In this work, the extractive distillation with heat integration process is extended to separate the pressure-insensitive benzene-cyclohexane azeotrope by using furfural as the entrainer. The optimal design of extractive distillation process is established to achieve minimum energy requirement using the multi-objective genetic algorithm, and the results show that energy saving for this heat integration process is 15.7%. Finally, the control design is performed to investigate the system’s dynamic performance, and three control structures are studied. The pressure-compensated temperature control scheme is proposed based on the first two control structures, and the dynamic responses reveal that the feed disturbances in both flow rate and benzene composition can be mitigated well. In this work, the extractive distillation with heat integration process is extended to separate the pressure-insensitive benzene-cyclohexane azeotrope by using furfural as the entrainer. The optimal design of extractive distillation process is established to achieve minimum energy requirement using the multi-objective genetic algorithm, and the results show that energy saving for this heat integration process is 15.7%. Finally, the control design is performed to investigate the system’s dynamic performance, and three control structures are studied. The pressure-compensated temperature control scheme is proposed based on the first two control structures, and the dynamic responses reveal that the feed disturbances in both flow rate and benzene composition can be mitigated well.