Journal of Industrial and Engineering Chemistry 20 (2014) 759766

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Journal of Industrial and Engineering Chemistry

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Liquid phase catalytic dehydration of glycerol to acrolein over

Brnsted acidic ionic liquid catalysts
Lingqin Shen, Hengbo Yin *, Aili Wang, Xiufeng Lu, Changhua Zhang,
Fen Chen, Yuting Wang, Huijuan Chen
Faculty of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, China

A R T I C L E I N F O A B S T R A C T

Article history: Liquid phase dehydration of glycerol to acrolein catalyzed by Brnsted acidic ionic liquids (BAILs) using
Received 6 March 2013 semi-batch reaction technique was investigated. For the BAILs catalysts, the acrolein yields were in
Accepted 2 June 2013 an order of [Bmim]H2PO4 > [Bmim]HSO4 > [BPy]HSO4 > [PSPy]HSO4 > [N2224]HSO4 > [PSPy]H2PO4
Available online 13 June 2013
> [BPy]H2PO4 > [N2224]H2PO4. When [Bmim]H2PO4 and [Bmim]HSO4 were used as the catalysts at
270 8C with the molar ratio of catalyst to glycerol of 1:100, the acrolein yields were 57.4% and 50.8%,
Keywords: respectively, at complete conversion of glycerol. The BAILs with [Bmim] cation and moderate acidity
Acrolein
favored the formation of acrolein in liquid phase glycerol dehydration.
Glycerol
Brnsted acidic ionic liquid
2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
Dehydration reserved.

1. Introduction enthalpy of 19.8 kJ mol1 [8], the synthesis of acrolein from

Conversion of biomass and their derivatives into high-valued
chemicals and fuels is emerging as an important aspect of modern
chemical industry [13]. The rapidly rising production of biodiesel
from vegetable oil and lipid leads to a drastic surplus of byproduct
glycerol in chemical market. Currently, the price of glycerol has
decreased from $0.43 kg1 in 2003 to $0.18/kg in 2010 for pure
glycerol, and to only $0.02/kg for crude glycerol [2]. Thus,
conversion of the surplus glycerol to valuable ne chemicals,
such as acrolein, propanediol, acrylic acid, and lactic acid, is
attracting researchers attention. The conversion processes include
catalytic oxidation, reforming, hydrogenolysis, etherication, and
dehydration [36]. One promising route is the acid-catalyzed
dehydration of glycerol to acrolein, which is an important
feedstock for the production of acrylic acid. The carbon-neutral
chemical transformation of glycerol to acrolein will make an
appreciable contribution to the present acrolein production by
partial oxidation of costly petroleum-derived propylene [7].
Glycerol molecule contains three hydroxyl groups and acrolein
can be prepared by a double-dehydration reaction between two
terminal hydroxyl groups and one middle hydroxyl group of
glycerol. Typically, when glycerol is subjected to acidic condition
and high temperature, it undergoes dehydration reaction to
produce acrolein. As an endothermic reaction with a standard
* Corresponding author. Tel.: +86 511 88787591; fax: +86 511 88791800.
E-mail address: yin@ujs.edu.cn (H. Yin).
glycerol dehydration is usually performed in the temperature
range of 260350 8C.
Brnsted acid catalysts show excellent catalytic activity in
glycerol dehydration to acrolein [4,5,812]. The acidic strength and
nature of acid sites in catalysts are of vital importance for
controlling the selective dehydration of glycerol to acrolein [4,8,9].
It was reported that high acid strength is necessary to facilitate the
double intramolecular dehydration of glycerol to acrolein although
strong acidity may be responsible for coke formation [4,5,8]. Chai
et al. [9] reported that the highest steady acrolein selectivity was
obtained by those catalysts having the strongest acid strength with
a Hammett acidity between 8.2 and 3.0. But Liu et al. [10]
arrived at the conclusion that weak acidity efciently promoted
the reaction while limiting coke formation and rapid deactivation.
Although elegant works have been done in the dehydration of
glycerol to acrolein, there still exist some drawbacks in the above-
mentioned systems, such as low yield of acrolein and high coking.
For example, when H2SO4 was used as the catalyst, the acrolein
yield was only ca. 27% [5]. Therefore, exploitation of new catalyst
system for the dehydration of glycerol to acrolein is still an
attractive research topic.
Recently, ionic liquids have gained rising attention from many
elds, such as catalysis, separation, and electrochemistry [1316].
As environmentally benign and efcient catalysts, Brnsted acidic
ionic liquids (BAILs) bearing acid anions and organic cations, such
as HSO4, H2PO4, [Bmim]+, and [BPy]+, have been used in many
typical acid-catalyzed organic reactions to replace traditional
mineral acids, such as sulfuric, phosphoric, and hydrochloric acids,

1226-086X/$ see front matter 2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jiec.2013.06.004
760 L. Shen et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 759766
because the mineral acid catalysts have problems involving high
toxicity, corrosion, and difculty in separation or recovery [17].
The acidity of BAILs can be tuned by changing their components of
anion counterparts, which is suitable for determining the acidity
effect on the glycerol dehydration reaction. Furthermore, the
acidity of BAILs also can be affected by their organic cation
counterparts. Munshi et al. [18] reported the gas phase
dehydration of glycerol to acrolein in a xed-bed reactor over
several silica-supported BAIL catalysts. The selectivity of acrolein
was in a range of 2958% and the supported triphenyl (3-
sulfopropyl) phosphonium 4-methylbenzenesulfonate gave good
activity and selectivity. Liu et al. [19] reported the gas phase
dehydration of glycerol to acrolein over Al2O3-supported
[Bmim]HSO4 catalyst. They found that the selectivity of acrolein
reached 90% at 300 8C and complete conversion of glycerol. The
structure of BAILs signicantly affected the selectivity of acrolein.
The effect of the ion counterparts of BAILs on their catalytic activity
in the glycerol dehydration reaction is still ambiguous.
The boiling points of the derivatives produced via the
dehydration of glycerol, such as acrolein (52.5 8C), acetaldehyde
(20.8 8C), acrylic acid (141 8C), and acetic acid (117.9 8C), are
quite lower than that of glycerol (290 8C). The evaporation energy
of acrolein is 558 kJ kg1 at 25 8C and atmospheric pressure [8].
Semi-batch reaction technique, with which acrolein and other
products with low boiling points are directly distilled from the
reactor during reaction process, is suitable for the dehydration of
glycerol to the valuable derivatives in the viewpoint of saving
energy and avoiding side reaction between the resultant
products.
In our present work, the catalytic performances of the BAILs
with H2PO4 and HSO4 as the anion counterparts and N-
methylimidazolium, 1-butyl-3-methylimidazolium, 1-butylpyri-
dinium, 1-(3-sulfonic acid)-propyl-pyridinium, and triethylbuty-
lammonium as the cation counterparts in the liquid phase
dehydration of glycerol were investigated using semi-batch
reaction technique. The products with low boiling points, such
as acrolein, acetaldehyde, acrylic acid, and acetic acid, formed in
the liquid phase glycerol dehydration were evaporated from the
reaction system at high reaction temperatures in a range of 250
270 8C. Acrolein was produced as the main product. The acidities of
the BAILs were evaluated by UVvis spectroscopy. The effect of the
acidity and the structure of the BAILs on their catalytic activity in
the glycerol dehydration reaction was discussed. The reaction
mechanism was also briey illustrated.
2. Experimental
2.1. Materials
Pyridine, triethylamine, butyl bromide, phosphoric acid, sulfu-
ric acid, 4-nitroaniline, glycerol, dichloromethane, and tetrahy-
drofuran were of reagent grade and were purchased from
Sinopharm Chemical Reagent Co. N-methylimidazole (98%), 1,3-
propanesultone (99%), and acrolein (98%) were purchased from
Cale, Mengde, and Xiya Chemical Reagents Co. Ltd., respectively.
All solvents and chemicals were used without further purication.
2.2. Synthesis of Brnsted acidic ionic liquids
The Brnsted acidic ionic liquids, such as N-methylimidazolium
hydrogen sulfate ([Hmim]HSO4), N-methylimidazolium dihydro-
gen phosphate ([Hmim]H2PO4), 1-butyl-3-methylimidazolium
hydrogen sulfate ([Bmim]HSO4), l-butyl-3-methylimidazolium
dihydrogen phosphate ([Bmim]H2PO4), 1-butylpyridinium hydro-
gen sulfate ([BPy]HSO4), 1-butylpyridinium dihydrogen phosphate
([BPy]H2PO4), 1-(3-sulfonic acid)-propyl-pyridinium hydrogen
sulfate ([PSPy]HSO4), 1-(3-sulfonic acid)-propyl-pyridinium dihy-
drogen phosphate ([PSPy]H2PO4), triethylbutylammonium hydro-
gen sulfate ([N2224]HSO4), and triethylbutylammonium
dihydrogen phosphate ([N2224]H2PO4), were synthesized accord-
ing to literatures [2022]. The synthesis methods were briey
introduced as follows.
[Hmim]HSO4 and [Hmim]H2PO4 were prepared by the direct
reaction of N-methylimidazole with H2SO4 and H3PO4, respec-
tively. [Bmim]HSO4, [Bmim]H2PO4, [BPy]HSO4, [BPy]H2PO4,
[N2224]HSO4, and [N2224]H2PO4 were prepared by the reactions
of the inorganic acids with [Bmim]Br, [BPy]Br, and [N2224]Br,
respectively. [Bmim]Br, [BPy]Br, and [N2224]Br were synthesized
by the reactions of butyl bromide with N-methylimidazole,
pyridine, and triethylamine, respectively. [PSPy]HSO4 and
[PSPy]H2PO4 were synthesized as follows. Firstly, 1,3-propane-
sultone reacted with pyridine and then the resultant 3-(1-
pyridinio)-1-propanesulfonate reacted with H2SO4 and H3PO4 to
form [PSPy]HSO4 and [PSPy]H2PO4, respectively. All the synthesis
reactions were under nitrogen atmosphere. The as-prepared
Brnsted acidic ionic liquids were stored in a desiccator before
use.
2.3. UVvis acidity evaluation
The Hammett method is commonly used to evaluate the acidity
of a Brnsted acid in solution, performed with a basic indicator to
trap the dissociative proton. The Brnsted acidity was evaluated
from the determination of the Hammett acidity function, using
UVvis spectroscopy [2326]. This method consists of evaluating
the protonation extent of the uncharged indicator base (named I)
in a solution, in terms of the measurable ratio [I]/[IH+]. In a given
solvent, assumed as being dissociated, the Hammett function (H0)
is dened as:
Is
H0 pKIaq log (1)
IH s
Herein, we evaluated the acidities of these ten Brnsted acidic ionic
liquids using 4-nitroanline as the indicator (Hammett content is
0.99, concentration is 10 mmol/L) in dichloromethane. After
adding equivalent mole of BAILs into the dichloromethane solution
of 4-nitroanline, the UVvis absorbance of the unprotonated 4-
nitroanline was recorded with an Analytik Jena S600 spectropho-
tometer at 349 nm.
2.4. Catalytic test
Catalytic dehydration of glycerol to acrolein was carried out in
a 250 mL of Pyrex four-necked Pyrex ask under atmospheric
pressure. An external electric heater (216 W) was used as a
heating source, which was maintained at different reaction
temperatures of 250, 260, and 270 8C, respectively, during the
catalytic test. One mole of glycerol and given amount of BAIL
were added into the Pyrex ask before reaction. The mole ratios
of BAIL to glycerol were 0.5:100, 0.75:100 and 1.0:100,
respectively. When the reaction temperature was raised to given
value, the reaction was timed and sample was taken at different
reaction times. The resultant products with low boiling points
were evaporated and condensed with a water-cooling condenser.
The boiling points of the derivatives produced via the dehydra-
tion of glycerol, such as acrolein (52.5 8C), acetaldehyde (20.8 8C),
acrylic acid (141 8C), and acetic acid (117.9 8C), are quite lower
than the reaction temperatures of 250270 8C. Therefore, the
resultant products with low boiling points can be evaporated
from the reaction system during the reaction process. After
reaction, the polymer-like residue in the ask was washed away
with brush and ethanol.
 L. Shen et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 759766 761

2.5. Product analysis Table 1

H0 values of various Brnsted acidic ionic liquids in dichloromethane.a

The composition of the condensed reaction products and the Brnsted acidic ionic liquids Absorbance [AU] [I] [%] [HI+] [%] H0
unreacted glycerol in the reactor was analyzed on a gas chromato- Blank 2.251 100 0
graph equipped with a SE-54 packed capillary column [Hmim]H2PO4 2.169 96.4 3.6 2.41
(0.25 mm  30 m) and a ame ionization detector. The temperature [N2224]H2PO4 2.067 91.8 8.2 2.04
program of column oven was: 70 8C, 2 min; heating rate, 37 8C/min; [Bmim]H2PO4 1.944 86.4 13.6 1.79
[BPy]H2PO4 1.551 68.9 31.3 1.33
250 8C, 1 min. The products and the unreacted glycerol were analyzed
[PSPy]H2PO4 1.331 59.1 40.9 1.15
by the internal standard method and tetrahydrofuran was used as the [Hmim]HSO4 1.272 56.5 43.5 1.10
internal standard. The glycerol conversion and the product yield were [N2224]HSO4 1.118 49.7 50.3 0.98
used as the parameters to evaluate the catalyst performance. They are [Bmim]HSO4 0.934 41.5 58.5 0.84
[BPy]HSO4 0.799 35.5 64.5 0.73
calculated according to the following equations.
[PSPy]HSO4 0.648 28.8 71.2 0.60

mole of glycerol fed  mole of gycerol remaining a

Conversion
mole of glycerol fed
 100%
mole of product
Yield  100%
mole of glycerol fed
3. Results and discussion
3.1. Acidities of Brnsted acidic ionic liquids
Fig. 1 shows the UVvis absorbance of 4-nitroaniline with
adding equivalent BAIL sample. The values of [I], [I]/[IH+], and H0
are listed in Table 1. The H0 values were in an order of
[Hmim]H 2PO4 > [N2224]H 2PO4 > [Bmim]H2PO4 > [BPy]H2PO4 >
[PSPy]H 2 PO 4 > [Hmim]HSO 4 > [N 2224] HSO 4 > [Bmim]HSO 4 >
[BPy]HSO4 > [PSPy]HSO4. The results showed that [PSPy]HSO4 had
the strongest Brnsted acidity while [Hmim]H2PO4 had the weakest
Brnsted acidity. The BAILs with hydrogen sulfate anion showed
higher Brnsted acidity than those with dihydrogen phosphate anion.
It can be explained as being that HSO4 had stronger Brnsted acidity
than H2PO4. The style of cation counterpart also affected the Brnsted
acidity of the BAILs. The cations on increasing the Brnsted acidity
were in an order of [PSPy]+ > [BPy]+ > [Bmim]+ > [N2224]+ > [Hmim]+.
3.2. Catalytic test
3.2.1. Conversion of glycerol
To investigate the catalytic activity of the as-prepared BAILs in
the liquid phase glycerol dehydration, the conversions of glycerol
2.5
1: blank
1 80
Concentration: 10 mmol/L; indicator: 4-nitroanline.
catalyzed by the BAILs at 250, 260, and 270 8C for 40 min are shown
(2) in Fig. 2. The mole ratio of BAIL to glycerol was 1.0:100 and the
products were directly evaporated from the reactor.
Fig. 2 shows that when the BAILs were used as the catalysts in
(3) glycerol dehydration, the conversion of glycerol increased with
increasing the reaction temperature. When the reaction tempera-
ture was raised to 270 8C, the glycerol conversions reached 100%,
90.8%, 75.3%, 48.7%, 45.6%, 45.0%, 42.6%, 40.9%, 20.9%, and 15.4% for
[PSPy]HSO4, [BPy]HSO4, [Bmim]HSO4, [N2224]HSO4, [Hmim]HSO4,
[PSPy]H2PO4, [BPy]H2PO4, [Bmim]H2PO4, [N2224]H2PO4, and
[Hmim]H2PO4, respectively. The catalytic activities of the BAILs
for glycerol dehydration were in an order of [PSPy]HSO4 > [BPy]
HSO4 > [Bmim]HSO4 > [N2224]HSO4 > [Hmim]HSO4 > [PSPy] H2PO4
>[BPy] H2PO4 > [Bmim]H2PO4 > [N2224]H2PO4 > [Hmim] H2PO4.
The relationship between the catalytic activity and the acid strength
is shown in Fig. 3. Fig. 3 clearly shows that BAILs with high acid
strength had high catalytic activity in the glycerol dehydration
reaction. The order of the catalytic activities was consistent with that
of their acid strengths.
3.2.2. Yields of products
The yields of products at complete conversion of glycerol are
listed in Table 2. From Table 2, it was found that in addition to the
conversion of glycerol to acrolein, small amounts of hydroxyace-
tone, acetaldehyde, and acetic acid with the total yield of less than
9% were produced. However, coking occurred seriously. In this
section, acrolein was taken as the desired product for evaluating
100
270 C
260 C
250 C
Glycerol conversion (mol%)

2 2: [Hmim]H2PO4
2.0 3
4 3: [N2224]H2PO4
60
4: [Bmim]H2PO4
1.5 5 5: [Bpy]H2PO4
Absorbance

6 6: [PSPy]H2PO4 40
7
8 7: [Hmim]HSO4
1.0
9 8: [N2224]HSO4
10 20
9: [Bmim]HSO4
11
0.5 10: [Bpy]HSO4
11: [PSPy]HSO4 0
1 2 3 4 5 6 7 8 9 10
0.0 BAILs
300 400 500 600 700 800
Fig. 2. Conversion of glycerol catalyzed by the Brnsted acidic ionic liquids at
Wavelength (nm) different reaction temperatures for 40 min with the mole ratio of Brnsted acidic
ionic liquid to glycerol of 1:100. 1, [PSPy]HSO4; 2, [BPy]HSO4; 3, [Bmim]HSO4; 4,
Fig. 1. Absorbance spectra of 4-nitroaniline for various Brnsted acidic ionic liquids [N2224]HSO4; 5, [Hmim]HSO4; 6, [PSPy]H2PO4; 7, [BPy]H2PO4; 8, [Bmim]H2PO4; 9,
in CH2Cl2. [N2224]H2PO4; 10, [Hmim]H2PO4.
762 L. Shen et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 759766

100 When the mole ratio of BAIL to glycerol was 1:100 and the liquid
phase glycerol dehydration reaction was carried out at the high
270 C reaction temperature of 270 8C, at complete conversion of glycerol,
80 260 C the acrolein yields were 22.7%, 57.4%, 30.7%, and 32.7% for
Glycerol conversion (mol%)

250 C [N2224]H2PO4, [Bmim]H2PO4, [BPy]H2PO4, and [PSPy]H2PO4, re-

60
40
20
0
0.4 0.6
Fig. 3. Correlation between H0 values and catalytic activities for Brnsted acidic
ionic liquids.
the performances of the BAILs in the liquid phase glycerol
dehydration reaction.
The acrolein yields in the liquid phase dehydration of glycerol
catalyzed by the BAILs are shown in Figs. 4 and 5. The catalyst
loading and reaction temperature were predicted as the inuence
factors to the acrolein formation via glycerol dehydration. The
mole ratios of BAIL to glycerol were 0.5:100, 0.75:100, and 1.0:100,
and the reaction temperatures were 250, 260, and 270 8C,
respectively.
For all the BAIL catalysts, the acrolein yields generally increased
with increasing the catalyst loading and the reaction temperature.
spectively (Fig. 4). For the BAILs containing hydrogen sulfate
anion, at complete conversion of glycerol, the acrolein yields were
33.7%, 50.8%, 49.4%, and 38.8% for [N2224]HSO4, [Bmim]HSO4,
[BPy]HSO4, and [PSPy]HSO4, respectively (Fig. 5). Surprisingly,
acrolein was not collected at complete conversion of glycerol
when [Hmim]HSO4 and [Hmim]H2PO4 were used as the catalysts
at 270 8C. For the BAILs catalysts, the acrolein yields were in
an order of [Bmim]H2PO4 > [Bmim]HSO4 > [BPy]HSO4 > [PSPy]
HSO4 > [N2224]HSO4 > [PSPy]H2PO4 > [BPy]H2PO4 >[N2224] H2PO4.
The order of the acrolein yields for the BAIL catalysts was
inconsistent with that of their acidities.
0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6
H0 values of BAILs
When [PSPy]HSO4 with the highest Brnsted acidity was used
as the catalyst, the acrolein yield was not the highest. Although
[PSPy]HSO4 with both hydrogen sulfate and hydrogen sulfonate
anions could supply more acid sites for the dehydration reaction,
the acid sites not only catalyzed the glycerol dehydration to
acrolein but also catalyzed the polymerization of resultant acrolein
and the intermolecular condensation of glycerol, lowering acrolein
yield. However, when [N2224]H2PO4 with low acidity was used as
the catalyst, low acrolein yield was obtained. It can be explained as
that low acidity cannot effectively activate glycerol, which has a
very high activation barrier of 296.6 kJ mol1 for the dehydration
of the middle hydroxyl group [27].
The BAILs with hydrogen sulfate anions generally exhibited
higher catalytic activity for the glycerol dehydration to acrolein
than those with dihydrogen phosphate anions because hydrogen
sulfate anions had higher Brnsted acidity than dihydrogen
phosphate anions. On the other hand, the BAILs also catalyzed

60
[N2224]H2PO4 60
[Bmim]H2PO4
1.0:100
30 270 C 0.75:100 30 1.0:100
Acrolein yield (mol%)

270 C 0.75:100
Acrolein yield (mol%)

0.5:100
60 0.5:100
60
1.0:100
30 260 C 0.75:100
30 1.0:100
0.5:100 260 C 0.75:100
60 0.5:100
60
1.0:100
250 C 0.75:100
30 0.5:100 30 1.0:100
250 C 0.75:100
0 0.5:100
0 20 40 60 80 100 120 140 160 180 200 220 240 0
0 20 40 60 80 100 120 140 160 180 200 220 240
Reaction time (min)
Reaction time (min)
60
60
[BPy]H2PO4
[PSPy]H2PO4
30 1.0:100
30 1.0:100
270 C 0.75:100
Acrolein yield (mol%)

270 C 0.75:100
Acrolein yield (mol%)

0.5:100
60 0.5:100
60

30 1.0:100
30 1.0:100
0.75:100
260 C 260 C 0.75:100
0.5:100
60 0.5:100
60
1.0:100
30 1.0:100
30
0.75:100 0.75:100
250 C 0.5:100 250 C 0.5:100
0
0 20 40 60 80 100 120 140 160 180 200 220 240 0
0 20 40 60 80 100 120 140 160 180 200 220 240
Reaction time (min)
Reaction time (min)

Fig. 4. Yield of acrolein in the liquid phase glycerol dehydration catalyzed by the Brnsted acidic ionic liquids with dihydrogen phosphate anion.
 L. Shen et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 759766 763

Table 2
Results of glycerol dehydration catalyzed by Brnsted acidic ionic liquids.a

Catalysts BAIL:GLY (mol/mol) T (8C) R.T. (min) Yields of products (%)

AC HA AD AA PLRb

[Hmim]H2PO4 0.5:100 250 280 0 2.3 1.6 2.4 93.7

0.75:100 280 0 2.4 1.9 2.7 93.0
1.0:100 240 0 2.5 2.1 3.5 91.9
0.5:100 260 260 0 2.3 2.0 3.5 92.2
0.75:100 260 0 2.5 2.1 3.7 91.7
1.0:100 240 0 2.6 2.2 3.8 91.4
0.5:100 270 240 0 2.5 2.0 3.8 91.7
0.75:100 240 0 2.6 2.2 3.9 91.3
1.0:100 220 0 2.7 2.3 4.0 91.0

[N2224]H2PO4 0.5:100 250 240 15.6 2.1 1.8 2.7 77.8

0.75:100 240 16.6 2.5 2.0 2.9 76.0
1.0:100 220 19.4 2.7 2.3 3.4 72.2
0.5:100 260 220 16.1 2.3 2.0 3.0 76.6
0.75:100 220 18.0 2.7 2.2 3.1 74.0
1.0:100 200 21.4 2.8 2.4 3.5 69.9
0.5:100 270 200 17.2 2.6 2.3 3.4 74.5
0.75:100 200 20.4 2.8 2.4 3.5 70.9
1.0:100 180 22.7 2.9 2.5 3.6 68.3

[Bmim]H2PO4 0.5:100 250 220 40.5 2.3 1.8 2.4 53.0

0.75:100 220 43.0 2.7 2.0 2.6 49.7
1.0:100 200 44.2 2.9 2.2 2.9 47.8
0.5:100 260 200 43.7 2.8 2.1 2.6 48.8
0.75:100 200 47.0 2.9 2.2 2.7 45.2
1.0:100 180 54.2 3.1 2.3 3.0 37.4
0.5:100 270 180 51.4 2.9 2.5 3.1 40.1
0.75:100 180 53.4 3.1 2.5 3.2 37.8
1.0:100 160 57.4 3.2 2.6 3.2 33.6

[BPy]H2PO4 0.5:100 250 200 20.3 2.2 1.7 2.3 73.5

0.75:100 200 21.6 2.8 2.0 2.5 71.1
1.0:100 180 25.4 3.1 2.4 2.7 66.4
0.5:100 260 180 21.2 2.9 2.2 2.5 71.2
0.75:100 180 23.5 3.1 2.4 2.8 68.2
1.0:100 160 28.4 3.2 2.5 2.9 63.0
0.5:100 270 160 22.2 3.0 2.6 2.8 69.4
0.75:100 160 24.2 3.2 2.6 2.9 67.1
1.0:100 140 30.7 3.3 2.7 3.0 60.3

[PSPy]H2PO4 0.5:100 250 180 22.3 2.7 2.3 1.4 71.3

0.75:100 180 24.6 3.0 2.5 1.5 68.4
1.0:100 160 27.7 3.2 2.6 1.8 64.7
0.5:100 260 160 23.7 2.9 2.5 1.7 69.2
0.75:100 160 26.5 3.2 2.6 1.8 65.9
1.0:100 140 29.1 3.2 2.7 1.9 63.0
0.5:100 270 140 24.9 3.1 2.6 2.3 67.1
0.75:100 140 27.8 3.4 2.7 2.5 63.6
1.0:100 120 32.7 3.4 2.8 2.7 58.4

[Hmim]HSO4 0.5:100 250 180 0 3.0 2.6 1.7 92.7

0.75:100 180 0 3.1 2.4 2.0 92.5
1.0:100 160 0 3.3 2.7 2.3 91.7
0.5:100 260 160 0 3.0 2.6 2.0 92.4
0.75:100 160 0 3.2 2.6 2.1 92.1
1.0:100 140 0 3.4 2.8 2.5 91.3
0.5:100 270 120 0 3.2 2.7 2.4 91.7
0.75:100 120 0 3.4 2.8 2.5 91.3
1.0:100 100 0 3.5 2.9 2.6 91.0

[N2224]HSO4 0.5:100 250 160 23.3 2.5 2.0 1.4 70.8

0.75:100 160 26.6 3.0 2.6 1.9 65.9
1.0:100 140 29.9 3.2 2.9 2.1 61.9
0.5:100 260 140 24.6 3.0 2.5 2.1 67.8
0.75:100 140 27.4 3.2 2.8 2.3 64.3
1.0:100 120 31.0 3.4 3.0 2.3 60.3
0.5:100 270 120 25.9 3.3 2.9 2.3 65.6
0.75:100 100 28.3 3.4 3.0 2.4 62.9
1.0:100 100 33.7 3.5 3.1 2.4 57.3

[Bmim]HSO4 0.5:100 250 140 34.8 2.8 2.4 1.4 58.6

0.75:100 140 37.2 3.1 2.5 1.7 55.5
1.0:100 120 38.4 3.4 2.9 1.9 53.4
0.5:100 260 120 36.7 3.1 2.5 1.7 56.0
0.75:100 120 41.6 3.3 2.8 1.9 50.4
1.0:100 100 42.3 3.6 3.0 2.0 49.1
0.5:100 270 100 39.1 3.4 2.8 2.0 52.7
764 L. Shen et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 759766

Table 2 (Continued )

Catalysts BAIL:GLY (mol/mol) T (8C) R.T. (min) Yields of products (%)

AC HA AD AA PLRb

0.75:100 100 42.3 3.5 3.0 2.2 49.0

1.0:100 80 50.8 3.7 3.1 2.2 40.2

[BPy]HSO4 0.5:100 250 120 33.4 2.9 2.2 0.8 60.7

0.75:100 120 36.3 3.1 2.7 1.4 56.5
1.0:100 100 37.4 3.3 3.0 1.9 54.4
0.5:100 260 100 35.8 3.1 2.3 1.1 57.7
0.75:100 100 40.6 3.4 2.8 1.6 51.6
1.0:100 80 41.6 3.6 3.2 2.0 49.6
0.5:100 270 80 36.8 3.4 2.8 1.5 55.5
0.75:100 80 39.2 3.6 3.1 1.9 52.2
1.0:100 80 49.4 3.7 3.3 2.0 41.6

[PSPy]HSO4 0.5:100 250 80 37.2 3.4 3.0 0.6 55.8

0.75:100 80 39.1 3.7 3.2 0.9 53.1
1.0:100 80 41.1 3.8 3.3 1.0 50.8
0.5:100 260 60 36.6 3.5 3.2 0.8 55.9
0.75:100 60 38.5 3.9 3.3 0.9 53.4
1.0:100 60 40.2 3.9 3.6 1.1 51.2
0.5:100 270 40 36.3 3.7 3.3 0.8 55.9
0.75:100 40 37.2 4.0 3.6 1.0 54.2
1.0:100 40 38.8 4.1 3.7 1.2 52.2
a
T, reaction temperature; R.T., reaction time; GLY, glycerol; AC, acrolein; HA, hydroxyacetone; AD, acetaldehyde; AA, acetic acid; PLR, polymer-like residue. Glycerol was
completely converted under present conditions.
b
Yield of PLR = 1  SYieldi, i = AC, HA, AD, and AA.

the polymerization of resultant acrolein and the intermolecular reasonable to conclude that organic counterparts also had effect
condensation of glycerol, lowering acrolein yield. on the formation of acrolein.
It is interesting to nd that high acrolein yields were obtained
when [Bmim]HSO4 and [Bmim]H2PO4 were used as the catalysts 3.2.3. Reaction routes
and no acrolein was detected when [Hmim]HSO4 and When the BAILs were used as the catalysts in the dehydration of
[Hmim]H2PO4 were used as the catalysts. Therefore, it is glycerol, acrolein was produced as the main product. Small

60 60
[N2224]HSO4 [Bmim]HSO4

30 1.0:100 30 1.0:100
270 C 0.75:100 270 C 0.75:100
Acrolein yield (mol%)

Acrolein yield (mol%)

0.5:100 0.5:100
60
0 60
0

1.0:100 1.0:100
30 30
260 C 0.75:100
260 C 0.75:100 0.5:100
0.5:100
60 60

1.0:100
30 30 1.0:100
0.75:100 250 C 0.75:100
250 C 0.5:100
0.5:100
0 0
0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160
Reaction time (min) Reaction time (min)
60 60
[BPy]HSO4 [PSPy]HSO4

30 1.0:100 30 1.0:100
270 C 0.75:100 270 C 0.75:100
Acrolein yield (mol%)

Acrolein yield (mol%)

0.5:100 0.5:100
60 60
0

30 1.0:100 30 1.0:100
260 C 0.75:100 260 C 0.75:100
0.5:100 0.5:100
60
0 60

1.0:100 1.0:100
30 30
250 C 0.75:100 250 C 0.75:100
0.5:100 0.5:100
0 0
0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160
Reaction time (min) Reaction time (min)

Fig. 5. Yield of acrolein in the liquid phase glycerol dehydration catalyzed by the Brnsted acidic ionic liquids with hydrogen sulfate anion.
 L. Shen et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 759766
Scheme 1. Reaction routes of glycerol dehydration catalyzed by Brnsted acidic ionic liquids.
amounts of acetaldehyde, acetic acid, and acrylic acid were
detected. At the same time, polymer-like residue was also formed
in the reactor, indicating that the BAILs also catalyzed the
polymerization of resultant acrolein and the intermolecular
reaction among glycerol molecules. The reaction mechanism in
the glycerol dehydration catalyzed by different BAILs was
suggested as Scheme 1.
For the dehydration of glycerol to acrolein catalyzed by BAILs, it is
suggested that glycerol starts with the protonation at the middle
hydroxyl group by a proton from Brnsted site and then the resultant
protonated glycerol is transformed to enol intermediate by release of
a proton and followed by a keto-enol rearrangement to give 3-
hydroxypropionaldehyde. Acrolein was formed by the dehydration
of 3-hydroxypropionaldehyde [812]. Under the present experi-
mental conditions, enol intermediate and 3-hydroxypropionalde-
hyde were not detected, indicating that the reactions of keto-enol
rearrangement and 3-hydroxypropionaldehyde dehydration to
acrolein were very quick. At the same time, hydroxyacetone was
formed by the keto-enol rearrangement of enol. With the reaction
going on, the resultant acrolein can be oxidized to acrylic acid [28].
The spent Brnsted acid sites can be re-protonated by the
aforementioned released protons [4,8,2932].
Acetaldehyde and acetic acid were detected as byproducts with
low yields in the dehydration of glycerol catalyzed by BAILs using
semi-batch reaction technique. The reaction mechanism was
suggested as follows. When one terminal hydroxyl group of
glycerol is attacked by the proton of BAIL, it can be cracked to form
acetaldehyde, which produces the acetic acid with further
oxidation. Besides, acetaldehyde can be produced through the
cracking of 3-hydroxypropionaldehyde [5,27].
4. Conclusions
Liquid phase dehydration of glycerol to acrolein was catalyzed
by BAILs using semi-batch reaction technique at 250270 8C with
765
the mole ratios of BAIL to glycerol of 0.5: 100, 0.75: 100, and 1.0:
100, respectively. The acidities of the BAILs were in an order of
[Hmim]H2PO4 < [N2224]H2PO4 < [Bmim]H2PO4 < [BPy]H2PO4 <
[PSPy]H2PO4 < [Hmim]HSO4 < [N2224]HSO4 < [Bmim]HSO4 <
[BPy]HSO4 < [PSPy]HSO4. For the BAIL catalysts, the acrolein
yields were in an order of [Bmim]H2PO4 > [Bmim]HSO4 >
[BPy]HSO4 > [PSPy]HSO4 > [N2224]HSO4 > [PSPy]H2PO4 > [BPy]-
[BPy]H2PO4 > [N2224]H2PO4, which was inconsistent with that
of their acidities. When [Hmim]HSO4 and [Hmim]H2PO4 were
used as the catalysts, no acrolein was collected under the
present experimental conditions. The cation and anion counter-
parts synergistically catalyzed the glycerol dehydration to
acrolein. When [Bmim]H2PO4 was used as the catalyst with
the mole ratio of [Bmim]H2PO4 to glycerol of 1:100, the
maximum acrolein yield of 57.4% was reached at 270 8C. While
[Bmim]HSO4 was used as the catalyst, the acrolein yield reached
50.8%. When the BAILs with [Bmim] cation and moderate acidity
were used as the catalysts, high acrolein yield was obtained in
the liquid phase glycerol dehydration. In the viewpoint of the
high acrolein yield, the low catalyst consumption, and the
energy saving, glycerol dehydration to acrolein catalyzed by
Brnsted acidic ionic liquids using semi-batch reaction tech-
nique is probably a potential alternative to the other processes.
Acknowledgment
This work was nancially supported by research funds from
Jiangsu Province Education Bureau (CXZZ12-0683).
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