Article pubs.acs.org/jced
Ternary Liquid−Liquid Equilibrium of Azeotropes (Water +2Propanol) with Ionic Liquids ([Dmim][NTf2]) at Different Temperatures Xicai Xu, Tingran Zhao, Yongkun Wang, Xueli Geng, and Yinglong Wang* College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, China ABSTRACT: The liquid−liquid equilibrium (LLE) of a ternary system of water (H2O) + 2-propanol + 1-decyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Dmim][NTf2]) ionic liquid was measured in the temperature range from 278.15 to 298.15 K at atmospheric pressure. The distribution coefficient and selectivity were calculated to determine the influence of the temperature on the LLE. The results indicate that a decrease in temperature reduces the solubility of H2O in [Dmim][NTf2] and increases the immiscibility region of the ternary phase diagram. The experimental data were correlated using the nonrandom two liquid and the universal quasichemical models, and the critical properties for [Dmim][NTf2] were determined.
data at other temperatures using the NRTL model.28 It can be seen from these reports that the increase in the temperature leads to a decrease in the ILs’ separation capability. One study investigated systems of alcohols and alkanes with ILs.30 Ram et al. studied systems of hexadecane, ethanol, and imidazoliumbased ILs and examined the influence of temperature on 1,3dimethylimidazolium methyl sulfate ([Mmim][MeSO4]) using the NRTL model.30 Rodriguez studied ethanol + hexane + ILs at different temperatures using the NRTL model.31 As shown in these reports, when the temperature decreases, the phaseseparation capability of the ILs increases. Some researchers studied the effect of temperature in systems of water−alcohols−ILs.4,32 Garcia-Chavez et al. provided LLE data for mixtures of dihydric alcohols (monoethylene glycol, propylene glycol, 2,3-dihydroxybutane) and water with the IL tetraoctyl ammonium 2-methyl-1-naphtoate.25−27 Nann et al. investigated systems of H2O + 1-butanol (NBA) + ILs, and the perturbed-chain statistical associating fluid theory (PC-SAFT) was used to correct the experimental data.11 Chafer et al. researched the systems for H2O + ethanol (ET) + 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Bmim][NTf2]) and H2O + ET + 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([Bmp][NTf2]) at different temperatures using the NRTL and universal quasichemical
1. INTRODUCTION Liquid−liquid extraction plays an important role as a separation method in the chemical industries.1 Thermodynamics data such as liquid−liquid equilibrium (LLE) data and binary interaction parameters are important for the design of the separation process. 2-Propanol (IPA) is widely used in chemical production and as a solvent.2 The separation of 2-propanol from hydrofacies is of importance in engineering applications, thus in recent years, many different processes have been examined for the recovery of pure 2-propanol.3 The key to obtaining a suitable extraction process to separate mixtures is the choice of extraction agent. Ionic liquids (ILs) are usually composed of an organic or inorganic anion and bulky organic cation. ILs have some special properties that make them advantageous for liquid−liquid extraction, such as a large liquid range, which allows for ease of separation. ILs are salts, the melting point of which is below 373.15 K, which makes them easily recoverable. ILs are “green solvents” that can reduce the emissions of volatile organic compounds (VOCs) compared with the conventional organic solvents.4 Many scholars have studied systems including alcohols and ILs,4−27 and many of them researched the effect of temperature on the extraction power. Some researchers studied systems of alcohols and esters with ILs.28 Cai et al. studied the LLE of 1alkyl-3-methylimidazolium dialkylphosphate with methanol (MEI) and dimethyl carbonate (DMC) using the nonrandom two liquid (NRTL) model.29 Cai et al. studied the system of methanol + methyl acetate +1-ethyl-3-methylimidazolium acetate ([Emim][Ac]) at 299.15 K and calculated the LLE © XXXX American Chemical Society
Received: January 20, 2017 Accepted: April 5, 2017
A
DOI: 10.1021/acs.jced.7b00058 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Table 1. List of Chemicals chemical ethanol 2-propanol 1-decyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide a
molecular formula
CAS number
molar mass/(g·mol−1)
purity (mass fraction)
C2H6O C3H8O C16H27O4N3S2F6
64-17-5 67-63-0 433337-23-6
46.07 60.10 503.52
0.995a 0.995a 0.990a
manufacturer Tianjin Kermel Chemical Reagent Co., Ltd. Tianjin Kermel Chemical Reagent Co., Ltd. Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences
Analysis by supplier.
(UNIQUAC) models.4,32 With the decrease in temperature, the miscibility of the water and the ILs studied in the literature was reduced, and this illustrates that a low temperature is more suitable for separations of these systems containing ILs. This study focuses on the investigation of the effect of temperature on the LLE behavior of a ternary mixture containing 2-propanol, water, and [Dmim][NTf2]. In our previous23 work, ternary systems of H2O + IPA with different ionic liquids were studied. [Dmim][NTf2] showed the best separation performance among the ILs studied, so it was chosen as the extraction agent in this work. The IL studied in this work was not assumed to be in ionic form at all. The ability of an IL to serve as a liquid−liquid extraction agent was evaluated through the distribution coefficient (β) and selectivity (S). The UNIQUAC33 and NRTL34 models were used to correlate the experimental data. The values of the root-meansquare-deviation (rmsd) between the experimental data and calculated data were determined to measure the applicability of the NRTL and UNIQUAC models to the water−IPA− [Dmim][NTf2] system.
The compositions of IPA and water were determined by a gas chromatograph (GC-2014C) equipped with a thermal conductivity detector (TCD) and using an internal standard method to analyze the compositions. The gas chromatographic column is a packed column (2 m × 3 mm), and the stationary phase is GDX-104. To prevent the IL from reaching the gas chromatographic column, a precolumn was used. The gas chromatographic operating conditions used in this work are as follows: the temperature of the injector was 433.15 K, the temperature of the oven was 523.15 K, and the temperature of the detector was 533.15 K. The gravimetric method was used to determine the IL composition in this work. The differences in the liquid sample before and after vaporization were calculated to determine the content of IL. A vacuum drying oven (model number DZF-6020) supplied by Shanghai Boxun was used to vaporize the liquid sample. The method used in this work is the gravimetric method, although other methods such as the method by comparison to density data and the cloud point method51 have been widely used in the study of the LLE for ternary systems containing ILs.
2. EXPERIMENT 2.1. Chemicals. Information about the materials used in this work is provided in Table 1. The purity of the IPA and ethanol in this work was verified by gas chromatography. Ethanol was used as an internal standard. The purity of the [Dmim][NTf2] was provided by the supplier, and the water used in this work was doubly distilled and deionized. All materials were used without further purification. 2.2. Apparatus and Procedure. The procedure and equipment used to measure the experimental data have been described in a previous work.23 Mixtures with various mass compositions in the two-phase region were used to determine the LLE data. The equilibrium cell used in this work was designed by us. The mixtures described above were put into the equilibrium cell, and a mechanical stirrer was used to stir these mixtures to achieve complete mixing. The apparatus used to control the temperature was a low-temperature thermostat supplied by Changliu Instrument Factory of Beijing in China, model number HX-105, and the temperature was controlled within 0.05 K. The mixed system studied in this paper was stirred rigorously in the equilibrium cell for 3 h and then settled for approximately 15 h to ensure the complete splits of the equilibrium phases at different temperatures from 278.15 to 298.15 K. The cloud point method36 was used in the preexperiment to make the compositions of every component cover the scope of the two-phase region to the greatest extent possible. The masses of the IL and water were fixed and equal, 2-propanol was added into the mixture of IL and water dropwise until the ternary mixture became one phase, and then the compositions of the two phases were measured until they were unchanged, and the experimental time was determined. This method was described in our previous work.23,52,53
3. EQUATIONS TO CORRELATE EXPERIMENTAL DATA The NRTL and UNIQUAC models4,24,28,37−44 have been widely used in correlating LLE data. In this work, the experimental data were also correlated by these two models. The nonlinear least-squares method was used to obtain the binary interaction parameters of the NRTL and UNIQUAC models through data regression using MATLAB. In our previous work,23,52,53 the method of modeling was described in detail. The model for liquid−liquid equilibrium in this paper is as follows: γi IxiI = γi IIxiII
(1)
where xIi is the component percentage of component i in mole in water rich phase, xIIi is the component percentage of component i in mole in IL rich phase, γIi is the activity coefficients of component I in upper phase and γIIi is the activity coefficients of component i in lower phase. The molecular volume structure parameter r and the molecular surface area parameter q were calculated by the polarizable continuum model (PCM)45 after the IL structure was optimized using Density Functional Theory (DFT).46 The quantum chemistry approach can solve the problem of the missing parameters for a new IL. Parameters r, q and q′ of ILs in the UNIQUAC model are listed in Table 2.47 For most substances, q is equal to q′, except for water and some small alcohols. The Lydersen−Joback−Reid method48 was used to calculate the critical properties of [Dmim][NTf2] due to the values that are missing, and the results are shown in Table 3. B
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Table 4. LLE Data, Solute Distribution, β and Selectivity, S for Ternary Systems of Water (1) + 2-Propanol (2) + [Dmim][NTf2] (3) at T = 278.15 K, 288.15 K, and 298.15 K and p = 0.1 MPaa
Table 2. UNIQUAC Structural Parameters of Pure Components
a
component
ri
qi
q′i
[Dmim][ [NTf2] ethanola 2-propanola watera
16.9766 2.5755 2.7791 0.9200
13.7052 2.5880 2.5080 1.3997
13.7052 0.920 2.5080 1.0000
upper phase x1
4. RESULTS AND DISCUSSION 4.1. Experiment Data. The data obtained by experiment for a ternary system of H2O (1) + IPA (2) + [Dmim][NTf2] (3) at different temperatures and 101.325 kPa are shown in Table 4, where xi is the component percentage of component i in mole in every sample in this work. As shown in Figure 1 to Figure 3, the system in this work was a Treybal type I. The solubility of water in [Dmim][NTf2] increased with the temperature, while the two-phase region decreased with the increasing temperature. Figure 4 shows the effect of temperature was illustrated. The selectivity (S) was used to measure the efficiency of the IL as an extraction agent, and the distribution coefficient (β) determines the solvent capacity of the IL, which determines the amount of extraction agent required in the extraction process. The values of β and S are shown in Table 4 and were calculated by the equations
S=
x 2II x 2I
(2)
(x 2II/x1II) (x 2I/x1I)
x1
x2
β
S
Water (1) + 2-Propanol (2) + [Dmim][NTf2] (3) T = 278.15 K 1.000 0.000 0.105 0 0.948 0.053 0.116 0.144 2.75 22.55 0.929 0.071 0.141 0.217 3.06 20.16 0.900 0.100 0.160 0.321 3.22 18.20 0.873 0.127 0.251 0.393 3.09 10.71 0.861 0.139 0.325 0.416 2.99 7.92 0.842 0.157 0.374 0.418 2.66 5.99 0.823 0.176 0.419 0.411 2.34 4.59 Water (1) + 2-Propanol (2) + [Dmim][NTf2] (3) T = 288.15 K 1.000 0.000 0.188 0.000 0.971 0.029 0.228 0.165 5.61 23.90 0.957 0.043 0.268 0.247 5.75 20.56 0.940 0.060 0.304 0.312 5.24 16.21 0.920 0.079 0.382 0.358 4.52 10.88 0.909 0.090 0.443 0.368 4.09 8.39 0.888 0.111 0.464 0.391 3.54 6.77 0.870 0.127 0.533 0.353 2.79 4.55 Water (1) + 2-Propanol (2) + [Dmim][NTf2] (3)b T = 298.15 K 1.000 0.000 0.243 0.000 0.980 0.020 0.347 0.175 8.77 24.82 0.970 0.030 0.387 0.235 7.87 19.74 0.958 0.042 0.429 0.285 6.82 15.22 0.940 0.059 0.500 0.322 5.43 10.21 0.932 0.068 0.540 0.321 4.76 8.21 0.913 0.085 0.598 0.310 3.64 5.55 0.880 0.116 0.664 0.279 2.41 3.19 0.863 0.131 0.700 0.256 1.96 2.41
From reference Santiago et al.49
β=
lower phase
x2
(3)
where xII2 is component percentage of IPA in mole in the [Dmim][NTf2]-rich phase, xI2 is the component percentage of IPA in mole in the water-rich phase, xI1 is the component percentage of water in mole in the water-rich phase and xII1 is the component percentage of water in mole in the [Dmim][NTf2]-rich phase. As can be observed, the capability of the studied IL decreased with the addition of IPA, and the β and S of the studied alcohol decreased with the increasing temperature. As shown in Figure 1 to Figure 3, the slope of the tielines shows that 2-propanol has a greater affinity to the [Dmim][NTf2]-rich phase than to the water-rich phase, and the slope of the tie-lines also show that the IL studied was suitable to extract 2-propanol from the mixture of water and 2propanol. The values of β increased slightly with the temperature. The values of S were greater than unity, which indicates that [Dmim][NTf2] was compatible to separate the system studied in this work; this result is consistent with the slope of the tie-lines. Elevating the temperature has a negative effect on the separation ability of [Dmim][NTf2] for the extraction of alcohols from water, similar to the results of the study of Chafer et al.4,32 Gao et al. studied the systems of H2O
a Standard uncertainties u are u (xi) = 0.005 u(T) = 0.05 K and u(p) = 0.0015 MPa. bFrom ref 23.
+ (ET/NPA) + [Dmim][NTf2],35 and Chafer et al. studied the systems of H2O + NPA with [Hmim][NTf2] and [Emim][NTf2].50 A comparison between the results of these studies and those of this work indicates that the IL studied in this work is suitable to separate a mixture of water + 2-propanol. 4.2. LLE Correlation. To make the binary interaction parameters of the NRTL and UNIQUAC models correlating the experimental data as accurate as possible, the deviations between the experimental and calculated compositions for every component were determined, and the binary parameters were determined by minimizing the sum of squares difference between these deviations. The objective function (OF) used was defined as M
OF =
2
3
∑ ∑ ∑ (xijkexp − xijkcalc)2 (4)
k=1 j=1 i=1
Table 3. Critical Properties of [Dmim][NTf2], Calculated by Group Contributiona [Dmim][NTf2]
Tb (K)
Tc (K)
pc (bar)
Vc (cm3/mol)
ω
T (K)
ρ(g/cm3)
1033.9
1378.3
18.5
1322.1
0.6291
298.15
1.0293
Notation: T, temperature; Tb, normal boiling temperature; Tc, critical temperature; Pc, critical pressure; Vc, critical volume; ω, acentric factor; ρ, liquid density.
a
C
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Figure 1. LLE phase diagram for the systems of water (1) + 2propanol (2) + [Dmim][NTf2] (3) at T = 278.15 K; ■, experimental value; ○, calculated value by NRTL model; □, calculated value by UNIQUAC model.
Figure 3. LLE phase diagram for the systems of water (1) + 2propanol (2) + [Dmim][NTf2] (3) at T = 298.15 K. ■, experimental value; ○, calculated value by NRTL model; □, calculated value by UNIQUAC model.
Figure 2. LLE phase diagram for the systems of water (1) + 2propanol (2) + [Dmim][NTf2] (3) at T = 288.15 K. ■, experimental value; ○, calculated value by NRTL model; □, calculated value by UNIQUAC model.
Figure 4. LLE phase diagram for the systems of water (1) + 2propanol (2) + [Dmim][NTf2] (3) at different temperatures. ■, experimental data at 278.15 K; ○, experimental data at 288.15 K; □, experimental data at 298.15 K.
where x is the mole fraction of each component and the subscripts i, j, and k denote the component, phase, and tie-line, respectively.
where M is the number of tie-lines, xexp indicates the experimental data in the form of mole fractions, xcalc is the calculated data in the form of mole fractions, i is a component, j is a phase, and k indicates a tie-line. The value of OF was set to 10−6 in the regression procedure. As shown in Figure 1 to Figure 3, the experimental data correlates well with both the NRTL and UNIQUAC models. The obtained NRTL and UNIQUAC binary interaction parameters for ternary systems H2O + IPA + [Dmim][NTf2] at T = 278.15 K, 288.15 K, 298.15 K and p = 0.1 MPa are presented in Table 5. The root-mean-square-deviation (rmsd) was used to measure the consistency of the calculated data and experimental data and is defined as ⎛ M 2 3 (x exp − x calc)2 ⎞1/2 ijk ijk ⎟ rmsd = ⎜⎜∑ ∑ ∑ ⎟ 6M ⎠ ⎝k=1 j=1 i=1
5. CONCLUSION In this work, we study a ternary system containing water, 2propanol, and [Dmim][NTf2] at different temperatures and atmospheric pressure. The LLE data for the system studied were correlated by the NRTL and UNIQUAC models. The comparative results of the rmsd between the experimental and calculated compositions show that both models correlate the data for the system studied properly. Then, the capability of the IL as a liquid−liquid extraction solvent was assessed using the distribution coefficient and selectivity. The distribution coefficient and selectivity decrease with the increasing temperature, and thus the efficiency of the ionic liquid for the extraction decreases with the increasing temperature. The effects of the temperature were analyzed, showing that the decrease in temperature reduces the solubility of water in
(5) D
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Table 5. NRTL and UNIQUAC Binary Interaction Parameters for Ternary Systems Water (1) + 2-Propanol (2) + [Dmim][NTf2] (3) at T = 278.15 K, 288.15 K, 298.15 K, and p = 0.1 MPa NRTL parameters i−j
Δgij (kJ·mol−1)
Δgji (kJ·mol−1)
rmsd
α
Water (1) + 2-Propanol (2) + [Dmim][NTf2] (3) T = 278.15 K 1−2 4.8546 3.2461 0.0113 0.3 1−3 28.6358 10.3106 2−3 8.7764 1.6325 Water (1) + 2-Propanol (2) + [Dmim][NTf2] (3) T = 288.15 K 1−2 5.5617 2.2018 0.0128 0.3 1−3 18.1978 4.3563 2−3 −1.9900 2.6998 Water (1) + 2-Propanol (2) + [Dmim][NTf2] (3) T = 298.15 K 1−2 4.6083 1.7122 0.0052 0.3 1−3 12.4449 2.2192 2−3 1.9907 3.5078 UNIQUAC parameters i−j
Δuij (kJ·mol−1)
Δuji (kJ·mol−1)
rmsd
Water (1) + 2-Propanol (2) + [Dmim][NTf2] (3) T = 278.15 K 1−2 −0.6796 4.928 0.0157 1−3 −0.7015 9.5685 2−3 −0.8378 3.1091 Water (1) + 2-Propanol (2) + [Dmim][NTf2] (3) T = 288.15 K 1−2 0.6532 13.7579 0.0101 1−3 −1.3746 12.9702 2−3 53.8932 −0.7356 Water (1) + 2-Propanol (2) + [Dmim][NTf2] (3) T = 298.15 K 1−2 1.2558 2.2062 0.0081 1−3 1.0454 8.6475 2−3 5.7698 0.0557
[Dmim][NTf2] and increases the size of the immiscibility region of the ternary phase diagram.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. ORCID
Yinglong Wang: 0000-0002-3043-0891 Funding
Financial support from the National Natural Science Foundation of China (Project 21676152) is gratefully acknowledged. Notes
The authors declare no competing financial interest.
■
REFERENCES
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DOI: 10.1021/acs.jced.7b00058 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
