Epoxidation of Propylene with Hydrogen Peroxide Over TS-1 Catalyst Synthesized in the Presence of Polystyrene

Titanium silicalite-1 (TS-1) catalyst was synthesized in the presence of polystyrene (PS) particles (denoted as TS-1_PS catalyst) for use in the epoxidation of propylene with hydrogen peroxide. For the purpose of comparison, TS-1 catalyst was also synthesized by a conventional method (in the absence of polystyrene particles). In the epoxidation of propylene, the TS-1_PS catalyst showed a higher conversion of hydrogen peroxide and a higher selectivity for propylene oxide (PO) than the TS-1 catalyst. Consequently, the TS-1_PS catalyst showed a higher yield for PO than the TS-1 catalyst. Characterization results showed that the high catalytic performance of TS-1_PS was attributed to the enhanced hydrophobic property of the catalyst and the suppressed formation of anatase TiO₂ in the catalyst.     

On the Limited Selectivity of Silica-Based Epoxidation Catalysts

Epoxidation of 2-cyclohexen-1-ol with TBHP and TiO₂–SiO₂, Fe₂O₃–SiO₂ and SiO₂ aerogels has been studied. The influence of surface silanol groups and transition metal impurities in titania–silica on the product distribution has been analyzed. The results, supported by literature data, indicate that high surface area silica cannot generally be regarded as an inert matrix in epoxidation catalysts. Contribution of Ti-free silica limits the selectivity of Ti- and Si-containing catalysts in demanding epoxidation reactions. The activity of silica – together with the background oxidation of the olefin – may lead to overestimated intrinsic activities when the reaction rate is related to the Ti content of the catalyst.     

Epoxidation of 1-hexene with hydrogen peroxide over nitrogen-incorporated TS-1 zeolite

Nitrogen-incorporated TS-1 zeolite (N-TS-1) was synthesized by direct calcining the as-synthesized TS-1 powder in NH₃ flow at high temperature. Epoxidation of 1-hexene with dilute H₂O₂ over N-TS-1 was studied. The results showed that the catalytic activity and selectivity of TS-1 were greatly improved upon post-synthetic nitridation. A new TiOOH intermediate with double hydrogen bonds was proposed. The new intermediate was more stable due to the presence of another hydrogen bond, which was formed between the stable nitrogen species and the H atom of the conventional five-member-ring intermediate, thereby improving the epoxidation activity.     

Gas-Phase Propylene Epoxidation over Ag/TS-1 Prepared in W/O Microemulsion: Effects of the Molar Ratio of Water to Surfactant and the Reaction Temperature

Ag/TS-1 was prepared by microemulsion method in which dioctyl sulfosuccinate sodium salt (AOT) was used as the surfactant and n-heptane as the organic solvent. The synthesized Ag/TS-1 was characterized by UV–Vis and TEM and its catalytic properties in gas-phase propylene epoxidation were carried out in a fixed bed reactor. The results show that Ag is highly dispersed on TS-1 and the crystal size can be adjusted through the adjusting of the molar ratio of water to surfactant ([H₂O]/[surfactant] = R). The catalyst prepared with R = 4.74 exhibits the highest catalytic activity for propylene epoxidation in gas-phase, the optimal reaction temperature scope is between 363 and 383 K. Over the catalyst prepared with R = 4.11, propylene conversion and the selectivity to propylene oxide (PO) are 1.1% and 91.0%, respectively.     

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.     

环氧丙烷的洁净生产技术TS-1催化丙烯环氧化过程研究进展

介绍了钛硅分子筛催化剂（ＴＳ－１）和它催化下的丙烯与Ｈ２Ｏ２的环氧化反应,以及以此为基础发展起来的环氧化过程与Ｈ２Ｏ２生产相结合的集成过程。     

EPOXIDATION OF FUNCTIONALIZED OLEFINS OVER SOLID CATALYSTS

Heterogeneous catalytic epoxidation of functionalized olefins in the liquid phase has been reviewed, focusing on catalyst performance and its interrelation with the crucial parameters of the catalytic systems. Efficient catalysts include supported and mixed oxides, framework-substituted (“redox”) molecular sieves, layered-type materials, heterogenized homogeneous catalysts, and some others. Among the various substrates, allylic and homoallylic alcohols, and unsaturated carbonyl compounds have received most attention so far. The great variety of available catalysts enables selective epoxidation of most substituted olefins. The mechanistic understanding of heterogeneous catalytic epoxidation is still underdeveloped, rendering catalyst design rather empirical. A considerable potential for future development lies in the area of “heterogenization” of successful homogeneous catalysts especially for asymmetric epoxidation. Crucial requirements in the development of heterogeneous catalytic epoxidation catalysts are, besides good catalytic performance and cheap oxidant, recyclability and resistance to leaching of the active component. Some of the examples shown in the literature do not fulfill the latter requirement.     

EPOXIDATION OF FUNCTIONALIZED OLEFINS OVER SOLID CATALYSTS

Heterogeneous catalytic epoxidation of functionalized olefins in the liquid phase has been reviewed, focusing on catalyst performance and its interrelation with the crucial parameters of the catalytic systems. Efficient catalysts include supported and mixed oxides, framework-substituted (“redox”) molecular sieves, layered-type materials, heterogenized homogeneous catalysts, and some others. Among the various substrates, allylic and homoallylic alcohols, and unsaturated carbonyl compounds have received most attention so far. The great variety of available catalysts enables selective epoxidation of most substituted olefins. The mechanistic understanding of heterogeneous catalytic epoxidation is still underdeveloped, rendering catalyst design rather empirical. A considerable potential for future development lies in the area of “heterogenization” of successful homogeneous catalysts especially for asymmetric epoxidation. Crucial requirements in the development of heterogeneous catalytic epoxidation catalysts are, besides good catalytic performance and cheap oxidant, recyclability and resistance to leaching of the active component. Some of the examples shown in the literature do not fulfill the latter requirement.     

Titanium silicate molecular sieves (TS-1 and TS-2) catalyzed Michael reaction of silyl enol ethers with α,β unsaturated carbonyl compounds

The Michael addition reaction has been carried out with silyl enol ether and Michael acceptors such as acrylates, and , - unsaturated ketones over aluminum-free titanium silicates (TS-1 and TS-2) in the absence of H₂O₂. The reaction was carried out slightly above room temperature (40°C) in the presence of dry solvents giving moderate to good yield. The effect of various modified zeolites like RE-Y, La-Y, steamed-Y, Na-Y, VS-1, SnS-1, Zn/ZSM-5 and different solvents has been studied. The catalytic activity is explained on the basis of oxophilic Lewis acidity of titanium silicate molecular sieves.     

Epoxidation of Styrene by Anhydrous H2O2 over TS-1 and γ-Al2O3 Catalysts: Effect of Reaction Water, Poisoning of Acid Sites and Presence of Base in the Reaction Mixture

The styrene conversion and product (viz. styrene oxide, phenyl acetaldehyde, benzaldehyde) selectivity in the liquid-phase epoxidation of styrene by H₂O₂ (H₂O₂/styrene = 2) over TS-1 (Si/Ti = 80) and -Al₂O₃ are strongly influenced by the presence of water and/or base (viz. urea and pyridine) in the reaction mixture. The TS-1 showed high styrene conversion activity but no epoxide selectivity in the absence of any base. When anhydrous H₂O₂ (24% H₂O₂ in ethyl acetate), with the continuous removal of the reaction water (using the DeanStark trap), was used instead of 50% aqueous H₂O₂, both the conversion and epoxide yield are increased drastically for the -Al₂O₃, whereas for the TS-1, the increase in the conversion was quite small and there was also no improvement in the epoxide selectivity and/or yield. However, when urea or pyridine was added in the reaction mixture, the epoxide selectivity for both the catalysts was increased depending on the concentration of the base added; the increase in the selectivity was very large for the TS-1 but small for the -Al₂O₃. Poisoning of the acid sites of the -Al₂O₃ by the chemisorbed ammonia or pyridine (at 100 °C) caused a small decrease in the conversion, but it also caused a large decrease in the epoxide selectivity. However, the pyridine poisoning of the TS-1 caused a little beneficial effect, a small increase in the epoxide selectivity. The ammonia poisoning of the TS-1, however, resulted in a small decrease in the conversion with no improvement in the epoxide selectivity. As compared to the TS-1, the -Al₂O₃ catalyst showed a much better performance in the epoxidation by anhydrous H₂O₂ with the continuous removal of the reaction water. However, the reaction water, if not removed continuously, is detrimental to the -Al₂O₃, causing a large decrease in the catalytic activity and selectivity for styrene oxide but an increase in the selectivity for benzaldehyde.     

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。     

Silica islands regulated external Ti-site environment of TS-1 for enhanced performance of 1-hexene epoxidation

Rational regulation of the local environment of Ti-sites in TS-1 harbors tremendous industrial and scientific significance to epoxidation reactions. Herein, we report a facile and environment-friendly strategy to boost catalytic selectivity by covering the Ti-sites on an external surface of TS-1 (ITS-1) without sacrificing activity of internal Ti sites. By a quantitative analysis of d₃-acetonitrile and quinoline-DRIFTS, ¹H MAS NMR and XPS, it is found that the percentage of external Ti-sites decreased from 11% to 6% after depositing surface silica islands. This successfully inhibits ring-opening reaction of 1,2-epoxyhexane on catalyst surface, as demonstrated by slower kinetic decomposition rate of 1,2-epoxyhexane. Compared with conventional TS-1 catalyst, selectivity of 1,2-epoxyhexane over ITS-1 catalyst significantly increased from 83.5% to 98.5% while maintaining high 1-hexene conversion. Furthermore, overmuch surface silica coverage only leads to extremely low conversion (2%) due to inhibition of mass transfer. This work paves the way for rational construction of Ti-containing catalysts for 1-hexene epoxidation.     

Epoxidation of Linear Olefins over Stacked TS-1 Zeolite Catalysts

Stacked TS-1 [NSTS-1(MW)] has been prepared by microwave synthesis and applied to the epoxidation of linear olefins with H₂O₂ under mild conditions, and the epoxidation activities were compared with the non-stacked TS-1 and the conventional TS-1, which were also synthesized by microwave and by typical hydrothermal method, respectively. Stacking of TS-1 crystals was accomplished by using microwave which facilitated the dehydration of hydroxyl groups on the external surface of crystallites through the selective absorption of microwave onto Ti species. The stacked crystallites seemed to allow the running pore structure in the b-axis orientation through the crystallites in the stacked morphology. Besides this unique pore structure, the stacked TS-1 showed peculiar features like higher hydrophobicity and enhanced catalytic property than typical TS-1. Moreover, the NSTS-1(MW) showed the highest activity in the epoxidation of linear olefins among three catalysts, and also coincided with the differences in the adsorption of linear aliphatics due to strong interaction with the straight channel in the stacked morphology, which gave larger Henry’s constants, obtained by the tracer chromatographic analysis, as the increase in the carbon chain length.     

Kinetics simulation of propylene epoxidation over different Ti species in TS-1

A thorough experimental investigation on the kinetic behavior of liquid-phase propylene epoxidation over TS-1 and tetrapropylammonium hydroxide (TPAOH) treated TS-1 catalysts was conducted in a fixed-bed reactor. The amounts of different coordinated Ti species in the catalysts were quantified by spectroscopies, and their catalytic performances of the epoxidation and alcoholysis of propylene oxide were measured by kinetic modeling. The study shows that the TPAOH treatment converted some of the tetrahedrally coordinated Ti to octahedrally coordinated Ti, and both species were active for the epoxidation and alcoholysis. The superior catalytic performance observed over the TPAOH treated TS-1 is due to two factors, the increased percentage of active sites, and reduced energy barrier for epoxidation on the octahedrally coordinated Ti. In addition, as the H₂O₂ conversion increases, the adsorption equilibrium constant of propylene oxide plays a more decisive role than the activation energy for the selectivity of propylene glycol monomethyl ethers.     

TiO2–ZrO2 mixed oxide as a support for hydrotreating catalyst

Pure TiO₂, ZrO₂ and TiO₂–ZrO₂ mixed oxides are prepared by urea hydrolysis. Hydrotreating catalysts containing 12 wt% molybdenum are prepared using these oxides and characterized by BET surface area, pore volume, XRD and oxygen chemisorption. It is observed that oxides produced by the method of urea hydrolysis have higher surface area as compared to those available commercially. With increasing zirconia content in the mixed oxide, the surface area increases and a maximum value is obtained for a mixed oxide having Ti and Zr molar ratio of 65/35. XRD results indicate that mixed oxides are poorly crystalline in nature. Thiophene hydrodesulfurization, cyclohexene hydrogenation and tetrahydrofuran hydrodeoxygenation are taken as model reactions for evaluating catalytic activities. It is found that both O₂ uptake and catalytic activities increase with increasing zirconia content in mixed oxide and reach maximum values for the 12 wt% Mo/TiO₂–ZrO₂ (65/35) catalyst. With further increases in zirconia content, O₂ uptake and catalytic activities decrease and the lowest values are observed for the pure ZrO₂ supported catalyst.     

Uncalcined TS-2 immobilized Au nanoparticles as a bifunctional catalyst to boost direct propylene epoxidation with H2 and O2

Developing stable yet efficient Au–Ti bifunctional catalysts is important but challenging for direct propylene epoxidation with H₂ and O₂. This work describes a novel strategy of employing uncalcined titanium silicalite-2 (TS-2-B) to immobilize Au nanoparticles as a bifunctional catalyst for the reaction. Under no promoter effects, the Au/TS-2-B catalyst compared to the referenced Au/TS-1-B catalyst delivers outstanding catalytic performance, that is, exceptionally high stability over 100 hr, propylene oxide (PO) formation rate of 118 g_PO·hr⁻¹·kg_cat⁻¹, PO selectivity of 90% and hydrogen efficiency of 35%. The plausible relationship of catalyst structure and performance is established by using multiple techniques, such as UV–vis, high-angle annular dark-field scanning transmission electron microscopy, thermogravimetric analysis, and X-ray photoelectron spectroscopy. A unique synergy of Au–Ti⁴⁺–Ti³⁺ triple sites is proposed for our developed Au/TS-2-B catalyst with the higher stable PO formation rate and hydrogen efficiency. The insights reported here could shed new light on the rational design of highly stable and efficient Au–Ti bifunctional catalysts for the reaction.     

Synthesis of TS-1 by microwave heating of template-impregnated SiO2–TiO2 xerogels

TS-1 was prepared by microwave heating of a SiO₂–TiO₂ xerogel dry-impregnated with the template, TPAOH. A highly crystalline product was obtained within 30 min after microwave irradiation with yields over 90%. These are significant advantages over the TS-1 obtained by conventional oven heating using alkoxide precursors in liquid phase, which requires 1–2 day crystallization time with low product yields. Characterization of the TS-1 obtained was carried out using XRD, SEM, FT-IR, and UV-vis spectroscopy, and catalytic activity was examined for 1-hexene epoxidation using H₂O₂ as oxidant. These studies revealed that the material obtained by microwave heating of the mixed oxide gel shows essentially identical physicochemical properties to those prepared by conventional means.     

Propylene Epoxidation Over Silver Supported on Titanium Silicalite Zeolite

Epoxidation of propylene to propylene oxide over Ag/TS-1 in the presence of oxygen and hydrogen was carried out in a fixed-bed, quartz flow reactor. The effects of Ag loading, Si/Ti ratio of TS-1 and calcination temperature and calcination method of Ag/TS-1 on the propylene epoxidation were investigated. The results show that Ag loading, the calcination temperature and calcination method of Ag/TS-1 as well as the Si/Ti ratio of TS-1 have a great effect on the catalytic properties. The optimum Ag loading, calcination temperature and calcination method of Ag/TS-1 and Si/Ti ratio of TS-1 are 2 wt%, 450 °C in air and 64 respectively. Over 2.0 wt% Ag/TS-1(n_Si/n_Ti = 64) catalyst, at a space velocity of 3000 h^-1, 0.92% propylene conversion with 91.21% selectivity to propylene oxide is obtained at 150 °C. The deactivation of Ag/TS-1 catalyst is not due to the changes of active species, but because of the coke of the catalyst, which can be easily regenerated by calcination at 450 °C in air.     

Characterization and catalytic properties of titanium silicalite-1 catalyst

Titanium silicalite 1 (TS-1) catalyst was prepared by three different hydrothermal synthesis methods. XRD, elemental analysis, SEM, IR,²⁹Si MAS NMR, UV-vis DRS, physical adsorption of nitrogen, and EXAFS analysis were then performed to evaluate its physical properties. For a test of catalytic activity, liquid phase 2-butanol oxidation and 1-hexene epoxidation using hydrogen peroxide as an oxidant were conducted. The crystal size of the TS-1 catalyst was shown to have a considerable effect on the 1-hexene epoxidation, and smaller crystals resulted in higher activity.     

Author Index

Catalytic epoxidation of styrene with hydrogen peroxide over copper hydroxyphosphate Cu₂(OH)PO₄ was studied. Catalytic data shows that the catalyst Cu₂(OH)PO₄ is very active, and the main products are styrene epoxide and benzaldehyde, particlularly giving high selectivity for styrene epoxide. In contrast, over TS-1 a large amount of phenylacetaldehyde product is formed. Some important factors associated with the catalytic activity and selectivity are investigated extensively.