environment & chemicals _old_abb

8/3/2019 Environment & Chemicals _old_abb

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Umwelt-und Ressourcen-schonendeSynthesen und Prozesse

Perspektiven der industriellen Nutzungnachwachsender 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 20%

Others* 5%

*fats, proteins,terpenes,alkaloids, nucleic acids

Carbohydrates

Lignin


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2.200 mio t 1.800 mio t

2.000 mio t

3.700 mio t2.000 mio t


Global production/utilisation

Annual production used by man6.000.000.000 tonnes = 3.5%

Annual utilisation62% food, 5% non food

Wood Cereals

Food Energy &Housing

Non Food300 mio t =5 %

Oil seeds, Sugar cane, Sugar beet,

Fruits, Vegetables

Annual Biomass Production : 170.000.000.000 tonnes


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3.250 mio t

2.250 mio tO.E

1.800 mio tO.E.

Renewable/Fossil Resources

Renewable Resources Fossil Resources

Total use: 6.000 mio t/a Total use: 7.300 mio t OE/a93% energy, 7%RM Chem. Ind

Wood Cereals Oil Coal

Natural gasOilseeds, sugar cane,

sugar beets, fruits, vegetables

Total available: 170.000 mio t/aTotal available: coal 850.000 mio t

gas 120.000 billion m3

oil 135.000 mio tSource: M. Eggersdorfer et al. FEMS Microbiol. Rev. 103 (1992) 355

2.200 mio t 1.800 mio t

2.000 mio t


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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 syntheticproducts, if their special functional properties like

biocompatibility, biodegradability, non toxicity and theirfavourable CO2 balance are utilised in an intelligent way

Their utilisation is especially attractive, if the natural syntheticpower of nature can be (partially) used in the target product


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CoalRRM

Gas

Oil

Renewable Raw MaterialsUtilisation by the Chemical Industry (D) 1991

Raw Materials (total )22.4 mio t

Renewable Raw materials1.8 mio t

Oil 18.4 mio t 82%

Gas 1.7 mio t 8%RRM 1.8 mio t 8%Coal 0.5 mio t 2%

Fats/Oils 0.900 mio t 50%

Starch 0.465 mio t 28%Cellulose 0.250 mio t 14%

Sugar 0.032 mio t 2 %Other 0.100 mio t 6 %

Source: VCI1994

Sugar

Other

Starch

Fats/Oils

Cellulo

se


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18.6 mio t(23.2%)

17 mio t(21.2%)

37 mio t(46.1%)

7.7 mio t(9.6%)

European Production of Main

Agricultural Commodities

Starch

SucroseVegetable Oils

Cellulose

StarchSucrose : 0.3 mio t

(0.7%)

Cellulose

Total annual production : 80,3 mio t Annual non food use : 42,3 mio t

Vegetable oils : 2.6 mio t (6.2%)

3.4mio

t

(8.0%)

36 mio t(85.1%)


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European Non-Food Applications of

Agricultural CommoditiesRaw material % of total

productiontonnes Application

Cellulose 94.8 35.075.000 Paper & pulp

2.5 342.250 Chemical Industries (37%)

582.750 Regenerate, textile, tires (63%)

36.000.000 total

Sucrose 1.8 300.000 Chemicals, FermentationStarch 44.2 1.900.000 Paper & Corrugating

1.000.000 Chemicals, Fermentation

500.000 Binders, Adhesives

3.400.000

Vegetable oils &fats

14 2.600.000 Tensides, softeners (~1.3)Lubricants, plasticisers (~0.6)Lacquers, dyes (~0.4)

Biodiesel


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Technical Requirements

for Renewable ResourcesGeneral Specific

Availability (Bio)compatibility

Uniformity Biodegradability

Purity Non-toxicity

Workability Molecular structuree.g. chirality

Economy Reactivity

Ecology


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CleaningCleaning

SeparationSeparation

Agricultural Raw MaterialAgricultural Raw MaterialCerealsTubers

Wood

Oil SeedsFruits

Sugar cane & beets

Main Products

Cellulose Starch Sucrose

Oils

Co-Products

Proteins Lecithins Molasses

Pectins

By-Products

Pulps Lignin Bran

Steepwater

Product Classification of



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StarchStarch

Cereals / TubersCereals / Tubers

Maltodextrins

Hydrolysates

Derivatives

Modified Starches

HydrolysedOxidisedEstersEthersCrossbondedDextrins

Modified Starches

Hydrolysed

OxidisedEstersEthersCrossbondedDextrins

Fibers, hemicellulose, branGerm oilGlutenSteepwater

Paper & corrugating (27%)

Thickeners

Binders

CobuildersThermoplastics

Complexing agents

Flocculating agents

Coatings

Polyols

SurfactantsPharma & Cosmetic aids

Latex copolymers

Fermentation feedstocks

Industrial Uses of Starch


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SORBITOL

Maltose

SYRUPSMALTODEXTRINS

Polycarboxylates

Liquefacts

Maltitol

GLUCOSE

Glucoside esters

Gluconates

GlucaratesAminosorbitols

Glucamides

DAS

FRUCTOSE

Mannitol

HMF

MANNOSE

STARCH

Glucosan

GlycolGlycerol

Cracked Products

SAP

Graft Polymers

DEXTRINS

WhiteYellowGums

Cyclodextrins

MOD STARCHES

HydrolysedOxidisedEstersEthers (cationic)

Solutions

Emulsions

Block-Copolymers

EthanolButanol

Alcohols

Erythritol

Biopolyols

LysineGlutamic acidTryptophane

Amino Acids

Citric acidLactic acidItaconic acid

Organic acids

APG's

Alkyl glucosides

Vitamin C Sorbitan Esters

Sorbose

2-KGA

HFCS

SORMAN


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Sucrose Derivatives

Esters Ethers

Acetals

Sucrose Derivatives

Esters Ethers Acetals

SucroseSucrose

Sugar Cane / Sugar BeetsSugar Cane / Sugar Beets

Beet Pulp

BagasseMolasses

Fermentation feedstocks

Polycondensates (starter)Building units (Pharma)

Surfactants

Glucose + Fructose

Furan resins

Industrial Uses of Sucrose


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Sucrose utilisation

SucroseIsomaltuloseIsomalt Fructose HMF

Furan dicarboxylic acid

Dihydroxymethyl furan

3-Keto sucrose

Sucrose tricarboxylic acid

Sucroseester(emulsifyer)

Sucrose polyester(Olestra; fat replacer)

Fructooligosaccharides(Neosugar, Actilight)

Dextran, Levan, AmyloseOrganic acidse.g Citric acid,

Lactic acidAmino acids

Filler in phenol/formaldehyde resins Component in PU foams

SucraloseO

OO

O

O

O

Biotechn. ConversionChemical conversionO


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3-Keto sucrose

O

H

HO

H

HO

H

OHHH

OH

CH 2OHH

HO

H OH

O

H

OHOH 2C

Agrobacterium tumefaciens

O

H

HO

H

OHHH

OH

CH 2OHH

HO

H OH

O

H

OHOH 2C

O

Sucrose 3-Keto-sucrose

Reductive

aminationa) NH3/H 2/cat.b) RNH2/H2/cat.

a) 3-Amino sucroseb) 3-N-alkyl-amino sucrose

>p,>T

Buchholz et al.


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Fructooligosaccharides (scFOS)

(Neosugar, Actilight)

O

OH

OH

OH

OHOH

OHOHO

O OH

Fructosyltransferase

pH 5-6, 60-65 C, 60% ds

Sucrose

(whole cells/immobilised)

O

OH

OH

OH

OH

OH

O

HO

O

OH

OH

O

HO

O OH

OH

n

1 2

FOS G FOS P(>70% d.s.) (>70% d.s.)

Fructose + Glucose 41 >72

FOS


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Isomaltulose/Isomaltitol

O

H

HO

H

HO

H

OHH

H

OH

CH 2OH

O

H

HO

H OH

O

H

H

HOH 2C

O

H

HO

H

HO

H

OCH 2

OHH

H

OH

CH 2 OH

OH

H

HO

H OH

O

H

H

1

2 '

1Pro taminobac te rrubrum

O

transglucos idat ion

H 2 /N i

I soma l t u lose

>p,>T

Glucosy l - ( 1 6 )sorb i to l 50%

Glucosy l - (1-6)mann i to l 50%

Isomalt i to l

O

H

HO

H

HO

H

O

OHH

H

OH

OH

OH

NH 2

OH

2-Amino-2-deoxy- isomalt i to l

H 2 /NH 3 /Cat.

O

H

HO

H

HO

H

O

OHH

H

OH

>p,>T

OH

OH OH

O

OH

5-O- ( D-glucopyranosyl ) -D-arabinonic

acid

O 2 /KOH

Sucr ose

Sdzucke r AG

6 '

2 '

1 '


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Fractionated PulpsFractionated Pulps

Enriched Pulps

Cellulose enriched Pectin enriched

Enriched Pulps

Cellulose enriched Pectin enriched

Beet Pulps

Hemicellulose 29%Pectins 29%Cellulose 27%Protein 5%Insoluble ash 4%

Lignin 3%Sugar 3%

Beet Pulps

Hemicellulose 29%Pectins 29%Cellulose 27%Protein 5%Insoluble ash 4%

Lignin 3%Sugar 3%

Industrial Uses of Beet Pulp

Paper additive

Thermoplastic fillerParticle board adhesive

Biotechnological processes

Alcohol

Methane

Single cell protein

Food Applications


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Correlation basic properties /

application properties

Rheology

Water binding

Retention

Adhesive / Bindingpower

Gel strength

Degradability

Specific customer

demands

Gelatinisation -

Temperature

Solubility

Viscosity as functionof (c, T, t, D)

Gel formation

Ionic charge

Specific manufacturing

conditions

Molweight

MW-Distribution

Nature of substituent

Degree of substitution

Salt content

MolweightMW-Distribution

Amylose /Amylopectin ratio

Crystallinity

Non - starchcomponents

BasicProperties

Modification Key-propertiesApplicationproperties 90%starch

Molds, films, expandedproducts with lowerwater resistance /

mechanical propertiesDisintegrated reactivestarch

Composite materialwith different syntheticpolymers

> 50%starch

Molds, films,expanded products(loose fill)

Granular native starch Filler for polyethylenepolypropylene

6-20%starch

Molds and filmsbut not biodegradable

Starch

in Thermoplastic Polymers


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Starch based Products for Pharma and

CosmeticsPharma

Excipients for tabletting, binder for coatings, desintegrating

agents, carriers, lubricants, matrices for controlled release Conformity with Pharmacopeia (US, EU, Jpn)

Cosmetics

Emollients, humectants, thickeners, film forming agents,emulsifyers

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 CosmeticsNative starch Maltodextrins Polyols 2-KGA Polyol Derivatives

Modified starches Glucose syrups Sorbitol Anhydropolyols

Esters Dextrose Maltitol Erythrulose

Ethers Glucosides Mannitol Citric Acid

Hydrophobic Glucoside esters Xylitol Citrates

Cyclodextrins Erythritol Caramel

Formulation aids Excipients diluents

- Emollients- Surfactants / Emulsifiers

Skin careFragrances

Cough syrups desintegrating agents binders

- Thickeners- Humectants

Decorative cosmeticsHair care

Parenteral / enteralnutrition

bulking agents / carriers lubricants

- Film forming agents- Preservatives

Oral / dental hygieneDeodorants

Intermediates Acidulants / AntiacidulantsInfusion solutions

Synthons for drugs

Pharma Cosmetics

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


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Starch Hydrolysates for Fermentation

Low cost sugar beet- and cane molasses are traditionally used bythe fermentation industry as cheap carbon sources, causing highcosts during refining and purification of end products.

Melanoidins and sulphate in waste waters and solid by-productslike gypsum have to be treated and to be disposed of

Increasing environmental consciousness, legislation and thenecessity to control investment and operating costs, force the

fermentation industry to use new technologies with pure rawmaterials

The starch industry is offering a broad range of carbohydratefeedstocks, e.g. cryst. dextrose, glucose syrups, maltose

syrups,maltodextrins.. in high purity and adapted composition

Possible advantages to use pure adapted raw materials: lowercapital investment per unit of installed fermenter capacity, lowerenergy consumption at higher d.s., higher space/time yield


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Starch Hydrolysates for Fermentation

Vital Gluten Corn Oil

Corn Steep Liquor

CORNWHEAT

STARCHMaltodextrins

Liquefaction

Saccharification

Refining

Refining

Very HighMaltoseSyrup

97 DESyrup

90 DESyrup

99%DextroseSyrup

HighMaltoseSyrup

CrystallineDextrose

Mannose

Epimerisation

Dry milling &Separation

Steeping

Wet milling &Separation


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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 availabilityat 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 whenbased on renewable resources

Renewable resources cannot serve as cheap fillers : functionalityis 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 Combination

q Complementary effectsq Synergistic effects

Make use of special functionalities like :q Biodegradability

q Biocompatibilityq Non-toxicity

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

Chirality effects Benefit from environmental requirements for new systems like :

q Solventless inks, paints, gluesq Biodegradable detergentsq Biodegradable packaging materialsq Controlled release agrochemicals


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Future R&D Requirements

for Renewable Raw MaterialsAgricultural 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

q Application development :- Simplified model systems for easier products screening

- Combination with petrochemical products for achieving complementary or synergisticeffects

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