ichs, international conference on hydrogen safety, september 8-10, 2005, pisa (italy) 1 role of...

11ICHS, International Conference on Hydrogen Safety, September 8-10, 2005, Pisa (Italy)

Role of Chemical Kinetics onRole of Chemical Kinetics on the Detonation Properties of the Detonation Properties ofHydrogen / Natural Gas / Air Hydrogen / Natural Gas / Air

MixturesMixtures

N. Chaumeix, S. Pichon, F. Lafosse, N. Chaumeix, S. Pichon, F. Lafosse, N. Udari, C.-E. PaillardN. Udari, C.-E. Paillard

Laboratoire deCombustion etSystèmesRéactifs


MOTIVATIONSMOTIVATIONS

GREEN HOUSE EFFECT REDUCTIONGREEN HOUSE EFFECT REDUCTIONCombustion is a major contributor, CO, COCombustion is a major contributor, CO, CO22, NOx, Soot …, NOx, Soot …BiofuelsBiofuelsNatural gasNatural gasHydrogenHydrogen

NATURAL GASNATURAL GAS Relatively low emission, CORelatively low emission, CO22, PAH and soot, PAH and sootHigh octane numberHigh octane number

HYDROGEN AS AN ADDITIVE TO NATURAL GASHYDROGEN AS AN ADDITIVE TO NATURAL GAS Increase of the flammability domain,Increase of the flammability domain, Increase of the stability rangeIncrease of the stability range


MOTIVATIONSMOTIVATIONS

HYDROGEN AS AN ADDITIVE TO HYDROGEN AS AN ADDITIVE TO NATURAL GASNATURAL GASProduction and StorageProduction and StorageEconomically interestingEconomically interesting Adaptation for multiple useAdaptation for multiple useIncrease the risk of explosion and detonationIncrease the risk of explosion and detonation


AIMS OF THE STUDYAIMS OF THE STUDY

Oxidation of Hydrogen / Methane based Oxidation of Hydrogen / Methane based MixturesMixtures For conditions close to detonationFor conditions close to detonation Auto-ignition delay timesAuto-ignition delay times Validation and selection of a detailed kinetic Validation and selection of a detailed kinetic

mechanimmechanim

Determination of the detonation parametersDetermination of the detonation parameters Chapman-Jouguet and ZND conditionsChapman-Jouguet and ZND conditionsExperimental measurements of cell size Experimental measurements of cell size


{H2/CH4/O2} mixture : CH4/CH4+H2 = 0.4, =0.75; P1 = 10 kPa; T1 = 20°C

Velocity : DC.J = 1800 m.s-1 (Dexp = 2218 14 m.s-1) Von Neumann parameters:

T2N = 1380 K P2N =250 kPa

TripleTriple pointspoints

Leading shockLeading shock

Reaction zoneReaction zone

: : induction distanceinduction distance

: ignition delay time: ignition delay time behind the leading shockbehind the leading shock

Evaluation of For these conditions

CORRELATION BETWEEN CORRELATION BETWEEN AND AND


EXPERIMENTAL SETUPEXPERIMENTAL SETUPAuto-ignition Delay TimesAuto-ignition Delay Times

I.E.E.E

PUMPS

Pressure Gage0 - 100 T

AirMixture

He

Driven Section

Diaphragm

HighPressure

Knife

N2

C4 C3 C2 C1

4 3 2 1 1 2


EXPERIMENTAL SETUPEXPERIMENTAL SETUPAuto-ignition Delay TimesAuto-ignition Delay Times

0 .0 x 1 0 0 2 .0 x 1 0 -4 4 .0 x 1 0 -4 6 .0 x 1 0 -4

T im e (µ s)

Arb

itra

ry u

nit

s

x C H 4 /(x C H 4+ x H 2) = 0 .4 ; = 0 .4P 5 = 9 2 4 k P a ; T 5 = 1 6 2 0 K

A u to -ign ition D ela y tim e

ign = 70 .5 µ sRef

l ec t

e d S

hock

Inci

dent

Sho

c kO H E m iss io n S ig n a l

P re ssu re S ig n a l


EXPERMENTAL SETUPEXPERMENTAL SETUP

Detonation Parameter MeasurementsDetonation Parameter Measurements

-0 .0 0 0 1 0 0 .0 0 0 1 0 .0 0 0 2 0 .0 0 0 3

T em p s (s)

Cap

teur

N°7

Cap

teur

N°8

Cap

teu

r N

°9C

apte

ur

N°1

0

C H 4/{C H 4+ H 2}= 0 ,40 ,2 4 32 H 2 + 0 ,1 6 22 C H 4 + 0 ,5 9 46 O 2

2 9 8 K ; 1 0 k P a ; = 0 ,7 5

V d et = 2 21 8 m .s-1


EXPERIMENTAL CONDITIONSEXPERIMENTAL CONDITIONS

Auto-ignition Delay timesAuto-ignition Delay timesMixtures:Mixtures: CHCH44/H/H22/O/O22 in 99% of Argonin 99% of ArgonCHCH44/CH/CH44+H+H22 = 0 ;0,4; 0,8 = 0 ;0,4; 0,8 =0,4; 0,75; 1=0,4; 0,75; 11000 K 1000 K T T5 5 1500 K 1500 K0,15 0,15 P P5 5 0,25 MPa 0,25 MPa

Detonation ParametersDetonation ParametersMixtures: CHMixtures: CH44/H/H22/O/O22

CHCH44/CH/CH44+H+H22 = 0 ; 0,2 ; 0,4 ; 0,6 = 0 ; 0,2 ; 0,4 ; 0,6 =0,75 ; 1=0,75 ; 1PP11 = 10 et 20 kPa = 10 et 20 kPa


AUTO-IGNITION DELAY TIMESAUTO-IGNITION DELAY TIMES

Strong decrease withStrong decrease with TemperatureTemperatureEquivalence ratioEquivalence ratio

6.5x10 -4 7.0x10 -4 7.5x10 -4 8.0x10 -4 8.5x10 -4 9.0x10 -4

1 /T (K - 1)

100

1000

Aut

o-ig

niti

on d

elay

tim

es (

µs)

C H 4 /(C H 4+ H 2 ) = 0

= 0 ,4

= 0 ,7

= 1



Strong decrease withStrong decrease with TemperatureTemperatureEquivalence ratioEquivalence ratio

4.0x10 -4 5.0x10 -4 6.0x10 -4 7.0x10 -4 8.0x10 -4

1 /T (K -1)

100

1000

Aut

o-ig

niti

on D

elay

tim

es (

µs)

C H 4 / (C H 4+ H 2 ) = 0 ,4

= 0 ,4

= 0 ,7

= 1

4.8x10 -4 5.6x10 -4 6.4x10 -4 7.2x10 -4

1 /T (K -1)

100

1000

10000

Aut

o-ig

niti

on D

ealy

tim

es (

µs)

C H 4 / (C H 4+ H 2 ) = 0 .8

= 0 .4

= 1



Strong increase withStrong increase with Methane contentMethane content

4.0x10 -4 5.0x10 -4 6.0x10 -4 7.0x10 -4 8.0x10 -4 9.0x10 -4

1 /T (K -1)

100

1000

10000

Aut

o-ig

niti

on D

elay

Tim

es (

µs)

E q u iv a le n c e R a t io = 0 .7 50% CH 4

40% CH 4

5.0x10 -4 6.0x10 -4 7.0x10 -4 8.0x10 -4 9.0x10 -4

1 /T (K -1)

100

1000

10000

Aut

o-ig

niti

on D

elay

Tim

es (

µs)

E q u iv a le n c e R a tio = 0 .40% CH 4

40% CH 4

80% CH 4



Strong increaseStrong increasewith Pressurewith Pressure

5x10 -4 6x10 -4 6x10 -4 7x10 -4 7x10 -4 8x10 -4 8x10 -4

1 /T (K -1)

10

100

1000

10000

Aut

o-ig

niti

on D

elay

Tim

es (

µs)

C H 4 / (C H 4+H 2 ) = 0 ,4 e t = 0 ,4

P 5 = 1 9 03 0 k P a

P 5 = 1 1 3 03 0 0 k P a


CORRELATIONSCORRELATIONS

From the experimental dataFrom the experimental data

KT

9815expOH1014.1µs 65.0

240.0

22

H2

KT

12180expOHCH96.5µs 10.1

212,0

235.1

4HCH 24

Average error < 14 %


DETAILED KINETIC DETAILED KINETIC MECHANISM VALIDATIONMECHANISM VALIDATION

REFERENCEREFERENCE SPECIESSPECIES REACTIONSREACTIONS

Gas Research InstituteGas Research Institute 5353 325325

Lawrence Livermore Lawrence Livermore National LaboratoryNational Laboratory

155155 689689

LEEDSLEEDS 3737 175175

KONNOVKONNOV 127127 10271027


MODEL vs EXPERIMENTSMODEL vs EXPERIMENTS

6.5x10 -4 7.0x10 -4 7.5x10 -4 8.0x10 -4 8.5x10 -4 9.0x10 -4

1 /T 5 (K -1 )

1 0

1 0 0

1 0 0 0

1 0 0 0 0

Aut

o-ig

nitio

n de

lay

times

(µ

s)

E x p e rim en tsG R I3 .0L E E D SL L N L

Konnov

C H 4 / (C H 4 + H 2 ) = 0

= 0 ,4 - P 5 = 2 2 0 1 0 k P a

7.2x10 -4 7.6x10 -4 8.0x10 -4 8.4x10 -4 8.8x10 -4

1 /T 5 (K -1 )

1 0 0

1 0 0 0

Aut

o-ig

niti

on d

elay

tim

es (

µs)

E x p e rim e n tsG R I3 .0L E E D SL L N L

Konnov

C H 4 / (C H 4 + H 2 ) = 0

= 0 ,7 5 - P 5 = 2 1 3 1 7 k P a

Konnov’s MechanismKonnov’s Mechanism

is most suitableis most suitable

7.2x10 -4 7.6x10 -4 8.0x10 -4 8.4x10 -4 8.8x10 -4

1 /T 5 (K -1 )

1 0 0

1 0 0 0

Aut

o-ig

niti

on D

elay

tim

es (

µs)

E x p e rim e n tsG R I3 .0L E E D SL L N L

Konnov

C H 4 / (C H 4 + H 2 ) = 0

= 1 - P 5 = 2 1 0 3 0 k P a



Konnov’s Mechanism is most suitableKonnov’s Mechanism is most suitable

4.8x10 -4 5.6x10 -4 6.4x10 -4 7.2x10 -4

1 /T 5 (K -1 )

1 0 0

1 0 0 0

1 0 0 0 0

1 0 0 0 0 0

Aut

o-ig

nitio

n D

elay

Tim

es (

µs)

C H 4 / (C H 4+ H 2 ) = 0 ,8

= 1 - P 5 = 1 9 4 2 3 k P aE x p e rim e n tsG R I3 .0L E E D SL L N L

Konnov

5.6x10 -4 6.0x10 -4 6.4x10 -4 6.8x10 -4 7.2x10 -4

1 /T 5 (K -1)

1 0

1 0 0

1 0 0 0

1 0 0 0 0

Aut

o-ig

niti

on D

elay

tim

es (

µs)

C H 4 / (C H 4+ H 2 ) = 0 ,8

= 0 ,4 - P 5 = 1 9 0 2 0 k P aE x p e rim e n tsG R I3 .0L E E D SL L N L

K onnov



depends on the equivalence ratiodepends on the equivalence ratio

4.8x10 -4 5.6x10 -4 6.4x10 -4 7.2x10 -4 8.0x10 -4

1 /T 5 (K -1 )

1 0 0

1 0 0 0

1 0 0 0 0

Aut

o-ig

niti

on D

elay

tim

es (

µs)

C H 4 / (C H 4+ H 2 ) = 0 ,4

= 1 - P 5 = 1 8 4 1 3 k P aE x p e rim e n tsG R I3 .0L E E D SL L N L

Konnov

4.8x10 -4 5.6x10 -4 6.4x10 -4 7.2x10 -4

1 /T 5 (K -1 )

1 0

1 0 0

1 0 0 0

1 0 0 0 0

Aut

o-ig

niti

on D

elay

tim

es (

µs)

C H 4 / (C H 4+ H 2 ) = 0 ,4

= 0 ,7 5 - P 5 = 1 8 8 4 2 k P aE x p e rim e n tsG R I3 .0L E E D SL L N L

Konnov



Different mechanisms from the Different mechanisms from the literature were usedliterature were used

The comparison between the The comparison between the experiments and the prediction depends experiments and the prediction depends on the amount of Hon the amount of H22 in the mixture in the mixture

The most reliable is The most reliable is KONNOV’sKONNOV’s mechanism which will be usedmechanism which will be used

Needs to be improvedNeeds to be improved


DETONATION PARAMETERSDETONATION PARAMETERS

Chapman- Jouguet (TChapman- Jouguet (TCJCJ, P, PCJCJ, V, VCJCJ) Parameters) Parameters

ZND (TZND (TZNDZND, P, PZNDZND) Parameters) Parameters

Auto-ignition Delay Times of CHAuto-ignition Delay Times of CH44/H/H22/air Mixtures/air Mixtures

Package CHEMKINPackage CHEMKINEQUIL & SENKIN codesEQUIL & SENKIN codes


RESULTSRESULTS

0 0 .2 0 .4 0 .6 0 .8

C H 4/(C H 4+ H 2)

1

1 0

1 0 0

PC

J (at

m)

KO N N O V- =0.750,1bar1bar

GR I- =0.750,1bar1bar

0 0 .2 0 .4 0 .6 0 .8

C H 4/(C H 4+ H 2)

1 6 4 0 0 0

1 6 8 0 0 0

1 7 2 0 0 0

1 7 6 0 0 0

1 8 0 0 0 0

1 8 4 0 0 0

VC

J (cm

/s)

G R I - = 0,750,1bar1bar

KO N N O V - = 0,750,1bar1bar

0 0 .2 0 .4 0 .6 0 .8

C H 4/(C H 4+ H 2)

2 4 0 0

2 4 5 0

2 5 0 0

2 5 5 0

2 6 0 0

2 6 5 0

2 7 0 0

TC

J (K

)

G R I0,1bar - = 0,75

1bar - = 0 ,75

K O N N O V0,1bar - = 0 ,75

1bar - = 0 ,75


CONDITIONS ZNDCONDITIONS ZND

0 0.2 0.4 0.6 0.8

C H 4 /(C H 4+ H 2)

0

10

20

30

P ZN

D (

atm

)

G R I0,1bar - = 0 ,75

1bar - = 0 ,75

K O N N O V1bar - = 0 ,75

0,1bar - = 0 ,75

0 0.2 0.4 0.6 0.8

C H 4/(C H 4+ H 2)

1360

1380

1400

1420

1440

TZ

ND (

K)

G R I0,1bar - = 0,75

1bar - = 0,75

K O N N O V0,1bar - = 0 ,75

1bar - = 0 ,75


AUTO-IGNITION DELAY TIME AUTO-IGNITION DELAY TIME BEHIND THE LEADING SHOCKBEHIND THE LEADING SHOCK

0 0.2 0.4 0.6 0.8

C H 4/(C H 4+ H 2)

1x10 -6

1x10 -5

1x10 -4

1x10 -3

1x10 -2

Aut

o-ig

niti

on d

elay

tim

es (

s)

G R I - 1 0 kP a = 0,4

= 0,75

= 1

K O N N O V - 1 0 k P a= 0,4

= 0,75

= 1

0 0.2 0.4 0.6 0.8

C H 4/(C H 4+ H 2)

1x10 -7

1x10 -6

1x10 -5

1x10 -4

1x10 -3

1x10 -2

1x10 -1

Au

to-i

gnit

ion

Del

ay T

imes

(s)

G R I - 1 0 0 kP a = 0 ,4

= 0 ,75

= 1

K O N N O V - 1 0 0 k P a= 0,4

= 0,75

= 1


DETONATION CELL SIZEDETONATION CELL SIZE

Sensitivity to detonationSensitivity to detonation with equivalence ratiowith equivalence ratio with methane contentwith methane content

0 0.2 0.4 0.6 0.8 1

C H 4/{C H 4+ H 2}

0

20

40

60

80

Lar

geu

r d

e ce

llu

le (

mm

)

: =0,75 - P 1=10 kPa

: =1 - P 1=10 kPa

: =1 - P 1=20 kPa


CONCLUSIONCONCLUSION

A new experimental databaseA new experimental databaseAuto-ignition delay timesAuto-ignition delay timesCorrelations valide for detonation conditionsCorrelations valide for detonation conditionsDetonation cell sizeDetonation cell size

Validation of a detailed chemical kinetic Validation of a detailed chemical kinetic mechanismmechanismKonnov’s Mechanism the most reliableKonnov’s Mechanism the most reliableNeeds to be improvedNeeds to be improved


AKNOWLEDGEMENTAKNOWLEDGEMENT

This work was financially supported by This work was financially supported by Commissariat à l’Energie Atomique (CEA) Commissariat à l’Energie Atomique (CEA) under the contract number CNRS / CEA under the contract number CNRS / CEA N°SAV 32030.N°SAV 32030.


COMPARISON WITH CHENG & COMPARISON WITH CHENG & OPPENHEIMOPPENHEIM

4 .8 E -0 0 4 5 .2 E -0 0 4 5 .6 E -0 0 4 6 .0 E -0 0 4 6 .4 E -0 0 4 6 .8 E -0 0 4 7 .2 E -0 0 4

1 /T (K -1)

1 0 0

1 0 0 0

1 0 0 0 0

Dél

ai d

'aut

oinf

lam

mat

ion

(µs)

C H 4 / (C H 4+ H 2 ) = 0 ,8

e x p , = 0 ,4

e x p , = 1

corr se lo n [1 1 ], = 0 ,4

corr se lo n [1 1 ], = 1

4 .0 E -0 0 4 5 .0 E -0 0 4 6 .0 E -0 0 4 7 .0 E -0 0 4 8 .0 E -0 0 4

1 /T (K -1)

1 0 0

1 0 0 0

Dél

ai d

'aut

oinf

lam

mat

ion

(µs)

C H 4 / (C H 4+ H 2 ) = 0 ,4

e x p , = 0 ,4

e x p , = 0 ,7

e x p , = 1

C H 4 / (C H 4+ H 2 ) = 0 ,4

corr se lo n [1 1 ], = 0 ,4

corr se lo n [1 1 ], = 0 ,7

corr se lo n [1 1 ], = 1


Détonation : Couplage entre une onde de Détonation : Couplage entre une onde de choc (choc (||) et une zone réactionnelle () et une zone réactionnelle ())

INTRODUCTIONINTRODUCTIONDéflagration : Inflammation qui se propage Déflagration : Inflammation qui se propage par diffusion de chaleur et de radicaux par diffusion de chaleur et de radicaux

Zone réactionnelle

(gaz brûlés) (gaz frais)

Délai

(gaz frais)(gaz brûlés)

P et T élevées

ichs, international conference on hydrogen safety, september 8-10, 2005, pisa (italy) 1 role of...

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