Mmt vs Ferrocene Presentation 170611

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 1950’s

► 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 1990’s.

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 50’s

– Realised there was no way to overcome engine wear problems.

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

– Marketed by Pluto (part of VEBA)

Octel Purchased Pluto in late 90’s

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)

Ferrocene

(Plutocen® G)

Discovered in 1950’s Yes Yes

Ownership in 1950’s Afton Afton

Ownership in 1960’s Afton Pluto

Ownership in 1990’s and 2000’s Afton Octel / Innospec

Anti-Knock Effectiveness Best Good

1974 - First Introduction to US Yes No

1978 – Clean Air Act bans use in UL Yes Yes

1979 – EPA Grants Temporary Waiver Yes No

80’s – 1994 Used in Leaded gasoline Yes No

1995 – EPA Grants Waiver in UL Yes No

History & Experience (cont.)

mmt®

(HiTEC 3000)

Ferrocene

(Plutocen® G)

Used by multi-national oil companies Yes No

Used in European Union Yes No

Used in US & Canada Yes No

Used in Asia, Americas Yes No

Used in China Yes No

Used in Russia Yes ?

Features & Benefits

mmt®

(HiTEC 3000)

Ferrocene

(Plutocen® G)

Max recommended treat for cars with

catalyst 18 mg Mn/l 6 mg Fe/l

RON gain at recommended treat 1.8 – 3.0 0.5 – 1.2

RON gain at equal metals (10 mg/l) 1.5 – 2.5 0.8 – 1.6

Reduces Refinery Emissions Yes Yes

Reduces Crude Oil Consumption Yes Yes

Protects Against Valve Seat Wear Yes No

Features & Benefits (cont.)

mmt®

(HiTEC 3000)

Ferrocene

(Plutocen® G)

Promotes Catalyst Efficiency Yes No

Lowers CO, NOx, & N2O Emissions Yes No

Approved for Pipeline Use Yes No

Safely Store & Handle at Refinery Yes No

Easy to Safely Transport as Liquid Yes N/A

Extensively Tested Yes No

Approved by Majors for Exchange Yes No

Approved for ULG in USA Yes (Afton) No (Octel)

Automotive Fleet Testing

mmt®

(HiTEC 3000)

Ferrocene

(Plutocen® G)

Number of Cars in Fleet Tests >150 Unknown

Number of Miles Driven in Fleet Tests >10 million Unknown

Fleets/Fuels Approved by US EPA and

OEMs Yes No

Fleets Run at Independent Laboratories Yes No

Fleets Represent 50% of USA Car Sales Yes No

Fleets Designed to Evaluate Emissions Yes No

Fleet Maintenance Records Open for

Inspection Yes No

Automotive Fleet Testing (cont.)

mmt®

(HiTEC 3000)

Ferrocene

(Plutocen® G)

Fleets Equipped with Latest Catalysts and

OBD Yes No

Independent Statistical Analysis of Data Yes No

No Harm Testing on Spark Plugs,

Catalysts, OBD Yes No

US EPA Statement Confirming Lower

Emissions Yes No

US EPA Statement Confirming No Harms Yes No

Canadian Statement Confirming No Harms Yes No

Cases of Fuel Pump Failures No Yes

Automotive Fleet Testing (cont.)

mmt®

(HiTEC 3000)

Ferrocene

(Plutocen® G)

25 Years of Safe Usage in CFR /

Octane Engines Yes No

15 Years of Safe Usage with

Detergents in Bulk Fuel Yes No

Superior BMW Deposit Control with

Detergents Yes No

Controls Deposits in Gasoline Direct

Injection Engines Yes 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] EPA’s 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 on-

board diagnostic systems…Furthermore, 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)

Ferrocene

(Plutocen® G)

Additive in Pure Form Pure Liquid Solid Powder

(Wear Material)

Stability of Additive Stable

Indefinitely

Short Term – solid

precipitate

possible

Wear Metals in Used Oil Analysis No Yes

Treat Rate Limit Due to ORI No 5 ppm Fe (Pluto)

Treat Rate Limit on Wear No 6 ppm Fe (Pluto)

Banned Due to Wear No Yes – China ’99

Sequence VE Performance Pass Fail

Wear Performance

mmt®

(HiTEC 3000)

Ferrocene

(Plutocen® G)

Valve Seat Protection Yes No

Fleet Cars Used Oil Analysis Yes No

Fleet Test Subject to Ind. Review Yes No

>20 years Experience in Canadian

Fuels

Yes No

Canadian Govt. and Court Review of

Data

Yes No

Marketing Rights Sold because of

Wear Concerns

No Yes

Wear Concerns in CFR / Octane

Engines

No Yes

Health, Safety & Environmental Issues

Manganese Iron

Essential Element for Human Health Yes Yes

Abundant in Nature Yes Yes

Abundant in Food Yes Yes

Included in Vitamin Supplements Yes Yes

Normally Found in the Air (dust suspension) Yes Yes

Released in the Air (mostly from Steel

Production) Yes Yes

Toxic in High Concentrations Yes Yes

Safe in Low Concentrations Yes Yes

*US EPA alternative Tier 2 health assessment

performed and accepted Yes No

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

Typical Octane Response mmt® (HiTEC® 3000)

vs. Ferrocene (Plutocen® G)

0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

1.8

2

0 9 18

mg metal/liter

Rese

arch

Octa

ne N

um

ber G

ain

MMT

Ferrocene

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 aren’t 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!