The phenol and pyridine of coal gasification wastewater (CGW) are extremely toxic pollutants. Thus, there is an urgent need to develop a new process for the effective treatment of phenol and pyridine in CGW. Vapor-liquid equilibrium (VLE) and COSMO-SAC model analysis were used to select the entrainer, and interaction region indicator analysis was applied to elucidate the separation mechanism. Aiming to minimize total annual cost (TAC), the optimal process parameters were established through a sequential iterative procedure; extractive pressure-swing distillation process: separation sequence E (EPSDP-SE) process exhibiting the best performance. Heat integrated extractive pressure-swing distillation with dividing wall column process: separation sequence E (HI-DWC-EPSDP-SE) was developed by integrating a thermal process and dividing wall distillation technology. In comparison to EPSDP-SE, HI-DWC-EPSDP-SE achieved reductions of 26.97% in TAC, 38.89% in total operation cost, and 6.21% in total capital cost. Additionally, it lowered total acid gas emissions and energy consumption by 39.98% and enhanced thermodynamic efficiency by 54.72%. The HI-DWC-EPSDP-SE process showcases exceptional separation performance in terms of economy, energy consumption, and environmental impact.
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