The electrolytic process replaced the Wöhler process, which involved the reduction of anhydrous aluminium chloride with potassium. Both of the electrodes used in the electrolysis of aluminium oxide are carbon. Once the refined alumina is dissolved in the electrolyte, its ions are free to move around. The reaction at the cathode (negative electrode) is
Al3+ + 3 e− → Al
Here the aluminium ion is being reduced (electrons are added). The aluminium metal then sinks to the bottom and is tapped off.
At the anode (positive electrode), oxygen is formed:
2 O2− → O2 + 4 e−
This carbon anode is then oxidized by the oxygen, releasing carbon dioxide.
O2 + C → CO2
The anodes in a reduction cell must therefore be replaced regularly, since they are consumed in the process.
Unlike the anodes, the cathodes are not oxidized because there is no oxygen present, as the carbon cathodes are protected by the liquid aluminium inside the cells. Nevertheless, cathodes do erode, mainly due to electrochemical processes and metal movement. After five to ten years, depending on the current used in the electrolysis, a cell has to be rebuilt because of cathode wear.
World production trend of aluminiumAluminium electrolysis with the Hall-Héroult process consumes a lot of energy, but alternative processes were always found to be less viable economically and/or ecologically. The worldwide average specific energy consumption is approximately 15±0.5 kilowatt-hours per kilogram of aluminium produced (52 to 56 MJ/kg). The most modern smelters achieve approximately 12.8 kW·h/kg (46.1 MJ/kg). (Compare this to the heat of reaction, 31 MJ/kg, and the Gibbs free energy of reaction, 29 MJ/kg.) Reduction line currents for older technologies are typically 100 to 200 kA; state-of-the-art smelters operate at about 350 kA. Trials have been reported with 500 kA cells.
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