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

2. 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.

3. 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
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.

4. Ethanol History
3000 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: 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.

5. 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.

6. 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:

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

8. 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.

9. 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

10. 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 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.

11. 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

12. Carbon Monoxide emissions levels and sources – CO is a major contributor to ground level ozone formation.

13. Emissions Comparison Source: American Water Works Association
Formaldehyde: a breakdown product of MTBE
Source: American Water Works Association

14. Reductions for varying levels of Ethanol usage.

15. Argonne National Laboratory – U.S. DOE

17. 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.

18. 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.

19. 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

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

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

22. 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 (

23. 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.

24. 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)

25. MTBE vs Ethanol Production
Source of fact:
Source: Department of Energy
January, 2003: First month in which Ethanol production beat MTBE

26. 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.
Source: Department of Energy

27. 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.

28. 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

29. 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.

30. 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 million barrels of oil.
Added $2.5 billion in tax income.
Profitable byproducts are produced in the ethanol production process.

31. Plant Locations

32. 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

33. 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

34. 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

35. 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.

36. 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

37. 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.

38. Questions & Comments

39. Resources Renewable Fuels Association – Ethanol
DOE renewable Fuel Site
Gasoline Prices
Ethanol Fuel Prices Analysis
American Coalition for Ethanol
Effects of Fuel Ethanol Use on Fuel-Cycle Energy and Greenhouse Gas Emissions
Canadian Renewable Fuels Association
Air Quality and Ethanol in Gasoline