Article pubs.acs.org/jced
Liquid−Liquid Equilibrium in the Ternary Systems Water + Cyclohexanone + Benzene or Methyl Isobutyl Carbinol at 303.15 and 323.15 K: Experimental Data and Correlation Hai Liu, Xuemin Yu, Peng Cui, Midong Shi, Kun Xin, 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, Shandong, P. R. China ABSTRACT: Liquid−liquid equilibria provide fundamental data for designing and simulating a proper extraction process. The aim of this work is to extract cyclohexanone from wastewater using appropriate solvents. Liquid−liquid equilibrium experimental results were measured for water + cyclohexanone + benzene or methyl isobutyl carbinol ternary systems at 303.15 and 323.15 K under 101.3 kPa. The distribution ratios as well as selectivity values were calculated according to the experimental data to assess the extracting behaviors of the selected solvents. The selectivity value has a slight decrease with the increasing temperature from 303.15 to 323.15 K, which indicates that temperature has an adverse effect and the low temperature is more suitable for extraction. Besides, the consistency and reliability of the obtained experimental results were ascertained by applying both the Hand and Bachman equations. The obtained experimental tie-line data fitted well with the nonrandom two-liquid and universal quasichemical activity coefficient models, yielding root-mean-square deviation (rmsd) values as low as 0.17 and 0.16 for the two models, respectively. LLE data for these ternary systems. Pei et al.12 investigated the distribution of cyclohexanone between cyclohexane and water at 303.2−333.2 K. Considering that the liquid−liquid equilibrium (LLE) data of the water + cyclohexanone + benzene and water + cyclohexanone + methyl isobutyl carbinol (MIBC) ternary systems are unavailable, it is of great necessity to obtain reliable thermodynamic LLE data of these ternary systems, which is quite crucial to simulate, design, and optimize appropriate extraction operations.13 This study is aimed at experimentally determining the LLE data for water + cyclohexanone + benzene or MIBC ternary system. The experiments were performed for the studied ternary systems at desired temperatures (303.15 and 323.15 K) under pressure of 101.3 kPa. To the best of our knowledge, there are no reports for these LLE data in literature up to now. The reliability and consistency of the experimental results were assessed by applying both the Bachman14 and Hand15 correlation equations. The distribution ratios (D) and selectivity values (β) were calculated from the LLE data to evaluate the separation capacity of the selected extractants. The nonrandom two-liquid (NRTL)16 and universal quasichemical (UNIQUAC)17 models were also employed to regress the
1. INTRODUCTION Cyclohexanone is a widely utilized bulk chemical in the production of lots of nylon polymers where they are mainly used in the manufacture of adipic acid and caprolactam, respectively, as well as a very common organic solvent and an important intermediate in synthesizing a series of useful fine chemicals. Cyclohexanone is produced industrially by catalytic oxidation cyclohexane at 423−433 K using cobalt-based catalysts, forming a mixture containing cyclohexanol and cyclohexanone (called KA oil).1−3 Nowadays, cyclohexanone has become a common organic water pollutant, which was derived from the process of manufacturing and separating.4−6 Thus, to prevent the environmental contamination, various treating techniques have been used to remove cyclohexanone from wastewater before charging them into nature, such as steam striping method, microelectrolysis technology, and solvent extraction. However, the steam striping method requires a large amount of investment and huge energy consumption. Besides, microelectrolysis technology also consumes a lot of electric power.7,8 In contrast, solvent extraction has emerged as a preferable choice owing to its high efficiency and low energy consumption, which has been widely used as a classical separation process.9 To facilitate the development of cyclohexanone extraction from wastewater, Vozin et al.10,11 reported the use of several solvents such as hexane, heptane, benzene, and toluene with no © 2017 American Chemical Society
Received: June 6, 2017 Accepted: September 6, 2017 Published: September 15, 2017 3512
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Table 1. Materials Major Description and the UNIQUAC Structural Parameters of the Chemicals UNIQUAC structural parameters component
CAS
water cyclohexanone benzene MIBC a
7732-18-5 108-94-1 71-43-2 108-11-2
supplier
reported GC purity (mass %)
self-made Sinopharm Sinopharm Aladdin Chemistry Co.
⩾99.9 ⩾99.5 ⩾99.0 ⩾99.0
r
q
0.9200 4.1140 3.1878 4.8016
1.3997 3.3400 2.4000 4.1240
analysis method a
GC GCa GCa GCa
Gas chromatograph.
Table 2. Experimental LLE Data (Mole Fraction) for the Water (1) + Cyclohexanone (2) + Solvent (3) System at 303.15 K under 101.3 kPa, Together with Distribution Ratios (K1, K2) and Selectivity Values (β)a organic phase
aqueous phase
solvent
x1
x2
x3
x1
x2
x3
K1
K2
β
benzene
0.0049 0.0053 0.0062 0.0075 0.0088 0.0133 0.0145 0.0155 0.2271 0.2406 0.2467 0.2473 0.2591 0.2653 0.2686 0.2783
0.0082 0.0338 0.0498 0.0689 0.0957 0.1244 0.1523 0.1821 0.0228 0.0467 0.0923 0.1165 0.1612 0.1824 0.2042 0.2239
0.9869 0.9609 0.9440 0.9236 0.8955 0.8623 0.8332 0.8024 0.7502 0.7127 0.6610 0.6362 0.5797 0.5523 0.5273 0.4978
0.9988 0.9985 0.9985 0.9980 0.9978 0.9973 0.9971 0.9967 0.9950 0.9948 0.9939 0.9934 0.9934 0.9931 0.9924 0.9920
0.0001 0.0004 0.0006 0.0008 0.0012 0.0016 0.0018 0.0022 0.0005 0.0010 0.0019 0.0025 0.0035 0.0039 0.0045 0.0050
0.0011 0.0011 0.0010 0.0011 0.0011 0.0011 0.0011 0.0011 0.0045 0.0042 0.0042 0.0041 0.0032 0.0030 0.0031 0.0030
0.0049 0.0053 0.0063 0.0075 0.0089 0.0133 0.0145 0.0156 0.2282 0.2419 0.2482 0.2489 0.2608 0.2672 0.2706 0.2805
82.00 84.50 83.00 86.13 79.75 77.75 84.61 82.77 47.81 49.02 47.81 46.53 46.70 46.74 45.50 44.85
16735 15943 13175 11484 8961 5846 5835 5306 209.5 202.7 192.7 186.9 179.0 175.0 168.2 159.9
MIBC
a Standard uncertainties u are u(T) = 0.1 K, u(p) = 1 kPa, and u(x) = 0.002 except for mole fractions of MIBC and water in the water + cyclohexanone + MIBC organic phase where u(x) = 0.02.
systems. The liquid mixture was agitated vigorously for approximate 3 h and left to settle for another 6 h to ensure that a compete phase equilibrium was reached and forming into two liquid layers. Different LLE tie-line data were obtained with the variation of the composition or the temperature of the system, and the uncertainty of the operational temperature was estimated to be ±0.1 K. To determine the compositions of the two layers, the samples from both the upper phase and the lower phase were withdrawn by a long needle syringe carefully. An Agilent gas chromatography (GC6820) with a Porapak N column (3 mm × 3 m) was applied in the experiments to analyze the samples collected from two layers, whose detector is a thermal conductivity detector (TCD). The operational program of GC was as follows: The initial oven temperature was held at 393.15 K for 1.5 min, subsequently increased at a rate of 20 K min−1 to reach 523.15 K, and kept at this temperature for another 1 min. The temperatures of injector and the detector were maintained at 523.15 K. We used the high-purity hydrogen (99.999%) as the carrier gas with a constant flow rate of 1.0 mL s−1. The quantitative analysis of the samples was achieved by using internal standard method, where 2-propanol was used as the internal standard substance. Each sample was assayed by GC more than three times with a standard deviation below 0.1% to ensure the reliability, and the mean value was presented. In addition, the GUM standard20 was used to calculate the standard uncertainty of the compositions for the
experimental tie-line data for the different ternary systems and the binary parameters of the two models were obtained.
2. EXPERIMENTAL SECTION 2.1. Chemicals. The major details of the used chemical regents are presented in Table 1. Cyclohexanone and benzene were supplied from Sinopharm Chemical Reagent Co., while MIBC was purchased from Aladdin Reagents Co. Their declared purities (in mass fraction) were all >0.990. Ultrapure water was self-made and used throughout the entire experimental process. The purities of all of the materials were checked by gas chromatography (GC), where no obvious peaks of impurities were detected. All of the chemicals were used without further purification. 2.2. Apparatus and Procedure. The experimental LLE data of the studied ternary system water + cyclohexanone + solvents (benzene or MIBC) were obtained at desired temperatures (303.15 and 323.15 K) under 101.3 kPa. The experimental apparatus and analytical method employed in this research have been described in typical published paper18 and our previous work.19 The LLE equilibrium experiments were conducted by using an approximate 80 mL round-bottom glass equilibria cell, and the temperature was kept constant by connecting with a thermostatic water bath with an accuracy of ±0.1 K. Besides, a rubber stopper was used to seal the bottle and prevent the evaporation of the components. The agitation and setting time were investigated, and the results demonstrated that 5 h was enough to reach equilibrium for the studied 3513
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Table 3. Experimental LLE Data (Mole Fraction) for the Water (1) + Cyclohexanone (2) + Solvent (3) System at 323.15 K under 101.3 kPa, Together with Distribution Ratios (K1, K2) and Selectivity Values (β)a organic phase
aqueous phase
solvent
x1
x2
x3
x1
x2
x3
K1
K2
β
benzene
0.0076 0.0090 0.0106 0.0115 0.0126 0.0158 0.0189 0.0203 0.2541 0.2670 0.2821 0.2912 0.2975 0.3041 0.3090 0.3222
0.0070 0.0324 0.0506 0.0659 0.0885 0.1208 0.1535 0.1825 0.0235 0.0464 0.0682 0.0912 0.1339 0.1777 0.1982 0.2151
0.9854 0.9587 0.9388 0.9227 0.8988 0.8635 0.8276 0.7972 0.7223 0.6867 0.6497 0.6176 0.5686 0.5183 0.4928 0.4628
0.9991 0.9983 0.9980 0.9978 0.9975 0.9965 0.9958 0.9959 0.9956 0.9951 0.9946 0.9949 0.9932 0.9931 0.9930 0.9932
0.0001 0.0004 0.0006 0.0007 0.0009 0.0019 0.0020 0.0022 0.0004 0.0008 0.0013 0.0017 0.0027 0.0036 0.0039 0.0042
0.0009 0.0013 0.0014 0.0015 0.0016 0.0017 0.0022 0.0019 0.0040 0.0041 0.0041 0.0035 0.0041 0.0034 0.0031 0.0026
0.0076 0.0090 0.0106 0.0115 0.0127 0.0158 0.0190 0.0204 0.2553 0.2683 0.2836 0.2928 0.2996 0.3062 0.3111 0.3244
100.80 86.27 90.26 88.97 97.33 65.24 77.10 83.20 58.32 56.51 53.24 54.59 49.91 49.83 50.66 51.05
13226 9625 8520 7755 7683 4126 4060 4072 228.5 210.6 187.7 183.6 166.6 162.7 162.8 157.4
MIBC
a Standard uncertainties u are u(T) = 0.1 K, u(p) = 1 kPa, and u(x) = 0.002 except for mole fractions of MIBC and water in the water + cyclohexanone + MIBC organic phase where u(x) = 0.02.
two layers. The standard uncertainty of the compositions (in mole fraction) for the both layers was 0.002.
3. RESULTS AND DISCUSSION 3.1. Experimental LLE Data. The determined LLE results of water (1) + cyclohexanone (2) + solvents (benzene or MIBC) (3) ternary systems at 303.15 and 323.15 K were tabulated in Tables 2−3, and all of the compositions were listed in mole fraction. The triangle phase diagrams for each ternary system at desired temperatures (T = 303.15 and 323.15 K) were presented in Figures 1−4. As can be depicted, the feed
Figure 2. LLE data for the {water + cyclohexanone + benzene} ternary system at 323.15 K: (☆) feed composition; (∗) experimental data; (△) calculated data from the NRTL model; (▽) calculated data from the UNIQUAC model.
Figure 1. LLE data for the {water + cyclohexanone + benzene} ternary system at 303.15 K: (☆) feed composition; (∗) experimental data; (△) calculated data from the NRTL model; (▽) calculated data from the UNIQUAC model.
composition points agree with tie-line accurately, which satisfies the lever rule and demonstrate the conservation of mass in all the experimental operations.21 The area of the biphasic region increased in the following order of the selected solvents: MIBC < benzene. This can be explained by the fact that the area of the biphasic region was affected by the mutual solubility of water and the selected solvents.22 The increasing temperature from
Figure 3. LLE data for the {water + cyclohexanone + MIBC} ternary system at 303.15 K: (☆) feed composition; (∗) experimental data; (△) calculated data from the NRTL model; (▽) calculated data from the UNIQUAC model.
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Figure 4. LLE data for the {water + cyclohexanone + MIBC} ternary system at 323.15 K: (☆) feed composition; (∗) experimental data; (△) calculated data from the NRTL model; (▽) calculated data from the UNIQUAC model.
Figure 5. Hand plot for the system water (1) + cyclohexanone (2) + solvents (3) (benzene or MIBC) at desired temperatures. Experimental data: □, benzene at 303.15 K; ●, benzene at 323.15 K; △, MIBC at 303.15 K; ▼, MIBC at 323.15 K.
303.15 to 323.15 K does not have vital effect on the phase behaviors of the studied ternary systems. To confirm the reliability and consistency of the experimental results, the Hand and Bachman correlation equations were both adopted. The equations are listed as follows: ⎛ xo⎞ ⎛xw⎞ ln⎜ 2o ⎟ = a + b ln⎜ 2w ⎟ ⎝ x1 ⎠ ⎝ x3 ⎠
(1)
⎛ xo ⎞ x3o = c + d⎜ 3w ⎟ ⎝ x1 ⎠
(2)
where a, b and c, d represent the adjustable parameters of these two empirical equations, x2w and x1w denote the mole composition of cyclohexanone and water in the water-rich phase, respectively. xo3 and xo2 represent the mole content of solvents and cyclohexanone in the solvent-rich phase, respectively. The fitting parameters and regression coefficients R2 were given in Table 4. The Hand and Bachman plots were also presented in Figures 5 and 6. As can be observed, all of the correlation factors, R2, are >0.98, indicating a good agreement with the experimental results. Also, the obtained results showed that the Bachman equation was more suitable than the Hand equation for the studied ternary systems. 3.2. Evaluation of the Extractive Solvents. The distribution ratio (K) and selectivity value (β) are key parameters, which can be used to estimate the extraction efficiencies of the selected solvents and the components distributed in the two equilibrium phases, respectively. They are defined in the following forms:
Figure 6. Bachman plot for the ternary system water (1) + cyclohexanone (2) + solvents (3) (benzene or MIBC) at desired temperatures. Experimental data: □, benzene at 303.15 K; ●, benzene at 323.15 K; △, MIBC at 303.15 K; ▼, MIBC at 323.15 K.
K1 =
x1o x1w
(3)
K2 =
x 2o x 2w
(4)
Table 4. Parameters of the Hand and Bachman Equations for Water (1) + Cyclohexanone (2) + Solvent (3) System at Desired Temperatures (303.15 and 323.15 K) Hand
Bachman
T/K
a
b
R2a
c
d
R2a
benzene, 303.15 benzene, 323.15 MIBC, 303.15 MIBC, 323.15
5.0490 4.3571 5.1809 5.1104
1.0746 0.9727 1.1379 1.0952
0.9989 0.9907 0.9987 0.9947
−0.0093 −0.0143 −0.0047 −0.0041
1.0082 1.0132 1.0013 1.0011
0.9999 0.9999 0.9999 0.9999
a 2
R is the linear correlation coefficient. 3515
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β=
K2 K1
Article
other typical published papers.23,24 It could also be found that the extraction performance of the selected solvents has a slight decrease with the temperature from 303.15 to 323.15 K. 3.3. Data Correlation. The two activity coefficient models, NRTL and UNIQUAC, were both utilized to correlate the determined tie-line data of each ternary system by using Aspen 8.4 software. For the UNIQUAC correlation model, the structural parameters of pure component r and q originated from literature25,26 and are also listed in Table 1. By using these two models, the determined LLE data were correlated, and the binary parameters (aij, aji and bij, bji) for each system were obtained. Table 5 shows the calculated binary energy parameters (Δgij, Δgji and Δuij, Δuji) from the two models for water + cyclohexanone + solvents (benzene or MIBC) ternary systems. As presented in Table 5, the NRTL nonrandomness parameters αij was fixed at 0.2 or 0.3, and the value was derived from the literature.27 The binary parameters of these two models are essential, which could be yielded by minimizing the objective function (OF), given as follows:
(5)
where K1 and K2 are the distribution ratio of water or cyclohexanone between organic and aqueous phases, respectively; xw2 and xw1 denote the mole composition of cyclohexanone and water in the water-rich phase, respectively. xo2 and xo1 represent the mole content of cyclohexanone and water in the solvent-rich phase, respectively. The calculated values of K1, K2, and β at each temperature are also presented in Tables 2 and 3. As can be observed, the temperature does not have an obvious effect on the distribution ratio for each system. Meanwhile, all of the selectivity values (β) for the two systems are greatly larger than 1, revealing that the extraction process is feasible. Besides, benzene has larger β values than MIBC because of its low solubility in water, demonstrating that benzene is a more appropriate solvent for separation cyclohexanone from wastewater. The selectivity (β) versus cyclohexanone mole fraction in the solvents-rich phase at 303.15 and 323.15 K are presented in Figures 7 and 8. As
k
OF =
2
3
exp cal 2 − xαβγ ) ∑ ∑ ∑ (xαβγ
(6)
α=1 β=1 γ=1
where the subscripts α, β, and γ denote the components, the phases as well as the tie lines, respectively, k refer to the number of tie-lines, xexp represents the experimental mole composition, and xcal is the calculated mole concentration. Also, the root-mean-square deviation (rmsd) values were employed to evaluate the consistency between the calculated results and the experimental data, given by the following form: 1/2 exp cal 2 ⎫ ⎧ k 2 3 − xαβγ (xαβγ ) ⎪ ⎪ ⎬ rmsd = 100 × ⎨∑ ∑ ∑ ⎪ ⎪ 6k ⎩ α β γ ⎭
Figure 7. Experimental selectivity value (β) versus the cyclohexanone mole fraction (xo2) in the solvent phase for the ternary system water (1) + cyclohexanone (2) + benzene (3) at different temperatures. Experimental data: ●, T = 303.15 K; △, T = 323.15 K.
(7)
where all of the parameters are the same as those in eq 6. The calculated rmsd values are presented in Table 4, and all of them were less than 0.46, which indicates that all of the measured LLE data can be fitted well by these two models, while the UNIQUAC model was superior to the NRTL model for the correlation. Moreover, the correlated results at different temperatures using both two models were also given in Figures 1−4. As can be seen from these figures, the correlated results show a good agreement with the measured experimental data, which demonstrates that all of the LLE data of each ternary system could be simulated well by two correlation models.
4. CONCLUSIONS The liquid−liquid equilibria data of water + cyclohexanone + benzene and water + cyclohexanone + MIBC ternary systems were determined at the temperatures (303.15 and 323.15 K) under 101.3 kPa. The Hand and Bachman equations were both employed to validate the reliability and accuracy of the obtained LLE tie-line data and received good results. The calculated distribution ratios and selectivity values reflect the feasibility of separating cyclohexanone from wastewater by using benzene as well as MIBC. Additionally, the extraction capability decreases with the increasing temperature. Moreover, the experimental tie-line data were correlated well with both the NRTL and the UNIQUAC activity coefficient models, and the corresponding interaction energy parameters of these two models were yielded. The calculated rmsd values were less 0.46 and 0.45 for
Figure 8. Experimental selectivity value (β) versus the cyclohexanone mole fraction (xo2) in the solvent phase for the ternary system water (1) + cyclohexanone (2) + MIBC (3) at different temperatures. Experimental data: ●, T = 303.15 K; △, T = 323.15 K.
presented in the figure, the β values decrease with the increasing mole fraction of cyclohexanone in aqueous phase for the same temperature, indicating that the separating capability of solvents decreases and a low concentration is suitable for an extraction operation, which is similar to those in 3516
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Table 5. Binary Energy Interaction Parameters of NRTL and UNIQUAC Models for the System Water (1) + Cyclohexanone (2) + Solvents (3) at Desired Temperatures (303.15 and 323.15 K) NRTL parameters
UNIQUAC parameters
T/K
i−j
Δgij(J mol−1)
Δgji(J mol−1)
αij
benzene, 303.15
1−2 1−3 2−3 1−2 1−3 2−3 1−2 1−3 2−3 1−2 1−3 2−3
131184.97 301113.28 7666.49 139691.67 323753.14 8698.66 133364.10 13855.25 −1324.80 144486.28 15056.81 474.87
213606.71 118237.52 −4958.25 230870.31 125976.57 −5911.80 211985.46 −194.79 1743.53 227805.50 −574.59 −673.99
0.20 0.20 0.30 0.20 0.20 0.30 0.20 0.20 0.30 0.20 0.20 0.30
benzene, 323.15
MIBC, 303.15
MIBC, 323.15
AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. ORCID
Qingsong Li: 0000-0003-1425-8822 Notes
The authors declare no competing financial interest.
■
0.22
0.46
0.17
0.30
Δuij(J mol−1)
Δuji (J mol−1)
−604.04 490.30 1881.72 −918.01 −884.30 2146.46 85.99 −6527.65 2399.74 235.12 −207.04 −260.82
4569.21 7134.43 −1927.41 6109.33 6876.92 −2318.74 1149.73 2407.30 783.98 298.01 2257.25 −298.79
rmsd 0.19
0.45
0.16
0.31
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the NRTL and the UNIQUAC models, respectively, implying that both the models fitted satisfactorily to the experimental data, but the UNIQUAC model performs better.
■
rmsd
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DOI: 10.1021/acs.jced.7b00511 J. Chem. Eng. Data 2017, 62, 3512−3517
