基于多功能填充剂构筑高效CO2传递通道强化膜过程的研究

High performance CO2 separation membrane materials are important requirements for CO2 separation. In this project, the multifunctional fillers, which are core-shell fillers are filled into polymer matrix to fabricate the novel mixed matrix membranes (MMMs) by a physical blending method. The core layer and shell layer of core-shell fillers are designed by changing their functional groups, morphologies and pore structures for intensifying CO2 solubility selectivity, diffusivity selectivity and reactivity selectivity to controllably construct the efficient CO2 passageways. The microenvironments of inner/outer surface of the passageways and free volume in MMMs are regulated by selecting the high optimized composition of the core layer and shell layer, the best matching rules of the core layer and shell layer are obtained. The relationship between the multifunctional structure with the core layer and shell layer of the fillers and separation performance of membranes is revealed by studying on membrane separation performance. Based on the modified Maxwell model, CO2 transport mechanisms in efficient passageways constructed by the multifunctional fillers are elucidated. The separation process of membranes is intensified. MMMs with high permeability and high selectivity are obtained. The project provides the theory supports for designing the novel high performance CO2 membranes materials.

高性能CO2分离膜材料是膜法用于CO2分离的重要需求。本项目以构筑高效CO2传递通道强化膜过程为目标，采用物理共混法将多功能填充剂填充至高分子基质制备新型混合基质膜，设计多功能填充剂—核壳型填充剂，通过设计调控填充剂核层和壳层的功能团种类、形貌和孔结构使其具备同时强化CO2溶解、扩散、反应选择机制的多功能特性，以实现高效CO2传递通道的可控构筑；优选高匹配的核壳层组成，调控CO2传递通道内、外表面微环境和自由体积特性，获得最佳核壳层匹配规律；研究膜的分离特性，揭示填充剂核层、壳层的多功能结构与膜分离性能间的构效关系；基于修正的Maxwell模型，阐明多功能填充剂构筑的高效传递通道中CO2传递机制；对膜分离过程进行强化，获得高渗透性、高选择性的新型混合基质膜；为设计开发新型高性能CO2分离膜材料提供基础理论依据。

面向能源气净化的重要需求，本项目提出了对多功能核壳填充剂核层和壳层的官能团种类、形貌和孔结构进行调控，在混合基质膜内构筑了零维、一维、二维、三维不同维度结构的高速CO2传递通道，实现了能源气净化过程的高效强化，获得了多功能填充剂最佳核壳层的匹配规律，形成了CO2传递通道内、外表面微环境的调控方法，实现了膜内溶解、扩散、反应多重渗透选择机制的集成，揭示了膜通道结构-物理化学微环境-载体传递机制间的内在联系，初步形成了基于不同维度结构CO2传递通道的混合基质膜设计与制备基础理论。本研究所制备的混合基质膜CO2渗透系数达1431±35 Barrer，CO2/CH4选择性达46±1.4，CO2/N2选择性达69±2.7，超过了2008年的Robeson上限。此外，本项目通过在膜内引入CO2载体制备促进传递膜，通过调控CO2载体种类和含量构筑CO2传递通道，强化了CO2分离性能。本项目的研究成果为高性能气体分离膜材料的开发提供了理论依据与技术参考。本项目在ACS Applied Materials & Interfaces、Separation and Purification Technology、International Journal of Greenhouse Gas Control等化工、材料领域高水平期刊上发表SCI学术论文5篇，其中中科院一区论文3篇，中科院二区论文2篇；发表中文核刊1篇；获授权中国发明专利4件；2人入选兵团中青年科技创新领军人才计划；1人入选国际著名SCI期刊Frontiers in Chemistry客座编辑；获兵团自然科学二等奖1项；培养硕士研究生10人。