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Chemical Process Industries

Question No. 01 :

a. What are soaps and detergents and how they differ?

b. Describe raw materials used to make soaps and
detergents.
c. Explain the manufacturing of soaps and detergents
using flowsheet diagrams.

Answer:

Soaps are sodium or potassium fatty acids salts, produced from the hydrolysis
of fats in a chemical reaction called saponification.

Soap-making was an established craft in Europe by the seventh century. Soap-

maker guilds guarded their trade secrets closely. Vegetable and animal oils were
used with ashes of plants, along with fragrance. Gradually more varieties of soap
became available for shaving and shampooing, as well as bathing and laundering.

Soaps are denoted by the general formula RCOO-Na+, where R is any long chain
alkyl group consisting 12 to 18 carbon atoms.

Each soap molecule has a long hydrocarbon chain, sometimes called its 'tail', with
a carboxylate 'head'. In water, the sodium or potassium ions float free, leaving a
negatively charged head.

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What are Detergents?

Detergents are primarily surfactants that are used as water-soluble cleansing
agents. They lower the surface tension of water, essentially making it ‘wetter’ so
that it is less likely to stick to itself and more likely to interact with oil and grease.
So, they combine with dirt to make it more soluble.

Detergents also possess germicidal properties which makes them useful in

hospitals.

Molecular structure of detergents consists of a long hydrocarbon chain and a

water-soluble ionic group.

Types of detergents:
1. Cationic detergents
2. Anionic detergents
3. Non-ionic detergents

Most detergents have a negative ionic group and are called anionic detergents.
The majority are alkyl sulfates. Others are "surfactants" (from surface active
agents) which are generally known as alkyl benzene sulfonates.

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Detergents having positive ionic group are called cationic detergents. Most of
these are derivatives of ammonia and are mostly found in a shampoo or clothes
rinse. The purpose is to neutralize the static electrical charges from residual
anionic (negative ions) detergent molecules. Since the negative charges repel
each other, the positive cationic detergent neutralizes this charge.

Nonionic detergents are used in dish washing liquids. Since the detergent does
not have any ionic groups, it does not react with hard water ions. In addition,
nonionic detergents foam less than ionic detergents. However, these detergent
molecules have some polar parts to provide the necessary water solubility.

Examples:

Difference between Soaps and Detergents:

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Properties Soaps Detergents

Sources Natural sources i.e. Synthetic sources i.e.
Plants or animals Petroleum fractions
Molecular Structure R COO- Na+ RSO4- where R can be phenyl
Chemically Sodium salts of Sodium salts of alkyl
fatty acids sulphonates or alkyl benzene
sulphonates
Effectiveness in hard water Forms scum Does not form scum
Effectiveness in acidic water Forms precipitates Does not form precipitates
Solubility in water Takes time to Dissolve faster
dissolve
Cleaning power Less powerful More powerful
Effect to the environment More Less biodegradable
biodegradable

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Selection of Raw Materials:

The first phase in the manufacturing of soaps and detergents is the selection of
raw materials. Raw materials are selected on the basis of the following factors:

▪ Cost
▪ Human and environmental safety
▪ Compatibility with other ingredients
▪ Performance characteristics
▪ Appearance of the final product

Raw materials for soaps:

Soaps are commonly made from fats and oil and inorganic water-soluble bases.
The prime sources of fats are beef and mutton tallow.

Fatty acids present in tallow are:

▪ Lauric Acid ▪ Oleic Acid

▪ Myristic Acid ▪ Linoleic Acid
▪ Palmitic Acid ▪ Ricinoleic Acid
▪ Stearic Acid
Main oils used in soap making are:

▪ palm oil ▪ kernel oil

▪ coconut oil ▪ ground nut oil
▪ castor oil ▪ rice bran oil
▪ neem oil

Oils and fats can be classified either lauric or non-lauric oils /fats.

Properties Lauric fats Non-lauric fats

Relative amount of lauric acid Higher Lower
Source Coconut, palm Cocoa, palm
kernel oil
Cost Expensive Less expensive

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Different oils produce soaps of varying hardness, odor, and lathering properties.
Normally 75-85% tallow and 15-25 % coconut oil are used in soap making.

▪ C12 and C14 soaps lather quickly but they produce an unstable, coarse
bubble foam
▪ C16 and C18 soaps lather slowly but lead to stable, fine bubble foamed.

Some of the other ingredient in soap are:

▪ Talc as filler which also act as carrier for perfume.

▪ Fragrance oil to add scent to the soap.
▪ Sodium silicate to give firmness to the soap.
▪ Sodium carbonate to rapidly neutralize the free fatty acids present in oil
and complete the saponification reaction.
▪ Caustic lye (50% caustic soda) for saponification.
▪ Dyes to impart colour.

The raw materials of a bar soap can be pretreated to remove impurities and to
achieve the desired color, odor and performance characteristics desired in the
finished bar.

Raw materials for detergents:

• Basic ingredients:
1. Crude oil as a hydrocarbon source.
2. Sulfuric acid is added to the processed hydrocarbon to produce a molecule
like the fatty acids present in soap.
3. Alkali to the mixture creates a surfactant molecule.

Other ingredients include:

‘Builders’ that have several functions including:

• To increase the efficiency of the surfactant.

• To sequester minerals in hard water, meaning that they hold them in
solution, preventing them from precipitating out.
• To emulsify oil and grease into tiny globules that can be washed away.
• To inhibit corrosion and help assure that the detergent will not damage a
washing machine e.g. sodium silicate.

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• Still other builders contribute to the chemical balance of the wash water,
making sure that it conduces to effective washing.

Ant redeposition agents i.e. chemicals that help prevent soil from settling back on
washed clothes.

Fluorescent whitening agents: By converting invisible ultraviolet light into

visible blue light, these help to maintain brightness or whiteness.

Oxygen bleaches such as sodium perborate improve the detergency of the

mixture, especially in low-phosphate or no-phosphate products, as well as helping
to remove some types of stains.

Processing aids such as sodium sulfate are also used to prevent caking and to
standardize product density.

Enzymes break down some stains to make them easier to remove and are an
essential ingredient in various pre-soak products used to treat heavily soiled
clothes prior to laundering.

Perfumes or fragrances cover the odor of the dirt and any chemical smell from
the detergent itself.

Suds control agents also have a role in detergents—too many suds (foam or
lather) can cause mechanical problems with a washing machine.

MANUFACTURING OF SOAPS AND DETERGENTS:

Soap manufacturing process:
The manufacturing of soaps consists of a comprehensive range of processing and
packaging activities. The complexity the activities involved in soap
manufacturing process may vary from small plants that employ a few people to
those with many hundred workers. Products may range from all purposes and
uses to those that for used for a specific application or requirement.

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Mixer

CSTR (Continuous Stirred Tank Reactor)

Filter-press

Cutting machine

Drying machine

Stamping

While the actual production process may vary from company to company and
manufacturer to manufacturer, there are some steps, which are common to all
types of soaps.

The industrial soap making involves five basis steps -

1. Saponification
2. Glycerin Removal
3. Soap Purification
4. Salt Removal
5. Finishing

These different steps involve various processing steps and operations in their
own. A brief description of these different steps is given below -

1. Saponification:
The saponification process involves the mixing of tallow (animal fat) and coconut
oil with sodium hydroxide and the application of heat. The process results in
formation of soap, which is a salt of long chain carboxylic acid.

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2. Glycerin Removal:
Glycerin is more valuable than soap, and hence most of it is removed for its uses
in more expensive cosmetic products. Some of the glycerin is left in the soap to
make it soft and smooth. Soap is generally not very soluble in salt water, while
glycerin is, hence the salt is added to the wet soap thereby causing it to separate
out into glycerin and soap in salty water.

3. Soap Purification:

In the soap purification stage, any dissolved soap and remaining sodium
hydroxide are removed to obtain pure soap.

The spent lye contains a small quantity of dissolved soap which must be removed
before the evaporation process. This is done by treating the spent lye with ferrous
chloride.

However, if any hydroxide ions remain the ferrous ions react with them instead,
so these are first removed with hydrochloric acid:

HCl + NaOH → NaCl + H2O

The ferrous chloride is then added. This reacts with the soap to form an insoluble
ferrous soap:

FeCl2 + 2RCOONa → 2NaCl + (RCOO)2Fe

This precipitate is filtered out and then any excess ferrous chloride removed with
caustic:

2NaOH + FeCl2 → Fe(OH)2 (s) + 2NaCl

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This is filtered out, leaving a soap-free lye solution.

4. Salt Removal:

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

5. Finishing:
The final stage of industrial soap manufacturing process, finishing stage involves
mixing of additives, such as colors, preservatives, and perfume into soap, which
is then shaped into bars for sale.

Block Diagram of the process is presented below:

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Toilet Soap Manufacturing

▪ Toilet soap generally has less water and more fatty material than laundry
soap and because of this, the base soap intended for manufacturing toilet
soap usually has extra fatty acids that are blended with preservatives before
it is vacuum dried.
▪ These measures ensure that there is no unreacted caustic remains in the
soap by the time it reaches the consumer, and also make the soap softer.
▪ Additives, such as perfume, dye and opacifier are then mixed to the dried
soap and the mixture is milled to ensure even mixing.
▪ It is then plodded and extruded out as a continuous bar, which is cut into
billets and stamped ready for packaging and sale.

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FLOWSHEET DIAGRAM

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Chemical Process in Bar Soap Manufacturing:

Bar soap can be manufactured by either using batch or continuous process. Soap
was manufactured by using batch kettle boiling method, until shortly after World
War II, when continuous processes were developed. Now days, continuous
process of soap making are preferred because of their speed, flexibility, and cost
economy.

Both the batch as well as continuous soaps making processes produce the soap in
liquid form (known as neat soap), and a valuable by-product, glycerin.

• Following are the flowsheet diagrams for batch and continuous processes.

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FLOWSHEET DIAGRAM FOR BATCH PROCESS:

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FLOWSHEET DIAGRAM FOR BATCH PROCESS:

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Detergent manufacturing process:

Although there are three ways of manufacturing dry laundry detergent, only two
are commonly used today.

1. Blender process:

In the blender process favored by smaller companies, the ingredients are mixed
in large vats before being packaged. The machines used are very large: a common
blender holds 4,000 pounds (1,816 kilograms) of mixed material, but the blenders
can accommodate loads ranging from 500 to 10,000 pounds (227 to 4,540
kilograms). By industry standards, these are small batches for which the blender
process is ideal. While some settling may occur, the resulting detergent is of high
quality and can compete with detergents made by other processes.

Following are the steps involved:

I. First, ingredients are loaded into one of two machines: a tumbling blender
or a ribbon blender.
II. The tumbling blender, shaped like a rectangular box, is turned and shaken
from outside by a machine, while the ribbon blender is a cylinder fitted
with blades to scrape and mix the ingredients.
III. After the ingredients inside the blender have been mixed, a doorway at the
bottom of the bowl is opened.
IV. With the blender still agitating the ingredients, the mix is allowed to run
out onto a conveyor belt or other channeling device.
V. The belt then moves the detergent to another area of the factory where it
can be dropped into boxes or cartons for delivery to wholesalers or
distributors.
2. Agglomeration process:
The second commonly used method of production is called the agglomeration
process. Unlike the blender process, it is continuous, which makes it the choice
of very large detergent manufacturers. The agglomeration process can produce
between 15,000 and 50,000 pounds (6,800 and 22,700 kilograms) of detergent
per hour.

Following are the steps involved:

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I. In this method, dry ingredients for a detergent are first fed into a large
machine known as a Shuggi agglomerator (Shuggi is the manufacturer).
Inside the agglomerator, sharp, whirling blades mix the material to a fine
consistency; the process resembles food being textured inside a food
processor.

II. After the dry ingredients have been blended, liquid ingredients are sprayed
on the dry mix through nozzles fitted into the agglomerator's walls. The
blending continues, causing an exothermic (heat-producing) reaction to
occur. The resulting mixture is a hot, viscous liquid similar to gelatin that
hasn't hardened.

III. Next, the liquid is allowed to flow out of the agglomerator. As it leaves
the machine, it collects on a drying belt where its own heat, exposure to
air, and hot air blowers render it friable—easy to crush or crumble. The
newly made detergent is then pulverized and pushed through sizing screens
that ensure that no large lumps of unmixed product go out to the market.
The result of this process is a dry detergent made up of granules of the
mixed detergent.

3. The slurry method:

In this process, ingredients are dissolved in water to create a slurry. With a
pump, the slurry is blown through nozzles inside the top of a cone shaped
container as hot, dry air is simultaneously forced into the bottom of the cone.
As the slurry dries, "beads" of dry detergent fall to the bottom of the cone,
where they can be collected for packaging.

Although the resulting product is of high quality, the fuel costs and engineering
problems associated with venting, reheating, and reusing the air have led to this
method being largely replaced by agglomeration.

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FLOWSHEET DIAGRAM

1. Austin G.T. “Soap and detergent”., Shreve’s Chemical Process Industries, 5th
Edition, McGraw Hill Publication, 1975, p.529

2. Dixit,S.” Toilet soaps and bathing bars” Chemical business,

October,2011,p.18

3. Israel, A.U., Obit, I.B., Asquo, J.E. “Recovery of glycerol from spent soap
lye by-E-Journal

of Chemistry Vol 5, No.4, pp. 940-945, October 2008 http://www.e-

journal.net].

4. James A. K., Riegle’s Handbook of Industrial Chemistry 9th Edition, CBS

Publication, 1997.
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5. New Zealand institute of Chemistrynzic.org.nz/ChemProcess/detergents

6. Zhu S., Chambers J.G., Naik V., Encyclopaedia of Chemical Technology

Kirk-other, fifth

edition, Vol.22, 2004

7. http://www.cirec.com/2011/01/soap-and-detergent-industry-in-india.

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Q No. 1: What is the importance of fatty acids in soaps?

Answer:

Soap is the alkali salt of fatty acid. Fatty acids have varying chain length and
may be saturated or unsaturated. Fatty acid content of the oils varies.
Unsaturated fatty acids give softer soap with lower melting point and are less
stable while soap from saturated fatty acids are firm, slowly soluble, milder and
have good detergency. Total fatty acid is considered beneficial ingredient of
toilet soap. Property of soap depends on the chain length of fatty acids in blend,
amount of saturation and unsaturation, formulation, and soap structure. A
judicious blend of oils and fats are necessary to obtain soaps of ideal properties.

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