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 Cl2 gas to get gaseous bromine which when condensed in a
condenser gives Liquid Bromine.

Overall Reaction:-

NaBr + H2SO4 → HBr + Na2So4

HBr + Cl2 → HCl + Br2

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. H2SO4 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 oC and a pressure of 1kg/mm2.

Reaction taking place in the reactor is given by

NaBr + H2SO4 → HBr + Na2So4

Page 1
Since the reaction temperature is maintained at 110 oC 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 oC.

Liquid HBr is allowed to pass from the top and steam and Cl2 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 + Cl2 → HCl + Br2

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. Br2
vapours along with unreacted Cl2 gas & H2O is condensed in a condenser & sent to a
distillation unit for further separation.

Page 2
Distillation Unit: -

Distillation unit is also made up of glass & is also 6 m tall. Packing used is rasching rings
and temperature is maintained 80oC.

The liquid mixture obtained from condenser is allowed to be heated using steam. Cl2 gas
having least boiling point in the mixture evolves first & is recycled back to reactor 2.
Around 62 to 65oC Br2 starts to evolve which is sent to the condenser where its
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 3
 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.

1. Saving of labour.
Page 4
 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 5
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 110˚C, 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 112˚C or 114˚C the
temperature is controlled to 110˚C. 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 6
 MATERIAL BALANCE FOR REACTOR 1

Chemical reaction:-

2NaBr + H2SO4 → Na2SO4 + 2HBr

Required data:-

Chemicals Molecular weight

H2SO4 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 H2SO4

Amount of 98% H2SO4 required for 100 kg of NaBr

= (485.5 × 98)/.98

=48.55 kg

Similarly,

971 mol of NaBr → 485.5 mol of Na2SO4 and 971 mol of HBr

Amount of Na2SO4 formed = 485.5 × 142

= 68.94 kg.

Page 7
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 H2SO4 – Wt. of

HBr solution)

= (1000 kg + 48.55 kg – 393.255 kg )

= 655.295 kg

Page 8
 MATERIAL BALANCE FOR REACTOR 2

Chemical reaction:

2HBr + Cl2 → 2HCl + Br2

Basis: - 1kmole of product POCl3

Compound Molecular Weight

Br2 80

HCl 36.5

HBr 81

Chlorine 35.5

From the stoichiometry of the reaction,

971 mol of HBr → 485.5 mol of Cl2

971 mol of HBr → 78.65 kg/hr of HBr

Amount of Cl2 required for 78.65 kg of HBr

= (485.5 × 71)

=34.47 kg

Similarly,

971 mol of HBr → 485.5 mol of Br2 and 971 mol of HCl

Amount of Br2 formed = 485.5 × 80

Page 9
 = 38.84 kg.

Amount of HCl formed = 971 × 36.5

=35.44 kg/hr

At bottom, we obtain

Wt. of 12% HCl = 35.44/.12

= 295.33 kg/hr

Wt. of water in HCl solution = 295.33 – 35.44

= 259.9 kg/hr

For reaction, we provide

Cl2 flowrate = 50kg/hr

Steam flowrate = 16kg/hr

At top, we obtain

Wt. of Cl2 = 50 – 34.47

= 15.53 kg/hr

Wt of Br2 = 38.84

Wt. of steam = ( Wt.of water in HBr solution + steam feed – Wt. of

water in HCl solution)

= ( 314.6 + 16 - 259.9)

= 70.7 kg/hr

Page 10
 MATERIAL BALANCE FOR DISTILLATION

Feed contains 38.84 kg of Br2 and 70.7 kg of water.

i.e. .41% of Br2 and 59% 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= 70.7 - .8

= 69.9 kg

Page 11
 ENERGY BALANCE FOR REACTOR 1

Reaction 1

2NaBr + H2SO4 → Na2SO4 + 2HBr

Chemicals Standard heat of reaction Heat Capacity

(KJ/mol) (cal mol-1K-1)

H2SO4 -814 25

NaBr -361 11.74 + .00233T

HBr -36.4 6.8 + .000084T

Na2SO4 -1387.1 32.8

Total heat of reaction at standard temperature

ΔHR 0 = ∑ΔHo PRODUCTS - ∑ΔHoREACTANTS

= [ 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

ΔHR383 = ΔHR 0 + ∫ ΔCp dt

= 18200 + ( 2.08T + .00298T2/2]383298

= 18200 - ( 176.8 + 86.248 )

= 17936.952 cal/mol of H2SO4

= 8708413 cal

Steam required is given by

Page 12
ΔHR383 = mass of steam * Latent heat of vaporisation

ΔHR383 = m * λ

8708413 = m 540

m = 16 kg/hr of steam

ENERGY BALANCE FOR REACTOR 2

Reaction 2

2HBr + Cl2 → 2HCl + Br2

Chemicals Standard heat of reaction Heat Capacity

(KJ/mol) (cal mol-1K-1)

HCl -72.31 6.7 + .00084T

Cl2 0 8.28 + .00056T

HBr -66.36 6.8 + .000084T

Br2 30.91 9

Total heat of reaction at standard temperature

ΔHR 0 = ∑ΔHo PRODUCTS - ∑ΔHoREACTANTS

= [ 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

ΔHR353 = ΔHR 0 + ∫ ΔCp dt

Page 13
 = 4400 + ( .54T + .000056T2/2]353298

= 18200 + ( 29.7 - 10 )

= 4419.7 cal/mol of Cl2

= 2145910 cal

Steam required is given by

ΔHR353 = mass of steam * Latent heat of vaporisation

ΔHR353 = m * λ

2145910 = m 540

m = 3.97 kg/hr of steam

ENERGY BALANCE FOR DISTILLATION TOWER

Balance on Bromine, bromine loss at bottom is neglected.

38.84 = D .98

Page 14
 ENERGY BALANCE for POCl3

 HR (333K) = - 279.5kJ/mole

Total heat of reaction at (333K) Reaction temperature

=No. of moles of POCl3 × (279.5) kJ/mole

 No. of moles of POCl3 = (6281.54kg/ batch)/157.5

= 39.883 × 103 gm mole

 HR (333K) = 39.883 × 103 × (279.5) kJ/mole

= -11.147 × 103 kJ/mole

HR (333K) = Q = Heat evolved = Heat absorbed

During reaction by cold water

Q = mW CpW T

Where mw = Mass flow rate of chilled water

Cpw = Specific heat of water

T = (Inlet temperature – Outlet temperature)

-11,147.17 × 103 = mw × 4.182 × (25-35)

mw = 266.551 × 18 kg/batch

mw = 4797.92 kg/batch

Mass flow rate of water required = 599.74 kg/ hr

Page 15
 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

POCl3 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 PCl3 & POCl3 2.0

Liquid O2 storage 8.0

Pump (4) 3.2

A= 35.20

Page 16
 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 17