Raw Materials and Processes in Oleochemistry - abiosus
Raw Materials and Processes in Oleochemistry - abiosus
Raw Materials and Processes in Oleochemistry - abiosus
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<strong>Raw</strong> <strong>Materials</strong> <strong>and</strong> <strong>Processes</strong> <strong>in</strong><br />
<strong>Oleochemistry</strong><br />
Markus Dierker<br />
Markus Dierker
Contents<br />
• <strong>Raw</strong> <strong>Materials</strong><br />
• Basic Oleochemical Transformations<br />
• Oleochemical Products<br />
• Summary<br />
Markus Dierker
<strong>Raw</strong> <strong>Materials</strong><br />
World Production of Oils <strong>and</strong> Fats 2002 (mil mt)<br />
29.7<br />
Soy<br />
24.9<br />
Palm<br />
13.3<br />
Rape<br />
vegetable (approx. 80%)<br />
animal (approx. 20 % decl<strong>in</strong><strong>in</strong>g)<br />
7.6<br />
Sunflower<br />
8.4<br />
Tallow<br />
Markus Dierker<br />
6.3<br />
Butter<br />
6.1<br />
Laurics<br />
24.0<br />
8<br />
16<br />
Other
<strong>Raw</strong> <strong>Materials</strong><br />
Regions of Production / Share of World Production 2002 (%)<br />
18<br />
12<br />
20<br />
Markus Dierker<br />
40
<strong>Raw</strong> <strong>Materials</strong><br />
World Consumption of Oils <strong>and</strong> Fats (mil mt)<br />
120.3<br />
97.4<br />
16.8<br />
Markus Dierker<br />
6.1<br />
Total Food Chemistry Feed<br />
81 % 14 % 5 %<br />
World Consumption of M<strong>in</strong>eral Oil <strong>in</strong> 2004: approx. 4.000 mil mt
<strong>Raw</strong> <strong>Materials</strong><br />
Natural Generation of Triglycerides<br />
CO 2<br />
O 2<br />
Energy<br />
Carbohydrates<br />
H 2 O<br />
Nutrients<br />
Triglycerides<br />
Waxes<br />
Prote<strong>in</strong>s<br />
O<br />
O<br />
O O<br />
O<br />
O<br />
• l<strong>in</strong>ear, sat./unsat. FA with<br />
even numbered C-cha<strong>in</strong>s<br />
• renewable resources<br />
• biodegradable<br />
• balanced life cycle analysis<br />
Markus Dierker
<strong>Raw</strong> <strong>Materials</strong><br />
Distribution of Fatty Acids <strong>in</strong> Triglycerides<br />
glycer<strong>in</strong>e<br />
backbone<br />
O<br />
O<br />
O<br />
O<br />
O<br />
O<br />
Carbon Carbon Cha<strong>in</strong> Cha<strong>in</strong><br />
Material 8 10 12 14 16 18 20 22<br />
coconut oil 8 7 48 17 9 10<br />
palm kernel oil 4 5 50 15 7 18<br />
palm oil 2 42 56<br />
rape oil a<br />
2 38 7 51<br />
rape oil b<br />
4 90 2 3<br />
sunflower c (old) 6 93<br />
sunflower d Material 8 10 12 14 16 18 20 22<br />
coconut oil 8 7 48 17 9 10<br />
palm kernel oil 4 5 50 15 7 18<br />
palm oil 2 42 56<br />
rape oil (old) 2 38 7 51<br />
rape oil (new) 4 90 2 3<br />
sunflower (old) 6 93<br />
sunflower (new) 4 93 1<br />
soy oil 8 91<br />
lard 1 31 65 2<br />
Markus Dierker<br />
fatty acids<br />
C18<br />
0 1 2 3<br />
2 7 1<br />
2 15 1<br />
5 41 10<br />
1 15 15 7<br />
1 60 20 9<br />
4 28 61<br />
4 84 5<br />
4 28 53 6<br />
13 46 6
<strong>Raw</strong> <strong>Materials</strong><br />
Distribution of Fatty Acids <strong>in</strong> Triglycerides<br />
glycer<strong>in</strong>e<br />
backbone<br />
O<br />
O<br />
O<br />
O<br />
O<br />
O<br />
• no statistic distribution of fatty acids <strong>in</strong> triglycerides<br />
example cocoa butter: PSO: 36%<br />
SOS: 25%<br />
PPO: 15%<br />
PPS: 1%<br />
Markus Dierker<br />
fatty acids<br />
P = palmitic acid S = stearic acid O = oleic acid
Basic Oleochemical Transformations<br />
Esterification / Ester Cleavage<br />
R<br />
R<br />
OH<br />
OH<br />
+<br />
+<br />
R<br />
HO<br />
Transesterification<br />
O<br />
Hydrogenation<br />
HO<br />
O<br />
O<br />
O<br />
[cat]<br />
[cat]<br />
R<br />
O<br />
R<br />
O<br />
+ H2O OH<br />
+<br />
H2 [cat]<br />
R<br />
O<br />
O<br />
HO<br />
O<br />
Markus Dierker
Production Flow Scheme<br />
<strong>Raw</strong> <strong>Materials</strong><br />
oils<br />
&<br />
fats<br />
fatty acid<br />
methyl<br />
ester<br />
fatty<br />
acids<br />
glycer<strong>in</strong>e<br />
Oleochemicals Specialties<br />
fatty<br />
alcohols<br />
Markus Dierker<br />
sulpho fatty acid esters<br />
guerbet alcohols<br />
alkyl chlorides<br />
fatty alcohol ethoxylates<br />
fatty alcohol sulfates<br />
technical esters<br />
alkyl polyglycosides<br />
conjugated fatty acids<br />
alkyl epoxyesters<br />
dimer acids<br />
fatty acids ethoxylates<br />
azelaic/pelargonic acids<br />
fatty acid esters<br />
triacet<strong>in</strong><br />
partial glycerides
Oleochemicals<br />
Chemical Conversion of Triglycerides<br />
• Splitt<strong>in</strong>g<br />
O<br />
O<br />
O<br />
O<br />
O<br />
O<br />
∆T<br />
[cat]<br />
OH<br />
OH<br />
OH<br />
+ 3 R OH<br />
water fatty acids<br />
TG + glycer<strong>in</strong>e +<br />
alcohol fatty acid esters<br />
+<br />
RO<br />
RO<br />
RO<br />
O<br />
O<br />
O<br />
Markus Dierker
Oleochemicals<br />
Glycer<strong>in</strong>e / Derivatives<br />
Glycer<strong>in</strong>e<br />
• purification by distillation or ion exchange<br />
pharma-grade glycer<strong>in</strong>e (86%, > 99%)<br />
cosmetics, pharma, nutrition, graphic & pr<strong>in</strong>t<strong>in</strong>g, ...<br />
Glycerides<br />
• esterification / transesterification<br />
special mono-, di-, tri-glycerides<br />
• GMO (glycer<strong>in</strong>e monooleate)<br />
• triacet<strong>in</strong> (triacetyl glycer<strong>in</strong>e)<br />
O<br />
OH<br />
O<br />
OH<br />
Markus Dierker<br />
OH<br />
OH<br />
OH
Production Flow Scheme<br />
<strong>Raw</strong> <strong>Materials</strong><br />
oils<br />
&<br />
fats<br />
fatty acid<br />
methyl<br />
ester<br />
fatty<br />
acids<br />
glycer<strong>in</strong>e<br />
Oleochemicals Specialties<br />
fatty<br />
alcohols<br />
Markus Dierker<br />
sulpho fatty acid esters<br />
guerbet alcohols<br />
alkyl chlorides<br />
fatty alcohol ethoxylates<br />
fatty alcohol sulfates<br />
technical esters<br />
alkyl polyglycosides<br />
conjugated fatty acids<br />
alkyl epoxyesters<br />
dimer acids<br />
fatty acids ethoxylates<br />
azelaic/pelargonic acids<br />
fatty acid esters<br />
triacet<strong>in</strong><br />
partial glycerides
Oleochemicals<br />
Fatty Acids<br />
Distilled FA C6-18 broad cuts<br />
Fractionated FA C8-18 f<strong>in</strong>e cuts, purity > 98%<br />
Stear<strong>in</strong>es C16/C18 saturated<br />
Ole<strong>in</strong>es C18 monounsaturated<br />
Polyunsaturated FA C18 polyunsaturated<br />
100<br />
80<br />
60<br />
40<br />
20<br />
0<br />
8 10 12 14 16 18 20<br />
distilled FA<br />
100<br />
80<br />
60<br />
40<br />
20<br />
0<br />
8 10 12 14 16 18 20<br />
fractionated FA<br />
soaps, detergents, emulsifiers, other oleochemicals, ...<br />
Markus Dierker<br />
100<br />
80<br />
60<br />
40<br />
20<br />
0<br />
8 10 12 14 16 18 20<br />
polyunsaturated FA
Oleochemicals<br />
Fatty Acids - Ma<strong>in</strong> Technologies<br />
• Splitt<strong>in</strong>g<br />
• Distillation<br />
• Fractionation<br />
• Crystallisation (Hydrophilisation)<br />
• Hydrogenation (partial or full)<br />
• Esterification<br />
Markus Dierker
Oleochemicals<br />
Fatty Acids – Oleic Acid<br />
• Production<br />
• crystallisation (hydrophilisation)<br />
• saturated acids as by-products<br />
• Properties<br />
• compromise of low melt<strong>in</strong>g po<strong>in</strong>t <strong>and</strong> oxidative stability<br />
• melt<strong>in</strong>g po<strong>in</strong>t: 5 – 8 °C, esters even lower<br />
• relative good stability compared to e.g. rape seed fatty acid due to<br />
low amount of polyunsaturated acids<br />
• same behavior <strong>in</strong> oleic acid derivatives<br />
Markus Dierker<br />
tallow<br />
C 16/18 fatty acids<br />
techn. stearic aicd oleic acid
Oleochemicals<br />
Fatty Acids - Specialties<br />
HO<br />
O<br />
Azelaic Acid<br />
esters, plasticizer, soaps, polyamides, nylon, adhesives, coat<strong>in</strong>gs<br />
Pelargonic Acid<br />
esters plasticizers, lubricants, corrosion <strong>in</strong>hibitors<br />
HO<br />
O 3<br />
O O<br />
OH<br />
Markus Dierker<br />
+<br />
HO<br />
O
Oleochemicals<br />
Conjugated Fatty Acids<br />
RO<br />
O<br />
UKD Fatty Acids ®<br />
mixture of many isomers<br />
alkyd res<strong>in</strong>s<br />
+ +<br />
isomers<br />
Tonal<strong>in</strong> ®<br />
two isomers: c9,t11- / t10,c12- CLA<br />
functional foods<br />
Markus Dierker
Specialties<br />
Monomer / Dimer Acids<br />
O<br />
HO<br />
O<br />
HO<br />
+<br />
∆T<br />
[cat]<br />
monomer acid<br />
C18<br />
Isostearic Acids Emersol ®<br />
hydrogenation, fractionation isostearic acid<br />
cosmetics, lubricants, plastic auxilliaries<br />
Dimer Acids Empol ®<br />
purification<br />
polyamides, polyesters, lubricants, corrosion <strong>in</strong>hibitors<br />
+<br />
Markus Dierker<br />
HO<br />
O<br />
O<br />
dimer acid<br />
C36<br />
OH
Production Flow Scheme<br />
<strong>Raw</strong> <strong>Materials</strong><br />
oils<br />
&<br />
fats<br />
fatty acid<br />
methyl<br />
ester<br />
fatty<br />
acids<br />
glycer<strong>in</strong>e<br />
Oleochemicals Specialties<br />
fatty<br />
alcohols<br />
Markus Dierker<br />
sulpho fatty acid esters<br />
guerbet alcohols<br />
alkyl chlorides<br />
fatty alcohol ethoxylates<br />
fatty alcohol sulfates<br />
technical esters<br />
alkyl polyglycosides<br />
conjugated fatty acids<br />
alkyl epoxyesters<br />
dimer acids<br />
fatty acids ethoxylates<br />
azelaic/pelargonic acids<br />
fatty acid esters<br />
triacet<strong>in</strong><br />
partial glycerides
Oleochemicals<br />
Fatty Acid Methyl Esters<br />
fatty alcohols<br />
<strong>in</strong>termediate to production of special esters<br />
solvents, lubricants<br />
Biodiesel (rape seed oil methyl ester)<br />
Markus Dierker
Oleochemicals<br />
Fatty Alcohols<br />
RO<br />
O<br />
+H2 [cat]<br />
- ROH<br />
• production by cont<strong>in</strong>uous hydrogenation of esters<br />
• over 1 mil mt produced from renewable raw materials<br />
• ma<strong>in</strong> raw material for saturated alcohols:<br />
coconut <strong>and</strong> palm kernel oil<br />
• compet<strong>in</strong>g processes us<strong>in</strong>g petrochemical sources<br />
• Ethylene: Ziegler, Alfol-Process<br />
• Olef<strong>in</strong>s: Hydroformylation/Reduction<br />
• share of natural sources is ris<strong>in</strong>g<br />
HO<br />
Markus Dierker
Oleochemicals<br />
Fatty Alcohols<br />
ma<strong>in</strong> <strong>in</strong>termediate to other oleochemicals<br />
fatty alcohol phosphates<br />
carboxylic esters<br />
sulfosucc<strong>in</strong>ates<br />
acrylates<br />
methacrylates<br />
alkylhalogenides<br />
fatty alcohols<br />
alkyl polyglucosides<br />
fatty am<strong>in</strong>es<br />
ma<strong>in</strong> application as detergents<br />
Markus Dierker<br />
fatty alcohol ethoxylates<br />
fatty alcohol sulfates<br />
fatty alcohol ether sulfates
Oleochemicals<br />
Fatty Alcohols<br />
Saturated Alcohols Lorol ® , Hydrenol ® , Stenol ®<br />
C 6-10 plasticizer range solubiliser, defoam<strong>in</strong>g agents, ...<br />
C12-14 detergent range foam stabilisers, lubricant additives, …<br />
C12-18 consistency giv<strong>in</strong>g factors,<br />
C16-22 melt<strong>in</strong>g po<strong>in</strong>t regulators,<br />
lubricants for cosmetics <strong>and</strong> pharma, ...<br />
Unsaturated Alcohols HD-Ocenols ®<br />
RO<br />
O<br />
+H2 [cat]<br />
- ROH<br />
C16-18 solvents, defoamers, plasticizer,<br />
emulsifier, oil component <strong>in</strong> cosmetics<br />
HO<br />
Markus Dierker
Oleochemicals<br />
Fatty Alcohols Specialties<br />
Branched Alcohols Speziol ®<br />
C16-18 satur. / unsatur. detergents<br />
cosmetics<br />
f<strong>in</strong>e chemicals<br />
Diols Speziol ®<br />
C8 / C10 / C12 / C18 cosmetics<br />
agro chemicals<br />
pharmaceuticals<br />
plasticizer<br />
Markus Dierker
Specialties<br />
Guerbet Alcohols<br />
HO<br />
[cat]<br />
∆T, ∆p<br />
- [H]<br />
aldol cond.<br />
- H2O Guerbet Alcohols Rilanit ®<br />
O<br />
O<br />
C16 / C20 plasticizers<br />
spray lubrication (metalwork<strong>in</strong>g)<br />
solubilizer for water-miscible MWF<br />
mold release agents<br />
oil components <strong>in</strong> cosmetic application<br />
dispers<strong>in</strong>g agents<br />
Markus Dierker<br />
+ [H]<br />
HO
Surfactants<br />
Fatty Alcohol Ethoxylates (FAEO)<br />
FAEO<br />
Narrow Range Ethoxylates (NRO)<br />
End-Capped Ethoxylates<br />
Fatty Alcohol EO/PO Adducts<br />
OH + n<br />
O ethoxylation<br />
O<br />
O<br />
H<br />
n<br />
• nonionic surfactant, low foam<strong>in</strong>g<br />
good emulsifiers for W/O <strong>and</strong> O/W emulsions<br />
<strong>in</strong>termediate to oleochemical products<br />
Markus Dierker<br />
O<br />
O<br />
O<br />
O<br />
n<br />
O<br />
O<br />
O<br />
H<br />
n<br />
n<br />
O H<br />
m
Surfactants<br />
Fatty Alcohol Sulfates (FAS)<br />
• anionic surfactants<br />
• <strong>in</strong>sensitive to water hardness<br />
• good foam<strong>in</strong>g power<br />
fire ext<strong>in</strong>guisher foams<br />
detergents for home care <strong>and</strong> cosmetic application<br />
Fatty Alcohol Ether Sulfates (FAES)<br />
O<br />
OH<br />
O H<br />
n<br />
sulfation<br />
sulfation<br />
• anionic surfactants<br />
• <strong>in</strong>sensitive to water hardness<br />
• very good sk<strong>in</strong> compatibability • very good water-solubility<br />
• very good foam<strong>in</strong>g power<br />
basic surfactants <strong>in</strong> cosmetic detergents <strong>and</strong> cleaners<br />
Markus Dierker<br />
O<br />
O<br />
O S O<br />
O<br />
Na<br />
O<br />
n<br />
O<br />
O<br />
O S O<br />
Na
Surfactants<br />
Alkyl Polyglucosides (APG)<br />
OH<br />
HO<br />
• nonionic surfactant<br />
• very good biodegradability<br />
+<br />
HO<br />
O<br />
OH<br />
OH OH<br />
detergent for home care applications, cosmetics<br />
Markus Dierker<br />
O<br />
HO<br />
O<br />
O<br />
O<br />
HO<br />
OH OH<br />
OH<br />
OH O H
Specialties<br />
Polyols - Polymers<br />
RO<br />
O<br />
+ R OH<br />
[cat]<br />
H 2O 2<br />
• hydrophobic fatty acid polyol<br />
• adjustable properties / performance<br />
self-stabilis<strong>in</strong>g softeners, PU components<br />
RO<br />
RO<br />
O HO O R<br />
+ isomers<br />
Markus Dierker<br />
O O
Specialties<br />
Polyol Esters - Synlubes<br />
lubricants, hydraulic fluids, power transmission, MWF, ...<br />
challeng<strong>in</strong>g requirements<br />
• temperature<br />
• oxidative stress<br />
• long service-life<br />
• price<br />
Polyol Esters<br />
R<br />
R<br />
O<br />
O<br />
O<br />
O<br />
O<br />
O<br />
R<br />
• structural variability<br />
• viscosity<br />
• CP/PP<br />
• emulsify<strong>in</strong>g properties<br />
• tunable properties / performance<br />
• biodegradable<br />
Markus Dierker
Specialties<br />
Castor Oil<br />
O<br />
O<br />
O<br />
O<br />
O<br />
O<br />
• maily produced <strong>in</strong> India, Ch<strong>in</strong>a <strong>and</strong> Brazil<br />
OH<br />
OH<br />
OH<br />
• liquid at room temperature<br />
• conta<strong>in</strong>s ca. 85% of 12-hydroxy-9-octadedenoic acid<br />
triglyceride used as component of polyurethans (often with res<strong>in</strong>s)<br />
ric<strong>in</strong>oleic acid / ric<strong>in</strong>oleic acid methyl ester<br />
12-hydroxy-stearic acid<br />
Markus Dierker
Specialties<br />
Ric<strong>in</strong>oleic Acid<br />
<strong>in</strong>termediate to sebacic acid (used for Nylon) <strong>and</strong> 2-octanol<br />
HO<br />
O OH<br />
270 °C<br />
caustic ox.<br />
HO<br />
O<br />
Markus Dierker<br />
O<br />
OH<br />
+<br />
OH
Specialties<br />
Ric<strong>in</strong>oleic Acid Methyl Ester<br />
<strong>in</strong>termediate to undecylenic acid / Nylon 11<br />
• undecylenic acid methyl ester<br />
O<br />
O OH<br />
• Nylon 11<br />
O<br />
O<br />
450 °C<br />
alkal<strong>in</strong>e cond.<br />
brom<strong>in</strong>ation<br />
O<br />
Br<br />
O OH<br />
+<br />
O<br />
am<strong>in</strong>ation<br />
H2N O<br />
Nylon 11<br />
Markus Dierker<br />
O<br />
O
Summary - Production Flow Scheme<br />
<strong>Raw</strong> <strong>Materials</strong><br />
oils<br />
&<br />
fats<br />
fatty acid<br />
methyl<br />
ester<br />
fatty<br />
acids<br />
glycer<strong>in</strong>e<br />
Oleochemicals Specialties<br />
fatty<br />
alcohols<br />
Markus Dierker<br />
sulpho fatty acid esters<br />
guerbet alcohols<br />
alkyl chlorides<br />
fatty alcohol ethoxylates<br />
fatty alcohol sulfates<br />
technical esters<br />
alkyl polyglycosides<br />
conjugated fatty acids<br />
alkyl epoxyesters<br />
dimer acids<br />
fatty acids ethoxylates<br />
azelaic/pelargonic acids<br />
fatty acid esters<br />
triacet<strong>in</strong><br />
partial glycerides
Oleochemicals<br />
Literature<br />
• Encyclopedia of Chemical Technology, 4th Edition, 1991,<br />
Kirk-Othmer<br />
• Alcohols, higher aliphatic Vol. 1, p. 865<br />
• Carboxylic acids Vol. 5, p. 147<br />
• Fats <strong>and</strong> Oils Vol. 10, p. 252<br />
• Ullmann´s Encyclopedia of Industrial Chemistry, 5th Edition, 1987,<br />
• Fatty Acids Vol. A 10, p. 245<br />
• Fatty Alcohols Vol. A 10, p. 277<br />
• The Lipid H<strong>and</strong>book, 1986<br />
edited by F. D. Gunstone, J. L. Harwood, F. B. Padley<br />
Chapman <strong>and</strong> Hall Ltd.<br />
Markus Dierker
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