AbstractBACKGROUNDThe triple‐column extractive distillation (TCED) process for the ternary multi‐azeotropic mixture of N‐hexane/acetone/chloroform is a significant step in waste recovery and purification. Given the common occurrence of feed disturbances in practical industrial production, a feasible dynamic control scheme should effectively resist feed disturbances and ensure product quality, enabling the process to run steadily and safely with a high efficiency. However, it is challenging to design a robust control scheme for separation processes accompanied by side‐stream capability. In this work, dynamic control schemes were designed for four separation processes: conventional and double side‐stream TCED processes with single and double entrainers. A multipoint temperature control scheme, composition‐temperature cascade control scheme and variable ratio control were combined to improve the dynamic performance of the control schemes.RESULTSThe results showed that the control schemes designed for the four extractive distillation processes are highly robust, resisting ±20% feed flow and composition disturbances. A variable ratio control combined with composition‐temperature cascade was found to be vital for double side‐stream TCED schemes.CONCLUSIONThe conventional TCED with a single entrainer (CS‐TCED) is an optimal process for N‐hexane/acetone/chloroform separation both from control and economic perspectives. The designed control scheme is simple, low‐cost and easy‐to‐implement with a superior dynamic performance over other separation schemes. This study has a certain theoretical guidance for N‐hexane/acetone/chloroform separation in terms of economic benefits and practical production. © 2022 Society of Chemical Industry (SCI).