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Aluminium smelting is the process of extracting aluminium from its oxide, alumina, generally by the Hall-Héroult process. Alumina is extracted from the ore bauxite by means of the Bayer process at an alumina refinery.
This is an Electrolysis process, so an aluminium smelting uses huge amounts of electric power; smelters tend to be located close to large power stations, often hydro-electric ones, in order to hold down costs and reduce the overall carbon footprint. Smelters are often located near ports, since many smelters use imported alumina.
An aluminium smelter consists of a large number of cells (pots) in which the electrolysis takes place. A typical smelter contains anywhere from 300 to 720 pots, each of which produces about a ton of aluminium a day, though the largest proposed smelters are up to five times that capacity. Smelting is run as a batch process, with the aluminium deposited at the bottom of the pots and periodically siphoned off. Particularly in Australia these smelters are used to control electrical network demand, and as a result power is supplied to the smelter at a very low price. However power must not be interrupted for more than 4–5 hours, since the pots have to be repaired at significant cost if the liquid metal solidifies.
Although the formation of carbon monoxide (CO) is thermodynamically favoured at the reaction temperature, the presence of considerable overvoltage (difference between reversible and polarization potentials) changes the thermodynamic equilibrium and a mixture of CO and is produced.K. Grjotheim and C. Krohn, Aluminium electrolysis: The chemistry of the Hall-Heroult process: Aluminium-Verlag GmbH, 1977.F. Habashi, Handbook of Extractive Metallurgy vol. 2: Wiley-VCH, 1997. Thus the idealised overall reactions may be written as
By increasing the current density up to 1 A/cm2, the proportion of increases and carbon consumption decreases.
As three electrons are needed to produce each atom of aluminium, the process consumes a large amount of electricity. For this reason aluminium smelters are sited close to sources of inexpensive electricity, such as hydroelectric.
Cathode: Carbon cathodes are essentially made of anthracite, graphite and petroleum coke, which are calcined at around 1200 °C and crushed and sieved prior to being used in cathode manufacturing. Aggregates are mixed with coal-tar pitch, formed, and baked. Carbon purity is not as stringent as for anode, because metal contamination from cathode is not significant. Carbon cathode must have adequate strength, good electrical conductivity and high resistance to wear and sodium penetration. Anthracite cathodes have higher wear resistance and slower creep with lower amplitude 15 than graphitic and graphitized petroleum coke cathodes. Instead, dense cathodes with more graphitic order have higher electrical conductivity, lower energy consumption 14, and lower swelling due to sodium penetration. Swelling results in early and non-uniform deterioration of cathode blocks.
Anode: Carbon anodes have a specific situation in aluminium smelting and depending on the type of anode, aluminium smelting is divided in two different technologies; "Soderberg" and "prebaked" anodes. Anodes are also made of petroleum coke, mixed with coal-tar-pitch, followed by forming and baking at elevated temperatures. The quality of anode affects technological, economical and environmental aspects of aluminium production. Energy efficiency is related to the nature of anode materials, as well as the porosity of baked anodes. Around 10% of cell power is consumed to overcome the electrical resistance of prebaked anode (50–60 μΩm). Carbon is consumed more than theoretical value due to a low current efficiency and non-electrolytic consumption. Inhomogeneous anode quality due to the variation in raw materials and production parameters also affects its performance and the cell stability.
Prebaked consumable carbon anodes are divided into graphitized and coke types. For manufacturing of the graphitized anodes, anthracite and petroleum coke are calcined and classified. They are then mixed with coal-tar pitch and pressed. The pressed green anode is then baked at 1200 °C and graphitized. Coke anodes are made of calcined petroleum coke, recycled anode butts, and coal-tar pitch (binder). The anodes are manufactured by mixing aggregates with coal tar pitch to form a paste with a doughy consistency. This material is most often vibro-compacted but in some plants pressed. The green anode is then sintered at 1100–1200 °C for 300–400 hours, without graphitization, to increase its strength through decomposition and carbonization of the binder. Higher baking temperatures increase the mechanical properties and thermal conductivity, and decrease the air and CO2 reactivity.W. K. Fischer, et al., "Baking parameters and the resulting anode quality," in TMS Annual Meeting, Denver, CO, USA, 1993, pp. 683–689 The specific electrical resistance of the coke-type anodes is higher than that of the graphitized ones, but they have higher compressive strength and lower porosity.M. M. Gasik and M. L. Gasik, "Smelting of aluminum," in Handbook of Aluminum: Volume 2: Alloy production and materials manufacturing. vol. 2, G. E. Totten and D. S. MacKenzie, Eds., ed: Marcel Dekker, 2003, pp. 47–79
Soderberg electrodes (in-situ baking), used for the first time in 1923 in Norway, are composed of a steel shell and a carbonaceous mass which is baked by the heat being escaped from the electrolysis cell. Soderberg Carbon-based materials such as coke and anthracite are crushed, heat-treated, and classified. These aggregates are mixed with pitch or oil as binder, briquetted and loaded into the shell. Temperature increases bottom to the top of the column and in-situ baking takes place as the anode is lowered into the bath. Significant amount of hydrocarbons are emitted during baking which is a disadvantage of this type of electrodes. Most of the modern smelters use prebaked anodes since the process control is easier and a slightly better energy efficiency is achieved, compared to Soderberg anodes.
The Soderberg process which bakes the Anthracite/pitch mix as the anode is consumed, produces significant emissions of polycyclic aromatic hydrocarbons as the pitch is consumed in the smelter.
The linings of the pots end up contaminated with cyanide-forming materials; Alcoa has a process for converting Spent potlining into aluminium fluoride for reuse and synthetic sand usable for building purposes and inert waste.
Alternatively metal anodes boast high mechanical strength and conductivity but tend to corrode easily during the reduction process. Some material systems that are used in inert metal anodes include Al-Cu, Ni-Cu, and Fe-Ni-Cu systems. Additional additives such as Sn, Ag, V, Nb, Ir, Ru can be included in these systems to form non reactive oxides on the anode surface, but this significantly increases the cost and embodied energy of the anode.
Cermet anodes are the combination of a metal and ceramic anode, and aim to take advantage of the desirable properties of both; the electrical conductivity and toughness of the metal and stability of the ceramic. These anodes often consist of a combination of the above metal and ceramic materials. In industry, Alcoa and Rio Tinto have formed a joint venture, Elysis, to commercialize inert anode technology developed by Alcoa. The inert anode is a cermet material, a metallic dispersion of copper alloy in a ceramic matrix of nickel ferrite. Unfortunately, as the number of anode components increases , the structure of the anode becomes more unstable. As a result. cermet anodes also suffer from corrosion issues during reduction.
To reduce the energy cost of the smelting process, alternative electrolytes such as Na3AlF6 are being investigated that can operate at a lower temperature. However, changing the electrolyte changes the kinetics of the liberated oxygen from the Al2O3 ore. This change in bubble formation can alter the rate the anode reacts with Oxygen or the electrolyte and effectively change the efficiency of the reduction process.
Inert anodes, used in tandem with vertical electrode cells, can also reduce the energy cost of aluminum reduction up to 30% by lowering the voltage needed for reduction to occur. Applying these two technologies at the same times allows the anode-cathode distance to be minimized which decreases resistive losses.
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