环己酮肟贝克曼重排制己内酰胺绿色催化研究进展  

Research progress in Green catalytic Beckmann rearrangement of cyclohexanone oxime into caprolactam

作　　者：周云[1] 卢建国 朱明乔[1] 

机构地区：[1]浙江大学化学工程与生物工程学院,浙江杭州310027 [2]岳阳东润化工有限公司,湖南岳阳414002

出　　处：《合成纤维工业》2015年第2期51-56,共6页China Synthetic Fiber Industry

基　　金：浙江省自然科学基金(Y4080247);工业控制技术国家重点实验室开放课题基金(ICT120);广西石化资源加工及过程强化技术重点实验室开放课题基金(K002)

摘　　要：己内酰胺是一种重要的有机化工原料,其传统的环己酮肟贝克曼重排制己内酰胺是以发烟硫酸为催化剂的生产工艺,存在污染环境、设备腐蚀以及成本高等缺点。综述了环己酮肟贝克曼重排反应制己内酰胺的绿色催化研究进展;介绍了氧化物催化剂、钛硅分子筛催化剂,及离子液体在催化中的应用;氧化物催化剂具有较好的催化活性,但存在寿命短、再生性差的缺点;TS-1型分子筛催化剂成本高,重现性差,工业化生产有待进一步研究;S-1型分子筛催化剂催化性能好,但反应条件较苛刻,使用寿命短;离子液体作为催化剂选择性不高。指出气相重排工艺绿色催化的高硅分子筛,特别是S-1型分子筛,具有较理想的催化效果,进一步提高全硅分子筛催化剂的选择性、延长使用寿命是今后研究的重点。Caprolactam is an important organic chemical material. The traditional Beckmann rearrangement of cyclohexanone oxime into caprolactam has the disadvantages of environment pollution,equipment corrosion and high production cost due to using fuming sulfuric acid as catalyst. The research progress in green catalytic Beckmann rearrangement of cyclohexanone oxime into caprolactam was reviewed. The application of oxide catalyst,titanium silicalites and ionic liquid in the catalytic reaction was introduced. Oxide catalysts have relatively high catalystic activity,but short service life and poor reproducibility; TS-molecular sieve has high catalysis cost and poor repeatability,whose application in commercial production should be further developed; S-1molecular sieve has favorable catalytic performance,but stict reaction conditions and short service life; and ionic liquid has low selectivity as a catalyst. It was pointed out that high-silica zeolite used as the green catalyst in vapor-phase rearrangement,especially S-1 molecular sieve,could provide a satisfying catalytic effect,and the research focus should be attached on the improvement of silica zeolite selectivity and service life.

关 键 词：己内酰胺 环己酮肟 贝克曼重排 绿色催化 

分 类 号：TQ225.261[化学工程—有机化工]