The Application Of Modified TS-1 On Oxidation Reaction And Amination Reaction

As a new type of green materials.titanium siliealite-1 has been the highlight since the first report of TS-1 in 1983. It is reviewed that there are different demands of different reaction to the TS-1. the influential factors for TS-1 properties are metal impurity, non-skeleton titanium and molecular sieve acid. So in older to make it can suited better for different reaction. Using the means of modification to improve its properties have become another focal point of modern research. In the background, the catalysis of modified TS-1 to oxidation reaction and amination are studied systematically in this paper.TS-1 was modified by the steep of different substances solution, modification substances included acid, alkali and salty. Modified TS-1 was used to catalyze the oxidation of sec-Butyl Alcohol to methyl ethyl ketone. Reaction conditions, the reasons of catalytic properties increase and stability were studied. Due to rare reports on this kind of reaction was catalyzed on TS-1. so the study had played the role of theoretical research data accumulated. Conclusions were as follow. Pd(NO3)2-modified TS-1 was the optimum catalyst, modification temperature was 100℃. Pd(NO3)2 solution concentration was 60g/L, roasting temperature was 500℃. The reaction temperature was 60℃, n(SBA)/n(H2O2) =2:1. the dosage of catalyst was 10g/mol SBA. reaction time was 3h, XSBA was 76.9%. SMEK could amount to 100%. The reasons of catalytic properties increase were increase of skeleton titanium and the amount of acid. Its stability was good. and it was regenerated by the high-temperature calcinations.TS-1 was modified by a two-step steep mean. modification substances were the combination of TPAOH and various salts. Modified TS-1 was used to catalyze the ammonium oxidation of methyl ethyl ketone to methyl ethyl ketone oxime. The reactions condition. the reasons of catalytic properties increase and stability were studied to solve the problem of much dosage of catalyst. long reaction time. low stability. Conclusions were as follow. TPAOH-Zn(NO3)2:modified TS-1 was the optimum catalyst, modification conditions were influential to reaction result. The reaction temperature was 70℃. NH3 and H2O2 were fed continuously. n(NH3):n(MEK):n(H2O2)=4:1:2. the dosage of catalyst was 12g/molMEK. reaction time was 2.5 h. XMEK was 99.8%. SMEKO was 99.8%. The reason of catalytic properties increase was increase of the catalytic reaction space, and its stability was better than previous work. and it was regenerated by the high-temperature calcinations.Modified TS-1 was used to catalyze the amination of n-butanol to n-butyl amine. The reaction conditions and catalytic stability were studied to validate the properties of TS-1 carrier.lt was concluded that the loading of active constituent CuO was 20wt%. the loading of cocatalyst Cr2O3 was 8wt %. The Si/Ti of TS-1 was 38.7 as the carrier. Catalyst forming methods was kneading into strips. Roasting temperature was 500℃. The reaction temperature was 240℃. H2 pressure was 1.5 MPa, the molar ratios of NH3 and NBA was 6:1, the airspeed of NBA was 25h-1. XNBA was 96.6%, SNBAM was 89.7%. Its stability was good, and it could be accumulated using 100h, the process of deactivation included initial period.smooth process and decline period.