铜镍双金属催化剂用于乙二醇氨化制乙二胺反应性能研究  

Study on copper-nickel bimetallic catalysts for amination of ethylene glycol to ethylenediamine

作　　者：樊沛征 郭贝琳 郎超群 吴亚娟 FAN Peizheng;GUO Beilin;LANG Chaoqun;WU Yajuan(Key Laboratory of General Chemistry of the National Ethnic Affairs Commission,School of Chemistry and Environment,Southwest Minzu University,Chengdu 610041,Sichuan,China)

机构地区：[1]西南民族大学化学与环境学院国家民委化学基础重点实验室,四川成都610041

出　　处：《低碳化学与化工》2024年第5期36-43,共8页Low-Carbon Chemistry and Chemical Engineering

基　　金：国家自然科学基金(22002122);西南民族大学研究生创新型科研项目(ZD2022971)。

摘　　要：乙二醇(EG)催化氨化制乙二胺(EDA)是一条绿色、高效和经济的获取EDA的路线,但仍存在反应条件苛刻和产物选择性差等问题亟待解决。通过调整n(Cu):n(Ni),采用共沉淀法制备了一系列Cu_(a)-Ni_(1-a)-Al-O(a取值分别为0.09、0.30、0.50、0.70和0.91)催化剂并用于EG催化氨化制EDA反应。采用X射线衍射(XRD)、N_(2)吸/脱附和高分辨率透射电子显微镜(HR-TEM)等对催化剂进行了表征,并对EG催化氨化制EDA的反应条件进行了优化。结果表明,Ni的引入可以显著提高Cu基单金属催化剂的比表面积,其中Cu_(0.09)-Ni_(0.91)-Al-O具有最大的比表面积(150.20 m^(2)/g)和最小的平均孔径(5.84 nm)。Cu_(a)-Ni_(1-a)-Al-O中的Cu和Ni以CuNi合金形式存在,并且随着a减小,催化剂晶体结晶度和晶体尺寸减小。在最优反应条件(200 mg Cu_(0.09)-Ni_(0.91)-Al-O、1 mmol EG、15 mL1,2-二甲氧基乙烷、7 g NH_(3)、3 MPa H2、180℃以及反应13 h)下,EG转化率和EDA产率分别为100%和60%。Cu_(0.09)-Ni_(0.91)-Al-O在最优反应条件下循环使用4次,其催化性能未表现出明显改变。Catalytic amination of ethylene glycol(EG)to ethylenediamine(EDA)is a green,efficient and economical route to obtain EDA,but there are still some problems to be solved,such as harsh reaction conditions and poor product selectivity.By adjusting n(Cu):n(Ni),a series of Cu_(a)-Ni_(1-a)-Al-O(the value of a is 0.09,0.30,0.50,0.70 and 0.91,respectively)catalysts were prepared by co-precipitation method and used for amination of EG to EDA.The catalysts were characterized by X-ray diffraction(XRD),N_(2) absorption/desorption and high-resolution transmission electron microscopy(HR-TEM),etc,and the reaction conditions of catalytic amination of EG to EDA were optimized.The results show that the specific surface area of Cu-based monmetallic catalyst can be significantly increased by the introduction of Ni,and Cu_(0.09)-Ni_(0.91)-Al-O has the largest specific surface area(150.20 m^(2)/g)and the smallest average pore size(5.84 nm).The Cu and Ni in Cua-Ni1-a-Al-O exist in the form of CuNi alloy,and the crystallinity and crystal size of the catalyst decrease with the decrease of a.Under the optimal reaction conditions(200 mg Cu_(0.09)-Ni_(0.91)-Al-O,1 mmol EG,15 mL 1,2-dimethoxy-ethane,7 g NH_(3),3 MPa H_(2),180℃and reaction for 13 h),the EG conversion rate and EDA yield are 100%and 60%,respectively.Cu_(0.09)-Ni_(0.91)-Al-O is recycled for four times under the optimal reaction conditions,and the catalytic performance of Cu_(0.09)-Ni_(0.91)-Al-O does not change significantly.

关 键 词：铜镍双金属催化剂 催化氨化 乙二胺 乙二醇 

分 类 号：TQ42[化学工程] O643.32[理学—物理化学]