Article

pubs.acs.org/IECR

LiquidLiquid Phase Equilibria for Soybean Oil Methanolysis:

Experimental, Modeling, and Data Prediction
Abraham Casas, Jose Francisco Rodrguez, Gonzalo L. del Peso, Rosala Rodrguez,
Gemma Vicente,,* and Alicia Carrero

Department of Chemical and Energy Technology, ESCET, Universidad Rey Juan Carlos, c/Tulipan s/n, 28933 Mostoles, Madrid,
Spain

Repsol Technology Center, 28935 Mostoles, Madrid, Spain

S Supporting Information
*

ABSTRACT: Liquidliquid equilibrium data of the system composed by soybean oil, fatty acid methyl esters (FAMEs),
methanol, and glycerol were experimentally determined at temperatures of 25, 45, and 65 C. Three binary systems (oil +
methanol, oil + glycerol, and FAMEs + glycerol) and all the ternary combinations were evaluated. With these data, universal
quasichemical (UNIQUAC) and non-random two-liquid (NRTL) binary interaction coecients were calculated and validated.
According to the results, the UNIQUAC model tted the experimental data better than the NRTL one. In order to complete this
study, UNIQUAC binary interaction coecients for the mixtures of oil, FAMEs, methanol, and glycerol with monoglycerides and
diglycerides were also predicted using a group contribution model (universal quasichemical functional-group activity coecients)
and checked using experimental data from the soybean oil transesterication reaction.

1. INTRODUCTION
Nowadays, base-catalyzed transesterication of vegetable oils
with methanol (also called methanolysis) is the most widely
used technology to produce fatty acid methyl esters (FAMEs)
as biodiesel on an industrial scale.1 This reaction is essentially
biphasic from the beginning (methanol has a low solubility in
triglycerides) to the end (glycerol is practically immiscible in
FAMEs) under the reaction conditions usually employed in the
industrial process (methanol:oil molar ratio of 6:1 and 60
C).1,2 Therefore, the determination of the liquidliquid
equilibrium (LLE) data is crucial for a better understanding
of the reaction pathway and the separation of the products.
Furthermore, in the recent years there has been an increasing
interest in the study of the transesterication reaction from the
point of view of mass transfer between phases,36 which
requires LLE data, thus complementing the large number of
existing kinetic studies.710
Six major compounds coexist until the end of the triglyceride
methanolysis reaction: triglycerides, FAMEs, methanol, glycerol, diglycerides, and monoglycerides. However, previous
literature has focused mainly on the FAMEsmethanol
glycerol equilibrium, which represents the end of the
reaction.1116 The remaining binary and ternary systems
formed by these six compounds have hardly been studied,12,17,18 with the exception of the oilmethanol binary
mixture, which corresponds to the initial stage of the
reaction.6,1821
Given this situation, it is necessary to complete this
information with new experimental data. It should be noted
that mono-, di-, and triglycerides and FAMEs are actually
groups of compounds whose composition varies according to
the fatty acid prole. In this sense, only soybean oil and
monoglycerides, diglycerides, and FAMEs derived from this oil
were selected in this study as models for these compounds.
XXXX American Chemical Society

Moreover, high-purity mono- and diglycerides are dicult to

purchase in sucient quantities. Thus, their activity coecients
in mixtures of soybean oil, FAMEs, methanol, and glycerol were
predicted with the UNIFAC (universal quasichemical functional-group activity coecients) model.
Therefore, the aim of this work is the measurement of the
LLE data of all the binary and ternary systems among soybean
oil, FAMEs, methanol, and glycerol at temperatures from
299.15 to 341.85 K. These new experimental data were used to
estimate the binary interaction coecients of the universal
quasichemical (UNIQUAC) and non-random two-liquid
(NRTL) models. New data from the quaternary system were
acquired to test the validity of the estimated parameters.
Finally, binary interaction coecients including those of
monoglycerides and diglycerides were predicted using the
UNIFAC model and checked with experimental data from the
soybean oil methanolysis reaction.

2. MATERIALS AND METHODS

2.1. Materials. Rened soybean oil was provided by Gustav
Heess S.L. The fatty acid prole of this vegetable oil is shown in
Table S1 in Supporting Information. Methanol (99%), glycerol
(99%), acetic acid (99%), and 3A molecular sieves were
supplied by Scharlab, S.L. Sodium methoxide (32 wt % in
methanolic solution) was obtained from Merck. FAMEs were
synthesized through soybean oil methanolysis using sodium
methoxide as a catalyst and following the procedure described
in a previous publication.22
Received: November 19, 2013
Revised: February 5, 2014
Accepted: February 5, 2014

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xiIi I = xiIIi II

Gas chromatographic analysis required heptane (99.5%)

and methyl heptadecanoate (99.7%) from Fluka and Nmethyl-N-(trimethylsilyl)triuoroacetamide (MSTFA, synthesis
grade), butanetriol (analytical standard), and tricaprin (analytical standard) from Sigma-Aldrich.
2.2. Equipment and Procedure. Liquidliquid equilibrium experiments were performed in 100-mL sealed-cap glass
vessels placed over a heating magnetic stirrer (JP Selecta
AGIMATIC-ED). Temperature was measured using a Pt-100
probe (Heidolph EKT 3001) immersed in the 100-mL glass
vessel and connected to the heater plate (error 0.1 K). Feed
mixtures comprised of dierent proportions of soybean oil,
FAMEs, methanol, and glycerol were added to the vessel,
heated to the chosen temperature, and stirred during 120 min.
After reaction, the resulting layers were allowed to separate
until both phases were clear. Samples of 5 mL were taken from
both phases for further analysis, using a Transferpette pipet
(Brand GmbH).
Low-conversion soybean oil methanolysis was carried out in
a 200-mL cylindrical reactor with a spherical bottom, immersed
in a thermostated silicon bath. This reactor was initially lled
with soybean oil and the mixture of methanol (6 mol/mol of
oil) and sodium methoxide (0.2 mol/mol of oil) and preheated
at 25 C. The stirrer, located in the oil phase, was then turned
on (100 rpm). After 4 h, samples were withdrawn from the
nonpolar (oil/FAMEs) and polar (methanol/glycerol) phases
and neutralized with a stoichiometric amount of acetic acid to
stop the reaction. Finally, these samples were analyzed by gas
chromatography.
2.3. Analytical Methods. FAME content was determined
following EN 14103 standard in a Hewlett-Packard 6890 gas
chromatograph with a column DB-WAX (30 m length, 0.25 m
thickness and 0.32 mm of internal diameter). Oven temperature was set at 200 C and the pressure at 80 kPa, using He as
carrier gas. Three analyses of a reference sample were carried
out to calculate the experimental error, obtaining a value of
0.6 wt % of FAMEs.
Triglycerides, diglycerides, monoglycerides, and glycerol
measurements were carried out in an Agilent 6890N gas
chromatograph following the procedure shown in the EN
14105 standard. A special column for high temperatures (DB5ht, 15 m length, 0.10 m thickness and 0.32 mm of internal
diameter) and derivatization with MSTFA were used due to the
high boiling points of these compounds. The column pressure
was set at 24.1 kPa. The oven temperature was set at 120 C for
5 min and was increased to 180 C at a rate of 15 C min1 and
then to 230 at 7 C min1 and nally to 370 at 10 C min1.
This analysis was repeated twice, showing an error value of
0.015 wt % for triglycerides and diglycerides, 0.025 wt % for
monoglycerides, and 0.0015 wt % for glycerol.
Methanol determination was performed by gravimetric
analysis. The sample was weighed in a Sartorius TE214 S
analytical scale with a precision of 0.0001 g. Then, the sample
was placed in a vacuum rotary evaporator (60 C) and after 30
min was weighed again. This procedure was repeated until the
sample weight remained constant, and the weight dierence
corresponded to the methanol amount, due to its lower boiling
point. This analysis showed an error value below 0.1 wt %.

(1)

where xIi and xIIi are the molar fractions of the component i in
phases I and II, respectively, whereas Ii and IIi are the activity
coecients of the component i in phases I and II, respectively.
Thereby, the determination of equilibrium data requires the
calculation of Ii and IIi , which can be accomplished by
estimating parameters of activity coecient models (such as
UNIQUAC or NRTL) with LLE experimental data or by the
prediction of these coecients (e.g., determination by group
contribution models such as UNIFAC).
UNIQUAC23 and NRTL24 have been selected for the
modeling of activity coecients in this work. In the UNIQUAC
model, activity coecients (i) are calculated by taking into
account the contribution of the combinatorial contribution, Ci ,
due to the size and shape of the molecules and the residual
contribution, iR, caused mainly by interaction energy as
expressed in eq 2:

ln i = ln iC + ln i R

(2)

The rst term is calculated with the eq 3

ln iC = (1 Vi + ln Vi )

V
V
z
qi1 i + ln i
2
Fi
Fi

(3)

where z has a usual value of 10. ri and qi are the van der Waals
molecular volume and molecular supercial area, respectively,
which were calculated using the UNIFAC model25,26 (Table S2
in Supporting Information). Finally, Vi and Fi are calculated
with eqs 4 and 5, xj being the molar fraction of j compound:
ri
Vi =
j rjxj
(4)

Fi =

qi
j qjxj

(5)

The residual contribution term was calculated with the eq 6

j qjxjji
ln i R = qi1 ln

j qjxj

k qk xkkj
qjxjij

(6)

where ij is calculated with the following equation:

Uij
ij = exp

(7)

In this equation, parameter

coecient between compounds
in K. Note that for each pair
coecients (Uij Uji; Uii = 0).
In the NRTL model, activity
using this expression
ln i =

j xjjiGji
k xkGki

Uij is the binary interaction

i and j and T the temperature
of compounds there are two
coecients (i) are calculated

x G
ij m m mj mj
k xkGkj
k xkGkj
xjGij

(8)

3. MODELING OF LIQUIDLIQUID EQUILIBRIUM

DATA
3.1. Activity Coecient Models. In LLE, the following
condition must be satised

where x is the molar fraction.

The value of Gij is obtained with the eq 9:
Gij = exp( ijij)
B

(9)

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ij values were considered 0.3 if compounds i and j were

completely miscible and 0.2 when they were immiscible (Table
S3 in Supporting Information).24 ij is calculated with the
equation
Aij
ij = exp
T

Table 1. Experimental Equilibrium Compositions (wt %) for

the Binary Systems Oil (1)Methanol (3), Oil (1)Glycerol
(4), and FAMEs (2)Glycerol (4)
phase I

(10)

where Aij is the binary interaction coecient between

compounds i and j in NRTL model (Aij Aji; Aii = 0) and
T the temperature in K.
Finally, LLE of binary mixtures with diglycerides and
monoglycerides has been predicted using the last revision25
of the original UNIFAC method developed by Fredenslund et
al.26
3.2. LiquidLiquid Equilibrium Calculation. LLE
calculation has been performed through the minimization of
Gibbs free energy (GT)
GT =

(11)

methanol (3)

oil (1)

94.38
92.72
89.98

5.62
7.28
10.02

0.25
0.55
0.84

99.75
99.45
99.16
phase II

oil (1)
0.10
0.17
0.84

glycerol (4)
99.90
99.83
99.16
phase II

oil (1)
99.93
99.87
99.85

glycerol (4)
0.07
0.13
0.15
phase I

methanol (3)

T (C)

FAMEs (2)

glycerol (4)

FAMEs (2)

glycerol (4)

26
46.2
68.7

99.96
99.93
99.88

0.04
0.07
0.12

0.66
0.83
1.34

99.34
99.17
98.66

Table 2. RMSD Values for All the Systems Studied in This

Work

where R is the ideal gas constant, T is the temperature (in K),

nT is the total number of moles, nI is the number of moles in
the phase I, nII is the number of moles in the phase II, and GE
(excess Gibbs free energy in each phase) is calculated as
(12)

This condition must be satised with the following equation:

ni = niI + niII

oil (1)

28
47.7
63.7

phase I

nT

T (C)

T (C)
27
46.2
68.7

n I (RT i xiI ln xiI + GE(I )) + n II (RT i xiII ln xiII + GE(II ))

GE = RT xi ln i

phase II

(13)

system

UNIQUAC

NRTL

oil (1)methanol (3)

oil (1)glycerol (4)
FAMEs (2)glycerol (4)
oil (1)FAMEs (2)methanol (3)
oil (1)FAMEs (2)glycerol (4)
oil (1)methanol (3)glycerol (4)
FAMEs (2)methanol (3)glycerol (4)
all systems

0.0118
0.0022
0.0022
0.0139
0.0056
0.0492
0.0248
0.0249

0.0511
0.0025
0.0019
0.0556
0.0058
0.0443
0.0385
0.0412

3.3. Parameters Estimation. The binary interaction

coecients of UNIQUAC (Uij) and NRTL (Aij) models were
estimated by minimizing the objective function, in this case the
residual squares sum, RSS:
NTL

RSS =

NP

NC

(xiIexp xiIcalc)2
N =1 I=1 i=1

xIiexp

(14)

xIicalc

where
and
were the experimental and calculated molar
fraction of the compound i in the phase I, respectively. NTL are
the number of tie lines, NP the number of phases in
equilibrium, and NC the number of compounds.
Minimization was carried out with the MATLAB software
using a direct search function such as pattern search and default
options (patternsearch) to nd a proper rst assumption of the
global minimum, followed by a local minimum solver
(f minsearch with Algorithm and Interior point options
activated) to converge to the optimized answer.
The computer codes for NRTL and UNICUAC models have
been included as Supporting Information.

Figure 1. Liquidliquid equilibrium for methanol (1)FAMEs (2)

soybean oil (3) at 47.7 C. Composition in mass fractions. Empty
symbols, experimental data; blue solid lines, equilibrium curve and tie
lines calculated with UNIQUAC; red dashed lines, calculated with
NRTL.

4. RESULTS AND DISCUSSION

Experimental equilibrium compositions of the binary mixtures
are shown in Table 1 (in wt %) and in Table S4 of the
Supporting Information (in molar fractions). Methanol
solubility in the soybean oil phase ranged between 5.62 and
10.02 wt % with temperatures from 28 to 63.7 C. These values
corresponded to methanol:oil molar ratios from 1.6:1 to 3:1
(stoichiometric ratio of transesterication reaction) and were
consistent with previous values shown in the literature (5.03
and 7.30 wt % at 25 C).6,20 Furthermore, the concentration of

oil in the methanol phase did not exceed the value of 0.84 wt %
in the temperature range studied. Table 1 also shows high
immiscibility of the soybean oil and FAMEs with glycerol
binary mixtures. In all cases, glycerol solubility in oil and
FAMEs was below 0.15 wt %. The values reported previously
C

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Figure 2. Liquidliquid equilibrium for FAMEs (1)methanol (2)

glycerol (3) at 45.7 C. Composition in mass fractions. Empty
symbols, experimental data; blue solid lines, equilibrium curve and tie
lines calculated with UNIQUAC; red dashed lines, calculated with
NRTL.

Figure 4. Liquidliquid equilibrium for soybean oil (1)glycerol (2)

methanol (3) at 46.2 C. Composition in mass fractions. Empty
symbols, experimental data; blue solid lines, tie lines calculated with
UNIQUAC; red dashed lines, calculated with NRTL.

Table 3. UNIQUAC Parameters (Uij) Estimated for the

System Soybean Oil (1)FAMEs (2)Methanol (3)
Glycerol (4)
Uij

soybean oil
(1)

FAMEs
(2)

methanol
(3)

glycerol
(4)

soybean oil (1)

FAMEs (2)
methanol (3)
glycerol (4)

0
585.00
13.49
544.44

331.21
0
56.06
83.94

520.74
579.24
0
65.03

69.75
315.25
28.00
0

fractions) and they are also collected in Tables S5S8 of the

Supporting Information (in molar fractions) at each temperature. Figure 1 shows the LLE for the methanol (1)FAMEs
(2)soybean oil (3) mixture. As can be observed, the presence
of FAMEs increased the solubility of methanol in the oil phase,
while the equilibrium content of soybean oil remained low in
the methanol phase. These data add to the limited literature
information for this mixture, which is crucial for understanding
the behavior in the initial stage of the methanolysis reaction.6,17
This could contribute to an enhanced design of the agitation
mixing system in biodiesel industrial production. LLE of the
FAMEs (1)methanol (2)glycerol (3) mixture is shown in
Figure 2. In this case, the substitution of soybean oil by glycerol
led to a system with a higher biphasic region.
It is well-known that the low solubility of glycerol in the
FAME phase represents an advantage in the production of
biodiesel through triglyceride methanolysis. The glycerol
byproduct formed in this reaction is released from the FAME
phase and the reaction equilibrium is shifted toward product
formation. This situation is less favored when the methanol to
oil ratio is high, because the glycerol solubility in the FAME
phase increases. For this reason, methanol to oil ratios higher
than 6 are not usually used in the industrial production of
biodiesel.
As commented before, glycerol is hardly miscible in soybean
oil and FAMEs; thus, the glycerol (1)soybean oil (2)
FAMEs (3) data plot in Figure 3 represents a practically
immiscible system for almost the whole concentration range.
The same situation was found for mixtures of soybean oil (1),

Figure 3. Liquidliquid equilibrium for glycerol (1)soybean oil (2)

FAMEs (3) at 46.2 C. Composition in mass fractions. Empty
symbols, experimental data; blue solid lines, tie lines calculated with
UNIQUAC; red dashed lines, calculated with NRTL.

were only slightly higher (0.25 and 0.33 wt % at 25 and 45 C,

respectively).15
These experimental data from binary mixtures were used to
obtain a rst approximation of their binary interaction
coecients in the UNIQUAC and NRTL models. Rootmean-square deviations (RMSD) between calculated and
experimental values in these binary mixtures are shown in
Table 2. The results showed that UNIQUAC and NRTL
accurately tted the data from soybean oil and FAMEs with
glycerol. However, only the UNIQUAC model achieved an
acceptable t for the experimental data in the soybean oil
methanol mixture. The UNIQUAC method has also shown an
adequate t of LLE data for these mixtures in previous
publications.1517
The next step of this work was to evaluate the LLE of all the
possible ternary mixtures in the soybean oilFAMEs
methanolglycerol system. LLE experimental data for these
ternary mixtures are represented in Figures 1 4 (in mass
D

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Table 4. Experimental (exp) and Calculated (calc) Equilibrium Compositions (wt %)

soybean oil phase
T (C)
23
45.7
65.7
a

methanol phase

data

oil

FAMEs

methanol

glycerol

oil

FAMEs

methanol

glycerol

exp
calca
exp
calca
exp
calca

49.14
47.46
47.82
48.25
47.97
45.75

45.34
46.20
44.14
44.75
44.24
45.26

5.30
6.29
7.47
6.93
7.40
8.89

0.22
0.04
0.57
0.07
0.39
0.11

0.63
0.01
0.13
0.01
0.04
0.01

2.67
0.82
1.86
0.65
2.37
1.18

67.25
66.92
58.93
60.10
58.32
62.22

29.45
32.26
39.08
39.24
39.27
36.59

LLE data were calculated using the UNIQUAC model and parameters from Table 3.

Table 5. Experimental (exp) and Calculated (calc) Compositions (wt %) after Soybean Oil Methanolysisa
soybean oil phase
data
b

exp
calcc

methanol phase

oil

FAMEs

methanol

glycerol

diglycerides

monoglycerides

oil

FAMEs

methanol

glycerol

diglycerides

monoglycerides

69.5
72.0

12.0
10.09

6.6
6.8

0.1
0.01

11.5
10.9

0.3
0.2

0.1
0.2

0.8
0.7

84.2
81.5

1.7
1.6

8.7
10.5

4.5
5.5

Reaction conditions: T = 25 C; Methanol:oil molar ratio = 6:1; Catalyst (CH3OK):oil molar ratio = 0.2:1; N = 100 rpm; time =240 min.
Experimental content values were normalized excluding catalyst concentration. cLLE data were calculated using the UNIQUAC model and
parameters from Table 3 and Table S10 (Supporting Information).
a
b

reaction. In this case, the diglycerides and monoglycerides are

distributed between the oil phase and the methanol phase.
These compounds possess fatty acid chains and OH groups
that favor the solubility in both phases. In a recent study,28
contents higher than 10 wt % of these compounds were also
found after low-conversion palm oil methanolysis. UNIQUAC
calculated values were similar to the experimental ones, thus
proving the validity of the model and parameters estimated in
this work. Future studies focusing on the eect of the
concentration of catalyst (in each phase) on the activity
coecients would be convenient to have a thorough knowledge
of the phase equilibrium during the reaction.

glycerol (2), and methanol (3), the ternary diagram of which is

shown in Figure 4.
Each ternary mixture was used to calculate initial values of
the binary coecients (Uij or Aij) for the UNIQUAC and
NRTL models (starting with estimations from binary mixtures).
RMSD values (from Table 2) reveal a proper t for both
models except for the soybean oil (1)FAMEs (2)methanol
(3) system with NRTL.
Having estimated the initial values of all binary coecients,
these were re-estimated taking into account all the experimental
data (binary and ternary mixtures) simultaneously. The nal
estimated values for UNIQUAC and NRTL are collected in
Tables 3 and S9 (Supporting Information), respectively. The
RMSD value for this overall estimation was much lower for the
UNIQUAC model than for the NRTL one. Moreover,
comparing the LLE calculated with experimental values
(Figures 14), it can also be seen that UNIQUAC was more
suitable for the LLE modeling of these four compounds, as
previously observed in the literature.1517,19,27
Next, a new set of experimental data obtained from a
quaternary mixture (at three dierent temperatures) was
evaluated to check the validity of the estimated parameters
with UNIQUAC. The initial mixture chosen for this purpose
was 0.5 mol of soybean oil, 4.5 mol of methanol, 0.5 mol of
glycerol, and 1.5 mol of FAMEs. Results are shown in Table 4.
As can be seen, UNIQUAC adequately reproduced the LLE for
this quaternary mixture in the temperature range studied.
Finally, the set of binary interaction coecients (Uij) was
completed, including values of mixtures with diglycerides and
monoglycerides. For this purpose, these UNIQUAC binary
interaction parameters were estimated using the activity
coecient data (i) predicted by UNIFAC for binary mixtures
that included these compounds. Estimated parameters are
shown in Table S10 in the Supporting Information. The validity
of the whole set of Uij parameters for UNIQUAC was tested by
comparing calculated LLE with experimental data from the
soybean oil methanolysis. Both sets of data are collected in
Table 5. Experimental data corresponded to a reaction with a
conversion below 15%. This low-conversion prole concentration was chosen because the reaction mixture contained
signicant amounts of all of the components involved in the

5. CONCLUSIONS
Methanol solubility in soybean oil was much higher (5.62
10.02 wt %) than that of this oil in methanol (0.250.84 wt %),
whereas the solubility of soybean oil and FAMEs with glycerol
was very low in the temperature range studied (2565 C).
Ternary mixtures with soybean oil and glycerol were practically
immiscible in all of the concentration ranges. Diglyceride and
monoglyceride solubility in methanol was higher than that of
soybean oil. The liquidliquid equilibrium of all the
compounds involved in soybean oil methanolysis was
adequately determined using UNIQUAC instead of NRTL.
Finally, UNIQUAC binary interaction coecients for the
mixtures with diglycerides and monoglycerides were correctly
estimated with coecient activities predicted with UNIFAC.
However, further experiments should be carried out with pure
diglycerides and monoglycerides to complete the estimation of
UNIQUAC parameters.

ASSOCIATED CONTENT

S Supporting Information
*

Tables S1S10 and computer codes for calculating activity

coecients for NRTL and UNIQUAC models. This material is
available free of charge via the Internet at http://pubs.acs.org.
E

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(19) Batista, E.; Monnerat, S.; Kato, K.; Stragevitch, L.; Meirelles, A.
J. A. Liquidliquid equilibrium for systems of canola oil, oleic acid, and
short-chain alcohols. J. Chem. Eng. Data 1999, 44, 1360.
(20) Yaginuma, R.; Moriya, S.; Yoshikazu, S.; Kodama, D.; Tanaka,
H.; Kato, M. Homogenizing effect of ethers added to immiscible
methanol/oil binary mixtures. Sekiyu Gakkaishi 2001, 44, 401.
(21) Mohsen-Nia, M.; Dargahi, M. Liquidliquid equilibrium for
systems of (corn oil + oleic acid + methanol or ethanol) at (303.15
and 313.15) K. J. Chem. Eng. Data 2007, 52, 910.
(22) Casas, A.; Ruiz, J. R.; Ramos, M. J.; Perez, A . Effects of triacetin
on biodiesel quality. Energy Fuels 2010, 24, 4481.
(23) Abrams, D. S.; Prausnitz, J. M. Statistical thermodynamics of
liquid mixtures: A new expression for the excess Gibbs energy of partly
or completely miscible systems. AIChE J. 1975, 21, 116.
(24) Renon, H.; Prausnitz, J. M. Local compositions in
thermodynamic excess functions for liquid mixtures. AIChE J. 1968,
14, 135.
(25) Fredenslund, A.; Jones, R. L.; Prausnitz, J. M. Groupcontribution estimation of activity coefficients in nonideal liquid
mixtures. AIChE J. 1975, 21, 1086.
(26) Wittig, R.; Lohmann, J.; Gmehling, J. Vaporliquid equilibria by
UNIFAC group contribution. 6. Revision and extension. Ind. Eng.
Chem. Res. 2003, 42, 183.
(27) Lee, M. J.; Lo, Y. C.; Lin, H. M. Liquidliquid equilibria for
mixtures containing water, methanol, fatty acid methyl esters, and
glycerol. Fluid Phase Equilib. 2010, 299, 180.
(28) Oh, P. P.; Chong, M. F.; Lau, H. L. N.; Chen, J.; Choo, Y. M.
Liquidliquid equilibrium (LLE) study for six-component transesterification system. Clean Technol. Environ. Policy 2013, 15, 817.

AUTHOR INFORMATION

Corresponding Author

*E-mail: gemma.vicente@urjc.es. Phone:+34 91 4888531. Fax:

+34 91 4887068.
Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
Financial support from REPSOL, S.A. is gratefully acknowledged.

REFERENCES

(1) Santori, G.; Di Nicola, G.; Moglie, M.; Polonara, F. A review

analyzing the industrial biodiesel production practice starting from
vegetable oil refining. Appl. Energy 2012, 92, 109.
(2) Casas, A.; Fernandez, C. M.; Ramos, M. J.; Perez, A.; Rodrguez,
J. F. Optimization of the reaction parameters for fast pseudo singlephase transesterification of sunflower oil. Fuel 2010, 89, 650.
(3) Frascari, D.; Zuccaro, M.; Pinelli, D.; Paglianti, A. A pilot-scale
study of alkali-catalyzed sunflower oil transesterification with static
mixing and with mechanical agitation. Energy Fuels 2008, 22, 1493.
(4) Frascari, D.; Zuccaro, M.; Paglianti, A.; Pinelli, D. Optimization of
mechanical agitation and evaluation of the mass-transfer resistance in
the oil transesterification reaction for biodiesel production. Ind. Eng.
Chem. Res. 2009, 48, 7540.
(5) Brasio, A. S. R.; Romanenko, A.; Santos, L. O.; Fernandes, N. C.
P. Modeling the effect of mixing in biodiesel production. Bioresour.
Technol. 2011, 102, 6508.
(6) Csernica, S. N.; Hsu, J. T. The phase behavior effect on the
kinetics of transesterification reactions for biodiesel production. Ind.
Eng. Chem. Res. 2012, 51, 6340.
(7) Freedman, B.; Butterfield, R. O.; Pryde, E. H. Transesterification
kinetics of soybean oil 1. J. Am. Oil. Chem. Soc. 1986, 63, 1375.
(8) Noureddini, H.; Zhu, D. Kinetics of transesterification of soybean
oil. J. Am. Oil. Chem. Soc. 1997, 74, 1457.
(9) Vicente, G.; Martinez, M.; Aracil, J.; Esteban, A. Kinetics of
sunflower oil methanolysis. Ind. Eng. Chem. Res. 2005, 44, 5447.
(10) Casas, A.; Ramos, M. J.; Perez, A. Kinetics of chemical
interesterification of sunflower oil with methyl acetate for biodiesel
and triacetin production. Chem. Eng. J. 2011, 171, 1324.
(11) Negi, D. S.; Sobotka, F.; Kimmel, T.; Wozny, G.; Schomacker,
R. Liquid-liquid phase equilibrium in glycerolmethanolmethyl
oleate and glycerolmonooleinmethyl oleate ternary systems. Ind.
Eng. Chem. Res. 2006, 45, 3693.
(12) Zhou, H.; Lu, H.; Liang, B. Solubility of multicomponent
systems in the biodiesel production by transesterification of Jatropha
curcas L. oil with methanol. J. Chem. Eng. Data 2006, 51, 1130.
(13) Andreatta, A. E.; Casas, L. M.; Hegel, P.; Bottini, S. B.; Brignole,
E. A. Phase equilibria in ternary mixtures of methyl oleate, glycerol,
and methanol. Ind. Eng. Chem. Res. 2008, 47, 5157.
(14) Csernica, S. N.; Hsu, J. T. Reverse-phase ternary phase diagram,
tie lines, and plait point for commercial biodieselglycerolmethanol.
Ind. Eng. Chem. Res. 2011, 50, 1012.
(15) Rostami, M.; Raeissi, S.; Mahmoudi, M.; Nowroozi, M. Liquid
liquid phase equilibria of systems of palm and soya biodiesels:
Experimental and modeling. Ind. Eng. Chem. Res. 2012, 51, 8302.
(16) Rostami, M.; Raeissi, S.; Mahmoudi, M.; Nowroozi, M. Liquid
liquid equilibria in biodiesel production. J. Am. Oil. Chem. Soc. 2013,
90, 147.
(17) Cheng, L.; Cheng, Y.; Yen, S.; Chen, J. Application of
UNIQUAC and SVM to ultrafiltration for modeling ternary mixtures
of oil, FAME and methanol. Chem. Eng. Sci. 2009, 64, 5093.
(18) Liu, X.; Piao, X.; Wang, Y.; Zhu, S. Model study on
transesterification of soybean oil to biodiesel with methanol using
solid base catalyst. J. Phys. Chem. A 2010, 114, 3750.
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