甘油叔丁基醚（glycerol tert-butyl ethers, GTBE）的合成已成為提高甘油價值的一種可行途徑，而甘油是生質柴油過剩產生的產業副產品。本研究旨在深入探討以叔丁醇（tert–butanol alcohol, TBA）作為共反應物，透過甘油醚化反應生產高級GTBE的過程，以增加生質柴油的經濟價值。本研究以Aspen Plus製程設計工具提出的製程包括三個反應器串聯並設有進料分流，並利用甘油作為重質萃取劑進行萃取蒸餾，以分離水與TBA的共沸混合物。再提出更具優勢的反應蒸餾（reactive distillation, RD），來取代反應端反應器串連的設計。反應蒸餾具有提高反應的轉化率、反應產生的熱量可節省外部能源，降低操作成本、將反應器與分離設備整合於單一設備中，簡化流程、減少設備與佔地，進一步降低投資成本等。在兩製程經過模擬退火演算法最適化總效益（Profit）以及經濟評估後，反應器串聯製程與CSTR串聯製程在相同的產物價格下，擁有較低的回收年（Pay back year），總獲利可高出80.4%。本研究結果不僅顯示以TBA為共反應物進行甘油醚化反應生產高級GTBE具有良好的技術與經濟可行性，亦顯示反應蒸餾技術相較於傳統反應器串聯製程在經濟效益與流程整合上具有明顯優勢。透過製程模擬與最適化結果可知，反應蒸餾不僅提升了產率與能源利用效率，更有效降低設備與操作成本，為未來推動甘油增值利用與生質柴油產業整合提供具體可行的策略與方向。

The synthesis of higher glycerol tert-butyl ethers (GTBE) presents a promising approach to valorize glycerol, a byproduct abundantly generated by the biodiesel industry. This study aims to enhance the economic value of biodiesel by investigating the etherification of glycerol using tert-butanol (TBA) as a co-reactant for GTBE production. Two process configurations were developed and analyzed using Aspen Plus: a traditional cascade of three reactors with feed splitting, and a reactive distillation (RD) process, which integrates reaction and separation within a single column. Reactive distillation offers several benefits, including improved reaction conversion, utilization of reaction heat to save external energy, reduced operating costs, and integration of the reactor and separation units into a single piece of equipment, thereby simplifying the process, reducing equipment footprint, and lowering capital investment. After process optimization using the simulated annealing algorithm for maximum total profit and subsequent economic evaluation, the series reactor process and the CSTR series process achieved a lower payback period under the same product price, with total profits up to 80.4% higher. The results confirm the technical and economic feasibility of producing GTBE via the etherification of glycerol with TBA. Furthermore, the RD process offers superior process integration, higher energy efficiency, and greater profitability compared to traditional designs. This study provides a practical and scalable strategy for integrating glycerol valorization into the biodiesel production chain.

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