J. Chem.

Thermodynamics 43 (2011) 731–736

Contents lists available at ScienceDirect

J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

Chemical equilibrium of glycerol carbonate synthesis from glycerol

Jiabo Li, Tao Wang ⇑
State Key Laboratory of Chemical Engineering, Department of Chemical Engineering, Tsinghua University, Beijing 100084, China

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

Article history: In this paper, the chemical equilibrium for the glycerol carbonate preparation from glycerol was investi-
Received 30 September 2010 gated. The chemical equilibrium constants were calculated for the reactions to produce glycerol carbon-
Received in revised form 2 December 2010 ate from glycerol. The theoretical calculation was compared with the experimental results for the
Accepted 23 December 2010
transesterification of glycerol with dimethyl carbonate. Transesterification of glycerol with cyclic carbon-
Available online 30 December 2010
ates or alkyl carbonates is thermodynamically favourable for producing glycerol carbonate from glycerol
according to the equilibrium constant. Increasing temperature can increase the chemical equilibrium
Keywords:
constant for the reaction of glycerol with dimethyl carbonate. For the reaction of glycerol with ethylene
Glycerol carbonate
Glycerol
carbonate, increasing temperature can decrease the chemical equilibrium constant. The reaction of glyc-
Dimethyl carbonate erol with carbon dioxide is thermodynamically limited. High temperature and low pressure are favour-
Chemical equilibrium able to the reaction of glycerol and urea.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction example, using Al/Ca-mixed oxide (AlCaMO) as the catalyst, the

Recently, much attention has been focused on the utilization of
glycerol (G), as a by-product with the amount as one tenth of bio-
diesel, for producing value-added chemicals [1]. Among the chem-
icals derived from glycerol, glycerol carbonate (GC) is a high value-
added product with many potential applications [2–6].
Glycerol carbonate can be prepared from glycerol by different
methods. The first method is the reaction of glycerol with urea
(scheme 1). With c-zirconium phosphate as the catalyst, the yield
of glycerol carbonate from glycerol and urea can reach 80% for 3 h,
at T = 418 K and 20 Pa when the mole ratio of glycerol to urea is
1:1 [7]. The reaction can also be catalyzed at 145 °C and
3,999.87 Pa by mixed oxides HTc-Zn derived from hydrotalcite,
and the yield of glycerol carbonate can be 72% for 5 h with mole ratio
of glycerol to urea 1:1 [8]. Carbonation of glycerol with carbon diox-
ide (scheme 2) is another method for the production of glycerol
carbonate [9–11]. Glycerol was reacted with carbon dioxide at
T = 453 K and 5 MPa catalyzed by n-Bu2Sn(OMe)2, although the
yield of glycerol carbonate is only 5.72% [10]. A 35% yield of glycerol
carbonate was obtained from glycerol and carbon dioxide in meth-
anol by using 1 mol% nBu2SnO as the catalyst for 4 h at 13.8 MPa and
120 °C [11].
Glycerol carbonate can also be prepared from glycerol by the
transesterification with cyclic carbonate such as ethylene carbon-
ate (EC) (scheme 3) [7,12] or alkyl carbonates such as dimethyl car-
bonate (DMC) (scheme 4) [6,13–15] and diethyl carbonate [16]. For
⇑ Corresponding author. Fax: +86 10 62773017.
E-mail addresses: Lijb07@mails.tsinghua.edu.cn (J. Li), taowang@tsinghua.edu.cn
(T. Wang).
yield of glycerol carbonate can reach 87% at T = 308 K for 1 h when
the mole ratio of ethylene carbonate to glycerol is 2 [7].
The yield of glycerol carbonate is significantly dependent on the
chemical thermodynamic of the reaction. For example, due to the
chemical equilibrium, the high mole ratio of alkyl carbonates to glyc-
erol is favourable for converting glycerol to glycerol carbonate by the
transesterification of glycerol with alkyl carbonates, because the
transesterification of glycerol with the alkyl carbonate is reversible
and a high mole ratio of the alkyl carbonate to glycerol can shift pos-
itively the chemical equilibrium. In the literature, the mole ratio of
dimethyl carbonate to glycerol was usually 3 to 5 [6,13,14]. Marya
[16] reported the synthesis of glycerol carbonate from glycerol and
diethyl carbonate catalyzed by the hydrotalcite-like compounds
with the mole ratio of diethyl carbonate to glycerol as high as 17.
As far as we are aware, the chemical equilibrium constants for
preparing glycerol carbonate from glycerol have not been reported.
In this work, the chemical equilibrium for the preparation of glyc-
erol carbonate from glycerol was investigated. The chemical equi-
librium constants were calculated for the reactions. For the
transesterification of glycerol with dimethyl carbonate to produce
glycerol and methanol (ME), the calculated results were compared
with the data derived from the experimental results.
2. Methodology
2.1. Chemical equilibrium constants at the standard conditions
(T = 298.15 K and 101,325 Pa)
The chemical equilibrium constants at standard conditions
(T = 298.15 K and 101,325 Pa) can be calculated as follows. The

0021-9614/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jct.2010.12.013
732 J. Li, T. Wang / J. Chem. Thermodynamics 43 (2011) 731–736

O O Usually, the liquid standard molar entropy Shm;l could be calculated

OH OH OH from the gas phase standard molar entropy Shm;g and DV Hhm , accord-
C NH2 O O
CH2 CH CH2 + H2N + 2NH3 ing to equation (6)

OH DV Hhm
Shm;l ¼ Shm;g   103 : ð6Þ
T
SCHEME 1. Preparation of glycerol carbonate from glycerol and urea.
Nowadays, the Shm;g of dimethyl carbonate has been calculated [22].
But, Shm;g of glycerol carbonate and ethylene carbonate have not been
O reported. The functional group method by Benson [23] can be used
OH OH to estimate Shm;g of the substances (equation (7))
OH
CO2 O X
CH2 CH CH2 + O + H2 O
Shm;g ¼ ni Shi  R ln d þ R ln g þ Shcorrection ; ð7Þ
OH i

ni, the number of functional group i; Shi , the additivity value of group
SCHEME 2. Preparation of glycerol carbonate from glycerol and carbon dioxide.
i; R, the mole gas constant; d = din  dext, the symmetry number of
molecular; din, the internal symmetry number of molecular; dext,
the external symmetry number of molecular; g, the number of
O O enantiomer; Shcorrection , the cyclic correction data.
OH OH OH OH OH
O O O O A molecule can be divided into several functional groups
+
CH2 CH CH2 + CH2 CH according to the structure. Every functional group i has contributed
OH value Shi to Shm;g of the molecule. The d and g are the correction
parameters for Shm;g of the molecule based on molecular symmetry
SCHEME 3. Preparation of glycerol carbonate from glycerol and ethylene carbonate. and the enantiomer. The Shcorrection is the cyclic correction factor for
Shm;g of the molecule if it is a cyclic compound.
Because glycerol carbonate and ethylene carbonate are cyclic
compounds, the cyclic correction factor of the cyclic compound
O
OH OH OH
O was needed to modify the summation of the group additivity in
O O + 2 CH 3OH the functional group method of Benson. However, the Shcorrection of
CH 2 CH CH 2 + CH 3O C OCH 3
cyclic alkylene carbonate in this functional group method was
OH not reported. The reported equilibrium data for the liquid phase
reaction involving ethylene carbonate, methanol (ME), dimethyl
SCHEME 4. Preparation of glycerol carbonate from glycerol and dimethyl carbonate, and ethylene glycol (EG) was used to deduce the value
carbonate.
of Shm;l for ethylene carbonate and Shcorrection of cyclic alkylene carbon-
ate via the functional group method of Benson. Then, the values of
Shm;g and Shm;l of glycerol carbonate were calculated according to
change of standard molar enthalpy Dr Hhm and change of standard
equations (6) and (7).
molar entropy Dr Shm of the reaction can firstly be calculated using
equations (1) and (2), if the standard molar enthalpy of formation
2.2. The effect of temperature on the chemical equilibrium constants
Df Hhm and standard molar entropy Shm of all reactants and products
in the corresponding phase involved in the reaction can be ob-
The values of the liquid heat capacity Cp,m,l of dimethyl carbon-
tained. Then, Dr Ghm and Kh for each reaction can be calculated from
ate, glycerol carbonate, and ethylene carbonate were estimated by
Dr Hhm and Dr Shm using equations (3) and (4)
X X using the Rozicka-Domalski functional group method [24], which
Dr Hhm ¼ ni Df Hhm;i  nj Df Hhm;j ; ð1Þ is a method normally used to estimate the liquid heat capacity
product Reactant according to the molecular structure. In this method, the cyclic alk-
X X ylene carbonate correction factor for the liquid heat capacity is also
Dr Shm ¼ ni Shm;i  nj Shm;j ; ð2Þ needed. In this work, we use the correction factor for 1,3-dioxa-
product Reactant cyclopentane over the temperature range (175 to 300) K instead
of cyclic alkylene carbonate because the correction factor of cyclic
Dr Shm alkylene carbonate has not been reported until now. The heat
Dr Ghm ¼ Dr Hhm  T  ; ð3Þ
1000 capacity for other substances in a different phase could also be ob-
tained from the literature [24]
Dr Ghm X X
ln K h ¼ : ð4Þ Dr C p;m ¼ ni C p;m;i  nj C p;m;j ; ð8Þ
RT
product Reactant
Except for dimethyl carbonate, glycerol carbonate, and ethylene
 
carbonate, the thermodynamic properties such as standard molar d Dr H m
enthalpy of formation and standard entropy of the reactants and ¼ Dr C p;m ; ð9Þ
dT p
products in the corresponding phases involved in the above reac-
tions, can be obtained from the handbook [17]. For dimethyl car-  
dðDr Gm =TÞ
bonate, glycerol carbonate, and ethylene carbonate, only the gas ¼ Dr Hm =T 2 : ð10Þ
dT
phase standard molar enthalpy of formation Df Hhm;g and standard p

molar enthalpy of vaporization DV Hhm had been reported [18–21].
So, the liquid standard molar enthalpy of formation Df Hhm;l can be
calculated from Df Hhm;g and DV Hhm , according to equation (5)
Df Hhm;l ¼ Df Hhm;g  DV Hhm :
The change of molar heat capacity of reaction DrCp,m can be calcu-
lated (equation (8)). Here, it is assumed that DrCp,m and DrHm are
independent of the pressure. Then, the change of molar enthalpy
ð5Þ for each reaction DrHm at different temperatures can be calculated
based on equation (9). The value of DrGm(298.15K, P) can be
 J. Li, T. Wang / J. Chem. Thermodynamics 43 (2011) 731–736 733

obtained by Eq. (14). Based on equation (10) and DrGm(298.15 K, P), By integration, equation (12) becomes equation (14). The value
the change of Gibbs free energy of reaction DrGm(T, P) and the effect of DrGm(T, Ph) can be calculated according to equations (8)–(10).
of temperature on the thermodynamic equilibrium constant K can Then, the chemical equilibrium constants at different pressure
be obtained. can be calculated according to equation (15)

Dr Gm ðT; PÞ ¼ Dr Gm ðT; Ph Þ þ DnRT lnðP=Ph Þ; ð14Þ

2.3. The effect of pressure on the chemical equilibrium constants

For the reaction involving gas, pressure also has an influence on

Dr Gm ðT; PÞ ¼ RT ln K: ð15Þ
the thermodynamic equilibrium. When the reaction temperature is
constant, 2.4. Chemical equilibrium constant from experimental data
 
@ Dr Gm
¼ DV m : ð11Þ The transesterification of glycerol with dimethyl carbonate was
@p T
chosen for comparing the theoretical calculation and the experi-
Assuming the gas involved in the reaction is ideal for the reaction at mental results. As described above, this is a reversible reaction
low pressure, then and higher mole ratio of dimethyl carbonate to glycerol favours
  the yield of glycerol carbonate. To obtain a sufficiently high yield
@ Dr Gm
¼ DnRT; ð12Þ of glycerol carbonate, a relatively high mole ratio of dimethyl car-
@p T bonate to glycerol was used for the experiments. The detailed
X X experiment conditions are as follows: 2:1 mole ratio of dimethyl
Dn ¼ miðgÞ  mjðgÞ ð13Þ carbonate to glycerol, 4% mole ratio of initial amount of CaO to
product reactant
glycerol, stirring rate 300 rpm, reaction temperature from 40 °C
mi(g), mj(g) stoichiometric coefficient of gas substance. to 70 °C. In the reaction process, samples were taken every
10 min and analyzed by a Gas Chromatograph (HP 5890) equipped
TABLE 1 with a capillary column DM-FFAP (30 m  0.25 mm) and a flame
Group and group parameter in UNIFAC. ionisation detector. When the compositions of the samples did
Groupa 1 2 3 4 5 6 7 not change with time, the equilibrium mole compositions were
CH3 CH3O COO OH CH2 CH CH2O obtained.
_ðDMCÞ
1 1 1 0 0 0 0 The activity coefficients at different temperatures and equilib-
mi
_ðGCÞ
0 0 1 1 1 1 1
rium composition were calculated by UNIFAC [25] with the groups
mi
_ðGÞ
and group parameter listed in table 1. The equilibrium constant at
mi 0 0 0 3 2 1 0
_ðMEÞ
each temperature was obtained using equations (16) and (17)
mi 1 0 0 1 0 0 0
Rk 0.9011 1.145 1.38 1 0.6744 0.4469 0.9183 ai ¼ ci xi ; ð16Þ
Qk 0.848 1.088 1.2 1.2 0.54 0.228 0.78
_ðDMCÞ
mi
_ðGCÞ
; mi ; mi ; mi
_ðGÞ _ðMEÞ
are the number of group i in DMC, GC, G, and ME, aGC ðaME Þ2
K¼ : ð17Þ
respectively. aG aDMC
Rk, Qk are the volume parameter and area parameter of group i, respectively.
a
The group parameter could be referenced in the literature [25].
3. Results and discussion

TABLE 2 3.1. Calculation of the standard molar entropy for glycerol carbonate
Equilibrium mole fraction and activity coefficients of the substances in reaction (5) at
T = 298.15 K and 101,325 Pa. It was reported that dimethyl carbonate and ethylene glycol (EG) could be pro-
duced from the reaction of ethylene carbonate with methanol (ME). Table 2 shows
Mole fraction EC ME DMC EG the equilibrium mole fraction of reactants and products in this reaction (scheme 5)
xib 0.0196 0.8235 0.0784 0.0784 at T = 298.15 K and 101,325 Pa [26] and the calculated activity coefficient by UNI-
cic 1.941 1.014 4.571 0.890 FAC [25].
Then, the activity ai of involved substances, the standard equilibrium constant
xi is the equilibrium mole fraction. ci is the activity coefficient. Kh and change of standard molar Gibbs free energy Dr Ghm of reaction (5) were calcu-
b
Data can be obtained from the reported data in the literature [26]. lated. According to the liquid standard molar enthalpies of formation of ethylene
c
Data were calculated using the UNIFAC method. carbonate, methanol, dimethyl carbonate, and ethylene glycol in table 6, the change
of standard molar enthalpy Dr Hhm of reaction (5) was obtained. Then, the change of
standard mole entropy Dr Shm of reaction (5) was calculated from Dr Hhm and Dr Ghm (Eq.
(3)). Based on Dr Shm and Shm;l for methanol, dimethyl carbonate, and ethylene glycol
O listed in table 5, the value of Shm;l for ethylene carbonate was then calculated. It was
C
O reported that DV Hhm for ethylene carbonate was 62.8 kJ  mol1 [18]. Then, the Shm;g of
CH2 CH2
O O + 2CH3OH ethylene carbonate was determined to be 438.45 J  K1  mol1 using equation (6).
CH3O C OCH3 +
The results are listed in table 3.
OH OH
Based on the functional group and the group additivity values [23] in the
Benson method for ethylene carbonate as listed in table 4, and Shm;g of ethylene car-
SCHEME 5. Transesterification of ethylene carbonate and methanol. bonate as listed in table 3, the Shcorrection of cyclic alkylene carbonate was determined

TABLE 3
Thermodynamic data of reaction (5) at T = 298.15 K and 101,325 Pa.

Kh Dr Hhm =ðkJ  mol

1
Þ Dr Ghm =ðkJ  mol
1
Þ Dr Shm =ðJ  K1  mol
1
Þ Shm;l ðECÞ=ðJ  K1  mol
1
Þ
1
Shm;g ðECÞ=ðJ  K1  mol Þ

0.943 19.67 0.145 66.49 227.71 438.45

Kh is the calculated equilibrium constant from reported experiment data. Dr Hhm is the change of standard molar enthalpy of reaction. Dr Ghm is the change of standard molar
Gibbs energy of reaction. Dr Shm is the change of standard molar entropy of reaction. Shm;l ðECÞ is the liquid standard molar entropy of ethylene carbonate from experiment data.
Shm;g ðECÞ is the gas standard mole entropy of ethylene carbonate calculated according to equation (6).
734 J. Li, T. Wang / J. Chem. Thermodynamics 43 (2011) 731–736

to be 229.69 J  K1  mol1 according to equation (7). Combined with the functional
group and group additivity values [23] in the Benson method for glycerol carbonate
as listed in table 5, and Shcorrection of cyclic alkylene carbonate, the Shm;g of glycerol car-
bonate was calculated to be 525.56 J  K1  mol1 according to equation (7). It was
reported that DV Hhm of glycerol carbonate was 85.9 J  mol1[18]. So, the Shm;l of glyc-
erol carbonate was determined to be 237.45 J  K1  mol1 according to equation
(6). The standard molar enthalpies of formation and standard molar entropies of
the substances involved in reactions for glycerol carbonate synthesis are listed in
table 6.
3.2. Chemical equilibrium constants at the standard condition (T = 298.15 K and
101,325 Pa)
According to the standard molar enthalpies of formation and standard molar
entropies listed in table 6, Dr Hhm and Dr Shm of the reactions for GC synthesis can be
obtained. Then, Dr Ghm and Kh for each reaction can be calculated from Dr Hhm and
Dr Shm . The results are listed in table 7. Compared with the transesterification of glyc-
erol with cyclic carbonate or alkyl carbonates, the standard chemical equilibrium
constant for the reaction of glycerol with carbon dioxide or urea was quite small
at the standard conditions. Transesterification of glycerol with cyclic carbonate or
alkyl carbonates has thermodynamic advantages for the preparation of glycerol car-
bonate from glycerol at standard conditions.
TABLE 4
The functional group and the group additivity values for EC.
ECd Number of group Shi =ðJ K
3.3. The effect of temperature on the chemical equilibrium constants
In order to calculate chemical equilibrium constants at different temperatures,
liquid heat capacity Cp,m,l of dimethyl carbonate, glycerol carbonate and ethylene
carbonate were estimated by the functional group method of Rozicka-Domalski
and heat capacity values for other substances in a different phase were obtained
from the handbook [24]. The data of the heat capacity are listed in table 8. The effect
of temperature on the chemical equilibrium constant was determined, as described
in section 2.2 using equations (8)–(10), (and) (14), and the results are shown in
table 9. For the reaction of glycerol with dimethyl carbonate, the by-product is
methanol which has a low boiling temperature. Methanol and dimethyl carbonate
can also form an azeotrope at 63.5 °C and 101,325 pa. Because the pressure for the
reaction of glycerol with dimethyl carbonate is usually 1 atm, the reaction temper-
ature is usually not very high to prevent dimethyl carbonate escaping as the azeo-
trope. For the reaction of glycerol with ethylene carbonate, the reaction
temperature is also usually not very high because a high yield of glycerol carbonate
can be obtained at 1 atm and lower temperature. As reported, the yield of glycerol
carbonate can reach 87% at low temperature (35 °C) for 1 h with 2 mole ratio of eth-
ylene carbonate to glycerol [7]. Due to these reasons, the chemical equilibrium con-
stants above T = 353.15 K were not calculated for the reaction of glycerol with
dimethyl carbonate or ethylene carbonate.
TABLE 7
Thermodynamic data for the reactions for GC synthesis at T = 298.15 K and
101,325 Pa.
Dr Hhm = Dr Shm = Dr Ghm = Kh
1
 mol
1
Þ ðkJ  mol
1
Þ ðJ  K1  mol
1
Þ ðkJ  mol
1
Þ

C–(H)2(O)(C) 2 41.03 G Urea (Scheme 1) 126.2 314.52 32.43 2.07  106

O–(C)(CO) 2 35.31 G CO2 (Scheme 2) 9.13 110.85 23.92 6.41  105
CO–(O)2 1 61.84 G EC (Scheme 3) 6.1 14.76 1.70 1.985
G DMC (Scheme 4) 13.57 51.66 1.83 2.100
Shi is the additivity value of group i at standard condition.
d
For EC, the symmetry number of molecular d = 2, the number of enantiomer g = 1. Dr Hhm is the change of standard molar enthalpy of reaction, Dr Ghm is the change of
The group additivity values are from the literature [23]. standard molar Gibbs free energy of reaction, Dr Shm is the change of standard molar
entropy of reaction, Kh is the theoretical equilibrium constant at standard
conditions.

TABLE 5
The functional group and the group additivity values for GC.
TABLE 8
GCe Number of group 1 Heat capacity of all substances involved in reactions for GC synthesis.
Shi =ðJ  K1  mol Þ

C–(H)2(O)(C) 2 41.03 Cp,m/(J  K1  mol1) = a + b(T/K) + c(T/K)2 + d(T/K)3 + e(T/K)4

O–(C)(CO) 2 35.31 a b  102 c  104 d  106 e  1010
CO–(O)2 1 61.84 l
C–(C)2(H)(O) 1 46.05 G(L) 132.145 86.007 19.745 1.806 0
O–(H)(C) 1 121.63 DMC(L)m 49.320 43.950 29.930 0 0
ME(L)l 40.152 31.046 10.291 1.459 0
Shi is the additivity value of group i at standard condition. GC(L)m 6.970 99.040 44.700 0 0
e
For GC, the symmetry number of molecular d = 1, the number of enantiomer g = 2. EC(L)m 108.920 17.968 44.730 0 0
The group additivity values are from the literature [23]. CO2(g)l 27.090 1.127 1.248 1.973 0.878
EG(L)l 75.878 64.182 16.493 1.694 0
Urea(S)l 38.430 4.980 7.050 0.861 0
NH3(g)l 35.235 3.504 1.697 0.176 0.633
TABLE 6 H2O(L)l 92.053 3.995 2.110 0.534 0
Standard molar enthalpy of formation and standard mole entropy of all substances
Cp,m is the mole isobaric heat capacity. a, b, c, d, e are coefficients in the equation of
involved in reactions for GC synthesis.
C p;m .
l
Phase Df Hhm =ðkJ  mol1 Þ Shm =ðJ  K1  mol
1
Þ The heat capacity was obtained from the literature [24].
m
The heat capacity was calculated by Rozicka-Domalski functional group method.
f
G Liquid 668.52 204.47
MEf Liquid 239.1 127.24
DMC Liquid 608.74g 235.8h
GC Liquid 785.32g 237.45i TABLE 9
CO2f Gas 393.5 213.78 Chemical equilibrium constants K at different temperatures.
Ureaf Solid 333 104
T/K G Urea G CO2 G EC G DMC
NH3f Gas 45 192.77
(Scheme 1) (Scheme 2) (Scheme 3) (Scheme 4)
H2Of Liquid 285.83 69.950
(20 Pa) (5 MPa) (101,325 pa) (101,325 pa)
EC Liquid 573.5g 227.71j
EG Liquid 462.8f 179.9k 298.15 0.516  102 3.27  103 1.981 2..34
313.15 0.575  103 2.723  103 1.704 2.607
Df Hhmis the standard molar enthalpy of formation. Shm
is the standard molar entropy. 333.15 9.611  103 2.161  103 1.296 3.406
f
Data were retrieved in the handbook [17]. 353.15 1.110  105 1.769  103 0.917 4.205
g
Data were obtained from equation (5) and the literature [18–21]. 373.15 9.547  105 1.513  103
h
Data were obtained from equation (6) and the literature [22]. 393.15 6.491  106 1.366  103
i
The data were calculated using the Benson functional group method (equation 413.15 3.658  107 1.314  103
(7)). 433.15 1.780  108 1.355  103
j
Data were calculated from the reported data in literature [26]. 453.15 7.670  108 1.506  103
k
Data were obtained from http://webbook.nist.gov/chemistry.
 J. Li, T. Wang / J. Chem. Thermodynamics 43 (2011) 731–736 735

TABLE 10 TABLE 12
Effect of reaction pressure on K for the reaction of glycerol with urea or carbon Activity coefficients and experimental equilibrium constants for Scheme 4.
dioxide
T/K ci Kexperiment K
P/Ph G Urea (Scheme 1) G CO2 (Scheme 2)
DMC GC G ME
(T = 413.15 K) (T = 453.15 K)
7 9 313.15 1.586 1.102 1.903 1.227 2.903 2.607n
0.000197 3.705  10 2.19  10
323.15 1.567 1.098 1.862 1.218 3.806 3.005n
0.001 1.434  106 1.11  108
333.15 1.528 1.091 1.853 1.216 4.920 3.406n
0.01 1.428  105 1.11  107
343.15 1.508 1.087 1.819 1.208 6.197 3.808n
0.1 1.423  102 1.11  106
1 1.417 1.11  105 ci is the activity coefficient. Kexperiment is the equilibrium constant calculated from
10 1.411  102 1.11  104 the experimental data. K is the theoretically calculated equilibrium constant.
20 3.525  103 2.22  104 n
Data were calculated according to the effect of temperature on the chemical
30 1.566  103 3.33  104 equilibrium constants for reaction of glycerol and dimethyl carbonate in section 3.3.
40 0.88  103 4.44  104
50 0.563  103 5.55  104
The activity coefficients at different temperatures and equilibrium composi-
P/Ph is the ratio of reaction pressure to the standard pressure 101,325 Pa. tions were calculated by using UNIFAC [25]. The chemical equilibrium constants
at different temperatures were obtained by using equations (16) and (17). The re-
sults are listed in table 12.
It is seen from table 9 that the chemical equilibrium constant decreases with It can be seen from table 12 that the experimental equilibrium constant was not
increasing reaction temperature for the reaction of glycerol with ethylene carbon- exactly same as the theoretically calculated value. There was a larger error at higher
ate. For the reaction of glycerol with carbon dioxide, the chemical equilibrium con- temperature. The deviation may be due to the estimation of liquid heat capacity for
stant also decreased slightly with the increase of reaction temperature. It can be glycerol carbonate. As described in section 2.2, the heat capacity is critical to the
concluded that the reaction of glycerol with carbon dioxide is thermodynamically estimation for the effect of temperature on the chemical equilibrium constant.
unfavourable because the chemical equilibrium constant is quite small. Usually, The Rozicka-Domalski group method was adopted to estimate the liquid heat
the yield of glycerol carbonate was small when the reaction of glycerol with carbon capacity based on the molecular structure, in which cyclic alkylene carbonate cor-
dioxide was adopted to produce glycerol carbonate [9,10]. For the reaction of glyc- rection factor for liquid heat capacity is needed. The correction factor for 1,3-dioxa-
erol with urea, the chemical equilibrium constant increased dramatically as the cyclopentane within the temperature range (175 to 300) K was used instead of
reaction temperature increased when the pressure is very low. It was reported that cyclic alkylene carbonate, because cyclic alkylene carbonate correction data have
high temperature is favourable to the yield of glycerol carbonate from glycerol and not been reported until now. The correction factor for the liquid heat capacity at
urea. However, there should be an optimum temperature because glycerol carbon- a temperature lower than 300 K was used for higher temperature conditions. This
ate may be decomposed at high temperature [8]. For the reaction of glycerol with may lead to the greater error of the chemical equilibrium constant at higher tem-
dimethyl carbonate, the reaction condition is mild because its reaction pressure is perature. However, the experimental equilibrium constant increased as the reaction
usually 1 atm. The chemical equilibrium constant of the reaction of glycerol with temperature increased. This was identical to the results obtained from the theoret-
dimethyl carbonate increased as the reaction temperature increased. ical calculation.

3.4. The effect of pressure on the chemical equilibrium constants 4. Conclusions

For the reaction of glycerol with dimethyl carbonate or ethylene carbonate, the
The chemical equilibrium constants were calculated for the
reaction pressure does not influence the chemical equilibrium because Dn of the
reaction is 0. For reaction of glycerol with urea or carbon dioxide, Dn is not 0, so reactions for producing glycerol carbonate from glycerol. Transe-
the reaction pressure can influence the DrGm(T, P) and the corresponding chemical sterification reactions of glycerol with cyclic carbonates or alkyl
equilibrium. The effect of reaction pressure on the K for the reaction of glycerol with carbonates are thermodynamically favourable for the preparation
urea or carbon dioxide was determined using equations (8)–(10), (14), and (15) of glycerol carbonate. Increasing temperature can increase the
(described in section 2.3), and the results are shown in table 10.
For the reaction of glycerol with carbon dioxide, increasing pressure is favour-
chemical equilibrium constant for the reaction of glycerol with di-
able to the chemical equilibrium. However, the chemical equilibrium constant is methyl carbonate. For the reaction of glycerol with ethylene car-
still very small even at pressure as high as 5 MPa. Combined with the effect of tem- bonate, increasing temperature can decrease the chemical
perature on the equilibrium constant described as above, it can be concluded that equilibrium constant. The reaction of glycerol with carbon dioxide
the reaction of glycerol with carbon dioxide is truly limited in thermodynamics.
is thermodynamically limited. Higher temperature and low pres-
For the reaction of glycerol with urea, decreasing the pressure is favourable to yield
glycerol carbonate. Usually, the pressure is about 20 Pa when the reaction of glyc- sure are favourable to the reaction of glycerol and urea.
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JCT 10-347