Umwelt-und Ressourcen-schonende Synthesen und Prozesse

Perspektiven der industriellen Nutzung nachwachsender Rohstoffe, insbesonders von Stärke und Zucker H. Röper 4.-6.Sept. Oldenburg
HR/Oldenburg 8/8/00

Renewable Raw Materials
Annual biomass production (photosynthesis) 170 billion t

Carbohydrates 75% Lignin Others* 20% 5%

Lignin

Carbohydrates

*fats, proteins,terpenes,alkaloids, nucleic acids…
HR/Oldenburg 8/8/00

Renewable Raw Materials
Global production/utilisation Annual production used by man 6.000.000.000 tonnes = 3.5% Annual utilisation 62% food, 5% non food
Non Food
300 mio t =5 %

Wood
2.200 mio t 1.800 mio t

Cereals Food
3.700 mio t 2.000 mio t Energy & Housing

2.000 mio t

Oil seeds, Sugar cane, Sugar beet, Fruits, Vegetables

Annual Biomass Production : 170.000.000.000 tonnes
HR/Oldenburg 8/8/00

800 mio t O. Rev. sugar cane.Renewable/Fossil Resources Renewable Resources Total use: 6.000 billion m3 oil 135. vegetables Natural gas . fruits. Ind Cereals 2. FEMS Microbiol. 103 (1992) 355 HR/Oldenburg 8/8/00 Oilseeds.250 mio t O.E Coal 2.800 mio t Wood Oil 3.200 mio t 1.000 mio t Total available: 170. sugar beets.000 mio t 1. Eggersdorfer et al. 7%RM Chem.000 mio t Source: M. Total available: coal 850.250 mio t 2.E.300 mio t OE/a 93% energy.000 mio t/a Fossil Resources Total use: 7.000 mio t/a gas 120.

biodegradability.Fossil/Renewable Raw Materials ➤ The total substitution of fossil raw materials by renewable raw materials is not possible ➤ Renewable raw materials can be competitive to synthetic products. non toxicity and their favourable CO2 balance are utilised in an intelligent way ➤ Their utilisation is especially attractive. if their special functional properties like biocompatibility. if the natural synthetic power of nature can be (partially) used in the target product HR/Oldenburg 8/8/00 .

032 mio t 2 % 0.Renewable Raw Materials Utilisation by the Chemical Industry (D) 1991 Raw Materials (total ) 22.900 mio t 50% 0.4 mio t Gas 1.8 mio t Other l lu el C os e Sugar Starch Oil Fats/Oils Oil 18.100 mio t 6 % .5 mio t HR/Oldenburg 8/8/00 82% 8% 8% 2% Source: VCI 1994 Fats/Oils Starch Cellulose Sugar Other 0.4 mio t Gas RRM Coal Renewable Raw materials 1.7 mio t RRM 1.8 mio t Coal 0.250 mio t 14% 0.465 mio t 28% 0.

6 mio t (6.3 mio t Starch (0.4 (8 m .6%) 17 mio t (21.0 % io ) t Vegetable Oils Sucrose 18.2%) Starch 37 mio t (46.1%) Cellulose HR/Oldenburg 8/8/00 Cellulose .6 mio t (23.European Production of Main Agricultural Commodities Total annual production : 80.7 mio t (9.3 mio t Vegetable oils : 2.3 mio t Annual non food use : 42.1%) 36 mio t (85.7%) 3 .2%) Sucrose : 0.2%) 7.

000 1.000 3. tires (63%) total Chemicals.3) Lubricants. plasticisers (~0.000 Vegetable oils & fats 14 2.8 44.000 342. Fermentation Binders. textile.900.250 582.000 Tensides. Adhesives HR/Oldenburg 8/8/00 .4) Biodiesel Application Paper & pulp Chemical Industries (37%) Regenerate. Fermentation Paper & Corrugating Chemicals.600.5 tonnes 35.2 300.000.000 1.6) Lacquers.075. softeners (~1.000 Sucrose Starch 1.European Non-Food Applications of Agricultural Commodities Raw material Cellulose % of total production 94. dyes (~0.400.8 2.000.000 500.750 36.

g. chirality Reactivity HR/Oldenburg 8/8/00 .Technical Requirements for Renewable Resources General Availability Uniformity Purity Workability Economy Ecology Specific (Bio)compatibility Biodegradability Non-toxicity Molecular structure e.

Product Classification of Renewable Raw Materials Cereals Tubers Wood Agricultural Raw Material Agricultural Raw Material Oil Seeds Fruits Sugar cane & beets Cleaning Cleaning Separation Separation Main Products • • • • HR/Oldenburg Co-Products • • • • Proteins Lecithins Molasses Pectins By-Products • • • • Pulps Lignin Bran Steepwater Cellulose Starch Sucrose Oils 8/8/00 .

hemicellulose. bran Germ oil Gluten Steepwater Paper & corrugating (27%) Thickeners Binders Cobuilders Thermoplastics Complexing agents Flocculating agents Coatings Latex copolymers Fermentation feedstocks Polyols Surfactants Pharma & Cosmetic aids Starch Starch Modified Starches Modified Starches Hydrolysed Hydrolysed Oxidised Oxidised Esters Esters Ethers Ethers Crossbonded Crossbonded Dextrins Dextrins Maltodextrins Hydrolysates Derivatives HR/Oldenburg 8/8/00 .Industrial Uses of Starch Cereals / /Tubers Cereals Tubers Fibers.

Cracked Products Glycol Glycerol DEXTRINS White Yellow Gums Cyclodextrins Graft Polymers SAP STARCH Glucosan MOD STARCHES Hydrolysed Oxidised Esters Ethers (cationic) Biopolyols Erythritol Liquefacts MALTODEXTRINS Block-Copolymers Solutions Emulsions Polycarboxylates Maltitol Glucoside esters Alkyl glucosides APG's Citric acid Lactic acid Itaconic acid GLUCOSE HFCS Aminosorbitols Gluconates SYRUPS Maltose Alcohols Organic acids Ethanol Butanol Amino Acids Lysine Glutamic acid Tryptophane SORBITOL Glucamides Sorbose DAS 2-KGA Vitamin C Sorbitan Esters MANNOSE FRUCTOSE Glucarates SORMAN Mannitol HMF HR/Oldenburg 8/8/00 .

Industrial Uses of Sucrose Sugar Cane / /Sugar Beets Sugar Cane Sugar Beets Beet Pulp Bagasse Molasses Sucrose Sucrose Sucrose Derivatives Sucrose Derivatives •• •• •• Esters Esters Ethers Ethers Acetals Acetals Fermentation feedstocks Polycondensates (starter) Building units (Pharma) Surfactants Glucose + Fructose HR/Oldenburg 8/8/00 Furan resins .

Conversion O Chemical conversion HR/Oldenburg 8/8/00 Dextran. Lactic acid Amino acids Biotechn. Actilight) • Filler in phenol/formaldehyde resins • Component in PU foams .g Citric acid. Amylose Fructooligosaccharides (Neosugar. fat replacer) 3-Keto sucrose Furan dicarboxylic acid Isomalt O Isomaltulose Sucrose O Fructose O HMF Dihydroxymethyl furan Organic acids e.Sucrose utilisation Sucrose tricarboxylic acid Sucroseester (emulsifyer) Sucralose O O O Sucrose polyester (Olestra. Levan.

b) R N H 2/ H 2 /cat.>T R eductiv e am ination a) N H 3 /H 2 /cat. a) 3-A m ino sucrose b) 3-N -alkyl-am ino sucrose Buchholz et al. HR/Oldenburg 8/8/00 .3-Keto sucrose H OH H H O HO H H OH OH H O H HO HO H A grobacterium tum efaciens OH H HOH 2 C O O OH CH 2 OH O HOH 2 C O H H HO H OH O H H HO CH 2 OH H S ucrose 3-K eto-sucrose > p.

s. 60% ds OH OH HO O HO O OH 1 2 β O O OH OH OH n O OH OH OH Sucrose FOS n=0 n=1 n=2 n=3 GF1 GF2 GF3 GF4 Fructose + Glucose Sucrose 1-Kestose Nystose Fructosylnystose FOS FOS G FOS P (>70% d.s.Fructooligosaccharides (scFOS) (Neosugar. Actilight) OH O OH OH OH HO O OH O OH OH Fructosyltransferase (whole cells/immobilised) pH 5-6.2 9 1.) (>70% d.) <25 0.7 21 37 20 36 1 2 >41 >72 HR/Oldenburg 8/8/00 . 60-65 C.

> T H 2 /N i S u c ro s e H OH H HO HO H H O OH H OH OH NH 2 S üdzuck er A G O OH G lu c o s y l-α − (1 − 6 )s o rb ito l 5 0 % G lu c o s y l-α − (1 -6 )m a n n ito l 5 0 % Is o m a ltito l 2 -A m in o -2 -d e o x y -is o m a ltito l HR/Oldenburg 8/8/00 . > p .Isomaltulose/Isomaltitol H OH H HO HO H H OH H O OH O O OH OH OH H OH H H OH 5 -O -( α − D -g lu c o p y ra n o s y l)-D -a ra b in o n ic a c id H O O HO HO H H HOH 2C 1 H H OH O O H OH P ro ta m in o b a c te r ru b ru m O tra n s g lu c o s id a tio n HO HO H H H OH 1 H O 2 /K O H 6' H OH O OH OCH 2 2' 2' H CH 2 OH CH 2 OH HO H H HO H 1' H 2 /N H 3 /C a t.> T Is o m a ltu lo s e > p .

Industrial Uses of Beet Pulp Beet Pulps Beet Pulps Hemicellulose Hemicellulose Pectins Pectins Cellulose Cellulose Protein Protein Insoluble ash Insoluble ash Lignin Lignin Sugar Sugar Enriched Pulps Enriched Pulps •• Cellulose enriched Cellulose enriched •• Pectin enriched Pectin enriched Fractionated Pulps Fractionated Pulps HR/Oldenburg 8/8/00 29% 29% 29% 29% 27% 27% 5% 5% 4% 4% 3% 3% 3% 3% Paper additive Thermoplastic filler Particle board adhesive Biotechnological processes • Alcohol • Methane • Single cell protein Food Applications .

starch components Molweight MW-Distribution Nature of substituent Degree of substitution Salt content Gelatinisation Temperature Solubility Viscosity as function of (c. D) Gel formation Ionic charge Specific manufacturing conditions HR/Oldenburg 8/8/00 Modification Key-properties Application properties< Specific customer demands Rheology Water binding Retention Adhesive / Binding power Gel strength Degradability . t.Correlation basic properties / application properties Basic Properties Molweight MW-Distribution Amylose / Amylopectin ratio Crystallinity Non . T.

Penetration of gelatinised starch into the paper sheet by size press. size press. coater ➤ Wet end: cationic starch (0. e. and controlled ink receptivity ➤ Coating of surface with coating colours to improve gloss. spraying. drying section. improving of paper sheet dry strength. Improving of paper stiffness. dewatering and machine runnability. Fibre retention.g. strength.5-2% on cellulose). ➤ Surface sizing. Cheap way to improve sheet strength in the drying section of the paper machine. magazine paper HR/Oldenburg 8/8/00 .Application of Starch in Paper Production ➤ Process steps: wet end. ➤ Spraying of starch on wet sheet. improved flocculation.

Application of Starch in Paper Production HR/Oldenburg 8/8/00 .

due to difficult environmental control HR/Oldenburg 8/8/00 . briquettes for further processing ➤ Replacement of cheap binders like sulphite liquors. bitumen and pitch to reduce the burden on the environment ➤ Replacement of urea/formaldehyde and phenol/formaldehyde binders. bars.New Starch Based Binders ➤ Use of native and modified starches as binders for compacting of powders and dust to pellets.

green bonding HR/Oldenburg 8/8/00 . ceramic powder aluminium dust coal powder filter dust Dough Pieces e.g.ambient temp.New Starch Based Binders Powder e. Pellets bars briquettes cylinders sheets Drying .about 200°C .g.about 300°C Effect hot bonding carbonisation .

Starch Based Detergent Products Surfactants OH OH OH H O O R HO H HO C H2 H OH OH H C H2O H C H3 O N R A lkyl poly g lucosides COOH OH O OH O OH OH OH O OH OH Glucamides C H2 C O O H HO C COOH C H2 C O O H Builder/Cobuilder Citric Acid C H 2 O Ac H O Ac O Ac H O Ac Oxidised Starch H AcO H AcO H2C C H2 O Ac H O Ac O Ac H O Ac + A cO H H AcO H2C Bleach activators “Sorman” HR/Oldenburg 8/8/00 .

and incineration causes emission problems ➤ Development of biodegradable (compostable) materials for applications. HR/Oldenburg 8/8/00 . Reuse. seems to be logical. which contains 25-30 volume % (5-10 weight %) of plastic materials. disposable diapers).g.Starch in Biodegradable Polymers ➤ More than 100 million tonnes of solid municipal waste (SMW) per year are produced in Western Europe. one-way packaging for fast food items. predominantly packaging material ➤ Landfill space is running short. 2. containers for pralines and ampoules. 5. where long term stability is not required. and hygiene articles (e. Composting of renewable raw materials into biomass.3. Disposal in landfills.g. loose fill (chips) ➤ EU legislation (order) for waste management 1. Prevention. mulch foils and planting pots for agriculture. water and CO2 is seen as biological recycling. 4. Controlled incineration. e.

fibres. films. films. expanded products (loose fill) Molds and films but not biodegradable . Polylactic acid) 100% Molds. films.Starch in Thermoplastic Polymers Disintegrated reactive starch HR/Oldenburg 8/8/00 BI O Granular native starch Filler for polyethylene polypropylene DE G Composite material > 50% with different synthetic starch polymers 6-20% starch RA DA BI L Extruded plastified starch Thermoplastic starch > 90% starch IT Y Biopolymers based on Polyester fermentation products (PHB. expanded products with lower water resistance / mechanical properties Molds. based on medical implants starch Molds.

no colour. carriers. non critical impurities. matrices for controlled release ➤ Conformity with Pharmacopeia (US. film forming agents. tactile characteristics. emulsifyers thickeners. no odour natural-compatible-non-toxic-functional-controlled release-nutritional-chiral HR/Oldenburg 8/8/00 . desintegrating agents. stability. ➤ Skin compatibility. environmental compatibility.Starch based Products for Pharma and Cosmetics Pharma ➤ Excipients for tabletting. humectants. processibility. EU. lubricants. skin protection. binder for coatings. Jpn) Cosmetics ➤ Emollients.

natural .Starch based Products for Pharma and Cosmetics Native starch Modified starches • Esters • Ethers • Hydrophobic Maltodextrins Glucose syrups Dextrose Glucosides • Glucoside esters Cyclodextrins Polyols • Sorbitol • • • • Maltitol Mannitol Xylitol Erythritol 2-KGA Polyol Derivatives • Anhydropolyols • Erythrulose Citric Acid • Citrates Caramel Formulation aids Cough syrups Parenteral / enteral nutrition Intermediates Excipients • diluents • desintegrating agents • binders • bulking agents / carriers • lubricants Acidulants / Antiacidulants Infusion solutions Synthons for drugs Pharma .chiral .Surfactants / Emulsifiers Thickeners Humectants Film forming agents Preservatives Skin care Fragrances Decorative cosmetics Hair care Oral / dental hygiene Deodorants Cosmetics non-toxic functional controlled release nutritional .compatible - HR/Oldenburg 8/8/00 .Emollients .

.maltodextrins….s.Starch Hydrolysates for Fermentation ➤ Low cost sugar beet. e. legislation and the necessity to control investment and operating costs. Melanoidins and sulphate in waste waters and solid by-products like gypsum have to be treated and to be disposed of ➤ Increasing environmental consciousness. in high purity and adapted composition ➤ Possible advantages to use pure adapted raw materials: lower capital investment per unit of installed fermenter capacity. maltose syrups.and cane molasses are traditionally used by the fermentation industry as cheap carbon sources. cryst.g. glucose syrups. force the fermentation industry to use new technologies with pure raw materials ➤ The starch industry is offering a broad range of carbohydrate feedstocks.. dextrose. higher space/time yield HR/Oldenburg 8/8/00 . causing high costs during refining and purification of end products. lower energy consumption at higher d.

Starch Hydrolysates for Fermentation WHEAT CORN Steeping Dry milling & Separation Wet milling & Separation Corn Steep Liquor Vital Gluten Corn Oil STARCH Liquefaction Refining Saccharification Refining Maltodextrins Very High Maltose Syrup High Maltose Syrup 90 DE Syrup 97 DE Syrup 99% Dextrose Syrup Crystalline Dextrose Epimerisation Mannose HR/Oldenburg 8/8/00 .

Economic Evaluation of Renewable Resources ➤ Sufficient quantities for non-food applications will be available in the EU through set aside regulation ➤ Reformation of the EU agronomical system will ensure availability at world market prices ➤ Basic chemicals can be cheaper produced from petrochemical resources ➤ Intermediate products can be more economic on the basis of renewable resources ➤ Finished products with higher added value are favoured when based on renewable resources ➤ Renewable resources cannot serve as cheap fillers : functionality is a prerequisite to their utilisation HR/Oldenburg 8/8/00 .

Product Possibilities for Renewable Raw Materials ➤ Regain traditional application areas where synthetic products have replaced natural materials through : q q q Combination Complementary effects Synergistic effects Biodegradability Biocompatibility Non-toxicity Molecular recognition Chirality effects Solventless inks. paints. q q ➤ Benefit from environmental requirements for new systems like : q q q q HR/Oldenburg .g. glues Biodegradable detergents Biodegradable packaging materials Controlled release agrochemicals 8/8/00 ➤ Make use of special functionalities like : q q q ➤ Make use of structural elements (Synthesis power of nature) e.

Chemoenzymatic modification .Combination with petrochemical products for achieving complementary or synergistic effects HR/Oldenburg 8/8/00 .g.Biotransformation q Application development : . : . e.Future R&D Requirements for Renewable Raw Materials ➤Agricultural products : q Classical breeding and genetic engineering for new or improved plants with : Better separability Resistance against diseases and pests Higher yields Uniform composition / monocomposition New functionalities ➤Technical processing : q Better separation technologies as well as enrichment & purification techniques: .Chromatographic separation ➤Modification and derivatisation : q New technologies for the incorporation of interesting functionalities.Simplified model systems for easier products screening .Ultra & nanofiltration .

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