环己酮肟在条形TRBS-1催化剂上的气相Beckmann重排反应  

Vapor Phase Beckmann Rearrangement of Cyclohexanone Oxime over Extruded TRBS-1 Catalyst

作　　者：刘飞翔[1] 程时标[2] 

机构地区：[1]中国石化催化剂分公司湖南建长石化股份有限公司,湖南岳阳414012 [2]中国石化石油化工科学研究院,北京100083

出　　处：《中外能源》2012年第12期78-82,共5页Sino-Global Energy

摘　　要：条形TRBS-1催化剂的主要组成为Silicalite-1分子筛,该分子筛属于具有MFI拓扑学结构的无铝全硅分子筛,是ZSM-5型结构分子筛家族中组成最简单的一种分子筛,其骨架仅含有硅原子和氧原子,基本结构单元为SiO4四面体。本文制备了条形TRBS-1催化剂用于环己酮肟气相Beckmann重排反应生产ε-己内酰胺。运用XRD、N2吸附-脱附、TEM等技术,对条形TRBS-1催化剂进行了表征。结果显示,条形TRBS-1催化剂具有MFI结构特征;BET比表面积达到360m2/g,非微孔比表面积为30m2/g,孔体积和微孔体积分别为0.48mL/g和0.15mL/g,N2吸附-脱附等温线在p/p0=0.45～0.98范围存在滞后环;条形TRBS-1催化剂的颗粒尺寸为200～300nm,大小均匀,其表面存在大量20～50nm小颗粒的黏结剂。环己酮肟在条形TRBS-1催化剂上的气相Beckmann重排反应具有很高的环己酮肟转化率和ε-己内酰胺选择性,且催化剂稳定性和再生性能良好。The key component of extruded TRBS-1 catalyst is the Silicalite-1 molecular sieve,which is an aluminum-free,all-silicon molecular sieve with an MFI topological structure.The Silicalite-1 molecular sieve has the simplest composition among all ZSM-5 molecular sieve family members,with its framework containing only silicon atom and oxygen atom and a basic structural unit of SiO4 tetrahedron.This article describes the preparation of extruded TRBS-1 catalyst used in the production of ε-caprolactam(CPL) by vapor-phase Beckmann rearrangement of cyclohexanone oxime(CHO).XRD,N2 adsorption-desorption and TEM technologies were used to characterize the extruded TRBS-1 catalyst.The results show that the catalyst has the characteristics of the MFI topological structure,the BET specific surface area reaches 360m2/g,the non-micropore specific surface area is 30m2/g,the volumes of pores and micropores are 0.48mL/g and 0.15mL/g respectively,the N2 adsorption-desorption isotherm has hysteresis loop in the range when p/p0=0.45-0.98,the grain size of the extruded TRBS-1 catalyst ranges from 200 to 300nm,and that there is a large amount of adhesive in the form of 20-50nm granules on the surface of the catalyst.The vapor-phase Beckmann rearrangement of cyclohexanone oxime over the extruded TRBS-1 catalyst has a very high CHO conversion rate and ε-caprolactam selectivity and the catalyst has good stability and regeneration properties.

关 键 词：条形TRBS-1催化剂 环己酮肟(CHO) ε-己内酰胺(CPL) 气相Beckmann重排反应 

分 类 号：TQ203.2[化学工程—有机化工]