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

7.6 8.4
6.3 6.1 16
er

w
y

er
r
e
lm

te
So

ic
ap

llo
w

th
Pa

ut

ur
lo
R

O
Ta

La
nf
Su

Markus Dierker
Raw Materials

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

20
40
18

12

Markus Dierker
Raw Materials

World Consumption of Oils and Fats (mil mt)

120.3
97.4

16.8
6.1

Total 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

O
Energy H2O
O
CO2 Nutrients O
O
O
O

• linear, sat./unsat. FA with

even numbered C-chains
• renewable resources
• biodegradable
O2 Proteins • balanced life cycle analysis
Carbo- Triglycerides
hydrates Waxes

Markus Dierker
Raw Materials

Distribution of Fatty Acids in Triglycerides

O
O
O
glycerine
O fatty acids
backbone O
O

Carbon Chain C18

Material 8 10 12 14 16 18 20
20 22
22 0 1 2 3
coconut oil 8 7 48 17 9 10 2 7 1
palm kernel oil 4 5 50 15 7 18 2 15 1
palm oil 2 42 56 5 41 10
a
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
d
sunflower (new)
(new) 4 93 11 4 84 5
soy oil 8 91 4 28 53 6
lard 1 31 65 2 13 46 6

Markus Dierker
Raw Materials

Distribution of Fatty Acids in Triglycerides

O
O
O
glycerine
O fatty acids
backbone O
O

• no statistic distribution of fatty acids in triglycerides

example cocoa butter: PSO: 36%
SOS: 25%
PPO: 15%
PPS: 1%

P = palmitic acid S = stearic acid O = oleic acid

Markus Dierker
Basic Oleochemical Transformations

Esterification / Ester Cleavage

O
R OH + HO

O
[cat] R
O + H 2O

Transesterification
O
R OH R
+ O

O
[cat] R
R OH + O

Hydrogenation
O O
H2
HO [cat] HO

Markus Dierker
 Production Flow Scheme

Raw Materials Oleochemicals Specialties

fatty acid sulpho fatty acid esters

methyl guerbet alcohols
ester alkyl chlorides
fatty fatty alcohol ethoxylates
alcohols fatty alcohol sulfates
technical esters
oils alkyl polyglycosides
& fatty conjugated fatty acids
fats acids alkyl epoxyesters
dimer acids
fatty acids ethoxylates
azelaic/pelargonic acids
fatty acid esters
triacetin
glycerine
partial glycerides

Markus Dierker
Oleochemicals

Chemical Conversion of Triglycerides

• Splitting
O
O
O
O + 3 R OH
O
O

OH RO
O
∆T
OH + RO
[cat]
O
OH
RO

water fatty acids

TG + Æ glycerine +
alcohol fatty acid esters

Markus Dierker
Oleochemicals

Glycerine / Derivatives

Glycerine
• purification by distillation or ion exchange OH

Æ pharma-grade glycerine (86%, > 99%) OH

Æ cosmetics, pharma, nutrition, graphic & printing, ... OH

Glycerides
• esterification / transesterification O

Æ special mono-, di-, tri-glycerides O

OH
• GMO (glycerine monooleate)
OH
• triacetin (triacetyl glycerine)

Markus Dierker
 Production Flow Scheme

Raw Materials Oleochemicals Specialties

fatty acid sulpho fatty acid esters

methyl guerbet alcohols
ester alkyl chlorides
fatty fatty alcohol ethoxylates
alcohols fatty alcohol sulfates
technical esters
oils alkyl polyglycosides
& fatty conjugated fatty acids
fats acids alkyl epoxyesters
dimer acids
fatty acids ethoxylates
azelaic/pelargonic acids
fatty acid esters
triacetin
glycerine
partial glycerides

Markus Dierker
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 0
8 10 12 14 16 18 20 8 10 12 14 16 18 20 8 10 12 14 16 18 20

distilled FA fractionated FA polyunsaturated FA

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

Markus Dierker
Oleochemicals

Fatty Acids - Main Technologies

• Splitting

• Distillation

• Fractionation

• Crystallisation (Hydrophilisation)

• Hydrogenation (partial or full)

• Esterification

Markus Dierker
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

Markus Dierker
Oleochemicals

Fatty Acids - Specialties

O O3
HO

O O O
+ HO
HO OH

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

Pelargonic Acid
Æ esters plasticizers, lubricants, corrosion inhibitors

Markus Dierker
Oleochemicals

Conjugated Fatty Acids

O
RO

+ + isomers

UKD Fatty Acids® Tonalin®

mixture of many isomers two isomers: c9,t11- / t10,c12- CLA
Æ alkyd resins Æ functional foods

Markus Dierker
Specialties

Monomer / Dimer Acids

O O
O
HO OH
HO ∆T
+ monomer acid +
O [cat] C18
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

Markus Dierker
 Production Flow Scheme

Raw Materials Oleochemicals Specialties

fatty acid sulpho fatty acid esters

methyl guerbet alcohols
ester alkyl chlorides
fatty fatty alcohol ethoxylates
alcohols fatty alcohol sulfates
technical esters
oils alkyl polyglycosides
& fatty conjugated fatty acids
fats acids alkyl epoxyesters
dimer acids
fatty acids ethoxylates
azelaic/pelargonic acids
fatty acid esters
triacetin
glycerine
partial glycerides

Markus Dierker
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)

Markus Dierker
Oleochemicals

Fatty Alcohols

+ H2
O
[cat]
RO HO
- ROH

• 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

Markus Dierker
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

Markus Dierker
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 consistency giving factors,
C16-22 melting point regulators,
lubricants for cosmetics and pharma, ...

Unsaturated Alcohols HD-Ocenols®

+ H2
O
[cat]
RO - ROH HO

C16-18 solvents, defoamers, plasticizer,

emulsifier, oil component in cosmetics

Markus Dierker
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

Markus Dierker
Specialties

Guerbet Alcohols

[cat]
∆T, ∆p
HO O
- [H]

aldol cond. + [H]

- H2O 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

Markus Dierker
Surfactants

Fatty Alcohol Ethoxylates (FAEO)

O ethoxylation O
OH + n 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
H
n
Narrow Range Ethoxylates (NRO) O
O
n
End-Capped Ethoxylates
O O
Fatty Alcohol EO/PO Adducts O O H
n m

Markus Dierker
Surfactants

Fatty Alcohol Sulfates (FAS)

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

• anionic surfactants • insensitive to water hardness

• very good skin compatibability • very good water-solubility
• very good foaming power
Æ basic surfactants in cosmetic detergents and cleaners

Markus Dierker
Surfactants

Alkyl Polyglucosides (APG)

OH
O
OH + OH
HO
HO OH

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

• nonionic surfactant
• very good biodegradability
Æ detergent for home care applications, cosmetics

Markus Dierker
Specialties

Polyols - Polymers

O H2O2 O O
RO RO

R
O HO O
+ R OH
[cat] RO

+ isomers

• hydrophobic fatty acid polyol

• adjustable properties / performance
Æ self-stabilising softeners, PU components

Markus Dierker
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 • structural variability
R O
O R • tunable properties / performance
O
R O • biodegradable
O

Markus Dierker
Specialties

Castor Oil

O OH
O
O OH
O
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

Markus Dierker
Specialties

Ricinoleic Acid

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

O OH
HO

O OH
270 °C
OH +
caustic ox. HO
O

Markus Dierker
Specialties

Ricinoleic Acid Methyl Ester

Æ intermediate to undecylenic acid / Nylon 11

• undecylenic acid methyl ester

O OH
O

O OH
450 °C
O +
alkaline cond.

• Nylon 11

O O
bromination
O Br O

O
amination Nylon 11
H2N O

Markus Dierker
 Summary - Production Flow Scheme

Raw Materials Oleochemicals Specialties

fatty acid sulpho fatty acid esters

methyl guerbet alcohols
ester alkyl chlorides
fatty fatty alcohol ethoxylates
alcohols fatty alcohol sulfates
technical esters
oils alkyl polyglycosides
& fatty conjugated fatty acids
fats acids alkyl epoxyesters
dimer acids
fatty acids ethoxylates
azelaic/pelargonic acids
fatty acid esters
triacetin
glycerine
partial glycerides

Markus Dierker
Oleochemicals

Literature

• Encyclopedia of Chemical Technology, 4th Edition, 1991,

Kirk-Othmer
• Alcohols, higher aliphatic Vol. 1, p. 865
• Carboxylic acids Vol. 5, p. 147
• Fats and Oils Vol. 10, p. 252

• Ullmann´s Encyclopedia of Industrial Chemistry, 5th Edition, 1987,

• Fatty Acids Vol. A 10, p. 245
• Fatty Alcohols 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