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Winter Barley Ethanol – An Advanced Biofuel for the Mid Atlantic States
Kevin B. HicksSustainable Biofuels and CoProducts Research
Eastern Regional Research Center ARS, USDA
600 E. Mermaid LaneWyndmoor, PA 19038
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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
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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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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?
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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
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6
There is Such a Crop! And it is There is Such a Crop! And it is Winter Barley!Winter Barley!
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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!
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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
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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.
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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
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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
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THOROUGHBRED DOYCE
Breeding Improved Barley was Conducted at Virginia Tech
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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15
Fractionation of Kernels for Value Added Fractions – Roller Milling
0
10
20
30
40
50
60
70
80
90
Shorts
Bra
n
Bre
ak
Flo
ur
Reduct
ion
Flo
ur
Shorts
Bra
n
Bre
ak
Flo
ur
Reduct
ion
Flo
ur
Shorts
Bra
n
Bre
ak
Flo
ur
Reduct
ion
Flo
ur
Doyce Merlin Commercial Hulled
Sta
rch
(%
db
)
Buhler Ross Rolls Quadrumat Senior Chopin CD1 One Pass Chopin CD1 Two Passes
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
ET
OH
LO
W C
HO
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How Did We Solve the -Glucan Viscosity Issue?
With better Enzymes
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-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.
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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
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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.
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20
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
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21
Fermentation Results with Thoroughbred (Hulled Barley)
-Glucosidase Ethanol at DDGS Composition (% DB)
Dosage (kg/MT) 72 H (% v/v) -Glucan Protein Starch
0 14.86±0.19 0.18±0.02 21.62±0.79 1.92±0.12
1.22 15.15±0.09 0.11±0.01 23.72±0.62 1.91±0.01
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
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22
Technical Model Of Fuel Ethanol Production From Barley Using The EDGE Process.
SACCHARIFY FERMENTOR
RECTIFIER
CENTRIFUGE
EVAPORATOR
DRYER
MASH
WHOLE STILLAGE
WET GRAINS
SYRUP
DDG
LIQUEFY
COOKED
MOL SIEVESAZEOTROPE
ETHANOL
AIR
EXHAUST
THIN STILLAGE
SCRUBBER
OFF GAS
CO2
PROCESS WATER
BACKSET
WATER
BEER
α-AMYLASE
AMMONIA
LIME
BARLEY
YEASTG-AMYLASE
ACID
SACCHARIFY FERMENTOR
RECTIFIER
CENTRIFUGE
EVAPORATOR
DRYER
MASH
WHOLE STILLAGE
WET GRAINS
SYRUP
DDG
LIQUEFY
COOKED
MOL SIEVESAZEOTROPE
ETHANOL
AIR
EXHAUST
THIN STILLAGE
SCRUBBER
OFF GAS
CO2
PROCESS WATER
BACKSET
WATER
BEER
α-AMYLASE
AMMONIA
LIME
BARLEY
YEASTG-AMYLASE
ACIDß-GLUCANASES
PROTEASE
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23
Differences In Ethanol Production Costs Using The EDGE Process With Hulled Barley Feedstock.
0.08720.1221
0.15700.1919
0.2268
1.32
3.31
6.62
-0.01
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
Ethanol cost difference ($/gal)
Barley cost ($/kg)
Enzyme allowance ($/kg)
1.32
3.31
6.62
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What about Valuable CoProducts?
CoProducts are key to economically viable fuel ethanol processes.
24
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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
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26
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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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% 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.
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28
CoProducts from Hulls
Cellulosic Ethanol
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29
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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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).
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3141
Growing winter barley for ethanol feedstock does notcompete with food production and it actually improves soiland water quality!
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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“Vision without action is merely a dream. Action without vision just passes the time. Vision with action can change the world.”
Barker, Joel A.
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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
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34
Osage Bio Energy is Turning a Vision into a Reality by Building the First Winter Barley Ethanol Plant in Hopewell Virginia!
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3541
Growing winter barley for ethanol feedstock does notcompete with food production and it actually improves soiland water quality!
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
and Action
Contact: [email protected]
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36
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
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Thanks for Your Attention!
37
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