权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

Liquid-phase oxidation process using titanosilicate catalysts with mordenite structure.

使用具有丝光沸石结构的钛硅酸盐催化剂的液相氧化过程。

基本信息

批准号：
07555248
负责人：
YASHIMA Tatsuaki
金额：
$ 6.4万
依托单位：
TOKYO INSTITUTE OF TECHNOLOGY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1997
项目状态：
已结题

项目摘要

Titanosilicate with mordenite structure was prepared by Atom-planting method using dealuminated mordenite and TiCl_4. A strong absorption at 220 nm in UV spectra indicated tetrahedral coordination of Ti species. An absorption band also appeared at 963 cm^<-1> in IR spectra. Its absorbance was in proportion to the concentration of Ti. This was an evidence of framework incorporation of all the Ti species. A TiCl_4 reacts with a defect site, hydroxyl nest, to form four Ti-O-Si bonds.Liquid-phase hydroxylation of toluene with hydrogen peroxide was carried out on titanosilicate. Cresol isomers were produced with selectivity higher than 99%. Turnover number (TON) increased with increasing hydrophobisity of catalyst by dealumination. Benzene, ethylbenzene and cumene gave almost the same TON as toluene, while TON in the hydroxylation of t-butylbenzene was much lower. On MFI-type titanosilicate, however, only benzene was reacted with the same TON ; the others showed much less reactivity. It was revealed that titanosilicate with mordenite structure is effective catalyst for the hydroxylation of large aromatic molecules compared with that with MFI structure. The framework Ti species in titanosilicate catalyzes ammoximation of ketones with ammonia and hydrogen peroxide, because absorbance of the 963 cm^<-1> IR band was in proportion to the reaction rate of ammoximation. Dealumination of the parent mordenite caused the increase in oxime selectivity as well as activity through the increase in hydrophobic nature of the catalyst.

以脱铝丝光沸石和TiCl_4为原料，采用原子植入法制备了丝光沸石结构的钛硅酸盐。紫外光谱在220 nm处有较强的吸收，表明Ti物种为四面体配位。在红外光谱中，在963 cm-1处也出现吸收带<-1>。其吸光度与钛的浓度成正比。这是所有Ti物质的骨架结合的证据。一个TiCl_4与一个缺陷位羟基巢反应生成四个Ti-O-Si键。以高于99%的选择性生产甲酚异构体。转化率（TON）随着脱铝催化剂疏水性的增加而增加。苯、乙苯和异丙苯的TON几乎与甲苯相同，而叔丁基苯羟基化的TON要低得多。然而，在MFI型钛硅酸盐上，只有苯与相同的TON反应;其他的反应性要小得多。结果表明，丝光沸石结构的钛硅酸盐催化剂对芳香族大分子羟基化反应的催化效果优于MFI结构的钛硅酸盐催化剂。钛硅酸盐中的骨架Ti物种催化酮与氨和过氧化氢的氨肟化反应，因为963 cm-1 IR带的吸光度<-1>与氨肟化反应速率成比例。脱铝的母体丝光沸石引起的增加肟的选择性以及通过增加催化剂的疏水性的活性。