Catalysis for energy: New challenges for a sustainable energetic development

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 ?



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 oilFuels &

products

BiomassClosed 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.

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 ”


• 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

Others5 %

OilsFats ProteinsTerpenesAlkaloidsTerpenoidsWaxes

Energy

Chemicals

¿?


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


• Biorefinery concept is built on different “Platforms”


BIOMASS






Sugars

Syngas

Fuels

Chemicals

Heat&

Power

Bio-oil

Bio-oil

Biogas

Oils





• 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


• 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+


BIOMASS






Sugars

Syngas

Fuels

Chemicals

Heat&

Power

Bio-oil

Bio-oil

Biogas

Oils





• Bioil platform


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. %


• Bioil platform


Fast Pyrolysis

Bio-oil



• Bioil platform


Fast Pyrolysis

Bio-oil


• 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

ActivatedCarbon

Extraction Chemicals


BIOMASS






Sugars

Syngas

Fuels

Chemicals

Heat&

Power

Bio-oil

Bio-oil

Biogas

Oils





• Biogas platform

BiogasOrganicWaste

Anaerobic

Fermentation

Digestate

55-65 CH435-45 CO2

HeatElectricity

CHPCogeneration

FertilizersCompost

Gas distributionnetwork


BIOMASS






Sugars

Syngas

Fuels

Chemicals

Heat&

Power

Bio-oil

Bio-oil

Biogas

Oils





• 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


• 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


• 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


BIOMASS






Sugars

Syngas

Fuels

Chemicals

Heat&

Power

Bio-oil

Bio-oil

Biogas

Oils





• 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


Chemical/Enzymatic

Hydrolysis

Cellulose (35-50 %)

C6Glucose

Hemicellulose (15-25 %)

C5-C6

Forest ResiduesAgricultural ResiduesLignocelullosic Crops

StrawCorn StoverBagasse

Lignin (20-25 %)


• Sugar platform : Sugars transformation

Sim

ple

suga

rs(h

exos

esan

d pe

nto

ses)

Transportation fuels

Chemicals


• 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


• Sugar platform : Sugars towards transportation 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


• 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



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

HydrogenolysisOxidationDehydrationPolymerizationEtherification

Chemical – Transesterification of oilsOH

OH

HO OH

OH

HO


3- Hydroxypropionic acidBio-transformations – Fermentation of sugars

Chemical routes

HydrogenationDehydration


1-4- Four carbon diacids(Succinic, Fumaric and Malic)

Bio-transformations – Fermentation of sugars

Chemical routes

HydrogenationAminationsPolymerizations


Aspartic acid

Bio-transformations – Fermentation and enzymatic conversion of sugars

Chemical – Amination of fumaric acid

Chemical routes

HydrogenationDehydrationsPolymerizations


3-Hydroxybutyrolactone

Chemical – Oxidative degradation of starch (H2O2)

Chemical routes

HydrogenationPolymerizations


Levunilic acid

Chemical – Catalytic dehydration of sugars (C6)

Chemical routes

HydrogenationOxidationsCondensations


Glutamic acid


Chemical routes

Hydrogenation


Itaconic acid


Chemical routes

HydrogenationPolymerization


Xylitol

Chemical – Hydrogenation of xylose (C5)

Chemical routes

HydrogenolysisOxidationPolymerization


Sorbitol

Chemical – Hydrogenation of glucose (C6)

Chemical routes

HydrogenolysisOxidationPolymerization


Glucaric acid

Chemical – Oxidation of starch with nitric acid

Chemical routes

DehydrationPolymerization


2,5- Furan dicarboxylic acid (FDCA)

Chemical – Oxidative dehydration of C6 sugars

Chemical routes

HydrogenationPolymerizations



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


• Biorefineries: Future outlook

Fuels

Chemicals

Heat&

Power

Fossil

Sources

CmHnCmHnOx

Biomass

¿?

Yes

But …



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


1st Generation

2nd Generation

Biorefinery



• 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.


• 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


Catalysis for energy: New challenges for a sustainable energetic development

Technology

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