介孔CuO-CeO_(2)复合氧化物负载Au催化剂催化氧化甘油制备二羟基丙酮  

Selective Catalytic Oxidation of Glycerol to Dihydroxyacetone by CuO-CeO_(2) Mesoporous Composite Oxide Supported Au Catalyst

作　　者：柯义虎 余小梅 王学 徐换换 曹馨怡 朱钰卿 王非[2] KE Yihu;YU Xiaomei;WANG Xue;XU Huanhuan;CAO Xinyi;ZHU Yuqing;WANG Fei(School of Chemistry and Chemical Engineering,State Ethnic Affairs Commission,Ningxia Key Laboratory of Solar Chemical Conversion Technology,North Minzu University,Yinchuan 750021,China;School of Petrochemical Engineering,Jiangsu Province Key Laboratory of Fine Petrochemical Engineering,Changzhou University,Changzhou 213164,China)

机构地区：[1]北方民族大学化学与化学工程学院,国家民委化工技术基础重点实验室,宁夏太阳能化学转化技术重点实验室,宁夏银川750021 [2]常州大学石油化工学院,江苏省精细石油化工重点实验室,江苏常州213164

出　　处：《化学反应工程与工艺》2022年第6期491-501,共11页Chemical Reaction Engineering and Technology

基　　金：国家自然科学基金项目(21862001);北方民族大学高层次人才项目(2019BGGZ12);宁夏低品质资源高值化利用技术研发人才小高地;江苏省精细石油化工重点实验室开放课题基金资助项目(KF2107);江苏高校自然科学研究面上项目(20KJD530001);催化基础国家重点实验室(中国科学院大连化物所)开放课题(N-20-12)。

摘　　要：以SBA-15为硬模板制备一系列不同Cu和Ce物质的量之比(Cu/Ce比)的介孔CuO-CeO_(2)复合氧化物,并采用均匀沉积沉淀法成功制备了负载型Au催化剂,在无碱条件下,将此催化剂用于催化甘油氧化制备1,3-二羟基丙酮(DHA)反应体系。通过X射线衍射(XRD)、透射电镜(TEM)、X射线光电子能谱(XPS),H_(2)程序升温还原(H_(2)-TPR)和CO_(2)程序升温脱附(CO_(2)-TPD)等方法表征了CuO-CeO_(2)复合氧化物以及其负载Au催化剂。结果表明:不同Cu/Ce比下,由于载体结构发生明显的改变,导致催化剂中活性组分Au与载体间、Cu与Ce之间的相互作用以及催化剂的结构存在差异,因此在催化反应中,表现出不同的催化活性。当Cu/Ce比为5:1时,Au/CuO-CeO_(2)催化剂具有较好的催化性能,在反应温度为80℃,初始氧气压力为1 MPa,反应2 h时,甘油转化率为80.3%,DHA的选择性为89.7%。A series of CuO-CeO_(2) mesoporous composite oxides with different molar ratios of Cu to Ce(Cu/Ce ratio)were prepared using SBA-15 as a hard template.Then supported Au catalysts were prepared by deposition-precipitation.These catalysts were tested for the selective catalytic oxidation of glycerol to 1,3-dihydroxyacetone(DHA)in base-free conditions.Surface characterization using X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),transmission electron microscopy(TEM),temperature-programmed reduction of H_(2)(H_(2)-TPR),and temperature-programmed desorption of CO_(2)(CO_(2)-TPD).The results showed that under different Cu/Ce ratios,the support structure changed significantly,leading to differences in the interaction between the active component Au and the support and between Cu and Ce in the catalyst,so the catalysts showed different catalytic activities.When the Cu/Ce ratio was 5:1,the Au/CuO-CeO_(2) catalyst showed a better catalytic performance.Under the conditions of reaction temperature of 80℃,initial oxygen pressure of 1 MPa,and reaction time of 2 h,the conversion rate of glycerol was 80.3%,and the selectivity of DHA was 89.7%.

关 键 词：甘油 1 3-二羟基丙酮 催化氧化 负载Au催化剂 CuO-CeO_(2)复合氧化物 

分 类 号：O643.36[理学—物理化学] TQ426.83[理学—化学]