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Second and Third Generation Second and Third Generation
BiofuelsBiofuels: : A Review of the Chemistry, A Review of the
Chemistry, FeedstocksFeedstocks, Processes and Projects, Processes
and Projects
AIChEAIChE--Chicago Symposium 2008Chicago Symposium 2008Recent
Developments in Refining, Energy, and BiotechnologyRecent
Developments in Refining, Energy, and Biotechnology22 22 -- 23
September, 200823 September, 2008
Dale A. MonceauxPrincipal
Cincinnati, Ohio, USA
LignoLigno--cellulosiccellulosic FeedstocksFeedstocks
ConversionConversionState of the TechnologyState of the
Technology
Introduction Transportation Fuels First Generation Biofuels
Biofuels Technology Matrix
Feedstock Basic Chemistry Feedstock Composition
Second Gen. Biofuels Sugar Platform Thermo-chemical Platform
Third Gen Biofuels
Petroleum & Petroleum & First Generation First
Generation BiofuelsBiofuels
World Oil ConsumptionWorld Oil Consumption
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World Oil ConsumptionWorld Oil Consumption
OECD: Organization for Economic Cooperation and Development:
Australia, Austria, Belgium, Canada, the Czech Republic, Denmark,
Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy,
Japan, Luxembourg, Mexico, the Netherlands, New Zealand, Norway,
Poland, Portugal, Slovakia, South Korea, Spain, Sweden,
Switzerland, Turkey, the United Kingdom, and the United States.
Million Barrels per DayMay, 2008 Statistics
First Generation Biofuels First Generation Biofuels --
ProductionProduction
First Generation Biofuels First Generation Biofuels --
FeedstocksFeedstocks
(1) United States Department of Agriculture, 2006-2007 Crop
Year,
(2) Food and Agricultural Organization of the United Nations,
2005 Crop Year
261 mm gpy ethanol11.3 mm bpd gasoline
General CommentGeneral Comment
Oil prices increase 700% in ten years.
Exxon records $40 billion in profits - 2007.
US spends $500 billion + and countless lives protecting Middle
Eastern oil fields.
Corn prices increase 200% in 100 years.
America can stop paying farmers not to farm.
Americas migration from farms to cities will be reversed.
BADGOOD
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Second Generation Second Generation BiofuelsBiofuels
TechnologiesTechnologiesBiomass Process MatrixBiomass Process
Matrix
LIGN
OC
ELLULO
SE FEEDSTO
CKS
ACIDHYDROLYSIS
PRETREAT ENZYMEHYDROLYSIS
GASIFICATION
DILUTE ACID
CONC. ACID
DILUTE H2SO4
CONC. H2SO4
CAUSTIC
ORGANOSOLV
THERMO-MECHANICAL
CATALYTIC REFORMING
H2SO3
SYNTHESIS
HCl
H2SO4
H2SO4
HCl GAS
HCl LIQUID
2-STAGEPROCESS
ENZYMEHYDROLYSIS
ENZ. HYDROLYSIS& FERMENTATION
FERMENTATION
SUGAR
SUGAR
PRODUCT
PRODUCT
PRODUCT
Second Generation Second Generation BiofuelBiofuel
TechnologiesTechnologiesResearch & Development AreasResearch
& Development Areas
Sugar Platform Chemical Chemical / Biochemical
Thermochemical Metallic Catalyst Biocatalyst
Second Generation Second Generation -- Sugar Platform Sugar
Platform Chemistry and Process BasicsChemistry and Process
Basics
Carbohydrate ChemistryCarbohydrate Chemistry
Simple Sugars Monosaccharides (reducing sugars)
Xylose, Glucose / Dextrose Fructose
Disaccharides Sucrose, Maltose
Complex Sugars Polysaccharides
Starch, Cellulose, Hemi-cellulose, Beta-glucan, Arabinoxylan
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General Carbohydrate ClassesGeneral Carbohydrate Classes
Simple sugars Building blocks Quick access energy
Starches Energy storage
Cellulose, Hemicellulose Structural
Simple SugarsSimple Sugars
GlucoseC-6
123
4 56
XyloseC-5
1
23
4
5
Starch StructureStarch Structure
Amylose
Amylopectin
Starch Starch -- Cellulose ComparisonCellulose Comparison
Amylose
Cellulose
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GlucanGlucan StructureStructure
Cellulose
CrystallineCellulose
Beta Glucan
ArabinoxylanArabinoxylan StructureStructure
Lignin StructureLignin Structure Constituents of
BiomassConstituents of Biomass
Lignin: 15%25% Complex aromatic structure Very high energy
content Resists biochemical conversion
Hemicellulose: 23%32% Xylose is the second most
abundant sugar in the biosphere Polymer of 5- and 6-carbon
sugars, marginal biochemical feed
Cellulose: 38%50% Most abundant form of carbon
in biosphere Polymer of glucose, good
biochemical feedstock
O
OO
O H
O H
O H
HOH O
O HO
O
OO
O H
O H
O H
H O
H O
O HO
O
OO
O H
O H
O H
H O
H O
O HO
O
OO
O H
O H
O H
H O
H O
O HO
O
OO
O H
O H
O H
H O
H O
O HO
O
OO
O H
O H
O H
HO
H O
O HO
O
OO
OH
O H
O H
HO
H O
O HO
O
OO
O H
O H
O H
H O
H O
O HO
O HO
HO
H 3C O
O H
OC H 3
O C H 3
O
O
O
O H
O C H 3
O C H 3
H 3C O
OO
H O
H3C O
H O
O C H 3
O C H 3
OH
O
H O
H 3C O
O H
O C H 3
O C H 3
O
O
O H
O C H 3
O C H 3
O C H3
O
O
O
O H
H O
O
O
O
O
O H
H O
O H
O H
O
O
O
O H
H O
O H
O H
O
O
O
O H
HO
O H
O H
O
OO
O H
O H
O H
H O
H O
O HO
O
OO
O H
O H
O H
H O
H O
O HO
O
OO
O H
O H
O H
H O
H O
O HO
O
OO
O H
O H
O H
HO
HO
O HO
O
OO
O H
O H
O H
HO
H O
O HO
O
OO
O H
O H
O H
H O
HO
O HO
O
OO
O H
O H
O H
H O
H O
O HO
O
OO
O H
O H
O H
HO
H O
O HO
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Plant Cell Wall ModelPlant Cell Wall Model
Buckeridge et al., 2004John Brady, CornellNREL subcontractor
CHARMM1 ns simulationSDSC DataStar
Cellulose Crystalline Structure Cellulose Crystalline
Structure
Cellulose is a crystalline Cellulose is a crystalline structure
that resists structure that resists water penetrationwater
penetration
This makes disassembly very This makes disassembly very
difficult since the enzymes and difficult since the enzymes and
acid catalysts are in solution.acid catalysts are in solution.
John Brady, Cornell
CHARMM1 ns simulationSDSC DataStar
Water boundary layer is ~1.7x bulk water
Computer Simulations of Water Structuring Adjacent to
Microcrystalline Cellulose 1beta Surfaces, J.F. Matthews, C.E.
Skopec, P.E. Mason, P. Zuccato, R.W. Torget, J. Sugiyama, M.E.
Himmel, and J.W. Brady, Carb. Res. 341, 138-152, 2006.
Detail of Water Boundary LayerDetail of Water Boundary Layer
Biomass Biomass FeedstocksFeedstocksGeneral CompositionGeneral
Composition
0 10 20 30 40 50 60 70 80 90 100
Bagasse
Wheat Straw
Corn Stover
Soft Wood
Hard Wood
Wt. Percent (dry basis)
Cellulose Hemicellulose Lignin Extractives Uronic Acid Ash
0 10 20 30 40 50 60 70 80 90 100
Bagasse
Wheat Straw
Corn Stover
Soft Wood
Hard Wood
Wt. Percent (dry basis)
Cellulose Hemicellulose Lignin Extractives Uronic Acid Ash
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Corn Stover CompositionCorn Stover Composition
Cellulose 33.9%
Xylan Lignin
Extractives
24.2% 11.4% 9.7%
Other Hemi. 5.2%
UronicAcid 4.0%
Acetyl 3.9%
Ash 3.5%
Protein 1.2%
Sucrose 6.2%
Corn Stover
(dry weight basis)(dry weight basis)
Biomass Biomass FeedstocksFeedstocksImprovements in
AnalysisImprovements in Analysis
0
10
20
30
40
50
60
70
80
90
100
Old methods New methods
P
e
r
c
e
n
t
D
r
y
W
e
i
g
h
t
ligninproteinstructural inorganicssoluble inorganicsashuronic
acidsacetylminor sugarssucroseextractivesxylanglucan
Biomass FeedstocksBiomass FeedstocksSpecific CompositionSpecific
Composition
0
10
20
30
40
50
60
70
80
90
100
HARDWOOD SOFT WOOD CORN STOVER SUGAR CANEBAGASSE
CORN FIBER
P
e
r
c
e
n
t
D
r
y
W
e
i
g
h
t
starchfatcutinproteinashextractives
ligninuronic acids
acetylarabinangalactanmannan
xylanglucan
0
10
20
30
40
50
60
70
80
90
100
$0.96
$0.98
$1.00
$1.02
$1.04
$1.06
$1.08
$1.10
$1.12
$1.14
$1.16
$1.18
$1.20
$1.22
$1.24
$1.26
$1.28
$1.30
$1.32
$1.34
$1.36
$1.38
MESP ($/gal)
N
u
m
b
e
r
o
f
O
c
c
u
r
a
n
c
e
s
Effect of Stover Compositional VariabilityEffect of Stover
Compositional Variability
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StarchStarch HydrolysisHydrolysis Reaction MechanismsReaction
Mechanisms
Substrate + H2O(Starch)
Energy + Enzyme
(Alpha Amylase)
Product(Dextrins)
Substrate + H2O(Dextrins)
Enzyme
(Gluco Amylase)
Product(Glucose)
Substrate(Glucose)
Yeast + Nutrients Product(Ethanol, CO2, Biomass)
Biomass Hydrolysis Reaction MechanismsBiomass Hydrolysis
Reaction Mechanisms
Substrate + H2O(Biomass = Cellulose, Hemicellulose, Lignin)
Energy + Catalyst
(Acid)
Product(Xylose, Xylans,
Cellulose, Lignin)
Substrate + H2O(Cellulose)
Enzyme
(Cellulase Package)
Product(Glucose)
Substrate(Glucose)
Yeast + Nutrients
(Cellulase Package)
Product(Ethanol, CO2, Biomass)
Substrate(Glucose, Glucans,
Xylose, Xylans)
GMO + Nutrients Product(Ethanol, CO2, Biomass)
PilotPilot--Scale Acid Pretreatment SystemScale Acid
Pretreatment System Tracking Composition and MassTracking
Composition and Mass
6.6% 3.6%
1.9%
2.4%
Pretreated Corn Stover Solids Liquor Furfural
60.3% 30.7%
Other XyloseGlucosePretreatment?
Cellulose 33.9%
Xylan Lignin 24.2% 11.4% 9.7%
ExtractivesSucrose
Other HemiUronic Acid
AcetylAsh
Protein
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Cellulose HydrolysisCellulose Hydrolysis
BAGASSE
CORN STOVER
Higher C6 cake solids are critical to reducing production
costs.
Cellulose Enzymatic Hydrolysis ReactionCellulose Enzymatic
Hydrolysis Reaction
Sugar Platform FermentationsSugar Platform FermentationsChoices
and ChallengesChoices and Challenges
Second Generation Second Generation ThermochemicalThermochemical
Platform Platform Chemistry and Process BasicsChemistry and Process
Basics
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ThermochemicalThermochemical Pretreatment Pretreatment
GasificationGasification
Process Partial combustion in
controlled O2atmosphere
Types Air Oxygen Steam
Air / Oxygen Blown Gasifier Stoichiometry
8 CH2O + O2 +(4 N2) 6 CO + 2 CO2 + 8 H2 + (4 N2)Biomass
Steam Blown Gasifier Stoichiometry
5 CH2O + 2 H2O 3 CO + 7 H2 + 2 CO2Biomass
ThermochemicalThermochemical Pretreatment Pretreatment
Gasification Gasification StoichiometryStoichiometry
Ethanol from Synthesis GasEthanol from Synthesis GasCatalytic
RouteCatalytic Route
Ethanol from Synthesis GasEthanol from Synthesis GasBiological
RouteBiological Route
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Clostridium ljungdahlii Tanner, et. al., 1993
Ethanol from Synthesis GasEthanol from Synthesis GasBiological
RouteBiological Route
6 CO + 3 H2O CH3CH2OH + 4 CO2
6 H2 + 2 CO2 CH3CH2OH + 3 H2O
Ethanol from Synthesis GasEthanol from Synthesis GasBiological
Route Biological Route Basic ReactionsBasic Reactions
Air / Oxygen Blown Gasifier8 CH2O + O2 + (4 N2) 2.33 CH3CH2OH +
3.33 CO2 + H2O + (4 N2)
Theoretical Yield : 136 Gal / Dry Ton BiomassBiomass
Steam Blown Gasifier8 CH2O 1.67 CH3CH2OH + 1.67 CO2
Theoretical Yield : 136 Gal / Dry Ton Biomass - Air Blown155 Gal
/ Dry Ton Biomass - Steam Blown
Biomass
Ethanol from Synthesis GasEthanol from Synthesis GasBiological
Route Biological Route -- StoichiometryStoichiometry
Third Generation Biofuel TechnologiesThird Generation Biofuel
Technologies
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Third Generation TechnologiesThird Generation Technologies
LS9 Sugar GMO Fermentation Hydrocarbon properties
Virent Sugar Catalytic / Chemical Hydrocarbon properties
Third Generation TechnologiesThird Generation Technologies
DuPont / British Petroleum Sugar GMO Fermentation Hydrocarbon
properties
Greenfuel Technology CO2 Algae Lipids and carbohydrates
Third Generation TechnologiesThird Generation Technologies
Amyris Sugar GMO Fermentation Hydrocarbons
Synthetic Genomics CO2 , Carbohydrates GMO Fermentation Lipid
and carbohydrates
LignocellulosicSugar Platform
AnaerobicDigestion
BiodieselDerivative
Chemistries
Biodiesel
LignocellulosicThermochemical
Platform
BioethanolDerivative
Chemistries
Starch & SugarBioethanol
Operations & MaintenanceManagement
THANK YOU
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CINCINNATI, OHIO, USA
Thank You
Always remember.....a bad day fishing is still better than a
good day at work.
