碳氮复合镍催化剂催化的高选择性己二腈加氢制备环己亚胺

Highly Selective Hydrogenation of Adiponitrile to Hexamethyleneimine Catalyzed by Carbon Nitrogen Composited Nickel Catalysts

环己亚胺是一种重要的医药农药中间体,可用于合成青霉素、除草剂和杀菌剂等.本文应用溶剂辅助机械球磨和热解法制备了一系列的负载型Ni基催化剂Ni/IM-C(R),研究了该催化剂对于1,6-己二腈加氢制备环己亚胺的工艺.结果表明,由乙酸镍、 2-甲基咪唑及活性炭共同球磨、煅烧还原所制备的Ni/IM-C(R)具有优良的1,6-己二腈加氢活性和98%以上的环己亚胺收率.通过X射线衍射(XRD)、 X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、能量色散X射线(EDX)、透射电子显微镜(TEM)和N2吸附-脱附测试等表征手段研究了Ni/IM-C(R)催化剂的表面织构性质和化学性质.结果表明,氮掺杂碳材料改善了Ni/IM-C(R)催化剂活性金属Ni纳米颗粒的分散性.在Ni/IM-C(R)催化剂中,镍物种具有高活性,尺寸较小且表面Ni0含量高.在无添加剂存在下, Ni/IM-C(R)催化1,6-己二腈加氢环化制备环己亚胺时显示出良好的加氢活性和环己亚胺的高选择性.Ni/IM-C(R)催化剂制备方法简单、反应后易于分离、多次反应循环后仍具有稳定的催化性能,具有良好的工业应用前景.

Hexamethyleneimine(HMI)is a crucial intermediate in the production of pharmaceuticals and agrochemi⁃cals,including penicillin,herbicides,and fungicides.In this study,supported Ni-based catalysts were prepared using solvent-assisted mechanochemical ball milling and pyrolysis,and the catalytic performance for the hydrogena⁃tion of 1,6-adiponitrile(ADN)to HMI was evaluate.The results demonstrated that the supported Ni-based catalyst Ni/IM-C(R)exhibited high activity for the hydrogenation of ADN to HMI in 98%yield.The catalyst Ni/IM-C(R)was prepared by co-ball milling nickel acetate,2-methylimidazole and activated carbon,followed by calcination in N2 and then reduced by H2.The surface structures and the chemical properties of the Ni/IM-C(R)catalyst were charac⁃terized via various techniques,including X-ray diffraction,X-ray photoelectron spectroscopy,scanning electron microscopy,energy-dispersive X-ray spectroscopy,transmission electron microscope,and N2 adsorption-desorption measurements.The characterization results indicated that nitrogen-doped carbon improved the dispersion of Ni nanoparticles in the Ni/IM-C(R)catalyst.The catalyst Ni/IM-C(R)displayed small Ni nanoparticles with high surface,which directed the high activity for the hydrogenation of ADN to HMI.Without additives,the Ni/IM-C(R)catalyzed hydrogenation of ADN exhibited excellent activity and high selectivity towards HMI.The Ni/IM-C(R) catalyst is stable and recyclable for several times without deactivation. The Ni/IM-C(R) catalyst is simple to be prepared and the Ni/IM-C(R) catalyzed hydrogenation of ADN is promising for industrial applications.