磺酸树脂催化环己酮肟液相贝克曼重排反应.doc

D-72磺酸树脂催化环己酮肟液相贝克曼重排制己内酰胺 游奎一1，曾珍1，王良芥1，刘平乐1，吴剑1，李松1，尹笃林2，罗和安1第一作者: 游奎一（1979-）, 男, 博士, 副教授。主要从事有机催化合成方面的研究。 联系人：罗和安. Tel: (0731 E-mail:  HYPERLINK mailto:hluo@xtu.edu.cn hluo@xtu.edu.cn 基金来源：国家自然科学基金项目; 湖南省教育厅资助科研项目（09C955）; 湘潭大学校级课题（08XZX14，08QDZ26） （1. 湘潭大学化工学院；教育部化工过程模拟与优化工程研究中心，湖南湘潭 411105； 2. 湖南师范大学化学化工学院， 湖南长沙 410081） 摘要：在以二甲亚砜作溶剂，以D-72固体磺酸树脂为催化剂的两相体系中，实现了由环己酮肟液相贝克曼重排制备己内酰胺的反应。主要考察了环己酮肟在固体酸催化剂上的吸附热力学规律以及溶剂、反应温度、反应时间、催化剂用量以及催化剂的重复使用性等因素对重排反应的影响。结果表明，环己酮肟在磺酸树脂上的等温吸附过程符合Langmuir吸附模型，吸附等温线可用Langmuir等温方程和速率方程来描述。在二甲亚砜溶剂中，当反应温度在130 ℃，催化剂用量为0.5 g（催化剂:环己酮肟=1:2（质量比））的条件下反应6小时，环己酮肟的转化率高达100%，己内酰胺的选择性为86.2%，主要副产物为环己酮。该法对环境无害，反应条件温和，催化剂容易分离和可重复使用等优点。 关键词：D-72磺酸树脂；二甲亚砜；液相贝克曼重排；环己酮肟；己内酰胺 中图分类号: O643. 32　　　文献标识码: A Liquid Phase Beckmann Rearrangement of Cyclohexanone Oxime into ε-Caprolactam Catalyzed by D-72 Sulfonic Acid Resin YOU Kui-yi1, ZENG Zhen1, WANG Liang-jie1, LIU Ping-le1, WU Jian1, LI Song1, YIN Du-lin2, LUO He-an1* College of Chemical Engineering, Xiangtan University; Engineering Research Center of Chemical Process Simulation Optimization of Ministry of Education, Xiangtan 411105, China; College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081, China) Abstract: The liquid phase Beckmann rearrangement of cyclohexanone oxime into ε-caprolactam was successfully developed by using D-72 sulfonic acid resin as catalyst and dimethylsulfoxide as solvent in a two-phase system. The effects of solvent, reaction temperature, reaction time and amount of catalyst on the rearrangement of cyclohexanone oxime were examined. The results indicate that the adsorption behavior of cyclohexanone oxime on sulfonic acid resin accords with Langmuir adsorption model and can be described by Langmuir isotherm and speed equation. And the conversion of cyclohexanone oxime can reach 100% with 86.2% of selectivity to ε-caprolactam when the reaction was carried out at 130 ℃ for 6 h in dimethylsulfoxide solvent (m (catalyst): m (o