Catalysis for energy: New challenges for a sustainable energetic development

Grupo de Ingeniería
Química y Ambiental
Catalysis for energy: New challenges for
a sustainable energetic development
Juan Antonio Melero Hernández
Catedrático de Ingeniería Química
Departamento 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 ?

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 %
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

Fossil
Broken cycle
Release
of CO2
Chemical industry
Crude oil
Fuels &
products
Biomass
Closed
cycle
Photosynthesis
Biomass
Release
of CO2
Chemical industry
Fuels &
products
• 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.

• Integration of biomass conversion processes to yield fuels,
power and chemicals.
Feedstocks
Conversion
Processes
Biofuels
Ethanol
Renewable diesel
Liquid fuels
Power
Electricity
Heat
Chemicals
Plastics, resins, foams
Phenolic resins
Solvents
Chemical intermediates
Adhesives
Fatty Acids
Paints, Coating
Dyes, Pigments
Detergents
Lubricating Fluids
Plant and animal oils
Agricultural Crops
Agricultural Residues
Forest Residues
Animal Wastes
Municipal Wastes
Non-edible
biomass
Hydrolysis
Fermentation
Bioconversion
Chemical Conversion
Gasification
Pyrolysis
Combustion
CO2 Mass Energy
HVLV
“ Profit ”
LVHV
“ Cover
Costs ”

• Target: Maximize the value derived from the biomass
feedstock
Lignocelullosic
Wastes¿ ?
• Target: Maximize the value derived from the biomass
feedstock

• Biorefinery: “The concept ”
An “interesting” first step
• Biomass co-processing on refineries

• Biorefinery: “The concept ”
Biorefinery
• Lignocellulosic biomass
Lignin
Cellulose
Hemicellulose

• Starch-rich biomass (Cereals)
Starch
• Sugar rich biomass (sugar beet, sugar cane, …)
Sucrose

• Triglyceride rich biomass (vegetables oils, fats, …)
• Biomass resources
Biomass
Carbohydrates
(Sugars)
75 %
20 %
Lignin
Others
5 %
Oils
Fats
Proteins
Terpenes
Alkaloids
Terpenoids
Waxes
Energy
Chemicals
¿?

BIOMASS
Sugar Platform
“Biochemical”
Syngas Platform
“Thermochemical”
Biogas Platform
“Biochemical”
Oil crops Platform
“Chemical”
Pyrolysis
Sugars
Syngas
Fuels
Chemicals
Heat
&
Power
Bio-oil
Bio-oil
Biogas
Oils
Lignocelullosic
Residues
Lignocelullosic
Residues
• Biorefinery concept is built on different “Platforms”
BIOMASS
Sugar Platform
“Biochemical”
Syngas Platform
Biogas Platform
“Biochemical”
Oil crops Platform
“Chemical”
Pyrolysis
Sugars
Syngas
Fuels
Chemicals
Heat
&
Power
Bio-oil
Bio-oil
Biogas
Oils
Lignocelullosic
Residues
Lignocelullosic
Residues

• Syngas platform
Lignocelullosic
Biomass
GASIFICATION
H2 - CO - CO2 - CH4
Syngas
Source for the production
of biofuels and chemicals
T= 850 – 1400 º C
P= 1-60 bar
Air
O2
Steam
Syngas Cleaning
Conditioning
CO2
Tar
Ash
Inorganic
CHP
Cogeneration
• Syngas platform
H2 / CO
WGS
H2
Methanol
Catalytic
Reform
ing
DME
Fuel
Cells
Bio-Gasoline
MTG
MTBE
Fischer-Tropsch
Liquid Fuels SNG
Bio-Olefins (C2-C4)
MTO
Acetic
acid
Formaldehyde
Ammonia
Fertilizers
BIOMASS
Alcohol
C2+

BIOMASS
Sugar Platform
“Biochemical”
Syngas Platform
Biogas Platform
“Biochemical”
Oil crops Platform
“Chemical”
Pyrolysis
Sugars
Syngas
Fuels
Chemicals
Heat
&
Power
Bio-oil
Bio-oil
Biogas
Oils
Lignocelullosic
Residues
Lignocelullosic
Residues
• Bioil platform
Lignocelullosic
Biomass
Fast Pyrolysis
Bio-oil
Fast heating
Short Residence Time
T= 450 – 550 º C
P= 1-5 atm
Absence of air
60-75 wt. %
15-25 wt. %
10-20 wt. %

• Bioil platform
Lignocelullosic
Biomass
Fast Pyrolysis
Bio-oil
Fast heating
• Bioil platform
Lignocelullosic
Biomass
Fast Pyrolysis
Bio-oil
Fast heating
• 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

• 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
Activated
Carbon
Extraction Chemicals
BIOMASS
Sugar Platform
“Biochemical”
Syngas Platform
Biogas Platform
“Biochemical”
Oil crops Platform
“Chemical”
Pyrolysis
Sugars
Syngas
Fuels
Chemicals
Heat
&
Power
Bio-oil
Bio-oil
Biogas
Oils
Lignocelullosic
Residues
Lignocelullosic
Residues

• Biogas platform
Biogas
Organic
Waste
Anaerobic
Fermentation
Digestate
55-65 CH4
35-45 CO2
Heat
Electricity
CHP
Cogeneration
Fertilizers
Compost
Gas distribution
network
BIOMASS
Sugar Platform
“Biochemical”
Syngas Platform
Biogas Platform
“Biochemical”
Oil crops Platform
“Chemical”
Pyrolysis
Sugars
Syngas
Fuels
Chemicals
Heat
&
Power
Bio-oil
Bio-oil
Biogas
Oils
Lignocelullosic
Residues
Lignocelullosic
Residues

• Oil platform : Oil extraction
Oil seeds
(rape, palm, sunflower, soybean)
Dedicated oils crops
(Jatropha, algae, ..)
Extraction
Refining
Vegetable
Oil
Protein
Fraction
Cattle
Feed
Refining
Crude
Oil
Lignocellulosic
Fraction
Sugar Platform
Syngas Platform
Bio-oil Platform
Waste oils
(Fried oils, Yellow-grease, …)
Non-edible animal fats
• Oil platform
Oil
Transesterification
Biodiesel
Transport Fuel
O
O
Glycerol Transport Fuel
Chemicals
Catalytic Cracking
Bio-Gasoline
Bio-olefins
Transport Fuel
Chemicals
Chemical / Enzymatic
modifications
Bio-Surfactants
Oleochemical-products
Hydrogenation Green-Diesel
Transport Fuel
Proceso Ecofining
Eni/UOP

• Oil platform: Glycerol chemistry
Branched polyesters
and nylons
OH
OH
HO
Glycerol
OH
OH
HO
Glycerol
OHHO
H3C
OH
OH
CH3
HO
HO
O
CO2H
OH
HO
O
O
O
R1
R2
R3
O
OH
HO OH
OH
OH
OO
O
HO O
O
O
O
Glycidol
1,3-Propanediol
Propylene glycol
Propanol
Mono-, 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
Fuels
formulation
Oxidation
Polyester fibers
Polycarbonates
Polyurethanes
Polymerization
BIOMASS
Sugar Platform
“Biochemical”
Syngas Platform
Biogas Platform
“Biochemical”
Oil crops Platform
“Chemical”
Pyrolysis
Sugars
Syngas
Fuels
Chemicals
Heat
&
Power
Bio-oil
Bio-oil
Biogas
Oils
Lignocelullosic
Residues
Lignocelullosic
Residues

• Sugar platform : Sugars extraction
Simplesugars
(hexosesandpentoses)
Starch-rich
Biomass
Sugar-rich
Biomass
Extraction Starch Hydrolysis
C6
Glucose
Lignocelullosic
Biomass
Chemical/Enzymatic
Hydrolysis
Cellulose (35-50 %)
C6
Glucose
Hemicellulose (15-25 %)
C5-C6
Forest Residues
Agricultural Residues
Lignocelullosic Crops
Straw
Corn Stover
Bagasse
Lignin (20-25 %)
• Sugar platform : Sugars transformation
Simplesugars
(hexosesandpentoses)
Transportation fuels
Chemicals

• Sugar platform : Sugars towards transportation fuelsSimplesugars
(hexoses)
C6O6H122C2H5OH+2CO2
FERMENTATION
Anaerobic
reaction with
enzymes
15 %
BIOETHANOL
DISTILLATION
DRYING
96 %
Water content
99 %
Transport Fuel
DDGS
Cattle Feed
BIOBUTANOL
Transport Fuel
• Sugar platform : Sugars towards transportation fuels

• Sugar platform : Lignin valorization
Lignin
Chemical
Transformations
Added value chemicals
Catalytic hydrogenation
Current
Technology
Petroleum 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 Fuel
Heat & Electricity (CHP)
Catalytic oxidation
More complex molecules
• 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.
Sugars
Glucose
Fructose
Xylose
Arabinose
Lactose
Bio-transformations
Chemical Transformation
Added value bio-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
Glycerol
Chemical routes
Hydrogenolysis
Oxidation
Dehydration
Polymerization
Etherification
Chemical – Transesterification of oilsOH
OH
HO OH
OH
HO

3- Hydroxypropionic acid
Bio-transformations – Fermentation of sugars
Chemical routes
Hydrogenation
Dehydration
1-4- Four carbon diacids
(Succinic, Fumaric and Malic)
Chemical routes
Hydrogenation
Aminations
Polymerizations

Aspartic acid
Bio-transformations – Fermentation and enzymatic
conversion of sugars
Chemical – Amination of fumaric acid
Chemical routes
Hydrogenation
Dehydrations
Polymerizations
3-Hydroxybutyrolactone
Chemical – Oxidative degradation of starch (H2O2)
Chemical routes
Hydrogenation
Polymerizations

Levunilic acid
Chemical – Catalytic dehydration of sugars (C6)
Chemical routes
Hydrogenation
Oxidations
Condensations
Glutamic acid
Chemical routes
Hydrogenation

Itaconic acid
Chemical routes
Hydrogenation
Polymerization
Xylitol
Chemical – Hydrogenation of xylose (C5)
Chemical routes
Hydrogenolysis
Oxidation
Polymerization

Sorbitol
Chemical – Hydrogenation of glucose (C6)
Chemical routes
Hydrogenolysis
Oxidation
Polymerization
Glucaric acid
Chemical – Oxidation of starch with nitric acid
Chemical routes
Dehydration
Polymerization

2,5- Furan dicarboxylic acid (FDCA)
Chemical – Oxidative dehydration of C6 sugars
Chemical routes
Hydrogenation
Polymerizations
Sugars
Bio-
Chemical-
Transformations
Platform
Molecules
Added value
bio-chemicals
Chemical-
Transformations
Most of them are new processes
Most of them are not commercial
Most 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

• Biorefineries: Future outlook
Fuels
Chemicals
Heat
&
Power
Fossil
Sources
CmHn
CmHnOx
Biomass
¿?
Yes
But …
Challenges
&
Opportunities
New feedstock New processes
and 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 petrochemicals
Short- Medium- term solution
Technologies
integration

1st Generation
2nd Generation
Biorefinery
• References
J. J. Bozell, G. R. Petersen. Technology development for the production of bio-based products from biorefinery
carbohydrates – 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.

• References
Grupo de Ingeniería
Química y Ambiental
Catalysis for energy: New challenges for
a sustainable energetic development
Juan Antonio Melero Hernández
Catedrático de Ingeniería Química
Departamento de Tecnología Química y Ambiental
Biorefineries: A sustainable solution to the
environmental risks of fossil fuels ?

Catalysis for energy: New challenges for a sustainable energetic development

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Catalysis for energy: New challenges for a sustainable energetic development