J. Chem.

Thermodynamics 68 (2014) 60–70

Contents lists available at ScienceDirect

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

Experimental (liquid + liquid) equilibrium data for ternary

and quaternary mixtures of fatty acid methyl and ethyl esters
(FAME/FAEE) from soybean oil
Stéphani C. Beneti a,b,⇑, Marcelo Lanza c, Marcio A. Mazutti d, Marcos Hiroiuqui Kunita e,
Lúcio Cardozo-Filho f, J. Vladimir Oliveira a,c
a
Department of Food Engineering, URI – Campus de Erechim, Erechim, RS 99700-000, Brazil
b
Department of Food Engineering and Technology, Federal University of Parana Technological, UTFPR, Campo Mourão, PR 87301-006, Brazil
c
Department of Chemical and Food Engineering, UFSC, Florianópolis, SC 88040-900, Brazil
d
Department of Chemical Engineering, UFSM, Santa Maria, RS 97105-900, Brazil
e
Department of Chemistry, State University of Maringa, Av. Colombo, 5790 Maringá, PR, Brazil
f
Department of Chemical Engineering, UEM, Maringá, PR 87020 900, Brazil

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

Article history: This work is aimed at providing an easy and quick determination of the biodiesel products using near
Received 25 June 2013 infrared spectroscopy (NIR) by combination with the multivariate calibration in the analysis of (liqui-
Received in revised form 27 August 2013 d + liquid) equilibrium (LLE) data for ternary and quaternary mixtures containing soybean fatty acid
Accepted 31 August 2013
methyl (FAME) and ethyl (FAEE) esters, glycerol, ethanol, methanol and water, at various temperatures.
Available online 8 September 2013
The mass balance for the compositions obtained for each phase was carried out so as to demonstrate the
reliability of the models generated by the multivariate calibration. Two distinct phases are observed, a
Keywords:
glycerol-rich and the other ester-rich, while ethanol is dissolved among the phases hence reducing the
FAME
FAEE
partial mutual miscibility between glycerol and ester. Through (liquid + liquid) equilibrium (LLE) results,
LLE systems containing FAEE at T = 318.15 K and 303.15 K (calibration using data obtained at temperature of
Near-infrared spectroscopy 318.15 K), a good agreement is verified among the values determined using conventional and NIR tech-
nique for alcoholic phase (AP) or aqueous phase (WP) and biodiesel phase (BP). Likewise in the systems
containing FAME at 318.15 K, 303.15 K and 333.15 K (calibration using data obtained at temperature of
318.15 K), the LLE results were reproduced at the upper and lower temperature to the tests of the repro-
ducibility of the models generated by the multivariate calibration.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction alkyl esters (biodiesel) and glycerol. The transesterification

Biodiesel is a renewable biofuel, biodegradable, and environ-
mentally benign, reducing the emission of toxic gases, such as,
SO2, CO, and hydrocarbons [1–3]. Biodiesel is nowadays seen as
one of the most worthy alternatives to conventional fossil fuels
[4], and due to increases in crude oil prices, limited resources of
fossil oil and environmental concerns there has been a renewed
focus on vegetable oils and animal fats to make biodiesel fuels
[5]. Biodiesel fuel consists of a blend of fatty acid methyl or
ethyl esters that can be mixed in all proportions with regular
diesel [6].
The most used process to produce biodiesel is the transesterifi-
cation, a reaction between oil and alcohol producing fatty acid
⇑ Corresponding author at: Department of Food Engineering and Technology,
Federal University of Parana Technological, UTFPR, 87301-006 Campo Mourão, PR,
Brazil. Tel.: +55 (44) 3518 1400.
E-mail address: stephanibeneti@yahoo.com.br (S.C. Beneti).
reaction in traditional production of biodiesel is catalysed by
acid/base catalysts using excess of alcohol to shift the equilibrium
reaction to formation of products. Methanol is the alcohol com-
monly used because of its low cost and its physical and chemical
advantages (polar and shortest chain compared to other alcohols)
[5]. However, in the Brazilian context, ethanol is the predominant
alcohol due to its low cost and accessibility [1–3,7].
The drawback associated with the use of ethanol in the produc-
tion of biodiesel is that the phase separation is more difficult when
compared to methanol. Although there are several works reporting
the reaction process, few works have been presented concerning
the separation and purification steps. The separation of products
and non-reacted components in the biodiesel production requires
knowledge of the phase equilibrium of binary and multi-compo-
nent mixtures containing water, alcohols, glycerol and/or fatty
esters as well as the salt produced from the alkali neutralisation
[6]. The glycerol formed separates from the oil phase at the exit
of the reactor, where two liquid phases co-exist: one rich in

0021-9614/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jct.2013.08.032
 S.C. Beneti et al. / J. Chem. Thermodynamics 68 (2014) 60–70 61

TABLE 1 and the (FAEE + ethanol + glycerol) system were drawn on the
Provenance and purity of the compounds employed in this work. basis of the solubility data. Andrade et al. [5] determined liquid–
Chemical name Provenance Minimum mole fraction purity liquid equilibrium values at two different temperatures for the
Ethanol Merck 0.999 ternary system (ethyl stearate + ethanol + glycerol).
Ethylene glycol Merck 0.990 It is important to mention that all works cited above employed
Glycerol Nuclear 0.995 conventional analytical techniques for the determination of the LLE
Hexane Aldrich >0.998 values, where each compound is determined by a different meth-
Methanol Merck 0.999 od. In a general way, these techniques are time-consuming, since
Sodium Hydroxide Quimex 0.970
Sulfuric Acid Merck 0.990
each requires sample preparation, leading, inevitably, to error
tert-Butanol Merck 0.990 propagation. In recent years, there has been a growing interest in
Tetrahydrofuran Aldrich 0.990 the use of near infrared spectroscopy (NIR) coupled with multivar-
iate calibration for the transformation of qualitative data into
quantitative results of the sample components [15]. The NIR tech-
nique is being widely used due to ease of use, speed of response, no
TABLE 2 pre-treatment of samples before the readings and storage of the
Chemical compositions of the refined soybean. sample data, besides the low cost of analysis. In this sense, the
Fatty acid Cx:ya Molqr mass/(g  mol1) Composition/(wt%) use of near infrared spectroscopy coupled with multivariate cali-
Palmitic C16:0 256.43 11.20 bration appear as a promising alternative to quantify the com-
Stearic C18:0 284.49 3.45 pounds of biodiesel mixtures, since after calibration of the
Oleic C18:1 282.47 23.41 system, quantification of the compounds can be performed in a
Linoleic C18:2 280.45 54.21 straight forward manner without the need of sample preparation
Linolenic C18:3 278.44 5.75
Translinolenicb C18:3Tb 278.44 1.06
[16].
Arachidic C20:0 312.54 0.43 Based on these aspects, the aim of this work was to determine
Behenic C22:0 340.59 0.49 (liquid + liquid) equilibrium of systems containing the fatty acid
a methyl (FAME) and ethyl (FAEE) esters, water, glycerol, ethanol
Cx:y, x = number of carbons and y = number of double bonds.
b
Trans isomers. and methanol using the near infrared spectroscopy coupled with
multivariate calibration (NIR method). In this work, LLE data
determined by the NIR technique are compared to the conven-
glycerol and the other in fatty acid methyl/ethyl esters, while the tional analytical techniques.
non-reacted alcohol is distributed between these two liquid
phases. The conventional process for biodiesel purification involves 2. Experimental
washing with hot water [8].
In this context, a systematic study, comprising prediction and 2.1. Materials
correlation of (liquid + liquid) equilibrium (LLE) data of biodiesel
and related systems are required for process design. However, All the materials were used as received without further purifica-
equilibrium data for the products of the transesterification only tion. Commercial refined soybean oil (Soya) was used as reagent with-
recently became available [3,9–14]. Zhou et al. [3] have measured out previous treatment. Relevant information on the provenance and
the liquid + liquid equilibrium of glycerol-methanol-fatty acid mass fraction purity of the materials used is given in table 1. The water
methyl ester (FAME) by transesterification of Jatropha curcas L. used was distilled and deionised (2  106 S  cm1).
using potassium hydroxide (KOH) as catalyst at temperatures
between 298 K and 328 K. Andreatta et al. [9] reported liquid–li- 2.2. Methyl/ethyl esters production from soybean oil
quid equilibrium data for the ternary system (methyl ole-
ate + methanol + glycerol) in the range of 313 K and 393 K and The transesterification reaction was carried out for soybean oil
pressures up to 0.5 MPa. Liu et al. [14] have measured the mutual whose composition is shown in table 2. The transesterification
solubility of soybean oil, ethanol, glycerol and fatty acid ethyl ester reactions were carried under continuous mechanical agitation in
(FAEE) obtained by transesterification with NaOH as homogeneous a three-necked flask coupled to a condenser with circulating water
catalyst. The phase diagrams of the (FAEE + ethanol + soybean oil) at T = 278.15 K. Initially, the reactor was filled with 150 g of

FIGURE 1. Schematic diagram of the equilibrium cell. A: sample withdrawal phase. B: Digital thermometer. C: alcoholic or aqueous-rich phase. D: oil or biodiesel-rich phase.
E: Water circulation; F: Thermostatic bath (based on Silva et al. [22]).
62 S.C. Beneti et al. / J. Chem. Thermodynamics 68 (2014) 60–70

Hexane TABLE 4
0,00 1,00 Deviations in the global mass balance of the equilibrium phases for the system
{refined rice bran oil (1) + anhydrous ethanol (4) + water (5) + hexane (8)} at
T = 298.15 K.a
OP (Calibration)
AP (Calibration) APb calculated OPc calculated Total calculated Total added
0,25 0,75 OP (Validation) mass/g mass/g mass/g mass/g

AP (Validation) 17.995 21.081 39.076 39.101

17.439 20.788 38.227 38.352
17.090 21.439 38.529 38.573
16.461 23.335 39.796 39.676
0,50 0,50
a
Estimated standard error of 0.4 %.
b
AP is alcoholic phase (rich in ethanol).
c
OP is oil phase (rich in rice bran oil).

0,75 0,25

after the transesterification reaction, 0.1 wt.% aqueous citric acid

was used as a washing solution to remove residual catalyst. Finally,
esters were dried in a conventional dryer vessel, under nitrogen
1,00 0,00
stream for 1 h at T = 343.15 K. The ester content was determined
0,00 0,25 0,50 0,75 1,00
by EN14103 standard [17], with values always above 99.0 wt.%.
Oil Ethanol

(a)
Hexane
2.3. Apparatus and conventional procedures of analysis
0,00 1,00
NIR 2.3.1. Determination of solubility curves (Binodal)
NIR (Dalmolin et al., [21]) The solubility curves were determined by cloud-point method
following the modified methodology used by Lanza et al. [18,19],
0,25 0,75 Priamo et al. [20] and Dalmolin et al. [21] necessary to obtain pre-
liminary information about the phase behaviour of the systems.
Solubility curves were used to select the validation and calibration
standards for the NIR technique. Initially, known amounts of two
0,50 0,50 components partially miscible were weighed on an analytical
balance with a precision of 0.0001 g (Mettler Toledo, Model XS
205 - Dual Range) and added to the equilibrium glass cells
(50 mL) similar to those used by Silva et al. [22] and Stragevitch
0,75 0,25 and d’Ávila [23]. After this preparation, the next compound was
added to the cells using an automatic burette (Metrohm, Model
Dosimat 715, Herisan, Switzerland) until translucent system ap-
peared, indicating a homogeneous liquid phase. All measurements
1,00 0,00 were carried out with temperature control using a thermostatic
0,00 0,25 0,50 0,75 1,00 bath (Nova Ética, Model 521/5D, Brazil), and a magnetic stirrer
Oil Ethanol (Ika Werke, Model RH–KT/C, Staufen, Germany) to promote the
(b) agitation in the mixture and a digital thermometer (Alla, Model
223.15 K to 473.15 K, France) with 0.1 K precision. This digital
FIGURE 2. (a) Selection of calibration and validation standards and solubility curve thermometer was previously calibrated with standard thermome-
for the system {refined rice bran oil (1) + anhydrous ethanol (4) + water (5) + hex- ter over the temperature range of 293.15 to 333.15 K. Thus, the
ane (8)}at T = 298.15 K (OP is oil phase, AP is alcoholic phase). (b) LLE data
corresponding solubility curve was calculated based on the
determined by NIR and compared with Dalmolin et al. [21].
amount of each component added.

soybean oil and heated to 333.15 K. The catalytic solution, pre-

pared with 1 wt.% of the catalyst (sodium hydroxide) dissolved in
the alcohol (molar ratio of oil:alcohol = 1:6), was then added to
reactor. Afterwards, the reactor was closed and the reaction
started. After completion 90 min of reaction, glycerol was sepa-
rated in a funnel. The catalyst and unreacted alcohol were removed
by hot water washings. In order to avoid the formation of emulsion
2.3.2. Determination of water content
To determine the water content, samples were taken from the
equilibrium phases and quantified directly through Karl Fischer
titration (Mettler Toledo, Model DL50-Graphix) according to the
official method Ca 23 to 55 of the AOCS [24]. The validation of this
technique is reported in section 3.

TABLE 3
LLE data for the system {refined rice bran oil (1) + anhydrous ethanol (4) + water (5) + hexane (8)} at T = 298.15 K.

Overall composition Alcoholic phase Oil phase

100w1 100w4 100w5 100w8 100w1 100w4 100w5 100w8 100w1 100w4 100w5 100w8
49.84 48.30 1.86 0.00 3.25 93.09 3.66 0.00 89.67 10.13 0.20 0.00
44.46 48.11 1.85 5.58 3.25 90.14 3.69 2.91 79.34 13.16 0.16 7.35
40.65 47.45 1.82 10.08 3.58 88.03 3.77 4.62 70.31 15.21 0.17 14.30
35.30 46.65 1.79 16.26 3.30 80.52 3.76 12.42 57.32 22.35 0.20 20.13
 S.C. Beneti et al. / J. Chem. Thermodynamics 68 (2014) 60–70 63

Ethanol sample previously weighed in 50 mL of distilled water. Then, 5 to 7

0.00 1.00 drops of bromothymol blue (Merck, Germany) and sulfuric acid
AP a (Calibration) (0.2 N) were added to the sample to reach pH 4. The solution
BP b (Calibration) was neutralised with NaOH (0.05 N) until the blue colour ap-
AP (Validation)
peared. In parallel, a standard solution (blank solution) was pre-
BP (Validation)
0.25 0.75 pared containing 50 mL of distilled water without the presence
Solubility Curve
of glycerol adopting the same procedure for blank solution. Then,
100 mL of sodium periodate solution (60 g  L1) was added to
the sample and kept in the dark for 30 min. After this period, a total
0.50 0.50
of 10 mL of solution of ethylene glycol (Merck, Germany) (1:1) was
added to the mixture and left again in the dark for another 20 min.
The samples were diluted to 300 mL with distilled water and
0.75 0.25
titrated with a NaOH solution (0.125 N) using pH-metre (Mettler
Toledo, Model S40-SeventMulti) to determine pH 6.5 and 8.1 for
the blank and collected sample, respectively. The percentage of
glycerol in the sample was determined by the following
1.00 0.00 expression:
0.00 0.25 0.50 0.75 1.00
FAEE Gly cerol 9:209  N  ðV 1  V 2 Þ
Glycerol ðwt%Þ ¼ ; ð1Þ
(a) ma
where: ma, total mass used; N, normality of NaOH; V1, volume
Ethanol of NaOH solution spent in the sample (mL) and V2, is the volume
0,00 1,00
of NaOH solution spent in the blank (mL). The validation of this
technique is reported in section 3.

NIR (LANZA [27])

NIR
2.3.4. Determination of (liquid + liquid) equilibrium data
0,25 0,75
Solubility Curve The equilibrium data were determined using the same equilib-
rium glass cells (50 mL) mentioned above. From solubility curves
determined, amounts of each component were individually
weighed on an analytical balance with a precision of 0.0001 g
0,50 0,50
(Mettler Toledo, Model XS 205 – Dual Range) and added to the
equilibrium glass cells. The cell temperature was controlled using
a thermostatic bath (Nova Ética, model 521/5D, Brazil). Digital
thermometers (Alla, Model 223.15 K to 473.15 K, France) with
0,75 0,25
0.1 K of variation were used for monitoring the cell temperature.
The mixture was stirred vigorously with a magnetic stirrer (Ika
Werke, Model RH-KT/C, Staufen, Germany) for 30 min and left to
1,00 0,00
rest for (20 to 24) h. This led to the formation of two clear, translu-
0,00 0,25 0,50 0,75 1,00 cent phases, with a well-defined interface and finally, the samples
FAEE Glycerol
of the phases were carefully collected for subsequent quantifica-
tion of the components present. The experimental apparatus used
(b) to determine the (liquid + liquid) equilibrium data is present in
FIGURE 3. (a) Selection of calibration and validation standards and solubility curve figure 1 and validation of this technique is reported in section 3.
for the system containing {FAEE (soybean oil) (2) + anhydrous ethanol (4) + glycerol
(6)} at T = 298.15 K (AP is alcoholic phase, BP is FAEE phase). (b) LLE data and
2.4. NIR technique
solubility curve for the system containing {FAEE (soybean oil) (2) + anhydrous
ethanol (4) + glycerol (6)} at T = 298.15 K determined by NIR technique and
compared with Lanza [27]. The near infrared spectroscopy and multivariate calibration
called ‘‘NIR technique ‘‘ in this work, as described below, was used
for the determination of components content in each equilibrium
2.3.3. Determination of glycerol content phase using a spectrometer Perkin Elmer (Spectrum 100 N, FT-
The periodate method was used to quantify the content of glyc- NIR Spectrometer, series no: 82803). Near-infrared transmittance
erol in the samples of equilibrium phases and was described by spectra were registered in the range from (4000 to 11000) cm1,
Cocks and van Rede [25]. The method involves the reaction of recovering 64 scans with 4 cm1 resolution using a quartz cuvette
glycerol in the sample with sodium periodate (NaIO4) in aqueous (Agillent HP) with a 2 mm optical path. Before collect of the sam-
acid solution to produce formaldehyde and formic acid, using this ples spectra was carried out a spectrum background (64 scans at
latter as a measure of glycerol. The procedure consists to dilute the 4 cm1 resolution, with empty cell), to reduce instrument noise.

TABLE 5
LLE data for the system containing {FAEE (soybean oil) (2) + anhydrous ethanol (4) + glycerol (6)} at T = 298.15 K.

Overall composition Alcoholic phase Biodiesel phase

100w2 100w4 100w6 100w2 100w4 100w6 100w2 100w4 100w6
50.90 34.82 14.28 4.76 56.36 38.88 71.85 25.64 2.15
39.98 34.74 25.28 2.00 51.60 46.40 80.45 18.14 1.42
44.91 29.64 25.45 3.07 47.02 49.91 86.62 13.38 0
64 S.C. Beneti et al. / J. Chem. Thermodynamics 68 (2014) 60–70

Glycerol carried out at temperatures of (298.15, 303.15, 318.15 and

0.00 1.00 333.15) K. After validation of the equipment with pre-determined
WP a (Calibration) systems from literature, determination of phase compositions
BP b (Calibration) were performed with calibration models generated at 318.15 K,
WP (Validation) so that was possible to calculate the phase compositions at lower
BP (Validation)
0.25 0.75 and higher temperatures without development of a new multivar-
Solubility Curve
iate calibration. The calibration models were developed by regres-
sion using the software PLS_ToolboxÒ (Partial Least Square),
version 5.8 of Eigenvector Research (USA), and the Matlab 7.0Ò
0.50 0.50
(The MathWorks Inc, USA). The number of PLS factors used for
model predictions was determined by cross-validation ‘‘leave one
out’’. With the generated models, it was possible to quantify the
components involved in LLE. Several models were generated, and
0.75 0.25
the choice of one of these was decided by the best responses for
each tie line system.

1.00 0.00
2.4.1. Choice of calibrations and validation standards
0.00 0.25 0.50 0.75 1.00 Calibration and validation standards of the systems were cho-
FAEE Water sen very close to the solubility curve, since as closer is the solubil-
ity curve, the generated errors in the model are minimized by
(a) multivariate calibration. The solubility curve obtained previously
was divided into two regions: (i) one with high content of solvent,
Glycerol named alcoholic phase (AP) or aqueous phase (WP), and (ii) one
0.00 1.00 with high content of refined rice oil named as oil phase (OP) and
FAEE or FAME named as biodiesel phase (BP).
For each phase, 30 experimental points were chosen totalizing
NIR technique 60 points to calibrate the NIR equipment and 20 other points used
0.25 0.75
Analytical technique to multivariate validation (10 points used to validate the alcohol or
Solubility Curve aqueous phase and plus 10 used to validate the oil or biodiesel
phase). Both calibration and validation points have been produced
at pre-determined concentrations of the samples, gravimetrically
0.50 0.50
prepared on the analytical balance (with accuracy of ±0.0001 g).
The different systems investigated in this work exhibit the for-
mation of two phases of samples prepared at room temperature, so
that it was decided to perform the dilution at 1:1 (wt/wt) with sol-
0.75 0.25
vent to avoid phase separations. Samples were vigorously stirred
with a magnetic stirrer (Ika Werke, Model RH–KT/C, Staufen, Ger-
many) to ensure the homogeneity of the mixture. Tetrahydrofuran
(Aldrich, mass fraction purity 0.99) was used as solvent for the
1.00 0.00
0.00 0.25 0.50 0.75 1.00 samples. This solvent allows the samples to be solubilized in a sin-
FAEE Water gle translucent phase and was used in both calibration and valida-
tion steps. For the systems involving glycerol, tert-butanol was
(b) used (Merck, mass fraction purity 0.99).
FIGURE 4. (a) Selection of the calibration and validation standards and solubility The experimental apparatus used for determining LLE is the
curve for the system {FAEE (soybean oil) (2) + water (5) + glycerol (6)} at same used in analytical technique described above, but following
T = 318.15 K (WP aqueous phase, BP biodiesel phase). (b) LLE data obtained by a distinct procedure. Samples were collected with a syringe that
NIR technique and compared with data obtained in the conventional analytical
reached the centre of each phase of the equilibrium cell. Samples
technique and solubility curve for the system of {FAEE (soybean oil) (2) + water
(5) + glycerol (6)} at T = 318.15 K. of the fatty acid ethyl or methyl ester phase (BP) and alcohol-rich
phase (AP) or aqueous phase (WP) were obtained and diluted with
1:1 (m  m1) sample to solvent, exactly as was done in the gener-
ation of calibration and validation standards, agitated and placed in
TABLE 6 the quartz cuvette for reading in the NIR spectrometer. The amount
Deviations in the global mass balance of the equilibrium phases for the system {FAEE of solvent used was based on the LLE and thus data are presented
(soybean oil) (2) + anhydrous ethanol (4) + glycerol (6)} at T = 298.15 K.a in solvent-free basis.
APb calculated BPc calculated Total calculated Total added
mass/g mass/g mass/g mass/g 2.4.2. Calculation of the deviations in the mass balance of the phases
12.506 27.579 40.085 40.178 The quality and accuracy of the results of the (liquid + liquid
19.572 18.322 37.894 37.968
equilibrium experiments were tested according to the procedure
19.252 19.254 38.507 39.525
developed by Marcilla et al. [26] and already applied to fatty sys-
a
Estimated standard error of 0.4 %. tems by several researchers [18–21]. The balance equations and
b
AP is alcoholic phase (rich in alcohol).
c
calculations for relative deviation for the global mass balance
BP is biodiesel phase (rich in FAEE).
and for mass balance of each component used in this work were
also used by Lanza et al. [18], Priamo et al. [20] and Dalmolin
et al. [21].
The calibration of infrared spectrometer for each system was Mass balance calculations were carried out taking into account
performed at T = 318.15 K, however the experiments of LLE were the independent mass balance by component and its global
 S.C. Beneti et al. / J. Chem. Thermodynamics 68 (2014) 60–70 65

TABLE 7
LLE data for the system {FAEE (soybean oil) (2) + water (5) + glycerol (6)} at T = 318.15 K.

Overall composition Aqueous phase Biodiesel phase

100w2 100w5 100w6 100w2 100w5 100w6 100w2 100w5 100w6
35.95 16.65 47.40 0.64 25.70 73.66 99.68 0.16 0.16
38.98 37.10 23.92 0.25 60.50 39.25 99.64 0.22 0.14
40.15 42.60 17.25 0.44 69.98 29.57 98.88 0.90 0.22

Table 3 presents the overall composition added to the equilib-

TABLE 8
Deviations in the global mass balance of the equilibrium phases for the system {FAEE
rium cells and compositions obtained for the alcohol (AP) and oil
(soybean oil) (2) + water (5) + glycerol (6)} at T = 318.15 K.a phases (OP) for the system containing {rice bran oil (1) + anhy-
drous ethanol (4) + water (5) + hexane (8)} at T = 298.15 K,
WPb calculated BPc calculated Total calculated Total added
mass/g mass/g mass/g mass/g
obtained by the NIR technique. The mass balance for the composi-
tions obtained for each phase was calculated to demonstrate the
25.636 14.214 39.850 39.868
24.060 15.352 39.412 39.398
reliability of the models generated by the multivariate calibration.
23.557 15.837 39.394 39.259 Table 4 shows the mass balance calculated for the alcoholic and oil
a
phases and the deviations obtained by varying the mass calculated
Estimated standard error of 0.4 %.
b added to the equilibrium cell, according to Marcilla et al. [26].
WP is aqueous phase (rich in water).
c
BP is biodiesel phase (rich in FAEE). According to the results obtained, the NIR methodology can be
considered reliable and hence valid, making possible the use of
the method to other systems because spectroscopy equipment
mixture composition for both liquid phases and comparing their and chemometric correlation reproduced the data in a consistent
sums with the real value for total mass used in the experiments. manner.
Such calculations make possible the evaluation of the quality and Additionally, the NIR technique was validated using experimen-
accuracy of the experimental results obtained [26]. The relative tal results for the system {FAEE (soybean oil) (2) + anhydrous
deviations obtained were never higher than 0.4%. The expression ethanol (4) + glycerol (6)} at T = 298.15 K reported by Lanza [27],
2 shows the calculation for the relative deviation. who also used the NIR technique to obtain the experimental LLE
  values. The data were reproduced in order to compare the results
Am  C m
Relativ e dev iation ¼  100; ð2Þ to a system involving FAEE and glycerol, because this compound
Am is difficult to quantify. The NIR equipment used in this work has
where: Am is added mass and Cm is calculated mass. no temperature control, unlike the equipment used by other
authors [18–21]. In this case, the calibration curve of the equipment
was performed using data presented by Lanza [27]. After the deter-
3. Results and discussion
mination of the calibration curve, the tie lines were determined.
Figure 3(a) shows the calibration and validation points selected
3.1. Validation of NIR technique using literature data
for alcoholic and biodiesel phases, and the solubility curve for the
system containing {FAEE (soybean oil) (2) + anhydrous ethanol
In order to validate the (liquid + liquid) equilibrium data and
(4) + glycerol (6)} at T = 298.15 K. The calibration and validation
check the reproducibility of the experimental apparatus used, we
adopted as reference the quaternary system containing {refined
rice bran oil (1) + anhydrous ethanol (4) + water (5) + hexane (8)}
Glycerol
at T = (298.15 ± 0.2) K taken from Dalmolin et al. [21] In the work
0.00 1.00 NIR technique
of Dalmolin et al. [21], the amount of distilled water in the system
was set to 4.14% for calibration and validation. The anhydrous eth- Analytical technique
anol was prepared to be added into the equilibrium cells. However, Solubility Curve
in this study the amount of water added to the sample preparation
for calibration and validation was only 3.72%, because preliminary 0.25 0.75
tests indicated that with 4.14% of water in the system it was not
possible to obtain a single phase at the temperature studied. The
calibration and validation of the alcoholic and oil phases for the
system containing {rice bran oil (1) + anhydrous ethanol 0.50 0.50
(4) + water (5) + hexane (8)} at T = 298.15 K are shown in figure
2(a). (Liquid + liquid) equilibrium data obtained using the NIR
technique as well as the comparison with data obtained by Dalm-
olin et al. [21] for the same system are shown in figure 2(b). It is
0.75 0.25
important to observe that the difference in water content between
the systems provides a concentration difference in the other
system components.
The slight difference presented in figure 2 between experimen-
tal values reported in this work and those taken from the literature 1.00 0.00
0.00 0.25 0.50 0.75 1.00
can be justified by the difference in composition of rice bran oil and
the amount of water added to the system while maintaining the FAEE Water
miscibility between the compounds. Although there is a difference FIGURE 5. LLE data obtained by NIR technique and by conventional analytical
between the analyzed data, it can be seen that the results follow technique and solubility curve for the system of {FAEE (soybean oil) (2) + water
the same trend. (5) + glycerol (6)} at T = 303.15 K.
66 S.C. Beneti et al. / J. Chem. Thermodynamics 68 (2014) 60–70

TABLE 9
LLE data for the system {FAEE (soybean oil) (2) + water (5) + glycerol (6)} at T = 303.15 K.

Overall composition Aqueous phase Biodiesel phase

100w2 100w5 100w6 100w2 100w5 100w6 100w2 100w5 100w6
38.29 15.75 45.96 0.06 25.09 74.85 98.84 0.72 0.44
41.78 34.33 23.88 0.58 58.01 41.41 99.27 0.43 0.30
40.20 42.41 42.41 1.47 69.84 28.68 99.52 0.32 0.16

Glycerol WP a (calibration)
TABLE 10 BPb (calibration)
0.00 1.00
Deviations in the global mass balance of the equilibrium phases for the system {FAEE WP (validation)
(soybean oil) (2) + water (5) + glycerol (6)} at T = 303.15 K.a
BP (validation)
WPb calculated BPc calculated Total calculated Total added Solubility curve
mass/g mass/g mass/g mass/g
0.25 0.75
24.139 15.259 39.399 39.427
22.965 16.427 39.393 39.350
23.689 15.460 39.150 39.140
a
Estimated standard error of 0.4 %.
b 0.50 0.50
WP is aqueous phase (rich in water).
c
BP is biodiesel phase (rich in FAEE).

experimental points were chosen close to solubility curve. 0.75 0.25

Figure 3(b) shows the results obtained in this study using the
NIR technique (also presented at table 5) and compares to data
reported by Lanza [27] as well as the solubility curve.
According to figure 3, it is possible to note that the data are 1.00 0.00
reproducible and that the tie lines determined passed through 0.00 0.25 0.50 0.75 1.00
the global mixture point. In addition, the compositions of the equi- FAME Water
librium phases were near solubility curve, which is desirable, since
this is the limit for the occurrence of the two-phase region for the (a)
temperature under consideration. It should also be noticed that the
Glycerol
mixture of esters and glycerol forms two distinct phases, viz. glyc-
erol-rich and an ester-rich. Ethanol is dissolved among the phases 0.00 1.00 NIR technique
Analytical technique
reducing the partial mutual miscibility among glycerol and ester. Solubility curve
With the phase compositions and the mixture points used, it is
possible to determine the global mass balance for the system con-
taining {FAEE (soybean oil) (2) + anhydrous ethanol (4) + glycerol 0.25 0.75

(6)} at T = 298.15 K, whose data are presented in table 6. The rela-

tive deviations obtained for tie lines are low, indicating that the
models are effective for the reproduction of the experimental val-
ues. Data obtained in this work for this system containing {FAEE 0.50 0.50

(soybean oil) (2) + anhydrous ethanol (4) + glycerol (6)} at

T = 298.15 K are close to those obtained by Lanza [27], hence con-
firming the reproducibility of the NIR technique.
0.75 0.25

3.2. Determination of LLE data for FAEE and FAME and their related
systems using the NIR technique

Systems containing {FAEE (soybean oil) (2) + water (5) + glycerol 1.00 0.00
0.00 0.25 0.50 0.75 1.00
(6)} at T = (318.15 and 303.15 ± 0.2) K. The system containing {FAEE
FAME Water
(soybean oil) (2) + water (5) + glycerol (6)} was calibrated at the
temperature of 318.15 K and tie lines were determined in this (b)
same temperature. Figure 4(a) presents the choice of validation
FIGURE 6. (a) Selection of calibration and validation standards and solubility curve
and calibration standards and the binodal curve for the system for the system {FAME (soybean oil) (3) + water (5) + glycerol (6)} at T = 318.15 K
whereas figure 4(b) shows the LLE data determined by the NIR (WP aqueous phase, BP biodiesel (FAME) phase). (b) LLE data determined by NIR
technique and compared to LLE data obtained by the conventional and conventional technique for the system containing {FAME (soybean oil)
analytical technique. Table 7 contains LLE results for the system (3) + water (5) + glycerol (6)} at T = 318.15 K.

{FAEE (soybean oil) (2) + water (5) + glycerol (6)} at T = 318.15 K

and table 8 shows the mass balances for the system obtained by
the NIR technique.
According to results shown in figure 4 and table 8, good agree-
ment is verified among the values determined using conventional
and NIR technique for aqueous phase (WP) and biodiesel phase
(BP).
Figure 5 shows LLE results and the binodal curve for the system
containing {FAEE (soybean oil) (2) + water (5) + glycerol (6)} at
T = 303.15 K determined using the NIR technique and conventional
analytical technique. The LLE values in the NIR technique were cal-
culated by correlations performed for the calibration standards for
 S.C. Beneti et al. / J. Chem. Thermodynamics 68 (2014) 60–70 67

TABLE 11
LLE data for system {FAME (soybean oil) (3) + water (5) + glycerol (6)} at T = 318.15 K.

Overall composition Aqueous phase Biodiesel phase

100w3 100w5 100w6 100w3 100w5 100w6 100w3 100w5 100w6
23.66 25.99 50.348 1.09 34.15 64.76 99.11 0.37 0.52
33.76 32.045 34.20 1.58 47.55 50.86 98.05 0.67 1.28
48.37 45.81 5.81 1.74 87.62 10.64 99.31 0.48 0.20

TABLE 12
Deviations in the global mass balance of the equilibrium phases for the system {FAME TABLE 14
(soybean oil) (3) + water (5) + glycerol (6)} at T = 318.15 K.a Deviations in the global mass balance of the equilibrium phases for the system {FAME
(soybean oil) (3) + water (5) + glycerol (6)} at T = 333.15 K.a
WPb calculated BPc calculated Total calculated Total added
mass/g mass/g mass/g mass/g WPb calculated BPc calculated Total calculated Total added
mass/g mass/g mass/g mass/g
30.378 9.057 39.435 39.353
26.463 13.247 39.710 39.713 36.368 9.150 45.518 45.492
20.777 19.084 39.861 39.920 27.730 12.191 39.914 39.906
22.751 16.807 39.559 39.540
a
Estimated standard error of 0.4 %. a
b
WP is aqueous phase (rich in water). Estimated standard error of 0.4 %.
b
c WP is aqueous phase (rich in water).
BP is biodiesel phase (rich in FAME). c
BP is biodiesel phase (rich in FAME).

Glycerol
0.00 1.00
NIR technique glycerol and water need to be removed from the FAEE-rich phase
Analytical technique in the biodiesel production process. It can be seen that glycerol
Solubility curve and water are completely mutually soluble, while FAEE and water
are practically insoluble in each other. An increase in temperature
0.25 0.75 has a small influence on the solubility of FAEE in the glycerol. The
LLE phase behaviour of the systems containing glycerol is generally
similar to that of the systems containing water [28].
Systems containing {FAME (soybean oil) (3) + water (5) + glycerol
(6)} at T = (318.15 and 333.15 ± 0.2) K. The systems containing
0.50 0.50
methyl soybean biodiesel were also calibrated and validated using
the NIR technique. Figure 6(a) shows the calibration and validation
points for the aqueous and biodiesel phases (also presented at ta-
ble 11) whereas figure 6(b) shows the binodal curve and the equi-
0.75 0.25 librium (liquid + liquid) data obtained for the same system using
conventional and NIR technique. Table 12 shows the relative devi-
ations and mass balance system obtained by {FAME (soybean oil)
(3) + water (5) + glycerol (6)} at T = 318.15 K.
1.00 0.00 It can be noted that the NIR technique is able to predict the (li-
0.00 0.25 0.50 0.75 1.00 quid + liquid) equilibrium data in the present study. Results are
FAME Water similar for both analytical techniques, NIR and conventional. As
done for the previous system, after calibration, validation and gen-
FIGURE 7. LLE data determined by NIR and conventional technique for the system
eration of models at a temperature of 318.15 K, LLE was carried out
containing {FAME (soybean oil) (3) + water (5) + glycerol (6)} at T = 333.15 K.
at temperatures above to assess the ability of the model. Figure 7
shows the binodal curve and LLE results for the system containing
the system at 318.15 K. Table 9 contains LLE results for the system {FAME (soybean oil) (3) + water (5) + glycerol (6)} at T = 333.15 K
{FAEE (soybean oil) (2) + water (5) + glycerol (6)} at T = 303.15 K (also presented in table 13), and the data predicted were generated
and table 10 presents values from the mass balance for the same from the models with the calibration and validation at
system. Again, experimental values are well reproduced, demon- T = 318.15 K. Table 14 shows the mass balance relative deviations
strating that is possible to calibrate the system at one temperature for the system containing {FAME (soybean oil) (3) + water
and use this correlation to predict the composition at other (5) + glycerol (6)} at T = 333.15 K.
temperatures. From figures 6(b) and 7 it can be seen that FAME is practically
Figures 4(b) and 5 show that glycerol is favourably distributed insoluble in both glycerol and water, and an increase in tempera-
within the aqueous phase, indicating that only a small amount of ture improves the mutual solubility of glycerol and water. This

TABLE 13
LLE data for the system {FAME (soybean oil) (3) + water (5) + glycerol (6)} at T = 333.15 K.

Overall composition Aqueous phase Biodiesel phase

100w3 100w5 100w6 100w3 100w5 100w6 100w3 100w5 100w6
20.71 31.05 48.24 0.87 38.97 60.16 99.51 0.20 0.29
31.11 33.28 35.61 1.04 48.00 50.96 99.47 0.35 0.18
43.04 42.55 14.40 1.43 73.50 25.07 99.32 0.54 0.14
68 S.C. Beneti et al. / J. Chem. Thermodynamics 68 (2014) 60–70

Methanol Methanol
0.00 1.00 0.00 1.00
NIR technique
AP a (calibration) Analytical technique
BP b (calibration)
Solubility curve
AP (validation)
0.25 0.75 BP (validation) 0.25 0.75
Solubility curve

0.50 0.50
0.50 0.50

0.75 0.25
0.75 0.25

1.00 0.00
0.00 0.25 0.50 0.75 1.00
1.00 0.00
FAME Glycerol 0.00 0.25 0.50 0.75 1.00
(a) FAME Glycerol

(a)
Methanol
0.00 1.00
Methanol
NIR technique 0.00 1.00
Analytical technique NIR technique
Solubility curve Analytical technique
0.25 0.75 Solubility curve

0.25 0.75

0.50 0.50

0.50 0.50

0.75 0.25

0.75 0.25

1.00 0.00
0.00 0.25 0.50 0.75 1.00
1.00 0.00
FAME Glycerol 0.00 0.25 0.50 0.75 1.00
(b) FAME Glycerol
FIGURE 8. (a) Selection of calibration and validation standards and solubility curve (b)
for the system {FAME (soybean oil) (3) + glycerol (6) + methanol (7)} at T = 318.15 K
(AP alcoholic phase, BP biodiesel (FAME) phase). (b) LLE data determined by NIR FIGURE 9. (a) LLE data determined using the NIR and conventional technique for
and conventional method for the system containing {FAME (3) + glycerol the system containing {FAME (soybean oil) (3) + glycerol (6) + methanol (7)} at
(6) + methanol (7)} at T = 318.15 K. T = 303.15 K. (b) LLE data determined using the NIR and conventional technique for
the system containing {FAME (3) + glycerol (6) + methanol (7)} at T = 333.15 K.

TABLE 15
LLE data for the system {FAME (soybean oil) (3) + glycerol (6) + methanol (7)} at T = 318.15 K.

Overall composition Alcoholic phase Biodiesel phase

100w3 100w6 100w7 100w3 100w6 100w7 100w3 100w6 100w7
45.94 47.19 6.87 0.080 90.77 9.15 95.69 0 4.31
34.25 34.22 31.52 1.40 53.38 45.21 91.72 0.14 8.14
17.36 20.74 61.89 6.35 24.27 69.37 78.97 0.48 20.55

TABLE 16
Deviations in the global mass balance of the equilibrium phases for the system {FAME (soybean oil) (3) + glycerol (6) + methanol (7)} at T = 318.15 K.a

APb calculated mass/g BPc calculated mass/g Total calculated mass/g Total added mass/g
20.659 19.059 39.718 39.733
24.873 14.101 39.074 39.070
34.362 6.143 40.505 40.533
a
Estimated standard error of 0.4 %.
b
AP is alcoholic phase (rich in alcohol).
c
BP is biodiesel phase (rich in FAME).
 S.C. Beneti et al. / J. Chem. Thermodynamics 68 (2014) 60–70 69

TABLE 17
LLE data for the system {FAME (soybean oil) (3) + glycerol (6) + methanol (7)} at T = 303.15 K.

Overall composition Alcoholic phase Biodiesel phase

100w3 100w6 100w7 100w3 100w6 100w7 100w3 100w6 100w7
41.31 38.13 20.55 0.25 68.15 31.60 90.69 2.51 6.79
47.24 45.51 7.25 0.22 89.19 10.59 93.35 2.01 4.64
25.39 27.50 47.10 1.87 37.56 60.58 90.48 1.67 7.85

TABLE 18
Deviations in the global mass balance of the equilibrium phases for the system {FAME TABLE 20
(soybean oil) (3) + glycerol (6) + methanol (7)} at T = 303.15 K.a Deviations in the global mass balance of the equilibrium phases for the system {FAME
(soybean oil) (3) + glycerol (6) + methanol (7)} at T = 333.15 K.a
APb calculated BPc calculated Total calculated Total added
mass/g mass/g mass/g mass/g APb calculated BPc calculated Total calculated Total added
22.245 18.550 40.795 40.842 mass/g mass/g mass/g mass/g
19.747 19.996 39.743 39.620 22.736 17.886 40.662 40.526
28.822 10.390 39.212 39.114 20.682 20.264 40.945 40.945
a 26.756 14.003 40.759 40.739
Estimated standard error of 0.4 %.
b a
AP is alcoholic phase (rich in alcohol). Estimated standard error of 0.4 %.
c b
BP is biodiesel phase (rich in FAME). AP is alcoholic phase (rich in alcohol).
c
BP is biodiesel phase (rich in FAME).

behaviour is interesting for the purpose of biodiesel purification

since water could be used to remove the glycol generated from
the mixture, since water and glycerol are completely mutually
soluble.
Systems containing {FAME (soybean oil) (3) + glycerol (6) + metha-
nol (7)} at T = (318.15, 303.15 and 333.15 ± 0.2) K. For this system
under study, after calibration using data obtained at temperature
of 318.15 K, the LLE values were reproduced at the upper and lower
temperature to test the reproducibility of the models generated by
the multivariate calibration (NIR technique). Figure 8(a) shows the
calibration and validation points for the alcohol and biodiesel
phases for the system containing {FAME (soybean oil) (3) + glycerol
(6) + methanol (7)} at T = 318.15 K (also presented in table 15),
whereas figure 8(b) shows the LLE results for this system, compar-
ing the data determined by the NIR technique and conventional
analytical technique. Table 16 presents the relative deviations in
the global mass balance of phases in equilibrium for the system
{FAME (soybean oil) (3) + glycerol (6) + methanol (7)} at
T = 318.15 K.
The models generated by the calibration and validation of the
system at T = 318.15 K were used to determine the LLE values at
303.15 K in order to evaluate the ability of the model to predict
the data. Figure 9(a) shows the LLE results for the system {FAME
(soybean oil) (3) + glycerol (6) + methanol (7)} at 303.15 K (also
presented in table 17). Table 18 presents the relative deviations
in global mass balance for the same system. Figure 9(b) shows
the LLE results for the same system at 333.15 K (also presented
in tables 19) and 20 shows the relative deviations in global mass
balance for the same system.
Figures 8(b) and 9(a) and (b) show that the influence of temper-
ature is weak, as already noted by Wang and Lu [29], who studied
the system containing (dimethyl carbonate + methanol + glycerol)
at T = (303.15, 313.15, 323.15 and 333.15) K and by França et al.
[30], who presented a study for the system {castor oil biodie-
sel + glycerol + alcohol} at T = (298.15 and 333.15) K. In addition,
FAME and methanol, glycerol and methanol are completely mutu-
ally soluble, but glycerol and FAME are only partially soluble in
each other. The solubility of FAME in the glycerol phase is slightly
greater than that of glycerol in the FAME phase. Furthermore, the
solubility in the ternary mixture changes insignificantly with
temperature in the range from 303.15 K to 333.15 K. The reaction
conversion is usually very high with catalysts such as NaOH. The
final product can be considered to be a ternary mixture of FAME,
glycerol and methanol.
The solubility results indicate that the separation of glycerol can
be conducted in situ under reaction conditions, which is beneficial
for simplifying the process and reducing the associated costs. Sim-
ilar phase behaviour was verified for FAME from (Jatropha curcas
oil + methanol + glycerol), possibly due to the existing similar
chemical composition of the oils [3].
The relatively higher solubility of glycerol and alcohol in castor
oil biodiesel affords more difficulty during separation and purifica-
tion steps. Biodiesel solubility in the glycerol-enriched phase is
slightly higher for the ternary mixture containing ethanol
compared to methanol, and the mutual solubility of the system
increases with temperature [28], but such effects are small [30].
Mesquita et al. [31] studied the systems containing {(soybean
and sunflower) biodiesel + glycerol + ethanol} at T = (293.15 and
323.15) K and mentioned that the slopes of the lines show that eth-
anol prefers the glycerol-rich phase rather than the biodiesel-rich
phase. This phenomenon indicates that alcohol can be considered
as a good extracting component for soybean and sunflower biodie-
sels. The large region in the two-phase domain indicates a high de-
gree of immiscibility between biodiesel and glycerol even in the
presence of ethanol.

TABLE 19
LLE data for the system {FAME (soybean oil) (3) + glycerol (6) + methanol (7)} at T = 333.15 K.

Overall composition Alcoholic phase Biodiesel phase

100w3 100w6 100w7 100w3 100w6 100w7 100w3 100w6 100w7
41.44 42.25 16.30 0.29 73.07 26.63 93.51 2.56 3.93
48.77 47.35 3.87 2.18 92.87 4.95 96.32 0.89 2.78
30.95 32.75 36.30 1.47 49.89 48.64 87.44 1.96 10.59
70 S.C. Beneti et al. / J. Chem. Thermodynamics 68 (2014) 60–70
As described by Zhou et al. [3], the solubility of glycerol in the
biodiesel phase is slightly greater than that of biodiesel in the glyc-
erol phase. From the experimental results, it is also possible to see
that the biodiesel phase is richer in glycerol than the glycerol phase
is in biodiesel [4]. In the biodiesel processing, binary and ternary
systems containing methanol, ethanol, water, and glycerol are
found in the downstream of the biodiesel manufacturing process
[32].
4. Conclusions
According to the results obtained, near infrared spectroscopy
methodology can be considered reliable and hence valid for the
systems investigated, viz. soybean fatty acid methyl (FAME) and
ethyl (FAEE) esters, glycerol, ethanol, methanol and water, at vari-
ous temperatures. Experimental values were reproduced well,
demonstrating that is possible to calibrate these systems at one
temperature (i.e. 318.15 K) and use this correlation to predict the
composition at other temperature. Based on the LLE results ob-
tained, glycerol and water are completely mutually soluble, while
FAEE or FAME and water are practically insoluble in each other.
This behaviour is interesting for the purpose of biodiesel purifica-
tion since water could be used to remove the generated glycerol
from the mixture. The advantages of the NIR plus multivariate
analysis comprise a reliable, non-destructive, fast and low-cost
technique, eliminating the need for previous preparation of the
samples and generating a minimum waste, making possible the
use of these to other systems because spectroscopy equipment
and chemometric correlation can reproduce the data within a con-
sistent manner.
Acknowledgements
The authors thank CNPq and Pró-Engenharias/CAPES (Grant no.
076/2008) for the financial support of this work and scholarships.
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