Biotechnology and Our Material Future New Products and Processes John Pierce DuPont BioBased Materials & Central Research September 6, 2006
2 Global Drivers: Raw Materials Sources of Raw Materials Agriculture: 30 trillion lbs of grain equivalents Fossil sources: 10 trillion lbs of diverse hydrocarbons Corn and Oil: Cost the same, about 6 cents per lb Supplies approximate needs for both, but distribution of consumption is very uneven among countries Biotechnology is starting to allow access to even lower cost, high volume raw materials streams such as wood, grasses, etc. as well as production of a variety of materials and chemicals by metabolic engineering of microbes.
3 Biofuels & Biomaterials - Becoming more important Record petroleum feedstock prices Stable or flat corn prices
3.500 PRICE RATIO: CORN / OIL ($ per LB Corn/$ per LB Oil) 3.000 2.500 2.000 1.500 1.000 0.500 0.000 4 1955 1957 1959 1961 1963 1965 1967 1969 1971 1973 1975 1977 1979 1981 1983 1985 1987 1989 1991 1993 1995 1997 Raw Materials Current Prices (2005) Oil (1 lb): $0.17 Corn (1 lb): $0.04 YEAR RATIO
5 Biological Production of Chemicals DNA sequence specifies sequence of protein catalyst Thousands of specific catalysts are made in each cell Biotechnologies manipulate the type and amount of catalysts produced by manipulating the DNA sequence This provides a general approach to specifying catalysts: Microbes for complex transformations Enzymes for specific transformations DNA Fibers Food Fuel PROTEIN, CATALYSTS Chemicals Polymers
6 So what shall we make with Biotech? Existing materials and chemicals Low market risk Price is paramount; generally lower capital intensity and profitability at smaller scale can favor bio-processes New materials and chemicals High market risk and high technical risk when bioapproach is only approach feasible Very favorable attributes required at proper cost point
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Petroleum-Based Feedstocks 8
Analogous Bio-Based Feedstocks 9
10 Top Sugar Derived Building Blocks 1,4 diacids (succinic, fumaric and malic) 2,5 furan dicarboxylic acid 3 hydroxy propionic acid aspartic acid glucaric acid glutamic acid itaconic acid levulinic acid 3-hydroxybutyrolactone glycerol sorbitol xylitol/arabinitol
11 3-Hydroxypropionic acid platform Cargill
Industries starting to collaborate and compete with governmental encouragement 12 RAWS REFINING CONVERSION MARKETS POLYMERS INTERMEDIATES OIL DISTILL CRACK REACT FORM BASICS FUELS FOOD FEED/CHEMS CORN WET MILL SEPARATE FERMENT SEPARATE FIBER
13 Cargill - NatureWorks PLAs (polylactic acid) Blair, Nebraska. Gruber et al. Polylactides: NatureWorks PLA. Biopolymers Vol. 4, Wiley-VCH. Germany. Capacity of 140,000 metric tons for production of NatureWorks PLA. From: http://www.dowcargill.com
14 PHAs (polyhydroxyalkanoates) Uses: hydrophobic coatings pressure-sensitive and other adhesives packaging films, tapes moulded containers Compatible with: repulping operations composting other modes of biodegradation. http://www.metabolix.com
3GT (Sorona ) HO C OH C C 1,3-Propanediol (3G) Sorona (3GT) - An Advanced + HO C O Polymer/Fiber O C OH Terephthalic Acid O O C O C C C O O C C C O C Polypropylene terephthalate (3GT) O O C 15 Superior Properties: Stretch & recovery Softness Vibrant color Stain resistance UV & chlorine resistance Easy care
16 Why a Bioprocess? Chemical Process CH 2 =CHCH 3 Propylene Catalyst HOCH 2 CH 2 CH 2 OH 3G 3G will be produced by a fermentation process using cornstarch as feedstock Targeted advantages over chemical process: ~25% Lower cost of manufacture ~50% Lower capital ~50% Smaller environmental footprint Bioprocess Biocatalyst C 6 H 12 O 6 Glucose HOCH 2 CH 2 CH 2 OH 3G
17 Nature then Metabolic Engineering In Nature: Two microorganisms convert sugar to 3G stepwise. Glucose Glycerol 3G Yeast Bacterium For an Industrial Process: A single microorganism is required. OH OH
Gluc ATP 1 2 PEP Pyr NADPH NADPH CO 2 G6P 26 PG 29 Ru5P Manipulating Metabolic Pathways Pathways involved in production of PDO from glucose 73 Gly 19 HPA PDO 69 18 20 ATP 15 14 17 NADH 22 NADPH 21 23 ATP (1/2)O 2 Gly3P DHA 67 CO 2 68 HP NADH 12 13 FADH 2 CO 2 NADH NADPH 16 FADH 2 ATP DHAP 49 50 48 24 MGO 2ATP 51 52 47 41 3 F6P 4 5 FBP ATP NADH 44 MAL 43 FUM 42 7 SUCC ATP 6 CO 2 OAA 40 GAP 8 PGA PEP PYR 35 9 ATP 10 11 2ATP NADH CO 2 46 (1/2)O 2 AcCoA 36 28 56 Glyox 45 SucCoA CIT 39 27 KDPG 25 2ATP 60 62 37 OGA NADH 63 icit 38 ATP 53 55 X5P GAP F6P ATP NADH 64 NADPH CO 2 NADH CO 2 30 31 59 Acetald 65 32 33 34 Lact Form 58 CO 2 Acet R5P S7P E4P FADH 2 EtOH 54 57 61 66 H 2 Bio 73 NADH 70 NAD FADH 2 71 FAD NADH 72 NADPH
E. coli Host Modifications to make PDO 19 Glucose transport Glycerol metabolism Glycolysis Entner-Doudoroff Pentose phosphate TCA cycle Respiration Amino acid biosynthesis Anapleurotic reactions Global regulators E. coli 4,288 genes
20 Bio-PDO Status Summary! " # $ % $ & " ' ( ) * * + ) * *, + - + ) * " ", Loudon Plant of DuPont Tate & Lyle Bio Products Company 3/17/06
21 It takes more than biology... Polymerization Fiber Quality Modifications Unique Compositions Spinning Productivity Fiber Design Aesthetics Quality Texturing Productivity Bulk Quality Fabric Design Dye and Finishing Quality Supply/operations Process engineering Fermentation Separations Waste management
22 Bio-PDO Product Family Sorona Polymer Apparel Flooring Engineered Resins Bio-PDO Bio-PDO Direct Applications Coatings Polyols Elastomers Fibers
23 Sorona Polymers Applications Due to their unique properties, Sorona polymers can be used in a wide variety of applications, such as: Fibers: For apparel and home furnishings Packaging Non-woven structures Engineering resins
24 Bio-PDO in Polyols Sorona Polymer Apparel Flooring Engineered Resins Bio-PDO Bio-PDO Direct Applications Bio-PO3G Polyols H[ C C O C ]OH Coatings Elastomers Fibers
Markets for PO3G as a Polymer Soft Segment 25
26 Greenhouse warming Natural CO 2 cycle vs. fossil fuels National security Reduce imported petroleum Sustainability Alternative to petroleum-derived fuels and chemicals Rural economic benefit Reduce balance of trade deficit
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Biofuels Growth Opportunity 2020 Estimates by Region 28 North America Biofuels - 30 B gals Current Production > 4.0 B gals CAGR ~ 15 % EU & Eurasia Biofuels - 20 B gals Current Production ~ 1.1 B gals CAGR ~ 25 % Asia Pacific Biofuels - 30 B gals Current Production ~ 1.7 B gals CAGR ~ 25 % South & Central America Biofuels - 7 B gals Current Production ~ 4.0 B gals CAGR ~ 5 % Source: Dept of Energy and DuPont estimates
29 Biofuels: More than just Ethanol and Bio-diesel Improved Performance From Renewable Sources Bio-butanol
30 Sustainable Energy DOE Vision of Oil Savings 35 EXISTING EMERGING ADVANCED Ethanol (Billions of gal/yr) 30 25 20 15 10 5 Advanced Corn Mills Starch-based Sugar Platform -New Enzymes -Pretreatment -Fermentation Cellulose Fundamental Advances in Lignocellulose Processing and fermentation Energy Crop Grain? 0 2000 2005 2010 2015 2020 2025 Year Re: J.D. McMillan, NREL
Fossil Energy Ratio (FER) = 6 5.3 5 Energy Delivered to Customer Fossil Energy Used to Create 31 4 3 2 1 1.4 0.8 0.4 0 Cellulosic Ethanol Biorefinery Corn Ethanol Gasoline Electricity Source: J. Sheehan & M. Wang (2003)
US Biomass inventory = 1.3 billion tons 32 ) ' ( $ %& $!" #$ *+! From: Billion ton Vision, DOE & USDA 2005
Mato Grosso Brazil Soybean Harvest and Corn (Safrinha) Planting 33
Bagasse Biomass Residues South of Lake Okeechobee, Florida 34
Corn Stover Bales 35
Other energy crops on the horizon. 36,- *!". +(&*"# /+ 0 *"1 $ /+)"&0 23 +**2 &1% ):2*. *1*4566782- &946
37 Ethanol from Corn Relative Opportunities 40 Gal/Acre 391 Gal/Acre 310 Gal/Acre Images: www.ca.uky.edu & www.nativeaccess.com
Corn Stover The First Target 38 Composition Glucan (6 carbon sugars) Xylan (5 carbon sugars) Arabinan Mannan Galactan Lignin Protein Acetyl Ash Uronic Acid Non-structural Sugars 36.1 % 21.4 % 3.5 % 1.8 % 2.5 % 17.2 % 4.0 % 3.2 % 7.1 % 3.6 % 1.2 % Re: B. Dale - MSU Corn Stover is the largest U.S. single biomass source and is densely distributed. The challenge is to collect and convert the biomass efficiently. David Glassner, Jim Hettenhaus, 1999
Integrated Corn-Based Biorefinery Feedstock Transport Feedstock Conversion Fermentation Production Ethanol & Chemicals 39 Feedstock Harvest Separation Feedstock Production Downstream Markets
40 Cellulosic Ethanol Process Development Stover Milling Pre-treatment Saccharification enzymes Glucose/Xylose C6/C5 Fermentation ethanologen Separation Ethanol Steam Electricity
Pretreatment & Enzymatic Saccharification 41 Mild Pretreatment Novel Reactor System High Solids
42 Hydrolysate Fermentation Stover Milling Pre-treatment Saccharification Glucose/Xylose C6/C5 Fermentation Separation Ethanol Steam Electricity
Hydrolysate Fermentation Performance Zymomonas mobilis 43 120 100 Good conversion with 40% as-is hydrolysate. Concentration (g/l) 80 60 40 20 Glucose Xylose Ethanol 0 0 10 20 30 40 50 60 Time (hr)
Cellulosic Ethanol Process Development 44 Requirements! " # $" " %&"'() * +"!'"!" # $"+ *+"+" # $ " # $ Milling Pre treatment - Saccharification Glucose/Xylose C6/C5 Fermentation Separation Ethanol enzymes ethanologen Steam Electricity
45 Biofuels Outlook Biofuels are becoming increasingly important Large established ethanol infrastructure will continue to develop Addition of advanced biofuels such as butanol will provide for more rapid penetration of biofuels by enhancing ethanol performance and through new opportunities for distribution and use Cellulosic conversion technologies will be applicable in the future
46 Biotechnology and Our Material Future Technical complexity of bio-conversions to marketable industrial products necessitates an extraordinary degree of multidisciplinarity Picking the right targets is enormously complex Getting cost of production right is essential Partnerships with strong relationships- are essential Technology is ready; raw material costs are appropriate
47 History of Biotechnology at DuPont? "Six of the first group of scientists attached to DuPont's fundamental research program pose under the chemical symbols for rubber, silk, cellulose, and formaldehyde polymer. Though these chemists knew enough in 1927 to chart their structures, they did not understand how they were formed. To synthesize similar materials they would have to probe an uncommunicative Nature. Left to right: George L. Dorough, Glen A. Jones, Julian W. Hill, James E. Kirby, Gerard J. Berchet, Frank J. Van Natta." From: "DuPont: The Autobiography of an American Enterprise." New York: Charles Scribner's Sons, 1952.
48 Mario s cool chart So what else shall we make?
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