Unit 2

Chemical Process Technology I

Lesson 1
Chlor-Alkali industry
Chlor-Alkali industry
Chlor-alkali industry produces three major chemicals
Caustic soda (NaOH), Chlorine (Cl2) and Soda ash (Na2CO3)
uses rock salt (natural deposit of sodium chloride) or brine (aqueous solution
of sodium chloride) Ex: sea water or inland salt lakes
by electrolysis of this solution produces simultaneously chlorine, sodium
hydroxide and hydrogen.
Soda ash is produced mostly by Solvay process
Soda Ash
• Soda ash is sodium carbonate (Na2CO3) used in large quantities in glass, textile,
soap, and paper industries.
• Soda in Latin refers to certain kind of plants and in 18 th century sodium carbonate
was obtained from the ash of these plants and hence this name.
• Produced by Leblanc process in 19th century ;
Step I: Sodium chloride is treated with sulfuric acid yielding salt cake.

Step 2: Mixture of the salt cake, crushed limestone heated with coal.
;
• Soda ash is extracted from the black ash with water. Evaporation of this extract
yields solid sodium carbonate.
• Polluting process and became obsolete.
Ammonia absorption

tower
Soda Ash
Dual or Modified Solvay Process
• This process does not use limestone in contrast to Solvay process.
• Carbon dioxide (from shift converters or thermal power plants) is used.
• Lime kiln and the ammonia recovery sections in Solvay process are replaced with
ammonium chloride section where ammonium chloride is from ammoniated brine
solution by cooling followed by filtration.
• The end products are ammonium chloride and soda ash.
• These plants are located nearer to the fertilizer plants.
Natural Soda ash
• 25 per cent of the world soda ash production is from natural sodium carbonate bearing
deposits
Ex. Trona, trisodium hydrogen dicarbonate dihydrate (Na2CO3. NaHCO3·2H2O).
• Trona is calcined in a rotary kiln and converted to soda ash, carbon dioxide and water.
• Almost entire soda ash production in USA is from such deposits.
Electrolytic Processes for Caustic Soda
Types of electrolysis cells
1. Diaphragm cell
2. Mercury cathode cell
3. Membrane cell
Nelson Diaphragm cell
Nelson Diaphragm cell
• consists of a perforated steel tube having a thin lining of asbestos on the inside.
• steel tube acts as the cathode and is suspended in side a outer tank.
• Brine solution is introduced into this tube in which graphite anode is kept immersed.
• Cl- ions in the brine solution attracted to anode, get oxidized to Cl 2 gas, which leave
through the outlet on the right side.
• Brine solution seep through the asbestos lining and reaches the underlying steel cathode.
• Water is a weak electrolyte, feebly dissociates
H2O ↔ H+ + OH-
• Na+ and H+ both are attracted to steel cathode.
• only the H+ get reduced to H2 gas due to its high reduction potential and leave through the
outlet in the outer vessel.
• solution containing Na+, OH- and unreacted Cl- are collected in the outer vessel.
Nelson Diaphragm cell
• solution is evaporated by steam.
• concentrated solution is cooled to crystallize out NaCl and filtered.
• concentrated NaOH solution is obtained.
Disadvantages
• The NaOH solution is still contaminated with NaCl.
• Products chlorine attack caustic soda solution even in the cold, resulting in sodium
chloride and hypochlorite.

• To preclude the above reaction, it is necessary that NaOH and Cl 2 once formed
must not come in to contact with one another.
• This is done in the Castner-Kellner cell.
Castner-Kellner cell
 consists of large rectangular tank,
divided into three compartments.
 layer of the mercury at the
bottom, circulated from one
compartment to another by the
movement of eccentric wheel.
 Compartment A and C are fitted
with graphite anodes dipped in
brine and mercury act as cathode
by induction.

At Graphite Anode
2Cl- → Cl2 + 2e-
At Mercury cathode
Na+ + e- → Na (amalgam)
Castner-Kellner cell
 Chlorine formed at graphite anode leaves the compartments A and C.
 sodium formed at mercury cathode dissolves in mercury, forming amalgam which move
to central compartment.
 Iron roads suspended in the central compartment filled with water act as cathodes and
here mercury act as anode by induction.
At Iron cathode At Mercury anode
2H2O + 2e- → 2OH- + H2 2Na(amalgam) + 2OH- → 2NaOH + 2e-

 OH¯ ions move to the mercury anode and react with the sodium in the amalgam to form
sodium hydroxide and comes to aqueous layer.
 solution of NaOH is formed in the central compartment.
 Advantage
NaOH is not contaminated by NaCl.
 Disadvantage
toxic nature of mercury
 
Membrane Cell
Membrane Cell

Advantages:
• More concentrated brine can be used.
• Purer and concentrated products (28% NaOH containing 50 ppm of NaCl) are
produced.
• Saving of energy and transportation cost
Disadvantages
• Membrane gets clogged readily
• Pretreatment of brine is required to remove calcium and magnesium salts
Thank You