3032

Energy & Fuels 2009, 23, 30323038

Zn-Containing Ionic Liquids for the Extractive Denitrogenation of a

Model Oil: A Mechanistic Consideration
Eun Soo Huh, Alexey Zazybin, Jelliarko Palgunadi,, Sungho Ahn, Jongki Hong,
Hoon Sik Kim,*, Minserk Cheong,*, and Byoung Sung Ahn*,
Department of Chemistry and Research Institute of Basic Sciences, and College of Pharmacy, Kyung Hee
UniVersity, 1 Hoegi-dong, Dongdaemoon-gu, Seoul 130-701, Korea, Clean Energy Research Centre, Korea
Institute of Science and Technology, 39-1 Hawolgok-dong, Seongbuk-gu, Seoul 136-791, Korea
ReceiVed January 25, 2009. ReVised Manuscript ReceiVed April 13, 2009

Imidazolium-based zinc-containing ionic liquids (ILs), [1-R-3-R-imidazolium]alkylsulfate-ZnCl2 (R and

R ) H or alkyl), were highly effective for the denitrogenation of a model oil containing quinoline, indole, or
acridine in n-heptane. Fast atom bombardment (FAB)-mass spectra and a computational study imply that the
interaction of 1-ethyl-3-methylimidazolium ethylsulfate ([EMIm]EtSO4) with ZnCl2 produces Zn-containing
ILs, presumably [EMIm]ZnCl2(EtSO4) and [EMIm]ZnCl(EtSO4)2 as the major ionic species. The interaction
of EtSO4- and ZnCl2(EtSO4)- with a heterocyclic N compound was theoretically investigated. The zinccontaining IL, [EMIm]ZnCl2(EtSO4), used for the extraction of quinoline was successfully regenerated by
employing diethyl ether as a back extractant.

Introduction
In recent years, desulfurization and denitrogenation of
transportation fuels have attracted increasing interest because
of the stringent regulation on the environmental pollution caused
by exhaust gases, such as SOx and NOx, to the atmosphere. To
protect the environment against contamination, many developed
countries, including countries in Europe and Japan, are enforcing
the regulation to reduce the allowable sulfur level in diesel fuel
down to 10 parts per million by weight (ppmw) by 2010.1-3
Industrially, the removal of organosulfur and organonitrogen
compounds in fuel oils is being carried out by means of a
simultaneous hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) process at around 350 C using catalysts based
on CoMo or NiMo, which involves the C-S and C-N bond
cleavage to produce H2S and NH3, respectively.4-7 However,
current hydrotreating catalysts used for this purpose are not very
effective for the removal of aromatic sulfur compounds, such
as benzothiophenes (BTs) and dibenzothiophenes (DBTs), and
aromatic nitrogen compounds. Furthermore, a HDS catalyst is
* To whom correspondence should be addressed. Telephone: +82-2961-0432 (H.S.K.); +82-2-961-0239 (M.C.); +82-2-958-5854 (B.S.A.). Fax:
+82-2-965-4408. E-mail: khs2004@khu.ac.kr (H.S.K.); mcheong@khu.ac.kr
(M.C.); bsahn@kist.re.kr (B.S.A.).
Department of Chemistry and Research Institute of Basic Sciences,
Kyung Hee University.
Korea Institute of Science and Technology.
College of Pharmacy, Kyung Hee University.
(1) Zhou, A.; Ma, X.; Song, C. J. Phys. Chem. B 2006, 110, 4699
4707.
(2) Kim, J. H.; Ma, X.; Zhou, A.; Song, C. Catal. Today 2006, 111,
7483.
(3) Babich, I. V.; Moulijn, J. A. Fuel 2003, 82, 607631.
(4) Ferrari, M.; Maggi, R.; Delmon, B.; Grange, P. J. Catal. 2001, 198,
4755.
(5) Dumeignil, F.; Sato, K.; Imamura, M.; Matsubayashi, N.; Payen,
E.; Shimada, H. Appl. Catal., A 2006, 315, 1828.
(6) Pawelec, B.; Mariscal, R.; Fierro, J. L. G.; Greenwood, A.;
Vasudevan, P. T. Appl. Catal., A 2001, 206, 295307.
(7) Caeiro, G.; Costa, A. F.; Cerqueira, H. S.; Magnoux, P.; Lopes, J. M.;
Matias, P.; Ribeiro, F. R. Appl. Catal., A 2007, 320, 815.

easily deactivated by small amounts of aromatic nitrogen

compounds present in the fuel, which is preferably adsorbed
on the surfaces of the catalyst. Although the allowable nitrogen
content is not strictly specified,2,7 the development of new
approaches to drastically reduce the nitrogen content in transportation fuel oils presumably below 10 ppmw is urgently
demanded to meet the need of ultra-clean fuel for environmental
protection.
Several alternative processes, including extraction,8,9 membrane,10 and selective oxidation,11 were proposed for the removal
of nitrogen compounds, which can be classified into two groups:
basic (pyridine, quinoline, and acridine) and neutral (indole and
carbazole). Adsorption by ion-exchange resins12 and liquid-liquid
extraction with carboxylic acids8 as well as ionic liquids
(ILs)13,14 have been employed to remove basic nitrogen compounds. A much more restricted set of methods including
adsorption2,16 and extraction with highly polar organic solvents15
and ILs13,14 has been reported for the removal of neutral nitrogen
compounds. Among these, denitrogenation based on solvent
extraction has been most extensively studied because of its facile
operation, less energy consumption, and the retention of the
(8) Qi, J.; Yan, Y.; Su, Y.; Qu, F.; Dai, Y. Energy Fuels 1998, 12, 788
791.
(9) Gao, P.; Cao, Z.; Zhao, D.; Li, D.; Zhang, S. Pet. Sci. Technol. 2005,
23, 10231031.
(10) Matsumoto, M.; Mikami, M.; Kondo, K. J. Jpn. Pet. Inst. 2006,
49, 256261.
(11) da Conceicao, L.; de Almeida, C. L.; Egues, S.; Dallago, R. M.
Energy Fuels 2005, 19, 960963.
(12) Prudich, M. E.; Cronauer, D. C.; Vogel, R. F.; Solash, J. Ind. Eng.
Chem. Proc. Des. DeV. 1986, 25, 742746.
(13) Eber, J.; Wasserscheid, P.; Jess, A. Green Chem. 2004, 6, 316
322.
(14) Xie, L. L.; Favre-Reguillon, A.; Wang, X. X.; Fu, X.; PelletRostaing, S.; Toussaint, G.; Geantet, C.; Vrinat, M.; Lemaire, M. Green
Chem. 2008, 10, 524531.
(15) Merdrignac, I.; Behar, F.; Albrecht, P.; Briot, P.; Vandenbroucke,
M. Energy Fuels 1998, 12, 13421355.
(16) Liu, D.; Gui, J.; Sun, Z. J. Mol. Catal. A: Chem. 2008, 291, 17
21.

10.1021/ef900073a CCC: $40.75 2009 American Chemical Society

Published on Web 05/06/2009

Zn-Containing Ionic Liquids

chemical structures of the fuels. Considering the energy

consumption, ILs seem to be more attractive than organic
solvents17 because of their negligible volatility, immiscibility
with fuel oils, and higher affinity to sulfur- and nitrogencontaining compounds, and therefore, target compounds can be
easily removed from the fuel oils through a simple layer
separation.18-20 Several papers were published describing the
use of imidazolium-based ILs as extractants in the denitrogenation process,13,18,19 but the interaction between ILs and N
compounds was never a subject of detailed investigation.
Recently, Lewis acidic ILs bearing metal halide anions based
on AlCl3,19,20 FeCl3,21 and CuCl22 were shown to exhibit
promising performances on the selective removal of aromatic
sulfur compounds. Being motivated by these results, we have
tested metal-containing Lewis acidic ILs as extractants for the
selective removal of aromatic nitrogen compounds from hydrocarbon mixtures. During the course of our study on the
denitrogenation of fuel oils, we have found that Zn-containing
imidazolium-based ILs have strong affinities to aromatic
nitrogen compounds.
We now report on the use of Zn-containing imidazoliumbased ILs for the extraction of nitrogen compounds present in
hydrocarbon mixtures at an ambient temperature as well as on
the theoretical investigation on the interaction between ILs and
heterocyclic N compounds.
Experimental Section
General. All of the chemicals used for the synthesis of RTILs
were purchased from Aldrich Chemicals Co. and used as received.
1
H nuclear magnetic resonance (NMR) spectra were recorded on a
400 MHz Bruker NMR spectrometer using DMSO-d6 as the solvent.
Fourier transform infrared (FTIR) spectra were recorded in an inert
atmosphere on a Nicolet 380 spectrophotometer equipped with a
smart MIRacle ATR accessory (Thermo Electron Co.). Fast atom
bombardment (FAB)-mass spectra for the characterization of Zncontaining ILs were recorded with a JMS-700 Mstation doublefocusing mass spectrometer (JEOL, Tokyo, Japan) using a MSMP9020D data system. The ion source was operated at 10 kV
accelerating voltage, with a mass resolution of 1500 (10% valley).
Fast atoms were produced by FAB using a xenon atom gun
operating at 6 keV. Samples were dissolved in methanol and mixed
with 1 L of 3-nitrobenzyl alcohol (NBA, Sigma, St. Louis, MO)
on a FAB probe tip. Calibration was performed with an Ultramark
1621 (PCR, Gainesville, FL) in the positive-ion mode as a standard
compound. Analysis of the upper heptane layers was conducted
using an Agilent 6890 gas chromatograph equipped with a flameionized detector and a DB-wax capillary column (30 m 0.32
mm 0.25 m), and an Agilent 6890-5973 GC-MSD mass
spectrometer equipped with a HP-5MS capillary column (30 m
0.32 mm 0.5 m).
Synthesis of Room Temperature Ionic Liquids (RTILs).
RTILs, 1-alkyl-3-methylimidazolium alkylsulfate,23 1-alkyl-3methylimidazolium alkylphosphite,24 and 1-alkyl-3-methylimida(17) Funakoshi, I.; Aida, T. U.S. Patent 5,753,102, 1998.
(18) Zhao, H.; Xia, S.; Ma, P. J. Chem. Technol. Biotechnol. 2005, 80,
10891096.
(19) Zhang, S.; Zhang, Q.; Zhang, Z. C. Ind. Eng. Chem. Res. 2004,
43, 614622.
(20) Gao, Z. R.; Liao, K. J.; Liu, D. S.; Dai, Y. L. Pet. Sci. Technol.
2005, 27, 10011008.
(21) Ko, N. H.; Lee, J. S.; Huh, E. S.; Lee, H.; Jung, K. D.; Kim, H. S.;
Cheong, M. Energy Fuels 2008, 22, 16871690.
(22) Huang, C.; Chen, B.; Zhang, J.; Liu, Z.; Li, Y. Energy Fuels 2004,
18, 18621864.
(23) Holbrey, J. D.; Reichert, W. M.; Swatloski, R. P.; Broker, G. A.;
Pitner, W. R.; Seddon, K. R.; Rogers, R. D. Green Chem. 2002, 4, 407
413.
(24) Nguyen, H.-P.; Baboulene, M. PCT Int. Appl., WO 2008101881A2,
2007.

Energy & Fuels, Vol. 23, 2009 3033

Scheme 1. Structures of ILs Tested for the Denitrogenation of
the Model Oil

zolium dialkylphosphate,25 were prepared using the methods

described in the literature. RTILs containing ZnCl2 were prepared
by dissolving anhydrous ZnCl2 in a RTIL at 60 C with vigorous
stirring. The weight ratio of RTIL/ZnCl2 was varied from 1 to 20.
All of the Zn-containing ILs obtained were liquids at room
temperature with a moderate viscosity.
Computational Details. The formation of [EMIm]ZnCl2(EtSO4)
and [EMIm]ZnCl(EtSO4)2 and the interactions of [EMIm]ZnCl2(EtSO4) and [EMIm]EtSO4 with quinoline and indole were theoretically investigated using Gaussian 03.26 The geometry optimizations
and thermodynamic corrections were performed with a hybrid
Becke 3-Lee-Yang-Parr (B3LYP) exchange-correlation functional
with the 6-31+G* basis sets for C, H, N, and O and LanL2DZ(ECP)
basis sets for S, Cl, and Zn. To investigate the structures of the
complexes, all kinds of possible interaction patterns were optimized,
giving rise to the most stable final geometries. No restrictions on
symmetries were imposed on the initial structures. All stationary
points were verified as minima by full calculation of the Hessian
and a harmonic frequency analysis.
Denitrogenation Experiments. Unless otherwise stated, all of
the denitrogenation experiments were conducted under a nitrogen
atmosphere. A typical denitrogenation experiment is as follows:
In a 50 mL Schlenk tube, an IL (1 g) was mixed with 5 g of model
oil containing 5000 ppm of quinoline, acridine, or indole and 20 000
ppm of n-octane as an internal standard in n-heptane. The resulting
mixture was stirred for 20 min and then allowed to stand for 10
min at room temperature. After the extraction was completed, the
upper heptane layer was analyzed by GC and GC-mass. The
bottom IL layer was characterized by 1H NMR.
Back Extraction and Regeneration of RTIL. Recycle experiments were performed using [EMIm]EtSO4-ZnCl2 (1 g, [EMIm]EtSO4/ZnCl2 ) 2) as an extractant and diethyl ether as a back
extractant. In a 25 mL Schlenk tube, 5 g of model oil containing
5000 ppm of quinoline and 20 000 ppm of n-octane as an internal
standard in n-heptane was mixed with 1 g of IL with vigorous
stirring for 10 min and then allowed to stand for 5 min. After the
extraction, the upper layer was removed by layer separation and
the remaining IL layer was washed with 3 g of diethyl ether with
vigorous shaking for 5 min, followed by standing for 5 min. The
upper diethyl ether layer was then separated, evaporated, and
analyzed by 1H NMR spectroscopy. The bottom IL layer was
evaporated under a vacuum to remove diethyl ether and used for
further extraction with a fresh charge of the model oil.

Results and Discussion

Denitrogenation with Neat RTILs. The denitrogenation of
the model oil containing 5000 ppm of quinoline and 20 000
ppm of n-octane as an internal standard in n-heptane was
conducted at room temperature using RTILs shown in Scheme
1. The Nernst partition coefficient KN,13,27 defined as the mass
ratio of the nitrogen content in a RTIL to the nitrogen content
in the model oil [mg (N) g (IL)-1/mg (N) g (oil)-1], was
measured for each extraction. As listed in Table 1, all of the
(25) Kuhlmann, E.; Himmler, S.; Giebelhaus, H.; Wasserscheid, P. Green
Chem. 2007, 9, 233242.
(26) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; et al. Gaussian 03,
revision C.02, Gaussian, Inc., Pittsburgh, PA, 2004.
(27) Nie, Y.; Li, C.-X.; Wang, Z. H. Ind. Eng. Chem. Res. 2007, 46,
51085112.

3034

Energy & Fuels, Vol. 23, 2009

Huh et al.

Table 1. Denitrogenation of the Model Oil Containing Quinoline

Using Various Types of ILsa
IL

DEb (%)

KNc

[DMIm]MeSO4
[EMIm]MeSO4
[BMIm]MeSO4
[OMIm]MeSO4
[HEIm]EtSO4
[EMIm]EtSO4
[BEIm]EtSO4
[EMIm]EtPHO3
[BMIm]BuPHO3
[EMIm]Et2PO4
[BMIm]Bu2PO4
[EMIm]Cl
[EMIm]2ZnCl2Br2d

36.2
47.9
52.7
57.3
40.8
40.6
55.3
40.7
45.7
54.0
52.7
29.0
49.3

2.84
4.60
5.57
6.71
3.45
3.42
6.19
3.43
4.21
5.89
5.57
2.04
4.86

a The extraction of quinoline was conducted at room temperature with

the model oil containing 5000 ppm of quinoline and 20 000 ppm of
n-octane as an internal standard in n-heptane. The weight ratio of model
oil/IL was set at 5. b DE ) degree of extraction (%). c Nernst partition
coefficient ) [mg (N) g (IL)-1/mg (N) g (oil)-1]. d A total of 20 wt %
in [BEIm]EtSO4.

RTILs showed KN values in the range of 2.8-6.7, which are

equivalent to 36-58% quinoline extraction. The quinoline
extraction ability of IL or the KN value increased with an
increasing chain length of the alkyl group on the cation and
anion for the same series of RTILs. For methylsulfate series,
the KN value was found in the order: 1,3-dimethylimidazolium methylsulfate ([DMIm]MeSO4) < 1-ethyl-3-methylimidazolium methylsulfate ([EMIm]MeSO4) < 1-butyl-3-methylimidazolium methylsulfate ([BMIm]MeSO4) < 1-octyl-3-methylimidazolium methylsulfate ([OMIm]MeSO4). The reason for this
is not clear at the moment, but the extraction ability of IL seems
to be related to the free volume in an IL because the molar
volume increases going from [DMIm]MeSO4 to [OMIm]MeSO4. The interrelation between the length of the alkyl chain
of the IL and free volume was well-described in the literature.28,29
On the contrary, the extraction ability of RTIL was not
affected by the type of anion, as long as the RTIL possesses
the equivalent number of the same alkyl groups: the degree of
extraction with [EMIm]EtSO4 and 1-ethyl-3-methylimidazolium
ethylphosphite ([EMIm]EtPHO3) was found to be 40.6 (KN )
3.42) and 40.7% (KN ) 3.43), respectively. However, when
phosphate and phosphite series ILs were compared, phosphate
series ILs showed better extraction ability than the phosphite
series ILs. For example, the extraction abilities of 1-ethyl-3methylimidazolium diethylphosphate ([EMIm]Et2PO4) and
[EMIm]EtPHO3 were determined as 54.0 (KN ) 5.89) and
40.7% (KN ) 3.43), respectively. The presence of one more
ethyl group in [EMIm]Et2PO4 than in [EMIm]EtPHO3 seems
to provide a larger free volume in the IL, thereby resulting in
higher extraction ability. On the other hand, stronger basicity
of phosphite anion is likely to result in a stronger interaction
between the imidazolium cation and phosphite anion, thereby
reducing the interaction of quinoline with the C(2)-H of the
imidazolium cation.
As expected from the physical state, [EMIm]Cl, existing as
a solid at room temperature, showed a greatly reduced extraction
ability compared to sulfate, phosphite, and phosphate series
RTILs.
Characterization of Zn-Containing RTILs: FTIR. Even
though the neat RTILs exhibited some ability to extract quinoline
(28) Jacquenmin, J.; Husson, P.; Padua, A. A. H.; Majer, V. Green Chem.
2006, 8, 172180.
(29) Blanchard, L. A.; Gu, Z.; Brennecke, J. F. J. Phys. Chem. B 2001,
105, 24372444.

Figure 1. FTIR spectra of (a) [EMIm]EtSO4, (b) [EMIm]EtSO4-ZnCl2

(molar ratio of IL/ZnCl2 ) 2), and (c) ZnCl2.

from the model oil, their performances are far from being
commercialized. For the complete extraction of Lewis basic
heterocyclic nitrogen compounds, the complexation with Lewis
acidic metal halide, such as ZnCl2 and AlCl3, would be more
desirable but the following recovery of the nitrogen compound
and metal halide from the resulting metal complexes would be
much more difficult. It is well-known that amines interact with
Lewis acidic zinc halide to form stable bisamine zinc halide
complexes, (amine)2ZnX2.30-33 Therefore, to facilitate the
recovery of amines, the bond strength between amine and ZnX2
should be reduced. One way to weaken the bond strength would
be the lowering of the Lewis acidity on the Zn center, by
transforming zinc halide into zincate anion (ZnX42-, X ) halide)
through a reaction with an imidazolium halide. It is reported
that the reaction of zinc halide, ZnX2 (X ) Cl and Br) with 2
equiv of [BMIm]Cl produces an IL, [BMIm]2ZnCl2X2, which
possesses both Lewis acidity and basicity.33 We hoped that these
imidazolium zinc tetrahalides would exhibit high quinoline
extraction ability from the model oil. However, contrary to our
expectation, the addition of 20 wt % [EMIm]2ZnCl2Br2 did not
improve the extraction ability of [BEIm]EtSO4. It is likely that
the Zn center is fully occupied by strongly coordinating halide
ligands, and thus, no vacant site is generated for the coordination
of a nitrogen compound. This result may suggest that the Zncontaining IL should possess at least one labile ligand to provide
a vacant site for the interaction with a nitrogen compound. In
this regard, an attempt was made to replace two halide ions
(X2) in [EMIm]2ZnCl2X2 by a weakly coordinating ligand or
ligands such as EtSO4-. For this purpose, ZnCl2 was treated
with 2 equiv of [EMIm]EtSO4 and the resulting viscous liquid
was investigated by FTIR spectroscopy. As can be seen in Figure
1, the FTIR spectrum of the viscous liquid is quite different
from those of ZnCl2 and [EMIm]EtSO4, indicating the formation
of a new ionic species. The broad peak centered at 3103 cm-1,
associated with the interaction of aromatic C(2)-H with EtSO4in [EMIm]EtSO4,34-37 shifted to a higher frequency at 3109
(30) Jain, B.; Singh, J. M.; Goyal, R. N.; Tandon, S. N. Can. J. Chem.
1980, 58, 15581561.
(31) Wang, W.; Zhang, X.; Huang, D.; Zhu, H.; Chen, C.; Liu, Q. Acta
Crystallogr., Sect. E: Struct. Rep. Online 2001, 57, m561m563.
(32) Mahan, R. I.; Bailey, J. R. J. Am. Chem. Soc. 1937, 59, 2449
2450.
(33) Palgunadi, J.; Kwon, O.-S.; Lee, H.; Bae, J. Y.; Ahn, B. S.; Min,
N.-Y.; Kim, H. S. Catal. Today 2004, 98, 511514.
(34) Tait, S.; Osteryoung, R. A. Inorg. Chem. 1984, 23, 43524360.
(35) Dieter, K. M.; Dymek, C. J., Jr.; Heimer, N. E.; Rovang, J. W.;
Wilkes, J. S. J. Am. Chem. Soc. 1988, 110, 27222726.
(36) Shiraishi, Y.; Tachibana, K.; Hirai, T.; Komasawa, I. Ind. Eng.
Chem. Res. 2001, 40, 49194924.
(37) Kim, Y. J.; Varma, R. S. J. Org. Chem. 2005, 70, 78827891.

Zn-Containing Ionic Liquids

Energy & Fuels, Vol. 23, 2009 3035

Figure 2. FAB-MS spectra of [EMIM]EtSO4-ZnCl2 in negative-ion

mode (A ) EtSO4-). Molar ratio of [EMIM]EtSO4/ZnCl2: (a) 1, (b)
1.5, (c) 2, and (d) 5.

cm-1 upon treating with ZnCl2. The SdO asymmetric stretching

frequency centered at 1214 cm-1 also moved to a higher
frequency at 1289 cm-1, implying that EtSO4- is bonded to
ZnCl2.
Characterization of Zn-Containing RTILs: FAB-Mass.
To confirm the formation of the new Zn-containing IL,
FAB-mass spectral analyses were carried out with ILs obtained
from [EMIm]EtSO4 and ZnCl2 (molar ratio of [EMIm]EtSO4/
ZnCl2 ) 1-5). FAB-mass spectra in Figure 2 showed that the
major anionic ZnII species observed were 1:1 and 2:1 adduct
species, ZnCl2(EtSO4)- (MW ) 261) and ZnCl(EtSO4)2- (MW
) 349), irrespective of the molar ratio of [EMIm]EtSO4/ZnCl2.
The absence of the 2:1 dianionic species, ZnCl2(EtSO4)22-,
similar to ZnCl2Br22-, can be attributed to the chelating property
of EtSO4- through oxygen atoms.
Computational Studies on the Structures of Zn-Containing
RTILs. The formations of [EMIm]ZnCl2(EtSO4) and [EMIm]ZnCl(EtSO4)2 were also supported by the theoretical investigation at the B3LYP level of the theory (6-31+G* for C, H, and
O and LanL2DZ(ECP) for S, Cl, and Zn) using Gaussian 03.26
The optimized structures of [EMIm]ZnCl2(EtSO4) and
[EMIm]ZnCl2(EtSO4) are shown in Figure 3. As can be deduced
from the bidentate character of ethylsulfate, ZnCl2(EtSO4)shows a stable tetrahedral arrangement of ligands around Zn,
with the Gibbs free energy of formation of -35.8 kcal/mol for
the reaction between ZnCl2 and [EMIm]EtSO4. Coordination
of one more ethylsulfate ligand with a concomitant loss of a
strongly coordinating Cl- ligand seems to give a less stable
square pyramidal complex (G ) -27.1 kcal/mol) for the
reaction between ZnCl2 and 2[EMIm]EtSO4. The computational
results on the formation of two major species, [EMIm]ZnCl2(EtSO4) and [EMIm]ZnCl(EtSO4)2, are in good agreement
with those from the FAB-mass spectral analysis.
Denitrogenation with Zn-Containing RTILs. The effect of
ZnCl2 content in [EMIm]EtSO4 was evaluated for the denitrogenation of the model oil containing 5000 ppm of quinoline
and 20 000 ppm of n-octane as an internal standard in n-heptane.
ZnCl2 was completely dissolved first in [EMIm]EtSO4 at 60
C with vigorous stirring to form Zn-containing ILs,
[EMIm]EtSO4-ZnCl2. As shown in Table 2, the extraction

Figure 3. Optimized structures of the species formed from the

interaction of ZnCl2 with ethylsulfate: (a) ZnCl2 + [EMIm]EtSO4 f
[EMIm][ZnCl2(EtSO4)] (G ) -35.8 kcal/mol) and (b) ZnCl2 +
2[EMIm]EtSO4 f [EMIm]Cl + [EMIm][ZnCl(EtSO4)2] (G ) -27.1
kcal/mol).
Table 2. Effect of the [EMIm]EtSO4/ZnCl2 Molar Ratio on the
Extraction of Quinoline Present in the Model Oila
molar ratio ([EMIm]EtSO4/ZnCl2)

DEb (%)

KNc

d
20
10
5
4
3
2
1
2e
2f
ZnCl2

40.6
81.6
84.6
85.3
86.8
88.8
89.2
90.2
68.8
59.2
42.3

3.42
22.2
27.5
29.0
32.9
39.6
41.3
46.0
44.1
43.5
5.48

a The extraction of quinoline was conducted at room temperature with

the model oil containing 5000 ppm of quinoline and 20 000 ppm of
n-octane as an internal standard in n-heptane. The weight ratio of model
oil/[EMIm]EtSO4 was set at 5. b DE ) degree of extraction (%).
c Nernst partition coefficient ) [mg (N) g (IL)-1/mg (N) g (oil)-1].
d [EMIm]EtSO only. e Weight ratio of model oil/[EMIm]EtSO ) 20.
4
4
f Weight ratio of model oil/[EMIm]EtSO ) 30.
4

ability of [EMIm]EtSO4 expressed in the KN value increased

from 8.1 to 46.0 when an equimolar amount of ZnCl2 was
dissolved in [EMIm]EtSO4. Although the KN value decreased

3036

Energy & Fuels, Vol. 23, 2009

Huh et al.

Table 3. Effect of the Alkyl Substituent on the Extraction

Ability of [RRIm]RSO4-ZnCl2a
IL

DEb (%)

KNd

[HEIm]EtSO4-ZnCl2
[EMIm]EtSO4-ZnCl2
[BEIm]EtSO4-ZnCl2
[EMIm]MeSO4-ZnCl2
[BMIm]MeSO4-ZnCl2
[OMIm]MeSO4-ZnCl2
[EMIm]Et2PO4-ZnCl2
[BMIm]Bu2PO4-ZnCl2
[EMIm]EtPHO3-ZnCl2
EMImCl-ZnCl2d
EMImCl-ZnCl2e

86.5
89.2
91.2
88.4
89.8
93.9
47.5
43.1
38.3
64.3
68.9

32.0
41.3
51.8
38.1
44.0
77.0
4.52
3.79
3.10
9.00
11.1

a The extraction of quinoline was conducted at room temperature with

the model oil containing 5000 ppm of quinoline and 20 000 ppm of
n-octane as an internal standard in n-heptane. The molar ratio of IL/
ZnCl2 and the weight ratio of model oil/IL were set at 2 and 5,
respectively. b DE ) degree of extraction (%). c Nernst partition
coefficient ) [mg (N) g (IL)-1/mg (N) g (oil)-1]. d [EMIm]Cl-ZnCl2
([EMIm]Cl/ZnCl2 ) 1). e [EMIm]Cl-ZnCl2 ([EMIm]Cl/ZnCl2 ) 2).

Table 6. Recycling Study with [EMIm]EtSO4-ZnCl2a

recycle number

DEb (%)

KNc

1
2
3
4
5
6
7
8

89.0
87.3
86.7
86.2
82.9
82.0
81.4
80.5

40.5
34.4
32.6
31.2
24.2
22.8
21.9
20.6

a The extraction of quinoline was conducted at room temperature with

the model oil containing 5000 ppm of quinoline and 20 000 ppm of
n-octane as an internal standard in n-heptane. The molar ratio of
[EMIm]EtSO4/ZnCl2 and the weight ratio of model oil/IL were set at 2
and 5, respectively. Diethyl ether (3 g) was used as the back extractant
to regenerate IL. b DE ) degree of extraction (%). c Nernst partition
coefficient ) [mg (N) g (IL)-1/mg (N) g (oil)-1].

Scheme 2. Structures of Aromatic Nitrogen Compounds

Table 4. Denitrogenation of the Model Oil Containing Indole or

Acridine by Various Types of Neat ILs and Zn-Containing ILsa
indole

acridine

IL

DEb (%)

KNc

DE (%)

KN

[EMIm]EtSO4
[EMIm]EtSO4
[EMIm]EtSO4-ZnCl2
[EMIm]EtSO4-ZnCl2
[BEIm]EtSO4
[BEIm]EtSO4-ZnCl2
[DMIm]MeSO4
[DMIm]MeSO4-ZnCl2

98.7
94.5d
100
92.7d
100
100
97.8
98.7

380
344

38.7

3.16

84.7

27.7

40.2
86.5
33.5
83.8

3.36
32.0
2.52
25.9

253
222
380

a The extraction of indole or acridine was conducted at room

temperature with the model oil containing 5000 ppm of indole or 5000
ppm of acridine and 20 000 ppm of n-octane as an internal standard in
n-heptane. The weight ratio of model oil/IL and the molar ratio of neat
IL/ZnCl2 were set at 5, respectively. b DE ) degree of extraction (%).
c Nernst partition coefficient ) [mg (N) g (IL)-1/mg (N) g (oil)-1].
d Weight ratio of model oil/IL ) 20.

Table 5. Denitrogenation of the Model Oil Containing

Quinoline, Acridine, and Indole with [EMIm]EtSO4 and
[EMIm]EtSO4-ZnCl2a
IL
[EMIm]EtSO4
[EMIm]EtSO4-ZnCl2

N compound

DEb (%)

KNc

indole
quinoline
acridine
indole
quinoline
acridine

98.9
40.8
39.2
100
85.8
84.2

450
3.45
3.22
30.2
26.6

a The extraction of quinoline, acridine, and indole was conducted at

room temperature with the model oil containing 5000 ppm of nitrogen
compounds (1:1:1) and 20 000 ppm of n-octane as an internal standard
in n-heptane. The molar ratio of [EMIm]EtSO4/ZnCl2 and the weight
ratio of model oil/IL were set at 5, respectively. b DE ) degree of
extraction (%). c Nernst partition coefficient ) [mg (N) g (IL)-1/mg (N)
g (oil)-1].

with the increase of the molar ratio of [EMIm]EtSO4/ZnCl2,

the quinoline extraction was maintained above 80% in the molar
ratio range of 1-20. In contrast to [EMIm]EtSO4-ZnCl2,
powdered ZnCl2 only exhibited a much lower quinoline extraction ability, supporting the role of [EMIm]EtSO4 in dissolving

Figure 4. 1H NMR spectra of the IL ([EMIm]EtSO4-ZnCl2, molar

ratio of [EMIm]EtSO4/ZnCl2 ) 2) in DMSO-d6 before and after
regeneration: (a) [EMIm]EtSO4-ZnCl2, (b) model oil (5000 ppm of
quinoline), (c) bottom IL layer after denitrogenation, (d) upper ether
layer recovered after washing, and (e) bottom IL layer after washing
with diethyl ether. Characteristic 1H NMR peaks: (*) IL, (2) quinoline,
and (b) diethyl ether.

ZnCl2 and consequently forming an active species for the

extraction of N compounds. The quinoline extraction was also
conducted at much higher mass ratios of model/IL ) 20 and
30 (IL ) [EMIm]EtSO4-ZnCl2, [EMIm]EtSO4/ZnCl2 ) 2) to
obtain more meaningful results in terms of an economic point
of view. High KN values of 44.1 and 43.5 were maintained even
at higher molar ratios of 20 and 30, respectively, suggesting
that the Zn-containing RTILs could be used as promising N
extractants for the practical application.
The effect of the alkyl substituent on the imidazolium ring
was also investigated for the removal of quinoline using various
Zn-containing ILs, [1-R-3-R-imidazolium]RSO4-ZnCl2
([RRIm]RSO4-ZnCl2), at the molar ratio of [1-R-3-R-imidazolium]RSO4/ZnCl2 ) 2. It was expected that the presence of
an acidic H (N-H) atom on the imidazolium ring could promote
the interaction between [1-H-3-R-imidazolium]RSO4-ZnCl2
with quinoline through a hydrogen bond. However, the presence
of the H atom was not helpful in improving the performance of
ILs to extract quinoline. As listed in Table 3, the IL with an
acidic H atom on the imidazolium ring, [ethylimidazolium]EtSO4-ZnCl2 ([HEIm]EtSO4-ZnCl2), exhibited a similar

Zn-Containing Ionic Liquids

Energy & Fuels, Vol. 23, 2009 3037

Figure 5. Optimized structures showing the interactions of [EMIm]ZnCl2(EtSO4) or [EMIm]EtSO4 with quinoline, diethyl ether, or indole to form
(a) [EMIm]ZnCl2(EtSO4) + quinoline f [EMIm]Zn(quinoline)Cl2(EtSO4), (b) [EMIm]ZnCl2(EtSO4) + diethyl ether f [EMIm]Zn(Et2O)Cl2(EtSO4),
(c) [EMIm]ZnCl2(EtSO4) + indole f [EMIm]Zn(indole)Cl2(EtSO4), and (d) [EMIm]EtSO4 + indole f [EMIm](indole)EtSO4.
Scheme 3. Plausible Mechanism of the Reversible Quinoline
Extraction ([EMIm] Moiety Was Omitted for Clarity)

extraction ability to [EMIm]EtSO4-ZnCl2. Moreover, the variation of the chain length of the alkyl group on the imidazolium
ring did not exert any noticeable effect on the extraction ability,
supporting the pivotal role of the Zn-containing anion.

For a comparison, the performances of other types of Zncontaining ILs, prepared from ZnCl2 and [EMIm]Cl, [EMIm]Et2PO4, or [EMIm]EtPHO3, were tested for the removal of
quinoline from the model oil (see Table 3). However, the
extraction ability of these ILs was significantly lower than that
of the corresponding [EMIm]EtSO4-ZnCl2 ([EMIm]EtSO4/
ZnCl2 ) 2). The higher extraction ability of ZnCl2-[EMIm]EtSO4 seems to be attributed to the easier formation of the
anionic species, such as [ZnCl2(EtSO4)]-, or the easier bonding
mode change of the ligand, EtSO4-, from bidentate to monodentate to provide a vacant site for the coordination of quinoline.
Zn-containing ILs were also tested for the extraction of indole
and acridine (Scheme 2). As listed in Table 4, indole was
completely extracted from the model oil containing 5000 ppm
of indole in n-heptane when treated with [EMIm]EtSO4-ZnCl2
([EMIm]EtSO4/ZnCl2 ) 5, weight of model oil/weight of
ZnCl2-[EMIm]EtSO4 ) 5). The Zn-containing IL, [EMIm]EtSO4-ZnCl2, was also effective for the denitrogenation of the
model oil containing 5000 ppm of acridine, but the degree of
acridine extraction was lower than those of indole and quinoline
extractions. To find the ease of extraction for the nitrogen
compounds, [EMIm]EtSO4-ZnCl2 was mixed with the model
oil containing three nitrogen compounds: quinoline, indole, and
acridine. As expected from the extraction of a single N
compound, the degree of extraction was found in the following
order: indole > quinoline > acridine (see Table 5).
The same trend was also observed for the extraction with a
neat IL, [EMIm]EtSO4, suggesting that the interaction of IL with
a N compound is affected by the presence of the N-H bond

3038

Energy & Fuels, Vol. 23, 2009

and also by the steric crowding around the nitrogen atom or

the basicity of the nitrogen compound.38 As shown in Tables 4
and 5, over 99% of indole was removed from the model oil
using the neat IL only at the molar ratio of oil/IL ) 5, most
likely because of the strong interaction between the H atom of
N-H and the basic anion of IL. Such a high indole extraction
from fuel oil was previously observed by Wasserscheid et al.
using [BMIm]OcSO4.7 The extraction of indole was also
conducted at the higher mass ratio of oil/IL ) 20 to see more
clearly the effect of ZnCl2. As shown in Table 4, [EMIm]EtSO4
exhibited a slightly higher extraction ability than [EMIm]EtSO4-ZnCl2. This result is a strong indication that the indole
extraction by an IL is mostly governed by the interaction of
N-H of indole with EtSO4-. The effect of the interaction
between indole and the Zn center through the N atom seems to
be negligible.
Regeneration of RTIL and Back Extraction of Trapped
Quinoline. The regeneration of [EMIm]EtSO4-ZnCl2 ([EMIm]EtSO4/ZnCl2 ) 2) used for the extraction of quinoline was
performed using diethyl ether as a back extractant. As listed in
Table 6, the Zn-containing IL, [EMIm]EtSO4-ZnCl2, was
shown to be recyclable up to 8 cycles without a significant loss
of initial performance, demonstrating that diethyl ether is highly
efficient in the regeneration of IL and in the recovery of trapped
quinoline out of the IL layer. The excellent performance of
diethyl ether as a back extractant was further verified by the 1H
NMR experiments. Panels a and b of Figure 4 are the 1H NMR
spectra of [EMIm]EtSO4-ZnCl2 and the model oil, respectively.
The 1H NMR spectrum in Figure 4c clearly shows that quinoline
was extracted from the model oil to the bottom IL layer after
denitrogenation. Quinoline trapped in the bottom IL layer was
successfully removed from the bottom IL layer using diethyl
ether as a back extractant. The 1H NMR spectrum of the diethyl
ether layer after evaporation in Figure 4d reveals that quinoline
trapped in the IL layer was transferred to the diethyl ether layer.
The characteristic peak of the IL at 9.176 ppm was not observed
in the diethyl ether layer. Figure 4e is the 1H NMR spectrum
of the IL layer after back extraction with diethyl ether. It is
noteworthy that the peaks corresponding to diethyl ether can
be seen in the spectrum of the bottom IL layer, suggesting that
diethyl ether is coordinated to the Zn center in place of quinoline
after the back extraction. This could be rationalized by considering the stronger affinity of Zn to the oxygen atom than to the
nitrogen atom. The coordinated and/or free diethyl ether present
in the IL layer can be easily removed under vacuum (spectrum
is not shown here).
Theoretical Consideration of the Extraction with RTILs. The
interactions of ZnCl2(EtSO4)- and EtSO4- with quinoline and
indole were theoretically investigated at the B3LYP level of
theory using Gaussian 03.26 As shown in Figure 5a, there is a
substantial interaction between [EMIm]ZnCl2(EtSO4) and quinoline, and the interaction enthalpy (H) was calculated as -5.7
kcal/mol. A similar interaction can also be seen between
[EMIm]ZnCl2(EtSO4) and diethyl ether (see Figure 5b). The
calculated interaction enthalpy of -12.7 kcal/mol is larger by
1.8 kcal/mol than that between [EMIm]ZnCl2(EtSO4) and
quinoline. This is probably the reason why diethyl ether is
capable of back extracting trapped quinoline in the IL layer.
Both of the structures in panels a and b of Figure 5 show that
the coordination of a Lewis base, such as quinoline or diethyl
(38) Harper, J. B. Compr. Heterocycl. Chem. III 2008, 7, 140.

Huh et al.

ether, changes the binding mode of the ethylsulfate in

ZnCl2(EtSO4)- from bidentate to monodentate, thereby retaining
a tetrahedral environment around Zn. In contrast, as shown in
panels c and d of Figure 5, indole was found to interact more
strongly with an ethylsulfate anion via hydrogen bonding than
with the Zn atom in ZnCl2(EtSO4)-. The enthalpy for the
interactions of indole with [EMIm]EtSO4 and [EMIm]ZnCl2EtSO4 was calculated as -7.6 and -4.3 kcal/mol, respectively,
suggesting that indole extraction is mainly influenced by the
interaction between the H atom of N-H and EtSO4- rather than
that between the N atom and Zn center.
From the experimental, spectroscopic, and computational
results, the plausible extraction mechanism of the isomerization
is suggested as in Scheme 3. The active species 1 is likely to
form by the reaction of [EMIm]EtSO4 and ZnCl2. The interaction of 1 with quinoline would produce quinoline-coordinated
species 2, which in turn transforms into diethyl-ether-coordinated
species 3 upon treated with diethyl ether, a back extractant. The
coordinated ether can be removed under vacuum to regenerate
the active species 1.
Conclusions
Zn-containing ILs, prepared from the interaction of ZnCl2
with imidazolium-based IL bearing a alkylsulfate anion, were
proven to be effective extractants for the denitrogenation of a
model oil containing quinoline, acridine, and/or indole. In
particular, the performance of dialkylimidazolium alkyl sulfate
RTIL for the extraction of basic nitrogen compounds, such as
quinoline and acridine, was significantly improved up to more
than 2 times by the co-presence of Lewis acidic ZnCl2.
Diethyl ether was found to be an efficient back extractant
for the regeneration of [EMIm]EtSO4-ZnCl2, used for the
denitrogenation of quinoline from the model oil, and to recover
trapped quinoline in the IL. The quinoline extraction ability of
[EMIm]EtSO4-ZnCl2 was maintained up to 8 cycles without a
significant loss of the initial performance using diethyl ether as
the back extractant. Computational studies show that active Zncontaining anionic species, such as [EMIm]ZnCl2(EtSO4) and
[EMIm]ZnCl(EtSO4)2, can be generated from the interaction of
ZnCl2 with [EMIm]EtSO4, and thus, the extraction of quinoline
can be facilitated through the coordination of quinoline to the
Zn center. The bonding mode of ethylsulfate ligand in
ZnCl2(EtSO4)- is changed from bidentate to monodentate for
the coordination of quinoline, thereby retaining a tetrahedral
environment around Zn. The larger calculated interaction
enthalpy for the coordination diethyl ether suggests that the
coordinated quinole can be replaced by diethyl ether. The
formation of anionic Zn species, ZnCl2(EtSO4)- (MW ) 261)
and ZnCl(MeSO4)2- (MW ) 349), was supported by FAB-MS
spectroscopic results.
In the case of the denitrogenation of a neutral nitrogen
compound, such as indole, the extraction by an IL seems to be
mostly governed by the interaction between the anion of IL and
the H atom of N-H rather than by the coordination of indole
to the Zn center through the N atom, as supported by
computational calculation.
Acknowledgment. This work has been performed as an Energy
Technology Innovation (ETI) Project under the Energy Resources
Technology Development program.
EF900073A