Umwelt-und Ressourcen-schonende Synthesen und Prozesse

Perspektiven der industriellen Nutzung nachwachsender Rohstoffe, insbesonders von Strke und Zucker H. Rper 4.-6.Sept. Oldenburg
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Renewable Raw Materials

Annual biomass production (photosynthesis) 170 billion t

Carbohydrates 75% Lignin Others* 20% 5%

Lignin

Carbohydrates

*fats, proteins,terpenes,alkaloids, nucleic acids

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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

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Renewable/Fossil Resources
Renewable Resources Total use: 6.000 mio t/a Fossil Resources Total use: 7.300 mio t OE/a 93% energy, 7%RM Chem. Ind Cereals
2.200 mio t 1.800 mio t

Wood

Oil
3.250 mio t 2.250 mio t O.E

Coal

2.000 mio t

1.800 mio t O.E.

Total available: coal 850.000 mio t Total available: 170.000 mio t/a gas 120.000 billion m3 oil 135.000 mio t Source: M. Eggersdorfer et al. FEMS Microbiol. Rev. 103 (1992) 355
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Oilseeds, sugar cane, sugar beets, fruits, vegetables

Natural gas

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, if their special functional properties like biocompatibility, biodegradability, non toxicity and their favourable CO2 balance are utilised in an intelligent way Their utilisation is especially attractive, if the natural synthetic power of nature can be (partially) used in the target product

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Renewable Raw Materials

Utilisation by the Chemical Industry (D) 1991 Raw Materials (total ) 22.4 mio t
Gas RRM Coal

Renewable Raw materials 1.8 mio t

Other
l lu el C os e

Sugar

Starch

Oil

Fats/Oils

Oil 18.4 mio t Gas 1.7 mio t RRM 1.8 mio t Coal 0.5 mio t
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82% 8% 8% 2%

Source: VCI 1994

Fats/Oils Starch Cellulose Sugar Other

0.900 mio t 50% 0.465 mio t 28% 0.250 mio t 14% 0.032 mio t 2 % 0.100 mio t 6 %

European Production of Main Agricultural Commodities

Total annual production : 80,3 mio t Annual non food use : 42,3 mio t Vegetable oils : 2.6 mio t (6.2%) Sucrose : 0.3 mio t Starch (0.7%)
3 .4 (8 m .0 % io ) t

Vegetable Oils

Sucrose

18.6 mio t (23.2%) 7.7 mio t (9.6%)

17 mio t (21.2%)

Starch

37 mio t (46.1%)

36 mio t (85.1%)

Cellulose
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Cellulose

European Non-Food Applications of Agricultural Commodities

Raw material Cellulose % of total production 94.8 2.5 tonnes 35.075.000 342.250 582.750 36.000.000 Sucrose Starch 1.8 44.2 300.000 1.900.000 1.000.000 500.000 3.400.000 Vegetable oils & fats 14 2.600.000 Tensides, softeners (~1.3) Lubricants, plasticisers (~0.6) Lacquers, dyes (~0.4) Biodiesel Application Paper & pulp Chemical Industries (37%) Regenerate, textile, tires (63%) total Chemicals, Fermentation Paper & Corrugating Chemicals, Fermentation Binders, Adhesives

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Technical Requirements for Renewable Resources

General Availability Uniformity Purity Workability Economy Ecology Specific (Bio)compatibility Biodegradability Non-toxicity Molecular structure e.g. chirality Reactivity

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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
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Co-Products Proteins Lecithins Molasses Pectins

By-Products Pulps Lignin Bran Steepwater

Cellulose Starch Sucrose Oils

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Industrial Uses of Starch

Cereals / /Tubers Cereals Tubers Fibers, 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
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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

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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
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Furan resins

Sucrose utilisation
Sucrose tricarboxylic acid Sucroseester
(emulsifyer)

Sucralose
O O O

Sucrose polyester
(Olestra; fat replacer)

3-Keto sucrose
Furan dicarboxylic acid

Isomalt

Isomaltulose

Sucrose

Fructose

HMF

Dihydroxymethyl furan

Organic acids
e.g Citric acid, Lactic acid Amino acids Biotechn. Conversion O Chemical conversion
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Dextran, Levan, Amylose Fructooligosaccharides

(Neosugar, Actilight) Filler in phenol/formaldehyde resins Component in PU foams

3-Keto sucrose

OH H

H O HO H H OH

OH H

O H

HO HO

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

H H HO

CH 2 OH

S ucrose

3-K eto-sucrose

> p,>T

R eductiv e am ination a) N H 3 /H 2 /cat. b) R N H 2/ H 2 /cat.

a) 3-A m ino sucrose b) 3-N -alkyl-am ino sucrose

Buchholz et al.

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Fructooligosaccharides (scFOS)
(Neosugar, Actilight)

OH O OH OH OH

HO O OH

OH OH

Fructosyltransferase (whole cells/immobilised) pH 5-6, 60-65 C, 60% ds

OH OH HO O HO O OH 1 2 O O OH OH OH
n

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.) (>70% d.s.) <25 0.2 9 1.7 21 37 20 36 1 2 >41 >72

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Isomaltulose/Isomaltitol
H OH H HO HO H H OH H O

OH

O OH OH

OH

OH

H H

OH

5 -O -( 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

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'
H CH 2 OH CH 2 OH HO H

H HO H

1'

H 2 /N H 3 /C a t. > p ,> T

Is o m a ltu lo s e > p ,> 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 dzuck er A G

O
OH

G lu c o s y l- (1 6 )s o rb ito l 5 0 % G lu c o s y l- (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
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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
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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

Correlation basic properties / application properties

Basic Properties
Molweight MW-Distribution Amylose / Amylopectin ratio Crystallinity Non - starch components Molweight MW-Distribution Nature of substituent Degree of substitution Salt content Gelatinisation Temperature Solubility Viscosity as function of (c, T, t, D) Gel formation Ionic charge Specific manufacturing conditions
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Modification

Key-properties

Application properties<
Specific customer demands

Rheology Water binding Retention Adhesive / Binding power Gel strength Degradability

Application of Starch in Paper Production

Process steps: wet end, spraying, drying section, size press, coater Wet end: cationic starch (0.5-2% on cellulose). Fibre retention, improved flocculation, dewatering and machine runnability, improving of paper sheet dry strength. Spraying of starch on wet sheet. Cheap way to improve sheet strength in the drying section of the paper machine. Surface sizing. Penetration of gelatinised starch into the paper sheet by size press. Improving of paper stiffness, strength, and controlled ink receptivity Coating of surface with coating colours to improve gloss, e.g. magazine paper
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Application of Starch in Paper Production

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New Starch Based Binders

Use of native and modified starches as binders for compacting of powders and dust to pellets, bars, 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, due to difficult environmental control

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New Starch Based Binders

Powder
e.g. ceramic powder aluminium dust coal powder filter dust

Dough

Pieces
e.g. Pellets bars briquettes cylinders sheets

Drying
- about 200C - about 300C

Effect
hot bonding carbonisation

- ambient temp. green bonding

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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
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Starch in Biodegradable Polymers

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

Disintegrated reactive starch

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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, Polylactic acid)

100% Molds, films, fibres, based on medical implants starch Molds, films, expanded products with lower water resistance / mechanical properties Molds, films, expanded products (loose fill) Molds and films but not biodegradable

Starch based Products for Pharma and Cosmetics

Pharma Excipients for tabletting, binder for coatings, desintegrating agents, carriers, lubricants, matrices for controlled release Conformity with Pharmacopeia (US, EU, Jpn) Cosmetics Emollients, humectants, emulsifyers thickeners, film forming agents,

Skin compatibility, skin protection, tactile characteristics, non critical impurities, environmental compatibility, stability, processibility, no colour, no odour

natural-compatible-non-toxic-functional-controlled release-nutritional-chiral
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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

- Emollients - 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 - chiral

- natural - compatible

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Starch Hydrolysates for Fermentation

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

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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
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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, glues Biodegradable detergents Biodegradable packaging materials Controlled release agrochemicals
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Make use of special functionalities like :

q q q

Make use of structural elements (Synthesis power of nature) e.g.

q q

Benefit from environmental requirements for new systems like :

q q q q
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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:

- Ultra & nanofiltration - Chromatographic separation

Modification and derivatisation :

q

New technologies for the incorporation of interesting functionalities, e.g. :

- Chemoenzymatic modification - Biotransformation

Application development :
- Simplified model systems for easier products screening - Combination with petrochemical products for achieving complementary or synergistic effects

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