C3140 – Kimia Industri

By
Assoc. Prof. Dr. Sharifah
Bee Abdul Hamid

Part 3
 Topics to be covered (P3)
Š Processing of Vegetable Oil Š Case Study
„ Oil Refining and Treatment „ Palm Oil Processing
z Degumming and Dewaxing „ Palm Kernel Oil
z Neutralization Extraction
z Washing and Drying
z Bleaching and Filtration
z Winterization and Stearin
removal
z Deodorization
Š Oil Hydrogenation and
Shortening
„ Hydrogen Injection and
Autoclaving
„ Cooling and Filtration
„ Refining of Oil Shortening
 Introduction (2)
The palm fruit looks
like a plum.

The Palm Fruit yields two

kinds of oils:

• The outer fleshy

Mesocarp contains about
49% Palm Oil (C16 &
higher)

• The Kernel (which is

inside a hard shell) gives
about 50% Palm Kernel
Oil (C14 & lower which is
similar to coconut oil)

Each oil palm fruit consists of a hard kernel

(seed) inside a shell (endocarp) which is
surrounded by a fleshy mesocarp.
 Introduction (4)

Š After the milling process the oil is collected in large

tanks and transported by tankers for processing into
cooking oil, cosmetic quality oil or soap.
Š The oils obtained are:
„ Refined Bleached Deodorized (RBD) Palm Olein
„ Refined Bleached Deodorized (RBD) Super Olein
„ Refined Bleached Deodorized (RBD) Palm Stearin
„ Lauric Oil
 Introduction (7)
Š What is a fat?
„ Vegetable cooking oils and animal fats consisting
mainly of triglycerides.
Š What are triglycerides
„ Triglycerides are chemical compounds consisting of
one molecule of glycerol and three fatty acids.

Example of fatty acid Glycerol Trigylcerides

„ Triglycerides have lower densities than water, and at

normal room temperatures may be solid (called "fats“)
or liquid (called "oils").
Oil & Fats Market - General (1)
OILS/FATS 2000 2001(e) +/-% 2002(f) +/-%
Palm Oil 21,810 23,453 7.5 23,750 1.3
Palm Kernel Oil 2,683 2,897 8.0 2,951 1.9
Soya bean Oil 25,516 27,592 8.1 29,495 6.9
Cottonseed Oil 3,841 3,997 4.1 4,419 10.6
Groundnut Oil 4,543 4,932 8.6 5,579 13.1
Sunflower Oil 9,648 8,340 (13.6) 7,177 (13.9)
Rapeseed Oil 14,395 13,743 (4.5) 13,570 (1.3)
Corn Oil 1,965 2,017 2.6 2,190 8.6
Coconut Oil 3,282 3,571 8.8 3,469 (2.9)
Olive Oil 2,545 2,694 5.9 2,550 (5.3)
Castor Oil 495 524 5.9 475 (9.4)
Sesame Oil 717 737 2.8 755 2.4
Linseed Oil 697 639 (8.3) 645 0.9
Total vegetable oils 92,137 95,136 3.3 97,025 2.0
Butter 6,016 6,059 0.7 6,198 2.3
Tallow 8,248 8,195 (0.6) 8,321 1.5
Fish Oil 1,427 1,173 (17.8) 1,208 3.0
Lard 6,823 6,957 2.0 7,140 2.6
Total animal oil / fats 22,514 22,384 (0.6) 22,867 2.2
GRAND TOTAL 114,651 117,520 2.5 119,892 2.0
 Chemical Composition of Fats

Š Major Component
„ Triglycerides
Š Minor Components
„ Free Fatty Acids
„ Phosphatides
„ Sterols
„ Fatty Alcohols
„ Tocopherols & Tocotrienols
„ Carotenoids & Chlorophyll
„ Squalene *
 Chemical Composition of Fats (1)

Š Triglycerides (Major component )

„ Properties of fats and oils are dependent on the melting point
and degree of unsaturation from the component fatty acids
„ Generally, unsaturated fatty acids are more chemically reactive
and have lower melting points than the corresponding saturated
fatty acid (i.e., carbon chain of the same length)
„ Examples are shown in table below:

Fatty Acid Structure (the R groups in Triglycerides) Ratio

Stearic Acid CH3(CH2)16COOH 18:0

Oleic Acid CH3(CH2)7 CH=CH(CH2)7COOH 18:1n-9

Linolenic CH3CH2CH=CHCH2CH=CHCH 18:3n-3

Acid 2CH=CH(CH2)7COOH
 Chemical Composition of Fats (2)

Š Triglycerides (Major component) – (Continued)

„ Fats (generally from animal source) are triglycerides
that are solid @ RT due to saturated fatty acids
„ Oils (generally from plant source) are liquid @ RT due
to the unsaturated fatty acids

*This reaction is called esterification

*The reverse reaction is called hydrolysis

 Simple & Mixed Triglycerides
Š Triglycerides (Major component ) - (Continued)
„ Most fats & oils are mixed triglycerides that contain
two or three different fatty acids

A Simple Triglyceride A Mixed Triglyceride

 Chemical Composition of Fats (3)

Š Minor Components
„ Mono- and Diglycerides
z Used frequently as emulsifiers
z Prepared commercially by the
reaction of Glycerol +
Triglycerides or Esterification
of Glycerol + Fatty Acids
z Presence in palm oil affects
crystallization behavior of the
oil
 Chemical Composition of Fats (4)

Š Minor Components
Fatty Acids
„ Free Fatty Acids (FFA) O OH
O OH

C
z Unattached fatty acids C
CH 2
H 2C H 2C
(several %) present in fats CH 2
CH 2
H 2C
& oils CH 2
H 2C

CH 2

z Levels of FFA are H 2C H 2C

CH 2
CH 2
reduced in the refining H 2C
HC

HC CH 2
process CH 2
CH
H 2C

z Refined fats & oils ready CH 2

H 2C CH

H 2C
H 2C
for use as food usually CH 2
CH 2

H 2C
have a free fatty acid H 3C CH 3

content of only a few Myristic 14:0 Linoleic 18:2w6 (18.2 9c12c)

hundredths of 1%
 Chemical Composition of Fats (5)

Š Minor Components
„ Phosphatides
z Consist of alcohols
(usually glycerol) + fatty
acids + phosphoric acid+
nitrogen-containing
compound
z Refining removes
phosphatides from the fat
or oil
 Chemical Composition of Fats (6)

Š Minor Components
„ Sterol
z Also referred to as steroid
alcohols
z Occur in both animal fats
(primarily as cholesterol) &
vegetable oil sterols (collectively
termed as phytosterols)
z In palm oil, the amount of
sterols present is far lower than a
lot of other vegetable oils
 Chemical Composition of Fats (7)

Š Minor Components
„ Fatty Alcohols
z Long chains alcohols of little importance in most
edible fats

Fatty alcohols 22 to 32C - even

CH3(CH2)yCH2OH
(primary) numbered

Fatty alcohols 23 to 33C - odd

CH3(CH2)xCHOH(CH2)yCH3
(secondary) numbered
 Chemical Composition of Fats (8)

Š Minor Components
„ Tocopherols & Tocotrienols
z Vitamin E should be used as the generic descriptor for all
tocol & tocotrienol derivatives exhibiting biological activity
of a tocopherol.
z One of the most important phytonutrients in edible oils
z Consists of eight naturally occurring isomers, a family of
four tocopherols (alpha, beta, gamma and delta) and four
tocotrienols (alpha, beta, gamma and delta) homologues.
 Chemical Composition of Fats (9)

Š Minor Components
„ Tocopherols & Tocotrienols (Continued)
z All the eight isomers share some important traits:
Š The head, or chroman ring in technical term
Š The tail, which is called the phytyl tail for tocopherols
Š The active group on the head of the molecule, which is
called the hydroxy group
 Chemical Composition of Fats (10)
Š Minor Components
„ Carotenoids and Chlorophyll
z Carotenoids are a class of natural fat-soluble pigments found in
plants
z Carotenoids are usually red, orange, or yellow pigments
z Responsible for coloration in plants & fruits
z The structure of a carotenoid ultimately determines what potential
biological function(s) that pigment may have Carotenoids are
defined by their chemical structure
z Majority carotenoids are derived from a 40-carbon polyene chain,
which could be considered the backbone of the molecule (figure
below)
 Chemical Composition of Fats (11)

Š Minor Components
„ Carotenoids and Chlorophyll - (Continued)
z Chlorophylls are greenish pigments
z Contains a porphyrin ring (a stable ring-shaped molecule
around which electrons are free to migrate)
z Several kinds of chlorophyll: Chorophyll “a”, “b”, “c”

The most important being chlorophyll "a"

This molecule makes photosynthesis
possible, by passing its energized
electrons on to molecules which will
manufacture sugars.
 Physical Properties of Oil & Fats (4)
Factors Affecting the Physical Properties of Oil & Fats:
Systematic Name Common No. of Melting Typical Fat
of Saturated Name Carbon Point ° C Source
fatty acids Atoms*

Ethanoic Acetic 2 -- -- Š Length of Carbon

Butanoic Butyric 4 -7.9 Butterfat Chains in Fatty
Hexanoic Caproic 6 -3.4 Butterfat Acids (continued)
Octanoic Caprylic 8 16.7 Coconut oil „ As the length of
Decanoic Capric 10 31.6 Coconut oil
the saturated
Dodecanoic Lauric 12 44.2 Coconut oil
fatty acids
Tetradecanoic Myristic 14 54.4 Butterfat,
coconut oil increases, the
Hexadecanoic Palmitic 16 62.9 Most fats melting point
and oils also increases
Octadecanoic Stearic 18 69.6 Most fats
and oils
Eicosanoic Arachidic 20 75.4 Peanut oil
Docosanoic Behenic 22 80.0 Peanut oil

*A number of saturated odd and even chain acids are present in trace quantities in many fats and oils.
 Physical Properties of Oil & Fats (5)
Factors Affecting the Physical Properties of Oil & Fats:
Systematic Name Common # of # of Mpt
of Unsaturated fatty Name Double C °C Typical Fat Source
acids Bonds Š Length of Carbon
9-Decenoic Caproleic 1 10 - Butterfat Chains in Fatty
9-Dodecenoic Lauroleic 1 12 - Butterfat Acids
9-Tetradecenoic Myristoleic 1 14 18.5 Butterfat „ Coconut oil contains
9-Hexadecenoic Palmitoleic 1 16 - Some fish oils, beef fat
almost 90%
saturated fatty acids
9-Octadecenoic Oleic 1 18 16.3 Most fats and oils with a high
9-Octadecenoic* Elaidic 1 18 43.7 Partially hydrogenated proportion of
oils relatively short
chain low melting
11-Octadecenoic* Vaccenic 1 18 44 Butterfat fatty acids, is a clear
9,12-Octadecadienoic Linoleic 2 18 -6.5 Most vegetable oils liquid at 80°F
9,12,15- Linolenic 3 18 -12.8 Soybean oil, canola oil „ In contrast, lard
Octadecatrienoic which contains only
9-Eicosenoic Gadoleic 1 20 - Some fish oils
about 37%
saturates, most with
5,8,11,14- Arachidonic 4 20 -49.5 Lard longer chains, is
Eicosatetraenoic semi-solid at 80ºF.
13-Docosenoic Erucic 1 22 33.4 Rapeseed oil

Melting properties of triglycerides are related to their fatty acids

 Introduction
Š To produce a clean, attractive looking and palatable oil or fat by
removing ‘impurities’ which cause the oil to have an unattractive
colour and taste.
Š Impurities in crude vegetable oils can be classified into 4 groups:
„ Hydrolytic, e.g. moisture, dirt, free acids, partial glycerides and enzymes
„ Oxidative, e.g. metals, oxidation products, pigments, tocopherols and
phosphatides
„ Catalyst poisons, e.g compunds containing nitrogen, sulphur and halogens.
„ Hydrocarbons, e.g. terpenes, resins, waxes and unsaturated compunds
Š Two methods to refine crude vegetable oil (CPO/CPKO)
„ Chemical/alkali refining
2 to 3 times more expensive, uses alkali to neutralise the free fatty acids,
which are then removed as soap
„ Physical refining
Subjects the oil to steam distillation under high temperature and vacuum.
 Crude palm oil

0.1%-0.2% ortho-phosphoric acid.

Impurities, odour, Degumming Temp: 85°C
colour component Time: 15 minutes

0.5%-0.2% Bleaching earth.

Bleaching Temp: 95°C
Time: 30 minutes

FAA, impurities odour, Filtration Temp: 60°C-70°C

colour component

Deodorization Temp: 240°C-270°C

Time: ± 30 minutes

Refined bleached and

deodorized palm oil

Flow chart for physical refining

 Physical/Steam Refining

Š Highly efficient, low operating cost and capital

cost, negligible effluent handling
Š Common steps:
„ Pre-treatment
z Gum conditioning
z Earth bleaching

„ Deacidification/deodorisation
 CRUDE PALM OIL

Soap Alkali-neutralization
stock NaOH

Acidulation NEUTRALIZED PALM OIL

using H2SO4
Bleaching Bleaching clay

Acid oil
NEUTRALIZED BLEACHING PALM OIL

Deodorization Steam
Temp: 220°C-240°C

NEUTRALIZED BLEACHING DEODORIZED PALM OIL

Flow diagram of chemical/alkali refining process for palm oil

 Oil Refining & Treatment
Caustic Soda Hot Water

Crude Oil Storage Free Acid Refined Oil

Washing Oil Drying Unit
Neutralization

Soap Stock Washing Water Fresh Bleaching

Earth
Edible
Oil Deodorizer Oil Winterization Filter Press Oil Bleaching*
For (0.1 – 1.5% clay)
Packing

Deodorizer distillate Spent Solid Clay

* Temperature @ 105oC
 Oil Refining & Treatment (1)
Š Crude oils usually contain undesirable constituents that needed to be removed to
make the oil suitable for edible use
Š The constituents are:
„ Free Acids
„ Coloring matter (pigments)
„ Odoriferous substances
„ Gummy substances
„ Waxes
Š The first three constituents are the basic impurities in all types of crude
vegetable oils
Š Generally, in Physical Refining Process
„ The oil bleaching proceeds the refining process.
„ The bleaching process removes coloring matter & phospholipids which can cause
problems during physical refining process
„ This process suits oils such as palm oil & soybean
Š For Chemical Refining Process
„ The oil bleaching process using bleaching earth follows the refining process of the oil
„ This methods generally suit oils like cottonseed
 Oil Refining & Treatment (2)
Degumming & Dewaxing
Š Amount of gums & waxes present in the crude oil depends on the type of
oilseed being processed
Š Oils with high levels of phosphatides (ex. Soybean) may be degummed
prior to refining
Š Degumming can be carried out by adding phosphoric acid solution to
help precipitate out the gums
Š In Soybean, the gums separated from the crude soybean is also a natural
emulsifier, i.e., lecithin
Š Sunflower oil contains some waxes that needs to be dewaxed @ low
temperature, solidified & filtered off prior to processing
Š Crude cottonseed oil is refined using NaOH to remove free acids &
acidic pigments which impart the dark color to the oil but degumming is
not necessary since the small amount of phosphatides present can be
removed easily during the chemical refining steps
Š These steps (degumming and/or dewaxing) can be added or excluded
according to the type of oil processed
 Oil Refining & Treatment (3)
Neutralization
Š Extracted Crude oils are usually acidic due to high levels of FFA
Š Removal via chemical method
„ FFA removed using varying concentration of caustic soda
depending on oil type & quality
„ A black semi-solid organic substance called mucillage is
obtained
„ Settles out from the neutralized crude oil together with the
gummy & coloring substances
„ Separated by:

z Gravity Settling
z Centrifuging
Š Removal via Physical method
„ FFA is distilled out of the crude oil @ high temperature &
low pressure
 Oil Refining & Treatment (4)
Washing & Drying
Š Refined oil from neutralization step normally
contains traces of entrained soap from the
heavier mucillage phase
Š This Oil is washed with hot water in 2 stages,
separated via centrifuge & dried under
vacuum
Š Final step is essential as any traces of water
can cause deactivaiton of the bleaching earth
used in the next stage of the refining process
 Oil Refining & Treatment (5)
Bleaching & Filtration
Š Bleaching of oils by adsorption involves the removal of
pigments which are:
„ Dissolved in the oil
„ Present in the form of dispersed colloidal particles
Š After adsorption step:
„ Oil is passed to filter press to separate it from adhering bleaching
clay & returned to the bleaching kettle for clarification
„ The cake of spent clay in the filter press is blown with air and steam
to recover as much as possible of the entrained oil
Š Adsorbents used are usually bentonite clay (Fuller Earth &
Tonsil Clays)
Š The desired amount of the Adsorbent (~1% of oil weight) is
used @ temperature range of 100 – 120oC
 Oil Refining & Treatment (6)
Winterization and Stearine Removal
Š Winterization is a process whereby material is crystallized &
removed from oil by filtration prevent clouding of the liquid
fraction @ cooler temperature
Deodorization
Š Purpose is to remove substances which cause undesirable
flavor or odor from the bleached oil
Š The oil stock is heated @ 250oC (by superheated steam)
under v. low pressure (6-12mm Hg)
Š The substance responsible for the odor is volatilized and
then condensed in a barometric condenser
Š Last step of refining crude oil
 Oil Refining & Treatment (7)
Aid Effect Mode of Removal
Sodium hydroxide Refining aid Acid neutralization
Carbon/clay Bleaching aid Filtration
(diatomaceous earth)
Nickel Hydrogenation catalyst Filtration
Sodium methoxide Rearrangement catalyst Water or acid neutralization, SOME
filtration, and deodorization PROCESSING AIDS
USED IN
MANUFACTURING
Phosphoric acid Refining acids, metal Neutralization with base,
EDIBLE FATS AND
Citric acid chelators filtration, or water washing
OILS
Acetone Crystallization media for Solvent stripping and
Hexane fractionation of fats and deodorization
Isopropanol oils
Nitrogen Oxygen replacement Diffusion
Polyglycerol esters Crystallization None
modification
Silica hydrogel Adsorbent Filtration
Sodium lauryl sulfate Fractionation aid, Washing and centrifugation
wetting agent
Processing of Palm Oil & Palm
Kernel Oil