BioFueling The FutureChallenges – OpportunitiesGT

Art J. RagauskasGeorgia Institute of Technology

School of Chemistry and Biochemistry

Top Global Challenges

• ENERGY• WATER• FOOD• CHEM 2312• ENVIRONMENT • TERRORISM & WAR

GT Chem 2312 Students

Research Opportunities: New Industrial EconomyDavid Morris - early 1980s • Coined the term "carbohydrate economy"• Envisaged shifting society's engine toward renewable, environmentally benign

materials from agro/forestry-based materials

- Agricultural Risk Protection Act of 2000 Title III: Biomass R&D Act of 2000, established the Biomass Research & Development Board.

Dr. Arden L. Bement, Jr.Director, National Science Foundation

Defining a Biobased EconomyAn economy based on renewable raw materials to produce products and energy in a sustainable manner

Biofuels FutureBiomass Resources

OHO

HO

OH

OH

OH

OHO

HO

OH

OH

Future Biomass

DeconstructionCatalyst

orEnzymes

Fermentation

H3C

H2C

OH

OHO

HO

HO

OH

HO

Ethanol

FermenationSaccharificationToday

Biofuels Future - Biomass Resources

Lower Cost Higher AvailabilityNo Competition with Food Demand

PineSwitchgrass

PoplarSycamoreSweetgumSorghum

Black LocustMiscanthus

Biofuels FutureIntegrated Biorefinery

The Path Forward for Biofuels and Biomaterials. Ragauskas, A.J.; Williams, C.K.; Davison, B.H.; Britovsek, G.; Cairney, J.; Eckert, C.A.; Frederick, W.J., Jr.; Hallett, J.P.; Leak, D.J.;

Liotta, C. L.; Mielenz, J.R.; Murphy, R.; Templer, R.; Tschaplinski, T. Science (2006), 311(5760), 484-489

The integrated biorefinery is facility that fully integrates biomass production and conversion to produce fuels, power, and chemicals from biomass. It fully

utilizes all components of biomass to make a range of foods, fuels, chemicals, feeds, materials, heat and power in proportions

that maximizes sustainable economic development.

Imperial College Georgia Institute Oak Ridge NationalLondon of Technology Laboratory

Biofuels Research Challenges: Plant Science

Georgia – GA Tech Challenges• Can we Tailor Georgia’s Wood Resources for Biofuels

• Reduced lignin – Increased carbohydrates • Faster growing Loblolly Pine – Poplar/Hardwoods• Improved Switchgrass

• GA Tech School of Biology/Forest Biology/Systems BiologySchool of Chemistry/Biochemistry

Society Issues: “If we build it – Will they come?”

“More, Bigger, Better;” the mantra of modern consumerism, ironically, summarizes the goals of research aimed at modifying plants for use in sustainable biomass production

Research Objective

5-year old tree

Biofuels Research Challenges: Separations

Extraction of Value Added Chemical• Neutraceuticals• Bioactive agents

HO

H

Pine Sitostanol

BioFuels• Ethanol • Dimethyl ether • Biodiesel • Biogasoline

Wang et al.Argonne 1999

Value Added Materials• Nanocellulose/hemicellulose • Lignin for carbon fibers

DOE

System SolutionsNeed IntegratedResearch Teams

BioFuels Research Challenges Conversion

Efficient Depolymerization of Cellulose• Biomass Pretreatments

– Conventional Solvents– New Solvents

• Deconstruction Enzymes– Improved hydrolysis active – In-situ Expression – cellusomes– Fundamental biomass chemistry

Bioethanol <<<< Sugars <<<< Hemi/Cellulose << Biomass

Societal Issue: Leadership-Education

Biofuel - Bioethanol

BiofuelResearch Challenges

Biofuels Research - Ongoing StudiesOverview of Processing Biomass to Bioethanol

Biomass BiomassPretreatment

HydrolyzedBiomass

Fermentation of Hydrolyzed

Biomass

Bioethanol+

Residue

The efficient processing of lignocellulosics into biofuels is contingent on the characterization of the chemical constituents of plant carbohydrates and lignin and their changes in structure throughout the process.

Several key parameters need to be addressed to facilitate practical bioconversion of non-food agricultural/woody biomass into ethanol including: • Amounts and degree of cellulose crystallinity• Amounts and structure of hemicelluloses, lignin, and low-molecular extractives • Inorganic elements

OHO

HO

OH

OH

OH

OHO

HO

OH

OHLoblolly PineHybrid PopularSwitchgrass – Miscanthus giganteus

Early Adoption

Paper Mill Sludge- Virgin/Recycled- negative value stream

Recycled Paper

Cellulose: Iα is more abundant in lower plants/bacteriaIβ is more abundant in higher plants

Analysis of Cellulose Crystallinity: X-ray, NMR, FT-IR

O

OO

CH2OH

OHO

OH

HOOH

CH2OH1

2

3

45

6

4

1

C-1

C-4

C-2, 3, 5

C-6

Biofuels: Enzymatic Hydrolysis of Cellulosics

Question: What role, if any, does cellulose ultra structure have on enzymatic hydrolysis?

Cellulase from Trichoderma reesei

0 5 10 15 20 253

4

5

6

7

8

Rel

ativ

e in

tens

ity, %

Hydrolysis time, hr

ΙβCellulose: Iβ

0

20

40

60

80

100

0 10 20 30 40 50

Hydrolysis Time, h

Glu

cose

yie

ld, %

Pulpavicel

Cellulose: Iα

0 5 10 15 20 252.5

3.0

3.5

4.0

4.5

5.0

Rel

ativ

e in

tens

ity, %

Hydrolysis time, hr

ΙαCellulose: Iα

Biofuels: Enzymatic Hydrolysis of Cellulosics

• Cellulolytic filamentous fungus

cellobiohyrolasesendoglucanasesβ-glucosidasesNREL

0

20

40

60

80

100

0 10 20 30 40 50

Hydrolysis Time, h

Post

-hyd

roly

sis p

erce

ntag

e, %

avicelpulp

• First study quantifying changein para-crystalline phase

• First to quantify changes in ultrastructure of kraft celluloseafter cellulase treatment

• Complements recent study byHayashi on cellulase changes toIα:Iβ from Cladophora microcryst.cellulose

Biofuels: Enzymatic Hydrolysis of Cellulosics

0 5 10 15 20 25

33

34

35

36

37

Rel

ativ

e in

tens

ity, %

Hydrolysis time, hr

Para-crystallinePara-crystalline

0 5 10 15 20 25

46

48

50

Rel

ativ

e in

tens

ity, %

Hydrolysis time, hr

AmorphousAmorphous

Today- Tomorrow’s Forest Products BioRefiner

Wood Debarking Collection Wood Chipping

Pulp Bleaching

Papermaking

EnergyPulping Chemicals

Bark Energy

Unbleached PulpPapermaking

Wood

Chips

Pulping Combustion ofChemical Pulp

Waste

Proposed HemicelluloseExtraction Stage

Extracted WoodchipsWoodHemicellulose

Sugars

Bioethanol

Fermentation

WoodExtractives

ChemicalMarkets

Biofuels

Value-AddedChemicals

Current Products: Pulp, Tall Oil, TurpentineFuture Select Hemicellulose, “Wood Extractives”

BioRefinery: Hemicellulose ExtractionOverview of Experimental Plan

Southern Loblolly Pine Chips

ControlKraft Pulping

Wood ChipsKraft Pulping

Pulp YieldFiber PropertiesPaper Properties

Hemi-Extracts

Pulp YieldFiber PropertiesSheet Properties

Hemi YieldLignin Yield

Hemi Composition

Wood Chip Pre-extractionAcidic – Basic

BioRefinery: Hemicellulose ExtractionAcidic Pre-Extracted Woodchips: Pretreatment Modification

Prior StudiesDirect H2SO4/H2O

t=0

H2SO4/H2Ot= 10 - 50 hSpray Chips 1 h, 150 oC

AlternativeApproachDelayed

Novel Oxidative Chemistry In Ionic Liquids for Lignin

OH

OH

OCH3HO

OCH3

O

HO

HO

H3COO

HO

HO OCH3

O

HOOCH3

OHO OH

OOH3CO

HO

HO

O

OH

OH

OCH3

OCH3

OH

OH

OOCH3

OO

OCH3

O

OCH3

HO

HO

OCH3

O

O

OCH3

HOO

HO

HO

OCH3 C8 – C22

Need New Fundamental Green Chemistry StudiesCatalytic Oxidative System (s) Preferably in Ionic Liquid

• Inert solvent • Tailor solubility of lignin• Almost no vapor pressure• Facilitate isolation of oxidized fragments

OH

HO

O OCH3

O

OCH3

O

HO

O OCH3

O

OCH3

Oxid.

∼ C800 – C900

N NR1 R2

R2

N+R1R3

N

R

Imidazolium Pyridinium

+

R

R2

P+R1R3

R

Cations Salts

Ammonium Phosphonium

Anions

PF6 BF4

CF3SO3

(CF3SO3)2N

MeOSO3

AlCl4

Cl(Br)

+

Classical Ionic Liquids

BiodieselBiochemicalsBiomaterials

BioFuels Research Challenges Conversion

BiomassBiomaterials – Biochemicals (Waste)

Biofuels (Waste)

Gasification

PowerHeatElectricity

Research Needs• Gas cleanup/tars • New catalyst• Biological ‘Fisher Tropsch’ routes

Pyrolysis

Syn Gas

Biofuels

Biochemicals

BioFuels – Path ForwardGT Strengths

SEI mission is to actively engage in and facilitate energy technology development, assessments, demonstration projects and policy guidance based on scientific facts, engineering principles and economic realities.

Several Programs• Woody Cellulose for Ethanol Transportation Fuel in Georgia

• Energy Security – Rural Development – GA Advantage

Georgia Institute of Technology Strategic Energy Institute

GA SW/HW

Conversion

Distribution

Performance/Policy

GATech

Today’s TechnologicalNeeds

Tomorrow’s TechnologicalBreakthroughs

AcknowledgementsAcknowledgements

NSF, USDAGT FRP Biomass to Biofuels,

Biopower, Biomaterials