Article

pubs.acs.org/jced

Isobaric Vapor−Liquid Equilibrium for Three Binary Systems of

Acetaldehyde + Ethanol, Ethyl Acetate, 1‑Butanol at 101.3 kPa
Huanhuan Sun, Cheng Liu, Zhongfeng Geng,* Yang Lu, and Yixuan Chen
Key Laboratory for Green Chemical Technology of Ministry of Education, Research and Development Center of Petrochemical
Technology, Tianjin University, Tianjin 300072, PR China
Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, PR China

ABSTRACT: In this article, isobaric vapor−liquid equilibrium

(VLE) data for three binary systems of acetaldehyde + ethanol,
acetaldehyde + ethyl acetate, and acetaldehyde +1-butanol were
determined using a modified Rose−Williams equilibrium still at
101.3 kPa. The experimental data were confirmed by the area
method of Herington and point-to-point method of Van Ness.
Activity coefficient models, Wilson, NRTL, and UNIQUAC were
employed to correlate the experimental VLE values. Both models
showed a good agreement and the binary interaction parameters
were estimated.

1. INTRODUCTION In previous works, quite a few studies related to acetaldehyde

1,3-Butadiene (BD) is one of the most important basic organic
materials in the chemical industry. It is a high-value added
chemical intermediate which is mainly used for synthetic styrene
butadiene rubber (SBR), acrylonitrile butadiene styrene (ABS),
adiponitrile, nylon, and so on for a very wide range of uses.1
With the growing demand of 1,3-butadiene in domestic and
overseas markets,2 the production process of 1,3-butadiene is
getting more and more significant attention.
Currently, there are two techniques widely used for the
production of 1,3-butadiene. One is dehydrogenation of butene
or butane.3 The other is extraction from the unsaturated
hydrocarbon mixtures of ethylene cracking.4 But, considering the
serious environmental problem associated with the use of
petroleum fuels, an alternative technology for the innovation of
producing 1,3-butadiene is especially crucial to develop.5,6 Along
with the development of bioethanol technology, most of studies
have indicated that using ethanol as the renewable and eco-
friendly fuels to produce 1,3-butadiene is a more promising and
potential method.7−10 And also, lots of great breakthroughs and
progress have been gained from 1920s to this day.11−16 In the
process of making 1,3-butadiene from ethanol, ethanol is first
oxidized to acetaldehyde and then acetaldehyde reacts with
ethanol to produce 1,3-butadiene.17 And the main byproducts
were ethyl acetate, ethyl ether, 1-butanol, acetic acid, water, and a
mixture of materials called oils.18−22 Therefore, there is a strong
urge to design a reasonable and feasible process flow sheet
for separating the 1,3-butadiene.23 During the design process,
a distillation train is used for the recovery of ethanol and
acetaldehyde. But the phase equilibrium data containing
acetaldehyde are not all available in the literature. To ensure
the accuracy of simulation results, a set of reliable experimental
vapor−liquid equilibrium data containing acetaldehyde is needed
to be measured at atmospheric pressure.
have been investigated. For example, isobaric vapor−liquid
equilibrium for the binary systems of acetaldehyde + ethylene
oxide,24 acetaldehyde + diethyl ether,25 acetaldehyde +
ethanol,25−27 acetaldehyde + water,24−26 and acetaldehyde +
ethanoic acid27,28 at atmospheric pressure have been obtained
and reported by many researchers. Meanwhile, the ternary
systems of acetaldehyde + diethyl ether + water25 and
acetaldehyde + ethanol + ethanoic acid27 have been determined
by Suška and Zhu et al. However, no literature data are available
on the phase behavior of binary systems involving acetaldehyde +
ethyl acetate and acetaldehyde +1-butanol.
In this article, to provide basic data for industrial production,
isobaric vapor−liquid phase equilibrium data containing
acetaldehyde, ethanol, ethyl acetate, and 1-butanol were
measured. First, isobaric vapor−liquid phase equilibrium data
of acetaldehyde + ethanol at 101.3 kPa was determined by a
modified Rose−Williams equilibrium still, and there were five
data sources listed in the NIST Thermodynamics Research
Center. So it was used to verify the reliability of the apparatus
used in this work. After that, the experimental data of
vapor−liquid equilibrium for acetaldehyde + ethyl acetate and
acetaldehyde + 1-butanol systems were measured. Then all
of the data were checked by thermodynamic consistency with
the method of Herington29 and van Ness.30 Next, Wilson,31
nonrandom two-liquid (NRTL),32 and universal quasi-chemical
(UNIQUAC)33 models were applied to correlate the experimental
data. What’s more, the binary parameters played a significant role
for many simulation processes.
Received: March 3, 2017
Accepted: May 17, 2017
Published: May 31, 2017

© 2017 American Chemical Society 2136 DOI: 10.1021/acs.jced.7b00231

J. Chem. Eng. Data 2017, 62, 2136−2142
Journal of Chemical & Engineering Data Article

Table 1. Materials Description Purities of these materials were checked by gas chromatography
(GC-7890A) equipped with a flame ionization detector (FID).
purity purification analysis
chemical name source (mass %) method method All of them were used in experiments without any further
acetaldehyde Nanjingshengbicheng, China ≥99.5 none GCa
purification because of no significant impurities. The boiling
ethyl acetate Tianjin Jiangtian, China ≥99.5 none GCa points (Tb) of the four pure compounds at 101.3 kPa were
1-butanol Aladdin, China ≥99.5 none GCa measured using a modified Rose−Williams equilibrium still.
ethanol Tianjin Jiangtian, China ≥99.7 none GCa Both the measured and literature values are gathered in Table 2.
a
Gas chromatograph. 2.2. Apparatus and Procedures. In this work, the
vapor−liquid equilibrium data were determined by a modified
Table 2. CAS, Molecular Weights (M), and Experimental Rose−Williams equilibrium still (Beiyang Analytical Instru-
Boiling Points with the Literature Data of the Pure ment Company) at 101.3 kPa. The experimental pressure was
Compounds at 101.3 kPaa controlled by a vacuum pump and a U-shaped differential
manometer with a precision of 0.03 kPa. The temperature was
boiling temperature, Tb/K obtained with a precise mercury thermometer (Tianjin Glass
component CAS M/g·mol−1 exp.a lit.b lit.c Instrument Factory) with a precision of 0.02 K. The uncertainties
acetaldehyde 75−07−0 44.05 293.84 294.00 293. 6 of the pressure and temperature measurements were 0.30 kPa
ethyl acetate 141−78−6 88.11 350.20 350.21 350.261 and 0.05 K, respectively. The detailed descriptions of the appara-
1-butanol 71−36−3 74.12 390.78 391.90 390.875 tus and the experimental method were given in the previous
ethanol 64−17−5 46.07 351.38 351.44 351.44 literature.35−38
a In each measurement process, different ratio of light com-
Standard uncertainties u are u(T) = 0.05 K, and u(P) = 0.30 kPa.
b
Taken from Aspen properties databank. cRef 34. ponent and heavy component were prepared and added into the
circulation still. Water and ethylene glycol were used as the
condensed fluid to provide low temperature for total con-
2. EXPERIMENTAL SECTION densation. In this equilibrium process, temperature was recorded
2.1. Materials. The materials used in this work were all from every 3 min and the equilibrium state between vapor and
commercial companies. Details about them are listed in Table 1. liquid phases was assumed when the temperature kept constant

Table 3. Isobaric Measured and Calculated VLE Data for Acetaldehyde (1) + Ethanol (2), Acetaldehyde (1) + Ethyl Acetate (2),
and Acetaldehyde (1) + 1-Butanol (2) Systems at 101.3 kPaa
T/K x1 y1 α12 T/K x1 y1 α12
acetaldehyde (1) + ethanol (2)
293.84 1.0000 1.0000 322.98 0.3641 0.8240 8.18
294.85 0.9665 0.9987 26.63 329.44 0.2722 0.7209 6.91
296.92 0.8935 0.9950 23.72 332.17 0.2358 0.6670 6.49
298.17 0.8491 0.9921 22.32 334.66 0.2033 0.6075 6.07
302.95 0.7266 0.9793 17.80 338.35 0.1574 0.5049 5.46
306.24 0.6437 0.9656 15.54 341.49 0.1205 0.4082 5.03
309.44 0.5858 0.9507 13.64 345.16 0.0783 0.2756 4.48
311.52 0.5561 0.9388 12.24 347.97 0.0467 0.1626 3.96
315.21 0.4929 0.9107 10.49 350.19 0.0178 0.0612 3.60
317.96 0.4465 0.8825 9.31 351.38 0.0000 0.0000
acetaldehyde (1) + ethyl acetate (2)
293.84 1.0000 1.0000 322.95 0.3072 0.7560 6.99
294.94 0.9642 0.9967 11.21 324.95 0.2754 0.7122 6.51
295.83 0.9213 0.9922 10.87 329.37 0.2236 0.6532 6.54
297.12 0.8757 0.9859 9.92 332.98 0.1737 0.5686 6.27
299.42 0.7915 0.9742 9.95 335.49 0.1501 0.5071 5.83
303.41 0.6733 0.9514 9.50 337.50 0.1252 0.4447 5.60
305.91 0.6219 0.9393 9.41 340.61 0.0926 0.3577 5.46
311.12 0.5147 0.9007 8.55 345.43 0.0433 0.1884 5.13
316.53 0.4107 0.8392 7.49 349.15 0.0098 0.0467 4.95
318.43 0.3878 0.8178 7.09 350.20 0.0000 0.0000
acetaldehyde (1) + 1-butanol (2)
293.84 1.0000 1.0000 334.18 0.2672 0.9385 41.85
303.46 0.7555 0.9978 146.78 342.07 0.2058 0.9006 34.96
305.63 0.7049 0.9966 122.71 349.02 0.1634 0.8535 29.83
307.76 0.6566 0.9951 106.21 359.25 0.1109 0.7483 23.83
310.13 0.6055 0.9930 92.42 365.74 0.0842 0.6546 20.61
314.49 0.5205 0.9879 75.21 369.33 0.0708 0.5923 19.07
320.12 0.4309 0.9779 58.44 375.25 0.0495 0.4699 17.02
328.09 0.3272 0.9594 48.59 380.56 0.0316 0.3379 15.64
333.60 0.2725 0.9408 42.43 390.78 0.0000 0.0000
a
Standard uncertainties are u(T) = 0.05 K, u(p) = 0.30 kPa, and u(x1) = u(y1) = 0.002

2137 DOI: 10.1021/acs.jced.7b00231

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for 0.5 h or longer. Meanwhile, the temperature as well

as pressure was read. Also, the samples were taken for analysis
immediately.
2.3. Analysis. The compositions of the samples were analyzed
by a gas chromatography (GC-7890A, Agilent, America). The
chromatographic column used was a HP-INNOWax capillary
column (30m × 0.32 mm × 0.25 μm), and sharp peaks could be
gotten for polar compounds. The temperature of FID detector
and injector were maintained at 573.15 and 523.15 K. The oven
temperature was set at temperature programming. For the
acetaldehyde + ethanol and acetaldehyde + ethyl acetate systems,
the oven temperature was maintained from 313.15 K initially for
3 min to 403.15 K finally for 3 min. For the acetaldehyde +
1-butanol system, the oven temperature was kept from 313.15 K
initially for 3 min to 453.15 K finally for 3 min. Both the
temperature rising rates were 10 K·min−1. The sampled volume in
each equilibrium process was 0.2 μL. To decrease the experi- Figure 1. T-x-y diagram for the acetaldehyde (1) + ethanol (2) system at
mental errors and acquire accurate measurement data, analysis atmospheric pressure. (●), Ref 25; (★), Ref 26; (■), Ref 27; (▲),
for each sample were repeated at least four times, and the experimental data; (), calculated data by the Wilson equation; x1 and
average data were taken as experimental results. In addition, a y1 are the mole fractions of acetaldehyde in the liquid and vapor phases,
respectively.
series of standard samples with different compositions had been
prepared gravimetrically before. Based on the area normaliza-
tion method, the correction factors of the components were
obtained with an uncertainty of 0.0001 g. The uncertainties of
the compositions measured were estimated to be 0.002 in mole
fractions.

3. RESULTS AND DISCUSSION

3.1. Experimental Vapor−Liquid Equilibrium Results.
The isobaric experimental vapor−liquid equilibrium (VLE) data
for acetaldehyde (1) + ethanol (2), acetaldehyde (1) + ethyl
acetate (2), and acetaldehyde (1) + 1-butanol (2) systems
were measured at 101.3 kPa, which are all listed in Table 3.
For acetaldehyde (1) + ethanol (2) system, we compared the
experimental vapor−liquid equilibrium data with the literature.
The phase equilibrium diagram is presented in Figure 1, which is
close to the data of Suška and Zhu et al. Table 3 also shows the
Figure 2. T-x-y diagram for the acetaldehyde (1) + ethyl acetate
values of the relative volatilities α12 for these three binary systems, (2) system at atmospheric pressure. (●), experimental data; (),
which were obtained by eq 1: calculated data by the Wilson equation; x1 and y1 are the mole fractions
of acetaldehyde in the liquid and vapor phases, respectively.
y1 /x1
α12 =
(1 − y1)/(1 − x1) (1)

From Table 3, the relative volatilities for these three binary

systems are all much larger than 1, which illustrates that the three
binary mixtures are more likely to be separated by ordinary
distillation at atmospheric pressure. And apparently, it is much
easier to separate the mixture of acetaldehyde and 1-butanol than
the other two systems. In addition, the isobaric phase equilibrium
diagrams for all systems measured are shown in Figures 1, 2, and 3.
Azeotropic phenomenon could not be found in these three binary
mixtures.
3.2. Thermodynamic Consistency Test of the Exper-
imental Data. For the binary system at constant pressure,
Herington area test method, a semiempirical method, was
normally used to check the reliability of the measurement data.
Therefore, the isobaric binary vapor−liquid equilibrium data
for the three binary systems in this article were confirmed by Figure 3. T-x-y diagram for the acetaldehyde (1) + 1-butanol (2) system
Herington area test method.39 According to the Gibbs−Duhem at atmospheric pressure. (●), experimental data; (), calculated data
theorem, the experimental data would pass the test, if the by the Wilson equation; x1 and y1 are the mole fractions of acetaldehyde
difference between D and J were less than 10. in the liquid and vapor phases, respectively.

2138 DOI: 10.1021/acs.jced.7b00231

J. Chem. Eng. Data 2017, 62, 2136−2142
Journal of Chemical & Engineering Data Article

Table 4. Extended Antoine Parameters of Pure Componentsa

compound C1i C2i C3i C4i C5i C6i C7i C8i/K C9i/K
acetaldehyde 46.00 −4643.10 0 0 −4.51 2.70e-17 6 149.78 466.00
ethyl acetate 59.92 −6227.60 0 0 −6.41 1.79e-17 6 189.60 523.30
1-butanol 99.38 −9866.40 0 0 −11.66 1.08e-17 6 183.85 563.10
ethanol 66.40 −7122.30 0 0 −7.14 2.89e-06 2 159.05 514.00
a
Taken from Aspen properties databank.

Table 5. Results of Thermodynamic Consistency Test Table 6. Correlated Binary Interaction Parameters of the
Wilson, NRTL, and UNIQUAC Models
area test point test
systems D−J Δy a
Δyb Δyc results parameters Wilsona NRTLa UNIQUACa
acetaldehyde(1) + ethanol(2) 3.55 0.21 0.27 0.25 passed acetaldehyde (1) + ethanol (2)
acetaldehyde(1) + ethyl −2.58 0.34 0.35 0.33 passed aij 9.52 −6.35 3.68
acetate(2) aji −8.13 11.36 −6.97
acetaldehyde(1) + 1-butanol (2) 3.74 0.12 0.14 0.16 passed
bij −3131.16 1758.41 −999.42
a b
Calculated by Wilson model. Calculated by NRTL model. bji 2759.82 −3406.94 2056.64
c
Calculated by UNIQUAC model. cij 0.3
x1= 1
ADTb/K 0.16 0.24 0.23
|∫ ln(γ1/γ2)dx1| AD y1b 0.0002 −0.0003 −0.0005
x1= 0
D = 100 × x1= 1 AADTc/K 0.28 0.32 0.32
∫x = 0 |ln(γ1/γ2)|dx1 (2) AAD y1c 0.0021 0.0027 0.0025
1
RMSDTd/K 0.32 0.37 0.37
(Tmax − Tmin) RMSDy1d 0.0029 0.0035 0.0034
J = 150 ×
Tmin (3) acetaldehyde (1) + ethyl acetate (2)
aij 1.56 −2.15 1.85
Where, the values of D can be obtained from the ln (γ1/γ2) − x1 aji −6.24 2.98 −1.09
diagram, Tmax and Tmin are the maximum and minimum bij −196.55 493.33 −772.71
temperatures of the measurement system. For every binary bji 1426.67 −756.92 481.12
system, when the vapor and liquid phase reached equilibrium, cij 0.3
the fugacities of each component must be equal. The basic ADTb/K 0.09 0.17 0.11
thermodynamic equation is as follow:
AD y1b −0.0027 −0.0032 −0.0029
v l AADTc/K
fi ̂ = fi ̂ (4)
0.24 0.28 0.24
AAD y1c 0.0034 0.0035 0.0033
v l RMSDTd/K 0.30 0.36 0.31
Where fi ̂ is the fugacity of vapor component i; fi ̂ is the fugacity
RMSDy1d 0.0055 0.0057 0.0055
of liquid component i. According to the γ − φ method, the real acetaldehyde (1) + 1-butanol (2)
behavior of the liquid phase is described by activity coefficients γi,
aij 0.72 −8.59 4.36
while the real behavior of the vapor phase is described by fugacity
aji −23.57 18.54 −10.16
coefficients φvi :
bij 105.93 2574.90 −1248.57
φi v yP
i
= φi sPi sγixi exp(Vi l(P − Pi s)/(RT )) (5) bji 6802.33 −5774.00 3058.04
cij 0.3
In this work, the vapor pressure of pure component i at (Psi ) ADTb/K 0.07 0.03 0.10
temperature T was calculated by the following extended Antoine AD y1b 0.0003 −0.0011 −0.0006
equation: AADTc/K 0.14 0.14 0.23
ln Pi s = C1i + C2i /(T + C3i) + C4iT + C5i ln T + C6iT7i AAD y1c 0.0012 0.0014 0.0016
(6) RMSDTd/K 0.16 0.18 0.28
RMSDy1d 0.0019 0.0024 0.0023
For ≤ T ≤
Ci8 Ci9,
P is in kPa, T is in K. The extended Antoine
parameters were obtained from Aspen, which are presented
a
Wilson: ln Λ ij = a ij + b ij /T; NRTL: τ ij = a ij + b ij /T;
in Table 4. The measurement pressure in this work was UNIQUAC: ln τij = aij + bij/T b AD(y) = (∑in= 1 (yi cal − yi exp ))/n
101.3 kPa, therefore, the value of exp (Vli (P − Psi )/(RT)) n
AD(T ) = (∑i = 1 (Ti cal − Ti exp))/n c n
AAD(y) = (∑i = 1 |yi cal − yi exp |)/n;
is nearly equal to 1. And the vapor phase mixture is approxi- n
AAD(T ) = (∑i = 1 |Ti cal − Ti exp|)/n
mately considered as an ideal gas. The thermodynamic equa- n
tion for these three systems can be simplified as the following
d
RMSD(y) = (∑i = 1 (yi cal − yi exp )2 )/n ;
relation: RMSD(T ) =
n
(∑i = 1 (Ti cal − Ti exp)2 )/n
s
Pi xiγi = Pyi (7)
component i in the liquid mixture; Psi is the vapor pressure of
Where yi is the mole fraction of the component i in the vapor pure component at temperature T. The test results of
phase; xi is the mole fraction of the component i in the liquid thermodynamic consistency by Herington area test method
phase; P is the total pressure; γi is the activity coefficient of for the three binary systems are listed in Table 5.
2139 DOI: 10.1021/acs.jced.7b00231
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Journal of Chemical & Engineering Data Article

Figure 4. Absolute deviations between the calculated values (y1 and T)
and the experimental data with the liquid phase composition (x1) for the
binary system of acetaldehyde (1) + ethanol (2). (a): (■), calculated
temperature by Wilson model; (●), calculated temperature by NRTL
model; (▲), calculated temperature by UNIQUAC model; (b): (■),
calculated vapor phase composition by Wilson model; (●), calculated
vapor phase composition by NRTL model; (▲), calculated vapor phase
composition by UNIQUAC model.
Figure 5. Absolute deviations between the calculated values (y1 and T)
and the experimental data with the liquid phase composition (x1) for the
binary system of acetaldehyde (1) + ethyl acetate (2). (a): (■),
calculated temperature by Wilson model; (●), calculated temperature
by NRTL model; (▲), calculated temperature by UNIQUAC model;
(b): (■), calculated vapor phase composition by Wilson model; (●),
calculated vapor phase composition by NRTL model; (▲), calculated
vapor phase composition by UNIQUAC model.

In addition, point-to-point method of Van Ness were carried

to check the isobaric binary vapor−liquid equilibrium data for the were determined by the following objective function F
three binary systems.30 In this method, the experimental data (maximum likelihood method):
would pass the test, if Δy was less than or equal to 1.40,41 ⎧ m ⎡ cal
⎪ ⎢⎛ xi − xi exp ⎞
n 2 ⎛ y cal − y exp ⎞2
n
F = ∑ ⎨∑ ⎢⎜⎜ ⎟⎟ + ⎜⎜ i i ⎟
⎟
Δy = (∑ 100|yi cal − yi exp |)/n ⎪
k=1 i=1 ⎣ ⎝ σ ⎠ ⎝ σ ⎠
i=1 (8) ⎩ x , i y , i

⎫
Where n is the total number of experimental data; exp are measured ⎛ T cal − T exp ⎞2 ⎛ P cal − P exp ⎞2 ⎤⎪
⎥
values; cal are the calculated results which were obtained from + ⎜⎜ i i
⎟⎟ + ⎜⎜ i i
⎟⎟ ⎬
the Wilson, NRTL, and UNIQUAC models. The test results of ⎝ σT , i ⎠ ⎝ σP , i ⎠ ⎥⎦⎪
⎭ (9)
thermodynamic consistency by van Ness test method for the
three binary systems are also listed in Table 5. From Table 5, Where n is the total number of experimental data; m is the
all the experimental vapor−liquid equilibrium data passed the number of components; x and y are mole fractions in the
thermodynamic consistency. So the measured data in this work liquid phase and vapor phase; T and P represent equilibrium
were reliable. temperature and pressure for every equilibrium system. Cal and
3.3. Correlation of Vapor−Liquid Equilibrium Data. exp are the calculated results and experimental data; σ is the
In this work, acetaldehyde, ethanol, ethyl acetate, and 1-butanol standard deviation. The regression results of each model’s
are all polar compounds. Considering the nonidealities of binary interaction parameters for acetaldehyde (1) + ethanol (2),
the liquid phase, the Wilson,31 NRTL,32 and UNIQUAC33 acetaldehyde (1) + ethyl acetate (2), and acetaldehyde (1) +
thermodynamic models based on local composition theory 1-butanol (2) systems, the average deviations (AD), average
were applied to regress all the isobaric vapor−liquid equilibrium absolute deviations (AAD), and room-mean-squared deviations
measured data. The binary interaction parameters of models (RMSD) of the vapor phase mole fraction and temperature
2140 DOI: 10.1021/acs.jced.7b00231
J. Chem. Eng. Data 2017, 62, 2136−2142
Journal of Chemical & Engineering Data
Figure 6. Absolute deviations between the calculated values (y1 and T)
and the experimental data with the liquid phase composition (x1) for the
binary systems of acetaldehyde (1) + 1-butanol (2). (a): (■), calculated
temperature by Wilson model; (●), calculated temperature by NRTL
model; (▲), calculated temperature by UNIQUAC model; (b): (■),
calculated vapor phase composition by Wilson model; (●), calculated
vapor phase composition by NRTL model; (▲), calculated vapor phase
composition by UNIQUAC model.
between the calculated values and experimental data are all
listed in Table 6. The T-x-y phase diagrams fitted by Wilson
activity coefficient models are plotted in Figures 1−3. For these
materials used in this work, the sequence of the boiling points is
1-butanol > ethanol > ethyl acetate > acetaldehyde. Generally,
there were some differences in deviations among the three
correlation models. And the deviation plots can be found in
details in Figures 4, 5, and 6.
The calculated results correlated by Wilson, NRTL, and
UNIQUAC models compared to the experimental data, the AD,
AAD, RMSD values of the temperature and vapor compositions
for these three systems are all below 0.37 K and 0.0057. And no
significant differences for these three activity coefficient models
were found. The RMSD results and phase diagrams illustrated
that the measured VLE data in this work were successfully
regressed by these three models. For the acetaldehyde (1) +
ethanol (2) system, the RMSD of the temperature and vapor
compositions correlated by Wilson are 0.32 K and 0.0029, which
gives a better result than the other models. For the acetaldehyde
(1) + ethyl acetate (2) system, the RMSD of the temperature
and vapor compositions correlated by Wilson are 0.30 K and
0.0055, and also the Wilson model was the optimal model.
For the acetaldehyde (1) + 1-butanol (2) system, Wilson and
2141
Article
NRTL models all showed a good agreement with the experi-
mental data.
4. CONCLUSIONS
The isobaric vapor−liquid equilibrium data for the three binary
systems of acetaldehyde + ethanol, acetaldehyde + ethyl acetate,
and acetaldehyde +1-butanol were determined at 101.3 kPa.
The data of the acetaldehyde + ethanol system were in good
agreement with the literature. All the experimental data passed
the thermodynamic consistency test. Azeotropic behavior was not
found in these three binary systems. The experimental data were
successfully correlated by the Wilson, NRTL, and UNIQUAC
thermodynamics models. And the Wilson model presented a
much better result for these three systems. Furthermore, the
experimental VLE data and the binary parameters obtained can be
used in any design process containing these materials directly and
will be of great value in the future.
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: zfgeng@tju.edu.cn; Fax: +86-22-27406119; Telephone:
+86-22-27406119.
ORCID
Zhongfeng Geng: 0000-0002-8376-2574
Notes
The authors declare no competing financial interest.
■ REFERENCES
(1) Zubov, A.; Pokorny, J.; Kosek, J. Styrene−butadiene rubber (SBR)
production by emulsion polymerization: Dynamic modeling and
intensification of the process. Chem. Eng. J. 2012, 207, 414−420.
(2) Makshina, E. V.; Janssens, W.; Sels, B. F.; Jacobs, P.A. Catalytic
study of the conversion of ethanol into 1,3-butadiene. Catal. Today
2012, 198, 338−344.
(3) Bhasin, M. M.; Mccain, J. H.; Vora, B. V.; Imai, T.; Pujadó, P. R.
Dehydrogenation and oxydehydrogenation of paraffins to olefins. Appl.
Catal., A 2001, 221, 397−419.
(4) Zhai, Z.; Wang, X.; Licht, R.; Bell, A. T. Selective oxidation and
oxidative dehydrogenation of hydrocarbons on bismuth vanadium
molybdenum oxide. J. Catal. 2015, 325, 87−100.
(5) Huber, G. W.; Iborra, S.; Corma, A. Synthesis of transportation
fuels from biomass: chemistry, catalysts, and engineering. Chem. Rev.
2006, 106, 4044−98.
(6) Alvira, P.; Tomáspejó, E.; Ballesteros, M.; Negro, M. J.
Pretreatment technologies for an efficient bioethanol production
process based on enzymatic hydrolysis: A review. Bioresour. Technol.
2010, 101, 4851−4861.
(7) Makshina, E. V.; Janssens, W.; Sels, B. F.; Jacobs, P.A. Catalytic
study of the conversion of ethanol into 1, 3-butadiene. Catal. Today
2012, 198, 338−344.
(8) Angelici, C.; Weckhuysen, B. M.; Bruijnincx, P. C. Chemocatalytic
Conversion of Ethanol into Butadiene and Other Bulk Chemicals.
ChemSusChem 2013, 6, 1595−1614.
(9) Lewandowski, M.; Babu, G. S.; Vezzoli, M.; et al. Investigations into
the conversion of ethanol to 1, 3-butadiene using MgO: SiO2 supported
catalysts. Catal. Commun. 2014, 49, 25−28.
(10) Chae, H. J.; Kim, T. W.; Moon, Y. K.; et al. Butadiene production
from bioethanol and acetaldehyde over tantalum oxide-supported
ordered mesoporous silica catalysts. Appl. Catal., B 2014, 150, 596−604.
(11) Sushkevich, V. L.; Ivanova, I. I.; Taarning, E. Ethanol conversion
into butadiene over Zr-containing molecular sieves doped with silver.
Green Chem. 2015, 17, 2552−2559.
(12) Janssens, W.; Makshina, E. V.; Vanelderen, P.; et al. Ternary Ag/
MgO-SiO2 Catalysts for the Conversion of Ethanol into Butadiene.
ChemSusChem 2015, 8, 994−1008.
DOI: 10.1021/acs.jced.7b00231
J. Chem. Eng. Data 2017, 62, 2136−2142
Journal of Chemical & Engineering Data Article

(13) Larina, O. V.; Kyriienko, P. I.; Soloviev, S. O. Ethanol Conversion (35) Huang, X.; Xia, S.; Ma, P.; Song, S.; Ma, B. Vapor-Liquid
to 1,3-Butadiene on ZnO/MgO-SiO2 Catalysts: Effect of ZnO Content Equilibrium of N-Formylmorpholine with Toluene and Xylene at
and MgO: SiO2 Ratio. Catal. Lett. 2015, 145, 1162−1168. 101.33 kPa. J. Chem. Eng. Data 2008, 53, 252−255.
(14) Angelici, C.; Velthoen, M. E. Z.; Weckhuysen, B. M.; Bruijnincx, (36) Li, H.; Luo, H.; Xia, S.; Ma, P. Isobaric vapor−liquid equilibrium
P. C. A. Influence of acid−base properties on the Lebedev ethanol-to- for the three binary systems of C14 -C16 n-alkane + methyl myristate at
butadiene process catalyzed by SiO2-MgO materials. Catal. Sci. Technol. 5.00 kPa. Fluid Phase Equilib. 2016, 408, 47−51.
2015, 5, 2869−2879. (37) Yang, C.; Yin, X.; Ma, S. Correction to Organic Salt Effect of
(15) Chung, S.-H.; Angelici, C.; Hinterding, S. O. M.; Weingarth, M.; Tetramethylammonium Bicarbonate on the Vapor−Liquid Equilibrium
Baldus, M.; Houben, K.; Weckhuysen, B. M.; Bruijnincx, P. C. A. Role of of the Dimethyl Carbonate + Methanol System. J. Chem. Eng. Data
Magnesium Silicates in Wet-Kneaded Silica-Magnesia Catalysts for the 2011, 56, 3747−3751.
(38) Yang, C.; Feng, X.; Sun, Y.; Yang, Q.; Zhi, J. Isobaric Vapor−
Lebedev Ethanol-to-Butadiene Process. ACS Catal. 2016, 6, 4034−
Liquid Equilibrium for Two Binary Systems{Propane-1,2-diol + Ethane-
4045.
1,2-diol and Propane-1,2-diol + Butane-1,2-diol at p = (10.0, 20.0, and
(16) Sushkevich, V. L.; Ivanova, I. I. Ag-Promoted ZrBEA Zeolites
40.0) kPa. J. Chem. Eng. Data 2015, 60, 1126−1133.
Obtained by Post-Synthetic Modification for Conversion of Ethanol to (39) Huang, Z.; Li, L.; Zhou, M.; Jiang, H.; Qiu, T. Isobaric vapor−
Butadiene. ChemSusChem 2016, 9, 2216. liquid equilibrium of trifluoroacetic acid + water, trifluoroacetic acid +
(17) Kampmeyer, P. M.; Stahly, E. E. Butadiene from Ethyl Alcohol: ethyl trifluoroacetate and ethyl trifluoroacetate + ethanol binary
Improved Production Processes. Ind. Eng. Chem. 1949, 41, 550−555. mixtures. Fluid Phase Equilib. 2016, 408, 88−93.
(18) Kinsey, H. D.; Kelly, T. H.; Ferrara, P. J. Cyclic process for making (40) Ding, H.; Gao, Y.; Li, J.; et al. Vapor−Liquid Equilibria for
butadiene. U.S Patent No. 2393381, 1946. Ternary Mixtures of Isopropyl Alcohol, Isopropyl Acetate, and DMSO
(19) Murray, I. L. Recovery method for cyclic vapor phase reaction at 101.3 kPa. J. Chem. Eng. Data 2016, 61, 3013−3019.
products. U.S Patent No. 2249847, 1941. (41) Antón, V.; Martín, S.; Lafuente, C.; Gascon, I. Experimental and
(20) Marsh, J. L. Hitchcock M E. Recovery method in process for predicted vapour−liquid equilibrium of the binary mixtures n-heptane +
making butadiene. U.S Patent No. 2395057, 1946. chlorobutane isomers. Fluid Phase Equilib. 2016, 409, 72−77.
(21) Hitcheock, M. E.; Field, J. A. Cyclic butadiene process. U.S Patent
No. 2403743, 1946.
(22) Stahly, E. E. Manufacture of dienes. U.S Patent No. 2439587,
1948.
(23) Burla, J.; Fehnel, R.; Louie, P. Two-step production of 1,3-
butadiene from ethanol. Scholarly Commons; University of Pennsylvania:
Pennsylvania, 2012.
(24) Coles, K. F.; Popper, F. Vapor-Liquid Equilibria. Ethylene
Oxide−Acetaldehyde and Ethylene Oxide−Water Systems. Ind. Eng.
Chem. 1950, 42, 1434−1438.
(25) Gmehling, J.; Onken, U.; Rarey-Nies, J. R. Vapor-Liquid
Equilibrium Data Collection-Organic Hydroxy Compounds: Alcohols.
DECHEMA Chemistry Data Series, Supplement 3; DECHEMA:
Frankfurt, 1988; Vol. 1, p Part 2e.
(26) Gmehling, J.; Onken, U.; Arlt, W. Vapor−Liquid Equilibrium
Data Collection-Tables and Diagrams of Data for Binary and
Multicomponent Mixtures Up to Moderate Pressures; Constants of
Correlation Equations for Computer Use: Alcohols: Ethanol and 1,2-
Ethanediol. DECHEMA Chemistry Data Series, Supplement 6;
DECHEMA: Frankfurt, 2006; Vol. 1, p Part 2h.
(27) Zhu, D.; Gao, D.; Zhang, H.; et al. Geometric Structures of
Associating Component Optimized toward Correlation and Prediction
of Isobaric Vapor−Liquid Equilibria for Binary and Ternary Mixtures of
Ethanal, Ethanol, and Ethanoic Acid. J. Chem. Eng. Data 2013, 58, 7−17.
(28) Gmehling, J.; Onken, U.; Rarey-Nies, J. R. Vapor-Liquid
Equilibrium Data Collection: Aldehydes. DECHEMA Chemistry Data
Series, Supplement 1; DECHEMA: Frankfurt, 1993; Vol. 1, p Part 3a.
(29) Herington, E. F. G. Tests for the Consistency of Experimental
Isobaric Vapor-Liquid Equilibrium Data. J. Inst. Petrol. 1951, 37, 457−
470.
(30) Van Ness, H. C.; Byer, S. M.; Gibbs, R. E. Vapor-liquid
equilibrium: part I. An appraisal of data reduction methods. AIChE J.
1973, 19, 238−244.
(31) Wilson, G. M. Vapor-Liquid Equilibrium. XI. A New Expression
for the Excess Free Energy of Mixing. J. Am. Chem. Soc. 1964, 86, 127−
130.
(32) Renon, H.; Prausnitz, J. M. Local compositions in thermodynamic
excess functions for liquid mixtures. AIChE J. 1968, 14, 135−144.
(33) Abrams, D. S.; Prausnitz, J. M. Statistical Thermodynamics of
Liquid Mixtures: A new Expression for the Excess Gibbs Energy of
Partly or Completely Miscible Systems. AIChE J. 1975, 21, 116−128.
(34) Riddick, J. A.; Bunger, W. B.; Sakano, T. K. Organic Solvents:
Physical Properties and Methods of Purification, 4th ed.; Wiley-
Interscience: New York, 1986.

2142 DOI: 10.1021/acs.jced.7b00231

J. Chem. Eng. Data 2017, 62, 2136−2142