MEETING UNIQEMA 2-10-03
Present: Michel Poulina, Matthijs van der Haven, Martin Patel, Arancha Pera
Gilaberte
1.) FATTY ACIDS AND FATTY ALCOHOLS
Fats and oils of vegetable or animal origin are triacylglycerols, also called
triacylglycerides or triglycerides. They are transformed to produce fatty acids in the
following way:
+H2O
Diglyc. + F.A.
Monog + F.A.
Glycerol + F.A.
Therefore, the complete reaction is:
Oil + 3 H2O  3 Fatty Acid + 1 glycerine
This reaction takes place in a countercurrent reactor. It can be performed by ordinary
splitting or by enzymatic splitting.
Another source of fatty acids is refining of natural oils: the acid oil yield is about 510% of fatty acids which is used by the oleochemical industry.
 Production of 1.4 million ton fatty acids in Europe.
 The most important fatty acids (>C8) produce from natural fats and oils is the acid
with a chain of 18 C. Besides, fatty acids with C20 and C22 chains are produced to
some extent from some selected crops.
 Fatty acid  + methanol  FAMe + H2O
 + ethanol  FAEt + H2O
Prices of ethanol and methanol: ethanol is 2x price of methanol
 Production of fatty alcohols (note that it is not possible to hydrogenate fatty acids
directly to alcohols ):
Oil  methylester  hydrogenation  alcohol + MeOH
MeOH
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Less probable path from the economic point of view:
H2
Oil  fatty acid + glycerin  ester  fatty alcohol
+ MeOh
2.) TRANSESTERIFICATION
Transesterification of natural fats and oils (triglycerides) is possible by use of
1) alkali catalyst, (2) acid catalyst and (3) enzymatic catalyst.
 Problem: Enzymes are sensitive to methanol (enzyme poison) them. Novozymes
has developed an enzyme with (limited) methanol resistance.
Check articles from Bornscheuer on enzymatic transesterification (and be sceptical
towards Japanese publications). Transesterification with lipases is already used in the
food industry.
 There is a problem in transesterification, in producing margarines:
Refine
Triglyceride
hydr
Refined
oil
hardstock
Refined
oil
Transesterif. Oil
with a % of
hardstock
Catalyst
transesterif
Water
emulsify
Glycerine and more
transesterification
Margarine
Here, there is a problem. This is a hydrogenation and a trans-chemical is produced. It
has been related to cancer problems in humans, so the interest of industry has been to
find solutions for these problems.
Cis
trans
This has promoted transesterification of “hard stock”directly into the oil.
lipase
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 Stearine + refined oil
oleine + trans-esterified stock
This is a sort of fatty acid (it’s called “hard stock” too)
3.) GLYCERINE
 Glycerine production : Global World: 1 million ton
USA: 550 kt
Europe: 250 kt
 There are four sources of glycerine:
(1) Soap production (via Soaplye; purified in the Luwa reactor)
(2) Transesterification (normal or enzymatic)
(3) Normal splitting (normal or enzymatic)
(4) Synthetic production
(5) From sweetwater ( purified and used for pharmaceutical uses)
Ad 1) Soap production:
Oil + NaOH  sodium soap + glycerine + NaOH (residual)
10% glycerine
Formerly the glycerine remained in the soap, while it is removed nowadays.
The glycerine phase contains some NaOH residual which is neutralized with
HCl. The resulting product is SOAPLYE that is the mixture of glycerine and
5-7% of NaCl. There is a limited capacity to purify glycerol in the so-called
Luwa process.
Ad 2) Conventional transesterification (glycerine as byproduct of biodiesel
production):
Oil + 3 MeOH (in reality in excess: 6 mole)
 3 methylesters of fatty acid + 1 glycerol + residual catalyst (NaOH)
The top phase of the reactor contains the product methylester together
with some methanol. The bottom phase contains glycerine + soap +
NaOH which is neutralized with HCl. The resulting product is Soaplye
(mixture of glycerine and 5-7% of NaCl).
No NaOH in the case of enzymatic transesterification (byproduction of
glycerol not via Soaplye).
A problem with glycerine from the biodiesel industry is the use of catalysts
other then NaOH. This means complications in processing.
 The medium price of glycerine has undergone major fluctuations. In the recent
past there has been an important downward trend. The medium price was 1200
euro/ton.
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 In 2010, 500-600 kilotonnes of glycerine will be produced in Europe , of which
som 300 will be originated from bio-diesel) which is very likely to put glycerol prices
under pressure worldwide.
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-
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
As a consequence glycerine may be used as a feedstock for an increasing
number of products and processes (currently hampered by the high price of
glycerine).
For example, glycerol may be used as a substitute for sorbitol (current
production: glucose + hydrogen  sorbitol). Glucose is currently being
produced in food products and consumer products like toothpaste. An obstacle
for substitution is the change of flavour of the products.
Ethylenglycol and polyethylene glycol could also be affected since they are
similar to glycerol (3 OH groups vs. 2)
The new market situation may also put increased pressure on the synthetic
production of glycerine. DOW is nowadays the only company worldwide that
produces synthetic glycerine (used for polyol production in polymers; Shell
closed down their plant more than 10 years ago).
Glycerol  opportunities (potential blocks for chemical industry. Literature
analysis, patents on glycerol). Read some books and look for old uses of
glycerine that are not used nowadays because of the high price of glycerine.
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