Pressure-swing distillation has demonstrated prominent advantages in separating complex ternary azeotropic systems due to its ability to exploit pressure-dependent azeotropic shifts. This study proposed a novel decanter-assisted pressure-swing distillation configuration (NPSD) for the challenging separation of a benzene/n-propanol/water ternary azeotropic system. Building upon the NPSD framework, thermal efficiency was further enhanced via a vapor recompression heat pump, leading to the NPSD-HP process. Despite these advancements, plantwide dynamic controllability of such hybrid systems remained underexplored. To address this research gap, the controllability of conventional NPSD and heat pump-assisted NPSD-HP processes was systematically investigated through Aspen Dynamics. For the NPSD system, temperature sensitivity analysis employing a slope criterion identified critical control stages, enabling the design of two control configurations: a basic temperature-driven control structure (CS1) and an enhanced structure (CS2) that effectively reduced deviations and offsets of product purity with improved robustness. The NPSD-HP process was evaluated through three progressively sophisticated control schemes (CS3~CS5). The results showed that the component-temperature cascade-feed-forward control structure (CS5) demonstrated superior disturbance rejection capabilities, effectively handling ±20% feed flow and composition disturbances while maintaining favorable dynamic response characteristics. Comparative analysis of integral absolute error (IAE) metrics revealed that cascade control implementation reduced error accumulation through the correction effect of the component loop. This discovery demonstrated that composition control exhibited distinct advantages in complex distillation systems, including shorter response times and reduced overshoot, highlighting its significant application value. These findings underscored extensive research opportunities in dynamic control strategies for ternary azeotrope separation via advanced distillation technologies. Future investigations should focus on intelligent optimization frameworks integrating model predictive control with AI-driven algorithms, multivariable coordinated regulation mechanisms, and intensive energy conservation approaches. Such advancements are expected to further enhance disturbance rejection capabilities and economic performance in heat pump-assisted distillation processes.