Development of novel organozeolites and application to adsorption separation

尝试用水热法和水蒸气辅助转化法在多孔氧化铝载体上合成甲基膦酸铝薄膜。当拟薄水铝石、甲基膦酸、水和叔丁醇混合后，将部分混合溶液吸入基材，浸泡基材，然后在160℃的高压釜中进行水热处理，可能是由于基材内部形成了复合材料，AlMepO-β在基材上结晶形成了膜状聚集体。将相同的混合液吸入衬底，烘干衬底，然后在高压锅中蒸煮，可获得厚度为40μm的AlMepO-AlMepO-AlMepO薄膜，薄膜中生长着微晶，使衬底与衬底之间紧密接触。然而，氧气、空气和氢气的单一气体渗透实验表明，膜和基质之间的渗透几乎可以忽略不计。研究了由金属和含团的膦酸根组成的有机沸石的合成。虽然不可能获得能够吸附氮气的纳米孔化合物，但制备的几种化合物已经从叔丁基膦酸酯中稀释了长程有序。特别是当加入三氧六环时，锌/叔丁基膦/甲基膦酸盐体系在d=25Å处得到了具有X射线衍射峰的产物，其中两个膦酸根都被引入骨架中。此外，还尝试了由三磷酸腈和铝组成的有机沸石的制备。加入三氧六环后得到的产物似乎具有三维骨架，尽管没有能够吸附氮气的纳米孔。

Synthesis of aluminomethylphosphonate membranes on a porous alumina substrate was attempted by using a hydrothermal method and steam-assisted conversion method. When pseudo-boehmite, methylphosphonic acid, water and t-butyl alcohol were mixed, part of the mixture solution was sucked into the substrate, and the substrate was dipped in the solution, followed by hydrothermal treatment in an autoclave at 160℃, AlMepO-β was crystallized to form a membrane-like aggregates on the substrate probably as a result of composite formation inside the substrate. When the -same mixture solution was sucked into the substrate, and the substrate was dried, followed by steaming in an autoclave, AlMepO-α membrane 40μm thick was obtained where crystallites were grown so as to closely contact on and in the substrate. However, the single gas permeation experiments of oxygen, air and hydrogen gas revealed negligible differences in permeance between the membranes and the substrate alone.Synthesis of organozeolites composed of metals and a phosphonate with a bulky group was investigated. Although it was not possible to obtain a nanoporous compound that can adsorb nitrogen, several compounds prepared had long-range order deilved from t-butylphosphonate. Especially, a Zn/t-butylphosphonate/methylphosphonate system gave a product with an XRD reflection at d=25Å, in which both the phosphonates are incorporated in the framework, when trioxane was added. Also organozeolites composed of nitrilotrisphosphonate and alumimum were attempted to prepare. The product obtained when trioxane was added seemed to possess a three-dimensional framework though there is no nanopore that can adsorb nitrogen.