燃料燃烧反应机理

14200522•––TPCi–()–•–•H2COCmHn•–•••3•§4-1•–H2COHC\•–•–••4•Aliphatic-CH2-1:•-CH2-+1.5O2→H2O+CO2•1.56kcal/mol••–––OHOH–•51paraffinalkanes•,,,CmH2m+2•,Methane,CH4,•Normal-paraffin—n-butane•Iso-paraffin—i-butane6•iso-octane2,2,4-2,2,4-trimethylpentane,•MethylCH3••-C-C-C-109•C-C7•alkyl:1H•CH4C-HCH3•,n-butanen-butyli-butyl•,,•8•2naphthenes,(cycloalkanecyclanes)••CmH2m•Cyclopropanecyclohexane93olefinalkene––C=C––CmH2m–C2H4C=C•–1-(1-butene)2-(2-butene)•Vinyl–C=C.–1H10•4polyolefins•––––CmH2m-2(n-1)---n•:1-3-1-3-butadiene––:C=C-C=C114acetylene(alkyne)•Alkyne–––:CmH2m-2•:–acetylene:•H-C≡C-H–Propyne:•H-C≡C-C-H12•6aromatics•aromatics–,–6–benzene•C6H6–“”,•:–:,naphthalene,C10H8,–:,biphenyl,C12H10,C-C13•:,•:•-•6••66•,“”•,,14•7alcohols•alcohols•:ROH•:•CH3OH()•C2H5OH()•O•15•8—•NH4ClO4ammoniumperchlorate–•N2H4–•H2Fluorine–•,16•4-2H2CO•H2CO:–H2CO–H2CO–H2/CO/O2–H2CO,,171.H2/O2•:–P–T–TP,•T–––•TPPT18Fig.1•19••1)–H2+M→2H+M-r5–104.38kcal/mol,at298.15K•2),O2H2–H2+O2→HO2+H-r10–55kcal/mol,at298.15K•(),-r5,-r1020•H,•H+O2→O+OHr1•O+H2→H+OHr2•OH+H2→H+H2Or3•HOH,,•r1,•,,•H,O,OH→21••––•–,•–:H+O2+M→HO2+Mr9–,r1HO2,HO2,,r9–r1-r3r922••(r1-r3)r9,,H,(r1-r3);(r9)(r9)dt=0][M]dt0dt023•d[H]/dt=0•d[H]/dt=2k1[H][O2]-k9[H][O2][M]=0•2k1[H][O2]-k9[H][O2][M]=0•2k1=k9[M]•[M]•:•p=[M]RT•:•p=(2k1/k9)RT•,PT24Fig.125•••HO2+H2→H2O2+H-r16•H2O2+M→2OH+Mr15•,HO2•HO2,H2,H\O\OH,26•900K–HO2•HO2+HO2→H2O2+O2–HO•HO2+H→OH+OH•HO2+O→OH+O2•,(r9)(H+O2+M→HO2+M),27•1H2O2•1-4–•5-8–•9-13–HO2•14-19–H2O228•H2-O2•H+O2→O+OHr1•O+H2→H+OHr2•OH+H2→H+H2Or3•O+H2O→2OHr4•H2-O2•H2+M→2H+Mr5•2O+M→O2+Mr6•O+H+M→OH+Mr7•H+OH+M→H2O+Mr8•HO2•H+O2+M→HO2+Mr9•HO2+H→H2+O2r10•HO2+H→OH+OHr11•HO2+O→OH+O2r12•HO2+OH→H2O+O2r1329•H2O2•HO2+HO2→H2O2+O2r14•H2O2+M→OH+OH+Mr15•HO2+H2→H2O+OHr16•H2O2+H→H2+HO2r17•H2O2+O→HO+HO2r18•H2O2+OH→H2O+HO2r19•CO•CO+O+M→CO2+Mr20•CO+O2+M→CO2+Or21•CO+OH→CO2+Hr22•CO+HO2→CO2+OHr2330•2CO•CO-O2–CO+O2→CO2–E=48kcal/mol–•H2,•r1r3,r5,-r10OH•H+O2→O+OHr1•O+H2→H+OHr2•OH+H2→H+H2Or3•H2+M→2H+Mr5•H2+O2→HO2+H-r10•CO+OH→CO2+Hr2231•CO+OH→CO2+Hr22–R22CO–r22Hr1,CO•CO–O2+M→2O+M-r6–:O+H2O→2OHr4•(r22)OHCO–CO+OH→CO2+Hr22•(r1)–H+O2→O+OHr1•(ppm)•,CO32•3•––––:•H2/O2,H,(r1)•H+O2→O+OHr1•,H-r5,-r10•H2+M→2H+M-r5•H2+O2→HO2+H-r10–33•4-3••,•,•C1\C2\C3•,•••34•,,:–H+O2→OH+Or1–CO+OH→CO2+Hr22••r22COCO2•Hr135•••r1,r90–H+O2→O+OHr1–H+O2+M→HO2+Mr9––,(HO2)r9•36•3.1()•,,–τ–τ\•:–τ=2.2110-14exp(22659/T)[CH4]0.33[O2]-1.05––1250K~2500K•37••–CH4(+M)⇐⇒CH3+H(+M)r24–CH4+O2⇐⇒CH3+HO2r25–r24,•,r24r2538•r24()----:–H+O2→O+OHr1–CH4+H⇐⇒CH3+H2r26–CH4+OH⇐⇒CH3+H2Or27–CH4+O⇐⇒CH3+OHr28•R26–r1H–HCH339•r25()•–CH4+HO2⇐⇒CH3+H2O2r29–H2O2(+M)⇐⇒OH+OH(+M)r15•r24:CH4(+M)⇐⇒CH3+H(+M)––,r24,40•CH4+H⇐⇒CH3+H2r26•CH4+OH⇐⇒CH3+H2Or27•CH4+O⇐⇒CH3+OHr28•r26-28CH3()O2:–CH3+O2→r31•r31:–CH3+O2→CH3O+Or31a–CH3+O2→CH2O+OHr31b•–r31b–r31aCH3OCH2O41••CH3+CH3(+M)→C2H6(+M)r32•CH3+CH3→C2H5+Hr33•r32\r33–r32–r33H•CH5(+M)→C2H4+H(+M)r34•r32-42•,:–CH3+HO2→CH3O+OHr35––CH3O(),r31ar35–CH2O,•CH3O+M⇐⇒CH2O+H+Mr36•CH3O+O2⇐⇒CH2O+HO2r37–OHOHCO:•CH2O+OH⇐⇒HCO+H2Or38•CH2O+O2⇐⇒HCO+HO2r39•HCO:•HCO+M⇐⇒H+CO+Mr40•HCO+O2⇐⇒CO+HO2r41–r22COCO2–,r22CH3O43•3.2•Fig2–H\O\OHHr26-r28()–O•CH3+O⇐⇒CH2O+Hr42–CH2OHH•CH2O+H⇐⇒CHO+H2r43–(r38),OHCHO()CHOCOHHO2,H–CH3OH()()(CH2*)•CH3+OH⇐⇒CH2*+H2Or4444Fig.245•,,,,CH2*,CH2(2)•CH2*+M→CH2+Mr45•CH2*O2H\OH,•CH2*+O2→CO+H+OHr46•r45CH2*,CH2..–CH2+O2→HCO+OHr47•CH2HCH–CH2+H→CH+H2r4846•CHH2OO2,–CH2+H2O→CH2O+H–CH+O2→HCO+Or49•CH3r33\r32CH3\CH2C2–CH3+CH2→C2H4+H•C2C2H2()•Soot47•4-4\\•••\\••3C2•H\O\OH,H,C2H5:–C2H6+H→C2H5+H2r51–C2H6+O→C2H5+OHr52–C2H6+OH→C2H5+H2Or5348•C2H5,O2\HC2H4–C2H5+H→C2H4+H2r54–C2H5+O2→C2H4+HO2r55–C2H5(+M)→C2H4+H(+M)r34•C2H5O2CH3CHO–C2H5+O2→CH3CHO+HOr56•CH3CHOH\O\OH,CH3COCH3CO–CH3CHO+(H\O\OH)⇐⇒CH3CO+(H2\OH\H2O)r57–CH3CO(+M)⇐⇒CH3+CO(+M)r5849•OCH3CH2O•C2H5+O2→CH3+CH2Or59•–(),H–OOH–OCH3\HCO•C2H4+O→CH3+HCOr60–2r6050•–O–H\OH,H–C2H3–C2H4+H→C2H3+H2r61–C2H4+OH→C2H3+H2Or62••C2H3O2CH2O\HCO\CH2CHOOH–C2H3+O2→CH2O+HCOr63–C2H3+O2→CH2CHO+OHr6451•CH2CHOC1•r61CH3O2:–C2H3+H→C2H2+H2r65–C2H3+O2→C2H2+HO2r66–C2H3(+M)→C2H2+H(+M)r67••52•-CH2-•-CH2-→0.5C2H2+0.5H2–1600K32kcal/mol–?(1600K)H230.8cal/mol·KGibbs–∆G=32-30.810-3×1600=-17kcal/mol–KP≈200,1••,,53••,54kcal/mol•,•:–,–,54•,H•C-H131kcal/mol,C-H101kcal/mol.•O:–C2H2+O→CH2+COr68–C2H2+O→HCCO+Hr69•HCCO,H–HCCO+H→CH2*+COr7055•Hr67•r63r64•\\(CH3CH’sCH2OHCOCO)•CH4-O256•4-5•,H\OH•:,CH3OH:–CH3OH+H→CH2OH+H2r71–CH3OH+O→CH2OH+OHr72–CH3OH+OH→CH2OH+H2Or73•CH2OH(),O2CH2O–CH2OH(+M)→CH2O+H(+M)r74–CH2OH+O2→CH2O+HO2r7557•CH3OHHCH3O()–CH3OH+H→CH3O+H2r76–CH3OH+O→CH3O+OHr77–CH3OH+OH→CH3O+H2Or78•CH3Or36r37•–CH3OH(+M)→CH3+OH(+M)r79•–CH3OH(+M)→CH2*+H2O(+M)r8058•CH2*–CH2*+O2→CO+H+OHr45•r71-r79,r36,r37r1•H–C2H5OH+H→CH3CHOH+H2r81–C2H5OH+O→CH3CHOH+OHr82–C2H5OH+OH→CH3CHOH+H2Or83•CH3CHOH–CH3CHOH(+M)→CH3CHO+H(+M)r84–CH3CHOH+O2→CH3CHO+HO2r85–CH3CHO59•r57:CH3CHOHCH3CO•r58:CH3COCH3CO•C-C–C2H5OH(+M)→CH3+CH2OH(+M)r86•–C2H5OH+O2→CH3CHOH+HO2r87•\••–CH3COr51-r55r3460•4-6••H-CO-O2CH4-O2C2Hx-O2•9•ββ61•1β•BDE(BDE=bonddissociationenergy)•E•––BDE•BDEBDEBDE62•β•n-C3H7•BDE••C-CBDE24kcal/mol,C2H2CH3•βC-HBDE34kcal/mol,βC-HC3H6H63•n-hexyl••BDE22kcal/molβC-CC2H4-•36kcal/mol,βC-H,,1-(1-C6H12)H