Chemical Engineering Journal 297 (2016) 128–138

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Chemical Engineering Journal

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Production of glycerol carbonate from glycerol with aid of ionic liquid

as catalyst
Zati Ismah Ishak a,b, Nor Asrina Sairi a,b,⇑, Yatimah Alias a,b, Mohamed Kheireddine Taieb Aroua c,d,
Rozita Yusoff c,d
a
Department of Chemistry, Faculty of Science, University of Malaya, 50603 Kuala Lumpur, Malaysia
b
University of Malaya Centre for Ionic Liquids, Department of Chemistry, Faculty of Science, University of Malaya, 50603 Kuala Lumpur, Malaysia
c
Department of Chemical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia
d
Centre for Separation Science & Technology, Department of Chemical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia

h i g h l i g h t s

Green production of glycerol 1,2-carbonate with an environmentally friendly catalyst was proposed.

Screening and optimisation of the catalysts were comprehensively performed.

The basic ionic liquid (emim[Ac]) showed best catalytic activity and recyclability.

Detail understanding on the glycerol-catalysts and glycerol 1,2-carbonate-catalysts interactions has been well explored.

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

Article history: The rapid growth of biodiesel industry has led to a large surplus of its major unintentional byproduct par-
Received 3 November 2015 ticularly glycerol. Thus, finding a new application is necessary to convert glycerol to value added prod-
Received in revised form 13 March 2016 ucts. In this study, glycerol has been subjected to a transesterification reaction to synthesis glycerol
Accepted 19 March 2016
carbonate (GC) over several selected ammonium and imidazolium-based ionic liquids (ILs) as catalysts.
Available online 25 March 2016
It is believed that the variation of catalytic performance between ILs was due to the anion strength of
ILs. The glycerol conversion, yield and selectivity of GC were followed the anion order of [Ac] > [Dca] >
Keywords:
[Fmt] > [DMP] > [NO3] > [Cl] > [BF4]. Effects of reaction temperature, time, diethyl carbonate (DEC)/glyc-
Ionic liquids
Glycerol
erol molar ratio and catalyst loading on glycerol conversion and GC yield have been analysed. The IL,
Transesterification 1-ethyl-3-methylimidazolium acetate (emim[Ac]) shows best performance under solvent-free with con-
Glycerol carbonate version of glycerol and GC yield reached highest at 93.50% and 88.70%, respectively under reaction tem-
Catalysis perature of 120 °C reaction time of 2 h, DEC/glycerol molar ratio of 2 and catalyst loading of 0.5 mol%.
Also, this emim[Ac] can be reused as catalyst at least three times without any significant reduction in
conversion, yield and selectivity. Reaction mechanism of the transesterification reaction catalysed by
emim[Ac] has been proposed in this study.
Ó 2016 Elsevier B.V. All rights reserved.

1. Introduction products reported in the last 5 years is glycerol carbonate (GC).

Formation of glycerol (glycerine or 1,2,3-propanetriol) as a by-
product during biodiesel production has led to a major concern.
The surplus of glycerol has dropped its price [1] and exerts a great
impact on the refined glycerol market. Thus, it becomes a research
focus to find an innovative way to revalorize glycerol and trans-
form to value-added chemicals [2]. One of the most celebrated
⇑ Corresponding author at: Chemistry Department, Faculty of Science, University
of Malaya, 50603 Kuala Lumpur, Malaysia. Tel.: +60 3 79672147.
E-mail address: asrina@um.edu.my (N.A. Sairi).
GC has many applications in various industrial sectors. GC is useful
not only as a polar high boiling solvent or intermediate in organic
synthesis such as glycidol [3], it also can be used as green substitu-
tion for petro-derivatives compounds (ethylene carbonate or
propylene carbonate) [4]. In polymer and plastics industry, GC is
use as an intermediate for the synthesis of polycarbonates, polye-
sters, polyamides and hyper branched polyethers [5,6]. In addition,
GC also can be used as electrolytes and solvents in lithium-ion bat-
teries, by planting activating agent in agricultural industry and as
components for gas separation membranes [7].

http://dx.doi.org/10.1016/j.cej.2016.03.104
1385-8947/Ó 2016 Elsevier B.V. All rights reserved.
 Z.I. Ishak et al. / Chemical Engineering Journal 297 (2016) 128–138
GC having low toxicity and good biodegradability that can be
synthesized from glycerol as alcohol OH-source with various car-
boxylation sources, including carbon dioxide (CO2), urea, and dia-
lkyl carbonates [8,9]. The simple and effective of direct
carbonylation of glycerol with CO2 with tin complexes as catalyst
however facing major limitations particularly due to unfavourable
thermodynamic equilibrium and low yields (less than 8% of pro-
duct). The use of phosgene as the carbonylation sources somehow
has imparted a negative drawback in which highly toxic and corro-
sive nature of phosgene has turn the process become hazardous.
Alternatively, direct routes such as transesterification reaction
with alkylene or dialkyl carbonate to synthesis GC have been
explored. Transesterification reaction using alkylene carbonate
requires applying reduced pressure in order to separate by-
product from reaction medium [10]. Transesterification of glycerol
with dialkyl carbonate is the most attractive process for GC synthe-
sis since the process starts with non-toxic materials under mild
operation conditions and obtains a good GC yield [11–13]. More-
over, the non-toxicity, biodegradability and cleaner production
process of dialkyl carbonate make it as a green reagent to be used
as carbonylating agent [14]. This reaction is favoured using an
alkaline base catalyst compare to acidic catalysts as their catalytic
activity are extremely low [8].
Recently, researchers have shown an increased interest in
employing homogeneous [15–17] (inorganic metal salts, quater-
nary ammonium salts and ionic liquids (ILs)) as well as heteroge-
neous [18–21] (metal oxides, mixed metal oxides, hydrotalcites,
supported hydroxyapatite and Sn-complexes) catalysts for the
transesterification reaction. In attempt to find an alternative
energy source, Teng et al. [22] has successfully performed
microwave-assisted transesterification using CaO as catalyst. It is
noted that, 93.4% GC yield was obtained in five minutes reaction
time. However, despite its high activity and easily separate, hetero-
geneous catalyst suffers from several major drawbacks including
deactivation of catalyst in presence of water, leaching of catalyst
active sites and energy intensive process due to calcination step
needed. On the other hand, homogeneous catalysts possess highly
catalytic activity and enhanced reaction rate which is preferable to
be used as catalysts in view of the demerit of heterogeneous
catalysts.
As well established today, ILs present many advantages in many
reaction using as catalysts or due to the unique properties [23]. The
adjustable cation–anion pairing opens up the possibility of tailor-
ing to particular physical and chemical properties. This will also
allow the preparation of acidic/basic ILs. Moreover, dual function
of ILs often results in increase in rate and/or reactivity, compared
to some of the catalyst that need additional of solvent to enhance
the transesterification reaction [24,25]. In view of that, many stud-
ies using homogenous basic ILs have been reported as they showed
a good catalytic activity for GC formation [17,26,27]. Cation and
anion of ILs can cooperatively activate electrophiles and nucle-
ophiles to catalyse various reactions which involve carbonyl acti-
vation [28]. It has been reported that hydrogen bond basicity is
controlled by the anion, while the hydrogen bond donation is dom-
inated by the hydrogen bond basicity of the anions with a smaller
contribution from the hydrogen bond acidity of the cation. Chang-
ing to more basic anions leads to a dramatic drop in the acidity of
cation. Thus, anions have decisive influence on the catalytic perfor-
mance in the transesterification of glycerol. Apart from catalyst
activity, it is also expected that reaction parameters such as reac-
tion temperature, reaction time, molar ratio of reactants and sol-
vent, as well as impurity particularly water content and
methanol in the reaction mixture have significantly affected the
glycerol conversion and the GC yield [29].
Therefore, the production of GC from glycerol is an attractive
reaction that utilises two inexpensive and readily available raw
129
materials in a chemical cycle. Thus, the present work attempts to
explore on an alternative route of transesterification reaction of
glycerol with DEC over ammonium and imidazolium-based ILs as
catalysts for GC production. Selection of ILs were based on their
strength of anion which given by its hydrogen bond basicity
reported by parameter b. The effect of the different in b value of
anion on the glycerol and GC–IL interaction was examined in this
study. The pertinent factors affecting the performance of GC syn-
thesis were studied individually. A time online analysis study with
ATR-FTIR and 13C NMR conducted in this study help to further
understand the mechanism and theory of the reaction. Signifi-
cantly, the synthesis pathways of GC and the possibilities of by-
products catalysed by IL were addressed in this study. Scheme 1
shows the schematic reaction of transesterification of glycerol to
GC.
2. Experimental
2.1. Chemicals
Glycerol (99.5%), glycerol carbonate (GC) (99.5%), diethyl
carbonate (DEC) (99.5%) and glycidol (CAS: 556-52-5) were
supplied by Aldrich and used without any further purification.
Ionic liquids (ILs) namely methylammonium nitrate (MA[NO3]),
ethylammonium nitrate (EA[NO3]), 2-hydrozyethylammonium
formate (HEA[Fmt]) were purchased from IoLiTec Inc.
(USA). 1-ethyl-3-methylimidazolium dimethyl phosphate (emim
[DMP]), 1-butyl-3-methylimidazolium chloride (bmim[Cl]),
1-butyl-3-methylimidazolium tetrafluoroborate (bmim[BF4]),
1-butyl-3-methylimidazolium dicyanamide (bmim[Dca]) and 1-
ethyl-3-methylimidazolium acetate (emim[Ac]) were obtained
from Merck. All ILs were purchased having 99% of purity. Solvents;
chloroform (AR grade), ethyl acetate (AR grade), methanol (AR
grade) and methanol (GC grade-99.9%) were purchased from Fisher
Scientific. Deuterated methanol-d4 (99.8%) (Aldrich) was used as
solvent in NMR analysis.
2.2. Synthesis of glycerol carbonate
The reaction was carried out using a 150 mL round bottom
three-neck glass flask fitted with magnetic stirrer, reflux condenser
and sampling device. A constant heating energy was supplied to
the glass flask in oil bath with nitrogen gas flow at atmospheric
pressure. In a typical experiment, 27.4 mmol of glycerol was
heated first, followed with the addition of an excess of DEC into
the flask and heated to the desired temperature. Then, the selected
IL (0.1–10 mol% with respect to limiting substrate) was then added
to the biphasic system as catalyst to start the reaction. The trans-
esterification progress was monitored by analytical thin layer chro-
matography (TLC) with optimised developing solvent system of
ethyl acetate/methanol (4.8:0.2). Alternatively, the formation of a
sole phase could be taken as the end point of the reaction.
To recover IL upon completion of the reaction (as determined by
TLC and area of glycerol from GC-FID), chloroform (3  10 mL) was
added to the reaction mixture in order to recover IL. Later, the
H
H O H
O
O O
O
O 2CH3CH2OH
O
OH
O O
glycerol 1,2-carbonate
Scheme 1. Transesterification reaction of glycerol to glycerol 1,2-carbonate.
130 Z.I. Ishak et al. / Chemical Engineering Journal 297 (2016) 128–138

reaction was repeated again following the mentioned procedure
using the recovered IL. The recovered IL was analysed with 13C
NMR to confirm its purity, however any traces of remaining glyc-
erol was neglected.
2.3. Product analysis
The samples were withdrawn at interval 30 min and analysed
using gas chromatograph equipped with a flame ionisation detec-
tor (FID) (Agilent Technologies, model 7890A) and a capillary col-
umn FFAP (30 m long, 0.25 mm i.d.). The temperature of the
column was programmed to has a 5-min initial hold at 35 °C, a
10 °C/min ramp from 35 °C to 60 °C and 1-min hold at 60 °C, a
15 °C/min ramp from 60 °C to 230 °C and a 10-min hold at
230 °C. A good peak separation was achieved under the conditions
for all components. The concentrations of the glycerol and GC were
obtained directly from their respective peak areas in the gas chro-
matograph, as compared to peak’s retention time of glycerol and
GC standard. 1-butanol is used as an internal standard. The yields
of GC and conversions of glycerol were determined using Eqs. (1)
and (2), respectively:
Glycerolinitial þ Glycerolresidual
Conversion; C ¼  100%
Glycerolinitial
GC
Yield; Y ¼  100%
Glycerolinitial
Activity of ILs towards the transesterification reaction was
based on conversion of glycerol as limiting substrate measured
under standard conditions of reaction. The transesterification pro-
gress was monitored by TLC. The interactions of IL with glycerol or
GC were investigated using a Attenuated Total Reflectance-Fourier
Transform Infrared (ATR-FTIR) spectrometer (Perkin Elmer) in the
range of 400–4000 cm1 with 4 cm1 resolution of 40 scans. Anal-
ysis of 1H/13C NMR was conducted using Fourier Transform-
Nuclear Magnetic Resonance (FT-NMR) AVANCE III 400 MHz
(AVN 400).
3.1. Catalyst screening
The results obtained are presented in Table 2. It was found that,
reaction of glycerol and DEC does proceed slowly even in the
absence of a catalyst. However, the yield of GC did not exceed
10%. All ILs screened were active (moderate to high glycerol con-
version) for the reaction except for MA[NO3], EA[NO3], bmim
[BF4] having non-coordinating anion and halide based IL (bmim
[Cl]) giving less than 10% conversion of glycerol and only traces
amount of GC was formed in the reaction. This finding is in agree-
ment with the result reported by Yi et al. [27] and Zhou et al. [36].
[Dca] anion with b value 0.596 has gave 45% glycerol conversion
and GC yield, respectively. Larger size of [DMP] anion with low
hydrogen bond formation ability (b = 1.00) has reduced the cata-
lyst activity towards the transesterification reaction of glycerol
[34].
From the results, it was observed that the activity of the emim
[Ac] was good (93.50% conversion of glycerol) and also the GC yield
was 88.70% at 2 h with a molar ratio DEC/glycerol of 2 as compared
to [Cl] anion ionic liquid. [Ac] anion is conjugate base of acetic acid
(CH3COOH) which is weaker acid than hydrochloric acid (HCl) of
corresponding [Cl] anion hence ILs with [Ac] anion displaying
higher b value (b = 1.201) and higher activity [37]. Thus it is pro-
ð1Þ posed that b value solely governed by nature of the anions [38].
An increased of [Ac] anion basicity makes it more efficient in
abstracting primary hydroxyl proton of glycerol than [Cl] anion
ð2Þ [39]. Bmim[Cl] give less than 10% glycerol conversion and GC yield,
due to incapability of [Cl] anion to form hydrogen bonding with
hydroxyl group of glycerol. Hydrogen of hydroxyl group of glycerol
is expected to likely form bond to an electronegative O or N atom
rather than a Cl atom [40].
It is interesting to note that low glycerol conversion and GC
yield of [Fmt] anion was expected due to the absence of electron
donor CH3 group which decrease the ability of the hydrogen bond
formation [41]. This has led to lower b value (b = 0.73) as compared
to [Ac] anion (b = 1.201). Hence, emim[Ac] would be a rational
choice for further investigations with the aim of improving the

3. Results and discussion Table 2

Catalyst screening of selected ILs as catalyst for transesterification of glycerol.
Reaction conditions: temperature = 120 °C, Time = 2 h, molar ratio of DEC/glycerol = 2
In determining the potential catalyst, a series of imidazolium
and catalyst loading 0.5 mol% based on limiting reactant.
and ammonium-based ILs were selected with respect to the hydro-
gen bond basicity (b value) quantified by Kamlet and Taft parame- No. Ionic liquid Glycerol conversion (%) GC yield (%)
ter. Kamlet–Taft model is used to elucidate the solvation 1 Blank 5.00 5.00
parameters; which involves term a (hydrogen bond donor/H- 2 MA[NO3] <10.00 <10.00
3 EA[NO3] <10.00 <10.00
bond acidity), b (hydrogen bond acceptor/H-bond basicity) and
4 bmim[Cl] <10.00 <10.00
p⁄ (polarizability or dipolarity). These a, b, p⁄ values can be calcu- 5 bmim[BF4] <5.00 <5.00
lated by UV–VIS spectroscopy in presence of solvatochromic dyes 6 HEA[Fmt] 24.08 24.00
such as, N,N-diethyl-4-nitroaniline and 4-nitroaniline [30,31]. 7 emim[DMP] 22.20 22.00
Table 1 shows the list of ILs used as catalysts together with the 8 bmim[Dca] 45.00 45.00
9 emim[Ac] 93.50 88.70
reported b value.

Table 1
Ionic liquids used in this study and their reported hydrogen bond basicity (b value) of anion.

No. Ionic liquid (IL) Abbreviation b value

1 Methylammonium nitrate MA[NO3] 0.46 [32]
2 Ethylammonium nitrate EA[NO3] 0.46 [32]
3 2-Hydrozyethylammonium formate HEA[Fmt] 0.73 [33]
4 1-Ethyl-3-methylimidazolium dimethyl phosphate emim[DMP] 1.00 [34]
5 1-Butyl-3-methylimidazolium dicyanamide bmim[Dca] 0.596 [35]
6 1-Butyl-3-methylimidazolium chloride bmim[Cl] 0.95 [35]
7 1-Butyl-3-methylimidazolium tetrafluoroborate bmim[BF4] 0.55 [35]
8 1-Ethyl-3-methylimidazolium acetate emim[Ac] 1.201 [35]
 Z.I. Ishak et al. / Chemical Engineering Journal 297 (2016) 128–138
GC yield and selectivity. The effect of reaction temperature, time of
reaction, molar ratio of DEC/glycerol and catalyst loading was eval-
uated in detail.
3.2. Optimisation of reaction conditions
3.2.1. Effect of temperature
In general, increasing the temperature of the transesterification
reaction should lead to a dramatic effect towards the conversion of
glycerol. This is mainly due to that higher temperature can
improve the miscibility between hydrophobic DEC and hydrophilic
glycerol. According to Arrhenius equation, an increase in reaction
temperature can increase the collision rate between the reactants
and thus leading to a higher reaction rate and product yield [42].
Nevertheless, the optimum reaction temperature in transesterifi-
cation is closely dependent on the heat sensitive carbonates and
catalysts used. Hence, the effect of temperature on the conversion
of glycerol to GC catalysed by emim[Ac] was investigated at vari-
ous temperature ranging from 110 to 130 °C. The other parameters,
DEC/glycerol molar ratio at 2 and 0.5 mol% catalyst loading are
kept constant. As depicted in Fig. 1, less than 10% of the glycerol
conversion at room temperature. A rapid increase of glycerol con-
version and GC yield was observed when temperature increase
from 110 to 120 °C, possibly due to the increase of collision energy
when temperature is increased. Furthermore, at 110 °C, the reac-
tion solution still remains 2 phases after 2 h of reaction time, indi-
cating that the reaction was still not completed. About 93.50%
conversion of glycerol and 88.70% GC yield was successfully syn-
thesized at reaction temperature of 120 °C. Further increase of
reaction temperature at 130 °C give 95.87% glycerol conversion
and GC yield dramatically dropped to 64.17%. Moreover, a rapid
darkening of the reaction mixture was obtained as temperature
of the reaction increase (more than 120 °C). The decreased of GC
yield at 130 °C probably due to the conversion of GC resulting from
increasing reactivity of its hydroxyl moiety with temperature. At
high temperature its acidic primary hydroxyl pendant group could
react with the anion resulting in an hydroxide ion which could ini-
tiate the GC ring opening polymerization leading to a polymer
[10,15,17]. Rokicki et al. [43] also have described the base-
catalysed ring opening polymerization of GC at 170 °C which pro-
ceeds with CO2 evolution and yields hyper-branched aliphatic
polyethers.
As the reaction temperature plays a very crucial effect towards
glycerol conversion and GC yield, optimum reaction temperature
for the transesterification was selected at 120 °C and was then
used for checking the influence of the remaining reaction
parameters.
100
Yield of GC Conversion of glycerol
80
Percentage, %
60
40
20
0 [Ac] = 0.5 mol% based on limiting reactant.
Room 110 115 120
temperature
Temperature, C
Fig. 1. Effect of reaction temperature on the transesterification of glycerol with DEC
in the presence of emim[Ac] as catalyst. Reaction conditions: reaction time = 2 h,
DEC/glycerol molar ratio = 2 and emim[Ac] = 0.5 mol% based on limiting reactant.
131
100 Glycerol conversion GC yield
80
Percentage, %
60
40
20
0
0.5 1 1.5 2 2.5 3 3.5 4
Reaction time (hr)
Fig. 2. Effect of reaction time on the transesterification of glycerol with DEC in the
presence of emim[Ac] as catalyst. Reaction conditions: temperature = 120 °C, molar
ratio of DEC/glycerol = 2 and emim[Ac] = 0.5 mol% based on limiting reactant.
3.2.2. Effect of time
Higher reaction time could be advantageous as it allows more
time for the glycerol to react in chemical catalysed reaction. Fur-
thermore, the conversion rate of glycerol, selectivity and yield of
GC is expected to increase with reaction time. Fig. 2 shows the
influence of reaction time on the transesterification reaction catal-
ysed by emim[Ac], with respect to the glycerol conversion and GC
yield. The GC yield is improved from 42.40% to 88.70% when the
reaction time had increased from 1 h to 2 h and then decreased
over an extended time of reaction. It was also found that, one phase
of solution was only obtained after 1.5 h of heating, thus enhance
the reaction rate thereafter. However, time of reaction was very
crucial as GC selectivity drop to 68.00% when the reaction time is
prolonged up to 4 h. The formation of GDC and glycidol was
expected to decrease the GC selectivity whereas, glycerol conver-
sion was slightly enhanced with extended time of reaction.
3.2.3. Effect of DEC/glycerol molar ratio
Since the rate of reaction can be manipulated by varying the
amount of one of the reactant, the molar ratio of substrates is an
important parameter in affecting the course of reaction. According
to the stoichiometric calculations, the ratio for transesterification
reaction requires only 1 mol of carbonates and 1 mol of glycerol
to produce 1 mol of GC and 2 mol of relevant by-product. However,
it was reported that type of catalyst and reaction conditions
strongly affect the mechanism of reaction. In the transesterification
between the hydrophilic glycerol and hydrophobic carbonate
source, the reactants are not miscible and the reaction is reversible
which is in need of an excess carbonate source to give positive
effect on the conversion and yield [17]. The prevention of two-
phase formation between the reactants can be achieved either by
applying excessive amount of carbonate source over the glycerol
moiety to act as reactant and solvent or by adding organic solvent
Table 3
Effect of DEC/glycerol molar ratio on conversion of glycerol and GC yield and
selectivity. Reaction conditions: temperature = 120 °C, reaction time = 2 h and emim
125 130
DEC/glycerol ratio Glycerol conversion, % GC yield, % GC selectivity, %
1 28.90 28.00 96.90
2 93.50 88.70 94.90
3 96.00 78.10 81.40
4 92.91 72.92 78.50
132 Z.I. Ishak et al. / Chemical Engineering Journal 297 (2016) 128–138

[24]. In additional, emim[Ac] can also serve as solvent in this reac- 100 Conversion Yield Selectivity
tion as it possess dual function.
As tabulated in Table 3, low conversion and GC yield was
observed when equimolar of reactants was used in the transester- 80
ification giving 28.90% and 28.00%, respectively. The GC yield was

increased when the DEC/glycerol ratio is raised beyond 2 and keep
slightly decreased at molar ratio of 3. Further increase in the
amount of DEC beyond the molar ratio of 3 has adverse effect on
the yield and selectivity of GC and would incur additional cost
for the reactants. As a result, conversion of glycerol was slightly
decreased to 92.91% and also GC yield decreased to 72.92% at molar
ratio of 4. This is expected due to dilution of reaction by DEC or fur-
ther reaction of GC with excess DEC to form GDC. It has been men-
tioned by Ochoa-Gomez et al. [15] in their study that GDC
synthesis could not be prevented and glycidol was additionally
obtained in yields of 6–10% with respect to some parameters effect.
Therefore, the molar ratio of DEC: glycerol was fixed at 2:1 for fur-
ther experiments.
3.2.4. Effect of catalyst loading
Increasing of catalyst loading led to a gradual increase in GC
yield because more glycerol molecules would be catalysed in the
desired reaction. The effect of catalyst loading on conversion, yield
and selectivity was investigated in a range of 0.1–10 mol% keeping
other parameters constant (Fig. 3). Low emim[Ac] loading (0.1 mol
%) leads to a too slow reaction with 65.00% conversion and GC yield
was 64.82%, thus giving 87.10% GC selectivity. About 93.50% con-
version of glycerol and 88.70% GC yield was observed in 2 h reac-
tion time at a emim[Ac] loading of 0.5 mol%. Increase of emim
[Ac] loading to 10 mol% has increased the conversion slightly and
GC yield had decreased to 70.03%. Increase of catalyst concentra-
tion is believed to promote GDC formation [15] or glycerol decar-
boxylation [16] as described in ATR-FTIR and NMR studies
(Sections 3.3 and 3.4). It has been reported that, GC selectivity
decreased as low as 15.00% when concentration of [TMA][OH] cat-
alyst increase to 6 mol% [16]. Therefore, the use of 0.5 mol% of the
emim[Ac] was good enough for GC synthesis in this reaction.
3.2.5. Reusability of catalyst
There is a need to reuse the catalyst after every cycle. Thus,
reusability study was critically essential for the economic feasibil-
ity of reaction. The possibility of recycling emim[Ac] was also
investigated under the optimal reaction conditions. The perfor-
mance of emim[Ac] is shown in Fig. 4. From the results, it revealed
that the emim[Ac] could be recycled three times without any sig-
Percentage, %
60
40
20
0
0 1 2 3 4
Run
Fig. 4. Recycling of emim[Ac]. Reaction conditions: Temperature = 120 °C,
Time = 2 h, Molar ratio of DEC/glycerol = 2 and emim[Ac] = 0.5 mol% based on
limiting reactant.
nificant reduction in the conversion of glycerol, yield and selectiv-
ity of GC. The loss in activity and decrease in percent conversion
may be due to slight mass loss of emim[Ac] during the catalyst
recovery process. It is necessary to note that, electrostatic force
between the cation and anion in IL is stronger than Van-der Waals
force, thus give stable molecular structure of emim[Ac] and also
good reusability [44].
3.3. ATR-FTIR studies
In order to clearly understand the interaction of screened ILs
with glycerol or GC, ATR-FTIR analysis was conducted to corrobo-
rate with GC-FID analysis. Hypothesesly, degree of interaction
between hydroxyl group of glycerol and anion of an IL is of pivotal
importance in determining the activity of the ILs toward conver-
sion of glycerol and GC yield. This degree of interaction can be cor-
related in a form of hydrogen bond basicity of anion described by
the parameter b. Anion plays a major role in activating the O–H
of glycerol through the hydrogen-bonding interaction. The
strength of nucleophile of the anion must be high enough to

100 Glycerol conversion GC yield

80
Percentage, %

60

40

20

0
0 0.1 0.5 1 5 10
Catalyst loading, mol%
Fig. 5. ATR-FTIR spectra showing the interactions of glycerol with ILs: (a) glycerol,
Fig. 3. Effect of catalyst loading on the transesterification of glycerol with DEC in (b) glycerol-MA[NO3], (c) glycerol-EA[NO3], (d) glycerol-bmim[Cl] (e) glycerol-
the presence of emim[Ac] as catalyst. Reaction conditions: temperature = 120 °C, bmim[BF4] (f) glycerol-emim[DMP], (g) glycerol-bmim[Dca], (h) glycerol-HEA[Fmt]
time = 2 h, molar ratio of DEC/glycerol = 2. and (i) glycerol-emim[Ac]. The molar ratio of glycerol to IL was set at 1.
 Z.I. Ishak et al. / Chemical Engineering Journal 297 (2016) 128–138 133

hydrogen bond acceptor ability and weaken IL’s basicity. Therefore,

N N an assumption was made in which IL having b value more than 1.0
H would significantly catalyse transesterification reaction with good
O O glycerol conversion and GC yield.
O H O Further study was conducted using emim[Ac] as it shows a good
correlation between hydroxyl group of glycerol and acetate (Ac)
H anion together with high glycerol conversion and GC yield. Ac
O
anion tends to undergo a stronger interaction with the hydroxyl
Scheme 2. Hydrogen-bonding interaction between emim[Ac] and glycerol. group of glycerol. The three hydroxyl groups of glycerol are active
in transesterification reaction. As the glycerol has symmetrical
structure, it is believed that Ac anion can freely form H-bonding
pulling the proton from the hydroxyl group of glycerol, thus initi- between the available hydroxyl groups of glycerol at carbon 1
ate the reaction. and carbon 2 (Scheme 2). However, the primary alcohol (carbon
The effect on activity of screened ILs specifically anions toward 1) is presumably more reactive than secondary alcohol (carbon
the transesterification reaction of glycerol was demonstrated in 2). Once the transesterification reaction of primary alcohol occurs,
Fig. 5. As shown in the spectra, it was clearly observed when glyc- this will be resulting in the facile formation of the corresponding
erol was interacted with emim[Ac] which having a b values 1.201, glyceroxide anion, and secondary alcohol that will further reacted
the absorption band centred at 3287 cm1 corresponding to the with nearby carbonate group, which GC is formed.
hydroxyl group of glycerol shifted to the lower frequency of The ATR-FTIR study was proceed to investigate the formation of
3195 cm1 (Fig. 5i). Meanwhile, the O–H stretching frequency shift GC within selected time interval with the basis of peak intensity
to a slight lower frequency when glycerol was interacted with under reaction using emim[Ac] (Fig. 6). Throughout the reaction,
emim[DMP], bmim[Dca] and HEA[Fmt] of 3272, 3272 and peaks intensity correspond O–H bending in glycerol at
3278 cm1 (Fig. 5f–h). Upon contact of glycerol with MA[NO3], 1262 cm1 and 923 cm1 [48] reduced significantly after 2 h reac-
EA[NO3], bmim[BF4], bmim[Cl], the absorption band moved to tion time. The O–H bending is further supported by the –O–H
higher frequency of 3411, 3399, 3332 and 3348 cm1, respectively stretching centred at 3387 cm1 [49] that shows reduction in peak
(Fig. 5b–e). The higher O–H stretching frequency shift of glycerol
upon interacting with MA[NO3], EA[NO3], bmim[BF4] and bmim
[Cl] indicate that there is no interaction between the hydroxyl
group of glycerol and NO  
3 , BF4 and Cl anion. This can be ascribed
to the weakening of hydrogen-bonding interaction between glyc-
erol molecules due to the dilution with ILs (in this case bmim
[BF4] and bmim[Cl]), thereby resulting in the increase of the O–H
bond strength [45]. From FTIR study, our first hypothesis does
not fit well with the ATR-FTIR trend of glycerol-ILs interaction for
most of ILs according to their b values, except for emim[Ac]. The
performance of ILs towards the conversion of glycerol somewhat
was in line with reported findings by Yi et al. [27]. Surprisingly,
Cl anion which was known to be categorised as basic IL does
not performed well in this reaction. This can best be explained
by hydrogen (hydroxyl group of glycerol) be preferred to form
bond to an electronegative O or N atom rather than a Cl atom Fig. 7. FT-IR spectra of transesterification of glycerol using emim[Ac] as catalyst: (a)
[40]. Besides, the interaction of glycerol–IL can be related to the GC, (b) GC-emim[Ac], 0.1 mol%, (c) GC-emim[Ac], 0.5 mol% and (d) GC-emim[Ac],
complexity of anion structure [46] and intermolecular hydrogen 1 mol%, (e) GC-emim[Ac], 5 mol% and (f) GC-emim[Ac], 10 mol%. Reaction condi-
tions: temperature = 120 °C, time = 2 h, Molar ratio of DEC/GC = 2.
bonds in mixtures of glycerol–IL [47] which could reduce the

(h)

(g) d
b
(f) e
c f
(e) g
a

(d)

(c)

(b)

(a)

Fig. 6. ATR-FTIR spectra of transesterification of glycerol using emim[Ac] as catalyst: (a) 30 min, (b) 1 h, (c) 1.5 h, (d) 2 h, (e) 2.5 h, (f) 3 h, (g) 3.5 h and (h) 4 h. Reaction
conditions: temperature = 120 °C, Molar ratio of DEC/glycerol = 2 and emim[Ac] = 0.5 mol% based on limiting reactant.
134 Z.I. Ishak et al. / Chemical Engineering Journal 297 (2016) 128–138

(g)

(f) glycidol glycidol

(e)
GDC
GDC
GDC

(d)
GC GC
GC

(c)

(b) glycerol glycerol

(a)

Fig. 8. 13C NMR of reaction mixture at selected time interval which is (a) 0 min, (b) 30 min, (c) 1 h, (d) 1.5 h, (e) 2 h, (f) 2.5 h and (g) 3 h. Reaction conditions:
temperature = 120 °C, molar ratio of DEC/ GC = 2 and emim[Ac] = 0.5 mol% based on limiting reactant. Deuterated methanol-d4 (99.8%) was used as solvent in NMR analysis.

Fig. 9. 1H NMR analysis of emim[Ac] at (a) room temperature and (b) 120 °C, heated at reaction time of 2 h. Deuterated methanol-d4 (99.8%) was used as solvent in NMR
analysis.

intensity, presumably due to glycerol being converted into GC.
Peak at 1750 cm1 correspond to C@O of GC increased in intensity
when reaction time is prolonged up to 2 h. The peaks at range
(1200–1000) cm–1 also support the presence of GC where these
peaks indicate C–C and C–O stretching of 2-hydroxyethyl chain
[50]. All peaks correspond to GC shows increased in trend up to
2 h of reaction time and slight decreased thereafter, indicated that
selectivity of GC was reduced. Apart of that, it was found that there
was formation of GDC at peak 1264 cm1 as reaction time increase
at 2 h, however this peak was not seen thereafter [51]. It also can
be seen that, peak intensity at 923 cm1 correspond to O–H bend-
ing and 908 cm1 were slightly broaden when reaction proceed
(more than 3 h). This peak was expected corresponding to C–O–C
bond of glycidol [52,51]. The formation of GDC and glycidol were
also reported in other studies indicated that it was difficult to stop
the reaction at the targeted molecule [15,53]. It is necessary to
 Z.I. Ishak et al. / Chemical Engineering Journal 297 (2016) 128–138 135

Fig. 10. 13C NMR analysis of emim[Ac] at (a) room temperature and (b) 120 °C, heated at reaction time of 2 h. Deuterated methanol-d4 (99.8%) was used as solvent in NMR
analysis.

O-
O
N H
H H O H
N O
O
CH3CH2O- + H+ CH3CH2OH
O
O
O O
O
O
glycerol 1,2-carbonate O
O O O 1a
OH H O
H O H
-
O N
N
O
CH3CH2O- + H+ CH3CH2OH
O O O
H O

Scheme 3. Mechanistic pathway for synthesis of GC through transesterification of glycerol with DEC and emim[Ac] IL as catalyst.

mention that, the yield of GDC and glycidol in this reaction some-
how was not calculated in this study.
It would be reasonable to expect that the strength of emim[Ac]
as nucleophile to initiate the formation of glyceroxide anion can
somehow further react with GC, thus decrease its selectivity.
Owing to this postulate, ATR-FTIR study on the effect of emim
[Ac] loading towards the GC selectivity was investigated. As can
be seen in Fig. 7, a pronounced O–H stretching frequency shift of
GC was observed to shift to lower frequency when catalyst loading
(with respect to GC, mol%) have increased from 0.1 to 10 mol%. This
implies that interaction of Ac anion and O–H of GC is increasingly
strong with the increase of catalyst loading. As Ac anion has
higher b value which is 1.201, it was believed that 0.5 mol% cata-
lyst loading has sufficient capability to catalyse the transesterifica-
tion reaction with GC yield of 88.70%. Increase of catalyst loading
(more than 0.5 mol%) was believed to increase the GC yield. How-
ever, Fig. 7d–f show that increase of catalyst loading (more than
0.5 mol%) somehow helped to promote the formation of undesired
products provided decrease of peak intensity at 1750 cm1 corre-
spond to C@O of GC and appearance of peak at 1264 cm1 which
expected to belong to GDC as discussed earlier, thus decrease GC
selectivity. This is due to activation of hydroxyl end of GC by the
Ac anion thus, lead to the formation of undesired products either
through further carbonylation of GC to form GDC or decarboxyla-
tion of GC to form glycidol as been reported by other studies
[15,45,51].
From ATR-FTIR studies, it can be concluded that, the interaction
of the anion of the IL (b value > 1.0, neglecting the complexity of
IL’s structure) with glycerol should be strong enough and the inter-
action of anion with GC must be sufficiently weak in order to
obtain high glycerol conversion, GC yield and selectivity.
3.3.1. 13C NMR studies
Time on-time study of the reaction mixture shows that, only
glycerol peaks at 72.0 ppm and 62.5 ppm which are attributed to
the presence of –CH–O– and –CH2–O– were observed at the early
136 Z.I. Ishak et al. / Chemical Engineering Journal 297 (2016) 128–138

(a)

O- O O O
O
H O
N O
H O O O O CH3CH2OH
N O
O O
O
glycerol dicarbonate

(b)

O-
O
N O O
H CO2
N O O O OH
H
glycidol

Scheme 4. Mechanistic pathway for synthesis of possible by-products from GC, (a) glycerol dicarbonate (GDC) and (b) glycidol, with emim[Ac] as catalyst.

Table 4
Comparison of previous reported studies using ionic liquids as catalysts with respect to different anion.

Anion Reaction Temperature Ratio (DMC/G) Catalyst loading Conversion Yield/selectivity References
time (h) (°C) (mol%) (%) (%)
Acetate 2 120 2 (DEC/G) 0.5 93.50 88.70 Present work
Nitrate 2 120 2 (DEC/G) 0.5 <10 <10 Present work
Formate 2 120 2 (DEC/G) 0.5 24 24 Present work
Dimethyl phosphate 2 120 2 (DEC/G) 0.5 22.2 22 Present work
Chloride 2 120 2 (DEC/G) 0.5 <10 <10 Present work
Chloride 0.5 70 2 10 <10 NA [27]
Tetrafluoroborate 2 120 2 (DEC/G) 0.5 <5 <5 Present work
Dicyanamide 2 120 2 (DEC/G) 0.5 45 45 Present work
Dicyanamide 13 120 3 0.17 mmol 95 NA [17]
Dicyanamide 13 120 3 0.2 mmol 95 NA
Dicyanamide 13 120 3 0.4 mmol 100 NA
Bromide 6 120 2 3.3 NA 92 [54]
Bromide 1.25 80 3 0.217 mmol Very low NA [16]
Carboxylate 1.33 74 3.2 1 NA 100 [16]
Carboxylate 5 74 3.2 5 NA 93
Hydroxide 1.25 80 3 0.217 mmol 89 50/56 [16]
Hydroxide 0.5 70 2 10 59 59/100 [27]
Bis(trifluoromethylsulfonyl) imide 13 120 3 0.2 mmol 0 NA [17]
Hexafluorophosphate 13 120 3 0.13 mmol 0 NA [17]
Methylcarbonate 13 120 3 0.1 mmol 100 NA [17]
Imidazolide 0.5 70 2 10 73.4 73.4/100 [27]
Hydrogen sulphate 0.5 70 2 10 15 76 [27]
1,8-diazabicyclo [5.4.0] undecenc-7-ene 0.5 100 3 2.5 wt%a 96 79/82 [26]
(DBU)-methanol
1,8-diazabicyclo [5.4.0] undecenc-7-ene 0.5 100 3 2.5 wt%a 87 78/90 [16]
(DBU)-propylene glycol
1,8-diazabicyclo [5.4.0] undecenc-7-ene 0.5 100 3 2.5 wt%a 85 78/92 [26]
(DBU)-glycerol

NA = Not reported in the literature.

G = glycerol, DMC = dimethyl carbonate, DEC = diethyl carbonate, GC = glycerol carbonate.
Conversion (%) = ((mol glycerolinitial  mol glycerolresidual)/mol glycerolinitial)  100%.
Yield (%) = (mol GCproduced/mol glycerolinitial)  100%.
Selectivity (%) = Y/C.
a
Catalyst loading (wt%) = (gcatalyst/gglycerol)  100%.

stage of reaction (Fig. 8a and b). GC peaks at 61.5 ppm, 67 ppm and
77.5 ppm correspond to –CH2–O–, –CH2–OH and –CH–, respec-
tively are gradually increased thereafter. On the other hand, peaks
correspond to GDC, glycidol and other unknown peaks were
observed as the reaction time is prolonged. This assumption was
made based on the observation on ATR-FTIR peaks pattern which
has been discussed in Section 3.3, whereby, with increasing of
reaction time, the intensity of the respective peaks also increased.
Subsequently, further quantitative analysis was conducted using
GC-FID in order to calculate the glycerol conversion and GC yield.
It is necessary to mention that yield of GDC, glycidol and other
unknown peaks were not taken into account in this study.
Stability of emim[Ac] at working temperature (120 °C) were
confirmed by 1H (Fig. 9) and 13C NMR analyses (Fig. 10). No signif-
icant shiftment of chemical shifts were observed in both 1H and 13C
NMR spectra, indicating that, emim[Ac] IL has not undergo any
decomposition during transesterification reaction took place and
it is applicable to be reused several time.
 Z.I. Ishak et al. / Chemical Engineering Journal 297 (2016) 128–138
3.4. The reaction mechanism
The reaction mechanism of transesterification reaction of glyc-
erol is illustrated in Scheme 3. The reaction of the glycerol with
DEC has been described to take place via a mechanism through
the formation of the glyceroxide anion, initiated by nucleophilic
attack of Ac anion. It is expected that ILs with a strong hydrogen
bond basicity are effective in abstracting the proton from the pri-
mary hydroxyl group, thus initiate the reaction. Ethanol (1 mole-
cule) is produced during this step. The reaction is continued by
intermediate species (1a) resulting from the attack of the glycerox-
ide anion on the carbon of the carbonate group. The intermediate
species will subsequently undergo fast intramolecular cyclisation
to yield GC concomitantly with the production of a second ethanol
molecule.
The reaction does proceed with the formation of GDC and/or
glycidol, under various possible reaction conditions that have been
discussed in optimisation study (Section 3.2). Thus, it is necessarily
to consummate the reaction mechanism of GDC and glycidol for-
mation as in Scheme 4.
3.5. Comparison of the catalytic activity of emim [Ac] IL with other
reported ILs
The yield of GC during the transesterification of glycerol with
DEC was compared with other reported catalysts and the results
are presented in Table 4. Comparative results can be obtained from
previous reported ILs, as most of the reported findings used
dimethyl carbonate as carbonylating source. Thus, the result of this
study reiterate the high activity of emim[Ac] IL for transesterifica-
tion of glycerol with DEC to yield GC.
4. Conclusion
In this study, several selected ammonium and imidazolium-
based ILs as catalysts were screened for transesterification reaction
to synthesis GC. As a result, emim[Ac] is a good candidate as a cat-
alyst for transesterification reaction in view that it is biodegrad-
able, non-toxic and non-corrosive. Emim[Ac] shows high remark
activity towards the reaction as it gives 93.50% glycerol conversion
and 88.70% GC yield under optimal reaction conditions. Emim[Ac]
catalyst can be recycled three times with insignificant reduction in
the conversion of glycerol, yield and selectivity of GC. Interaction
between glycerol–IL and GC–IL shows that, anion plays a crucial
role in determining the activity of the IL toward conversion of glyc-
erol and GC yield. Conclusively, with the promising glycerol con-
version and GC yield catalysed by emim[Ac] it will lead to
further sharing on idea in exploration conversion of glycerol to
value added products.
Acknowledgement
The authors gratefully acknowledge the High Impact Research
MOE (HIR-MOE) Grant UM.C/625/1/HIR/MoE/ENG59 from the
Ministry of Education Malaysia. Our sincere appreciates are also
extended to PPP Grant (PG206-2014B) and University of Malaya
Centre of Ionic Liquid (UMCIL).
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