Fluid Phase Equilibria xxx (2015) 1e8

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Fluid Phase Equilibria

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / fl u i d

Vapor-liquid equilibria of binary and ternary mixtures containing

ethyl lactate and effect of ethyl lactate as entrainer
Hiroyuki Matsuda*, Koji Inaba, Hirofumi Sumida, Kiyofumi Kurihara, Katsumi Tochigi,
Kenji Ochi
Department of Materials and Applied Chemistry, Nihon University, 1-8-14 Kanda Surugadai, Chiyoda-ku, Tokyo 101-8308, Japan

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

Article history: This work investigated the effect of ethyl lactate as an entrainer for separation of a binary azeotropic
Received 1 October 2015 system. Isobaric vaporeliquid equilibria (VLE) were determined for three binary systems, including
Received in revised form methyl acetate þ methanol, methyl acetate þ ethyl lactate, and methanol þ ethyl lactate using ebulli-
4 December 2015
ometry. Experimental VLE data were represented by the Wilson and NRTL models. The effect of ethyl
Accepted 17 December 2015
Available online xxx
lactate was evaluated by two approaches, including residue curve maps and calculation of S12 separation
factors using binary Wilson parameters. Both the residue curve maps and the separation factors showed
that ethyl lactate acted as an entrainer for extractive distillation of the binary azeotropic system methyl
Keywords:
Vaporeliquid equilibria
acetate þ methanol. VLE for the ternary system methyl acetate þ methanol þ ethyl lactate were also
Ethyl lactate measured, and the prediction of the behavior of this ternary system using the binary Wilson or NRTL
Entrainer parameters showed excellent agreement with the experimental VLE data.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction entrainer is important. Gmehling and Mo €llmann [4] have defined

Ethyl lactate is a biomass-derived solvent. It can be easily pro-
duced from ethanol and lactic acid, which are obtained by
fermentation of biomass. It is found in beer, wine, and soy products.
Ethyl lactate has excellent properties as a solvent, such as low
toxicity, relatively low volatility, low viscosity, and good biode-
gradability, and recyclability. Consequently, it has attracted much
attention in recent years as a promising candidate to replace toxic
organic solvents and volatile organic compounds [1e3]. Because of
its low toxicity, ethyl lactate is approved by the US Food and Drug
Administration as a pharmaceutical and food additive [1,2]. It has
been widely used as a green solvent in several applications, such as
organic synthesis, and in fragrances, inks, and coatings. Because of
its features, ethyl lactate could be used as a solvent for green sep-
aration and purification.
Ethyl lactate could be applied as an entrainer for the separation
of a binary azeotropic system by extractive distillation. To design an
extractive distillation process, vaporeliquid equilibrium (VLE) data
are required. In particular, knowledge of the enhancement of the
separation factor in a binary azeotropic system with addition of an
* Corresponding author.
E-mail address: matsuda.hiroyuki@nihon-u.ac.jp (H. Matsuda).
the following criteria for selection of an entrainer for extractive
distillation: (a) the entrainer should exhibit zeotropic behavior
with all components of the system to be separated; (b) to achieve
separation factors far from unity, the entrainer should alter the
activity coefficients of the components to be separated to different
extents; and (c) for convenient recovery of the entrainer, its boiling
point must be sufficiently higher (e.g., DT ¼ 40 K) than that of any of
the components of the system to be separated.
The aim of this work was to investigate the use of ethyl lactate as
an entrainer. Ethyl lactate would satisfy the criteria of Gmehling
and Mo €llmann [4]. We selected methyl acetate þ methanol as the
binary azeotrope system. Isobaric VLE data for three binary sys-
tems, methyl acetate þ methanol, methyl acetate þ ethyl lactate,
and methanol þ ethyl lactate, were measured at pressures between
40.00 and 101.3 kPa by ebulliometry. The experimental VLE data
were evaluated using the Wilson and non-random two-liquid
(NRTL) models. The solvent effects of ethyl lactate were evaluated
by two approaches, including residue curve maps and calculation of
separation factors (S12) using the binary parameters obtained from
the binary VLE data. VLE data for the ternary system methyl
acetate þ methanol þ ethyl lactate were also measured, and the
predicted behavior of this ternary system using binary Wilson or
NRTL parameters was compared with the experimental VLE data.

http://dx.doi.org/10.1016/j.fluid.2015.12.029
0378-3812/© 2015 Elsevier B.V. All rights reserved.

Please cite this article in press as: H. Matsuda, et al., Vapor-liquid equilibria of binary and ternary mixtures containing ethyl lactate and effect of
ethyl lactate as entrainer, Fluid Phase Equilibria (2015), http://dx.doi.org/10.1016/j.fluid.2015.12.029
2 H. Matsuda et al. / Fluid Phase Equilibria xxx (2015) 1e8

Table 1
Chemicals used in this work.

Component Source Grade Molecular sieve Purity (mass fraction)

Methyl acetate 4A >0.999

Methanol Wako Pure Chemical Industries Special grade 3A >0.999
Ethyl lactate 13X >0.995

Table 2
Normal boiling points (Tb), densities at 298.15 K (r), and liquid molar volumes at 298.15 K ðvLi Þ of the pure components used in this study.a

Component Tb (K) r (298.15 K) (kg m3) vLi  106 (m3 mol1)

Experimental Literature Experimental Literature

Methyl acetate 330.04 330.018b 927.10 927.9b 79.90

Methanol 337.60 337.696b 786.56 786.37b 40.73
Ethyl lactate 426.10 427.7b 1028.08 1027.2b 114.90
424.98c 1028.0c
a
Standard uncertainties u are u(r) ¼ ±0.01 kg/m3, u(T) ¼ ±0.01 K, u(P) ¼ ±1 kPa.
b
Ref. [5].
c
Ref. [6].

Table 3 Antoine constants, respectively, of the compounds investigated in

Experimental vapor pressures of the pure components used in this work.a this work. The Antoine constants in Table 4 were determined from
P (kPa) T (K) the experimental vapor pressure data. The average deviations be-
Methyl acetate Methanol Ethyl lactate
tween the experimental values and those calculated using the
Antoine constants in the literature [7,8] were within 0.47 kPa.
40.00 305.65 315.49 396.91
Except for ethyl lactate, the vapor pressures calculated using the
53.33 312.68 321.98 405.49
66.66 318.45 327.23 412.44 Antoine constants determined in this work deviated from those in
79.99 323.36 331.66 418.34 the literature [9,10] by 0.51 kPa on average.
93.32 327.68 335.51 423.47
101.3 330.04 337.60 426.10
a
Standard uncertainties u are u(T) ¼ ±0.03 K, u(P) ¼ ±0.03 kPa. 2.2. Apparatus and procedure

A modified Swietoslawski-type ebulliometer was used to mea-

2. Experimental
2.1. Materials
The chemicals used in this work are summarized in Table 1. The
purities of the materials were checked by gas chromatography (GC-
4000, GL Sciences Co., Ltd., Tokyo, Japan) with a thermal conduc-
tivity detector. The water contents of all chemicals were checked
using a Karl Fischer moisture meter (CA-200, Mitsubishi Chemical
Co., Ltd., Tokyo, Japan), and were less than 100 ppm. Normal boiling
points (Tb) were measured using a modified Swietoslawski-type
ebulliometer (details are given in Section 2.2). The densities (r) at
T ¼ 298.15 K and P ¼ 0.1 MPa were also measured using a precision
digital oscillating U-tube density meter (DMA 4500, Anton Paar,
Graz, Austria) with a reproducibility of 102 kg/m3. The experi-
mental Tb and r at 298.15 K of the chemicals used in this work are
shown in Table 2 together with the literature values [5,6].
Tables 3 and 4 show the experimental vapor pressures and the
sure the boiling points. The equipment and the measurement
procedure have been described elsewhere [11,12]. The apparatus
consisted of an ebulliometer, a pressure-controlling circuit, and a
computer to analyze the data. Boiling points were measured with a
calibrated platinum resistance thermometer with an accuracy of
±0.01 K. The pressure in the apparatus was established by a pres-
sure controller (DPI515, Druck Co., Kirchentellinsfurt, Germany).
The uncertainty in the pressure was estimated to be ±0.03 kPa. For
our measurements, the ebulliometer was charged with approxi-
mately 160 cm3 of a mixture with known constituents. The liquid
mole fraction was determined gravimetrically (Mettler digital bal-
ance model AX504, Mettler-Toledo Inc., Columbus, OH, USA) with a
sensitivity of 0.1 mg. The uncertainty in the mole fraction was
estimated to be ±0.0001. Steady state was assumed when the
temperature oscillated by no more than 0.02 K/min. The uncer-
tainty in the experimental temperature boiling point was estimated
to be ±0.03 K. Boiling point measurements for a given mixture were
performed at progressively higher system pressures. For this work,

Table 4
Antoine equation constantsa determined for pure components used in this work.

s

s

Component Determined Antoine constants Literature Antoine constants
DP
(kPa)b Reference (vapor pressure)
DP
(kPa)c
i av: i av:

A B C A B C Reference

Methyl acetate 6.20814 1168.97 51.831 6.18621 1156.43 53.46 [7] 0.22 [9] 0.13
Methanol 7.13230 1553.46 34.588 7.20277 1580.08 33.65 [7] 0.44 [10] 0.51
Ethyl lactate 6.74990 1776.94 51.719 6.60607 1673.80 62.21 [8] 0.47
a s

s
i =kPaÞ
logðP ¼ A
 B=½ðT=KÞ þ C.

b
DP
¼ PNDP

P s s
s s
i av: k¼1 i;exptl  Pi;calcd
=NDP, where Pi;exptl is the experimental vapor pressure, and Pi;calcd is the vapor pressure calculated using Antoine constants from the
k
literature

s
values.


c
P
s

DPi
av: ¼ NDP s s s
k¼1
Pi;lit  Pi;calcd
=NDP, where Pi;lit is the literature vapor pressure, and Pi;calcd is the vapor pressure calculated using the Antoine constants determined in this
k
work.

Please cite this article in press as: H. Matsuda, et al., Vapor-liquid equilibria of binary and ternary mixtures containing ethyl lactate and effect of
ethyl lactate as entrainer, Fluid Phase Equilibria (2015), http://dx.doi.org/10.1016/j.fluid.2015.12.029
 H. Matsuda et al. / Fluid Phase Equilibria xxx (2015) 1e8 3

Table 5
340
Experimental boiling points, liquid phase mole fractions (x1), and temperatures (T)
for the three binary systems.a

x1 40.00 kPa 53.33 kPa 66.66 kPa 79.99 kPa 93.32 kPa 101.3 kPa

T (K) T (K) T (K) T (K) T (K) T (K)

Methyl acetate (1) þ Methanol (2) 330

0.0000 315.49 321.98 327.23 331.66 335.51 337.60
0.0998 310.28 316.91 322.29 326.86 330.85 333.01
0.2001 307.38 314.07 319.52 324.09 328.08 330.25
0.2999 305.58 312.31 317.75 322.39 326.45 328.65

T/K
0.4047 304.53 311.22 316.65 321.29 325.34 327.53
0.5001 303.72 310.41 315.90 320.60 324.74 326.96 320
0.6000 303.21 309.98 315.52 320.28 324.45 326.67
0.7003 302.92 309.67 315.30 320.13 324.38 326.66
0.8004 303.05 309.99 315.63 320.45 324.74 327.00
0.8996 304.13 311.05 316.68 321.48 325.68 327.97
1.0000 305.65 312.68 318.45 323.36 327.68 330.04
Methyl acetate (1) þ Ethyl lactate (2) 310
0.0000 396.91 405.49 412.44 418.34 423.47 426.10
0.1000 369.36 378.14 385.91 392.52 397.89 401.22
0.2000 353.28 362.97 370.83 376.97 382.75 386.00
0.2998 338.26 347.00 353.64 359.83 365.19 368.56
0.3999 331.08 340.09 347.02 352.17 357.48 360.37
0.5001 325.15 332.97 339.61 345.28 350.47 353.00 300
0.6000 318.77 326.57 333.17 338.72 343.93 346.56
0.0 0.2 0.4 0.6 0.8 1.0
0.7003 314.61 322.46 328.93 334.43 339.28 341.92 x1, y1
0.7998 311.23 318.69 325.09 330.67 335.30 337.88
0.9000 308.07 315.49 321.44 326.59 331.13 333.59 Fig. 1. Temperature-composition relationships for the system methyl acetate
1.0000 305.65 312.68 318.45 323.36 327.68 330.04 (1) þ methanol (2). This work: C, 40.00 kPa; :, 53.33 kPa; -, 66.66 kPa; ;,
Methanol (1) þ Ethyl lactate (2) 79.99 kPa; A, 93.32 kPa; +, 101.3 kPa; Literature: D, Dobroserdov and Bagrov [10] at
0.0000 396.91 405.49 412.44 418.34 423.47 426.10 53.33 kPa; ,, Nagata and Ohta [11] at 66.66 kPa; V, Dobroserdov and Bagrov [10] at
0.1055 372.42 380.91 387.65 394.50 401.49 405.09 79.99 kPa; *, Iliuta et al. [12] at 101.3 kPa; þ, Nagata at 101.3 kPa [13]; ; Topphoff
0.2097 355.98 364.10 370.86 374.40 379.00 382.88 et al. [14] at 101.3 kPa; , Tu et al. [15] at 101.3 kPa; , Wilson; 5, azeotropic point.
0.3128 344.84 353.04 361.01 366.29 371.03 373.81
0.4147 336.70 344.04 349.97 355.27 359.94 362.22
0.5138 331.33 339.30 344.07 349.14 353.53 356.01 40.00e101.3 kPa. The experimental VLE data are presented in
0.6145 327.05 333.90 339.52 344.31 348.49 350.82 Table 5, and are illustrated in Figs. 1e3 together with the literature
0.7125 323.14 330.00 335.59 340.35 344.59 346.88 values [6,14e19]. Fig. 1 shows that the experimental and literature
0.8095 320.18 327.13 332.67 337.56 341.76 344.04 VLE data of the methyl acetate þ methanol system agreed well at
0.9054 317.57 324.37 330.09 334.95 339.40 341.63
reduced pressures and 101.3 kPa. For the methyl acetate þ ethyl
1.0000 315.49 321.98 327.23 331.66 335.51 337.60
a
lactate and methanol þ ethyl lactate systems, Resa et al. reported
Standard uncertainties u are u(P) ¼ ±0.03 kPa, u(x1) ¼ ±0.0001, u(T) ¼ ±0.03 K.
VLE data at 101.3 kPa [6,20]. Compared to their data, the

the ratio of the amount of vapor hold-up to that of the initially

440
charged liquid was found to be less than 2.0  104, and the effect
of vapor hold-up was negligible, as in our previous work [11].
For the boiling point measurement at 101.3 kPa, the ebulli- 420
ometer was open to the atmosphere, and the atmospheric pressure
in the ebulliometer was measured using a Fortin barometer with an
accuracy of ±0.013 kPa (±0.1 mmHg). Because the atmospheric 400
pressure fluctuated slightly during the measurements, the experi-
mental boiling points were corrected to 101.3 kPa by the following
equation [13]: 380
T/K

1 101:3  Pexptl
T ¼ Texptl þ  2 ; 360
PNC Pexptl
2:303 i¼1 Bi xi Texptl þ Ci

(1) 340
where NC is the number of components; Texptl is the experimental
temperature at the actual atmospheric pressure; Pexptl, Bi, and Ci are 320
the Antoine constants of component i, as listed in Table 4; and xi is
the mole fraction in the liquid phase.
300
0.0 0.2 0.4 0.6 0.8 1.0
3. Experimental results of binary systems x1, y1
Fig. 2. Temperatureecomposition relationships for the system methyl acetate
In this work, VLE data for three binary systems, namely methyl (1) þ ethyl lactate (2). This work: C, 40.00 kPa; :, 53.33 kPa; -, 66.66 kPa; ;,
acetate (1) þ methanol (2), methyl acetate (1) þ ethyl lactate (2), 79.99 kPa; A, 93.32 kPa; +, 101.3 kPa; Literature: *, Resa et al. [6] at 101.3 kPa; ,
and methanol (1) þ ethyl lactate (2), were measured at Wilson.

Please cite this article in press as: H. Matsuda, et al., Vapor-liquid equilibria of binary and ternary mixtures containing ethyl lactate and effect of
ethyl lactate as entrainer, Fluid Phase Equilibria (2015), http://dx.doi.org/10.1016/j.fluid.2015.12.029
4 H. Matsuda et al. / Fluid Phase Equilibria xxx (2015) 1e8

440 Table 7
Deviations between the experimental and calculated boiling points (DT) for three
binary systems using the Wilson and NRTL models.a

420 Wilson NRTL

P (kPa) jDTjav. (K) jDTjmax. (K) P (kPa) a12 jDTjav. (K) jDTjmax. (K)

Methyl acetate (1) þ Methanol (2)

400 40.00 0.11 0.20 40.00 0.3 0.12 0.21
53.33 0.08 0.18 53.33 0.4 0.09 0.20
66.66 0.07 0.15 66.66 0.2 0.08 0.17
380 79.99 0.04 0.07 79.99 0.4 0.05 0.09
T/K

93.32 0.02 0.04 93.32 0.2 0.02 0.05

101.3 0.02 0.05 101.3 0.4 0.02 0.05
Overall 0.06 0.12 Overall 0.06 0.13
360 Methyl acetate (1) þ Ethyl lactate (2)
40.00 0.48 1.39 40.00 0.20 0.47 1.40
53.33 0.54 1.83 53.33 0.44 0.54 1.82
340 66.66 0.62 2.39 66.66 0.46 0.65 2.41
79.99 0.68 2.10 79.99 0.24 0.67 2.10
93.32 0.69 2.39 93.32 0.46 0.83 2.43
320 101.3 0.72 2.16 101.3 0.20 0.74 2.18
Overall 0.62 2.04 Overall 0.65 2.06
Methanol (1) þ Ethyl lactate (2)
40.00 0.11 0.25 40.00 0.24 0.13 0.30
300 53.33 0.19 0.61 53.33 0.46 0.21 0.65
0.0 0.2 0.4 0.6 0.8 1.0 66.66 0.46 1.29 66.66 0.25 0.46 1.33
x1, y1 79.99 0.67 1.87 79.99 0.37 0.70 1.98
93.32 0.88 2.56 93.32 0.36 0.92 2.88
Fig. 3. Temperatureecomposition relationships for the system methanol (1) þ ethyl 101.3 0.82 1.99 101.3 0.35 0.90 2.21
lactate (2). This work: C, 40.00 kPa; :, 53.33 kPa; -, 66.66 kPa; ;, 79.99 kPa; A, Overall 0.52 1.43 Overall 0.55 1.56
93.32 kPa; +, 101.3 kPa; Literature: *, Resa et al. [20] at 101.3 kPa; , Wilson. P
a
jDTj ¼ jTexptlTcalcdj; jDTjav: ¼ NDP
k¼1 jDTjk =NDP, where NDP is the number of
data points.

Table 6
Wilson and NRTL parameters determined for the three binary systems.

P (kPa) Wilson NRTL

Aij (J mol1) Bij (J mol1 K1) Cij (J mol1 K2) Aij (J mol1) Bij (J mol1 K1) Cij (J mol1 K2) a12
Methyl acetate (1) þ Methanol (2)
40.00 ij ¼ 12 5.34466  102 1.90076 2.01626  104 5.98717  101 0.3
ij ¼ 21 2.99018  104 8.68780  101 2.38227  103 1.20052  101
4
53.33 ij ¼ 12 1.33195  10 4.28011  101 2.13931  104 6.30445  101 0.4
ij ¼ 21 4.20272  104 1.23999  102 8.85039  102 2.06591
66.66 ij ¼ 12 2.35620  102 7.04389  101 1.30473  104 3.49863  101 0.2
ij ¼ 21 2.58029  104 7.07910  101 9.54835  102 6.38855
79.99 ij ¼ 12 1.6769  103 5.01334 1.54307  104 4.29859  101 0.4
ij ¼ 21 2.39877  104 6.40980  101 1.50847  103 2.13253  101
3
93.32 ij ¼ 12 5.62847  10 1.76295  101 3.23932  101 5.09264 0.2
ij ¼ 21 1.11156  104 2.38425  101 6.69240  103 1.65818  101
101.3 ij ¼ 12 8.81295  101 2.14231 1.32696  104 3.58407  101 0.4
ij ¼ 21 1.87069  104 4.69667  101 6.28270  101 5.00653
Methyl acetate (1) þ Ethyl lactate (2)
40.00 ij ¼ 12 6.33100  102 1.94390 1.64030  103 9.12518  102 5.03688 1.45422  102 0.20
ij ¼ 21 3.34798  103 7.93081 4.10031  102 3.73867  103 6.18974 1.15241  102
53.33 ij ¼ 12 3.84254  10 3
9.09446 1.06222  102 1.33917  103 3.83881 6.66220  103 0.44
ij ¼ 21 4.31136  10 3
8.89213 1.22024  102 2.96003  103 6.43264 6.54779
66.66 ij ¼ 12 1.12813  10 2
1.58787  101 7.15600  104 6.51437  103 1.15020  101 3.93885  102 0.46
ij ¼ 21 1.40264  103 4.81356 3.74370  105 9.68200  103 2.74695  101 1.77438  101
79.99 ij ¼ 12 5.43177  103 2.23389  101 1.32204  102 1.24280  103 3.24027 3.24027  102 0.24
ij ¼ 21 2.07113  103 7.26501 1.95968  103 1.04716  103 3.86469 1.77287  102
93.32 ij ¼ 12 3.77571  103 7.72574 4.65372  103 5.91851  103 3.87042 2.62259  102 0.46
ij ¼ 21 2.53539  10 3
2.77895 2.83027  102 1.74787  103 7.20180 2.16409  102
101.3 ij ¼ 12 2.27166  10 3
2.71773 2.67497  102 2.13079  104 7.01273  101 3.23620  102 0.20
ij ¼ 21 2.88338  10 3
1.39999 2.60837  102 4.91117  103 2.88113  101 2.60291  103
Methanol (1) þ Ethyl lactate (2)
40.00 ij ¼ 12 2.77348  103 2.31321 3.42319  102 1.41284  103 4.77800 2.42977  103 0.24
ij ¼ 21 7.62395  103 2.10519  102 5.97169  101 2.96178  103 5.41976 1.10960  102
53.33 ij ¼ 12 3.04006  103 4.82495 2.04646  103 4.39513  102 1.16545  101 3.37121  102 0.46
ij ¼ 21 9.32661  103 5.85635  101 1.08296  101 1.02395  103 4.25280 1.67009  103
66.66 ij ¼ 12 2.38429  10 3
5.63234  101 2.21131  102 3.81247  103 6.26090 4.27204  103 0.25
ij ¼ 21 6.53542  102 1.32812  101 6.15984  102 3.92942  102 9.23027 8.93123  103
79.99 ij ¼ 12 1.17653  102 2.54574 4.58634  103 9.23959  102 2.18557 9.74914  103 0.37
ij ¼ 21 6.71976  102 2.38023  101 7.45588  102 5.11467  10 1.01875  101 2.32744  102
93.32 ij ¼ 12 3.53181  103 3.67846 2.02620  102 4.48977  103 9.88213 6.83991  102 0.36
ij ¼ 21 9.22856  102 8.29971 5.47209  103 4.54872  103 4.63720 4.89659  102
101.3 ij ¼ 12 2.57761  10 3
6.16891 1.50281  102 1.9015210  103 2.36309 3.61845  102 0.35
ij ¼ 21 7.59479  10 3
6.02477 5.73634  102 9.41213  102 2.46891  101 1.64665  102

Please cite this article in press as: H. Matsuda, et al., Vapor-liquid equilibria of binary and ternary mixtures containing ethyl lactate and effect of
ethyl lactate as entrainer, Fluid Phase Equilibria (2015), http://dx.doi.org/10.1016/j.fluid.2015.12.029
 H. Matsuda et al. / Fluid Phase Equilibria xxx (2015) 1e8 5

Table 8 methanol (2)

Azeotropic temperature (Taz) and composition (y1,az) in mole fraction for the methyl 1.0 (315.49 K)
acetate (1) þ methanol (2) system.a

P (kPa) Wilson NRTL

y1,az T (K) y1,az T (K) 0.8

40.00 0.7101 303.10 0.7171 303.15
53.33 0.6969 309.88 0.7041 309.98
66.66 0.6821 315.44 0.6931 315.52
79.99 0.6734 320.19 0.6838 320.22 0.6
93.32 0.6651 324.38 0.6749 224.32
101.3 0.6591 326.60 0.6700 326.55

x2
a
Standard uncertainties u are u(P) ¼ ±0.03 kPa, u(y1,az) ¼ ±0.0001, u(T) ¼ ±0.03 K.
0.4
experimental boiling point temperatures obtained in the present azeotrope
study were higher in the ethyl lactate-rich region. (303.10 K)

0.2
4. Data reduction and prediction

In this work, the Wilson and NRTL models were used for cor-
relations or predications with the experimental boiling point data. 0.0
0.0 0.2 0.4 0.6 0.8 1.0
Liquid phase activity coefficients were calculated using the ethyl lactate (3) x1 methyl acetate (1)
following equation assuming ideal gas behavior: (396.91 K) (305.65 K)

Pyi Fig. 5. Residue curve map and isovolatility line for the system methyl acetate
gi ¼ ; (2) (1) þ methanol (2) þ ethyl lactate (3) at 40.00 kPa: , residue curve using Wilson
PiS xi
model; ————, isovolatility line; 5, unstable node [azeotropic point of methyl
acetate(1) þ methanol(2)]; C, stable node; B, saddle node.
where xi and yi are the equilibrium mole fractions of component i in
the liquid and vapor phase, respectively; gi is the liquid phase ac-
tivity coefficient of component i; P is the total pressure; and PiS is Wilson model and gijegjj in the NRTL model were expressed ac-
the saturated vapor pressure of pure component i. PiS was calcu- cording to the following polynomial temperature functions:
lated using the Antoine equation with the Antoine constants given .
in Table 4. Wilson : lij  lii J mol1 ¼ AWilson
ij þ BWilson
ij ðT=KÞ

þ CijWilson ðT=KÞ2 ; (3)

4.1. Binary systems
.
Experimental VLE data for the three binary systems were fitted NRTL : gij  gjj J mol1 ¼ ANRTL
ij þ BNRTL
ij ðT=KÞ þ CijNRTL ðT=KÞ2 :
to the Wilson and NRTL models. The binary parameters lijelii in the
(4)
330
The liquid molar volumes vLi required for the Wilson model were
treated as constant, and were determined from the experimental
density at 298.15 K. The values of vLi are listed in Table 2. The pa-
rameters Aij, Bij, and Cij in the Wilson and NRTL models were fitted
320 using the Marquardt method [21] for each system at each pressure.
The degree of Eqs. (3) and (4) was changed in each binary system
according to the correlation accuracy. The following objective
function (Fobj) was minimized during the optimization of the binary
Taz / K

Wilson or NRTL parameters:

310
X
NDP 2
Fobj ¼ Texptl  Tcalcd ; (5)
k
k¼1

where NDP is the number of experimental data points; and Texptl

300
and Tcalcd are the experimental and calculated boiling points,
respectively. Determined Wilson and NRTL parameters for Eqs. (3)
and (4) are summarized in Table 6. Absolute deviations between the
experimental and calculated boiling points at each experimental
290 pressure in both models are listed in Table 7. Good agreements
0.60 0.65 0.70 0.75 0.80 between the experimental and calculated boiling points were ob-
y1,az tained for all binary systems investigated. The calculated VLE from
the Wilson model are shown in Figs. 1e3 together with the calcu-
Fig. 4. Azeotropic temperature Taz and composition y1,az as mole fraction, on the basis lated vapor co-existence curves. In the methyl acetate þ methanol
of the experimental VLE data and literature values, for the system methyl acetate
(1) þ methanol (2). C, This work; B, Dobroserdov and Bagrov [17]; D, Figurski and
system, the azetropic points were determined from the binary
Von Weber [18]; ,, Iliuta et al. [12]; ◊, Nagata and Ohta [11]; :, Nagata [13]; -, Wilson or NRTL parameters. The azeotropic composition and
Serafimov and Balasho [19]; ;, Tu et al. [15]. temperature determined for the methyl acetate þ methanol system

Please cite this article in press as: H. Matsuda, et al., Vapor-liquid equilibria of binary and ternary mixtures containing ethyl lactate and effect of
ethyl lactate as entrainer, Fluid Phase Equilibria (2015), http://dx.doi.org/10.1016/j.fluid.2015.12.029
6 H. Matsuda et al. / Fluid Phase Equilibria xxx (2015) 1e8

4 approaches, including analysis of the residue curves and calculation

a of the separation factors. The residue curves are described by the
following set of differential equations:

dxi
¼ xi  yi ; i ¼ 1; …n  1; (6)
3 dx

where x is a dimensionless measure of time. In this work, xi was

solved using the RungeeKutta fourth-order method, coupled with
the Wilson model with the constituent binary parameters. Fig. 5
shows the calculated residue curves at 40.00 kPa for the ternary
S12

2
system of methyl acetate þ methanol þ ethyl lactate. From Fig. 5,
the azeotropic point of the methyl acetate þ methanol system was
an unstable node (residue curves begin), ethyl lactate was a stable
node (residue curves end), and methyl acetate and methanol were
1 saddle points (no residue curves enter or exit). All residue curves
approaching the ethyl lactate (entrainer) vertex were inflected to-
wards the methanol þ ethyl lactate face. Therefore, methanol and
ethyl lactate could be obtained as a bottom product, and methyl
acetate could be obtained as a distillate in an extractive distillation
0 column. Moreover, as described by Laroche et al. [25], if the iso-
0 0.2 0.4 0.6 0.8 1.0 volatility lines intersect the (1)e(3) (ethyl lactate) edge, component
sf
x1 1 could be recovered as a distillate in an extractive distillation
1.0 column, and component 2 could be recovered as a distillate in the
entrainer-recovery column. This was the case for the isovolatility
b lines in the ternary system of methyl acetate þ methanol þ ethyl
lactate. Consequently, methyl acetate could be obtained as a
0.8 distillate in the extractive distillation column, and methanol could
be obtained as a distillate in the entrainer-recovery column.
The separation factors were calculated using the Wilson model
with the binary parameters of the binary systems. The separation
0.6 factor, S12, is defined as follows [4]:
sf

K1 y1 =x1
y1

S12 ¼ ¼ : (7)
K2 y2 =x2
0.4
The separation factor S12 was calculated by predicting ternary
VLE data with several liquid mole fractions, x3, of ethyl lactate.
Fig. 6(a) shows the calculated S12 versus the ethyl lactate-free liquid
0.2 phase mole fraction, x1 sf , with several x3 values for ethyl lactate at
40.00 kPa. Fig. 6(b) also shows ethyl lactate-free vapor phase mole
fraction, y1 sf versus x1 sf . Without ethyl lactate (x3 ¼ 0.00), the bi-
nary system of methyl acetate þ methanol cannot be separated by
0.0 ordinary distillation, and this is shown as an intersection with
0.0 0.2 0.4 0.6 0.8 1.0 S12 ¼ 1 at the azeotropic point of this system. However, when ethyl
sf
x1 lactate was added as an entrainer (x3 ¼ 0.23), the apparent azeo-
tropic point of the methyl acetate þ methanol system disappeared,
Fig. 6. (a). Predicted separation factors a12 for the system methyl acetate
(1) þ methanol (2) þ ethyl lactate (3) at 40.00 kPa by the Wilson model with several
and S12 was >1 over the entire mole fraction range of x1 sf at
liquid mole fractions of ethyl lactate x3: ————, x3 ¼ 0.00; d$d, x3 ¼ 0.10; , 40.00 kPa. The results from 40.00 to 101.3 kPa showed that at lower
x3 ¼ 0.23. (b). Predicted ethyl lactate-free vapor phase mole fraction, y1 sf for the pressures the azeotropic point disappeared with less ethyl lactate.
system methyl acetate (1) þ methanol (2) þ ethyl lactate (3) at 40.00 kPa by the Therefore, ethyl lactate can be used as an entrainer for extractive
Wilson model with several liquid mole fractions of ethyl lactate x3: ————, x3 ¼ 0.00;
distillation of the binary azeotropic system of methyl
d$d, x3 ¼ 0.10; , x3 ¼ 0.23.
acetate þ methanol, especially at lower pressure.

are shown in Table 8. Azeotropic points determined by the Wilson

model are shown in Fig. 1. The pressure dependencies of the tem-
peratures and methyl acetate compositions of the determined
azeotropic points are also shown in Fig. 4, together with the liter-
ature values [14e17,19,22e24]. Fig. 4 shows there was reasonable
agreement between the determined and the literature azeotropic
points.
4.2. Effect as an entrainer
In this work, the effect of ethyl lactate was examined by two
5. Experimental results of ternary system and prediction
VLE data for the ternary system of methyl acetate þ meth
anol þ ethyl lactate were measured at pressures between 40.00 and
101.3 kPa. VLE measurements were performed at x3 ¼ 0.23, where
the apparent azeotropic point of the methyl acetate þ methanol
system disappears as described in Section 4.2. The experimental VLE
data are presented in Table 9. Fig. 7 shows a plot of the experimental
boiling points versus the ethyl lactate-free, liquid phase mole frac-
tion, x1 sf . VLE data for this system were also predicted using binary
Wilson or NRTL parameters obtained from the constituent binary

Please cite this article in press as: H. Matsuda, et al., Vapor-liquid equilibria of binary and ternary mixtures containing ethyl lactate and effect of
ethyl lactate as entrainer, Fluid Phase Equilibria (2015), http://dx.doi.org/10.1016/j.fluid.2015.12.029
 H. Matsuda et al. / Fluid Phase Equilibria xxx (2015) 1e8 7

Table 9
Experimental boiling points, liquid phase mole fractions (xi), temperatures (T), and vapor phase mole fractions (yi,calcd) calculated by Wilson model for the ternary system of
methyl acetate (1) methanol (2) þ ethyl lactate (3).a

x1 x2 x1 sf 40.00 kPa 53.33 kPa

T (K) y1,calcd y2,calcd y1 sf T (K) y1,calcd y2,calcd y1 sf

0.0000 0.7700 0.0000 321.36 0.0000 0.9930 0.0000 327.99 0.0000 0.9916 0.0000
0.0720 0.6928 0.0941 318.79 0.1779 0.8161 0.1790 325.37 0.1652 0.8275 0.1664
0.1542 0.6157 0.2003 316.04 0.3355 0.6597 0.3371 322.90 0.3122 0.6820 0.3140
0.2309 0.5391 0.2999 314.16 0.4487 0.5472 0.4505 321.02 0.4172 0.5778 0.4193
0.3068 0.4628 0.3986 312.87 0.5389 0.4575 0.5408 319.94 0.5013 0.4941 0.5036
0.3845 0.3846 0.4999 311.87 0.6173 0.3792 0.6195 319.05 0.5763 0.4194 0.5788
0.4619 0.3078 0.6001 311.37 0.6875 0.3091 0.6898 318.41 0.6458 0.3500 0.6485
0.5391 0.2309 0.7001 311.32 0.7555 0.2411 0.7581 318.30 0.7166 0.2792 0.7196
0.6129 0.1571 0.7960 311.29 0.8231 0.1733 0.8261 318.19 0.7910 0.2047 0.7944
0.6929 0.0772 0.8998 311.36 0.9040 0.0920 0.9076 318.99 0.8850 0.1104 0.8891
0.7699 0.0000 1.0000 312.10 0.9955 0.0000 1.0000 319.68 0.9950 0.0000 1.0000

x1 x2 x1 sf 66.66 kPa 79.99 kPa

T (K) y1,calcd y2,calcd y1 sf T (K) y1,calcd y2,calcd y1 sf

0.0000 0.7700 0.0000 333.33 0.0000 0.9916 0.0000 338.00 0.0000 0.9906 0.0000
0.0720 0.6928 0.0941 330.68 0.1552 0.8374 0.1564 335.17 0.1662 0.8258 0.1675
0.1542 0.6157 0.2003 328.79 0.2971 0.6970 0.2989 332.80 0.3082 0.6853 0.3102
0.2309 0.5391 0.2999 326.89 0.4033 0.5915 0.4054 331.08 0.4102 0.5840 0.4126
0.3068 0.4628 0.3986 325.62 0.4915 0.5036 0.4939 330.03 0.4935 0.5012 0.4961
0.3845 0.3846 0.4999 325.12 0.5717 0.4238 0.5743 329.33 0.5687 0.4262 0.5716
0.4619 0.3078 0.6001 324.17 0.6462 0.3494 0.6491 328.83 0.6392 0.3558 0.6424
0.5391 0.2309 0.7001 324.08 0.7207 0.2749 0.7239 328.83 0.7110 0.2839 0.7146
0.6129 0.1571 0.7960 324.55 0.7967 0.1987 0.8004 328.90 0.7862 0.2085 0.7904
0.6929 0.0772 0.8998 324.93 0.8893 0.1057 0.8938 329.85 0.8811 0.1132 0.8862
0.7699 0.0000 1.0000 325.76 0.9944 0.0000 1.0000 330.61 0.9936 0.0000 1.0000

x1 x2 x1 sf 93.32 kPa 101.3 kPa

T (K) y1,calcd y2,calcd y1 sf T (K) y1,calcd y2,calcd y1 sf

0.0000 0.7700 0.0000 342.17 0.0000 0.9899 0.0000 344.55 0.0000 0.9901 0.0000
0.0720 0.6928 0.0941 339.34 0.1614 0.8300 0.1628 341.76 0.1584 0.8331 0.1598
0.1542 0.6157 0.2003 337.09 0.2972 0.6957 0.2993 339.43 0.2930 0.7000 0.2951
0.2309 0.5391 0.2999 334.94 0.3949 0.5989 0.3974 337.57 0.3913 0.6025 0.3937
0.3068 0.4628 0.3986 334.24 0.4751 0.5192 0.4778 336.78 0.4733 0.5210 0.4760
0.3845 0.3846 0.4999 333.70 0.5483 0.4463 0.5513 335.96 0.5491 0.4455 0.5521
0.4619 0.3078 0.6001 333.39 0.6179 0.3769 0.6211 335.73 0.6214 0.3734 0.6246
0.5391 0.2309 0.7001 333.07 0.6898 0.3050 0.6934 335.38 0.6959 0.2988 0.6996
0.6129 0.1571 0.7960 333.61 0.7669 0.2277 0.7711 335.85 0.7745 0.2200 0.7788
0.6929 0.0772 0.8998 334.32 0.8676 0.1267 0.8726 336.85 0.8742 0.1199 0.8794
0.7699 0.0000 1.0000 335.76 0.9935 0.0000 1.0000 337.85 0.9933 0.0000 1.0000
a
Standard uncertainties u are u(P) ¼ ±0.03 kPa, u(x) ¼ ±0.0001, u(y) ¼ ±0.0001, u(T) ¼ ±0.03 K.

VLE data, and the predicted results were compared with the
experimental VLE data. These results are summarized in Table 10.
The vapor phase mole fractions calculated by Wilson model are also
340 presented in Table 9. Both models gave reasonable agreement be-
tween the experimental and predicted VLE data, but the Wilson
model had better predictive accuracy than the NRTL model. The
results predicted by the Wilson model are shown in Fig. 7.
T/K

330

Table 10
Deviations between the experimental and calculated boiling points (DT) for the
ternary system of methyl acetate (1) þ methanol (2) þ ethyl lactate (3) using the
Wilson and NRTL models.a
320 Wilson NRTL

P/kPa jDTjav./K jDTjmax./K P/kPa jDTjav./K jDTjmax./K

40.00 0.27 0.53 40.00 0.82 1.20

53.33 0.15 0.41 53.33 0.55 0.84
66.66 0.24 0.61 66.66 0.39 1.01
310 79.99 0.21 0.56 79.99 0.40 1.60
0.0 0.2 0.4 0.6 0.8 1.0 93.32 0.14 0.46 93.32 0.46 0.84
sf
x1 101.3
Overall
0.22
0.21
0.42
0.50
101.3
Overall
1.20
0.64
1.76
1.04
PNDP
Fig. 7. Temperatureecomposition relationships for the system methyl acetate
a
jDTj ¼ jTexptlTcalcdj; jDTjav: ¼ k¼1 jDTjk =NDP, where NDP is the number of
(1) þ methanol (2) þ ethyl lactate (3) at x3 ¼ 0.23. This work: C, 40.00 kPa; :, data points.
53.33 kPa; -, 66.66 kPa; ;, 79.99 kPa; A, 93.32 kPa; +, 101.3 kPa; , Wilson.

Please cite this article in press as: H. Matsuda, et al., Vapor-liquid equilibria of binary and ternary mixtures containing ethyl lactate and effect of
ethyl lactate as entrainer, Fluid Phase Equilibria (2015), http://dx.doi.org/10.1016/j.fluid.2015.12.029
8 H. Matsuda et al. / Fluid Phase Equilibria xxx (2015) 1e8

6. Conclusions r density (kg m3)

lij  lii Wilson model binary interaction parameter (J mol1)
Isobaric VLE data for three binary mixtures, methyl x dimensionless measure of time in Eq. (6)
acetate þ methanol, methyl acetate þ ethyl lactate, and
methanol þ ethyl lactate, were measured at pressures between Superscript
40.00 and 101.3 kPa. The experimental VLE data were represented L liquid phase
by the Wilson and NRTL models with good accuracy. The effect of S saturated
ethyl lactate as an entrainer was evaluated using two approaches, sf solvent-free
residue curve maps and calculation of separation factors (S12) using
the binary Wilson parameters. Both the residue curve maps and
separation factors showed that ethyl lactate could be used as an Subscripts
entrainer for extractive distillation of the binary azeotropic system 1, 2, i, j components 1, 2, i, and j
methyl acetate þ methanol. VLE data for the ternary system methyl az azeotrope
acetate þ methanol þ ethyl lactate were also measured at x3 ¼ 0.23, calcd calculated
where the apparent azeotropic point of the methyl exptl experimental
acetate þ methanol system disappears. The predicted behavior of
this ternary system using the binary Wilson or NRTL parameters References
agreed well with the experimental VLE data.
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g activity coefficient 1302e1319.

Please cite this article in press as: H. Matsuda, et al., Vapor-liquid equilibria of binary and ternary mixtures containing ethyl lactate and effect of
ethyl lactate as entrainer, Fluid Phase Equilibria (2015), http://dx.doi.org/10.1016/j.fluid.2015.12.029