Beckmann rearrangement of cyclohexanone oxime over borate-pillared LDHs

Article abstract of DOI:10.1002/jccs.199900106

Borate-pillared layered double hydroxides (LDHs) were studied as catalysts in vapor-phase Beckmann rearrangement of cyclohexanone oxime to caprolactam under atmospheric pressure. The results were compared with those over the physical admixture of LDH and boria, the co-precipitate of B-Mg-Al hydroxide, and the pristine LDH and boria compounds. Although oxime conversion and caprolactam selectivity declined with time-on-stream over all the catalysts, borate-pillared LDH catalysts could retain activity longer than pure boria or those prepared by other methods. The decay rate however was affected by the Mg/Al ratio, the boron content and the form of LDH precursor used. The LDH itself functioning as a basic catalyst contributed to the formation of side products such as cyclohexanone and 2-cyclohexen-1-one. The physical admixtures of LDH and boria had catalytic properties more close to that of pure boria, which gave high caprolactam selectivities but lost the activity in several hours on stream. The high resistance to decay of the pillared catalysts was attributed to that boria in the interlayer of LDH was stabilized and prevented from structural transformation to a glassy state of no activity.