Separation of Alkylbenzenes from n-Heptane Using Binary Mixtures of

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

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Separation of Alkylbenzenes from n‑Heptane Using Binary Mixtures of Ionic Solvents Mohammad S. AlTuwaim,* Khaled H. A. E. Alkhaldi, Adel S. Al-Jimaz, and Khaled M. Alanezi Chemical Engineering Department, College of Technological Studies, PAAET P.O. Box 42325, Shuwaikh 70654, State of Kuwait

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S Supporting Information *

ABSTRACT: A study of liquid−liquid extraction of alkylbenzenes (propylbenzene, butylbenzene, or p-xylene) from n-heptane using ionic solvent binary mixture of 1-octyl-3-methylimidazolium hexafluorophosphate [C8C1im][PF6] and 1-ethyl-3methylimidazolium methylsulfate [C2C1im][CH3SO4] is conducted at 313.2 K and a pressure of 101.3 kPa. The distribution ratio and selectivity for systems under study were calculated and compared to systems including other solvents such as sulfolane and other ionic liquids. The use of the present binary mixture of ILs provided a higher mole-based distribution ratio than the use of sulfolane, a pure IL, and a mixture of other ILs. On the other hand, the use of [C8C1im][PF6] and [C2C1im][CH3SO4] mixture contributed to a mass-based distribution ratio comparable to that of sulfolane and a higher distribution ratio than the others involving ILs and led to a higher selectivity than all the other solvents including sulfolane. Hence the extractive properties of [C8C1im][PF6] and [C2C1im][CH3SO4] mixture revealed a potential substitute for other solvents. Furthermore, the nonrandom two-liquid model was utilized to assess the data.

1. INTRODUCTION Various solvents, such as ethers, amines, alcohols, and other organic compounds have been used in the petroleum and chemical industries. The selection of suitable solvent in separation processes is a key to improve current industrial processes.1−10 To extract aromatics from aliphatics in mixtures with 20−65 wt % aromatic content, liquid−liquid extraction is widely used.11−15 Ionic liquids (ILs) were proposed as a substitute to conventional solvents in extraction processes because of their low volatility. This substantial property leads to an easier recovery of ILs using simple separation processes.16−21 A contender IL should have extractive properties comparable to or higher than that of the currently used solvents such as sulfolane. In addition, many industrial processes favor the mixed solvents power due to the improvement of certain physical and extractive properties.22−27 Consequently, using binary mixtures of ILs instead of using a single IL28−40 would result in more favorable properties such as the distribution coefficient, selectivity, and viscosity. In our previous work,40−47 [C8C1im][PF6] showed a high distribution ratio and viscosity but low selectivity, whereas [C2C1im][CH3SO4] showed a low © XXXX American Chemical Society

distribution coefficient and low viscosity along with high selectivity. Therefore, [C8C1im][PF6] and [C2C1im][CH3SO4] ILs were used as a binary mixture to separate aromatics (propylbenzene, butylbenzene, or p-xylene) from aliphatic (nheptane) at 313.2 K and a pressure of 101.3 kPa. The objective is to achieve higher values of a distribution ratio and/or selectivity than sulfolane and to offset the high viscosity of [C8C1im][PF6].18−21 Moreover, a screening procedure is applied to choose the best composition of the ILs binary mixture to be used in all investigated systems. Furthermore, the liquid−liquid equilibrium (LLE) data were used to calculate the extractive properties and the parameters of the NTRL model.48,49

2. EXPERIMENTAL SECTION Hydrocarbons (propylbenzene, butylbenzene, p-xylene and nheptane) were purchased from Sigma-Aldrich. The ILs, [C8C1im][PF6] and [C2C1im][CH3SO4], were purchased Received: November 20, 2018 Accepted: February 20, 2019

A

DOI: 10.1021/acs.jced.8b01100 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

pressure of 101.3 kPa are presented in Tables 2−4. The experimental tie lines of the mixtures under study are depicted

from Iolitec GmbH. A Mettler Toledo C20-KF coulometer was used to measure the water contents for all chemicals. Chemicals were used without any further purification. Details about the chemicals including CAS numbers and purities are shown in Table 1.

Table 2. Experimental Equilibrium Data of Mole Fractions (xi), Distribution Coefficient (Kx), [C8C1im][PF6] Mass Fraction in the Binary Mixtures of ILs (m3) and Selectivity (S) for the System n-heptane (1) + propylbenzene (2) + [C8C1im][PF6] (3) + [C2C1im][CH3SO4] (4) at m3 = 0.7 at T = 313.2 K and P = 101 kPaa

Table 1. Details of the Chemicals: Purities and Water Content compound

CASRN

supplier

[C8C1im][PF6]

304680-36-2

[C2C1im] [CH3SO4] n-heptane

516474-01-4

propylbenzene

103-65-1

butylbenzene

104-51-8

p-xylene

106-42-3

Iolitec GmbH Iolitec GmbH SigmaAldrich SigmaAldrich SigmaAldrich SigmaAldrich

142-82-5

mass fraction purity

water content (mass fraction)

0.99

≤0.0005

0.99

≤0.0005

0.997

≤0.00004

0.99

≤0.00004

0.99

≤0.00003

0.995

≤0.00005

n-heptane-rich phase

The hydrocarbons and ILs are mixed in a 60 mL glass cell heated to 313.2 K by a LUADA water bath and circulating unit. The mixture consisted of 20 g of n-heptane, 20 g of the mixed solvent with different amounts of propylbenzene, butylbenzene, or p-xylene weighed by a Denver Instrument Company A-250 model with an accuracy of ±0.0001 g. The mixture was stirred vigorsly for 1 h and then left to settle for 4 h to reach equilibrium. Screening LLE experiments were conducted to attain the best composition of the ILs mixture. The samples of the screening experiments comprise an equal amount of the hydrocarbon’s mixture, 20% p-xylene and 80% n-heptane in mass basis, added to the ILs binary mixture of [C8C1im][PF6] + [C2C1im][CH3SO4] starting with 0% up to 100% mass basis [C8C1im][PF6]. Then LLE data of the systems (n-heptane + propylbenzene, butylbenzene or p-xylene + [C8C1im][PF6] + [C2C1im][CH3SO4] were determined using the binary ILs mixture composition that gave the maximum percent p-xylene extraction. The samples from the ionic and aliphatic-rich layers were collected, weighed, and then analyzed using an Agilent gas chromatograph/mass selective detector system (GC/MSD 7890B) coupled with an Agilent autosampler (7693). The detailed measurement and analysis of phase composition is dicussed in a previously published work.50

IL-rich phase

x1

x2

x1

x2

Kx

S

1.000 0.974 0.961 0.949 0.936 0.907 0.879 0.852 0.826 0.779 0.737 0.698 0.662 0.630 0.600 0.574 0.549 0.526

0.000 0.026 0.039 0.051 0.064 0.093 0.121 0.148 0.174 0.221 0.263 0.302 0.338 0.370 0.400 0.426 0.451 0.474

0.011 0.012 0.011 0.011 0.011 0.010 0.010 0.010 0.009 0.009 0.008 0.008 0.007 0.007 0.007 0.006 0.006 0.006

0.000 0.019 0.027 0.035 0.043 0.061 0.078 0.092 0.105 0.129 0.149 0.166 0.179 0.189 0.201 0.212 0.221 0.229

0.72 0.70 0.69 0.67 0.66 0.64 0.62 0.60 0.59 0.57 0.55 0.53 0.51 0.50 0.50 0.49 0.48

60.74 59.86 58.86 57.81 56.73 55.61 54.46 53.29 52.10 50.88 49.64 48.38 47.09 45.79 44.46 43.11 41.74

a

Standard uncertainties (u) are u(T) = 0.1 K, u(P) = 1 kPa, u(x) = 1.0 × 10−3, u(m) = 1.0 × 10−3.

Table 3. Experimental Equilibrium Data of Mole Fractions (xi), Distribution Coefficient (Kx), [C8C1im][PF6] Mass Fraction in the Binary Mixtures of ILs (m3), and Selectivity (S) for the System n-Heptane (1) + Butylbenzene (2) + [C8C1im][PF6] (3) + [C2C1im][CH3SO4] (4) at m3 = 0.7 at T = 313.2 K and P = 101 kPaa n-heptane-rich phase

3. RESULTS AND DISCUSSION 3.1. Screening LLE Experiments with [C8C1im][PF6] + [C2C1im][CH3SO4] ILs Binary Mixture. The result of LLE screening experiments is shown in Table S1. The percent pxylene extraction is plotted versus the [C8C1im][PF6] mass fraction in the binary mixtures of ILs (m3) as shown in Figure S1. The maximum percent p-xylene extraction was attained at a mass fraction of 0.7. This mass fraction of the ILs mixture was used as the basis for liquid−liquid extraction of propylbenzene, butylbenzene, or p-xylene from n-heptane. 3.2. Experimental Data. The measured equilibrium mole fractions for the n-heptane-rich phase and the IL-rich phase of n-heptane + propylbenzene, butylbenzene or p-xylene + [C8C1im][PF6] + [C2C1im][CH3SO4] at 313.2 K and a

IL-rich phase

x1

x2

x1

x2

Kx

S

1.000 0.977 0.965 0.954 0.943 0.916 0.890 0.865 0.842 0.798 0.758 0.721 0.687 0.656 0.627 0.599 0.575 0.552

0.000 0.023 0.035 0.046 0.057 0.084 0.110 0.135 0.158 0.202 0.242 0.279 0.313 0.344 0.373 0.401 0.425 0.448

0.011 0.012 0.012 0.012 0.011 0.011 0.011 0.010 0.010 0.010 0.009 0.009 0.008 0.008 0.008 0.007 0.007 0.007

0.000 0.017 0.025 0.032 0.039 0.055 0.070 0.084 0.096 0.119 0.138 0.154 0.167 0.177 0.184 0.189 0.195 0.200

0.72 0.71 0.69 0.67 0.66 0.64 0.62 0.61 0.59 0.57 0.55 0.53 0.51 0.49 0.47 0.46 0.45

59.59 58.34 57.05 55.74 54.39 53.01 51.60 50.16 48.69 47.19 45.65 44.09 42.49 40.86 39.21 37.52 35.80

a Standard uncertainties (u) are u(T) = 0.1 K, u(P) = 1 kPa, u(x) = 1.0 × 10−3, u(m) = 1.0 × 10−3.

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widely used for evaluating the feasibility of using a solvent in a liquid extraction process. The K value represents the ability of the solvent to extract propylbenzene, butylbenzene, or p-xylene from the n-heptane-rich phase. Furthermore, the mole fraction basis is used to present the LLE diagrams, whereas the mass fraction basis is recommended for the comparison of ILs solvents with conventional solvents.8,20 The mole fraction distribution ratio, Kx, is calculated from the LLE experimental data as follows:

Table 4. Experimental Equilibrium Data of Mole Fractions (xi), Distribution Coefficient (Kx), [C8C1im][PF6] Mass Fraction in the Binary Mixtures of ILs (m3) and Selectivity (S) for the System n-Heptane (1) + p-Xylene (2) + [C8C1im][PF6] (3) + [C2C1im][CH3SO4] (4) at m3 = 0.7 at T = 313.2 K and P = 101 kPaa n-heptane-rich phase

IL-rich phase

x1

x2

x1

x2

Kx

S

1.000 0.971 0.956 0.942 0.929 0.896 0.865 0.836 0.809 0.759 0.714 0.673 0.636 0.603 0.573 0.545 0.519 0.496

0.000 0.029 0.044 0.058 0.071 0.104 0.135 0.164 0.191 0.241 0.286 0.327 0.364 0.397 0.427 0.455 0.481 0.504

0.011 0.011 0.011 0.011 0.011 0.010 0.010 0.009 0.009 0.008 0.008 0.007 0.007 0.007 0.006 0.006 0.006 0.005

0.000 0.021 0.031 0.040 0.049 0.070 0.089 0.106 0.121 0.149 0.173 0.193 0.209 0.223 0.234 0.242 0.251 0.258

0.72 0.71 0.70 0.68 0.67 0.66 0.64 0.63 0.62 0.60 0.59 0.58 0.56 0.55 0.53 0.52 0.51

61.32 60.59 59.84 59.09 58.32 57.55 56.76 55.96 55.15 54.33 53.50 52.66 51.81 50.95 50.07 49.19 48.29

Kx =

x 2II x 2I

xI2

(1)

xII2

where and are the mole fractions of propylbenzene, butylbenzene, or p-xylene in the n-heptane-rich phase and in the IL-rich phase, respectively, while the mass fraction distribution ratio, Kw, is calculated using Kw =

w2II w2I

(2)

where w is the corresponding mass fraction. On the other hand, the S value represents the effectiveness of the extraction and is calculated by S=

x 2IIx1I x 2Ix1II

(3)

where xI1 and xII1 are the mole fractions of n-heptane in the nheptane-rich phase and in the IL-rich phase, respectively. The distribution ratio and selectivity values are listed in Tables 2−4 for the three systems. The relationship between Kx and the alkylbenzenes mole fraction in the solvent-rich phase (x2) is plotted in Figure 1 where the Kx values decreased with x2 in the solvent-rich phase. The distribution ratio of the alkylbenzenes as a function of x 2 follows the trend: butylbenzene < propylbenzene < p-xylene. A comparison of Kx values for the system n-heptane + p-xylene + [C8C 1im][PF6] + [C2C1im][CH3SO4] with previous studies using

a Standard uncertainties (u) are u(T) = 0.1 K, u(P) = 1 kPa, u(x) = 1.0 × 10−3, u(m) = 1.0 × 10−3.

in Figure S2 as ternary diagrams. The solubility of n-heptane in the IL-rich phase is very small, (≤0.013) whereas there is no solubility of ILs in n-heptane-rich phase as shown in the diagrams. 3.3. Distribution Ratio and Selectivity. The distribution ratio (Kx or Kw) and the selectivity (S) were calculated to analyze and evaluate the use of mixed ILs as solvents in extraction of aromatic from aliphatic. These parameters are

Figure 1. Measured molar distribution coefficient (Kx) against aromatic mole fraction in the solvent rich phase (x2) at 313.2 K for the system: nheptane (1) + aromatic (2) + [C8C1im][PF6] (3) + [C2C1im][CH3SO4] (4) at m3 = 0.7: ●, propylbenzene; ○, butylbenzene; and ▼, p-xylene. C



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Figure 2. (a) Comparison of measured molar distribution coefficient (Kx) against aromatic mole fraction in the solvent-rich phase (x2) at 313.2 K with literature for the system: n-heptane (1) + p-xylene (2) + solvent; ▼, this work using mixed [C8C1im][PF6] (3) + [C2C1im][CH3SO4] (4) at m3 = 0.7; ●, sulfolane;5 ■, mixed [4empy][Tf2N] (3) + [C2C1im][DCA] (4);39 and ⧫, [BPy][NO3] (3).51 (b) Comparison of measured mass distribution coefficient (Kw) against aromatic mass fraction in the solvent rich phase (w2) at 313.2 K with literature for the system: n-heptane (1) + p-xylene (2) + solvent; ▽, this work using mixed [C8C1im][PF6] (3) + [C2C1im][CH3SO4] (4) at m3 = 0.7; ○, sulfolane;5 and □, mixed [4empy][Tf2N] (3) + [C2C1im][DCA] (4).39

sulfolane,5 other mixed ILs (n-heptane + p-xylene + [4empy][Tf2N] + [C2C1im] [DCA])39 and pure IL ([n-heptane + pxylene + [BPy][NO3 ]),51 as solvents, is depicted in Figure 2. The figure illustrates that binary mixture of [C8C1im][PF6] + [C2C1im][CH3SO4] ILs used in this work (with 0.7 mass fraction of [C8C1im][PF6]) led to a higher mole-based distribution ratio than the other solvents. Moreover, in the case of mass-based distribution ratio [C8C1im][PF6] + [C2C

1im][CH3SO4] ILs solvent shows comparable Kw values to sulfolane while it is higher than the [4empy][Tf2N] + [C2C 1im][DCA] mixed solvent (Figure 2). The selectivity of the binary mixture of [C8C1im][PF6] + [C2C1im][CH3SO4] ILs decreases as the propylbenzene, butylbenzene, or p-xylene mole fraction in the solvent-rich phase x2 increases as it is illustrated in Figure 3. In addition,

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Figure 3. Measured solvent selectivity (S) against aromatic mole fraction in the solvent-rich phase (x2) at 313.2 K for the system: n-heptane (1) + aromatic (2) + [C8C1im][PF6] (3) + [C2C1im][CH3SO4] (4) at m3 = 0.7: ●, propylbenzene; ○, butylbenzene; and ▼, p-xylene.

Figure 4. Comparison of measured solvent selectivity (S) against aromatic mole fraction in the solvent-rich phase (x2) at 313.2 K with literature for the system: n-heptane (1) + p-xylene (2) + solvent; ▼, this work using mixed [C8C1im][PF6] (3) + [C2C1im][CH3SO4] (4) at m3 = 0.7; ●, sulfolane;5 ■, mixed [4empy][Tf2N] (3) + [C2C1im][DCA] (4);39 and ⧫, [BPy][NO3] (3).51

the S values versus x2 decrease as the chain length increases where the selectivity of p-xylene being the highest. Moreover, the selectivity of the pseudoternary system n-heptane + pxylene + [C8C1im][PF6] + [C2C1im][CH3SO4] is higher than those of sulfolane and [4empy][Tf2N] + [C2C1im][DCA] as shown in Figure 4. 3.4. LLE Correlation by the NRTL Model. The experimental data were correlated using the nonrandom twoliquid (NRTL) model proposed by Renon and Prausnitz48,49 through the Sorensen’s iterative computer program.52 In the NRTL model, the excess Gibbs energy of mixing (GE) is

GE = RT

n

3

∑ xi

∑ j = 1 τjiGjixj

i=1

where τij =

gij − gjj RT

n

∑k = 1 Gkixk =

aij T

(5)

, Gij = exp (−αij τij), R is the gas

constant, T is the absolute temperature, g is the energy of interaction for each binary pair of compounds, G is the binary interaction parameter, τ is the adjustable parameter, and α is the nonrandomness parameter. The binary interaction parameters aij and aji were calculated, and the nonrandomness parameter (αij) was set to 0.2. E



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Table 5. NRTL Interaction Parameters aij, aji, and αij and Root Mean Square Deviation (rmsd) for Three Systems: n-Heptane (1) + Aromatic (2) + [C8C1im][PF6] (3) + [C2C1im][CH3SO4] (4) at T = 313.2 K and P = 101 kPa NRTL i n-heptane n-heptane propylbenzene n-heptane n-heptane butylbenzene n-heptane n-heptane p-xylene

aij

aji

α

rmsd

−132.11 1704.30 1584.90 −42.58 1705.70 1432.60 −199.87 1696.20 1559.70

588.24 954.84 −185.15 801.44 914.83 −17.45 878.30 936.84 −158.57

0.2

0.1772

0.2

0.1374

0.2

0.1485

j propylbenzene [C8C1im][PF6] [C8C1im][PF6] butylbenzene [C8C1im][PF6] [C8C1im][PF6] p-xylene [C8C1im][PF6] [C8C1im][PF6]

(3) + [C2C1im][CH3SO4] (4) (3) + [C2C1im][CH3SO4] (4) (3) + [C2C1im][CH3SO4] (4) (3) + [C2C1im][CH3SO4] (4) (3) + [C2C1im][CH3SO4] (4) (3) + [C2C1im][CH3SO4] (4)

The parameters and the root-mean-square deviation (RMSD) for the systems under study are presented in Table 5. The root-mean-square is defined by 1/2 l o o (xijk ,exp − xijk ,cal)2 | o o o o RMSD = 100m } ∑∑∑ o o o o 6n o k j i o n ~

Experimental equilibrium data of heptane (1) + p-xylene (2) + [C8C1im][PF6] (3) + [C2C1im][CH3SO4] (4) at 313.2 K as a function of [C8C1im][PF6] mole fraction in the mixed IL solvent; percentage extraction of p-xylene against mass fraction of [C C2C1im][PF6] in [C2C1im][CH3SO4] + [C2C1im][ PF6] mixed solvent at 313.2 K; experimental and predicted LLE data at 313.2 K for systems under study (PDF)

(6)

■

where n is the number of tie lines, i represents the component, j represents the phase, and k represents the tie lines. The experimental and the calculated tie lines plotted in Figure S2 illustrate that the NRTL model predicts the experimental data accurately.

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

4. CONCLUSIONS A binary mixture of [C8C1im][PF6] and [C2C1im][CH3SO4] has been used as a solvent to extract propylbenzene, butylbenzene, or p-xylene from n-heptane at at 313.2 K and a pressure of 101.3 kPa. The screening procedure determined the best composition of the binary mixture to be used afterward as the basis for all LLE experiments. Liquid−liquid equilibria experimental data were obtained for the three mixtures, and the distribution ratio along with the selectivity were calculated from these LLE data. Moreover, extractive properties were utilized to analyze and evaluate the use of mixed ILs as solvents in extraction of aromatic from aliphatic. The use of the current binary mixture of ILs provided a higher mole-based distribution ratio than sulfolane, a pure IL, and a mixture of ILs used for the extraction of p-xylene from n -heptane. In addition, the use of [C8C1im][PF6] and [C2C1im][CH3SO4] mixture contributed to a comparable mass-based distribution ratio to that of sulfolane and to a higher distribution ratio than the others involving ILs. Furthermore, the [C8C1im][PF 6] and [C2C1im][CH3SO4] mixture led to a higher selectivity than all the other solvents including sulfolane. Thus, the use of [C8C1im][PF6] and [C2C 1im][CH3SO4] binary mixture would be a potential candidate to extract aromatics from alphatic hydrocarbons based on its mole-based distribution ratio, mass-based distribution ratio, and selectivity. The NRTL model was utilized to adequately assess the experimental LLE data. The effect of the binary mixture composition on the distribution ratio of alkylbenzenes and solvent selectivity was investigated.

■

Mohammad S. AlTuwaim: 0000-0002-9638-8710 Adel S. Al-Jimaz: 0000-0002-1205-4968 Notes

The authors declare no competing financial interest.

■

REFERENCES

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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.8b01100. F



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