• A novel pressure-swing-assisted ternary heterogeneous azeotropic distillation (THAD) process is proposed to synergistically combine heterogeneous azeotropic and pressure-swing distillation, achieving significant energy savings.
• The integration of dividing-wall column and heat integration technologies further reduces energy consumption and CO2 emissions compared to published THAD processes.
• Genetic algorithm optimization is employed to handle the complex design variables, demonstrating superior energy efficiency and environmental performance.
• The proposed processes avoid aqueous phase remixing and reduce recycle stream flowrates, enhancing overall process sustainability.
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