Large Scale Production of Synthetic Fuels

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Large Scale Production of Synthetic Fuels

• Dr. Sam Heintz
• Southern Arkansas University

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• My father rode a camel.
• I drive a car.
• My son will fly a jet.
• My grandson will ride a camel.
• Arab saying.

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• Daily world demand of oil is over 80 billion
  barrels a day.
• Approximately ¼ of this demand is in U.S.
• World oil supplies are at historic peak of
  maximum production.
• Oil production in 18 production countries have
  passed their peak and declining.
• China is driving oil-demand due to higher levels
  of economic activity.

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• The United States turned its back on a sensible
  energy policy in 1980 and opted for endless
  growth.
• The economists all think that if you show up at
  the cashiers cage with enough currency, God will
  put more oil in the ground
• Matt Crensen, Associated Press, May 28, 2005

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• In 1956, a geologist named M. King Hulbert
  predicted that U.S. production would peak in
  1970. He was right. U.S. oil production did
  peak in 1970 and has declined ever since.

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August 8, 2005

• Energy Policy Act (EPACT) mandates the U.S. use a
  minimum of 4 billion gallons of renewable fuel in
  2006.
• Increases annually to 7.5 billion gallons in
  2012.
• Includes 150 million in 2007 for cellulosic
  ethanol research.

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January 31, 2006. State of the Union Address.

• We will also fund additional research in
  cutting-edge methods of producing ethanol, not
  just from corn but from wood chips and stalks or
  switch grass. Our goal is to make this new kind
  of ethanol practical and competitive within six
  years.

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U.S. Fuel Ethanol Production

• Currently 101 ethanol production facilities in
  the U.S. Nearly half are farmer-owned
  cooperatives.
• At least 30 new ethanol plants are under
  construction.
• Dozens more are in various stages of planning.

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U.S. Fuel Ethanol Production

• 1990 0.900 billion gallons
• 1995 1.400 billion gallons
• 2000 1.630 billion gallons
• 2005 3.904 billion gallons
• 2006 4.5 billion gallons (estimated)
• 2007 6.4 billion gallons (estimated)
• Source US Energy Information Adm.

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• There are 6 million U.S. vehicles, called
  flexible-fuel vehicles, on the road designed to
  use E85.
• Most run on gasoline because there isnt enough
  E85 pumps and many people dont know theyre
  driving a flex-fuel vehicle.
• Source National Ethanol Vehicle Coalition

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Did you know?

• The Ford Model T had a carburetor adjustment to
  switch between gasoline and ethanol. This was
  removed as cheap, plentiful gasoline became
  readily available.

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How is Ethanol Made?Traditional Process

• Milling. Mechanically grinding the corn as
  finely as practical.
• Liquefaction. Meal is mixed with water and
  enzyme. Heat is applied (120-150 C). Converts
  starch molecules to complex sugars.
• Saccharification. Mash is cooled and secondary
  enzyme is added to break down complex sugars into
  simple sugars.

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• Fermentation. Yeast is added to ferment the
  sugars to ethanol and carbon dioxide. Could be
  continuous or batch operation.
• Distillation. Liquid and solids are separated.
  The fermented mash contains about 10 ethanol.
  It is distilled to about 96 strength.

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• Dehydration. The remaining water is removed by
  molecular sieve. Anhydrous ethanol results (200
  proof).
• Denaturing. Ethanol is made unfit for human
  consumption with 2 5 gasoline.
• Co-products. Distillers grain and carbon
  dioxide.
• Distillation is usually fueled by natural gas,
  petroleum fuels, or coal.

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Batch vs. Continuous

• Problems with Batch
• Low conversion of feed
• Low concentration of product
• Product/water/feed need separating
• Its a batch process.

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Continuous Processing

• Usually cells are fixed within reactors and feed
  is slowly pumped pass the yeast.
• Ethanol is continuously removed from yeast
  colony. Colony can live for weeks without new
  inoculation.
• Reactors are arranged so that exit stream from
  one becomes feed to next. This brings ethanol
  concentration up to about 10.

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• A gallon of ethanol replaces only 2/3 of a gallon
  of gas and making it requires the fossil energy
  in about 1/2 gallon of gasoline. So we must make
  6 gallons of ethanol to save the fossil energy in
  one gallon of gas.
• It takes 1.5 gallons of ethanol to give the
  energy in 1 gallon of gasoline.
• Ethanol cannot be added to gasoline at refinery
  and pumped through pipeline because it tends to
  corrode the pipes.

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Corn ethanol is good for them but expensive for
us.

• Subsidy for ethanol production is 0.51/gallon,
  plus a small-producers credit of 0.10/gallon for
  producers of up to 60 million gallons per year.
• Total subsidy for 2005 was estimated to be 1.49
  billion (ADM received 500 million).

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• Adding up the energy costs of corn production and
  its conversion to ethanol, 131,000 BTUs are
  needed to make one gallon of ethanol. One gallon
  of ethanol has an energy value of 77,000 BTUs.
• Dr. Roger Segelken, Cornell University March
  13, 2006.

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• Global market for biofuels such as cellulosic
  ethanol will grow to exceed 10 billion by 2012.
• Enews Bulletin, May 2005

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Cellulosic Ethanol

• Can be produced from a wide variety of cellulosic
  biomass feedstocks including
• Agricultural waste
• (corn stover, cereal straws, sugarcane)
• Plant waste from industrial processes
• (sawdust, wood chips, paper pulp)
• Energy crops
• (switchgrass)

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Two Processing Options

• Acid hydrolysis breaks down complex
  carbohydrates into simple sugars.
• Enzymatic hydrolysis a pretreatment process
  reduces the size of the material, then employs
  enzymes to convert cellulosic biomass to
  fermentable sugars.

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Positive Environmental Benefits

• Cellulosic ethanol production substitutes biomass
  for fossil fuels to produce heat.
• Cellulosic ethanol showed greenhouse gas emission
  reductions of about 80 over gasoline production.
  
• Greenhouse gases produced are offset by the CO2
  absorbed by the biomass as it grows.
• Source Argonne National Laboratories.

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Switchgrass

• Excellent feedstock for cellulosic ethanol.
• Has a deep root system to prevent erosion and
  helps builds soil fertility.
• Uses water efficiently.
• Does not need a lot of fertilizers or pesticides.
  
• Source National Renewable Energy Lab.

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Barriers to Cellulosic Ethanol

• High cost of cellulose enzymes is key barrier to
  economic production.
• Enzymes did cost 5.00 per gallon of ethanol.
• Now enzyme costs 0.10 - 0.20.

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Barriers to Cellulosic Ethanol

• Production facility cost 200 - 250 million to
  build.
• Because of variety of feedstocks, biorefineries
  require a larger range of processing
  technologies.
• Because biomass contains a lower energy density,
  biorefineries need to be close to feedstock
  sources.

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The Future

• By 2050, U.S. will consume 180 to 290 billion
  gallons of gasoline, depending on vehicle
  efficiency.
• 50 billion gallons of cellulosic ethanol can be
  produced from waste streams.
• Switchgrass, grown on 114 million acres, can
  produce 165 billion gallons of ethanol,
  equivalent to 108 billion gallons of gasoline.

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• About 96 of energy used in ethanol production is
  consumed in the distillation step. Can the step
  be replaced with another separation process?
• How about liquid/liquid extraction?

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Liquid-Liquid Extraction

• Many solvents work great at removing the ethanol
  from the fermentation broth.
• Would like to recycle the raffinate after
  extraction to further reduce costs and increase
  production efficiency.
• New problem most solvents are not biocompatible
  with the yeast.
• New problem Solvents are expensive. How to
  separate the ethanol from the solvent?

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First extraction design
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Design and Modification

• Distillation to a concentration of 85 ethanol
  only uses about 30 of the energy required to
  distilled to 93 ethanol concentration.
• Gasoline makes a good solvent for extraction.
  Ethanol recovery as high as 99 is achievable
  with enough equilibrium stages.

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Second extraction design
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What is Biodiesel Fuel?

• Biodiesel is an alternative fuel produced from
  domestic, renewable resources. Biodiesel
  contains no petroleum but can be blended at any
  level with petroleum. It is biodegradable,
  nontoxic, and essentially free of sulfur and
  aromatics.

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Did you know?

• Rudolf Diesel employed peanut oil to power one
  of his engines at the Paris Exposition of 1900.

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Mud Puddle Chemistry

• Biodiesel is easy to make. The feedstock is
  filtered, mixed with an alcohol (methanol), and
  a catalyst (sodium or potassium hydroxide). The
  major products are a methyl ester (biodiesel) and
  glycerol. The chemical process is called
  transesterification.

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Vegetable Oil YieldsGal/Acre

• Corn 18 Cotton 35
• Soybean 48 Rice 88
• Sunflowers 102 Peanuts 113
• Olives 129 Pecan nuts 191
• Avocado 282 Oil Palm 635
• Source USDA/NASS

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Arkansas Crop Report

• 46 of U.S. production of rice.
• 10 of U.S. production of cotton.
• 4 of U.S. production of soybean.
• 0.4 of U.S. production of corn.

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Advantages of Base Catalyzed Reaction

• Low Temperature (150 F)
• High Conversion (98)
• Direct Conversion to Methyl Ester.
• Batch reaction but reaction time is only about a
  day.
• Continuous reaction can be done fairly easily.

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Nothing is Wasted

• Process Input
• Oil (Fatty Acid) 87
• Methanol 12
• Potassium Hydroxide 1
• Process Output
• Methyl Ester 86
• Glycerine 9
• Methanol 4
• By-Product (Fertilizer) 1

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Advantages of Biodiesel

• Less toxic than table salt.
• Biogrades as fast as sugar.
• Can be used in diesel engines with little or no
  modification.
• There is an excess production of soybeans in the
  U.S. This is an economical way to utilize the
  surplus.

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Advantages of Biodiesel

• Compared to petroleum diesel, biodiesel produces
  less particulate matter, CO, unburned
  hydrocarbons, and SO2.
• Biodiesel can be used in combination with heating
  oil to heat residential and industrial building.
  
• Even B01 can provide up to 65 increase in
  lubricity in distillate fuels.

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Advantages of Biodiesel

• 8. Is the only alternative fuel to fully complete
  the health effects testing required under 1990
  CAAA.
• Produced under industry specifications in ASTM
  D6751.
• Shows similar fuel consumption, horsepower, and
  torque as conventional diesel fuels.

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Disadvantages of Biodiesel

• Cost. About 2.95 per gallon to make.
• It still takes energy to produce biodiesel from
  crops.
• Pure biodiesel will soften and degrade certain
  types of elastomers and rubber compounds over
  time.
• Biodiesel does produce more nitrogen oxides than
  petroleum diesel.

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Disadvantages of Biodiesel

• 5. Biodiesel cleans the dirt from engines or
  pipelines after a period of operation with
  petroleum diesel. The dirt can collect in the
  fuel filter and clog it.
• 6. Cold weather can cloud and even gel biodiesel.
• 7. Distribution infrastructure in not in place.

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Batesville, Arkansas
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Eastman Chemicals
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Chemical Plant
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White River
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Equilibrium Pond
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Uses Four Different Feedstocks

• Cottonseed oil
• Soybean oil
• Poultry fat
• Pork lard

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Different Biodiesel Products
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• Current production is 18 million gallons annually
  (and increasing).
• Will be 25 million gallons by end of 2006.
• Plant capability is 100 million gallons.
• Selling every drop to fleets of vehicles.
• No distribution system, no piping of biodiesel.

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• Sells B100 at 2.94 a gallon.
• Sells B99.9 at 1.95 a gallon.
• For on-road use, users must pay additional state
  tax of 0.42 a gallon.
• Farmers or off-road, no state tax.

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CGI
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Biodiesel Plant
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Rail Yard
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3000 to 4000 Gallon Tanks
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Reaction Vessel
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Truck Loading Station
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Some notes on production

• Eastman uses glycerine as fuel.
• Eastman expresses concerns that glycerine from
  other manufacturers may contain methanol, which
  makes it a hazardous waste.
• ASTM D 6751 applies only to B100. B99.9 is not
  covered by standard.

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Potlatch Corporation

• Corporate Office is in Spokane, Washington
• Pulp and paperboard mill near McGehee, Arkansas
• First site in country for new type of
  biorefinery.
• Part of DOE grant program

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Potlatch Process
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Potlatch Process

• Uses thermochemical process to produce a
  synthetic gas from wood and agricultural waste.
• Once converted to a liquid, is sold to petroleum
  refinery for transportation fuel.
• Part of syngas is used as fuel within mill and
  waste heat is used to generate electricity
  on-site.

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• Potlatch estimates that it reduces its
• Natural gas usage by 1.6 billion cubic feet or
  80 percent.
• Purchased electricity by 80,000 megawatt hours
  annually or 60 percent.
• Source Arkansas Gazette, Jan. 8, 2006