Fats and Oils

Fats and oils are mixture of glycerides of fatty acids.

R1COOCH2

R2COOCH

R3COOCH2

Oils are all liquid and fats are solid at normal temperature. Number of double bonds in the fatty
acid radical (R) controls the melting point and chemical reactivity.

Name Composition Number of double bonds Melting point , oC Reactivity to oxygen

Stearic C17H35 0 69 Nil
Oleic C17H33 1 14 Fair
Linoleic C17H31 2 -5 Rapid
Linolenic C17H29 3 -11 Extremely rapid
The ability to react with oxygen enhances the use of unsaturated fatty acids as film forming
vehicle for paints. It also is the cause of rancidity in edible fat product which can be avoided by
use of:

 Hydrogenation- Removes reactive double bonds.

 Antioxidants- Compounds which oxidize preferentially to fats without increase in color
or odor.

Vegetable oils: Oils from soybean, peanut, sunflower, safflower, corn, palm, rapeseed and
coconut are edible oil, whereas oils from linseed and castorseed are non-edible oil.

Use of vegetable oil: Industrial Use of fats and oil:

Liquid oil 57% Fat & oil Use

Vanaspati 19 Animal fat Soaps, greases, paints, varnishes, fatty acid
Soaps and detergents 10 Coconut oil Fatty alcohol, soaps, detergents
cosmetics 9 Linseed oil Paint, varnish, lubricant, grease
Paints and varnishes 2 Soybean oil Do
Miscellaneous 1 Castor oil Lubricants, protective coatings

Methods of extracting vegetable oils

1. Mechanical

Seed cleaned and hulled, steam cooked at 220-250oF for 15-20 minutes, then processed in
either continuous screw extruder or expeller or batch hydraulic press.
2. Solvent extraction

High yields - 98-99% of available oil.

Poor quality – dark color, odoriferous, high free fatty acid content, combination of expeller
and solvent extraction methods yields over 80% as prime quality oil and only 18-19% poorer
grade oil.

Solvents used are petroleum cuts in the hexane range –flammable and trichloroethylene –
toxic.

3. Purification

Alkali such as NaOH or soda ash is added to remove free fatty acids as foots by
centrifugation. Bleaching is done with adsorbent clays such as Fuller’s earth and with
adsorption carbon. Filtration is done on pre-coat rotary filters (or plate and frame filter
press for small capacity plants.

An alternate route is to solvent extract by use of propane. This solvent is miscible with all of
the oil below 80oC but is immiscible with fatty acids and color bodies near the critical
 temperature of 96oC. Temperature gradients in an extraction column are used to effect a
two-phase separation.

Processing of oils

The usual processing of vegetable oils involves degumming and/or steam refining, adsorptive
bleaching, hydrogenation and deodorization.

The oils are degummed by coagulation with small amount (0.05%) of concentrated phosphoric
acid. In alkali refining methods, free fatty acids are neutralized with an excess of 0.1% NaOH
solution and the mixture heated to about 75oC to break any emulsions formed. The gums and
soaps are removed by centrifugation, and fatty acids are recovered by acidulation. Steam
refining involves degumming, bleaching if necessary, and treatment with sparging steam under
high vacuum so that fatty acids are removed by distillation.

Bleaching: Ii is accomplished by the use of adsorptive bentonite clay for edible oils, and
alternatively by chemical reactions for nonedible oils.

Hydrogenation: Hydrogenation or hardening, as applied to fats and oils, may be defined as

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. Its objectives are
to raise melting point, improve keeping quality, taste and odor. It frequently accompanied by
isomerization with significant increase in melting point.

As the reaction itself is exothermic, the chief energy requirements are the production of H2,
warming of the oil, pumping and filtering.
Ni
(C17H31COO)3C3H5+3H2 (C17H33COO)3C3H5 ΔH=-420.8 kJ/kg

Hydrocarbon-steam process for hydrogen gas production is employed widely but gaseous sulfur
compounds are strong catalyst poison even in trace amount, as is carbon monoxide, but to
lesser degree.

The catalyst and unsaturated oil are introduced into a specially designed tall, cylindrical closed
vessel equipped for accurate temperature control. The charge is heated as quickly as possible
to 190oC. Normal operating pressure is 200 to 700 kPa gauge. At about 150oC nickel formate
begins the reduction.

Ni(HCOO)2.2H2O Ni + 2CO2 + H2 + 2H2O

The charge is held at maximum temperature for about 1 hr. and then cooled. During reduction
and cooling period, hydrogen is bubbled through the oil solely to sweep decomposition
products from the oil.
The degree of hydrogenation is controlled by refractometer readings to indicate the physical
properties and hence melting point. Catalyst is filtered off and reused. In the exothermic
hydrogenation reaction, the heat is removed by an interchanger.

Deodorization: It is accomplished by blowing superheated steam through the oil under a high
vacuum of 138 to 800 Pa and 210 to 275oC.

Hydrogenated oil production

Raw materials requirements depend on the type of oil and extent of saturation desired. For
cottonseed oil requirements are:

Basis: 1 ton of hydrogenated oil

Hydrogen : 50 Nm3
Nickel catalyst losses: 0.6 kg
Steam : 0.5 ton
Cooling water : 4.5 ton
Process description

 Batch operation is employed of residence time 1-3 hr. It can treat 5-30 tons of oil per
batch; is equipped with coils for heating and cooling, and turbine agitators to disperse
the injected hydrogen.
 P-T relationship in the operation depends on the type of crude oil and degree of
saturation. Vanaspati shortening is accomplished at 2-3.5 atms. gage pressure and 120-
160oC temperature to maintain higher melting point fats of maximum stability for
cooking purpose.
 Oil is charged to the reactor, heated and evacuated to drive off air and water. A catalyst
and oil slurry of catalyst concentration of 5-15 kg/ton of oil is pumped in. Hydrogen is
introduced and stem heating is turned off. After the desired hydrogenation has
accomplished, the batch is cooled and filtered to reuse catalyst.
 The hydrogenated oil is deodorized in a Dowtherm hated, steam sparging vacuum tower
in continuous mode.
 Oil is decolorized with Fuller’s earth, carbon adsorbent, then filtered and vitamins are
added.

Major engineering problems

 Exothermic reaction: The energy liberation during hydrogenation reaction requires a

nominal amount of cooling water.
 Temperature: temperature control is required and should be kept below 200 oC to avoid
side reaction such as pyrolysis and to prevent sintering of the porous catalyst.
 Kinetic rate factors: In the vicinity of 100oC, surface reaction and adsorption control the
reaction rate; rates are increased by increasing hydrogen pressure (7 atms gage
pressure). At 180oC, mass transfers of hydrogen in the solution and catalyst pores are
rate controlling steps.
 H2 handling problem: Hydrogen gas has a wide explosive limit range (4.1-74.2%). All
equipments should be leak-tested with freon or helium detectors before operation. In
ammonia synthesis plants hydrogen embrittlement is a problem at high temperature
and pressure; carbon steel can be used as a material of construction for hydrogenator.