• Extractive distillation processes are studied for recovery and purification of ethanol and TBA. • Performance evaluation of three extractive distillation processes is implemented. • Direct sequence is the best scheme in terms of TAC. • Heat pump-assisted indirect sequence has the lowest energy consumption and CO 2 emission. 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 CO 2 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 CO 2 emissions by 14.78 % and 21.79 % than the direct ED. [ABSTRACT FROM AUTHOR]