PowerPoint%20Presentation%20%20-%20%20%20%20December,%202006

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Beyond Ethanol Synthesis and Commercialization
of High Value Bioproducts in Future Biorefineries
University of Nebraska Research Faculty Retreat
May 15, 2007
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Petroleum Refining Value-Add Chain
90 of volume 60 of value-add
10 of volume 40 of value-add
transportation fuels
chemicals polymers
petroleum
methanol ethene benzene toluene xylenes
propene butadiene
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Renewable Refining Value-Add Chain
biofuels
starch cellulose hemicellulose plant oils
glucose xylose arabinose glycerol
catalysts
microbes
chemicals polymers
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Aromatics from Petroleum
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Aromatics from Renewables
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Aromatics from Renewables
Economic Considerations
lower cost, stable pricing for feedstock carbon
U.S. wet-milled glucose 0.19/kg
U.S. dry-milled glucose 0.13/kg
Brazilian glucose 0.11/kg
U.S. cellulosic glucose 0.09/kg

• increased margins for chemicals and polymers

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Aromatics from Renewables
Chemical Considerations
new chemicals and new chemistries

• improved performance

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Aromatics from Renewables
Environmental Considerations

• volatile carcinogen associated with leukemia and
  non-Hodgkins lymphoma

toxic at levels lower than the U.S. exposure
limit of 1 ppm over 8 h (Science 2004, 306,
1774)
nonvolatile and nontoxic
consumption of CO2
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Phloroglucinol Platform
Target Rationale
Elevated oxygen content.
1.
2.
Requires a single enzyme for biosynthesis from
malonyl-CoA.
3.
Low toxicity LD50 4,000 mg/kg
4.
Unique electrophilic and nucleophilic reactivity.
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Phloroglucinol Platform
Pharmaceuticals, 7.5M market
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2
Energetic Materials, 4.5M market
Resorcinol, 360M market
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current market price 55.00/kg
Adhesive Resins, 3.3B market
2007 manufacturing cost 32.50/kg
4
Formaldehyde-based
2009 manufacturing cost 2.65/kg
Formaldehyde-free
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Phloroglucinol

• Existing Route to Phloroglucinol
• Synthesis of Phloroglucinol from Renewables

• Problems
• explosion risk
• toxic waste
• red water
• chromium salts
• multiple steps

(a) HNO3, H2SO4 (b) Na2Cr2O7, H2SO4 (c) Fe,
HCl (d) H2SO4

• Advantages
• nontoxic glucose
• no toxic waste
• single step

(a) E. coli W3110serA(DE3)/pJA3.131A
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Phloroglucinol
Phloroglucinol as an Active Pharmaceutical
Ingredient 7.5M Market

• Spasfon (anti-spasmodic) 58M total sales

• Buflomedil (vasodilator) 16M total sales

• High-value market opportunity for phloroglucinol

• Manufacturer (Cephalon) seeking alternative
  suppliers

• Annual demand 40 - 60 tons of phloroglucinol

• GMP manufacture required

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Energetic Materials
TATB is used in fuze and booster systems.
Advantages of TATB

• thermally-stable, impact-insensitive energetic
  material

• possesses a greater density and detonation
  velocity relative to 2,4,6-trinitrotoluene (TNT)

• reduced shock sensitivity and increased thermal
  stability relative to hexahydro-1,3,5-trinitro-1,3
  ,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro
  -1,3,5,7-tetrazocine (HMX).

Phloroglucinol is the starting material for TATB
manufacture.
Market opportunity

• Phloroglucinol is manufactured in China, India,
  and Pakistan but not in the U.S.

• U.S. Department of Defense is seeking a domestic
  source.

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Resorcinol
Manufacturing Route from Renewables

• Renewable feedstocks

• Nontoxic glucose

• Short synthetic sequence

• Mild reaction temperatures.

• Salt waste stream minimized

• Explosion risk minimized

(a) E. coli W3110serA(DE3)/pJA3.131A (b) H2,
Rh/Al2O3

• Use of contract manufacturing

current market price 6.50/kg
2009 manufacturing cost 3.80/kg
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Resorcinol
INDSPEC Manufacturing Route

• Challenges
• benzene
• high temperature
• salt byproduct

(a) SO3 (b) NaOH (c) NaOH fusion, 350 C (d)
H2SO4
Sumitomo Manufacturing Route

• Challenges
• benzene
• yield issue
• detonation risk

(a) propylene, HZSM-12 (b) O2, NaOH (c)
H2SO4, heat (d) H2SO4, H2O2
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Resorcinol Market
Application Major Buyers
Adhesives for tires and fiber-reinforced rubber goods Goodyear Michelin Bridgestone Continental Others
- Wood adhesives requiring room-temperature curing, structural integrity, waterproofing Hexion Georgia-Pacific Dynea National Casein
- UV screening agents - Dyestuffs - Pharmaceuticals - Other miscellaneous Akzo Nobel ISP Others
tires
wood adhesives
UV protection
other
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Resorcinol Market
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Resins
Phenol-Formaldehyde Adhesive Resins
Problems

• rising phenol prices

• rising resorcinol prices

• rising methanol prices

• formaldehyde toxicity

Resorcinol-Formaldehyde Adhesive Resins
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Regulation and Litigation Risk

• Formaldehyde a threat
• Formaldehyde classified as known human carcinogen
  in 2004 (International Agency for Research on
  Cancer)
• Companies exposed to regulation / litigation
• Danger to employees who handle phenol-formaldehyde
  
• Danger to consumers from formaldehyde
  off-gassing
• Specter of asbestos litigation
• Bankruptcy (e.g., Owens Corning)
• Demand for formaldehyde-free alternatives
• Johns Mansville (fiber-glass insulation) now
  using acrylic replacement
• Hexion introduced Ecobind adhesive resin with
  low emissions of formaldehyde
• Knauff seeking replacement for phenol-formaldehyde
  adhesives

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Resins
Phloroglucinol-Formaldehyde Adhesive Resins
Phloroglucinol Advantage

• curing temperature and time

• lower formaldehyde outgassing

• adhesive properties

Phloroglucinol-Aldehyde Adhesive Resins
Phloroglucinol Advantage

• formaldehyde-free

• 100 biobased

• adhesive properties

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Resins

• Replace formaldehyde with alternative, nontoxic
  aldehyde
• Options to source alternative aldehydes
• Plant oils
• Fischer-Tropsch products
• Sasol (multiple K metric tons)
• Exxon (300K metric tons, C6 through C15
  aldehydes)
• Shell (300K metric tons, C9 through C15
  aldehydes)
• Sterling Chemical (100K metric tons, C7 through
  C11 aldehydes)
• BASF
• Eastman

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Resins Market
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Resins Market
Application Major Buyers Manufacturers Volume
Wood adhesives - Plywood - Oriented Strand Board (OSB) - Laminated veneer lumber (LVL) - Hardboard - I-beam - Finger-joint - Weyerhauser - Georgia-Pacific - Louisiana-Pacific - Canfor - Hexion Specialty Chemicals - Dynea - Georgia-Pacific 1,239 Kt
Foundry - Binders for sand cores - Binders for mold production - Foundries - HA-International - Ashland Specialty Chemical - Georgia-Pacific Est. 446 Kt
Insulation - Glass Fiber - Waste Fiber - Mineral Wool - Knauf Insulation - Johns Manville - Owens Corning - CertainTeed - Hexion Specialty Chemicals - Dynea - Durez -Georgia-Pacific - Schenectady - Ranbar Electrical Materials - Von Roll Isola USA 334 Kt
Laminate - Decorative - Industrial - Wood products mfcts. - Hexion Specialty Chemicals - Dynea - Georgia-Pacific 389 Kt
Abrasive - Grinding and finishing wheels - Abrasive machining tools - Scrub and scouring pads - Sandpaper - 3M - Others - Hexion Specialty Chemicals - Dynea - Durez -Georgia-Pacific - Schenectady - 3M (captive product) Est. 92 Kt
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High Performance Polymers
Lexan SLX

• Amorphous polycarbonate copolymer.

• Photoisomerizes to a benzophenone.

• Maintains gloss and is scratch resistant.

• Targeted as a replacement for paint in the
  automotive industry.

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High Performance Polymers
Zylon

• Synthesized using polyphosphoric acid catalysis.

• Zylon is the strongest commercially available
  fiber.

• Zylons tensile strength is greater than that of
  Kevlar.

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Aromatics from Renewables
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Caprolactam Manufacture

• Benzene toxicity

• Cost of petroleum

• Waste streams

(a) H2, Pt (b) i) O2, Co, ii) Cu/Zn (c) i)
propylene, Hn2PnO3n1, 200 atm, 200 C ii) O2
90-120 C (d) H2, Pd (e) i) (NH2OH)2H2SO4, ii)
NH3 (f) i) H2SO4SO3, ii) NH3.

• HCN toxicity

• Cost of petroleum

(a) HCN, Ni (b) H2, Raney Ni/NH3 c) H2O/NH3,
300-360C, TiO2 or Al2O3
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Caprolactam
Caprolactam, 8.8B Market
Problems

• Volume 4M mt
• Price 2.20 / kilogram
• Primary Applications
• Nylon-6 textile, resin, film, filament
• Primary Manufacturers
• BASF
• DSM
• Honeywell
• China Petrochemical Development
• Ube Industries
• Sumitomo Chemical
• Bayer
• Others
• Buyers Various

Costs driven up by benzene prices Large volumes
of ammonium sulfate waste
Solutions
Chemical synthesis of caprolactam from
glucose-derived lysine Enables renewable
structural material Reduction of salt waste
streams
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Synthesis of Caprolactam from Renewables

• Shielded from benzene price fluctuation
• Significant reduction in waste
• Enables renewable fiber

(a) microbial synthesis (b) cyclization (c)
catalytic hydrodenitrogenation
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Lysine Supply

• Major producers currently building capacity

Major Lysine Producers Ajinomoto ADM CJ BASF
Global Bio-Chem (China) Degussa / Shandong
(China)
Capacity (kmt / y) 290 160 110 90 145
290 120
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Aromatics from Renewables
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Synthesis of Aromatics from Renewables
(a) E. coli W3110serA(DE3)/pJA3.131A (b) H2,
Rh/Al2O3
(a) microbial synthesis (b) H2O, 290C.
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Vanillin Manufacture
(a) MeOH, H3PO4 (b) glyoxylic acid, NaOH (c)
O2 (d) H
Catechol Manufacture
(a) propene, Hn2PnO3n1, 200 atm, 200 C (b)
O2 90-120 C (c) 60-70 H2O2, H3PO4/HClO4.
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Synthesis of Aromatics from Renewables
(a) microbial synthesis (b) HOCl or
Ag3PO4/K2S2O8
Quinic Acid
Isolated from Cinchona tree bark primarily in
Zaire.
Starting material for the original Gilead
synthesis of Tamiflu.
Biologically active component in extract of
Uncaria tomentosa (cats claw) bark.
Cats claw extract stimulates the immune system
and accelerates DNA repair.
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Synthesis of Aromatics from Renewables
(a) microbial synthesis (b) H2O, 330 C.
Shikimic Acid
Extracted from star anise in China.
Starting material for the synthesis of Tamiflu.
As Tamiflu came out of clinical trials in 1998,
shikimic acid cost 50,000/kg.
The manufacturing cost of microbe-synthesized
shikimic acid is 20/kg.
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Synthesis of Aromatics from Renewables
Generic Approach
Two-step syntheses microbial catalysis followed
by chemical catalysis.
The first steps product is less toxic to
microbes than the second steps product.
The first steps product is higher value-added
relative to the second steps product.
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Polyhydroxybenzenes
(a) E. coli KL7/pSK6.161 (b) E. coli
RB791serAaroB/pSK6.234.
Gallic Acid
Isolated from a wasp carapace in China.
Powerful antioxidant.
Most favorable toxicological profile of the
large-volume antioxidants (BHA, BHT, TBHQ) .
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Polyhydroxybenzenes
(a) Gluconobacter oxydans ATCC 621 (b) H, H2O.
apionol
Natural product found in trace quantities in wood
grain distillate.
Powerful antioxidant.
myo-inositol
A supplement used in aquaculture and animal feed
applications.
Can be derived from phytic acid or microbially
synthesized from glucose.
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Aromatics from Renewables

Green
Performance