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1Niall Kearns Brent Lemberg MTBE or Ethanol?Niall KearnsBrent Lemberg
2NomenclatureEthanol – Ethyl Alcohol, “(CH3CH2OH) 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 (C5H12O)Fuel additive (up to 10-15%) for two reasonsOxygenate (Clean Air Act of 1990)Boost octane ratingGallstonesOne of the strokes is the compression stroke, where the engine compresses a cylinder-full of air and gas into a much smaller volume before igniting it with a spark plug. The amount of compression is called the compression ratio of the engine. A typical engine might have a compression ratio of 8-to-1.an oxygenate reduces the amount of unburned hydrocarbons and carbon monoxide in the exhaust.MTBE is also used to dissolve gallstones. Patients treated in this way have MTBE delivered directly to their gall bladders through special tubes that are surgically inserted.
3MTBE History1960s: Italian company creates MTBE initially as a solvent, then octane enhancer1960s: Development of catalytic converters, leading to removal of lead from gasoline1973: first MTBE plant opens in ItalyLate 1970s: Several plants opened in U.S. to boost octane ratings of unleaded gas1980s: MTBE use continues to increase1990: Clean Air Act (requires MTBE, or other oxygenates)1999: California first state to create plan to eliminate MTBE as a fuel additive2003: Wisconsin Act 45: Wisconsin gasoline cannont contain more than .5% MTBE by Aug. 1, 2004Due to its detrimental effect on the efficiency of the catalyst, lead is gradually removed from gasoline.combining a by-product of the chemical industry of limited value (isobutylene) with methyl alcohol (an alcohol completely unrelated to the petroleum cycle), thus recovering and valorising the by-product and making it available for use in petrol blending.
4Ethanol History3000 B.C. Earliest known written record of alcohol consumption.1859: Ethanol sales for lamp fuel exceeded 25 million gallons.: 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: ProhibitionIt 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.
5More Ethanol History1979: Amoco markets the first Ethanol fuel blends.1979: Interior and Related Agencies Appropriation ActAppropriated $19 billion to stimulate production of alternative fuels.1980: Fewer than 10 ethanol production facilities exist.1980: Energy Security ActOffered 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 ActMandates that 39 areas use oxygenated fuel in the winter and 9 areas use it year round.
6MTBE Health Effects Class 3 Carcinogen Laboratory Animals Kidney and testicular tumorsLymphoma and LeukemiaShort Term Effects:Odor and Taste ConcernsIrritation of the eyes, nose, throatHeadacheDisorientationBreathing ProblemsClass 3 -- Not classifiable for human carcinogenicity.This category is used most commonly for agents, mixtures and exposure circumstances for which the evidence of carcinogenicity is inadequate in humans and inadequate or limited in experimental animals. Exceptionally, agents (mixtures) for which the evidence of carcinogenicity is inadequate in humans but sufficient in experimental animals may be placed in this category when there is strong evidence that the mechanism of carcinogenicity in experimental animals does not operate in humans. When exposed to high levels of MTBE over a long period of time, some laboratory animals developed kidney tumors, testicular tumors, lymphoma and leukemia.Source:
8Ethanol 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.
9MTBE Facts Accounted for 25% of total ozone reductions Equivalent to taking 3.5 million cars off the roadReduces the daily emission of pollutants in California alone by more than 3 million pounds
10Ethanol Facts – Benefits Ethanol provides a renewable domestic source of fuel!Observing the carbon cycle shows that net CO and CO2 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 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.
11Ethanol 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
12Carbon Monoxide emissions levels and sources – CO is a major contributor to ground level ozone formation.
13Emissions Comparison Source: American Water Works Association Formaldehyde: a breakdown product of MTBESource: American Water Works Association
17This was attached to the report commissioned by the U. S This was attached to the report commissioned by the U.S. Department of Energy that contained the previous two slides information.
18An co-analysis on exhaust emissions also showed that there was neither a increase or decrease in overall emissions, it varied by vehicle.Some Evidence shows that the use of Ethanol as a fuel actually decreases the mileage that a vehicle can obtain.
19MTBE Environmental Discharge Leaking Underground Storage TanksSpillage at the pumpVolatilizationMotorized Water RecreationAccidentsAlthough MTBE supplements gasoline in only 16 states, it has been detected in water supplies in 49 states. As many as 55 percent of large, urban water systems have detected some level of MTBE in their water supplies, according to the U.S. Geological Survey's July 2003 Water Quality Assessment. Three years earlier, only 15 percent of drinking water sites tested in the Northeast were found to contain MTBE. Conservative estimates place the contaminant in about 500 public drinking water wells and in about 45,000 private wells across the U.S.MTBE isnt as large a problem in the air, as it is broken down by UV. Half life in air of about 4 hours.In the soil, it biodegrades very slowly- very long half life
20Chemical Properties-Relatively low vapor pressure allows it to readily vaporize-high solubility-low henry’s constant (prefers to stay in the water phase)
21State MTBE Bans State Effective Date 20 Total States Arizona Effective CaliforniaColoradoConnecticutIllinoisIndianaIowaKansasPending Federal ActionKentuckyMaineMichiganMinnesotaMissouriNebraskaNew HampshireNew YorkOhioSouth DakotaWashingtonWisconsin20 Total StatesState MTBE Bans
22Wisconsin 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 EffluentsWisconsin Groundwater Standard60 ppbIn California: a primary maximum contaminant level (MCL) of 13 micrograms per liter (µg/L), effective May 2000, that addresses health concerns — its public health goal is also 13 µg/La secondary MCL of 5 µg/L, effective January 1999, that addresses concerns about taste and odor (http://www.dhs.ca.gov/ps/ddwem/chemicals/MTBE/mtbeindex.htm)
23Microbial 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.
24MTBE ProductionCH3OH + CH2=C(CH3)2+ H+ CH3OC(CH3)3 + H+Two Major types of plants (Differ in Isobutylene source)Refinery/Petrochemical PlantsIsobutylene produced as a byproductCheaper, but smaller capacityMerchant PlantsIsobutylene produced from butane2-5 times as expensive, larger capacityMethanolNatural Gas Derivative (same for both plants)Refinery/Petrochemical plants: Isobutylene, produced as a byproduct in refinery catalytic crackers and in petrochemical ethylene plants, is reacted with methanol to produce MTBE. These are the smallest and the least expensive MTBE plants to build at $6,000 to $10,000 per daily barrel of capacity.(3)Merchant plants: Merchant plants isomerize normal butane to isobutane, dehydrogenate isobutane to isobutylene, and then react the isobutylene with methanol to produce MTBE. The merchant plants are the most expensive to build at $20,000 to $28,000 per daily barrel of capacity.(3)
25MTBE vs Ethanol Production Source of fact:Source: Department of EnergyJanuary, 2003: First month in which Ethanol production beat MTBE
26MTBE Costs Source: Department of Energy The price of MTBE is largely dictated by the price of natural gas for both types of plants. Both of the spikes on the graph corresponded to increased natural gas prices in this time span. For a 10 cent increase in cost of natural gas, MTBE increases by 4 cents. The Merchant plant also depends on the price of butane. For a 10 cent increase in butane, there is a 10 cent increase in the price of MTBE.Source: Department of Energy
27Ethanol 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.
28Ethanol Base Stock Sources Ethanol can be made from virtually any biomass source.Those currently in use are:CornCheese WheyBarleyWaste BeverageWaste Beer/Brewery Waste (Coors & Miller)Wheat StarchSugars and starchesGrain Sorghum
29Economics 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.
30EconomicsIncreased 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 million barrels of oil.Added $2.5 billion in tax income.Profitable byproducts are produced in the ethanol production process.
32Byproducts of Production Wet MillingDry MillingProductsEthanolCarbon Dioxide (used as a refrigerant, in carbonated beverages, to help vegetables grow quicker in greenhouses, and to flush oil wells)Carbon DioxideCo-productsCorn 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)Taken from
34MTBE Treatment in Water Estimated $29 billion to clean up MTBE contaminated waterEstablished TechnologiesO3/H2O2UV/H2O2UV/O3Activated CarbonAuthors:Preston, MarkSource:American City & County; Apr2004, Vol. 119 Issue 4, p28, 1p, 1c
35Incentives/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.
36MTBE Overview Advantages Disadvantages Reduces emissions more effectively than ethanolCosts Less than EthanolLess volatile than Ethanol in gas (makes transport significantly easier)DisadvantagesNatural Gas DerivativeNon-renewableVolatile pricesPossible Carcinogen and other unknown long-term health effectsCostly TreatmentVery mobile in soil, air, water
37Ethanol Overview Advantages Disadvantages 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.DisadvantagesMore 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.
39Resources Renewable Fuels Association – Ethanol DOE renewable Fuel SiteGasoline PricesEthanol Fuel Prices AnalysisAmerican Coalition for EthanolEffects of Fuel Ethanol Use on Fuel-Cycle Energy and Greenhouse Gas EmissionsCanadian Renewable Fuels AssociationAir Quality and Ethanol in Gasoline