The Biorefinery in New York: Woody Biomass Into Commercial Ethanol Implementation Will Come Through

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The Biorefinery in New YorkWoody Biomass Into
Commercial EthanolImplementation Will Come
Through Multi-Institution Collaboration

• Dr.Tom Amidon Dr. Gary Scott
• Faculty of Paper Science and Engineering, SUNY
  ESF
• October 20, 2006

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A Hemicellulose Example of closing the Separation
and Conversion gaps Ethanol from glucose is well
developed but, if practiced as currently applied
in commerce, would use the currently most
valuable cellulose (hydrolyzed to glucose) as the
predominant sugar source. Commercial adaptation
of the process to wood hemicelluloses is a
prerequisite for using this less currently valued
component available from biomass and wood. These
hemicelluloses are predominately glucurono-xylan
in hardwoods and galactoglucomannan in softwoods
(with a significant softwood component of an
Arabino-xylan) and will yield fermentation
substrates different from cellulose. ---From
Solutions April 2002, T.E. Amidon.
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Outline

• 6 Ws
• What, Where, When, Why, Who, How
• With special appreciation for Dr. A. Stipanovic
  who
• developed a significant portion of the material
  included in this presentation.

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Composition of Dried Woody Biomass

• Cellulose (1-4)-?-D-Glucan
• Lignin Complex X-Linked Polymer
• Hemicellulosic Polysaccharides
• Different in Hardwoods / Softwoods
• Extractives, Ash

Cellulose
Glucose
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SO What are these Sugars and Why Should I
Care?C6 H12 O6 Hexose, Glucose is the main
oneC5 H10 O5 Pentose, Xylose is the main one
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Cellulose Utilization

• Whole Wood Fibers Paper
• Fiber Crystallites Lite Composites and SRMs
• Cellulose--gt Glucose--gt Ethanol
• Glucose --gt Levulinic Acid

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Structure of simple sugar units comprising
hemicelluloses From Paper Chemistry An
introduction. D. Eklund T. Lindstrom, 1991
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A qualitative comparison of the occurrence of
hemicelluloses in hardwood softwood. From
Eklund Lindstrom
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From Paper Chemistry An introduction. D.
Eklund T. Lindstrom, 1991
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Shortened formula for Glucuronoxylan Sugar
units ß-D-xylopyranose (Xylp) and
4-O-methyl-a-D-glucopyranosyluronic acid (GlcpA).
R is an acetyl group (CH3CO-). From Paper
Chemistry An introduction. D. Eklund T.
Lindstrom, 1991
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The Short Answer The sugars are not much
different but the bugs do sometimes care and the
polymers of them are different.

• Some microorganisms are selective and some are
  omnivorous.
• Some change product ratios with substrate.
• Some prefer, grow or produce better on certain
  sugars.
• Some are easy to dissolve/hydrolyze and some are
  not.

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What

• Biorefinery in New York Enhancing the speed to
  application of a new technology by erecting a
  virtual enterprise from multiple companies with
  much to gain in their core businesses from the
  parts of the novel technology that look easy to
  them.

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What - The Wood-Based Biorefinery
Renewable, Sustainable Bioproducts Fuels,
Chemicals, Materials
Biomass Feedstock
Renewable Resources to Green Bio-Products
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What

• Wood Growing, Procurement, Chipping, Chemical
  Processing Pulp and Paper
• Willow Biomass Growing, harvesting, Burning
  Farmers/Wood Fuel Industry
• Fermentation of sugars to products and marketing
  Ethanol Industry

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Where

• Conventional Wood Processing -Pulp in
  Ticonderoga,Oneonta/Lyonsdale for fuel
• Biomass Willow New York Field Trials in Tully,
  NY and Lyons Falls, NY
• Fermentation of Sugars in Fulton and Oneonta, NY

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When

• In the next year
• Extraction of wood sugars at ESF Pilot
• Pilot extraction, fermentation, and burning of
  Extracted Wood at Lyonsdale
• Ethanol from Wood Sugars at ESF Pilot
• Northeast Biofuels reconfiguration

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When

• Over the next two years
• Extraction of wood sugars at Lyonsdale, Oneonta,
  and Ticonderoga
• Burning of Extracted Wood at Lyonsdale/Oneonta
• Ethanol from Wood Sugars at Oneonta and
  NEB,Fulton

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When

• Over the next three years
• Commercial Scale Extraction of wood sugars at
  Oneonta and ethanol production and
  extraction/shipping at Ticonderoga
• Extraction, Shipping, and Burning at Lyonsdale
• Ethanol from Ticonderoga/LyonsdaleWood Sugars
  produced at Northeast Biofuels

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Why - Targets for a National Biobased Industry
NRC Report - 2000
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Agenda 2020 Focus for the Future Meeting the
Challenge of Deployment
Positively Impacting the Environment ?Significant
Reduction in Greenhouse Gases ?Decreased
Ecological Footprint
CO2
O2
Breakthrough Mfg. Technologies ?Major
Manufacturing Cost/Capital
Reduction ?Significant Enhancement in
Product Properties with Existing
Assets ?Substantial Improvement in Energy
Efficiency for Existing Processes
Advancing the Wood Products Revolution ?
Improved Building Systems ? Reduced System Costs
Technologically Advanced Workforce ?From
Workforce to Knowledge Workers in 7 years
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Why Paper Industry

• Paper Industry Cellulose for Paper and Lignin
  for Energy yields low profitability
• Insert a new process in front of the digester to
  extract hemicellulose and convert to ethanol,
  PHAs etc. recover acetic acid and enhance energy
  efficiency
• Estimated Profit increase for complete Paper
  Industry application is 3.3 Billion per year
  (Thorp PIMA 04 Presentation)
• Total estimated at 1.9 Billon gallons ethanol and
  600 Million gallons acetic acid for industry
  wide application

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Why Wood Burning Industry

• Wood burning industry Marginal Economics and
  only lowest quality wood economic
• Evolutionary Change - Wood cost at 40-80 per dry
  ton (0.02-0.04/dry pound) and extraction at 15
  of mass with 2/3 as sugars and 1/3 as acetic
  acid/extractives
• Sugars at 0.07/pound and acetic acid/extractives
  at 0.30/pound - .046 .10 0.146/lb. produces
  value for the 300 pounds extracted from
  ½ to all of the wood cost
• Residue burned with cost reduction greater than
  the 15 of mass lost
• Biomass Willow an economic fuel crop

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WhyWood Sugar Ethanol Production in Fulton New
York

• New York Corn for Dairy Use Most commodity corn
  shipped from Mid-West.
• Corn Market Price fluctuation are a serious
  business risk
• Sugar source diversification has beneficial short
  term and long term impact on business model
• Wood sugars locally grown and lower in cost
• Adjacent to Tug Hill Plateau with abundant low
  cost hardwood forests and Ontario Lake Plain
  with excellent Biomass Willow growing potential

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Who

• International Paper Ticonderoga, NY
• Lyonsdale Biomass in Lyons Falls, NY
• Northeast Biofuels in Fulton, NY
• The Glue to get them to stick SUNY
  College of Environmental Science and Forestry,
  SUNY Center for Sustainable and Renewable Energy,
  Syracuse Center of Excellence in Environmental
  and Energy Systems.
• Case-New Holland USA- a critical industrial
  partner in Biomass Willow harvesting equipment
  development.

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How

• Fractionate Woody Biomass with a low cost and
  environmentally preferable system that preserves
  current uses
• Obtain a low cost easy to clean up sugar stream
• Process advantageous for Hardwoods
• Easy separation of valuable co-products

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How

• Use water as the solvent
• Use Membrane Technology
• Commercialize pentose fermentations
• Use conventional wood chips and preserve
  structure in process
• Use membrane and filtration technology

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Acetic Acid Concentration
RO - Water
Industrial Acetic Acid
Extracted Chips To Pulping or Burning
Wood Chips
Nanofiltration
Water Extraction
Ethanol
Water
Polyhydroxyakanoates
Enzyme hydrolysis of sugars
Fermentation
Xylanase
Calcium Acetate?
Neutralization
Lignin Separation
Lime
Lignin to Boiler or products
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Biorefinery Core Competencies

• Feedstock Selection (Fast Growing and, perhaps
  Low or High Lignin/hemicellulose)
• Biodelignification (fungi, enzymes)
• Cellulose, hemicellulose, and lignin separation
  yielding usable fractions (ESF Process)
• Cellulose, hemicellulose and lignin applications
• Waste and energy recovery
• -Gasification for new products

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Conclusions

• Wood holds great promise as the Biorefinery
  feedstock of choice.
• Cellulose, Hemicellulose, and Lignin will all
  enjoy broad utilization.
• Advances in separations systems,
  biotechnology,biomass gasification, silviculture,
  and agro-forestry will establish the 21st century
  and beyond as the Age of Wood.
• We need to start with the low hanging fruit.

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Future Industrial Connections

• Paper Industry Cellulose for Paper and Lignin
  for Energy with Hemicellulose and extractable
  such as acetic acid, turpentine, fatty acids etc.
  for New Materials
• Wood burning industry Lignin as Fuel and all
  other components for New Materials
• Purpose-built Biorefinery All components
  available for New Materials
• Technology appropriate may well differ depending
  on the industry
• Waste and energy recovery
• -Gasification evolution has begun

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Why do this at all?-Paper Industry has had
returns below the cost of capital
10years-Profit increase potential in excess of
25 over cellulose alone-Would raise returns
above COC-A healthy Industry requires that
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Preparation of Cellulose Nanocrystals
Treatment with Acid plus Mechanical
Shearing 12-65 H2SO4, 40-100C, 1-3 hours (W.T.
Winter et. al)
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Magnetic Cellulose FibersLumen Loaded With Fe3O4
Fe3O4 lt 5 micron Particle Size
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Stimuli Responsive Elastomer
Base Elastomer Penreco Versagel C HP Particles
Ionic Cellulose Derivative
Alignment Perpendicular to Shear Direction
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Biofine Levulinic Acid Process
2 Stages Cellulose -gt Glucose -gt LA

• Dilute Aqueous H2SO4 at Elevated Temperatures. 2
  Reactors
• Conversion Time 25 minutes vs. hours / days for
  enzymatic processes
• Continuous, Reasonable Yield (40-50 based on dry
  cellulose)
• Byproducts formic acid, furfural and a high BTU
  char

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Levulinic Acid (LA)

• a.k.a 4-oxopentanoic acid , 4-ketovaleric acid
• Current Market 2 MM pounds / year at 3.50 / lb
• Derived from Maleic Anhydride (petroleum based)
• Estimated Cellulose based Cost 1/3-1/8 oil base

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LA as a Platform Chemical
MTHF
DALA
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Levulinic Acid as a Biodiesel Fuel and Home
Heating Oil

• LA in diesel fuel / heating oil provides poor
  miscibility
• LA Esterified with Ethyl Alcohol Yields Ethyl
  Levulinate (ELA)
• 79 diesel 20 ELA 1 isoamyl alcohol meets
  ASTM D975 standard for diesel fuel (low S !)

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Levulinic Acid Production of Biodegradable
Plastics

• Most consumer plastics are petroleum based and
  are not biodegradable.
• 20-25 of the US landfill volume is plastic
  although trash is only 7 plastic
• 62 of trash found on beaches is plastic
• Biodegradable plastics are a very helpful
  development for many uses

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Biodegradable Materials From Woody Biomass

• Certain Bacteria Can Utilize LA to
• Produce Intracellular Polyesters
• (Nakas, Keenan at ESF).
• These polyesters are thermoplastic
• (Heat em up they melt)
• Thermoplastics are useful for
• disposable consumer items
• Such polyesters are biodegradable
• (Good News for Landfills, etc.)

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Applications for Hemicellulose

• Polymer composites and blends
• Fibers from liquid crystalline phases
  (co-extrusion with cellulose)
• Acetic Acid Separation
• Conversion to xylose
• Bioplastics (with levulinic acid)
• Ethanol and organic acids
• Furfural and furan polymers
• Xylitol and 2,3 butanediol

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Progress in Lignin Utilization

• Fungal biodelignification and / or ligninanse
  enzymes
• Oxygen / Alkali Sulfur-Free pulping to separate
  lignin.
• Applications for Sulfur-Free Lignin
• Adhesives and Plastics
• Biodispersants / Emulsifiers
• Cosmetics and Pharmaceuticals
• Cattle Feed

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Meeting the Challenge of Deployment
At the close of Summit 1 ( May, 2001).a strong
consensus Summit 1 and what followed has
generated breakthrough ideas Our challenge as
an industry is to break through the time-to-
market barrier for new technology
(deployment) Our industry must use technology
to help attract investment capital Our issue
is not our access to technology it is our will
to use it, the skill to practice it and the
speed to implement it in time.
adapted from Del Raymonds Forward to Setting
the Industry Technology Agenda. Atlanta. TAPPI
Press, 2002
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Compelling Deal Criteria - ROI approx 35 or
more - Risk seen a zero by user and
approver -Solves a major long term problem,
especially if other approaches have failedFrom
Vincent Summit II
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Expectations for Post-Summit Alliance Formation

• Prioritization of Proposed Alliances (April,
  04),
• Review of the Prioritized Set with CEOs (Mid,
  04)
• Engage CEOs council to sponsor, network and make
  deals
• necessary to form the alliances (End of
  04)
• Realization of the recommended set of alliances
  and
• deployments (05- 09)

dates are approximate goals
Alliance Financing Take care to invest good
money before it goes bad by being impatient
for profit, and patient for growthstart early,
start small and demand early success.
Experimental Orientation the rate at which
aniance can learn by experimentation depends on
how well it can fail -- first, fast, frequently
and in the field. Expectations for Post-Summit
Alliance Formation
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Conclusions

• The Paper Industry needs more profits and wood is
  what they know.
• Non-traditional wood based products have the
  potential to restore the financial health of the
  paper industry.
• The Paper Industry is well positioned and needs
  more profit from its efforts, therefore the Paper
  Industry will lead the Age of Wood.

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The Coming Age of WoodEgon Glesinger, 1949
. forests can be made to produce fifty times
their present volume of end products and still
remain a permanently self-renewing source for
raw materials... Only forests - no other raw
material resource - can yield such returns. The
forest can, and so must, end the
chronic scarcities of material goods that have
harassed mans experience since the beginning of
history.
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The Biorefinery in New York Woody Biomass to
Ethanol Thank You