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
animal
(approx. 20 % declining)
24.9
24.0
8
13.3
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6.1
16
O
th
er
B
ut
te
r
6.3
La
ur
ic
s
8.4
Ta
llo
w
er
w
lo
Su
nf
R
ap
e
Pa
lm
So
y
7.6
Raw Materials
Regions of Production / Share of World Production 2002 (%)
20
18
12
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40
Raw Materials
World Consumption of Oils and Fats (mil mt)
120.3
97.4
16.8
Total
6.1
Food
Chemistry
Feed
81 %
14 %
5%
World Consumption of Mineral Oil in 2004: approx. 4.000 mil mt
Markus Dierker
Raw Materials
Natural Generation of Triglycerides
Energy
CO2
O
H2O
Nutrients
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
glycerine
backbone
O
O
fatty acids
O
O
Carbon Chain
Material
8
coconut oil
8
7
48 17
9
palm kernel oil
4
5
50 15
7
palm oil
C18
10 12 14 16 18 20
20 22
22
2
a
0
1
2
10
2
7
1
18
2
15
1
42 56
5
41
10
3
rape oil (old)
2
38
7
51
51
1
15
15
7
b
rape oil (new)
4
90
2
33
1
60
20
9
c
sunflower (old)
(old)
6
93
4
28
61
sunflower (new)
(new)
4
93
4
84
5
soy oil
8
91
4
28
53
13
46
6
d
lard
1
31 65
11
2
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6
Raw Materials
Distribution of Fatty Acids in Triglycerides
O
O
glycerine
backbone
O
O
fatty acids
O
O
• no statistic distribution of fatty acids in triglycerides
example cocoa butter:
P = palmitic acid
PSO:
SOS:
PPO:
PPS:
36%
25%
15%
1%
S = stearic acid
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O = oleic acid
Basic Oleochemical Transformations
Esterification / Ester Cleavage
O
R OH
+
HO
[cat]
O
R
+
O
Transesterification
O
R OH
+
R
O
O
[cat]
R OH
+
R
O
Hydrogenation
O
HO
H2
[cat]
O
HO
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H 2O
Production Flow Scheme
Raw Materials
Oleochemicals
sulpho fatty acid esters
fatty acid
methyl
ester
fatty
alcohols
oils
&
fats
Specialties
fatty
acids
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
glycerine
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Oleochemicals
Chemical Conversion of Triglycerides
• Splitting
O
O
O
O
+
3 R OH
O
O
O
RO
OH
O
∆T
OH
[cat]
TG
+
alcohol
RO
O
OH
water
+
Æ
RO
fatty acids
glycerine
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+
fatty acid esters
Oleochemicals
Glycerine / Derivatives
Glycerine
• purification by distillation or ion exchange
OH
Æ pharma-grade glycerine (86%, > 99%)
OH
Æ cosmetics, pharma, nutrition, graphic & printing, ...
Glycerides
• esterification / transesterification
Æ special mono-, di-, tri-glycerides
• GMO (glycerine monooleate)
• triacetin (triacetyl glycerine)
O
O
OH
OH
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OH
Production Flow Scheme
Raw Materials
Oleochemicals
sulpho fatty acid esters
fatty acid
methyl
ester
fatty
alcohols
oils
&
fats
Specialties
fatty
acids
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
glycerine
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Oleochemicals
Fatty Acids
Distilled FA
C6-18
broad cuts
Fractionated FA
C8-18
fine cuts, purity > 98%
Stearines
C16/C18
saturated
Oleines
C18
monounsaturated
Polyunsaturated FA
C18
polyunsaturated
100
100
100
80
80
80
60
60
60
40
40
40
20
20
20
0
0
8
10
12
14
16
distilled FA
18
20
0
8
10
12
14
16
18
20
fractionated FA
8
10
12
14
18
20
polyunsaturated FA
Æ soaps, detergents, emulsifiers, other oleochemicals, ...
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16
Oleochemicals
Fatty Acids - Main Technologies
• Splitting
• Distillation
• Fractionation
• Crystallisation (Hydrophilisation)
• Hydrogenation (partial or full)
• Esterification
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Oleochemicals
Fatty Acids – Oleic Acid
tallow
• Production
• crystallisation (hydrophilisation)
• saturated acids as by-products
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
O3
HO
O
HO
O
O
OH
+
HO
Azelaic Acid
Æ esters, plasticizer, soaps, polyamides, nylon, adhesives, coatings
Pelargonic Acid
Æ esters plasticizers, lubricants, corrosion inhibitors
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Oleochemicals
Conjugated Fatty Acids
O
RO
+
+
isomers
UKD Fatty Acids®
Tonalin®
mixture of many isomers
Æ alkyd resins
two isomers: c9,t11- / t10,c12- CLA
Æ functional foods
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Specialties
Monomer / Dimer Acids
O
O
HO
+
O
∆T
[cat]
O
HO
monomer acid
C18
OH
+
HO
dimer acid
C36
Isostearic Acids
Emersol®
hydrogenation, fractionation Æ isostearic acid
Æ cosmetics, lubricants, plastic auxilliaries
Dimer Acids
Empol®
purification
Æ polyamides, polyesters, lubricants, corrosion inhibitors
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Production Flow Scheme
Raw Materials
Oleochemicals
sulpho fatty acid esters
fatty acid
methyl
ester
fatty
alcohols
oils
&
fats
Specialties
fatty
acids
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
glycerine
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Oleochemicals
Fatty Acid Methyl Esters
Æ fatty alcohols
Æ intermediate to production of special esters
Æ solvents, lubricants
Æ Biodiesel (rape seed oil methyl ester)
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Oleochemicals
Fatty Alcohols
O
RO
+ H2
[cat]
- ROH
HO
• 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
Æ main intermediate to other oleochemicals
fatty alcohol phosphates
alkyl polyglucosides
fatty alcohol ethoxylates
carboxylic esters
sulfosuccinates
fatty alcohols
fatty alcohol sulfates
acrylates
methacrylates
fatty alcohol ether sulfates
alkylhalogenides
fatty amines
Æ main application as detergents
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Oleochemicals
Fatty Alcohols
Saturated Alcohols
Lorol®, Hydrenol®, Stenol®
C 6-10
plasticizer range
solubiliser, defoaming agents, ...
C12-14
detergent range
foam stabilisers, lubricant additives, …
C12-18
C16-22
consistency giving factors,
melting point regulators,
lubricants for cosmetics and pharma, ...
Unsaturated Alcohols
HD-Ocenols®
O
RO
C16-18
+ H2
[cat]
- ROH
HO
solvents, defoamers, plasticizer,
emulsifier, oil component in cosmetics
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Oleochemicals
Fatty Alcohols Specialties
Branched Alcohols
Speziol®
C16-18 satur. / unsatur.
detergents
cosmetics
fine chemicals
Diols
Speziol®
C8 / C10 / C12 / C18
cosmetics
agro chemicals
pharmaceuticals
plasticizer
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Specialties
Guerbet Alcohols
[cat]
∆T, ∆p
HO
O
- [H]
aldol cond.
- H2O
+ [H]
O
HO
Guerbet Alcohols
Rilanit®
C16 / C20
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
+
n
O
ethoxylation
O
O
H
n
• nonionic surfactant, low foaming
Æ good emulsifiers for W/O and O/W emulsions
Æ intermediate to oleochemical products
FAEO
O
O
Narrow Range Ethoxylates (NRO)
H
n
O
O
n
End-Capped Ethoxylates
Fatty Alcohol EO/PO Adducts
O
O
O
n
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O
H
m
Surfactants
Fatty Alcohol Sulfates (FAS)
O
sulfation
O
OH
O
S
O
Na
• anionic surfactants
• insensitive to water hardness
• good foaming power
Æ fire extinguisher foams
Æ detergents for home care and cosmetic application
Fatty Alcohol Ether Sulfates (FAES)
O
O
O
sulfation
O
H
n
O
O
O
S
O
Na
n
• insensitive to water hardness
• anionic surfactants
• very good water-solubility
• very good skin compatibability
• very good foaming power
Æ 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
• nonionic surfactant
• very good biodegradability
Æ detergent for home care applications, cosmetics
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HO
OH
OH
O
OH
H
Specialties
Polyols - Polymers
O
O
H2O2
RO
O
RO
O
+ R OH
[cat]
HO
O
R
RO
+ isomers
• hydrophobic fatty acid polyol
• adjustable properties / performance
Æ self-stabilising softeners, PU components
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Specialties
Polyol Esters - Synlubes
lubricants, hydraulic fluids, power transmission, MWF, ...
challenging requirements
• temperature
• viscosity
• oxidative stress
• CP/PP
• long service-life
• emulsifying properties
• price
Polyol Esters
O
R
• structural variability
O
O
R
O
R
O
• tunable properties / performance
• biodegradable
O
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Specialties
Castor Oil
O
O
O
OH
O
OH
O
OH
O
• maily produced in India, China and Brazil
• liquid at room temperature
• contains ca. 85% of 12-hydroxy-9-octadedenoic acid
Æ triglyceride used as component of polyurethans (often with resins)
Æ ricinoleic acid / ricinoleic acid methyl ester
Æ 12-hydroxy-stearic acid
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Specialties
Ricinoleic Acid
Æ intermediate to sebacic acid (used for Nylon) and 2-octanol
O
OH
HO
O
270 °C
caustic ox.
OH
OH
HO
O
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+
Specialties
Ricinoleic Acid Methyl Ester
Æ intermediate to undecylenic acid / Nylon 11
• undecylenic acid methyl ester
O
OH
O
O
450 °C
alkaline cond.
OH
+
O
• Nylon 11
O
O
bromination
O
Br
O
O
amination
H2N
O
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Nylon 11
Summary - Production Flow Scheme
Raw Materials
Oleochemicals
sulpho fatty acid esters
fatty acid
methyl
ester
fatty
alcohols
oils
&
fats
Specialties
fatty
acids
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
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
• Ullmann´s 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