低阻力通道混合基质膜的构建及CO2分离性能调控

At present, the inorganic material as a mixed matrix film dopant is mostly solid structure, the resistance to gas transfer is too large, and the compatibility between the dopant and the polymer is poor, and it is difficult to simultaneously improve the permeability of the gas in the film and Selectivity. This project proposes the construction of a poly dopamine modified hollow MOFs nanospheres to prepare a modified MOFs mixed matrix membrane with a "low resistance" delivery channel with both high CO2 permeability and selectivity. The MOFs nanospheres with hollow structure were constructed by controlling the mass transfer and reaction rate of MOFs precursors at the microemulsion interface, and the low permeability channels were built in the membrane to improve the gas permeability of the films. As the interface binder, the surface polymerization of the hollow MOFs nanospheres was controlled to achieve a high degree of compatibility between the MOFs and the polymers to improve the gas selectivity of the films. The interfacial strength, MOFs self-assembly parameters and dopamine polymerization conditions were investigated. The effect of dopamine modified MOFs on the structure and properties of hollow nanospheres was investigated by adjusting the interfacial adhesion and hollow core channels of MOFs nanospheres. The effects of "low resistance" channels on the mass transfer process were investigated, and the polyphenamine modified MOFs hollow nanospheres Structural parameters and mixed matrix membrane properties of the associated model, the effective balance of mixed matrix membrane permeability and selectivity. This project will provide a new idea for the study of MOFs mixed matrix membrane for CO2 separation.

目前作为混合基质膜掺杂物的无机材料多为实心结构，对气体传递阻力过大，且掺杂物与聚合物之间相容性较差差，难以同时提高气体在膜中的渗透性和选择性。本项目提出构建一种聚多巴胺改性的中空MOFs纳米球，制备具有“低阻力”传递通道的性能可调MOFs混合基质膜，兼具高CO2渗透性和选择性。项目将以微乳液界面为自组装中心，控制MOFs前驱体在模板界面传质和反应速率，构建具有中空结构的MOFs纳米球，在膜内构建低阻力通道，提高膜的气体渗透性；以多巴胺为界面粘合剂，控制其在中空MOFs纳米球表面聚合，实现MOFs与聚合物间高度相容，提高膜的气体选择性；揭示液膜界面强度、MOFs自组装参数和多巴胺聚合反应条件对聚多巴胺改性MOFs中空纳米球结构和性能的影响规律，调控MOFs纳米球的界面粘合性和中空内核通道；探索“低阻力”通道对传质过程的影响，建立聚多巴胺改性MOFs中空纳米球结构参数与混合基质膜性能的关联模型

随着近年来全球工业化程度的提高，作为化石燃料的主要燃烧产物，越来越多的CO2被排放到大气中，导致日益严重的温室效应。相比于其他方法，膜分离具有环境友好，设备及操作费用低，占地面积小，易于与其他过程进行耦合等优点受到了广泛应用。本项目针对混合基质膜掺杂物的无机材料多为实心结构，对气体传递阻力过大，且掺杂物与聚合物之间相容性较差，难以同时提高气体在膜中的渗透性和选择性的问题，本项目提出使用具有纳米空心结构的填料，构建具有低阻力传递通道且性能可调控的混合基质膜，兼具高CO2渗透性和选择性。本项目在资助下，取得了如下成果：（1）ZIF-8和ZIF-8复合填料设计及低阻力气体传递通道混合基质膜构建及性能调控，使用微乳液界面自组装的方法制备了不同尺寸的纳米ZIF-8，并设计了胺基功能化ZIF-8，以其为填料的混合基质膜较纯膜性能提高了107.6%；（2）为解决常规二维材料透气性差导致混合基质膜气体传递阻力高得问题，提出使用二维微孔碳纳米片作为填料，构建具有低气体传递阻力通道得混合基质膜，进而提高CO2的渗透分离性能；（3）设计了双膜分离器应实现了H2/CO2/CH4三元气体混合物的有效分离，在高切割比工况下，双膜分离器比单膜分离器具有明显的优势。本项目相关成果在Journal of Membrane Science、Separation and Purification Technology等本领域高水平国际期刊上发表SCI收录论文12篇，全部标注本项目资助，申请中国发明专利8项，其中以项目负责人为第一发明人申请2项，项目骨干作为第一发明人申请3项。参加国内外学术会议8人次，口头报告1人次，墙报1人次。项目负责人作为主要参与人，获得2018年国家科技进步二等奖（9/10）。项目负责人作为主要参与人，获得第45届日内瓦国际发明展展会评判特别嘉许金奖（5/7），所在团队于2019年获批中国石油和化学工业联合会创新团队，项目负责人是团队的骨干，主要负责用于CO2捕集和VOCs分离的低阻力膜的研制。