PRODUCT DESCRIPTION

Sulfonic Acid

A sulfonic acid ​refers to a member of the class of ​organosulfur compounds with the general
formula R−S(=O)​2​−OH, where R is an organic ​alkyl or ​aryl group and the S(=O)​2​(OH) group, a
sulfonyl​ hydroxide.

Figure 1. Sulfonic Acid Structure

In LABSA, the R group is the alkylbenzene (LAB) in the sulfonic acid structure and the
hydrophobic tail.

Linear Alkylbenzene Sulfonic Acid (LABSA)

Figure 2. Hydrophilic and hydrophobic parts of LABSA structure

 MANUFACTURING PROCESS

PROCESS 1

Production of Linear Alkylbenzene Sulfonic Acid via Sodium Trioxide Technique from
Linear Alkylbenzene (LAB) and Sulfur

Major Raw Material/s:

● Sulfur Rocks/Flakes
● Linear Alkylbenzene (LAB)

Minor Raw Material/s:

● Air
● Sodium Hydroxide
● Monoethylene Glycol (Coolant)
● Silica Gel
● Vanadium Pentoxide

LIST OF EQUIPMENT
● Humid Air Compressor - 1
● Humid Air Cooler - 1
● Dehumidifying Tower - 1
● Sulfur Melter - 1
● Reactor - 3
● Heat Exchanger - 6
● Separator - 1
● Cyclone Separator - 1
● Gas Absorption Column - 1
● Mixer - 1
● Storage Tank - 5
 PROCESS DESCRIPTION

The manufacturing of LABSA is a continuous process. An interval of 1 day after a period of

20-21 days for the purpose of shutdown and start-up is essential for maintenance purposes.

1. Air Drying

Humid Air Compressor

The air taken from outside is compressed and dehumidified. ​The cooling has the
purpose to remove the humidity from the air, up to a saturation humidity of 2 °C and
also to convey low ​temperature air to the dehumidifying tower, thus favoring the water
absorption in the silica gel. The equipment for air drying is a vertical cylindrical vessel,
which is horizontally divided into two parts by a partition containing insulating material.

Heat Exchanger

Air is cooled by passing it through a heat exchanger containing the coolant

Monoethylene Glycol ​at a temperature of ​0 to -2 °C​. The air flow is then conveyed at
a constant temperature (less than 5 °C) to the silica gel dryers.

Silica Gel Dehumidifying Tower

After cooling the air to the required temperature, it has to be dried to remove
traces of moisture present in it. For this purpose, air is passed through a cylinder filled
with silica gel. The silica gel brings the dew point of the water in the air down to stay
-40 °C. This means that the air is dry as if the ​air was cooled down to -40 °C​.

Silica Gel: Appearance – white color, granules of 3-6 mm approximately

The silica gel adsorbs moisture from the air, preventing damage at the point of
use of the compressed air due to condensation or moisture.

In practice, two cylinders with silica-gel are used:

● for drying the air
● for reconditioning

In general, the changing of the cylinders is done automatically.

2. Sulfur Melting

Sulfur Melter

Sulfur is melted to allow sulfur that has been acquired has to be melted prior to
its ignition. This is done by heating it in the melter at temperatures of 135 °C to 145 °C.
If the temperature exceeds 145 °C it would result in vaporization of sulfur while
temperatures less than 135 °C would be insufficient to melt sulfur. Therefore, ​a
temperature of 140 °C is maintained to prevent wastage of sulfur due to the above
mentioned causes.

The solid sulfur is melted using steam and filtered to avoid the pump valves
clogging and then fed to the sulfur burner using the pump.

3. Sulfur Dioxide Production

S-SO​2​ Converter (Reactor 1)

In the furnace, the ​molten sulfur with a temperature of ​140 °C is fed through a
pipe and falls on a surface of refractory balls, while the combustion air is supplied in
counter current, thus obtaining the complete combustion of sulphur without its spraying
through a nozzle; which might often clog owing to sulfur impurities. The ​air inlet
temperature is -40 °C​. The oxidation reaction of the sulfur dioxide is exothermic and
heat produced by it is quite sufficient to maintain the catalyst layers at the required
temperature to obtain a good conversion progress. In order to get the best efficiency,
the gas inlet temperature in the ​first catalyst layer h
​ as to be about ​400 - 450 °C​.

S​(l)​ + O​2 (g)​ → SO​2 (g)

It does not require any maintenance and the gas composition does not change.
The ​temperature of the gas at the burner outlet is around 700 °C (corresponding
approximately to an SO​2​ concentration of 7% by volume).

Primary and Secondary Cooling Towers

A heat exchanger cools the gas so that it reaches the conversion tower at the
required temperature.
4. Sulfur Trioxide Production

SO​2​ - SO​3​ Converter (Reactor 2)

The conversion tower is composed of three layers of ​(Vanadium pentoxide,

V​2​O​5​) catalyst at ​400 - 450 °C​. The gas, passing from a layer to next one, crosses a
heat exchanger to take the ​gas temperature to optimum conversion values on every
stage. In order to allow quick startup, a preheating system has been provided.

Primary and Secondary Cooling Towers

A heat exchanger cools the gas so that it reaches the conversion tower at the
required temperature.

5. Sulfonation

Reactor 3

The sulfur trioxide is sent to the third reactor where it reacts with Linear Alkyl
Benzene (LAB). This group is composed by a film reactor, multi-tube type, having
dimensions and number of tubes proportional to the plant capacity. The sulphonation
gas is automatically fed on the reactor top and distributed in part strictly equal on each
of the pipes composing the reactor. The raw material to be sulphonated is fed in
co-current with the gas. Outside the reaction tubes in the reactor jacket the cooling
water circulates in co-current with the film, thus allowing a control of the ​reaction
temperature​ by heat removing.

Due to the presence of some water vapor in air some ​oleum ​is also formed. This
should be avoided as it can cause blockage. The reactor has small tubes in which the
SO​3 passes and the LAB passes through its sides. The main reaction takes place at
the bottom of these tubes and during maintenance these tubes are thoroughly cleaned
because if the LAB leaks to the centre part then the reaction will take place there only
and no SO​3​ will pass through.
6. Separation

Separator

The mixture of LABSA (desired product), LAB, SO​3 and a mixture of other waste
materials including oleum is sent to a separator. The gases are sent to the cyclone
separator while the liquid product is sent to the mixer.

Mixer

The product, after sulfonation, is mixed with water to neutralize it.

Cyclone Separator

Cyclone separation is the method of removing particulates from an air (or gas)
stream, without the use of filters, through vortex separation. Rotational effects and
gravity are used to separate mixtures of solids and fluids. Here, a high speed rotating
air-flow is established within a cylindrical or conical container called a cyclone. Air
flows in a spiral pattern, beginning at the top (wide end) of the cyclone and ending at
the bottom (narrow) end before exiting the cyclone in a straight stream through the
center of the cyclone and out the top.

Larger (denser) particles in the rotating air stream have too much inertia to follow
the tight curve of the air stream and strike the outside wall, falling then to the bottom of
the cyclone where they can be removed. In a conical system, as the rotating air-flow
moves towards the narrow end of the cyclone the rotational radius of the air stream is
reduced, separating smaller and smaller particles from the stream. The cyclone
geometry, together with air flow rate, defines the cut point of the cyclone.

This is the size of particles that will be removed from the air stream with a 50%
efficiency. Particles larger than the cut point will be removed with a greater efficiency
and smaller particles with a lower efficiency. The liquid product and reactants which
still have to react are sent to the mixer.
7. Exhaust Gas Treatment

Gas Scrubber

The unit is designed to treat exhaust gas stream coming from the sulfonation
reactor before being sent to the atmosphere in order to remove any possible organic,
unreacted SO₃ traces and unconverted SO₂. The residual unconverted SO​2 is
absorbed in the scrubbing column in which a water and caustic soda solution is
continuously recycled.

8. Packaging

LABSA is packaged into plastic drums and then transported. Each drum contains
210 kg of the product. Second-hand plastic drums can be used to reduce costs.
 OPERATING PARAMETERS
Air Compressor
Air Outlet Temperature: <5 °C
Monoethylene Glycol Temperature: 0 to -2 °C

Air Dehumidifying Tower

Air Inlet Temperature: <5 °C
Air Outlet Temperature: -40 °C

S-SO​2​ Converter (Reactor 1)

Air Inlet Temperature: -40 °C
Molten Sulfur Temperature: 140 °C ​(9)
Temperature of Sulfur Dioxide at Burner Outlet: 700 °C ​(5)
Cooling Water Temperature: (?)
SO2:air ratio: 1:1 by volume ​(6)

Heat Exchanger 1
Sulfur Dioxide Inlet Temperature: 700 °C
Sulfur Dioxide Outlet Temperature: (?)

Utility Fluid (?) Inlet Temperature: (?)

Utility Fluid Outlet Temperature: (?)

Heat Exchanger 2
Sulfur Dioxide Inlet Temperature: (?)
Sulfur Dioxide Outlet Temperature: 420 °C ​(10)

Utility Fluid Inlet Temperature: (?)

Utility Fluid Outlet Temperature: (?)

Conversion Tower (Reactor 2)

Operating Temperature: 400 - 625 °C ​(7)
Sulfur Dioxide Inlet Temperature: 420 °C ​(10)
Air Inlet Temperature: -40 °C
Cooling Water Temperature: (?)
V​2​O​5​: 400-450 °C
V​2​O​5​ - 1-2 atm ​(6)

Sulfur Trioxide Outlet Temperature: 400 - 625 °C ​(7)

Heat Exchanger 3
Sulfur Trioxide Inlet Temperature: 400 - 625 °C ​(7)
Sulfur Trioxide Outlet Temperature - (?)
 Utility Fluid Inlet Temperature - (?)
Utility Fluid Outlet Temperature - (?)

Heat Exchanger 4
Sulfur Trioxide Inlet Temperature - (?)
Sulfur Trioxide Outlet Temperature - (?)

Utility Fluid Inlet Temperature - (?)

Utility Fluid Outlet Temperature - (?)

Sulfonation Reactor (Reactor 3)

Reactor (Type) Operating Temperature:

Sulfur Trioxide Inlet Temperature - (?)

Air Inlet Temperature - (?)
LAB Inlet Temperature - (?)
Cooling Water Temperature - (?)

LABSA Outlet Temperature - (?)

Separator
LABSA Inlet Temperature - (?)

LABSA Outlet Temperature - (?)

SO3 Rich Stream Outlet Temperature - (?)

Cyclone Separator
SO3 Rich Stream Inlet Temperature - (?)

LABSA Outlet Temperature - (?)

SO3 Stream Outlet Temperature - (?)

Gas Absorption
SO3 Stream Inlet Temperature - (?)
NaOH Inlet Temperature - (?)

SO3 Rich Stream Outlet Temperature - (?)

NaOH Rich Stream Outlet Temperature - (?)

Sulphonation Stage - Falling Film Reactor or Jet Reactor, Stirred Tank Reactor/Cascade
Reactor or Multitube Falling Film Reactor (4)
PROCESS FLOW DIAGRAM
REFERENCES

1. March, Jerry​ (1992), ​Advanced Organic Chemistry: Reactions, Mechanisms, and

Structure​ (4th ed.), New York: Wiley, ​ISBN​ ​0-471-60180-2
2. https://educheer.com/term-paper/production-operations-manufacturing-processes-of-lab
sa/
3. https://www.slideshare.net/SaadBinHasan3/rhymer-chemical-industries-ltd-presentation
4. https://www.linkedin.com/pulse/20140929075018-128703936-production-of-linear-alkyl-b
enzene-sulphonic-acid-labsa
5. https://www.slideshare.net/SaadBinHasan3/rhymer-chemical-industries-ltd-presentation
6. https://www.chemguide.co.uk/physical/equilibria/contact.htm
7. https://www.sciencedirect.com/topics/chemical-engineering/sulfur-dioxide
8. https://application.wiley-vch.de/books/sample/3527311262_c01.pdf
9. https://patents.google.com/patent/US2341887
10. https://www.slideshare.net/guruict/falling-film-sulphonation