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.

Studies of Cyclohexane Catalytic Oxidation Processes over Titanium Silicate-1 Zeolite

The catalytic oxidation processes for cyclohexane/H_2O_2/acetone system overthe TS-1 zeolite was studied. Study results have revealed that the cyclohexane conversion was 27%after the reaction proceeded at 100℃ for 2 hours at a cyclohexane/H_2O_2 molar ratio of 0.8. Thecyclohexanol/cyclohexanone molar ratio was 1.3 along with a certain amount of organic acids andesters, the formation of which was closely associated with the oxidation of reaction solvent anddeep oxidation of cyclohexanone and cyclohexanol contained in the reaction products. With respect tothe catalytic oxidation of cyclohexane/H_2O_2 system the selection of appropriate solvent wascritically important.

Seed-induced synthesis of small-crystal TS-1 using ammonia as alkali source

Small-crystal TS-1 was synthesized via a seed-induced approach using ammonia as the alkali source and tetrapropylammonium bromide as an auxiliary structure-directing agent. The TS-1 samples were characterized using X-ray diffraction, N2 adsorption-desorption, Fourier-transform infrared spectroscopy, inductively coupled plasma atomic emission spectroscopy, scanning electron microscopy, and ultraviolet-visible spectroscopy. The use of the colloidal seed reduced the crystal size, and an appropriate amount of silicalite-1 seed assisted Ti incorporation into the TS-1 framework. This method reduces the cost of TS- 1 synthesis because a significantly smaller amount of tetrapropylammonium hydroxide is used. The catalytic performance of the synthesized small-crystal TS-1 samples in cyclohexanone ammoximation was better than that of bulk TS-1 as a result of improved diffusion and a larger number of active tetrahedral Ti centers.

对氨基吡啶合成的研究

研究了由吡啶制备对氨基吡啶的方法 ,在两个方面取得了进展。其一是用 TS— 1分子筛代替醋酸或邻苯二甲酸酐作为合成 N—氧化吡啶的催化剂 ;其二是用 Pd/Al2 O3 作为催化剂通过催化加氢制备对氨基吡啶。TS— 1及 Pd/Al2 O3 作为催化剂不仅具有较强的催化活性 ,稳定性和重复使用性 ,而且极大地减少了副产物的生成 。

Zr还原法制备高纯度Ti_4O_7及其电催化处理2,4-二氨基甲苯废水

基于Zr高温还原锐钛型TiO_2法,制备出了电催化材料Ti_4O_7,并用XRD和SEM技术对样品的组成、形貌进行了表征。结果表明,在氩气气氛下,反应温度为1 050℃,反应时间为8h,Zr和TiO_2的摩尔比为1∶3时可以得到较为纯净的Ti_4O_7。以自制Ti_4O_7/Ti电极为阳极,Pt电极为阴极,恒电流0.3A,电流密度为0.15A/cm2条件下电解处理2,4-二氨基甲苯(TDA)废水,结果表明,Ti_4O_7/Ti电极对TDA废水具有一定催化作用,反应180min,废水TDA去除率为62.0%,COD去除率为40.3%。