biofueling the future challenges – opportunities art j ...€¢ envisaged shifting society's...
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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
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