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Since it was claimed by EniChem in 1983 for the first time, titanium silicate‐1 (TS‐1) zeo‐ lite presented the most delightful catalytic performance in the area of selective organic oxidation reactions. To enhance the mass diffusion property, hierarchical titanium silicate with hollow cavities within crystal was prepared by using a post‐synthesis treatment in the presence of organic template, and then, it was commercially produced and employed in many industrial catalytic oxidation processes, such as propylene epoxidation, phenol hydroxylation, and cyclohexanone ammoximation. Moreover, we also developed several totally novel oxidation reactions on hollow titanium silicate (HTS) zeolite, i.e., Baeyer‐ Villiger oxidation of cyclohexanone and chlorohydrination of allyl chloride with HCl and H 2 O 2 . In all cases, HTS shows much better catalytic performance than TS‐1, attribut‐ ing to the mass diffusion intensification by introducing hollow cavities. On the other hand, enormous works on synthesizing hierarchical TS‐1 zeolites with open intracrystal‐ line mesopores have been done via silanization treatment and recrystallization. Based on them, several bulk molecule oxidation processes with tert‐butyl hydroperoxide, such as epoxidation of fatty acid methyl ester (FAME) and large olefins, have been carried out. As a consequence, hierarchical TS‐1 zeolites supply a platform for developing environ‐ mental‐friendly catalytic oxidation processes to remarkably overcome the drawbacks of traditional routes.

Environmental-Friendly Catalytic Oxidation Processes Based on Hierarchical Titanium Silicate Zeolites at SINOPEC