Raw Materials and Processes in Oleochemistry

Markus Dierker

Markus Dierker

Contents

Raw Materials Basic Oleochemical Transformations Oleochemical Products Summary

Markus Dierker

Raw Materials
World Production of Oils and Fats 2002 (mil mt)

vegetable (approx. 80%)

29.7 24.9

animal

(approx. 20 % declining)

24.0 8 13.3 7.6 8.4 6.3 6.1 16

er

Ta llo w

So y

La ur ic s

Su nf

Markus Dierker

B ut te r

O th er

R ap e

Pa lm

lo

Raw Materials
Regions of Production / Share of World Production 2002 (%)

20 18

40

12

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Raw Materials
World Consumption of Oils and Fats (mil mt) 120.3 97.4

16.8

6.1
Feed 5%

Total

Food 81 %

Chemistry 14 %

World Consumption of Mineral Oil in 2004: approx. 4.000 mil mt

Markus Dierker

Raw Materials
Natural Generation of Triglycerides
Energy CO2 H2O Nutrients
O O O O O O

linear, sat./unsat. FA with even numbered C-chains renewable resources

O2 Proteins Carbo- Triglycerides hydrates Waxes

biodegradable balanced life cycle analysis

Markus Dierker

Raw Materials
Distribution of Fatty Acids in Triglycerides
O O O

glycerine backbone

O O

fatty acids
O

Carbon Chain Material coconut oil palm kernel oil palm oil rape oil (old)
b rape oil (new) c sunflower (old) (old) a

C18 0 2 2 5
7 2 51 51 3 3 1 1 2

8 8 4

10 12 14 16 18 20 20 22 22 7 5 48 17 50 15 2 9 7 2 4 6 4 8 1 10 18 38 90 93 93 91

1 7 15 41 15 60 28 84 28 46

2 1 1 10 15 20 61 5 53 6

42 56

1 1 4 4 4 13

7 9

sunflower (new) (new) soy oil lard

31 65

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Raw Materials
Distribution of Fatty Acids in Triglycerides

O O O

glycerine backbone

O O

fatty acids
O

no statistic distribution of fatty acids in triglycerides example cocoa butter: PSO: SOS: PPO: PPS: 36% 25% 15% 1%

P = palmitic acid

S = stearic acid

O = oleic acid

Markus Dierker

Basic Oleochemical Transformations

Esterification / Ester Cleavage
O R OH + HO

[cat]

O R O

H 2O

Transesterification
O R OH + R O O R OH + R O

[cat]

Hydrogenation
O HO H2 [cat] O HO

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Production Flow Scheme

Raw Materials Oleochemicals
fatty acid methyl ester fatty alcohols

Specialties
sulpho fatty acid esters guerbet alcohols alkyl chlorides fatty alcohol ethoxylates fatty alcohol sulfates technical esters alkyl polyglycosides conjugated fatty acids alkyl epoxyesters dimer acids fatty acids ethoxylates azelaic/pelargonic acids fatty acid esters triacetin partial glycerides

oils & fats

fatty acids

glycerine

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Oleochemicals
Chemical Conversion of Triglycerides Splitting
O O O O
O OH T [cat] OH OH RO O

+
O

3 R OH

RO O RO

water TG + alcohol

fatty acids glycerine + fatty acid esters

Markus Dierker

Oleochemicals
Glycerine / Derivatives Glycerine
purification by distillation or ion exchange
pharma-grade glycerine (86%, > 99%) cosmetics, pharma, nutrition, graphic & printing, ...
OH OH OH

Glycerides
esterification / transesterification
special mono-, di-, tri-glycerides
O OH OH O

GMO (glycerine monooleate) triacetin (triacetyl glycerine)

Markus Dierker

Production Flow Scheme

Raw Materials Oleochemicals
fatty acid methyl ester fatty alcohols

Specialties
sulpho fatty acid esters guerbet alcohols alkyl chlorides fatty alcohol ethoxylates fatty alcohol sulfates technical esters alkyl polyglycosides conjugated fatty acids alkyl epoxyesters dimer acids fatty acids ethoxylates azelaic/pelargonic acids fatty acid esters triacetin partial glycerides

oils & fats

fatty acids

glycerine

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Oleochemicals
Fatty Acids Distilled FA Fractionated FA Stearines Oleines Polyunsaturated FA
100 80 60 40 20 0 8 10 12 14 16 18 20

C6-18 C8-18 C16/C18 C18 C18

100 80 60 40 20 0 8 10 12 14

broad cuts fine cuts, purity > 98% saturated monounsaturated polyunsaturated
100 80 60 40 20 0
16 18 20

10

12

14

16

18

20

distilled FA

fractionated FA

polyunsaturated FA

soaps, detergents, emulsifiers, other oleochemicals, ...

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Oleochemicals
Fatty Acids - Main Technologies

Splitting Distillation Fractionation Crystallisation (Hydrophilisation) Hydrogenation (partial or full) Esterification

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Oleochemicals
Fatty Acids Oleic Acid

Production
crystallisation (hydrophilisation) saturated acids as by-products

tallow

C16/18 fatty acids

techn. stearic aicd

oleic acid

Properties
compromise of low melting point and oxidative stability melting point: 5 8 C, esters even lower relative good stability compared to e.g. rape seed fatty acid due to low amount of polyunsaturated acids same behavior in oleic acid derivatives

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Oleochemicals
Fatty Acids - Specialties

O HO O HO

O3

O OH + HO

Azelaic Acid
esters, plasticizer, soaps, polyamides, nylon, adhesives, coatings

Pelargonic Acid
esters plasticizers, lubricants, corrosion inhibitors

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Oleochemicals
Conjugated Fatty Acids

O RO

isomers

UKD Fatty Acids

mixture of many isomers alkyd resins

Tonalin
two isomers: c9,t11- / t10,c12- CLA functional foods

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Specialties
Monomer / Dimer Acids
O HO + O HO T [cat] HO O O OH

monomer acid C18

dimer acid C36

Isostearic Acids

Emersol

hydrogenation, fractionation isostearic acid

cosmetics, lubricants, plastic auxilliaries

Dimer Acids purification

Empol

polyamides, polyesters, lubricants, corrosion inhibitors

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Production Flow Scheme

Raw Materials Oleochemicals
fatty acid methyl ester fatty alcohols

Specialties
sulpho fatty acid esters guerbet alcohols alkyl chlorides fatty alcohol ethoxylates fatty alcohol sulfates technical esters alkyl polyglycosides conjugated fatty acids alkyl epoxyesters dimer acids fatty acids ethoxylates azelaic/pelargonic acids fatty acid esters triacetin partial glycerides

oils & fats

fatty acids

glycerine

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Oleochemicals
Fatty Acid Methyl Esters

fatty alcohols

intermediate to production of special esters

solvents, lubricants

Biodiesel (rape seed oil methyl ester)

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Oleochemicals
Fatty Alcohols
+ H2 [cat] - ROH HO

O RO

production by continuous hydrogenation of esters over 1 mil mt produced from renewable raw materials main raw material for saturated alcohols: coconut and palm kernel oil competing processes using petrochemical sources Ethylene: Ziegler, Alfol-Process Olefins: Hydroformylation/Reduction share of natural sources is rising

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Oleochemicals
Fatty Alcohols
main intermediate to other oleochemicals
fatty alcohol phosphates carboxylic esters sulfosuccinates fatty alcohols acrylates methacrylates fatty alcohol ether sulfates alkylhalogenides fatty amines fatty alcohol sulfates alkyl polyglucosides fatty alcohol ethoxylates

main application as detergents

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Oleochemicals
Fatty Alcohols Saturated Alcohols
C 6-10 C12-14 C12-18 C16-22 plasticizer range detergent range

Lorol, Hydrenol, Stenol

solubiliser, defoaming agents, ... foam stabilisers, lubricant additives, consistency giving factors, melting point regulators, lubricants for cosmetics and pharma, ...

Unsaturated Alcohols
O RO

HD-Ocenols
+ H2 [cat] - ROH HO

C16-18

solvents, defoamers, plasticizer, emulsifier, oil component in cosmetics

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Oleochemicals
Fatty Alcohols Specialties

Branched Alcohols
C16-18 satur. / unsatur.

Speziol
detergents cosmetics fine chemicals

Diols
C8 / C10 / C12 / C18

Speziol
cosmetics agro chemicals pharmaceuticals plasticizer

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Specialties
Guerbet Alcohols
[cat] T, p HO - [H] O

aldol cond. - H2O O

+ [H] HO

Guerbet Alcohols
C16 / C20

Rilanit
plasticizers spray lubrication (metalworking) solubilizer for water-miscible MWF mold release agents oil components in cosmetic application dispersing agents

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Surfactants
Fatty Alcohol Ethoxylates (FAEO)

OH

ethoxylation

O H n

nonionic surfactant, low foaming

good emulsifiers for W/O and O/W emulsions intermediate to oleochemical products

FAEO Narrow Range Ethoxylates (NRO) End-Capped Ethoxylates Fatty Alcohol EO/PO Adducts
O

O H n
O n

O n

H m

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Surfactants
Fatty Alcohol Sulfates (FAS)
sulfation OH O O S O O Na

anionic surfactants insensitive to water hardness good foaming power fire extinguisher foams detergents for home care and cosmetic application

Fatty Alcohol Ether Sulfates (FAES)

O O sulfation H n O O O n O S O O Na

insensitive to water hardness anionic surfactants very good water-solubility very good skin compatibability very good foaming power basic surfactants in cosmetic detergents and cleaners

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Surfactants
Alkyl Polyglucosides (APG)

OH OH O + HO HO OH OH

OH O O O O HO HO OH OH O OH H

nonionic surfactant very good biodegradability

detergent for home care applications, cosmetics

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Specialties
Polyols - Polymers

O RO

H2O2 RO

+ R OH
[cat] RO

HO

+ isomers

hydrophobic fatty acid polyol adjustable properties / performance

self-stabilising softeners, PU components

Markus Dierker

Specialties
Polyol Esters - Synlubes lubricants, hydraulic fluids, power transmission, MWF, ... challenging requirements
temperature oxidative stress long service-life price viscosity CP/PP emulsifying properties

Polyol Esters
O R O O R O O O R

structural variability tunable properties / performance biodegradable

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Specialties
Castor Oil
O O O O O O OH OH OH

maily produced in India, China and Brazil liquid at room temperature contains ca. 85% of 12-hydroxy-9-octadedenoic acid

triglyceride used as component of polyurethans (often with resins) ricinoleic acid / ricinoleic acid methyl ester 12-hydroxy-stearic acid

Markus Dierker

Specialties
Ricinoleic Acid

intermediate to sebacic acid (used for Nylon) and 2-octanol

O HO

OH

270 C caustic ox. HO

O OH O +

OH

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Specialties
Ricinoleic Acid Methyl Ester
intermediate to undecylenic acid / Nylon 11

undecylenic acid methyl ester

O O 450 C alkaline cond. O O + OH OH

Nylon 11
O O bromination Br O H2N O Nylon 11 O O

amination

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Summary - Production Flow Scheme

Raw Materials Oleochemicals
fatty acid methyl ester fatty alcohols

Specialties
sulpho fatty acid esters guerbet alcohols alkyl chlorides fatty alcohol ethoxylates fatty alcohol sulfates technical esters alkyl polyglycosides conjugated fatty acids alkyl epoxyesters dimer acids fatty acids ethoxylates azelaic/pelargonic acids fatty acid esters triacetin partial glycerides

oils & fats

fatty acids

glycerine

Markus Dierker

Oleochemicals
Literature
Encyclopedia of Chemical Technology, 4th Edition, 1991, Kirk-Othmer Alcohols, higher aliphatic Carboxylic acids Fats and Oils Vol. 1, p. 865 Vol. 5, p. 147 Vol. 10, p. 252

Ullmanns Encyclopedia of Industrial Chemistry, 5th Edition, 1987, Fatty Acids Fatty Alcohols Vol. A 10, p. 245 Vol. A 10, p. 277

The Lipid Handbook, 1986 edited by F. D. Gunstone, J. L. Harwood, F. B. Padley Chapman and Hall Ltd.

Markus Dierker

End of Presentation