Biofuels and Emerging Issues for Emergency Responders An overview of the biofuels industry and EPA case studies SCAA 2012 Annual Meeting March 8, 2012
Feedstocks, Conversion Processes, and Fuel Types Feedstock Agricultural Crops Agricultural Residues Animal Residues Food Processing Waste Woody Biomass MSW and Construction and Demolition (C&D) Wastes Conversion Technology Thermo-chemical: - Pyrolysis - Hydrothermal Depolymerization - Gasification - Combustion - Fuel Synthesis Biochemical: - Fermentation - Acid Hydrolysis - Pretreatment t t & Enzymatic Hydrolysis - Anaerobic Digestion Chemical: - Transesterification Products and Uses Fuel Types: - Ethanol - Biodiesel - Renewable Diesel - Green Diesel - FT Diesel & Gasoline - Higher Alcohols - Dimethyl Ether - Synthesis Gas, Biogases, & H 2 - Hydrogen Other Products: - CHP (steam & electricity) - Chemical Feedstock 2
Biofuels Supply Chain Feedstock Production Feedstock Logistics Biofuels Production Biofuels Distribution Biofuels End Use Ag Crops Ag Residues Energy Crops Forest Residues Wastes Algae Harvesting & Collecting Storage Pre-Processing Transportation Fuel types Biochemical Conversion Thermochemical Conversion Biological Conversion Chemical Conversion Blending Distribution by barge, truck, rail, pipeline Storage in tanks Dispensing Transportation fuels in light & heavy duty vehicles & trucks, Off - Road vehicles, Locomotives, Flight technologies, Boats/Ships Power & Generators Feedstocks for Manufacturing
Biofuels Integration into Infrastructure Oil Field Production Pipeline/Vessel Vessels with Crude Petroleum Oil as Cargo Animal Fats/Vegetable Oils (AFVO) Biorefinery Ethanol/biodie sel Biofuel Generator Railcar Denaturant Traditional Petroleum Refinery Railcar Pipelines (under development) Railcar or Tanker Truck Pipeline Blending Terminal Terminal Vessels with Petroleum Products as Cargo Denatured Fuel Ethanol C Transloading Tanker Truck Truck Dealer Company Dealer Company Dealers Biodiesel Wholesale/Jobber Consumer 4
ETHANOL
Typical Ethanol Dry Mill Process Grain (Corn) Cleaning and Milling Mash Preparation Enzymes Denaturant Distillation Fermentation ~ 2-5% Gasoline 190 Proof Dehydration Molecular l Sieves 200 Proof Ethanol Storage DDGS Separation DDGS Drying Dried Distillers Grains with Solubles (DDGS) Fuel Ethanol DDGS Storage Livestock 6
Ethanol and Gasoline Blends E100: Non-denatured fuel ethanol E95: Denatured fuel ethanol ASTM 4806 Min 92% ethanol Denaturants: 2% to 5% Natural gasoline Gasoline components Unleaded gasoline E85: Flex Fuel ASTM D 5798 Three ethanol classes: 70%, 74%, 79% E10: may contain 10% ethanol ~90% gasoline E00 ethanol free gasoline 7
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 i oxide process emission, i VOCs process emission, i 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
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) 10
EXPECTED FATE OF ETHANOL Release in Soil Release in air as result of - Ethanol tends to biodegrade in spill/fire soil. -Ethanol vapor, like gasoline vapor, is denser than air and Release in Water tends to settle in low areas. However, ethanol vapor - Fuel ethanol will mix with disperses rapidly. water, and at high enough concentrations of water, the gasoline will separate from the Release to storm/sanitary ethanol. sewers ers - Ethanol preferentially -Ethanol released to water may biodegrades relative to BTEX in volatilize and biodegrade. The groundwater and surface water. potential decrease in dissolved - Some studies are focusing on oxygen as a result of ethanol the possibility of ethanol degradation can upset microbial inducing the transport of other functions at wastewater chemicals such as benzene. treatment plants. The potential flammability hazard must be addressed when ethanol is released to a sanitary or storm system.
Spill to Broadland Creek May 17, 2008 Info. Courtesy of Kim McIntosh, SD-DENRDENR Dry Mill plant in Huron, South Dakota Transfer line hose broke during filling of tank car Approx. 6000 gallons of denatured ethanol discharged 100s of fish killed in creek Minnows, bullhead, carp Recreational lake closed for 10 days 12
Response Deploy boom and aerators 3 mi downstream Daily check of temperature, dissolved oxygen, ph, conductivity 5/20/2008 am D.O. 0.2 to 10.6 mg/l 5/21/2008 am D.O. 0.3 to 5.4 mg/l 5/21/2008 pm D.O. 1.0 to 7.6 mg/l 5/22/2008 am D.O. 1.0 to 6.0 mg/l 5/22/2008 pm D.O. 1.2 to 5.7 mg/l (downstream) 5/22/2008 pm D.O. 0.4 to 8.0 mg/l 5/23/2008 am D.O. 1.0 to 6.6 mg/l (upstream) 5/23/2008 pm D.O. 0.3 to 5.8 mg/l 5/23/2008 pm D.O. 0.1 to 5.6 mg/l (downstream) 5/24/2008 am D.O. 0.2 to 5.9 mg/l 5/27/2008 am D.O. 1.0 to 8.0 mg/l Moved aerators as plume moved downstream 13
Huron, S.D., May 17, 2008 6000 gal ethanol spill Broadlands Cr Fish Kill. 10 Day Closing of Recreational Lake 14
Comments No gasoline observed 4 water samples for VOCs 5/21 BTEX, tri-methylbenzenes, th ethanol, methanol Most results ND, one sample ethanol at 6800 ppb Generally increased D.O. by 5/27/2008 Fish kill happened before oxygen sparging Does the depletion of oxygen kill the fish? Does the ethanol + hydrocarbons kill the fish? (replenishing the D.O. may not save the fish) 15
BIODIESEL
What is BioDiesel? General Definition of Biodiesel: Biodiesel is a domestic, renewable fuel for diesel engines derived from natural oils like soybean oil, and which meets the specifications of ASTM D 6751. Clarifying language to general definition: Biodiesel can be used in any concentration with petroleum based diesel fuel in existing diesel engines with little or no modification. Biodiesel is not the same thing as raw vegetable oil. It is produced by a chemical process which removes the glycerin from the oil. Technical Definition for Biodiesel (ASTM D 6751) and Biodiesel Blend: Biodiesel, n a a fuel comprised of mono-alkyl esters of long chain fatty acids derived from vegetable oils or animal fats, designated B100, and meeting the requirements of ASTM D 6751. Biodiesel Blend, n a a blend of biodiesel fuel meeting ASTM D 6751 with petroleum-based diesel fuel, designated BXX, where XX represents the volume percentage of biodiesel fuel in the blend. Biodiesel is typically produced by a reaction of a vegetable oil or animal fat with an alcohol such as methanol or ethanol in the presence of a catalyst to yield mono-alkyl esters and glycerin, which is removed.
Current Biodiesel Plants
Typical Biodiesel Generation Vegetable Oil NaOH Methanol Feedstock Preparation Transesterification Reaction Catalyst Preparation Acid Crude Biodiesel Phase Separation Glycerin Phase Acid Neutralization i Acidification i & FFA Separation Water Drying Water Washing Methanol Recovery Crude Glycerin Free Fatty Acids FFA Finished Biodiesel Glycerin Refining Purified Glycerin 19
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). 21
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 t oils form gum balls and varnishes in presence of oxygen, which resist biodegradation Some saturated or unsaturated 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.
Appropriate Mitigation Measures for Release of Biodiesel Fuel Proper Air Monitoring i 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 h (ºF). Proper Spill Containment Containment/response should follow typical oil containment procedures. Example: use oil-dry, petroleum-compatible p 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 Release in Air as result of -Biodegradation, with faster spill/fire rates under aerobic -Combustion produces carbon conditions than anaerobic monoxide, carbon dioxide conditions, if it doesn t along with thick smoke. polymerize 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, gy and can have a high biochemical oxygen demand (BOD). These can disrupt wastewater treatment plant operations.
Defiance Biofuel Spill Initial report called in to state: COMPANY HAD AN EXPLOSION. THERE ARE 2 LARGE TANKS ON SITE CONTAINING GLYCERIN. SEWER BEING IMPACTED WITH FF WATER. Ohio EPA OSC responded Two tanks were in the fire: 10,000 gallon and 4,000 gallon Only 1650 gallons of glycerin reported on hand Also about 700 gallons of biodiesel Empty 55-gallon drums Release to ground and storm sewer Release threatened creek and river via storm sewer
Defiance Biofuel Spill (continued) Fire and release point
Defiance Biofuel Spill (continued) Ohio EPA responded and assessed situation Called EPA spill phone duty officer Duty officer coordinated d with OSC Both told Ohio EPA to respond as if diesel spill Were not sure what regulations applied to biodiesel production Both continued research that night Advised state on limited info obtained Ohio EPA determined spill contained, but not cleaned up They decided to wait till morning for removal
Defiance Biofuel Spill (continued) Drums consumed in fire Release came out of structure with fire fighter water
Defiance Biofuel Spill (continued) Fats floated 3 layers in water observed Some suspended d in water Milky layer observed
Defiance Biofuel Spill (continued) Response Techniques Ohio EPA made PRP hire a contractor The on-land spills were excavated The spill to the ditch was collected and put in frac tanks 3 distinct layers were noted in ditch waters Analytical results of frac tank water revealed styrene and perchloroethylene Showed more than glycerin spilled Some wastes suspended d in the water column were lost
Additional Resources DOT PHMSA Guide 127 - Flammable Liquids Polar/Water- miscible. 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 pdf http://epa.gov/region07/priorities/agriculture/ethanol_plants_manual.pdf 31
QUESTIONS???