Oils and Fats Processing Technology - Lecture Note

SECTION OF CHEMICAL ENGINEERING TECHNOLOGY
MALAYSIAN INSTITUTE OF CHEMICAL AND BIOENGINEERING TECHNOLOGY

UNIVERSITI KUALA LUMPUR
Chapter 1.
Introduction:
Source of oils and fats
Properties of oils and fats
What is oils and fats

Oils and fats are organic substances that are
useful in human nutrient.
Oils and fats are distinguished by their phase.
Oils are usually liquid, while fats are solid.
Edible oils and fats are mostly produced by
plants and animals. However, they can be
synthesized by chemical processes.
Fatty acids and lipids are main constituent of fats
and oils
Importance of oils and fats

Human nutrition: source of energy, carrier for
vitamins, source of fatty acid essentials that cant
produced by human body.
Raw materials of several consumer goods, e.g.
cooking oil, margarine, butter, flavor enhancer,
pharmaceutical products, etc.
Thus, oils and fats become an important
commodity around the world significant
economical impact.
Malaysia received total revenue of 80.4 billion
RM in 2011 from palm oil industries.
Sources of oils and fats

VEGETABLE
Palm oil Soybean Olive Sunflower Corn
OILS
AND
FATS
LAND ANIMAL
Lard (pig) Tallow (sheep, cow)
MARINE ANIMAL
Fish oil
SYNTHETICS
Whale oil/wax
Chemically synthesized from

petroleum derived products
Worlds oils and fats production in 2011
Vegetable Oils
Vegetables oils can be obtained from:
1. Seeds, e.g. canola, soybean, corn, cottonseed,
sunflower
2. Fruits and kernels, e.g. Palm oil, coconut oil, olive
oil, palm kernel oil
Vegetable oil availability depends on some factors:
- Geographical area (e.g. some plants can only be
cultivated in sub-tropical continent)
- Local climate and seasons
- Other eternal factors e.g. natural disaster, war,
national policy, etc.
Vegetable Oils: Oil Content, Yield, and Producing Areas
Vegetable Oils: Oil Content, Yield, and Producing Areas
2. Chemical Constituent
of Fats and Oils
MAJOR COMPONENT
OILS
AND
FATS
GLYCERIN
GLYCERIDES
FATTY ACID
PHOSPOLIPIDS
~98%
~2%
TOCOPHEROLS
MINOR COMPONENT
TOCOTRIENOLS
STEROLS
PESTICIDES
STEROL ESTERS
CAROTENOIDS
TRACE METALS
in ppb
in ppm
2.1. Glycerides (acylglycerols)

GLYCEROLS
FATTY ACIDS
GLYCERIDES
(ESTERS)
Refer to the
number of FA
MONOGLYCERIDES
1%
DIGLYCERIDES
2%
Composition of
glycerides found in
natural fats and oils
TRIGLYCERIDES
97%
Formation of glycerides
(ESTERIFICATION OF GLYCEROL FATTY ACIDS)
OH
R1COOH
OCOR1
OH
R2COOH
OCOR2
OH
R3COOH
OCOR3
H
Glycerol
H
Fatty acids
Glyceride
H2O
Triglycerides
These are fatty acid triesters of glycerol.
The fatty acids may be all different, two may be
different, or all may be alike (monoacid triglycerides)
Properties of triglycerides
Chemical, physical & biological properties of oil
and fats determined by type of fatty acid groups
and their distribution over the triglycerides
molecules
Melting point increase when long chain of fatty
acid or decrease of proportion of unsaturated
fatty acid.
As example: milk fat (butterfat) and coconut oil
which contains a high proportion of C6-C12 fatty
acids- have lower melting point compare to fats
such as tallow or lard which consist of C16-C18.
2.2. Fatty acids

Structure
Fatty acids are aliphatic, usually straight chain,
monocarboxylic acids.
most natural fatty acids have even chain lengths
between C4 and C22, with C18 the most common.
The structure of a fatty acid may be denoted by a
systematic name after the nomenclature of its parent
hydrocarbon, by the biochemist system, by its
common name, or by a convenient shorthand
designation showing the number of carbon atoms and
the number of double bonds
Structure, systematic, trivial, and shorthand names of some

common fatty acids
Saturated fatty acids

Saturated fatty acids form a homologous series of
monocarboxylic acids (CnH2n+1COOH).
Naturally occurring saturated acids are mainly of
even chain length between C4 and C24.
Odd chain acids are usually minor or trace
components of plant and animal lipids, but some
are more abundant in bacterial lipids.
Fats rich in saturated acids are high melting and
are characteristic of many tropical species.
Systematic, trivial, and shorthand names and melting

points of saturated fatty acids
Systematic, trivial, and shorthand names and melting

points of saturated fatty acids (continued)
Number of C atoms
Melting point
Unsaturated Fatty Acids

Contains one (mono-unsaturated FA) or more double
bounds (poly-unsaturated FA) in its aliphatic C chain.
Oleic acid,
palmitoleic acid,
vaccenic acid, erucic
acid, nervonic acid
Linoleic acid,
linolenic
acid, ARA,
EPA, DHA,
Natural sources of mono-unsaturated fatty acids
Oleic acid: in most plant and animal lipids e.g

olive oil (70 - 75%) and several nut oils (e.g.,
macadamia, pistachio, pecan, almond, hazelnut,
50 - 70%), sunflower and safflower (75 - 80%).
Vaccenic acid: bacteria lipids
Palmitoleic acid: Fish oil, nut oils
Erucic acid: rape, mustard, crambe and some
Tropaeolum species
Nervonic acid: Lunaria annua seed oil
Natural sources of poly-unsaturated fatty acids

Linoleic acid: corn, sunflower, and soybean oils(>50%),
safflower oil (>70%).
-linolenic acid: evening primrose (~10%), borage
(~20%), blackcurrant (~15%),echium (~25%).
Arachidonic acid: animal tissues (small amounts), some
fungi, e.g., Mortierella species (50%)
-linolenic acid: soybean and canola (8 10%), linseed
oil (>50%), perilla oil (65 75%), chloroplast (50%)
Stearidonic acid: animal lipids, fish oils, seed oils, e.g.,
blackcurrant (up to 5%) & echium (~7%).
EPA, DHA: Fish oil, dinoflagellate Crypthecodinium cohnii
and marine protist Schizochytrium species (commercial
single-cell oil sources of DHA)
Cis and trans fatty acids

Some unsaturated fatty acids may form isomers
(same molecular formula, different structure)
Naturally occurring fatty acids are generally in the cis

configuration.
Trans fatty acids usually produced as side effect of partial
hydrogenation of mono unsaturated fatty acid.
Trans fatty acid has undesirable nutritional properties.
2.3. Phospholipids (phosphatides)

Frequently referred as gums (together with small
quantities of carbohydrates and resins), which
have adverse effects on product quality and
refined oil yield.
Phosphatides consist of polyhydric alcohols
esterified with fatty acids and phosphoric acid,
which is combined with a nitrogen-containing
compound.
Classified into hydratable and nonhydratable,
depending on the effect that water has on them.
Phospholipids (phosphatides)
Hydratable can be separated from the oil phase with
water.
Nonhydratable remain in the oil after water
degumming (together with the calcium and magnesium
salts of these acids).
Water degumming process will remove the hydratable
phosphatides (to a level of 200 ppm phosphorus)
Pretreatment with phosphoric or citric acid before
refining removing both nonhydratable and hydratable
phosphatides to 20 to 30 ppm phosphorus
Two common phosphatides in vegetable oils: lecithins and
cephalins.
2.4. Tocopherols & Tocotrienols

(Vitamin E)
Systematic name: 2-methyl-2-(4',8', 12trimethyltridecyl)-6-hydroxychromane
Structure of Tocopherols & Tocotrienols

Contains chromane ring with one hydroxyl
group, methyl groups and an aliphatic chain in
the other side.
Tocopherols: saturated aliphatic chain
Tocotrienols: unsaturated aliphatic chain with 3
double bonds
Isomers: designated as alpha (), beta (),
gamma (), and delta () depending on the
number and position of methyl groups on a
chromane ring
Tocopherols & Tocotrienols as antioxidant

Antioxidant: inhibit lipid oxidation in foods by
stabilizing hydroperoxy and other free radicals.
The antioxidant activity of tocopherols in foods is
least for -tocopherols, while the - and isomers have intermediate activities and the isomer is the most active.
Tocotrienols are less effective than their
corresponding tocopherols.
The stability of many vegetable oils has been
credited to the presence of these natural
antioxidants
Sources of Tocopherols & Tocotrienols

Seed oils are the major sources of tocopherols
and there seems to be a direct relationship
between the degree of unsaturation and the total
tocopherol content, that is, higher tocopherol
concentrations are present when the
unsaturation level indicates a need to prevent
oxidation.
The tocotrienols are found predominantly in
palm oil and cereal oils, such as barley and rice
bran oil.
2.5. Sterols
Sterols are minor components of all natural fats and
oils and comprise most of the unsaponifiable matter,
the remainder consists essentially of hydrocarbons.
The sterols are high melting, colorless, and
somewhat inert.
Cholesterol is the main sterol component of animal
fat and fish oil and is found in vegetable oils in only
trace amounts (can be considered as free
cholesterol).
Vegetable oil sterols are collectively called
phytosterols. Campesterol, stigmasterol, and
sitosterol are the best-known vegetable sterols
Molecular structure of sterols
Cholesterol is often linked with heart diseases
2.6. Carotenoid
Also known as pigments that give the color of fat/oils
(e.g. red-yellowish color in palm oils)
Normally consists of terpenes and terpene alcohol.
Can be found in fats/oils in form of tetrapenes, carotene, - carotene, lycopene, xanthophyl, etc.
-carotene is well known as pro vitamin A.
Carotene concentrations are low in most fats and oils
except for palm oil, which contains 0.05 to 0.2%.
The carotenes are heat sensitive and readily
adsorbed by bleaching earths.
2.7. Other minor constituent

Pesticides are used to increase agriculture
production throughout the world. Sometimes they
are also traced in oils and fats. Pesticides are
removed by volatilization during deodorization
process.
Trace metals (Cu, Fe, Mn, Ni, Ca, Na, Mg, etc.) are
absorbed during the growing season and during fats
and oils processing. Most are harmful to product
quality and human health and reduce the efficiency
of the process. The metals effects can be diminished
by the use of chelating agents (e.g. citric and
phosphoric acids) at various processing points to
sequester the trace metals.
2.8. Main chemical composition

of selected fats/oils
Type of oil/fat
Palm Oil
C12:0
C14:0
C16:0
0.2
1.1
Olive Oil
Avocado Oil
C18:0
C18:1
C18:2
44.0
4.5
39.2
10.1
16.0
4.0
64.0
5.0
2.5
10.0
5.0
7.0
C16:1
76.0
Coconut Oil
41.0
18.0
9.0
3.0
7.6
10.0
Palm Kernel Oil
45.0
17.0
10.0
3.0
18.0
3.0
Cocoa Butter Oil
46.0
21.0
12.0
3.0
37.0
4.0
Sunflower Oil
5.0
6.0
30.0
59.0
Soybean Oil
4.4
6.8
33.4
51.5
Lard (Pork Fat)
2.0
26.0
14.0
44.0
10.0
Beef Tallow
3.0
24.0
19.0
43.0
3.0
Cod Liver Oil
8.0
17.0
22.0
5.0
C12:0 lauric, C14:0 myristic, C16:0 - palmitic, C18:0 stearic

C16:1 palmitoleic, C18:1 oleic, C18:2 linoleic, C18:3 - linolenic
C18:3
5.0
2.3
1.0
3. Physical properties of fats

and oil
Freshly prepared fats and oils are colorless,
odorless and tasteless. Any color or taste is due
to association with foreign substances.
Fats have specific gravity less than 1 and
therefore they float on water.
Fats are insoluble in water but soluble in organic
solvents as ether and benzene.
Melting points of fats are usually low but higher
that solidification point.
Viscosity
3. Chemical Reactions
Hydrolysis
Saponification
Halogenation
Hydrogenation
Oxidation
Hydrolysis
CH2 O
O
R2
C H
CH2 O
O
C
O
C
Triacylglycerol
R1
R3
H2C
Lipase or Acid
3 H2O
HO
H2C
OH
H
OH
O
R1 C
O
OH
+ R C
2
OH
O
C
OH
R3
Glycerol Free fatty acids
Saponification
CH2 O
O
R2
CH2 O
O
C
H2C
R1
HO
O
C
Triacylglycerol
R3
3 NaOH
H2C
OH
H
OH
R1
+ R
2
R3
O
C
O
ONa
ONa
O
C
ONa
Glycerol Sodium salts of

fatty acids (soap)
Alkaline hydrolysis produces glycerol and salts of fatty

acids
Soap cause emulsification of oily material this help easy
washing of fatty materials
Halogenation
CH3
(CH 2)4
CH
CH
CH2
CH
CH
(CH 2)7
COOH
CH
CH
(CH 2)7
COOH
Linoleic acid
2 I2
CH3
(CH 2)4
CH
CH
CH2
Stearate-tetra-iodinate
Hydrogenation
It is a type of addition reactions accepting

hydrogen at the double bonds of unsaturated
fatty acids.
The hydrogenation is done under high pressure
of hydrogen and is catalyzed by finely divided
nickel or copper and heat.
It is the base of hardening of oils (margarine
manufacturing), e.g., change of oleic acid of fats
(liquid) into stearic acid (solid).
It is advisable not to saturate all double bonds;
otherwise margarine produced will be very hard,
of very low biological value and difficult to
digest.
Advantages of hydrogenated:
It is more pleasant as cooking fat.
It is digestible and utilizable as normal animal
fats and oils.
It is less liable to cause gastric or intestinal
irritation.
It is easily stored and transported and less
liable to rancidity.
Disadvantages of hydrogenated:
fats include lack of fat-soluble vitamins (A, D, E
and K) and essential fatty acids
Oxidation
This toxic reaction of triglycerides leads to
unpleasant odour or taste of oils and fats
developing after oxidation by oxygen of air,
bacteria, or moisture.
Also this is the base of the drying oils after
exposure to atmospheric oxygen.
Example is linseed oil, which is used in paints
and varnishes manufacturing
Rancidity (caused by oxidation)

Definition:
It is a physico-chemical change in the natural
properties of the fat leading to the development
of unpleasant odor or taste or abnormal color
particularly on aging after exposure to
atmospheric oxygen, light, moisture, bacterial or
fungal contamination and/or heat.
Saturated fats resist rancidity more than
unsaturated fats that have unsaturated double
bonds.
Types and Causes of Rancidity

1. Hydrolytic rancidity
2. Oxidative rancidity
3. Ketonic rancidity
CPB 30303 (SEPT 2015)
48
1. Hydrolytic rancidity
It results from slight hydrolysis of the fat by

lipase from bacterial contamination leading to
the liberation of free fatty acids and glycerol at
high temperature and moisture.
Volatile short-chain fatty acids have
unpleasant odor.
CPB 30303 (SEPT 2015)
49
2. Oxidative rancidity
It is oxidation of fat or oil catalyzed by exposure
to oxygen, light and/or heat producing peroxide
derivatives which on decomposition give
substances, e.g., peroxides, aldehydes, ketones
and dicarboxylic acids that are toxic and have
bad odor.
This occurs due to oxidative addition of oxygen at
the unsaturated double bond of unsaturated fatty
acid of oils.
CPB 30303 (SEPT 2015)
50
3. Ketonic rancidity
It is due to the contamination with certain fungi
such as Asperigillus Niger on fats such as coconut
oil.
Ketones, fatty aldehydes, short chain fatty acids
and fatty alcohols are formed.
Moisture accelerates ketonic rancidity.
CPB 30303 (SEPT 2015)
51
Prevention of Rancidity
1. Avoidance of the causes (exposure to light, oxygen,
moisture, high temperature and bacteria or fungal
contamination). By keeping fats or oils in wellclosed containers in cold, dark and dry place (i.e.,
good storage conditions).
2. Removal of catalysts such as lead and copper that
catalyze rancidity.
3. Addition of anti-oxidants to prevent peroxidation
in fat (i.e., rancidity). They include phenols,
naphthols, tannins and hydroquinones. The most
common natural antioxidant is vitamin E that is
important in vitro and in vivo.
CPB 30303 (SEPT 2015)
52
Hazards of Rancid Fats

1. The products of rancidity are toxic, i.e., causes
food poisoning and cancer.
2. Rancidity destroys the fat-soluble vitamins
(vitamins A, D, K and E).
3. Rancidity destroys the polyunsaturated
essential fatty acids.
4. Rancidity causes economical loss because
rancid fat is inedible.
CPB 30303 (SEPT 2015)
53
CHAPTER 2:
Palm Oil Extraction
Process
Faridah Ghafar
PALM OIL MILL PROCESSING

A palm oil mill produces crude palm oil (CPO)
and crude palm kernel oil (CPKO) as the primary
products and biomass as secondary products.
Capacity of mill varies between 60 100 tons
FFB/h.
55

The typical mill have many unit operations which
of sterilization, stripping, digestion and pressing,
clarification, purification, drying and storage. For
the kernel line, there are steps such as nut/fibre
separation, nut conditioning and cracking,
cracked mixture separation, and kernel drying,
storage.
56
57
TRADITIONAL CRUDE PALM OIL PROCESSING
58
MODERN CRUDE PALM OIL PROCESSING
59
CRUDE PALM OIL RECOVERY
Weight
Bridge
Sterilisation
Threshing
Pressing
Vacuum
Drying
Screening
Clarifying
Recovered
Oil
Purifying
Oil Recovery
Sludge
Storage Tank
Effluent Treatment Plant

60
1. Reception
Weight bridge
FFB Truck
Loading Ramp
Grading FFB
Over Ripe Bunch
Unripe Bunch
Under ripe bunch
Ripe bunch
View FFB Grading
Empty bunch
Old Crop
Long stalk bunch
61
1. Reception
Fresh fruit arrives from the field as bunches or
loose fruit.
Weight the fresh fruit in the truck using weight
bridge.
Grading the FFB to identify the quality of
bunches.
The quality standard achieved is initially
dependent on the quality of bunches arriving at
the mill.
62
1. Reception
The mill cannot improve upon this quality but
can prevent or minimize further deterioration.
The field factors that affect the composition and
final quality of palm oil are genetic, age of the
tree, agronomic, environmental, harvesting
technique, handling and transport
CPB 30303 (SEPT 2015)
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2. Sterilisation
Receive
Sterilizer
64
2. Sterilisation
The purposes of sterilization are:
prevents build-up of free fatty acids (FFA) in the oil by
inactivates the lipases in the fruits
loosens the fruits from bunches to facilitate stripping
softens the fruit mesocarp for digestion and release of
oil
preconditioning of nuts to reduce kernel breakage
65
2. Sterilisation
The sterilisers consists of a long cylindrical
pressure vessel of about 1.8m diameter, with
rails running along the length of the interior.
The fruit is loaded into cages
These cages are pushed on the rails into the
steriliser.
Once the steriliser has been loaded and closed,
steam is introduced.
66
2. Sterilisation
Pressure is built up to about 3 kg/cm2 which
corresponds to a temperature above 130oC for
1hr.
When high-pressure steam is used for
sterilization, the heat causes the moisture in the
nuts to expand.
CPB 30303 (SEPT 2015)
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2. Sterilisation
When the pressure is reduced the contraction of
the nut leads to the detachment of the kernel
from the shell wall, thus loosening the kernels
within their shells.
68
3. Threshing/Stripping Station
Reception
Sterilisation
Thresher
Mulching at field
Empty Bunches
69
3. Threshing/Stripping
The purpose of stripping is to separate the fruits
from the empty bunch
Modern mills used drum stripper
The drum rotates at about 22 rpm
Sterilized FFBs are fed into a drum stripper and
the drum is rotated, causing the fruits to be
detached from the bunch
70
The bunch stalks are removed as they do not
contain any oil and being disposed by
incineration, giving ash as potash fertilizer, and
fuel for boilers
It is important to ensure that oil loss in the bunch
stalk is kept to a minimum
Prolonged sterilization will increase oil loss in
stalks
CPB 30303 (SEPT 2015)
71
Irregular feeding of the stripper may also result
in increase of oil loss in stalks.
Stalks which have fruits still attached on them
are called hard bunches, and have to be recycled
back to sterilizers for further cooking. Hard
bunches are detected by visible inspection
72
4. Digestion and Pressing
Reception
Sterilisation
Threshing
Function:
to digest the fruit lets
Maximize oil extraction with minimize broken nut
To break press cake before depericarping
Digester
Oil Recovery Plant

Kernel Recovery Plant
Screw Press
73

The purpose are:
To digest the fruits
To maximize oil extraction with minimize broken nut
To break press cake before depericarping
74

After stripping, the fruits are moved into a
digester where, the fruits are reheated to loosen
the pericarp.
Digestion is the process of releasing the palm oil
in the fruit through the rupture or breaking
down of the oil-bearing cells.
The digester consists of a steam-heated
cylindrical vessel fitted with a central rotating
shaft carrying a number of beater (stirring)
arms.
75

The fruits are rotated about, causing the
loosening of the pericarps from the nuts
The digester is kept full and as the digested fruit
is drawn out, freshly stripped fruits are brought
in
The fruits are passed into a screw press, where
the mixture of oil, water, press cake or fibre and
nuts are discharged.
76

Contamination from iron is greatest during
digestion when the highest rate of metal wear is
encountered in the milling process. Iron
contamination increases the risk of oil oxidation
and the onset of oil rancidity.
77
5. Clarification
The crude oil from the press consists of a mixture
oil, water and other non-oily solids
Consists of 4 stages:
Screening
Clarifying
Oil recovery
Purifying
78
5. Clarification (Screening)
Reception
Sterilisation
Threshing
Pressing
Vibrating Screen
Waste
screen
Oil have
been screen
79
The main purpose is to separate crude oil from
dirt
A mixture of oil, water, solids from the bunch
fibres is delivered from the press to a
clarification tank.
The mixture containing the crude oil is diluted
with hot water to reduce its viscosity
80
The dilution (addition of water) provides a
barrier causing the heavy solids to fall to the
bottom of the container while the lighter oil
droplets flow through the watery mixture to the
top when heat is applied to break the emulsion
(oil suspended in water with the aid of gums and
resins)
A vibrating screen helps remove some of the
solids
81
5. Clarification Station (Clarifying)
Reception
Sterilisation
Purifying
Threshing
Pressing
Screening
CPO
Clarifier Tank
Underflow
Sludge
Oil Recovery
82
5. Clarification (Clarifying)
The purpose is to collect oil from crude oil using
continuous settling tank.
Separation of the oil from the rest of the liquor is
achieved by setting tanks based on gravity.
The screened mixture is boiled from one or two
hours and then allowed to settle by gravity in the
large tank so that the palm oil, being lighter than
water, will separate and rise to the top
83
5. Clarification (Oil Recovery)
Reception
Sterilisation
Threshing
Pressing
Screening
CPO
Recovered Oil
Clarifier
Purifying
Function:
To collect oil from sludge
using decanter
Effluent
Treatment
Plant
Sludge
Clarifying
Underflow
Sludge
DECANTER
84
5. Clarification (Oil Recovery)

The purpose is to collect oil from sludge using
decanter
85
5. Clarification (Purifying)
Reception
Sterilisation
Threshing
Pressing
Screening
Clarifier
CPO
Purifier
Dirt < 0.02%
86
5. Clarification (Purifying)
The purpose is to purified the crude palm oil
Oil from the top is skimmed off and purified in
the centrifuge prior to drying
The dirt level must be less than 0.02%
87
6. Drying
Reception
Sterilisation
Threshing
Pressing
Screening
Clarifying
Purifying
Vacuum Dryer
Oil Recovery
Moisture < 0.18%

Sludge
88
6. Drying
The purpose is to reduce moisture content of
crude palm oil using vacuum dryer
The oil must be dried to prevent increasing of
FFA through autocatalytic hydrolysis of the oil
The moisture content must be less than 0.18%
89
7. Storage of CPO
Reception
Sterilisation
Moisture< 0.18%
Dirt
< 0.02%
DOBI
> 2.3
FFA
< 3%
Threshing
Pressing
Vacuum
Drying
Screening
Clarifying
Recovered
Oil
Purifying
Oil Recovery
Sludge
Storage Tank

90
7. Storage of CPO
The purpose is to keep CPO with controlling of
quality
The final crude palm oil is then cooled and
stored.
Storage is in welded steel tanks contain heating
coils to prevent crystallization and subsequent
settling out of the solid phase.
91
7. Storage of CPO
May be filled with carbon dioxide or other inert
gas above the oil to prevent oxidation
The temperature is controlled between 32 40oC
during storage
Temperature should be kept as low as possible to
minimise deterioration in quality during storage
92
7. Storage of CPO
The quality of CPO have to maintain at:
Moisture< 0.18%
Dirt
< 0.02%
DOBI
> 2.3
FFA
< 3%
93
8. Palm Oil Mill (POM )- Buyer

(Refinery- Extract Plant)
Moisture< 0.18%
Dirt
< 0.02%
DOBI
> 2.3
FFA
< 3%
CPO Storage Tank
Palm Oil Mill
Buyer
Function:
To keep CPO before delivery to Buyer
94
PALM KERNEL RECOVERY
Reception
Sterilisation
Threshing
Pressing
Depericarping
Heater
Hydro Clay bath
Kernel
Despatch Silo
Shell
&
Fiber
Winnower
Boiler
Nut Cracking
Turbine
Cyclones
95
9. Nut Recovery (Depericarping)
Reception
Sterilisation
Fibre
Fibre
Cyclone
Threshing
Pressing
Depericarper
Polishing Drum
Nuts
96
9. Nut Recovery
(Depericarping)
The purpose are:
To separate fiber from nut
To clean up nut from fiber
The residue from the press consists of a mixture

of fibre and palm nuts
The press cake from the digester is fed to a
vertical column (depericarper) where air is
channeled to lift the fibre, thus separating the
fibre from the nuts
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9. Nut Recovery
(Depericarping)
The nuts are passed to a polishing drum at the
bottom of the depericarper, where pieces of
stalks are removed.
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10. Nut Cracking
Reception
Sterilisation
Threshing
Pressing
Nut
Cracker
CPB 30303 (SEPT 2015)
Depericarping
Secondary
Depericarper
99
10. Nut Cracking

The purpose is to crack kernel with minimize
broken kernel
A nutcracker cracks the nuts after the
conditioning and drying process.
100
11. Kernel Separation (Winnower)
Reception
Sterilisation
Threshing
Pressing
Depericarping
Shell
Nut Cracking
Winnower
Winnower
Cyclone
Nut
Function:
Separately shell from
kernel with pneumatic
system
Kernel
&
Shell
101
11. Kernel Separation

(Winnower)
The purpose to separate shell from kernel with
pneumatic system
The mixture of cracked nuts and shells are
separated via a winnowing system
102
12. Kernel Separation (Hydro Clay Bath)
Reception
Sterilisation
Threshing
Pressing
Depericarping
Heating
Kernel
Winnower
Shell
Shell
Cyclone
Nut Cracking
Hydro Clay bath
103
12. Kernel Separation (Hydro

Clay Bath)
The purpose is to separate shell and kernel using
hydro clay bath
The mixture of cracked nuts and shells are then
separated by a hydrocyclone or a clay bath.
A hydrocyclone uses centrifugal force to separate
the kernel from the shell using water.
104
12. Kernel Separation (Hydro

Clay Bath)
The clay bath principle works on the specific
gravity of kernel of 1.07 and the shell of 1.17.
The kernels will float while the shells sink in a
clay bath mixture of SG 1.12.
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13. Kernel Storage
Reception
Sterilisation
Threshing
Pressing
Depericarping
Heater
Admixture< 6%
Moisture < 7%
FFA
< 5%
Hydro Clay bath
Winnower
Nut Cracking
Function
To dry and Keeping The
kernel
Kernel
Despatch Silo
Shell
&
Fiber
Boiler
Turbine
Cyclones
106
13. Kernel Storage

The kernels are then dried in hot air silos to
moisture content of less than 7%
Quality control of kernel
Admixture < 6%
Moisture < 7%
FFA < 5%
107
Chapter 3
Palm Oil Refining
Faridah Ghafar
Objectives
To expose students about palm oil refining
processes
To introduce terms in refining crude palm oil
such as RBD, Olein & Stearin
Learning Outcomes
At the end of this chapter, students should
be able to:
state basic refining process from crude oil until
intermediate products such as palm olein, palm stearin
and others
describes important parameters such pressure,
temperature and others in the processes
Refining Process
Introduction
Crude palm oil extracted commercially from the fresh
fruit bunches contains a small but variable amount of
undesirable components and impurities.
These include some mesocarp fibers, moisture and
insolubles, free fatty acids, phospholipids, trace metals,
oxidation products, and odoriferous substances
Introduction
As a result, palm oil is normally refined to a
bland, stable product before it is used for direct
consumption or for formulation of edible
product.
Impurities in Crude Palm Oil

Hydrolytic
Moisture, dirt, free fatty acids, partial glycerides and
enzymes
Oxidative
Metals, oxidation products, pigment, tocopherols ,
and phospatides
Impurities in Crude Palm Oil

Catalyst poison
Compounds containing nitrogen, sulphur & halogens
Hydrocarbons
Terpenes, resdin, waxes ad unsaturated compounds
Refining Process
The objectives of refining process are:
to convert the crude oil to quality edible oil by
removing objectionable impurities to the desired
levels in the most efficient manner.
to neutralized Free Fatty Acid present in the crude oil
Refining Process
The refining routes of palm oil is quite identical
and depends on its characteristic:
Product approach and refiners requirement
Higher oil yield,
Reduction of the use of chemical
Reduction in water use
Effluent 75 to 90% reduce
Quality and acidity of crude oil
Ability to remove soapstock
Environmental legislation
Refining Process
There are two routes are taken to process crude oil into
refined oil:
chemical refining
physical refining
They differ basically in the manner in which the free fatty
acids are removed.
Refining Process
Characteristics of Crude Palm Oil
Refining Process
Refining basically involves 4 stages:
1. Degumming- to remove phospholipids
2. Neutralization to remove fatty acids (chemical
refining)
3. Bleaching- to remove pigments by adsorptive
treatment
4. Deodorization- to remove odor in vacuum
condition
Physical Refining
Physical refining is a refining process using steam
distillation under higher temperature and vacuum to
remove free fatty acids .
Pretreatment : Degumming & Bleaching
Steam distillation: Deodorization
Physical Refining
Degumming
Bleaching
Deodorization
Physical Refining
Physical Refining
Suit when raw materials is low gums and high FFA,
unsaponifiable and others by stream stripping
Need pretreatment with 2 steps:
Addition of chemical to remove small amount of gums
Using steam distillation to remove FFA and
impurities.
Step 1: Degumming
Chemical used for degumming process is phosphoric
acids
Crude palm oil is first heated up to a temperature about
90 110oC before added with phosphoric acids.
The dosage of phosphoric acids normally used is 80
85% concentration at the rate of 0.05 0.2% feed oil.
Step 1: Degumming
The purpose of phosphoric acids is to precipitate the non
hydratable phosphatides and coagulate the phosphatides
making it insoluble and thus easily removed during
bleaching.
Step 2: Bleaching
Degummed oil is passed to bleacher where bleaching
earth is added as slurry.
The dosage of bleaching earth within the range of 0.8
2.0% by weight of oil.
Bleaching is carried out under a vacuum of 2025 mmHg
and at a temperature of 95110oC with retention time of
3045 min
Step 2: Bleaching
The functions of bleaching earth are:
to adsorb the undesirable impurities such as
trace metals, moisture, insolubles, and part of the
carotenoids and other pigments
to reduce the oxidation products
to adsorb the phospholipids precipitated by the
phosphoric acid
to remove any excess phosphoric acid present in
the oil after degumming
Step 2: Bleaching
During bleaching process, traces metal
complexes, pigments, phosphatides, oxidation
products and any residual of phosphoric acids
are removed by adsorptive effect of the
bleaching earth.
The slurry containing the oil and earth is then
filtered using plate and frame presses or
vertical or horizontal pressure filters to recover
a clear, light orange color pretreated oil
Step 2: Bleaching
A small amount of diatomaceous earth is used to precoat
the filter leaves to improve the filtration process
As a quality precaution, the filtered oil is polished
through another security filter bag in series, to trap any
earth particles that escape through the first filter.
Step 2: Bleaching
This is essential as the presence of spent earth particles
in the pretreated oil reduces the oxidative stability of the
final RBD oil
The spent earth from the filter normally contains about
2040% oil, and this is the major source of oil loss in the
refining process.
Step 3: Deodorization
The pretreated oil is then ready for deodorization
process to remove FFA using steam distillation.
The pretreated oil is first deaerated followed by heating
to 240270C in an external heat exchanger before
pumping into the deodorizer, which is kept under a
vacuum of 25 mm Hg
Superheated high-pressure steam is used as a heating
medium
Temperatures above 270C are to be avoided to minimize
loss of neutral oil, tocopherols/tocotrienols, and also the
possibilities of isomerization and undesirable
thermochemical reactions
During this process, the free fatty acids, which
were still present in the pretreated oil, are
distilled together with the more volatile
odoriferous and oxidation products such as
aldehydes and ketones
At the same time, the residual carotenoids
present are also thermally decomposed
The residual carotenoids present are also thermally
decomposed and the end result is the production of a
light-colored, bland RBD palm oil
Desired Quality of RBDPO
Advantages of Physical Refining

Higher efficiency
Less operating cost
Simple effluent treatment
Physical Refining.
Low Phosphatides
Crude fats & Oil
High Phosphatide
Crude Fats & Oil
Physical refining
process flow diagram
Acid Refining or
Degumming (Water Acid,
Enzymatic or Another
Process
Dry Degumming or
Bleaching
Dry Degumming
Dewaxing,
fractionation
Hydrogenation
Steam Distillation
Deodorized Fat or Oil
Chemical Refining
Chemical refining is the refining process using
appropriate amount of caustic soda (lye) to
remove free fatty acids by neutralization.
The neutralization process will produce
soapstock.
Chemical Refining
Degumming
Neutralization
Bleaching
Deodorization
Chemical Refining
Degumming
Neutralization
Bleaching
Deodorization
Step 1: Degumming
The crude oil is heated to a temperature of 8090oC.
Phosphoric acid of 8085% concentration is then dosed
in at a rate of 0.050.2% (of the feed oil)
Step 2: Neutralization
the degummed oil is further treated with a
caustic soda solution of about 4 N
concentration with a calculated excess (based
on free fatty acid content of the crude oil) of
about 20%
The phosphatides and gums are absorb alkali
and coagulated through hydration or
degradation
The reaction between caustic soda and the free fatty
acids in the degummed oil results in the formation of
sodium soap (soapstocks)
The lighter phase discharged consists mainly of
neutralized oil containing 5001000 mg/kg of soap and
moisture
The heavy phase is mainly soap, insoluble impurities,
gums, phosphatides, excess alkali, and a small quantity of
oil loss through emulsification
As an excess of alkali is used, it is unavoidable that a
slight loss of neutral oil through saponification also
occurs.
The non-hydratable phosphatides are separated from the
oil by using centrifugal separator.
The neutralized palm oil (NPO) is then washed with 10
20% hot water to remove traces of soap still present
The washed oil is then dried under vacuum to a moisture
level below 0.05%.
Step 3: Bleaching
The neutralized palm oil is treated with
bleaching earth in a similar manner as that
described in physical refining
However, the bleaching earth also removes traces
of soap that are present
The neutralized and bleached oil is then
channeled to the deodorizer in a similar manner
to that in the physical refining.
The oil is subjected to distillation at a
temperature of 240260C and a vacuum of 25
mm Hg with direct steam injection
During this process, residual free fatty acids,
volatile oxidation products, and odoriferous
materials are removed together with thermal
decomposition of carotenoids
The final product, called neutralized, bleached, and
deodorized (NBD) palm oil is then cooled down to 60C
and passed through polishing filter bags before pumping
to the storage tanks
Desired Quality of NBD Palm Oil
RESULTS
Colour of oil
Chapter 4:
Fatty Acids Clusters &
Derivatives
Faridah Ghafar
153
Learning Outcomes
At the end of this chapter, student should be able
to:
Explain the process of fatty acids derivation
Analyze source of fatty acids
Analysis and evaluate the synthesis of the
process related of fatty acid
154
Contents
Types of fatty acids

Isomerization
Principal production process
155
FATTY ACIDS
Introduction
Fatty acids are is a carboxylic acid with a long
aliphatic tail (chain), which is either saturated or
unsaturated.
Most natural fatty acids have even chain lengths
between C4 and C28, with C18 the most common.
When they are not attached to other molecules,
they are known as "free" fatty acids.
157
Introduction
Over 1000 fatty acids are known with different:
chain lengths
positions, configurations and types of unsaturation
additional substituent along the aliphatic chain.
158
Introduction
Natural fatty acid structures reflect their common
biosynthesis the chain is built in two-carbon units
and cis double bonds are inserted at specific
positions relative to the carboxyl carbon.
However, only around 20 fatty acids occur widely in

nature; palmitic, oleic, and linoleic acids make up
~80% of commodity oils and fats.
Figure 1.1 shows the basic structure of fatty acids
and a number of the functional groups found in fatty
acids.
159
160
161
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167
Types of Fatty Acids

2 types of fatty acids:
Saturated fatty acids
Fatty acids without double bonds
Unsaturated fatty acids

Fatty acids that have carboncarbon double bonds
168
1.0 Saturated Fatty Acids

Contain no double between carbon
Chain length between 4 to 24 carbon atoms
Have straight and even numbered carbon chains
Least reactive and higher melting point
3 subgroups:
Short chain fatty acid
Medium chain fatty acid
Long chain fatty acid
169
170
171
1.1 Short chain fatty acids

Saturated fatty acid with 2 to 6 carbon atoms:
acteic, butyric and caproic.
Can be found in natural fats and oils
No effect to cholesterol
Liquid at room temperature
Vaporize readily at high temperature
Contribute to rancidity( having the strong
disagreeable smell or taste of decomposing fats
or oils) flavor of butter
172
1.2 Medium chain fatty acids

Saturated fatty acids with 8 to 12 carbon atoms:
caprylic, capric and lauric.
Directed to the liver and burned as energy rather
than being stored in the body as fat.
Do not raise serum cholesterol level.
173
1.2 Medium chain fatty acids

Lauric fatty acids
Lauric acid increases total serum cholesterol
LDL-low density lipoprotein concentration compare
to oleic fatty acid
Come from: coconut and palm kernel
Exhibit low melting point
174
1.3 Long chain fatty acids

Saturated fatty acids with 14 to 24 carbon atoms
More than C18 only exist in few vegetable oil
175

Myristic fatty acid
- Greatest effect on blood plasma cholesterol
level
- Sources : coconut, palm kernel, milk and meat
- animal fat also contain this fatty acid but at low
level.
176

Palmitic fatty acid
Major saturated fatty acid in animal fat and vegetable
oils.
In aspect of nutrition, palmitic has been found to be
more hypercholesterolemia( hypercholesterol ) when
compare to lauric
Increase LDL cholesterol level
Can crystallize in the beta form (`) desirable in
plasticity, smooth texture, aeration & creaming
properties
The stabilization effect related to triglyceride position
177

Stearic fatty acids
Normally come from hydrogenation of 18 carbon
atom unsaturated
Minimal effect on LDL cholesterols and no effect on
HDL cholesterols
Nutrition: does not affect cholesterol serum compare
to C12-C16
178
2.0 Unsaturated fatty acids

Contain double bonds between carbon atoms.
Cis form cause bends in the carbon chain
This bends become more pronounced as the
number of double bonds increased
Low melting point
More chemically reactive
Subgroup of unsaturated:
Monounsaturated fatty acid
Omega-6 polyunsaturated
Omega-3 polyunsaturated
179
2.1 Monounsaturated fatty acids

Have only one double bond
Least reactive unsaturated fatty acids
Oleic and palmitoleic are the most widely
distributed
180

Oleic fatty acids
Most widely distributed natural fatty acid.
Claim to be low health effect due to low saturated
fatty acid, minimal trans-isomer and reduce LDL
cholesterol in blood and high oxidative stability
Liquid oil with oleic have good flavor and frying
stability
#Palm oil has 46%-50% of C18:1
181

Erucic fatty acids
Found in plants of the mustard family and in marine
animal oil.
182
2.2 Polyunsaturated fatty acids

Have 2 or more double bonds
Chemically reactive as the number of double
increase
Polyunsaturated fatty acid with 2 to 6 double bonds
are of considerable nutritionally.
Vegetable oil are principle source of the two
essential fatty acids: linoleic and linolenic
Known as essential fatty acid
Must be obtained from food because the human
body lacks the enzymes required for their
production.
183

Linoleic: corn oil or safflower
C18:2 with double bonds in 9,12 and 15 position
known as Omega 6
Linolenic: canola and soybean

C18:3 with double bonds in 9,12 and 15 position
known as Omega 3
184
185

This diet important:
Stimulate skin and hair growth

Maintaining bone health and reproductive capability
Prevent eczema, hair loses, neurological dysfunction.
Decrease LDL cholesterol
Help fetus(baby) growth
Prevent heart disease and arthritis
186

Omega 3 fatty acid family
Have 3, 4, 5 or 6 double bonds in a carbon chain of 18,
20 or 22 carbon atoms.
Double bond in cis configuration
3 major types of Omega 3 fatty acid:
linolenic fatty acid
Eicosapentaenoic fatty acid
Docosahexaenoic fatty acid
187

Omega 6 fatty acid family
Have 2, 3 or 4 double bond in a carbon chain of
18, 20 or 22 carbon atoms.
Double bond in cis configuration
188
ISOMERIZATION
189
Isomerization
Isomerisation is the process by which one molecule is
transformed into another molecule which has exactly the
same atoms, but different arrangement of atoms.
In some molecules and under some conditions, isomerisation
occurs spontaneously.
Many isomers are equal or roughly equal in bond energy, and
so exist in roughly equal amounts, provided that they can
interconvert relatively freely, that is the energy barrier
between the two isomers is not too high.
When the isomerisation occurs intramolecularly it is
considered a rearrangement reaction.
190
Isomerization of fatty acids

Isomers of unsaturated fatty acid have identical
numbers of carbon, hydrogen and oxygen atoms
but the double bonds differ in position or
geometric arrangement.
2 types of isomerization:
geometric isomerization
positional isomerization
191
1. Geometric Isomerization
Geometric isomerization is the changes of
double bond configuration from cis form to trans
form.
192
Natural vegetable oils and fats contain
unsaturated acids almost exclusively in the cis
form.
Occur at high temperature (around 150"C), with
surface active components (such as Kieselgur
and bleaching earth) present, and during
hardening, these double bonds can be
isomerized into the trans form.
As mentioned previously, vegetable oils and fats
are almost trans free (below detection limit in
seeds).
193
Trans fatty acids occur in most animal fats, e.g., in
butterfat at a level of 2.545% (varying between
summer- and winter-butter) (Patton et al. 1960).
Kaufmann and Mankel(1964) found considerable
amounts of trans fatty acids in beef tallow (4.6l0%), goat (6.8-11.1%) and mutton (10.7-15.8%)
Double bond contain in cis or trans position
Normal cis transform to trans require low energy
Trans fatty acid can cause increase of LDL
cholesterol in blood trans fatty acid form at very
high temperature(hydrogenation or deodorization)
194
2. Positional Isomerization
Positional isomerization is the changes of double
bond position from isolated double bonds
toward a structure containing more conjugated
double bonds.
195
2. Positional Isomerization
This isomerization can occur at very high
temperatures during alkali treatment.
Such conditions do not occur during correct
processing of oils and fats for edible purposes.
196
FATTY ACIDS CLUSTER
197
Fatty Acids Cluster
Saturated
Monoenoic Acids(Monounsaturated)
Methylene-Interrupted Polyunsaturated Acids..
Conjugated Acids
198
1. Saturated Fatty Acids

Saturated fatty acids form a homologous series
of mono-carboxylic acids (CnH2n+1COOH).
Naturally occurring saturated acids are mainly of
even chain length between C4 and C24.
199
2. Monoenoic acids
(Monounsaturated)
Straight-chain, cis-monoenoic acids with an
even number of carbons are common
constituents of many lipids and commodity oils.
Normally the double bond of monoenoic acids is
cis- or Z-configuration.
They are named systematically from the
saturated hydrocarbon with the same number of
carbon atoms, the final 'ane' being changed to
'enoic'.
200
2. Monoenoic acids (Monounsaturated)
201
2. Monoenoic acids (Monounsaturated)

The most common monoene is oleic acid (18:1
9c).
Cis-monoenes with 18 or less carbons are liquids
at room temperature or low-melting solids;
higher homologues are low-melting solids.
Trans-monoenes are higher melting, closer to the
corresponding saturated acids.
202
2. Monoenoic acids
(Monounsaturated)
Double bond position also influences the melting
point; both cis and trans C18 monoenes are
higher melting when the double bond is at even
positions than at odd positions; a pattern most
distinct for double bonds between C4 and C14.
The solid acids may exist as a number of
polymorphs, with different melting points,
resulting from subtly different packing in the
crystal
203
204
205
3. Methylene-interrupted
polyunsaturated acids
Most unsaturated fatty acids with two or more
double bonds show a characteristic methyleneinterrupted pattern of unsaturation, with one
CH2 between cis double bonds.
This pattern results from the operation of a few
specific desaturases and chain-elongation
enzymes.
206
3.Methylene-interrupted
polyunsaturated acids
207
4. Conjugated Acid
Fatty acids with two or more conjugated double
bonds are found in some plants and animals.
208
PRODUCTION OF FATTY
ACIDS
209
Production of Fatty Acid

Fatty acids are normally market in the form of:
Lipids, waxes, sterol ester and ester of triterpene
alcohol.
Sources came from plants and animals lard

Can be produced by natural or synthetic.
For palm oil :
Palmitic acid, myristic acid, stearic acid, arachidic acid,
oleic acid, linoleic acid, iodine value(4454),saponification value(194-206),
210
Product of Fatty Acid
211
Product of Fatty Acid
212
Uses & Product

Product
Derivatives
Candle
Stearin(saturated C16C18.)
Intermediates for
emulsifiers, lubricants
and etc.
Fatty alcohol, fatty

amines, fatty acid esters
213
Modification of Fatty Acid

Many processes :
Hydrogenation
Isomerization
Dehydration
214
Hydrogenation
Used unsaturated fatty acid by catalyst
Prefer unsaturated(PUFA) than
monounsaturated(MUFA)
Also known as hardening
Unsaturated
saturated
Resulted: more stable and resistant to oxidation
Catalyst: nickel in presence of water and O2.
215
Isomerization
Two isomerization techniques:
Cis-trans isomerization of oleic acid to elaidic acid
Treating with SO2 , NO, selenium or acid activated earth
Increase the melting point
Conjugation of polyunsaturated fatty acid.

Alkali catalyst isomerization of non conjugated (PUFA)
216
Dehydration
Fatty acid in hydroxyl group in the carbon chain
be hydrated
Exp: Ricinenic acid from Ricinoleic acid
217
Production of Natural Fatty Acid

Refer to chapter 4 under fat splitting
Just glance :
Esterification
Glycerol + Fatty acids
Triglyceride
Splitting
Splitting agents (Reverse process)
Water= hydrolisis
Methanol= methanolysis
Caustic soda=saponification
Amines = aminolysis
218

Transesterification
Fatty acid (Methyl ester+

glycerol
Fatty acid + glycerol
Hydrolisis
Triglycerides
Saponification
Aminolysis
Fatty acid (soap)+

glycerol
Fatty acid (amides) +
glycerol
219
220

Distillation of Fatty acid:
After splitting crude fatty acids contain a series of
high boiling impurities such as unreacted partial
glycerides, soaps, glycerol, sterols, phosphatides,
pitch water aldehydes and methyl ketones
Purification of Glycerine
221
Production of Synthetic Fatty Acid

Processes:
Oxidation of alkanes(Ziegler alcohol process)

Hydroformylation( Oxo Process)
Hydrocarboxylation
Ozonolysis of oleic acid
Thermal decomposition of ester from castor oil
Caustic fusion of alcohols
Telormerization
222
Production of Synthetic Fatty Acid

Fatty alcohols are mainly employed as
intermediates
Fatty alcohols and their derivatives are used in
polymers, surfactants, oil additives, and
cosmetics and have many specialty uses
223
Synthetic based oil

Synthetics : to form fatty alcohol besides from natural sources
feed for synthetic :
1- olefins
N-paraffins
Types of synthetic fatty acids(SFA)
Straight chain SFA

Branched chain SFA
224
Fatty Alcohols
They are predominantly linear and monohydric, and can be
saturated or have one or more double bonds.
Alcohols with a carbon chain length above C22 are referred to
as wax alcohols.
Diols whose chain length exceeds C8 are regarded as
substituted fatty alcohols.
The character of the fatty alcohols (primary or secondary,
linear or branched-chain, saturated or unsaturated) is
determined by the manufacturing process and the raw
materials used
225
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228
1. Oxo (Hydroformylation)
Reaction
Most of the oxo plants in the world, except those
belonging to the Shell Group, use processes in
which the intermediate aldehydes are isolated,
purified, and then hydrogenated in a second
reactor.
229
Reaction
The sequence of steps includes the following:
hydroformylation, catalyst removal and recycle,
aldehyde distillation, aldehyde hydrogenation,
and finally purification of the product alcohols
230
Reaction
In some cases, particularly with the higher
olefins that yield high-boiling aldehydes along
with smaller quantities of the corresponding
alcohols, effective fractionation of
thealdehydes is difficult, so the crude
hydroformylation reactor product is
hydrogenated directly.
231
2. Oxidation of Alkanes
(Ziegler Alcohol Process)
Ethyl linear alpha olefin process is commonly
called stoichiometric Ziegler process
Ethylene can be added to triethylaluminum to
build a mixture of high-molecular-weight trialkyl
aluminums known as the ethylene growth
product.
232
2. Oxidation of Alkanes
(Ziegler Alcohol Process)
When this growth product is oxidized with air, it
is converted to the corresponding aluminum
alkoxide.
Hydrolysis of this alkoxide leads to a mixture of
linear primary alcohols having the same number
of carbon atoms as the alkyl groups in the
trialkyl aluminum growth product.
233
3. Hydrocarboxylation
In a similar reaction, the Koch Haaf method,
carbon monoxide is added to the double bond of
olefins in the presence of strong acids.
In a second step, the intermediate product reacts
with water to form branched-chain fatty acids.
Concentrated sulfuric acid, phosphoric acid,
hydrogen fluoride, or boron trifluoride can be
used as catalyst.
The reaction mechanism involves a carbonium
ion, which reacts with carbon monoxide to form
an acylium ion.
234
3. Hydrocarboxylation
This then reacts with water to form carboxylic
acid.
Fatty acids with highly branched chains result
from rearrangement of the carbonium ion.
The process operates under mild conditions up
to 80 C and 10 MPa.
Shell manufactures Versatic acids by this method
(for Koch process see Carboxylic Acids, Aliphatic
Carboxylation of Olefins, Koch Process and for
Versatic acids see Carboxylic Acids, Aliphatic
Versatic Acids and Neo Acids).
235
Chapter 5:
Advanced Processing of
Oils and Fats
Fat Splitting and

Glycerine Recovery
Faridah Ghafar
Objectives
To define the terms such as fat splitting, glycerine
and others
To rectify and comprehend the method of fat
splitting
To classified the process parameter such as
enzymes and etc
To acknowledge and summarize the principle of
production of glycerine.
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Introduction
The importance of fatty acid and glycerine in
chemical industry is well known and they are
used in a very wide range of applications such as:
Fatty acid: soap & detergents, cosmetics,
lubricants, paint industry, rubber chemicals,
textile chemicals & emulsifier.
Glycerine: toothpaste, alkyd resins, explosive,
cosmetics, food & beverages, pharmaceutical
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Fat Splitting
Fat splitting or hydrolysis is the main reaction
step in fatty acid technology.
Fat splitting is the process to split or hydrolyzed
the triglyceride molecules of fats and oils in the
presence of splitting agents such as water,
methanol, caustic soda and amines to yield
glycerine and a mixture of fatty acids.
It can be carried out by chemical modification
(catalyzed or uncatalyzed) or enzyme
modification.
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Fat Splitting
Esterification
Glycerol + Fatty acids
Triglyceride +
3H2O
Splitting
Splitting agents (Reverse process)
Water= hydrolisis
Methanol= methanolysis
Caustic soda=saponification
Amines = aminolysis
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Fat Splitting
Natural fats consists of mainly glycerol ester of fatty acids
or triglycerides.
Fats normally means material of solid consistency,
whereas liquid materials are referred to as oil
Terms depends on parameter
State
Temperature
Fat posses a characteristic of fatty acid
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Fat Splitting: Chemical

Modification
Chemical modification:
Transesterification
Hydrolysis
Aminolysis
Saponification
Splitting agent:
Water = hydrolysis
Methanol = transesterification
Caustic soda = saponification
Amines = aminolysis
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Fat Splitting: Chemical

Modification
Transesterification
Fatty acid (Methyl

ester+ glycerol
Fatty acid + glycerol
Triglyceride
Hydrolysis
Saponification
Aminolysis
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glycerol
Fatty acid (amides) +
glycerol
244
Fat Splitting (Hydrolysis)

Principle:
Homogeneous reaction between fat and small
amount of water dissolved in fats
Fatty acids and glycerol will be discolored and
may have to be distilled
Reversible process in equilibrium with
esterification
Endothermic reaction
Uncatalyzed or added catalyst such as lipases
(bioenzyme) and zinc oxide (dibasic metal
oxides)
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Method of Fat Splitting

Twitchell process
Batch autoclave process
Continuous process
Enzymatic process
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Twitchell Process
Advantages: have low initial cost and simplicity of
installation and operation
Disadvantages: long reaction period, high energy
consumption and discoloration of fatty acid.
The process make use Twitchell reagents and sulfuric
acid to catalyze the hydrolysis.
The reagents is a sulfonated mixture of oleic or other
fatty acid and naphthalene.
Batch time : 12-24 hours
Degree of splitting almost 80-85%
Normally based in wooden container
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Batch autoclave process
Oldest commercial method for splitting higher grade
stock to produce light colored fatty acids.
More rapid than Twitchell process, take 6 to 10 hours.
Distillation normally performed to remove glyceride
esters.
This process use catalyst such as zinc, magnesium or
calcium oxides. Zinc is most active.
2 4% catalyst is used, a small amount of zinc dust is
added to improve color of fatty acid.
Conversion more than 95%
The autoclaves are tall cylinders, made of corrosionresistant alloy and fully insulated.
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Batch autoclaves process
An injection of live steam provides the agitation
although in addition use mechanical agitator.
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Continuous process
High pressure fat splitting known as Colgate-Emery
process.
High pressure (5000 kPa) and temperature (250
260oC) used permit short reaction time.
Full countercurrent flow of oil and water produces a
high degree of splitting without the need of catalyst.
The crude fat passes as a coherent phase from the
bottom of tower whereas the heavier splitting water
travels downward as a dispersed phase.
Degree of splitting more than 99%.
Reaction time only 2 to 3 hours.
Advantages: short reaction time, low energy
consumption, little CPB
discoloration
of fatty acids.
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Enzymatic splitting
Use lipolytic enzymes such as Candida Rugosa,
Aspergillus Niger and Rhizopus Arrhizus.
Crude fatty acid is predried and degassed under
vacuum and fed to distillation unit.
Operated at vacuum of 1.2 kPa or less and a
temperature approximately 200o C.
The distilled fatty acid has an almost water white
color and is free of impurities.
The bottom ends are charred viscous polymerized
material.
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Enzymatic splitting
Hydrolytic reaction is brought about by the action of
lipolytic microorganisms acting on the triglyceride
molecule in the presence of water.
It survive through with certain moisture and dirt
level.
Amount moisture required for the survival is
relatively 0.8 (ratio between vapor pressure of water
in the oil to the vapor pressure of free water at the
same temperature.)
Range 0.16 to 0.32 % of moisture in the temperature
range for handling product.
Dirt level more than 0.15%
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Fatty Acid Distillation

The fatty acid produced from the various fat splitting
process are purified and separated into fraction or even
individual fatty acids by distillation and fractionation.
Distillation of crude fatty acids removes both the low and
high boiling impurities such as unreacted partial
glycerides, soaps, glycerol, sterols, phosphatides, pitch
water aldehydes and methyl ketones as well as odors.
Fatty acids are extremely sensitive to heat, oxidation and
corrosion effect due to reactive acid group at the end of
carbon chain.
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Distillation of heat sensitive fatty acids is a highly
complex and difficult operation requiring specialized
process and equipment.
It is specially designed to obtain premium quality fatty
acids, free from odors and low molecular weight
components and minimum color contaminants, with the
help of a pre-run column.
The process involves stripping the maximum amount of
unwanted volatiles from the fatty acids.
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Distillation is carried out under high vacuum and lower
temperatures with the shortest residence time allowable.
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EQUIPMENT
The plant consists of a de-gassing and de-watering stage,
complete with a condenser/gas cooler and a condensate
receiver, two pumps, a pre-run column with falling film
evaporator, a product pre-heater, one reflux condenser,
two other condensers.
The main distillation column with a falling film
evaporator and a residue stage falling film evaporator, a
condenser serving as a product pre-heater for the degassing and de-watering stage, a final condenser, a gas
cooler, a residue cooler, a distillate receiver and three
pumps
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PROCESS DESCRIPTION
The color and odor carriers of split crude fatty acidssecondary components,
Created by oxidation and decomposition with a much
lower boiling point - are drawn off together with the fatty
acids in the de-gassing / de-watering stage, mainly with
the stripping steam added to the bottom.
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PROCESS DESCRIPTION
The fatty acids are then continuously fed to the pre-run
column, where most of the remaining secondary
components, the odour and colour, are removed by steam
distillation. The deodorisation of fatty acids, and the
separation of odour and colour components is effected by
the addition of steam to the bottom.
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The fatty acids from the bottom are pumped back
partially to the column through a falling film evaporator,
where the temperature is raised to above 200C by
heating with thermal fluid. The reflux is brought about by
the reflux condenser.
The control is effected via circulation water. The odor and
color material moves to the next condenser due to initial
cooling by the reflux condenser. The vapors entering the
next two condensers help obtain maximum recovery
from the first running separated in the liquid phase
separation tank
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The fatty acids from the pre-run column are fed
into the distiller column. The acids from the
bottom of this column are then pushed back
partially through the column via the falling film
evaporator, where the appropriate temperature
to achieve the maximum rate of evaporation
inside the distiller column is maintained.
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The distilled fatty acid vapors leaving the column
transfer heat partially to the crude fatty acid in a
condenser and then enter the next condenser,
where the maximum recovery of the distilled
fatty acids is effected.
These are then collected in the distillate receiver.
The necessary reduction in the temperature of
the distilled fatty acids is achieved with the help
of the distillate cooler.
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As the level inside the distiller column increases
the fatty acids from the bottom of the column are
pumped into the residue falling film evaporator,
which are then fed back to the distiller column.
With an increase in the falling film evaporator
level, the accumulated residue is then discharged
and after proper cooling in the residue cooler,
conveyed to residue storage
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Production of Glycerine
Glycerine is a tribasic alcohol occurring in nature
in the form of triglycerides which are glyceryl
esters of fatty acids.
It is an important high value by product obtained
from the processing of oils and fats.
Also can be synthesized from petrochemical.
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Over the years, the demand for glycerine in the
world, has continued to grow, far outstripping
the supply. It's a highly strategic chemical, used
in the manufacture of explosives,
pharmaceuticals, foods, paints, chemicals and
dyes.
All-out efforts are therefore being made to bridge
this gap between supply and demand by
increasing the present fatty acid industry
capacity, and also to step up the production of
glycerine in globally.
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Steps in production:
1. Pre-treatment:
Objectives: to prepare feedstock for glycerine
recovery (remove impurities)
Can cause fermentation produce trimethylene
glycol and acids
How to remove:
Cooling and settling
Skimmed and settling
Adding Coagulant: AlSO3 or Fe(11) chloride
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2. Evaporation
Concentrated to 80-88%
Two types :
Natural circulation
Forced circulation
Entrainment separation:
To reduce losses of glycerine in the vapor stream.
Salt removal;
Fat settling
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3. Refining glycerine
Distillation: using steam under high vacuum (5-6mm
Hg)and temperature(290C). Certain reactions occur:
Nitrogen formation
Volatile components such glycerol esters
Polyglycerols
Acrolein
Recovery
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HYDROGENATION OF
OILS AND FATS
FATS AND OIL
HYDROGENATION
PHYSICAL
PROPERTIES
improve
Hydrogenated edible fats and oils products can be

prepared with creaming properties, sharp melting
properties, and the other functional characteristics
desired for specific applications
CHEMICAL
PROPERTIES
Increase oxidative stability Flavor stability is
necessary to maintain product acceptability
for prolonged periods after processing and
packaging and for use as an ingredient in a
finished product
The products of hydrogenation

1. saturation of double bonds,
2. cis-/trans-isomerization of double bonds,
3. shifts of double-bond locations, usually to the
lower energy conjugated state.
Basic reaction of hydrogenation
UNSATURATE
D
FATTY ACID
HYDROGEN
CATALYST
HYDROGENATED
FATTY ACID
Reaction mechanism
Presence of unsaturated fat, hydrogen and catalyst at desired
operating condition
The hydrogen gas is dissolved in the liquid oil
Diffusion of hydrogen and fat into catalyst surface
Reaction between hydrogen and fat to complete the saturation
of the double bond, shift it to a new position, or twist it to a
higher melting trans form.
If the unsaturated oil to hydrogenation contains mono-, di-,
and triunsaturates, there may be competition for the catalyst
surface.
The di- and triunsaturates are preferentially absorbed and
partially isomerized or hydrogenated to a monounsaturate
until their concentration is very low, permitting the
monounsaturate to be absorbed and reacted.
Operating Variables
The variables that can affect the results of the
hydrogenation:
Temperature
degree of agitation
hydrogen pressure in the reactor
catalyst amount
type of catalyst
hydrogen gas purity
feedstock source
feedstock quality.
Temperature
Hydrogenation is an exothermic reaction
generate heat by the reaction
Temperature increases will increase the reaction
rate until an optimum is reached.
At optimum temperature, a cooling system must
be attached to the reactor to absorb heat
generated by reaction.
The optimum temperature varies for different
products, but most oils probably reach their
maximum temperature at 450 to 500F (230 to
260C)
Pressure
Most edible fats and oils hydrogenations are
performed at hydrogen pressures ranging from
0.7 to 4.0 bar (10 to 60 psig).
At low pressures, the hydrogen gas dissolved in
the oil does not cover the catalyst surface, while
at high pressure, hydrogen is readily available for
saturation of the double bonds.
Agitation
The main function of agitation is to supply
dissolved hydrogen to the catalyst surface, but
the reaction mass must also be agitated for the
distribution of heat or cooling for temperature
control and suspension of the catalyst
throughout the oil mixture for uniformity of
reaction.
Agitation has a significant effect on selectivity
and isomerization both are decreased because
the catalyst is supplied with sufficient hydrogen
to increase the reaction rate.
Catalyst Level
The hydrogenation reaction rate increases as the
catalyst concentration is increased up to a point
and then levels off.
The increase in rate is caused by an increase in
active catalyst surface; however, a maximum is
reached because at very high levels hydrogen
will not dissolve fast enough to adequately
supply the higher catalyst levels.
Both selectivity and trans-isomer formation are
increased with catalyst concentration increases,
but only slightly.
Catalyst Type
Nickel catalysts are used almost exclusively for
edible fats and oils hydrogenation.
usually prepared by the reduction of a nickel salt
and supported on an inert solid.
The activity of a catalyst depends on the number
of active sites available for hydrogenation.
These active sites may be located on the surface
of the catalyst or deep inside the pores.
Copper chromite
Copper chromite catalysts have been used for
selective hydrogenation of linolenic fatty acid to
linoleic fatty acid in soybean oil for a more
flavorful, stable salad oil with higher yields.
The selectivity offered by these catalysts is
excellent, but the activity is poor and they are
more sensitive to catalyst poisons.
Precious metals
Palladium modified with silver and bismuth enhance the
selectivity
Subsequent evaluations have shown that the precious metals
are more active at lower temperatures than nickel.
Oils have been hydrogenated at 60C (140F) with precious
metals, while temperatures above 130 to 140C (265 to 285F)
are required with a nickel catalyst.
Palladium has been found to be some 30 times as active as
nickel, as only 6 ppm is required to replace 200 ppm nickel.
High initial cost.
However, with an adequate recovery system, the precious
metal catalysts can be more cost effective than a nickel catalyst
due to lower utility costs, a long life cycle and spent catalyst
recycling directly into fresh catalyst
Catalyst Poisons
Refined oils and the hydrogen gas can contain impurities that
modify or poison the catalyst.
Catalyst poisons are a factor that can have a significant effect
on the product.
The poisons effectively reduce catalyst concentration with a
consequent change in the selectivity, isomerization, and rate of
reaction.
Impurities present in both the feedstock oil and hydrogen gas
are known to have a deleterious effect on the nickel catalyst.
Hydrogen gas may contain carbon monoxide, hydrogen sulfide,
or ammonia.
Refined oil can contain soaps, sulfur compounds,
phosphatides, moisture, FFA, mineral acids, and a host of other
materials that can change the catalyst.
Catalyst poisons
1 ppm sulfur poisons 0.004% nickel, 1 ppm phosphorus
poisons 0.0008% nickel, 1 ppm bromine poisons
0.00125% nickel, and 1 ppm nitrogen poisons 0.0014%
nickel.
Sulfur primarily affects the activity to promote
isomerization by inhibiting the capacity of the nickel
catalyst to absorb and dissociate hydrogen.
Phosphorus in the form of phosphatides and soaps
affects selectivity by residing at the catalyst pore
entrance to hinder the triglyceride exit for a higher
degree of saturation.
Water or moisture and FFA are deactivators that decrease
the hydrogenation rate by reacting chemically with the
catalyst to form nickel soaps.
Catalyst Reuse
Catalyst can be reuse to reduce the cost as long
as it still show adequate activity and selectivity.
Basically, used catalyst has lower activity and
selectivity than fresh catalyst. Thus, there is
maximum cycles in reusing the catalyst.
Separating the catalyst from product by using
filtration sometimes face problems such as:
1. FFA in the oils reacting with the catalyst to form
nickel soaps, which can blind filters
2. decreased particle size from mechanical attrition
resulting in colloidal nickel, which will pass through
the filter screens;
Source Oils
Hydrogenation selectivity
depends on the type of
unsaturated fatty acids
available and the number of
unsaturated fatty acids per
triglyceride.
Those oils with high linolenic
or linoleic fatty acid levels
hydrogenate more rapidly and
to higher melting points than
oils with high oleic fatty acid
levels.
Hydrogenation Systems
Batch hydrogenation is most commonly used in the
edible-oil industry, primarily because of its
simplicity and flexibility for use with different source
oils.
Essentially all that is required is a reaction vessel,
usually referred to as a converter, that can withstand
7 to 10 bar (105 to 150 psig) pressure, with an
agitator, heating and cooling coils, a hydrogen gas
inlet, piping and pumps to move the oil in and out,
and a sample port for process control of the reaction.
The converter must also be provided with the means
to control the three reaction variables: pressure,
temperature, and rate of agitation.
Batch hydrogenation process flow.
Batch vs. continuous process

Most hydrogenations of edible fats and oils are performed
both in the United States and in the rest of the world in batch
converters.
Continuous hydrogenation systems have been available for
quite some time, but their commercial usage has been limited
for several reasons.
The maximum value for any continuous operation is realized
when it is used to produce large quantities of the same
product.
Considerable out-of-specification product can be produced
during a change from one product to another.
Because most fats and oils processors produce a variety of
products, several different basestocks are routinely required
that can be produced more uniformly with batch
hydrogenation systems.
Hydrogenation Control
Physical consistency of most finished shortenings,
margarines, and other fats and oils products is
identified by analytical methods, such as solids fat
index (SFI), iodine value (IV), and/or melting points.
However, time restraints during hydrogenation
require more rapid controls.
Hydrogenation controls used to determine basestock
endpoints include:
Refractive index
Mettler dropping point
Quick titer
Refractive index
Hydrogenation reduces both the iodine value and the
refractive index of oils.
The relationship between the iodine value and
refractive index depends on the molecular weights of
the glycerides, which is very nearly the same for
most oils.
The exceptions are the oils high in either lauric or
erucic fatty acids.
Correlation between iodine value and refractive
index is not precise, but will be within one or two
units, which should be adequate to monitor the
hydrogenation reaction and indicate when to
interrupt the reaction for more precise evaluations.
Mettler dropping point

The relationship of iodine value to melting point can be
changed by varying hydrogenation conditions, catalyst
types, and levels, therefore, it is necessary to measure
both refractive index and melting characteristics for most
basestocks with iodine values below 90.
Mettler dropping point analysis can provide a reliable
result in less than 30 minutes for these basestocks.
Usually, the oil is hydrogenated to a refractive index
before determining the Mettler dropping point, which is
the controlling analysis.
If the melting point (dropping point) is lower than
desired, hydrogenation is continued and the process is
repeated until the specified melting point is obtained.
Quick titer
Refractive indices are rarely used for low-IV hard fat
hydrogenation control.
The refractometers are generally kept at 40.0C ( 0.1C), and
the hardfats would solidify on the prism at this temperature.
It is too hard for dropping point determinations, and IV or
official titer determinations are too time consuming.
A nonstandardized quick titer evaluation is usually used for
endpoint control for the hardfats.
In this evaluation, a titer thermometer is dipped into a hot
sample directly from the converter and rotated in the air until
the fat forms clouds on the thermometer bulb.
The correlation between iodine value and quick-titer results is
different for each source oil, therefore, quick-titer limits must
be predetermined for each product.
Hydrogenated Basestock
System
The difference specification of finish product of
hydrogenated oil cause problems in
hydrogenated oil storage.
It is important to have a basestock systems with
a limited number of hydrogenated stock products
for blending to meet the finished product
requirements are utilized by most fats and oils
processors.
The advantages provided by a well-designed
basestock system are basically control and
efficiency
Types of basestock
Brush hydrogenated basestocks
Partially hydrogenated flat basestocks
Partially hydrogenated steep basestocks
Low IV hardfats
POSTBLEACHING
A separate bleaching operation, immediately following the
hydrogenation process, has three general purposes:
1. to remove traces of nickel that escape the catalyst
recovery filtration;
2. to remove undesirable colors, generally of greenish hue;
3. to remove peroxides and secondary oxidation products.
This bleaching process generally employs a bleaching
earth and a metal-chelating acid to reduce the residual
nickel content to the lowest possible level.
As much as 50 ppm nickel, mostly in colloidal form, can remain

in the hydrogenated oil after the black press filtration.
Trace amounts of nickel remaining in the oil adversely affect
the stability of the oil by accelerating the oxidation process.
After postbleaching, the trace metal levels in the oils should be
reduced to <0.1 ppm nickel and <0.02 ppm copper for
oxidative stability.
Green colors can emerge in the hydrogenated oils because of
the heat bleaching of yellow and red masking pigments during
hydrogenation.
Process condition
Vacuum batch systems are normally selected over
atmospheric processes for the oxidative protection
afforded the oils.
The bleaching conditions are normally 0.1 to 0.2%
activated bleaching earth with approximately 10
ppm phosphoric acid or 50 ppm citric acid added as
a chelating agent and bleached at 180F under a 25inHg minimum vacuum.
After bleaching, the spent earth and adsorbed
impurities are removed with a pressure filter, and
the oil is cooled to 130F before further processing
or is inventoried for basestock blending.
FRACTIONATION
Purpose of fractionation
To provide new materials more useful than the
natural product.
To remove an undesirable component.
To provide two or more functional products from
the same original product (e.g. production of
cocoa butter, or olein stearin)
Basic principle of the

fractionation process
Difference of melting point of chemical
constituent in fat and oil.
Difference of solubility for each component in
specific solvent. The solubility differences are
directly related to the type of triglycerides in the
fat system.
Stages of fractionation
1. Cooling of the oil to supersaturation to form the
nuclei for crystallization
2. Progressive growth of the crystalline and liquid
phases
3. Separation of the crystalline and liquid phases
Modes of fractionation
Dry Crystal Fractionation
Detergent Fractionation
Solvent Fractionation
Dry Crystal Fractionation

Dry crystal fractionation procedures are commonly
used for separation of hard stearine and soft olein
fractions from natural products that contain high
levels of each like palm oil and the lauric fats
The principal of this fractionation procedure is based
on slowly cooling the oil under controlled conditions
without the aid of a solvent.
The stearine and olein fractions can be separated by
various processes, such as filtration, centrifugation,
hydraulic pressing, rotary drum, or other separation
processes.
The aqueous detergent fractionation procedure utilizes
the same basic principals of dry fractionation; that is,
crystallization is induced by cooling the oil under
controlled conditions without the addition of a solvent.
The difference is that an aqueous detergent solution is
added to the crystallized material to assist in the
separation of the liquid olein and the solid stearine.
The aqueous solution contains about 5% of a detergent
such as sodium lauryl sulfate, which preferentially wets
the surface of the crystals displacing the liquid oil.
About 2% of an electrolyte such as magnesium or
aluminum sulfate is added to the solution to assist in
uniting the liquid olein droplets.
(contd.)
Aqueous detergent fractionation is more
expensive than dry fractionation, but more
complete separation of the soft and hard
fractions can be achieved, thus producing a
higher olein yield and a harder stearine fraction.
Solvent Fractionation
Solvent fractionation is an expensive process that
can be justified only for preparation of valueadded, high-quality products.
Fractional crystallization from dilute solution
results in more efficient separation with
improved yields, reduced processing times, and
increased purity than can be achieved by
fractionation carried out without a solvent.
Product of solvent fractionation

Cocoa-butter equivalents (CBEs) CBEs are fats with
chemical compositions similar to cocoa butter and
capable of replacing it in any proportion in
chocolates
Lauric cocoa-butter replacers (CBRs) These are
products made from fractionated coconut or palm
kernel oils with physical properties closely
resembling cocoa butter.
Nonlauric CBRs The most widely used products in
this classification are based on solvent-fractionated,
hydrogenated liquid oils, such as soybean,
cottonseed, and palm oils.
Product of solvent fractionation

(ctd.)
Confectionery products Fat systems with a low melting
point but a high SFI content at room temperature can
provide products with a quick melt at body temperature,
which results in a cooling sensation when eaten. Highquality candy centers and whipped toppings are two
specific applications for fractionated products.
Medium-chain triglycerides Lauric oil fractions
containing C-6:0, C-8:0, and C-10:0 saturated fatty acids,
which are soluble in both oil and water systems for quick
absorption by the body and transported via the portal
system.
High-stability liquid oils Modification of oils by
utilization of hydrogenation with fractionation has
permitted the development of liquid oils with high
resistance to oxidative degradation.
Solvent fractionation process

Modes of process: batch, semicontinuous, or
continuous.
Unit operations required: Crystallizers, filters,
and solvent recovery systems
Solvent used: mostly organic solvent, e.g.
acetone, hexane, and 2-nitropropane
Process parameters and control

Feedstock selection, which can include natural
oils and blends, hydrogenated oils and blends,
randomly rearranged oils and blends, and blends
of any or all of these
Concentration of the fat in the solvent
Fractionation temperature
Cooling rate and residence time in the
crystallizer
Separation conditions
Typical solvent fractionation

process flow
1.
Heating the feedstock oil to a temperature above the completed melting point
2.
Blending with warm solvent (oil : solvent = 1 : 3 5)
3.
The solution is then cooled to crystallize the hard fractions.
Crystallization temperatures vary, depending on the nature of the solvent, the concentration of oil in
the solution, and the characteristics needed in the final fractions.
For example, for lauric oils in acetone solvent, temperatures of 28 to 68F (2 to 20C) have been
used to obtain stearine iodine values of 1.8 to 8.3.
4.
The crystallized slurry is separated by filtration or by a settling technique.
5.
The solid material is then stripped of solvent for one fraction.
6.
Removal of the solvent from the filtrate yields another fraction.
7.
Further fractionation may then be achieved by redissolving either fraction and repeating
the process.
ESTERIFICATION OR
ALCOHOLYSIS
(PRODUCTION OF EMULSIFIER)
Emulsifiers
Food emulsifiers act as an interface between the
conflicting components of food like water and oil.
Mono- and diglycerides were the first fatty
emulsifiers to be added to foods.
These emulsifiers were first used in margarine
for Danish pastry and puff pastry shortening.
The first U.S. patents for mono- and diglycerides
granted in 1938 disclosed the usefulness of
surfactants in emulsions and margarine
Esterification
Emulsifiers are usually made either by
alcoholysis or by direct esterification.
In direct esterification, fatty acids and
polyalcohols are reacted together under
controlled conditions to form esters.
In alcoholysis, fats are reacted with polyalcohols
to make the surfactants. (For example, the
production of mono- and diglycerides from fat is
an alcoholysis reaction with glycerine as the
alcohol)
Emulsifier reactor
Mode: batch
Reactor material: acid-resistant stainless steel, e.g
type 304 (T < 150C), and type 316 (T > 150C)
Internal reactor coils capable of handling highpressure steam and cooling water, as well as a
vacuum system with 0.1-mmHg capabilities, are
necessary for emulsifier reactors.
A condenser for the recovery of the excess glycerine,
glycol, or other alcohols should be sized for the
largest volume of the polyalcohol to be recovered.
Mono- and Diglycerides

Mono- and diglycerides are the most dominate
food emulsifier
The mono- and diglycerides consist of glycerol
esters of various edible fatty acids and fat blends.
Three types of standard mono- and diglycerides
are manufactured: 40 to 46% -monoglyceride
content, 52 to 56% -monoglyceride content,
and distilled monoglycerides with 90% monoglyceride content.
There are three basic physical forms of monoand diglycerides: hard, soft, and intermediate.
Mono- and diglyceride batch

process flow.
Monoglyceride Derivatives
Lactylated Monoglycerides
Esterification is conducted with addition of lactic acid
Utilized primarily for aeration in cakes and whipped toppings
Acetylated Monoglycerides
Produced by direct acetylation of monoglycerides with acetic anhydride
Utilized as whipped toppings and other foams
Ethoxylated Mono- and Diglycerides

Formed when ethylene oxide are reacted with a mono- and diglyceride
Enhance the consistencies for yeast-raised products, and for cakes and icings
Succinylated Monoglycerides
This product is manufactured by reacting monoglyceride with succinic anhydride at
temperatures ranging from 175 to 350F
bread-softening agent
Other types of emulsifier

Polyglycerol Esters
Polyglycerols are polymers formed by the dehydration of

glycerine.
The polyglycerol esters are functional in a very broad
range of applications, either singly or blended with other
emulsifiers, to include crystal inhibitors; aeration of
batters, icings, fillings, and toppings; antispattering agents
for cooking oils and margarine; low-fat products; ice
cream and mellorine; confectionery antibloom agent;
viscosity control; nondairy creamers; cake mixes;
lubricants; etc.
Propylene Glycol Monoester
Formed by alcoholysis of monoglycerides with propylene

glycol
effective emulsifiers for cake baking and whipped
toppings.
BLENDING
Purpose of blending: to produce the specified
composition, consistency, and stability
requirements for the various edible fat and oil
products
Products of blending: shortenings, frying fats,
margarine oils, specialty products, and even
some salad oils.
Blending equipment
Main equipment: scale tanks and meters to
proportion the basestocks accurately for each
different product.
mechanical agitators
heating coils
Capacities of the blend tanks should be sized to
accommodate the next process, probably
deodorization.
Nitrogen protection should be provided for the
long holding times required
Blending process sequence

1. Determine the proportions for each basestock
for the product to be blended.
2. Add the basestocks to the blend tank at the
identified proportions.
3. Heat the blend, if necessary, to the specified
temperature and agitate for 20 minutes.
4. Sample and submit to the laboratory for the
specified analysis.
5. Transfer to the next process if the analytical
characteristics meet the specified limits.
Blending process sequence

6. Adjust blends outside the specified limits to
bring them into the allowed consistency control
ranges; however, use only specified basestocks
within the allowed ranges for any adjustments.
7. Resample the adjusted blend after agitating for
20 minutes to achieve a uniform product and
resubmit to the laboratory for consistency
analysis.
8. Transfer to the next process after the specified
analytical objectives have been met.
FINISHED FATS AND OILS

HANDLING
Main objectives of handling:
Protection against Oxidative Deterioration
Protection against Contamination
Protection against Oxidative

Deterioration
Nitrogen Blanketing
Temperature Control
Light Control
Storage Time
Antioxidant Addition
Nitrogen Blanketing
Oxygen contact can be reduced by keeping the
entire edible fats and oils handling process
protected with an inert gas.
In finished oil processing, preferably the product
is protected by nitrogen gas in the storage tanks
and bulk transports as well as in the packaging.
Effective protection against oxidation for
packaged products requires that the air in the oil
and the package headspace be evacuated and
then replaced by a protective gas, such as
nitrogen
Temperature Control
Fats and oils temperatures should be maintained
as low as possible during handling because heat
accelerates the oxidation reaction
The speed of oxidation is doubled for each 15C
temperature increase in the 20 to 60C range.
To keep the oil in liquid state, they must be
stored at 5.5 to 8.5C above the melting point.
Light Control
Light exposure contributes to the flavor
deterioration of all edible fat and oil products.
Limited exposure of an oil product to sunlight or
ultraviolet rays from fluorescent lighting will
increase peroxide value results and decrease
flavor ratings.
Storage Time
Most shortenings and other similar products will
maintain an acceptable flavor and oxidative
stability for two to three weeks in melted form
with adequate controls.
Therefore, edible fats and oils storage systems
should be designed for turnovers of less than two
to three weeks or within the established storage
life of the product
Antioxidant Addition
Antioxidants are chemical compounds that
provide greater oxidative stability and longer
shelf life for edible fats and oils by delaying the
onset of oxidative rancidity.
Some of antioxidant types:
Tocopherols and tocotrienols

Propyl gallate (PG)
Butylated hydroxyanisole (BHA)
Butylated hydroxytoluene (BHT)
Tertiary Butylhydroquinone (TBHQ)
Protection against
Contamination
A contaminant is any undesirable material that
may taint, infect, corrupt, modify, or degrade by
contact or association.
Edible fats and oils must be protected from
contamination at all stages of processing and
especially after deodorization because that is the
last opportunity to remove undesirable flavors,
odors, colors, and other compounds.
Types of contaminant
Moisture
Impurities
Commingling
Odors and flavors
Moisture
The presence of water can lead to the hydrolysis
reaction
Hydrolysis is the reaction of water with a fat or
triglyceride to break it down into a diglyceride and a
free fatty acid.
This hydrolytic reaction of fats and oils can be
prevented by maintaining a moisture-free
environment for the product.
Potential sources of moisture contamination during
storage and handling are ruptured heating or cooling
coils, leaking coolers, inadequate drying of washed
tanks, condensation, steaming of lines, etc.
Impurities
Foreign material in a finished product is usually
caused by a malfunctioning polish filter,
precipitant of metal salts, polymerized oil from
dead spaces in lines, inadequate tank cleaning,
etc.
It is a good policy to polish filter all finished
products during each transfer, preferably as near
to the destination as possible.
Commingling
Commingling: Inadvertent mixing of two
different fats and oils products together
Commingling with another product can change
the composition, consistency, performance, and
oxidative stability of the contaminated product.
The resultant product in most cases requires
reprocessing to another product due to potential
changes in labeling, religious constraints, and
performance.
Commingling is usually the result of human error
or malfunction of a valve.
Odors and flavors

Fats and oils easily absorb odors and flavors
from other foods, spices, solvents, gases,
chemicals, paints, and any other odoriferous or
flavorful material.
Extreme care must be exercised to protect the fat
and oil products at all times after deodorization
including storage, handling, and transportation
of bulk liquid or packaged products.
OILS AND FATS

APPLICATION
Classification of product type
Edible product
Non-edible product
Edible application
Butter
Margarine
Shortening
Frying oil and salad oil
Mayonnaise
Vegetable cream
Emulsifier
Butter
Butter is a solid dairy product made by churning
fresh or fermented cream or milk, to separate the
butterfat from the buttermilk.
It is generally used as a spread on plain or
toasted bread products and a condiment on
cooked vegetables, as well as in cooking, such as
baking, sauce making, and pan frying.
Butter consists of butterfat, milk proteins and
water.
Raw material of butter: milk, mostly cow milk
Butter how to produce?

MILK TREATMENT
SOURING
CREAM SEPARATION
& HEAT TREATMENT
CREAM RIPPENING
BUTTERING/CHURNING
Flowchart of
butter
production
Milk Treatment
The milk supplied is pasteurized by heating it
and holding it at 71-74C for 30-40 s.
Under these conditions, most bacteria are killed.
Only some thermophilic bacteria may survive;
however, these are not pathogenic
Usually this pasteurization is done via plate heat
exchangers.
Temperatures applied may be higher for
technological reasons.
Cream Separation and Heat

Treatment
Cream is separated via cream-centrifuges and
then pumped into a buffer. There it is adjusted to
the right fat content by the addition of skim milk.
centrifuges have a throughput of -20 to& with a
revolution speed of 6500/min.
To increase storage stability of butter and to
improve ripening of sour cream butter, the cream
is heated to at least 95C. At this temperature,
those microorganisms that survived
pasteurization are also killed.
Souring (Sour Cream Butter)

Souring of cream when producing sour cream butter
is usually done with cultures of Streprococcus
diacetilacris, Streptococcus cremoris and Leuconostoc
citrovorum.
The amount of souring culture as well as the cooling
temperature, the souring temperature and the
ripening temperature depend on the hardness of the
milk fat, which is proportional to the iodine value
During souring, flavors develop, with diacetyl
(butane-2,3-dione) as the most prominent.
The presence of oxygen is essential for the formation
of diacetyl from acetoin. The reaction can be
promoted by the addition of citric acid.
Cream Ripening
The cream is held in the
cream ripeners for 4-20 h
at 6-10C.
At this temperature, part
of the milk fat solidifies
along the hulls of the
globules, thus stabilizing
them.
Buttering (Churning)
Milk fat appears in
both milk and cream
in droplets that
consist of a hull of
phosphatide and
protein molecules
filled with fat and oil
these phosphatides
stabilize the
emulsion milk, i.e.,
the emulsion oil in
water.
At buttering temperature, the fat in these globules is

fractionated into a fat layer that precipitates along the
phosphatide/protein hull, reinforcing that hull, and a liquid
kernel.
For buttering, the globules have to be broken up so that liquid
fat from these globules can float together to form larger
globules
As a prerequisite, there must be a certain minimal distance
between the fat globules in the cream, which depends on the
concentration stage of the cream
Once the fat globules are concentrated enough, mechanical
stress (beating) can destroy the phosphatide and fat hull so
that the liquid portions can coalesce and the empty hulls can
agglomerate to butter grains
Continuous butter making

machine
MARGARINE
A prize was offered by

Emperor Louis Napoleon III
of France for an inexpensive
butter substitute
186
9
187
4
Oleomargarine, first
margarine based
from oleo-oil (derived
from beef fat) was
developed by MegMouris in France
The History of
Margarine
First margarine
was produced in
US, based from
oleo-oil
188
6
The Oleomargarine
Act was passed by US
Congress to restrict
the application of
margarine, and
protect butter
industries
Vegetable oil
(coconut oil) was
introduced as fat
blend in margarine
192
0
192
3
First
margarine
fortified by
vitamin A was
introduced
Recognition of the
food value of
margarine by USDA
and FDA
194
1
195
0
New Margarine Act

was passed by US
Congress to end the
restriction the
margarine application
and production
195
7
Margarine
overtook
butter in U.S.
per capita
consumption
Tablespread consumption
history
Composition of Margarine
Margarine is an emulsion of the type water in oil,
consisting of 80% fats and oils and 20% of an aqueous
phase, which like the oil phase contains soluted
ingredients.
About 20% (minimal -12%) of the triglycerides of the fat
blend are solid at room temperature, the remainder is
liquid.
The fat/oil phase contains the fat-soluble ingredients.
These are usually fat soluble flavors, vitamins as well as
emulsifiers and carotenes.
The aqueous phase holds the water-soluble ingredients,
which are generally water-soluble flavors, salt, milk or
milk solids, and in special cases, preservatives.
Composition of Margarine
1.
2.
3.
4.
5.
6.
7.
Fat blend
Emulsifiers
Milk component
Acids
Salt
Flavors
Preservatives
8. Thickening
agents/stabilizers
9. Colorants
10. Vitamins
11. Water
12. Air, Nitrogen
13. Starch
Fat blend
Purpose: Composition of fat blend can be optimized
to achieve certain physical properties (e.g. melting
point etc.)at the lowest cost of production.
The blend composition for margarine has changed
dramatically over the last century of its development
in the market:
in 1917, >60% of the U.S. margarine fat blend was of

animal origin
Today, animal fat has almost completely disappeared, and
vegetable oils and fats are dominant in almost all countries
Nowadays, typical composition of margarine is 35 %

palm stearin and 65 % unsaturated fat (rapeseed oil,
soybean oil, or palm olein)
Emulsifiers
Purpose of emulsifiers is to stabilize the
emulsion.
The main emulsifiers used are lecithin and
monodiglycerides
Emulsifiers reduce surface tension between
aqueous fraction and fat/oil fraction
The addition of tiny amounts of soy lecithin
(0.002%) decreases surface tension to 10%
Adding monoglycerides (0.3%) decreases surface
tension to 80%,
Milk Components
The optional ingredients of the aqueous phase
include water, milk, or milk products.
Initially, cows milk was used, but now water can
be used with or without an edible protein
component.
Initially, the margarine standards promulgated in
1941 required that the aqueous system contain
10% milk solids; however, that requirement has
been removed, and most margarines produced
with milk or another protein contain
considerably lower levels, usually less than 1.5%.
Acids
Acids have to fulfill several tasks:.
lower the pH value, improving bacteriological
stability.
Create a better, fresh taste. The use of lactic acid
gives a peaked, fresh taste.
Citric acid is a milder acid with the additional
benefit of binding metals such as iron in a
complex, which tremendously reduces the
sensitivity of the oil to autoxidation.
Salt
Salt has two functions: to decrease the
microbiological sensitivity; and act as a flavorer
Salt content differs greatly from country to
country.
In Middle Europe, it is -0.2%; in the UK, it is much
higher and in some overseas countries it can go up to
3%
It can be explained because of different eating habits.
As antimicrobial agent, presence of more than

10% salt in an aqueous solution can completely
stop the activity of microorganisms
Flavors
The flavor cocktails used in margarine making
work as flavors and flavor enhancers; they also
mask off-flavors.
The flavors used depend on the geographical
region, i.e., the local taste, and can range from
bland to over-buttery to cheesy.
Dosage also is done according to localpreference.
Preservatives
Preservatives are rarely used in 80% fat margarines
in countries with moderate climate, households
equipped with refrigerators and well developed
logistic chains.
In reduced-fat margarines, they are not necessary for
production, but are needed to protect the product
during open shelf life.
The most common preservatives: benzoic acid and
sorbic acid
When benzoic acid is used, the amount is usually
<0.1%.
Sorbic acid usually is allowed up to 0.12%, but the
amount used is normally lower
Thickening Agents, Stabilizers

In half-fat margarines or margarines with an
even lower amount of fat, the emulsion on its
own is no longer able to stabilize the product.
Therefore, thickening agents or stabilizers, (for
example, gelatin), are used to stabilize the water
phase.
Colorants
In Europe, margarines usually are not colored
with artificial colors.
Often, however, -carotene is added; it dissolves
in the oil to give a reddish color. In many
countries, The addition of -carotene is also
allowed for butter and is used to color winter
butter.
If unbleached palm oil is used in the blends, a
natural yellow-reddish color can be obtained by
the carotenes without later addition.
Vitamins
Vitamins are added to almost all household
margarines.
In some countries, the addition at the level that is
usually present in butter is mandatory.
Usually, fat-soluble vitamins A, D and E are used.
In geographical regions with deficiencies in
water-soluble vitamins, vitamination with
vitamins B and C is also common.
Water
Water usually stems from wells on the margarine
factory sites or is taken from the municipal net.
Water quality must be monitored constantly.
Air, Nitrogen:
Some margarines and fats are whipped with nitrogen or
air to soften the products (so-called soft margarines).
In most countries, the gas used for whipping has to be
declared on the ingredients list.
Starch
Until some years ago, in some European countries,
starch had to be added to margarine to enable
adulteration of butter with margarine to be detected.
This legal requirement stems from the last century,
because current modem analytical techniques allow
easy detection of adulteration without the addition
of marker substances such as starch or sesamol.
Starch has no function at all in margarine.
On the contrary, it negatively influences its
spattering behavior.
Liquid Oil
Liquid Oil
COOKING OIL
Liquid and clear at room
temperature and may be used for
cooking.
Cooking oils are used for pan and
deep-fat frying and in packaged
mixes or wherever a clear, liquid oil
has application without
refrigeration.
Cooking oils may solidify at
refrigerator temperatures.
Higher stability
SALAD OIL
Remain substantially liquid at
refrigerator temperatures, 4.4C.
Salad oils may be used for
cooking but are low in saturated
fatty acids to prevent or delay
clouding and graining during
refrigeration.
Lower stability
Trend in usage of liquid oil
The history
In sub-tropical region, oil will be solidify partially in
winter season. The remained liquid fraction of oil
then separated from the mixture through a decanter.
The fraction of oil that remain as liquid is called as
winter oil. Nowadays, winter oil is also known as
salad oil
The solid fraction that is separated in winter season,
then become cooking oil. Since this fraction will be
liquid in summer season, it is also known as
summer oil, or cooking oil.
A process namely winterization was developed to
separate liquid oil into two fraction: salad oil and
cooking oil
Winterization of liquid oil

Winterization is a simple fractionation.
Liquid oil is cooled to reach the temperature of
winter season (5-15C) and allowed to rest for
up to 36 h.
Liquid fraction of winterized oil can be used as
salad oil.
Requirements of a winter oil: resist clouding for
more than 5-1/2 hours at 32F (0C).
Cooking oil can be defined as liquid oil without
winterization process
MAYONNAISE
Mayonnaise, the most prominent savory dressing
with a high oil content, is an oil-in-water emulsion.
It is used both in homes and in restaurants for
preparing sandwiches, salads, and similar cold
dishes.
In mayonnaise, salad oil is the dispersed phase,
vinegar and water are the continuous phase, and egg
yolk is the emulsifying agent.
Salt and sugar are dissolved in the water and vinegar,
and the spices are held in suspension in the water
phase.
Composition of mayonnaise
Oil At least 65% of one or a blend of two or more
edible vegetable oils; the oil may contain oxystearin,
lecithin, or polyglycerol ester to inhibit crystal formation.
Acidifying ingredient acetic acid or citric acid, can be
prepared from vinegar or lemon or lime juice.
Egg-yolk-containing ingredient Liquid, frozen, or dried
egg yolks; liquid, frozen, or dried whole eggs; or either,
mixed with liquid or frozen egg whites. No minimum
requirement is stated.
Optional ingredients Mayonnaise may also contain salt,
nutritive carbohydrate sweeteners (which would include
sugar, dextrose, corn syrup, honey, other syrups),
monosodium glutamate, and any spice
Mayonnaise Processing
The classic batch system disperses the dry
ingredients into beaten eggs along with half of the
vinegar/water mixture.
Then, the oil and remaining vinegar/water mixture
are added simultaneously in separate streams.
The oil addition should be completed slightly before
the vinegar/water mixture.
After all the ingredients are added, the emulsion is
mixed 1 minute at low speed before filling.
Mayonnaise can be produced by continuous process
also, either in single stage or two stages process.
SHORTENING
Originally, shortening was the term used to describe
the function performed by naturally occurring solid
fats such as lard and butter in baked products.
These fats contributed a short (or tenderizing)
quality to baked products by preventing the cohesion
of the flour gluten during mixing and baking.
Today, shortening has become virtually synonymous
with fat and includes many other types of edible fats
designed for purposes other than baking.
Description of shortening
Shortening can be described as processed fats and oils
products that affect the stability, flavor, storage quality,
eating characteristics, and eye appeal of prepared foods by
providing emulsification, lubricity, structure, aeration, a
moisture barrier, a flavor medium, or heat transfer.
Source of oil/fat utilized for

shortening
Shortening Product Forms

Plasticized semisolid shortenings For all
purpose, unemulsified, emulsified, animal
vegetable blends, or the like, whereas the trend is
toward classifying most other shortenings by the
intended usage (e.g., cake and icing, mellorine,
bread, frying, and so on).
Liquid shortenings The liquid or pumpable
shortening, was developed for bulk handling and
metering at room temperature and easier
handling of packaged product that can be
volumetrically measured and poured.
Non-Dairy Creams
Products in which milk fat is replaced by vegetable
oil/fat are called vegetable cream or non-dairy
cream.
These creams are used in bakeries, for example, for
the production of cake fillings.
They are usually more stable than dairy cream when
whipped and allow for much higher overrun.
Most of these products cannot be mixed with dairy
cream because of the incompatibility of their crystal
modifications.
The compositions for such non-dairy creams are
manifold and depend on the purpose for which they
are made.
Flow chart of
vegetable cream
production
Non Edible application:

SOAP AND DETERGENTS
Surfactants
Surfactants are surface active molecules
that lower the surface tension of a
liquid, allowing easier spreading and
lowering the interfacial tension between
two liquids or between a liquid and a
solid.
It is used relatively in cleaning solution
which are able to remove dirt from
substances, textiles and other solid
when dissolves in water.
393
Surfactants
Surfactants are produced both by the
petrochemical and oleochemical industries
The molecular structure of surfactant is
amphiphilic consists of hydrophobic group
(lipophilic) and hydrophilic group
(lipophobic)
The hydrophobic tail will repels water and
attracted to oil and grease in dirt while the
hydrophilic head is more attracted to water
molecule.
394
395
396
Amphiphilic molecules can exist comfortably

at an oilwater interface and reduce the
surface tension at such interfaces.
Amphiphilic molecules influence a range of
important surfactant properties, such as
emulsification, deemulsification, wetting,
foaming, defoaming, water-repelling,
dispersing, solubilising, detergency,
sanitising, lubricity, and emolliency.
The simplest and oldest examples are soaps,
such as sodium palmitate in which the
palmitic acid chain is lipophilic and the
carboxylate group is hydrophilic
397
How Surfactants Work?

Surfactant molecules will migrate to the
water surface
The water insoluble hydrophobic group
may extent out of the bulk water phase
or if water is mixed with an oil, into the
oil phase in dirt.
The water soluble head group remains
in the water phase and pulls the stain
away from fabric.
398
399
Types of Surfactants
4 major types of surfactants:
Anionic surfactant
Nonionic surfactant
Cationic surfactant
Zwitterionic (amphoteric) surfactant
Classified according to the nature of

head group.
400
Anionic Surfactants
Anionic surfactant is a substance that
have a negatively charged species at
hydrophilic part.
Sensitive to water hardness.
Widely used for laundering,
dishwashing products and shampoo.
Examples: carboxylates, sulfonates,
sulfates and phosphates.
401
Cationic Surfactants
Cationic surfactant is a surfactant that
have positively charged such as
trimethylalkylammonium chlorides in
hydrophilic part.
Have the ability to adhere to and modify
solid surfaces.
Does not provide effective cleaning and
mainly used in the application concern
with germicidal, hydrophobisation and
antistatic effect.
402
Cationic Surfactants
Widely used in fabric softening, hair
conditioning, corrosion inhibitation,
mineral floatation and as
bactericides.
Examples: esterquat and mono alkyl
quarternary
403
Nonionic Surfactants
Nonionic surfactant is a surfactant that
contain non-charged species at hydrophilic
part.
The head group is not charged, but is polar
through the presence of an appropriate
collection of hydroxy, amino, or ether
groups
Not sensitive to water hardness
Widely use in textiles
Example: polyglycerol esters
404
Zwitterionic Surfactants
Have both positive charge and negative
charge in hydrophilic part depending on
acidity or pH of solution.
Can act as anionic in alkaline solution or as
cationic in acidic solution.
It is highly soluble and effective although in
the presence of high concentrations of
electrolytes, acids and alkalis.
Widely used for personal care and
household cleaning products.
405
Soap
Soap is one example of a broader class
of materials known as surface-active
agents, or surfactants.
Soap are mainly use for washing,
bathing, and cleaning purposes.
Surfactant molecules contain both a
hydrophilic or water-liking portion and
a separate hydrophobic or waterrepelling portion.
406
The hydrophilic portion of a soap molecule

is the carboxylate head group and the
hydrophobic portion is the aliphatic chain.
Soluble in aqueous and organic phases or
preferential aggregate at air-water
interfaces.
This special chemical structure that leads to
the ability of surfactants to clean dirt and
oil from surfaces and produce lather
407
Soap Production
Soap can be produced from the
saponification reaction where caustic
soda (NaOH) react with triglyceride
to yields glycerol and soap
CH2 O
O
R2
CH2 O
O
C
H2C
R1
HO
O
C
Triacylglycerol
R3
3 NaOH
H2C
OH
H
OH
R1
+ R
2
R3
O
C
O
ONa
ONa
O
C
ONa
Glycerol Sodium salts of

fatty acids (soap)
408
Soap Production
Saponification can proceed directly as a
one-step reaction as shown above, or it
can be achieved indirectly by a two-step
reaction.
In two step reaction, the intermediate
step generates fatty acids through
simple hydrolysis of the fats and oils and
the finishing step forms soap through
the neutralization of the fatty acid with
caustic soda.
409
Soap Production
Compositional differences in the fats
and oils give rise to their significantly
different physical properties and those
of the resulting fatty acids and soaps.
High levels of unsaturated (containing
double bonds) or short-chain-length
components produce fatty acids that are
liquid and soaps that have high water
solubility at room temperature.
410
Soap Production
High levels of saturated, long-chainlength components produce waxy
and hard fatty acids and soaps that
are essentially insoluble at room
temperature.
A key to producing soaps with
acceptable qualities is the proper
blending of these fats and oils.
411
Commercial Processing of
Soap
Commercial
Processing
Direct
saponification
Kettle Boiled
Batch Process
Fatty acid
neutralization
Continuous
Saponification
system
412
Direct Saponification - Kettle Boiled

Batch Process
413
Direct Saponification
Kettle Boiled Batch Process
This process produces soap in large, open

steel tanks known as kettles, which can
hold up to 130,000 kg of material
Kettles are cylindrical tanks with conical
bottoms, which contain open steam coils for
heating and agitation.
Fats and oils, caustic soda, salt, and water
are simultaneously added to the kettle.
The addition of steam to the system
facilitates mixing and the saponification
reaction.
414
Upon completion of the saponification
reaction, additional salt is added to the
kettle while boiling with steam to convert
the mixture from a pure neat-soap phase
composition into the curd soap-lye seat
biphasic composition
The mixture is allowed to separate for
several hours, after which the aqueous
solution or lye seat is removed from the
bottom of the kettle.
415
The lye seat is usually transferred to a
glycerol recovery system.
The curd soap remaining in the kettle is
typically washed a few times by adding
water, converting it back into neat soap and
repeating the salt addition, boiling, and
separation process
This washing process provides a more
complete removal of glycerol and other
impurities from the soap
416
After the final wash, the water level in
the curd soap remaining in the kettle is
adjusted to achieve the proper physical
properties for additional processing.
What remains in the kettle is pure neat
soap at 70% concentration with low
levels of salt and glycerol.
This process is time-consuming and
requires several days to complete.
417
Continuous Saponification System
These systems have led to improved
manufacturing efficiency and considerably
shorter processing times.
Blended fat and oil feedstocks are continuously
and accurately metered into a pressurized,
heated vessel
The vessel is an autoclave, along with the
appropriate amount of caustic, water, and salt.
The concentrations of these ingredients are
adjusted to yield a mixture of neat soap and a
lye seat.
418
At the temperatures (~120C) and pressures
(~200 kPa) used, the saponification
reaction proceeds quickly (<30 min).
After a relatively short resident time in the
autoclave, the neat soap and lye seat
reaction blend is pumped into a cooling
mixer where the saponification reaction is
completed and the reaction product is
cooled to below 100C.
419
The reaction product is pumped next into a

static separator, where the lye phase
containing a high level of glycerol (25-30%)
is separated from the neat soap through
gravitational force or settling
The neat soap is then washed with a lye and
salt solution using a countercurrent flow
process.
The neat soap is introduced into the bottom
of the column and the lye/salt (washing)
solution is pumped into the top.
420
The less dense neat soap rises up in the

column while the lye/salt solution falls to
the bottom.
Final separation of the lye seat from the
neat soap is commonly achieved using
centrifugation.
After centrifugation, the remaining caustic
or residual alkalinity in the separated neat
soap is neutralized through the accurate
addition of fatty acid in a steam-jacketed
mixing vessel (crutcher)
421
CPB 303O3 (SEPT 2015)
422
Fatty Acid Neutralization

Step 1: Hydrolysis
The reaction is carried out under conditions
where water possesses appreciable
solubility (10 25%) in fats and oils.
In practice, this is achieved under high
pressure 4 5.5 MPa (580800 psi) and
with high temperatures (~240270C) in
stainless steel columns.
ZnO is sometimes added as a catalyst to the
feedstock fats and oils to facilitate the
reaction.
423

Step 1: Hydrolysis
The fat and oil feedstock is injected at the

bottom and water is injected at the top of
the column.
As these materials intermix at the high
temperatures and pressures employed, the
ester linkages in the fats and oils hydrolyze
to create fatty acids and glycerol.
The newly formed fatty acids continue to
rise up the column, while the resulting
glycerol is carried (washed out) downward
with the water phase.
424

Step 1: Hydrolysis
The hydrolyzer process provides around

99% efficiency for the conversion of the fats
and oils to fatty acids and glycerol, and
requires around 90-min residence time.
This fatty acid is passed into a vacuum
dryer stage where the water is removed
through vaporization and the fatty acid
cooled as a result of this vaporization
process.
The dried product stream is then passed to
a distillation system.
425

Step 1: Hydrolysis
The distillation system allows for improved
fatty acid quality, i.e., odor and color,
through the separation of the fatty acid
from partially saponified fats and oils, the
Zn catalyst, and odor and color bodies.
The vaporized fatty acids are then passed
through a series of cold water condensers
for fractionation and collection.
426

A heated fatty acid blend (5070C) and
causticsaltwater (2530C) streams are
metered into some form of a high shear
mixing system, commonly referred to as a
neutralizer.
The mixed stream heats to between 85C
and 95C on account of the latent heat of
reaction and is pumped into a receiver tank
that effectively mixes the soap through both
a recirculation system and agitation.
427

The resulting neat soap is pumped into
storage tanks or to the finishing
operations.
428
Soap Formulation: Soap

Bars
Primary surfactant is sodium salts of
fatty acid contain 70% - 80% of
soap.
Soap bars contain 8% - 20% water,
0.5% - 1% NaCl and low levels of
glycerol.
429

Bars Additives
Free fatty acid
Alkaline in nature
Manufacturing process yield base soap
having a very slight excess of free caustic.
Free fatty acid such as coconut or palm
kernel is added to neutralize the slight
excess of caustic.
Glycerols
Added into formulation (10%) to change

significantly the consumer skin softness,
and smoothness perception
430

Bars Additives
Colorants, dyes and pigments
To modify the appearance of bar soap
through the incorporation of various
colorants and opacifiers.
Most common used is titanium dioxide
(<0.8%).
Fragrance
To mask the fatty base odor of the soap.
In the range of 0.7% to 1.5%
431

Bars Additives
Chelants and antioxidants
To minimize the oxidation of the base soap
and other minor ingredients in soap bars.
Soap, fatty acid and fragrances are
susceptible to oxidation during aging.
Chelants (0.1% to 0.2%) is used to improve
oxidative stability through the
complexation of trace metal.
Example chelants: pentasodium
diethylenetriaminepentaacetic acid (DTPA),
citric acid.
432

Bars Additives
Chelants and antioxidants
Antioxidants (100 - 200 ppm) is used to further
improve product odor and color stability.
Example antioxidants: butylated hydroxytoluene
(BHT)
Mildness and skin additives

To improve the skin mildness of the product by
decreasing the level of soap and surfactant in
the bar.
Examples: laurate and quatenary amines
compound
433

Bars Additives
Antimicrobial agents
To provide additional deodorant protection

through their residual effectiveness on
suppressing the growth of odor-causing
bacteria.
Deposit on the skin during washing process
and provide a reservoir of active
ingredients that is effective at suppressing
bacterial growth between washing.
Examples: trichlorocarbanalide (TTC),
trichlorohydroxydiphenyl ether (TCS)
Used at concentration of 0.25% to 1.5%.
434
OILS AND FATS

APPLICATION
RENEWABLE ENERGY
Disadvantage of biodiesel
Slightly higher fuel consumption due to the lower calorific value of biodiesel.
Slightly higher nitrous oxide (NOx) emissions than diesel fuel.
Higher freezing point than diesel fuel. This may be inconvenient in cold climates.
It is less stable than diesel fuel, and therefore long-term storage (more than six months) of
biodiesel is not recommended.
May degrade plastic and natural rubber gaskets and hoses when used in pure form, in which
case replacement with Teflon components is recommended.
It dissolves the deposits of sediments and other contaminants from diesel fuel in storage
tanks and fuel lines, which then are flushed away by the biofuel into the engine, where they
can cause problems in the valves and injection systems. In consequence, the cleaning of
tanks prior to filling with biodiesel is recommended.
However, these disadvantages are significantly reduced when biodiesel is used in blends with
diesel fuel
Raw Materials for Biodiesel

Production
Rapeseed/Canola
Soybean
Oil Palm
Sunflower
Peanut
Jatropha
Microalgae
Flax, cotton,
safflower, castor seed,
coconut, etc
Biodiesel Production Process

Biodiesel is produced from vegetable oils or animal fats
and an alcohol, through a transesterification reaction
A catalyst is used to accelerate the reaction (can be acid,
basic or enzyme)
generic
transesterification
reaction
Basic
transesterification
reaction with
methanol
Transesterification Reactions
for Biodiesel Production
Basic. Most frequently used at all production scales.
Acid. Less frequent in industrial production,
sometimes used a first stage with highly acidic raw
materials.
Enzymatic. Less used; the enzymes are usually
lipases.
Stages of Biodiesel Production

Process
1.
2.
3.
4.
5.
Treatment of raw materials

Alcohol-catalyst mixing
Chemical reaction
Separation of the reaction products
Purification of the reaction products
Treatment of raw materials

The content of free fatty acids, water and nonsaponificable substances are key parameters to
achieve high conversion efficiency in the
transesterification reaction.
The use of basic catalysts in triglycerides with high
content of free fatty acids is not advisable, since part
of the latter reacts with the catalyst to form soaps
Basic transesterification is viable if the content of
free fatty acids (FFAs) is less than 2%
An acid transesterification may be carried out as a
preliminary stage, to reduce the level of FFAs
Alcohol-Catalyst Mixing
Catalyst must be completely dissolved in the alcohol.
Sodium and potassium hydroxides are among the
most widely used basic catalysts.
The reaction is reversible, thus excess alcohol as a
reactant will shift the equilibrium to the right side of
the equation, increasing the amount of products
Usually, a 100% alcohol excess is used in practice,
that is, 6 mol of alcohol per mole of oil. This
corresponds to a 1:4 alcohol-to-oil volume ratio (R =
0.25).
The necessary amount of catalyst is determined
taking into account the acidity of the oil, by titration
Chemical Reaction
The chemical reaction takes place when the oil is
mixed with the alkoxide (alcoholcatalyst mix)
Since alcohols and oils do not mix at room
temperature, the chemical reaction is usually
carried out at a higher temperature and under
continuous stirring, to increase the mass transfer
between the phases.
The temperature for transesterification at
atmospheric pressure is usually in the range
between 50 and 60 C.
Separation of the Reaction

Products
Glycerin can be separated from the products
mixture by decantation
The mixture of FAME and glycerin forms two
phases immediately after the stirring of the
mixture is stopped.
Most of the catalyst and excess alcohol will
concentrate in the lower phase (glycerin), while
most of the mono-, di-, and triglycerides will
concentrate in the upper phase (FAME)
Separation of two phases can be conducted by
using gravity (decanter) or centrifugal separator
Purification of the Reaction

Products
After the separation of glycerin, the FAME
mixture contains impurities such as remnants of
alcohol, catalyst and mono-, di-, and triglycerides.
These impurities confer undesirable
characteristics to FAME, for instance, increased
cloud point and pour point, lower flash point, etc.
In consequence a purification process is
necessary for the final product to comply with
standards.
Purification of the Reaction

Products
Successive washing steps with water remove the
remains of methanol, catalyst and glycerin, since
these contaminants are water-soluble.
The first washing step is carried out with acidified
water, to neutralize the mixture of esters. Then, two
additional washing steps are made with water only.
The traces of water must be eliminated by a drying
step. After drying, the purified product is ready for
characterization as biodiesel according to
international standards.
An alternative to the purification process described
above is the use of ion exchange resins or silicates

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SECTION OF CHEMICAL ENGINEERING TECHNOLOGY

MALAYSIAN INSTITUTE OF CHEMICAL AND BIOENGINEERING TECHNOLOGY

What is oils and fats

Importance of oils and fats

Sources of oils and fats

Chemically synthesized from

Worlds oils and fats production in 2011

Vegetable Oils: Oil Content, Yield, and Producing Areas

Vegetable Oils: Oil Content, Yield, and Producing Areas

2.1. Glycerides (acylglycerols)

2.2. Fatty acids

Structure, systematic, trivial, and shorthand names of some

Saturated fatty acids

Systematic, trivial, and shorthand names and melting

Systematic, trivial, and shorthand names and melting

Unsaturated Fatty Acids

Natural sources of mono-unsaturated fatty acids

Oleic acid: in most plant and animal lipids e.g

Natural sources of poly-unsaturated fatty acids

Cis and trans fatty acids

Naturally occurring fatty acids are generally in the cis

2.3. Phospholipids (phosphatides)

2.4. Tocopherols & Tocotrienols

Structure of Tocopherols & Tocotrienols

Tocopherols & Tocotrienols as antioxidant

Sources of Tocopherols & Tocotrienols

Molecular structure of sterols

Cholesterol is often linked with heart diseases

2.7. Other minor constituent

2.8. Main chemical composition

Palm Kernel Oil

Cocoa Butter Oil

Lard (Pork Fat)

Cod Liver Oil

C12:0 lauric, C14:0 myristic, C16:0 - palmitic, C18:0 stearic

3. Physical properties of fats

Glycerol Free fatty acids

Glycerol Sodium salts of

Alkaline hydrolysis produces glycerol and salts of fatty

It is a type of addition reactions accepting

Rancidity (caused by oxidation)

Types and Causes of Rancidity

CPB 30303 (SEPT 2015)

It results from slight hydrolysis of the fat by

CPB 30303 (SEPT 2015)

CPB 30303 (SEPT 2015)

CPB 30303 (SEPT 2015)

Hazards of Rancid Fats

CPB 30303 (SEPT 2015)

PALM OIL MILL PROCESSING

PALM OIL MILL PROCESSING

PALM OIL MILL PROCESSING

TRADITIONAL CRUDE PALM OIL PROCESSING

MODERN CRUDE PALM OIL PROCESSING

CRUDE PALM OIL RECOVERY

Effluent Treatment Plant

View FFB Grading

CPB 30303 (SEPT 2015)

CPB 30303 (SEPT 2015)

CPB 30303 (SEPT 2015)

4. Digestion and Pressing

Oil Recovery Plant

4. Digestion and Pressing

4. Digestion and Pressing