Biomass Conversion and Biorefinery

https://doi.org/10.1007/s13399-022-02540-y

REVIEW ARTICLE

A review on direct carboxylation of glycerol waste to glycerol

carbonate and its applications
Najaa Rozulan1 · Siti Atikah Halim2 · Nurul Razali1 · Su Shiung Lam3

Received: 2 November 2021 / Revised: 1 March 2022 / Accepted: 2 March 2022

© The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2022

Abstract
Concern over global warming, energy demand and the economic impact of exploiting fuel reserves have driven the com-
mercial interest and action to produce biodiesel as the substitute for fossil fuel. Biodiesel produced via the transesterification
reaction of triglyceride with methanol is known to be a promising renewable and clean energy. However, increase in the
biodiesel production leads to undesirable generation of glycerol waste, considering that 1 kg of glycerol can be generated
as by-product from every 10 kg of biodiesel production. Utilising and upgrading of glycerol waste into high-value chemi-
cal can reduce the waste volume and increase the market value of the glycerol itself and the sustainability of the biodiesel
production towards achieving circular economy. Direct carboxylation of glycerol waste is an emerging alternative to utilise
and convert the abundance and easily available waste into glycerol carbonate (GC). GC has various applications as solvent,
additives and chemical intermediate. It has properties such as high boiling and melting point, low volatility and biode-
gradable. This review aims to reveal the impact of both homo- and heterogeneous catalysts employed and their impact on
glycerol conversion and selectivity to GC. Also, the impact of dehydrating agents, solvents and other reaction conditions is
thoroughly discussed, aiming to provide insights into further development of the carboxylation of glycerol to GC. The use
and application of GC are also reviewed.

Keywords  Biodiesel · Glycerol · Glycerol carbonate · Carboxylation of glycerol

1 Introduction Monteiro et al. (2018) stated that the biodiesel production

Biodiesel produced via transesterification of triglyceride
with methanol is known to be a promising renewable,
environmental friendly and clean energy [1]. Increase in the
number of biodiesel plant worldwide has made the biodiesel
industry one of the most rapidly growing industries, but
it also produces glycerol as one of the by-product [2].
* Nurul Razali
nrazali@umt.edu.my
1
Faculty of Ocean Engineering Technology and Informatics,
Universiti Malaysia Terengganu, 21030 Kuala Nerus,
Terengganu, Malaysia
2 as acrolein, lactic acid, bioethanol, biobutanol and the many
Malaysian Institute of Chemical and Bioengineering
Technology, Universiti Kuala Lumpur, Branch Campus,
78000 Alor Gajah, Melaka, Malaysia
3
Pyrolysis Technology Research Group, Higher Institution
Centre of Excellence (HICoE), Institute of Tropical
Aquaculture and Fisheries (AKUATROP), Universiti
Malaysia Terengganu, 21030 Kuala Nerus, Terengganu,
Malaysia
is expected to rise by 4.5% annually reaching 41 ­Mm3
in 2022 [3]. This biodiesel production has contributed
about 67% of glycerol production as a waste reaching
approximately 2.7 billion in 2020, where every 1 kg of
glycerol is produced for every 10 kg of biodiesel [4, 5]. The
abundance of crude glycerol creates concerns related to the
disposal of the glycerol waste which would otherwise lead
to environmental problem [6, 7]. The rising of biodiesel
industry is proportional to the increase in glycerol supply
that resulted in reduction of the market price for glycerol
from 25 cents/lbs in 2004 to about 8 cents/lbs in 2011
[8, 9]. Therefore, utilisation of glycerol waste to produce
glycerol carbonate (GC) or any value-added products such
more uses of GC in pharmaceutical and cosmetic industries
is seen as a great opportunity to resolve the problem [10-
[11]12]. GC, also known as 4-hydroxymethyl-1,3-dioxolan-
2-one, is a five-membered ring carbonate that can be formed
from glycerol [10]. GC consisting of two functional group
(hydroxyl group and 2-oxo-1,3-dioxolan group) as shown

13
Vol.:(0123456789)

Fig. 1  Classification and structure of GC
in Fig.1, 2 and 3 has gained attention from the industry. It
has a variety of applications in commercial sector due to
its wide range of reactivity and it may be used to valorise
glycerol, which is becoming easily available as by-product
generated from the production of biodiesel [11].
OH
HO OH CO2
Fig. 2  Carboxylation of glycerol with C
­ O2 to produce GC and water
Fig. 3  The reaction scheme of glycerol and C
­ O2 over ­La2O2CO3 [28]
13
Biomass Conversion and Biorefinery
GC can be synthesised from numerous techniques such
as reaction with carbon monoxide (CO), phosgene, urea,
carbon dioxide (­ CO2) and organic carbonates (e.g. dimethyl
carbonate (DMC)). However, the use of phosgene and CO
possessed problems in terms of their toxicity and difficulty
to carry out the reaction [12]. Therefore, the preference is
given to the reaction that is considered to be a green syn-
thesis reaction or using green catalyst in order to reduce the
environmental problems and for safer chemical usage. Direct
carboxylation of glycerol has been proposed to be an envi-
ronmentally friendly technique for the conversion to GC as
it uses a safer chemical, simpler reaction, least toxic reaction
of by-product as well as the use of readily available and low-
cost materials. Glycerol has a large potential in the chemical
industry and the combination with C ­ O2 to produce GC is an
attraction to the scientists and chemists for commercial and
environmental concern as shown in Fig. 4 and 5.
1.1 GC
The increasing production of biolubricants and biofuels
from biomass as well as the existing industrial processes
generating glycerol have produced large quantities of glyc-
erol exceeding the current demand. The consequence for this
excessive production is the risk of glycerol accumulated as
a waste posing environmental concern [10]. Ochoa-Gómez
et al. (2012) have listed several basic sets of conditions for
industrial manufacturing of GC [13]. The first requirement
is that the catalyst used is preferred to be from low-cost
material, easily separable and recyclable. Next, a simple
O
O H2 O
HO
Biomass Conversion and Biorefinery
OH
CO2 HO
glycerol
OH CH3COO
OOCH3C OH HO OH
1-monoacetin 2-monoacetin
OH CH3COO
OOCH3C OOCH3 OOCH3C OH
1,3-diacetin 1,2-diacetin
Fig. 4  Reaction pathway between glycerol and ­CO2 in the presence of acetonitrile. Adapted from Zhang and He [30]; copyright (2021) Elsevier
separation and purification method is required, eliminating
or reducing the use of solvents with high conversion and
selectivity. Shorter reaction time is good and lastly the reac-
tion must be safe from the start, which means any highly
flammable and toxic chemicals should be avoided. Thus,
in this review, we discuss the routes to produce GC, focus-
ing on the GC synthesis by direct reaction of glycerol with
­CO2, advantage and disadvantages of the conversion route
to synthesise GC, the reaction pathway of GC and the effect
of certain parameters on carboxylation of glycerol as well
as direct and indirect application of the glycerol. This study
also summarised the progress of direct carboxylation of
glycerol using various catalysts, solvents and dehydrating
agents from earlier publications until recent study.
2 Main routes for GC synthesis
The conversion of glycerol waste into valuable product is
promising ways to reduce the waste. GC is a bifunctional
chemical that can be used as a solvent, surfactant or in the
manufacture of polyurethanes and polycarbonates [14].
Hence, there are four routes for the conversion of glycerol
into GC as discussed below focusing on the carboxylation
of glycerol.
2.1 Direct reaction of glycerol with ­CO2
Figure 4 shows the reaction of glycerol with ­CO2. This reac-
tion can be considered as green reaction theoretically as the
reaction only produces GC and water. However, this reac-
tion is thermodynamically limited and has small equilibrium
constant that makes this reaction undesirable for industrial
O
catalyst
OH O O H2O
OH
glycerol carbonate CH3CN
acetonitrile
CH3COOH CH3CONH2
acetic acid acetamide
NH3
production [15]. Besides, the C ­ O2 is very stable resulting in
a low glycerol conversion rate, and the conversion of ­CO2
necessitates a highly reactive catalyst and a large amount
of energy [14, 16]. ­CO2 is thermodynamically stable and
found in oxidised form (G∆f0 = -394 kJ/mol) which must be
taken into consideration when utilising ­CO2 as a chemical
feedstock. [17–19]. Although the reaction is limited by ther-
modynamics, high yield of GC can be attained by employing
suitable dehydrating agents to remove water [19]. Then, only
a commercial system to utilising both glycerol and ­CO2 to
GC can be developed.
The first publication related to carboxylation of glycerol
was reported by Vieville et al. (1998) using zeolites and ion
exchange resins as catalysts under condition of supercriti-
cal ­CO2 [20]. The catalyst used was zeolite Purosiv, zeolite
13X and Amberlyst A26 where these catalysts successfully
enhanced the reaction of adsorption of glycerol onto the
solid catalyst and the ethylene carbonate was dissolved in a
supercritical ­CO2 (SC-CO2). High yield of GC was achieved
that contributed to 24.8% and 32.1% using zeolites 13X and
Purosiv zeolite, respectively.
George et al. (2009) reported that reaction between glyc-
erol and ­CO2 is totally selective to 1,2-GC at 120 °C using
­CO2 pressure of 13.8 MPa. The result showed that the GC
yield was increased from 30 to 35% when 13X zeolite was
employed. 13X zeolite was used to trap the water produced
from the reaction. The inclusion of methanol as a solvent
between glycerol and supercritical C ­ O2 ­(scCO2) ensures
total solubility, allowing for a more homogeneous reaction
and improving the yield [21]. Since then, more study on car-
boxylation of glycerol using both homo- and heterogeneous
catalyst have been reported employing oxides, organic bases
or Rh complexes [22].
13
 Biomass Conversion and Biorefinery

O O
A

OH

H2O
OH OH NH2
CO2 NH3
HO OH HO O O HO O O

OH OH
CO2 H2O
H2O

O O

O OH O NH B1
HO OH
OH

H2O NH3

O
O
O OH
O NH B2
HO NH2
H2O HO

Fig. 5  Reaction pathway of glycerol and ­CO2 to GC (A) and 4-HMO (B1 and B2). Adapted from Razali et al. [5]

Ezhova et al. (2012) reported the use of rhodium com-
plexes with phosphine ligands. The selectivity towards GC
is 100% under condition of 140 °C and pressure of 40 atm
but the yield was only 0.24%. This shows that the reaction
is thermodynamically limited [22]. The development of
heterogeneous catalyst has been investigated and is prefer-
able than homogeneous catalyst due to the ease of catalyst
recovery [10]. The progress of the reaction of glycerol
and ­CO2 has been updated with the use of catalyst such as
hydrotalcites modified with halogen anion [23], ­CeO2 [24]
and ­La2O2CO3/ZnO [25].
Li et al. (2013) first reported the reaction of glycerol and
­ O2 using lanthanum doped with ZnO in the addition of ace-
C
tonitrile [26]. The reaction condition was 170 °C, pressure
of 40 bars for 12 h. La:Zn molar ratio was highly respon-
sible for the higher conversion of glycerol and yield of GC
at optimum ratio of 1:4. 30.3% of glycerol conversion and
14.3% and 47.3% yield and selectivity to GC were recorded.
Mono- and diacetin were also detected as the by-products of
this reaction aside from GC as shown in Fig. 6.
Carboxylation of glycerol using halogen anion such
as ­F−, ­Cl− and ­Br− modified with Zn/Al/La derived from

13
Biomass Conversion and Biorefinery
Fig. 6  The possible reaction
pathway of C­ O2 and PO to O
synthesised GC. Reproduced CO2
from Ma et al. [60] with permis-
sion from the Royal Society of PO
Chemistry.
O O
O O
O O
PC
hydrotalcites as catalyst has also been reported with C ­ l− giv-
ing good result with a glycerol conversion of 35.5%, selec-
tivity of 45.2% and yield of 16% [23]. Similar study was
conducted by Li et al. (2014) using Li-, Mg- and Zr-mod-
ified Zn/Al/La catalysts using a co-precipitation method.
The result showed that 39.5% of glycerol conversion and
18.7% of GC yield were recorded under optimum condition
of 170 °C, ­CO2 pressure 6 MPa for 14 h with molar ratio
of Zn/Al/La = 4:1:1. The catalytic reaction has been greatly
affected by the halogen anion, large specific surface area,
high surface content of Zn as well as the high binding energy
of Zn atom while the number of basic sites may affect the
selectivity towards GC.
Zhang & He (2014) employed copper (Cu) supported
on lanthanum oxide to synthesise GC in the presence of
acetonitrile that acts as water trapping agents. At reaction
condition of 150 °C, pressure of 70 bars for 12 h, the glyc-
erol conversion was 33.4%, and the selectivity of GC and
monoacetin was 45.4% and 52.9%, respectively, while the
yield of GC was 14.3%. Monoacetin was the only by-product
detected; and due to hydrolysis of acetonitrile, the reaction
between glycerol and acetic acid happened. The reaction
would not take place in the absence of acetonitrile because
acetonitrile has the ability to shift the reaction to thermo-
dynamic equilibrium and leads to the formation of GC by
reacting with water [27]. Further research have been pub-
lished that employed Cu-based catalyst supported on acid
and basic, acid sites only, basic sites only or no acid or basic
site support [28]. The study showed that the formation of
glycerol into GC and monoacetin was affected by the particle
size of Cu and acid and basic sites of the catalysts. The big-
ger the Cu particle size, the slower the reaction rate. Lewis
base catalyst favoured the GC formation, while Lewis acid
catalyst promoted the monoacetin formed.
Li et al. (2014) studied the carboxylation of glycerol using
solid catalyst derived from Zn/Al/La/M (M = Li, Mg, Zr)
OH
HO OH
Glycerol
OH
HO
step 2 OH
PG
GC
hydrotalcites. The best result obtained for glycerol conver-
sion, selectivity and yield towards GC is 35.7%, 42.2% and
15.1%, respectively, under reaction condition of 170 °C,
4 MPa for 12 h using Zn:La:Al with molar ratio of 4:1:1
introduced with lithium [29]. Liu et al. (2015) reported the
use of ­CeO2 as the catalyst together with 2-cyanopyridine
and dimethyl formamide (DMF) that acts as water trapping
agent and also as solvent in his study. The result of 78.9%
of GC yield has been observed in 5 h at 150 °C and 4 MPa.
After 5 recycling cycles, the catalyst can be regenerated
without losing any activity by calcination at 400 °C for 5 h
[24].
Ozorio et al. (2015) has employed metal-impregnated
zeolite Y catalyst that was treated with aqueous solution of
Ag(NO3), Zn(NO3) and ­SnCl2. The catalyst was then tested
in carboxylation of glycerol reaction at 180 °C, 100 bar for
3 h in the absence of solvent. Only 5.8% of GC yield were
observed [30]. Recently, carboxylation of crude glycerol has
been reported for the first time using L
­ a2O3 as catalyst with
adiponitrile as dehydrating agents [5]. Selectivity of crude
glycerol was greatly reduced to 2.3% when compared to
refined glycerol, which had a selectivity of 17%. The conver-
sion was 54% while the yield was only 1.2%. With the excep-
tion of methanol, which exhibited the positive impact on the
measured selectivity, which increased from 17 to 22%, other
contaminants in the crude glycerol influenced the catalytic
process thus reducing the yield of GC. However, impuri-
ties such as water, methyl palmitate and sodium methoxide
could play the role of reducing the selectivity towards GC,
instead of enhancing the production of 4-(hydroxymethyl)
oxazolidin-2-one.
Li et  al. (2020) [31] have prepared a series of
­La2O2CO3–ZnO catalyst using hydrothermal method in a
photo-thermal condition to convert glycerol and ­CO2 to glyc-
erol carbonate. The study shows that in the thermally driven
reaction, the number of basic sites of ­La2O2CO3–ZnO was
13

discovered to be a crucial determinant. These were observed
to increase as the ­La2O2CO3 content increased. Under light
irradiation condition using 20% ­La2O2CO3–ZnO catalyst
with optimum reaction of 150 °C, 5.5 MPa for 6 h gives the
highest GC yield of 6.1% which doubled the result compared
to the yield obtained under thermally driven reaction (3.3%).
In the recent study by Hu et al. (2021) [32] introduced the
use of inorganic dehydrating agents to improve the conver-
sion, yield and selectivity of the reaction between glycerol
and ­CO2 using La/ZIF-8 catalyst. The study shows that La/
ZIF-8 catalyst exhibits higher catalytic activity compared to
La/modified ZnO attributed to large specific surface area and
also strengthened Lewis acidity and basicity. The conver-
sion, yield and selectivity reached 36.6%, 34.8% and 95%,
respectively, using ­MgCO3 as the water trapping agent in
the presence of 5La/ZIF-8 under condition of 150 °C, 7 bar
for 15 h.
Li et al., (2016) studied the recyclability of CeO2 catalyst
[33]. This study was carried out in the presence of 2-cyano-
pyridine and dimethyl formamide (DMF) that acts as dehy-
drating agent and solvent, respectively. The regeneration of
the used catalyst was performed by calcination at 400 °C for
5 h. The result shows that the GC and 2-picolinamide yield
are almost similar as fresh ­CeO2 catalyst even after 5 times
of usage. (GC yield for fresh C ­ eO2 catalyst and used catalyst
are 29.4% and 28.0%, respectively). The catalyst leaching
was tested using ICP and proved that the leaching was below
the detection limit. This suggested that the microstructure of
the catalyst was stable and the active sites of the catalyst can
be regenerated using simple calcination procedure.
Another study conducted by Liu et al., (2018) investigated
the recyclability of C ­ eO2-ZrO2 as catalyst in the presence
of 2-cyanopyridine and DMF [34]. The used catalyst was
washed with ethanol for 3 times and dried at 110 °C for
24 h (without calcination). The used ­CeO2-ZrO2 catalyst
performed much lower catalytic activity. The conversion
of glycerol and GC yield over used C ­ eO2-ZrO2 was only
14.2% and 9.7% in contrast to the reaction with fresh catalyst
(40.9% and 36.3% of glycerol conversion and GC yield).
Then, the used catalyst was also pre-treated and calcined at
400 °C for 5 h in air. The glycerol conversion and GC yield
were 41.4% and 36.3%, respectively. The recyclability of
catalyst is possible and can be achieved. The active sites of
used catalyst (for, e.g. ­CeO2 and C­ eO2-ZrO2) can be regener-
ated through calcination process.
The list of catalyst used for this reaction is summarised
in Table 1. By reviewing the studies on direct carboxylation
of glycerol, it is found that homogeneous and heterogeneous
catalyst can be used to obtain GC in this reaction. Homoge-
neous catalyst shows promising result in the conversion and
selectivity towards GC in direct carboxylation of glycerol
under mild conditions. However, this homogeneous catalyst
becomes less appealing due to the separation and recycling
13
Biomass Conversion and Biorefinery
challenges in addition with the complexities of the corrosion
of reactors [35]. Thus, the recent study has shifted the use of
homogeneous catalyst to heterogeneous catalyst due to the
ease of catalyst recovery and separation and the most of the
reaction does not require the use of solvents. Basic hetero-
geneous catalyst will favour the formation of GC while the
acid sites of the catalyst favour the formation of acetins that
also caused the reduction of catalytic activity. The addition
of water trapping agents such as adiponitrile, acetonitrile,
­MgCO3 and 2-cyanopyridine also have been used in the
study for the water elimination and shifts the equilibrium in
favour of the products side. There is still need to find new
approaches to develop more efficient and low-cost catalyst
systems in the presence of dehydrating agents to get good
GC yields. For the catalyst design, future perspectives may
focus on the preparation of cheaper, stable and catalyst
with high selectivity. Designing efficient catalyst systems
that are reusable and efficient in the direct carboxylation of
crude glycerol with C ­ O2 is crucial, so these catalysts can
be employed in industry [35]. In order to enhance electron
donation for the ­CO2 and glycerol reaction, the intensity of
Lewis acidity and basicity of the catalysts could be modi-
fied and optimised. Furthermore, searching for more effi-
cient organic or inorganic basic dehydrating agents for water
removal should be considered. The previous studies have
focused on valorisation of pure glycerol but there is one
more attractive approach which is the conversion of crude
glycerol from the biodiesel industry to eliminate the needs
for expensive purification methods.
2.2 Transcarbonation of glycerol with phosgene
The benefits of this reaction are that it is simple and gives
good results in terms of the yield [11, 39]. However, some
of the significant disadvantages is that this process has a low
atom economy and phosgene is regarded as highly poison-
ous and corrosive in nature [29, 40]. Several nations have
outlawed its usage in the industry for safety reasons, making
this method not widely employed due to its negative effect
[14].
2.3 Reaction of glycerol with urea
There are many studies conducted for the synthesis of GC
and urea. Yoo & Mouloungui (2003) studied the reaction
of glycerol with urea using heterogeneous zinc catalysts
such as zinc sulphate, zinc organosulphate and zinc ion
exchange resins. The result showed that calcined ­ZnSO4
is the best catalyst to be used in the reaction with urea at
150 °C with a pressure of 4 kPa for 2 h reaction, yielding
86% of GC. However, this reaction is a homogeneous reac-
tion as ZnSO4 salt is soluble in glycerol [42]. The previous
study of dual-catalyst over Zn/mixed oxide catalyst has
Biomass Conversion and Biorefinery

Table 1  Summarisation of comparative study of catalyst with different reaction parameters

Catalyst Dehydrating Solvent Reaction parameters Glycerol Selectivity Yield Ref
agent conversion (%) (%)
Temp Time Pressure (%)
(°C) (hr) (MPa)

Heterogeneous catalyst
With solvent and dehydrating agent
Ce0.98Zr0.02O2 2-cyanopyridine DMF 150 5 4 40.9 - 36.3 [34]
CeO2 (different 2-cyanopyridine DMF 150 5 4.0 - - 20.8 [24]
preparation
methods)
Without solvent and dehydrating agent
2%Au/ZnWO4- - - 150 - 8.0 - 100 10.6 [36]
ZnO (Using photo-
thermal catalysis)
DVB-based polymer 100 4 2 82 - 81.0 [15]
ZnO, SnO, ­Fe2O3, - - 180 12 15.0 - - 8.1 [37]
La2O3
NaY, AgY, ZnY, - - 180 3 10.0 5.8 [30]
SnY
With solvent, without dehydrating agent
20%La2O2CO3–ZnO - DMF 150 6 5.5 6.9 - 6.1 [31]
(Using light irradiation)
50%La2O2CO3–ZnO - DMF 150 6 5.5 4.5 - 4.1 [31]
(Using thermal-driven condition)
ZnWO4–ZnO - DMF 150 6 5.0 - 100 6.5 [38]
(10%W–Zn)
Without solvent, with dehydrating agent
5La/ZIF-8 Acetonitrile - 150 15 0.7 46.5 75 35.3 [32]
5La/ZIF-8 MgCO3 - 150 15 0.7 36.6 92 34.8 [32]
ZIF-67 Acetonitrile - 210 12 0.3 32 92 29 [8]
Biochar Acetonitrile - 160 22 3.0 - - 0.048 [39]
and biochar ash mol/L
La2O3 Adiponitrile - 160 18 4.5 54 2.3 1.2 [5]
La2O2CO3 /ZnO Acetonitrile - 170 12 4.0 24.3 59.2 14.4 [25]
CeO2 2-cyanopyridine - 180 - 15.0 - - 18.7 [40]
Zn/Al/La–Cl Acetonitrile - 170 12 4.0 35.5 45.2 16.0 [23]
Cu-based Acetonitrile - 150 3 7.0 8.9 29.3 - [28]
Catalyst
2.3 wt.% Cu/La2O3 Acetonitrile - 150 12 7.0 33.4 45.4 14.3 [27]
Zn/Al/La–Li Acetonitrile - 170 12 4.0 35.7 42.2 15.1 [29]
La2O2CO3–ZnO Acetonitrile - 170 12 4.0 30.3 47.3 14.3 [26]
Homogeneous catalyst
With solvent and dehydrating agent
n-Bu2SnO 13X (soda) MeOH 120 4 13.8 - 100 35 [21]
zeolite
Without solvent and dehydrating agent
n-Bu2Sn(OMe)2 - - 180 15 5.0 - - 7 [41]
With solvent, without dehydrating agent
RhCl3 + ­PPh3 + KI - MeOH 140 59 5.0 0.24 100 0.24 [22]

not been extended to Zn/mixed oxide catalyst that com- study conducted by Nguyen-phu et al. (2020), use ZnMeO
prised of other metal component that are beneficial to the mixed oxide catalyst with two ratios which is high and
development of Zn/mixed oxide catalysts [43, 44]. The low ZnMe2O ratio. The result showed that Zn-rich mixed

13

oxide gave better result in glycerol conversion and GC
yield compared to that shown by Zn-poor mixed oxide
[45]. Another recent study has utilised ­SnO2 with ­MoO3
and ­WO 3 catalyst using fusion and wet impregnation
method for the production of GC. High conversion and
selectivity towards GC were shown upon the use of M ­ oO3/
SnO 2 catalyst due to their smaller crystallite size, high
surface area and has more acidic sites [46]. The advan-
tages of using this route for the production of GC are that
it is low-cost material, readily available, and the catalyst
is easily recoverable and recyclable [45, 47]. However, in
order to eliminate the ammonia formed during glycerolysis
of urea and push the equilibrium closer to completion, the
reaction must be done in a vacuum condition or must be
done at a reduced pressure [7, 46].
2.4 Transesterification with DMC
Transesterification between glycerol and DMC is one of the
favourable methods for the production of GC as DMC has
high reactivity as well as less time of reaction and higher
product obtained [39, 40]. The catalyst used for this reaction
can be either homo- or heterogeneous catalyst. Based on the
previous study, homogeneous catalyst that has been investi-
gated is ­K2CO3, NaOH and ­H2SO4 [48, 49], while example
of heterogeneous catalyst is CaO-based catalyst [50] and
Mg/ZnO [51].
In the study by Bai et al. (2013), NaOH/γ-Al2O3 catalyst
demonstrated an excellent catalytic activity with the glyc-
erol conversion and selectivity to GC reached up to 97.9%
and 99.0%, respectively. This shows that homogeneous cata-
lyst enhanced the reaction activity. Meanwhile, LiCl/CaO
showed good catalyst for the transesterification reaction as
the ­Li2O2 species has moderate basic site which contributed
to the great catalytic reaction of the transesterification pro-
cess in the study [50]. The highest yield obtained for GC is
94.19% under reaction condition of temperature at 65 °C for
1 h with CaO loaded with 10% of LiCl. Pradhan & Sharma
(2021) used Mg/ZnO base catalyst in their study using wet
impregnation method, where 98.4% of glycerol conver-
sion and 96.7% GC yield were obtained. The research also
studied the optimisation condition of temperature, molar
ratio of DMC/Glycerol, catalyst loading and reaction time.
However, this route also has some disadvantages which are,
when using homogeneous catalyst and enzymes, there were
difficulties in separating the catalyst and corrosion of reac-
tors and pipelines [52]. This had then shifted the favour to
the use of heterogeneous catalyst but the problem was that
several steps were needed for the recovery and regeneration
of the catalyst which needed washings with methanol for a
few times, drying above 100 °C for 2 to 5 h before it can be
reused again [53].
13
Biomass Conversion and Biorefinery
3 Reaction mechanism and pathways
on the carboxylation of glycerol
Many researchers have proposed reaction mechanism or reac-
tion pathway specifically according to their study to find the
understanding of how the reaction happens between glycerol
and ­CO2 as reactant molecule to produce GC either in the pres-
ence of catalyst, solvent and dehydrating agent. The details of
each reaction pathway are discussed in the subsection below.
3.1 Reaction pathway of carboxylation of glycerol
over acetonitrile
Zhang & He (2014a) showed the reaction pathway for the
between glycerol and ­CO2 in the presence of acetonitrile
(dehydrating agent) and promotes the formation of GC and
water (Fig. 7). Water and acetonitrile were generated, which
were subsequently changed into acetamide, and then further
reaction between acetamide and water formed acetic acid.
Monoacetin and diacetin can still be produced by esterifying
glycerol with acetic acid. However, in their study, there is no
sign of acetic acid in the reaction products, implying that the
acetic acid produced during the reaction has been transformed
to mono- and diacetin [27].
3.2 Reaction route of producing GC from glycerol
and ­CO2 using adiponitrile
Razali et al. (2019) showed the reaction route of converting
glycerol and C ­ O2 to GC and 4-(hydroxymethyl)oxazolidin-
2-one ­(C4H7NO3, 4-HMO) using adiponitrile as dehydrating
agent as shown in Fig. 8. 4-HMO is proposed to be produced
by the reaction of glycerol, ­CO2 and ­NH3 derived from adi-
pamide decomposition. C ­ O2 reacts with the glycerol’s main
and secondary alcohol groups to form 2,3-hydroxypropyl
hydrogen carbonate and [2-hydroxy-1-(hydroxymethyl)ethyl]
hydrogen carbonate. After reacting with ­NH3, these species
generate (2-amino-3-hydroxy-propyl) hydrogen carbonate
and [1-(aminomethyl)-2-hydroxy-ethyl] hydrogen carbonate,
respectively. The generation of 4-HMO isomers (B1 and B2)
follows the cyclisation of these intermediates. By-products
such as acetamide have been detected in prior studies of GC
synthesis using nitrogen-containing dehydrating agents, but
the generation of 4-HMO has never been reported [26].
3.3 Reaction pathway of conversion of glycerol
and ­CO2 using propylene oxide as coupling
agent
Ma et al. (2012) are the first to use potassium iodide (KI)
and propylene oxide (PO) as a coupling agent, thus overcom-
ing the thermodynamic limitation. In the coupling reaction
Biomass Conversion and Biorefinery
N N
N O N O
C HO
O O
O H+
NH
H+
O O
N N
O O
O
HO HO
H+
O HO
O
O
NH2 O
N
OH
Fig. 7  The proposed mechanism for GC formation from glycerol and C
­ O2 over 2-cyanopyridine. Reproduced from Su et al. [42] with permission
from the Royal Society of Chemistry
involving PO, glycerol and C ­ O2 includes cycloaddition of
­CO2 with PO (step 1, Fig. 9) followed by transesterification
of glycerol with propylene carbonate. Then, the GC and pro-
pylene glycol (PG) were synthesised (step 2, Fig. 9). Using
KI as the homogeneous catalyst, it is possible to transform
glycerol and ­CO2 simultaneously via the coupled reaction.
Another study conducted by Song et al. (2018) introduced
functionalised heterogeneous catalyst using imidazole-based
ionic liquids into DVB-based polymers, showing good per-
formance of ionic liquid groups in the coupling reaction of
PO and C ­ O2. The reaction with prepared PDVB-(vIm-BuBr)
catalyst demonstrated stability throughout the reaction and
enhanced catalytic activity even after five cycles of reaction
[54].
3.4 Reaction route for the reaction glycerol and ­CO2
over 2‑cyanopyridine
Su et al. (2017) have proven that, without the use of any
metal catalysts or additives, the addition of 2-cyanopyridine
together with glycerol and C ­ O2 can produce GC gradually.
The possible reaction route is shown in Fig. 10. ­CO2 was
activated by 2-cyanopyridine to form a five-membered ring
intermediate, which then interacted with glycerol to form
N N
O O OH
N N
OH
O
H+
NH N
H+
O
H+ OH
N
O O OH
OH
GC. 2-cyanopyridine are formed into 2-picolinamide during
the process, which functioned as a dehydrating reagent as
well as a promoter in the current carbonylation reaction [40].
3.5 Catalytic path for carboxylation of glycerol
using methanol as solvent
Figure 1 depicts a possible catalytic route using methanol as
a solvent in the study by George et al., (2009). The finding
suggested that dibutyltin(IV)oxide (nBu2SnO) was activated
by methanol and undergoes continuous removal of water to
overcome thermodynamic limitation to obtain higher yield.
Then, it reacts with glycerol to produce tin–glycerol complex
and underwent C ­ O2 insertion leading to GC via 7-membered
key intermediate tin–glycerolcarbonate complex. Methanol
exchange was followed by a rearrangement inside this inter-
mediate executing product to complete the cycle [21].
3.6 Catalytic path for carboxylation of glycerol
in dimethyl formamide (DMF) solvent
The study conducted by Liu & He (2018) proposed a reac-
tion pathway for the carboxylation of glycerol with ­CO2
using xW–Zn composite in DMF solvent (Fig. 2). Glycerol
13
 Biomass Conversion and Biorefinery

2 MeOH H2O OH
R
Sn OH
O
R
1 OH
R OMe
2 MeOH
Sn
O R OMe
2
O

R
OH O
Sn
H2O R
O 4

OH
2 MeOH

O
CO2
O
R
Sn
R O
O

5
R= nBu
OH

Fig. 8  Possible catalytic route for GC formation. Adapted from George et al. [23]; copyright (2021) Elsevier

and ­CO2 were first activated as zinc glycerolate and bridged
bidentate carbonate species, respectively, on an xW–Zn
catalyst. The zinc glycerolate was subsequently introduced
into the activated bridged bidentate carbonate, generating a
seven-member ring cyclic carbonate. This cyclic carbonate
was then formed GC by intramolecular nucleophilic attack
of the alkoxy oxygen atom on the carbonyl carbon atom [38].
3.7 Plausible mechanism of glycerol and ­CO2
over 2‑cyanopyridine and DMF solvent
Liu et  al. (2018c) presented a mechanism for the
carboxylation of glycerol over 2-cyanopyridine and
DMF, where ­CeO2-based has been employed as catalyst
(Fig. 10). The OH group of glycerol was initially absorbed
on the Lewis basic site ­(Ce 4+ ). Cerium glyceroxide
species was formed and the ­CO2 was activated as cheating
bidentate carbonate species. Following that, ring esters
with seven-membered were synthesised by directly
introducing activated ­CO2 into the cerium alkoxides, as
well as the formation of the adsorbed water molecules. The
2-cyanopyridine was transformed to 2-picolinamide. Then,
GC was synthesised via an intramolecular nucleophilic
attack of the alkoxy group (next to Ce) on carbonyl carbon
atoms [34].

13
Biomass Conversion and Biorefinery

O HO OH

O O O O
Zn W Zn
O OH
HO O
O
O
O
Zn
O O C O
Zn

OH

H O O
O
O O O H
Zn W Zn
O
O O O O O
Zn W Zn O
O
O Zn
O O O
O Zn
HO O O
Zn
O O
Zn

O
O O
O O Zn
W Zn Zn
O
O O O
O O C

O
HO

Fig. 9  Possible catalytic route for GC formation from glycerol and ­CO2 in DMF employing ZnWO4–ZnO. Adapted from Liu and He [40]; copy-
right (2021) Elsevier

3.8 Proposed mechanism of glycerol and ­CO2
in the absence of dehydrating agents
and solvents
Figure 11 shows the proposed mechanism to synthesise GC
over zinc oxide as catalyst. The glycerol reacted with zinc
oxide surface to produce adsorbed alkoxide, which attacked
the ­CO2 molecule to produce a carboxylate intermediate.
The secondary hydroxyl of the glycerol might attack the
carboxyl group in the sequence, resulting in production of
cyclic carbonate [37].

13
 Biomass Conversion and Biorefinery

OH
HO OH
O O O O
HO O O
Ce Ce OH
Ce
Ce O
O
O H

O O
O O
O O
Ce OH
O
HO

N
OH H N
N O NH2
N
OH N H
N
Ce Ce Ce Ce O N
O O Ce Ce
H O
H

Fig. 10  Proposed mechanism of carboxylation of glycerol employing ­CeO2-based catalyst over 2-cyanopyridine in DMF. Adapted from Liu et al.
[36]; copyright (2021) Elsevier

4 Influence of reaction parameters decomposition of glycerol carbonate to occur where higher

on the direct carboxylation of glycerol
After reviewing papers and research regarding direct carbox-
ylation of glycerol, it is found that there are several factors
affecting the catalytic reaction to produce GC such as reac-
tion temperature, pressure and time. These factors affecting
the glycerol conversion, GC selectivity and yield have been
discussed in the subsequent sections.
4.1 Reaction temperature
Li et al. (2014) [29] in their study stated that the conver-
sion of glycerol and GC yield increase with the increase
in reaction temperature in the range of 150–170 °C. How-
ever, future increase in temperature leads to the decrease
in the GC yield which due to the significant decrease in
GC selectivity. In the case of higher temperature or in
the presence of amino groups, there is possibility for the
temperature leads to lower catalytic activity. Thus, in this
study, the optimum reaction temperature is at 170 °C.
Liu & He, (2018) [38] study the use of novel
­ZnWO4ZnO prepared by two different methods; conven-
tional hydrothermal and wet impregnation method in the
direct synthesis of glycerol and C­ O 2. The effect on the
reaction conditions was studied using 10%W–Zn cata-
lyst. The reaction temperature ranges between 110 °C and
190 °C. The yield of GC increased drastically from 0.6% to
6.5% with the increasing temperature of 110 °C to 150 °C
which suggested that the reaction of glycerol and ­CO 2
occur the most during this time interval. However, as the
reaction temperature goes higher from 170 °C to 190 °C,
the yield of GC decrease to 5.0% and 1.7%, respectively,
as the other by-products which is 3-(dimethylamino)-
1,2-propanediol that comes from glycerol reacting with
N,N-di-methyl formamide (solvent) was detected specifi-
cally in 190 °C.

13
Biomass Conversion and Biorefinery
Fig. 11  The proposed mecha-
nism to synthesised GC using
zinc oxide as catalyst. Adapted HO
from Ozorio and Mota [39] with
permission from the John Wiley
and Sons O
O
O OH
Zn
OH
HO
O
HO
O
O
O
Zn
Zn
Liu et al. (2016) investigated the catalytic temperature
ranging from 90  °C to 190  °C and discovered that the
best optimum temperature was 170 °C with the result of
GC yield boost drastically from 0.9% to 21.2%. As the
temperature been more than 170 °C, the material balance
of glycerol started to deteriorate due to the result of the
by-products formation reaction. The glycerol conversion at
lower temperature (90 °C) was only 4.5% and it improved
drastically at higher temperature of 170 °C contribute to
39.3% [27]. The rising of temperature from 110  °C to
170 °C led to higher GC selectivity contributed to 46.6%
but lower selectivity of monoacetin which significantly
decreased from 62.2% to 51.6%.
Zhang and He (2014) studied the influence of reac-
tion temperature between 90 °C and 170 °C and the result
indicated that higher temperature promotes more glycerol
carbonate formation under certain reaction conditions
[27]. The conversion of glycerol at reaction temperature
of 90 °C is the lowest contribute to 4.5% and gradually
increases when the reaction temperature goes up to 110 °C.
The selectivity towards GC was significantly increased
along with the rise in temperature. From temperature
110 °C to 170 °C, the conversion of glycerol and selectiv-
ity towards GC formation increased from 26.1% to 39.3%
and 37.2% to 46.6%, respectively. However, the trend for
monoacetin decreased with the increasing temperature.
This concludes that higher temperature enhances the for-
mation of GC in the study. Therefore, the optimisation of
OH
OH
H2O
HO
O
Zn
OH
O
O
Zn
Zn
CO2
O
O O OH
O
Zn
Zn OH
temperature is crucial to obtain higher GC yield and favour
the selectivity towards GC formation.
4.2 Reaction time
For the reaction time, the previous study recorded the range
of reaction time is between 1 and 24 h. Hu et al. (2021)
studied the reaction time between 3 and 12 h of reaction
employing ZIF-67 as the catalyst in direct synthesis of glyc-
erol and ­CO2. The result showed increasing pattern from 3 to
12 h which is 17% to 92% and 4% to 29% for selectivity and
yield of GC, respectively. Same trend was recorded for the
GC yield that increased from 4.6% to 16.8% as the reaction
time increased from 1 to 12 h [40]. However, the conversion
of glycerol after 6 h of reaction is almost the same. This
concludes that yield of GC increased with the increase in
reaction time.
In another study conducted by Li et al. (2014) conducted
the experiments within range period of time between 8
and 16 h of reaction. The study shows that there was rapid
increase in glycerol conversion and GC yield within 12 h
of reaction, however, the reaction had not improved after
14 h of reaction [29]. Similar result was observed in the
study by Ozorio and Mota (2017) which varies the reaction
time up to 24 h. The result shows that the yield of GC after
12 h of reaction is almost stagnant that can be attributed to
equilibrium conditions [37]. Li et al. (2014) conducted the
study which varies time reaction between 8 and 16 h. The
13

result shows from 8 to 12 h of reaction, the conversion of
glycerol and GC yield increase. As the time increases to
16 h, the conversion and GC yield have not improved which
proved that the reaction has approaching thermodynamic
equilibrium [29].
Liu and He (2018) [38] studied the influence of reac-
tion time on the catalytic activity between 1 and 20 h. As
the reaction time increases, the conversion of glycerol also
increased; however, the yield of GC was only increased from
1 to 5 h of reaction, but after 6 h of reaction time, the yield
is slightly decreased. This study concludes that prolonged
reaction time will facilitate the side reactions hence reduce
the selectivity towards GC formation [38].
4.3 Reaction pressure
Increasing ­CO2 pressure may improve the glycerol conver-
sion, yield and selectivity to GC as discussed in the study by
Li et al. (2014). The result showed that, from 2.0 to 6.0 MPa,
the conversion of glycerol increased from 27.3% to 39.5%
and yield of GC increased from 11.5% to 18.7% [29]. Under
optimum condition of 170 °C, 14 h and 6.0 MPa, the con-
version of glycerol and GC yield reached 39.5% and 18.7%,
respectively. Increase in ­CO2 pressure means higher concen-
tration of ­CO2 dissolved in the acetonitrile, thus promoting
the conversion of glycerol. Similar result was reported by
Liu and He (2018) [38] which studied the pressure range
between 0.6 and 6.0 MPa. The GC yield increase with the
increase in C ­ O2 pressure which the highest yield of GC
(7.5%) obtained at 6.0 MPa.
The study conducted by Su et al. (2017), set the ­CO2 pres-
sure between 4.0 and 20.0 MPa. The result for both glycerol
conversion and GC yield increased from 28.7% to 46.4%
and 6.8% to 17.8%, respectively. The formation of 2-pico-
linamide also increased with the increasing ­CO2 pressure
[40]. Meanwhile, the study using Cu/La2O3 catalyst varied
the ­CO2 pressure from 1.5 to 8.0 MPa and discovered that
both glycerol conversion and the selectivity to GC keep ris-
ing from 24.6% to 37.2% and 38.9% to 47.5%, respectively,
but, the selectivity to monoacetin decreased from 59.7% to
50.7% [27]. Ozorio and Mota (2017) conducted a study with
a higher ­CO2 pressure of 150 bar, reaction temperature of
180 °C for 12 h that gives the result of GC yield maximum
of 6.8%.
4.4 Reaction design
Reaction design is also one of most significant influence
on the catalytic reaction that affects the glycerol conversion
since the access to the active site of the catalyst is aggravated
[12]. There is more study was been done using a batch reac-
tor compared to fixed-bed reactor as the result for glycerol
conversion is much higher obtained using batch reactor [55].
13
Biomass Conversion and Biorefinery
However, there is not much information available for this
factor to be implemented in a large scale of GC production,
thus extensive research and study needs to be done to study
the best design configuration for industrial and commercial
purposes.
5 Applications of GC
Since 2007, GC has been commercialised under the name
of Glycerine Carbonate by the Huntsman Corporation. The
molecular structure of GC is slightly similar between ethyl-
ene and propylene carbonate as well as glycerol. However,
GC has higher density compared to ethylene and propylene
carbonate because of the presence of H-bonding with the
hydroxyl group of GC [11]. Other advantages of GC are
soluble in water, high boiling point, low toxicity, good bio-
degradability and has high flashing point [56]. Besides that,
GC is commonly recognised as a high boiling solvent, a gas
separation membrane component, a surfactant component
and also component of industrial coatings, polymers, deter-
gent, inks, paints, lubricants and electrolytes [1, 54, 55]. All
of these good properties of GC contributed to wide applica-
tion in the industry as shown in Fig. 12. Table 2 summarises
the properties of GC and pure glycerol.
5.1 Solvent
GC can be used as biobased solvent due to its advantages
such as low volatility, low toxicity and biodegradability [57].
GC also can substitute ionic liquid because it is inexpensive,
safe and being a renewably sourced co-solvent in acid-cata-
lysed dehydration of fructose and inulin to 5-hydroxy-meth-
ylfurfural [58]. The study by Benoit et al. (2010) showed that
approximately 90 wt% of ionic liquid can be replaced using
GC, thus reducing the environmental cost of traditional ionic
liquid-based processes [58].
5.2 Lithium and lithium‑ion batteries
When GC was properly employed in lithium-ion cells, GC
has the ability to create a solid electrolyte interface layer on
graphite anodes. Moreover, GC can improve cell longevity
by forming oligomers under proper condition and forming
electrode passivation layers. GC has high dielectric constant
compared to other carbonate solvents used in lithium cell
electrolyte, making it a better lithium solvation [11].
5.3 Cosmetics
In general, nitrocellulose is the main component of nail
enamels contain. In conventional nail lacquer removers
to remove coatings of the nail lacquer, acetone and ethyl
Biomass Conversion and Biorefinery

Fig. 12  Direct and indirect

application of GC. Reproduced
from Sonnati et al. [14] with
permission from the Royal Soci-
ety of Chemistry

Table 2  The properties of GC and pure glycerol [44] surfactant [63]. For GC ester, it can be synthesised from the
Properties Units GC Pure glycerol
reaction of GC and aliphatic acyl chlorides as these compounds
have a good thermal and oxidation stability [64].
Molecular weight g/mol 118.09 92.094
Density at 25 °C g/ml 1.4 1.261
5.7 Chemical intermediate
Boiling point °C 354 290
Melting point °C -69 17.8
GC can split off ­CO2 and yield glycidol that can act as chem-
Vapour pressure at 177 °C bar 0.008 0.003
ical intermediate [65]. Glycidol also has been an attraction
Flash point °C 190 177
to the industry as it can be used as raw materials for glycidyl
Dielectric constant at 20 °C ESU 111.5 42.5
ethers, polyglycerols and polyurethane, as well as in per-
Viscosity at 25 °C cP 85.4 1500
fume, paints, detergents and dye-levelling agents [63, 64].
In addition, glycidol is one of the chemical intermediates
that is widely used in textile, plastics, pharmaceutical and
acetate which act as a solvent can dissolve the nitrocellu- cosmetic industries [44]. The route for synthesis of glycidol
lose. Conventional nail lacquer remover, on the other hand, from GC is shown in Fig. 13.
is extremely flammable and can cause nail cracking [59].
To overcome this problem, combine GC with 1,3-dimethyl-
2-imidazolidinone, hydroxypropyl cellulose and water to 5.8 Polymers
make a nail lacquer remover. This nail lacquer remover
contains cyclic alkylene carbonate, which is low in flam- Polycarbonate can be synthesised from GC that exhibits
mability, does not cause drying and breaking [59]. five-membered cyclic-carbonate end groups. The reaction
of diamine and the cyclic-carbonate end group may pro-
5.4 Blowing agents duce non-isocyanate polyurethane polymer [66]. Further-
more, inexpensive GC also can be a source of new polymeric
GC can generate C­ O2 when reacted with isocyanate [60], materials for the production of polyurethanes and polycar-
GC can thus be employed as blowing agents such as for bonates [67].
polyurethane foams, for example [11].

5.5 Detergents 6 Conclusions

GC also can be used as one of composition in solid detergent
[61]. Interestingly, the best hand-feel performance can come
from hydrolysing GC in wash liquor to form glycerol [62].
5.6 Surfactants
Some examples of surfactants as indirect application of GC
are sorbitan polyglycerol and GC esters. Reaction of sorbitan
carboxylic acid ester with GC may produce polyglycerol
This review summarises the related literature on direct car-
boxylation of glycerol using different catalysts. Advantages
and disadvantages of four major routes to produce GC are
listed and discussed, focusing on the GC synthesis by direct
reaction of glycerol with ­CO2. The reaction pathway of GC
is presented. The effect of certain parameter on carboxyla-
tion of glycerol as well as direct and indirect application of
the glycerol also has been discussed. More summarisation
of key conclusions is listed below:

13

OH
O
HO Cl
OCH3 OCH3
Fig. 13  Route synthesis of glycidol from GC. Republished with permission of Zhou et al. [76]; copyright (2021) Elsevier
1. Conversion of glycerol to GC can be tested out using
either homogeneous or heterogeneous catalyst; however,
the use of heterogeneous catalyst is preferred because
there are some limitations to use homogeneous catalyst,
such as difficulty in catalyst recovery and low conversion
of glycerol due to low ­CO2 reactivity.
2. Direct carboxylation of glycerol is thermodynamically
limited and has small equilibrium constant. To achieve
high glycerol conversion, the equilibrium must be
shifted towards the product side which is the formation
of GC by addition of acetonitrile to remove the water
produced during the reaction.
3. The carboxylation of glycerol has limitations in terms
of upgrading into large-scale production of GC com-
pared with other routes to produce GC. Therefore, it is
fundamental to keep searching for the suitable catalyst
to be used for the generation of GC using this reaction
which is cheaper and environmental friendly compared
to commercial catalyst.
4. The previous studies have focused on valorisation of
pure glycerol but there is one more attractive approach
which is the conversion of crude glycerol from the bio-
diesel industry to eliminate the needs for expensive puri-
fication methods
5. Most of the reaction is catalysed by basic mechanism,
thus catalyst with high basicity may favour the formation
of GC.
6. The review article presents various applications of
GC in various industries such as solvents, surfactants,
polymers, cosmetics and detergents. Furthermore, this
review article also demonstrates the possibility of using
new catalyst that can be used as alternative catalyst to
replace commercial catalyst in the direct carboxylation
of glycerol for the production of GC.
Author contribution  Najaa Rozulan contributed to writing, data col-
lection and validation; Siti Abdul Halim contributed to data managing,
organising and editing; Nurul Razali contributed to writing, data col-
lection, conceptualisation and supervision; and Lam Su Shiung con-
tributed to validation, review and editing.
13
Biomass Conversion and Biorefinery
O
OH
O O
Step 1 Step 2
O
HO
Funding  NR would like to thank Universiti Malaysia Terengganu for
the financial support (RIGS 55192/11).
Data availability  The data analysed during the current study are pub-
licly available and stated in References section.
The authors declare no competing interest.
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