LiquidâLiquid Equilibria for the Ternary Systems Dodecane +

Article pubs.acs.org/jced

Liquid−Liquid Equilibria for the Ternary Systems Dodecane + Toluene or Thiophene or Pyridine + 1‑Ethyl-3-methylimidazolium Methyl Sulfate Abdelaziz Chikh Baelhadj†,‡ and Fabrice Mutelet*,‡ †

Laboratoire de Thermodynamique et de Modélisation Moléculaire, Faculté de Chimie, USTHB, BP 32 El-Alia 16111 Bab-Ezzouar, Alger, Algérie ‡ Laboratoire Réactions et Génie des Procédés (UMR CNRS 7274), Ecole Nationale Supérieure des Industries Chimiques, Université de Lorraine, 1 rue Grandville, 54000 Nancy, France ABSTRACT: Liquid−liquid equilibria for the three ternary systems (dodecane + toluene + 1-ethyl-3-methylimidazolium methyl sulfate ([EMIM][MeSO4])), (dodecane + thiophene + [EMIM][MeSO4]) and (dodecane + pyridine + [EMIM][MeSO4]) were measured at 298.15 K and at atmospheric pressure. Experimental data were used to calculate the distribution coefficient and selectivity values. Results indicate that [EMIM][MeSO4] is a potential solvent for the extraction of pyridine from n-dodecane. It was found that NTRL and UNIQUAC models can used to represent with good accuracy ternary systems containing [EMIM][MeSO4]. Then, we have shown that [EMIM][MeSO4] can be used as solvent for the extraction of pyridine from a synthetic mixture.

1. INTRODUCTION Liquid−liquid extraction is a widely used process in the field of chemical engineering and often seen as a process that responds best to the problem related to separation and purification. However, this process needs continuous and sustainable improvements in order to satisfy the economic and environmental requirements. Indeed, environmental protection laws are more and more drastic and the scientific community has to propose new technologies with solvents more environmentally friendly such as ionic liquids or deep eutectic solvents. Since 2009, European Union and Environmental Protection Agency (EPA) have imposed to the petroleum industry to produce diesel fuel containing less than 10 ppm sulfur.1,2 To respond to these exigencies, industries have to design new processes or enhance the existing ones. To do so, a good knowledge of physicochemical properties of the key systems of the process is required. Ionic liquids are regarded as green compounds and their use in processes of extraction could be an alternative to the problems mentioned above.3−20 The main advantages of ILs are their thermal stability, their solvating properties for numerous materials, their wide liquid range, and their negligible vapor pressure. Nevertheless, their use in processes may be compromised due to their high viscosity, their poor biodegradability and their toxicity. One of the main objective is then to find the IL structure appropriate to the demands of the process. Recent works show the efficiency of imidazolium-based ILs21 as an extracting solvent for aromatic, sulfur, or nitrogen compounds from aliphatic media.22−28 In the field of liquid− © XXXX American Chemical Society

liquid extraction, it is well established that the best performances are obtained using ILs with moderate chain length. Indeed, an increase of the alkyl chain on the cation increases the distribution ratios but decreases the selectivity.29,30 Moreover, Shah et al. have demonstrated that the separation of thiophene or pyridine from cyclohexane with [MMIM]based ILs requires large quantity of the ionic liquids.31 In their review, Canales et al.32 have found few ILs with higher selectivities than sulfolane for the extraction of aromatics from aliphatic. Numerous papers had focused on systems containing1-ethyl-3-methylimidazolium methyl sulfate ([EMIM][MeSO4]), sulfur, or nitrogen compounds and aliphatics. Among others, Anantharaj and Balaji have shown that ternary systems {[EMIM][EtSO4] or [EMIM][MeSO3] + thiophene or benzothiophene + n-hexadecane} present large selectivity values (from 30 to 80).2 Distribution coefficients obtained with [EMIM][MeSO3] that are higher than unity at low solute concentration proved that this IL may be used for the desulfurization of diesel. The effect of ILs structure and alkane chain length on the equilibrium behavior was also studied.33 The influence of experimental conditions was evaluated on the extraction of propylbenzene from dodecane or tetradecane using [MMIM][EtSO4] or [EMIM][MeSO3]. It appears that the solubility of ILs in the alkane-rich phase is not affected by a change of temperature and/or concentration of propylbenzene. However, Received: May 30, 2016 Accepted: April 27, 2017

A

DOI: 10.1021/acs.jced.6b00437 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

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Table 1. Characteristics of the Studied Substances compound name

chemical formula

molar mass/g mol−1

purity (%)

CAS registry number

supplier

toluene thiophene pyridine n-dodecane 1-ethyl-3-methylimidazolium methyl sulfate

C7H8 C4H4S C5H5N C12H26 C7H14N2O4S

92.14 84.14 79.10 170.33 222.26

99 99.8 99.8 >99 99

108-88-3 110-02-1 110-86-1 112-40-3 516474-01-4

Sigma-Aldrich Sigma-Aldrich Sigma-Aldrich Sigma-Aldrich Iolitec

2.2. Apparatus and Procedure. The apparatus and the procedure used for the liquid−liquid equilibria measurements were described in our previous work.51 Briefly, measurements were carried out using jacketed glass cells at the temperature T = 298.15 K under atmospheric pressure. The temperature inside the cell was maintained constant using thermostatic bath (model Polystat 37 from Fisher Scientific). During the measurements, the working temperature inside the cell was controlled by a platinum resistance thermometer Pt-100 with an uncertainty of 0.1 K. The ternary mixtures with compositions inside the system immiscibility region were weighted by a METTLER analytical balance with a accuracy of 0.0001 g. To thoroughly mix the prepared samples, the mixtures were stirred for at least 4 h by using a magnetic stirrer at speed of 450 rpm to achieve equilibrium. Afterward, the mixtures were left to settle for at least 14 h in order to ensure the two phases were entirely separated. After the phase equilibrium state of the ternary system was reached, samples of both hydrocarbon-rich phase and ionic liquid-rich phase were taken from the cell using a syringe. The compositions of each phase were determined by gas chromatography (GC). The operating conditions of the GC apparatus are given in Table 2. The capillary column was

both parameters have some effect on alkane solubility in the ionic solvent-rich phase. Selectivity values obtained on these four separation problems are quite large (from 30 to 120) but distribution ratio values are small (from 0.18 to 0.41). Recent study on tricyanomethanide-based ILs have shown that selectivity values of 1-butyl-4-methylpyridinium tricyanomethanide vary from 10 to 40 and the distribution ratios are higher than classical solvents.34 Kedra−Krolik et al. evaluated the performance of three dialkylimidazolium ILs for the desulfurization and denitrogenation of synthetic gasoline and diesel. Desulfurization in three steps leads to a reduction of 94% sulfur compounds content.35 Although there are a large number of studies performed on this class of ionic liquids and their application in desulfurization and denitrogenation of gasoline oil,36−55 their LLE data are still lacking. In this work, LLE for three ternary systems, namely, (dodecane + toluene +1-ethyl-3-methylimidazolium methyl sulfate), (dodecane + thiophene +1-ethyl-3-methylimidazolium methyl sulfate), and (dodecane + pyridine +1-ethyl-3methylimidazolium methyl sulfate) are measured at 298.15 K and at atmospheric pressure. The distribution coefficient and selectivity values obtained from experimental data are also reported. Then, the experimental results are correlated using Nonrandom Two-Liquid equation (NTRL) and UNIversal QUAsiChemical (UNIQUAC) activity coefficient models.

Table 2. Operating Conditions of Gas Chromatography Apparatus

2. EXPERIMENTAL SECTION 2.1. Chemicals. Toluene, thiophene, pyridine, and ndodecane were provided by Sigma-Aldrich with a purity of 99%, 99.8%, 99.8%, and >99%, respectively. 1-Ethyl-3methylimidazolium methyl sulfate ([EMIM][MeSO4]) with a purity of 99% was purchased from Iolitec. All chemicals were used without further purification. The chemicals used in this work, their chemical formulas, and their molecular weights are summarized in Table 1. Figure 1 shows the molecular structure of the ionic liquid. The water content measured by the Karl Fischer volumetric titration (TIM550 - Titralab) was found to be 178 ppm for 1,3-dimethylimidazolium methylsulfate.

capillary column carrier gas carrier gas pressure column oven program injector temperature detector type detector temperature

SPBTM-5 30 m × 0.25 mm × 0.25 μm (Supelco) Helium 100 kPa 80 °C during 4 min; 80 to 110 (5 °C·min−1) during 6 min 250 °C FID 250 °C

protected with a precolumn in order to avoid the IL reaching the column. 3-Pentanone was chosen as internal standard for the GC analysis. The Galaxy software was used to obtain the peak areas of the thiophene or pyridine, n-dodecane, and 3pentanone. All samples were injected at least three times and the average value of peak areas was used to determine the molar fraction of toluene, thiophene, pyridine, or n-dodecane. The ionic liquid content in each phase is then deduced from molar fraction of the other components. The standard uncertainty in the determination of mole fraction compositions is 0.005 for compositions of both phases.

3. RESULTS AND DISCUSSION 3.1. Experimental LLE Data. The obtained LLE results at 298.15 K for ternary systems: {dodecane + toluene + [EMIM][MeSO 4 ]},{dodecane + thiophene + [EMIM][MeSO4]}, and {dodecane + pyridine + [EMIM][MeSO4]} are presented in Table 3. LLE diagrams are shown in Figures 2

Figure 1. Chemical structure of the aromatic compounds and ionic liquid. B



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Table 3. Experimental LLE Data (Mole Fraction x), Solute Mass Distribution Coefficient (β), and Selectivity (S) for Dodecane (1) + Toluene or Thiophene or Pyridine (2) + [EMIM][MeSO4] (3) at 298.15 K and P = 0.1 MPaa hydrocarbon-rich phase (HC) x1HC 0.820 0.711 0.695 0.595 0.559 0.523 0.492 0.439 0.415 0.395 0.860 0.738 0.663 0.552 0.497 0.422 0.367 0.314 0.307 0.288 0.954 0.917 0.887 0.828 0.730 0.703 0.694 0.654 0.650 0.637 a

x2HC

x3

HC

ionic liquid-rich phase (LI) x1LI

x2LI

x3LI

β

Dodecane (1) + Toluene (2) + [EMIM][MeSO4] (3) 0.152 0.028 0.014 0.034 0.952 0.17 0.250 0.039 0.011 0.049 0.940 0.14 0.272 0.033 0.011 0.051 0.937 0.13 0.398 0.007 0.009 0.067 0.924 0.11 0.441 0.000 0.009 0.076 0.916 0.11 0.476 0.001 0.008 0.081 0.911 0.11 0.507 0.001 0.007 0.087 0.906 0.11 0.547 0.015 0.006 0.095 0.899 0.11 0.578 0.007 0.006 0.100 0.894 0.10 0.599 0.006 0.006 0.110 0.884 0.11 Dodecane (1) + Thiophene (2) + [EMIM][MeSO4] (3) 0.137 0.002 0.001 0.103 0.896 0.57 0.255 0.007 0.000 0.187 0.813 0.56 0.335 0.002 0.011 0.230 0.759 0.51 0.438 0.010 0.008 0.297 0.691 0.50 0.492 0.011 0.007 0.314 0.680 0.46 0.560 0.018 0.000 0.351 0.650 0.44 0.602 0.031 0.003 0.371 0.627 0.43 0.642 0.044 0.003 0.372 0.620 0.40 0.647 0.046 0.002 0.379 0.619 0.40 0.655 0.057 0.002 0.382 0.609 0.40 Dodecane (1) + Pyridine (2) + [EMIM][MeSO4] (3) 0.038 0.008 0.045 0.126 0.829 2.70 0.080 0.004 0.038 0.211 0.751 2.28 0.110 0.003 0.030 0.295 0.675 2.42 0.171 0.001 0.019 0.402 0.579 2.22 0.257 0.013 0.013 0.539 0.448 2.14 0.285 0.012 0.012 0.573 0.415 2.09 0.289 0.018 0.012 0.583 0.405 2.12 0.344 0.002 0.009 0.609 0.381 1.83 0.341 0.010 0.009 0.640 0.351 2.02 0.353 0.010 0.008 0.651 0.341 1.98

S 13.63 12.26 11.55 11.49 11.02 11.11 11.36 12.06 11.69 11.88

Figure 3. LLE for (dodecane + thiophene + [EMIM][MeSO4]) system at T = 298.15 K. Red circle, experimental points; --, UNIQUAC model; -.-, NRTL model.

646.63 42.17 44.14 48.07 80.74 91.12 105.61 112.78 68.79 63.64 78.45 101.02 120.35 123.30 123.46 122.39 145.28 155.25

Figure 4. LLE for (dodecane + pyridine + [EMIM][MeSO4]) system at T = 298.15 K. Red circle, experimental points; --, UNIQUAC model; -.-, NRTL model.

to 4. In order to check the reproducibility of the experimental results, the Othmer−Tobias56 and Bachman57 equations were applied. These two equations are respectively given by

u(T) = 0.1 K; u(x) = 0.005; and u(p) = 3 kPa.

⎛ 1 − x IL ⎞ ⎛ 1 − x HC ⎞ 3 1 ⎟ ⎜ ⎟ = + ln⎜ ln a b IL HC ⎝ x1 ⎠ ⎝ x3 ⎠

(1)

⎛ x IL ⎞ 2 ⎟ x 2 = a + b⎜ HC ⎝ x1 ⎠

(2)

where subscripts 1, 2, and 3 stand for dodecane, the solute (thiophene, toluene, or pyridine), and the ionic liquid, respectively. a and b are parameters to be regressed. Values of the latter as well as the coefficient of determination (R2) values are reported in Table 4. It can be noticed that R2 values are close to unity, which indicates a satisfactory reliability of the obtained data. The extraction efficiency can be evaluated through the distribution coefficient and the selectivity. Values of mass distribution coefficient D and selectivity S for the three solutes (toluene, thiophene, or pyridine) reported in Table 3 were calculated according to the eqs 3 and 4

Figure 2. LLE for (dodecane + toluene + [EMIM][MeSO4]) system at T = 298.15 K. Red circle, experimental points; --, UNIQUAC model; -.-, NRTL model.

C



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Table 4. Othmer−Tobias and Bachman Equation Parameters and their Coefficients of Determination (R2) Othmer-Tobias

Bachman

system

a

b

R2

a

b

R2

dodecane (1) + toluene (2) + [EMIM][MeSO4] (3) dodecane (1) + thiophene (2) +[EMIM][MeSO4] (3) dodecane (1) + pyridine (2) + [EMIM][MeSO4] (3)

0.536 0.599 0.942

−2.284 −0.867 1.207

0.948 0.948 0.972

0.321 0.204 0.5806

0.026 0.145 0.086

0.965 0.861 0.981

S=

Figure 6. Variation of solute distribution coefficient with its mole fraction in the hydrocarbon-rich phase for the three studied systems. Blue circle, {dodecane (1) + toluene (2) + [EMIM][MeSO4]}; orange circle, {dodecane (1) + thiophene (2) + [EMIM][MeSO4]}; gray circle, {dodecane (1) + pyridine (2) + [EMIM][MeSO4]}; black circle, {dodecane (1) + thiophene (2) + [C8mim][NTf2] (3)};32 yellow circle, {dodecane (1) + thiophene (2) + [hmmpy][Ntf2] (3)}.32

Table 5. UNIQUAC Geometrical Parameters for Studied Compounds compound

ri

qi

8.546230 3.922861 2.856961 2.999361 7.577430

7.096030 2.968061 2.140061 2.113061 6.028030

Di =

m

ln γi =

∑ j = 1 xjτjiGji m

∑k = 1 xkGki

m

+

∑ j=1

m ⎛ ∑k = 1 xkτkjGkj ⎞ ⎜ ⎟ τ − m ij m ∑k = 1 xkGkj ⎜⎝ ∑k = 1 xkGkj ⎟⎠

xjGij

(5) Δgij

gij − Δgjj

with Gij = exp(−αijτij) and τij = RT = RT . Here, Δgij is the energy parameter characterizing the interaction between component i and j. αij = αji = α. In this work, the nonrandomness parameter α is taken equal to 0.3. UNIQUAC:

wiIL wiHC

(4)

where w is the mass fraction of component i in HC and IL rich phases. HC and IL indicate the hydrocarbon-rich phase and the ionic liquid-rich phase, respectively. Subscripts 1 and 2 stand for dodecane and the solute, respectively. In order to obtain an efficient extraction, values of solute distribution coefficient have to be superior than 1. The values of D and S correspond to the three ternary systems studied in this work and data taken from the literature for {dodecane + thiophene + [C8mim][NTf2]}32 and {dodecane + thiophene+ [hmmpy][Ntf2]}32 are represented in Figures 5 and 6. Binary mixture {pyridine + [EMIM][MeSO4]} is completely miscible while {thiophene or toluene + [EMIM][MeSO4]} is partially miscible. The same behavior was found in our previous works with tricyanomethanide or thiocyanate-based ionic liquids. Therefore, it is not surprising that [EMIM][MeSO4] is an excellent medium for the extraction of pyridine. The extraction performance of this IL decreases with thiophene or toluene. These results are in good agreement with previous works.58,59 Figure 5 shows that toluene has a distribution coefficient less than 0.17. This value is of the same order of magnitude as D values obtained for the ternary system {[EMIM][MeSO4] + propylbenzene + dodecane}.36 These results indicate that methylsulfate-based ILs are not efficient for the extraction of aromatic compounds. Concerning thiophene distribution coefficients, their values vary from 0.4 to 0.57. At low concentration of thiophene, the distribution coefficient value obtained by Anantharaj and Balaji2 was around 1.30 in a mixture containing [EMIM][MeSO4] and n-hexadecane. Therefore, increasing the length of the hydrocarbon chain increases the solubility of thiophene in this ionic liquid. Indeed, it is well established that polar compound become less soluble when the hydrocarbon chain increases.30 Figures 5 and 6 show that the performance of [EMIM][MeSO4] for the extraction of thiophene from dodecane is quite similar than those obtained with [C8MIM][NTf2] or [hmmpy][Ntf2]. Finally, [EMIM][MeSO4] appears to be an excellent extraction media while pyridine distribution coefficients and selectivity are relatively high especially for low mole fractions (D ≈ 2.70 and S ≈ 60). 3.2. Data Correlation. The LLE data of the investigated ternary systems were correlated using the NTR)60 and the UNIQUAC model.61 NRTL:

Figure 5. Solute distribution coefficient against xHC 2 for the following ternary systems. Blue circle, {dodecane (1) + toluene (2) + [EMIM][MeSO4]}; orange circle {dodecane (1) + thiophene (2) + [EMIM][MeSO4]}; gray circle, {dodecane (1) + pyridine (2) + [EMIM][MeSO4]}; black circle, {dodecane (1) + thiophene (2) + [C8mim][NTf2] (3)};32 yellow circle, {dodecane (1) + thiophene (2) + [hmmpy][Ntf2] (3)}.32

dodecane toluene thiophene pyridine [EMIM][MeSO4]

D2 D1

(3) D



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Table 6. Values of Binary Parameters for the NRTL Equation for the Ternary Mixtures system

ij

Δgij (J mol−1)

Δgji (J mol−1)

rmsd

n-dodecane (1) + thiophene (2) + [EMIM][MeSO4] (3)

12 13 23 12 13 23 12 13 23

178 12372 6110 −1326 6208 16990 4770 8670 14872

5518 16140 948 4422 8994 4042 17890 5454 706

0.0077

n-dodecane (1) + toluene (2) + [EMIM][MeSO4] (3)

n-dodecane (1) + pyridine (2) + [EMIM][MeSO4] (3)

0.0046

0.0064

Table 7. Values of the Binary Parameters for the UNIQUAC Equation system

ij

Δuij (J mol−1)

Δuji (J mol−1)

rmsd

n-dodecane (1) + thiophene (2) + [EMIM][MeSO4] (3)

12 13 23 12 13 23 12 13 23

3022 685 −489 −300 988 2431 3056 4972 7122

−879 1668 2695 478 687 204 200 −870 −536

0.0057

n-dodecane (1) + toluene (2) + [EMIM][MeSO4] (3)

n-dodecane (1) + pyridine (2) + [EMIM][MeSO4] (3)

N

Fobj =

0.0066

0.0074

3

∑ ∑ {(xi HC,exp − xi HC,cal)2 + (xi IL,exp − xi IL,cal)2 } k=1 i=1

(9)

where N is the number experimental points, xiHC,exp and xiHC,cal are the experimental and calculated mole fractions, respectively. HC and LI stand for hydrocarbon-rich phase and ionic liquidriche phase, respectively. The binary interaction parameters and root mean-square deviation (rmsd) calculated using eq 10 are given in Tables 6 and 7, respectively. N

rmsd =

Figure 7. Solute extraction rates as a function of time. Blue diamond, toluene; red square, thiophene; green triangle, pyridine. C

ln γi = ln γi + ln γi ln γiC = ln

ϕi xi

+

R

⎡ ln γi = qi⎢1 − ln(∑ θτ j ji) − ⎢⎣ j R

Z

It can be noticed, through Figures 2 to 4, that experimental results are fairly well represented by both NRTL and UNIQUAC models. Indeed, the rmsd for both models varies mostly between 0.004 and 0.008. 3.3. Application of [EMIM][MeSO4] as Solvent for the Extraction of Toluene, Thiophene, Pyridine from nDodecane. The possible use of [EMIM][MeSO4] to extract such components from synthetic system was evaluated. A synthetic mixture containing 5, 6, 6.5 and 82.5% mole fraction of toluene, thiophene, pyridine, and dodecane was prepared. The variation of solute extraction rates as a function of time is shown in Figure 7. Most of the solute extraction takes place within first 10 min. After, solute extraction increases slowly until saturation was reached. Approximately 30%, 50%, and 90% for toluene, thiophene, and pyridine, respectively, may be extracted from n-dodecane. Therefore, [EMIM][MeSO4] seems to be a good media for the extraction of sulfur and nitrogen compounds. Temperature and ratio quantity of ndodecane/quantity of IL can be two adjustable parameters to increase the efficiency of the process.

∑ j

with li = 2 (ri − qi) − (ri − 1), θi =

∑ xjlj j

⎤ ⎥ ∑k θkτkj ⎥⎦

(7)

θτ j ji

qixi ∑ qixi

and ϕi =

6N

(10)

(6)

ϕi θi ⎛Z⎞ ⎜ ⎟q ln l + − i ⎝2⎠ i ϕ xi i

3

∑k = 1 ∑i = 1 {(xi HC,exp − xi HC,cal)2 + (xi IL,exp − xi IL,cal)2 }

(8) rx i i where ∑ xjrj

ri and qi are, respectively, the relative volume and surface area of the pure component i. θi and ϕi are the surface and volume fractions of component i. Z is the number of coordination. It is generally taken to be equal to 10. Details about calculation of ri and qi are reported elsewhere.62,63 Values of volume and surface compound parameters, ri and qi, summarized in Table 5 are taken from the literature.33,64 Binary interaction parameters for both thermodynamic models are determined by minimizing the function (eq 7) E



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4. CONCLUSION LLE for the ternary systems (dodecane + toluene + [EMIM][MeSO4]), (dodecane + thiophene + [EMIM][MeSO4]), and (dodecane + pyridine + [EMIM][MeSO4]) were determined at 298.15 K. The extraction efficiency was evaluated using the distribution coefficient and selectivity values corresponding to each solute. Results indicate that [EMIM][MeSO4] is a good solvent for denitrogenation. Desulfurization efficiency using [EMIM][MeSO4] as extractant media is still poor compared to other ILs. NRTL and UNIQUAC thermodynamic models are good tools for the representation of liquid−liquid equilibria of ternary systems containing [EMIM][MeSO4].

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Fabrice Mutelet: 0000-0001-5259-6991 Notes

The authors declare no competing financial interest.

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REFERENCES

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