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Fuel and Emission Control System Effects on Unregulated Emissions in APBF-DEC

Fuel and Emission Control System Effects on Unregulated Emissions in APBF-DEC. John Storey, Sam Lewis, Linda Lewis, Brian West Oak Ridge National Laboratory Jim Ball (co-chair), Kirby Baumgard, Joe DeVita, Doug Lawson, Mani Natarajan APBF Toxics and Unregulateds Committee

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Fuel and Emission Control System Effects on Unregulated Emissions in APBF-DEC

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  1. Fuel and Emission Control System Effects on Unregulated Emissions in APBF-DEC John Storey, Sam Lewis, Linda Lewis, Brian West Oak Ridge National Laboratory Jim Ball (co-chair), Kirby Baumgard, Joe DeVita, Doug Lawson, Mani Natarajan APBF Toxics and Unregulateds Committee 2005 Fuels Technologies Program Merit Review March 7-9, 2005 Sponsor: U.S. Department of Energy, OFCVT Program Managers: Stephen Goguen and Kevin Stork

  2. Toxics and Unregulated Emissions Working Group Members and Team • Jim Ball (Ford) and John Storey (ORNL), co-chairs • Kirby Baumgard (John Deere), Doug Lawson (NREL), Joe De Vita (CARB), Mani Natarajan (Marathon Ashland Petroleum) • Analyses and Methods Development by: • Desert Research Institute (elements) • Southwest Research Institute (PAH, NPAH) • Joe Pan • ORNL (urea decomposition, nitroxy-alkanes) • Sam Lewis, Linda Lewis, Gerald Devault

  3. Project Overview Scope: Determine the effect of 2006 fuels reformulation on unregulated emissions and air toxics with and without advanced emissions-control systems; “Do no harm” • Develop analytical methods for “unusual” compounds, potential problem compounds formed in both urea-SCR and NOx adsorber systems. • Specify measurements of unregulated emissions and methods for all three teams. • Lubricants • Urea-SCR • NOx Adsorber • Began November 2000 – ends in 2005

  4. General Approach • Survey of recent, active and planned projects • Test Program • Committee identified likely and critical mobile source air toxic compounds to measure • Identified potential emission control system-specific emissions • urea decomposition products from SCR • nitro-organic compounds from NOx adsorbers • Develop analytical methods when needed • Provide test labs with equipment and guidance as needed • Reporting results in the literature

  5. NOx Adsorber Project UnRegEm Plan • Compounds • HCs, N2O, NH3on site • Nitroalkanes, Alkyl Nitrates, Nitrites via ORNL method • PAHs in particulate and gas phase • Nitro-PAHs in particulate and gas phase • Formaldehyde and acetaldehyde • Elemental analysis of PM • Methods • FTIR or on-line MS • Nitro-PAHs, PAHs: Extraction then GC/MS (Hi-res for nitro-PAH) • Elemental: X-Ray Fluorescence (XRF) and ICP-MS

  6. Urea-SCR Project UnRegEm Plan • Compounds • Bag HCs, N2O, NH3 on site • Urea decomposition products • PAHs in PM, semi-volatile phase • Aldehydes and ketones • Elemental on PM • Methods • FTIR or on-line MS • Nitro-PAHs, PAHs: Extraction then GC/MS (Hi-res for nitro-PAH) • Elemental: X-Ray Fluorescence (XRF) • Urea decomposition products with ORNL method

  7. Industry collaboration • APBF has been a government – industry partnership all along • Unregulated Emissions Committee members include ORNL, NREL, an energy company, engine and automotive companies, and state government - all very active • Ford published research on urea decomposition – a key reason to examine all unregulated emissions for the APBF program

  8. Technical accomplishment summary • Methods developed and deployed for urea decomposition products and nitroxy-alkanes • Sampling plans and apparatuses to the labs • ORNL designed and built two large-volume samplers for PAH/nitro-PAH based on published work at SwRI • Analysis completed: Lubricant project and HD-NOx Adsorber • sample analysis on other projects finishing up • Publications submitted and in preparation • methods development • light-duty NOx adsorber project

  9. Results Summary • Lubricants Project: • Additive metals not enhanced in PM; PAHs not found to vary with lube properties • NOx Adsorber Projects • DPF removes PAHs, metals • Exhaust warmer in SUV project may influence PAHs • Nitroxy-alkane formation during cold operation: not an important NOx sink • Urea-SCR Project • DPF removes PAHs • No urea decomposition products detected

  10. Light-Duty NOx Adsorber DPF system removes 1,3 Butadiene 14 Eng Out 12 A 50 hrs B 50 hrs 10 B 300 hrs 8 1,3 Butadiene Emissions (mg/mi) 6 4 2 0 CLA4 HLA4 US06 HwFET

  11. Formaldehyde equivalent to engine-out levels after 300 hrs on system B 30 Eng Out A 50 hrs 25 B 50 hrs B 300 hrs 20 Formaldehyde Emissions (mg/mi) 15 10 5 0 CLA4 HLA4 US06 HwFET

  12. Wide array of PAHs measured in APBF

  13. Cold-start may be source of most PAH – related to auxiliary exhaust heating? (SwRI SUV project)

  14. B(a)A Chr Good news – aging in NOx Adsorber system does not affect PAH (SwRI SUV Project) This detail from previous chart shows that the levels of PAH remain constant or decline over 2000 hrs of aging

  15. DPF traps sulfur and lube metals; likely mobile source air toxic metals, tooSwRI SUV NOx adsorber project

  16. Other than nitromethane, nitroxy-alkane formation is minimal: no “hidden” NOx(SwRI SUV NOx Adsorber data)

  17. Ideally, injected urea goes to NH3; then reacts with NOx to form N2 Heat 2 NH3 + CO2 H2O, O2 2 NH3 + NO + NO2  2 N2 + 3 H2O

  18. urea melamine ammelide cyanuric acid ammeline dicyandiamide NH4NO3 biuret Ammonium nitrate Structures of urea decomposition products

  19. Summary of Literature Search on the Toxicity of Selected Urea-Decomposition Products(Jim Ball: SAE 2001-01-3621) • Urea and cyanate used in the treatment of Sickle Cell Anemia. • Long-term treatment may cause cataracts. • No data on biuret – similar to urea (probably non-toxic). • Ammonia is acutely toxic at high concentrations; irritating at lower levels. • Cyanuric acid is not acutely toxic - used in swimming pools. • Melamine has been extensively studied - not acutely toxic in animals. • No data on ammelide; one paper on the effect of ammeline on the growth of mice – no effects.

  20. Urea Decomposition Products in the APBF-DEC program • Identified methods for urea decomposition products (ammelide, ammeline, cyanuric acid, melamine, etc.) • Paper submitted to Analytical Chemistry • Analyzed real impinger and particulate samples from ORNL diesel engine-DPF-urea-SCR catalyst system and found the decomposition products - due to pooling in exhaust pipe? • Exhaust sampled during APBF Heavy-Duty Urea SCR project yielded no identifiable decomposition products → 2000 hrs • Difference was quality and quantity of urea injection: Bosch injector more sophisticated and many hours were spent optimizing injection amounts; also, “cleanup” catalyst was used

  21. Future plans • Program finishes in 2005 • Several papers in process or submitted • Can use new methods and analytical approach to understanding impact of Non-Petroleum Based Fuels • Results directly applicable to ACES activity • Applicable to new combustion regimes, new fuels • e.g. low NOx and low PM, but what about air toxics like aldehydes? • do cyclic hydrocarbon species in fuels become PAH in exhaust?

  22. Summary • Relevance: New fuels/emissions technology must avoid creating new problems • Approach: Measure unregulated emissions from all APBF projects • Technical Accomplishments: Developed critical analytical methods; identified impact of emissions control and fuel S on unregulated emissions • Collaboration: Industry/Lab/ARB tech team very involved in all aspects • Future Plans: Approach is widely applicable to upcoming Non-Petroleum Based Fuels, new combustion regimes, ACES health effects activity

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