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GLOBAL CONSUMPTION OF OILS AND FATS
OLEOCHEMICAL

OLEOCHEMICAL

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Chemlcal derlves from naLural olls
and faLs as opposed Lo chemlcal
derlved from peLrochemlcal
feedsLock
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Most common biodiesel production
Production of detergents (lauric acid used to produce sodium lauryl sulfate, the main
ingredient in many personal care products)
Production of lubricants, green solvents, bioplastics, cosmetics
APPLICATION OF OLEOCHEMICAL

Started in the early 1979 (10,000 tonnes of fatty acids and glycerol)
Palm oil and its deivatives and palm kernel oil as feedstock
Local and several joint-venture companies with multinationals
MALAYSIAN OLEOCHEMICAL INDUSTRY
Malaysia is the leading producer and exporter of basic oleochemicals in the world
MALAYSIAS PALM OIL INDUSTRY

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MALAYSIAN PALM OIL INDUSTRY EXPORT (2011)


- derived from renewable resources, as
compared to petrochemicals which are obtained
from exhaustible or non-renewable petroleum
- more readily biodegradable and hence do
not pose a threat to the environment
- products derived from petroleum sources use more energy and cause higher emissions of
pollutants such as NO
2
, SO
2
, CO & hydrocarbons
OLEOCHEMICAL VS PETROCHEMICAL
- Costs of crude oil and fuel remain high
- Continued price increase in petrochemical-derived ingredients
OLEOCHEMICAL - AN ALTERNATIVE FEEDSTOCK

- Renewable raw materials
- Expanding global oilseed production
- Government subsidies and incentives
- Increasing regulation for synthetic/petrochemical-based ingredients
- Increased in R & D for vegetable oil-based industrial products and fuel
- Increased interest from traditional petro-based manufacturers
- Growing importance of biotechnology
- Consumer preference for naturals
- Growing trend in green chemistry
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WORLDWIDE SOURCES OF RAW MATERIALS FOR
OLEOCHEMICALS

RAW MATERIALS FOR OLEOCHEMICAL

Prior to 1985, tallow was an important raw material for the oleochemical industry
Main feedstock: tallow and coconut oil
due to BSE, tallow has been replaced in most of the personal care by PO
RAW MATERIALS FOR OLEOCHEMICAL

Coconut oil, the only other oil with short- and medium- chain FA, has not been growing in
the last years, and has therefore lost ground to palm kernel oil
source: U. R. Sahasranamam
M
i
l
l
i
o
n

M
T

stagnant global availability of tallow & coconut oil, greater availability of palm oil & palm
kernel oil
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COCONUT OIL VS PALM KERNEL OIL

PALM KERNEL OIL

2006 1.99 million tonnes of PO & PKO (60% PKO and 5% PO) processed into
oleochemicals
PKO extremely important due to its short (C8-C10) and medium-chain (C12-C14) FA
whereas PO its long chain (C16-C18) FA
PO & PKO covering the total needs of the oleochemical industry with the exception of high-
erucic rapeseed oil (C20 and C22 )
Source : Wolfgang Rupilius, Salmiah Ahmad
ADVANTAGES OF PALM KERNEL OIL

come from the same source, unlike coconut oil and tallow
constant supply of raw materials
PO & PKO advantages over tallow & coconut oils:
palm based oleochemicals derived from vegetable sources, unlike tallow which is
animal-based
palm based oleochemicals enjoy the versatility of various palm-based derivatives
palm-based products are more economical
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BASIC OLEOCHEMICAL

Malaysia is one of the world's leading basic oleochemicals producers and net exporters
BASIC & INTERMEDIATES OLEOCHEMICALS USES

BASIC OLEOCHEMICAL

source: Dr Salmiah Ahmad
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BASIC OLEOCHEMICALS, OLEODERIVATIVES & END-PRODUCTS

BASIC OLEOCHEMICALS
FATTY-ACID

Direct uses As derivatives Intermediate chemicals
for
Rubber processing
Candles
Cosmetic products
Medium chain
triglycerides(MCT)
Soap
Production of mettalic
soap
Fatty alcohols
Fatty amines
Fatty esters
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FATTY-ACIDS

gate way to other oleochemicals
Palm oil/Palm
Kernel oil
(Fat Splitting)
hydrolisis
Crude fatty acid
Separation
-Distillation
-Hydrogenation
-Fractional
distillation
-distilled Fatty acid
-saturated fatty acid
-unsaturated fatty acid
-fractionated fatty acid
FATTY-ACIDS

palmitic acid or stearic acid obtained from both PO & PKO via hydrolytic splitting,
fractional distillation and hydrogenation
shorter chain fatty acids (C14 or lower) esp. lauric acid are from coconut or palm kernel
oil (only commercially available lauric oils)

a reversible reaction
FAT-SPLITTING/HYDROLYSIS
in stages (tri to di to mono)
initial stage : reaction proceeds slowly (low solubility of the water in the oil phase)
second stage : reaction proceeds fairly rapidly (greater solubility of water in the fatty acids)
nal stage : diminishing reaction rate (reach equilibrium)
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FAT-SPLITTING
increasing temperature & pressure accelerates the reaction (increased solubility of the water in the
oil phase & higher activation energy)
glycerine byproduct must be withdrawn continuously to force the reaction to completion
small amounts of mineral acids (sulfuric acid) or certain metal oxides (zinc or magnesium
oxide) accelerates the splitting reaction

SPLITTING COLUMNS
1he deaeraLed faL ls
lnLroduced by means
of a sparge rlng,
around 1 m from Lhe
bouom wlLh a hlgh-
pressure pump.
WaLer ls lnLroduced
near Lhe Lop aL a
rauo of 40-30 of
Lhe welghL of Lhe faL.
1he hlgh spllmng
LemperaLure (230-
260C) and a pressure
(30-33 bar) ensures
adequaLe dlssoluuon of
Lhe waLer phase lnLo Lhe
faL
Crude lauy acld SweeLwaLer(glycerol)

CONTINUOUS HIGH PRESSURE FAT-SPLITTING PROCESS
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production involves pretreatment to remove phosphatides, heavy metals & solid matters
FATTY ACIDS
pretreated oils are then split using demineralized water at 250 255
o
C and a pressure of
50-55 bar into fatty acids & sweetwater (15% glycerol)
crude FA produced are then purified to remove colour bodies, partial glycerides,
unsaponifiable matter, polymerized FA and free glycerol by simple distillation or separated into
component homologues by fractional distillation
hydrogenation is carried out if high quality saturated acids are required
separation of palmitic & stearic acids, a fractionator with a single column of 20 trays may be
used
separation of PKO into C8/C10, C12, C14,C16/C18 uses multi-columns
FATTY METHYL ESTERS

development of biodiesel (clean burning with no sulfur dioxide emission) methyl esters have
become the fastest growing oleochemicals

FATTY METHYL ESTERS
usually manufactured directly from oils via methanolysis with alkaline catalysts (eg. Sodium
methylate)
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FATTY METHYL ESTER
GLOBAL BIODIESEL PRODUCTION


fatty acid methyl esters (FAME) have increasingly replaced fatty acids as starting materials for
many oleochemicals
FATTY ACID METHYL ESTER
1. production of methyl esters requires much lower reactor temperatures and pressures than
the splitting of fats and oils to obtain fatty acids
2. methyl ester are noncorrosive & are produced at lower operating temperature & pressure
(processed in carbon steel equipment); FA are corrosive (heavy-duty stainless steel
equipment)
3. transesterification is a dry reaction & yelds conc. glycerine, while fat splitting produces
glycerine water which has more than 80% water (uses more energy to recover)
4. esters are more easily distilled because of their lower boiling points & are more heat
stable than the corresponding FA
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MPOB PALM BIODIESEL PRODUCTION


in Malaysia, fatty methyl esters are prepared via 2 routes:
TRANSESTERIFICATION
1. Transesterification (methanolysis) of triglycerides with methanol (most common method)
alkaline catalysts are used with sodium methylate (most effective) although sodium
hydroxide can also be used
sequence of steps is triglyceride to diglyceride to monoglyceride with1 mole of methyl ester
formed at each cleavage

ESTERIFICATION
2. Esterification of fatty acids with methanol (more cost intensive)

reversible reaction thus, water must be removed to drive the reaction to the right and
obtain a high-ester yield
acid catalysts like sulfuric acid are employed
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FATTY ALCOHOLS

one of the major basic oleochemicals enjoying a continuing growth rate (primary raw material
for surfactants [80%])

FATTY ALCOHOLS - PROCESS
direct hydrogenation of fatty acids
Natural fatty alcohol:
hydrogenauon of fauy meLhyl esLers

HIGH PRESSURE HYDROGENATION USING SUSPENSION PROCESS
a two-step reaction:
Lurgi method
overcomes the damaging effects of the fatty acids on the copper-bearing analyst
both reactions occur simultaneously in the same reactor
fatty alcohol recirculated, more than 250 times the fatty acid feed, effectively dilutes the feed,
hence rapid and complete esterication
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FATTY ALCOHOLS


FATTY ALCOHOL
crude fatty alcohol undergoes fractionation to produce different cuts of alcohol
FATTY AMINES

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FATTY AMINES
bases for the manufacture of quaternary ammonium compounds used as fabric softeners
and biocides
most important nitrogen derivatives of fatty acids
produced by the reaction of fatty acids with ammonia and hydrogen
main raw material is the fatty nitrile derived from the reaction of fatty acid with ammonia
fatty amine oxides are mild to the skin with good cleaning and foaming properties and nd
application as a shampoo ingredient
catalytic hydrogenation of the nitrile produces the amines

FATTY AMINES
available as primary, secondary, and tertiary amine, depending on the number of the alkyl
groups attached to the nitrogen atom
which amines are produced depends on the reaction conditions (NH
3
pressure & temperature)
& catalyst choice (Raney Ni or supported Ni powders)

CHEMISTRY OF FATTY AMINES PRODUCTION
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GLYCEROL

chemical formula, C
3
H
8
0
3
also known as glycerin/glycerine (commercial grades)
by-product of fatty acid, methyl esters & biodiesel and fatty alcohol production

used in cosmetics, pharmaceuticals, explosives, food & tobacco

supply increasing due to increasing production of biodiesel & use of oil & fats as
industrial feedstock

colourless, odorless, viscous & non-liquid, have slight sweet taste
GLYCEROL

GLYCEROL PRODUCTION

Clycerol
roducuon
1rans-
esLerlcauon
Pydrolysls Saponlcauon
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SAPONIFICATION

also known as soap formation
oil/fat reacts with caustic soda to form soap and soap lye
soap lye formed contains 4 20% glycerol (also known as sweetwater)
SPLITTING

also known as hydrolysis
under pressure and at high temperature to produce fatty acids and sweetwater
sweetwater contains 10 20% glycerol
TRANSESTERIFICATION

oil reacts with methanol in the presence of catalyst to yield methyl esters
glycerine concentration in excess of 90% can be obtained as this is basically a dry
reaction
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GLYCEROL PURIFICATION

sweetwater or glycerine obtained from the three processes contains impurities and must
undergo further purification and concentration
DISTILLING & REFINING GLYCEROL

distilled under a high vacuum of 6601330 Pa absolute
condensed glycerine (99.5%, purity) undergoes steam deodorization by in a deodorizer under
high vacuum
bleached with activated carbon and ltered to yield pharmaceutical-grade glycerine with a
purity of 99%
Lower quality distillate is collected and sold separately as technical-grade glycerine