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Markus Dierker
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Contents
Markus Dierker
Raw Materials
World Production of Oils and Fats 2002 (mil mt)
29.7 24.9
animal
(approx. 20 % declining)
er
Ta llo w
So y
La ur ic s
Su nf
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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 %
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Raw Materials
Natural Generation of Triglycerides
Energy CO2 H2O Nutrients
O O O O O O
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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
31 65
Markus Dierker
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
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[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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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
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
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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
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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
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
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
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Oleochemicals
Fatty Acids - Main Technologies
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Oleochemicals
Fatty Acids Oleic Acid
Production
crystallisation (hydrophilisation) saturated acids as by-products
tallow
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
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
Isostearic Acids
Emersol
Empol
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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
fatty acids
glycerine
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Oleochemicals
Fatty Acid Methyl Esters
fatty alcohols
solvents, lubricants
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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
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Oleochemicals
Fatty Alcohols Saturated Alcohols
C 6-10 C12-14 C12-18 C16-22 plasticizer range detergent range
Unsaturated Alcohols
O RO
HD-Ocenols
+ H2 [cat] - ROH HO
C16-18
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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
+ [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
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
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
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Specialties
Polyols - Polymers
O RO
H2O2 RO
+ R OH
[cat] RO
HO
+ isomers
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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
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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
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Specialties
Ricinoleic Acid
O HO
OH
O OH O +
OH
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Specialties
Ricinoleic Acid Methyl Ester
intermediate to undecylenic acid / Nylon 11
Nylon 11
O O bromination Br O H2N O Nylon 11 O O
amination
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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
fatty acids
glycerine
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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