raw materials and processes in oleochemistry
TRANSCRIPT
Markus Dierker
Raw Materials and Processes in Oleochemistry
Markus Dierker
Markus Dierker
Contents
• Raw Materials
• Basic Oleochemical Transformations
• Oleochemical Products
• Summary
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World Production of Oils and Fats 2002 (mil mt)
24.0
6.16.38.4
29.7
24.9
13.3
7.6
8
16
Soy
Palm Rape
Sunflower
Tallow
Butter
Lauric
s
Other
vegetable (approx. 80%)animal (approx. 20 % declining)
Raw Materials
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Regions of Production / Share of World Production 2002 (%)
18
12
2040
Raw Materials
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Raw Materials
World Consumption of Oils and Fats (mil mt)
120.3
97.4
16.86.1
Total Food Chemistry Feed81 % 14 % 5 %
World Consumption of Mineral Oil in 2004: approx. 4.000 mil mt
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Raw Materials
Natural Generation of Triglycerides
EnergyCO2
H2O
TriglyceridesWaxes
Nutrients
ProteinsCarbo-
hydrates
O2
O
O O
O
O
O
• linear, sat./unsat. FA witheven numbered C-chains
• renewable resources• biodegradable• balanced life cycle analysis
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Material 8 10 12 14 16 18 20 22coconut oil 8 7 48 17 9 10palm kernel oil 4 5 50 15 7 18palm oil 2 42 56
rape oil a 2 38 7 51
rape oil b 4 90 2 3
sunflower c (old) 6 93
sunflower d (new) 4 93 1soy oil 8 91lard 1 31 65 2
Carbon Chain
Distribution of Fatty Acids in Triglycerides
0 1 2 32 7 12 15 15 41 101 15 15 71 60 20 94 28 614 84 54 28 53 613 46 6
C18
Raw Materials
Material 8 10 12 14 16 18 20 22coconut oil 8 7 48 17 9 10palm kernel oil 4 5 50 15 7 18palm oil 2 42 56rape oil (old) 2 38 7 51rape oil (new) 4 90 2 3sunflower (old) 6 93sunflower (new) 4 93 1soy oil 8 91lard 1 31 65 2
Carbon Chain
O
O
O
O
O
O
glycerine backbone fatty acids
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• no statistic distribution of fatty acids in triglycerides
example cocoa butter: PSO: 36%SOS: 25%PPO: 15%PPS: 1%
Distribution of Fatty Acids in Triglycerides
Raw Materials
O
O
O
O
O
O
glycerine backbone fatty acids
P = palmitic acid S = stearic acid O = oleic acid
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+
+[cat] O
OR
OHR
OHR
O
OR
O+
[cat]
OH
O
R
OR H2O+
HO
Basic Oleochemical Transformations
Esterification / Ester Cleavage
Transesterification
Hydrogenation
HO
O
[cat]H2
HO
O
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Production Flow Scheme
Raw Materials
oils&
fats
fattyalcohols
glycerine
Oleochemicals Specialties
fattyacids
fatty acidmethylester
sulpho fatty acid esters
guerbet alcoholsalkyl chloridesfatty alcohol ethoxylatesfatty alcohol sulfatestechnical estersalkyl polyglycosides
triacetinpartial glycerides
conjugated fatty acidsalkyl epoxyestersdimer acidsfatty acids ethoxylatesazelaic/pelargonic acidsfatty acid esters
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RO
O+
OH
OH
OH
RO
O
RO
O
[cat]∆T
O
O
O
O
O
O3+ R OH
Chemical Conversion of Triglycerides
Oleochemicals
• Splitting
water fatty acids
alcohol fatty acid estersTG + glycerine +
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OH
O
OH
O
OH
OH
OH
Glycerine / Derivatives
Oleochemicals
Glycerine• purification by distillation or ion exchange
pharma-grade glycerine (86%, > 99%)
cosmetics, pharma, nutrition, graphic & printing, ...
Glycerides• esterification / transesterification
special mono-, di-, tri-glycerides
• GMO (glycerine monooleate)
• triacetin (triacetyl glycerine)
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Production Flow Scheme
Raw Materials
oils&
fats
fattyalcohols
glycerine
Oleochemicals Specialties
fattyacids
fatty acidmethylester
sulpho fatty acid esters
triacetinpartial glycerides
conjugated fatty acidsalkyl epoxyestersdimer acidsfatty acids ethoxylatesazelaic/pelargonic acidsfatty acid esters
guerbet alcoholsalkyl chloridesfatty alcohol ethoxylatesfatty alcohol sulfatestechnical estersalkyl polyglycosides
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Fatty Acids
Oleochemicals
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
fractionated FAdistilled FA
0
20
40
60
80
100
8 10 12 14 16 18 200
20
40
60
80
100
8 10 12 14 16 18 200
20
40
60
80
100
8 10 12 14 16 18 20
polyunsaturated FA
soaps, detergents, emulsifiers, other oleochemicals, ...
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Fatty Acids - Main Technologies
Oleochemicals
• Splitting
• Distillation
• Fractionation
• Crystallisation (Hydrophilisation)
• Hydrogenation (partial or full)
• Esterification
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Fatty Acids – Oleic Acid
Oleochemicals
• Production• crystallisation (hydrophilisation)• saturated acids as by-products
• 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
tallow
C16/18 fatty acids
techn. stearic aicd oleic acid
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Fatty Acids - Specialties
Oleochemicals
Pelargonic Acidesters plasticizers, lubricants, corrosion inhibitors
Azelaic Acidesters, plasticizer, soaps, polyamides, nylon, adhesives, coatings
HO
O
HO
O O
OH
O
HO+
O3
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Conjugated Fatty Acids
Oleochemicals
UKD Fatty Acids®
mixture of many isomersalkyd resins
Tonalin®
two isomers: c9,t11- / t10,c12- CLAfunctional foods
RO
O
+ isomers+
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Monomer / Dimer Acids
Specialties
Isostearic Acids Emersol®
hydrogenation, fractionation isostearic acidcosmetics, lubricants, plastic auxilliaries
Dimer Acids Empol®
purificationpolyamides, polyesters, lubricants, corrosion inhibitors
monomer acidC18
dimer acidC36
+
O
HO
O
OHO
HO
O
HO
∆T[cat]
+
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Production Flow Scheme
Raw Materials
oils&
fats
fattyalcohols
glycerine
Oleochemicals Specialties
fattyacids
fatty acidmethylester
sulpho fatty acid esters
triacetinpartial glycerides
conjugated fatty acidsalkyl epoxyestersdimer acidsfatty acids ethoxylatesazelaic/pelargonic acidsfatty acid esters
guerbet alcoholsalkyl chloridesfatty alcohol ethoxylatesfatty alcohol sulfatestechnical estersalkyl polyglycosides
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Fatty Acid Methyl Esters
fatty alcohols
intermediate to production of special esters
solvents, lubricants
Biodiesel (rape seed oil methyl ester)
Oleochemicals
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RO
O[cat]+ H2
- ROHHO
Fatty Alcohols
Oleochemicals
• 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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Fatty Alcohols
Oleochemicals
main intermediate to other oleochemicals
carboxylic esterssulfosuccinates
fatty alcohol sulfates
fatty alcohol ethoxylates
fatty alcohol ether sulfates
fatty alcohol phosphates alkyl polyglucosides
alkylhalogenides
acrylatesmethacrylates
fatty amines
fatty alcohols
main application as detergents
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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, ...
Oleochemicals
Unsaturated Alcohols HD-Ocenols®
C16-18 solvents, defoamers, plasticizer, emulsifier, oil component in cosmetics
RO
O [cat]+ H2
- ROH HO
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Fatty Alcohols Specialties
Oleochemicals
Diols Speziol®
C8 / C10 / C12 / C18 cosmeticsagro chemicalspharmaceuticalsplasticizer
Branched Alcohols Speziol®
C16-18 satur. / unsatur. detergentscosmeticsfine chemicals
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Guerbet Alcohols
Specialties
Guerbet Alcohols Rilanit®
C16 / C20 plasticizersspray lubrication (metalworking)solubilizer for water-miscible MWFmold release agentsoil components in cosmetic applicationdispersing agents
HO∆T, ∆p
O
HOOaldol cond.
- H2O
- [H]
+ [H]
[cat]
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FAEO
Narrow Range Ethoxylates (NRO)
End-Capped Ethoxylates
Fatty Alcohol EO/PO Adducts OO
Hm
OO
n
O O
nH
Fatty Alcohol Ethoxylates (FAEO)
• nonionic surfactant, low foaming
good emulsifiers for W/O and O/W emulsions
intermediate to oleochemical products
Surfactants
OO
n
OH + OO O
Hn
n ethoxylation
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Fatty Alcohol Sulfates (FAS)
Surfactants
Fatty Alcohol Ether Sulfates (FAES)
• anionic surfactants• very good skin compatibability• very good foaming power
basic surfactants in cosmetic detergents and cleaners
• insensitive to water hardness• very good water-solubility
• anionic surfactants• good foaming power
fire extinguisher foamsdetergents for home care and cosmetic application
• insensitive to water hardness
OS
O
OO
NaOHsulfation
OO
Hn
sulfationO
O
nO
SO
OO
Na
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OHO
OHOH
HOHO
OH
+
O
OHOH
HO
O
O
OHOH
OH
HOO
Alkyl Polyglucosides (APG)
• nonionic surfactant• very good biodegradability
detergent for home care applications, cosmetics
Surfactants
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Polyols - Polymers
• hydrophobic fatty acid polyol• adjustable properties / performance
self-stabilising softeners, PU components
Specialties
+ isomers
R OH+[cat]
H2O2RO
O ORO
O
RO
O HO OR
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lubricants, hydraulic fluids, power transmission, MWF, ...
challenging requirements• temperature• oxidative stress• long service-life • price
Polyol Esters
Polyol Esters - Synlubes
Specialties
• viscosity• CP/PP• emulsifying properties
• structural variability
• tunable properties / performance
• biodegradableO
O
R
O
O
R
O
R
O
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Castor Oil
Specialties
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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Ricinoleic Acid
Specialties
intermediate to sebacic acid (used for Nylon) and 2-octanol
HO
O OH
HO
O
OOH
OH+
270 °Ccaustic ox.
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Ricinoleic Acid Methyl Ester
Specialties
intermediate to undecylenic acid / Nylon 11
450 °C
O
O OH
alkaline cond. O
O OH+
• Nylon 11
O
O
O
O
Br
O
O
H2N
bromination
amination Nylon 11
• undecylenic acid methyl ester
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Summary - Production Flow Scheme
Raw Materials
oils&
fats
fattyalcohols
glycerine
Oleochemicals Specialties
fattyacids
fatty acidmethylester
sulpho fatty acid esters
guerbet alcoholsalkyl chloridesfatty alcohol ethoxylatesfatty alcohol sulfatestechnical estersalkyl polyglycosides
triacetinpartial glycerides
conjugated fatty acidsalkyl epoxyestersdimer acidsfatty acids ethoxylatesazelaic/pelargonic acidsfatty acid esters
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Literature
Oleochemicals
• 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. PadleyChapman and Hall Ltd.
End of Presentation