Production of Ethanol from Barley and DDGS containing reduced Beta-Glucan and Phytic Acid

Genencor, A Danisco DivisionLeiden, The Netherlands

3rd

Bioethanol Technology Meeting,

Detmold, Germany

April 24-25, 2007

Pauline Teunissen, PhD

2

Agenda

Current Status of Fuel Ethanol Production from Corn in the U.S.

Why Barley?

What are the Challenges?

STARGENTM Process for Barley Fermentation• Viscosity Reduction• STARGENTM Process• Compare the advanced enzyme technology

with conventional barley fermentation • Mass Balance Study

Summary

3

Number of Ethanol Plants, Locations, and Their Capacities as of Dec06

Source: John Urbanchuk and Renewable Fuels Association= operating, = under construction

109 Operating Plants with 19.7 Billion Liter Capacity

53 Plants under Construction will Provide

another 15.9 Billion Liters

Total Capacity When Completed = 35.6 Bil. Ltr.

Hundreds of New Plants in Planning Stage!

4

Today About 95% of the Fuel Ethanol in the U.S. is Made from Corn!

Corn for Grain 2005

5

We used about 20% of the US Corn Supply in 2006 to Make Enough Ethanol to Replace only ~3-4% of our Gasoline (18.9 billion liters)!

Corn Utilized in Ethanol Production

0

20

40

60

80

100

120

140EthanolProduced2006

Fuel Neededfor USAutomobilesin 2006

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Lignocellulosic Ethanol Production by Pre-treatment,Saccharification, and Fermentation Processes (uses enzymes)

Thermochemical Processes to Convert Biomass into Syn-Gas or Bio-Oil, and conversion of these intermediates into Liquid Fuels (noenzymes)

Alternative Grains Like Barley, Wheat, Pearl Millet, Sorghum, and Field Peas can Play a Big Role!

Alternatives

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Why Barley For Fuel Ethanol ?

To avoid “fuel versus food” issuesCan be grown in any StateCan grow in non-corn growing areas offering additional Farm incomeFarmers on the East Coast can grow barley as a winter crop (double crop)Cheaper than cornHigher protein and digestible amino acids than corn, especially lysineBottom Line: ~3.79 Billion Liters of Ethanol from Barley

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These “barley belts” can provide feedstock for ethanol plants outside the corn belt where transportation fuels are needed!

Barley 2005-production by County-

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Composition of Barley

Minerals&Others

6.6 %

Water13%

Protein11.5 %

Cellulose5.0 %Beta Glucan

4.6 %

Arabinoxylan5.9 %

Starch52.6 %

Fructan0.8%

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Non Starchy Polysaccharides of Grains

Grains like rye, barley and wheat contain higher levels of hemicelluloses (Beta Glucans, Pentosans) = higher viscosity due to high water-binding capacity.This reduces the efficiency of• Heat exchange operation• Centrifugal separation of solids• Evaporation• Mass transfer in fermentationHigh viscosities limit solid concentration in mashing.Negative effect on the energy balance of the process.

(lower solids, higher water content, lower ethanol yield, etc.) Residual Hemicelluloses may contribute to fouling of

heat exchanger and distillation equipment.

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Major Challenges using Barley in the Ethanol Production

Abrasive nature of hull – destructive to grain handling and grind 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 processing difficult and expensive and limits the feed use of the ethanol co-products, DDGS to only ruminant animals

Phytic acid-nutritional and environmental issues

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Table 1. Chemical and physical characterization of hulled barley

Moisture % (ground kernels) 7.85Ash % 2.32Oil % 1.92Starch % 59.89Protein % 7.6Beta-glucan % 3.9Acid Detergent Fiber (% ADF) 5.47Neutral Detergent Fiber (% NDF) 17.22Crude Fiber (% CF) 4.66lbs/bu 52.94

Table 2. Particle size distribution of hulled barley> 20 mesh 20-30 mesh < 30 mesh

46.90% 27.10% 26.00%

Hulled Barley—chemical and physical characterization

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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

Conventional Barley Process

Pre-liquefaction Liquefaction

SSF

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Fresh water

Milled Barley

Evaporation condensate

Acid alpha amylase

Beta Glucanase

30-33°CpH 3.3

Steam

57°CpH 3.71.5 hour

STARGEN™ 001

57°C30-40 min

pH 3.7

Thin stillage

Protease

Urea

STARGEN™ Process

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STARGENTM Process forHulled Barley

• 27-30% DS hulled barley• pH 3.6 @ 57°C• OPTIMASH™ BG 0.2 kg/MT• Acid Stable alpha amylase 0.13 kg/MT• 90 minutes

• STARGENTM 001 1.56 kg/MT• FERMGENTM 0.1 kg/MT• Fermentation: 50-60 hr

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Vis

cosi

ty [

mPa

s]

Tem

pera

ture

[°C

]

0 40 80 120 160 200

t [min]

0

500

1000

1500

20

30

40

50

60

70

80

90

No Beta Glucanase

+ OPTIMASH™ BG

Lower ViscosityIn Mash Cooler

Gelatinization &Liquefaction

Gel formation of

Beta Glucan

BARLEY Mashing –Viscosity Determination(pH 5.5, 29 % DS)

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STARGENTM Process for Hulled Barley-Viscosity Reduction

0100200300400500600700800900

1000

0 2000 4000 6000 8000

Time (s)

Visc

osity

(mPa

S)

0

10

20

30

40

50

60

Tem

pera

ture

(oC

)

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STARGENTM Process for Hulled Barley-HPLC profile, Brix, and %solubilization

DS%%

DP1%

DP2%

DP3 % HS Brix%

solubilization

27 19.78 20.90 8.80 50.53 6.5 28.4

30 11.43 15.00 12.36 61.21 7.0 27.1

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STARGENTM Process for Hulled Barley-Fermentation

Fermentation of 27% DS Hulled Barley: 1.56 kg/MT STARGEN™ ,0.1 kg/MT FERMGEN™

02468

101214

0 10 20 30 40 50 60

Hours

% V

/V E

than

ol

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STARGENTM Process for Hulled Barley-Fermentation

Fermentation of 30 % DS Hulled Barley:1.56 kg/MT STARGEN™, 0.1 kg/MT FERMGEN™

02468

10121416

0 10 20 30 40 50 60 70 80

Hours

% V

/V E

than

ol

0246810121416

% D

P1

%W/V

Glucose

0.0670.0660.0670.0650.0520.048

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Mass Balance Study- STARGENTM Process

Distillation

kg Ethanol/kg starch 0.538

kg Ethanol/MT Barley 322

Liter /MT Barley 408

Gallon/MT Barley 108

Fermentation Efficiency% 95.84

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Comparison of Barley fermentation at 30% DS

EtOH % V/V Standard Deviation %

Conventional Process

14.60 0.08

STARGEN™Process

14.87 0.06

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Residual starch and beta-glucancontent in DDGS

Residual Starch %

beta-glucan %

STARGEN™Process

2.51 0.37

Conventional Process

0.96 0.39

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Phytic Acid & Phytases of Grains in ethanol process

Environmental Protection–Phosphate disposal

Animal Nutrition-Complexes the trace metals

Phytic acid decreases the digestibility of proteins by proteolyticenzymes

Phytic acid -starch complex is resistant to amylases

Phytic acid decreases the amylase activity at high temperature (chelating calcium)

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Phytate Content in grains

Grain/Cereals Phytate, (% ds)

Corn 0.8-1.2

Sorghum 0.8-1.1

Wheat 0.25-1.37

Barley 0.38-1.16

Rye 0.54-1.46

Triticale 0.50-1.89

Oat 0.42-1.16

Reference:Food Phytases,Edited by Reddy,N. R and Sathe,S. K (2002) CRC Press, New York

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Action of Phytase on Reduction of Phytate in Grains

Grain Phytase Source % Reduction

Wheat Endogenous 82

Barley Endogenous 40

Rye Endogenous 78

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Summary

OPTIMASH™ BG can effectively reduce the viscosity problems associated with barley slurries containing high levels of beta-glucan.

Demonstrated STARGENTM process for more ethanol yield, DDGS containing reduced beta-glucan and no phytic acid, with great simplicity.

Mass balance study: GSHE process—322 kg Ethanol/MT Barley

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Mian Li

Gerhard Konieczny-Janda

Jay Shetty

Oreste Lantero

Kees-Jan Guijt

Brad Paulson

Jim Miers

David Bates

Kevin Hicks Jennifer Thomas

David Johnston Jhanel Wilson

John Nghiem Amy Wanner

Gerry Senske

Andy McAloon

Winnie Yee

Karen Kohout

Mike Kurantz

USDA Agricultural Research Service

Eastern Regional Research Center

Acknowledgements

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Thanks for your Attention!

Any questions?