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Catalysis for Renewables: Catalysis for Renewables: Opportunities and ChallengesOpportunities and Challenges

Main Area Research Priorities Timeline

0 5 10

Main Area Research Priorities Timeline

0 5 10

Research Priorities in RenewablesResearch Priorities in Renewables

0 5 10 years BGtL process (Bio-Gas to Liquid)

More robust and stable catalysts for gasification and gas upgrading (tar cracking)

Bioalcohols New catalytic approaches for the pre-treatment and hydrolysis of (lingo)cellulose biomass to fermentable sugars

Robust and poisons tolerant (bio)catalysts

Biocatalysts able to use a large spectrum of substrates and/or to produce other alcohols than ethanol (butanol, in particular)

Solid base catalysts with a high conversion

0 5 10 years BGtL process (Bio-Gas to Liquid)

More robust and stable catalysts for gasification and gas upgrading (tar cracking)

Bioalcohols New catalytic approaches for the pre-treatment and hydrolysis of (lingo)cellulose biomass to fermentable sugars

Robust and poisons tolerant (bio)catalysts

Biocatalysts able to use a large spectrum of substrates and/or to produce other alcohols than ethanol (butanol, in particular)

Solid base catalysts with a high conversion

Biodiesel

Solid base catalysts with a high conversion efficiency Efficient coupling of catalysts and membrane Trans-esterification catalysts stable in the presence of water and impurities

(Bio)catalysts for trans-esterification of waste products

Thermochemical BtL (Biogass to Liquids) Catalytic pyrolysis for wet biomass

Biodiesel

Solid base catalysts with a high conversion efficiency Efficient coupling of catalysts and membrane Trans-esterification catalysts stable in the presence of water and impurities

(Bio)catalysts for trans-esterification of waste products

Thermochemical BtL (Biogass to Liquids) Catalytic pyrolysis for wet biomass

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Biorefineries

yNew and/or improved catalytic processes for chemicals production through the integration of the biorefinery concept and products into the existing chemical production chain

New advanced catalytic solutions to reduce waste emissions (solid, air and especially Biorefineries

yNew and/or improved catalytic processes for chemicals production through the integration of the biorefinery concept and products into the existing chemical production chain

New advanced catalytic solutions to reduce waste emissions (solid, air and especially

Main Area Research Priorities Timeline

0 5 10 years

Main Area Research Priorities Timeline

0 5 10 years

Biorefineries water) New catalysts to selectively de-oxygenate products from biomass transformation

Catalysts to selectively convert chemicals in complex multicomponents feedstocks

New biomimetic catalysts able to operate under mild conditions

Small catalytic pyrolysis process to produce stabilized oil for further processing in larger plants

Valorization of byproducts

New routes for glycerol and bioethanol upgrading Improved and more efficient catalysts to produce H from byproducts and waste in

Biorefineries water) New catalysts to selectively de-oxygenate products from biomass transformation

Catalysts to selectively convert chemicals in complex multicomponents feedstocks

New biomimetic catalysts able to operate under mild conditions

Small catalytic pyrolysis process to produce stabilized oil for further processing in larger plants

Valorization of byproducts

New routes for glycerol and bioethanol upgrading Improved and more efficient catalysts to produce H from byproducts and waste inproduce H2 from byproducts and waste in liquid phase

Chemicals from biomass

Optimised combination of biotechnology processes with classical and new (bio)catalytic processes to produce at low cost new monomers

Catalytic methods to produce smart and/or advanced materials by functionalization of polymeric and dendrimeric materials

New catalysts for polymer matrix nanocomposite Nano-biotech catalytic methods to produce high performance materials

produce H2 from byproducts and waste in liquid phase

Chemicals from biomass

Optimised combination of biotechnology processes with classical and new (bio)catalytic processes to produce at low cost new monomers

Catalytic methods to produce smart and/or advanced materials by functionalization of polymeric and dendrimeric materials

New catalysts for polymer matrix nanocomposite Nano-biotech catalytic methods to produce high performance materials

Factors driving the future of bioFactors driving the future of bio--feedstocks feedstocks

• Availability of biomass– no competition with food (1st to 2nd generation)– use of waste and agro-food residues

• Maintain actual investment in infrastructure (refinery, cars, etc.)

• Competition with alternative renewable energy (PV, etc) →focus on transport (H2 ?)

• Supply-chain logistic

• Integration with chemicals (→ biorefineries)

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Tools for bioTools for bio--resource based societyresource based societyBiomass

Products

Main areas of activitiesMain areas of activities• Biofuels

– Bio-diesel (direct or via syn-gas / FT/hydrocrack.)– Bio-gasoline (ligno-cellulosic pre-treatment, bioalcohol upgrading, liq.

phase reforming to HC, oxygenated via syn-gas, FAME-FAEE, ETBE, p g , yg y g , , ,alcohol to gasoline)

– Bio-oils from pyrolisis (upgrading)– Bio-gas (cleaning SNG)– Bio-H2 (liq. or gas phase reforming, photo reforming)– Reduce environmental impact (water, air)– Bio-refineries

• Chemicals– Valorizat. byproducts (ex. glycerol) – Use carboxydrate, oils, terpenes, etc. for fine chemicals, some large-

scale products, or building blocks

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Product Product flowflow--chart chart for for biomass feedstocksbiomass feedstocksStarch HemicelluloseBiomass

FeedstocksCellulose Lignin Oil Protein

IntermediatePlatforms

SugarsGlucose, Fructose, Xylose

Arabinose, Lactose, Sucrose, Starch

BiobasedSyn gas

AromaticsGallic, Ferulic

acid, …

DirectPolymers & 

Gums

Building Blocks

SynGas C2 C3 C4 C5 C6

H2, methanol & higheralcohols, oxo and iso‐synthesis products, Fischer‐Tropsch

chemicals

Glycerol, Lactic, 3‐Hydroxypropionate, Malonic acid, 

Serine

Succinic, fumaric& malic acids, 

Aspartic acid, 3‐Hydroxy 

Butyrrolactone, Acetoin, Threonine

Itaconic acid, Furfural, Levulinicacid, Glutamic

acid, Xylonic acid, Xylitol/Arabitol

Citric/Acotonicacid, 5‐Hydroxy methyl furfural, Lysine, Gluconicacid, Glucaric acid, 

Sorbitol

Biofuel production pathwaysBiofuel production pathways

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BiodieselBiodiesel process chartprocess chart

BiodieselBiodiesel technologytechnology• Transesterification reaction – Predominantly uses homogeneous base

catalysts e.g. sodium methoxide, sodium hydroxide and potassium hydroxide.

• Differences between commercial processes:p– Reactor Design: Continuous Stirred Tank Reactor (CSTR), Loop

Reactor, Tubular Reactor.– Purification Step: Residual catalysts and soap need to be removed

from biodiesel and glycerol. (main drawback)• Purification processes: Water washing process and adsorbent

treatment process (water-free process):– Water washing process – need waste water treatment plants– Water washing process – need waste water treatment plants.– Evaporate and recover water for re-use: energy intensive.– Adsorbent treatment process e.g. Magnesium Silicate – high cost of

adsorbent and disposal of spent adsorbents• Eliminate catalyst cleaning up step and simplify biodiesel and

glycerol purification (solid catalysts, enzymatic transesterification)

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Transesterification with solid catalystsTransesterification with solid catalysts

ESTERFIP processESTERFIP process

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Catalysts for biodiesel transesterificationCatalysts for biodiesel transesterification

• Acid– deactivation in the presence of free fatty acids

• Basic– alkaline (Na+, K+) or alkal.-earth (Ca2+, Sr2+) metals– oxide or mesoporus materials as support

Vegetable oils processing routes Vegetable oils processing routes -- Green dieselGreen diesel

FeedFeed ProcessProcess ProductProduct

BiodieselBiodieselBiodieselMethanol Biodiesel Biodiesel

GlycerolBiodieselBiodiesel

Vegetable OilBiodiesel

Green DieselVegetable Oil

H2 Hydro-processing

SMEs vs refinery

99 BBL99 BBL

• 8 vol-% of product is low value glycerol• Requires methanol as a feedstock, higher priced vegetable oil

100 BBL100 BBLVegetable OilVegetable Oil(Triglycerides)(Triglycerides)

13 BBL13 BBLMethanolMethanol

8 BBL8 BBLGlycerolGlycerol++ ++

99 BBL 99 BBL Mixed Fatty Mixed Fatty Acid EstersAcid Esters(Bio Diesel)(Bio Diesel)

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Green Diesel BalanceGreen Diesel Balance

100 BBL100 BBLVegetable OilVegetable Oil HH22

99 BBL 99 BBL GreenGreen ++++ 9 BBL 9 BBL

PropanePropane++ COCO22HH OO

• Equivalent volume yield of diesel fuel• Uses available hydrogen as a feedstock• No low value liquid by-products

C f tt id i l t t bl il

Vegetable OilVegetable Oil(Triglycerides)(Triglycerides)

22 Green Green DieselDiesel

Propane Propane ++ HH22OO

• Can process fatty acids in lower cost vegetable oils

Green diesel reactionsGreen diesel reactions

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EcofiningEcofining process to green dieselprocess to green diesel

• Upgrade vegetable oil using hydroprocessing

Make-up Hydrogen

Vegetable Oil

y p g• Product is an high cetane

diesel blending component• Hydrocarbon product, not an

oxygenated compound• Co-production of propane,

naphtha, and high quality jet f l ibl

Reactor CO2

Propane & Light Ends

Separator

Acid Gas Removal

NaphthaJ t fuel possible

Water

Diesel Product

or Jet

Green diesel fuel propertiesGreen diesel fuel properties

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Green diesel economicsGreen diesel economics

$500$400$300

Sensitivity to Veg Oil Price$560MT w/Tax Incentive$560MT

NPV

, $M

M

$300$200$100

$0-$100-$200-$300-$400-$500

30.00 40.00 50.00 60.00 70.00 80.00

$420MT

• Palm oil ($420/MT;$1.47/gal): Profitable at crude > $52/bbl • Soy oil ($560/M ;$1.96/gal): Profitable at crude > $67/bbl • Soy oil w/ $1/gallon subsidy: Profitable at crude > $38/bbl

Crude Price, $/bbl

Driven by Feedstock Cost

Ecological impact of various diesel fuelsEcological impact of various diesel fuels

Single Environmental Impact Score Climate Active CO2

4300

00.5

11.5

22.5

33.5

4

Kg

CO

2/Kg

Fuel

0

50

100

150

200

250

300

Impa

ct P

oint

s

• Soybean feed • Higher points mean higher environmental impact• Green Diesel is best option

0Petroleum

DieselBiodiesel Green

Diesel

0Petroleum

DieselBiodiesel Green

Diesel

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Process chain analysisProcess chain analysisW

ELL-

TO-W

HEE

L

WEL

L-TO

-TA

NK

TAN

K-

TO-

WH

EEL

L.C.A. L.C.A. -- Impact assessmentImpact assessment

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Global warming potentialGlobal warming potential

Economic vs. environmental aspectsEconomic vs. environmental aspects

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Greenhouse gas emission Greenhouse gas emission -- bioethanolbioethanol

22ndnd Gen. ethanol process from celluloseGen. ethanol process from cellulose

Large part of the costis due to enzymatic

hydrolysis

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Lignin conversionLignin conversion

H2-free processes H2 processes

Wood Pulp & paper mill

Liquid residues e g

Paper

2 p(suitable for paper mill

infrastructure)

2 p(require petro refinery infrastructure)

Vapour phasecatalytic cracking

Liquid phasecatalytic

d l i iBio fuel

H2-freeUp-Grading

Bio oilintermediate

Crude Bio oil

HDO

Liquid residues e.g.- black liqour (lignin rich)- carbohydrate degradation products

Logging

Solid residues

-trea

tmen

t

Solid phasedirect catalytic

conversion

depolymerization

Oxygenates Chemicals

Logging residues

Bark (highlignin content)

Bio

mas

s pr

e-

Separation

LignoLigno--cellulose biorefinerycellulose biorefinery

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Technical biomass potentialTechnical biomass potential

Former SovietUnion

Woody by-products

Herbeaceous by-products

M

Latin America +

Asia

Afica

Europe

Middle East Manure

Energy crops

40%36%

Worldw ide (2000)approx. 104 EJ/a

0 5 10 15 20 25

North America

Latin America Caribbean

Technical biomass potenial (base case 2000) [EJ/a]

17%7%

First generation First generation biofuelsbiofuels

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Emerging issuesEmerging issues

Second generation Second generation biofuelsbiofuels