Ternary and Quaternary Liquid–Liquid Equilibria for Systems of Methyl

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Ternary and Quaternary Liquid−Liquid Equilibria for Systems of Methyl Butyl Ketone + Water + Hydroquinone + Phenol at 313.2 K and Atmospheric Pressure Huimin Wang, Zhuo Wang, Libo Li, and Yun Chen* Key Laboratory of Heat Transfer Enhancement and Energy Conservation of Ministry of Education, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, P. R. China ABSTRACT: Liquid−liquid equilibria (LLE) data of the quaternary system {methyl butyl ketone + phenol + hydroquinone + water} and two relevant ternary systems, {methyl butyl ketone + phenol + water} and {methyl butyl ketone + hydroquinone + water}, were measured at T = 313.2 K and p = 101.3 kPa. The experimental data were correlated with the nonrandom two-liquid (NRTL) and universal quasichemical (UNIQUAC) models. The root-mean-square deviation of the NRTL and UNIQUAC models were 0.144 and 0.0476%, respectively. Good agreement was found between experimental LLE data and those calculated from the NRTL or UNIQUAC equations for all systems studied in this work.

1. INTRODUCTION Phenol and its derivative hydroquinone are toxic pollutants frequently found in the wastewater of various processes, such as oil refining, coking, coal processing, petrochemical manufacture, wood processing, and so forth. Phenols are very harmful to the environment even at low concentrations in water. According to the World Health Organization, the maximum concentration of phenols allowed in drinking water is 0.001 mg L−1.1 Thus, it is necessary to remove phenols from industrial wastewater streams before discharging them into the environment. For treating high concentration phenol wastewater (over 1000 mg L−1), solvent extraction is a preferred method, and many organic solvents, such as butyl acetate, methyl isobutyl ketone (MIBK), and diisopropyl ether (DIPE), are frequently used to extract the phenols.2 However, many industrial phenolic wastewaters have very complex compositions that contain polyhydric phenols, such as dihydric and trihydric phenols, with concentrations of hundreds or even thousands of milligrams per liter. These polyhydric phenols are more difficult to extract due to their high affinity for water and low affinity for organic solvents. In this work, phenol is selected as the representative of monohyeric phenol and hydroquinone as the representative of polyhydric phenol. Specifically, phenol and hydroquinone are two major phenolic pollutants according to Yang et al.3 A wide range of solvents have been developed to extract phenolic pollutants from wastewater, such as DIPE, butyl acetate, and MIBK, to name just a few. However, most of these extractants suffer from some flaws, e.g., low boiling point or azeotropic point with water, low distribution coefficients, hydrolysis, considerable water concentration in the azeotrope, which leads to higher energy consumption when stripping water from it, and so forth. Nevertheless, methyl butyl ketone (MBK) is an excellent extractant recently © XXXX American Chemical Society

developed by our group, which has overcome these shortcomings and has very promising application potential in wastewater treatment. Thus, we study the performance of MBK to extract phenol and hydroquinone in this work with the aim to improve the current industrial wastewater extraction method. Liquid−liquid equilibria (LLE) data are important for phenol extraction processes. Some studies have been carried out in recent years measuring LLE data for different quaternary solvent + phenol + hydroquinone + water systems. Yang et al.3 reported LLE data for the MIBK + water + phenol + hydroquinone system at 298.15 K. Lei et al.4 measured LLE data for the MTBE + phenol + hydroquinone + water system at 313.15 K. In our previous work,5 LLE data for MBK + phenol + water and for MBK + hydroquinone + water at 298.15 K and 323.15 K have been reported. In this work, LLE data for ternary systems {MBK+ water + phenol} and {MBK + water + hydroquinone} were measured at 313.2 K under atmospheric pressure. The other relevant quaternary system, {MBK + water + phenol + hydroquinone}, was also studied under the same conditionS. The nonrandom two-liquid (NRTL)6 and universal quasi-chemical activity coefficient (UNIQUAC)7 models were used to correlate our measured LLE data to obtain binary interaction parameters among MBK, phenol, hydroquinone, and water. All of these results should be useful for designing and simulating extraction processes for phenols with MBK. Other predictive models like UNIFAC-Dortmund were also attempted, which yielded larger RMSDs of ∼0.01 and thus are not shown. Received: October 29, 2015 Accepted: March 17, 2016

A

DOI: 10.1021/acs.jced.5b00918 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Table 1. Physical Properties and Purity Grade (Mole Fraction) of Studied Chemicals at 101.325 kPaa density (g cm−3)

a

chemical

purity (mole fraction)

analysis method

MBK (293.2 K) phenol (314.5 K) hydroquinone (293.2 K) 1-octanol (293.2 K) n-propyl acetate (293.2 K)

0.99 0.995 0.99 0.995 0.999

GC GC GC GC GC

b

refractive index

purification method

exp.

lit.9,10

exp.

lit.9,10

none none none none none

0.811 1.0581 1.332 0.8236 0.889

0.810 1.0576 1.332 0.8239 0.889

1.40065 1.54182

1.40072 1.54178

1.4288 1.3842

1.4292 1.3844

Standard uncertainties u are u(T) = 0.1 K, u(p) = 1 kPa, u(density) = 0.001 g cm−3, and u(nD) = 0.0002. bGas chromatography.

2. EXPERIMENTAL SECTION 2.1. Materials. MBK and n-propyl acetate were purchased from XiYa Reagent Co., Ltd. Phenol was obtained from GuangZhou Chemical Reagent Factory. Hydroquinone and 1-octanol were obtained from TianJin Kemiou Chemical Reagent Co., Ltd. The purity grade (expressed as mole fraction) for chemicals used in this work are listed in Table 1. Their purities were confirmed by gas chromatography. The density was obtained with a DH-120T density meter (can measure the density of solid and liquid) supplied by HongTuo instruments (Dong Guan Co., Ltd.; standard uncertainty u(density) = 0.001 g cm−3).8 The refractive index was measured by an Abbe refractometer (WAY-2S; standard uncertainty u(nD) = 0.0002). Deionized or distilled water was used in our experiments. All chemicals in this study were used without further purification. 2.2. Apparatus and Procedures. Methods and procedures employed in our LLE experiments were similar to those in Yang’s work.3 The quaternary mixture was prepared by mixing MBK and a preprepared phenol-hydroquinone [(1 − M)×phenol + M×hydroquinone] aqueous solution, where M denotes the mass ratio of hydroquinone to phenol + hydroquinone. Figure 1

temperature constant. Considering the temperature of industrial wastewater, LLE data were measured at 313.2 K and 101.3 kPa. The temperature was controlled by a thermostatic bath with a fluctuation of ±0.1 K. The quaternary mixture was loaded into the glass cell, vigorously agitated by a magnetic stirrer for at least 2 h, and then left to stand for at least 12 h to reach phase equilibrium. After the mixture formed two separate phases, samples from both phases were collected by syringes and were analyzed using gas chromatography (GC6820, Agilent Technologies) equipped with a flame ionization detector (FID) and a DB-5MS capillary column (30 m × 0.32 mm × 0.25 μm). The temperatures of injector and detector were set at 523.15 K and 543.15 K, respectively. The initial temperature of the column was kept at 313.2 K for 2 min and then increased at a rate of 30 K min−1 to reach 463.15 K. The carrier gas was nitrogen with a rate of 30 mL min−1. The sample compositions were analyzed with an internal standard method (Yang analyzed their samples with an external standard method,3 which is the main difference between our procedure and theirs). Samples and internal standards were weighed on an analytical balance (Shimadzu, AUW220D, standard uncertainty u(mass) = 0.1 mg). N-Propyl acetate was chosen as the internal standard for MBK, and 1-octanol was chosen for phenol and hydroquinone. Water concentration was obtained by deducting all other component concentrations from 1. Each sample was analyzed at least 3 times, and the resulting standard deviation was less than 0.2%; thus, the average result was reported as the sample’s composition.

3. RESULTS AND DISCUSSION 3.1. LLE Experimental Data. Experimental results for ternary systems MBK + water + phenol and MBK + water + hydroquinone are listed in Tables 2 and 3, respectively. LLE data for the quaternary system MBK + water + phenol + hydroquinone are listed in Table 4. All concentrations are expressed as mole fraction. A diagram for the quaternary system is shown in Figure 1, and the LLE data for ternary systems were also plotted in triangular diagrams as in Figure 2, where (a) is the system of {MBK + water + phenol} at T = 313.2 K and (b) is the system of {MBK + water + hydroquinone} at T = 313.2 K. For the ability of MBK to extract phenol or hydroquinone from wastewater to be estimated, the distribution coefficient (D) and separation factors (S) are determined as

Figure 1. Diagram for the quaternary system MBK + water + (1 − M)×phenol + M×hydroquinone (with M being the mass ratio of hydroquinone to phenol + hydroquinone) at 313.2 K.

shows the constitution for the quaternary system in this work schematically; the values of M were 0.1998, 0.3990, 0.5984, and 0.7971. As this study is focused on the recovery of dilute phenol and hydroquinone from industrial wastewater, the LLE data are determined for low total concentrations of phenol and hydroquinone where MBK is completely miscible with phenol or hydroquinone. The experiment was carried out using a 100 mL glass equilibrium cell equipped with a heating jacket to keep the

D=

xiI xiII

S=D

(1)

x 2II x 2I

where superscripts I and II denote organic solvent phase and aqueous phase, respectively. The distribution coefficients and B

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Table 2. Experimental LLE Data (Mole Fraction) for the Ternary System MBK (1) + Water (2) + Phenol (3) at T = 313.2 K and p = 101.3 kPaa organic phase xI1 0.6860 0.7065 0.7419 0.7740 0.7945 0.8066 0.8195 0.8232 0.8374 0.8672 a

aqueous phase

xI2

xI3

0.2022 0.1944 0.1809 0.1686 0.1608 0.1562 0.1513 0.1499 0.1445 0.1328

1.118 9.913 7.725 5.736 4.467 3.721 2.921 2.693 1.818 0

× × × × × × × × ×

xII1 −1

10 10−2 10−2 10−2 10−2 10−2 10−2 10−2 10−2

× × × × × × × × × ×

2.087 2.100 2.122 2.139 2.149 2.155 2.161 2.162 2.168 2.185

xII2 −3

10 10−3 10−3 10−3 10−3 10−3 10−3 10−3 10−3 10−3

0.9976 0.9976 0.9977 0.9977 0.9977 0.9978 0.9978 0.9978 0.9978 0.9978

xII3 3.299 2.822 2.067 1.435 1.067 8.661 6.631 6.070 3.982 0

× × × × × × × × ×

10−4 10−4 10−4 10−4 10−4 10−5 10−5 10−5 10−5

D

S

339.0 351.2 373.7 399.8 418.6 429.6 440.6 443.6 456.5

1672.5 1802.2 2061.0 2365.8 2597.2 2744.3 2905.7 2952.8 3152.2

Standard uncertainties u are u(T) = 0.1 K, u(p) = 1 kPa, u(x) = 0.002 for x > 0.1, and u(x) = 0.0001 for x < 0.1.

Table 3. Experimental LLE Data (Mole Fraction) for the Ternary System MBK (1) + Water (2) + Hydroquinone (3) at T = 313.2 K and p = 101.3 kPaa organic phase xI1 0.7286 0.7589 0.7857 0.8055 0.8133 0.8254 0.8351 0.8507 0.8567 0.8611 0.8672 a

aqueous phase

xI2

xI3

0.1922 0.1792 0.1678 0.1594 0.1561 0.1509 0.1467 0.1401 0.1375 0.1357 0.1328

7.920 6.182 4.645 3.509 3.065 2.374 1.812 9.189 5.734 3.235 0

× × × × × × × × × ×

xII1 −2

10 10−2 10−2 10−2 10−2 10−2 10−2 10−3 10−3 10−3

1.604 1.756 1.879 1.961 1.994 2.043 2.080 2.133 2.151 2.164 2.185

× × × × × × × × × × ×

xII2 −3

10 10−3 10−3 10−3 10−3 10−3 10−3 10−3 10−3 10−3 10−3

0.9966 0.9969 0.9972 0.9974 0.9974 0.9975 0.9976 0.9977 0.9978 0.9978 0.9978

xII3 1.764 1.297 9.201 6.685 5.691 4.193 3.038 1.417 8.560 4.693 0

× × × × × × × × × ×

10−3 10−3 10−4 10−4 10−4 10−4 10−4 10−4 10−5 10−5

D

S

44.9 47.7 50.5 52.5 53.9 56.6 59.6 64.9 67.0 68.9

232.8 265.4 300.1 328.5 344.4 374.1 405.3 462.2 486.2 506.6

Standard uncertainties u are u(T) = 0.1 K, u(p) = 1 kPa, u(x) = 0.002 for x > 0.1, and u(x) = 0.0002 for x < 0.1.

Table 4. Experimental LLE Data (Mole Fraction) for the Quaternary System MBK (1) + Water (2) + Phenol (3) + Hydroquinone (4) at T = 313.2 K and p = 101.3 kPaa organic phase xI1

xI2

xI3

aqueous phase xI4

xII1

× 10

3

xII2

0.6678 0.7330 0.7600 0.7826 0.7987 0.8115 0.8237 0.8362 0.8447

0.2105 0.1853 0.1748 0.1660 0.1597 0.1548 0.1500 0.1452 0.1419

0.1039 0.0689 0.0547 0.0429 0.0346 0.0280 0.0218 0.0154 0.0111

0.0178 0.0128 0.0105 0.0085 0.0069 0.0057 0.0045 0.0032 0.0023

1.9610 2.0420 2.0740 2.0990 2.1160 2.1290 2.1410 2.1530 2.1600

0.9973 0.9975 0.9976 0.9976 0.9977 0.9977 0.9977 0.9978 0.9978

0.6780 0.7376 0.7555 0.7881 0.8024 0.8153 0.8261 0.8380 0.8459

0.2080 0.1845 0.1774 0.1645 0.1589 0.1537 0.1494 0.1447 0.1416

0.0788 0.0523 0.0446 0.0311 0.0253 0.0201 0.0158 0.0111 0.0080

0.0352 0.0256 0.0224 0.0163 0.0135 0.0109 0.0087 0.0062 0.0045

1.8370 1.9590 1.9950 2.0560 2.0810 2.1040 2.1210 2.1390 2.1500

0.9971 0.9973 0.9974 0.9976 0.9976 0.9977 0.9977 0.9977 0.9978

0.6837 0.7477 0.7738 0.7903 0.8056 0.8154

0.2073 0.1816 0.1710 0.1643 0.1582 0.1541

0.0546 0.0336 0.0257 0.0208 0.0165 0.0137

0.0543 0.0372 0.0295 0.0245 0.0198 0.0167

1.7080 1.8900 1.9610 2.0070 2.0470 2.0720

0.9968 0.9972 0.9974 0.9975 0.9975 0.9976

xII3 × 104 M = 0.1998 3.1500 1.8500 1.3870 1.0390 0.8084 0.6420 0.4911 0.3383 0.2397 M = 0.3990 2.2830 1.3620 1.1150 0.7393 0.5901 0.4584 0.3559 0.2456 0.1759 M = 0.5984 1.5080 0.8376 0.6180 0.4899 0.3794 0.3115 C

xII4 × 104

Dphenol

Dhydroquinone

Sphenol

Shydroquinone

3.9990 2.6240 2.0610 1.5630 1.2530 1.0000 0.7619 0.5222 0.3751

329.7 372.4 394.5 413.0 427.7 436.2 443.7 456.4 464.7

44.5 48.8 51.0 54.2 55.4 57.0 58.9 61.7 62.4

1562.0 2004.7 2251.4 2482.0 2672.0 2811.3 2951.2 3136.3 3267.6

210.8 262.7 291.1 325.7 346.1 367.4 391.8 424.0 438.8

8.5560 5.6010 4.6930 3.1380 2.5010 1.9260 1.4890 1.0150 0.7271

345.1 383.7 399.8 420.0 428.0 437.6 443.2 451.8 457.1

41.1 45.7 47.8 52.0 54.0 56.6 58.2 60.8 62.0

1654.3 2074.1 2247.8 2547.1 2687.1 2840.6 2959.7 3115.1 3221.0

197.0 247.0 268.7 315.3 339.0 367.4 388.7 419.2 436.9

13.1600 8.1670 6.1700 4.8600 3.7340 3.0300

362.0 401.1 415.4 424.8 434.1 440.0

41.3 45.5 47.8 50.5 53.1 55.2

1740.7 2202.5 2422.9 2579.1 2737.1 2848.4

198.6 249.8 278.8 306.6 334.8 357.3

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Table 4. continued organic phase xI1

xI2

xI3

aqueous phase xI4

xII1 × 103

xII3 × 104

xII2

0.8277 0.8376 0.8455

0.1491 0.1451 0.1419

0.0103 0.0077 0.0056

0.0128 0.0096 0.0070

2.1010 2.1220 2.1390

0.9977 0.9977 0.9977

0.6767 0.6983 0.7531 0.7723 0.7960 0.8162 0.8289 0.8456

0.2120 0.2032 0.1805 0.1725 0.1627 0.1543 0.1490 0.1421

0.0312 0.0268 0.0168 0.0136 0.0099 0.0069 0.0051 0.0028

0.0801 0.0717 0.0496 0.0415 0.0314 0.0226 0.0170 0.0095

1.5240 1.6110 1.8210 1.8880 1.9710 2.0400 2.0800 2.1280

0.9965 0.9966 0.9971 0.9972 0.9974 0.9975 0.9976 0.9977

M = 0.5984 0.2321 0.1702 0.1218 M = 0.7971 0.8098 0.6807 0.4017 0.3199 0.2286 0.1568 0.1142 0.6188

xII4 × 104

Dphenol

Dhydroquinone

Sphenol

Shydroquinone

2.2010 1.5990 1.1220

445.4 451.5 458.0

58.1 60.1 62.7

2980.4 3104.5 3220.2

388.8 413.2 440.8

19.4000 16.8500 10.6400 8.6430 6.1810 4.1260 2.9320 1.5090

385.1 393.2 417.5 426.0 434.6 443.2 450.0 457.8

41.3 42.6 46.6 48.0 50.7 54.7 57.8 63.1

1810.2 1928.5 2306.3 2462.7 2664.2 2865.1 3012.9 3214.3

194.1 208.9 257.4 277.5 310.8 353.6 387.0 443.0

a M is the mass ratio of hydroquinone to phenol + hydroquinone. Standard uncertainties u are u(T) = 0.1 K, u(p) = 1 kPa, u(x) = 0.002 for x > 0.1, and u(x) = 0.0002 for x < 0.1.

Figure 2. LLE data for ternary systems (a) {MBK + water + phenol} at T = 313.2 K and (b) {MBK + water + hydroquinone} at T = 313.2 K. ■, experimental data; −, tie lines.

Figure 4. Distribution coefficient of hydroquinone versus its mole fraction in organic phase at temperatures (T) of (□) 298.2, (▲) 313.2, and (○) 323.2 K.

the quaternary system, and they indicate that MBK is an efficient solvent to remove both phenol and hydroquinone from water. The distribution coefficients for the two ternary subsystems are also shown in Figures 3 and 4 as compared with our previously reported values at different temperatures,5 which indicate that the distribution coefficients decrease as the temperature increases. 3.2. Reliability of Experimental Tie-Line Data. The Othmer−Tobias correlation (eq 2) and the Bachman correlation (eq 3)11,12 were used to evaluate the reliability of experimental tie-line data.

Figure 3. Distribution coefficient of phenol versus its mole fraction in organic phase at temperatures (T)6 of (□) 298.2, (▲) 313.2, and (○) 323.2 K.

⎛ 1 − x II ⎞ ⎛1 − xI ⎞ 1 2 ⎜ ⎟ ⎟ ln⎜ ln = a + b I II ⎝ x2 ⎠ ⎝ x1 ⎠

(2)

⎛ xI ⎞ x1I = c + d⎜ 1II ⎟ ⎝ x2 ⎠

(3)

where a,b and c,d are parameters for Othmer−Tobias and Bachman equations, respectively, xI1 is the mole fraction of MBK in the MBK-rich phase, and xII2 is the mole fraction of water in the water-rich phase. The fitted parameters, with

separation factors for phenol and hydroquinone are presented in Tables 2 and 3 for the two ternary subsystems and Table 4 for D

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Table 5. Fitted Parameters for the Othmer−Tobias and Bachman Equationsa Othmer−Tobias

a

Bachman

M

a

b

R2

c

d

R2

0.0000 0.1998 0.3990 0.5984 0.7971 1.0000

55.3022 30.8680 20.2571 14.8570 11.4061 10.3250

9.3051 5.3230 3.5934 2.7136 2.1504 1.9819

0.9867 0.9857 0.9911 0.9947 0.9968 0.9923

−0.0008 −0.0015 −0.0024 −0.0033 −0.0043 −0.0055

0.9987 0.9995 1.0005 1.0017 1.0028 1.0042

0.9997 0.9999 0.9997 0.9999 0.9999 0.9998

M is the mass ratio of hydroquinone to phenol + hydroquinone.

fraction for species i, respectively, and τ is an adjustable parameter. The pure component structural parameters (γi and qi), taken from refs 19 and 20, are shown in Table 6. The equation for the NRTL model is

Table 6. UNIQUAC Structural (Area and Volume) Parameters19,20 component

r

q

water MBK phenol hydroquinone

0.9200 4.5967 3.5517 3.9156

1.4000 3.9560 2.6800 3.0080

corresponding regression coefficients (R2), are listed in Table 5. All R2 are greater than 0.98, which suggests that our LLE data are reliable. The mutual solubilities (mass fractions) of MBK and water for the binary MBK + water system in our work agree with other published values,13−18 which also indicates that our experimental results are reliable. 3.3. Thermodynamic Modeling. Experimental LLE data for ternary and quaternary systems were correlated with NRTL and UNIQUAC models. For the UNIQUAC model, the excess Gibbs energy is gE = RT

3

3

ψi

θ ∑ xi ln + 5 ∑ xiqi ln i − ψ x i i i=1 i=1

3

τji =

θi =

xiqi 3 ∑i = 1 xiqi

n

∑l = 1 Glixl

(5)

gji − gii RT

4

3

OF =

2

n

∑ ∑ ∑ (xijkexp − xijkcal)2 (6)

i=1 j=1 k=1

j=1

exp

cal

where n is the number of the tie-lines, and x and x are experimental and calculated mole fractions, respectively. The subscripts i, j, and k refer to components, phases, and tie-lines, respectively. Table 7 lists the regressed results of binary interaction parameters for the quaternary system MBK + water + phenol + hydroquinone at 313.2 K. Root-mean-square deviation (RMSD) was used to verify the agreement between experimental and calculated data and was defined as

where

xiγi 3 ∑i = 1 xiγi

i=1

where R is the ideal gas constant, and T is the absolute temperature. The binary interaction parameters for both models were calculated from an Aspen Plus Simulator by minimizing the objective function (OF)

(4)

ψi =

∑ xi

∑ j = 1 τjiGjixj

Gji = exp( −αjiτji)

∑ xiqi ln(∑ θτj ji) i=1

n

n

gE = RT

⎛ uij − ujj ⎞ ⎟ τij = exp⎜ − ⎝ RT ⎠

⎡ ∑4 ∑2 ∑n (x exp − x cal)2 ⎤1/2 ijk i=1 j=1 k = 1 ijk ⎥ RMSD = ⎢ ⎢ ⎥ 8 n ⎣ ⎦

⎛ uji − uii ⎞ ⎟ τji = exp⎜ − ⎝ RT ⎠

Here, qi and γi are UNIQUAC area and volume for species i, respectively, θi and ψi represent area fraction and volume

(7)

The RMSD values of the aforementioned two models are listed in Table 7. It is found that experimental LLE data

Table 7. Binary Interaction Parameters for NRTL and UNIQUAC Models for the Quaternary System MBK (1) + Water (2) + Phenol (3) + Hydroquinone (4) at T = 313.2 Ka components

a

UNIQUAC

NRTL

i−j

bij/K

bji/K

100 RMSD

bij/K

bji/K

αij

100 RMSD

1−2 1−3 1−4 2−3 2−4 3−4

−373.371 409.242 −292.856 −240.079 175.708 −561.241

−145.663 −109.231 310.678 128.320 −63.880 366.566

0.0476 0.0476 0.0476 0.0476 0.0476 0.0476

1421.81 −1435.53 −205.197 908.890 1112.72 −52.508

−1957.10 −57.467 −242.055 −436.122 −329.974 7481.79

0.2 0.3 0.3 0.2 0.2 0.2

0.144 0.144 0.144 0.144 0.144 0.144

The NRTL and UNIQUAC model parameters bij and bji are defined as bij = (gij − gii)/R and bji = (uij − uii)/R, respectively. E

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coefficients suggest that MBK is a suitable extraction solvent to separate phenol and hydroquinone from wastewater. For the quaternary system, the distribution curves show that the existence of one phenolic solute (phenol or hydroquinone) will decrease the other one’s distribution coefficient. Furthermore, the measured LLE data for both ternary and quaternary systems were correlated with the NRTL and UNIQUAC models. Good agreement was found between experimental data and those calculated from NRTL or UNIQUAC models. The resulting interaction parameters from both models can be used to design or optimize extraction processes for phenol or hydroquinone.

correlates well with the data from both NRTL and UNIQUAC models as indicated by small RMSD values. The distribution curves of phenol and hydroquinone are shown in Figures 5 and 6, respectively. The solid lines are

■

AUTHOR INFORMATION

Corresponding Author

*Tel.:+86 13632384249. E-mail: [email protected]. Funding

Financial support from the Fundamental Research Funds for the Central Universities, SCUT (2014ZZ0057 and 2015ZM046), Guangdong Science Foundation (2014A030310260), National Science Foundation of China (20906028 and 21506066), and Project of the Science & Technology New Star of Pearl River in Guangzhou (2011J2200056) are gratefully acknowledged.

Figure 5. Distribution curve for the mole fraction of phenol in aqueous phase against that in organic phase for M = (■) 0 (ternary system), (□) 0.1998, (▲) 0.3990, (Δ) 0.5984, and (●) 0.7971; −, calculated data from the NRTL model (M is the mass ratio of hydroquinone to phenol + hydroquinone).

Notes

The authors declare no competing financial interest.

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REFERENCES

(1) Alvarez Gonzalez, J. R.; Macedo, E. A.; Soares, M. E.; Medina, A. G. Liquid-liquid equilibria for ternary systems of water-phenol and solvents: Data and representation with models. Fluid Phase Equilib. 1986, 26, 289−302. (2) Yang, C.; Qian, Y.; Jiang, Y.; Zhang, L. Liquid-liquid equilibria for the quaternary system methyl isobutyl ketone-water-phenol-hydroquinone. Fluid Phase Equilib. 2007, 258, 73−77. (3) Yang, C.; Qian, Y.; Zhang, L.; Feng, J. Solvent extraction process development and on-site trial-plant for phenol removal from industrial coal-gasification wastewater. Chem. Eng. J. 2006, 117, 179−185. (4) Lei, Y.; Chen, Y.; Li, X.; Qian, Y.; Yang, S.; Yang, C. Liquid− Liquid Equilibria for the Ternary System 2-Methoxy-2-methylpropane + Phenol + Water. J. Chem. Eng. Data 2013, 58, 1874−1878. (5) Chen, Y.; Wang, Z. Liquid−Liquid Equilibria for Ternary Systems: Methyl Butyl Ketone + Phenol + Water and Methyl Butyl Ketone + Hydroquinone + Water at 298.15 and 323.15 K. J. Chem. Eng. Data 2014, 59, 2750−2755. (6) Renon, H.; Prausnitz, J. M. Local compositions in thermodynamic excess functions for liquid mixtures. AIChE J. 1968, 14, 135− 144. (7) Abrams, D. S.; Prausnitz, J. M. Statistical thermodynamics of liquid mixtures: A new expression for the excess Gibbs energy of partly or completely miscible systems. AIChE J. 1975, 21, 116−128. (8) Chirico, R. D.; Frenkel, M.; Magee, J. W.; et al. Improvement of Quality in Publication of Experimental Thermophysical Property Data: Challenges, Assessment Tools, Global Implementation, and Online Support. J. Chem. Eng. Data 2013, 58, 2699−2716. (9) Cheng, N. Solvents Handbook, 3rd ed; Chemical Industry Press: Beijing, 2002. (10) Liu, G. Q.; Ma, L. X.; Liu, J. Physical Properties Handbook of Chemicals; Chemical Industry Press: Beijing, 2002. (11) Othmer, D. F.; Tobias, P. E. Tie-line correlation. Ind. Eng. Chem. 1942, 34, 693−700. (12) Zhang, H.; Gong, Y.; Li, C.; Zhang, L. Liquid-Liquid Equilibria for the Quaternary System Water (1) + Acrylic Acid (2) + Acetic Acid (3) + Cyclohexane (4) at (293.15, 303.15, and 313.15) K. J. Chem. Eng. Data 2011, 56, 2332−2336. (13) Jones, J. H.; Mccants, J. F. Ternary Solubility Data. Ind. Eng. Chem. 1954, 46, 1956−1958.

Figure 6. Distribution curve for the mole fraction of hydroquinone in aqueous phase against that in organic phase for M = (●) 0.1998, (□) 0.3990, (▲) 0.5984, (Δ) 0.7971, and (■) 1 (ternary system); −, calculated data from the NRTL model (M is the mass ratio of hydroquinone to phenol + hydroquinone).

results calculated by the NRTL model. It can be seen that phenol and hydroquinone interact on their equilibrium distributions between MBK and water. In other words, the distribution coefficient of phenol or hydroquinone in the quaternary mixture decreases upon increasing the concentration of the other solute. Such an effect becomes more noticeable for higher phenol or hydroquinone concentrations.

4. CONCLUSIONS The LLE data of two ternary systems, {MBK + phenol + water} and {MBK + hydroquinone+ water}, and a quaternary system, {MBK + phenol + hydroquinone + water}, were measured at T = 313.2K and p = 101.3 kPa. The experimental distribution F

DOI: 10.1021/acs.jced.5b00918 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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(14) Gross, P. M.; Rintelen, J. C.; Saylor, J. H. Energy and Volume Relations in the Solubilities of Some Ketones in Water. J. Phys. Chem. 1939, 43, 197−205. (15) Ginnings, P. M.; Plonk, D.; Carter, E. Aqueous Solubilities of Some Aliphatic Ketone. J. Am. Chem. Soc. 1940, 62, 1923−1924. (16) Stephenson, R. M. Mutual solubilities: water-ketones, waterethers, and water-gasoline-alcohols. J. Chem. Eng. Data 1992, 37, 80− 95. (17) Taghikhani, V.; Vakili-Nezhaad, G. R.; Khoshkbarchi, M. K.; Shariaty-Niassar, M. Liquid−Liquid Equilibria of Water + Propionic Acid + Methyl Butyl Ketone and of Water + Propionic Acid + Methyl Isopropyl Ketone. J. Chem. Eng. Data 2001, 46, 1107−1109. (18) Otero, J. J.; Comesana, J. F.; Correa, J. M.; Correa, A. Liquid− Liquid Equilibria of the System Water + Acetic Acid + 2-Hexanone at 25 and 35 °C. J. Chem. Eng. Data 2001, 46, 1452−1456. (19) Mafra, M. R.; Krähenbühl, M. A. Liquid-liquid Equilibrium of (Water + Acetone) with Cumene or α-Methylstyrene or Phenol at Temperatures of (323.15 and 333.25) K. J. Chem. Eng. Data 2006, 51, 753−756. (20) Magnussen, T.; Rasmussen, P.; Fredenslund, A. UNIFAC parameter table for prediction of liquid-liquid equilibriums. Ind. Eng. Chem. Process Des. Dev. 1981, 20, 331−339.

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DOI: 10.1021/acs.jced.5b00918 J. Chem. Eng. Data XXXX, XXX, XXX−XXX