Winter Barley Ethanol – An Advanced Biofuel for the Mid Atlantic States Kevin B. Hicks Sustainable...

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

[email protected]

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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


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 5-10 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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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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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!


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.

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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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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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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


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.


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


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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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


How Did We Solve the -Glucan Viscosity Issue?

With better Enzymes


-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.


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


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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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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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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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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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


What about Valuable CoProducts?

CoProducts are key to economically viable fuel ethanol processes.

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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

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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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 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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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]


“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.

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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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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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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


Thanks for Your Attention!

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