Soap and Detergents

Batch saponification production

Continuous hydrolysis and saponification process
Sulfated fatty alcohols
Alkyl-aryl sulfonates.
• Soaps are water-soluble sodium or potassium salts of fatty acids.
Soaps are made from fats and oils, or their fatty acids, by treating
them chemically with a strong alkali.
• Soaps are used for human comfort, cleanliness and for industrial use.
• Soap is a surface active agent or surfactant. The soap molecules
contain both hydrophilic part and hydrophobic part.
• The success of any cleaning agent is to supply compounds with
hydrophilic part and hydrophobic groups which decreases surface
tension & Increases wettability
• The hydrophilic part of soap is carboxylate head group and
hydrophobic part is aliphatic chain.
• The dirt or grease is cleaned by key mechanism.
Difference between Soap & Detergent
• soap" and "detergent" are used interchangeably, but really they're
quite different things. A detergent is a chemical substance you use to
break up and remove grease and grime, while soap is simply one kind
of detergent.
• Detergents differ from soaps in their action in hard water.
• Soaps from insoluble compounds with the calcium & magnesium ions
present in water. These insoluble precipitate out & reduce foaming
and cleaning action.
• Detergents may react with hard water ions, but the resulting products
are either soluble or remain colloidally dispersed in water
Chemical Reactions:
• Fat splitting reaction:
(RCOO)3C3H5 + 3H20 --------------- 3RCOOH + C3H5(OH)
3 triglycerides water fatty acid glycerin
• Saponification Reaction:
RCOOH + MOH --------------- RCOOM + H2O
Fatty acid base soap water
Saponification
Process of making soap from animal fat or vegetable oil using a base.

O
CH2 – O – C – (CH2)14CH3 CH2 – OH
O O
CH – O – C – (CH2)14CH3 + 3 NaOH CH – OH + 3 Na+ -OC – (CH2)14CH3
O
CH2 – O – C – (CH2)14CH3 CH2 – OH

glyceryl tripalmitate sodium glycerol 3 sodium palmitate

(tripalmitin) hydroxide (soap)
 Fats and Oils
• The fats and oils used in soap making come from animal or plant sources. Each fat or oil is made up of
a distinctive mixture of several different triglycerides.

• In a triglyceride molecule, three fatty acid molecules are attached to one molecule of glycerin. There
are many types of triglycerides; each type consists of its own particular combination of fatty acids.

• Fatty acids are the components of fats and oils that are used in making soap. They are weak acids
composed of two parts:
A carboxylic acid group consisting of one hydrogen (H) atom, two oxygen (O) atoms, and one carbon (C)
atom, plus a hydrocarbon chain attached to the carboxylic acid group. Generally, it is made up of a long
straight chain of carbon (C) atoms each carrying two hydrogen (H) atoms.
• Common fatty acids used are oleic acid, stearic acid, palmitic acid, lauric acid and myristic acid.

Typical vegetable oils used in soap making are palm oil, coconut oil, olive oil, and laurel oil. Each species
offers quite different fatty acid content and hence, results in soaps of distinct feel. The seed oils give
softer but milder soaps. Soap made from pure olive oil is sometimes called Castile soap and is reputed
for being extra mild.
 Alkali
• An alkali is a soluble salt of an alkali metal like sodium or potassium.
Originally, the alkalis used in soap making were obtained from the
ashes of plants, but they are now made commercially. Today, the term
alkali describes a substance that chemically is a base (the opposite of
an acid) and that reacts with and neutralizes an acid.

• The common alkalis used in soap making are sodium hydroxide

(NaOH), also called caustic soda; and potassium hydroxide (KOH), also
called caustic potash
 Batch saponification process

• Acid Hydrolysis of glycerides followed by alkali addition slowly/

direct saponification using a strong caustic in batch process.
Continuous hydrolysis and saponification process

• This method is of greater use as it has following advantages over

batch process.
1. Greater control of product distribution.
2. Higher glycerin yields(>80%).
3. Less off-color production during the short-time hydrolysis step.
Hydrolyser
• Zinc oxide catalyst is used during the hydrolysis step that takes place
when water along with high-pressure steam is made contact with
counter flow of oil in a separating column. 40-45 atm pressure and
250-260oC temperature are maintained in the column.
• Intimate mixing is required for the water oil immiscible phase. Water
has 10 – 15% solubility in oil and fats.
• Liquid-liquid contact column(20m ht,60 cm dia) is used for this
operation, from its bottom the separated glycerol is removed
continuously and from top fatty acids is sent to vacuum dryer and
separator. Bottom stream from hydrolyser contains 15-20% glycerine,
ZnO and partially saponified fats.
Fatty acid stream block
Flash tank: Fatty acids from the hydrolyser enters the steam flash tank to remove water & concentrate the
fatty acids.
Vacuum still:
• The concentrated fatty acids enter a high vacuum still.
• Jet ejecter is used to generate vacuum in the still.
• Wastes are separated from the bottom.
• Fatty acid is also taken out as a marketable product.
Mixer: Fatty acid produced from vacuum still is now pumped to mixer. Base such as NaOH or KOH is mixed in
appropriate proportions and mixed thoroughly. After mixing a viscous mass is produced.
(Neautralization reaction with 50% Caustic Soda).
Blender:
• The viscous mass from the mixer (Neat soap at 93C) is sent to the blender.
(0.002-0.1%NaOH, 0.3-0.6%NaCl,30%water)
• Ingredients like scents, anti fungal & anti bacterial chemicals etc. is mixed in the blender.
• The mixture is then homogenized and achieves a uniform texture
• The blender removes the solid mass which is then sent to:
1. Chipping rolls: to manufacture soap strips.
2. Spray dryer: To get soap powder (used in manufacture of liquid soaps).
3. Bar Press Stock: To press and cut the viscous mass into bars of soap.
Finishing Operations
• Pressure is raised to 3.5Mpa, soap is heated to 200C. The heated soap
is released to a flash tank at atm.pr., where partial drying (to20%)
takes place because the soap sol. Is well above the boiling point at
atm.pr.
• This viscous pasty soap is cooled by brine circulation from 105C-65C.
At this temp. soap is continuously extruded & is cut in to bar length.

• Further cooling, stamping, wrapping completes the operation.

Finishing Operations
• it is easy and convenient to make toilet soap directly from soap noodles (or soap
chips) (raw soap).
• In that case main raw materials used for making toilet soap from is soap noodles
(ready-made raw soap), water, color, perfume, preservatives, additives etc.
• This process is started from soap mixer machine where desired color, perfume
preservatives, additives etc. are added. The mixed soap is then fed in to the soap
roller machine where it get homogenized, finishing and final output soap in form
of thin ribbon.
• The same thin ribbon is fed in to the duplex extruder machine which used for
highest compression, finishing of soap and which produced final output of soap in
bar form.
• Automatic soap bar cutting machine is kept next to duplex extruder outlet and
which cut soap in bar form. The next process is cutting of soap bar in to cake
(table) which will be with suitable size of soap stamping process. Then the soap
stamping machine (automatic soap stamping machine in big capacity) is used to
stamp final soap in tablet (cake) form. The stamping dies of stamping machine are
made specially according to buyer's selected logo, design, brand name so buyer
will get final soap with desired logo, design and brand name.
Glycerin stream block
Ion Exchange: 15 – 20% glycerin (sweet water) along with impurities from
the hydrolyser is put to the successive beds of anion and cation exchange
resin. The glycerin reacts with salts. Ion exchange removes the color and
dissolved salts.
Triple effect evaporator: The product stream from ion exchanger is sent to
triple effect evaporator. The glycerin solution is concentrated in evaporator.
Vacuum still: The glycerin obtained from vacuum still is called yellow
glycerin. It is used for industrial use. The steam produced from evaporator is
used in vacuum still to further concentrate the glycerin.
Mixer: For removing color, yellow glycerin is treated with activated carbon in
mixer.
Filter: Activated carbon is separated from the solution. 99% white glycerin is
produced. The yield is 30 – 35kg per ton of soap produced.
Detergents
• Detergents have better surface tension lowering action than soaps.
• Due to excessive foaming, it is unable to reduce organic content of sewage effluent. Biodegradation of
detergent is an important environmental factor.
• Detergents react with hard water ions.
• Detergents are of four types - anionic, cationic, non- ionic and amphoteric.
• Most common type is anionic which is generally made up of sodium salts of an organic sulfate or sulfonate.
• Cationic Agents: These are not normally classified as detergents as their uses are not comparable with soap.
Their chief value is their germicidal properties. The quaternary ammonium compounds are the most
important members.
• Nonionic Agents: These products possess excellent soil removal and grease emulsification accompanied by
low foam. The ethers are extremely stable, in acid and alkaline solutions.
General method to make synthetic detergents:
• Alkyl benzene + oleum -------- alkyl benzene sulfonate
• Tallow fatty alcohol + oleum ---------- fatty alcohol sulfate
• Sulfonate + sulfate + NaOH ---------- sodium salts
• Sodium salts + builders ----------- Detergents
Composition
• Typically, a detergent is a mixture of various substances and is generally
made by compounding the different ingredients, sometimes in the form of
a slurry and is then spray-dried to yield free-flowing granules. A detergent
contains following ingredients, in varying proportions, usually like
• A surfactant (detergent) (8-18%)
• A builder (20-45%) e.g. phosphates or zeolites
• A bleach (15-30%) e.g. sodium perborate
• A fluorescer - 'whiter than white' (0.1%)
• A filler (5-45%) e.g. sodium sulphate
• The detergent also contains water (4-20%) and may also contain up to
0.75% enzyme
Surfactants
• Any compound that affects(usually reduces) surface tension when dissolved in water or
water solutions, or which similarly affects interfacial tension between two liquids.
• Soap is such a material, but the term is most frequently applied to organic derivatives
such as sodium salts of high m.w. alkyl sulfates or sulfonates.
• The cleaning process consists of
1. Thoroughly wetting the dirt and surface.
2. Removing dirt from the surface.
3. Maintaining the dirt in a stable solution(detergency).
Alkyl benzene sulfonates or ABS (also linear alkyl benzene sulfonates or LAS, linear alkyl
sodium sulfonates).
synthetic surfactants often derived from petroleum. Some names of surfactants: Sodium
Lauryl Sulfate (SLS), Sodium Laureth Sulfate (SLES) , Ammonium Lauryl Sulfate (ALS) ,
Ammonium Laureth Sulfate (ALES), Sodium Methyl Cocoyl Taurate, Sodium Lauroyl
Sarcosinate, Sodium Cocoyl Sarcosinate, Potassium Coco Hydrolysed Collagen, TEA
(Triethanolamine) Lauryl Sulfate, TEA (Triethanolamine) Laureth Sulfate, Lauryl or Cocoyl
Sarcosine, Disodium Oleamide Sulfosuccinate, Disodium Laureth Sulfosuccinate, Disodium
Dioctyl Sulfosuccinate, etc.
Detergent Builders
• Builders enhance the quality of the water, thereby making the detergents work in a more effective and
efficient manner.

• Detergent builders soften water by holding free water ions, such as magnesium and calcium. This prevents
these particles to react with other ingredients of detergent, which would have caused them to work less
efficiently or precipitate from solution (soap scum).

• Sometimes more than one detergent builder is used in a product, to develop a builder system with more
effective cleaning performance.

• Traditionally, sodium tripolyphosphate (STPP) was the builder of choice. It offers superior water softening
because of its high binding capacity for heavy metals and calcium ions, good buffering properties that
contribute to detergency action and superior anti-redeposition properties. In addition, the position of STPP
as a preferred builder during 1940s-1970s was further boosted because of its low toxicity. Although STPP has
low toxicity, as a nutrient, it has the potential result in eutrophication (a term used to describe water that is
'over rich' in nutrients, and may to an excessive growth of algae). This led to the search for alternative
products and the development of synthetic detergent Zeolite, which now days, is the principle alternative to
phosphate builders.
 Bleaches
• Bleaches are compounds that are used to clean, whiten and brighten fabrics and
help remove the stubborn stains. Bleaches have proved to be highly effective and
useful in converting the soils into colorless, soluble particles, which can be
removed and carried away by detergents in the wash water. Bleaches can be used
for different cleansing applications, including - laundry, dishwash cleaning and in
household cleaning products.

Types Primary Function Example

Along with whitening, brightening and
Chlorine Bleach removing stains, it also works as an Sodium Hypochlorite
disinfectant

Oxygen bleach can be combined with bleach

Sodium Perborate, Sodium
Oxygen Bleach activators in some products for improved
Percarbonate
performance in lower temperatures.
Detergent fillers
• Detergent fillers are the materials, which are added in detergents to alter their physical characteristics and
properties. The objective of adding fillers to detergents is to make detergents fluid or to turn the fluidized
detergents in powder form. Generally the fillers are bulk components in various detergents with their
primary role to modify and alter the physical properties of the material.

We can also define detergent fillers as additives that can be added in detergents (along with bleaches, bleach
activators, antistatic agents, fabric softners, optical brighteners and antiredeposition agents) to improve the
cleansing performance.

Materials
• The different materials that can be used as fillers in detergents, include -Sodium sulfate,Sodium
chloride,Borax,Alcohols,Anti-foaming agents
• s Borax can be used in solid detergents to make the detergent powder free-flowing. Alcohols can be added
in liquid detergents to increase the solubility of compounds and to reduce the freezing point of mixture.
The addition of anti-foaming agents help in lowering the production of foam thereby making the presence of
detergents in wastewater less obvious. Sodium chloride or sodium sulphate can also be used as fillers.
Sodium sulfate comes at an economical price and has some cleansing effect, especially when it is mixed with
a cleansing agent. Corrosion inhibitors, such as sodium silicate can be added to increase the lifetime of the
washing machines. Generally the usual content of fillers in detergents is about 5-45%.
Methods of detergent mfg
1. Sulfated Fatty Alcohols: (Orvus, Dreft, Duponol, etc.)
These are strong competitors to soap because they are stable in acid,
alkaline, or hard water. Sodium lauryl sulfate, prepared from coconut oil,
represents the bulk of the sulfated fatty alcohols. It is believed that sulfated
fatty alcohols accounted for nearly 20 per cent of the synthetic detergents.
2. Alkyl-aryl Sulfonates. (Oronite, Ultrawet, Santomerse, Tide, Fab, Surf,
Cheer, etc.)
Because of their low price, this group is extensively used in both the home
and industry. Accounted for 58 percent of the synthetic detergents. Their
stability and soil-suspending power is not so good as Sulfated Fatty Alcohols,
but by adding sodium carboxy-methyl cellulose, the suspending power can
be increased.
Sulfated Fatty Alcohols
• The two most important fatty alcohol sulfates are made from
mixtures of fatty alcohols derived from coconut oil, pre-dominantly
lauryl alcohol(C12H25OH), and oleyl alcohol(C18H35OH).
• These high-molecular-weight alcohols are usually prepared either by
sodium reduction or by catalytic hydrogenation of the fatty
glycerides. Sulfitation of these Alcohols then follows.
Catalytic hydrogenation of coconut oil :
• The hydrogenation processes manufacture the higher alcohols by
both continuous and batch wise reaction in the liquid phase at
temperatures of 200 to 300°C., pressures of 100 to 220 atm., with
copper chromite or other catalysts.
• Sodium reduction of coconut oil:
For each batch of coconut oil, 1 ton of molten sodium is dropped into the reactor
which already contains 1 ton of toluene, the latter acting as a solvent for the
reaction mass and as a dispersing medium for the sodium. reducing alcohol such
as Amyl Alcohol is added.
After the reaction is completed, the mixture is dropped into water where
hydrolysis occurs. The mixture settles into three layers, the top containing the
product alcohol and the middle layer contains regenerated reducing alcohol.
Bottoms have caustic soda and glycerin.
This crude product is separated by continuous distillation.

Sulfitation of fatty alcohols:

• The saturated fatty alcohols are usually treated with an excess of concentrated
sulfuric acid under moderate conditions, producing the sulfate which is then
converted to the corresponding sodium salt with alkali.
• The excess sodium sulfate may be separated or left in, where it acts as a filler or
inert, and the whole mixture dried.
 (1) combining the alkyl group with the aromatic hydrocarbon,

Alkyl-aryl Sulfonates (2) sulfonating the resulting compound, and

(3) neutralizing the sulfonic acid.

• The alkyl portion is derived from a kerosene distillate fraction obtained from the refining of
paraffinic crudes.
• When kerosene is used, it is chlorinated at 60-70C in a agitated, jacketed reactor with a catalyst
added, usually iodine.
• The monochlorinated kerosene is reacted with an excess of benzene in the presence of AlCl3 in a
agitated, jacketed reactor.
• One part of chlorinated kerosene to 6 parts of benzene to 0.1 parts of AICl3 are the approximate
molar ratios used in this reaction.
• The alkyl-benzene crude is purified by distillation and then sulfonated.
• Sulfonation procedures may vary in each plant. For 100 per cent H2S04, the reaction temperature
and time would be, respectively; 65 to 80°C. and 1 hr.
• Usually the alkyl-benzene is mixed with about 1.25 times its weight of acid. The reaction
temperature is closely controlled. After sulfonation the mass is allowed to settle, and the spent
H2S04 and unreacted hydrocarbon layers are removed.
• The sulfonated material is drowned in ice water and neutralized with NaOH in a agitated tank
provided with cooling coils. After neutralization it may be dried, depending on the finished
product.