The middle vessel batch distillation process for separating the methyl formate/methanol/water ternary system was simulated using Aspen Plus and Aspen Plus Dynamics. The composition control structure (CCS) and temperature control structure (TCS) were studied in a dynamic simulation based on the results of a steady-state simulation. Two temperature control structures, one the traditional TCS and the other TCS with high selectors, show better control performances than CCS. The two control structures can stably control the product purities and liquid holdups in the product vessels at the end of the batch. The results show that TCS with high selectors is better than traditional TCS in terms of the liquid holdups. The performance of the TCS with high selectors is assessed, and controllability is demonstrated.