Salt-based deep eutectic solvents (DESs) have been proposed in this work for the separation of the azeotrope of acetonitrile and water (H2O). The vapor–liquid equilibrium experiments indicated that (ChCl:U:CaCl2)1:2:0.36 exhibits an higher selectivity among all of the entrainers investigated and eliminates the azeotropic point of acetonitrile and water mixture. Moreover, the calculated values by NRTL model coincide well with the experimental data for the systems (acetonitrile + H2O + (ChCl:U:CaCl2)1:2:0.36). Based on the thermodynamic study, the conceptual process design was established to evaluate the competitiveness of the suggested entrainers for the separation of acetonitrile and water. It was determined that the thermodynamic efficiency (η) in the extractive distillation (ED) process utilizing the new salt-based DESs entrainers increases 60.31 % compared with the benchmark entrainer ethylene glycol (EG). Conversely, the ED process using (ChCl:U:CaCl2)1:2:0.36) entrainer can reduce the total annual cost (TAC) by about 7.81 % and the CO2 emissions (ECO2) by 14.74 %. The ED process using (ChCl:U:CaCl2)1:2:0.36) as entrainer shows the high energy efficiency, low economy cost and low CO2 emissions with a great industrial application prospect when compared to the bench marked process.
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