吡喃木糖和O鄄乙酰基吡喃木糖热解形成羟基乙醛的机理-燃料化学学报.PDFVIP

第43卷 第2期 燃摇 料摇 化摇 学摇 学摇 报 Vol.43 No.2 2015年2月 Journal of Fuel Chemistry and Technology Feb. 2015 文章编号:0253鄄2409(2015)02鄄0185鄄10 吡喃木糖和O鄄乙酰基吡喃木糖热解形成羟基乙醛的机理研究 田慧云,胡摇 斌,张摇 阳,陆摇 强,董长青,杨勇平 (华北电力大学 生物质发电成套设备国家工程实验室,北京摇 102206) 摘摇 要:以半纤维素主要成分木聚糖的两种单体———吡喃木糖和O鄄乙酰基吡喃木糖为模型化合物,运用密度泛函理论(DFT), 采用B3LYP方法和6鄄31+G(d,p)基组进行计算,研究了吡喃木糖热解形成HAA的6条可能的反应路径和O鄄乙酰基吡喃木糖热 解形成HAA的3条可能的反应路径。 由此确定了吡喃木糖热解形成HAA 的最优路径为:吡喃木糖首先开环得到链式木糖,然 后C3羟基和C2氢脱水,随后经重排和逆醇醛缩合反应生成包含 C4/ C5 的HAA;该路径的决速步骤为脱水反应,能垒为 253.3kJ/ mol。 O鄄乙酰基吡喃木糖热解形成HAA的最优路径为:O鄄乙酰基吡喃木糖首先支链断裂脱出乙酸(AA),开环后的链 式中间体经氢转移反应得到包含C4/ C5 的HAA;该路径的决速步骤为最后的氢转移反应,能垒为317.6kJ/ mol。 关键词:吡喃木糖;O鄄乙酰基;热解;羟基乙醛;密度泛函理论 中图分类号:TK6摇 摇 文献标识码:A Mechanism for the formation of hydroxyacetaldehyde by the pyrolysis of xylopyranose and O鄄acetyl鄄xylopyranose TIAN Hui鄄yun,HU Bin,ZHANG Yang,LU Qiang,DONG Chang鄄qing,YANG Yong鄄ping (NationalEngineering LaboratoryforBiomass Power Generation Equipment,North China ElectricPower University,Beijing摇 102206,China) Abstract:Xylopyranose and O鄄acetyl鄄xylopyranose,the two monomersof xylan,were employed asthe model compoundsto study the mechanism for the formation of hydroxyacetaldehyde (HAA) from xylan by pyrolysis. Six possible pathwaysfrom xylopyranose and three from O鄄acetyl鄄xylopyranose wereproposedby employing the density functional theory (DFT) at B3LYP/ 6鄄31+G(d,p) level;the energetically favored pathways for HAA formation were revealed. Xylopyranose may undergo ring鄄opening,dehydration,rearrangement and retro鄄aldol reactions sequentially,to form HAA that contains C4/ C5;the rate鄄determining step isthe dehydration reaction, with anenergybarrier of253.3kJ/ mol. From O鄄acetyl鄄xylopyranose,the sidechainiscleavedinthefirstplace, forming acetic acid (AA) and a cyclic intermediate;the