Vapor–Liquid Equilibrium and Design of Energy-Efficient High-Vacuum Pressure-Swing Distillation for Bio-Based Alcohol/Alkane Separation

Fatty alcohols and aliphatic hydrocarbons occur abundantly in nature and serve as critical feedstocks for the surfactant and fuel industries, respectively. However, their industrial-scale separation and purification are significantly hampered by high boiling points and the formation of complex azeotropes. To address these challenges, this study explores a five-column high-vacuum pressure-swing distillation (HVPSD-5C) strategy. Vapor–liquid equilibrium (VLE) analysis of the key components (n-hexanol, n-octanol, n-dodecane, and n-tridecane) validated the thermodynamic viability of the process and established optimal operating conditions. To further enhance efficiency, a heat-pump-integrated configuration (HPI-HVPSD-5C) featuring vapor recompression and heat integration was designed, optimized, and evaluated. Comparison with the baseline HVPSD-5C process demonstrates that the HPI-HVPSD-5C configuration significantly improves sustainability and economics, reducing the total annual cost (TAC) by 17.48%, CO2 emissions by 16.09%, and energy consumption cost by 12.79%. These findings provide a robust framework for the efficient separation of fatty alcohols from aliphatic hydrocarbons, offering a valuable reference for the purification of other pressure-sensitive azeotropic mixtures.