UNIT II

OILS, FATS, SOAPS AND DETERGENT INDUSTRIES

Fats and oils & 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 Waxes:

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.
Oilis classification as:
(i) Non drying oil (iii) Semi drying oil. (ii)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:

Mechanical extraction
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 2030%
Expellers 3437%
Solvent 4043%

Solvent extraction:

Fig. Extraction of vegetable oil by solvent extraction method

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.

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. 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. 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 275 0C. 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 75 0C 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. 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 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 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

Soap Detergent

It produce less surface tension Better surface tension

Cleaning is not effective Cleaning is better than soap

It does not form foam It form foam

It does not reduce surfactant It increases 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:
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. 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. 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). 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.
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:
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.