Ni-Fe-Al-O双金属催化剂在生物质基2-羟基四氢吡喃还原胺化合成5-氨基-1-戊醇中的性能研究  

Reductive Amination of Biomass-Derived 2-Hydroxytetrahydropyran to 5-Amino-1-Pentanol over Bimetallic Ni-Fe/Al_(2)O_(3)Catalysts

作　　者：杨坚 李雪梅[1] 张佳[1,2] 刘海龙 田俊英[1] 夏春谷 黄志威[1] YANG Jian;LI Xue-mei;ZHANG Jia;LIU Hai-long;TIAN Jun-ying;XIA Chun-gu;HUANG Zhi-wei(State Key Laboratory for Oxo Synthesis and Selective Oxidation,Lanzhou Institute of Chemical Physics,Chinese Academy of Sciences,Lanzhou 730000,China;University of Chinese Academy of Sciences,Beijing 100049,China)

机构地区：[1]中国科学院兰州化学物理研究所羰基合成与选择性氧化国家重点实验室,甘肃兰州730000 [2]中国科学院大学,北京10049

出　　处：《分子催化》2022年第2期118-128,共11页Journal of Molecular Catalysis(China)

基　　金：国家自然科学基金(21872155,21902164);中国科学院战略性先导科技专项项目(XDA21010700);中国科学院西部青年学者项目和兰州市城关区科技发展项目(2020JSCX0051)

摘　　要：采用共沉淀法制备了不同Fe/Ni摩尔比(0、0.125、0.25、0.5和0.75)的Al_(2)O_(3)负载型NiFe单、双金属催化剂,并考察了它们在生物糠醛衍生2-羟基四氢吡喃(2-HTHP)还原胺化合成高附加值5-氨基戊醇反应中的催化性能.研究发现当Fe/Ni摩尔比为0.25时表现出最高的5-氨基戊醇收率(在80℃和2 MPa优化条件下达90%).利用N_(2)吸脱附、X射线衍射(XRD)、氢气程序升温还原(H_(2)-TPR)、透射电镜(TEM)等技术对催化剂进行了表征,结果表明适量Fe的掺入可以提高催化剂的分散性和还原性,同时在还原活化催化剂中形成Ni-Fe合金相,继而使相应催化剂表现出更优异的催化活性.通过固定床对比考察了催化剂的稳定性,NiFe(0.25)-Al-O双金属催化剂表现出明显优于NiFe(0)-Al-O单金属催化剂的稳定性,运行120 h前者只有微弱失活而后者显著失活.对比反应后催化剂表征发现,金属Fe的修饰可以有效抑制金属活性颗粒的烧结和流失,从而显著提高其反应稳定性.Al_(2)O_(3)supported NiFe bimetallic catalysts with different Fe/Ni molar ratios(0,0.125,0.25,0.5 and 0.75)were prepared by co-precipitation method for the reductive amination(RA)of biofurfural-derived 2-hydroxytetrahydropyran(2-HTHP)to synthesis valuable 5-amino-1-pentanol(5-AP)and best catalytic performance was obtained when the Fe/Ni mole ratio is 0.25.The effect of metal Fe modification on the catalyst structure,in combination with the evaluation of the catalytic activity and stability was studied in 2-HTHP reductive amination.The results show that incorporation of appropriated Fe could improve the dispersity and reducibility of the catalyst.Moreover,the formation of Ni-Fe alloy structure showed better catalytic activity and stability on bimetallic catalyst.Through the XRD and TEM analysis of the used catalyst showed that the Ni-Fe alloy structure could effectively inhibit the sintering and leaching of active metal particles,thus significantly improving its stability.

关 键 词：NiFe双金属 生物质 还原胺化 氨基醇 构效关系 

分 类 号：TQ226.34[化学工程—有机化工] TQ426