Upgrading of BioUpgrading of Bio- -oil oil for Fuel...
Transcript of Upgrading of BioUpgrading of Bio- -oil oil for Fuel...
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NREL is a national laboratory of the U.S. Department of Energy Office of Energy Efficiency and Renewable Energy operated by the Alliance for Sustainable Energy, LLC
1313thth Annual Green Annual Green Chemistry & EngineeringChemistry & Engineering
ConferenceConference
Luc Moens, Ph.DLuc Moens, Ph.D
June 25, 2009June 25, 2009
Upgrading of BioUpgrading of Bio--oil oil for Fuel Productionfor Fuel Production
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Topics
• What is bio-oil?
• Lignocellulosic biomass – composition
• Bio-oil • properties• chemical composition
• Upgrading
• Future R&D: catalytic pyrolysis
National Renewable Energy Laboratory Innovation for Our Energy Future
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From Biomass to Bio-oil: Pyrolysis
National Renewable Energy Laboratory Innovation for Our Energy Future
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T (°C)
GasificationGasification
PyrolysisPyrolysis
CO + H2
syngas
BioBio--oiloil
Liquid Fuels
BiomassBiomass
???
Fischer-Tropschprocess
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From Biomass to Bio-oil: Pyrolysis
National Renewable Energy Laboratory Innovation for Our Energy Future
300
900
600
T (°C)
PyrolysisPyrolysis
BioBio--oiloil
BiomassBiomass
Fast pyrolysisFast pyrolysis
no oxygen 450°- 550°Crapid heating (>1000°C/s)short residence times (1-2 s)
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From Biomass to Bio-oil: Pyrolysis
National Renewable Energy Laboratory Innovation for Our Energy Future
300
900
600
T (°C)
PyrolysisPyrolysis
BioBio--oiloil
BiomassBiomass
Fast pyrolysisFast pyrolysis
~75 wt% liquid product yield(25 wt% = char + gas)
can be transported / storedconversion into
fuels & chemicals
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Biomass feedstocks
National Renewable Energy Laboratory Innovation for Our Energy Future
Ag residues
Forest residues
Willow
Switch grass
Hybrid poplar
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Lignocellulosic Biomass
National Renewable Energy Laboratory Innovation for Our Energy Future
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O H
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H O
H O
O HO
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H O
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H O
O HO
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H 3C O
O H
O C H 3
O C H 3
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O C H 3
O C H3
H 3C O
OO
H O
H 3C O
H O
O C H 3
O C H 3
O H
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H O
H 3C O
O H
O C H 3
O C H3
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O C H 3
O C H 3
O C H 3
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LigninLignin 15% - 25%• complex aromatic structure• resists biochemical conversion
HemicelluloseHemicellulose 23% - 32%• carbohydrate polymer• C5 and C6 sugars(xylose-based)
Cellulose Cellulose 38% - 50%• glucose polymer (C6 )
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Fast Pyrolysis Bio-oil
National Renewable Energy Laboratory Innovation for Our Energy Future
5% methanol addition
Homogenization
• Density ~ 1.2 kg/L
• Combustible (HHV~18 MJ/kg)
• Contains 20-30% H2O
Partly miscible with water
Non-miscible with hydrocarbons
• Highly acidic: pH ~ 2.5 (corrosive!)
• Strong phenolic odor
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Fast Pyrolysis Bio-oil
National Renewable Energy Laboratory Innovation for Our Energy Future
5% methanol addition
HomogenizationHigh degree of oxygenation
C 40-48%, H 7-8%, O 44-52% (wet basis)
C 53-57%, H 7-7.5%, O 36-40% (dry basis)
(cfr. heavy fuel oil - C 85%; H 11%; O 1%)
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Fast Pyrolysis Bio-oil
National Renewable Energy Laboratory Innovation for Our Energy Future
5% methanol addition
Homogenization
Bio-oil changes properties during storage
• increase in viscosityrate = 2.317∗1013 exp(-9659/T) cP/day
• decreased volatility• phase separation• formation of gums and deposits
Instability is caused by thermochemical processes that lead to cross-linking of C=O compounds
(Diebold, J.P.; Czernik, S., Energy Fuels 1997, 11, 108)
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Bio-oil: chemical composition
National Renewable Energy Laboratory Innovation for Our Energy Future
Fresh bio-oil is a homogeneous emulsion of > 300 organic compounds
Wt % of bio-oilC1 (formic acid, methanol) 5 - 10C1-C4 aldehydes, glyoxal,hydroxyketones, carboxylic acids 15 - 35
C5-C6 furfuraldehydes, furanones,pyranones 10 - 20
Anhydrosugars (levoglucosan) 6 - 10Carbohydrate oligomers 5 - 10Phenolics 6 - 15Pyrolytic lignin (oligomeric phenolics) 15 - 30
“unidentified” ~ 20
Radlein, D., The Production of Chemicals from Fast Pyrolysis Bio-oils, in Fast Pyrolysis of Biomass; A Handbook
ligninderived
cellulosederived
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Bio-oil properties
National Renewable Energy Laboratory Innovation for Our Energy Future
Bio-oil + water
Phase separation
5% methanol addition
Homogenization
Oasmaa, A.; Czernik, S., Energy & Fuels, 1999, 13, 914-921.
• Bio-oil contains ~ 20% H2O• [H2O] ≥ 30% phase separation
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From Bio-oil to Liquid Transportation Fuels
National Renewable Energy Laboratory Innovation for Our Energy Future
Refinery
PetroleumPetroleum
BioBio--oiloil
Diesel
Liquid FuelsLiquid Fuels
• High acidity (corrosive)• High oxygen content (~40%)
(too high for hydrotreatment/hydrocracking)
Technical barriersTechnical barriers
Jet fuelGasoline
Diesel
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From Bio-oil to Liquid Transportation Fuels
National Renewable Energy Laboratory Innovation for Our Energy Future
Refinery
PetroleumPetroleum
BioBio--oiloil
Diesel
Liquid FuelsLiquid Fuels
Jet fuelGasoline
Diesel
“UpgradingUpgrading” through chemical modification
• neutralization of acids• stabilization (no cross-linking by C=O groups)
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Bio-oil Neutralization & Stabilization
National Renewable Energy Laboratory Innovation for Our Energy Future
R OH
OR1OH
R OR1
OH2O
acid
R H
O
aldehyde
2 R1OHR OR1
OR1
H2O
alcohol
alcohol
ester
acetal
H+
H+
• Reactions are equilibrium-limited 20 wt% residual acid • Excess water from crude bio-oil (20-30%) and condensation reaction• Acid catalyst required • Stoichiometric amount of ROH needed (high cost!)
DisadvantagesDisadvantages
Moens, L.; Black, S. K.; Myers M. D.; Czernik, S. Energy Fuels 2009, 23, 2695
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Bio-oil Hydroprocessing (H2)
National Renewable Energy Laboratory Innovation for Our Energy Future
• Review: Elliott D. C. Energy Fuels 2007, 21, 1792
• Commercial catalysts: NiMo, CoMo, precious metals
• High T / P conditions achieve hydrodeoxygenation
• Compatible with petroleum refinery infrastructure
• Range of hydrocarbon products (gasoline-type):
aromaticscycloalkanes
• Only lignin-derived phenolics are relevant (only ~25% of biomass)
• use of added H2 cost is an issue
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Lignocellulosic Biomass
National Renewable Energy Laboratory Innovation for Our Energy Future
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LigninLignin 15% - 25%• complex aromatic structure• resists biochemical conversion
HemicelluloseHemicellulose 23% - 32%• carbohydrate polymer• C5 and C6 sugars(xylose-based)
Cellulose Cellulose 38% - 50%• glucose polymer (C6 )
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Synthesis of larger Carbon Units
National Renewable Energy Laboratory Innovation for Our Energy Future
HO CHO CH3CHO OHC-CHO OHO
OCHO
OCHO
OH
… ongoing R&D
Can these small oxygenates be “polymerized” to form larger molecules (C9 – C20 units)?
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Catalytic Pyrolysis
National Renewable Energy Laboratory Innovation for Our Energy Future
Diesel
Liquid FuelsLiquid Fuels
Jet fuel DieselGasoline
Catalytic Pyrolysis
BiomassBiomass
catalyst system “improved”bio-oilvapors modified
vapors
• eliminate coking• mechanisms of thermochemistry• “multifunctional” catalysts
R&D needsR&D needs
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Acknowledgment
Co-workers:
Dr. Stefan Czernik (mentorship)Stuart K. BlackMichele Myers
US Dept. of Energy – Office of Biomass Program
National Renewable Energy Laboratory Innovation for Our Energy Future