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

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

MTBE Routes of Entry

• Inhalation – 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

Reductions for varying levels of Ethanol usage.

Argonne National Laboratory – U.S. DOE

•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

Chemical Properties

State MTBE Bans

State Effective Date

Arizona Effective

California Effective

Colorado Effective

Connecticut Effective

Illinois Effective

Indiana Effective

Iowa Effective

Kansas Pending Federal Action

Kentucky 01-01-06

Maine 01-01-07

Michigan Effective

Minnesota Effective

Missouri 07-01-05

Nebraska Effective

New Hampshire Pending Federal Action

New York Effective

Ohio 07-01-05

South Dakota Effective

Washington Effective

Wisconsin Effective

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

• 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)

MTBE vs Ethanol Production

Source: Department of Energy

January, 2003: First month in which Ethanol production beat MTBE

MTBE Costs

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

  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)

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

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

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.

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