DOE 1435-04-03-CA-70224
Ray W. Miller
DuPont Bio Based Materials
January 27, 2005
DuPont Bio Based Materials
3G & Sorona®
Medical
Science
Performance
Materials
Biosensors
Specialty
Chemicals
Biorefinery
Bio-Based Materials
Market
Need
Energy
Applied
Biosciences
Surface
Engineering
Process
Engineering
Metabolic
Engineering
Materials
Engineering
Personal
Care
DuPont Bio-PDO Process
OH
HO
O
Gene 1
OH
HO
O
HO
HO
OH
Glucose
Gene 3
O
3GT
Sorona™
Polymers
O
HO
Gene 4
HO
O
n
OH
PDO
(3G)
DMT
OPO3=
OH
HO
O
Fibers, Resins, etc
OH
Gene 2
Presidential Green
Chemistry Award 2003
O
OPO3=
OH
A Highly Collaborative Bio-PDO Endeavor
Biocatalyst
&
Intellectual
Property
Fermentation
& Process
Separations
Refining
Integrated
Development
Raw Materials
3GT Polymer
Production
&
Market Access
Bio-3G
Bio-PDO
• Strategic partnerships.
Sorona™
• Unique competencies.
• Three companies, five locations, more than a dozen organizational units.
• “DuPont Tate & Lyle BioProducts, LLC” Joint Venture formed May 27, 2004
for Bio-PDO production
World’s First Bio 3G Plant – Loudon, TN
National Energy Security
USPetroleum
Crude Oil
Supply
is ~ 15x10^6
barrels / day = 1.7 trillion pounds per year*
Flow
in Millions
Barrels / Day
11.5MM
bpd
8 MM
bpd
Source : DOE_EIA
*1 Barrel = 0.1590 m3; 1 barrel of medium crude
= 900 kg/m3
Or 1 barrel of medium crude = 143.1 kg or 315.48 lbs
15Million barrels = 4.732 billion pounds/day
4/22/03
DOE Program Goal—A Vision of
Oil Savings
Ethanol (Billions of gal/yr)
35
30
25
EXISTING
EMERGING
Advanced
Corn
Mills
Sugar
Platform
-New Enzymes
-Pretreatment
-Fermentation
20
15
10
Fundamental
Advances in
Lignocellulose
Processing
and fermentation
Cellulose
Renewable
Fuel
Standard
5 bgy in 2012
Grain
2005
 Advanced technology
provides the leap to
substantial oil
displacement
 Government role is high
risk R&D
5
0
2000
 Existing and emerging
technology supports
targets of a renewable
fuel standard
ADVANCED
2010
2015
2020
 Industry role is to
commercialize
2025
Year
Re: J.D. McMillan, NREL
4/22/03
The Unique Role of Biomass
While the growing need for sustainable
electric power can be met by other
renewables…
Biomass is our only
renewable source
of carbon-based
fuels and chemicals
Fossil Energy Replacement Ratio
6
5.3
5
4
3
2
The road to petroleum
displacement is
is paved with
Cellulosic Biomass
1.4
0.8
1
0
0.4
Cellulosic Corn Ethanol
Corn
Cellulose
Ethanol
Ethanol
Biorefinery
Ethanol
Gasoline
Electricity
Gasoline Electricity
Source: J. Sheehan & M. Wang (2003)
Major Components
In Lignocellulosic
Biomass
H3CO
HO
H3CO
O
OCH3
O
O
OH
OCH3OCH3
Lignin: 15-25%
OCH3
OH
OH
Hemicellulose: 23-32%
O HO
O
OH
HO
OH O
O
HO
OH O
O
OH
OH O
O
O
OH
O HO
O
OH
O
OH
HO
OH O
OH
O HO
OH
OH
O
O
OH
OH O
O HO
OH
OH
O
OH
O
HO
O HO
OH O
HO
O
OH
OH O
OH
OH
O
OH
O
O HO
OH
OH
O
O HO
OH
OH O
O HO
O
OH
OH
O
OH
HO
OH O
HO
HO
O HO
OH
OH
O
O
O
O
OH
OH
O
HO

O
OH
OH
O
OH
OH O
HO
HO
O HO
OH
O
OH
HO
OH O
O HO
OH
OH
O
O
OH
OH O
O HO
OH
Cellulose: 38-50%
OH O
HO
O HO
OH
O
O
OH
HO
O HO
O
OH
O
OH
HO
O
OH
OH
OH
O
O
OH
OH
OH
HO
OH
H3CO
OCH3
OH
O
OH O
O
HO
O
O
O
O HO
HO
O
Complex network of
aromatic compounds
 High energy content
 Treasure trove of novel
chemistry
HO
O
OH
OH
OH
OCH3OCH3

O
OH
O
OCH3
A collection of 5- and 6-carbon
sugars linked together in long,
substituted chains- branched
 Xylose, arabinose, glucose,
mannose and galactose
O
OH
O
HO
OH
H3CO
OCH3
OH
O
OCH3
OH
HO
O
HO
O
OCH3
O
OH
OH
O
OH
OH O
HO
Long chains of beta-linked glucose
 Semicrystalline structure

Re: J.D. McMillan, NREL
O HO
OH
O
OH
OH O
OH
4/22/03
Grass
Secondary
Cell Wall
http://digital.library.okstate.edu/oas/oas_pdf/v72/p51_56.pdf
Integrated Bio Refinery Industry
Feedstock
Transport
Feedstock
Conversion
Fermentation
Production
Feedstock
Harvest
Ethanol &
Chemicals
Separation
+
Feedstock
Production
Downstream
Markets
DOE 1435-04-03-CA-70224
ICBR Project Objectives
• Goal:
– Develop and demonstrate technical and
economic feasibility of the ICBR process for
renewable fuels & chemicals
• Expected benefits:
– Fuels & chemicals made competitively with
petrochemical routes, improving energy security
– Economics that generate a fair return to secure
investment and rural development
– A reduced environmental footprint and
particularly GHG emissions
DuPont Bio-refinery Concept
Corn Grain Stream
Corn Stover Stream
Milling
Milling
Pre-treatment
Separation
75%
Starch
Fiber +
25% Starch
Enzymatic
De-Polymerization
C6 Saccharification
Lignin
Fermentation
Cellulose
Down Stream Processing
Value Added
Chemicals (ie:
PDO)
Hemicellulose Sacchar.
Electricity
Steam
C5/C6 Sugar Fermentation
Ethanol
Major Products
4/22/03
Main Tasks in the ICBR Project
1. An ICBR flow sheet with high value creation to
investment ratios
2. A corn stover collection, processing & saccharification
process to convert cellulosics to fermentables for fuel
ethanol production.
3. A metabolically-effective biocatalyst to convert stover
derived sugars to fuel ethanol.
4. An efficient grain process to extract fermentable sugar
plus a metabolically engineered biocatalyst that
maximizes production of higher value chemicals.
The four “Miracles of Science”
Corn Stover – The First Target
Composition
Glucan
36.1 %
Xylan
21.4 %
Arabinan
3.5 %
Mannan
1.8 %
Galactan
2.5 %
Lignin
17.2 %
Protein
4.0 %
Acetyl
3.2 %
Ash
7.1 %
Uronic Acid
3.6 %
Non-structural Sugars
1.2 %
Re: B. Dale - MSU
4/22/03
Critical Success Factor 1:
Sustainable Biomass Collection
Crop Residue
• “Sustainable” means:
• Soil Erosion Controlled
• Maintain Soil Organic Matter
• Preserve Productivity
• Low Cost
 Studies indicate 20-50% of corn stover can be removed while
preserving soil quality – need system to track
ICBR LCA Advisory Panel
Dr. Jane Bare
US EPA
Richard Glass
National Corn Growers’ Association
Dr. Allen Hershkowitz Natural Resources Defense Council
Charles Kubert
Environmental Law and Policy Center
Larry Russo
US DOE
Dr. John Sheehan
National Renewable Energy Laboratory
Lyle Stephens
Deere and Co.
Dr. John Sullivan
Ford Motor Company
Dr. Greg Wandrey
Pioneer Hi-Bred
Steve Lewis
Broin
Stakeholders guide our development efforts
Critical Success Factor 2:
Upstream Biomass Availability
Crop Residue
• Infrastructure must be developed to:
• Collect
• Transport
• Store
 While maintaining feedstock integrity and low cost
– need incentives to encourage
A truck load of corn stover
Corn Stover Collection
NREL: Lignocellulosic Biomass to Ethanol Process Design , A. Aden, 2002
Low Cost Biomass
Effect of Stover Cost on Ethanol at High Sugar Conversion
$0.70
$0.11/gal change for every $10/DT change
$0.60
/gal EtOH
$0.50
$0.40
$0.30
$0.20
$0.10
$$-
$10
$20
$30
$40
/dry Ton
$50
$60
$70
Millions Dry Tons per
Year
2020 U.S. Biomass Supply Potential
600
Forest Residues
Urban Wastes
Ag Residues
Mill Residues
Energy Crops
500
400
300
200
100
0
$20
Ref: NREL
$30
$40
Delivered Price ($/dry ton)
$50
Critical Success Factor 3:
Manage Biomass Variability
• Natural Product
• Large Amount of Feedstock Variability caused by:
 Growing Season
 Corn Seed
 Geographic Area
 Farmer Practices
 Input measurement will be important to establish
fair prices and manage biorefinery operations
Substantial Feedstock Variability
NIR Composition of 731 corn stover samples from the 2001 harvest
Xylan (% dry weight)
26
R2 = 0.028
24
• 22
20
18
16
14
28
J.D. McMillan, NREL
30
32
34
36
38
Structural Glucan (% dry weight)
40
Critical Success Factor 4:
Cost-effective Biomass Processing
• Low-Cost Pretreatment
 Low Investment
 Low Chemical Usage
 Low Energy Intensity
 High Yield – Low Impurities
 Integrate with downstream processing essential for success
 Minimize Inhibitors to Fermentation Organism
 Maintain high solids concentrations
Processing Technology
Utilize all the sugars = lower cost fuels
Ethanol Yields from Stover Sugars
Ethanol Yield (gal/dry ton)
120
100
80
60
40
20
0
95% Glucose
+ 90% Xylose
+ 90% Arabinose
+ 90% Gallactose &
Mannose
Project Highlights
Selected Accomplishments:
– Collaboration Database in place and working
– Benchmarked Existing and Future Processes
– Identified
~200
Thermostable Enzymes – all novel
– Successfully integrated a 1,6-glucosidase gene into
chromosome of PDO Production Strain:
3G Accumulation (g/L)
glucose
isomaltose
4
3
2
1
0
TTab109f1
pSYC-K1
pSYC-Dex
- Established a Dry Grind Lab with
Analytical Support
ICBR ROADMAP
Year 1
Task 1
Process
Optimization
Process
Flowsheets/
Economic
Evaluation
Scout
Hydrolysis/
Cellulase
Screening &
Discovery
Benchmark Z.,
Xylose Utilization
Genome
Sequenced
Rate/Yield/Titer/
Tolerance
Improved
Rate/Yield/Titer/
Tolerance
Optimized on
Hydrolysate
Scout Grain
Syrup Process;
1,6-glucosidase
Integrated
Grain Syrup
Development &
Co-metabolism of
other sugars
Optimized Grain
Syrup Process &
PDO Organism
Test Process
Concepts/Obtain
Critical Data
Pretreatment
Process Develop/
Cellulase Discovery
& Evolution
Year 4
Stage
Gate Review
Task 2
Process
Development
Stage
Gate Review
Task 3
Stage
Gate Review
Year 3
Task 4
Process
Understanding
Year 2
Process Develop &
Optimization/
Cross-site
Validations
Pretreatment
Optimization/
Scale-Up;
CBH & bG Evolution
Concept
Demonstration
Rigorous
Models/Large
Scale Equip
Trials
Pretreatment
Scale-up/
Strain
Development
Fermentation
Studies of
Optimized
Ethanologen
Scale-Up of Grain
Process &
10 L Fermentation
Optimization
Tech
Package:
ICBR
Pilot
Plant
Critical Success Factor 5:
Consistent Program Management
•
•
Extremely complex inter-connected problems
-
Multidisciplinary approach essential
-
No single entity has all the skills
Multi-year effort required

Critical mass is necessary

Managed goals with milestones and deliverables

Appropriate levels of support with incentives
 DOE budget “ear-marking” is undermining management
for success.