钛硅分子筛TS-1合成及催化环己酮氨氧化的研究进展

钛硅分子筛TS- 1催化的环己酮氨氧化反应是一个绿色过程。介绍了TS- 1分子筛的合成、TS- 1分子筛催化的环己酮氨氧化及环己酮氨氧化与过氧化氢生产的集成。指出提高催化剂的性能、降低其生产成本是今后研究的重点 ,绿色氧化剂过氧化氢的生产与氨氧化过程的集成是今后环己酮肟生产的发展方向     

钛硅分子筛TS-1催化烯烃环氧化反应的研究进展

TS-1催化的烯烃环氧化反应具有条件温和、环境友好、符合绿色化学理念、应用前景广阔等优点.该文首先介绍了不同介质中TS-1催化过氧化氢(H2O2)氧化脂肪烯烃反应的进展,结果表明,在甲醇等质子溶剂中,溶剂可以和Ti—OOH(钛氧活性中心)通过氢键作用形成活性中间体,实现烯烃的环氧化;同时,TS-1的酸中心易引发环氧化物...     

钛硅分子筛TS-1催化合成4-甲基邻苯二酚的研究

采用清洁生产工艺,以钛硅分子筛TS-1为催化剂,使用绿色氧化剂低浓度H2O2水溶液氧化合成4-甲基邻苯二酚,并考察了影响产品收率的主要因素。结果表明,在n（过化氢）：n（4-甲酚）=0．33,催化剂用量为10％,反应温度：83℃,滴加30％H2O2水溶液,滴加时间4h,滴加完毕后继续反应2h的条件下,4-甲酚转化率：21．82％,4-甲基邻苯二酚收率：15．86％,选择性：72．7％。     

钛硅分子筛TS-1动态过滤的研究

对钛硅分子筛TS 1微粉催化剂应用动态过滤技术 ,在动态旋叶压滤机上进行了过滤性能的研究 ,得到了过滤速率随时间的变化规律 ,并分析了操作压力对过滤速率的影响。为了结合实际工业生产的要求 ,对过滤介质进行了再生实验。该研究为TS 1微粉催化剂的过滤分离提供了一个可行的方法 ,为确定适宜的操作条件及工业应用提供了实验依据     

钛硅分子筛(TS-1)催化氧化二甲基硫醚制备二甲基砜的研究

以二甲基硫醚和双氧水为原料、钛硅分子筛为催化剂制备了二甲基砜,确定了最佳工艺条件,即常温下钛硅分子筛为二甲基硫醚质量的7%,二甲基硫醚与双氧水的摩尔比1∶1.05,反应时间1.5 h,二甲基硫醚转化率达99%以上,二甲基砜收率达98%以上。     

钛硅分子筛的技术现状及国内专利分析

钛硅分子筛由于其优异的催化氧化性能而受到极大关注,已成为催化领域的一个研究热点。简述了钛硅分子筛发展历程、合成概况和在有机领域的应用,重点分析了国内钛硅分子筛的相关专利分布情况,主要从国内钛硅分子筛的专利申请量年度分布情况、申请人类型统计和申请人排名情况3个方面进行统计分析,通过对数据的比较和分析,得出了我国的钛硅分子筛材料的研究现状、应用水平和研究趋势,并展望了钛硅分子筛材料今后的发展方向。     

基于羧酸改性TS-1分子筛的制备与环氧化性能研究

钛硅分子筛（TS-1分子筛）催化烯烃环氧化反应具有条件温和、环境友好等特点。以有机羧酸代替传统的无机酸TS-1分子筛的处理,有效降低了TS-1分子筛的非骨架钛含量。有机羧酸的酸性相对无机酸较弱,对骨架钛的损害较小。并且,TS-1分子筛在煅烧时,有机酸根会降解并逸出体系,不会形成额外的酸性位点。在3-氯丙烯环氧化反应中,三氯乙酸处理后的TS-1分子筛具有较高的环氧氯丙烷选择性和收率以及H2O2利用率。此外,三氯乙酸处理后的TS-1分子筛具有良好重复性能,以及更长的使用寿命。由此可见,三氯乙酸等有机酸可以有效替代盐酸等无机酸对TS-1分子筛进行处理。     

钛硅分子筛TS-1合成及应用的研究进展

综述了钛硅分子筛TS－1合成，表征以及催化性能方面的研究进展，着重讨论了合成过程中影响钛进入分析筛骨架的因素，详细介绍了XRD，FT－IR，UV－Vis,XPS,^29SiMAS,NMR等表征技术对TS－1分子筛的分析结果。TS－1双氧水体系的应用研究进展。     

催化新材料—钛硅分子筛的制备与应用

对具有独特氧化性能的含钛分子筛的制备和应用进行了述评,简述了ＴＳ－１,ＴＳ－２,Ｔｉ－ＭＣＭ－４,Ｔｉ－ＨＭＳ,Ｔｉ－β型等含钛分子筛的合成及合成中不同的硅源,钛源,模板剂,合成条件对结构性能的影响。介绍了含钛分子筛在苯与苯酚的羟基化,烯烃的环氧化,环己酮的肟化,妥和饱和烃的氧化等反应中的应用及催化的作用机理,并对钛硅分子筛研究中存在的问题和应用前景提出了看法。     

无机钛硅原料体系TS-1催化环己酮氨氧化反应的研究

研究了自制的无机钛硅原料体系TS - 1催化环己酮氨氧化反应 ,结果表明 :钛进入了分子筛的骨架中 ,构成了TS - 1催化活性中心。考察了以水为溶剂时 ,催化剂用量、氧酮比、氨氧比对氨氧化反应的影响 ,得出了无机钛硅原料体系TS - 1催化环己酮氨氧化反应的最优反应条件。在此条件下 ,环己酮的转化率可达 97%以上 ,环已酮肟的收率可达 96 %     

纳米TS-1分子筛的合成及环己酮肟化反应性能

采用预晶化后补充硅源的合成方法,在模硅物质的量比0.15条件下,合成晶粒尺寸300 nm的TS-1分子筛。考察模板剂用量和预晶化时间对分子筛合成的影响,并采用XRD、SEM、TEM、UV-vis和N2吸附-脱附对分子筛进行表征,通过环己酮肟化反应考察分子筛催化性能。结果表明,相对于传统法合成的TS-1分子筛,采用预晶化补硅法合成的TS-1分子筛具有较大的比表面积和介孔体积,而且其非骨架钛含量减少,能够有效地提高环己酮肟化反应的转化率、选择性和催化剂寿命。     

Epoxidation of allyl alcohol to glycidol using titanium silicalite TS-1: effect of the method of preparation

The epoxidation of allyl alcohol with hydrogen peroxide catalysed by the microporous titanium silicalite TS-1 has been investigated with respect to the effect of the method of catalyst preparation. Three methods of TS-1 synthesis have been studied using the standard tetrapropyl-ammonium cation as template (i) using tetraethyl orthosilicate, tetraethyl orthotitanate as reagents, (ii) using a fluoride method and (iii) using tetrabutyl orthotitanate as the titanium source. The TS-1 samples were characterised by electron microscopy, X-ray diffraction and infrared spectroscopy. The method of preparation controlled the morphology of the TS-1 crystals and in particular the crystallisation time was found to be an important parameter. Data are presented that correlate the activity for the epoxidation of allyl alcohol with the morphology of TS-1. In addition it is found that the catalytic activity of TS-1 for this reaction is not related to the intensity or presence of the infrared absorption band at ca. 960 cm^–1.     

低成本TS-1分子筛的制备及其苯酚羟基化性能研究

以四丙基氢氧化铵为模板剂,采用较低碱浓度水解成胶和较高模板剂浓度晶化的新工艺合成了低成本的TS-1分子筛,并优化了合成条件。样品的XRD和FT-IR表征证明,Ti原子成功进入分子筛的骨架中。结果表明,在水解成胶碱浓度为8%左右、晶化模板剂浓度20%时合成的TS-1分子筛,其催化苯酚羟基化反应中,苯酚的转化率达到20.56%。该合成在保证TS-1分子筛高催化活性的基础上,模板剂四丙基氢氧化铵（TPAOH）的用量明显降低,从而大大降低合成成本。     

Effects of TS-1 zeolite structures on physical properties and enzymatic degradation of Poly (butylene succinate) (PBS)/TS-1 zeolite hybrid composites

The objective of this study was to investigate how the water uptake features and carrier characteristics of the TS-1 zeolite affected the physical and rheological properties, morphological parameters, and enzymatic hydrolysis of Poly (butylene succinate) (PBS). The introduction of TS-1 zeolite as catalyst was developed for the preparation of PBS/TS-1 zeolite hybrid composites (PTHC) without heavy metal toxic substance in the context on clean technology. The TS-1 zeolite can act as a catalyst as well as a reinforcement filler with the result that PTHC can show marked increases in tensile properties and elongation at breakage in the solid state. The rheological properties of PTHC with high zeolite contents showed low values of complex viscosity, as compared with PTHC with low TS-1 zeolite contents, due to the volatilization of water released from the zeolite pores during esterification. The introduction of the TS-1 zeolite in the PBS matrix was not significantly affected by changes in the size of the long period, lamella thickness, or the amorphous region, indicating that PBS chains do not penetrate into zeolite pores, as confirmed by SAXS profiles. In enzymatic hydrolysis over 90 days, the enzymatic hydrolysis rates of PTHC significantly accelerated with increasing TS-1 zeolite contents, compared with Homo PBS. This result indicated that TS-1 zeolite can act as a carrier for enzyme activation, resulting in enzymatic hydrolysis, occurring from the amorphous area on the surface into the inside of the film.     

Selective oxidation of secondary amines over titanium silicalite molecular sieves,TS-1 and TS-2

Titanium silicalite molecular sieves, TS-1 and TS-2 having MFI and MEL structures, respectively, catalyze the oxidation of secondary amines to the corresponding hydroxylamines using hydrogen peroxide as the oxidant. Higher concentrations of H₂O₂ lead to further oxidation of hydroxylamine to nitrone. Diffuse reflectance spectroscopy shows the formation of a titanium peroxo complex upon addition of hydrogen peroxide to the TS-1 catalyst. The titanium peroxo complex oxidizes the substrate and reforms to a titanyl group.     

纳米尺度高配位活性钛TS-1的制备及性能评价

采用低成本模板剂和硅源（四丙基溴化铵和硅溶胶）,利用蒸汽辅助干胶晶化法,通过添加晶种的方式合成出纳米级TS-1分子筛。再经二次水热晶化,采用乙胺和四丙基溴化铵的混合溶液对其进行处理,制备出了含有六配位钛的高活性TS-1分子筛。采用X射线衍射、紫外漫反射可见光谱、紫外拉曼光谱、傅里叶变换红外光谱、固体核磁共振、N2物理吸附-脱附等手段对其物理化学性质等进行表征,并考察其对丙烯环氧化反应的催化性能。结果表明,纳米级TS-1分子筛后处理生成了活性更为优异的六配位钛物种,且其孔道结构得到了改善,比表面积明显增大;其催化丙烯环氧化反应的活性明显提高,双氧水转化率由47.59%增至85.79%,有了明显的提升。     

无机方法制TS-1催化剂上的环己酮氨氧化反应

用无机方法合成了钛硅分子筛催化剂TS-1,并优化了TS-1催化环己酮氨氧化反应的条件。结果表明,无机催化剂可以取代有机催化剂。同时,物料比、溶剂以及温度都对氨氧化反应有很大影响。适当调整反应条件,可得到较好的结果。其最优的反应条件为：n(氨)∶n(酮)＝2,n(H₂O₂)∶n(酮)＝1.5,溶剂用蒸馏水,n(水)∶n(酮)＝7.5,反应温度为74 ℃。     

TS-1合成时晶种与模板剂的协同导向作用

在无机钛硅原料体系合成TS - 1时 ,加入晶种 ,模板剂TPABr (orTPAOH)的用量大量减少甚至可以低于极限用量。实验发现晶种和模板剂具有协同导向作用 ,并对产生这种协同作用进行了讨论。     

Epoxidation of allyl alcohol to glycidol using titanium silicalite TS-1: effect of the reaction conditions and catalyst acidity

The epoxidation of allyl alcohol to glycidol using the titanium silicalite TS-1 with hydrogen peroxide as the oxidant is described and discussed in detail. The reaction conditions (alcohol, solvent, temperature) required to obtain 100% selectivity to glycidol are described and this selectivity has been observed at conversions of allyl alcohol of up to 20%. Addition of excess hydrogen peroxide enhances conversion but does not appear to affect selectivity to glycidol deleteriously, whereas addition of hydrogen peroxide over an extended time period is not particularly beneficial. The major side reactions are the oxidation of the alcohol solvent and the ring opening solvolysis of the glycidol that leads to the formation of alkoxy diols. Base treatment of the TS-1 using sodium azide enhances the glycidol selectivity, whereas the incorporation of Brønsted acid sites by addition of aluminium into the framework structure of TS-1 enhances the selectivity to the products of solvolysis ring opening reactions.