Au/CeO2-cube催化1,3-丙二醇氧化酯化反应性能  

The Influence of CeO_2-Cube Supported Gold Nanoparticle on the Catalytic Performance of 1,3-Propanediol Oxidative Esterification

作　　者：赵广震 赵国明[2,3] 咸漠[2] 党明岩[1] 梁俊杰[2] 陈维民[1] 田原宇[3] Zhao Guangzhen;Zhao Guoming;Xian Mo;Dang Mingyan;Liang Junjie;Chen Weimin;Tian Yuanyu(School of Environmental and Chemical Engineering, Shenyang Ligong University, Shenyang 110159, China;CAS Key Laboratory of Biobased Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101, China;Laboratory of Chemical Engineering and Technology for Low-carbon energy, College of Chemical and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266590, China)

机构地区：[1]沈阳理工大学环境与化学工程学院,辽宁沈阳110159 [2]中国科学院青岛生物能源与过程研究所,中国科学院生物基材料重点实验室,山东青岛266101 [3]山东科技大学化学与环境工程学院,低碳能源化工实验室,山东青岛266590

出　　处：《化学反应工程与工艺》2016年第1期39-48,共10页Chemical Reaction Engineering and Technology

基　　金：国家自然科学基金(21206185);中国科学院创新促进会首批会员专项经费(Y11A031105);青岛市博士后研究人员应用研究项目资助(2015202)

摘　　要：采用沉积-沉淀法制备了高活性的Au/CeO2-cube 催化剂，并对催化剂进行了电感耦合等离子发射光谱、透射电镜、X 射线衍射和X 射线光电子能谱表征。将制得的催化剂用于1,3-丙二醇选择性氧化酯化反应，考察了沉淀剂尿素的用量、CeO2-cube 载体焙烧温度、催化剂焙烧温度、Au 负载量和沉积温度对反应性能的影响，结果表明：尿素和CeO2-cube 的质量比为6、沉积温度80 ℃、CeO2-cube 焙烧温度400 ℃、催化剂焙烧温度200 ℃制备的1.5%Au/CeO2-cube，具有最优的催化活性。在100 ℃、O2 分压2 MPa、1,3-丙二醇和Au的物质的量比为75.5 的条件下反应4 h，1,3-丙二醇的转化率达到97.5%，3-羟基丙酸甲酯和丙二酸二甲酯的选择性分别达到90.1%和6.1%。将用过的催化剂在200 ℃焙烧2 h 烧掉表面的中毒物质后循环使用4 次，催化性能略有降低，性能下降主要是由催化反应过程中Au 颗粒粒径的长大造成的；催化剂上2.0～4.0 nm 左右的具有少量Auδ+的负载纳米Au 单质颗粒有助于醇的氧化酯化反应。Au nanoparticles supported on CeO2 nanocubes were successfully prepared by adeposition-precipitation method and tested for the oxidative esterification of 1,3-propanediol. The catalystwas characterized by inductively coupled plasma atomic emission spectrometry, transmission electronmicroscope (TEM), X-ray diffraction, and X-ray photoelectron spectroscopy. The different parameters whichmay affect catalytic performance, such as dosage of urea, the calcination temperature of CeO2 nanocubes,the calcination temperature of Au/CeO2-cube, Au loading and the loading temperature were investigated. Theoptimized preparation conditions of Au/CeO2-cube were obtained as follows: the mass ratio of urea/ceria 6,the calcination temperature of CeO2 nanocubes 400 ℃,the calcination temperature of Au/CeO2-cube200 ℃,Au loading 1.5% and the loading temperature 80 ℃. Under the condition of 100 ℃, pressure of O22 MPa, the mole ratio of 1,3-propanediol to Au 75.5 and the reaction time 4 hours, the conversion of1,3-propanediol was 97.5% and the selectivities to methyl 3-hydroxypropionate and dimethyl malonate were 90.1% and 6.1%, respectively. It was found that the catalytic performance decreased slightly when usedcatalyst was calcined at 200 ℃ for 2 h to burn the surface poisoning substance and recycled four times.This was mainly caused by the fact that Au particle size grew larger in the process of catalytic reaction. Itwas found that nano Au elemental catalyst particles with the size of 2.0-4.0 nm supported on CeO2 favors forthe 1,3-propanediol oxidative esterification.

关 键 词：纳米金二氧化铈立方体 1 3-丙二醇 3-羟基丙酸甲酯氧化酯化反应 

分 类 号：O643.32[理学—物理化学]