华南理工大学学报(自然科学版) ›› 2015, Vol. 43 ›› Issue (6): 15-21.doi: 10.3969/j.issn.1000-565X.2015.06.003

• 化学化工 • 上一篇    下一篇

5-羟甲基糠醛热解机理的 PY-GC-MS 及原位红外法分析 

廖艳芬 郭振戈 曹亚文 马晓茜 林延   

  1. 华南理工大学 电力学院,广东 广州 510640
  • 收稿日期:2014-11-05 修回日期:2015-01-20 出版日期:2015-06-25 发布日期:2015-05-04
  • 通信作者: 廖艳芬(1976-),女,教授,博士生导师,主要从事固体废弃物高效低污染燃烧研究. E-mail:yfliao@scut.edu.cn
  • 作者简介:廖艳芬(1976-),女,教授,博士生导师,主要从事固体废弃物高效低污染燃烧研究.
  • 基金资助:

    国家“973”计划项目(2013CB228100);国家自然科学基金资助项目(51476060);国家质检公益项目(20140159);广东省能源高效清洁利用重点实验室项目(2013A061401005)

Analysis of Pyrolysis Mechanism of 5-Hydroxymethyl Furfural by Using PY-GC-MS and In-Situ FT-IR

Liao Yan-fen Guo Zhen-ge Cao Ya-wen Ma Xiao-qian Lin Yan   

  1. School of Electric Power,South China University of Technology,Guangzhou 510640,Guangdong,China
  • Received:2014-11-05 Revised:2015-01-20 Online:2015-06-25 Published:2015-05-04
  • Contact: 廖艳芬(1976-),女,教授,博士生导师,主要从事固体废弃物高效低污染燃烧研究. E-mail:yfliao@scut.edu.cn
  • About author:廖艳芬(1976-),女,教授,博士生导师,主要从事固体废弃物高效低污染燃烧研究.
  • Supported by:

    Supported by the National Program on Key Basic Research Project of China(2013CB228100),the National Nat-ural Science Foundation of China(51476060),and the General Administration of Quality Supervision,Inspection of Public Projects (20140159)

摘要: 采用 PY-GC-MS(快速热裂解 - 色质联用)对 5-羟甲基糠醛(5-HMF)进行热裂解实验,发现裂解产物中将近 86%为呋喃环类物质,同时存在小分子物质,表明其热解主要为侧链降解,但也存在呋喃环的开环断裂. 结合原位红外光谱分析,实时监测 5-HMF 热裂解产物随反应过程的转化规律,发现在130 ~230℃之间主要生成糠醛、5-甲基糠醛,250℃后主要生成2-糠醇及5-乙酰甲氧基-2-糠醛,这两者的生成持续至反应中后期;作为 5-HMF热解最主要产物的 2,5-呋喃二甲醛的生成则在整个反应过程持续进行. 结合快速热解及原位红外实验结果,推测 5-HMF 的热解机理如下:侧链羟甲基处连续两次脱氢生成 2,5-呋喃二甲醛是最主要的反应,羟甲基去羟基后加氢生成 5-甲基糠醛,羟甲基侧链及醛基侧链的整体断裂分别生成糠醛及糠醇,在此基础上还会发生二次裂解反应生成 2-甲基呋喃.

关键词: 生物质, 热裂解, 5-羟甲基糠醛, PY-GC-MS, 原位红外

Abstract: Pyrolysis experiments of 5-hydroxymethyl furfural (5-HMF) were conducted and the product composi-tion was detected by using a PY-GC-MS analyzer. The results show that nearly 86% of the pyrolysis product is fu-ran ring-contained substance,and that a certain amount of small molecules exist in the product,which means that the pyrolysis process of 5-HMF is mainly a side-chain degradation process concomitantly with the fracture of furan rings. Moreover,the converting law of the product in the pyrolysis process was supervised in real time via in-situ FT-IR. The results show that furfural and 5-methyl furfural mainly form when the temperature ranges from 130 to 230℃,furfuryl alcohol and 5-formyl-2-furfurylacetate mainly form after 250 ℃ and the formation continues to the middle and later periods of the whole process,while the dominant pyrolysis product of 5-HMF,namely furan-2,5-dicarbaldehyde,forms throughout the whole pyrolysis process. According to the results obtained from fast pyrolysis experiment and in-situ FT-IR,the pyrolysis mechanism is speculated as follows: as the most primary reaction,fu-ran-2,5-dicarbaldehyde forms from two consecutive dehydrogenations and then converts into 5-methyl furfural after the dehydroxylation and hydrogenation of hydroxymethyl; the whole fracture of hydroxymethyl side chain and alde-hyde group side chain leads to the formation of furfural and furfuryl alcohol; and 2-methylfuran may be produced via the secondary pyrolysis of furfural and furfuryl alcohol.

Key words: biomass, pyrolysis, 5-hydroxymethyl furfural, PY-GC-MS, in-situ FT-IR

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