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600BC.
- First recorded manufacture of soap.
2800 B.C. (Babylon )
-A soap-like material found in clay cylinders
during the excavation of ancient Babylon
1500 B.C.
-Ebers Papyrus, a medical document from about
1500 B.C., describes combining animal and vegetable oils
with alkaline salts to form a soap-like material.

• Soap-making was an established craft in Europe by the
seventh century. Vegetable and animal oils were used
with ashes of plants, along with fragrance.
• The English began making soap during the 12th century.
• The soap business was so good that in 1622, King
James I granted a monopoly to a soap-maker for
$100,000 a year.

• A major step toward large-scale commercial soap-making
occurred in 1791 when a French chemist, Nicholas
Leblanc, patented a process for making soda ash*, or
sodium carbonate, from common salt.
• 20 years later - The science of modern soap-making was
born with the discovery by Michel Eugene Chevreul,
(another French chemist), of the chemical nature and
relationship of fats, glycerine and fatty acids.
• mid-1800s - Ernest Solvay (Belgian chemist)- the
ammonia process, which used common table salt, or
sodium chloride, to make soda ash. “Solvay's process”
History of Soap Making _

• Soap is a cleansing agent created by the chemical reaction
of a fatty acid with an alkali metal hydroxide.
• water-soluble sodium or potassium salts of fatty acids
• made from fats and oils, or their fatty acids, by treating them
chemically with a strong alkali
• has the general chemical formula RCOOX.
COMPONENTS
• The three main components of soap by both cost and
volume are oils, caustic and perfumes.

The typical composition of a couple of common classes of
commercial soap are:
• Tallow soaps:
40-45% oleate,
25-30% palmitate,
15-20% stearate
• Coconut oil soaps (even more impure):
45-50% various C12 carboxylates,
5-6% oleate,
10-15% various C12 or shorter carboxylates

 A soap molecule has two
ends with different
properties:
1. A long hydrocarbon part
which is hydrophobic (i.e. it
dissolves in hydrocarbon).
2. A short ionic part
containing COO-Na+
which is hydrophilic (i.e. it
dissolves in water).

 Fats and Oils
- used in soap-making come from animal or plant
sources. Each fat or oil is made up of a distinctive mixture of
several different triglycerides.
Alkali
• - An alkali is a soluble salt of an alkali metal like
sodium or potassium. Originally, the alkalis used in soap-
making were obtained from the ashes of plants, but they
are now made commercially. Today, the term alkali
describes a substance that chemically is a base (the
opposite of an acid) and that reacts with and neutralizes an
acid.

Soap is produced industrially in four basic steps:
1. Saponification
- A mixture of tallow (animal fat) and coconut oil is
mixed with sodium hydroxide and heated. The soap
produced is the salt of a long chain carboxylic acid.
2. Glycerine removal
- Glycerine is more valuable than soap, so most of it
is removed. Some is left in the soap to help make it soft
and smooth.

3. Soap purification
- Any remaining sodium hydroxide is neutralized
with a weak acid such as citric acid and two thirds of the
remaining water removed.
4. Finishing
- Additives such as preservatives, colour and
perfume are added and mixed in with the soap and it is
shaped into bars for sale.

THE COLGATE-PALMOLIVE SOAP MANUFACTURING PROCESS

This is a continuous process
(Figure 1) which uses a plant
built by Binacchi & Co. The
process is best understood in
terms of two streams: soap
flowing in the order given below
against a counter-current of lye.

This reaction is exothermic, and progresses quickly and efficiently at
around 125oC inside an autoclave type reactor.

• The raw materials are continually fed into a reactor in
fixed proportions. Assuming a production rate of 1000 kg
wet soap per hour and a 80:20 tallow:coconut oil mix.
• These ingredients alone would give a low water, high
glycerine soap. Soap needs to be about 30% water to be
easily pumpable, and even then needs to be held at
around 70oC, so excess lye is added to hydrate the soap
and dissolve out some of the glycerine.

• The wet soap is pumped to a "static separator" - a
settling vessel which does not use any mechanical
action. The soap / lye mix is pumped into the tank where
it separates out on the basis of weight. The spent lye
settles to the bottom from where it is piped off to the
glycerine recovery unit, while the soap rises to the top
and is piped away for further processing.

• The soap still contains most of its glycerine at this stage, and
this is removed with fresh lye in a washing column. The
column has rings fixed on its inside surface. The soap
solution is added near the bottom of the column and the lye
near the top. As the lye flows down the column through the
centre, a series of rotating disks keeps the soap / lye mixture
agitated between the rings. This creates enough turbulence
to ensure good mixing between the two solutions.

• The lye is added at the top of the washing column, and
the soap removed from the column as overflow. As the
lye is added near the overflow pipe the washed soap is
about 20% fresh lye, giving the soap unacceptably high
water and caustic levels. Separating off the lye lowers
the electrolyte levels to acceptable limits. The soap and
lye are separated in a centrifuge, leaving a soap which is
0.5% NaCl and 0.3% NaOH, and about 31% water. The
lye removed is used as fresh lye.

• Although the caustic levels are quite low, they are still
unacceptably high for toilet and laundry soap. The NaOH
is removed by reaction with a weak acid such as coconut
oil (which contains significant levels of free fatty acids),
coconut oil fatty acids, citric acid or phosphoric acid, with
the choice of acid being made largely on economic
grounds. Some preservative is also added at this stage.

• Sodium stearate (Chemical formula: C17H35COO-Na+)
• Sodium palmitate (Chemical formula: C15H31COO-
Na+)
•
• Sodium oleate (Chemical formula: C17H33COO-Na+)

• Cheaper Toilet Soaps
• Run and Glued Up
Soaps
• Curd Soap
• Cold made toilet soaps
• Medicinal Soap
• Sulphur Soap
• Tar Soap
• Carbolic Soap
• Peroxide Soap
• Mercury Soap
• Castile Soap
• Eschweger Soap
• Transparent Soap
• Shaying Soap
• Pumice/ Sand Soap
• Liquid Soap
• Textile Soap
• Wool Throwers

Glycerine recovery
As has already been stated, glycerine is more valuable
than the soap itself, and so as much of it as possible is
extracted from the soap. This is done in a three step
process.
• Step 1 - Soap removal
The spent lye contains a small quantity of dissolved
soap which must be removed before the evaporation
process. This is done by treating the spent lye with
ferrous chloride.

• Step 2 - Salt removal
Water is removed from the lye in a vacuum
evaporator, causing the salt to crystallize out as the
solution becomes supersaturated. This is removed in a
centrifuge, dissolved in hot water and stored for use as
fresh lye. When the glycerine content of the solution
reaches 80 - 85% it is pumped to the crude settling tank
where more salt separates out.

• Step 3 - Glycerine purification
A small amount of caustic soda is added to the
crude glycerine and the solution then distilled under
vacuum in a heated still. Two fractions are taken off - one
of pure glycerine and one of glycerine and water. The
glycerine thus extracted is bleached with carbon black then
transferred to drums for sale, while the water/glycerine
fraction is mixed with the incoming spent lye and repeats
the treatment cycle.

• The lye is a main effluent source in this industry and it
mainly consists of unreacted fatty matter, caustic soda,
sodium chloride and glycerol.
• According to the above effluent analysis, it is shown that
the effluent is highly polluted and that it should not be
discharged into the surface drains. The effluent should be
treated to satisfy the tolerance levels specified for
discharge into inland surface waters.
• Treatment could be done either to recover glycerol and
sodium chloride from spent lye or by increasing the
glycerol content of the spent lye to an economical level.

Advantages
• Very effective as a
bactericide
• It will form gels, emulsify
oil and lower the surfaces
tension of water.
• Excellent everyday
cleaning agent.
• Good biodegradability
Disadvantages
• Oils and perfume are
immiscible in water and if
spilled create havoc,
although the oils do
solidify at room
temperature.
• When used in hard water,
soap can produced a
scum.
**Soaps, will react with metal ions in the water
and can form insoluble precipitates (soap scum).

• The chemistry of soap manufacturing stayed essentially
the same until 1916, when the first synthetic detergent
was developed in Germany in response to a World War I-
related shortage of fats for making soap.
• Known today simply as detergents, synthetic detergents
are washing and cleaning products without soap,
"synthesized" or put together chemically from a variety of
raw materials.

• Detergents are the sodium salts of long chain benzene
sulphuric acids.
• uses a synthetic surfactant in place of the metal fatty acid
salts used in soaps
• both in powder and liquid form, and sold as laundry
powders, hard surface cleansers, dish washing liquids,
fabric conditioners etc.
• primarily surfactants, which could be produced easily from
petrochemicals.

• The cleansing action is exactly similar to that of soaps
whereby the formation of micelles followed by
emulsification occurs.
STRUCTURE
*Detergents are similar in structure and function to soap,
and for most uses they are more efficient than soap and
so are more commonly used. In addition to the actual
'detergent' molecule, detergents usually incorporate a
variety of other ingredients that act as water softeners,
free-flowing agents etc.

TYPICAL INGREDIENTS:
• Sodium carbonate
• Sodium bicarbonate
• Sodium perborate
• Sodium sulphate
• Tetrahydrate
• Sodium tripolyphosphate
• Sodium silicates
• Sodium percarbonate
• Anionics
• Encapsulated enzymes
• Colored beads
• Anti-foaming powder
• Polymers that release
stains
• Polymers that prevent new
stains
• Sodium silicates

The first “self-acting” laundry detergent
was launched by Henkel in the German
market on June 6, 1907, and was given
the name “Persil”.
The name derived from the two most
important chemical raw materials in the
product, perborate and silicate.
Today, both Henkel and Unilever
manufacture their own formulations. Persil
is Unilever's premium brand in the United
Kingdom and the Republic of Ireland.

• Step 1 - Slurry making
The solid and liquid raw ingredients are dropped
into a large tank known as a slurry mixer. 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 alkylbenzenesulphonic acid. The
mixture is then further heated to 85oC and stirred until
it forms a homogeneous slurry.

• Step 2 - Spray drying
The slurry is deaerated in a vacuum chamber and
then separated by an atomiser into finely divided droplets.
These are sprayed into a column of air at 425oC, where
they dry instantaneously. The resultant powder is known
as 'base powder', and its exact treatment from this point on
depends on the product being made.

• Step 3 - Post dosing
Other ingredients are now added, and the air
blown through the mixture in a fluidiser to mix them into a
homogeneous powder. Typical ingredients are listed in
Table 3.

• Step 1 - Soap premix manufacture
Liquid detergent contains soap as well as
synthetic surfactants. This is usually made first as a
premix, then other ingredients are blended into it. This step
simply consists of neutralising fatty acids (rather than fats
themselves) with either caustic soda (NaOH) or potassium
hydroxide.

• Step 2 - Ingredient mixing
All ingredients except enzymes are added
and mixed at high temperature. The ingredients used in
liquid detergent manufacture are typically sodium
tripolyphosphate, caustic soda, sulphonic acid, perfume
and water. The functions of these ingredients has been
covered above.

• Step 3 - Enzyme addition
The mixture is cooled and milled, and the
enzymes added in powder form.

Advantages
• biodegradable
• do not decompose in
acidic medium.
• As detergents are derived
from petroleum they save
on natural vegetable oils.
• can lather well even in
hard water*
Disadvantages
• Their elimination from
municipal wastewaters by
the usual treatments is a
problem.
• have a tendency to produce
stable foams in rivers that
extend over several hundred
meters of the river water.
• danger to aquatic life.
• Some surfactants are
incompletely broken down
with conventional treatment
processes
• inhibit oxidation*

• Phosphate Builders
• Excess of detergent foam
• Effluent
• Excess chemicals

• Within the plant, all the process areas are also bunded,
and the trade waste from there piped to an interception
tank before draining to the council's trade waste system.
• The contents of the interception tank are continuously
monitored for acidity or alkalinity, and is designed to
settle out excess solids or light phase chemicals.
• If a spill is detected in the plant itself, a portion of the
interception tank can be isolated off and the effects of the
spill neutralized before the waste is dumped.
• Phosphates can be removed from sewage and recycled,
either back into industrial products, or into food
production.

• The manufacturing process itself is closely monitored to
ensure any losses are kept to a minimum. Continuous
measurements of key properties such as electrolyte
levels and moisture both ensure that the final product is
being made to spec, and ensures the manufacturing
process is working as it was designed to.
• To determine the safety of a cleaning product ingredient,
industry scientists evaluate the toxicity of the ingredient.

Number of Factors Affecting Exposure:
- duration and frequency of exposure to the ingredient
- the concentration of the ingredient at the time of exposure
- the route and manner in which the exposure occurs

Personal Cleansing laundry
dishwashing Household
Cleaning

• The origins of the chemical industry in the Philippines can
be traced back during the 19th century. This mainly
involved the small-scale and rudimentary production
involving some chemical processes.
• As early as the 1950s, leather for slippers, harness, and
soles were already being produced in Meycauayan,
Bulacan, with the leather being tanned through the use of
vegetable oil tannin extract from guamachili tree, or
'kamachile'.
• Shortly after, around 1875, soap making as a trade --
involving the mixing of coconut oil with alkali (lye)
obtained from leaching wood ashes in small iron pots --
started in the country.

• It was not until the early 20th century that more
significant and advanced chemical activities began to
take place.
• In 1911, the first modern soap factory was built, followed
quickly by others. Intensive sales and advertising drives
developed the Philippines market for soap.
• By the time World War II broke out, there were already
135 soap establishments in the country, with only three
processors using modern methods.

SOAP
• They are metal salts of
long chain higher fatty
acids.
• prepared from vegetable
oils and animal fats.
• cannot be used effectively
in hard water as they
produce scum i.e.,
insoluble precipitates of
Ca2+, Mg2+, Fe2+ etc.
DETERGENT
• These are sodium salts of
long chain hydrocarbons
like alkyl sulphates or
alkyl benzene
sulphonates.
• prepared from
hydrocarbons of
petroleum or coal.
• do not produce insoluble
precipitates in hard water.
They are effective in soft,
hard or salt water.
• more soluble in water

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