Chlor-alkali Industries

Major Chemicals
• Soda ash (Sodium carbonate- Na2CO3)
• Caustic Soda (Sodium hydroxide- NaOH)
• Chlorine (Cl2)
Sodium carbonate
• Molecular weight 106
• M.P 8510C
• B.P Decomposes
• Soluble in water 8.9 gm per 100 gm at 200C
Uses
Methods of Production
• Le Blanc process- 1773

• Gypsum or Calcium sulphate was the troublesome side product

• Solvay or ammonia soda process- 1864

• Dual process (Na2CO3 + NH4Cl)
• Natural soda ash from deposits
• Trona ore (Sodium sesquicarbonate) found in US

• Heating the ore gives soda ash

Solvay process

Overall reaction: CaCO3 + 2 NaCl  Na2CO3 + CaCl2

Raw materials
• Salt (NaCl)
• Limestone
• Ammonia
• Coke
• Steam
Process
• Ammonia is dissolved in NaCl solution
• Then reacted with CO2.
• A precipitate of NaHCO3 is obtained
• This is calcined to produce Na2CO3
Process
• Ammonia is dissolved in NaCl solution
NH3 + H2O  NH4+ + OH-
• Then reacted with CO2.
CO2 + OH-  HCO3-
CO2 + H2O  HCO3- + H+
Na+ + Cl- + NH4+ + HCO3- NH4+ + Cl- + NaHCO3
• A precipitate of NaHCO3 is obtained
Na+ + Cl- + NH4+ + HCO3- NH4+ + Cl- + NaHCO3
• This is calcined to produce Na2CO3
2NaHCO3  Na2CO3 + CO2+ H2O
Solvay process
Reactions
Solvay process
a) Overall reaction: CaCO3 + 2 NaCl  Na2CO3 + CaCl2
b) CaCO3  CaO + CO2
c) C + O2  CO2
d) CaO + H2O  Ca(OH)2
e) NH3 + H2O  NH4+ + OH-
f) CO2 + OH-  HCO3-
g) CO2 + H2O  HCO3- + H+
h) Na+ + Cl- + NH4+ + HCO3- NH4+ + Cl- + NaHCO3
i) 2NaHCO3  Na2CO3 + CO2+ H2O
j) 2NH4Cl + Ca(OH)2  2 NH3 + CaCl2 + 2 H2O
Major engineering problems
• Development of suitable calcining equipment
• Carbonating tower design
• Ammonia recovery
• Waste disposal
Modified Solvay (Dual Process)
• NH4Cl is recovered as a co-product
• Liquor from bicarbonate filter is mixed with washed
salt to precipitate NH4Cl
• It is crystallized in refrigerated tanks at 00C
• Slurry is centrifuged and crystals are dried in rotary
drum hot air dryer
• Packed for shipping
Major Engineering Problems
• Salt purification
• Corrosion
• Refrigeration
Industries
• Manufacturing Na2CO3