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Oleochemicals and Catalysts Used
The document outlines various chemical intermediates and products derived from natural triglycerides, including the five basic oleochemicals: fatty acids, fatty alcohols, fatty methyl esters, fatty amines, and glycerine. It discusses the sources of these materials, the processes for their production such as esterification and hydrogenation, and the role of catalysts in these processes. Additionally, it highlights the growing demand for biodiesel and other applications in personal care and pharmaceuticals, emphasizing the importance of operational and financial management in production.
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Oleochemicals and Catalysts Used
- 1. Gerard B. Hawkins ManagingDirector
- 2. Chemical intermediatesand products derived from natural triglycerides 5 basic oleochemicals: ◦ fatty acids ◦ fatty alcohols ◦ fatty methyl esters ◦ fatty amines ◦ glycerine
- 3. Glycerine Fatty Acids Fatty Acid Methyl Esters Fatty Alcohol Oils & Fats splitting esterification trans-esterification Partial glycerides Triacetine FattyAcid esters F.A. ethoxylates Soaps Fatty Amines Alkyl chlorides F. OH ethoxylates F.OH sulfates Esters F.A. Alkanolamides Fatty Alcohols esterification esterification ethoxylation neutralization amination hydrogenation amidation direct hydrogenation Adapted from: Zoeblein, INFORM, Vol 3. no.6 a b c d
- 4. Lubricants Detergents Plasticizer Cosmetics
- 5. • Palm Oil(PO)- Primarily derived from the palm oil plantations in Malaysia and Indonesia is the major feedstock in Asia. • Coconut - Major source Philippines. Declining in use. • Fish oil (FH) - Predominantly used in Chile/Peru. Was popular in UK, Norway, Japan. • Canola/Rapeseed - Predominantly grown in Canada and northern Europe. Typically has higher poisons than soya. • Soyabean Oil (SO)- Primarily derived from the major soya states in the US, Brazil and Argentina. • Tallow - animal fat, usually a by-product of rendering. Lard from pigs also used. Where do they come from? • Whales - major source of oleochemicals for many years - oils, waxes, ester, spermaceti, squaleen. No longer available due to over- hunting
- 6. Alcohols ◦ OH OH O CR OH H CR H H H NR O O CR H R1 •Amines – NH2 • Esters – COOR1 • Carboxylic Acids – COOH
- 7.
- 8. Splitting Hydrogenation Distillation
- 9. Different Process ◦Twitchell used catalyst ◦ Continuos Colgate-Emery higher T & P than Twitchell ◦ Enzymatic lipases limited interest to date
- 10. Usually tofull saturatiuon ◦ i.e. break all double bonds Catalysts used ◦ Ni on silica powder; slurry phase ◦ Pd on C powder; slurry phase ◦ Pd on C; fixed bed Reactor systems ◦ Batch Dead End reactors ◦ Continuous Plug flow continuous reactors ◦ Loop reactors ◦ typical conditions 200°C & 20bar
- 11. Typically a22-25% Ni on silica or kieselguhr support Used by the majority of the market Particle diameter 6-14 microns Narrow pores to prevent Ni dissolution Used once and then must be discarded Dissolved Ni soaps end up in distillate residues
- 12. Equilibrium is determinedby hydrogen concentration ! Ni(fa)2 + H2 low pressure/ hydrogen shortage high pressure/ abundance of hydrogen Ni + 2 ffa
- 13. Fate of nickelcrystallites: Nickel dissolution is chemically reversible, but catalytic surface vanishes drastically thereby (loss of Nickel dispersion): + ffa - ffa + Ni-soaps fresh catalyst 100 m²/g Ni used catalyst 10-20 m²/g Ni
- 15. 0 5 10 15 20 25 0 0.1 0.20.3 0.4 0.5 0.6 1/H2 pressure (bar-1) DissolvedNi(ppm) 2 bar10 bar30 bar Ni2+ = K.(H+)2/H2 Ni + 2H+ = Ni2+ + H2 Note Ni dissolution decreases by factor 100 for every pH unit rise! (data based on fatty acid hydrogenation 180 C)
- 16. Smaller pore sizesimpede diffusion of larger molecules, i.e. triglycerides (Gly(fa)3) or nickel soaps (Ni(fa)2)
- 17. Soybean soap stockfatty acids, 15 bar, 200°C 1 10 100 1 10 pore size diameter (nm) final iodine value presumable course
- 18. tallow oleinfatty acids vacuum 140°C fast stirring catalyst dosage 450 ppm Nickel 50 55 60 65 70 75 80 85 90 95 100 0 50 100 time (min) relativeactivity(%)
- 19. Loss ofNickel dispersion Nickel soap formation Residual Nickel in final product
- 20. Minimize contacttime in absence of hydrogen ◦ Dose Ni to reactor just before addition of H2 or when it is already under H2 pressure ◦ Filter catalyst from FA as quickly as possible If melting of catalyst pellets required, melt in triglyceride
- 21. Ni residues Environment
- 22. Pd/C slurryphase Typical 5% Pd on a carbon support Can be re-used Must have very efficient recovery Current Pd price - $737/ounce Financial management as important as operational management
- 23.
- 24. Pd/C fixedbed Extrudates / Gauze High working capital use Efficient, continuous production Ni fixed bed has proved difficult (basic supports, posion resistance) IV < 1 unsat FA
- 25. Fatty Alcohols Surfactants 80% Shampoo Powders Bath gels etc Cosmetics Lubricants in polymerprocessing Emulsifying agents OH O CR
- 26. “Natural” fattyalcohols ◦ Hydrogenation (hydrogenolysis) of fatty methyl esters ◦ direct hydrogenation of fatty acids Synthetic fatty alcohols ◦ Oxo-Alcohols ◦ Ziegler process
- 27. Catalysts used: ◦CuCr ◦ CuZn ◦ CuSi ◦ Raney Cu Fixed bed and slurry phase units in operation Move to eliminate Cr
- 28. Feed: methylesters Gas phase FB ◦ 2900-3600psi; 230-250°C Trickle-bed ◦ 2900-4350psi; 250 °C
- 29. Higher catconsumption than FB Greater flexibility Vertical plug-flow reactor ◦ 3600psi; 250-300°C Direct hydrogenolysis of fatty acids (Lurgi) ◦ Acid-resistant catalyst required ◦ Excess of fatty OH and loop employed ◦ 4350psi; 300°C
- 30. Carbonyls infatty OH can give unwanted color, odor, etc Can be removed by hydrogenation with Ni ◦ e.g. fixed bed process with PRICAT HTC Ni impregnated alumina trilobe extrudate ◦ 100-150°C; 20-50bar
- 31.
- 32. Usually manufactureddirectly from oils via methanolysis with alkaline catalysts (e.g. sodium methylate) CH2OH CHOH CH2OH 3CHOH 3RCOOCH3 RCOOCH2 RCOOCH RCOOCH2 NaOCH3 + + methyl ester
- 33. Lower energyconsumption Less corrosive -> less expensive equipment More concentrated glycerine Easier to distill Superiority in some reactions However the use of MeOH can have its downsides
- 34. 3-armed highviscosity molecule broken down to single chain low viscous fuel Similar to cetane (C16) • Growth industry due to: – green movement and agricultural incentives in Europe – agricultural lobby and aim for domestic fuel production in USA cetane (C16) biodiesel
- 35. Most uses dependon the cationic nature of the amine Fatty Amines Corrosion Inhibitors Fabric Softeners Lubricant Additive Organoclays Sanitizing Agents H H NR
- 36. Primary amine Secondary amine Tertiaryamine R-NH2 R2NH R3N
- 37. Which amines areproduced depends on: reaction conditions ◦ NH3 pressure ◦ temperature Catalyst choice ◦ Raney Ni ◦ Supported Ni powders
- 38. Fatty nitriles FattyacidsAl2O3 NH3 Unsaturated primary amine Saturated primary amine Saturated and unsaturated secondary amines Dialkyl monomethyl tertiary amine Ni(P) Raney Ni(D) Ni(D) Formaldehyde
- 39. Batch slurryphase most common Fixed bed or continuous slurry phase also used Product Temp (C) Pressure (bar) Catalysts Special Conditions Primary 80-150 10-550 nickel, raney nickel, cobalt Ammonia added to feed to suppress secondary and tertiary amine formation Secondary 150-200 50-200 nickel, cobalt Ammonia removed by purging with hydrogen Tertiary 160-230 7 - 14 nickel, cobalt Secondary Amine used as feed; hydrogen purge necessary to remove ammonia Unsaturated copper chromite, nickel powder similar to abovesimilar to above
- 40. R-COOH + NH3R-COONH4 R-COONH4 R-CONH2 + H2O ammonium salt amide R-CONH2 R-CN + H2O nitrile R-CN + 2H2 FATTY AMINES
- 41. R-C≡N + H2 R-CH=NH imine Firstreaction step
- 42. R-CH=NH + H2 imine Primaryamine formation R-CH2NH2
- 43. Secondary amine formation R-CH=NH+ R-CH2NH2imine R-CH-NH-CH2-R NH2 1-aminodialkylamine
- 44.
- 45. Secondary amine formation R-CH2-NH-CH2-R secondaryamine R-CH=N-CH2-R imine +H2
- 46. Secondary amine formationvia hydrogenolysis R-CH-NH-CH2-R NH2 1-aminodialkylamine R-CH2-NH-CH2-R - NH3 secondary amine +H2
- 47. Tertiary amine formation proceedsvia the same route as with the secondary amine formation. However, secondary amine condenses with imine to yield tertiary intermediates.
- 48. By-product duringmanufacture of ◦ fatty acid ◦ methyl esters & bio-diesel ◦ fatty alcohols Also synthetic manufacturing Supply-Demand balance always difficult What to do with it all?
- 49.
- 50. Supply willincrease ◦ increasing production of biodiesel and use of oils and fats as industrial feedstock New demands must be found/created ◦ some of these may involve catalytic processes ◦ e.g. glycerine to glyceric acid over gold catalyst