alternative fuels and potential material compatibility...

The miracles of science™

Alternative Fuels and Potential Material Compatibility Issues

DuPont Automotive Annual Fuel Luncheon April 16, 2008

2007© FUEL QUALITY SERVICES, INC.The miracles of science™

OVERVIEWBackgroundFuel System MaterialsRisk Factors Metals and Non-metalsFuel Chemistry ComparisonBiodieselE85Conclusion


Background• Industrialized countries are the

largest consumers of oil but until 1998 had not been the most important growth market,

= Industrialized and Newly Industrialized Countries

Newly industrialized countries since 2007

Andorra Czech Rep. Hong Kong Japan New Zealand Slovenia TurkeyAustralia Denmark Hungary Latvia Norway South Africa UKAustria Estonia Iceland Lithuania Philippines South Korea USABelgium Finland India Luxembourg Poland SpainBrazil France Ireland Malaysia Portugal Sweden

Canada Germany Israel Mexico San Marino SwitzerlandChina Greece Italy Netherlands Slovakia Thailand


Background• OECD countries account for 2/3 of

the daily global oil consumption,• From 1991-1997, demand in the

OECD only grew by 11% whereas demand outside the OECD grew by 35%

OECD – Organization for Economic Cooperation and Development

Australia Finland Ireland New Zealand SpainAustria France Italy Norway SwedenBelgium Germany Japan Poland SwitzerlandCanada Greece Luxembourg Portugal Turkey

Czech Rep. Hungary Mexico Slovakia UKDenmark Iceland Netherlands South Korea USA


Background

• Developed economies use crude more intensively than developing economies,

• For example:– U.S & Canada ~3 gal. per day per capita

– OECD* Countries ~1.4 gal per day per capita

– Outside OECD ~0.2 gal per day per capita* OECD – Organization for Economic Cooperation and Development


Background

• The United States and Canada use crude oil more for transportation than for heat and power,

• For the rest of the world, the emphasis is reversed, crude is used for power and heat and much less on transportation,


Background

• In the United States, ~2/3 of all crude oil is used for transportation fuels:

• On average, for every 2 gallons of crude per day per capita:– Gasoline accounts for 1.28 gal of crude,

– Diesel accounts for 0.68 gal of crude,

– Jet fuel accounts for 0.18 gal of crude.


Background

• Therefore, the current solution is to offset the demand on petroleum based transportation fuels through the use of alternative or biomass fuels:

• Current solutions: – Fuels replacements such as B100 and E85 – Non- petroleum additives / fuel extenders such as

B20/E10.


BackgroundKey Cost Drivers to Justify Manufacturing Biofuels: • Price of crude oil >$60.00 per barrel• Desire for energy and power self sufficiency• Access to land• Cost effective labor• Access to capital• Infrastructure and technology• Domestic & export markets• Availability and cost of feedstock


Background• Spark Ignition Engines:

– Alcohol Fuels• Methanol (Aggressive to metal and non-metals-California)• E85 (Fuel Replacement or blend stock)• E10 (Fuel Extender)• Butanol (Currently under R&D-Less Aggressive)

• Compression Ignition Engines:– Biodiesel & Blends

• SVO (Leaves residue in engine cylinder)• FAEE (Belgium patent in 1937 no further development)• B100 (FAME-current common blend stock)• B5, B20 (FAME used as a fuel extender)


Background

In general, several issues must be considered when evaluating material compatibility, :

1. Changes in the physical, chemical or mechanical properties of a material from exposure to the fuel product,

2. Exposure or contact of a fuel to a metal or non-metal should not alter the performance of the material, induce new or enhance existing failure mechanisms.

3. Conversely, metals or non-metals in contact with a fuel should not corrode thus contaminating the fuel and impairing engine performance.


Fuel System Materials

• Automotive fuel systems can be made from a variety of materials that include:– Metals such as

• aluminum, brass, copper, steel, zinc

– Non-metals may include: • Elastomers• Thermoplastics,• Thermosets


General Risk Factors for Metal Corrosion

• Fluids with conductive properties• Presence of ionic contaminants such as chlorides and acids, • Macro/micro environments with an acidic pH,• The presence of microorganisms that facilitate/accelerate known

corrosion mechanisms, • Dissimilar metals joined electrically by a conductive fluid.


Conductivities of Various FluidsElectrical Conductivity

1.00E-14

1.00E-13

1.00E-12

1.00E-11

1.00E-10

1.00E-09

1.00E-08

1.00E-07

1.00E-06

1.00E-05

1.00E-04

1.00E-03

1.00E-02

1.00E-01

1.00E+00Gasoline Diesel B100 E100 M100 Pure Water

Product

Con

duct

ivity

(Sie

men

per

Cen

timet

er)


* **

**

*

*

Risk Factor -

Metals

Galvanic Series


PERMEATION: Solvent ingress is related to a system potential driven by a chemical or activity gradient,SWELLING: The result of interaction between the solvent molecule and the polymer matrix which may include hydroxyls, esters, free radicals and peroxides.

LEACHING: Loss of antioxidants, fillers, heat stabilizers, plasticizers during solvent permeation and extraction,PLASTICIZATION: Degradation in the performance of the non-metal as a result of solvent diffusion, potentially affecting strength and integrity of the non-metal matrix

General Risk Factors for Non-metal Degradation

µ = µo

+RT ln a/ao

OH C

O

O CH3R

H•O--O

--


Fuel Chemistry ComparisonPetroleum Base Fuels: Biomass fuels:Have low conductivities Are more conductive Low dissolved water content 0.006%- 0.01%

Increased dissolved water content E10 (0.5%) - E85 (11%)B100 1200-2500 ppm

Nonpolar hydrocarbon species EtOH - Short chain polar 1º alcohol , FAME

Ester functional group. Peroxides

• Do not absorb or permeate through metals,• Potential compatibility issues have been noted with elastomeric and thermoplastic materials• Functional groups can increase chemical activity, reactivity, and bioavailability


Biodiesel

• Composition/Feedstock– Feedstock vegetable oils, used grease, or

animal fats.– Different feed stocks for FAME will influence

some properties of the fuel (i.e., saturated vs. unsaturated)


Made By Transesterification

Source: Understanding Biodiesel Fuel Quality and Performance

Soy Used GreaseAnimal Fat

+(Catalyst NaOH / KOH)

Biodiesel*

+ Glycerin

+ Byproducts*Vegetable oils will contain natural antioxidants


Biodiesel & Potential Reactive Sites

More Reactive(Bis-Allylic Site)

Most Reactive(Bis-Allylic Site)

Least Reactive

Reactive Sites(Allylic Site)

C16:0

C18:0

C18:1

C18:2

C18:3

Saturated Molecules

Unsaturated Molecules


Various Biodiesel FeedstocksDistribution of saturated and polyunsaturated constituents


Biodiesel

• Potential Issues and Concerns (B100):– B100 can act as a solvent, degrade, soften, seep through certain

hoses, gaskets, seals with prolonged exposure– Biodiesel material compatibility issues decrease proportionally

with the concentration of biodiesel, – Biodiesel has a greater propensity to support microbial growth,


BiodieselCompatible and Incompatible Non-Metals

Materials1,2 Fuel Compared to Diesel Fuel PerformanceTeflon® PTFE B100 Little Change

Nylon-6/6 B100 Little Change

PPA3 B100 Little Change

Viton® A401-C B100 Little Change

Viton® GFLT B100 Little Change

Polyurethane / Fluorosilicone B100 Hardness No Change : Swell ↑6%

Polypropylene B100 Hardness ↓10% : Swell ↑8-15%Nitrile B100 Hardness ↓20% : Swell ↑18%

Polyvinyl / Silicone B100, B10-B50 Significant Performance Degradation1. E.A Frame, G.B. Bessee and H.W. Marbach, Biodiesel Fuel Technology for Military Application, U.S. Army TARDEC Fuels and Lubricants Research Facility,

Southwest Research Institute, Interim Report TFLP No. 317, December 19972 Biodiesel, Use and Handling Guidelines, NREL/TP-580-30004, September 2001. 3 Data provided by DuPont


Biodiesel (B100) and Biodiesel Blends (B5-B20)

Metals (B100- BXX) Non-Metals (BXX)Such as brass, bronze, copper, lead, tin, and zinc which may act as catalysts leading to oxidative degradation and the formation insoluble, soaps and gels

Problems with non-metals tend to diminish as biodiesel concentration decreases

Biodiesel, Use and Handling Guidelines, DOE/GO-102004-1999, Revised November 2004.


Ethanol Fuels Ed

85

• Compositions & Feedstocks:– 75% - 85% Ethanol (EtOH) &

15% - 25% Unleaded gasoline – Formulation seasonally adjusted

• Sources Benefits / Comments:– Fermentation from corn (primary source)– Chemically from ethylene,– Cellulose agricultural waste, starch, or sugar,


Ed

85 Issues and Concerns

• Potential Issues and Concerns– Increased Conductivity which affects metals– Solvent Action– Compatibility / Permeability which affects non-metals– Phase Separation


Ethanol Fuels Ed

85Compatible Non-Metals Successfully Used with E85

Material1,2,3 Fuel PerformanceViton® E85 Used SuccessfullyTeflon® E85 Used Successfully

PPA4 E85 Used SuccessfullyBuna-N E85 Used Successfully

Neoprene E85 Used SuccessfullyPolyethylene E85 Used Successfully

Polypropylene E85 Used SuccessfullyNitrile E85 Used Successfully

1. Guidelines for Handling, Storing & Dispensing Fuel Ethanol, U.S. Department of Energy, Control W-31-109-Eng-36.2. Handbook s for Handling, Storing & Dispensing E85, NREL, DOE/GO-1002001-956, April 2002.3. Properties of Alcohol Transportation Fuels, Biofuel System Division, Office of Alternate Fuels, US DOE July 1991 4. Data provided by DuPont.


Ethanol Fuels Ed

85Incompatible Non-Metals Not Successfully Used with E85

Material1,2,3 Fuel PerformanceNatural Rubber E85 Performance DegradationPolyurethane E85 Performance DegradationCork Gasket E85 Performance Degradation

Leather E85 Performance DegradationPolyester Bonded Fiberglass E85 Performance Degradation

Polyvinyl Chloride E85 Performance DegradationNylon E85 Performance Degradation

•Guidelines for Handling, Storing & Dispensing Fuel Ethanol, U.S. Department of Energy, Control W-31-109-Eng-36.•Handbook s for Handling, Storing & Dispensing E85, NREL, DOE/GO-1002001-956, April 2002.•Properties of Alcohol Transportation Fuels, Biofuel System Division, Office of Alternate Fuels, US DOE July 1991


Ethanol Fuels Ed

85

Metals That Are Compatible Metals That Are Incompatible– Black Iron– Bronze– Mild steel– Stainless steel– Unplated steel– Nickel Plating for soft metals (i.e.,

aluminum)

– Aluminum– Brass– Copper Alloys– Lead– Lead Solder– Tern-plated steel (Fuel Tanks)– Zinc


Ed

85-

Example of Corrosion

• Same facility• Same install date• Top is E85 STP• Bottom is standard

petroleum fuel STP

Photograph Courtesy of Rounds and Associates (Public Domain Information)


Ed

85 –

Vent Pipe Deterioration



Ed

85 -

Seals and Gasket Leak



Ed

85 -

Catastrophic Failure



Conclusion• As a result of economics and geopolitics, crude oil is

increasing in cost and becoming a limited resource, • It is only reasonable to expect that the chemistry of

transportation fuels will change in the future,• The industry needs to continue its research as well as

develop materials to address the challenges associated with future transportation fuels as it applies not only to the automotive industry but also the fuel storage and distribution network.


Thank You

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