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1 Beyond Ethanol: Synthesis and Commercialization of High Value Bioproducts in Future Biorefineries University of Nebraska Research Faculty Retreat May.

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Presentation on theme: "1 Beyond Ethanol: Synthesis and Commercialization of High Value Bioproducts in Future Biorefineries University of Nebraska Research Faculty Retreat May."— Presentation transcript:

1 1 Beyond Ethanol: Synthesis and Commercialization of High Value Bioproducts in Future Biorefineries University of Nebraska Research Faculty Retreat May 15, 2007

2 2 methanol ethene benzene toluene xylenes propene butadiene petroleum transportation fuels chemicals polymers 90% of volume 60% of value-add 10% of volume 40% of value-add Petroleum Refining Value-Add Chain

3 3 Renewable Refining Value-Add Chain starch cellulose hemicellulose plant oils glucose xylose arabinose glycerol chemicals polymers biofuels microbes catalysts

4 4 Aromatics from Petroleum

5 5 Aromatics from Renewables

6 6 lower cost, stable pricing for feedstock carbon increased margins for chemicals and polymers Economic Considerations: U.S. wet-milled glucose: $0.19/kg U.S. dry-milled glucose: $0.13/kg U.S. cellulosic glucose: $0.09/kg Brazilian glucose: $0.11/kg

7 7 Aromatics from Renewables Chemical Considerations: new chemicals and new chemistries improved performance

8 8 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 CO 2

9 9 Phloroglucinol Platform Requires a single enzyme for biosynthesis from malonyl-CoA. Elevated oxygen content Low toxicity: LD 50 = 4,000 mg/kg Target Rationale: 4. Unique electrophilic and nucleophilic reactivity.

10 10 Phloroglucinol Platform Resorcinol, $360M market Pharmaceuticals, $7.5M market Formaldehyde-based Formaldehyde-free Adhesive Resins, $3.3B market Energetic Materials, $4.5M market 2 current market price: $55.00/kg 2007 manufacturing cost: $32.50/kg 2009 manufacturing cost: $2.65/kg

11 11 Phloroglucinol Existing Route to Phloroglucinol Synthesis of Phloroglucinol from Renewables Problems explosion risk toxic waste red water chromium salts multiple steps (a) HNO 3, H 2 SO 4 ; (b) Na 2 Cr 2 O 7, H 2 SO 4 ; (c) Fe°, HCl; (d) H 2 SO 4 (a) E. coli W3110serA(DE3)/pJA3.131A Advantages nontoxic glucose no toxic waste single step

12 12 Phloroglucinol High-value market opportunity for phloroglucinol Annual demand: tons of phloroglucinol GMP manufacture required Spasfon (anti-spasmodic): $58M total sales Buflomedil (vasodilator): $16M total sales Manufacturer (Cephalon) seeking alternative suppliers Phloroglucinol as an Active Pharmaceutical Ingredient: $7.5M Market

13 13 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). Energetic Materials Advantages of TATB: Phloroglucinol is the starting material for TATB manufacture. TATB is used in fuze and booster systems. 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.

14 14 (a) E. coli W3110serA(DE3)/pJA3.131A; (b) H 2, Rh/Al 2 O 3 Resorcinol Manufacturing Route from Renewables Renewable feedstocks Nontoxic glucose Short synthetic sequence Mild reaction temperatures. Salt waste stream minimized Explosion risk minimized Use of contract manufacturing current market price: $ 6.50/kg 2009 manufacturing cost: $ 3.80/kg

15 15 Resorcinol (a) SO 3 ; (b) NaOH; (c) NaOH fusion, 350 °C; (d) H 2 SO 4 INDSPEC Manufacturing Route Sumitomo Manufacturing Route (a) propylene, HZSM-12; (b) O 2, NaOH; (c) H 2 SO 4, heat; (d) H 2 SO 4, H 2 O 2 Challenges benzene high temperature salt byproduct Challenges benzene yield issue detonation risk

16 16 Resorcinol Market ApplicationMajor 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 other UV protection wood adhesives

17 17 Resorcinol Market

18 18 Resins Phenol-Formaldehyde Adhesive Resins Resorcinol-Formaldehyde Adhesive Resins Problems: formaldehyde toxicity rising phenol prices rising resorcinol prices rising methanol prices

19 19 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

20 20 Resins Phloroglucinol-Formaldehyde Adhesive Resins Phloroglucinol Advantage: adhesive properties curing temperature and time lower formaldehyde outgassing Phloroglucinol-Aldehyde Adhesive Resins Phloroglucinol Advantage: adhesive properties formaldehyde-free 100% biobased

21 21 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, C 6 through C 15 aldehydes) Shell (~300K metric tons, C 9 through C 15 aldehydes) Sterling Chemical (~100K metric tons, C 7 through C 11 aldehydes) BASF Eastman

22 22 Wood Adhesive Foundry Insulation Laminate Abrasives $1,342M $883M $472M $422M $222M Wood Adhesive Foundry Insulation Laminate Abrasives $1,342M $883M $472M $422M $222M Resins Market

23 23 Resins Market ApplicationMajor BuyersManufacturersVolume 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

24 24 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.

25 25 Zylon Synthesized using polyphosphoric acid catalysis. Zylon is the strongest commercially available fiber. Zylons tensile strength is greater than that of Kevlar. High Performance Polymers

26 26 Aromatics from Renewables

27 27 Caprolactam Manufacture (a) H 2, Pt; (b) i) O 2, Co, ii) Cu/Zn; (c) i) propylene, H n+2 P n O 3n+1, 200 atm, 200 °C; ii) O 2 ; °C; (d) H 2, Pd; (e) i) (NH 2 OH) 2 H 2 SO 4, ii) NH 3 ; (f) i) H 2 SO 4 SO 3, ii) NH 3. (a) HCN, Ni; (b) H 2, Raney Ni/NH 3 ; c) H 2 O/NH 3, °C, TiO 2 or Al 2 O 3 Benzene toxicity HCN toxicity Cost of petroleum Waste streams Cost of petroleum

28 28 Caprolactam Caprolactam, $8.8B Market 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 Problems 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

29 29 Shielded from benzene price fluctuation Significant reduction in waste Enables renewable fiber (a) microbial synthesis; (b) cyclization; (c) catalytic hydrodenitrogenation Synthesis of Caprolactam from Renewables

30 30 Lysine Supply Major Lysine Producers Ajinomoto ADM CJ BASF Global Bio-Chem (China) Degussa / Shandong (China) Capacity (kmt / y) – Major producers currently building capacity

31 31 Aromatics from Renewables

32 32 Synthesis of Aromatics from Renewables (a) E. coli W3110serA(DE3)/pJA3.131A; (b) H 2, Rh/Al 2 O 3 (a) microbial synthesis; (b) H 2 O, 290°C.

33 33 Vanillin Manufacture (a) MeOH, H 3 PO 4 ; (b) glyoxylic acid, NaOH; (c) O 2 ; (d) H + (a) propene, H n+2 P n O 3n+1, 200 atm, 200 °C; (b) O 2 ; °C; (c) 60-70% H 2 O 2, H 3 PO 4 /HClO 4. Catechol Manufacture

34 34 (a) microbial synthesis; (b) HOCl or Ag 3 PO 4 /K 2 S 2 O 8 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. Synthesis of Aromatics from Renewables

35 35 (a) microbial synthesis; (b) H 2 O, 330 °C. 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. Extracted from star anise in China. Shikimic Acid Synthesis of Aromatics from Renewables

36 36 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. Synthesis of Aromatics from Renewables Generic Approach:

37 37 Polyhydroxybenzenes (a) E. coli KL7/pSK6.161; (b) E. coli RB791serA::aroB/pSK Isolated from a wasp carapace in China. Powerful antioxidant. Most favorable toxicological profile of the large- volume antioxidants (BHA, BHT, TBHQ). Gallic Acid:

38 38 (a) Gluconobacter oxydans ATCC 621; (b) H +, H 2 O. apionol: Natural product found in trace quantities in wood grain distillate. Powerful antioxidant. Polyhydroxybenzenes myo-inositol: A supplement used in aquaculture and animal feed applications. Can be derived from phytic acid or microbially synthesized from glucose.

39 39 Aromatics from Renewables $ Green Performance


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