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1/26/2015

DieselOxidationCatalyst

Diesel Oxidation Catalyst


W. Addy Majewski

Abstract: Diesel oxidation catalysts promote chemical


oxidation of CO and HC as well as the SOF portion of diesel
Commercial DOC Technologies
particulates. They also oxidize sulfur dioxide which is
present in diesel exhaust from the combustion of sulfur
Particle Oxidation Catalysts
containing fuels. The oxidation of SO2leads to the
generation of sulfate particulates and may significantly
increase total particulate emissions despite the decrease of
the SOF fraction. Modern diesel oxidation catalysts are
designed to be selective, i.e., to obtain a compromise between sufficiently high HC and SOF activity and
acceptably low SO2activity.
Catalytic Reactions
Catalyst Types and Functionality
CO & HC Performance
Nitrogen Oxides Performance
Particulate Matter Performance
Sulfate Formation & DOC Selectivity
Effect on Unregulated Emissions

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.

Catalyst Types and Functionality


Thefunctionalityofthedieseloxidationcatalystisnotlimitedtocatalyticoxidation.
AdvancedDOCsincludecomponentsthatpromoteotherreactionsandprocesses,themost
importantofwhicharesummarizedinTable1.DifferenttypesofDOCsmayshowadifferent
activityinrespecttovariouscomponentsofdieselexhaust.Therefore,thetypesofcatalysts
andtheirfunctionsshouldbeintroducedbeforewediscussDOCperformance.
Table 1
Diesel Oxidation Catalyst Functionality
Functionality

Catalytic
Components

Comments

Oxidation of
gases & SOF

Noble metals
(Pt, Pt/Pd)

High Pt loadings required for CO & HC oxidation, especially at low


temperatures.

Cracking and/or
oxidation of SOF

Base metals
(e.g., cerium)

Base metal catalysts (often including a low Pt loading) are effective


for PM emission control, especially in high SOF engines.

Washcoat storage
of HCs

Zeolites

Zeolite HC traps are commonly included in DOC washcoats to


improve cold start performance.

Lean NOx activity

Platinum

Small NOx reductions possible at low-to-moderate temperatures,


but typically not required in commercial DOCs.

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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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Figure 1. Conversion of CO and HC in Diesel Oxidation Catalyst

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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Figure 2. Effect of CO & HC Concentration on Light-Off Temperature


Solid lines: data (laboratory flow gas reactor), dashed lines: model. Propylene as HC.
Catalyst: 400 cpsi, washcoat (containing zeolite) 1.75 g/in3, Pt/Pd 105 g/ft3, SV 30,000 h-1.
(Courtesy of Ford Motor Company)

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.

Figure 3. Effect of Hydrogen on CO & HC Light-Off Temperature


Gas composition (without/with H2): H20/257 ppm, CO 750/770 ppm, C3H61200/1480 ppm,
O25/6%, NO 100/100 ppm, H2O 3.5/3.6 %, CO26/5.8%, N2: balance. Catalyst: See note under
Figure 2.
(Courtesy of Ford Motor Company)

Pt&PdFormulations.Amongthetwocommonoxidationcatalystsplatinumand
palladiumPtismostactivefortheoxidationofCOandHCindieselexhaust,asillustratedin
Figure4[Harayama1992].COemissionswiththePtcatalystwerelessthanahalfofthosewith
thePdcatalyst.Alsothehydrocarbonemissionswerelowerwhentheplatinumcatalystwas
used,althoughtheperformancedifferencebetweenPtandPdwassmaller.

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Figure 4. Platinum and Palladium Diesel Oxidation Catalyst


6.925 liter DI turbocharged aftercooled diesel engine, 5.07 liter 400 cpsi catalyst
HD FTP Transient test, 400 ppm S fuel

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].

Nitrogen Oxides Performance


Effect on Total NOx Emissions
Inmostcases,thetotalnitrogenoxidesemissions(NOx)arenotchangedoverthediesel
oxidationcatalyst.Morecomplexcatalysttechnologies,suchasSCRcatalystsorNOx
adsorbers,arerequiredtoremoveNOxfromleanexhaust.
NOxReduction.SmallNOxreductions,usuallynotmorethanafewpercent,aresometimes
measuredoverdieseloxidationcatalysts.Thereareseveralpossibleexplanationsofsuch
activity,including:
leanNOxperformance,
storageofnitratesincatalystwashcoat,
reactionswithdieselPMorHCs.
Somecatalystsystems,includingPt/Al2O3,exhibitleanNOxperformanceviaselective
catalyticreductionofnitrogenoxidesbyhydrocarbons.Dieseloxidationformulationswhich
containcomponentswithleanNOxactivitymayfacilitatesomeNOxreduction,especiallyat
higherHC/NOxratios.Inthecaseofplatinum/aluminacatalysts,maximumleanNOx
activityoccursatlowtemperaturesofapproximately200250C.Itshouldalsobenotedthat
NOxisreducedmainlytonitrousoxide(N2O)overPtcatalysts.N2Obeingapotent
greenhousegasisnotadesirablereactionproduct.
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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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Figure 5. Concentration of NO2with Diesel Oxidation Catalyst

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.

Figure 6. DOC Impact on NO2/NOx Ratio Over FTP Transient Test


(Courtesy of Navistar Inc.)

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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Figure 8. Conversion of NO over Diesel Oxidation Catalyst

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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Particulate Matter Performance


Transformation of PM in Oxidation Catalyst
Thetotaldieselparticulatematter(TPM)emissioniscomposedofthreemajorfractions
includingthecarbonaceousparticulates,theorganicparticulates(SOF),andsulfates(SO4).
Eachofthesefractionsbehavesdifferentlyoverthedieseloxidationcatalyst.Ingeneral,the
overalleffectoftheDOConthetotalPMemissioncouldbeadecrease,aswellasanincrease.
TypicaltransformationsofthethreefractionsandtheresultingtotalPMemissionsare
schematicallyillustratedinFigure9(forthesakeofsimplicity,thedependenceofengineout
PMcompositiononexhausttemperaturehasbeenneglected).Asapparentfromthechart,
PMemissionscanbereducedbytheDOCthroughtheremovaloftheirorganicfraction
(SOF).Undercertainconditions,however,theSOFdecreasecanbemorethanoffsetbyan
increaseofsulfatePM,leadingtoanoverallincreaseinTPMemission(ifhighsulfurfuelsare
used,sulfateparticulateemissionsmaybemuchhigherthanshowninFigure9).

Figure 9. DOC Impact on PM Emissions with Sulfur Containing Fuels

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).

Figure 10. PM and SOF Conversion over Pt and Pd Catalysts


3.1 L IDI NA diesel engine @2000 rpm; 2.5 L catalyst; Pt: 2 g/L; Pd: 0.4 g/L; Fuel sulfur: 300 ppm

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.

Oxidation of Solid Carbon (Soot)


ReportsonchangesinPMcarbonfractionoverDOCsmustbealwaysapproachedwithcareful
scrutiny.Themagnitudeofchangeinmanyofsuchreportsisonthethresholdofdetection.
Measurementerrorcanbemagnifiedduetotheanalyticalmethodsthatdetermineinsolubles
onlyindirectly,bysubtractingsulfateandSOFfromtotalPM.Ifsulfuricacidreactswith
metals,suchaswithcalciumfromlubeoiladditives,theresultingsulfatesaltsmaybe
accountedforasinsolublematerial.Sincestorageofsolidparticlesonthecatalystsurfaceand
withinitsporenetworkasdiscussedbelowplaysanimportantroleinsolidPMconversion,
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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).

Figure 11. Conversion of Solid Carbon Fraction As a Function of SOF Content


JP 13-mode test using three engines of different SOF content. Two catalysts with the same
substrate (400 cpsi, 35% porosity) and noble metal (Pt = 2 g/L) but different washcoat loading
and formulation.

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

Mean Pore size, m

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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Figure 12. Schematic Representation of Particle Trapping Mechanisms on Catalyst Surface

Moresophisticated,specialcatalystsubstrateshave
beendevelopedthatcancaptureandstorecarbon

Particle Oxidation Catalysts

particles,whichareoxidizedbyNO2generatedinan
upstreamcatalyst.Thesespecializeddieseloxidationcatalystsystemsarereferredto
asparticleoxidationcatalysts.

Mechanism of SOF Removal


ToanalyzethemechanismofcatalyticremovalofSOF,oneneedstorecallagainthedefinition
ofdieselparticulatematter.DieselPMisdefinedaseverythingthatiscollectedfromdiluted
dieselexhaustgasonaninlinefilteratatemperaturenothigherthan52C.Temperaturesin
therawexhaustandinthecatalystaremuchhigher,usuallysomewherebetween150and
450C.AsignificantproportionofthehydrocarbonspecieswhichcontributetotheSOF
materialareinthevaporphaseundertheseconditionsandcanundergocatalyticoxidationin
exactlythesamewayasthegasphaseHC.Afterthecatalyst,whenexhaustgasesmixwithair
inthedilutiontunnel,heavyhydrocarbonscondenseand/oradsorbontothecarbonparticles
toformtheSOF.
WhiletheabovereasoningexplainshowSOFcompoundscancomeintocontactwiththe
catalyst,closerexaminationofthecontrolofPMbycatalystsrevealedfactsthatwerenot
consistentwiththeoxidationtheory,suggestingthatothermechanismsofSOFremovalmust
bealsotakingplaceintheDOC.Oncepastthelightoff,emissioncontrolcatalystsoperatein
themasstransfercontrolregime.Reactionratesdependonmasstransfercoefficientsforthe
particularreactants,whichinturndependontheirdiffusioncoefficients.Ifso,hydrocarbons
ofshortercarbonchains,characterizedbyhigherdiffusioncoefficients,shouldhavehigher
conversionratesoverthecatalystincomparisontoheavier,longercarbonchain
hydrocarbons(providedallspeciesareabovetheirlightoffshortchainHCsareknownto
havehighlightofftemperatures).Experiments,however,wereindisagreementwith
theoreticalmodelingbasedonoxidationalone,showinghigherconversionrateswith
increasingHCmolecularweight[Johnson1994][Voss1997].Thisbehaviorislikelyexplained
bycatalyticcrackingofheavyHCsintolightercompounds,catalyzedbybasemetals
(washcoatoxides).Crackingappearstobeveryimportant,maybeeventhedominant,SOF
removalmechanismoverbasemetalcatalysts,asreportedwithceriumoxide
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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.

Figure 13.HC Storage in Diesel Oxidation Catalyst


Temperature ramp experiment (10 min. wait @ 59C); Feed gas contains 3-4% water; SV =
33,333 hr-1

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].

Sulfate Formation & DOC Selectivity


Catalystselectivitywasthefocusinthedevelopmentofthedieseloxidationcatalystthrough
the1990s.Aselectivecatalystwouldexhibithighactivitytowardstheoxidationof
hydrocarbonsbut,atthesametime,lowactivityintheoxidationofsulfurdioxideandlow
sulfateparticulatemake.Alotofresearchhadbeenconductedtounderstandthemechanisms
ofcatalyticsulfateformationondifferentcatalystsystemsandwithfuelsofdifferentsulfur
contents.Anumberofcommercialcatalystshadbeendevelopedforthe500ppmSfuelwhich
representedthecertificationfuelintheUSA(1994),Europe(1996),andJapan(1996).The
selectivityofdieselcatalystsandthesulfateemissionproblembecamelessimportantwiththe
introductionofultralowsulfurdieselfuelsof1015ppmScontent.However,sulfate
suppressedcatalystformulationsstillmustbeusedformarketswithfuelsofhighersulfur
content.
Thegenerationofsulfatesinthedieseloxidationcatalystdependsonthefollowingfactors:
sulfurcontentinthefuel
catalysttemperature
catalystformulation.
Sulfurdioxide,theprecursorofsulfateparticulates,originatesfromthefuelsulfur.Thelower
thecontentofsulfurinthefuel,thelessSO2ispresentintheexhaustgas,andtheless
sulfatesaregeneratedinthecatalyst.IfthecatalyticconversionofSO2intoSO3,Equation
(3),andthebrakespecificfuelconsumptionareknown,onecaneasilyestimatethesulfate
particulateemissions.Thefollowingformulascanbeusedforthecalculation.Itisassumed
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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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Figure 14. Particulate Emissions with an Oxidation Catalyst

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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Figure 15. Thermodynamic Equilibrium for Oxidation of SO2to SO3

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.

Figure 16. Particulate Emissions over Repeated FTP Cycle

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DieselOxidationCatalyst

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.

Effect on Unregulated Emissions


Particle Number Emission
Contradictoryliteraturereportsexistontheeffectofdieseloxidationcatalystsonparticle
numberemissions.Sincedieselparticlenumberemissionscanbeattributedprimarilyto
nucleimodeparticles,whicharecomposedmostlyofhydrocarbonandsulfuricacid
condensates,onecaneasilyexplaintheperformanceoftheDOCbyanalyzingitseffecton
nucleimodeparticleprecursors.Ifthecatalystremoveshydrocarbons(gasphaseandSOF),it
preventstheirsubsequentnucleation,thusreducingtheparticlenumberemission[Westphal
2012].If,however,thecatalystproducessulfatesaneffectmoreprominentwithhighsulfur

fuelsandmoreactive,noblemetalcatalyststheparticlenumbersmaybeincreaseddueto
sulfuricacidnucleation.
ExperimentswhichattempttoquantifytheimpactofDOCsonparticlenumbersmustbevery
carefullydesigned.Catalystscanbeasourceofadditionalerror,suchassamplelossdueto
thermophoreticforcesorsampleadditionsduetosolidparticleblowoffand/orreleaseof
condensatesfromthewashcoat.

Polynuclear Aromatic Hydrocarbons


PAHemissionsaredividedbetweenthegasandparticulatephases.TheheaviestPAHs
constitutepartoftheSOFfractionofdieselparticulates,whilethelighterspeciescanbe
identifiedaspartofthegasphaseHCemission.TheHCandSOFeffectivenessofthediesel
oxidationcatalystsextendsonthePAHclassofcompoundsandotherHCderivatives.Table3
listsPAHresultsfromtwoDOCs(medium(B)andlow(D)activityformulations)tested
onaheavydutydieselengine(testcycle:FTPTransientengine:1998model12.7literDDC
series60EUIengine,turbochargedandaftercooled,rated400hp@1800rpm).Thetwo
catalystsprovidedaveragePAHemissionreductionsof68and54%,respectively[MECA
1999].
Table 3
Catalytic Conversion of PAH Emissions
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Emissions
Compound

Baseline

Cat B

Reduction
Cat D

g/bhp-hr g/bhp-hr g/bhp-hr

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.

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