MMT Update (Methylcyclopentadienyl Manganese Tricarbonyl)

Transcription

1 MMT Update (Methylcyclopentadienyl Manganese Tricarbonyl) Dr. Haren Gandhi ( ) Technical Fellow and Manager Research and Advanced Engineering Chemical Engineering Department Presented by Dr. Leandro H. Benvenutti Technical Expert on Fuels & Lubricants October 14, 2010 p. 1

2 Agenda We Have a Problem! Report on MMT - Canada Data Canadian Manganese (Mn) Fuel Survey Trends Warranty Information Review Contaminated Catalyst Samples Mn Deposit Analysis and Impacts What we tell our Customers Owner Guide What s Happening around the World Alternative Octane Enhancer Conclusions and Recommendations p. 2

3 We Have A Common Problem Advanced Catalysts Are Showing High Occurrence of Plugging emission systems are affected! What do we want? We are asking Gasoline Producers and Distributors to stop using metal additives We are recommending to the government that emission controlled vehicles should not be exposed gasoline containing metal additives including manganese. p. 3

4 Multi-year, Multi-manufacturer Effort p. 4

5 Conclusions from the Report Executive Summary Section: The use of manganese-containing fuels in vehicles negatively impacts both engine and aftertreatment components (spark plugs, exhaust valves, oxygen sensors and catalysts). Observations: Physical plugging of catalyst channels Driveability problems Increased tailpipe emissions MIL (Malfunction Indicator Light) illumination Canadian warranty rates slowed in direct response to the reduction in the use of MMT in Canadian gasoline. There is no demonstrated method, other than eliminating manganese from the fuel, to ensure that an engine/emission control system will not experience customer driveability complaints or in the more severe case, requiring complete engine components/emission system replacement. p. 5

6 Canadian Fuel Survey Information - Manganese 26,4mg/l 23,8 21,1 18,5 15,9 Surveys for Argentina indicate a range up to 94 mg/gal Manganese (2009/2010) Max limit in Arg 13,2 10,6 7,9 5,3 2,6 0 mg/liter From 2003 to 2006, the Canadian gasoline content of manganese decreased from an average of ~32mg/gal to 0 due to voluntary actions by oil companies. p. 6

7 Canada vs US Cumulative Rate of Return for Catalytic Converters p. 7 Source: SR

8 Canada Incidents per Thousand for Catalytic Converters p. 8 Source: SR

9 All Photos Should Be Viewed in Color Canadian Sample Sample Canadian Catalyst Photographs US Sample ~22,000 miles ~55% Blockage Canadian Sample ~100,000 miles 0% Blockage ~41,000 miles ~95+% Blockage Canadian Sample Source: SR Canadian Sample Canadian Sample ~46,000 miles ~30% Blockage ~46,000 miles ~75% Blockage p. 9 ~72,000 miles ~85% Blockage

10 All Photos Should Be Viewed in Color Additional Canadian Catalyst Photographs p. 10 Source: SR

11 All Photos Should Be Viewed in Color Additional Pictures of Catalysts from Other Parts of the World Blocked Catalyst: 83,000 km operation in Southern Africa on MMT doped fuel Ref.: ACEA p. 11

12 All Photos Should Be Viewed in Color Additional Pictures of Catalysts from Another Parts of the World Blocked Catalyst: 33,000 km operation in China on MMT doped fuel Ref.: ACEA p. 12

13 All Photos Should Be Viewed in Color Additional Pictures of Catalysts from Another Parts of the World Blocked Catalyst: km in service vehicle in Argentina in 2009 on MMT doped fuel p. 13 Ref.: FORD

14 All Photos Should Be Viewed in Color Additional Pictures of Catalysts from Another Parts of the World Blocked Catalyst: km in service vehicle in Argentina in 2009 on MMT doped fuel Ref.: FORD p. 14

15 All Photos Should Be Viewed in Color Additional Pictures of Catalysts from Another Parts of the World Blocked Catalyst: 3,722 km in service vehicle in Argentina in 2010 on MMT doped fuel p. 15 Ref.: FORD

16 Sample X-Ray Diffraction Info Sierra Report XRD results from these samples confirmed the presence of Mn 3 O 4. Source: SR p. 16

17 Canada Catalyst System Return Vehicle Emission Testing (sec-by-sec) p. 17 NOTE: Vehicle used in this study for testing are the models associated with in field vehicle catalyst returns. Certification gasoline used.

18 Engine-Dyno Catalyst System Evaluation p. 18 Source: SR

19 MMT Emission System Impacts SAE Paper # SAE Paper # Model Year 100,000 miles using 32mg/gal Mn Alliance Study Part 2 Mn vehicle AE16 Mn-deposit over layer Open Channel Blocked Channel Blocked Washcoat Catalytic washcoat Catalytic Washcoat Mn-Deposits Clear vehicle CE16 Substrate wall Substrate wall p. 19

20 MMT Impacts on Components Spark Plugs Alliance Study Spark Plugs Part 2 Part 1 CE16 100,000 miles AE16 100,000 miles Part 2 CE16 100,000 miles AE16 100,000 miles Exhaust Valve p. 20

21 MMT Impacts on Components HEGO Sensor Alliance Study Spark Plugs Part 1 Oxygen Sensors from another Mn study (Sheath removed) Part 2 Static Response of HEGO Sensors in Propane/O2/N2 Mixture Response signal for MMT exposed Front HEGO deteriorated to a much greater degree than the HEGO exposed to Clear fuel CE16 Front 100,000 miles AE16 Front 100,000 miles p. 21

22 Owner Guide Regular Fuel Recommendation Choosing the right fuel User manuals of Ford Vehicles in Argentina are aligned with WorldWide Ford Recommendations with regards to Mn-based additives. p. 22

23 Ford Supports Voluntary Pump Labeling The use of manganese-based gasoline additives is a Backward Step Considering revisions to the Owner Guide to recommend using fuels that are labeled manganese-free Considering informing our dealers that if the fuel is not labeled, they should tell customers to purchase fuel only from pumps labeled Manganese-free p. 23

24 Canada Is Manganese-FREE! Shell Canada Effective January 2004 Irving Chevron As of November 2003 Sunoco Ultra94 Manganese-free Since 2001 Since Automaker s Choice Introduction prior to 2003 All other oil companies stopped using manganese additives in Canada. p. 24

25 What s Happening around the World? US Ban on manganese in California and US RFG Surveys indicate rare use in other US fuels Russia, Germany and Czech Republic also Ban on manganese Other countries which do not use manganese Western Europe Japan Australia Canada India Brazil Africa (BP removal of manganese) Argentina: Manganese use increasing Trend is contrary to the rest of the world p. 25 * Surveys indicate no use

26 Opportunity Gasoline and Ethanol Blend Argentinean Legislation allows the blend from 5% to 10% of ethanol in gasoline (Resolucion 733/2009). 5% of ethanol blended with gasoline provide a higher octane response than the MMT in the concentration used today in Argentina: 1.5 points with 5% ethanol for 95 RON gasoline against 1 point max with MMT. p. 26

27 Conclusions DO NOT USE Mn-CONTAINING GASOLINE IN CATALYST EQUIPPED VEHICLES. Gasoline containing manganese (Mn) has been eliminated from Canada as of Summer 2006, according to the Alliance of Automobile fuel survey data. As a result, catalyst rate of returns declined in Canada to match trends in the US, where manganese containing gasoline is not available. Internal testing of returned samples show reduced emission performance for samples with Mn-deposits from Canada compared to US clear samples. Post mortem catalyst and component testing from the Alliance study confirms the presence of Mn deposits and resulting decline in functionality. p. 27

28 Summary and Recommendations Field issues are associated with Advanced Emission Technology mileage and Mn concentration are very important factors for system contamination Engine-Dynamometer and Vehicle Testing replicate the plugging concern found in the field Post Mortem analyses confirm Mn-deposits (Mn 3 O 4 ) on engine and emission components REMOVE ALL METAL-BASED FUEL ADDITIVES FROM ARGENTINEAN MARKET Consistent with NA / European / Brazil Practice p. 28

29 THANK YOU. QUESTIONS? p. 29