CH6502 CHEMICAL PROCESS INDUSTRIES II

UNIT II OILS, FATS, SOAPS AND

DETERGENT INDUSTRIES
 Vegetable oils and animal fats, their nature,
analysis and extraction methods,
hydrogenation of oils, fatty acids and
alcohols, waxes, soaps, synthetic detergents.
FATS , OILS AND THEIR USES:

 Vegetable fats and oils are lipid materials derived from

plants.
 Physically, oils are liquid at room temperature, and fats
are solid.
 Chemically, both fats and oils are composed of
triglycerides, as contrasted with waxes which lack
glycerin in their structure.
 Although many plant parts may yield oil, in commercial
practice, oil is extracted primarily from seeds.
 Examples of inedible vegetable fats and oils include
processed linseed oil, tung oil, and castor oil used in
lubricants, paints, cosmetics, pharmaceuticals, and
other industrial applications.
DIFFERENCES BETWEEN OILS AND FATS:

 The melting temperature distinction between oils

and fats is imprecise, since definitions of room
temperature vary, and typically natural oils have a
melting range instead of a single melting point
since natural oils are not chemically
homogeneous.
 Although thought of as esters of glycerin and a
varying blend of fatty acids, fats and oils also
typically contain free fatty acids, monoglycerides
and diglycerides, and lipids which cannot be
undergo saponification reaction.
INDUSTRIAL USES OF FATS AND OIL:

 Animal fats:- Soaps, greases, paints, varnishes,

syndics
 Coconut oil:- Fatty alcohols, soaps and detergents
 Linseed oil:- paints, varnishes, floor coverings,
lubricants and greases
 Soybean oil:- paints, varnishes, floor coverings,
lubricants and greases
 Castor oil:- Protective coatings, plastics,
plasticizers, lubricants, hydraulic fluids
 Tall oil:- Soap, leather, paints, emulsifiers,
adhesives, ink
SOURCES OF OIL:

 VEGETABLE SOURCE: Ground nut oil, castor oil,

coconut oil, mustard oil, palm oil.

 ANIMAL SOURCE: Mutton, beef

 OCEAN SOURCE: Fish, Cod-liver oil.

Oils classification as:
(i) Non drying oil
(ii) Semi drying oil.
(iii) Drying oil.
IODINE VALUE:

 It is the degree of unsaturation of fats and is

expressed as the no. of milligram of iodine
absorbed by 1g of fat under specified
condition.
Iodine value range for the oils:
 For semidrying oil, iodine value lies in the range
of 90-120.
 For drying oil, iodine value is less than 90.
 For drying oil, iodine value is more than 120.
Acid number:
Acid value is a measure of free fatty acid content.
It refers to the degree of hydrolyte decomposition
that the fat undergoes on storage.

Rancidity:
Moisture and oxygen cause deterioration of fats,
which is termed as rancidity.

Peroxide value:
It is a measure of degree of oxidative deterioration
that the fat undergoes.
Saponification value:
 It is defined as number of milligram of KOH required
to saponify one gm of fat or oil completely.

Winterisation:
 Separation of solid fats by cooling and chilling is
known as winterisation
THE VARIOUS METHODS OF OIL EXTRACTION:

1. Mechanical extraction
2. Solvent extraction -Petroleum cuts in the hexane
range, generally propane is used as solvent.

 To produce vegetable fats and oils, the oil first needs

to be removed from the oil-bearing plant components,
typically seeds or legumes.
 This can be done via mechanical or chemical
extraction.
 The extracted oil can then be purified and, if required,
refined or chemically altered
MECHANICAL EXTRACTION:
 Oils can also be removed via mechanical extraction, termed
"crushing" or "pressing."
 This method is typically used to produce the more traditional oils
(e.g., olive, coconut etc.), and it is preferred by most "health-food"
customers in the United States and in Europe.
 There are several different types of mechanical extraction.
 Expeller-pressing extraction is common, though the screw press, ram
press, and Ghani (powered mortar and pestle) are also used.
 Oil seed presses are commonly used in developing countries, among
people for whom other extraction methods would be prohibitively
expensive; the Ghani is primarily used in India.
 The amount of oil extracted using these methods, varies widely, as
shown in the following table for extracting mowrah butter in India:
Method Percentage extracted
Ghani 20–30%
Expellers 34–37%
Solvent 40–43%
SOLVENT EXTRACTION:
EXTRACTION OF VEGETABLE OIL BY SOLVENT
EXTRACTION METHOD
SOYABEANS OIL - SOLVENT EXTRACTION
COTTON SEED OIL SOLVENT EXTRACTION
SOLVENT EXTRACTION
 The processing vegetable oil in commercial
applications is commonly done by chemical
extraction, using solvent extracts, which produces
higher yields and is quicker and less expensive.
 The most common solvent is petroleum-derived
hexane. This technique is used for most of the
"newer" industrial oils such as soybean and corn
oils.
 Supercritical carbon dioxide can be used as a non-
toxic alternative to other solvents.
HYDROGENATION OF VEGETABLE OILS:
 Hydrogenation or hardening of oils may be defined as the
conversion of various unsaturated radicals of fatty
glycerides into more highly or completely saturated
glycerides by the addition of hydrogen in the presence of
catalyst.

 Various fats and oils such as soybean, cottonseed, fish,

whale and peanut are converted by partial hydrogenation
into fats suitable for shortenings, margarine and other
edible purposes as well as for soap making and numerous
other industrial uses.

 The object of hydrogenation is not only to raise the melting

point but to greatly improve the keeping qualities, taste
and odour for many oils.
HYDROGENATION OF VEGETABLE OILS:
 Oils may be partially hydrogenated to produce various
ingredient oils.
 Lightly hydrogenated oils have very similar physical
characteristics to regular soy oil, but are more
resistant to becoming rancid.
 Margarine oils need to be mostly solid at 32 °C (90
°F) so that the margarine does not melt in warm
rooms, yet it needs to be completely liquid at 37 °C
(98 °F), so that it doesn't leave a "lardy" taste in the
mouth.
 Hardening vegetable oil is done by raising a blend of
vegetable oil and a catalyst in near-vacuum to very high
temperatures, and introducing hydrogen.
HYDROGENATION OF VEGETABLE OILS:
 This causes the carbon atoms of the oil to break
double-bonds with other carbons, each carbon
forming a new single-bond with a hydrogen atom.
 Adding these hydrogen atoms to the oil makes it more
solid, raises the smoke point, and makes the oil more
stable.
 Hydrogenated vegetable oils differ in two major ways
from other oils which are equally saturated.
 During hydrogenation, it is easier for hydrogen to come
into contact with the fatty acids on the end of the
triglyceride, and less easy for them to come into
contact with the centre fatty acid.
HYDROGENATION OF VEGETABLE OILS:
 This makes the resulting fat more brittle than
tropical oil; soy margarines are less "spreadable".
 The other difference is that trans fatty acids (often
called trans fat) are formed in the hydrogenation
reactor, and may amount to as much as 40
percent by weight of a partially hydrogenated oil.
 Hydrogenated oils, especially partially
hydrogenated oils with their higher amounts of
trans fatty acids are increasingly thought to be
unhealthy.
Deodorization:
 Deodorization is accomplished by blowing superheated
steam through the oil under a vacuum of 138 to 800 Pa
and 210 to 2750C.
 This removes most of the odour-causing compounds and
also destroys many of the colour-producing pigments
present.
Bleaching:
 Bleaching is accomplished by the use of adsorptive
bentonite clays for edible oils and alternatively by chemical
reactions for nonedible oils.
 The bleached oil is subjected to Winterizing, which removes
any material that will solidify out at refrigerator
temperatures. This is accomplished by cooling to about 50C
and filtering out any solidified material.
REFINING OF OILS:

 The usual processing of vegetable oils involves

Degumming and/or steam refining, bleaching,
hydrogenation and deodorization.
 The oils are degummed by coagulation with small
amount of (0.05%) of concentrated phosphoric acid.
 In Alkali refining methods, the free fatty acids are
neutralized with an excess of 0.1% NaOH solution and
the mixture is heated about 750C to break any
emulsions formed. The gums and soaps are removed
by centrifugation. The free fatty acids are recovered by
acidulation.
 Steam refining involves degumming and treatment
with sparging steam under high vacuum so that the
free fatty acids are removed by distillation.
FATTY ACIDS AND ALCOHOLS

 Complex lipids contain long-chain carboxylic acids

called fatty acids. These fatty acids have 10-24 carbon
atoms in the carbon chain.
 Saturated fatty acids contain no carbon-carbon double
or triple bonds. Unsaturated fatty acids contain one
(monounsaturated) or more double bonds
(polyunsaturated).
STEARIC ACID: A TYPICAL SATURATED FATTY ACID WITH 18
CARBONS IN THE CHAIN
OLEIC ACID: A TYPICAL UNSATURATED FATTY ACID WITH 18
CARBONS IN THE CHAIN
SOAPS AND DETERGENTS
Chemistry of Soap and Detergent Function:
 All soaps and detergents contain a surfactant1 as
their active ingredient.
 This is an ionic species consisting of a long, linear,
non-polar ’tail’ with a cationic or anionic ’head’ and a
counter ion.
 The tail is water insoluble and the head is water
soluble - a difference in solubility which has two
important implications.
SOAPS AND DETERGENTS
Chemistry of Soap and Detergent Function:

 Firstly, this makes the surfactant molecule a wetting

agent: the tails migrate to align themselves with the
solid: water interface, lowering the surface tension at
that point so that it penetrates the fabric better.
 Secondly, it allows the oily dirt particles to form an
emulsion with the water: the tails of many surfactant
molecules surround an oily dirt particle, forming a
micelle with a drop of oil in the centre and the ionic
heads of the surfactant molecules pointing outwards
and hence keeping the micelle in the polar solution.
Soaps
 Soaps are the compounds of R.COO.M
 Where R is fatty acid radical represents oleic, palmitic,
lauric, and myristic. These present in soaps as mixtures
based on glyceride raw materials. M is an alkali
element such as Na or K.

Chemical reactions involved in soap manufacture

a) FAT SPLITTING

 (RCOO)3. C3H5 + 3H2O → 3RCOOH+C3H5 (OH)3

b) SAPONIFICATION

 RCOOH + MOH → RCOOM + H2O

DETERGENTS

 Detergents are synthetic organic chemicals which

promote better surface tension lowering than soaps.
 These chemical compounds are used for human
comfort, cleanliness and for industrial surface active
applications.
 Their actions are based on colloidal chemistry
principles.
CLASSIFICATION OF DETERGENTS:

 Anionic (give R- in water)

 Sulfated fatty alcohols

 Sulfonates-ABS (Aryl benzene sulfonate)-

 Sulfated esters and acids

 Cationic (give R+ in water)

 Non-ionic
 Alkyl-aryl-ethylene oxide derivatives

 Aliphatic polyhydric alcohol esters

 Fatty acid amides

ANIONIC DETERGENTS:
 Typical anionic detergents are alkylbenzenesulfonates.
 The alkylbenzene portion of these anions is lipophilic and
the sulfonate is hydrophilic.
 Two varieties have been popularized, those with branched
alkyl groups and those with linear alkyl groups.
 The former were largely phased out in economically
advanced societies because they are poorly
biodegradable.
 An estimated 6 billion kilograms of anionic detergents are
produced annually for domestic markets.
 Bile acids, such as deoxycholic acid (DOC), are anionic
detergents produced by the liver to aid in digestion and
absorption of fats and oils.
 Three kinds of anionic detergents: a branched sodium
dodecylbenzenesulfonate, linear sodium
dodecylbenzenesulfonate, and soap.
Cationic detergents:
 Cationic detergents are similar to the anionic ones, with
a hydrophobic component, but, instead of the anionic
sulfonate group, the cationic surfactants have
quaternary ammonium as the polar end.
 The ammonium center is positively charged.
Non-ionic detergents
 Non-ionic detergents are characterized by their
uncharged, hydrophilic head groups.
 Typical non-ionic detergents are based on
polyoxyethylene or a glycoside.
 These materials are also known as ethoxylates or
PEGylates. Glycosides have a sugar as their uncharged
hydrophilic headgroup.
 Examples include octyl-thioglucoside and maltosides.
HEGA and MEGA series detergents are similar,
possessing a sugar alcohol as head group.
ZWITTERIONIC DETERGENTS
 Zwitterionic detergents possess a net zero charge
arising from the presence of equal numbers of +1 and
-1 charged chemical groups.
 Phosphates such as sodium tripolyphosphate and
tetrasodium pyrophosphate used s much as 30-50%
in detergent formulations to extend foam
 Sodium carboxycellulose (1-3%) to improve soil and
dirt suspension
 Fluorescent dyes as brighteners
 Sodium silicate to avoid corrosion in washing
machines
DIFFERENCE BETWEEN SOAP AND DETERGENTS

Soap Detergent

It produce less surface Better surface tension

tension
Cleaning is not effective Cleaning is better than
soap
It does not form foam It form foam

It does not reduce It increases surfactant.

surfactant
INDUSTRIAL USES OF SOAPS AND DETERGENTS:

 Textile manufacture
 Sanitation
 Food processing
 Shaving soaps
 Synthetic rubber and plastic emulsion polymerization
 Paints-water emulsion formulations
 Paper-application of sizing
 Oil production-drilling fluid oils
 Inks- water in oil emulsions
 Agriculture – emulsifying agents for sprays
METHODS OF SOAP PRODUCTION:
Batch saponification: (Oldest Process)
 TWITCHELL Process (acid hydrolysis of glycerides followed by
alkali addition) Or
 Direct saponification using caustic
Continuous hydrolysis & saponification
 This method is in greater use because of the following
advantages over the batch process:
 Flexibility in control of product distribution

 Higher glycerin yields (>80%)

 Less off-color production

 Requires less space and man power

RAW MATERIALS:

 Principal Fatty constituents- Refined Tallow, Recovered

and refined grease, Coconut and palm oils
 Metal oxides such as ZnO are added as fat splitting
catalyst.
 Alkali (NaOH or KOH) for saponification
 Builder-type additives mainly rosin
THE ESSENCE OF SOAP PRODUCTION IS THE
SAPONIFICATION REACTION:
PROCESS DESCRIPTION
 This reaction is exothermic, and progresses quickly
and efficiently at around 125oC inside an autoclave
type reactor.
 The most common fats and oils used are tallow (beef
or mutton/beef blend), coconut oil, and palm kernel
oil.
 Different oils produce soaps of varying hardness,
odour and lathering, so the ratios of the oils used are
closely monitored to produce a blend with the most
desirable characteristics for the most reasonable cost.

PROCESS DESCRIPTION

 However, pure soap is hard and easily oxidized,

so various additives are added to correct this
and to make a more aesthetically pleasing
product.
 The first such "additive" is glycerin, which is
produced in the saponification reaction.
Glycerin makes the soap smoother and softer
than pure soap.
PROCESS DESCRIPTION
 However, it is also much more valuable than soap
itself, so only a minimum of glycerin is left in the soap
and the remainder is extracted, purified and sold.
 The glycerin is extracted from the soap with lye2 - a
brine solution that is added to the soap at the
saponification stage.
 Wet soap is soluble in weak brine, but separates out
as the electrolyte concentration increases.
 Glycerin, on the other hand, is highly soluble in brine.
 Wet soap thus has quite a low electrolyte concentration
and is about 30% water (which makes it easily pump able
at 70oC).
PROCESS DESCRIPTION
 To remove the glycerin, more electrolyte is added,
causing the the wet soap to separate into two layers:
crude soap and a brine/glycerin mixture known as
spent lye, neutral lye or sweet waters.
 The soap still contains some salt, which itself
functions as an additive, altering the viscosity and
colour of the soap.
 Once the spent lye has been removed the soap is
dried, chipped, mixed with other additives such as
perfumes and preservatives and then plodded
(squeezed together), formed into tablets and
packaged for sale.
SYNTHETIC DETERGENTS
 Synthetic detergents have similar molecular structures
and properties as soap.
 Although the cleansing action is similar, the detergents do
not react as readily with hard water ions of calcium and
magnesium.
 A detergent is a formulation comprising essential
constituents (surface active agents) and subsidiary
constituents (builders, boosters, fillers and auxiliaries).
 Synthetic detergents dissolve or tend to dissolve in water
or other solvents. To enable them to do this, they require
distinct chemical characteristics.
 Hydrophilic (water loving) groupings in their molecular
structure, and hydrophobic (water hating) groupings, help
the detergent in “detergency” action.
SYNTHETIC DETERGENTS
 The basic component of a synthetic detergent is a
'surface active agent' ('surfactant') which binds to
grease and dirt and keeps it suspended in water.
 Other constituents include fillers to improve the free-
flowing properties of powder detergents, foam
stabilizers, optical brighteners, silicates, bleaches and
fragrances.
 Phosphates or zeolites are added to control the
alkalinity and soften the water.
 Foam stabilizers, optical brighteners and fragrances are
not essential for detergent effectiveness. The
formulation of the detergent depends on the application.
WAXES

 Wax refers to a class of chemical compounds that are

plastic (malleable) near ambient temperatures.
 Characteristically, they melt above 45 °C (113 °F) to
give a low viscosity liquid.
 Waxes are insoluble in water but soluble in organic,
nonpolar solvents.
 All waxes are organic compounds, both synthetic and
naturally occurring.
TYPES OF WAXES

 Waxes are organic compounds that characteristically

consist of long alkyl chains.
 Natural waxes are typically esters of fatty acids and
long chain alcohols.
 Synthetic waxes are long-chain hydrocarbons lacking
functional groups.
PLANT AND ANIMAL WAXES
 Waxes are biosynthesized by many plants and
animals.
 They typically consist of several components, including
wax esters, wax acids, wax alcohols, and
hydrocarbons.
 Wax esters are typically derived from a variety of
carboxylic acids and a variety of fatty alcohols.
 The composition depends not only on species, but
also on geographic location of the organism.
 Because they are mixtures, naturally produced waxes
are softer and melt at lower temperatures than the
pure components.
ANIMAL WAXES

 The most commonly known animal wax is beeswax,

but other insects secrete waxes.
 A major component of beeswax is the ester
myricylpalmitate substance which is used in
constructing their honeycombs.
 Its melting point is 62-65 °C. Spermaceti occurs in
large amounts in the head oil of the sperm whale.
 One of its main constituents is cetylpalmitate, another
ester of a fatty acid and a fatty alcohol.
 Lanolin is a wax obtained from wool, consisting of
esters of sterols.
PLANT WAXES
 Especially in warm climates, plants secrete waxes as a
way to control evaporation and hydration.
 From the commercial perspective, the most important
wax is Carnauba wax, a hard wax obtained from the
Brazilian palm.
 Containing the ester myricylcerotate, it has many
applications.
 Other more specialized vegetable waxes include
candelila wax, ouricury wax, sugarcane wax, retamo
wax, jojoba oil.
 The epicuticular waxes of plants are mixtures of
substituted long-chain aliphatic hydrocarbons,
containing alkanes, fatty acids, primary and secondary
alcohols, diols, ketones, aldehydes.
PETROLEUM DERIVED WAXES

 Although most natural waxes are esters, paraffin waxes

are hydrocarbons, mixtures of alkanes usually in a
homologous series of chain lengths.
 These materials represent a significant fraction of
petroleum.
 They are refined by vacuum distillation. Paraffin waxes are
mixtures of saturated n- and isoalkanes, naphthenes, and
alkyl- and naphthene-substituted aromatic compounds.
 The degree of branching has an important influence on
the properties.
 Millions of tons of paraffin waxes are produced annually.
They are used in adhesives, in foods (such as chewing
gum and cheese wrapping), in cosmetics, and as coatings.
MONTAN WAX

 Montan wax is a fossilized wax extracted from coal

and lignite.
 It is very hard, reflecting the high concentration of
saturated fatty acids and alcohols, not esters that
characterize softer waxes.
 Although dark brown and smelly, they can be purified
and bleached to give commercially useful products
POLYETHYLENE AND RELATED DERIVATIVES

 Some waxes are obtained by cracking polyethylene at

400 °C.
 The products have the formula (CH2) nH2, where n
ranges between about 50 and 100.
 As of 1995, about 200 million kilograms/y were
consumed.
USES

 Waxes are mainly consumed industrially as

components of complex formulations, often for
coatings.
 The main use of polyethylene and polypropylene
waxes is in the formulation of colourants for plastics.
 Waxes confer matting effects and wear resistance to
paints.
 Polyethylene waxes are incorporated into inks in the
form of dispersions to decrease friction.
 They are employed as release agents.
 They are also used as slip agents, e.g. in furniture,
and corrosion resistance.