 N (CH3 )3 ] + > [C16 H33 N (CH3 )3 ] +. Based on the results obtained,
[(C12 H25 )N+(CH3 )3 ]4 [Mo8 O26 ] was chosen for further experiments.

3.2.2 Influence of temperature and time on the sulfur removal

Figure 2 shows the removal of DBT in n-octane versus reaction time at various temperatures. In
this desulfurization system, DBT was oxidized to corresponding sulfones by the octamolybdate. So a
continuous decrease in the concentration of DBT in n-octane was observed at various temperatures.
The higher the reaction temperature was, the faster the oxidation rate of DBT was. From the results,
the favorable temperature can be recommended as 70◦ C.

3.2.3 Influence of O/S and the amount of catalyst on the sulfur removal

According to the stoichiometric reaction, 2 mol of H2 O2 are consumed for 1 mol of sulfur com-
pound. It was noteworthy that there was a competition between the hydrogen peroxide decomposition
side reaction and DBT oxidation reaction. The sulfur removal of different molar ratios of H2 O2 and
DBT are shown in Table 3. Sulfur removal of model oil increased monotonically with increasing O/S
molar ratio, these results also indicated the optimal O/S molar ratio was 4 at 70◦ C. From Table 3, it
also can be seen, when the DBT/catalyst molar ratio was changed from 100:1 to 10:1, sulfur removal
of model oil could reach 100%. These results indicated that the amount of catalyst in the reaction
also had a vital effect on DBT removal.
 120 J. GE ET AL.
Downloaded by [University of Sussex Library] at 11:25 11 February 2015

FIGURE 2 Influence of temperature and time on the sulfur removal. Conditions: Catalyst = [(C12 H25 )
N+ (CH3 )3 ] 4 [Mo8 O26 ], n (DBT)/n (catalyst) = 100, n (H2 O2 )/n (DBT) = 4, V (model oil) = 5 mL,
V ([(CH2 )3 SO3 HMIm]BF4 ) = 1 mL.

3.2.4 Influence of the a different acidic ionic liquid on the sulfur removal

The desulfurization results of the model oil catalyzed by [(C12 H25 )N+(CH3 )3 ]4 [Mo8 O26 ] in
different acidic ionic liquids are shown in Figure 3. When the n (DBT)/n (catalyst) = 100 and
(H2 O2 )/n (DBT) = 4, the oxidative desulfurization ability of the acidic ionic liquids is affected by
their chemical properties, such as the cation and anion structure. As data shows, with the same
anions (BF− − −
4 , HSO4 , H2 PO4 ), the removal of organic sulfur ability of model oil followed the order:
N-methylimidazolium-based acidic ionic liquids > triethylammonium-based acidic ionic liquids >
pyridinium-based acidic ionic liquids. But when the cations of acidic ionic liquids are the same
([(CH2 )4 SO3 HMIm]+, [(CH2 )4 SO3 HPy]+, [(CH2 )4 SO3 HTEA]+), the desulfurization ability acidic
ionic liquids connect with the property of anions. It was shown that the desulfurization ability of the
anions of acidic ionic liquids for sulfur component followed the order: BF− −
4 >HSO4 >H2 PO4 .
−

TABLE 3
Influence of O/S and the Amount of Catalyst on the Sulfur Removal

Sulfur Removal of Different Desulfurization Systems, %

O/S 100:1 50:1 25:1 10:1

1:1 25.6 27.1 63.4 96.6

2:1 47.2 67.8 88.6 97.6
4:1 98.3 98.8 98.9 99.1
6:1 98.5 99.2 99.3 99.5
8:1 98.7 99.4 99.6 100.0

Conditions: Catalyst = [(C12 H25 )N+(CH3 )3 ] 4 [Mo8 O26 ], V (model oil) = 5 mL, V ([(CH2 )3 SO3 HMIm]BF4 ) = 1 mL,
T = 70◦ , t = 3 h.
 DESULFURIZATION BY SURFACTANT-TYPE OCTAMOLYBDATE 121
Downloaded by [University of Sussex Library] at 11:25 11 February 2015

FIGURE 3 Influence of the different type of acidic ionic liquid on the sulfur removal. Conditions: Catalyst =
[(C12 H25 )N+(CH3 )3 ] 4 [Mo8 O26 ], n (DBT)/n (catalyst) = 100.

3.2.5 Recovery/regeneration of ionic liquids

After reaction, the reaction system was still a biphasic system in which the acidic ionic liquid
phase, along with the catalyst and excess H2 O2 were still the lower layer, so the oil could be separated
by decantation from biphasic system of the acidic ionic liquid easily. The H2 O2 and model oil were
then evaporated from the acidic ionic liquid phase at 120◦ C in oil bath for 2 h. Fresh H2 O2 and
model oil then were added into the reaction system for the next run. From the results in Figure 5
indicate that the catalytic system could be recycled six times without obviously decrease in activity
at the same reaction conditions.

3.2.6 Possible mechanism of desulfurization system

As seen in Figure 4, during the reaction, surfactant-type octamolybdate were homogeneous

distributed in the acidic ionic liquid after the system was stirred vigorously. It is well known that
H2 O2 is a strong oxidant in the acidic medium. When octamolybdate was dissolved in H2 O2 solution
and then octamolybdate was rapidly oxidized to peroxomolybdic compound by H2 O2 , which has been
widely recognized as active intermediate for oxidations of many organic compounds by H2 O2 . The
lipophilic quaternary ammonium cations and the hydrophilic peroxomolybdic compounds played
different roles in the system consisted of acidic ionic liquid and model oil. The cation with long carbon
chain transferred peroxo species to the substrates DBT, and formed the DBTO2 , whose polarity was
high enough to be extracted into acidic ionic liquid continuously, and made the oxidation reaction
accomplish completely. Due to the excess H2 O2 , a circulatory system is form. Once the H2 O2 was
consumed up, the catalyst precipitated from the reaction system.

3.2.7 Mutual solubility of acidic ionic liquid and n-octane

Due to a noticeable mutual solubility of a nitrogen-bearing acidic ionic liquid and n-octane could
lead to NOx pollution and separation cost. So it is important to investigate the mutual solubility
 122 J. GE ET AL.
Downloaded by [University of Sussex Library] at 11:25 11 February 2015

FIGURE 4 Influence of the recycle times on sulfur removal. Conditions: n(DBT)/n (catalyst) = 100, catalyst =
[(C12 H25 )N+(CH3 )3 ]4 [Mo8 O26 ], n (H2 O2 )/n (DBT) = 4, V (model oil) = 5 mL, V ([(CH2 )3 SO3 HMIm]BF4 ) =
1 mL, T = 70◦ C, t = 3 h.

between the acidic ionic liquid and the oil in the desulfurization system. By analyzing the acidic
ionic liquid-saturated oil sample (acidic ionic liquid was stirred with n-octane) with elementary
analyses. No nitrogen element was found in the sample of acidic ionic liquid-saturated n-octane,
which was a proof that ionic liquid has negligible solubility in model oil. The solubility of oil in
acidic ionic liquid at room temperature can be overcome by back extraction with water, since acidic
ionic liquids are highly hydrophilic. Hence, the problem of the mutual solubility between the acidic
ionic liquid and model oil could be avoided.

FIGURE 5 The proposed mechanism of the deep desulfurization using octamolybdate in acidic IL.
 DESULFURIZATION BY SURFACTANT-TYPE OCTAMOLYBDATE 123

4. CONCLUSIONS

In this work, four surfactant-type octamolybdates and nine acidic ionic liquids were synthesized.
Among four surfactant-type octamolybdates [(CH3 )3 NC12 H25 ]4 Mo8 O26 showed the best catalytic
activity. Under the optimal conditions, the sulfur of removal can get to 100%. This desulfurization
system can be recycled five times by distillation without obviously decrease in activity, and the
mechanism of desulfurization was also elaborated.

ACKNOWLEDGMENTS
Downloaded by [University of Sussex Library] at 11:25 11 February 2015

This work was supported by the National Nature Science Foundation of China (No. 51077013,
50873026), Production and research prospective joint research project of Jiangsu Province of China
(BY2009153), the Key Program for the Scientific Research Guiding Found of Basic Scientific
Research Operation Expenditure, Southeast University (3207040103), 333 high-level talent training
project, Jiangsu Province of China (BRA2010033), and Student Research Training Program of
Southeast University (No. 091028644).

REFERENCES

Alonso, L., Arce, A., Francisco, M., and Soto, A. (2008). Solvent extraction of thiophene from n-alkanes (C7 , C12 , and C16 )
using the ionic liquid [C8 mim][BF4 ]. J. Chem. Thermodynam. 40:966–972.
Babich, I. V., and Moulijn, J. A. (2003). Science and technology of novel processes for deep desulfurization of oil refinery
streams: A review. Fuel 82:607–631.
Fei, Z., Zhao, D., Geldbach, T. J., Scopelliti, R., and Dyson, P. J. (2004). Brønsted acidic ionic liquids and their zwitterions:
Synthesis, characterization and pKa determination. Chemistry 10:4886–4893.
Gao, J., Wang, S., Jiang, Z., Lu, H., Yang, Y., Jing, F., and Li, C. (2006). Deep desulfurization from fuel oil via selec-
tive oxidation using an amphiphilic peroxotungsten catalyst assembled in emulsion droplets. J. Mol. Catal. A: Chem.
258:261–266.
He, L., Li, H., Zhu, W., Guo, J., Jiang, X., Lu, J., and Yan, Y. (2008). Deep oxidative desulfurization of fuels using
peroxophosphomolybdate catalysts in ionic liquids. Ind. Eng. Chem. Res. 47:6890–6895.
Jiang, X. C., Nie, Y., Li, C. X., and Wang, Z. (2008). Imidazolium-based alkylphosphate ionic liquids - A potential solvent
for extractive desulfurization of fuel. Fuel 87:79–84.
Klemperer, W. G., and W. Shum (1976). Synthesis and interconversion of the isomeric, α- and β-molybdate (Mo8 O4− 26 ) ions.
J. Am. Chem. Soc. 98:8291–8293.
Li, H. M., He, L. N., Lu, J. D., Zhu, W. S., Jiang, X., Wang, Y., and Yan, Y. S. (2009). Deep oxidative desulfurization of fuels
catalyzed by phosphotungstic acid in ionic liquids at room temperature. Energy Fuels 23:1354–1357.
Lo, W. H., Yang, H. Y., and Wei, G. T. (2003). One-pot desulfurization of light oils by chemical oxidation and solvent
extraction with room temperature ionic liquids. Green Chem. 5:639–642.
Lu, L., Cheng, S. F., Gao, J. B., Gao, G. H., and He, M. Y. (2007). Deep oxidative desulfurization of fuels catalyzed by ionic
liquid in the presence of H2 O2 . Energy Fuels 21:383–384.
Wang, R., Zhang, G., and Zhao, H. (2010). Polyoxometalate as effective catalyst for the deep desulfurization of diesel oil.
Catal. Today 149:117–121.
Yang, C., Jin, Q., Zhang, H., Liao, J., Zhu, J., Yu, B., and Deng, J. (2009). Tetra-(tetraalkylammonium)octamolybdate catalysts
for selective oxidation of sulfides to sulfoxides with hydrogen peroxide. Green Chem. 11:1401–1405.
Zhao, D. S., Wang, J. L., and Zhou, E. P. (2007). Oxidative desulfurization of diesel fuel using a Brønsted acid room
temperature ionic liquid in the presence of H2 O2 . Green Chem. 9:1219–1222.
Zhu, W., Li, H., Jiang, X., Yan, Y., Lu, J., and Xia, J. (2007). Oxidative desulfurization of fuels catalyzed by peroxotungsten
and peroxomolybdenum complexes in ionic liquids. Energy Fuels 21:2514–2516.
Zhu, W. S., Li, H. M., Jiang, X., Yan, Y. S., Lu, J. D., He, L. N., and Xia, J. X. (2008). Commercially available molybdic
compound-catalyzed ultra-deep desulfurization of fuels in ionic liquids. Green Chem. 10:641–646.