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Enzyme Sugar-Ethanol Platform Project
National Renewable Energy Laboratory
Operated for the U.S. Department of Energy by Midwest Research Institute • Battelle • Bechtel
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Project Goal
• Objective: Develop and demonstrate economical bioethanol technology based on enzymatic cellulose hydrolysis
• Feedstock Constraint: Develop the technology for an abundant biomass resource that can support production of at least 3 billion gallons of ethanol per year
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Approach• Select corn stover as feedstock
– Most abundant, concentrated domestic biomass resource
– Potential to leverage existing corn harvesting and processing (esp. to produce fuel ethanol) infrastructure and “bridge” industrial contacts
• Utilize low cost enzymes now being developed
– Genencor International and Novozymes Biotech Inc. are leading enzyme development work through cost-shared subcontracts from the USDOE. Lower cost enzymes are anticipated in 2003-2004.
• Demonstrate compelling process economics
– Validate improved process performance and identify potentially attractive commercialization scenarios.
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Project Scope
Process Development
DetailedInvestigation
Prelim.Studies
Testing andValidation
CommercialLaunch
Stage 1 Stage 3Stage 2 Stage 4 Stage 5
Gov. & Univ. & Corp. R&D
Industry-led deployment
Increasing Cost & Industrial Involvement
NREL-ledDevelopment
Industry-ledCommercialization
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Strategic Fit
• The project demonstrates enabling technology for a lignocellulose-based biorefinery
• The project focuses on the core steps needed to produce sugars, fractionated lignin, and ethanol
• Industry is focusing on the application of this technology to make new products
Pretreatment Enzymatic Hydrolysis
Ethanol Production
Glucose to BioProducts
Lignin to Electricity
C5 Sugars to BioProducts
Key:
Enabling Technology
Energy Technology
Industry Technology
Fractionated Lignin to BioProducts
Ethanol Recovery
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External Drivers or Showstoppers
• Price of Oil and Gasoline (Transportation Fuels)– Global supply and demand issue
– Contingent on fuel standards and energy policy
• Price and Availability of Starch (Grain) Ethanol– Existence of renewable fuel standard
– Markets for starch ethanol co-products
• Price and Availability of Corn Stover– How much can be removed and what does it cost?
– What infrastructure needed for collection, storage and delivery?
– Are there alternative markets that will out compete ethanol?
• Environmental Regulations and Policies– Greenhouse gas mitigation, carbon tax, etc.
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Simplified Process Schematic
Feed Handling
Utilities
FermentationPretreatment
Burner/BoilerTurbogenerator
ConditioningWaste WaterTreatment
Distillation &StillageTreatment
Storage
Corn Stover
Hydrolyzate BrothRecycle &Condensate
Waste Water
Ethanol
Cake
Biogas & Sludge
Waste Water
Enzyme
Recycle Water
Steam
Electricity
Steam
Steam & Acid
S/L SepSolids
Liquor
Waste Water
S/L SepSyrup
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Relative Cost Contribution by Area
Biomass Feedstock
Feed Handling
Pretreatment / Conditioning
SSCF
Cellulase
Distillation and Solids
Recovery
Wastewater Treatment
Boiler/Turbogenerator
Utilities
Storage
(0.30) (0.20) (0.10) - 0.10 0.20 0.30 0.40
Capital Recovery Charge Raw Materials Process ElectricityGrid Electricity Total Plant Electricity Fixed Costs
33%
5%
18%
12%
9%
10%
4%
4%
4%
1%
(after ~10x cost reduction)
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Process Economics
• Production costs dominated by– Feedstock– Enzymes - cellulases– Capital equipment throughout the plant
The focus of the project is to work closely with USDOE, ORNL, USDA, and others, to decrease these key cost factors.
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Key Cost Reduction Strategies• Minimize feedstock cost
– Work with ORNL, USDA, and others to reduce the cost of corn stover by developing policies and infrastructure for efficient collection, storage and delivery
• Minimize enzyme cost
– Exploit anticipated thermo-stability of lower cost enzymes being developed by Genencor and Novozymes to reduce enzyme and capital costs for process
• Reduce processing plant capital cost
– Demonstrate improved integrated process performance
– Use process engineering techno-economic models to explore potential benefits of co-location and co-products
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Market Goals
• The project targets achieving a commercial production cost of $1.10 per gallon by 2010
• This target is based on a combination of technical conversion process performance goals and market considerations
• The market for ethanol is driven by refinery demand for ethanol as a gasoline blend stock
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Ethanol Value-Demand Curve
• Oak Ridge National Lab’s linear programming model for a generic oil refinery used to estimate ethanol value as a function of demand (usage)
• Results quantify how the value of ethanol decreases as more of it is used
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Refiner Ethanol Demand CurveReference conditions Higher ethanol
demand scenario
From G. Hadder (ORNL, 1999)
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Demand Curve Findings
• At $1.10 per gallon, refiners can afford to use 1-5 billion gallons per year of ethanol, depending on the future price of petroleum
• This estimate does not include the effect of a tax incentives
• If the tax incentive continues at $0.50 per gallon ethanol, refiners can afford to use 10-11 billion gallons per year
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Possible ProcessPossible Process ScenarioScenario
Feedstock Handling
CO2
Ethanol
LigninResidue
Enzyme
Corn Stover
Steam
Electricity
Steam & Acid SolidsLiquor
Pretreatment S/L Separation
ConditioningSaccharification&
FermentationDistillation &Ethanol Purification
WastewaterTreatment
Burner/BoilerTurbogenerator
Lime
Steam
Gypsum
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Feedstock – Corn StoverFeedstock – Corn Stover
Model Parameter Value
Feedstock Cost $35/dry ton
Cellulose Fraction 37.1%
Xylan Fraction 19.9%
Arabinan Fraction 2.5%
Mannan Fraction 1.3%
Galactan Fraction 1.7%
Lignin Fraction 20.7%
* Composition is average of 5 stover pretreatment runs at NREL
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Feedstock – Corn StoverFeedstock – Corn Stover
Rationale for data:
• Feedstock Cost: – Walsh, et.al. (ORNL)
– Demonstrated at Harlan, IA
• Feedstock Composition:– Averaged stover data (NREL)
– Research underway to improve analysis methods and understand major sources of compositional variance
Model Parameter Value
Feedstock Cost $35/dry ton
Cellulose Fraction 37.1%
Xylan Fraction 19.9%
Arabinan Fraction 2.5%
Mannan Fraction 1.3%
Galactan Fraction 1.7%
Lignin Fraction 20.7%
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Feedstock – Corn StoverFeedstock – Corn StoverLarge Cost Impact
Feedstock Cost Impact
$0.83
$1.28
$1.48
$0.00
$0.50
$1.00
$1.50
Process Case
Min
imu
m E
than
ol S
ellin
g P
rice
($/
gal
eto
h)
$0.65/gal
$0 / BDT
$35 / BDT
$50 / BDT
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Feedstock HandlingFeedstock Handling• Brings biomass into facility
• Prepares biomass for pretreatment
• Subcontract work to develop less expensive handling systems
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Pretreatment - ExamplePretreatment - Example• Converts hemicellulose to monomeric sugars
• Makes cellulose more susceptible to enzymatic hydrolysis
Conditions:
Technology Dilute Acid
Reactor Solids Concentration
30 %
Residence Time 2 min
Acid Concentration 1.1 %
Temperature 190 °C
Reactor Metallurgy Incoloy 825-clad
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Pretreatment - ExamplePretreatment - Example• Converts hemicellulose to monomeric sugars
• Makes cellulose more susceptible to enzymatic hydrolysis
Conditions:
Technology Dilute Acid
Reactor Solids Concentration
30 %
Residence Time 2 min
Acid Concentration 1.1 %
Temperature 190 °C
Reactor Metallurgy Incoloy 825-clad
Rationale for Data:
• Corn stover steam gun expts
• Hot wash process expts
• Prior research on hardwood feedstocks
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Pretreatment - ExamplePretreatment - ExampleReactor Solids Cost Impact:
Prehydrolysis Solids Concentration Sensitivity
$1.20
$1.25
$1.30
$1.35
$1.40
$1.45
$1.50
10% 15% 20% 25% 30% 35% 40%
Prehydrolysis Solids Concentration inside Reactor
Min
imu
m E
tha
no
l S
ell
ing
Pri
ce
($
/ga
l)
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Pretreatment - ExamplePretreatment - ExampleXylose Yield Cost Impact:
Xylose Yield Cost Impact
$1.23
$1.50
$1.28
$0.00
$0.50
$1.00
$1.50
Process Case
Min
imu
m E
than
ol
Sel
lin
g P
rice
($/
ga
l et
oh
)
$0.27/gal
50% xylose
85% xylose
95% xylose
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Solid/Liquid SeparationSolid/Liquid Separation
Conditions:
Equipment Pressure Filter
Separation Temp 135 °C
Separation Pressure 5 atm
Conditioning Overlime only
Wash / Hydrolysate Ratio 0.58 kg/kg
• Separate pretreated solids from liquor
• Countercurrent hot water wash increases enzymatic digestibility and solubilizes recoverable lignin
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Solid/Liquid SeparationSolid/Liquid Separation
Rationale for Data:– Lower acetylation of corn
stover hemicellulose means IX not needed to reduce acetic acid levels
– Hot wash process expts
– Harris subcontract
– Working towards pilot scale demonstration at NREL
Conditions:
Equipment Pressure Filter
Separation Temp 135 °C
Separation Pressure 5 atm
Conditioning Overlime only
Wash / Hydrolysate Ratio 0.58 kg/kg
• Separation of pretreatment solids from liquor
• Countercurrent hot water wash increases enzymatic digestibility and solubilizes recoverable lignin
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Solid/Liquid SeparationSolid/Liquid SeparationCost Impact:
Conditioning Sensitivity
$1.20
$1.25
$1.30
$1.35
$1.40
$1.45
$1.50
OL only IX / OL
Process Case
Min
imu
m E
tha
no
l S
ell
ing
Pri
ce
($
/ga
l e
toh
)
$0.08 / gal
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Saccharification & FermentationSaccharification & Fermentation
• Enzymatic hydrolysis of cellulose to glucose
• Microbial conversion of sugars to ethanol
Saccharification:
Enzyme Source purchased
Enzyme Cost $0.11/gal EtOH
SHF vs. SSF Hybrid
Temperature 65 °C
Residence Time 1.5 days
Cellulose to Glucose Yield
90%
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Saccharification & FermentationSaccharification & Fermentation
• Enzymatic hydrolysis of cellulose to glucose
• Microbial conversion of sugars to ethanol
Saccharification:
Enzyme Source purchased
Enzyme Cost $0.11/gal EtOH
SHF vs. SSF Hybrid
Temperature 65 °C
Residence Time 1.5 days
Cellulose to Glucose Yield
90%
Rationale for Data:• Enzyme Cost is 10x-reduction
from Glassner-Hettenhaus parameters
• 10x-reduction is goal of enzyme subcontracts
• Hybrid design advantageous for more thermotolerant enzyme system
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Saccharification & FermentationSaccharification & Fermentation
• Enzymatic hydrolysis of cellulose to glucose
• Microbial conversion of sugars to ethanol
Fermentation:
Residence Time 2 days
Temperature 37 °C
Nutrient Requirement 0.25% CSL
0.33 g/L DAP
Effective Solids Conc. 20%
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Saccharification & FermentationSaccharification & Fermentation
• Enzymatic hydrolysis of cellulose to glucose
• Microbial conversion of sugars to ethanol
Fermentation:
Residence Time 2 days
Temperature 37 °C
Nutrient Requirement 0.25% CSL
0.33 g/L DAP
Effective Solids Conc. 20%
Rationale for Data:• Previous work based on
conversion of hardwood hydrolyzates using Z. mobilis
– Nutrients
• Strain improvements
– 2nd Gen. ethanologen projects at NREL
– Literature search
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Saccharification & FermentationSaccharification & Fermentation
• Enzymatic hydrolysis of cellulose to glucose
• Microbial conversion of sugars to ethanol
Yields:
Glucose to Ethanol Yield 92%
Xylose to Ethanol Yield 85%
Arabinose to Ethanol Yield 85%
Contamination Loss 5%
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Saccharification & FermentationSaccharification & Fermentation
• Enzymatic hydrolysis of cellulose to glucose
• Microbial conversion of sugars to ethanol
Yields:
Glucose to Ethanol Yield 92%
Xylose to Ethanol Yield 85%
Arabinose to Ethanol Yield 85%
Contamination Loss 5%
Rationale for Data:• Initial work based on
glucose and xylose cofermenting Z. mobilis
• Improved strains constructed with broader pentose and hexose substrate ranges
– rDNA yeast
– Ingram et al. constructs
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Saccharification & FermentationSaccharification & FermentationEnzyme Cost Impacts:
Enzyme Cost Impact
$1.23
$1.67
$2.24 $1.07 / gal
$0.00
$0.50
$1.00
$1.50
$2.00
Process Case
Min
imu
m E
than
ol S
ellin
g P
rice
($/
gal
eto
h)
$1.01/gal
$0.06 / gal
$0.11 / gal
$.50 / gal
$1.28
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Saccharification & FermentationSaccharification & FermentationCost Impacts:
Fermentation Residence Time Cost Impact
$1.25
$1.32
$1.28
$1.20
$1.25
$1.30
$1.35
$1.40
$1.45
$1.50
Process Case
Min
imu
m E
tha
no
l S
ell
ing
Pri
ce
($
/ga
l e
toh
)
$0.07/gal
1 day
3.5 days
7 days
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Saccharification & FermentationSaccharification & FermentationCost Impacts:
Fermentation Yield Cost Impact
$1.23$1.28
$1.33
95%
92%
70%
$1.20
$1.50
$1.80
$2.10
$2.40
glucose only add 85% xylose add 85% arabinose all other sugars85%
Min
imu
m E
than
ol S
ellin
g P
rice
($/
gal
)
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Saccharification & FermentationSaccharification & FermentationCost Impact:
Contamination
5% 7% equates to $0.02/gal increase
Nutrient Cost
$0.035/gal
89% CSL, 11% DAP
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Distillation & Ethanol PurificationDistillation & Ethanol Purification• Separation of ethanol and CO2 from “beer”
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Wastewater TreatmentWastewater Treatment• Anaerobic and aerobic treatment
• Reduce Biochemical Oxygen Demand (BOD)
• Recycle water
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Burner/Boiler/TurbogeneratorBurner/Boiler/Turbogenerator• Biomass boiler generates steam from lignin residue
• Excess electricity from generator sold to power grid ($0.04/kWh credit)
• High capital cost area
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Current Status
• Completing Stage 2– Compelling scenario identification
• Technology selection
– Stage 3 plan development
• Next step: Gate 3 review– Planned for January 2002
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Conversion-relatedCost Reduction Opportunities
• Stage 2 technology selection focus– Is a better pretreatment technology available?
• Higher yields, lower capital or operating costs
– Is a better fermentation strain available?• Broader sugar utilization range, higher ethanol yields,
better compatibility with enzyme
• Stage 3 technology improvement focus– Are better cellulases available and how do they
benefit integrated process economics?
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Technology Selection
• Tiered screening approach being applied to ensure best options will be studied in Stage 3– 1st screen: Efficacy– 2nd screen: Readiness and availability
• Stage 2 focus:– Pretreatment technology
– Fermentation strain
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Co-location-relatedCost Reduction Opportunities
• Better feedstock price– Proximity to transportation– Farmer cooperative
• Reduce capital cost– Utilize existing utilities and processing
infrastructure within site constraints
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Cost Reduction Strategies, cont.
• Reduce conversion plant capital cost– co-locate into a dry mill expansion– co-locate with a coal-fired power plant– co-locate with both a dry mill and power plant
• Reduce capital cost through better financing– Loan guarantee?– City/county/state/federal support or tax benefits?
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Cost Reduction through Co-products
• New process case potentially enables “sugar platform” and “lignin platform” co-products– Value-added co-products can increase upside of
process commercialization and mitigate overall risk
• While we can explore the possibilities, development of prospective co-products must be led by industry!
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Potential Bioethanol Co-products
Soluble Lignin (Low/Medium MW Phenolics)
Hemicellulose Hydrolyzate
(Xylose)
Cellulose Hydrolyzate
(Glucose)
Insoluble Lignin (High MW Phenolics)
1o EnzymaticCellulose
Hydrolysis
PretreatmentHemicellulose
Hydrolysis
2o EnzymaticHydrolysis &Fermentation
EthanolRecovery &Purification
Cell Mass, Enzymes
(Protein, etc.)
Process Residue Solids
Process Residue Liquids
Biomass EtOH
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Concentration & Purification of
Sugar Product(s)
Sugar & Lignin Platform Biorefinery
Sugar-rich HydrolyzateFeedstock
HandlingBiomass
Fractionation
Waste WaterTreatment
Renewable Biomass
Feedstock
WasteWater
Residual Solids & Syrup
Biogas& Sludge
Sugar Product(s)
RecycleWater
Steam
Steam
CatalystSteam, Acid,Enzyme, etc.)
SteamGeneration
PowerProduction
(Turbogenerator)
Ethanol Production& Recovery
Hydrolyzate& Residual
Solids FuelEthanol
Make-up Water
Waste Water
Unrecovered Sugars
Electricity
SteamWater
RecoveredLignin Purification
& Drying ofLignin Product(s)
LigninProduct(s)
SteamWater
Unrecovered Lignin
UnrecoveredLignin