Chlorination Roasting

• Isolate metal values and/or convert them

into a more amenable form
• Convert pure oxides to chlorides since
chlorides are easier to reduce than the
corresponding oxides

Ian Wark Research Institute

Australian Research Council Special Research Centre
For Particle and Material Interfaces
 Chlorination Roasting
May be conducted

1. Without volatilisation
2. With volatilisation
3. Segregation

Ian Wark Research Institute

Australian Research Council Special Research Centre
For Particle and Material Interfaces
 Chlorination Reactions with Cl2
• MO + Cl2 = MCl2 + 1/2O2
• MO2 + 2Cl2 = MCl4 + O2
• Possible only if the chloride is more stable
than the oxide
• ΔGo for chlorination reaction must be -ve

Ian Wark Research Institute

Australian Research Council Special Research Centre
For Particle and Material Interfaces
Free Energy of Chlorination Reactions

Ian Wark Research Institute

Australian Research Council Special Research Centre
For Particle and Material Interfaces
 Chlorination Reactions with Chlorides

• MO + 2HCl = MCl2 + H2O

• MO + MeCl2 = MCl2 + MeO
These can be broken into two reactions
• MO + Cl2 = MCl2 + 1/2O2
• H2O (MeO) + Cl2 = 2HCl (MeCl2) + 1/2O2
The yield is good only if the value of ΔGo for
second reaction is less negative than the first.
Volatilisation of MCl2 makes ΔGo more negative

Ian Wark Research Institute

Australian Research Council Special Research Centre
For Particle and Material Interfaces
 Chlorination Roasting
• Chlorination reaction is reversible so
oxygen must be continually removed as
soon as it forms to prevent metal oxide
reforming
• Can do this by adding carbon to the
mixture
• This also reduces ΔGoconsiderably

Ian Wark Research Institute

Australian Research Council Special Research Centre
For Particle and Material Interfaces
 Chlorination of TiO2
• TiO2 + 2Cl2 = TiCl4 + O2 ΔGo = +146 kJ
• TiO2 + 2Cl2 + C = TiCl4 + CO2 ΔGo = -251
kJ at 500oC
• At high temperatures CO will be formed
• C + CO2 = 2CO
• Can use CO instead of C
• MO + CO +Cl2 = MCl2 + CO2

Ian Wark Research Institute

Australian Research Council Special Research Centre
For Particle and Material Interfaces
Chlorination with CO present

Ian Wark Research Institute

Australian Research Council Special Research Centre
For Particle and Material Interfaces
 Titanium Tetrachloride Production
• All commercially produced titanium metal
is manufactured by reduction of titanium
tetrachloride with either molten Mg (Kroll
process) or Na (Hunter Process) in retorts
to form titanium sponge.
• Need to produce high purity titanium
tetrachloride to give high purity titanium

Ian Wark Research Institute

Australian Research Council Special Research Centre
For Particle and Material Interfaces
 Kroll Process

Ian Wark Research Institute

Australian Research Council Special Research Centre
For Particle and Material Interfaces
 Chlorination of Rutile

Ian Wark Research Institute

Australian Research Council Special Research Centre
For Particle and Material Interfaces
 TiCl4 Production
• Four materials may be chlorinated to
form titanium tetrachloride
1. Rutile (TiO2)
2. Leucoxene (hydrated TiO2)
3. Ilmenite (FeO.TiO2)
4. High titanium slags

Ian Wark Research Institute

Australian Research Council Special Research Centre
For Particle and Material Interfaces
 Synthetic Rutile
• Aim to produce high grade feed for TiCl4
production from inexpensive feedstock
such as ilmenite
• Partial chlorination is possible but
produces large quantities of FeCl3 which
must be disposed or dechlorinated to
regenerate chlorine

Ian Wark Research Institute

Australian Research Council Special Research Centre
For Particle and Material Interfaces
Ian Wark Research Institute
Australian Research Council Special Research Centre
For Particle and Material Interfaces
Synthetic Rutile: Kerr McGee Process

Ian Wark Research Institute

Australian Research Council Special Research Centre
For Particle and Material Interfaces
Synthetic Rutile AMA Process

Ian Wark Research Institute

Australian Research Council Special Research Centre
For Particle and Material Interfaces