SOAP AND SOAP-PRODUCTS

INDUSTRIES
 TABLE OF CONTENTS
1.0 INTRODUCTION
1.1 Historical
1.2 Differences between soap and detergent
1.3 Soap-kindred products
2.0 SOAP INDUSTRIES
2.1 Raw materials for soap manufacture
2.1.1 Fatty acids and allied materials
2.1.2 Non-fatty acid materials
2.1.3 Preparation of raw materials
2.1.4 Recipe
2.2 Space and raw material needs for soap
manufacture
2.2.1 General process flowchart
2.2.2 Typical equipment
2.2.3 Typical space arrangement
2.2.4 soap manufacturing processes
2.2.4.1 Cold process
2.2.4.2 Semi-hot process
2.2.4.3 Hot process
2.2.4.4 Glycerol recovery
2.2.4.5 Rationalized kettle process
2.2.4.6 Production from fatty acids
Chemistry of soap formulation
2.2.4.7 Finishing processes
2.2.4.7.1 Finishing processes for laundry soaps
2.2.4.7.2 Finishing processes for toilet soaps
2.2.4.8 Soap qualities and quality control
Soap analysis
2.2.4.9 Various markets (uses) for soap
2.2.4.10 Other soaps and soap-kindred products
2.2.4.10.1 Deodourant or antiseptic or medicated soap
2.2.4.10.2 Superfatted soaps
2.2.4.10.3 Liquid soaps
2.2.4.10.4 Soap powder
2.2.4.10.5 Scouring soaps
2.2.4.10.6 Transluscent and transparent soaps
2.2.4.10.7 Depilatory and shaving powder/cream
2.2.4.10.8 Shampoos
3.0 SYNTHETIC DETERGENT INDUSTRIES
3.1 Surfactants
3.1.1 Anionic surfactants
3.1.1.1 Anionic detergent
3.1.1.1.1 Processes
3.1.1.1.2 Biodegradability
3.1.1.2 Other anionic biodegradable surfactants
3.1.1.2.1 Olefin sulphonates
3.1.1.2.2 Alky sulphates
3.1.1.2.3 Alkanesulphonates
3.1.2 Non-ionic surfactants
3.1.3 Cationic surfactants
3.2 Detergent formulation
3.2.1 Fabri-washing liquids
3.2.2 Heavy-duty fabric-washing powders
3.2.3 Dishwashing liquids
3.3 Deodourant
3.4 Anti-perspirant
3.5 Dental powder
3.6 Toothpaste
1.0 INTRODUCTION
Soap and Soap-related Products Industries is simply the Washing Industry also known
as the Soap Industry. Soap is a class of products that serves for cleaning of human,
property and surrounding. Hence, soap in its various forms, is in high demand society.
For generations its use has increased until its manufacture has become an industry
essential to the comfort and health of civilised man.

1.1 HISTORICAL
Soap evolved from crude mixtures of alkaline and fatty mixtures. The manufacture of
soap dates back to the first century, and by the thirteenth century the soap industry had
taken stand to produce sufficient quantities of soap.
It has been revealed that the soap factory dates back to over 2000 years ago.
Chevreul, a French chemist, showed that soap formation was actually a chemical
reaction, while Domeier completed his research on the recovery of glycerin from
saponification mixtures.
For 2000 years soap making involved batchwise saponification of oils and fats with
alkali and salting out of the resulting soap. Changes have occurred in the pretreatment
of oils and fats, plant procedure, and in the processing of finished products, eg. Spray
drying.
Better raw-materials have resulted from solvent crystallization, liquid extraction and
hydrolysis hydrogenation of various oils and fats. Continuous processes came through
Procter and Gamble who installed high-pressure-hydrolysis continuous-neutralization
process in 1937. Sharples and Lever Brothers first developed and installed jointly a
continuous- saponification process in 1945.

1.3 SOAP-RELATED PRODUCTS

Basically, all soap is made by saponification, that is the hydrolysis of naturally
occurring fats and oils by sodium hydroxide (caustic soda) or potassium hydroxide
(caustic potash). Various additives have been used to impart some specific
characteristics to the products.
By blending the caustics and/or fats/oils, varying the additives and/or the process of
soap making, and blending soaps, or blending soap with chemical(s), many types of
soap and soap-related products can be made. These include: Washing soaps, toilet
soaps, deodorant soaps, liquid soaps, shaving creams, translucent soaps, transparent
soaps, scouring soaps and synthetic detergents.
Synthetic detergents, made from artificial chemicals, have also been varied in the
production-process and blending, to give other soap-kindred products, including
surfactants, emulsifiers, wetting agents, and penetrants. Soaps and synthetic detergents
have been incorporated into some cleaning products to obtain yet some other soap-
kindred products which include shampoo, dental powder, toothpaste, cleansing cream,
hair relaxer, hair conditioner, gels, disinfectant, etc.

SOAP INDUSTRIES
RAW MATERIALS FOR SOAP MANUFACTURE
Ordinary soap is made by the reaction between caustic soda or causlic potash and fats
or oil in a chemical process called saponification which yield’s glycerol (glycerine,) as
a byproduct.
Some other chemicals are required for specified purposes and soap qualities. Thus, the
chemical raw-materials for soap making can be conveniently divided into fatty and non-
fatty (mainly inorganic) chemicals.
2.1.1 FATTY AND ALLIED MATERIALS
Fats and oils are esters - compounds of organic acids with alcohols. These acids are
termed fatty acids with glycerol as the alcohol base. Different fatty acids are contained
in the fat or oil in varying proportions based on the type and source.
For obvious reasons, the type and quantity of fats/oils available to the soap-maker
varies.
Coconut and palm kernel oils belong to the group of lauric oils and are the most valuable
fat raw-material for the soap maker.
They can be saponified by the cold process with very strong caustic solutions. If the hot
process is used, lower concentrations of caustic are suitable. Palm oil in crude form is
red and needs to be bleached to a buff shade if a light-coloured soap is required.
The bleaching can be heat, steam or chemical treatment or a combination of these as in
acid fuller’s earth oil heat treatment to remove coloured impurities. This oil is easily
saponifiable and may be used in the cold process.
The blending of soap fatty materials depends on the qualities they impart to the soap
as well as economic considerations.
OIL/FAT CONSISTENCY FOAM DETERGE MEAN AVE.CAUSTIC
NT SAPONIFICATION SODA (PER 100
QUALITY VALUE PARTS
OILS/FATS)
Coconut Very hard, brittle Quick, big, Good also in 253 18.1
short, lasting cold water
Palm kernel // // // 248 17.7
Oil palm Very hard Slow, small Very good 199 14.2
bubbles,
lasting
Groundnut Firm Fairly good Fairly good 193 13.8

2.1.2 NON-FATTY MATERIALS

Caustic soda, or sodium hydroxide, is the major caustic alkali used in converting
fats/oils into sodium soaps. Caustic potash or potassium hydroxide, is the next caustic
alkali which converts fats/oils to potassium soaps. It is more expensive a chemical.
Each fat/oil has saponfIcation value which enables the soap maker to calculate the
amount of alkali needed for completer saponification for a given quantity of oil/fat.
The saponification value is the amount in milligram (mg) of potassium hydroxide
required to saponify one gram(g) of oil/fat. Thus, the actual amounts of caustic soda
required per 100 parts of oil or fat is derived as follows:

𝑠𝑎𝑝𝑜𝑛𝑖𝑓𝑖𝑐𝑎𝑡𝑖𝑜𝑛 𝑣𝑎𝑙𝑢𝑒 𝑚.𝑤𝑡 𝑁𝑎𝑂𝐻

Amount of caustic soda = × × 100
1000 𝑚.𝑤𝑡 𝐾𝑂𝐻

40 1
= saponification value × × 10
56.1

The corrosive nature of caustic dictates that personnel wear protective clothing, gloves
and goggles.
Iron and steel are corroded at high temperatures. Welded steel plates are used for
storage tanks, while black iron pipe can serve for pipelines transporting caustic
solutions at low temperatures. Nickel steel should be used for high temperatures. Special
lining paints have been used to protect iron and steel.
Salt or sodium chloride used in soap manufacture must be of high grade, containing
not more than 0.5% of magnesium and calcium salt. It helps in precipitating out soap
from the suspension. This process is called salting out of soap.
The perfume used for soap making is added to the soap mix, and must be resistant to
alkali. It is either synthesised or isolated from essential oils.
Oil-soluble dyes or colourants are recommended for cold process, while ultramarine
blue or red clay are suggested for hot process soap. Titanium dioxide is a whitening
agent.
Soda ash or sodium carbonate has been used to increase bulk, reduce corrosiveness,
improve lathering and hardening of soap products. The dense anhydrous grade is
recommended for bar/tablet soaps, while the light anhydrous grade powder soap or
Sodium silicate adds body, the soap product.
Borax or citric acid serve as fillers and preservatives. One of these suffices.
Magnesium sulphate is used as a dehydrating agent and it helps to preserve the colour
and glossiness of the soap.
Butylated hydroxy toluene (BHT), an antioxidant and potential virus inactivator, can
stop the problem of colour shedding in coloured soaps.
Very small quantities of aluminium sulphate and hydrochloric acid are required for
the glycerol recovery process.
The recovered and purified glycerol is used in pharmacy, in making explosives and
plastics, and as an anti-freeze. It is syrupy and sweetish, and normally not recovered
in small-scale manufacture.
2.1.3 PREPARATION OF THE RAW-MATERIALS
All the raw-materials are either solid or liquid. The solid ones need to be made into
solutions for effective uniform reaction with the solid ones.

1. The caustic is dissolved by stirring in water usually three times the proportion of the
caustic, to get a hydrometric reading of about 1275. This solution can be adjusted to
this figure (reading) by the addition of more solid caustic or water, as applicable.
2. The solution of soda ash of hydrometric reading 1250 is similarly prepared.
The use of hydrometer avoids weighing the hazardous caustic. The caustic solution is
fermented for upwards of 48 hours and ash for upwards of 24 hours.
3. Borax or citric acid and magnessium sulpate are dissolved in a small portion of the
4. caustic or ash solution, to minimize the quantity of water entering the reaction.
5. Sodium silicate often sells as liquid, or made into solutions before use.
The colourant is dissolved in the oil (if oil-colour) or caustic solution (if water-colour)
prior to the reaction. The perfume is usually liquid. The older formulations not
involving additives used 25-50% caustic solution.
TYPICAL EQUIPMENT
This requires dissolution and fermentation tanks for caustic and ash, heater,
thermometer, hydrometer, fat/oil storage tanks, reaction vessel (mixer), stirrer, brine
tank, salting out chamber, moulds, dryer, cutting machines, stamping machines,
packages and standby generating plant.

SOAP MANUFACTURING PROCESSES

Three common saponification processes are cold, semi-hot and hot processes.

COLD PROCESS
This is the simplest process, usually employed in small-scale and small batch
production. Fat/oil of better quality is required than in the hot process. A higher
concentration or strength of caustic solution is used than for the hot process.
To the oil (or melted hard fats) in a mixer is added the caustic solution and stirred
continuously or up to 2 hours till an intimate mix results.
If molten hard fats are to be incorporated, they should be introduced when oil-caustic
exothermic reaction has progressed to generate heat to keep the hard fats in liquid state
and thus prevent settling out of fats.
The additives are added at this stage. Colours (if not dissolved previously in fats/oil or
caustic or ash solution) and perfumes are next added. The mixture thickens as the
process proceeds.
When the mix is considered ready, it is transferred into the moulds (frames) usually
designed with wood or metal to hold the molten soap during the long process of cooling.
The sides are detachable to facilitate the removal of the cooled, solid soap block. There
is a temporary rise in temperature prior to the normal cooling in the mould. This
indicates continued saponification even in the mould. This heat should be conserved to
ensure complete saponification and elimination of free caustic from the final product.
Cooling and hardening may continue up to 8-12 days after packaging.

SEMI-HOT PROCESS
A modified cold process, semi-hot process, allows fats of higher melting points and
rosins to be included in the raw- material mix. The liquid fat/oil is raised to the operation
temperature of 70-80°C, as well as the caustic solution. They are then reacted as in cold
process.
The time required by this process is considerably shorter than in the cold process. The
perfume and colourant are added at a later stage to prevent their loss by evaporation.
Soap fillers can be more easily incorporated in this process. Heating allows for the
correction of inaccurate mixes, and makes for more complete saponification and higher
yield.
Soap scraps, which arise from the cutting and slabbing of cooled soap and which are
wastes in cold process (except when rolled into sellable soap balls) may easily be
incorporated into the material feed by first melting them in the mixer before introducing
suitable supplementary fats/oils. The extra cost for the extra heating apparatus would
have been a disadvantage of this process over the cold process, but the extra yield soon
off-sets it.

HOT PROCESS
THE CHEMISTRY OF SOAP FORMATION
Palm kernel oil reacts with caustic soda (or caustic potash) to form soap. The active
ingredient in the oil for this reaction is lauric acid, C11H23CH2C00H. This acid exists
in the oil in its triester form called Trilaurin. The trimester reacts with caustic to form
scap as expressed in theequation below

CH2C00C11H23

CHC00C11H23 + 3NaOH 3 C11H23CH2C00Na + Glycerol

CH2C00C11H23
Taking the relative atomic mass of 0=16.0, C 12.0, H = 1.011 and Na = 23.0, we
calculate the masses of the reactants to be 638.74g of trilaurin plus 120g of caustic soda,
according t their ratio in the stoichiometric (balanced) equation. Thus, 638.74g of the
oil will need (to react with) 120g of caustic soda to form soap. Taking 0.9192 as the
density of the oil we can convert 638.74g of oil to the volume equivalent, using the
equation.
 𝒎𝒂𝒔𝒔
Density=
𝒗𝒐𝒍𝒖𝒎𝒆

Thus, rearranging the equation, we get the volume of oil required to form soap with 120g of caustic
soda as Converting this volume to litres gives 0.695 litres just as 120g is 0.120kg.
𝟔𝟑𝟖.𝟕𝟒
Volume = = 694.89ml
𝟎.𝟗𝟏𝟗𝟐
That is 0.695 litres of oil need 0.120kg of caustic soda to form soap. Multiplying both numbers by
3.783 (i.e. taking 3.783 batches of the reactants together) means that 2.63 litres of oil will need
454g or 0.454kg of caustic soda to form soap. That is, 2.63 litres of oil would be needed if the oil
were trilaurin.
But the trilaurin content of the oil is only 48%. Thus, if 100% needs 2.63 litres, by simple
proportion, 48% concentration of trilaurin would need more oil for the same amount of caustic
Soda.
𝟏𝟎𝟎
X 2.63 = 5.48litres
𝟒𝟖

This approximates the ideal proportion. In practice however, the ratio of the reactants may vary
slightly due to the varying richness of different samples of oil which results to differences in
density and trilaurin-content.
It could be recalled that agricultural produce varies in component-ratio due to climatic, soil and
cultivation variations. The varying concentrations of the manufactured caustic as well as the use
of a mixture of oils/fats and/or caustics for soap making also necessitates a deviation from the ideal
oil-caustic ratio.
The result is that there are many soap formulations. The soap chemist will have to formulate a
product particular to the industry. The formula is usually the industry’s secret. Thus, no soaps from
different industries are exactly the same.

FINISHING PROCESSES
The finishing processes in Laundry soap production include
1. Cooling and Solidifying
2. Slabbing, Slicing and Barring
3. Drying
4. Stamping and Pressing
5. Wrapping and Packaging
For Toilet soap additional processes required are:
6. Milling
7. Plodding and
8. Chipping

FINISHING PROCESSES FOR LAUNDRY SOAPS

Cooling and Solidifying:
Neat soap from the saponification pan may be cooled in a number of ways. The
traditional method runs hot soap into cooling frames to air-cool for about two days.
Modem methods of reducing the cooling time include causing the soapmix to play in a
thin stream on to the outer surfaces of a series of internally cooled, revolving cylinders
where it solidifies to be scraped off, or employing a vacuum cooling unit. The dried
soap emerges as noodles, which must then be fed into a compressor to convert them
into soap bars.
Slabbing, Slicing, Barring and Cutting:
Cooled soap blocks are reduced to slabs (slabbing) which are cut or sliced into bars
Drying:
Soaps are traditionally stacked on trays to weather- dry. Vacuum cooled soap is usually,
subject to forced drying by hot air (204°C) in a special weathering unit. This is more
exact and reduces moisture content to about 20%. The surface hardens during the drying
process. The pasty soap is now cooled (to about104 to 66°C) by brine circulation in the
outer shell.
Stamping and pressing:
This embosses a trade name upon, and gives the bar or tablet its final consistent shape.
Stamping may be manual or automatic.
Wrapping and Packaging:
Two coverings are normal: a waterproof outer covering that prevents loss of moisture
from the soap tablet, and an inner wrapping which prevents the outer cover from
sticking to the soap. Loss of moisture is undesirable, for it causes cracking, shrinkage,
and wrapping of the soap. Both wrappings can be combined into one. The wrapped
products are packed in boxes or cartons for distribution.
2.2.4.8.2 FINISHING PROCESSES FOR TOILET SOAPS
The manufacturing process is the same as in the Laundry soap up to the barring, except
that caustic potash (less corrosive) or a mixture of caustic soda and potash may replace
the caustic soda (more corrosive), and additives are with - held. Also, a longer
drying period is required for toilet bars to reduce to 12% moisture content.
The dried bars are fed into a chipper. The soap chips are fairdried and passed to an
amalgamator fitted with strong mixing blades for mix-blending the chips with additives
(fillers, builders, colourant, perfume, preservative, etc. as in laundry soap). Pine oil (100
parts) and glycerol (200 parts) may be added to the recipe (for laundry soap) to obtain
a nice toilet soap. Titanium dioxide, TO2 may be added as a whitener. Purest of toilet
soaps contain no additives.
Milling is carried out two to three times, first to ensure a thorough mixing or kneading
of the moist mix from the amalgamator and also to reduce the mix to soap ribbons of
3/4 inch in width. Milled soap lathers better and has a generally improved performance,
especially in cold water.
In the plodder, the strips of soap are forced, by screw feed into a compression chamber,
and the resulting mix forced out or extruded through a nozzle die plate to the required
shape. This plodding process may be repeated, or two or three chambers interconnected
by vacuum tunnels incorporated. Improper temperature control results to cracking in
products. Most plodders have water – jacket for temperature control.
The soap is next cut by rotary cutters into tablets of suitable size, and stamped and
passed as in laundry bars.
The wrapping and packing of toilet soaps are more tasteful than for laundry soaps. An
inner wrapper helps to retain the perfume, while an outer covering protects against sun
and moisture.
Mould inhibitors may be used.

SOAP QUALITIES AND QUALITY CONTROL

For the safety of consumers, soap should not contain an
• excessive amount of caustic, free fat/oil which could lead to rancidity, or
inconsistent moisture content.
• A satisfactory soap making process must saponify the fats/oils, produce soap
with a low water content (10-15%).
• Good soaps lather very well. Insufficient foaming may be due to wrong
formulation, poor or incomplete saponification and excessive additives.
• Good soaps are lustrer and bright-looking. Dull appearance may be due to
absence of, or insufficient, silicate or gum resin. Titanium dioxide may be added
prior to addition of colourant, to prepare the crude soap for the reception of the
colourant.
Soap Analysis
Some of the more important in-process and post-process analytical tests carried out in
the quality control laboratory of the soap industry include:
1. Total Fatty Acids.
The weighed sample is hydrolysed with acid, the fatty acids are extracted with diethyl
ether, which is evaporated off or recovered by condensation, and the residue is weighed
to ascertain the weights of the sample.
2. Free alkalinity:
A sample is dissolved in alcohol and titrated with a standard acid using phenolphthalein
indicator. The result is usually expressed in terms of Na20.
3. Salt:
The salt is determined by titration with silver nitrate using potassium dichromate as an
indicator.
4. Glycerol:
The soap is hydrolysed with mineral acid, and glycerol determination is made on the
aqueous phase by oxidation with either potassium dichromate or sodium periodate.