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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




                                                         1
            Petroleum Refining Value-Add Chain


                        90% of volume
                       60% of value-add

                                                 10% of volume
                       transportation fuels
                                                40% of value-add

petroleum                                          chemicals
                                                   polymers
                          methanol ethene
                      benzene toluene xylenes
                         propene butadiene




                                                                   2
            Renewable Refining Value-Add Chain



                                                         biofuels



starch cellulose              glucose
 hemicellulose           xylose arabinose
    plant oils                glycerol
                                                  catalysts

                                       microbes
                                                          chemicals
                                                          polymers




                                                                      3
Aromatics from Petroleum

        O        HO2C                 OH
                              CO2H
            NH      adipic acid
                                 HO          OH
 caprolactam                       phloroglucinol
                                           OH
HO                                   HO         OH

                                                OH
     phenol                              apionol
                        benzene
HO                                              OH

HO                                              OH
 catechol     HO         OH         OH     OH
                                         pyrogallol
                         HO
              resorcinol  hydroquinone




                                                      4
Aromatics from Renewables

         O        HO2C                 OH
                               CO2H
             NH      adipic acid
                                  HO          OH
  caprolactam                       phloroglucinol
                                            OH
 HO                    glucose        HO         OH
                          xylose
                                                 OH
      phenol             arabinose
                                          apionol
                          glycerol
 HO                                              OH

 HO                                              OH
  catechol     HO          OH        OH     OH
                                          pyrogallol
                          HO
               resorcinol  hydroquinone




                                                       5
          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




                                                         6
     Aromatics from Renewables


Chemical Considerations:
      new chemicals and new chemistries
     improved performance




                                          7
                       Aromatics from Renewables

Environmental Considerations

                                     benzene

 volatile carcinogen associated with leukemia and non-Hodgkin’s lymphoma
 toxic at levels lower than the U.S. exposure limit of 1 ppm over 8 h
    (Science 2004, 306, 1774)

                 OH             OH
                      OH             OH        HO
             O              O                          OH         OH
                      OH                                     HO          OH
                                     OH                OH
        HO    OH              OH          HO
          D-glucose         D-xylose           L-arabinose    glycerol

 nonvolatile and nontoxic
 consumption of CO2

                                                                              8
                 Phloroglucinol Platform


                   Target Rationale:

                       1.   Elevated oxygen content.
      OH

                       2.   Requires a single enzyme for
                            biosynthesis from malonyl-CoA.
HO         OH
phloroglucinol         3.   Low toxicity: LD50 = 4,000 mg/kg

                       4.   Unique electrophilic and nucleophilic reactivity.
      O


HO         OH
keto tautomer
                                                                           9
                     Phloroglucinol Platform


                                        1   Pharmaceuticals, $7.5M market
                  OH

                                        2   Energetic Materials, $4.5M market
            HO         OH
            phloroglucinol              3   Resorcinol, $360M market
    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




                                                                            10
                                                       Phloroglucinol

  Existing Route to Phloroglucinol
 CH3                 CH3                         CO2H                                                Problems
              O2N            NO2       O2N          NO2       H2N         NH2       HO         OH
          a                        b                      c                     d                    • explosion risk
                                                                                                     • toxic waste
                     NO2                         NO2                NH2                   OH              • “red water”
toluene             TNT                                                             phloroglucinol        • chromium salts
                                                                                                     • multiple steps
    (a) HNO3, H2SO4; (b) Na2Cr2O7, H2SO4; (c) Fe°, HCl; (d) H2SO4


  Synthesis of Phloroglucinol from Renewables
                             OH                                                                      Advantages
                                   OH            HO           OH
                         O                   a                                                       • nontoxic glucose
                                   OH                                                                • no toxic waste
                    HO       OH                         OH                                           • single step
                         glucose                  phloroglucinol

               (a) E. coli W3110serA(DE3)/pJA3.131A

                                                                                                                          11
                          Phloroglucinol

Phloroglucinol as an Active Pharmaceutical Ingredient: $7.5M Market

            OH               OH                 CH3O     O
                                                                N

       HO        OH    HO          OH       CH3O         OCH3

                     Spasfon                     Buflomedil
                 (antispasmodic)                (vasodilator)


              • 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

                                                                        12
                                Energetic Materials
          OH                     OH                      OEt                       NH2
                         O2N           NO2       O2N           NO2         O2N           NO2

   HO           OH        HO           OH         EtO          OEt         H2N           NH2
                                 NO2                     NO2                       NO2
   phloroglucinol                                                               TATB
                                                                  1,3,5-triamino-2,4,6-trinitrobenzene
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.

                                                                                                           13
                                          Resorcinol

Manufacturing Route from Renewables
           OH                                                    • Renewable feedstocks
                OH       HO          OH              OH
       O             a                    b                      • Nontoxic glucose
                OH                                               • Short synthetic sequence
  HO       OH                   OH              OH               • Mild reaction temperatures.
       glucose           phloroglucinol       resorcinol         • Salt waste stream minimized
(a) E. coli W3110serA(DE3)/pJA3.131A; (b) H2, Rh/Al2O3           • Explosion risk minimized
                                                                 • Use of contract manufacturing




                                     current market price: $ 6.50/kg
                              2009 manufacturing cost: $ 3.80/kg



                                                                                                   14
                                                 Resorcinol
INDSPEC Manufacturing Route
                   SO3H               SO3Na NaHSO ONa                         OH
                                                 3
           a                   b             c                      d                                                Challenges
                        SO3H               SO3Na             ONa                   OH
                                                                                                                     • benzene
 benzene                                                disodium
                                                                                                                     • high temperature
               benzene-1,3-        disodium benzene-                    resorcinol
               disulfonic acid       1,3-disulfonate   resorcinate                                                   • salt byproduct

      (a) SO3; (b) NaOH; (c) NaOH fusion, 350 °C; (d) H2SO4

                                                                                                    H
                                                                                               O
Sumitomo Manufacturing Route                                d                          HO          O
                                                                                                                     Challenges
                                                                H                      H       AP         OH
                                                                O                      O                             • benzene
           a               b               OH               O                     O        c                         • yield issue
                                                                                                                OH
 benzene                                                                                       O        resorcinol
                                                                                                                     • detonation risk
                                                                              O
                                      OH             OH                  O         H
       m-diisopropylbenzene         DC             HHP                  DHP
                                                                                           acetone

                                                   d

     (a) propylene, HZSM-12; (b) O2, NaOH; (c) H2SO4, heat; (d) H2SO4, H2O2

                                                                                                                                   15
                                 Resorcinol Market


Application                     Major Buyers

- Adhesives for tires and       - Goodyear
fiber-reinforced rubber goods   - Michelin            $80
                                - Bridgestone         M
                                - Continental
                                - Others            $29             $198
                                                    M               M
- Wood adhesives requiring      - Hexion             $54
room-temperature curing,        - Georgia-Pacific
structural integrity,           - Dynea
                                                     M
waterproofing                   - National Casein

- UV screening agents           - Akzo Nobel
                                - ISP                       tires
- Dyestuffs
- Pharmaceuticals               - Others                    wood adhesives
- Other miscellaneous
                                                            UV protection
                                                            other

                                                                             16
                 Resorcinol Market


Manuf acturers              Volume    Market Size

INDSPEC                     ~20K mt     $130M

Sumitomo                    ~18K mt     $117M

Mitsui                      ~15K mt     $98M

Other Manufacturers         ~2K mt      $13M




                                                    17
                                  Resins

  Phenol-Formaldehyde Adhesive Resins

                       OH                     OH                 Problems:
      O
                                                                     • rising phenol prices
  H       H                                          n
                                                                     • rising resorcinol prices
                                                                     • rising methanol prices
formaldehyde         phenol        phenol-formaldehyde polymer       • formaldehyde toxicity


  Resorcinol-Formaldehyde Adhesive Resins

                       OH                     OH
      O
  H       H                                          n
                HO                      HO


formaldehyde         resorcinol    resorcinol-formaldehyde polymer



                                                                                              18
                    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




                                                                                          19
                                      Resins

Phloroglucinol-Formaldehyde Adhesive Resins
                         OH                          OH             Phloroglucinol Advantage:
        O
                                                            n        • curing temperature and time
    H       H
                   HO         OH           HO             OH         • lower formaldehyde outgassing
                                                                     • adhesive properties
  formaldehyde     phloroglucinol     phloroglucinol-formaldehyde
                                                polymer


Phloroglucinol-Aldehyde Adhesive Resins
                         OH                  R       OH R           Phloroglucinol Advantage:
        O
                                                            n         • formaldehyde-free
    R       H
                   HO         OH           HO             OH          • 100% biobased
                                                 R                    • adhesive properties
  aldehyde         phloroglucinol     phloroglucinol-aldehyde
                                              polymer




                                                                                              20
                                       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




                                                                              21
          Resins Market

  $222M


$422M                Wood Adhesive
                     Foundry
           $1,342M
$472M                Insulation
                     Laminate

    $883M            Abrasives




                                     22
                                                Resins Market

Application                       Major Buyers             Manufacturers                   Volume
Wood adhesives                    - Weyerhauser            - Hexion Specialty Chemicals    1,239 Kt
- Plywood                         - Georgia-Pacific        - Dynea
- Oriented Strand Board (OSB)     - Louisiana-Pacific      - Georgia-Pacific
- Laminated veneer lumber (LVL)   - Canfor
- Hardboard
- I-beam
- Finger-joint

Foundry                           - Foundries              - HA-International              Est. 446 Kt
- Binders for sand cores                                   - Ashland Specialty Chemical
- Binders for mold production                              - Georgia-Pacific
Insulation                        - Knauf Insulation       - Hexion Specialty Chemicals    334 Kt
- Glass Fiber                     - Johns Manville         - Dynea
- Waste Fiber                     - Owens Corning          - Durez
- Mineral Wool                    - CertainTeed             -Georgia-Pacific
                                                           - Schenectady
                                                           - Ranbar Electrical Materials
                                                           - Von Roll Isola USA

Laminate                          - Wood products mfcts.   - Hexion Specialty Chemicals    389 Kt
- Decorative                                               - Dynea
- Industrial                                               - Georgia-Pacific
Abrasive                          - 3M                     - Hexion Specialty Chemicals    Est. 92 Kt
- Grinding and finishing wheels   - Others                 - Dynea
- Abrasive machining tools                                 - Durez
- Scrub and scouring pads                                   -Georgia-Pacific
- Sandpaper                                                - Schenectady
                                                           - 3M (captive product)

                                                                                                         23
                   High Performance Polymers

Lexan SLX

         isoterephthate-resorcinol               polycarbonate segment
                 segment

          O        O                 O   O       O               O       O
                       O        O            O                       O
                                                     H3C CH3

    • Amorphous polycarbonate copolymer.
    • Photoisomerizes to a benzophenone.
    • Maintains gloss and is scratch resistant.
    • Targeted as a replacement for paint in the automotive industry.




                                                                             24
               High Performance Polymers

Zylon

        HO      OH                  CO2H               N         N

                                                       O         O
    H2N         NH2     HO2C
                                                             Zylon


        • Synthesized using polyphosphoric acid catalysis.
        • Zylon is the strongest commercially available fiber.
        • Zylon’s tensile strength is greater than that of Kevlar.




                                                                     25
Aromatics from Renewables

         O        HO2C                 OH
                               CO2H
             NH      adipic acid
                                  HO          OH
  caprolactam                       phloroglucinol
                                            OH
 HO                    glucose        HO         OH
                          xylose
                                                 OH
      phenol             arabinose
                                          apionol
                          glycerol
 HO                                              OH

 HO                                              OH
  catechol     HO          OH        OH     OH
                                          pyrogallol
                          HO
               resorcinol  hydroquinone




                                                       26
                         Caprolactam Manufacture


               cyclohexane
                                                                              O                • Benzene toxicity
                             b            O                 NOH
                a                             e                    f
                                                                              NH               • Cost of petroleum
    benzene
                c            d
                                  cyclohexanone    cyclohexanone        caprolactam            • Waste streams
                                                        oxime
                             OH


                    phenol

(a) H2, Pt; (b) i) O2, Co, ii) Cu/Zn; (c) i) propylene, Hn+2PnO3n+1, 200 atm, 200 °C; ii)
O2; 90-120 °C; (d) H2, Pd; (e) i) (NH2OH)2H2SO4, ii) NH3; (f) i) H2SO4•SO3, ii) NH3.



          a
                NC
                                          b                             c
                                                                                               • HCN toxicity
                                   CN             H2N              CN                      O
                                                                                      NH
                                                                                               • Cost of petroleum
(a) HCN, Ni; (b) H2, Raney Ni/NH3; c) H2O/NH3, 300-360°C, TiO2 or Al2O3


                                                                                                                27
                                            Caprolactam


           Caprolactam, $8.8B Market                                 Problems
Volume: 4M mt                                       Costs driven up by benzene prices

Price: ~$2.20 / kilogram                            Large volumes of ammonium sulfate waste

Primary Applications
 • Nylon-6 textile, resin, film, filament

Primary Manufacturers
 • BASF
 • DSM
 • Honeywell                                                         Solutions
 • China Petrochemical Development
 • Ube Industries                                   Chemical synthesis of caprolactam from
 • Sumitomo Chemical                                glucose-derived lysine
 • Bayer
 • Others                                           Enables “renewable” structural material

Buyers: Various                                     Reduction of salt waste streams


                                                                                              28
    Synthesis of Caprolactam from Renewables

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


                                NH3                     NH2
               OH                                             O                     O
                    OH   a                     b                     c
           O                       CO2
                                                              NH                    NH
                    OH                   NH3   NaCl                   NH3
      HO       OH                        Cl
        glucose                 lysine             aminocaprolactam         caprolactam




           (a) microbial synthesis; (b) cyclization; (c) catalytic hydrodenitrogenation




                                                                                          29
                                        Lysine Supply

     Major producers currently building capacity


                                                                                            Market size      Price

     Major Lysine Producers   Capacity (kmt / y)                       1200                                                        2.5


Ajinomoto                            290                               1000
                                                                                                                                   2

ADM                                  160                               800




                                                   Marke Size (K mt)




                                                                                                                                         Price ($ / kg)
                                                                                                                                   1.5
CJ                                   110                               600

                                                                                                                                   1
BASF                                 90                                400


Global Bio-Chem (China)           145 – 290                            200
                                                                                                                                   0.5



Degussa / Shandong (China)           120                                 0                                                         0
                                                                              2001   2002   2003          2004       2005   2006




                                                                                                                                   30
Aromatics from Renewables

         O        HO2C                 OH
                               CO2H
             NH      adipic acid
                                  HO          OH
  caprolactam                       phloroglucinol
                                            OH
 HO                    glucose        HO         OH
                          xylose
                                                 OH
      phenol             arabinose
                                          apionol
                          glycerol
 HO                                              OH

 HO                                              OH
  catechol     HO          OH        OH     OH
                                          pyrogallol
                          HO
               resorcinol  hydroquinone




                                                       31
Synthesis of Aromatics from Renewables

         OH
                OH            HO         OH                     OH
     O                a                           b
                OH
  HO OH                            OH                      OH
    glucose                   phloroglucinol           resorcinol

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


           OH                      CO2H
                 OH
       O                  a                   b
                 OH           HO                      HO
  HO      OH                        OH                    OH
       glucose                     PCA                 catechol

           (a) microbial synthesis; (b) H2O, 290°C.




                                                                     32
                             Vanillin Manufacture
                                                          O                        O
                                                 HO                            O                        O    H
                                                              OH                       OH
            a                     b                                c                    d
HO               CH3O                         CH3O                      CH3O                    CH3O
      OH                  OH                        OH                    OH                                OH
catechol               guaiacol           4-hydroxy-3-methoxy- 4-hydroxy-3-methoxy-                    vanillin
                                              mandelic acid        glyoxylic acid

                      (a) MeOH, H3PO4; (b) glyoxylic acid, NaOH; (c) O2; (d) H+



                           Catechol Manufacture
                                                     OH                    OH

                  a                   b                            c
                                                                                       HO
       benzene         cumene             O      phenol                     OH                 OH
                                                                       hydroquinone         catechol
                                  acetone

      (a) propene, Hn+2PnO3n+1, 200 atm, 200 °C; (b) O2; 90-120 °C; (c) 60-70% H2O2, H3PO4/HClO4.

                                                                                                                  33
      Synthesis of Aromatics from Renewables

                       OH               HO    CO2H               OH
                            OH   a                      b
                   O
                            OH       HO           OH
              HO       OH                    OH                  OH
                   glucose              quinic acid         hydroquinone

                   (a) microbial synthesis; (b) HOCl or Ag 3PO4/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 (cat’s claw) bark.

   Cat’s claw extract stimulates the immune system and accelerates DNA repair.
                                                                              34
     Synthesis of Aromatics from Renewables
                     OH                   CO2H
                          OH
                 O             a                      b
                          OH        HO         OH
            HO       OH                   OH                       OH
                glucose              shikimic acid               phenol

                     (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.


                                                                               35
       Synthesis of Aromatics from Renewables


Generic Approach:

    Two-step syntheses: microbial catalysis followed by chemical catalysis.

    The first step’s product is less toxic to microbes than the second step’s product.

    The first step’s product is higher value-added relative to the second step’s product.




                                                                                    36
              Polyhydroxybenzenes

       OH                      CO2H
            OH
   O              a                       b
                                                HO         OH
            OH          HO           OH               OH
HO OH                           OH                 pyrogallol
  glucose                  gallic acid

  (a) E. coli KL7/pSK6.161; (b) E. coli RB791serA::aroB/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) .



                                                                    37
                      Polyhydroxybenzenes
                OH                        OH
           HO        OH             HO         OH                         OH
                             a                       b
           HO        OH             HO         O           HO             OH
                OH                       OH                        OH
            myo-inositol           myo-2-inosose                apionol

                (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.

                                                                               38
              Aromatics from Renewables

        O        HO2C                 OH
                              CO2H
            NH      adipic acid
                                 HO          OH
 caprolactam                       phloroglucinol        $
                                           OH
HO                    glucose        HO         OH
                         xylose
                                                       Green
                                                OH
     phenol             arabinose
                                         apionol
                         glycerol
HO                                              OH    Performance
HO                                              OH
 catechol     HO          OH        OH     OH
                                         pyrogallol
                         HO
              resorcinol  hydroquinone




                                                                    39

				
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