Understanding SWING Architecture CS 4170 UI Design Hrvoje Benko Oct. 9, 2001.
Development of a Bio-Based Process for...
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Development of a Bio-Based
Process for Isoprene
October, 2012
David Benko, Frank Feher, and Tang Wong
The Goodyear Tire & Rubber Co.
Akron, OH
Greg Bohlmann, Greg Whited, Maggie Cervin,
Joe McAuliff, Rich LaDuca, and Karl Sanford
Genencor Division of Danisco USA
Palo Alto, CA
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Typical Passenger Tire Composition
Synthetic &
Natural Rubber
43%
Carbon Black
& Silica
27%
Steel
10%
Fabric
5% Chemicals
10%
Oil
5%
Oil and
Natural Rubber
Oil + Energy
Oil
+
Energy
Energy
+
Raw
Materials
Over 70% petroleum derived
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Natural Rubber (NR) is a Key Resource for Tires
• Large volumes available
– Global NR production is ~20 B lbs/yr
– Approximately 70% is used to make tires
• Superior physical properties
– Excellent resistance to wear and tear; low hysteresis
– Essential for demanding applications (e.g., aircraft,
military, trucks)
– Major ingredient (25-50%) in better consumer tires
• No alternatives available at comparable price and volume
– Commercial NR based on single species (i.e., Hevea brasiliensis)
– Synthetic polyisoprene is best alternative but limited by relative scarcity of
isoprene monomer
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Threats to Supply of Natural Rubber
• Global demand increases well beyond supply
• Political instability in growing regions (Southeast Asia, W Africa) – Rubber trees grow in a very narrow band at +/- 12 degrees from the
equator.
• Economic instability – Dominance of small holders
– Economic alternatives from industrialization
• Widespread plant disease from lack of genetic diversity
Significant threats to NR supply exist
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World Map Showing NR Production Regions
+ 12°
Hevea Brasilienis (The Rubber Tree) is widely distributed in the Equatorial Belt
The solid areas show the main centers of production
Rubber is a Tropical Tree (best at Equatorial zone) that grows best at temp of 24-30°C (75-86°F)
Needs annual rainfall of 1,780-2,030mm (70-80in)
Up to 610m (2,000ft) above sea level. Prime area ±12 degrees latitude
L. AMERICA
2.0%
Tropic of Cancer 22½ N
Tropic of Capricorn 22½ S
Equator
AFRICA
4.3%
- 12°
Thailand, Indonesia
& Malaysia account
for 71.3%
China
India ASIA
93.7%
Hainan, China (outside zone)
not best,
but strategic
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The Vision: Isoprene from
Biomass
We aim to develop an efficient and sustainable fermentation
route to isoprene from carbohydrate feedstocks
2-Methyl-1,3-butadiene
Corn Switchgrass
Sugar cane
MolassesWoody
biomass
Isoprene
BiomassSugars
D-Glucose
+
other C5 and C6
sugars
O
OH
HOHO
OH OH
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Biochemical Basis for Feedstock Conversion
CO2 + H2O
α-D-Glucose β-D-Glucose
enzymes
enzymes
enzymes
cellulose
starch
isoprene
enzymes
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Bioprocess to Isoprene Enables:
• Decreased dependence on natural rubber sourcing
• Reduced petroleum price impact on isoprene costs
• Supply of isoprene de-linked from petroleum processing
• Stability of monomer supply
• Potential for significant savings associated with rubber supply
• Potential for product performance enhancement
Synthetic rubber from sustainable nonpetroleum based sources
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Isoprene Production
TREES BIOBASED
PROCESS
CHEMICAL
SYNTHESIS
PETROLEUM
CRACKING
• Slow
• Not commercially relevant
• Extractive distillation from ethylene & propylene production
• Price linked to oil prices
• Moving to “light” streams
• High cost
• Petroleum feedstocks
• Mfg. infrastructure in Russia & Japan
• Renewable feedstocks
• Biochemical and biofuel products
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Building Block Biochemicals (2006):
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Partnership for BioIsopreneTM
• Leading manufacturer of synthetic elastomers
• Technology for producing synthetic polyisoprene
• Expertise for isolating, purifying, handling, storing and shipping isoprene
• Leading industrial biotechnology
company
• Technology for producing
genetically-modified organisms for
industrial applications
• Ability to develop complete process
for producing isoprene from
biomass
Collaborative research initiative with joint multimillion-dollar investments
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Goodyear and Genencor leveraging each
others’ expertise …
CH2
CC
H2C
CH3H
Integrated biobased process for production of BioIsopreneTM
Renewable Feedstock(s)
Microbial Strain Development
Large Scale Fermentation
BioIsopreneTM recovery & purification knowhow
Polymer-Grade BioIsopreneTM
Product
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BioIsopreneTM Technology:
• Multiple feedstocks possible
• Two feeder pathways to isoprene precursor
• Isoprene synthase
C6 3C (C5)
3C 2C
16C 2C
Isoprene Synthase
Isoprene Recovery
Glucose
Sucrose / Biomass
Glycerol
Plant Oils
DXP Pathway
MVA Pathway
Cells
Conceptual View of Cell Factory
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Metabolic Pathways
Bouvier (2005) Prog. Lipid Res. 44, 357–429.
• Two known pathways for
producing precursors to
isoprene (MVA, DXP)
• Both capable of using
fermentable sugars as
feedstocks
• Same isoprene-producing
reaction
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Genetic Engineering Optimizes Bacteria for Isoprene Production
Enterococcus
Yeast
Archea
Kudzu
E. Coli
Genes from 5 different organisms were used to create the 1st-
generation isoprene-producing bacteria
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• Engineered E. coli
• 14-L fed batch fermentation from glucose
• Extensive IP portfolio: 14 published applications to date
BioIsoprene™ Titer
0
50
100
150
200
250
0 8 16 24 30 37
Time (h)
OD
600
0
10
20
30
40
50
60
70
Tit
er
(g/L
)
Jan 2009
Titer
OD600
Isoprene Production
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Integrated Process Overview
PF
FF
PF
FF
L
FR
P
I
P
R
P
R
Polymerization Fermentation Recovery - Purification Feedstock
BioIsoprene™
Product
BioNatsyn™ (Synthetic
Rubber)
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BioIsopreneTM Polymerization
Frequency Sweep of Tan d for PetroNatsyn & BioNatsyn
0.0
0.1
0.2
0.3
0.4
0.5
1 10 100 1000 10000
Frequency (cpm)
Tan
d
Petro Natsyn
BioNatsyn
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Tread Compound Properties
BioNatsyn
Polyisoprene Natsyn Polyisoprene
Cure time, min
(t90 at 150°C)
19.6 21.8
300% modulus,
MPa
9.2 7.2
Tensile strength,
MPa
16.5 16.1
Elongation at
break, %
542 598
Mooney viscosity 45 45
Shore A hardness 71 62
The recipe consisted of 100 phr cis-1,4-polyisoprene, 60 phr carbon black, 12.5 phr
silica, 13 phr oils and waxes, 8.25 phr antidegradants, 10.8 phr curatives
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Concept Tire
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2010 - Add isoprene to the list