Liquid-phase Beckmann rearrangement of cyclohexanone oxime over mesoporous molecular sieve catalysts

A series of mesoporous molecular sieves with various SiO₂/ Al₂O₃ ratios have been applied to the liquid-phase Beckmann rearrangement of cyclohexanone oxime. The influences of solvent, aluminum content, aluminum-incorporating method, and catalyst structure on the catalytic performance have been investigated. Benzonitrile has been found to be a suitable solvent. The surface silanol groups ineffectively catalyze the rearrangement, whereas the acid sites generated by incorporation of aluminum improve the activity and the selectivity to ε-caprolactam remarkably. Moreover, an Al-containing MCM-41 catalyst prepared by the postsynthetic method using AlCl₃ as an aluminum precursor exhibits higher lactam selectivity than a directly synthesized one. For a given aluminum content, MCM-41 shows superior performance to beta zeolite and other mesoporous catalysts, SBA-1 and SBA-15. It has been suggested that a sufficient amount of acid sites with appropriate strength is of importance to the liquid-phase Beckmann rearrangement.