Vapor–Liquid Equilibrium for Binary Systems of Allyl Alcohol + Water

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Vapor−Liquid Equilibrium for Binary Systems of Allyl Alcohol + Water and Allyl Alcohol + Benzene at 101.3 kPa Jing Li,†,‡ Chao Hua,*,‡ Shuai Xiong,‡,§ Fang Bai,‡ Ping Lu,‡ and Jiayi Ye‡ †

Institute of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences, Beijing 101408, China Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China § State Key Laboratory of Heavy Oil Processing, China University of Petroleum (Beijing), Beijing 102249, China ‡

ABSTRACT: Vapor−liquid equilibrium (VLE) data for allyl alcohol + water and allyl alcohol + benzene systems have been determined at 101.3 kPa using a circulation VLE still. The experimental data were checked both with the Herington consistency test and van Ness consistency test methods, which indicates that the experimental data satisfy the examination of the thermodynamic consistency. Moreover, all equilibrium data were correlated with Wilson, nonrandom two-liquid (NRTL), and universal quasichemical (UNIQUAC) activity coefficient models to obtain the binary interaction parameters of these models using Aspen Plus commercial software. The results show that the two systems forms a minimum temperature binary azeotrope.

Wisniak’s modification8 of the Herington test9 and van Ness test.10 The VLE data were correlated with Wilson,11 nonrandom two-liquid (NRTL),12 and universal quasichemical (UNIQUAC)13 activity coefficient models to obtain the binary interaction parameters of these models using Aspen Plus commercial software.

1. INTRODUCTION Allyl alcohol has been widely used as a valuable synthetic intermediate and fine chemical in the total synthesis of many natural products and biologically active compounds.1 It can be used to manufacture resin pharmaceutical products and herbicides.2 Due to its extensive use in the chemical industry, it is essential and economic to recover it from the mixture for reuse. However, allyl alcohol + water is an azeotropic system, which leads to the difficulty in purifying allyl alcohol from its aqueous solution. Azetropic distillation is an effective way to solve this problem, especially when the water content is low.3 Benzene is a common entrainer for separating azeotropes in industrial process, which presents low energy consumption, good thermo stability, and low corrosiveness. So it is selected as an entrainer to separate the mixture. Unfortunately, very few vapor−liquid equilibrium data of these systems of allyl alcohol + water and allyl alcohol + benzene have been reported in the literature.4−7 For one of them, the allyl alcohol + benzene binary system at normal pressure is still not available in the literature. Obviously, these data are not sufficient for the actual demand of chemical engineering calculation and simulation. This paper was carried out to provide fundamental data for the separation of allyl alcohol + water mixture by azeotropic distillation using benzene as the entrainer. The isobaric vapor− liquid equilibrium (VLE) data for binary systems of allyl alcohol + water and allyl alcohol + benzene were measured at 101.3 kPa by a modified Othmer VLE still, in which the VLE determination of allyl alcohol + benzene at normal pressure was first reported in this work. The thermodynamic consistency of the experimental data were checked out by means of the © 2017 American Chemical Society

2. EXPERIMENTAL SECTION 2.1. Chemicals. The chemicals used were allyl alcohol, benzene, and water. All of the chemicals were analytical reagents. The source, molecular formula, CAS RN, and mass fraction of the reagents are list in Table 1, respectively. The mass fraction was measured by a gas chromatograph (GC) equipped with a thermal conductivity detector. No further purification has been made for the chemicals before use. Table 1. Material Description at 101.3 kPa component source molecular formula CASRN mass fraction purity analysis method

allyl alcohol

benzene

water

Mingxing, China C3H6O 107-18-6 0.997

Sinopharm, China C6H6 71-43-2 0.995

Sinopharm, China H2O 7732-18-5 0.999

GC

GC

GC

Received: October 20, 2016 Accepted: July 20, 2017 Published: August 22, 2017 3004

DOI: 10.1021/acs.jced.6b00893 J. Chem. Eng. Data 2017, 62, 3004−3008

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2.2. Analysis. All of the samples of the equilibrium phases were analyzed by a gas chromatography (GC) equipped with a thermal conductivity detector (TCD). A column packed with Porapak Q (80−100 mesh, 3 mm × 2 m) was used. High-purity hydrogen (hydrogen generator) was taken as carrier gas at a flow rate of 50 mL·min−1. The injector and detector temperatures were maintained at 473.15 K. The column of the GC was kept at temperatures between 393.15 and 473.15 K using a temperature program (initial temperature 393.15 K for 1 min, temperature ramp 30 K·min−1 to 473.15 K, and temperature maintained at 473.15 K for another 10 min). Calibration analyses using gravimetrically prepared standard solutions were carried out to convert the peak area ratios to mole fraction of the samples. 2.3. Apparatus and Procedure. The VLE measurement were made with an all-glass dynamic circulation vapor−liquid equilibrium still (a modified Othmer still), and the detailed description and validity check of experimental apparatus has been reported in our previous publication.14 First, a series of solution samples (about 30 mL) with different concentrations were prepared in advance and added into the equilibrium kettle. Then, the cooling water was turned on, and the heating rate was regulated to keep the vapor condensation speed at 60−100 drops per minute. After running for 1 h to maintain stabilization of the reflux, the temperature was read every 5 min; while the temperature is stable, the equilibrium state was thought to be reached. Then the equilibrium temperature was recorded, and the vapor and liquid samples were collected. The temperature was measured with a calibrated thermometer graduated in 0.01 K, while the uncertainty of the thermometer is 0.05 K. The composition determination was repeated for three times to reduce the error.

Table 2. Experimental VLE Data: Equilibrium Temperature T, Liquid Phase Mole Fraction x1, Vapor Phase Mole Fraction y1, and Activity Coefficient γi for the Binary System Allyl Alcohol (1) + Water (2) at 101.3 kPaa

L

y1

γ1

1 0.9048 0.8059 0.6652 0.6098 0.4829 0.4720 0.4436 0.4113 0.3612 0.3109 0.2557 0.2348 0.1191 0.0564 0

1 1.0073 1.0021 1.0206 1.0893 1.2547 1.4055 1.5173 2.2666 2.9616 4.4735 5.3208 6.6140 8.1101 7.5913

γ2 2.6213 2.9132 2.3496 2.0647 1.6367 1.4691 1.3881 1.1550 1.0877 1.0376 1.0395 0.9871 1.0036 1.0037 1

Standard uncertainties u are u(P) = 0.1 kPa. u(T) = 0.05 K, u(x1) = u(y1) = 0.005.

Table 3. Experimental VLE Data: Equilibrium Temperature T, Liquid Phase Mole Fraction x1, Vapor Phase Mole Fraction y1, and Activity Coefficient γi for the Binary System Allyl Alcohol (1) + Benzene (2) at 101.3 kPaa

s

(1)

where P is the total pressure of the equilibrium system, yi and xi are the mole fraction of vapor and liquid phases, respectively, φVi is the fugacity coefficient of component i in the gas phase, PSi is the saturated vapor pressure of component i at temperature T, φsi is the fugacity coefficient of the pure component i in the saturated state, γi is activity coefficient of i in the liquid phase with respect to the reference fugacity, VLi is the mole volume of pure liquid, and R is the gas constant. At low pressure, the nonideality of vapor phase can be L S neglected, that is, φVi = 1, φsi = 1, and the term e[Vi (P−Pi )]/RT is approximately equal to 1; thus, eq 1 can be simplified to eq 2. Pyi = PiSγixi

x1 1 0.9566 0.9149 0.8029 0.7250 0.5201 0.4540 0.3936 0.2406 0.1560 0.0852 0.0564 0.0392 0.0147 0.0070 0

a

3. RESULTS AND DISCUSSION 3.1. Experimental Results. The VLE experimental data and the corresponding calculated activity coefficients for allyl alcohol (1) + water (2) and allyl alcohol (1) + benzene (2) at 101.3 kPa are listed in Tables 2−3, respectively. The general equilibrium relationship between the vapor phase and the liquid phase of the binary systems can be described as follows.15,16 Pyi φi V = Pisφisγixie(Vi (P − Pi )/ RT )

T (K) 369.75 368.24 366.44 364.31 362.97 361.85 361.84 361.95 362.35 363.30 364.43 365.60 367.25 369.95 371.64 373.15

T (K)

x1

y1

γ1

369.75 367.40 363.95 358.74 355.64 353.45 352.55 352.05 351.33 350.24 350.03 349.64 349.74 350.85 352.05 353.25

1 0.9764 0.9388 0.8484 0.7771 0.6947 0.6421 0.5955 0.5436 0.4256 0.3710 0.2857 0.2037 0.0641 0.0236 0

1 0.8915 0.7523 0.5690 0.4712 0.3979 0.3744 0.3510 0.3200 0.2856 0.2636 0.2445 0.2114 0.1233 0.0615 0

1 1.0027 1.0002 1.0217 1.0436 1.0763 1.1364 1.1724 1.2059 1.4378 1.5356 1.8798 2.2701 4.0189 5.1832

γ2 3.0339 2.9458 2.4094 2.2066 1.9613 1.7873 1.6662 1.58234 1.36676 1.29509 1.18449 1.1056 1.0099 0.9982 1

a

Standard uncertainties u are u(P) = 0.1 kPa. u(T) = 0.05 K, u(x1) = u(y1) = 0.005.

ln(PiS/kPa) = C1i + + C6iT C7i

C 2i + C4iT + C5i ln T T + C 3i

for

C 8i ≤ T ≤ C 9i

(3)

The value of parameters for all components were obtained from the databank of Aspen Physical Property System, as presented in Table 4. 3.2. Consistency Check of the Experimental Data. The thermodynamic consistency of the experimental VLE data for binary systems was checked out by means of the Wisniak’s modification8 of the Herington test9 and van Ness test.10 According to the Wisniak’s modification of the Herington test,

(2)

The vapor pressure of pure component i can be calculated from the extended Antoine equation, which is shown as follows: 3005

DOI: 10.1021/acs.jced.6b00893 J. Chem. Eng. Data 2017, 62, 3004−3008

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Table 4. Parameters of the Extended Antoine Equationa

a

compound

C1i

C2i

C3i

C4i

C5i

C6i (× 106)

C7i

C8i/K

C9i/K

allyl alcohol benzene water

84.739 83.107 73.649

−8057.6 −6486.2 −7258.2

0 0 0

0 0 0

−8.7051 −9.2194 −7.3037

1.66 × 10−11 6.9844 4.1653

6 2 2

144.15 278.68 273.16

545.1 562.05 647.1

Taken from Aspen Plus physical properties databanks.

of the maximum likelihood principle,17 was adopted for the regression calculation.

the isobaric VLE data pass the consistency test if the check result |D − J| is less than 10. D and J are defined as follows:

⎡⎛ exp cal ⎞2 ⎛ P exp − P cal ⎞2 ⎢⎜ Ti − Ti ⎟ i i ⎟⎟ OF = ∑ ⎢⎜ ⎟ + ⎜⎜ σT σP ⎠ ⎝ ⎠ i ⎣⎝

1

|∫ ln(γ1/γ2)dx1|

N

0 1

D = 100 ×

∫0 |ln(γ1/γ2)|dx1 J = 150 ×

(4)

Tmax − Tmin Tmin

2 ⎛ x exp − x cal ⎞2 ⎛ y exp − y cal ⎞ ⎤ i i i i ⎟⎥ ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎥ σ σ ⎝ ⎠⎝ x y ⎠⎦

(5)

where Tmax and Tmin (K) are the maximum and minimum boiling point of the system, respectively. As to the van Ness test, the criteria is that Δy should be less than 1. Δy was the mean absolute deviation between the experimental data and the calculated results of mole fractions in the vapor phase, which is presented as follows: Δy =

1 N

where N is the number of experimental points, x, y, T, and P are mole fractions in liquid phase and vapor phase, equilibrium temperature, and pressure, respectively, subscripts of exp and cal are abbreviations of the experiment and calculations, respectively, and σ presents the standard deviation of the indicated data. This objective function takes the uncertainties of all measured variables into account simultaneous, so the determined optimal values of the model parameters are much more statistically sound. The correlated binary interaction parameters of Wilson, NRTL, and UNIQUAC models are given in Table 6, together with root-mean-square deviations (RMSD) and the average absolute deviation (AAD) for the temperature and the mole fraction of the vapor phase. Comparing the RMSD with another reference,18 of which VLE data of allyl acohol and benzene are measured under different pressure, the three model show better fitness, which can be seen from Table 7. For the three binary systems of (allyl alcohol + water) and (allyl alcohol + benzene) the calculated curves by NRTL and the determined data are compared graphically in Figures 1−4, respectively. For the binary systems of allyl alcohol + water and allyl alcohol + benzene, it is obviously to be seen that, in Table 6, the AAD of the vapor compositions, the equilibrium temperatures between the calculated results and the experimental data are less than 0.008 and 0.17, respectively. These results suggest that all three models give good prediction with reasonable deviations. As can been from Figure 1, 2, 3, and 4, the

N

∑ 100|yiexp − yical |

(6)

i=1

where N is the number of experimental points, exp stands for measured data, and cal stands for the calculated results by the NRTL model. Pertinent consistency details are presented in Table 5. These result confirm that the experimental VLE data are thermodynamically consistent, which means the NRTL is not suitable for this system. Table 5. Results of Thermodynamic Consistency Test system

D

J

|D − J|

Δy

allyl alcohol + water allyl alcohol + benzene

3.12 2.66

3.28 8.63

0.16 5.97

0.83 0.35

(7)

3.3. Data Regression. For rigorous simulation of azeotropic distillation, it is crucial to obtain the model parameters of related binary systems. Therefore, the experimental VLE data of three binary systems were correlated by the Wilson, NRTL, and UNIQUAC models with Aspen software. The following objective function (OF), on the basis

Table 6. Binary Interaction Parameters, the Root Mean-Square Deviation (RMSD) and the Average Absolute Deviations (AAD) for the Equilibrium Temperature (T) and Mole Fractions of the Vapor Phase (y1) of the Wilson, NRTL, and UNIQUAC Activity Coefficient Models binary interaction parameters model

aij

aji

Wilson NRTL UNIQUAC

2.56 −1.62 31.44

5.66 6.73 −27.92

Wilson NRTL UNIQUAC

−7.36 1.04 0.78

0.07 9.23 −5.15

bij/K

RMSD bji/K

α

Allyl Alcohol (1) + Water (2) −1711.80 −2158.2 571.65 −1667.96 0.3 −11634.1 10161.7 Allyl Alcohol (1) + Benzene (2) 2050.13 −147.25 −366.69 −2623.62 0.3 −181.51 1454.93 3006

AAD

T/K

y1

δ(y1)

δ(T)

0.17 0.18 0.19

0.008 0.010 0.009

0.007 0.008 0.007

0.14 0.13 0.17

0.12 0.12 0.12

0.004 0.004 0.004

0.003 0.003 0.003

0.10 0.10 0.10

DOI: 10.1021/acs.jced.6b00893 J. Chem. Eng. Data 2017, 62, 3004−3008

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Table 7. Root-Mean-Square Deviation (RMSD) Comparison of This Study and Reference RMSD for Allyl Alcohol (1) + Benzene (2) P = 101.3 KPa

T = 313.15 K18

T = 323.15 K18

T = 333.15 K18

model

T/K

y1

P/Pa

y1

P/Pa

y1

P/Pa

y1

Wilson NRTL UNIQUAC

0.12 0.12 0.12

0.004 0.004 0.004

949.9 396.6 271.4

0.0360 0.0417 0.0449

299.2 664.5 452.9

0.0636 0.0629 0.0659

476.8 664.5 665.0

0.0615 0.0629 0.0633

Figure 1. Experimental data and calculated data for the system of allyl alcohol (1) + water (2) at 101.3 kPa. ▲, T−x1 for experimental data; □, T−y1 for experimental data; ---, T−x1 for calculated data with NRTL; , T−y1 for calculated data with NRTL.

Figure 3. Experimental and calculated y1−x1 diagram for the binary system allyl alcohol (1) + water (2) at 101.3 kPa. ▲, experimental data; □, literature data;4 ○, literature data;7 , NRTL.

Figure 4. Experimental and calculated y1−x1 diagram for the binary system allyl alcohol (1) + benzene (2) at 101.3 kPa. ▲, experimental data; , NRTL.

Figure 2. Experimental data and calculated data for the system of allyl alcohol (1) + benzene (2) at 101.3 kPa. ▲, T−x1 for experimental data; □, T−y1 for experimental data; ---, T−x1 for calculated data with NRTL; , T−y1 for calculated data with NRTL.

4. CONCLUSIONS Sets of experimental VLE data were obtained for the binary systems of allyl alcohol + water and allyl alcohol + benzene at 101.3 kPa. All of the three systems present an azeotrope. In the system of allyl alcohol + water, the azeotropic temperature and composition were T = 361.84 and x1 = 0.456. In allyl alcohol + benzene, the azeotropic temperature and composition were T = 349.68 and x1 = 0.221. The data have been shown to be thermodynamically consistent. Wilson, NRTL, and UNIQUAC models fit accurately the experimental data of allyl alcohol +

determined VLE data are close to the reported literature or calculated data. Meanwhile, it revealed the azeotropic behavior. The azeotropic temperature and composition of ally alcohol + water and allyl alcohol + benzene at 101.3 kPa are 361.84 K, 0.456 mol % allyl alcohol, 349.68 K, and 0.221 mol % allyl alcohol. 3007

DOI: 10.1021/acs.jced.6b00893 J. Chem. Eng. Data 2017, 62, 3004−3008

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(17) Anderson, T. F.; Abrams, D. S.; Grens, E. A. Evaluation of parameters for nonlinear thermodynamic models. AIChE J. 1978, 24, 20−29. (18) Lubomska, M.; Banas, A.; Malanowski, S. K. Vapor-Liquid Equilibrium in Binary Systems Formed by Allyl Alcohol with Benzene and with Cyclohexane. J. Chem. Eng. Data 2002, 47, 1466−1471.

water and allyl alcohol + benzene, which is valuable for the chemical engineering calculation and simulation.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Shuai Xiong: 0000-0003-2875-9687 Funding

The author wish to extend their deep gratitude for the support by the National Natural Science Foundation of China (grant no. 21306198). Notes

The authors declare no competing financial interest.

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REFERENCES

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DOI: 10.1021/acs.jced.6b00893 J. Chem. Eng. Data 2017, 62, 3004−3008