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SUSTOIL, Foggia- Italy, Friday 24 April 2009

Levulinic acid as platform chemical Levulinic acid as platform chemical from oil plant strawfrom oil plant straw

presented by:

Prof. Dr. Birgit Kamm Scientific Director, Research Institute biopos e.V., 14513 Teltow-Seehof, Germany, kamm@biopos.de

and Brandenburg University of Technology Cottbus

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Content:1. Fractionation from whole oil plants2. Yields of straw from oil crops3. Model for Production of Platform Chemicals (Levulinic acid) Acidolyse of carbohydrates Production and Application4. LA-derived transport fuels5. Next steps

Levulinic acid as platform chemical Levulinic acid as platform chemical from oil plant strawfrom oil plant straw(involved in WP 1, WP 2)(involved in WP 1, WP 2)

SUSTOIL, Foggia- Italy, Friday 24 April 2009

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1. Fractionation of whole crop oil plantExample: rape chain flow chart

source: ifeu / supplement: biorefinery.de GmbH

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(1)Harvesting rape plant: 7 tons / ha

(2) FractionationSeed: 3 tons/ haStraw: 4 tons/ ha

2 tons straw left in field2 tons straw go to processing

(3) Press cake fractionation

Crude fibres from rapeseed:10,3 % (on d.m.)Crude fibres from sunflower-seed:17,3 % (on d.m.)

SUSTOIL, Foggia- Italy, Friday 24 April 2009

2. Yields of straw from oil crops

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BuildingBlocks

SecondaryChemicals

IntermediatesPlatformsPrecursorsBiomass

Starch

Hemicellulose

Cellulose

Lignin

Lipids, Oil

Protein

Carbohydrates

SynGas

Sugar- Glucose- Fructose- Xylose

Lignin

Lipids/Oil

Protein

SynGasC1

C2

C3

C4

C6

Aro-matics

C5

directPolymers

Glycerol

Lactic acid

Propionicacid

Lysine

Carnitine

Products/Uses

Ethanol

MethanolEther Fuel additives

IndustrialSolvents

Olefins Green solvents Transportation

Diacids, Esters

Emulsifiers

Textiles

Dilactid

PLA

Furfural

Levulinicacid

CaprolactamNylons

Furane

…..

Polyurethanes

……

Acrylate

Polyacrylate1,3-PDO

THF

Safe Food Supply

Environment

Communication

Housing

Recreation

Health a. Hygiene Gallic acid

Polysaccharides

Resins

Chemicalintermediates

Phenolics

….

3. Model for Production of platform chemicals (such as levulinic acid)

Kamm, B.; Gruber, P.R.; Kamm, M.; Biorefineries, Industrial Processes and Products, Wiley-VCH, 2006

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Acidolysis of carbohydrates

Levulinic acid yields in 20% HCL, T = 108°C

Basic materialCarbohydrate/ acid ratio

t [h] yield [%]

C6H12O6 x H2O 1 : 2,5 5 46,7

glucose 1 : 10 5 62

potato starch (11,7% H2O) 1 : 10 6-7 60,1

cellolignin (wood process.)

cellulose-content 48,6% 1 : 10 8 60,3

Levulinic acid + esteruse: cosmetics industry, odoriferous substance, solvent, textile printing

C6H12O6(H+) H3C C

O

CH2 CH2 COOH + HCOOH + H 2O

Fp: 37°C, Kpo.1: 95-96°Cl.l. in H2O, alcohol, ether

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Demonstration Plant in EuropeBiofine ProcessCaserta /Italy

3000 t/day

The feedstock is hydrolysed with 1-5% mineral acid in two The feedstock is hydrolysed with 1-5% mineral acid in two reactors. reactors. The first has a temperature of 210-230°C and a residence The first has a temperature of 210-230°C and a residence time of 13-25 seconds. Hydroxymethyl furfural is produced time of 13-25 seconds. Hydroxymethyl furfural is produced and goes to a second reactor where it is hydrolysed further and goes to a second reactor where it is hydrolysed further at 195-215 °C for 15-30 minutes to produce levulinic acid at 195-215 °C for 15-30 minutes to produce levulinic acid from cellulose.from cellulose.

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SUSTOIL, Foggia- Italy, Friday 24 April 2009

FeedstocksFeedstocks Levulinic acid-derivates

Levulinic acid-derivates

Consumer products

Consumer products

plant hexoses(press cake a.o.)

papermill sludge

scrap paper

wood waste

forestry residuals

organic acids

solvents

biopolymers

fuels

misc. organics

• coatings• dyes• herbicides• adhesives• cosmetics• fuel -additives• plastic- substitutes• food-additive• nylon• pesticides• pharmaceuticals• PVC-plastics• textiles• resins (auto & electrical parts)

Levulinic acid — Production and UseLevulinic acid — Production and Use

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4. LA-Derived Transport Fuels4. LA-Derived Transport Fuels

Methyltetrahydrofuran (MTHF) is produced Methyltetrahydrofuran (MTHF) is produced via the catalysed hydrogenation of LA to g-valerolactone (GVL), via the catalysed hydrogenation of LA to g-valerolactone (GVL), which, on further hydrogenation, yields 1,4-pentanediol and which, on further hydrogenation, yields 1,4-pentanediol and MTHF in high yield (92% theoretical MTHF in high yield (92% theoretical ~110 litres MTHF for 100 ~110 litres MTHF for 100 litres of LA).litres of LA).

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LA-Derived Transport FuelsLA-Derived Transport Fuels

ETHYL LEVULINATE ETHYL LEVULINATE

An ester of LA that is used as an oxygenate diesel additive. Allows An ester of LA that is used as an oxygenate diesel additive. Allows diesel and ethanol to mix. diesel and ethanol to mix.

Up to 20% of total volume in regular diesel engines, no adverse Up to 20% of total volume in regular diesel engines, no adverse effects on performance.effects on performance.

High oxygen content and lubricity allows a cleaner burn.High oxygen content and lubricity allows a cleaner burn.

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5. Next steps

Evaluation of further product lines and applications based on levulinic acid

Estimation of potential market volumes of platform chemical

Proposals for further research and development in Europe

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Contact

Prof. Dr. Birgit KammDirector of the Institute Biopos e.V.and BTU CottbusResearch Centre Teltow-Seehof,

Potsdam and Teltow in the Greater Berlin, Germany

biorefinery.de company (GmbH)Main Seat: Stiftstraße 2, D-14471 Potsdam, GermanyEmail: office@biorefinery.de Laboratories Teltow-Seehof Kantstraße 55, D-14513 TeltowWeb: www.biorefinery.de, www.biorefinica.de

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Thank you for the invitation and your attention

City of Potsdam - Market SquareState of Brandenburg,

Greater Berlin, Germany