This document provides a history of soap making and the development of detergents. It discusses how soap making has evolved from ancient times using animal and vegetable oils combined with alkalis. It describes the traditional soap making process and key developments in commercial production. The document also summarizes the history of detergents, from the first synthetic detergent created in 1916 to their widespread use replacing soap after World War 2. The chemistry and components of detergents are briefly outlined.

1. BY:
A manse, B ragais, C ledera

2. • The first recorded manufacture of soap was in 600BC.
• A soap-like material found in clay cylinders during the
excavation of ancient Babylon is evidence that soap-
making was known as early as 2800 B.C. Such materials
were later used as hair styling aids.
• Records show that ancient Egyptians bathed regularly.
• The 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 used
for treating skin diseases, as well as for washing.

3. • At about the same time, Moses gave the Israelites
detailed laws governing personal cleanliness. He also
related cleanliness to health and religious purification.
• Soap got its name, according to an ancient Roman
legend, from Mount Sapo, where animals were sacrificed.
• Rain washed a mixture of melted animal fat, or tallow,
and wood ashes down into the clay soil along the Tiber
River. Women found that this clay mixture (soap) made
their wash cleaner with much less effort.

4. • The first of the famous Roman baths, supplied with water
from their aqueducts, was built about 312 B.C. The baths
were luxurious, and bathing became very popular.
• By the second century A.D., the Greek physician, Galen,
recommended soap for both medicinal and cleansing
purposes.
• After the fall of Rome in 467 A.D. and the resulting
decline in bathing habits, much of Europe felt the impact
of filth upon public health. This lack of personal
cleanliness and related unsanitary living conditions
contributed heavily to the great plagues of the Middle
Ages, and especially to the Black Death of the 14th
century.

5. • It wasn't until the 17th century that cleanliness and
bathing started to come back into fashion in much of
Europe.
History of Soap
Making___________________
• 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.
• Italy, Spain and France were early centres of soap
manufacturing, due to their ready supply of raw materials
such as oil from olive trees.

6. History of Soap Making _
• Italy, Spain and France were early centres of soap
manufacturing, due to their ready supply of raw materials
such as oil from olive trees.
• 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.
• In the 19th century, soap was heavily taxed as a luxury
item in several countries. When the high tax was
removed, soap became available to ordinary people, and
cleanliness standards improved.

7. History of Soap Making _
• 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”

8. History of Soap Making
_
• 1850 - soap-making, one of North America's fastest-
growing industries. Its broad availability changed soap
from a luxury item to an everyday necessity.

9. • 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.

10. 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,
16-20% various C14 carboxylates,
8-10% various C16 carboxylates,
5-6% oleate,
10-15% various C12 or shorter carboxylates

11.  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).

14.  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.
• In a triglyceride molecule, three fatty acid molecules are
attached to one molecule of glycerine. There are many types of
triglycerides; each type consists of its own particular
combination of fatty acids. Fatty acids are the components of
fats and oils that are used in making soap. They are weak acids
composed of two parts: A carboxylic acid group consisting of
one hydrogen (H) atom, two oxygen (O) atoms, and one carbon
(C) atom, plus a hydrocarbon chain attached to the carboxylic
acid group. Generally, it is made up of a long straight chain of
carbon (C) atoms each carrying two hydrogen (H) atoms.

15. 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.
• The common alkalis used in soap-making are sodium
hydroxide (NaOH), also called caustic soda; and
potassium hydroxide (KOH), also called caustic potash.

16. Soaps are the product of the reaction between a fat and
sodium hydroxide:

17. 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.
*Saponification - process of making soap by the hydrolysis of fats and oils with alkalies

18. 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. Soap is not very soluble in salt water,
whereas glycerine is, so salt is added to the wet soap
causing it to separate out into soap and glycerine in salt
water.
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.

19. 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.

20. THE COLGATE-PALMOLIVE SOAP MANUFACTURING PROCESS

21. 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.

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

23. • 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 lye added is
known as "half spent lye" and is the lye discharged from
the washing column (see below). This lye already
contains some glycerine, but it is further enriched by that
formed in the saponification reaction.

24. • 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.

25. • 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 rate of glycerine production is calculated and the rate at
which fresh lye is added to the washing column then set such
that the spent lye is 25 - 35 % glycerine. Glycerine is almost
infinitely soluble in brine, but at greater than 35% glycerine
the lye no longer efficiently removes glycerine from the soap.
The soap is allowed to overflow from the top of the column
and the lye ("half spent lye") is pumped away from the bottom
at a controlled rate and added to the reactor.

26. • 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.

27. • 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.

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

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

31. 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.

32. • 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.

33. • 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.

34. • 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.

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

37. _________History of Detergents/Detergent
Making__________
• 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.

38. • Household detergent production in North America began in the
early 1930s, but did not really take off until after World War II.
• The first detergents were used chiefly for hand dishwashing
and fine fabric laundering.
• The breakthrough in the development of detergents for all-
purpose laundry uses came in 1946, when the first "built"
detergent (containing a surfactant/builder combination) was
introduced in the United States.
• By 1953, sales of detergents in the United States had
surpassed those of soap. Now detergents have all but
replaced soap-based products for laundering, dishwashing
and household cleaning. Detergents (alone or in combination
with soap) are also found in many of the bars and liquids used
for personal cleansing.

39. • 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. *Surfactants lower the surface tension of
water, essentially making it 'wetter' so that it is less likely to
stick to itself and more likely to interact with oil and grease.
• * SURFACTANTS - SURFACE ACTIV AGENTS

40. • 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.

41. • petrochemicals

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

43. 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.

44. (DETERGENT)

46. • 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.

47. • 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.

48. • 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.

49. • 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.

50. • 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.

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

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

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

56. • 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.
• Often an off-spec product can be reprocessed and
blended rather than dumped, and even washout water
can be reprocessed to minimised the discharges from the
plant.

57. • Phosphates can be removed from sewage and recycled,
either back into industrial products, or into food
production.
• They are thus the only recyclable detergent ingredient.

58. PHYSICAL
This information applies to ingredients
processed through household septic tank
systems as well as municipal treatment
plants.
Two basic steps occur in the treatment of
wastewater in both systems.:
• The first step, called primary treatment,
consists of the removal of solid material,
such as grit or grease, from the wastewater
by physical means, i.e., settling and
flotation in tanks.
• The second step, called secondary
treatment, removes the dissolved material
by biological means, i.e., consumption by

59. Any small amounts of chemicals which
are not biodegraded or removed during
sewage treatment are diluted in surface
waters, soil and the ocean. They
continue to biodegrade or be removed
from water by attaching to solids, a
process known as adsorption.

60. • 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. Hence the
losses in the plant will indirectly be minimised because
the process itself is being monitored.

61. • 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

62. • Manufacturers constantly monitor the quality of their detergents,
and they utilize the same testing methods to assess the
effectiveness of new products. In one method, light is shined onto a
piece of fabric that has been soiled and then washed in the test
detergent. The amount of light reflected, compared to the amount
reflected by a sample of the original fabric, is a measure of
cleanliness. A reflection rate of 98 percent is considered quite good
and indicates that the detergent has cleaned properly.
• Another method involves laboratory burning of a small amount of
material that has been soiled and then laundered. The weight of the
ashes, plus the weight of the gaseous results of the burning, reveal
how much of the dirt remained in the fabric after laundering. A
result that is much higher than a clean test sample indicates that a
significant amount of dirt was retained in the laundered sample.
Naturally, the goal is to come as close to the weight of a clean
control sample as possible.

63. Personal Cleansing laundry
dishwashing Household
Cleaning

64. Four General Categories:
• Personal Cleansing – include bar soaps, gels, liquid soaps
and heavy duty hand cleaners.
• Laundry – available as liquids, powders, gels, sticks, spray
pumps, sheets and bars
• Dishwashing – include detergents for hand and machine
dishwashing as well as some specialty products. (liquids,
gels, powders, solids)
• Household Cleaning – available as liquids, gels, powders,
sheets and pads for use on painted, plastic, metal,
porcelain, glass and other surfaces, and on washable floor
coverings.

65. IN THE PHILIPPINES

66. • 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.

67. • 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.

68. THE COMPARISON

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

70. Chemical Process Industries © 2012