Measurement and Correlation of Ternary (Liquid+ Liquid) Equilibria for

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

pubs.acs.org/jced

Measurement and Correlation of Ternary (Liquid + Liquid) Equilibria for Separation of Cyclohexanone from Water via Isophorone or Mesityl Oxide Chong Yang, Hai Liu, Chuanfu Zhu, Midong Shi, Gaoyin He, and Qingsong Li* State Key Laboratory of Heavy Oil Processing, College of Chemical Engineering, China University of Petroleum (East China), Qingdao, Shandong 266580, China

ABSTRACT: Liquid−liquid equilibria provide basic data and guidance regarding the design, simulation, and development of an appropriate solvent extraction process. In the current work, the data for the liquid−liquid equilibrium (LLE) of water + cyclohexanone + isophorone and water + cyclohexanone + mesityl oxide systems have been measured at temperatures of 308.15−328.15 K and pressure of 101.3 kPa. The empirical Bachman and Hand equations were utilized to confirm the consistency of experimentally determined LLE data. Meanwhile, the solute distribution ratio and separation parameter were obtained from the experimental equilibrium data to evaluate the extraction properties of the selected solvents. Additionally, a mathematical regression of experimental tie-line compositions for all of the investigated ternary mixtures was performed by means of the nonrandom two-liquid and universal quasi-chemical activity coefficient models to acquire corresponding optimized binary interaction parameters. The correlation results were verified to be coincident with the experimental ones and revealed that the above two thermodynamic models were of high-accuracy and suitable to regress the tie-line compositions for the investigated ternary systems.

1. INTRODUCTION

Scheme 1. Simplified Process for the Production of Cyclohexanol and Cyclohexanone

Cyclohexanone is becoming an increasingly significant industrial commodity since it is extensively employed as a major intermediate in the chemical industry for the fabrication of caprolactam and adipic acid, used as the key precursors in manufacturing nylons.1−3 In addition, it is also utilized as a superior industrial solvent, owing to its low volatility and high solubility, having a considerable variety of applications in various areas such as paints, plastics, resins, and printing inks as well as homogenizers and stabilizers for synthetic detergent emulsions and soaps.4,5 Industrially, it mainly adopts a liquid-phase oxidation of cyclohexane using a soluble cobalt species as catalysts to yield cyclohexanol and cyclohexanone (the mixture is known as KA oil).6−8 The reaction of cyclohexane oxidation initially produces cyclohexyl hydroperoxide as a key intermediate, which is later resolved into cyclohexanol and cyclohexanone rapidly in an alkaline aqueous solution containing a small amount of cobalt salt catalyst, as illustrated in Scheme 1. Nevertheless, the flaw in this process is that the experimental equipment is susceptible to corrosion in the practical production. Moreover, it would exhaust plenty of cyclohexanone-containing © XXXX American Chemical Society

wastewater, which causes serious harm to the environment and human health. Thus, the separation of cyclohexanone from wastewater is of paramount significance from both environmental as well as economic points of view. It is clearly established that cyclohexanone and water can form a homogeneous and azeotropic mixture;9 therefore, the conventional distillation technique is not viable to achieve Received: September 2, 2017 Accepted: November 27, 2017

A

DOI: 10.1021/acs.jced.7b00787 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

mesityl oxide, were procured from Sinopharm Chemical Reagent Co., Ltd., China. Gas chromatography (GC6820, Agilent Technologies) was utilized to check the purities of these compounds, and no dramatic peaks of impurities were detected. Distilled water was utilized throughout all experiments. All of the chemicals were employed as obtained without additional treatment, and the major details of the reagents are manifested in Table 1.

efficient separation of the mixture. Several special distillation strategies, including reactive distillation, extractive distillation, and azeotropic distillation, could be used for treating the binary azeotrope or close-boiling systems,10−13 although these approaches require a large investment and consume an excessive amount of energy.14 In view of the above problems, the liquid− liquid extraction, which emerges as a beneficial separation technology due to its low energy consumption and high separation efficiency, has been extensively employed to separate lots of azeotropic mixtures in chemical engineering.15−19 Screening a desirable extractant is critical to the design and development of a feasible extraction process for the recovery of cyclohexanone from aqueous solution. For instance, Vozin and co-workers20 investigated the separation of cyclohexanone from water using various extractants and concluded that acetate esters and aromatic hydrocarbons are better than paraffin for the extraction process. In another report, Pei et al.4 performed valuable studies on LLE measurements of water + cyclohexane + cyclohexanone at 303.2, 313.2, 323.2, and 333.2 K. However, further investigations regarding the phase behavior and thermodynamic properties of the cyclohexanone-containing aqueous solution are still required for various academic and industrial objectives. More LLE data involving the aqueous solution of cyclohexanone with different extractants, toluene, and p-xylene have been reported in our previous work.21 Recently, Ershova and co-workers19 carried out LLE experiments on the recovery of furfural from its mixture with water by isophorone and stated that isophorone was a very promising extractant for furfural upgrading. Colombo et al.22 investigated the extraction of acetic acid from water using different solvents and found that isophorone can exhibit a better separation capability for acetic acid because of its lower miscibility with water compared with ethyl acetate.23,24 Chen and co-workers explored the utilization of mesityl oxide as an extracting solvent for the separation of propionic acid, butyric acid, or phenol from water in achieving superior extraction performance.25,26 According to quantum chemical calculations and experiments, Feng et al.27 verified that mesityl oxide can be employed as a desirable extracting solvent to separate phenols from coal-gasification wastewater, and designed a reasonable phenols recovery process. Inspired by these features of both the above-mentioned solvents, as a continuation, we analytically determined the experimental LLE data for the recovery of cyclohexanone from its mixture with water using isophorone or mesityl oxide as extracting solvents at 308.15, 318.15, and 328.15 K under 101.3 kPa in the current work. To our knowledge, there have so far been no existing reports about the LLE data and thermodynamic properties of these investigated ternary systems. The consistency and reliability of experimentally determined LLE data for each system were corroborated by Bachman28 and Hand29 empirical equations. Also, the experimental distribution ratios and separation parameters, derived from the obtained LLE data, were employed to assess the extractive efficiency of the studied extractants for the recovery of cyclohexanone from aqueous solution. Furthermore, the determined LLE data were regressed via the nonrandom two-liquid (NRTL)30 and the universal quasi-chemical (UNIQUAC)31 thermodynamic models, and the numerical values for the optimized interaction parameters between different components of the ternary mixtures were obtained from the data correlation.

Table 1. Details of the Chemicals Used in This Work chemical name

CASRN

source

cyclohexanone isophoronea mesityl oxideb isopropanol distilled waterc

108-94-1 78-59-1 141-79-7 67-63-0 7732-18-5

Sinopharm Sinopharm Sinopharm Sinopharm Homemade

stated mass fraction purityd

analysis method

≥99.5% ≥99.0% ≥98.5% ≥99.7%

GCe GCe GCe GCe GCe

a Isophorone = 3,5,5-trimethyl-2-cyclohexen-1-one. bMesityl oxide = 4-methyl-3-penten-2-one. cThe electrical conductivity of distilled water used in the work is 8.35 μS/cm.18 dMass fraction purity is stated by the manufacturer. eGas chromatography.

2.2. Apparatus and Experimental Procedure. Experimental LLE data for investigated ternary mixtures of water + cyclohexanone + solvents (isophorone or mesityl oxide) were determined at (308.15−328.15) K under 101.3 kPa. The detailed information regarding the apparatus utilized in this work was described in our earlier report and the reliability of the experimental system was also appraised.32 Briefly, the equilibrium runs were implemented in a jacketed glass cell with a total capacity of approximately 100 cm3, and the temperature of the instrument was maintained constant via a connection with a superthermostatic water bath, which was controlled at the desired temperature with a fluctuation of ±0.1 K. The prepared mixtures with a synthetic composition comprising water, cyclohexanone, and solvents were fed into the extraction vessel and agitated at a rate of 900 rpm for 2 h by a magnetic stirrer (model ZNCL-BS). After that, the resulting solutions were allowed to stand for 6 h to achieve a complete phase separation of the two layers. A series of other LLE experiments were conducted by altering either compositions or temperatures of the mixtures. At the end of the setting period, the prepared mixtures were completely divided into the water-rich phase and the solventrich phase. To figure out the compositions of both phases, the samples were carefully withdrawn by 1-μL glass syringes, and the injection volume was 0.6 μL. All samples of the two layers were analyzed using Agilent 6820 gas chromatography (GC) composed of a Porapak N column (3 m × 3 mm) and a thermal conductivity detector (TCD). High purity hydrogen, provided by Qingdao Tianyuan Gases Produce Co., Ltd., served as a carrier gas with a flow rate of 1 cm3 s−1. The temperatures of the injection port and TCD detector were both fixed at 523.15 K. The operational program of GC was as follows: the initial column temperature was set at 393.15 K for 1.5 min, subsequently enhanced at a ramp rate of 20 K per minute to reach the final temperature of 523.15 K, and kept at the temperature for the other 3 min. The quantitative result was determined by a calibration area normalization approach, which was calibrated by binary mixtures of known concentration by weighing using a Mettler AL204 analytical balance with a measuring sensitivity of 0.1 mg.32,33 In this analysis, isopropyl

2. EXPERIMENTAL SECTION 2.1. Materials. The materials utilized in the present work, consisting of cyclohexanone, isophorone, isopropyl alcohol, and B



Article

alcohol was selected as a standard substance to acquire relative mass correction factors of water, cyclohexanone, isophorone, and mesityl oxide, respectively; a similar analytical approach was utilized in Ershova’s study.19 The sample of each distinct layer was analyzed three times or more, and the mean result in mass fraction was adopted for the component composition. In addition, the uncertainties for mass compositions in both liquid phases were determined according to the GUM standard,34 which has been used elsewhere.32,35 2.3. Evaluation of the Extractive Solvent. Extracting capability of the selected solvents was estimated in terms of the solute distribution ratio (D) and separation parameter (S), which can be expressed as follows:26,33 D=

S=

(1)

n

component

r

q

cyclohexanonea isophoroneb mesityl oxidec watera

4.1140 5.9315 4.3632 0.9200

3.3400 4.9400 3.8600 1.4000

(2)

wII2

where and denote the mass fraction of water and cyclohexanone, respectively, in the upper layer (solvent-rich phase). wI1 and wI2 mean the mass fraction of water and cyclohexanone in the lower layer (water-rich phase), respectively. 2.4. Thermodynamics Modeling. Two well-known thermodynamic models, NRTL30 and UNIQUAC,31 were utilized to regress the raw LLE data for water + cyclohexanone + solvents (isophorone or mesityl oxide) ternary systems via using Aspen Plus (version 8.4). With regard to the NRTL equation, the nonrandomness parameter, α, was fixed at 0.3 for each binary pair of compounds.30 In the UNIQUAC model, the structural parameters of pure components, r (volume parameter) and q (surface area parameter), were derived from associated works of literature4,22,25 and presented in Table 2. The regression interaction parameters of the two models could be obtained through minimizing the objective function (OF),36 which was defined as

Table 2. UNIQUAC Structural Parameters for the Pure Component

a

w2I /w1I

wII1

w2II w2I

w2II/w1II

OF =

2

3

∑ ∑ ∑ (wijkexp − wijkcal)2 (3)

k=1 j=1 i=1

where n denotes the total number of tie-lines, wexp means the experimental LLE results, and wcal represents the calculated values by both models. Subscripts i, j, and k are the

Taken from ref 4. bTaken from ref 22. cTaken from ref 25.

Table 3. Experimental LLE Data (Mass Fraction) For Water (1) + Cyclohexanone (2) + Isophorone (3) at Temperatures of 308.15, 318.15, and 328.15 K under 101.3 kPaa organic phase w1

a

w2

aqueous phase w3

0.0425b 0.0431 0.0442 0.0466 0.0492 0.0517 0.0526 0.0528 0.0528

0.0000 0.1821 0.2293 0.3234 0.3692 0.4494 0.4923 0.5255 0.5532

0.9575b 0.7748 0.7265 0.6300 0.5816 0.4989 0.4551 0.4217 0.3940

0.0454b 0.0426 0.0453 0.0458 0.0471 0.0484 0.0486 0.0488 0.0507

0.0000 0.0923 0.1385 0.1819 0.2778 0.3262 0.3771 0.4236 0.4717

0.9546b 0.8651 0.8162 0.7723 0.6751 0.6254 0.5743 0.5276 0.4776

0.0484b 0.0406 0.0415 0.0430 0.0457 0.0487 0.0521 0.0549 0.0553

0.0000 0.0441 0.0915 0.1807 0.2235 0.2711 0.3685 0.4469 0.5064

0.9516b 0.9153 0.8670 0.7763 0.7308 0.6802 0.5794 0.4982 0.4383

w1

w2

T/K = 308.15 0.9870b 0.0000 0.9517 0.0198 0.9474 0.0250 0.9363 0.0363 0.9340 0.0406 0.9252 0.0511 0.9209 0.0564 0.9177 0.0610 0.9140 0.0655 T/K = 318.15 0.9880b 0.0000 0.9642 0.0088 0.9612 0.0132 0.9574 0.0174 0.9516 0.0263 0.9493 0.0303 0.9464 0.0349 0.9415 0.0404 0.9404 0.0444 T/K = 328.15 0.9881b 0.0000 0.9558 0.0046 0.9550 0.0097 0.9457 0.0194 0.9420 0.0244 0.9397 0.0289 0.9369 0.0375 0.9314 0.0457 0.9229 0.0547

w3

D

S

0.0130b 0.0285 0.0276 0.0274 0.0254 0.0237 0.0227 0.0213 0.0205

9.20 9.17 8.91 9.09 8.79 8.73 8.61 8.45

203.08 196.60 179.00 172.63 157.38 152.82 149.73 146.20

0.0120b 0.0270 0.0256 0.0252 0.0221 0.0204 0.0187 0.0181 0.0152

10.49 10.49 10.45 10.56 10.77 10.81 10.49 10.62

237.40 222.63 218.53 213.41 211.15 210.41 202.29 197.06

0.0119b 0.0396 0.0353 0.0349 0.0336 0.0314 0.0256 0.0229 0.0224

9.59 9.43 9.31 9.16 9.38 9.83 9.78 9.26

225.69 217.07 204.85 188.81 181.01 176.71 165.90 154.50

Standard uncertainties u are u(T) = 0.1 K, u(p) = 0.3 kPa and u(w) = 0.0032. bObtained from ref 23 by interpolation. C



Article

Table 4. Experimental LLE Data (Mass Fraction) For Water (1) + Cyclohexanone (2) + Mesityl Oxide (3) at Temperatures of 308.15, 318.15, and 328.15 K under 101.3 kPaa organic phase w1

a

w2

aqueous phase w3

w1

0.0406b 0.0356 0.0390 0.0405 0.0448 0.0486 0.0538 0.0541 0.0577

0.0000 0.0485 0.1049 0.1486 0.2486 0.2952 0.3372 0.4305 0.4684

0.9594b 0.9159 0.8561 0.8109 0.7066 0.6562 0.6090 0.5154 0.4739

0.9771b 0.9610 0.9587 0.9550 0.9501 0.9487 0.9467 0.9398 0.9385

0.0438b 0.0392 0.0394 0.0415 0.0442 0.0471 0.0509 0.0514 0.0531

0.0000 0.0463 0.1951 0.2422 0.2929 0.3867 0.4342 0.4771 0.5428

0.9562b 0.9145 0.7655 0.7163 0.6629 0.5662 0.5149 0.4715 0.4041

0.9794b 0.9673 0.9587 0.9559 0.9536 0.9481 0.9457 0.9422 0.9398

0.0473b 0.0431 0.0451 0.0478 0.0522 0.0531 0.0578 0.0633 0.0652

0.0000 0.0470 0.1488 0.2004 0.2469 0.3441 0.4251 0.4579 0.4932

0.9527b 0.9099 0.8061 0.7518 0.7009 0.6028 0.5171 0.4788 0.4416

0.9814b 0.9542 0.9526 0.9495 0.9481 0.9443 0.9410 0.9378 0.9326

w2 T/K = 308.15 0.0000 0.0039 0.0085 0.0124 0.0208 0.0248 0.0285 0.0377 0.0409 T/K = 318.15 0.0000 0.0032 0.0144 0.0183 0.0221 0.0302 0.0342 0.0387 0.0440 T/K = 328.15 0.0000 0.0038 0.0119 0.0167 0.0204 0.0285 0.0354 0.0393 0.0447

w3

D

S

0.0229b 0.0351 0.0328 0.0326 0.0291 0.0265 0.0248 0.0225 0.0206

12.44 12.34 11.98 11.95 11.90 11.83 11.42 11.45

335.70 303.37 282.58 253.47 232.36 208.20 198.37 186.27

0.0206b 0.0295 0.0269 0.0258 0.0243 0.0216 0.0201 0.0191 0.0162

14.47 13.55 13.23 13.25 12.80 12.70 12.33 12.34

357.03 329.67 304.85 285.94 257.75 235.88 225.98 218.34

0.0186b 0.0420 0.0355 0.0338 0.0315 0.0272 0.0236 0.0229 0.0227

12.37 12.50 12.00 12.10 12.07 12.01 11.65 11.03

273.83 264.11 238.37 219.82 214.71 195.50 172.62 157.82

Standard uncertainties u are u(T) = 0.1 K, u(p) = 0.3 kPa, and u(w) = 0.0058. bObtained from ref 26 by interpolation or extrapolation.

Figure 1. Ternary phase diagram for the system of water + cyclohexanone + isophorone at 308.15 K: (☆) feed composition; (■) experimental data; (▲) calculated data from the NRTL model; (●) calculated data from the UNIQUAC model.

Figure 2. Ternary phase diagram for the system of water + cyclohexanone + isophorone at 318.15 K: (☆) feed composition; (■) experimental data; (▲) calculated data from the NRTL model; (●) calculated data from the UNIQUAC model.

constituents, phases, and tie lines, respectively. The function represents the discrepancy between the results calculated by the

respective method and experimentally determined over all of the tie lines in the investigated ternary systems.37 D



Article

Figure 3. Ternary phase diagram for the system of water + cyclohexanone + isophorone at 328.15 K: (☆) feed composition; (■) experimental data; ▲() calculated data from the NRTL model; (●) calculated data from the UNIQUAC model.

Figure 5. Ternary phase diagram for the system of water + cyclohexanone + mesityl oxide at 318.15 K: (☆) feed composition; (■) experimental data; (▲) calculated data from the NRTL model; (●) calculated data from the UNIQUAC model.



Furthermore, the value of root-mean-square deviation (RMSD) was employed to assess the quality of the optimization results via the NRTL and UNIQUAC models, which was expressed based on the following formula: ⎧ n 2 3 exp cal 2 ⎫1/2 − wijk (wijk ) ⎪ ⎪ ⎬ RMSD = ⎨∑ ∑ ∑ ⎪ 6n ⎪k=1 j=1 i=1 ⎭ ⎩

Here the corresponding n, i, j, k, w those in eq 3.

exp

and w

cal

(4)

are the same as

3. RESULTS AND DISCUSSION 3.1. Experimental LLE data. The experimentally determined LLE data for the investigated ternary mixtures of water + cyclohexanone + isophorone and water + cyclohexanone + mesityl oxide at several temperatures of 308.15, 318.15, and

Figure 7. Effect of temperature on phase equilibrium behavior for water + cyclohexanone + isophorone system.

328.15 K under 101.3 kPa are tabulated in Tables 3 and 4, where concentrations are presented in mass fraction. Water, E



Article

Table 5. Parameters and Correlation Factor (R2) of the Bachman and Hand Equations for the Ternary Systems Water + Cyclohexanone + Isophorone and Water + Cyclohexanone + Mesityl Oxide at Various Temperatures Bachman T/K

Figure 8. Effect of temperature on phase equilibrium behavior for water + cyclohexanone + mesityl oxide system.

Figure 9. Bachman plots for the ternary system water + cyclohexanone + solvents (isophorone or mesityl oxide) at 308.15, 318.15, and 328.15 K.

A

308.15 318.15 328.15

−0.0354 −0.0300 −0.0309

308.15 318.15 328.15

−0.0255 −0.0237 −0.0190

B

Hand R

2

Isophorone 0.9999 0.9999 0.9998 Mesityl Oxide 0.9864 1.0000 0.9896 0.9999 0.9742 1.0000 0.9928 0.9960 0.9859

a

b

R2

4.1325 4.0183 3.6009

1.4541 1.3478 1.2686

0.9960 0.9949 0.9878

3.7161 3.8396 3.8545

1.2256 1.2141 1.2523

0.9943 0.9894 0.9934

Figure 11. Experimental separation factor (S) versus cyclohexanone mass fraction (wII2 ) in the organic phase for the ternary system water (1) + cyclohexanone (2) + isophorone (3) at 308.15, 318.15, and 328.15 K.

much greater solubility in the extract phase than in the raffinate phase. An analogous result has also been observed in the previously published article.4 Furthermore, the equilibrium phase diagrams for the investigated ternary systems of water + cyclohexanone + solvents (isophorone or mesityl oxide) are classified as type II based on Treybal’s contribution38 because they consist of one completely miscible binary component (cyclohexanone + solvents) and two partially miscible binary components (water + cyclohexanone and water + solvents).19,26,39 Besides, it can be found from the LLE phase diagrams that the feed composition points can match the tie lines with a good degree of accuracy, which is in congruence with the lever rule and implies that the mass balance is satisfied for all the experimental operations.15,40 As demonstrated in Figures 7 and 8, the temperature has an insignificant effect on the phase equilibrium behavior in the measured temperature range for the two studied systems in the present work. The consistency and reliability of the experimental LLE results are tested using Bachman28 and Hand29 equations, which are given as follows:

Figure 10. Hand plots for the ternary system water + cyclohexanone + solvents (isophorone or mesityl oxide) at 308.15, 318.15, and 328.15 K.

cyclohexanone, and solvent are identified as ingredient 1, 2, and 3, respectively. Meanwhile, the corresponding triangular phase diagrams for each ternary system, together with the tie lines and feed composition, are plotted and depicted in Figures 1−6. The slopes of the tie lines indicate that cyclohexanone has a

⎛ w II ⎞ w3II = A + B⎜ 3I ⎟ ⎝ w1 ⎠ F

(5) DOI: 10.1021/acs.jced.7b00787 J. Chem. Eng. Data XXXX, XXX, XXX−XXX


Article

obtain an excellent separation of cyclohexanone from water. Simultaneously, it is worth noting that the values of the separation parameter in all cases are considerably greater than unity, suggesting that cyclohexanone can be efficiently recovered from aqueous solution by isophorone or mesityl oxide. The variation of separation factor against the cyclohexanone mass fraction in the solvent-rich phase for the investigated ternary mixtures is typically illustrated in Figures 11 and 12. As the figures show, the values of S decrease as the content of cyclohexanone increases at the same temperature, which could occur because the biphase zone shrinks with the increase of cyclohexanone content, meaning that the extracting capability of the selected solvents reduces and low concentration is appropriate for the extraction process; similar phenomena have been observed in earlier reports.15,16 In addition, the ternary mixture with mesityl oxide shows higher values of the separation factor than other mixtures containing isophorone probably because of an appreciable solvent effect.41 This shows that mesityl oxide is superior to isophorone for the extraction of cyclohexanone from aqueous solution. 3.2. LLE Data Correlation. By utilizing both the aforementioned thermodynamic models, NRTL as well as UNIQUAC, the experimentally determined tie-line compositions can be regressed. The binary interaction parameters of the two models are acquired through data correlation. The values of optimized NRTL and UNIQUAC interaction parameters, together with the corresponding values of RMSD, are given in Table 6. It can be apparently observed that all the calculated RMSD values in the present study are less than 0.015, which implies that the correlation result is satisfactory. The compositions calculated using the NRTL and UNIQUAC thermodynamic models for each ternary system are shown in Figures 1−6 with a comparison to experimental results; it reveals that the correlation results are in good accordance with the experimentally measured LLE data.

Figure 12. Experimental separation factor (S) versus cyclohexanone mass fraction (wII2 ) in the organic phase for the ternary system water (1) + cyclohexanone (2) + mesityl oxide (3) at 308.15, 318.15, and 328.15 K.

⎛ w II ⎞ ⎛ wI ⎞ ln⎜ 2II ⎟ = a + b ln⎜ 2I ⎟ ⎝ w1 ⎠ ⎝ w3 ⎠

w1I

(6)

w2I

where and represent the mass fraction of water and cyclohexanone, respectively, in the water-rich phase. w2II and w3II indicate the mass fraction of cyclohexanone and solvent, respectively, in the solvent-rich phase. A, a and B, b denote intercepts and slopes of the Bachman and Hand equations, fitted from the equilibrium compositions.16,17 The Bachman and Hand plots are described in Figures 9 and 10, and the fitting parameters, as well as corresponding correlation factors (R2), are reported in Table 5. According to Table 5, all of the values of R2 are near to 1, and the plots exhibit good linear correlation, suggesting high reliability of experimentally measured tie-line compositions in the current study.4 To shed light on the extraction capacity of the solvents (isophorone or mesityl oxide) selected to separate cyclohexanone from water, the calculated values of D and S for each ternary system are summarized in Tables 3 and 4. The large values of D indicate that a small quantity of extractant could

4. CONCLUSIONS The experimental tie-line compositions for the studied ternary mixtures of water + cyclohexanone + isophorone and water + cyclohexanone + mesityl oxide were reported over the temperature range of 308.15 to 328.15 K under 101.3 kPa. It was observed that the solubility of cyclohexanone in the extract phase was distinctly higher than that of cyclohexanone in the raffinate phase. The equilibrium phase diagrams of the studied

Table 6. Binary Interaction Parameters of NRTL and UNIQUAC Models for the Ternary Systems of Water (1) + Cyclohexanone (2) + Solvents (3) at (308.15−328.15) K model NRTL

UNIQUAC

NRTL

UNIQUAC

i−j 1−2 1−3 2−3 1−2 1−3 2−3 1−2 1−3 2−3 1−2 1−3 2−3

aij

aji

bij/K

Water (1) + Cyclohexanone (2) + Isophorone (3) 68.32 93.23 −4784.27 2.32 5.25 734.80 41.64 2.56 −10000.00 −1.32 −10.36 1097.91 1.24 −5.85 −365.59 0.33 −0.49 −115.41 Water (1) + Cyclohexanone (2) + Mesityl Oxide (3) 60.52 101.09 −2604.85 3.31 −1.26 290.90 −0.65 −0.19 90.57 4.77 −31.00 −892.74 −1.04 3.66 242.76 1.49 1.21 −11714.73 G

bji/K

α

RMSD

−2484.74 −1440.47 −848.33 −2776.40 1401.34 165.85

0.3 0.3 0.3

0.0118

−4790.04 766.72 183.10 3823.90 −1543.88 −83.14

0.3 0.3 0.3

0.0147

0.0031

0.0043



Article

methanol + 1-alkyl-3-methylimidazolium dialkylphosphates at 101.3 kPa. J. Chem. Eng. Data 2017, 62, 816−824. (14) Vozin, V. G.; Diyarow, I. N.; Gainullin, I. F. Study of extraction of cyclohexanone and ethyl acetate from aqueous solutions. J. Appl. Chem. USSR (Engl. Transl.); (United States) 1986, 58, 1525−1528. (15) Li, Y. X.; Xu, Q.; Liu, S. L.; Li, H. M.; Zhang, F. B.; Zhang, G. L.; Xia, Q. Liquid-liquid equilibrium for the ternary system of isopropyl acetate + 2-propanol + glycerol at different temperatures under atmospheric pressure. Fluid Phase Equilib. 2016, 412, 199−204. (16) Cai, F. F.; Ibrahim, J. J.; Niu, L.; Xu, W.; Xiao, G. M. Liquidliquid equilibrium for ternary system methanol + methyl acetate + 1,3dimethylimidazolium dimethylphosphate at several temperatures and atmospheric pressure. J. Chem. Eng. Data 2015, 60, 57−64. (17) Xu, D. M.; Zhang, L. Z.; Gao, J.; Pratik, D.; Zhao, L. W.; Cui, Z. F. Liquid-liquid equilibrium for ternary systems of ethyl acetate/ isopropyl acetate + 2,2,3,3-tetrafluoro-1-propanol + water at 298.15, 318.15 K. J. Chem. Thermodyn. 2017, 106, 218−227. (18) He, G. Y.; Wang, L. P.; Shi, M. D.; Li, Q. S.; Wang, Y. F. Measurements and thermodynamic models for the separation of 2methoxyethanol and water azeotropic mixtures via different solvents. J. Chem. Eng. Data 2017, 62, 2084−2089. (19) Ershova, O.; Pokki, J. P.; Zaitseva, A.; Alopaeus, V.; Sixta, H. Vapor pressure, vapor-liquid equilibria, liquid-liquid equilibria and excess enthalpy of the system consisting of isophorone, furfural, acetic acid and water. Chem. Eng. Sci. 2018, 176, 19−34. (20) Vozin, V. G.; Diyarov, I. N.; Gainullin, I. F. Thermodynamic characteristics of cyclohexanone distribution between extractants and water. J. Appl. Chem. USSR (Engl. Transl.); (United States) 1986, 58, 7. (21) Liu, H.; Cui, P.; Xin, K.; Sun, L. Y.; Wang, Y. F.; Li, Q. S. Experimental determination and correlation of liquid-liquid equilibria for water + cyclohexanone + solvents (Toluene or p-Xylene) ternary systems at 303.15 and 323.15 K under 101.3 kPa. J. Chem. Eng. Data 2017, 62, 2367−2373. (22) Colombo, A.; Battilana, P.; Ragaini, V.; Bianchi, C. L.; Carvoli, G. Liquid-liquid equilibria of the ternary systems water + acetic acid + ethyl acetate and water + acetic acid + isophorone (3,5,5-trimethyl-2cyclohexen-1-one). J. Chem. Eng. Data 1999, 44, 35−39. (23) Stephenson, R. M. Mutual solubilities: water-ketones, waterethers, and water-gasoline-alcohols. J. Chem. Eng. Data 1992, 37, 80− 95. (24) Stephenson, R.; Stuart, J. Mutual binary solubilities: wateralcohols and water-esters. J. Chem. Eng. Data 1986, 31, 56−70. (25) Chen, Y.; Wang, Y. C.; Zhou, S. M.; Chen, H.; Liu, D.; Li, L. B. Liquid phase equilibrium of the ternary systems, water + propionic or butyric acid + mesityl oxide, at (298.2 and 323.2) K. J. Chem. Thermodyn. 2017, 111, 72−79. (26) Liu, D.; Li, L. B.; Lv, R.; Chen, Y. Liquid-liquid equilibria for the ternary system mesityl oxide + phenol + water at 298.15, 313.15, and 323.15 K. J. Chem. Eng. Data 2016, 61, 2493−2498. (27) Feng, Y. R.; Song, H. B.; Xiao, M.; Lin, K.; Guo, K.; Gai, H. J. Development of phenols recovery process from coal gasification wastewater with mesityl oxide as a novel extractant. J. Cleaner Prod. 2017, 166, 1314−1322. (28) Bachman, I. Tie lines in ternary liquid systems. Ind. Eng. Chem., Anal. Ed. 1940, 12, 38−39. (29) Hand, D. B. Dineric distribution. J. Phys. Chem. 1930, 34, 1961− 2000. (30) Renon, H.; Prausnitz, J. M. Local compositions in thermodynamic excess functions for liquid mixtures. AIChE J. 1968, 14, 135−144. (31) 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. (32) Dai, F. F.; Xin, K.; Song, Y. H.; Shi, M. D.; Yu, Y. M.; Li, Q. S. Liquid-liquid equilibria for the ternary system containing 1-Butanol + methoxy (methoxymethoxy) methane + water at temperatures of 303.15, 323.15 and 343.15 K. Fluid Phase Equilib. 2016, 409, 466−471. (33) Gao, J.; Zhang, L. Z.; Xu, D. M.; Wei, Y.; Zhang, Z. S.; Cui, Z. F. Liquid-liquid equilibrium for the ternary system 2,2,3,3,4,4,5,5-

ternary systems were Treybal’s type II. Moreover, the Bachman and Hand empirical equations were utilized to ascertain the consistency of the obtained LLE tie-line compositions, with an R2 > 0.98. The resultant separation factors were remarkably greater than unity, confirming the feasibility of studied extractants for separating cyclohexanone from its mixture with water. In addition, the experimentally determined tie-line compositions were correlated accurately using NRTL and UNIQUAC methods with all the RMSD values being less than 0.015. The present work provides a valuable reference for the design and development of solvent extraction technology in the process of separating cyclohexanone from industrial wastewater.

■

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Qingsong Li: 0000-0003-1425-8822 Funding

Financial support from the Fundamental Research Funds for the Central Universities (No. 15CX06048A) is gratefully acknowledged. Notes

The authors declare no competing financial interest.

■

REFERENCES

(1) Suresh, A. K.; Sharma, M. M.; Sridhar, T. Engineering aspects of industrial liquid-phase air oxidation of hydrocarbons. Ind. Eng. Chem. Res. 2000, 39, 3958−3997. (2) Shi, C. F.; Zhu, B.; Lin, M.; Long, J.; Wang, R. W. Cyclohexanone mild oxidation catalyzed by new titanosilicate with hollow structure. Catal. Today 2011, 175, 398−403. (3) Schuchardt, U.; Cardoso, D.; Sercheli, R.; Pereira, R.; Cruz, R. S. D.; Guerreiro, M. C.; Mandelli, D.; Spinacé, E. V.; Pires, E. L. Cyclohexane oxidation continues to be a challenge. Appl. Catal., A 2001, 211, 1−17. (4) Pei, Y. C.; Wang, Q. B.; Gong, X.; Lei, F. Q.; Shen, B. W. Distribution of cyclohexanol and cyclohexanone between water and cyclohexane. Fluid Phase Equilib. 2015, 394, 129−139. (5) Sakthivel, A.; Selvam, P. Mesoporous (Cr)MCM-41: A mild and efficient heterogeneous catalyst for selective oxidation of cyclohexane. J. Catal. 2002, 211, 134−143. (6) Weissermel, K.; Arpe, H. J. Industrial Organic Chemistry, 2nd ed.; VCH Press: Weinheim, 1993. (7) Carabineiro, S. A. C.; Martins, L. M. D. R. S.; Avalos-Borja, M.; Buijnsters, J. G.; Pombeiro, A. J. L.; Figueiredo, J. L. Gold nanoparticles supported on carbon materials for cyclohexane oxidation with hydrogen peroxide. Appl. Catal., A 2013, 467, 279−290. (8) Guo, C. C.; Chu, M. F.; Liu, Q.; Liu, Y.; Guo, D. C.; Liu, X. Q. Effective catalysis of simple metalloporphyrins for cyclohexane oxidation with air in the absence of additives and solvents. Appl. Catal., A 2003, 246, 303−309. (9) Cheng, N. L. Solvents Handbook, 4th ed.; Chemical Industry Press: Beijing, 2008. (10) Guo, Z.; Chin, J.; Lee, J. W. Feasibility of continuous reactive distillation with azeotropic mixtures. Ind. Eng. Chem. Res. 2004, 43, 3758−3769. (11) Yuan, S. F.; Zou, C. C.; Yin, H.; Chen, Z. R.; Yang, W. D. Study on the separation of binary azeotropic mixtures by continuous extractive distillation. Chem. Eng. Res. Des. 2015, 93, 113−119. (12) Dohnal, V.; Baránková, E.; Blahut, A. Separation of methyl acetate + methanol azeotropic mixture using ionic liquid entrainers. Chem. Eng. J. 2014, 237, 199−208. (13) Cao, J.; Yu, G. R.; Chen, X. C.; Abdeltawab, A. A.; Al-Enizi, A. M. Determination of vapor-liquid equilibrium of methyl acetate + H



Article

octafluoro-1-pentanol + ethanol + water at (298.15, 308.15, and 318.15) K. J. Chem. Eng. Data 2015, 60, 2733−2738. (34) BIPM; IEC; IFCC; ILAC; ISO; IUPAC; IUPAP; OIML. Evaluation of measurement data−Guide to the expression of uncertainty in measurement. Joint Committee for Guides in Metrology, 2008. (35) Shi, M. D.; He, G. Y.; Gan, F.; Yu, X. M.; Li, Q. S. Extraction of low concentration aqueous solution of methylal: liquid-liquid equilibrium in water + methylal + (cyclohexane and n-heptane) ternary systems. J. Chem. Eng. Data 2017, 62, 2183−2190. (36) Sørensen, J. M.; Magnussen, T.; Rasmussen, P.; Fredenslund, A. Liquid-liquid equilibrium data: their retrieval, correlation and prediction. Part II: correlation. Fluid Phase Equilib. 1979, 3, 47−82. (37) Hwang, I. C.; Park, S. J. 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. (38) Treybal, R. E. Liquid Extraction; McGraw-Hill; New York, 1963. (39) Ghanadzadeh, H.; Ghanadzadeh, A.; Asgharzadeh, S.; Moghadam, M. Measurement and correlation of phase equilibrium data of the mixtures consisting of butyric acid, water, cyclohexanone at different temperatures. J. Chem. Thermodyn. 2012, 47, 288−294. (40) Almeida, B. F.; Waldrigui, T. M.; Alves, T. C.; Oliveira, L. H.; Aznar, M. Experimental and calculated liquid−liquid equilibrium data for water + furfural + solvents. Fluid Phase Equilib. 2012, 334, 97−105. (41) Gilani, H. G.; Gilani, A. G.; Saadat, S. L. S. Experimental and correlational study of phase equilibria in aqueous solutions of formic and butyric acids with isoamyl acetate and methyl isoamyl ketone at T = 298.15 K. J. Chem. Eng. Data 2014, 59, 917−925.

I


Measurement and Correlation of Ternary (Liquid+ Liquid) Equilibria for

Recommend Documents