Selective Production of Intermediate Compounds of Reaction In Series by Use of Catalytic Zeolite Membrane Reactor

沸石是晶态硅酸铝，广泛用作催化剂和吸附剂。MFI型沸石的晶体内有细小的孔隙，其直径与苯的分子尺寸几乎相同。因此，该沸石具有较高的分子筛分效果。当成功将沸石制备成膜的形状时，该膜可以实现新的分离和高性能的同时反应和分离。本项目的主要目标是开发MFI型分子筛催化膜，并将其应用于高分离和同时反应分离过程。通过本研究工作，我们在2001财年取得了以下成果：(1)采用均匀混合水热合成法成功制备了无针孔的MFI型催化膜。(2)采用液相氧化法成功制备了高耐酸亲水性分子筛膜。这种膜只允许水渗透。(3)我们开发了一种控制沸石孔径和酸性中心位置分布的新方法，称为硅烷催化裂解(CCS)法。当采用二乙氧基甲基硅烷作为CCS法时，孔内的有效孔径减小。2002财年，采用三苯基硅烷的CCS法控制沸石膜上活性中心(酸中心)的分布，制备了孔内仅含酸中心的分子筛膜。用该膜进行甲醇反应，在甲醇转化率为0~70%，渗透液侧与进料侧压降为零的条件下，可制得选择性在85%以上的有用烯烃。

Zeolites are crystalline alumino-silicate, and widely used as catalysts and adsorbents. MFI-type zeolite has fine pores within its crystals, the diameter of which is almost the same as the molecular size of benzene. Hence, the zeolite shows high molecular-sieving effect. When the zeolite is succeeded to be prepare in the shape of membrane, the membrane can enable to realize new separation and simultaneous reaction and separation with high performance. The main objective of this project is to development of MFI-type zeolite catalytic membrane, and to apply it to high separation and simultaneous reaction and separation processes. We obtained the following results through this research work :In fiscal year of 2001 :(1) MFI-type catalytic membrane was succeeded to prepared without any pin-holes by a new method, well-mixed hydrothermal synthesis.(2) Hydrophilic zeolite membrane with high acid-proof was successively prepared by the liquid phase oxidation method. This membrane allows the permeation for only water.(3) We developed a new method, called "Catalytic Cracking of Silane (CCS) method", for controlling the pore diameter and the location of acid sites distribution of zeolite. When diethoxymethyl-silane was employed for the CCS method, the effective pore diameter was decreased in pores. On the other hand, tri-phenyl silane was used, the effective pore diameter was decreased only at pore months.In fiscal year of 2002 :The CCS method with tri-phenyl sliane was applied to contorol the distribution of active sites (acid sites) on the zeolite membranes, to prepared the membrane with acid sites only within pores. When the reaction of methanol was conducted by use of this treated membrane, useful olefins were produced at selectivity above 85% under the conditions of the conversion of methanol of around 0 to 70% and zero pressure drop between the permeate and the feed sides.