USDRIVEAdvancedCombustionandEmissionControl(ACEC)TechTeam:

Low-TemperatureStorageCatalystTestProtocol

2017CLEERSWorkshop,AnnArbor,MichiganOctober3,2017

LowTemperatureAftertreatment(LTAT)TeamCraigDiMaggio,Vence Easterling(FCA)

JoeTheis(Ford)SeOh,MingYang(GM)

JimParks,JoshPihl(ORNL)KenRappé,MarkStewart(PNNL)

GalenFisher(UMich)KenHowden(DOE)

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- ProtocolsareACECsresponsetotheidentifiedindustryneedtoharmonize performancemetricsandrealistictestconditionsofaftertreatmentcatalystsforcommunicatingperformance

- Intentofprotocolsistoacceleratethepaceofcatalystinnovationanddiscovery- Protocolsaddressakeystage-gateforpotentialtechnologyevaluation

1OxidationLow-TemperatureOxidationCatalystTestProtocol 2

AdsorptionLow-TemperatureStorageCatalystTestProtocol 3

TWCLow-TemperatureThree-WayCatalystTestProtocol

Additionalprotocolstobedetermined(e.g.,multi-functional,SCR,etc.)

InnovativeTechnologyDevelopmentProcess*

SystemRequirementsandBoundaryConditions VehicleScale

SystemIntegrationandDemonstration

EngineScaleProcessStudiesandDemonstration

BenchScaleProcessStudiesandDemonstration

MaterialsDevelopment,

Downselection,andRefinementMaterials

Discovery

Modeling:FundamentalMaterials

Modeling:CatalysisKineticsand

MaterialProperties

Modeling:Processand

System

InnovationDiscovery

Fundamentals

Protocolimpactarea

SystemsIntegration

IndustryLimitsAppliedR&DProcessStudiesModeling

Time

Effor

t (Pr

e-co

mpeti

tive)

*courtesyofJerryGibbs

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ACEC-LTATteamactivity

ProtocolDevelopment• Low-TemperatureStorageCatalystTestProtocol

– CompleteandwillbereleasedtotheCLEERSwebsiteshortly• http://cleers.org/low-temperature-protocols/

– Focusedonlowtemperaturestorage catalysts• Simpletoexecute,realistic• comprehensiveenoughtoaccurately&realistically

reportperformance

– Comparisontooxidationcatalystprotocol• Samedocumentstructure• Differencestoaccountfor:

– Storage/releasevs.conversion– Transientnatureofstorage&release

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ACEC-LTATteamactivity

ProtocolDevelopment• Scopeofthelowtemperaturestorage catalystprotocol

– Assessmentofmaterialsforstorage/release‘functionality’

– Storageandreleasecatalystsarenotstand-alonedevices;theymustbecoupledwithconversioncatalysts

• HCtrapsmustbeintegratedwithoxidation• PNAsmusthavedownstreamNOx reduction

– Therefore,conversionmustbeconsideredintheevaluation

– However,conversionisnotthefocus;itisincludedsolelyasatooltohelpassesstheefficacyofstorage/releasematerials

– Tocapturebothstorage/releaseandconversionproperties,Itissuggestedtheuserconducttheprotocolinduplicate1. Withthetrapmaterialtoassessstorageandreleaseproperties

ofthedevelopmentalmaterial2. Withthetrapmaterialandconversioncatalyst(integrated

appropriatetotheapplication)toassessdevice-levelsolution,andrelationofreleasetoconversion

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Low-Temperature Storage Catalyst Test Protocol FormatSimilarities and Differences in Structure (vs. Oxidation)

Ø ProtocolElementsinCommon• Generalformat(4mainsections)• ReactorConfiguration

• Catalystdetail(powder/monolith)• Temperaturemeasurement• Bestpractices

• Samplepreparation• De-greening,aging,sulfurpoisoning• Focusonbestpractices

Low-Temperature Storage Catalyst Test Protocol FormatSimilarities & Differences in Structure (vs. Oxidation Protocol)

Ø ProtocolDifferences (vs.OxidationProtocol)1. Systemconfiguration/gasanalysis

• Additionalcomplexity2. Exhaustsimulation3. Protocolexecution4. Reporting

PERFORMANCEEVALUATIONPre-treatment – Table2

Storage – Table3

Release – Table4

AGE– Table6

DE-GREEN– Table5

LNTonly

POISON – Table8

SELECTENGINETYPEANDCOMBUSTIONMODE

S-GDICDCL-GDILTC-GLTC-DExhaustComposition – Table1

SelectReleaseConditionsHC NOx

PERFORMANCEEVALUATIONTables2,3,4

AGE– Table7

PERFORMANCEEVALUATIONTables2,3,4

PERFORMANCEEVALUATIONTables2,3,4

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Simulatedexhaust

Storagecatalyst

ValveActuator Air/N2

Vent

Gasanalysis

Low-Temperature Storage Catalyst Test ProtocolUnique Testing Requirements

– Thedynamicandtransientnatureofstoragecharacterizationrequirescertainuniquesystemhardwarecapabilities

– Accuratelycharacterizingstoragerequirestheabilitytoswitchbetween• Afullreactorbypasswiththesimulatedexhauststreamtostabilizeandcharacterizethefeedconcentrationspriortostorage

and• Flowingthroughthecatalystbed

1. Systemconfiguration/gasanalysis

– Thisdiffersfromconversion(oxidation),whichis

• Steady-state,and• Inlet&outletslipstreamsareappropriate

Exampleofahardwareschematicforafull-reactor

bypassconfiguration

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Low-Temperature Storage Catalyst Test ProtocolUnique Testing Requirements

– Quantitativeanalysisofstoredspeciesand potentialby-products• NO:NO,NO2,N2O• HC:TotalHC,CO,CO2 – preferredanalysisofeach HC,andpotentialHCby-products

– Frequencyofanalysis&rateofanalyticalresponseareimportant• Differsfromsteady-stateconversionmeasurements• Frequencyofsampleacquisition/analysis

– Fidelityofdatafordeterminingstorage/releaseamounts&kinetics– 1-Hzpreferablesamplefrequency

• Rateofanalyticalresponse– Accuratelycharacterizestorage/releaseproperties&releaseprofile– ≤15sec.toreach≥90%steady-stateconcentrationafterstep-changeinfeed

• Necessitatesa‘real-time’analysisstrategy– FT-IR,MassSpec,NOx chemiluminescence,FID,etc.– Excludeschromatography

1. Systemconfiguration/gasanalysis

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Low-Temperature Storage Catalyst Test ProtocolUnique Testing Requirements

– HCisrepresentedasacombinationof:• Smallalkene(ethylene)• Aromatic(toluene)• Unburnedfuelsurrogate

– n-Dodecane (fordieselapplicationsonly)– Ethanol+iso-octane(forgasolineapplications)

2. ExhaustsimulationTable1–Simulatedengine-outexhaustparametersforstoragecharacterization

Constantcomponents S-GDI CDC L-GDI LTC-G LTC-D[O2] 0.74% 12% 9% 12% 12%[H2O] 13% 6% 8% 6% 6%[CO2] 13% 6% 8% 6% 6%

Variablecomponents allin[ppm][CO] 5000 500 2000 2000 2000[H2] 1670ppm 100ppm 670ppm 670ppm 400ppm[NO] 1000 200 500 100 100 Hydrocarbon–[ppm]onC1basis

Total[HC] 3000 1400 3000 3000 3000[C2H4] 900 400 400 400 900

[C2H5OH] 110 110 110 [C7H8] 900 300 1400 1400 900[i-C8H18] 1090 - 1090 1090 -[n-C12H26] - 700 - - 1200*BalanceN2

Unchangedfromoxidationprotocol

Requiresliquid-HCcomponents;

significantdifferenceversusoxidation

prototol9

Low-Temperature Storage Catalyst Test ProtocolUnique Testing Requirements

3. Protocolexecution(2) STORAGE

20min@600°C(1) PRE-TREATMENT20min@600°C20min@600°C

Cooldownto100°C

Stabilizeinlet

Characterizestorage30min@100°C

(3) RELEASE

Ramp20°C/minto600°C

5090

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-30 -20 -10 0 10 20 30 40 50 60

Catalystte

mpe

rature,°C

Testtime,min

600

500

400

300

200

100

Pre-treatment:20min@600°C

+cool down

Release:20°C/min

to600°C

Storage:30min@100°C

1 2 3

10

5090

130170210250290330370410450490530570610

-30 -20 -10 0 10 20 30 40 50 60

Catalystte

mpe

rature,°C

Testtime,min

600

500

400

300

200

100

Pre-treatment:20min@600°C

+cool down

Release:20°C/min

to600°C

Storage:30min@100°C

1 2 3

Low-Temperature Storage Catalyst Test ProtocolUnique Testing Requirements

3. Protocolexecution

1) Pre-treatment– 20minutes@600°C– Conductedlean forallcombustionmodes**– OxidizeallcarbonaceousspeciesordepositsandreleasestoredNOx– Conductedpriortoeach storage/releaseevent– **Stoichiometriccombustionapplicationsrequireacatalystreductionstep

• Reducethemetalonthecatalyst• 5minutes@350°Cunderreducingconditions

PRE-TREATMENT–CDC,LTC-D,LTC-G,L-GDIStepNo. Temperature Exhaustmake-up(balanceN2)(a) BypassLTP-2-1P Pretreat20min@600°C - - - - [O2] [H2O] [CO2] OffLTP-2-2P Cool600°Cto100°C - - - - [O2] [H2O] [CO2] OffLTP-2-3P Hold5min@100°C - - - - [O2] [H2O] [CO2] Off

• Concentrationsrefertothoseshownin‘Exhaustsimulation’onslide9

(2) STORAGE20min@600°C

(1) PRE-TREATMENT20min@600°C20min@600°C

Cooldownto100°C

Stabilizeinlet

Characterizestorage30min@100°C

(3) RELEASE

Ramp20°C/minto600°C

(2) STORAGE20min@600°C

(1) PRE-TREATMENT20min@600°C20min@600°C

Cooldownto100°C

Stabilizeinlet

Characterizestorage30min@100°C

(3) RELEASE

Ramp20°C/minto600°C

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(2) STORAGE20min@600°C

(1) PRE-TREATMENT20min@600°C20min@600°C

Cooldownto100°C

Stabilizeinlet

Characterizestorage30min@100°C

(3) RELEASE

Ramp20°C/minto600°C

5090

130170210250290330370410450490530570610

-30 -20 -10 0 10 20 30 40 50 60

Catalystte

mpe

rature,°C

Testtime,min

600

500

400

300

200

100

Pre-treatment:20min@600°C

+cool down

Release:20°C/min

to600°C

Storage:30min@100°C

1 2 3

Low-Temperature Storage Catalyst Test ProtocolUnique Testing Requirements

3. Protocolexecution

2) Storage– 100°Cdefaultstoragetemperature

• Toinvestigateeffectofstoragetemperatures,protocolshouldbere-runinitsentiretyatthedifferentstoragetemperatures

– Fullsimulatedexhaust– Inletshouldbefirststabilizedonfull-reactorbypass

(2) STORAGE20min@600°C

(1) PRE-TREATMENT20min@600°C20min@600°C

Cooldownto100°C

Stabilizeinlet

Characterizestorage30min@100°C

(3) RELEASE

Ramp20°C/minto600°C

(2) STORAGE20min@600°C

(1) PRE-TREATMENT20min@600°C20min@600°C

Cooldownto100°C

Stabilizeinlet

Characterizestorage30min@100°C

(3) RELEASE

Ramp20°C/minto600°C

STORAGE–allmodesStepNo. Temperature Exhaustmake-up(balanceN2)(a) Time BypassLTP-2-3S Hold100°C [HC] [CO] [H2] [NO] [O2] [H2O] [CO2] -(b) OnLTP-2-4S Hold100°Cfor30min [HC] [CO] [H2] [NO] [O2] [H2O] [CO2] 30min Off

• Concentrationsrefertothoseshownin‘Exhaustsimulation’onslide9 12

5090

130170210250290330370410450490530570610

-30 -20 -10 0 10 20 30 40 50 60

Catalystte

mpe

rature,°C

Testtime,min

600

500

400

300

200

100

Pre-treatment:20min@600°C

+cool down

Release:20°C/min

to600°C

Storage:30min@100°C

1 2 3

Low-Temperature Storage Catalyst Test ProtocolUnique Testing Requirements

3. Protocolexecution

3) Release– Compositiondictatedbyexpected conditionsofrelease

• Aboveoxycat/TWClight-off;subsequentNOx reduction– Forstudyofrelease/conversioninterplay

• IncludereductantwhentestingPNAs• Include[O2]inS-GDIwhentestingHCtraps

(2) STORAGE20min@600°C

(1) PRE-TREATMENT20min@600°C20min@600°C

Cooldownto100°C

Stabilizeinlet

Characterizestorage30min@100°C

(3) RELEASE

Ramp20°C/minto600°C

• Concentrationsrefertothoseshownin‘Exhaustsimulation’onslide9

(2) STORAGE20min@600°C

(1) PRE-TREATMENT20min@600°C20min@600°C

Cooldownto100°C

Stabilizeinlet

Characterizestorage30min@100°C

(3) RELEASE

Ramp20°C/minto600°C

NOxRELEASE–allmodesStepNo. Temperature Exhaustmake-up(balanceN2)(a) Time BypassLTP-2-5RN Ramp20°C/minto600°C - - - [NO] [O2] [H2O] [CO2] 26min Off

HCRELEASE–CDC,LTC-D,LTC-G,L-GDI StepNo. Temperature Exhaustmake-up(balanceN2)(a) Time BypassLTP-2-5RH Ramp20°C/minto600°C - - - [NO] [O2] [H2O] [CO2] 26min Off

HCRELEASE–S-GDI StepNo. Temperature Exhaustmake-up(balanceN2)(a) Time BypassLTP-2-5RHS Ramp20°C/minto600°C - - - - - [H2O] [CO2] 26min Off

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• Catalystsampledetailo Sampledimensionsormass,substrate,etc.o Informationoncatalystcomposition

• Reactorconfigurationo Reactordetail,thermocouplesandplacement,etc.o Processdescription,methodofgassampling,bypasso Chemicalanalysis

• Testconditionso Application(i.e.,enginecombustion/operatingmode)o Procedures/conditionsforde-greeningoraging,pre-treating,S-poisoning,andmeasuring

performanceo Heatingrateextremelyimportant

• Testresults/performancedatao Quantitativestorage,release,andconversionresultso Concentration(s)andtemperatureversustime

Low-Temperature Storage Catalyst Test ProtocolUnique Reporting Procedures

4. Reporting SameasOxidationProtocolUniquefromOxidationProtocol

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Low-Temperature Storage Catalyst Test ProtocolUnique Reporting Procedures

4. Reporting

• Testresults/performancedata– Storage

• QuantityofNOx/HCstored• NOx/HCstorageefficiency

– Release• QuantityofNOx/HCreleased• By-productformation(e.g.,N2O)• Releasetemperature

– e.g.,T10,T50,T90

– Conversion• DesorbedNOx/HCconversionefficiency• Netemissionbenefitimpact

– Storageefficiency+conversionefficiencyofstoredcomponent

• Byproductformation

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rature[°C]

Concen

tration[ppm

]

Time[min]

HC Inlet

CatalystTemperature

HC Outlet

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Released

storage release

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Low-Temperature Storage Catalyst Test ProtocolUnique Reporting Procedures

Summary• TheLow-TemperatureStorageCatalystTestProtocolwillbethe2nd low-

temperatureprotocolreleasedtotheCLEERSwebsite– http://cleers.org/low-temperature-protocols/– TWCtestprotocoliscurrentlyunderdevelopment,andwillbethe3rd protocolreleased

in2018

• ThetestprotocolsareaproductoftheLTATsub-groupoftheACEC.TheyareassembledwithinputfromOEMs(Ford,FCA,GM),thenationallabs(PNNL,ORNL),academia(Univ.ofMichigan),andDOE.

• PleaseconsideruseoftheLow-TemperatureStorageCatalystTestProtocolasaformatforrelayingperformanceofnovelstoragecatalysts(e.g.,PNAs,HCtraps)tothetechnicalcommunity

• Pleasereviewthetestprotocolindetailpriortouse,andcontactanymemberoftheLTATteamwithquestions.

• Thankyou!!16