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    二甲醚羰基化反应用分子筛催化剂研究进展

    Advances in zeolites for dimethyl ether carbonylation

    • 摘要: 含碳资源以合成气为枢纽经二甲醚羰基化合成乙酸甲酯。乙酸甲酯加氢制备乙醇工艺路线反应条件温和,催化剂成本低廉且易于制备,是实现包括煤炭在内的诸多含碳资源清洁高效利用,特别是推动煤炭向高价值化学品转变的重要途径。二甲醚羰基化反应为该工艺的核心步骤,分子筛催化剂在二甲醚羰基化反应中的应用得到广泛关注。综述了分子筛催化剂在二甲醚羰基化反应上的反应路线与失活机理研究进展,讨论了不同分子筛,特别是丝光沸石,在二甲醚羰基化反应中的应用,明确了分子筛催化剂的活性位点。基于对反应路径、失活机理与活性位点的理解,进一步梳理了分子筛催化剂的改性策略。这些策略主要围绕以下目标展开:精确调控活性中心的数量与空间分布,有效抑制导致积炭的酸性位点,以及通过优化晶体尺寸或孔道结构以提高反应传质效率。具体内容主要涉及酸性位点调控与微结构调控,并总结了与之相关的催化剂再生行为、制备条件优化及成型技术的研究成果。最后,基于现有研究成果的总结,对分子筛催化剂在二甲醚羰基化反应中存在的问题及未来研究方向进行展望。

       

      Abstract: The process route for producing ethanol via carbon-containing resources (coal-derived) syngas through dimethyl ether (DME) carbonylation to methyl acetate (MA), followed by MA hydrogenation, offers advantages such as mild reaction conditions and the use of cost-effective, easily prepared catalysts. This pathway represents a significant approach for achieving clean and efficient coal utilization, as well as promoting the transformation of coal into high-value chemicals. The DME carbonylation reaction serves as the core step of this process, and the application of zeolite catalysts in DME carbonylation has attracted widespread attention. This review summarizes recent advances in the understanding of the reaction pathways and deactivation mechanisms of zeolite catalysts in DME carbonylation. It discusses the application of various zeolites, particularly mordenite, in DME carbonylation and clarifies the nature of the active sites in zeolite catalysts. Building on the understanding of reaction pathways, deactivation mechanisms, and active sites, the review further outlines modification strategies for zeolite catalysts. These strategies primarily aim to precisely regulate the number and spatial distribution of active centers, effectively inhibit the acid sites responsible for coke formation, and enhance the mass transfer efficiency by optimizing the crystal size or pore structure. Specific discussions cover three main aspects: acid site regulation, microstructural modulation, along with summaries of research findings related to catalyst regeneration, optimization of preparation conditions, and industrial molding technologies. Finally, based on a summary of existing research, the review identifies current challenges and outlines future research directions for zeolite catalysts in DME carbonylation.

       

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