Detergent manufacture

SYNTHETIC DETERGENTS

A detergent is defined as a cleaning agent. The advantages of synthetic detergents

over soaps are – a) high detergency action in soft & hard water alike, since they do
not react with calcium & magnesium salts present in water, b) small concentration of
detergents give rise to large detergency action, c) detergency action is reached
even at low temp, d) synthetic detergents do not hydrolyze hence are almost
neutral.

Detergent molecule consists of two different parts, one is hydrophilic part & the
other one is hydrophobic. Hydrophilic molecules are usually SO32-, COO-, O-,
NH2+, CO- groups that are soluble in water, where as the hydrophobic part consists
of long chain hydrocarbons.

The steps in the production of sodiumdodecylbenzene sulphonate consists of the

attachment of alkyl straight chain dodecane (C12H26) to benzene & then
sulphonation of the ring structure followed by neutralization with caustic soda.
Process

Aluminum chloride acts as a catalysts for the alkylation of benzene. Alkylation is possible either with
an olefin or with the chloride of a paraffin. After the alkylation is over, the product is distilled to
separate benzene and is allowed to recycle, the heavy product is again distilled to separate light alkylate
from heavy alkylate a close fractionation gives rise to alkylate of suitable molecular weight for
detergent manufacture. Heavy alkylate can be used to manufacture inferior quality detergents. Oleum is
used as a sulfonating agent & the reaction takes place in a water jacketed agitated kettle .The mass is
then pumped into a settler ,where acid is separated & is sent for concentration .the acid slurry is
neutralized with caustic soda. The mass is then mixed with builders like sodium triphosphates, silicates
etc, carboxy methyl cellulose(CMC) is added at this stage. The slurry is then concentrated & spray
dried.

All household detergents in India are manufactured from paraffins found in kerosene range cut. The
aromatics from the cut are removed either by adsorption (in molecular sieves ) or liquid extraction. The
paraffins are chlorinated in the liquid phase. Usually two reactors in series are used for chlorination.
Excess of chlorine (which is recycled) & hydrochloric vapour are stripped off. The chloro-paraffins
contain some unconverted paraffin which can be separated by distillation & sent back to the chlorinator.
The chloroparaffins are dehydrated & then alkylated with benzene (Friedel Crafts reaction) in presence
of AlCl3 catalyst. The alkylated hydrocarbon mixture is settled and washed to remove catalyst, then
separated from the remaining hydrocarbons and impurities like HCl and Cl2. The fraction is sulfonated
with oleum. After sulfonation, the mixture is neutralized with sodium hydroxide. Filler, builder, colour
and other additives are added & the slurry is finally concentrated and spray dried.
Linear alkylbenzene (LAB) is the most common raw material in the manufacture of biodegradable household
detergents.LAB is produced using normal paraffins as a raw material. Normal paraffins are derived from straight run
kerosene.
Until 1995, alkylation used hydrofluoric (HF) acid as thecatalyst. In 1995, the first commercial Detal process unit using
a solid bed catalyst alkylation process was commissioned.This revolutionary technology abolished the use of liquid acid
in the plant, reducing capital investments,maintenance costs, and waste treatment.
There are two major sections in a LAB complex: production of normal paraffins, and production of LAB from normal
paraffins.

Production of normal paraffins:

Kerosene pre-fractionation is often used to tailor the kerosene feed to the desired carbon range. Kerosene is stripped of
light ends and heavier components so that the heart cut, containing the desired n-paraffins for the production of LAB of
a certain range of molecular weight, is produced.
The distillate UnionfiningTM process hydrotreats kerosene at sufficient severity to remove sulfur, nitrogen, olefins and
oxygenate compounds which might otherwise poison the Molex adsorbent.
The Molex process is a liquid state separation of normal paraffins from branched and cyclic components using
SorbexTM technology. The simulated moving bed adsorptive separation results from using a proprietary multi-port
rotary valve. The extract stream is a high-purity normal paraffins stream. The raffinate stream, consisting mainly of
iso- or cyclic-kerosene range compounds, is often blended into jet fuel.

Production of LAB from normal paraffins:

In the Pacol process, the normal paraffins are dehydrogenated in a vapor phase reaction to corresponding mono-olefins
over a highly selective and active catalyst. The DeFine process is a liquid phase, selective hydrogenation of diolefins
in the Pacol reactor effluent to corresponding mono-olefins over a catalyst bed.
The PEP process allows the selective removal of aromatics in the feed to the Detal or Detergent Alkylate unit.
Detergent Alkylate is a process in which benzene is alkylated with mono-olefins produced in the Pacol Unit to LAB
using HF acid as a catalyst.