Diploma in Chemical Engineering - 6th Semester

Unit- IV : Synthetic Detergent

Subject Petrochemicals (Elective- II)
Baishakhi Kayal
Lecturer in Chemical Engineering
Hooghly Institute of Technology, Hooghly
 SUBJECT : PETROCHEMICALS (ELECTIVE II )
( D.Ch .E - 6th Semester )
SYNTHETIC DETERGENT : UNIT : IV

INTRODUCTION :

A detergent is a surfactant or a mixture of surfactants having cleaning properties

in dilute solutions. Commonly, "detergent" refers to alkylbenzene sulfonates, a
family of compounds that are similar to soap but are less affected by hard water.

The advantages of synthetic detergent over soap are grouped below :

• High detergency in soft and hard water (they do not react with Ca and Mg
salts present in water.)
• Small concentration of detergent is sufficient to give rise large detergency
action.
• Detergency action is reached at low temperature
• Do not hydrolyses

STRUCTURE OF DETERGENT :

Detergents are made up of hydrophilic and hydrophobic parts. Detergent when

placed in water arranges in two constituents namely hydrophilic and hydrophobic
parts. During washing of fabric hydrophilic heads firmly remain in water carrying
the dirt particles while the hydrophobic tails repelled by water project outwards.
Thus these tails are attracted by the tails of another layer of hydrophobic tails and
form chains. The rust or dirt particles which is surrounded by heads of hydrophilic
molecules are easily removed by agitation.

Detergent molecules have ionisable inorganic groups such as SO3- , COO- , CO- ,
NH+ , NH2- , Cl- etc which are soluble in water and the long chain hydrocarbons
act as hydrophobic constituents. These will pierce the surface of water reducing the
surface tension. All detergents should wet the fibres / materials so that dust can be
 dispersed. Hense they should possess good emulsifying , froyhing and detergent
properties.

CLASSIFICATION OF DETERGENT

Detergents are basically two types , ionic and non ionic.

IONIC DETERGENT :

The ionic types are further classified into anionic and cationic.

ANIONIC DETERGENT :

When the long hydrophobic part of the detergent molecule behaves as an anion in
aqueous solution , the compound is called an anionic detergent. Example of anionic
detergent is Dodecyl benzene sulphonate. The detergency of the anionic detergent is
vested in the anion. The anion is neutralized with an alkaline or basic material, to
produce full detergency. Typical anionic detergents are alkylbenzene sulfonates.
There are three kinds of anionic detergents: a branched sodium dodecylbenzene
sulfonate, linear sodium dodecylbenzene sulfonate, and soap. The alkylbenzene
portion of these anions is lipophilic and the sulfonate is hydrophilic.

CATIONIC DETERGENT :

When the hydrophobic part behaves as a cation in aqueous solution, it is called

cationic detergent , example is Hexadecyltrimethyl ammonium chloride. The
detergency is in the cation, which can be a substantially sized molecule. Strong acids
are used, such as hydrochloric acid to produce the CI anion as the neutralizing agent
although in essence, no neutralization takes place in the manufacturing process .
Cationic detergents are similar to the anionic ones, with a hydrophobic component,
but instead of the anionic sulfonate group, the cationic surfactants have quaternary
ammonium as the polar end. The ammonium center is positively charged.
NON-IONIC OR ZWITTERIONIC DETERGENTS :

Non ionic detergents have same hydrophobe- hydrophil balance but they differ
from ionic detergents in that they have a multiplicity of oxygen groups or linkage
that make them water soluble. Example is Ethylene oxide adducts. This detergent
consists of no ionic constituents which are ionically inert. The vast majority of all
non-ionic detergents are condensation products or ethylene oxide with a
hydrophobe. This group of detergents is enormous, and the permutation endless.
These are characterized by their (net) uncharged, hydrophilic head groups. They
are based on polyoxyethylene (i.e. Tween, Triton and Brij series), Chaps,
glycosides (i.e. octyl-thioglucoside, maltosides), bile acids such as DOC, lipids
(HEGAs), or phosphine oxides. Zwitterionic detergents possess a net zero charge
arising from the presence of equal numbers of +1 and -1 charged chemical groups.

AMPHOLYTIC DETERGENT :

Another class of detergent is ampholytic. These contain both cationic and anionic
groups. They are electrically neutral in an aqueous solution . They behave as
cationic in acid pH and anionic in alkaline pH. Example is N-fatty-ẞ amino
propionic ester.

ETHOXYLATES: Ethoxylates are compounds that have long hydrocarbon

chains, but terminate with (OCH2CH2)nOH group. These groups are not charged,
but they are highly hydrophilic owing to the presence of many oxygen centres.

BASIC COMPONENTS OF DETERGENT

• Detergent (Linear alkyl benzene sulphonate)
• Builders: Phosphate (Sodium tripolyphosphate boost detergent powder),
citrates, silicates, carbonates, zeolite
• Fillers and Processing Aids: Sodium carbonate, sodium sulphonate
 • Corrosion inhibitors: Sodium silicate
• Anti redeposition agent: Carboxy methyl cellulose
• Fabric Brightners: Fluoroscent dyes
• Bluing: Improve whiteners by counteracting natural yellowing tendency
• Antimicrobiol agents: Carbinilides, salicylanilides
• Enzymes: Decompose or alter the composition of soil and render the
particles more easily removable.
Some of the enzymes used in detergent are protease,amlases,liapse and celolases.
The enzymes catalyses the breakdown of chemicalds through addition of water and
helps in the removal of soils.[Saini,2001a].Polymers and enzymes play important
role in improving the detergency. Polymers help in soil removal, prevent insoluble
salt incrustation work as anti-soil re-deposition, inhibit dye transfer. Use of optical
brightner enhance the brightness and whiteness. processing aids when added to
slurries of detergent powder improve stability and homogeneity of slurries during
mixing and reduce viscosity.
MANUFACTURING OF DODECYL BENZENE SULPHONATE ( Anionic
Synthetic Detergent)

Basic Chemistry :

AlCl3
4C3H6 -----------------------------> C12H24
0C , 5-7 MPa pressure Propylene Tetramer ( Dodecene )
Propylene 180- 200

Dodecyl Benzene Sulphonate is mainly anionic detergent. The main raw material of
this detergent are Benzene, Dodecene , oleum and NaOH and different additives.
Dodecene or propylene tetramer is produced by the catalytic polymerization of
propylene containing about 50 % propane over kieselguhr impregnated
phosphoric acid catalyst at about 5 to 7 MPa and 200 0C. The effluent from the
fractionators contains unreacted propane which is used as fuel, propylene trimer is
recycled to the reactor and the third bottom fraction called propylene tetramer (
dodecene ) is used for alkylation.

Manufacturing process involves the following steps :

1) Benzene and propylene tetramer ( Dodecene) are reacted in alkyllator in

presence AlCl3 or HF catalyst promoted by either water or HCl. The mole ratio
of benzene to tetramer is kept between 5 to 10 : 1 and the temperature is
 maintained around 500C . Residence time of the reactor varies from several min
to an hour.
2) Catalyst used is recovered , purified and recycled.
3) The product from the alkylator contains unreacted benzene , lighter product ,
dodecyl benzene and heaviour alkylate.
4) Dodecyl benzene is separated from other products of alkylator by fractionation
several times.
5) Benzene is separated by fractionation and recycled.
6) Lighter products and heavier alkylates are separated from dodecyl benzene by
fractionation.
7) Dodecyl benzene are fed to the sulphonator which is reacted with oleum .
Dodecyl benzene sulphonate is formed.
8) Acidic sludge is separated through settler.
9) Dodecyl benzene sulphonate is neutralized in neutralizer by the addition of
NaOH. Other additives are also added here to get Dodecene Benzene
Sulphonate.
Flow-sheet of Manufacturing Dodecyl Benzene Sulphonate
MANUFACTURING OF KERYL BENZENE SULPHONATE ( Surf) :

All household detergents in India are manufactured from paraffins found in

kerosene range. The manufacturing of keryl benzene sulfonate involves the
following steps.

1) Kerosene is chlorinated first . Ratio of kerosene to chlorine is 1: 3 to 1: 10 on

mole basis. Liquid phase reaction occurs in chlorinator. Usually two reactors in
series are used for chlorination.
2) Chlorinated kerosene and benzene are reacted in reactor in presence of AlCl3
catalyst. Excess chlorine and HCl are stripped off for recycling .
3) The alkylated hydrocarbon ( Keryl benzene ) is settled in settler , tar is
removed after settling.
4) Mainly alkylated hydrocarbon contains benzene , kerosene and keryl benzene.
Benzene and kerosene are separated by fractionating and recycled.
5) Pure keryl benzene is sulphonated in sulphonator by sulfuric acid.
6) Spent acid and acidic sludge is withdrawn from separator.
7) Sulphonated Keryl Benzene (surf) is neutralized in neutralizer by NaOH. Water
is circulated and surf is collected in powder form and packaged. Filler ,colours
and other additives are added and the slurry is finally concentrated and spray
dried.
 Flow- sheet of manufacturing Surf

1. Chlorinator
2. Chlorinator
3. Settler
4. Benzene column ( Distillation column )
5. Kerosene column ( Distillation column )
6. Keryl Benzene column ( Distillation column )
7. Sulphonator
8. Neutralisation tank
9. Spray dryer.
Different Additives used in Detergent Industry :

1) Builder : Function : The builder is used for buffering pH , soil dispersion, soil
anti redeposition , solubilisation of water insoluble materials and neutralization.
Example of builder used are metal carbonate , phosphate , borate and silicate
etc.

2) Bleaching agent and whitner: Function : used for easy removal of dirt.
Example – sodium hypochlorite , sodium perborate.

3) Processing aids : Function : They are used for adjuctment of pH, removal of
moisture , prevention of caking during storage.
Example : sodium sulphonate or sodium carbonate.

4) Perfume : Function : To reduce offensive odours.

Example : citrous , lemon grass oil , rose oil etc.

5) Corrosion inhibitor : Function : Used when dish washing and metal washing are
desirable.
Example : silicate , borax.

6) Foaming agent : Function : Foaming agent are used to create foam.

Example : n- alkylated amino tri azines.

7) Brightner : Function : used to increase brightness.

Example : Highly coloured organic compounds.

8) Hydrotopes : Function : hydrotopes are added to reduce the viscosity of the

detergent slurry. They are used even to increase the solubility in water.
Example : Sodium toluene sulphate.

9) Other additives :

a) Dyes and pigments are used to give colour.

b) Fillers are used to decrease the bulk weight of detergent , i.e, to reduce cost.
c) Enzymes are also used to remove special stains made by proteins like milk ,
blood etc.
d) Some special agents propagate mildness towards skin , are also incorporated in
detergents.
e) Bacteriostats are added to prevent the growth of bacteria.

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