Separation of azeotrope (allyl alcohol + water): Isobaric vapour-liquid phase equilibrium measurements and extractive distillation

Separation of azeotrope (allyl alcohol + water): Isobaric vapour-liquid phase equilibrium measurements and extractive distillation

J. Chem. Thermodynamics 118 (2018) 139–146 Contents lists available at ScienceDirect J. Chem. Thermodynamics journal homepage: www.elsevier.com/loca...

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J. Chem. Thermodynamics 118 (2018) 139–146

Contents lists available at ScienceDirect

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

Separation of azeotrope (allyl alcohol + water): Isobaric vapour-liquid phase equilibrium measurements and extractive distillation Jingyu Wu a,1, Dongmei Xu a,1, Puyun Shi a, Jun Gao a,⇑, Lianzheng Zhang a, Yixin Ma a, Yinglong Wang b a b

College of Chemical and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266590, China College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, China

a r t i c l e

i n f o

Article history: Received 20 September 2017 Received in revised form 18 November 2017 Accepted 18 November 2017 Available online 21 November 2017 Keywords: Allyl alcohol Azeotrope Vapour-liquid equilibrium Extractive distillation

a b s t r a c t To separate the azeotrope of (allyl alcohol + water) by extractive distillation, N-methyl-2-pyrrolidone, N-methyl formamide and ethylene glycol were selected as extractive agents, and the isobaric VLE data for the binary systems of (allyl alcohol + N-methyl-2-pyrrolidone), (allyl alcohol + N-methyl formamide) and (allyl alcohol + ethylene glycol) were determined at 101.3 kPa by a modified Rose type recirculating still. The thermodynamic consistency of the experimental data was checked by the Herington, van Ness, infinite dilution, and pure component consistency method. Meanwhile, the experimental data were correlated by the NRTL, UNIQUAC and Wilson activity coefficient models, and the binary interaction parameters of the three models were regressed. All the correlated results by the NRTL, UNIQUAC, and Wilson models agreed well with the experimental data. Furthermore, the extractive distillation processes with the extractive agents were presented to separate the azeotrope of (allyl alcohol + water). Ó 2017 Elsevier Ltd.

1. Introduction Allyl alcohol is widely used in the production of medicine, spices, agricultural chemicals and other engineering applications because of its excellent physical and chemical properties [1–4]. For example, allyl alcohol can be used as a reaction solvent during the synthesis of trimethylolpropane diallyl ether. After the reaction, the mixture of allyl alcohol and water is generated [5,6]. To recover allyl alcohol, it is necessary to separate allyl alcohol from its aqueous solution, which is also beneficial for environmental protection and resource reutilization. However, allyl alcohol and water can form an azeotrope at atmospheric pressure. For the separation of such an azeotrope, special distillations are needed, such as extractive distillation, pressure-swing distillation, azeotropic distillation, reactive distillation and so on [7]. In this work, extractive distillation was adopted to separate the azeotrope of allyl alcohol and water. For design of the extractive distillation process, a reliable knowledge of vapour–liquid equilibrium (VLE) data for the system of allyl alcohol and water is required. Particularly, the selection of the entraniners is important, which can enhance the separation factor for the azeotropic mixture allyl (alcohol + water) [8]. Therefore, based on the criteria for the selection of entrainers for extractive distillation by Gmehling and ⇑ Corresponding author. 1

E-mail address: [email protected] (J. Gao). Jingyu Wu and Dongmei Xu contributed equally.

https://doi.org/10.1016/j.jct.2017.11.009 0021-9614/Ó 2017 Elsevier Ltd.

Möllmann [9], N-methyl-2-pyrrolidone, N-methyl formamide and ethylene glycol were selected as the entrainer candidates for the separation of the azeotropic mixture allyl alcohol + water. In recent years, some investigators have reported the VLE data for the system allyl alcohol + water. Grabner [10] and Zhang [2] determined the isobaric VLE data for the system allyl alcohol + water at 101.3 kPa. Aucejo [11], Harper [12] and Lesteva [13] determined the isothermal VLE data of allyl alcohol + water at different pressures and salt effect to the VLE of allyl alcohol + water system was determined by Zhang [14]. However, the isobaric VLE data for the systems of allyl alcohol with N-methyl-2-pyrrolidone, Nmethyl formamide and ethylene glycol have not been found in the NIST [15] and Dortmund Data Bank (DDB) [16]. In this work, the isobaric VLE data for the systems allyl alcohol + N-methyl-2-pyrrolidone, allyl alcohol + N-methyl formamide, and allyl alcohol + ethylene glycol at 101.3 kPa were measured by a recirculating type equilibrium still. The thermodynamic consistency of the VLE data was checked by the method of Herington test [17], van Ness test [18], infinite dilution test [19], and pure component consistency test [20]. Furthermore, the NRTL [21], UNIQUAC [22] and Wilson [23] activity coefficient models were used to correlate the VLE data, and the interaction parameters of the three models were obtained. Meanwhile the values of excess Gibbs energy, GEm , were calculated by fitting the VLE data. Also, the extractive distillation process was presented to separate allyl alcohol from its aqueous solution in this work.

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J. Wu et al. / J. Chem. Thermodynamics 118 (2018) 139–146

2. Experimental

3. Results and discussion

2.1. Chemicals

3.1. Experimental results

All chemicals were supplied by Shandong Xiya Chemical Co, Ltd. The CAS and mass fraction confirmed by GC (SP6890, Shandong Lunan Rui Hong Chemical Instrument Co., Ltd.) are listed in Table 1. All the chemicals were used without further purification. All chemicals were analytical pure reagents. The water content of the reagents was checked and confirmed by GC. The purecomponent boiling temperatures were compared with literature data and the detailed information is presented in Table S1 in the Supplementary Material. The pressure was maintained with a manometer (Nanjing Hengyuan Automatic Gauge Co., Ltd.) and the pressure fluctuation was controlled within 0.1 kPa by the two-step automatic control scheme.

In this work, the VLE data for three binary mixtures (allyl alcohol + N-methyl-2-pyrrolidone), (allyl alcohol + N-methyl formamide), and (allyl alcohol + ethylene glycol), were measured at pressure of 101.3 kPa. The experimental VLE data with the values of the activity coefficients and excess Gibbs energy GE for the three systems are summarized in Tables 2–4. Also, the T-x-y phase diagrams for the systems are presented in Figs. 1–3. 3.2. VLE calculation The VLE relationship is usually expressed as follows [31]:

" # L s ^ i y p ¼ xi c Us ps exp V i ðp  pi Þ / i i i i RT

2.2. Apparatus and procedure

ð1Þ

Since the pressure for the VLE measurements was 101.3 kPa, the The VLE measurements for the systems (allyl alcohol + Nmethyl-2-pyrrolidone), (allyl alcohol + N-methyl formamide), and (allyl alcohol + ethylene glycol) were performed at pressure of 101.3 kPa by a modified Rose type recirculating equilibrium still, which has been presented in detail in previous literature [25,26]. During the measurement, the liquid and condensed vapour phases were recirculated continuously to ensure sufficient contact. The equilibrium temperature was determined when the equilibrium temperature was kept constant for more than 50 min. Then the samples of the vapour and liquid phases were withdrawn for analysis. The details of the VLE measurement can be found in the literatures [27–29].

^ i and /s associated with non-ideality are all close Poynting factor, / i to 1. Considering the non-idealities of the liquid phase, ci for the three systems can be calculated by Eq. (2), and the calculated values of ci are presented in Tables 2–4.

ci ¼

Pyi P si xi

ð2Þ

where xi presents mole fraction of component i in vapour phase and yi presents mole fraction of component i in liquid phase; P is the system pressure, 101.3 kPa, and Psi is the saturation pressure of pure component i, which was obtained by the extended Antoine expression. The extended Antoine expression is shown as follows:

lnðP si =kPaÞ ¼ C 1i þ

2.3. Analysis

C 2i þ C 4i T þ C 5i lnT þ C 6i T C7i C 8i 6 T 6 C 9i T þ C 3i ð3Þ

The samples of vapour and liquid phases were analysed using a gas chromatograph (SP6890, Shandong Lunan Rui Hong Chemical Instrument Co., Ltd.) equipped with a thermal conductivity detector (TCD), and a packing column (ULBON HR-20M, 50 m  0.25 mm I.D., 0.50 m film thickness, Shinwa Chemical Industries Ltd., Kyoto, Japan) was used. Hydrogen with the purity of 99.999% was used as carrier gas at a flow rate of 50 mLmin1. The detector temperature was maintained at 483 K. The sample compositions were determined by the area correction normalization method [30]. GC was calibrated by the standard samples which were prepared gravimetrically by an electronic balance (Ohaus Corporation, AR1140) with the accuracy of ±0.0001 g. The phase equilibrium temperature was measured by a precise mercury thermometer (Tianjin lass Instrument Factory) with the accuracy of ±0.1 K. The pressure of the system was measured by a manometer (Nanjing Hengyuan Automatic Gauge Co., Ltd) with the accuracy of ±0.1 kPa.

The constant values for all components were obtained directly from the Aspen databank [37] and presented in Table 5. To assess the non-ideality for the systems, the excess Gibbs energy GE was calculated by the following equation:

GE ¼ RTðx1 lnc1 þ x2 lnc2 Þ

ð4Þ

where the activity coefficients ci was calculated from the NRTL model. The calculated results of the excess Gibbs energy (GE ) for the three binary systems are presented in Fig. 4. 3.3. Thermodynamic consistency test The consistency of the experimental results for the three binary systems were checked by Herington [17,32], van Ness [18,33],

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

Allyl alcohol N-methyl-2-pyrrolidone N-methyl formamide Ethylene glycol a b

CAS

107-18-6 872-50-4 123-39-7 107-21-1

Suppliers

Shandong Shandong Shandong Shandong

Xiya Xiya Xiya Xiya

Chemical Chemical Chemical Chemical

Co, Co, Co, Co,

Ltd Ltd Ltd Ltd

Water content (mass fraction)

Mass fraction

Tb/Kb This work

Literature

0.008 0.005 0.009 0.004

0.99 0.990 0.990 0.990

369.95 475.44 472.25 470.32

369.75 475.45 473.15 470.39

[2] [22] [23] [24]

Gas chromatograph. The experimental pressure for the measurement of boiling temperature is 101.3 kPa, the standard uncertainties u of P and T are u(P) = 0.1 kPa, u(T) = 0.1 K.

Analysis method

GCa GCa GCa GCa

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J. Wu et al. / J. Chem. Thermodynamics 118 (2018) 139–146 Table 2 Experimental VLE values for the binary system of allyl alcohol (1) + N-methyl-2-pyrrolidone (2), activity coefficient (c) and Gibbs energy (GE) at 101.3 kPa.a

a

T/K

x1

y1

c1

c2

GE/(Jmol1)

371.00 380.73 389.64 397.17 403.11 410.71 416.48 424.19 436.30 442.43 448.66 454.49 461.87 467.37 470.91

0.9490 0.6399 0.4399 0.3151 0.2617 0.1932 0.1574 0.1217 0.0790 0.0614 0.0454 0.0320 0.0189 0.0114 0.0066

0.9983 0.9828 0.9590 0.9297 0.9044 0.8684 0.8369 0.7872 0.6840 0.6185 0.5408 0.4557 0.3307 0.2240 0.1475

1.0143 1.0572 1.1229 1.2045 1.1833 1.2406 1.2537 1.2462 1.2365 1.2453 1.2760 1.3399 1.4055 1.4137 1.4856

1.1171 1.0459 1.1149 1.1677 1.1816 1.1343 1.1042 1.0711 1.0388 1.0257 1.0152 1.0091 1.0042 1.0018 1.0013

58.95 163.83 362.52 544.27 560.49 489.48 412.47 307.09 187.97 137.29 94.88 68.63 40.46 22.15 15.16

Standard uncertainties u of T, P, x and y are u(T) = 0.1 K, u(P) = 0.1 kPa, u(x) = 0.0029, u(y) = 0.0029.

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

a

T/K

x1

y1

c1

c2

GE/(Jmol1)

372.35 375.67 378.63 382.18 384.67 391.95 395.10 400.67 404.24 409.46 418.50 426.54 434.45 440.40 447.65 455.34 462.64 470.43

0.9052 0.7840 0.6843 0.5950 0.5351 0.4153 0.3638 0.3002 0.2655 0.2199 0.1602 0.1138 0.0839 0.0654 0.0451 0.0278 0.0136 0.0028

0.9960 0.9902 0.9846 0.9770 0.9713 0.9527 0.9435 0.9250 0.9112 0.8870 0.8340 0.7723 0.6946 0.6250 0.5228 0.3921 0.2440 0.0611

1.0111 1.0331 1.0633 1.0769 1.0968 1.0988 1.1273 1.1332 1.1373 1.1527 1.1629 1.2310 1.2359 1.2373 1.2707 1.3044 1.4189 1.4894

1.4378 1.3215 1.2454 1.2385 1.2079 1.1661 1.1256 1.0885 1.0701 1.0527 1.0360 1.0208 1.0207 1.0174 1.0154 1.0140 1.0116 1.0062

137.49 267.84 350.34 415.40 438.98 420.29 390.36 322.67 281.97 242.70 187.37 148.48 132.03 109.95 94.52 79.04 62.16 4.31

Standard uncertainties u of T, P, x and y are u(T) = 0.1 K, u(P) = 0.1 kPa, u(x) = 0.0029, u(y) = 0.0029.

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

a

T/K

x1

y1

c1

c2

GE/(Jmol1)

372.93 376.27 379.17 383.96 387.16 392.16 396.45 401.16 406.60 411.13 417.52 426.76 433.50 437.49 442.15 448.76 455.80 459.55 467.25 469.40

0.8721 0.7718 0.6584 0.5308 0.4454 0.3599 0.3110 0.2660 0.2216 0.1901 0.1530 0.1103 0.0852 0.0722 0.0588 0.0418 0.0260 0.0184 0.0046 0.0012

0.9950 0.9905 0.9863 0.9786 0.9733 0.9638 0.9532 0.9387 0.9186 0.8978 0.8622 0.7927 0.7261 0.6795 0.6180 0.5124 0.3755 0.2906 0.0872 0.0235

1.0271 1.0282 1.0869 1.1402 1.2182 1.2742 1.2787 1.2789 1.2840 1.2878 1.2920 1.2964 1.3008 1.3057 1.3059 1.3115 1.3216 1.3369 1.3730 1.3926

1.9117 1.7134 1.4195 1.2705 1.1434 1.0620 1.0450 1.0397 1.0253 1.0221 1.0140 1.0116 1.0103 1.0089 1.0053 1.0050 1.0041 1.0038 1.0032 1.0023

329.25 451.53 550.22 580.88 522.25 409.88 351.93 313.51 253.01 224.88 177.10 138.12 114.45 99.82 76.10 60.15 42.73 34.72 17.90 10.49

Standard uncertainties u of T, P, x and y are u(T) = 0.1 K, u(P) = 0.1 kPa, u(x) = 0.0029, u(y) = 0.0029.

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

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

  1 XN  100yexp  ycal i i i¼1 N   Pexp  Pcal  1 XN  i i  100 P¼  i¼1   Pexp N i



ð7Þ

ð8Þ

where N is the experimental point number, Pexp and P cal are the i i and ycal are mole fractions of vapour phase. The superpressure, yexp i i scripts ‘‘exp” and ‘‘cal” represent the experimental data and calcucal were calculated by the NRTL model with lated values. The Pcal i , yi the binary parameters as given in Table 11. The van Ness test requires that Dy and DP should be less than 1. The results of the consistency test are reported in Table 7. As shown in Table 7, all the values of Dy and DP are less than 1, that confirms the measured VLE values are reliable. The infinite dilution test is defined as follows:

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

  GE =ðx x RTÞ  lnðc =c Þ  1 2 1 2  I1 ¼ 100    lnðc1 =c2 Þ

ð9Þ

  GE =ðx x RTÞ  lnðc =c Þ  1 2 1 2  I2 ¼ 100    lnðc1 =c2 Þ

ð10Þ

x1 ¼0

x2 ¼0

infinite dilution [19], and pure component consistency tests, following the algorithm proposed by Kang et al. [20,36]. The Herington test method is expressed as follows:

  ðA  BÞ  D ¼ 100 ðA þ BÞ

ð5Þ

  T max  T min   J ¼ 150  T

ð6Þ

min

where A is the area above the zero line on the diagram of ln(c1/c2) vs x, B is the area under the zero line on this diagram; T max and T min are the highest and the lowest boiling temperature, respectively. For the Herington test, the value of jD  Jj should be less than 10. The values of D-J for the three binary systems are presented in Table 6, which are all less than 10 indicating that the experimental VLE data for the three systems are thermodynamic consistency. The van Ness test is defined as follows:

GE =RT and lnðc1 =c2 Þ are calculated from the extended RedlichKister’s equation Eqs. (11) and (12) [34,35]

GE =RT ¼ x1 x2 ½C 0 þ C 1 ðx1  x2 Þ þ C 2 ðx1  x2 Þ2 

ð11Þ

lnðc1 =c2 Þ ¼ D0 þ D1 ðx2  x1 Þ þ D2 ð6x1 x2  1Þ þ D3 ðx2  x1 Þð1  8x1 x2 Þ ð12Þ In the infinite dilution test, I1 and I2 must be less than 30. The results of I1 and I2 are listed in Table 8 The pure component consistency test is presented as follows:

  Pbubble ðx1 ! 1Þ  p01   P01 ¼   0 p1

ð13Þ

  Pbubble ðx1 ! 0Þ  p02   P02 ¼   p0

ð14Þ

2

143

J. Wu et al. / J. Chem. Thermodynamics 118 (2018) 139–146 Table 5 Parameters (Ci) of the extended Antoine equation.a

a

Component

C1i

C2i

C3i

C4i

C5i

C6i (1018)

C7i

C8i/K

C9i/K

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

77.83 61.57 63.22 77.18

8057.60 8467.90 8851.00 10411.00

0 0 0 0

0 0 0 0

8.71 6.36 6.48 8.20

16.60 3.22 2.39 1.65

6.00 6.00 6.00 6.00

144.15 249.15 269.35 260.15

545.10 721.60 721.00 720.00

Taken from Aspen property databank [37].

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

DP01 < 1

DP02 < 1

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

0.00 0.00 0.00

0.00 0.00 0.00

Q VLE ¼

F Pure ðF Herington þ F v anNess þ F Inf :Dil Þ 3  0:25

ð15Þ

The quality factors for the Herington, van Ness, infinite dilution, and pure-component consistency tests and the values of QVLE are listed in Table 10. The quality factors for the pure component consistency test (FPure) are equal to 1, since the vapour pressures agree within 0.01P0 for both components in the three systems. The overall quality factors QVLE for the three systems are equal to 1, which indicate that the VLE data are thermodynamically consistent. Fig. 4. Experimental excess Gibbs energy for the three binary systems at 101.3 kPa and the calculated values by the NRTL model against mole fraction: j, allyl alcohol (1) + N-methyl-2-pyrrolidone (2); d, allyl alcohol (1) + N-methyl formamide (2); N, allyl alcohol (1) + ethylene glycol (2); the solid line is the trend line.

Table 6 Thermodynamic consistency check by the Herington test (D and J defined variables in the test). System

D

J

D-J < 10

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

48.4358 43.4480 35.5472

42.7720 41.5799 41.0326

5.6638 1.8681 5.4854

Table 7 Thermodynamic consistency check by the van Ness test (DP and Dy defined variables in the test). System

DP < 1

Dy < 1

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

0.1541 0.1871 0.1322

0.8291 0.4472 0.3016

Table 8 Thermodynamic consistency check by the infinite dilution test (I1 and I2 defined variables in the test). System

I1 < 30

I2 < 30

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

12.77 18.15 21.12

21.40 9.18 11.84

where p01 and p02 are the pure component vapour pressures, pbubble is the bubble point pressure. In this test,

DP01

and

DP02

should be less

than 1. The results of DP01 and DP02 are listed in Table 9, which indicate that all the experimental data pass this criterion. The overall quality factor, QVLE, was used to check the VLE data for the three systems. Combining the above four consistency tests, QVLE can be established as follows [20,38]:

3.4. VLE data correlation The VLE data for the systems (allyl alcohol + N-methyl-2pyrrolidone), (allyl alcohol + N-methyl formamide), and (allyl alcohol + ethylene glycol) were correlated by the NRTL [21], UNIQUAC [22], and Wilson [23] activity coefficient models. The interaction parameters of the models were obtained by minimizing the following objective function according to the maximum likelihood method: 2 3 !2  2  exp 2 XN pexp  pcal 2 T exp  T cal xexp  xcal yi  ycal i i i i i i i 4 5 F¼ þ þ þ i¼1

rp

rT

rx

ry

ð16Þ

where N represents the number of data points; T, P, x and y are equilibrium temperature, and pressure, mole fractions in liquid phase and vapour phase, respectively; r represents the standard deviation; the superscripts ‘‘exp” and ‘‘cal” represent the experimental data and calculated values. The values of the structural parameters r (van der Waals volume of molecular) and q (van der Waals surface area of molecular) of the components for the UNIQUAC model are listed in Table 11. The regressed interaction parameters of the three models and the root-mean-square deviation (RMSD) are given in Table 12. As shown in Table 12, the RMSDðy1 Þ and RMSDðTÞ are less than 0.0075 and 0.45, respectively. The results indicate that the NRTL, UNIQUAC and Wilson activity coefficient models are suitable for the VLE calculation for the three binary systems. 4. Extractive distillation process design 4.1. Solvent effects of entrainers The solvent effects of the three entrainers N-methyl-2pyrrolidone, N-methyl formamide and ethylene glycol were examined by calculation of the separation factor. The relative volatility is another criterion used for solvent selection, which is the ratio of

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J. Wu et al. / J. Chem. Thermodynamics 118 (2018) 139–146

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

FHerington

FVanNess

FInf.Dil.

Fpure

QVLE  1

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

0.25 0.25 0.25

0.25 0.25 0.25

0.25 0.25 0.25

1.00 1.00 1.00

1.00 1.00 1.00

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

a

Component

r

q

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

2.550 3.981 2.403 2.409

2.300 3.200 2.192 2.248

Taken from Aspen property databank [37].

volatilities between the light and heavy components after the addition of a solvent. The relative volatility was calculated using the UNIQUAC model with the binary parameters listed in Table 12. The x-y diagram of allyl alcohol and water was used to reflect the change of the relative volatility. As shown in Fig. 5, the relative volatility of allyl alcohol increased when the entrainer was added. The three entrainers could effectively break the azeotropic point of (allyl alcohol + water). Compared to the three entrainers, N-methyl-2-pyrrolidone shows the greatest deviation from the diagonal, which indicates that the relative volatility of allyl alcohol was changed effectively. Therefore, N-methyl-2-pyrrolidone was selected as the entrainer to design the extractive distillation process for the separation of the azeotrope (allyl alcohol + water).

4.2. Extractive distillation process design for the azeotrope of allyl alcohol + water The flow diagram for the separation of the azeotrope of (allyl alcohol + water) is shown in Fig. 6. The feed (stream F) was pumped into column 1 (extraction column). And the solvent N-methyl-2-pyrrolidone (stream S) was fed near the top of the

Fig. 5. Influence on VLE with different solvents: -d-, N-methyl-2-pyrrolidone; -N-, ethylene glycol; -j-, N-methyl formamide.

column 1 above the binary feed mixture. The allyl alcohol with the purity of 99.9 mol% (stream D1) was obtained from the top of the column 1. Meanwhile, the mixture of water + N-methyl-2pyrrolidone went to the column 2 (recovery column) as the feed stream (stream B1). Water was separated from the top of the column 2 with the purity of 99.5 mol% (stream D2). The N-methyl2-pyrrolidone (stream B2) was recycled back to column 1 crossed the stream 1. In the whole separation process, N-methyl-2pyrrolidone had a slight loss and the additional solvent (stream M) was added as a make-up feed. The calculated results of all the streams are listed in Table 13.

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

Parameters

RMSD

aij

aji

bij/K

bji/K

allyl alcohol (1) + N-methyl-2-pyrrolidone (2) NRTLc 6.7272 UNIQUACd 4.0312 Wilsone 0.5355

0.8576 1.1989 11.6695

1999.21 1265.26 59.5597

7.0905 280.81 3894.61

0.0074 0.0075 0.0074

0.44 0.45 0.42

allyl alcohol (1) + N-methyl formamide (2) NRTL 2.5377 UNIQUAC 0.7170 Wilson 0.5824

3.2469 0.8384 0.3959

829.80 225.58 132.97

942.78 213.18 173.87

0.0042 0.0042 0.0041

0.44 0.42 0.40

0.6152 0.4811 0.2398

509.97 154.06 333.94

191.24 124.29 330.07

0.0029 0.0028 0.0029

0.27 0.29 0.29

allyl alcohol (1) + ethylene glycol (2) NRTL 0.5870 UNIQUAC 0.0452 Wilson 0.8592 rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 2 PN ðyexp ycal Þ a 1;i 1;i . RMSDðy1 Þ ¼ i¼1 N rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 2 PN ðT exp T cal b i Þ i . RMSDðTÞ ¼ i¼1 N c d e

Tb/K

y1a

NRTL, sij ¼ aij þ bij =T, the value of aij was set at 0.3 for binary systems. UNIQUAC, sij ¼ expðaij þ bij =TÞ. Wilson, lnAij ¼ aij þ bij =T.

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

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

F S D1 B1 D2 B2 M

Mole flow/(kmolh1)

Mole fraction

Allyl alcohol

Water

N-methyl-2-pyrrolidone

Allyl alcohol

Water

N-methyl-2-pyrrolidone

50 0 50 trace trace trace 0

50 0 0.043 49.957 49.975 trace 0

0 295 0.007 294.993 0.243 294.75 0.25

0.5 0 0.999 trace trace trace 0

0.5 0 850PPM 0.145 0.995 trace 0

0 1 149PPM 0.855 0.005 1 1

5. Conclusions The isobaric VLE values for the binary systems of (allyl alcohol + N-methyl-2-pyrrolidone), (allyl alcohol + N-methyl formamide) and (allyl alcohol + ethylene glycol) were determined at 101.3 kPa by a modified Rose type recirculating still. The thermodynamic consistency of the experimental results was validated by the Herington, van Ness, infinite dilution, and pure component consistency methods. The results show that the VLE data for the three binary mixtures are thermodynamically consistent. Meanwhile, the experimental VLE values for three binary mixtures were correlated using the NRTL, Wilson and UNIQUAC models. The values of RMSD for the vapour-phase compositions and the temperature were less than 0.0075 and 0.45 K, respectively. Furthermore, the selectivity of the three investigated entrainers was evaluated. The results show that N-methyl-2-pyrrolidone, N-methyl formamide and ethylene glycol could be used as entrainers for the extractive distillation of the binary azeotropic mixture (allyl alcohol + water). The N-methyl-2-pyrrolidone is the best one among the three entrainers. Finally, the extractive distillation process was designed for the separation of the azeotrope of (allyl alcohol + water). Acknowledgement This work was supported by the National Scientific Research Found of China (NSC 21306106). Appendix A. Supplementary data Supplementary data associated with this article can be found, in the online version, at https://doi.org/10.1016/j.jct.2017.11.009. References [1] O. Eric, M. John, A new stereoselective method for the preparation of allylic alcohols, J. Am. Chem. Soc. 119 (1997) 9065–9066.

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JCT 17-781