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DieselOxidationCatalyst
Catalytic Reactions
Thedieseloxidationcatalyst(DOC)owesitsnametoitsabilitytopromoteoxidationof
severalexhaustgascomponentsbyoxygen,whichispresentinamplequantitiesindiesel
exhaust.Whenpassedoveranoxidationcatalyst,thefollowingdieselpollutantscanbe
oxidizedtoharmlessproducts,andthuscanbecontrolledusingtheDOC:
carbonmonoxide(CO),
gasphasehydrocarbons(HC),
organicfractionofdieselparticulates(SOF).
AdditionalbenefitsoftheDOCincludeoxidationofseveralnonregulated,HCderived
emissions,suchasaldehydesorPAHs,aswellasreductionoreliminationoftheodorofdiesel
exhaust.
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TheemissionreductionsintheDOCoccurthroughchemicaloxidationofpollutantsoccurring
overtheactivecatalyticsites.Theseprocessescanbedescribedbythefollowingchemical
reactions.
[Hydrocarbons]+O2=CO2+H2O
CnH2m+(n+m/2)O2=nCO2+mH2O
CO+1/2O2=CO2
(1)
(1a)
(2)
Hydrocarbonsareoxidizedtoformcarbondioxideandwatervapor,asdescribedbyreaction
(1)orinamorestoichiometricallyrigorouswaybyreaction(1a).Infact,reactions(1)and
(1a)representtwoprocesses:theoxidationofgasphaseHC,aswellastheoxidationofSOF
compounds.Reaction(2)describestheoxidationofcarbonmonoxidetocarbondioxide.
Sincecarbondioxideandwatervaporareconsideredharmless,theabovereactionsbringan
obviousemissionbenefit.
However,anoxidationcatalystwillpromoteoxidationofallcompoundsofareducing
charactersomeoftheoxidationreactionscanproduceundesirableproductsand,ineffect,be
counterproductivetothecatalystpurpose.Oxidationofsulfurdioxidetosulfurtrioxidewith
thesubsequentformationofsulfuricacid(H2SO4),describedbyreactions(3)and(4),is
perhapsthemostimportantoftheseprocesses.
2SO2+O2=2SO3
SO3+H2O=H2SO4
(3)
(4)
Whentheexhaustgasesaredischargedfromthetailpipeandmixedwithair,eitherinthe
environmentorinthedilutiontunnelwhichisusedforparticulatemattersampling,their
temperaturedecreases.UndersuchconditionsthegaseousH2SO4combineswithwater
moleculesandnucleatesforming(liquid)particlescomposedofhydratedsulfuricacid.This
material,calledsulfateparticulates,contributestothetotalparticulatematteremissionsfrom
theengine.Catalyticformationofsulfates,especiallyinconjunctionwithhighsulfurcontent
dieselfuel,cansignificantlyincreasethetotalPMemissionsand,thus,becomeprohibitivefor
thecatalystapplication.
OxidationofNOtoNO2isanotherreactionwhichmaybeconsideredundesirableinsome
applications:
NO+1/2O2=NO2
(5)
ConcernshavebeenraisedthatthecatalyticgenerationofNO2whichismoretoxicthanNO
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cancreateairqualityproblemsinsomeapplications,forinstanceinunderground
mines[Ambs1993].Duetothethermodynamicequilibriumofreaction(5),whichisreachedin
theatmosphereaftersometimeregardlessoftheoriginalcompositionofNOx,theoxidation
ofNOisoflessconcerninmostsurfaceapplications.Interestinglyenough,nitrogendioxide
canbeeffectivelyusedtofacilitatetheregenerationofdieselparticulatefiltersortoenhance
theperformanceofcertaintypesofSCRcatalysts.IncreasedNO2levelsmayresultfromthe
useofthesedevices.
Thereactionmechanismindieseloxidationcatalystsisexplainedbythepresenceofactive
catalyticsitesonthesurfaceofthecatalystcarrier,thathavetheabilitytoadsorboxygen.In
general,thecatalyticoxidationreactionincludesthefollowingthreestages:
i. oxygenisbondedtoacatalyticsite,
ii. reactants,suchasCOandhydrocarbons,diffusetothesurfaceandreactwiththe
bondedoxygen,and
iii. reactionproducts,suchasCO2andwatervapor,desorbfromthecatalyticsiteand
diffusetothebulkoftheexhaustgas.
Catalytic
Components
Comments
Oxidation of
gases & SOF
Noble metals
(Pt, Pt/Pd)
Cracking and/or
oxidation of SOF
Base metals
(e.g., cerium)
Washcoat storage
of HCs
Zeolites
Platinum
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Inadditiontocatalyticoxidation,importantprocessesthataffectthecatalystperformance
includecatalyticcrackingand/orpartialoxidationoflongchainhydrocarbons,aswellas
storageandreleaseofgascomponentsforinstanceHCorSO2fromthewashcoat.
NobleMetals.Catalyticoxidationofgasesispromotedbypreciousmetals,withplatinum
onaluminawashcoat(Pt/Al2O3)beingthemostbasicDOCformulation.Preciousmetal
formulationsareusedwhenevertheDOCisrequiredtoreduceCO&HCemissions.In
applicationsthatrequirehighCOconversionsatlowexhausttemperatures,highPtloadings
areusedontheorderof50100g/ft3andabove.
Beforetheintroductionofultralowsulfurdiesel(ULSD)fuels,Ptwaspracticallytheonly
noblemetalusedindieseloxidationcatalysts.WithULSDfuels,Ptcanbepartially
substitutedbypalladium.ThefirstmassproducedPt/PdDOCswerelaunchedinEuropeon
Euro4/5passengercars.
Othernoblemetalshavealsobeensuggested,forinstancePdAualloys[Kapur2011].These
formulationsstillremainattheresearchstage.
BaseMetals.IftheroleoftheDOCistocontrolPMemissions,andnoreductionoronly
moderatereductionsofCO/HCemissionsarenecessary,abasemetalcatalystcanbeused.A
numberofbasemetalcatalystsincludingCe,Fe,V,Cu,andotherscanpromotecatalytic
crackingandpartialoxidationoflongchainhydrocarbonswhichconstitutetheSOFfraction
ofdieselparticulates.However,basemetalsusuallyhavelowactivityfortheoxidationofgas
phasehydrocarbonsandCO.ToprovidesomedegreeofcontrolforCO/HCemissionsandthe
dieselodor,manybasemetalcatalystsalsoincludealowloadingofPt,typicallyontheorder
of110g/ft3.
Asanalternativeapproach,catalystsforPMemissioncontrolcanutilizelowtomedium
platinumloadingsratherthanbasemetals.
WashcoatStorage.Severalcomponentsofthegasphasecanbestoredinthecatalyst
washcoat,andthenreleasedbackintotheexhaustgas.Thereleasemaybetriggeredbya
changeintemperatureorotherexhaustgasconditions.Thestorageandreleasephenomena
canhaveasignificantimpactontheDOCperformance.Storageandreleasephenomenaare
notalwayseasytodetecttheyareoftenoverlookedduringcatalysttesting.Theroleof
storageandreleasemaybecomeapparentonlyaftermanyrepetitionsofthetest.
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Storageandreleasephenomenacanbecounterproductiveorbeneficialforthecatalyst
performance.Anexampleofacounterproductiveprocessisthewashcoatstorageofsulfur
dioxide.CatalystswithanaffinityforSO2storagetendtoproducemoresulfateparticulates
and,thus,belesseffective(orevenineffective)incontrollingdieselPMemissions.
Washcoatstorageandreleaseofhydrocarbons,ontheotherhand,canbeutilizedtoenhance
coldstartperformanceofdieseloxidationcatalysts.Zeolites,optimizedtoeffectivelyadsorb
dieselexhaustHCspecies,canbeaddedtothewashcoatformulationtotrapHCsatlow
temperatures,whenthecatalystisstillinactive.Oncethetemperatureincreasesabovethe
catalystlightoff,thestoredHCspeciesarereleasedfromthewashcoatandcatalytically
oxidized.Anaddedbenefitofthisapproachisthereductionofdieselexhaustodor
immediatelyafterenginestartup.ZeolitebasedHCtrapshavebecomeacommon
componentofDOCwashcoatinbothlightandheavydutyapplications.HCstorageinthe
washcoatalsoplaysaroleinSOFandNO/NO2conversion,evenwithwashcoatsthatdonot
containHCtraps.
Theeffectofthevariouscatalystcomponents(washcoatandpreciousmetals)oncatalyst
performanceisdiscussedinthefollowingsections.FurtherdetailsonDOCformulationscan
befoundinthepaperoncommercialcatalysts.
CO & HC Performance
Thedieseloxidationcatalystisveryeffectiveincontrollingcarbonmonoxideand
hydrocarbonemissionsfromdieselengines,includingthePAHandhydrocarbonderivatives
suchasaldehydes.Figure1illustratescatalystperformanceasafunctionoftemperature.The
catalystshowsnoactivityatlowexhaustgastemperatures.Asthetemperatureincreases,so
doestheoxidationrateofCOandHC.Athightemperaturesthecatalystperformance
stabilizestoformthecharacteristicplateauonthelightoffcurve.Itshouldbenotedthatthe
highCO&HCconversionsandlightoffbehaviorinFigure1aretypicalfornoblemetal
catalysts,whilebasemetalDOCsaregenerallylessactive.Formostcatalystsystems,
includingtheclassicPt/Al2O3,theconversionofcarbonmonoxideishigherthanthatof
hydrocarbonsatanygiventemperature.
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ThehightemperatureconversionrateforCOorHC,ortheheightoftheplateau,dependson
themasstransferconditionsinthecatalyst.Consequently,itcanbeincreasedordecreasedby
changingfactorswhichaffecteitherthemasstransfercoefficientorthemasstransfersurface
area.Forexample,themaximumconversionofCOorHCwillincreasewhenalargercatalyst
orahighercelldensitysubstrateisused.Infact,thehightemperatureconversionefficiency
canbebroughtnear100%byenlargingthecatalystsize.Ifneeded,theconversionefficiency
canbelimitedbyusingasmallercatalyst,oroneofalowercelldensity(largercells).
Thelightofftemperature,ontheotherhand,dependsmainlyonthechemicalreaction
kineticsinthecatalyst.Therefore,itisinfluencedprimarilybythecatalystnoble
metal/washcoatsystem.Theoverallperformanceofacatalystsystem,asmeasuredon
standardemissiontestcycles,is,thus,acombinedresultoftheappliedcatalysttechnology
andthesubstrategeometry.
GasCompositionEffects.Inagivencatalystthereisacompetitionbetweentheoxidation
ofCOandHCspecies,causingtheconversionratesinamixtureofgases,suchasinengine
exhaust,tobelowerthanlaboratoryconversionsdeterminedusingpureCOgasinthe
absenceofHC,orviceversa.ThefourchartsinFigure2illustratetheeffectofCOandHC
concentrationsonthecatalyticconversionratesofbothgases[Katare2009].
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Inthefirstchart,increasingHCconcentrationfrom0to2000ppmincreasedtheCOlightoff
temperaturebymorethan40C.Similarly,inthefourthchart,increasedCOlevelshavea
detrimentaleffectonHClightoff.ItcanbealsonotedthatincreasedCOlevelshavean
adverseeffectonCOconversion,andincreasedHCshaveanegativeimpactonHC
conversion,asapparentfromtheremainingchartsinFigure2.Whiletheeffectsaregenerally
nonlinear,modelsarebeingdeveloped(dashedlinesinFigure2)thatcanpredictconversion
ratesinamixtureofgases.
Inconventionaldieselengines,COandHCconcentrationsareusuallywellbelowtheir
respectivemaximumlevelsshowninFigure2.TheinterestinDOCperformanceathigh
CO/HCconcentrationsisdrivenbyadvancedcombustionmodessuchaslowtemperature
combustion(LTC).DuringLTCcombustion,relativelyhighCOandHCemissionsmaybe
generatedatlowexhausttemperaturesandlowoxygenconcentrations,makingtheDOC
applicationverychallenging.Evenatoxygenconcentrationsandtemperaturesthatwouldbe
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normallysufficientforthecatalystlightoff,catalystsmaybedeactivatedbythehigh
concentrationsofCO/HC[Jacobs2007].Catalystmanufacturershavebeendevelopingcatalyst
formulationsforLTCapplications.Oneofthesuggestedapproacheswastoincorporate
oxygencarryingadditivesinthecatalystwashcoattoimprovetheactivityatlowoxygen/high
COconditions[Sumiya2009].
Catalystperformanceisalsoaffectedbythepresenceofothergases.Thiscouldbeillustrated
bytheexampleofhydrogenanotherspeciespresentintheexhaustgasesfromLTC
combustion.AstudyoftheimpactofH2onDOCperformancehasfoundthathydrogencould
actuallyimprovethecatalystlightoffperformance[Katare2009].AdditionofH2tothe
feedgasatamolarCO/H2ratioofabout3inalaboratoryflowreactordecreasedtheCOand
HClightofftemperaturebyabout20C,Figure3.
Pt&PdFormulations.Amongthetwocommonoxidationcatalystsplatinumand
palladiumPtismostactivefortheoxidationofCOandHCindieselexhaust,asillustratedin
Figure4[Harayama1992].COemissionswiththePtcatalystwerelessthanahalfofthosewith
thePdcatalyst.Alsothehydrocarbonemissionswerelowerwhentheplatinumcatalystwas
used,althoughtheperformancedifferencebetweenPtandPdwassmaller.
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LoweractivityofPdindieselexhausthasbeenconfirmedbyanumberofauthors[Kawanami
1998][Majewski1995].OneofthereasonsforthelowactivityofPdcatalystsisthehigher
susceptibilityofpalladiumtosulfurpoisoning.Inapplicationswithultralowsulfurfuels,Pt
canbepartiallysubstitutedbyPd,uptoabout30%bymass.
Evenwithultralowsulfurfuels,Pt/PdformulationstendtoshowsomewhatlowerCO/HC
conversioncomparedtoPtonlycatalysts[Makino2006].However,thepresenceofPdwas
reportedtoimprovethecatalystdurability,withagedPt/Pdcatalystsperformingequallyor
betterthanPtonlycatalysts.Thedurabilityimprovementmaybeexplainedbybettercatalyst
dispersionandlowerpreciousmetalparticlesizesinthePt/Pdsystem.Inthesamestudy,the
Pt/Pdparticlesizesweremeasuredat1030nm(basedonTEMimaging),comparedto3040
nmforPtonlyformulations[Makino2006].Duetothepricedifferencebetweenthemetals,
substitutionofPtbyPdmayproduceacostsaving.
TheloweractivityofPdindieselapplicationsisquiteoppositetoitsactivityingasoline
exhaust.Palladium,duetosuperiorlowtemperaturehydrocarbonactivity,iscommonlyused
inclosecoupledlightoffcatalystsingasolinecars[Eastwood2000].Thedifferenceinactivity
isexplainedbydifferentchemicalcompositionofgasolineanddieselexhausthydrocarbons.
GasolineHCshaveshortcarbonchainsandcontainmanyunsaturatedcompounds,while
dieselhydrocarbonsarecharacterizedbylongcarbonchainsandmostlysaturatedbonds.
Theheateffectassociatedwiththeoxidationofcarbonmonoxideandhydrocarbonsisalso
differentinthegasolineanddieseloxidationcatalyst.TheoxidationofCOandHCinvolves
exothermicreactionswithsignificantreleaseofheat.Ofcourse,theheatofreactionfor
particularchemicalcompoundsisthesamewhethertheyoriginatefromdieselorgasoline
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exhaust.ThedifferenceisintheconcentrationsofCOandHC,whicharehigheringasoline
exhaustthanindieselexhaust.Asaresult,atemperatureincreaseuptoafewhundred
degreesCelsiusmaybeobservedingasolinecatalyticconverters,whilethetemperaturerise
acrossthedieselcatalystisrarelymorethan1020C.
OdorControl.TheremovalofhydrocarbonsandtheirderivativesovertheDOCalsoresults
inreductionsinthelevelsofodorindieselexhaust[Zelenka1994].Theeffectivenessof
catalystsisdifficulttoquantify,becausenouniversalmethodsexisttomeasuretheintensity
ofodors.Authorswhoworkedondevelopingsuchmethodsreporteddecreasesofthreshold
valueofdieselodorbetween317%onaheavydutyenginewitha10g/ft3Ptcatalyst,and
between5262%onalightdutyenginewitha90g/ft3Ptcatalyst[Hamm1999].
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Storageofnitratesmayoccuronsomecatalysts,causinganapparentNOxreductioneffect.
Catalystmaterialscapableofreactingwithnitrogenoxidestoformnitratesincludebarium,a
commonaluminawashcoatstabilizerinoxidationcatalysts.Sincebariumnitrateisnot
decomposingundertypicalconditionsindieselexhaust,repeatedtestingshowsadeclining
NOxactivityinthistypeofcatalyst.NOxadsorbersacatalysttechnologybasedonthistype
ofchemistryrequirealternatingadsorptionandregenerationcycles.
NOxreductionsmaybealsocausedbyreactionsbetweenNO2anddieselparticulatesorHCs
(includingHCsstoredinthewashcoat).Asreactionswithsolidparticulatesrequirealong
residencetimeinthecatalystzone,theyaremorelikelytooccurinsystemswithcatalyst
supportsthatcanprovidesomesootholdingcapacity(e.g.,ceramicfoams).
NOxIncrease.SmallNOxincreasesovertheDOCareoccasionallyreported[Yamamoto
2006],themechanismofwhichremainsunclear.ItisgenerallybelievedthatNOxcannotbe
synthesizedfromnitrogenandoxygenunderthelowpressureandtemperatureconditionsin
theexhaustsystem.Onereactionpathwaythathasbeensuggestedisviaformationofnitrated
HCspecies,followedbytheircatalyticoxidation.
NO2Formation
WhilethetotalNOxremainsessentiallyunchanged,nitrogenoxidesdoundergochemical
changesoverthedieseloxidationcatalyst.EngineoutNOxemissionsarecomposedofnitric
oxidethemainNOxcomponentandnitrogendioxide.AdditionalquantitiesofNO2maybe
generatedviacatalyticoxidationofNOaccordingtoEquation(5),resultinginincreased
NO2/NOratiosdownstreamoftheDOC.Figure5showsexampleNO2concentrationsbefore
andafterthecatalyst,plottedversusexhaustgastemperature[Ambs1993].Thedatacomes
fromoneofthefirststudiesthatidentifiedtheDOCasasourceofundesirableNO2emissions
inundergroundmines.
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7 liter Caterpillar 3304 PCNA engine rated 100 hp at 2200 rpm. High sulfur diesel fuel. 2.5 liter
diesel oxidation catalyst.
AlargeincreaseinNO2concentrationwasobservedatatemperatureofabout300C.The
nitrogendioxideconcentrationincreasedfromabout10ppmintherawexhausttoa
maximumof120ppmafterthecatalyst.Whentemperaturesapproached400C,the
NO2concentrationdecreasedtoreachpracticallyzeroatabout460C.Thatdecreasein
NO2isrelatedtothethermodynamicequilibriumofthereaction.Sincetheconcentrationof
nitricoxideduringtheexperimentwasbetween800and900ppm,theobservedmaximum
conversionefficiencyofNOtoNO2wasapproximately12%.
TheNO/NO2chemistryoveraDOCdependsonanumberoffactors,includingthecatalyst
formulationandsize,temperature,thesulfurlevelinthefuelandthecompositionofthe
exhaustgas.HigherNOconversionsareseenwithultralowsulfurfuels,asthecatalytic
oxidationofnitricoxideisinpartblockedbysulfur.NOoxidationisalsoinhibitedbyCOand
otherreductants,includingHCandsoot[Crocoll2005].
Inthepresenceofreductants,NO2inthefeedgasisbelievedtobefirstreducedtoNO.Only
afterthereductants(CO,HC)areoxidizedoverthecatalyst,theNOisreoxidizedtoNO2.It
hasbeensuggestedthattheNO2reductionsteptakesplacemostlyatthecatalystinletface
andisrelativelyindependentofspacevelocity,whilethefollowingNOoxidationoccurs
throughoutthecatalystlengthanddependsonthecatalystvolume[Katare2007].Thus,if
reductantsarepresent,theDOCmayeitherincreaseordecreaseNO2emissions.Asageneral
trend,catalyststhatareveryactiveinoxidizingCOandHCarelikelytoincrease
NO2emissions,whilecatalystoflowerCO/HCactivitymayactuallyreduceNO2.
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ExamplesofNO2activityofcatalystsonheavyandlightdutydieselenginesareshowninthe
followingfigures.ThedatainFigure6suggeststhattheNO/NO2chemistryoveraDOCcan
bealsoinfluencedbywashcoatstoragephenomena[Strots2008].Theupperchartshowsthe
NO2/NOxratiobeforeandafterthecatalyst,measuredoverthedurationoftheFTPTransient
test.ThelowerchartrepresentstheDOCinletandoutlettemperaturesduringthetest.An
activecatalystformulationwasused(designedtoincreaseNO2levelsinanSCRsystem)but
inthebeginningofthetest,untilapproximately250seconds,theDOCactuallyreduced
NO2levels.Thisreductionismostlikelyexplainedbyreactionsbetweentheengineout
NO2andhydrocarbonsstoredincatalystwashcoat,intheabsenceofNOconversiondueto
lowcatalysttemperature.Onlyaftertheinitialperiod,anetincreaseinNO2concentration
wasobserved.
ThedatainFigure7showsthatundercertainconditionsaDOCcanbeanetconsumerof
NO2[Katare2007].Thechartdepictscumulativeemissions(aswellasthecatalystinlet
temperature)measuredfromalightdutyvehicleovertheFTPtestcycle.Thecatalystaged
to120,000milesandexposedtotherelativelylowFTPtemperaturesprovidedasignificant
nitrogendioxidereduction,asapparentfromtheDOCinandDOCoutNO2lines.Inthe
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samestudy,acatalystagedto50,000milesalsoreducedNO2,buttoasmallerdegree,whilea
fresh(degreened)catalystincreasedNO2emissions.
Figure 7. Impact of Aged DOC on Cumulative NO2Emissions Over Light-Duty FTP Test
LiteraturedataoncatalystformulationsofsuppressedNO/NO2activityisscarce.Thereare
opinionsthatformulationsdevelopedforsulfatesuppressedcatalysts,oratleastsomeof
them,arealsoeffectiveinpreventingNO2formation.Publisheddatasupportsthisnotionin
thecaseofvanadium,theadditionofwhichsuppressedboththesulfatemakeandthe
NO/NO2shift[Layrer1994].
NO2Catalysts.Incertaindieselemissioncontrolsystems,increasednitrogendioxide
concentrationsaregeneratedonpurposetofacilitateparticulatefilterregenerationorSCR
reactions.Speciallyformulatedoxidationcatalystsofhighactivityareusedtogeneratethe
NO2.ToachievehighNOconversions,catalystwithPtloadingsofabout100g/ft3andabove
areoftenused.Duetothehighcostofthesecatalysts,astrongincentiveexiststousePt/Pd
formulations[Doumeki2006][Makino2006].
NOconversionefficiencyasafunctionoftemperatureoveranNO2generatingcatalystis
illustratedinFigure8.Theparticularcurves,generatedinalaboratoryflowreactor,illustrate
theeffectofthefeedgascompositionandcatalystconditionsonNOoxidation[Katare2007a].
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Inallcases,beginningataround275325CtheNOconversionefficiencydeclinesdueto
thermodynamicconstrains.ThereactionofNOoxidation,Equation(5),hasanequilibrium
whichshiftstotheleftsideoftheequationathighertemperatures,asindicatedbythe
EquilibriumcurveinFigure8(theexactlocationofthecurvedependsonthe
concentrationsofreactingspeciesintheexhaustgas).
ThemaximumNOconversionstronglydependsonthecompositionofthegas.Aconversion
inexcessof90%wasreachedwithdryNO+O2gas,whileadditionofwaterhadaninhibiting
effect(solidlinesinFigure8).ThereactionwasfurtherinhibitedbyCOandHC.Amaximum
conversionofonlyabout50%wasobservedwith0.2%COand0.2%HC(and4.5%H2O).
Whilesimilarfeedgaswasusedinallthreeexperimentsshownindashedlines,afurtherdrop
inNO2activitywasseenafteragingthecatalystwithphosphorus(theothercatalystswere
agedwithsulfuronly)andaftercoatingthecatalystwithsoot.Inthelattercase,NO2was
likelyconsumedviareactionswiththesoot.
Inreallifedieselengineapplications,agedNO2catalyststypicallyhavemaximumefficiencies
oflessthan50%[Makino2006].NO2/NOxratiosof3050%havebeenmeasureddownstream
ofvarioustypesofcatalyticparticulatefilters[LeTavac2002][Ayala2001].The
NO/NO2reactionisfurtherdiscussedinDieselFilterRegenerationpaper.
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Whileliteraturereportsexistthatshowbothsmalldecreasesandsmallincreasesofsolid,
insolublePMintheDOC,itisgenerallyagreedthatcarbonaceousparticulatespassvirtually
unchangedthroughoxidationcatalysts[Eastwood2000].Consideringtheirlargesizein
comparisontogasmolecules,carbonparticlesarenotlikelytocomeintocontactwiththe
catalyst.Eveniftheydo,boththeresidencetimeandthetemperatureindieselexhaustare
insufficientforanysignificantoxidationrates.
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Theorganicfraction(SOF)ofdieselparticulates,composedofheavyhydrocarbons,isvery
effectivelyoxidizedinthecatalyst.SOFremovalisthemajoreffectcontributingtoadecrease
intheTPMemissionsoverthedieseloxidationcatalyst.SOFoxidationissimilartothe
oxidationofgasphasehydrocarbons,i.e.,acertaintemperaturehastobereachedforthe
catalysttolightoff(Figure1).Afterthelightofftemperatureisreached,theconversionof
SOFshowslittlechangewithfurthertemperatureincrease.
Thesulfatefractionofdieselparticulates(SO4)isincreasedintheDOCduetotheoxidation
ofSO2withsubsequentformationofsulfuricacid,Equation(3)andEquation(4).Thisisa
counterproductiveprocesscausinganincreaseinTPMemissions.Theintensityofsulfate
makeincreaseswithexhaustgastemperatureandbecomescriticalatabout400C.Withhigh
sulfurfuels,theDOCislikelytoincreaseTPMemissionsduetosulfateformation.Withlow
sulfurfuels(approximately300500ppmS),specialcatalystformulationsarenecessaryto
suppressthatprocessand,thus,tomakethedieseloxidationcatalystaviablePMreduction
approach.OnlyULSDfuelseliminatethesulfateproblem,allowingformostflexibilityin
dieseloxidationcatalystformulation.
TheneteffectoftheDOCondieselparticulatematterisacombinationoftheSOFandSO4
reactivities,asitwasshowninFigure9.ThecatalyticoxidationofSOFcontributestothe
decreaseinTPMwhilethegenerationofsulfatesincreasesparticulateemissions.Thedesired
SOFeffectprevailsatlowtemperatures.Inpractice,ifsulfurispresentinthefuel,thereis
alwaysatemperatureabovewhichanincreaseofPMemissionswillbeobserved.
Selectivedieselcatalystsspecificallyoptimizedforparticulatemattercontrolcantolerate
certainsulfurlevelsinthefuelandstillcontrolPMemissions.Theseselectiveformulations,
however,compromisethecatalystactivity,resultinginlesseffectivegasphaseHCandCO
control.Onlyultralowsulfurfuelscaneliminatetheseconstrainsandmaximizethebenefits
ofcatalyticemissioncontroltechnologies.
PM Emission Reduction
ThepotentialofcatalyticPMemissionreductioncriticallydependsonthecompositionof
engineoutparticulates.OnlyparticulatesofhighSOFcontents,socalledwetparticulates,
canbeeffectivelycontrolledbycatalysts.Duetodifferentcombustionsystemdesign,the
organicPMportionthatissusceptibletocatalyticoxidationvariesbetweenengines.Ina
givenengine,SOFcontentdependsontheoperatingconditions,changingfromwellabove
50%insomecasesapproaching90%atlowloadstojustafewpercentathighengineloads.
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ExampledataillustratingSOFcontentasafunctionofengineoperatingconditionswas
presentedinthepaperondieselparticulatematter.
Figure10showstypicalconversioncurvesfortotalPMandforSOFoveraPtandaPdcatalyst
usingdieselfuelof300ppmS[Matsumoto2003].BothcatalystsareeffectiveinreducingPM
emissionsatlowertemperatures(withthePtcatalystbeingactiveatlowertemperaturesthan
thePdformulationduetoitsbetterHC/SOFlightoff).Astemperaturesincrease,thePM
conversiondrops,despitetherelativelysteadySOFconversion.InthecaseofthePtcatalyst,
whichisveryactiveintheoxidationofSO2,thedropinefficiencyismainlycausedbythe
formationofsulfates.TheactivePtformulationinFigure10becomesanetPMproducerfrom
justabove250C.InthecaseofthePdcatalystwithitslowSO2activitythedecreasing
efficiencyiscausedmainlybythedecreasingSOFfraction,withsulfatemakeplayingacertain
roleathighertemperatures(450500C).
TheaverageSOFcontentoveranenginetestcycledependsonitsaverageloadfactor.Cold
testcyclesoflowengineloadswillproducewetparticulates,whichcanbeeffectively
controlledbytheDOC(aslongasthetemperaturesaresufficientforthecatalysttolightoff).
Hot,highlyloadedtestcycles,ontheotherhand,tendtoproducedryparticulates,whichare
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noteffectivelycontrolledusingtheDOC.Wetparticulatescollectedoverlightlyloadedtest
cyclescanhaveSOFcontentsofmorethan50%,whichcanbealmostentirelyremovedby
thecatalyst.Indeed,PMremovalefficienciesof50%andmorehavebeenobservedwithdiesel
carstestedontherelativelycoldECE+EUDCcycleusingfuelsoflessthan500ppm
sulfur[Kharas1998].
Inheavydutyapplications(usingthesame500ppmsulfurfuel),thePMemissionreduction
potentialisinmostcaseslimitedto2030%.IntheUSEPAUrbanBusRetrofitRebuild
(UBRR)program,anumberofcatalystswerecertifiedtoachievea25%PMemission
reductionoverthe(mediumload)FTPtransientcycleontwostrokeengines.Mostofthese
catalystswerenotabletoachievethesame25%PMemissionreductiononfourstroke
engines,whichproducePMemissionoflowerSOFcontentthanthetwostroketechnology.
Evenwhentestedonrathercoldtestcycles,suchastheJapanese13mode,PMemissionfrom
heavydutyenginescouldbereducedbyonlyabout20%,duetohighsulfateproduction
duringthehightemperaturemodes[Mogi1999].Theoxidationcatalysttechnologyhasnot
beensuccessfulincontrollingdieselparticulatesfromveryhotapplicationsandtestcycles,
suchastheR49,ESCandETC.ImprovedperformanceandhigherPMemissionreductions
dependingontheSOFlevelsmaybepossiblewithultralowsulfurdieselfuels.
Finally,itshouldberememberedthatdieselparticulatesaresometimesdefinedindifferent
ways,whichmayhaveimplicationsforcatalyticcontroltechnologies.Insomeoccupational
healthregulations,dieselparticulatesaredeterminedaselementalcarbon(EC).Insuchcase,
theDOCtechnologywouldbeineffectiveincontrollingPMemissions.Incertainother
regulations,dieselparticulatesaredefinedastotalcarbon(TC),i.e.,includingtheSOFpart,
butexcludingsulfates.Inthiscase,catalystscanbeaveryeffectivecontrolapproach,even
withsulfurcontainingfuels,assulfatemakeisnolongeranissue.
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thecatalystperformancemaybealsopronetoparticleblowoff,suchasduringengine
transients.
ThemarginallevelofperformanceorthelackthereofoftheconventionalDOCtooxidize
andreduceemissionsofthesolid,carbonaceousPMfraction(a.k.a.soot)isattributedtothe
insufficientresidencetimeoftheparticleswithinthecatalystandtotheirpoorcontactwith
thecatalystsites.Duetotheirlargermassandsize,solidparticlesarelesslikelytoenterthe
porenetworkinthewashcoat/substratesystemthangasmolecules.Iftheydo,moretimeis
requiredforthecatalyticreactionstocomplete.
CatalystscanbeoptimizedforimprovedsolidPMconversionthroughincreasingtheir
capacitytotrapandstore(atleasttemporarily)solidparticles.Forinstance,washcoatand
substrateoptimizationthatwouldmakemoresubstrateporosityavailabletotheexhaustgas
couldresultinmorestorageandoxidationofsolidparticles.Amongthetwocatalystsin
Figure11,catalystBwasaconventionalDOC,whilethecoatingofcatalystCwasoptimized
forsolidcarbonconversion[Matsumoto2003].Itisclearthatthewashcoatoptimizationindeed
increasedtheconversionofsolidPM.Itisalsointerestingtonotethatthesolidcarbon
conversionwasimprovedwithbothcatalystsinthepresenceofahigherSOFfraction(the
threeSOFcontentpointsrepresentmeasurementsonthreedifferentengines).
TheresultsinFigure11representmeasurementsovertheJapanese13modecycle,with
catalystinlettemperaturesincreasingfromapproximately100Cto450Cduringthetest.In
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thesamestudy[Matsumoto2003],steadystatemeasurementswereperformedat500Cusing
catalystscoatedondifferentsubstrates,Table2.Atthattemperature,thePMhadaverylow
SOFcontentof5%.Acorrelationwasfoundbetweenthesubstrateporosityandconversionof
carbonparticulatessolidPMconversionofnearly30%wasmeasuredwithsubstrateofthe
highest,65%porosity.Lowerwashcoatloadingshadtobeusedonsubstratesoflowercell
densityandhigherporositytoavoidfillingtheporositywithwashcoat.Thismighthave
causedthetradeoffbetweenthesolidPMandthegasphaseperformance,thelatter
illustratedbytheHCconversionratesinthetable.
Table 2
Effect of Substrate Porosity on Solid PM Conversion at 500C
Catalyst B Catalyst C Catalyst D Catalyst E
Call Density, cpsi
400
400
300
300
Porosity, %
35
35
59
65
12
12
24
22
Solid PM Conversion
0%
0%
20%
29%
90%
83%
80%
HC Conversion
Note:
Steady-state engine test @500C.
PM composition: 5% SOF, 5% sulfate (30 ppm S fuel).
All catalysts 2 g/L Pt, but different washcoat loadings.
Catalyst designations consistent with Figure 11.
TheresultsinFigure11andinTable2implicatethatsolidparticletrappingwithinthe
catalystmayinvolveacombinationoftwomechanisms[Matsumoto2003].Atlower
temperatures,SOFandheaviergasphaseHCsmaybecondensingonthecatalystsurface,
facilitatingbetteradhesionofcarbonparticles,Figure12.Inaddition,HCoxidationwhenthe
temperatureincreasesmaycausealocaltemperatureincrease,enablingfasteroxidationrates
ofthecarbon(viaeithertheNO2orO2mechanisms).Athightemperatures,theSOFcontent
islowanditseffectisnotsignificant,withparticletrappingintheporesbecomingthe
dominantmechanism(Figure12,righthandside).
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Moresophisticated,specialcatalystsubstrateshave
beendevelopedthatcancaptureandstorecarbon
particles,whichareoxidizedbyNO2generatedinan
upstreamcatalyst.Thesespecializeddieseloxidationcatalystsystemsarereferredto
asparticleoxidationcatalysts.
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catalysts[Farrauto1997]orzeolitecatalysts(arareearthmetalexchangedzeoliteoxidation
catalyst,notoptimizedforHCstorage)[Standt1995].Thecracked,shortchainHCproducts
arethenmeasuredasgasphaseHCs,andnotapartofSOF.ThisnonoxidationSOFremoval
pathseemstobealsoconfirmedbytheobservationthatwhilecatalyticoxidationofCOand
gasphaseHCincreaseswithplatinumloading,theconversionofSOFisrelatively
independentfromPtload[Mogi1999][Farrauto1997].
TheexplanationofthefateofSOFoverthedieseloxidationcatalystbyacombinationof
catalyticoxidationandcatalyticcrackingisstillnotentirelysufficient.Anotherimportant
mechanismthatinfluencestheDOCperformanceisHCstorageandreleaseinthewashcoat.
HCstorageeffectsareseenmostlyatlowcatalysttemperatures.Resultsoflaboratory
experimentsonstorageandreleaseusingfeedgaseswithdifferentHCsareillustratedin
Figure13[Adams1996].Adsorptionofsomegasesinthewashcoat,especiallythoseofhigher
boilingpointsuchasdecaneortoluene,resultedinapparentconversionefficiencyofasmuch
as90%atverylowtemperatures.Astemperatureincreased,theHCsweredesorbed,butthe
desorptiontemperaturesvariedamongspecies.Toluenewasalmostentirelydesorbedat
70C,whilethedesorptionofdecaneextendedthrough190C.ItwasalsoobservedthatHCs
andwateradsorbedincompetition.
SinceHCsinFigure13werereleasedfromthewashcoatmostlybelowthelightoff
temperature,therewaslittleornoemissionbenefitduetothestorageeffect.Catalyst
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manufacturershavedevelopedmaterialsthatareabletoholdtheadsorbedHCsintohigher
temperatures,say250C,inordertocatalyticallyoxidizethemoncereleasedfromthe
washcoat.Thesematerials,whichtypicallyarevarioustypesofzeolites,areknown
ashydrocarbontraps.Hydrocarbontrapseventuallyreachtheirsaturation,thuslosingtheir
effectivenessinasteadystateexperiment,butmaybeveryeffectiveinenhancingPM
conversionandimprovingtheapparentHClightoffovertransienttestcycles.Many
commercialdieselcatalystsintroducedsincethelate1990sforbothlightandheavyduty
applicationsincludezeolitesoptimizedforHCtrapping[Sawyer1998][Yavuz2001].
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thatthesulfateparticulatesincludeallofthesulfuricacidandthehydrationwater.Thewater
contributiondependsontheassumedhydrationratio,asdiscussedintheDieselParticulate
Matterpaper.Thermodynamicallyfavoredratioduringsulfateformationis2.67,while
typicalhydrationratioinsamplescollectedandpreconditionedforTPMdeterminationis
about7.Equation(6)providesresultsing/kWh,Equation(10)producesconcentrationsin
kg/m3.Themassandvolume(m,V)arebrakeenergyspecificmagnitudes(perkWh).
msulfate=KmFwSMsulfate/MS
(6)
Msulfate=MH SO +xMH O
2 4
2
(7)
mexh=mF(1+RA/F)
(8)
Vexh=mexh/exh
(9)
csulfate=msulfate/Vexh
(10)
where:
KfractionalconversionofSO2toSO3
mmass,kg/kWh
wSweightfractionofsulfurinfuel
Mmolarmass,kg/kmole
Vvolume,m3/kWh
RA/Fengineairfuelratio,kg/kg
exhexhaustgasdensity,kg/m3
xhydrationratioofH2SO4insulfateparticulates
cconcentrationintheexhaustgas,kg/m3
Indexes:FfuelSsulfursulfatesulfateparticulatesexhexhaustgas
Averyillustrativeexperimentalresultsonthedependenceofsulfateformationonthefuel
qualityareshowninFigure14,whichcomparesthetotalparticulatematteremissionswitha
platinumbasednonselectiveoxidationcatalystforthreedifferentdieselfuelscontaining
1500ppm,500ppm,and25ppmofsulfur[Smedler1995].Forthesakeofclarity,the
compositionofPM(carbon,sulfate,SOF)isnotshowninthegraph.Theparticulatesare
composedmostlyofSOFatthelowest,130C,temperature.Athighertemperatures,the
particulatesarecomposedprimarilyofsulfates.Thecarbonfractionisnotmorethan0.01
g/kWhatanycatalysttemperature.
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AsubstantialincreaseintheTPMemissionswasobservedwiththe1500ppmSfuel.
Obviously,thenonselectivecatalystwastotallyinappropriateforthisapplication.Whenused
withthelowsulfur(500ppmS)fuel,thenonselectivecatalyststillincreasedtheengineout
PMemissionsseveraltimes,especiallyathighertemperatures,duetosulfatemake.Onlywith
the25ppmSfuelthecatalystsulfatemakewasalmostinsignificantovertheentire
temperaturerange.Hence,anonselectiveoxidationcatalystcanbeusedonlyinconjunction
withfuelsofverylowsulfurlevels,withoutincreasingPMemissions.
ThegenerationofsulfatesinFigure14increaseswithtemperatureuptoabout450C,where
itexhibitsamaximum.Thismaximumcanbeexplainedbythethermodynamicequilibrium
oftheoxidationofSO2toSO3,reactionEquation(3).Athightemperaturesthereaction
equilibriumshiftstotheleftsideoftheequation,i.e.,thehigherthetemperaturetheless
SO2canbeoxidizedandlessSO3isproduced.Anequilibriumcurve,computedforconditions
typicalfordieselexhaust,ispresentedinFigure15[Henk1992].
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Theequilibriumisexpressedintermsofmaximum(equilibrium)conversionofsulfurdioxide
asafunctionoftemperature.ThedecliningequilibriumconversionofSO2isinagreement
withexperimentaldatawhichtypicallyshowagradualincreaseofPMemissionswith
temperatureuptoabout400C.Atthesetemperaturesthesulfateformationincreasesdueto
theincreasedreactionkineticsathighertemperatures.Afterthetemperaturereaches400
450C,thereactionequilibriumlimitstherateofsulfateformationand,despiteveryhigh
reactionrates,theoverallrateofsulfateformationdecreases.
InadditiontothesteadystateoxidationofSO2withthefollowingformationofsulfuricacid,
asdescribedbyequations(3)and(4),storageandreleaseofsulfatesfromthewashcoatcan
occurinthedieseloxidationcatalyst.SulfurcanbestoredeitherasSO2orasaluminum
sulfateonalumina,orothermaterials,usedasthecatalystwashcoat.Atacertain
temperature,thestoredmaterialcanbereleasedandconvertedtosulfate.Thesulfurrelease
canbedescribedbythefollowingreactions:
Al2(SO4)3=Al2O3+3SO3
Al2O3SO2=Al2O3+SO2
(11)
(12)
Somestudiesmeasuredthequantityofstoredsulfuratuptoaround2%ofthecatalyst
washcoatmass[Henk1992].Consideringtypicalcatalystsizesandwashcoatloads,thesulfur
storagecaninfluencethesulfateresponseofthedieselcatalyst.
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Figure16showstheresultsof12emissiontestrepetitionsofacatalystequippeddieselengine
overtheUSheavydutytransientcycle[Harayama1992].Thesulfurcontentinthetestfuelwas
400ppmbyweight.AnincreaseofTPMemissionswasrecordedoverthesubsequenttests.
Theparticulateanalysisindicatedthatthesulfateparticulateswereincreasingwiththetest
repetitions.InthefirsttestthecatalystwasreducingthePMemissionsbyabout25%.Inthe
lasttest,thePMemissionswereincreasedbyabout30%,relativetotheenginebaseline.
Apparently,sulfateswerestoredinthecatalystwashcoatbutwerenotreleasedunderthetest
conditions.Duringthefirsttests,sulfuroxideswereadsorbedinthewashcoatand,thus,
removedfromthesystem.AnetdecreaseofTPMemissionswasobserved.Asthecatalyst
washcoatgraduallysaturated,moresulfateparticulatesappearedafterthecatalyst,eventually
leadingtoanincreaseinthePMemissions.
Theaboveexampleshouldberememberedwheneveremissionperformanceoffreshcatalysts
istested.Itisimportanttopreconditionordegreenfreshcatalystsbeforetesting.Ifthe
degreeningisnotproperlydone,thetestresultsmaybeverymisleading.
Thesulfurstoragephenomenawereextensivelystudiedinlaboratories.Acorrelationwas
foundbetweenthecatalystsulfurstoragecapacityandtheformationofsulfateparticulates.
Thecatalystwashcoatwhichstoresthehighestamountofsulfurisalumina.ThePt/alumina
catalystisknownasthemostactiveoxidationcatalyst,veryeffectiveforoxidationofSOFbut
alsogeneratingthehighestsulfateparticulateemissions.Thesulfurretentioninthe
Pt/aluminacatalystmaybecloseto2%ofthewashcoatmass.Thealuminasurfaceareaisnot
sufficientforamonolayeradsorptionofthatquantityofsulfur.Thestoragemechanismmust
alsoinvolvesomeformationofbulkaluminumsulfates.Catalystsystemswithlowersulfur
storagecapacityalsoexhibitlowerratesofsulfateparticulateformation.Examplesofsuch
systemsarePtonsilicaorPdonsilicawithsulfurretentiontypicallylessthan0.05%ofthe
washcoatmass.
Inspiteofthecorrelationbetweensulfurstorageandthecatalystsulfatemake,itisnotclear
ifthesulfatereleaseisanimportantcontributiontosulfateemissions.Itisdifficulttosetup
anexperimentthatwouldconvincinglyseparatethecontributionofthesteadystate
SO2oxidationfromthatofthesulfatereleasefromthewashcoat.Thesetwoprocessesarealso
interconnectedbytheequilibriumoftheSO2oxidation.IfSO3isreleasedfromthewashcoat
athighertemperatures,itinfluencestheequilibriumofreaction(3)preventingmore
SO2frombeingoxidized.
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SelectiveCatalysts.Catalystselectivitywasthefocusinthedesignofcatalyststocontrol
particulateemissionsfromdieselenginesoperatedwithlowsulfurfuels.Thereisalwaysa
tradeoffbetweenthecatalystactivityanditsselectivity.Acatalystwithasuppressedsulfur
dioxideactivitywillalsoshowlowerHCandCOconversions.Andviceversa,catalystswhich
aremostactiveintheoxidationofCOandHC(andSOF)generatemostsulfateparticulates.
TheobjectiveintheselectivecatalystdesignwastominimizetheCO/HCactivitypenaltyfora
givensulfatesuppression.Thefollowingapproacheshadbeenusedtodesignselectivediesel
catalysts:
specialcatalystpreparationmethodssuchasprecalcination
selectionandloadingofthenoblemetal
selectionofwashcoatmaterials
sulfatesuppressingwashcoatadditives.
Thermaltreatment(calcination)ofthefinishedPt/Al2O3catalystimprovesitsselectivity.
Duringthatprocesssomesinteringofplatinumoccurs.Apparently,thefinerdispersionsofPt
favortheoxidationofSO2toSO3,whilelargerPtgrainsmakethecatalystmoreselective.
Platinumcatalystsaremuchmoreactiveintheoxidationofsulfurdioxidethanpalladium
basedsystems.Theuseofpalladiumratherthanplatinum,orPt/Pdblends,hadbeen
suggestedasameansofsulfatesuppression.Theadditionofrhodiumwasalsofoundeffective
incontrollingsulfateformation.TheactivityofplatinumtowardsSO2oxidationdependson
thePtloadingtoamuchhigherdegreethanotherfunctionsofthecatalyst.Someselective
dieseloxidationcatalystsusedplatinumatverylowloadingsof0.52g/ft3.
Washcoatformulationcanstronglyinfluencethecatalystperformance.Severalnonsulfating,
chemicallyinertoxides,suchassilica,titania,andzirconia,canbeusedtosuppressthe
sulfate.Somewashcoatoxides,suchasceria,exhibitcatalyticpropertiesoftheirownandcan
reduceSOFemissionevenwithoutthepresenceofnoblemetals.
Variousbasemetaloxides(V,Mo,Nb,...)canbeaddedtothecatalystwashcoattoinhibitthe
oxidationofSO2.Vanadiumoxide,whichhasbeenidentifiedasoneofthemosteffective
sulfatesuppressingadditives[Wyatt1993],wasusedinsomecommercialdieseloxidation
catalysts(andstillisinmarketswithhighersulfurfuels).
Theadditionofasulfatesuppressingagentmayalsohaveanegativeimpactoncatalyst
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durability.Theexactmechanismvariesfromsystemtosystem,butaccelerationofsupport
sintering,poreblockage,andformationofinactivesurfacecompoundswiththenoblemetal
componentarepossible.
fuelsandmoreactive,noblemetalcatalyststheparticlenumbersmaybeincreaseddueto
sulfuricacidnucleation.
ExperimentswhichattempttoquantifytheimpactofDOCsonparticlenumbersmustbevery
carefullydesigned.Catalystscanbeasourceofadditionalerror,suchassamplelossdueto
thermophoreticforcesorsampleadditionsduetosolidparticleblowoffand/orreleaseof
condensatesfromthewashcoat.
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Emissions
Compound
Baseline
Cat B
Reduction
Cat D
Cat B
Cat D
Napthalene
295
159
182
46.1%
38.3%
2-Methylnapthalene
635
278
277
56.2%
56.4%
Acenapthalene
40
13
13.6
67.5%
66.0%
Acenapthene
46
25
24.4
45.7%
47.0%
Fluorene
72
29
28.9
59.7%
59.9%
169
54
56
68.0%
66.9%
Anthracene
10
2.6
2.8
74.0%
72.0%
Fluoranthene
7.7
2.6
4.9
66.2%
36.4%
Pyrene
14
6.4
64.3%
54.3%
Benzo(a)anthracene
0.22
0.05
0.18
77.3%
18.2%
Chrysene
0.51
0.16
0.33
68.6%
35.3%
Benzo(b)fluoranthene
0.26
0.09
0.12
65.4%
53.8%
Benzo(k)fluoranthene
0.15
0.05
0.08
66.7%
46.7%
Benzo(e)pyrene
0.26
0.08
0.14
69.2%
46.2%
Perylene
0.01
Indeno(123-cd)pyrene
0.13
0.04
0.07
Dibenz(ah)anthracene
0.01
Benzo(ghi)perylene
0.32
0.1
0.22
68.8%
31.3%
1290.57
568.77
597.14
55.9%
53.7%
68.5%
54.1%
Phenanthrene
Total
Average Reduction
100.0% 100.0%
69.2%
46.2%
100.0% 100.0%
Biological Activity
Theactivityofuntreatedandcatalysttreateddieselexhaustonlivingorganismscanbe
evaluatedthroughanumberofspecializedbiologicaltests.AnexampleistheAmestest,
whichwasusedbymanystudies,especiallyinthe1980sand1990s,toevaluatethemutagenic
activityofdieselexhaust.
SeveralstudiesspecificallyexaminedtheeffectoftheDOConexhaustmutagenicity,butno
consensuswaseverreached.Somestudiesreportedanincreaseofthemutagenicitywhen
dieselcatalystswereused[Hunter1990].Inotherstudies,mutagenicityofdieselexhaust
extractsdecreasedwiththeuseofdieseloxidationcatalysts.Forinstance,McClure[McClure
1992]foundthatthemutagenicityoftheSOFportionofdieselparticulatesdecreasedby41%
andthemutagenicityoftheTPMsampledecreasedby51%withaDOC.Inanotherstudy,a
DOCeliminatedAmesmutagenicityinthegasphase,butonlyslightlyreducedmutagenicity
oftheparticlephase[Westphal2012].
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Thebiologicalactivityofdieselexhaustcanbereasonablyanticipatedtodependonanumber
offactors,includingfuelproperties[Rasmussen1990],engineandcatalysttechnology,aswell
asengineoperatingconditions.Inviewofthiscomplexity,morerecenthealthstudiestendto
focusontheeffectsofagivenenginetechnologyinitsentirety[Khalek2009],ratherthan
attemptingtostudytheeffectsoftheDOCasanisolatedsystemcomponent.
References
Adams,K.M.,etal.,1996.LaboratoryScreeningofDieselOxidationCatalystsandValidationwith
VehicleTesting:TheImportanceofHydrocarbonStorage,SAETechnicalPaper
962049,doi:10.4271/962049
Ambs,J.L.,B.T.McClure,1993.TheInfluenceofOxidationCatalystsonNO2inDieselExhaust,SAE
TechnicalPaper932494,doi:10.4271/932494
Ayala,A.,Kado,N.,Okamoto,R.,2001.ARBStudyofEmissionsfromLatemodelDieselandCNG
HeavydutyTransitBuses,CaliforniaAirResourcesBoard
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