Cellulosic Ethanol: Beyond Corn and Sugarcane

Michael R. Ladisch and Eduardo Ximenes

Laboratory of Renewable Resources EngineeringAgricultural and Biological Engineering

Purdue UniversityWest Lafayette, IN 47907

http://engineering.purdue.edu/LORREand

Mascoma CorporationLebanon, NH

www.mascoma.com

BECA, Medellin, ColombiaAugust 5, 2011

Acknowledgements

Colombia-Purdue Institute for Advanced ScientificResearch ( https://engineering.purdue.edu/CPIASR )

Center for Research and Innovation in Energy(C11EN) – Sergio Montoya, CEO

Bolivar Group, S.A.S. – William Bolivar, CEO

Purdue University Global Policy Research Institute (GPRI)Colleges of Agriculture and Engineering

Kimberly Clark CorporationMascoma CorporationUS Department of Energy GO18103

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World Energy Use: World Energy Use: 13% is Renewable

International Energy Agency (IEA) 2008.

Coal

(Sergio Montoya, Jose Roberto Moreira, Michel Dwyer, BECA, 2011)

Brazilian vs World Energy MatrixBrazilian vs World Energy Matrix

Source: MINISTÉRIO DE MINAS E ENERGIA - Brasil, 2008

RenewableRenewable

Non RenewableNon Renewable

Brazil

World

Colombian AgricultureCurrent and Future

Current: coffee, cut flowers, bananas, rice, tobacco, corn, sugarcane, cocoa beans, oilseed, vegetables

Future: Biodiesel from palm. Oil from algal biotechnology (Lucia Atehortua, U. Antioquia )Ethanol from sugar cane, 300,000 gal / day, 8%

mandateEthanol from cellulose (sugar cane bagasse)

(Sergio Montoya, William Bolivar, Fitzroy Beckford, Phillipe Conil BECA, 2011)

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Current Experience from US and Brazil(Michael Dwyer, Jose Roberto Moriera, BECA, 2011)

Corn: Approaching 15 Billion Gals / YrLimited by madated use (10 or 15%) and economicsCorn fiber, stalks, leaves (cellulose)

= more ethanolSugar cane

Approaching 7 billion Gal / YrBagasse, stalks, leaves (cellulose)

= more ethanol

CPIASR

Technology / Cost Determines Timing of Cellulose Feedstock

VacuumCrystallize

Centrifuge

Multi-StageEvaporationClarifyMill

Raw Sugar

Syrup~65oBrix

Juice10-15oBrix

Water

Sugarcane

Bagasse - Cellulose

Sugar Manufacture at a Sugarcane FactorySugar Manufacture at a Sugarcane FactoryFrom Eggleston, USDA ARS, 2008

Molasses

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Energetic Potential of SugarcaneSugar vs Cellulose

http://bioenfapesp.org

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appmx $80. Sugar cane = $100. Oil

2/3 of energy is in cellulose fraction

Red Ocean / Blue Ocean

Red Ocean : is where every industry is today: there is a defined market, defined competitors, and a typical way to run a business in any industry.

Blue Ocean: On the other hand, is where everyone would like to be. It is where you create uncontested markets and capture new demand, is where you break the value-cost trade-off and is where you make the competition irrelevant.

Chan Kim & Renee Mauborgne, Blue Ocean Strategy, 2005

CPIASR

Agricultural Markets in the AmericasWhat can be done?

GrainSugar

Vegetable Oils

Cellulosic Biomass

Food(People)

Feed(Animals)

LiquidFuels Chemicals

EthanolBiofuel

OrganicMolecules

AcidsAldehydes

CPIASR

Blue Ocean Strategy ThinkingRed Ocean

Components of plant cell walls 2/3 is made from sugars

AshExtractives

Lignin

Cellulose

Hemicellulose(need special yeast to convert to ethanol)

AshExtractives

Lignin

Cellulose

Chapple, 2006; Ladisch, 1979

Fermentable glucose sugar obtained from cellulose in 1819 (Sergio Montoye, Beca, 2011)

CPIASR

David Dayton, NREL, IEA, 2007

Production: Biochemical vs. Chemical Conversion

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Blue Ocean Strategy Thinking

Max Ethanol Yields from selected FeedstocksHardwoods

PoplarRed

MapleCorn

Stover Switchgrass

Cellulose 43.8 41.0 34.6 33.2

Xylan 14.9 15.0 18.3 21.0

Arabinan, Mannan, Galactan 5.6 0.0 2.5 3.2

Acetyl 3.6 4.7 na 2.5

Extractives 3.6 3.0 10.8 10.2

Protein na na na 5.7

Lignin 29.1 29.1 17.7 17.9

Ash 1.1 1.0 10.2 3.7

Total % 101.7 93.8 94.1 97.4

Ethanol Theoretical Yields assuming 100% hydrolysis, 100% fermentation

Est max gal / dry ton biomass 124 108 107 111Kim et al, 2008

Old biochemical conversion technology:Conversion of Cellulose to Ethanol requires many steps

6 Combustion orGasification

54321

CO2

Co-products

Pretreatment Hydrolysis FermentationFeedstockPreparation

Feedstock

Catalysts

Enzymes

Microbes(Yeast, Bacteria)

Separations

Fuel

ResidueEnergy

Acid Hydrolysis of Cellulose

C

C*

Gn GDegradation Products

k1

k2

k3k4

K

k2, k3, >> k1 k4, k3 same magnitude

Degradation products include organic acids that catalyze further hydrolysis and degradation

High temperatures (140 to 200 C), Short times (5 to 50 min)

PretreatmentAvoids Side-reactions during Cellulose Pretreatment

C

C*

Gn GDegradation Products

k1

k2

k3k4

K

k2, k3, >> k1 k4, k3 same magnitude

G = glucose sugar

17

Amorphous Region

CelluloseLignin

Hemicellulose

Pretreatment

Pretreatment gives enzyme accessible substrate

Crystalline Region

Mosier et al, 2005

CPIASR

Teeri 1997

Ref: Himmel, M. et al NREL (2000)

Cellulase from Trichoderma ressei: Multiple synergistic components

Endoglucanase CBHHuang et al, 2008

Fermentation Scale-up: Making Mash from Cellulosic Material

Untreated, 150 g / L

Pretreated and Processed, Pre-fermentation

Enhances ability to mix / ferment slurries

Pretreatment

CPIASR

Blue Ocean Canvas

Enzyme Hydrolysis

Overcoming the recalcitrance of cellulosic biomass

• Most costly• Greatest potential for R&D-driven cost reduction• Advances necessary & sufficient to create cellulosic biofuels industry, generically enablingfor all fuel molecules

• Ultimate advances in fuel production from soluble sugars or other intermediates will not enable a cellulosic biofuels industry

Improved fuels, fuel production

Cellulosicbiomass

Reactive Intermediates:e.g. Sugars, Syn gas

Fuels

• Advances usually fuel-specific

We Would Have a Cellulosic Biofuels Industry Today…If it Were not for the Recalcitrance of Cellulosic Biomass

Lynd et al, 2005

Cost of catalyst roughly doubles feedstock cost unacceptable for a commodity product

0.00

0.10

1.00

10.00

Est

imat

ed C

ellu

lase

Cos

t($

/gal

EtO

H)

1990 1995 2000 2005

The Cost of Cellulase Enzyme (50% of total): Largest Component of Recalcitrance Barrier

e) $0.10 to $0.20 a) $0.03

d) $5.00

c) $0.45

b) $0.50

f) $0.5 to $1.00

g) $1.00 to $1.50

a) Hinman et al. 1991. Appl. Biotechnol. Bioeng. 34/35:639-657. b) Hettenhaus & Glassner, 1997 (http://www.ceassist.com/assessment.htm). c) NREL, 1998. Bioethanol from the corn industry. DOE/GO-1009-577. d) Schell, 2004. ASM National Meeting; McMillan, 2004. DOE/NASULGS Biomass & Solar Energy Workshops.e) Genencor & Novozyme, 2004. Press releases (e.g. http://www.genencor.com/wt/groc/pr 109831360). f) Petiot, Novozymes, Platts Cellulosic Ethanol & Second Generation Biofuels, 2007. g) Sheridan (Novozymes) Nature Biotech, 2008

Lynd, Wyman, et al

Yeast Platform

Established ethanol producer

Cellulase expression engineering into yeast

Organism developed initiated with a xylose-utilizing recombinant strain

Hydrolyzes and ferments cellulose to ethanol at the same time (Consolidated Bioprocessing or CBP)

DNA mRNA Protein

Information

Possibilities

Polymer of Amino Acids

Fact

Assembly Point Disbands

CPIASR

Gene

Enzyme

Blue Ocean = Game - changers, New Frontiers

Biology In Action

DNA

Replication

RNA Proteins

Amino Acids

Transcription

Translation

Roat-Malone, 2002

Yeast = Self Replicating catalysts

CPIASR

Challenges and Opportunities

1. Implementing large scale systems2. “De-risking” integrated technologies3. Establishing test-beds4. Reducing capital and operational costs5. Maintaining investment environment6. 10 year consistent policy (long term)

sustained commitment policy investment research

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Sergio Montoya, BECA, 2011

Entrepreneurial EngineeringPre-requisites

Recognition of opportunity Technology ready when opportunity presents itself“Angel” Investors with business experienceDepartment, College, University Level

Encouragement and SupportNetworking with others who have done it

(entrepreneurial / business support system)Local attorney(s) with business experience

Plan A: with goals, timelines, exit strategyPlan B: (in case Plan A does not work out)

CPIASR

From a professor’s perspectivePre-requisites

Recognition of opportunity Technology ready when opportunity presents itself“Angel” Investors with business experienceDepartment, College, University Level

Encouragement and SupportNetworking with others who have done it

(entrepreneurial / business support system)Local attorney(s) with business experience

Plan A: with goals, timelines, exit strategyPlan B: (in case Plan A does not work out)

Educational Opportunity

Why not develop a case study approach?

Goal Translate laboratory discovery to societal use

Classify by type of new technology and capital intensity a. New industry (advanced biofuels) b. Established industry (automobiles, computers) c. Biopharmaceutical d. Biomedical e. Instrumentation f. Software

Purdue UniversityLand–grant institution, founded 1869, W. Lafayette, IN

74,000 students (40,000 in W. Lafayette campus )6,100 international students2,600 faculty, 4 campuses, 10 technology sites416,820 alumni

Discovery ParkNo. 1 Industrial Research Park in the US US News & World Report Doctoral Program Rankings:

1. Agricultural & Biological EngineeringAnalytical Chemistry

4. Civil Engineering, 6. Aerospace & Aeronautical Eng. 9. Mechanical Engineering,

10. Industrial Engineering, 11. Electrical Engineering

Laboratory of Renewable Resources Engineering (LORRE)

• Established in 1978

• Applied and fundamental research in– Biotechnology– Bio-nanotechnology, – Bioproducts from agriculture and renewable resources, – Biorecovery.

• Interdisciplinary research approach across biology, biochemistry, agronomy, food science, engineering, agriculture

• Colombian-Purdue Institute for Advanced Research

CPIASR

Muchas GraciasJuan Ernesto De Bedout, Juan Guillermo Ochoa,

Ramiro Garces, KCC

Michael R. Ladisch+

Laboratory of Renewable Resources EngineeringAgricultural and Biological Engineering

Weldon School of Biomedical Engineering

Colombia-Purdue Institute for Advanced Scientific Research https://engineering.purdue.edu/CPIASR

Purdue University

ladisch@purdue.edumladisch@mascoma.com

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+ CTO, Mascoma