Gasification kinetics of bulk coke in the CO_2/CO/H_2/H_2O/N_2 system simulating the atmosphere in the industrial blast furnace
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摘要
The gasification characteristics and gasification kinetics of coke in complex CO_2/CO/H_2/H_2O/N_2 systems similar to the gas system of industrial blast furnace(BF) were studied by the method of isothermal thermogravimetric analysis. The experimental gas compositions and the corresponding temperature were chosen according to data reported for industrial BFs. The gasification behavior of coke was described by the Random Pore Model(RPM), Volumetric Model(VM), and Grain Model(GM). Results showed that the gas composition of the coke gasification zone in BF changes slightly and that the temperature is the most important factor affecting coke gasification. The lower activation energy of coke samples(Coke Reaction Index(CRI)>50) is due to the high Fe_2O_3 in the ash, lower degree of graphitization, and larger pore structure. In addition, the choice of kinetic model does not differ substantially in describing the gasification mechanism of coke in a BF.
The gasification characteristics and gasification kinetics of coke in complex CO_2/CO/H_2/H_2O/N_2 systems similar to the gas system of industrial blast furnace(BF) were studied by the method of isothermal thermogravimetric analysis. The experimental gas compositions and the corresponding temperature were chosen according to data reported for industrial BFs. The gasification behavior of coke was described by the Random Pore Model(RPM), Volumetric Model(VM), and Grain Model(GM). Results showed that the gas composition of the coke gasification zone in BF changes slightly and that the temperature is the most important factor affecting coke gasification. The lower activation energy of coke samples(Coke Reaction Index(CRI)>50) is due to the high Fe_2O_3 in the ash, lower degree of graphitization, and larger pore structure. In addition, the choice of kinetic model does not differ substantially in describing the gasification mechanism of coke in a BF.
The gasification characteristics and gasification kinetics of coke in complex CO_2/CO/H_2/H_2O/N_2 systems similar to the gas system of industrial blast furnace(BF) were studied by the method of isothermal thermogravimetric analysis. The experimental gas compositions and the corresponding temperature were chosen according to data reported for industrial BFs. The gasification behavior of coke was described by the Random Pore Model(RPM), Volumetric Model(VM), and Grain Model(GM). Results showed that the gas composition of the coke gasification zone in BF changes slightly and that the temperature is the most important factor affecting coke gasification. The lower activation energy of coke samples(Coke Reaction Index(CRI)>50) is due to the high Fe_2O_3 in the ash, lower degree of graphitization, and larger pore structure. In addition, the choice of kinetic model does not differ substantially in describing the gasification mechanism of coke in a BF.
引文
[1]K.J.Li,J.L.Zhang,Y.P.Zhang,Z.J.Liu,and X.Jiang,Critical analyses about the development of iron-making process based on the principle of energy-saving and emission reduction,Chin.J.Proc.Eng.,14(2014),No.1,p.162.
[2]M.M.Sun,X.J.Ning,J.L.Zhang,K.J.Li,G.W.Wang,and H.Y.Wang,Research status and progress of energy saving and emission reduction technology for ironmaking,Chin.Metall.,28(2018),No.3,p.1.
[3]A.K.Biswas,Principles of Blast Furnace Ironmaking:Theory and Practice,Cootha Publishing House,Brisbane,1981,p.46.
[4]K.J.Li,Structural Evolution Behavior and Muti-phase Reaction Mechanism of Coke in Blast Furnace[Dissertation],University of Science and Technology Beijing,Beijing,2017,p.5.
[5]M.Grigore,R.Sakurovs,D.French,and V.Sahajwalla,Properties and CO2 reactivity of the inert and reactive maceral-derived components in cokes,Int.J.Coal Geol.,98(2012),p.1.
[6]S.Pusz,M.Krzesińska,L.Sm?dowski,J.Majewska,B.Pilawa,and B.Kwiecińska,Changes in coke structure due to reaction with carbon dioxide,Int.J.Coal Geol.,81(2010),No.4,p.287.
[7]M.Grigore,R.Sakurovs,D.French,and V.Sahajwalla,Influence of mineral matter on coke reactivity with carbon dioxide,ISIJ Int.,46(2006),No.4,p.503.
[8]Z.Y.Chang,P.Wang,J.L.Zhang,K.X.Jiao,Y.Q.Zhang,and Z.J.Liu,Effect of CO2 and H2O on gasification dissolution and deep reaction of coke,Int.J.Miner.Metall.Mater.,25(2018),No.12,p.1402.
[9]S.Gupta,M.Dubikova,D.French,and V.Sahajwalla,Effect of CO2 gasification on the transformations of coke minerals at high temperatures,Energy Fuels,21(2007),No.2,p.1052.
[10]W.T.Guo,Q.G.Xue,Y.L.Liu,Z.C.Guo,X.F.She,J.S.Wang,Q.Q.Zhao,and X.W.An,Kinetic analysis of gasification reaction of coke with CO2 or H2O,Int.J.Hydrogen Energy,40(2015),No.39,p.13306.
[11]Z.S.Liu and Q.Wang,Non-isothermal kinetics of metallurgical coke gasification by carbon dioxide,Coke Chem.,60(2017),No.4,p.140.
[12]W.Wang,J.Wang,R.S.Xu,Y.Yu,Y.Jin,and Z.L.Xue,Influence mechanism of zinc on the solution loss reaction of coke used in blast furnace,Fuel Process.Technol.,159(2017),p.118.
[13]L.W.Ren,J.L.Yang,F.Gao,and J.D.Yan,Laboratory study on gasification reactivity of coals and petcokes in CO2/steam at high temperatures,Energy Fuels,27(2013),No.9,p.5054.
[14]J.H.Zou,Z.J.Zhou,F.C.Wang,W.Zhang,Z.H.Dai,H.F.Liu,and Z.H.Yu,Modeling reaction kinetics of petroleum coke gasification with CO2,Chem.Eng.Process.,46(2007),No.7,p.630.
[15]J.L.Zhang,J.Guo,G.W.Wang,T.Xu,Y.F.Chai,C.L.Zheng,and R.S.Xu,Kinetics of petroleum coke/biomass blends during co-gasification,Int.J.Miner.Metall.Mater.,23(2016),No.9,p.1001.
[16]F.Trejo,M.S.Rana,and J.Ancheyta,Thermogravimetric determination of coke from asphaltenes,resins and sediments and coking kinetics of heavy crude asphaltenes,Catal.Today,150(2010),No.3-4,p.272.
[17]M.Malekshahian and J.M.Hill,Kinetic analysis of CO2 gasification of petroleum coke at high pressures,Energy Fuels,25(2011),No.9,p.4043.
[18]W.Huo,Z.J.Zhou,X.L.Chen,Z.H.Dai,and G.S.Yu,Study on CO2 gasification reactivity and physical characteristics of biomass,petroleum coke and coal chars,Bioresour.Technol.,159(2014),p.143.
[19]S.M.Shin and S.M.Jung,Gasification effect of metallurgical coke with CO2 and H2O on the porosity and macrostrength in the temperature range of 1100 to 1500?C,Energy Fuels,29(2015),No.10,p.6849.
[20]J.W.Kook,I.S.Gwak,Y.R.Gwak,M.W.Seo,and S.H.Lee,A reaction kinetic study of CO2 gasification of petroleum coke,coals and mixture,Korean J.Chem.Eng.,34(2017),No.12,p.3092.
[21]Y.M.Zhang,M.Q.Yao,S.Q.Gao,G.G.Sun,and G.W.Xu,Reactivity and kinetics for steam gasification of petroleum coke blended with black liquor in a micro fluidized bed,Appl.Energy,160(2015),p.820.
[22]H.B.Zuo,W.W.Geng,J.L.Zhang,and G.W.Wang,Comparison of kinetic models for isothermal CO2 gasification of coal char-biomass char blended char,Int.J.Miner.Metall.Mater.,22(2015),No.4,p.363.
[23]K.Jayaraman,I.G?kalp,and S.Jeyakumar,Estimation of synergetic effects of CO2 in high ash coal-char steam gasification,Appl.Therm.Eng.,110(2017),p.991.
[24]S.C.Hu,X.Q.Ma,Y.S.Lin,Z.S.Yu,and S.W.Fang,Thermogravimetric analysis of the co-combustion of paper mill sludge and municipal solid waste,Energy Convers.Manage.,99(2015),p.112.
[25]Z.S.Yu,X.Q.Ma,and A.Liu,Thermogravimetric analysis of rice and wheat straw catalytic combustion in air-and oxygen-enriched atmospheres,Energy Convers.Manage.,50(2009),No.3,p.561.
[26]W.S.Carvalho,T.J.Oliveira,C.R.Cardoso,and C.H.Ataíde,Thermogravimetric analysis and analytical pyrolysis of a variety of lignocellulosic sorghum,Chem.Eng.Res.Des.,95(2015),p.337.
[27]G.W.Wang,J.L.Zhang,J.G.Shao,and S.Ren,Characterisation and model fitting kinetic analysis of coal/biomass co-combustion,Thermochim.Acta,591(2014),p.68.
[28]Y.S.Shen,B.Y.Guo,C.Sheng P.Austin,and A.B.Yu,Three-Dimensional modeling of flow and thermochemical behavior in a blast furnace,Metall.Mater.Trans.B,46(2015),No.1,p.432.
[29]P.Zhou,H.L.Li,P.Y.Shi,and C.Q.Zhou,Simulation of the transfer process in the blast furnace shaft with layered burden,Appl.Therm.Eng.,95(2016),p.296.
[30]Q.F.Hou,E.Dianyu,S.B.Kuang,Z.Y.Li,and A.B.Yu,DEM-based virtual experimental blast furnace:A quasi-steady state model,Powder Technol.,314(2017),p.557.
[31]A.S.Jayasekara,B.J.Monaghan,and R.J.Longbottom,The kinetics of reaction of a coke analogue in CO2 gas,Fuel,154(2015),p.45.
[32]E.E.Peterson,Reaction of porous solids,AICh E J.,3(1957),No.4,p.443.
[33]S.K.Bhatia and D.D.Perlmutter,A random pore model for fluid-solid reactions:I.Isothermal,kinetic control,AICh E J.,26(2010),No.3,p.379.
[34]E.M.A.Edreis,G.Q.Luo,A.J.Li,C.F.Xu,and H.Yao,Synergistic effects and kinetics thermal behaviour of petroleum coke/biomass blends during H2O co-gasification,Energy Convers.Manage.,79(2014),p.355.
[2]M.M.Sun,X.J.Ning,J.L.Zhang,K.J.Li,G.W.Wang,and H.Y.Wang,Research status and progress of energy saving and emission reduction technology for ironmaking,Chin.Metall.,28(2018),No.3,p.1.
[3]A.K.Biswas,Principles of Blast Furnace Ironmaking:Theory and Practice,Cootha Publishing House,Brisbane,1981,p.46.
[4]K.J.Li,Structural Evolution Behavior and Muti-phase Reaction Mechanism of Coke in Blast Furnace[Dissertation],University of Science and Technology Beijing,Beijing,2017,p.5.
[5]M.Grigore,R.Sakurovs,D.French,and V.Sahajwalla,Properties and CO2 reactivity of the inert and reactive maceral-derived components in cokes,Int.J.Coal Geol.,98(2012),p.1.
[6]S.Pusz,M.Krzesińska,L.Sm?dowski,J.Majewska,B.Pilawa,and B.Kwiecińska,Changes in coke structure due to reaction with carbon dioxide,Int.J.Coal Geol.,81(2010),No.4,p.287.
[7]M.Grigore,R.Sakurovs,D.French,and V.Sahajwalla,Influence of mineral matter on coke reactivity with carbon dioxide,ISIJ Int.,46(2006),No.4,p.503.
[8]Z.Y.Chang,P.Wang,J.L.Zhang,K.X.Jiao,Y.Q.Zhang,and Z.J.Liu,Effect of CO2 and H2O on gasification dissolution and deep reaction of coke,Int.J.Miner.Metall.Mater.,25(2018),No.12,p.1402.
[9]S.Gupta,M.Dubikova,D.French,and V.Sahajwalla,Effect of CO2 gasification on the transformations of coke minerals at high temperatures,Energy Fuels,21(2007),No.2,p.1052.
[10]W.T.Guo,Q.G.Xue,Y.L.Liu,Z.C.Guo,X.F.She,J.S.Wang,Q.Q.Zhao,and X.W.An,Kinetic analysis of gasification reaction of coke with CO2 or H2O,Int.J.Hydrogen Energy,40(2015),No.39,p.13306.
[11]Z.S.Liu and Q.Wang,Non-isothermal kinetics of metallurgical coke gasification by carbon dioxide,Coke Chem.,60(2017),No.4,p.140.
[12]W.Wang,J.Wang,R.S.Xu,Y.Yu,Y.Jin,and Z.L.Xue,Influence mechanism of zinc on the solution loss reaction of coke used in blast furnace,Fuel Process.Technol.,159(2017),p.118.
[13]L.W.Ren,J.L.Yang,F.Gao,and J.D.Yan,Laboratory study on gasification reactivity of coals and petcokes in CO2/steam at high temperatures,Energy Fuels,27(2013),No.9,p.5054.
[14]J.H.Zou,Z.J.Zhou,F.C.Wang,W.Zhang,Z.H.Dai,H.F.Liu,and Z.H.Yu,Modeling reaction kinetics of petroleum coke gasification with CO2,Chem.Eng.Process.,46(2007),No.7,p.630.
[15]J.L.Zhang,J.Guo,G.W.Wang,T.Xu,Y.F.Chai,C.L.Zheng,and R.S.Xu,Kinetics of petroleum coke/biomass blends during co-gasification,Int.J.Miner.Metall.Mater.,23(2016),No.9,p.1001.
[16]F.Trejo,M.S.Rana,and J.Ancheyta,Thermogravimetric determination of coke from asphaltenes,resins and sediments and coking kinetics of heavy crude asphaltenes,Catal.Today,150(2010),No.3-4,p.272.
[17]M.Malekshahian and J.M.Hill,Kinetic analysis of CO2 gasification of petroleum coke at high pressures,Energy Fuels,25(2011),No.9,p.4043.
[18]W.Huo,Z.J.Zhou,X.L.Chen,Z.H.Dai,and G.S.Yu,Study on CO2 gasification reactivity and physical characteristics of biomass,petroleum coke and coal chars,Bioresour.Technol.,159(2014),p.143.
[19]S.M.Shin and S.M.Jung,Gasification effect of metallurgical coke with CO2 and H2O on the porosity and macrostrength in the temperature range of 1100 to 1500?C,Energy Fuels,29(2015),No.10,p.6849.
[20]J.W.Kook,I.S.Gwak,Y.R.Gwak,M.W.Seo,and S.H.Lee,A reaction kinetic study of CO2 gasification of petroleum coke,coals and mixture,Korean J.Chem.Eng.,34(2017),No.12,p.3092.
[21]Y.M.Zhang,M.Q.Yao,S.Q.Gao,G.G.Sun,and G.W.Xu,Reactivity and kinetics for steam gasification of petroleum coke blended with black liquor in a micro fluidized bed,Appl.Energy,160(2015),p.820.
[22]H.B.Zuo,W.W.Geng,J.L.Zhang,and G.W.Wang,Comparison of kinetic models for isothermal CO2 gasification of coal char-biomass char blended char,Int.J.Miner.Metall.Mater.,22(2015),No.4,p.363.
[23]K.Jayaraman,I.G?kalp,and S.Jeyakumar,Estimation of synergetic effects of CO2 in high ash coal-char steam gasification,Appl.Therm.Eng.,110(2017),p.991.
[24]S.C.Hu,X.Q.Ma,Y.S.Lin,Z.S.Yu,and S.W.Fang,Thermogravimetric analysis of the co-combustion of paper mill sludge and municipal solid waste,Energy Convers.Manage.,99(2015),p.112.
[25]Z.S.Yu,X.Q.Ma,and A.Liu,Thermogravimetric analysis of rice and wheat straw catalytic combustion in air-and oxygen-enriched atmospheres,Energy Convers.Manage.,50(2009),No.3,p.561.
[26]W.S.Carvalho,T.J.Oliveira,C.R.Cardoso,and C.H.Ataíde,Thermogravimetric analysis and analytical pyrolysis of a variety of lignocellulosic sorghum,Chem.Eng.Res.Des.,95(2015),p.337.
[27]G.W.Wang,J.L.Zhang,J.G.Shao,and S.Ren,Characterisation and model fitting kinetic analysis of coal/biomass co-combustion,Thermochim.Acta,591(2014),p.68.
[28]Y.S.Shen,B.Y.Guo,C.Sheng P.Austin,and A.B.Yu,Three-Dimensional modeling of flow and thermochemical behavior in a blast furnace,Metall.Mater.Trans.B,46(2015),No.1,p.432.
[29]P.Zhou,H.L.Li,P.Y.Shi,and C.Q.Zhou,Simulation of the transfer process in the blast furnace shaft with layered burden,Appl.Therm.Eng.,95(2016),p.296.
[30]Q.F.Hou,E.Dianyu,S.B.Kuang,Z.Y.Li,and A.B.Yu,DEM-based virtual experimental blast furnace:A quasi-steady state model,Powder Technol.,314(2017),p.557.
[31]A.S.Jayasekara,B.J.Monaghan,and R.J.Longbottom,The kinetics of reaction of a coke analogue in CO2 gas,Fuel,154(2015),p.45.
[32]E.E.Peterson,Reaction of porous solids,AICh E J.,3(1957),No.4,p.443.
[33]S.K.Bhatia and D.D.Perlmutter,A random pore model for fluid-solid reactions:I.Isothermal,kinetic control,AICh E J.,26(2010),No.3,p.379.
[34]E.M.A.Edreis,G.Q.Luo,A.J.Li,C.F.Xu,and H.Yao,Synergistic effects and kinetics thermal behaviour of petroleum coke/biomass blends during H2O co-gasification,Energy Convers.Manage.,79(2014),p.355.