Isobaric Vapor–Liquid Equilibrium Data for the ... - ACS Publications

Aug 28, 2018 - Vapor–liquid equilibrium (VLE) data for the binary system of acetone (1) + hexamethyl disiloxane (HMDSO, 2) and the ternary system of...
0 downloads 0 Views 755KB Size
Download PDF
Article pubs.acs.org/jced

Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Isobaric Vapor−Liquid Equilibrium Data for the Acetone + Hexamethyl Disiloxane + Ethyl Acetate Ternary System at 101.3 kPa: Determination and Correlation Chunli Li, Siqi Gong, and Hao Li* School of Chemical Engineering, Hebei University of Technology, Tianjin 300401, China

J. Chem. Eng. Data Downloaded from pubs.acs.org by UNIV OF SOUTH DAKOTA on 08/29/18. For personal use only.

S Supporting Information *

ABSTRACT: Vapor−liquid equilibrium (VLE) data for the binary system of acetone (1) + hexamethyl disiloxane (HMDSO, 2) and the ternary system of acetone (1) + HMDSO (2) + ethyl acetate (EAC, 3) were obtained at 101.3 kPa. The acetone (1) + HMDSO (2) mixture had azeotropic temperature of 329.00 K, x1,az = 0.9661. The binary VLE values and ternary VLE values were confirmed to be thermodynamically consistent using the Herington method and the McDermott−Ellis method, respectively. The binary VLE data were correlated using the nonrandom two-liquid (NRTL), universal quasichemical activity coefficient (UNIQUAC), and Wilson models, and the NRTL model has the best correlation with the experimental data. Furthermore, the acetone (1) + HMDSO (2) + EAC (3) ternary VLE data were predicted with the NRTL model using the binary interaction parameter obtained by association of the contained binary system, and the calculated data were in good agreement with the ternary experimental data. To further describe the ternary system, the residue curves were provided by Aspen Plus using the NRTL model.

1. INTRODUCTION

2. EXPERIMENTAL SECTION

Hexamethyl disiloxane (HMDSO) is an important organic solvent and chemical synthesis raw material1,2 and is widely used in the synthesis of pharmaceutical intermediates because of its excellent solubility.3 In the production of cephalexin, hexamethyl disiloxane was used as a hydroxyl protector. A considerable amount of effluent consisting of acetone, ethyl acetate (EAC), and HMDSO needs to be separated and recovered. While azeotrope exists in the acetone (1) + HMDSO (2) + EAC (3) ternary system, methods to separate this ternary system have not been reported yet. Nowadays, extractive distillation is widely used to separate azeotropic systems.4,5 However, the VLE data of this ternary system have not been reported. Therefore, the VLE data for the acetone (1) + HMDSO (2) + EAC (3) ternary system were needed for the design of an extractive distillation process. The VLE data for the HMDSO (2) + EAC (3) system and the acetone (1) + EAC (3) system have been reported in literature.6,7 The VLE data for the acetone (1) + HMDSO (2) binary system and the acetone (1) + HMDSO (2) + EAC (3) ternary system at 101.3 kPa were measured in this experiment. The measured data were tested by the Herington test and the McDermott−Ellis test.8,9 Moreover, the nonrandom two-liquid (NRTL),10 universal quasichemical activity coefficient (UNIQUAC),11 and Wilson12 equations were employed to correlate the experimental data, and the NRTL model was adopted to predict the ternary phase equilibrium.

2.1. Materials. The materials acetone, HMDSO, and EAC were used in this study. The properties of these materials are reported in Table 1. All materials were analyzed by gas chromatography (GC Smart from Shimadzu), and no detectable impurity was observed. All of the materials were used without further purification. 2.2. Procedure. In this study, the VLE modified Othmer still was used to determine the VLE data.13−15 The device

© XXXX American Chemical Society

Table 1. Physical Properties of the Pure Componentsa property

acetone (1)

HMDSO (2)

EAC (3)

formula CAS M/g·mol−1 Tb/K Tc/K Pc/kPa supplier purity (mass %)

CH3COCH3 67−64−1 58.08 329.44 508.20 4701.00 Fuchen, China ≥99.5%

C6H18Si2O 107−46−0 162.38 373.67 518.70 1914.00 Aladdin, China ≥99.7%

C4H8O2 141−78−6 88.11 350.21 523.30 3880.00 Chemart, China ≥99.5%

a M, molecular weight; Tb, boiling point; Tc, critical temperature; Pc, critical pressure. Taken from Aspen Plus physical properties databanks.

Received: June 13, 2018 Accepted: August 15, 2018

A

DOI: 10.1021/acs.jced.8b00488 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

mainly consists of liquid-phase sample port, vapor-phase sample port, vapor-phase condenser, liquid-phase sample reservoir, heating bar, and thermometer casing. A precision thermometer was used to ensure that the temperature measurement error was within ±0.05 K. Furthermore, the temperature was corrected based on the temperature of the spot at half of the thermometer mercury column and the internal pressure of the still. A differential manometer and a vacuum pump were used to keep the pressure in the still stabilized at 101.3 ± 0.05 kPa. About 45 mL mixture of the different ratio liquid was put into the still. A small fraction of liquid and vapor left the boiling room and went into the separator room. Then, the vapor left the liquid, entered the gas condenser, and was condensed into droplets immediately. The vapor-phase sample was collected in the vapor-phase sampling pool. Meanwhile, the liquid-phase sample gathered at the liquid-phase sampling pool. The spilled vapor-phase and liquid-phase samples returned to the boiling room, mixed, and continued to be heated. Stability of the studied system was achieved after only 1−2 h. The heating rate was adjusted to keep the condensate dripping down at a consistent frequency. 2.3. Analysis. GC Smart (GC-2018, from Shimadzu), equipped with a flame ionization detector (FID) and a CBFFAP column (30 m × 0.32 mm × 1.2 μm), was applied to analyze the samples.16 The pressure of carrier gas was set to 0.03 MPa. The detector and the injector were kept at 150 °C. The standard curve was made to calibrate the gas chromatographic results. Compared with known mixture samples, the maximum absolute deviation was within 0.5%.

Table 2. VLE Data for the Acetone (1) + HMDSO (2) Systema T/K

x1

x2

y1

y2

γ1

374.12 369.09 364.46 356.78 349.03 343.64 339.51 335.53 334.01 333.31 332.72 331.54 330.70 330.30 329.78 329.50 329.20 329.04 329.01 329.24 329.33

0.0000 0.0164 0.0317 0.0758 0.1376 0.2102 0.2847 0.3884 0.4378 0.5178 0.5613 0.6429 0.7417 0.7896 0.8401 0.8793 0.9140 0.9460 0.9692 0.9874 1.0000

1.0000 0.9836 0.9683 0.9242 0.8624 0.7898 0.7153 0.6116 0.5622 0.4822 0.4387 0.3571 0.2583 0.2104 0.1599 0.1207 0.0860 0.0540 0.0308 0.0126 0.0000

0.0000 0.1552 0.2674 0.4396 0.5871 0.6930 0.7586 0.8105 0.8288 0.8448 0.8544 0.8688 0.8828 0.8882 0.9047 0.9197 0.9341 0.9522 0.9690 0.9863 1.0000

1.0000 0.8448 0.7326 0.5604 0.4129 0.3070 0.2414 0.1895 0.1712 0.1552 0.1456 0.1312 0.1172 0.1118 0.0953 0.0803 0.0659 0.0478 0.0310 0.0137 0.0000

2.8618 2.8907 2.4619 2.2719 2.0706 1.9059 1.6978 1.6195 1.4286 1.3595 1.2557 1.1378 1.0900 1.0622 1.0416 1.0283 1.0183 1.0126 1.0036 1.0017

γ2 0.9894 0.9870 1.0021 1.0258 1.0500 1.0289 1.0369 1.1030 1.1478 1.2459 1.3140 1.5217 1.9424 2.3110 2.6452 2.9832 3.4766 4.0400 4.5892 4.9341

a

xi, mole fraction of component i in the liquid phase; yi, mole fraction of component i in the vapor phase; T, equilibrium temperature; γi, tabulated activity coefficient of component i; pressure P = 101.3 kPa. The standard uncertainty is u(T) = 0.05 K, u(P) = 0.3 kPa, and u(x1) = u(y1) = 0.004.

3. RESULTS AND DISCUSSION 3.1. Experimental Data. The VLE data for the acetone (1) + HMDSO (2) binary system were obtained at 101.3 kPa (shown in Table 2 and Figure 1). The results show that an azeotrope exists in this system at 329.00 K and x1 = 0.9661. Since its location is close to pure acetone, it is difficult to discern the azeotrope. The VLE data for the acetone (1) + HMDSO (2) + EAC (3) ternary system, obtained at 101.3 kPa, are listed in Table 3. The pairs of the ternary VLE data together with the residue curves are respectively represented in Figure 2 and Figures S1−S4 in the Supporting Information. 3.2. Thermodynamic Consistency Test. To check the thermodynamic consistency of the binary VLE data, the Herington method was adopted.8,9 The equation to calculate the tabulated activity coefficient (γi) was:17 ij V L(P − Pi s) yz zz φiPyi = γixiPisφi sexpjjj i zz j RT k {

Figure 1. T vs x1, y1 diagram for the acetone (1) + HMDSO (2) system. Solid black square and triangle, experimental data; blue solid line, calculated with the NRTL model; pink dotted line, calculated with the UNIQUAC model; blue dash/dot line, calculated with the Wilson model. Coordinates of azeotrope (with the NRTL model): x1,az = 0.9661, Taz = 329.00 K.

(1)

where R is the gas constant, ViL is the molar volume of pure liquid i, xi is the mole fraction of component i in the liquid phase, and yi is the mole fraction of component i in the vapor phase. When it is at low or intermediate pressure, the Poynting

(

factor exp

Vi L(P − Pi s) RT

) is approximately equal to 1. φ is the i

The Antoine equation with some simple extension by

fugacity coefficient of i in the mixture vapor phase, φis is the fugacity coefficient of pure vapor i, and are both approximately equal to 1.18 So, the following simplified equation was adopted: Pyi = γixiPis

additional terms from Aspen Plus was used to calculate the saturation vapor pressure of component i (Pis).19 The additional parameters increase the flexibility of the equation

(2)

and allow the description of the entire vapor pressure curve. B

DOI: 10.1021/acs.jced.8b00488 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 3. VLE Data for the Acetone (1) + HMDSO (2) + EAC (3) Systema T/K

x1

x2

x3

y1

y2

y3

D

Dmax

330.63 330.83 331.48 333.46 335.01 337.36 338.95 339.59 340.64 343.16 346.52 346.81 330.69 330.97 333.01 334.87 335.12 335.78 338.07 339.58 341.86 346.35 332.43 332.66 333.91 335.70 338.30 341.30 346.55 332.36 334.75 337.66 343.06 346.48 335.90 339.29 343.62 345.90

0.8977 0.8577 0.7869 0.6987 0.6047 0.4596 0.4124 0.3605 0.2874 0.2085 0.1184 0.0842 0.8282 0.7935 0.6516 0.5984 0.5575 0.4779 0.4181 0.3215 0.2325 0.1246 0.7178 0.6639 0.5710 0.4737 0.3503 0.2521 0.1034 0.5859 0.4880 0.3468 0.2010 0.1073 0.4087 0.2912 0.1897 0.1662

0.0408 0.0378 0.0391 0.0480 0.0472 0.0516 0.0489 0.0489 0.0543 0.0547 0.0539 0.0559 0.0951 0.0812 0.1162 0.1077 0.1039 0.1302 0.1224 0.1264 0.1254 0.1132 0.2057 0.2072 0.2186 0.2320 0.2495 0.2487 0.2669 0.3258 0.3353 0.3667 0.3898 0.3904 0.4969 0.5134 0.5189 0.7281

0.0615 0.1045 0.1740 0.2532 0.3481 0.4888 0.5387 0.5905 0.6583 0.7368 0.8277 0.8599 0.0767 0.1252 0.2322 0.2940 0.3386 0.3918 0.4595 0.5521 0.6421 0.7622 0.0764 0.1289 0.2104 0.2943 0.4002 0.4991 0.6296 0.0883 0.1767 0.2865 0.4092 0.5023 0.0945 0.1954 0.2915 0.1057

0.9301 0.9130 0.8741 0.8203 0.7505 0.6401 0.6064 0.5501 0.4648 0.3666 0.2353 0.1742 0.8952 0.8778 0.7893 0.7581 0.7279 0.6685 0.6227 0.5245 0.4241 0.2612 0.8403 0.8119 0.7620 0.7013 0.5906 0.4796 0.2478 0.8229 0.7431 0.6290 0.4573 0.2868 0.7642 0.6415 0.4935 0.5676

0.0401 0.0366 0.0384 0.0450 0.0450 0.0483 0.0438 0.0419 0.0438 0.0479 0.0510 0.0448 0.0706 0.0666 0.0838 0.0768 0.0776 0.0897 0.0897 0.0915 0.0953 0.0920 0.1013 0.1056 0.1095 0.1148 0.1314 0.1410 0.1664 0.1370 0.1410 0.1633 0.1953 0.2179 0.1760 0.1975 0.2240 0.3073

0.0298 0.0504 0.0875 0.1346 0.2045 0.3115 0.3499 0.4080 0.4913 0.5856 0.7137 0.7810 0.0342 0.0556 0.1269 0.1650 0.1946 0.2418 0.2876 0.3840 0.4806 0.6468 0.0584 0.0825 0.1285 0.1839 0.2781 0.3794 0.5858 0.0401 0.1158 0.2077 0.3474 0.4953 0.0598 0.1610 0.2826 0.1251

0.0318 0.0374 −0.0344 0.0271 0.0272 −0.0477 0.0503 0.0564 −0.0339 −0.0507 0.0581 −0.1687 0.0352 0.0380 −0.0616 0.0416 0.0587 −0.0745 0.0671 0.0046 −0.0621 0.2146 0.0221 −0.0032 −0.0107 0.0292 −0.0174 0.0015 −0.1339 0.0156 0.0274 −0.0513 0.0366 −0.1186 0.0357 −0.0232 −0.0080 0.0318

0.0872 0.0863 0.0839 0.0813 0.0789 0.0763 0.0758 0.0752 0.0736 0.0717 0.0698 0.2097 0.0918 0.0918 0.0847 0.0831 0.0824 0.0808 0.0790 0.0764 0.0745 0.2526 0.0889 0.0903 0.0892 0.0867 0.0821 0.0802 0.1554 0.1011 0.0910 0.0851 0.0787 0.1212 0.0965 0.0860 0.0864 0.0872

a

xi, mole fraction of component i in the liquid phase; yi, mole fraction of component i in the vapor phase; T, equilibrium temperature; D, local deviation; Dmax, local value of the maximum deviation; pressure P = 101.3 kPa. The standard uncertainty is u(T) = 0.05 K, u(P) = 0.3 kPa, and u(xi) = u(yi) = 0.004.

ln Pis = C1 +

temperature of the system, hE is the molar excess enthalpy in the mixing process, hEmax was the numerically largest value of hE, gE is excess Gibbs function, gEmax is the maximum value of gE. Herington declared that the function |hEmax/gEmax| would seldom exceed the value 3.0.8 The following relation is widely used for determining consistency:

C2 + C4T + C5 ln T + C6T C7 T + C3

C8 ≤ T ≤ C 9

(3)

The extended Antoine equation can be used in the range of C8 (K) to C9 (K). The values of C1−C9 for these pure components are shown in Table 4. The results of the Herington test are shown in Figure 3. Under this method, the experimental binary data should satisfy the following equation: 1

D=

2

∫0

ln

γ1 γ2

D=

γ

2

1

γ1

∫0 ln γ dx1 2

γ1

∫0 ln γ dx1 1

1

∫0 ln γ1 dx1

dx1

× 100 < 50 ×

h

E max

g E max

θ =J Tm

× 100 < 150 ×

|θ | =J Tm (5)

Herington declared that if (D − J) < 10, the data were consistent.8 In this acetone (1) + HMDSO (2) binary system, D = 2.1455, J = 20.5662, (D − J) < 10, so the VLE data are considered consistent. The McDermott−Ellis method was conducted to test the reliability of the ternary VLE data.8 This method showed that

(4)

where θ is the difference between maximum and minimum equilibrium temperatures, Tm is the minimum equilibrium C

DOI: 10.1021/acs.jced.8b00488 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

where a and b are the two points to be tested, n is the amount of components in the system. Wisniak and Tamir20 used a local value of the maximum deviation as a fixed value for Dmax, defined by8,21 ij

1 1 1 yz + + zzzzΔx x yia xib yib z i=1 k ia { n n ΔP + ∑ |ln γib − ln γia|Δx + ∑ (xib + xia) P i=1 i=1 n ÅÄÅ ÑÉÑ ÅÅ ÑÑ 1 1 Å ÑΔT + ∑ (xib + xia)BÅÅ + 2 2Ñ Å (Tb + C) ÑÑÑÑÖ ÅÅÇ (Ta + C) i=1

∑ (xib + xia)jjjjj 1 n

Dmax =

+

(7) Figure 2. Residue curves of the acetone (1) + HMDSO (2) + EAC (3) ternary system. Black solid circle, experimental liquid phase composition; red open circle, experimental vapor phase composition; pink solid line, pairs of VLE data; blue dashed line, residue curves.

where Δx, ΔP, and ΔT are the errors in the measurement of mole fraction, the pressure, and temperature, respectively. B, and C are the pertinent coefficients in the Antoine equation ln Psi = A − B/(Ti + C), and are shown in Table S1 in the Supporting Information. As is shown in Table 3, the value of D is less than the value of Dmax, indicating that these equilibrium points determined in this work are consistent by the McDermott−Ellis test. 3.3. Data Regression and Prediction. In the regression of the binary VLE data, the maximum likelihood objective function was used.22

Table 4. Parameters of Extended Antoine Equationa C1 C2 C3 C4 C5 C6 C7 C8 C9

acetone (1)

HMDSO (2)

EAC (3)

62.0982 −5599.60 0 0 −7.0985 6.2237 × 10−6 2.00 178.45 508.20

44.0212 −5597.00 0 0 −4.1262 6.3815 × 10−18 6.00 204.93 518.70

59.9162 −6227.60 0 0 −6.4100 1.7914 × 10−17 6.00 189.60 523.30

Ä É2 Ä É jijÅÅÅ Texp, i − Tcal, i ÑÑÑ2 ÅÅÅÅ yexp, i − ycal, i ÑÑÑÑ zyz j Å Ñ Å ÑÑ zzz j Å ÑÑ + ÅÅ F = ∑ jjÅÅ ÑÑ zz ÑÑ ÅÅ jjÅÅÇ σ σ ÑÑÖ z Ñ T y Å Ö i=1 Ç k { n

a

Temperature units, K; pressure units, kPa. Taken from Aspen Plus physical properties databanks.

(8)

where σ is the standard deviation of the measured variables. The standard deviations of temperature σT and vapor mole fraction σy used in this VLE data correlation are 0.1 K and 0.001. The experimental VLE data for the acetone (1) + HMDSO (2) system were used to calculate the binary correlated parameters for the NRTL, UNIQUAC, and Wilson models as available in Aspen Plus. The equations for the NRTL model are ln γi = Figure 3. Herington test for the VLE data of acetone (1) + HMDSO (2) system. Black solid circle, values of ln(γ1/γ2); blue solid line, fitted curve.

∑j xjτjiGji ∑k xkGki

+

∑ j

ij y jjτ − ∑m xmτmjGmj zzz jj ij z ∑k xkGkj zz ∑k xkGkj j k { xjGij

Gij = exp( −αijτij) τij = aij + bij /T + eij ln T + fij T αij = cij + dij(T − 273.15 K) τij = 0

when D < Dmax, the selected two points are thermodynamically consistent, where D is the local deviation given by

Gii = 1

n

D=

∑ (xib + xia)(ln γib − ln γia) i=1

(9) (6)

The equations for the UNIQUAC model are D

DOI: 10.1021/acs.jced.8b00488 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 5. Binary Interaction Parameters of the NRTL, UNIQUAC, and Wilson Models for Systems of Acetone (1) + HMDSO (2), HMDSO (2) + Ethyl Acetate (3), and Acetone (1) + Ethyl Acetate (3) binary interaction parameters a12

model

a21

NRTL UNIQUAC Wilson

1.8041 −0.1614 1.0587

0.8672 −0.7065 −9.5241

NRTL UNIQUAC Wilson

−1.1785 38.3523 30.2471

−1.2664 9.0866 −2.0273

NRTL UNIQUAC Wilson

0.0000 0.0000 0.0000

0.0000 0.0000 0.0000

b12

b21

c12

acetone (1) + HMDSO (2) −23.0966 −303.8612 78.7334 24.4555 −449.5900 2656.2091 HMDSO (2) + ethyl acetate (3)a 376.3715 776.5236 −2201.8321 −507.3313 −2130.9940 −431.2395 acetone (1) + ethyl acetate (3)b 109.1500 −42.7758 23.8829 −54.1759 16.6058 −81.9807

c21

0.3000 0.0000 0.0000

0.0000 0.0000

0.3000 −5.5422 −4.2531

−1.2776 0.5391

0.3000 0.0000 0.0000

0.0000 0.0000

a

Calculated with data from literature.6 bTaken from Aspen Plus physical properties databanks.

The values of F calculated with the maximum likelihood objective function as well as the maximum deviations (MD) and standard deviations (σ) of temperature and vapor mole fraction for the acetone (1) + HMDSO (2) system can be seen in Table 6. The value of F calculated with the NRTL model is

qi′ ∑j θj′τij Φi θ z + qi ln i − qi′ln ti′ − + li + qi′ 2 xi t ′j Φi Φ − i ∑ xjl j xi j

ln γi = ln

θi = qixi /qT ; qT =

Table 6. Maximum Deviations of Temperature ΔTMD, Maximum Deviations of Vapor Mole Fraction ΔyMD, Standard Deviations of Temperature σT, Standard Deviations of Vapor Mole Fraction σy, and the Value of F using the NRTL, UNIQUAC, and Wilson Models for the Acetone (1) + HMDSO (2) System

∑ qkxk k

θi′ = qi′xi /qT′ ; q′T =

∑ qk′xk k

Φi = rx i i / rT ; rT =

∑ rkxk k

li =

z (ri − qi) + 1 − ri 2

ti′ =

∑ θk′τki k

z = 10 (10)

The equations for the Wilson model are

∑ j

Aji xj ∑k Ajk xk

ln Aij = aij + bij /T + cij ln T + dijT + eij/T 2

(11)

In which dij, dji, eij, eji, f ij, and f ji can be approximated to zero.17 The binary correlated parameters for the acetone (1) + HMDSO (2) system are shown in Table 5. The standard deviations of temperature (σT) and vapor mole fraction (σy) are given by ij N yz σT = jjjj∑ (Texp, i − Tcal, i)2 /N zzzz j i=1 z k {

1/2

ij N yz σy = jjjj∑ (yexp, i − ycal, i )2 /N zzzz j i=1 z k {

ΔTMD

ΔyMD

σT

σy

F

NRTL UNIQUAC Wilson

0.7555 0.8318 1.2130

0.0176 0.0183 0.0233

0.3819 0.3971 0.4892

0.0062 0.0065 0.0083

1106.9521 1214.3550 1957.9664

smaller than that of the other models, indicating that the NRTL model has the best correlation. The values of F and the standard deviations of vapor mole fraction and temperature of the three models were compared with those in some other studies. When modeling the HMDSO + EAC system in Zhang’s work, the standard deviations of vapor mole fraction and temperature were 0.3844 and 0.1698, respectively.6 The smaller deviations in our work illustrated that the NRTL model had a good correlation with experimental data for this system. For the binary system, the comparisons between experimental data and calculated data using the NRTL, UNIQUAC, Wilson models can be seen in Figure 1. It can be obtained that the NRTL model was more suitable to correlate the experimental data in the whole range of compositions considered. It was known from previous literature that the binary parameters of every two components of the ternary system can be used to make a prediction of the ternary VLE data.17 The binary interaction parameters of the related systems are listed in Table 5. Compared with other models, the NRTL model was more suitable for the correlation of the VLE data for the acetone (1) + HMDSO (2) system, the acetone (1) + EAC (3) system, and the HMDSO (2) + EAC (3) system.6,7 Then, the NRTL model was adopted to predict the acetone (1) + HMDSO (2) + EAC (3) ternary VLE data. The predicted

τij = exp(aij + bij /T + cij ln T + dijT + eij/T 2)

jij zyz ln γi = 1 − lnjjj∑ Aij xjzzz − jj zz k j {

model

(12)

1/2

(13) E

DOI: 10.1021/acs.jced.8b00488 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 7. Maximum Deviations and Standard Deviations of the Equilibrium Temperature and the Vapor-Phase Mole Fraction for the Acetone (1) + HMDSO (2) + EAC (3) System Using the NRTL Model ΔTMD

Δy1,MD

Δy2,MD

Δy3,MD

σT

σ y1

σy2

σy3

1.2130

0.0104

0.0056

0.0142

0.4458

0.0055

0.0027

0.0074

values were compared with the experimental values, the deviations are listed in Table 7. When modeling the ternary system of isopropyl alcohol, isopropyl acetate, and dimethyl sulfoxide in Ding’s work, the standard deviations of the temperature (σT) and vapor mole fraction (σy1, σy2, and σy3) were 0.43, 0.0026, 0.0028, and 0.0011, respectively.17 The slightly bigger deviations in our work were mainly because of a common deficiency of the general models, which indicated the deviations were acceptable. Therefore, the NRTL model could make a good prediction of the VLE data of the ternary system. The maximum likelihood objective function for the regression of the ternary VLE data was:22 Ä É2 n i jjÅÄÅÅ Texp, i − Tcal, i ÑÉÑÑ2 ÅÅÅÅ y1,exp, i − y1,cal, i ÑÑÑÑ jjÅÅ Å ÑÑ Ñ ÑÑ + ÅÅ F = ∑ jjÅÅ ÅÅ ÑÑÑ ÑÑ jjÅÅ σ σ ÑÖ T y1 i = 1 jÇ ÅÅÇ ÑÑÖ k ÅÄÅ y ÑÉÑ2 y ÅÅÅ 2,exp, i − y2,cal, i ÑÑÑ zzzz + ÅÅÅ ÑÑÑ zzz ÅÅ ÑÑ zz σy ÅÇ ÑÖ { 2 (14)

4. CONCLUSIONS To simulate the separation process of the acetone (1) + HMDSO (2) + EAC (3) ternary system with Aspen Plus, the new VLE data for the acetone (1) + HMDSO (2) binary system and the acetone (1) + HMDSO (2) + EAC (3) ternary system were measured with a VLE modified Othmer still at 101.3 kPa. The experimental data successfully passed the thermodynamic consistency test. Compared with the Wilson and UNIQUAC models, the NRTL model was more suitable to correlate the measured VLE data of the (acetone + HMDSO) binary system. Furthermore, the obtained binary interaction parameters of the NRTL model were adopted to predict the (acetone + HMDSO + EAC) ternary phase equilibrium, and the calculated results agreed well with the experimental values. The measured data obtained in this experiment provide support for the simulation and design of industrialized processes involving related systems.

The standard deviations of temperature σT and vapor mole fractions σy1 and σy2 used in this VLE data correlation are 0.1 K, 0.001, and 0.001. The interaction parameters of the acetone (1) + HMDSO (2) system were also obtained from the ternary VLE data by being fitted with the NRTL model in Aspen Plus. The VLE data of the acetone (1) + HMDSO (2) system were calculated by the obtained parameters and compared with the experimental data; the deviations are listed in Table 8. The

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jced.8b00488. Figures S1−S4: residue curves of the acetone (1) + HMDSO (2) + EAC (3) ternary system; Table S1: Antoine equation parameters (PDF)

■ ■

model

ΔTMD

ΔyMD

σT

σy

F

0.8785

0.0108

0.4519

0.0071

1496.7282

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Table 8. Maximum Deviations and Standard Deviations of the Equilibrium Temperature and Vapor-zphase Mole Fraction and the Value of F for the Acetone (1) + HMDSO (2) System between Experimental Data and Calculated Data zusing Parameters from the Regression of Ternary Data NRTL

ASSOCIATED CONTENT

S Supporting Information *

Chunli Li: 0000-0003-1495-5740 Hao Li: 0000-0002-4151-0707 Funding

Financial support is acknowledged from the National Key Research and Development Program of China (Grant 2017YFB0602500). Notes

The authors declare no competing financial interest.

■

results show that the binary interaction parameters obtained from the ternary experimental data can make a good prediction of the binary VLE data for the acetone (1) + HMDSO (2) system, but the deviations are slightly larger than those of the prediction obtained from binary experimental data, compared with values in Table 6. Furthermore, the residue curves calculated with the NRTL model are presented in Figure 2. The experimental points of the acetone (1) + HMDSO (2) + EAC (3) ternary system are also shown in the diagram. At the liquid-phase point, the connections between each liquid-phase point and its corresponding vapor-phase point are tangent with the residue curves, indicating that the predicted residue curves represent the experimental data well.23

REFERENCES

(1) Curphey, T. J. Thionation with the Reagent Combination of Phosphorus Pentasulfide and Hexamethyldisiloxane. J. Org. Chem. 2002, 67, 6461−6473. (2) Denes, A. R.; Tshabalala, M. A.; Rowell, R.; Denes, F.; Young, R. A. Hexamethyldisiloxane−Plasma Coating of Wood Surfaces for Creating Water Repellent Characteristics. Holzforschung 1999, 53, 318−326. (3) Lozinsky, E.; Eilat, E. Pharmaceutical liquid adhesive compositions for treatment of anorectal disorders. WO 2014064703 A1, 2014. (4) Widagdo, S.; Seider, W. D. Journal review. Azeotropic distillation. AIChE J. 1996, 42, 96−130. (5) Ma, Y.; Gao, J.; Li, M.; Zhu, Z.; Wang, Y. Isobaric vapour−liquid equilibrium measurements and extractive distillation process for the azeotrope of (N,N−dimethylisopropylamine + acetone). J. Chem. Thermodyn. 2018, 122, 154−161. F

DOI: 10.1021/acs.jced.8b00488 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

(6) Zhang, W.; Meng, N.; Sun, R.; Li, C. Determination and Correlation of Vapor−Liquid Equilibrium Data for the Ethyl Acetate + Hexamethyl Disiloxane System at 101.3 kPa. J. Chem. Eng. Data 2011, 56, 5078−5080. (7) Acosta, J.; Arce, A.; Martinez−Ageitos, J.; Rodil, E.; Soto, A. Vapor−Liquid Equilibrium of the Ternary System Ethyl Acetate + Hexane + Acetone at 101.32 kPa. J. Chem. Eng. Data 2002, 47, 849− 854. (8) Wisniak, J.; Ortega, J.; Fernández, L. A fresh look at the thermodynamic consistency of vapour−liquid equilibria data. J. Chem. Thermodyn. 2017, 105, 385−395. (9) Wisniak, J. The Herington test for thermodynamic consistency. Ind. Eng. Chem. Res. 1994, 33, 177−180. (10) Liu, Y.; Zhang, L.; Watanasiri, S. Representing Vapor−Liquid Equilibrium for an Aqueous MEA−CO2 System Using the Electrolyte Nonrandom−Two−Liquid Model. Ind. Eng. Chem. Res. 1999, 38, 2080−2090. (11) Thomsen, K. Modeling electrolyte solutions with the extended universal quasichemical (UNIQUAC) model. Pure Appl. Chem. 2005, 77, 531−542. (12) Orye, R. V.; Prausnitz, J. M. Multicomponent equilibriathe Wilson equation. Ind. Eng. Chem. 1965, 57, 18−26. (13) Zudkevitch, D. Temperature Differences inside Vapor−Liquid Apparati: the Quest for the Isothermal Othmer Still. Chem. Eng. Commun. 1992, 116, 41−65. (14) Li, Q.; Zhang, J.; Lei, Z.; Zhu, J.; Wang, B.; Huang, X. Isobaric Vapor-Liquid Equilibrium for (Propan−2−ol + Water + 1Butyl3− methylimidazolium Tetrafluoroborate). J. Chem. Eng. Data 2009, 54, 2785−2788. (15) Giner, B.; Artigas, H.; Gascón, I.; Cea, P.; Royo, F. M. Experimental data of isobaric vapour−liquid equilibrium for binary mixtures containing tetrahydrofuran and isomeric chlorobutanes. Phys. Chem. Liq. 2005, 43, 299−307. (16) Jorgensen, A. D.; Picel, K. C.; Stamoudis, V. C. Prediction of gas chromatography flame ionization detector response factors from molecular structures. Anal. Chem. 1994, 62, 683−689. (17) Ding, H.; Gao, Y.; Li, J.; Qi, J.; Zhou, H.; Liu, S.; Han, X. Vapor−Liquid Equilibria for Ternary Mixtures of Isopropyl Alcohol, Isopropyl Acetate, and DMSO at 101.3 kPa. J. Chem. Eng. Data 2016, 61, 3013−3019. (18) Zhang, X.; Hu, D.; Zhao, Z. Measurement and Prediction of Vapor Pressure for H2O + CH3OH/C2H5OH + [BMIM][DBP] Ternary Working Fluids. Chin. J. Chem. Eng. 2013, 21, 886−893. (19) Aspentech. Aspen Property System: Physical Property Methods and Models 11.1; Aspen Technology, Inc.: Burlington, MA, 2001; pp 20−33. (20) Wisniak, J.; Tamir, A. Vapor−liquid equilibriums in the ternary systems water−formic acid−acetic acid and water−acetic acid− propionic acid. J. Chem. Eng. Data 1977, 22, 253−260. (21) Wisniak, J.; Tamir, A. Ternary vapor−liquid equilibriums in the system methyl ethyl ketone−diethyl ketone−methyl isobutyl ketone. J. Chem. Eng. Data 1976, 21, 185−187. (22) Hsueh, A. C.; Mendel, J. M. Perturbation analysis of a maximum−likelihood objective function. IEEE Trans. Autom. Control 1983, 28, 1122−1124. (23) Widagdo, S.; Seider, W. D. Journal review. Azeotropic distillation. AIChE J. 1996, 42, 96−130.

G

DOI: 10.1021/acs.jced.8b00488 J. Chem. Eng. Data XXXX, XXX, XXX−XXX