Study On Catalysts And The Reaction Behaviour Of Oxime For Industrial Preparation Methyl Ethyl Ketone Oxime Catalyzed By Titanosilicate/Hydroperoxide System

Methyl ethyl ketone oxime, cyclohexanone oxime and other oximes are important bulk chemicals that contain oxygen in their structures, with the scale of tens of thousands to several millions of tons in the international market. The preparation process of oxime over Titanosilicate/H2O2 system is a friendly green process for our environment. The dissertation has been carried out to study the new modified method how to gain higher activity Ti-MWW, analysis the reaction behaviour of methyl ethyl ketone oxime catalyzed by titanosilicate/H2O2 system, and study the deactivation reasons of the catalyst and find the regeneration methods based on the preparation process of methyl ethyl ketone oxime over Titanosilicate/H2O2 system. It has made very instructive and practical application of the results. The main results are as follows:In the first part, we designed an experiment according to the transition metals Ti and some complexing agents (EDTA, ox…) can form a stable complex to eliminate the extraframework Titanium, we carried out our experiment from the amount of complexing agent, temperature, nitric acid consumption. Rerults showed that, EDTA is a suitable complexing agent, gain the high activity Ti-MWW. According to fluoride ion system and the transition metals can generate complex fluoride, it is beneficial to make transition metals into the framework of the zeolite modified by fluoride treatment, we carried out our experiment from silicon fluoride from the ratio,treated time and other aspects of the system. The results show that the use of ammonium fluoride post-treatment made us get highly active catalyst.In the second part,There occours some problems which influence the stability of MEKO according its industrial process, we studied the factors from Titanosilicate, H2O2,or the Ti-MWW and H2O2 together resulted in the hydrolysis of metyl ethyl ketone oxime to methyl ethyl ketone, NOx, etc. Thus, the system was from alkalescence to acidity. The same phenomena also existed in the TS-1/H2O2 system for cyclohexanone oxime. This was beneficial for the increase of the efficiency and the stability of the process over titanosilicate/H2O2 system.Finally, Studied the deactivated catalyst and explorded the regeneration methods. Various measurements(XRD/SEM/BET/UV-Vis/ICP/TG) were adopted to study the deactivation reasons of the catalyst. The most important reason of the inactivity of the catalyst is the deactivation caused by carbon deposit.We tried many regenerated methods,and found that,first acid treatment,and then a secondary synthesis caused a structural rearrangement of Ti-MWW framework could revive the catalyst. Regeneration of the deactived catalyst is very important for economy and society.