纤维素快速热解生成左旋葡聚糖的机理研究进展

doi:10.3969/j.issn.1673-5854.2014.03.011

生物质化学工程 ›› 2014, Vol. 48 ›› Issue (3): 53-59.doi: 10.3969/j.issn.1673-5854.2014.03.011

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纤维素快速热解生成左旋葡聚糖的机理研究进展

张阳, 胡斌, 陆强, 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 102206

收稿日期:2013-10-24 出版日期:2014-05-30 发布日期:2014-05-29
通讯作者: 陆强（1982- ），男，博士，副教授，硕士生导师，研究方向：生物质高效热解转化;E-mail：qianglu@mail.ustc.edu.cn。 E-mail:qianglu@mail.ustc.edu.cn
作者简介:张阳（1991- ），男，河北保定人，硕士生，研究方向：生物质高效热解转化的机理研究工作
基金资助:
“十二五”国家科技支撑计划资助（2012BAD30B01）；苏州市科技计划项目（SYG201216）

A Review on the Formation Mechanism of Levoglucosan during Fast Pyrolysis of Cellulose

ZHANG Yang, HU Bin, LU Qiang, DONG Chang-qing, YANG Yong-ping

National Engineering Laboratory for Biomass Power Generation Equipment, North China Electric Power University, Beijing 102206, China

Received:2013-10-24 Online:2014-05-30 Published:2014-05-29

摘要/Abstract

摘要： 左旋葡聚糖（LG）是纤维素中温快速热解最重要的产物，其生成机理获得了广泛的关注。本文首先总结了国内外不同学者提出的LG生成机理，将其按照反应类型分为4类，即糖苷键均裂反应、糖苷键异裂反应、生成葡萄糖中间体反应以及协同反应，并指出了实验研究在确定反应机理方面的不足。随后总结了近年来一些学者采用密度泛函理论对LG生成机理的研究，具体比较了研究内容和结果，指出了现有研究的不足。最后提出了今后的研究方向以确定LG的生成途径。

关键词: 纤维素, 快速热解机理, 左旋葡聚糖

Abstract: During the fast pyrolysis of cellulose at medium temperature, levoglucosan (LG) is the most abundant product. Its formation pathway has gained extensive attention. This paper firstly concludes and compares the different LG formation pathways proposed by scholars from home and abroad. The formation mechanisms of LG are classified into 4 kinds, namely homolysis cleavage mechanism, heterolysis cleavage mechanism, mechanism via glucose and concerted decomposition mechanism. Drawbacks of analyzing reaction mechanism using experimental methods are also pointed out. The paper then summarizes the recent development, i.e. application of the Density Functional Theory (DFT). Its contents and results are compared in detail. Finally, future investigation in determination of the LG formation pathway is proposed.

Key words: cellulose, fast pyrolysis mechanism, levoglucosan

中图分类号:

张阳, 胡斌, 陆强, 董长青, 杨勇平. 纤维素快速热解生成左旋葡聚糖的机理研究进展[J]. 生物质化学工程, 2014, 48(3): 53-59.

ZHANG Yang, HU Bin, LU Qiang, DONG Chang-qing, YANG Yong-ping. A Review on the Formation Mechanism of Levoglucosan during Fast Pyrolysis of Cellulose[J]. bce, 2014, 48(3): 53-59.

参考文献

[1] HUBER G W, IBORRA S, CORMA A.Synthesis of transportation fuels from biomass: Chemistry, catalysts, and engineering[J].Chemical Reviews, 2006, 106(9):4044-4098.
[2] 蒋剑春.生物质能源转化技术与应用(Ⅰ)[J].生物质化学工程, 2007, 41(3):59-65.
[3] BRIDGWATER A V.Review of fast pyrolysis of biomass and product upgrading[J].Biomass and Bioenergy, 2012, 38:68-94.
[4] 徐俊明, 戴伟娣, 许玉, 等.生物质快速热解技术及产物提质改性研究进展[J].生物质化学工程, 2011, 45(6):43-48.
[5] 王予, 马文超, 朱哲, 等.生物质快速热解与生物油精制研究进展[J].生物质化学工程, 2011, 45(5):29-36.
[6] 刘守新, 张世润.生物质的快速热解[J].林产化学与工业, 2004, 24(3):95-101.
[7] CZERNIK S, BRIDGWATER A V.Overview of application of biomass fast pyrolysis oil[J].Energy & Fuels, 2004, 18(2):590-598.
[8] 李允超, 王贤华, 杨海平, 等.生物油分离精制技术的研究进展[J].生物质化学工程, 2010, 44(6):46-51.
[9] 顾帅, 杨洪雪, 苗玮, 等.生物油精制技术研究进展[J].林产化学与工业, 2012, 32(2):55-60.
[10] PISKORZ J, RADLEIN D, SCOTT D S.On the mechanism of the rapid pyrolysis of cellulose[J].Journal of Analytical and Applied Pyrolysis, 1986, 9(2):121-137.
[11] LIN Y, CHO J, TOMPSETT G A, et al.Kinetics and mechanism of cellulose pyrolysis[J].Journal of Physical Chemistry(C), 2009, 113(46):20097-20107.
[12] 黄承洁, 姬登祥, 于凤文, 等.生物质热解动力学研究进展[J].生物质化学工程, 2010, 44(1):39-43.
[13] 廖艳芬, 王树荣, 马晓茜.纤维素热裂解左旋葡聚糖生成过程模拟研究[J].林产化学与工业, 2006, 26(2):1-6.
[14] LU Q, YANG X, DONG C, et al.Influence of pyrolysis temperature and time on the cellulose fast pyrolysis products:Analytical Py-GC/MS study[J].Journal of Analytical and Applied Pyrolysis, 2011, 92(2):430-438.
[15] PAKHOMOV, A M.Free-radical mechanism of the thermodegradation of cellulose and formation of levoglucosan[J].Russian Chemical Bulletin, 1957, 6(12):1525-1527.
[16] SHEN D K, GU S.The mechanism for thermal decomposition of cellulose and its main products[J].Bioresource Technology, 2009, 100(24):6496-6504.
[17] GOLOVA O P.Chemical effects of heat on cellulose[J].Russian Chemical Reviews, 1975, 44(8):687-697.
[18] KILZER F J, BROIDO A.Speculations on the nature of cellulose pyrolysis[J].Pyrodynamics, 1965, 2(2):151-163.
[19] SHAFIZADEH F, BRADBURY A G W.Thermal degradation of cellulose in air and nitrogen at low temperatures[J].Journal of Applied Polymer Science, 1979, 23(5):1431-1442.
[20] GARDINER D.The pyrolysis of some hexoses and derived di-, tri-, and poly-saccharides[J].Journal of the Chemical Society(C):Organic, 1966:1473-1476.
[21] RICHARDS G N.Glycolaldehyde from pyrolysis of cellulose[J].Journal of Analytical and Applied Pyrolysis, 1987, 10(3):251-255.
[22] PONDER G R, RICHARDS G N, STEVENSON T T.Influence of linkage position and orientation in pyrolysis of polysaccharides:A study of several glucans[J].Journal of Analytical and Applied Pyrolysis, 1992, 22(3):217-229.
[23] IVANOV V I, GOLOVA O P, PAKHOMOV A M.Main direction of reaction in the thermal decomposition of cellulose in a vacuum[J].Russian Chemical Bulletin, 1956, 5(10):1295-1296.
[24] BYRNE G A, GARDINER D, HOLMES F H.The pyrolysis of cellulose and the action of flame-retardants[J].Journal of Applied Chemistry, 1966, 16(3):81-88.
[25] MAMLEEV V, BOURBIGOT S, BRAS M L, et al.The facts and hypotheses relating to the phenomenological model of cellulose pyrolysis:Interdependence of the steps[J].Journal of Analytical and Applied Pyrolysis, 2009, 84(1):1-17.
[26] ASSARY R S, CURTISS L A.Thermochemistry and reaction barriers for the formation of levoglucosenone from Cellobiose[J].ChemCatChem, 2012, 4(2):200-205.
[27] CHOI S, KIM M, KIM Y.Influence of silica on formation of levoglucosan from carbohydrates by pyrolysis[J].Journal of Analytical and Applied Pyrolysis, 2011, 90(1):56-62.
[28] 黄金保, 刘朝, 魏顺安, 等.纤维素热解形成左旋葡聚糖机理的理论研究[J].燃料化学学报, 2011, 39(8):590-594.
[29] ZHANG X, LI J, YANG W, et al.Formation mechanism of levoglucosan and formaldehyde during cellulose pyrolysis[J].Energy & Fuels, 2011, 25(8):3739-3746.
[30] MAYES H B, BROADBELT L J.Unraveling the reactions that unravel cellulose[J].The Journal of Physical Chemistry(A), 2012, 116(26):7098-7106.

纤维素快速热解生成左旋葡聚糖的机理研究进展

A Review on the Formation Mechanism of Levoglucosan during Fast Pyrolysis of Cellulose

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