金属取代型AlPO-5分子筛催化剂上环己烷亚硝化一步法合成己内酰胺(英文)  

One-Step Cyclohexane Nitrosation to ε-Caprolactam over Metal Substituted AlPO-5

作　　者：郝芳[1] 钟俊[1] 刘平乐[1] 游奎一[1] 魏超[2] 罗和安[1] 

机构地区：[1]湘潭大学化工学院,湖南湘潭411105 [2]长沙理工大学化学与生物工程学院,湖南长沙410004

出　　处：《催化学报》2012年第4期670-676,共7页

基　　金：supported by the Program for New Century Excellent Talents in University(NCET-10-0168);the National Natural Science Foundation of China(20976148,21006081);the Scientific Research Fund of Hunan Provincial Education Department(09CY007,CX2010B257);Project of Hunan Provincial Science and Technology Department(2010WK2008,2010GK3169)~~

摘　　要：采用水热法制备了一系列结晶态的AlPO-5(磷酸铝分子筛),SAPO-5(硅磷酸铝分子筛)和MeAlPOs(金属取代型磷酸铝分子筛)催化剂,利用X射线衍射、N2吸附脱附法、扫描电镜、粒度分布、电感耦合等离子光谱、红外光谱、NH3程序升温脱附、H2程序升温还原和热重-微分热重分析对催化剂进行了表征,并考察了其催化环己烷亚硝化一步法制备己内酰胺的反应活性.结果表明,随着Si或金属原子引入AlPO-5结构中,催化剂的Lewis弱酸中心增加,同时出现了Brnsted强酸中心.相对于AlPO-5,具有较大比表面积和较多酸中心的SAPO-5和CrAPO-5表现出较好的环己烷亚硝化反应活性,后者环己烷转化率为8.16%,己内酰胺选择性达68.17%.Crystalline AlPO-5,SAPO-5,and metal substituted AlPO-5（MeAlPOs） were prepared by the hydrothermal method and characterized by X-ray diffraction,N 2 adsorption-desorption,scanning electron microscopy,particle size distribution,inductively coupled plasma（ICP） spectroscopy,Fourier transform infrared（FT-IR） spectroscopy,NH 3 temperature-programmed desorption（TPD）,H 2 temperature-programmed reduction,and thermogravimetric-differential thermogravimetric（TG-DTG） analysis.All the samples crystallized with the AFI structure.TPD profiles showed that stronger Br nsted acid sites appeared and the number of Lewis acid sites increased when Si or a metal was introduced into the framework of AlPO-5.ICP,FT-IR spectra,and TG-DTG curves confirmed that Si or the metals were incorporated into the framework of the AlPO-5.The catalytic properties of the samples in cyclohexane nitrosation to ε-caprolactam were studied.SAPO-5 with a larger BET surface area,more Lewis acid sites,and stronger Br nsted acid sites gave better activity and selectivity than AlPO-5.Among the MeAlPOs,CrAPO-5 with the larger BET surface area,more Lewis acid sites,and stronger Br nsted acid sites gave the better result with a conversion of 8.16% and ε-caprolactam selectivity of 68.17%.

关 键 词：金属取代型磷酸铝分子筛 己内酰胺 环己烷 一步法 亚硝化 

分 类 号：TQ225.261[化学工程—有机化工]