Acidity Control and Catalysis of Pentasil Zeolites

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Abstract
Acidities of pentasil zeolites were measured and correlated with aluminum content using the following methods: (1) Acid-base indicator method, (2) NH3-TPD spectra, (3) GC pulse adsorption of pyridine and 4-methylquinoline, and (4) FTIR spectroscopy of adsorbed pyridine. By controlling the acidity of pentasil zeolites, we have succeeded in obtaining high catalytic performance both in paraselective dealkylation of cymenes and in vapor-phase Beckmann rearrangement of cyclohexanone oxime to ∊-caprolactam. In the dealkylation, moderate acidity of Li-ZSM-5 was the key to avoid side reactions while keeping a high conversion of cymenes. In the Beckmann rearrangement, neutrality and crystallinity of the pentasil zeolite were keys to obtain a high lactam selectivity, and a high lactam selectivity of 95% was attained by the surface treatment with chlorotrimethylsilane. The active sites were elucidated to be neutral silanols on the external surface of zeolite.