01 Fats and Oils

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Faculty of Chemical & Food Engineering

Food Engineering Program

Prepared By:
Fat and Oil Processing Technology
Tadlo Yitayew

1
Chapter 1- Introduction to Fats and Oils

Outlines

1. Introduction

2. Raw Materials

3. Commercially Important Oil Seeds

2
1. Introduction

What is fat?

What is oil?

What is the similarity and difference between them?

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Fats and oils are the group of lipids

Fats Oils

Solid at ambient temperatures Liquid at ambient temperatures

Found in animals Found in marine animals & plants

Saturated Unsaturated
 The composition of any given fat or oil depends on the source (plant or animal) as
well as on dietetic and climatic factors
 example, lard from corn fed hogs is more highly saturated than lard from
peanut fed hogs
 Palmitic acid is the most abundant of the saturated fatty acids, while oleic acid is
the most abundant unsaturated fatty acid 4
 They are naturally occurring esters (fatty acids + glycerol’s)

 Fats and oils are called triglycerides (triacylglycerols) because they are esters composed
of three fatty acid units joined to glycerol, a trihydroxy alcohol

Functional Groups

 If all three OH groups on the glycerol molecule are esterified with the same fatty acid, the
resulting ester is called a simple triglyceride 5
Fatty Acids

 Fats and oils are derivatives of fatty acids

 Fatty acids are carboxylic acid consisting of


hydrocarbon chain & terminal carboxyl group

 Most fatty acids have common name,


indicates the origin of the acid, e.g.
 Palmitic acid from palm oil

 Oleic acid from olive oil

 Linoleic and linolenic acid from linseed oil

 Ricinoleic acid from castor oil


 Common names are simple, however they used only for a single structure (not for groups of
isomeric compounds) and it does not provide structural information 6
 Fatty acids also have systematic names, which shows

 The number of carbon atoms

 The number, position, type and configuration of unsaturated centers

 For example, oleic acid is correctly named cis-9-octadecenoic acid

 This systematic name indicates

 oic indicates carboxylic acid

 octadec indicates the carbon number (18 carbon atoms)

 en indicated the double bond which is in the cis configuration and between carbon
atoms 9 (and 10) counting from the COOH group

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Saturated acids

 Short and medium chain acids (4:0 - 14:0)

 Milk fats contain all these acids and some vegetable oils

 The milk fats contain more of the shorter chain acids

 Palmitic (16:0) and stearic acids (18:0)

 Palmitic acid (16:0) is the most common of all the saturated fatty acids, however,
Stearic acid (18:0) is less common,

 Long chain fatty acids

 Saturated acids with more than 18 carbon atoms are rare

 Groundnut oil contains low levels (4-7%) of such acids including arachidic (20:0),
behenic (22:0) and lignoceric (24:0)
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Unsaturated fatty acids

1. Monounsaturated acids
 They have 16-22 carbon atoms

 Generally Δ9 or ω9 as a consequence of the presence of a very active Δ9

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2. Polyunsaturated acids
 Polyunsaturated fatty acids are hydrocarbon chains containing two or more double
bonds
 The characterization of PUFAs as either an n-3 PUFA or n-6 PUFA refers to the
position of the first double bond relative to the methyl end of the fatty acid
 Methylene interrupted polyene acids are the most common type of polyunsaturated
fatty acids

10
Saturated acids Unsaturated acids

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2. Raw Materials
 Various vegetables & animals can be used as a source of fats and oils

 The vegetable oils may be further subdivided into three categories

1. Byproducts: the crop is grown for another purpose other than seed oil (cotton, corn,
soybean, etc.)

2. Tree crops: slow to mature but produce crops regularly for many years (palm, palm
kernel, coconut, olive, etc.)

3. Crops: replanted each year to produce an annual harvest (rape/canola, sunflower,


groundnut, linseed, sesame, castor, etc.)

 Soybean, palm, rapeseed and sunflower are the most important oil seeds

 Cow, cattle, pig and fish are the most important animal source of fat and oils

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Commercially Important Oil Seeds

Soybean

 Soybean (Glycine max), is one of the richest


and cheapest sources of protein (79%) and oil
(18%)
 Oil is the minor product in terms of quantity
but in terms of value, oil has the greater value
 Soybean oil is an unsaturated oil containing
useful proportions of the two essential fatty
acids of linoleic and linolenic

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 Soybean oil is characterized by the presence of

Linoleic (53%)

Oleic (23%)

Palmitic (11%)

Linolenic (8%)

Stearic acids (4%)

 Due to its high level of linoleic acid (>50%) over half its triacylglycerols
contain two or three linoleic chains

 Most of the remainder have one linoleic chain


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Sunflower

 Sunflower seed oil is obtained from Helianthus annuus

 The oil normally contains


 60 - 75% of linoleic acid
 >90% of oleic and linoleic acids combined
 No linolenic acid
 It is widely used as a cooking oil and is valued as an
important component of soft spreads

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Palm oil

 Palm oil can be obtained from the fleshy endosperm and


palm kernel

 Palm trees are give higher oil yields, have a more


unsaturated oil

 The oil contains almost equal proportions of saturated


(palmitic ~44% and stearic ~4%) and unsaturated acids
(oleic ~39% and linoleic ~10%)

 The oil is used mainly for food purposes but finds some
nonfood uses as it is a source of valuable byproducts such
as carotene, and tocopherols and tocotrienols (vitamin E)
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 Palm oil with a melting range 21 – 27oC can be

 Crystallized to give solid (palm stearin, 25 - 35%, melting between 48 and 50oC) and

 Liquid fractions (palm olein, 65 - 70%, melting between 18 and 20oC)

 Palm olein is used as a high quality, highly stable, frying oil and the export of palm oil
from Malaysia is mainly in the form of palm olein

 Palm stearin is the less valuable component, but it can be used as a hard fat in the
production of spreads and as a vegetable alternative to tallow in the oleochemical
industry

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Rapeseed Oil (Canola Oil)

 The seed oil of Brassica napus or B. campestris was typically


rich in erucic acid (22:1) and the seed meal had an
undesirably high level of glucosinolates

 These components reduced the value of both the oil and the
protein meal but they have been bred out of modern rapeseed
which is now known as double zero or canola

 Rapeseed (of all kinds) is now the third largest source of oil,
after soybean oil and palm oil

 It contains palmitic (4%), stearic (2%), oleic (62%), linoleic


(22%) and linolenic (10%) acids and has less saturated acids
than any other commodity oil
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Sesame oil

 Sesame oil comes from the plant Sesamum indicum

 The seed has 40 – 60% of oil with almost equal levels of


oleic (range 33 - 50%, typically 41%) and linoleic acids
(range 33 - 50%, typically 43%) and some palmitic acid
(range 7 - 12%, typically 9%) and stearic acid (range 3 -
6%, typically 6%)

 The oil contains sesamin (0.1 - 1.1%) and sesamolin (0.1


- 0.6%) which together give the oil high oxidative stability

 It may be added to other oils to enhance oxidative


stability such as in the preparation of frying oils

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Butter Fat
 Milk fat has a complex fatty acid composition with high levels
of short and medium chain acids and with many uncommon
fatty acids, including those with trans unsaturation, present at
low levels

 Milk fat is mainly triacylglycerols (97-98%) along with some


free acids, monoacylglycerols and diacylglycerols

 Also cholesterol (0.2-0.4%), phospholipids (0.2-1.0%) traces of


carotenoids, squalene and vitamins A and D are present

 The fatty acid composition of milk depends on the diet of the


cow so that there is a difference in composition of milk fat

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Lard

 Lard is the body fat of pigs and is typically rich in


palmitic (26%) and oleic acid (44%) with lower levels
of linoleic (11%) and palmitoleic acid (5%)

 Compared with vegetable oils, animal fats are rich in


cholesterol and deficient in natural antioxidants

 Despite their relatively saturated nature, therefore,


animal fats have to be stabilized against oxidation by
addition of natural or synthetic antioxidants

21
Tallow
 Tallow is mainly fat from cattle

 It may contain some fat from sheep but should be free of pig fat

 The major fatty acids in the higher quality edible grades include

 Myristic (1-8%)

 Palmitic (17-37%)

 Stearic (6-40%)

 Oleic (26-50 percent, including isomeric acids with trans unsaturation)

 the fat also contains acids with an odd number of carbon atoms, branched chain acids,
and linoleic acid (up to 5%)

22
Fish oils

 Fish oil comes from many types of fish

 It is rich in two important omega-3 fatty acids called eicosapentaenoic


acid (EPA) and docosahexaenoic acid (DHA)

 The benefits of fish oil seem to come from its omega-3 fatty acid content

 Fish that are especially rich in these oils include mackerel, herring, tuna,
and salmon

 The body doesn't produce many of its own omega-3 fatty acids

 Omega-3 fatty acids reduce pain and swelling, and also prevent
the blood from clotting easily

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Chapter 2: Extraction and Refining Process

Outlines
1.Cleaning, Drying and Storage
2. Pretreatments of oil seeds
3. Oil seeds extraction
4. Crude oil refining process

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1. Cleaning, Drying and Storage

 The crude fats and oils can be extracted from

 Oilseeds, fruits and animal tissues

 However, the quality of raw material has influence the quality of oil extracted

 The most important quality parameters oilseeds during reception is

Percent impurity

Moisture content

 Proper handling, cleaning, drying and storage of oilseeds is important to processing


them into quality products

25
Cleaning
 At the time of harvest most oil seeds are likely to contain contaminants, that have inedible
components or variable physical characteristics

 The main contaminants are

 Unwanted parts of the plant

 Soil/dust particles, sand, stones, metallic particles

 Insects and their eggs, animal excreta, hairs, etc.

 Pesticides and fertilizers residues

 Microorganisms and their toxins


 Cleaning is required
 To produce high quality product and consumer health
 To keep process equipment from damaging
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 Cleaning is the unit operation in which contaminating materials are removed from food
substances

 Cleaning may occur before and after storage

 Cleaning before storage helps to minimize storage deterioration, which is aggravated by


the presence of a wide variety of contaminants

 Precleaning helps to improve the storage potential of the oilseeds by:

 Removing immature kernels by aspiration

 Removing microorganisms with dust light impurities & shriveled kernels

 Separating insect infested kernels and insect fragments

 Cleaning can be accomplished by screening, aspiration, destoner and magnetic separator

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Drying

 The moisture content of oilseeds at the time of harvest is usually high which affects their
storage
Thus, the oilseeds need to be dried prior to their storage

 High moisture seeds respire faster as a consequence the oxygen uptake increases
leading to the
 Generates excessive heat that raises the temperature of seed and thereby
accelerates its deterioration
 Oxidation of polysaturated fatty acids which reduces the nutritive value and
organoleptic quality of oils present in oilseeds

 Therefore, the seed should be dried below the critical moisture (8.5 - 13), but the drying
temperatures should not exceeds 63oc
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Storage

 The moisture content of oilseeds, RH and T of storage condition are the most
important factor in proper storage of oilseeds

 In the case of inadequate storage

 The triglycerides may be decomposed (favor the activity of lipolytic enzymes that
increases the FFA content)

 The non-triglyceride constituents of the seeds also degrade and produce oil
soluble pigments which darken the color of the oil and undesirable flavor changes

 Growth of MOs and production of metabolites and mycotoxins, particularly


aflatoxins

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2. Pretreatments of Oilseeds

 Treatment of the oil bearing seeds before oil extraction has multiple advantages

 Seeds pretreatment increase

 Oil yield

 Oxidative stability

 Recovery of bioactive compounds recovery

 Commonly reported seeds pretreatment techniques include dehulling, sorting, cleaning,


grinding/milling and preheating

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Dehulling (decortications)

 The hulls of oilseeds are fibrous and have low oil content (<1%)
 The hulls
 Reduce the total oil yield by absorbing or retaining oil in the pressed cake
 Therefore, the outer husk or shell should be separated from the seeds prior to
extraction
 This process is called dehulling or shelling or decorticating
 Dehulling increases oil production efficiency, capacity of the extraction equipment and
reduces wear in the expeller
 Wax and color compounds present in the husk also entered to the extracted oil, which
are not desirable in edible oils and need to be removed during the refining process

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Size reduction and flaking

 Size reduction of oilseeds facilitate hull removal, heating, drying, flaking and extraction

process

 The oil is quite strongly bound within other components

 Flaking ruptures seed cellular structure to liberate the oil from its surroundings

 Flaking, increase surface area to volume ratio, thus,

 Reduce distance for diffusion and

 The cell wall becomes more permeable to release the oil

 Flaking is essential for preparing oil seeds before solvent extraction

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Cooking/Tempering

 Oilseeds are cooked or tempered to release oil from the cells and inactivate enzymes
 Oilseeds are heated or cooked (80 - 105°C) in order to:

1. Increase the yield (facilitate the extraction)


 The cell wall weaken and complete breakdown of the oil cells
 Coagulates of seeds proteins, causes coalescence of oil droplets and making
the seed permeable to the flow of oil
 Decreases the affinity of oil for the solid surfaces of seed
2. Improve processing quality (oil and cake quality)
 Destroying moulds and bacteria
 Destroying enzymes (lipase, lipoxygenase, myrosinase,etc.)

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3. Improve nutritional value and safety
 Destroys the moulds and bacteria
 Destroying the heat labile anti nutritional factors to improve the nutritive
value of oilseed cake
 Reducing the viscosity of the oil
 Increasing the plasticity of crushed seeds

 Normal cooking of oilseeds has little effect on oil color, however, over cooking
of oilseeds produces oil and cake of dark color

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4. Extraction

 Oil can be extracted from a number of fruits, nuts and seeds for use in cooking and
soapmaking

 Oilseeds and nuts should be properly cleaned to remove sand, dust, leaves and other
contaminants before extraction, to reduce the undesirable effect

 Oil can be extracted from its source by using

 Traditional methods  The choice of extraction method depends upon


 The quantity of oil present in the oilseed
 Mechanical press
 The quantity of oil that can remain in the cake
 Solvent extraction
 The investment capital available

 The environmental laws regarding emissions of organic compounds


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Traditional Methods
 Traditionally, oil can be extracted from its source by milling and boiling it in water

 The traditional extraction methods is inefficient, often yielding low amount of oil, below
the range of plant oil content

 In the traditional extraction method, the major operations are

1. Shelling of the pods/winnowing

2. Grinding of seeds to form paste

3. Mixing the paste with water/boiling to extract oil

4. Scooping of oil and drying the oil by heating

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Mechanical Pressing

 Mechanical expression involves the application of


pressure (using hydraulic or screw presses) to force oil
out of an oil bearing material

 Mechanical press methods are often used to extract oil


from oilseeds having oil content >20%

 Increasing the operating pressures, durations and


product bulk temperatures, increases the oil yield

 With regard to oil yield, screw presses have an advantage


over hydraulic presses for churning out slightly higher
yields, in addition to their continuous mode of operation

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 Double pressing of cooked oilseeds, results in low oil content of the cake (3-4%)

 Choice of double pressing depends on

 The economics of the processes

 The end use of the cake

 Excessive use of pressures to express more oil in single/double pressing affects

 The quality of oil

 The nutritional value of the oilseed cake

 Reduces the capacity of expellers

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 Mechanical press methods have low operation cost and producing high quality light
colored oil with low concentration of free fatty acids (FFAs)

 However, it has a relatively low yield compared to solvent extraction and it is time
consuming and labor intensive

 There are two types of mechanical press methods namely

 Cold press

 Hot press

 Cold press is carried out at low temperature (below 500C) and pressure, whereas the hot

press method is carried out at elevated temperature and pressure

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 Cold pressed oils are safer than hot pressed seed oils

 The high temperature are decreased oxidative stability, degradation of valuable oil

components and reduced oil keeping quality

 In cold pressed oils, the purity and natural properties of seed oils are preserved

 Valuable nutraceuticals like phytosterols and tocopherols are retained

 Hot press methods give higher oil yield due to decreased in oil viscosity

 Thus high temperature increases the efficiency of the extraction process about 80%

 But they may also causes oil degradation

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Prepress Solvent Extraction

 The prepress solvent extraction technique is used to extract oil that are first expelled at
low pressure from oilseeds

 In prepress solvent extraction

 A portion of oil is extracted with expellers (low pressure)

 The remainder of the oil (the prepress cake) is extracted with an organic solvent

 Generally, prepress solvent extraction is a combination of mechanical and solvent


extraction method

41
Solvent extraction

 The solvent extraction method is commonly applied to oilseeds with low oil content
(<20%)

 It is the most efficient methods in vegetable oil extraction, with less residual oil left in the
cake

 Solvents commonly used are hexane, diethyl ether, petroleum ether and ethanol

 The choice of solvent is based mainly on

 The maximum leaching characteristics of the desired solute substrate

 Solvent-Solute ratio

 Relative volatility of solvent to oil

 Cost and market availability


42
 Oil extraction ability of solvent during solvent extraction is enhanced with

 Increase in extraction time

 Solvent-Solute ratio

 The disadvantages of solvent extraction method is that

 Long extraction times

 Relatively high solvent consumption, high investment, high energy requirement

 Plant security problems, emission of volatile organic compounds into the atmosphere

 In addition, the removal of organic solvents brings additional cost and labor

 For solvent extraction method, flaking is important to rapture the cell walls of oilseeds

 Heating before flaking makes the seed particle easy for subsequent flaking or pressing

 Proper plastic texture is necessary to produce thin, fines and maximal cell distortion to

makes them soft and pliable enough to be flaked 43


 For better oil extraction

 Good contact and penetration of the solvent

 There must be enough clean solvent to dissolve the solute

 Enough time and heat to quickly dissolve more solute

 The oilseeds extraction involves a combination of leaching, diffusion, and dialysis

 The transfer of oil from distorted cells probably is governed by capillary flow and
rate of flow depends on viscosity

 Intact undistorted cells and must be transferred by diffusion, characterized by


slow extraction

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 Factors affecting rate of extraction is

 Flake thickness

 Solvent temperature

 Extraction time

 Soxhlet extraction process is example of extracting vegetable oil from


oily materials

 The major advantage of the Soxhlet extraction is solvent recycling (over


and over) during extraction

 In solvent extraction is the separation of solvent from the oil is required

 Solvent is separated from the crude oil by distillation, the miscella is


heated under vacuum to evaporate the solvent

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5. Refining

 These compounds are not toxic, but their


presence in oils is undesirable
 They affect the stability & sensorial
acceptability of consumers (bad taste
& smell)

 These affects the safety of products

 The oil must be odorless, neutral in taste,


transparent, colorless and it must be safe
and free from contaminants

 Treatment that eliminates undesirable and toxic components in


crude oils is known as refining 46
 Refining is practically mandatory for crude oils that cannot be consumed as virgin oils to
provide a product with an attractive appearance, neutral taste, and more resistance to
oxidation

 Refining allows us to

 Obtain suitable oils for various industrial uses

 Getting rid of undesirable substances such as pesticide residues

 Minimizing oil loss during processing

 Increases the shelf life of oils

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 However, refining has several disadvantages

 The loss of substances responsible for healthy and pharmaceutical properties such as
tocopherols, phospholipids, squalene, polyphenols, and phytosterols
 The formation of undesirable compounds such as glycidyl ester, 3-MCPD-esters,
harmful trans fatty acids, and polymeric triacylglycerols

 These can directly influence the safety level of refined oils

 Crude oils can be refined using

 Chemical refining and

 Physical refining methods

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 Chemical refining follows six processes:

1. Degumming with the goal of the elimination of phospholipids and gums

2. Neutralization which allows the elimination of free fatty acids (FFA), phospholipids,
metals, and chlorophylls

3. Washing and drying in order to eliminate residuals of soaps and water

4. Bleaching aims at eliminating pigments, peroxides and residuals fatty acids and salts

5. Dewaxing aims in removing the waxes

6. Deodorizing which allows the elimination of volatiles, carotenoids and free fatty acids

 However, the chemical refining has several drawbacks


 Removing certain bioactive molecules (mainly of tocopherols & polyphenols), which
can act as antioxidants
 Requires higher cost and might result in the release of polluting effluents
49
Degumming

 Degumming is treating of crude oils with water or dilute acid (phosphoric or citric) to remove
phospholipids and other impurities

 Phospholipids or phosphatides are naturally present in oils

 Purpose of Degumming:

 To decrease oil losses (the emulsifying action of phospholipids )

 To prevent discoloration of oil

 Prevent crude oil settling during storage or transport

 Commercial Lecithin production

 Retard oxidative degradation of oil

 Generally, vegetable oils contains hydratable and nonhydratable phospholipids


50
 The degumming stage is focused on eliminating all compounds susceptible to becoming
insoluble through hydration (phospholipids, glycolipids, proteins, etc.)

 There are four types of degumming processes

 Water degumming

 Acid degumming

 Dry degumming

 Enzymatic degumming

51
Water degumming

 The main purpose of the water degumming process is to produce


an oil that does not deposit a residue during transportation and
storage

 In this process large part of hydratable and small proportion of the


NHP are removed

 The removed hydratable phospholipids (gums) are considered as


raw lecithin

 Too little water produces dark viscous gums and hazy oil, while
too much water causes excess oil losses through hydrolysis

 At higher temperatures the solubility of the phosphatides in the oil


is increased and at lower temperatures the oil viscosity increases
52
Acid degumming

 The oil is mixed with small quantity of acid such of phosphoric or citric acid to dissociate
nonhydratable phospholipids

 Two types of acid degumming

 Dry acid degumming

 Wet acid degumming

 Dry acid degumming is particularly suitable for processing oils with low gum contents such
as palm oil, coconut oil, palm kernel oil or animal fats

 In dry degumming, the oil is treated with an acid to decompose the phosphatide complexes
and then mixed with bleaching earth to absorb the gums and separated by filtration

53
 The benefits of the dry acid degumming process are

 Efficiency as a result of low energy consumption, low operation and maintenance costs

 Low investment costs

 Environmental friendly as no wastewater or soap stock occur

 Wet acid degumming

 It uses a combination of water and acid

 The nonhydratable gums, can be conditioned into hydratable forms with a degumming acid

 Suitable for processing for initially oils with higher gum contents (e.g. corn oil)

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 The acid liberates the NHP and forms a binding complex with the calcium and magnesium
divalent metal ions that can be removed with the aqueous phase

 Phosphoric and citric acids are used because they are food grade, sufficiently strong, and
they bind divalent metal ions

 Citric acid is usually preferable because it does not increase the phosphorus content in
the oil

 This process is beneficial as

 Centrifuges enable easy separation of gums in oil types with higher non-hydratable
gums contents (e.g. soybean oil)
 Reduce the consumption of bleaching earth

55
Dry degumming

 The dry degumming process is recommended for oils with a low phospholipid content

 The technique uses a concentrated acid (phosphoric or citric) combined with bleaching
earth (1 to 3 g/100g)

 The acid (0.05 to 1.2 g/100g) is dispersed in oil at 80°C

 This acid dissociates the nonhydratable phosphatides into phosphatidic acid, and it is
eliminated by centrifugation

 The remaining amount is further adsorbed through bleaching earth

 The degumming process combines the acid degumming step with the bleaching process,
thus eliminating the water addition and centrifugation of the gums

 Its main benefit is the lack of generation of aqueous effluents


56
Enzyme degumming

 Enzymatic degumming was first introduced by the German Lurgi Company as the
“EnzyMax process”

 The EnzyMax process can be divided into four different steps

1. Adjustment the optimal conditions for the enzyme reaction, i.e. optimal pH with a
citrate buffer and the optimal temperature

2. Addition of the enzyme solution

3. The enzyme reaction takes place

4. The separation of lysophosphatide from the oil at about 75°C

 The degumming enzyme changes the phospholipids into Lysophospholipids (NHP) & FFA

57
Neutralization
 Vegetable oils containing a high percentage of free fatty acids (hydrolysis/oxidation)

 The presence of these compounds in crude oils causes storage problem and result in an
undesirable color and odor in the final product

 Chemical refining with caustic soda neutralization and physical refining based on steam
distillation can be used to remove FFA

 During neutralization, the oil is treated with an alkali solution (caustic soda) that reacts
with the free fatty acids (FFA)

58
Washing and Drying
 This operation eliminates alkaline substances in the oil from coming out of the
neutralization as well as last metallic and phospholipids traces and other impurities

 Washing water should be hot (85–90°C) and should represent 5–15% of treated oil

 It is preferable to use softened water

 The oil free of gums, traces of soapstock, and other impurities, is pumped through a
plate heat exchanger where it is heated by steam

 It is then sent to the centrifugal mixer to be combined with water and further centrifuged
in a centrifuge for water washing

59
Bleaching

 The bleaching is a critical step in the refining process of oils

 The objective of bleaching is to reduce the levels of colored pigments (carotenoids and
chlorophylls)

 Bleaching also removes residue of traces of phosphatide, soap, phospholipid


contaminants, lipid peroxidation products, and other impurities

 To perform bleaching, adsorption bleaching clays, activated carbon, special silica, or a


combination of these are used

 The bleaching earth is the most popular adsorbent for decolorization of oil and the most
widely used adsorbent material by the oil industry

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Dewaxing or Winterization

 Waxes are esters of long chain primary alcohols and long fatty acids

 These acids have

 Low solubility in oils

 High melting point, usually crystalline during the winter season at low & room
temperature

 The wax generally does not negatively affect the functionality of the oil

 The presence of wax affects the quality aspect of the oil, which gives it a cloudy hazy
appearance especially during the winter season, due to the precipitation of dissolved
waxes

 The dewaxing process is also called winterization


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 The term winterization appears as during winter when the temperature is low, the waxes
present in the oil crystallize, thereby giving a hazy appearance to the oil

 The dewaxing process includes three main processing steps

1. The bleached oil should be heated to 55°C to make sure the oil is completely liquid

2. The oil is cooled slowly to 10–15°C, for several hours

3. The cooled oil is pumped into a filter machine to separate the wax from oil

 The filtration yields a clear liquid oil and the byproduct waxes

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Deodorization

 Deodorization is a simple distillation process, which allows the elimination of free fatty
acids and removes odors, different off flavor components, contaminants (pesticides, light
polycyclic aromatic hydrocarbons, and other volatile components)

 Deodorization also removes residues of mineral oil saturated hydrocarbons (MOSH) and
mineral oil aromatic hydrocarbons

 A deodorized oil is free of any taste, even pleasant ones

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 However, deodorization also has other negative effects

 Important bioactive molecules such as tocopherols, squalene, sterols, and


polyphenols may be removed
 The destruction of some essential nutrients; unwanted side reactions like cis – trans
isomerization (the double bond isomerizes from cis to trans), conjugation, and
polymerization
 Sometimes it generates other unwanted compounds

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Physical Refining
 The process consists of the same steps described in chemical refining, except for the alkali
neutralization process

 Chemical refining consists of removing free fatty acids by adding caustic soda and
separating the soap by centrifugation (mechanical separation), while physical refining,
removes free fatty acids and other compounds by steam distillation

 This process is also known as steam refining

 In general, physical refining includes the following three main processing steps:

1. Degumming to remove phosphatides

2. Bleaching and filtration to eliminate color pigments

3. Deodorization allows the elimination of free fatty acids and other volatile compounds

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Chapter 3 - Modification & Handling of the Fats and Oils

Outlines
1.Introduction
2.Physical Modification (Blending, Fractionation, Winterization)
3.Chemical Modification (Hydrogenation, Esterification)

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1. Introduction

 As natural products, fats and oils do not always have the properties required for

specialized purposes, and not optimized for their end use

 Modification offers the possibility of changing the properties of oils and fats

within wide ranges, thus making them suitable for many uses

 The processes that offer the possibility of modifying fats and oils are: blending,

fractionation, hydrogenation and interesterification

 The benefits of applying the processes include the possibility of stabilizing highly

unsaturated oils that can degrade easily as a result of oxidation

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2. Blending

 The mixing of oils and fats to:

 Produce blends with improved nutritional or physical properties

 Obtain the desired mix at minimum cost

 Mixtures of vegetable oils with appropriate fatty acid composition, sometimes containing
fish oils, and effective antioxidants are healthy oils

 Most spreads, for example, contain blends of two or more oils in order to achieve
desirable nutritional and essential physical properties

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3. Fractionation

 Fractionation is a process of adding value to an oil or fat

 Fractionation involves the separation of triacylglycerol under controlled cooling


conditions into olein and stearin fractions with distinct chemical and physical
properties, based on their melting point
 Why fractionation?

 To change physical properties and so increase the oil's range of usefulness


 To provide two or more useful new materials more useful than the natural product
 To remove an undesirable component to produce liquid oils that resist clouding at cool
temperatures

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 How we fractionate?
 Separation of fats & oils fractions is based on the solubility difference of triglycerides

 The type of triglycerides in the fat system and

 The FA composition and the distribution of the FA

 The successive stages of fractionation can be distinguished as:

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

 The cooling rate determines final crystal composition 71


 Crystals can exist in three main forms: α, β' and β in order of increasing stabilities and
melting points

 In general the oil crystallizes into the unstable α-form and then rapidly transforms into
the more stable β'-form, and much more slowly into the β-form

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Fractionation Methods

Dry fractionation

 Dry crystal fractionation process are used for separation of hard stearin and soft
olein fractions from natural products that contain high levels of stearin and olein

 Stearin fraction the crystals will be less soluble, higher melting and more saturated.

 Olein fraction the portion that remains liquid, more soluble, lower melting, more
unsaturated

 The principle is based on slowly cooling the oil under controlled conditions without
the aid of a solvent and then separation of two fraction using filtration,
centrifugation, hydraulic pressing
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Detergent Fractionation

 The basic principles is the same as dry fractionation

 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 stearin

 How aqueous detergent solution assist the separation?

 Wets the surface of the crystals and displacing the liquid oil

 An electrolyte (magnesium or aluminum sulfate) is added to the solution to assist in


uniting the liquid olein droplets

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Solvent Fractionation

 At a given temperature the solubilities of components


triacylglycerols differ markedly from each other

 In solvent fractionation

1. The fat dissolved or melted in a suitable solvent

2. Crystallizing out fat crystals from the solvent

3. Separating the fat crystals from the solvent

 Solvent fractionation result in:


 More efficient separation
 Improved yields
 Reduced processing times
 Increased purity
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4. Hydrogenation

 Number of double bonds in oils and fats affects physical property (melting point,
crystallinity)

 Generally, double bonds reduce the oil’s melting point

 Hydrogenation is a process of adding hydrogen atoms into double bonds of unsaturated


fatty acids, as a result the liquid oil becomes solid or semi solid

 Vegetable oil is hydrogenated with gaseous H2 in the presence of a metal catalyst


(usually nickel catalyst)
 If the hydrogenation is completely performed, all the double bounds are converted to the
saturated ones with the same carbon number

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 Oil is hydrogenated for two reasons :

1. To change physical/functional characteristics (melting point) of fats and oils (to


convert liquid oils or soft fats into plastic or hard fats)

2. To increase oxidative stability

 Undesirable consequence of hydrogenation of oil:

 Decrease nutritional value

 Formation of acids with trans unsaturation

 Hydrogenation of oil is complex reactions due to simultaneous reactions that occur:


1. Saturation of double bonds
2. Cis-/trans-isomerization of double bonds and
3. Shifts of double-bond locations, usually to the lower energy conjugated state

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 Hydrogenation can take place only when the three reactants (unsaturated oil, catalyst, and
hydrogen gas) have been brought together

 The hydrogen gas dissolved in the liquid oil and then diffuse to the solid catalyst surface

 Then the absorbed unsaturated fatty acid can react with hydrogen atom 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 triunsaturated, there may be
competition for the catalyst surface

 The di and triunsaturated are preferentially absorbed and partially hydrogenated to a


monounsaturate until their concentration is very low, permitting the monounsaturate to be
absorbed and reacted

 The variables that can affect the rate and results of the hydrogenation are temperature,
pressure, agitation, catalyst type & level, and source of oil
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5. Esterification

 Esterification includes chemical reactions where an ester in fat/oil is reacted with alcohol
(alcoholysis), acid (acidolysis), or another ester (interesterification or ester exchange)
 To generate a new ester

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Interesterification
 Interesterification of oil changes its molecular composition

 During interesterification, the fats and oils fatty acid esters react with other esters or FA
to produce new esters by an interchange of FA groups

 The interesterification processes can alter the original order of distribution of the fatty
acids in the triglyceride producing products with melting and crystallization characteristics
different from the original oil or fat
 Breakup of a specific glyceride

 Removal of FA at random

 Shuffling it among the rest of the FA pool

 Replacement at random by another FA


 Interesterification does not change the FA composition of the starting material but rearranges the
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FAs on the glycerol molecule
 The general types of interesterification or rearrangement are

1.Random rearrangement
 The fatty acid radicals freely move from one position to another in a single glyceride or from
one glyceride to another

2.Direct interesterification
 One or more of the triglyceride products of the interesterification reaction are selectively
removed from the ongoing reaction, to produce a particular type of glyceride

3.Enzymatic interesterification
 Enzymatic interesterification is now used to produce high value added structured fats and oils
products
 The major advantages of the enzymatic interesterification over chemical processes are the
specificity

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