Infinite dilution activity coefficient measurements of organic solutes in selected deep eutectic solvents by gas-liquid chromatography

Abstract

Many separation processes in the chemical and petrochemical industries are energy intensive, and unfortunately, involve a range of solvents that are environmentally harmful and destructive. Alternative, sustainable separation techniques are desired to replace these conventional methods used in the separation of azeotropic as well as close-boiling mixtures, with the intention of reducing energy costs and adverse impact on the environment.

In the present study, a new class of solvents called deep eutectic solvents (DESs) of Type III were investigated as alternatives to conventional solvents currently employed in separation processes. DESs are classified as ‘green’ solvents because of a range of favourable properties including lower cost, desirable solubility properties and reduced environmental impact (Abbott et al., 2003b; Smith et al., 2014). The infinite dilution activity coefficients (IDACs) values of 24 solutes – including alk-1-anes, alk-1-enes, alk-1-ynes, cycloalkanes, alkanols, alkylbenzenes, heterocyclics, esters, and ketones – were measured at 313.15, 323.15, 333.15 and 343.15 K by gas-liquid chromatography (GLC) in DESs. The four investigated DESs were as follows: 1) Tetramethylammonium chloride + Glycerol (DES1); 2) Tetramethylammonium chloride + Ethylene Glycerol (DES2); 3) Tetramethylammonium chloride + 1,6 Hexanediol (DES3); and 4) Tetrapropylammonium bromide + 1,6 Hexanediol (DES4).

This work focused on the performance of DESs as extractive solvents for selected azeotropic and close-boiling binary mixtures. The two key performance criteria for these extractive solvents – selectivity and capacity – were determined from experimental infinite dilution activity coefficients (IDACs) of various solutes. The effect of solute molecular structure on IDAC values was investigated. Moreover, the effect of varying the hydrogen bond donors (HBDs) in DESs on IDAC values was examined. Partial excess molar enthalpies at infinite dilution were determined from the experimental IDAC data. Moreover, common industrial separation problems were selected to investigate DES potential to separate various mixtures by determining selectivity and capacity at infinite dilution.

The results obtained in this study indicate that the use of a long carbon chain HBDs greatly decreases miscibility of DESs with organic solutes. For systems such as n-heptane - toluene, acetone - ethanol, cyclohexane - benzene and n-hexane - benzene systems, DES4 was the best solvent regarding the separation performance index.

However, further investigation for DES4 by measurements of vapour-liquid equilibria (VLE) and liquid-liquid equilibria (LLE) data is suggested, as these data would provide additional pertinent information regarding the separation of such mixtures using DES4. The data produced from this study can be used to extend the applicability range of predictive models such as Universal Quasi- Chemical Functional Group Activity Coefficients (UNIFAC) and modified UNIFAC (Do) which are already incorporated in some chemical engineering process simulators.