STATUS REPORT THE DEVELOPMENT OF RAPID AGING AND POISONING PROTOCOLS FOR DIESEL AFTERTREATMENT DEVICES Bruce Bunting and Todd Toops Oak Ridge National Laboratory Fuels, Engines, and Emissions Research Center Ke Nguyen, Scott Eaton, Hakyong Kim and Adam Youngquist University of Tennessee at Knoxville Presentation at DEER 2006 August 24, 2006 OAK RIDGE NATIONAL LABORATORY U. S. DEPARTMENT OF ENERGY
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The Development of Rapid Aging and Poisoning … POISONING PROTOCOLS FOR DIESEL AFTERTREATMENT DEVICES Bruce Bunting and Todd Toops Oak Ridge National Laboratory Fuels, Engines, and
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STATUS REPORT
THE DEVELOPMENT OF RAPID AGINGAND POISONING PROTOCOLS FOR
DIESEL AFTERTREATMENT DEVICES
Bruce Bunting and Todd ToopsOak Ridge National Laboratory
Fuels, Engines, and Emissions Research Center
Ke Nguyen, Scott Eaton, Hakyong Kim and Adam YoungquistUniversity of Tennessee at Knoxville
Presentation at DEER 2006August 24, 2006
OAK RIDGE NATIONAL LABORATORY U. S. DEPARTMENT OF ENERGY
Rapid Aging and Poisoning Protocols
• An accelerated test protocol which simulates longer mileage field-service for evaluating durability and understandingmechanisms of deterioration.
• Benefits include: – More understanding of processes and mechanisms – More rapid product development – Verification of application early in life cycle – Testing for uncommon situations – Research basis for new materials or applications
OAK RIDGE NATIONAL LABORATORY U. S. DEPARTMENT OF ENERGY
Development of Rapid Protocols
HIGH MILEAGE OR ENGINE BENCH AGED
CATALYSTS
EXTENSIVE MATERIAL
CHARACTERIZATION
ACCELERATED ENGINE OR BENCH
PROTOCOL
COMPARE PERFORMANCE
CHANGES
EVALUATE APPLICATION AND DEVELOP
PROTOCOL
COMPARE MATERIAL CHANGES
OAK RIDGE NATIONAL LABORATORY U. S. DEPARTMENT OF ENERGY
Current Research Focuses
• Current research was developed through extensive discussionwith engine, auto and catalyst companies. – Diesel oxidation catalysts - Phosphorous poisoning – Lean NOx traps - High temperature lean-rich thermal aging – Diesel particulate filters - Ash effects on performance – Selective catalytic reduction catalysts - Aging and
poisoning of combined DPF-SCR
• Catalysts from Engelhard and Delphi • Substrates from NGK and Dow
• This research is supported by DOE OFCVT Fuels Technology Program and our program managers are Kevin Stork, Dennis Smith, and Steve Goguen
OAK RIDGE NATIONAL LABORATORY U. S. DEPARTMENT OF ENERGY
Catalyst and DPF Holder Assemblies
CATALYST BRICK
CATALYST CAN
DPF BRICK
DPF CAN
OAK RIDGE NATIONAL LABORATORY U. S. DEPARTMENT OF ENERGY
DOC
Syringe Pump
Drive Motor
Hatz Engine
Throttle Controller
Exhaust Sampling
Exhaust HC Injection
Engine Bench Setup
OAK RIDGE NATIONAL LABORATORY U. S. DEPARTMENT OF ENERGY
Summary of DOC Poisoning Effects
DEACTIVATION METHOD
METHODOLOGY FIELD-SERVICE EQUIVALENCE
PERFORMANCE DEGRADATION
PHOSPHORUS/SULFUR ADSORPTION (CERIUM
AND ALUMINUM PHOSPHATES)
INJECTING INTO INTAKE
MANIFOLD
NORMAL BUS OPERATION
HYDROCARBON OXIDATION
DENSE SOOT OVERLAYER
MIXING LUBEOIL WITH FUEL
EXCESSIVE LUBE-OIL
CONSUMPTION
CARBON MONOXIDE AND HYDROCARBON
OXIDATION ZINC PHOSPHATE
GLAZE INJECTING INTO
EXHAUST MANIFOLD
NOT OBSERVED (POOR OIL
CONTROL?)
CARBON MONOXIDE OXIDATION
OAK RIDGE NATIONAL LABORATORY U. S. DEPARTMENT OF ENERGY
Phosphorus Exhaust Chemistry
Zinc sulfate
Phosphoric acid
Electrospray MS Intake manifold
injection poisoning
• Representative of fuel and intake manifold injection poisoning
• Phosphoric acid (H3PO4)
• Zinc sulfate (ZnSO4)
OAK RIDGE NATIONAL LABORATORY U. S. DEPARTMENT OF ENERGY
UT Bench-Flow Reactor for LNT Aging
CONDITION TIME, sec.
O2, % CO2, % H2O, % NO, ppm CO, % H2, % N2, %
EVALUATION LEAN 20 0 5 10 1000 0 0 bal
EVALUATION RICH 4 0 0 0 0 4 1.3 bal
AGING LEAN, 800ºC* 158* 0 5 10 1000 0 0 bal
AGING RICH, 800ºC* 22* 3* 0 0 0 6* 2* bal
GAS MIXTURES USED FOR LNT AGING
* TIMES AND CONCENTRATIONS VARY SLIGHTLY WITH TARGET AGING TEMPERATURE
OAK RIDGE NATIONAL LABORATORY U. S. DEPARTMENT OF ENERGY
T=704
T=825
T=953
T 1058
Deterioration of Hi-Temp LNTs as Functionof Temperature and Number of Aging Cycles
70.00
80.00
90.00
100.00
0 50 100 150 200 250 300 350 NUMBER OF AGING CYCLES
% N
Ox
RED
UC
TIO
N
=
T=704oC
T=825oC
T=953oC
T=1058oC
OAK RIDGE NATIONAL LABORATORY U. S. DEPARTMENT OF ENERGY
OAK RIDGE NATIONAL LABORATORY U. S. DEPARTMENT OF ENERGY
Mechanisms of Deterioration for Hi-Temp LNTs
400 500 600 700 800 900 1000
AGING TEMPERATURE, C
BARIUM TRANSFORMATION
EVA
LUA
TIO
N T
EMPE
RA
TUR
E
AG
ING
TEM
PER
ATU
RES
PLATINUM SINTERING
POTASSIUM MIGRATION AND LOSS
BARIUM AGGLOMERATION
TEM IMAGE PROCES
BaCO3
γ-Al2O3
Fresh
Pt
Aged at 1000C and 250cyclesBaCO3 Pt γ-Al2O3
LNT Material Changes
FRESH
800oC/50 cycles
800oC/300 cycles PARTICLE SIZE DISTRIBUTION OBTAINED FROM TEM POTASSIUM MIGRATION TO INTERFACE
BaCO3
γ-Al2O3
Fresh
Pt
Aged at 1000C and 250cycles BaCO3 Pt γ-Al2O3
BARIUM AGGLOMERATION TRANSFORMATION OF BaCO3 (TO BaAl2O4)
OAK RIDGE NATIONAL LABORATORY U. S. DEPARTMENT OF ENERGY
Temperature Profile During LNT Thermal Aging
OAK RIDGE NATIONAL LABORATORY U. S. DEPARTMENT OF ENERGY
500
600
700
800
900
1000
1100
700 800 900 1000
TARGET TEMPERATURE, C
AC
TUA
L TE
MPE
RA
TUR
E, C
front middle rear
MAXIMUM TEMPERATURES IN LNT VARY AXIALLY DURING THERMAL AGING
TEMPERATURE VARIES DURING AGING CYCLING
Aging time and temperature are needed to extract deactivation kinetics
• Extract rates for aging mechanisms – Performance loss (global deactivation) – PGM sintering and NOx storage media agglomeration/loss – Applicable temperature ranges
• Model deactivation with simple kinetics
OAK RIDGE NATIONAL LABORATORY U. S. DEPARTMENT OF ENERGY
DPF Plan and Progress
• Plan – Study confounding issues of phosphorous, ash, and soot – Evaluate performance and microstructure analysis
• Progress – Received samples – Performed first tests – Blended lube oil into fuel to increase ash loading rate – Performed light-off and forced regeneration
• See DEER poster for more information: – B.G. Bunting and C.G. Li, “The Development of a Small Engine-
Based Accelerated Ash Loading Protocol and Application to a New Substrate Material”, DEER 2006, Tuesday, 9/22/06
OAK RIDGE NATIONAL LABORATORY U. S. DEPARTMENT OF ENERGY
SCR Aging and Poisoning
• Research just starting • Inputs from industry gathered so far
– Focus on zeolite-based SCR – Topics of concern
• Aging of SCR during active DPF regeneration • Phosphorous poisoning of SCR catalyst
OAK RIDGE NATIONAL LABORATORY U. S. DEPARTMENT OF ENERGY
SCR Aging and Poisoning Concept
ENGINE NH3 OR
EXHAUST FUEL UREAINJECTION INJECTION
DOC+DPF
LUBE OIL AND ZDDP
SCR
ACCELERATED POISONING
HIGH TEMPERATURE
AGING NOx REDUCTION
PERFORMANCE
OAK RIDGE NATIONAL LABORATORY U. S. DEPARTMENT OF ENERGY
Conclusions
• Rapid aging and poisoning protocols require three tasks – Develop rapid cycle based on application – Compare performance changes to field-aged catalysts – Compare material changes to field-aged catalysts
• Rapid aging and poisoning protocols provide an understanding of the processes taking place – Extensive materials characterization – Kinetic modeling of deactivation mechanisms
• General schemes can be applied to other situations • It is difficult to obtain field-aged catalysts (hint! hint!) ☺
OAK RIDGE NATIONAL LABORATORY U. S. DEPARTMENT OF ENERGY
Upcoming References
• DOC poisoning – S.J. Eaton, K. Nguyen, and B.G. Bunting, “Deactivation of Diesel
Oxidation Catalysts by Oil Derived Phosphorous”, SAE 2006 International Powertrain Conference, SAE 2006-01-3275.
• General – B.G. Bunting, J.P. Szybist, T.J. Toops, K. Nguyen, S.J. Eaton, A.D.
Youngquist, and A. Gopinath, “The Use of Small Engines as Surrogates for Research in Aftertreatment, Combustion, and Fuels”, SAE 2006 Small Engine Technology Conference, 06SETC-62.
• LNT aging – H. Kim, K. Nguyen, B.G. Bunting, and T.J. Toops, “Rapid Aging of
Diesel Lean NOx Traps through High Temperature Thermal Cycling”, SAE 2007 World Congress, 07-PFL-227.
OAK RIDGE NATIONAL LABORATORY U. S. DEPARTMENT OF ENERGY