Preparation of aldoxime through direct ammoximation using titanium silicalite-1 catalyst

The liquid phase direct ammoximation of 5-isooctyl salicylaldehyde with ammonia and hydrogen peroxide was studied using titanium silicalite-1(TS-1)catalyst.The effect of reaction parameters on the yield of the product was studied,which include reaction temperature,reaction time,molar ratio of ammonia to aldehyde as well as hydrogen peroxide to aldehyde.The influence of the amount of catalyst on the reaction results was also investigated.The maximum 5-isooctyl salicylaldoxime yield of 98.76%was achieved under the following optimal reaction conditions:the molar ratio of 5-isooctylaldehyde to hydrogen peroxide and ammonia of 1:1.4:1.6,the reaction temperature of 70℃,the amount of TS-1 of 17.5 g·mol^(-1)(5-isooctyl salicylaldehyde),and the feeding time of 2 h.This method has the mild reaction conditions and avoids the shortcomings of traditional methods.Moreover,useless inorganic salts by-products are avoided,and there is no environmental pollution.

Titanium Silicalite-1的合成和应用进展

综述了Titanium silicalite-1分子筛国内外在降低合成成本方面的进展,并介绍了其催化应用。

A Novel Method for Synthesizing p-Benzoquinone by Direct Catalytic Oxidation of Benzene with Hydrogen Peroxide over Copper-Doped TS-1

E xisting methods for synthesizing p -benzoquinone have drawbacks with respect to environmental protection, production scale, or industrial value. Therefore, it is imperative that a simple and environmentally friendly alternative be developed. The approach that involves preparing p -benzoquinone by the catalytic oxidation of benzene with hydrogen peroxide (H 2 O 2 ) over copper-modi ed titanium silicalite-1 (Cu/TS-1) has a certain superiority due to its green synthesis and mild reaction condi- tions. In this study, Cu/TS-1 catalyst was prepared by the wet impregnation of TS-1 with an aqueous solution of Cu(NO 3 ) 2 and then characterized by X-ray di raction, Fourier transform infrared spectroscopy, di use re ectance UV Vis spectros- copy, scanning electron microscopy, inductively coupled plasma mass spectrometry, X-ray uorescence, and analysis of the N 2 adsorption desorption isotherms. The results reveal that Cu species exist mainly in the form of amorphous CuO that is well dispersed on the surface of catalysts, with no major change in the molecular sieve framework. After optimizing the reaction conditions, a desirable p -benzoquinone selectivity (88.4%) and benzene conversion (18.3%) were obtained when the doping of Cu in Cu/TS-1 is 1.95 wt%. In addition, Cu/TS-1 can be conveniently regenerated, showing a slight decrease in catalytic capability after initial use, which then stabilizes in subsequent circulations. The satisfactory stability and low cost of synthesizing Cu/TS-1 give this method considerable potential for further industrialization.

Synthesis of Phenyl Acetate from Phenol and Acetic Anhydride over Synthetic TS-1 Containing Template

In this article, phenyl acetate was synthesized from phenol and acetic anhydride over titanium silicalite-1, in which the organic structure-directing agents were immobilized(TS-1-U). The reaction conditions were specified at a phenol to acetic anhydride molar ratio of 1:1.2, a catalyst dosage of 6 m%, and a reaction temperature of 70 ℃. A total of 96.5% of phenol was converted to phenyl acetate without producing any byproducts after 2.5 h of reaction. Besides, although the catalyst deactivation is inevitable, TS-1-U could be recycled for at least four times.

Novel method for synthesis of titanium silicalite-1 (TS-1)

Titanium silicalite-1 (TS-1) was easily synthesized using inorganic silicon and titanium source, tetrapropylammonium bromide (TPABr) or TPAOH as templating molecule, NH3H2O, HDA or TEAOH etc. as base sources. In this system, TPA+ cations (come from TPABr or TPAOH) served as templating agents to direct the MFI structure. NH3H2O, TEAOH or HDA etc. provides the alkalinity necessary for crystallization. X-ray diffraction, UV-Vis, IR spectroscopies, SEM, 29Si MAS NMR showed that the zeolites obtained possessed all the structural characteristics of TS-1, and titanium atoms were introduced into the framework in TS-1. This material was proved to have high crystallinity and high catalytic activity to allyl chloride epoxidation and propylene epoxidation. All the samples synthesized had similar catalytic properties with a standard TS-1 through compared inorganic reactant system with organic synthesis system using propylene epoxidation. The effects of silicon source and TPABr/SiO2 ratio were discussed.

Au/TS-1 catalyst for propylene epoxidation with H_(2)and O_(2):Effect of surface property and morphology of TS-1 zeolite

The catalytic performances over propylene epoxidation with H_(2)and O_(2)(HOPO process)are significantly affected by the properties(e.g.,surface properties,Ti coordination,morphology)of titanosilicate zeolite.Introducing urea into zeolite synthesis is a simple and convenient method to modify these properties of titanosilicate zeolite.Uncalcined pore-blocked titanium silicalite-1(TS-1,i.e.,TS-1-B)with the lower urea dosage possesses more defective structure and unsaturated coordinated Ti sites verified by 29Si nuclear magnetic resonance(NMR)and X-ray photoelectron spectroscopy(XPS)analysis,which results in a high initial activity and hydrogen efficiency;while the high surface acidity generated by these Ti species leads to a continuous decrease in the activity and the propylene oxide(PO)selectivity during the reaction.As the amount of urea gradually increases,the TS-1-B samples present the reduced surface defects and defective and unsaturated Ti species.Specially,TS-1-B-0.30U presents the weaker PO adsorption on PO-diffusion reflectance infrared Fourier transform spectra(DRIFTS),thus results in the high stable PO formation rate and selectivity over its Au catalyst.Furthermore,a flat-plate-like shape with a shorter thickness of 100 nm along the b-axis direction is observed on the urea-modified TS-1.Compared with the conventional ellipsoidal TS-1 with crystal sizes of 200 and 500 nm,the flat-plate-like TS-1-0.30U displays the less surface defects,unsaturated Ti species,the weaker Lewis acid,which is favorable for the desorption and intracrystalline diffusion of PO,thus reduces the occurrence of side reactions for the improved selectivity and stability.This work may provide a reference for developing titanium-containing materials with high activity and stability over HOPO reaction.

Effect of triethylamine treatment of titanium silicalite-1 on propylene epoxidation

Titanium silicalite- 1 （TS- 1） treated with triethy- lamine （TEA） solution under different conditions was characterized by X-ray powder diffraction （XRD）, Fourier- transform infrared spectrum （FTIR）, ultraviolet-visible diffuse reflectance spectrum （UV-Vis）, nitrogen physical adsorption and desorption, scanning electron microscopy （SEM） and transmission electron microscopy （TEM）. The characterization results show that many irregular hollows are generated in the TS-1 crystals due to the random dissolution of framework silicon and the volume of the hollow cavities increase with increasing the TEA con- centration, and the treatment temperature and time. The modified TS-1 samples improved in varying degrees the catalyst life for the epoxidation of propylene in a fixed-bed reactor probably due to the generation of the hollows to make it easy for the reactants and products to diffuse out of the channels.

Effect of sodium ions in synthesis of titanium silicalite-1 on its catalytic performance for cyclohexanone ammoximation

Titanium silicalite-1 （TS-1） has been hydrothermally synthesized with tetrapropylammonium hydroxide （TPAOH） as the template in the presence of various amounts of Na＋, characterized by inductively coupled plasma, X-ray diffraction, scanning electron microscope, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and ultro-violet-visible spectroscopy and studied in cyclohexanone ammoximation. The characterization results show that with the increase of Na＋ concentration in the synthesis, both the crystal sizes of TS- land extra framework Ti increase but framework Ti decreases. The addition of Na＋ below 3 mol-% of TPAOH in the synthesis does not influence the catalytic properties with above 98% conversion of cyclohexanone and 99.5% selectivity to cyclohexanone oxime. However, at the concentrations of Na＋≥3mol-% of TPAOH in the synthesis, the catalysts are deactivated faster with the increase of Na＋ addition, which can be attributed to more high molecular weight byproducts deposited in the large TS-1 particles and the loss of the frame-work titanium. The results of this work are of great importance for the industry.

Study on Crystallization of Titanium Silicalite Zeolite (Ⅱ)

In order to investigate the rules on formation of zeolite during crystallization of titanium silicalite zeolite (TS-1) the X-ray diffractometry and Foulier transform infra-red spectrometry were applied to track the process of crystallization of titanium silicalite zeolite. The research results revealed that at the initial stage of crystallization the interactions between silica gel and titania gel in the polymer blend could gradually lead to the formation of tiny crystal nuclei with complicated structure that could slowly grow up to form molecular sieves. Quite different from the conventional zeolites that use the acid sites as the catalytically active centers, the oxidative reactivity of the titanium silicalite zeolite was not proportional to its crystallinity and is associated with the oxidative centers of titanium contained in the zeolite.

Study on Crystallization of Titanium Silicalite(Ⅰ)

In order to investigate the rules on preparation of titanium silicalite （TS-1） the ^1H →^13C CP/ MAS NMR spectrometers were applied to track the function of template TPAOH in the process of crystallization of titanium silicalite. The research results revealed that at the initial stage of crystallization the TPA＋ ions acting as the template could predominantly absorb the polymers of negatively charged silicatitania sol and the interactions between silica sol and titania sol could gradually lead to the formation of tiny crystal nuclei that could slowly grow up to form molecular sieves. Upon investigating the course of crystallization of titanium silicalite the ^1H →^13C CP/MAS NMR spectrometers were applied to effectively enhance the resolution of 29Si signals in the titanium silicalite. Study results have shown that during the formation of tiny crystal nuclei upon interaction between titania sol and silica sol the influence of titania sol on the silica sol was insignificant. However, when tiny crystal nuclei broke out into molecular sieves the titania sol could enter the zeolite framework that could apparently impose an enhanced effect on the silica sol.

Preparation of Magnetic TS-1 and Its Catalytic Activity

Magnetic TS-1 was synthesized thesis and solvent vaporation method. The with nanosized nickelferrite particles prepared samples were characterized as nuclei via the hydrothermal syn- with N2 adsorption-desorption iso- therms, FTIR spectrometry, Raman spectrometry, X-ray diffraction, Ultraviolet-visible spectroscopy and Vibrating sample magnetometry. The results show that the composite obtained was composed of TS-1 with MFI structure and NiFe204 with spinel structure, its specific surface area was about 316 m2/g, pore volume was 0.12 cm3/g and pore size distribution was in the range of 0.5-0.7 nm. The catalytic activity of the composite was also investigated by its catalyzing the decomposition of rhodamine B oxidized by H2O2 in aqueous solution. In this case Rhodamine B pollutant could be completely degraded within 150 min. Magnetic TS-1 exhibited high photocatalytic efficiency and super paramagnetic nature for cleaning polluted water with the help of magnetic separation.