Development and Industrialization of the Vapor-Phase Beckmann Rearrangement Process
- 11 July 2007
- journal article
- research article
- Published by Oxford University Press (OUP) in Bulletin of the Chemical Society of Japan
- Vol. 80 (7), 1280-1287
- https://doi.org/10.1246/bcsj.80.1280
Abstract
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 ε-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 ε-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.Keywords
This publication has 11 references indexed in Scilit:
- The Catalysis of Vapor-Phase Beckmann Rearrangement for the Production of ε-CaprolactamCatalysis Surveys from Asia, 2003
- Some aspects of the vapor phase Beckmann rearrangement for the production of ε-caprolactam over high silica MFI zeolitesCatalysis Today, 2002
- Acidity Control and Catalysis of Pentasil ZeolitesCatalysis Reviews, 1997
- The use of zeolites in the synthesis of fine and intermediate chemicalsCatalysis Today, 1997
- Caprolactam via AmmoximationPublished by American Chemical Society (ACS) ,1996
- Ammoximation of Cyclohexanone on Titanium Silicalite: Investigation of the Reaction MechanismStudies in Surface Science and Catalysis, 1993
- Cyclohexanone Ammoximation: A Break Through In The 6-Caprolactam Production ProcessStudies in Surface Science and Catalysis, 1990
- Some Catalytic Applications of ZSM-5 Zeolite: Para-Selective Dealkylation and Vapor Phase Beckmann RearrangementStudies in Surface Science and Catalysis, 1986
- Chemical and physical properties of the ZSM-5 substitutional seriesJournal of Catalysis, 1980
- The Beckmann Rearrangement.Chemical Reviews, 1933