Sugar Biorefinery

Wolfgang Wach, Südzucker AG Mannheim/Ochsenfurt IEA-Bioenergy Task 42 Biorefineries – German Workshop on Biorefineries 15th September 2009, Worms Content

 Südzucker Group

 Sugar factory and logistic aspects

 Sugar as raw material for biobased economy

 Bioenergy

 Palatinose™ Isomalt

 Gluconic acid

 Summary

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 2 The Südzucker Group: Overview

 Global operating German food group  Segments sugar, special products, CropEnergies and fruit  18.000 employees  € 5.9 billion annual revenues  Sugar production: 4.2 million tonnes  Leader in the European sugar market  Member of the German MDAX

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 3 Core Competence of the Südzucker Group

“From Farm to Fork”

Transformation of agricultural raw materials into food/feed ingredients and agrochemicals

 The Südzucker Group relies on its close cooperation with the agricultural industry, the basis of its commodities, the group's in- house research expertise, its extensive manufacturing knowledge in connection with processing renewable raw materials and its marketing experience, particularly in the B2B area.

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 4 Südzucker Group – Segment Overview

Sugar Special products CropEnergies Fruit segment segment segment segment

30 sugar factories and BENEO-Group Bioethanol Fruit preparations 3 refineries in (Orafti/Palatinit/ 4 sites in Germany, Fruit juice concentrates Germany, Austria, Remy) Belgium and France 37 production sites Belgium, Freiberger worldwide Bosnia-Herzegovina, PortionPack Europe The Czech Republic, Starch France, Hungary, Moldova, Poland, Romania, Slovakia

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 5 Sites of the sugar factories/refineries today

 Südzucker  Raffinerie Tirlemontoise  Saint Louis Sucre Germany  AGRANA Poland

Warburg Brottewitz Wabern Zeitz Strzyzów Belgium Swidnica Strzelin Tienen Otmuchów Cerekiew Ropczyce Roye Wanze Offstein Ochsenfurt Czech. Eppeville Offenau Republic Opava Etrépagny Hrusovany Cagny Rain Slovakia Plattling Leopoldsdorf Sered Moldova

Tulln Drochia Alexandreni Austria Hungary Roman Kaposvár Falesti France

Romanie ^ Brcko Buzau Bosnia- Marseille Herzegovina Status at: Mai 2009

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 6 Agricultural raw Products material Sugar beet Sucrose Invert sugar syrup, Fructose syrup, “From PalatinoseTM, Isomalt, Caramel sugar agricultural raw Rice Flour materials to food Starch ingredients and Proteins Rice Bran agrochemicals” ” Maize, Potatoes Starch Modified starches Inulin derivatives Chicory Inulin Oligofructose Inulin derivatives Sugar beet Ethanol Maize Wheat Fruit Fruit juice concentrates Fruit preparations

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 7 Sugar beets – a powerful sugar producing crop

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 8 Südzuckers core competence ‚From Agrocrops to Agrochemicals‘

biomass logistics processing conversion product market

Best available technology

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 9 Content

 Südzucker Group

 Sugar factory and logistic aspects

 Sugar as raw material for biobased economy

 Bioenergy

 Palatinose™ Isomalt

 Gluconic acid

 Summary

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 10 Sugar plant data

 Grown under contract  campaign: mid September to begin January  Typical sugar factory:  15.000 t beets/day, beet storage on site for max. 3 days  800 trucks/day, 24-h-delivery, 30 bis 40 trucks/h  1,5 … 2 million t beets/campaign  200.000 bis 300.000 t sugar/campaign  130.000 bis 180.000 t dry feed pulp/campaign  or 330.000 bis 440.000 t pressed pulp/campaign  Costs for Logistics  Transportation approx. 40 km  Costs for loading, cleaning and transport approx. 6 €/t beets

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 11 Sugar Yield [t sugar/ha grown] - the last 26 Years

[t Sugar/ha]

13

12 11 10 9

8 7 6 5

4 8 04 06 94 02 0 0 82 84 88 92 9 99 000 0 2 9 9 9 990 9 1 1996 1 2 2 2 1 1 1986 1 1 1

SZ

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 12 Amounts of nitrogen- phosphor- and potassium-commercial fertilizer used in sugar beet cultivation 1980 - 2005 (Trials within „Verband Süddeutscher Zuckerrübenanbauer e.V., Würzburg“)

kg fertilizer / t sugar yield 300 30 N N P2O5 250 25 P2O5 K2O K2O 200 20 -1 150 15 kg ha 100 10

50 5

0 0

1980 1982 1984 1986 1988 1990 1992 1994 1996 1998 2000 2002 2004 2006 1980 1982 1984 1986 1988 1990 1992 1994 1996 1998 2000 2002 2004 2006

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 13 Sugar beet harvest with topping of beets

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 14 Directly on the truck or beet clamp after harvest

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 15 Coverage of beet clamp soil cleaning freeze protection reducing sugar losses

Only short term storage – not for months

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 16 Loading of the beets to trucks (no tractors)

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 17 Soil separation during loading

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 18 Unloading of the beets in the plant

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 19 Unloading – here: dry

in many plants as well wet unloading

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 20 Storage and ventilation of beets in the plant

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 21 Sugar logistic – mainly on road

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 22 Feed material from sugar beet – wet or dry beet pulp (pellets)

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 23 Offstein site (located 15 km from Worms) – biorefinery ‚nucleus‘

Sugar factory campaign daily beet capacity 15.800 t about 19.000 ha beet area Sugar production 1.500 … 1700 t/d Thick juice storage 2 x 50.000 m³ thick juice storage

Isomalt R&D Syrups / Burnt Sugars Fructose

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 24 Content

 Südzucker Group

 Sugar factory and logistic aspects

 Sugar as raw material for biobased economy

 Bioenergy

 Palatinose™ Isomalt

 Gluconic acid

 Summary

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 25 From classical beet process to sugar biorefinery

Slicing Machine Press- water

Thickening Filter

Unloading Thin Juice to Liming Juice Evaporation Cosette / Tower Extractor Beet Storage Beet Washer Juice Mixture Carbonation Raw Juice Exhausted Cossettes Thin Juice

Raw Juice fermentation Thick Juice to Bioethanolbioethanol Biomethan from Molasses beet pulp

Evaporating White Refinade Crystallizers Raw- After Thick Juice sugar sugar sugar product To Juice Heat Exchangers and Crystallization Steam

Steam turbine

Fuel Minglers Run off Centrifugals Steam Boiler syrup Run off Exhaust syrup steam Cooling and Thin Juice drying drums Multiple Effect Evaporator Dissolving White sugar Sugar Refinade sugar Silo Molasses Melted Screening Liquior Filter Packaging Dispatch green syrup

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 26 CropEnergies sugar based bioethanol plant in Zeitz, Germany

 Raw material:  150,000 t of thick juice/a  Ethanol  100,000 m3/a  Side product: Fermentation  35,000 t/a vinasse  Fermentation:  Batch wise  Start of production:  June 2008

Distillation

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 27 Principle of ethanol production from thick juice (Zeitz)

1. Thick juice (65-70 % dry matter) fresh water

backset vinasse 2. Diluted thick juice

3. Pasteurisation at about 80 °C

N-source, yeast, trace elements

4. Batch fermentation

Partial yeast separation 5. Distillation, rectification Ethanol

6. Evaporation of vinasse Feed, fertiliser

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 28 AGRANA opens first-of-its-kind biogas plant in Kaposvár, Hungary

 In 2007 at the site of the Kaposvár sugar factory in Hungary, AGRANA installed a large-scale biogas facility that to date is unique in the European sugar industry.

 The feedstock consists of the spent beet pulp produced during sugar beet processing, as well as of beet syrup. These organic by-products now supply a large portion of the energy needs of the sugar plant.

 About 860 tonnes of beet pulp per day is fed into the plant’s fermentation process, corresponding to roughly one-half of the factory’s daily output of beet pulp. This results in the production of 110,000 cubic metres of biogas per day.

Quelle: press release 15.11.2007; www.agrana.com

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 29 71. IIR-Kongress am 13./14. Februar 2008 in Brüssel Eugen Gaschler

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 30 71. IIR-Kongress am 13./14. Februar 2008 in Brüssel Eugen Gaschler

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 31 Product Groups with high Potential

 Product categories with revenue potential >> 1€

 Food ingredients with special features / properties (functional food)

 Renewable feedstocks, e. g. products with additional properties to

petro chemicals

 Maximum utilization of intrinsic molecular structure, i. e.

 Pursuing these targets beyond the present utilisation means:

„R & D in new technologies"

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 32 Sugar based Biorefinery

new technoloy chrom. Glucose Gluconic acid Fru/Glu mixture catalysis Specific catalysts Fructose Mannitol-solution Sucrose

catalysis cryst. cat. Isomaltulose (solution) Isomaltulose Isomalt 50 GPM : 50GPS

new catalyst Isomalt GS Technology for material conversion 40GPM : 60 GPS

new drying Chemical catalytic processes Isomalt LM • Hydrolysis • Hydrogenation new agglo. • Oxidation Isomalt DC cat. Biochemical catalytic processes Isomalt HC • Hydrolysis • Isomerisation • Transferases

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 33 OH HO O HO OH H2 HO OH OH OH catalyst HO OH OH OH HO O OH Glucose Sorbitol HO O OH HO Hydrolyse O OH Invertase, H+ OH Sucrose OH OH OH H OH 2 O OH catalyst HO OH HO OH OH HO

Fructose Sorbitol + Mannitol

 Applied by Südzucker: H+ -fixed-bed ion exchanger (about 200kt/a)  Large-scale production of fructose by Südzucker  Mannitol (sorbitol)-production of SZ-products by customers

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 34 OH

O OH HO O HO HO Sucrose OH O OH OH

PalatinoseTM IsomaltTM Fructooligosaccharide Neoamylose OH OH OH O HO O OH HO O HO OH OH HO OH HO HO O OH OH HO OH O O OH OH HO HO HO O O OH O O OH OH OH HO O OH HO OH OH O O OH O O HO HO OH n OH

O OH O HO n

OH - sweet - sweet - less sweet OH - not sweet - crystalline - crystalline - crystalline - crystalline - water-soluble - water-soluble - very well water-soluble - insoluble in water - delayed digestible glucose - little digestible - indigestible - indigestible source - caloric energy - caloric energy ~ 1,5 kcal/g - caloric energy 1 kcal/g - caloric energy 4 kcal/g regulatory EU: 2,4 kcal/g - very low GI - very low GI physiological USA: ~2 kcal/g - very low GI - very low I I - very low I I - very low GI - very low I I - fiber - fiber - very low I I - bifidogenic - fiber - higher mineral resorption - bifidogenic (long-chain inulin) - toothfriendly - toothfriendly ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 35 Production of PalatinoseTM

OH 3 HO O OH 1 Palatinose™ Protaminobacter rubrum HO O 2 OH HO 2 Trehalulose Pseudomonas mesoacidophila O OH 3 Leucrose Leuconostoc ssp. OH 1

OH OH HO O HO O OH HO O HO OH OH HO Protaminobacter rubrum OH O OH O O 1,2 1,6 HO OH Saccharide OH Palatinose™ Technical production OH

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 36 What is Palatinose™?

 Palatinose™: The ONLY fully digestible, low GI carbohydrate providing prolonged energy release in the form of glucose  Like sucrose composed of glucose and fructose  A natural constituent of honey  Produced via non-GMO enzymatic rearrangement of sucrose

• Generic name: Isomaltulose • (6-0-α-D-glucopyranosyl-D-fructofuranose) • CAS Reg. No. 13718-94-0

• Total molecular formula: C12H22O11 x H2O • Molecular weight: 360.32

Sugar

Origin and molecular structure of Palatinose™

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 37 Hydrogenation of Palatinose™ to Isomalt

 Chemical catalytic process with Ni-catalyst OH  in fixed bed HO O OH OH HO OH OH OH O O HO OH OH

HO H2 1,1 GPM OH O OH 1-O--D-glucopyranosyl- O HO OH D-mannitol Palatinose™ OH OH HO O OH OH HO OH OH Isomalt is the only bulk sweetener O made from sucrose which can OH OH replace sugar in a 1:1 ratio 1,6 GPS 6-O--D-glucopyranosyl- D-sorbitol

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 38 Palatinose™/Isomalt - Production plant

Offstein, Deutschland

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 39 Oxidation of Carbohydrates

Sugar Beet T = 40-60°C pH = 7-9 Milk

Complexing agent, acid regulator ingredient for cosmetics, pharmaceuticals & cleaners Starch

COOH CH2OH Oxidation on Au / Al2O3 Glucose H C OH H OH or CH OH OH H COOH HO C H 2 High activity OH O O or H C OH Extreme high selectivity > 98% OH H H OH H H High long term performance H C OH H OH Lactose Simple synthesis CH2 OH No leaching Gluconic Acid Lactobionic Acid

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 40 Oxidation of Carbohydrates using supported gold catalyst Advantages vs. fermentative process

OH OH OH O HO O NaOH + ½ O HO + H O 2 ONa 2 HO OH Au/Al2O3 OH OH OH Glucose Sodium gluconate

 Simple synthesis  Applicable for diverse feed (Glucose /- syrups, Maltose, Lactose)  Outstanding properties (high activity, selectivity, long-term stability)  High productivity -1 -1 -1 -1  130 gGluc l h vs. 15 gGluc l h fermentative -1 -1 -1 -1  63 gglucon acid g Kat h vs. 5 gglucon acid g BioM h fermentative  Economically and environmentally friendly process

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 41 Summary

 Sugar biorefinery needs strong  agricultural industry  research expertise (along the value chain)  extensive manufacturing knowledge in connection with processing renewable raw materials  crossfunctional teams

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 42 Thank you for your attention!

Contact:

Dr. Wolfgang Wach Südzucker AG Mannheim/Ochsenfurt Wormser Straße 11 67283 Obrigheim/Pfalz Germany [email protected]

ZAFES Offstein, Dr. Wolfgang Wach 2009/09 IEA Task42 Geman Workshop on Biorefineries in Worms 9105z-wa-wa, Bild 43