Catalysis Today, Vol.97, No.4, 241-247, 2004
Novel synthesis of epsilon-caprolactam from cyclohexanone-oxime via Beckmann rearrangement over mesoporous molecular sieves MCM-48
Vapor-phase synthesis of epsilon-caprolactant (E-C) from cyclohexanone-oxime (CHO) has been studied at 1 atm and 300-400 degreesC using SiMCM-48 and AIMCM-48(X) with Si/Al molar ratios X in a fixed-bed, continuous flow reactor. The catalysts were characterized with ICP-AES, XRD, TEM, FT-IR, N-2-adsorption, Al-27 and Si-29 MAS NMR and TPD of ammonia. An increase of X value in AIMCM-48(X) enhances both the BET surface area and the unit cell parameter but diminishes the acid amount. In the reaction of CHO, benzene, toluene, ethanol and 1-hexanol were utilized as solvents. The CHO conversion increases with the reaction temperature, whereas the F-C selectivity exhibits the opposite trend due to side reactions. The catalyst stability is greatly enhanced by using ethanol and 1-hexanol as the solvents due to their production of water vapor via dehydration. Excellent catalytic performance of AIMCM-48(10) is attained at 1 atm, 350 degreesC and W/Fc 74.6 g h/ mol by using 1-hexanol in the feed; the CHO conversion and the F-C selectivity exhibit higher than 99% and 90%, respectively, during at least 130 h process time. (C) 2004 Elsevier B.V. All rights reserved.