锆改性Cu/SiO_(2)催化剂催化3-羟基丙酸甲酯选择性加氢  

Selective hydrogenation of methyl 3-hydroxypropionate over zirconiummodified Cu/SiO_(2)catalysts

作　　者：李伟杰 康金灿[1] 张传明 林丽娜 李昌鑫 朱红平[1] LI Weijie;KANG Jincan;ZHANG Chuanming;LIN Lina;LI Changxin;ZHU Hongping(State Key Laboratory of Physical Chemistry of Solid Surfaces,National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,Fujian,China)

机构地区：[1]厦门大学化学化工学院,固体表面物理化学国家重点实验室,醇醚酯化工清洁生产国家工程实验室,福建厦门361005

出　　处：《化工进展》2024年第3期1328-1341,共14页Chemical Industry and Engineering Progress

基　　金：国家自然科学基金(21972112,22172123)。

摘　　要：采用蒸氨法制备了锆(Zr)改性的Cu/SiO_(2)催化剂,用于3-羟基丙酸甲酯(3-HMP)气相加氢制1,3-丙二醇(1,3-PDO)。采用比表面积及孔分布测试、XRD、ICP-OES、H_(2)-TPR、NH_(3)-TPD、CO_(2)-TPD、FTIR、TGDTG、HRTEM、XPS和AES等手段对催化剂进行了详细表征,发现Zr物种的加入使得Cu和Zr物种之间发生了强相互作用,产生了较多的层状硅酸铜,在结构方面提高了催化剂的比表面积,降低了铜物种的粒径,促进铜物种的分散,且在电子调控方面提高了Cu^(+)的含量,增强了催化剂吸附酰基和甲氧基的能力。与未改性的Cu/SiO_(2)催化剂相比,在相同反应条件下,Zr掺杂量为0.5%的Cu/SiO_(2)催化剂表现出更高的催化性能,获得3-羟基丙酸甲酯转化率为96.0%和1,3-丙二醇选择性为84.3%,1,3-PDO的总收率达80.9%。这是目前在高液时空速0.10h^(-1)的条件下取得的最佳结果。A series of the zirconium(Zr)-modified Cu/SiO_(2)catalysts were synthesized by ammoniaevaporation method and applied in the gas-phase hydrogenation of methyl 3-hydroxypropionate(3-HMP)to 1,3-propanediol(1,3-PDO).N_(2) adsorption-desorption,XRD,ICP-OES,H_(2)-TPR,NH_(3)-TPD,CO_(2)-TPD,FTIR,TG-DTG,HRTEM,XPS and AES techniques were used for detailed characterizations.Introduction of the Zr species results in a strong interactions between the Cu and Zr species,leading to the generation of more copper phyllosilicate,and thus increasing the specific surface area of the catalyst as well as reducing the particle sizes of the copper species.The addition of Zr also made the copper species better be dispersed over the SiO_(2)support,increased the Cu^(+) content and enhanced the electronic absorption of the substrate 3-HMP by the acyl and methoxide groups.Compared with the unmodified Cu/SiO_(2)catalyst,the Zr-added(0.5%)Cu/SiO_(2)catalyst showed better catalytic performance.The conversionof 3-HMP as 96.0%was achieved along with the 1,3-PDO selectivity of 84.3%,Resulting in a total yield of 80.9%for 1,3-PDO.These were the best results obtained currently at a high liquid hourly space velocity(LHSV)of 0.10h^(-1).

关 键 词：3-羟基丙酸甲酯 加氢 1 3-丙二醇 铜/二氧化硅 Zr改性 

分 类 号：O643.38[理学—物理化学] TQ426[理学—化学]