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 lm pe Soy a Pa R Butter Other Tallow Laurics Sunflower 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 • balanced life cycle analysis O2 Proteins Carbo- Triglycerides hydrates Waxes Markus Dierker Raw Materials Distribution of Fatty Acids in Triglycerides O O O glycerine fatty acids backbone O O O CarbonCarbon ChainChain C18 Material 8 10121416182022 0123 coconut oil 87481791010 271 palm kernel oil 45501571818 2151 palm oil 2422425656 54110 rape oil a(old) 22 3838 77 5151 115157 rape oil b(new) 44 9090 22 33 160209 sunflower c(old) (old) 66 9393 42861 sunflower d(new) (new) 44 9393 11 4845 soy oil 88 9191 428536 lard 11 3131 65 65 22 13 46 6 Markus Dierker Raw Materials Distribution of Fatty Acids in Triglycerides O O O glycerine fatty acids backbone O 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 + H2O Transesterification O R R OH + 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 ROH O 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 • GMO (glycerine monooleate) OH 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 101214161820 8 101214161820 8 101214161820 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 OH HO 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 +H O 2 [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® +H O 2 [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] O HO - H2O 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 n ethoxylation O OH + O H n • nonionic surfactant, low foaming Æ good emulsifiers for W/O and O/W emulsions Æ intermediate to oleochemical products O FAEO O H n Narrow Range Ethoxylates (NRO) O O End-Capped Ethoxylates n 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 O O S 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 + HO OH HO OH OH O O O HO OHH O O OH HO OH • nonionic surfactant • very good biodegradability Æ detergent for home care applications, cosmetics Markus Dierker Specialties Polyols - Polymers O O O H2O2 RO RO R + ROH O HO O [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