Chemical Engineering Journal 221 (2013) 99–104

Contents lists available at SciVerse ScienceDirect

Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Synthesis, characterization, and properties of imidazole dicationic ionic

liquids and their application in esterification
Dishun Zhao a,⇑, Mengshuai Liu a, Juan Zhang a, Junpan Li a, Peibing Ren a,b
a
College of Chemical and Pharmaceutical Engineering, Hebei University of Science and Technology, Shijiazhuang 050018, China
b
Shijiazhuang Coking & Chemical Group Co., Ltd., Shijiazhuang 050031, China

h i g h l i g h t s

" Three kinds of imidazole based dicationic ionic liquids were synthesized efficiently.
" Key physicochemical properties of dicationic ionic liquids were determined.
" Dicationic ILs as catalyst, esterification has been carried out at room temperature.
" Catalytic activity of three kinds of dicationic ILs with C2, C3, C4 differed little.
" The IL catalysts can be easily recovered without any other chemical residued.

a r t i c l e i n f o a b s t r a c t

Article history: Three kinds of imidazole based dicationic [C2(Mim)2], [C3(Mim)2], [C4(Mim)2] with traditional counter
Received 30 August 2012 anion HSO4 ionic liquids (ILs) were synthesized. Key physicochemical properties, such as thermal stabil-
Received in revised form 18 January 2013 ity, solubility in common solvents, acidic property and corrosion of ILs for Austenitic stainless steel 316
Accepted 23 January 2013
were determined. Esterification of alcohols by carboxylic acids has been carried out at room temperature
Available online 6 February 2013
in a group of imidazole dicationic ionic liquid. The catalytic performance was found to be much better
than that of conventional non-cation functionalized ionic liquids and the corrosion was five times weaker
Keywords:
than sulfuric acid. The esters were easily recovered due to immiscibility with the ionic liquid and
Dicationic ionic liquid
Esterification
reported imidazole dicationic ionic liquids were a promising catalyst for esterification reaction.
Catalyst Ó 2013 Elsevier B.V. All rights reserved.
Brønsted acidity

1. Introduction Currently, ionic liquids (ILs) are receiving a widespread atten-

Esters made from carboxylic acids are important intermediates
in chemical and pharmaceutical industries, and they are mostly
produced by acid-catalyzed esterification reactions [1]. It is well
accepted that mineral acids, such as H2SO4, HF, and H3PO4 have
been widely used as catalysts in the production of esters. However,
many drawbacks of this traditional method have shown up: firstly,
removal of water or/and use of an excess amount of the reactants is
needed to attain satisfactory conversion [2]. Furthermore, the
removal of the liquid inorganic acid or the separation of the prod-
uct from the catalyst also calls for a large effort, and pollution may
be produced if a large amount of volatile organic solvents and
liquid inorganic acid are used [3]. Its low efficiency use makes
environment and health problems more serious, which urge
researchers to develop and apply clean catalytic technology that
suits Chinese special conditions.
⇑ Corresponding author. Tel./fax: +86 0311 88632231.
E-mail address: dishunzhao@yahoo.com.cn (D. Zhao).
tion as mediums for a variety of reactions [4]. The main driving
force to explore ionic liquids is the fact that these compounds have
a very low vapor pressure, so that they are candidates to replace
volatile organic solvents in organic reactions. Because the proper-
ties of ionic liquids (miscibility with water and other solvents, dis-
solving ability, polarity, viscosity, density, etc.) can be tuned by an
appropriate choice of the anion and the cation, ionic liquids are
often considered as designer solvents [5–7]. The application of
ILs as catalyst and medium for the Fischer esterification reaction
have been an area of intense investigation. Fraga-Dubreuil et al.
[8] reported the first esterification of acetic acid and methyl
malonic acid with alcohols of chain lengths C5–C10 in imidazoli-
um-based IL with acidic counterions, HSO4 and H2 PO4 . Along with
the quick development of room temperature ionic liquids, Lewis
acidic ILs [9], alkylamines ILs [1,4,10] and phosphonium salt ILs
[11,12] have also been reported in the literature. Tao et al. [1] re-
ported seven Brønsted acidic ionic liquids composed of [HSO4] as
catalysts of low dosage in various esterification reactions. The ILs
were found to be nearly noncorrosive and could be reused.

1385-8947/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2013.01.077
100 D. Zhao et al. / Chemical Engineering Journal 221 (2013) 99–104

O O
[C4(Mim)2]2HSO4
N N N
2HSO4- R' OH
N 30-80°C R
R OH OR'
H3C (CH2)2 CH3
Fig. 3. Esterification in ionic liquids.
[C2(Mim)2]2HSO4-

(Tianjin, China). FTIR spectra were measured on a USA Bio-Rad

N N N
2HSO4- FTS-135 using the KBr pellet technique. Thermal gravimetric anal-
N
H3C (CH2)3 ysis (TGA) measurements were performed on a SII TG/DTA 209 at a
CH3
heating rate of 10 °C/min. 1HNMR spectra were obtained as solu-
-
[C3(Mim)2]2HSO4 tions in either D2O or DMSO. Gas chromatographic analyses were
performed using an Agilent 6850 system (FID).

N N N
2HSO4-
N
H3C (CH2)4 CH3
[C4(Mim)2]2HSO4 -
Fig. 1. Structure of three imidazole dicationic ionic liquid.
However, these results are not entirely satisfactory because of the
low conversion and ester yield. A new approach using alkyl sulfo-
nate functionalized ILs have been focused on more efforts, but have
not crossed the barrier of corrosivity. Chinnappan and Kim [13]
synthesized and characterized a series of pyridinium based dicat-
ionic ILs, their catalytic activity were evaluated in the esterification
and the results showed that carboxylic acids were successfully
converted into esters with good yields and high selectivity. Mean-
while, multifunctional cationic ILs are attracting more attention as
alternative reaction media in green chemistry than conventional
monocationic ionic liquid [14–28], especially as the catalyst of
esterification reaction [29–31].
There is now a general consensus that higher acidity of the
anion in the ionic liquid resulted in high yield of the ester
[1,4,32]. Only few researches have focused on different carbon
lengths of imidazole dicationic cation in promoting chemical reac-
tions. Our research is mainly devoted to design and synthesis of
different carbon lengths of imidazole dicationic ionic liquid with
traditional counter anion HSO4 , observe the characterization, prop-
erties and tested for the esterification of carboxylic acids by react-
ing with fatty alcohol. The reusability of ILs and the corrosion rate
of stainless steel by ILs were also explored.
2. Experimental
2.1. General information
1-Methylimidazole, 1,2-Dibromoethane, 1,3-Dibromopropane,
and 1,4-Dibromobutane were purchased from Aladdin Chemistry
Co., Ltd. and were used without further purification. Sulfuric acid
(98%), ethyl acetate, cyclohexane, acetic acid, ethanol, n-propanol,
1-butanol, pentanol, benzyl alcohol and octanol were of analytical
grade and purchased from YongDa Chemical Reagent Co., Ltd.
2.2. Synthesis of imidazole dicationic ionic liquid
Three ILs composed of [HSO4] anion and different cations were
prepared in the paper (Fig. 1). The FT-IR and 1HNMR spectrum of
these ILs were recorded, and the detailed preparation methods
and characterization results are as follows.
Preparations of ionic liquid [C4(Mim)2]2HSO4: firstly, 1-methyl-
imidazole (8.21 g, 0.10 mol) and 1,4-Dibromobutane (10.80 g,
0.05 mol) were charged into a 100 ml round bottom flask, carried
on in cyclohexane around 80 °C for 24 h. The white solid interme-
diate product [C4(Mim)2]2Br was washed repeatedly with ether to
remove non-ionic residues and dried at 80 °C in vacuum
(0.005 MPa) for 6 h. Second, the formed solid (11.40 g, 0.03 mol)
was dissolved in 100 ml H2O in a 250 ml round bottom flask, sulfu-
ric acid (5.88 g, 0.06 mol) and Ag2O (6.96 g, 0.03 mol) were slowly
added in turn at 0 °C. After the dropping was finished, the mixture
was stirred for 8 h at room temperature. Finally, the formed wine-
colored liquid was washed with ethyl acetate for 3 times and dried
in vacuum (0.005 MPa) at 80 °C for 12 h (Fig. 2). Preparations of
ionic liquid [C3(Mim)2]2HSO4 and [C2(Mim)2]2HSO4 were similar
to that of [C4(Mim)2]2HSO4.
Take [C4(Mim)2]2HSO4 for example, characterization results:
1
HNMR (500 MHz, DMSO): d 1.82 (s, 4H), 3.79 (s, 6H), 4.16
(s, 4H), 7.39 (d, 4H), 8.66 (s, 2H); FT-IR (Film): 3141, 3071, 2970,
1631, 1573, 1457, 1396, 1050, 575 cm 1.
2.3. Typical procedure for the esterification reaction
Taking the esterification of acetic acid with 1-pentanol as an
example. Acetic acid (6.01 g, 0.10 mol), 1-pentanol (8.82 g,
0.10 mol) and ionic liquid [C4(Mim)2]2HSO4 (0.50 g, 1.21 mmol)
were taken in a round bottom flask of 100 ml capacity. The flask
was fitted with a condenser and flushed with nitrogen gas. A nitro-
gen balloon was fitted at the top of the condenser to maintain inert
atmosphere. Then the reaction was allowed to proceed at desired
temperature for 3 h (Fig. 3). After the reaction, the esterification
system often forms a liquid–liquid biphase. The upper phase, con-
taining mainly the desired ester, can be isolated simply by decan-
tation. Quantification of product was done by GC 6850 analysis.
Whereas the lower phase composed of ionic liquid and water can
be recycle after removing the water under vacuum at 90 °C.

2 (CH2)4Br2 2Br- H2SO4

N N N N N N
H3C H3C (CH2)4 CH3

2HSO4- AgBr
N N N N
H3C (CH2)4 CH3

Fig. 2. Preparation of [C4(Mim)2]2HSO4.

 D. Zhao et al. / Chemical Engineering Journal 221 (2013) 99–104 101

Table 2
100 C4 (Mim) 2
C3 (Mim) 2 The acidity of H2SO4 and various ionic liquids in water.
C2 (Mim) 2
w(IL)/% pHa
80
0.2% 0.4% 0.6% 0.8% 1.0%
C2(Mim)2HSO4 1.99 1.81 1.67 1.55 1.51
Weight loss (%)

60 C3(Mim)2HSO4 1.78 1.63 1.52 1.40 1.32

C4(Mim)2HSO4 2.09 1.97 1.84 1.74 1.63
H2SO4 1.06 0.87 0.68 0.54 0.45
40
a
pH Values were determined at 25 °C with different concentrations of ILs in
water. After the ILs were dissolved in water the solutions were allowed to stand for
20 0.5 h and then the pH was determined.

0 3.2. Solubility
0 200 400 600 800

The solubilities of ILs in both organic compounds and metal

Fig. 4. TGA curves of synthesized dicationic ionic liquid HSO4 anion with
[C2(Mim)2], [C3(Mim)2] and [C4(Mim)2].
3. Results and discussion
3.1. Thermal stability
Thermal decomposition temperatures of all imidazole dication-
ic ILs were measured by thermogravimetric analyzer (TGA) under a
nitrogen atmosphere with a heating rate of 10 °C/min. The TGA
curves for [C2(Mim)2]HSO4, [C3(Mim)2]HSO4 and [C4(Mim)2]HSO4
were shown in Fig. 4, respectively. As shown in Fig. 4, the three
imidazole dicationic ionic liquids showed a similar thermal decom-
position process consisting of gradual and continuous weight loss
between 210 °C and 320 °C. This was followed by a major weight
loss event around 320–400 °C. Small amount of weight loss within
210 °C was attributed completely to the loss of adsorbed water
molecules. [C2(Mim)2]HSO4 started to decompose at 270 °C,
whereas [C3(Mim)2]HSO4 and [C4(Mim)2]HSO4 began to decom-
pose at 250 °C and 235 °C respectively. At 50% weight loss, the
decomposition temperature was at 360 °C for [C2(Mim)2]HSO4,
320 °C for [C3(Mim)2]HSO4, and 298 °C for [C4(Mim)2]HSO4. These
figures implied that the thermal stability of both [C3(Mim)2]HSO4
and [C4(Mim)2]HSO4 were lower than that of [C2(Mim)2]HSO4.
The results reveal that there is an effect on dicationic ILs thermal
stabilities by changing the alkyl chain of halohydrocarbon, and
thermal stabilities decrease with the increase of alkyl carbon
length. But at the same time these imidazole dicationic ILs show
much higher thermal stabilities than traditional monocationic
ILs. The thermal decomposition temperature for traditional mono-
cationic ILs ranges from 145 °C to 185 °C, e.g., 1-butyl-3-methyl-
imidazolium chloride and 1-butyl-3-methylimidazolium bis
(trifluoromethylsulfonyl) imide [13,33,34].
salts are important with regard to stoichiometric chemical synthe-
sis and catalytic processes. Not only must reagents and catalysts be
sufficiently soluble in the solvent, but differential solubilities of
reagents, products, and catalysts are required in order to enable
effective separation and isolation of products. Extractions and sep-
arations in two-phase systems require knowledge of the miscibili-
ties and immiscibilities of ILs with other solvents compatible with
the process. However, only limited systematic data on these prop-
erties are available in the literature. In the experiment, we defined
the criteria used for considering soluble ionic liquid or insoluble
ionic liquid as follows: transferred 0.25 g of ILs to 10 mL of differ-
ent organic solvents, and mixed at room temperature. If the IL was
totally dissolved in organic solvent, we considered it to be soluble
ionic liquid, otherwise we considered it to be insoluble ionic liquid.
Table 1 showed the solubility behavior of synthesized imidazole
dicationic ILs in polar and non polar solvents. They exhibited good
solubility in high polar solvents such as water, acetic acid, acetoni-
trile, and dimethylformamide. And they cannot be dissolved in
cyclohexane, ether, ethyl acetate, etc. non polar solvents. Then
these imidazole dicationic ILs can be considered to be polar
solvents, and have polarititied similar to those of short-chain alco-
hols and other polar, aprotic solvents (DMSO, DMF, etc.) [35–36].
3.3. Determination of acidity
The Brønsted acidity is an essential property of ILs, according to
the literatures, the Brønsted acidity of H2SO4 and various ionic liq-
uids in water were investigated [37]. The results were shown in
Table 2. Three kinds of ILs showed strong acidity, the main reason
why they could efficiently promote esterification when they were
used as catalysts should be the contribution of ‘‘strong acidity’’. For
the same ILs concentration, the acidity order is as follows:
H2SO4 > C3(Mim)2HSO4 > C2(Mim)2HSO4 > C4(Mim)2HSO4. For the

Table 1
Solubility of dicationic ILs in various organic solvents.a

Ionic liquid Solubility of solvent

Water Acetone Acetic acid Ethanol Dichloromethane Cyclohexane
C2(Mim)2HSO4 s s s s i i
C3(Mim)2HSO4 s i s s i i
C4(Mim)2HSO4 s i s i i i
H2SO4 s r s r s s
Ether Toluene Acetonitrile n-hexane Dimethylformamide Ethyl acetate
C2(Mim)2HSO4 i i s i s i
C3(Mim)2HSO4 i i s i s i
C4(Mim)2HSO4 i i s i s i
H2SO4 r s r i r s
a
Test conditions: V(solvent) = 10 ml, m(IL) = 0.25 g, m(H2SO4) = 0.25 g, r.t.; s: soluble; i: insoluble, r: reaction.
102 D. Zhao et al. / Chemical Engineering Journal 221 (2013) 99–104

same IL, the acidity increased with increasing concentration. Theo- Table 4
retical studies demonstrate that the hydrogen bonding plays a key Results of esterification of amyl acetate under different conditions.a

role in tuning the acidity of ILs [38]. It is obvious that H2SO4 Entry Catalysts Mass fraction of Time Temperature Yield
exhibits the strongest acidity. In ionic liquids, the Brønsted acidity IL (%)b (h) (°C) (%)c
is due to the presence of HSO4 and imidazolium C–H (2-position). 1 C2(Mim)2HSO4 13.3 2 r.t. 85
As to [C2(Mim)2], [C3(Mim)2], [C4(Mim)2] with same anion HSO4 2 C2(Mim)2HSO4 10.0 2 r.t. 87
ionic liquids (ILs), it is clear that the cationic structures of imidaz- 3 C2(Mim)2HSO4 6.7 2.5 r.t. 81
4 C2(Mim)2HSO4 3.3 2.5 r.t. 80
ole dicationic ILs have significant influence on their Brønsted acid- 5 C2(Mim)2HSO4 10.0 4 r.t. 86
ities. The acidity of C3(Mim)2HSO4 is comparatively higher than 6 C3(Mim)2HSO4 13.3 2 r.t. 94
that of C2(Mim)2HSO4 and C4(Mim)2HSO4. Probably because that 7 C3(Mim)2HSO4 10.0 2 r.t. 91
the –(CH2)3– group made the imidazolium C–H (2-position) more 8 C3(Mim)2HSO4 6.7 2.5 r.t. 89
9 C3(Mim)2HSO4 3.3 2.5 r.t. 83
active, and on the other hand, the acidic sites of unit space
10 C3(Mim)2HSO4 10.0 4 r.t. 88
decreased with increasing of cationic size. 11 C4(Mim)2HSO4 13.3 2 r.t. 93
12 C4(Mim)2HSO4 10.0 2 r.t. 89
13 C4(Mim)2HSO4 6.7 2.5 r.t. 86
3.4. Corrosion test 14 C4(Mim)2HSO4 3.3 2.5 r.t. 81
15 C4(Mim)2HSO4 10.0 4 r.t. 87
As an important property, corrosion of ILs to a great extent 16 H2SO4 33.3 6 110 76
determine the security and economy of esterification process a
Reaction conditions: n(acetic acid) = 0.25 mol: n(1-pentanol) = 0.20 mol.
which applied ILs as the catalyst. Acidity usually refers to ionizing b
Based on the mass of acetic acid.
ability to generate hydrogen ions of the substance in a solvent, the c
Yield was achieved by GC analysis.
higher the degree of ionization, the stronger of the acidity. The cor-
rosion refers to the dissolving ability or reaction activity to some
objects, such as metal utensils, clothing, skin. In most cases, the
the yield just could reach 76% (Table 4, Entries 16) at 110 °C for 6 h,
stronger the acidity, the stronger the corrosive action on metals.
and could only reach 22% at room temperature which was far low-
However, both are not necessarily linked. That is to say that the
er than that catalyzed by C3(Mim)2HSO4. The results indicated that
acid–base properties is not the only factor affecting the corrosive
the synthesis of amyl acetate catalyzed by imidazole dicationic ILs,
strength, there are many needs to be considered, such as material
not only improved the product yield, but reduced energy consump-
being in contact, temperature and water. A 316L Austenitic stain- tion and enhanced production efficiency.
less steel plate with 20 mm length, 20 mm width and 0.5 mm
In further experiments, we investigated the esterification reac-
thickness was immersed in the esterification system containing a tions of acetic acid, n-butyric acid, benzoic acid, succinic acid with
given imidazole dicationic IL catalyst for corrosion test under the
ethanol, n-propanol, 1-butanol, methanol and iso-propyl alcohol in
following conditions: acetic acid, 1-pentanol and the IL being various ionic liquids, and the results were summarized in Table 5.
charged into a flask was stirred at 25 °C for 15 h. The treatment
As expected, carboxylic acids were successfully converted into es-
method of the steel immersed was according to the literature ters with good to high yields and high selectivity under mild reac-
[39]. The results were summarized in Table 3. It is observed that
tion conditions and without any additional organic solvent.
the corrosion rate of 316L stainless steel in the reactive solution Through investigating solubility of dicationic ILs (Table 1), it is
containing C2(Mim)2HSO4, C3(Mim)2HSO4, C4(Mim)2HSO4, or
identified in the paper that ILs can be dissolved in carboxylic acids
H2SO4 is 1.97, 2.12, 1.79, and 12.34 g m 2 h 1, respectively. The
and alcohols, when discussed from the kinetic point of view, the
ILs are almost noncorrosive (Table 3, Entries 1–3), and H2SO4 is
reaction is homogeneous which helps to improve the reaction rate
obviously the most corrosive catalyst because of its strongest acid-
and shorten balance time. In addition, catalytic activity of three
ity (Table 3, Entry 4). It is fantastically to note that although acidity
kinds of imidazole dicationic ILs with –(CH2)2–, –(CH2)3–,
of ILs are slightly weaker than sulfuric acid, corrosion of sulfuric
–(CH2)4– differed little, and chemical structures, characteristics
acid is more than five times stronger than ILs.
and application in the esterification of dicationic ILs with –(CH2)n
– (n P 5) have been studying. As the ionic liquid and the esters
3.5. Catalytic activities of imidazole dicationic ILs were immiscible, the ionic liquid was easily separated by simple
decantation, and it could be reused directly without any treatment.
The esterification of acetic acid with 1-pentanol is typically cat- Thus, reported imidazole dicationic IL was a promising catalyst for
alyzed by imidazole dicationic ILs. The results listed in Table 4. esterification reaction.
There is no doubt imidazole dicationic ILs showed excellent cata-
lytic performance (Table 4, Entries 2, 6, 11), and a good yield of 3.6. Recycling of the imidazole dicationic ionic liquid
amyl acetate was observed in the presence of 13.3% (based on
the mass of acetic acid) C3(Mim)2HSO4 at room temperature for The feasibility and sustainable development of any catalytic
2 h (Entry 6). Comparatively speaking, using H2SO4 as the catalyst, process depends on the reusability of the catalyst. One of the pri-
mary aims of our study was to investigate the recycling of imidaz-
ole dicationic IL. As [C4(Mim)2]HSO4 applied to synthesis amyl
Table 3 acetate for example, [C4(Mim)2]HSO4 can be easily separated by
Corrosion of ILs for Austenitic stainless steel 316 after immersion.a decantation and regenerated by vaporization in vacuum
Entry IL m(IL) t T Mass Corrosion rate (0.005 MPa) at 90 °C for 0.5 h in our experiments for the regenera-
(g) (h) (°C) loss (g) (g m 2 h 1) tion of [C4(Mim)2]HSO4 to ensure that there are no other chemical
1 C2(Mim)2HSO4 1.00 15 25 0.0249 1.97 residued in the sample to affect the calculation of catalyst recovery.
2 C3(Mim)2HSO4 1.00 15 25 0.0267 2.12 The catalyst recycle results are shown in Table 6. It can be seen that
3 C4(Mim)2HSO4 1.00 15 25 0.0225 1.79 eight cycles have been successively completed and no obvious
4 H2SO4 1.00 15 25 0.1555 12.34
change is observed on the recovered catalytic activity and quantity.
a
Test conditions: n(acetic acid) = 0.25 mol:n(1-pentanol) = 0.20 mol, mass frac- The slight decrease in the yield of amyl acetate should be ascribed
tion of catalyst = 2.98%. to the slight loss of [C4(Mim)2]HSO4 due to the transferring of
 D. Zhao et al. / Chemical Engineering Journal 221 (2013) 99–104 103

Table 5
Esterification of carboxylic acids with different alcohols in imidazole dicationic ILs.a

Entry Acid Alcohol ILs Molar ratio (Acid:ROH:IL) Temperature (°C) Time (h) Yield (%)b
1 Acetic acid Ethanol C2(Mim)2HSO4 1.25:1:0.026 r.t. 2.5 93
2 Acetic acid n-Propanol C3(Mim)2HSO4 1.25:1:0.025 r.t. 2.5 90
3 Acetic acid 1-Butanol C4(Mim)2HSO4 1.25:1:0.024 r.t. 2.5 91
4 n-Butyric acid Ethanol C2(Mim)2HSO4 1:1.25:0.026 r.t. 3 87
5 n-Butyric acid n-Propanol C3(Mim)2HSO4 1:1.25:0.025 r.t. 3.5 91
6 n-Butyric acid 1-Butanol C4(Mim)2HSO4 1:1.25:0.024 r.t. 3 83
7 Benzoic acid Ethanol C2(Mim)2HSO4 1:1.2:0.052 r.t. 2.5 81
8 Benzoic acid n-Propanol C3(Mim)2HSO4 1:1.2:0.050 r.t. 3 72
9 Benzoic acid 1-Butanol C4(Mim)2HSO4 1:1.2:0.048 r.t. 3.5 79
10 Succinic acid Methanol C2(Mim)2HSO4 1:3:0.052 60 3 76
11 Succinic acid Ethanol C3(Mim)2HSO4 1:3:0.050 60 3.5 68
12 Succinic acid iso-Propyl alcohol C4(Mim)2HSO4 1:4:0.048 60 4 74
a
Reaction conditions: n(acetic acid) = 0.25 mol; n(n-Butyric acid) = 0.2 mol; n(benzoic acid) = 0.1 mol; n(succinic acid) = 0.1 mol; m(IL) = 2.0 g.
b
Yield was achieved by GC analysis.

Table 6 [C3(Mim)2]HSO4 and [C4(Mim)2]HSO4, and can be widely used in

Recycling of [C4(Mim)2]HSO4 for the esterification of acetic acid with 1-pentanol.a
Entry Weight of IL at each recycle Cumulative recovery of
step (g) IL (%)
1 1.20 100
2 1.19 99.2
3 1.16 96.7
4 1.15 95.8
5 1.13 94.2
6 1.09 90.8
7 1.05 87.5
8 1.01 84.2
a
Reaction conditions: acetic acid 1.00 mol, 1-pentanol 0.80 mol, [C4(Mim)2]HSO4
with a dosage of 2.00% (w/w) (base on the mass of acetic acid), refluxed for 2 h at
25 °C. No byproducts were found by GC.
samples during the regeneration. Inversely, for mononuclear ionic
liquids, some gave no separate phases for ester and ILs. As the
structure was not as stable as dicationic ionic liquid and might
be destroyed in the ILs-recovery procedure which resulted in
decreasing of catalytic performance [4].
4. Conclusions
We have synthesized three kinds of imidazole dicationic ionic
liquids, and their thermal stability, solubility, acidity and corrosion
were measured. The synthesis is concise and practical due to the
commercial availability of the starting materials and convenient
reaction conditions of their synthesis. In our study, the dicationic
ILs were separately used as catalyst for Fischer esterification and
high ester yields have been obtained at room temperature as the
water formed in the reaction is effectively solvated by the ionic
liquid. Often the ionic liquid and the water forms one phase and
the ester remains in a separate phase at the top. The product is
conveniently separated from the catalyst. Therefore, their easy
accessibility, clear separation of the product phase, and no leaching
of ionic liquids into the product phase show the potential of these
ionic liquids for development as industrial esterification catalysts
and mediums.
In conclusion, imidazole dicationic ionic liquids show superior
catalytic activity than reported systems, and can be reused for at
least eight cycles without any pre-treatment or significant loss of
activity. Use of ionic liquids also obviates need of volatile organic
solvents generally used for azeotropic removal of water formed
in the esterification. Therefore, ionic liquids provide environ-
ment-friendly alternative to the conventional solvents. On the
other hand, [C2(Mim)2]HSO4 shows superior thermal stability than
other related reactions or operations which have the water pro-
Yield duced and need to be removed in high temperature. The aforemen-
(%) tioned approach will be studied in future work.
86
87 Acknowledgements
85
85 The authors are grateful for the financial support of this
83
research from the National Natural Science Foundation of China
81
80 (Nos. 20576026, 21106032) and College of Chemical and Pharma-
80 ceutical Engineering (Hebei University of Science and Technology).
References
[1] D.J. Tao, X.M. Lu, J.F. Lu, K. Huang, Z. Zhou, Y.T. Wu, Chem. Eng. J. 171 (2011)
1333–1339.
[2] A.S.Y. Lee, H.C. Yang, F.Y. Su, Tetrahedron Lett. 42 (2001) 301–303.
[3] P. Mäki-Arfela, T. Salmi, M. Sundell, K. Ekman, R. Peltonen, J. Lehtonen, Appl.
Catal. A 184 (1999) 25–32.
[4] P.A. Ganeshpure, G. George, J. Das, J. Mol. Catal. A: Chem. 279 (2008) 182–186.
[5] R. Sheldon, Chem. Commun. (2001) 2399–2407.
[6] V.I. Pârvulescu, C. Hardacre, Chem. Rev. (2007) 1–46.
[7] K. Binnemans, Chem. Rev. 105 (2005) 4148–4204.
[8] J. Fraga-Dubreuil, K. Bourahla, M. Rahmouni, J.P. Bazureau, J. Hamelin, Catal.
Commun. 3 (2002) 185–190.
[9] S. Sunitha, S. Kanjilal, P.S. Reddy, R.B.N. Prasad, Tetrahedron Lett. 48 (2007)
6962–6965.
[10] F. Xu, H.Y. Chen, H.B. Zhang, X.H. Zhou, G.Z. Cheng, J. Mol. Catal. A: Chem. 307
(2009) 9–12.
[11] J. McNulty, S. Cheekoori, J.J. Nair, V. Larichev, A. Capretta, A.J. Robertson,
Tetrahedron Lett. 46 (2005) 3641–3644.
[12] D.C. Forbes, K.J. Weaver, J. Mol. Catal. A: Chem. 214 (2004) 129–132.
[13] A. Chinnappan, H. Kim, Chem. Eng. J. 187 (2012) 283–288.
[14] M. Iglesias, R. Gonzalez-Olmos, I. Cota, F. Medina, Chem. Eng. J. 162 (2010)
802–808.
[15] V. Pino, Q.Q. Baltazar, J.L. Anderson, J. Chromatogr. A 1148 (2007) 92–99.
[16] A.H. Jadhav, H. Kim, I.T. Hwang, Catal. Commun. 21 (2012) 96–103.
[17] M. Rostami, A.R. Khosropour, V. Mirkhani, I. Mohammadpoor-Baltork, M.
Moghadam, S. Tangestaninejad, C. R. Chimie 14 (2011) 869–877.
[18] A.H. Jadhav, H. Kim, Tetrahedron Lett. 53 (2012) 5338–5342.
[19] A.H. Jadhav, H. Kim, Chem. Eng. J. 200–202 (2012) 264–274.
[20] J.C. Chang, W.Y. Ho, I.W. Sun, Y.L. Tung, M.C. Tsui, T.Y. Wu, S.S. Liang,
Tetrahedron 66 (2010) 6150–6155.
[21] A. Chinnappan, H. Kim, Int. J. Hydrogen Energy 37 (2012) 8851–8859.
[22] P.C. Wang, M. Lu, Tetrahedron Lett. 52 (2011) 1452–1455.
[23] T.T. Lu, Y. Mao, K. Yao, J. Xu, M. Lu, Catal. Commun. 27 (2012) 124–128.
[24] Y. Leng, J. Wang, D.R. Zhu, L. Shen, P.P. Zhao, M.J. Zhang, Chem. Eng. J. 173
(2011) 620–626.
[25] A. Chinnappan, H. Kim, C. Baskar, I.T. Hwang, Int. J. Hydrogen Energy 37 (2012)
10240–10248.
[26] C. Zafer, K. Ocakoglu, C. Ozsoy, S. Icli, Electrochim. Acta 54 (2009) 5709–5714.
[27] T. Mandai, M. Imanari, K. Nishikawa, Chem. Phys. Lett. 543 (2012) 72–75.
[28] J.C. Chang, W.Y. Ho, I.W. Sun, Y.K. Chou, H.H. Hsieh, T.Y. Wu, Polyhedron 30
(2011) 497–507.
[29] W.M. Xiong, M.Z. Zhu, L. Deng, Y. Fu, Q.X. Guo, Energy Fuels 23 (2009) 2278–
2283.
[30] J.H. Liang, X.Q. Ren, J.T. Wang, M. Jinag, Z.J. Li, J. Fuel Chem. Technol. 38 (2010)
275–280.
[31] X.F. Liu, Y.W. Zhao, Z. Li, J. Chen, C.G. Xia, Chin. J. Chem. 28 (2010) 2003–2008.
104 D. Zhao et al. / Chemical Engineering Journal 221 (2013) 99–104

[32] Y.W. Zhao, J.X. Long, F.G. Deng, X.F. Liu, Z. Li, C.G. Xia, J.J. Peng, Catal. Commun. [35] A.J. Carmichael, K.R. Seddon, J. Phys. Org. Chem. 13 (2000) 591–593.
10 (2009) 732–736. [36] D. Behar, C. Gonzalez, P. Neta, J. Phys. Chem. A 105 (2001) 7607–7609.
[33] L.A. Jared, D. Rongfang, E. Arkady, W.A. Daniel, J. Am. Chem. Soc. 127 (2005) [37] Y.W. Zhao, Z. Li, C.G. Xia, Chin. J. Catal. 32 (2011) 440–445.
593–604. [38] R. Kore, R. Srivastava, J. Mol. Catal. A: Chem. 345 (2011) 117–126.
[34] D.H. Zaitsau, Y.U. Paulechka, G.J. Kabo, J. Phys. Chem. A 110 (2006) 11602– [39] GB/T 4334.6, Method of 5% sulfuric acid test for stainless steel, 2000, (in
11604. Chinese).