NAME: LALICHETTI SURESH

ROLL NUMBER: 04/S4/128

REGISTRATION NUMBER: M/111/10/29
TITLE OF THE PROBLEM: Manufacturing of
Sodium Dodecyl Benzene Sulfonate of 10,000,000
Kg /annum.

SYNOPSIS

INTRODUCTION
The washing industry, usually known as the soap industry, has roots
over 2000 years in the past, a soap factory having been found in the
Pompeii excavations. However, among the many chemical process
industries, none has experienced such a fundamental change in chemical
raw materials as have the washing industries. It has been generally
accepted that the per-capita use of toilet soap is a reliable guide to the
standard of living for any country.
Soap itself was never actually discovered, but instead gradually evolved
from the crude mixtures of alkaline and fatty materials. Pliny and Elder
described the manufacture of both hard and soft soap in the first century,
but it was not until the thirteenth century that soap was produced in such
quantities to call it an industry. Up to the early 1800s soap was believed to
be a mechanical mixture of fat and alkali; then Chevreul, a French chemist,
showed that soap formation was actually a chemical reaction. Domeier
completed his research on the recovery of glycerin from saponification
mixtures in this period.
The raw material shortages of World War I led the Germans to develop
synthetic soaps or Detergents. These were composed of short-chained
alkyl naphthalene sulfonates, which were good wetting agents but only fair
in detergent action. This sparked the interest worldwide in developing

detergents, and new developments are continuing to the present time.

From the original short-chain compounds the development has progressed
through long chain alcohol sulfates in the 1920s and 1930s, through the
alkyl-aryl long chain sulfonates in the 1940s,to branched chain compounds
in the 1950s and 1960s. During the 1960s the requirement of
biodegradability became important and caused the return to linear long
chains, because only the linear chains can be easily biodegraded.
Detergents differ from soap in their action in hard water. Soaps form
insoluble compounds with the calcium and magnesium ions present in
hard water. These insoluble compounds precipitate out and reduce
foaming and cleaning action. Detergents may react with the hard water
ions, but the resulting products are either soluble or remain colloidal in
composition and manufacture. Scientifically, the term detergent covers
both soap and synthetic detergents, or syndets as it is widely used to
indicate synthetic cleaning compounds, as distinguished from soap.

MANUFACTURING METHODS
Linear alkyl benzene (LAB) is manufactured in large scale industrial
processes by
Alkylating benzene with linear mono-olefins or alkyl halides such as chloroparaffins by using HF or AlCl3 as the alkylation catalyst.

1) Over heterogeneous solid super acids in a fixed bed reactor.

Alkylation with AlCl3 was the first commercial process used in mid 60s
when branched Dodecyl Benzene was replaced by Linear Alkyl Benzene
(LAB). At the end of the 60s the HF technology was applied for the first
time and immediately it became the preferred technology to be used
around the world to produce LAB.
In the mid 90s a new alkylation technology based on the heterogeneous
catalyst in a fixed-bed reactor, Detal, appeared on the market and was
rapidly adopted, as testified by several new units recently installed with
this technology. The new technology offers considerable advantages over
the old ones, namely: process simplification, elimination of acid handling
and disposal (HF, HCl, AlCl3) as well as an overall production yield
improvement.
Total LAB world production capacity in the year 2000 was estimated to be
nearly
3 million tons, with a split by technology as follows: 80%HF, 10%AlCl3,
10% fixed-bed. Several commercial processes are found: MOLEX (UOP),
ENSORB (EXXON), ISOSIEVE (Union Carbide) etc..

PROCESS DESCRIPTION:

The process involves reaction of Dodecene(C12H24) with benzene(C6H6) in

the presence of Aluminium Chloride(AlCl3) catalyst, fractionation of the
resulting crude mixture to recover the desired boiling range of
dodecylbenzene(C6H5C12H25), sulfonation of the dodecylbenzene and
subsequent neutralization of the sulfonic acid with caustic soda(NaOH),
blending the resulting slurry with chemical builders and drying.
Dodecene is charged into a reaction vessel containing benzene and
aluminiumchloride. The reaction mixture is agitated and cooled to
maintain the reaction temperature of about 450C. An excess of benzene is
used to suppress the formation of by-products. Aluminiumchloride
requirement is 5 to 10wt% of dodecene. Aluminiumchloride is a strong
Lewis acid. It reacts vigorously and exothermically with water forming HCl,
which is both corrosive and poisonous. Any spills are to be cleaned
immediately. Granular AlCl3 (+ 4 to -14 mesh) is preferred metal halide to
employ. It is easy to handle in air without fuming problems and has good
flow properties.
After removal of AlCl3 catalyst sludge, the reaction mixture is
fractionated to recover excess benzene (which is recycled to the reaction
vessel) unreacted dodecene and dodecyl benzene.
Sulfonation of the dodecyl benzene may be carried out continuously
or batch-wise under a variety of operating conditions using sulfuric acid
(100%), Oleum (usually 20% SO3) or anhydrous sulfurtrioxide. The
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optimum sulfonation temperature is usually in the range of 37oC to 60oC

depending on the strength of acid employed, mechanical design of the
equipment, etc. Removal of the spent sulfuric acid from the sulfonic acid
is facilitated by adding water to reduce the sulfuric acid strength to about
78%. This dilution prior to neutralization results in a final neutralized slurry
having approximately 85% active agent based on the solids. The inert
material in the final product is essentially NaSo4.
The sulfonic acid is neutralized with 20 to 50% caustic soda (NaOH)
solution to a pH of 8 at a temperature of about 500C. Chemical builders
such as trisodium phosphate, tetrasodiumphosphate, sodium silicate,
sodiumchloride, sodiumsulfate, carboxymethyl cellulose etc are added to
enhance the detersive, wetting or other desired properties in the finished
product. A flaked, dried product is obtained by drum drying or a bead
product is obtained by spray drying.
The basic reactions which occur in the process are the following.
ALKYLATION
Reaction 1
C6H6 + C12H24

C6H5C12H25

SULFONATION
Reaction 2

C6H5C12H25 + H2SO4 C12H25C6H4SO3H + H2O

NEUTRALISATION
Reaction 3
C12H25C6H4SO3H + NaOH C12H25C6H4SO3Na + H2O
Reaction 4
H2SO4 + 2NaOH Na2SO4 + 2H2O
A literature search indicates that yields of 85% to 95% have
been obtained in the alkylation step, while yields for the sulfonation
process are substantially 100%.Yields for the neutralization step are
always 95% or greater .All the reaction steps are exothermic and require
some form of jacketed cooling around the stirred reactor to maintain
isothermal reaction temperatures.

RAW MATERIALS REQUIREMENT

The chemicals that are required in the manufacture of Sodium Dodecyl
Benzene Sulfonate (C12H25C6H4SO3Na) involve the following.
1)
2)
3)
4)
5)
6)

Benzene ( C6H6 )
Do-Decene (C12H24 )
Aluminium Chloride ( AlCl3 )
Oleum ( H2S2O7 )
Sodium Hydroxide ( NaOH )
Water ( H2O )
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PROCESS DESIGN OF THE EQUIPMENT

The process design of the equipment involves design of a Reactor and a
Distillation Column. The Reactor that is involved is a Continuous Stirred
Tank Reactor type having a volume of 25m3 with a wall thickness of .004m
and having a diameter of 2.65m and a height of 3.7 m, has to be designed
for the process. The Distillation Column that has to be designed is of a
binary Distillation Column type having the lighter key as Benzene and
the heavier key as Dodecene, which operates at

1 Kg/cm2 pressure

and having an overhead temperature of 830C and a bottom temperature of

2650C.

MECHANICAL DESIGN OF THE EQUIPMENT

The Continuous Stirred Tank Reactor that is used should be made of Cast
Steel having a diameter of 2.65m, height of 3.7m with a wall thickness of .
004m having an operating pressure of 1Kg/cm2.The distillation column that
has to be designed should be made of Cast Steel, operates at a pressure of
1Kg/cm2 having an overhead temperature of 830C and a bottom head
temperature of 2650C.

CONSIDERATION OF SAFETY AND POLLUTION OF THE

PLANT
Linear Alkyl Benzene sulfonates as adequately biodegradable. These
are bio soft surfactants. But they are not broken down as readily and
completely as soaps and other surfactants derived from fats or
synthesized to contain a completely unbranched chain with an even
number of carbon atoms and no benzene ring. Years of systematic
monitoring of sewage treatment plants and rivers has shown that in
general the residual concentration of surfactants in streams is extremely
small.
Biodegradation in sewage treatment plant models shows
Primary Biodegradation
OECD confirmatory test

90 95

%MBA/BiAS/DAS removal

Ultimate Biodegradation
Coupled units test,

73+6 (C)

%C/COD/removal

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High biodegradable anionic surfactants allowed by the law are

of only marginal toxicity to fish. It is shown that toxicity is inversely
proportionate to biodegradability.
Toxicity data of alkylbenzene sulfonate
(mg/l)
LC50 (fishes)

3 - 10

LC50 (daphnaie)

8 - 50

NOEC (algae, growth inhibition)

30 300

For anionic surfactants the length of the alkyl chain has been
found to be closely related to skin irritability. Straight chain or Linear alkyl
benzene sulfonate show weak effects to skin, since they are bio-soft.

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