Kinetic models of natural gas combustion in an internal combustion engine

ScienceDirectNATURALGASCHEMISTRYKinetic models of natural gas combustion in aninternal combustion engineA.R saleI. Department of Chemical Engineering, University of Engineering Technology, Lahore 54570, Pakistan;2. SUPARCO, HOs, Karachi 49430, PakistanIn this study, combustion of methane was simulated using four kinetic models of methane in CHEMKIN 4. 1. 1 for O-D closed intermal combus-tion(IC)engine reactor. Two detailed(GRIMECH30& UBC MECH2. 0)and two reduced(One step Four steps)models were examined forvarious IC engine designs. The detailed models(GRIMECH30, UBC MECH2.0) and 4-step models successfully predicted the combustionwhile global model was unable to predict any combustion reaction. This study illustrated that the detailed model showed good concordances inthe prediction of chamber pressure, temperature and major combustion species profiles. the detailed models also exhibited the capabilities topredict the pollutants formation in an IC engine while the reduced schemes showed failure in the prediction of pollutants emissions. Althoughre discrepancies among the profiles of four considered model, the detailed models(GRIMECH3 0& UBC MECH2.0)produced theptable agreement in the species prediction and formation of pollutantsKey wordskinetic models; detailed models; reduced models; combustion; methane; IC engine1 IntroductionBC as high temperature and high pressure gases push the pis-ton down and force the crank to rotate. During an exhaustThe combustion of hydrocarbon fuel removes O2 from stroke, the remaining bumed gases exit the cylinder, first be-he atmosphere and releases equivalent amount of H20 and cause the cylinder pressure may be substantially higher thanother compounds including hydrocarbons(CH4, C2H2, C H6, as it moves towards TC. When the piston approaches thecO2 inevitably mingled with trace amounts of numerous the exhaust pressure; then as they are swept out by the pistoCH2, CHO, etc. ) carbon monoxide(CO), nitrogen oxidethe inlet valve opens, Just after TC, the exhaust valve closes(NO, N2O) and reduced nitrogen(NH3 and HCN), suland the cycle starts again. An illustrative example of possiblegases(SO, oCS, CS2), halo-carbons(CHCI and CH3 Br), trend of measured cylinder pressure is given in Figure Iand particles [ 1]Because of the unique tetrahedral molecular structureHeywood [ 2] described that in light duty 4-stroke engine, with large C-H bond energies, methane exhibits some uniquepremixed fuel-air mixture(CNG-Air)enters the engine dur- combustion characteristics. For example it has high ignitioning the intake stroke, which starts when the piston is at top temperature, low flame speed and it is essentially unreactive incenter(TC)and ends with the piston at bottom center(bc),hotochemical smog chemistry chemical kinetics of methaneand draws fresh mixture into the cylinder. To increase the is the most widely studied topic. Kaufman 16), in a reviewmass inducted, the inlet valve opens shortly before the intake of combustion kinetics indicated that the methane combustionstroke starts and closes after it ends. The mixture is com- models evolved in the period of 1970-1982 from less thanpressed to small fraction of its volume in the compression 15 elementary steps with 12 species to 75 elementary steps,stroke.Towards the end of the compression stroke, combus- plus the 75 reverse reactions, with 25 species. Recently, sev-tion is initiated by the spark plug typically. As the combus- eral research groups have collaborated in the creation of antion progresses, the cylinder pressure rises more rapidly when optimizedkinetic model [71. This mechanism desig-both intake and exhaust valves are closed. The power stroke, nate中国煤化工 optimization techniquesor expansion stroke starts with the piston at TC and ends at of FrCNMHiled reaction models areCorresponding author. Tel: +92-333-4847327: E-mail: muhammad mansha @uet. edu. pkCopyrighto2010, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. All rights reserveddoi:l0.106S10039953(09)60044Joumal of Natural Gas Chemistry Vol. 19 No I 2010reported in the literature [9]. They can be divided into full Simulation of the CHa combustion in an internal combustionmodels, skeletal models, and reduced models. These mod- engine is very important to the design of engine and the conels differ with respect to the considered species and reactions trol of air pollutants derived from the exhaust. One of the key[10). In literature, several models of methane combustion ex- objectives is to establish a kinetic model, in which the pres-exasure and temperature profile in the engine, and the importantDetailed models include those of Westbrook [11], Glar- reactants and products can be simulatedorg et al. [12], Miller and Bowman [13], Konnov [14],In current study, consequences of the selected( detailedHughes et al. [15], and the standard GRI MECH3.0[16]reduced)models for the profiles of temperature, pressure andReduced models include Westbrook and Dryer [17], major species produced are discussed. An appropriate modelDuterque et al. [ 18](1 to 2 global reactions, Peters [19], which predicts combustion species like NO-, CO, CO2,andHautman et al, [201, Jones and Lindstedt [21](more than H20 etc. in engine combustion chamber is identified. The2 global reaction), Edelman and Fortune [22], and Edelman simple criteria of comparing simulation results(profiles) ofand Harsha[23]-one step global reaction with many elemen- detailed and reduced models as followed in the study was de-tary reactions;( these models are called quasi-global models). scribed in Ref[26]All chemical models used in combustion share the same de-scription of elementary chemical reactions, based on an Ar-rhenius law, leading to a rate coefficient expressed as k2. Materials and methodsATe-Ea/RT, The values of A, Ea(or Ta= Ea/R)and thetemperature-dependent coefficient B are thus reaction depen-CHEMKiN is a powerful set of software tools for solvdent. Based on this expression, different levels of approxima- ing complex chemical kinetics problems. It is used to studytion can be defined to describe the kineticsreacting flows, such as those found in combustion, catalysis,chemical vapour deposition, and plasma etching. CHEMKINnetics in a variety of reactor models that can be used to rep-resent the specific set of systems of interest. It provides abroad capability that addresses needs of both non-expert andexpert users [27]. The IC model is for O-D closed system,the simulation is only valid within the time period when bothintake and exhaust valves are closed. Conventionally, enginecylinder events are expressed in crank rotation angle relativeto the top dead center (TDC). The intake valve close (Ivc)time of our test engine is 142 degrees(crank angle) beforeTDC (BTDC)In this study, we set our simulation starting crank angleCrank angle142 degrees in the software input. Other simulation param-eters we used in the software simulation were cycles end timeFigure 1 Measured cylinderne operating at 1500 rpm, dgle cylinder st en as 0.043 sec or for 257 degor 257 degrees crank angle to 115 degrees af-ter TDC. The gas mixture pressure and temperature at IVC areOxidation models of methane combustion, reported in 107911 Pa(or 1.065 atm) and 550 K, respectively, The fol-the literatures [6-251, were used to study methane combus- lowing four mechanisms were investigated for methane com-tion/burning in fumaces, burners, bunsen flame burner etc. bustion in internal combustion engines as given in Table 1Table 1. Tested models of methane combustionSr No Kinetic model typeReactionsTa(k)1 Global one-step reaction [18Four step reaction models of Jones and Lindstedt [21] (i)CH 4+1/202=C0+2H2 4.40E+14(i)CHa+H20=C0+3H23.00E+14000.0(i)H2+l/2O2=H2O-1.0320000(iv)CO+H0=CO+H22.75E+12160000GRIMECH 3.0(53 species 325 reactions)(available on Internet)[71UbcMech2.0KineticmechanismavailableonInternetathttp://kbspc.mechubcca/kinetics.htmlWhere, A, B, Ta (Ta= Ea/T) are the parameters for Ar-(Globrhenius Law defined below: k= ATe RT. Two of these TwoYH中国煤化工CNMH Gd to input for execu-model are the detailed such as GRIMECH 3.0& UBC tion of CHEMKIN module; () Mechanism data files andMECH2.0 and other two are reduced such as Uterque (i) thermodynamic data files. The details of mechanism8M. Mansha et al/ Joumal of Natural Gas Chemistry Vol. 19 No. I 2010and thermodynamics files can be found in references at dependent) of both detailed models are given in Table 2 to[7, 18, 28]. Some important species and reaction (pressure Table 4Table 2. Important species considered in UBC MECH 2.0 and GRI MECH 3.0 kinetic modelsDetailed kinetic model No of species No of reactioUBC MECH2. 0H2, H, O, O, OH, H2O. HO2, H2O2, C, CH, CHCO, CH2O, CH2OH, CH3 0, CH3OH, C2H, C2H2, C2H3, C2H4. C2Hs, C2H6HCCO, CH2CO, HCCOH, N2, AR, CH3Oz, CH3 O2H, C2HsO C2HsO. C2HsO2HCH3 CO CH3 CHO, C2H,O C?H30. C3H8, n C3H7, iC3H7, nC3H7O2, iC3H702nC3H7O2H, iC3 H7O2H, n C3H7O. iC3H7O, C3 H6, C3H5, C3H4, C2H4OzHGR3.0O, Oz, OH, H2O, HO2, H202, C, CH, CH2, CH2(S), CH3, CH4, CO, CO2, HCO,CH2O, CH2OH, CH3O CH3OH, C2H, C2H2, C2H3, C2H4, C2H5, C2H6, HCCOCH2 CO, HCCOH. N, NH. NH2 NH3 NNH. NO, NOz, N2O, HNO, CN, HCN, HiCNHCNN, HCNO, HOCN, HNCO, NCO, N2, AR, C3H7, C3Hg, CH2 CHOTable 3. Some important reactions of GRI MECH 3.0 mechanism(pressure temperature dependent reactions are listed)A7二FTA(mol- sec.K)O+H2←≯H+OH3.87E+040+H202 OH+HO2963E+06l.02E+09O+CH3OH÷→OH+CH2OH3.88E+0531000+CH3 OH +*OH+CH3O130E+05O+C2H2+→H+HCCo135E+07)C2H2 < OH+C2H4.60E+19+C2H2+→CO+CH26.94E+062H4←→CH3+HCO1.25E+07O+C2H6←→→OH+C2Hs8.98E+07+0260+OH2.65E+160.7+H21E+0T5200H+CH3(+M)÷CH4(+M)139E+16H+CH+→CH3+H2660E+0815H+HCO(+M)专冷CH2O+M)l.09E+12HCH2O(+M)专→CH2OH(+M5,40E+11H+CH2O(+M)÷→÷CH3O(+M)5.40E+ll5.74E+0767890123456789012H+CH2OH(+M)←→CH3OH(+M1.06E+12H+CH2OH◆→OH+CH31.65E+l1H+CH2OH→CH2(S)+H2O3.28E+13H+CH3O(+M)÷→CH3OH(+M)2.43E+12HHCH3O÷H+CH2OH4.L5E+07H+CH3O←OH+CH3H+CH3O÷÷CH2(S)+H2O262E+140.21070HHCH3OH→→CH2OH+H21. 70E+0H+CH3OH+→CH3O+H4.20E+062.14870H+C2H3(+M)+→C2H4(+M)6.08E+125.40E+111820H+C2H4 <*C2H3+H2H+C2H5(+M)+C2H6(+M)5.2lE+17H+C2H6+ C2Hs+Hz.15E+08H2+CO+M)÷CH2O(+M)4.30E+0779600123456789042345OH+H2÷→H+H202.6E+083.57E+04OH+CH3(+M)÷→÷CH3OH(+M)2.79E+18OH+CH+→CH2+H2O560E+07OH+CH3÷→CH2(S)+H2O644E+17OH+CH4 + CH3+H2O100E+083120CH3+CH3OH←→CH2OH+CH43.00E+07中国煤化工CH3+CH3OH←→CH3O+CH41. 00E+07CNMHGcH+C2H4←C2H+CH42.27E+059200CH3+C2H6←→C2Hs+CI6.l4E+06HCO+H20+= H+CO+H20L.50E+l8HCO+M←→H+CO+M1.87E+17Joumal of Natural Gas Chemistry VoL. 19 No I 2010ble 3. ContinueReactionsk=ATP exp(E/RT)A(mol-cm-sec K)E(carmol)CH30+O + HO2+CH2O4.28E-13C2H+H2÷→H+C2H钢05254567890C2H3+O2→HCO+CH2OC2H4(+M)←→H2+C2H2(+M)0486770N+O2+→NO+900E+091065001.28E+0NH2+OH→NH+H2O900E+071.5-460NNH+M→N2+H+M1.30E+140.1H+NO+M←HNO+M448E+19740900E+110.7HNO+OH÷→NO+H2O1.30E+07cN+H2+→HCN+H2.95E+05NCO+NO+÷N2O+CO1.90E+17902鼠66780012345NCO+NO÷→N2+CO2380E+18HCN+M←>H+CN+M1.04E+26600HCN+O←NCO+H203E+04HCN+0←NH+COHCN+O<→CN+OHHCN+OH←HOCN+HCH2+NO÷÷H+HNCoCH2+NO +* OH+HCN0.7CH2+NO→H+HCNOCH2(SHNO→H+HNCO3.10E+17CH2(S)+NO÷→OH+HCN2.90E+14CH2(S)+NO÷H+HCNO3.80E+13HNCO+O←→NH+Co980E+0714HNCO+◆→÷HNO+CO1.50E+081.644000HNCO+0e NCO+OH20E+06HNCO+H÷◆NH2+CO2.25E+071.7y082888HNCO+H÷→H2+NCO1.05E+05HNCO+OH NCO+H2O1.5HNCO+OH←NH2+CoHCNO+H←◆H+HNCoHCNO+H←◆OH+HCN2.70E+110.22120HCNO+H÷→NH2+CO1.70E+1482890HOCN+H←◆H+HNCo200E+07Table 4. Some important reactions of UBC MECH2.0 mechanism(only pressure temperature dependent reactions are listed)k= ATsexp(-E/RT)A(mol.K)E(cal/mol)O+H2+→H+OH5.0OE+046290O+H202 OH+HO2963E+0640002345670+CH4台→OH+CH1.02E+09O+CH3OH+→OH+CI3.88E+05O+CH3OH÷→OHCH3O1.30E+05O+C2H2←OH+C2H1.02E+07O+C2H4←CH890123456789OC2H6÷OHC2HsHHCH3(+M)→CH4(+M)L.2TE+16H+CH4÷→CH3+H660E+08H+HCO(M)+ CH2 O(+M)09E+12H+CH2O(+M)←CH2OH(+M540E+l1H+CH2O(+M)→CH3O(+M)H+CH2O→HCO+H230E+10中国煤化工H+CH3OH→CH2OH+Hl.70E+07CNMHGH+CH3OH÷CH3O+H24.20E+06HHC2H3(+M)+→C2H4(+M608E+12HC2H4(+M)÷C2H5(+M)1.08E+12M. Mansha et al/ Journal of Natural Gas Chemistry VoL. 19 No, I 2010Table 4. ContinueReactionsk=AT exp(-E/RT)A(mol-cmsecK)E(carmol)C2H4台→C2H+H21.32E+06122402345%mH+C2H5(+M)←÷C2H6(+M)521E+17H+C2H6→C2Hs+Hl.15E+081,9OH+H2→H+H202.16E+08OHCH2+→÷CH+H2O1.13E+07OH+CH3←→→CH2+H2OOH+CH4→CH3+H2OOH+CO←H+CO2OH+CH2O←冷HCO+H2O3.43E+09OH+CH, OHCH,OH+H2OO+H,0OH+C2H2←→H+CH2CO4.5OHC2H2←→H+ HCCOH13500OH+C2H2+→C2H+H20OH+C2H2←→CH3+COOHC2H4+→C2H3+H203.60E+06OH+C2H6÷+C2H5+H2O3.54E+06CH+H2→H+CH21. 11E+0878944234567H2+H+→H+CH500E+05CH2+CH4→2CH32.46E+06CH2+CO(+M)< CH2CO(+M)8.10E+l10.52CH3(+M)÷→C2H6(+M)2l2E+164.99E+12CH3+CH2O←◆HCO+CH3.32E+032.8CH+CH3OH÷CH2OH+CH4300E+07CH3+CH3OH÷→CH3O+CH41.00E+0CH3+C2H4←→C2Hy+CH4CH3+C2H6 +>C2Hs+CHaL.7HCO+M←◆ H+C0+M4.28E-lC2H+H2+→H+C2H2C2H4(+M)←H2+C2H2(+M)800E+1288770CH3+024567890C2H5+O2÷C2H5O21.10E+4714830C2H5+O2←C2H5O+01.10E+13-0.227926C2H5+O2 4 CH3 CHO+OH60E+1412C2H3+O2÷→C2H3O+066lE+06C2H3+Oz C2H2+HO28.40E+05DH+C3Hs iC3H7+H20708E+06999Table 2 shows some common species and intermediatesTable 6. General input parameters(or radicals) present in the reacting mixture for both detailedParameterskinetic models and these models have about 44 common reac.Heat transfer corelation coefficients Coefficient ations. In Table 3& 4, only the pressure dependent reactionsCoe fficient b0.71re listed as apparent from value of Arrhenius parameter"A'Coefficient cWe have simulated the combustion of methane with fouWoschni correlation coefficients2.28models(Table 1)with different engine specifications(An ex3.24ample of engine specifications is given in Table 5)Wall temperature(K)More details about the engine specifications, used in thissimulation, exist in studies cited at References (5, 27, 29). Theother simulation inputs to the ChEMKin software are givenThe composition of the initial gas mixture is a combina-in Table 6 and adopted from Heywood [2].tion of natural gas, air, and exhaust gas recirculation(EGR)gas as given in Table 7.Table 5. Example of test engines specifications used insimulation of methane combustionParametersof initial gas mixtureompression ratIo100中国煤化工-volume(cm)1530CNMHGConnecting rod to crank radius ratio297729Cylinder bore diameter(mm)00205Journal of Natural Gas Chemistry Vol. 19 No. 1 20103. Results and discussionric conditions(Initial inlet temperature, Tini=447 K, initial=1.07 bar and o= 1.0). As shown in theFigures, the reduced model(Uterque, Jones and Lindstedt)The combustion of methane in engine cylinder was sim- predicts the earlier combustion as the detailed models. Theulated with four kinetic model schemes and we used various reason of this deviation in delay is that the species and tem-Input parametersperature reach their end values very sharply. Each pressureIn this section, we focus more on the consequences of the profile clearly shows that the peak cylinder pressure occursused four kinetic reaction schemes(models)of methane oxi- close to TC (top-center). At TC, this pressure built up isdation for the predicted pressure, temperature profiles and ma- closely related to the rate of burning of the premixed fuel mixjor combustion species including gaseous pollutants. The pre- ture. There is an early built up of pressure with the reduceddicting capabilities of theses models under the similar simulmodel(Uterque, Jones and Lindstedt)than the detailed re-tion conditions were also discussed and an appropriate reac- action schemes(UBC MECH2.0 GRIMECH 3.0). The de-n scheme(detailed &e reduced)was identified simply based tailed models predict the maximum cylinder pressure and tem-on the simulation resultsperature of approximately of 40 atm and 2000 K, respectively.Figure 2 &3 shows the pressure and temperature profiles In case of reduced models, the predicted pressure and temperspectively of four models for the adiabatic and stoichiomet- ature significantly deviate8020L⊥LCrank rotation angleFigure 2, Predicted pressure profiles for equivalence ratio of o=1.0(Tini=447 K, Pini=1.07 bar)TTTTTTFigure 3. Predicted temperature profiles for equivalence ratio中国煤化工CNMHGThese deviations in the prediction of pressure and temper-trates une main combustion speciesature occur due to reaction paths for the detailed and reduced profiles of fuel(methane, CH4), carbon dioxide(CO2), andwater vapours(H2O)at stoichiometric conditions. ObviouslM. Mansha et al/ Joumal of Natural Gas Chemistry VoL. 19 No. 1 2010the 4-step model better predicts the early consumption of fuel idized to Co2than both the detailed models. If we look at the profiles of theIt is clear from Figure 4 that, both detailed modelsproduced species( CO2 and H2O), 4-step model indicates that (GRIMECH 3.0 UBC MECH2. 0)and 4-steps model prethese species are formed at the earlier stage very rapidly and dict Co emissions and one step global model fails in thislater on, these are consumed at the intermediate steps( which regard because there is no Co pathway in the model. In eachindicate the pyrolysis of fuel) and then produced. These in- graph of CO and NO(as NOz), the reduced model shows thetermediate then further are oxidized to co which is then ox- earlier formation than the detailed models00350030三F0025002000200011500100.0050.000Crank rotation angle0070.500060.002Crank rotation angle04門 T0.35o=ee0.08中国煤化工CNMHGFigure 4. Major species profiles(a)CH4, (b)CO2, (c)H2O for equivalence ratio of o=1.0(Tini=447 K, Pini= 1.07 bar)Journal of Natural Gas Chemistry Vol. 19 No. 1 2010Each profile of n20 graph illustrates that N2O is formed ther conversion into NO2 and NO. There is more rapid forma-immediately during the combustion and then its fraction is de- tion of No than NO2 on the whole, the reduced models(onlycreased as shown in Figure 5. The reason for this production the 4-steps mechanism) predict the higher fractions than theof N2O production is the oxidation of N2 with O2 and the fur. detailed reaction schemes20X10X1045x80×1051.0X106g60X10310X10650×10740x1050X100500.150004000200.001595乏0.003esign II-GRIMECH3 0 0.1000020.00100.001000050.00000.000Crank rotation angleFigure 5. NO,(a)and Co(b)emissions for equivalence ratio of o =1.0(Tini=447 K, Pni=1.07 bar). NO is used as collective term for NOz N2oIn the light of the above simulation results, detailed mod- emission for detailed models identified some of the discrepels are more appropriate in prediction of combustion species cies but on the whole the detailed models(GRIMECH3 0&and pollutants formation in IC engine chamber. The results UBC MECH2.0)can be superseded over the reduced model(Figures 2-5)of present study predict that GRIMECH3 0 (4-steps model of Jones and Lindstedt in prediction of polmodel could be utilized in practical design on an IC engine lutants emissions of Co& oxides of nitrogen(NO, N2ofor low emissions4. ConclusionsAcknowledgementsAuthors are thankful to the Higher Education Commission(HEC)for financial support for this study and Mr. Jamal Gul forCombustion in an IC engine was simulated using four re- his continuous technical support during simulation experiments foraction models(two detailed and two reduced ) The effect of keeping the system operationathese reaction schemes on the pressure profiles, temperatureprofiles and major species profiles was compared under vari- ReferH中国煤化工ous simulation conditions(equivalence ratios, engine parameters keeping initial gas composition constant). The detailedCNMHmodels showed the encouraging results but the computational iIndamentals and Technol-ogy of Combustion. Boston: Elsevier, 2002ost of a simulation is high. The comparison of the predicted [2] Heywood J B Internal Combustion Engine Fundamentals. Newtemperature profiles, major species profiles and pollutantsYork: McGraw-Hill. 1988M. Mansha et al/ Journal of Natural Gas Chemistry Vol 19 No. I 2010[3] Stephen R. Turns. An Introduction to Combustion: Concept and [ 16] Smith G P, Golden D M, Frenklach M, Moriarty n w, Eit-Applications. Singapore: McGraw-Hill, 2000enter B, Goldenberg M, Thomas Bowman C, Hanson R[4] Zheng P Zhang HM, Zhang D E. FueL, 2005, 84(12-13), 1515K, Song S, Gardiner w C, Jr Lisianski v V, Qin Z w[5] Abdullah S, Kurniawan W H, Shamsudeen A Joumal of Ap-http://www.me.berkeley.edw/gri_mech/plied Fluid Mechanics, 2008, 1(2), 65[17] West Brook C K, Dryer F L. Combust Sci Technol, 1981, 27(1[6] Kaufman F Nineteenth Symposium(International) on Combus-2),31tion. Pittsburgh, PA: The Combustion Institutes, 1982. I[18] Uterque J, Roland B, Helene T. Combust Sci Technol, 1981[7] Bowman CT, Hanson R K, Davidson D F. Gardiner W C, Jr Lis-sianski V, Smith G P, Golden D M, Frenlach M, Goldenberg M. [191 Peters N. In: Glowinski R, Larrouturou B, Temam R, ed. Lec-Gri-MechHomepageshttp://www.me.berkeley.edu/gri_mech/ture Notes in Physics, Vol 241. 1985. 90[81 Frenklach M, Wang H, Rabinowitz M J Prog Energy Combust [20] Hautman D J, Dryer F L, Schug K P, Glassman L Combust Sci18(1):47echnol,1981,25(56),219[9] Peters N, Rogg B. Lecture Notes in Physics, 1993, 15(1): 1[21] Jones W., Lindstedt R P Combust Flame, 1988, 73(3), 233[10] Magel H C, Schnell U, Hein K R C. Proceedings of 26th Sym- [22] Edelman R B, Fortune O F. AIAA, 1969, 69posium(International)on Combustion, Vol L. Pittsburgh, Penn, (231 Edelman R B, Harsha PT. Prog Energy Combust Sci, 1978, 4(1),USA: The Combustion Institute, 1997. 67[11] Westbrook C K Report No. PB-86-168770/XAB, Lawrence (241 Lu T F, Law C K. Proc Combust Inst, 2005, 30(1), 1333Livermore National Laboratory, Livermore, CaL., USA, 1985 [25] Lavoie G A, Heywood J B, Keck J C. Combust Sci TechnoL,[12] Glarborg P. Miller J A, Kee r J Combust Flame, 1986. 65(2).1970,1(4),313[26 Mallampalli H P, Fletcher T H, ChenJY. Paper 96F-09828, Pro-13] Miller J A, Bowman C T. Prog Energy Combust Sci, 1989,ceeding of Meeting of Western States Section of the Combustion5(4),287Institute University of Southen California, Los Angeles, CA[14] Konnov aA. Detailed Reaction Mechanism for28-29 October,1996.Small Hydrocarbons Combustion, Release 0.5, 2000, [27] Reaction Design, Theory Manual, Chemkin Software. 2004ttp: //homepages. vub ac be/ akonnov/[28] Huang J, Bushe W K Combust Flame, 2006, 144(1-2), 74[15] Hughes K J, Turanyi T, Clague A R, Pilling M J. Int J Chem (291 Cao L, Zhao H, Jiang X. Combust Sci Technol, 2008, 180(1)Kiner,2001,3y(9),513中国煤化工CNMHG