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Soap and Soap-kindred Products Industries

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i
ii
 SOAP AND SOAP-KINDRED
PRODUCTS INDUSTRIES
By
ONYENEKENWA CYPRIAN ENEH

Copywright © 2005 by
Welfare & Industrial Promotions (WIPRO) International

ISBN
978-044-891-8

Second edition – January, 2017

Conditions for Sale

All rights reserved. No part of this publication may be
reproduced, stored in a retrieval system, or transmitted in any
form or by any means, electronic, mechanical, photocopying,
recording or otherwise without the prior permission of the
publisher.
iii
 DEDICATION
To God who gives wisdom, knowledge and understanding.
To my parents who gave the teething training.
To my beloved wife, Amuche, and children: Chimezie,
Chinelo, Chinemelum & Chinedum (Oluebube Chukwu), who
gave the support for writing.

iv
 PREFACE AND
ACKNOWLEDGEMENTS
A man would do nothing, if he waited until he could do it so
well that no one could find fault with what he had done –
Cardinal Newman

Self-help project is the only sustainable solution to the problems of a

developing econmy. Good a thing, the successive national budgets, rolling
plans, and United Nations assisted programmes often focus on enterprises
development as a major propeling force towards addressing the problems
of a poor economy.
In developing economies, published materials are hardly available to the
students and entrepreneurs. Africans are particularly poor in handing down
their discoveries, let alone industrial or trade secrets, to others in this or
successive generations who aspire in the same field.
This book is a modest presentation of simplified facts on soap and soap-
kindred products industries for success in studies, research and
entrepreneurial endeavours.
The supports from my family and colleagues are gratefully acknowledged.

Onyenekenwa Cyprian Eneh (PhD, fcsn, c.chemist)

P.O. Box 9060, Enugu, Nigeria
Email: onyenekenwa.eneh@unn.edu.ng
Website: oceneh.com
January 2017

v
 TABLE OF CONTENTS
Publishers page ii
Dedication iii
Preface and acknowledgements iv

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

vi
 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

vii
 3.2.3 Dishwashing liquids
3.3 Deodourant
3.4 Anti-perspirant
3.5 Dental powder
3.6 Toothpaste
BIBLIOGRAPHY

viii
 TABLES AND FIGURES
Table 2.1: Fatty acid distribution in tallow and coconut oil
Table 2.2: Fatty materials and their sodium soap
product characteristics
Figure 1: Process chart of soap plant
Figure 2: Sequence of plant used in saponification
Figure 3: Plant for production of molten soap
(semi-hot process)
Figure 4: Slabbing machine and cooling frames
Figure 5: Soap bar and tablet soap cutting macine
Figure 6: Simplified continuous flowchart for the
production of heavy-duty detergent granules
Figure 7: Continuous series sulphonation-sulphation
neutralization

viii
 1.0 INTRODUCTION
Soap and Soap-Kindred 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. In fact, modern civilization may be gauged by the
per capita consumption of soap and detergents

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. Pompeii excavations revealed that
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.
The alkali required for soap formation was obtained by the crude
leaching of wood ashes or from the evaporation of naturally
occurring alkaline waters, Nile River, until Leblanc produced
cheap sodium carbonate from sodium chloride.
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.
The introduction of synthetic detergents, however, has dwarfed the
continuous soap processes. In the seventies detergent sales reached
between $400 and $500 million in United States of America.
There is no statistics in the developing countries.

1.2 DIFFERENCES BETWEEN SOAP AND DETERGENT

Soap - a classical example of detergent (cleaning agent) differs
from detergent in processes of manufacture and chemical
composition. These result in differences in action. Soap depends
for its washing action on the fact that molecules possess one ionic
(polar, water-attracting hydrophilic end and one covalent (non-
polar, water-repelling hydrophobic) end which attracts oils and
greases. Thus, can make water and oils come into an emulsion
This is the modern concepts of surfactants: soap, detergents,
Emulsifiers, wetting agents and penetrants.
Soap is not, however, satisfactory, forms scum (precipitate of
insoluble calcium and magnesium salts) in hard and
acidic waters. Synthetic detergents, on the other hand, do not form
a scum in hard or acidic water as their calcium and magnesium
salts are soluble; are usually more soluble in water than soap is;
enable water to spread and penetrate more fully over or through an
article being cleaned; and can generally be used equally well under
alkaline or acidic conditions. Soaps are essentially the sodium or
potassium salts of various fatty acids, while detergents are very
complex mixtures of many substances, all chosen to impart a
particular action in cleaning. The polar end of the detergent
molecule consists of sulphonic acid (-SO3H) or hydrogen sulphate
(-OSO3H) group present in the form of its sodium salt to increase
solubility. The non-polar end of the detergent molecule is a long
alkyl or alkyl-substituted benzene chain. Extensively branched
chains are not biochemically degradable and such detergents cause
pollution in rivers and sewage waters. Detergents may be mixed
with inorganic phosphates (to soften hard water), sodium silicate
(to increase the bulk and the handling properties), oxidizing
agents, e.g. sodium perborate (to act as a bleach), fluorescent
materials (to act as whiteners) and other additives. Enzyme
detergents contain added enzymes which help to remove
biological stains by biochemical action on the proteins involved.
Antiredeposition agents, e.g. sodium carboxymethyl cellulose, are
added fabric-washing detergents to suppress redeposition of dirt on
to cotton). Builders (to remove free calcium and magnesium ions
from solution) are added, e.g. ethylendiaminetetra-acetic acid
(EDTA), sodium polyacrylate, and sodium sulphate (Na5P3H10).
Soap also contains additives for some desired qualities. These
include salt, soda ash, sodium silicate, sodium bicarbonate,
perfume, colour, citric acid, borax, magnesium sulphate, and
trisodium phosphate. A combination of inexpensive builders, e.g.
soda ash with more effective (and expensive) tetrasodium
pyrophosphate or sodium triphosphate, is sometimes superior to
the phosphate used alone.
Although the use of soap has declined since World War II,
majority of the world’s toilet tablets are still soap, and in the
developing countries hard soap bars are still the most important
fabric-washing products. Also, a substantial proportion of the
fabric-washing powder used in the United Kingdom is soap
powder. Other uses of soaps are in textile finishing, emulsion
polymerization, cosmetics and polishes.

1.3 SOAP-KINDRED 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-
kindred 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.
 2.0 SOAP INDUSTRIES
2.1 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. Table 2.1
displays fatty acids distribution in coconut oil and tallow.
Table 2.1: Fatty acids distribution in tallow and count oil
ACID STRUCTURE PROPORTION (%) CONTAINED IN

COCONUT OIL BEEF TALLOW

Caprylic CH3(CH2)6C00H 8-9

Capric CH3(CH2)6C00H 7-10
Laurie CH3(CH2)10C00H 45-51
Myristic CH3(CH2)12C00H 16-18 2-4
Palmitic CH3(CH2)14C00H 7-10 29-32
Stearic CH3(CH2)16C00H 1-3 19-26
Oleic cis-CH3(CH2)7CH 5-8 10-43
= CH(CH2)7C00H
Linoleic cis, cis-CH3(CH2)4 1-3 2
CH=CHCH2CH=
CH (CH2)7C00H

Source: Tedder et al
For obvious reasons, the type and quantity of fats/oils available to
the soap-maker varies. Table 2.2 contains a list of materials and
their sodium soap product characteristics. The first six fats/oils
derived from oilseeds are widely available in the tropical or
subtropical developing countries. Other vegetable fatty materials,
like olive oil (not widely available in the tropics) and neem oil
(non-edible, with undesirable characteristics) are not included.
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 (vide infra) with very
strong caustic solutions. If the hot process (vide infra) 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. It is
TABLE 2.2: Materials, their sodium soap products and characteristics
OIL/FAT CONSISTENCY ODOUR FOAM DETERGENT SKIN USE MEAN AVE.CAUSTIC
QUALITY REACTION SAPONIFICATION SODA (PER 100
VALUE PARTS OILS/FATS)
1. Coconut Very hard, brittle Slight Quick, big Good also in Makes skin All kinds of 253 18.1
odour of nut short, lasting cold water rough soaps, esp.
toilet
2. Palm kernel “ “ “ “ “ Household, 248 17.7
toilet, soap
powder
3. Oil palm Very hard Original oil Slow, small Very good Very mild “ 199 14.2
bubbles,
lasting
4. Groundnut Firm “ Fairly good Fairly good “ Household, 193 13.8
textile,
toilet soap
5. Soyabean Soft “ Mediocre Mediocre “ “ 192 13.7
6. Cottonseed Fairly soft “ “ Good Mild Household 194 13.9
soap
7. Tallow Very hard Neutral Slow, small
bubbles,
lasting
8. Lard “ “ “ “ “ “ 198 14.1
9. Fish Fairly soft Fishy Greasy Fairly good Mild Soft soap 188 13.4

Source: Oil World Weekly, USDA, Public Ledger

normal to combine palm oil with lauric oil. The characteristics of
soap made from palm oil and tallow are similar. Bleached palm oil
can substitute for tallow, but the product will be softer in texture.
The soyabean oil is saponified in crude or refined form. It is
blended with other oils, especially coconut, to give it the necessary
form and detergent power.
Dark reddish brown cotton-seed oil is refined to a light colour by
treatment with caustic soda, and saponified with difficulty to
obtain sodium soap with yellow colour and poor keeping qualities.
Thus, blending with other oils is necessary.
Tallow, a fat obtained from the tissues of beef (cattle) and mutton
(sheep) by heat treatment, varies in colour from a light shade in
edible grade to very dark shade in the lower grades. In Britain,
there are six grades of tallow, the first two used for toilet soap and
fourth and fifth for laundry soap. Tallow is generally blended with
other fats. The cheap tallow can be produced in developing
countries where modern meat factory exists.
Lard is similar to, and obtained in the same way as tallow, from
the fat tissues of pigs. The higher grades of lard are valuable raw
materials for high grade toilet soaps and have been used in
combination with coconut oil for this purpose.
Greases used in soap manufacture are obtained from animal
wastes and waste cooking fat from hotels and restaurants, or may
be recovered from town refuse. They are used for low grade soaps.
They are used for low [t into fatty acids and glycerol, the fatty
acids being excellent material for high grade soaps. Fish oil in
crude form rapidly tends to become rancid. Its fishy odour, brown
colour and low detergent power make it suitable for only low-
grade soaps. The particularly hydrogenated form may be partially
substituted for tallow. The world supply of fish oil is, however,
restricted.
Rosin and Tall ‘oil’ are two other organic raw-materials which,
though neither fats nor oils, have been used in soap production.
Rosin is derived from trees of the Pinus species (of Central
America and the Caribbean, and now found growing in developing
countries). The exudate from the tree trunk is a viscous solution of
about 75% rosin in turpentine, known as oleoresin. The rosin is
obtained by distillation of oleoresin or solvent extraction of the
wood. Rosin can be treated as a fatty acid and used to make
sodium soaps in combination with other fats. Rosin has been
displaced in the soap industry by nut oils with similar properties
and lower prices.
Groundnut oil is edible and easily saponifiable in crude, refined or
hydrogenated (hardened) form. It is combined with other fats to
modify consistency.
Taft oil or liquid rosin is obtained from wood as a by-product of
the paper pulp industry using the sulphite process. Pure sodium
soaps produced from tall oil alone vary in colour from yellow-to
dark brown and are soft and tacky. For hard soaps tall oil normally
constitutes not more than 25% of the fat input. Unlike the
production of gum and wood rosin which has been stagnant,
the production of tall oil raisin has increased with world
production of paper by the sulphite process. The only developing
country producing tall oil is Swaziland, although it may be
produced in others such as Brazil and Chile where pine is being
pulped.
The blending of soap fatty materials depends on the qualities they
impart to the soap as well as economic considerations. Thus, when
combined with tallow, coconut oil contribute lathering quality and
solubility while the former will contribute mildness and long-
lasting lather. Rancidity in crude cottonseed oil soap can be
counteracted by tallow and coconut oil. Depending on price and’
or availability advantage, palm oil and tallow may substitute each
other. Because rosin and coconut oil soaps are similar, rosin
replaced coconut oil during World War II, when supplies of
coconut were sharply reduced.
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:

. .
Amount of caustic soda = x x 100
, . .

= saponification value x .
x

The corrosive nature of caustic dictates that personnel wear

protective clothing, gloves and goggles. Besides, it dissolves tin,
zinc, aluminium, and their alloys. 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.
Hard water can still be used for sodium soap making, since the
calcium carbonate is absorbed harmlessly into the product, with a
small loss of soap, though. Soft water is required for the boiler
feed, all the same.
Salt or sodium chloride used in soap manufacture must be of high
grade, containing not more than 0.5% of magnesium and calcium
salt.
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, and includes citronella oil (Ceylon or Java
type) which contains the alkali resistant alcohol geraniol as a
major component and may therefore be employed for use in the
cold process in place of the imported isolate or synthetic chemical.
Oil-soluble dyes or colourants are recommended for cold process,
while ultramarine blue or red clay are suggested for hot process
soap (vide infra). 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
scouring soap powder. Sodium silicate adds body, the soap
product.
Borax and 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.
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.
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.
Borax or citric acid and magnessium sulpate are dissolved in a
small portion of of the caustic or ash solution, to minimize the
quantity of water entering the reaction.
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.

2.1.4 RECIPE
Materials and their proportions for soap manufacture are:
1. Fat/oil 12,000 parts
2. Caustic solution (1275 hydrometric reading) 6,000 parts
3. Soda ash solution (1250 hydrometric reading) 250-2,000 parts
4. Sodium silicate solution 250-500 parts
5. Borax or Citric acid (dissolved in 2 or 3 above) 125 parts
6. Magnesium sulphate (dissolved in 2 or 3 above) 100 parts
7. BHT (dissolved in 2 or 3 above) 100 parts
8. Colourant (dissolved in oil/fat or water) to taste
9. Perfume (dissolved in oil/fat or water) to taste

2.2 SPACE AND EQUIPMENT NEEDS FOR SOAP

MANUFACTURE

2.2.1 GENERAL PROCESS FLOWCHART

The general process flowchart for soap manufacture can be
outlined thus:

Preparation of Saponification Separation of Finishing

raw-materials by-products process
More specifically, the outline can be broken down to:

Dissolutio Saponificat
Framin Sizing
n of Dissolution ion,
g and and
Caustic + of other separation
drying packagi
ash and solid of by-
ng
Fermentat additives productes
ion and
introductio
n of
additives
Figure 1 depicts a process chart of a soap plant, while figure 2
gives a detailed sequence of saponification plant.

Figure 1: Process chart of a soap plant

1. Fat melting tank 10. Filter
2. Fat feed pump 11. Brine solution melting tank
3. Fat storage tank 12. Fat meltingtank
4. Fat feed pump 13. Caustic soda solution metering tank
5. Caustic soda solution tank 14. Saponification pan
6. Caustic soda solution pump 15. Saponification lye tank
7. Tank for diluting soda solution 16. Neutralized lye tank
8. Brine solution storage tank 17. Neutralized lye pump
9. Brine solution feed pump 18. Soap pump
19. Soap crutcher
2.2.2 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. (See 2.1.2. for comments on choice
of materials). Figures 3, 4 and 5 show samples of soap making
equipment.
Figure 3: Special process plant for molten soap (semi-hot
process)
2.2.3 TYPICAL SPACE ARRANGEMENT
Thus, the space requirement will depend on the scope of the
industry, but a typical arrangement will look like

Layout for soap industry

2.2.4 SOAP MANUFACTURING PROCESSES
Saponification processes described here are simple ones, while
mention is merely made of technologically complex processes.
Three common saponification processes are cold, semi-hot and hot
processes.

2.2.4.1 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 continie up to 8-12 days after
packaging.

2.2.4.2 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.

2.2.4.3 HOT PROCESS

Boiling the soap reaction mix produces soap of the highest
quality. Heating is by steam produced in the boiler plant and
passed under pressure to steam coils incorporated in the boiling-
kettle. The injected steam both heats and agitates the mixture.
Fats/oils are melted from their tanks by means of steam jets, into a
storage tank. They are then pumped via meters to the
saponification pan. Suitable solutions of caustic and salt are
pumped via measuring devices to tanks for introduction later in the
process.
As the fat/oil and alkali boil in the soap vessel, a vigorous
saponification reaction takes place. It may be necessary to boil up
a little of the soap from a previous batch with the reaction mix, to
ensure adequate mixing between the oily and aqueous phases and
allow the reaction to proceed smoothly.
Although saponification time varies with size and shape of the
vessel as well as with the raw-materials, two to four hours may be
representative.
When saponification is complete, hot salt solution is
passed into the reaction vessel where it is boiled with saturated salt
solution (brine). Glycerol dissolves easily in the salt water, but
soap only to a limited extent. The mix is allowed to stand for
several hours, resulting to two separate layers - top layer of soap
and a lower layer lye, a mixture of brine and glycerol. The soap
layer may be washed with more brine to remove more glycerol.
Counter current washing system is mostly adopted. A lie from a
batch of soap in a more advanced stage of the process is used to
wash a freshly saponified charge. Although it requires the use of
more than one pan, this system has the advantage that the process
becomes semi-continuous in the production of soap and that the
spent lye contains higher oncentration of glycerol than when
washing were carried out with fresh brine. With careful regulation
of the size of the washes lye of 8 to 10% glycerol results.
Market for spent lye exists in advanced countries, otherwise this
waste must be disposed of so as not to cause pollution.
The next stage is the fitting operation. The mixture of the
right consistency (depending on operator’s skill and experience) is
allowed to settle for up to three days to resolve into two layers- top
layer of good quality soap curd and a lower layer of lye which is a
mixture of dark impure soap and lye. The phases are then
separated and more salt and water are added to the soap phase to
separate more of the glycerol in a second lye. Next, critical amount
of water added to the curd results to the separation of nigre, a thin
phase containing coloured impurities and some soap, from neat
soap layer containing 30% water.
One week is typical for a whole cycle of kettle operation. This
long production period imposes a constraint on throughput. To
overcome this delay, large-scale manufacturers have adopted
continuous process.

2.2.4.4 GLYCEROL RECOVERY

The spent lye (about 12% glycerol) is boiled with fatty acids to
reduce the excess caustic. On cooling the solid soap is
skimmed off and returned to the soap plant. Hydrochloric acid and
alum are added to precipitate impurities which are filtered out.
Further addition of caustic neutralizes the acid and prevents
corrosion in the next plant. The treated lye is concentrated to 80%
crude glycerol by evaporation of water in a single or double or
triple-effect evaporation, depending on the size of operation. The
crude (78% glycerol, 0.2% fatty acids, and 22% water) is settled
for 48 hours at elevated temperatures, and then distilled at
60mmHg and 204°C. The distillate is condensed in three stages of
decreasing temperature, the first stage yielding 9900 glycerol.
Carbon bleaching followed by filtration in ion exchange gives
final product.

2.2.4.5 CENTRIPURE PROCESS

The production of soap from neutral fats can be carried out
continuously in three stages. The saponification takes place in a
column. Pumps convey fat/oil and caustic to various sections of
the column and also circulate soap throughout the column, thereby
catalyzing subsequent saponification and very quick reaction.
Glycerol is removed by counter-current washing with brine. The
soap mix is passed to a centrifuge for a quick separation of the
soap, as against the three-day long separation of kettle process.
Continuous quality control is an advantage here.

2.2.4.6 RATIONALIZED KETTLE PROCESS

This is a combination of certain features of the centripure process
with the standard kettle process, to decrease production time (and
hence increase throughput) without the heavy capital outlay
involved in continuous specification units. Centrifuges are used to
take soap from the pans and in the finishing stages, thereby
shortening the process time.

2.2.4.7 PRODUCTION FROM FATTY ACIDS

Raw fats/oils are split using superheated steam to produce
fatty acids and sweet water which contains glycerol. The glycerol
is removed before the saponification of the fatty acids to yield
soap.

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,
C11H2300H. This acid exists in the oil in its triester form called

Trilaurin,
The trimester reacts with caustic to form scap as expressed in the
equation below

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.

Thus, rearranging the equation, we get the volume of oil required

to form soap with 1 20g of caustic soda as
Converting this volume to litres gives 0.695 litres just as 120g is
0.120kg.
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% (Table 2.1). 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

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.

2.2.4.8 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

2.2.4.8.1 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 liquid mix
enters a vacuum spray unit through a revolving nozzle which
sprays a very thin film of soap on to the internal walls of the unit.
On its entrance into the vacuum spray unit the soap volume
expands causing instant reduction in humidity, and at the same
time cooling occurs. 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
(barring or slicing)
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 about
104 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.

2.2.4.9 SOAP QUALITIES AND QUALITY CONT1OL

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. If soap were anhydrous, it would be
too hard to dissolve easily.
A satisfactory soap making process must saponify the fats/oils,
produce soap with a low water content (10-15%), remove coloured
impurities, and possibly separate the byproducts for convenient
recovery.
Top grade soaps are made from a blend of bleached tallow and nut
oils. Soaps from crude individual fats/oils exhibit the
properties (odour and other properties) of these materials. Toilet
soaps usually contain 20-50% coconut-oil soap and 50-80%
tallow’s soap and also contain up to 10%, unneutralized fatty acid.
The more expensive coconut-oil soap gives good lathering and
satisfactory dissolution properties.
Good soaps lather very well. Insufficient foaming may be due to
wrong formulation, poor or incomplete saponification and
excessive additives.
Some soaps develop, on storage, some whitish skin (dust). This
may be due to too high concentration of caustic or ash solution
used.
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.
Some soaps smell like caustic. This may be due to excess caustic,
or insufficient or weak perfume used. Other soaps may smell
oily, due to incomplete saponification process or inadequate
caustic used, leading to excess unsaponified oil.
Good soaps should be harmless not only to the skin, but also to the
substrate, after use. Some poor-quality soaps peel the skin after
wash due to high strength of caustic solution used. Such solution
should be thinned down before use.
Soaps are very durable products, lasting many years. Defective
soaps have very poor shelf-life.
Weak perfumes soon evaporate from the product, leaving the
unpleasant unmasked caustic odour. The soap may lose its shape
due to too high water-content, which after evaporation, disfigure
the shape of the product.
Washing power is often linked to foaming or lathering. This is
because lathering tends to be proportional to washing power,
except in scouring soaps or low-sudsing detergents (vide infra).
Mould inhibitors may be incorporated in toilet soaps.
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.
5. Colour: The colour of the soap is usually closely related to
the colour of the washed fatty acids split from the sample.
The fatty acid colour is compared with standard colours in a
Lovibond tintometer (for light-coloured fatty acids) or Fat
Analysis Committee (FAC) discs (for darker fatty acids).

2.2.4.10. VARIOUS MARKETS (USES) FOR SOAP

Soap is widely used for personal hygiene, domestic and
commercial cleaning operations. The detersive and emulsifying
properties have been exploited for related purposes.
Soap is not only used for laundering, but also in textile mills for
scouring wool, degumming silk to remove impurities, and to
improve fabric feel or finishing. Soap is used in emulsion-
polymerization encountered in rubber and plastic industries. Soap
is widely used in cosmetic industry to emulsify a variety of skin
cleaners and conditioners.
Sodium and lithium soaps are extensively used to thicken mineral
oil in the manufacture of lubricating greases.
Soap (the 105dsmg type) is used as degreat on leather and metal
(machine) parts.
Liquid soap serves as the emulsifying and wetting med for
antiseptic, shampoos, etc. The shampoo could be designed for
cleaning rug (carpet), ulpholstery, motor parts, walls, tiles, floors,
hair, leather, etc.
Specialty soaps of ammonia and alkanolamines (such as mono-
and triethanolamines, monoisopropanolamine, and 2-amino-2-
methyl-1-propanol for AMP) are good emulsifiers for preparations
for cosmetics, soluble cutting oils, furniture/floor/automobile
polishes and emulsion paints.
2.2.4.11. OTHER SOAP AND SOAP-K1NDRED PRODUCTS
2.2.4.11.1 DEODOUNT OR ANTISEPTIC OR MEDICATED
SOAP
These are modern antibacterial agents containing chemicals which
not only suppress the growth of skin bacteria responsible for body
odour at low concentration but also have substantivity for skin
such that rinsing is resisted. The medicated or antiseptic toilet
soaps are toilet soaps containing 0.01 - 0. 1% of one or more of the
following skin nourishers, toners or disinfectants: phenol or
carbolic acid, irgasan, mercuric iodide, vitamin E, hydroquinone,
trichlorophenol, chloroxylenol, chlorhexidine, triclorocarbanilide,
etc.
The antiseptic soap can also be liquid (e.g. Dettol and Savlon) to
which has been added the active chemical disinfectant or
ingredient (e.g. chloroxylenol in Dettol and chlorhexidine in
Savlon).
2.2.4.4.2 SUPERFATTED SOAPS
These are toilet soaps superfatted by adding 2-6% excess of
unsaponified oil or fatty acid or lanolin to produce a soft cold-
cream effect by leaving a residual film on the skin after washing
and rinsing.

2.2.4.11.3 LIQUID SOAPS

These are formulations with the more soluble potassium,
ammonium or triethanolamine soaps of coconut, olive or other
low-titre oils.
A. Typical recipe is
1. Caustic potash 3/4kg
2. Alcohol (Ethanol) 10 litres
3. Coconut or Palm kernel or (bleached) palm oil 1.5litres
4. Water (soft)
5. Perfume to taste
6. Colourant to taste
Procedure
Dissolve caustic in alcohol, add oil and stir to mix. Heat gently to
boil, till no more oil globules result when a drop of mixture is
mixed with a little water. Note the volume. Boil off (or recover by
condensation) as much alcohol as possible, to get a molten soap
paste. Allow a 3-hour rest. Add as much hot water as the removed
alcohol. Dilute further (if need be) to taste of viscosity with hot
water. Add perfume and colourant (optional, to taste). Store for 2
weeks, if possible.
Results
Cloudiness disappears, to give a clear product requiring no longer
storage, centrifuge or decanting. Viscosity increases on storage,
and a further dilution might be needful. The resulting golden-
yellow liquid soap vigorous persistent lather.
Note
With the same procedure the materials below give a good product:
Vegetable oil 50 parts
Caustic potash (40%) 27 parts
Water 23 parts
Sequestering agent 0.25 parts
Colourant/perfume 0.25 parts
The formulation is, however, wasteful of caustic and oil, and will,
thus, yield an expensive product.
Sequestertng agents are chelating agents. Their demand is
increasing as stabilizers to prevent deterioration and increase shelf-
life and stability. Ethylenediarninetetra-acetic acid (EDTA) is
popular for the inactivation of trace-metal ion and other
contaminants.

2.2.4.11.4 SOAP POWDERS

This is used extensively for fabric and washing. A typical
formulation consists of:
1. Sodium soap 50-60 parts
2. Sodium perborate 8-20 parts
3. Sodium silicate powder 3-6 parts
4. Sodium carboxyrnethylcellulose small amount
5. Fluorescent whitening agent small amount
6. Lather boosters small amount
7. Sodium carbonate small amount
8. Sodium phosphate small amount
9. Perfumes and water small amount
Procedure
The spray-cooled product is prepared by mixing the ingredients
less the heat-sensitive materials, like sodium perborate (bleach,
effective below 70°C), superheating the resultant slurry under
pressure, spray-cooling through a nozzle, and dry-mixing the
resulting powder granules with the heat-sensitive ingredients to
give the finished product. Small batch product can be produced,
from base raw materials, using:
1. Palm kernel or (bleached) palm oil 16.5 litres
2. Caustic soda 3kg
3. Soda ash or salt 2kg
4. Water 2kg
5. Colourant/perfume to taste
Procedure
Dissolve the caustic and ash or salt in the water and ferment for 48
hours. Warm the oil to which has been added the oil-colour. (The
water-colour to be dissolved in the caustic solution.) Add the
caustic solution (in which is dissolved the water-colour) to the oil
and stir continuously. Before it thickens and when the temperature
of the exothermic saponification reaction has reduced to 40-50°C,
add the perfume and blend. Spread the hardening soap or send it to
dryer. Grind, sieve and air-dry for 2-3 days. Package.

2.2.4.11.5 SCOURING SOAPS

These are scrubbing soaps in form of bar, paste or powder. They
contain one or more finely-powdered insoluble abrasive materials
which assist a particular cleaning of say, mechanic hands, pots,
tiles, walls, floors, chain, ring, etc. The abrasive materials may be
talc, quartz, feldspar, sand, etc. Alkaline builders, such as
sodium silicate (powder), soda ash or trisodium phosphate, are
frequently incorporated. Soap content in such a product is
generally low (5-10%), since no great amount of sudsing is
desired.
A product can be obtained by grinding and blending the following
mixture:
1. Soap powder (unground, of colour of choice) 1 part
2. Sand grains or egg shells (dry) 9 parts
or soda ash (light) 2 parts
Air-dry the product for 2-3 days and package.

2.2.4.11.6 TRANSLUCENT AND TRANSPARENT SOAPS

Transparent soaps are made by the semi-hot process followed by
framing. Additions of alcohol, sugar solution, and glycerol to the
hot soap inhibit the growth of soap crystallites during frame
cooling and promote a glassy, transparent condition. Milled
translucent soaps have been produced without the additives
by controlling the processing conditions.

2.2.4.11.7 DEPILATORY AND SHAVING

POWDER/CREAM
This is a harmless preparation or agent that removes hair within 10
minutes by denaturing (depilating) it at given pH medium and
temperature The depilatory, calcium thioglycolate in pH 12.3
(achieved by addition of adequate amount of slaked lime, is mixed
with small amount of welling agent (soap), a considerable amount
of a filler (such as soda ash, corn starch, talc, etc) and an alkali-
stable perfume, to give a non-irritating, innocuous, efficient
depilatory. A formulation contains corn starch, calcium hydroxide,
calcium carbonate, barium suiphide, talc, magnesium carbonate
and fragrance.
Shaving creams result from the saponification of a mixture of
coconut oil and stearic acid with mixed caustics (soda and potash).
4 - 8% of the stearic acid may be left unneutralized to supply a
pearly lustre, and 5-10 % glycerol may be added to give body to
the product.

2.2.4.11.8 SHAMPOOS
These are liquid soaps or liquid detergents with special
ingredients. They are classified according to the special ingredients
they contain or according to their physical appearance: Clear,
Cream, Lotion, Colour, Cream paste, Egg, Herbal, Dry, Selsium
and Aerosol shampoos. Addition of other suitable ingredients
could qualify the product as antiseptic, antidandruff or baby
shampoo.
Cream shampoos require opacifying agents such as stearyl
alcohol, cetyl alcohol and their sulphates, alkaline-earth-metal
metal stearates, polyethylene glycol stearates, or magnesium
silicate. Sparkling clear shampoos require solibilizing agents to
prevent turbidity due to poorly soluble organic constituents. Some
inorganic insolubles are dissolved and sequestered by
rnetal-complexing agents such as EDTA (vide supra). Organic
materials causing cloudiness may be high- molecular-weight alkyl
sulphates or high-titre soaps, but are more likely to be finishing
ingredients, such as lanolin or mineral oil, which tend to come out
of solution in some cases as the temperature decreases (and
occasionally as it increases). Such problems are treated by the
addition of solvents or surface-active solubilizing agents and
hydrotropes. Included in the latter group are the polyethylene
oxide fatty derivatives, fatty alkanolamides, sodium
xylenesulphates, short-chain alkylnaphthalene sulphonates,
benzoates, and phthalates.
Body (or viscosity) in shampoos is generally desirable. Gum and
cellulose derivatives have been used for such purposes.
A special problem in soap shampoo formulation is that of oil
building in hard-water resistance. This can be done reasonably
well by the use of sequestrants, or better by the use of lime-soap
dispersants. EDTA is incorporated in relatively small
quantities to prevent deposition of lime soap on the hair during the
rinse operation, and alkanolamides and ethylene oxide condensates
are incorporated to enhance lather during the actual shampooing.
In shampoos using synthetic detergents, a special problem is posed
by their drying action, due probably to both excessive defatting
and adsorption of scroop-producing surface-active agents on the
hair and scalp. A variety of material including sulphonated
vegetable oil, carhoxyrnethylcellulose, lanolin, lecithin,
polypeptides, amino acids, and their fatty acid condensates, have
been found useful in this regard.
The foam-stabilizing agents are added as 2-10% of the weight of
the syndet or soap, to obtain flash foam and quick lathering on oily
scalps. The alkanolamides, particularly monoethanolarnine,
monoisopropanolamine, and high-purity diethanolamine
condensates of lauric acid, are satisfactory. Germicidal agents,
such as chlorinated derivates of phenols and bisphenols have been
prominently applied here.
A typical recipe for shampoo is:
1. Soap liquid or detergent liquid (e.g. sulphonic acid) 400 parts
2. Viscosity agent (e.g. Park R, baravis, carboxyrnethylceilulose) 100 parts
3. Preservative (e.g. Formaline) 25 parts
4. Bodies (e.g. equal amount of light soda ash and STPP) 200 parts
5. Vitamin E (optional) to taste
6. Colour/perfume to taste
Process
Soak Park R overnight in a little water. Add, with stirring,
sulphonic acid to it. Stir very well as you add the ash, STPP and
formaline. Allow to settle. (Filter if need be).
 3.0 SYNTHETIC DETERGENT
INDUSTRIES
3.1 SURFACTANTS
Surfactants are classified according to the charge carried by the
head group e.g.

CH3(CH2)110S03Na+ anionic surfactant

CH3(CH2)11 (0CH2CR2)80H non-ionic surfactant
[CH3(CH2)17]2N+(CH3)2Cl- cationic surfactant

3.1.1 ANIONIC SURFACTANTS

The anionics, made up of C10-15 saturated hydrocarbon chains
attached directly or indirectly to sulphonate or sulphate groups, are
the most important surfactants and find their major uses in
domestic fabric washing and dishwashing. Small-scale detergent
industries are based on the anionics as outlined below.
Other surfactants will only be highlighted briefly
By tetramerizing propylene and adding the resultant mixture of
highly branched dodecenes to benzene, alkylbenezes are

Where alkylbenzenes are available as petrochemicals, their

synthesis is avoided.
The dodecylbenzes can be converted into sodium
dodecylbenzesulphonate, a very good surfactant with excellent
foaming properties, as outlined below:
Sodium tripolyphosphate, Na5P3O10, is an efficient and cheap
builder added to make the product effective in hard water.
Corrosion inhibitors and other additives (sodium sulphate, sodium
perborate, fluorescent dyes, colours, etc.) are incorporated to get a
good synthetic detergents.

3.1.1. ANIONIC DETERGENT

A good formulation of anionic synthetic detergent is outlined
below as adapted from Shreve and Brink.
Surfactants
alkylbenzene 75 parts
fatty alcohol 75 parts
oleum 150 parts
caustic soda solution 200 parts
Corrosion inhibitor
sodium silicate 125 parts
Builder
sodium tripolyphosphate 500 parts
Miscellaneous additives 30 parts
Water 500 parts

Figure 6 is simplified continuous flowchart for the production of

the detergent.
Figure 6: Simplified continuous flow chart for the production of
heavy-duty detergent granules (Procter & Gamble Co.)
3.1.1.1.1. Processes
Sulphonation-sulphation: The alkyibenzene is introduced
continuously with the oleum into the sulphonator. Bath principle is
used to control the heat of conversion and maintain the
temperature of about 54.4°C. Fatty alcohol and more oleum are fed
into the sulphonated mixture, and the temperature maintained
between 49 and 54.4°C.
Gaseous sulphur trioxide sulphonation has been preferred to the
oleum method.
Neutralization: Caustic soda solution is used to neutralize the
sulphonated-sulphated product under controlled temperature to
maintain fluidity of the surfactant slurry, which, together with the
sodium tripolyphosphate (STPP) and most of the miscellaneous
additives, is introduced into the crutcher. The paste thickens as
water is removed by the STPP as per equation below:
Na5P3O + 6H2O Na5P3O10.6H2O
STPP STPP hexahydrate
This mixture is sprayed under high pressure to give granules of
wanted shape, size and density which are air-cooled and dried and
stabilized from 115.6°C. Fig. 7 shows the continuous series
Suiphonation-Suiphation and Neutralisation.
Figure 7: Continuous series Sulphonation-Sulphation, ending
with Neutralisation, in the circulating heat-exchanging
dominant bath to control heat (Procter &Gamble Co.)
3.1.1.1.2 Biodegradability
This is the ease with which a surfactant is decomposed by
microbial action. The tetrapropylene-derived product decomposes
or degrades slowly, thus leaving persistent residues even after
sewage treatment and threatening aquatic lives. Thus, the
propylene-tetramer-based surfactants had to be withdrawn from
the market.

3.1.1.2. Biodegrable anionic surfactants

On the other hand, sodium alkyhlenzene sulphonate, with straight-
chain alkyl groups are much more rapidly biodegraded. The
straight-chain alkyl group is derived either from n-paraffins in the
C10-15 range or from paraffin waxes (C10-15). The n-paraffins are
isolated from kerosene petroleum fractions and converted into
either monochloroparaffins or non-terminal olefins used to
alkylate benzene under Friedel Crafts conditions employing HF
and AICI3. Paraffin waxes are cracked and fractionated to
obtain the C10-15 fraction used to alkylate benzene. The straight-
chain paraffins are also made by polymerizing ethylene, using
Ziegler-type and other polymerizations, e.g. the Alfol process.
Thus, the tetrapropylene benzene sulphonate (TPBS) has been
replaced.

3.1.1.2.1 Other anionic biodegradable surfactants

Other efficient surfactants without benzene ring have been
developed. They include:

3.1.1.2.1.1 Olefin-sulphonates: These are produced in two ways:

a) cracking of paraffin waxes, and
b) conversion of ethylene into a mixture of long-chain olefins
using triethylaluminium catalyst (telomerization). The
olefins are sulphonated using sulphur trioxide in film
reactors. Neutralization hydrolysis of the sulphonation
products with aqueous caustic soda follows. The
 resulting mixture of sulphonates, termed alpha-olefin
sulphonate, is rapidly biodegradable an excellent surfactant.

3.1.1.2.1.2 Alkyl sulphates: Natural oils and fats can be reduced

either directly to give fatty alcohols and glycerol or transesterified
with short-chain alcohol before reduction. Two other industrial
routes to long-chain primary alcohols are also practised.
First, the aluminum alkyls, products of telomerization of ethylene
with triethylaluminium, are oxidized with air to alkoxides which
are hydrolysed to alcohols. The second route uses
hydroformylation in which an olefin reacts with carbon monoxide
and hydrogen in the presence of a cobalt-based catalyst. The
primary products are aldehydes but the process conditions can be
arranged to reduce these in situ to alcohols, thus:
Sulphur trioxide is the most convenient sulphating agent.
Sulphuric acid and chlorosulphonic acid can also be used for the
sulphation but are less convenient in practice.
Primary alkyl sulphates are more expensive. The related alkyl
ether sulphates, e.g. CH3(CH2)11(OCH2CH2)3OSO3Na, prepared by
condensing primary alcohols with ethylene oxide and sulphonating
the resulting ethoxylates, are widely used in dishwashing liquids.
Secondary alkyl sulphates are prepared by treating long- chain
olefines with 90-95% sulphuric acid in excess.

13. 1.1.2.1.3 Alkanesulphonates: Linear paraffins are converted

directly into surfactants of general formula RR1CHSO3Na
by reaction with sulphur dioxide and oxygen in a radical-chain
reaction, termed sulphoxidation, initiated by either ultraviolet or
gamma-irradiation.

3.1.2 NON-IONIC SURFACTANTS

Although some industrially produced non-ionic surfactants are
based on sugars and related polyols, by far the most important
class are those represented by the general formular below:

in which the hydrophilic group is a polyoxyethylene chain, R

contains a long hydrocarbon chain and X is a linking group such as
-O- or -COO-. These are produced by treating a substrate RXH
with ethylene oxide in ethoxylation reactions to get mixtures of
materials with different numbers of oxyethylene (-OCH2CH2-)
groups attached to the hydrophobic R group, n, in the general
formula representing the average number of oxyethylene
groups.
Non-ionic surfactants are liquids or waxy solids that are more
easily adsorbed and produce lower surface tensions at equivalent
concentration as the charged surfactants. They also show unusual
solubility characteristics. At the cloud point (temperature), a
heated and aqueous solution of polyoxyethylene non-ionic
surfacant becomes turbid. Above this temperature, a surfactant-
rich second phase separates, leaving very little surfactant in the
water. Below the cloud point, most non-ionic surfactants are
miscible in all proportions with water. The cloud point of a given
surfactant depends on the structure of its hydrophobic group and
the number of oxyethylene units it contains.
Ethoxylation reactions can be (a) base-catalyzed, (b) acid-
catalyzed, and (c) highly exothermic.
Alkyiphenol ethoxylates or ethoxylated alkylphenols were the first
non-ionic surfactants widely used. Nonylphenol was produced by
BF3-catalyzed alkylation of phenol with propylene trimer.
Dodecyl and octyl-phenol were produced by use of propylene
tetramer and diisobutene respectively. Being products of branch-
chain phenols, they are biologically hard and are being replaced by
biodegradable materials.
Other ethoxylates include alcohol ethoxylates (from long-chain
primary alcohols), amine ethoxylates (from the reaction of
alkylamines with ethylene oxide to first give diethanolamines).

3.1.3 CATIONIC SURFACTANTS

The industrially important materials of cationic surfactants are
based on quaternary nitrogen compounds or amines. The most
widely used route to them, termed the fatty route, starts from long-
chain fatty acids converted by NH3 at 200-300°C into nitriles
which are hydrogenated either to the corresponding primary
amines or to amines containing two long-chain alkyl groups. The
amines are converted into a number of derivatives used
technically, the most important being quaternary compounds,
e.g. (n-C18H37)2N+(CH3)2Cl-.

3.2 DETERGENT FORMULATIONS

Tedder et al gave categories of detergents and their formulations.

3.2.1 FABRIC-WASHING POWDER

1. Sodium soap (mostly tallow-based) 50-60%
2. Sodium perborate (heat-sensitive bleach, effective at 70°C and below) 8-20%
3. Sodium silicate (anticorrosion agent) 3-6%
4. Fluorescer (whitener) 0.02-0.8%
5. Lathering booster small amount
6. Sodium carboxymethylcellulose (antiredeposition agent) small amount

7. Perfumes small amount

8. Water small amount

3.2.2 HEAVY-DUTY FABRIC-WASHING POWDERS

Heavy-duty fabric-washing powders are designed primarily
for the main wash (white and heavily soiled articles and most
coloured items); and light-duty powders and liquids are designed
for washing woolens, sensitive coloured articles and the more
delicate fabrics.
Proteolytic enzymes are now included in the formulations of
washing powders to break down proteinaceous stains, e.g. blood.
Such products function best when used in a cold water soaking
operation prior to the hot wash, although they are also very
effective when used in the wash itself. They break down
proteinaceous material during the soak and the result of the soak-
wash cycle is very effective removal of the difficult stains.
Component Concentration (%)
low-subdising high-subdising
formulation formulation
1. Sodium alkylbenzenesulphonate
(usually C10-15 straight-chain alkyl) 3-12 14-20
2. Sodium soap (usually tallow-soap) 2-10
3. Non-ionic surfactant
(eg. C12-18 or C9 alkylphenol condensed
with 9-18 moles of ethylene oxide) 2-5
4. Lather-booster (usually
 C11-17-alkyl-(CONHCH2CH2OH) 2
5. Sodium tripolyphosphate (usually 80%) 25-60 30-50
6. Sodium perborate 0-30 0-20
7. Sodium silicate 4-8 5-10
8. Sodium sulphate 4-18 10-15
9. Sodium carboxymethyl cellulose 1-2 0 5-1.5
10 Fluorescers, perfume, enzyme (if present)
and water to 100 to 100

Unlike for soap powders, high with good cleaning for products
surfactants. Most automatic washing tolerate high-sudsing
products (owing to overflow hence low-sudsing products are
becoming all the more important. High-sudsing is usually achieved
by an anionic surfactant in combination with a lather-booster such
as the ethanolamide, n-C11H23CONHCH2CH2OH, and an amine
oxide such as n-C12H25N+(CH3)2O. Low-sudsing is achieved by
using a mixture of anionic surfactant, soap and non-ionic
surfactant.
After repeated wash-wear cycles, many white articles tend to
develop a yellow or grey appearance. Fabric-washing products
usually contain fluorescent whitening agents to combat this.
The fluorescers do this by absorbing ultra-violet and re-emitting
the absorbed energy by fluorescence in the blue region of the
visible spectrum. The resultant ‘blueing’ corrects the tendency of
fabrics to look yellow and makes them appear whiter and brighter.
Bleach provides general cleaning and deals with localized stains
from, e.g. food and drink. Sodium perborate (NaBO2H2O2.3H2O),
incorporated in the fabric-washing formulation, releases hydrogen
peroxide, H202, which bleaches effectively at about 70°C. A
separate bleach, usually aqueous sodium hypochlorite, added to the
wash, also does a good bleaching job.
A cationic surfactant, added to the final rinse water in the fabric-
washing process, is adsorbed on the fabric and imparts a pleasant
soft feel. The best softeners are quaternary compounds, such as (n-
C18H37)2N+(CH3)2Cl-. Typical commercial fabric-softening
products are aqueous solutions or dispersions containing 5-8% of
quaternary salt, 0-1% of non-ionic surfactant, fluorescent
whitening agents and perfume.
2.2.3 DISHWASHING LIQUIDS
Component Concentration (%)
Type 1 type 2
Surfactants
1. Sodium alkyibenzenesulphonate 18-26 10-25
2. Sodium alkyl ether sulphate
(n-C12H25(OCH2CH2)30S03Na
or a mixture of compounds with
Similar chain length) 10-18
3. Alkylphenol-based non-ionic
(e.g. octyl- or nonyl-phenol
condensed with 10-12moles of ethylene oxide) 2-10
4. N-alkylethanolamide (e.g.
n-C12H25(OCH2CH2)30S03Na 1-5
5. Ethanol 5-15 5-15
6. Urea 2-8 2-8
7. Sodium xylenesulphonate 2-8 2-8
Other additives
8. Perfume, colourants, other
additives and water to 100 to 100

Dishwashing is more pleasant if the water is hot and foaming

throughout the operation. Hence the product must both aid
removal and suspension of food residues and give a high level of
foam that is not easily depressed by fats and other food residues. It
must also be mild to skin. One or two of the solubilizing agents
(not all three) may be present and serve to keep the surfactants in
solution and give the product a suitable viscosity. The cheap
products contain 10% surfactant concentrations, while the more
expensive ones (such as in the formulations above) contain 40%.

3.3 DEODOURANT
This is a disinfectant that not only eliminates and inhibits the
growth of infection-responsible and odour-fouling
microorganisms but also imparts a pleasant odour on the target
environment, such as car, room, Whitehouse, bathroom, office,
hotel room, etc. It is prepared as cream, lotion, stick, powder, gel,
aerosol or soap.
In formulating one such products (lotion), caustic soda and a
surfactant (e.g. sulphonic acid) are dissolved in water with
vigorous stirring. Confirm that the surfactant has neutralized the
caustic soda, to create room for perfume absorption, by getting pH
reading of 7-8, using a pH testing paper or pH metre. Add
formaline and colourant. Stir for proper mixing and add perfume
and stir more. Filter.

The proportions of the raw-materials are as follows:

Component Concentration (%)
1. Surfactant 0.8
2. Caustic soda 1.5
3. Formaline 0.3
4. Perfume 1.5
5. Colourant (water-soluble) to taste
6. Water 96

Stick products include alcohol solutions ot deodourant chemicals

solidified with soap.
Chemical agents that provide deodourant properties are usually
chlorophenols, such as hexachlorophenes, chlorohexydenes,
chloroxylenols, trichiorophenol (TCP), and monsanto (actamer).

3.4 ANTIPERSPIRANT
This is a deodourant applied to the skin and which also controls
perspiration. Like deodourant, it is prepared as cream, lotion, stick,
powder, gel, aerosol or soap.
Stick antiperspirant is made with modified aluminium salts (basic
chlorides partially complexed with lactic acid). It contains less
alcohol than the deodourant stick formulations. Chemical agents
that provide antiperspirant properties are the chloride and
sulphate of aluminium, zirconium salts and some zinc salts.
Aluminium chloride, which is probably one of the better
antiperspirant agents, has a pH of about 2.25 in 20% solution in
water. It is successfully used in some antiperspirants, but must,
however, be buffered, to reduce both irritation to the skin and its
effect on clothing. The most common buffer used is urea.
Aluminium sulphate with a pH of 2.7 or 2.9 is not quite as acidic,
but still acidic enough to require a buffer. Aluminiun
chlorhydroxide complex (approximately Al2(OH)5Cl, a basic
aluminium chloride complex) with a pH of about 4.3 does not
require a buffer which is a great advantage. However, it is not as
good an antiperspirant as aluminium chloride or sulphate.

3.5 DENTAL POWDER

This is a powder product used with toothbrush for cleansing the
mouth system. It contains a disinfectant (e.g. sodium fluoride) to
stop and prevent mouth odour and tooth decay. It also contains
a surfactant (e.g. sodium lauryl or dodecyl sulphate) to wash the
system, an abrasive (e.g. calcium carbonate) to aid the washing,
and a flavour (e.g. Menthol).
In formulating one such product, menthol is ground and mixed
with sodium fluoride, calcium carbonate, and sodium lauryl or
dodecyl sulphate. Table salt may be added, or may replace the
fluoride in cheaper preparations. Kaolin, silica and talcum powder
(talc), are other abrasives used. The proportions are as outlined
below:
Component Concentration (%)
1. Disinfectant (e.g. Sodium fluoride) 1.9
2. Abrasive (e.g. calcium carbonate,
talc, kaolin, silica) 95.0
3. Surfactant (e.g. lauryl sulphate) 3.8
4. Menthol (flavour) to taste
3.6 TOOTHPASTE
This is a paste product used with toothbrush for cleansing the
mouth system. It has the same contents as dental powder plus
other additives, which include glycerine, saccharine and
proportions are as outlined below:
Component Concentration (%)
1. Disinfectant (eg. Sodium fluoride) 1.9
2. Surfactant (e.g. sodium
dodecylsuphate) 3.8
3. Abrasive (e.g. calcium carbonate,
kaolin, talc, silica) 94.0
4. Menthol (flavour) to taste
5. Saccharine (sweetener) to taste
6. Glycerine (or glycerol) to taste
7. Water to taste
Procedure
The ground menthol is mixed well with the disinfectant,
abrasive and surfactant. The preparation is made pasty with water,
slurry with the glycerine, and tasty with the saccharine. Glycerine
also cottributes to the sweet taste. The product is packaged in
collapsible tubes.
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