Chapter no 2 Process Selection

Chapter no 2

Process Selection
This chapter gives information about types of process used for production of sodium hydroxide and comparison
between different processes and discuss about process selection and description of the process and also show
process flow diagram.

2.1 Manufacturing Processes for Caustic Soda:

Generally all the caustic soda is contrived by the Electrolytic Process. The foremost raw material used for the
manufacture of caustic soda is Industrial salt which is further mixed with water to form brine. For the prevention
of chlorine reaction with NaOH is stop by the following three process:

 Mercury Cell
 Diaphragm Cell
 Membrane Cell

A salt solution is electrolyzed by the action of a direct electric current that transforms chloride ions to elemental
chlorine in each process. The overall process reaction is:

2NaCl + 2H2O → Cl2 + H2 + 2NaOH Eq 2.1

Chlorine is formed on anode but caustic soda and hydrogen is produced on cathode in above three processes. The
three processes contrast in the method by which the anode products are kept discrete from the cathode products.

2.1.1 Diaphragm Cell:

In Diaphragm cell anode territory is parted from cathode by a penetrable diaphragm. Then brine is commenced in
anode area by the way brine pass through diaphragm towards cathode. Diluted Caustic brine leaves the cell if
required the caustic soda can be concentrated to 50% and have any salt removed. The chlorine reaction with
caustic soda is prevent from porous diaphragm which is generally made up of asbestos fibers

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Chapter no 2 Process Selection

Figure 1 Diaphragm cell

Advantages:

 Use of Well Brine in diaphragm cell.

 It has Low Electrical energy Consumption

Disadvantages:

 Use of Asbestos is harmful when release into the product, ground or environment.

 Expansive multistage evaporators have high Steam Consumption for Caustic concentration.

 Diaphragm cell produces low purity Caustic.

 Diaphragm cell has low Chlorine quality.

 Cell Sensitivity to various conditions of pressure.

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Chapter no 2 Process Selection

2.1.2 Mercury Cell:

In this cell, the brine solution floats over mercury which reacts and form sodium mercury amalgam, and chlorine
bubbles out at anode and goes out of cell. But sodium, mercury amalgam reacts with water in which sodium
mercury amalgam decomposes to caustic soda, mercury, and hydrogen. Mercury is recycled to the cell. [1]

Reactions taking place in the cell are given below:

a) 2Cl- → Cl2 + 2e- Eq 2.2

+ -
b) Na + e → Na Eq 2.3
c) Na + Hg → Na/Hg (sodium amalgam, a dense liquid) Eq 2.4
d) 2Na/Hg + 2H2O → 2NaOH + H2 + 2Hg (slow reaction) Eq 2.5

The secondary reactor consists of carbon balls, which catalyze and increase the rate of this reaction. The sodium
hydroxide is manufactured at up to 50% concentration.

Figure 2 Mercury cell

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Chapter no 2 Process Selection

Advantages:

 50% of Caustic Soda from mercury cell is produced.

 Mercury cell produces high purity Chlorine and Hydrogen.
 There is simple brine purification in mercury cell.

Disadvantages:

 In mercury cell, cathode is made of mercury which is very toxic.

 Solid Salt is required to maintain the saturation of salt water in mercury cell but it has adverse effect on
environmental activities.
 Mercury cell has Expensive Cell Operation
 In mercury cell Environment Protection is costly.
 Large floor space in mercury cell. [3]

2.1.3 Membrane Cell:

The most common and productive for the production of caustic soda is membrane cell which involves the
electrolysis of brine. Used to prevent the reactions between chlorine and hydroxide ions made from a membrane
such as a nafion flamion and aciphex. Chloride (Cl −) is oxidized to chlorine at the anode. The ion-selective
membrane allows the cation Na+ to flow freely across but prevents anions such as hydroxide (OH −) and chloride
from spreading across. In cathode, water is reduced to hydroxide and hydrogen gas. Pure process is the
electrolysis of an aqueous solution of NaCl in industrially useful products sodium hydroxide (NaOH) and chlorine
gas. [1]

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Chapter no 2 Process Selection

Figure 3 Membrane cell

Advantages of Membrane Cell:

 Membrane cell has low capital investment.

 It has low total energy Consumption.
 It has Inexpensive cell operation.
 High purity Caustic soda is obtained in membrane cell.
 Membrane cell is insensitive to cell load variations and shutdowns.
 It is Environmental friendly process.
 It is extremely safe process.
 High quality caustic soda is obtained in membrane cell.

Disadvantages:

 High Purity brine is required in membrane cell.

 High cost of membranes.
 In membrane cell there is high oxygen content in Chlorine.

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Chapter no 2 Process Selection

2.2 Comparison of different cell Technologies:

Table 2.1 Brine Purification and Caustic Quality

Mercury Cell Diaphragm Cell Membrane Cell

High , < 30ppm NaCl 1.0-1.5% by weight NaCl

5-150 µg Hg/l
Caustic Quality (Before treatment the Hg
level is between 2.5-25
mg Hg/l)
(Before treatment the NaCl
High, < 50 ppm NaCl
content is about 18%)
0.1 % NaCl03
Not suitable for some application

33%,requires concentration to
12 % requires concentration
50% for some applications
Caustic to 50% for some
50% Concentration is done by evaporation
Concentration applications
using high pressure steam in a simple
evaporator.

Contains low levels of Oxygen content between 0.5%

Oxygen content between
Chlorine oxygen (<0.1%) and and 2% depending on whether an
1.5-2.5%
Quality hydrogen acidified electrolyte is used

Some purification Some purification required

required but depends on
Brine feed stock
purity of salt or brine used
Very high purity brine is required
but depends on purity of
as impurities affect membrane
salt or brine used
performance

Table 2.2 Comparison of mercury, diaphragm and membrane cell

Components Mercury Diaphrag Membrane

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Chapter no 2 Process Selection

m
Operating current density (kA/m2) 8-13 0.9-2.6 3-5
Cell voltage (V) 3.9-4.2 2.9-3.5 3.0-3.6
NAOH strength (wt. %) 50 12 33-35
Energy consumption (kwh/MTCl2) at a current density of (KA/m2) 3360(10) 2720(1.7) 2500(5)
Steam consumption (kwh/MT Cl2) for concentration to 50% NaOH 0 610 180
(“Sodium hydroxide.” : http://www.essentialchemicalindustry.org/chemicals/sodium-hydroxide.html.)

Table 2.3 Energy consumption of the end product in different processes

Diaphragm cell Membrane cell

Parameters Mercury cell method
method method
Cheaper relative to
Principal (constructional)cost Very high Cheapest
mercury method
To remove toxic Hg from Diaphragm must be Low maintenance
Operational cost
effluents frequently replaced cost
Energy consumption
3360 kWh 2720kWh 2500kWh
(per ton of Cl2 produced)
Energy requirement for
Concentration to 50% (w/w) None 700kWh 250kWh
(per ton of Cl2 produced)
Labor force required Least More Less
Brine, Hg can be reused Brine, H2 can be
Raw material renewal No
(though it is expensive) reused
Time of processing Least More Less
(“Sodium hydroxide.” : http://www.essentialchemicalindustry.org/chemicals/sodium-hydroxide.html.)

2.3 Selection of process:

When we compare diaphragm cell with membrane cell

 It is seen that diaphragm cell are clogged with use, therefore they are constantly replaced. While
membrane cell can be up to safety limit of 2 to 3 years.

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Chapter no 2 Process Selection

 Output limit of diaphragm cell up to 11% NaOH while NaCl is 15% and output of membrane is reached
up to 40%
 When we compare the titanium anode with graphite anode it is observed that graphite anode is less
dimensionally stable due to high chlorine potential.
 This high chlorine potential in graphite anode causing gradual oxidation of oxygen to CO 2 which result in
electrolytic ohmic drop and respectively high energy consumption than Titanium anode.
 The chlorine production is less in membrane cell than in diaphragm cell.
 The energy consumption of membrane cell is 15.2% less than diaphragm cell.
 Ni cathode enhances the operative, area causing high electrolytic and electrochemically active surface in
membrane cell.
 By comparing catalytic anode it is seen that membrane cell shows voltage saving of 100-120 mv and life
growth of about two years using ultra-pure brine.
 Membrane cell does not used harmful substances such as mercury or asbestos and there can be no
potential release of these materials into the product, ground or environment.
 Lowest power consumption when compared to mercury and diaphragm cells.
 Higher quality of sodium hydroxide produced when compared to the diaphragm cell.

2.4 Process Description:

Introduction to Membranes:

 Membranes are made from ion exchange polymers. The perfluorinated polymer provides
chemical and thermal stability similar to that of teflon. The polymer is permeable to cations and
can almost completely reject anions and non-polar species. They are used as separator in a wide
range of applications.

 The primary application for nafion membrane is production of chlorine and caustic by
electrolysis. This technology is environmentally sound and has become the preferred method
for chlorine and caustic production, having significant operating cost advantages over mercury
and diaphragm technologies.
 Other applications include electrochemical synthesis, spent acid regeneration ,metal ion recovery
and fuel cells
 About 40% of Chlor-alkali capacity

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Chapter no 2 Process Selection

 Over 20 cell types in use

 Electrode gaps from 0-3 mm
 Wide range of brine supplies to over 290 plants
 In 55 countries
 Safe and reliable plant operation
 Environment Friendly
 Achieve plant production schedule
 Minimize operating cost

2.5 Working of Membranes:

Solvated Na+, i.e. Na+ coupled to an electro-osmotic water flow migrate towards cathode passing
through the membrane from one fixed anionic groups to another and enter the cathodic compartment.
The membrane, which, in operation , can be approximately described as about 40 % by weight of an
aqueous solution of sodium ions in a matrix of polytetrafluoroethylene, to which negatively charged
groups are attached to make the membrane neutral. OH ions flow from cathode to anode is promoted by
the difference of OH ions concentration and by the direction of electric field across the membrane. The
hydroxyl ions can enter the membrane but once in does not move easily as it faces repulsive forces of
fixed negative charges from the region near the surface of the cluster and channels.

2.5.1 Physical Damage to Membranes:

1- Blistering

2- Pinhole Development

3- Cathode Layer Damage

Blistering:

Blistering is the separation of two layers. Typically these blisters are greater than 5mm in dia occur in
the electroactive area and increase voltage. Smaller microblister or voids in the carboxylate layer may
occur in the non active and active area decrease current efficiency. Either type of the blister is visible to

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Chapter no 2 Process Selection

the naked eye viewing the cathode side of the membrane. Blister may increase electrical resistance
causing uneven current distribution, weakens the membrane and lead to premature failure and should be
prevented.

Causes:

Table 2.4 Causes of Blistering in Membrane

Mechanism Causes
 Backward installation of membrane.
Elimination caused by high interlayer  Reverse water transport during shut down.
pressure  Excessive anolyte depletion.

 Excessive anolyte acidity.

Voids Caused by inadequate
 Too low temperature and too high concentration of
conductivity.
NaOH or brine
 Excessive local current density
Voids caused by precipitation in
 Anode side blinding
carboxylate layer
 Precipitation of impurities

Pinholes:

Pinholes are defined as small holes, normally less than 1mm in size, through the membrane sheet.If
affected area is small, voltage does not change.

Cathode Layer Damage:

The membrane cathode side layer may be physically damaged through precipitation of impurities and by
void formation in the cathode side layer decreasing current efficiency and occasionally in the thicker
anode side layer which can lower membrane resistance.

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Chapter no 2 Process Selection

2.5 Block Diagram of Membrane Cell:

Figure 4

2.6 Process Description:

Brine specifications of the cell process of membrane are much harder than mercury and diaphragm
process and demand impurities on surface of parts-per billion (ppb) level. The membrane will
deteriorate if it does not reach the surface. For this reason brine is purified in two parts. Brine is then
sent to the cell house to produce 32% Caustic Soda. Basic units of the industry are:

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Chapter no 2 Process Selection

 10 MW power plant including diesel generator & boiler house.

 1800 MT water storage tank including two-pump house & cooling tower.
 Bi-polar membrane cell house including rectifier, rectifier transformer, DCS control room.
 Anolyte & Catholyte tank, de-chlorination building as well as quality control department.
 Utility building including DM plant, Nitrogen plant, absorption chillers & compressors. This
block has got HCl synthesis building including storage tank and delivery platform.
 Primary & Secondary brine purification area including Salt Saturator, Reactor, Chemical Dosing
Tanks, Main Clarifier, Anthracite Filter, Candle Filter, Polished Brine Tank, Ion Exchange Resin
Column and Purified Brine Storage Tank.
 Automatic Salt Washer unit including separate storage area for raw & washed salt, conveyers,
small clarifier etc. Chlorine Drying & Compression Building including Bottling area as well as
four large storage tank and delivery platform.
 Caustic Evaporation and Flaking Building including bagging and storage facility.
 Hydrogen gas Compression and bottling building.
 Automatic Effluent treatment plant for industrial water treatment.

2.6.1 Primary brine purification section:

The raw material for the production is industrial salt and it contains some impurities which is to be
removed for good quality caustic soda

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Chapter no 2 Process Selection

Figure 5

Table 2.5 Composition of raw material

Composition Percentage
2+
Ca 0.227%
Mg2+ 0.049%
SO42- 0.645%
Total iron 13.2ppm
NaCl 95.43%
Moisture 3.649%
“Journal of Chemical Society of Pakistan Volume 29 No 6,” Chemical Society of Pakistan, 2007

Salt Washer Unit:

There is a fully automated modern salt washer unit to purify this imported salt. The raw salt is initially put in
hopper by a pay loader or robot and extracted by bucket lift screw conveyer. Salt is then dissolved in the salt
saturator. Then the saturated brine obtained is sent into the process of purification to remove impurities.

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Chapter no 2 Process Selection

Salt Saturator:

Pumping of return brain solution for melting of solid salt in salt saturator is under continuous process at about
85oC from return brine tank which is extracted from cell and not converted into caustic soda .The solution is
passes through a plate filter to remove the salt-bearing floating substance and impurities after melting the raw salt
in the salt saturator. Then the solution is fed to the dosing unit.

Regeneration:

Impurities or sludge that comes from salt dissolves at the bottom of the salt saturator and reduces the efficiency
of the salt saturator. Due to this the salt saturator is washed to make it clean.

Dosing:

From analysis of the raw salt the dissolved impurities are the Ca +, Mg+, SO42- and mud. Chemical doses are
required to remove these impurities BaCl 2 is used to remove the SO 42-. Na2CO3 is used to remove Ca+ and also
NaOH for the Mg+. After the dosing of these chemical dosing the salt solution is sent to the reactor for the proper
mixing. Five different dosing have been performed in this plant and these are as follows:

1. Soda Ash (Na2CO3) dosing

2. Barium Chloride (BaCl2) dosing 16

3. Sodium Sulphide (Na2SO3) dosing

4. Caustic Soda (NaOH) dosing

5. Flocculants dosing for production of 8333.33 kg/hr. Sodium hydroxide, 6385.774 kg/hr. salt is needed.

Chemical dosing:

Ca2+ in raw materials

 For removing Ca2+, Na2CO3 needed:

 NaOH needed for removing Mg2+:
 BaCl2 needed for removing SO4 2- :
 Reactor which is used here mainly a CSTR.

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Chapter no 2 Process Selection

In this reactor the following reaction occurs:

1. Na2SO4+BaCl2 → NaCl+BaSO4 Eq 2.6

2. Na2CO3+Ca2+ →CaCO3+2Na2+2NaOH Eq 2.7
3. +Mg2+ →Mg(OH)3 Eq 2.8

After complete mixing of the brine and dosing solution is added to a flocculent named solution called Megna floc
is added to the solution. Then the solution is send to the clarifier for the removing the precipitate of the solution
precipitation and also increasing the turbidity of the solution training. Reactor concentration range of brine is 310-
315 gpl and is continuously monitored by a Hydrometer. Reactor temperature is 60-65 oC and is continuously
monitored by a Thermometer.

Clarifier:

In the clarifier the soil, precipitated produced from the dosing which is carried out by the saturated brine solution
is precipitated in the bottom of the clarifier. Coarse solution of saturated brine from the bottom of clarifier is
pumped onto the decanter and mud is separated and collected to dispose off the sludge as waste product. The
brine solution extracted from the clarifier is stored in clarified brine tank and then send to anthracite filter for
removal floc particles.

Anthracite filter:

Filter medium of the anthracite filter is essential the anthracite. Solid adsorption has occurred, three types of
carbon: large, small and medium lies in the anthracite filter. When the brine solution is passed through the fine
anthracite filter medium the floc particles cannot pass through the medium and get trapped in the anthracite
medium. Then the solution is stored in the anthracite filter tank to make the process continuous.

Table 2 Primary Brine Purification

Impuritie Amount
s
SO4- 7-8 g/l
Mg 1.0-2.4 ppm
Ca 2.0-5.0 ppm
pH 10-11
Turbidity 1

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Chapter no 2 Process Selection

2.6.2 Secondary brine purification section:

Brine specification in the membrane cell process are much tougher mercury and diaphragm processes and the
discontent should be at ppb level. This is brine obtained in a pre-coat type secondary filter. The filtered brine of
the primary cleaning part is meet this requirement is also called a brine candle filter. [2]

Candle filter:

Candle filter is a special type of filter with filter medium is activated carbon and the filter aid is alpha cellulose.
This alpha cellulose blocks the micro level particles from the brine solution. To maintain the layer of the alpha
cellulose which is extracted externally into the upper surface of the activated carbon filter 1-2 atm pressure is
permanently removed. If the pressure reduced, there will be no more alpha cellulose layer on the activated carbon
filter. Alpha cellulose is constantly added to the candle filter to maintain filter aid performance. Brine solution is
feed at the bottom of the filter and a sludge free solution has emerged at the top of the filter. After filtering in the
candle filter the turbidity becomes -3 or -4 and brine solution is 3 to 4 times transparent than water.

Figure 6 Cross section of candle filter

Regeneration of candle filter:

The candle of the alpha cellulose is washed out using the previous flow of the air. The new alpha cellulose has
been added from the pre-coat tank.

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Chapter no 2 Process Selection

Ion Exchanger:

Multivalent ions exchange resin are exchange with the amino diacetic acid in ion exchange. But sodium is
monovalent ion so it is not exchange with this resin. Na ion is replaced by Ca 2+ and Mg2+. The resin used in an
ion-exchanger only passed Na+ and since it is a cation exchanger so Na+ so penetrated into cell house.

Figure 7 Ion exchanger

Regeneration of ion-exchange resin: Resin can work very well as long as its performance is high or moderate. But
when concentration of Ca2+ is less than 10 ppm and concentration of Mg 2+ is 2-3 ppb the bed is needed to
regenerate. The regeneration process is as follows:

Wash-1

As before the continuous flow washes the bed of resin with the demineralized water at constant flow 1600 L/h and
it lasts 1 hour as all ash and dust will washed.

Back wash:

Back wash is done by DM water at a flow rate of 1.6m 3/h over 30 minutes. DM water provided at the bottom of
the tower was circulate with water and resin tower. Water flow is maintained at a constant rate so that resin is not
overflowing. After making sure all the dishes washed and returned.

HCl regeneration:

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Chapter no 2 Process Selection

Then 18% concentrated HCl is supplied at 600 L/h flow rate over 30 to 50 minutes. By adding DM water at rate
1000L/h, 5% concentrated HCl made up. When the pH of HCl becomes 1 supply of HCL will closed. During the
maintenance of HCL 1 amino diacetic acid was replaced by Cl 2 and the media become acidic.

Wash-2:

To remove the acidic media then DM water provided at a flow rate 1600L/h over 1 hour. Consequently all Cl 2 will
replace by H+ ion of water.

NaOH regeneration:

Now 32% NaOH passed through the bed at a rate 200L/h with DM water of rate 1400L/h over 40 to 50 minutes.
As a result COOH of 1 amino diacetic acid will converted to COONa and resin regeneration will completed.

Wash-3:

Again the bed will washed with DM water at a flow rate of 1600L/h over 1 hour to maintain the pH 10. Water
supply stop if pH 10 is obtained.

2.6.3 Electrolyzer section:

Membrane technology is the unique Single Element, which consists an anode half shell, a cathode half shell and
an individual sealing system with external flanges. Single Elements are suspended in a frame and are pressed
against each other by a clamping device to form a "Bipolar stack”. Each Single element can be replaced quickly
and easily. The elements are assembled in the Electrolyser workshop, where tightness tests are also carried out.

Sodium hydroxide is produced (along with chlorine and hydrogen) via the Chlor alkali process. This involves the
electrolysis of an aqueous solution of sodium chloride. The sodium hydroxide builds up at the cathode, where
water is reduced to hydrogen gas and hydroxide ion:

1. 2Na++2H2O+2e- →H2+2NaOH Eq 2.9

2. 2Na++Cl-+2H2O+2e-→H2+2Cl-+2NaOH Eq 2.10

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Chapter no 2 Process Selection

The Cl- ions are oxidized to chlorine gas at the anode.

Figure 8 Cell House

In the process, three products are produced. It is vital that these are not allowed to mix. Thus, a requirement of a
commercial cell for the electrolysis of brine is that it separates the three products effectively. Electrolysis in a
simple vessel (described as a ‘one-pot’ vessel) leads to the reaction of chlorine with sodium hydroxide to give
unwanted sodium hypochlorite (NaClO), sodium chlorate (NaClO3) and oxygen by the following reactions:

1. Cl2+OH-→Cl-+HOCl Eq 2.11
2. HOCL→H++OCl- Eq 2.12
3. 2HOCl +OCl-→ClO3-+2Cl-+2H+ Eq 2.13
4. 4OH-→O2+2H2O+4e- Eq 2.14
5. Thus, in a commercial cell, sodium hypochlorite, sodium chlorate and oxygen could be formed as by-
products. To produce NaOH it is necessary to prevent reaction of the NaOH with the chlorine.
Important Feature of this Membrane:
 Perfluro Sulphonate Polymer act as an anode coating.
 Perfluro Carboxylate Polymer act as a cathode coating.
 High caustic flow is maintained as coating could not attach with the membrane body.
 Hence chlorine is a heavy gas so it pulled from separator by a compressor.
 This membrane is only permeable to Na+ ion.

2.6.4 Brine De-chlorination:

Removal of chlorine from Depleted brine. Brine is dechlorinated by three methods.

1) Vacuum Stripper
2) By addition of Sodium Sulfite
3) Activated Carbon

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Chapter no 2 Process Selection

Depleted brine from electrolyzer contains 0.3 g/l dissolved Cl2 at 3.5 – 4 pH & 1.0 g/l as available
chlorine in the form of Hypochlorite ions . depleted brine also carries 2000-2500 ppm of free chlorine.

Why removal of chlorates is necessary from the depleted brine?

1) The removal of impurities in the primary brine purification becomes difficult.

2) In the presence of high contents of chlorine, the impurities in the rock salt are more easily
dissolved during brine saturation.
3) Chlorine oxidizes ion exchange resins , hence increasing its consumption.
4) It decreases the sodium chloride solubility resulting in decreased efficiency , possible salt
precipitation and adverse chlorate conc in caustic Soda product.

Formation of chlorates

Chlorates are formed in the anodic compartment of the cell of electrolyzer via chemical or
electrochemical reactions. The side reactions taking place between chlorine and hydroxyl ions migrated
from cathodic side are as

4OH + CL2 CLO + CL + H2O

6CLO + 3H2O 2CLO3 + 4C + 1.5O2 + 6H + 6e

3CLO CLO3 + 2CL

Chlorates removal rate is a function of the

1) Chlorate concentration so that it is convenient to operate at a relatively high chlorate

concentration in the feed brine
2) High temperature is also favorable , a temperature of 85-90 C is recommended .
3) Low pH, A low pH less than 2 is favorable for removal of chlorates.

Process description

Depleted brine leaving the electrolyzer flows into the acidification pot 07D005 where it is mixed with
acidified stream of brine from reactor R-5050. Then it is collected in depleted brine storage tank
07D001. Brine is then pumped through 07P001A/B.

The discharge of the pump is divided into two streams.

a) One leads to vacuum stripper C-5010 (70-75%)

b) Second leads to acid mixing tank DM-5050.(25-30%)

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Chapter no 2 Process Selection

In DM-5050, 33% HCL is added to lower its pH almost zero, after acidification the brine flows down by
gravity into the reactor R-5050 where it is mixed with chlorinated steam coming from the vacuum
stripper C-5010.

Common ion effect

The common ion effect is the phenomenon in which the addition of an ion common to two solutes
causes precipitation or reduces ionization.

Le- Chatelier's principle,

It states that a reaction stays in equilibrium unless acted on by an outside force; then the reaction will
shift to accommodate the force and re-establish equilibrium.

This means that if you want a reaction to shift, you just apply an outside force, such as temperature,
concentration or pressure. In the case of the common ion effect, a reaction can be shifted by adding an
ion that is common to both solutes, thus changing the concentration of the ion in solution and shifting
the equilibrium of the reaction.

The net effect of the common ion is that it reduces the solubility of the solute in the solution. The
common ion effect can make insoluble substances more insoluble.

In the solution of an electrolyte in water, there exists an equilibrium between the ions & the unionized
molecules to which the law of Mass Action can be applied.

The common ion effect is used to reduce the concentration of one of the products in an aqueous
equilibrium. This may mean reducing the concentration of a toxic metal ion or controlling the pH of a
solution. The latter case is known as buffering.

Consider the ionization of an electrolyte;

AB ↔ A+ + B΄

[A+] [B΄] = K (ionization constant)

[AB]

If another electrolyte yielding the ions A+ or B΄ be added to the above solution, it will result in the
increase of concentration of the ion A+ or B΄. In order that K may remain the same, the concentration
[AB] must evidently increase.

In other words, the degree of ionization of a weak electrolyte is suppressed by the addition of another
strong electrolyte containing a common ion

In DM-5050, brine containing dissolved chlorine in the form of HOCL. As HCL is added , the
concentration of CL increases because HCL is highly ionized. The ionic product [OH] x [Cl-] thus

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Chapter no 2 Process Selection

considerably increases so much so that it exceeds the solubility product at the given temperature. The
results is a supersaturated solution of HOCL from which HOCL precipitate out in order to restore the
equilibrium.

HOCL + HCL CL2 + H20

HCL H + CL Strong electrolyte

HOCL OH +CL weak electrolyte

In R-5050, at low pH and high temperature, chlorates are decomposed, producing free chlorine which is
vented in the chlorine sniff line. The overflow of R-5050 entered in the acidification pot and lower the
pH of depleted brine ranging 1.5-2.0.

NaCLO3 + 2HCL NaCL + 1/2CL2+H20 + CLO2

NaCLO3 + 6HCL NaCL + 3CL2 + 3H20

These two reactions complete in the reaction mixture, but the second reaction is preferred to minimize
ClO2 production. To achieve this , 6 moles of acid per mole of NaClO3 and excess of Acid.

1) By Vacuum Stripper
Brine containing absorbed chlorine enters from the upper part of the packed tower C-5010 where
vacuum is generated by means of steam ejector. Henry law is applicable on this Vacuum Stripper.

Henry law

At constant temperature, the amount of given gas that dissolves in a given type and volume of liquid is
directly proportional to the partial pressure of that gas in equilibrium with that liquid.

OR

Solubility of a gas is directly proportional to the partial pressure of the gas.

C = KP

Where C= solubility of gas in liquid

K= henry Constant
P = Partial pressure of gas in liquid

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Chapter no 2 Process Selection

So here pressure is reduced via steam ejector and chlorine solubility in brine is reduced and is vented
off. Packing in the tower promote the intimate contact between the phases, thus increasing the
desorption process. Brine leaving the tower has 20-50 ppm of chlorine. The wet chlorine stripped from
the brine leaving the tower and is cooled in the heat exchanger E-5010. The condensed chlorinated water
is returned in the depleted brine Tank 07D001 while the chlorinated steam is sent to reactor R-5050.

Chlorate decomposer Tank R-5050

It is tank provided with a sparger pipe carrying low pressure steam and chlorinated steam from ejector.

The brine flows down by gravity in the dechlorinated brine Tank D-5020. The tank is vented to chlorine
sniff line.

Vacuum conditions = 0.62 kg/cm2

High alarm setting = 0.75 kg/cm2;

Low alarm setting = 0.48 kg/cm2

2) By Sodium Sulphite Treatment

Sodium sulphite is added to the depleted brine leaving the tank D-5020 by means of an in-line injection
on suction of p-5020A/B.

Sodium sulphite is prepared in the tank 5250-B by absorbing of So2 in sodium carbonate solution and
sent in D-5300 by means of P-5250A/B. Sulphur dioxide is prepared by burning Sulphur mud in the
Sulphur furnace which is sucked through an absorber by a blower. The gas is entered from the bottom of
the absorber and left from the top.

Sodium carbonate solution is prepared by adding 25kg of Na2CO3 in water in stirred tanks D-5250.The
sodium carbonate solution is fed from the upper side of the absorber and flows down back to the same
tank. When the solution is ready it is transferred in tank 5250A.

During chlorates decomposition , following reaction takes place

Na2SO3 + CL2 + H2O NA2SO4 + 2HCL

3) Activated Carbon.
After treatment with sodium sulfite, brine is passed through an activated carbon bed in tower C-5020.Care must
be taken that the carbon should work with acidic brine pH less than 2 and chlorine less than 50ppm.

a)High Cl2 contents in brine feeding to tower causes a violent reaction with Carbon, a vigorous increase of
absorption temperature & gas evaluation into the pores of carbon, with subsequent breaking of carbon.

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Chapter no 2 Process Selection

b)Relatively high PH (more than 3 causes carbon degradation in the form of finer particles which can plug the
tower

c)Very high pressure drops through C which breaks mechanically the carbon. Pressure drop across Carbon tower
= 0.8 bar( Alarm setting).

The brine passing out of the tower is made alkaline by the addition of dilute caustic effluent from tank D-5150 B
and Caustic Ring Tank. The pH is raised up to 6-9 before it is transferred in primary brine. Static mixer installed
in the line is used for mixing of caustic with acid and neutralization takes place.

NaOH + HCL NaCl + H20

When pressure drop across the carbon bed became more frequent, then it is packed with fresh activated carbon.
Normally this situation occurs after 40-45 days.

Caustic Temperature Across Evaporators:

E-203
Inlet 55 114-120 114-120
67-75 65-75 165-171
Tempereature
E-202
in 0C

2.6.4 Chlorine section:

Chlorine production and storage are consists of four basic section. These are follows:

 Drying section
 Compression section
 Liquefaction section
 Storage Very occasionally it can be used directly from the electrolyzers.

Extra chlorine are gas then send to chlorine unit. Chlorine gas leaving the electrolyzer is at approximately 80-90
ºC and saturated with water vapor. It also contains brine mist, impurities such as N 2, H2, O2, CO2 and traces of

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Chapter no 2 Process Selection

chlorinated hydrocarbons. Electrolyzers are mainly worked on atmospheric pressure with only a few milli-
atmospheres differential pressure between the anolyte and the Catholyte.

Drying section:

Drying of chlorine is done with about 78% concentrated sulphuric acid. Drying is obtained in counter-current
sulphuric acid contact towers. H2SO4 act as an adsorber and it adsorb almost all moisture present in chlorine. 98%
H2SO4 charges at the top side of tower which always keeps the downward pressure constant. Dry chlorine passes
through high efficiency reduction to prevent the growth of sulphuric acid droplets leaving the top of the drying
tower. 78% H2SO4 exit at the bottom of the tower and assemble permanently in the jar. [1]

Figure 9 Drying of Chlorine

Compression section:

After drying, chlorine gas might be scrubbed with liquid chlorine can be treated with ultra violet radiation to
reduce nitrogen trichloride levels. The dry chlorine is compressed into a centrifugal compressor to maintain outlet
pressure at 8 bar.

Liquefaction section:

Liquefaction can be obtained at different pressure and temperature levels, at ambient temperature and high
pressure (for example 18 ºC and 7-12 bar), at low temperature and low pressure (for example -35 ºC and 1 bar) or
any other intermediate combination of temperature and pressure in a reciprocating compressor. Freon-22 is used
as refrigerator. Liquefaction after converting gaseous chlorine into liquid chlorine and liquid Freon is converted to
gaseous Freon.

Storage section:

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Chapter no 2 Process Selection

The Liquid chlorine gas is then sent to storage tank at 8 bar in four tanks. Four tanks are collected so that one is
in production, one is in storage, one is in cleaning and other is in delivery.

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Chapter no 2 Process Selection

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Chapter no 2 Process Selection

Reference:

[1] O’Brien Thomas F. Hand Book of Chlor Alkali Technology, Springer, Boston, MA

[2] “Journal of Chemical Society of Pakistan Volume 29 No 6,” Chemical Society of Pakistan, 2007

[3] Haynes, William M., ed. (2011). CRC Handbook of Chemistry and Physics (92nd ed.).

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