Biofuels and Emerging Issues
for
Emergency Responders
An overview of the biofuels industry and an introduction to
basic response guides
RRT 3
September 15, 2009
Goals

Discuss hazards and clean up techniques for
biodiesel and ethanol discharges

Discuss other biofuels hazards

Discuss background of the industry

Look at what the response community is
actually dealing with

Present response guides as a tool for
responders

Discuss possible alternative approaches to
response
Legislative Initiatives
 Energy Policy Act of 2005 (P.L. 109-58)
 Biofuel mandates increase from 4 bgy (2006) to 7.5 bgy
(2012)
 Requires EPA to promulgate regulations implementing
a renewable fuel program. (§ 1501)
 Specifies the total volume of renewable fuel used in
gasoline sold
 Specifies the total volume increases over time
 Renewable Fuel Standard (RFS 1)
 Provides enhanced tax incentives for biofuel usage.
 Energy Policy Tax Incentives (Title XIII)
 Renewable diesel from “thermal depolymerization”
Legislative Initiatives cont.
 Energy Independence & Security Act
(EISA) (2007)
 Requires EPA to develop a new RFS. (§ 202)
 Expand biofuels to 36 billion gallons by 2022
 Lifecycle GHG assessments of different fuel types
and blends compared to petroleum fuel
 Ethanol pipeline feasibility study (§ 243)
 Biofuels distribution and advanced biofuels
infrastructure (§ 248)
 R&D on existing transportation fuel distribution
infrastructure and new alternative distribution
infrastructure.
Legislative Initiatives cont.
 Energy Independence & Security Act (EISA)
(2007)
 Focus on the physical/chemical properties of biofuels
and efforts to prevent or mitigate against adverse
impacts of those properties in the areas:
 corrosion of metal, plastic, rubber, cork, fiberglass, glues, or
any other material used in pipes and storage tanks
 dissolving of storage tank sediments
 contamination from water or other adulterants or
pollutants
 poor flow properties related to low temperatures
 oxidative and thermal instability in long-term storage
and uses
 microbial contamination
Biofuels Regulatory Mandates
 Renewable Fuel Standard (RFS) 1 & 2
 40 CFR part 80 – Regulation of Fuels and Fuel Additives
 RFS - 1 (EPAct 2005)
 Federal Register on May 1, 2007 (72 FR 23900)
 Assessed first order impacts including emissions, air quality, and
GHG impacts of RFS standards
 RFS - 2 (EISA) – Signed Proposed Rule on May 5, 2009
 Expand use of renewable fuels to 36 billion gallons per year (bgy)
by 2022
 Ethanol production from corn starch is capped at 15 bgy
 Cellulosic Biofuel (renewable fuel from any cellulose,
hemicellulose, lignin)
 0.5 billion gallons by 2012
 3 billion gallons by 2015
 16 billion gallons by 2022
 Advanced Biofuels (biomass-based diesel, other biofuels)
6
Biofuels Supply Chain
Feedstock
Production
Feedstock
Logistics
Energy
Crops
Forest
Residues
Wastes
Algae
Biofuels
Distribution
Fuel types
Ag Crops
Ag Residues
Biofuels
Production
Harvesting &
Collecting
Biochemical
Conversion
Storage
Thermochemical
Conversion
Pre-Processing
Transportation
Biological
Conversion
Chemical
Conversion
Distribution
by barge,
truck, rail,
pipeline
Storage in
tanks
Dispensing
Biofuels
End Use
Transportation fuels
in light & heavy duty
vehicles & trucks, Off Road vehicles,
Locomotives, Flight
technologies,
Boats/Ships
Power & Generators
Feedstocks for
Manufacturing
Feedstocks, Conversion Processes, and Fuel Types
Feedstock
Conversion
Technology
Products
and Uses
Agricultural Crops
Thermo-chemical:
Fuel Types:
Agricultural Residues
-
-
Animal Residues
Food Processing
Waste
Woody Biomass
MSW and
Construction and
Demolition (C&D)
Wastes
-
Pyrolysis
Hydrothermal
Depolymerization
Gasification
Combustion
Fuel Synthesis
Biochemical:
-
Fermentation
Acid Hydrolysis
Pretreatment &
Enzymatic Hydrolysis
Anaerobic Digestion
Chemical:
- Transesterification
-
Ethanol
Biodiesel
Renewable Diesel
Green Diesel
FT Diesel & Gasoline
Higher Alcohols
Dimethyl Ether
Synthesis Gas,
Biogases, & H2
Hydrogen
Other Products:
- CHP (steam & electricity)
-
Chemical Feedstock
8
Biofuels Integration into
Infrastructure
Oil Field
Production
Pipeline/Vessel
Traditional
Petroleum Refinery
Animal Fats/Vegetable Oils (AFVO)
Biofuel
Generator
Vessels with Crude
Petroleum Oil as Cargo
Ethanol/biodie
sel
Railcar
Denaturant
Terminal
Dealers
Railcar
Pipeline
Vessels with Petroleum
Products as Cargo
Pipelines (under development)
Biorefinery
Company
Blending
Terminal
Railcar or Tanker Truck
Dealer
Company
Denatured Fuel Ethanol
Tanker Truck
Truck
Transloading
Biodiesel
Wholesale/Jobber
Dealer
Consumer
9
ETHANOL
MANUFACTURING
FACILITY RESPONSE
OVERVIEW
Description of Ethanol Fuel and
the Production Process
 Ethanol, which contains hydrogen, carbon, and oxygen in its
chemical structure, is also known as ethyl alcohol or grain alcohol.
 Fuel ethanol can be used as a fuel for spark-ignited internal
combustion engines. When burned in engines without active
catalytic converters on the engine exhaust, the presence of oxygen
allows ethanol to burn with lower carbon monoxide emissions
than gasoline, although aldehyde emissions tend to be higher.
 In the U.S., ethanol is primarily produced from corn. To prevent
ingestion, ethanol is denatured at the plant by mixing the ethanol
with some type of hydrocarbon, such as gasoline. Denatured
ethanol may contain 2-15 percent (%) gasoline, making it an
ethanol and gasoline fuel blend. For example, ethanol E-85
typically contains 85% ethanol and 15% gasoline.
 The ethanol production process takes place through two methods:
dry milling and wet milling. The dry milling method is more
common and accounts for 82 % of U.S. ethanol production.
Typical Ethanol Dry Mill Process
Grain (Corn)
Cleaning and
Milling
Distillation
Denaturant
~ 2-5% Gasoline
Enzymes
Fermentation
190 Proof
Dehydration
Molecular
Sieves
Mash
Preparation
DDGS Dried Distillers Grains
Separation with Solubles (DDGS)
200 Proof
Ethanol
Storage
Fuel
Ethanol
DDGS
Drying
DDGS
Storage
Livestock
12
Major Chemicals Involved in
Ethanol Production








Corn – Used product
Sodium Hydroxide – pH control during fermentation
Ammonia – pH control and yeast nutrient during fermentation
Sulfuric Acid – separates corn into starch, germ, fiber, and
protein
Fuel for process heat, Yeast – used in fermentation, Enzymes
(amylase) – converts starch to dextrose, Antibiotic such as
penicillin – controls bacteria during fermentation
Carbon Dioxide – byproduct, Hydrogen Sulfide – process
emission, Sulfur dioxide – process emission
Nitric oxide – process emission, VOCs – process emission,
Ethanol – final product
Gasoline – final product additive (if used)

2-5% of natural gasoline, conventional unleaded gas, straight run gas, naptha, kerosene
 Denatured Ethanol – final blended product
Current Ethanol Plants
http://www.card.iastate.edu/research/bio/tools/ethanol.aspx as of 01/16/2008
Ethanol Production (supply) – Coastal Consumers (demand)
15
Biofuels Infrastructure
 Infrastructure includes:
 Pipelines, rail lines/railcars,
barges/waterways, tank
trucks
 Terminals, Storage tanks,
Blending facilities, Transfer
hubs
 Ethanol and biodiesel currently
do not use many of the
traditional petroleum products
infrastructure (i.e., pipelines)
 Ethanol and biodiesel
infrastructure needs may be
different
 In 2005, rail: 60% of ethanol (approximately 2.9 billion
gallons of ethanol), tank trucks: 30%, and barges: 10%
16
Transloading Biofuels
 Federal and local jurisdictional
issues
 Typical individual railcar
capacity
 ~30,000 U.S. gallons
 Shipped in unit trains
 Can be as high as 100 railcars
 Transferred from rail cars to
tank trucks for delivery to
blending terminals
 Transfer process equipment
not necessary “fixed” in a single
location
17
Relevant Emergency Response
Issues



Fires and spills involving ethanol
and ethanol/gasoline blends pose
some complex challenges for
emergency responders
Ethanol is a polar/water-miscible
flammable liquid (one that mixes
readily with water)
 Degrades the effectiveness
of fire fighting foams that
are not alcohol resistant
DOT Guide 127 - Flammable
Liquids Polar/Water-miscible,
2008 Emergency Response
Guidebook (ERG2008)
18
Relevant Emergency Response Issues
 Alcohol-Resistant – Aqueous Film Forming Foam

(AR-AFFF)
 Effective with ethanol blends from E10 through E95
 E10 can be extinguished with AFFF and AR-AFFF but
require higher application rates to prevent burn back
 Passes a sprinkler application, which is typical of the fire
suppression systems at many storage terminal loading
racks
 Creates a physical, polymer-membrane barrier between
the foam blanket and fuel surface
 Alcohol Resistant – Film Forming Fluoroproteins (AR-FFFP)
 Burn back test
19
Ethanol/Gasoline blends and Placards

DOT Federal Register notice (73 FR 4699)

Published on January 28, 2008
Ethanol/Gasoline Blend
Example of Shipping Name
Gasoline, with not more than
10% ethanol
Gasohol, UN1203 or Gasoline,
UN1203
Gasoline/ethanol blends with
more than 10% ethanol
Ethanol and Gasoline Mixture,
UN3475
E85 (85% ethanol, 15% gasoline) Ethanol and gasoline mixture,
UN3475
Alcohol mixtures containing
up to 5% gasoline
E95 (95% ethanol, 5% gasoline)
E100
Denatured alcohol, NA1987
Alcohols, n.o.s., UN1987
Ethanol or Ethyl Alcohol, UN1170
Appropriate Mitigation Measures
for Release of Ethanol Fuel
 Proper Air Monitoring Equipment
 Combustible Gas Indicator (CGI) and Flame Ionizing Detector (FID)
or MultiRAE Plus Five-Gas Air Monitoring Instrument; Photo
Ionizing Detector (PID). Must review response factors prior to using
PID.
 Proper Spill Containment
 Ventilate area and eliminate ignition sources. Fire-fighting measures
must use ALCOHOL-RESISTANT FOAMS.
Containment/response should follow typical containment procedures.
Example: use non-combustible oil-dry, absorbent socks, booms, etc
that are ALCOHOL-RESISTANT. Avoid entry into sewers and
waterways due to flammability hazards, potential aquatic toxicity, and
potential microbial upsets at wastewater treatment plants. Waste
generated from the clean-up may exhibit the flammability
characteristic for hazardous waste.
Note: The Response Overview includes measures for the other major
chemicals involved in the manufacturing process.
EXPECTED FATE OF ETHANOL

Release in Soil
- Ethanol tends to biodegrade in
soil.

Release in Water
- Fuel ethanol will mix with
water, and at high enough
concentrations of water, the
gasoline will separate from the
ethanol.
- Ethanol preferentially
biodegrades relative to BTEX in
groundwater and surface water.
- Some studies are focusing on
the possibility of ethanol
inducing the transport of other
chemicals such as benzene.

Release in air as result of
spill/fire
-Ethanol vapor, like gasoline
vapor, is denser than air and
tends to settle in low areas.
However, ethanol vapor
disperses rapidly.

Release to storm/sanitary
sewers
-Ethanol released to water may
volatilize and biodegrade. The
potential decrease in dissolved
oxygen as a result of ethanol
degradation can upset microbial
functions at wastewater
treatment plants. The potential
flammability hazard must be
addressed when ethanol is
released to a sanitary or storm
system.
Overall Health Risks of Ethanol

Human Health Effects
 Exposure to fuel ethanol can occur
by breathing its vapors
(inhalation), getting it on the skin
or in the eyes (skin absorption), or
accidentally swallowing it
(ingestion).
 The following symptoms of
exposure to fuel ethanol may
appear immediately: Dullness of
memory and concentration;
impaired motor coordination; and
drowsiness, stupor, and finally
coma. May cause skin irritation as
a result of defatting.
 Carcinogenic compounds are not
present in pure ethanol; however,
because gasoline is used in the
blend, E85 is considered to be
potentially carcinogenic.

Ecological Effects
 Pure ethanol has
demonstrated lethal
concentrations for fish
(rainbow trout) at 11,200 to
15,300 milligrams per liter
(mg/L).
 Pure ethanol is expected to
biodegrade and not
bioaccumulate or
concentration in the food
chain. However, the
biodegradation may decrease
the dissolved oxygen in
surface water resulting in fish
kills.
BIODIESEL
MANUFACTURING
FACILITY RESPONSE
OVERVIEW
Current Biodiesel Plants
Typical Biodiesel Generation
NaOH
Vegetable Oil
Feedstock
Preparation
Acid
Transesterification
Reaction
Crude Biodiesel
Phase
Separation
Water
Washing
Drying
Catalyst
Preparation
Glycerin Phase
Neutralization
Water
Methanol
Acid
Acidification &
FFA Separation
Free Fatty Acids
FFA
Methanol
Recovery
Crude Glycerin
Finished
Biodiesel
Glycerin
Refining
Purified
Glycerin
26
Major Chemicals Involved in
Biodiesel Production
 Soybean hulls and fines
 Hexane – extracts soybean oil
 Sodium and Potassium Hydroxide – removes
fatty acids from soybean oil
 Methanol – replaces glycerol in soybean oil to
make oil less viscous (transesterification)
 Glycerol – byproduct of transesterification
 Fuel for process heat (i.e. natural gas,
propane, etc.)
Biodiesel Feedstock Spill
 Properties similar to petroleum
 Light non-aqueous phase liquid (LNAPL).
 Harmful effects: coating of feathers, fur, and gills
 Absence of odor and sheen results in reduced
avoidance.
 Reduces thermal insulation and buoyancy.
 May burn if ignited
 May clog water treatment plants (due to the
polymerization property).
28
Effects of Biodiesel Feedstock
Spills
 High BOD may cause oxygen depletion
 Greater effect on DO than petroleum oils
 Unsaturated oils (liquids at cold temperatures) are
subject to (abiotic) oxidation
 Polymerization due to chemical oxidation and cross-linking
 Rancid odors may develop rapidly
 Unsaturated oils form gum balls and varnishes in presence of
oxygen, which resist biodegradation
 Some saturated or unsaturated oils turn solid or semisolid at cool temperatures, highly resistant to
biodegradation
 May be toxic or form toxic products
 Especially free fatty acids and chemical oxidation products.
Appropriate Mitigation Measures
for Release of Biodiesel Fuel
 Proper Air Monitoring Equipment
 Biodiesel fuel has a very low volatility at normal ambient
temperatures and vapors are not typically an issue. However,
vapors/mists may be generated when heated above ~266 degrees
Fahrenheit (ºF).
 Proper Spill Containment
 Containment/response should follow typical oil containment
procedures. Example: use oil-dry, petroleum-compatible absorbent
socks, booms, etc; the absorbent material used should be resistant to
alcohol in the event methanol has further commingled with the
biodiesel release. Disposal of biodiesel-contaminated soil or products
can be considered non-hazardous provided methanol and/or hexane
have not commingled with the release to meet the flammability
characteristic for hazardous waste.
Note: The Response Overview includes measures for the other major
chemicals involved in the manufacturing process.
EXPECTED FATE OF BIODIESEL
 Release in Soil
-Biodegradation, with faster
rates under aerobic
conditions than anaerobic
conditions, if it doesn’t
polymerize
 Release in Air as result of
spill/fire
-Combustion produces carbon
monoxide, carbon dioxide
along with thick smoke.
 Release in Water
-Insoluble in water.
Degradation varies in aquatic
environments.
 Release to storm/sanitary
sewers
-May be high in free fatty
acids and glycerol, and can
have a high biochemical
oxygen demand (BOD). These
can disrupt wastewater
treatment plant operations.
Overall Health Risks of a
Biodiesel Release

Human Health Effects
 Inhalation effects are negligible
unless heated to produce vapors.
 If biodiesel fuel were to be ingested,
enzymes in the body called esterases
would break the biodiesel fuel
molecules into the component fatty
acids and alcohol molecules. The
alcohol is usually methanol and
methanol is toxic. Thus, methanol
toxicity could be a concern for
ingestion of biodiesel fuel.
 Neat biodiesel fuel is approximately
11 percent methanol by weight, so
ingestion of 100 grams of biodiesel
would release 11 grams, or
14 milliliters (mL) of methanol. For a
70 kilogram (kg) adult, the fatal dose
of methanol ranges from 60 to 160
mL.

Ecological Effects
 Biodiesel may biodegrade more
rapidly than conventional diesel.
It depends!
 When biodiesel is present in bulk
in the environment, it can coat
animals that come in contact
with it and may reduce the
ability of oxygen to reach aquatic
systems. In this respect, its
action is similar to petroleum
diesel fuel.
 The treatment of oiled birds and
animals would be similar to the
treatment provided when an oil
spill occurs.
 However, in water it has a high
oxygen demand which can lead
to massive fish kills
The following are examples of federal laws & regulations that
may apply to biofuels manufacturing facilities when they meet
the thresholds for the requirements of the regulation. Note
that state-specific regulations may also apply
 Emergency Planning and Community Right Know Act
(EPCRA)
 Federal Water Pollution Control Act (aka Clean Water
Act)
 Oil Pollution Prevention regulations
 SPCC and FRP (40 CFR part 112)




Oil Pollution Act of 1990 (OPA 90)
Resource Conservation and Recovery Act (RCRA)
Clean Air Act (CAA)
DOT Hazardous Materials Regulations (HMR); as
amended by Homeland Security Act of 2002
Biofuels & Hazardous Chemical Reporting
EPCRA - sections 311 & 312
 Gasoline - 75,000 gallons
 At a retail gas station, stored entirely underground, in compliance at
all time in the previous calendar year with UST requirements)
 Gasohol (90% gasoline and 10% ethanol) - 75,000 gallons
 At a retail gas station, stored entirely underground, in compliance at
all time in the previous calendar year with UST requirements)
 Diesel - 100,000 gallons
 At a retail gas station, stored entirely underground, in compliance at
all time in the previous calendar year with UST requirements)
 All other non-EHS hazardous chemicals -10,000 lbs
 Alternative Fuels (Ethanol and Methanol mixtures; E85, E95, M95),
aviation fuel, heating fuel, kerosene
34
Response Guides
Response Guides
Layout – intended for responders

Description of Process

The chemicals involved (1st important table)

How releases may occur (what to look for)

Responding to releases (and byproduct
releases, 2nd table)

Environmental receptors/concerns (3rd table)

Health risks

Summary of applicable regulations
Response Guides
Use – want more functionality

Tables were included for quick location of info

Many spills are not the end product

Tables reflect the “may be” scenario of spills

Need your input
http://www.epaosc.org/site_profile.asp?site_id=4022
Summary
 Biofuels may have different fate and
transport properties
 Causes extreme DO issues in creeks and
other water bodies
 Not great for water treatment plants
 Other removal/cleanup techniques
 Treating “in stream” besides aeration
 Other sorbent technologies
 Fast degradation can make cleanups faster
 “Biofuel” spills are many times not biodiesel
or ethanol, but production products and
byproducts
Summary
 Biofuel production can be anywhere
 Field experience suggests “Manufacturers” are
often unaware of federal regulations
 Some facilities are being abandoned or going
bankrupt due to market fluctuations
 Glycerin spills seem to be prevalent
 Output from the transesterification
 Not that much use for it as product
 People are storing it and not disposing of it
 Some waiting for “value” to increase
Additional Resources
 DOT PHMSA Guide 127 - Flammable Liquids Polar/Watermiscible.
 2008 Emergency Response Guidebook (ERG2008)
 http://hazmat.dot.gov/pubs/erg/g127.pdf
 Ethanol Emergency Response Coalition (EERC)
 http://www.ethanolresponse.com
 Guidebook for Handling, Storing, & Dispensing Fuel Ethanol
(DOE)
 http://www.nrel.gov/docs/fy02osti/30849.pdf
 EPA Region 5 - Ethanol & Biodiesel Response Manuals
 OSC website
 EPA Region 7 - Ethanol & Biodiesel plant Manuals
 http://epa.gov/region07/priorities/agriculture/biodiesel_manual.pdf
 http://epa.gov/region07/priorities/agriculture/ethanol_plants_manual.pdf
40
QUESTIONS ???