Biofuels from Common Local Diffuse Source Seed Crops:

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Biofuels from Common Local Diffuse Source Seed
Crops

• Biodiesel from Acorns

Eddie D. Luzik Jr. PhD.
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Biofuels from Common Local Diffuse Source Seed
Crops Biodiesel from Acorns

• Connecticut being a small and populous state,
  common wisdom is that we cannot be a source
  material producer for renewable transport fuels
  without serious alteration of the landscape. In
  this presentation the chemistry, agricultural and
  intellectual opportunities for benignly
  generating biofuel in Connecticut will be
  discussed through our experiments with
  unrecognized campus seed crops.
• An overview of the current renewable fuels used
  for transportation highlights the difficulties
  for sourcing them in Connecticut. The issues
  discussed are also of concern on a global scale
  and support agricultural diversification of seed
  crops multiple fuel sources and fuel-use
  platforms can reduce risk as well as
  environmental impact. A pictorial description of
  our model study into making biodiesel from acorns
  at UNH highlights the chemistry processes
  involved in going from seeds to fuel. A New
  England Puritan approach to supplying a portion
  of modern energy is using existing landscape
  waste to produce a high value commodity
  biodiesel. A conclusion is formed that a wide
  fuel portfolio opens production opportunities for
  Connecticut as well as the potential to engineer
  clean efficient engines that use the new fuels.

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Biofuels from Common Local Diffuse Source Seed
Crops Biodiesel from Acorns

• Chemically, what is vehicle fuel?
• Traditionally, a mixture of petroleum
  hydrocarbons.
  

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Biofuels from Common Local Diffuse Source Seed
Crops Biodiesel from Acorns

• Biodiesel has a chain length similar to diesel
  and an ester group at the end.
  

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Biofuels from Common Local Diffuse Source Seed
Crops Biodiesel from Acorns

• Biodiesel is made from triglyceride oils.

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Biofuels from Common Local Diffuse Source Seed
Crops Biodiesel from Acorns

• Biodiesel FAME is often made with fossil sourced
  methanol while FAEE is made with fermented-sugar
  derived ethanol making it more green.

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Biofuels from Common Local Diffuse Source Seed
Crops Biodiesel from Acorns

• Fatty Acid Methyl Ester (FAME) and Fatty Acid
  Ethyl Ester (FAEE) are made from triglycerides
  that contain fatty acids that are often
  unsaturated, poly-unsaturated or
  trans-unsaturated.

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Biofuels from Common Local Diffuse Source Seed
Crops Biodiesel from Acorns

• The Fatty Acid Part of Triglycerides
• Saturated Fats Bad for food Good for Fuel
• Think about the food vs. fuel issue
• Unsaturated Fats More healthy for humans, but
  less chemically stable fuels.
  
• What are the natural sources of mostly saturated
  triglycerides?
  

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Biofuels from Common Local Diffuse Source Seed
Crops Biodiesel from AcornsMost Prevalent
Chain Length and Type for Sample Oils
(1) Values from Biology Data Book H.J.Harwood,
R.P.Geyer
1964 FASEB Washington D.C. p380-382
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Biofuels from Common Local Diffuse Source Seed
Crops Biodiesel from Acorns

• Saturated Oils are most common in waste food oils
  like grease, used cooking oil and lard but this
  source is insufficient for fuel demand.
  
• Growing oil seeds - soy, corn, coconut creates
  an issue of land use and product consumption as
  fuel in place of food.

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Biofuels from Common Local Diffuse Source Seed
Crops Biodiesel from Acorns

• Connecticut is a small state 4585 sq mi.
• Limited surplus land available for farming.
• Undesirable to alter the landscape.
• Potential to use marginal lands. (polluted
  land, brownfields, highway periphery.
  
• Glean wasted unrecognized crops from existing
  urban and suburban landscapes.
  

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Biofuels from Common Local Diffuse Source Seed
Crops Biodiesel from Acorns

• Non-Food Crops on Non-Food Acreage
• Canola or Mustard Seed grown along highways,
  industrial sites, airports, etc. provide oil
  without contaminant concern.
  
• Tree seeds from landscape waste provide oil from
  urban and suburban lands and encourage
  continuation of our treescape.
  

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Biofuels from Common Local Diffuse Source Seed
Crops Biodiesel from Acorns

• Tree Seeds!
• Already often collected, but not separated at
  compost site.
  
• Could be of added value to landscapers.
• Collection could stabilize rodent populations.
• Encourage continuation and care for our trees.

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Biofuels from Common Local Diffuse Source Seed
Crops Biodiesel from Acorns

• Seed Trees
• Cut A/C Costs
• Wind abatement
• Cut noise pollution
• Absorb Air Pollution
• Uptake ground water nutrients

• Provide habitat
• Provide biomass
• Provide lumber or firewood
• Preserve landscape

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Biofuels from Common Local Diffuse Source Seed
Crops Biodiesel from Acorns

• How to get oil from a seed

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Biofuels from Common Local Diffuse Source Seed
Crops Biodiesel from Acorns

• Grind cherry seeds
• weigh seed flour

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Biofuels from Common Local Diffuse Source Seed
Crops Biodiesel from Acorns
Soxhlet extraction of cherry oil
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Biofuels from Common Local Diffuse Source Seed
Crops Biodiesel from Acorns

Cherry oil extract was filtered and the solvent
removed at reduced pressure.
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Biofuels from Common Local Diffuse Source Seed
Crops Biodiesel from Acorns
Recovered oil was transesterified with methanol
and sodium hydroxide.
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Biofuels from Common Local Diffuse Source Seed
Crops Biodiesel from Acorns
Extraction, separation, and washing then vacuum
distilling of FAME
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Biofuels from Common Local Diffuse Source Seed
Crops Biodiesel from Acorns

• Vegetable oils from pressing or extracting
  (solvent or carbon dioxide methods)
  
• Animal oils from cooking down and skimming
  processes
  
• Waste grease from fryers etc
• Triglyceride feedstock to be processed

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Biofuels from Common Local Diffuse Source Seed
Crops Biodiesel from Acorns

• into biodiesel.

Gas chromatograph data from cherry FAME
Data from Gillian Lazarus 2008
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Biofuels from Common Local Diffuse Source Seed
Crops Biodiesel from Acorns

• Raw transesterified product FAME is backyard
  biodiesel and has impurities
  
• Alcohols and trace water,
• Glycerol and partially reacted glycerides,
• Residual catalyst and sodium salts (soap),
• Terpines and aromatic substances,
• Unsaturated and saturated ester mixture.

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Biofuels from Common Local Diffuse Source Seed
Crops Biodiesel from Acorns

• Washing with water removes some impurities
  (methanol, glycerol, soap) but creates waste.
  
• Vacuum distilling purifies the product, but with
  added energy consumption and unsaturated
  components remain reactive.
  

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Biofuels from Common Local Diffuse Source Seed
Crops Biodiesel from Acorns

• Hydrotreating a process also used on petroleum
  fuels and to make margarine produces a fully
  saturated FAME
  
• (to reduce cost here, it is best to have an oil
  of mostly saturated fatty acids).
  
• Product is then more stable to air, light, and
  mold.

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Biofuels from Common Local Diffuse Source Seed
Crops Biodiesel from Acorns

• Yield how much oil is in a seed?
• Acorns and cherries (pits) collected around
  campus average 22-18 oil by weight.
  
• An oak produces 2-10 buckets of acorns,
• A drywall bucket is about ½ bushel.
• One bushel of acorns is about 53 pounds.
• Average 80 mass is viable
• oil stock.

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Biofuels from Common Local Diffuse Source Seed
Crops Biodiesel from Acorns

• How many acorns can we get?
• An average northern red oak tree (50 years, 60
  tall, landscape at 27 trees per acre. (About 1 to 8
  suburban/urban yards).
• At only 20 trees per acre we could get 125-25(low
  mast year) gallons of biodiesel/acre.
  
• This compares to soy at 56gal/acre and in best
  years almost to castor at 156gal/acre(3).

(2) L.J.Wolgast Wildlife Society Bulletin,
V.7,No3,1979,p176-8
(3) www.farmgate.uiuc.edu/archive/2006/10/october1
9
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Biofuels from Common Local Diffuse Source Seed
Crops Biodiesel from Acorns

• Oak trees the ultimate no-till crop?
• Last year soy produced 73 of our biodiesel
• 75,000,000 gal.
• But we used mostly petro diesel
• 63,000,000,000gal
• Just in the USA

(3) www.farmgate.uiuc.edu/archive/2006/10/october1
9
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Biofuels from Common Local Diffuse Source Seed
Crops Biodiesel from Acorns

• To replace all of our diesel with acorn biodiesel
  we would need 1.6 billion acres of average trees,
  about 1000 x current number of home yards.
  
• There is no single replacement but we can create
  value and jobs in using diverse fuel sources,
  with each displacing some fossil fuel tonnage.
  
• The Puritan approach not waste anything!

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Biofuels from Common Local Diffuse Source Seed
Crops Biodiesel from Acorns

• Biofuels present the opportunity to offer
  consumers a selection of pure-substance fuel
  products.
  
• Ethanol, (bio)Methanol, FAEE, FAME, etc.
• Biofuels offer engine designers opportunities to
  exploit pure substance properties for greatest
  efficiencies and low emissions.
  
• Low sulfur, cool flame low NOx
• Biofuels could keep biomatter out of landfills
  and compost sites, and thus utilize the carbon
  content.
  

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Biofuels from Common Local Diffuse Source Seed
Crops Biodiesel from Acorns

• Continuing and future work at UNH
• Collaboration with Marine Biology to evaluate
  Connecticut Algae for oil potential.
  
• Move extraction methods to Super Critical Fluid
  carbon dioxide technology.
  
• Investigate FAEE including acid catalyzed
  synthesis routes.
  
• Evaluate biodiesel product by HPLC protocols.

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Biofuels from Common Local Diffuse Source Seed
Crops Biodiesel from Acorns

• Biofuels at UNH offer exciting learning
  experiences with real materials undergoing
  relevant chemistries!
  
• Thanks to Biofuel group Robert Almeida, Gillian
  Lazarus,
  
• John Karstens, Heather McClure, Kyle Whitten.
• UNH Summer Faculty Research Fellowship.
• Department of Chemistry and Chemical Engineering
  Laboratories and Instrumentation resources.
  
• Special thanks to Cynthia Shea-Luzik for aiding
  and abetting seed collecting.
  
• All pictures by EDL and Biofuel Students.