交互反应对生物质焦炭官能团结构的影响
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摘要
为解析挥发分-焦炭交互反应对生物质焦炭官能团结构的影响,利用一维固定床/流化床反应器及快速热裂解仪,采用傅里叶红外光谱仪从定性与半定量角度分析交互反应对生物质焦炭官能团结构的影响.结果表明:相比于温度的作用,交互反应对生物质焦炭官能团结构的影响更为剧烈;交互反应使焦炭中的各个特征官能团对应的特征峰强度有所减弱,峰的种类也有所减少;交互反应对焦炭烷基侧链有破坏作用,并加快了其从芳香环上的脱落;在无交互反应下,焦炭有机质的成熟度随着温度的上升而增高;在交互反应下,较低的温度时该规律成立,而较高温度时该参数逐渐下降;在高温下,挥发分裂解产生的自由基会引起芳香环的缩合,导致Car含量增多.
To study the effect of volatile-char interaction on biochar functional groups,the one-stage fluidized bed/fixed bed reactor and Py were used in the experiment,and the biochar structure was analyzed by Fourier transform infrared spectrometer in the qualitative and semi-quantitative aspects. The results show that with the increase of temperature,the influence of interaction on biochar structure is more intense. The characteristic peaks of biochar functional groups are reduced and the species of peaks are reduced due to the volatile-char interaction which has a destructive effect on the alkyl side chain and accelerates its detachment from aromatic ring. Without the volatilechar interaction or with the interaction but at low temperature,the maturity of organic matter of biochar increases with the increasing of temperature. However at high temperature,the parameters decrease and the free radicals generated by the volatile splitting can cause the condensation of aromatic ring,which leads to the increase of Car content.
To study the effect of volatile-char interaction on biochar functional groups,the one-stage fluidized bed/fixed bed reactor and Py were used in the experiment,and the biochar structure was analyzed by Fourier transform infrared spectrometer in the qualitative and semi-quantitative aspects. The results show that with the increase of temperature,the influence of interaction on biochar structure is more intense. The characteristic peaks of biochar functional groups are reduced and the species of peaks are reduced due to the volatile-char interaction which has a destructive effect on the alkyl side chain and accelerates its detachment from aromatic ring. Without the volatilechar interaction or with the interaction but at low temperature,the maturity of organic matter of biochar increases with the increasing of temperature. However at high temperature,the parameters decrease and the free radicals generated by the volatile splitting can cause the condensation of aromatic ring,which leads to the increase of Car content.
引文
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[3]冯冬冬.生物质热解焦炭理化特性的研究[D].哈尔滨:哈尔滨工业大学,2014.FENG D D.Research on pysical and chemical characteristic of biomass pyrolysis char[D].Harbin:Harbin Institute of Technology,2014.
[4]GEORGAKOPOULOS A.Study oflow rank greek coals using FTIR spectroscopy[J].Energy Sources,2003,25(10):995-1005.DOI:10.1080/00908310390232442.
[5]ZHAO Y J,FENG D D,ZHANG Y,et al.Effect of pyrolysis temperature on char structure and chemical speciation of alkali and alkaline earth metallic species in biochar[J].Fuel Processing Technology,2016,141(2):54-60.DOI:10.1016/j.fuproc.2015.06.029.
[6]C∨ERNJ.Structural dependence of CH bond absorptivities and consequences for FTIR analysis of coals[J].Fuel,1996,75(11):1301-1306.DOI:10.1016/0016-2361(96)00103-2.
[7]石金明,孙路石,向军,等.兖州煤气化半焦表面官能团特征试验研究[J].中国电机工程学报,2010,30(5):17-22.SHI J M,SUN L S,XIANG J,et al.Experimental study on functional groups of semi coke in Yanzhou coal gasification[J].Journal of Chinese Electrical Engineering Science,2010,30(5):17-22.
[8]IBARRA J,MUNOZ E,MOLINER R.FTIR study of the evolution of coal structure during the coalification process[J].Organic Geochemistry,1996,24(6/7):725-735.DOI:10.1016/0146-6380(96)00063-0.
[9]段春雷.低中变质程度煤的结构特征及热解过程中甲烷、氢气的生成机理[D].太原:太原理工大学,2007.DUAN C L.Structural characteristics and formation mechanism of methane and hydrogen during pyrolysis of low medium metamorphic coal[D].Taiyuan:Taiyuan University of Technology,2007.
[10]IBTTA J,MOLINER R,BONET J.FTIR investigation on char formation during the early stages of coal pyrolysis[J].Fuel,1994,73(6):918-924.DOI:10.1016/0016-2361(94)90287-9.
[11]IBTTA J,MOLINER R,GAVIL 6)AN M P.Functional group dependence of cross-linking reactions during pyrolysis of coal[J].Fuel,1991,70(3):408-413.DOI:10.1016/0016-2361(91)90131-S.
[12]YANG J B,CAI N S.A TG-FTIR study on catalytic pyrolysis of coal[J].Journal of Fuel Chemistry&Technology,2006,34(6):650-654.DOI:10.1016/S1872-5813(07)60002-4.
[13]黄晓宏,柳朝晖,尹志强,等.无烟煤热解过程中表面官能团的演变[J].工程热物理学报,2013,34(5):969-972.HUANG X H,LIU Z H,YIN Z Q,et al.The evolution of surface functional groups during the pyrolysis of anthracite[J].Journal of engineering thermal physics,2013,34(5):969-972.