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Catalysis for Renewables: Opportunities and Challenges

Research Priorities in Renewables

Main Area

Research Priorities 0

Timeline 5 10 years

BGtL process (Bio-Gas to Liquid) Bioalcohols

Biodiesel

More robust and stable catalysts for gasification and gas upgrading (tar cracking) New catalytic approaches for the pretreatment 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 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 Catalytic pyrolysis for wet biomass

Thermochemical BtL (Biogass to Liquids)

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Main Area

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

Timeline 0 5 10 years

Biorefineries

Valorization of byproducts

Chemicals from biomass

Factors driving the future of biobio-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 biobio-resource based society Biomass

Products

Main areas of activities

Biofuels Bio-diesel (direct or via syn-gas / FT/hydrocrack.) Bio-gasoline (ligno-cellulosic pre-treatment, bioalcohol upgrading, liq. phase reforming p g to HC, , oxygenated yg via syn-gas, y g , FAME-FAEE, , ETBE, , 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 largescale products, or building blocks

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Product flowflow-chart for biomass feedstocks

Biomass Feedstocks Starch Hemicellulose Cellulose Lignin Oil Protein

Intermediate Platforms

Biobased Syn gas

Sugars
Glucose,Fructose, Xylose Arabinose,Lactose,Sucrose, Starch

Aromatics
Gallic,Ferulic acid,

Direct Polymers & Gums C6

Building Blocks

Syn Gas

C2

C3
Glycerol,Lactic, 3Hydroxy propionate, Malonic acid, Serine

C4
Succinic,fumaric & malic acids, Aspartic acid,3 Hydroxy Butyrrolactone, Acetoin,Threonine

C5

H2,methanol &higher alcohols,oxo andiso synthesis products, FischerTropsch chemicals

Itaconic acid, Citric/Acotonic Furfural,Levulinic acid,5Hydroxy acid,Glutamic methyl furfural, acid,Xylonic acid, Lysine,Gluconic Xylitol/Arabitol acid,Glucaric acid, Sorbitol

Biofuel production pathways

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Biodiesel process chart

Biodiesel technology
Transesterification reaction Predominantly uses homogeneous base catalysts e.g. sodium methoxide, sodium hydroxide and potassium hydroxide. Differences between commercial p processes: 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 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 catalysts

ESTERFIP process

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Catalysts 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 - Green diesel

Feed
Methanol Vegetable Oil H2 Vegetable Oil SMEs vs refinery
Hydroprocessing 99 BBL Mixed Fatty Acid Esters (Bio Diesel)

Process
Biodiesel Biodiesel

Product
Biodiesel Glycerol Green Diesel

13 BBL 100 BBL + Methanol Vegetable Oil (Triglycerides)

+ Glycerol

8 BBL

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

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Green Diesel Balance

100 BBL Vegetable Oil + H2 (Triglycerides)

99 BBL Green Diesel

CO2 9 BBL + Propane + H O 2

Equivalent volume yield of diesel fuel Uses available hydrogen as a feedstock No low value liquid by-products Can C process fatty f tt acids id in i lower l cost t vegetable t bl oils il

Green diesel reactions

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Ecofining process to green diesel

Vegetable Oil
Acid Gas Removal

Make-up Hydrogen CO2

Reactor

Separator

Propane & Light Ends Naphtha or Jet J t Water

Upgrade vegetable oil using hydroprocessing 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 possible fuel ibl

Diesel Product

Green diesel fuel properties

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Green diesel economics

$500 $560MT w/Tax Incentive $400 $560MT $300 $420MT $200 $100 $0 50.00 60.00 30.00 40.00 -$100 -$200 -$300 -$400 -$500

Sensitivity to Veg Oil Price

NPV, $MM

70.00

80.00

Crude Price, $/bbl

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

Driven by Feedstock Cost

Ecological impact of various diesel fuels

Single Environmental Impact Score
300
Kg CO2/Kg Fuel Impact Points

Climate Active CO2

4 3.5 3 2.5 2 1.5 1 0.5 0 Petroleum Biodiesel Diesel Green Diesel

250 200 150 100 50 0 Petroleum Diesel Biodiesel Green Diesel

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

10

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Process chain analysis

WELL-TO-WHEEL

TANKTOWHEEL

WELL-TO-TANK

L.C.A. - Impact assessment

11

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Global warming potential

Economic vs. environmental aspects

12

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Greenhouse gas emission - bioethanol

2nd Gen. ethanol process from cellulose

Large part of the cost is due to enzymatic hydrolysis

13

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Lignin conversion
Wood Pulp & paper mill
Liquid residues e e.g. g - black liqour (lignin rich)
- carbohydrate degradation products Vapour phase
Bio oil intermediate Crude Bio oil

Paper H2-free p processes H2 p processes

(suitable for paper mill infrastructure) (require petro refinery infrastructure)

HDO

Biomass pre-treatment

catalytic cracking
Liquid phase

Solid residues Logging residues

(high lignin content)

catalytic d depolymerization l i i
Solid phase

H2-free Up-Grading

Bio fuel

Separation
Oxygenates Chemicals

Bark

direct catalytic conversion

LignoLigno -cellulose biorefinery

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Technical biomass potential

Former Soviet Union Middle East Woody by-products Herbeaceous by-products M Manure Energy crops Europe 36% 40% Afica Worldw ide (2000) approx. 104 EJ/a

Asia Latin America + Caribbean North America 0 5 10 15 20 25

7% 17%

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

First generation biofuels

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Emerging issues

Second generation biofuels

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