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
Agric. Residues: bagasse
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
Pyrolysis/Other Thermochemical
2nd Generation Biofuels: Biochemical
Water Sources
5
2nd Generation Biofuels: Thermochemical 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 & Enzymes
Bio-oil
Methane, H2, Syngas
Chemicals
Algae
Hydrocarbons/ Gasoline
Pyrolysis/Other Thermochemical
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
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
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
• 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
Waste WaterTreatment
Distillation &StillageTreatment
Storage
Soybean Hulls
Broth
FeedWaste Water
Ethanol
Cake
Biogas & Sludge
Waste Water
Enzyme
Recycle Water
Steam
Electricity
Steam
S/L Sep
S/L Sep
Burner/BoilerTurbogenerator
Syrup
Adapted from NREL
Soybean Hull Ethanol: Soybean Hull Ethanol: A Simplified Process SchematicA Simplified Process Schematic
BiomassHandling FermentationHydroheater
Waste WaterTreatment
Distillation &StillageTreatment
Storage
Soybean Hulls
Broth
FeedWaste Water
Ethanol
Cake
Biogas & Sludge
Waste Water
Enzyme
Recycle Water
Steam
Electricity
Steam
S/L Sep
S/L Sep
Burner/BoilerTurbogenerator
Syrup
Soybean Hull Ethanol: Soybean Hull Ethanol: A Simplified Process SchematicA Simplified Process Schematic
BiomassHandling FermentationHydroheater
Waste WaterTreatment
Distillation &StillageTreatment
Storage
Soybean Hulls
Broth
FeedWaste Water
Ethanol
Cake
Biogas & Sludge
Waste Water
Enzyme
Recycle Water
Steam
Electricity
Steam
S/L Sep
S/L Sep
Burner/BoilerTurbogenerator
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?
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