Nomenclature Ethanol – Ethyl Alcohol, “(CH 3 CH 2 OH) a colorless, flammable liquid produced by fermentation of sugars. Ethanol is used as a fuel oxygenate. Ethanol is the alcohol found in alcoholic beverages.” (US DOE) Oxygenate – A compound which contains oxygen in its molecular structure. Oxygenated fuel improves combustion efficiency and reduces tailpipe emissions of CO. Knocking – when the fuel/air mixture ignites prematurely, usually due to compression and hot spots in the cylinder. It is also known as detonation or ping. Octane Rating- How much the fuel can be compressed before spontaneously combusting (low rating leads to knocking) MTBE- Methyl Tertiary Butyl Ether (C 5 H 12 O) –Fuel additive (up to 10-15%) for two reasons Oxygenate (Clean Air Act of 1990) Boost octane rating –Gallstones
MTBE History 1960s: Italian company creates MTBE initially as a solvent, then octane enhancer 1960s: Development of catalytic converters, leading to removal of lead from gasoline 1973: first MTBE plant opens in Italy Late 1970s: Several plants opened in U.S. to boost octane ratings of unleaded gas 1980s: MTBE use continues to increase 1990: Clean Air Act (requires MTBE, or other oxygenates) 1999: California first state to create plan to eliminate MTBE as a fuel additive 2003: Wisconsin Act 45: Wisconsin gasoline cannont contain more than.5% MTBE by Aug. 1, 2004
Ethanol History 3000 B.C.Earliest known written record of alcohol consumption. 1859:Ethanol sales for lamp fuel exceeded 25 million gallons. 1876-1908:Ethanol used as fuel in autos. –Otto Cycle (1876) was the first combustion engine designed to use ethanol, followed by the Model T (1908) which was designed to use ethanol, gasoline or any combination of the two. 1920:Prohibition –It is illegal to consume alcoholic beverages. 1940s:First ethanol fuel plant built in the US. –The Army built and operated the plant in Omaha, NE to provide fuel for itself and the region. 1973:OPEC oil embargo causes energy crisis. 1974:The oil embargo ends. 1978:Energy Tax Act. –Gave a $0.04/gal exemption for blended fuels and a 10% investment credit for biomass-ethanol conversion equipment.
More Ethanol History 1979:Amoco markets the first Ethanol fuel blends. 1979:Interior and Related Agencies Appropriation Act –Appropriated $19 billion to stimulate production of alternative fuels. 1980:Fewer than 10 ethanol production facilities exist. 1980:Energy Security Act –Offered loans for up to 90% of construction costs for ethanol plants. 1980s:Numerous Acts that gave and extended tax credits for ethanol production. 1985:163 Ethanol production plants exist, but only 74 operate. 1988:Denver is first city to require use of Ethanol as an oxygenate. 1990:Clean Air Act –Mandates that 39 areas use oxygenated fuel in the winter and 9 areas use it year round.
MTBE Health Effects Class 3 Carcinogen Laboratory Animals –Kidney and testicular tumors –Lymphoma and Leukemia Short Term Effects: –Odor and Taste Concerns –Irritation of the eyes, nose, throat –Headache –Disorientation –Breathing Problems
Ethanol Health Effects Acts as a depressent, although initially shows the opposite – an increase in mood and behavior. Leads to mild euphoria; memory and concentration become impaired. At high doses vomiting and nausea can occur. We all should recognize these effects as being intoxicated. The body easily metabolizes any consumed ethanol, although with constant and high exposure liver damage can occur as well as physical dependence. Effects of withdrawal can lead to death in severe cases.
MTBE Facts Accounted for 25% of total ozone reductions Equivalent to taking 3.5 million cars off the road Reduces the daily emission of pollutants in California alone by more than 3 million pounds
Ethanol Facts – Benefits Ethanol provides a renewable domestic source of fuel! Observing the carbon cycle shows that net CO and CO 2 emissions are lower by ~40%. A net energy gain of about 20,000 Btu per gallon of ethanol. When using E10 fuel there is a: –6% reduction in petrolium use. –1% reduction in GHG emissions. –3% reduction in fossil energy use. Reduced the trade deficit by $5.1 billion in 2004 by eliminating the need for 143.3 million barrels of oil. Ethanol (~113) is an octane additive, replacing benzene which is a known carcinogen. Does not release hydrocarbons into the air which produce ground- level ozone. As an oxygen additive for fuel it helps reduce the overall CO emission levels by up to 30%. Reduces particulate emissions by reducing the amount of aromatics in the fuel. Readily biodegrades when released into the atmosphere or water supply.
Ethanol Facts – Negatives Combustion of ethanol fuels produces more aldehydes than non-oxygenated gasoline. Due to how readily ethanol absorbs water it can not be transported by the current pipeline system, must be transported via train or truck. More expensive than Petroleum based counterparts such as MTBE and pure gasoline. Ethanol has a lower vapor pressure which causes it to more readily
Carbon Monoxide emissions levels and sources – CO is a major contributor to ground level ozone formation.
Emissions Comparison Source: American Water Works Association
Reductions for varying levels of Ethanol usage.
This was attached to the report commissioned by the U.S. Department of Energy that contained the previous two slides information.
Some Evidence shows that the use of Ethanol as a fuel actually decreases the mileage that a vehicle can obtain. An co-analysis on exhaust emissions also showed that there was neither a increase or decrease in overall emissions, it varied by vehicle.
MTBE Environmental Discharge Leaking Underground Storage Tanks Spillage at the pump Volatilization Motorized Water Recreation Accidents
State MTBE Bans StateEffective Date ArizonaEffective CaliforniaEffective ColoradoEffective ConnecticutEffective IllinoisEffective IndianaEffective IowaEffective KansasPending Federal Action Kentucky01-01-06 Maine01-01-07 MichiganEffective MinnesotaEffective Missouri07-01-05 NebraskaEffective New HampshirePending Federal Action New YorkEffective Ohio07-01-05 South DakotaEffective WashingtonEffective WisconsinEffective 20 Total States
Wisconsin Regulation of MTBE Act 45 (August 26, 2003) –Beginning August 1, 2004, Gasoline cannot contain more than.5% MTBE (by volume) DNR Regulates Industrial Air Effluents Wisconsin Groundwater Standard –60 ppb
Microbial process for the breakdown of Ethanol when released into the environment. Once it becomes Acetyl-CoA it is in a form that is part of the energy cycle in cells.
MTBE Production CH 3 OH + CH 2 =C(CH 3 ) 2 + H+ CH 3 OC(CH 3 ) 3 + H+ Two Major types of plants (Differ in Isobutylene source) –Refinery/Petrochemical Plants Isobutylene produced as a byproduct Cheaper, but smaller capacity –Merchant Plants Isobutylene produced from butane 2-5 times as expensive, larger capacity Methanol –Natural Gas Derivative (same for both plants)
MTBE vs Ethanol Production Source: Department of Energy January, 2003: First month in which Ethanol production beat MTBE
Ethanol Production Capacity In 2004, 3.41 billion gallons of Ethanol were produced. This represents a 21% increase from 2003 and a 109% increase from 2000. Currently there are 16 plants and 2 major expansions under construction. These will total another 750 million gallons of production capacity. 75% of capacity is produced by dry milling, and 25% is produced by wet milling.
Ethanol Base Stock Sources Ethanol can be made from virtually any biomass source. Those currently in use are: –Corn –Cheese Whey –Barley –Waste Beverage –Waste Beer/Brewery Waste (Coors & Miller) –Wheat Starch –Sugars and starches –Grain Sorghum
Economics Cost Comparison Ethanol from corn costs $1.74/gallon to produce. $1.05/gallon comes from growing the corn. If a car were run 10,000 miles on pure ethanol, it would take 11 acres for the corn to grow. If all the automobiles in the U.S. were run on pure ethanol 97% of U.S. land area would be required to grow the needed amount of corn. Gasoline costs $0.95/gallon to produce.
Economics Increased corn value by $0.25 – 0.50 per bushel; totaling about $5.5 billion. Supported the creation of about 147,000 jobs, boosting household income by $4.4 billion. Reduced trade deficit by $5.1 billion by eliminating the need for 143.3 million barrels of oil. Added $2.5 billion in tax income. Profitable byproducts are produced in the ethanol production process.
Wet MillingDry Milling Products Ethanol Carbon Dioxide (used as a refrigerant, in carbonated beverages, to help vegetables grow quicker in greenhouses, and to flush oil wells) Ethanol Carbon Dioxide Co-products Corn oil (used in producing food products for human consumption) Amino Acids (used as animal feed additives) Corn Gluten Meal (used as a high protein livestock feed additive, valued especially in poultry feeds) Corn Gluten Feed (used as a high protein livestock feed supplement, used widely in dairy and beef production) Dry Distiller’s Grains (used as a high protein and energy animal feed) Fibrotein (used as a high fiber and protein food additive) Byproducts of Production Taken from www.ethanol-crfa.org
MTBE Treatment in Water Estimated $29 billion to clean up MTBE contaminated water Established Technologies –O 3 /H 2 O 2 –UV/H 2 O 2 –UV/O 3 –Activated Carbon
Incentives/Subsidies Once subsidies and tax incentives, as well as other costs such as military protection spending, the true cost of gasoline is estimated to be between $5.60 to $15.14 per gallon. Ethanol has a partial exemption from the federal excise tax on fuel sales, exactly how much depends on the amount of ethanol in the blend. Totaling about $7.1 billion from 1979 to 1995. Ethanol also has a partial income tax credit of $0.54/gallon for producers and resellers of gasoline blended with ethanol.
MTBE Overview Advantages –Reduces emissions more effectively than ethanol –Costs Less than Ethanol –Less volatile than Ethanol in gas (makes transport significantly easier) Disadvantages –Natural Gas Derivative Non-renewable Volatile prices –Possible Carcinogen and other unknown long-term health effects –Costly Treatment –Very mobile in soil, air, water
Ethanol Overview Advantages –Allows for domestically dependent energy sources. –Is renewable. –Readily metabolizes in cells and the environment. –Is only mildly toxic to the environment. –Produces profitable by- products. –Reduces carbon release by incorporating the carbon cycle. Disadvantages –More expensive than MTBE or gasoline. –Not as easy to transport. –Decreases vehicle mileage. –Has a large land usage cost associated with production. –Miscible in water decreases ease at which it can be cleaned up.
Resources Renewable Fuels Association – Ethanol –www.ethanolrfa.orgwww.ethanolrfa.org DOE renewable Fuel Site –http://www.eia.doe.gov/cneaf/solar.renewables/renewable.energy.annual/backgrnd/chap8d.h tmhttp://www.eia.doe.gov/cneaf/solar.renewables/renewable.energy.annual/backgrnd/chap8d.h tm Gasoline Prices –http://www.eia.doe.gov/neic/brochure/oil_gas/primer/primer.htmhttp://www.eia.doe.gov/neic/brochure/oil_gas/primer/primer.htm Ethanol Fuel Prices Analysis –http://www.news.cornell.edu/releases/Aug01/corn-basedethanol.hrs.htmlhttp://www.news.cornell.edu/releases/Aug01/corn-basedethanol.hrs.html American Coalition for Ethanol –http://www.ethanol.org/index.htmhttp://www.ethanol.org/index.htm Effects of Fuel Ethanol Use on Fuel-Cycle Energy and Greenhouse Gas Emissions –http://www.ethanol.org/pdfs/ethanol_effects_99.pdfhttp://www.ethanol.org/pdfs/ethanol_effects_99.pdf Canadian Renewable Fuels Association –http://www.greenfuels.org/index.htmlhttp://www.greenfuels.org/index.html –Air Quality and Ethanol in Gasoline http://www.greenfuels.org/images/NEC-Whitten.pdf