Co@NC选择性催化木糖氢解制备1,2-二元醇  

Selective xylose hydrogenolysis to 1,2-diols using Co@NC catalysts

作　　者：梁缘 李志坚 刘琪英[2,4] 马隆龙[2,4] LIANG Yuan;LI Zhi-jian;LIU Qi-ying;MA Long-long(Department of Engineering Science,University of Science and Technology of China,Hefei 230026;Guangzhou Institute of Energy Conversion,Chinese Academy of Sciences,Guangzhou 510640;Nano Science and Technology Institute,University of Science and Technology of China,Suzhou 215123;CAS Key Laboratory of Renewable Energy,Guangzhou 510640)

机构地区：[1]中国科学技术大学工程科学学院,安徽合肥230026 [2]中国科学院广州能源研究所,广东广州510640 [3]中国科学技术大学纳米学院,江苏苏州215123 [4]中国科学院可再生能源重点实验室,广东广州510640

出　　处：《燃料化学学报》2021年第12期1898-1910,共13页Journal of Fuel Chemistry and Technology

基　　金：国家重点科研项目(2018YFB1501402);国家自然科学基金(51976220);广东省“珠江人才计划”本土创新科研团队项目(2017BT01N092)资助。

摘　　要：本研究采用bottom-up法,制备了具有加氢和异构活性的碳包裹金属催化剂Co@NC,用于催化木糖氢解制备1,2-二元醇。结合XRD、TEM、XPS等表征手段对比了不同焙烧温度制备的Co@NC催化剂的物理和化学性质。研究发现,600℃焙烧的Co@NC催化剂具有最高的二元醇的总收率(70.1%),其中,乙二醇、1,2-丙二醇和1,2-戊二醇的收率分别达到17.6%、25.1%和27.4%。机理研究表明,N的掺杂为Co@NC提供了碱性位点,在碱的催化作用下促进木糖向木酮糖的异构,再通过Retro-aldol反应得到乙醇醛和丙酮醇中间产物,最后经加氢得到乙二醇和1,2-丙二醇。1,2-戊二醇来源于木糖的加氢脱氧,其产率高于文献报道的最佳结果。本研究工作发展的水热稳定性优异的Co@NC催化剂为生物质高效制备1,2-二元醇提供了新的研究思路。Xylose is the predominant component of hemicellulose,and converting xylose to valuable compounds is essential to achieve biomass utilization.Herein,N-doped carbon nanotubes encapsulated metal catalysts(Co@NC)with hydrogenation and isomerization capacities were synthesized via bottom-up method for catalyzing xylose hydrogenolysis into 1,2-diols.The physicochemical properties of Co@NC prepared with different calcination temperature were determined by XRD,TEM,XPS and so on.The Co@NC prepared at 600℃exhibited the optimal catalytic activity,and the yield of diols reached 70.1%with ethylene glycol,1,2-propylene glycol and 1,2-pentanediol being 17.6%,25.1%and 27.4%,respectively.The doping N species served as the basic sites which benefited the isomerization of xylose to xylulose.Xylulose was subsequently converted to glycolaldehyde and acetol through Retro-aldol reaction,followed by hydrogenation to produce ethylene glycol and 1,2-propylene glycol.1,2-Pentanediol derived from the selective hydrodeoxygenation of xylose,the yield of which surpassed the results that had been reported.The Co@NC catalysts with high robustness under harsh hydrothermal conditions provided new insights into the effective conversion of lignocellulosic biomass to 1,2-diols.

关 键 词：Co@NC 木糖 氢解 1 2-二元醇 1 2-戊二醇 

分 类 号：TK6[动力工程及工程热物理—生物能] TQ223.162[化学工程—有机化工] TQ426