J. Chem.

Thermodynamics 118 (2018) 139–146

Contents lists available at ScienceDirect

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

Separation of azeotrope (allyl alcohol + water): Isobaric vapour-liquid

phase equilibrium measurements and extractive distillation
Jingyu Wu a,1, Dongmei Xu a,1, Puyun Shi a, Jun Gao a,⇑, Lianzheng Zhang a, Yixin Ma a, Yinglong Wang b
a
College of Chemical and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266590, China
b
College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, China

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

Article history: To separate the azeotrope of (allyl alcohol + water) by extractive distillation, N-methyl-2-pyrrolidone,
Received 20 September 2017 N-methyl formamide and ethylene glycol were selected as extractive agents, and the isobaric VLE data
Received in revised form 18 November 2017 for the binary systems of (allyl alcohol + N-methyl-2-pyrrolidone), (allyl alcohol + N-methyl formamide)
Accepted 18 November 2017
and (allyl alcohol + ethylene glycol) were determined at 101.3 kPa by a modified Rose type recirculating
Available online 21 November 2017
still. The thermodynamic consistency of the experimental data was checked by the Herington, van Ness,
infinite dilution, and pure component consistency method. Meanwhile, the experimental data were
Keywords:
correlated by the NRTL, UNIQUAC and Wilson activity coefficient models, and the binary interaction
Allyl alcohol
Azeotrope
parameters of the three models were regressed. All the correlated results by the NRTL, UNIQUAC, and
Vapour-liquid equilibrium Wilson models agreed well with the experimental data. Furthermore, the extractive distillation processes
Extractive distillation with the extractive agents were presented to separate the azeotrope of (allyl alcohol + water).
Ó 2017 Elsevier Ltd.

1. Introduction Möllmann [9], N-methyl-2-pyrrolidone, N-methyl formamide and

Allyl alcohol is widely used in the production of medicine,
spices, agricultural chemicals and other engineering applications
because of its excellent physical and chemical properties [1–4].
For example, allyl alcohol can be used as a reaction solvent during
the synthesis of trimethylolpropane diallyl ether. After the reac-
tion, the mixture of allyl alcohol and water is generated [5,6]. To
recover allyl alcohol, it is necessary to separate allyl alcohol from
its aqueous solution, which is also beneficial for environmental
protection and resource reutilization. However, allyl alcohol and
water can form an azeotrope at atmospheric pressure. For the sep-
aration of such an azeotrope, special distillations are needed, such
as extractive distillation, pressure-swing distillation, azeotropic
distillation, reactive distillation and so on [7].
In this work, extractive distillation was adopted to separate the
azeotrope of allyl alcohol and water. For design of the extractive
distillation process, a reliable knowledge of vapour–liquid equilib-
rium (VLE) data for the system of allyl alcohol and water is
required. Particularly, the selection of the entraniners is important,
which can enhance the separation factor for the azeotropic mixture
allyl (alcohol + water) [8]. Therefore, based on the criteria for the
selection of entrainers for extractive distillation by Gmehling and
⇑ Corresponding author.
E-mail address: gao@sdust.edu.cn (J. Gao).
1
Jingyu Wu and Dongmei Xu contributed equally.
ethylene glycol were selected as the entrainer candidates for the
separation of the azeotropic mixture allyl alcohol + water. In recent
years, some investigators have reported the VLE data for the sys-
tem allyl alcohol + water. Grabner [10] and Zhang [2] determined
the isobaric VLE data for the system allyl alcohol + water at
101.3 kPa. Aucejo [11], Harper [12] and Lesteva [13] determined
the isothermal VLE data of allyl alcohol + water at different pres-
sures and salt effect to the VLE of allyl alcohol + water system
was determined by Zhang [14]. However, the isobaric VLE data
for the systems of allyl alcohol with N-methyl-2-pyrrolidone, N-
methyl formamide and ethylene glycol have not been found in
the NIST [15] and Dortmund Data Bank (DDB) [16].
In this work, the isobaric VLE data for the systems allyl alcohol
+ N-methyl-2-pyrrolidone, allyl alcohol + N-methyl formamide,
and allyl alcohol + ethylene glycol at 101.3 kPa were measured
by a recirculating type equilibrium still. The thermodynamic con-
sistency of the VLE data was checked by the method of Herington
test [17], van Ness test [18], infinite dilution test [19], and pure
component consistency test [20]. Furthermore, the NRTL [21],
UNIQUAC [22] and Wilson [23] activity coefficient models were
used to correlate the VLE data, and the interaction parameters of
the three models were obtained. Meanwhile the values of excess
Gibbs energy, GEm , were calculated by fitting the VLE data. Also,
the extractive distillation process was presented to separate allyl
alcohol from its aqueous solution in this work.

https://doi.org/10.1016/j.jct.2017.11.009
0021-9614/Ó 2017 Elsevier Ltd.
140 J. Wu et al. / J. Chem. Thermodynamics 118 (2018) 139–146

2. Experimental 3. Results and discussion

2.1. Chemicals 3.1. Experimental results

All chemicals were supplied by Shandong Xiya Chemical Co, Ltd.
The CAS and mass fraction confirmed by GC (SP6890, Shandong
Lunan Rui Hong Chemical Instrument Co., Ltd.) are listed in Table 1.
All the chemicals were used without further purification.
All chemicals were analytical pure reagents. The water content
of the reagents was checked and confirmed by GC. The pure-
component boiling temperatures were compared with literature
data and the detailed information is presented in Table S1 in the
Supplementary Material. The pressure was maintained with a
manometer (Nanjing Hengyuan Automatic Gauge Co., Ltd.) and
the pressure fluctuation was controlled within 0.1 kPa by the
two-step automatic control scheme.
2.2. Apparatus and procedure
The VLE measurements for the systems (allyl alcohol + N-
methyl-2-pyrrolidone), (allyl alcohol + N-methyl formamide), and
(allyl alcohol + ethylene glycol) were performed at pressure of
101.3 kPa by a modified Rose type recirculating equilibrium still,
which has been presented in detail in previous literature [25,26].
During the measurement, the liquid and condensed vapour phases
were recirculated continuously to ensure sufficient contact. The
equilibrium temperature was determined when the equilibrium
temperature was kept constant for more than 50 min. Then the
samples of the vapour and liquid phases were withdrawn for
analysis. The details of the VLE measurement can be found in the
literatures [27–29].
2.3. Analysis
The samples of vapour and liquid phases were analysed using a
gas chromatograph (SP6890, Shandong Lunan Rui Hong Chemical
Instrument Co., Ltd.) equipped with a thermal conductivity detec-
tor (TCD), and a packing column (ULBON HR-20M, 50 m
0.25
mm I.D., 0.50 m film thickness, Shinwa Chemical Industries Ltd.,
Kyoto, Japan) was used. Hydrogen with the purity of 99.999%
was used as carrier gas at a flow rate of 50 mLmin1. The detector
temperature was maintained at 483 K. The sample compositions
were determined by the area correction normalization method
[30]. GC was calibrated by the standard samples which were pre-
pared gravimetrically by an electronic balance (Ohaus Corporation,
AR1140) with the accuracy of ±0.0001 g. The phase equilibrium
temperature was measured by a precise mercury thermometer
(Tianjin lass Instrument Factory) with the accuracy of ±0.1 K. The
pressure of the system was measured by a manometer (Nanjing
Hengyuan Automatic Gauge Co., Ltd) with the accuracy of ±0.1 kPa.
In this work, the VLE data for three binary mixtures (allyl alco-
hol + N-methyl-2-pyrrolidone), (allyl alcohol + N-methyl for-
mamide), and (allyl alcohol + ethylene glycol), were measured at
pressure of 101.3 kPa. The experimental VLE data with the values
of the activity coefficients and excess Gibbs energy GE for the three
systems are summarized in Tables 2–4. Also, the T-x-y phase dia-
grams for the systems are presented in Figs. 1–3.
3.2. VLE calculation
The VLE relationship is usually expressed as follows [31]:
" #
L
^ i y p ¼ xi c Us ps exp V i ðp  pi Þ
s
/ i i i i ð1Þ
RT
Since the pressure for the VLE measurements was 101.3 kPa, the
^ i and /s associated with non-ideality are all close
Poynting factor, / i
to 1. Considering the non-idealities of the liquid phase, ci for the
three systems can be calculated by Eq. (2), and the calculated val-
ues of ci are presented in Tables 2–4.
Pyi
ci ¼ ð2Þ
P si xi
where xi presents mole fraction of component i in vapour phase and
yi presents mole fraction of component i in liquid phase; P is the
system pressure, 101.3 kPa, and Psi is the saturation pressure of pure
component i, which was obtained by the extended Antoine expres-
sion. The extended Antoine expression is shown as follows:
C 2i
lnðP si =kPaÞ ¼ C 1i þ þ C 4i T þ C 5i lnT þ C 6i T C7i C 8i 6 T 6 C 9i
T þ C 3i
ð3Þ
The constant values for all components were obtained directly
from the Aspen databank [37] and presented in Table 5.
To assess the non-ideality for the systems, the excess Gibbs
energy GE was calculated by the following equation:
GE ¼ RTðx1 lnc1 þ x2 lnc2 Þ ð4Þ
where the activity coefficients ci was calculated from the NRTL
model. The calculated results of the excess Gibbs energy (GE ) for
the three binary systems are presented in Fig. 4.
3.3. Thermodynamic consistency test
The consistency of the experimental results for the three binary
systems were checked by Herington [17,32], van Ness [18,33],

Table 1
The CAS, mass fraction purity and boiling temperature (Tb) of the chemicals.

Component CAS Suppliers Water content Mass Tb/Kb Analysis

(mass fraction) fraction method
This Literature
work
Allyl alcohol 107-18-6 Shandong Xiya Chemical Co, Ltd 0.008 0.99 369.95 369.75 [2] GCa
N-methyl-2-pyrrolidone 872-50-4 Shandong Xiya Chemical Co, Ltd 0.005 0.990 475.44 475.45 [22] GCa
N-methyl formamide 123-39-7 Shandong Xiya Chemical Co, Ltd 0.009 0.990 472.25 473.15 [23] GCa
Ethylene glycol 107-21-1 Shandong Xiya Chemical Co, Ltd 0.004 0.990 470.32 470.39 [24] GCa
a
Gas chromatograph.
b
The experimental pressure for the measurement of boiling temperature is 101.3 kPa, the standard uncertainties u of P and T are u(P) = 0.1 kPa, u(T) = 0.1 K.
 J. Wu et al. / J. Chem. Thermodynamics 118 (2018) 139–146 141

Table 2
Experimental VLE values for the binary system of allyl alcohol (1) + N-methyl-2-pyrrolidone (2), activity coefficient (c) and Gibbs energy (GE) at 101.3 kPa.a

T/K x1 y1 c1 c2 GE/(Jmol1)
371.00 0.9490 0.9983 1.0143 1.1171 58.95
380.73 0.6399 0.9828 1.0572 1.0459 163.83
389.64 0.4399 0.9590 1.1229 1.1149 362.52
397.17 0.3151 0.9297 1.2045 1.1677 544.27
403.11 0.2617 0.9044 1.1833 1.1816 560.49
410.71 0.1932 0.8684 1.2406 1.1343 489.48
416.48 0.1574 0.8369 1.2537 1.1042 412.47
424.19 0.1217 0.7872 1.2462 1.0711 307.09
436.30 0.0790 0.6840 1.2365 1.0388 187.97
442.43 0.0614 0.6185 1.2453 1.0257 137.29
448.66 0.0454 0.5408 1.2760 1.0152 94.88
454.49 0.0320 0.4557 1.3399 1.0091 68.63
461.87 0.0189 0.3307 1.4055 1.0042 40.46
467.37 0.0114 0.2240 1.4137 1.0018 22.15
470.91 0.0066 0.1475 1.4856 1.0013 15.16
a
Standard uncertainties u of T, P, x and y are u(T) = 0.1 K, u(P) = 0.1 kPa, u(x) = 0.0029, u(y) = 0.0029.

Table 3
Experimental VLE values for the binary system of allyl alcohol (1) + N-methyl formamide (2), activity coefficient (c) and Gibbs energy (GE) at 101.3 kPa.a

T/K x1 y1 c1 c2 GE/(Jmol1)
372.35 0.9052 0.9960 1.0111 1.4378 137.49
375.67 0.7840 0.9902 1.0331 1.3215 267.84
378.63 0.6843 0.9846 1.0633 1.2454 350.34
382.18 0.5950 0.9770 1.0769 1.2385 415.40
384.67 0.5351 0.9713 1.0968 1.2079 438.98
391.95 0.4153 0.9527 1.0988 1.1661 420.29
395.10 0.3638 0.9435 1.1273 1.1256 390.36
400.67 0.3002 0.9250 1.1332 1.0885 322.67
404.24 0.2655 0.9112 1.1373 1.0701 281.97
409.46 0.2199 0.8870 1.1527 1.0527 242.70
418.50 0.1602 0.8340 1.1629 1.0360 187.37
426.54 0.1138 0.7723 1.2310 1.0208 148.48
434.45 0.0839 0.6946 1.2359 1.0207 132.03
440.40 0.0654 0.6250 1.2373 1.0174 109.95
447.65 0.0451 0.5228 1.2707 1.0154 94.52
455.34 0.0278 0.3921 1.3044 1.0140 79.04
462.64 0.0136 0.2440 1.4189 1.0116 62.16
470.43 0.0028 0.0611 1.4894 1.0062 4.31
a
Standard uncertainties u of T, P, x and y are u(T) = 0.1 K, u(P) = 0.1 kPa, u(x) = 0.0029, u(y) = 0.0029.

Table 4
Experimental VLE values for the binary system of allyl alcohol (1) + ethylene glycol (2), activity coefficient (c) and Gibbs energy (GE) at 101.3 kPa.a

T/K x1 y1 c1 c2 GE/(Jmol1)
372.93 0.8721 0.9950 1.0271 1.9117 329.25
376.27 0.7718 0.9905 1.0282 1.7134 451.53
379.17 0.6584 0.9863 1.0869 1.4195 550.22
383.96 0.5308 0.9786 1.1402 1.2705 580.88
387.16 0.4454 0.9733 1.2182 1.1434 522.25
392.16 0.3599 0.9638 1.2742 1.0620 409.88
396.45 0.3110 0.9532 1.2787 1.0450 351.93
401.16 0.2660 0.9387 1.2789 1.0397 313.51
406.60 0.2216 0.9186 1.2840 1.0253 253.01
411.13 0.1901 0.8978 1.2878 1.0221 224.88
417.52 0.1530 0.8622 1.2920 1.0140 177.10
426.76 0.1103 0.7927 1.2964 1.0116 138.12
433.50 0.0852 0.7261 1.3008 1.0103 114.45
437.49 0.0722 0.6795 1.3057 1.0089 99.82
442.15 0.0588 0.6180 1.3059 1.0053 76.10
448.76 0.0418 0.5124 1.3115 1.0050 60.15
455.80 0.0260 0.3755 1.3216 1.0041 42.73
459.55 0.0184 0.2906 1.3369 1.0038 34.72
467.25 0.0046 0.0872 1.3730 1.0032 17.90
469.40 0.0012 0.0235 1.3926 1.0023 10.49
a
Standard uncertainties u of T, P, x and y are u(T) = 0.1 K, u(P) = 0.1 kPa, u(x) = 0.0029, u(y) = 0.0029.
142 J. Wu et al. / J. Chem. Thermodynamics 118 (2018) 139–146

Fig. 1. T-x-y diagram for the binary system allyl alcohol (1) + N-methyl-2-
pyrrolidone (2) at 101.3 kPa: d, T-x, for experimental values; s, T-y, for experi-
mental values; — calculated by the NRTL model;    calculated by the UNIQUAC
model; — calculated by the Wilson model.
Fig. 3. T-x-y diagram for the binary system allyl alcohol (1) + ethylene glycol (2) at
101.3 kPa: d, T-x, for experimental values; s, T-y, for experimental values; —
calculated by the NRTL model;   calculated by the UNIQUAC model; — calculated
by the Wilson model.

1 XN  
y¼ 100yexp
i  ycal
i
 ð7Þ
N i¼1

 
1 XN Pexp  Pcal 
 i i 
P¼ 100  ð8Þ
N i¼1  Pexpi


where N is the experimental point number, Pexp

i and P cal
i are the
pressure, yexp
i and ycal
i are mole fractions of vapour phase. The super-
scripts ‘‘exp” and ‘‘cal” represent the experimental data and calcu-
lated values. The Pcal cal
i , yi were calculated by the NRTL model with
the binary parameters as given in Table 11. The van Ness test
requires that Dy and DP should be less than 1. The results of the
consistency test are reported in Table 7. As shown in Table 7, all
the values of Dy and DP are less than 1, that confirms the measured
VLE values are reliable.
The infinite dilution test is defined as follows:
 
GE =ðx x RTÞ  lnðc =c Þ
 1 2 2 
I1 ¼ 100 1
 ð9Þ
Fig. 2. T-x-y diagram for the binary system allyl alcohol (1) + N-methyl formamide  lnðc1 =c2 Þ 
x1 ¼0
(2) at 101.3 kPa: d, T-x, for experimental values; s, T-y, for experimental values; —
calculated by the NRTL model;   calculated by the UNIQUAC model; — calculated  
GE =ðx x RTÞ  lnðc =c Þ
by the Wilson model.  1 2 2 
I2 ¼ 100 1
 ð10Þ
 lnðc1 =c2 Þ 
x2 ¼0

infinite dilution [19], and pure component consistency tests, fol- GE =RT and lnðc1 =c2 Þ are calculated from the extended Redlich-
lowing the algorithm proposed by Kang et al. [20,36].
Kister’s equation Eqs. (11) and (12) [34,35]
The Herington test method is expressed as follows:
  GE =RT ¼ x1 x2 ½C 0 þ C 1 ðx1  x2 Þ þ C 2 ðx1  x2 Þ2  ð11Þ
ðA  BÞ
D ¼ 100  ð5Þ
ðA þ BÞ
lnðc1 =c2 Þ ¼ D0 þ D1 ðx2  x1 Þ þ D2 ð6x1 x2  1Þ þ D3 ðx2  x1 Þð1  8x1 x2 Þ
 
T max  T min  ð12Þ
J ¼ 150 
 ð6Þ
T min In the infinite dilution test, I1 and I2 must be less than 30. The
where A is the area above the zero line on the diagram of ln(c1/c2) results of I1 and I2 are listed in Table 8
vs x, B is the area under the zero line on this diagram; T max and T min The pure component consistency test is presented as follows:
 
are the highest and the lowest boiling temperature, respectively. Pbubble ðx1 ! 1Þ  p01 
For the Herington test, the value of jD  Jj should be less than 10. P01 ¼  0

 ð13Þ
p1
The values of D-J for the three binary systems are presented in
Table 6, which are all less than 10 indicating that the experimental  
Pbubble ðx1 ! 0Þ  p02 
VLE data for the three systems are thermodynamic consistency. P02 ¼  
 ð14Þ
p0
2
The van Ness test is defined as follows:
 J. Wu et al. / J. Chem. Thermodynamics 118 (2018) 139–146 143

Table 5
Parameters (Ci) of the extended Antoine equation.a

Component C1i C2i C3i C4i C5i C6i (
1018) C7i C8i/K C9i/K
allyl alcohol 77.83 8057.60 0 0 8.71 16.60 6.00 144.15 545.10
N-methyl-2-pyrrolidone 61.57 8467.90 0 0 6.36 3.22 6.00 249.15 721.60
N-methyl formamide 63.22 8851.00 0 0 6.48 2.39 6.00 269.35 721.00
ethylene glycol 77.18 10411.00 0 0 8.20 1.65 6.00 260.15 720.00
a
Taken from Aspen property databank [37].

Table 9
Thermodynamic consistency check by the pure component consistency test (DP01 and
DP02 defined variables in the test).

System DP01 < 1 DP02 < 1

allyl alcohol + N-methyl-2-pyrrolidone 0.00 0.00
allyl alcohol + N-methyl formamide 0.00 0.00
allyl alcohol + ethylene glycol 0.00 0.00

F Pure ðF Herington þ F v anNess þ F Inf :Dil Þ

Q VLE ¼ ð15Þ
3
0:25
The quality factors for the Herington, van Ness, infinite dilution,
and pure-component consistency tests and the values of QVLE are
listed in Table 10. The quality factors for the pure component con-
sistency test (FPure) are equal to 1, since the vapour pressures agree
within 0.01P0 for both components in the three systems. The over-
all quality factors QVLE for the three systems are equal to 1, which
indicate that the VLE data are thermodynamically consistent.

Fig. 4. Experimental excess Gibbs energy for the three binary systems at 101.3 kPa
and the calculated values by the NRTL model against mole fraction: j, allyl alcohol 3.4. VLE data correlation
(1) + N-methyl-2-pyrrolidone (2); d, allyl alcohol (1) + N-methyl formamide (2); N,
allyl alcohol (1) + ethylene glycol (2); the solid line is the trend line. The VLE data for the systems (allyl alcohol + N-methyl-2-
pyrrolidone), (allyl alcohol + N-methyl formamide), and (allyl alco-
hol + ethylene glycol) were correlated by the NRTL [21], UNIQUAC
Table 6
Thermodynamic consistency check by the Herington test (D and J defined variables in [22], and Wilson [23] activity coefficient models. The interaction
the test). parameters of the models were obtained by minimizing the follow-
ing objective function according to the maximum likelihood
System D J D-J < 10
method:
allyl alcohol + N-methyl-2-pyrrolidone 48.4358 42.7720 5.6638
2 !2  3
allyl alcohol + N-methyl formamide 43.4480 41.5799 1.8681
XN pexp  pcal 2 T exp  T cal xexp  xcal
2  exp
yi  ycal
2
allyl alcohol + ethylene glycol 35.5472 41.0326 5.4854 F¼ 4 i i
þ i i
þ i i
þ i 5
i¼1 rp rT rx ry
ð16Þ
Table 7
Thermodynamic consistency check by the van Ness test (DP and Dy defined variables
where N represents the number of data points; T, P, x and y are equi-
in the test).
librium temperature, and pressure, mole fractions in liquid phase
System DP < 1 Dy < 1 and vapour phase, respectively; r represents the standard devia-
allyl alcohol + N-methyl-2-pyrrolidone 0.1541 0.8291 tion; the superscripts ‘‘exp” and ‘‘cal” represent the experimental
allyl alcohol + N-methyl formamide 0.1871 0.4472 data and calculated values.
allyl alcohol + ethylene glycol 0.1322 0.3016
The values of the structural parameters r (van der Waals vol-
ume of molecular) and q (van der Waals surface area of molecular)
Table 8
of the components for the UNIQUAC model are listed in Table 11.
Thermodynamic consistency check by the infinite dilution test (I1 and I2 defined The regressed interaction parameters of the three models and the
variables in the test). root-mean-square deviation (RMSD) are given in Table 12.
System I1 < 30 I2 < 30
As shown in Table 12, the RMSDðy1 Þ and RMSDðTÞ are less than
0.0075 and 0.45, respectively. The results indicate that the NRTL,
allyl alcohol + N-methyl-2-pyrrolidone 12.77 21.40
UNIQUAC and Wilson activity coefficient models are suitable for
allyl alcohol + N-methyl formamide 18.15 9.18
allyl alcohol + ethylene glycol 21.12 11.84 the VLE calculation for the three binary systems.

4. Extractive distillation process design

where p01 and p02 are the pure component vapour pressures, pbubble is
the bubble point pressure. In this test, DP01 and DP02
than 1. The results of DP01 and DP02 are listed in Table 9, which indi-
cate that all the experimental data pass this criterion.
The overall quality factor, QVLE, was used to check the VLE data
for the three systems. Combining the above four consistency tests,
QVLE can be established as follows [20,38]:
should be less 4.1. Solvent effects of entrainers
The solvent effects of the three entrainers N-methyl-2-
pyrrolidone, N-methyl formamide and ethylene glycol were exam-
ined by calculation of the separation factor. The relative volatility is
another criterion used for solvent selection, which is the ratio of
144 J. Wu et al. / J. Chem. Thermodynamics 118 (2018) 139–146

Table 10
Quality factors (F) and overall quality factor (QVLE) for thermodynamic consistency test.

System FHerington FVanNess FInf.Dil. Fpure QVLE  1

allyl alcohol (1) + N-methyl-2-pyrrolidone (2) 0.25 0.25 0.25 1.00 1.00
allyl alcohol (1) + N-methyl formamide (2) 0.25 0.25 0.25 1.00 1.00
allyl alcohol (1) + ethylene glycol (2) 0.25 0.25 0.25 1.00 1.00

Table 11
van der Waals volume (r) and surface area (q) of the components for the UNIQUAC
equation.a

Component r q
allyl alcohol 2.550 2.300
N-methyl-2-pyrrolidone 3.981 3.200
N-methyl formamide 2.403 2.192
ethylene glycol 2.409 2.248
a
Taken from Aspen property databank [37].

volatilities between the light and heavy components after the addi-
tion of a solvent. The relative volatility was calculated using the
UNIQUAC model with the binary parameters listed in Table 12.
The x-y diagram of allyl alcohol and water was used to reflect
the change of the relative volatility. As shown in Fig. 5, the relative
volatility of allyl alcohol increased when the entrainer was added.
The three entrainers could effectively break the azeotropic point of
(allyl alcohol + water).
Compared to the three entrainers, N-methyl-2-pyrrolidone Fig. 5. Influence on VLE with different solvents: -d-, N-methyl-2-pyrrolidone; -N-,
shows the greatest deviation from the diagonal, which indicates ethylene glycol; -j-, N-methyl formamide.

that the relative volatility of allyl alcohol was changed effectively.

Therefore, N-methyl-2-pyrrolidone was selected as the entrainer to
design the extractive distillation process for the separation of the
azeotrope (allyl alcohol + water).
4.2. Extractive distillation process design for the azeotrope of allyl
alcohol + water
The flow diagram for the separation of the azeotrope of (allyl
alcohol + water) is shown in Fig. 6. The feed (stream F) was
pumped into column 1 (extraction column). And the solvent
N-methyl-2-pyrrolidone (stream S) was fed near the top of the
column 1 above the binary feed mixture. The allyl alcohol with
the purity of 99.9 mol% (stream D1) was obtained from the top
of the column 1. Meanwhile, the mixture of water + N-methyl-2-
pyrrolidone went to the column 2 (recovery column) as the feed
stream (stream B1). Water was separated from the top of the col-
umn 2 with the purity of 99.5 mol% (stream D2). The N-methyl-
2-pyrrolidone (stream B2) was recycled back to column 1 crossed
the stream 1. In the whole separation process, N-methyl-2-
pyrrolidone had a slight loss and the additional solvent (stream
M) was added as a make-up feed. The calculated results of all the
streams are listed in Table 13.

Table 12
Binary interaction parameters of the NRTL, UNIQUAC and Wilson models, and root-mean-square deviations (RMSD) of vapour mole fraction (y1) and boiling temperature (T) for
the three binary systems.

Model Parameters RMSD Tb/K

aij aji bij/K bji/K y1a
allyl alcohol (1) + N-methyl-2-pyrrolidone (2)
NRTLc 6.7272 0.8576 1999.21 7.0905 0.0074 0.44
UNIQUACd 4.0312 1.1989 1265.26 280.81 0.0075 0.45
Wilsone 0.5355 11.6695 59.5597 3894.61 0.0074 0.42
allyl alcohol (1) + N-methyl formamide (2)
NRTL 2.5377 3.2469 829.80 942.78 0.0042 0.44
UNIQUAC 0.7170 0.8384 225.58 213.18 0.0042 0.42
Wilson 0.5824 0.3959 132.97 173.87 0.0041 0.40
allyl alcohol (1) + ethylene glycol (2)
NRTL 0.5870 0.6152 509.97 191.24 0.0029 0.27
UNIQUAC 0.0452 0.4811 154.06 124.29 0.0028 0.29
Wilson 0.8592 0.2398 333.94 330.07 0.0029 0.29
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
a PN ðyexp ycal Þ
2

RMSDðy1 Þ ¼ i¼1
1;i
N
1;i
.
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
b PN ðT exp T cal
i Þ
2

RMSDðTÞ ¼ i¼1
i
N .
c
NRTL, sij ¼ aij þ bij =T, the value of aij was set at 0.3 for binary systems.
d
UNIQUAC, sij ¼ expðaij þ bij =TÞ.
e
Wilson, lnAij ¼ aij þ bij =T.
 J. Wu et al. / J. Chem. Thermodynamics 118 (2018) 139–146 145

Fig. 6. Flow diagram for the separation process of the mixture allyl alcohol + water by adding N-methyl-2-pyrrolidone as extractive solvent.

Table 13
The information of all the streams for the extractive distillation process.

Streams Mole flow/(kmolh1) Mole fraction

Allyl alcohol Water N-methyl-2-pyrrolidone Allyl alcohol Water N-methyl-2-pyrrolidone
F 50 50 0 0.5 0.5 0
S 0 0 295 0 0 1
D1 50 0.043 0.007 0.999 850PPM 149PPM
B1 trace 49.957 294.993 trace 0.145 0.855
D2 trace 49.975 0.243 trace 0.995 0.005
B2 trace trace 294.75 trace trace 1
M 0 0 0.25 0 0 1

5. Conclusions [2] M. Bandini, M. Tragni, p-Activated alcohols: an emerging class of alkylating

The isobaric VLE values for the binary systems of (allyl alcohol
+ N-methyl-2-pyrrolidone), (allyl alcohol + N-methyl formamide)
and (allyl alcohol + ethylene glycol) were determined at 101.3
kPa by a modified Rose type recirculating still. The thermodynamic
consistency of the experimental results was validated by the Her-
ington, van Ness, infinite dilution, and pure component consis-
tency methods. The results show that the VLE data for the three
binary mixtures are thermodynamically consistent. Meanwhile,
the experimental VLE values for three binary mixtures were corre-
lated using the NRTL, Wilson and UNIQUAC models. The values of
RMSD for the vapour-phase compositions and the temperature
were less than 0.0075 and 0.45 K, respectively. Furthermore, the
selectivity of the three investigated entrainers was evaluated.
The results show that N-methyl-2-pyrrolidone, N-methyl for-
mamide and ethylene glycol could be used as entrainers for the
extractive distillation of the binary azeotropic mixture (allyl alco-
hol + water). The N-methyl-2-pyrrolidone is the best one among
the three entrainers. Finally, the extractive distillation process
was designed for the separation of the azeotrope of (allyl alcohol
+ water).
Acknowledgement
This work was supported by the National Scientific Research
Found of China (NSC 21306106).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at https://doi.org/10.1016/j.jct.2017.11.009.
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JCT 17-781