Pt/ReO_(x)/TiO_(2)催化剂选择氢解生物基糠醛制备1,5-戊二醇的研究  

Selective Catalytic Hydrogenolysis of Bio-Based Furfural to 1,5-Pentanediol Based on Pt/ReO_(x)/TiO_(2) Catalyst

作　　者：白小薇 王梦菲 邱腾龙 郭丽[1,2] 李建 BAI Xiaowei;WANG Mengfei;QIU Tenglong;GUO Li;LI Jian(School of Chemical Engineering,Xinjiang University,Urumqi Xinjiang 830017,China;Xinjiang Uygur Autonomous Region Metrology and Testing Research Institute,Urumqi Xinjiang 830011,China)

机构地区：[1]新疆大学化工学院,新疆乌鲁木齐830017 [2]新疆维吾尔自治区计量测试研究院,新疆乌鲁木齐830011

出　　处：《新疆大学学报（自然科学版）（中英文）》2023年第3期313-319,共7页Journal of Xinjiang University(Natural Science Edition in Chinese and English)

基　　金：国家自然科学基金“新疆棉杆生物质在微量氧气下实现热解反应自供热与产物调控的机理研究”(52266016);“纤维素在超临界甲醇中‘一步法’定向解聚制备C2-C6高级醇的机理研究”(52106274)。

摘　　要：生物质基戊二醇优异的热稳定性使其在聚酯市场中有望替代石油基1,6-己二醇和1,4-丁二醇,且能作为有机化工和精细化工原料.研究了催化剂元素组成、反应温度、H_(2)压力、反应时间对生物质基糠醛氢解制备1,5-戊二醇的调控作用.结果表明:稀土元素Re引入显著促进催化剂中Pt平均粒径增加,颗粒尺寸分布更广,当Pt/Re质量比为3∶4时,四氢糠醇C-O键断裂反应与呋喃环加氢反应活性显著高于其它Pt/Re质量比;提高反应温度,不仅有利于环醚C-O的断裂,同时促进呋喃环C=C的加氢反应;增加H_(2)压力对C-OH键的氢解反应无明显促进作用.ReO_(x)和TiO_(2)层区域之间的边界处Re-(OH)-Ti位点为糠醛到四氢糠醇和1,5-戊二醇氢解过程的反应活性中心.边界处Re-(OH)-Ti吸附位点数量的增加促进了醇盐和二级碳正离子化反应生成1,5-戊二醇.以Pt/ReO_(x)/TiO_(2)催化剂、糠醛在130℃、6 MPa下反应8 h,1,5-戊二醇获得最高产率为29.72%.Pentylene glycol derived from biomass is predicted to replace 1,6-hexanediol and 1,4-butanediol derived from petroleum on the polyester market and can be utilized as an organic chemical and fine chemical raw material.The effect of catalyst element composition,reaction temperature,hydrogen pressure and reaction duration on the hydrogenolysis of biomass-derived furfural to produce 1,5-pentanediol is investigated.The results indicate that the addition of the rare earth element Re greatly increased the average particle size and particle size distribution of Pt in the catalyst.When the Pt/Re mass ratio was 3∶4,the reaction of C-O bond breaking with furan ring hydrogenation was significantly higher than that of other Pt/Re mass ratios;Increasing the reaction temperature is not only conducive to the rupture of cyclic ether C-O,but it also promotes the hydrolysis reaction of the furan ring C=C;Increasing the H_(2) pressure has no appreciable effect on the hydrolysis reaction of the C-OH bond.At the interface of the ReO_(x) and TiO_(2) layer zones,the Re-(OH)-Ti site is the center of hydrogenation from furfural to tetrahydrofurfuryl alcohol and 1,5-pentanediol.When the number of Re-(OH)-Ti adsorption sites at the boundary increased,the reaction of alkoxide and secondary carbon positive ionization to generate 1,5-pentanediol was accelerated.1,5-pentanediol was produced with the maximum yield of 29.72% by reacting a Pt/ReO_(x)/TiO_(2) catalyst with furfural at 130 ℃ and 6 MPa for 8 hours.

关 键 词：糠醛 1 2-戊二醇 1 5-戊二醇 选择性氢解 Pt基催化剂 

分 类 号：TQ233.16[化学工程—有机化工] O621.25[理学—有机化学]