Journal of the Taiwan Institute of Chemical Engineers 102 (2019) 276–282

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Journal of the Taiwan Institute of Chemical Engineers

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Microwave-assisted synthesis of glycerol carbonate by the

transesterification of glycerol with dimethyl carbonate using Musa
acuminata peel ash catalyst
Bishwajit Changmai a, Ikbal B. Laskar b, Lalthazuala Rokhum a,∗
a
Department of Chemistry, National Institute of Technology Silchar, 788010 Assam, India
b
Department of Mechanical Engineering, National Institute of Technology Silchar, 788010 Assam, India

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

Article history: Musa acuminata peel ash (MAPA), a biowaste-derived solid base catalyst is investigated for the transester-
Received 2 April 2019 ification of glycerol with dimethyl carbonate (DMC) to glycerol carbonate (GC), a potential fuel additive,
Revised 20 May 2019
under microwave irradiation. High basicity, high surface area and mesoporous nature of the catalyst ef-
Accepted 15 June 2019
fectively promote the conversion of glycerol to GC. Moreover, the catalyst being a biowaste is abundantly
Available online 27 June 2019
available, cheap, biodegradable, renewable, sustainable and environment-friendly. Microwave irradiation
Keywords: shows higher conversion (99%) and greater selectivity (99.5%) as compared to conventional heating (18%
Glycerol carbonate conversion and 98.5% selectivity) under our optimized reaction conditions such as 1:2 molar ratio of
Fuel additives glycerol/dimethyl carbonate, catalyst loading of 6 wt%, temperature of 75 °C and time of 15 min. The syn-
Microwave and Musa acuminata peel ash thesized GC was characterized by gas chromatography, 1 H and 13 C NMR, and mass spectrometry. The
reusability of the catalyst was investigated up to 6 successive cycles and it shows great stability towards
the transesterification of glycerol to GC.
© 2019 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction Among all, transesterification of glycerol with dimethyl carbonate

Increasing energy demands, environmental pollution and deple-
tion of fossil fuels has led to the search for the new alternative
green source of energy [1–3]. In this regard, biodiesel is widely in-
vestigated as an alternative to fossil fuels owing to its renewability,
sustainability and environmentally friendly nature [4,5]. The rapid
development of the biodiesel market encourages the co-production
of glycerol. Around 10 wt% of crude glycerol has been formed
during biodiesel production and dumped as industrial waste [6].
Therefore, research focused on the exploitation of glycerol to other
value-added chemical products is gaining significant attention in
recent years.
Glycerol carbonate (GC), a transesterification product of glyc-
erol, is widely investigated derivative of glycerol. It has some in-
teresting properties like biodegradability, high boiling point, water
solubility, low viscosity etc. [7,8]. Owing to these, GC is used as an
intermediate in organic transformation reactions, solvent, surfac-
tant, fuel additive, in cosmetic industries etc. [9–11].
A variety of methods are reported for the synthesis of GC from
glycerol e.g., the reaction between glycerol with phosgene [12],
carbon dioxide [13], urea [9] and dimethyl carbonate (DMC) [14].
∗
Corresponding author.
E-mail address: rokhum@che.nits.ac.in (L. Rokhum).
is mostly investigated as the method is eco-friendly and it releases
only methanol as a byproduct that can be easily recovered [15].
Both homogeneous and heterogeneous base catalyst can be used
for the conversion of glycerol to GC [16,17]. But the heterogeneous
catalyst is gaining much interest in comparison to homogeneous
catalyst due to its facile recoverability and reusability [18,19]. Al-
kali metals and alkali metal oxide based heterogeneous base cat-
alyst are mostly used towards transesterification of glycerol due
to the presence of highly basic sites [20]. However, high basicity
(Hammett indicator, H_ > 18) leads to the decomposition of GC or
decarbonylation to glycidol [21]. Several heterogeneous base cata-
lyst were already reported for the conversion of glycerol to GC e.g.,
Ca–Al hydrocalumite [22], LiNO3 /Mg4 AlO5.5 [23], MgO–ZrO2 [24],
Co3 O4 /ZnO [25], Li/ZnO [26], MgO/Al2 O3 [27] etc. Despite their own
advantages, preparation of such catalyst often requires multi-steps
synthesis, toxic chemicals and drastic reaction conditions, which
increases the overall cost of GC production [28,29]. Therefore, de-
velopment of a heterogeneous base catalyst, which is recoverable,
reusable, active towards the transesterification of glycerol and es-
pecially cost-effective is a major concern.
A worldwide rapid growth of human population has resulted
in the exponential generation of food waste, which causes both
environmental and economic problems. It is expected that food
waste will rise to 126 Mt in 2020 if the management of food waste

https://doi.org/10.1016/j.jtice.2019.06.014
1876-1070/© 2019 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
 B. Changmai, I.B. Laskar and L. Rokhum / Journal of the Taiwan Institute of Chemical Engineers 102 (2019) 276–282
is not undertaken. Therefore, waste management is a major con-
cern for both developed countries and the industrial world [30,31].
The exploitation of bio-waste for the production of catalyst has
drawn significant attention due to their excellent catalytic activ-
ity and they are being biogenic, biodegradable and cost-effective as
well as a way to boost conservation of natural resources [32–34].
In recent years, several bio-waste derived catalyst such as dispos-
able baby diapers waste (DBDW) [35], fishmeal biochar [36], boiler
ash (BA) waste [37], oil palm empty fruit bunch [38] and waste
red mud [39] etc. have been reported for transesterification reac-
tions. However, preparation of these catalysts requires high calci-
nation temperature for several hours; hence catalyst preparation is
not energy efficient.
In recent decades, due to high energy consumption in con-
ventional methods and the need to develop more energy ef-
ficient techniques, ultrasound and microwave-assisted synthesis
have been widely investigated. Microwave irradiation technique in-
volves rapid and homogeneous heating of the reaction mixture,
thus improving the rate and selectivity of the reaction to a larger
extent than conventional heating techniques [40–43]. The drastic
increase in the rate of microwave-assisted reactions is due to two
simultaneous effects: (1) thermal effects, where radiation field im-
poses heat to the reaction medium resulting enhanced reaction
rate and (2) non thermal effect, where bond breaking and bond
making process is occurring due to the physical interaction be-
tween the electromagnetic radiation of microwave radiation and
reactant molecules [44]. Since glycerol is a very good absorber of
microwave radiation, it is a wise choice to apply microwave irradi-
ation technique in the transesterification of glycerol to GC [40]. Till
date, only a few literature reported a microwave-assisted GC syn-
thesis from glycerol using certain synthetic chemicals as a catalyst
[40–42]. Hence synthesis of GC using biowaste-derived material is
highly desirable to make the process cheap, renewable and eco-
friendly.
In continuation of our research interest in the development of
renewable, sustainable and environmental friendly heterogeneous
catalyst [18,19,45,46], here we, for the first time, report on the
transesterification of glycerol to GC using MAPA as a heterogeneous
catalyst under microwave irradiation.
2. Experimental
2.1. Chemicals used
Glycerol was purchased from Sigma Aldrich (AR, purity ≥99.5%),
dimethyl carbonate was purchased from HiMedia (LR, purity
≥99.5%) and methanol was purchased from Fisher Scientific with
purity 99%. The chemicals were used without further purification.
2.2. Preparation of catalyst
MAPA was prepared using a reported procedure [46]. The fresh
Musa acuminata peels were collected from Mizoram, India and
washed properly with distilled water, cut into small pieces and
dried under the sun. The dried peels were burned in the open air
to form Musa acuminata peel ash. Then the ash is used as a catalyst
for transesterification of glycerol to GC.
2.3. Synthesis of GC
2.3.1. Microwave irradiation method
Glycerol (0.92 g, 10 mmol), DMC (1.8 g, 20 mmol) and catalyst
(55 mg, 6 wt% with respect to glycerol) were taken in a 10 mL mi-
crowave tube. Then the reaction mixture was stirred at 600 rpm in
the microwave reactor at 75 °C and 50 W ample power (Discover
277
Scheme 1. Formation of GC from glycerol and DMC under microwave irradiation.
SP Microwave System). The reaction was completed in 15 min. Af-
ter completion of the reaction, the catalyst was separated via fil-
tration. Then the product was isolated by removing excess DMC
and methanol using rotary evaporator. The final product was ana-
lyzed by gas chromatography. The conversion of glycerol, yield and
selectivity of GC was calculated using the expressions reported in
the literature [35,36]. The structural depiction of synthesis of GC
from glycerol and DMC under microwave irradiation is shown in
Scheme 1.
Glycerol conversion :
Initial glycerol concentration − final glycerol concentration
Initial glycerol concentration
× 100 %
Concentration of GC in molar
GC yield : × 100 %
Initial molar concentration of glycerol
Yield of GC
GC selectivity : × 100 %
Conversion of glycerol
2.3.2. Conventional method
Glycerol (0.92 g, 10 mmol), DMC (1.8 g, 20 mmol) and catalyst
(55 mg, 6 wt% with respect to glycerol) were taken in a round bot-
tom flask and the mixture was stirred at 600 rpm and 75 °C tem-
perature. For comparison with the microwave irradiation method,
the conversion of glycerol to GC was investigated every 15 min us-
ing gas chromatography. It was observed that the reaction took 2 h
for completion.
2.4. Methods of characterization
Gas chromatography was taken on Agilent 7890 instrument
equipped with head space injector mode, a CPSIL 8CB capillary
column (30 m × 0.25 mm × 0.25 μm) and GC-FID detector. The oven
temperature was started from 55 °C and increase with a rate of
10 °C min−1 up to a final temperature of 230 °C. The temperature
of the detector and the injector were 300 °C and 250 °C, respec-
tively. For quantitative analysis of the products, biphenyl was used
as an internal standard. 1 H NMR (Nuclear magnetic resonance) and
13 C NMR was performed on JEOL ECZR series instrument with a
spectrometer frequency of 600 MHz and tetramethyl silane (TMS)
was used as an internal standard., mass spectrometry was per-
formed on JEOL model: AccuTOF GCV) with mass range from 10 to
600 amu, SEM (Scanning electron microscope) and EDX was taken
in JEOL model JSM – 6390LV instrument; operating conditions:
80 mA beam current, 20 kV and 1500 X magnification power. The
samples were first dispersed in ethanol via ultrasonication and
dried in oven over a copper grid and finally, the copper grid was
placed in SEM. EDX analysis was performed on the same instru-
ment by changing it to EDX mode with 0.28 sr of solid angle. HR-
TEM (high-resolution transmission electron microscope) was per-
formed on JEOL/JEM 2100 instrument with a magnifying power of
278 B. Changmai, I.B. Laskar and L. Rokhum / Journal of the Taiwan Institute of Chemical Engineers 102 (2019) 276–282
20 0 0 X-1,50 0,0 0 0 X; condition: 20 0 kV voltage. The samples were
dispersed in ethanol and dried in the oven over a copper grid
and placed on TEM. X-ray fluorescence analysis was performed in
Bruker; model: S4 pioneer. Operating conditions: the powdered
sample was placed on a circular shape block having a diameter
of 38–40 mm and 10% methane, 90% argon were used as a de-
tector gas. N2 adsorption–desorption was taken on Micromerit-
ics ASAP 2010 surface area and porosity analyzer. Operating con-
ditions: bath temperature 77 K and degassed at 200 °C for 10 h.
Thermo gravimetric analysis was performed on PerkinElmer TGA
40 0 0 instrument. Operating conditions: The sample was taken in
a very small silica crucible and weight loss of the sample was
recorded within the temperature range 30–10 0 0 °C with a heating
rate of 0.1–200 °C min−1 under a constant flow of N2 .
3. Results and discussion
3.1. Characterization of fresh catalyst
The characterization of Musa acuminata peel ash was reported
in our previous work [45,46]. X-ray fluorescence (XRF) data (Sup-
plementary information, Table S1) shows the presence of K2 O as a
major component i.e., 65.11%, which is mainly responsible for the
high basicity of the catalyst. SiO2 , CaO and MgO are present as a
minor component with wt% of 10.86%, 7.78% and 2.42%, respec-
tively.
Both transmission electron microscope (TEM) (Supplementary
information, Fig. S1) and scanning electron microscope (SEM) (Fig.
S2) images show microporous and mesoporous structure with
spongy nature of the catalyst. Moreover, TEM images show that
the particles are highly aggregated and the average particle size
is ̴ 30 nm.
Energy dispersive X-ray (EDX) spectrum (Fig. S3) shows the
presence of K, C and O as a major element in the catalyst with
atomic wt% of 20.77%, 34.34% and 40.61%, respectively, which sup-
ports the XRF data. The presence of a higher amount of K improves
the basicity of the catalyst.
The basicity of the catalyst was investigated using Ham-
mett indicator method, where phenolphthalein, bromothymol blue,
Alizarine yellow R and 2,4,6-trinitroaniline were used as an indica-
tor. When the catalyst was mixed with the indicators individually,
first three indicator shows a change in color. However, the color
of the 4th indicator did not change. Thus the basic strength of the
catalyst is in the range of 11.0 ≤ H_ ≤ 12.2. To further investigate
the basicity of the catalyst benzoic acid titration was performed
using bromothymol blue as an indicator and it was found to be
0.169 mmol g−1 .
Brunauer–Emmett–Teller (BET) isotherm (Fig. S4) shows type IV
isotherm, which indicated the mesoporous nature of the catalyst.
The surface area, pore diameter and pore volume of the catalyst
were reported as 539 m² g−1 , 3.38 nm and 0.522 cc g−1 , respectively.
Due to its high surface area and mesoporous nature, the catalyst
shows excellent catalytic activity.
Thermogravimetric analysis (TGA) shows very good stability of
the catalyst with respect to the temperature. The catalyst shows
a mass loss of 12 wt% at around 150 °C, due to evaporation of ad-
sorbed moisture. Further increase in the temperature leads to an-
other mass loss at around 400 °C, which may be attributed to de-
carboxylation of carbonaceous materials (Fig. S5).
3.2. Characterization of GC
Formation of GC was confirmed by 1 H and 13 C NMR. 1 H
NMR (Fig. S6) shows a singlet at 5.41 ppm, which is attributed
to the –OH proton. A multiplet was observed at around 4.79–
4.78 ppm, which corresponds to the –CH proton (proton attached
Fig. 1. Influence of catalyst loading on transesterification of glycerol to GC. Reaction
conditions: 1:2 glycerol to DMC molar ratio, 75 °C, 15 min and 50 W ample power.
with the tertiary carbon). The multiplets at 4.50–4.27 ppm and
3.68–3.48 ppm correspond to –CH2 cyclic and –CH2 linear protons
respectively.
13 C NMR shows peaks at 156.61, 75.06, 66.57 and 61.67 ppm,
which corresponds to C=O, CH, H2 C–O linear and H2 C–O cyclic car-
bon atoms respectively (Fig. S7). 13 C NMR supports the 1 H NMR
data.
To further confirm the formation of GC, mass spectrometry (Fig.
S8) was also performed and it shows the characteristic peaks with
relative intensity at m/Z: 118 (M+ , 2%), 87.00734 (53%), 60.10 (6%),
55(6%), 43 (100%), 31.007 (51%) and 15 (15%).
3.3. Influence of reaction parameters
3.3.1. Effect of catalyst amount on transesterification of glycerol to GC
Catalyst plays a crucial role in a chemical reaction as it can ac-
celerate product formation by lowering the activation energy of the
reaction. The effect of a catalyst on the transesterification of glyc-
erol was investigated by increasing the catalyst amount from 2 to
10 wt% as illustrated in Fig. 1. Gradual increase of catalyst loading
from 2 wt% to 4 wt% enhanced the percentage conversion and per-
centage yield from 56.5% and 54% to 87.5% and 85%, respectively.
However, the increase in catalyst amount to 6 wt%, a conversion of
99% was obtained as higher catalyst loading provide higher num-
ber of available basic sites. Further, an increase in the catalyst load-
ing to 10 wt% leads to a slight decrease in the selectivity and con-
version of glycerol since a large number of basic sites facilitates
the decarboxylation of GC to glycidol [36].
3.3.2. Influence of glycerol to DMC molar ratio
The molar ratio of glycerol to DMC plays a vital role in the con-
version of glycerol via transesterification reaction. Fig. 2 shows the
variation of conversion of glycerol with a variation in glycerol/DMC
molar ratio. A maximum conversion of 99% was observed when the
glycerol/DMC molar ratio is 1:2. Further, an increase in the molar
ratio of glycerol/DMC does not improve the conversion of glycerol
rather the conversion decreases as a higher amount of DMC re-
duces the contact between glycerol and the catalyst [35].
3.3.3. Influence of reaction temperature of transesterification of
glycerol
To increase the miscibility and contact between the reactants,
heating plays a significant role. The effect of temperature on the
transesterification of glycerol to GC is illustrated in Fig. 3 shows
a significant increase in the conversion of glycerol and yield of
GC from 88% and 86% to 99% and 98%, respectively, indicating an
increase in the temperature increase the miscibility and contact
between the reactants. A slight decrease in the selectivity and
 B. Changmai, I.B. Laskar and L. Rokhum / Journal of the Taiwan Institute of Chemical Engineers 102 (2019) 276–282
Fig. 2. Influence of glycerol: DMC molar ratio on transesterification of glycerol to
GC. Reaction conditions: 6 wt% catalyst, 75 °C temperature under microwave irradi-
ation of power 50 W for 15 min.
Fig. 3. Influence of reaction temperature on the conversion of glycerol to GC. Reac-
tion conditions: 1:2 glycerol/DMC molar ratio, temperature 60–100 °C, 6 wt% cata-
lyst, 15 min and 50 W ample power.
Fig. 4. Influence of time on transesterification of glycerol to GC. Reaction con-
ditions: 1:2 glycerol/DMC molar ratio, 75 °C temperature, 6 wt% catalyst, time 5–
20 min and 50 ample power.
conversion was observed when the temperature further rises to
105 °C, as higher temperature leads to the formation of glycidol
[47]. Thus 75 °C is the optimized temperature for transesterifica-
tion of glycerol to GC.
3.3.4. Influence of reaction time
The effect of reaction time on the transesterification of glyc-
erol to GC was investigated by changing the reaction time from
5–20 min and keeping other reaction parameters constant (Fig. 4).
A maximum conversion of 99% was observed when the time is in-
creased from 10 to 15 min. There is no change in the conversion
279
Fig. 5. Influence of microwave irradiation power on glycerol conversion. Reaction
conditions: 1:2 glycerol/DMC molar ratio, 75 °C temperature, 6 wt% catalyst, 15 min
time and 25–100 W ample power.
of glycerol was observed when the reaction time was increased to
20 min. Thus 15 min is the optimized time for transesterification of
glycerol to GC using MAPA.
3.3.5. Influence of microwave irradiation power
Microwave irradiation involves the rapid heating and vigorous
collision between the reactants in a reaction mixture results in
a reduction of reaction time. The effect of irradiation power on
transesterification of glycerol has been investigated as shown in
Fig. 5. When the irradiation power is 25 W, conversion of glycerol
56%. A maximum conversion of 99% was observed when the irradi-
ation power was increased to 50 W. Further increase in the irradia-
tion power to 100 W leads to a slight decrease in the conversion of
glycerol and selectivity of the reaction because the increase in the
irradiation power results in high instantaneous temperature and
violent collision between the reactants, which leads to the slight
formation of glycidol.
3.4. Comparison of the conventional heating method with microwave
irradiation
For comparison, we have performed the reaction using the
same reaction condition i.e., 1:2 glycerol/DMC molar ratio, cata-
lyst loading of 6 wt%, temperature of 75 °C and reaction time of
15 min under conventional heating. After 15 min of reaction merely
18% conversion was observed which is insignificant as compared to
microwave irradiation which shows 99% conversion to GC within
15 min. Thus microwave-assisted synthesis of GC using MAPA as a
catalyst is more preferable than the conventional heating synthesis
of GC in terms of reaction time.
3.5. Comparison of MAPA with reported homogenous and
heterogeneous catalysts
Several literatures have been found regarding the synthesis of
GC using both homogeneous and heterogeneous catalysts. Compar-
ison between the previously reported work and the present work
is listed in Table 1. Homogeneous catalysts such as K2 CO3 [48],
KOCH3 [49] etc., show very high activity using Focused Beam Re-
flectance Measurements (FBRM) technique, but the main drawback
is the problem associated with the reusability and recoverability
of these catalysts. Despite the stability of Zn–Al–LDH [40], Ca–AL–
LDH [42] and Li-palm oil zeolite [50] in the production of GC,
preparation of these catalysts involves complex chemical processes
and high cost. Eventhough several other solid catalysts used for the
synthesis of GC such as DBDW [35], K-zeolite [49], red mud [39],
280 B. Changmai, I.B. Laskar and L. Rokhum / Journal of the Taiwan Institute of Chemical Engineers 102 (2019) 276–282

Table 1
Comparison study of the MAPA with the other reported catalysts.

Entry Catalyst Temp ( °C) Time (min) Conversion (%) Technique MW power (W) References

1 K2 CO3 66–70 60 90 FBRM – [48]

2 KOCH3 75 240 96 FBRM – [49]
3 Waste oil palm empty fruit bunch 90 45 96.5 Conventional heating – [38]
4 Waste red mud 75 90 95.21 –do– – [39]
5 Diaper waste 75 60 95.6 –do– – [35]
6 K-Zeolite 75 90 100 Conventional heating – [50]
7 Li-oil palm ash zeolite 70 90 100 –do– – [51]
8 Boiler ash 150 240 93.6 –do– – [37]
9 Fishmeal biochar 85 60 100 –do– – [36]
10 Zn–Al LDH 120 60 93 MW 1000 [40]
11 CaAl–LDH 90 180 95 MW – [42]
12 Na2 SiO3 95 15 96.7 MW 175 [41]
13 MAPA 75 15 99 MW 50 Present work
14 MAPA 75 15 18 Conventional heating – Present work
15 – 75 15 5 MW 50 Present work

boiler ash [37] etc., can be prepared from natural waste, require-
ment of high calcination temperature and longer time for synthesis
of GC limits their wide applications in industrial scale. In contrast,
MAPA can be easily prepared by burning Musa acuminata peel in
the open air and a conversion of 99% glycerol to GC was obtained
using MAPA as a catalyst under our optimized reaction conditions
(1:2 molar ratio of glycerol/DMC, 6 wt% MAPA, 75 °C, 15 min, mi-
crowave irradiation) as shown in Table 1, (Entry 13). However, un-
der the same reaction conditions, conversion of only 18% glycerol
to GC was obtained in 15 min using conventional heating (Entry
14). Ironically, a low conversion (5%) was obtained without using
catalyst (Entry 15).

4. Reusability of the catalyst

The reusable nature of heterogeneous catalyst lowers the overall

cost of a chemical reaction and hence makes them to use widely
in industrial applications. To check the reusability of MAPA, the
catalyst was filtered by centrifugation, washed with methanol to
remove any organic compound after the reaction and dried in an
oven for 3–4 h at 80 °C. Then the catalyst was used for the next
5 successive catalytic cycles by performing the same chemical re-
action under our optimized reaction conditions and same recovery
method. A conversion of 91% glycerol to GC was obtained after the
6th catalytic cycles (Fig. 6). A slight decrease in the conversion is
due to the leaching of active sites in each catalytic cycle as indi-
cated by EDX spectra.
To investigate the change in the morphology of the recovered
catalyst after the 6th cycle, TEM has been performed. TEM image
Fig. 6. Reusability test of the catalyst up to 6 successive cycles.
(Fig. 7(B)) of the recovered catalyst did not show any significant
change in the morphology from the fresh catalyst (Fig. 7(A)), which
indicates that the catalytic activity of the catalyst retained after 6th
cycles.
SEM and EDX of the reused catalyst after 6 cycles were also per-
formed to investigate the surface morphological change. Fig 8(A)
and (B) shows the SEM images of fresh catalyst and recovered cata-
lyst (after 6 successive cycles). SEM image of the recovered catalyst
show deformation of surface morphologies. EDX (Fig. S9) shows a

Fig. 7. TEM images of fresh catalyst (A) and recovered catalyst after 6 successive runs (B).
 B. Changmai, I.B. Laskar and L. Rokhum / Journal of the Taiwan Institute of Chemical Engineers 102 (2019) 276–282 281

Fig. 8. SEM images of fresh catalyst (A) and recovered catalyst after 6 successive runs (B).

Table 2 References
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