Welcome to Scribd, the world's digital library. Read, publish, and share books and documents. See more
Download
Standard view
Full view
of .
Look up keyword
Like this
0Activity
0 of .
Results for:
No results containing your search query
P. 1
H2

H2

Ratings: (0)|Views: 2|Likes:
Published by Joseph Arnold

More info:

Published by: Joseph Arnold on Jul 02, 2012
Copyright:Attribution Non-commercial

Availability:

Read on Scribd mobile: iPhone, iPad and Android.
download as PDF, TXT or read online from Scribd
See more
See less

07/02/2012

pdf

text

original

 
HYDROGEN-OXYGENREACTIONMECHANISMANDITSIMPLICATIONTOHYDROGENENGINECOMBUSTION
LM.DAS
CentreforEnergyStudies,IndianInstituteofTechnology,Delhi.NewDelhi,
110016,
India
{Receivedforpublicatioll
15
December19951
Abstract-Combustion
of
hydrogenwithairisreceivingincreasingattentioninthefutureenergyscenario.Thispaperbroadlydiscussesthehydrogencombustiontechniquesinvariousthermalsystems.
A
more:elaboratediscussion
has
beenmadewithrespecttointernalcombustionengineswhereabigroleforhydrogenisenvisionedparticularlyinthepresentcontextofenergycrisisandenvironmentaldegradation.
INTRODUCTION
If
onetriestofindforthedefinitionofaperfectfuel,hydrogenprobablysatisfiesmostofthedesirablechar-acteristicsofsuchafuel.Plentifulandclean-burning,hydrogenhasaveryhighenergycontent.
It
isnotonlyadaptabletopowergenerationbutalsotoindustrial,residentialandtransportationuses.Hydrogenpossessesexcellentphysicochemicalpropertiessuchaslowmini-mumignitionenergywideignitionlimitsandhighflamepropagationrate.Fundamentally,hydrogenasafuelisnomoredangerousthangasolineornaturalgas,butithasdifferentpropertiesfromtheconventionalfuelswhichneedadifferentsetofprecautionarymeasurestohandIeit.
It
isthecombustion-relatedpropertiesofhydrogenwhichmustbecarefullystudiedbeforeplanningoutanylarge-scaleutilisationofhydrogenfuelintheindustrial,residentialandtransportationsector.Anefforthas
been
madeinthispapertodiscusstherelevanthydrogen-oxygenreactionmechanismanditsapplicationtovariousthermalsystems.
A
moredetaileddescriptionhasbeenmadepossibleinrespectofinternalcombustionengines,becauseoftheauthor'sinvolvementisthisfieldofstudy.HYDROGEN-DXYGENREACTIONMECHANISMThehydrogen-oxygenreactionmechanismhasbeenextensivelystudiedovertheyearsandhasalreadygotwidespreadapplicationsuchasin
high
energyrocketengines.Morerecentlyithasbecomeextremelyevidentthatcombustionofhydrogen
with
air
will
continuetoreceiveincreasingapplicationprimarilybecauseofthenon-pollutingcharacteristicsofthiscombustionprocess.Inthiscontextit
is
essentialtodiscussthehydrogenoxygenandhydrogenaircombustionreactivemechan-ism.Ithasbeenobservedthatunderambientconditionsoftemperature,hydrogenandoxygendonotenterintoanydirectreactionbetweentheminabsenceofacatalyst.Itisfurther
seen
ifamixtureofhydrogenandoxygengetsexposedtolightoxygengetsactivatedusuallybywayofdissociation.Inthepresenceofthe
sensitizersof
Cl,
N
20,
andNH
J,
asetofsecondaryreactionstakeplaceandfonnHatoms.TheseHatomsenterintoareaction
with
theactivatedoxygenthusforming
H
2
0.
A
catalyticreactiontakesplacewithmetalssuchasplatinum,undersuchcircumstances.
H
2
0
gets
formed
asabyproduct.Schlosser
[I]
reportsasimilarcatalyticreaction,calledbranching-chainreactionwhichisex-tremelyimportant.Insuchamechanism,eachcycleofthechainresults
in
anetincreaseintbenumberofchaincarrierssuchasradicalsoratoms.
A
typicalexampleoftbehydrogen-oxygenbranchingchainexplosionisgiven
in
Ref.[2].
H2
+
02
--;>
20H
(Initiating)\H
+
O
2
OH
+
0(Branching)
I
0+H,OH+H(Branching)
>
BranchedchainOH
+
~!-
H
2
0
+
H(Propagating)
J
H
+
H
+
M_,.
H
2
+
M
(Terminating)
It
hasbeenconclusivelyestablishedthatnnecycleofthisreactionproducesanetincreaseoftwohydrogenatomsinthereactivesystem.Unlessthesetwohydrogenatomsareusedupinthesamelengthoftimethereactionrategoesonincreasingexponentiallywithtimeand
 
704
10,000500020001000
~
500
;I::
200
e
~
100
e
50
'"
n
'"
,
..
20
~
10
5
Noexploston
Explosion
2
1'----'----'---'---_"_--=-"'-----
360400440480520560600Temperature
("C)
Fig.I.
Explosionlimitsora
hydrogen-oxygen
system.resultsinanexplosion.Suchasituationcanhoweverbeavoidediftheterminatingprocessesarerapid.FigureIshowsatypicalexplosion-limitdiagramforachainbranchingreaction,ofahydrogen-oxygensystem[3].Thephenomenonofdifferenttypesofpre-ignitioncanbebestunderstoodbyadoseexaminationofthismap.Preignitioncanoccurduringtheintakestrokespecifiedbythesecondexplosionlimitof50mmHg.Thisusuallyoccursbywayofheattransferfromthewallorfromhotparticles.Duringthepre-ignitionatintakestroke,thetemperaturelevelremainsequaltoorgreaterthanthesecondexplosionlimitcorrespondingtoaparticularpressure.Infact,toensureconditionsleadingtopre-ignitionchargehastoremainatthetemperaturelevelforaminimumperiodspecifiedbytheinductionlime.Thisholdsgoodfortemperaturerangesmuchabovetheexplosionlimit.Suchatrendiswell-illustratedinFigure2.AccordingtoMomthilotf
etal.
[4],inductiontimeisproportionaltothereciprocaloftheexponentialofthereciprocaloftheabsolutetemperatures.Diffusion-con-trolledwallreactionsaccompaniedbyrecombinationhelpreducetheamountofactiveatomsandradicals
in
thevolume.Examplesofwallreactionsinvolvingrecom-binationaregivenby
H
+
H-H
2
0+0-02
OH
+
OH-H
2
0
2•
Thebehaviourofsuchwallreactionsdependstoalargeextent,ontheoperatingpressureranges.Withinpressurerangesbelow5mbarthereactionofhydrogen
L.
M.DAS
100
*
~~
Hydrogen-Air1atmosphere
;1
=
1.0
Datapoints:
o
Mullins
x
Foure
<>
DasGupta+
Ncholls
/!.SC<JUand
Kinsey0.01
~
0
0
0
,-.,
<n
~
.,
e
-
:
.~
0.1
to
::0
~
.s
+
<>00
+
+
tiS
0.004'--___.__---'-___..___-'-__
...J.____
1.1
1.0
0.80_5.70.6
.9
Temperature
(11K)
Fig.2.Effectoftemperatureoninductiontime.withoxygentakesplaceatarelativelylowerintensity.
If
thepressureisfurtherincreased,theexplosivecombustionstageisreached.Furtherincreaseinpressurebringsthesystemtoanotherrangewithoutexplosivecombustion.H
+
O
2
+
M-H
2
0
+
MstopthechainreactioninthegasphaseM
=
NeutralMoleculesinthegas.Thecombustionphenomenontakesaninterestingturn
if
thepressureisfurtherincreased.Theprocessofdiffusionslowsdown.
H0
2
+
Hl-
H
2
0
2
+
H
H
2
0
2
+
M.....20H
+
M.
With
H0
2
radicalasachaincarrierasshownintheabovereactions,theprocessofcombustionturnsintoaheatexplosion.FigureIverydistinctlyshowstheoccur-renceofanexplosionpeninsulaandtheexistenceofthreewell-identifiablepressurelimitsoverashorttemperaturerange.Theselimitsareusuallyreferredtoasthefirstlimit(Cduetowail),recombinationsecondlimit(Cduetogasphaserecombination)andthethirdlimit(hightemperature).Chainbranchingtheoryisnotabletopredicttheoccurrenceofthethirdlimit.
 
HYDROGEN-OXYGENREACTIONANDHYDROGENENGINECOMBUSTION
It
hasbeenreportedintheliteraturethatthesecondexplosionlimitvarieswithgeometry,sizeandthesurfacematerialofthesystem.Concentrationofanyinertspecies,
(if
present)alsohavesomedefiniteinfluenceonthesecondexplosionlimit.Thisisgivenbytherelation
"
PH,
+
ho,Po,
+
L
biPi
=
K
j;;::l
wherehiisthecoefficientoftheparticularspecies
Pi
isthepartialpressureofspecies'i'
K
istheconstant.MinkoffandTipper
[5)
haveexperimentallyevaluatedthevalueof
hI
(thepressurecoefficientforsecondexplosionlimit).Pre-ignitionwhichusuallytakesplaceduringcompres-sionstrokeisexplainedbythethirdexplosionlimit.Asaconsequenceoftheincreaseinpressure,thethirdexplosionlimit(thetemperaturelevel)getsdecreased.Thisisclearfromthebranchingrelations.Thereoccurs
a
rapid
self-heating
fromthesebranchingreactions.MinkoffandTipper
(5]
suggestthattheinertgasesslowthereactionrateaccordingtotheformula
"
r
=
K(PH/Po,
L
CjP
i
i~
where,.
=
reactionrate
K
=
constantofproportionality
C
1
=
Effectivenessconstantforeachofthe'
II'
variousinertspecies.Thisisalsoreferredtoasthethirdexplosionlimitpressurecoefficient.PI
=
Partialpressureofspecies.Table
I
givesacomparativepictureofthesecondexplosionlimitpressurecoefficient
(b
j)
andeffectivenessconstant(C
d
forvariousspecies[3,5·7].Table
I.
SpeciesSecondexplosionlimitpressUTecoefficient
(h,)
Thirdexplosionlimit
pressurecoefficien
t
(e,l
Ar0.2CO
2
1.0
He0.4
HlO10
N,0.4-
0)
0.4
!J
1.0
0.3
\.7-23
1.0
1.0
Thedescriptiongivenaboverelatestothehydrogen-oxygenreaction.But,whileconsideringthehydrogen-aircombustionmechanism,thepartplayedbynitrogenshouldalsobetakenintoaccount[8).AsiswidelyacceptedZeldovichmechanismgivenbytheequationsbelowexplainsthereactionandformationofnitricoxide.
o
+-
N.l
=
NO+N
N
+
O!
=
NO
+
0Infact,
Zeldovich
wasthefirsttoexplainthesignificanceofthesereactions.Lavoie
etal.
[9]
haveadded
the
reaction
N
+
OH
=
NO
+
HtotheZeldovichMechan-ismandthisreactionhasbeenfoundveryusefulinexplainingtheprincipalreactions.NewhallandShahed
[10]
havereportedthat'NO'formulationtakesplacemostlybehindtheflamefront.EXPLOSIONANDDETONATIONHydrogengas,likeotherfuelscanburnintwomodes.Theordinarymodeofburningincalled
deflagrarion,
inwhichtheflametravelsthroughthemixtureatsubsonicspeed.Thishappenswhenanunconfinedcloudofhy-drogen-airmixtureisignitedbyasmallignitionsource.UnderthesecircumstancestheHarnetravelsoveraverywiderangeanywherefrom
10
toseveralhundredmetrespersecond.Therapidexpansionofhydrogengassetsinapressurewave.Thisgeneratesaveryloudnoise
giving
theimpressionofanexplosion.Thepressurewavefromrapidunconfinedburningisnotextremelysevere,al-thoughsometimesitisstrongenoughtodamagethestructuresintheneighbourhood.Theothermodeofburningiscalleddetonation,inwhichaflameandshockwavetraveltogetherthroughthemixtureatsupersonicspeed.Adetonationoftenbuildsupfromanordinarydeflagrationthathasbeenignitedinaconfinedorpartly-confinedmixture.Thisistrueeventhoughignitionmayhavebeencausedby
a
minimalignitionenergy.Yu
etal.
[II]
carriedoutaninvestigationinvolvingmethane-airand
propane-air
mixtureswithandwithouttheadditionofstoichiometricallysmallamounts
of
hydrogen.Theywereabletoevaluatethelaminarflamespeedoftheabovementionedmixturesusingthe
syrn-
metrical,adiabaticandcounterflowarrangement.In-itiallytheymeasuredthefamespeedswithstretchandthenmadealinearextrapolationofthesevaluestozerostretch.Theirresultsconclusivelyshowedthattheflamespeedgetssubstantiallyincreasedwithhydrogenaddi-tion.Themethodologydevelopedbytheseresearchershasbeenveryusefulindeterminingquiteaccuratelythelaminarflamespeedoveraverywiderangeofequivalenceratio.STEADYANDUNSTEADYHYDROGEN
COMBUSTIONINVARIOUSSYSTEMS
Dependingupontheapplicationrangethetypesofcombustioncanbeclassifiedassteadyorunsteady.Steadycombustionofhydrogenmanifestsitselfdistinctlyonsystemsrangingfromsimpleflameburners(forheating)tocatalyticheater.steamandgasturbines.rocket

You're Reading a Free Preview

Download
scribd
/*********** DO NOT ALTER ANYTHING BELOW THIS LINE ! ************/ var s_code=s.t();if(s_code)document.write(s_code)//-->