Beruflich Dokumente
Kultur Dokumente
SelectiveCatalyticReduction(SCR)
ofNObyNH3inaFixedbedReactor
HeeJeSeong
1.Introduction
Fossilfuelshavebeenmainsourcesforenergyintermsofcombustion,wherechemicalenergyin
fuelsisconvertedintothermalandmechanicalenergies.Whenairreactswithfuelsathightemperature,
NOxrepresentingNO,NO2,N2O,N2O5andetcisunavoidableduetothereactionbetweenoxygenand
nitrogeninair[1,2].NOxistoxicasitselfaswellasaprecursorofacidrain,soitsregulationhasbeen
becomingmorestringentalloverthecountries.TherehasbeenmuchinterestinreducingNOxfrom
enginesintermsoffuelinjectionstrategies[3],exhaustgasrecirculation[4]andcatalyticreactions[5],
amongwhichselectivecatalyticreduction(SCR)hasbeensuccessfullyappliedinstationaryapplications
suchasboilersandpowerplants[6].Althoughtherearemanyreducingagentssuggested,gaseous
ammoniashowsthebestperformanceforthisreaction[7]:
4NH3+4NO+O24N2+6H2O(1.1)
Althoughtheequation(1.1)isamajorpathwayforNOinthepresenceofO2,theequation(1.2)isalso
importantwhenNO2ishighinthemixtureofNOandNO2[8].
4NH3+2NO+2NO24N2+6H2O(1.2)
TherehavebeenmanycatalystsdevelopedfortheSCRreaction[9,10],amongwhichaV2O5/TiO2
catalysthasbeenwidelyusedincommercialapplications[10].Althoughtheequation(1.1)isanoverall
reactionforSCR,manyelementarystepsareinvolvedduringthereactionbetweenNOandNH3[11].
SinceNOisreactedwithNH3oncatalysts,itsdetailedreactionmechanismhasbeenofgreatinterestin
ordertodevelopkineticmodelsofSCRdependinguponcatalysts[1214].Accordingtomanystudies,it
isacceptedthatNOisreactedviatheLangmuirHinshelwoodmechanisminV2O5WO3/TiO2catalysts
[13],wheregaseousNOandNH3areadsorbedonthecatalystsandadsorbedNOandNH3arereacted
onthesurface.
TherehavebeenmanyresearchesformodelingofammoniaSCRsystems[1519].Asevidencedby
experiments,oxygenconcentrationintheexhaustgasesiscrucialfortheSCR.Therefore,somekinetic
modelstookintoaccounttheoxygenconcentration[18,19].However,Chaeetal.onlyconsideredNO
andNH3concentrationsfortheirmodelalthoughoxygeneffectwasalreadyemployedintheirmodel
[16].AnotherimportantparameterintheSCRmodeliswhetherNH3isoxidizedbyreactingoxygenas
shownintheequation(1.3)[17,18].Sincethisreactionisactiveathightemperatureover400oC,itis
observedthatNOremovalactivitydecreasesoverthistemperaturebecauseNH3whichneedsforNO
reactionisconvertedintoNO.
4NH3+5O24NO+6H2O(1.3)
Inthisstudy,thereactionbetweenNOandNH3wassimulatedinCOMSOLusingfundamentalmass
andmomentumequations.ThemodelwasstudiedifitisappropriatetodescribeSCRreaction,which
hasbeenexperimentallyproven.
2.GoverningEquations
Therearetwogoverningequationsemployedinthismodel;oneisamassequation,andthe
otherisamomentumequation.AlthoughthereisaheatevolvedduringthereactionofNOandNH3,an
energyequationwasnotconsideredbecauseitisverysmallduetosmallamountsoftworeactants.The
equation(2.1)indicatesamassequationinanadvectiveflow.
(2.1)
wherecisaconcentration,Disadiffusioncoefficient,Risachemicalreaction,andvisavelocitywhich
isavectorform.Sincethemassequationisassumedatasteadystate,the1sttermiscanceledoutand
finallytheequationbecomestheequation(2.2)
(2.2)
Foramomentumequation,theincompressibleNavierStokesequationinalaminarflowwasemployed
asshownintheequation(2.3)and(2.4)
(2.3)
0(2.4)
Sincethereisnoconvectiveforceandtheintertialforceisassumednegligible,thentheequation(2.3)
becomesasfollows.
(2.5)
3.Formulation
ThereactionofNOandNH3wassimulatedin2DaccordingtoFig.3.1,wheretheboxisacross
sectioninthecenterofthetubularreactor.Theboundaryconditionsarealsogiveninthefigure.
Inlet
W=0.1(m)
WallH=0.072(m)Wall
Outlet
Fig.3.1Modelforthesimulationanditsboundarycondition
Themassequation(2.2)isuseddirectlyinthismodelandthereactionratesofNOandNH3aregivenin
(3.1)(3.5)referringtoChaeetal.skineticmodel[16]becauseitincludesthereactionkineticsand
relatedkineticconstantswiththeirexperimentalandsimulatedresults.Thekineticconstantsemployed
inthismodelaretabulatedinTable3.1aswell.
(3.1)
(3.2)
exp (3.4)
exp (3.5)
Table3.1Kineticparametersatthegivenreactionrates
Theequation(2.5)wasalsousedforthemomentumequationinthismodel,butitiscorrectedforthe
modeltakingintoaccountBrinkmanequationasshownin(3.6)sincethereactorsimulatedinthemodel
isporous.
(3.6)
IntheChaeetal.smodel,theporosityofthereactorisnotavailable,sothereisnoinformation
availableforpermeabilityandpressuredropacrossthereactor.Accordingly,pressuredropand
permeabilitywerecalculatedusingErgunsequationandDarcyslaw,respectively,asindicatedin(3.7)
and(3.8).
.
(3.7)
WhereLisareactorlength,dpisaparticlediameter,and isadensityofthefluid.
(3.8)
whereQisaflowratethroughthereactorandAisacrosssectionalareaoftheflow.
Thefluidflowingthroughthereactorisassumedasairbecauseitisnotmuchdifferentfromtheexhaust
gasesinrealplantsanditspropertiesatdifferenttemperaturesareavailableinTurnsbook[2].Since
thedensityandthedynamicviscosityofairaretemperaturedependent,theirvalueswereplottedasa
functionoftemperatureasshowninFig.3.2.Fromthefittedequations,thedensityandthedynamic
viscosityaregivenasafunctionoftemperatureandtheequationswereusedforthecalculationof
pressuredropandpermeabilityin(3.7)and(3.8).
.
9.66 10 (3.9)
.
(3.10)
1.4 0.0001
y=9.66E10x1.70E+00
1.2
Dynamicviscosity(m^2/s)
8E05
1
Density(kg/m^3)
0 0
250 350 450 550 650 750 850
Temperature(K)
Fig.3.2Densityanddynamicviscosityofair
4.Solution
TheCOMSOLmodelwassimulatedusingtheformulationexplainedintheprevioussection,and
theresultislikeFig.4.1.
Fig.4.1NOconcentrationdistributiononthebed
ItshowsthatmuchportionoftheinitialNOconcentrationisconsumedintheinletofthereactor.In
ordertounderstandhowtheNOandNH3concentrationschangeasgasesflowthroughthereactor,they
areplottedalongthecenterlineofthereactorasshowninFig.4.2.
1.E02
Concentration(mol/m^3]
NOconcentration
8.E03
NH3concentration
6.E03
4.E03
2.E03
0.E+00
0 0.02 0.04 0.06 0.08
Length(m)
Fig.4.2NOandNH3concentrationsalongthecenterlineinthereactor
ThefiguredisplaysthatNOconsumptionisfasterthanthatofNH3,andthehalfoftheinitialNO
concentrationisconsumedat0.015m.Atthisvelocityof1m/s,theNOandNH3removalefficienciesat
theexitisalmost91.4%and80%,respectively.SincetheNH3slipisalsoregulatedintheemissions,the
resultindicatesthatNH3concentrationshouldbelessthanNOconcentration.Intheparametricstudy,
thevariousNH3concentrationswereemployedtounderstandtheeffectoftheinitialNH3concentration
ontheNOremovalperformance.
5.Validation
InordertovalidatetheCOMSOLmodelemployedinthissimulation,Chaeetal.sresultswere
comparedinFig.5.1for100,000h1and200,000h1.
100
ConversionofNO(%)
80
60
40 Chae'smodel
Thismodel
20
0
200 250 300 350 400 450 500
Temperature(oC)
(a)Spacevelocity=100,000h1
100
CoversionofNO(%)
80
60
40 Chae'smodel
Thismodel
20
0
200 250 300 350 400 450 500
Temperature(oC)
(b)Spacevelocity=200,000h1
Fig.4.1ComparisonofChaeetal.smodelandtheCOMSOLmodel
Asshowninthefigures,theCOMSOLmodelwelldepictsthetrendsofChaeetal.sresultsinthe
conversionofNOasafunctionoftemperaturefortwospacevelocities.However,theresultsbythe
COMSOLmodelarefoundtobenotthesameasChaeetal.smodelinspiteofthesamekinetic
reactions.Sincethepaperdidntincludeanydetailedinformationaboutthemodelconductedintheir
calculationexceptthekineticdataforNOandNH3consumptions,theremightbethedifferenceinthe
resultsbetweentwomodels.TakingintoaccountthelimitationoftheCOMSOLmodeltopredictChaeet
alsresult,themodelappearstobeusefultoevaluatethekineticsimulationofNOandNH3reaction.
Accordingly,theparametricstudywasalsoconductedusingthismodelinthefollowingsectiontofind
theeffectofvariousparameterssuchasNH3NOratioandpressuredropinthecatalyticbedonthe
reaction.
6.ParametricStudy
Inthissession,threeparametricstudieswereemployed;NH3/NOeffect,porosityeffectand
watereffect.
Asdiscussedinthesolutionpart,theconsumptionofNH3throughthecatalyticreactorisnotthe
sameasthatofNO.Therefore,NH3/NOneedstobecontrolledtominimizeNH3slipwithkeepinghigh
NOremovalreactivity.AsshowninFig.6.1,conversionofNOwastestedforNH3/NOof0.85,1and1.15
asafunctionoftemperature.ThefigureindicatesthatthereisnovariationintheconversionofNOup
to350oCwithchangingtheratioandtheconversionincreaseswiththeincreaseintheratioabovethe
temperature.And,theresultalsoshowsthatabove400oC,theconversionisincreasedby46.5%for
theratioof1withrespectto0.85anditisincreasedby24.5%fortheratioof1.15withrespectto1.
Consequently,theeffectofincreasedNH3/NOisnotsignificantfortheratioof1.15.Accordingly,itis
concludedthatNH3/NOshouldbelessthan1below350oCanditshouldbecontrolledtakingaccountof
theconversionabove400oCifthereisNH3slipregulated.
100
ConversionofNO(%)
80
60
NH3/NO=0.85
40
NH3/NO=1
20 NH3/NO=1.15
0
150 250 350 450 550
Temperature(oC)
Fig.6.1EffectofNH3/NOonconversionofNO
AccordingtoChaeetal.spaper,theporosityofaV2O5WO3/TiO2catalystusedintheir
experimentis0.38,butthereisnoadditionalinformationabouttheporosityoftheircatalyticreactor.
Sincetheporosityofthereactoraffectspermeabilityandpressuredropinthismodelsignificantly,NO
removalactivityisalsocomparedfortheporosityof0.5and0.7asshowninFig.6.2.Inspiteofobvious
changesinpermeabilityandpressuredropdisplayedinTable6.1,thereisnochangeobservedinthe
conversionofNO.Therefore,theeffectofpermeabilityandpressuredropusedinthissimulationonthe
kineticsseemstobenegligible.
100
ConversionofNO(%)
80
60
Porosity=0.5
40
Porosity=0.7
20
0
150 250 350 450 550
Temperature(oC)
Fig.6.2EffectofporosityinareactorbedonconversionofNO
Table6.1PermeabilityandPressuredropfortheporosityof0.5and0.7
Porosity=0.5 Porosity=0.7
Temperature(oC)
P(Pa) K(m2) P(Pa) K(m2)
200 29492 3.33x1010 4390 2.23x109
250 33308 3.49x1010 4861 2.40x109
300 37529 3.62x1010 5353 2.54x109
350 42119 3.72x1010 5921 2.65x109
400 47057 3.80x1010 6539 2.73x109
450 52323 3.86x1010 7205 2.80x109
500 57901 3.90x1010 7915 2.86x109
WatereffectonNH3SCRisknowntobesignificantduetothecompetitionbetweenH2Oand
NH3inordertoadsorbonactivesitesofacatalyst[20].Sincekineticparametersatwetconditionare
alsoavailableinChaeetal.spaper,theyarecomparedinTable6.2andtheconversionofNOis
comparedforwetanddryconditionsinFig.6.3.AsdiscussedintheDumesicetal.spaper[20],itis
clearlyobservedthatNOremovalactivityishinderedbyH2Obelow400oC,butitappearsthatthe
activityisevenincreasedabovethetemperaturebecausehighertemperatureenablestoovercome
higheractivationenergiesofNOandNH3.Consequently,thewetconditionisbettertooperateathigh
temperatureinordertoreachhigherNOremovalactivity.Sincewateriscontainedintheexhaustgases
fromactualplants,themodelatwetconditionwillbemorerealisticinordertoevaluatethe
performanceofthiscatalyticreactor.
Table6.2Comparisonofkineticparametersatdryandwetconditions
100
ConversionofNO(%)
80
60
drycondition
40 wetcondition
20
0
150 250 350 450 550
Temperature(oC)
Fig.6.3ComparisonofNOconversionsatdryandwetconditions
Conclusion
NOxemissionsfromengines,incineratorandpowerplantsareoneofthemostproblematic
pollutants.SinceitiswellknownthatNOxintheexhaustgasesiseffectivelyremovedbyNH3ina
catalyticreactor,whichiscalledselectivecatalyticreduction(SCR),acatalyticfixedbedreactorwas
simulatedin2DusingCOMSOLforthereaction.ThemodelwelldescribesthetrendofNOremovalwith
respecttotemperaturewhenitiscomparedtoChaeetal.skineticmodel.ItisshownthatmuchofNO
concentrationisconsumedintheinletofthereactor,andtheNOconsumptionrateisslightlyhigher
thanthatofNH3.WhentheratioofNOandNH3isvaried,themodeldisplaysthatwiththeincreasing
ratio,thereisnoincreaseintheconversionofNObelow350oC.And,thereisaslightincreaseabove
400oCwhentheratioisbeyond1,sotheratioshouldbecontrolledtakingintoaccountNH3slipandNO
conversionatspecifictemperatures.Themodelalsoshowsthatthereisnoeffectontheconversion
withdifferentporositiesinthereactoreventhoughpressuredropandpermeabilitythroughthereactor
aredependentmuchontheporosity.Whenthekineticmodelwascalculatedfordryandwetconditions,
themodelalsoclearlyindicatesthatNOconversionisloweredbelow400oCatwetcondition,resulted
fromtheinhibitionofNH3adsorptionontoactivesitesbywateratlowtemperatures.Accordingly,itis
concludedthattheCOMSOLmodelcanbeusefullyemployedtounderstandNOandNH3reactioninthis
catalyticreactor.
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