AbstractThe batch distillation is significant and flexible to separate liquid mixtures. However, it is usually energy intensive. The dividing‐wall column (DWC) is a promising and practical energy‐saving process intensification technology. The DWC for batch distillation (batch DWC) to separate benzene, toluene, and xylene mixtures was examined with composition and temperature control structures to verify its controllability. Besides, the batch DWC outperforms the conventional single‐column batch distillation and middle‐vessel batch distillation in terms of distillation time and energy consumption under the same conditions. In terms of more practical temperature control results, the batch DWC saves 63 % of energy compared with the conventional single‐column batch distillation and 47 % of energy compared with the middle‐vessel batch distillation.