Liquid–Liquid Equilibrium for Ternary Systems ... - ACS Publications

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Liquid−Liquid Equilibrium for Ternary Systems Water + Acetic Acid + m‑Xylene and Water + Acetic Acid + o‑Xylene at (303.2 to 343.2) K Zhipeng Shen,† Qinbo Wang,*,† Binwei Shen,‡ Chuxiong Chen,‡ and Zhenghua Xiong‡ †

Department of Chemical Engineering, Hunan University, Changsha, 410082 Hunan, P. R. China Quzhou Qunying Chemical Technology Co. Ltd., Quzhou, 324002 Zhejiang, P. R. China

‡

ABSTRACT: Liquid−liquid equilibrium (LLE) for ternary systems water + acetic acid + m-xylene and water + acetic acid + o-xylene were measured at (303.2 to 343.2) K and under atmospheric pressure. The consistency of the experimental tie-line data was checked by both the Othmer−Tobias and the Hand equations as well as verified by comparison with the literature data. Both the nonrandom two-liquid (NRTL) and universal quasichemical activity coefficient (UNIQUAC) models were adopted to correlate the measured LLE data, and the binary interaction parameters were obtained by data-fitting. The predicted LLE data by using the obtained model parameters show good consistency with the literature data. It indicates the obtained binary NRTL and UNIQUAC model interaction parameters could be used in the calculation of LLE for the ternary systems water + acetic acid + m-xylene and water + acetic acid + o-xylene as well as for the design, simulation, and optimization of the related separation process. Othmer−Tobias and Hand equations.22,23 NRTL 24 and UNIQUAC25 models were applied to correlate the experimental results, and the relevant model interaction parameters were obtained. To verify the reliability of the regressed NRTL model parameters, the LLE data at 293.2 K were predicted by using these model parameters and compared with literature data. It indicates that the obtained NRTL parameters are predictable and can be extrapolated to a wider temperature range.

1. INTRODUCTION Isophthalic acid and o-toluic acid are important chemical raw materials.1,2 Incipiently, they were manufactured by the oxidation of xylene isomers using nitric acid as an oxidant. Thus, this process requires strong corrosion resistant materials to protect the equipment and produces a large amount of NOx which is undesirable and pollutes environment seriously.3,4 Currently, the environmentally friendly technology of manufacturing isophthalic acid and o-toluic acid is the liquid-phase catalytic oxidation of xylene isomers, in which acetic acid (HOAc) is used as solvent, cobalt/manganese/bromide is used as catalyst.5,6 In the oxidation process, water is one of the byproducts. Due to the existence of water, the reaction mixture would split into two liquid phases, an upper xylene-rich phase essentially containing the unconverted xylene isomers, HOAc solvent, and water, and a lower water-rich phase essentially containing HOAc, water, and xylene isomers. In order to simulate, design, and optimize the related separation process, it is essential to measure the liquid−liquid equilibrium (LLE) data for ternary systems water + acetic acid + m-xylene and water + acetic acid + o-xylene. From the literature survey results, the LLE data for binary systems of water + m-xylene7−18 and water + o-xylene7−9,18−20 could be found. Furthermore, only Ratkovics21 measured the LLE data for the ternary system water + acetic acid + o-xylene at 293.15 K and 101.3 kPa, and the measured data were difficult to extrapolate to other temperature. Meanwhile, there are no reports or publications for the ternary system water + acetic acid + m-xylene. In this work, the LLE data of water + acetic acid + m-xylene and water + acetic acid + o-xylene have been measured at temperatures T = (303.2 to 343.2) K and atmospheric pressure. The reliability of the experimental tie-line data were tested by © XXXX American Chemical Society

2. EXPERIMENTAL SECTION 2.1. Materials. HOAc, m-xylene and N,N-dimethylformamide were purchased from Sinopharm Chemical Reagent Co. and were both received with a declared purity of >0.990 mass fraction. o-Xylene was purchased from Guangfu Chemical Reagent Co and the declared purity is >0.990 in mass fraction. Purified water produced by Hangzhou Wahaha Group Co was bought from supermarket, and had the measured resistivity of 18.2 MΩ·cm. The relevant chemical reagent purities were checked by gas chromatograph (GC). The chemicals were used without further purifications. The detailed information about the chemicals is listed in Table 1. 2.2. Apparatus and Procedures. The details of apparatus and procedures described by Wang et al.26 and our recent work27−29 have good use for reference to this work. Before the experiment, the prepared mixtures (water + acetic acid + m-xylene and water + acetic acid + o-xylene) were added into a 100 mL round-bottom glass bottle by mass at known ratios. The bottle was Received: January 13, 2015 Accepted: August 10, 2015

A

DOI: 10.1021/acs.jced.5b00043 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 2. Experimental LLE Data in Mass Fractions, w, of the Ternary System Water (1) + Acetic Acid (2) + m-Xylene (3) at (303.2 to 343.2) K and Pressure p = 101.3 kPaa

Table 1. Suppliers and Mass Fraction of the Chemicals components acetic acid m-xylene o-xylene N,Ndimethylformamide 1,3,5trimethylbenzene a

suppliers Sinopharm Chemical Reagent Co. Sinopharm Chemical Reagent Co. Guangfu Chemical Reagent Co. Sinopharm Chemical Reagent Co. Adamas Reagent, Ltd.

mass fraction purity

analysis method

> 0.990

GCa

> 0.990

GCa

> 0.990

GCa

> 0.990

GCa

> 0.990

GCa

T K

w13

w23

w33

w11

w21

w31

0.0006 0.0035 0.0039 0.0047 0.0051 0.0052 0.0055 0.0058 0.0098 0.0350 0.0010 0.0058 0.0074 0.0079 0.0106 0.0107 0.0124 0.0166 0.0200 0.0482 0.0009 0.0057 0.0067 0.0074 0.0075 0.0081 0.0083 0.0121 0.0145

0.0000 0.0026 0.0103 0.0169 0.0262 0.0418 0.0707 0.1163 0.2120 0.4169 0.0000 0.0011 0.0075 0.0169 0.0247 0.0419 0.0712 0.1128 0.1949 0.4686 0.0000 0.0037 0.0064 0.0155 0.0248 0.0384 0.0712 0.1035 0.1772

0.9994 0.9939 0.9858 0.9783 0.9687 0.9530 0.9238 0.8780 0.7782 0.5481 0.9990 0.9931 0.9850 0.9752 0.9647 0.9473 0.9163 0.8706 0.7851 0.4832 0.9991 0.9905 0.9869 0.9771 0.9676 0.9535 0.9205 0.8844 0.8083

0.9998 0.9061 0.8094 0.7044 0.6118 0.5203 0.4227 0.3172 0.2334 0.1084 0.9996 0.9030 0.7986 0.7000 0.6042 0.5166 0.4105 0.3121 0.1969 0.0750 0.9996 0.9055 0.8120 0.7044 0.6175 0.5221 0.4131 0.3143 0.2111

0.0000 0.0935 0.1900 0.2944 0.3850 0.4738 0.5631 0.6552 0.7076 0.6865 0.0000 0.0964 0.2005 0.2983 0.3914 0.4761 0.5747 0.6577 0.7362 0.6460 0.0000 0.0936 0.1869 0.2938 0.3790 0.4709 0.5703 0.6526 0.7156

0.0002 0.0004 0.0005 0.0012 0.0032 0.0059 0.0142 0.0275 0.0589 0.2051 0.0004 0.0006 0.0010 0.0017 0.0044 0.0073 0.0148 0.0301 0.0669 0.2790 0.0004 0.0009 0.0011 0.0018 0.0035 0.0070 0.0166 0.0330 0.0733

333.2

0.0011 0.0042 0.0047 0.0072 0.0077 0.0091 0.0100 0.0124 0.0155

0.0000 0.0043 0.0094 0.0170 0.0288 0.0454 0.0720 0.1162 0.2078

0.9989 0.9915 0.9859 0.9757 0.9635 0.9455 0.9180 0.8714 0.7767

0.9991 0.9011 0.8103 0.6981 0.6135 0.5161 0.4023 0.3080 0.2025

0.0000 0.0980 0.1883 0.2993 0.3824 0.4747 0.5780 0.6536 0.7092

0.0009 0.0009 0.0015 0.0025 0.0041 0.0092 0.0197 0.0384 0.0882

343.2

0.0015 0.0049 0.0065 0.0071 0.0076 0.0080 0.0116 0.0146 0.0173

0.0000 0.0031 0.0093 0.0191 0.0300 0.0438 0.0750 0.1480 0.1994

0.9985 0.9920 0.9842 0.9738 0.9624 0.9482 0.9133 0.8374 0.7833

0.9993 0.9037 0.8076 0.7015 0.6079 0.5096 0.3929 0.3155 0.2040

0.0000 0.0953 0.1910 0.2958 0.3873 0.4791 0.5855 0.6413 0.7040

0.0007 0.0011 0.0015 0.0026 0.0048 0.0113 0.0216 0.0432 0.0920

313.2

323.2

3. RESULTS AND DISCUSSION 3.1. Experimental Results. The experimentally measured LLE data of the ternary systems of water (1) + acetic acid (2) + m-xylene (3) and water (1) + acetic acid (2) + o-xylene (3) at (303.2, 313.2, 323.2, 333.2, and 343.2) K and atmospheric pressure are presented in Tables 2 and 3, and the experimental data of the ternary system at different temperatures are plotted in Figures 1 and 2. All concentrations are listed in mass fraction. Tables 2 and 3 give the result that two liquid phases in the last bottle have been miscible homogeneous phase at (323.2 and 313.2) K. Hence, the tenth tie line data are not presented in Tables 2 and 3, and plotted in Figures 1 and 2 at (323.2 to 343.2) K and (313.2 to 343.2) K for the ternary systems of water + acetic acid + m-xylene and water + acetic acid + o-xylene, respectively. To ascertain the reliability of the experimental tie-line results, the Othmer−Tobias22 (eq 1) and Hand equations23 (eq 2) were used. These equations are shown as ⎛ 1 − w33 ⎞ ⎛ 1 − w11 ⎞ ln⎜ ⎟ ⎟ = m + n ln⎜ ⎝ w11 ⎠ ⎝ w33 ⎠

aqueous phase

303.2

Gas chromatograph.

sealed by a rubber stopper to ensure that the prepared mixtures were not polluted. Then, the bottle was stirred in a thermostatic water bath and heated to the desired temperature within ± 0.1 K. After the mixture was stirred for 2 h, it would be left undisturbed to reach liquid- liquid equilibrium in the following 18 h. To analyze the composition of each liquid phase, the samples were carefully taken from the organic phase and the aqueous phase and accurately weighed by an electronic balance (type AL204, Mettler Toledo instrument Co. Ltd., uncertainty of 0.0001 g), respectively. The samples were diluted with N,Ndimethylformamide and measured by the gas chromatograph (KeXiao GC1690) with a flame ionization detector (FID) and a capillary column (30 m long, 0.32 mm i.d.). The injection-port temperature was fixed at 513.15 K, and the detector was held at 533.15 K. The internal standard method was used to quantify the amount of substances involved in the LLE system, and mesitylene was chosen as the internal standard substance. The water content in each sample was measured by a Karl Fisher titrator (Mettle-Toledo V20). The normalization method was used to calculate the concentrations of water and xylene in the aqueous phase and the organic phase, respectively. In order to verify the reliability and the repeatability of the analytical method of gas chromatography, five acetic acid + m-xylene and acetic acid + o-xylene solutions of known concentration were analyzed. For each solution, the composition was measured at least five times. The relative standard uncertainty are ur(w) = 0.005 for w ≥ 0.02, and u(w) = 0.0001 for w < 0.02, where w is the mass fraction of component.

organic phase

a Standard uncertainties u are u(T) = 0.1 K, ur(w) = 0.005 for w ≥ 0.02, and u(w) = 0.0001 for w < 0.02.

⎛w ⎞ ⎛w ⎞ ln⎜ 21 ⎟ = A + Bln⎜ 23 ⎟ ⎝ w11 ⎠ ⎝ w33 ⎠

(2)

where m, n, A, and B are the parameters in Othmer−Tobias equation and Hand equation, respectively. w11 and w21 are the mass fraction of water and HOAc in aqueous phase, and w23 and

(1) B

DOI: 10.1021/acs.jced.5b00043 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 3. Experimental LLE Data in Mass Fractions, w, of the Ternary System Water (1) + Acetic Acid (2) + o-Xylene (3) at (303.2 to 343.2) K and Pressure p = 101.3 kPaa T

organic phase

aqueous phase

K

w13

w23

w33

w11

w21

w31

303.2

0.0006 0.0041 0.0058 0.0070 0.0097 0.0100 0.0104 0.0111 0.0117 0.0656 0.0009 0.0058 0.0065 0.0073 0.0085 0.0087 0.0096 0.0107 0.0127

0.0000 0.0034 0.0087 0.0141 0.0182 0.0457 0.0688 0.1146 0.1821 0.4836 0.0000 0.0035 0.0096 0.0165 0.0285 0.0424 0.0684 0.1141 0.1869

0.9994 0.9925 0.9855 0.9789 0.9721 0.9443 0.9207 0.8743 0.8062 0.4508 0.9991 0.9907 0.9839 0.9761 0.9631 0.9488 0.9219 0.8751 0.8004

0.9995 0.8907 0.8008 0.6809 0.6129 0.5153 0.3966 0.3141 0.2258 0.0905 0.9997 0.8993 0.7991 0.7093 0.6116 0.5134 0.4122 0.3114 0.2141

0.0000 0.1085 0.1980 0.3172 0.3838 0.4780 0.5883 0.6551 0.7095 0.6033 0.0000 0.1001 0.1999 0.2889 0.3848 0.4793 0.5718 0.6548 0.7137

0.0005 0.0009 0.0012 0.0019 0.0033 0.0067 0.0151 0.0308 0.0647 0.3062 0.0003 0.0007 0.0010 0.0019 0.0036 0.0073 0.0159 0.0338 0.0722

0.0010 0.0060 0.0063 0.0086 0.0093 0.0103 0.0104 0.0106 0.0143

0.0000 0.0027 0.0081 0.0175 0.0302 0.0434 0.0663 0.1108 0.1888

0.9990 0.9913 0.9856 0.9739 0.9605 0.9464 0.9234 0.8787 0.7969

0.9996 0.8930 0.8003 0.7121 0.5874 0.5152 0.4098 0.3110 0.2171

0.0000 0.1061 0.1987 0.2861 0.4083 0.4768 0.5726 0.6508 0.7022

0.0004 0.0009 0.0010 0.0018 0.0043 0.0081 0.0177 0.0381 0.0807

313.2

323.2

333.2

343.2

given in Table 4, respectively. As can be seen from Table 4, the minimum correlation factor is 0.98. It indicates that the experimental data have a high degree of consistency. 3.2. Verification of Measured Binary LLE Data. The binary LLE data of water + m-xylene and water + o-xylene have been studied by some researchers.7−20 To confirm the accuracy of the measured data, the experimentally measured binary LLE data were compared with the aforementioned literature data. The results are shown in Figures 3 and 4, as can been seen, the experimental data have no significant errors with the literature data. Therefore, the obtained binary LLE data of water + m-xylene and water + o-xylene are accurate. 3.3. Correlation of Experimental Data. The LLE as the other phase equilibrium should comply with the criterion of phase equilibrium. The basic relationship of the LLE can be expressed by an activity coefficient model. In these models, the relationships for each component i in two coexistent liquid phase of a system at equilibrium are

0.0012 0.0062 0.0065 0.0078 0.0085 0.0092 0.0095 0.0096 0.0176

0.0000 0.0014 0.0058 0.0172 0.0266 0.0447 0.0729 0.1174 0.1947

0.9988 0.9924 0.9878 0.9750 0.9649 0.9461 0.9176 0.8730 0.7877

0.9997 0.9000 0.7981 0.7123 0.6000 0.5110 0.4081 0.3066 0.2122

0.0000 0.0994 0.2008 0.2856 0.3955 0.4795 0.5717 0.6503 0.6971

0.0003 0.0006 0.0010 0.0021 0.0045 0.0095 0.0202 0.0432 0.0908

0.0017 0.0045 0.0071 0.0087 0.0089 0.0093 0.0111 0.0114 0.0192

0.0000 0.0036 0.0101 0.0185 0.0281 0.0474 0.0748 0.1173 0.1936

0.9983 0.9919 0.9829 0.9728 0.9630 0.9432 0.9142 0.8714 0.7872

0.9997 0.9049 0.8001 0.7148 0.6138 0.5068 0.4071 0.3059 0.2116

0.0000 0.0946 0.1988 0.2829 0.3811 0.4823 0.5700 0.6462 0.6864

0.0003 0.0005 0.0012 0.0023 0.0050 0.0108 0.0229 0.0479 0.1019

xiIγi I = xiIIγi II

(3)

∑ xiI = 1

(4)

∑ xiII = 1

(5)

where xIi , xIIi , γIi , and γIIi are the mole fractions and activity coefficients of i in the aqueous phase and organic phase, respectively. Both the NRTL and UNIQUAC activity coefficients are widely used to calculate activity coefficients and correlate experimental data. Therefore, the measured experimental results were correlated with NRTL and UNIQUAC models. The NRTL equation used in this work is24 3

ln γi =

∑ j = 1 τjiGjixj 3 ∑k = 1 Gkixk

3

+

Gijxj 3 j = 1 ∑k = 1 Gkjxk

∑

3 ⎛ ∑ τ G x ⎞ ⎜τ − k = 1 kj kj k ⎟ 3 ⎜ ij ∑k = 1 Gkjxk ⎟⎠ ⎝

τij = aij +

(6)

bij (7)

T

Gij = exp( −αijτij) αij = αji

τij ≠ τji

(8)

τii = 0

(9)

where, xi is the mole fraction of the component i and γi is the activity coefficient of component i, T is the absolute temperature. aij and bij are the parameters needed to be regressed. The upper and lower limit of bij is 10 000 K and −10 000 K, respectively. The UNIQUAC equation used in this work is25

a Standard uncertainties u are u(T) = 0.1 K, ur(w) = 0.005 for w ≥ 0.02, and u(w) = 0.0001 for w < 0.02.

ln γi = ln

w33 are the mass fraction of HOAc and xylene in the organic phase, respectively. By linear fitting the experimental data listed in Table 4 with eqs 1 and 2, the parameters of Othmer−Tobias and Hand equation together with the correlation factors (R2) were obtained and

φi xi

+

φ θi ⎛z⎞ ⎜ ⎟q ln + li − i i ⎝2⎠ xi φi

3 ⎡ + qi⎢1 − ln(∑ θτ j ji) − ⎢⎣ j=1

C

3

∑ j=1

3

∑ xjlj j=1

⎤ ⎥ 3 ∑k = 1 θkτkj ⎥⎦ θτ j ji

(10)

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Figure 1. LLE data of the ternary system water (1) + acetic acid (2) + m-xylene (3) at different temperatures: ■■, experimental data tie line; □□, calculated data tie line using NRTL model; ◇◇, calculated data tie line using UNIQUAC model. wi is the mass fraction of component of i in water (1) + acetic acid (2) + m-xylene (3) solvent mixtures.

where θi and φi represent the area fraction and the volume fraction of component i, respectively. These parameters of UNIQUAC are calculated by the following equations: li =

θi =

z (ri − qi) − (ri − 1) 2 qixi 3

∑i = 1 qixi

φi =

interaction parameters listed in Table 6 were obtained by data regression. The optimization algorithm of Nelder−Mead Simplex approach30 was applied in the parameters estimation program, which has been applied successfully in our previous work.27−29 Function f minsearch in the optimization toolbox of Matlab (Mathwork, MA) uses the Nelder−Mead Simplex approach and can be employed for the minimization of the objective function. The objective function (OF) used in this work is

(11)

rx i i 3

∑i = 1 rx i i

⎛ bij ⎞ τji = exp⎜aij + ⎟ T⎠ ⎝

⎛ ⎛ x exp − x calc ⎞2 ijkt ijkt ⎜ ⎟ OF = min⎜∑ ∑ ∑ ∑ ⎜⎜ exp ⎟ ⎜ t k j i ⎝ xijkt ⎠ ⎝

(12)

where z is the number of close interacting molecules around a central molecule and set to 10. aij and bij are UNIQUAC coefficients of the equations for binary interaction parameters needed to be regressed. The upper and lower limit of bij is 10 000 K and −10 000 K, respectively. The pure component structural parameters (r and q) are listed in Table 5. Using the Matlab program, the experimental data were correlated by both the NRTL and UNIQUAC models, the binary

⎛ x expI × γ I − x expII × γ II ⎞2 ⎞ ikt ikt ikt ikt ⎟ ⎟ + ∑ ∑ ∑ ⎜⎜ ⎟ ⎟⎟ expI I xikt × γikt ⎠⎠ t k i ⎝

(13)

cal where xexp ijkt and xijkt are the experimental and calculated mole expI expII I fractions. xikt ,xikt , γikt and γIIikt are the experimental mole fractions

D

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Figure 2. LLE data of the ternary system water (1) + acetic acid (2) + o-xylene (3) at different temperatures: ■■, experimental data tie line; □□, calculated data tie line using NRTL model; ◇◇, calculated data tie line using UNIQUAC model. wi is the mass fraction of component of i in water (1) + acetic acid (2) + o-xylene (3) solvent mixtures.

Table 4. Parameters of the Othmer−Tobias and Hand Equations for Water (1) + Acetic Acid (2) + m-Xylene (3) System and Water (1) + Acetic Acid (2) + o-Xylene (3) System at (303.2 to 343.2) K Equation

T

Othmer−Tobias

K 303.15 313.15 323.15 333.15 343.15 K 303.15 313.15 323.15 333.15 343.15

Hand

m-xylene system m 2.5440 2.5724 2.9499 3.6131 2.6188 A 2.1369 2.1069 2.4881 3.2690 2.2423

o-xylene system R2 a 0.9868 0.9966 0.9806 0.9956 0.9857 R2 a 0.9944 0.9874 0.9925 0.9957 0.9935

n 0.9166 0.9378 1.0498 1.2077 0.9741 B 0.7434 0.6798 0.8198 1.0153 0.7789

m 2.3721 2.8692 2.7835 2.6571 2.7729 A 2.0894 2.4186 2.2706 2.0157 2.3822

n 0.8570 1.0408 1.0072 0.9567 1.0261 B 0.7020 0.8155 0.7586 0.6651 0.8234

R2 a 0.9824 0.9903 0.9936 0.9903 0.9958 R2 a 0.9817 0.9994 0.9964 0.9892 0.9990

a 2

R is the linear correlation factor E

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and calculated activity coefficients of component i in the aqueous phase and organic phase, respectively. The subscripts i, j, k, t denote component, phase, and tie-line, temperature, respectively. In order to evaluate the quality of the used models, the root mean square deviation (rmsd) between experimental and calculated data was determined by using the following equation: 1/2 exp calc 2 ⎞ ⎛ (xijkt − xijkt ) ⎜ ⎟ rmsd = ⎜∑ ∑ ∑ ∑ ⎟ 6N ⎝ t k j i ⎠

where N is the number of the tie-lines. To obtain a unique set of parameters valid for all the range of temperatures studied, a simultaneous regression of all experimental data was carried out. Table 6 gives the optimized NRTL and UNIQUAC model parameters obtained in a simultaneous correlation of all data assuming temperature independent parameters. For water (1) + acetic acid (2) + m-xylene (3) system, as listed in Table 6, the rmsd values for the NRTL and UNIQUAC model were 0.0200 and 0.0074, respectively, and for water (1) + acetic acid (2) + o-xylene (3) system, the rmsd values for the NRTL and UNIQUAC model were 0.0085 and 0.0041, respectively. By the criterion of phase equilibrium, it is known that the activities of each component i in two coexistent liquid phases of a system at equilibrium are equal. In this paper, the activities of HOAc in two liquid phases are illustrated in Figures 5 and 6 for the ternary systems water + acetic acid + m-xylene and water + acetic acid + o-xylene, respectively. As can be seen from Figures 5 and 6, it is obvious that the points representing the activities of HOAc in two liquid phases are close to the line which is composed of the points of equal activities. Therefore, the measured LLE data for the ternary systems water + acetic acid + m-xylene and water + acetic acid + o-xylene are successfully correlated, and the used objective function and obtained model parameters are reliable. 3.4. Model Verification. Ratkovics21 measured the LLE data for the ternary system water + acetic acid + o-xylene at 293.15 K under atmospheric pressure. The experimental data are illustrated in Figure 7. In this work, LLE data for the ternary system water + acetic acid + o-xylene have been measured at (303.2 to 343.2) K under atmospheric pressure. The relevant NRTL model parameters listed in Table 6 were regressed at all the range of temperatures. In order to verify the reliability of the regressed NRTL model parameters and to evaluate the precision of model extrapolation, the LLE data at 293.15 K were predicted by using these NRTL model parameters. The predicted data are illustrated in Figure 7, too. As can be seen from Figure 7, the predicted results have

Figure 3. Comparisons between experimental solubility of m-xylene in water and water in m-xylene with solubility data reported in literature: ■, solubility of m-xylene in water; ●, solubility of water in m-xylene; □, Polak et al;7 △, Sanemasa et al;8 ⊗, Chernoglazova et al;9 ▽, Miller et al;10 ○, Sawamura et al;11 ◁, Pryor et al;12 ◇, Anderson et al;13 ☆, Tu et al;14 ⊙, Mathis et al;15 + , Economou et al; 16 × , Englin et al;17 ⊕, Högfeldt et al.18 w3 is the mass fraction of m-xylene.

Figure 4. Comparisons between experimental solubility of o-xylene in water and water in o-xylene with solubility data reported in literature: ■, solubility of o-xylene in water; ●, solubility of water in o-xylene; □, Polak et al;7 △, Sanemasa et al;8 ⊕, Högfeldt et al;18 ⊖, Ben-Naim et al;19 ◁, Letcher et al.20 w3 is the mass fraction of o-xylene.

Table 5. UNIQUAC Structural Parameters r and q component

r

q

acetic acid water m-xylene o-xylene

2.2024 0.9200 4.6578 4.6578

2.0720 1.4000 3.5360 3.5360

(14)

Table 6. Binary Interaction Parameters of NRTL and UNIQUAC Models for the System Water (1) + Acetic Acid (2) + m-Xylene (3) + o-Xylene (4) at (303.2 to 343.2) K model NRTL

UNIQUAC

i−j

aij

bij

aji

bji

αij = αji

rmsd

1−2 1−3 2−3 1−4 2−4 1−2 1−3 2−3 1−4 2−4

6.69 1.34 3.27 1.13 −0.34 −4.88 −2.76 7.00 −2.30 2.44

−1306.90 2193.90 −118.95 2205.20 953.39 1456.40 658.67 −2318.50 483.78 −792.15

−2.81 −2.74 −0.03 −0.50 −0.54 0.78 0.53 −9.10 −0.94 −4.53

137.56 1777.50 −212.99 1043.50 6.50 27.99 −739.88 2804.20 −229.36 1287.20

0.30 0.20 0.30 0.20 0.30

0.0200

F

0.0085 0.0074

0.0041

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4. CONCLUSIONS Liquid−liquid equilibrium (LLE) data for the ternary systems water + acetic acid + m-xylene and water + acetic acid + o-xylene were determined at T = (303.2 to 343.2) K and at atmospheric pressure. The reliability of determined binary data was verified by comparison with the literature data. The degree of consistency of the experimental data was confirmed by applying the Othmer− Tobias and the Hand equations. The experimental results were correlated with both the NRTL and the UNIQUAC activity coefficient models. The relevant parameters were regressed by data fitting. The calculated results show good agreement with the experimentally determined ternary LLE data. Thus, the obtained interaction parameters are useful for the calculation of LLE for the ternary systems water + acetic acid + m-xylene and water + acetic acid + o-xylene as well as for the design and optimization of the related separation process.

Figure 5. Activity of acetic acid in the organic phase versus the activity of acetic acid in the aqueous phase at different temperatures for the ternary system water + acetic acid + m-xylene, NRTL model: ■, 303.2K; ●, 313.2K; ▲, 323.2K; ▼, 333.2K; ⧫, 343.2K. UNIQUAC model: □, 303.2K; ○, 313.2K; △, 323.2K; ▽, 333.2K; ◇, 343.2K.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest. Funding

The project was granted financial support from Key S&T Special Project of Zhejiang Province (2012C13007-2) and the Fundamental Research Funds for the Central Universities.

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REFERENCES

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Figure 6. Activity of acetic acid in the organic phase versus the activity of acetic acid in the aqueous phase at different temperatures for the ternary system water + acetic acid + o-xylene, NRTL model: ■, 303.2K; ●, 313.2K; ▲, 323.2K; ▼, 333.2K; ⧫, 343.2K. UNIQUAC model: □, 303.2K; ○, 313.2K; △, 323.2K; ▽, 333.2K; ◇, 343.2K.

Figure 7. Correlated LLE data for the ternary water (1) + acetic acid (2) + o-xylene (3) system at 101.3 kPa: ●, literature data binodal curve; ■■, literature data tie line; □□, correlated data tie line using NRTL model. wi is the mass fraction of component i in water (1) + acetic acid (2) + o-xylene (3) solvent mixtures.

no important deviations with the experimental liquid−liquid envelop so that the NRTL model parameters listed in Table 6 are predictable and can be extrapolated to a wider temperature range. G

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H

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