In this study, a few extractive distillation processes with ethylene glycol as solvent are proposed to separate high-purity ethanol and tert-butanol from industrial effluents, including direct ED, indirect ED and heat pump assisted indirect ED. All these processes are optimized with targeting minimum annual total costs by a sequential iteration algorithm. After that, a head-to-head comparison is completed regarding distributions of cost, energy and CO2 emission. The results showed that the direct ED is the most economical process reducing minimum annual total costs by 30.15 % than the heat-pump assisted indirect ED, while the latter is the most energy-efficient process saving energy consumption and CO2 emissions by 14.78 % and 21.79 % than the direct ED. (C) 2020 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.