环己酮氨肟化直接合成己内酰胺反应过程的研究-化学工艺专业论文.docxVIP

环己酮氨肟化直接合成己内酰胺反应过程的研究 STUDY ON DIRECT SYNTHESIS OF ε-CAPROLACTAM BY CYCLOHEXANONE AMMOXIMATION ABSTRACT The synthesis of ε-caprolactam from cyclohexanone, NH3 and H2O2 is usually composed of two processes. The first step is the synthesis of cyclohexanone oxime by cyclohexanone ammoximation. Then, the following step is the Beckmann rearrangement of cyclohexanone oxime to ε-caprolactam. The integrated process of the two reactions can removal the intermediate separation unit,simplify technological process,rasie utilization ratio of raw material, decrease energy consumption, and reduce equipment investment. Based on this, the integrated process synthesis of cyclohexanone oxime by cyclohexanone ammoximation and Beckmann rearrangement of cyclohexanone oxime to ε-caprolactam is studied in the paper. A novel Br?nsted acidic ionic liquid N,N,N-trimethyl-N-sulfobutyl hydrogen sulfate ([HSO3-b-N(CH3)3]HSO4), is synthesized through a two-step method. its structure are characterized by FT-IR, NMR, ESI-MS, elementary analysis,et al. A novel catalyst system, [HSO3-b-N(CH3)3]HSO4-ZnCl2 is used as catalyst perpared for the Beckmann rearrangement of cyclohexanone oxime to ε-caprolactam. Under the optimized conditions, the cyclohexanone conversion is 100% and the selectivity to ε-caprolactam is 94.9%. The reaction mechanism of cyclohexanone oxime rearrangement over [HSO3-b-N(CH3)3]HSO4-ZnCl2 catalyst is also investigated by React IR IC-10. The direct synthesis of ε-caprolactam from cyclohexanone and (NH2OH)2·H2SO4 has been investigated in [HSO3-b-N(CH3)3]HSO4. Under the optimized conditions, the cyclohexanone conversion is 95.1% and the selectivity to ε-caprolactam is 95.2%. Moreover, the ionic liquid can be used for three times with a little decrease of the yield of ε-caprolactam. TS-1-[HSO3-b-N(CH3)3]HSO4 is used as catalyst prepared for the direct synthesis of ε-caprolactam by cyclohexanone ammoximation. Under the optimized conditions, the cyclohexanone conversion is 39.4% an