Emerging Issues About Biofuels Under EPA's Emergency Response Program

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Emerging Issues About Biofuels Under EPA's
Emergency Response Program
Gregory J. Wilson U.S. EPA - Office of Emergency
Management Washington, DC 20460 wilson.gregory_at_epa
.gov
Regional Response Team 2 West Point, New
York April 7, 2009
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Legislative Background

• Energy Policy Act of 2005
• Biofuel mandates increase from 4 bgy (2006) to
  7.5 bgy (2012).
• Requires EPA to promulgate regulations
  implementing a renewable fuel program.
• Energy Independence Security Act (EISA) (2007)
• 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)

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Biofuels Supply Chain
Ag Crops Ag Residues Energy Crops Forest
Residues Wastes Algae
Fuel types Biochemical Conversion Thermochemical
Conversion Biological Conversion Chemical
Conversion
Transportation fuels in light heavy duty
vehicles trucks, Off -Road vehicles,
Locomotives, Flight technologies,
Boats/Ships Power Generators Chemical
Feedstocks for Manufacturing
Harvesting Collecting Storage Pre-Processing Tra
nsportation
Distribution by barge, truck, rail,
pipeline Storage in tanks Dispensing
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Ethanol Production (supply) Coastal Consumers
(demand)
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Biofuels Integration Roadmap
Vessels with Crude Petroleum Oil as Cargo
Oil Field Production
Pipeline/Vessel
Traditional Petroleum Refinery
Animal Fat / Vegetable Oil (AFVO)
Company
AFVOs Generator
Terminal
Vessels (barges) with Petroleum Products as Cargo
Dealers
Railcar
Pipeline
Pipelines (under development)
Biorefinery Ethanol/biodiesel
Blending Terminal
Denatured Fuel Ethanol/Vessels
Railcar
Transloading
Truck
Dealer
Denaturant
Company
Wholesale/Jobber
Biodiesel
Dealer
Consumer
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Current Ethanol Plantshttp//www.card.iastate.edu
/research/bio/tools/ethanol.aspx as of 01/16/2008
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Typical Ethanol Dry Mill Process
Cleaning and Milling
Mash Preparation
Enzymes
Grain (Corn)
Fermentation
Distillation
Denaturant
190 Proof
2-5 Gasoline
DDGS Separation
Dried Distillers Grains with Solubles (DDGS)
Dehydration
Molecular Sieves
200 Proof
Ethanol Storage
DDGS Drying
GTL Ethanol/Biodiesel
Gasification
DDGS Storage
Fuel Ethanol
Livestock
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Denaturant Why How Much

• U.S. Department of the Treasury - Alcohol and
  Tobacco Tax and Trade Bureau (TTB)
• Render ethanol unfit for human consumption
• At least 2 gallons of denaturant to every 100
  gallons of fuel ethanol
• Natural Gasoline
• Conventional Unleaded Gasoline
• Straight Run Gasoline
• Naphtha
• Kerosene
• Ethanol producers add 4.76 volume

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Ethanol Plant Process Chemicals

• Ethanol production process (pH adjustment,
  nutrients)
• Sulfuric Acid - Corrosive
• Sodium Hydroxide (Caustic Soda) Corrosive
• Ammonia Source - Anhydrous, Hydrous - Corrosive
• Cleaning chemicals keep fermentation clean
• Chlorine-based Solution - Corrosive
• Caustic Soda - Corrosive
• General water treatment chemicals
• Chlorine- or Bromine-based Solution - Corrosive
• Ammonia-related Solution - Some Hazards
• Surfactants - Some hazards, typically mild
• Ethanol and Ethanol Blended Fuels, Emergency
  Response Training and Safety Issues, National
  Association of State Fire Marshals, July 1, 2008
• www.firemarshals.org/data/File/docs/Emergency-Resp
  onse-IAFC.pdf
• EPA (R5) Ethanol Manufacturing Facility
  Response Overview

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Potential Risks of Ethanol

• Human Health Effects
• Exposure to fuel ethanol may occur by breathing
  its vapors (inhalation), getting it on the skin
  or in the eyes (skin absorption), or swallowing
  it (ingestion).
• Exposure to ethanol vapors in high concentrations
  or for prolonged periods can be harmful to human
  health.
• Ethanol can cause local dehydration and lesions.
• Absorption, which occurs swiftly from the
  gastrointestinal tract, causes euphoria, with
  subsequent dizziness, inebriation, paralysis,
  diminished reflex, and respiratory paralysis.

• Ecological Effects
• Pure ethanol can be toxic to fish at high enough
  concentrations
• Lethal concentrations for fish (rainbow trout)
  11,200 to 15,300 milligrams per liter (mg/L).
• Pure ethanol is completely miscible in water
• Pure ethanol may biodegrade aerobically and
  anaerobically
• Biodegradation may decrease the dissolved oxygen
  in surface water, resulting in fish kills and
  other adverse impacts to oxygen-dependent species
  (direct or indirect).

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Ethanol Spill
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Ethanol Spill
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Typical Biodiesel (e.g., FAME) Generation
Methanol
NaOH
Vegetable Oil
Feedstock Preparation
Catalyst Preparation
Transesterification Reaction
Phase Separation
Crude Biodiesel
Glycerin Phase
Acid
Acid
Neutralization
Acidification FFA Separation
Free Fatty Acids
Water
Water Washing
FFA
Methanol Recovery
Drying
Crude Glycerin
Purified Glycerin
Glycerin Refining
Finished Biodiesel
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Current Biodiesel Plants
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Biodiesel Plant Process Chemicals

• Biodiesel production process
• Methanol
• Volatile Flammable (Class 3)
• Sodium Hydroxide (Caustic Soda)
• Corrosive Catalyst
• Potassium Hydroxide
• Corrosive Catalyst
• Sodium Methylate
• Catalyst
• Hexane
• Volatile Flammable (Class 3)
• Glycerol (glycerine)
• EPA (R5) Biodiesel Manufacturing Facility
  Response Overview

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Biofuel Spill

• Fire and release point

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Vegetable Oil (Biodiesel Feedstock) Spill

• Properties similar to petroleum.
• Light non-aqueous phase liquid (LNAPL).
• Toxic effects coating of feathers, fur, and
  gills is harmful.
• 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).

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Effects of Vegetable Oil Spills

• High BOD may cause oxygen depletion.
• Greater effect on DO than petroleum oils.
• Unsaturated oils (liquids at cold temperatures)
  are subject to chemical (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.
• Saturated oils turn solid or semi-solid at cool
  temperatures, highly resistant to biodegradation.
• May be toxic or form toxic products.
• Especially free fatty acids and chemical
  oxidation products.

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Biofuels InfrastructureTransportation and
Non-transportation Related

• Distribution terminals
• Blending facilities
• Transfer hubs
• Rail lines railcars
• Barges waterways
• Transport trucks
• Pipelines
• Ethanol and biodiesel currently do not use many
  of the traditional petroleum products
  infrastructure

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Transloading Biofuels

• 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

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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 PHMSA Guide 127 - Flammable Liquids
Polar/Water-miscible, 2004 Emergency Response
Guidebook (ERG2004) http//hazmat.dot.gov/pubs/erg
/g127.pdf Ethanol Emergency Response Coalition
(EERC), http//www.ethanolresponse.com
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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
• 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)

Ethanol and Ethanol Blended Fuels, Emergency
Response Training and Safety Issues, National
Association of State Fire Marshals, July 1,
2008 www.firemarshals.org/data/File/docs/Emergency
-Response-IAFC.pdf
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EPA Regulations

• Spill Prevention, Control, and Countermeasures
• Facility Response Plans
• Risk Management Plans
• Emergency Planning and Community Right to Know

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Summary

• Recent energy legislation mandates biofuel usage.
• Requires EPA to develop a new Renewable Fuel
  Standard.
• Expand biofuels to 36 billion gallons by 2022.
• New generation, storage, and distribution
  infrastructure challenges
• Integrating biofuels into traditional fuel supply
  chain
• Infrastructure challenges
• Fires and spills involving ethanol and
  ethanol/gasoline blends pose some complex
  challenges for emergency responders
• Biodiesel other substances in biofuels
  generation

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Additional Resources

• DOT PHMSA Guide 127 - Flammable Liquids
  Polar/Water-miscible.
• 2004 Emergency Response Guidebook (ERG2004)
• 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
• EPA Region 7 - Ethanol Biodiesel Plant Manuals
• http//epa.gov/region07/priorities/agriculture/bio
  diesel_manual.pdf
• http//epa.gov/region07/priorities/agriculture/eth
  anol_plants_manual.pdf