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Chapter - 4 - The Chlor-Alkali Industry
Chapter - 4 - 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
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
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.
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
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.
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
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.
.
water
DC power
(Mercury and
membrane)
(Diaphragm)
Chlorine Hydrogen
Caustic soda
The energy requirement of cell
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