biofuels research opportunities/needs georgia institute of ...biorefinery.utk.edu/posters/thursday...

BioFuels Research Opportunities/Needs

Georgia Institute of TechnologySchool of Chemistry and Biochemistry

Art J. Ragauskas

19001910 1920 1930 1940 1950 1960 1970 1980 1990 2000 2005 2010

0

50

100

150

200

250

300

Brief Biofuels: History

1898 Rudolph Diesel demonstrated his compressionignition engine at the World's Exhibition in Paris with peanut oil

1908 Henry Ford’s Model T was powered by ethanol generated from bioethanol plants he owned in the midwest was partnered with Standard Oil

Bioethanol Biodiesel

Giant Oil Field DiscoveryBillion BBls/Decade

Million BBls/day

G. W. Bush 2006 State of Union Address “America is addicted to oil, which is often imported from unstable parts of the world. The best way to break this addiction is through technology…”.

Brief Biofuels: Perspective

Energy/Transportation Fuels

Costs Options

Modern LifestyleEconomy

Environment

Benefits

Brief Biofuels: Perspective

0

1000

2000

3000

4000

5000

6000

7000

1980 1982 1984 1986 1988 1990 1992 1994 1996 1998 2000 2002 2004 2012

U.S.A. Bioethanol MM Gal. Annual

US: Currently Bioethanol 2%Biodiesel 0.01%

BioFuel Resources• USA - Corn• Brazil – Sugar Cane• Europe – Sugar beet, Potato

Rapeseed/sunflower

Reference

87% Reduction in MTBE

Cellulose Ethanol Credit

5 additional Northeast States Ban MTBE

14 States Ban MTBEStarting in 2004

Total Renewable Fuels Consumption for Transportation Three Cases, 2003-2020 (Billion Gallons/Year)

S.517

2003 2006 2012 2020

RFS Schedule6

5

4

3

2

1

0

Reference

87% Reduction in MTBE

Cellulose Ethanol Credit

5 additional Northeast States Ban MTBE

14 States Ban MTBEStarting in 2004

Total Renewable Fuels Consumption for Transportation Three Cases, 2003-2020 (Billion Gallons/Year)

S.517

2003 2006 2012 2020

RFS Schedule6

5

4

3

2

1

0

Methyl tert-butyl ether (MTBE) Additive in unleaded gasoline.

Biofuels FutureBiomass Resources

OHO

HO

OH

OH

OH

Today Amylase Yeast

H3C

H2C

OH

OHO

HO

OH

OH

OH

Today Amylase Yeast

H3C

H2C

OH

OHO

HO

OH

OH

OH

OHO

HO

OH

OH

Future Biomass

AcidCatalyst

orEnzymes

Fermentation

H3C

H2C

OH


OO

O OAcO

O

HOOAc

O

HOO

OO

AcOOH

O-XylanO

O

HOOAc

OO

AcOOAc

O

O

HO

HO

OHO

OHO

HO OH

HO

O

O

HO

OH

O

O

O

H3CO

OH

OH

OH

OO

HOOH

OO

HOOH

OH

OH

O

HOOH

OO

HOOH

O

OH

OH

O

OH

OH

OCH3HO

OCH3

O

HO

HO

H3COO

HO

HO OCH3

O

HOOCH3

OHO OH

OOH3CO

HO

HO

O

OH

OH

OCH3

OCH3

OH

OH

OOCH3

OO

OCH3

O

OCH3

HO

HO

OCH3

O

O

OCH3

HOO

HO

HO

OCH3

Lower Cost Higher AvailabilityNo Competition with Food Demand

Lignin

PolymerDerived from

MajorGlobal

Biopolymers

HemiCellulose

Short chainbranched,substituted

polymer of pentosesand hexoses

Degree of Polymerization ~70 - 200

Cellulose

Polymer of β-(1,4)-glucan

Degree of Polymerization~300 – 15,000

O

HOOH

OH

OH

HO

OHOHOH

OH

OCH3

OH

H3CO

OH

OCH3

Production:~ 35 – 50%

OHO

HOOH

OH

OH

OHO

HO

OH

OH

OH

O

OH

HOOH

OH

OH

OHO

HOOH

OHO

OH

HOOH

OH

Prod

uctio

n: ~

20

- 30%

Production: ~ 15 –30%

Lignin

PolymerDerived from

MajorGlobal

Biopolymers

HemiCellulose

Short chainbranched,substituted

polymer of pentosesand hexoses

Degree of Polymerization ~70 - 200

Cellulose


Degree of Polymerization~300 – 15,000

O

HOOH

OH

OH

HO

OHOHOH

OH

OCH3

OH

H3CO

OH

OCH3

Production:~ 35 – 50%

OHO

HOOH

OH

OH

OHO

HO

OH

OH

OH

O

OH

HOOH

OH

OH

OHO

HOOH

OHO

OH

HOOH

OH

Prod

uctio

n: ~

20

- 30%

Production: ~ 15 –30%


Lignin

PolymerDerived from

Coniferyl, Coumaryl,Sinapyl, Alcohol

Major Global Biopolymers Hemi

Cellulose

Short chainbranched,substitutedpolymer of sugarsDP: ~ 70 - 200

Cellulose


DP: ~300 – 15,000

Content: ~ 35 – 50%

Cont

ent:

~ 20

-30

%

Content: ~ 15 –30%

Lignin

PolymerDerived from

Coniferyl, Coumaryl,Sinapyl, Alcohol

Major Global Biopolymers Hemi

Cellulose

Short chainbranched,substitutedpolymer of sugarsDP: ~ 70 - 200

Cellulose


DP: ~300 – 15,000

Content: ~ 35 – 50%

Cont

ent:

~ 20

-30

%

Content: ~ 15 –30%

BioResource % ∼ Lignin Hemicellulose CelluloseSoftwood 27 28 39Hardwood 25 30 40Corn Stover 18 22 38Wheat Straw 23 21 38Fine Paper - 20 80Switch Grass 18 21 31

Need to utilize all Bioresources BioPolymers

Biofuels FutureIntegrated Biorefinery

The Path Forward for Biofuels and Biomaterials. Ragauskas, A.J.; Williams, C.K.; Davison, B.H.; Britovsek, G.; Cairney, J.; Eckert, C.A.; Frederick, W.J., Jr.; Hallett, J.P.; Leak, D.J.;

Liotta, C. L.; Mielenz, J.R.; Murphy, R.; Templer, R.; Tschaplinski, T. Science (2006), 311(5760), 484-489

The biorefinery is facility that integrates biomass conversion processes and equipment to produce fuels, power, and chemicals from biomass. It fully

utilizes all components of biomass to make a range of foods, fuels, chemicals, feeds, materials, heat and power in proportions

that maximizes sustainable economic development.

Imperial College Georgia Institute Oak Ridge NationalLondon of Technology Laboratory

Biofuels Research Challenges: Plant Science

• ~ 8 dry Mg Ha-1 yr-1 for willow in Sweden to 10-22 dry metric tons per hectare yr-1 in U.S.for short-rotation woody crops, commercial plantations in Brazil up yo 20 dry Mg ha-1 yr-1.

• Manipulating photosynthesis genes to increase the initial capture of light energy• Manipulation of genes involved in nitrogen metabolism• Overexpressing a Glutamine Synthase (GS1) gene transgenic poplar, tree height increased to 41% greater than control plants

• Repressing a single lignin biosynthetic gene, 4 CL, resulted in a reduction in lignin content with a concomitant increase in cellulose

“More, Bigger, Better;” the mantra of modern consumerism, ironically, summarizes the goals of research aimed at modifying plants for use in sustainable biomass production

Research Objective

Biofuels Research Challenges: Plant Science

• Lignin biosynthetic gene CCR is downregulated in poplar, the cellulose component of theplant cell wall is more easily digested by the bacterium Clostridium cellulolyticum, and twiceas much sugar is released

• Enhanced plant oils, waxes, naval stores• Endogenous production of polysaccharide hydrolyase enzymes could also be coupled withenhanced plant biomass production made possible by recent advances in molecular farming

> Soil productivity/management> Collection systems

“More, Bigger, Better;” the mantra of modern consumerism, ironically, summarizes the goals of research aimed at modifying plants for use in sustainable biomass production

Research Objective

BioFuels Research Challenges Conversion

Efficient Depolymerization of Cellulose – Glucose• Biomass Pretreatments

– Conventional, Organic Solvents, Steam Explosion– Ionic Liquids, Nearcritical Water, Gas Expanded Liquids

• Acid Catalyzed Hydrolysis of Cellulose– Catalysis– Conditions– Reduction/elimination of fermentation inhibition by-

products

Bioethanol <<<< Glucose <<<< Cellulose << Biomass

Biofuels Research Challenges:Biomass Characterization

Enhanced biomass production/ acre by reducing perception of

nearest neighbor by manipulating photomorphogenic responses of

phytochrome Red/FR light perception system

Greater carbon allocation to stem diameter vs. height growth

Less extensive root system to maximize aboveground biomass

Optimal nitrogen acquisition and use

Increased photosynthesis Optimized photoperiod response

Optimized crown/leaf architecture

Regulated dormancy Delayed leaf senescence

Pest/disease resistance, Drought/cold tolerance

Floral sterility

Controlled and readily processable cellulose, hemicellulose, and lignin. Tailored biomass composition with value-added chemicals

Need for Rapid, Inexpensive Detailed Topochemical Characterization of Biomass Initial/Processed• Cellulose – Structure, DP, Ultrastructure, Location • Hemicelluloses – Chemical constituents, Structure, DP, Location• Lignin - Chemical constituents, Structure, DP, Location• Extractives - Structure

φφ

OCHOCH33

φφ--OHOH

C=OC=ORORROR

DMSODMSO

φφ--CHCH22--φφ

φφ

OCHOCH33

φφ--OHOH

C=OC=ORORROR

DMSODMSO

φφ--CHCH22--φφ1100.0 1500 2000 2500.0

0.00

0.1

0.2

0.3

0.4

0.50

NM

A

Advanced SpectroscopicBio-Analysis – High Volume

ComputationalData Analysis

800 1000 1200 1400 1600 1800 2000

m/z

Biofuels Research Challenges: Separations

Extraction of Value Added Chemical• Neutraceuticals• Drugs• Bioactive agents

HO

H

Pine Sitostanol

BioFuels• Ethanol • Butanol• Dimethyl ether • Biodiesel • BiogasolineWang et al.

Argonne 1999

Value Added Materials• Nanocellulose/hemicellulose • Lignin for carbon fibers• Chemicals/Polymers

DOE


Efficient Depolymerization of Cellulose – Glucose• Cellulase Hydrolysis of Cellulose

– Enhanced thermostability– Improved hydrolysis– In-situ Expression– Cellulose ultra-structure

Bioethanol <<<< Glucose <<<< Cellulose << Biomass

NREL


Bioethanol <<< C6/C5 Sugars <<< Hemicellulose << Biomass

C6 C5 Fermentation Research Issues:• Minimize fermentation inhibitors suchas furans, phenolics, carboxylic acids

• Ability to efficiently ferment C6 and C5 sugars

• Manipulate ethanol and sugar tolerancefermentation

OO

HOOH

OO

HO

OHOH

OH

O

HOOH

OO

HO

OHOH

OH

O

OO

HOOH

OO

HO

OHO

OH

O

AcO

OH

OO

HO

OHOH

OH

O

O

HO HO

OH

HO

OO

O OAcO

OHO

OH OHO

OO

OHO

OAcO-XylanOHO

OO

OH

O

H3CO HO

OHHO2C O

OHO

OHO

H3CO OH

AXE

AXE

α-L-arabinofuranosidaseFeruloyl Esterase

OO

O OHO

OHO

OH OHO

OHO

OHO

OHO-XylanO

HOO

OOH

O

H3CO HO

OHHO2C

Endoxylanaseβ-Xylosidaseα-D-glucuronidase

OH

OHHO

OHO

OHOH3CO

HOOH

CO2H


OO

HOOH

OO

HOOH

OH

OH

O

HOOH

OO

HOOH

O-Cellulose

OH

OH

O

n: 150 - 7500

O

HOOH

O

OH

HO

H

Cellulase

C6(H2O)6

Loss of H2O

OHO

O

+ other organic acids

O

O

OH

Polymers

Loss of CO2 and H2O

Potential CatalyticO

O

O

H2O

Chemical Pathway to Fuel Precursors Sugar Research Needs• Decarboxylation Catalyst• Dehydration Catalyst• Hydrogenation Catalyst

Lignin Research Needs• Depolymerization Catalyst• Hydrodeoxygeneation Catalyst

C10 – C22


BiomassBiomaterials – Biochemicals (Waste)

Biofuels (Waste)

Gasification

PowerHeatElectricity

SyngasCO + H2

Methanol

H2OWGSPurify

H2N2 over Fe/FeO

(K2O, Al2O3, CaO)NH3

Cu/ZnOIsosynthesis

ThO2 or ZrO2

i-C4

Alkali-doped

ZnO/Cr2 O

3

Cu/ZnO; Cu/ZnO/Al2 O3

CuO/CoO/Al2 O3

MoS2

MixedAlcohols

Oxosynthesis

HCo(CO)4

HCo(CO)3 P(Bu

3 )

Rh(CO)(PPh3 )

3

AldehydesAlcohols

Fischer-Tropsch

Fe, C

o, R

uWaxesDiesel

OlefinsGasoline

Ethanol

Co, Rh

FormaldehydeAg

DME

Al2O

3

zeolites

MTOMTG

OlefinsGasoline

MTBEAcetic Acid

carb

onyla

tion

CH3O

H +

COCo

, Rh,

Ni

M100M85DMFC

Direct Use

hom

olog

atio

nC

o

isob

utyl

ene

acid

ic io

n ex

chan

geResearch Needs• Gas cleanup/tars • New catalyst• Biological ‘Fisher Tropsch’ routes

BioFuels Social Policy Challenges

Biorefinery – Biofuels Has Arrived at a Key Tipping Point

• Biorefinery concepts can/need to be evaluated for environmental as well as their technical and economicpotential.

• Such environmental impact assessments are best conducted using Life Cycle Assessment –LCA

• LCA is a systems analysis tool to describe the ‘cradle-to-grave’ environmental impacts of products and processes

BioFuels Educational Challenges

Sustainability, Environmental, Energy Security• Societal Issues• Student Issues – K-12, Undergraduate, Graduate• Opportunity of Lifetime to re-engage students to Science and Engineering

• Need to introduce additional concepts inBiomass Chemistry/BiochemistryBiomass BiosynthesisSystems BiologyChemistry/Biochemistry of Cellulose, Hemicellulose, LigninGreen Chemistry of Processing Biomass Biorefinery – SustainabilityAnalytical Chemistry of Bioresources

Grand Challenge for the New Millennium

Development of Sustainable, Renewable BioFuels and BioMaterials for

9 Billion People by 2050

BioFuels - Challenge

Equivalent

1961: J.F. Kennedy “The goal, before this decade is out, of landing,a man on the moon and returning him safely to the earth”

1990: Human Genome Grand Challenge

Thank You!

W.J. BryanDestiny is not a matter of chance, it is a matter of choice, it

is not a thing to be waited for, it is a thing to be achieved

biofuels research opportunities/needs georgia institute of ...biorefinery.utk.edu/posters/thursday...

Documents