a winter barley biorefinery producing advanced biofuels and coproducts k. hicks*, n. nghiem, a....
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A Winter Barley Biorefinery Producing Advanced Biofuels and Coproducts
K. Hicks*, N. Nghiem, A. Boateng, C. Mullen, D. Johnston, and R. Moreau
Sustainable Biofuels and CoProducts ResearchEastern Regional Research Center
ARS, USDA600 E. Mermaid LaneWyndmoor, PA 19038
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Number of Ethanol Plants, Locations, and Their Capacities as of 3/3/2011
204 Plants with 14.1 Billion Gallons Capacity
5 Plants under Construction will Provide another 0.5 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
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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).
*
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Cellulosic Ethanol • Outstanding Potential• Uses Non Food Feedstocks• Still Major Research Challenges to Solve• Still 5 years away from commercial viability?
Pyrolysis and Gasification-Based Bio-Fuels• Outstanding Potential• Uses Non Food Feedstocks• Still Major Research Challenges to Solve• Still a few years away from commercial viability
How will we meet these goals?
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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).
*
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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 advanced fuel
ethanol and valuable food and feed products• One that wouldn’t compete with food crop
production• One that wouldn’t harm the environment
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There is Such a Crop and it is Winter Barley!
These “barley belts” can provide feedstock for ethanol plants outside the corn belt where transportation fuels and economic development are needed!
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Why Winter Barley For Fuel Ethanol ?
Provides feedstock for ethanol plants outside the Corn Belt
Farmers on the East Coast of the United States and other areas with mild winters can grow barley as a winter crop, allowing double cropping with soy or corn (More grain on same acreage)
Winter barley is grown on “winter 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.
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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
• 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
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ERRC/ARS Created A Barley Research Program to Solve These Technical Issues
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THOROUGHBRED DOYCE
We Worked with Breeders at Virginia Tech to Develop Better Barley Varieties
Prof. Carl Griffey Wynse BrooksBarley 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.
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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)
STARCH 54.8 59.9 63.8
-GLUCAN 5.0 3.9 4.1
PROTEIN 8.8 7.6 10.0
OIL 2.5 1.9 1.9
ASH 2.3 2.3 1.7
NDF 26.0 17.2 11.0
TEST WT (LB/BU) 48.1 52.9 60.8
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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.
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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.
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How Did We Solve the -Glucan Viscosity Issue?
By Working with Genencor, a Danisco Division, to Develop Better Enzymes and Processes
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The State-of-the-Art with -Glucanase Enzymes in 2001
Commercial Enzyme Preparations Contained Mixtures of Enzymes that Partially Degraded Viscous High Molecular Weight -Glucans, Producing Low Viscosity Oligosaccharides in the Process.
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Our Studies Showed How to Take it a Step Further
We found that complete conversion of -glucan to glucose can be achieved with use of additional amounts of a key enzyme, -Glucosidase
This completely hydrolyses -glucan producing additional fermentable glucose, Increasing Yields
• Barley containing 65% starch and 5% -glucan should be equivalent to corn’s 70% starch!This is What Provides the “Edge” to the Barley EDGE Process
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Fresh water
Milled Barley
Evaporation condensate
SPEZYME® Xtra
OPTIMASH™ BG
30-33°CpH 3.8-4.2
Steam
85-90°CpH 5.2
85-90°CpH 5.2
FERMENZYME®L-400
58 - 60°C60 min
Thin stillage
OPTIMASH™ TBG
OPTIMASH™ BG
Urea
Barley EDGE* Process *Enhanced Dry Grind Enzymatic
Pre-liquefaction Liquefaction
SSF
-gluco-sidase
Nghiem , N.P et al. Biotechnology for Biofuels. 3:8. 2010.
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The EDGE Process Accomplishes Three Major Goals
Reducing Viscosity of Mash
Increasing Ethanol Yields
Improves composition and quality of DDGS
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.
Nhuan P. Nghiem, Edna C. Ramírez, Andrew J. McAloon, Winnie Yee, David B. Johnston, Kevin B. Hicks. Economic analysis of fuel ethanol production from winter hulled barley by the EDGE (Enhanced Dry Grind Enzymatic) process. Bioresource Technology 102 (2011) 6696–6701.
Nhuan P. Nghiem • Frank Taylor • Kevin B. Hicks • David B. Johnston • Jay K. Shetty. Scale-up of ethanol production from winter barley by the EDGE (enhanced dry grind enzymatic) process in fermentors up to 300 liters. Applied Biochemistry and Biotechnology, In Press 2011.
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1941
Growing winter barley for ethanol feedstock does notcompete with food production and it actually improves soiland water quality while giving farmers a new source of income!
Premium DDGS
The EDGE Process
The Winter Barley Ethanol Process
Contact: [email protected]
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In 2008, Osage Bio Energy Began Building A Winter Barley Ethanol Plant in Hopewell VA
First US Winter Barley Ethanol Facility
Products To Be Produced:65 million gallons of fuel-grade ethanol250 thousand tons of high-value DDGS
65 thousand tons of barley hull fuel pellets170 thousand tons of carbon dioxide
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Can the Winter Barley Ethanol Process make Money??
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1 X 48 lb bushel of barley = $2.00
2 gal ethanol at $2.00 per gallon = $4.00
DDGS
16 lb DDGS = $0.64
$2.64 Value Added
1 X 48 lb bushel of barley = $6.50
2 gal ethanol at $2.50 per gallon = $5.00
DDGS
16 lb DDGS = $1.90
$0.40 Value Added
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YES!
Can We Expand this Fuel Ethanol Process into a Biorefinery to Produce Additional Biofuels and
CoProducts and Additional Revenue?
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CoProducts from Hulls
Cellulosic Ethanol
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Ammonia recycling
Barley (100 lb)60% starch
(0% moisture)
Recombinant microorganism
(example: KO11)
Roller Mill Aspirator
Starch 55 lb*
15 lb Hulls
Saccharification Fermentation
Glucose (67 lb)-Glucan (4 lb)Protein (10 lb)Others (14 lb)
32.4 lb of EtOH32.4 lb of EtOH Saccharification
SAA Reactor
15 lb
Co-Fermentation
Making Ethanol From Barley Starch and Barley Hulls
SSCF
Approx. 11% ethanol yield increase by
utilization of hulls. 16%*16%* increase if 100% conversion
Sta
rch
Eth
ano
l
35.9 lb (5.5 gallons) of
Washing (ex.counter current
leaching)
Enzyme + Starch (5 lb)*Enzyme + Starch (5 lb)*Destarching
Starch 60 lb85 lb Kernels
Cellulosic Ethanol
3.5* lb of EtOH3.5* 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.
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Thermochemically Derived BioFuels and CoProducts
Conversion of Barley Hulls, Straw, and DDGS by Pyrolysis can yield valuable Bio-Oil and Bio-Char
Bio-Oiland 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).
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YES!
Can We Also Make High Valued Nutraceutical CoProducts?
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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
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Nutraceuticals in Barley
Phytosterols• Anticholesterolemic
Tocopherols• Antioxidants• Vitamin E
Tocotrienols• Antioxidants• Anticancer• Anticholesterolemic
CH3
H3C
HO
CH3
CH3
CH3
CH3
CH3 CH3
O
CH3
H3C
HO
CH3
CH3
CH3
CH3
CH3 CH3
O
HO
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Bio-Refinery CoProducts: Fractionation of Kernels for Value Added Fractions – Scarification and Nutraceutical Lipid Extraction
Scarification
Whole Barley Kernels ~2% oil
Abraded Kernels< 2% oil
Fines and Germ
Fragments 3-9% oilBarley oil can be extracted from whole kernels or, more
efficiently, from lipid enriched abraded fines and germfragments.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.
Moreau, R.A., Wayns, K.E., Flores, R.A., and Hicks, K.B. Cereal Chem. 84:587-592. 2007.
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3141
Growing winter barley for ethanol feedstock does notcompete with food production and it actually improves soiland water quality while giving farmers a new source of income!
High starch fractionsare used for fermentation,
and Fuel EthanolProduction plusPremium 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: [email protected]
?
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ACKNOWLEDGEMENTSARS• 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