基于组分分析的农业废弃物类生物质热裂解机理研究
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摘要
目的:研究农业废弃物类生物质原料特性对热裂解行为的影响,探讨热裂解机理。方法:利用热重-红外联用技术(TG-FTIR)对四种农业废弃秸秆生物质及其混合配比秸秆进行热裂解实验。结果:热重实验结果表明,油菜秆、玉米秆、毛豆秆分别与棉秆混合后最大失重速率降低,油菜秆的加入使焦炭产率增加.红外光谱表明,半纤维素、木质素含量的升高均抑制了左旋葡聚糖的生成;纤维素对2-糖醛、酚类物质生成有较好的选择性,木质素和半纤维素分别对2-糖醛和酚类物质的生成有抑制作用。结论:农业废弃生物质热解行为及典型热解产物析出受原料特性和组分含量变化的共同影响,对生物质快速热裂解从源头的原料筛选以及特定产物的调控提供了实际理论指导。
Aims: This paper aims to study the effect of the material characteristics of agricultural waste biomass on pyrolysis behavior and discuss the pyrolysis mechanism. Methods: Pyrolysis experiments of four kinds of agricultural waste straw biomass and two-straw mixing straw were carried out by thermogravimetric-infrared combination technology(TG-FTIR). Results: The results of thermogravimetric analysis showed that the maximum weight loss rate of mixed straw decreased when rape stalk, corn stalk and soybean stalk were mixed with cotton stalk respectively, and the char yield increased with the addition of rape stalk. Infrared spectroscopy showed that the increase of hemicellulose and lignin content inhibited the formation of levoglucose. Cellulose had better selectivity for the formation of 2-furfural and phenols products. Lignin and hemicellulose inhibited the formation of 2-furfural and phenols products, respectively. Conclusions: The pyrolysis behavior of agricultural waste biomass and the precipitation of typical pyrolysis products were affected by material characteristics and the change of component content. It has practical guiding significance for the selection of materials from source and the regulation of specific products by rapid pyrolysis of biomass.
Aims: This paper aims to study the effect of the material characteristics of agricultural waste biomass on pyrolysis behavior and discuss the pyrolysis mechanism. Methods: Pyrolysis experiments of four kinds of agricultural waste straw biomass and two-straw mixing straw were carried out by thermogravimetric-infrared combination technology(TG-FTIR). Results: The results of thermogravimetric analysis showed that the maximum weight loss rate of mixed straw decreased when rape stalk, corn stalk and soybean stalk were mixed with cotton stalk respectively, and the char yield increased with the addition of rape stalk. Infrared spectroscopy showed that the increase of hemicellulose and lignin content inhibited the formation of levoglucose. Cellulose had better selectivity for the formation of 2-furfural and phenols products. Lignin and hemicellulose inhibited the formation of 2-furfural and phenols products, respectively. Conclusions: The pyrolysis behavior of agricultural waste biomass and the precipitation of typical pyrolysis products were affected by material characteristics and the change of component content. It has practical guiding significance for the selection of materials from source and the regulation of specific products by rapid pyrolysis of biomass.
引文
[1] 农业部新闻办公室.我国2015年主要农作物秸秆综合利用率超过80%[EB/OL].(2019-01-17)[2016-05-26].http://www.xinnong.net/news/20160526/1306813.html.
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[3] 王琦.生物质快速热裂解制取生物油及其后续应用研究[D].杭州:浙江大学,2008:65-68.WANG Q. Research on Production and Utilization of Biooil from Biomass Fast Pyrolysis[D].Hangzhou: Zhejiang University,2008:65-68.
[4] 刘姗,杨雪银,任学勇,等.生物质热解油基绿色化学品与化工产品研究进展[J].化工新型材料,2017,45(11):17-20.LIU S, YANG X Y, REN X Y, et al. Research progress of biomass pyrolysis oil based green chemicals and products[J].New Chemical Materials,2017,45(11):17-20.
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[6] WANG S R, GUO X J, WANG K G, 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.
[7] HOSOYA T, KAWAMOTO H, SAKA S. Cellulose-hemicellulose and cellulose-lignin interactions in wood pyrolysis at gasification temperature[J].Journal of Analytical and Applied Pyrolysis,2007,80(1):118-125.
[8] 刘倩.基于组分的生物质热裂解机理研究[D].杭州:浙江大学,2009:110-112.LIU Q. Biomass Pyrolysis Mechanism Based on the Multi-components[D].Hangzhou: Zhejiang University,2009:110-112.
[9] NOWAKOWSKI D J, JONES J M, BRYDSON R, et al. Potassium catalysis in the pyrolysis behaviour of short rotation willow coppice[J].Fuel,2007,86(15):2389-2402.
[10] YANG H. Characteristics of hemicellulose, cellulose and lignin pyrolysis[J].Fuel,2007,86(12):1781-1788.
[11] COATS P. Kinetic parameters from thermograwimetric data[J].Nature,1964,201(4914):68-69.
[12] WORASUWANNARAK N, SONOBE T, TANTHAPA-NICHAKOON W. Pyrolysis behaviors of rice straw, rice husk, and corncob by TG-MS technique[J].Journal of Analytical and Applied Pyrolysis,2007,78(2):265-271.
[13] 宋飞跃.基于组分的生物质混合热解实验研究[D].合肥:中国科学技术大学,2017:33-34.SONG F Y. Experimental Study of Biomass Mixture Pyrolysis Based on Components[D].Hefei: University of Science and Technology of China,2017:33-34.
[14] LI S, LYONS-HART J, BANYASZ J, et al. Real-time evolved gas analysis by FTIR method: An experimental study of cellulose pyrolysis[J].Fuel,2001,80(12):1809-1817.
[15] LIU Q, WANG S R, ZHENG Y, et al. Mechanism study of wood lignin pyrolysis by using TG-FTIR analysis[J].Journal of Analytical and Applied Pyrolysis,2008,82(1):170-177.
[16] LIU Q, WANG S R, WANG K G, et al. Pyrolysis of wood species based on the compositional analysis[J].Korean Journal of Chemical Engineering,2009,26(2):548-553.
[17] HOSOYA T, KAWAMOTO H, SAKA S. Solid/liquid- and vapor-phase interactions between cellulose- and lignin-derived pyrolysis products[J].Journal of Analytical and Applied Pyrolysis,2009,85(1-2):237-246.
[18] 朱玲莉,仲兆平,王佳,等.基于PY-GC/MS的生物质组分间相互作用的热解实验[J].化工进展,2016,35(12):3879-3884.ZHU L L, ZHONG Z P, WANG J, et al. The interactions among the pyrolysis of biomass components based on the PY-GC/MS[J].Chemical Industry and Engineering Progress,2016,35(12):3879-3884.
[19] GUO X J, WANG S R, WANG Q, et al. Properties of biooil from fast pyrolysis of rice husk[J].Chinese Journal of Chemical Engineering,2011,19(1):116-121.
[20] ERIKA M, JAKAB E, GáBOR V. TG/MS, Py-GC/MS and THM-GC/MS study of the composition and thermal behavior of extractive components of Robinia pseudoacacia[J].Journal of Analytical and Applied Pyrolysis,2007,79(1-2):61-70.
[2] BRIDGWATER A V, MEIER D, RADLEIN D. An overview of fast pyrolysis of biomass[J].Organic Geochemistry,1999,30(12):1479-1493.
[3] 王琦.生物质快速热裂解制取生物油及其后续应用研究[D].杭州:浙江大学,2008:65-68.WANG Q. Research on Production and Utilization of Biooil from Biomass Fast Pyrolysis[D].Hangzhou: Zhejiang University,2008:65-68.
[4] 刘姗,杨雪银,任学勇,等.生物质热解油基绿色化学品与化工产品研究进展[J].化工新型材料,2017,45(11):17-20.LIU S, YANG X Y, REN X Y, et al. Research progress of biomass pyrolysis oil based green chemicals and products[J].New Chemical Materials,2017,45(11):17-20.
[5] 王树荣,骆仲泱.生物质组分热裂解[M].北京:科学出版社,2013:1-27.
[6] WANG S R, GUO X J, WANG K G, 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.
[7] HOSOYA T, KAWAMOTO H, SAKA S. Cellulose-hemicellulose and cellulose-lignin interactions in wood pyrolysis at gasification temperature[J].Journal of Analytical and Applied Pyrolysis,2007,80(1):118-125.
[8] 刘倩.基于组分的生物质热裂解机理研究[D].杭州:浙江大学,2009:110-112.LIU Q. Biomass Pyrolysis Mechanism Based on the Multi-components[D].Hangzhou: Zhejiang University,2009:110-112.
[9] NOWAKOWSKI D J, JONES J M, BRYDSON R, et al. Potassium catalysis in the pyrolysis behaviour of short rotation willow coppice[J].Fuel,2007,86(15):2389-2402.
[10] YANG H. Characteristics of hemicellulose, cellulose and lignin pyrolysis[J].Fuel,2007,86(12):1781-1788.
[11] COATS P. Kinetic parameters from thermograwimetric data[J].Nature,1964,201(4914):68-69.
[12] WORASUWANNARAK N, SONOBE T, TANTHAPA-NICHAKOON W. Pyrolysis behaviors of rice straw, rice husk, and corncob by TG-MS technique[J].Journal of Analytical and Applied Pyrolysis,2007,78(2):265-271.
[13] 宋飞跃.基于组分的生物质混合热解实验研究[D].合肥:中国科学技术大学,2017:33-34.SONG F Y. Experimental Study of Biomass Mixture Pyrolysis Based on Components[D].Hefei: University of Science and Technology of China,2017:33-34.
[14] LI S, LYONS-HART J, BANYASZ J, et al. Real-time evolved gas analysis by FTIR method: An experimental study of cellulose pyrolysis[J].Fuel,2001,80(12):1809-1817.
[15] LIU Q, WANG S R, ZHENG Y, et al. Mechanism study of wood lignin pyrolysis by using TG-FTIR analysis[J].Journal of Analytical and Applied Pyrolysis,2008,82(1):170-177.
[16] LIU Q, WANG S R, WANG K G, et al. Pyrolysis of wood species based on the compositional analysis[J].Korean Journal of Chemical Engineering,2009,26(2):548-553.
[17] HOSOYA T, KAWAMOTO H, SAKA S. Solid/liquid- and vapor-phase interactions between cellulose- and lignin-derived pyrolysis products[J].Journal of Analytical and Applied Pyrolysis,2009,85(1-2):237-246.
[18] 朱玲莉,仲兆平,王佳,等.基于PY-GC/MS的生物质组分间相互作用的热解实验[J].化工进展,2016,35(12):3879-3884.ZHU L L, ZHONG Z P, WANG J, et al. The interactions among the pyrolysis of biomass components based on the PY-GC/MS[J].Chemical Industry and Engineering Progress,2016,35(12):3879-3884.
[19] GUO X J, WANG S R, WANG Q, et al. Properties of biooil from fast pyrolysis of rice husk[J].Chinese Journal of Chemical Engineering,2011,19(1):116-121.
[20] ERIKA M, JAKAB E, GáBOR V. TG/MS, Py-GC/MS and THM-GC/MS study of the composition and thermal behavior of extractive components of Robinia pseudoacacia[J].Journal of Analytical and Applied Pyrolysis,2007,79(1-2):61-70.