稀土修饰对Cu/Al_(2)O_(3)催化乙酰丙酸乙酯加氢性能的影响  

Effect of Rare Earth Modification on the Catalytic Performances of Cu/Al_(2)O_(3)-Based Catalysts for Hydrogenolysis of Ethyl Levulinate

作　　者：商宗玲 张弨[3] 赵凤玉[1,2,3] SHANG Zong-Ling;ZHANG Chao;ZHAO Feng-Yu(State Key Laboratory of Electroanalytical Chemistry,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022,China;School of Applied Chemistry and Engineering,University of Science and Technology of China,Hefei 230026,China;Jilin Province Key Laboratory of Green Chemistry and Process,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022,China)

机构地区：[1]中国科学院长春应用化学研究所,电分析化学国家重点实验室,长春130022 [2]中国科学技术大学应用化学与工程学院,合肥230026 [3]中国科学院长春应用化学研究所,吉林省绿色化学与过程重点实验室,长春130022

出　　处：《应用化学》2024年第3期340-348,共9页Chinese Journal of Applied Chemistry

基　　金：国家自然科学基金(No.22072142)资助。

摘　　要：生物质催化转化制大宗化学品符合低碳战略的重要研究方向,将纤维素衍生物乙酰丙酸乙酯转化为1,4-戊二醇是最具前景的技术路线之一。非贵金属铜基催化剂在该反应中表现出较好的活性,Cu/Al_(2)O_(3)在160℃、4 MPa H_(2)条件下催化乙酰丙酸乙酯氢解制1,4-戊二醇收率为50.8%,经稀土改性后催化剂的活性和选择性显著提升,其中CuNd0.25/Al_(2)O_(3)催化剂上获得1,4-戊二醇的收率高达92.7%。通过对催化剂性能以及X射线衍射(XRD)、透射电子显微镜(TEM)、氢气程序升温还原(H_(2)-TPR)、氢气程序升温脱附(NH3-TPD)和CO红外吸附(CO-DRIFT)等表征结果的分析发现,稀土元素的存在不仅改变了Cu活性中心的还原性质、分散度和电子结构,还改变了催化剂表面酸、碱性位点的分布。稀土元素的修饰既促进了催化剂表面反应物的吸附与活化,又抑制了目标产物1,4-戊二醇的脱水副反应,从而提高了活性和选择性。Catalytic conversion of biomass to bulk chemicals is in line with the important research strategy of low-carbon,transferring cellulose derivative ethyl levulinate to 1,4-pentanediol is one of the most promising technological routes.The non-precious metal copper-based catalysts show good activity in this reaction,and the yield of 1,4-pentanediol from ethyl levulinate hydrogenolysis is only 50.8%on the Cu/Al_(2)O_(3) catalyst at 160℃with 4 MPa H_(2).The catalytic performances are significantly improved after being modified with rare earth element,and the yield of 1,4-pentanediol reaches 92.7%on the CuNd0.25/Al_(2)O_(3) catalyst.Based on the catalytic performances and the characterizing results of X-ray diffraction(XRD),transmission electron microscope(TEM),hydrogen temperature programmed reduction(H_(2)-TPR),ammonia temperature programmed desorption(NH3-TPD)and diffuse reflectance infrared Fourier transform(CO-DRIFT),the presence of rare earth elements not only changes the reduction properties,dispersion,and electronic structure of Cu species,but also alters the distribution of acidic and basic sites on the catalyst surface.The doping of rare earth element could promote both the adsorption and activation of reactants on the catalyst surface and inhibit the side reaction of the target product 1,4-pentanedioldehydration,thus improving the activity and selectivity.

关 键 词：Cu/Al_(2)O_(3)催化剂 稀土修饰 1 4-戊二醇 乙酰丙酸乙酯 氢解 

分 类 号：O643[理学—物理化学]