Synthesis of Some Kinds of Metallosilicates by Atom-Planting Method and Their Catalytic Properties

原子植入法合成几种金属硅酸盐及其催化性能

基本信息

批准号：
03453083
负责人：
YASHIMA Tatsuaki
金额：
$ 4.48万
依托单位：
Tokyo Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1991
资助国家：
日本
起止时间：
1991 至 1993
项目状态：
已结题

项目摘要

Some kinds of metallosilicate could be prepared by Atom-Planting method using highly silicious MFI type zeolite and dealuminated mordenite, and metal chlorides. When vapor of metal chloride contacts with highly silicious zeolites at the higher temperatures, the metal cation can occupy the defect sites in zeolite framework.The acidity of metallosilicates ion-exchanged by proton deferred to the kind of trivalent metal cation inserted into the framework. The order of acid strength of some metallosilicates was measured as follows ;As-> Ga-> Fe-> In-> Sb-> As-When these metallosilicates were used as a catalyst for the alkylation of monoalkylbenzene, the fraction of para isomer in dialkylbenzene produced reached 80-100%. It can be concluded from the results obtained by using metallosilicate catalysts with same pore window size but different acid strength that para isomer is shape-selectively produced through the transition state restriction.The transition-metal cation inserted into the zeolite framework was a tetrahedral state and was not easily reduced nor oxidized. Therefore, it is expected that the catalytic properties of transition-metal cations in zeolite framework would be different from those in oxides and coplex compounds. Iron cation with tri-valent state in zeolite framework showed the high activity for the oxidative dehydrogenation and the low activity for the complete oxidation of lower paraffins, while iron oxide showed the high activity for the complete oxidation of lower paraffins. On the other hand, titanosilicate with mordenite type structure could be prepared by Atom-Planting method, and showed high catalytic activity for the liquid phase hydroxylation of benzene ring with hydrogen peroxide.From these results it is concluded that Atom-Planting is a good method for the preparation of metallosilicates and these metallosilicates will show the unique catalytic properties for some reactions.

可以使用高度硅酸盐的MFI型沸石和交易的灰矿和金属氯化物来制备某些类型的金属硅酸盐。当金属氯化物与高度温度下的高度硅质沸石的蒸气时，金属阳离子可以占据沸石框架中的缺陷位点。金属纤维素的酸度是由质子递延到插入框架中的三价金属阳离子的质子的离子离子的酸性。测量某些金属硅酸盐的酸强度顺序如下； as->> ga-> fe-> in-> in-> in-> sb-> as-当这些金属纤维酸盐用作单烷基苯烯烷基化的催化剂时Diarkylbenzene产生的达到80-100％。可以通过使用具有相同孔隙窗口尺寸的金属硅酸盐催化剂获得的结果得出结论，但帕拉异构体是通过过渡状态限制形状选择性产生的不同酸强度。不容易减少或氧化。因此，预计沸石框架中过渡金属阳离子的催化特性将与氧化物和旋转化合物中的催化特性不同。在沸石框架中具有三价状态的铁阳离子显示出氧化脱氢作用的高活性，而在下部石蜡完全氧化中具有低活性，而氧化铁则表现出高的氧化活性，用于完全氧化下部石蜡的完全氧化。另一方面，可以通过原子植入方法制备钛硅酸盐，并可以制备高催化活性，用于用过氧化氢的苯环液相羟基化。为了制备金属硅酸盐和这些金属硅酸盐将显示一些反应的独特催化特性。