0.0.1.

Glycerol carbonate synthesis

Glycerol is a by-product formed from biodiesel synthesis (Sankaranarayanan and
Srinivasan, 2012). Due to the large amount of glycerol produced every year, the market
value of refined glycerol has reduced from ∼ $ 1750/¿ tonne to ∼ $ 750 /tonne since
2005 and crude glycerol is about $ 100/ ¿ tonne (Quispe et al., 2013). Therefore,
valorisation of both glycerol and crude glycerol is crucial (Sandra et al., 2016).

GlyC synthesis from glycerol and C O2 attracted much attention for several reasons: this
process utilises two types of undesired products and GlyC has wide-ranging reactivity
that can be applied in many applications, e.g., electrolyte in lithium ion battery,
cosmetic, as chemical intermediate and as the solvent (Sonnati et al., 2013). Sonnati
outlines other methods of synthesising the GlyC via hydrocarbon chain; which do not
involve C O2 as a reactant. These routes include the reaction of glycerol and (i) urea (ii)
dimethyl carbonate and diethyl carbonate (iii) phosgene (iv) ethylene carbonate and
propylene carbonate. However, carboxylation of glycerol is proposed as a green route to
synthesise GlyC through avoiding the use of phosgene. Cyclic compounds including
cyclic carbamates and cyclic carbonates are commonly manufactured from phosgene
which is toxic and hazardous in nature (Narkhede and Patel, 2015). The carboxylation of
glycerol via heterogeneous catalysis produces water as the by-product (Sonnati et al.,
2013). A range of solid catalysts have previously been investigated in this reaction:
zeolites, basic ion-exchange resins, tin complexes and Ce-based catalysts (Aresta et al.,
2006; Vieville et al., 1998). This reaction is further investigated by developing active
heterogeneous catalysts such as A l 2 O 3 ( C e O 2 − A l 2 O 3 ) or N b2 O 5 ( C e O 2 − N b2 O5 ) .
Table 2.4. Comparative study of catalysts with different reaction conditions.

Catal Reaction condition Gly. Select Ref.

yst Dehydrating Yield
Conv. ivity
agent Temp Time Pa Pb ( %)
(% ) (%)
(∘ C ) (hr) ( M P a) ( M P a)
c
C e O2 2− 150 5 3 4 N/A N/A 20 (J. Liu et ¿
cyanopyridine ¿
Acet
Z n / A l / Lonitri
aF 170 12 4 N/A 30.6 46 14 (Li et al. ¿
le ¿

(H. Li,
Z n / A l / LAcet
a
onitri 170 12 4 N/A 35.7 42.2 15.1 Jiao, et al.,
− L i le
2015)

Acet (Zhang and

C u /L a2 O
onitri
3 150 3 4 7 8.9 29.3 N/A
le He, 2014b)

2.3 wt. %Acet (Zhang and

onitri 150 12 4 7 33.4 45.4 15.2
C u /L a2 O 3le He, 2014a)
 L a2 O 2 C OAcet
3− (Li et al.,
onitri 170 12 4 N/A 30.3 47.3 14.3
Z n O le 2013 )

a
Initial pressure of C O2 at room temperature
b
Reaction pressure of C O 2 at reaction temperature.
c
Reaction was carried out in the presence of dimethyl formamide.

Carboxylation of glycerol in the presence of L a2 O 2 C O3 − Z n O and acetonitrile was first

reported by Li et al. (2013). Acetonitrile acts as the chemical water trap, consequently
shifting the reaction equilibrium to the product side. C u /L a2 O 3 has also been employed
to synthesise the GlyC (Zhang & He, 2014a). Further studies have been carried out
employing C u -based catalysts supported on: (i) acid and basic supports (ii) supports
with acid sites only (iii) supports with basic sites only and (iv) supports with neither acid
nor basic site (Zhang & He, 2014b). Further research employing Zn/Al/La/M ¿ and Z r )
hydrotalcite as the catalysts for this reaction. Z n / A l/ L a/Z r , calcined at 500 ∘ C , resulted
in a 14.1 % yield of GlyC (43.3%). In order to improve the yield of GlyC at a lower
temperature and pressure, 100 ∘ C and 2.5 M P a , the reaction was carried out by reacting
3-chloro-1,2-propanediol and C O 2 in the present of trimethylamine (Ochoa-Gómez et
al., 2011). Ozorio and co-worker have studied the mechanism of glycerol carboxylation
over metal impregnated zeolites in absence of dehydrating agent; however, the reaction
must take place at high pressure, 100 bar. This resulted in a 6 % yield of GlyC (Ozorio et
al., 2015). Research shows the success of synthesising GlyC from glycerol and C O2 over
heterogeneous catalysts in presence or absence of acetonitrile, however, the yield of
products formation is considered low. Recently 2-cynopyrine has been employed;
resulting in a 20 % yield of GlyC with 2-picolinamide as the by-product (J. Liu et al.,
2016; Su et al., 2017). The list of catalysts used for the carboxylation of glycerol are
summarised in Table 2.4.

0.1. Conventional routes to glycerol carbonate

0.1.1. Phosgene
Transcarbonation of glycerol using phosgene is shown in Figure 2.3. Table 2.5 shows the
examples of linear and cyclic carbonates; in which both linear and cyclic carbonates have
an industrial interest and are mainly produced from phosgene (Aresta and Dibenedetto,
2007). The use of phosgene as carbonate source to synthesise glycerol carbonate must be
eliminated because it is toxic and highly corrosive. However, Shukla & Srivastava in their
review highlight the phosgene-free methods available to synthesise diethyl carbonate
(linear carbonate) (2016).

Figure 2.3. Transcarbonation of glycerol using phosgene (Sonnati et al., 2013).