严红燕等：气相质谱法研究Fe与C0,C0氧化反应动力学 285· ·实验数据 10 。文献19明 ·实验数据 10 。文献19] 10 10 .o 10 ● 1gk=-1.749-7192/T 10 10 6.0 6.57.07.58.08.59.09.5 Peo Peo T10K) 图6反应速率常数k与Pco2pcm(a)和温度(b)的关系 Fig.6 Dependence of the rate constant on Pco poo ratio (a)and temperature (b) 1473K范围内，铁片在C0,C0混合气体下的氧化反 [7]Bohn C D,Cleeton J P,Muller C R,et al.The kinetics of the re- 应过程.反应包含三个阶段：反应初始阶段反应速率 duction of iron oxide by carbon monoxide mixed with carbon diox- ide.A1ChEJ,2010,56(4):1016 快速增加、中间阶段保持最大反应速率以及反应速率 [8] Morris L.A,Smeltzer WW.The kinetics of wustite scale formation 逐渐下降阶段.最大反应速率与气体中的CO,分压呈 on iron-nickel alloys.Acta Metall,1967,15(10)1591 线性关系，表明其控速环节是CO,的界面解离反应. Pettit FS,Wagner J B.Oxidation of cobalt in CO-CO2 mixtures 反应速率常数随C02/C0体积比增大而减小，铁片氧 in the temperature range 920 C-1200 C.Acta Metall,1964,12 化反应的表观活化能为(137.7±15.8)kJ·mol-.与 (1):41 文献相比较，该方法得到的结果是可靠的，说明用气相 o] Hauffe K,Pfeiffer H.The kinetics of the wustite growth in the oxidation of iron.Z Metallkd,1953,44:37 质谱法研究铁片与C0,一C0气体的氧化反应动力学 是可行的 [11]Wagner C.Kinctics in Metallurgy.Cambridge:Massachusetts In- stitute of Technology Press,1955:83 参考文献 [12]Hu X J.Zhang T,Yan H Y,et al.Interfacial rate of CO2CO [Fruehan RJ,Belton G R.Adranced Physical Chemistry for Process reaction with the solid iron and iron oxide by isotope exchange Metallurgy.New York:Academic Press,1997:366 technique at 1273 K.IS/J Int,2012,52(9):1529 [2] Wan X F,Li D G,Liao X W,et al.Development and its applica- 03] Hu X J,Zhang T,Chou K C,et al.Determination of the rate of tion of analytical technology on converter off-gas.Angang Technol, COCO reaction with magnetite by isotope exchange technique. 2009(5):7 Steel Res Int,2012,83(9):886 (万雪峰，李德刚，廖相巍，等.转炉炉气分析技术的发展及 [14]Zhang T,Hu X J,Chou K C.Kinetic study on the reaction be- 应用.鞍钢技术，2009(5)：7) tween CO,-CO and wustite using the isotope exchange method. B]Hu Z G,He P,Liu L,et al.Continuous determination of bath Int J Miner Metall Mater,2013,20(2):125 carbon in BOF by off-gas analysis.Res fron Steel,2003,31 (3) [15]Pettit FS,Wagner J B.Transition from the linear to the parabol- 12 ie rate law during the oxidation of iron to wiistite in CO-CO,mix- (胡志刚，何平，刘浏，等.利用炉气分析进行转炉钢水连续 tures.Acta Metall,1964,12(1)35 定碳.钢铁研究，2003,31(3)：12) 16] Pettit F S,Yinger R,Wagner J B.The mechanism of oxidation 4]Wang S Y,He JZ,Huang H Y,et al.Application of mass spec- of iron in carbon monoxide-carbon dioxide mixtures.Acta Metall, trometer gas analysis system in RH refining furnace.Autom Appl, 1960,8(9):617 2010(12):41 [17]Bredesen R,Kofstad P.On the oxidation of iron in CO2 +CO (王书懿，何俊正，黄海永，等.质谱炉气分析系统在H精 mixtures:II.Reaction mechanisms during initial oxidation.Oxid 炼炉中的应用.自动化应用，2010(12)：41) M,1991,35(12):107 [5]Corbari R,Fruehan R J.Reduction of iron oxide fines to wustite [18]Worral E J,Coley K S.Kinetics of the reaction of CO,/CO gas with CO/CO gas of low reducing potential.Metall Mater Trans B, mixtures with iron oxide.Metall Mater Trans B,2010,41(4): 2010,41(2):318 813 6]Mondal K,Lorethova H,Hippo E,et al.Reduction of iron oxide [19]Himmel L,Mehl R T,Birchenall C E.Self-diffusion of iron in in carbon monoxide atmosphere:reaction controlled kinetics.Fuel iron oxides and the Wagner theory of oxidation.Trans AlME, Process Technol,2004,86(1):33 1953,197:827严红燕等: 气相质谱法研究 Fe 与 CO2 --CO 氧化反应动力学 图 6 反应速率常数 k 与 pCO2 /pCO ( a) 和温度( b) 的关系 Fig． 6 Dependence of the rate constant on pCO2 /pCO ratio ( a) and temperature ( b) 1473 K 范围内，铁片在 CO2 --CO 混合气体下的氧化反 应过程． 反应包含三个阶段: 反应初始阶段反应速率 快速增加、中间阶段保持最大反应速率以及反应速率 逐渐下降阶段． 最大反应速率与气体中的 CO2 分压呈 线性关系，表明其控速环节是 CO2 的界面解离反应． 反应速率常数随 CO2 /CO 体积比增大而减小，铁片氧 化反应的表观活化能为( 137. 7 ± 15. 8) kJ·mol － 1 ． 与 文献相比较，该方法得到的结果是可靠的，说明用气相 质谱法研究铁片与 CO2 --CO 气体的氧化反应动力学 是可行的． 参 考 文 献 ［1］ Fruehan Ｒ J，Belton G Ｒ． Advanced Physical Chemistry for Process Metallurgy． New York: Academic Press，1997: 366 ［2］ Wan X F，Li D G，Liao X W，et al． Development and its applica￾tion of analytical technology on converter off-gas． Angang Technol， 2009( 5) : 7 ( 万雪峰，李德刚，廖相巍，等． 转炉炉气分析技术的发展及 应用． 鞍钢技术，2009( 5) : 7) ［3］ Hu Z G，He P，Liu L，et al． Continuous determination of bath carbon in BOF by off-gas analysis． Ｒes Iron Steel，2003，31( 3) : 12 ( 胡志刚，何平，刘浏，等． 利用炉气分析进行转炉钢水连续 定碳． 钢铁研究，2003，31( 3) : 12) ［4］ Wang S Y，He J Z，Huang H Y，et al． Application of mass spec￾trometer gas analysis system in ＲH refining furnace． Autom Appl， 2010( 12) : 41 ( 王书懿，何俊正，黄海永，等． 质谱炉气分析系统在 ＲH 精 炼炉中的应用． 自动化应用，2010( 12) : 41) ［5］ Corbari Ｒ，Fruehan Ｒ J． Ｒeduction of iron oxide fines to wustite with CO /CO2 gas of low reducing potential． Metall Mater Trans B， 2010，41( 2) : 318 ［6］ Mondal K，Lorethova H，Hippo E，et al． Ｒeduction of iron oxide in carbon monoxide atmosphere: reaction controlled kinetics． Fuel Process Technol，2004，86( 1) : 33 ［7］ Bohn C D，Cleeton J P，Muller C Ｒ，et al． The kinetics of the re￾duction of iron oxide by carbon monoxide mixed with carbon diox￾ide． AIChE J，2010，56( 4) : 1016 ［8］ Morris L A，Smeltzer W W． The kinetics of wustite scale formation on iron-nickel alloys． Acta Metall，1967，15( 10) : 1591 ［9］ Pettit F S，Wagner J B． Oxidation of cobalt in CO--CO2 mixtures in the temperature range 920 ℃ --1200 ℃ ． Acta Metall，1964，12 ( 1) : 41 ［10］ Hauffe K，Pfeiffer H． The kinetics of the wustite growth in the oxidation of iron． Z Metallkd，1953，44: 37 ［11］ Wagner C． Kinetics in Metallurgy． Cambridge: Massachusetts In￾stitute of Technology Press，1955: 83 ［12］ Hu X J，Zhang T，Yan H Y，et al． Interfacial rate of CO2 --CO reaction with the solid iron and iron oxide by isotope exchange technique at 1273 K． ISIJ Int，2012，52( 9) : 1529 ［13］ Hu X J，Zhang T，Chou K C，et al． Determination of the rate of CO2 --CO reaction with magnetite by isotope exchange technique． Steel Ｒes Int，2012，83( 9) : 886 ［14］ Zhang T，Hu X J，Chou K C． Kinetic study on the reaction be￾tween CO2 --CO and wustite using the isotope exchange method． Int J Miner Metall Mater，2013，20( 2) : 125 ［15］ Pettit F S，Wagner J B． Transition from the linear to the parabol￾ic rate law during the oxidation of iron to wüstite in CO--CO2 mix￾tures． Acta Metall，1964，12( 1) : 35 ［16］ Pettit F S，Yinger Ｒ，Wagner J B． The mechanism of oxidation of iron in carbon monoxide-carbon dioxide mixtures． Acta Metall， 1960，8( 9) : 617 ［17］ Bredesen Ｒ，Kofstad P． On the oxidation of iron in CO2 + CO mixtures: II． Ｒeaction mechanisms during initial oxidation． Oxid Met，1991，35( 1-2) : 107 ［18］ Worral E J，Coley K S． Kinetics of the reaction of CO2 /CO gas mixtures with iron oxide． Metall Mater Trans B，2010，41( 4) : 813 ［19］ Himmel L，Mehl Ｒ T，Birchenall C E． Self-diffusion of iron in iron oxides and the Wagner theory of oxidation． Trans AIME， 1953，197: 827 · 582 ·