Chlorine - Methods 2520of 2520production

METHODS OF PRODUCTION AND PROCESS SELECTION
1. KEL – CHLORINE PROCESS:

This process was developed by KELLOG, which uses HCl as a raw
material from the waste gases of a fluorinated hydrocarbon plant.
Concentrated sulphuric acid and 1% nitrosylsulphuric acid are used as
catalysts.
Sulphuric acid catalyst is fed from the top of the stripper column. The
HCl gas reacts with the catalyst to form nitrosyl – chloride. O2, the ultimate
oxidizing agent blows the remaining HCl out of the H2SO4, which becomes
more concentrated and then get cooled in the flash vaporizer. This acid is
then fed back into the process. Nitrosyl – chloride, HCl, O2 and water
vapour flows as gaseous streams into the oxidizer and reacts there, resulting
increase in the temperature. In the absorber rest of the HCl is oxidized.
Concentrated H2SO4 acid is fed at the top, reacts with the oxides and N2 to
form nitrosyl – sulphuric acid, absorbs the water that has formed and is fed
back into the stripper.
The cooled dried chlorine gas still contains 2% HCl and up to 10%
O2. Both are removed by liquefaction.
On the account of the aggressive nature of the chemicals, expensive
materials, such as tantalum plated equipment and pipes must be used.
2. OXIDATION OF HCl BY NITRIC ACID:

The nitrosyl – chloride route to chlorine is based on the strongly
oxidizing properties of nitric acid.
The practical problem lies in the separation of the chlorine from HCl
and other gaseous components. The dilute nitric acid must be concentrated
for further use. Corrosion problems are severe.
3. DEACON PROCESS:
Air oxidizes HCl in vapour phase, over a hot copper containing

catalyst (CuCl2). The principal difficulties of fugitive CuCl2, low Cl2
composition in the exit stream, limited available materials of construction
with high maintenance and poor catalyst activity makes this process
unsuitable.
4. AIRCO – PROCESS:
The Air Reduction Company has made a number of developments in

the basic Deacon process in recent years using both air and O2. The net
result indicates that the process is practical today from an industrial by
product containing HCl.
HCl is mixed with air or O2 and preheated in a heat exchanger and
sent to the fluidised bed reactor that operates at 300°C to 500°C.
4 HCl + O2 2 Cl2 + 2 H2O + ∆

The product gases from reactor is cooled to 110°C and fed to the
product gas cooler where substantially all the water from reaction is
condensed. The top stream of the product gas cooler contains mainly Cl2, O2,
N2, H2O and HCl. This stream is sent to product gas absorber where the HCl
gas is absorbed with 22% HCl solution and the rest of the gases leave the
absorber from the top. This stream is then taken to liquefaction system from
which the pure chlorine is obtained.
This process is chosen for the production since the problem of
catalysis has been solved by the use of improved copper base catalyst bodies
with at least one year of useful activity, utilizing rare earth as promoters and
accelerators in a special reverse in flow reactor which makes the reaction
self sustaining without the addition of external heat. New methods, materials
of construction and engineering technique make this process economically
feasible.
PROCESS DESCRIPTION
HCl is mixed with air, fed into a fluidised bed reactor containing
cupric chloride catalyst, and maintained at a suitable temperature in the
range of 300 - 500°C. HCl in the feed reacts with oxygen or oxidizes to give
chlorine and water. The product gas containing chlorine, water, unchanged
HCl and inert gases are passed to a packed tower cooler/ scrubber, operating
somewhat above the atmospheric pressure. In the tower the gases comes in
contact with 33 – 36% HCl, thereby cooling the insoluble gases and
absorbing the unchanged HCl. The acid enters the tower at 20°C. Most of
the water and some amount of HCl contained in the product gas are
dissolved in the acid. The liquid effluent coming out of the scrubber is split
up into two streams. One stream is passed to the top of the scrubber through
a cooler, which lowers the temperature to 20°C while the other is sent to the
top of a stripper column (Expeller). In the stripper, the HCl present in the
incoming stream from the product gas cooler is stripped off and hence a gas
containing around 98% HCl (the other constituents being water and
chlorine) leaves the stripper from the top that is fed back into the reactor. A
mixture of water and HCl containing 20 – 22% HCl leaves from the base of
the expeller at a temperature of 147°C, which is fed to a HCl absorber
through a cooler and the flow rate is maintained around 1000 kg/ hr. In the
absorber, almost all of the HCl coming from the product gas cooler/ scrubber
are absorbed. The liquid leaving the base of the HCl absorber contains 33 –
36% of HCl which is then mixed with fresh 36% HCl and then fed to the top
of the expeller. The gaseous chlorine leaving the top of the HCl absorber
column is then dried and sent to liquefaction unit to get pure liquid chlorine.
The workings of various equipments are described as follows:

1. The catalytic reactor consists of a U – shaped steel container
with “Foamsil” lined catalyst container. Both feed and
discharge ports are at the bottom. Periodic reversal of flow,
controls reaction temperature, preheats the feed. The copper
catalyst acts as an efficient heat regenerator. Gases leaves the
reactor slightly below 200°C
2. In the cooler, product gas is scrubbed by cold 33 – 36% HCl
solution. Substantially all the water of reaction condenses to
produce a concentrated solution of HCl, which is stripped of its
HCl content in the expeller described below. The cooler is
internally lined with non – corrosive material.
3. In the absorber, the cooled reactor gas stripped of its water
content is absorbed in cold 20 – 22% HCl solution in a falling
film unit of karbate and plastic construction. It leaves as 33 –
35% solution, which is then stripped in the expeller. The
absorbing liquid (22% HCl) is the cooled “foots” of the
expeller.
4. The expeller or stripper is a karbate packed tower which is fed
with strong & cold HCl solution which is stripped to produce a
product of 98% HCl gas and foots as close as 20% solution of
HCl. The water build up is discharged from the system by
stripping HCl as gas, in a separate system.
5. The dry gas from the absorption tower is then fed to the
liquefaction unit where most of the sniff gases and O2 is
removed and chlorine emerges as the pure liquid.
THERMODYNAMIC CONSIDERATIONS
The oxidation of hydrogen chloride is a reversible reaction and hence

the feasibility of the desired forward reaction is highly dependent upon
various factors such as temperature, pressure, etc. Arnold and Kobe have
studied the effect of varying these factors. They have calculated the
thermodynamic functions of hydrogen chloride and chlorine from
spectroscopic measurements. The reaction is:
4 HCl + O2 2 Cl2 + H2 O ; ∆Hr = - 192 kcal / kg HCl

The equilibrium constant K for this reaction has been calculated from
the following equation.
-∆G° / T = 2.303 R log K
where ∆G° = change in free energy of the reaction
= - 274460 + 8.65 T – 0.00229 T2 +
0.263 x 10-6 T3
T = temperature
R = gas constant
Effect of other variables:

Pressure:
Increase in the pressure gives an increase in the HCl conversion and
hence increase in the chlorine content. However, the pressure chosen for
operation is only 1 atm. This is done after considering the economics point
of view of the plant. High-pressure operation involves the compression of
gases, which requires considerable amount of money. Secondly, the reactor
will have to be designed to withstand the pressure too. At high pressure, the
equipment is highly prone to failure due to stress corrosion cracking.
Dilution of oxygen with inert gases:

If pure oxygen is used instead of air, higher content of chlorine is
obtained in the product gas. At 350°C, the HCl conversion increases by 2%.
And the chlorine recovery also becomes simpler. But due to the high cost of
O2 as compared to the air, one usually goes for air.
Hydrogen chloride / Air Ratio:

Increasing the excess oxygen content from 0 to 300% increases the
conversion by 10% at 700°K, but the chlorine content decreases by 12%.
Thus the cost of recovery increases.

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METHODS OF PRODUCTION AND PROCESS SELECTION

1. KEL – CHLORINE PROCESS:

2. OXIDATION OF HCl BY NITRIC ACID:

Air oxidizes HCl in vapour phase, over a hot copper containing

The Air Reduction Company has made a number of developments in

4 HCl + O2 2 Cl2 + 2 H2O + ∆

The workings of various equipments are described as follows:

The oxidation of hydrogen chloride is a reversible reaction and hence

4 HCl + O2 2 Cl2 + H2 O ; ∆Hr = - 192 kcal / kg HCl

Effect of other variables:

Dilution of oxygen with inert gases:

Hydrogen chloride / Air Ratio:

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