Liquid–Liquid Equilibria for the Ternary System Methyl Isobutyl Ketone

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Liquid−Liquid Equilibria for the Ternary System Methyl Isobutyl Ketone + m‑Benzenediol + Water Chufen Yang,*,†,‡ Yu Qian,‡ Jianwei Guo,† Jingrui Chen,† and Jinping Peng† †

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 + m-benzenediol + water were measured at temperatures of (298.15, 308.15, and 318.15) K and atmosphere 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 (NRTL) and universal quasichemical (UNIQUAC) models. The binary interaction parameters of these two models were reported. Both models correlated the experimental data successfully.

1. INTRODUCTION Phenols are priority organic pollutants listed as a priority pollutant by the US Environmental Protection Agency.1 They are harmful to the human body and ecological environment. mBenzenediol, which has two hydroxyls in its molecule, is one of the main phenolic pollutants that generally appear in the wastewater from many industrial processes, such as refineries, coking, coal gasification, and petrochemical manufacture.2,3 Because of their high toxicity and hazardous character, phenols must be decontaminated from wastewaters before discharge. On the other hand, all of phenols including m-benzenediol are important chemical materials widely used in industries. Therefore, for high concentrated phenolic wastewater, solvent extraction is often adopted to deal with these effluents not only to decontaminate them, but also to recover them. Many solvents, such as benzene, diisopropyl ether, butyl acetate, etc., have been used to extract phenols from wastewater.4,5 However, they show weak decontamination ability in the wastewater which has a high concentration of m-benzenediol or other polyhydroxy phenols. Methyl isobutyl ketone, a low boiling point solvent (boiling point 115.9 °C), has been found a preferable solvent to extract phenolic pollutants, as its extraction distribution coefficients for polyhydroxy phenols, including m-benzenediol, are much higher than other solvents.6 Liquid−liquid equilibria (LLE) data of solvent−phenolic component−water and their corresponding thermodynamic parameters are essential for simulation and design of the solvent extraction process.7 For the solvent extraction process of phenolic wastewater using methyl isobutyl ketone as the solvent, the LLE data of the ternary methyl isobutyl ketone− phenol−water system,8 the ternary methyl isobutyl ketone− hydroquinone−water system,9 and the quaternary system methyl isobutyl ketone−water−phenol−hydroquinone system10 have been reported. However, the LLE data of methyl isobutyl ketone + m-benzenediol + water have not been reported until now. In this work, to obtain reliable data for the simulation of m-benzenediol recovery from wastewater, the © 2014 American Chemical Society

LLE data of the ternary system methyl isobutyl ketone + mbenzenediol + water were measured at temperatures of (298.15, 308.15, and 318.15) K and atmospheric pressure. The nonrandom two-liquid (NRTL)11 and universal quasichemical (UNIQUAC)12 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 Table 1. Suppliers and Mass Fraction Purities of the Chemical Reagents chemical reagent methyl isobutyl ketone m-benzenediol

supplier Shanghai Lingfeng Chemical Reagents Co., Ltd. Tianjin Kemiou Chemical Reagents Co., Ltd.

water a

initial mass fraction purity

GCa mass fraction purity

0.99

0.9935

0.995

0.9968 0.9998

Gas chromatography.

purities of the 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, and its purity was also checked by gas chromatography. Procedure. The mixtures with a volume of approximately 100 cm3 loaded in the equilibrium cell were stirred vigorously using a magnetic stirrer. The cell temperature was controlled by a thermostatic bath with an uncertainty of ± 0.1 K. In order to Received: April 7, 2014 Accepted: September 8, 2014 Published: September 18, 2014 3324

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confirm the equilibrium time of the experimental systems, a preliminary experiment at different stirring times and settling times was completed. It was found that the mixture could not be completely mixed for stirring time (0.5 or 1.0) h but completely mixed for (1.5 and 2.0) h. On the other hand, the complete phase separation (clear two-phase) could not be observed for settling time (1.0, 2.0, and 4.0) h, but it was very well for (5.0, 8.0, and 10.0) h, and the compositions (mass fraction by GC) of two phases for settling time (5.0, 8.0, and 10.0) h were almost consistent. For this reason, the stirring and settling times of the experimental systems were selected as (2.0 and 10.0) h, respectively. After phase equilibrium has been reached, samples of two layers were withdrawn with precision Hamiltion syringes and immediately placed in 2 cm3 chromatographic vials, and their compositions were analyzed by a gas chromatography (Agilent 7820A) equipped with a 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 rate of 0.75 mL· min−1 for the separation column. A GC capillary column (DB624, 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 by gravimetrically weighed mixtures. Each sample was analyzed at least three times, and the mean value was used. The measurement deviation in the composition analysis is less than 0.42 %. Therefore, the accuracy of the measurements was estimated within ± 0.0021 in mass fraction.

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

D=

w1

w2

w3

w1

w2

w3

0.9802 0.9766 0.973 0.9653 0.9408 0.8959 0.8434 0.7993 0.7504 0.6489 0.5618 0.4341 0.3782 0.3217 0.9780 0.9753 0.9716 0.9645 0.9387 0.8979 0.8463 0.8095 0.7548 0.6665 0.5949 0.5013 0.4339 0.3517 0.9766 0.9740 0.9707 0.9633 0.9365 0.9036 0.8421 0.7949 0.7616 0.6903 0.5955 0.4885 0.4176 0.3710

0.0000 0.0032 0.0057 0.0111 0.0327 0.0726 0.1182 0.1554 0.195 0.2779 0.3408 0.4323 0.4654 0.4904 0.0000 0.0023 0.0047 0.0107 0.0337 0.0693 0.1155 0.1487 0.1940 0.2670 0.3207 0.3899 0.4330 0.4730 0.0000 0.0024 0.0053 0.0121 0.0354 0.0645 0.1186 0.1586 0.1868 0.2461 0.3214 0.3974 0.4405 0.4572

0.0198 0.0202 0.0213 0.0236 0.0265 0.0315 0.0384 0.0453 0.0546 0.0732 0.0974 0.1336 0.1564 0.1879 0.0220 0.0224 0.0237 0.0248 0.0276 0.0328 0.0382 0.0418 0.0512 0.0665 0.0844 0.1088 0.1331 0.1753 0.0234 0.0236 0.0240 0.0246 0.0281 0.0319 0.0393 0.0465 0.0516 0.0636 0.0831 0.1141 0.1419 0.1718

0.0181 0.0180 0.0179 0.0179 0.0175 0.0169 0.0162 0.0157 0.0154 0.0154 0.0166 0.0185 0.0212 0.0267 0.0159 0.0159 0.0159 0.0157 0.0155 0.0150 0.0144 0.0142 0.0139 0.0140 0.0149 0.0154 0.0180 0.0239 0.0146 0.0146 0.0145 0.0144 0.0142 0.0138 0.0134 0.0131 0.0130 0.0131 0.0141 0.0165 0.0189 0.0222

0.0000 0.0001 0.0002 0.0004 0.0014 0.0040 0.0093 0.0161 0.0240 0.0475 0.0809 0.1508 0.1844 0.2177 0.0000 0.0001 0.0002 0.0005 0.0017 0.0046 0.0099 0.0136 0.0256 0.0474 0.0777 0.1220 0.1635 0.2130 0.0000 0.0001 0.0003 0.0007 0.0023 0.0049 0.0116 0.0205 0.0260 0.0449 0.0807 0.1386 0.1799 0.2171

0.9819 0.9819 0.9819 0.9817 0.9811 0.9791 0.9745 0.9682 0.9606 0.9371 0.9025 0.8307 0.7944 0.7556 0.9841 0.984 0.9839 0.9838 0.9828 0.9804 0.9757 0.9722 0.9605 0.9386 0.9074 0.8626 0.8185 0.7631 0.9854 0.9853 0.9852 0.9849 0.9835 0.9813 0.9750 0.9664 0.9610 0.9420 0.9052 0.8449 0.8012 0.7607

318.15

w2O w2W

T/K 298.15

308.15

3. RESULTS AND DISCUSSION LLE Experimental Data. The compositions of the LLE tieline data of the ternary system methyl isobutyl ketone + mbenzenediol + water at temperatures of (298.15, 308.15, and 318.15) K and atmospheric pressure are listed in Table 2. w1, w2, and w3 are mass fractions for the composition methyl isobutyl ketone, m-benzenediol, and water. Figures 1, 2, and 3 show, respectively, the equilibrium diagrams for the ternary systems at the three temperatures. To examine the extraction ability of methyl isobutyl ketone for m-benzenediol from water, the distribution coefficient (D) is defined as follows:

(1)

where the superscripts O and W refer to the organic phase and the aqueous phase, respectively. Figure 4 compares the trend and difference of experimental distribution coefficients of mbenzenediol 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 m-benzenediol in the organic phase, the distribution coefficient decreases. On the other hand, the distribution coefficient decreases obviously as the system temperature increases when the mass fraction of mbenzenediol (w2) in the organic phase is small. However, the distribution coefficient’s decreasing trend dependence on temperature gradually become small when w2 in the organic phase increases until the distribution coefficient becomes the same. It means that for this ternary system, to gain a high distribution coefficient for the extraction of m-benzenediol from

aqueous phase

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 and u(w) = 0.0021.

water using methyl isobutyl ketone, low temperatures and low m-benzenediol concentrations are more feasible. The reliability of the experimental tie-line data was evaluated by using the Hand13 and Bachman14 equations, given by eqs 2 and 3, respectively. ⎛ w2 ⎞ W ⎛ w2 ⎞O ln⎜ ⎟ = a1 + b1 ln⎜ ⎟ ⎝ w1 ⎠ ⎝ w1 ⎠ 3325

(2)

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Figure 3. LLE data (mass fraction) for methyl isobutyl ketone + mbenzenediol + water at 318.15 K. ●, experimental tie-line; ▽, correlation by NRTL with binary parameters from Table 6; △, correlation by UNIQUAC with binary parameters from Table 6.

Figure 1. LLE data (mass fraction) for methyl isobutyl ketone + mbenzenediol + water at 298.15 K. ●, experimental tie-line; ▽, correlation by NRTL with binary parameters from Table 6; △, correlation by UNIQUAC with binary parameters from Table 6.

Figure 4. Experimental distribution coefficients of m-benzenediol in methyl isobutyl ketone and water at (298.15, 308.15, and 318.15) K. ■, 298.15 K; ○, 308.15 K; △, 318.15 K.

Figure 2. LLE data (mass fraction) for methyl isobutyl ketone + mbenzenediol + water at 308.15 K. ●, experimental tie-line; ▽, correlation by NRTL with binary parameters from Table 6; △, correlation by UNIQUAC with binary parameters from Table 6.

⎛ wO ⎞ w1O = a 2 + b2⎜ 1W ⎟ ⎝ w3 ⎠

Table 3. Hand and Bachman Equation Parameters a and b and Regression Coefficients R2 for the Methyl Isobutyl Ketone + m-Benzenediol + Water System at Temperature Ta Hand

(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 3. 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 binary parameters τij for the NRTL and UNIQUAC equations are defined as eqs 4 and 5, respectively. τij = Aij +

⎛ Bij ⎞ τij = exp⎜Aij + ⎟ T⎠ ⎝

T/K

a1

b1

R

298.15 308.15 318.15

0.7525 0.7785 0.7837

1.3941 1.4021 1.3250

0.9961 0.9933 0.9958

a2

b2

R2

1.1516 1.1707 1.1931

−0.1614 −0.1774 −0.1974

0.9988 0.9984 0.9982

a

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

where Aij and Bij are the binary interaction parameters and can be obtained from experimental phase equilibrium data. For the UNIQUAC equation, the structural parameters, van der Waals volume ri, and surface area qi, are estimated using the Bondi method,15 listed in Table 4. For the NRTL equation, the nonrandomness parameter (αij) is fixed, and the values are given in Table 5. The binary interaction parameters Aij, Aji, Bij, and Bji for the studied system are listed in Table 5. They are obtained by minimizing the objective function (OF) given in the following equation:16

Bij T

Bachman 2

(4)

(5) 3326

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Table 4. UNIQUAC Structural Parameters van der Waals Volume ri and Surface Area qi component

ri

qi

methyl isobutyl ketone m-benzenediol water

4.59591 3.91562 0.92000

3.952 3.008 1.400

Table 6. Relative Root-Mean-Square Deviation (%) for the Studied System organic phase

exp cal 2 ⎤ ⎡ exp (wijk ) − wijk (Tk − Tkcal)2 ⎢ ⎥ OF = ∑ ∑ ∑ + 2 2 ⎢ ⎥⎦ σ σ T w ⎣ i=1 j=1 k=1 3

2

UNIQUAC

NRTL

methyl isobutyl ketone m-benzenediol water

1.13 3.56 3.25

0.83 2.81 3.03

3.52 3.23 0.48

2.16 2.48 0.25

AUTHOR INFORMATION

*Email: [email protected]. Phone: 86-020-39322231. Fax: 86-020-39322231.

exp

where n is the number of the tie-lines, w and T 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, 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 data. The RMSD value is defined as the following: ⎡ ∑n ((w exp − w cal)/w exp)2 ⎤1/2 ijk ijk ijk k=1 ⎥ RMSD = ⎢ ⎢⎣ ⎥⎦ n

NRTL

Corresponding Author

(6) exp

UNIQUAC

■

n

aqueous phase

component

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. Notes

The authors declare no competing financial interest.

■

REFERENCES

(1) Toxic Substances Control Act (TSCA); US Environmental Protection Agency (EPA): Washington, DC, 1979. (2) Kohl, A. I.; Nielsen, R. Gas Purification, 5th ed.; Gulf Publishing Company: Houston, 1997. (3) Gai, H. J.; Jiang, Y. B.; Qian, Y.; Kraslawski, A. Conceptual design and retrofitting of the coal-gasification wastewater treatment process. Chem. Eng. J. 2008, 138, 84−94. (4) Douglas, C.; King, C. J. Solvent extraction of phenols from water. Ind. Eng. Chem. Process Des. 1982, 21, 51−54. (5) 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. (6) 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. (7) Mohammad Doulabi, F. S.; Mohsen Nia, M. Ternary LiquidLiquid Equilibria for Systems of (Sulfolane + Toluene or Chloronaphthalene + Octane). J. Chem. Eng. Data 2006, 51, 1431− 1435. (8) 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. (9) 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. (10) Yang, C. F.; Qian, Y.; Jiang, Y. B.; Zhang, L. J. Liquid-Liquid Equilibria for the Quaternary System Methyl Isobutyl Ketone-WaterPhenol- Hydroquinone. Fluid Phase Equilib. 2007, 25, 873−877.

(7)

The RMSD values of the two models are shown in Table 6. It can be seen that both models show good correlation of the tieline data for the studied system, as the RMSD for every component in both phase are all less than 4 %. However, the NRTL model is more accurate than the UNIQUAC model according to the average RMSD.

4. CONCLUSIONS LLE data for the ternary system methyl isobutyl ketone + mbenzenediol + 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 result that all of the regression coefficients (R2) are close to 1 shows a high consistency of the experimental data. The experimental LLE data were correlated with the NRTL and UNIQUAC models. The binary interaction parameters of these two models were obtained. Both models correlated the experimental data successfully. The RMSD for every component in both phase are all less than 4 %, and the NRTL model is more accurate than the UNIQUAC model according to the average RMSD.

Table 5. Binary Interaction Parameters Aij, Aji, Bij, and Bji of the NRTL and UNIQUAC Equations, the Non-randomness Parameter αij for the NRTL Equation for the Methyl Isobutyl Ketone (1) + m-Benzenediol (2) + Water (3) NRTL

UNIQUAC

component (i−j)

1−3

1−2

2−3

1−3

1−2

2−3

Aij Aji Bij/K Bji/K αij

−0.84 9.60 463.30 −1344.50 0.20

−4.48 1.03 2536.93 −1181.05 0.30

2.77 −2.60 −1361.41 2002.81 0.20

1.10 −1.70 −781.48 423.48

3.420 −0.95 −1319.06 619.99

−2.59 4.06 868.94 −1202.04

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(11) Renon, H.; Prausnitz, J. M. Local Compositions in Thermodynamic Excess Functions for Liquid Mixtures. AIChE J. 1968, 14, 135−144. (12) 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. (13) Hand, D. Dineric Distribution. J. Phys. Chem. 1929, 34, 1961− 2000. (14) Bachman, I. Tie Lines in Ternary Liquid Systems. Ind. Eng. Chem., Anal. Ed. 1940, 12, 38−39. (15) Bondi, A. Physical Properties of Molecular Crystals, Liquids and Gases; Wiley: New York, 1968. (16) Lei, Y.; Chen, Y.; Li, X. X.; Qian, Y.; Yang, S. Y.; Yang, C. F. Liquid-Liquid Equilibria for the Ternary System 2-Methoxy-2methylpropane + Phenol + Water. J. Chem. Eng. Data 2013, 58, 1874−1878.

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