Chapter 1 :

Introduction of Oleochemistry
(Spheres of environmental chemistry)

By: Miss Noraishah Binti

Abdullah
Oleochemistry
• Oleochemicals are chemicals derived from
biological oils or fats.

• The hydrolysis or alcoholysis of oils or fats

form the basis of the oleochemical industry.
• basic oleochemical substances are:-
– fatty acids
– fatty acid methyl esters (FAME),
– fatty alcohols,
– fatty amines and
– Glycerols

• Intermediate chemical substances

produced from these basic oleochemical
substances include
alcohol ethoxylates alcohol ether sulfates
diacylglycerols (DAG), alcohol sulfates
quaternary ammonium monoacylglycerols (MAG),
substances

triacylglycerols (TAG) sugar esters.

Application of oleochemistry
• The most common application of
oleochemicals is biodiesel production.
• Another common application is in the
production of detergents; lauric acid is
used to produce sodium lauryl sulfate,
the main ingredient in many personal
care products.
• Other applications include the
production of lubricants, green
solvents, and bioplastics.
Introduction to oleochemical industry
in Malaysia
• The oleochemical industry in Malaysia started
in the early 1980s. It comprise the basic
oleochemicals and oleochemical derivatives
sub-sectors. Malaysia is one of the world's
leading basic oleochemicals producers and
net exporters.
• The oleochemical industry is almost totally
dependent on indigenous raw materials, i.e.
palm oil and its derivatives and palm kernel
oil as feedstocks in the various basic
oleochemical products.
• The industry comprises manufacturers of both
local and several joint-venture companies with
multinationals.
Emergence of palm oil industry
Chapter 2 : Fat Splitting
Miss Noraishah Binti Abdullah
2.0 Fat splitting
• Fatty acids are obtained by
hydrolysing the fats or what is
popularly known of fat splitting
process.
• Fat + water  Glycerol + Fatty
acids
• The mixed fatty acid from fat
splitting is separated from
glycerine and further purified by
pressing or distillation to gets
desirable cuts for particular uses.
2.1 Pre-treatment
• Before coming to fat splitting, it
will be desirable to consider the
various impurities present in the
various fatty raw-materials and
their purification.
• These impurities should be
removed before proceeding with
the main process, as they interfere
and cause difficulties with the
process of fatty acids.
Why we need pre-treatment?
• land animals containing 60±90 per
cent fat,
• whole fish with 10±20 per cent oil,
• or vegetable seeds and soft plant
tissue with 20±70per cent oil.

In order to get pure products of

fatty acids, impurities need to be
extracted from fats and oils
Extraction
• Animal fats, from whole animals, depot
fats, contain active enzymes, so the fat
should be extracted as quickly as possible
• highly unsaturated nature of fish oils also
make them liable to rapid oxidation.
• Vegetable fruits, such as those from the oil
palm, have a high moisture content and
here also the oil should be extracted as
quickly as possible to minimise enzymic
hydrolysis.
• Pre-treatment process includes:-
a) Refining
b) Degumming
c) Neutralization
d) Bleaching
a) Refining
• removal of undesirable
components and will usually result
in a product with minimal colour
and flavour
• The compounds removed by
refining include phospholipids, free
acids, mono- and di-acylglycerols,
colour, trace metals, oxidation
products and environmental
contaminants.
b) Degumming
• Degumming is the treatment of crude
oils with water or dilute acid (phosphoric
or citric) to remove phospholipids,
lecithin, cephalin.
• The popular method- hydrolytic
degumming process
• Oil+water- heated with additive such as
Ba(OH) or H3PO4 refine and emulsified,
removed hydrated gum.
c) Neutralization

This is effected by treatment with alkali

soapstock is separated and can be

acidified to give fatty acids.

Soapstock- cheap acidic oil -Soapstock contains free

acids
as sodium salts (usually) contaminated with
triacylglycerols
and phospholipids.

Traditionally, this has been acidified with sulfuric

acid to provide crude fatty acids for soap making or
as additives to animal feeds
d) Bleaching
• Bleaching is carried out mainly to
reduce colour (carotenes, chlorophyll)
and involves heating the oil at
80±180°C (mainly at 90±120°C) in the
absence of oxygen with a bleaching
earth such as bentonite, fullers' earth,
activated carbon, or amorphous silica
• There are at least four known methods
of fat splitting:-
(1) Twitchell process
(2) batch autoclave process
(3) continuous process
(4) enzymatic process.
(1) Twitchell process
• one of the earliest processes developed
for fat splitting low initial
• cost and simplicity of installation and
operation-no commercial value
Method.
• sulfuric acid to catalyze the hydrolysis.
• reagent is a sulfonated mixture of oleic
or other fatty acid and naphthalene
• The operation is carried out in a wooden, lead-
lined, or acid-resistant vad
• the fat, water amounting to approximately half the
fat, 1–2% sulfuric acid, and
• 0.75–1.25% Twitchell reagent are boiled at
atmospheric pressure for 36–48 h, using open
steam.
• The process is usually repeated two to four times,
drawing off the glycerine–water solution after each
stage.
• At the last stage, water is added and the mixture
boiled to wash off any remaining acid.
• The long reaction period, high-steam consumption,
and discoloration of the fatty acids are
disadvantages of the process and are the reasons
for its limited use today.
(2) batch autoclave process

• The batch autoclave process is the

oldest commercial method used for
splitting higher grade stock to produce
light-colored fatty acids.
• more rapid than the Twitchell process,
taking about 6–10 h to complete.
Method
• process uses a catalyst, usually zinc,
magnesium,or calcium oxides.-zinc is the
most active.

• 2–4% catalyst is used, and a small amount

of zinc dust is added to improve the color
of the fatty acids.

• The autoclaves are tall cylinders, 1220–

1829 mm in diameter and 6–12 m high
made of corrosion-resistant alloy and fully
insulated. An injection of live steam
provides the agitation, although some, in
addition, use mechanical agitators.
• In operation, the autoclave is charged
with the fat, water amounting to about
half the fat, and the catalyst.
• Steam is blown through to displace any
dissolved air, and the autoclave is
closed.
• Steam is admitted to raise the pressure
to 1135 kPa and is injected continuously
at the bottom while venting a small
amount to maintain the desired agitation
and operating pressure.
• More than 95% conversion is achieved
after 6–10 hour.
• The contents of the autoclave are
transferred to a settling tank
• two layers are formed: the fatty acid
upper layer and the glycerine
(sweetwater) lower layer. The fatty acid
layer is drawn off, treated with mineral
acid to split the soap formed, and finally
washed to remove traces of the mineral
acid.
(3) continuous process
• The continuous countercurrent, high-pressure
fat-splitting process, knownly as the Colgate–
Emery process.
• The high temperature and pressure used permit
short reaction time.
• Full countercurrent flow of oil and water
produces a high degree of splitting without the
need of a catalyst. However, a catalyst may be
used to increase reaction rate.
• The splitting tower is the heart of the
process.
• Most splitting towers have the same
configuration and basically operate the
same way.
• Depending on the capacity,the tower can
be 508–1220 mm in diameter and 18–25
m high and is made of corrosion-resistant
material such as stainless steel 316 or
Inconel alloy
• designed to operate at a pressure of
about 5000 kPa.
• The deaerator fat is introduced by means of a
sparge ring, around 1 m from the bottom with
a high-pressure pump.
• Water is introduced near the top at a ratio of
40–50% of the weight of the fat.
• The high splitting temperature (250–260°C)
ensures adequate dissolution of the water
phase into the fat
• so that mechanical means for bringing the
two phases into contact are not required.
• The empty volume of the tower is used as the
reaction compartment.
• The crude fat passes as a coherent phase from the
bottom to the top through the tower,
• whereas the heavier splitting water travels
downward as a dispersed phase through the
mixture of fat and fatty acid.
• Degrees of splitting up to 99% can be reached
• reaction time of only 2–3 h.
• Little discoloration of the fatty acids occur.
• Reaction produce efficient internal heat exchange,
this process affords high steam economy.
• The utilities consumption per ton of feed
is as follows.

• Steam (6000 kPa) 190 kg

• Cooling water (20°C) 3 m3
• Electrical energy 10 kWh
• Process water 0.6 m3
Method.
(4) enzymatic process.
• Fat splitting through the use of lipolytic
enzymes had been carried out in experimental
trials. However, at present, this process is of
doubtful importance because of its high cost
and long reaction time.
• The enzymatic splitting of fats and oils by
lipase from Candida Rugosa, Aspergillus niger,
and Rhizopus arrhizus had been studied at a
temperature range of 26–46C for a period of
48–72 h.
• About 98% splitting is possible
Purification and fractionation of FA
• The FAs obtained by the fat-splitting unit are in a
crude state and require purification, which is
accomplish by distillation.
• The boiling points of most of the fatty acids are
above 300°C and most of the unsaturated fatty
acids decompose at this temperature.
• In order to purify them without decomposition,
distillation should be carried out at lowest
possible temperature and hence at the lowest
possible pressure.
Fatty Acid Distillation and Fractionation
Operations

• Fatty Acid Distillation. Distillation of crude

fatty acids removes both the low and high
boiling impurities as well as odor bodies.
• Fatty acids are extremely sensitive to heat,
oxidation, and corrosion effects-due to the
reactive acid group at the end of the long
carbon chain.
• These factors are taken into consideration in
the
design of the distillation unit and its operating
parameters.

Distillation is carried out under high vacuum

and lower temperatures and shorter time.
• Technical design of most distillation
units features high vacuum
• NO Allowance for air leakage, effective
heating to achieve short contact time,
good circulation for effective mass
transfer between vapor and
condensate, and steam economy.
• Crude fatty acid is predried and degassed under
vacuum and fed to the distillation unit, which is
operated at a vacuum of 1.2 kPa or less and a
temperature of approximately 200°C.

Fatty Acid Fractionation.

• developments in fractionation technology can now
readily meet this challenge. Purities of 99.5% can be
achieved for pure cuts of C12 or C14 fraction.
• The detergent-grade feedstock C12–C18
fraction is separated from the whole cut by topping off
the C8–C10 fraction.
• middle cut, C12–C14, can be further fractionated from
the C12–C18 cut through the use of multistage
fractionation employing two or more columns.
• Basically, each process uses a
deaerator, heat source, fractionation
column, condensing system, and
vacuum source