Development of novel organozeolites and application to adsorption separation

采用水热法和蒸汽辅助转化法在多孔氧化铝基体上合成了甲基膦酸铝膜。将拟薄水铝石、甲基膦酸、水和t-丁醇混合后，将部分混合溶液吸入底物中，将底物浸入溶液中，然后在160℃的高压釜中进行水热处理，AlMepO-β结晶，在底物上形成膜状聚集体，这可能是底物内部复合形成的结果。将相同的混合溶液吸入衬底，干燥衬底，然后在高压灭菌器中蒸煮，得到40μm厚的AlMepO-α膜，膜上生长有晶体，并与衬底紧密接触。然而，氧气、空气和氢气的单一气体渗透实验表明，膜与单独的底物之间的渗透差异可以忽略不计。研究了由金属和一大块基团的膦酸盐组成的有机沸石的合成。虽然不可能获得可以吸附氮的纳米多孔化合物，但所制备的几种化合物具有从膦酸丁酯中分离出来的长阶。特别是在锌/膦酸t-丁酯/膦酸甲酯体系中，当加入三氧环时，两种膦酸盐均加入骨架中，产物的XRD反射值为d=25Å。并尝试制备了由三磷酸硝基和铝组成的有机沸石。虽然没有吸附氮的纳米孔，但加入三氧环后得到的产物似乎具有三维骨架。

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.