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 Research Eastern Regional Research Center ARS, USDA 600 E. Mermaid Lane Wyndmoor, PA 19038 [email protected]

Transcript of A Winter Barley Biorefinery Producing Advanced Biofuels and Coproducts K. Hicks*, N. Nghiem, A....

Page 1: A Winter Barley Biorefinery Producing Advanced Biofuels and Coproducts K. Hicks*, N. Nghiem, A. Boateng, C. Mullen, D. Johnston, and R. Moreau Sustainable.

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

[email protected]

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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.

Page 19: A Winter Barley Biorefinery Producing Advanced Biofuels and Coproducts K. Hicks*, N. Nghiem, A. Boateng, C. Mullen, D. Johnston, and R. Moreau Sustainable.

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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]

Page 20: A Winter Barley Biorefinery Producing Advanced Biofuels and Coproducts K. Hicks*, N. Nghiem, A. Boateng, C. Mullen, D. Johnston, and R. Moreau Sustainable.

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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 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

Page 23: A Winter Barley Biorefinery Producing Advanced Biofuels and Coproducts K. Hicks*, N. Nghiem, A. Boateng, C. Mullen, D. Johnston, and R. Moreau Sustainable.

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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.

Page 26: A Winter Barley Biorefinery Producing Advanced Biofuels and Coproducts K. Hicks*, N. Nghiem, A. Boateng, C. Mullen, D. Johnston, and R. Moreau Sustainable.

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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

Page 29: A Winter Barley Biorefinery Producing Advanced Biofuels and Coproducts K. Hicks*, N. Nghiem, A. Boateng, C. Mullen, D. Johnston, and R. Moreau Sustainable.

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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

Page 30: A Winter Barley Biorefinery Producing Advanced Biofuels and Coproducts K. Hicks*, N. Nghiem, A. Boateng, C. Mullen, D. Johnston, and R. Moreau Sustainable.

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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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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