PEI

PEI // NACS
NACS 2006
2006
Alternative
Alternative Fuels
Fuels and
and
Material
Material Compatibility
Compatibility
Edward W. English, II
Vice President – Technical Director
Fuel Quality Services, Inc.
[email protected]
OVERVIEW

§ General Background
§ Introduction
§ System Configuration / Materials
§ Fuels (Petroleum / Biomass)
§ Risk Factors for Compatibility
§ Other Issues to Consider
§ Ethanol Fuels
§ Conclusion
Introduction
§ Why alternative fuels?:
§ Legislated by EPAct 1992 to:
§ Reduce reliance on foreign oil & Improve air quality,
§ Alternative fuels include
§ Methanol, Ethanol, and their blends (10% - 85%)
§ Biodiesel - B100, B20
§ Natural Gas and LPG
§ Coal derived fuels (Fisher-Tropsch)
§ Hydrogen
§ Electricity
§ P-Series Fuel
Introduction
§ Ethanol (EtOH):
§ Quite a long history of use, most notably Henry Ford use of
ethanol to power his earlier cars and WWII,
§ Currently E10 comprises 30% of our fuel as,
§ Fuel extender, octane improver, and improved vehicle
emissions
§ Industry slowly shifting to E85 but can only be use in AFV/FFV,
§ AFV/FFV Manufacturers:
§ General Motors Mazda
§ Daimler Chrysler Mercedes
§ Ford Mercury
§ Isuzu Nissan
Introduction
§ Material Compatibility
§ Compatibility issues with fueling systems and
vehicles identified while evaluating M85 fuels in
California during 1980’s and 1990’s, (Methanol
Fueling Systems March 1996)

§ Technical issues involving EtOH fuels,

§ System preparation & system conversion, and Storage &
material compatibility Dispensing
§ Phase Separation
§ Conductivity issues
§ Compatibility issues
§ Solvent Action
Introduction
§ Biodiesel
§ Similar history, most notable Rudolf Diesel 1898 powered his
engine with peanut oil at the Paris World’s Fair and WWII,
§ Feedstock includes
§ Vegetable oil
§ Animals fats
§ Used greases
§ Improves air quality but still has issues with NOx in
compression ignition engines
§ Readily useable in diesel engines, no engine conversion
necessary, registered with EPA as a fuel and fuel additive,
Introduction Storage &
Dispensing

§ Materials Compatibility
§ Material compatibility issues identified with
metals and non-metals, primarily with B100
and to a lesser extent B20

§ Technical issues involve

§ System preparation & system conversion, and
material compatibility
§ Source of feedstock
§ Dissolved and free water
§ Biodegradation
System Configuration / Materials

§ Will discuss materials that are

found in a UST and dispensing
system configuration:
§ Tank & Piping
§ Pump System
§ Dispenser & Nozzle
§ Vapor Recovery System
System Configuration / Materials
§ Typical materials include,
§ Metals generally found in fueling systems:
§ aluminum, brass, copper, steel, zinc
§ Non-metals generally used in fueling systems:
§ Elastomers - Flexible hoses, seals, gaskets and packing,
§ Thermoplastics - Underground flex piping, sumps and
vapor recovery tubing,
§ Thermosets - Rigid piping and USTs,
§ Ceramics, pipe dope, and organic coatings
System Configuration / Materials
§ Elastomers
§ Generally 3% cross linkage, can be Polymers
stretched to 2x original length, will
contract to original size; tend to be
long coiled chains
Elastomers Plastics
§ Thermoplastics
§ Softened when heated, hardened
when cooled, can be repeatedly
melted, most are linear and branched Thermoplastics
polymers, with no to little cross
linking.
Thermoset
§ Thermoset
§ Do not soften upon heating, cannot
be remelted, extensive cross linking,
tend exhibit 3D structure
Fuels - Petroleum
§ There are 100’s-1000’s Compounds in Petroleum Fuels:

§ Linear & branched

R
§ Cyclic

§ Aromatic & Polyaromatic

Fuels - Biomass
§ Ethanol Fuel Blends § Biodiesel Fuel Blends
O
Methyl CH3
O
Palmitate16:0
O
CH3
Methyl Stearate
O
18:0
Methyl Oleate O
CH3
18:1 O

Methyl O
CH3
Linoleate 18:2 O

Methyl O
CH3
Linolenate 18:3 O
Fuels Comparison
Petroleum Base Fuels: Biomass fuels:
Have low conductivities Are more conductive
§ Gasoline 1x10-14 mho/cm § Neat Ethanol 1x10-9 mho/cm,
§ Diesel 1x10-12 mho/cm § B100 5x10-12 mho/cm
Hold very little water dissolved water Hold much more water dissolved water
§ 60-100 ppm § EtOH 4900 ppm (~0.5%)
§ Biodiesel 1200-2500 ppm
§ do not absorb or permeate through metals,
§ To date no information in the public domain indicating, compatibility issues with
thermoset USTs,
§ Compatibility issues have been noted thermoplastic and elastomeric materials
§ Biomass fuels contain functional groups that increase chemical activity, reactivity,
and bioavailability
Risk Factor - Metals
§ Recognized risk factors for metal corrosion:
§ Anodic metals tend to corrode more readily in a given
environment or in the presence of cathodic metals (relative
position on a galvanic series)
§ Water. chemical contaminants, and salts in the fuel system can
increase system conductivity,
§ Microbial involvement can accelerate galvanic and pitting
corrosion of metal that would normally take much longer under
“sterile” conditions,
Risk Factor - Metals

*
*

*
*
* *
Risk Factors – Water
Refinery Water Intrusion Storage
Storage and Distribution Level
Pipeline
Retail
Distribution

Water Intrusion at the

Retail Level
Courtesy of Steel Tank Institute: “ Keeping Water Out of Your
Storage System,”
System,” March 2004
Risk Factors - Microorganisms
Diesel

Gasoline

Biodiesel
Risk Factors for Non-metals
Recognized risk factors for degradation of non-metals include

Solvent ingress related to chemical µ = µo+RT ln a/ao

potential driven by activity gradient,
Interaction between the solvent O
OH
molecule and the polymer matrix, R C O CH3

Loss antioxidants, fillers, heat Loss of plasticizers from

stabilizers, plasticizers due to solvent polymer matrix
permeation,
Result of solvent diffusion Potentially affecting
strength and integrity of
the non-metal matrix,
Risk Factors for Non-metals
Activity of MtBE, Toluene, and Activity of EtOH, Toluene, and
Isooctane as a function of ether in Isooctane as a function of ether in
ASTM Fuel C ASTM Fuel C

EtOH
MtBE

Toluene Toluene
-+
-
Isooctane
Isooctane
Risk Factors for Non-metals
§ Symptoms of polymer
incompatibility:,
§ Discoloration
§ Swelling
§ Degradation
§ Elongation/Creep
§ Softening / Jellying
§ Embrittlement
§ Delamination

Courtesy: Ernest M. Roggelin, FDEP/UST, Lustline #47

ETHANOL BLEND FUELS

E10
10% Ethanol
 Ethanol Blends – E10

§ Main technical issues:

§ Phase Separation
§ Solvent action could
dissolve tank lacquer,
§ Compatibility /
Permeability Relative Electrical Conductivities

1.00E-06

§ Increased Fuel 1.00E-07

Gasoline #2 Diesel B100 EtOH Ultra Pure
H2O
Conductivty (mhos/cm)

Conductivity
1.00E-08

1.00E-09

1.00E-10

1.00E-11

1.00E-12

1.00E-13

1.00E-14
Product Type
 Ethanol Blends – E10
Generally Compatible Materials
§ Metals § Elastomers § Polymers
§ Aluminum, § Fluorocarbons § Acetal
§ Brass, § Fluorosilicone, § Polyamides
§ Bronze, § Buna-N (hoses & § Polypropylene
§ Carbon steel, gaskets), § PTFE
§ Stainless steel, § Natural rubber § Thermoplastics
§ Polychloroprene § Thermoset
(hoses & gaskets),
§ Polysulfide rubber
Ethanol Blends – E10
Vulnerable Materials
§ Metals § Elastomers § Polymers
§ Zinc-galvanized § Buna-N (seals only), § Polyurethane
§ Polychloroprene § Alcohol-based
(seals only), pipe dope
§ Urethane rubber
Ethanol Blends – E10
§ E10 blends have been in use for nearly three decades and most, if
not all, material compatibility issues have been identified and
corrected,
§ However, there may be some instances where aged gasoline
dispensing systems that are not properly converted to dispense
E10 may see issues with:
§ Mechanical seals
§ Meters
§ Filters
§ Accelerated Corrosion
§ Metals, elastomers, and polymers that are compatible with 100%
MeOH or E85 should be certainly compatible with E10 fuel,
Ethanol Blends – E10

§ A surveillance and housekeeping program is recommended to

monitor the UST and dispenser system for leaks or
operational issues as a result of:
§ Corrosion mechanisms to metals,
§ Potential degradation of polymers,
§ Microbial growth,
 Ethanol Blends – E85 1.00E-06
Relative Electrical Conductivities

Gasoline #2 Diesel B100 EtOH Ultra Pure H2O

1.00E-07

Conductivty (mhos/cm)
1.00E-08

1.00E-09

1.00E-10

§ Four main issues 1.00E-11

1.00E-12

§ Increased 1.00E-13

1.00E-14

Conductivity Driving gradient,

Product Type

§ Solvent Action Solvent & polymer interaction,

Loss antioxidants, fillers, heat stabilizers,
§ Compatibility / plasticizers due to solvent permeation,

Permeability Solvent diffusion effecting strength and

integrity,

§ Phase Separation
Ethanol Blends – E85
§ Potential Issues and Concerns:
§ Materials that are in continuous contact with E85 fuel,
§ Improper system inspection prior to conversion,
§ Certain metals and non-metals are vulnerable to corrosion
or degradation due to E85,
§ Fuel filters with improper pore size or efficiency rating may
allow dissolved contaminants from the UST and dispensing
system to enter the vehicle fuel tank significantly
compromising vehicle driveability,
 Ethanol Blends – E85
Generally Compatible Materials
§ Metals* § Elastomers § Polymers
§ Black Iron § Buna-N § Polypropylene
§ Bronze § Fluorocarbons § Thermoplastic
§ Mild steel § Nitrile Rubbers piping*,
§ Stainless steel § Polychloroprene § Thermoset
§ PTFE reinforced fiberglass
§ Unplated steel
tanks*
§ Nickel Plating for soft
metals (i.e., aluminum)
*As listed by UL
*In the fuel path
 Ethanol Blends – E85
Vulnerable Materials
§ Metals § Elastomers § Polymers
§ Aluminum § Natural rubber § Certain polyamides
§ Brass § Cork gasket § Polyurethane,
§ Copper Alloys material, * § Polyvinyl chloride,
§ Lead § Leather, * § Methyl-methacrylate,
§ Lead Solder § Certain polymer
§ Tern-plated steel * Natural material not elastomer liners*
(Fuel Tanks)
§ Zinc *Epoxy and polyester resins
manufactured between
1970’s and 1980’s
Ed85-In Review
§ Whether for a new or converted system make sure the tank,
lines, and dispenser are thoroughly cleaned and inspected by a
bonded and experience company,
§ Ensure all metal and non-metal parts are compatible with E85
and will properly in the presence of E85,
§ Install and use a properly sized dispenser filter with the
appropriate efficiency rating as the last line of defense to protect
vehicle fuel tanks from dissolved contaminants,
§ Ensure that the dispenser hose is E85 compatible and will not
degrade or leach fillers or binders,
§ Consult with State and Local agencies regarding installation or
conversion guidelines or requirements,
Ed85- Accelerated Corrosion
§ Same facility
§ Same install date
§ Top is E85 STP
§ Bottom is standard non-
E85 fuel STP

Photograph Courtesy of Rounds and Associates (Public Domain Information)

Ed85 – Vent Pipe Deterioration

Photograph Courtesy of Rounds and Associates (Public Domain Information)

Ed85 - Seals and Gasket Leak

Photograph Courtesy of Rounds and Associates (Public Domain Information)

Ed85 - Catastrophic Failure

Photograph Courtesy of Rounds and Associates (Public Domain Information)

Biodiesel
Biodiesel
§ Biodiesel is a fuel manufactured from vegetable oils, used
grease, or animal fats.
§ The fuel typically contains different types of oils and fats
that are chemically transformed into fatty acid methyl
esters (FAME).
§ Different fractions of FAME present in various feedstocks
influence some of the properties of the fuel (e.g.,
saturated vs. unsaturated FAME) .
Biodiesel
§ Potential Issues and Concerns (B100):
§ B100 is a strong solvent and will release varnish and gums
from diesel fuel tank walls and piping into the bulk fuel
plugging in-line filters,
§ B100 can degrade, soften, seep through certain hoses,
gaskets, seals, elastomers glues and plastics with prolonged
exposure
§ Biodiesel will retain more dissolved water 1200-2500 ppm,
§ Biodiesel not meeting ASTM D6751 can potentially damage
equipment, plug filters, and shutdown vehicles,
Biodiesel – B100
Generally Compatible Materials
§ Metals § Elastomers § Polymers
§ Aluminum § Fluorocarbon § Fluorinated
§ Steels § PTFE polyethylene
§ Fluorinated
polypropylene
§ Polyamide
§ Fiberglass
Reinforces
Polymers.
Biodiesel – B100
Vulnerable Materials
§ Metals § Elastomers § Polymers
§ brass, bronze, § Buna-N § Polyethylene
copper, lead, tin, § Nitrile Rubber § Polypropylene
and zinc § Natural rubber § Polyvinyl
§ Lead solders, zinc § Polyvinyl chloride
linings, copper chloride
pipes, brass
regulators and
copper fittings
should be avoided,
Biodiesel
Elastomers Blend Compared to Diesel
PTFE B100 Little Change
Polyamide B100 Little Change
Fluorocarbon B100 Little Change
Nitrile B100 Hardness ? - 20% : Swell ? - 18%
Fluorosilicone B100 Hardness Neg. : Swell ? - 7%
Polyurethane B100 Hardness Neg. : Swell ? - 6%
Polypropylene B100 Hardness ? - 10% : Swell ? - 8-15%
Polyvinyl B100-B30 Worse
Polyvinyl B20 – B10 Comparable
Polyvinylchloride B100 Worse
Biodiesel – B20
Generally Compatible Materials*
§ Metals § Elastomers § Polymers
§ stainless steel, § Fluorocarbon § Fluorinated
§ carbon steel, or § PTFE Plastics
§ Aluminum § Polyamide
Most metals found in a
§ Thermoplastics
retail dispensing facility § Thermoset

* Strongly recommend consulting with UL or OEM

Biodiesel – B20
Vulnerable Materials*
§ Metals § Elastomers § Polymers
§ brass, bronze, § Problems tend § Problems tend
copper, lead, tin, to diminish as to diminish as
and zinc biodiesel biodiesel
§ Lead solders, zinc concentration concentration
linings, copper decreases decreases
pipes, brass
regulators and
copper fittings
should be avoided,

* Strongly recommend consulting with UL or OEM

Biodiesel / Biodeterioration
§ Other Important Issues and Concerns:
§ Biodiesel has a very favorable biodegradation profile
§ Aerobically, biodiesel will biodegrade in seven (7) days
§ Anaerobically, biodiesel will biodegrade in 14 days,
§ B100 can biodegrade 4 times faster than petroleum
diesel
§ B20 can biodegrade twice as fast as petroleum diesel,
Biodiesel / Biodeterioration
§ Fatty Acid Methyl Ester:
O Enzymatic attack of

O the terminal methyl group

O-
CH3

Fatty Acid + free methyl group

(Solubility proportional to carbon length)
Biodiesel / Biodeterioration
§ Fatty Acid:
O

-
O
ß Carbon
Fatty Acid Acetic Acid

Incorporated into the Enter intermediate metabolism

microbe cell wall for further degradation
Biodiesel
Biodiesel Metabolism EPA Standard 560/6-82-003

CO2 Evolution (%)

Days Rape Rape Soy Soy Neat Neat #2 Dextrose
Ethyl Methyl Ethyl Methyl Rape Soy Diesel
Ester Ester Ester Ester

0 0 0 0 0 0 0 0.00 0.00

7 69.01 66.32 67.68 68.4 58.39 60.57 13.20 59.84

14 79.15 80.72 78.40 77.83 70.47 70.12 21.04 80.19

28 86.92 88.49 86.40 85.54 78.45 75.95 26.24 87.79

Biodiesel

Cometabolism EPA Standard 560/6-82-003

CO2 Evolution (%) From REE/Diesel Mixture

Days REE100 R80/D20 R50/d50 R20/D80 D100

0 0 0 0 0 0

7 64.09 52.33 37.85 25.24 2.08

14 77.51 61.26 45.74 31.59 2.08

28 84.37 67.82 51.90 35.67 14.96

Conclusion
 Be Informed
§ Installing new equipment for storing and dispensing ethanol fuel or
biodiesel fuel or blends:
§ Talk to the manufacturer/installer about material compatibility and
warranty issues regarding the fuel to be stored.
§ Confirm that everything in the system is compatible with fuel and
will work as designed,
§ Keep water/contaminant issues to a minimum,
§ Install proper filter (pore size and efficiency rating) to protect
against transferring dissolved contaminants to client vehicles,
§ Contact state regulators/trade association for additional technical
information,
§ Document! Document! Document!
 Be Informed
§ Converting existing gasoline/diesel fuel system to store and dispense
ethanol fuel or biodiesel fuel or blends:
§ Talk to the manufacture/installer about material compatibility and
warranty issues for the new fuel type to be stored.
§ Confirm that everything in the system will remain compatible with
fuel and will work as designed,
§ Keep water/contaminant issues to a minimum,
§ Install proper filter (pore size and efficiency) to protect against
transferring contaminants and corrodants to client vehicles,
§ Contact state regulators/trade association for technical information,
§ Document! Document! Document!
Be Informed
Be Informed
Be Informed
Conclusion

Thank You