核壳微介孔复合分子筛的组装制备与合成过程机理研究

The fully refined processing of high-sulfur crude oil, heavy oil and residual oil has been one important issue that current oil industry faces, meanwhile, the synthesis and application of porous catalysis material which take composite molecular sieves as representative become one of the topic research hotspot of this project. Studying the forming rule and influencing factors of the primary and secondary structure unit of silicon aluminium nano cluster in the synthesizing process using nano assembly method, analyzing the relation rule between acid and stability during the formation of mesoporous composite molecular sieves by the self-assembly of them and micelle template mesoporous; Discussing the realtion rule between nuclear diameter and the shell thickness, composition and structure, morphology and properties of molecular sieves with same skeletal strcture and different acidity or coreshell strcture composite molecular sieves by the assembling and with crystal growth of the same primary structure unit；Studying the forming mechanism and influencing factors of the process which is the forming of core-shell composite molecular sieves by the self-assembly between ZSM-5 molecular sieves and molecular sieves with low hydrogen transfer activity and large pore diameter under alkaline conditions; Taking the micro-mesoporous zeolites and coreshell composite molecular sieves which we composite as the carriers to prepare corresponding catalysts by unconventional means, analysing catalytic mechanism and rule of the probe reaction that is hydrodesulfurization of thiophenes in the oil, and establishing the theoretical foundation for the synthesis process and mechanism of new catalytic materials which are based on composite molecular sieves.

高硫原油、重油及渣油的充分炼制加工成了当前石油工业面临的重要课题，同时以复合分子筛为代表的多孔催化材料的合成与应用成为该课题的研究热点之一。研究探讨采用纳米组装法合成过程中硅铝纳米簇初级和次级结构单元的形成规律与影响因素，分析它们与胶束模板自组装形成介孔复合分子筛的酸性和稳定性的关系规律；探讨具有相同骨架结构、不同酸性的分子筛或相同初级结构单元进行组装附晶生长合成核壳结构复合分子筛的核径与壳厚、组成与结构、形貌与性能的关系规律；研究碱性条件下ZSM-5分子筛与低氢转移活性、孔径较大分子筛制成核壳复合分子筛的自组装形成机理与影响因素；以组装制备的微介孔复合分子筛和核壳复合分子筛为载体，采用特殊手段制得相应催化剂，以油品中噻吩类硫化物加氢脱硫作为探针反应分析其催化作用机理与规律，为制备复合分子筛基础的新催化材料合成过程与机理奠定理论基础。

本项目以高硫原油、重油、及渣油的充分炼制加工为目标，设计、构建和制备新型分子筛基催化剂，并系统研究了目标材料的制备、表征和催化转化性能关系。通过水热合成法、溶胶-凝胶法分别制备了系列HMS、MCM-41、TS-1等分子筛，并采用FTIR，XRD，SEM，TEM，BET等手段对催化剂的结构和形貌进行表征，探讨了纳米组装法合成过程中硅铝纳米簇初级和次级结构单元的形成规律与影响因素，分析它们与胶束模板自组装形成介孔复合分子筛的酸性和稳定性的关系规律。以组装制备的微介孔复合分子筛和核壳复合分子筛为载体，采用超声辅助浸渍法、原位合成法等手段负载金属Cu，Ni，W，Ti等制得相应催化剂，以模型油中噻吩类硫化物的脱除作为探针反应，探讨了催化反应过程中反应中间物的动态转化行为，揭示了催化剂的动态特性与其构效关系，研究了催化转化机制、催化作用及失活机理，为复合分子筛为基础的新催化材料合成过程与机理奠定理论基础。