偏三甲苯低温氧化实验和理论研究
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摘要
利用射流搅拌反应器研究了偏三甲苯在当量为1.0、温度范围为700-1100 K条件下的低温氧化过程。根据实验和理论计算结果,发展了一个544物种3248反应的机理,更新了偏三甲苯分解、异位加成和氢提取等反应的速率常数,并在新机理中引入了偏三甲苯1位和2位甲基上的脱氢反应。本机理可以很好地预测实验结果。反应路径分析表明,1、2和4位脱氢是偏三甲苯的主要消耗路径。根据灵敏度分析可知,脱氢反应和HO_2+二甲基苄基分别起抑制和促进作用。
The present work aims to perform the experimental and kinetic study of 1,2,4-trimethylbenzene(TMB124) low-temperature oxidation under stoichiometric condition in a Jetstirred reactor(JSR). The experiment was carried out in the temperature range of 700-1100 K at atmospheric pressure. According to the measurements and theoretical calculations, a detailed chemical kinetic model involving 544 species and 3248 reactions was developed. Rate constants of TMB124 decomposition, reaction with HO_2, ipso-additions and metatheses with abstraction of methyl H-atom were updated. New pathways of H-abstraction from the 1-and 2-methyl groups were considered. The established model reproduces the measured mole fraction profiles of the major species and intermediates well. Rate-of-production analysis indicates that TMB124 is dominantly consumed by metatheses giving rise to three dimethyl benzyl radicals. Sensitivity analysis shows that the H-abstraction reactions of TMB124 exhibit strong inhibiting effect, while the reactions of HO_2 radical and the three dimethyl benzyl radicals have promoting effect.
The present work aims to perform the experimental and kinetic study of 1,2,4-trimethylbenzene(TMB124) low-temperature oxidation under stoichiometric condition in a Jetstirred reactor(JSR). The experiment was carried out in the temperature range of 700-1100 K at atmospheric pressure. According to the measurements and theoretical calculations, a detailed chemical kinetic model involving 544 species and 3248 reactions was developed. Rate constants of TMB124 decomposition, reaction with HO_2, ipso-additions and metatheses with abstraction of methyl H-atom were updated. New pathways of H-abstraction from the 1-and 2-methyl groups were considered. The established model reproduces the measured mole fraction profiles of the major species and intermediates well. Rate-of-production analysis indicates that TMB124 is dominantly consumed by metatheses giving rise to three dimethyl benzyl radicals. Sensitivity analysis shows that the H-abstraction reactions of TMB124 exhibit strong inhibiting effect, while the reactions of HO_2 radical and the three dimethyl benzyl radicals have promoting effect.
引文
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[27]Baulch D L,Cobos C J,Cox R A,et al.Evaluated Kinetic Data for Combustion Modeling Supplement-I[J].Journal of Physical and Chemical Reference Data,1994,23(6):847-1033
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[2]Honnet S,Seshadri K,Niemann U,et al.A Surrogate Fuel for Kerosene[J].Proceedings of the Combustion Institute,2009,32(1):485-492
[3]Won S H,Sun W T,Ju Y G.Kinetic Effects of Toluene Blending on the Extinction Limit of n-Decane Diffusion Flames[J].Combustion and Flame,2010,157(3):411-420
[4]Saggese C,Frassoldati A,Cuoci A,et al.A Wide Range Kinetic Modeling Study of Pyrolysis and Oxidation of Benzene[J].Combustion and Flame,2013,160(7):1168-1190
[5]Yuan W H,Li Y Y,Dagaut P,et al.Investigation on the Pyrolysis and Oxidation of Toluene Over a Wide Range Conditions.I.Flow Reactor Pyrolysis and Jet Stirred Reactor Oxidation[J].Combustion and Flame,2015,162(1):3-21
[6]Yuan W H,Li Y Y,Dagaut P,et al.Investigation on the Pyrolysis and Oxidation of Toluene Over a Wide Range Conditions.II.A Comprehensive Kinetic Modeling Study[J].Combustion and Flame,2015,162(1):22-40
[7]Ga?l S,Dagaut P.Experimental Kinetic Study of the Oxidation of p-Xylene in a JSR and Comprehensive Detailed Chemical Kinetic Modeling[J].Combustion and Flame,2005,141(3):281-297
[8]Battin-Leclerc F,Bounaceur R,Belmekki N,et al.Experimental and Modeling Study of the Oxidation of Xylenes[J].International Journal of Chemical Kinetics,2006,38(4):284-302
[9]Gudiyella S,Malewicki T,Comandini A,et al.High Pressure Study of m-Xylene Oxidation[J].Combustion and Flame,2011,158(4):687-704
[10]Li Y Y,Cai J H,Zhang L D,et al.Experimental and Modeling Investigation on Premixed Ethylbenzene Flames at Low Pressure[J].Proceedings of the Combustion Institute,2011,33(1):617-624
[11]Dagaut P,Karsenty F,Dayma G,et al.Experimental and Detailed Kinetic Model for the Oxidation of a Gas to Liquid(GtL)jet Fuel[J].Combustion and Flame 2014,161(3):835-847
[12]Roubaud A,Minetti R,Sochet L R.Oxidation and Combustion of low Alkylbenzenes at High Pressure:Comparative Reactivity and Auto-Ignition[J].Combustion and Flame,2000,121(3):535-541
[13]Bikas G.Kinetic mechanisms for Hydrocarbon Ignition[D].Aachen,Germany:RWTH Aachen University,2001
[14]Hui X,Das A K,Kumar K,et al.Laminar Flame Speeds and Extinction Stretch Rates of Selected Aromatic Hydrocarbons[J].Fuel,2012,97:695-702
[15]Hui X,Sung C J.Laminar Flame Speeds of Transportation-Relevant Hydrocarbons and Jet Fuels atElevated Temperatures and Pressures[J].Fuel,2013,109:191-200
[16]Won S H,Dooley S,Dryer F L,et al.Kinetic Effects of Aromatic Molecular Structures on Diffusion Flame Extinction[J].Proceedings of the Combustion Institute,2011,33(1):1163-1170
[17]Weng J J,Liu Y X,Wang B Y,et al.Experimental and Kinetic Investigation of 1,2,4-Timethylbenzene Oxidation at Low Temperature[J].Proceedings of the Combustion Institute,2017,36:909-917
[18]Glarborg P,Kee R J,Grcar J F,et al.A Fortran Program for Modelling Well Stirred Reactors[R].Albuquerque,USA:Sandia National Laboratories,1986:Report No.SAND86-8209
[19]Dievart P,Kim H H,Won S H,et al.The Combustion Properties of 1,3,5-Trimethylbenzene and a Kinetic Model[J].Fuel,2013,109:125-136
[20]Montgomery J A,Frisch M J,Ochterski J W,et al.A Complete Basis set Model Chemistry.VI.Use of Density Functional Geometries and Frequencies[J].Journal of Chemical Physics,1999,110(6):2822-2827
[21]Muller C,Michel V,Scacchi G,et al.A Computer Program for the Evaluation of Thermochemical Data of Molecules and Free Radicals in the Gas Phase[J].Journal de Chimie Physique et de Physico-Chimie Biologique,1995,92:1154-1177
[22]Oehlschlaeger M A,Davidson D F,Hanson R K.Thermal Decomposition of Toluene:Overall Rate and Branching Ratio[J].Proceedings of the Combustion Institute,2007,31(1):211-219
[23]Tian Z Y,Pitz W J,Fournet R,et al.A Detailed Kinetic Modeling Study of Toluene Oxidation in a Premixed Laminar Flame[J].Proceedings of the Combustion Institute,2011,33(1):233-241
[24]Brezinsky K,Litzinger T A,Glassman I.The high Temperature Oxidation of the Methyl Side Chain of Toluene[J].International Journal of Chemical Kinetics,1984,16(9):1053-1074
[25]Colket M B,Seery D J.Reaction Mechanisms for Toluene Pyrolysis[J].Proceedings of the Combustion Institute,1994,25(1):883-891
[26]Tappe M,Schliephake V,Wagner H G.Reactions of Benzene,Toluene and Ethylbenzene With Atomic Oxygen(o-3p)in the Gas-Phase[J].Zeitschrift of Physikalische Chemie,1989,162:129-145
[27]Baulch D L,Cobos C J,Cox R A,et al.Evaluated Kinetic Data for Combustion Modeling Supplement-I[J].Journal of Physical and Chemical Reference Data,1994,23(6):847-1033
[28]Metcalfe W K,Dooley S,Dryer F L.Comprehensive Detailed Chemical Kinetic Modeling Study of Toluene Oxidation[J].Energy&Fuels,2011,25(11):4915-4936