Beckmann rearrangement mechanism of cyclohexanone oxime, based on the characteristic of self-catalyzed reaction and polymorphism was proposed. According to the suggested mechanism, the basic approach was the rearrange...Beckmann rearrangement mechanism of cyclohexanone oxime, based on the characteristic of self-catalyzed reaction and polymorphism was proposed. According to the suggested mechanism, the basic approach was the rearrangement of OXH+ while the SO3 acts as dehydrating agent and OXSO3 can turn to CPLSO3 ultimately. Considering self-catalyzed reaction between OXSO3 and CPLH+, kinetic model for Beckmann rearrangement was established. Corresponding parameters were estimated by using float genetic algorithm （GA） and simulation results agree well with the experimental data below -19.3℃. Industrial equipment was simulated and analyzed. Effects of key process parameters such as molar ratio of sulfuric acid to oxime and circulation ratio on the residual oxime are also discussed. The results show that the caprolactam exists as CPLH+ finally in oleum and the minimum molecular ratio of sulfuric acid to oxime can be 0.5 theoretically.展开更多
环己酮肟气相Beckmann重排反应RBS-1催化剂在高温反应时易失活,导致催化剂费用居高不下。为提高技术经济性,实现失活催化剂性能的高效恢复,系统研究RBS-1催化剂失活机理、再生手段及催化性能。采用N_(2)物理吸附-脱附技术考察催化剂失...环己酮肟气相Beckmann重排反应RBS-1催化剂在高温反应时易失活,导致催化剂费用居高不下。为提高技术经济性,实现失活催化剂性能的高效恢复,系统研究RBS-1催化剂失活机理、再生手段及催化性能。采用N_(2)物理吸附-脱附技术考察催化剂失活前后与再生前后的比表面积及孔结构变化,并结合XRD、FT-IR和^(29)Si MAS NMR表征技术探讨了RBS-1催化剂在失活与再生过程中活性中心的演变规律。研究发现,失活RBS-1催化剂物相结构保持完好,但BET比表面积和孔体积均有明显降低,说明催化剂失活主要为积炭覆盖催化剂活性位点并堵塞孔道所致。针对积炭堵孔导致的催化剂失活问题,采用烧炭、含氮化合物改性处理构建巢式硅羟基活性位点等手段对失活催化剂进行再生研究。结果表明,在530℃下烧炭能将催化剂表面及孔道内的大部分积炭烧除,催化剂性能可恢复90%以上;对脱炭后的催化剂进一步改性处理,最优催化剂性能可恢复98%以上。展开更多
基金Project(20233040) supported by the National Natural Science Foundation of China and SI NOPEC
文摘Beckmann rearrangement mechanism of cyclohexanone oxime, based on the characteristic of self-catalyzed reaction and polymorphism was proposed. According to the suggested mechanism, the basic approach was the rearrangement of OXH+ while the SO3 acts as dehydrating agent and OXSO3 can turn to CPLSO3 ultimately. Considering self-catalyzed reaction between OXSO3 and CPLH+, kinetic model for Beckmann rearrangement was established. Corresponding parameters were estimated by using float genetic algorithm （GA） and simulation results agree well with the experimental data below -19.3℃. Industrial equipment was simulated and analyzed. Effects of key process parameters such as molar ratio of sulfuric acid to oxime and circulation ratio on the residual oxime are also discussed. The results show that the caprolactam exists as CPLH+ finally in oleum and the minimum molecular ratio of sulfuric acid to oxime can be 0.5 theoretically.
文摘环己酮肟气相Beckmann重排反应RBS-1催化剂在高温反应时易失活,导致催化剂费用居高不下。为提高技术经济性,实现失活催化剂性能的高效恢复,系统研究RBS-1催化剂失活机理、再生手段及催化性能。采用N_(2)物理吸附-脱附技术考察催化剂失活前后与再生前后的比表面积及孔结构变化,并结合XRD、FT-IR和^(29)Si MAS NMR表征技术探讨了RBS-1催化剂在失活与再生过程中活性中心的演变规律。研究发现,失活RBS-1催化剂物相结构保持完好,但BET比表面积和孔体积均有明显降低,说明催化剂失活主要为积炭覆盖催化剂活性位点并堵塞孔道所致。针对积炭堵孔导致的催化剂失活问题,采用烧炭、含氮化合物改性处理构建巢式硅羟基活性位点等手段对失活催化剂进行再生研究。结果表明,在530℃下烧炭能将催化剂表面及孔道内的大部分积炭烧除,催化剂性能可恢复90%以上;对脱炭后的催化剂进一步改性处理,最优催化剂性能可恢复98%以上。
