乙炔氢氯化Au-Cu/AC催化剂中Cu价态对Au价态稳定性的影响  

Effect of Cu valence on the stability of Au valence in Au-Cu/AC catalysts for acetylene hydrochlorination

作　　者：王宁 赵基钢[1] 丛梅[1] 董志林 袁向前[1] 孙辉 WANG Ning;ZHAO Jigang;CONG Mei;DONG Zhilin;YUAN Xiangqian;SUN Hui(International Joint Research Center for Green Energy Chemical Engineering,School of Chemical Engineering,East China University of Science and Technology,Shanghai 200237,China)

机构地区：[1]绿色能源化工国际联合研究中心,华东理工大学化工学院,上海200237

出　　处：《化工进展》2020年第11期4480-4487,共8页Chemical Industry and Engineering Progress

基　　金：国家自然科学基金委重大研究计划培育项目(91634112)。

摘　　要：Au-Cu/AC无汞催化剂在乙炔氢氯化反应中具有潜在的工业应用价值。本文采用蒸汽诱导还原及H2还原对Au-Cu/AC催化剂上负载的Cu价态进行调控制备,并采用X射线多晶衍射、程序升温脱附、程序升温还原、X射线光电子能谱、扫描电镜等对反应前后的催化剂进行对比表征,研究了其对Au价态和对乙炔氢氯化反应催化活性的影响。结果表明,分别制备得到含Cu(Ⅱ)83.68%、Cu(Ⅰ)70.92%、Cu(0)77.37%的催化剂,以Au/AC催化剂为基准,在新鲜催化剂上,Cu(Ⅱ)使Au(Ⅰ)的含量从47.65%降低至15.71%,Au(0)增加至62.09%,Cu(Ⅰ)使得Au(Ⅲ)、Au(Ⅰ)的含量下降至14.83%和33.2%,Cu(0)使Au(0)的含量增加至69.99%;在反应过程中,Cu(Ⅱ)、Cu(Ⅰ)分别使Au(0)含量的增长百分比减少为13.81%和15.03%,Cu(Ⅰ)有利于维持Au(Ⅰ)的稳定,抑制Au离子还原为Au(0),促使反应前后Au(Ⅰ)的含量稳定在33%左右,Cu(Ⅱ)在反应中还原为Cu(Ⅰ),继而提高Au(Ⅰ)含量,Cu(0)吸附大量乙炔引发副反应,促进了Au被还原为Au(0),Au(Ⅲ)、Au(Ⅰ)的总含量降低至10.35%,催化剂稳定性下降,丰富了乙炔氢氯化无汞催化剂中铜协同金的应用基础理论。Au-Cu/AC mercury-free catalyst has potential in industrial application for acetylene hydrochlorination.In this paper,vapor-induced selective reduction and H2 reduction were used to control the Cu valence on the Au-Cu/AC catalyst.The structures of fresh and used catalysts were characterized by XRD,C2H2-TPD,H2-TPR,XPS,SEM,etc.,and the effects of Cu valence on the valence state of Au as well as the catalytic activity of acetylene hydrochlorination were studied.Catalysts containing 83.68%Cu(Ⅱ),70.92%Cu(Ⅰ),and 77.37%Cu(0)were prepared.Compared with the Au/AC catalyst,the Cu(Ⅱ)on the fresh Au-Cu/AC catalyst reduced the content of Au(Ⅰ)from 47.65%to 15.71%,increased that of Au(0)to 62.09%,and Cu(Ⅰ)caused Au(Ⅲ)and Au(Ⅰ)contents decreased to 14.83%and 33.2%respectively,while the Cu(0)increased Au(0)content to 69.99%.During the reaction,Cu(Ⅱ)and Cu(Ⅰ)reduced the percentage increase of Au(0)content to 13.81%and 15.03%respectively.Cu(Ⅰ)is beneficial to maintain the stability of Au(Ⅰ),inhibit the reduction of Au ions to Au(0),and promote Au(Ⅰ)content being maintained at about 33%.Cu(Ⅱ)was reduced to Cu(Ⅰ)in the reaction,which increased the Au(Ⅰ)content.Cu(0)adsorbed a large amount of acetylene to initiate side reactions,which promoted the reduction of Au to Au(0),reduced the total contents of Au(Ⅲ)and Au(Ⅰ)to 10.35%,and thus lowered the stability of the catalyst.The results have enriched the basic theory of copper synergism in mercury-free catalyst for acetylene hydrochlorination.

关 键 词：乙炔氢氯化 催化剂 制备 稳定性 金 铜 

分 类 号：O643[理学—物理化学]