煤热解反应热测定方法研究进展
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摘要
煤热解既是煤炭燃烧、气化、直接液化等工艺的初始反应和伴随过程,也是煤转化的主要工艺之一,而煤热解反应热是反应器设计、热解机理研究、建模及工艺能效评估等过程所需的重要热力学参数。本文首先对煤及其他非均质有机物热解反应热测定方法和技术的研究现状做了综述性评介,分析比较了模型预测法(Merric模型、Strezov模型)和实验测定法(热值法、电功率法、计算机辅助热分析法、差示扫描量热法等)方法的优势以及存在的问题,特别关注将这些方法应用于煤热解反应热测定过程中的适应性。结果表明,在研究掌握测试参数影响煤热解反应热测定精度的规律、解决数据处理方法的前提下,基于TG-DSC同步联用法或可建立相对简单、易行、普适的煤热解反应热测定方法和技术。
In nature pyrolysis can be considered as the initial stage and/or paralleling part of coal combustion,gasification and direct liquefaction,and pyrolysis itself is also one of the fundamental technologies in coal conversion processes. Thus it is understandable that reaction heat of coal pyrolysis is of significance that it is the important thermodynamic parameter used in reactor design,mechanism study,and energy efficiency assessment. This paper presents a critical survey on the status of methods and techniques for measurement of pyrolysis reaction heat of coal and relevant heterogeneous organic matters,and a detailed analysis and comparison of these methods,such as model prediction methods(Merric model,Strezov model)and experimental measuring methods(heat value method,electricity power method,computer aided thermal analysis,and differential scanning calorimetry method)were conducted,in which especial attention was paid to the possibility of application of these methods in the measurement of pyrolysis reaction heat. Results show that an easy,but rational and considerable accurate method for measurement of coal pyrolysis heat on the basis of TG-DSC technique could be established under conditions that the effects of measuring parameters on measurement precision are thoroughly studied and elucidated,as well as the measurement data resolution process is constructed.
In nature pyrolysis can be considered as the initial stage and/or paralleling part of coal combustion,gasification and direct liquefaction,and pyrolysis itself is also one of the fundamental technologies in coal conversion processes. Thus it is understandable that reaction heat of coal pyrolysis is of significance that it is the important thermodynamic parameter used in reactor design,mechanism study,and energy efficiency assessment. This paper presents a critical survey on the status of methods and techniques for measurement of pyrolysis reaction heat of coal and relevant heterogeneous organic matters,and a detailed analysis and comparison of these methods,such as model prediction methods(Merric model,Strezov model)and experimental measuring methods(heat value method,electricity power method,computer aided thermal analysis,and differential scanning calorimetry method)were conducted,in which especial attention was paid to the possibility of application of these methods in the measurement of pyrolysis reaction heat. Results show that an easy,but rational and considerable accurate method for measurement of coal pyrolysis heat on the basis of TG-DSC technique could be established under conditions that the effects of measuring parameters on measurement precision are thoroughly studied and elucidated,as well as the measurement data resolution process is constructed.
引文
[1]GARY J S,RUSSELL C M.Gasification technologies:the path to clean affordable energy in the 21st century[J].Fuel Processing Technology,2001,71:79-97.
[2]解强,梁鼎成,田萌,等.升温速率对神木煤热解半焦结构性能的影响[J].燃料化学学报,2015,43(7):798-805.XIE Q,LIANG D C,TIAN M,et al.Influence of heating rate on structure of chars derived from pyrolysis of Shenmu coal[J].Journal of Fuel Chemistry and Technology,2015,43(7):798-805.
[3]Frau C,Ferrara F,Orsini A,et al.Characterization of several kinds of coal and biomass for pyrolysis and gasification[J].Fuel,2014,152:138-145.
[4]STANGER R,XIE W,WALL T,et al.Dynamic behaviour of coal macerals during pyrolysis-associations between physical,thermal and chemical changes[J].Proceeding of the Combustion Institute,2013,34(2):2393-2400.
[5]STANGER R,XIE W,WALL T,et al.Dynamic measurement of coal thermal properties and elemental composition of volatile matter during coal pyrolysis[J].Journal of Materials Research and Technology,2014,3(1):2-8.
[6]李超,郑长征,王晓红.热解气氛对煤热解行为的影响[J].西安工程大学学报,2013,27(5):616-621.LI C,ZHENG C Z,WANG X H.Influence of atmosphere on the behavior of coal pyrolysis[J].Journal of Xi’an Polytechnic University,2013,27(5):616-621.
[7]王瑞杰,宋长忠,勒振一,等.升温速率对混合煤样热解的影响及动力学分析[J].洁净煤技术,2014,20(4):73-76.WANG R J,SONG C Z,LE Z Y,et al.Influence of heating rate on mixed coal sample pyrolysis and dynamic analysis[J].Clean Coal Technology,2014,20(4):73-76.
[8]KRZESINSKA M,SZELUGA U,CZAJKOWSKA S,et al.The thermal decomposition studies of three Polish bituminous coking coals and their blends[J].International Journal of Coal Geology,2009,77:350-355.
[9]STREZOV V,LUCAS J A,STREZOV L.Quantifying the heats of coal devolatilization[J].Metallurgical and Materials Transactions,2000,31:1125-1131.
[10]STREZOV V,LUCAS J A,STREZOV L.Experimental and modeling of the thermal regions of activity during pyrolysis of bituminous coals[J].Journal of Analytical and Applied Pyrolysis,2004,71:375-392.
[11]JERZY T,HENEYK P.Specific heat capacity and enthalpy of coal pyrolysis at elevated temperatures[J].Fuel,1996,75(9):1089-1093.
[12]赵渊.煤直接液化反应热的测定与计算[D].北京:煤炭科学研究总院,2010.ZHAO Y.Determination and calculation of direct coal liquefaction reaction heat[D].Beijing:China Coal Research Institute,2010.
[13]ANUP K S,PARTHAPRATIM G,RANAJIT K S.Modeling and experimental studies on pyrolysis of biomass particles[J].Journal of Analytical and Applied Pyrolysis,2008,81(2):183-192.
[14]HESELI Y,JAV O,LPHD G.Modeling biomass particle pyrolysis with temperature-dependent heat of reactions[J].Journal of Analytical and Applied Pyrolysis,2011,90(2):140-154.
[15]MERRICK D.Mathematical models of the thermal decomposition of coal—1.The evolution of volatile matter[J].Fuel,1983,62(5):534-539.
[16]MERRICK D.Mathematical models of the thermal decomposition of coal—2.Specific heats and heats of reaction[J].Fuel,1983,62(5):540-546.
[17]张世煜.焦炉炭化室热过程的数值模拟[D].鞍山:辽宁科技大学,2012.ZHANG S Y.Numerical simulation of thermal processes in a coke oven chamber[D].Anshan:University of Science and Technology Liaoning,2012.
[18]张世煜,谢安国.焦炉炭化室热过程的二维数值模拟[J].冶金能源,2013,32(1):20-25.ZHANG S Y,XIE A G.Two dimensional numerical simulations of thermal processes in a coke oven chamber[J].Energy for Metallurgical Industry,2013,32(1):20-25.
[19]沈祥智,严建华,池涌.垃圾热解能耗及反应热测试方式的探讨[J].热力发电,2008,37(11):30-34.SHEN X Z,YAN J H,CHI Y.An approach to test method of energy consumption and reactive heat in MSW pyrolysis[J].Thermal Power Generation,2008,37(11):30-34.
[20]胡艳军,郑小艳,宁方勇.污水污泥热解过程的能量平衡与反应热分析[J].动力工程学报,2013,33(5):399-404.HU Y J,ZHENG X Y,NING F Y.Analysis on energy balance and reaction heat of sewage sludge pyrolysis process[J].Journal of Chinese Society of Power Engineering,2013,33(5):399-404.
[21]KWON H B,VASTOLA F J.Thermal analysis of coal under conditions of rapid heating[J].Fuel Processing Technology,1995,44:13-24.
[22]郭晓娟,左远志,秦贯丰,等.废弃印刷线路板热解能耗实验研究[J].节能技术,2013,31(3):205-208.GUO X J,ZUO Y Z,QIN G F,et al.Experimental study on pyrolysis energy consumption of waste printed circuit board[J].Energy Conservation Technology,2013,31(3):205-208.
[23]STREZOV V,LUCAS J A,STREZOV L.Computer aided thermal analysis[J].Journal of Thermal Analysis and Calorimetry,2003,72:907-918.
[24]STREZOV V,MOGHTADERI B,LUCAS J A.Computational calorimetric investigation of the reactions during thermal conversion of wood biomass[J].Biomass and Bioenergy,2004,27:459-465.
[25]魏兴海,顾永达,沈平,等.TG-DSC法研究煤、焦的燃烧[J].煤炭学报,1994,19(4):439-444.WEI X H,GU Y D,SHEN P,et al.The study of coal and char combustion with TG-DSC technique[J].Journal of China Coal Society,1994,19(4):439-444.
[26]MAHAJAN O P,TROMP A,WALKER P L.Differential scanning calorimetry studies on coal.1.Pyrolysis in an inert atmosphere[J].Fuel,1976,55(1):63-69.
[27]TROMP P J J,KAPTEIJN F,MOULIJN J A.Characterization of coal pyrolysis by means of differential scanning calorimetry.1.Quantitative heat effects in an inert atmosphere[J].Fuel Processing Technology,1987,15:45-57.
[28]LOPEZ-PEINADO A J,TROMP P J J,MOULIJN J A.Quantitative heat effects associated with pyrolysis of coals,ranging from anthracite to lignite[J].Fuel,1989,68:999-1005.
[29]王娜.煤/焦燃烧过程反应热的研究及动力学参数的测定[D].武汉:华中科技大学,2012.WANG N.Investigation on the enthalpy and kinetics parameter of pulverized coal/char combustion[D].Wuhan:Huazhong University of Science&Technology,2012.
[30]HEFTA R S,SCHOBERT H H,KUBE W R.Calorimetric pyrolysis of a North Dakota lignite[J].Fuel,1986,65(9):1196-1202.
[31]ELDER J P,MARY B H.Thermogravimetry and differential scanning calorimetry of Kentucky bituminous coals[J].Fuel,1984,63:262-267.
[32]RATHA J,WOLFINGERA M G,STEINER G,et al.Heat of wood pyrolysis[J].Fuel,2003,82:81-91.
[33]何芳,徐梁,柏雪源,等.生物质热解过程吸热量[J].太阳能学报,2006,27(3):237-241.HE F,XU L,BAI X Y,et al.Heat requirement of biomass pyrolysis[J].Acta Energiae Solaris Sinica,2006,27(3):237-241.
[34]段佳,罗永浩,陆方,等.稻秆热解的实验研究[J].动力工程,2007,27(2):297-300.DUAN J,LUO Y H,LU F,et al.Experimental study on rice stalk pyrolysis[J].Journal of Power Engineering,2007,27(2):297-300.
[35]CHEN Q,YANG R M,ZHAO B,et al.Investigation of heat of biomass pyrolysis and secondary reactions by simultaneous thermogravimetry and differential scanning calorimetry[J].Fuel,2014,134:467-476.
[36]SHEN J C,IGATHINATHANE C,YU M L,et al.Biomass pyrolysis and combustion integral and differential reaction heats with temperatures using thermogravimetric analysis/differential scanning calorimetry[J].Bioresource Technology,2015,185:89-98.
[37]ANCA-COUCE A,ZOBEL N,BERGER A,et al.Smouldering of pine wood:kinetics and reaction heats[J].Combustion and Flame,2012,159:1708-1719.
[38]STENSENG M,JENSEN A,DAM-JOHANSEN K.Investigation of biomass pyrolysis by thermogravimetric analysis and differential scanning calorimetry[J].Journal of Analytical and Applied Pyrolysis,2001,58-59:765-780.
[39]GOMEZ C,VELO E,BARONTINI F,et al.Influence of secondary reactions on the heat of pyrolysis of biomass[J].Ind.Eng.Chem.Res.,2009,48(23):10222-10233.
[40]陈祎,罗永浩,陆方,等.稻秆慢速热解的需热量及动力学分析[J].化学工程,2008,36(1):44-47.CHEN Y,LUO Y H,LU F,et al.Caloric requirement and kinetic analysis of rice straw during slow pyrolysis[J].Chemical Engineer(China),2008,36(1):44-47.
[41]HENDERSON J B,WIEBELT J A,TANT M R.A model for the thermal response of polymer composite materials with experimental verification[J].Journal of Composite Materials,1985,19:579-595.
[42]HENDERSON Y B,EMMERICH W D,WASSMER E.Measurement of the specific heat and heat 3of decomposition of a polymer composite to high temperatures[J].Journal of Thermal Analysis,1988,33:1067-1077.
[43]LATTIMER B Y,OUELLETTE J,TRELLES J.Measuring properties for material decomposition modeling[J].Fire Mater,2011,35:1-17.
[44]AGANWAI G,LATTIMER B.Method for measuring the standard heat of decomposition of materials[J].Thermochimica Acta,2012,545:34-47.
[45]常娜,甘艳萍,陈延信.升温速率及热解温度对煤热解过程的影响[J].煤炭转化,2012,35(3):1-5.CHANG N,GAN Y P,CHEN Y X.Study on the effects of heating rate and temperature to coal pyrolysis[J].Coal Conversion,2012,35(3):1-5.
[2]解强,梁鼎成,田萌,等.升温速率对神木煤热解半焦结构性能的影响[J].燃料化学学报,2015,43(7):798-805.XIE Q,LIANG D C,TIAN M,et al.Influence of heating rate on structure of chars derived from pyrolysis of Shenmu coal[J].Journal of Fuel Chemistry and Technology,2015,43(7):798-805.
[3]Frau C,Ferrara F,Orsini A,et al.Characterization of several kinds of coal and biomass for pyrolysis and gasification[J].Fuel,2014,152:138-145.
[4]STANGER R,XIE W,WALL T,et al.Dynamic behaviour of coal macerals during pyrolysis-associations between physical,thermal and chemical changes[J].Proceeding of the Combustion Institute,2013,34(2):2393-2400.
[5]STANGER R,XIE W,WALL T,et al.Dynamic measurement of coal thermal properties and elemental composition of volatile matter during coal pyrolysis[J].Journal of Materials Research and Technology,2014,3(1):2-8.
[6]李超,郑长征,王晓红.热解气氛对煤热解行为的影响[J].西安工程大学学报,2013,27(5):616-621.LI C,ZHENG C Z,WANG X H.Influence of atmosphere on the behavior of coal pyrolysis[J].Journal of Xi’an Polytechnic University,2013,27(5):616-621.
[7]王瑞杰,宋长忠,勒振一,等.升温速率对混合煤样热解的影响及动力学分析[J].洁净煤技术,2014,20(4):73-76.WANG R J,SONG C Z,LE Z Y,et al.Influence of heating rate on mixed coal sample pyrolysis and dynamic analysis[J].Clean Coal Technology,2014,20(4):73-76.
[8]KRZESINSKA M,SZELUGA U,CZAJKOWSKA S,et al.The thermal decomposition studies of three Polish bituminous coking coals and their blends[J].International Journal of Coal Geology,2009,77:350-355.
[9]STREZOV V,LUCAS J A,STREZOV L.Quantifying the heats of coal devolatilization[J].Metallurgical and Materials Transactions,2000,31:1125-1131.
[10]STREZOV V,LUCAS J A,STREZOV L.Experimental and modeling of the thermal regions of activity during pyrolysis of bituminous coals[J].Journal of Analytical and Applied Pyrolysis,2004,71:375-392.
[11]JERZY T,HENEYK P.Specific heat capacity and enthalpy of coal pyrolysis at elevated temperatures[J].Fuel,1996,75(9):1089-1093.
[12]赵渊.煤直接液化反应热的测定与计算[D].北京:煤炭科学研究总院,2010.ZHAO Y.Determination and calculation of direct coal liquefaction reaction heat[D].Beijing:China Coal Research Institute,2010.
[13]ANUP K S,PARTHAPRATIM G,RANAJIT K S.Modeling and experimental studies on pyrolysis of biomass particles[J].Journal of Analytical and Applied Pyrolysis,2008,81(2):183-192.
[14]HESELI Y,JAV O,LPHD G.Modeling biomass particle pyrolysis with temperature-dependent heat of reactions[J].Journal of Analytical and Applied Pyrolysis,2011,90(2):140-154.
[15]MERRICK D.Mathematical models of the thermal decomposition of coal—1.The evolution of volatile matter[J].Fuel,1983,62(5):534-539.
[16]MERRICK D.Mathematical models of the thermal decomposition of coal—2.Specific heats and heats of reaction[J].Fuel,1983,62(5):540-546.
[17]张世煜.焦炉炭化室热过程的数值模拟[D].鞍山:辽宁科技大学,2012.ZHANG S Y.Numerical simulation of thermal processes in a coke oven chamber[D].Anshan:University of Science and Technology Liaoning,2012.
[18]张世煜,谢安国.焦炉炭化室热过程的二维数值模拟[J].冶金能源,2013,32(1):20-25.ZHANG S Y,XIE A G.Two dimensional numerical simulations of thermal processes in a coke oven chamber[J].Energy for Metallurgical Industry,2013,32(1):20-25.
[19]沈祥智,严建华,池涌.垃圾热解能耗及反应热测试方式的探讨[J].热力发电,2008,37(11):30-34.SHEN X Z,YAN J H,CHI Y.An approach to test method of energy consumption and reactive heat in MSW pyrolysis[J].Thermal Power Generation,2008,37(11):30-34.
[20]胡艳军,郑小艳,宁方勇.污水污泥热解过程的能量平衡与反应热分析[J].动力工程学报,2013,33(5):399-404.HU Y J,ZHENG X Y,NING F Y.Analysis on energy balance and reaction heat of sewage sludge pyrolysis process[J].Journal of Chinese Society of Power Engineering,2013,33(5):399-404.
[21]KWON H B,VASTOLA F J.Thermal analysis of coal under conditions of rapid heating[J].Fuel Processing Technology,1995,44:13-24.
[22]郭晓娟,左远志,秦贯丰,等.废弃印刷线路板热解能耗实验研究[J].节能技术,2013,31(3):205-208.GUO X J,ZUO Y Z,QIN G F,et al.Experimental study on pyrolysis energy consumption of waste printed circuit board[J].Energy Conservation Technology,2013,31(3):205-208.
[23]STREZOV V,LUCAS J A,STREZOV L.Computer aided thermal analysis[J].Journal of Thermal Analysis and Calorimetry,2003,72:907-918.
[24]STREZOV V,MOGHTADERI B,LUCAS J A.Computational calorimetric investigation of the reactions during thermal conversion of wood biomass[J].Biomass and Bioenergy,2004,27:459-465.
[25]魏兴海,顾永达,沈平,等.TG-DSC法研究煤、焦的燃烧[J].煤炭学报,1994,19(4):439-444.WEI X H,GU Y D,SHEN P,et al.The study of coal and char combustion with TG-DSC technique[J].Journal of China Coal Society,1994,19(4):439-444.
[26]MAHAJAN O P,TROMP A,WALKER P L.Differential scanning calorimetry studies on coal.1.Pyrolysis in an inert atmosphere[J].Fuel,1976,55(1):63-69.
[27]TROMP P J J,KAPTEIJN F,MOULIJN J A.Characterization of coal pyrolysis by means of differential scanning calorimetry.1.Quantitative heat effects in an inert atmosphere[J].Fuel Processing Technology,1987,15:45-57.
[28]LOPEZ-PEINADO A J,TROMP P J J,MOULIJN J A.Quantitative heat effects associated with pyrolysis of coals,ranging from anthracite to lignite[J].Fuel,1989,68:999-1005.
[29]王娜.煤/焦燃烧过程反应热的研究及动力学参数的测定[D].武汉:华中科技大学,2012.WANG N.Investigation on the enthalpy and kinetics parameter of pulverized coal/char combustion[D].Wuhan:Huazhong University of Science&Technology,2012.
[30]HEFTA R S,SCHOBERT H H,KUBE W R.Calorimetric pyrolysis of a North Dakota lignite[J].Fuel,1986,65(9):1196-1202.
[31]ELDER J P,MARY B H.Thermogravimetry and differential scanning calorimetry of Kentucky bituminous coals[J].Fuel,1984,63:262-267.
[32]RATHA J,WOLFINGERA M G,STEINER G,et al.Heat of wood pyrolysis[J].Fuel,2003,82:81-91.
[33]何芳,徐梁,柏雪源,等.生物质热解过程吸热量[J].太阳能学报,2006,27(3):237-241.HE F,XU L,BAI X Y,et al.Heat requirement of biomass pyrolysis[J].Acta Energiae Solaris Sinica,2006,27(3):237-241.
[34]段佳,罗永浩,陆方,等.稻秆热解的实验研究[J].动力工程,2007,27(2):297-300.DUAN J,LUO Y H,LU F,et al.Experimental study on rice stalk pyrolysis[J].Journal of Power Engineering,2007,27(2):297-300.
[35]CHEN Q,YANG R M,ZHAO B,et al.Investigation of heat of biomass pyrolysis and secondary reactions by simultaneous thermogravimetry and differential scanning calorimetry[J].Fuel,2014,134:467-476.
[36]SHEN J C,IGATHINATHANE C,YU M L,et al.Biomass pyrolysis and combustion integral and differential reaction heats with temperatures using thermogravimetric analysis/differential scanning calorimetry[J].Bioresource Technology,2015,185:89-98.
[37]ANCA-COUCE A,ZOBEL N,BERGER A,et al.Smouldering of pine wood:kinetics and reaction heats[J].Combustion and Flame,2012,159:1708-1719.
[38]STENSENG M,JENSEN A,DAM-JOHANSEN K.Investigation of biomass pyrolysis by thermogravimetric analysis and differential scanning calorimetry[J].Journal of Analytical and Applied Pyrolysis,2001,58-59:765-780.
[39]GOMEZ C,VELO E,BARONTINI F,et al.Influence of secondary reactions on the heat of pyrolysis of biomass[J].Ind.Eng.Chem.Res.,2009,48(23):10222-10233.
[40]陈祎,罗永浩,陆方,等.稻秆慢速热解的需热量及动力学分析[J].化学工程,2008,36(1):44-47.CHEN Y,LUO Y H,LU F,et al.Caloric requirement and kinetic analysis of rice straw during slow pyrolysis[J].Chemical Engineer(China),2008,36(1):44-47.
[41]HENDERSON J B,WIEBELT J A,TANT M R.A model for the thermal response of polymer composite materials with experimental verification[J].Journal of Composite Materials,1985,19:579-595.
[42]HENDERSON Y B,EMMERICH W D,WASSMER E.Measurement of the specific heat and heat 3of decomposition of a polymer composite to high temperatures[J].Journal of Thermal Analysis,1988,33:1067-1077.
[43]LATTIMER B Y,OUELLETTE J,TRELLES J.Measuring properties for material decomposition modeling[J].Fire Mater,2011,35:1-17.
[44]AGANWAI G,LATTIMER B.Method for measuring the standard heat of decomposition of materials[J].Thermochimica Acta,2012,545:34-47.
[45]常娜,甘艳萍,陈延信.升温速率及热解温度对煤热解过程的影响[J].煤炭转化,2012,35(3):1-5.CHANG N,GAN Y P,CHEN Y X.Study on the effects of heating rate and temperature to coal pyrolysis[J].Coal Conversion,2012,35(3):1-5.