Theory:

Soap is one of the oldest chemical created over two thousand years
ago by soaponification animal fats with the ashes from plants.
Although soap are generally used as surfactant for washing,
Bathing cleaning, but they are also being used in textile spinning
and as important component of lubricating fat. Now soap and
detergent have become essential part of our society. There has
been continuous development Soap production technology starting
with batch kettle making process in cottage industry and to present
continuous present soap making process using either fat
soaponification or by fatty acid neutralization utilizing a wide
variety of natural and synthetic feed stock [Zhu et al., 2004]. Soaps
are also key components of most lubricating grease which are
usually mixture of, calcium, sodium, lithium soaps and mineral
oil.( ‫من ملف‬lec1 ‫ على ديسكتوب‬... ‫)في كراجويشن‬
From a chemical standpoint, is a salt (or a mixture of salts) of fatty
acids. As with all salts, soap contains a positive ion, usually Na+ or
K+, and a negative ion, usually the anions of long-chained
carboxylic acids obtained by the hydrolysis of animal or vegetable
fats. These fatty acids, of which there are about 20 naturally
happening members, are carboxylic acids containing 14, 16, or 18
carbon atoms in an unbranched chain. The even numbered chains
result from the fact that fats are synthesized in cells by the
polymerization of a 2-carbon acetate unit.(9-soap-down)
a soap factory is an industrial and marketable project, and even if
modest in range and on the scale of a cottage industry, it has a
responsibility to be viable and capable of ensuring its survival,
profitability and growth. This being the case, the marketable aspect
is very important and needs to be studied in depth. The soap
market is in fact a user goods market on which there is generally
fierce competition between soap formed locally and soap imported
at low prices.

This is why the success of any soap plant project - which,

moreover, very often develops in a very complex technological,
economic, financial and socio-cultural context - depends more on
the ability of the managers and the quality of the operational,
strategic and commercial organization than on purely technical
factors. At a technological level, facilities are more than enough
for developing a production line which is perfectly placed to meet,
in terms of capacity and facilities, any clearly-defined and
reasonable commercial objectives.(Soap Production (CDI, 1995, 70 p.)
History:
The first type of purification agent, used by humankind for
centuries, was soap. Although it has now been supplemented by
different synthetic detergents in highly developed countries for
laundry and household use, it is still favorite for personal hygiene.
In less developed countries it is preferred for laundry use.

O
NaOH ||
fats glycerol + R-C-O-Na+

The origin of personal purity dates back to very old times. Since
water is essential for life, the first people lived near water and
learnt on its purification properties. Soap got its name, according
to an ancient Roman legend, from increase Soap, where animals
were sacrificed to appease the gods. The mixture of decayed
animal fat and wood ash that ran down to the clayey soil close to
the river was found to make washing simple for women inhabiting
the area. According to the medical document Papyrus, soap-
making dates back to about 1500 BC, and that a mixture of animal
30 and vegetable oil with alkaline salts was used to form a soap-
like material.1 In ancient India too, people used soap preparations
made from plant or animal fats. Soap was made by boiling tallow
(or other hard animal fat) or vegetable or fish oil in an alkaline
solution. new technology has led to the evolution of synthetic
detergents that have gradually replaced soaps. Earlier, detergents
were used chiefly for hand dishwashing and fine fabric laundering.
This was followed by the development of all purpose detergents
for laundry introduced in the United States of America in 1946.
Soaps are the sodium or potassium salts of certain fatty acids
obtained from the hydrolysis of triglycerides. The potassium salts
form the "soft soaps" that have become popular recently. The fats
used in soap manufacture come from diverse natural sources.
Animal tallows and coconut oil are the favored sources of the
triglycerides, and quite often mixtures from different sources are
used to vary hardness, water solubility, and cleansing action of the
final product. Palm, olive, cottonseed, castor, and tall oil are other
sources. The side chains are usually Cn-Ci8 in length.
Manufacturing processes are both batch and continuous.
Sometimes the triglyceride is steam-hydrolyzed to the fatty acid
without strong caustic and then in a separate step it is converted
into the sodium salt. Either way gives a similar result. Soaps have
some disadvantages compared to synthetic detergents: they are
more expensive, they compete with food uses for fats and oils, and
their calcium and magnesium salts formed in hard water are very
insoluble and precipitate onto the clothing being washed.

Figure 24.3 U.S. consumption of soaps vs. total synthetic detergents. (Source:
Chemical Economics Handbook)
Raw material:

Two major materials plus one by-product dominate soap-making

operations, the final-product user performance, and the associated
costs. These are triglyceride (TG) fatty matter, caustic soda, and
glycerine, respectively. They dominate because two major
processes for making soap are available-the TG process and the
distilled fatty acid (DFA) process. The details of each process are
different. However, both processes convert TG fatty matter and
caustic soda into soap (i.e., the sodium salt of fatty acids),
with the by-product glycerine released during the processing.
In the TG process, the TG is first cleaned of impurities and then
reacted directly with caustic soda to produce an aqueous solution
of soap and glycerine. This mixture is then separated by extracting
the glycerine into a brine solution for recovery. For glycerine soap,
the separation step is dispensed with, and all the glycerine is left in
the final soap-bar product.
In the DFA process, the TG is hydrolyzed at high temperature with
an excess of water which releases the fatty acids. 'The glycerine
passes from the process in the excess water stream for recovery.
The crude fatty acid is cleaned of impurities by distillation, and
then reacted with caustic soda to form the soap. Should glycerine
soap be required to be made by this process, then the recovered
glycerine is added back.
These three materials are:

1) Triglyceride Fatty Matter:

Fatty matter is by far the largest constituent of a soap bar, typically

occupying about 7040% of its total weight and over 80% of its
total ex works cost. Therefore, a considerable part of this chapter is
devoted to fatty matter. TG oils are esters of three fatty acids and
glycerine with generic structures as shown in the diagram
below. R , R , and R”’ are carbon chains with lengths mostly
ranging from 7-19 which can be fully saturated or mono- or
polyunsaturated.The fatty matter is usually transported and stored
at ambient temperature, if possible, or at about 5-10°C above its
melting point, to ensure that it is mobile for pumping but not too
hot to cause degradation. Preferably, the heating medium is
temperature-controlled hot water or electrical tracing to ensure no
hot spots which again cause degradation.

  
lauric oils hard fats soft oils

 coconut oil  tallow (cattle, sheep)  soya bean oil

 palm kernel oil  palm oil (stearin)  groundnut oil
 cotton seed oil

Lauric oils, found in high proportions in coconut oil and palm

kernel oil, are the fatty materials with the best combination of the
properties generally desired in soap. They are used in the majority
of formulations because they provide high lathering power and
detergency. They are used in cold or hot saponification, in
combination with other oils and fats, to improve hardness and to
slow down the rate of dissolution of manufactured soaps.

Tallow and palm oil, usually after bleaching and deodorisation,

are the fatty materials most often used in combination with lauric
acids.( Soap Production (CDI, 1995, 70 p.))

Soft oils are sometimes used in limited proportions in the

manufacture of low-grade soaps because of their poor properties.

2)Glycerine:

Glycerine is mostly produced as a by-product from soap making

and oleochemical production, the latter being principally fatty
acids but more recently including biodiesel. The dilute glycerine
from these processes is usually treated to remove gross
contaminants, and then concentrated by evaporation
to about 80 wt% for soap making or 90 wt% for oleochemical
production. The difference between the two is that the soaper's
crude contains about 10 wt% of salt which originated in the soap-
washing step. Both of these crudes are traded internationally, but
eventually nearly all are refined by distillation and adsorption on
ion-exchange resin and/or activated carbon to a set of grades which
contain greater than 99.5 wt% of glycerine. The remainder of this
refined product is mostly water. Like caustic soda, no market
exchange is available for glycerine as for agricultural products
such as TG oils. This is because relatively few producers exist
worldwide, and the production of the oleochemical/ glycerine
complex can, within reason, be turned up and down at will to suit
major seasonal fluctuations in demand. However, market-
intelligence organizations confidentially obtain negotiated prices
for recent large contracts and from traders who sell to smaller
users.
 3)Caustic soda:

Caustic soda is a co-product with the chlorine

ofelectrolyzingsodium chloride brine. The two coproducts
are locked by chemistry into being produced in stoichiometric
proportions, that is, 40 caustic soda to 35.5 of chlorine or 1.13: 1.
Production is carried out all over the world, and most of the two
products are used locally. However, local production and use for
both are seldom in balance, and so caustic soda, being the most
easily transported, is the one traded globally. Caustic soda and
chlorine are basic chemicals for many industries, and their
production has increased in North America and Western Europe by
about 2-3% per year for the last 10 years but by 50% in China in
the last 5 years. World caustic-soda production was at about 50
million dry tonnes in 2007, with about 27% in the United States;
21% in Europe; and 20% in China, 7% in Japan, and 12% in other
Asian countries. Most soap-making plants receive their caustic
soda in bulk in road tankers or rail cars. Caustic soda is corrosive,
and so operating staff must be protected, usually wearing full
personal protection and following strict safety procedures and
permits when working with it during deliveries or when
maintaining any equipment.( 13 ‫ملف‬soap)

manufacture of caustic soda by diaphragm cells: the main raw

material for the manufacture of caustic soda by electrolytic method
is the common salt. In india this salt is found in many parts such as
sambhar, kharagoda ,…. (industrial chemistry M.G.arora,M.singh)
Other Names: Sodium Hydroxide
MF: NaOH
EINECS No.: 215-185-5
Purity: 96%
Appearance: White Solid
Application: Textile
HS CODE: 28151100
Color: white
Boiling Point: 1390 c
Shape: Flake,solidOther Names: Sodium Hydroxide
MF: NaOH
EINECS No.: 215-185-5
Purity: 96%
Appearance: White Solid
Application: Textile
HS CODE: 28151100
Color: white
Boiling Point: 1390 c
Shape: Flake,solid
Type of soap:

1) Laundry soaps : Laundry soaps are formulated to eliminate

grease, solid particles and organic compounds from clothes.
They can be found in liquid, powder and gel forms.

2) Cleaning soaps: Cleaning soaps have different

formulations to clean grease and soil. The difference between
cleansers and cleaning soaps is that cleaning soaps don't
contain harsh abrasives.

3) Personal soaps: This kind of soap is made in many forms

and special formulations for specific personal hygiene needs.
One type of the personal soap is the antibacterial soap that is
made to prevent bacteria and viruses from spreading. There
are also body and hair soaps that have a mix of ingredients
that cleans both the skin and hair.

4) Novelty soaps: Novelty soaps are especially manufactured

for the kids and include the soaps in the shapes of various
items, such as a rubber ducky or the soap-on-the-rope. There
are made not only to clean dirt and grime, but for amusement
and enjoyment as well.

5) Perfumed soaps: Perfumed soaps are produced by adding a

few additional ingredients and perfume.
6) Guest soaps: Guest soaps are miniature soaps that are
made and shaped into attractive shapes and they are basically
designed for the use by guests either in the main bathroom or
separate guest bathroom. Popular and commonly used shapes
are flowers, sea shells and rounds

7) Beauty soap : Beauty soaps are produced to feature

attractive fragrances, and ingredients for a variety of skin
types. They can feature glycerin, or special oil blends.

8) Medicated soaps: Medicated soaps and original soap are

very similar. Unlike original soap, medicated soap has
the addition of antiseptics and disinfectants.

9) Glycerin soaps: Glycerin is a normally produced during

the process of soap production. Soaps which include glycerin
in them tend to make your skin feel moister.

10)Transparent soap: Transparent soap uses slightly

different ingredients and usually some form of alcohol to
alter the process which is also conducted at higher
temperatures. Not all transparent soaps are glycerin soaps.

11)Liquid soaps: Liquid soaps are actually very difficult to

produce and many of the commercial liquid soaps are just in
fact detergents.(website of soaphistory)

12) Castile soap : a mild soap originally made in Spain with

pure olive oil. Today many “castile” soaps are made with
other vegetable oils. Castile is a marvelous cleanser,
producing a rich lather.
13) Cream soaps : soaps containing cold cream materials,
moisturizers and emollients. Cream soaps are particularly good
for dry and delicate skin

14) Deodorant soaps : soaps to which antibacterial agents have

been added to reduce odor-causing bacteria.

15) Floating soaps : soaps having air bubbles incorporated to

lower the density. This causes the bar to float.

16) Hypo-allergenic soaps : Mild formula soaps, low in

potential irritants. They usually produce a poor lather.

17) Medicated soaps : soaps containing medications such as

tar, sulphur, or antibacterial ingredients, used to treat acne and
other skin disorders. Medicated soaps require through rinsing
and are not recommended for sensitive skin.

18) Milled soaps : these are the most commonly used, mass
produced soaps. Milling refers to the combination of color,
smell and soap flakes.

19) Oatmeal soap : A rough –textured soap to which oatmeal

has been added as a mild abrasive and lather. Good for oily, dry,
and normal skin.(9-soap)
Global and local market demand:

The market for soaps

Soap is generally classified as a staple commodity alongside

detergents. It also figures in the bathing and personal care market.
Only rarely, statistics for soap is directly separable from those for
detergents or toiletries.

Recent market analysis by Euromonitor(2000) showed that in

1999 soaps and detergents together represented around 12.4% of
consumer expenditure in household goods of industrialized
countries and between 2.6 and 5% only in the developing
countries. Statistics and market data for soap and detergents are
quite readily available for the markets of North America and
Europe besides other key areas of Australia and Japan. There is
only minimal information on sales of soap in less developed
regions such as Africa, the Middle East and a few pockets of Asia.

The world market for soaps and detergents was worth US $ 88

billion in the year 2000. Asia, Western Europe and North America
account for about 87% of the total soap and detergent
consumption(chapter2). This is illustrated in figure().(Datamonitor)

Sales
Asia
Western Europe
Latin America&caribbean
North America
Middle East
East &Central Europe
Africa
Australia&Pacific Rim
The US market continues to dominate in the world, although the
Japanese market has grown significantly during the period under
review. Sales of soaps have received a strong impetus in China due
to its recent economic development. The Indian market has
also grown significantly, largely due to the reduction in rates of
excise duty on soap and detergents in 1995. Effectively, that year
witnessed a 100% jump in production and sales.
The global market for soaps is dominated by a small number of
multinational companies with strong brand identity and
enormous advertising budgets. There is cut-throat competition
between these multinationals. The top global players include
Unilever, Procter and Gamble, Colgate Palmolive and Johnson &
Johnson. Important regional players include Beiersdorf in Europe,
the Kao Corporation in AsiaPacific, Paterson Zochonis in Africa and
Nirma and Godrej in South Asia.( [Fats and oils in main commercial use for soap-
making]. Chemical Business, February 2000)

Markets in the developed countries

The world market for soaps and detergents has continued to

experience steady growth since 1995, with retail sales increasing
from US $ 68.4 billion in 1996 to US $ 88.2 billion in 2000(Mintel
Keynote,2000 ). The market comprises soaps, products for washing
fabric, dishwashing and household cleaning. The greatest growth
came from soaps with an increase of 21% over the same period.
The market was characterized by growing maturity and fierce
competition among major brands. Market expansion has been
attributed mainly to the development of new products, such as
liquid soaps, supported by heavy media advertising and
promotional activity by the manufacturers of major brands.
Success in any market, always, boils down to delivering what the
consumer demands. Consumers are today looking for milder soaps
and detergents. They are also preferring to products that possess
fragrance. They are also looking for in the speciality-segment
soaps using vegetable-based fats. They prefer a mild soap and are
increasingly well aware of products and are selective in their
purchase. Consumers seek for healthy, natural, and eco-friendly,
vegetable formulations, attractive packaging, pleasing shapes,
colors, and fragrance. They are also looking for a long-lasting
product like bar soaps that will retain its shape. In essence,
consumers are looking for values.

The soap market in developing countries:

The market for soap and detergents is growing much faster in

developing countries than in developed countries, as it should be.
Wide and growing income differences exist in developing
countries and each segment of the population consumes the
products it can afford while aspiring to a better product for a future
date. This, together with the increase in population has been the
motivation for the soap industry.
Income pyramid in developing countries (based on annual income in 1998-2000)( derived
from UN statistical yearbook (2000)

50.00%

40.00%

30.00%

20.00% percent of people

10.00%

0.00%
Higher Upper Middle Lower lower
Middle Middle Middle
The highest income group (more than US $ 2250 per annum)
showed an increase of between 10-20% in the decade 1990-2000.
This was the group which consumed the most expensive or
premium soaps. The premium soap products were well received by
the top 20% (Middle-middle, Upper-middle and High income
segments), while the less expensive products were used by the
majority of 80% of people (30% by lower middle and 50% by low
income groups).

Detailed breakdown of trends in developing and emerging

markets in Latin-America, Asia, Africa and the Middle East,
Central and Eastern Europe are given below:

1) Latin America
There had been a 20% growth in the sales of soaps and detergents
in the last five years. There was heavy investment in the
development of new product, their launching and advertising.
Greater competition led to fall in prices and increasing
consumption as soap became more affordable. The major
multinationals in Latin America are Unilever, Colgate Palmolive,
Avon, Procter & Gamble.

2) Asia
With the majority of the population living under the poverty line,
low cost items such as the bar soap, form the dominant sector of
the market. In terms of population size, there is a huge market
potential. As income increases, consumers go for more expensive
types of soap. Unilever is the dominant player in the region.
Procter &Gamble, Colgate Palmolive and Johnson & Johnson are
also active in this region.
 3) Africa and the Middle East
Unilever dominates the market in Africa. In West Africa, market
penetration of soap is estimated at 98%, due to strong hygiene
habits and a large raw material base. Production tends to be
localized for economic reasons. Manufacturing soap locally is
strong in rural areas, with 10 to 15% of soap manufactured through
local enterprises rather than multinationals.

4) Central and Eastern Europe

In 1999 total consumption of soap was estimated at US $ 222.2
million. The potential market' is estimated at about US $ 663.8
million. Initially, as soap was imported from the West, response
was enthusiastic, but this has slowed due to drastic reduction in
spending power of consumer.

SOAP PRODUCTION AND PROMOTION IN THE

GLOBAL MARKET:

The global soap market is dominated by a small number of

multinational companies. Soap is only one sector of their product
range. In multinational companies such as Unilever and Procter &
Gamble, soap and detergent account for less than 20% of the total
turnover.

Major costs such as research and development and advertising can

be spread across the whole structure of a company. In the
developed countries, these multinationals face stiff competition
from the major supermarkets who are increasingly introducing
their own-brand products. In the developing countries, the
competition to the multinationals is from local companies,and from
small producers who sell in markets on a house to house basis. The
largest soap and detergent company is the Unilever Group and
which has strong presence in all regional markets in the world.
Table 2.2 lists the top 20 companies dominating the global soap
and toiletries industry. In terms of value, recent acquisitions have
slightly altered the positions among the top ten leading players.

Table 2.2
The top 20 global players in the soaps and toileteries market

position company %value of world

1 Unilever 10.07
2 Procter& Gamble 7.41
3 Gillete Group 7.66
4 Colgate Palmolive 4.5
5 Johnson &Johnson 4.45
6 Shiseido 4.32
7 Estee Lauder 4.21
8 Revion 3.42
9 Wella 2.27
10 Henkel 2.27
11 Kanebo 2.13
12 LVMH 1.94
13 Avon Products 1.91
14 Kao 1.88
15 Reckitt-Benckicer 1.88
16 Beiersdorf 1.56
17 Amway 1.55
18 Mary Kay 1.54
19 Coty 1.49
20 Lion 1.07
Source: Euromonitor,2000.
Formulation:

Traditional soap consists of sodium or potassium salts of

triglycerides and fatty acids, notably from beef tallow, coconut oil,
and palm kernel oil, and to a lesser extent from such oils as grape
seed, sweet almond oil, rice bran oil, and others. Varieties of soap
include transparent, opaque, and translucent soaps, and specialty
bases such as shaving, nonmarring opaque, creamjpaste, and
powdered soaps. (Chambers et al., 1990)
The formulation of soap bars has become more complex over the
years due to an ever-increasing number of soap bases that
incorporate more and more additives. The “green” and “natural”
market segments have led to soap products with new materials.
Also, consumers have become more accustomed to multihnctional
products offered by the cosmetic industry, including conditioning
shampoos, antiperspirants, sunscreens, lotions, and creams.
Traditional soaps were designed for cleaning skin and
clothes, but as time passed soaps came to be used as a delivery
system for perfumes and superfatting agents. Today, the cleansing
aspect seems almost secondary to the effects of the various
additives that are delivered through the soap system. The 2006
International Cosmetic Dictionary published by the Cosmetic,
Toiletry, and Fragrance Association, now called the Personal Care
Products Council, lists over 13,000 monographs of INCI names as
well as 3,000 suppliers and 57,000 trade names reportedly used in
cosmetic applications. (Gottschalck & McEwen, 2006).
Table from site CC By 4.0
Properties of Soap Bases

Chemical Properties of Bar Soaps

Variations in the primary materials of the base formula influence
the chemical properties of the soap. For instance, transparent bases
can be made from detergents and fats and oils using combinations
ofsodium hydroxide, potassium hydroxide, and alkanlolamines
such as triethanolamine. Synthetic systems can be plasticized with
saturated fatty acids, fatty alcohols, or a combination. The ratio of
fats and oils (e.g.,80% tallow/20% coconut oil vs. 70%tallow/3O%
coconut oil) and the choice of manufacturing process (e.g.,
continuous, full-boiled vs. serniboiled) also affects the chemical
properties. However, the choice of the preservation system is
critical to the long-term chemical stability of the cleansing
system. George & Serdakowski, 1987

Antioxidants are useful as fat, oil and fatty acid preservatives.

However, when these materials are converted to soap, we have
found that chelators provide better protection than antioxidants
such as BHT. We have found that as a preservative in traditional
soap systems at a pH of 10, chelators provide better protection than
antioxidants such as BHT. Additionally, BHT can cause severe
yellowing of soap products when stored under certain wrapping
and warehouse conditions. It is hypothesized that certain
quinones form when BHT reacts with nitrogen-based exhaust
products produced by warehouse motor trucks and lifts, which lead
to the undesirable yellowing.( Davidsohn et al., 1953)
Physical Characteristics of Bar Soaps
The physical characteristics of the soap bar also influence the
amount and types of additives that are incorporated into the final
formula. With each formulation, the following important bar
characteristics and their parameters should be established in order
to generate complete product profiles: wear rate, crack resistance
and sloughing, wash down, lathering, color, and odor. Additives
tend to influence some or all of these aspects of the soap bar, and
the potential for negative impacts on them must be determined
prior to production.

1. Wear Rate
Wear rate describes the lasting power of the soap bar under use
conditions. It is influenced by the solubility of the base, which is
determined by the titer of the fats and oils, the type of alkali used,
and the amount of water.

2. Crack Resistance and Sloughing

Crack resistance relates to the tendency of soap bars to crack
and/or disintegrate when subjected to repeated weddry cycles. It is
measured in the laboratory by submersing one half of the bar in
ambient water for 4 to 24 hours, then air-drying it until completely
dry. Cracks will appear if the system is prone to cracking.
Sloughing is often described as the dissipation, crumbling or
shedding away of soap during use. Related to wear rate, the
amount of sloughing is similarly determined by submersing,
drying, and calculating the weight loss

3. Wash down
The feel of a bar during use can be determined by a wash down
test. This is usually performed at a relatively low temperature, such
as 85-90”F, in order to determine if there is any grit, drag, or
sandiness in the bar. Synthetic and combo systems are prone to this
problem, as well as formulas containing sodium cocoyl isethionate.
 4. Lathering
Although lathering and detergency are not necessarily related, and
foam may actually be just a visual aid allowing the user to see
where the product has been applied, consumers associate quick,
copious foam with quality and cleaning.

5. Color
Soap bases tend to yellow, so that the color of the final bar
formulations will also change. This, coupled with additive and
fragrance instability, can produce color variations over a short
period of time. Accelerated stability testing in oven, sunlight,
and/or fluorescent light can help predict the stability of the system.

6. Odor
Olfactory evaluation of soap bases and finished soap products is as
important as any other measurements of physical characteristics.
Consumers tend to view fragrance perceptions as being at least as
important as any other product characteristic. 'Therefore it is
important that fragrances be formulated for soap to ensure as much
stability as possible. Odor stability can be evaluated under similar
conditions as color stability. Trained technicians and odor
evaluation panels usually review the results of olfactory tests.
Dahlgren, RM.; M.E Lukacovic; S.E. Michaels; M.O. Visscher. Effects of Bar Soap Constituents on Product Mildness.
In Second World Congress on Detergents, Baldwin, A.R, Ed.; Amercian Oil Chemists' Society: Champaign, IL,
1987.