JOURNAL OF FUEL CHEMISTRY AND TECHNOLOGY

Volume 35, Issue 3, June 2007

Online English edition of the Chinese language journal

Cite this article as: J Fuel Chem Technol, 2007, 35(3), 293−296 RESEARCH PAPER

Desulfurization of gasoline by extraction with

N-alkyl-pyridinium-based ionic liquids
WANG Jian-long1, ZHAO Di-shun1,2,*, ZHOU Er-peng1, DONG Zhi3

1
School of Chemical Engineering, Tianjin University, Tianjin 300072, China
2
School of Chemical and Pharmaceutical Engineering, Hebei University of Science and Technology, Shijiazhuang 050018, China
3
School of Chang’an, Hebei University of Science and Technology, Shijiazhuang 050091, China

Abstract: Six N-alkyl-pyridinium-based ionic liquids, N-butyl-pyridinium nitrate ([BPy]NO3), N-ethyl-pyridinium nitrate
([EPy]NO3), N-butyl-pyridinium tetrafluoroborate ([BPy]BF4), N-ethyl-pyridinium tetrafluoroborate ([EPy]BF4), N-ethyl-pyridinium
acetate ([EPy]Ac), and N-butyl-pyridinium acetate ([BPy]Ac), were prepared and tested in the extraction desulfurization of gasoline. It
is found that [BPy]BF4 has the best effect on the selective removal of sulfur-containing compounds from gasoline at room temperature
among these ionic liquids. The extraction rate of [BPy]BF4 is 45.5%. The desulfurization effect of [EPy]BF is the lowest. The used
ionic liquids can be regenerated by rotary evaporation or re-extraction using tetrachloro-methane.
Key Words: ionic liquids; model gasoline; desulfurization; extraction

In recent years, deep desulfurization of transportation fuels
has been attracted much attention in the worldwide and
decreasing the sulfur content in gasoline is an urgent object
in the petroleum refining industry. Low-sulfur fuel is often
obtained by hydrocracking processes or hydrotreating
processes, which can eliminate the sulfur in aliphatic and
alicyclic sulfur compounds[1,2]. However, alkyl thiophenes
and benzothiophenes are difficult to be eliminated in these
two processes because of the sterically hindered adsorption
of these compounds on the catalyst surface. Moreover,
during the deep hydrodesulfurization processes the energy
and hydrogen consumption will be evidently increased, and
undesirable side reactions (such as the saturation of olefins)
also will be induced[3]. Such side reactions can result in the
decrease of the octane number of gasoline. Thus, alternative
ways without hydrogen consumption, such as oxidative
desulfurization, biodesulfurization, extractive desulfurizaton,
and adsorptive desulfurization, have hold many researchers’
interest[4−13].
Ionic liquids (ILs) have the ability of extracting aromatic
sulfur-containing compounds at ambient conditions without
H2 consumption. In addition ILs are immiscible with fuel,
and the used ILs can be regenerated and recycled by solvent
washing or distillation. In previous researches,
N-alkyl-imidazolim-based ionic liquids are mostly used in
extraction desulfurization of fuels[9−13]. In this article,
N-alkyl-pyridinium-based ionic liquids, N-butyl-pyridinium
nitrate ([BPy]NO3), N-ethyl-pyridinium nitrate ([EPy]NO3),
N-butyl-pyridinium tetrafluoroborate ([BPy]BF4),
N-ethyl-pyridinium tetrafluoroborate ([EPy]BF4),
N-ethyl-pyridinium acetate ([EPy]Ac), and
N-butyl-pyridinium acetate ([BPy]Ac), were prepared and
tested in the extraction desulfurization of the model oil and
gasoline.
1 Experimental
1.1 Preparation of ILs
N-butyl-pyridinium bromide was prepared as the
following procedure: pyridine (0.5 mol) and 1-bromobutane
(0.5 mol) were added to a magnetic stirred slurry of
cyclohexane (50 mL) in a round-bottom flask fitted with a
reflux condenser and a drying tube. The mixture was stirred
at 64 °C for 24 h until no more precipitate formed. The white
precipitate was filtrated off, and then the resulting solid was
washed two times with ethyl acetate. The resulting
N-butyl-pyridinium bromide was evaporated in a vacuum
drying oven to remove the remaining ethyl acetate, raw
material, and solvent. N-ethyl-pyridinium bromide was

Received: 2006-11-09; Revised: 2007-03-11

* Corresponding author. Tel/Fax: +86-311-88632009; E-mail: zhao_dsh@hebust.edu.cn
Foundation item: Supported by the National Natural Science Foundation of China (20576026).

Copyright©2007, Institute of Coal Chemistry, Chinese Academy of Sciences. Published by Elsevier Limited. All rights reserved.
 WANG Jian-long et al. / Journal of Fuel Chemistry and Technology, 2007, 35(3): 293−296
prepared as the same procedure as N-butyl-pyridinium
bromide.
Ionic liquid N-butyl-pyridinium tetrafluoroborate was
prepared by adding N-butyl-pyridinium bromide (0.3 mol)
and sodium fluoroborate (0.35 mol) to acetone (300 mL), and
then the mixture was agitated at room temperature for 24 h.
Then the resulting precipitate was filtered off, and the
solvent was removed by rotary evaporation to leave a
yellowish liquid. The trace quantity of acetone was removed
by vacuum evaporation. N-ethyl-pyridinium tetrafluoroborate
was prepared as the same procedure as N-butyl-pyridinium
tetrafluoroborate.
Ionic liquid N-butyl-pyridinium nitrate was prepared by
adding equal amount (mole) of N-butyl-pyridinium bromide
and ammonium nitrate to methyl alcohol, and then the
mixture was agitated at room temperature for 48 h. Then the
resulting precipitate was filtered off, and the solvent was
removed by rotary evaporation to leave a brown liquid. The
trace quantity of methyl alcohol was removed by vacuum
evaporation. N-ethyl-pyridinium nitrate, N-butyl-pyridinium
acetate, N-ethyl-pyridinium acetate were prepared as the
same procedure as N-butyl-pyridinium nitrate.
1.2 The desulfurization procedure
Desulfurization of the model oil was carried out as follows:
thiophene was dissolved in a solution of n-heptane and xylol
with the volume ratio of 1:1. The sulfur concentration of the
model oil is 498 ng/µL. The real gasoline was obtained from
the Shijiazhuang refinery.
All the desulfurization experiments were conducted in a
100 mL glass flask. The model oil or gasoline and ionic
liquids were added into the flask at room temperature except
[EPy]BF4. The mass ratio of ILs to the model oil or gasoline
was 1:1. The biphasic mixture was then stirred for 30−40
min. The sulfur content of stratified mixture was quantitative
analyzed by a WK-2D microcoulometric detector.
2 Results and discussion
2.1 Desulfurization of the model oil with different ILs
The desulfurization results of N-alkyl-pyridinium-based
ILs are shown in Table 1. When the mass ratio of ILs to the
model oil is 1:1, [BPy]BF4 has the best extracting ability to
remove thiophene from the model oil among the six ILs at
the same conditions, and its extracting ability increases with
the mass ratio of ILs to the model oil. The extraction
desulfurization ability of ILs connects with their chemical
properties, such as the cation or anion structure, the size of
ILs. As data shows, with the same anions (BF4−, NO3−, Ac−),
N-butyl-pyridinium-based ILs with the substitution of a
longer alkyl group to the pyridinium ring, have higher
desulfurization ability than N-ethyl-pyridinium-based ILs.
But when the cations of ILs are the same (BPy, EPy), the
desulfurization ability of ILs connects with the chemical
property of anion. The lone pair electrons of pyridine and the
electron-donating ability of alkyl substitutions make the
N-alkyl-pyridinium have higher polarizable aromatic
π-electron density than pyridine. The strong affinity of the
ILs for the aromatics sulfur compounds is related to the high
polarity of the ILs. The mechanisms for the extraction of
sulfur-containing compounds with non-Lewis-acidic ILs are
because the formation of liquid-clathrate compounds and π-π
interactions between aromatic structures of the extraction
target and the pyridinium ring system[13,14].
Table 1 Desulfurization results of ILs at different mass ratios of
ILs to model gasoline
Sulfur removal η/%
ILs mass ratio of ILs to the model oil
1:1 1:2 1:3
[BPy]BF4 45.5 28.6 16.9
[BPy]NO3 30.1 19.1 9.4
[BPy]Ac 32.1 20.3 10.2
[EPy]BF4a 21.8 12.6 8.9
[EPy]NO3 27.1 17.3 13.8
[EPy]Ac 23.0 15.7 9.7
Condition: room temperature (except a: 50 °C); extraction time 30−40 min
It is also found that the desulfurization ability of ILs is
relation to the agitation. When the mixture is stirred
vigorously, the desulfurization of ILs is high. This is because
that the viscosity of ILs is higher than that of oil, and
vigorously stirring can mix them together. When the reaction
temperature is downed to the room temperature, the ionic
liquid [EPy]BF4 is solid and the sulfur removal decreases
from 21.9% to 17.9%. The reason may be that the partial
thiophene in liquid-clathrate compounds returns the oil
phase.
2.2 Desulfurization of gasoline with different ILs
The data in Table 2 show the desulfurization results of
gasoline with different ILs. For the six ILs the sulfur
removals of gasoline are all lower than those of the model oil.
Gasoline contains more heteronuclear compounds than the
model oil, such as nitrogen-containing compounds and
sulfur-containing aromatic compounds (alkythiophene,
benzothiophene), which decreases the sulfur removal ability
of N-alkyl-pyridinium ILs. Because of the steric effect of
alkyl groups in the aromatic rings, methylthiophene,
methylbenzothiophene, methyldibenzothiophene, etc,
sulfur-containing compounds in gasoline are extracted less
 WANG Jian-long et al. / Journal of Fuel Chemistry and Technology, 2007, 35(3): 293−296

than thiophene in the model oil by ILs. 2.3 Effect of temperature on desulfurization of ILs

Table 2 Desulfurization results of gasoline with different ILs The effect of temperature on the sulfur removal from the
Before treatment After treatment Sulfur removal model oil using [BPy]BF4 is shown in Table 3. With the
ILs
ρ / ng⋅µL−1 ρ / ng⋅µL−1 η/% increase of temperature the viscosity of ILs is reduced, and
[BPy]BF4 735 455 38.1 then the ILs molecule and the sulfur-containing compounds
[BPy]NO3 735 568 22.8 in the model oil have more chance to contact each other,
[BPy]Ac 735 542 26.3 which results in the high sulfur removal. However, the effect
[EPy]BF4 a
735 649 11.7 of temperature on the desulfurization is limited.
[EPy]NO3 735 585 20.4
[EPy]Ac 735 614 17.5 Table 3 Desulfuriation results of [BPy]BF4 at different
Condition: room temperature (except a: 50 °C); mass ratio of ILs/gasoline = temperatures
1:1; extraction time 30−40 min Temperature t / °C 25 32 40 50 60
Sulfur removal η/% 45.5 45.8 46.0 46.9 48.3
Figs. 1 and 2 show the GC-FPD chromatogram of gasoline Condition: [BPy]BF4, mass ratio of ILs/model gasoline = 1:1; extraction time
before and after desulfurization with ILs. It can be seen that 30−40 min
the aliphatic and alicyclic sulfur compounds that do not have
the aromatic property and polarity can not form π-π 2.4 Performance of [BPy]BF4 on deep desulfurization
interactions with ILs, thus these compounds can not be
extracted by ILs. The aromatic sulfur-containing molecules Results of multistage desulfurization of the model oil with
with highly delocalized electron density can be readily [BPy]BF4 are shown in Fig. 4. It can be seen that the sulfur
polarized through their interaction with the ILs. Molecules concentration of the model oil decreases from 498 ng/µL to
with highly polarizable π-electron density preferably insert 18 ng/µL after six extraction cycles. Therefore,
into the dynamic molecular structure of the ILs. The N-alkyl-pyridinium ionic liquid can be employed in the deep
favorable electronic interaction of polarized aromatic desulfurization.
molecules with the charged ion pairs of ILs is the driving
force for the molecular insertion[13]. On the other hand, the 600
formation of liquid-clathrate compounds of ILs and olefin in
gasoline also influence the sulfur extraction[12−15]. 500
Sulfur content ρ (ng/µL)

400

300

200

100

0
0 1 2 3 4 5 6
Extraction times
Fig. 1 GC-FPD chromatogram of gasoline before extraction
Fig. 3 Multistage desulfurization of the model oil extracted by
[BPy]BF4

2.5 Regeneration of used ILs

The desulfurization results of ILs before and after

Fig. 2 GC-FPD chromatogram of gasoline after extraction
regeneration are shown in Table 4. The ILs saturated with
sulfur-containing compounds can be readily regenerated by
rotary evaporation at 100 °C or by re-extraction in
tetrachloro-methane. The results also suggest that the
re-extraction method is better than the rotary evaporation
method.
 WANG Jian-long et al. / Journal of Fuel Chemistry and Technology, 2007, 35(3): 293−296

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