生物质与煤共气化的热重实验研究
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摘要
本文利用热重分析仪对不同生物质、两种不同煤化程度的煤及两者以不同比例混合的混合样品进行了气化实验研究。结果表明,在混合燃料气化过程中,随着稻秆、松木屑及废轮胎在掺混样品中所占比例的增大,其开始气化温度和气化终止温度的提前幅度增大,改善了混合燃料的气化特性;在低温段,生物质和煤共气化过程中存在协同作用。在燃料单独气化过程中,随着升温速率的增大,最大失重速率、最大失重速率对应的峰值温度及失重反应段的温度区间变宽,而反应时间缩短。采用均相反应模型和未反应收缩核模型对所得热重曲线的实验数据进行处理,得到气化反应动力学参数。
In this paper, the gasification experiments of kinds of raw materials, including biomass samples, coal with different grade and the mixture samples with different blending ratio, were conducted in situ through thermal gravimetric analysis. It was found that the characteristics of mixture gasification, in situ refer to the staring temperature and the end temperature of reactions, have been proven to be improved owing to increasing the blending ratio of the biomass samples including rice straw, pine sawdust and waste tire; moreover, at the low temperature scale, the synergy effect occurred in the co-gasification of biomass with coal. With the respect of the increase of heating rate, the max weight-loss rate and the peak temperature with max weight-loss rate as well as the range of temperature scale corresponding to weight-loss scale were all shown the positive trend underlying the gasification of either biomass or coal alone, and that a subsequent the reaction time was favorable to reduce. The kinetics were calculated, based on the data of TGA curves, meanwhile, employed the Homogeneous Model and Shrinking Core Model for data analysis.
In this paper, the gasification experiments of kinds of raw materials, including biomass samples, coal with different grade and the mixture samples with different blending ratio, were conducted in situ through thermal gravimetric analysis. It was found that the characteristics of mixture gasification, in situ refer to the staring temperature and the end temperature of reactions, have been proven to be improved owing to increasing the blending ratio of the biomass samples including rice straw, pine sawdust and waste tire; moreover, at the low temperature scale, the synergy effect occurred in the co-gasification of biomass with coal. With the respect of the increase of heating rate, the max weight-loss rate and the peak temperature with max weight-loss rate as well as the range of temperature scale corresponding to weight-loss scale were all shown the positive trend underlying the gasification of either biomass or coal alone, and that a subsequent the reaction time was favorable to reduce. The kinetics were calculated, based on the data of TGA curves, meanwhile, employed the Homogeneous Model and Shrinking Core Model for data analysis.
引文
[1]唐炼.世界能源供需现状与发展趋势.国际石油经济,2005,13(1):30～33
[2]马经国.新能源技术.南京:江苏科学技术出版社,1992:1～2
[3] J. Chang, D. Y. C. Leung, C. Z. Wu, et al. A review on the energy production, consumption, and prospect of renewable energy in China. Renewable and Sustainable Energy Reviews, 2003,7:453～468
[4]米铁.生物质气化过程的综合实验研究:[博士学位论文].武汉:华中科技大学,2002
[5]段菁春,肖军,王杰林,等.生物质与煤共燃研究.电站系统工程,2004,20(1):1～4
[6] M. Sadakata, K. Takahashi, M. Saito, T. Sakai. Productions of fuel gas and char from wood, lignin and holocellulose by carbonization. Fuel, 1987, 66:1667～1671
[7] S. Lee. Alternative Fuels. Taylor & Francis.1996
[8]金淳.150万千卡时上吸式木材气化炉试验报告.林产化工通讯,1994,(3)
[9]张进平.生物质流态化催化气化技术研究.林产化学与工业,2001,21(3):16～20
[10] Y. Dennis. A review on the development and commercialization of biomass gasification technologies in China. Renewable and Sustainable Energy Reviews, 2001, 8
[11]易维明.玉米芯热解裂解气化机理的研究及在设计热解装置中的应用:[博士学位论文].北京:北京农业工程大学,1994
[12]董良杰.生物质热裂解技术及其反应动力学研究:[博士学位论文].沈阳:沈阳农业大学,1997
[13]袁振宏,吴创之,马隆龙,等.生物质能利用原理与技术.北京:化学工业出版社,2005:369～383
[14] T. Reed. Biomass gasification-principles and technology. Park Ridge, 1981, 2
[15]蒋剑春.生物质能源应用研究现状与发展前景.北京:化学工业出版社,2002,22(2):75～80
[16]汪家铭.Shell煤气化技术及其在我国的应用.化肥工业,2006,33(6):1～5
[17] K. Sjostrom, E. Bjombom, C. Guanxing, et a1.In:APAS, clean coal technology program, 1992～1994 Volume 3, C3
[18] T. R. McLendon, A. P. Lui, R. L. Pineault, et a1. High-pressure co-gasification of coal and biomass in a fluidized bed. Biomass and Bioenergy,2004,26:377～388
[19] A.G. Collot, Y. Zhuo, D. R. Dugwell. Co-pyrolysis and co-gasification of coal and biomass in bench-scale fixed-bed and fluidised bed reactor. Fuel, 1999, 78:667～679
[20] K. Sjostrom, G. Chen, Q. Yu, et a1. Promoted reactivity of char in cogasification of biomass and coal:synergies in the thermochemical process. Fuel, 1999, 78(10):1189～1194
[21] R. C. Brown, Q. Liu, G. Norton. Catalytic effects observed during the co-gasification of coal and switchgrass. Biomass and Bioenergy, 2000, 18(6):499～506
[22]宋新朝,李克忠,王锦凤,等.流化床生物质与煤共气化特性的初步研究.燃料化学学报,2006,34(3):303～308
[23]闫秋会,郭烈锦,梁兴.煤及生物质共超临界水气化过程中的协同效应.西安交通大学学报,2006.40(5):506～509
[24]黄元.二氧化碳富氧气化的设想.中氮肥,1998,(5):62～64
[25]张祥德,霍建生,杜进祥.放空CO2气体返回造气炉工艺的探讨.天津化工,2003,(5):41～44
[26]赵登凌,彭波,梁杰华.CO2及O2气化焦炭制备高纯CO成套工业化新技术的开发与应用.煤化工,2002,(1):29～32
[27]龚欣,郭晓镭,代正华,等.气流床粉煤加压气化制备合成气新技术.煤化工,2005,(6):5～8
[28]马斌,刘建生,李大尚.CO生产新工艺和新炉型在济南石化二厂的应用.煤化工,1998,(3):17～19
[29]邓渊.煤炭加压气化.北京:中国建设出版社,1981
[30]阴秀丽.固体生物质循环流化床气化炉数学模型的研究:[硕士学位论文].广州:中国科学院广州能源研究所,1993
[31]沙兴中,杨南星.煤的气化与应用.上海:华东理工大学出版社,1995:33～34
[32]朱子彬,马智华,张成芳,等.活性点数对煤焦气化反应的影响Ⅰ.气化活性的评价.燃料化学学报,1994,22(3):321～328
[33] R. L. Walker, F. J. Rusinkoa, L. G. Austin. Gas Reaction of carbon. Adv, Catal, 1959, 11:135
[34]文芳.热重法研究煤焦H2O气化反应动力学.煤炭学报,2004,29(3):350～353
[35] T. Kodma, A. Aoki, H. ohtake. Thermochemical CO2 Gasification of coal using a Reactive Coal-In2O3 system. Energy and Fuels, 2000, 14:202～211
[36]李余增.热分析.北京:清华大学出版社,1987
[37]蔡正千.热分析.北京:高等教育出版社,1992:54～57
[38] S. Kawakami, K. Lnoue, H. Tenaka, et al. Thermal Conversion of Solid Wasters and Biomass[C]//American Chemical Society Symposium Series 130,Washington D C,1980:423～557
[39]崔洪,杨建丽,刘振宇.废旧轮胎热解行为的TG/DTG研究.化工学报,1999,50(6):826～833
[40]谢克昌.煤的结构与反应性.北京:科学出版社.2002:294～297
[41]朱学栋.煤化程度和升温速率对热分解影响的研究.煤炭转化,1999,4(2):43～47
[42] A. Demirbas. Biomass resource facilities and biomass conversion processing for fuels and chemicals. Energy Conversion and Management, 2001,42(11):1357～1378
[43] M. J. Safi, I. M. Mishra, B. Prasad. Global degradation kinetics of pine needles in air. Thermochimica Acta, 2004, 412:155～162
[44] A. G. Barea, P. Ollero. An approximate method for solving gas-solid non-catalytic reactions. Chemical Engineering Science 2006, 61:3725～3735
[45]林荣英,张济宇.低活性无烟煤二氧化碳催化气化动力学.化工学报,2005,56(12):2333～2341
[46] D. P. Ye, J. B. Agenw, D. K. Zhang. Gasification of a south Australian low-coal with carbon dioxide and steam: kinetics and reactivity studies. Fuel,1998, 77(11):1209～1219
[47] C. Y. Wen. Noncatalytic heterogeneous solid-fluid reaction models. Ing. Eng. Chem 2006, 60(9):34～54
[48] Alejandro Molina, Fanor Mondragon. Reactivity of coal gasification with steam and CO2. Fuel, 1998, 77(15):1831～1839
[49] J. W. Cumming. Combustion kinetics of polymers.Fuel,1984, 63(10):1436~1440
[50]张力,冉景煜,屈超蜀,等.城市生活垃圾物性与热解特性的实验研究.环境科学学报,2000,20(5):645～647
[2]马经国.新能源技术.南京:江苏科学技术出版社,1992:1～2
[3] J. Chang, D. Y. C. Leung, C. Z. Wu, et al. A review on the energy production, consumption, and prospect of renewable energy in China. Renewable and Sustainable Energy Reviews, 2003,7:453～468
[4]米铁.生物质气化过程的综合实验研究:[博士学位论文].武汉:华中科技大学,2002
[5]段菁春,肖军,王杰林,等.生物质与煤共燃研究.电站系统工程,2004,20(1):1～4
[6] M. Sadakata, K. Takahashi, M. Saito, T. Sakai. Productions of fuel gas and char from wood, lignin and holocellulose by carbonization. Fuel, 1987, 66:1667～1671
[7] S. Lee. Alternative Fuels. Taylor & Francis.1996
[8]金淳.150万千卡时上吸式木材气化炉试验报告.林产化工通讯,1994,(3)
[9]张进平.生物质流态化催化气化技术研究.林产化学与工业,2001,21(3):16～20
[10] Y. Dennis. A review on the development and commercialization of biomass gasification technologies in China. Renewable and Sustainable Energy Reviews, 2001, 8
[11]易维明.玉米芯热解裂解气化机理的研究及在设计热解装置中的应用:[博士学位论文].北京:北京农业工程大学,1994
[12]董良杰.生物质热裂解技术及其反应动力学研究:[博士学位论文].沈阳:沈阳农业大学,1997
[13]袁振宏,吴创之,马隆龙,等.生物质能利用原理与技术.北京:化学工业出版社,2005:369～383
[14] T. Reed. Biomass gasification-principles and technology. Park Ridge, 1981, 2
[15]蒋剑春.生物质能源应用研究现状与发展前景.北京:化学工业出版社,2002,22(2):75～80
[16]汪家铭.Shell煤气化技术及其在我国的应用.化肥工业,2006,33(6):1～5
[17] K. Sjostrom, E. Bjombom, C. Guanxing, et a1.In:APAS, clean coal technology program, 1992～1994 Volume 3, C3
[18] T. R. McLendon, A. P. Lui, R. L. Pineault, et a1. High-pressure co-gasification of coal and biomass in a fluidized bed. Biomass and Bioenergy,2004,26:377～388
[19] A.G. Collot, Y. Zhuo, D. R. Dugwell. Co-pyrolysis and co-gasification of coal and biomass in bench-scale fixed-bed and fluidised bed reactor. Fuel, 1999, 78:667～679
[20] K. Sjostrom, G. Chen, Q. Yu, et a1. Promoted reactivity of char in cogasification of biomass and coal:synergies in the thermochemical process. Fuel, 1999, 78(10):1189～1194
[21] R. C. Brown, Q. Liu, G. Norton. Catalytic effects observed during the co-gasification of coal and switchgrass. Biomass and Bioenergy, 2000, 18(6):499～506
[22]宋新朝,李克忠,王锦凤,等.流化床生物质与煤共气化特性的初步研究.燃料化学学报,2006,34(3):303～308
[23]闫秋会,郭烈锦,梁兴.煤及生物质共超临界水气化过程中的协同效应.西安交通大学学报,2006.40(5):506～509
[24]黄元.二氧化碳富氧气化的设想.中氮肥,1998,(5):62～64
[25]张祥德,霍建生,杜进祥.放空CO2气体返回造气炉工艺的探讨.天津化工,2003,(5):41～44
[26]赵登凌,彭波,梁杰华.CO2及O2气化焦炭制备高纯CO成套工业化新技术的开发与应用.煤化工,2002,(1):29～32
[27]龚欣,郭晓镭,代正华,等.气流床粉煤加压气化制备合成气新技术.煤化工,2005,(6):5～8
[28]马斌,刘建生,李大尚.CO生产新工艺和新炉型在济南石化二厂的应用.煤化工,1998,(3):17～19
[29]邓渊.煤炭加压气化.北京:中国建设出版社,1981
[30]阴秀丽.固体生物质循环流化床气化炉数学模型的研究:[硕士学位论文].广州:中国科学院广州能源研究所,1993
[31]沙兴中,杨南星.煤的气化与应用.上海:华东理工大学出版社,1995:33～34
[32]朱子彬,马智华,张成芳,等.活性点数对煤焦气化反应的影响Ⅰ.气化活性的评价.燃料化学学报,1994,22(3):321～328
[33] R. L. Walker, F. J. Rusinkoa, L. G. Austin. Gas Reaction of carbon. Adv, Catal, 1959, 11:135
[34]文芳.热重法研究煤焦H2O气化反应动力学.煤炭学报,2004,29(3):350～353
[35] T. Kodma, A. Aoki, H. ohtake. Thermochemical CO2 Gasification of coal using a Reactive Coal-In2O3 system. Energy and Fuels, 2000, 14:202～211
[36]李余增.热分析.北京:清华大学出版社,1987
[37]蔡正千.热分析.北京:高等教育出版社,1992:54～57
[38] S. Kawakami, K. Lnoue, H. Tenaka, et al. Thermal Conversion of Solid Wasters and Biomass[C]//American Chemical Society Symposium Series 130,Washington D C,1980:423～557
[39]崔洪,杨建丽,刘振宇.废旧轮胎热解行为的TG/DTG研究.化工学报,1999,50(6):826～833
[40]谢克昌.煤的结构与反应性.北京:科学出版社.2002:294～297
[41]朱学栋.煤化程度和升温速率对热分解影响的研究.煤炭转化,1999,4(2):43～47
[42] A. Demirbas. Biomass resource facilities and biomass conversion processing for fuels and chemicals. Energy Conversion and Management, 2001,42(11):1357～1378
[43] M. J. Safi, I. M. Mishra, B. Prasad. Global degradation kinetics of pine needles in air. Thermochimica Acta, 2004, 412:155～162
[44] A. G. Barea, P. Ollero. An approximate method for solving gas-solid non-catalytic reactions. Chemical Engineering Science 2006, 61:3725～3735
[45]林荣英,张济宇.低活性无烟煤二氧化碳催化气化动力学.化工学报,2005,56(12):2333～2341
[46] D. P. Ye, J. B. Agenw, D. K. Zhang. Gasification of a south Australian low-coal with carbon dioxide and steam: kinetics and reactivity studies. Fuel,1998, 77(11):1209～1219
[47] C. Y. Wen. Noncatalytic heterogeneous solid-fluid reaction models. Ing. Eng. Chem 2006, 60(9):34～54
[48] Alejandro Molina, Fanor Mondragon. Reactivity of coal gasification with steam and CO2. Fuel, 1998, 77(15):1831～1839
[49] J. W. Cumming. Combustion kinetics of polymers.Fuel,1984, 63(10):1436~1440
[50]张力,冉景煜,屈超蜀,等.城市生活垃圾物性与热解特性的实验研究.环境科学学报,2000,20(5):645～647