Liquid–Liquid Equilibria for the Ternary Systems Water +

Dec 12, 2017 - The distribution coefficient (D) and selectivity value (S) were employed to assess the separation capability of MIBC and MIBK. The Hand...
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Article Cite This: J. Chem. Eng. Data 2018, 63, 95−101

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Liquid−Liquid Equilibria for the Ternary Systems Water + Cyclohexanol + Methyl Isobutyl Carbinol and Water + Cyclohexanol + Methyl Isobutyl Ketone at Different Temperatures Hai Liu, Xuemin Yu, Peng Cui, Bing Jia, Yingmin Yu, and Qingsong Li* The State Key Lab of Heavy Oil Processing, College of Chemical Engineering, China University of PetroleumEast China, Qingdao, 266580, P. R. China ABSTRACT: Liquid−liquid equilibria (LLE) data provide fundamentals for the design and simulation of an extraction operation. The objective of this work is to extract cyclohexanol from aqueous solution using appropriate solvents. Liquid−liquid extractions for two ternary systems comprising water + cyclohexanol + solvents (methyl iso-butyl carbinol, MIBC) as well as methyl iso-butyl ketone, MIBK) were carried out at 303.15, 323.15 K and 308.15, 318.15 K, respectively. The distribution coefficient (D) and selectivity value (S) were employed to assess the separation capability of MIBC and MIBK. The Hand and Bachman empirical equations were both used to ascertain the consistency of the experimental results. The nonrandom twoliquid model and the universal quasi-chemical model were applied to fit the obtained LLE results and yielded corresponding binary interaction parameters. Moreover, the root-mean-square deviation (rmsd) values were evaluated for two studied ternary systems, demonstrating both models can regress the experimental data well. cyclohexylamine) at 298.15 K and 323.15 K. Pei et al.13 investigated the ternary LLE systems of water + cyclohexanol + cyclohexane at the temperatures from 303.15 K to 333.15 K. The ternary LLE system of water + 1,4-dioxane + cyclohexanol at different temperatures (313.15 to 343.15 K) have been studied by Qiu et al.14 However, accurate LLE data for ternary systems of water + cyclohexanol + methyl isobutyl carbinol (MIBC) and water + cyclohexanol + methyl isobutyl ketone (MIBK) were unavailable. The aim of this work is to extract cyclohexanol from aqueous solution using suitable organic solvents. Although a series of solvents have been chosen as extractants for the recovering of cyclohexanol, searching for alternate and excellent extraction solvents is still of great significance. From the literature survey, it was found that MIBC (the boiling point is 404.65 K) and MIBK (the boiling point is 389.15 K) are desirable solvents due to their proper physical and chemical properties. Thus, in recently published articles15−17 they have been selected as extractants to recover chemicals from aqueous solution and received ideal results. Taking into account the appropriate properties and high extraction efficiency of MIBC as well as MIBK, both solvents were employed in this work. The LLE experimental data for the ternary systems of water + cyclohexanol + MIBC and water + cyclohexanol + MIBK were determined at the desired temperatures (303.15, 323.15 and 308.15, 318.15 K, respectively) under 101.3 kPa. The different temperature ranges adopted for these two ternary

1. INTRODUCTION Cyclohexanol is an important bulk chemical in the nylon industry and is used as an intermediate to synthesize caprolactam and adipic acid, further manufacturing a series of nylon polymers. Owing to the importance of nylon fibers, cyclohexanol has been produced on a large scale. There are three main industrial routes for cyclohexanol production, the cyclohexane oxidation method, the direct hydration of cyclohexane, and the hydrogenation of phenol, of which the cyclohexane oxidation is the most commonly used route.1−3 The manufacture and utilization of cyclohexanol produce a large amount of wastewater, which has a severe influence on the environment.4,5 Thus, recovering cyclohexanol from wastewater before its discharging into nature is of great economic and environmental interest. As a widespread separation method in industry, solvent extraction has many advantages, such as high efficiency, energysaving, and ease of operation.6 In this way, a solvent extraction technique has been applied to recover phenols, N,Ndimethylacetamide (DMAC), and other useful chemicals.7−9 The selection of solvent becomes a critical factor to carry out a proper extraction process. The physical and chemical properties (such as molecular structure, density, and polarity as well as boiling point) must be considered when an organic solvent is chosen.10 LLE data provide a basis for extraction operation, which are vital to perform a proper extraction process simulation and optimization.11 The ternary systems of water + cyclohexanol + solvents have been studied by lots of researchers in recent years. Mandy Klauck12 and his team reported the LLE data of four ternary systems containing water + cyclohexanol + solvents (heptane, toluene, cyclohexane, and © 2017 American Chemical Society

Received: July 24, 2017 Accepted: November 27, 2017 Published: December 12, 2017 95

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2.3. Analysis Method. The samples collected from the upper and lower phase were assayed by means of a gas chromatograph (GC-Agilent Technologies, 6820, USA) equipped with a packed column (Porapak N column, 3 mm × 3 m) and a thermal conductivity detector (TCD). Highpurity hydrogen with a stable flow velocity of 1.0 mL s−1 was used as the carrier gas. The internal standard method was chosen to determine the contents of components in each phase, where 2-propanol was selected as the internal standard substance. In each GC analysis, the injector and detector were both operated at 523.15 K; the initial oven temperature was maintained at 393.15 K for 1.5 min, after which the temperature was increased to 523.15 K at a rate of 20 K min−1 and held at this temperature for the other 1 min. Each sample was analyzed by GC more than three times with a standard deviation less than 0.08% to ensure the accuracy, thus the average result was used as the final composition. Furthermore, the GUM standard24 was employed to calculate the standard uncertainty of the compositions in two separate phases in this work.

systems were to used investigate the temperature effect on the separation capability. To the best of the authors’ knowledge, none of these LLE data have been given in the literature. Distribution coefficients (D) and selectivity values (S) were adopted to assess the extraction effect of the selected solvents. Additionally, the empirical Hand equation18 and Bachman equation19 were both applied to examine the reliability of the obtained tie-line data. Furthermore, the nonrandom two-liquid (NRTL)20 and the universal quasi-chemical (UNIQUAC)21 model were employed to regress the LLE results, and the values of binary interaction parameters for these two models were generated.

2. EXPERIMENTAL SECTION 2.1. Materials. Cyclohexanol and MIBC were supplied by the Aladdin Chemistry Co., isopropyl alcohol and MIBK were supplied by Sinopharm Chemical Reagent Co. Ultrapure water was produced in our laboratory and used throughout all the operations. The declared purities (mass fraction) of these chemicals were all >0.99, and gas chromatography (GC) was employed to check the purities of them. Thus, all these chemicals were directly used without further purification. The CAS number, suppliers, and declared mass fractions of the used materials were summarized in Table 1.

3. RESULTS AND DISCUSSION 3.1. LLE Experimental Data. The obtained LLE experimental results for the ternary systems cyclohexanol + water + MIBC and cyclohexanol + water + MIBK at desired temperatures under 101.3 kPa were reported in Tables 2 and 3, where x1, x2, and x3 denote the mole fractions of water, cyclohexanol, and solvent, respectively. The corresponding standard uncertainties for temperature, pressure, and components are also presented on the footnotes of Tables 2 and 3. As can be seen from these two tables, the water content in the solvent-rich phase and the cyclohexanol content in the waterrich phase increase with the feed amount of cyclohexanol. However, the opposite trend was observed for the solvent concentrations in the water-rich phase. The triangle phase diagrams for different ternary systems at desired temperatures were plotted in Figures 1−4. Generally, the area of heterogeneous region at the same temperature for the ternary system containing MIBK is larger than the system containing MIBC, which can be attributed to the smaller mutual solubilities between water and MIBK. Also, the feed-point compositions of the studied ternary systems were also presented in Figures 1−4. All the feed points agree with the tie-lines accurately, demonstrating the balance of material and the reliability of the obtained data.25 To examine the capability of MIBC as well as MIBK to separate cyclohexanol from dilute aqueous solution, two important parameters in liquid−liquid extraction, distribution coefficient (D) and selectivity value (S), were applied in this work listed as following forms:

Table 1. Main Description of the Chemicals analysis method

component

CASRN

water isopropyl alcohol methyl isobutyl ketone (MIBK) methyl isobutyl carbinol (MIBC)

7732-18-5 67-63-0 108-10-1

self-made Sinopharm Sinopharm

⩾99.9 ⩾99.7 ⩾99.0

GCa GCa GCa

108-11-2

⩾99.0

GCa

cyclohexanol

108-93-0

Aladdin Chemistry Co. Aladdin Chemistry Co.

⩾99.0

GCa

a

suppliers

declared mass fractions

Gas chromatography.

2.2. Experimental Apparatus and Procedure. A 100 cm3 round-bottom glass jacketed phase equilibrium cell was used in this work, which was connected to a superthermostatic water bath to keep the temperature constant. The fluctuation of the system temperature was ±0.1 K. A glass condenser was utilized to cooled the steam down and prevent it from evaporating. The detail apparatus was shown in our recent work22 and other typical ternary LLE work.23 First, water, cyclohexanol, and the selected solvent were fed into the cell to form a liquid mixture. After the desired temperature of the system was reached, the liquid mixture was vigorously agitated for more than 3 h by a magnetic stirrer and then left to stand for a minimum 8 h to reach a phase equilibrium and splitting. A long needle syringe was used to take out samples when two liquid phases were formed. Each layer was sampled by a separate syringe to avoid contamination and the injection volume of each sample was 0.8 μL. The collected samples were analyzed as quickly as possible to prevent phase splitting. A series of LLE data were attained by quantitative addition of cyclohexanol or changing the temperatures of the ternary systems.

D=

S=

x 2II x 2I

(1)

x 2II/x 2I x1II/x1I

(2)

where D is the distribution coefficient of cyclohexanol between the organic and aqueous phases; xI2 and xI1 denote the mole concentrations of cyclohexanol and water in the water-rich phase, respectively. xII2 and xII1 represent the mole contents of cyclohexanol and water in the solvent-rich phase, respectively. 96

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Table 2. Experimental LLE Results in Mole Fraction for Water (1) + Cyclohexanol (2) + MIBC (3) System at 303.15 and 323.15 K under 101.3 kPaa MIBC-rich phase x1

a

x2

water-rich phase x3

0.2994 0.3084 0.3127 0.3356 0.3551 0.3568 0.3621 0.3651

0.0365 0.0716 0.1091 0.1738 0.2366 0.2667 0.2969 0.3273

0.6640 0.6199 0.5783 0.4906 0.4083 0.3766 0.3410 0.3076

0.3212 0.3316 0.3365 0.3472 0.3563 0.3642 0.3657 0.3830

0.0356 0.0702 0.1008 0.1377 0.1701 0.2006 0.2336 0.3143

0.6432 0.5982 0.5627 0.5151 0.4737 0.4352 0.4007 0.3026

x1

x2

T/K = 303.15 0.9955 0.0004 0.9952 0.0008 0.9951 0.0014 0.9952 0.0021 0.9947 0.0028 0.9934 0.0036 0.9929 0.0042 0.9923 0.0049 T/K = 323.15 0.9961 0.0004 0.9961 0.0007 0.9958 0.0011 0.9955 0.0015 0.9952 0.0019 0.9948 0.0023 0.9946 0.0027 0.9946 0.0036

x3

D

S

0.0041 0.0040 0.0035 0.0028 0.0025 0.0030 0.0029 0.0029

88.57 85.60 78.71 83.11 84.43 74.29 71.24 67.44

294.4 276.2 250.5 246.4 236.5 206.9 195.4 183.3

0.0036 0.0032 0.0031 0.0030 0.0029 0.0029 0.0027 0.0018

96.44 96.82 95.44 92.32 89.23 86.45 85.58 86.66

299.1 290.8 282.5 264.7 249.3 236.1 232.7 225.0

Standard uncertainties u are u(T) = 0.1K, u(p) = 1 kPa, and u(x) = 0.004.

Table 3. Experimental LLE Results in Mole Fraction for Water (1) + Cyclohexanol (2) + MIBK (3) System at 308.15 and 318.15 K under 101.3 kPaa MIBK-rich phase x1

a

x2

water-rich phase x3

0.1250 0.1512 0.1777 0.1938 0.2239 0.2458 0.2693 0.2942 0.3152 0.3344

0.0409 0.0849 0.1247 0.1632 0.1919 0.2255 0.2571 0.2838 0.3089 0.3349

0.8340 0.7639 0.6976 0.6429 0.5841 0.5287 0.4736 0.4220 0.3759 0.3306

0.1518 0.1684 0.2296 0.2449 0.2749 0.2987 0.3232 0.3321

0.0404 0.0815 0.1952 0.2300 0.2582 0.2862 0.3103 0.3409

0.8078 0.7501 0.5752 0.5251 0.4669 0.4151 0.3665 0.3270

x1

x2

T/K = 308.15 0.9932 0.0008 0.9936 0.0013 0.9936 0.0018 0.9938 0.0022 0.9940 0.0026 0.9937 0.0030 0.9931 0.0034 0.9930 0.0037 0.9925 0.0042 0.9930 0.0043 T/K = 318.15 0.9942 0.0006 0.9936 0.0013 0.9937 0.0025 0.9936 0.0029 0.9933 0.0033 0.9930 0.0036 0.9928 0.0040 0.9924 0.0046

x3

D

S

0.0060 0.0051 0.0046 0.0040 0.0034 0.0034 0.0035 0.0033 0.0033 0.0028

53.74 63.67 70.08 72.95 75.05 76.17 75.53 75.92 73.04 78.46

426.9 418.4 391.8 374.0 333.1 307.9 278.5 256.2 230.0 233.0

0.0052 0.0051 0.0038 0.0035 0.0034 0.0033 0.0032 0.0031

63.11 64.48 77.24 80.05 79.41 78.52 76.89 74.67

413.3 380.5 334.3 324.7 287.0 261.0 236.2 223.1

Standard uncertainties u are u(T) = 0.1 K, u(p) = 1 kPa and u(x) = 0.004.

The values of D and S for the two studied ternary systems were also listed in Tables 2 and 3. The large D and S values mean that cyclohexanol is more soluble in MIBC and MIBK than in water, indicating that both MIBC and MIBK perform an excellent job for extracting cyclohexanol. The temperature effects on the selectivity values (S) for these two ternary systems were presented in Figures 5 and 6. As can be observed from these figures, the values of S have an apparent downward trend as the cyclohexanol concentration in the solvent-rich phase increases. Additionally, slightly larger selectivity values were obtained at a higher temperature for each ternary system,

demonstrating that the effect of temperature on tie-line data is negligible. Thus, it is appropriate to carry out the extraction operations at a low concentration of cyclohexanol in aqueous solution and a lower temperature under the premise of economy. 3.2. Consistency and Reliability of LLE Data. The reliability and consistency of the obtained experimental results were tested by the Hand and Bachman empirical correlation equations. These equations are shown as follows:18,19 97

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Figure 1. LLE ternary phase diagram (in mole fraction) for water + cyclohexanol + MIBC system at 303.15 K: (∗) experimental data; (△) NRTL model; (●) UNIQUAC model; (☆) feed composition; () tie-lines.

Figure 4. LLE ternary phase diagram (in mole fraction) for water + cyclohexanol + MIBK system at 318.15 K: (∗) experimental data; (△) NRTL model; (●) UNIQUAC model; (☆) feed composition; () tie-lines.

Figure 2. LLE ternary phase diagram (in mole fraction) for water + cyclohexanol + MIBC system at 323.15 K: (∗) experimental data; (△) NRTL model; (●) UNIQUAC model; (☆) feed composition; () tie-lines. Figure 5. Experimental selectivity values (S) versus the cyclohexanol mole fraction in the solvent rich phase (x2II) for the ternary system water (1) + cyclohexanol (2) + MIBC (3) at desired temperatures: (■) at 303.15 K; (●) at 323.15 K.

Figure 3. LLE ternary phase diagram (in mole fraction) for water + cyclohexanol + MIBK system at 308.15 K: (∗) experimental data; (△) NRTL model; (●) UNIQUAC model; (☆) feed composition; () tie-lines.

⎛ x II ⎞ ⎛xI⎞ ln⎜ 2II ⎟ = a1 + b1 ln⎜ 2I ⎟ ⎝ x1 ⎠ ⎝ x3 ⎠

⎛ x II ⎞ x3II = a 2 + b2⎜ 3I ⎟ ⎝ x1 ⎠

(3) Figure 6. Experimental selectivity values (S) versus the cyclohexanol mole fraction in the solvent rich phase (x2II) for the ternary system water (1) + cyclohexanol (2) + MIBK (3) at desired temperatures: (■) at 308.15 K; (●) at 318.15 K.

(4) 98

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where a1, b1 and a2, b2 refer to the constants of these two equations, respectively; subscripts 1, 2, and 3 represent water, cyclohexanol, and the selected solvents, respectively; I and II denote the aqueous and organic phases, respectively. The Hand plots and Bachman plots for two ternary systems at desired temperatures were shown in Figures 7 and 8. The fitting

constants and corresponding linear correlation coefficients (Rsquare) for each ternary system at the desired temperatures were listed in Table 4. As can be observed from this table, all the values of R2 approach 1, exhibiting a high consistency of our tie-line data. 3.3. Data Correlation and Prediction. The NRTL and UNIQUAC models are two typical activity coefficient models, which have been widely used in the correlation of ternary LLE data. The detail description for these two models were shown in other typical LLE work.26,27 In this work, both models were adopted to regress the experimental results by applying the Aspen V8.4 software. The fitted results of the aforementioned two models at the desired temperatures were also presented in the triangle diagrams shown in Figures 1−4. Just as we can see, the calculated data show an excellent agreement with the experimental results at each temperature, demonstrating that both models can simulate the extraction process well. The structural parameters of UNIQUAC model, r and q originated from the literature13,28,29 and are listed in Table 5. Table 5. Structural parameters13,28,29 (r and q) for the UNIQUAC Modela

Figure 7. Hand plots for the ternary system water + cyclohexanol + solvents (MIBC or MIBK) at different temperatures: (■) MIBC at 303.15 K; (●) MIBC at 323.15 K; (▲) MIBK at 308.15 K; (▼) MIBK at 318.15 K. a

component

r

q

water cyclohexanol MIBK MIBC

0.9200 4.2740 4.5967 4.8016

1.3997 3.2840 3.9560 4.1240

Notation: r, volume parameter; q, surface area parameter.

The obtained binary interaction parameters (aij, aji and bij, bji) were derived from regressing the experimental results using two correlation models and are presented in Tables 6 and 7. For the NRTL correlation, the nonrandomness parameter αij was set at 0.2 or 0.3 and the values were obtained from the literature.30 The binary interaction parameters of these two models could be generated by minimizing the square of the difference between the phase equilibrium compositions. The objective function F is given as follows: m

F=

2

3

∑ ∑ ∑ (xijkexptl − xijkcal)2 (5)

i=1 j=1 k=1 exptl

cal

where m represents the number of tie-lines; x and x are the experimental and calculated mole fractions, respectively, the subscripts i, j, and k refer to the components, the phases, and the tie lines, respectively. In addition, the root-mean-square deviation (rmsd) values were used to judge the correlation quality between the calculated and experimental data by applying the following equation:

Figure 8. Bachman plots for the ternary system water + cyclohexanol + solvents (MIBC or MIBK) at different temperatures: (■) MIBC at 303.15K; (●) MIBC at 323.15K; (▲) MIBK at 308.15K; (▼) MIBK at 318.15K.

Table 4. Constants and Linear Correlation Coefficients of the Hand and Bachman Equations for Water (1) + Cyclohexanol (2) + Solvents (3) System at Desired Temperatures Hand T/K MIBC-303.15 MIBC-323.15 MIBK-308.15 MIBK-318.15

K K K K

Bachman

a1

b1

R2a

a2

b2

R2a

6.5620 6.8347 9.1224 8.4150

1.2270 1.2421 1.7070 1.5718

0.9939 0.9874 0.9918 0.9910

−0.0017 −0.0012 −0.0003 −0.0008

0.9981 0.9979 0.9940 0.9950

0.9999 0.9999 0.9999 0.9999

a 2

R is the linear correlation coefficient for the two equations. 99

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Table 6. Binary Interaction Parameters of NRTL and UNIQUAC Models for the Ternary System Water (1) + Cyclohexanol (2) + MIBC (3) at the Temperatures T = (303.15 and 323.15) K and p = 101.3 kPa model NRTL

UNIQUAC

NRTL

UNIQUAC

i−j

aij

1−2 1−3 2−3 1−2 1−3 2−3

94.17 10.23 16.95 −29.85 −2.04 −2.27

1−2 1−3 2−3 1−2 1−3 2−3

90.97 10.28 −0.42 −0.35 −0.23 −3.69

aji

bji

αij

rmsd/%

−5187.36 926.25 −2.42 539.60 −992.21 105.66

0.2 0.2 0.3

0.65

−4742.85 941.56 179.26 97.31 −80.72 428.77

0.2 0.2 0.3

bij

T = 303.15K 106.40 −5078.17 −3.47 −1371.72 −0.01 5138.64 −20.43 1699.79 2.58 489.69 0.52 −643.26 T = 323.15K 106.03 −4720.35 −3.41 −1407.71 0.55 −137.43 −0.59 −43.78 −0.32 −35.93 −0.64 1104.34

0.67

0.20

0.30

Table 7. Binary Interaction Parameters of NRTL and UNIQUAC Models for the Ternary System Water (1) + Cyclohexanol (2) + MIBK (3) at the Temperatures T = (308.15 and 318.15) K and p = 101.3 kPa model NRTL

UNIQUAC

NRTL

UNIQUAC

i−j

aij

1−2 1−3 2−3 1−2 1−3 2−3

90.80 1.03 −0.76 −30.12 −1.95 0.15

1−2 1−3 2−3 1−2 1−3 2−3

89.33 1.00 −0.74 −30.01 −1.94 0.16

1/2 ⎧ m 2 3 (x exptl − x cal)2 ⎫ ⎪ ⎪ ijk ijk ⎬ rmsd = ⎨∑ ∑ ∑ ⎪ ⎪ 6m ⎩ i=1 j=1 k=1 ⎭

aji

bji

αij

rmsd/%

−4859.85 −12865.04 440.20 694.88 −1154.68 −191.39

0.2 0.2 0.3

0.33

−4674.59 −12816.88 449.60 732.12 −1149.85 −194.76

0.2 0.2 0.3

bij

T = 308.15K 105.84 −4507.83 282.74 −831.60 1.43 −233.34 −20.38 1762.85 2.06 519.12 −0.46 92.54 T = 318.15K 105.41 −4110.02 282.43 −829.13 1.41 −236.29 −20.60 1740.28 2.13 521.51 −0.46 93.48

0.38

0.37

0.51

the experimental results were regressed well with both the NRTL and UNIQUAC activity coefficient models, and the corresponding binary parameters were obtained. The calculated minimum rmsd values were 0.20% and 0.30% for the NRTL and UNIQUAC simulations, respectively, showing that both models fit satisfactorily to the experimental LLE results, but the NRTL model performs slightly better.

(6)

where all the parameters are consistent with those in eq 5. The calculated rmsd values of NRTL and UNIQUAC models at desired temperatures were also listed in Tables 6 and 7. The minimum rmsd values of all the studied ternary LLE systems were 0.20% and 0.30% for the NRTL and UNIQUAC correlations, respectively, which indicates that all the measured LLE data could be correlated well by these two models. Moreover, the NRTL model has a slighter better correlation performance for the two ternary systems, since the rmsd values are smaller.

■

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Yingmin Yu: 0000-0002-0444-232X Qingsong Li: 0000-0003-1425-8822 Notes

4. CONCLUSIONS The LLE data for water + cyclohexanol + MIBC and water + cyclohexanol + MIBK ternary systems were measured at desired temperatures (303.15 K, 323.15 K and 308.15 K, 318.15 K, respectively) under 101.3 kPa. The large distribution coefficients (D) and selectivity values (S) reflect the excellent ability of extracting cyclohexanol from aqueous solution by using MIBC as well as MIBK. The Hand and Bachman empirical equations were both used to verify the reliability of the obtained LLE data and received good results. Additionally,

The authors declare no competing financial interest.

■

REFERENCES

(1) Hidalgo, P.; Toro, C.; Ciudad, G.; Schober, S.; Mittelbach, M.; Navia, R. Evaluation of Different Operational Strategies for Biodiesel Production by Direct Transesterification of Microalgal Biomass. Energy Fuels 2014, 28, 6. (2) Katariya, A.; Freund, H.; Sundmacher, K. Two-Step Reactive Distillation Process for Cyclohexanol Production from Cyclohexene. Ind. Eng. Chem. Res. 2009, 48, 9534−9545.

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DOI: 10.1021/acs.jced.7b00683 J. Chem. Eng. Data 2018, 63, 95−101