有序介孔CuCoZr催化剂的制备及其催化合成气制乙醇及高级醇性能  

Preparation of ordered mesoporous CuCoZr catalyst and its catalytic performance for syngas to ethanol and higher alcohols

作　　者：刘瑞琴 孟凡会[1] 王立言 张鹏[1] 张俊峰[2] 谭猗生[2] 李忠[1] LIU Ruiqin;MENG Fanhui;WANG Liyan;ZHANG Peng;ZHANG Junfeng;TAN Yisheng;LI Zhong(State Key Laboratory of Clean and Efficient Coal Utilization,Taiyuan University of Technology,Taiyuan 030024,Shanxi,China;State Key Laboratory of Coal Conversion,Institute of Coal Chemistry,Chinese Academy of Sciences,Taiyuan 030001,Shanxi,China)

机构地区：[1]太原理工大学省部共建煤基能源清洁高效利用国家重点实验室,山西太原030024 [2]中国科学院山西煤炭化学研究所煤转化国家重点实验室,山西太原030001

出　　处：《化工进展》2022年第11期5870-5878,共9页Chemical Industry and Engineering Progress

基　　金：国家自然科学基金重点项目(U1510203);山西省自然科学基金(202103021224073);山西省重点研发计划项目(国际科技合作)(201803D421011)。

摘　　要：改性费托合成催化剂(尤其是CuCo催化剂)在合成气制乙醇及高级醇反应中具有高的催化活性和总醇选择性,被认为是潜在的工业催化剂。采用蒸发诱导自组装(EISA)法和共沉淀(CP)法制备了一系列CuCoZr催化剂,考察了制备方法及EISA法制备的催化剂Cu/Co原子比对合成气制乙醇及高级醇性能的影响。采用N物理吸附-脱附、小角X射线衍射(XRD)、原位XRD、透射电镜(TEM)、H_(2)-程序升温还原(TPR)、CO-程序升温脱附(TPD)和原位红外漫反射光谱(DRIFT)对催化剂进行表征,分析了合成气在Cu/Co原子比为3∶1的Cu_(3)Co_(1)Zr催化剂表面的反应路径。结果表明,EISA法制备的Cu Co Zr催化剂为有序介孔结构,比表面积随Cu/Co原子比的增加先增大后减小,其中Cu_(3)Co_(1)Zr催化剂比表面积和CO吸附量均为最大,分别为143m^(2)/g和0.33mmol/g,催化剂的Cu晶粒尺寸仅为9.1nm。在催化合成气制醇的反应中CO转化率达到74.9%,总醇中的高级醇时空收率达到75.2mg/(g_(cat)·h),乙醇物质的量分数为31.0%,明显优于共沉淀法制备的组成相同的CuCoZr-CP催化剂。Modified Fischer-Tropsch catalysts,especially the CuCo catalyst,are potential industrial catalysts for ethanol and higher alcohols production from syngas,due to their high catalytic activity and total alcohols selectivity.A series of Cu Co Zr catalysts were prepared by evaporation-induced self-assembly(EISA)and co-precipitation(CP)method.The effect of preparation method and Cu/Co atomic ratio of EISA catalyst on its catalytic performance of ethanol and higher alcohols synthesis from syngas were investigated.The catalysts were characterized by Nphysical adsorption-desorption,small-angle XRD,in-situ XRD,TEM,H_(2)TPR,CO-TPD and in-situ DRIFT,and the reaction path of syngas on Cu_(3)Co_(1)Zr catalyst with Cu/Co atomic ratio of 3∶1 was analyzed.The results showed that Cu Co Zr catalyst prepared by EISA method possessed ordered mesoporous structure,and the specific surface area increased firstly and then decreased as the Cu/Co ratio.Cu_(3)Co_(1)Zr catalyst showed the largest specific surface area and CO adsorption capacity,which were 143m^(2)/g and 0.33mmol/g,respectively.Moreover,the crystalline size of Cu was only 9.1nm.During the catalytic reaction,Cu_(3)Co_(1)Zr catalyst gave a CO conversion of 74.9% and a higher alcohol yield of 75.2mg/(g_(cat)·h)with ethanol mole fraction of 31.0%,much better than those given by the co-precipitated CuCoZr-CP catalyst with the same composition.

关 键 词：合成气 加氢 乙醇 高级醇 催化剂 制备方法 介孔结构 

分 类 号：TQ426[化学工程]