Non edible application of oil and Fat (Unit 6 b)

CHAPTER 6: OIL
AND FAT
APPLICATIONS
6 . 2 N O N - E D I B L E A P P L I C AT I O N
6 . 2 . 1 S O A P
6 . 2 . 2 D E T E R G E N T
6 . 2 . 3 L U B R I C A N T
6 . 2 . 4 PA I N T
6 . 2 . 5 B I O D I E S E L
11/7/2020
Dr. Mohammed Danish (UnikL-MICET)/ Oil and Fat
Technology (CPB 30303)
1

NON-EDIBLE APPLICATIONS OF OIL
AND FAT
Soap Detergent Lubricant
Paint Biodiesel
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2

• Soap was used by the Phoenicians and Romans, and soap-making
process was recorded by Plinius in AD 70.
• The early soaps were made from animal fats and wood ash, found
traces from as early as 2800 BCE, the word “soap” comes from
ancient Rome, where animal fat unintentionally mixed with wood
ash during religious ceremonies of Mount Sapo. People discovered
the resulting paste was an effective cleaning agent, and they called
it “sapo” in recognition of its origin.
SOAP
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• Improved soap products with vegetable oils were introduced in the middle Ages by the
Arabs.
• By the twelfth century, soap was being made commercially in Bristol, England.
• Saponification reaction can be shown as:
• In 1778, Leblanc invented caustic soda (NaOH) production, which open the road for
large scale industrial soap production.
• Some large soap manufacturing units are established such as, Crossfields (1814 A.D.),
Pears (1879 A.D.), Lever in (1884 A.D.)
• With the development of inorganic and organic chemistry in 18th and 19th century, the
variety of acid and alkali produced on scientific basis. The organic chemistry helps in
understanding lipids and variation of lipid raw materials.
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CHEMICALS IN SOAP
In modern soaps with lots of variety in consistency, fragrance, pH, and anti bacterial
properties, the ingredients list extends far beyond fats and bases.
• Sodium Benzoate and Benzoic acid: used as an anti-corrosive and preserving agent in a
wide range of industries, it has other commercial names such as benzoate of soda,
sobenate, natrium benzoicum, and benzoic acid. In cleaning, sodium benzoate is beneficial
for its antifungal and intrinsic preserving qualities. As a preservative, sodium benzoate
extend the shelf life of liquid soap and prevents fungi like yeast and moulds from
colonizing.
• Sodium Laureth sulfate (SLS): it acts as both surfactant and elusifier and contributes a
sudsing and foaming element in soap. A commonly known SLS is sodium dodecyl sulfate, it
is highly effective in removing oil residues. Since it can clean grease from engines and
floors, industrial settings often use high SLS containing liquid soaps.
• Personal care soaps contain less concentration of SLS. I addition of emulsifying oils, SLS
suspends dirt and soil in water, allowing it to wash away easily. SLS reduces the surface
tension of water, allowing it to more thoroughly wet and clean surfaces.
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• Methylisothiazolinone (MIT) and chloromethylisothiazolinone (CMIT): MIT and CMIT are
common preservatives in many liquid soaps. Both chemicals individually work to inhibit
bacterial growth, but they are often used in combination. Typically MIT and CMIT are the
integral part of ingredients of the personal care product. They act as powerful biocides,
eradicate the slime-forming fungi, algae and bacteria that can developed in many
settings, including fuel storage tanks, water cooling systems, paper, and pulp mill
oil extraction systems.
• Cocamidopropyl Betaine (CAPB): it is a surfactant derived from coconut oils by mixing the
raw coconut oil in the dimethylaminopropylamine. Classified as an amphoteric surfactant
detergent, CAPB can function as either and acid or a base, depending on its chemical
surroundings. With a polar head and a hydrocarbon tail, CAPB helps soap break down
debris and wash it away in water. CAPB can acts as a thickening agent in many liquid
Manufacturers include CAPB in their liquid soap formulas for its surfactant aw well as
foaming properties. CAPB creats a rich and thicker lather. CAPB also has some antiseptic
properties, which makes it a common addition in personal sanitary products.
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• Fragrance: the exact ingredients of soaps fragrance vary from manufacturer to
manufacturer- the current law allow them to hide the specific chemicals used for their
specialized products. Scents. In one fragrance, there could be hundreds of ingredients or
just a few- more than 3,500 oils and chemicals are approved for use in fragrance
These add a perfuming elements in the soap, helping it deodorized as well as clean
surfaces. Synthetically produced fragrant oils are the most popular choice for scented
soaps, because natural essential oil and scented products are more expensive.
• pH Adjusters: the human body has a natural pH of 7.4, by nature, soap is an alkaline
substance and will have a high pH balance. However, it a soap will come in contact with
humans, it should never have a pH higher than 10- the closer the soap’s pH is the pH of
human skin, the better. If the pH of the soap is too high, it will be irritating and even toxic
to humans. In liquid soaps, some chemical ingredients alter the pH balance of Soap. Most
often, the pH adjusters in liquid soaps will be citric acid or sodium chloride. Citric acid is
naturally occurring chemical found in citrus fruits and can be resulted form the
fermentation of carbohydrates. Addition of citric acid lowers the soap pH, making them
alkaline. It also enhances the effectiveness of preservative and antioxidant ingredients in
soaps. NaCl is salt, it also reduces the pH of the soap solutions. It acts as a stabilizing
helping pH levels remain steady. A thickening agent, sodium chloride also has a de-
greasing effect, enhancing the cleaning potential of the liquid soap.
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• Dyes: dyes give the soap an
appealing color. Like fragrances, the
exact ingredients of synthetic dyes
depend on the specific manufacturer.
Often, they chemically derived from
petroleum and coal tar. The purpose
using dyes in soap is purely aesthetic-
they make the product visually
appealing and have little to no
functional values. Because of this,
many companies choose synthetically
produced dyes and colorants, as
opposed to naturally derived
compounds, since synthetic dyes are
almost always cheaper and more
readily available. The best dyes have
long term color stability and resists
fading. Common color choices for
liquid soaps are yellow, blue, and
green, but the right dye can achieve
almost any colour.11/7/2020 Dr. Mohammed Danish (UnikL-MICET)/ Oil and Fat Technology (CPB 30303) 8

STEPS OF LIQUID
SOAP MAKING
1. Select a type of fat or oil—the most commonly used fats
derived from plants, such as palm kernel oil, coconut oil,
and olive oil etc. you can either one type of oil or
combination of it, for example if selected two oils
(Coconut oil and Olive oil) you can take 70% of coconut
oil and 30% of olive oil.
2. Make lye water—Mix the caustic soda with water until it
dissolves. Reaction of NaOH with water is exothermic,
use caution during lye water preparation.
3. Combine the oils with the lye water— once mixed, allow
the soap to rest up to 24 hours.
4. After the soap has set, slowly add heat and water until
the soap is smooth and at a proper liquid consistency.
11/7/2020 Dr. Mohammed Danish (UnikL-MICET)/ Oil and Fat
Technology (CPB 30303) 9

DETERGENTS
• It was the development of the petrochemical industry in the period 1940-1970 that
brought about a revolution in the type of surfactant available in the market.
• Detergents are the petroleum products in which the hydrophobic groups usually
saturated paraffinic chain of C12-18 are available at much cheaper price than lipids.
The acid functional group is sulphate groups attached in one end.
• Detergent compositions based essentially on surface active compounds, such as
anionic, cationic, or amphoteric or non-ionic surfactants. In 1940 the surfactants are
prepared in laboratory scale. For example non-ionic surfactants are based on the
ethylene oxide, that have good detergency and excellent solubility in both soft and
hard water over a wide pH range.
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• With the rise of petrochemical industries in 1940-1970 brought the revolution in the
type of surfactants available in the market. The reason was twofold. (1) the
hydrophobic groups in the carbon range of 12-18 was now available in large quantity
at much cheaper prices than the equivalent hydrophobic groups from animal fats and
vegetable oils. (2) hydrophobic groups containing the benzene ring were now available
in large quantities that allowed far more variety in attaching hydrophilic groups to the
hydrophobic groups for example sulfonation using sulfur trioxide. As a result a large
number of “synthetic” surfactants appeared in the market from 1940 onwards.
• Detergent products were successful because of their superior cleaning quality over
soaps in both hard and soft waters. Soaps replaced in most house-hold, and this
decline in soap production still continues in western Europe.
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• The principal anionic surfactants that have replaced soap in detergent are listed in
given below table.
• The surfactant is the component that has the major influence on the properties of an
aqueous solution in relation to wetting, foaming, dispersing solids, emulsifying oils,
and removing dirt from the fabric.
• A modern heavy-duty laundry detergent will have at least two surfactants, a builder, a
bleaching system, an enzyme, anti redeposition agents, foam stabilizer and control
additive, fluorescent whitening agents or optical brighteners, corrosion inhibitor,
perfume, dyestuff, and fillers.
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• Fillers: fillers in detergent are materials which are added in detergent to alter their
physical characteristics and properties. The objective of adding fillers to detergents is
to make detergents fluid or to turn the fluidized detergent in powder form. Generally
the fillers are bulk components in various detergents with their primary role to modify
and alter the physical properties. Some common filler materials used in detergents
sodium sufate, sodium chloride, borax alcohols etc.
• Builders in detergent: builders are materials which can be used to bind cations
(mainly calcium, Ca2+, and magnesium Mg2+) contained in washing water that results
water softening. Builder enhance the quality of water, thereby making the detergents
work in a more effective and efficient manner. Example of commonly used builder in
detergent are sodium tripolyphosphate (STPP).
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LUBRICANT
• Lubricants: Lubricants are those substances, which are used to reduce the force of
friction between two sliding surfaces.
• Lubrication: lubrication is the process, or technique employed to reduce wear on
surfaces in close proximity, and moving relative to each other.
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COMPOSITION OF LUBRICANTS
• Typically lubricants contains 90% base oil (petroleum-mineral oil) and less than 10%
additives.
• Non liquid lubricants contains Grease, powder (dry graphite, Molibdenum disulphite),
Teflon tape used in plumbing etc.
• Those non liquid lubricants provide lubrication at higher temperature (up to 350 °C).
• Lubricants are not especially hazardous from an environment point of view; their
innumerable applications make them omnipresent. Mineral oil, representing the largest
single component in lubricants (>90%), and some chemical additives are
environmentally undesirable because of their poor biodegradability.
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ENVIRONMENTALLY FRIENDLY
LUBRICANTS
• The synthesis of environmentally friendly lubricants is the driving force behind the use
of vegetable oils and fats and their derivatives.
• To understand the development of lubricants based on natural fatty oils and their
derivatives, one must examine the criteria used to define the environmental
compatibility of lubricants.
• Vegetables oils and their oleochemical derivatives have significantly better chances
than petrochemical alternatives even though industrially manufactured synthetic
carboxylic acids have produce good results in lubricants.
• More than one-third of lubricants available in the market are end up polluting the
environment either via total loss applications, spillages, evaporation, or in other ways.
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BIODEGRADABILITY OF THE
LUBRICANTS
• Rapid biodegradability is generally desirable feature of the lubricants that may
eventually enter the soil and water and also for biological purification plants.
• An important aspect of natural degradation is the distribution of the substance to be
degraded. Biodegradation is more rapid if the substance is finely distributed in the soil
or water and there is sufficient oxygen.
• The biodegradability of used lubricants can be altered by contamination.
Measurements have shown that a deterioration of up to 15% can occur. This means
that a lubricant that is 90% degradable when fresh may only be 75% degradable when
used.
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BASE OIL FOR RAPIDLY
BIODEGRADABLE LUBRICANTS
• The selection of the base oils concentrates mainly on ester substances.
• Natural oils such as castor oil, palm oil, rapeseed oil, neatsfoot oil, lard and degras oil
have been used in lubricants for years. Over the past decade, these oils have been
used mainly as additives.
• The concentration of saturated long-chain fatty acids in the triglyceride molecule
(palmitic, stearic acid) increases; the low temperature behaviour worsens. As the
polyunsaturated fatty acids (e.g. linolenic acid, linoleic acid)increase, the
thermal/oxidative resistance worsens.
• A very long monounsaturated fatty acids (e.g. erucic acid, 22:1)worsen the low
temperature behavior.
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• The weakness of vegetable oil based lubricants can best be described by the structural
elements of the double bond and the –CH group, they cause thermal and oxidative
instability.
• The ester groups can be hydrolyzed i.e. split by water.
• Lubricant applications generally employ fully refined rapeseed oil. That is oil has
undergone all refining stages such as dewatering, desliming, neutralization, bleaching,
and steaming (water vapour).
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CHEMICAL MODIFICATION OF
NATURAL FATTY ACIDS
• Chemistry offers a wide variety of possibilities in the area of synthetic esters. A major
development objective is to find inexpensive esters among all the possible substances that
meet the specific requirements of a particular application.
• An interesting example from lubrication technology is the manufacture of 12-
hydroxystearic acid from castor oil. It is an alkaline or earth alkaline soap (mainly lithium
soap) is the most important thickener for greases and is obtained by hydrogenation.
• Ester oils were used in special lubricants for technical reasons, e.g., as base fluids for
aviation turbine oils and components for fuel economy oils.
• The most important groups ester include monesters, diesters, polyol ester, and complex
esters. At present, polyol esters such as trimethylolpropane esters (TMP esters) or
pentaerythritol ester dominate.
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PAINT
• Paint and surface coating agents are generally seen as those materials applied to
substrate ranging from wood and paper to a variety of metals, plastic and many
composite assemblies.
• They generally have a dual role, which is to protect and to decorate, the latter
including an ability to disguise.
• The protective role is that of shielding the substrate from such environmental agents
as radiation, moisture, and oxygen and possibility from more aggressive attackers such
as atmospheric SO2 in industrial environments.
• Paint may disguise inferior construction materials or even prevent recognition of the
object.
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COMPONENTS OF PAINTS
Paints consists of three principal components:
• Binder
• Pigment
• Solvent
The binder and pigment are the permanent constituents, with the binder providing the
adhesion and cohesion, keeping the pigment within the coating and ensuring that the paint
remains attached to the substrate.
Oils have played a dominant role in paint and surface coating over at least the last 200 years,
with various blending and enhancing modifications.
Although the overall use of oils has decreased in recent years, a number of reasons make
prediction of their imminent demise premature.
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OIL USE IN PAINTS
• The principal oils now used in surface coatings are linseed, soybean castor, and
coconut oils are all derived from seeds or nuts.
• Tall oil (in fact available only as fatty acid and not combined with glycerol) is a by-
product of paper manufacture and derives its name from the Swedish name for pine.
• Dehydrated castor oil, included in order to give its fatty acid content here for
comparison.
• Oils used in the coatings industry will always have been refined, to remove waxes, free
fatty acids, lecithins, and other natural contaminants, because the presence of those
substances would in almost all cases have deleterious effects on the derived coating
resins.
• Tall oil is particular is now used almost exclusively in distilled form, in order to free it
from any rosin content.
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• All oils except tall oil occur naturally as a triglyceride, free fatty acids are available from
almost all oils as alternative reactants to extend formulating flexibility.
• The use of both oils and fatty acids in coating resins.
• Oils used in coatings and their Fatty acid composition.
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Oils Saturated
acid
Oleic acid 9,12
linoleic
acid
9,12,15-
Linolenic
acid
Other
acids
Soybean oil 14 22-28 52-55 5-9 0
Tall fatty
acid
3 30-35 35-40 2-5 10-15
Linseed oil 10 20-24 14-19 48-54 0
Castor oil 2-4 6-8 3-6 0 85-87
Castor oil,
dehydrated
2-4 6-8 48-50 0 40-42
Coconut oil 89-94 6-8 0-2 0 0

CLASSIFICATION OF OIL
• Oils are classified based on sufficient unsaturation in its total fatty acid chains to
autoxidize to fully dried films.
• Drying: linseed oil, with 60% of its fatty acids doubly or triply unsaturated is termed as
drying oil.
• Semidrying: Soybean, tall and dehydrated castor oil are generally termed as semidrying
oil.
• Non-drying: castor oil and coconut oil are non-drying oils.
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BIODIESEL
• Many researchers have investigated the possibility of the using vegetable oils straight
or blended as diesel substitutes. Use of vegetable oils as fuel for compression-ignition
engines is not new.
• The inventor of diesel engine Sir Rudolf Diesel displayed an engine fueled with peanut
oil at the Paris Exposition of 1900.
• The use of palm oil as a diesel fuel was reported as early as 1920.
• The term biodiesel refers to methyl or ethyl esters derived from vegetable oil. It can
also refers to pyrolysis products such as diesel-vegetable oil blends, microemulsions of
alcohols and water in vegetable oils, and fermentation butanols.
• Ester are used because they have lower viscosity and better fuel properties than
vegetable oils.
• Engines run on vegetable oil esters are known to emit less dark smoke and CO and no
SO2.
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SYNTHESIS OF BIODIESEL
• Methyl esters of fatty acids can be synthesized either by esterification of fatty acids or
by transesterification of fat triglycerides.
• The predominant method of synthesis of methyl esters is the transesterification of fats
and oils with methanol.
• The ester interchange i.e. the replacement of the alcohol components glycerol by
methanol, takes place quite easily at low temperatures 50-70 °C and under
atmospheric pressure with an excess of methanol and in the presence of an alkaline
catalyst such as sodium or potassium hydroxide.
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SOME OF THE
AVAILABLE BIODIESEL
PRODUCTION
TECHNOLOGY
• It is possible to convert
vegetable oils such as
crude palm oil esters with
varying amounts of free
fatty acids in a continuous
process by combining the
esterification and
transesterification
processes as developed
by PORIM. This has been
successfully demstrated in
a 3000 tpa pilot plant.
11/7/2020 Dr. Mohammed Danish (UnikL-MICET)/ Oil and Fat Technology (CPB 30303) 28

HIGHLIGHTS OF VEGETABLE OIL ALKYL
ESTER AS BIOFUEL
• Methyl esters of vegetable oils are better diesel substitutes than the original oils.
• Simple alkyl esters, in contrast to triglycerides, improves viscosity, but volatility remain poor.
This may cause a problem in direct injection engines.
• Introduction of a double bonds resulted in increased efficiency; thus ethyl oleate had the
highest thermal efficiency.
• Among the methyl esters f saturated acids, thermal efficiency is inversely related to the chain
length of the fatty acid.
• A study of the efficiency of various ester of fatty acid as diesel fuel suggests that a vegetable oil
having a high content of oleic acid or short-chain saturated acid transesterified to produce
ethyl esters should produce a good test materials as an alternative diesel fuel.
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29

END OF THE
SLIDES HERE!
T H A N K S F O R Y O U R PAT I E N C E !
11/7/2020
Dr. Mohammed Danish (UnikL-MICET)/ Oil and Fat Technology (CPB
30303) 30

Non edible application of oil and Fat (Unit 6 b)

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