biocombustibles de segunda generación a partir de nuevas …€¦ · syrup. adapted from nrel....

Jonathan R Mielenz BioEnergy Science Center Oak Ridge National Laboratory Oak Ridge, Tennessee USA 22 Marzo 2013 Bioeconomía Argentina 2013 Biomasa, innovación y valor agregado

Biocombustibles de segunda generación a partir de nuevas

materias primas / Second generation biofuels from new feedstocks

http://www.bioenergycenter.org/

2

“Definitions” in bioenergy deployment • 1st generation (full commercial exists)

– Sucrose and starch to ethanol – Oil-seeds into biodiesel

• 2nd generation (in deployment) – Cellulosics into ethanol (& butanol) – Cellulosics to thermochemical biocrude

• 3rd generation and beyond (technology development) – Whole biomass to advanced biocrude/ and bio-oil – Cellulosic fermentation to advanced biofuels – Sucrose and starch fermentation into advanced

biofuels (petroleum compatible like (iso)butanol) – Algal oils into biodiesel

3

First Generation Biofuels

Process Technologies

Output/ Products LAND

Cropland Oil crops

Grain/ food crops

Agric. Residues: bagasse

Animal wastes

Grasses

Wood

Rangeland

Forestland

Marginal Land

Fallow Land

Feedstocks

Biodiesel

Ethanol/ Butanol

Anaerobic Digestion

Fischer-Tropsch conversion

Gasification

Fermentation or chemistry

Bio-oil

Methane, H2, Syngas

chemicals

Algae

Hydrocarbons/ gasoline

Pyrolysis/Other Thermochemical

Water Sources

4

Process Technologies

Output/ Products LAND

Cropland

Oil crops

Grain/ food crops


Animal wastes

Grasses

Wood

Rangeland

Forestland

Marginal land

Fallow land

Feedstocks

Biodiesel

Ethanol/ Butanol

Anaerobic digestion

Fischer-Tropsch Conversion

Gasification

Fermentation & Enzymes

Bio-oil

Methane, H2

Chemicals

Algae

Hydrocarbons/ Gasoline


2nd Generation Biofuels: Biochemical

Water Sources

5

2nd Generation Biofuels: Thermochemical Process

Technologies Output/ Products LAND

Cropland

Oil crops

Grain/ food crops


Animal wastes

Grasses

Wood

Rangeland

Forestland

Marginal land

Fallow land

Feedstocks

Biodiesel

Ethanol/ Butanol

Anaerobic digestion

Fischer-Tropsch Conversion

Gasification

Fermentation & Enzymes

Bio-oil

Methane, H2, Syngas

Chemicals

Algae

Hydrocarbons/ Gasoline


Water Sources

6

A Basic Problem of Biomass Utilization: Transport economics due to the low density of biomass

Est. 40 MT/load of chips

Coal

7 Source: NREL Pix

Artist vision of a biorefinery with biomass storage adjacent

8

Global Biofeedstocks (2030): 914 Million MT of residues* can be available in eight regions and can replace half of the gasoline needs

16 177

221 151 180

Million MT of Agricultural residues only Main crop residues listed

39

20 110

US & Canada Corn, wheat, soy

China Wheat, corn, rice

EU-27 Wheat, barley, corn

Mexico Cane, wheat, corn

Brazil Cane, soy, corn

Argentina Soy, cane, corn

India Cane, wheat, rice Australia

Cane, wheat, barley

*This assumes 75% of residues are left on field Based on presentation from Novozymes Brian Davison ORNL

9 Large-scale facilities that are under construction or planned. Capacity in million U.S. gallons per year

Source: publicly available information.

Volumes and launch dates as announced by the respective companies Brian Davison ORNL

Cellulosic Biofuels Industry is Emerging (2013)

Millions of liters per year by

2017

76 Mascoma Michigan, USA Launch: 2013

23 Fiberight Iowa, USA

Launch: 2013

95 Dupont CE

Iowa, USA Launch: 2013

95 Abengoa Kansas, USA Launch: 2013

57 COFCO/

SINOPEC China

Launch: 2013

49 M&G-Chemtex

Italy Launch: 2013

5 Inbicon Denmark

Launch: 2009

15 Petrobras

Brazil Launch: 2013

95 Poet

Iowa, USA Launch: 2013

5 Abengoa

Spain Launch: 2009

50 KiOR

Mississippi, USA Launch: 2012

76 M&G-Chemtex

North Carolina Launch: 2014

30 INEOS

Florida, USA Launch: 2013

Biochemical Thermochem

10

KiOR Biocrude Production in the US

• Technology uses Fluid Catalytic Cracking (FCC) technology

• KiOR converts wood chips from Southeastern US

• Product is bio-crude oil and process gas for cogen of electricity

• Biocrude must be refined to fuels and KiOR works with Chevron

• First plant converts ~500 MT wood/day to ~50 million L/ year

• This week KiOR, Inc. announced first shipments of cellulosic diesel from its first commercial-scale facility in Columbus, Mississippi.

• KiOR plans a second facility in Natchez, MS

@ ~150 million L/ y

• Company interested in conversion of

bagasse to crude oil

www.kior.com

11

DuPont Cellulosic Ethanol in the US • DuPont technology uses enzyme breakdown & fermentation

• DuPont bought the enzyme producer Genencor

• DCE operated a ~950,000 L/yr demo plant in Tennessee since 2009

• Plant being build in Iowa corn belt in the US: Nevada, Iowa

• Produce ~95 million liters of cellulosic ethanol per year, using corn residues and expected complete mid-2014

• $9 million grant from the Iowa Power Fund, combined with over $226 million in matching funds by DuPont Cellulosic Ethanol

• Facility will use 375,000 dry tons of corn

residues (stover) per year

• DuPont is interested in collaboration

Biofuels.dupont.com

12

Millions of liters per year by

2017

Second generation biofuels – announced biorefineries (2017)

182 Asia

182 at 7 sites

Australia

1570 at >5 sites Brazil

390 at 9 sites Canada

610 at 8 sites China

1200 Indonesia

1200 Malaysia

844 Singapore

231 Thailand

7600 at >20 sites

EU 11700 at >80 Sites

USA

1890 at 4 sites

Other Latin America

Advanced Biofuels & Biobased materials Project Database (2012) Brian Davison ORNL

13

A Two-pronged Approach to Increase the Accessibility of Biomass Sugars

Switchgrass example (USDA-BESC)

Yeast example (Mascoma-BESC)

14

Potential of non-transgenic plant feedstock for bioenergy applications

Natural variation • Wide range of compositional characteristics • Potential to mine natural sources of plant material • Non-GMO accelerates development of feedstock resources Switchgrass variation • Upland and lowland varieties • Distributed across the Eastern US • and Canada Populus • Distributed in northwestern US and Canada • Found in diverse climates and terrain • Genome sequence is known (P. trichocarpa)

Canada

United States

15

High-throughput Screening to Analyze Natural Populus Trees

• Screening of ~1200 natural Populus trees, grow in three common gardens in California •Sugar release varies from 25% to over 90% – huge •Lignin varied from 17% to 27% of dry weight – huge •Environmental vs genetics? Fermentation testing of common garden trees underway – appears to be genetics

Populus common garden

16

Benefits of switchgrass Panicum virgatum L.

• Native U.S. prairie grass, non-invasive

• Perennial crop good for ten+ years

• Production starts by the second year

• High production possible (>25 MT/hectare)

• Requires low nitrogen, water inputs

• Harvested with convention

equipment

• Numerous varieties available

for most of the Eastern U.S.

Bob Perlack ORNL

17

Genetic Block in Lignin Biosynthesis in Switchgrass Increases Ethanol Yields

feruloyl CoA O

CoAS OH

OCH3

O

H OH

4-coumaraldehyde

HOH2C OH

4-coumaroyl alcohol

O

R- O OH

OH

caffeoyl shikimic acid or quinic acid

4-coumaroyl shikimic acid or quinic acid

O OH

R- O

Phenylalanine

H lignin

O

CoAS OH

4-coumaroyl CoA

O

CoAS OH

OH

caffeoyl CoA

HCT

C3H

HCT

PAL HOOC

cinnamate

CCoAOMT

HOOC OH

4-coumaric acid

C4H

4CL

coniferaldehyde O

H OH

OCH3

OCH3

coniferyl alcohol

OH HOH2C

G lignin

CAD

5-hydroxyconiferaldehyde

O

H OH

OCH3

OH sinapaldehyde

O

H OH

OCH3

CH3O

5-hydroxyconiferyl alcohol

OCH3

OH

OH

HOH2C

sinapyl alcohol

OCH3

OH

OCH3

HOH2C S lignin F5H

F5H

CAD

CAD

CCR

CCR Lignin

Pathway

ORNL Ethanol Yield in Wild-type and Noble Foundation Transgenic

Switchgrass

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

Wild-type COMT TransgenicLine

Etha

nol Y

ield

per

Wei

ght o

f Bio

mas

s (g

/g)

25% More Ethanol

Agrobacterium- mediated

Transformation of Switchgrass

X. Fu, Z. Wang, Noble J Mielenz, ORNL

The Samuel Roberts

NOBLE Foundation Funded by NRCS 68-3A75-5-239 USDA DOE Joint Solicitation

COMT COMT

Proc Natl Acad Sci USA 108 (9), 3803-3808

18

COMT Mutant Switchgrass is similar to Wild-type

•Lignin decreased about 16% in COMT2 & 3 •Plant grew normally compared to wild-type (WT)

•Height, stem diameter, growth rate •Decreased lignin content did not impact cellulose levels •Small increase in hemicellulose was detected

Wild-type (L) and 3 Transgenic switchgrass plants (R)

19

Reduction of bioprocess steps: Consolidated Bioprocessing (CBP)

Better Plants Better Bugs

Various Biofuels

Enzymes produced by the microbe

Minimal Separation

20

Fermentation by modified switchgrass and genetically engineered Mascoma yeast

• Variables: native and modified yeast and switchgrass • Biomass used was wild type and transgenic COMT

switchgrass after dilute acid pretreatment (180°C, 0.5% H2SO4 7.5 min.)

• Mascoma yeast expressing cellulase enzyme (cellobiohydrase II)

• Determined rate of fermentation and net ethanol yield on substrate

21

Improved switchgrass and new fermentation yeast demonstrate synergy

0

50

100

150

200

250

300

350

Normal yeast Mascoma yeast Normal yeast Mascoma yeast

Wild Type NF Swg Transgenic NF Swg

Eth

ano

l Pro

du

ctio

n (

mg

eto

h/ g

cel

lulo

se)

+26% +67%+41%

0

50

100

150

200

250

300

350

Normal yeast Mascoma yeast Normal yeast Mascoma yeast

Wild Type NF Swg Transgenic NF Swg

Eth

ano

l Pro

du

ctio

n (

mg

eto

h/ g

cel

lulo

se)

+26% +67%+41%

COMT Transgenic Switchgrass Produced More Ethanol

0

50

100

150

200

250

300

350

Wild Type COMT 2 COMT 3

mg

etha

nol/

g ce

llulo

se

+27% +24%

Mascoma Corp yeast expressing a cellobiohydrolase

22

Ultimate process of improved feedstock and improved bioconversion

23

2011 Soybean Production Worldwide • One of the largest cultivated crops worldwide • Products include soy meal, soy oil, and soybean hulls • Soybean hulls account for 5-8% of crop destined for animal feed

– Contain 9-11% Protein – High fiber content limits feeding to only ruminant animals

• Excludes large pig and poultry market

Dartmouth College

72 Brazil

Millions Metric Tons

in 2011 4.2

Canada

13.5 China

13.1 Others

6.4 Paraguay

11 India

48 Argentina

83.2 USA

*www.soybeanpremiums.org/

24

Commercial Cellulosic Ethanol Production

Noral pretreatment discroyts proteins

Better Plants Better Bugs

Various Biofuels

Enzymes produced by the microbe

Minimal Separation

Many pretreatment processes destroys proteins and feed value

Question: Can soybean hull sugars be fermented to ethanol?

25

Answer: Soybean Hulls Require NO Pretreatment for

Fermentation Ethanol Fermentation of Selected Biomass

and SBH w/o Pretreatment

0

0.1

0.2

0.3

0.4

0.5

0.6

0 5 10 15Time (d)

Wt

Lo

ss (

g)

SBH

Corn Stover

SwitchgrassWheat Straw

Other biomass sources fail to produce significant levels of ethanol without pretreatment

[ethanol] %

~2.5%

~0.8% 1.1%

(WO/2008/033842)

26

Potential Process Simplification: Biomass Ethanol: Biomass Ethanol:

A Simplified Process SchematicA Simplified Process Schematic

BiomassHandling FermentationPretreatment

Burner/BoilerTurbogenerator

Waste WaterTreatment

Distillation &StillageTreatment

Storage

Corn Stover

Hydrolyzate BrothRecycle &Condensate

Waste Water

EthanolCake

Biogas & Sludge

Waste Water

Enzyme

Recycle Water

Steam

Electricity

Steam

Steam & Acid

S/L SepSolids

Liquor

Waste Water

S/L Sep

Conditioning

Syrup

Adapted from NREL

Biomass Ethanol: Biomass Ethanol: A Simplified Process SchematicA Simplified Process Schematic





Storage

Corn Stover


Waste Water

EthanolCake

Biogas & Sludge

Waste Water

Enzyme

Recycle Water

Steam

Electricity

Steam

Steam & Acid

S/L SepSolids

Liquor

Waste Water

S/L Sep

Conditioning

Syrup

Biomass Ethanol: Biomass Ethanol: A Simplified Process SchematicA Simplified Process Schematic





Storage

Corn Stover


Waste Water

EthanolCake

Biogas & Sludge

Waste Water

Enzyme

Recycle Water

Steam

Electricity

Steam

Steam & Acid

S/L SepSolids

Liquor

Waste Water

S/L Sep

Conditioning

Syrup

Adapted from NREL

• Potential for about 20% cost reduction with no pretreatment

• Other biomass types lack protein co-product sales

Soybean Hull Ethanol: Soybean Hull Ethanol: A Simplified Process SchematicA Simplified Process Schematic

BiomassHandling FermentationHydroheater



Storage

Soybean Hulls

Broth

FeedWaste Water

Ethanol

Cake

Biogas & Sludge

Waste Water

Enzyme

Recycle Water

Steam

Electricity

Steam

S/L Sep

S/L Sep


Syrup

Adapted from NREL





Storage

Soybean Hulls

Broth

FeedWaste Water

Ethanol

Cake

Biogas & Sludge

Waste Water

Enzyme

Recycle Water

Steam

Electricity

Steam

S/L Sep

S/L Sep


Syrup





Storage

Soybean Hulls

Broth

FeedWaste Water

Ethanol

Cake

Biogas & Sludge

Waste Water

Enzyme

Recycle Water

Steam

Electricity

Steam

S/L Sep

S/L Sep


Syrup

Adapted from NREL

Dartmouth College

27

Technology Advantages:

Dartmouth College

• Process concentrates 10% protein material to >25% protein by weight with target at 47%

– Soybean products valued by protein content (%) • Potential for ethanol production co-located with soybean processing. • Potential for >2 million MT of high protein feed

– Current market price at $420/T @47% protein • Low fiber opens up poultry and pig feed market

Market potential in Brazil plus Argentina surpasses US production and both countries produce ethanol and soybeans

*www.soybeanpremiums.org/ United soybean board

28

Summary • 2nd generation biofuels are moving to market via

multiple commercial operations

• Both thermochemical and biochemical processes are being commercialized with some feedstock preferences

• Improvement of the bioconversion economics for biorefineries will occur via synergy of improved feedstock AND better fermentation microorganisms

• Bagasse and other agricultural residues such as soybean hulls provide opportunities for Argentina and SA to produce 2nd generation biofuels

• International partnering will occur as feedstock is local but the processing technology can be transferred.

29

Questions later?

Notice: 35th Annual Symposium on Biotechnology for

Fuels and Chemicals April 29 - May 2, 2013 Portland, Oregon, USA 19 sessions of 7 speakers plus 400 posters 700+ attendees ~25% international, ~30% industry Chairs: Jim McMillan, Steve Decker, NREL, USA Jonathan Mielenz, ORNL, Thomas Klasson, USDA, USA

Slide Number 1“Definitions” in bioenergy deploymentSlide Number 3Slide Number 4Slide Number 5A Basic Problem of Biomass Utilization: �Transport economics due to the low density of biomassSlide Number 7Global Biofeedstocks (2030):�914 Million MT of residues* can be available in eight regions and can replace half of the gasoline needsCellulosic Biofuels Industry �is Emerging (2013)�KiOR Biocrude Production in the USDuPont Cellulosic Ethanol in the USSecond generation biofuels –�announced biorefineries (2017)A Two-pronged Approach to �Increase the Accessibility of Biomass SugarsPotential of non-transgenic plant feedstock for bioenergy applicationsHigh-throughput Screening to Analyze Natural Populus TreesSlide Number 16Slide Number 17Slide Number 18Reduction of bioprocess steps: Consolidated Bioprocessing (CBP)Slide Number 20Slide Number 21Ultimate process of improved feedstock and improved bioconversion2011 Soybean Production WorldwideCommercial Cellulosic Ethanol ProductionSlide Number 25Potential Process Simplification:Technology Advantages:�SummaryQuestions later?

biocombustibles de segunda generación a partir de nuevas …€¦ · syrup. adapted from nrel....

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