微孔金属-有机骨架材料应用于烯烃纯化

Ethylene, propylene, 1,3-butadiene and styrene are the most important chemical products in the industry today. In the process of production, these olefins contain a large amount of alkane, the purity of the olefin product will affect its polymerization reaction, thus affecting the performance of polymer materials. Therefore, in the industry, to achieve the purity of the product to meet the requirements of polymerization, great energy consumption and high cost of equipment investment are necessary. Pressure swing adsorption (PSA) technology is considered to be the most promising alternative, and the optimization and improvement of the separation performance of the porous materials of adsorbent bed becomes the key problem. In recent years, gas separation application of the metal organic frameworks (MOFs) has been developed, and show promising performance. However, most of the MOF materials have a greater selectivity for olefins over alkan, resulting in lower purification performance. In order to reduce the energy consumption and production cost of olefins purification, the alkane selective MOFs materials with specific molecular recognition were designed to optimize the supramolecular interactions in the restricted space. As a result, with a single breakthrough operation, the olefins purity is enough for the requirement of polymerization reactor. The olefins purification of these MOFs will be studied deeply, and the relationship between the structure and properties will be investigated to provide a scientific basis for further exploration of the design of high performance materials for olefins purification.

乙烯、丙烯、1,3-丁二烯和苯乙烯是工业最重要的化工产品。为了获得达到聚合纯度要求的烯烃产品，工业界通常以极大的能量消耗和高昂的设备投资为代价。变压分离技术被认为是最具发展前景的替代者，吸附床填料的性能成为核心问题。近年来，具有该性能的金属有机框架(MOF)被陆续研发出来，并展现出良好的发展前景。但是大部分的MOF材料对烯烃有更强的选择性，导致其需要经过多次纯化过程才能获得满足纯度要求的 烯烃产品，纯化性能较低，难以满足工业需求。本项目以降低烯烃纯化能耗和生产成本为出发点，以限域空间超分子作用优化为理论指导，以功能为导向，通过合理的配体设计，构筑系列对烷烃分子具有特异性分子识别的微孔MOF材料，实现仅需要经过一次的吸附过程，就能获得满足聚合度纯度要求的烯烃产品。通过系统研究其烯烃纯化性能，探究结构与性能的关系，为进一步探索高效低能耗纯化烯烃材料的设计提供科学基础。

在本项目的资助下，开展了金属有机框架在气体吸附分离与催化方面的应用，发表包括J. Am. Chem. Soc.、Angew. Chem. Inter. Edit.和Chem. Sci.等SCI论文10篇。.在烃类气体小分子分离方面，利用氧气氧化修饰多孔材料获得目前最好的丙烯/丙烷分离性能，相关成果以通讯作者身份在国际化学顶级期刊Angew. Chem. Inter. Edit.上发表。在二氧化碳催化转化方面，首次利用框架中氢氧根的氢键协同促进二氧化碳光催化还原，实现烟道气气氛条件高效催化还原二氧化碳。相关成果以通讯作者身份在国际化学顶级期刊J. Am. Chem. Soc.上发表，论文入选ESI高被引。