Development of mesoporous Al,B-MCM-41 materials - Effect of reaction temperature on the catalytic performance of Al,B-MCM-41 materials for the cyclohexanone oxime rearrangement

A series of aluminum-boron-silicate MCM-41 mesoporous materials and their counterparts treated with NH4F aqueous solution were synthesized and characterized by using XRD, MAS NMR, nitrogen physisorption, DRIFT, TG-DTA, TP/MS and pyridine adsorption. All of the samples showed typical MCM-41 structural and textural properties. Al-27 MAS NMR showed that the aluminum environment was mainly four coordinated and six-coordinated aluminum for non-fluorinated samples and fluorinated ones, respectively. Boron was in the trigonal framework environment at ca. catalytic reaction temperatures and the NH4F treatment did not affect the boron environment in our Al,B-MCM-41 materials. All of the Al,B-MCM-41 materials studied contained both Bronsted and Lewis acid sites. However, the strong acid Bronsted/Lewis ratios decreased in the fluorinated catalysts. Moreover, the influence of temperature was studied on the cyclohexanone oxime conversion and the product selectivity in the 623-798 K range. Results indicated that temperatures lower than 748 K favored Beckmann rearrangement to E-caprolactam, whereas, at higher temperatures the main reaction was cyclohexanone oxime hydrolysis to cyclohexanone. The aluminum-boron-silicate MCM-41 mesoporous materials treated with NH4F improved both the selectivity to epsilon-caprolactam (related mainly to boron content) and their life span (related to their lower ratios of strong Bronsted/Lewis acid sites). (c) 2006 Elsevier B.V. All rights reserved.