五种甘蔗渣分离木质素热解特性及动力学

doi:10.16085/j.issn.1000-6613.2017-0002

化工进展 ›› 2017, Vol. 36 ›› Issue (08): 2910-2915.DOI: 10.16085/j.issn.1000-6613.2017-0002

五种甘蔗渣分离木质素热解特性及动力学

崔兴凯¹, 赵雪冰^1,2, 刘德华^1,2

1. 清华大学化学工程系, 北京 100084;
2. 东莞深圳清华大学研究院创新中心, 广东东莞 523808

收稿日期:2017-01-03 修回日期:2017-02-20 出版日期:2017-08-05 发布日期:2017-08-05
通讯作者: 赵雪冰,研究员,博士生导师,研究方向为生物质化学工程、木质纤维素生物炼制的多元化转化与多尺度分析。
作者简介:崔兴凯(1990-),男,博士研究生,研究方向为木质纤维素基生物源。E-mail:cxingkai@163.com。
基金资助:
国家自然科学基金（21106081）及东莞市社会科技发展项目（2015108101004）。

Pyrolysis characteristics and kinetics of five isolated lignins from sugarcane bagasse

CUI Xingkai¹, ZHAO Xuebing^1,2, LIU Dehua^1,2

1. Department of Chemical Engineering, Tsinghua University, Beijing 100084, China;
2. Tsinghua Innovation Center in Dongguan, Dongguan 523808, Guangdong, China

Received:2017-01-03 Revised:2017-02-20 Online:2017-08-05 Published:2017-08-05

摘要/Abstract

摘要： 木质素是自然界中最丰富的芳香类化合物，也是制浆造纸和木质纤维素生物炼制过程的主要副产物。热解是将木质素资源化、能源化利用的一个有效途径。但由于分离方法不同，所得的木质素产品具有不同的热解特性。本文通过有机酸处理、碱处理和氧化处理从甘蔗渣中分离得到5种木质素，即乙酸木质素（AAL）、Acetosolv木质素（AsL）、Milox木质素（ML）、过氧乙酸木质素（PAAL）和碱木质素（AL）。采用差示扫描量热（DSC）和热重分析（TGA）对5种木质素的热解性质进行了研究。发现5种木质素的热解过程均可分为水分脱除、玻璃化转变、热解和缓慢结焦4个阶段。采用非等温的Coats-Redfern积分法对热重数据进行动力学拟合。结果表明，PAAL在200~700℃范围内的热解为二级动力学反应，另外4种木质素则在250~700℃范围内为二级动力学反应。5种木质素的热解表观活化能分别为AAL 33.33kJ/mol、AsL 36.36kJ/mol、ML 31.10kJ/mol、PAAL 24.74kJ/mol以及AL 36.93 kJ/mol。

关键词: 甘蔗渣, 分离木质素, 热解, 动力学, 分子量

Abstract: Lignin is the most abundant natural aromatic polymer on earth. It is also a major byproduct of pulp and papermaking industry and lignocellulose biorefinery. Pyrolysis is one of the most promising ways to utilize lignin for production of fuels and chemicals. However,the pyrolysis characteristics of lignin products are greatly dependent on the isolation methods. In present work,five lignin products were isolated from sugarcane bagasse by organic acid,alkaline,and oxidative pretreatments,respectively,namely acetic acid lignin(AAL),acetosolve lignin(AsL),milox lignin (ML),peracetic acid lignin(PAAL)and alkaline lignin(AL). The pyrolysis of these isolated lignins was investigated using differential scanning calorimetry(DSC)and thermogravimetric analysis(TGA). As indicated by TGA,all of the lignin products showed four stages of weight losses,namely water removal,glass transition,pyrolysis to small molecules and slow coking. The pyrolysis kinetics was analyzed by Coats-Redfern method. The results indicated that the pyrolysis process could be described as a second-order reaction in temperature range of 200-700℃ for PAAL,and 200-700℃ for the other four lignins. The activation energies were determined as 33.33kJ/mol,36.36kJ/mol,31.10kJ/mol, 24.74kJ/mol and 36.93kJ/mol for AAL,AsL,ML,PAAL and AL,respectively.

Key words: sugarcane bagasse, isolated lignin, pyrolysis, kinetics, molecular weight

中图分类号:

O636.2
TQ351

崔兴凯, 赵雪冰, 刘德华. 五种甘蔗渣分离木质素热解特性及动力学[J]. 化工进展, 2017, 36(08): 2910-2915.

CUI Xingkai, ZHAO Xuebing, LIU Dehua. Pyrolysis characteristics and kinetics of five isolated lignins from sugarcane bagasse[J]. Chemical Industry and Engineering Progress, 2017, 36(08): 2910-2915.

参考文献

[1] CALVO-FLORES F G,DOBADO J A. Lignin as renewable raw material[J]. ChemSusChem,2010,3(11):1227-1235.
[2] 穆环珍,杨问波,黄衍初. 造纸黑液木质素利用研究进展[J]. 环境污染治理技术与设备,2001,2(3):26-30. MU H Z,YANG W B,HUANG Y C. Research progress in application of papermaking black liquor and lignin[J]. Technigues and Equipment for Enviro. Poll. Cont,,2001,2(3):26-30.
[3] 杨淑蕙. 植物纤维化学[M]. 北京:中国轻工业出版社,2001:69. YANG S H. Plant fiber chemistry[M]. Beijing:China Light Industry Press,2001:69.
[4] 曲音波,陈冠军,高培基. 木质纤维素降解酶与生物炼制[M]. 北京:化学工业出版社,2011:35-36 QU Y B,CHEN G J,GAO P J. Lignocellulose degrading enzymes and biorefinery[M]. Beijing:Chemical Industry Press,2011:35-36
[5] 周海峰,杨东杰,伍晓蕾,等. 漆酶改性木质素磺酸钠的结构表征及吸附特征[J]. 高等学校化学学报,2013,34(1):218-224. ZHOU H F,YANG D J,WU X L,et al. Structure and adsorption characterization of sodium lignosulfonate by laccase modification[J]. Chem. J. Chinese U.,2013,34(1):218-224.
[6] MICHELIN M,RUIZ H A,SILVA D P,et al. Cellulose from lignocellulosic waste[M]//Polysaccharides:Bioactivity and Biotechnology. New York:Springer,2015:475-511.
[7] YABUSHITA M,KOBAYASHI H,FUKUOKA A. Catalytic transformation of cellulose into platform chemicals[J]. Applied Catalysis B:Environmental,2014,145:1-9.
[8] ZHAO X,WU R,LIU D. Production of pulp,ethanol and lignin from sugarcane bagasse by alkali-peracetic acid delignification[J]. Biomass and Bioenergy,2011,35(7):2874-2882.
[9] 陈洪章,李佐虎. 木质纤维原料组分分离的研究[J]. 纤维素科学与技术,2003,11(4):31-40. CHEN H Z,LI Z H. Lignocellulose fractionation[J]. Journal of Cellulose Science and Technology,2003,11(4):31-40.
[10] ZHANG Y H P. Reviving the carbohydrate economy via multi-product lignocellulose biorefineries[J]. Journal of Industrial Microbiology & Biotechnology,2008,35(5):367-375.
[11] KAI D,TAN M J,CHEE P L,et al. Towards lignin-based functional materials in a sustainable world[J]. Green Chemistry,2016,18(5):1175-1200.
[12] HOUGH B R,SCHWARTZ D T,PFAENDTNER J. Detailed kinetic modeling of lignin pyrolysis for process optimization[J]. Industrial & Engineering Chemistry Research,2016,55(34):9147-9153.
[13] HUANG M,LUO J,FANG Z,et al. Biodiesel production catalyzed by highly acidic carbonaceous catalysts synthesized via carbonizing lignin in sub-and super-critical ethanol[J]. Applied Catalysis B:Environmental,2016,190:103-114.
[14] LI Y,HU Y S,LI H,et al. A superior low-cost amorphous carbon anode made from pitch and lignin for sodium-ion batteries[J]. Journal of Materials Chemistry A,2016,4(1):96-104.
[15] BAKER D A,RIALS T G. Recent advances in low-cost carbon fiber manufacture from lignin[J]. Journal of Applied Polymer Science,2013,130(2):713-728.
[16] DING R,WU H,THUNGA M,et al. Processing and characterization of low-cost electrospun carbon fibers from organosolv lignin/polyacrylonitrile blends[J]. Carbon,2016,100:126-136.
[17] NOR N M,LAU L C,LEE K T,et al. Synthesis of activated carbon from lignocellulosic biomass and its applications in air pollution control:a review[J]. Journal of Environmental Chemical Engineering,2013,1(4):658-666.
[18] SHEN D K,GU S,LUO K H,et al. The pyrolytic degradation of wood-derived lignin from pulping process[J]. Bioresource Technology,2010,101(15):6136-6146.
[19] MUDRABOYINA B P,FARAG S,BANERJEE A,et al. Supercritical fluid rectification of lignin pyrolysis oil methyl ether (LOME) and its use as a bio-derived aprotic solvent[J]. Green Chemistry,2016,18(7):2089-2094.
[20] DE S,SAHA B,LUQUE R. Hydrodeoxygenation processes:Advances on catalytic transformations of biomass-derived platform chemicals into hydrocarbon fuels[J]. Bioresource Technology,2015,178:108-118.
[21] WANG S,RU B,LIN H,et al. Pyrolysis behaviors of four lignin polymers isolated from the same pine wood[J]. Bioresource Technology,2015,182:120-127.
[22] SLUITER A,HAMES B,RUIZ R,et al. Determination of structural carbohydrates and lignin in biomass[J]. Laboratory Analytical Procedure,2008,1617.
[23] NIMZ H H,GRANZOW C,BERG A. Acetosolv pulping[J]. European Journal of Wood and Wood Products,1986,44(9):362-362.
[24] ZHAO X B,LIU D H. Chemical and thermal characteristics of lignins isolated from siam weed stem by acetic acid and formic acid delignification[J]. Industrial Crops and Products,2010,32(3):284-291.
[25] SUNDQUIST J. Chemical pulping based on formic acid:summary of Milox research[J]. Paper and Timber,1996,78(3):92-95.
[26] PAN X J,SANO Y. Atmospheric acetic acid pulping of rice straw Ⅳ:Physico-chemical characterization of acetic acid lignins from rice straw and woods. Part 1. Physical characteristics[J]. Holzforschung,1999,53(5):511-518.
[27] 刘贵生. 木素官能团分析[M]. 哈尔滨:东北林业大学出版社,1996:140-146 LIU G S. Functional group analysis of lignin[M]. Harbing:Northeast Forestry University Press,1996:140-146
[28] YANG H,YAN R,CHEN H,et al. Characteristics of hemicellulose,cellulose and lignin pyrolysis[J]. Fuel,2007,86(12):1781-1788.
[29] TSUJIYAMA S,MIYAMORI A. Assignment of DSC thermograms of wood and its components[J]. Thermochimica Acta,2000,351(1):177-181.
[30] SHUKRY N,FADEL S M,AGBLEVOR F A,et al. Some physical properties of acetosolv lignins from bagasse[J]. Journal of Applied Polymer Science,2008,109(1):434-444.
[31] PAN X J,SANO Y. Comparison of acetic acid lignin with milled wood and alkaline lignins from wheat straw[J]. Holzforschung,2000,54(1):61-65.
[32] COATS A W,REDFERN J P. Kinetic parameters from thermogravimetric data[J]. Nature,1964,201(4):68-69.

五种甘蔗渣分离木质素热解特性及动力学

Pyrolysis characteristics and kinetics of five isolated lignins from sugarcane bagasse

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