Bioenergy ProgramBioenergy ProgramDepartment of Forest Department of Forest BiomaterialsBiomaterials

Faculty in Bioenergy Science and Technology

Dimitris ArgyropoulosProfessor

Wood Chemistry

Med ByrdAssociate Professor

Process Development

Hou-min ChangProfessor Emeritus

Wood Chemistry

Vincent ChiangProfessor

Forestry Biotechnology

Martin HubbeProfessor

Surface Chemistry

Stephen KelleyDept Head & Professor

Polymer Chemistry

Adrianna KirkmanProfessor

Process Simulation

Lucian LuciaAssociate Professor

Wood Chemistry

Sunkyu ParkAssistant ProfessorBioenergy Process

Richard PhillipsExecutive in ResidenceBioenergy Economics

Orlando RojasAssociate ProfessorSurface Chemistry

Daniel SaloniAssistant Professor

Process Development

David TilottaAssociate Professor

Wood Chemistry

Richard VendittiAssociate ProfessorLife Cycle Analysis

Hasan JameelProfessor

Process Engineering

John HeitmannProfessor

Enzyme Biotechnology

Bioenergy Projects

• Wood-to-Ethanol Research Consortium

• Value Prior to Pulping (VPP)

• Ethanol from Transgenic Hardwoods

• Ethanol from Coastal Bermuda Grass

• Enhancing Wood Penetration for More Efficient Hydrolysis and Optimized Saccharification

• Opportunities with Dissolved Wood for the Forest Biorefinery

• Validation of Therminator Syngas Cleanup

• Advanced Technology for Low Cost Ethanol from Engineered Cellulosic Biomass

• Economics and Feasibility of North Carolina Biomass Conversion

• Producing Ethanol from Biomass by Extracting Value Prior to Extraction

• Low Cost Conversion of Industrial Sludges to Ethanol

• Integrated Torrefaction-Gasification for the Production of Biofuels

• Economic Analysis of Pine Biomass Varieties for Ethanol Production

• Life Cycle Analysis for the Production of Transportation Fuels

• Fast Pyrolysis of Forestry Biomass

Wood to Ethanol Research Consortium (1)

• Industry consortium of six companies

• Repurposing a kraft pulp mill into a ethanol mill

• Develop cost effective process by reusing existing assets

Background

• Majority of bioethanol in United States is produced from corn, none from wood– Wood is competitive with corn in carbohydrate content with corn– Cheaper raw material– Capital cost to build large scale plant 2-3 X Corn Plant– Increasing controversy over use of corn for fuel vs food

• Demand for paper and board declining in United States– > 9 Million tons of capacity have permanently closed in United

States since 2000– Kraft pulp mills can potentially be repurposed to ethanol production

5

Background

• Concept inception October 2006

• Ponderosa Consortium 2007– Arborgen– BE&K Engineering– International Paper– Genencor– Metso Paper– Stone Smurfit– Syngenta– Weyerhaeuser– Xethanol

6

Advantages of Repurposing a Kraft Mill to Ethanol

1. Assets can largely be reused without serious compromise

2. Biomass supply chain in place to grow – harvest – deliver large amounts of wood

3. Low cost harvesting residuals frequently left behind in a kraft mill can be effectively used in ethanol production

4. Equipment in place is commercially proven and needs no additional development

5. Workforce in place, trained, likely motivated to succeed

6. Environmental permitting likely to straightforward

7

Pulp and Paper - Base Case Mill

8

Ponderosa Asset Reuse

9

Lignin To Power Boiler

Repurpose Cases Considered

• Repurpose A– Same wood volume by species and form as Base Case

• Repurpose B1– Same as Repurpose A + 10%

• Repurpose B2– Same as B1 except 100% Pine – no debarking + 15% Harvesting

Residuals

• Repurpose B4– Same as B1 except 100% Hardwood – no debarking + 40%

Harvesting Residuals

10

Capital Costs1

in $2009

11

Repurpose B1 Repurpose B2 Repurpose B4 Repurpose B6 Repurpose B7 Repurpose B8Ethanol, Liters 241,015,752 240,225,758 274,062,729 380,216,046 169,866,977 249,278,852

Ethanol, Gallons 63,669,622 63,461,129 72,399,939 100,442,766 44,874,248 65,852,711

Batch Digester Modifications 12,478,000$ -$ -$ -$ -$ 1,191,000$

Continous Digester Modifications 12,296,000$ 32,564,000$ 32,564,000$ 32,564,000$ 5,475,960$ 3,132,000$

Hydrolysate Cleanup 1,762,000$ 1,892,000$ 1,879,000$ 1,869,000$ 1,611,522$ -$

Additional Hydrolysis Retention 4,769,000$ 5,178,000$ 5,350,000$ 5,817,000$ 3,290,436$ 5,350,000$

Alcohol Plant 150,127,000$ 160,423,000$ 165,459,000$ 172,721,000$ 109,847,934$ 155,340,324$

Lignin Separation and Burning 16,100,000$ 16,991,000$ 17,212,000$ 30,341,000$ 12,857,326$ 17,212,000$

Bleach Plant Modifications 3,480,000$ 3,480,000$ 3,480,000$ 3,480,000$ 3,480,000$ 3,480,000$

Total 201,012,000$ 220,528,000$ 225,944,000$ 246,792,000$ 136,563,000$ 185,705,000$

Capital Cost per Gallon Ethanol 3.16$ 3.48$ 3.12$ 2.46$ 3.04$ 2.82$

1 BE&K Estimates based on file histories

Manufacturing CostEnzyme at $0.30 per Gallon

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ConstantWood

+10% Wood

100%Pine +

Residuals

100%HWD +

Residuals

• Hardwood cost per ton higher thansoftwood but ethanol yield is greater

• Higher ethanol yield leads to lowerIndirect costs

• Cash Cost of Repurpose B4 –100% Hardwood

• $1.90 per Gallon Total Cash Cost• $0.25 per Gallon Energy Cost• $0.30 per Gallon Enzyme Cost• $0.61 per Gallon Biomass Cost

ConstantWood

+10% Wood

100%Pine +

Residuals

100%HWD +

Residuals

Summary

• Repurposing existing Kraft Pulp Mill Promising:

– Many practical advantages

– Wood – to – Ethanol process with a potential Internal Rate of Return > 20%

– Ethanol cash manufacturing cost ~ $1.60 per Gallon ($0.42 per liter) with enzymes at $0.30 per Gallon

• Requires simplification

– Too many people on payroll due to complex process

– Higher maintenance cost compared to corn

– Distillation and fermentation costs high due to low sugar concentrations

13

WERC Consortium

• Used Ponderosa as guidance for second consortium aimed at simplification (currently in progress)– WERC – “Wood Ethanol Research Consortium”

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2008 – 2009

•American Process

•Arborgen

•Andritz

•BE&K Engineering

•Catchlight Energy/Weyerhaeuser

•Evolution Resources

•Nippon Paper/JPPRI

•NC State Natural Resources Foundation

• Pretreatment methods in a Repurposed Mill– Autohydrolysis (AH)

• Acetic acid prehydrolysis (Hac)

– Sodium Carbonate (SC)– Green liquor (GL)

• Autohydrolysis/green liquor (AH-GL & HAc-GL)– Sodium Carbonate/Sodium Hydroxide

Yongcan Jin

Simplification of Pretreatment

Summary

Pretreatment Sugar Recovery

Autohydrolysis 45%

Acetic Acid Autohydrolysis 73%

Sodium Carbonate 50%

Green Liquor 80%

Autohydrolysis Green Liquor 74%

Acetic Acid Autohydrolysis- Green Liquor

79%

Sodium Carbonate-Sodium Hydroxide 68%

woodintescarbohydraTotal

monomerasSugarserySugar covRe

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Green Liquor Repurpose Case B10

RecoveryBoiler

WasteTreatment

PM2

Sawdust

Woodyard

BrownstockWashers

Screens

PM1Brownstock

WashersScreens

Evaporators

PowerBoiler

NaturalGas

DistillationBeer

Column

FermentationFiber

HydrolysisPrehydrolysis

Cook

Dehydration

EthanolProduct

HydrolysateCleanup

ClO2Generation

Wood+ Forest Residues

PowerSales

LigninRecovery

LimeKiln

PowerGeneration

Causticizing

ContinuousDigester

18

19

Use of Oxygen and Refining for Softwood

• Oxygen delignification and refining can improve enzymatic hydrolysis– Both these unit operations may be available in a repurposed mill

Softwood Options in a Repurposed Mill

ProcessTot. sugar in pulp

(% on wood)Sugar recovery (%)

Softwood 62.8 Basis on Tot. sugar in wood

GL16-25S-170 42.4

GL16-40S-170 45.9

GL16-25S-170-R 58.8

GL16-40S-170-R 64.0

GL16-25S-170-O 62.6

GL16-40S-170-O 68.0

GL16-25S-170-O-R 69.8

GL16-40S-170-O-R 74.4

Hardwood Fiber, Enzyme Costs Critical to successMaintenance and Energy Cost next most critical

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$1.79 per Gallon

Softwood Cash Costs better than Hardwood

23

$1.70 per Gallon

Commercialization Status

• One consortium member negotiating to acquire 1-3 assets that have been shut down or in the process of being closed– Bastrop, Louisiana: Uncoated free sheet, high HW– Franklin, Virginia: Uncoated free sheet, high HW– Pineville, Louisiana: Linerboard, SW

• Engineering studies are being conducted at one location with estimates of capital cost

• Propose to start up in 1.5 years

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Ethanol from Transgenic Hardwoods

• Sungrant (DOT)

• Evaluate potential for simplifying pretreatments for low/modified lignin hardwoods

– Autohydrolysis

– Ozone

– Mild alkaline

Samples Lignin S/G GlucanWildtype 23 2.2 44TG96 24 6.4 45TG141 11 2.6 54

Figure 1. Effect of lignin content on glucose yield from wildtype and transgenic woods

Advanced Technology for Low Cost Ethanol from Engineered Cellulosic Biomass

• USDA - DOE

• Demonstrate transgenic tree plantations with fast growing low lignin/high cellulose transgenic trees

• Demonstrate on a pilot scale the improved processability and economics, including simplified pretreatment strategies

• Economic evaluation of the different biomass and process options, using standard investment analysis techniques, including all applicable subsidies

Economics and Feasibility of North Carolina Biomass Conversion

• Indentify the most suitable and profitable scheme

to produce ethanol in North Carolina with a

complete analysis of the Supply Chain

Forest biomass1. Hardwoods: Eucalyptus, poplar, mixed hardwood 2. Pine3. Forest residues

Agriculture biomass1. Switch grass2. Myscanthus3. Coastal bermuda grass4. Corn stover5. Sugar beet6. Arundo donax7. Sweet sorghum

13,400 10,050 8,040

66,999

50,249

40,200

0

10

20

30

40

50

60

70

80

0

10,000

20,000

30,000

40,000

50,000

60,000

70,000

80,000

7.5 BDT/acre/year 10 BDT/acre/year 12.5 BDT/acre/year

Lan

d in

vest

men

t (M

illio

ns $

)

Acres to harvest Total acres Land investment ($)

Acr

es

Ethanol from Coastal Bermuda Grass

• Develop simplified pretreatments for the conversion of coastal Bermuda grass to ethanol– Autohydrolysis– Sodium Carbonate– Ozone– Ammonia Explosion– Microwave/NaOH– Lime

Untreated AFEX treated

Coastal Bermuda Grass Bales

Bio-ethanol

PretreatmentPretreatment

Economic Analysis of Pine Biomass Varieties as Feedstock for the Production of Ethanol

• Characterize 178 pine varieties to identify those with varying lignin and cellulose content

• Select 20 varieties with different wood properties, and perform chemical and physical characterization of the wood properties

• Measure fermentable sugar yield using three pretreatments (dilute-acid, weak alkaline, organosolv)

• Compare feedstock value of different pine and poplar and recommend ideal loblolly pine feedstock

Low Cost Conversion of Industrial Sludges to Ethanol

• Biofuels Center of North Carolina

• Demonstrate an effective technology to convert industrial papermaking sludge as a cost effective feedstock for the efficient biochemical biomass conversion to ethanol

Papermaking Sludges

Negative feedstock costContains CaCO3 and inorganics

Value Prior to Pulping

• DOE and Consortium of Companies and various research organizations

and universities

• Extract hemicelluloses prior to pulping and convert to ethanol and

chemicals

31ETHANOLFERMENTATION

WOOD CHIPS PULP & PAPER

DIGESTER

CHEMICALS

Producing Ethanol from Biomass by Extracting Value Prior to Combustion

• Develop a process for hot water treatment of wood to extract the hemicelluloses.

• Following extraction, the wood residue is sent to a boiler and burned as conventionally

practiced

CombustionWoody BiomassHot WaterExtraction

Ethanol – Acetic Acid

Certain Ionic Liquids Can Completely Dissolve Wood

Time

Opportunities with Dissolved Wood for the Forest Biorefinery

Cellulose Fibers

Lignin BasedComodity

Chemicals / PhenolicsNew Value –Added Materials

Component Fractionation

FullyDissolved

Wood & Components

Kraft LigninOxidative DealkylationWood

Modification

Cellulose

Novel Exruded Wood Products

Liquid Wood

recycling of IL’s

Wood BasedComodity &Speciality

Chemicals/Furanoids

Hemicellulose

Biofuels

Dimitris S. Argyropoulos

Enhancing Wood Penetration for More Efficient Hydrolysis and Optimized Saccharification

The metal (IrCp*)-cellulase complex is later recovered and the SOW (Surfactant Oil-Water) micro-emulsion may also be recycled

Morphology of a microemulsion represented by a random bicontinuous

structure or a Schwartz surface.

IrH2O OH2

H2O

IrNO3 NO3

2+

= surfactant

Life Cycle Analysis for the Production of Transportation Fuels

• Perform detailed material and energy balances on a set of biofuel manufacturing processes and feedstocks

• Develop equipment and facility engineering plans for the processes/feedstocks

• Perform a life cycle analysis on the processes/feedstocks and report the relative impacts of the different processes/feedstocks

Production Transportation Use Disposal

Raw Materials

Energy EnergyEnergy Energy

Waste WasteWasteWaste

Emissions to air and water

Emissions to air and water

Emissions to air and water

Emissions to air and water

CORRIM Consortium for Research on Renewable Industrial Material

Validation of Therminator Syngas Cleanup

36

• US Department of Energy

• Validate syngas cleanup technology (“Therminator”, RTI International) and syngas conversion unit operation

• Integrate into the gasification process at the University of Utah

• A fixed bed or slurry bubble column reactor will be integrated downstream of the “Therminator” to produce FT waxes from RTI’s proprietary iron-based catalyst

Integrated Torrefaction-Gasification for the Production of Biofuels

• Turn woodchips into a substitute for coal by using a process called torrefaction that is greener, cleaner and more efficient than traditional coal burning.

• Quantify relationship between time and temperature to produce torrefied wood

• Use of torrefied wood for gasification

• Scale up process to pilot plant evaluation

• Economic and life cycle analysis of combine process

Fast Pyrolysis Bio-oil from Forest Resources

• NSF I/UCRC (Industry/University Cooperative Research)

• 43mm fluidized bed reactor for fast pyrolysis

• Assess the quality of bio-oils produced from forest resources including forest residue, small diameter wood, and deconstruction materials

• Investigate statistical relationships between feedstock lignin content and specific bio-oil properties