芳香烃/脂肪烃分离功能导向的金属-有机骨架材料微环境构筑与性能调控研究

Metal-organic frameworks (MOFs) are a novel class of porous materials with unique chemical and structural characteristics, which endow them with promising applications in separation in petrochemical engineering. At present, one major problem is the low efficiency for the development of MOFs with high separation performance, as well as the lack of targeted design for the specific system. In this project, microstructure of MOFs will be constructed and modified for the separation of aromatic/aliphatic hydrocarbon mixtures as an example. The key research method is an algorithm for high-throughput self-assembly hypothetical MOFs, combined with computational chemistry method (quantum chemistry calculation and molecular simulation). Using “application-oriented” bottom design idea, physical and chemical properties of guest molecules will first be investigated by quantum chemistry calculations, as well as their microscopic interaction mechanisms with second building units of MOFs. Based on these information, microstructure of MOFs will be built including the structure-property relationship. Tremendous hypothetical targeted materials can be generated through high-throughput algorithm, followed by the screening for separation performance using the combination of molecular simulation and experiments. In addition, the microstructures of potential materials are modified and the optimum operation process conditions are confirmed. The main focus of this project is the full utilization of the unique characteristics of MOFs, (such as “modularity”, designability and functionality in chemistry and structure), and the power of computational chemistry method in the large-scale design and screening of materials. Therefore, the results of this project are significant for providing technological reserves for separation materials in petrochemical engineering, and promoting the transformation from fundamental study to practical research in MOF area.

金属-有机骨架材料(MOFs)独特的化学、结构特点，使其有望在石油化工分离领域发挥作用。但目前存在的主要问题是，针对于特定分离体系，设计合成高效分离材料的效率不高，且缺少针对性。本项目以高通量虚拟MOF材料导向生成算法，结合量化计算与分子模拟为关键技术，以芳香烃/脂肪烃分离为例，系统研究MOFs微环境的构筑与调控。以“订单式”底层设计的思路，结合二级结构单元大数据，构筑适用于芳香烃与脂肪烃体系的微环境；用分子模拟方法，结合相关材料的实验合成，验证并筛选材料的分离性能，优化微环境的设计，确定最优操作工艺条件。本项目侧重点是充分利用MOF材料“模块化”以及可设计性、可功能化强等特点，发挥理论计算在大规模材料设计与高效筛选方面优势，深入研究对芳香烃/脂肪烃的高效分离，将为石油化工分离领域中高性能材料的开发提供技术储备，并促进MOF领域研究从基础转向实用，具有重要意义。

本项目以新型纳微结构材料（金属-有机骨架材料，metal-organic frameworks, MOFs）为主，以包含芳香杂环、脂肪烃结构客体分子的吸附分离为应用导向，采用高通量虚拟MOF材料组装与模拟筛选方法，结合多尺度计算，系统构筑了相应的MOF微环境，开展新材料的设计开发以及相应的吸附分离工艺研究。以“订单式”底层设计思路，针对于客体分子的化学、结构特征，研究了包括含有芳香杂环结构的抗生素分子、染料分子、乙二醇、CH4等多种体系与MOF骨架片段之间的相互协同作用力，利用前期通过高通量方法构筑的MOF材料大规模数据库，结合量化计算和分子模拟等关键技术，建立构效关系，设计并合成了多种具有高效分离性能的MOF材料以及MOF复合膜材料。所获得材料在吸附分离效果上优于已有大多数多孔材料；所提出的制备MOF复合材料以及膜材料的方法，可推广至其他体系的分离材料。在此基础上，以CH4/N2分离为例，设计了基于所开发材料的变压吸附分离过程，并对操作条件进行了优化。这些结果促进了MOF材料在化工等领域中的应用基础研究，并为相关体系的高效分离提供了新材料和新技术储备。.项目按照原计划顺利进行，完成了预定目标，共发表SCI论文12篇（其中1篇影响因子大于10.0，3篇影响因子大于6.0，2篇在化工领域TOP期刊AIChE J.上）；申请专利7件；获得省部级奖励一项（2018年，中国石油和化学工业联合会科技进步奖一等奖，项目负责人排名第二）。