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Br(o)nsted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,N2 adsorption-desorption,scanning electron microscopy,particle size distribution,inductively coupled plasma (ICP) spectroscopy,Fourier transform infrared (FT-IR) spectroscopy,NH3 temperature-programmed desorption (TPD),H2 temperature-programmed reduction,and thermogravimetric-differential thermogravimetric (TG-DTG) analysis.All the samples crystallized with the AFI structure.TPD profiles showed that stronger Bronsted 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 A1PO-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(o)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(o)nsted acid sites gave the better result with a convarsion of 8.16％ and ε-caprolactam selectivity of 68.17％.
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