新型填隙式分子筛/聚醚砜复合膜材料的制备及气体分离性能研究

With the development of petrochemical and industrial catalysis technology, the consumption of fossil energy has been increased, which produces large amounts of greenhouse gases. Due to the demand for clean energy development and environment protection, research and development on efficient gas separation technology of H2 and CO2 have received world-wide attention. Adsorption and separation processes are also important parts in catalysis research. However, current gas separation techniques are apt to be less efficient, high cost, and hard to be fabricated in large scales, which limit their industrial application. In this proposed research, we plan to design a novel Pore-filled Zeolite/PES Composite Membrane used for gas separation, which will combine the advantages of high gas selectivity of zeolite molecular sieves with easy fabrication of polymer membranes. Synthesis dry-gels of zeolites will be perfused into pores of polyethersulfone (PES) membranes, followed by in-situ crystallization of zeolites. The inorganic-organic composite membranes with gas separation properties will be obtained. On the basis of full characterizations of the membrane materials, the structures and compositions as well as the gas permeation and separation properties of the composite membranes will be studied. In addition, the mechanisms for the gas permeation and diffusion in the composite membranes will be revealed. The long-term goal in this proposed research is to optimize the compositions and structures of the composite membranes, with expectation of developing an easy preparation, low-cost route to obtain membranes featuring excellent gas separation performances. The results to be produced from the proposed research will lay a solid foundation for the industrial applications of this type of composite membranes.

随着石油化工和工业催化技术的发展，化石能源的消耗日益增加，产生大量温室气体。出于清洁能源开发和环境治理的需求，针对H2和CO2的高效气体分离技术的研发受到全球性的关注。吸附分离过程亦是催化领域研究的重要内容。但现有气体分离技术存在效率低、成本高、不易放大等局限。本课题结合沸石分子筛选择性高的优点和聚合物膜良好的加工性能，提出设计制备一种新型填隙式分子筛/聚醚砜复合膜材料，并将其应用于CO2和H2的气体分离。通过将分子筛合成干凝胶灌注入多孔聚醚砜（PES）膜表面的孔隙中，结合原位晶化，得到具有气体分离功能的无机–有机复合膜材料。通过对膜材料进行充分的表征，深入研究这种复合膜的气体渗透分离性能，探索气体在该复合膜中的渗透扩散机理，优化复合膜材料的结构和组成，得到利于工业制备、成本低、气体分离效果好的膜材料，为其工业化应用打下基础。

随着石油化工和工业催化技术的发展，化石能源的消耗日益增加，针对H2和CO2的高效气体分离技术的研发受到全球性的关注。膜技术是分离气体混合物的一种高效、便捷的方法，分子筛膜作为无机膜的一种，具有均一的孔径、良好的水热稳定性，而被广泛用于气体分离。分子筛气体分离膜多数以氧化铝、不锈钢等刚性载体，采用二次生长法在载体表面成膜，分子筛也被作为聚合物膜的填料制成混合基质膜材料用于气体分离。而以聚合物为载体制备分子筛膜的研究，目前鲜有报道。本课题结合沸石分子筛选择性高的优点和聚合物膜良好的加工性能，以自制聚醚砜超滤膜为载体，利用原位水热合成法在聚醚砜表面合成分子筛晶体层，深入研究了该体系下制备分子筛晶体膜层的最佳条件。采用聚二甲基硅氧烷（PDMS）对分子筛膜表面进行涂覆，以填充无机-有机界面及膜表面的晶间缺陷。最终得到了具有较高气体渗透速率和针对能源气体具有良好分离性能的新型分子筛-聚醚砜复合膜材料。在分子筛-聚合物基质间不同结合方式上，本课题采用对银离子交换的分子筛进行表面改性，再与聚合物共混制膜，研究开发了具有抗菌性能的分子筛-聚偏氟乙烯混合基质膜材料。在其它无机多孔材料与聚合物膜材料的复合方面，本课题通过对聚醚砜膜载体进行表面化学接枝改性，诱导金属有机骨架材料的成核与生长，设计制备了聚醚砜支撑体上高质量的金属有机骨架膜材料。这些结果为开发新型分子筛-聚合物复合膜材料提供了科学依据和技术支持。