Ternary (liquid–liquid) equilibria of nitrate based ionic liquid + alkane + benzene at 298.15 K: Experiments and correlation

doi:10.1016/j.fluid.2012.12.025

Fluid Phase Equilibria

Volume 341, 15 March 2013, Pages 35-41

https://doi.org/10.1016/j.fluid.2012.12.025 Get rights and content

Abstract

Liquid–liquid equilibria (LLE) were determined for the ternary systems of ionic liquid + alkane (hexane, heptane or octane) + benzene at T = 298.15 K and atmospheric pressure. 1-Butyl 3-methylimidazolium nitrate [Bmim][NO₃] or 1-methyl 3-octylimidazolium nitrate [Omim][NO₃] were used as ionic liquid. The selectivities values for the ternary systems with [Bmim][NO₃] are higher than [Omim][NO₃]. The selectivities values show that [Bmim][NO₃] is more suitable solvent for benzene extraction than [Omim][NO₃]. The reliability of the LLE data was tested using Othmer–Tobias and Hand equations. The experimental data was correlated using the NRTL thermodynamic model. The results show the NRTL model can correlate the experimental data with good accuracy.

Highlights

► The extraction of benzene from hexane, heptane or octane was studied using ionic liquid. ► The ionic liquids [Bmim][NO₃] and [Omim][NO₃] were used. ► The selectivities values for the ternary systems with [Bmim][NO₃] are higher than [Omim][NO₃]. ► [Bmim][NO₃] is more suitable solvent for extraction of benzene than [Omim][NO₃]. ► The NRTL model were used for correlation of the experimental data.

Introduction

Extraction of aromatic from alkane is a major process in the oil refineries. This process cannot be made through distillation process because of the presence of the azeotropic points in these systems. Liquid extraction is the common process for separation of these compounds and the typical solvent are polar component such as sulfolane, N-methylpyrrolidone (NMP), N-formylmorpholine (NFM) and ethylene glycol [1]. These solvents are toxic, flammable and volatile those generate different problems in process. Ionic liquids (ILs) are a good alternative for these solvents. These non-flammable solvents have negligible vapor pressure, low melting point, and high solubility for polar and nonpolar substances [2]. The extractions of benzene from alkane using ILs have been studied by many researchers in last decades [3], [4], [5], [6], [7], [8], [9], [10], [11]. Recently, Pereiro et al. has been reviewed the application of ILs in separation of azeotropic mixtures [12]. This research is the continuation of our previous work on the extraction of aromatic from their mixtures with alkane and ILs [13], [14]. In the present work, the liquid–liquid equilibria (LLE) data for the ternary systems of benzene + alkane (hexane or heptane or octane) + IL (1-butyl 3-methylimidazolium nitrate [Bmim][NO₃] or 1-methyl 3-octylimidazolium nitrate [Omim][NO₃]) were determined at 298.15 K. These ILs are halogen free and thus more environment friendly [15]. The experimental data for these ILs have not been reported in the literature. The reliability of the experimental data was tested by Othmer and Tobias [16] and Hand [17] equations. The non random two liquid (NRTL) activity coefficient model [18] was used to correlate the experimental data for the ternary systems.

Section snippets

Materials and methods

The suppliers and the purities of the chemicals are given in Table 1.

[Bmim][NO₃] and [Omim][NO₃] were synthesized in our laboratory from [Bmim][Cl] or [Omim][Cl] according to the procedure in literature [19]. [Bmim][Cl] or [Omim][Cl] were prepared according to the method described in the literature [20], [21]. The detail description of the procedure is available in our previous work [2], [13]. The structure of the synthesized IL was checked with nuclear magnetic resonance (NMR) spectroscopy.

Experimental data

The experimental data for the ternary systems of [Bmim][NO₃] (1) + hexane (2) + benzene (3), [Bmim][NO₃] (1) + heptane (2) + benzene (3), [Bmim][NO₃] (1) + octane (2) + benzene (3), [Omim][NO₃] (1) + hexane (2) + benzene (3), [Omim][NO₃] (1) + heptane (2) + benzene (3) and [Omim][NO₃] (1) + octane (2) + benzene (3) were determined. The experimental data are reported in Table 2, Table 3.

In these tables, the benzene distribution coefficient (β) and the selectivity were calculated according to the following equations: $β = x_{3}$

Conclusion

The potential of the ILs [Bmim][NO₃] and [Omim][NO₃] for extraction of benzene from alkane (hexane, heptane or octane) was examined. The experimental data for the ternary systems of IL + alkane + benzene were reported at 298.15 K and atmospheric pressure. The reliability of the experimental was confirmed by the Othmer–Tobias and Hand equations. The selectivity and distribution coefficient values were calculated. The selectivity values for the systems with [Bmim][NO₃] are higher than the systems with

References (24)

B. Mokhtarani et al.
J. Chem. Thermodyn.
(2009)
T.M. Letcher et al.
J. Chem. Thermodyn.
(2003)
T.M. Letcher et al.
J. Chem. Thermodyn.
(2005)
G.W. Meindersma et al.
Fluid Phase Equilib.
(2006)
R.M. Maduro et al.
Fluid Phase Equilib.
(2008)
U. Domanska et al.
Fluid Phase Equilib.
(2007)
E.J. González et al.
J. Chem. Thermodyn.
(2009)
E.J. González et al.
J. Chem. Thermodyn.
(2010)
A.B. Pereiro et al.
J. Chem. Thermodyn.
(2012)
M.R. Heidari et al.
J. Chem. Thermodyn.
(2012)

A.A. Strechan et al.

Thermochim. Acta

(2008)

A. Marciniak et al.

J. Chem. Thermodyn.

(2012)

Cited by (40)

Liquid-liquid equilibria of Aliquat 336 + green solvents + water for replacement of petroleum-based solvents: Intramolecular analysis and thermodynamic behavior
2024, Journal of Industrial and Engineering Chemistry
The investigations of Aliquat 336 dissolved in green solvents: corn oil, rice bran oil, and sunflower oil, compared with toluene and kerosene to replace the petroleum-based solvents. Liquid-liquid equilibria of adjusted pH water + Aliquat 336 + solvents were evaluated at 303.2 K, 313.2 K, and 323.2 K and 0.1 MPa. The mass fraction of Aliquat 336 was carried out in the range 25–75 wt%. The performance of solvents was explored through the distribution coefficient (D) and selectivity factor (S). The Van’t Hoff, Jouybran – Acree model, modified Jouybran - Acree - Van’t Hoff, and nonrandom two liquid (NRTL) models were investigated. The mixed Gibbs free energy topology (G^M(L)) analysis was applied to verify the accuracy of binary interaction parameters from the model. It is seen that corn oil at 303.2 K proved to be the most efficient solvent to dilute Aliquat 336. As verified by the good, correlated root mean square deviations and the G^M(L) analysis, the NRTL model fits in well with the tie-line experimental data. The density functional theory reveals the stronger molecular interaction between Aliquat 336 and green oils than petroleum-based solvents. In line with the properties effect, the dielectric constants and viscosity are seen to further support the experimental results.
The extraction and the removal of Cd(II) using polymer inclusion membrane containing symmetric room temperature ionic liquid as ion carrier
2023, Journal of Environmental Chemical Engineering
Since cadmium is a hazardous material for environment, various techniques have been developed for safe removal of cadmium. Among these techniques, ionic polymer inclusion membranes (IPIMs) have a higher membrane structural stability that can be used to separate and recover cadmium ions with a higher selectivity. Also, the ion transport capacity of IPIMs can be further increased by selecting suitable ion carriers and plasticizers. In this study, preparation of IPIMs was accomplished by selecting newly synthesized symmetric and having different alkyl chain room temperature ionic liquids as ion carriers for selective the separation of cadmium from iodide-containing acidic solutions. The highest mass transport was determined as 0.958 μmol s⁻¹ cm⁻² from 25 mg L⁻¹ and 2.02 μmol s⁻¹ m⁻² from 75 mg L⁻¹ Cd(II) solution, respectively, when using the optimized IPIM containing 24.97% (w/w) 2-nitrophenyl octyl ether as plasticizer and 35.12% (w/w) 1,3-decyl-1 H-imidazol-3-ium bromide as carrier. The mass transport of cadmium was determined as 0.567 μmol s⁻¹ m⁻² in the presence of Cr³⁺, Fe²⁺, Co²⁺, Ni²⁺ and Zn²⁺. Surface analyses were explored by scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX), while the structural analysis was carried on by Fourier infrared spectroscopy (FTIR) before/after Cd transport experiments.
The mutual solubility of organic-liquid membrane and aqueous phases at different water pH for the stability of SLM using Aliquat 336 as an ionic-liquid extractant
2019, Journal of Molecular Liquids
Regarding supported liquid membrane (SLM), the mutual solubility of both the organic and aqueous phases has an influence on its stability. Investigation into causes of mutual solubility is very important to prevent instability of the system. This work focuses on the influence of water pH as regards the solubility and stability of SLM. For the organic phase, ionic-liquid extractant viz. Aliquat 336, combining with various organic solvents, was used. As for the aqueous phase, acidic, neutral and basic water was prepared. The solubility of the liquid-liquid ternary systems (adjusted pH water + Aliquat 336 + organic solvents) was carried out at T = 303.2 K and atmospheric pressure. Tie-line data of the ternary systems were also determined. Good correlation of tie-line data from the NRTL model and experiments was confirmed and validated by the root-mean square deviation values which were <2%. For SLM stability, response surface methodology combined with Box-Behnken design was applied to obtain optimal conditions for platinum extraction and stripping. The stability of the system was observed under the different feed pH and optimal conditions.
Liquid–liquid extraction-based process concepts for recovery of carboxylic acids from aqueous streams evaluated for dilute streams
2018, Chemical Engineering Research and Design
In this manuscript carboxylic acid extraction processes are reviewed and compared on energy efficiency, especially in situations with very low carboxylic acid concentrations. Production of carboxylic acids by fermentation rather than petrochemical routes aims at reducing dependency on petroleum resources. Wastewater streams are potential carbon sources for fermentation. However, their limited carbon content results in low carboxylic acid concentrations (∼1 wt%) that render separation of waste-derived carboxylic acids challenging. This necessitates implementation of cost-effective separation concepts. The incentive to review liquid–liquid extraction (LLX)-based processes for carboxylic acids was to evaluate their applicability to low carboxylic acid concentrations. Although a thorough study of recent solvent developments was beyond the scope of this work, a brief discussion on their families supported the LLX-based process developments that were assessed in terms of energy demand by simulating their thermal unit operations with Aspen Plus. They were simulated both under their reported conditions and with their initial concentration set to 1 wt%. A process proposed by Urbas (1983) that makes use of CO₂, CO₂-switchable solvents and low-boiling organic solvents outperformed the others for low carboxylic acid feed concentrations. With a heating duty of about 36 MJ/kg_product, it could recover both volatile and non-volatile carboxylic acids from fermentation broths with 1 wt% initial carboxylic acid loading. Future developments in the field may be based on this process design, but with more environmentally friendly solvents such as the bio-based furan derivatives.
Experimental measurement and thermodynamic modelling of liquid-liquid equilibria for the separation of 1,2-dichloroethane from cyclohexane using various extractants
2018, Journal of Molecular Liquids
Citation Excerpt :
Essentially, this means that the lower the concentration of 1,2-dichloroethane is, the higher separation efficiency would be obtained. Analogous findings have also been reported elsewhere [17,18,35]. Based on the obtained interaction parameters of NRTL model, a conceptual countercurrent extraction process for separating 1,2-dichloroethane from cyclohexane can be designed, as illustrated in Fig. 15.
Experimental liquid-liquid equilibrium (LLE) data for the cyclohexane + 1.2-dichloroethane + solvent ternary systems were determined at T = 313.15 K and p = 101.3 kPa, where the extracting agents are sulfolane, dimethyl sulfoxide, 1,4-butanediol and N,N-dimethylmethanamide. According to the experimental values, solute distribution coefficient and selectivity were obtained to estimate the feasibility of the utilization of the selected solvents for extraction of 1,2-dichloroethane from cyclohexane. The reliability and consistency of the experimentally measured LLE results were then corroborated by employing the Hand and Bachman equations. In addition, the experimental tie-line compositions were successfully regressed with the universal quasi-chemical (UNIQUAC) and nonrandom two-liquid (NRTL) thermodynamic models, and the values of relevant binary energy parameters were reported as well. Further, the solvent cost analysis indicated that dimethyl sulfoxide was a desirable extractant for separation of 1,2-dichloroethane from cyclohexane.
The experimental investigations on viscosity, surface tension, interfacial tension and solubility of the binary and ternary systems for tributyl phosphate (TBP) extractant in various organic solvents with water: Thermodynamic NRTL model and molecular interaction approach
2018, Journal of Molecular Liquids
In order to provide a database for supporting stability in the separation processes, the physical properties of the mixing solutions between extractant and organic solvents, with/without water, were investigated at temperature 303.2 K and pressure 0.1 MPa. The extractant of tributyl phosphate (TBP) as well as the following organic solvents i.e. cyclohexane, n-heptane, kerosene and toluene were selected for use in this work. Further, the physical properties of the mixing solutions such as viscosity, surface tension, interfacial tension and solubility with water were observed when the percent weights of the extractant increased. The principle of intermolecular attraction between the molecules in the mixing solutions was considered in order to explain the tendencies of results. Tie-line data were determined for ascertaining the solubility of extractant in the organic and aqueous phases. A thermodynamic NRTL model was also evaluated and its data compared with the experimental results. Consequently, good correlations were displayed by the root-mean square deviation (rmsd) at values about 2%. Finally, for understanding the solvation of solute and solvent, the molecular interaction behaviors of the molecules in the mixing solutions were examined by spectroscopic analyses.

View all citing articles on Scopus

View full text

Ternary (liquid–liquid) equilibria of nitrate based ionic liquid + alkane + benzene at 298.15 K: Experiments and correlation

Abstract

Highlights

Introduction

Section snippets

Materials and methods

Experimental data

Conclusion

J. Chem. Thermodyn.

J. Chem. Thermodyn.

J. Chem. Thermodyn.

Fluid Phase Equilib.

Fluid Phase Equilib.

Fluid Phase Equilib.

J. Chem. Thermodyn.

J. Chem. Thermodyn.

J. Chem. Thermodyn.

J. Chem. Thermodyn.

Thermochim. Acta

J. Chem. Thermodyn.