Liquid–Liquid Equilibria for the Ternary System Methyl Isobutyl Ketone

Article pubs.acs.org/jced

Liquid−Liquid Equilibria for the Ternary System Methyl Isobutyl Ketone + 1,2-Benzenediol + Water Chufen Yang,*,†,‡ Yu Qian,‡ Jianwei Guo,† and Jingrui Chen† †

Faculty of Chemical Engineering & Light Industry, Guangdong University of Technology, Guangzhou 510006, P. R. China School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, P. R. China

‡

ABSTRACT: Liquid−liquid equilibria data for the ternary system methyl isobutyl ketone +1,2-benzenediol + water were measured at temperatures of (298.15, 308.15, and 318.15) K and atmospheric pressure. The reliability of the experimental tie-line data was verified by the Hand and Bachman equations. The experimental data were correlated with the nonrandom two liquid and universal quasichemical models. The binary interaction parameters of these two models were reported. Both models correlated the experimental data successfully.

1. INTRODUCTION 1,2-Benzenediol is a phenolic derivative that has two adjacent hydroxyls in its molecule. As an important chemical intermediate, it is widely used in the fine chemical industries, such as pharmacy, rubber, electroplating etc.1 However, the wastewater containing 1,2-benzenediol is harmful to the human body and ecological environment. As one of the nonvolatile phenolic compounds, 1,2-benzenediol is toxic, listed as priority pollutant by US Environmental Protection Agency.2 With the increasing demand for 1,2-benzenediol, the emissions of its wastewater is also increasing. For its high toxicity and hazardous character, 1,2-benzenediol must be decontaminated from wastewaters before discharge. Because 1,2-benzenediol is an important chemical material, in dealing with the emissions of its wastewater, it is important to recover them, rather than degrade them. In industry, for high concentrated phenolic wastewater (phenolic compounds > 1000 mg/L), solvent extraction is often adopted to deal with these effluents, which can not only remove phenolic compounds from wastewater but also recover them. For extraction of phenols from water, many solvents, such as benzene, diisopropyl ether, butyl acetate, tributyl phosphate, N,N-dibutyl-1-butanamine, etc., have been used.3,4 However, either they possess weak ability in extraction of dihydroxy phenols, or they are high boiling point solvents that are not suitable for using distillation as a solvent recovery method. Methyl isobutyl ketone, a low boiling point solvent (boiling point 115.9 °C), has been found to be a preferable solvent to extract polyhydroxy phenols.5 Liquid−liquid equilibria (LLE) data and their corresponding thermodynamic parameters are essential for simulation and design of the solvent extraction process.6 Various studies have been carried out on the LLE data of the ternary solvent−phenolic component− water system. The experimental data for the aromatic hydrocarbons (toluene or ethylbenzene) + phenols + water system and the aliphatic hydrocarbons (heptane or octane) + phenols + water system have been reported by Martin et al.7,8 The LLE data of the dimethyl carbonate + phenol + water and diphenyl carbonate + phenol + water systems have been studied by Hwang et al.9 In our © 2014 American Chemical Society

previous work, the LLE data of the ternary methyl isobutyl ketone−phenol−water system,10 the ternary methyl isobutyl ketone−hydroquinone−water system,11 and the quaternary methyl isobutyl ketone−water−phenol−hydroquinone system12 have been reported. However, the LLE data of methyl isobutyl ketone + 1,2-benzenediol + water has not been reported until now. In this work, to obtain thermodynamic data for simulating and designing the solvent extraction process of 1,2-benzenediol from its wastewater using methyl isobutyl ketone as solvent, the LLE data of the ternary system methyl isobutyl ketone + 1, 2-benzenediol + water were measured at temperatures of (298.15, 308.15, and 318.15) K and atmospheric pressure. The nonrandom two liquid (NRTL) and universal quasichemical (UNIQUAC) models were used to correlate the LLE data to obtain the binary interaction parameters of these components.

2. EXPERIMENTAL SECTION Materials. Suppliers and purities (mass fraction) of the chemical reagents used in this work are listed in Table 1. The purities of the Table 1. Suppliers and Mass Fraction of the Chemical Reagents chemical reagent

supplier

methyl isobutyl ketone Shanghai Lingfeng Chemical Reagents Co., Ltd. 1,2-benzenediol TianJin Kemiou Chemical Reagents Co., Ltd. water

mass fraction 0.99 0.995 1.000

materials were checked and confirmed by gas chromatography. All of the chemicals in the study were used without further purification. Bidistilled water was used in all experiments. Physical properties of Received: June 19, 2014 Accepted: October 21, 2014 Published: November 4, 2014 3663

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the chemical reagents, including density ρ, boiling point bp, refractive index nD for methyl isobutyl ketone and density ρ, melting point mp for 1,2-benzenediol are given in Table 2 along with

Procedure. The mixtures with a volume of approximately 100 cm3 loaded in the equilibrium cell were stirred vigorously by using a magnetic stirrer for 2 h, and were allowed to settled for 12 h at the constant temperature to separate the two phases. The cell temperature was controlled by a thermostatic bath. The temperature of the thermostatic bath was controlled by a thermocouple relay and its apparatus accuracy was 0.1 K, a value provided by the manufacturers. After phase equilibrium had been reached, samples of two layers were withdrawn with precision Hamiltion syringes and immediately placed in 2 cm3 chromatographic vials. Their compositions were analyzed by a gas chromatograph (Agilent 7820A) equipped with thermal conductivity detector (TCD), and a 16-sample automatic liquid sampler. The temperatures of the injection port and TCD detector were set at 553.15 K. The initial temperature of oven was kept at 373.15 K for 1 min, then increased at a rate of 30 K· min−1 to reach 523.15 K, and kept for 2 min. The carrier gas was hydrogen with a flow rate of 0.75 mL·min−1 for the separation column. A GC capillary column (DB-624, 30 m × 0.32 mm × 0.25 mm) was used to separate every component. The peak area of the components, detected to analyze with EzChrom Elite Compact software, was calibrated based on an external standard to determine the compositions. The external standard calibrated lines of 1,2-benzenediol and water in the methyl isobutyl ketone phase, and 1,2-benzenediol and methyl isobutyl ketone in the aqueous phase were measured beforehand. Each sample was

Table 2. Physical Properties of Density ρ, Boiling Point bp, Refractive Index nD, and Melting Point mp for Chemical Reagentsa chemical reagent

property

exp value

lit. value

methyl isobutyl ketone

ρ(25 °C)/g·cm−3 bp (°C) nD (25 °C) ρ(25 °C)/g·cm−3 mp (°C)

0.799 116.6 1.3965 1.346 105.7

0.79613 115.913 1.393713 1.3414 105.214

1,2-benzenediol

a Standard uncertainties u are u(ρ) = 0.001 g·cm−3, u(bp) = 0.1 °C, u(nD) = 0.0002, u(mp) = 0.5 °C.

literature values.13,14 Both densities of methyl isobutyl ketone and 1,2-benzenediol were measured by an electronic densitometer (Alfa Mirage, MD-300S). Boiling point and refractive index of methyl isobutyl ketone were measured by a ebulliometer (Beijing Zhongxi Company, SJN-XH-616) and a digital Abbe refractometer (Shanghai Physical Optics Instrument Factory, WYA-2S). The melting point of 1,2-benzenediol was measured by a digital meldometer (Shanghai Physical Optics Instrument Factory, WRS-2).

Table 3. Experimental LLE Data (Mass Fraction) for the Ternary System Methyl Isobutyl Ketone (1) + 1, 2-Benzenediol (2) + Water (3) in Mass Fraction w at Temperature T and Pressure p = 0.1 MPaa organic phase w1

w2

0.9802 0.9796 0.9788 0.9779 0.9707 0.9576 0.9311 0.8834 0.8115 0.7557 0.7263 0.6731 0.6158 0.5753 0.5350 0.4854 0.4387 0.4058

0.0000 0.0004 0.0006 0.0019 0.0081 0.0192 0.0430 0.0866 0.1483 0.1864 0.2214 0.2618 0.2997 0.3342 0.3605 0.3957 0.4279 0.4360

0.9762 0.9746 0.9741 0.9724 0.9671 0.9524 0.9266 0.8713 0.7966

0.0000 0.0006 0.0010 0.0025 0.0072 0.0202 0.0429 0.0905 0.1541

organic phase

aqueous phase w3

w1

T/K = 298.15 0.0198 0.0190 0.0200 0.0182 0.0206 0.0181 0.0202 0.0178 0.0212 0.0167 0.0232 0.0163 0.0259 0.0161 0.0300 0.0161 0.0402 0.0155 0.0579 0.0154 0.0523 0.0151 0.0651 0.0131 0.0845 0.0119 0.0905 0.0111 0.1045 0.0113 0.1189 0.0109 0.1334 0.0101 0.1582 0.0099 T/K = 308.15 0.0238 0.0169 0.0248 0.0169 0.0249 0.0168 0.0251 0.0166 0.0257 0.0162 0.0274 0.0160 0.0305 0.0153 0.0382 0.0159 0.0493 0.0132

w2

w1

w3

0.0000 0.0001 0.0001 0.0001 0.0003 0.0007 0.0017 0.0042 0.0088 0.0123 0.0158 0.0207 0.0285 0.0354 0.0397 0.0452 0.0491 0.0513

0.9810 0.9817 0.9818 0.9821 0.9830 0.9830 0.9821 0.9797 0.9757 0.9723 0.9691 0.9662 0.9596 0.9535 0.9490 0.9439 0.9408 0.9388

0.0000 0.0001 0.0001 0.0001 0.0003 0.0009 0.0022 0.0051 0.0099

0.9831 0.9830 0.9831 0.9833 0.9835 0.9831 0.9825 0.9790 0.9769

w2

0.7562 0.7199 0.6557 0.6072 0.5583 0.5309 0.4919 0.4688 0.4375

0.1872 0.2104 0.2587 0.2945 0.3321 0.3518 0.3789 0.3946 0.4124

0.9722 0.9722 0.9721 0.9713 0.9635 0.9502 0.9223 0.8696 0.7965 0.7433 0.7202 0.6586 0.6064 0.5608 0.5201 0.4933 0.4603 0.4396

0.0000 0.0002 0.0005 0.0012 0.0079 0.0197 0.0435 0.0878 0.1486 0.1884 0.2051 0.2485 0.2842 0.3188 0.3477 0.3658 0.3819 0.3945

aqueous phase w3

w1

T/K = 308.15 0.0566 0.0131 0.0697 0.0127 0.0856 0.0122 0.0983 0.0111 0.1095 0.0109 0.1173 0.0109 0.1292 0.0108 0.1366 0.0103 0.1501 0.0099 T/K = 318.15 0.0278 0.0152 0.0276 0.0149 0.0274 0.0148 0.0275 0.0147 0.0286 0.0145 0.0301 0.0137 0.0342 0.0132 0.0426 0.0131 0.0549 0.0124 0.0683 0.0121 0.0747 0.0118 0.0929 0.0113 0.1094 0.0103 0.1204 0.0096 0.1322 0.0093 0.1409 0.0091 0.1578 0.0090 0.1659 0.0089

w2

w3

0.0137 0.0160 0.0217 0.0303 0.0387 0.0433 0.0492 0.0526 0.0561

0.9732 0.9713 0.9661 0.9586 0.9504 0.9458 0.9400 0.9371 0.9340

0.0000 0.0001 0.0001 0.0001 0.0004 0.0010 0.0025 0.0058 0.0113 0.0150 0.0183 0.0293 0.0345 0.0417 0.0487 0.0551 0.0589 0.0636

0.9848 0.9850 0.9851 0.9852 0.9851 0.9853 0.9843 0.9811 0.9763 0.9729 0.9699 0.9594 0.9552 0.9487 0.9420 0.9358 0.9321 0.9275

a w1, w2, and w3 are mass fractions for the composition methyl isobutyl ketone, m-benzenediol and water. Standard uncertainties u are u(T) = 0.1 K, u(w) = 0.0023.

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analyzed at least three times, and the mean value was used. The measurement deviation in the composition analysis was less than 0.46 %, and the largest concentration of the composition in the calibrated solution was 0.5000 in mass fraction. Therefore, the uncertainty of the measurements was estimated within ± 0.0023 in mass fraction.

3. RESULTS AND DISCUSSION LLE Experimental Data. The experimental LLE tie-line data of the ternary system methyl isobutyl ketone +1,2-benzenediol + water at temperature of (298.15, 308.15, and 318.15)) K and atmosphere pressure are listed in Table 3. All compositions are expressed in mass fraction. Figures 1, 2, and 3 show, respectively,

Figure 3. Experimental tie-line for methyl isobutyl ketone + 1,2-benzenediol + water at 318.15 K.

Figure 1. Experimental tie-line for methyl isobutyl ketone + 1,2-benzenediol + water at 298.15 K. Figure 4. Experimental distribution coefficients of 1,2-benzenediol in methyl isobutyl ketone and water at (298.15, 308.15, and 318.15) K.

where the superscripts O and W are the organic phase and the aqueous phase, respectively. Figure 4 compares the trend and difference of experimental distribution coefficients of 1,2-benzenediol in methyl isobutyl ketone and water at (298.15, 308.15, and 318.15) K. It shows that for the ternary system, at the same temperature, with the increase of 1,2benzenediol in the aqueous phase, the distribution coefficient decreases. On the other hand, the distribution coefficient decreases slightly as the system temperate increases. The reliability of the experimental tie-line data was evaluated by using the Hand15 and Bachman16 equations, given by eqs 2 and 3, respectively.

Figure 2. Experimental tie-line for methyl isobutyl ketone + 1,2-benzenediol + water at 308.15 K.

the equilibrium diagrams for the ternary systems at the three temperatures. To examine the extraction ability of methyl isobutyl ketone for 1,2-benzenediol from water, the distribution coefficient (D) is defined as follows:

D=

(2)

⎛ wO ⎞ w1O = a 2 + b2⎜ 1W ⎟ ⎝ w3 ⎠

(3)

where a1, b1 and a2, b2 are the parameters of the Hand and Bachman equations. The parameters together with the regression coefficients are given in Table 4. All of the regression coefficients (R2) close to 1 represent a high consistency of the experimental data. Data Correlation. The experimental LLE data were correlated by using the NRTL and UNIQUAC equations. The adjustable

w2O w2W

⎛ w ⎞W ⎛ w ⎞O ln⎜ 2 ⎟ = a1 + b1 ln⎜ 2 ⎟ ⎝ w1 ⎠ ⎝ w1 ⎠

(1) 3665

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respectively. σT and σw denote the standard deviation of the temperature and the mass fraction. The relative root-mean-square deviation (rmsd) of component i in the phase j is used to check the agreement between the experimental data and the calculated ones. The rmsd value is defined as the following:

Table 4. Hand and Bachman Equations Parameters a and b and Regression Coefficients R2 for the Methyl Isobutyl Ketone +1, 2-Benzenediol + Water System at Temperature Tc Hand

Bachman 2

T/K

a1

b1

R

a2

b2

R2

298.15 308.15 318.15

0.9273 0.9184 0.9290

2.6521 2.4921 2.3939

0.9989 0.9994 0.9992

1.0210 1.0313 1.0408

−0.0383 −0.0468 −0.0541

0.9998 0.9998 0.9997

⎡ ∑3 ∑2 ∑n (w exp − w cal)2 ⎤0.5 ijk ijk i=1 j=1 k=1 ⎥ rmsd = ⎢ ⎢ ⎥ 6 n ⎣ ⎦

c

a1 and b1 are the parameters of the Hand equations, and a2 and b2 are the parameters of the Bachman equations.

Table 7. rsmd Values for the Studied System at Temperature T

binary parameters τij for the NRTL and UNIQUAC equations are defined as eqs 4 and 5, respectively. Aij τij = (4) T ⎛ Aij ⎞ τij = exp⎜ ⎟ ⎝T ⎠

(7)

T/K

NRTL

UNIQUAC

298.15 308.15 318.15 average

0.004824 0.003304 0.004807 0.004312

0.006819 0.003975 0.009361 0.006718

(5)

The rmsd values of the two models are shown in Table 7. It can be seen that both models show good correlation of the tie-line data for the studied system, as the rmsd values are all less than 0.0100. However, the NRTL model is more accurate than the UNIQUAC model according to the average rmsd. The quality of the correlations for the studied ternary system is also shown in Figures 5, 6, and 7 where the experimental data and

where Aij is the binary interaction parameter and can be regressed from the experimental phase equilibrium data, T is temperature. For the UNIQUAC equation, the structural parameters, van der Waals volume ri and surface area qi, are estimated using the Bondi method,17 listed in Table 5. For the NRTL equation, the Table 5. UNIQUAC Structural Parameters Van Der Waals Volume ri and Surface Area qi component

ri

qi

methyl isobutyl ketone 1,2-benzenediol water

4.59591 3.91562 0.92000

3.952 3.008 1.400

nonrandomness parameter (αij) is fixed, and the values are given in Table 6. The binary interaction parameter Aij for the studied system is also listed in Table 6. They are obtained by minimizing the objective function (OF) given in the following equation: exp cal 2 ⎤ ⎡ exp (wijk ) − wijk (Tk − Tkcal)2 ⎢ ⎥ OF = ∑ ∑ ∑ + 2 2 ⎢ ⎥⎦ σ σ T w i=1 j=1 k=1 ⎣ 3

2

n

Figure 5. Comparison of experimental and calculated data at 298.15 K. (6)

where n is the number of the tie-lines, wexp and Texp are the experimental mass fraction and temperature, and wcal and Tcal are the calculated mass fraction and temperature, respectively. The subscripts i, j, and k refer to the component, the phase, and the tie-line,

the calculated data are compared. In the Figures almost all data points fall on the diagonals that denote that the calculated data are equal to the experimental data. It means both NRTL and UNIQUAC models show good correlation for the studied system.

Table 6. Binary Interaction Parameters Binary interaction parameters Aij, Aji of the NRTL and UNIQUAC equations, the Nonrandomness Parameter αij for the NRTL Equation for the Methyl Isobutyl Ketone (1) + 1,2-Benzenediol (2) + Water (3) NRTL

UNIQUAC

T/K

i−j

Aij/K

Aij/K

αij

Aij/K

Aij/K

298.15

1−2 1−3 2−3 1−2 1−3 2−3 1−2 1−3 2−3

881.34 222.46 −705.26 987.59 177.02 −742.71 −30.32 152.94 −786.84

−723.33 1522.60 1884.66 −768.69 1635.67 1912.98 −441.41 1751.12 1880.15

0.3 0.2 0.2 0.3 0.2 0.2 0.3 0.2 0.2

−239.63 −465.34 239.71 −260.53 −425.31 270.11 −610.86 −396.27 −155.03

240.07 −82.74 −410.02 254.42 −103.86 −456.52 385.63 −128.15 160.04

308.15

318.15

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REFERENCES

(1) Zhou, Y. Z.; Tang, W. M.; Dang, F. F.; Chai, S. N.; Zhang, L. Electrochemical characterization of poly-beryllon II modified carbon paste electrode and its application to selective determination of pyrocatechol and hydroquinone. Colloids and Surfaces B: Biointerfaces. 2014, 118, 148−153. (2) Toxic Substances Control Act (TSCA); USEPA: Washington, DC, 1979. (3) Douglas, C.; King, C. J. Solvent extraction of phenols from water. Ind. Eng. Chem. Pro. Des. 1982, 21, 51−54. (4) Yu, Z. J.; Chen, Y.; Feng, D. C.; Qian, Y. Process Development, Simulation, and Industrial Implementation of a New Coal-Gasification Wastewater Treatment Installation for Phenol and Ammonia Removal. Ind. Eng. Chem. Res. 2010, 49, 2874−2881. (5) Yang, C. F.; Yang, S. Y.; Qian, Y.; Guo, J. W.; Chen, Y. Simulation and Operation Cost Estimate for Phenol Extraction and Solvent Recovery Process of Coal-Gasification Wastewater. Ind. Eng. Chem. Res. 2013, 52, 12108−12115. (6) Mohammad, D. F. S.; Mohsen, N. M. Ternary Liquid−Liquid Equilibria for Systems of (Sulfolane + Toluene or Chloronaphthalene + Octane). J. Chem. Eng. Data 2006, 51, 1431−1435. (7) Martin, A.; Klauck, M.; Grenner, A.; Meinhardt, R.; Martin, D.; Schmelzer, J. Liquid−Liquid(−Liquid) Equilibria in Ternary Systems of Aliphatic Hydrocarbons (Heptane or Octane) + Phenols + Water. J. Chem. Eng. Data 2010, 56, 741−749. (8) Martin, A.; Klauck, M.; Taubert, K.; Precht, A.; Meinhardt, R.; Schmelzer, J. Liquid−Liquid Equilibria in Ternary Systems of Aromatic Hydrocarbons (Toluene or Ethylbenzene) + Phenols + Water. J. Chem. Eng. Data 2010, 56, 733−740. (9) Hwang, I.; Park, S. Liquid−liquid Equilibria of Ternary Mixtures of Dimethyl Carbonate, Diphenyl Carbonate, Phenol and Water at 358.15 K. Fluid Phase Equilib. 2011, 301, 18−21. (10) Yang, C. F.; Qian, Y.; Zhang, L. J.; Jiang, Y. B. Measurement and Correlation of Liquid−Liquid Equilibrium Data for Methyl Isobutyl Ketone-Water-Phenol Ternary System. J. Chem. Ind. Eng. (China) 2007, 58, 805−809. (11) Yang, C. F.; Jiang, Y. B.; Zhang, L. J.; Qian, Y. Liquid−Liquid Equilibria for the Ternary System Methyl Isobutyl Ketone +Water + Hydroquinone. J. Chem. Eng. Data 2006, 51, 2107−2109. (12) Yang, C. F.; Qian, Y.; Jiang, Y. B.; Zhang, L. J. Liquid−Liquid Equilibria for the Quaternary System Methyl Isobutyl Ketone−Water− Phenol−Hydroquinone. Fluid Phase Equilib. 2007, 25, 873−877. (13) Cheng, N. L. Solvents Handbook, 3rd ed.,; Chemical Industry Press: Beijing, China, 2002. (14) Liu, G. Q.; Ma, L. X.; Liu, J. Physical Properties Handbook of Chemicals; Chemical Industry Press, Beijing, China, 2002. (15) Hand, D. Dineric Distribution. J. Phys. Chem. 1929, 34, 1961− 2000. (16) Bachman, I. Tie Lines in Ternary Liquid Systems. Ind. Eng. Chem. Anal. Ed. 1940, 12, 38−39. (17) Bondi, A. Physical Properties of Molecular Crystals, Liquids and Gases; Wiley: New York, 1968.

Figure 6. Comparison of experimental and calculated data at 308.15 K.

Figure 7. Comparison of experimental and calculated data at 318.15 K.

4. CONCLUSIONS LLE data for the ternary system methyl isobutyl ketone + 1,2-benzenediol + water were measured at temperatures of (298.15, 308.15, and 318.15) K and atmospheric pressure. The reliability of the experimental tie-line data was evaluated by using the Hand and Bachman equations. The results that all of the regression coefficients (R2) are close to 1 show the high consistency of the experimental data. The comparison of experimental distribution coefficients of 1,2-benzenediol in methyl isobutyl ketone and water at (298.15, 308.15, and 318.15) K shows that the distribution coefficient decreases when the mass fraction of 1,2-benzenediol increases, as well as the system temperature. The experimental LLE data were correlated with the NRTL and UNIQUAC models. The binary interaction parameters of these two models were obtained. The rmsd values and the comparison of experimental and calculated data show that both models correlated the experimental data successfully.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Tel.: 86-020-39322231. Fax: 86-020-39322231. Notes

The authors declare no competing financial interest. Funding

Financial support from the National Natural Science Foundation of China (No. 21106021) and China Postdoctoral Science Foundation funded project (No.2012M511568) is gratefully acknowledged. 3667

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