石油炼制与化工 ›› 2023, Vol. 54 ›› Issue (10): 78-84.

• 催化剂 • 上一篇    下一篇

环己酮肟气相贝克曼重排S-1分子筛催化剂研究

赵俊琦,张晓昕,慕旭宏,宗保宁   

  1. 中石化石油化工科学研究院有限公司
  • 收稿日期:2023-03-22 修回日期:2023-06-07 出版日期:2023-10-12 发布日期:2023-09-24
  • 通讯作者: 张晓昕 E-mail:zhangxx.ripp@sinopec.com

STUDY ON S-1 ZEOLITE CATALYST FOR THE VAPOR PHASE BECKMANN REARRANGEMENT OF CYCLOHEXANONE OXIME

  • Received:2023-03-22 Revised:2023-06-07 Online:2023-10-12 Published:2023-09-24
  • Contact: Xiao XinZHANG E-mail:zhangxx.ripp@sinopec.com

摘要: 采用水热法合成S-1分子筛,并引入助剂Fe调节分子筛不同硅羟基的比例,经含氮化合物缓冲溶液后处理后获得S-1催化剂;采用X射线衍射、N2吸附-脱附、傅里叶变换红外光谱、等离子体电感耦合原子发射光谱、扫描电子显微镜等手段对合成分子筛进行表征,进而考察了助剂Fe含量和含氮化合物缓冲溶液后处理对分子筛物化性质及其催化环己酮肟气相贝克曼重排制ε-己内酰胺性能的影响。结果表明:助剂Fe最佳质量分数为254 μg/g,经过含氮化合物缓冲溶液处理后,合成分子筛的相对硅羟基总量和巢式硅羟基比例显著增加,其催化环己酮肟气相贝克曼重排转化率和己内酰胺选择性最高,分别达到99.9%和95.0%。

关键词: 环己酮肟, 气相贝克曼重排, ε-己内酰胺, S-1分子筛, 硅羟基

Abstract: S-1 zeolites were synthesized by hydrothermal method, Fe was introduced to adjust the proportion of different silicon hydroxyl groups in the S-1 zeolites, and S-1 catalysts were obtained after post-treatment of the S-1 zeolites with N-containing buffer solution. The S-1 zeolites were characterized by XRD, N2 adsorption-desorption isotherm, FT-IR, ICP-AES, and SEM. The influences of Fe content and post-treatment of N-containing buffer solution on the physicochemical properties of the S-1 zeolites and their catalytic performances for the vapor phase Beckmann rearrangement of cyclohexanone oxime to produce ε-caprolactam were investigated. The results showed the optimum Fe content of S-1 zeolites was 254 μg/g, relative total amount of siloxane hydroxyl and the ratio of nested siloxane hydroxyl groups increased obviously after the post-treatment of N-containing buffer solution, and the conversion of cyclohexanone oxime to gas phase Beckmann rearrangement and the selectivity of cyclohexanone oxime to epsilon-caprolactam were to 99.9% and 95.0%, respectively.

Key words: cyclohexanone oxime, vapor phase Beckmann rearrangement, ε-caprolactam, S-1 zeolite, silanol