original slides by: Drew Sowersby (May 2011) _technical contributor for Advanced Biofuels USA

original slides by: Drew Sowersby (May 2011) _technical contributor for Advanced Biofuels USA

Fuels of the FutureThe Bioalcohol Paradigm

CDC PHIL /James Gathany

yeast

ethanol

liquid fueladvanced biofuels phytomass

fermentation

lignocellulosic feedstocks

synthetic biology

branched-chainalcohols

bridge fuels

energy

www.AdvancedBiofuelsUSA.org

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

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.

1. Energy: The Root of All Civilization

2. Why Bioalcohols? Blending Bridges to Sustainability

3. Leaping Barriers: Squeezing the Sun

Section 1

Energy: The root of all civilization

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?

In the beginning there was…..biofuels?

In this section the ongoing energy crisis can be visualized in a series of graphs depicting the startling connection between:

1. Energy Consumption2. GDP per capita (prosperity)3. Population growth4. Debt (deficit spending)

chart by : http://perotcharts.com/2008/05/growth-of-us-population-1790-2050/

http://8020vision.com/2010/06/21/the-real-population-problem/

U.S. Energy Information Administration (Washington, DC, June 2009) Projections: AEO2010 National Energy Modeling System

1980 1995 2008 2020 20350

20

40

60

80

100

120

Renewables

Liquids

Biofuels

Natural gas

Nuclear

Coal

Projections

U.S. primary energy use by fuel (1980-2035) 1.

0 ×

1015

Btu 40%

Breakdown of the U.S.liquid fuel market

• 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

1. Energy Information Administration, Annual Energy Review 2008, Petroleum Consumption: Transportation Sector, 1949-2008. 2009, U.S. Department of Energy, Washington, D.C

2. O’Donnell, M. Master’s Thesis, University of Texas at Austin, 2009

Global transportation energy consumption vs. GDP in 2006

graph from: http://environmentalresearchweb.org/blog/2009/07/high-debt-and-energy-return-on.html

Energy and Economic Interconnectedness

http://tclocal.org/images/failure-feedback.jpg

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.

Why Bioalcohols?Blending Bridges to Sustainability

Section 2

In contrast to fossil fuels, biofuels….1. Are sustainable (1-100 yrs vs. 106-108 yrs)2. Can be carbon neutral or negative3. Have a more diversified, distributed means of

production4. Can be created as reagent grade molecules (pure)

Biofuels are any biologically derived solid, liquid, or gas that stores energy used in combustion applications.

What are biofuels?

BiowasteBiocrude

Bioalcohol

Biogasoline (grassoline)

Biogas

Biodiesel

BIOFUELTYPES

Biomass

Commercially availableMethanol

Natural Gas Propane

Biodiesel Electricity Ethanol

Hydrogen

Under investigation and developmentBiobutanol

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)

Alternative Transportation Fuels

Source: The Energy Policy Act (EPAct) of 1992

biomass

biofuels

adapted by: Drew Sowersby

conversion

Milli

on B

arre

ls pe

r Day

chart by: http://tclocal.org/images/eia-liquidfuels.jpg

Source: U.S. Department of Energy’s Energy Information Agency (EIA).

Global biofuel supplies expected to increase dramatically

BP p.l.c., Statistical Review, BP Energy Outlook 2030, London, January 2011

Milli

on b

arre

ls da

y less than 2% of totalliquid consumption

more than 90% of all carsuse sugarcane ethanol

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…

The evolution of biofuels is defined in terms of the carbon feedstock used for production

CO2impact factor

net 0

(medium to high lignin content)

(low to no lignin)

The BioalcoholParadigm

biomass

sugarfeedstocks

fermentation

product recoverymarket 1

chemical Storagemarket 2

market 3

Bioalcohols currently dominatecommercially available biofuels

http://www.vsjf.org/project-details/13/biomass-to-biofuels-resources

Biomass to Biofuels

biomass bioalcohols process generalization

Lignocelluloses represent the most abundant source of bioenergy

Rubin, E. Nature, 2008, 454, 841-845.

Glucose

Treatment with cellulases and/or acids releases glucose monomers for fermentation

Most cellulosic material, like woods and grasses, contains lignin

1. Liu, Z. L.; Slininger, P. J.; Gorsich, Appl Biochem. Biotechnol., 2005, 124, 451-460.

organic acids

phenols

aldehydes

ketones

CLASSES of inhibitors

But lignocellulosic feedstocks are not easily converted to sugar substrate and can introduce over 100 inhibitors into fermentation batches1

The yeast cell factory has been used by humans for over 8000 years to create a host of useful

renewable products

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)

insulin

lactic acid

carotenoids

alcohols

carbon dioxide

polymer precursors

So far, Saccharomyces cerevisiae have demonstrated the ability to perform with a

lignocellulosic feedstock.

Ehr

lich

Path

way

Glucose

PyruvateO2

Glycolysis(regulated and irreversible steps)

CO2 + H2O respiration

Fermentation

amino acid synthesis

CO2 + CH3CH2OH

Standard fermentation in yeast

Higher alcohol synthesis

Ketoaldehydes+

CO2

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.

2MB2MP

3MB

(leucine, valine, isoleucine)

2-Keto acids

Ehrlich Pathwaybranched-chain alcohol synthesis

Yeast cells naturally create C4 and C5 alcohols using fermentation enzymes

superior alcohol fuel surrogates

Nitrogen Source

Gases (CO2 and O2)

Water

Excess sugar

Ionic Strength

pHInhibitors

Viscosity

Fluid Motion

Temperature

Biocatalyst

Fermentation as a complex adaptive system

Hypothetical Interaction Map

Isobutanol (2MP) is a viableplatform molecule

conventional motorgasolineisobutanol

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.

C4-C5 Alcohol Platform

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)

HighlightsAfter 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

ButylFuel, LLC

C4-C5 alcohols have advantagescompared to ethanol

higher energy density lower vapor pressure lower air/fuel ratio less corrosive less hygroscopic higher gasoline blend ratios

o “drop-in” fuel compatible with gasoline engines,

existing storage facilities, and distribution infrastructure

1. Harvey, B. J.; Meylemans, H. A. J Chem Technol Biotechnol., 2011, 86, 2–9.2. Dürre, P. Biotechnol. J., 2007, 2, 1525-1534.

Fuel Cn

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 275-475Ethanol 2 21 78 miscible 59

2-methyl-1-propanol* 4 26 108 95 9

3-methyl-1-butanol 5 28 130 30 2

2-methyl-1-butanol 5 28 128 36

(at 30°C ) 3

--information obtained from MSDSs, Sigma-Aldrich website, and NIST chemistry WebBook.* a.k.a. isobutanol ~ 1-butanol

Selected bioalcohol and gasoline properties

Liquid Fuel Energy DensitiesM

J/L

MJ/kgAdapted by Drew SowersbySource:Scott dial http://en.wikipedia.org/wiki/File:Energy_density.svg

butanol/pentanol sweet spot?

Right now fuel blends are showing up at pumps across the U.S.

E10 o Up to 10% ethanol to replace MTBE

E15 - E85o contains 15% to 85% ethanolo requires post 2001 or Flexfuel engine

technology

B20o contains 20% biodiesel / 80% dieselo made commercially from soybeans

How long until we see C4 and C5 advanced alcohols at the pump?

BRIDGE FUELS

Section 3

Leaping Barriers:Squeezing the Sun

The Obstacle CourseIt 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.

Technical Barriers

Low cropenergy density

Kerr, R. Science, 2010, 329, 780-781

Supply continuity

Geographic distribution

Sheer size required for economic

growth

GOAL

START

The Bright SideThe 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

http://pvcdrom.pveducation.org/SUNLIGHT/AVG.HTM

≈ 4.00 peak sun hours avg./day11 peak sun hour = 3.6 MJ

14.4 MJ/(m2)day × 365 days × 9.83 × 1012 m2

≈ 5.20 × 1016 MJ/year

1 MJ = 994.78 Btu

≈ 4.90 × 1019 Btu/year

1. Solar Radiation Data Manual for Flat-Plate and Concentrating Collectors National Renewable Energy Laboratory (NREL), 2006

U.S. example?

US land area

this is roughly 500X the current amount of US energy usage

≈ 2.00-3.00 peak sun hours/day

7.2 MJ/(m2)day × 365 days × 5.14 × 1014 m2

≈ 1.35 × 1018 MJ/year

≈ 1.28 × 1021 Btu/year

Earth?

“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.” -- http://cee.illinois.edu/cai_biofuel_land

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.

What will the next transition be?

Paradigm Shiftstandard fermentation

toadvanced fermentation

2nd generationbiofuels

1st generationbiofuels

NON-FOOD crops and waste/residues

FOOD crops

CO2 and the SUN

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: http://advancedbiofuelsusa.info/resources/companies-involved-with-advanced-biofuels

Find out more at www.AdvancedBiofuelsUSA.org