1. Winter Barley Ethanol – An Advanced Biofuel for the Mid Atlantic States Kevin B. Hicks Sustainable Biofuels and CoProducts Research Eastern Regional Research Center ARS, USDA 600 E. Mermaid Lane Wyndmoor, PA 19038 kevin.hicks@ars.usda.gov

2. Apply name/department/presentation title in 'header and footer' Number of Ethanol Plants, Locations, and Their Capacities as of 9/30/2010 204 Plants with 13.8 Billion Gallons Capacity Plants under Construction will Provide another 0.8 Billion Gallons Total Capacity When Completed = 14.6 Bil. Gal. 14.6 Billion Gallons meets about 10% of our total transportation fuel needs! Corn is Still the #1 Feedstock Source: RFA

3. Apply name/department/presentation title in 'header and footer' The 2007 Energy Independence and Security Act Requires Aggressive Increase in Advanced Biofuels! * Advanced biofuels is renewable fuel other than ethanol derived from corn starch that is derived from renewable biomass, and achieves a 50 percent greenhouse gas (GHG) emissions reduction (compared to gasoline). *

4. Apply name/department/presentation title in 'header and footer' 4 Cellulosic Ethanol Outstanding Potential Uses Non Food Feedstocks Still Major Research Challenges to Solve Still 5-10 years away from commercial viability? Pyrolysis and Gasification-Based Bio-Fuels Outstanding Potential Uses Non Food Feedstocks Still Major Research Challenges to Solve Still 5 years away from commercial viability? How will we meet these goals?

5. Apply name/department/presentation title in 'header and footer' 5 Is There a Simpler Way? Wouldn’t it be great if there were another feedstock we could use right now to make Advanced Biofuels? One that we could convert to “low-carbon” fuel ethanol and valuable food and feed products One that wouldn’t compete with food crop production One that wouldn’t harm the environment

6. Apply name/department/presentation title in 'header and footer' 6 There is Such a Crop! And it is Winter Barley!

7. Apply name/department/presentation title in 'header and footer' 7 Barley is A Crop Grown Outside the Corn Belt These “barley belts” can provide feedstock for ethanol plants outside the corn belt where transportation fuels and economic development are needed!

8. Apply name/department/presentation title in 'header and footer' How Did This Research Effort Begin? At a Biofuels Workshop held at ERRC on August 31, 2001 (in which Shirley Ball was a guest of honor) a Virginia Tech Extension Professor, Dr. Dan Brann insisted that I have a special meeting with him regarding winter barley and why my research team should partner with VT to develop new varieties good for making fuel ethanol. Over the next 9 years, we worked with many partners to solve the major problems that existed at that time, with using barley for making fuel ethanol. 8

9. Apply name/department/presentation title in 'header and footer' 9 Why Winter Barley For Fuel Ethanol ? Provides feedstock for ethanol plants outside the Corn Belt Farmers on the East Coast and other areas with mild winters can grow barley as a winter crop, allowing double cropping with soy followed by corn the next year! (3 crops in 2 years – More grain on same acreage) Winter barley is grown on “fallow ground” and doesn’t compete with food production thus there are no Indirect Land Use Change effects. Winter barley acts as a cover crop, preventing soil and nutrient losses to the environment- this is critical for sustainability of soil and water. Especially important for the Delaware and Chesapeake Bays. Higher protein and digestible amino acids than corn, especially lysine means that barley DDGS should sell at a premium relative to other grain DDGS.

10. Apply name/department/presentation title in 'header and footer' 10 Major Challenges with Barley for Ethanol Production in 2001 Abrasive nature of hull – destructive to grain handling and grinding equipment Low starch content (~50-55%) compared to corn’s (~70%) – results in low ethanol yields plus too much fiber High viscosity of mash due to beta-glucans – makes ethanol production difficult and expensive and limits the feed use of the ethanol co-products, DDGS to primarily ruminant animals Phytoliths

11. Apply name/department/presentation title in 'header and footer' 11 ERRC/ARS Created A Barley Research Program to Solve These Technical Issues Working with breeders at Virginia Tech to develop better hull-less and hulled barley with high starch content for fuel ethanol production Developing dry fractionation and other processes to separate barley grain into fermentable and non- fermentable fractions and coproducts Working with Genencor, A Danisco Division to develop new enzymes to reduce viscosity, increase ethanol yield, and develop energy saving fuel ethanol processes

12. Apply name/department/presentation title in 'header and footer' THOROUGHBRED DOYCE Breeding Improved Barley was Conducted at Virginia Tech Prof. Carl Griffey Wynse Brooks Barley Breeder Griffey, C., Brooks, W., Kurantz, M., Thomason, W., Taylor, F., Obert, D., Moreau, R., Flores, R., Sohn, M., and Hicks, K. Grain composition of Virginia winter barley and implications for use in feed, food, and biofuels production. Journal of Cereal Science. 51: 41–49. 2010.

13. Apply name/department/presentation title in 'header and footer' Composition of Barley is Critical for Fuel Ethanol Production COMPONENT (%, DWB) “NOMINI”- HULLED FEED BARLEY (POOR) “THOROUGHBRED” V.T. ELITE HULLED (BETTER) “EVE”- V.T. ELITE HULL-LESS (BEST) STARCH54.859.963.8  -GLUCAN 5.03.94.1 PROTEIN8.87.610.0 OIL2.51.9 ASH2.3 1.7 NDF26.017.211.0 TEST WT (LB/BU)48.152.960.8

14. Apply name/department/presentation title in 'header and footer' What about those Abrasive Hulls? Many of the barley varieties developed were hull-less varieties We also developed methods to remove the abrasive hulls and to produce starch-enriched fractions for ethanol production. 14 Flores, R.A., Hicks, K.B., Eustace, D.W., and Phillips, J.G. High- starch and high-ß-glucan barley fractions milled with experimental mills. Cereal Chem. 82(6):727-733. 2005.

15. Apply name/department/presentation title in 'header and footer' 15 Fractionation of Kernels for Value Added Fractions – Roller Milling High-Starch and High-β-Glucan Barley Fractions Milled with Experimental Mills. R.A. Flores, K.B. Hicks, D.W. Eustace and J.G. Phillips. Cereal Chemistry 82 (2005) 727-733 ETOH LOW CHO

16. Apply name/department/presentation title in 'header and footer' How Did We Solve the  -Glucan Viscosity Issue? With better Enzymes

17. Apply name/department/presentation title in 'header and footer'  -Glucanases Effectively Lower Viscosity of Barley Mashes by Partial Hydrolysis of  -Glucan Commercial  -Glucanase enzyme preparations contain mixtures of enzymes that partially degrade viscous high molecular weight  - glucans, producing low viscosity oligosaccharides in the process.

18. Apply name/department/presentation title in 'header and footer' We Discovered How to Completely Hydrolyze  -Glucans and Simultaneously Increase Ethanol Yields Our studies showed that complete conversion of  -glucan to glucose can be achieved when we also add another key enzyme,  -Glucosidase What are the benefits of this? Additional Viscosity Reduction Additional Glucose Produced is Fermented to Ethanol, Increasing Yields This is What Provides the “Edge” to the Barley EDGE Process

19. Apply name/department/presentation title in 'header and footer' The EDGE Process Increases Ethanol Yields Now both starch and  -glucan are converted to ethanol. Barley containing 65% starch and 5%  - glucan should be equivalent to corn’s 70% starch! Nghiem, N.P., Hicks, K.B., Johnston, D.B., Senske, G., Kurantz, M., Li, M., Shetty, J., and Konieczny-Janda, G. Production of ethanol from winter barley by the EDGE (enhanced dry grind enzymatic) process. Biotechnology for Biofuels 3:8. 2010.

20. Apply name/department/presentation title in 'header and footer' 20 Fresh water Milled Barley Evaporation condensate SPEZYME® Xtra OPTIMASH™ BG 30-33°C pH 3.8-4.2 Steam 85-90°C pH 5.2 85-90°C pH 5.2 FERMENZYME® L-400 58 - 60°C 60 min Thin stillage OPTIMASH™ TBG OPTIMASH™ BG Urea Barley EDGE* Process * Enhanced Dry Grind Enzymatic Pre-liquefaction Liquefaction SSF  -gluco- sidase

21. Apply name/department/presentation title in 'header and footer' 21 Fermentation Results with Thoroughbred (Hulled Barley) Notes: 1. Experiments were performed in 250-mL shakeflasks containing 150 g mash total. 2. OPTIMASH TBG was not used in liquefaction step. ■ Ethanol Yield Was Improved by Addition of  -Glucosidase ■ Extremely Low Levels of  -Glucan Makes Barley DDGS Suitable for Use in Feeds for Monogastric Animals

22. Apply name/department/presentation title in 'header and footer' 22 Technical Model Of Fuel Ethanol Production From Barley Using The EDGE Process.

23. Apply name/department/presentation title in 'header and footer' 23 Differences In Ethanol Production Costs Using The EDGE Process With Hulled Barley Feedstock.

24. Apply name/department/presentation title in 'header and footer' What about Valuable CoProducts? CoProducts are key to economically viable fuel ethanol processes. 24

25. Apply name/department/presentation title in 'header and footer' 25 Anatomy of a Barley Kernel T = Thoroughbred Hulled Barley Kernel g = Germ (Embryo) e = Endosperm h = Hull Images: Paul Pierlott, ERRC Starch, Protein,  -glucan, Tocotrienols Triacylglycerols, Tocopherols, Phytosterols Cellulose, Hemicellulose, Lignin, Ash

26. Apply name/department/presentation title in 'header and footer' 26 Nutraceuticals in Barley Phytosterols Anticholesterolemic Tocopherols Antioxidants Vitamin E Tocotrienols Antioxidants Anticancer Anticholesterolemic

27. Apply name/department/presentation title in 'header and footer' 27 Bio-Refinery CoProducts: Fractionation of Kernels for Value Added Fractions – Scarification and Nutraceutical Lipid Extraction Whole Barley Kernels ~2% oil Scarification Abraded Kernels < 2% oil Fines and Germ Fragments 3-9% oil Barley oil can be extracted from whole kernels or, more efficiently, from lipid enriched abraded fines and germ fragments. Barley oil is rich in Phytosterols (1.2 – 10g/100 gram oil), Tocopherols (T) (0.15-0.28 g/100 gram oil), and Tocotrienols (T3) (0.1-0.3 g/100 gram oil). Barley Oil has the highest levels of Tocotrienols reported for a natural oil: ( Rice Bran and Palm oils only have 0.05-0.08 g T3 /100 gram oil) Moreau, R.A., Flores, R., and K.B. Hicks, Cereal Chem. 84:1-5, 2007.

28. Apply name/department/presentation title in 'header and footer' 28 CoProducts from Hulls Cellulosic Ethanol

29. Apply name/department/presentation title in 'header and footer' 29 Ammonia recycling Barley (100 lb) 60% starch (0% moisture) Recombinant microorganism (example: KO11) Roller Mill Aspirator Starch 55 lb* 15 lb Hulls SaccharificationFermentation Glucose (67 lb)  -Glucan (4 lb) Protein (10 lb) Others (14 lb) 32.4 lb of EtOH Saccharification SAA Reactor 15 lb Co-Fermentation Making Ethanol From Barley Starch and Barley Hulls SSCF 16%* Approx. 11% ethanol yield increase by utilization of hulls. 16%* increase if 100% conversion Starch Ethanol 35.9 lb (5.5 gallons) of Washing (ex.counter current leaching) Enzyme + Starch (5 lb)* Destarching Starch 60 lb 85 lb Kernels Cellulosic Ethanol 3.5* lb of EtOH Kim, T.H., Taylor, F., and Hicks, K.B. Bioethanol production from barley hull using SAA (soaking in aqueous ammonia) pretreatment. BioResource Technology 99:5694 5702. 2008.

30. Apply name/department/presentation title in 'header and footer' 30 Thermochemically Derived CoProducts Conversion of Barley Hulls, Straw, and DDGS by Pyrolysis can yield valuable Bio-Oil and Bio-Char Bio-Oil and Bio-Char Hulls, Straw, DDGS Green Gasoline and Diesel Improves soil fertility and sequesters carbon Boateng, A.A., K.B. Hicks, R.A. Flores and A. Gutsol. Pyrolysis of hull-enriched byproducts from scarification of barley (Hordeum vulgare L.). J. Analy. & Appl. Pyrolysis, 78: 95-103 (2007). Mullen, C.A., A.A. Boateng, N.M. Goldberg, K.B. Hicks, and R. Moreau. Analysis and Comparison of bio-oil produced by fast pyrolysis from three barley biomass/byproduct streams. Energy & Fuels 24:699–706 (2010).

31. Apply name/department/presentation title in 'header and footer' 31 41 Growing winter barley for ethanol feedstock does not compete with food production and it actually improves soil and water quality! High starch fractions are used for fermentation, and Fuel Ethanol Production plus Premium DDGS Low starch fractions (high-protein, high-Tocol, high-  -glucan) for health-promoting, obesity-fighting, foods and nutraceuticals FRACTIONATION PROCESSES High fiber (hulls) and straw from barley can be used to make cellulosic ethanol and pyrolysis oil for producing “green” transportation fuels. The Winter Barley BioRefinery Vision Contact: kevin.hicks@ars.usda.gov

32. Apply name/department/presentation title in 'header and footer' “Vision without action is merely a dream. Action without vision just passes the time. Vision with action can change the world.” Barker, Joel A. 32

33. Apply name/department/presentation title in 'header and footer' Looking for Commercialization Partners Between 2001 and 2007 we met with many different groups who were interested in building barley ethanol plants in the US and in Canada. None of those groups were successful in completing their projects. Phil Madson of Katzen International and our team discussed the issues and possibilities of barley ethanol plants for the last 5 years. Katzen has more experience than any other company with small grain ethanol plants. In February 2007 we met with Management Team of Osage Bio Energy. We provided technical and cost information and discussed our vision for barley ethanol. Where others failed, OBE succeeded. 33

34. Apply name/department/presentation title in 'header and footer' 34 Osage Bio Energy is Turning a Vision into a Reality by Building the First Winter Barley Ethanol Plant in Hopewell Virginia!

35. Apply name/department/presentation title in 'header and footer' 35 41 Growing winter barley for ethanol feedstock does not compete with food production and it actually improves soil and water quality! High starch fractions are used for fermentation, and Fuel Ethanol Production plus Premium DDGS Low starch fractions (high-protein, high-Tocol, high-  -glucan) for health-promoting, obesity-fighting, foods and nutraceuticals FRACTIONATION PROCESSES High fiber (hulls) and straw from barley can be used to make cellulosic ethanol and pyrolysis oil for producing “green” transportation fuels. The Winter Barley BioRefinery Vision and Action Contact: kevin.hicks@ars.usda.gov

36. Apply name/department/presentation title in 'header and footer' 36 ACKNOWLEDGEMENTS ARS John Nghiem, Andy McAloon, Winnie Yee, Edna Ramirez, Frank Taylor, David Johnston, Rolando Flores, Bob Moreau, Gerry Senske, Akwasi Boateng, Charles Mullen, Mike Kurantz, Robyn Moten, Mike Powell, Jhanel Wilson. Virginia Tech Dan Brann, Carl Griffey, Wynse Brooks, Wade Thomason, Bruce Beahm, and Mark Vaughn Genencor, a Danisco Division Bruce Strohm, Jay Shetty, Mian Li, Gerhard Konieczny-Janda, Brad Paulson, Pauline Tenuissen, and Bob Randle Osage Bio Energy Craig Shealy, Joel Stone, Pat Simms, Eric Lee, Hank Bisner, Bill Scruggs, Tim Richter, Earl Spruill, John Warren. Katzen International -- Phil Madson

37. Apply name/department/presentation title in 'header and footer' Thanks for Your Attention! 37

38. Apply name/department/presentation title in 'header and footer' Eastern Regional Research Center Philadelphia City Center The Phillies Liberty Bell Come visit us in Philadelphia Philly Cheese Steak Email: kevin.hicks@ars.usda.gov Philly Art Museum