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In this study, deep eutectic solvents (DESs) were prepared using choline chloride as hydrogen bond acceptor (HBA) and ethylene glycol (EG) or glycerol (GLY) or urea (U) as hydrogen bond donor (HBD) and were evaluated as solvents in the extraction of benzene from n-hexane. Six of such solvents were prepared using different molar ratios of HBA: HBD and code named DES1, DES2, DES3, DES4, DES5 and DES6. Liquid–liquid equilibria (LLE) data for the ternary systems of n-hexane-benzene-DESs were measured at 303 K and 101.3 kPa. Solubility data and mutual solubilities between n-hexane and DES were measured using the traditional cloud point method. The tie lines were obtained using titration and refractive index measurements on both phases (n-hexane phase and DES-phases). The ternary systems exhibit type-1 phase behavior. The Othmer-Tobias and Hands equations were applied to examine the reliability of the LLE data. The tie-line data were correlated using the nonrandom two-liquid (NRTL) and universal quasichemical (UNIQUAC) thermodynamic models, and their corresponding binary interaction parameters were determined. The results show that the maximum separation factors were 31.24, 462.00, 15.24, 37.83, 174.60 and 126.00 for DES1, DES2, DES3, DES4, DES5 and DES6, respectively. The glycerol based DES (DES2 and DES5) show the highest separation factors and thus considered the most suitable for separating benzene from hexane. The regression coefficient for both Othmer-Tobias and Hand equations are higher than 0.99 for all DESs, indicating the reliability and consistency of the data. Both NRTL and UNIQUAC models adequately capture the experimental data.

Deep eutectic solvents (DESs) have high viscosities, but known to be mitigated by addition of suitable co-solvent. The effect of such co-solvent on the extraction efficiency of the hybrid solvent is hardly known. This study examined the effect of ethanol on three choline chloride-based DESs (glyceline, reline, and ethaline) by mixing each in turn with ethanol in various volume proportions. The hybrid solvents were evaluated for the extraction of benzene from n-hexane. Pseudo-ternary liquid–liquid equilibrium data were obtained using the refractive index method at 303 K and 1 atm for the systems, n-hexane (1) + benzene (2) + hybrid solvent (glyceline/ethanol, ethaline/ethanol, reline/ethanol) (3), and used to evaluate distribution coefficient (D) and selectivity (S). Furthermore, the physicochemical properties of the hybrid solvents were also determined. The results indicate increase in selectivity with increasing ethanol addition up to 50% and decrease with further addition. All hybrid solvents with 50% ethanol outperform sulfolane and are suitable replacement for same as green and sustainable extractant for aromatics from aliphatics. The glyceline + 50% ethanol emerged the overall best with 49.73% elevation in selectivity and 41.15% reduction in viscosity relative to the neat glyceline. The finding of this study is expected to fillip the drive for paradigm shift in petrochemical industries. Supplementary Information The online version contains supplementary material available at 10.1007/s13203-021-00282-y.