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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@epa.gov. Regional Response Team 2 West Point, New York April 7, 2009. Legislative Background. Energy Policy Act of 2005

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emerging issues about biofuels under epa s emergency response program

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@epa.gov

Regional Response Team 2

West Point, New York

April 7, 2009

legislative background
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)
biofuels supply chain

Feedstock

Production

Feedstock

Logistics

Biofuels

Production

Biofuels

Distribution

Biofuels

End Use

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

Transportation

Distribution by barge, truck, rail, pipeline

Storage in tanks

Dispensing

biofuels integration roadmap
Biofuels Integration Roadmap

Vessels with Crude

Petroleum Oil as Cargo

Oil Field

Production

Pipeline/Vessel

Animal Fat / Vegetable Oil (AFVO)

Traditional

Petroleum Refinery

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

Wholesale/Jobber

Company

Biodiesel

Dealer

Consumer

5

current ethanol plants http www card iastate edu research bio tools ethanol aspx as of 01 16 2008
Current Ethanol Plantshttp://www.card.iastate.edu/research/bio/tools/ethanol.aspx as of 01/16/2008
typical ethanol dry mill process
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

denaturant why how much
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
ethanol plant process chemicals
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-Response-IAFC.pdf
  • EPA (R5) – Ethanol Manufacturing Facility Response Overview
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).

Potential Risks of Ethanol
typical biodiesel e g fame generation
Typical Biodiesel (e.g., FAME) Generation

Methanol

NaOH

Vegetable Oil

Feedstock

Preparation

Transesterification

Reaction

Catalyst

Preparation

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

Finished

Biodiesel

Glycerin

Refining

biodiesel plant process chemicals
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
biofuel spill
Biofuel Spill

Fire and release point

vegetable oil biodiesel feedstock spill
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).
effects of vegetable oil spills
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.
biofuels infrastructure transportation and non transportation related
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
transloading biofuels
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
relevant emergency response issues
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
relevant emergency response issues1
Relevant Emergency Response Issues

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

  • 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)

22

epa regulations
EPA Regulations
  • Spill Prevention, Control, and Countermeasures
  • Facility Response Plans
  • Risk Management Plans
  • Emergency Planning and Community Right to Know
summary
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
additional resources
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/biodiesel_manual.pdf
    • http://epa.gov/region07/priorities/agriculture/ethanol_plants_manual.pdf