Methyl Isobutyl Ketone + Quinoline or Isoquinoline ... - ACS Publications

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

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Liquid−Liquid Equilibrium for the Ternary Systems (Methyl Isobutyl Ketone + Quinoline or Isoquinoline + Water) at 298.15, 318.15, and 338.15 K Yinshuang Zhang, Bokun Chen, and Siyu Yang* School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, P.R. China

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S Supporting Information *

ABSTRACT: Liquid−liquid equilibrium (LLE) data for the ternary systems (methyl isobutyl ketone + quinoline or isoquinoline + water) were measured at T = 298.15, 318.15, and 338.15 K and atmospheric pressure. Distribution coefficients and separation factors were calculated to evaluate extraction efficiency. The Hand, Bachman, and Othmer−Tobias equations were applied to verify the reliability of the experimental tie-line data. The NRTL and UNIQUAC models were used to correlate all of the experimental values at different temperatures simultaneously. The binary interaction parameters of these two models were obtained. The root-mean-square deviation between the experimental and calculated data indicates that the NRTL model presents a better prediction than the UNIQUAC model. The effect of temperature on the extraction performance of methyl isobutyl ketone was investigated. The extraction process of quinoline or isoquinoline by methyl isobutyl ketone is exothermic. The increase of temperature is not a benefit to extract quinoline or isoquinoline.

1. INTRODUCTION Nitrogen-containing compounds are common pollutants in wastewater. These pollutants are often found in the wastewater from many industrial processes, e.g., the wastewater from coal gasification, coal coking, coal liquefaction, and the coal semicoke process.1,2 There are three types of nitrogencontaining compounds that contain acidity, alkalinity, and neutrality. In coal-gasification wastewater, the neutral nitrogencontaining compounds mainly contain a large amount of quinoline, pyridine, and ureide and their homologues. Taking the typical coal gasification technique as a case, He et al.3 investigated the node occurring from wastewater and water quality features. Table S1 presents the chemical oxygen demand (COD) of nitrogen-containing compounds in the Lurgi coal gasification wastewater (see the Supporting Information for a detailed description). Nitrogen-containing compounds have relatively large amounts in coking wastewater with the total content being 2500−4000 mg/L. This content accounts for 20−30% of the total organic pollutants.4 In addition, nitrogen-containing compounds are toxic and biorefractory pollutants with a very low BOD5/COD level. For example, the BOD5/COD of quinoline or isoquinoline is less than 0.2, while the BOD5/ COD of ureide is between 0.02 and 0.1 and the BOD5/COD of pyridine is between 0 and 0.02.5,6 It is very difficult to biodegrade such nitrogen-containing compounds. The nitrogen-containing compounds in coking wastewater are a huge © XXXX American Chemical Society

obstacle for current treatment processes to meet the standard of all-around water. As a result, it is important to remove nitrogen-containing compounds from wastewater. In coking wastewater treatment processes, solvent extraction is an efficient treatment unit to remove highly concentrated pollutants from wastewater before the biochemical treatment unit.7 It is easy to recover them from the extraction phase with the method of solvent extraction. The liquid−liquid equilibrium (LLE) of the ternary systems (solvent + phenolic compound + water) has been extensively researched.8−11 The extraction efficiency of several solvents, such as methyl isobutyl ketone,12 methyl isopropyl ketone,13 methyl propyl ketone,14 3-heptanone,15 and cineole,16 has been investigated. Yang et al.17 measured the LLE data of ternary systems (methyl isobutyl ketone + hydroquinone + water). Martin et al.18,19 reported the experimental data of the aromatic hydrocarbons (toluene or ethylbenzene) + phenols + water system and the aliphatic hydrocarbons (heptane or octane) + phenols + water system. Hwang et al.20 researched the LLE of the (dimethyl carbonate + phenol + water) and (diphenyl carbonate + phenol + water) systems. However, little attention has been focused on removing nitrogen-containing compounds from wastewater. The LLE data of the ternary system (solvent + Received: January 30, 2018 Accepted: June 15, 2018

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DOI: 10.1021/acs.jced.8b00096 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 1. Chemical Structure, CAS Number, Suppliers, and Purities of the Chemicals Used in the Work

a

Gas chromatograph.

nitrogen-containing compounds + water) have not been reported until now. Methyl isobutyl ketone, a low boiling-point solvent (boiling point 115.9 °C, azeotropic point 88.4 °C), is currently one of the industrial extractants used in industrial wastewater treatment processes. In addition to phenolic compounds, wastewater also contains a large number of heterocyclic nitrogen-containing compounds. As a result, it is necessary to investigate the extraction efficiency of methyl isobutyl ketone to nitrogen-containing compounds. In this paper, methyl isobutyl ketone was used to extract quinoline or isoquinoline from the aqueous phase. To obtain reliable data for the simulation of quinoline or isoquinoline recovery from the aqueous phase, the experimental LLE data for ternary systems (methyl isobutyl ketone + quinoline + water) and (methyl isobutyl ketone + isoquinoline + water) were measured at 298.15, 318.15, and 338.15 K under atmospheric pressure. Then, the NRTL21 and UNIQUAC22 models were applied to correlate the experimental LLE data, as well as to obtain binary interaction parameters of ternary systems (methyl isobutyl ketone + quinoline or isoquinoline + water).

Figure 1. Schematic diagram for the static apparatus for the LLE measurement.

2. MATERIALS AND METHODS 2.1. Materials. The detailed information on chemicals used in this work is presented in Table 1. The purity of the materials was checked by gas chromatography, where no obvious peaks of impurities were detected. All of the chemicals in the study were used without further purification. Deionized water was applied throughout the experiment. 2.2. Apparatus and Procedure. The LLE determination apparatus in our laboratory consists of three parts: an equilibrium glass vessel jacket, a thermostat (HX-1050) with a system that precisely measures the temperature (JK5016U), and a magnetic stirrer (HS-19). The temperature of the liquid sample in the equilibrium vessel was regulated by the thermostat to within ±0.1 K of the set point. Figure 1 shows the schematic diagram of the static apparatus for the LLE measurement. Figure 2 shows the schematic diagram of this LLE measurement system. The sample mixture was put into the glass vessel, vigorously agitated by the magnetic stirrer for at least 2 h, and then kept 12 h to reach phase equilibrium. After

Figure 2. Flowchart summarizing the analytical protocol for the two sampled phases in LLE experiments. C1α and C2α are the concentrations of the MIBK and of quinoline or isoquinoline, respectively, in the aqueous phase. C1β and C2β are the concentrations of the MIBK and of quinoline or isoquinoline, respectively, in the organic phase. ρα and ρβ are the densities of the aqueous and organic phases, respectively.

arriving at the equilibrium state for the two liquid phases, samples were carefully taken from the top for the upper organic phase and from the bottom for the lower aqueous B



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Table 2. Experimental LLE Data (Mass Fraction) for the Ternary System {Methyl Isobutyl Ketone (1) + Quinoline (2) + Water (3)} at T = 298.15, 318.15, and 338.15 K and p = 0.1 MPaa feed

aqueous phase

T (K)

w1

w2

ww1

298.15

0.1659 0.1651 0.1630 0.1614 0.1593 0.1575 0.1520 0.1501 0.1660 0.1636 0.1624 0.1619 0.1613 0.1601 0.1586 0.1521 0.1662 0.1646 0.1638 0.1627 0.1601 0.1598 0.1582 0.1538

0.0085 0.0186 0.0248 0.0385 0.0483 0.0621 0.0737 0.0920 0.0084 0.0183 0.0304 0.0421 0.0513 0.0682 0.0723 0.0851 0.0079 0.0193 0.0328 0.0516 0.0520 0.0595 0.0753 0.0902

0.0158 0.0157 0.0156 0.0155 0.0152 0.0151 0.0148 0.0145 0.0144 0.0142 0.0139 0.0137 0.0136 0.0132 0.0130 0.0127 0.0135 0.0134 0.0133 0.0131 0.0128 0.0125 0.0122 0.0118

318.15

338.15

organic phase ww2

wo1

wo2

D

S

0.0004 0.0009 0.0013 0.0020 0.0025 0.0030 0.0036 0.0042 0.0003 0.0008 0.0015 0.0021 0.0027 0.0033 0.0038 0.0044 0.0003 0.0011 0.0019 0.0026 0.0033 0.0041 0.0047 0.0053

0.9205 0.8703 0.8338 0.7735 0.7232 0.6657 0.6268 0.5724 0.9151 0.8552 0.7986 0.7456 0.6938 0.6435 0.5903 0.5362 0.9222 0.8503 0.7698 0.7083 0.6582 0.6045 0.5585 0.5259

0.0463 0.0917 0.1224 0.1816 0.2297 0.2801 0.3201 0.3726 0.0353 0.0951 0.1413 0.1914 0.2407 0.2841 0.3305 0.3740 0.0352 0.0973 0.1669 0.2168 0.2601 0.3058 0.3453 0.3720

101.21 98.71 94.10 92.18 90.41 92.72 88.67 88.72 96.43 95.23 93.85 91.14 89.79 86.10 86.97 85.01 90.35 89.27 87.84 83.38 78.82 74.57 73.47 70.19

2824.26 2557.19 2113.64 2016.19 1883.95 1681.56 1639.44 1582.95 2810.40 2358.04 1539.03 1422.95 1347.92 1170.62 1093.51 1047.43 2304.28 1678.87 1366.62 1095.80 949.19 817.11 750.99 675.80

a

Standard uncertainties u are u(T) = 0.1 K, u(p) = 1 kPa, and u(w) = 0.0048.

Table 3. Experimental LLE Data (Mass Fraction) for the Ternary System {Methyl Isobutyl Ketone (1) + Isoquinoline (2) + Water (3)} at T = 298.15, 318.15, and 338.15 K and p = 0.1 MPaa feed

aqueous phase

organic phase

T (K)

w1

w2

ww1

ww2

wo1

wo2

D

S

298.15

0.1658 0.1641 0.1631 0.1619 0.1604 0.1586 0.1545 0.1506 0.1661 0.1658 0.1624 0.1601 0.1586 0.1565 0.1534 0.1518 0.1663 0.1651 0.1647 0.1634 0.1615 0.1562 0.1546 0.1523

0.0081 0.0176 0.0250 0.0326 0.0476 0.0591 0.0753 0.0920 0.0075 0.0103 0.0272 0.0383 0.0508 0.0603 0.0756 0.0897 0.0073 0.0213 0.0316 0.0438 0.0569 0.0761 0.0903 0.1021

0.0158 0.0157 0.0156 0.0155 0.0152 0.0151 0.0147 0.0145 0.0144 0.0143 0.0142 0.0140 0.0137 0.0134 0.0131 0.0128 0.0136 0.0134 0.0132 0.0131 0.0129 0.0125 0.0123 0.0121

0.0004 0.0010 0.0015 0.0019 0.0026 0.0031 0.0037 0.0043 0.0003 0.0007 0.0014 0.0019 0.0026 0.0032 0.0038 0.0045 0.0004 0.0012 0.0017 0.0024 0.0030 0.0039 0.0047 0.0051

0.9205 0.8653 0.8138 0.7735 0.7132 0.6657 0.6218 0.5724 0.9197 0.8788 0.8021 0.7610 0.6931 0.6526 0.6097 0.5601 0.8982 0.8313 0.7778 0.7173 0.6672 0.6045 0.5545 0.5259

0.0452 0.0961 0.1403 0.1751 0.2343 0.2752 0.3214 0.3646 0.0360 0.0675 0.1320 0.1724 0.2297 0.2711 0.3103 0.3597 0.0452 0.1064 0.1471 0.1993 0.2406 0.3029 0.3473 0.3685

100.24 96.12 93.53 92.15 90.12 88.78 86.86 84.80 98.82 96.43 94.29 90.74 88.36 84.73 81.66 79.93 91.35 88.67 86.53 83.04 80.20 77.67 73.89 72.25

2813.54 2451.11 2002.92 1760.97 1686.25 1476.17 1501.44 1321.32 2208.36 1768.75 1408.42 1340.75 1126.07 1092.64 1003.47 979.48 2249.25 1402.44 1134.98 980.23 856.02 824.98 739.69 672.37

318.15

338.15

a

Standard uncertainties u are u(T) = 0.1 K, u(p) = 1 kPa, and u(w) = 0.0048.

C



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phase without cross contamination during the sampling procedure. The sample analysis was performed using a gas chromatograph (GC6820, Agilent Technologies) equipped with a DB-5MS capillary column (30 m × 0.32 mm × 0.25 μm) and a flame ionization detector (FID). The carrier gas was nitrogen with a rate of 30 mL·min−1 in the column. The temperatures of the injector and the detector were held at 523.15 and 543.15 K. The initial temperature of the column was set at 318.15 K, held for 2 min, and then increased at a rate of 10 K·min−1 to reach 493.15 K, and kept at this temperature for 2 min. The injection volume was 2 μL, and the split ratio was 25:1. The sample composition was determined on the basis of the internal standard method. n-Propyl acetate was selected as the internal standard of methyl isobutyl ketone and naphthalene as the internal standard of quinoline or isoquinoline. The water concentration was obtained by deducting all other components’ mass fractions from 1. Each sample was analyzed three times under the same conditions to investigate the repeatability, as well as to obtain the average composition of each sample.

Figure 3. Ternary phase diagram for the system of (methyl isobutyl ketone + quinoline + water) at 298.15 K: (★) feed composition; (■, solid lines) experimental data; (●, dashed lines) calculated data from the NRTL model; (▲, dotted lines) calculated data from the UNIQUAC model.

3. RESULTS AND DISCUSSION 3.1. Tie-Line Data and Ternary Diagrams. To obtain the reliability of experimental LLE data, the mutual solubilities of methyl isobutyl ketone and water at T = 298.15, 318.15, and 338.15 K are measured under atmospheric pressure. The analytical method and apparatus are the same as those for the experimental LLE data of ternary systems (methyl isobutyl ketone + quinoline + water) and (methyl isobutyl ketone + isoquinoline + water). The results are shown in Table S2 (see the Supporting Information for a detailed description). The data from the literature23 come from the Dortmund Data Bank (DDB). Compared to the experimental mutual solubility data and reference data, there is a very small difference. The comparison indicates that the experimental method is reasonable and reliable. The experimental LLE tie-line data of the ternary systems (methyl isobutyl ketone + quinoline + water) and (methyl isobutyl ketone + isoquinoline + water) at T = 298.15, 318.15, and 338.15 K and atmosphere pressure are listed in Table 2 and Table 3. All concentrations are expressed in the mass fractions. Here, wo1, wo2, and wo3 represent the mass fractions of methyl isobutyl ketone, quinoline (or isoquinoline), and water in the organic phase, respectively, and ww1 , ww2 , and ww3 denote the mass fractions of methyl isobutyl ketone, quinoline (or isoquinoline), and water in the aqueous phase. Meanwhile, the corresponding triangular phase diagrams for each ternary system, together with the tie-lines, are plotted and depicted in Figures 3−8. According to Figures 3−8, we found that the slope of the tie-lines slightly increases with an increase of the quinoline or isoquinoline mass fraction in the organic phase, while the tie-line length slightly increases with a decrease in temperature. The slopes of the tie-lines indicate that quinoline or isoquinoline has a much greater solubility in the extract phase than in the raffinate phase. 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 of the experimental operations. 3.2. Evaluation of Extraction Capacity. To examine the extraction ability of methyl isobutyl ketone to separate quinoline or isoquinoline from the aqueous phase, the


distribution coefficient (D) and selectivity (S) are determined as follows D=

w2o w2w

(1) o

S=

(w2 /w3) (w2 /w3)w

(2)

wo2

where is the mass fraction of quinoline or isoquinoline in the organic phase and ww2 is the mass fraction of quinoline or isoquinoline in the aqueous phase. wo3 and ww3 represent the mass fraction of water in the organic and aqueous phase, respectively. The distribution coefficients and separation factors of quinoline or isoquinoline are calculated and D



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Figure 7. Ternary phase diagram for the system of (methyl isobutyl ketone + isoquinoline + water) at 318.15 K: (★) feed composition; (■, solid lines) experimental data; (●, dashed lines) calculated data from the NRTL model; (▲, dotted lines) calculated data from the UNIQUAC model.



Table 4. Othmer−Tobias Equation Parameters for Ternary Systems (Methyl Isobutyl Ketone + Quinoline or Isoquinoline + Water)

presented in Table 4 and Table 5. The variation of distribution coefficients and separation factors is shown in Figures S1−S4 (see the Supporting Information for a detailed description). The result indicates that methyl isobutyl ketone provides a high distribution coefficient and high separation factors for quinoline or isoquinoline. It is also found that the distribution coefficient of quinoline or isoquinoline slightly decreases with the increase of temperature and the mass fraction of solute in the aqueous phase, which are the same as many literature reports.24−26 The results indicate that methyl isobutyl ketone is a good solvent for removal of quinoline or isoquinoline from the aqueous phase. The reliability of LLE data was evaluated by the Othmer− Tobias,27 Hand,28 and Bachman29 equations, given by eqs 3,

T (K) 298.15 318.15 338.15 298.15 318.15 338.15

E

A

B

Methyl Propyl Ketone + Quinoline + Water 57.0619 14.2184 55.1982 13.6426 41.7224 10.3138 Methyl Propyl Ketone + Isoquinoline + Water 54.5695 13.8494 52.1846 12.9447 37.9300 9.3831

R2 0.9912 0.9806 0.9911 0.9913 0.9916 0.9812



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the (methyl isobutyl ketone + quinoline or isoquinoline) binary pair it was set as 0.3. These values produced better goodness-of-fits. The molecular volume structure parameters r and the molecular surface area parameters q are shown in Table 5. The binary interaction parameters for the two models were obtained through minimizing the objective function (OF) which is defined as follows Ä É exp cal 2 Ñ ÅÅ (T exp − T cal)2 n Å 3 2 (wijk ) ÑÑÑÑ − wijk ÅÅ k k ÑÑ OF = ∑ ∑ ∑ ÅÅÅ + ÑÑ ÅÅ σT 2 σw 2 i=1 j=1 k=1 Å ÑÑÖ Ç

Table 5. Structural Parameters for the UNIQUAC Model (ri Represents Area Parameter, and qi Represents Volume Parameter)a component

ri

qi

methyl isobutyl ketone quinoline isoquinoline water

4.5959 4.7923 4.7923 0.9200

3.952 3.153 3.153 1.400

a

From the Dortmund Data Bank.

S1, and S2, respectively. See the Supporting Information for a detailed description of the NRTL and Bachman equations

yz ij 1 zz = A + B lnjjj zz j (3) { k where A and B are the intercept and slopes of the Othmer− Tobias equation. wo1 is the mass fraction of methyl isobutyl ketone in the organic phase, and ww3 is the mass fraction of water in the aqueous phase. The parameter values of straight line calculated from the Othmer−Tobias equation, together with the corresponding regression coefficients (R2), are given in Table 4, while those of the Hand and Bachman equations are given in Table S3. All of the R2 are more than 0.98. It means a good degree of reliability of the measured LLE data. 3.3. Thermodynamic Modeling. There are many papers that have correlated the LLE data by the NRTL and UNIQUAC models.30−32 In this paper, the two models were used to correlate experimental data. In the correlation process using the NRTL model, it is important to apply the best value of the nonrandomness (αij) to achieve the closest result to experimental points. For this reason, different values of αij between 0.1 and 0.5 were tested and finally the optimum value for the nonrandomness parameter was obtained. The values of αij for binary pairs (methyl isobutyl ketone + water) and (quinoline or isoquinoline + water) were set as 0.2, while for ij 1 lnjjj j k

− w1o yzz z w1o zz{

(4)

− w3w w3w

cal

cal

where n is the number of the tie-lines, w and T are the calculated mass fraction and temperature, and wexp and Texp are the experimental mass fraction and temperature, respectively. The subscripts are i = 1−3 for ternary mixtures, j = 1, 2 (phases), and k = 1 to n (tie-lines). σT and σw denote the standard deviation of the temperature and the mass fraction. The root-mean-square deviation (RMSD) of component i in phase j is used to check the agreement between the experimental data and the calculated data. The RMSD value is defined as the following ÄÅ 3 É ÅÅ ∑ ∑2 ∑n (w exp − w cal)2 ÑÑÑ0.5 ÅÅ i = 1 j = 1 k = 1 ijk ÑÑ ijk ÑÑ RMSD = ÅÅÅ ÑÑ ÅÅ 6n ÅÅÇ ÑÑÑÖ (5) where wexp, wcal, n, i, j, and k have the same meaning as those in eq 4. As can be seen in Table 6, the maximum value for RMSD is less than 1%. This indicates that the liquid−liquid equilibrium data of the ternary systems (methyl isobutyl ketone + quinoline or isoquinoline + water) are well correlated with both the NRTL and UNIQUAC models. Moreover, the NRTL model with a smaller RMSD value showed a better correlation performance.

Table 6. Binary Interaction Parameters of NRTL and UNIQUAC Models for the Ternary Systems {Methyl Isobutyl Ketone (1) + Quinoline or Isoquinoline (2) + Water (3)} NRTL T (K)

i−j

bij (K)

298.15

1−2 1−3 2−3 1−2 1−3 2−3 1−2 1−3 2−3

−177.31 1059.85 −522.58 420.63 1044.63 −565.20 545.45 1155.14 −774.09

1−2 1−3 2−3 1−2 1−3 2−3 1−2 1−3 2−3

−159.87 1063.73 −642.37 371.78 1039.51 −604.45 484.14 1067.98 −724.22

318.15

338.15

298.15

318.15

338.15

bji (K)

UNIQUAC αij

RMSD (%)

bij (K)

Methyl Isobutyl Ketone (1) + Quinoline (2) + Water (3) 2313.66 0.30 0.212 −158.70 −1140.42 0.20 −1140.77 2614.93 0.20 −1240.60 −428.93 0.30 0.135 −204.94 −1123.81 0.20 −1126.80 2472.44 0.20 −1206.08 −564.78 0.30 0.012 −229.64 −1217.74 0.20 −1241.13 2772.05 0.20 −1211.45 Methyl Isobutyl Ketone (1) + Isoquinoline (2) + Water (3) 3438.49 0.30 0.420 −173.17 −1143.41 0.20 −1150.09 2730.80 0.20 180.19 −412.81 0.30 0.031 −202.47 −1116.98 0.20 −1127.84 2497.88 0.20 279.10 −498.08 0.30 0.601 −217.31 −1146.96 0.20 −1162.92 2725.19 0.20 340.42 F

bji (K)

RMSD (%)

155.89 420.55 −620.13 186.09 414.07 −862.96 204.08 450.75 −1053.14

0.251

164.49 423.19 −347.05 189.42 414.18 −530.23 199.74 424.41 −659.68

0.185

0.352

0.547

0.068

0.843



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3.4. The Enthalpy Estimation in Quinoline or Isoquinoline Extraction. The influences of temperature on the performance of methyl isobutyl ketone extracting quinoline or isoquinoline were also investigated. The aqueous solution of quinoline or isoquinoline at 2 g·L−1 was extracted by methyl isobutyl ketone at different temperatures. The distribution coefficient D was determined with results shown in Table S4. According to the Van’t Hoff equation,33 the following expression can be obtained ln D = −

ΔH ΔS + RT R

4. CONCLUSIONS Experimental liquid−liquid equilibrium data of the ternary systems (methyl isobutyl ketone + quinoline + water) and (methyl isobutyl ketone + isoquinoline + water) were determined at T = 298.15, 318.15, and 338.15 K and atmospheric pressure. The high distribution coefficients and selectivity factors reflect that methyl isobutyl ketone is an efficient solvent to extract quinoline or isoquinoline from the aqueous phase. The Hand, Bachman, and Othmer−Tobias equations were used to check the reliability of the experimental LLE data. The experimental results were correlated with the NRTL and UNIQUAC models, and the comparison between experimental and calculated results for both models indicates that the NRTL model is more accurate for LLE calculations in this work. Moreover, the binary interaction parameters were obtained. The physical meaning for the regressed binary interaction parameters is explained in terms of intermolecular attractive energy. By analyzing the NRTL binary parameter boundary for total and partial miscibility for the ternary systems, the results indicate that these parameters respond to the behavior in the miscible regions of the system. Using the enthalpy change in the extraction process, the effect of temperature on the extraction performance of methyl isobutyl ketone was investigated. The results denote that methyl isobutyl ketone extracts quinoline or isoquinoline in the aqueous phase in an exothermic process. There is no benefit to extracting quinoline or isoquinoline by increasing temperature. The research provides a valuable reference for the design and simulation of the quinoline or isoquinoline extraction process and the solvent recovery process from industrial wastewater.

(6)

where ΔH means the enthalpy of apparent thermal effects in the extraction process and ΔS represents the entropy change. Plotting ln D versus 1000/T, the straight lines are obtained in Figure S5 and Figure S6. From the slope of Figure S5, we found the ΔH = −2.23 kJ·mol−1. For Figure S6, we found ΔH = −2.57 kJ·mol−1. This means that the intermolecular forces between water and quinoline or isoquinoline in the aqueous phase are weaker than those for methyl isobutyl ketone and quinoline or isoquinoline in the organic phase. Thus, the quinoline or isoquinoline extraction process by methyl isobutyl ketone is exothermic. The increase of temperature does not benefit to extract quinoline or isoquinoline. 3.5. Checking of Binary Subsystems Consistency. In the Treybal classification,34 ternary LLE systems are grouped according to the number of partially miscible binary subsystems (PMBS), which is divided into four types: type I (one PMBS), type II (two PMBS), type III (three PMBS), and type 0 or island (zero PMBS). When a set of experimental LLE ternary data is correlated with a model, it is very important not only to obtain a good agreement between experimental and calculated data but also to guarantee that the parameters obtained are consistent with the type of system (type I, II, III, or island for three components) being correlated.35 This means that the parameters must not only reproduce well the LLE splitting corresponding to the experimental tie-lines but also the miscibility regions of the system including the miscible binary subsystems. The equilibrium phase diagrams for the investigated ternary systems of (methyl isobutyl ketone + quinoline or isoquinoline + water) are classified as type II on the basis of Treybal’s contribution. The system consists of one completely miscible binary component (methyl isobutyl ketone + quinoline or isoquinoline) and two partially miscible binary components (water + quinoline or isoquinoline) and (water + methyl isobutyl ketone). On the basis of these ideas, we have developed a simple but very useful tool, using a Graphical User Interface36 written in MatLab software code, to systematically check all of the binary parameters in the present study. According to the experimental data and the binary interaction parameters, the NRTL binary parameter boundaries for total and partial miscibility for the ternary systems (methyl isobutyl ketone + quinoline or isoquinoline + water) are plotted in Figures S7 and S8, which indicate that binary components (methyl isobutyl ketone + quinoline or isoquinoline) are in the homogeneous region and binary components (water + quinoline or isoquinoline) and (water + methyl isobutyl ketone) are in the heterogeneous region. The results guarantee that these parameters respond to the behavior in the miscible regions of the system and indicate a good agreement between experimental and calculated data.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jced.8b00096.

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Hand and Bachman equations; figures showing distribution coefficients, separation factors, ln D, and the NRTL binary parameter boundary for total and partial miscibility for the ternary systems; and tables showing the COD of nitrogen-containing compounds, experimental and literature values of mutual solubility (mass fraction), Hand and Bachman equation parameters and regression coefficients, and distribution coefficients (PDF)

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Phone: +86-20-87112056, +86-18588887467. ORCID

Siyu Yang: 0000-0002-4871-7460 Funding

We would like to express our appreciation to the National Key Research and Development Program of China (No. 2016YFB0600501) and the National Natural Science Foundation of China (No. 21736004) for their great funding and support of this study. Notes

The authors declare no competing financial interest. G



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