2. Chemical intermediates and 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 Fatty Acid 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. Fatty Acids Soap CosmeticsLubricants Plasticizer
Intermediates OH O CR
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 to full 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 200C & 20bar
11. Typically a 22-25% 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 determined by hydrogen concentration !
Ni(fa)2 + H2 low pressure/ hydrogen shortage high pressure/
abundance of hydrogen Ni + 2 ffa
13. Fate of nickel crystallites: Nickel dissolution is
chemically reversible, but catalytic surface vanishes drastically
thereby (loss of Nickel dispersion): + ffa - ffa + Ni-soaps fresh
catalyst 100 m/g Ni used catalyst 10-20 m/g Ni
14. 0 5 10 15 20 25 0 0.1 0.2 0.3 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)
15. Smaller pore sizes impede diffusion of larger molecules,
i.e. triglycerides (Gly(fa)3) or nickel soaps (Ni(fa)2)
16. Soybean soap stock fatty acids, 15 bar, 200C 1 10 100 1 10
pore size diameter (nm) final iodine value presumable course
18. Loss of Nickel dispersion Nickel soap formation Residual
Nickel in final product
19. Minimize contact time 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
20. Ni residues Environment
21. Pd/C slurry phase 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
22. 4 Fresh Catalyst 6 Spent catalyst 7 Incineration spent
catalyst 8 Precious metal ash 2 Precious metal sponge 3 Precious
metal salt solution 1 Precious metal 5 Customers process 9 Precious
metal ash refining
23. Pd/C fixed bed Extrudates / Gauze High working capital use
Efficient, continuous production Ni fixed bed has proved difficult
(basic supports, posion resistance) IV < 1 unsat FA
24. Fatty Alcohols Surfactants 80% Shampoo Powders Bath gels
etc Cosmetics Lubricants in polymer processing Emulsifying agents
OH O CR
25. Natural fatty alcohols Hydrogenation (hydrogenolysis) of
fatty methyl esters direct hydrogenation of fatty acids Synthetic
fatty alcohols Oxo-Alcohols Ziegler process
26. Catalysts used: CuCr CuZn CuSi Raney Cu Fixed bed and
slurry phase units in operation Move to eliminate Cr
27. Feed: methyl esters Gas phase FB 2900-3600psi; 230-250C
Trickle-bed 2900-4350psi; 250 C
28. Higher cat consumption than FB Greater flexibility Vertical
plug-flow reactor 3600psi; 250-300C Direct hydrogenolysis of fatty
acids (Lurgi) Acid-resistant catalyst required Excess of fatty OH
and loop employed 4350psi; 300C
29. Carbonyls in fatty 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 100-150C;
20-50bar
30. Fatty M.E. Intermediates Biodiesel O O CR H R1
31. Usually manufactured directly from oils via methanolysis
with alkaline catalysts (e.g. sodium methylate) CH2OH CHOH CH2OH
3CHOH 3RCOOCH3 RCOOCH2 RCOOCH RCOOCH2 NaOCH3 + + methyl ester
32. Lower energy consumption Less corrosive -> less
expensive equipment More concentrated glycerine Easier to distill
Superiority in some reactions However the use of MeOH can have its
downsides
33. 3-armed high viscosity 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
34. Most uses depend on the cationic nature of the amine Fatty
Amines Corrosion Inhibitors Fabric Softeners Lubricant Additive
Organoclays Sanitizing Agents H H NR
38. Batch slurry phase 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
46. Tertiary amine formation proceeds via the same route as
with the secondary amine formation. However, secondary amine
condenses with imine to yield tertiary intermediates.
47. By-product during manufacture of fatty acid methyl esters
& bio-diesel fatty alcohols Also synthetic manufacturing
Supply-Demand balance always difficult What to do with it all?
48. Personal Care Glycerine Tobacco Pharmaceutical Food
Explosives
49. Supply will increase 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