3-羟基丙酸甲酯加氢合成1,3-丙二醇反应中La对Cu/SiO_(2)催化剂的修饰作用  

Modification of La on Cu/SiO_(2) catalyst for hydrogenation synthesis from methyl 3-hydroxypropionate to 1,3-propanediol

作　　者：林丽娜 康金灿[1] 张传明 李伟杰 李昌鑫 赖恩义 朱红平[1] LIN Lina;KANG Jincan;ZHANG Chuanming;LI Weijie;LI Changxin;LAI Enyi;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,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,醇醚酯清洁生产国家工程实验室,福建厦门361005

出　　处：《厦门大学学报（自然科学版）》2024年第1期63-72,共10页Journal of Xiamen University：Natural Science

基　　金：国家自然科学基金(21972112,22172123);福建省高校产学研项目(2021H6002)。

摘　　要：[目的] 3-羟基丙酸酯加氢制备1,3-丙二醇(1,3-PDO)过程中存在β-羟基脱除等副反应,导致1,3-PDO的选择性和收率不高,其中高效催化剂的开发是解决该问题的关键.[方法]采用蒸氨法制备了不同添加量La修饰的20Cu/SiO_(2)催化剂,对其进行催化性能评价,并通过H_(2)程序升温还原(H_(2)-TPR)、X射线衍射(XRD)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)和N_(2)物理吸附-脱附对其进行表征.[结果] 20Cu-0.50La/SiO_(2)的催化性能最佳,它显著地提高了3-羟基丙酸甲酯(3-HMP)加氢制1,3-PDO的催化活性和稳定性,其中3-HMP转化率为91.8%,1,3-PDO的选择性和收率分别为85.2%和78.2%.这是在高液时空速(LHSV=0.10 h^(-1))的条件下取得的最佳结果.[结论] La的加入与Cu产生了强相互作用,增强了催化剂中Cu的分散性,同时提高了Cu^(+)物种表面浓度,使活性Cu的比表面积增加,从而提高了加氢反应的活性和稳定性.[Objective] 1,3-Propanediol(1,3-PDO) is widely utilized as a raw material in industry,particularly as the key monomer for manufacturing polytrimethylene terephthalate(PTT),a well-known fiber resin,through a reaction with p-phthalic acid(PTA).Currently,the technology for production of 1,3-PDO is grasped by foreign companies,hindering the application and development of the advanced fiber resins.In this regard,it is necessary to develop technology for the production of 1,3-PDO.Recent progress has focused on the method involving epoxide hydroesterification that includes 3-hydroxypropionate methyl ester(3-HMP) as an intermediate,and hydrogenation to 1,3-PDO is of the current challenge.This study aims at preparing the La metal-promoted Cu/SiO_(2) catalyst and investigating its catalytic property.[Methods] Catalysts formulated as 20Cu-xLa/SiO_(2) were prepared using materials such as Cu(NO_(3))_(2)·3H_(2)O,La(NO_(3))_(3)·6H_(2)O,silica sol(containing 30% SiO_(2) by mass),ethanol,and NH_(3)·H_(2O) through the ammonia distillation method.The catalytic performance of 3-HMP hydrogenation to 1,3-PDO was tested over the catalysts using a fixed bed reactor.The catalysts were characterized using H_(2) temperature-programmed reduction(H_(2)-TPR),H_(2) temperature-programmed desorption(H_(2)-TPD),X-ray diffraction(XRD),transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS),and N_(2) physical adsorption desorption.[Results] It is found that the catalyst 20Cu-0.50La/SiO_(2) has the best catalytic performance,achieving a 3-HMP conversion of 91.8% at a high liquid space velocity(LHSV) of 0.10 h^(-1),along with 1,3-PDO selectivity and yield up to 85.2% and 78.2%.The doping of La metal produces a strong interaction with the Cu in the SiO_(2) support,which increases the dispersity of the Cu and the surface concentration of Cu^(+) species.The surface area of the active Cu species is greatly enlarged,thereby improving the activity and stability of the catalysts in the hydrogenation reaction.Furthermore,the 20Cu-0.5

关 键 词：3-羟基丙酸甲酯 加氢 1 3-丙二醇 蒸氨法 CU催化剂 La助剂 

分 类 号：O643.38[理学—物理化学]