无碱条件下Ru/MgO催化5-羟甲基糠醛氧化并制备高纯度2,5-呋喃二甲酸  

Ru/MgO catalyzed oxidation of 5-hydroxymethylfurfural to prepare high-purity 2,5-furandicarboxylic acid under base-free conditions

作　　者：楚国宁 王赛 马骥 李菁 张爽 CHU Guoning;WANG Sai;MA Ji;LI Jing;ZHANG Shuang(Institute of Petrochemical Technology,Jilin Institute of Chemical Technology,Jilin 132022,China)

机构地区：[1]吉林化工学院石油化工学院,吉林吉林132022

出　　处：《化工科技》2024年第4期55-61,共7页Science & Technology in Chemical Industry

基　　金：吉林省科技厅自然科学基金项目(YDZJ202101ZYTS163);吉林化工学院博士启动基金项目(2020006)。

摘　　要：采用煅烧法制备载体MgO,再采用浸渍-还原法制备Ru/MgO催化剂。对催化剂进行表征分析,结果表明,MgO负载Ru后比表面积与碱量增加,Ru作为催化剂活性中心,将Ru/MgO催化剂用于无碱条件下5-羟甲基糠醛(HMF)的选择性氧化,催化活性显著提高。MgO在负载Ru后,转换频率(TOF)由2.82×10^(-4) h^(-1)提高至5.98×10^(-1) h^(-1)。Ru/MgO催化剂在最佳反应条件下,HMF转化率为100%,2,5-呋喃二甲酸(FDCA)的产率为95.7%,且在循环使用3次后仍能保持较高的活性,活性组分Ru不易浸出,MgO仅有少量溶解。并采用半制备液相色谱实现产物的绿色分离,最终得到纯度大于99%的FDCA粉末,避免了向体系加入浓盐酸分离出FDCA。该制备方法为无碱体系催化HMF高效合成FDCA提供参考。The support MgO was prepared using a calcination method,followed by the preparation of Ru/MgO catalysts through an impregnation-reduction method.Characterization analyses of the catalysts were conducted,and the results indicated that the specific surface area and alkalinity of MgO increased after loaded Ru.Ru,serving as the active center of the catalyst,significantly enhanced the catalytic activity of the Ru/MgO catalyst in the selective oxidation of 5-hydroxymethylfurfural(HMF)under base-free conditions.After loading Ru on MgO,the turnover frequency(TOF)value increased from 2.82×10^(-4) h^(-1) to 5.98×10^(-1) h^(-1).Ru/MgO catalyst under optimal reaction conditions,the conversion rate of HMF reached 100%,and the yield of 2,5-furandicarboxylic acid(FDCA)was 95.7%,and it can maintained high activity after three cycles of reuse,with the active component Ru not leaching significantly and only a minimal amount of MgO dissolving.Semi-preparative liquid chromatography was employed to achieve the green separation of the product,finally obtaining FDCA powder with a purity greater than 99%,thereby avoiding the addition of concentrated hydrochloric acid to separate FDCA.This preparation method provides a reference for the efficient synthesis of FDCA from HMF in an base-free system.

关 键 词：Ru纳米粒子 MGO 5-羟甲基糠醛 无碱催化 产物分离 2 5-呋喃二甲酸 

分 类 号：O643.3[理学—物理化学]