Catalysis for energy: New challenges for a sustainable energetic development
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Grupo de IngenieríaQuímica y Ambiental
Catalysis for energy: New challenges for a sustainable energetic development
Juan Antonio Melero HernándezCatedrático de Ingeniería QuímicaDepartamento de Tecnología Química y Ambiental
Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
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Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
Today’s primary energy is coming mainly from fossil fuels
Primary Energy coming from fossil fuels (2009): 80 %
Transport Energy coming from fossil fuels (2009): ∼ 99 %
Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
Today’s industrial chemical products are largely based on oil and gas
Paint Packaging Fibres
Cosmetics
Pharmaceuticals
Transport
Communication
Petroleum (90%)
Renewables(10%)
PRODUCTION OF CHEMICAL PRODUCTS
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Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
Fossil Broken cycle
Release of CO2
Chemical industry
Crude oilFuels &
products
BiomassClosed cycle
Photosynthesis
Biomass
Release of CO2
Chemical industry
Fuels & products
Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Sustainable biomass production around the world is enormous (specially, lignocelullosic biomass)
• There are a lot of transformation technologies of biomass into fuels and chemicals.
BUT …
• Currently, most of these technologies are in pilot-plant or even laboratory scale development stage. There are not in commercial stage due to the high-cost of the technology as well as low energy and mass yields as compared with those using fossil resources as raw material.
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Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Integration of biomass conversion processes to yield fuels, power and chemicals.
FeedstocksConversionProcesses
Biofuels
EthanolRenewable dieselLiquid fuels
Power
ElectricityHeat
Chemicals
Plastics, resins, foamsPhenolic resinsSolventsChemical intermediatesAdhesivesFatty AcidsPaints, CoatingDyes, PigmentsDetergentsLubricating FluidsPlant and animal oils
Agricultural CropsAgricultural Residues
Forest ResiduesAnimal Wastes
Municipal Wastes
Non-edible biomass
HydrolysisFermentationBioconversion
Chemical ConversionGasification
PyrolysisCombustion
CO2 Mass Energy
HVLV
“ Profit ”
LVHV
“ CoverCosts ”
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Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Target: Maximize the value derived from the biomass feedstock
Lignocelullosic Wastes¿ ?
Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Target: Maximize the value derived from the biomass feedstock
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Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Biorefinery: “The concept ”
An “interesting” first step
Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Biomass co-processing on refineries
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Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Biorefinery: “The concept ”
Biorefinery
Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Lignocellulosic biomass
Lignin
Cellulose
Hemicellulose
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Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Starch-rich biomass (Cereals)
Starch
Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Sugar rich biomass (sugar beet, sugar cane, …)
Sucrose
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Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Triglyceride rich biomass (vegetables oils, fats, …)
Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Biomass resources
Biomass
Carbohydrates
(Sugars)
75 %
20 %
Lignin
Others5 %
OilsFats ProteinsTerpenesAlkaloidsTerpenoidsWaxes
Energy
Chemicals
¿?
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Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
BIOMASS
Sugar Platform“Biochemical”
Syngas Platform“Thermochemical”
Biogas Platform“Biochemical”
Oil crops Platform“Chemical”
Pyrolysis“Thermochemical”
Sugars
Syngas
Fuels
Chemicals
Heat&
Power
Bio-oil
Bio-oil
Biogas
Oils
LignocelullosicResidues
LignocelullosicResidues
• Biorefinery concept is built on different “Platforms”
Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
BIOMASS
Sugar Platform“Biochemical”
Syngas Platform“Thermochemical”
Biogas Platform“Biochemical”
Oil crops Platform“Chemical”
Pyrolysis“Thermochemical”
Sugars
Syngas
Fuels
Chemicals
Heat&
Power
Bio-oil
Bio-oil
Biogas
Oils
LignocelullosicResidues
LignocelullosicResidues
• Biorefinery concept is built on different “Platforms”
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Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Syngas platform
Lignocelullosic Biomass
GASIFICATION
H2 - CO - CO2 - CH4
Syngas
Source for the production of biofuels and chemicals
T= 850 – 1400 º CP= 1-60 bar
AirO2Steam
Syngas CleaningConditioning
CO2
TarAshInorganic
CHPCogeneration
Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Syngas platform
H2 / CO
WGS
H2
Methanol
Catalytic
Reforming
DMEFuelCells
Bio-GasolineMTG
MTBEFischer-Tropsch
Liquid Fuels SNG
Bio-Olefins (C2-C4)MTO
Acetic acid
Formaldehyde
Ammonia
Fertilizers
BIOMASS
AlcoholC2+
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Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
BIOMASS
Sugar Platform“Biochemical”
Syngas Platform“Thermochemical”
Biogas Platform“Biochemical”
Oil crops Platform“Chemical”
Pyrolysis“Thermochemical”
Sugars
Syngas
Fuels
Chemicals
Heat&
Power
Bio-oil
Bio-oil
Biogas
Oils
LignocelullosicResidues
LignocelullosicResidues
• Biorefinery concept is built on different “Platforms”
Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Bioil platform
Lignocelullosic Biomass
Fast Pyrolysis
Bio-oil
Fast heating Short Residence Time
T= 450 – 550 º CP= 1-5 atm
Absence of air
60-75 wt. %
15-25 wt. %
10-20 wt. %
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Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Bioil platform
Lignocelullosic Biomass
Fast Pyrolysis
Bio-oil
Fast heating Short Residence Time
Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Bioil platform
Lignocelullosic Biomass
Fast Pyrolysis
Bio-oil
Fast heating Short Residence Time
• Oxygen content: 35-40 wt. %
• Low pH ∼ 2.5
• Water content: 10-15 wt. %
• Low stability (polymerization)
• Low heating value (16-19 MJ/kg)
• Corrosiveness
• Poor volatility
• Low miscibility with hydrocarbon fuels
Need of upgrading
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Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Bioil platform
Bio-oilBIOMASS
Catalytic
Upgrading
HydrodeoxygenationO2
Cracking
C6H8O4 + 4 H2 C6H8 + 4 H2O
C6H8O4 C4.5H6 + H2O + 1.5 CO2
Gasification H2 / CO
Char
ActivatedCarbon
Extraction Chemicals
Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
BIOMASS
Sugar Platform“Biochemical”
Syngas Platform“Thermochemical”
Biogas Platform“Biochemical”
Oil crops Platform“Chemical”
Pyrolysis“Thermochemical”
Sugars
Syngas
Fuels
Chemicals
Heat&
Power
Bio-oil
Bio-oil
Biogas
Oils
LignocelullosicResidues
LignocelullosicResidues
• Biorefinery concept is built on different “Platforms”
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Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Biogas platform
BiogasOrganicWaste
Anaerobic
Fermentation
Digestate
55-65 CH435-45 CO2
HeatElectricity
CHPCogeneration
FertilizersCompost
Gas distributionnetwork
Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
BIOMASS
Sugar Platform“Biochemical”
Syngas Platform“Thermochemical”
Biogas Platform“Biochemical”
Oil crops Platform“Chemical”
Pyrolysis“Thermochemical”
Sugars
Syngas
Fuels
Chemicals
Heat&
Power
Bio-oil
Bio-oil
Biogas
Oils
LignocelullosicResidues
LignocelullosicResidues
• Biorefinery concept is built on different “Platforms”
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Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Oil platform : Oil extraction
Oil seeds (rape, palm, sunflower, soybean)
Dedicated oils crops(Jatropha, algae, ..)
Extraction
Refining
VegetableOil
Protein Fraction
CattleFeed
RefiningCrude
Oil
LignocellulosicFraction
Sugar Platform
Syngas Platform
Bio-oil Platform
Waste oils(Fried oils, Yellow-grease, …)
Non-edible animal fats
Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Oil platform
Oil
TransesterificationBiodiesel
Transport Fuel
O
O
Glycerol Transport FuelChemicals
Catalytic CrackingBio-GasolineBio-olefins
Transport FuelChemicals
Chemical / Enzymatic modifications
Bio-SurfactantsOleochemical-products
Hydrogenation Green-DieselTransport Fuel
Proceso EcofiningEni/UOP
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Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Oil platform: Glycerol chemistry
Branched polyesters and nylons
OH
OH
HO
Glycerol
OH
OH
HO
Glycerol
OHHO
H3COH
OH
CH3
HO
HOO
CO2H
OH
HO
O
O
OR1
R2
R3
O
OH
HO OH
OH
OH
OO
O
HO O
O
O
O
Glycidol1,3-Propanediol
Propylene glycol
PropanolMono-, di-, or tri-
glycerate
Diglyceraldehyde
Glycerol carbonate
Glyceric acid
Applications: humectant, plasticizer, fibers, solvent, lubricant, sweetener, bodying agent, antifreeze, and fuel formulation.
Hydrogenolysis
Fermentation
Sorona Fiber
Antifreeze
Humectant
Fuelsformulation
Oxidation
Polyester fibers
Polycarbonates
Polyurethanes
Polymerization
Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
BIOMASS
Sugar Platform“Biochemical”
Syngas Platform“Thermochemical”
Biogas Platform“Biochemical”
Oil crops Platform“Chemical”
Pyrolysis“Thermochemical”
Sugars
Syngas
Fuels
Chemicals
Heat&
Power
Bio-oil
Bio-oil
Biogas
Oils
LignocelullosicResidues
LignocelullosicResidues
• Biorefinery concept is built on different “Platforms”
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Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Sugar platform : Sugars extraction
Sim
ple
suga
rs(h
exos
esan
d pe
nto
ses)
Starch-rich Biomass
Sugar-rich Biomass
Extraction Starch Hydrolysis
C6Glucose
Lignocelullosic Biomass
Chemical/Enzymatic
Hydrolysis
Cellulose (35-50 %)
C6Glucose
Hemicellulose (15-25 %)
C5-C6
Forest ResiduesAgricultural ResiduesLignocelullosic Crops
StrawCorn StoverBagasse
Lignin (20-25 %)
Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Sugar platform : Sugars transformation
Sim
ple
suga
rs(h
exos
esan
d pe
nto
ses)
Transportation fuels
Chemicals
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Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Sugar platform : Sugars towards transportation fuelsSi
mpl
e su
gars
(hex
oses
)
C6O
6H
122
C2H
5O
H +
2 C
O2
FER
MEN
TATI
ON
Anaerobic reaction with
enzymes
15 %
BIOETHANOL
DIS
TILL
ATI
ON
DR
YIN
G96 %
Water content
99 %
Transport Fuel
DDGSCattle Feed
BIOBUTANOLTransport Fuel
Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Sugar platform : Sugars towards transportation fuels
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Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Sugar platform : Lignin valorization
LigninChemical
TransformationsAdded value chemicals
Catalytic hydrogenationCurrent
TechnologyPetroleum Industry
J. Zakzeski. “The catalytic valorization of lignin for the production of renewable chemicals”Chem. Rev. 2010 , 110, 3552-3599
Syngas Platform
Bio-oil Platform
Transport FuelHeat & Electricity (CHP)
Catalytic oxidation
More complex molecules
Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Sugar platform : Sugars towards chemicals
Platform molecules (or building block chemicals) are molecules with multiple functional groups that possess the potential to be transformed into new families of useful molecules.
SugarsGlucoseFructoseXyloseArabinoseLactose
Bio-transformations
Chemical Transformation
Added value bio-chemicals
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Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Sugar platform : Sugars towards chemicals
The Office of the Biomass program, US has recently identified 12 building blocks that can be produced from sugars via biological or chemical conversions
Building Blocks
C3 Glycerol
3 hydroxypropionic acid
C4 1,4 succinic acid
1,4 fumaric acid
1,4 malic acids
Aspartic acid
3-hydroxybutyrolactone
C5 Levulinic acid
Glutamic acid
Itacomic acid
Xylitol/Arabinitol
C6 Sorbitol
Glucaric acid
2,5 furan dicarboxylic acid
Building Blocks
C3 Glycerol
3 hydroxypropionic acid
C4 1,4 succinic acid
1,4 fumaric acid
1,4 malic acids
Aspartic acid
3-hydroxybutyrolactone
C5 Levulinic acid
Glutamic acid
Itacomic acid
Xylitol/Arabinitol
C6 Sorbitol
Glucaric acid
2,5 furan dicarboxylic acid
Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
Glycerol
Chemical routes
HydrogenolysisOxidationDehydrationPolymerizationEtherification
Chemical – Transesterification of oilsOH
OH
HO OH
OH
HO
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Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
3- Hydroxypropionic acidBio-transformations – Fermentation of sugars
Chemical routes
HydrogenationDehydration
Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
1-4- Four carbon diacids(Succinic, Fumaric and Malic)
Bio-transformations – Fermentation of sugars
Chemical routes
HydrogenationAminationsPolymerizations
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Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
Aspartic acid
Bio-transformations – Fermentation and enzymatic conversion of sugars
Chemical – Amination of fumaric acid
Chemical routes
HydrogenationDehydrationsPolymerizations
Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
3-Hydroxybutyrolactone
Chemical – Oxidative degradation of starch (H2O2)
Chemical routes
HydrogenationPolymerizations
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Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
Levunilic acid
Chemical – Catalytic dehydration of sugars (C6)
Chemical routes
HydrogenationOxidationsCondensations
Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
Glutamic acid
Bio-transformations – Fermentation of sugars
Chemical routes
Hydrogenation
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Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
Itaconic acid
Bio-transformations – Fermentation of sugars
Chemical routes
HydrogenationPolymerization
Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
Xylitol
Chemical – Hydrogenation of xylose (C5)
Chemical routes
HydrogenolysisOxidationPolymerization
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Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
Sorbitol
Chemical – Hydrogenation of glucose (C6)
Chemical routes
HydrogenolysisOxidationPolymerization
Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
Glucaric acid
Chemical – Oxidation of starch with nitric acid
Chemical routes
DehydrationPolymerization
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Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
2,5- Furan dicarboxylic acid (FDCA)
Chemical – Oxidative dehydration of C6 sugars
Chemical routes
HydrogenationPolymerizations
Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Sugar platform : Sugars towards chemicals
SugarsBio-
Chemical-
Transformations
PlatformMolecules
Added value bio-chemicals
Chemical-
Transformations
Most of them are new processes
Most of them are not commercialMost of them are known processes
Commercial use
Low cost fermentation routes
New processes New building blocks
Challenges
New heterogeneous catalysts to replace homogenous.
New catalysts robust towards biomass impurities
Use of oxidant of low cost (air, oxygen , …)
Challenges
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Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Biorefineries: Future outlook
Fuels
Chemicals
Heat&
Power
Fossil
Sources
CmHnCmHnOx
Biomass
¿?
Yes
But …
Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• Biorefineries: Future outlook
Challenges&
Opportunities
New feedstock New processesand products
Development of low cost bio-transformation processes (fermentation and enzymatic)
New catalysts for this new feedstock
New processes for the hydrolysis of lignocelullosic feedstock (more efficient,
safe and environmentally friendly)
Scaling-up of the processes
Biomass valorization can use commercial technology developed
for petroleum refining nd petrochemicalsShort- Medium- term solution
Technologies integration
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Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
1st Generation
2nd Generation
Biorefinery
• Biorefineries: Future outlook
Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• References
J. J. Bozell, G. R. Petersen. Technology development for the production of bio-based products from biorefinerycarbohydrates – the US Department of Energy´s “Top 10” revisited. Green Chemistry 12 (2010) 539-554.
J. Zakzeski, P. C. A. Bruijinincx, A. L. Jongerius, B. M. Weckhuysen. The catalytic valorization of lignin for the production of renewable chemicals. Chemical Review 110 (2010) 3552-3599.
M. F. Demirbas. Biorefineries for biofuel upgrading: A critical review. Applied Energy 86 (2009) 151-161.
A. Demirbas. Biorefineries: Current activities and future developments. Energy Conversion and Management 50 (2009) 2782-2801.
S. Fernando, S. Adhikari, C. Chandrapal, N. Murali. Biorefineries: Current status, challenges and future direction. Energy & Fuels 20 (2006) 1727-1737.
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Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?
• References
Grupo de IngenieríaQuímica y Ambiental
Catalysis for energy: New challenges for a sustainable energetic development
Juan Antonio Melero HernándezCatedrático de Ingeniería QuímicaDepartamento de Tecnología Química y Ambiental
Biorefineries: A sustainable solution to the environmental risks of fossil fuels ?