ARTICLE

pubs.acs.org/IECR

Extraction of Thiophene or Pyridine from n-Heptane Using Ionic

Liquids. Gasoline and Diesel Desulfurization
Karolina Ke- dra-Kr
olik, Mutelet Fabrice,* and Jean-Noel Jaubert
Laboratoire R
eactions et G
enie des Proc
ed
es, Nancy-Universit
e, 1 rue Grandville, BP 20451 54001 Nancy, France
ABSTRACT: The aim of this study is to investigate the possible use of ILs as solvents for two separation problems frequently
encountered in petroleum industry: {aromatic sulfur compound aliphatic hydrocarbon} or {nitrogen compound aliphatic
hydrocarbon}. This work is focused on three ILs: 1-ethyl-3-methylimidazolium thiocyanate, 1,3-dimethylimidazolium methylphosphonate, and tris-(2-hydroxyethyl)-methylammonium-methylsulfate. In the rst part of this article, a study of new three ternary
systems is studied in view of dening the capacity of proposed ILs as solvents for extraction of sulfur and nitrogen containing organic
compounds from aliphatic hydrocarbons. Therefore, LLE measurements of ternary mixtures for ve systems were measured at
298.15 K and at atmospheric pressure: {thiophene n-heptane 1-ethyl-3-methylimidazolium thiocyanate}, {thiophene
n-heptane 1,3-dimethylimidazolium methylphosphonate}, {thiophene n-heptane tris-(2-hydroxyethyl)-methylammoniummethylsulfate}, {pyridine n-heptane 1-ethyl-3-methylimidazolium thiocyanate}, {pyridine n-heptane 1,3-dimethylimidazolium methylphosphonate}. The second section of this article presents results of extraction of synthetic fuels - model gasoline and
model diesel by the use of selected ILs. The inuence of extraction time or temperature as well as three stepped procedure using each
time a fresh portion of ILs on the nal fuel contamination was investigated.

INTRODUCTION
The separation of mixtures by liquid-liquid extraction is often
applied by many industrial procedures due to simplistic operation option, mild processes conditions, and economical advantages of this method. High eciency of this technique depends
largely on precisely selected the most suitable solvent for specic
separation process. However, conventional solvents commonly
used for extraction are highly volatile, ammable, and often toxic.
The environmental regulations all over the world are more stringent
so applications of green solvents in classical methods or new
economically and environmentally friendly technologies are in great
demand. Some of industrially important extraction processes are still
a challenge e.g. separations of aliphatic and aromatic hydrocarbons
or alcohols and aliphatic hydrocarbons. The components of such
systems have very narrow range of boiling points and several
combinations form azeotropes. This makes them also impracticable
to be separated by distillation.
In recent years considerable attention has been given to deep
desulfurization of gasoline and diesel due to the higher restrictions concerning sulfur-compounds content level in fuels. Sulfur
oxides that form in gasoil combustion process contribute to acid
rains, global warming eect, and air pollution. Those aect urban
as well as industrial areas and are harmful for human health due to
secondary inorganic aerosol gases formation. The European
Union gradually reduced the maximum sulfur concentration in
fuels to avoid high emission of gases resulting from combustion
of heavy fuels. Since 2010 the total sulfur content cannot be
higher than 10 ppm. Deep desulfurization of gasoline and diesel
is a very complex problem for petroleum industry and has to be
solved to minimize the pollutions from fuel oils exhaust gas.
Indeed, many research groups carry out deep investigations of
environmentally benign, energy saving, and eective methods.1
r 2011 American Chemical Society

The conventional method applied by reneries is hydrodesulfurization (HDS) and consists of catalytic hydrotreating with
Co-Mo/Al2O3, Ni-Mo/Al2O3, or Ni-W/Al2O3 catalysts.2
HDS is highly ecient for removal of aliphatic hydrocarbons
containing sulfur. However, the challenging task arises with
elimination of aromatic sulfur compounds such as thiophene
or dibenzothiophene and their alkyl derivatives such as 4-methyldibenzothiophene by use of the HDS method.3 Moreover, HDS
processes have to be conducted under elevated temperatures
(300-400
C) as well as elevated pressures (20-100 atm of H2)
which makes the method cost and energy consumptive. To face
these problems with the purpose of regard sulfur contamination
within the required levels, researchers have been making several
eorts to elaborate new catalysts or to enhance existing catalyst
activity and change HDS operation conditions. On the other
hand, many investigations have been directed toward expanding
on new original approaches to deep desulfurization of fuels, such
as processes based on distillation, adsorption, extraction, reactive alkylation, complexation, precipitation, photochemical desulfurization, selective oxidation, biodesulfurization, ultrasounds
accompanied extraction, and combinations of mentioned
methods.4
The use of ionic liquids (ILs) for liquid-liquid extraction
shows a great potential in comparison with conventional organic
solvents, due to their unique physicochemical properties. Negligible vapor pressure, high chemical and thermal stability,
nonammability, or recyclability makes them environmentally
friendly solvents. Moreover they are able to dissolve a wide range
of organic or inorganic substances, and it is possible to adjust
Received: September 1, 2010
Accepted: December 6, 2010
Published: January 20, 2011
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Industrial & Engineering Chemistry Research

some of their properties such as polarity or miscibility for certain
system requirements. They also have high ionic conductivity and
wide electrochemical window. These properties make ILs very
good solvents for liquid-liquid extractions as well as for a
number of applications e.g. catalysis, synthesis, gas separations
which was proved by some thermodynamic methods concerning
determination of activity coecients at innite dilution.5-7 The
use of ILs usually causes higher values of selectivities at innite
dilution for a specic separation process comparing to classical
solvents. This is generally caused by the high solubility of polar
compounds in ionic liquids and the low miscibility of aliphatic
compounds.
The interactions between aromatic sulfur compounds and
ionic liquids were conducted by many research groups.8-10
Revelli and co-workers demonstrated using Nuclear Magnetic
Resonance (NMR) that thiophene molecules are accommodated
into the ionic pair structure of the ionic liquids enabling the
selective and extractive removal of aromatic sulfur compounds
from fuels.8 A unique feature of ionic liquids as salts is their
mobility and exibility, which allow for a facile restructuring of
the ionic liquids in the process of thiophene dissolution. The
restructuring process is primarily driven by the interaction of
thiophene with the imidazolium cations of the ionic liquids, and
the maximum absorption capacity of thiophene by ionic liquids is
primarily determined by the size and structure of both cations
and anions.8
The rst investigations of fuels extractive desulfurization using
ionic liquids has been reported by Bossman et al. in 2001.11
These authors studied the dialkylimidazolium chlorides mixed
with AlCl3 as an extracting solvent and showed that the steric
factors of specic ionic liquids are responsible for S-containing
compounds extraction rather than chemical interactions involving the acid proton, as they supposed before. Among
many types of studied ionic liquids, those based on imidazolium cations and BF4- or PF6- anions showed high eciency
for organic sulfur as well as organic nitrogen compounds
extraction.12,13 It was proved that these ionic liquids interact
by coulombian forces with electrons of aromatic ring.
However, several liquid-liquid equilibrium data showed that
unwanted eect of aromatic hydrocarbons extraction proceeds parallel to desulfurization and decreases of fuel octane
number.14 Due to the stability and corrosion problems as well
as the total costs of deep fuel desulfurization the choice of
the most suitable ionic liquid is still a challenging task for
researchers. Among many investigated ionic liquids, the
imidazolium thiocyanate ones, e.g. [BMIM][SCN], [EMIM][SCN] were proved to show very small interactions between
alkanes and cycloalkanes and high selectivity with respect to
thiophene separation from such solvents, and they were highly
useful for the fuel desulfurization process.8,14,15 A less expensive alternative is the use of imidazolium-based phosphoric
ionic liquid which showed encouraging results.16-18 The
reported desulfurization facility of this type of ILs may be
ordered as follows: [BMIM][DBP] > [EMIM][DEP] .
[MMIM][DMP]. Additionally the selectivity for sulfur removal decreases from dibenzothiophene through benzothiophene up to 3-methylthiophene.17 On the other hand the fuel
solubility increases in the same way, so the compromise is
necessary to choose the most eective one which was proved
by Nie et al.18 The authors showed that partition coecients
values increases for ionic liquids containing longer alkyl
substitute of the anion or cation. Holbrey and co-workers19

ARTICLE

have investigated {dibenzothiophene dodecane IL} ternary systems for a range of ionic liquids with dierent cation
type (imidazolium, pyridinium, and pyrrolidinium) and a
range of anion types. The partition coecient of dibenzothiophene to the ionic liquids varies following the order with
cation class (dimethylpyridinium > methylpyridinium > pyridinium imidazolium pyrrolidinium). The anion type
inuence is much less important.
The aim of this study is to investigate the possible use of ILs as
solvents for two separation problems frequently encountered in
petroleum industry: {aromatic sulfur compound aliphatic hydrocarbon} or {nitrogen compound aliphatic hydrocarbon}. This
work is focused on three ILs: 1-ethyl-3-methylimidazolium thiocyanate, 1,3-dimethylimidazolium methylphosphonate, and tris-(2-hydroxyethyl)-methylammonium-methylsulfate.
The rst part of presented work consists on a study of new
ternary systems to acquire information about application of
proposed ILs as solvents for extraction of sulfur and nitrogen
containing organic compounds from aliphatic hydrocarbons.
Therefore, LLE measurements of ternary mixtures for ve
systems were measured at 298.15 K and atmospheric pressure:
{thiophene n-heptane 1-ethyl-3-methylimidazolium thiocyanate}, {thiophene n-heptane 1,3-dimethylimidazolium
methylphosphonate}, {thiophene n-heptane tris-(2-hydroxyethyl)-methylammonium-methylsulfate}, {pyridine n-heptane 1-ethyl-3-methylimidazolium thiocyanate}, {pyridine
n-heptane 1,3-dimethylimidazolium methylphosphonate}.
Moreover the temperature inuence for the best one of used
ILs and LLE measurement at 303.15 K and atmospheric pressure
for {thiophene n-heptane 1-ethyl-3-methylimidazolium
thiocyanate} system is shown. Experimental data were correlated
using the NRTL and UNIQUAC activity coecient models. The
second section of this article presents results of extraction of
synthetic fuels - model gasoline and model diesel by the use of
selected ILs. The inuence of extraction time or temperature and
three-step extraction using each time a fresh portion of ILs on the
nal fuel contamination were investigated.

EXPERIMENTAL SECTION
Thiophene and pyridine were supplied by Sigma-Aldrich with
purity of 99% and 99.8%, respectively. N-Heptane was purchased
from Fisher Scientic, with purity of 99%. 2,2,4-Trimethylpentane
was 99% pure from Merck. Toluene, dibenzothiophene, and n-hexane were supplied by Across Organics with a quoted purity of 99%
and 99% and 95%, respectively. N-Dodecane and n-hexadecane were
taken from Fluka and were over 98% pure. All those chemicals were
used for experiments without any further purication. The investigated ionic liquids: 1-ethyl-3-methylimidazolium thiocyanate,
[EMIM][SCN], and tris-(2-hydroxyethyl)-methylammoniummethylsulfate, [TEMA][MeSO4], were purchased from Fluka and
were over 95% pure. 1,3-Dimethylimidazolium methylphosphonate,
[DMIM][MP], was obtained from Solvionic with reported purity of
98%. Before measurements, the ionic liquids were puried under
vacuum for approximately 12 h to remove possible traces of solvents
and moisture. The water content of the ionic liquids determined
using the Karl Fischer technique was from 300 to 700 ppm.
DETERMINATION OF TIE LINES OF TERNARY MIXTURES
The LLE measurements of ternary mixtures have been
performed in jacketed glass cells. The experimental set up
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Industrial & Engineering Chemistry Research

Table 1. GC Operating Conditions for Composition Analysis
injector temperature
carrier gas

250
C
helium

capillary column

WCOT Ulti-Metal coated with HT-SIMDIST-CB

(10 m  0.53 mm  0.53 m) with

ow rate

an empty precolumn
2 mL.min-1

column oven

70
Cf125
C (5
C/min), 5 min

detector type

FID

detector temperature

250
C

consists of a cell with an internal volume of about 30 cm3 kept at

constant temperature of 298.15 K using a thermostated bath.
The temperature inside the cell is measured by a platinum
resistance thermometer PT-100 with an accuracy of (0.1 K.
The ternary mixtures, with compositions inside the immiscible
region of the system, are weighed using a METTLER analytical
balance with a precision of (0.0001 g. All the mixtures were
vigorously mixed using a Teon coated magnetic stirrer for 2 h to
reach a good contact between both phases and kept overnight in
order to settle down. Then, samples of both layers were taken
from the cell using a syringe. The compositions of organic
compounds such as n-heptane, thiophene, or pyridine were
determined by gas chromatography. The GC operating conditions are given in Table 1. All GC analysis were repeated three
times to check reproducibility. For determination of the ionic
liquid composition, density measurements of both phases were
performed at 298.15 or 302.15 K with a vibrating tube densimeter (Anton Paar, model DMA601). The uncertainty in the
measurements is (10-5 g 3 cm-3. The estimated uncertainty in
the determination of mole fraction compositions is (10-4.

MODELED FUELS DESULFURIZATION EXPERIMENTS

The commercial gasoline was modeled by the mixture of
26 wt % hexane, 26 wt % heptane, 26 wt % iso-octane, 10 wt %
toluene, 6 wt % thiophene, and 6 wt % pyridine. Commercial
diesel was represented by model mixture containing 26 wt %
heptane, 26 wt % dodecane, 26 wt % hexadecane, 10 wt %
toluene, 3 wt % thiophene, 3 wt % dibenzothiophene, and 6 wt %
pyridine. The inuence of time of extraction on the model-fuel
composition was investigated by introduction of equal volumes
of model gasoline and IL into thermostated, 30 cm3 cells. The
mixture was vigorously stirred to achieve good contact of both
phases and stopped after 15 min to separate the phases. The
gasoline phase samples were taken using syringe with needle after
0.5 h, 1 h, 2 h, and 6 h after stopping the stirring and their
compositions were analyzed by GC. The extraction in steps was
conducted three times by using new portion of IL and gasoline or
diesel as a feed in following extraction stages. The fuel composition after each step was determined by GC.
RESULTS AND DISCUSSION
Thermodynamic Study of the Ternary Systems {Thiophene or Pyridine/n-Heptane/IL}. The investigations of pos-

sible use of selected ionic liquids for sulfur or nitrogen containing

organic compounds extraction in fuel industry have been performed. For this purpose, LLE of five ternary systems were
determined: {thiophene n-heptane [EMIM][SCN]}, {pyridine n-heptane [EMIM][SCN]}, {thiophene n-heptane
[DMIM][MP]}, {pyridine n-heptane [DMIM][MP]},

ARTICLE

{thiophene n-heptane [TEMA][MeSO4]}. The influence

of water contents of 2 and 5 wt % on the desulfurization
selectivity and capacity of [EMIM][SCN] at 298.15 and
303.15 K have been studied. Moreover, synthetic gasoline
and diesel were prepared, and their desulfurizations by the use
of selected ILs have been conducted.
Table 2 shows the compositions of the experimental tie lines
for the ve investigated ternary systems at 298.15 K. The
equilateral triangular diagrams with LLE representation of these
systems are presented in Figures 1 - 5. All equilateral triangular
diagrams show a behavior that corresponds to the Type 2 with
two of their binary systems exhibiting partial immiscibility and
with only one immiscibility region. Values of solute distribution
ratio and selectivity S reported in Table 2 are calculated from
experimental data according to equations
xIL
1
1
HC
x1
S

HC
xIL
1 3 x2
IL
xHC
1 3 x2

where x is the mole fraction, subscripts 1 and 2 refer to solute

(pyridine, thiophene) and to hydrocarbon (n-heptane), respectively, and superscripts HC and IL indicate the hydrocarbon-rich
phase and the IL-rich phase, respectively.
In these ternary phase diagrams, the low thiophene or pyridine
concentration part should be considered in order to investigate
deep desulfurization of fuels using ionic liquids. Among investigated ionic liquids, [EMIM][SCN] shows the highest selectivity
for thiophene and pyridine (see Table 2). [DMIM][MP] is also
highly selective for thiophene, but the solute distribution ratio is
twice smaller than with [EMIM][SCN]. At low molar fraction
of thiophene, the selectivity with [EMIM][SCN] is about 1600
at 298.15 K. This high selectivity is mainly due to the immiscibility of n-heptane in this ionic liquid. The capacity of [EMIM][SCN] for thiophene extraction from hydrocarbon solvent
decreases with increment of temperature. Selectivity of numerous ternary systems {thiophene heptane ionic liquid} has
been reported in the literature. Our previous investigation on
[BMIM][SCN] showed lower values of selectivity ranging from
19 up to 284 than with [EMIM][SCN].8 Nevertheless, the
solute distribution ratio increases when the alkyl chain length
grafted on the cation increases. Arce and co-workers have also
investigated some other ionic liquids for the extraction of
thiophene from n-heptane: [HMMpy][Ntf2], [OMIM][Ntf2],
[OMIM][BF4], and [EMIM][EtSO4].20-24 For these ternary
systems, the highest selectivity was found for [EMIM][EtSO4],
and the capacity was ranging from 0.7 to 1.68. Compared to
[EMIM][SCN], [EMIM][EtSO4] has a lower selectivity but a
solute distribution ratio twice higher.
Figures 6 and 7 show the evolution of the solute distribution
ratio as a function of thiophene or pyridine mole fraction. The
thiophene distribution coecients are relatively low in all ternary
systems containing thiophene. Values of are below the unit for
all three investigated ionic liquids. In case of ternary systems
containing pyridine, values are over the unit for [DMIM][MP]
and [EMIM][SCN] in the whole range of concentration. The
highest values are obtained for [EMIM][SCN] indicating that
this ionic liquid would be the most advantageous as a solvent for
hydrocarbon fuels denitrication. Figure 8 shows the inuence of
water content of 2 or 5 wt % in ionic liquid for the ternary system
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Table 2. Compositions of Experimental Tie Lines, Solute Distribution Ratios , and Selectivity S for All Ternary Systems
hydrocarbon-rich phase

IL-rich phase
x3HC

x1IL

x2IL

x3IL

x1HC

x2HC

0.0824

0.9176

0.0523

0.0004

0.9473

0.64

1598.5

0.1561

0.8439

0.1082

0.8918

0.69

0.2045

0.7955

0.1287

0.0020

0.8694

0.63

252.5

0.3088

0.6596

0.0317

0.2311

0.7689

0.75

0.3701

0.6159

0.0140

0.2660

0.7340

0.72

0.4486

0.5514

0.3396

0.6604

0.76

0.5702

0.4298

0.4030

0.5970

0.71

0.7361

0.2639

0.5153

0.0017

0.4830

0.70

106.5

0.1133

0.8867

0.0683

0.0015

0.9302

0.60

346.8

0.2451

0.7549

0.1695

0.0010

0.8295

0.69

497.3

0.3482

0.6061

0.0457

0.2370

0.7630

0.68

0.3945

0.5750

0.0305

0.2575

0.7425

0.65

0.4386

0.5036

0.0578

0.3237

0.0019

0.6744

0.74

193.4

0.6035

0.3846

0.0119

0.4363

0.0017

0.5620

0.72

165.2

0.6884
0.7874

0.3116
0.2126

0
0

0.4790
0.5390

0.0018
0

0.5192
0.4610

0.70
0.68

119.0

0.1133

0.8867

0.0683

0.0015

0.9302

0.60

346.8

0.2200

0.7555

0.0245

0.0923

0.0002

0.9075

0.42

1756.2

0.2700

0.7300

0.1155

0.0002

0.8842

0.43

1261.2

0.3589

0.6411

0.1574

0.0013

0.8413

0.44

217.1

0.4777

0.5223

0.1927

0.0007

0.8067

0.40

303.7

0.5618

0.4305

0.0078

0.2039

0.7961

0.36

0.6154
0.6917

0.3846
0.3083

0
0

0.2003
0.2254

0.0026
0.0008

0.7971
0.7739

0.33
0.33

48.8
133.8

0.9273

0.0727

0.2402

0.0010

0.7588

0.26

18.9

0.1079

0.8873

0.0047

0.0087

0.0026

0.9887

0.08

27.5

0.2942

0.7058

0.0175

0.0024

0.9801

0.06

17.6

0.4443

0.5557

0.0227

0.0031

0.9742

0.05

9.3

0.4952

0.5048

0.0400

0.0007

0.9593

0.08

56.3

0.6279

0.3721

0.0453

0.0014

0.9534

0.07

19.7

0.6667
0.7905

0.3310
0.2095

0.0022
0

0.0525
0.0641

0.0011
0.0002

0.9465
0.9358

0.08
0.08

24.5
102.0

0.8321

0.1679

0.0733

0.0013

0.9254

0.09

11.1

0.0719

0.9155

0.0126

0.2769

0.0064

0.7167

3.85

549.3

0.1940

0.8060

0.0000

0.5485

0.0133

0.4382

2.83

170.7

0.0346

0.9654

0.0000

0.1670

0.0040

0.8290

4.82

1156.4

0.1104

0.8896

0.0000

0.4363

0.0133

0.5504

3.95

264.0

0.1542
0.5110

0.8458
0.4890

0.0000
0.0000

0.5078
0.7201

0.0187
0.0202

0.4734
0.2597

3.29
1.41

148.7
34.2

0.7164

0.2836

0.0000

0.8783

0.0507

0.1616

1.12

6.8

0.0263

0.9604

0.0133

0.0992

0.0030

0.8978

3.77

1208.9

0.0731

0.9269

0.0450

0.0115

0.9436

0.61

49.6

0.1408

0.8592

0.0924

0.0322

0.8754

0.66

17.5

0.1936

0.8064

0.2298

0.0393

0.7310

1.19

24.4

Thiophene (1) Heptane (2) [EMIM][SCN] (3) at T = 298.15 K

Thiophene (1) Heptane (2) [EMIM][SCN] (3) at T = 303.15 K

Thiophene (1) Heptane (2) [DMIM][MP] (3) at T = 298.15 K

Thiophene (1) Heptane (2) [TEMA][MeSO4] (3) at T = 298.15 K

Pyridine (1) Heptane (2) [EMIM][SCN] (3) at T = 298.15 K

Pyridine (1) Heptane (2) [DMIM][MP] (3) at T = 298.15 K

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Table 2. Continued
hydrocarbon-rich phase

IL-rich phase
x1IL

x2IL

x3IL

0.2976

0.0417

0.6607

1.02

17.3

0
0

0.3499
0.3729

0.0355
0.0292

0.6146
0.5979

0.99
0.88

18.1
17.2

0.5445

0.4104

0.0469

0.5428

0.90

10.5

0.4957

0.4404

0.0382

0.5214

0.87

11.3

0.3260

0.4947

0.0380

0.4674

0.73

6.3

x1HC

x2HC

0.2924

0.7076

0.3529
0.4254

0.6471
0.5746

0.4555
0.5043
0.6740

x3HC

Figure 1. Tie lines for ternary mixture {Thiophene Heptane

[EMIM][SCN]} at 298.15 K. Experimental data: and ;. NRTL
Correlation  (red) and ---- (red). UNIQUAC Correlation 0 (green)
and -- (green).

Figure 2. Tie lines for ternary mixture {Thiophene Heptane

[DMIM][MP]} at 298.15 K. Experimental data: and ;. NRTL
Correlation  (red) and ---- (red). UNIQUAC Correlation 0 (green)
and -- (green).

{thiophene heptane [EMIM][SCN]}. The solute distribution ratio is about three times higher for low thiophene concentration in the case of presence of water. An increase of
temperature decreases the solute distribution ratio.

Figure 3. Tie lines for ternary mixture {Thiophene Heptane

[TEMA][MeSO4] } at 298.15 K. Experimental data: and ;. NRTL
Correlation  (red) and ---- (red).

Figure 4. Tie lines for ternary mixture {Pyridine Heptane

[EMIM][SCN]} at 298.15 K. Experimental data: and ;. NRTL
Correlation and  (red) and ---- (red). UNIQUAC Correlation 0
(blue) and -- (blue).

The LLE data of the investigated ternary systems were

correlated using the Non-Random Two-Liquid equation
(NTRL) proposed by Renon and Prausnitz25 and the UNIversal QUAsi-Chemical (UNIQUAC) theory developed by
Abrams and Prausnitz.26
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Figure 5. Tie lines for ternary mixture {Pyridine Heptane

[DMIM][MP]} at 298.15 K. Experimental data: and ;. NRTL
Correlation  (red) and ---- (red). UNIQUAC Correlation and 0
(green) and -- (green).
Figure 7. Solute distribution ratio as function of mole fraction of
pyridine in the hydrocarbon-rich phase for two systems at 298.15 K.

Figure 6. Solute distribution ratio as function of mole fraction of

thiophene in the hydrocarbon-rich phase for the three systems at
298.15 K.

NRTL Model. For the NRTL Model, the activity coefficient i,

for any component i of the ternary system, is given by
m
P

ln i

ji Gji xj

j1
m
P

l1

Gli xl

m
P

xr rj Grj C
m
X
xj Gij B
C
B
r1
C 3
B

ij
m
m
A
@
P
P
j1
Glj xl
Glj xl
l1

Figure 8. Water inuence on solute distribution ratio as function of mole

fraction of thiophene in the hydrocarbon-rich phase for [EMIM][SCN] at
298.15 K.

UNIQUAC Model. For the UNIQUAC Model, the activity

coefficient i, for any component i of the ternary system, is given by
m
i z
i
i X
xj lj - qi lnj ji
ln i ln qi ln li xi 2
i
xi j 1

l1

with Gji = exp(-Rjiji), ji = (gji-gii)/(RT) = (gji)/(RT), and

Rji = Rij = R where g is an energy parameter characterizing the
interaction of species i and j, xi is the mole fraction of component
i, R is the nonrandomness parameter. Although R can be treated
as an adjustable parameter, in this study it was set equal to 0.3.27

qi - qi

m
X
j1

Pm

j ji
m
P
k kj

k1

P
where i = (rixi)/( j=1rjxj), i = (qixi)/( m
j=1qjxj), lj = z/
2(rj-qj)-(rj-1), and ji = exp((-uij)/(RT)). Here, the lattice
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Table 3. Values of Binary Parameters for the NRTL Equation for the Ternary Mixtures
system

ij

gij (J.mol-1)

gji (J.mol-1)

rmsd

Thiophene (1) Heptane (2) [DMIM][MP] (3)

12

5622.87

1771.01

0.3

0.0321

13

24275.07

6054.1

23

9001.6

20975.87

12

19100.2

5400.98

0.3

0.0056

13

18505.7

5836.4

23

9466.4

20557.2

12

12351.06

9629.64

0.3

0.0005

13
23

7913.05
15198.1

9420.3
5861.5

12

4521.7

1465.4

0.3

0.0338

13

12560.4

-3810

23

12602.3

19510.5

12

4605.5

-2679.5

0.3

0.0024

13

18003

5526.6

23

12058

12393

Thiophene (1) Heptane (2) [BMIM][SCN] (3)

Pyridine (1) Heptane (2) [DMIM][MP] (3)

Pyridine (1) Heptane (2) [BMIM][SCN] (3)

Thiophene (1) Heptane (2) [TEMA][MeSO4]

Table 4. Values of the Binary Parameters for the UNIQUAC Equation

system

ij

uij (J.mol-1)

Thiophene (1) Heptane (2) [DMIM][MP] (3)

12

1386

64

13

2720

524

Thiophene (1) Heptane (2) [BMIM][SCN] (3)

Pyridine (1) Heptane (2) [DMIM][MP] (3)

Pyridine (1) Heptane (2) [BMIM][SCN] (3)

uji (J.mol-1)

23

1072

3300

12

6400

-810

13

2600

450

23
12

-150
-340

3960
2298

13

-212

2498

23

6929

-172

12

510

2330

13

4910

-860

23

4900

150

rmsd
0.0055

0.0112

0.0058

0.0117

coordination number z is assumed to be equal to 10, and ri and qi are

respectively a relative volume and surface area of the pure component i. Parameters ri and qi are respectively relative to molecular van
der Waals volumes and molecular surface areas. They are calculated
as the sum of the group volume and group area parameters Rk and Qk
X
X
ri
ik Rk and qi
ik Qk
5
k

where ik is the number

of groups of type k in molecule i. The group

parameters Rk and Qk are obtained from van der Waals group
volumes and surface areas, and Vk and Ak are taken from the UNIFAC
group contributions28
Vk
Ak
and Qk
Rk
6
15:17
2:5  109
The values of 15.17 and 2.5  109 are respectively the standard
segment volume and standard segment area of a methylene group.28
This means that a total of two adjustable parameters per binary
gji or uji have to be tted for both models. Interaction
parameters for binary systems {thiophene n-heptane} and
{pyridine n-heptane} are not available in the literature at
298 K. These parameters are then tted using the three ternary
mixture data.

Figure 9. Evolution of model gasoline components weight % changes

during extractive desulfurization using [EMIM][SCN] as a solvent at
298.15 and 303.15 K.

Binary interaction parameters for both NRTL and UNIQUAC

equations are those which minimize the dierence between the
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Figure 10. Evolution of model gasoline components weight % changes

during extractive desulfurization using [DMIM][MP] as solvent, 298.15 K
and 303.15.

Figure 11. Evolution of model gasoline components weight % changes in

three-steps extraction process using [EMIM][SCN] as solvent at 298.15 K.

experimental and calculated mole fractions

Fobj:

N X
3
X
k1 i1

I , exp
fxi, k

I , calc
- xi, k 2

II , exp
xi, k

II , calc
- xi, k 2 g

I,calc
where N is the number of tie lines in the data set, xI,exp
i,k and xi,k are
the experimental and calculated mole fractions of one phase, and
and xII,calc
are the experimental and calculated mole fractions of
xII,exp
i,k
i,k
the second phase.
The binary parameters and root mean-square deviation (rmsd),
calculated using the procedure above, of the NRTL and UNIQUAC
equations are given in Tables 3 and 4, respectively. The rmsd values,
which provide a measure of the accuracy of the correlations, were
calculated according to the following equation:

11=2
N P
3
P
I , exp
II , exp
I , calc
II , calc
fxi, k - xi, k 2 xi, k - xi, k 2 gC
B
Bk 1 i 1
C
rmsd B
8
C
@
A
6N

Figure 12. Evolution of model gasoline components weight % changes in

three-steps extraction process using [DMIM][MP] as solvent at 298.15 K.

Figure 13. Evolution of model diesel components weight % changes in

three-steps extraction process using [EMIM][SCN] as solvent at 298.15 K.

For the ternary system {Thiophene Heptane [TEMA][MeSO4] }, the UNIQUAC model was not applied due to the lack
of volume, Rk, and area, Qk, parameters of van der Waals groups for
this ionic liquid. As can be inferred from the rmsd values, fairly good
correlation of the experimental values with NTRL and UNIQUAC
models was obtained.
In the case of ternary systems {Thiophene n-heptane
[DMIM][MP]} and {Pyridine n-heptane [BMIM][SCN]},
the UNIQUAC model ts much better than the NRTL equation.

MODEL FUELS EXTRACTION

The weight percentage of model gasoline components changes as
a function of extraction time using [EMIM][SCN] and [DMIM][MP] as an extractive solvent are shown at Figures 9 and 10, respectively. In both experiments, the concentration of sulfur and nitrogen
-containing compounds reached the minimum after 2 h. Thus, the
extraction period applied in all fuel desulfurization stages was 2 h.
The higher temperature of extraction process causes the higher
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Figure 14. Evolution of model diesel components weight % changes

in three-steps extraction process using [DMIM][MP] as solvent at
298.15 K.

ARTICLE

Figure 16. Evolution of thiophene content (wt%) in simulated gasoline

for investigated ionic liquids in three-step desulfurization process.

Figure 17. Evolution of thiophene content (wt%) in simulated diesel

for investigated ionic liquids in three-step desulfurization process.
Figure 15. Evolution of model diesel components weight % changes
in three-steps extraction process using [TEMA][MeSO4] as solvent at
298.15 K.

equilibrium content of thiophene as well as pyridine in rened

gasoline (Figures 9 and 10). Thus desulfurization conducted at
298.15 K for both examined [EMIM][SCN] and [DMIM][MP] is
more ecient, and this temperature was applied in all further
experiments presented in this work.
Model gasoline has been desulfurized in three steps at
298.15 K using [EMIM][SCN] and [DMIM][MP] as solvent.
Figures 11 and 12 show the composition of model gasoline
mixture and changes of weight percent of each component after
one, two, and three extraction steps. The same experiments have
been performed for simulated diesel oil. Desulfurization were
conducted with [EMIM][SCN], [DMIM][MP], and [TEMA][MeSO4] as an extractive solvents. Results are presented at
Figures 13-15. Sulfur and nitrogen containing compounds are
extracted from hydrocarbon fuels by all free investigated ionic

liquids. The best results have been obtained for [EMIM][SCN]

where after the third stage most of the thiophene and all of the
pyridine have been extracted. These results are in agreement with
obtained LLE data of ternary systems. However, deep desulfurization is also accompanied with unwanted reduction of aromatic
hydrocarbon concentration, which causes lower octane number
of the fuels. Comparison of investigated ionic liquids for gasoline and diesel desulfurization is presented in Figures 16-18.
[EMIM][SCN] ensures 94% of thiophene content reduction in
model gasoline and 88% in model diesel oil, while dibenzothiophene is completely extracted from diesel after three process
stages. This ionic liquid [TEMA][MeSO4] chosen due to its
relatively low price presents the lowest capacity for fuels desulfurization. The use of [TEMA][MeSO4] allows for extraction of
about 10% of thiophene and 20% of dibenzothiophene from
simulated diesel. It shows that this IL is useless for fuel desulfurization purpose. The third investigated ionic liquid [DMIM][MP] allows for more than 50% of sulfur containing compounds
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Figure 18. Evolution of dibenzothiophene content (wt%) in simulated

diesel for investigated ionic liquids in three-step desulfurization process.

extraction, eective denitrogenation without fuel dearomatization.

CONCLUSIONS
(Liquid liquid) equilibrium data for the ve ternary systems
{thiophene n-heptane [EMIM][SCN]}, {pyridine
n-heptane [EMIM][SCN]}, {thiophene n-heptane
[DMIM][MP]}, {pyridine n-heptane [DMIM][MP]},
and {thiophene n-heptane [TEMA][MeSO4]} at T =
298.15 K were determined. All ternary systems correspond to the
Type 2 category, with partial or total immiscibility of the IL with
the thiophene and the hydrocarbons. The NRTL and UNIQUAC
models were used to correlate the experimental LLE results.
In general, the LLE data of the ternary systems studied
are better correlated with the UNIQUAC model than with
the NRTL model. Then, it was found that [EMIM][SCN]
has a good capacity for fuels desulfurization. Indeed,
[EMIM][SCN] ensures 94% of thiophene content reduction
in model gasoline and 88% in model diesel oil, while dibenzothiophene is completely extracted from diesel in the third
process stage. This ionic liquid [TEMA][MeSO4] chosen due to
its relatively low price presents the lowest capacity for fuels
desulfurization.

AUTHOR INFORMATION
Corresponding Author

*Phone: 33 3 83 17 51 31. Fax: 33 3 83 17 53 95. E-mail:

mutelet@ensic.inpl-nancy.fr.

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