沉淀剂对Ni-Ce催化剂催化四氢糠醇选择性加氢开环性能的影响  

Effect of Precipitators on Selective Hydrogenation Ring-opening of Tetrahydrofurfuryl Alcohol over Ni-Ce Catalysts

作　　者：刘琪 李福伟 孙鹏[1] 高广[1] 席永杰 赵泽伦 黄志威[1] LIU Qi;LI Fuwei;SUN Peng;GAO Guang;XI Yongjie;ZHAO Zelun;HUANG Zhiwei(State Key Laboratory for Oxo Synthesis and Selective Oxidation,State Key Laboratory of Low Carbon Catalysis and Carbon Dioxide Utilization,Lanzhou Institute of Chemical Physics,Chinese Academy of Sciences,Lanzhou 730000,China;University of Chinese Academy of Sciences,Beijing 100049,China)

机构地区：[1]中国科学院兰州化学物理研究所低碳催化与二氧化碳利用全国重点实验室羰基合成与选择氧化国家重点实验室,甘肃兰州730000 [2]中国科学院大学,北京100049

出　　处：《分子催化(中英文)》2025年第1期14-22,I0001,共10页Journal of Molecular Catalysis(China)

基　　金：国家自然科学基金(22272187,22102196,22102193);甘肃省科技重大专项(22ZD6GA003,23ZDFA016);甘肃省科技计划基础研究创新群体项目(23JRRA568);中国科学院“西部之光”西部青年学者项目。

摘　　要：生物基呋喃化合物制备高值含羟基聚酯单体是绿色化学领域的研究热点,其中非贵金属催化剂对C—O键断裂的选择性和稳定性仍亟待提高.本文分别以草酸钠(Na_(2|)C_(2)O_(4))、碳酸钠(Na2CO3)、氢氧化钠(NaOH)和草酸(H_(2)C_(2)O_(4))为沉淀剂,采用共沉淀法制备了一系列Ni-Ce催化剂,考察了其在四氢糠醇(THFA)氢解开环制1,5-戊二醇反应中的催化性能.利用SEM、XRD、BET、准原位XPS、Raman等表征手段,研究了沉淀剂对催化剂结构的影响,探究了催化剂结构与氢解性能之间的关系.结果表明,以H_(2)C_(2)O_(4)为沉淀剂的催化剂由于具有较小的粒径尺寸和较高浓度的Ni-VO-Ce物种,明显优于其他催化剂的催化性能.在170℃,4 MPa H_(2),反应20 h条件下,该催化剂在THFA氢解反应中对1,5-戊二醇的选择性和收率分别为92.8%和90.4%.该催化剂表现出良好的稳定性,循环套用5次未见明显失活.The transformation of biomass-based furan compounds to high-valued hydroxy-containing polyester monomer has attracted attention in the fields of green chemistry,and the catalytic selectivity and stability of nonnoble metal catalysts in the selective scission of C—O bond needs to be improved.In this work,Ni-Ce catalysts are prepared by co-precipitation method using sodium oxalate(Na_(2|)C_(2)O_(4)),sodium carbonate(Na2CO3),sodium hydroxide(NaOH),and oxalic acid(H_(2)C_(2)O_(4))as precipitators,respectively.The structure of catalysts is characterized by SEM,XRD,BET,quasi in-situ XPS and Raman.The effects of different precipitants on catalytic performance of Ni-Ce catalysts in the transformation of tetrahydrofurfuryl alcohol(THFA)to 1,5-pentanediol are investigated,and the structure-activity relationship is preliminarily discussed.The Ni-Ce-H_(2)C_(2)O_(4)catalyst shows higher catalytic activity(the selectivity and yield of 1,5-pentanediol up to 92.8%and 90.4%,respectively)at 170℃under 4 MPa H_(2)for 20 h,which can be attributed to its smaller particle size and higher concentration of Ni-VO-Ce species.Furthermore,the catalyst shows good stability and can be recycled 5 times.

关 键 词：Ni-Ce催化剂 C—O键氢解 四氢糠醇 1 5-戊二醇 

分 类 号：O643.32[理学—物理化学]