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 Research
Eastern Regional Research Center
ARS, USDA
600 E. Mermaid Lane
Wyndmoor, PA 19038
kevin.hicks@ars.usda.gov
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!
Source: RFA
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Corn is Still the #1
Feedstock
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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How will we meet these goals?
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
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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
Phytoliths
• 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
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ERRC/ARS Created A Barley Research
Program to Solve These Technical Issues
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We Worked with Breeders at Virginia
Tech to Develop Better Barley Varieties
Wynse Brooks
Barley Breeder
Prof. Carl Griffey
THOROUGHBRED
DOYCE
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: title
41–49.
2010.
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Composition of Barley is Critical
for Fuel Ethanol Production
“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
b-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
COMPONENT
(%, DWB)
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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.
Flores, R.A., Hicks, K.B., Eustace, D.W., and Phillips, J.G. Highstarch 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 b-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 b-Glucanase
Enzymes in 2001
Commercial Enzyme Preparations Contained
Mixtures of Enzymes that Partially Degraded
Viscous High Molecular Weight b-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 b-glucan to glucose
can be achieved with use of additional amounts of a key
enzyme, b-Glucosidase
This completely hydrolyses b-glucan producing additional
fermentable glucose, Increasing Yields
• Barley containing 65% starch and 5% b-glucan should be
equivalent to corn’s 70% starch!
This is What Provides the “Edge” to the Barley EDGE Process
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Barley EDGE* Process
*Enhanced Dry Grind Enzymatic
Pre-liquefaction
Nghiem , N.P et al. Biotechnology for
Biofuels. 3:8. 2010.
Liquefaction
Steam
Thin stillage
Milled Barley
Evaporation
condensate
85-90°C
pH 5.2
85-90°C
pH 5.2
58 - 60°C
60 min
SPEZYME® Xtra
OPTIMASH™ BG
OPTIMASH™ TBG
Fresh water
30-33°C
pH 3.8-4.2
FERMENZYME®
L-400
SSF
OPTIMASH™ BG
b-glucosidase
Urea
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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
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Biochemistry
and Biotechnology,
IninPress
The Winter Barley Ethanol Process
The EDGE Process
Growing winter barley for
ethanol feedstock does not
compete with food production
and it actually improves soil
and water quality while giving
farmers a new source of
income!
Premium
DDGS
Contact: kevin.hicks@ars.usda.gov
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In 2008, Osage Bio Energy Began Building A
Winter Barley Ethanol Plant in Hopewell VA
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First US Winter Barley Ethanol Facility
Products To Be Produced:
65 million gallons of fuel-grade ethanol
250 thousand tons of high-value DDGS
65 thousand tons of barley hull fuel pellets
170 thousand tons of carbon dioxide
Can the Winter Barley Ethanol
Process make Money??
DDGS
1 X 48 lb
bushel of
barley = $2.00
2 gal ethanol at
$2.00 per gallon =
$4.00
$2.64
Value
Added
16 lb DDGS = $0.64
DDGS
$0.40
Value
Added
1 X 48 lb
2 gal ethanol at
16 lb DDGS = $1.90
bushel of
$2.50 per gallon =
barley
= $6.50
$5.00
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Can We Expand this Fuel Ethanol Process into
a Biorefinery to Produce Additional Biofuels and
CoProducts and Additional Revenue?
YES!
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CoProducts from Hulls
Cellulosic Ethanol
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Making Ethanol From Barley Starch and Barley Hulls
85 lb Kernels
Starch 55 lb*
Roller Mill
Aspirator
Saccharification
15 lb Hulls
Fermentation
Glucose (67 lb)
Destarching
Enzyme + Starch (5 lb)*
b-Glucan (4 lb)
Protein (10 lb)
Others (14 lb)
Starch Ethanol
Barley (100 lb)
60% starch
(0% moisture)
Starch 60 lb
15 lb
Ammonia
recycling
SAA Reactor
Washing
(ex.counter current
leaching)
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.
32.4 lb of EtOH
Saccharification
Co-Fermentation
Recombinant
microorganism
(example: KO11)
SSCF
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3.5* lb of EtOH
Approx. 11%
ethanol yield
increase by
utilization of hulls.
16%* increase if
100% conversion
35.9 lb (5.5
gallons) of
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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
Green Gasoline
and Diesel
Bio-Oil
and Bio-Char
Hulls,
Straw,
DDGS
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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Can We Also Make High Valued
Nutraceutical CoProducts?
YES!
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Anatomy of a Barley Kernel
Starch, Protein,
b-glucan,
Tocotrienols
Triacylglycerols,
Tocopherols,
Phytosterols
Cellulose,
Hemicellulose,
Lignin, Ash
T = Thoroughbred Hulled Barley Kernel
g = Germ (Embryo)
Images: Paul
Pierlott, ERRC
e = Endosperm
h = Hull
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Nutraceuticals in Barley
Phytosterols
•
Anticholesterolemic
HO
Tocopherols
•
•
Antioxidants
Vitamin E
CH3
O
H3C
CH3
CH3
CH3
CH3
CH3
HO
CH3
Tocotrienols
•
•
•
Antioxidants
Anticancer
Anticholesterolemic
CH3
O
H3C
CH3
CH3
CH3
CH3
CH3
HO
CH3
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Bio-Refinery CoProducts: Fractionation of Kernels for Value Added
Fractions – Scarification and Nutraceutical Lipid Extraction
Scarification
Moreau, R.A., Flores, R., and K.B.
Hicks, Cereal Chem. 84:1-5, 2007.
Whole Barley
Kernels ~2% oil
Moreau, R.A., Wayns, K.E., Flores,
R.A., and Hicks, K.B. Cereal Chem.
84:587-592. 2007.
Abraded Kernels
< 2% oil
Fines and
Germ
Fragments
Barley oil can be extracted from whole kernels or, more
3-9% oil
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)
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The Winter Barley BioRefinery Vision
High fiber (hulls) and straw from
barley can be used to make
cellulosic ethanol and pyrolysis oil
for producing “green” transportation fuels.
High starch fractions
are used for fermentation,
and Fuel Ethanol
Production plus
FRACTIONATION PROCESSES
Premium DDGS
Growing winter barley for
ethanol feedstock does not
compete with food production
and it actually improves soil
and water quality while giving
farmers a new source of
income!
Low starch fractions (high-protein, high-Tocol,
high-b-glucan) for health-promoting,
obesity-fighting, foods and nutraceuticals
Contact: kevin.hicks@ars.usda.gov
?
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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
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