Journal of Cleaner Production 295 (2021) 126437

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Journal of Cleaner Production

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

Valorization of glycerol into glycerol carbonate using the stable

heterogeneous catalyst of Li/MCM-41
Shivali Arora , Vijayalakshmi Gosu , U.K. Arun Kumar , Verraboina Subbaramaiah *
Department of Chemical Engineering, Malaviya National Institute of Technology Jaipur, 302017, India

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

Article history: The present study explored the catalytic activity of the heterogeneous catalyst for transesterification of
Received 19 September 2019 glycerol into glycerol carbonate, a versatile compound. Transesterification of glycerol was investigated
Received in revised form with different active metals (Li, La, Ce, Mg, K) impregnated on MCM-41 (Mobil Composition of Matter No.
12 February 2021
41) framework. Among these, lithium incorporated MCM-41 proved the better catalytic activity towards
Accepted 17 February 2021
the formation of glycerol carbonate. The shortening of a long-range hexagonal array was observed with
Available online 21 February 2021
active metal incorporation due to the accumulation of non-framework Li species in the MCM-41
Handling editor: Dr Sandra Caeiro structure. BET study revealed that Li/MCM-41 possess type IV hysteresis loop according to IUPAC stan-
dards. The average pore diameter was increased from 25.43 Å to 62.02 Å with active metal incorporation
Keywords: in the MCM-41 framework. The catalytic activity of Li/MCM-41 was observed by varying different weight
MCM-41 ratios of active metal and the calcination temperature. The results demonstrated that 5 wt% Li
Glycerol carbonate impregnated on MCM-41, calcined at 450
C, appeared to have a maximum yield of glycerol carbonate.
Glycerol Additionally, the influence of reaction operating parameters was also investigated. The results showed
Transesterification
that 99 ± 1.89% glycerol conversion and 93.14 ± 2.52% glycerol carbonate yield was achieved at dimethyl
Kinetics
carbonate-to-glycerol molar ratio of 3, catalyst dosage of 4 wt% (relative to glycerol mass) and a reaction
temperature of 90
C in 3 h. The recyclability and stability of the screened catalyst was also studied under
optimized conditions. The activation energy of the catalyst was determined by solving the differential
equation using MATLAB ODE15s tool, and the obtained value was 53.77 ± 3.26 kJ/mol. The E-factor and
PMI (Process mass intensity) values of glycerol carbonate synthesis were determined as 1.16 and 2.16,
respectively, which demonstrate the less waste generation during the process.
© 2021 Elsevier Ltd. All rights reserved.

1. Introduction Amongst, transesterification of GLY into glycerol carbonate (GLC)

The consumption of fossil fuels has increased drastically with
rise in concern about greenhouse gas emissions, and the stringent
laws imposed by government demands bio-based fuel alternatives.
Among various renewable resources, biodiesel has gained accept-
ability as an alternative fuel to the global petroleum calamity.
Transesterification of vegetable oil/fat with alcohol generates bio-
diesel. During the biodiesel producing process, approximately 10%
of glycerol (GLY) is produced as a by-product, which needs to be
utilized effectively to make the biodiesel industry sustainable
(Arora et al., 2020).
Therefore, faster commercialization of processes with low cap-
ital cost and the short energy-intensive route is highly desirable.
* Corresponding author.
E-mail address: vsr.chem@mnit.ac.in (V. Subbaramaiah).
had received significant attention as a promising chemical due to
its vast industrial applicability. As this GLC possess potential
properties such as non-toxicity, high density, excellent biodegrad-
ability, low freezing point, and high chemical reactivity (Song et al.,
2017; Rokicki et al., 2005). GLC can be used as a monomer in the
polymer and plastic industry, as a electrolyte in the semiconductor
industry, a curing agent in the cement industry, and plant activator
in the agricultural sector (Teng et al., 2014; Simanjuntak et al.,
2011).
The transesterification of GLY with dimethyl carbonate (DMC)
has proved to be an environmentally benign route for GLC syn-
thesis. Since the process occurs under mild reaction conditions
using non-toxic reactants (DMC and GLY). To improve process
selectivity and yield, a highly efficient alkaline active site catalyst is
required. Several homogeneous catalysts were explored to facilitate
the transesterification reaction, such as, KOH, K2CO3, and NaOH
(Rokicki et al., 2005; Herseczki et al., 2011; Ochoa-Go
mez et al.,

https://doi.org/10.1016/j.jclepro.2021.126437
0959-6526/© 2021 Elsevier Ltd. All rights reserved.
S. Arora, V. Gosu, U.K.A. Kumar et al.
Nomenclature
CGLY Concentration of glycerol at time t, mol/mL
CDMC Concentration of dimethyl carbonate at time t,
mol/mL
CGLC Concentration of glycerol carbonate at time t, mol/
mL
CM Concentration of methanol at time t, mol/mL
Ct Concentration of total active sites present on the
catalyst
Ea Activation energy, kJ/mol
k1 Forward reaction rate constant for the adsorption
of glycerol on active site of catalyst, min1
k-1 Backward reaction rate constant for the
adsorption of glycerol on active site of catalyst,
min1
k2 Forward reaction rate constant for adsorption of
dimethyl carbonate on active site of catalyst,
min1
k-2 Backward reaction rate constant for adsorption of
dimethyl carbonate on active site of catalyst,
min1
k3 Forward reaction rate constant for
transesterification of glycerol to glycerol
carbonate, min1
ke3 Backward reaction rate constant for
transesterification of glycerol to glycerol
carbonate, min1
k4 Forward reaction rate constant for desorption of
methanol, min1
k-4 Backward reaction rate constant for desorption of
methanol, min1
K1 Equilibrium constant for adsorption of glycerol on
active site of catalyst
K2 Equilibrium constant for adsorption of dimethyl
carbonate on active site of catalyst
K3 Equilibrium constant for desorption of glycerol
carbonate on active site of catalyst
K4 Equilibrium constant for desorption of methanol
on active site of catalyst
kˈ Apparent reaction rate constant for
transesterification of glycerol to glycerol
carbonate, min1
-rGLY Rate of depletion of GLY, mol/mL.min
2009). However, reusability and separation of catalyst from the
products are the significant constraints associated with these cat-
alysts (Song et al., 2017). These drawbacks initiate the use of the
heterogeneous alkaline active catalyst for the substantial conver-
sion of GLY. Heterogeneous catalysts, such as CaeAl hydrocalumite
(Zheng et al., 2015), SreAl mixed oxide (Algoufi et al., 2017),
hydrotalcite (Takagaki et al., 2010), hydroxyapatite (Bai et al., 2011),
and CaO (Simanjuntak et al., 2011) had been reported in the liter-
ature for tailoring transesterification reaction to produce GLC.
However, these catalysts have certain limitations, including long
reaction time and rapid deactivation rate. Hence, the high surface
area and stable catalyst are highly needed to overcome the existing
barrier. In the last few decades, MCM-41 received much attention in
material science due to its versatile properties such as large pore
volume, high surface area, high thermal stability, and ease to
incorporate active sites to enhance catalytic activity (Chen et al.,
2002; Ravikovitch et al., 1997). Bare MCM-41 does not possess
2
Journal of Cleaner Production 295 (2021) 126437
enough basic sites, so strengthening the basic site incorporation of
active metal is highly required. Apart from all alkali/alkaline earth
metals, lithium provides strong alkaline sites because of its strong
ion size effect (Corma et al., 2005). Besides, various authors
investigated Liþ as an active metal on different supports to boost
the basic sites of catalyst for the synthesis of biodiesel through
transesterification (Xie et al., 2007; Kaur and Ali, 2011; Wang et al.,
2012; Boro et al., 2014; Puna et al., 2014). The aforementioned
phenomenon necessitate the author’s interest to use Li as an active
metal on MCM-41 for transesterification of GLY into GLC. To the
best of the author’s knowledge, the investigation of Li/MCM-41
catalyst as a heterogeneous catalyst was not performed in the
transesterification of GLY with DMC to GLC conversion.
In the present manuscript, Li species were incorporated on
MCM-41 by wet-impregnation technique. Detailed characterization
has been used to investigate the prepared catalyst’s physico-
chemical properties using FT-IR, SEM, XRD, N2 adsorption-
desorption isotherm, and Hammett titration method. Trans-
esterification reaction was carried out, and the effect of reaction
influencing conditions as well as the catalyst recyclability was
optimized. Apart from the optimization of reaction conditions, re-
action kinetics for the transesterification reaction was also exam-
ined. The Langmuir-Hinshelwood-Hougen-Watson (LHHW) model
was used to develop the kinetics of the reaction since it was
identified as the most trust-worthy model to study heterogeneous
catalytic reactions.
2. Material and method
2.1. Materials
All chemicals used in this study were of analytical grade, and
used without further purification. Glycerol (99% purity), methanol
(99% purity), phenolphthalein, ammonium hydroxide, 2,4 nitro-
aniline, and cetyl trimethyl ammonium bromide (CTAB, surface
directing agent) were purchased from Fisher Scientific, Mumbai,
India. Dimethyl carbonate (98% purity) and lithium nitrate were
acquired from Loba Chemie, Mumbai, India. Tetraethylorthosilicate
(TEOS, silica source) and 4-nitroaniline were obtained from
Chemical Drug House (CDH) Pvt. Ltd., New Delhi, India. Ethanol was
purchased from Merck, Darmstadt, Germany. The standards used
for calibration was Glycerol carbonate (purity > 99.00%) and was
acquired from TCI Chemical Pvt. Ltd., India, pyridine (pu-
rity > 99.99%), and glycerol (purity > 99.50%) were purchased from
Sigma-Aldrich, Missouri, USA.
2.2. Catalyst preparation
MCM-41 (catalyst support) was prepared using CTAB and TEOS
as surface directing agent and silica source, respectively. In the
typical procedure, a clear and homogeneous solution of CTAB was
prepared by dissolving 4.8 g of CTAB in 240 ml of distilled water
under continuous stirring. After that, 16 ml of 25 wt% ammonium
hydroxide was added into it, and stirred for 5 min. Subsequently,
40 ml of TEOS was added drop-wise into the solution. The solution
was stirred for 12 h, and the resultant white material was filtered,
followed by its washing with ethanol and distilled water. There-
after, the obtained powder was kept for drying in a hot air oven at
100
C for 12 h. Then, the dried material was calcined in the muffle
furnace at 550
C for 5 h. The white powder was designated as
MCM-41.
Lithium (LiNO3), as an active species was incorporated into the
framework of MCM-41 through wet impregnation technique.
Further, the effect of synthesis conditions i.e. calcination tempera-
tures and metal loading amounts were investigated. The resultant
S. Arora, V. Gosu, U.K.A. Kumar et al. Journal of Cleaner Production 295 (2021) 126437

catalysts were labeled as Li/MCM-41 (x%, T), where x and T repre- pore volume.
sent lithium loading amount and calcination temperature in
C,
respectively. 2.4. Transesterification reaction

2.3. Catalyst characterization
Fourier transforms infrared (FT-IR) spectrometer (PerkinElmer,
Massachusetts, US) was used to analyze the functional group pre-
sent on the sample. FT-IR was conducted over the range of
4000 cm1 to 400 cm1. Catalyst samples were finely grounded
with KBr and pressed in a hydraulic press to obtain a homogeneous
transparent pallet. The morphology of catalyst samples were
investigated using field emission scanning electron microscope
(FE-SEM) (Nova Nano FE-SEM 450 (FEI), Thermo Fisher Scientific,
Massachusetts, US). The samples were mounted on aluminum
stubs using double-sided tape, coated with gold on Q150T ES
(Quorum Technologies Ltd, England) sputter coater and examined
under Nova Nano FE-SEM to determine their microscopic
morphology at an accelerating voltage of 40 kV. X-ray diffraction is
an analytical technique used to determine the crystal structure and
crystalline phases. The small-angle and wide-angle XRD patterns of
the samples were recorded on the X’Pert Powder XRD (PANalytical
X’Pert Pro, B.V., Netherlands) system. The uniformly powdered
samples were placed on sample holder, and the analysis was car-
ried out at operating condition of 40 kV and 40 mA using Cu Ka
radiation (l ¼ 1.540
). The small angle X-ray scattering was
measured in the range of 1.5
< 2q < 10
, whereas wide angle X-ray
Transesterification reaction of GLY and DMC was conducted in a
100 mL three-necked round-bottom flask equipped with a reflux
condenser. The whole system was placed in an oil bath kept on a
magnetic stirrer (5 MLH Plus, REMI, India) to maintain the desired
temperature and stirring speed. In a typical experiment, 5.02 g
(0.05 mol) of GLY and 14.41 g (0.16 mol) of DMC were charged into
the reactor and allowed to heat until the desired temperature was
attained. After achieving the desired reaction temperature, 0.2 g of
catalyst was added into the flask to initiate the reaction, and the
reaction was preceded for 3 h. After the completion of the reaction,
the catalyst was separated from the mixture using centrifugation
(Re12C plus, REMI, India). Subsequently, the product was filtered
and analyzed by gas chromatography (Trace 1310, Thermofisher
Scientific, USA) equipped with a capillary column (Quadrex, 007e5,
30 m  0.25 mm X 0.25 mm) and flame ionization detector. The
injector and detector temperatures were kept at 290
C and 325
C.
The oven temperature was initialized at 70
C and elevated to
300
C at the rate of 20
C/min. Pyridine was used as an internal
standard for the quantification of GLY and GLC. All the calculations
were done assuming GLY as a limiting reactant. GLC’s yield, con-
version of GLY, the selectivity of GLC, and turn over frequency of
catalyst (TOF) were determined using the following Eqs. (1)e(4):

Initial moles of GLY in feed  Unreacted moles of GLY

Conversion of GLY ¼ X 100 (1)
Initial moles of GLY in feed

Moles of GLC produced

Yield of GLC ¼ X 100 (2)
Initial moles of GLY in feed

Yield of GLC
Selectivity of GLC ¼ X 100 (3)
Conversion of GLY

Initial moles of GLY X Conversion of GLY X Molecular weight of GLY

TOF ¼ (4)
100 X Mass of catalyst used for the reaction X Reaction time

diffraction was performed in the range of 10
< 2q < 80
. PAN-
alytical software was used to analyze the XRD data. Thermal sta-
bilities of the samples were investigated through the
thermogravimetric analyzer (TGA). TGA of samples were performed
2.5. Kinetic study
on PerkinElmer simultaneous thermal analyzer (STA 6000).
Approximately, 5 mg of sample was placed in an alumina crucible
The obtained values of concentration of the species were used to
and heated at a rate of 20
C/min under the flow of nitrogen from
minimize the least-squares objective function (Eq. (5)). The opti-
ambient temperature to 900
C. The basic strength of the catalyst
mization stopped when the constraints satisfied within the limits
was determined through a Hammett indicator method. Phenol-
of the constraint tolerance. The concentration-time profiles at
phthalein (H_ ¼ 9.3), 2, 4-dinitroaniline (H_ ¼ 15), and 4-
constant temperatures were obtained by using stiff integrators-
nitroaniline (H_ ¼ 18.4) were adopted as indicators to measure
ODE15s from the MATLAB.
the basic strength of synthesized catalysts. The adsorption-
The principle for the evaluation of the rate constants is that, the
desorption isotherms of MCM-41 and Li/MCM-41(5%, 450) was
values of the sum of square error (SSE), root mean square error
obtained on Micromeritics (3Flex Version 4.01, USA). All the sam-
(RMSE), and chi-square (c2) should tend to zero (Eqs. (7)e(9))
ples were degassed at 350
C for 4 h before analysis. The total
(Hamid et al., 2012), whereas the value of the coefficient of deter-
surface area of the samples was calculated utilizing Brunauer-
mination should tend to one (Eq. (6)). This criterion was further
Emmet-Teller (BET) method and Barrett-Joyner-Halen (BJH)
used to authenticate the fit of the model with the estimated
method was employed to determine average pore diameter and
parameters.
3
S. Arora, V. Gosu, U.K.A. Kumar et al. Journal of Cleaner Production 295 (2021) 126437

# water molecule and surface silanols bonds (Sikarwar et al., 2018).

N 
X 2  2
i i i i The bands at 1085 cm1 and 808 cm1 were assigned to condensed
f¼ CGLY;exp  CGLY;pred þ CGLC;exp  CGLC;pred (5)
asymmetric and symmetric silica network (SieOeSi)
i¼1
(Kaiprommarat et al., 2016). The absorption band’s existence at
459 cm1 was due to SieO- bending vibration, indicating the for-
N 
P 2
1 Cexp;j;i  Cpred;j;i mation of hexagonal mesoporous silica structure (Sikarwar et al.,
N
j¼1 2018; Shu et al., 2015; Zhou et al., 2015; Yang et al., 2015). The
R2 ¼ 1  (6)
N 
P 2 band at 1384 cm1 was ascribed to NeO in NO2 3 , while the peak at
1 Cexp;j;i  Ci
N 1641 cm1 was endorsed to the OeH group (Song et al., 2017). Both
j¼1
peaks were strengthened with increase in Li species concentration
(Fig. 1b-f). In contrast, the reflection of the peak at 1384 cm1
2
decreased considerably in the spectra of regenerated catalyst
1 XN  
SSE ¼ C  Cpred;j;i (7) (Fig. 1g) due to leaching of active metal (Li) from the channels of
N j¼1 exp;j;i
MCM-41. The escape of Li metal from the catalyst or the deposition
of GLY molecule in the pores of catalyst reduced the catalytic ac-
N  0:5 tivity towards GLC formation; this was further advocated from the
1 X
RMSE ¼ Cpred;j;i  Cexp;j;i (8) reusability study.
N j¼1
Powder small-angle x-ray scattering (SAXS) of Li/MCM-41 (x%,
450) catalysts at different lithium loaded amount is represented in
N 
P 2 Fig. 2A. In SAXS profile of MCM-41 (Fig. 2A (a)), three characteristic
Cexp;j;i  Cpred;j;i peaks were observed corresponding to plane (1 0 0), (1 1 0), and (2
c2 ¼
j¼1
(9) 0 0) at 2q ¼ 2.0021
, 2.4241
and 4.3932
respectively. The reflec-
Nn tion of a broad peak at 2q ¼ 2.0021
displayed the typical feature of
the hexagonal structure of MCM-41, which also justifies the highly-
where, Cexp,j,i is the experimental concentration of component i at
ordered mesoporous structure of silica (Wu et al., 2015). The (1 0 0)
jth number of the experiment data. Cpred,j,i is the simulated con-
plane’s reflection shifted towards a higher scattering angle
centration of component i at jth number of simulated data. The
(2q ¼ 2.04
) when the Li ions were introduced into the MCM-41
number of the experimental data is represented by N, while n in-
framework. This could be ascribed to the reduction in inter-
dicates the number of proposed kinetic model constants.
planar d spacing at (1 0 0) plane from 45.70 Å to 41.27 Å
(Sikarwar et al., 2018). As a result shortening of a long-range hex-
3. Results and discussion agonal array of mesoporous MCM-41 was observed and it may be
beacuse of the accumulation of non-framework lithium species in
3.1. Characterization the structure of MCM-41, as compared to bare support material
(Fig. 2A (b-f)). This behavior might be addressed to the local
The FT-IR spectrum of prepared catalysts are presented in Fig. 1. distortion of pores of MCM-41 at higher loading of lithium species
In Fig. 1a, broadband at 3433 cm1 was assigned to the SieOH (Tang and Hong, 2016). Additionally, it was also observed that the
surface hydroxyl group due to physically intruded water molecule diffraction intensities of peaks at 2.4241
and 4.3932
decreased
(Sikarwar et al., 2018). The spectra of MCM-41 exhibited clear gradually with an increase in Li-ion loading and finally disappeared
doublet at 2926 and 2855 cm1 corresponding to symmetric CeH in the SAXS spectra of 10% Li loaded MCM-41.
vibrations and asymmetric CH2 vibration of adhered surfactant The wide-angle XRD profiles of bare MCM-41 and Li-ion incor-
molecule (Deshmane et al., 2015). A peak at 1641 cm1 was porated MCM-41, calcined at 450
C are presented in Fig. 2B. The
ascribed to the SieOH group formed due to the freely absorbed XRD pattern of bare MCM-41 depicted a broad hump at 2q ¼ 22
,
justifies its amorphous nature. No peaks were detected corre-
sponding to lithium oxide and/or lithium nitrate in Li/MCM-41 (1%
and 3%, 450) catalyst, as seen in Fig. 2B (b, c). This may be due to
complete dispersion of lithium species into the pores of MCM-41.
Since lithium species possess lower atomic weight and reflect
weak scattering which was dominated by higher intensities of silica
framework (Song et al., 2017). However, lithium silicates and
lithium oxide phases were detected in XRD profiles bearing lithium
weight percentage greater than three weight percentage. The
characteristic peaks of Li2SiO3 were identified at 18.93
and 26.99

(Pan et al., 2017; Ortiz-Landeros et al., 2011), while the reflection of
the peak at 33.04
was associated with the development of Li2O
phases formed due to the decomposition of lithium nitrate in the
structure of MCM-41 (Puna et al., 2014). The peaks intensified with
an increase in lithium metal (5 wt% - 10 wt%) in the assembly of
MCM-41 as shown in Fig. 2B (d-f), whereas no peaks of lithium
were observed in the XRD profile of reused catalyst (Fig. 2B (g)).
The morphological images of MCM-41 and Li/MCM-41 (5%, 450)
are displayed in Fig. 3. It can be clearly observed that the meso-
structured MCM-41 exhibited evenly dispersed spherical shaped
Fig. 1. FT-IR spectra of (a) MCM-41; (b) Li/MCM-41 (1%, 450); (c) Li/MCM-41 (3%, 450);
monolithic particles (Zhou et al., 2015; Dhokte et al., 2011; Liu et al.,
(d) Li/MCM-41 (5%, 450); (e) Li/MCM-41 (7%, 450); (f) Li/MCM-41 (10%, 450); (g) Li/ 2014). Li incorporated MCM-41 shows the uniform film on the
MCM-41 (5%, 450) regenerated to 4th cycle. spherical shaped particle due to multilayer dispersion of active
4
S. Arora, V. Gosu, U.K.A. Kumar et al. Journal of Cleaner Production 295 (2021) 126437

Fig. 2. XRD Pattern of (a) MCM-41; (b)Li/MCM-41 (1%, 450); (c) Li/MCM-41 (3%, 450); (d) Li/MCM-41 (5%, 450), (e) Li/MCM-41 (7%, 450), (f) Li/MCM-41 (10%, 450), (g) Li-MCM-41
(5%, 450) regenerated to 4th cycle.

Fig. 3. SEM micrographs of (A) MCM-41 (B) Li/MCM-41 (5%,450).

Fig. 4. TGA profile and N2 adsorption-desorption isotherms of MCM-41 and Li/MCM-41 (5%, 450).

metal in the MCM-41 framework (Fig. 3B), elucidating that the Thermal stability of MCM-41 and Li/MCM-41(5%, 450) was
active metal was successfully amalgamated into the framework of investigated through TGA analysis, and their profiles are presented
MCM-41 (Parida and Rath, 2009). in Fig. 4A. The Thermogram of MCM-41 displayed a total weight

5
S. Arora, V. Gosu, U.K.A. Kumar et al.
loss of 7% in the temperature ranging from room temperature to
900
C. However, the initial weight loss (below 200
C) was due to
loss of water molecules from the pores of MCM-41, while the
further losses (above 200
C) were due to the leftover surfactant
decomposition in the pores of MCM-41. However, Li incorporated
MCM-41 shows significant weight loss in the region 250e550
C
due to the decomposition of nitrate spices from lithium nitrate
precursor (Liu et al., 2014; Parida et al., 2009).
The N2 adsorption-desorption isotherms of MCM-41 and Li/
MCM-41 (5%, 450) are shown in Fig. 4B. It was noticed that the
isotherms depict the characteristic feature of type IV hysteresis
loop according to International Union of Pure and Applied Chemistry
(IUPAC) standards, with capillary condensation in the relative
pressure range (P/P0) of 0.3e0.5. This trend particularly signifies
that the formed material exhibit typical mesoporous nature. The
BET surface area, pore volume and average pore diameter of bare
MCM-41 was 861 m2/g, 0.577 cm3/g and 25.431 Å, respectively.
After incorporation of active metal in MCM-41 framework, the
surface area and pore volume declined significantly to 254 m2/g
and 0.330 cm3/g, respectively. The decrease in BET surface area and
pore volume might be due to the incorporation of lithium species in
the framework of MCM-41, and the scattering of metal oxides on
the boundaries of mesoporous channels. However, the average pore
diameter increased to 62.022 Å owing to the formation of metal
oxide bond on the wall of MCM-41 channels (Xu et al., 2017).
3.2. Screening of active metal for GLY transesterification
A series of catalysts were prepared by impregnating different
active metals on MCM-41 for the transesterification of GLY with
DMC. All the experiments were conducted thrice, and confidence
interval were calculated at a ¼ 0.05. Table 1 demonstrates the
catalytic performance of different active metal loaded on MCM-41.
Bare MCM-41 exhibited only 5% conversion of GLY. The GLY con-
version (10.56 ± 1.95%) was improved slightly when Ni/MCM-41
(5%, 450) was used as a catalyst. Further, the conversion of GLY
increased to 20.30 ± 1.53% with Mg/MCM-41 (5%, 450) catalyst. The
conversion of GLY influenced by different active metals including K,
La, and Ce was also determined. The improvement in trans-
esterification reaction was due to the development of basic sites by
incorporation of active metal in MCM-41 framework, which is
essential for GLY transesterification reaction. Nonetheless, lithium
species incorporated MCM-41 catalyst showed a better catalytic
activity. The conversion of GLY increased significantly to 75%
because lithium species provides strong basic sites due to its strong
ion size effect. Therefore, Li/MCM-41 was used as a potential
catalyst for the transesterification reaction.
3.3. Preparation parameters of catalyst
3.3.1. Effect of lithium loaded amount
The influence of active metal loading was investigated by varying
different weight percentage of lithium active species on MCM-41,
Table 1
Effect of various catalysts on conversion of GLY and yield of GLC with an interval of confidence at a ¼ 0.05.
Entry Catalyst Conversion of GLY
1 MCM-41 4.00
2 Ni/MCM-41 10.56
3 Mg/MCM-41 20.30
4 K/MCM-41 40.31
5 La/MCM-41 43.14
6 Ce/MCM-41 54.79
7 K/Mg-MCM-41 68.51
8 Li/MCM-41 75.00
Journal of Cleaner Production 295 (2021) 126437
calcined at 450
C, and the results depicted in Fig. 5A. As observed
from the experiments, the conversion of GLY escalated (35.24 ± 2.16
to 99.00 ± 3.15%) with an increase of active metal loading (1e5 wt%)
on MCM-41 (as shown in Table 2). The conversion of GLY increased
due to the improvement of the basicity of catalysts with lithium
species incorporation. However, when Li loading increased beyond
5 wt%, a slight decrease in yield and conversion of GLC and GLY was
observed, respectively. However, the highest total basicity,
11.0 mmol/g (shown in Table 2), was acquired for 10 wt% Li/MCM-41,
calcined at 450
C. The catalytic activity was declined even at higher
loading (>5 wt%), due to multilayer dispersion of lithium species on
MCM-41 framework takes place which leads to decrease in surface
area by blocking of pores of MCM-41 channel or agglomeration of
active metal takes places. Furthermore, the turn over frequency
(TOF) was calculated to investigate the catalyst performance. With
an increase in active metal loading amount from 1 wt% to 5 wt%, the
TOF value increased from 2.94 ± 0.40 h1 to 8.25 ± 0.45 h1. Further
increase of active species on MCM-41 (>5 wt%), TOF value decreased.
This is due to an in-accessibility of the reactant to the active sites
because of multilayer dispersion or may be due to pore blocking.
Kumar et al. (2015) investigated the GLC synthesis by using CaLa
catalyst: TOF was estimated in a range of 5.15e5.78 h1. Hence, it is
logical to accept that a moderate amount of basic sites are required to
obtain the maximum GLC yield. Therefore, 5 wt% of Li loading was
chosen as an optimum active metal loading on MCM-41 for the
synthesis of GLC.
3.3.2. Effect of calcination temperature
The impact of calcination temperature on basicity of the catalyst
surface was investigated with varying calcination temperature
from 250
C to 550
C. Fig. 5B and Table 2 showed the yield of GLC
and conversion of GLY. As expected, GLY conversion increased from
60 ± 2.58% to 99 ± 3.15% with an increase in a calcination tem-
perature from 250
C to 450
C. At lower temperature calcined
catalyst showed a considerably lower performance (60% conversion
of GLY). This may be due to an insufficient amount of basic sites
formation at a lower calcination temperature. Since at lower
calcination temperature, active metal precursor i.e. lithium nitrate,
may not decompose into lithium oxide species. Besides, TGA
investigation also confirmed that lithium nitrate species on MCM-
41 partially decomposed below 450
C, thereby there was less
formation of LiO2 as an oxide layer, which contributes to the basic
sites on the catalyst surface, and enhances higher yield and con-
version. It was perceived that the yield of GLC and conversion of
GLY was declined when a further increase of calcination tempera-
ture from 450
C to 550
C. The observed negative trend may be due
to the sintering of active metal in MCM-41 framework at higher
calcination temperature leads to the destruction of basic sites of the
catalyst (Wang et al., 2015). Hence, calcination temperature plays a
vital role in obtaining the maximum yield and selectivity of GLC. In
this study, 5 wt% Li/MCM-41 calcined at 450
C was adopted as an
optimized catalyst for investigating the effect of reaction variables
on transesterification reaction.
Interval of confidence Yield of GLC Interval of confidence
0.27 3.20 0.19
1.95 9.79 1.37
1.53 15.93 1.05
2.01 31.48 1.85
1.49 39.03 1.25
3.01 52.45 2.96
1.56 65.37 1.87
2.23 73.97 2.10
6
S. Arora, V. Gosu, U.K.A. Kumar et al. Journal of Cleaner Production 295 (2021) 126437

Fig. 5. Effect of catalyst preparation parameters on yield and conversion (A): DMC-to-GLY molar ratio: 3, temperature: 90
C, catalyst amount: 4 wt% of Li/MCM-41 (5%, 450),
reaction time: 3 h; (B): DMC-to-GLY molar ratio: 3, temperature: 90
C, catalyst amount: 4 wt% of Li/MCM-41 (5%, 450), reaction time: 3 h.

Table 2
Textural properties of Li/MCM-41.

Catalyst Basicity (mmol/g) Basic strength(H_) Yield of GLC Interval of confidenceb Conversion of GLY Interval of Confidenceb

MCM-41 5.70 H_  7.2 3.20 0.19 4.00 0.27

Li/MCM-41 (1%, 450) 6.80 7.2 H_ 9.8 35.08 2.89 35.24 2.16
Li/MCM-41 (3%, 450) 8.50 7.2  H_ 9.8 60.90 2.13 61.39 3.05
Li/MCM-41 (5%, 450) 9.80 9.8 H_ 15 93.13 3.11 99.00 3.15
Li/MCM-41 (7%, 450) 10.70 9.8 H_ 15 74.13 1.78 80.42 2.35
Li/MCM-41 (10%, 450) 11.00 15 H_ 18 49.29 2.23 53.94 2.61
Li/MCM-41 (5%, 250) 8.00 7.2  H_ 9.8 59.04 1.95 60.06 2.58
Li/MCM-41 (5%, 350) 8.60 9.8 H_ 15 74.48 3.00 75.28 2.36
Li/MCM-41 (5%, 550) 9.10 9.8 H_ 15 79.91 1.05 88.48 2.11
a
Li/MCM-41 (5%, 450) 8.90 9.8 H_ 15 80.85 2.63 81.49 3.11
a
Regenerated for four runs.
b
Interval of confidence at a ¼ 0.05.

3.4. Effect of reaction parameters on transesterification of GLY into
GLC
3.4.1. Effect of catalyst dosage
The effect of catalyst dose (with reference to GLY weight) was
investigated by varying catalyst (5 wt% Li/MCM-41) dose from 1 to
6 wt%, and the results are depicted in Fig. 6A. It observed that GLY
conversion and GLC yield increased from 45.74 ± 3.15 to 99 ± 1.89%
and 45.34 ± 2.01% to 93.14 ± 2.52%, respectively, on intensifying the
catalyst dosage from 1 to 4 wt% (based on GLY mass). This behavior
was anticipated due to the increase in active sites concentration to
initiate the transesterification reaction. However, with the further
increase of catalyst dose from 4 wt% to 6 wt% of GLY mass, GLC yield
was declined from 93.14 ± 2.52% to 85.37 ± 1.25%, but the con-
version of GLY was not influenced significantly. At higher catalyst
mass, the available excess active basic sites may participate in
transesterification reaction further leading to decarboxylation of
formed GLC into glycidol, due to which, the yield and selectivity of
GLC was declined (Algoufi et al., 2017; Liu et al., 2014). Hence the
catalyst dose of 4 wt% based on GLY mass was chosen as an effective
dosage for further studies.
3.4.2. Effect of DMC-to-GLY molar ratio
Transesterification reaction strongly influenced by reactant
concentration, in order to investigate the effect of reactant con-
centration, the study was conducted by varying molar ratio of
DMC-to-GLY. Since the transesterification reaction is reversible in
nature, so to shift the equilibrium towards the forward direction
(GLC production), an excess amount of DMC is required. The effect
7
of DMC-to-GLY molar ratio was investigated and results are
depicted in Fig. 6B. At an equal molar ratio of DMC-to-GLY (1:1),
only 50.40 ± 1.61% of GLY conversion, and 49.40 ± 1.13% of GLC yield
were observed. Further increase of DMC-to-GLY molar ratio (3:1),
the GLC yield increased and maximized to 93.14 ± 2.52%. It was
observed that when DMC-to-GLY molar ratio was increased from
3:1 to 5:1, the yield of GLC slightly declined from 93.14 ± 2.52% to
86.30 ± 1.58%. At a higher molar ratio of DMC-to-GLY (>3:1), the
catalyst concentration may be diluted due to the addition of a large
quantity of reactant molecule (DMC) into the reaction mixture,
which leads to a decrease in contact rate between the catalyst and
the reactants (Okoye et al., 2017). At a greater molar ratio of DMC-
to-GLY, the TOF also decreased from 8.25 ± 0.45 h1 to 8.00 ± 0.32
h1. Hence, a DMC-to-GLY molar ratio of 3:1 was chosen as an
optimum molar ratio for further studies.
3.4.3. Effect of reaction temperature
Influence of reaction temperature on the transesterification re-
action is displayed in Fig. 6C. It is a well-known fact that the vis-
cosity of reactant decreases with an increase in reaction
temperature: hence the miscibility of GLY and DMC increases. The
rate of collision between the reactant molecules increases, which
enhances the rate of transesterification reaction towards GLC for-
mation (Algoufi et al., 2017; Okoye et al., 2017; Malyaadri et al.,
2011). When the reaction temperature was raised from 60 to
90
C, the GLC yield increased from 34.18 ± 1.47% to 93.14 ± 2.52%.
Correspondingly, the TOF value of catalyst risen from 2.92 ± 0.26 to
8.25 h1 ± 0.45. This can be attributed to the well-established fact
that the reaction rate increases with an increase in reaction
S. Arora, V. Gosu, U.K.A. Kumar et al. Journal of Cleaner Production 295 (2021) 126437

Fig. 6. Effect of reaction influencing parameters on GLY conversion and GLC yield (A): DMC-to-GLY molar ratio: 3, temperature: 90
C, reaction time: 3 h; (B): Catalyst dosage 4 wt %
of Li/MCM-41 (5%, 450), temperature: 90
C, reaction time: 3 h; (C): Catalyst dosage 4 wt % of Li/MCM-41 (5%, 450), DMC-to-GLY molar ratio: 3, reaction time: 3 h; (D): DMC-to-GLY
molar ratio: 3; reaction temperature: 90
C; catalyst dosage: 4 wt% of Li/MCM-41 (5%, 450); reaction time: 3 h.

temperature (Yadav and Chandan, 2014). However, with a further catalyst’s basicity was dropped from 9.80 mmol/g to 8.90 mmol/g
increase in reaction temperature from 90 to 100
C, a slight (Table 2) after the 4th cycle. The spent catalyst must be regenerated
decrease in the GLC yield was observed. However, the GLY con- with a suitable technique to get a sufficient quantity of basic sites
version was not affected by increasing the reaction temperature on the catalyst surface. However, the present study was not
beyond 100
C. This may be due to decarboxylation of formed GLC explored any regeneration technique but asses the reusability of
into glycidol owing to ring-opening of GLC structure on available the catalyst. Besides, the absence of lithium species was observed in
vacant primary sites into other by-products. Thus, the reaction the spent catalyst XRD profile (Figs. 1g and Fig 2B (g)). It may be
temperature of 90
C has chosen as an adequate temperature for another possible reason for the decrease in catalyst activity because
tailoring the transesterification reaction of GLY into GLC. of the leaching of active sites from the MCM-41 framework. The
reasons, as mentioned earlier, are in good agreement with the
available literature. Malhotra and Ali (2018) investigated lithium-
3.5. Reusability study
doped ceria supported SBA-15 for biodiesel production, the yield
of biodiesel was declined from 98% to 60% after six successive re-
The reusability of the catalyst is an important criterion to eval-
cycles and the same trend was observed due to leaching of active
uate the catalyst stability and its industrial feasibility. The reus-
metal on the surface of catalyst during catalytic reaction.
ability of Li/MCM-41 (5%, 450) was carried out by separating the
catalyst from the product mixture through centrifugation. The
separated catalyst was washed with ethanol, dried in an oven at
100
C for 5 h, and reused for further transesterification reaction.
3.6. Green matrix study
The reusability has been carried before the next subsequent run.
After the 4th cycle, the GLC yield and GLY conversion reduced
The atom economy, environmental factor (E-factor), and process
significantly from 93.14 ± 2.52% to 81 ± 3.01% and 99 ± 1.89% to
mass intensity (PMI) were calculated to assess the efficiency and
85.49 ± 1.85%, respectively, as shown in Fig. 6D.
environmental performance of mesoporous Li/MCM-41 (5%, 450)
The reason behind gradual loss in the catalytic activity has been
catalyst. The atom economy, E-factor, and PMI of the process were
investigated using FTIR, Hammet titration, and XRD analysis for
determined using Eqs. (10)e(12), respectively.
spent catalyst after the 4th cycle. The spent catalyst FTIR spectra
revealed that the intensity of peak at 1384 cm1 (NeO in NO2 3 ) was
Molecular mass of GLC
decreased and because of a decline in the basic site, which is highly Atom economy ¼ X 100 (10)
responsible for reduction in yield and conversion. The aforemen- Molecular mass of reactants
tioned hypothesis was also confirmed with Hammet titration. The
8
S. Arora, V. Gosu, U.K.A. Kumar et al.
Total waste ðgÞ
E  factor ¼
Product ðgÞ
where, total waste ¼ total mass of material used in the process-total
mass of product formed
Total mass used in the process ðgÞ
PMI ¼
Mass of final product ðgÞ
During transesterification of GLY into GLC, methanol is the only
by-product produced, which could serve as a feedstock for bio-
diesel production. The catalyst’s reusability was not considered
during the calculation of the atom economy, environmental factor
(E-factor), and process mass intensity (PMI) values. Lower the
environmental factor (E-factor) and process mass intensity (PMI)
values, the lesser the waste generation during the process. The
atom economy of the process was calculated as 0.64, whereas the E-
factor and PMI values of GLC synthesis were determined as 1.16 and
2.16, respectively, which demonstrate the less waste generation
during the process. Pradhan and Sharma (2020) reported an E-
factor of 0.074 for GLC synthesis using NiMgOx catalyst by elimi-
nating solvent reusability and recyclability of catalyst. Olivares et al.
(2020) had observed E-factor of 0.5322 for GLC synthesis using an
apatite-like catalyst. Roy et al. (2020) reported E-factor of 0.153
(waste cooking oil methyl ester) and 0.157 (castor oil methyl ester)
for biodiesel production using potassium modified ceria oxide
catalysts.
3.7. Kinetic study
Transesterification of GLY with DMC into GLC was carried out in
the presence of Li/MCM-41 (5%, 450) as a catalyst in a heteroge-
neous reaction system. The Langmuir-Hinshelwood-Hougen-
Watson (LHHW) model was adopted to formulate the probable
dual-site mechanism assuming that the rate of external and inter-
nal mass transfer is very high as compared to the surface reaction
rate route (Das and Mohanty, 2019). Hence the model was devel-
oped based on adsorption, surface reaction, and desorption steps.
The heterogeneous reaction precedes in three major steps via (1)
adsorption of reactant species on to the active sites of catalyst
surface from bulk phase (2) surface reaction of GLY and DMC onto
the active sites to produce GLC (3) desorption of product molecules
(GLC and methanol) from the active sites of catalyst into bulk phase.
Eq. (13) was developed from the model, and its elaborated deri-
vation is provided in SI.
dCGLY k0 CGLY 0 present study also investigated the feasibility of mesoporous het-
 ¼ 2 ; k
dt CGLC CM
1 þ K1 CGLY þ K2 CDMC þ K3 þ K4
¼ CDMC kSR K1 K2 Ct2
The kinetic parameters (equilibrium constants and apparent
reaction rate constant) of Eq. (13) were optimized using MATLAB
R2015b. The experimental and simulated concentrations at varying
temperatures were compared, and the plots are presented in Fig. 7.
The simulation was performed at a constant density system, i.e. at
constant temperature and pressure. The ODE solver function was
called by the main ‘fmincon’ optimization function during the
execution. The values of reaction rate constants were constrained
within positive real numbers.
Table 3 summarizes the statistical parameters of the kinetic
model. The small value of SSE, RMSE, c2, and relatively higher
Journal of Cleaner Production 295 (2021) 126437
values of R2 (greater than 0.9499) suggest that the model best fits
with experimental data. Table 4 represents the equilibrium con-
(11)
stants and apparent reaction rate constant evaluated at different
temperatures (60e100
C). It was seen that the values of apparent
reaction rate constants increased with an increase of reaction
temperature, and facilitated the concentration of GLY and GLC to
attain equilibrium at a faster rate. However, a negligible difference
(12) in apparent reaction rate constants was seen at 90
C and 100
C.
The acquired values of apparent rate constants were used to eval-
uate the activation energy reaction using the Arrhenius equation
(shown in Table 4). Similar findings were reported by pankajakshan
et al. (Pankajakshan et al., 2018) for the acetylation of GLY on
sulfated alumina catalyst. A plot of ln (kˈ) vs 1/T used to calculate
the activation energy of 53.77 ± 3.26 kJ/mol (Fig. S1). Similar, re-
sults were reported in the literature for the transesterification of
GLY into GLC. Devi et al. (2018), Esteban et al. (2015), and Yadav and
Chandan (2014) reported the activation energies and are follows
39.2 kJ/mol using Ti/SBA-15 catalyst; 28.4 ± 1.5 kJ/mol using po-
tassium methoxide catalyst; and 53.77 52.50 kJ/mol employing
calcined hydrotalcite supported hexagonal silica catalyst,
respectively.
3.8. Comprehensive analysis of GLC synthesis routes
Various synthesis routes have been explored to synthesize GLC
from GLY using various carbonate sources, including carbon diox-
ide, urea, phosgene, and dialkyl carbonate. The yield and conver-
sion of the different processes were tabulated in Table 5. Liu et al.
(2018) investigated the catalytic conversion of GLY with CO2 into
GC using Ce0$98Zr0$02O2, and it was observed a 36.3% GLC yield and
40.90% GLY conversion. Further, this process requires continuous
water removal to eliminate thermodynamic limitations and ach-
ieve a higher yield. Chaves and Silva (2019) investigated the urea
route to convert GLY into GLC using Sn(OH)2. It obtained 87%
conversion, but these processes need to operate under vacuum to
remove formed ammonia as a by-product. Besides, researchers
explored the one-pot green synthesis route i.e., transesterification
of glycerol with dialkyl carbonate using homogeneous and het-
erogeneous catalysts. Ochoa-Go
mez et al. (2012) investigated GLC
synthesis using the transesterification of GLY with DMC in the
presence of a homogeneous catalyst. It was found that 98% GLC
yield and 99% GLY conversion. However, homogeneous catalysts
provide an excellent catalytic activity interms of yield and con-
version, but recovery and regeneration are major constraints. Devi
et al. (2018) examined the one-pot green synthesis route using a
heterogeneous catalyst. It was found that the Ti-SBA-15 catalyst has
potential catalytic activity with 82% yield and 94% conversion. The
erogeneous catalyst (Li/MCM-41) for a one-pot green synthesis
route for GC synthesis. It was observed that the present catalyst has
a potential catalytic activity with a high yield (93.14 ± 2.52%) and
(13)
conversion (99 ± 1.89%).
4. Conclusion
Transesterification of GLY with DMC was successfully investi-
gated using the heterogeneous mesoporous catalyst. 5 wt% Li/
MCM-41, calcined at 450
C illustrates the better basic sites for
transesterification of GLY to GLC. Li/MCM-41 catalyst showed stable
thermal stability up to 900
C. With the incorporation of active
metal species (5% Li) in the MCM-41 framework, the surface area
(861 m2/g to 254 m2/g) and pore volume (0.577 cm3/g to 0.330 cm3/
g) was declined but basic sites were increased (5.70 mmol/g to
9
S. Arora, V. Gosu, U.K.A. Kumar et al. Journal of Cleaner Production 295 (2021) 126437

Fig. 7. Comparison plots of the simulated and experimental concentration of GLY and GLC at different reaction temperatures: (a) 60
C, (b) 70
C, (c) 80
C, (d) 90
C, (e) 100
C at
DMC-to-GLC molar ratio of 3, and 4 wt % of catalyst dosage using Li/MCM-41 (5%, 450) catalyst.

Table 3
Statistical analysis for the mathematical parameter estimation for GLY and GLC.

Component 60
C 70
C 80
C 90
C 100
C
09 07 08 07
GLY SSE 3.51  10 8.65  10 9.71  10 2.70  10 5.11  1007
RMSE 3.34  1004 6.17  1004 9.45  1004 5.84  1004 6.19  1004
c2 9.37  1009 2.30  1006 2.59  1007 7.18  1007 1.36  1006
R2 0.9624 0.9499 0.9503 0.9819 0.9786
GLC SSE 4.00  1009 8.71  1007 9.82  1008 2.74  1007 5.14  1007
RMSE 2.97  1004 6.06  1004 7.48  1004 6.17  1004 8.11  1004
c2 1.07  1008 2.31  1006 2.62  1007 7.31  1007 1.37  1006
R2 0.9680 0.9608 0.9651 0.9766 0.9560

9.80 mmol/g). Langmuir-Hinshelwood-Hougen-Watson kinetic research work confirms that GLC production from GLY through
model was adopted to explain the reaction kinetics of Li/MCM-41 transesterification reaction using lithium loaded MCM-41 and has a
(5%, 450) catalyst in the transesterification reaction. The present great potential to increase the economy of the biodiesel plant.

10
 S. Arora, V. Gosu, U.K.A. Kumar et al.
Table 4
Fitted values of equilibrium constants, rate of GLY depletion and activation energy with an interval of confidence at a ¼ 0.05.

Temperature (
C) 60
C Interval of 70
C Interval of 80
C Interval of 90
C Interval of 100
C Interval of Activation energy Ea Interval of
confidence confidence confidence confidence confidence (kJ/mol) confidence

Equilibrium constant K1 11.358 1.389 11.025 1.648 11.109 2.035 11.226 2.035 10.966 1.235 53.77 3.26
K1 11.541 1.856 11.319 2.365 10.897 1.638 11.678 1.638 11.271 1.022
a
kˈˈ 0.123 0.019 0.294 0.031 0.443 0.042 0.955 0.042 0.909 0.025
K1 10.854 2.056 10.487 1.563 10.709 3.014 10.324 3.014 10.065 1.012
K1 10.399 1.956 10.057 2.635 10.071 1.032 9.585 1.032 9.383 1.145
Rate of reaction -rGLY 1.83  1005 5.08  1007 2.19  1005 1.15  1006 2.51  1005 1.38  1006 7.01  1006 1.38  1006 7.62  1006 6.46  1007
(mol/L.min)
a
Apparent reaction rate constant (min1).
11

Table 5
Comprehensive analysis of GLY synthesis routes.

S. Reaction system Catalyst Catalyst dosage Temperature Time Pressure Yield of GLC Conversion of GLY Reference


No. C (h) (%) (%)

1. GLY þ CO2 Ce0$98Zr0$02O2 0.52 g catalyst 150 5 CO2 (3.0 MPa) 36.3 40.9 Liu et al. (2018)
2 GLY þ urea Sn(OH)2 4.9 mol% Sn 140 4 e e 87 Chaves and Da Silva
(2019)
3 GLY þ CO CuCl2 0.60 mmol 130 3e4 O2 (0.7 MPa) and CO e >92 Casiello et al. (2014)
(3.3 MPa
4 GLY þ Ethylene Quaternary salt ionic liquid immobilized on MCM41 0.1 g 80 1.5 e e 94 Cho et al. (2010)
carbonate (RNX-MCM41)
5 GLY þ DMC Triethylamine (homogeneous catalyst) TEA/glycerol molar 90 2.5 e 98 99 Ochoa-Go
mez et al.
ratio ¼ 0.1 (2012)

Journal of Cleaner Production 295 (2021) 126437

6 GLY þ DMC Ti-SBA-15 5.5 wt% 87.5 2 e 82 94 Devi et al. (2018)
7 GLY þ DMC Li/MCM-41 (5%, 450) 4 wt% based on GLY wt. 90 3 e 93.14 99 Present work
S. Arora, V. Gosu, U.K.A. Kumar et al.
CRediT authorship contribution statement
Shivali Arora: Methodology, Investigation, Writing e original
draft. Vijayalakshmi Gosu: Validation, Writing e review & editing.
U.K. Arun Kumar: Writing e review & editing. Verraboina Sub-
baramaiah: Conceptualization, Supervision, Writing e review &
editing, Project administration.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgments
The author’s grateful to the Department of Science and Tech-
nology (DST), Government of India for financial support under the
Early Career Research (ECR) Award scheme (ECR/2015/000085,
Dated 20.08.2016). Ms. Shivali Arora thanks Ministry of Human
Resource Development (MHRD), Government of India for the award
of a fellowship.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jclepro.2021.126437.
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