1. Diesel Fuel Quality and Sulfur Effects on Catalyst-Based Exhaust Emission Controls: Manufacturers of Emission Controls Association May 2000

2. Presentation Outline  Introduction  Impact of Fuel Sulfur on Catalyst Emission Control Technology  Noble Metal Function  NOx Control Technology  PM Control Technology  Conclusions

3. Introduction  Fuel Quality Is an Integral Part of a Complete Emission Control System for Both Gasoline and Diesel Powered Vehicles  Although Other Fuel Constituents Affect Engine-Out Emissions, Fuel Sulfur Is the Single Most Important Constituent for Catalyst-Based Emission Control Technology  Sulfur in Diesel Fuel Adversely Affects the Emission Control Performance of All Catalyst-Based Emission Control Technologies

4. Introduction (cont.)  Near Zero Diesel Sulfur Levels Would Enable the Application of the Full Range of Control Technologies and Would Permit Each Technology to Be Optimized for Maximum Emission Control Performance  EPA Has Proposed Phase 2 On-Road HDE Standards of 0.2 g/bhp-hr NOx and 0.01 g/bhp-hr Particulate to Take Effect in the 2007 Timeframe  Fuel Sulfur Levels Will Be Instrumental in Meeting These Aggressive Targets

5. Zeolite or refractory oxide support Precious Metal SO 3 SO 4 = Transition Metal H 2 SO 4 O2O2O2O2 Sulfate make Sulfur inhibition Sulfate Poisoning SO 2 Sulfur Effects

6. Test procedure: Engine test bench, partial load, 1.9 L TDI engine Noble Metal Function: Sulfur Increases Light-Off Temperature and Reduces Peak Conversion 80 120 160 200 240 100 80 60 40 20 0 CO Conversion (%) Exhaust temperature before catalytic converter ( o C) Regular Diesel fuel (350 ppm S) Quissel et al, VDA-Fortschrittsberichte, 12 (348), Bd. 2, 225-246 (1998) 80 120 160 200 240 100 80 60 40 20 0 CO Conversion (%) Exhaust temperature before catalytic converter ( o C) Sweden Diesel fuel (<10 ppm S) 1/2 hr Conditioned 32 hr Aging Oxidation Catalyst

7. Sulfur Adversely Affects Non-Precious Metal Lean NOx Catalysts

8. NOx Adsorbers: Sulfur Effects  Sulfur Poisoning and Inhibition  Inhibits Conversion of Unregulated Emissions (e.g. toxic HC emissions)  Prevents NOx Conversion  Increases Fuel Economy Penalty  Sulfate Make

9. Sulfur Poisons NOx Adsorbers Storage Sites Sulfur Poisons NOx Adsorbers Storage Sites 30s/2s 30hrs at 400 C 0 10 20 30 40 50 60 70 80 90 100 200250300350400450500 Evaluation Temperature (C) NOx Conversion (%) 13 0 20 40 60 80 100 120 123456789101112 Depth into Washcoat S/Ba Molar Ratio (%) 200 ppm100 ppm0 ppm 40 ppm *equivalent fuel sulfur content* The extent of poisoning increases with fuel sulfur content and duration of exposure.

10. Low Levels of Sulfur Are Needed to Maintain NOx Adsorber Catalyst Efficiency 0 20 40 60 80 100 0500100015002000250030003500400045005000 Miles Traveled Catalyst NOx Breakthrough, % 7 ppm Sulfur Fuel Catalyst "A" 150 ppm Sulfur Fuel Catalyst "A" 300 ppm Sulfur Fuel Catalyst "B" 0.1 ppm Sulfur Fuel Catalyst "c" 7 ppm Fuel: 1700 Miles 150 ppm Fuel: 115 Miles 300 ppm Fuel: 55 Miles Mileage Interval vs Fuel Sulfur Content which Leads to a 5% Decrease in Catalyst Efficiency (Note: T/P NOx emissions double when catalyst efficiency drops from 95 to 90% ) 0.1 ppm Fuel: >5,000 Miles

11. 020406080100120140160 100 90 80 70 60 50 40 30 20 10 0 Poisoning period (hr) NOx Conversion (%) Gasoline fuel: California Phase 2 (ca. 30 ppm S) - Catalytic converter B Gasoline fuel: Super Plus (130 ppm S) Catalytic converter A Gasoline fuel: California Phase 2 (ca. 30 ppm S) Catalytic converter A Cycle during poisoning and measurement: 30/2 S lean/rich Test Procedure: Engine test bench, partial load operation Quissel et al, VDA-Fortschrittsberichte, 12 (348), Bd. 2, 225-246 (1998) Advances in NOx Adsorber Sulfur Resistance

12. Catalytic Particulate Filters: Sulfur Effects  Sulfur Poisoning and Inhibition  Inhibits Control of Unregulated Emissions  Increases Regeneration Temperature  Formation of Sulfate

13. Catalytic Filter Regeneration Is Adversely Affected by Sulfur  A Low Regeneration Temperature Insures Reliable Catalytic Filter Operation and Durability  A Low Regeneration Temperature Allows Filter Technology to Be Applied to a Broad Range of Vehicle Applications  Higher Sulfur Levels in Diesel Fuel Increase a Catalytic Filter’s Regeneration Temperature  In the DECSE Program, Increasing the Fuel Sulfur Content from 3 ppm to 30 ppm Increased the Regeneration Temperature of Two Different Catalytic Filter Systems by 23 to Over 30 o C.  Experience in Countries Characterized by Very Cold Temperatures, e.g. Sweden, Indicates that There Have Been No Durability Problems with Systems Having Accumulated in Excess of 475,000 km when Diesel Fuel with <10 ppm Is Used

14. Impact of Sulfur on Heavy-Duty PM Emissions 90% Reduction from 2004 Std.

15. Impact of Sulfur on Light-Duty PM Emissions

16. The DECSE Study Is Showing That Low Sulfur Is Critical to Achieving a 0.01 g/bhp-hr PM Standard (System 1) From DOE website; Diesel Emission Control - Sulfur Effects; Sponsored by DOE, EMA, MECA, and National Labs OICA 13-mode cycle; CAT 3126 engine ~95% efficiency at 3 ppm sulfur ~70% efficiency at 30 ppm sulfur ~0% efficiency at 150 ppm sulfur Negative efficiency at 350 ppm sulfur

17. The DECSE Study Is Showing That Low Sulfur Is Critical to Achieving a 0.01 g/bhp-hr PM Standard (System 2) From DOE website; Diesel Emission Control - Sulfur Effects; Sponsored by DOE, EMA, MECA, and National Labs OICA 13-mode cycle; CAT 3126 engine ~95% efficiency at 3 ppm sulfur ~70% efficiency at 30 ppm sulfur ~0% efficiency at 150 ppm sulfur Negative efficiency at 350 ppm sulfur

18. Status of Reducing Impacts of Sulfur on NOx Adsorbers  MECA Members Continue Research Efforts in Decreasing Sulfur Sensitivity  BUT,  Desulfurization Frequency Needs to Be Minimized for Commercial Viability of NOx Adsorbers  Minimize Fuel Economy Penalty  Maximizes the Opportunity for Operating Conditions Conducive to Desulfurization to Be Met Under Normal In- Service Operation  To Meet Very Low Emission Levels Only an Approximately 5% Decrease in Performance Can Be Tolerated  Control of Unregulated Emissions Is Inhibited  Off-Cycle Emissions During Desulfurization  Inhibition of the Performance of Other Emission Control Devices  Sulfur Inhibition Is Cumulative

19. Status of Reducing Impacts of Sulfur on Catalytic Particulate Filters  MECA Members Continue Research Efforts in Decreasing Sulfur Sensitivity  BUT,  Sulfur Significantly Increase the Balance Point Temperature Due to Sulfur Inhibition which Adversely Affects Filter Regeneration  Control of Unregulated Emissions Is Inhibited  Cold Climatic Conditions Exasperate the Effects of Sulfur Inhibition  Sulfur Inhibition Is Cumulative

20. Conclusion  To Help Insure that Diesel Fuel Remains Competitive with Other Fuels, It Is Incumbent on the Engine Manufacturers, the Emission Controls Industry, and the Fuel Providers to Work Together to Provide a “Truly Clean” Diesel Engine so that the Public Accepts the Fuel As an Environmentally Friendly, Safe, and Efficient Means to Meet the Nation’s Transportation Needs