Chapter 6- Oils, Fates and Detergents

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 Introduction fats and oils
 Fats and oils belong to a group of biological substance called lipids.

 Lipids are biological molecules soluble in organic solvents such as alcohols

and ethers.

 They include fats, oils, waxes, terpenes, steroids, prostaglandins, and

molecular components of membranes.

 They are the fatty acid esters of glycerol and are an important source of energy

in the diet.

 They are esters of the tri-alcohol, glycerol . Therefore, fats and oils are

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 Cont..

 Fats and oils share a common molecular structure, which is

represented by the formula below

Where Ra, Rb, and Rc, represents

groups of carbon and hydrogen
atoms.
• As glycerol is common to all fats and oils, whether animal or
vegetable, it is the fatty acid part of the fat (oil) that is of interest.

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Cont..

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 Cont…
 One of the reactions of triglycerides is hydrolysis of the ester
groups.

 Triglyceride molecules contain mostly carbon and hydrogen

atoms, with only six oxygen atoms per molecule. This means that
fats and oils are highly reduced (that is, un-oxidized).
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 Cont..
 They are, in this way, similar to the hydrocarbons in petroleum, and
like petroleum they are good fuels.
 The main biological function of triglycerides is as a fuel.
 The normal human body stores sufficient energy in fat for
several weeks’ survival.
 This storage ability helps the organism deal with unpredictable
variations in the food supply.
 Plants, too, store energy in fats and oils.

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 ..
Cont

 The differences among triglycerides (fats and oils) are because of;
the length of the hydrocarbon chains of the acids and the number
and position of double bonds (unsaturation). This means saturated
and unsaturated fatty acid
 Saturated fatty acids have no double bonds
 Unsaturated fatty acids do contain double bonds
 The double bond is normally in a cis configuration
 Double bonds lower the melting temperature

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Cont..

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  Properties of triglycerides..

 Triacylglycerols that are solids or semisolids at room temperature

are called fats.
 Fats are usually obtained from animals and are composed largely
of triacylglycerols with either saturated fatty acids or fatty acids
with only one double bond.
 The saturated fatty acid tails pack closely together, giving the
triacylglycerols relatively high melting points, causing them to be
solids at room temperature.

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 Cont..
 Liquid triacylglycerols are called oils.
 Oils typically come from plant products such as corn, soybeans,
olives, and peanuts.
 They are composed primarily of triacylglycerols with unsaturated
fatty acids that cannot pack tightly together.
 Consequently, they have relatively low melting points, causing
them to be liquids at room temperature.
 The hardness or consistency of the fat depends upon the relative
amount of saturated and unsaturated fatty acids present in the fat.

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 Cont….
 Fats are greasy to touch and leave an oily impression on paper.
 They are insoluble in water, but are readily soluble in fat solvents
like alcohol, ether, chloroform, etc
 Pure glycerides are tasteless, odorless, colorless and neutral in
reaction.
 But after exposure to air for sometime, they become acidic and
develop a yellow colour due to partial hydrolysis and oxidation of

unsaturated fatty acids contained in them.

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 Cont..

 It under go Esterification reaction : reacts fatty acids with

alcohols to form esters and water

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 Cont..

 They under go Saponification reaction

 It is the base-catalyzed hydrolysis of an ester

Products of the reaction are

An alcohol
An ionized salt which is a soap
• Soaps have a long uncharged hydrocarbon tail
• Also have a negatively charged carboxylate group at end
• Form
CH
micelles
O
O
C R
that dissolve oil andH dirt
C
particles
OH R 1
O
C ONa
2 1 2
O O
R2 C O C H HO C H + R C ONa
2
O
O
CH2 O C R3 3 NaOH H2C OH
R3 C ONa
Triacylglycerol Glycerol Sodium salts of15
fatty acids (soap)
 Cont..
 it under go Hydrogenation reaction
 It is an addition reaction unsaturated fatty acids can be
converted to saturated fatty acids.
 Hydrogenation is used in the food industry
 Halogenation reaction

CH3 (CH2)4 CH CH CH2 CH CH (CH2)7 COOH

Linoleic acid
2 I2

CH3 (CH2)4 CH CH CH2 CH CH (CH2)7 COOH

I I I I
Stearate-tetra-iodinate 16
 1.2.Classification of oils
 There are two classifications of oils;

1. Edible
 Various edible are cotton seed, olive, soya been, corn oil etc
 this oils are employed cooking purposes.

2. Inedible
 The oils which are used in various industries such as soap, paints,
varnishes and lacquers are known as industrial oils.
 coconut oil, palm oils, are commonly used a various industries such
as soap,in the manufacture of soap.
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 Cont..

 oils such as linseed oil and perillla oil are used in paints and varnishes

as drying oil.

 The vegetable oil processing industry involves the extraction and

processing of oils and fats from vegetable sources.

1.3. Manufacture of vegetable oils
 The oils and fats are extracted from a variety of fruits, seeds, and nuts.

 Vegetable oils and fats are principally used for human consumption

but are also used for medicinal purposes, and for certain technical

applications 18
 Cont..
 Extraction process
 The preparation of raw material includes husking, cleaning and
crushing.
 The extraction processes are generally mechanical (boiling for
fruits, pressing for seeds and nuts) or involve the use of solvent
such as hexane
 After boiling, the liquid oil is skimmed; after pressing, the oil
is filtered;
 The crude oil is separated and the solvent is evaporated and
recovered.
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 Cont..

 Refinement
 The crude oil is refined to remove undesired impurities such as
gums, free fatty acids (FFA), traces of metals, coloring components,
and volatile components.
 refining processes includes degumming, neutralization, bleaching,
deodorization, and further refining.
 Chemical Refining
 The crude oil or fat is warmed with a little alkali to neutralize any
free acids and also to coagulate the colloidal impurities present.

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 Cont..

 The oil or fat is then bleached with Plaster of Paris and finally
heated with superheated steam to remove any odors.
 Conventional chemical refining involves degumming for the
removal of phospholipid
 Residues are conditioned (for example, dried) and are reprocessed to
yield by-products such as animal feed.

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 Cont…
 Physical Refining
 Physical refining is a more simple process in which the crude oil is
degummed and bleached, and then steam stripped to remove FFA
(Free Fatty Acids that result from the hydrolysis of fats).
C) Other Modification
 Hydrogenation of oils
 It was developed as a result of the need to
 (1) convert liquid oils to the semi-solid form for greater utility in
certain food uses and
• (2) increase the oxidative and thermal stability of the oil.

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 Cont..

 If the hydrogenation is completely performed, all

the double bounds are converted to the
saturated ones with the same carbon number.
 For example, complete hydrogenation of linoleic
acid generates stearic acid.

Complete hydrogenation of linoleic acid,

giving stearic acid

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 Animal fats and oils
 Animal Fats and Oils are natural products obtained from the fatty
tissues of animals and consisting of mixed triglycerides of saturated
or unsaturated fatty acids.
 If saturated fatty acids predominate, animal fats have a solid
consistency and a comparatively high melting point
 Animal fats and oils are part of the makeup of the tissues of marine
mammals and fish and the bones of land animals.
 A characteristic of fats and oils of marine mammals and fish is the
presence of triglycerides of highly unsaturated fatty acids (with four,
five, or six double bonds) 25
 Cont..

Extraction of animal fat by Rendering

 This method is used for obtaining fats and oils
from animal sources.
 The animal tissues are treated with hot water or
stream when the oil or molten fat forms layer at
the top which is removed from time to time.

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 Analysis of Fats and oils

 Analysis of fats and oils is carried out for various reasons, viz.:

 Shelf life study (how long the item will remain without
deterioration in quality under a given set of conditions)

 Functional quality (e.g., suitability for use in biscuits, bakery,

hydrogenation, etc.)

 Sensory quality (e.g., rancidity)

 Nutritional quality (e.g., melting point, polyunsaturated fatty acids)

 Conformance to regulatory standards (e.g., with respect to free fatty

Acids, saponification value, peroxide value, moisture)

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 Cont..
 Some of the routine tests carried out on fats and oils are as follows:

✔ Acid value/Free fatty acid (FFA)

✔ Saponification value, SV (also termed Saponification number)
✔ Iodine value, IV (Also termed Iodine number)
✔ Un saponifiable matter
✔ Melting point (for solid and semisolid)
✔ Moisture content

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 Cont..

 Determination of free fatty acids (FFA) and acid value

 For the most part, natural fats and oils are in the triglyceride form
when freshly extracted from the source.
✔ With prolonged storage, however, the triglycerides begin to break
down giving rise to free fatty acids (FFA).
 The acidity of oil is given by the quantity of FAs derived from the

hydrolysis of the triglycerides i.e. separation between FA and the

glycerol in the triglyceride
 This alteration occurs under unsuitable conditions of treatment and
preservation of the oil.
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 The oil acidity, can therefore, indicates the purity of the oil
 Cont..
 Saponification value (SV)
 It is defined as the number of milligrams of potassium hydroxide
required to completely saponify one gram of the fat or oil.
✔ The saponification value gives an indication of the nature of the fatty
acids constituent of fat and thus, depends on the average molecular
weight of the fatty acids constituent of fat.
✔ The higher the SV, the lower the average molecular weight of
the fatty acid in the triglycerides

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 Cont…
 SV of fat/oil is a very valuable test for the determination of
adulteration.
 Since the oil from a given source has a remarkably constant SV, any
deviation found in the test is an indication to adulteration.
 the number of milligrams of potassium hydroxide required to
saponify 1gram of oil or fat

 Un saponifiable Matter
 The Un saponifiable matter (USM) of oil contains minor compounds
comprising sterols and fat soluble vitamins

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 Cont..

 It is a small portion of oil around one percent which is extracted by

organic solvent after the oil is saponified by an alkali Common
edible oils have USM ranging from 0.2 to 2.5%
 •Oil with high un saponifiable matter content have efficacy as skin
products

• where p…. Mass of extracted USM in g

M ….. Mass of saponified oil sample

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 Cont..
Iodine value
 Iodine value is a measure of unsaturation in a fat
or oil and gives an idea of its “drying” character .
More the iodine value, more is the degree of
unsaturation of the oil or fat

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 Cont..

 Peroxide Value (PV)

✔ defined as the amount of peroxide oxygen per 1 kilogram of fat or
oil.
✔ It is used as a measurement of the extent to which rancidity/decay
reactions have occurred during storage.
✔ The molecular structure of fats and oils play a role in autoxidation.
 Oils with a high degree of unsaturation are most susceptible to
autoxidation.
✔ The best test for autoxidation (oxidative rancidity) is determination of
the peroxide value, as peroxides are intermediates in the autoxidation
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 Soap and detergents

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 Cont…

 Soap is the alkali salt of fatty acid.

 Some of the important fatty acids used in soap manufacture are

lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid,

linoleic acid, linolenic acid, archidic acid.

 Unsaturated fatty acids give softer soap with lower melting point

and are less stable while soap from saturated fatty acids are firm,

slowly soluble, milder and have good detergency

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 Cont..
 It is obtained by the hydrolysis of oils and fats by sodium
hydroxide obtained by the hydrolysis of oils and fats by sodium
hydroxide.
 The process is also known as saponification process

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  Classification of soap
 Soaps has been graded in terms of total fatty matter.
 Soap may be categorized as
 toilet soaps,
 shaving soap,
 Laundry
 Ethanolamine
 specialty soap like baby( comparatively of high purity),
 transparent( soap with high glycerine content),
 herbal and antibacterial soap

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 Cont..

 Toilet soaps is soaps consists of mainly sodium oleate.

 Laundry soaps : This type of soap is usually consists of mixtures of
sodium palmitate and sodium stearate.
 laundry soap contain considerable amount of "fillers“ or "builders"
which mixed with soap in the crutcher .
 The commonly used fillers or builders are sodium carbonate ,
sodium phosphate , sodium silicate
 Shaving soaps and other soft soaps are mixtures of potassium salts of
higher acids and are obtained by carrying out the saponification with
potassium hydroxide
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 Cont..
 Ethanolamine soaps are used extensively in shampoos and
cosmetics
 HARD SOAPS = Soaps such as toilet and laundry soaps which are
sodium salts of higher acids are also known as hard soaps.
 SOFT SOAPS = Soaps such as shaving soaps which are potassium
salts of unsaturated fatty acid.
 Shaving soaps contain a considerable amount of potassium soap
and an excess of stearic acid

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 Cont..

Potassium soaps are more soluble than sodium soaps and readily
produce lather.
 Therefore, potassium soaps are used to make liquid soap and shaving
cream.
 Soaps from highly saturated, solid fats, such as tallow, lard, or
shortening, are hard.

 Saponification of an unsaturated oil, such as olive oil, gives a soft

soap.

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  The difference between soft soaps and hard soaps

 Sodium salts are called hard soap where as potassium salts are
soft soaps.
 A hard soap is moderately soluble in water and does not lather
easily whereas soft soap dissolve faster and lather readily.
 Soft soap performs better than hard soaps in cleansing action.

 Tallow, animal fats and coconut oils are the main sources of

hard soaps, while linseed oil, castor oil etc produces soft soaps.

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  Manufacture process of soap
 Two main processes are used for manufacturer of ordinary soap
from oils and fats.
A. Cold process :In this process , the molten fat or oil is mixed with a
calculated quantity of lye [sodium hydroxide] in an iron vessel .
 The mixture is an stirred vigorously by a mechanical stirrer.
 As soon as soap begins to set , it is drawn out into frames and
allowed to set there and the solid soap is cut into bars and dried.
 The major drawback of this method is that is not possible to recover
glycerol. More ever , the reaction between fat and oil and alkali
does not proceed to completion
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  Hot process
 The process follow Batch process
 Step 1 - Oil preparation: The mostly commonly used oils are tallow
and coconut oil.
 These are blended together and dried in a vacuum chamber. Once the
oils are dry, bleaching earth is added to remove any colored
impurities.
 After removing the bleaching earth by filtration, the oils are stored
ready for saponification.
 Step 2 – Saponification: The mixture of bleached oils is mixed with
recycled spent lye from the washing stage downstream and fresh
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caustic soda solution.
 Cont..
 The mixture is boiled for several hours after which it settles into two
layers with the mixture of soap and unreacted oils at the top.
 The bottom layer i.e. the lye which contains glycerine is pumped off.
 Step 3 – Washing: The crude soap is washed with a mixture of fresh
caustic solution and Niger lye.
 The washed soap is sent to the fitting pans, while the lye is used in
the next saponification.
 Step 4 – Fitting: Here the remaining unwanted glycerine is removed
from the soap by re boiling with water, NaCl and a small amount of
NaOH solution.
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 Cont…
 The electrolyte concentration in the water is such that the soap and
water separates out into two layers.
 The top layer is ’neat’ wet soap, which is pumped off to be dried.

 The bottom layer is known as the ’nigre’ layer, and consists of a

solution of soap, glycerine and NaCl.
 Step 5 – Drying: Finally, the water level is reduced down to about 12%
by heating the soap to about 125oC under pressure and then spraying it
into a flash tank at vacuum pressure of about 40 mm Hg (5.3 kPa).
 The latent heat of evaporation lost as the water boils off reduces the
soap temperature down to 45oC, at which temperature it solidifies onto
walls of the flash tank.
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  Detergent
 A detergent is an effective cleaning product because it contains
one or more surfactants.
 Because of their chemical makeup, the surfactants used in
detergents can be engineered to perform well under a variety of
conditions.
 Such surfactants are less sensitive than soap to the hardness
minerals in water and most will not form a film.
 Surfactants, also called surface active agents, are organic
chemicals that change the properties of water

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 Cont..
 Detergents are structurally similar to soaps, but differ in the water-
soluble portion.

 This difference in solubility has two important implications.

✔ Firstly, this makes the surfactant molecule a wetting agent.
 The tails migrate to align themselves with the solid-water interface,
thus lowering the surface tension at that point so that the surfactant
penetrates the fabric better
Secondly, it allows the oily dirt particles to form an emulsion with
the water.

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  Manufacture of detergents
 They are made both in powder and liquid form, and sold as laundry
powders, hard surface cleansers, dish washing liquids, fabric
conditioners etc.
 Detergents are complex formulations that contain different
ingredients, which can be categorized into the following main
groups:
1. Surfactants
2. Builders
3. Bleaching agents
4. Additives 49
 Cont..
 Surfactants represent the most important group of detergent
components.
 They are present in all types of detergents.

 They are water soluble surface active agents comprised of a

hydrophobic group (a long alkyl chain) attached to hydrophilic group.
 „ The hydrophilic group is usually added synthetically to a
hydrophobic material in order to produce a compound, which is
soluble in water.
 This solubilization does not necessarily produce a detergent, since
detergency depends on the balance of the molecular weight of
hydrophobic portion to that of the hydrophilic portion.
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 Cont..
 Builders enhance the detergency action so that less can be used of
the more expensive detergents of high activity.
 The combination of builders and surfactants exhibits a synergistic
effect to boost total detergency and cleaning efficacy.
 Detergent builders should have the ability to control water hardness
and other metal ions, i.e. by eliminating calcium and magnesium
ions, which arise from the water and from soil.
 „ Builders should be also compatible with other formulation
ingredients and detergent additives.

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 Cont..

 Bleaching agents
 Bleaches increase the reflectance of visible light at the expense of
absorption.
✔ It involves the removal or change of dyes and soil by mechanical
and/or physical means.
 Hydrogen peroxide is the main bleaching agent.

 Sodium perborate NaBO3 is incorporated in detergents as a source

of hydrogen peroxide.
 Other Additives like perfume, stabilizer, preservatives also added.

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  Detergent manufacture by the spray drying

Step 1 - Slurry making

 The solid and liquid raw ingredients are fed into a large tank known as
a slurry mixer or clutcher.

 As the ingredients are added the mixture heats up as a result of two

exothermic reactions: the hydration of sodium tripolyphosphate and

the reaction between caustic soda and linear alkylbenzene sulphonic

acid.

 The mixture is then further heated to 85oC and stirred until it forms a

homogeneous slurry. 53
 Cont..

 Step 2 - Spray drying

 The slurry is deaerated in a vacuum chamber and then

separated by an atomizer into finely divided droplets.
 These are sprayed into a column of air at about 425 oC, which
dries them instantaneously.
 The resultant powder is known as ’base powder’ from which
other products are made.
 Step 3 – Post dosing
 Other ingredients are now added, and the air blown through the mixture in a
fluidizer to mix them into a homogeneous powder and agglomeration is takes 54place
 Cont..

 Packaging

 Detergents, including household cleaners, are packaged in cartons, bottles,

pouches, bags or cans.
 The packaging materials and containers are selected on the basis of product
compatibility and stability, cost, package safety, solid waste impact, shelf
appeal and ease of use

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