1. The Bioalcohol Paradigm
Fuels of the Future
The Bioalcohol Paradigm
yeast
ethanol
liquid fuel
advanced biofuels
phytomass
fermentation
lignocellulosic
feedstocks
synthetic biology
main topics
branched-chain
alcohols
bridge fuels
energy
CDC PHIL /James Gathany
original slides by: Drew Sowersby (May 2011)
_technical contributor for Advanced Biofuels USA

2. Message to the reader
The following slide document has been created to inform a broad audience about the importance and likely dominance of bioalcohols in the transportation industry as the global transition from non-renewable fossil fuels to renewable advanced biofuels gains momentum. The information contained in these slides stands in support of the Advanced Biofuels USA mission.
“The Mission of Advanced Biofuels USA is to promote public understanding, acceptance, and use of advanced biofuels by promoting research, development and improvement of advanced biofuels technologies, production, marketing and delivery; and by promoting the sustainable development, cultivation and processing of advanced biofuels crops, and agricultural and forestry residues and wastes.”
These slides are for public consumption and can be duplicated, replicated, modified, adapted, distributed, transmitted, and/or shared as seen fit by the reader. Please credit sources accordingly. If you wish to modify this document, just add your name under mine on the first slide.
Note: Some slides contain additional information in notes section below

3. Energy: The Root of All Civilization 2. Why Bioalcohols?
Concerted efforts from scientists, farmers, politicians, and grassroots organizations like Advanced Biofuels USA to understand and advocate for sustainability are ongoing. Most of us are seeking the promise of global security, the development of a sustainable workforce, and an endless supply of clean renewable energy.
Converting biomass to biofuels for transportation fuel applications is currently one of the most active areas of investigative research in science and engineering. The following sections will offer an in-depth technical perspective of liquid fuels and demonstrate the overriding potential of bioalcohols to bridge transportation energy needs of modern society with the future of the human race.
Energy: The Root of All Civilization
2. Why Bioalcohols?
Blending Bridges to Sustainability
3. Leaping Barriers: Squeezing the Sun

4. The root of all civilization
Section 1
Energy:
The root of all civilization
This section will connect energy to GDP and population size to illustrate the rise of human civilization and prosperity.

5. In the beginning there was…..biofuels?
1 EJ = 1018 J
The post civil war exploitation of coal helped spawn the Industrial Age, while the subsequent incorporation of crude-oil and natural gas fossil resources helped spawn what has become a global economy. Is this pattern sustainable? Most believe the answer to this question is NO! Why?

6. In this section the ongoing energy crisis can be visualized in a series of graphs depicting the startling connection between:
Energy Consumption
GDP per capita (prosperity)
Population growth
Debt (deficit spending)

7. Almost a vertical slope!

8. And the United States population has been growing dramatically
And the United States population has been growing dramatically. Projections indicate that the US could have a population over 400 million by To sustain such a state given our free market culture would require much more energy or a breakthrough in energy conservation technology (smart grid).
chart by :

9. The fossil fuel dynasty has really just began, and yet it may already be more than half over.

10. U.S. primary energy use by fuel (1980-2035)
1.0 × 1015 Btu
40%
1.0 × 1015 Btu equals a 1 quadrillion Btu (a quad). Most energy data is reported in Btu (British Thermal Units).
U.S. Energy Information Administration (Washington, DC, June 2009)
Projections: AEO2010 National Energy Modeling System

11. Breakdown of the U.S. liquid fuel market less than 3% biofuels
35 quadrillion Btu’s (37 EJ) of liquid energy annually
~ 95% of all liquids since 1958 have come from petroleum 1
63% of refined petroleum was delivered to market as motor gasoline for transportation2
less than 3% biofuels
Energy Information Administration, Annual Energy Review 2008, Petroleum Consumption: Transportation Sector, , U.S. Department of Energy, Washington, D.C
O’Donnell, M. Master’s Thesis, University of Texas at Austin, 2009

12. Global transportation energy consumption
vs. GDP in 2006
A more specific look at transportation vs. prosperity. Many questions arise from this graph. For example, can the US sustain population growth, energy consumption, increasing debt, and a strong GDP growth?

13. World energy use approaches 500 quadrillion Btu’s, of which the US consumes approximately 1/5.
graph from:

14. Prosperity (GDP) correlates strongly with energy use
Prosperity (GDP) correlates strongly with energy use. We know that China has benefited greatly from US prosperity, but most of its vast population doesn’t use much energy. Prosperity (GDP) correlates strongly with energy use. We know that China has benefited greatly from US prosperity, but most of its vast population doesn't use much energy. Liquid fuel energy for transportation is a key driver of energy expansion and China will need much more of it as they expand their transportation and industrial sectors. Knowing the technical difficulties we are currently experiencing, once again this pattern is visibly unsustainable and it also appears the US has much to lose.

16. Energy and Economic Interconnectedness
This diagram depicts the feedback loops between an economy that is dependent on an aging oil industry.
Energy and Economic
Interconnectedness

17. Summary
It appears there exists a positive correlation between energy consumption, population growth rate, GDP, and the abstractions of expanding debt and monetary instability. So now what?
We must now consider alternatives to the current trends of fossil fuel dependence and moves toward sustainability. The next section will discuss the biofuels option with an in-depth analysis of the bioalcohol paradigm.

18. Blending Bridges to Sustainability
Why Bioalcohols?
Blending Bridges to Sustainability
Section 2

19. What are biofuels? In contrast to fossil fuels, biofuels….
Biofuels are any biologically derived solid, liquid, or gas that stores energy used in combustion applications.
In contrast to fossil fuels, biofuels….
Are sustainable (1-100 yrs vs yrs)
Can be carbon neutral or negative
Have a more diversified, distributed means of production
4. Can be created as reagent grade molecules (pure)

20. Bioalcohol Biodiesel BIOFUEL TYPES Biogas Biocrude Biowaste
Biogasoline (grassoline)
Biogas
Biodiesel
BIOFUEL
TYPES
Biomass

21. Commercially available Under investigation and development
Alternative Transportation Fuels
Commercially available
Methanol
Natural Gas
Propane
Biodiesel
Electricity
Ethanol
Hydrogen
Under investigation and development
Biobutanol
Fischer-Tropsch (FT) diesel
Gas to Liquids (GTL)
Biogas Biomass to Liquids (BTL)
Coal to Liquids (CTL)
Hydrogenation-Derived Renewable Diesel (HDRD)
P-Series (gasoline substitute)
Source: The Energy Policy Act (EPAct) of 1992

22. adapted by: Drew Sowersby
biofuels
conversion
biomass
Historical reminder of expansive energy consumption in the US ( ) and almost non-existent impact of biofuels. There is a very high mountain to climb for biofuels to replace fossil fuels. Before fossil fuels were available, humans relied almost 100% on biofuels (mostly wood for burning and feed for working animals such as horses, oxen, llamas, etc.) and human energy.
adapted by: Drew Sowersby

23. Source: U.S. Department of Energy’s Energy Information Agency (EIA).
Million Barrels per Day
chart by:
Source: U.S. Department of Energy’s Energy Information Agency (EIA).

24. Global biofuel supplies expected to increase dramatically
less than 2% of total
liquid consumption
Million barrels day
more than 90% of all cars
use sugarcane ethanol
BP p.l.c., Statistical Review, BP Energy Outlook 2030, London, January 2011

25. The evolution of biofuels is defined in terms of the carbon feedstock used for production
1st generation fuels
corn-starch
sugar from cane and beets
soy for diesel
2nd generation – multi-component cellulose
switchgrass
miscanthus
agriculture and food processing residues
poplar trees
3rd generation – high quality cellulose
microalgae
macroalgae (seaweed)
cyanobacteria
4th generation - sun fuels
carbon dioxide + light + biocatalyst…
CO2
impact factor
(medium to high lignin content)
(low to no lignin)
net 0

26. Bioalcohols currently dominate commercially available biofuels
biomass
sugar
feedstocks
fermentation
product recovery
market 1
chemical Storage
market 2
market 3
The Bioalcohol
Paradigm

27. Biomass to Biofuels
The process of biofuels production begins with the sun. Several crops with different properties can be grown in various climates and harvested as a feedstock for biofuels production. An array of processing and engineering techniques are used to convert or extract the biomass and produce energy for electricity, heat, and transportation. Notice that cellulosic ethanol, a second generation advanced biofuel, along with biodiesel represent the baseline targets for implementation into the liquid fuel chain. It is implied that many jobs will be created at each of these steps….and all are sustainable.

28. process generalization
biomass
bioalcohols
This is a basic (although already extremely complex) process for creating 2nd generation biofuels from cellulosic biomass. Essentially, most bioalcohols are produced via a very similar pathway. In addition, a gasification process can be used instead of the pre-hydrolysis and hydrolyse steps before fermentation.

29. Most cellulosic material, like woods and grasses, contains lignin
Lignocelluloses represent the most abundant source of bioenergy
Glucose
Treatment with cellulases and/or acids releases glucose monomers for fermentation
Rubin, E. Nature, 2008, 454,

30. But lignocellulosic feedstocks are not easily converted to sugar substrate and can introduce over 100 inhibitors into fermentation batches1
organic acids
phenols
aldehydes
ketones
CLASSES of inhibitors
Liu, Z. L.; Slininger, P. J.; Gorsich, Appl Biochem. Biotechnol., 2005, 124,

31. So far, Saccharomyces cerevisiae have demonstrated the ability to perform with a lignocellulosic feedstock.
insulin
lactic acid
carotenoids
alcohols
carbon dioxide
polymer precursors
Advantages
Are the most common microorganisms
used for production of biofuels
(primarily alcohols)
Are eukaryotic
Have simple nutrient requirements
Are prime targets for bioengineering
Convert glucose to ethanol with
unusual efficiency (FERMENTATION)
The yeast cell factory has been used by humans for over 8000 years to create a host of useful renewable products

32. Higher alcohol synthesis
Ehrlich Pathway
Glucose
Pyruvate O2
Glycolysis
(regulated and irreversible steps)
CO2 + H2O respiration
Fermentation
amino acid synthesis
CO2 + CH3CH2OH
Standard fermentation in yeast
Higher alcohol synthesis

33. BCAAs
Branched-chain alcohols
decarboxylation
(step 2)
NADH-dependent reduction
(step 3)
transamination
(step 1)
BAT1, BAT2
PDC1, PDC2, PDC3, PDC5, PDC6, ARO10, THI3 (KID1)
ADH1, ADH2, ADH3, ADH4, ADH5, ADH6, SFA1, etc.
2MB
2MP
3MB
(leucine, valine, isoleucine)
2-Keto acids
Yeast cells naturally create C4 and C5 alcohols using fermentation enzymes
Ehrlich Pathway
branched-chain alcohol synthesis
superior alcohol fuel surrogates
Ketoaldehydes +
CO2

34. Fermentation as a complex adaptive system
Nitrogen Source
Gases (CO2 and O2)
Water
Excess sugar
Ionic Strength pH
Inhibitors
Viscosity
Fluid Motion
Temperature
Biocatalyst
Hypothetical Interaction Map

35. Isobutanol (2MP) is a viable
platform molecule
conventional motor
gasoline
isobutanol
GEVO, Inc.
Highlights
High yield isobutanol yeast fermentation (105 g/L per batch)
Conversion to hydrocarbons
Carbon emissions reduction of 85%
Competes with oil at $65 a barrel
source: GEVO, Inc.

36. C4-C5 Alcohol Platform ButylFuel, LLC Highlights Case Study:
After logging 10,000 miles butanol….
increased auto mileage by 9%
reduced oxides of nitrogen by 37%
reduced carbon monoxide to 0.01%
reduced hydrocarbons by 95%
first American company to commercialize butanol
Case Study:
“Production of Butyric Acid and Butanol from Biomass”
Ramey D and Yang S-T, Phase II STTR Final Report for D.O.E. (2004)

37. C4-C5 alcohols have advantages
compared to ethanol
higher energy density
lower vapor pressure
lower air/fuel ratio
less corrosive
less hygroscopic
higher gasoline blend ratios
“drop-in” fuel
compatible with gasoline engines,
existing storage facilities, and
distribution infrastructure
Harvey, B. J.; Meylemans, H. A. J Chem Technol Biotechnol., 2011, 86, 2–9.
Dürre, P. Biotechnol. J., 2007, 2,

38. Selected bioalcohol and gasoline properties FuelCn
Energy density
(MJ/L)
Boiling point (°C )
Solubility in water at 20°C
(g/L)
Vapor pressure at 20°C (mm Hg)
Gasoline
4-12 33
38-204
negligable
Ethanol 2 21 78
miscible 59
2-methyl-1-propanol* 4 26
108 95 9
3-methyl-1-butanol 5 28
130 30
2-methyl-1-butanol
128 36
(at 30°C ) 3
Butanols have 4 carbons per molecule and pentanols have 5.
miscible = fully mixed or homogeneous
Cn = carbon atoms per molecule
MJ/L = mega joules per liter
mm/Hg = millimeters of mercury
--information obtained from MSDSs, Sigma-Aldrich website, and NIST chemistry WebBook.
* a.k.a. isobutanol ~ 1-butanol

39. Liquid Fuel Energy Densities
MJ/L
butanol/pentanol
sweet spot?
C4 alcohols such as 1-butanol (or isobutanol) have a lower knock-index, and burn more efficiently and cleanly than gasoline. C5 pentanols such as 3-methyl-1-butanol have not been thoroughly tested for combustion properties but are expected to behave similarly to 1-butanol.
MJ/kg
Source:Scott dial
Adapted by Drew Sowersby

40. Right now fuel blends are showing up at pumps across the U.S.
BRIDGE FUELS
E10
Up to 10% ethanol to replace MTBE
E15 - E85
contains 15% to 85% ethanol
requires post 2001 or Flexfuel engine technology
B20
contains 20% biodiesel / 80% diesel
made commercially from soybeans
How long until we see C4 and C5 advanced alcohols at the pump?

41. Section 3
Leaping Barriers:
Squeezing the Sun

42. The Obstacle Course
It would be irresponsible to assume that human energy needs will be fulfilled in a timely fashion. The transition to sustainable energy will likely be a long arduous process.
Moore’s Curse and the Great Energy Delusion (The American Magazine, November 19, 2008)
“There is one thing all energy transitions have in common: they are prolonged affairs that take decades to accomplish, and the greater the scale of prevailing uses and conversions the longer the substitutions will take. The second part of this statement seems to be a truism but it is ignored as often as the first part: otherwise we would not have all those unrealized predicted milestones for new energy sources.”
- Vaclav Smil-Distinguished Professor at the University of Manitoba.

43. Sheer size required for economic growth Geographic distribution
Technical Barriers
GOAL
Sheer size required for economic growth
Geographic distribution
START
Supply continuity
Low crop
energy density
Kerr, R. Science, 2010, 329,

44. The Bright Side The sun delivers about 1000 W/m2
of power to Earth’s surface.
1000 Wh = 1 kWh = 3.6 mega Joules (MJ)
peak sun hour = 1 kWh
peak sun hours per day based on geo location

45. U.S. example? ≈ 5.20 × 1016 MJ/year ≈ 4.90 × 1019 Btu/year
≈ 4.00 peak sun hours avg./day1
1 peak sun hour = 3.6 MJ
14.4 MJ/(m2)day × 365 days × 9.83 × 1012 m2
≈ 5.20 × MJ/year
1 MJ = Btu
≈ 4.90 × 1019 Btu/year
U.S. example?
US land area
this is roughly 500X the current amount of US energy usage
1. Solar Radiation Data Manual for Flat-Plate and Concentrating Collectors
National Renewable Energy Laboratory (NREL), 2006

46. Earth? ≈ 1.35 × 1018 MJ/year ≈ 1.28 × 1021 Btu/year
≈ peak sun hours/day
7.2 MJ/(m2)day × 365 days × 5.14 × 1014 m2
≈ 1.35 × MJ/year
≈ 1.28 × 1021 Btu/year

47. “Using detailed land analysis, Illinois researchers have found that biofuel crops cultivated on available land could produce up to half of the world's current fuel consumption – without affecting food crops or pastureland. Adding LIHD (low input high density) crops grown on marginal grassland to the marginal cropland estimate from earlier scenarios nearly doubled the estimated land area to 1,107 million hectares globally, even after subtracting possible pasture land – an area that would produce 26 to 56 percent of the world's current liquid fuel consumption.”
Published in the journal Environmental Science and Technology, the study led by civil and environmental engineering professor Ximing Cai identified land around the globe available to produce grass crops for biofuels, with minimal impact on agriculture or the environment.

48. What will the next transition be?
Paradigm Shift
standard fermentation to
advanced fermentation
2nd generation
biofuels
1st generation
NON-FOOD crops and waste/residues
FOOD crops
CO2 and the SUN

49. Taking Us from the Present to the Future
Many companies are engaged in making these transitions happen. See a list of more than 400 companies in the Resources section on the Advanced Biofuels USA web site: Find out more at