Modified Beta zeolites as catalysts for the Beckmann rearrangement of cyclohexanone oxime

被引:83
作者
Heitmann, GP [1 ]
Dahlhoff, G [1 ]
Hölderich, WF [1 ]
机构
[1] Univ Technol RWTH Aachen, D-52074 Aachen, Germany
关键词
cyclohexanone oxime; epsilon-caprolactam; beta-zeolite; FT-IR; acid treatment; silanol groups;
D O I
10.1016/S0926-860X(99)00126-X
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Aluminum or boron containing Beta zeolites were studied as catalysts for the Beckmann rearrangement of cyclohexanone oxime to E-caprolactam. Analogously to previous investigations on [B]-ZSM-5 zeolites, the selectivity to caprolactam could be enhanced by simultaneously decreasing reaction temperature and pressure to 300 degrees C and 100 mbar, respectively. Postsynthesis modifications, e.g. calcination, acid treatment, were applied on the initial materials in order to increase the amount of hydroxyl groups on the zeolites' surfaces, which was proved by FT-LR measurements. Nevertheless, such treatments did not lead to better catalytic performances. In the case of the [Al]-Beta zeolite, the maximum selectivity reached up to a value of 91%, whereas the [B]-Beta yielded selectivities around 97%. Despite very high initial conversions, both catalysts showed a significant loss of activity over time-on-stream, which was mostly pronounced using the [B]-Beta. The deactivation factor of the latter proved to be fifteen times higher compared to a [B]-ZSM-5 zeolite. Besides investigations of the zeolites' hydroxyls, FT-IR measurements of pyridine adsorption were used in order to obtain information on the nature of the catalytic active sites of the catalysts. (C) 1999 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:99 / 108
页数:10
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