Upload
others
View
7
Download
0
Embed Size (px)
Citation preview
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
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
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
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
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
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
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
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
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,
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
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.
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
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.
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
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
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
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)
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
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.
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
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
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
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.
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
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)
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
* **
**
*
*
Risk Factor -
Metals
Galvanic Series
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
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
--
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
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
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
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)
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
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
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
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
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
Various Biodiesel FeedstocksDistribution of saturated and polyunsaturated constituents
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
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,
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
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
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
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.
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
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,
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
Ed
85 Issues and Concerns
• Potential Issues and Concerns– Increased Conductivity which affects metals– Solvent Action– Compatibility / Permeability which affects non-metals– Phase Separation
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
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.
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
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
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
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
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
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)
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
Ed
85 –
Vent Pipe Deterioration
Photograph Courtesy of Rounds and Associates (Public Domain Information)
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
Ed
85 -
Seals and Gasket Leak
Photograph Courtesy of Rounds and Associates (Public Domain Information)
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
Ed
85 -
Catastrophic Failure
Photograph Courtesy of Rounds and Associates (Public Domain Information)
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
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.
2007© FUEL QUALITY SERVICES, INC.The miracles of science™
Thank You