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 ???