Development of novel organozeolites and application to adsorption separation

采用水热法和水蒸气辅助转化法在多孔氧化铝基底上制备了甲基膦酸铝盐膜。将拟薄水铝石、甲基膦酸、水和叔丁醇混合后，将部分混合溶液吸入基材中，浸渍基材，然后在160℃高压釜中进行水热处理，AlMepO-β在基材上结晶形成膜状聚集体，可能是在基材内部形成复合物的结果。当将相同的混合物溶液吸入基底中，并干燥基底，然后在高压釜中蒸汽处理时，获得40μm厚的AlMepO-α膜，其中微晶生长为在基底上和基底中紧密接触。然而，氧气，空气和氢气的单一气体渗透实验显示膜和基底之间的渗透率的差异可以忽略不计。合成的有机沸石由金属和膦酸酯与一个庞大的基团进行了研究。虽然不可能获得可以吸附氮的纳米多孔化合物，但制备的几种化合物具有从叔丁基膦酸酯衍生的长程有序。特别地，当加入三恶烷时，Zn/叔丁基膦酸酯/甲基膦酸酯体系给出了在d=25 nm处具有XRD反射的产物，其中两种膦酸酯都并入骨架中。还尝试了由次氮基三膦酸酯和铝组成的有机沸石的制备。当加入三恶烷时获得的产物似乎具有三维骨架，尽管没有可以吸附氮的纳米孔。

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.