生物质三组分真空热解特性及液化产物成分分析

doi:10.3969/j.issn.0253-2417.2015.01.015

摘要/Abstract

摘要： 以微晶纤维素、木聚糖和碱性木质素分别作为生物质3组分(纤维素、半纤维素和木质素)的模型物,利用傅立叶变换红外光谱技术(FT-IR)对生物质3组分结构进行了表征,并对3组分进行了真空热解特性分析,同时利用气质联用技术(GC-MS)对3组分真空热解液化后的生物油进行了成分分析,初步探讨了各组分的真空热解液化机理。研究结果表明,纤维素含有吡喃环、β-糖苷键等特征结构,真空热解时失重区间较窄(250~400 ℃),真空热解油产率较高(73.79%),产物主要有2,5-二甲基呋喃(9.32%)、2,6-二甲氧基苯酚(5.72%)和左旋葡聚糖(17.04%)等;木聚糖中存在β-糖苷键、阿拉伯糖侧链等结构,支链多,热稳定性差,真空热解油主要含有乙酸(10.11%)、羟基丙酮(18.42%)和糠醛(13.15%)等;木质素中含有较多的芳香族类物质结构,热解缓慢,失重区间较宽(185~550 ℃),热解终了时固体残留物较多,为29.67%,真空热解油中苯酚(16.24%)、愈创木酚(20.37%)等酚类物质较多。

关键词: 纤维素, 木聚糖, 木质素, 真空热解, 生物油

Abstract: The molecular structure of three components (cellulose, xylan, and lignin) in biomass was detected by Fourier transform infrared spectroscopy (FT-IR). The vacuum pyrolysis behavior and kinetics of the three components were investigated.The vacuum pyrolysis mechanism was studied on the basis of gas chromatography-mass spectrometer (GC-MS) analysis for bio-oils obtained from the vacuum pyrolysis. It was found that the cellulose contained molecular structures such as pyran ring and β-glucosidic bond. During the pyrolysis process temperature from 250 ℃ to 400 ℃, the yield was 73.79% and main products generated from pyrolysis were 2,5-dimethyl-furan (9.32%), hydroxyacetone (5.13%) 2,6-dimethoxy-phenol (5.72%) and levoglucosan (17.04%). Due to high content of side-chain groups, the xylan performed thermal unstability under high temperature. The main pyrolysis products were hydroxyacetone (18.42%), acetic acid (10.11%) and furfural (13.15%). Lignin contained amounts of aromatic substances, which trends to represent slow pyrolysis process and a wider range of pyrolysis temperature from 185 ℃ to 550 ℃. The solid residue from pyrolysis of lignin was up to 29.67% with the main pyrolytic products such as phenols (16.24%) and guaiacol (20.37%).

Key words: cellulose, xylan, lignin, vacuum pyrolysis, bio-oil

中图分类号:

TQ35
TK6

尹海云, 李小华, 樊永胜, 俞宁, 蔡忆昔. 生物质三组分真空热解特性及液化产物成分分析[J]. 林产化学与工业, 2015, 35(1): 94-100.

YIN Hai-yun, LI Xiao-hua, FAN Yong-sheng, YU Ning, CAI Yi-xi. Vacuum Pyrolysis Behavior of Cellulose, Xylan and Lignin and the Analysis of Liquefied Compositions[J]. Chemistry and Industry of Forest Products, 2015, 35(1): 94-100.

参考文献

[1] 徐莹,王铁军,马隆龙,等.真空热解松木粉制备生物油[J].农业工程学报,2013,29(1):196-201. XU Ying,WANG Tie-jun,MA Long-long,et al.Technology of bio-oil preparation by vacuum pyrolysis of pine straw[J].Transactions of the Chinese Society of Agricultural Engineering,2013,29(1):196-201.
[2] 涂军令,应浩,李琳娜.生物质制备合成气技术研究现状与展望[J].林产化学与工业,2011,31(6):112-118. TU Jun-ling,YING Hao,LI Lin-na.The state of the art of synthesis gas production technology from biomass[J].Chemistry and Industry of Forest Products,2011,31(6):112-118.
[3] 冯昊,郑志锋,蒋剑春,等.生物质热解液化产物制备酚醛树脂研究进展[J].林产化学与工业,2010,30(4):107-112. FENG Hao,ZHENG Zhi-feng,JIANG Jian-chun,et al.Research progress on production of phenolic resins from products of biomass pyrolysis & liquefaction[J].Chemistry and Industry of Forest Products,2010,30(4):107-112.
[4] SHEN D K,GU S.The mechanism for thermal decomposition of cellulose and its main products[J].Bioresource Technology,2009,100(24):6496-6504.
[5] 吴逸民,赵增立,李海滨,等.生物质主要组分低温热解研究[J].燃料化学学报,2009,37(4):427-432. WU Yi-min,ZHAO Zeng-li,LI Hai-bin,et al.Low temperature pyrolysis characteristics of major components of biomass[J].Journal of Fuel Chemistry and Technology,2009,37(4):427-432.
[6] 杨海平,陈汉平,晏蓉,等.油棕废弃物及生物质三组分的热解动力学研究[J].太阳能学报,2007,28(6):626-631. YANG Hai-ping,CHEN Han-ping,YAN Rong,et al.Thermodynamic analysis of pyrolysis of palm oil wastes and biomass components[J].Acta Energlae Solaris Sinica,2007,28(6):626-631.
[7] 胡松,ANDREAS J,向军,等.基于不同三组分模型解析生物质热解过程[J].化工学报,2007,58(10):2580-2586. HU Song,ANDREAS J,XIANG Jun,et al.Kinetic study of biomass pyrolysis based on different three-pseudocomponent models[J].Journal of Chemical Industry and Engineering (China),2007,58(10):2580-2586.
[8] BURHENNE L,MESSMER J,AICHER T,et al.The effect of the biomass components lignin,cellulose and hemicelluloses on TGA and fixed bed pyrolysis[J].Journal of Analytical and Applied Pyrolysis,2013,101:177-184.
[9] GIUDICIANNI P,CARDONE G,RAGUCCI R.Cellulose,hemicelluloses and lignin slow steam pyrolysis:Thermal decomposition of biomass components mixtures[J].Journal of Analytical and Applied Pyrolysis,2013,100:213-222.
[10] 樊永胜,蔡忆昔,李小华,等.真空热解工艺参数对生物油产率的影响研究[J].林产化学与工业,2014,34(1):79-85. FAN Yong-sheng,CAI Yi-xi,LI Xiao-hua,et al.Influence of process parameters on bio-oil yield by vacuum pyrolysis[J].Chemistry and Industry of Forest Products,2014,34(1):79-85.
[11] GANI A,NARUSE I.Effect of cellulose and lignin content on pyrolysis and combustion characteristics for several types of biomass[J].Renewable Energy,2007,32(4):649-661.
[12] 王树荣,郑赟,骆仲泱,等.生物质组分热裂解动力学研究[J].浙江大学学报:工学版,2007,41(4):585-588. WANG Shu-rong,ZHENG Yun,LUO Zhong-yang,et al.Kinetic study on pyrolysis of biomass components[J].Journal of Zhejiang University (Engineering Science),2007,41(4):585-588.
[13] YANG Hai-ping,YAN Rong,CHEN Han-ping,et al.Characteristics of hemicelluloses,cellulose and lignin pyrolysis[J].Fuel,2007,86:(12/13):1781-1788.
[14] PASANGULAPATI V,RAMACHANDRIYA K D,KUMAR A,et al.Effects of cellulose,hemicelluloses and lignin on thermochemical conversion characteristics of the selected biomass[J].Bioresource Technology,2012,114:663-669.
[15] WANG Gang,LI Wang,LI Bao-qing,et al.TG study on pyrolysis of biomass and its three components under syngas[J].Fuel,2008,87(4/5):552-558.
[16] QU Ting-ting,GUO Wan-jun,SHEN Lai-hong,et al.Experimental study of biomass pyrolysis based on three major components:Hemicellulose,cellulose,and lignin[J].Industrial and Engineering Chemistry Research,2011,50(18):10424-10433.
[17] WANG Shu-rong,GUO Xiu-juaN,WANG Kai-ge,et al.Influence of the interaction of components on the pyrolysis behavior of biomass[J].Journal of Analytical and Applied Pyrolysis,2011,91(1):183-189.
[18] 彭云云,武书彬.TG-FTIR联用研究半纤维素的热裂解特性[J].化工进展,2009,28(8):1478-1484. PENG Yun-yun,WU Shu-bin.Characteristics and kinetics of sugarcana bagasse hemicelluloses pyrolysis by TG-FTIR[J].Chemical Industry and Engineering Progress,2009,28(8):1478-1484.
[19] BERNHARD P.Prediction of pyrolysis of pistachio shells based on its components hemicelluloses,cellulose and lignin[J].Fuel Processing Technology,2011,92(10):1993-1998.
[20] 金湓,李宝霞.纤维素与木质素共热解试验及动力学分析[J].化工进展,2013,32(2):303-307. JIN Pen,LI Bao-xia.Experiments and kinetic analysis on the co-pyrolysis of cellulose and lignin[J].Chemical Industry and Engineering Progress,2013,32(2):303-307.
[21] 程辉,余剑,姚梅琴,等.木质素慢速热解机理[J].化工学报,2013,64(5):1757-1765. CHENG Hui,YU Jian,YAO Mei-qin,et al.Mechanism analysis of lignin slow pyrolysis[J].Journal of Chemical Industry and Engineering (China),2013,64(5):1757-1765.