INTRODUCTION

COMPANY PROFILE
Ultramarine & Pigments Ltd is one of the leading manufacture of pigments and surfactants in
India. This Thirumalai group company specialises in the manufacture of inorganic pigments,
organic surfactants & organic surfactants & dry mix detergents and has two manufacturing
units in TamilNadu,at Chennai and Ranipet.

The company is over 50 years old, so obviously there have been many
milestones for us. The ones that come to mind immediately getting into the sulphonation
business in 1975 and setting up a factory in remote Ranipet (TamilNadu),in 1991,the
company started a Blue(pigment) factory in Ranipet, so we doubled our capacity, in 2001,we
started making Alpha Olefin Sulphonate(AOS) and gotten QMS(Quality Management
System) and EMS(Environment Management System) certified. They also started the ITES
(Information Technology Enabled Service) business at the same time.

Over the past two decades, they won many awards from industry associations and the
state government for productivity, quality, safety and environment.

The Surfactants factory in Ranipet is running at full capacity. With a focus on optimising the
product mix, and increased value addition for the customer, the division has seen a 13%
increase in both sales volume and profit over the previous year. The Surfactants division
increased its revenues by 7% to 159.69 crores in financial year 2017 to 2018,as compared to
149.47 crores in financial year 2016 to 17.

UPL is setting up a Greenfield surfactants project with an annual installed

capacity of 30000 Tonnes in Naidupet, Andhra Pradesh. The estimated project capital outly
for the same is approximately 70 crores.

ULTRAMARINE & PIGMENTS LTD(UPL) PRODUCTS

They have three major verticals in the company- pigments, surfactants and ITES.

In terms of business models, they are focused on quality and customer satisfication.
They pride ourselves in giving our customers a menu of products to choose from, be it blue,
AOS(Alpha Olefin sulphonate), sodium lauryl ether sulphate(SLES),or linear alkyl benzene
sulphonic acid(LABSA). In surfactants, they make liquid, paste, noodles, powder and
needles.

In pigments, they make high quality grates for use in industrial applications, and they
cater to the local markets for whitewash and industry grades. They make over 50 grates of
pigments, controlling for as many physical and chemical properties as possible.

They are looking at many new products, including non-toxic pigments to expand our
stable of mixed metal oxides, and speciality surfactants to serve the personal care market.
AWARDS AND ACHIVEMENTS
 AOTS-CUMI TPM Annual award 2005 –II Prize
 AOTS TPM Annual award 2006-III Prize
 CII Kaizen completion-II Prize
 Safety award by Govt. Of TamilNadu-I Prize(2007)
 Safety award by Govt. Of TamilNadu-I Prize(2011)
 CFBP Award for fair business practices in 2014

ALPHA OLEFIN SULPHONATE(AOS) ORIGIN

The lion corporation, Japan are one of the principal producers and users of Alpha Olefin
Sulphonate. In addition to fabric washing powder, they also market fabric washing liquids,
shampoos, toothpaste and foam bath products containing this active. In the USA Minnetonka
have utilised AOS in hand cleaness/ liquid soaps.AOS is the potential replacement for alkyl
benzene sulphonate in dish wash detergent liquids formulations with performance peaking at
C14 chain length.

ALPHA OLEFIN SULPHONATES (AOS) PROFILE

Alpha Olefin Sulphonates(AOS) are surfactants with high detergency, very high wetting and
foaming properties and are compatible with the hard water often found in India. Indian
customers prefer detergents which contain AOS, due to their excellent foaming and cleaning
properties. Since AOS is used in both wet and dry formulations, We specialize in the
manufacture of ready to use liquid, paste, noodles, powder or needles.

Alpha Olefin Sulphonate is an anionic surfactant with nearly 100% biodegradability.

About 2,500,000 tons of Sulphonated anionic surfactants are produced annually in the
U.S, West Europe and Japan The total annual world production of sulphonated anionic
surfactants is estimated at about 4,000,000 tons.Sulphonation plants are scattered around the
globe in units with production capacities varying between 3,000 and 50,000 tons anionic
surfactants annually. Assuming an average production capacity of 5,000 tons per year, there
are at least 800 operational sulphonation plants around the world.

The Global Surfactants market is expected to reach$47.53 billion by 2022 growing at

a Compound Annual Growth Rate (CADR) of 6.2% during the forecast period 2015 to 2022.
ALPHA OLEFIN SULPHONATE (AOS) APLLICATIONS

 Personal care-baby products, bubble baths, skin creams and lotions, shower gels,
shampoos, liquid and bar soaps.
 Industrial and household cleaning- car cleaner, dishwashing detergents, all-purpose
cleaners.
 Launtry detergents- laundry detergents for households, laundry detergents for
industrial and communal washing.
 Industrial auxiliaries-fire-fighting agents, industrial foaming agents.

PHYSICAL PROPERTIES

PROPERTIES VALUE

Appearance at 20ºC Yellow liquid

Molecular weight 316

Density at 20ºC 1.05 g/cm3

Viscosity at 20ºC 40 mpa.s

Active matter 37±1 % wt

Sodium sulphate 1.0% wt,max

Biodegrability Increases with increasing linearity

pH, 10% solution 7.0-8.0

METHODS AND SELECTION OF PROCESS

METHODS OF ALPHA OLEFIN SULPHONATE(AOS) PRODUCTION

Only rhe Alpha Olefin Sulphonate commercially to make Alpha Olefin

Sulphonate(AOS). There are three different process has been carried out for the production of
Alpha Olefin Sulphonate(AOS).

1.ALPHA OLEFIN REACTING WITH SULPHURIC ACID(H2SO4)

C14H28 + H2SO4 C12H25CH(OH)CH2SO3Na + H2O

(Alpha Olefin) (Sulphuric acid) (Alpha Olefin Sulphonate)

The presence of water retards the sulphonation reaction,very large excess of H2SO4 is
used to bring the reaction to complete.

Separation and neutralization can take place in the same reactor.

2.ALPHA OLEFIN REACTING WITH OLEUM(H2S2O7)

C14H28 + H2S2O7 C12H25CH(OH)CH2SO3Na + H2SO4

(Alpha Olefin) (Oleum) (Alpha Olefin Sulphonate)

The presence of water retards the sulphonation reaction, very large excess of oleum
is used to bring the reaction to completion.

Separation and neutralization can take place in the same reactor.

3.ALPHA OLEFIN BY REACTING WITH SULPHUR TRI-OXIDE(SO3)

C14H28 + SO3 C12H25CH(OH)CH2SO3Na + H2O

(Alpha Olefin) (Alpha Olefin Sulphonate)

Alpha Olefin Sulphonate commonly manufactured by the sulphur trioxide by falling

film technology.After the reactor, the reactor, the SO3 exhaust gas is separated from the
organic acid.
SELECTION OF PROCESS

Since there are three types of method used to produce Alpha Olefin Sulphonate , we will deal
with sulphur trioxide process. Alpha Olefin Sulphonates commonly manufactured by Alpha
Olefin with Sulphur Trioxide by falling film technology.

DIFFERENT BETWEEN THE PROCESS

SULPHUR TRIOXIDE(SO3) PROCESS OLEUM(H2S2O7)/SULPHURIC
ACID(H2SO4) PROCESS
Contains 2-45 of free acid Contains13-15% of free acid
Less Caustic Soda is required to neutralize High caustic soda is required to neutralize free
free acid acid
More foaming in nature Less foaming in nature
Price is cheaper Price is higher
Lower moisture content Higher moisture content
Ease processing due to low viscosity Processing stringent
No sedimentation present Sedimentation present
Process is economic Process is not economic

RAW MATERIAL
Alpha Olefin(C14H28)

Sulphurtrioxide(SO3)

Sodium Hydroide(NaOH)

CHEMICAL REACTIONS

C14H28 + SO3 + NaOH C12H25CHOHCH2SO3Na + H2O

(Alpha Olefin) (Alpha Olefin Sulphonate)

SO2 + ½ O2 SO3

S + O2 SO2

(Sulphur)
PROCESS DESCRIPTION
SULPHUR MELTING

The sulphur melts at 120ºC. The liquid viscosity decreases with temperature increase.
The best temperature for liquid sulphur manipulation is in the range of 135-140ºC.

All the machinery,equioment, piping,valves and accessories handling sulphur are

jacketed and heated with steam(150ºC) at 4 bar pressure and thermally insulated.

The bottom and the walls of the melter are equipped with steam coil at 4 bar to melt
and keep the melted sulphur at 135-140ºC temperature, which corresponds to the minimum
viscosity value.

When solid sulphur is charged, it moves a corresponding volumetric amount of liquid

sulphur from melting zone to the separation zone, heavy impurities fall down, while light
ones over the liquid surface.

COMPRESSION AND COOLING

The process air is sucked from the surrounding and the air compressed by the
compressor upto 0.6-0.7 bar pressure. After the compression, air is cooled by the water and
glycol, to remove heat of compression and to condensate the large amount of moisture.

DRYING

After the compression and cooling, the process air is sent to the drier, where moisture
is adsorbed on a solid adsorbent(activated alumina) material.

The process is should be dried to prevent the formation of sulphuric acid mist.

For a certain time all the process air flow through Dryer, where it is dried before its
utilization as process air, while the other one regeneration.

Regeneration is made in two steps(heating and cooling);

-During heating step(4 hours), the hot atmospheric air goes through the tower from
the top to bottom(opposite direction than the one kept by the process air) and flowing on the
drying material, evaporates the water adsorbed from the process air, it is then discharge to the
atmosphere by fan.

-During cooling step(4hours), air is recirculated, from the bottom to top, in closed
cycle through the coolers.
SULPHUR BURNING

The sulphur burning oven is vertical cylindrical type and is composed of a steel shell
internally coated with refractory bricks.

The molten sulphur(145ºC) is pumped to the sulphur furnace where the sulphur is
converted to SO2 with an excess of oxygen from the process air.The furnace outlet
temperature of the SO2 IS 750ºC.It is the highly exothermic reaction.The SO2 is cooled in an
indirect air cooler from 750ºC to 410ºC.

SULPHUR(S) + DRY AIR(O2) SULPHUR DIOXIDE(SO2)

Sulphur is completely burnt at the oven bottom, in any case molten sulphur must not
accumulate.

CATALYTIC CONVERSION(SO2/SO3)

The converter is a cylindrical, vertical, insulated vessel in which four beds of

vanadium pentoxide catalyst on a silica carrier, the reaction is highly exothermic and at the
outlet of every bed the gas temperature increased.The catalyst of vanadium pentoxide at its
first contact with SO2 undergoes a “sulfation” process that provokes a high heat release to
avoid that the temperature reaches too high values dangerous for the catalyst stability.

SO2 + ½ O SO3

The conversion is carried out controlling the inlet temperature of gas for the four beds at a
constant and optimal value.

FIRST BED

The inlet temperature to be preferred for the 1st bed is the one that provokes
higher temperature increase into the bed.

Generally the best temperature for the gas inlet to the 1st bed is between 415-425ºC. The inlet
temperature to the 1st bed shouldn’t go down under 410ºC. The outlet temperature from the
1st bed shouldn’t reach a value higher than 600ºC since the catalyst can be damaged Max
74% conversion take place in the 1st bed.

SECOND BED

The consideration given for the 1st bed is also valid for the 2nd , but the inlet temperature that
will provoke the maximum temperature increase through the bed, generally is sensibly higher
than the 1st bed.

It reaches to a range of 435-480ºC in that temperature increases the

conversion(92%).
THIRD AND FOURTH BED

If the maximum possible yield into the first two beds is reached, the inlet temperature that
will guarantee the maximum(98%) yield ,will probably be about 430-450ºC.

REACTOR

The sulphonation reaction can be characterised by

The reaction between SO3 and organic feedstock is almost instantaneous.

The reaction is highly exothermic.

C14H28 + SO3 C14H28SO3 + HEAT

Sulphonation reactor is vertical, multi film type equipment,the inside of every tube forms a
reaction chamber.

The alpha olefin and SO3sulphonating mixture are fed continuously in the upper part
Of the sulphonator and are uniformly distributed, through a distributor. The gas in the tube
and liquid on the internal surface of each tube wetting them completely. The gas is forced to
run along them at high velocity, acting as driving force that pushes the fluid along the reactor,
the high velocity produces turbulence that allow a close contact between the reactant and the
outlet product has 45-50ºC.

After the reactor, the SO3 exchanged gas is separated from the organic acid. The
exhaust gas, containing small amounts of non-converted SO2,unreacted SO3 and small
amount of organic acid.

EFFLUENT GAS PURIFICATION

The exhaust gas leaving the sulphonation reactor must be purified before being discharged
into the atmosphere, as it contains,

Sulphur dioxide (SO2) (gas)

Sulphur trioxide (SO3) (gas)

Sulfonic acids (mists)

The mists are removed by means of an Electrostatic Precipitator(ESP), whereas SO2

and SO3 are absorbed by means of caustic soda in a scrubber.

The ESP consists of the cone type convergent and the electrodes are inserted in it.
The alternative arrangements of the positive and the negative electrodes are feasible. The
mixture is sent to the cone and the percolates in this can be ionized by means of electrodes.
From that the free gases from the ESP is separated from particulated matter and it is sent to
scrubber.
 In scrubber NaOH is sprayed at the top, which is diluted one. This caustic soda will
be treated with this gases and to remove SO2, SO3 gases. So that the contaminant fee gas is
sent to stack and it will be vent out to the atmosphere.

2NaOH + SO2 Na2SO3 + H2O

2NaOH + SO3 Na2SO4 + H2O

NEUTRALISATION

The neutralisation reaction is a substitution of a basic ion Na+ to the H+ of acid, which water
formation and heat developed.

C14H28 + SO3 + NaOH C12H25CHOHCH2SO3Na + H2O

(ALPHA OEFIN) (ALPHA OLEFIN SULPHONATE)

OVERALL MATERIAL BALANCE:

C14H28 + SO3 +NaOH C12H25(OH)CH2SO3Na + H2O

COMPONENTS MOLECULAR WEIGHT

Alpha Olefin(C14H28) 196
Sulphur Trioxide(SO3) 80
Sodium Hydroxide(NaOH) 40
Alpha Olefin Sulphonate 316
(C12H25(OH)CH2SO3Na)
Water(H2O) 18

Basis: 100 TPD = 50*1000/24 = 2083.33 kg//hr of Alpha Olefin Sulphonate.

Alpha Olefin = 196*2083.33/316 =1292.192 kg/hr.

Sulphhur Trioxide = 80*2083.33/316 = 527.425 kg/hr.

Amount of NaOH = 659.28 kg/hr.

Air(O2)=2356.25/28.84

=81.7 kmole/hr.

Air contains 79% of Nitrogen(N2),20.5% of Oxygen(O2),and 0.5% of Moisture(H2O)

Amount of Nitrogen present in air=81.7*0.79=64.543 kmole/hr

=64.543*28.84=1861.42 kg/hr

Amount of Oxygen present in air =81.7*0.205=16.7485 kmole/hr

=16.7485*32= 535.952 kg/hr

Amount of moisture present in air =81.7*0.005= 0.4085 kmole/hr

=0.4085*18=7.353 kg/hr

INDIVIDUAL MATERIAL BALANCE:

COMPRESSOR:

O2= O2=

535.952 kg/hr 535.952 kg/hr

N2= COMP N2=

REESS
1861.42 kg/hr OR 1861.42 kg/hr

Moisture= Moisture=

7.353 kg//hr 7.353 kg//hr

COMPONENT MOLECULAR INPUT ( kg/hr)
WEIIGHT
Oxygen(O2) 32 535.952
Nitrogen (N2) 28 1861.42
Moisture(H2O) 18 7.353
Total 2404.725

COMPONENT MOLECULAR OUTPUT ( kg/hr)

WEIIGHT
Oxygen(O2) 32 535.952
Nitrogen (N2) 28 1861.42
Moisture(H2O) 18 7.353
Total 2404.725

Inout = Output.

CYCLONE SEPARATOR:

O2=535.952 kg/hr O2=535.952 kg/hr

N2=1861.42 kg/hr N2=1861.42 kg/hr

Moisture=7.353 kg/hr Moisture=7.353 kg/hr

COMPONENT MOLECULAR INPUT ( kg/hr)
WEIIGHT
Oxygen(O2) 32 535.952
Nitrogen (N2) 28 1861.42
Moisture(H2O) 18 7.353
Total 2404.725

COMPONENT MOLECULAR OUTPUT( kg/hr)

WEIIGHT
Oxygen(O2) 32 535.952
Nitrogen (N2) 28 1861.42
Moisture(H2O) 18 7.353
Total 2404.725

Input = Output

DRYER:

O2=535.952 kg/hr O2=535.952 kg/hr

N2=1861.42 kg/hr N2=1861.42 kg/hr

Moisture=7.353 kg/hr Moisture=7.353 kg/hr

COMPONENT MOLECULAR INPUT ( kg/hr)

WEIIGHT
Oxygen(O2) 32 535.952
Nitrogen (N2) 28 1861.42
Moisture(H2O) 18 7.353
Total 2404.725
COMPONENT MOLECULAR OUTPUT ( kg/hr)
WEIIGHT
Oxygen(O2) 32 535.952
Nitrogen (N2) 28 1861.42
Moisture(H2O) 18 2.701
Removed
Moisture(H2O) 18 4.652
Total 2404.725

Input = Output

FURNACE:

Sulphur= SO2=

216.92 kg/hr 433.84 kg/hr

Oxygen= Oxygen=
Furnace

535.952 kg/hr 319.032 kg/hr

Nitrogen= Nitrogen=

1861.42 kg//hr 1861.42 kg//hr

Moisture= Moisture=

2.701 kg/hr 2.701 kg/hr

COMPONENT MOLECULAR INPUT(kg/hr)

WEIGHT
Sulphur 32 216.92
Oxygen(O2) 32 535.952
Nitogen(N2) 28 1861.42
Moisture(H2O) 18 2.701
Total 2616.993
COMPONENT MOLECULAR OUTPUT (kg/hr)
WEIGHT
Sulphurdioxide(SO2) 64 433.84
Oxygen(O2) 32 319.032
Nitogen(N2) 28 1861.42
Moisture(H2O) 18 2.701
Total 2616.993

INPUT=OUTPUT

CATALYTIC BED CONVERTOR:

SO2= SO3=

433.84 kg/hr 542.3 kg/hr

Oxygen= Oxygen=

319.032 kg/hr 210.572 kg/hr

Nitrogen= Nitrogen=

1861.42 kg//hr 1861.42 kg//hr

Moisture= Moisture=

2.701 kg/hr 2.701 kg/hr

COMPONENT MOLECULAR INPUT (kg/hr)

WEIGHT
Sulphur dioxide(SO2) 64 433.84
Oxygen(O2) 32 319.032
Nitrogen(N2) 28 1861.42
Moisture(H2O) 18 2.701
Total 2616.993
COMPONENT MOLECULAR OUTPUT (kg/hr)
WEIGHT
Sulphur trioxide(SO3) 80 542.3
Oxygen(O2) 32 210.572
Nitrogen(N2) 28 1861.42
Moisture(H2O) 18 2.701
Total 2616.993

Input = Output

DEMISTER:

SO3= SO3=

542.3 kg/hr 538.18 kg/hr

Oxygen= Oxygen=

210.572 kg/hr 210.572 kg/hr

Nitrogen= Nitrogen=

1861.42 kg//hr 1861.42 kg//hr

Moisture= Oleum=

2.701 kg/hr 6.821 kg/hr

COMPONENT MOLECULAR INPUT(kg/hr)

WEIGHT
Sulphur trioxide(SO3) 80 542.3
Oxygen(O2) 32 210.572
Nitrogen(N2) 28 1861.42
Moisture(H2O) 18 2.701
Total 2616.993
COMPONENT MOLECULAR OUTPUT(kg/hr)
WEIGHT
Sulphur trioxide(SO3) 80 538.18
Oxygen(O2) 32 210.572
Nitrogen(N2) 28 1861.42
Removed
Oleum - 6.821
Total 2616.993

Input = Output

REACTOR:

Alpha Olefin= Alpha Olefinic acid=

1318.56 kg/hr 1819.617 kg/hr

SO3= Oxygen=

538.18 kg/hr 210.752 kg/hr

Oxygen= Nitrogen=

210.572 kg/hr 1861.42 kg//hr

Nitrogen= Unreacted SO3=

1861.42 kg//hr 10.755 kg/hr

Unreacted Alpha
Oleefin= 26.368 kg/hr

COMPONENT MOLECULAR INPUT(kg/hr)

WEIGHT
Alpha Olefin 196 1318.56
SO3 80 538.18
Oxygen 32 210.572
Nitrogen 28 1861.42
Total 3928.732
COMPONENT MOLECULAR OUTPUT(kg/hr)
WEIGHT
Alpha Olefinic Acid 276 1819.617
Oxygen 32 210.572
Nitrrogen 28 1861.42
Unreacted Alpha Olefin 196 26.368
Unreacted SO3 80 10.755
Total 3928.732

Input = Output

GAS LIQUID SEPARATOR: Oxygen =210.572 kg/hr

Nitrogen=1861.42 kg/hr

Unreacted Alpha Olefin= 26.368 kg/hr

Unreacted SO3=10.755 kg/hr

Alpha Olefinic acid=

1819.617 kg/hr

Oxygen=

210.572 kg/hr

Nitrogen=

1861..42 kg//hr

Unreacted SO3= Alpha Olefinic acid =

10.755 kg/hr 1819.617 kg/hr

Unreacted Alpha
Oleefin= 26.368 kg/hr

COMPONENT MOLECULAR INPUT(kg/hr)

WEIGHT
Alpha Olefinic Acid 276 1819.617
Oxygen 32 210.572
Nitrrogen 28 1861.42
Unreacted Alpha Olefin 196 26.368
Unreacted SO3 80 10.755
Total 3928.732
COMPONENT MOLECULAR OUTPUT(kg/hr)
WEIGHT
Top
Oxygen 32 210.572
Nitrrogen 28 1861.42
Unreacted Alpha Olefin 196 26.368
Unreacted SO3 80 10.755
Bottom
Alpha Olefinic acid 276 1819.617
3928.732

Input = Output

NEUTRALISER:

Alpha Olefin
Alpha Oleinic
Sulphonate =
Acid=
1083.33 kg/hr
1819.617 kg/hr
H2O =
NaOH =
395.586 kg/hr
659.712 kg/hr

COMPONENT MOLECULAR INPUT(kg/hr)

WEIGHT
Alpha Olefinic Acid 276 1819.617
NaOH 40 659.2815
Total 2478.89

COMPONENT MOLECULAR OUTPUT(kg/hr)

WEIGHT
Alpha OlefiN Sulphonate 316 2083.33
H2O 18 395.5689
Total 2478.89

Input = Output
ELECTROSTATIC PRECIPITATOR: