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    二氧化碳加氢制低碳烯烃研究进展

    Research progress in hydrogenation of CO2 to light olefins

    • 摘要: 二氧化碳加氢制低碳烯烃是“双碳”目标下氢能转化及二氧化碳资源化利用的重要技术途径。文章综述了该领域的最新研究进展。首先,热力学分析表明,二氧化碳分子具有极高的热力学稳定性,其活化需要克服较高能垒,同时烯烃产物不如烷烃稳定,生成的烯烃容易过度加氢生成饱和烷烃,因此实现高选择性生成低碳烯烃是核心挑战。随后,详细阐述了两条主要技术路径:逆水煤气变换耦合费托合成(RWGS-FTO)路径与甲醇介导(CO2-MTO)路径。对于RWGS-FTO路径,重点探讨了铁基催化剂中活性相(Fe3O4与χ-Fe5C2)的动态演变及其协同机制,并总结了碱金属(Na、K)和过渡金属(Mn、Zn、Cu)等助剂的电子促进等效应及载体对催化性能的调控规律,指出该路径虽具有较高的CO2转化率,但产物分布受限于ASF分布模型,导致低碳烯烃选择性最高不超过58%。对于甲醇介导路径,重点论述了金属氧化物(如ZnZrOx固溶体、In2O3及尖晶石型氧化物)与分子筛(SAPO-34、SSZ-13等)组成的双功能催化体系,分析了分子筛的拓扑结构、酸性质以及双组分间耦合方式(空间距离)对中间体传递与产物选择性的关键作用,该路径可突破ASF限制,实现高达80%以上的低碳烯烃选择性,但面临CO2单程转化率偏低的挑战。最后,针对当前CO2转化率与低碳烯烃选择性难以兼顾的“跷跷板”难题,展望了未来在高效催化剂设计、反应机理深化研究以及反应工艺优化等方面的发展方向。

       

      Abstract: The hydrogenation of CO2 to light olefins is an important technological route for hydrogen energy conversion and CO2 resource utilization under the "dual carbon" goals. This article reviews the latest progress in this field. First, thermodynamic analysis indicates that CO2 molecules are highly stable and their activation must overcome a high energy barrier. Meanwhile, olefin products are less stable than alkanes, and the olefins formed are prone to over-hydrogenation to saturated alkanes. Achieving high selectivity to light olefins is therefore the central challenge. Subsequently, two main technological routes are elaborated: the reverse water-gas shift coupled with Fischer-Tropsch synthesis (RWGS-FTO) route and the methanol-mediated (CO2-MTO) route. For the RWGS-FTO route, the discussion focuses on the dynamic evolution and synergistic mechanism of active phases (Fe3O4 and χ-Fe5C2) in iron-based catalysts. The electronic promotion effects of promoters such as alkali metals (Na, K) and transition metals (Mn, Zn, Cu), as well as the regulatory role of supports on catalytic performance, are summarized. Although this route exhibits high CO2 conversation, the product distribution is constrained by the ASF model, limiting light olefin selectivity to no more than 58%. For the methanol-mediated route, the focus is on bifunctional catalytic systems composed of metal oxides (e.g., ZnZrOx solid solutions, In2O3, and spinel oxides) and zeolites (e.g., SAPO-34, SSZ-13). The critical roles of zeolite topology, acidity, and the spatial proximity between the two components in intermediate transfer and product selectivity are analyzed. This route can break the ASF limitation and achieve over 80% light olefin selectivity, but faces the challenge of low single-pass CO2 conversion. Finally, in response to the "seesaw" problem where CO2 conversion and light olefin selectivity are difficult to balance, future directions are proposed, including the design of efficient catalysts, in-depth investigation of reaction mechanisms, and optimization of reaction processes.

       

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