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Study on the Vapor-Phase Beckmann Rearrangement of Cyclopentanone Oxime
ZHENG Caizi, LI Zhuohan, LIN Hairui, CHENG Youwei
Key Laboratory of Materials and Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310058, China
Abstract Valprolactam (VL) has potential application value in the fields of medicine and chemical industry, which can be prepared by vapor-phase Beckmann rearrangement reaction of cyclopentanone oxime (CPOO). In this study, the suitability and kinetics of this reaction over a silicalite-1 (S-1) zeolite catalyst were systematically investigated using a micro fixed-bed reactor. The reaction conditions for the vapor-phase Beckmann rearrangement of CPOO were optimized, and a plausible reaction pathway on the S-1 catalyst surface was proposed based on the rearrangement mechanism. Furthermore, a Langmuir-Hinshelwood-Hougen-Watson (LHHW) kinetic model was established , with VL desorption as the rate-limiting step. Results indicate that the VL yield of 95% under the optimal reaction conditions: temperature of 380 ℃ and, weight hourly space velocities of 0.64 h-1, and ethanol as the solvent. Kinetic parameter fitting reveals that the activation energy of the rearrangement reaction and the adsorption energy of CPOO were (42.31±3.22) kJ/mol and (66.07±14.48) kJ/mol, respectively. The model predictions show excellent agreement with the experimental data. This study deepens the understanding of the catalytic mechanism of the gas-phase Beckmann rearrangement of CPOO and provides a robust theoretical basis for reactor design and process parameter optimization.
ZHENG Caizi,LI Zhuohan,LIN Hairui et al. Study on the Vapor-Phase Beckmann Rearrangement of Cyclopentanone Oxime[J]. Chemical Reaction Engineering and Technology, 2025, 41(5): 541-549.
ZHENG Caizi,LI Zhuohan,LIN Hairui et al. Study on the Vapor-Phase Beckmann Rearrangement of Cyclopentanone Oxime[J]. Chemical Reaction Engineering and Technology, 2025, 41(5): 541-549.
