煤基碳四烯烃绿色制造催化路线与催化材料的设计

Owing to our specific fossil energy structure of “deficient oil, lean gas, rich coal”, it is most important to develop new catalytic routes to coal-based C4 olefins. Starting from coal-based C2 raw materials, i.e. ethanol and acetic acid, C4 olefins can be synthesized via cascade reactions while multi-functional catalytic materials play decisive roles in determining the economy and success of the catalytic routes. In the proposed project, we will construct multi-functional catalytic systems confined in zeolites for typical cascade reactions, i.e. ethanol conversion to 1,3-butadiene and acetic acid conversion to isobutene, aiming to develop new catalytic routes toward green manufacturing of coal-based C4 olefins. Advanced dynamic spectroscopic techniques will be employed in studying the transition states of the cascade reactions to reveal the reliable reaction mechanism and further guide the rational design the multi-functional catalytic systems confined in zeolites. The researches of this project belong to content of “New Catalysts and Systems with Certain Functionalities” in catalytic chemistry with primary support, and also involve in the content of “In situ, Dynamic and High-resolution Characterization Methods and Techniques in Catalysis”. The research results are not only of practical significance for the new catalytic routes toward C4 olefins, but also of reference significance for the fundamental theory in confined catalysis, cooperative catalysis and spectroscopy in catalysis.

基于我国富煤贫油少气的化石能源结构，开发煤基碳四烯烃绿色制造的新催化路线具有非常重要的现实意义。以煤基碳二产品乙醇与乙酸为原料，可以通过多步连续反应制备碳四烯烃，而多功能催化材料是决定催化路线经济性与成败的关键。本项目中，我们拟构筑沸石分子筛结构限域多功能催化体系，应用于以乙醇制丁二烯与乙酸制异丁烯为代表的反应中，进而开发煤基碳四烯烃绿色制造新催化路线。我们拟将先进的动态谱学技术应用于多步连续反应过渡态研究中，从而获悉复杂催化反应机理，指导沸石分子筛结构限域多功能催化体系的理性设计。本项目研究属催化化学重点支持发展内容“具有特定功能的新催化剂和体系”，并涉及“原位、动态、高分辨的催化表征新方法和新技术”，研究结果对于碳四烯烃生产新路线具有现实意义，同时项目研究对于限域催化、协同催化以及催化谱学基础理论也具有参考意义。

基于我国富煤贫油少气的化石能源结构，开发煤基碳四烯烃绿色制造的新催化路线具有非常重要的现实意义。以煤基碳二产品乙醇与乙酸为原料，可以通过多步连续反应制备碳四烯烃，而多功能催化材料是决定催化路线经济性与成败的关键。本项目中，我们设计了构筑沸石分子筛结构限域多功能催化材料应用于乙醇制丁二烯与乙酸制异丁烯等反应，开发煤基碳四烯烃绿色制造催化新路线。具体研究内容涵盖沸石分子筛催化材料设计与制备、催化反应动力学、催化反应过渡态、催化反应机理与构效关系等诸多方面。项目成果于ACS Catal、Chinese J Catal、J Mater Chem A等知名学术期刊发表论文10篇，获国家发明专利授权5项。目前已成功开发高性能分子筛催化材料应用于乙醇制丁二烯与乙酸制异丁烯等反应中，为其工业应用奠定基础。