Isobaric Vapor–Liquid Equilibrium for Two Binary Systems (n-Butanol

Article pubs.acs.org/jced

Isobaric Vapor−Liquid Equilibrium for Two Binary Systems (n‑Butanol + 1,4-Butanediol and γ‑Butyrolactone + 1,4-Butanediol) at p = (30.0, 50.0, and 70.0) kPa Qian Yang, Fengmin Jin, Xue Feng, Juan Zhi, and Changsheng Yang* Key Laboratory for Green Chemical Technology of State Education Ministry, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China ABSTRACT: Isobaric vapor−liquid equilibrium (VLE) data for n-butanol + 1,4-butanediol and γ-butyrolactone + 1,4-butanediol have been experimentally determined by a improved Rose equilibrium still under pressures of 30.0, 50.0, and 70.0 kPa in this work. Additionally, the thermodynamic consistency tests of the experimental binary data were examined with the methods of the Herington area test and Van Ness point test, and then, three of the nonrandom activity coefficient models, which were twoliquid (NRTL), Wilson, as well as universal quasichemical (UNIQUAC), were selected to correlate the isobaric VLE data. All results demonstrated that the calculated values of the above-mentioned models achieved good agreement with the measured data.

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a Van Ness point-to-point test.9 Furthermore, the measured values of the two binary systems were regressed with the Wilson,10 nonrandom two-liquid (NRTL),11 and universal quasichemical (UNIQUAC)12 activity coefficient equations.

INTRODUCTION 1,4-Butanediol, often abbreviated as BDO, is a broadly applied diol among the four carbon-based diols in industry.1 BDO is generally used for a polymer raw material in the production of polybutylene terephthalate (PBT) and polyurethanes (PU), and it can also be converted to tetrahydrofuran (THF).2 In addition, BDO is widely used in pharmaceuticals, household and personal care chemicals, paper-making, and automobile and textile industries. The production of BDO by way of selective oxidation of n-butane to cis-butenedioic anhydride has attracted enormous interest in recent years.3 However, several byproducts are found during the reaction, such as n-butanol and γ-butyrolactone. And each of the byproducts has its own application. n-Butanol (or NBA for short) produced from renewable resources has drawn considerable research attention, mainly because of its potential application as a liquid biofuel for transportation.4 Besides, NBA is an indispensable raw material for the chemical industry, which is used to product plasticizers, extracting agents, and paint.5 γ-Butyrolactone (GBL) is not only an important solvent with several advantageous physicochemical properties such as high boiling point and fairly high viscosity but also an preferable fine chemical applied generally in petrochemicals, lithium batteries,6 pharmaceuticals, and textile and pesticide industries. In order to design a distillation column precisely, basic vapor− liquid equilibrium (VLE) data are essential. A survey of the published literature shows that there are very few papers on the VLE data of the (NBA + BDO) and (GBL + BDO) up to now. Edward et al.7 studied the isobaric molar heat capacities for the binary mixtures NBA and BDO. Therefore, the isobaric VLE data of (NBA + BDO) and (GBL + BDO) under pressures of 30.0, 50.0, and 70.0 kPa were measured in this paper. The thermodynamic consistency tests for all of the VLE data were performed by the Herington method8 and © XXXX American Chemical Society

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EXPERIMENTAL SECTION Materials. The solvents of NBA, BDO, and GBL were purchased from Tianjin Guangfu Reagent Co. The purities of the three materials were determined by gas chromatography (SP2100A) with a thermal conductivity detector (TCD). The amount of water in NBA, BDO, and GBL was 0.4, 2.0, and 2.0% (mass fraction), respectively. Therefore, vacuum distillation of impurities for BDO and GBL was necessary. Eventually, the mass fractions of the purified BDO and GBL were no less than 0.995 and 0.996, respectively. The descriptions of the three substances are presented in Table 1. Table 1. Suppliers and Mass Fractions of the Chemical Samples chemical namea NBA GBL BDO

source Tianjin Guangfu Reagent Co. Tianjin Guangfu Reagent Co. Tianjin Guangfu Reagent Co.

initial mass fraction

purification method

final mass fraction

analysis method

0.995

none

0.995

GCb

0.980

distillation

0.996

GCb

0.980

distillation

0.995

GCb

NBA: n-butanol; GBL: γ-butyrolactone; BDO: 1,4-butanediol. bGas chromatography. a

Received: January 27, 2016 Accepted: July 11, 2016

A

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Table 2. Experimental and Literature Values of Densities (ρ), Refractive Indexes (nD) at T = 298.15 K, and Boiling Points (Tb) at p = 101.3 kPa of Pure Components ρ (g/cm−3) (298.15 K)

a

nD (298.15 K)

Tb (K) (101.3 kPa)

compound

exptl

lit

exptl

lit

exptl

lit

NBA GBL BDO

0.8059 1.1245 1.0130

0.80589a 1.12390c 1.01264e

1.3971 1.4350 1.4449

1.3970a 1.4346c 1.4445e

390.82 477.80 501.05

390.875b 477.81d 501.15e

Reference 13. bReference 14. cReference 15. dReference 16. eReference 17. u(ρ) = 5 × 10−3; u(nD) = 5 × 10−3; u(Tb) = 2 K.

the equilibrium temperature was recorded using a mercury-inglass thermometer with a fluctuation range of 2 K. The condenser was filled with ethyl alcohol as a cooling agent, of which the operational temperature was set to (268.15−278.15) K. The main aim was to condense the evaporated solvent vapor into the liquid rapidly to prevent mass loss. In each experiment, all ground−glass joints were daubed with Vaseline and sealed with Teflon tapes so as to avoid vapor leakage from the system and make sure the results were reliable as much as possible. The maximum capacity of the equilibrium still was roughly 140 cm3, of which almost half of the volume (60 cm3) was filled with solutions. These samples were determined gravimetrically with an electronic balance (Sartorius BP210S) whose accuracy was 1 × 10−4 g. What is more, in each experiment, only when the temperature and pressure had reached steady state for about 30 min or longer were the equilibrium conditions presumed. Previous studies in our laboratory have verified the dependability of the experimental apparatus and process.18−22 Analysis. The contents of the liquid and condensed vapor phase were detected with a BFRL SP-2100A GC, which have a TCD and a Porapak QS (80-100), and the N2000 chromatography software was chosen to handle the response peaks. High-purity hydrogen (>0.999, mass fraction purity) was used as the carrier gas at a constant flow rate of 30 mL·min−1. For NBA and BDO, the column temperature was kept at 493.15 K; for GBL and BDO, the temperature of the column was 473.15 K; for the two binary systems, the temperatures of the injector and detector were held at the same conditions, which were 538.15 and 533.15 K, respectively. The injection volume of each sample was 0.2 μL. A good peak separation was achieved under these conditions. The external standard calibration curve was carried out from a set of gravimetrically prepared standard solvents, which was used to transform the peak area ratios into mole fractions of each sample. Meanwhile, to guarantee reproducibility and reliability of the results, each experimental sample was measured repeatedly three or four times at least. In this way, the standard deviations of the vapor mole fraction were less than 0.005, while the liquid samples were less than 0.002.

Figure 1. Schematic diagram of the VLE apparatus: (1) heating rod, (2) liquid-phase sampling port, (3) vapor-phase sampling port, (4) vapor condenser pipe, (5) coolant inlet, (6) coolant outlet, (7) U-shaped differential manometer, (8) vacuum pump, (9) buffer vessel, (10) needle valve, and (11) vapor temperature thermometer.

In this work, the experimental and the literature values of the densities (ρ), the refractive indexes (nD), and the boiling points (Tb) of pure components are listed in Table 2.13−17 The densities were tested at 298.15 K by an Anton Paar DMA 58 densimeter, and the refractive indexes were checked via an Abbe refractometer Atago 3T. The uncertainties of the densimeter and the refractometer were 5 × 10−3 g·cm−3 and 5 × 10−3, respectively. By the following apparatus (see Figure 1) and specific procedures, we measured the boiling temperatures of pure NBA, GBL, and BDO at p = 101.3 kPa. This experimental device could guarantee the vapor and liquid phases full contact by continuous circulation of the two phases and reach equilibrium rapidly. The measurements of the boiling temperatures were carried out when the temperature and pressure had reached steady state for about 30 min or longer. The experimental values derived from the three models showed good agreement with the literature data. Apparatus and Procedures. According to Figure 1, the Rose−Williams still and other apparatus were employed to measure the isobaric VLE data. As could be seen, the energy of the whole system was supplied with a heating rod. In our experiments, two layers of insulation cotton were wrapped around the still to keep the system temperature stable and reduce the systematic error, and then, the still was composed of a boiling chamber and condenser, which could guarantee that both the liquid and vapor phases were in intimate contact and achieved equilibrium rapidly during continual boiling. With the purpose of controlling the operating pressure of the system, a vacuum pump was linked to the equilibrium still. Besides, we could adjust the opening of the needle valve slowly to ensure that the experimental pressure could be kept in variant for a long period of time. In this case, we determined the system pressure via a U-shaped differential manometer of which the accuracy was estimated to be 0.13 kPa. In addition,

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RESULTS AND DISCUSSION Pure Component Vapor Pressures. The saturated vapor pressures of the pure compositions of NBA, GBL, and BDO were obtained according to the Antoine equation (eq 1) received from Yaws23 in different ranges of temperatures. The Antoine parameters A, B, C, D, and E are presented in Table 3. ⎛ 760ps ⎞ i /kPa⎟ log⎜ ⎝ 101.325 ⎠ B =A+ + C log(T /K) + D(T /K) + E(T /K)2 T /K (1) B

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Table 3. Parameters of the Extended Antoine Equation in This Work Antoine coefficients

a

compound

A

B

C

D

E

range T (K)

NBAa GBLa BDOa

39.6670 10.8996 22.4549

−4001.7 −2886.1 −4202.3

−10.2950 −0.38645 −4.20150

−3.26 × 10−10 −2.65 × 10−3 −7.45 × 10−10

8.67 × 10−7 1.27 × 10−6 6.18 × 10−7

183−563 229−739 293−667

Reference 23.

Table 4. Experimental VLE Data for the Equilibrium Temperature (T), the Mole Fraction of the Liquid Phase (x1) and the Vapor Phase (y1), and the Calculated Activity Coefficient (γi) for the (n-Butanol + 1,4-Butanediol) System at p = (30.0, 50.0, and 70.0) kPaa 30 kPa

50 kPa

70 kPa

T (K)

x1

y1

γ1

465.51 457.08 437.46 424.78 412.18 394.97 388.12 380.22 376.75 373.06 368.92 365.73 360.31 479.79 474.92 462.29 440.61 425.88 412.11 405.20 396.11 389.97 386.19 383.29 378.83 375.79 372.46 489.71 482.58 470.92 462.32 452.16 438.26 430.07 421.08 409.26 395.67 391.25 387.98 384.84 381.07

1.000 0.986 0. 945 0.907 0.853 0.731 0.658 0.543 0.482 0.403 0.301 0.204 0.000 1.000 0.990 0.961 0.895 0.827 0.732 0.667 0.558 0.461 0.390 0.329 0.215 0.120 0.000 1.000 0.985 0.958 0.935 0.902 0.843 0.797 0.732 0.612 0.400 0.306 0.222 0.132 0.000

1.000 0.716 0.322 0.180 0.100 0.042 0.022 0.018 0.013 0.009 0.007 0.003 0.000 1.000 0.839 0.521 0.208 0.107 0.054 0.039 0.024 0.017 0.013 0.010 0.006 0.001 0.000 1.000 0.784 0.504 0.362 0.241 0.134 0.091 0.059 0.032 0.010 0.007 0.004 0.001 0.000

1.000 1.000 1.000 1.009 0.999 0.990 0.984 0.972 0.963 0.951 0.933 0.913 1.000 1.000 1.000 0.998 0.993 0.983 0.973 0.952 0.928 0.908 0.889 0.850 0.813 1.000 1.000 1.000 1.000 0.999 0.997 0.995 0.991 0.980 0.951 0.935 0.918 0.898

Table 5. Experimental VLE Data for the Equilibrium Temperature (T), the Mole Fraction of the Liquid Phase (x1) and the Vapor Phase (y1), and the Calculated Activity Coefficient (γi) for the (γ-Butyrolactone + 1,4-Butanediol) System at p = (30.0, 50.0, and 70.0) kPaa

γ2

30 kPa 0.895 0.899 0.904 0.912 0.932 0.943 0.960 0.968 0.978 0.987 0.994 1.000

50 kPa

0.815 0.820 0.834 0.852 0.878 0.896 0.924 0.947 0.961 0.972 0.988 0.996 1.000

70 kPa

0.896 0.899 0.902 0.906 0.915 0.922 0.933 0.951 0.978 0.987 0.993 0.998 1.000

T (K)

x1

y1

γ1

465.51 460.76 458.60 455.21 452.88 448.21 445.63 443.48 441.56 439.81 437.37 432.99 479.79 477.23 476.28 473.18 470.06 466.63 463.98 461.99 459.93 458.00 455.28 450.33 489.72 484.33 481.02 477.58 474.81 471.29 469.72 468.48 467.99 467.07 465.35 462.61

1.000 0.871 0.814 0.721 0.654 0.523 0.448 0.381 0.319 0.262 0.178 0.000 1.000 0.889 0.848 0.734 0.633 0.527 0.449 0.388 0.324 0.267 0.179 0.000 1.000 0.898 0.820 0.722 0.628 0.483 0.411 0.348 0.321 0.275 0.178 0.000

1.000 0.718 0.625 0.484 0.393 0.271 0.201 0.152 0.129 0.093 0.063 0.000 1.000 0.812 0.740 0.567 0.430 0.318 0.239 0.192 0.145 0.114 0.068 0.000 1.000 0.749 0.621 0.490 0.393 0.278 0.232 0.194 0.177 0.162 0.107 0.000

1.000 0.999 0.998 0.994 0.991 0.984 0.978 0.972 0.967 0.961 0.952 1.000 0.997 0.994 0.983 0.967 0.945 0.926 0.910 0.890 0.872 0.841 1.000 1.004 1.013 1.032 1.059 1.118 1.156 1.196 1.214 1.248 1.331

γ2 0.948 0.955 0.964 0.970 0.981 0.986 0.990 0.993 0.995 0.998 1.000 0.824 0.838 0.875 0.905 0.933 0.950 0.963 0.974 0.982 0.992 1.000 1.389 1.317 1.240 1.178 1.102 1.073 1.052 1.044 1.032 1.014 1.000

a

Standard uncertainties u are u(T) = 2 K, u(p) = 0.13 kPa, u(x) = 0.002, and u(y) = 0.005.

and 70.0 kPa. Therefore, the liquid-phase activity coefficients γi were computed from the simplified equation24

a

Standard uncertainties u are u(T) = 2 K, u(p) = 0.13 kPa, u(x) = 0.002, and u(y) = 0.005.

γixipis = yp i

Experimental Data. The VLE data for the two systems of (NBA + BDO) and (GBL + BDO) at p = (30.0, 50.0, and 70.0) kPa are listed in Tables 4 and 5, respectively. In this work, the vapor-phase behavior of the binary systems could be presumed to be an ideal gas state under pressures of 30.0, 50.0,

(2)

In eq 2, xi and yi denote the liquid- and vapor-phase mole fractions, p refers to the experimental pressure of the system, γi represents activity coefficient in the liquid phase, and psi stands for the saturated vapor pressure of pure component i. C

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where the values of S+ and S− refer to the area of ln(γ1/γ2) − x1 above the zero line on the graph and under the curve.

The values of activity coefficients of component i are shown in Tables 4 and 5. Thermodynamic Consistency Test. To verify the reliability of the VLE data, thermodynamic consistency tests were carried by the Herington method and Van Ness point-to-point test. Herington indicated that the experimental data were consistent if |D − J| < 10. The D was calculated by D=

S+ − S− × 100 S+ + S−

J = 150 ×

a

(4)

In eq 4, Tmax and Tmin represent the highest and lowest boiling temperatures, respectively. For the Van Ness point-to-point test, the excess Gibbs energy could be evaluated by a four-parameter Legendre polynomial k

g=

(3)

Table 6. Results of the Area Test and Point Test for the Two Systems at Three Different Pressures system

P (kPa)

area test D − J

point test |Δy1|

NBA + BDO

30 50 70 30 50 70

−5.32 3.92 −9.83 5.84 −6.43 −6.41

0.005 0.006 0.005 0.004 0.005 0.004

GBL + BDO

(Tmax − Tmin) Tmin

a

GE = x1(1 − x1) ∑ ak Lk (x1) RT

(5)

Table 8. Area Parameters q, Molecule Volume Parameters r, Critical Temperature (Tc), Critical Pressure (Pc), and Critical Compressibility Factor of Component i (Zc) for the UNIQUAC Model

b

compound

q

r

Tca (K)

Pca (kPa)

Zca

NBA GBL BDO

3.0520b 2.5000c 3.3280d

3.45430b 3.02505c 3.75760d

562.93 739.00 666.30

4412.4 5940.0 4880.0

0.259 0.256 0.261

a

Reference 8. bReference 9.

Reference 23. bReference 25. cReference 26. dReference 27.

Table 7. Mathematical Forms of NRTL, UNIQUAC, and Wilson Equations Used in This Work

D

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Here, k is 4, and the objective function was minimized by a nonlinear regression approach F=

∑ (y1cal

+ y2cal − 1)

Table 6. We drew a conclusion that the data of the experiment were reliable. Data Correlation. In this work, all of the VLE data were correlated with NRTL,11 UNIQUAC,12 and Wilson10 activity coefficient models. The formulas of the three equations are illustrated in Table 7. In the NRTL equation, gij − gjj are the binary interaction energy parameters and the nonrandomness parameter (aij) is fixed as a constant of 0.3. With regard to the UNIQUAC model, gij denotes the energy parameter characterizing the interaction of species i and j; the value of Z is 10 and demonstrates the lattice coordination number; the volume parameters (ri) and the area parameters (qi) of the corresponding compounds are presented in Table 8.26,27 As for the Wilson model, gij − gii refer to the binary interaction energy parameters; the values23 of the critical temperature (Tci), critical pressure (Pci), and compressibility factor (Zci) are also shown in Table 8.

(6)

where y1cal and y2cal represent the calculated values of vapor-phase mole fractions of components 1 and 2, respectively. Simultaneously, Gmehling and Onken25 believed that the data could maintain consistency if the mean deflection of the vapor mole fraction was no more than about 0.01. The results of the thermodynamic consistency tests of the two systems are presented in Table 9. Interaction Energy Parameters for the UNIQUAC, NRTL, and Wilson Equations, Absolute Average Deviations of the Boiling Temperatures (AADT/K) and the VaporPhase Mole Fractions (AADy1)a for NBA (1) and BDO (2) at p = (30.0, 50.0, and 70.0) kPa 30.0 kPa g12 −g22 (J·mol−1) g21 −g11 (J·mol−1) AADT (K) AADy1 g12 −g22 (J·mol−1) g21 −g11 (J·mol−1) AADT (K) AADy1 g12 −g22 (J·mol−1) g21 −g11 (J·mol−1) AADT (K) AADy1 a

50.0 kPa

70.0 kPa

NRTL Parameters −213.08 −438.65 −214.70 −377.22 0.03 0.04 0.005 0.006 UNIQUAC Parameters −119.66 −284.79 −11.11 35.02 0.03 0.05 0.006 0.006 Wilson Parameters −212.15 −458.58 −215.16 −352.31 0.04 0.04 0.005 0.006

Average absolute deviations: AADT =

1 N

AADy1 =

−224.20 −225.94 0.04 0.005 −121.80 −15.33 0.04 0.006 −220.90 −228.32 0.04 0.005

N

∑i = 1 |Tical − Tiexp| 1 N

Figure 2. Experimental and calculated T−x1−y1 diagram for the system NBA (1) + BDO (2) at 30.0 kPa: ●, measured values for T−x1; ○, measured data for T−y1; , correlated results by the NRTL model; · · ·, correlated results by the UNIQUAC model; - - -, correlated results by the Wilson model.

N

∑i = 1 |yical − yiexp |

Table 10. Interaction Energy Parameters for the UNIQUAC, NRTL, and Wilson Equations, Absolute Average Deviations of the Boiling Temperatures (AADT/K) and the VaporPhase Mole Fractions (AADy1)a for GBL (1) and BDO (2) at p = (30.0, 50.0, and 70.0) kPa 30.0 kPa g12 −g22 (J·mol−1) g21 −g11 (J·mol−1) AADT (K) AADy1 g12 −g22 (J·mol−1) g21 −g11 (J·mol−1) AADT (K) AADy1 g12 −g22 (J·mol−1) g21 −g11 (J·mol−1) AADT (K) AADy1 a

50.0 kPa

70.0 kPa

NRTL Parameters −22.28 −474.65 −242.59 −479.68 0.05 0.04 0.004 0.004 UNIQUAC Parameters −54.30 −209.45 −54.26 −149.23 0.04 0.08 0.006 0.004 Wilson Parameters −112.07 −485.95 −93.58 −405.25 0.05 0.06 0.004 0.004

Absolute average deviations: AADT =

1 N

AADy1 =

N ∑i = 1 |Tical 1 N

853.28 838.18 0.05 0.004 −67.31 −501.79 0.14 0.006 −988.80 −812.22 0.08 0.005

−

N ∑i = 1 |yical

Figure 3. Experimental and calculated T−x1−y1 diagram for the system NBA (1) + BDO (2) at 50.0 kPa: ●, measured values for T−x1; ○, measured data for T−y1; , correlated results by the NRTL model; · · ·, correlated results by the UNIQUAC model; - - -, correlated results by the Wilson model.

Tiexp| − yiexp | E

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where Uexp and Ucal i i stand for the experimental and computed variable quantities and N indicates the quantity of experimental data points. As can be seen from Tables 9 and 10, the absolute average deviations of the vapor-phase mole fraction (AADy1) and the equilibrium temperature (AADT) are presented at three different pressures. For the two binary systems of (NBA + BDO) and (GBL + BDO) under pressures of 30.0, 50.0, and 70.0 kPa, the maximum absolute deviations of the temperatures (|ΔT|max) and vapor-phase components (|Δy1|max) correlated with activity coefficient models were (0.008, 0.012, and 0.010), (0.16, 0.14, and 0.18), (0.009, 0.010, and 0.009) and (0.009, 0.011, and 0.009), respectively. Furthermore, Figures 2−7 demonstrate the comparison of the experimental data and calculated values for the two binary systems with the form of T−x1−y1 diagrams. We can also draw a conclusion that there was no azeotrope in the systems. Thus, it turned out that the measured

The least-squares approach was applied to regress the model parameters the eq 7 ⎡⎛ ⎞2 ⎤ ⎢⎜ γexp − γcal ⎟ ⎥ OF = ∑ ⎢⎜ γexp ⎟⎠ ⎥ ⎣⎝ ⎦

(7)

where γexp and γcal refer to the experimental and calculated activity coefficients, respectively. In order to determine the agreement of the experimental data with calculated values, the mean absolute deviation of vaporphase mole fractions (AAD) and the equilibrium temperatures were both calculated with the following equation AAD =

1 N

N

∑ |Uiexp − Uical| i=1

(8)

Figure 6. Experimental and calculated T−x1−y1 diagram for the system GBL (1) + BDO (2) at 50.0 kPa: ●, measured values for T−x1; ○, measured data for T−y1; , correlated results by the NRTL model; · · ·, correlated results by the UNIQUAC model; - - -, correlated results by the Wilson model.

Figure 4. Experimental and calculated T−x1−y1 diagram for the system NBA (1) + BDO (2) at 70.0 kPa: ●, measured values for T−x1; ○, measured data for T−y1; , correlated results by the NRTL model; · · ·, correlated results by the UNIQUAC model; - - -, correlated results by the Wilson model.

Figure 5. Experimental and calculated T−x1−y1 diagram for the system GBL (1) + BDO (2) at 30.0 kPa: ●, measured values for T−x1; ○, measured data for T−y1; , correlated results by the NRTL model; · · ·, correlated results by the UNIQUAC model; - - -, correlated results by the Wilson model.

Figure 7. Experimental and calculated T−x1−y1 diagram for the system GBL (1) + BDO (2) at 70.0 kPa: ●, measured values for T−x1; ○, measured data for T−y1; , correlated results by the NRTL model; · · ·, correlated results by the UNIQUAC model; - - -, correlated results by the Wilson model. F

DOI: 10.1021/acs.jced.6b00088 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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values of the studied systems can be correlated satisfactorily by the NRTL, UNIQUAC, and Wilson models.

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CONCLUSIONS Isobaric VLE data of the binary systems have been determined by a improved Rose equilibrium still, and the measured values of the binary systems (NBA + BDO) and (GBL + BDO) not only satisfied the thermodynamic consistency tests with the Herington integral and point-to-point test methods but were also successfully correlated with the NRTL, Wilson, and UNIQUAC thermodynamic equations at the three subatmospheric pressures. For the two binary systems, AADy1 and AADT were below (0.006, 0.006, 0.006) and (0.05, 0.08, 0.14) K under pressures of 30.0, 50.0, and 70.0 kPa, respectively. Therefore, the experimental binary data measured in this study will be valuable and useful for the separation process of BDO including GBL and NBA in future research.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Fax: 022-27403389. Telephone: 022-27890907. Notes

The authors declare no competing financial interest.

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REFERENCES

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DOI: 10.1021/acs.jced.6b00088 J. Chem. Eng. Data XXXX, XXX, XXX−XXX