Beruflich Dokumente
Kultur Dokumente
R.K.Hanson,D.F.Davidson StanfordUniversity
1st InternationalWorkshoponFlameChemistry July2829,2012
StanfordShockTubes
Aerosol Shock Tube (10atm)
NewConstrainedReactionVolume(CRV)Facility
2Configurations
Sliding Valve
CRV1
GasPhase Experiments to100atm
Constrained ReactionVolume
CRV2
Aerosol Experiments to100atm Aerosol GenerationTank
Firstuseof tunable dyelasers inshock tubes (1982) Ultrafast lasersusedto extendUV tuningrange (2009)
StanfordLaserDiagnostics
Ultraviolet CH3 216nm NO225nm O2 227nm HO2 230nm OH306nm NH336nm Visible CN 388nm CH431nm NCO440nm NO2472nm NH2597nm HCO614nm Infrared H2O2.5m CO22.7m CH4 3.4m CH2O3.4m CO4.6m NO5.2m C2H410.5m
LaserAbsorptionYieldsHighSensitivity
RepresentativeDetectionLimits:PolyatomicMolecules
1000
CO2
Detection Limit [ppm]
100 10 1 0.1 0.01 1000
NH2 CH3
1atm,15cm,1MHz
1500 2000 2500 3000
Temperature [K]
Polyatomicmolecules@1500K:2200ppm
5
LaserAbsorptionYieldsHighSensitivity
RepresentativeDetectionLimits:DiatomicMolecules
1000
1atm,15cm,1MHz
100 10
CO OH
subppm sensitivityfor OH,CH,CN
CH
0.1 0.01 1000 1500 2000 2500
CN
3000
Temperature [K]
AdvancesinShockTube Methodology
1. Improveduniformitywithdriverinserts 2. Longertesttimeswithtailoredgas mixtures&extendeddriver 3. Reactivegasmodeling: problemandsolutions
ImprovementinReflectedShockTemperatureUniformity UsingDriverInserts
Conventionalshocktube operationcanprovide nearidealuniformflows for13ms But,boundarylayersand attenuation inducedP/dt anddT/dt atlongertimes
P5 T5
ImprovementinReflectedShockTemperatureUniformity UsingDriverInserts
Result:dP/dt = 0priorto ignition Properign forcomparison withConstantPsimulations
VRS
P5 T5
10
10
n-Dodecane/Air
=1
0.4 0.8 1.2 1.6
1000/T [1/K]
11
n-Dodecane/Air
=1
0.4 0.8 1.2 1.6
2xDriverExtension
1000/T [1/K]
ShocktubesnowcanoverlapwithRCMs
12
FirstUseofLongTestTimeFacility: LowPressurenHeptaneIgnitionintheNTCregime
Testtime=45ms at725K
Relative Pressure
6
2nd Stage Ignition
n-Heptane/21%O2/Ar
=1, 725K, 2.9 atm
Enablesfirstlowpressure (~3atm)nheptaneignition datainNTCregime Clearevidenceof2stage ignition:1 =8ms,2 =20ms Nextstep:adddriverinsertsto removedP/dt &dT/dt
4 3 2 1 0
Reactive Mix
Test time = 45 ms
OH Emission
10
20
30
40
50
Time [ms]
LowPressure,LowTemperatureStudies: NewResultsfornHeptaneintheNTCRegime
100
1000K
833K
714K
625K
3 atm
10
12 atm
40 atm 55 atm
0.1 1.0 1.2 1.4 1.6
Stanford Aachen
1000/T [1/K]
14
LowPressure,LowTemperatureStudies: NTCHeptane,ComparisonwithModel
100
1000K
833K
714K
625K
3 atm
10
12 atm
40 atm
1000/T [1/K]
15
ReactiveGasdynamics Modeling:AProblem
Mostcurrentreflectedshockmodelingassumes ConstantVolumeorConstantPressure But: Exothermic energyreleaseduringoxidationor endothermic coolingduringpyrolysischangesT&P behindreflectedshocks notaConstantVorConstantPprocess! Example:HeptaneIgnition
16
EffectofEnergyReleaseonPProfiles: nHeptaneOxidation
5
Pressure [atm]
3
2
ign
0
0 -100
100
200
300
400
500
600
Time [us]
Howdoesthiscomparewithmodels? NotaconstantPprocess!
17
EffectofEnergyReleaseonPProfiles: nHeptaneOxidation
5
Pressure [atm]
3
2
ign
0
ConstantP Model
0 -100
100
200
300
400
500
600
Time [us]
18
3ProposedSolutionstoEnableModelingthrough EntireCombustionEvent
1. Minimizefuelloadingtoreduceexothermically or endothermicallydrivenTandPchanges
enabledbyhighsensitivitylaserdiagnostics
3. Usenewconstrainedreactionvolumeconceptto minimizepressureperturbations
enablesconstantP(orspecifiedP)modeling
Examples:
1)Useofdilutereactivemixtures 2)Useofconstrainedreactionvolume
19
Example1:BenefitofDiluteMixtures 3PentanoneOxidation
LowFuelLoadingExperiment
2.0
OHMoleFraction
150
1.5
Const. H P Model
100
Pressure [atm]
1.0
OH Data
50
0.5
TfinalTInitial =45K
0 0 500 1000 1500
Time [s]
Time [s]
Example2:ConstrainedReactionVolumeApproach HydrogenIgnitionat950K
ConventionalShockTube
PreShock HeliumTestMixture PostShock
ConstrainedReactionVolume
PreShock HeliumNonReactiveMixTM PostShock
Reflected ShockWave
LargeRegionof EnergyRelease
SmallRegionof EnergyRelease
Example2:ConstrainedReactionVolumeApproach HydrogenIgnitionat950K
ConventionalShockTube
8
ConstrainedReactionVolume
8
Pressure [atm]
Pressure
Emission
0 0 1 2 3 4 5
0 0 1 2 3
Emission
Time [ms]
Time [ms]
ElementaryReactionRate Determinations
Goal Neardirectdeterminationofrate constantsforspecificreactions Examples OH+ketones:
acetone,2butanone,2 &3pentanone
ExperimentalStrategy
TBHPusedasapromptOHprecursor UsefulTrange(850to1350K) PioneeredbyBott andCohen(1984) AlsousedatArgonne Fuelinexcess,pseudofirstorderexperiment
+
tertbutylhydroperoxide Acetone
24
Representative3Pentanone+OHData: 1188Kand1.94atm
20
15
1 0 -1 -2 -3
10
0 0 50 100
-4
Time [s]
Time [s]
Resultsfor3Pentanone+OH Products
1429K 1E14 1250K 1111K 1000K 909K 833K
3-Pentanone + OH = Products
-1 -1 3 3
-1 -1
1E13
+/ 20%
Current Study Serinyel et al. - NUI Galway (2010)
1E12 0.7 0.8 0.9 1.0 1.1 1.2
1000/T [1/K]
Summary:OH+KetonesProducts
1429K 1250K 1111K 1000K 909K 833K
1E13
1000/T [1/K]
1E13
1E12 0.7
1000/T [1/K]
Dataagreewithin25%withSARestimatedrateconstants Currentwork:OH+aldehydes,alcohols
28
MultiSpeciesTimeHistories
Motivation Multispeciesprovidegreaterconstraint onmechanismrefinement/evaluation RecentWork
Ketones:Acetone,Butanone,3Pentanone Alcohols:1,2,tert,&isoButanol Alkanes:nHexadecane Esters:MethylFormate,MA,MP,MB,EP
29
MultiSpeciesApproach:3PentanonePyrolysis
300
1.2
1% 3-Pentanone / Ar
=3.39m
0.8
3Pent
0.1% 3-Pentanone / Ar
.
200
=216nm
1346 K, 1.67 atm
CH3
0.4
100
0 0 100 200
Time [s]
Time [s]
2.0
0.25% 3-Pentanone / Ar
3000
1.0
1000
0 0 500
=4.6m
1000
CO
0.5
=10.5m
0.0 0 500 1000
C2H4
1500
Time [s]
Time [s]
ExcellentSNR,highsensitivitydata
30
ComparisonwithSerinyel etal.(2010)GalwayNUI
300
1.2
1% 3-Pentanone / Ar
Serinyel et al.
3Pent
0.1% 3-Pentanone / Ar
Serinyel et al.
CH3
1346 K, 1.67 atm
200
0.8
0.4
100
0 0 100 200
Time [s]
Time [s]
2.0
0.25% 3-Pentanone / Ar
3000 Serinyel et al.
CO
1325 K, 1.60 atm
C2H4
1343 K, 1.60 atm
2000
1.0
1000
0.5
0 0 500 1000
Time [s]
Time [s]
TwoDifferences:1)3Pdecompositionrate;2)CO/C2H4 yields
31
3PDataEnablesRevisionofDecompositionRate
3PentanoneSensitivity
100000
ArrheniusPlot:3PentProducts
1429K 1250K 1111K
ktotal [1/s]
1000
100
2Channels
10
1 0.7
0.8
0.9
1000/T [1/K]
32
COYieldResolvedthroughUseofOAtomBalance
3PandCOdatayieldtotalOatoms
1.0
Oatomconcentrationat1.5ms LaserAbsorption
3Pentanone: CO: Sum: 23% 69% 92%
0.8
CO
3-Pentanone
0.6
0.4
Simulation(withnewk1+k2)
3Pentanone: 23% CO: 43% CH3CHCO: 27% Sum:93%
0.2
Time [s]
RevisedModelImproves3PSimulations
FinalModificationstoSerinyel etal. 3PentanoneMechanism Reviseddecompositionrate: 3pentanone products Additionalreaction: methylketene C2H4 +CO
CH3
CO
1403 K, 1.57 atm 1325 K, 1.60 atm 1272 K, 1.64 atm
C2H4
2000
1000
0 0 500 1000
Time [s]
Goodagreementwith3P,CH3,CO,andLowTC2H4 timehistories
34
OngoingWork
Diagnostics development & spectroscopy:
aldehydes (CH2O, CH3CHO) alkyl radicals (C2H5) methyl esters (methyl formate) Alkenes (C3H6, C4H8)
Acknowledgements
ARO,AFOSR,DOE,NSF Students: Genny Pang,MattCampbell,WeiRen,BrianLam,SijieLi, SreyashiChakraborty
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