mmt & Ferrocene

A Comparison

June 2011

Contents
History & Experience

Features and Benefits

Wear Performance Handling, Stability & Transport Issues

Health, Safety & Environment

Octane Performance International Reviews and Approvals

mmt (Methylcyclopentadienyl Manganese Tricarbonyl) HiTEC 3000

Organometallic Compound Based On Manganese
Pure Liquid (24.4 % Mn)
Compatible with all Fuel Components

Discovered in the late 1950s

Production Plant Completed in mid-1970

First Used by Refiners in Unleaded in 1974

Used in USA (including California) in low lead gasoline through early 1990s.

Ferrocene (Dicyclopentadienyl Iron) Plutocen G

Organometallic Compound Based on Iron.
Comes in Crystalline Powder (30 % Fe)
Low Solubility in Gasoline (10g/100g)

Discovered in 1951

Afton owned rights to Ferrocene in 50s

Realised there was no way to overcome engine wear problems.

Afton sold rights to VEBA/OEL in the 60s for $1.00

Marketed by Pluto (part of VEBA)

Octel Purchased Pluto in late 90s Octel renamed as Innospec in 2005

Unleaded Gasoline with mmt (HiTEC 3000)

Used in over 150 Refineries and Terminals in >50 Countries

Used by Refineries to make unleaded gasoline in:

US & Canada Europe Asia

Central & South America

Africa

Australia

History & Experience

mmt (HiTEC 3000) Discovered in 1950s Ownership in 1950s Ownership in 1960s Ownership in 1990s and 2000s Yes Afton Afton Afton Ferrocene (Plutocen G) Yes Afton Pluto Octel / Innospec

Anti-Knock Effectiveness
1974 - First Introduction to US 1978 Clean Air Act bans use in UL 1979 EPA Grants Temporary Waiver 80s 1994 Used in Leaded gasoline 1995 EPA Grants Waiver in UL

Best
Yes Yes Yes Yes Yes

Good
No Yes No No No

History & Experience (cont.)

mmt (HiTEC 3000) Used by multi-national oil companies Used in European Union Used in US & Canada Used in Asia, Americas Yes Yes Yes Yes Ferrocene (Plutocen G) No No No No

Used in China
Used in Russia

Yes
Yes

No
?

Features & Benefits

mmt (HiTEC 3000) Max recommended treat for cars with catalyst Ferrocene (Plutocen G)

18 mg Mn/l 1.8 3.0

1.5 2.5 Yes Yes Yes

6 mg Fe/l 0.5 1.2

0.8 1.6 Yes Yes No

RON gain at recommended treat

RON gain at equal metals (10 mg/l) Reduces Refinery Emissions Reduces Crude Oil Consumption Protects Against Valve Seat Wear

Features & Benefits (cont.)

mmt (HiTEC 3000) Promotes Catalyst Efficiency Lowers CO, NOx, & N2O Emissions Approved for Pipeline Use Safely Store & Handle at Refinery Yes Yes Yes Yes Ferrocene (Plutocen G) No No No No

Easy to Safely Transport as Liquid

Extensively Tested

Yes
Yes

N/A
No

Approved by Majors for Exchange

Approved for ULG in USA

Yes
Yes (Afton)

No
No (Octel)

Automotive Fleet Testing

mmt (HiTEC 3000)
Number of Cars in Fleet Tests Number of Miles Driven in Fleet Tests Fleets/Fuels Approved by US EPA and OEMs >150 >10 million Yes

Ferrocene (Plutocen G)
Unknown Unknown No

Fleets Run at Independent Laboratories

Fleets Represent 50% of USA Car Sales Fleets Designed to Evaluate Emissions Fleet Maintenance Records Open for Inspection

Yes
Yes Yes Yes

No
No No No

Automotive Fleet Testing (cont.)

mmt (HiTEC 3000)
Fleets Equipped with Latest Catalysts and OBD Yes

Ferrocene (Plutocen G)
No

Independent Statistical Analysis of Data No Harm Testing on Spark Plugs, Catalysts, OBD US EPA Statement Confirming Lower Emissions
US EPA Statement Confirming No Harms Canadian Statement Confirming No Harms Cases of Fuel Pump Failures

Yes
Yes

No
No

Yes
Yes Yes No

No
No No Yes

Automotive Fleet Testing (cont.)

mmt (HiTEC 3000) 25 Years of Safe Usage in CFR / Octane Engines 15 Years of Safe Usage with Detergents in Bulk Fuel Superior BMW Deposit Control with Detergents Controls Deposits in Gasoline Direct Injection Engines Ferrocene (Plutocen G)

Yes
Yes Yes Yes

No
No No No

mmt The Most Extensively Tested Fuel Additive in History

In support of its current application, Ethyl conducted the most extensive test program ever conducted by a waiver applicant [after seeking] and receiv[ing] EPAs help in design of a test program
57 Fed. Reg. 2535, 2538

(January 22, 1992)

mmt - Extensive Review

Ethyl has demonstrated that the use of HiTEC 3000 (MMT) will not cause or contribute to a failure of any emission control device or system.

US EPA (Fed. Reg. /59 FR 42227/August 17, 1994)

Current scientific information fails to demonstrate that MMT impairs the proper functioning of automotive onboard diagnostic systemsFurthermore, this no new scientific evidence to modify the conclusions drawn by Health Canada in 1994 that MMT is no health threat. Government of Canada Statement on mmt July 20, 1998

Ferrocene & Engine Wear

Afton saw Ferrocene as Possible Marketable Anti Knock Compound
Combustion Products Formed an Abrasive Powder

Found that Concentrations above 20 ppm Fe caused Significant Engine Wear

VEBA Marketed Product for Over 25 Years

Recommended dosage for gasoline was 5.5 ppm Fe max or approximately 4 mg Fe/l At higher dosages, the ORI of the engine grows faster than the gain of octane
Subsequently primarily marketed as additive for home heating oil

Ferrocene & Engine Wear (cont.)

In China, ferrocene was initially used in some unleaded gasoline.
The Iron in the fuel caused blockage of fuel injectors

Vehicles were shut down

Ferrocene now Banned in China !

Certain Major Oil Companies will not allow ferrocene to be tested in CFR engines. Engine Lubricants Iron in motor oil, did it come from engine wear or the fuel?

Wear Performance
mmt (HiTEC 3000)
Additive in Pure Form Pure Liquid Stable Indefinitely

Ferrocene (Plutocen G)
Solid Powder (Wear Material) Short Term solid precipitate possible

Stability of Additive

Wear Metals in Used Oil Analysis

Treat Rate Limit Due to ORI Treat Rate Limit on Wear Banned Due to Wear Sequence VE Performance

No
No No No Pass

Yes
5 ppm Fe (Pluto) 6 ppm Fe (Pluto) Yes China 99 Fail

Wear Performance
mmt (HiTEC 3000) Valve Seat Protection Fleet Cars Used Oil Analysis Fleet Test Subject to Ind. Review >20 years Experience in Canadian Fuels Canadian Govt. and Court Review of Data Marketing Rights Sold because of Wear Concerns Yes Yes Yes Yes Yes No Ferrocene (Plutocen G) No No No No No Yes

Wear Concerns in CFR / Octane Engines

No

Yes

Health, Safety & Environmental Issues

Manganese
Essential Element for Human Health Abundant in Nature
Abundant in Food

Iron
Yes Yes
Yes

Yes Yes
Yes

Included in Vitamin Supplements

Normally Found in the Air (dust suspension) Released in the Air (mostly from Steel Production)

Yes
Yes

Yes
Yes

Yes Yes
Yes Yes

Yes Yes
Yes No

Toxic in High Concentrations

Safe in Low Concentrations

*US EPA alternative Tier 2 health assessment performed and accepted

*Only Afton has completed these tests. No other additive has gone through this process

Typical Octane Response mmt (HiTEC 3000) vs. Ferrocene (Plutocen G)

Research Octane Number Gain
2 1.8 1.6 1.4 1.2 1 0.8 0.6 0.4 0.2 0 0 9
mg metal/liter

MMT Ferrocene

18

mmt (HiTEC 3000) Reviews

US EPA acceptance for unleaded gasoline (1995), updated (2000)

Canadian Government review and acceptance (1998), updated (2000 & 2010)) United Nations/ECE Task Force recommendation for Lead Replacement Petrol (LRP) (1998)
French government acceptance for unleaded and LRP (1999) UK Health Dept. & British Standards Institute acceptance, LRP (1999)

China National EPA of Peoples Republic of China and national specification approval for unleaded gasoline (1999)
Argentina IRAM (Government/industry) specification approval for unleaded gasoline (1999) Australia EPA accepted for LRP (2000), approval for unleaded (2001) Philippines Department of Energy, product registration (2000)

Global use of (HiTEC 3000) mmt

Use globally
For over 30 years, mmt has been in use by more than 150 refineries and terminals in over 53 countries as the most economic octane-enhancing

option to the global octane squeeze.

Why some arent using it

Refinery investment allowing to achieve required octane levels Use of existing Petrochemical products/supply

Excess octane, RON giveaway

mmt
(HiTEC 3000) Imagine the Potential

Thank you!