Fluid Phase Equilibria 284 (2009) 6469

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Fluid Phase Equilibria

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

Measurement and calculation of vaporliquid equilibria for methanol + glycerol

and ethanol + glycerol systems at 493573 K
Yusuke Shimoyama , Toshio Abeta, Liang Zhao, Yoshio Iwai
Department of Chemical Engineering, Faculty of Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan

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

Article history: The vaporliquid equilibria for methanol + glycerol and ethanol + glycerol systems were measured by
Received 20 February 2009 a ow method at 493573 K. The pressure conditions focused in this work were 3.0311.02 MPa for
Received in revised form 14 May 2009 methanol + glycerol system and 2.278.78 MPa for ethanol + glycerol system. The mole fractions of alcohol
Accepted 9 June 2009
in vapor phase are close to unity at the pressures below 7.0 MPa for both systems. The pressures of liquid
Available online 18 June 2009
saturated lines of the liquid phase for methanol + glycerol and ethanol + glycerol systems are higher than
that for the mixtures containing alcohol and biodiesel compound, methyl laurate or ethyl laurate.
Keywords:
The experimental data in this work were modelled with PengRobinson equation of state. A conven-
Alcohol at high temperature and pressure
Glycerol
tional mixing rule and PRASOG model were adopted for the energy and size parameters in the equation
Vaporliquid equilibrium of state. In the conventional mixing rule, two binary parameters were determined from the tting to
Equation of state the vaporliquid equilibrium data for each binary system. No tting parameters were required for the
PRASOG model. The calculated results by the conventional mixing rule are better than those by PRASOG
in liquid phase. In vapor phase, the calculated results by PRASOG model are more accurate than those by
the conventional mixing rule.
2009 Elsevier B.V. All rights reserved.

1. Introduction
Biodiesel fuel, consisting of fatty acid esters, obtained by the
transesterication of vegetable oil with the lower alcohol, methanol
or ethanol has received much attention in point of solving the fos-
sil fuel limitation and the environmental benets [1]. Supercritical
alcohol method [26] is superior to the conventional alkaline and
acid catalyst methods [79] for the production of biodiesel fuel. The
processes in supercritical alcohol method can solve the problems in
the conventional methods, long time treatments and complicated
separations for the products and the catalysts. In the supercriti-
cal alcohol processes, the phase separations of the alcohol and the
products are required for the recycles of the used alcohol after the
reactions. The knowledge of phase equilibria for the mixtures con-
taining alcohol, fatty acid esters and glycerol near the critical point
of alcohol are highly useful for the design and the operation of the
biodiesel produce process with supercritical alcohol.
Glisic et al. [10] have reported the measurements of the
vaporliquid equilibria (VLE) for methanol + sunower oil at
403503 K. In our previous works, the VLE for methanol + methyl
laurate, methyl myristate, ethanol + ethyl laurate and ethyl myris-
tate systems at 493543 K [11,12] have been investigated. The
correlations with cubic equation of states have been also studied
for the systems of alcohol, vegetable oil, and fatty acid alkyl esters
near the critical temperatures of methanol and ethanol [1012]. In
the biodiesel productions, glycerol is also produced as the byprod-
uct. The removal of glycerol is required for production of the high
quality biodiesel. It is useful for the design of the separation process
between biodiesel and glycerol to understand the phase behav-
ior for supercritical alcohol + glycerol systems as well as that for
supercritical alcohol + fatty acid ester systems.
To elucidate the phase behavior for supercritical alcohol +
glycerol systems, the vaporliquid equilibria for methanol +
glycerol and ethanol + glycerol systems were measured near the
critical temperatures of the alcohols by a ow method. The
vaporliquid equilibria were calculated by PengRobinson equa-
tion of state modied by StryjekVera [13]. A conventional mixing
rule and PRASOG model [14] were adopted for the energy and size
parameters in the equation of state. The calculated results are com-
pared with the experimental data.
2. Experiment
2.1. Materials

Methanol, ethanol and glycerol used in this work were sup-

Corresponding author. Tel.: +81 92 802 2771; fax: +81 92 802 2771. plied by Wako Pure Chem. Ind. Their purities were checked with
E-mail address: yshimo@chem-eng.kyushu-u.ac.jp (Y. Shimoyama). a gas chromatograph. The peak area percentages of the main com-

0378-3812/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.uid.2009.06.010
 Y. Shimoyama et al. / Fluid Phase Equilibria 284 (2009) 6469 65

pounds for methanol, ethanol and glycerol were more than 99.8, Table 1
Experimental results of vaporliquid equilibria for methanol (1) + glycerol (2)
99.5 and 99.0%, respectively. These materials were used without
system.
further purication.
T (K) p (MPa) N x1 Sx y1 Sy

2.2. Apparatus and procedure 493 3.03 5 0.478 0.85 n.d. 0.00
3.41 4 0.550 0.68 n.d. 0.00
3.86 4 0.645 0.74 n.d. 0.00
A ow method was adopted for the measurements of the 4.23 5 0.701 0.78 n.d. 0.00
vaporliquid equilibria for methanol + glycerol and ethanol + 4.67 5 0.850 0.73 n.d. 0.00
glycerol systems near the critical temperatures of the alcohols. The 5.12 6 0.965 0.28 n.d. 0.00
ow type apparatus was also used for the measurements of the 523 4.64 5 0.484 0.63 n.d. 0.00
5.21 4 0.565 0.44 n.d. 0.00
phase equilibria of the systems including, water, hydrocarbon, alco-
6.08 4 0.689 0.42 n.d. 0.00
hol, methyl ester and ethyl ester in the previous work [11,12,15]. 6.79 6 0.807 0.41 n.d. 0.00
The schematic diagram of the apparatus is shown in Fig. 1. The 7.16 4 0.868 0.29 n.d. 0.00
apparatus was composed of a material supplying system, an equi- 543 5.41 6 0.431 0.85 n.d. 0.00
librium cell, temperature and pressure controlling systems, and a 6.18 6 0.509 0.11 n.d. 0.00
6.99 6 0.592 0.84 n.d. 0.00
sampling system. The equilibrium cell was equipped with sapphire 7.91 6 0.697 0.31 n.d. 0.00
windows to observe the phase behavior inside the cell. The inner 8.61 5 0.780 0.47 0.990 0.047
diameter was 20 mm and the volume was 31 mL. A detailed descrip- 9.55 5 0.887 0.33 0.976 0.062
tion of the equilibrium cell was given in the previous work [15]. 573 6.90 4 0.433 0.46 n.d. 0.00
7.86 5 0.502 1.26 n.d. 0.00
The equilibrium cell was connected with four lines, a feed line, two
9.00 5 0.602 0.60 0.986 0.067
sampling lines for vapor and liquid phases, and a subsidiary line. 9.97 5 0.671 0.29 0.976 0.085
The subsidiary line was used to maintain the phase interface in the 11.01 4 0.758 0.73 0.963 0.18
equilibrium cell at the center of the cell. Superscriptsx: liquid phase; y: vapor phase. n.d.: glycerol was not detected.
In the measurements, rst of all, the system was heated to N: number of samples at constant temperature and pressure S x =
the desired temperature by electric heaters. The mixtures of 
N
x  
N
y 
1 1,n x1,ave 1 1,n y1,ave
methanol + glycerol or ethanol + glycerol were supplied by a non- N x1,ave
100 and S y = N y1,ave
100.
pulsating HPLC pump (PUS/PUD, GL sciences). The ow rates during n=1 n=1

the measurements were 2.06.5 g min1 . A line mixer was used

to promote the equilibrium condition. In the cell, uid was sep-
experimental uncertainties of mole fractions in vapor and liquid
arated into vapor and liquid phases. The phase behavior in the
phases were 0.0002 and 0.006 for methanol + glycerol and 0.0003
cell was observed with a 42-power telescope (CCD-TR3300, SONY).
and 0.004 for ethanol + glycerol systems.
The temperatures of entrance, top and bottom of the cell were
controlled within 0.5 K. The pressure was controlled by a back
pressure regulator. The pressure uctuation was controlled within 2.3. Results and discussion
0.02 MPa during the measurements. The efuents from vapor and
liquid phases were depressurized through expansion valves. Sam- The experimental results of the vaporliquid equilibria for
ples from the vapor and liquid phases were trapped into sampling methanol + glycerol and ethanol + glycerol systems at 493573 K
bottles every 15 min for 1 h. The sampling bottles were cooled are listed in Tables 1 and 2. In this work, the experimental
in water baths in order to prevent volatilization of methanol or
ethanol. The sample volume trapped for the analysis was about Table 2
10 mL. The samples from the liquid phase were diluted with 1- Experimental results of vaporliquid equilibria for ethanol (1) + glycerol (2) system.
propanol. The volume ratio of 1-propanol to the liquid phase sample T (K) p (MPa) N x1 Sx y1 Sy
was 10. The compositions in vapor and liquid phases were analyzed
493 2.27 5 0.540 0.31 n.d. 0.00
by a gas chromatograph with a ame ionization detector (GC-14, 2.66 4 0.663 0.28 n.d. 0.00
Shimadzu) using Inter Cap 1701 capillary column (GL science). The 2.81 4 0.698 0.17 n.d. 0.00
3.01 6 0.766 0.39 n.d. 0.00
3.15 6 0.833 0.52 n.d. 0.00
3.39 6 0.889 0.29 n.d. 0.00
523 2.51 5 0.346 0.49 n.d. 0.00
3.26 5 0.455 0.56 n.d. 0.00
3.94 6 0.591 0.28 n.d. 0.00
4.60 6 0.741 0.41 n.d. 0.00
5.32 6 0.879 0.27 n.d. 0.00
543 3.12 4 0.316 0.40 n.d. 0.00
3.76 6 0.414 0.48 n.d. 0.00
4.43 6 0.495 0.11 n.d. 0.00
5.12 6 0.603 0.58 n.d. 0.00
5.81 6 0.700 0.55 n.d. 0.00
6.54 6 0.809 0.08 0.985 0.12
573 4.73 6 0.364 0.50 0.9999 0.005
5.52 6 0.436 0.28 0.9999 0.00
6.52 6 0.531 0.36 0.983 0.21
7.51 5 0.634 0.23 0.959 0.083
8.78 6 0.773 0.32 0.931 0.14
Fig. 1. Schematic diagram of ow type apparatus. (1) Alcohol + glycerol mixture Superscriptsx: liquid phase; y: vapor phase. n.d.: glycerol was not detected.
reservoir, (2) electronic balance, (3) feed pump, (4) pressure gauge, (5) safety valve, N: number of samples at constant temperature and pressure S x =
(6) check valve, (7) stop valve, (8) precision pressure gauge, (9) preheating coil, (10) 
N
x  
N
y 
line mixer, (11) equilibrium cell, (12) lter, (13) back pressure regulator, (14) expan- 1 1,n x1,ave 1 1,n y1,ave
N x1,ave
100 and S y = N y1,ave
100.
sion valve, (15) sampling bottle, (16) water bath and RTD 13: resistance temperature
n=1 n=1
detector.
66 Y. Shimoyama et al. / Fluid Phase Equilibria 284 (2009) 6469

Fig. 2. Vaporliquid equilibria for methanol (1) + glycerol (2) and methanol (1) + methyl laurate (2) systems: glycerol () 493 K, () 523 K, () 543 K and () 573 K. Methyl
laurate [11] () 493 K, () 523 K and () 543 K.

data of the phase equilibria were determined from the averaged parisons between Figs. 2 and 3, it is found that the pressures of
value of several samples at a constant temperature and pressure. saturated liquid and vapor lines for methanol + glycerol system are
Figs. 2 and 3 show the comparisons of the phase behavior for higher than those for ethanol + glycerol system. This is resulted from
methanol + glycerol and ethanol + glycerol systems with those for the vapor pressures of methanol higher than those of ethanol.
methanol + methyl laurate and ethanol + ethyl laurate systems. The
mole fractions of alcohol in vapor phase for methanol + glycerol and
3. Calculation
ethanol + glycerol are very close to unity at the pressures lower than
7.0 and 6.0 MPa at 493573 K, respectively. The mole fractions of
3.1. PengRobinson StryjekVera equation of state
alcohol for alcohol + glycerol systems are higher than those for the
case of methyl laurate or ethyl laurate at constant temperatures. The
The vaporliquid equilibria for methanol + glycerol and
pressures of liquid saturated lines for alcohol + glycerol systems are
ethanol + glycerol systems were calculated by PengRobinson
higher than those for methanol + methyl laurate and ethanol + ethyl
StryjekVera equation of state (PRSV EOS) [13]. PRSV EOS is given
laurate systems. These results mean that the vaporliquid two
by the following equations
phase regions for alcohol + glycerol systems are larger than those
for alcohol + fatty acid ester systems. The phenomena are discrepant RT a
in consideration of the boiling points of fatty acid esters and glyc- p= (1)
vb v2 + 2bv b2
erol. These comparisons are highly useful for the optimizations of
the separation between the fatty acid esters and glycerol in the R2 Tc2
a = 0.457235 (2)
biodiesel production using supercritical alcohol. From the com- pc

Fig. 3. Vaporliquid equilibria for ethanol (1) + glycerol (2) and ethanol (1) + ethyl laurate (2) systems: glycerol () 493 K, () 523 K, () 543 K and () 573 K. Ethyl laurate
[12] () 493 K, () 523 K and () 543 K.
 Y. Shimoyama et al. / Fluid Phase Equilibria 284 (2009) 6469 67

Table 3
Critical properties and substance parameters in equation of state.

Substance Tc (K) pc (MPa) 1 ui (Tr = 0.4)

Methanol 512.64 [16] 8.097 [16] 0.56533 [16] 0.16816 [13] 1.0810 [14]
Ethanol 513.92 [16] 6.148 [16] 0.649 [16] 0.03374 [13] 1.0732 [14]
Glycerol 850 [17] 7.50 [17] 0.516 [18] 0.3075 [18] 1.0733 [14]

RTc where xi is the mole fraction of component i. The parameters kij

b = 0.077796 (3)
pc and lij are the binary parameters for components i and j. These
   T 2  2 parameters were determined from the vaporliquid equilibrium
data obtained in this work. The parameter kij is dependent on tem-
= 1+ 1 (4)
Tc perature given by the following equations
  T 0.5 
 T  176.7
k12 = 0.3977 for methanol (1) + glycerol (2) (9)
 = 0 + 1 1+ 0.7 (5) T
Tc Tc
36.49
0 = 0.378893 + 1.4897153 0.171318482 + 0.01965543 (6) k12 = 0.1899 for ethanol (1) + glycerol (2) (10)
T
where p is the pressure, R is the gas constant, T is the tempera- lij is independent of temperature. The optimized values of lij for
ture, and v is the molar volume. The parameters a and b are the methanol + glycerol and ethanol + glycerol are 0.099 and 0.088,
energy and size parameters, respectively. is the acentric factor, respectively.
1 is the substance parameter determined by tting the saturated
vapor pressures for pure substance. The subscript c denotes the crit- 3.2.2. PRASOG model
ical properties. The experimental data of the critical properties and PRASOG model [14] was also adopted for the energy and size
the acentric factors for methanol, ethanol and glycerol are available parameters of the equation of state. PRASOG model is given by the
from the literatures [1618]. The substance parameter of glycerol following equations
was determined from the vapor pressure data [18] in this work. The

critical properties and the substance parameters of the compounds a  ai ln Qi 2 2RT g0E  b   u1 
focused in this work are listed in Table 3. = + xi ln + xi ln
b bi ln Q ln Q RT bi ui 1
i i i

3.2. Mixing rule (11)


3.2.1. Conventional mixing rule 1+ 2+u 1+ 2 + ui v0i
A conventional mixing rule was used for the energy and size Q = , Qi = , u= xi ui , ui =
1+ 2u 1 + 2 ui bi
parameters of PRSV EOS. The energy and size parameters using the i
conventional mixing rule are as follows (12)
    
a= xi xj aij , aij = (1 kij ) ai aj (7) a aij
b = xi xj bij (13)
i j RT RT
i j
 bi + bj 1/3 1/3
b= xi xj bij , bij = (1 lij )
2
(8)  1/3
bi + bj
i j
aij = ai aj , bij = (1 lij ) (14)
2

Fig. 4. Calculated results of vaporliquid equilibria for methanol (1) + glycerol (2) system: Exp. () 493 K, () 523 K, () 543 K and () 573 K. Calc. () conventional mixing
rule and (- - -) PRASOG.
68 Y. Shimoyama et al. / Fluid Phase Equilibria 284 (2009) 6469

Fig. 5. Calculated results of vaporliquid equilibria for ethanol (1) + glycerol (2) system: Exp. () 493 K, () 523 K, () 543 K and () 573 K. Calc. () conventional mixing rule
and (- - -) PRASOG.

where g0E is the excess Gibbs free energy at zero pressure and is Table 4
Group interaction parameters in ASOG equation [19].
calculated using ASOG equation [19]. v0i denotes the molar volume
of component i at zero pressure and the reduced temperature of k l
0.4. The values of ui for methanol, ethanol and glycerol in Eq. (12) CH2 OH
are shown in Table 3. The mixture parameters a and b can be eval-
mkl nkl [K] mkl nkl [K]
uated by solving Eqs. (11) and (13). The excess Gibbs free energy
is calculated from ASOG equation [19] as shown by the following CH2 0 0 41.2503 7686.4
OH 4.7125 3060.0 0 0
equation

g0E 
= xi (ln iFH + ln iG ) (15)
RT vki means the atom number except hydrogen atom included in
i
group k in the component i. The superscript (i) denotes the pure
where  i and xi are the activity coefcient and the mole fraction component i. Xk and ckl are the number fraction of group k and the
of component i, respectively. The superscripts FH and G mean the group interaction parameter given as follows
FloryHuggins [20] and group interaction terms, respectively. The 
xi ki
group interaction term can be calculated from group activity coef- Xk =  i (18)
cient  k given as follows x
i i

l li

ln iG = ki (ln k ln k )
(i)
(16) nkl
ln ckl = mkl + (19)
T
k

  Xc The group parameters mkl and nkl in Eq. (19) for the group pairs
ln k = 1 ln Xl ckl  l lk (17) focused in this work are cited from the literature [19] and are listed
Xc
s s ls
l l in Table 4.

Table 5
Calculated results of vaporliquid equilibria for alcohol (1) + glycerol (2) systems.

Alcohol T (K) Nd Conventional mixing rule PRASOG model

x y x y

Methanol 493 6 3.43 0.51 6.73 0.26

523 5 2.11 1.31 5.21 0.78
543 6 2.63 1.82 5.33 1.22
573 5 0.80 3.34 3.47 1.86

Ethanol 493 6 2.33 0.50 8.22 0.46

523 5 2.92 1.51 5.83 1.29
543 6 1.60 2.40 5.53 1.95
573 5 1.25 3.20 5.16 2.66

Average 2.13 1.82 5.69 1.31

Nd : number of data points.


Nd
 (i) (i)  
Nd
 (i) (i) 
Superscriptsx: liquid phase; y: vapor phase. x = 100
Nd
xexp xcalc , y = 100
N
yexp ycalc .
d

i=1 i=1
 Y. Shimoyama et al. / Fluid Phase Equilibria 284 (2009) 6469
3.3. Results and discussion
The calculations of the vaporliquid equilibria were per-
formed at a xed temperature and pressure. The calculated
results of the vaporliquid equilibria for methanol + glycerol and
ethanol + glycerol systems are shown in Figs. 4 and 5, respectively.
The deviations between the experimental and calculated results are
listed in Table 5. The average deviations between the experimental
and calculated results in vapor and liquid phases are 0.0182 and
0.0213 with the conventional mixing rule, and 0.0131 and 0.0569
with PRASOG model, respectively. In liquid phase for both systems,
the calculated results with the conventional mixing rule repro-
duce the experimental data more accurate than those with PRASOG
model. While, the results with PRASOG model are better than those
with the conventional mixing rule in vapor phase for both sys-
tems. These results in vapor phase are highly remarkable because
there are no adjustable parameters in PRASOG model in spite of two
adjustable parameters in the conventional mixing rule.
4. Conclusion
The vaporliquid equilibria for methanol + glycerol and
ethanol + glycerol systems were measured at 493573 K by a ow
method. The vapor phase is composed of alcohol approximately at
the pressures lower than 7.0 and 6.0 MPa for methanol + glycerol
and ethanol + glycerol systems. The pressures of saturated liquid
lines for alcohol + glycerol systems are higher than those for
methanol + methyl laurate or ethanol + ethyl laurate systems.
PengRobinson StryjekVera equation of state was used for the
calculations of the vaporliquid equilibria for the systems focused
in this work. The conventional mixing rule and PRASOG model were
69
applied for the energy and size parameters in the equation of state.
In liquid phase, the results with the conventional mixing rule are
in better agreement with the experimental data than those with
PRASOG model. Interestingly, PRASOG model without adjustable
parameters reproduce the experimental data in vapor phase more
accurate than the conventional mixing rule with two adjustable
parameters.
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