焙烧温度对MOF衍生Cu@C催化剂催化草酸二甲酯加氢制乙二醇性能的影响  

Effects of calcination temperatures on performances of MOF-derived Cu@C catalysts for catalytic hydrogenation of dimethyl oxalate to ethylene glycol

作　　者：靳刘艳 赵江涛 张雨 艾培培 黄伟 JIN Liuyan;ZHAO Jiangtao;ZHANG Yu;AI Peipei;HUANG Wei(State Key Laboratory of Clean and Efficient Coal Utilization,College of Chemical Engineering and Technology,Taiyuan University of Technology,Taiyuan 030024,Shanxi,China)

机构地区：[1]太原理工大学化学工程与技术学院省部共建煤基能源清洁高效利用国家重点实验室,山西太原030024

出　　处：《低碳化学与化工》2025年第3期30-38,共9页Low-Carbon Chemistry and Chemical Engineering

基　　金：国家自然科学基金青年科学基金(22008166);山西省面上青年基金(201901D211047);山西省高等学校科技创新项目(2019L0185)。

摘　　要：草酸二甲酯(DMO)加氢制乙二醇(EG)是煤基合成气制EG的关键步骤,该步骤对于替代传统石油衍生路线生产EG并实现煤炭高附加值转化具有重要意义,而高效、稳定的催化DMO加氢制EG催化剂是推动煤基合成气制EG进一步发展的关键。以Cu-1,3,5-苯三羧酸金属有机骨架(Cu-BTC MOF)为前驱体,将其在N_(2)气氛、不同温度下焙烧得到了Cu@C-x(x为焙烧温度)催化剂,并将Cu@C-x催化剂用于催化DMO加氢制EG反应。通过XRD、SEM、H_(2)-TPR、XPS和N_(2)物理吸/脱附对催化剂进行了表征,研究了焙烧温度对其物相组成、形貌、还原性能、表面元素组成和织构性质的影响。结果表明,焙烧温度改变了Cu物种与碳载体(Cu—O—C)的相互作用,进而显著影响了Cu颗粒尺寸和n(Cu^(+))/n(Cu^(0)+Cu^(+))。得益于适中的Cu物种与碳载体的相互作用,Cu@C-500催化剂具有最小的Cu颗粒尺寸和最大的n(Cu^(+))/n(Cu^(0)+Cu^(+))。在240℃、2.5 MPa、反应空速为0.2 h^(-1)和n(H_(2))/n(DMO)为200反应条件下,Cu@C-500催化剂的DMO转化率达100%,EG选择性达94.13%,且在250 h内未出现失活现象。Hydrogenation of dimethyl oxalate(DMO)to ethylene glycol(EG)represents a pivotal step in EG production from coal-based syngas.This process is of great significance for replacing traditional petroleum-derived route to produce EG and achieving high value-added conversion of coal.Efficient and stable catalysts for catalytic hydrogenation of DMO to EG are crucial for promoting the further development of coal-based syngas for EG production.Cu-1,3,5-phenyltricarboxylic acid metal organic framework(Cu-BTC MOF)was used as a precursor and calcined under N_(2) atmosphere at different temperatures to obtain Cu@C-x(x is the calcination temperature)catalysts,and Cu@C-x catalysts were used to catalyze the hydrogenation of DMO to EG.The catalysts were characterized by XRD,SEM,H_(2)-TPR,XPS and N_(2) physical adsorption/desorption.The effects of calcination temperatures on phase compositions,morphologies,reduction performances surface element compositions and texture properties were also investigated.The results show that calcination temperatures change the interaction between Cu species and the carbon support(Cu—O—C),thereby significantly affecting the Cu particles sizes and n(Cu^(+))/n(Cu^(0)+Cu^(+)).Thanks to the moderate interaction between Cu species and the carbon support,Cu@C-500 catalyst has the smallest Cu particle size and largest n(Cu^(+))/n(Cu^(0)+Cu^(+)).Under the reaction conditions of 240℃,2.5 MPa,weight hourly space velocity of 0.2 h^(-1) and n(H_(2))/n(DMO)of 200,Cu@C-500 catalyst achieves the DMO conversion rate of 100%and EG selectivity of 94.13%,and no deactivation occurs within 250 h.

关 键 词：MOF CU催化剂 草酸二甲酯 乙二醇 焙烧温度 

分 类 号：TQ530.2[化学工程—煤化学工程]