Niall Kearns Brent Lemberg MTBE or Ethanol? Niall Kearns Brent Lemberg

Nomenclature Ethanol – 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 reasons Oxygenate (Clean Air Act of 1990) Boost octane rating Gallstones One 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.

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 http://www.efoa.org/newsletter/issue_2.htm Due 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.

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 Class 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: http://www.dhfs.state.wi.us/eh/ChemFS/fs/MTBE.htm

MTBE Routes of Entry Inhalation Ingestion Skin Absorption Exhaust, Pump Fumes, Showering Ingestion Skin Absorption

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 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 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 Formaldehyde: a breakdown product of MTBE Source: American Water Works Association

Reductions for varying levels of Ethanol usage.

Argonne National Laboratory – U.S. DOE

This 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.

An 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.

MTBE Environmental Discharge Leaking Underground Storage Tanks Spillage at the pump Volatilization Motorized Water Recreation Accidents Although 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

Chemical Properties -Relatively low vapor pressure allows it to readily vaporize -high solubility -low henry’s constant (prefers to stay in the water phase)

State MTBE Bans State Effective Date 20 Total States Arizona Effective California Colorado Connecticut Illinois Indiana Iowa Kansas Pending Federal Action Kentucky 01-01-06 Maine 01-01-07 Michigan Minnesota Missouri 07-01-05 Nebraska New Hampshire New York Ohio South Dakota Washington Wisconsin 20 Total States State MTBE Bans

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 In 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/L a 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)

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 CH3OH + CH2=C(CH3)2+ H+  CH3OC(CH3)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) 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)

MTBE vs Ethanol Production Source of fact: http://www.ethanolrfa.org/pr030320.html Source: Department of Energy January, 2003: First month in which Ethanol production beat MTBE

MTBE 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. http://www.eia.doe.gov/emeu/steo/pub/special/mtbecost.html Source: Department of Energy

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.

Plant Locations

Byproducts of Production   Wet Milling Dry Milling Products Ethanol Carbon Dioxide (used as a refrigerant, in carbonated beverages, to help vegetables grow quicker in greenhouses, and to flush oil wells) 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) Taken from www.ethanol-crfa.org

Possible Oxygenate Substitutes Ethyl Tertiary-Butyl Ether (ETBE) Tertiary-Amyl Methyl Ether (TAME) Di-isopropyl Ether (DIPE) Tertiary-Butyl Alcohol (TBA) Tertiary Amyl Ethyl Ether (TAEE) Methylcyclopentadienyl Manganese Tricarbonyl (MMT) Methanol

MTBE Treatment in Water Estimated $29 billion to clean up MTBE contaminated water Established Technologies O3/H2O2 UV/H2O2 UV/O3 Activated Carbon Authors:Preston, MarkSource:American City & County; Apr2004, Vol. 119 Issue 4, p28, 1p, 1c

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 Disadvantages 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 http://www.calgasoline.com/factprice.htm

Ethanol 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. 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.

Questions & Comments

Resources Renewable Fuels Association – Ethanol www.ethanolrfa.org DOE renewable Fuel Site http://www.eia.doe.gov/cneaf/solar.renewables/renewable.energy.annual/backgrnd/chap8d.htm Gasoline Prices http://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.html American Coalition for Ethanol http://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.pdf Canadian Renewable Fuels Association http://www.greenfuels.org/index.html Air Quality and Ethanol in Gasoline http://www.greenfuels.org/images/NEC-Whitten.pdf