EXTRACTION OF ALUMINIUM
ELECTRO REFINING OF ALUMINIUM :
HOOPE’S PROCESS: ( THREE LAYER PROCESS )
To achieve high degree of purity three layer processes are employed as
1. Bottom or Anode Layer: Specific gravity of this layer is maximum and consists of
impure Al alloyed with Cu. This layer serves as anode.
2. Middle or Electrolyte Layer: It consists of anhydrous fluorides and chlorides as AlF3
36%, Barium Fluoride 18%, and CaF2 16%.
3. Top or Cathode Layer: Pure Al layer acts as cathode.
Reaction (at anode) : Al ( liq) → Al+3 + 3e-
Reaction (at cathode) : Al+3 + 3e- → Al ( liq)
Purity of metal is 99.99%.
Fig. : Three-Layer Process
ANODE EFFECT :
If alumina content of bath (normally 5-10%) falls below 2% then normal contact
between the anode and bath is interrupted by the gas film in which abruptly increases
positive resistance. As a consequence the normal operation ceases. This effect is
called anode effect. Under certain conditions, the electrolytes of fused salt is
associated with the periodically occurring phenomena in which the terminal voltage
increases to high value and current density decreases to a lower value from their
normal value. This effect is known as anode effect.
If power consumption, electrolyte, and anode consumption increases during the
process. Then, current density exceeds above critical current density.
FACTORS AFFECTING ANODE EFFECT:
(i) Nature of electrolyte: Anode effect occurs most readily with fluoride and least
with iodides, Bromides and Chlorides required large critical current density than
iodide, fluoride both.
(ii) Purity of electrolyte: Greater purity lower in current density and vice verse.
(iii) Type of electrolytic Anode: The cryolite-Alumina melt anode effect at 4-5
amp/sq. cm. when C anode used and 7-8 amp/sq. cm. for graphite electrode.
(iv) Temperature: Increase in temperature reduces the current density.
CAUSE OF ANODE EFFECT:
Thermal Effect: Local overheating can lead formation of gaseous film which
deposits anode from electrolyte.
Electrostatic Causes: During electrolysis, gas bubbles form which is electrically
charged. The charge may be originated from the anions discharged at the boundary of
newly form gas bubbles at high current density. So, gas is partly ionized when gas
bubbles acquires opposite charge to that electrode i. e. negative charge there will be
formation of adherent gaseous film which could separate the molten electrolyte from
anode.
Role of Cryolites in Electrolysis: Al2O3 dissolve in cryolite and form Al+3 , O -2
(in
solute) and Na+ , AlF+3 , F- (in solvent).
Cathodic Reaction: Al2O3 → Al+3 + AlO32-
Al 3+ + 3e- → Al
Anodic Reaction: 2AlO2- → Al2O3 + 3[O] + 2e -
6F - + Al2O3 → 2AlF3 + 3[O] + 6e-
FACTORS AFFECTING ELECTROLYSIS:
1. Temperature: Increase in temperature, current efficiency increase. For every 40C rises
1% current efficiency increase. More number of side reaction and hence dissociation of metal
in bath.
2. Current Density: Current efficiency increase with increase in current density.
3. Inter polar Distance: As the distance increases along the bath from bottom to top,
current efficiency also increases.
4. Addition of Al2O3: At Al2O3 % is 4%, there no effect on current efficiency. But, decrease
or increase in Al2O3 from 4% cause increase or decrease in current efficiency.
5. Bath Density: With increase in bath density by AlF3 /NaF ratio. But, for large AlF3 %
cause bath conductivity and fluidity decreases and volume increases i. e. current efficiency
decreases.
