Final Project Synopsis 1 (2) .Docx S.docx 1

S.S.J.C.O.
E Mfg of Liquid Bromine

Page 1

Acknowledgement
We experience great pleasure in presenting the project report
entitled Manufacturing of Liquid Bromine.
With the profound feelings of immense gratitude we express our
whole hearted thanks to our guide Prof. Ananya Dey for her
valuable support and guidance throughout the process without
which it would have been impossible.
We would like to thank our principle Dr. J. W. Bakal and HOD
Mrs. Leelamani for their never ending encouragement, moral
support and patience during the preparation of our project.
We therefore sincerely thank the company Excel Industries Ltd. for
guiding us in our project.
We also sincerely acknowledge our sense of gratitude to the
Chemical Engineering Department, Shivajirao S. Jondhale
College of Engineering who has extended their support and
outmost co-operation for our project.
We also thank all those who have directly or indirectly contribute
for making this report.

Mr. Shyam Yadav

S.S.J.C.O.E Mfg of Liquid Bromine
Page 2

Mr. Paresh Agarwal.
Mr. Anil Jain.

Page 3

INTRODUCTION

Page 4

INTRODUCTION

The project is about the production of Liquid Bromine in our chosen liquid brome
producing company.
This project contains all the details about the plant of hazardous chemicals both
reactant & product included in this project. It will give an idea about how actually a
hazardous chemical is handled and what are the preventing measures has to be followed.
Our main aim for selecting this project is to study all the information which is
covered by our syllabus and to remember the factors to start an industry and to design of
all the apparatus & utilities.

Page 5

PRODUCT HISTORY

Page 6

PRODUCT HISTORY

Bromine was discovered by two scientists working independently. In the Autumn of 1825,
student Karl Lowig took a bottle of a reddish liquid with an unpleasant smell to the
Laboratory of Medicine and Chemistry of Prof. L. Gemlin, at the University of
Heidelberg. Lowig told Gemlin that the liquid, of mineral origin, resulted from the
treatment with gaseous chlorine, thus explaining the red colour. The substance responsible
for that red colour was extracted with the help of ether, giving origin to a pink liquid later
known as bromine.
Almost simultaneously, Antoine Balard, who was working in a pharmacy school in
Montpellier, isolated a substance with the same properties of the liquid obtained by
Lowig. At first he thought that it was a chlorine or iodine compound. As he could not
isolate the compound, he suggested to have found a new chemical element. Balard
suggested the name "muride", from the Latin word "muria" for brine.
The French Academy of Science, in turn, proposed the name "brome" from the Greek
word bromos meaning stench to indicate its strong irritating odour.
Bromine occurs in the hydrosphere mainly as soluble bromide salts. Its con-centration
ranges from 65 mg/L in seawater up to 6.5 g/L in the southern basin of the Dead Sea. In
1826, Antoine-Jerome Balard in France published the discovery of bromine, which was
isolated by chlorinating seawater bitterns and distilling out bromine. Bromine had been
prepared earlier by Joss and Liebig but neither of them recognized it as an element.
Around 1840 bromine wasused in photography. The rst mineral to contain bromine was
apparently silver bromide, discovered in 1941 by Berthier. Its rst medical use was in
1857 when bromides were used for the treatment of epilepsy. The rst commercial
bromine production from salt brines was in 1846 at Freeport, Pennsylvania. In
1858,potash was discovered in the Stassfurt salt deposits in Germany and bromine was a
by-product from the potash production. Herbert Dow invented the blowing out process
for Midland (Michigan) brines in 1889. The antiknock properties of tetraethyllead,

Page 7

(CH3CH2)4Pb, were discovered in 1921 and soon after ethylene dibromide, C2H4Br2,
was found to aid the removal of leadfrom combustion chambers.
At one time, 80% of all bromine was used to produce ethylene dibromide.
Bromine was rst commercially extracted from sea-water in 1934, using the Dow process.
The richest source of Br in the world is found in the Dead Sea brines, which contain up to
12 g/L of Br. Its commercial exploitation by DSBG started in 1957. In the 1950s, bromine
was discovered in south Arkansas brines, the only significant source of bromine in the
United States, with a bromine content of 25 g/L.
The biggest single bromine plant was erected by the Dead Sea in Israel, and is operated by
the Dead Sea Bromine Group (DSBG)

Page 8

PHYSICAL
&CHEMICAL
PROPERTIES

Page 9

Properties of Bromine
Physical properties:-
Molecular formula Br
Atomic number 35
Solubility in water Slightly souluble
Solubility in organic solvents - highly soluble.
Molar mass 79.901 g/mol
Appearance Reddish Brown Liquid
Density 3.1028 g/cm3
Melting point - -7.2C (265.8 K)
Boiling point 58.8 C (332 K)
Critical Point 588 K, 10.34 MPa
Heat of fusion - 10.571 KJ mol
1

Heat of vaporization - 29.96 kJ mol
1
Molar heat capacity - 75.69 J mol
1
K
1
Chemical properties:-
Being less reactive than chlorine but more reactive than iodine, bromine reacts vigorously
with metals, especially in the presence of water, to give bromide salts. It is also reactive
toward most organic compounds, especially upon illumination, conditions that favour the
dissociation of the diatomic molecule into bromine radicals:
Br
2
2 Br

Page 10

It bonds easily with many elements and has a strong bleaching action.
Bromine is slightly soluble in water, but it is highly soluble in organic solvents such
as carbon disulfide, carbon tetrachloride, aliphatic alcohols, and acetic acid.

Page 11

Properties of Chlorine
General
Chlorine has a characteristic penetrating and irritating odour. The gas is greenish
yellow in colour and the liquid is clear amber.
Atomic and Molecular Properties:
Atomic Symbol ........... Cl
2

Atomic Weight ........... 35.453
Atomic Number .......... 17
Molecular Weight ....... 70.906
Chemical Properties:
Flammability - Gas or liquid, is non-explosive and non-flammable. It is an oxidizer
and is capable of supporting combustion. Many organic chemicals react readily with
chlorine, sometimes violently.
Valence - Chlorine usually forms compounds with a valence of -1 but it can combine with
a valence of +1, +3, +4, +5 or +7.
Reactions With Water - Chlorine is only slightly soluble in water. (0.3 to 0.7 percent)
Reactions With Metals - At ordinary temperatures dry chlorine, gas or liquid, reacts with
aluminium, arsenic, gold, mercury, selenium,
tellurium, tin, and titanium. Carbon steel ignites near 251C.
Reactions With Organic Compounds - Chlorine reacts with many organic compounds.
Some reactions can be extremely violent or explosive.
Physical Properties:-

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The following properties are for pure chlorine. Standard conditions- At 32F (OC) and
an absolute pressure of 14.696 psi (101.325 kPa).
Boiling Point (Liquefying Point) = -29.15F (-33.97C)
Density- Gas at Standard Conditions = 0.2006 lb/ft3 (3.213 kg/m3)
Saturated Gas = At 32F (OC), 0.7632 lb/ft3 (12.23 Kg/m3)
Saturated Liquid = 91.56 lb/ft3 (1467 kg/m3) at 32F (0C);
Latent Heat of Vaporization = 123.9 Btu/lb (288.1 kJ/kg)
Melting Point - Freezing Point = -149.76F (-100.98C)
Solubility in Water = 6.93 lbs/100 gals. (60F and 14.696 psi)
Specific Gravity = Gas- 2.485 (air);
Liquid, 1.467 0/4C (water)
Vapour Pressure = 53.51 psi (368.9 kPa) at 32F (0C);
112.95 psi (778.8 kPa) at 77F (25C).
Viscosity - Sat. Gas = 0.0125 cP (0.0125 mPa s) at 32F (0C);
Liquid = 0.3863 cP (0.3863 mPa s) at 32F (0C)
Chlorine, liquefied under a pressure of 8 bar at room temp. The liquid column size is ca.
0.33 cm.

Page 13

Properties of HBr
Molecular formula HBr
Solubility in water Slightly soluble
Appearance Colourless
Density 3.645 g/cm3
Melting point -86.9C (186.1 K)
Boiling point -66.8 C (206 K)
Vapour Pressure 2.308 MPa (at 21 C)
Critical Point 363.15 K, 85.52 bar
Refractive Index 1.325
Specific heat capacity 350.7 mJ g
1
K
1

Page 14

Properties of NaBr

Molecular formula NaBr
Appearance White powder
Density 3.21 g/cm3(anhydrous)
2.18 g/cm3(dihydrate)
Melting point 747 C (anhydrous)
36 C (dihydrate)
Boiling point 1396 C
Solubility in water Miscible
Solubility in organic solvents highly soluble.
Refractive index 1.6459
Std enthalpy of formation -369 kJ.mol
-1

Std molar entropy 84 J.mol
-1
.K
-1

Flash Point 800 C

Page 15

Properties of H
2
SO
4

Molecular formula H
2
SO
4

Appearance Colourless
Molar mass 98 g/mol
Density 1.845 g/cm3
Melting point 10C (283.15 K)
Boiling point 337 C (610 K)
Solubility in water Miscible
Std enthalpy of formation -814 kJ.mol
-1

Std molar entropy 157 J.mol
-1
.K
-1

Page 16

Page 17

APPLICATIONS/ USES

Page 18

Uses/Applications of Bromine
In its liquid form, bromine is reddish-brown in colour. Its vapours give off a pungent
smell and are reddish in colour. It was found that bromine is more soluble in carbon
disulfide and solvents, like methanol and acetic acid than in the water. It needs only one
electron to complete an octet of electron in its outermost shell. This enables it to take part
in various chemical reactions and act as a strong oxidizing agent.

In Fire Retardant Chemicals
One of the important bromine applications is in manufacturing brominated flame
retardants. These are used as chemical flame retardants in the plastic industry and in
products, such as cables, connectors, plastic covers. Bromine's flame retardant property is
also employed to make products, like carpets, upholstery, paints and kitchen appliances
safe. It is also used in the clothing and furniture industries, to prevent the products from
catching fire. In the electronics industries, especially in computers, it is used to make
fireproof printed circuit boards. Polybrominated diphenyl ether, polybrominated biphenyl,
decabromodiphenyl ether, hexabromocyclododecane, tetrabromobisphenol are of flame
retardant.

As a Disinfectant
Bromine is a bleaching agent, and is used to disinfect water in cooling towers and the
swimming pools. In this case, bromine test strips are used to detect phenols and
unsaturated double bond compounds as well as alkalinity, pH and hardness of water. In
hospitals and commercial industries and homes, it is manly used as a sanitizer and a
germicide to neutralize bacteria, algae and fungi. It is also employed as a sanitizer, in
areas where there is less or no chances of it coming in contact with food. Bromine is also
preferred for disinfection of industrial water.

Page 19

In Water Purification Compounds
Bromine can be found in products that are used in water purification systems.
Tralomethrin is one such product used to purify drinking water. The amount of bromine
present in water should not be more than 100mg/decilitre, which is its lowest toxic level.
In Pesticides
Bromine is also used in agricultural products such as pesticides to destroy pests. It is most
preferred to get rid of pests which targets crops, such as potatoes, tomatoes, etc. Methyl
bromide, is a compound that acts as a fumigate. It is used to protect stored grains and
other produces by destroying pests.

In Photography Film
The most well-known use of bromine is in making photographic films. Silver bromide is
light-sensitive and is used to manufacture photography plates. Its microscopic particles
when exposed to light undergo a change as a result of chemical reaction. This property of
silver bromide is responsible for the production of the image, when the photographic film
is exposed to light when you click the shutter. Potassium bromide is used in photography,
to prevent undesired reduction of silver, which causes fogging in a photograph.

IN medicines
Bromine has been used as a drug, for a long time, in one or the other form. Primarily,
chemical compounds derived from it are used as oral sedatives, to treat epilepsy and as
diuretics. It is well-known for its central nervous system depressive role in bromide
poisoning. In the past, as late as the start of 20th century, potassium bromide was used as a
sedative.

Page 20

In Dyes
It was in 1909, when a German chemist Paul Friedlander found that the Tyrian purple
(red-purple to deep purple) contains bromine. In this form, it was known to man for
hundreds of years. Tyrian purple dye is nothing but a chemical 6,6'-dibromoindigo.
Another such dye used is tetra butyl ammonium bromide. These have many other
applications in the textile industry.

Other Uses
Salts of bromine formed with calcium, sodium, and zinc are water-soluble. The dense
solution thus, formed is used as a drilling fluid while drilling boreholes.
Ethidium bromide or EtBr is used as a DNA stainer, in the process of gel electrophoresis.
Normally this chemical, under ultraviolet light, gives out orange-glow which intensifies, if
EtBr binds with a DNA.
Bromine is employed to reduce mercury pollution that the coal consuming power plants
cause. Activated carbon and coal treated with bromine, does the trick.
5-bromouracil, is used as an artificial mutagen which helps scientists in forcing the genetic
materials, such as, DNA to change the bromides of the alkali and alkaline earth elements
find usage in pharmacy because of their sedative actions, in photography for preparing
silver bromide emulsions, and in the industrial drying of air as desiccants.
Zincbromine storage batteries (qv) are under development as load-levelling devices in
electric utilities.
Photovoltaic batteries have been made of seleni um or bor on doped wi t h
br omi ne.
Bromine and its salts are known to recover gold and other precious metals
from their ores.

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SELECTION OF
PROCESS

Page 22

SELECTION OF PROCESS
The two primary stripping vapours are steam and air. Steam is used when the
concentration of bromine in brine is>1000 ppm. The advantage is that bromine can be
condensed directly from the steam. Air is used, when seawater is the source of bromine
because very large volumes of stripping gas are needed and steam would be too expensive.
When air is used the bromine needs to be trapped in an alkaline or reducing solution to
concentrate it.
Blowing-out Process
Blowing-out process, used when the source of bromine is sea water, air is used instead of
steam to strip bromine from solution. At the pH of seawater, the liberated bromine
hydrolyzes to hypobromous acid and bromide. Bromide traps bromine as the tribromide
ion and little bromine is released. Before stripping, enough sulphuric acid is added to the
seawater to reduce the pH to 33.5. The exiting air containing bromine is absorbed in a
sodium carbonate solution.
3 Na
2
CO
3
+ 3 Br
2
5 NaBr + NaBrO
3
+3 CO
2

When the alkalinity of the absorbing solution becomes low it is moved to
storage. Acidifying the absorbing solution with sulphuric acid reconstitutes
the bromine that can then be steamed out.
NaBrO
3
+5NaBr +3 H
2
SO
4
3 Br
2
+ 3 Na
2
SO
4
+ 3 H
2
O
An alternative absorbing solution uses sulphur dioxide.
Br
2
+ SO
2
+2 H
2
O 2 HBr + H
2
SO
4

The bromine is recovered by oxidizing the bromide with chlorine and steaming it out of
solution. Treatment with sulphuric acid and fractional distillation are the main methods
used to purify bromine. It is especially important to reduce the water content to<30ppm to
prevent corrosion of metal transportation and storage containers.

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PROCESS DESCRIPTION

Page 24

FLOWSHEET

Page 25

Mfg of Liquid Bromine (in brief) :-
Liquid bromine is produced from organic waste (acidic & alkaline) obtained from
pharmaceutical & fertilizer industries. NaBr obtained from waste is first acidified and then
treated with HBr and Cl
2
gas to get gaseous bromine which when condensed in a
condenser gives Liquid Bromine.
Overall Reaction:-
NaBr + H
2
SO
4
HBr + Na
2
So
4
HBr + Cl
2
HCl + Br
2

Manufacturing Process:-
Raw Materials:-
Organic waste containing NaBr or HBr in significant quantity is obtained from fertilizer
and pharmaceutical industries.
Chlorine gas is used in substitution reaction to get liquid bromine.
Steam is used as heating medium as well as carrier gas.
Process: -
Reactor 1: -
Organic waste containing 10% to 25% concentration of NaBr is acidified in reactor 1. Due
to the corrosive nature of reactants reactor has to be glass lined. H
2
SO
4
is added as a
acidifying

medium. Acid used is of 98% conc. Steam of 1kg/hr mass flow rate is used to
attain reaction temperature of 110
o
C and a pressure of 1kg/mm
2
.
Reaction taking place in the reactor is given by
NaBr + H
2
SO
4
HBr + Na
2
So
4

Page 26

Since the reaction temperature is maintained at 110
o
C all the organics having boiling
point less than that of water along with water and HBr get seperated and are sent to
condenser where hot vapours get condensed.
Filtration: -
The condensed liquid obtained is a mixture of HBr, water, & low boiling organics. Here
organics are undesired product therefore it needs to be removed.
Thus the liquid mixture is passed over a filter cloth in a filtration unit which acts under
vacuum. Here all the organics are removed from the mixture & HBr of approx. 30% conc.
is obtained. HBr obtained is pumped in reactor 2 for substitution reaction.
Reactor 2: -
Reactor 2 is made up of glass and is 6 m tall. Rasching rings are used as packing so as to
increase liquid gas contact time. Reaction temperature is 80
o
C.
Liquid HBr is allowed to pass from the top and steam and Cl
2
gas is passed through
bottom. Here, steam performs dual jobs firstly, of a heating medium & secondly, as a
carrier gas. The reaction taking place in the reactor is given by
HBr + Cl
2
HCl + Br
2

HCl obtained is of 10% concentration which is of no significant use. It can either be
concentrated to 25% for sale or can be neutralised and discharged as an effluent. Br
2

vapours along with unreacted Cl
2
gas & H
2
O is condensed in a condenser & sent to a
distillation unit for further separation.
Distillation Unit: -
Distillation unit is also made up of glass & is also 6 m tall. Packing used is rasching rings
and temperature is maintained 80
o
C.
The liquid mixture obtained from condenser is allowed to be heated using steam. Cl
2
gas
having least boiling point in the mixture evolves first & is recycled back to reactor 2.
Around 62 to 65
o
C Br
2
starts to evolve which is sent to the condenser where its

Page 27

temperature is reduced below boiling point. Liquid bromine obtained is then stored in
amber coloured bottles. Water obtained from the bottom of distillation column and is
recycled for further use.

Page 28

INSTRUMENTATION &
PROCESS CONTROL

Page 29

INSTRUMENTATION AND PROCESS CONTROL
In any chemical industry quality has become the most important specification. This can be
achieved by proper instrumentation Precise process control is a reward to Production.
The measurement of the level of various energies and the control of the energy, which can
take place, is called instrumentation.
Instrumentation and process control are necessary in a plant for the following reasons:
1. Quality Control
2. Recording of certain variables (Viz. Temperature, Pressure, Viscosity, and pH) for
future analysis
3. To eliminate human errors while operating or running a plant
4. Safety of plant and efficient control
5. For controlling pollution free better control of plant emissions to meet more
stringent regulations
Since, in a chemical plant, the reactions are taking place in the reactor or column which
cannot be analyzed from outside and hence we have to rely on the reading indicated by
instruments and hence their reliability is to be accurately examined.
But only instrumentation cannot serve our purpose because instruments only indicated the
values of various parameters like pressure, temperature, level etc. And also, mere
indication is of no use. Sometimes there may be deflections in parameters and we have to
control it. So some systems are provided with these instruments and are termed as
Process Control.
In instrumentation and process control temperature, pressure, flow and level are the four
main variables, which are to be controlled for plant safety and from economic point of
view.
A well planned instrumentation and process control scheme leads to the following
advantages.

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1. Saving of labour.
2. Saving of service consumption.
3. Controlled speed of operation.
4. Accuracy
5. Continuous recording of process variables.
Instrumentation and process control does not mean automatic control of parameters.
Instrumentation also makes the use of local indicator. Local temperature and pressure
indicators are used to control the temperature and pressure indicators are used to control
the temperature and pressure manually in the emergency e.g. when there is power failure
at such time automatic controllers cannot work. Local indicators are installed with
equipments such as reactors, distillation columns, pumps, reboilers, heat exchangers etc.
Valves are installed at inlet and outlet with all the units of POCl
3
plant to control the inlet
outlet flow rates of the process and utility lines.
INSTRUMENTATION FOR SPECIFIC EQUIPMENTS:-
Distillation Column: -
Distillation column should be provided with feed flow controllers by using flow-recording
controllers.
At the top of the distillation column a pressure relief valve is installed to release the excess
pressure and maintain the inside pressure.
Condenser & Preheater: -
Condenser and Preheater are installed as heat exchanging equipments. In both the units
utility inlet valves are controlled by process outlet temperature by means of a control loop.
Reboilers: -
At the bottom of the distillation column reboilers is placed. In reboilers steam flow is
controlled by process temperature level indicator controller is used with reboilers to
control the level of the process fluid in the reboilers.

Page 31

Pump: -
For transporting the process liquid positive suction centrifugal pump are used. Before a
pump a strainer is used to remove the solid particles or impurities. A nonreturnable valve
is also installed at the pump outlet.
Reactor: -
Flow:
Being a batch plant, the production capacity is fixed & hence the flow rate of raw material
plays an important role. Flow indicators & Controllers along with flow measuring devices
such as Rotameter have to be installed flow lines
Temperature:
The reaction taking place inside the reactor is endothermic and temperature is to be
maintained at 110C, which requires perfect process control to have higher conversion
hence for temperature measurement RTD or Thermocouple is satisfactorily used. The
temperature is sensed by the measuring unit & when it approaches 112C or 114C the
temperature is controlled to 110C. By altering the flow rate of chilled water flowing into
the internal coils which is a manipulated variable.
Level: -
Shaft & float type indicators are economically used as a level measuring devices

Page 32

MATERIAL BALANCE

Page 33

MATERIAL BALANCE FOR REACTOR 1
Chemical reaction:-
2NaBr + H
2
SO
4
Na
2
SO
4
+ 2HBr
Required data:-
Chemicals Molecular weight
H
2
SO
4
98
NaBr 103
HBr 81

Basis: 1000 kg solution of 10% NaBr and 10% organics.
i.e. 1000 kg of solution contains 100 kg of NaBr, 100 kg of organics and 800
kg of water
100 kg NaBr 971 mol of NaBr
From the stoichiometry of the reaction,
971 mol of NaBr 485.5 mol of H
2
SO
4
Amount of 98% H
2
SO
4
required for 100 kg of NaBr
= (485.5 98)/.98
= 48.55 kg
Similarly,
971 mol of NaBr 485.5 mol of Na
2
SO
4
and 971 mol of HBr
Amount of Na
2
SO
4
formed

= 485.5 142
= 68.94 kg.

Page 34

Amount of HBr formed

= 971 81
= 78.651kg.
From top we get 20% HBr solution.
Wt. of HBr solution = 78.651/.2
= 393.255 kg
Wt. of water in HBr solution = 393.255 78.651
= 314.6 kg
At bottom, we obtain
Wt. of organics + water = (Wt. of feed solution + Wt. of H
2
SO
4
Wt of
HBr solution)
= (1000 kg + 48.55 kg 393.255 kg )
= 655.295 kg

Page 35

MATERIAL BALANCE FOR REACTOR 2

Chemical reaction:
2HBr + Cl
2
2HCl + Br
2
Basis: - 1kmole of product POCl
3

Compound Molecular Weight
Br
2
80
HCl 36.5
HBr 81
Chlorine 35.5

From the stoichiometry of the reaction,
971 mol of HBr 485.5 mol of Cl
2

971 mol of HBr 78.65 kg/hr of HBr
Amount of Cl
2
required for 78.65 kg of HBr
= (485.5 71)
= 34.47 kg

Similarly,
971 mol of HBr 485.5 mol of Br
2
and 971 mol of HCl
Amount of Br
2
formed

= 485.5 80 = 38.84 kg.

Page 36

Amount of HCl formed

= 971 36.5
= 35.44 kg/hr
At bottom, we obtain
Wt. of 10% HCl = 35.44/.1
= 354.4 kg/hr
Wt. of water in HCl solution = 354.4 35.44
= 318.96 kg/hr
For reaction, we provide
Cl
2
flowrate = 50kg/hr
Steam flowrate = 16kg/hr
At top, we obtain
Wt. of Cl
2
= 50 34.47
= 15.53 kg/hr
Wt of Br
2
= 38.84
Wt. of steam = ( Wt.of water in HBr solution + steam feed Wt. of
water in HCl solution)
= ( 314.6 + 16 - 318.96)
= 11.64 kg/hr

Page 37

MATERIAL BALANCE FOR DISTILLATION
Feed contains 38.84 kg of Br
2
and 11.64 kg of water.
i.e. .77% of Br
2
and 23% of water
At top,
Wt. of 98% Br = 38.84/.98
= 39.63 kg
Wt. of water = 39.63 38.84
= .8 kg
Wt of water at bottom= 11.64 - .8
= 10.84 kg

Page 38

ENERGY BALANCE FOR REACTOR 1

Reaction 1
2NaBr + H
2
SO
4
Na
2
SO
4
+ 2HBr
Chemicals Standard heat of reaction
(KJ/mol)
Heat Capacity
(cal mol
-1
K
-1
)
H
2
SO
4
-814 25
NaBr -361 11.74 + .00233T
HBr -36.4 6.8 + .000084T
Na
2
SO
4
-1387.1 32.8

Total heat of reaction at standard temperature
HR
0
= H
o

PRODUCTS
- H
o
REACTANTS
= [ 2(-36.4) + (-1387.1) ] - [ 2(-361) + (-184) ]
= 76.1 KJ/mol
= 18200 cal/mol
Total heat of reaction at operating temperature i.e. at 383 K
HR
383
= HR
0
+ Cp dt
= 18200 + ( 2.08T + .00298T
2
/2]
383
298
= 18200 - ( 176.8 + 86.248 )
= 17936.952 cal/mol of H
2
SO
4

= 8708413 cal

Page 39

Steam required is given by
HR
383
= mass of steam * Latent heat of vaporisation
HR
383
= m *
8708413 = m 540
m = 16 kg/hr of steam

Page 40

ENERGY BALANCE FOR REACTOR 2

Reaction 2
2HBr + Cl
2
2HCl + Br
2

Chemicals Standard heat of reaction
(KJ/mol)
Heat Capacity
(cal mol
-1
K
-1
)

HCl -72.31 6.7 + .00084T
Cl
2
0 8.28 + .00056T
HBr -66.36 6.8 + .000084T
Br
2
30.91 9

Total heat of reaction at standard temperature
HR
0
= H
o

PRODUCTS
- H
o
REACTANTS
= [ 2(-72.31) + (30.91) ] - [ 2(-66.36) + 0 ]
= 18.41 KJ/mol
= 4400 cal/mol
Total heat of reaction at operating temperature i.e. at 353 K
HR
353
= HR
0
+ Cp dt
= 4400 + ( .54T + .000056T
2
/2]
353
298
= 18200 + ( 29.7 - 10 )
= 4419.7 cal/mol of Cl
2

= 2145910 cal

Steam required is given by

Page 41

HR
353
= mass of steam * Latent heat of vaporisation
HR
353
= m *
2145910 = m 540
m = 3.97 kg/hr of steam

Page 42

ENERGY BALANCE FOR CONDENSER

CHEMICAL FEED
Kg/hr
TOP
Kg/hr
BOTTOM
Kg/hr
HEAT CAPACITY
kJ/(kg K)
Cl
2
15.53 15.53 - .477
Br
2
(liquid) - - 38.84 .946
Br
2
(gas) 38.84 - - .45
Steam 11.64 - 11.64 4.18

Energy Balance:
Q
H2O
= m x Cp x dt
= 11.64 x 4.18 x (70-50)
= 973.1 kJ
Latent heat of vaporization of Br
2
= .3745 kJ/(kg )
Q
Br2
= [(m x Cp x dt)
liquid
+ (m x Cp x dt)
gas
+ m ]
= 38.84[(.946 x 8) + (.45 x 12) + .3745]
= 518.22 kJ
Chlorine will be separated from the mixture gases as bromine liquidifies at 58
o
C and
boiling point of chlorine is very low.

Page 43

Q
Cl2
= 15.53 x .477 x 12
= 88.9 kJ
Q = Q
Cl2
+ Q
Br2
+ Q
H2O

= 88.9 + 518.22 + 973.1
= 1580.2 kJ
Cooling water required for temperature rise of 10
o
C
Q = m x Cp x dt
1580.2 = m x 4.18 x 10
m = 37.8 kg/hr

Page 44

ENERGY BALANCE FOR DISTILLATION TOWER
Balance on Bromine, bromine loss at bottom is neglected.
38.84 = Distillate * .98
D = 39.63kg/hr
Balance on Water,
Wt. of water in Br
2
solution = 39.63 38.84
= .8 kg/hr
Water at bottom W = 11.64 - .8
= 10.84 kg/hr
Energy Balance
Inputs: reboiler heat input Q
B
+ feed sensible heat H
F

Outputs: condenser cooling Q
C
+ top and bottom product sensible heat H
D
+ H
W
Basis: 30
o
C, 1 hr
Heat capacity data, average values
Br
2
: 30 50
o
C .94 kJ/(kg K)
water : 30 80
o
C 4.18 kJ/(kg K)
Heat capacity can be taken as additive.
Feed, 77% bromine = (.77 .946 + .23 4.18 ) = 1.69 kJ/(kg k)
Top, 98% bromine = (.98 .946 + .02 4.18 ) = 1.01 kJ/(kg k)
Bottom, water = 4.18 kJ/(kg k)

Page 45

Balance around condenser.
Reflux ratio R = 10
Also, R = L/D
where, L is reflux flow
D is distillate
Thus, L = 10 39.63 = 396.3 kg/hr
V = L + D = 396.3 + 39.63 = 435.93 kg/hr
where, V is vapour flow
At steady state,
Input = Output
H
V
= H
D
+ H
L
+ Q
C

Hence Q
C
= H
V
- H
D
- H
L

Assume complete condensation.
Enthalpy of vapour H
V
= latent + sensible heat
Latent heat of bromine at 59
o
C = 375 kJ/(kg k)

Latent heat of water at 59
o
C = 2355 kJ/(kg k)
Taking latent heats as additive.
H
V
= 435.93 [ (0.02 2355 + .98 375) + (59 - 30) 1.01] = 193505 kJ/kg
The enthalpy of top product and refux are zero, as they both are at base temperature.
Q
C
= H
V
= 193505 kJ/kg

Page 46

Q
B
is determined from balance over complete system
H
F
+ Q
B
= H
D
+ H
W
+ Q
C
H
F
= 50.48 1.69(50-30) = 1706.224 kJ/kg
H
W
= 10.84 4.18(80-30) = 2265.56 kJ/kg
Q
B
= H
D
+ H
W
+ Q
C
- H
F

= 0 + 2265.56+ 193505 1706.224
= 194064.3 kJ/kg
Q
B
is supplied by condensing steam
Latent heat of steam = 2174 kJ/kg
steam required = 194064.3/2174
= 89.26 kg/hr
Q
C
is removed by cooling water with a temperature rise of 10
o
C
Q
C
= water flow 10 4.18
thus, waterflow = 193505/(10 4.18)
= 463 kg/hr

Page 47

Page 48

THERMODYNAMIC
FEASIBILITY

Page 49

THERMODYNAMIC FEASIBILITY FOR POCL
3
Thermodynamics Feasibility is of great importance in chemical process. The following
points can state its importance:-
1) Because of thermodynamic calculation of equilibrium constant k from free
energy of reacting material is possible. Thus for reaction with only the equilibrium
constant known, the expected maximum attainable conversation so obtained will
be maximum one for given reaction. This calculation is nothing but
thermodynamic feasibility.
2) Thermodynamic gives the heat liberated or absorbed during the reaction and hence
the nature of reaction i.e., endothermic or exothermic
Reaction: - PCl
3
+ O
2
POCl
3
Due to non availability of thermodynamic data, from the literature the practical
value of heat of formation of compounds is accepted from Langes Handbook.
Now heat of formation at 298K or 25C
Sr. No. Chemicals Specific heat
Cal/molk (25C to
60C)
Heat of formation
Kcal/mol K
1. PCl
3
23.44 -76.4
2. Oxygen 7.016 0
3. POCl
3
33.17 -142.7

H
R
(298K) = H
f
(Product) - H
f
(Reactants)
= (-142.7) - (-76.4 + 0)
= -66.3 kcal/mol Heat of reaction.
We know that,

Page 50

G = H
R

- TS -------- (1)
G = - R T ln K -------- (2)
Since our reaction is liquid
SO
Therefore Equation (1) becomes
G = H
R
-------- (3)
Now from equation (2) & (3)
G = - R T ln k -------- (4)
Where
R = Universal gas constant = 1.987 cal/g mole
T = 298k
K = Equilibrium constant
H
R
= Heat of reaction at 298 k
From equation (4)
-66.310
3
= - (1.987) (298) ln k
p1

k
p1
= 40.24 10
48

H
R
at reaction temperature i.e. 333 k
H
R
(333k) = H
R
(298k) + C
p 298

333
dT -------- (A)
C
p
in range of 298K to 333K

Page 51

C
p
= [C
p
(product) - C
p
(reactant)]
= [33.17 23.44+ (0.51.016)]
= 6.222 cal/mole.K

From equation (A)
H
R
(333k) = -66.3 + 6.22 (333 298)
H
R
(333k) = -66.53 kcal/mole
= -279.3kJ/mole
S = 0.308 kcal/mole K
Now, to find the k at 333K, we use relation.
lnk
1
k
2
= H
R
(298k) R [1/T
1
1/T
2
]
ln (4.24 10
48
/ k
2
) = (-66.3/1.927) [(1/333)-(1/298)]
k
2
= 3.28 10
43
As the value of k
2
(at 333K) is very high i.e. equal to infinity.
So conversion is also high ( consider about 90 to 95% ).

Page 52

REACTOR DESIGN

Page 53

REACTOR DESIGN

Page 54

Page 55

PLANT UTILITIES

Page 56

In manufacturing of liquid bromine, three main utilities are involved. They are as follows:

Cooling water:
Cooling water is used in condenser and cooling water tower. In condenser it is used to
absorb heat so as to convert gaseous mixture of HBr, H
2
O, from reactor 1 to liquid state
and condense Br gas coming out of distillation column to obtain liquid bromine.
Steam:
It is used in reactor 1 and distillation column as a heating medium. In reactor 2 it is used
as heating medium and carrier gas to carry Cl
2
gas.
Electricity:
It is the common utility used in every plant to run electric motor, controllers, different
equipments and instruments.
Vacuum:
It is used in filtration to separate impurities from mixture coming out from reactor 1.

Page 57

MAINTENANCE

Page 58

MAINTENANCE
The world Maintain literally means, to cause to Continue. In a plant this means that
physical plant assets (machinery and equipment) continue to fulfill their intended function.
Maintenance is necessary so as to keep the machines, equipment etc. running at their
maximum operating efficiency. Thus smooth production with minimum breakdown is
achieved. Maintenance creates so far working condition in the plant and also help to
reduce the total working cost of the plant.
Maintenance of the equipment in the Liquid Bromine

plant is done as follows:-
Centrifugal Pump:-
1. The Suction and discharge pipes of the Centrifugal Pump should be cleaned by
flushing water.
2. Bearing should be lubricated.
3. If the shaft sleeves are worn out they should be replaced.
4. If the impeller is damaged it should be repaired or replaced. Run out of the shaft
should be prevented.
5. Alignment of the pump should be checked.
6. Power / voltage given should be measured.

Valves:-
1. Valves, which may be pneumatic, hydraulic etc, are used to stop completely or
regulate flow.
2. The Valve should be flushed with water to remove the rust, scale and dirt, which
may be present under the disc and washer between the threads and other place.
3. The threads and seating surface should be cleaned with brush. If needed the seats
and disc should be replaced.
4. All rotating and sliding parts must be lubricated.

Page 59

Piping:-
1. All the pipes are initially cleaned by mild acid and then by then by a neutralizing
agent followed by flushing with clean water. Pipe threads should be cleaned with
wire brush.
2. Leakage from the piping must be permanently stopped.
3. Pipes and pipe joints which have been attacked by corrosion should be replaced
immediately.

Process Control Instruments:
1. All process Control Instruments including indicators, controller, sensor, actuators
etc should be checked for their proper working.
2. Their calibrations should be checked with the master instruments. Any faulty
instruments should be replaced by new one or recalibrated.

Reactors:-
1. Initially all the material presents it inside the reactor must be drained off in a safe
point of discharge. If any undesirable gases are present it should be vented to the
stripping section.
2. The reactor is then thoroughly flushed with hot or cold water it should be seen that
the reactor contains no traces of PCl
3
& POCl
3
.
3. Reactor consist Rapture Disc, which is worked at the time of emergency i.e.
when the pressure developed inside the reactor goes to tolerance level. The person
entering the reactor should be properly examining it, after every month. He should
be checking its proper sound condition.

Page 60

4. The person entering the reactor should be wear his safety uniform & should carry
the safety permit with him. Before he enter the reactor he should be see that it is
sufficiently ventilated as well as illuminated.
5. The jobs to be performed by this worker also include cleaning the alignment of the
shaft.

Page 61

HANDLING AND
STORAGE

Page 62

HANDLING, SHIPPING & STORAGE
Liquid Bromine is classified by the ICC as a corrosive liquid, and DOT corrosive material
label is required by law, on individual containers. Glass lined and PTFE lined steel
equipment is frequently in reactors.
An exhaustive survey and awareness of safety hazards are among the basic and primary
conditions for the safe handling of materials at all stages, including: production, storage,
transportation and use.
Consequences of Exposure
Liquid bromine produces a mild cooling sensation on rst contact with the
skin, which is followed by a sensation of heat. If bromine is not removed immediately by
ooding with water, the skin becomes red and nally brown, resulting in a deep burn that
heals slowly. Contact with concentrated vapour can also cause burns and blisters. For
very small areas of contact in the laboratory, a 10% solution of sodium thiosulfate in water
can neutralize bromine and such a solution should be available when working with
bromine.
Bromine is especially hazardous to the tissues of the eyes where severely painful and
destructive burns may result from contact with either liquid or concentrated vapour.
Ingestion causes severe burns to the gastrointestinal tract.
Detection of Bromine Vapour
Bromine vapour in air can be monitored by using an oxidant monitor instrument that
sounds an alarm when a certain level is reached. An oxidant monitor operates on an
amperometric principle. The bromine oxidizes potassium iodide in solution, producing an
electrical output by depolarizing one sensor electrode.

Page 63

Protective Equipment
Totally enclosed systems should be used for processes involving bromine. For handling
bromine in the laboratory, the minimum safety equipment should include chemical
goggles, rubber gloves, laboratory coat, and fume hood. For handling bro-mine in a plant,
safety equipment should include hard hat, goggles, neoprene full coverage slicker,
neoprene rubber gloves, and neoprene boots. For escaping from an area where a bromine
release has occurred, a full face respirator with an organic vaporacid gas canister is
desirable. For emergency work in an area with bromine concentrations>0.1ppm, a self-
contained breathing apparatus can be used until the air supply gets low.

Safe production of bromine
In bromine production, as in any other production process in which bromine is involved
strict safety rules have to be observed11, based on a thorough understanding of the
hazards inherent in each of the processes, raw materials, intermediate products and
products.

The following precautions should be taken:
- All the production systems should be hermetically sealed.
- All outputs of the system should be treated appropriately (products,
by products, exhaust fumes, sewage and solid waste) to prevent
compromising safety and endangering the environment.
- Appropriate steps must be taken to prevent emission of toxic gases.
- All parts of the installation must be constructed from bromine-
resistant materials.

Page 64

Safe handling of bromine leakage
If an accident occurs and there is a bromine leakage, it is important to deal with the
leakage immediately in such a way as to limit the harm done to people and the
environment as much as possible. We saw how bromine is neutralized in the laboratory.
Different considerations may be put forward for the establishment of suitable industrial
bromine-neutralizing methods, adapted to large-scale processes. The use of larger
quantities of material requires that serious thought be given to such questions as: - Ease of
handling - Availability of neutralizing agents - Costs - Reaction enthalpy.
Safe storage of bromine
Safe storage of materials is an important issue, which over the years has itself become a
special expertise. Storage rules and methods must comply with the particular properties of
each material, its reactions with other materials and the different hazards involved. The
properties of bromine also have an important bearing on its storage: - The volatility of
bromine dictates the need to store it in a place protected from external damage. - Its
oxidizing capacity dictates the need to avoid contact with reducing agents, organic
compounds and combustible materials. - Its highly corrosive action in the presence of
water dictates the need to store it in a dry place and to build storage tanks with suitable
resistant coating. - Its ability to form light-induced free radicals requires storage in a
dark place. - In addition there are other requirements, such as: protection against static
electricity, etc.
Safe transportation of bromine
Accidents in which toxic materials are involved, and plants producing such materials,
quickly make headlines and are widely publicized. Usually these accidents are caused by
carelessness, negligence or human error. Many accidents during transportation of
hazardous materials occur as a result of speeding. These accidents could have been
prevented if everybody involved in the transportation of materials in general, and
hazardous materials in particular, had obeyed the rules that apply to them.

Page 65

Transportation of hazardous materials requires particular expertise and bromine is no
exception. International and local transportation of bromine is subject to international
control and regulations on transportation of hazardous materials.
Bromine is transported in liquid form, but its volatility and toxicity demand that it be
transported in the safest possible way, with complete sealing of the transporters and
precautions against the danger of bromine leakage to the air.
Safe use of bromine
Bromine is used for many purposes in research and industry. All safety rules observed
during the production, storage and transportation of bromine must also be obeyed during
its handling and use. Every customer who uses large amounts of bromine must have an
unloading station. The bromine is unloaded while connected to the isotank or the
container of the absorption tower to prevent bromine vapours escaping into the air.
Emptying of the isotank is monitored by weighing or by watching through a glass
window. When all the bromine is removed, the colour of the windows changes from
brownish-red to a light hue. At any such unloading station suitable neutralizing materials
and protective equipment must be available.

Page 66

Section 1
Chemical Product and Company Identification
Product Name : Liquid Bromine
Catalog Codes : SLB4777
CAS# : 7726-95-6
RTECS : EF9100000
TSCA : TSCA 8(b) inventory: Bromine
CI# : Not available.
Synonym :
Chemical Name : Bromine
Chemical Formula : Br
2

Contact Information : Sciencelab.com, Inc.14025 Smith Rd.
Houston, Texas 77396 US Sales: 1-800-901-7247
International Sales: 1-281-441-4400

Section 2
Composition and Information on Ingredients
Name CAS # % by Weight
Bromine 7726-95-6 100
Toxicological Data on Ingredients: Bromine: ORAL (LD50): Acute: 3100 mg/kg
[Mouse]. 4160 mg/kg [Rabbit]. 2600 mg/kg [Rat].

Page 67

Section 3
Hazards Identification
Potential Acute Health Effects : Very hazardous in case of skin
Contact (irritant), of eye contact
(irritant), of ingestion, of inhalation.
CARCINOGENIC EFFECTS : Not available.
MUTAGENIC EFFECTS : Not available.
TERATOGENIC EFFECTS : Classified.POSSIBLE for human.
DEVELOPMENTAL TOXICITY : Not available. Repeated or prolonged
exposure is not known to aggravate
medical condition.

Section 4
First Aid Measures
Eye Contact:
Check for and remove any contact lenses. In case of contact , immediately flush eyes with
plenty of water for atleast 15 minutes. Get medical attention immediately.
Skin Contact:
In case of contact, immediately flush skin with plenty of water. Cover the irritated skin
with an emollient. Remove contaminated clothing and shoes. Wash clothing before reuse.
Thoroughly clean shoes before reuse. Get medical attention.

Page 68

Serious Skin Contact:
Wash with a disinfectant soap and cover the contaminated skin with an anti-bacterial
cream. Seek immediate medical attention.
Inhalation:
If inhaled, remove to fresh air. If not breathing, give artificial respiration. If breathing is
difficult, give oxygen. Get medical attention.

Serious Inhalation:
Evacuate the victim to a safe area as soon as possible. Loosen tight clothing such as a
collar, tie, belt or waistband. If breathing is difficult, administer oxygen. If the victim is
not breathing, perform mouth-to-mouth resuscitation.
WARNING: It may be hazardous to the person providing aid to give mouth-to-mouth
resuscitation when the inhaled material is toxic, infectious or corrosive. Seek immediate
medical attention.
Ingestion:
Do NOT induce vomiting unless directed to do so by medical personnel. Never give
anything by mouth to an unconscious person. If large quantities of this material are
swallowed, call a physician immediately. Loosen tight clothing such as a collar, tie, belt or
waistband.
Serious Ingestion : Not available.
Section 5:
Fire and Explosion Data
Flammability of the Product : Nonflammable

Page 69

Auto-Ignition Temperature : Not applicable
Flash Points : Not applicable
Flammable Limits : Not applicable
Products of Combustion : Not available
Fire Hazards in Presence
of Various Substances : Flammable in presence of combustible
materials of reducing materials of organic
material of aluminium.
Explosion Hazards in Presence
of Various Substances : Risks of explosion of product in presence
of mechanical impact : not available.
Risks of explosions of the product in
Presence of static discharge: not available.
Fire fighting Media and instructions : Not applicable

Special Remarks on Fire Hazards: Flammable in the form of liquid or vapour by
spontaneous chemical reaction with reducing
materials. May cause fire in contact with
wood, sawdust, cotton, straw, etc.
Special Remarks on Explosion Hazards : Reacts explosively with Acetylene,
Acrylonitrile, Ammonia, Dimethyl Formaldehyde, Ethyl
Phosphine, H
2
, Ni, Nitrogen Triiodide, O
3
, O
2,
P, K, Ag, Na.

Page 70

Section 6:
Accidental Release Measures
Small Spill:
Absorb with an inert material and put the spilled material in an appropriate waste disposal.
Large Spill:
Corrosive liquid. Poisonous liquid. Stop leak if without risk. Absorb with DRY earth, sand
or other non-combustible material. Do not get water inside container. Do not touch spilled
material. Use water spray curtain to divert vapour drift. Use water spray to reduce
vapours. Prevent entry into sewers, basements or confined areas; dike if needed. Call for
assistance on disposal. Be careful that the product is not present at a concentration level
above TLV. Check TLV on the MSDS and with local authorities.
Section 7:
Handling and Storage
Precautions:
Keep locked up. Keep container dry. Do not ingest. Do not breathe gas/fumes/
vapour/spray. Never add water to this product. In case of insufficient ventilation, wear
suitable respiratory equipment. If ingested, seek medical advice immediately and show the
container or the label. Avoid contact with skin and eyes. Keep away from incompatibles
such as reducing agents, combustible materials, organic materials
Storage:
Keep container tightly closed. Keep container in a cool, well-ventilated area.
Section 8:
Exposure Controls/Personal Protection
Engineering Controls:

Page 71

Provide exhaust ventilation or other engineering controls to keep the airborne
concentrations of vapours below their respective threshold limit value. Ensure that
eyewash stations and safety showers are proximal to the work-station location.
Personal Protection:
Face shield, Full suit, Vapour respirator. Be sure to use an approved/certified respirator or
equivalent, Gloves, Boots.
Personal Protection in Case of a Large Spill:
Splash goggles, Full suit, Vapour respirator. Boots, Gloves. A self contained breathing
apparatus should be used to avoid inhalation of the product. Suggested protective clothing
might not be sufficient; consult a specialist BEFORE handling this product.
Exposure Limits:
TWA: 0.66 STEL: 1.3 (mg/m3) from ACGIH (TLV) [United States] TWA: 0.1 STEL: 0.2
(ppm) from ACGIH (TLV) [United States] TWA: 0.1 from OSHA (PEL) [United States]
TWA: 0.7 (mg/m3) from OSHA (PEL) [United States] TWA: 0.66 STEL: 2 (mg/m3)
[United Kingdom (UK)] TWA: 1 STEL: 0.3 (ppm) [United Kingdom (UK)] Consult local
authorities for acceptable exposure limits..
Section 9:
Physical and Chemical Properties
Physical state and appearance : Liquid
Odor : Pungent (Suffocating)
Taste : Not available.
Molecular Weight : 159.808 g/mole
Colour : Reddish Brown
pH (1% sol
n
/water) : Not available.

Page 72

Boiling Point : 58.78
o
C
Melting Point : -7.25
o
C.
Critical Temperature : 315
o
C.
Specific Gravity : 3.11
Vapor Pressure : 23.3 kPa.
Vapor Density : 7.1 (Air)
Volatility : Not available.
Odor Threshold : 0.05 ppm.
Water/Oil Dist. Coeff. : Not available.
Ionicity (in Water) : Not available.
Dispersion Properties : See solubility in water, diethyl ether
Solubility: Easily soluble in diethyl ether. Very
slightly soluble in cold water. Freely
soluble in alcohol, chloroform, carbon
disulfide, carbon tetrachloride,
concentrated hydrochloric acid, and
aqueous solution of bromides.

Section 10:
Stability and Reactivity Data
Stability : The product is stable.
Instability Temperature : Not available.
Conditions of Instability : Incompatible materials.

Page 73

Incompatibility with various
Substances : Not available.
Corrosivity : Extremely corrosive in presence of
aluminum, of zinc, of stainless steel(304), of
stainless steel(316). Highly corrosive in presence of
copper. Non-corrosive in presence of glass
Special Remarks on Reactivity :Incompatible with organic compounds containing
active hydrogen atoms adjacent to the carbonyl
group (aldehydes, ketones, carboxylic acids).
Special Remarks on Corrosivity : Corrodes iron, stainless steel and copper.
Severe corrosive effect on bronze
Polymerization : Will not occur.

Section 11:
Toxicological Information
Routes of Entry : Inhalation, Ingestion.Dermal contact.
Toxicity to Animals : Acute oral toxicity (LD50): 1271 mg/kg
[Rat].
TERATOGENIC EFFECTS : Classified POSSIBLE for human.
Other Toxic Effects on Humans : Slightly hazardous in case of skin contact
(irritant), of ingestion, of inhalation.

Special Remarks on Toxicity to Animals : Not available.

Page 74

Special Remarks on Chronic Effects on Humans:
Not available.
Special Remarks on other Toxic Effects on Humans:
Acute Potential Health Effects: Skin: Contact with liquid is corrosive and causes
ulceration and skin burns. In milder cases, it might cause skin rash, pustles, measle-like
erruptions, furuncles, and cold and clammy skin with cyanosis or pale color. Eyes: It is a
lacrymator and causes eye irritation, eyelid inflammation at low concentration. At higher
concentrations it may cause blepharospasm, photophobia, conjunctivitis, and burns.
Inhalation: Inhalation of smaller amounts may cause severe irritation of the respiratory
tract with coughing, chest tightness, shortness of breath, and nosebleed. Inhalation of
larger amounts may cause pulmonary edema, chemical pneumonitis, bronchospasm,
pneumomidiastinum, glottal spasm, glottal edema, inflammatory lesions in the mucous
membranes, inflammed tongue and palate, chemical burns of the lungs, asthmatic
bronchitis, and severe choking. Death may occur due to circulatory collapse, asphyxiation
from edema of the glottis, aspiration pneumonia, or pulmonary edema. It may also affect
behavior/central nervous system and gastrointestinal tract, cardiovascular system, thyroid,
Symptoms may include dizziness, headache, fatigue, disturbances of sleep and sexual
function, feeling of opression, vertigo, anxiety, depression, muscle incoordination,
emotional instabililty, delirium, stupor, vomiting, diarrhea, abdominal pain, tachycardia,
hypotension. Ingestion: May cause severe and permanent damage to the digestive tract. It
may cause gastrointestinal tract burns, burning pain of the mouth and esphagous, corrosive
gastroenteritis with vomiting, abdominal pain, diarrhea, and possible bloody feces. It may
cause kidney damage (hemmorrhagic nephritis with oliguria or anuria, and liver damage,
brownish discoloration of lips, tongue and mucous membranes It may also affect the
cardiovascular system (tachycardia, hypotension, and cyanosis and behavior/central
nervous system (symptoms similar to inhalation) Chronic Potential Health Effects:
Inhalationand Ingestion: Prolonged or repeated exposure may affect respiration and

Page 75

endocrine system (thyroid), metabolism, behavior/central nervous system, and
cardiovascular system, and cause kidney and liver damage. Effects may be delayed.

Section 12:
Ecological Information
Ecotoxicity : Not available.
BOD5 and COD : Not available.
Products of Biodegradation : Possibly hazardous short term degradation
products are not likely. However,
long term degradation products may arise.
Toxicity of the Products
of Biodegradation : The products of degradation are less toxic
than the product itself.
Special Remarks on the Products
of Biodegradation : Not available.

Section 13:
Disposal Considerations
Waste Disposal:
Waste must be disposed of in accordance with federal, state and local environmental
control regulations.

Page 76

Section 14:
Transport Information
DOT Classification :Class 8: Corrosive material CLASS 6.1:
Poisonous material
Identification : Bromine UNNA: 1744 PG: I.
Special Provisions for Transport : Poison-inhalation hazard, Zone A

Section 15:
Other Regulatory Information
Federal and State Regulations :
Connecticut hazardous material survey.: Bromine Illinois toxic substances disclosure to
employee act: Bromine Illinois chemical safety act: Bromine New York release reporting
list: Bromine Rhode Island RTK hazardous substances: Bromine Pennsylvania RTK:
Bromine Minnesota: Bromine Massachusetts RTK: Bromine Massachusetts spill list:
Bromine New Jersey: Bromine New Jersey spill list: Bromine Louisiana RTK reporting
list: Bromine California Director's list of Hazardous Substances: Bromine TSCA 8(b)
inventory: Bromine SARA 302/304/311/312 extremely hazardous substances: Bromine
SARA 313 toxic chemical notification and release reporting: Bromine.
Other Regulations:
OSHA: Hazardous by definition of Hazard Communication Standard (29 CFR
1910.1200). EINECS: This product is on the European Inventory of Existing Commercial
Chemical Substances.

Page 77

Other Classifications:
WHMIS (Canada):
CLASS D-1A: Material causing immediate and serious toxic effects (VERY TOXIC).
CLASS E: Corrosive liquid.
DSCL (EEC):
R26- Very toxic by inhalation. R35- Causes severe burns. R50- Very toxic to aquatic
organisms. S1/2- Keep locked up and out of the reach of children. S7/9- Keep container
tightly closed and in a well-ventilated place. S26- In case of contact with eyes, rinse
immediately with plenty of water and seek medical advice. S45- In case of accident or if
you feel unwell, seek medical advice immediately (show the label where possible). S61-
Avoid release to the environment. Refer to special instructions/Safety data sheets
HMIS (U.S.A.)
Health Hazard : 3
Fire Hazard : 0
Reactivity : 0
National Fire Protection Association (U.S.A.)
Health : 3
Flammability : 0
Reactivity : 0

Specific hazard:
Protective Equipment: Gloves. Lab coat. Vapour respirator. Be sure to use an
approved/certified respirator or equivalent. Safety glasses.

Page 78

Section 16:
Other Information
References : Not available.
Other Special Considerations : Not available.
Created : 10/11/2005 1:06 PM
Last Updated : 06/09/2012 12:00 PM

MARKET SURVEY

Page 79

Bromine Production by area in 2008

China
Japan
USA
Isreal
Jordan
USA 36%
Isreal 27%
Jordan
14%
China 19%
Japan 3%
fig 2
from Isreal
Chemicals ltd.

Page 80

Bromine Consumption in 2008

China
30%
U.S.A
19%
Europe
13%
Japan
7%
India
6%
Others
25%
fig.3
from Israel
chemicals ltd.

Page 81

Bromine demand by applications

Flame
Retardants
48%
Drilling
Fluids
10%
Others
30%
Fumigates
3%
Water
Treatment
4% Industrial
Uses
5%

fig.4
from Israel
chemicals ltd.

Page 82

Page 83

SITE SELECTION

Page 84

SITE SELECTION
Selected Site Badlapur
The location of the plant has a very significant effect on the profitability of a project and
the scope for future expansion. The following are the factors which were examined for our
site selection.
Raw Material supply
This is one of the most important aspect to be examined to finalize a site. The availability
of raw materials for NaBr & HBr at the above selected site is discussed below.
A) NaBr: NaBr is obtained from pharmaceutical and fertilizer industry as an effluent.
These industries are situated in the nearby area so obtaining raw material is a very easy
task.
B) Chlorine in quantitative terms chlorine is the largest required raw material. Chlorine is
obtained from nearby plants in the MIDC region
C) Steam is easily available from boilers.
Location with respect of marketing area
Liquid Bromine is chiefly used in pharmaceutical indistries in manufacturing of
plastisicers as additive I hydraulic fluids, in lubricants amongst others. The badlapur
region and the Mumbai Ahmadabad industrial belt offer a very good potential market for
the product. Therefore the site is well located with respect to marketing area.
Transport facility.
Therefore transport facility is easily available for raw materials, products and equipments.
The proximity to railways also plays an important role in selecting this site.

Page 85

Availability of labour
The labour for plant construction and operation is readily available locally and cheaply.
Also due to its proximity to education center like Mumbai and being an already developed
industrial area it attracts semi skilled plant operators and managers from neighbors states
Availability of Utilities
The site is located near chikhaloli dam thus; water and power are supplied at reasonable
rates. Also the availability of fuel is no problem due to excellent facilities.
Availability of suitable land
Badlapur being an industrial zone, acquiring land is not difficult. The land soil has a good
bearing capacity and not terrain.
Local community consideration
The proposed plant would be acceptable to the local community since it is a chemical
zone. Also the plant is solely located away from the residential area. Adequate schools,
banks, housing, recreational and cultural faculties are available for the plant employees
near the site. Also there are no significant inter community tension.
Climate
The region experiences moderate to hot climate throughout the year and seasonal rainfall.
It is not prone to high winds or earthquakes.
Political and strategic consideration
There are no restrictions on development of industry at the location as it is allocated for
industrial development.
Besides the above factors communication, industrial infrastructure, medical and fire
fighting services are well established.

Page 86

Thus the above actors will give a strategic advantage to a liquid Bromine plant located at
the recommended site.

Page 87

PROJECT COST
ESTIMATION

Page 88

PROJECT COST ESTIMATION

The cost of the individual equipment is calculated on the basis of the Weight of the
equipment and the material of construction required for the particular equipment. The cost
is rounded up to the higher Value depending upon the complexity of the equipment.
The basic purchase of equipment used in the plant is calculated.
Equipment Cost Rs. Lakhs
Demister Tank 4.0
POCl
3
Reactor with Jacket and 2.0
Agitators
Condenser 8.0
Distillation Tower 5.0
Disaster Vessel 1.0
Noah Scrubber 0.8
Packed Tower along with Packing 1.2
Silica Gel Column 2.0
Storage of PCl
3
& POCl
3
2.0
Liquid O
2
storage 8.0
Pump (4) 3.2
A = 35.20

Page 89

INSTALLATION
Piping 8,80,000
Insulation 70,000ll
Utilities 7,04,000
Electrical 5,28,000
Instruments 3,52,000
Effluent treatment plant 5,28,000
B = 3,06,24,000
MAN POWER EMPLOYED
Manager 3,25,000
Plant Superintendent 1,95,000
Engineer 2 3,90,000
Skilled workers 10 3,90,000
Office staff 8 2,60,000
Transportation 4 6,24,000
C = 2,18,40,000
Total Cost = A + B + C = Rs.5,39,84,000

Page 90

Page 91

ENVIRONMENTAL
CONSIDERATIONS

Page 92

ENVIRONMENTAL DATA

CONCLUSION

Page 93

CONCLUSION

After completing this project, we have concluded that this project gives all that knowledge
for establishing a plant of such hazardous chemicals.
The complete project is arranged by taking consideration of properties, safety, precaution,
prevention method & various manufacturing method. This project gives brief idea about
behavior of such hazardous chemical.
Project itself describes importance of such chemical because not only these both
chemicals are very dangerous but also very importance especially for pharmaceutical
products. Therefore, such projects are guideline for future aspects.

Page 94

BIBLIOGRAPHY &
REFERENCES

Page 95

BIBLIOGRAPHY

Sr.
No.
Name of book Author
1. Perrys chemical engineering
Handbook.
Robert.H.Perry, Don Green
2. Material Handbook. Brady & Clauser
3. Safety management. Greemaldi, Simonds.
4. Chemical process & Equipment
design .

K.A.Gavhane.
5. Chemical Reaction Engineering. K.A.Gavhane.
6. Encyclopedia of Chemical Engg. Kirk Othmer.
7. Piping Handbook. Nayyar
8. Industrial Gases. Downie
9. Property of gases & liquids. Reid, Prausnitz, Paling

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