真空紫外光电离质谱研究稻壳和稻秆的热解
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摘要
利用同步辐射真空紫外光电离质谱(SVUV PIMS)对稻壳和稻秆的热解过程进行了研究。通过改变光子能量,获得了随光子能量变化的质谱图,并鉴定了热解过程的主要产物。本工作测量了不同热解温度下的产物质谱图,并结合热重分析,对两种样品热解产物与温度的关系进行对比研究。稻壳与稻秆的热重曲线非常相近,但二者的产物质谱图却差异明显,主要表现在m/z114和m/z96等几种半纤维素产物丰度随温度变化的趋势不同。本工作还测量了若干特征产物随时间变化的谱图,结果表明,半纤维素在低温下就开始出现,且生成速度较快,而大部分的木质素分解速度较慢,温度区间也相对较宽,其分解伴随着整个热解过程。
The pyrolysis of rice husk and rice straw were studied by tunable synchrotron vacuum ultraviolet photoionization mass spectrometry(SVUV PIMS).Main pyrolysis products of rice husk and rice straw were identified with mass spectra obtained at different photon energies.The work investigated the relation between pyrolysis products and reaction temperature,according to the mass spectra of rice husk and rice straw pyrolysis at different temperatures.Although the TGA spectra showed that the tendency of the TGA spectra of rice husk and rice straw were similar,their mass spectra were different obviously,especially that the m/z 96 and m/z 114,which came from the pyrolysis of hemicellulose,changed with temperature differently.The time-dependent profiles of some characteristic products showed that the pyrolysis products from hemicellulose appear rapidly at low temperature,while large proportion of lignin underwent slower thermal decomposition at wider temperature range during the overall pyrolysis process.
The pyrolysis of rice husk and rice straw were studied by tunable synchrotron vacuum ultraviolet photoionization mass spectrometry(SVUV PIMS).Main pyrolysis products of rice husk and rice straw were identified with mass spectra obtained at different photon energies.The work investigated the relation between pyrolysis products and reaction temperature,according to the mass spectra of rice husk and rice straw pyrolysis at different temperatures.Although the TGA spectra showed that the tendency of the TGA spectra of rice husk and rice straw were similar,their mass spectra were different obviously,especially that the m/z 96 and m/z 114,which came from the pyrolysis of hemicellulose,changed with temperature differently.The time-dependent profiles of some characteristic products showed that the pyrolysis products from hemicellulose appear rapidly at low temperature,while large proportion of lignin underwent slower thermal decomposition at wider temperature range during the overall pyrolysis process.
引文
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[19]EVANS R J,MILNE T A.Molecular character-ization of the pyrolysis of biomass.2.Applications[J].Energy&Fuels,1987,1(4):311-319.
[20]YANG H,YAN R,CHEN H,et al.Character-istics of hemicellulose,cellulose and lignin pyrol-ysis[J].Fuel,2007,86(12/13):1 781-1 788.
[21]REALE S,DI TULLIO A,SPRETI N,et al.Mass spectrometry in the biosynthetic and struc-tural investigation of lignins[J].Mass Spectrom-etry Reviews,2004,23(2):87-126.
[2]孙永明,袁振宏,孙振钧.中国生物质能源与生物质利用现状与展望[J].可再生能源,2006,(2):78-82.
[3]柏杰.发展生物柴油大有可为[J].中国科技产业,2002,(9):63-64.
[4]BRIDGWATER A V.Principles and practice of bi-omass fast pyrolysis processes for liquids[J].Journal of Analytical and Applied Pyrolysis,1999,51(1/2):3-22.
[5]宋春财,胡浩权,朱盛维,等.生物质秸秆热重分析及几种动力学模型结果比较[J].燃料化学学报,2003,(4):311-316.
[6]BAHNG M K,MUKARAKATE C,ROBICHAUDD J,et al.Current technologies for analysis of bi-omass thermochemical processing:A review[J].Anal Chim Acta,2009,651(2):117-38.
[7]齐飞.同步辐射真空紫外单光子电离技术及其应用[J].中国科学技术大学学报,2007,(Z1):414-425.
[8]FEI Q.Combustion chemistry probed by synchro-tron vuv photoionization mass spectrometry[J].Proc Combust Inst,2012,34(accepted).
[9]PAN Y,ZHANG L,GUO H,et al.Photoionisa-tion and photodissociation studies of nonvolatileorganic molecules by synchrotron vuv photoionisa-tion mass spectrometry and theoretical calculations[J].International Reviews in Physical Chemistry,2010,29(2):369-401.
[10]FANG W Z,GONG L,SHAN X B,et al.Ther-mal desorption/tunable vacuum-ultraviolet time-of-flight photoionization aerosol mass spectrome-try for investigating secondary organic aerosols inchamber experiments[J].Analytical Chemistry,2011,83(23):9 024-9 032.
[11]WENG J,JIA L,WANG Y,et al.Pyrolysis st-udy of poplar biomass by tunable synchrotronvacuum ultraviolet photoionization mass spec-trometry[J].Proceedings of the Combustion In-stitute,2012,34(in press,DOI:10.1016/j.proci.2012.05.077,2012).
[12]朱锡锋.生物质热解原理与技术[M].合肥:中国科学技术大学出版社,2006.
[13]EVANS R J,MILNE T A.Molecular character-ization of the pyrolysis of biomass.1.Fundamen-tals[J].Energy&Fuels,1987,1(2):123-137.
[14]FAIX O,MEIER D,FORTMANN I.Gas chro-matographic separation and mass spectrometriccharacterization of monomeric lignin derivedproducts[J].Holz als Roh-und Werkstoff,1990,48(7/8):281-285.
[15]HODGSON E M,NOWAKOWSKI D J,SHIE-LD I,et al.Variation in miscanthus chemicalcomposition and implications for conversion bypyrolysis and thermo-chemical bio-refining for fu-els and chemicals[J].Bioresour Technol,2011,102(3):3 411-3 418.
[16]SIMONEIT B R T,ROGGE W F,MAZUREKM A,et al.Lignin pyrolysis products,lignans,and resin acids as specific tracers of plant classesin emissions from biomass combustion[J].Envi-ron Sci Technol,1993,27(12):2 533-2 541.
[17]王述洋.生物质热解动力学建模及锥式闪速热解装置设计理论研究[D].哈尔滨:东北林业大学,2002.
[18]LI R,ZHONG Z P,JIN B S,et al.Influence ofreaction conditions and red brick on fast pyrolysisof rice residue(husk and straw)in a spout-fluidbed[J].Canadian Journal Of Chemical Engineer-ing,2012,90(5):1 202-1 211.
[19]EVANS R J,MILNE T A.Molecular character-ization of the pyrolysis of biomass.2.Applications[J].Energy&Fuels,1987,1(4):311-319.
[20]YANG H,YAN R,CHEN H,et al.Character-istics of hemicellulose,cellulose and lignin pyrol-ysis[J].Fuel,2007,86(12/13):1 781-1 788.
[21]REALE S,DI TULLIO A,SPRETI N,et al.Mass spectrometry in the biosynthetic and struc-tural investigation of lignins[J].Mass Spectrom-etry Reviews,2004,23(2):87-126.