Chapter -4

THE CHLOR-ALKALI INDUSTRY

 5. The chlor- alkali industry

Introduction
The Chlor-alkali process is an industrial process for the
electrolysis of sodium chloride. It is the technology used to
produce chlorine(Cl2) and alkali such as sodium hydroxide
(caustic soda) NaOH, which are commodity chemicals required by
industry.
Usually the process is conducted on a brine (an aqueous solution
of NaCl), in which case NaOH, hydrogen, and chlorine result.
When using calcium chloride or potassium chloride, the products
contain calcium or potassium instead of sodium. Related processes
are known that use molten NaCl to give chlorine and sodium metal
or condensed hydrogen chloride to give hydrogen and chlorine.
5.1. Properties of chlorine and caustic soda

I. Chlorine
Chlorine is widely distributed in nature although not as a free
element. Approximately two percent of the earths surface
material is chlorine which is mostly in the form of sodium
chloride in sea water and in natural deposits as
carnallite(MgCl2.KCl.6H2O) and as sylvite (KCl).
Chlorine is very poisonous gas and has a choking and irritating
odor. It must be handled with care.
The gas is greenish yellow in color and the liquid is clear amber.
Chlorine, gas or liquid, is non-explosive and non-flammable.
Chlorine is only slightly soluble in water, 0.3 to 0.7 percent. At
ordinary temperatures dry chlorine, gas or liquid, reacts with
aluminum, arsenic, gold, mercury, selenium, tin, and titanium.
Physical properties of chlorine

Physical properties parameters

Molecular weight 71 g/mole
Boiling point (liquefying point) -34C
Freezing point (or melting point) 100.98C at 1 atm
Solubility in water 1% 10C; 0.5% at 37.8C
Density
gas at standard conditions 3.213kg/m3 at STP
saturated gas 12.23 Kg/m3 at 0C
saturated liquid 1467 kg/m3 0C
Latent heat of vaporization 288.1 kg/kg, 20.41 kJ/mol
Heat of fusion 6.406kJ/mol
Specific heat Dry gas 0.113 gcal/g/C at 100 psia
Or less and 30.1 C to 26.7C
LC50 (Gas) 293 ppm/vol
 II. Caustic soda

Pure caustic soda or sodium hydroxide is a white solid available in

pellets, flakes, granules and can be a 50% saturated solution.
Caustic soda, as a 50% solution, is an odorless and colorless liquid.
In all forms caustic soda is highly corrosive and reactive. It reacts
with metals such as aluminum, magnesium, zinc, tin, chromium,
bronze, brass, copper, and tantalum.
It reacts with most animal tissues, including leather, human skin,
and eyes. It also reacts with various reducing sugars(i.e. fructose,
glucose, maltose, dry whey solids) to produce carbon monoxide.
Upon cooling, the viscosity of the solution increases rapidly as the
temperature falls below 18C.
Physical properties of NaOH

Physical properties Parameters

Molecular weight 40
PH 14
Vapor pressure 0.20 Kpa at 20C
Boiling point 145C
Freezing point 14C
Specific gravity at 20C 1.52 g/ml
Specific heat J/g C at 20C 1388
Refractive index at fusion, J/g 1.433
Lattice energy, KJ/mole 737.2
Entropy, J/mole at 25C and 101.3 Kpa 64.45
Heat of formation, KJ mol -1
form 422.46
form 426.6
Transition temperature, C 299.6
Free energy of formation, kg-cal/mol/K 12.43
at 25C, 760 mm Hg
5.2. Application and use of chlor- alkali industries

The application and use of chlorine

PVC(38%)

Other(20%) (pesticides,
pharmceuticals, water
treatment)
10% C1 and C2
12% derivatives(14%)(solvent,
38% refrigrants,floropolymer)
propylene oxide(12%)
14%
Phosgene(10%)(polycarbo
20% nates)

Hydrochloric
acid(3%)(Food processing)

Sodium
hypochlorite(3%)(bleachin
g disinfectant)
The application and use of caustic soda(NaOH)

.
5.3. GLOBAL PRODUCTION

Countries %sharing
.
United 26%
states(USA)
Western Europe 22%

Japan 10%

China 13%

Eastern Europe 6%
 5.4. Process technology

Chlorine, caustic soda and hydrogen are produced via electrolysis

of NaCl salt solution and this process requires intensive brine
purification and large inputs of electricity.
Electricity cost can reach about 60% of the production variable
cost
The electrolysis process cell that produce chlorine, sodium or
potassium hydroxide and hydrogen is classified in to three basic
processes on the nature cathode and anode reaction.
The three basic electrolytic (chlor-alkali) process processes.
a) The diaphragm cell process

b) The mercury cell process

c) The membrane cell processes

CONT

In all 3 methods, the chlorine (Cl2) is produced at the positive electrode

(anode) and the caustic soda(NaOH) and hydrogen (H2) are produced,
directly or indirectly, at the negative electrode (cathode).
The 3 processes differ in the method by which the anode products are
kept separate from the cathode products.

Chloride ions are oxidized and chlorine (Cl2) is formed at the anode in
all the three cells. In the cathode section of the mercury process a
sodium/mercury amalgam is formed and hydrogen (H2) and hydroxide
ions (OH-) are formed by the reaction of the sodium in the amalgam
with water in the denuder to finally form caustic soda.

In cathode compartments of the membrane and diaphragm cell, water

decomposes to form hydrogen (H2) and hydroxide ions(OH-) at the
cathode to react with sodium ion to produce caustic soda.
A) The diaphragm cell technology

The process differs from the mercury cell process in that all reaction
take place with in one cell and the cell effluent contains both salt and
caustic soda.
The diaphragm is employed to separate the chlorine liberated at the
anode, and the hydrogen and caustic soda produced directly at the
cathode. The diaphragm is usually made of asbestos and separates the
feed brine (anolyte) from the caustic- containing (catholyte).
The anode compartment was filled with saturated brine get ionized
by the action of electrical energy.
During the electrolysis of NaCl brine, chlorine is generated at the
anode. The sodium ions, along with sodium chloride and water,
percolated through the diaphragm in to the cathode compartment
from which sodium hydroxide is produced at the cathode.
Diaphragm cell operating principle
Cont

The ionic reactions taking place at anode and cathode compartments are
presented below.
Anode compartment
NaCl ionization 2NaCl 2Na+ + 2Cl-
Anode reaction 2Cl- Cl2 + 2e
Cathode compartment
Cathode reaction 2H2O + 2e- H2 + 2(OH)-
2NaCl + 2H2O 2NaOH

Overall reaction: 2NaCl + 2H2O 2NaOH + Cl2 + H2

The diaphragm cell have the advantage of operating at a lower voltage than
mercury of cell and can use less pure brine than required by membrane cell.
.
B) Mercury cell process

Mercury cell process involves two cell. The first cell is called
primary cell or electrolyser while the second one is known as
secondary cell or denuder/decomposer.

In the primary cell or electrolyser, purified and saturated brine

flows through an elongated trough that is slightly inclined from
the horizontal. In the bottom of this trough a shallow film of
mercury(Hg) flows along the brine co-currently with the brine.

Electric current flowing through the cell decomposes the brine

passing through the narrow space between the electrodes,
liberating chlorine gas (Cl2) at the anode and sodium hydroxide
(NaOH) at the cathode as per the following reaction.
CONT

Anode compartment: Reaction in the primary cell/electrolyser

2NaCl 2Na+ + 2Cl-
2Na+ + 2Cl- + 2Hg 2NaHg + Cl2(g)
Cathode compartment: Reaction in the secondary
cell/denuder/decomposer
2NaHg + 2H2O 2Na+ + 2OH- +H2(g) + 2Hg
2Na+ + 2OH- 2NaOH
A saturated brine solution floats on top of the cathode which is a thin
layer of mercury.
Chlorine is produced at the anode, and sodium is produced at the
cathode where it forms a sodium-mercury amalgam(NaHg) with the
mercury.
The chlorine is removed from the anode, cooled, dried, and
compressed.
 Mercury cell operating scheme

Reaction at the anode Chlorine(Cl2)

2 Cl- Cl2 + 2e-

Anode
Brine NaCl & Depleted brine
H2O

Power
supply
Cathode Mercury &
Hydrogen gas(H2)
Sodium
Reaction at the cathode
2 Na+ 2 Hg + 2e- 2 Na/Hg

Recycled 50% caustic soda

(NaOH)
mercury (Hg)
CONT..

The liquid Na/Hg amalgam then flows to a secondary reactor or

decomposer where reaction with water leads to the production
of hydrogen gas and concentrated sodium hydroxide.
The caustic and hydrogen are then separately cooled and the
mercury is removed before proceeding to storage, sales, or other
processes.
The mercury is then recycled to the primary cell. The mercury cell
is the least energy-efficient of the three designs, and also clearly
has the potential for loss of mercury to the environment, either as a
residue in the caustic soda product or due to handling or
evaporative losses.
Environmental concerns and legislation have led to a steady
decline in the use of mercury cells for chlorine production and
their replacement by membrane cell technologies that do not use
mercury.
.
C) The membrane cell process

The membrane cell is currently the most promising and fast-

developing technique for the production of chlor-alkali industries
and it is in the process of replacing the other two cell/techniques.
This can be deduced from the fact that practically 100% of the
new chlor-alkali plants currently established world-wide apply the
membrane process technology.
In this process, the anode and cathode are separated by a water-
impermeable ion-conducting membrane.
During the electrolysis of NaCl brine, chlorine is generated at the
anode while sodium hydroxide and hydrogen gas are produced at
the cathode in accordance to the following reactions.
CONT..

Anode compartment
NaCl ionization 2NaCl 2Na+ + 2Cl-
Anode reaction 2Cl- Cl2 + 2e-
Cathode compartment
Cathode reaction: H2O + 2e- H2 +2OH-
2Na+ + 2OH- 2NaOH
Brine solution flows through the anode compartment where
chloride ions are oxidised to chlorine gas.
The demineralized water added to the catholyte circuit is
hydrolysed, releasing hydrogen gas(H2) and hydroxide ions(OH-).
The sodium and hydroxide ions combine to produce caustic soda
which is typically brought to a concentration of 32-35% by
recirculating the solution before it is discharged from the cell.
Membrane cell operating scheme
CONT.

The membrane prevents the migration of chloride ions from the

anode compartment to the cathode compartment; therefore, the
caustic soda solution produced does not contain salt as in the
diaphragm cell process.
The membrane process not only saves energy, it also produces
consistently high-grade caustic soda.36.
Depleted brine is discharged from the anode compartment and
resaturated with salt. If needed, to reach a concentration of 50%
caustic soda, the caustic liquor produced has to be concentrated by
evaporation (using steam).
The cathode material used in membrane cells is either stainless
steel or nickel. The anodes used are metal and usually titanium.
The membranes used in the chlor-alkali industry are commonly
made of perfluorinated polymers.
CONT..

Membrane cells have the advantage of producing a very pure

caustic soda solution and of using less electricity than the other
processes . In addition, the membrane process does not use highly
toxic materials such as mercury and asbestos.
Disadvantages of the membrane process are that the caustic soda
produced may need to be evaporated to increase concentration
and, for some applications, the chlorine gas produced needs to be
processed to remove oxygen.
Further more, the brine entering a membrane cell must be of a
very high purity, which often requires costly additional
purification steps prior to electrolysis.
.
5.4. Major unit operation of chlor alkali industries

The unit operations employed in chlor-alkali industries can divide in

to three major processing houses. These processing houses are:
I. Brine purification house
II. Brine electrolysis house

III. Cell product treatment house

The major difference of the processing house of the three cell

technologies used in chlor-alkali industries is in the operation of
the cell/brine electrolysis house and in concentrating the caustic
soda output of each cell at the product treatment house.
There is a little or no difference in the content and arrangement
of unit operation(U.Os) involved in brine purification house as
well as in the processing of chlorine gas coming from all the cell
at product treatment house.
Major processing house of electrolytic chlor-alkali industries

.
water

CP salt depleted brine

DC power
(Mercury and
membrane)

(Diaphragm)

Chlorine Hydrogen
Caustic soda
The energy requirement of cell

The electrical energy required to produce chlorine and caustic soda

constitutes a major portion of the operating cost of chlor-alkali
industries.
Least energy cost is observed in membrane cell technology which is
35% less than the energy cost of diaphragm cell.
Although, the cost of electrical energy of mercury cell is higher than that
of diaphragm cell and much higher than the membrane cell, its steam
consumption is the least one which makes the total energy cost of
mercury cell to be 10% less than that of diaphragm cell.
Diaphragm cell plant with 10-12% cell liquor are the largest steam
consumers which is 2.5 tons per ton NaOH. In membrane cell plant, it is
0.5 tons per ton NaOH. Most mercury cell plant not major consumers of
steam.
Diaphragm cell and membrane cell requires multiple effect evaporation
to concentrate the alkali solution coming out of the cell 10-12% NaOH
to 50% NaOH in case of diaphragm and from 30-35% NaOH to 50%
Figure : The overall flow to storage of caustic soda from the different
technologies
.

Thank you!!!!