http://pubs.acs.

org/journal/acsodf Article

Separation of the Azeotropic Mixture Methanol and Toluene Using

Extractive Distillation: Entrainer Determination, Vapor−Liquid
Equilibrium Measurement, and Modeling
Shanshan He, Wenyang Fan, Huiwen Huang, Jun Gao, Dongmei Xu,* Yixin Ma, Lianzheng Zhang,
and Yinglong Wang
Cite This: ACS Omega 2021, 6, 34736−34743 Read Online
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ACCESS Metrics & More Article Recommendations *

sı Supporting Information

ABSTRACT: For separating the azeotropic mixture methanol and toluene, an

extractive distillation is applied with butyl propanoate, triethylamine, and butyl
Downloaded via 189.41.85.96 on December 30, 2023 at 01:59:14 (UTC).

butanoate as the extractive solvents, which were screened by relative volatility,

selectivity, and the x−y curve. The vapor−liquid equilibrium data of the binary and
ternary systems for (toluene + butyl propanoate), (toluene + triethylamine), (toluene +
butyl butanoate), and (methanol + toluene + butyl butanoate) were determined. The
reliability for the experimental vapor−liquid equilibrium (VLE) data was assessed with
the van Ness method. The measured data was fitted by the UNIQUAC, Wilson, and
NRTL models, and the correlated results were consistent with the determined VLE
data. In addition, the COSMO-UNIFAC model was used to predict the VLE data for
comparison.

1. INTRODUCTION propanoate), (toluene + triethylamine), and (toluene + butyl

1,2 butanoate) has not been found in the literature.
Methanol and toluene are extensively applied raw materials,
In this paper, the index selectivity at infinite dilution (S∞
12),
such as in the manufacture of styrene, which is prepared by
the relative volatility (α12), and the x−y diagram were adopted
side-chain alkylation with methanol and toluene as raw to select entrainers for separating the azeotropic mixture
materials, and p-xylene, which can also be prepared with methanol and toluene. The isobaric VLE data of the mixtures
methanol and toluene.1,3,4 From such production processes, a (toluene + butyl butanoate), (triethylamine + toluene), and
liquid mixture containing methanol and toluene can be (toluene + butyl propanoate) were determined under 101.3
produced. To maintain sustainable production, it is necessary kPa. In the meantime, the determined VLE data were
to separate the mixture. However, methanol and toluene can correlated by UNIQUAC,14 NRTL,15 and Wilson.16 Besides,
form an azeotrope with the azeotropic composition (toluene/ the COSMO-UNIFAC17 model was used to generate the VLE
methanol = 0.113:0.887, mole fraction) at 337.02 K under values for the systems for comparison.
101.3 kPa.1 In general, special distillation technologies are
utilized in the chemical industry for separating azeotropic 2. ENTRAINER DETERMINATION
mixtures, including azeotropic distillation,5 salt distillation,6
2.1. Selectivity. The index selectivity at infinite dilution S∞
12
extractive distillation,7−9 and pressure-swing distillation.10 was applied to assess the capacity of entrainers, which is
Here, extractive distillation is considered for separating the defined as follows18
azeotropic mixture methanol and toluene.
To develop the extractive distillation to separate the mixture ∞ γ1∞
methanol and toluene, the vapor−liquid equilibrium (VLE) S12 =
γ2∞ (1)
data including methanol, toluene, and the entrainers are
required. In a previous work, Burke et al.11 investigated the
VLE behavior of the system (toluene + methanol) under 101.3 Received: September 17, 2021
kPa. Wang et al.12 studied the VLE behavior of the mixture Accepted: November 26, 2021
(triethylamine + methanol) at 99.3 kPa. The VLE data for the Published: December 9, 2021
systems (methanol + butyl propanoate) and (methanol + butyl
butanoate) were determined by Espiau et al.13 So far, the
isobaric VLE data of the binary systems (toluene + butyl
© 2021 The Authors. Published by
American Chemical Society https://doi.org/10.1021/acsomega.1c05164
34736 ACS Omega 2021, 6, 34736−34743
ACS Omega http://pubs.acs.org/journal/acsodf Article

where γ∞ ∞
1 and γ2 stand for the infinite dilution activity
coefficients, which were determined using the UNIFAC
model.18 The infinite dilution activity coefficient is expressed
as follows19
ln γi∞ = lim ln γiC + lim ln γi R
xi → 0 xi → 0 (2)
where
Φi z θ Φ
ln γiC = ln + qi ln i + li − i ∑ lixj
xi 2 Φi xi j (3)

ÄÅ ÉÑ
ÅÅ Ñ
and

Å ij yz i
jj zzÑÑÑÑ
y
Å j zz
ln γi R = qiÅÅÅ1 − lnjjj∑ θτ j ji z z j
jj j ij k kj z
z
zzÑÑÑÑ
ÅÅ jj zz j
ÅÅÇ k { k {ÑÑÖ
− ∑ θτ / ∑ θ τ
j j k (4)
where θi and Φi are the area fraction and segment fraction, Figure 2. α12 vs x1 for methanol (1) + toluene (2) with the three
respectively, xi is the mole fraction of component i, ri and qi are entrainers calculated using the UNIFAC model: , triethylamine; red
the pure component parameters, and τij and τji are the , butyl butanoate; blue , butyl propanoate; and ---, without
adjustable parameters. entrainer.
Figure 1 shows the calculated results of S∞ 12 with the
entrainers. From Figure 1, it can be seen that for the system butyl propanoate reveal apparent deviations from unity,
indicating that the three entrainers have the potential to
break the azeotropic point of the mixture methanol and
toluene.
2.3. Effect of Entrainers on VLE. Figure 3 shows the x−y
diagram calculated by the UNIFAC model for the mixture

Figure 1. S∞
12 by the UNIFAC model at T = 298.15 K.

methanol (1) + toluene (2), the capacity of the different

entrainers follows the order butyl butanoate > triethylamine >
butyl propanoate > propyl propionate > o-xylene. The Figure 3. Effect of the different entrainers on VLE for methanol (1) +
calculated selectivity values of butyl butanoate, butyl toluene (2) calculated with the UNIFAC model, red , triethyl-
propanoate, and triethylamine are higher than those of o- amine; , butyl butanoate; and blue , butyl propanoate, and using
xylene and propyl propionate. Therefore, the three entrainers the NRTL activity coefficient model with the regressed parameters:
were chosen for further analysis. red ---, triethylamine; ---, butyl butanoate; blue ---, butyl propanoate;
2.2. Relative Volatility. For selection of entrainers, the and ···, without the entrainer.
relative volatility (α12) of methanol and toluene with different
entrainers was calculated by the UNIFAC model, which is
expressed as follows7
methanol and toluene with the selected entrainers. As can be
y1 /x1 seen from Figure 3, the x−y curves for the mixture are deviated
α12 = from the diagonal line, indicating that the azeotropic point of
y2 /x 2 (5)
the mixture can be broken by the entrainers.
where xi stands for liquid mole fraction and yi stands for vapor Consequently, depending on the analysis of S∞12, α12, and the
mole fraction. x−y curve, butyl butanoate, triethylamine, and butyl
Figure 2 illustrates the relative volatility for the system propanoate can be the potential alternatives to separate the
methanol (1) + toluene (2) with the entrainers. As displayed in azeotropic mixture methanol and toluene using extractive
Figure 2, the α12 values of butyl butanoate, triethylamine, and distillation.
34737 https://doi.org/10.1021/acsomega.1c05164
ACS Omega 2021, 6, 34736−34743
ACS Omega http://pubs.acs.org/journal/acsodf Article

3. RESULTS AND DISCUSSION Table 3. Isobaric VLE Data of the Mixture Toluene (1) +
3.1. VLE Data. The measured VLE data of the systems Butyl Butanoate (2) under 101.3 kPaa
(toluene + butyl propanoate), (triethylamine + toluene), and T/K x1 y1 γ1 γ2
(toluene + butyl butanoate) under 101.3 kPa is summarized in 438.29 0.0000 0.0000
Tables 1−3 and illustrated in Figures 4−6, where x1 stands for 436.65 0.0091 0.0446 1.3413 1.0014
432.64 0.0439 0.1706 1.1589 1.0021
Table 1. Isobaric VLE Data of the Mixture Toluene (1) + 430.75 0.0601 0.2238 1.1566 1.0039
Butyl Propanoate (2) under 101.3 kPaa 427.21 0.0948 0.3208 1.1362 1.0050
T/K x1 y1 γ1 γ2 423.94 0.1295 0.4037 1.1262 1.0053
419.47 0.1814 0.5056 1.1152 1.0071
383.55 1.0000 1.0000
415.44 0.2332 0.5878 1.1083 1.0087
385.58 0.9228 0.9708 1.0012 1.0424
409.54 0.3199 0.6920 1.0964 1.0152
387.34 0.8516 0.9413 1.0013 1.0262
406.37 0.3747 0.7432 1.0871 1.0156
389.47 0.7701 0.9029 1.0015 1.0198
403.50 0.4289 0.7857 1.0789 1.0159
391.64 0.6916 0.8606 1.0017 1.0151
401.59 0.4725 0.8138 1.0636 1.0183
393.31 0.6338 0.8253 1.0020 1.0140
398.11 0.5505 0.8582 1.0535 1.0180
395.60 0.5585 0.7732 1.0021 1.0134
394.08 0.6488 0.9029 1.0463 1.0206
397.38 0.5021 0.7299 1.0038 1.0105
389.61 0.7814 0.9466 1.0281 1.0501
399.88 0.4280 0.6647 1.0048 1.0086
386.85 0.8736 0.9705 1.0164 1.1140
402.56 0.3534 0.5882 1.0052 1.0078
383.55 1.0000 1.0000
404.72 0.2964 0.5215 1.0061 1.0070
a
407.04 0.2382 0.4447 1.0075 1.0061 The standard uncertainties of u are u(P) = 0.35 kPa, u(T) = 0.35 K,
408.68 0.1990 0.3872 1.0082 1.0051 and u(x) = u(y) = 0.0062.
410.42 0.1589 0.3229 1.0091 1.0044
412.26 0.1179 0.2509 1.0106 1.0037
414.22 0.0737 0.1698 1.0438 1.0007
416.31 0.0299 0.0770 1.1103 1.0005
418.37 0.0000 0.0000
a
The standard uncertainties of u are u(P) = 0.35 kPa, u(T) = 0.35 K,
u(x) = 0.0069, and u(y) = 0.0082.

Table 2. Isobaric VLE Data of the Mixture Triethylamine

(1) + Toluene (2) under 101.3 kPaa
T/K x1 y1 γ1 γ2
383.55 0.0000 0.0000
382.93 0.0226 0.0471 1.1486 1.0002
381.64 0.0579 0.1140 1.1228 1.0012
380.42 0.0929 0.1753 1.1117 1.0027
379.26 0.1283 0.2334 1.1057 1.0033
378.15 0.1644 0.2882 1.0980 1.0041
Figure 4. T−x−y curves for the mixture toluene (1) + butyl
376.57 0.2148 0.3595 1.0944 1.0074
propanoate (2): blue ●, T−y (experimental); ■, T−x (experimental);
375.09 0.2709 0.4307 1.0829 1.0080
red ---, UNIQUAC model; , NRTL model; blue ---, Wilson model;
373.69 0.3284 0.4966 1.0709 1.0094 red , COSMO-UNIFAC model; and blue , UNIFAC model.
372.35 0.3866 0.5583 1.0616 1.0098
371.09 0.4457 0.6158 1.0527 1.0105
369.87 0.5079 0.6711 1.0421 1.0116
368.71 0.5698 0.7224 1.0339 1.0127 assumed as an ideal gas at 101.3 kPa for VLE calculation. The
367.23 0.6491 0.7826 1.0263 1.0186 VLE relation is defined as20,21
365.81 0.7379 0.8439 1.0145 1.0240
364.46 0.8195 0.8940 1.0071 1.0544 Pyi
361.96 1.0000 1.0000 γi =
a
Pisxi (6)
The standard uncertainties of u are u(P) = 0.35 kPa, u(T) = 0.35 K,
and u(x) = u(y) = 0.0061. where γi refers to the activity coefficient, xi stands for the mole
fraction in the liquid phase, yi stands for the mole fraction in
the vapor phase, and Psi stands for saturation vapor pressure of
liquid mole fraction and y1 stands for vapor mole fraction. the pure component and was determined using the extended
Besides, the x−y curves for the three mixtures are displayed in Antoine equation, which is defined as22
Figure 7. As shown in Figure 7, all the x−y curves deviate from
the diagonal line, indicating that the solvents can be recovered C 2i
ln(Pis/kPa) = C1i + + C4i(T /K) + C5i
by a common distillation technology. T / K + C 3i
3.2. VLE Calculation. For the investigated mixtures, the
liquid phase is a non-ideal solution, and the vapor phase can be ln(T /K) + C6i(T /K)C7i C8i ≤ T /K ≤ C9i (7)

34738 https://doi.org/10.1021/acsomega.1c05164
ACS Omega 2021, 6, 34736−34743
ACS Omega http://pubs.acs.org/journal/acsodf Article

Figure 7. x−y curves of the mixtures: red -○-, toluene (1) + butyl
butanoate (2); blue -△-, toluene (1) + triethylamine (2); and -□-,
Figure 5. T−x−y curves for the mixture triethylamine (1) + toluene toluene (1) + butyl propanoate (2).
(2): blue ●, T−y (experimental); ■, T−x (experimental); red ---,
UNIQUAC model; , NRTL model; blue ---, Wilson model; red ,
COSMO-UNIFAC model; and blue , UNIFAC model. Table 5 lists the values of ΔP and Δy. As given in Table 5, all
the values of ΔP, Δy do not exceed unity, indicating that the
obtained VLE data for the systems is thermodynamically
consistent.
3.4. VLE Data Correlation. The activity coefficient models
of NRTL, UNIQUAC, and Wilson were adopted to correlate
the isobaric VLE data for (toluene + butyl propanoate),
(triethylamine + toluene), and (toluene + butyl butanoate)
using Aspen Plus. The correlated results of the three systems
using the activity coefficient models are shown in Figures 4−7.
The parameters r and q of the components for the UNIQUAC
model are provided in Table 6. To fit the measured VLE data,

ÄÅ
the following expression is adopted26
N Å Å exp
ÅÅij P − Pical yz i exp cal y2
F = ∑ ÅÅÅÅjjjj i zz + jjj Ti − Ti zzz
zz jj zz
2

ÅÅ
i Å
ÅÇk { k {
É
σP σT
2Ñ
jij xi − xi zyz ij y exp − y cal yz ÑÑÑÑ
j i z
+ jjj zz + jj
z
j zz ÑÑÑÑ
z
cal 2

j z ÑÑ
exp

k { k { ÑÑÖ
i

Figure 6. T−x−y curves for the mixture toluene (1) + butyl σx σy

(10)
butanoate (2): blue ●, T−y (experimental); ■, T−x (experimental);
red ---, UNIQUAC model; , NRTL model; blue ---, Wilson model; where σ, T, and P denote the standard deviation, temperature,
red , COSMO-UNIFAC model; and blue , UNIFAC model. and pressure. The values of standard deviation23 are σP, 0.35
kPa; σT, 0.35 K; σx, 0.008; and σy, 0.006, respectively.
The RMSDs (root-mean-square deviations) and the
correlated interaction parameter values are presented in
where C1i to C9i are the coefficients of the equation, and the Table 7. As displayed in Table 7, the largest values of
values are presented in Table 4. The results of activity RMSDs(T) and RMSDs(y1) are 0.23 K and 0.0054, indicating
coefficient (γi) of the mixtures are presented in Tables 1−3 that the three models can fit the determined VLE data well.
3.3. Thermodynamic Consistency Test. The consistency Furthermore, the experimental vapor pressures of the system
test of van Ness24 was utilized to verify the reliability of the (toluene + triethylamine) at T = 298.14−333.13 K were
determined VLE data. The van Ness test is represented as predicted using the regressed parameters of the Wilson model
1
N and compared with the data reported in ref 27. The results are
Δy = ∑ 100|yiexp − yical | provided in Figure S1 in the Supporting Information. From
N i=1 (8) Figure S1, it can be seen that the predicted results agree with
N
the experimental data in the literature, indicating the reliability
1 P exp − P cal of the regressed model parameters. The UNIFAC and
ΔP = ∑ 100 i exp i COSMO-UNIFAC28,29 models were used to generate the
N i=1 Pi (9)
isobaric VLE values of the three binary mixtures for
where cal and exp refer to the values of calculation and comparison. As can be seen from Figures 4−6, for the mixture
experiments and N indicates the data point number. If all the toluene and butyl propanoate, the prediction results from the
values of ΔP and Δy do not exceed unity, it signifies that the UNIFAC and COSMO-UNIFAC model agree with the VLE
VLE data are thermodynamically consistent. data of the mixtures. For the mixtures (toluene + butyl
34739 https://doi.org/10.1021/acsomega.1c05164
ACS Omega 2021, 6, 34736−34743
ACS Omega http://pubs.acs.org/journal/acsodf Article

Table 4. Coefficients of the Extended Antoine Modela

component C1i C2i C3i C4i C5i C6i C7i C8i/K C9i/K
triethylamine 49.64 −5681.90 0 0 −4.98 1.24 × 10−17 6 158.45 535.15
toluene 70.04 −6729.80 0 0 −8.18 5.30 × 10−6 2 178.18 591.75
butyl butanoate 102.27 −9384.00 0 0 −12.77 7.47 × 10−6 2 181.15 616.00
butyl propanoate 64.32 −7709.80 0 0 −6.84 6.36 × 10−18 6 183.63 594.60
a
Collected from the Aspen databank.23

Table 5. Validated Values of the van Ness Test of methanol + toluene with butyl butanoate is plotted with the
feed ratio (mole fraction) of methanol/toluene/butyl
system ΔP Δy
butanoate = 0.25:0.25:0.5 in Figure 8. The values of relative
toluene + butyl propanoate 0.03 0.19 volatility were calculated and are presented in Table S1 in the
triethylamine + toluene 0.02 0.08
Supporting Information.
toluene + butyl butanoate 0.06 0.18

Table 6. Parameters r and q of the Components for the

UNIQUAC Modela
component r q
toluene 3.9229 2.9680
butyl propanoate 5.5017 4.7360
triethylamine 5.0119 4.2560
butyl butanoate 6.1892 5.2760
a
Taken from the Aspen property databank.25

butanoate) and (toluene + triethylamine), the predicted values

of the vapor phase are in agreement with the measured values,
while the predicted values of the liquid phase show little
deviations compared to the measured values.
To validate the UNIFAC prediction of the effect of these
entertainers on VLE of methanol and toluene, the NRTL
Figure 8. x−y curves for the mixture methanol (1) + toluene (2): ■,
activity coefficient model with the regressed parameter was experimental data with butyl butanoate; , by the NRTL model with
used to generate the VLE data of the mixture methanol and the regressed parameters; and △, from ref 30.
toluene with the three entrainers, which is added in Figure 3.
Also, the experimental ternary VLE data of the system
(methanol + toluene + butyl butanoate) with the best As displayed in Figure 8, with the help of the entrainer butyl
entrainer (butyl butanoate) was determined at 101.3 kPa butanoate, the x−y curve shows a large deviation from the
with the feed ratio (mole fraction) of methanol/toluene/butyl diagonal line with the feed ratio (mole fraction) of methanol/
butanoate = 0.25:0.25:0.5 and calculated by the NRTL and toluene/butyl butanoate = 0.25:0.25:0.5, which indicates that
UNIFAC models, which are provided in Tables S1 and S2 in the entrainer butyl butanoate can enlarge the relative volatility
the Supporting Information. The pseudo-binary x−y diagram of the system methanol and toluene compared to the VLE data

Table 7. Binary Parameters for the Mixtures under 101.3 kPa

parameters RMSD
model a12 a21 b12/K b21/K y1a T/Kb
toluene + butyl propanoate
NRTLc 0.1941 0.1581 −32.14 −112.16 0.0026 0.16
UNIQUACd 22.45 −6.2300 −2285.03 2185.63 0.0023 0.15
Wilsone 7.9342 5.3700 2880.91 −1892.58 0.0025 0.15
triethylamine + toluene
NRTL −15.77 11.76 6211.83 −4602.33 0.0024 0.18
UNIQUAC −3.0611 −4.4827 −2421.73 1850.92 0.0025 0.12
Wilson 9.8052 12.65 2453.72 −4973.45 0.0016 0.17
toluene + butyl butanoate
NRTL 5.9800 2.3171 −2160.88 −926.69 0.0028 0.23
UNIQUAC 19.41 −0.5803 −1538.96 407.64 0.0054 0.19
Wilson 17.06 2.3345 −97.81 −1438.50 0.0053 0.20

N (y1exp − y1cal )2 b N (Tiexp − Tical)2 c

a
RMSD(y1) = . ∑1 = i i
N
i
RMSD(T ) = ∑1 = i N
NRTL, τij = aij + bij/T, the αij value was fixed at 0.3. dUNIQUAC, τij =
exp(aij + bij/T). eWilson, ln Aij = aij + bij/T.

34740 https://doi.org/10.1021/acsomega.1c05164
ACS Omega 2021, 6, 34736−34743
ACS Omega http://pubs.acs.org/journal/acsodf Article

Table 8. Specifications of the Chemicals

T/K
component CAS suppliers mass fraction expa lit analysis methodb
36
toluene 108-88-3 Tianjin Yuanli Chemical Co., Ltd. 0.998 383.55 383.60 GC
382.9537
methanol 67-56-1 Aladdin reagent Shanghai Co., Ltd. 0.998 337.67 337.7511 GC
337.4213
butyl propanoate 590-01-2 Aladdin reagent Shanghai Co., Ltd. 0.990 418.37 418.2638 GC
418.6939
butyl butanoate 109-21-7 Shanghai Macklin Biochemical Co., Ltd. 0.990 438.29 438.3238 GC
438.1539
triethylamine 121-44-8 Aladdin reagent Shanghai Co., Ltd. 0.998 361.96 361.9240 GC
361.9741
a
The standard uncertainties of u are u(P) = 0.35 kPa and u(T) = 0.35 K, and the boiling temperature for the chemicals was determined to be under
101.3 kPa. bGas chromatograph.

for the system at 101.3 kPa reported in ref 30. Also, from Table equilibrium state. Afterward, the samples from the vapor and
S1, the values of relative volatility are greater than unity, liquid phases were gathered for analysis by GC. The more
suggesting that butyl butanoate can effectively break the specific experimental procedures can be referred to the
azeotropic point of the mixture methanol and toluene. literature.33−35
5.3. Sample Analysis. To determine the sample
4. CONCLUSIONS composition, GC (SP-6890) was used, and the information
For separating the azeotropic mixture methanol and toluene of the column type, carrier gas, and the temperatures of the
through extractive distillation, the extractive solvents butyl injector, detector, and column is given in Table 9.
butanoate, triethylamine, and butyl propanoate were chosen
according to selectivity, relative volatility, and the x−y curve. Table 9. Analysis Conditions of GC
With the selected extractive solvents, the isobaric VLE data for
name characteristic description
the mixtures (toluene + butyl propanoate), (triethylamine +
toluene) (butyl butanoate + toluene), and (methanol + column type packing column
toluene + butyl butanoate) were determined under 101.3 specification Porapak Q (3 mm × 2 m)
kPa. The validated results by the van Ness test show that the carrier gas type hydrogen (22 mL/min)
VLE data measured in this work are of thermodynamic pressure 0.18 MPa
consistency. Besides, the UNIQUAC, NRTL, and Wilson injection port temperature 463.15 K
equations were applied in fitting the isobaric VLE data. The volume 0.3 μL
largest values of RMSD(T) and RMSD(y1) are 0.23 K and column temperature 403.15 K
0.0054, respectively. Furthermore, the predictive model detector type thermal conductivity detector (TCD)
COSMO-UNIFAC was used to generate the isobaric VLE temperature 473.15 K

■
data of the three mixtures, and the predicted results show less
deviation from the measured values. Compared to butyl
propanoate and triethylamine, butyl butanoate displays the ASSOCIATED CONTENT
best effect on the separation of methanol and toluene. In *
sı Supporting Information

addition, the ternary VLE data for (methanol + toluene + butyl The Supporting Information is available free of charge at
butanoate) was determined under 101.3 kPa with the feed https://pubs.acs.org/doi/10.1021/acsomega.1c05164.
ratio (mole fraction) of methanol/toluene/butyl butanoate = Comparison of the isothermal VLE data for the mixture
0.25:0.25:0.5. The values of relative volatility are larger than (toluene + triethylamine), experimental isobaric VLE
unity, showing that butyl butanoate can effectively eliminate data, and predicted values by the NRTL and UNIFAC
the azeotropic point of the system. The determined VLE data models for the mixture (methanol + toluene + butyl
and the optimized model parameters are helpful for designing butanoate) (PDF)

■
the separation process.
AUTHOR INFORMATION
5. EXPERIMENTAL SECTION
Corresponding Author
5.1. Materials. The materials butyl butanoate, toluene, Dongmei Xu − College of Chemical and Biological
triethylamine, and butyl propanoate were commercially Engineering, Shandong University of Science and Technology,
obtained. The purity of the chemicals was verified using GC Qingdao 266590, China; orcid.org/0000-0002-5770-
and utilized directly. Table 8 lists the specific descriptions of 0513; Email: [email protected]
the materials.
5.2. Apparatus and Procedures. Measurements of the Authors
binary VLE data of the mixtures (toluene + butyl propanoate), Shanshan He − College of Chemical and Biological
(toluene + triethylamine), and (toluene + butyl butanoate) Engineering, Shandong University of Science and Technology,
were conducted in a Rose-Williams still under 101.3 kPa. Qingdao 266590, China
When the temperature of the prepared system in the still was Wenyang Fan − College of Chemical and Biological
maintained stable over 50 min,31,32 the mixture reached the Engineering, Shandong University of Science and Technology,
34741 https://doi.org/10.1021/acsomega.1c05164
ACS Omega 2021, 6, 34736−34743
ACS Omega http://pubs.acs.org/journal/acsodf Article

Qingdao 266590, China; orcid.org/0000-0002-6881- boiling side-stream pressure-swing distillation system: Preheating feed
9106 stream to dew or bubble point. Sep. Purif. Technol. 2021, 257, 117920.
Huiwen Huang − College of Chemical and Biological (11) Burke, D. E.; Williams, G. C.; Plank, C. A. Vapor-Liquid
Engineering, Shandong University of Science and Technology, Equilibria for the Methanol-Toluene System. J. Chem. Eng. Data 1964,
Qingdao 266590, China 9, 212−214.
(12) Yi-Xuan, W.; Zhao, J.; Dai, M. Vapor-liquid equilibrium for
Jun Gao − College of Chemical and Biological Engineering,
some polar aprotic solvents with methanol or 1,2-dichloroethane. Acta
Shandong University of Science and Technology, Qingdao Phys.-Chim. Sin. 1992, 8, 636−641.
266590, China; orcid.org/0000-0003-1145-9565 (13) Espiau, F.; Ortega, J.; Penco, E.; Wisniak, J. Advances in the
Yixin Ma − College of Chemical and Biological Engineering, correlation of thermodynamic properties of binary systems applied to
Shandong University of Science and Technology, Qingdao methanol mixtures with butyl esters. Ind. Eng. Chem. Res. 2010, 49,
266590, China 9548−9558.
Lianzheng Zhang − College of Chemical and Biological (14) Abrams, D. S.; Prausnitz, J. M. Statistical thermodynamics of
Engineering, Shandong University of Science and Technology, liquid mixtures: A new expression for the excess Gibbs energy of
Qingdao 266590, China; orcid.org/0000-0003-4827- partly or completely miscible systems. AIChE J. 1975, 21, 116−128.
7941 (15) Renon, H.; Prausnitz, J. M. Local compositions in
Yinglong Wang − College of Chemical Engineering, Qingdao thermodynamic excess functions for liquid mixtures. AIChE J. 1968,
University of Science and Technology, Qingdao 266042, 14, 135−144.
China (16) Wilson, G. M. Vapor-Liquid Equilibrium. XI. A New
Expression for the Excess Free Energy of Mixing. J. Am. Chem. Soc.
Complete contact information is available at: 1964, 86, 127−130.
https://pubs.acs.org/10.1021/acsomega.1c05164 (17) Zhu, R.; Taheri, M.; Zhang, J.; Lei, Z. Extension of the
COSMO-UNIFAC Thermodynamic Model. Ind. Eng. Chem. Res.
Notes 2020, 59, 1693−1701.
The authors declare no competing financial interest. (18) Wang, C.; Wang, C.; Guang, C.; Zhang, Z. Comparison of

■
extractive distillation separation sequences for acetonitrile/methanol/
benzene multi-azeotropic mixtures. J. Chem. Technol. Biotechnol. 2018,
ACKNOWLEDGMENTS 93, 3302−3316.
The authors are grateful to the support of the National Natural (19) Fredenslund, A.; Russell, L.; John, M. Group-contribution
Science Foundation of China (no. 21978155). estimation of activity coefficients in nonideal liquid mixtures. AIChE J.

■
1975, 21, 1086−1099.
(20) Smith, J.; Van Ness, H.; Abbott, M. Introduction to Chemical
REFERENCES
Engineering Thermodynamics, 6th ed.; McGraw-Hill: New York, 2001.
(1) Ma, J.; Li, W.; Ni, C.; Li, Y.; Huang, S.; Shen, C.; Xu, C. (21) Wang, S.; Dai, Y.; Qi, H.; Hou, Y.; Zhang, W.; Zhu, Z.; Wang,
Investigation of distillation systems using heavy or intermediate Y.; Gao, J. Flash/distillation for separating 2-pentanone/4-heptanone/
entrainers for separating toluene-methanol: process economics and water azeotropic mixture based equilibrium data and process design.
control. J. Chem. Technol. Biotechnol. 2016, 91, 2111−2124. Sep. Purif. Technol. 2020, 242, 116790.
(2) Wang, C.; Zhuang, Y.; Liu, L.; Zhang, L.; Du, J.; Zhang, Z. (22) Gao, J.; Li, H.; Xu, D.; Zhang, L.; Zhao, L.; Li, C. Isobaric
Design and control of a novel side-stream extractive distillation Vapor-Liquid Equilibrium for Binary Systems of Thioglycolic Acid
column for separating methanol-toluene binary azeotrope with with Water, Butyl Acetate, Butyl Formate, and Isobutyl Acetate at
intermediate boiling entrainer. Sep. Purif. Technol. 2020, 239, 116581. 101.3 kPa. J. Chem. Eng. Data 2017, 62, 355−361.
(3) Wang, C.; Zhuang, Y.; Liu, L.; Zhang, L.; Du, J. Control of (23) Aspen Plus Software, version 7.3; Aspen Technology, Inc.:
energy-efficient extractive distillation configurations for separating the Burlington, MA, 2001.
methanol/toluene azeotrope with intermediate-boiling entrainer. (24) van Ness, H. C.; Byer, S. M.; Gibbs, R. E. Vapor-Liquid
Chem. Eng. Process. 2020, 149, 107862. equilibrium: Part I. An appraisal of data reduction methods. AIChE J.
(4) Hao, C.; Wen, Y.; Wang, B.; Faraz, A.; Huang, W. Synthesis of
1973, 19, 238−244.
HTLcs modified by K3PO4 for side chain alkylation of toluene with
(25) Zhang, Y.; Liu, K.; Wang, Z.; Gao, J.; Zhang, L.; Xu, D.; Wang,
methanol. Green Energy Environ. 2021, 6, 961−967.
Y. Vapour-liquid equilibrium and extractive distillation for separation
(5) Shi, P.; Gao, Y.; Wu, J.; Xu, D.; Gao, J.; Ma, X.; Wang, Y.
of azeotrope isopropyl alcohol and diisopropyl ether. J. Chem.
Separation of azeotrope (2,2,3,3-tetrafluoro-1-propanol + water):
Isobaric vapour-liquid phase equilibrium measurements and azeo- Thermodyn. 2019, 131, 294−302.
tropic distillation. J. Chem. Thermodyn. 2017, 115, 19−26. (26) Li, J.; Hua, C.; Xiong, S.; Bai, F.; Lu, P.; Ye, J. Vapor-liquid
(6) Xu, L.; Xu, D.; Shi, P.; Zhang, K.; Ma, X.; Gao, J.; Wang, Y. Salts equilibrium for binary systems of allyl alcohol + water and allyl
effect on isobaric vapor-liquid equilibrium for separation of the alcohol + benzene at 101.3 kPa. J. Chem. Eng. Data 2017, 62, 3004−
azeotropic mixture allyl alcohol + water. Sep. Purif. Technol. 2018, 457, 3008.
11−17. (27) Kokkonen, P.; Hannu, A. Thermodynamic properties of binary
(7) Dong, Y.; Dai, C.; Lei, Z. Extractive distillation of methylal/ and ternary systems. Vapour-liquid equilibrium data in the trethyl-
methanol mixture using the mixture of dimethylformamide (DMF) amine + toluene system. Thermochim. Acta 1984, 77, 333−339.
and ionic liquid as entrainers. Fuel 2018, 216, 503−512. (28) Dong, Y.; Zhu, R.; Guo, Y.; Lei, Z. A united chemical
(8) Sapei, E.; Petri, U.; Kari I, K.; Juha-Pekka, P.; Ville, A. Vapor− thermodynamic model: COSMO-UNIFAC. Ind. Eng. Chem. Res.
liquid equilibrium for the binary systems tetrahydrothiophene + 2018, 57, 15954−15958.
toluene and tetrahydrothiophene + o-xylene at 368.15 K and 383.15 (29) Dong, Y.; Huang, S.; Guo, Y.; Lei, Z. COSMO-UNIFAC model
K. Fluid Phase Equilib. 2010, 296, 4−8. for ionic liquids. AIChE J. 2020, 66, No. e16787.
(9) Shen, W.; Dong, L.; Wei, S. a.; Li, J.; Benyounes, H.; You, X.; (30) Li, W.; Guan, T.; Cao, Y.; Zhang, Y.; Zhang, T. Isobaric vapor-
Gerbaud, V. Systematic design of an extractive distillation for liquid equilibrium for toluene-methanol system including three ionic
maximum-boiling azeotropes with heavy entrainers. AIChE J. 2015, liquids with acetate anion at 101.3 kPa. Fluid Phase Equilib. 2020, 506,
61, 3898−3910. 112412.
(10) Yang, S.; Zhang, Q.; Ma, Y.; Yuan, X.; Zeng, A. Novel eco- (31) Yang, J.; Pan, X.; Yu, M.; Cui, P.; Ma, Y.; Wang, Y.; Gao, J.
efficient vapor recompression-assisted arrangement for minimum- Vapor-liquid equilibrium for binary and ternary systems of

34742 https://doi.org/10.1021/acsomega.1c05164
ACS Omega 2021, 6, 34736−34743
ACS Omega http://pubs.acs.org/journal/acsodf Article

tetrahydrofuran, ethyl acetate and N-methyl pyrrolidone at pressure

101.3 kPa. J. Mol. Liq. 2018, 268, 19−25.
(32) Pla-Franco, J.; Lladosa, E.; Loras, S.; Montón, J. B. Azeotropic
distillation for 1-propanol dehydration with diisopropyl ether as
entrainer: equilibrium data and process simulation. Sep. Purif. Technol.
2019, 212, 692−698.
(33) Zhang, Y.; Diao, B.; Xu, D.; Jiang, H.; Zhang, L.; Gao, J.; Wang,
Y. Separation of the mixture (isopropyl alcohol + diisopropyl ether +
n-propanol): Entrainer selection, interaction exploration and vapour-
liquid equilibrium measurements. J. Chem. Thermodyn. 2019, 135,
27−34.
(34) Zhu, Z.; Ma, Y.; Gao, J. Isobaric Vapor−Liquid Equilibria for
Binary Systems of Acetic Acid + Benzene, Chloroacetic Acid +
Benzene, and Dichloroacetic Acid + Benzene at 101.33 kPa. J. Chem.
Eng. Data 2010, 55, 3387−3390.
(35) Gao, J.; Zhao, L.; Zhang, L.; Xu, D.; Zhang, Z. Isobaric Vapor-
Liquid Equilibrium for Binary Systems of 2,2,3,3-Tetrafluoro-1-
propanol + 2,2,3,3,4,4,5,5-Octafluoro-1-pentanol at 53.3, 66.7, 80.0
kPa. J. Chem. Eng. Data 2016, 61, 3371−3376.
(36) Parsana, V. M.; Parekh, U.; Dabke, S. P.; Ziniya, K.; Joshi, K.;
Vlugt, T. J. H.; Ramdin, M. Isobaric vapor-liquid equilibrium data of
binary systems containing 2-ethoxyethanol, 2-ethoxyethyl acetate, and
toluene. J. Chem. Eng. Data 2020, 65, 4798−4804.
(37) Luyben, W. L. Comparison of extractive distillation and
pressure-swing distillation for acetone/chloroform separation. Com-
put. Chem. Eng. 2013, 50, 1−7.
(38) Ortega, J.; Hernández, P. Thermodynamic Study of Binary
Mixtures Containing an Isobutylalkanol and an Alkyl (Ethyl to Butyl)
Alkanoate (Methanoate to Butanoate), Contributing with Exper-
imental Values of Excess Molar Enthalpies and Volumes, and Isobaric
Vapor−Liquid Equilibria. J. Chem. Eng. Data 1999, 44, 757−771.
(39) González, E.; Ortega, J. Densities and isobaric vapor-liquid
equilibria of butyl esters (methanoateto butanoate) with ethanol at
101.32 kPa. J. Chem. Eng. Data 1995, 40, 1178−1183.
(40) Yin, X.; Du, C.; Du, Z.; Jiang, W.; Ding, Y.; Du, H.; Yan, Z.;
Zhang, L. Measurement, modelling and molecular dynamics analysis
for isobaric vapour-liquid equilibria of binary or ternary system
(diethylamine, ethyl acetate, triethylamine). J. Chem. Thermodyn.
2020, 151, 106251.
(41) Teske, V.; Vogel, E. The viscosity of the binary vapor mixture
methanol-triethylamine at low densities and in the saturated vapor
phase of the vapor-liquid equilibrium. Fluid Phase Equilib. 2011, 303,
126−133.

34743 https://doi.org/10.1021/acsomega.1c05164
ACS Omega 2021, 6, 34736−34743