The development of a new catalyst effective for the vapor-phase Beckmann rearrangement of cyclohexanone oxime has made it possible to establish a commercial process for the production of "-caprolactam without producing any ammonium sulfate. Through fundamental studies of the catalyst, it was discovered that an MFI-type zeolite composed exclusively of silica had a high selectivity and activity for the vapor-phase Beckmann rearrangement. Based on acidity measurements and on the reactivity of oximes with different sizes as well as the calculation results of the deprotonation energies of some silanols, we have suggested that the active sites are nest silanols located close to their mouth of the micro pores. By addition of methanol into the reaction system, the selectivity for "-caprolactam was markedly improved to the levels required for industrialization. A fluidized bed reactor was used for the reaction system in order to maintain a continuous production. By combining the ammoximation process for production of cyclohexanone oxime using the TS-1 catalyst and the vapor-phase Beckmann rearrangement, a commercial plant has been operating on a 60000 tons per year scale since April 2003, without any troubles.

Organic chemistry Z 0200 Development and Industrialization of the Vapor-Phase Beckmann Rearrangement Process -[for the production of ε-caprolactam without producing ammonium sulfate; about 26 refs.]. -(IZUMI, Y.; ICHIHASHI, H.; SHIMAZU, Y.; KITAMURA*, M.; SATO, H.; Bull. Chem.