Experimental Measurement and Thermodynamic Model of Liquid

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

pubs.acs.org/jced

Experimental Measurement and Thermodynamic Model of Liquid− Liquid Equilibrium for the Ternary System of 1‑Dodecanol−Phenol− Water Meiling Jiang, Shuai Shen, and Yun Chen* Department of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, P.R. China

Downloaded by UNIV OF ROCHESTER at 05:11:23:778 on May 23, 2019 from https://pubs.acs.org/doi/10.1021/acs.jced.9b00176.

S Supporting Information *

ABSTRACT: 1-Dodecanol with low solubility in water is a potential solvent to extract phenol from wastewater. The liquid−liquid equilibrium data of the ternary system (1dodecanol−phenol−water) were measured at 298.15, 313.15, 323.15, 333.15, and 343.15 K under atmospheric pressure. The experimental data were correlated by the nonrandom two liquids (NRTL) and universal quasi-chemical (UNIQUAC) models, and the corresponding binary parameters were obtained. The results show that the two models agree well with experimental values. Comparison of the average values of the root mean squared deviation (RMSD) from both models reveals that the NRTL model is more accurate than the UNIQUAC model. The effect of temperature on the extraction process is discussed, and temperature has little effect on extraction efficiency. The van’t Hoff equation is used to correlate the relationship of distribution coefficient to temperature. The enthalpy change of the extraction process was calculated, and the result shows that extraction of phenol from water by 1-dodecanol is an exothermic process. dodecanol−propionic acid−water system. Gilani et al.18 obtained the LLE data for water−phosphoric acid−1dodecanol at different temperatures. Stoicescu et al.19 determined the liquid−liquid equilibrium data for the ternary system 1-propanol−water−1-dodecanol. Senol et al.20 investigated the ability of a series of alcohols and alamine 336 mixtures to extract pyruvic acid from water and evaluated the separation factors. The extraction effect of mixed solvents 1dodecanol and alamine 336 was found to be the best among the different solvents. However, as far as we know, the LLE ternary data for 1-dodecanol, phenol, and water does not exist in the literature. Generally, most LLE data on solvent− phenol−water focuses on the range from 298.15 K (a temperature under standard conditions) to 323.15 K. However, the operating temperature for extracting phenolic compounds from industrial wastewater, especially in the coalchemical industry, is usually set above 333 K in order to greatly reduce the pipeline clogging problems from paraffin (melting point 328.15−335.15 K) in the phenol recovery unit.21,22 For example, industrial applications for treating phenolic effluent with methyl isobutyl ketone (MIBK) as solvent have been implemented in some plants or companies, such as China Harbin Coal-chemicals Inc.,23,24 Erdos Coal-Chemicals Inc.,25 and Xinjiang Guanghui Coal Clean Refining & Chemical Co., Ltd. In this work, the ternary liquid−liquid equilibrium data of the system 1-dodecanol (1)−phenol (2)−water (3) were

1. INTRODUCTION Phenol-containing wastewater mainly comes from chemical industries such as coking plants, gas plants, petrochemical plants, and insulating materials plants.1,2 The concentration of phenolic substances in wastewater generated from the Lurgi gasification process is very high, and treating 1 ton of coal will produce about 0.8−1.1 tons of phenol-containing wastewater.3,4 Phenol has germicidal activity and degrades protein.5 Wastewater containing such a high concentration of phenol must be pretreated to reduce phenolic content before the wastewater flows into the biochemical treatment section.6 For removing and recycling phenol from wastewater, solvent extraction is one of the most effective and economical methods to deal with it.7−9 The extraction process can be carried out continuously or intermittently, and the amount of treated water is relatively large. Research on liquid−liquid equilibrium (LLE) of ternary systems of organic solvent−phenol−water is of great significance for the treatment of phenol-containing wastewater from the coal chemical industry. Recently many authors have studied the LLE of various organic solvents and phenol solutions and measured related phase equilibrium data. The main solvents for extraction of phenol from water are alcohols,10 ketones,4,11,12 esters,13 ethers,14 alkanes,15 aromatic hydrocarbons.16 However, these solvents have relatively high water solubility and require relatively high energy consumption in the solvent recovery stage. Thus, 1-dodecanol with low solubility in water was selected as a potential solvent to extract phenol from water. Previously, 1-dodecanol has been used as an extractant for organic acids. Kırbaşlar et al.17 studied the LLE of the 1© XXXX American Chemical Society

Received: February 22, 2019 Accepted: May 8, 2019

A

DOI: 10.1021/acs.jced.9b00176 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 1. Details of Chemicals Used in This Work compound

supplier

methanol phenol 3,4-xylenol 1-dodecanol 1-tetradecanol

Xiya Xiya Xiya Xiya Xiya

Reagent Reagent Reagent Reagent Reagent

mass fraction purity (%)

purification method

purity analysis method

CAS no.

99.31 99.51 99.22 99.52 99.14

none none none none none

GCa GCa GCa GCa GCa

67-56-1 108-95-2 95-65-8 112-53-8 112-72-1

Ltd. Ltd. Ltd. Ltd. Ltd.

a

Gas chromatography.

Table 2. Experimental LLE Values (Mass Fraction) For the Ternary System 1-Dodecanol (1)−Phenol (2)−Water (3) at 101.3 kPaa organic phase

aqueous phase

T, K

wo1

wo2

wo3

ww1

ww2

ww3

298.15

0.98635 0.94774 0.87240 0.81106 0.74307 0.68221 0.61502 0.55868 0.51731 0.98573 0.92590 0.85644 0.79088 0.72257 0.67354 0.62239 0.57570 0.53389 0.98199 0.94749 0.87728 0.81560 0.74281 0.67716 0.62779 0.57963 0.53884 0.98058 0.92312 0.84210 0.76880 0.683418 0.62153 0.55834 0.51324 0.48402 0.97657 0.91733 0.84136 0.77291 0.70944 0.64676 0.57811 0.500756 0.466049

0.00000 0.03666 0.10811 0.16546 0.22994 0.28695 0.35175 0.40532 0.44307 0.00000 0.05599 0.12136 0.18238 0.23913 0.29183 0.33931 0.38219 0.41991 0.00000 0.03189 0.09806 0.15635 0.22452 0.27612 0.31217 0.35556 0.39221 0.00000 0.05525 0.13197 0.20127 0.28218 0.34026 0.39954 0.44055 0.46587 0.00000 0.05603 0.12767 0.19242 0.25161 0.31119 0.37494 0.449067 0.479740

0.01365 0.01560 0.01949 0.02348 0.02699 0.03084 0.03323 0.03600 0.03962 0.01427 0.01811 0.02220 0.02674 0.03087 0.03463 0.03830 0.04211 0.04620 0.01801 0.02063 0.02467 0.02805 0.03267 0.03672 0.04005 0.04481 0.04895 0.01942 0.02163 0.02593 0.02993 0.03440 0.03821 0.04211 0.04621 0.05011 0.02343 0.02664 0.03098 0.03467 0.03895 0.04205 0.04695 0.05018 0.05421

0.00059 0.00055 0.00048 0.00042 0.00034 0.00031 0.00026 0.00023 0.00015 0.00084 0.00074 0.00068 0.00061 0.00056 0.00049 0.00043 0.00037 0.00031 0.00110 0.00103 0.00096 0.00088 0.00080 0.00064 0.00054 0.00048 0.00040 0.00121 0.00103 0.00095 0.00089 0.00078 0.00064 0.00051 0.00049 0.00039 0.00130 0.00114 0.00105 0.00091 0.00088 0.00080 0.00061 0.00055 0.00048

0.00000 0.00150 0.00530 0.01007 0.01753 0.02441 0.03245 0.04209 0.05101 0.00000 0.00259 0.00710 0.01312 0.02028 0.02815 0.03720 0.04525 0.05217 0.00000 0.00151 0.00579 0.01196 0.02110 0.02884 0.03529 0.04162 0.04796 0.00000 0.00296 0.00989 0.01958 0.03071 0.03932 0.04846 0.05518 0.06135 0.00000 0.00318 0.01065 0.02003 0.02919 0.03866 0.04957 0.061351 0.068183

0.99941 0.99796 0.99422 0.98951 0.98212 0.97529 0.96730 0.95769 0.94883 0.99942 0.99666 0.99222 0.98627 0.97916 0.97136 0.96237 0.95438 0.94751 0.99890 0.99746 0.99325 0.98717 0.97810 0.97053 0.96416 0.95790 0.95165 0.99879 0.99601 0.98916 0.97953 0.96851 0.96003 0.95103 0.94433 0.93826 0.99870 0.99568 0.98830 0.97906 0.96993 0.96054 0.94981 0.93810 0.93134

313.15

323.15

333.15

343.15

Db

Sb

24.53 20.40 16.43 13.11 11.76 10.84 9.63 8.69

1569.20 1040.62 692.34 477.21 371.79 315.61 256.18 207.98

21.58 17.09 13.90 11.79 10.37 9.12 8.45 8.05

1187.46 763.95 512.77 373.98 290.75 229.23 191.43 165.06

21.13 16.93 13.08 10.64 9.58 8.84 8.54 8.18

1021.99 681.53 460.27 318.67 253.06 212.95 182.60 159.00

18.68 13.34 10.28 9.19 8.65 8.24 7.98 7.59

859.94 508.86 336.51 258.64 217.39 186.17 163.13 142.18

17.61 11.99 9.61 8.62 8.05 7.56 7.32 7.04

658.14 382.40 271.29 214.64 183.85 153.00 136.85 120.88

a

Standard uncertainties: u(T) = 0.1 K, u(P) = 1 kPa, u(wo1) = 0.01057, u(wo2) = 0.01005, u(wo3) = 0.01117, u(ww1 ) = 0.00002, u(ww2 ) = 0.00143, u(ww3 ) = 0.00152. bD is the distribution coefficient calculated by eq 3, and S is separation factor calculated by eq 4.

B



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3. RESULTS AND DISCUSSION 3.1. Ternary Experiment Data. To obtain related parameters for simulating phenol recovery from wastewater, the LLE data for 1-dodecanol−phenol−water systems at different temperatures under atmospheric pressure were measured. This study focuses on recovering phenol from water in which the initial concentration of phenol is lower than 50 000 mg·L−1. In order to ensure the accuracy of the determination method, the binary solubility of water and 1dodecanol was determined under the same measurement conditions and compared with the binary solubility data from the literature.29 These mutual solubility data are listed in Table 2. Comparison this work with the literature is shown in Figure 1. It is found that the differences between them are small.

measured at 298.15, 313.15, 323.15, 333.15, and 343.15 K, and efficiency and selectivity factors at different temperatures were used to evaluate the extraction efficiency of 1-dodecanol and calculate enthalpy of extraction. The experimental ternary data for the system 1-dodecanol (1)−phenol (2)−water (3) were correlated by the NRTL26 and UNIQUAC27 thermodynamic models.

2. EXPERIMENTAL SECTION 2.1. Materials. Details of the chemical reagents used in this work are shown in Table 1. They were purchased from Xiya Reagent Company. The purity of all the chemical reagents is above 99% by gas chromatography. So reagents used in the present study were used as purchased. 2.2. Apparatus and Procedures. The equilibrium experiments for 1-dodecanol−phenol−water ternary systems were carried out at 298.15−343.15 K under atmospheric pressure in a self-designed equilibrium vessel shown in previously published papers.21,22 The separately quantified deionized water, 1-dodecanol, and phenol were fed into the equilibrium vessel, and they were agitated drastically with a magnetic stirrer for 2 h to obtain a homogeneous mixture. Then, the ternary mixture was put into a constant temperature thermostatic bath with an accuracy of ±0.1 K for 22 h. When phase equilibrium was reached, samples of both phases were drawn using syringes and weighed on an electronic balance (SHIMADZU, AUW220D) with an accuracy of 0.1 mg. The samples were analyzed using gas chromatograph (GC-6820, Agilent Technologies) equipped with a flame ionization detector (FID) and capillary column (DB-5MS, 30 m × 0.32 mm × 0.25 μm). The temperatures of injector and detector were set at 250 and 270 °C, separately. The oven temperature program was held at 40 °C for 2 min and then the temperature was raised to 200 °C at a temperature increase rate of 20 °C· min−1 and held for 4 min. N2 was the carrier gas. The mass fraction of every component in the two phases was determined by the internal standard method. 3,4-Xylenol and ntetradecanol were selected as internal standards for phenol and 1-dodecanol, respectively. The concentration of water in the organic phase was determined by the Karl Fischer method. The samples and internal standards were weighed using an analytical balance. Each sample was measured three times, and the average value was obtained. 2.3. Uncertainty Estimate. Generally, the results are expressed as the average of multiple measurements. Therefore, the standard deviation expression of the mean value, S(Xi), is as follows. X̅i =

1 n

Figure 1. Comparison of experimental values with literature values of water in 1-dodecanol and 1-dodecanol in water.

The LLE data for ternary system 1-dodecanol−phenol− water at T = 298.15, 313.15, 323.15, 333.15, and 343.15 K are listed in Table 2. Component concentrations in the two phases are expressed as mass fraction. The ternary phase diagrams are shown in Figure 2. The slopes of the tie lines presented in Figure 2 reveal that phenol is more soluble in 1-dodecanol than in water. Obviously from these ternary diagrams, the two-phase regions are sufficiently wide to provide sufficient possibilities for extraction. 3.2. Extraction Efficiency. Distribution coefficients (D) and separation factors (S) can be used to evaluate the efficiency with which 1-dodecanol extracts phenol from aqueous solution, and these measures were calculated as follows:

n

∑ Xi , k k=1

ÄÅ ÅÅ 1 Å uA (xi) = S(X̅i ) = ÅÅÅ ÅÅ m(n − 1) ÅÇ

n

∑ (X i , k k=1

ÉÑ1/2 ÑÑ 2Ñ − X̅i ) ÑÑÑ ÑÑ ÑÖ

(1)

(2)

where Xi,k is n times equal precision measurement column, Xi is the mean value, and m is the number of samples. Equation 2 is an expression for type A uncertainty.28 The physical meaning of S(Xi) in the equation is to reflect the dispersion degree of measurement results.

D=

w2o w2w

S=

(w2o/w3o) (w2w /w3w )

wo2

(3)

(4)

ww2

where and are the mass fractions of phenol in the organic phase and the aqueous phase, respectively, and wo3 and ww3 are the mass fraction of water in the organic phase and the aqueous phase, respectively. C



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Figure 2. Ternary phase diagrams for the system of (1-dodecanol−phenol−water) at different temperatures: (a) 298.15 K; (b) 318.15 K; (c) 328.15 K; (d) 338.15 K; (e) 348.15 K; (∗) experimental data; (red ▲) calculated data from the NRTL model; (green ●) calculated data from the UNIQUAC model.

All the distribution coefficients and separation factors are listed in Table 2. The effect of temperature and phenol concentration on D and S are showed in Figures 3 and 4. At each measured temperature, the initial material compositions are close, and the determination procedure is similar. As shown in Table 2, all distribution coefficients are greater than 1. This

indicates that phenol is more soluble in dodecanol than in water. The hydroxyl group of water has both hydrogen bond donor ability and hydrogen bond acceptor ability. It participates in hydrogen bonding not only with other substances but also with itself. Phenol has hydrogen bond donor capacity due to conjugation effects. 1-Dodecanol has D



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3.3. Correlation of LLE Data. The NRTL26 and UNIQUAC27 models were used to correlate the ternary LLE data. The UNIQUAC structural parameters (r and q) used for these systems were taken from the literature8,19 and are presented in Table 3. The optimum value of the nonrandomTable 3. UNIQUAC Structural Parameters component

ri

qi

1-dodecanol phenol water

9.3195 3.552 0.920

7.988 2.680 1.400

ness parameter (α) was placed at 0.3 and 0.2. The adjustable parameters of the NRTL and UNIQUAC models were calculated by the following equations: NRTL model: gij − gjj bij τij = = RT T

Figure 3. Experimental distribution coefficient versus mass fraction of phenol in the organic phase at different temperatures under atmospheric pressure.

(5)

ij bij yz i uij − ujj yz zz = expjjj− zzz τij = expjjj− j Tz RT { k { k

UNIQUAC model:

(6)

The parameters τij are related to the characteristic energy of the interaction between the i-type and j-type molecules. Parameters gij and gji represent the intermolecular attractive energy (J·mol−1), individually, and gij = gji. Parameters bij and bji separately represent binary parameters obtained by regression of experimental LLE values at each temperature, and uij is the interaction energy of the molecular pair i−j, uij ≠ uji, and its value is determined by the measured data. The corresponding binary interaction parameters of the NRTL and UNIQUAC models are obtained by minimizing the square of the difference between the experimental and calculated data in mole fraction of the two liquid phases in each ternary system. The minimum objective function (OF) is Ä É expt calc 2 Ñ n Å 3 2 ÅÅÅ (Tkexpt − Tkcalc)2 ÑÑÑ ( w w ) − ijk ijk ÑÑ OF = ∑ ∑ ∑ ÅÅÅÅ + ÑÑ 2 2 Å ÑÑ σ σ T w i=1 j=1 k=1 Å ÅÇ ÑÖ

Figure 4. Experimental separation factor versus mass fraction of phenol in the organic phase at different temperature under atmospheric pressure.

(7)

where w and T are the mass fraction and temperature, respectively, i, j, and k are the number of components, the number of phases, and the number of experimental data sets, respectively, n is the total number of all data sets, expt and calc represent experimental and calculated values, respectively, and σT and σw are standard deviations of temperature and mass fraction. In order to investigate the degree of deviation between the regression values and the experimental results, a relative root-mean-square deviation (RMSD) is introduced for comparison, as defined by the following expression: ÄÅ 3 É ÅÅ ∑ ∑2 ∑n (w expt − w calc)2 ÑÑÑ1/2 ÅÅ i = 1 j = 1 k = 1 ijk ÑÑ ijk ÑÑ RMSD = ÅÅÅ ÑÑ ÅÅ 6 n ÑÑ (8) ÅÅÇ ÑÖ

hydrogen bond acceptor ability because of its long carbon chain. So it is shown that phenol is more accessible to the oil phase. Increasing the extraction temperature in the measured system results in a decrease of the distribution coefficient. This may be the reason that the interaction between molecules is weakened after the temperature rises. The separation factors at all temperatures of each group are much greater than 100, which means that the 1-dodecanol is a potential solvent to extract phenol from aqueous solution. The separation factors will also decrease as the concentration of phenol increases or the temperature rises. As the amount of phenol added to the system increases, the two-phase region shrinks. This indicates that the extraction performance of the 1-dodecanol weakens. Meanwhile, there is a gradual reduction in the extraction abilities of the 1-dodecanol with the increase of temperature. Lower extraction temperature is beneficial for extraction. This conclusion is in line with most liquid−liquid extraction processes.

The binary interaction parameters regressed by the NRTL and UNIQUAC models are listed in Table 4. The predicted values of the system are compared with the experimental values at different temperatures, as shown in Figure 2. For all investigated experiments, concentration of phenol in water is E



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Table 4. Binary Interaction Parameters of the NRTL and UNIQUAC Models for the 1-Dodecanol (1)−Phenol (2)−Water (3) System NRTL

UNIQUAC

T, K

component i−j

bij

bji

αij

RMSD, %

bij

bji

RMSD, %

298.15

1−2 1−3 2−3 1−2 1−3 2−3 1−2 1−3 2−3 1−2 1−3 2−3 1−2 1−3 2−3

−688.38417 267.92142 −70.62338 −428.48015 251.92211 −126.66739 −540.26937 175.39832 −127.77495 −367.30439 180.18833 −79.953137 −277.14258 110.53499 −76.89411

123.47572 2662.86544 1084.50284 −124.42806 2693.41245 1235.9132 26.10259 2741.48084 1272.66137 −101.67356 2808.89525 1297.95698 −181.51753 2920.90633 1324.12988

0.3 0.2 0.2 0.3 0.2 0.2 0.3 0.2 0.2 0.3 0.2 0.2 0.3 0.2 0.2

0.4203

9.78494 −484.60723 −55.05800 −411.87685 −526.27071 −261.67138 −244.54408 −508.95266 −184.08385 −155.53432 −491.29551 −62.70832 −283.4035 −474.03346 −247.5713

141.49429 −74.43983 −41.06456 331.72238 −58.47921 75.39850 262.27335 −55.23763 22.10832 223.87561 −56.90070 −54.06074 282.65421 −63.63445 63.80619

0.4148

313.15

323.15

333.15

343.15

0.2042

0.3430

0.4314

0.3486

0.1342

0.3227

0.4264

0.4641

Table 5. Values of bij + bji and (bij + bji)/T by the Regression of the NRTL Model at Different Temperatures bij + bji

(bij + bji)/T

T, K

1−2

1−3

2−3

1−2

1−3

2−3

298.15 313.15 323.15 333.15 343.15

−564.908 −552.908 −514.167 −468.978 −458.66

2930.787 2945.335 2916.879 2989.084 3031.441

1013.879 1109.246 1144.886 1218.004 1247.236

−1.89471 −1.76563 −1.59111 −1.40771 −1.33662

9.829907 9.405507 9.026394 8.972185 8.834158

3.400568 3.542219 3.542895 3.656022 3.634666

much lower than saturated concentration at corresponding temperature.30 All RMSD values are smaller than 0.4641%. It shows that the fitting of the NRTL and UNIQUAC models for the ternary system 1-dodecanol−phenol−water has high accuracy. The RMSD average of the NRTL and UNIQUAC models are 0.3495 and 0.3524, respectively. The NRTL model is more suitable than the UNIQUACL model to correlate the LLE data of this work. The physical meaning of the binary interaction parameters is further discussed. According eq 5, τij and τji were added, then new equation is as follows: τij + τji = =

gij − gjj

+

gji − gii

RT RT 2gij − (gii + gjj) RT bji + bij (9)

Figure 5. Effect of temperature on (bij + bji)/T for 1-dodecanol− phenol, 1-dodecanol−water, and phenol−water.

where all attractive energies g are defined as negative values. According to eq 9, if the attraction energy between unlike molecules is greater than the attractive energy between like molecules, bij+ bji is negative, and if the converse is true, bij+ bji is positive. The smaller bij+ bji is, the greater the interaction between unlike molecules is. The bij+ bji and (bij+ bji)/T values at different temperatures are listed in Table 5. The effect of temperature on (bij+ bji)/T is shown in Figure 5. As can be seen from the figure, (b12 + b21)/T is negative, whereas both (b13 + b31)/T and (b23 + b32)/T are positive within the measured temperature range. When the temperature rises, the absolute value of (b12 + b21)/T gradually decreases. This

indicates that high temperature is not conducive to the progress of the extraction, which is consistent with the rule observed in the experimental measurements in Table 2. The (b13 + b31)/T of 1-dodecanol and water has the largest value. It turns out that the attraction energy between them is the smallest, which is also consistent with the mutual solubility of 1-dodecanol and water. The attractive energy between 1dodecanol and phenol is stronger than that between water and phenol. So extraction of phenol from water by 1-dodecanol can be successfully achieved. 3.4. Thermodynamic Studies. At a certain temperature, a solute is dissolved in two mutually incompatible liquid

=

T

F



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solvents. When the system reaches equilibrium, the solute is distributed in the two solvents to a certain degree. If the solute is neither dissociated nor associated in either phase, the equilibrium can be expressed as follows when equilibrium is reached at a certain temperature: C6H6OH (dilute phase) ↔ C6H6OH (organic phase)

where phenol on the left indicates the components in the dilute phase and phenol on the right indicates the components in the organic phase. In light of the phase equilibrium rule, the chemical potential of phenol in the two phases is equal, and according to the chemical potential expression of the solute component, the ratio of the activity of phenol in the two solvents is a constant, which can be expressed as Kd. If both solutions are relatively dilute, the ratio of their relative concentrations, named as the distribution coefficient (D), is approximately equal to Kd. The Kd in the van’t Hoff equation is replaced by D, and the expression is as follows: ln D = −

ΔH ΔS + RT R

Figure 6. Plot of ln D vs 1000/T. (10)

where ΔH represents the enthalpy change and ΔS represents the entropy change during extraction, respectively, and xo2 and xw2 represent the mole fraction of phenol in organic phase and aqueous phase, respectively. In order to reduce the difference between D and Kd, some experiments were carried out at a lower phenol concentration, about 1 g·L−1, with 1-dodecanol at different temperatures (298.15−343.15 K) in the present work. The distribution coefficients (D) at different temperatures are listed in Table 6. The value of ln D was plotted

system obtained from the LLE data were successfully correlated by the NRTL and UNIQUAC models. Comparison of RMSD values showed that the NRTL model is more accurate in correlation to data than the UNIQUAC model. The positive and negative (bij + bji)/T values indicate that the solubility of phenol in 1-dodecanol is greater than that in water. The van’t Hoff equation was used to fit the distribution coefficient dependence on temperature, and extraction enthalpy was obtained. The results show that extraction of phenol from water with 1-dodecanol is an exothermic process. Lowering the temperature is beneficial to the progress of the extraction process.

Table 6. Distribution Coefficient of Phenol in the 1Dodecanol and Water Mixture

S Supporting Information *

D=

x 2o x 2w

(11)

T, K

Da

1/T, K−1

ln D

298.15 313.15 323.15 333.15 343.15

354.94 205.15 155.26 125.18 104.06

3.3540 3.1934 3.0945 3.0017 2.9142

5.7560 5.3238 5.0451 4.8298 4.6450

■

ASSOCIATED CONTENT

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jced.9b00176. Internal standard curves of phenol and 1-dodecanol and standard uncertainty evaluation (PDF)

■

AUTHOR INFORMATION

Corresponding Author

a

D is the distribution coefficient calculated by eq 11.

*Tel: + 86 13632384249. E-mail address: [email protected]. cn.

against 1/T in Figure 6. A value of ΔH equal to −21.20 KJ· mol−1 was obtained from the slope of the fitting line. The negative ΔH means that the extraction process is an exothermic process. Lowering the temperature will increase the value of D, and it is beneficial to the extraction. The theoretical results of extraction thermodynamics are consistent with the LLE experiment results.

ORCID

Yun Chen: 0000-0001-5784-2602 Notes

The authors declare no competing financial interest.

■

REFERENCES

(1) Asrami, M. R.; Saien, J. Salting-out effect on extraction of phenol from aqueous solutions by [Hmim][NTf 2 ] ionic liquid: Experimental investigations and modeling. Sep. Purif. Technol. 2018, 204, 175−184. (2) Jourshabani, M.; Badiei, A.; Shariatinia, Z.; Lashgari, N.; Mohammadi Ziarani, G. Fe-Supported SBA-16 Type Cagelike Mesoporous Silica with Enhanced Catalytic Activity for Direct Hydroxylation of Benzene to Phenol. Ind. Eng. Chem. Res. 2016, 55 (14), 3900−3908. (3) Yang, C.; Qian, Y.; Zhang, L.; Feng, J. Solvent extraction process development and on-site trial-plant for phenol removal from industrial coal-gasification wastewater. Chem. Eng. J. 2006, 117 (2), 179−185.

4. CONCLUSIONS The liquid−liquid equilibrium for the ternary system 1dodecanol−phenol−water was determined at 298.15, 313.15, 323.15, 333.15, and 343.15 K under atmospheric pressure. The distribution coefficients and selectivity factors indicate that 1dodecanol can effectively extract phenol from wastewater. As the phenol concentration increases or the temperature rises, the distribution coefficients (D) and selectivity factors (S) decrease. The binary interaction parameters of the ternary G



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