1. Butanol as Fuel – View From the Field
NREL
March 11, 2010
Sam Nejame
Promotum
Thank you for having me here.
I’m Sam Nejame and my company is Promotum, a consulting firm focused on commercialization of next gen biofuels and green routes to chemicals. We provide business development, corporate development, due diligence, strategic planning and other services that help grow companies and markets.
Poll: Know your audience. Show of hands. How many policy? Commercialization? Scientists? 1 1

2. Agenda What is Butanol? Brief History ABE Process
Today’s Butanol From Petroleum
The Future of Butanol Fuels
Questions 2 2

3. What is Butanol? Family of 4 Carbon Alcohols
Most common forms are normal butanol (n-buoh) and iso-butanol (i-buoh)‏
n-buoh primarily used to make butyl acrylates for coatings and adhesives
Both n-buoh and iso-buoh have good fuel properties 3 3

4. Butanol Physical & Fuel Properties
Physical Property
i-butanol
n-butanol
Ethanol
Density at 20°C (g/cm³)‏
0.802
0.810
0.794
Boiling Point at 1 atm (⁰C)‏
108
118 78
Water Solubility at 20⁰C (g/100mL water)‏
8.0
7.7
Miscible
Net Heat of Combustion (BTU/gal)‏
95,000
93,000
80,000
R+M/2
103.5 87
112
Blend RVP (psi at 100⁰F) 1
5.0
4.3
18-22
This is a good time to distinguish between n-buoh and iso-buoh.
Both have similar energy content and vapor pressure and solubility characteristics,
but iso has a higher octane number (R+M/2) and is a better choice for blending w/gasoline.
n-buoh has higher a higher cetane number and is a better choice for blending with diesel.
Promotum, Gevo 4 4

5. Summary Comparison Butanol to Ethanol Fuel
Higher energy content
Less hydrophilic
More compatible w/oil infrastructure
More compatible w/installed base of autos
Reduces blend vapor pressure
Less corrosive
Iso-butanol works well with gasoline
n-butanol works well with diesel
Compatibility w/oil infrastructure. Butanols are not corrosive to aluminum (etoh is). Butanols are much less hydrophilic and can be transported through existing pipelines.
Reduction in blend vapor pressure means fewer VOC emissions and lower cost formulations can be used in EPA non attainment areas. 5 5

6. Butanol a Brief History
Acetone, Butanol, Ethanol (ABE) Process
First Industrial Fermentation Commercialized (1918)‏
Clostridium acetobutylicum bacteria
Acetone for Cordite
Later butanol for butyl paint & coatings (1930’s)‏
RAF planes flew on butanol during WWII
Petroleum based production becomes cheaper (1950s)‏
Fermentation of Clostridium for the production of acetone, n-buoh and etoh is the oldest industrial fermentative process.
Originally utilized for the production of acetone and smokeless gunpowder.
In the 1930s butanol’s value for paints and coatings was realized.
Production of butanol via ABE continued up until the 1950s when the modern petro-chemical industry was born.
China continues to use traditional ABE fermentation. 6 6

7. ABE Fermentation Reaction Kinetics
Although ABE is no longer current technology it forms the basis of many new bio routes to butanol.
Actually half a mixed acid fermentation: acetic, propionic, butyric. Metabolic shift conversion to acetone, butanol,
etoh. Traditionally in a 3:6:1 ratio A:B:E
Ramey & Yang 7 7

8. Problems w/Traditional ABE Process
Toxicity to the organism
Low product concentrations
Low yield
Toxicity to the organism (~1% concentration) impedes growth and product formation.
Low product concentrations mean high water separation costs,
Low yields increase size of all up front materials handling 8 8

9. Butanol Production From Petroleum (1950s-Present)‏
Production of Butanol by oxo Alcohol Process
Players & Market Share
US & Global Manufacturing Capacity
Price history of butanol, ethanol, gasoline
So what replaced ABE?
The creation of the modern petro-chemical industry created a new cost effective route to butanol. 9 9

10. Butanol Production From the oxo Process
At a refinery naptha is cracked to propylene
Propylene is the primary raw material and cost driver of n-buoh production.
The oxo process produces ~90% n-buoh and ~10% iso-buoh.
Global market for nbuoh is 3.8 M mtons/Yr
Global iso-buoh is ~ 0.4 M mtons/Yr
Metex 10 10

11. Market Share of Leading n-Butanol Producers
Biggest producers are German giant BASF and Dow Chemical.
Metex 11 11

12. Global Butanol Industry Capacity - Facility Cost Curve
Cash Cost ($ / mton)‏
Cost curve shows every butanol facility manufacturing capacity and cost of production.
Each bar is a facility. Width is capacity. Height is cost.
Least competitive plants (far right) are eastern European and Japanese plants.
Cumulative Capacity (K mtons)‏
Source: Tetra Vitae, SRI; company analysis
Assumptions: $70 oil, range of feedstock cost 12 12

13. Domestic Butanol Production Cumulative Capacity (K mtons)‏
DOMESTIC DEMAND
exports
Butanol Cash Cost
($ / mt)‏
Cumulative Capacity (K mtons)‏
Source: Tetra Vitae, SRI; company analysis
Assumptions: $70 Oil 13 13

14. Chemical Strategies, Inc.
Price of butanol is typically 2X-3X the price gasoline and ethanol.
Chemical Strategies, Inc. 14 14

15. The Future of Bio-Butanol Fuels
“Our goal is to build a supply chain from lignocellulose to butanol.”
Tony Hayward, CEO British Petroleum
So, who thinks there’s a business in butanol? 15 15

16. Summary Bio-Butanol Process Goals
Power & Price of Biotechnology Tools... systems biology, pathway engineering...
Over expression butanol
Suppression of other pathways
Organism tolerance
Improving yield
Increasing productivity (rate)‏
Flexible feedstocks
What’s changed to make biological processes competitive again? 16 16

17. Status Domestic Butanol Companies
Company
Bug
Bug Strategy
Molecule
Fermentation Process
Separation Strategy
Development Status
Gevo
Yeast
GMO UCLA Valine metabolism
iso-buoh
Semi batch
vacuum flash in situ removal followed by distillation trains
2010 Operating pilot in St. Johns, MO Commercial
Cobalt Biofuels
Clostridium
Non GMO strain reduced etoh and acetone
n-buoh for blending w/gasoline, diesel, jet
Continuous modified ABE Fermentation
vapor compression distillation
2010 pilot 10-35k gpy demo 2-5m gpy commercial
Tetra Vitae
Clostridium beijerinckii
Non GMO selected for reduced etoh production
n-buoh and acetone 2:1
Semi batch "AB" Fermentation
Carbon dioxide stripping continuous in situ removal followed by distillation trains
liter bench ,000 liter pilot
Butyl Fuel
Clostridiums Aceto & tyro
GMO & mutant strain
n-buoh
Continuous two stage dual path anaerobic fermentation
stripping following immobilized cell bioreactors
Unknown
Syngas Biofuels Energy
Fermentation of Syngas
GMO
Thermochemical catalyst NA 17 17

18. Status International Butanol Companies
Company
Bug
Bug Strategy
Molecule
Fermentation Process
Separation Strategy
Development Status
Butamax (DuPont/BP)‏
1.Clostridium 2.E.Coli
GMOs
iso-buoh
Semi batch
continuous in situ removal followed by distillation trains
2010 Salt End Hull, UK Commercial Additional Feedstocks 2013+
Green Biologics (UK)‏
Clostridium. Mixed populations
GMOs high tolerance (4%)‏
n-buoh
Continuous fermentation
In situ removal unknown.
Building demo in India. Consulting w/Chinese firms
Metex (FR)‏
"Well known bacteria“
Unkown
Unknown
Butalco (Switzerland)‏
Yeast
unclear
China
Clostridium
Currently selected strain. Migrating to GMOs
Migrating from traditional ABE Fermentation.
May include in situ removal
MM gpy traditional ABE X migration beyond ABE. Plans to add 350 MM gpy new capacity. 18 18

19. Bio-Butanol Projecting the 3rd Wave
An optimistic projection for the future of butanol manufacture and acceptance.
Some predict the entire petro chemical butanol market will be replaced with bio-butanol in 5 years.
Highly unlikely. 19
Green Biologics 19

20. Bio Iso-Butanol Fuel Commercialization Forecast
---$6bn chemicals
We are likely to see some ethanol facilities retrofitted by Gevo, Butamax and Cobalt.
It is very possible we will see 4 or 5 (80MM gallon plants) go online
They will initially sell into the chemicals market for isobutanol (and possibly n-buoh)‏
If the facilities are economical we will see them enter the fuels market within 10 years 20
Promotum 20

21. Thoughts on Butanol Adoption1
Pricing/Economics have to work
Markets for butanol, petroleum and sugar feedstocks change daily. 2
Avoid Food v. Fuel Round II
Butanol is a better alcohol, but for now corn is still the feedstock 3
Tax credits, biorefinery grants, loan guarantees
Need to be extended to butanol. Government and private investment are necc. 4
Enlist/Co-exist w/current ethanol producers
Infighting will slow production & adoption. Oil companies like BP (Butamax) may not be politically correct market driver. 5
Autos/Engine makers must approve
May be catalytic converter issues. Manufacturer's warrantees essential. 6
Consumer education
Higher energy content means a gallon isn't a gallon. Odor maybe a problem. 7
Technology improvements must continue
Anything beyond ethanol is new territory at this scale 21 21

22. Acknowledgements Jim Evangelow Chemical Strategies
Gorden Cheng ChemaLogic
Jay Kouba Tetra Vitae
Hans Blachek University of Illinois-Urbana
Adam Schubert Butamax
Ron Bray SRI Consulting 22 22

23. Thank You Sam Nejame Promotum 617.576.9084 Sam@Promotum.com
Twitter.com/renewables 23 23