AU708455B2 - Aluminium electrowinning cell with improved cathode bottom - Google Patents

Description

ALUMINIUM ELECTROWINNING CELL WITH IMPROVED CATHODE BOTTOM Field of the Invention The present invention concerns a cell for the electrowinning of aluminium by the electrolysis of alumina dissolved in a fluoride-based molten electrolyte such as cryolite, incorporating an improved cathode bottom.

Background of the Invention The technology for the production of aluminium by the electrolysis of alumina, dissolved in molten cryolite containing salts, at temperatures around 950°C is more than one hundred years old.

This process, conceived almost simultaneously by Hall and H6roult, has not evolved as much as other electrochemical processes, despite the tremendous growth in the total production of aluminium that in fifty years has increased almost one hundred fold. The process and the cell design have not undergone any great change or improvement and carbonaceous materials are still used as electrodes and cell linings.

The electrolytic cell trough is typically made of a steel shell provided with an insulating lining of refractory material covered by pre-baked anthracite-graphite or all graphite carbon blocks at the wall and at the cell floor bottom which acts as 20 cathode and to which the negative pole of a direct curlas of steel conductor bars embedded in the carbon blocks.

The anodes are still made of carbonaceous material and must be replaced every few weeks. The operating temperature is still approximately 950C in order to have a sufficiently high rate of dissolution of alumina which decreases at lower temperatures and to have a higher conductivity of the electrolyte.

The carbonaceous materials used in Hall-Heroult cells as cell lining deteriorate under the existing adverse operating conditions and limit the cell life.

The anodes have a very short life because during electrolysis the oxygen which should evolve on the anode surface combines with the carbon to form CO 2 and small amounts of CO. The actual consumption of the anode is approximately 13/5/98GC9865.SPE,2 450 kg/ton of aluminium produced which is more than 1/3 higher than the theoretical amount.

The carbon lining of the cathode bottom has a useful life of a few years after which the operation of the entire cell must be stopped and the cell relined at great cost. Despite an aluminium pool having a thickness of 15 to 20 cm maintained over the cathode, the deterioration of the cathode carbon blocks cannot be avoided because of penetration of sodium into the carbon which by chemical reaction and intercalation causes swelling, deformation and disintegration of the cathode carbon blocks, as well as penetration of cryolite and liquid aluminium.

The carbon blocks of the cell side wall do not resist oxidation and attack by cryolite and a layer of solidified cryolite has to be maintained on the cell side walls to protect them. In addition, when cells are rebuilt, there are problems of disposal of the carbon cathodes which contain toxic compounds including ,15 cyanides.

Another major drawback, however, is due to the fact that irregular electromagnetic forces create waves in the molten aluminium pool and the anodecathode distance (ACD), also called inter-electrode gap (lEG), must be kept at a safe minimum value of approximately 50 mm to avoid short circuiting between the "•020 aluminium cathode and the anode or re-oxidation of the metal by contact with the

CO

2 gas formed at the anode surface.

5 The high electrical resistivity of the electrolyte, which is about 0.4 ohm.

cm., causes a voltage drop which alone represents more than 40% of the total voltage drop with a resulting energy efficiency which reaches only 25% in the most modern cells. The high cost of energy together with the low efficiency, has become an even bigger item in the total manufacturing cost of aluminium since the oil crisis, and has decreased the rate of growth of this important metal.

In the second largest electrochemical industry following aluminium, namely the caustic and chlorine industry, the invention of the dimensionally stable anodes

(DSA

based on noble metal activated titanium metal, which were developed around 1970, permitted a revolutionary progress in the chlorine cell technology 1315/98GC9865.SPE,3 resulting in a substantial increase in cell energy efficiency, in cell life and in chlorine-caustic purity. The substitution of graphite anodes with DSA® increased drastically the life of the anodes and reduced substantially the cost of operating the cells. Rapid growth of the chlorine caustic industry was retarded only by ecological concerns.

In the case of aluminium production, pollution is not due to the aluminium produced, but to the materials and the manufacturing processes used and to the cell design and operation.

However, progress has been reported in the operation of modern aluminium plants which utilise cells where the gases emanating from the cells are in large part 00' collected and adequately scrubbed and where the emission of highly polluting gases during the manufacture of the carbon anodes and cathodes is carefully controlled.

0O While progress has been reported in the fabrication of carbon cathodes by the application of coatings or layers using new aluminium wettable materials which are also a barrier to sodium penetration during electrolysis, no progress has been achieved in design of cathodes for aluminium production cells with a view to io restraining movement of the molten aluminium in order to reduce the interelectrode gap and the rate of wear of its surface.

U.S. Patent 4,560,488 (Sane et al) discloses a recent development in molten salt electrolysis cells concerning making materials wettable by molten aluminium. However, the carbon or graphite anodes and cathodes are of conventional design with no suggestion leading to the present invention.

U.S. Patent 4,681,671 (Duruz) illustrates another improvement in molten salt electrolysis wherein operation at lower than usual temperatures is carried out utilising permanent anodes, e.g. metal, alloy, ceramic or a metal-ceramic composite as disclosed in European Patent Application No. 0030834 and U.S.

Patent 4,397,729. Again, while improved operation is achieved at lower temperatures, there is no suggestion of the subject matter of the present invention.

13/5/98GC9865.SPE,4

~I

PCT Application WO 89/06289 (La Camera et al) deals with an improved molten electrolysis wherein attention is directed to an electrode having increased surface area. However, again, there is no disclosure leading one to the present invention.

U.S. Patents 3,400,061 (Lewis et al) and 4,602,990 (Boxall et al) disclose aluminium electrowinning cells with sloped drained cathodes arranged with the cathodes and facing anode surfaces sloping across the cell. In these cells, the molten aluminium flows down the sloping cathodes into a median longitudinal groove along the centre of the cell, or into lateral longitudinal grooves along the cell sides, for collecting the molten aluminium and delivering it to a sump.

U.S. Patent 5,203,971 (de Nora et al) discloses an aluminium electrowinning cell having a partly refractory and partly carbon based cell lining.

The carbon-based part of the cell bottom may be recessed in respect to the refractory part, which assists in reducing movement of the aluminium pool.

5 US Patent 3,856,650 (Kugler) proposed lining a carbon cell bottom with a ceramic coating upon which parallel rows of tiles are placed, in the molten aluminium, in a grating-like arrangement in an attempt to reduce wear due to movements of the aluminium pool.

To restrict movement in a "deep" cathodic pool of molten aluminium, US Patent '20 No 4,824,531 (Duruz et al) proposed filling the cell bottom with a packed bed of loose pieces of refractory material. Such a design has many potential advantages but, because of the risk of forming a sludge by detachment of particles from the packed bed, the design has not found acceptance. US Patent No 4,443,313 (Dewing et al) sought to avoid this disadvantage of the previously mentioned loose packed bed by providing a mono-layer of closely packed small ceramic shapes such as balls, tubes or honeycomb tiles.

The following references disclose several other improvements in cell operation.

European Patent Application No. 0308015 (de Nora) discloses a novel current collector; 1315/98GC9865.SPE,5 Zr European Patent Application No. 0308013 (de Nora) deals with a novel composite cell bottom; and European Patent Application No. 0132031 (Dewing) provides a novel cell lining.

While the foregoing references indicate continued efforts to improve the operation of molten cell electrolysis operations, none suggest the invention and all proposals for means to restrain movement of the aluminium pool or layer on the cell bottom have proven to be ineffective.

Summary of the Invention This invention aims to overcome problems inherent in the conventional design of drained cells used in the electrowinning of aluminium via electrolysis of alumina dissolved in molten fluoride-based melts in particular cryolite, notably by proposing an improved cell bottom which incorporates means for collecting and evacuating the drained molten aluminium.

The present invention permits more efficient cell operation by modifying the cell bottom design. Such a modified design may then be utilised in drained cell configurations.

The invention concerns an electrolytic cell for the electrowinning of aluminium from alumina dissolved in a fluoride-based molten electrolyte, having a 20 cathode cell bottom comprising a series of sloped, V-shaped, aluminium-wettable cathode surfaces and a series of anodes face the sloped cathode surfaces. Each sloped cathode surface forms a drained cathode surface down which a layer of produced molten aluminium is continuously drained. The cell bottom is further provided with means for collecting and evacuating the drained molten aluminium.

In the improved cell bottom according to the invention, the means for collecting and evacuating the drained molten aluminium comprise a series of parallel recessed grooves or channels located along the bottom of the V-shaped cathode surfaces and extending below the sloped cathode surfaces for collecting and evacuating the molten aluminium drained from the bottom of the sloped cathode surfaces.

13/5/98GC9865.SPE,6 I I 5 I Ir As described below and illustrated in the drawings the cell bottom incorporates carbon cathode blocks, each cathode block having at least one sloped top surface, side surfaces and a bottom surface. The cathode blocks are connected side-by-side transversally of the cell for example with ramming paste as in conventional cells or, preferably, by glue. The blocks are usually further provided with steel or other conductive bars for the delivery of current, the conductive bars are generally parallel to one another and transverse to the cell.

The surfaces of the blocks making up the cathode cell bottom are most preferably coated with a layer of aluminium-wettable refractory material, advantageously a particulate refractory hard metal boride applied from a slurry containing colloid, for example as disclosed in US Patent 5,651,874 (Sekhar et al).

When the cell is in use the surfaces of the cathode cell bottom are covered .by a layer of molten aluminium forming a drained cathode surface, the recessed channels or grooves forming a canal serving to guide the flow of aluminium across the cell. The flow of aluminium may be maintained at a constant level in the recessed grooves or channels. In this drained configuration, the channels or grooves are partly filled with molten aluminium and the electrolysis takes place between the aluminium-wetted cathode and the facing anode surface. In this drained cathode configuration, as explained below, an arrangement will be provided for removing aluminium from the sides of the cell.

In this drained configuration the inter-electrode distance is reduced with a concomitant reduction of cell voltage and an increase in energy efficiency.

The recessed grooves or channels are so configured and arranged, in particular as regards their depth and the shape and angle of their walls, that the molten aluminium contained in the channels is restrained from movement in the longitudinal direction of the cell. In such a drained cell configuration, the aluminium can flow along the recessed groove or channel into a collection channel.

An advantage obtained with this channeled drained-cell bottom is that its life is extended in comparison with other electrolytic aluminium production cells.

Moreover, the channeled cathode improves the uniformity of the current distribution and increases the current efficiency. In addition, the recessed grooves -7 13/5198GC9865.SPE,7 or channels can serve to eliminate sludge which collects in the grooves or channels but is flushed out with the molten aluminium.

In most embodiments, the recessed channels or grooves have a generally U-shaped cross-section designed to permit the evacuation and collection of aluminium.

Advantageously, there may be at least one cross channel or groove which extends along the cell and intersects with the recessed channels or grooves. Such cross channels or grooves may serve to drain the aluminium down the inclined cathode surfaces, hence guiding the flow of molten aluminium down these surfaces into the recessed channels or grooves. Cross channels or grooves of suitable dimensions can also serve for the removal of the molten aluminium to an aluminium reservoir.

Cross channels or grooves may run down the sloping cathode bottom S surface to facilitate drainage of the aluminium.

In general, the recessed channels or grooves may lead into at least one o, channel arranged longitudinally of the cell for collecting the molten aluminium, and So :o preferably having means such as a weir for maintaining a constant level of ~aluminium in the recessed channels or grooves. This aluminium collection channel may extend along one or both sides of the cell, or could be a deep central channel machined in the cathode blocks.

Preferably, the cell bottom is made of carbon blocks whose surfaces are treated to reduce sodium penetration, for example as described in US Patent 5,378,327 or in US Patent 5,679,224, or are coated with a layer which reduces sodium penetration, for example a refractory hard metal boride applied from a slurry containing colloid as disclosed in US Patent 5,651,874 (all in the name of Sekhar et al).

In general, carbon cathode blocks are made resistant to chemical attack and to mechanical attack. The surfaces of carbon blocks making up the cathode cell bottom can also be coated with a layer which prior to use or in use becomes harder than the carbon cathode block and thereby protects the surface against abrasive wear by limited movement of the molten aluminium. Moreover, the 6/5/99GC9865.SPE,8 f l c I1 3

I--

hardened cathode surface remains dimensionally stable whereas a facing carbon anode may erode and conform to the shape of the cathode. This surface-hardening effect can be achieved with the aforementioned refractory boride or other aluminium wettable refractory layers which provide an essentially dimensionally stable surface.

In this way, a carbon cathode cell bottom can remain dimensionally stable during electrolysis, and because of this, it is both possible and advantageous to provide channels in the tops of the carbon cathode blocks because these channeled blocks will remain dimensionally stable during cell operation.

The cell incorporating the channeled cell bottom can employ conventional carbon anodes whose shape adapts to the channeled cathode bottom. Speciallyshaped carbon anodes designed to co-operate with the channeled cathode design, and in particular to facilitate gas release at the anode while assisting drainage of woo 0 molten aluminium at the cathode can also be used. Dimensionally stable anodes can also be employed.

The invention also relates to a carbon cathode block suitable for the drained-cathode electrolytic cell as described here above for the electrowinning of aluminium from alumina dissolved in a fluoride-based molten electrolyte, ready to be installed in a cell. Such a block has at least one sloped top surface, side surfaces and a bottom surface, so that when several blocks are laterally placed side-by-side their top surfaces form a series of juxtaposed V-shaped surfaces. Each sloped surface, when coated with an aluminium-wettable refractory material, forms a drained cathode surface down which a layer of produced molten aluminium is continuously drained when the cathode block is in use to electrowin aluminium.

According to the invention, the top surface of the cathode block comprises at least one recessed groove or channel; or a cut-out along at least one edge located at the bottom of the sloped surface, so that when two cathode blocks are placed side-by-side to form a V-shaped top surface a recessed groove or channel is formed between them. The recessed grooves or channels are located along the bottom of the V-shaped surfaces and extend below the V-shaped surfaces. Each recessed groove or channel is such that when in use for the electrowinning of -9- 13/5/98GC9865.SPE,9 aluminium it collects and evacuates the molten aluminium drained from the bottom of the sloped cathode surfaces.

This recessed channel or groove in the top sloped surfaces of the block, or formed between two blocks, is so shaped and dimensioned that when the cathode blocks are used to electrowin aluminium, molten aluminium collected in the channel or groove is restrained from moving transversally to the channel or groove, providing substantial advantages in operation, as explained above.

These blocks, which can incorporate all of the features described in relation to the complete cell, may have a flat top surface, or its top surface may be sloping or may comprise two roof-like inclined sections such that the blocks can be assembled side-by-side to form a cell bottom with alternately sloping sections 0.0. which, at their lower intersections, form the aforesaid channels in the blocks' top surfaces.

A further aspect of the invention is a process to electrowin aluminium in a cell as described hereabove. The method comprises dissolving alumina in the electrolyte and electrolysing the dissolved alumina to produce aluminium on the sloped, V-shaped cathode surfaces. The product aluminium is then drained from the bottom of the sloped cathode surface into the recessed groove or channel where it is collected and evacuated.

Description of the Drawings 0:0 Reference is now made to the drawings wherein: .000 Figures 1 and 2 show comparative drained cells which do not incorporate the recessed groove or channel according to the invention; Figure 3 is a similar view of an electrolytic cell according to the invention, incorporating channeled cathode blocks and dimensionally stable anodes; and Figure 4 is a schematic plan view of the cell bottom of Figure 2 during operation, partly cut-away and with the anodes and cell superstructure not visible.

Detailed Description of the Invention Figures 1 and 2, show parts of comparative aluminium drained cells whose cell bottoms are made up of a series of V-shaped carbon blocks 10 joined by ramming paste 14, but which are not provided with recessed grooves or channels 13/5198GC9865.SPE, according to the invention. Each V-shaped cathode bottom is formed by juxtaposing blocks 10. In Figure 1 each block 10 has an inclined top surface 26 or 27, the blocks 10 being arranged alternately facing one another so as to form a series of V-shaped channels 28 between adjacent blocks 10. In Figure 2 each block 10 has roof-like sloped top surfaces 26,27 so that when two blocks 10 are juxtaposed the roof-like top surfaces form a V-shaped channel 28 between the adjacent blocks In both Figures 1 and 2 the V-shaped channels 28 receive a stream or canal 40' of molten aluminium in their bottom part, running across the cell. Above the V-shaped channel 28 and the aluminium canal 40' are carbon anodes 15 with corresponding V-shaped active faces 16 terminating with a lower flattened part 17 o.s. opposite the aluminium canal 40'. This flattened part 17 can be formed in use.

The cells operate as drained cathode cells, wherein the aluminium produced on the inclined cathode surfaces 26 and 27 coated with an aluminium- 5 wettable refractory coating 35 flows down the inclined surfaces 26,27, in the longitudinal direction of the cell, into the V-shaped channel 28 where it is collected in the aluminium canal 40'. The V-shaped channels 28 join into one or two side channels inclined in the longitudinal direction of the cell in order to permanently a 0 drain the product aluminium, at a rate to keep the level of aluminium canal r q stable.

1.:1 In this drained configuration, the V-shaped channels 28 are partly filled with molten aluminium so that the electrolysis takes place between the inclined aluminium-wetted cathode surfaces 26,27 and the facing inclined surfaces 16 of anode 15, as well as between the aluminium canal 40' and the facing flattened part 17 of the anode 15 which will wear in such a way as to conform to the opposing surfaces (26,27 and the flat top of canal Moreover, the inclination of the anode surfaces 16 assists in release of the anodically-formed gases.

Figure 3 illustrates a cell according to the invention, where the same elements are designated by the same references, but which includes dimensionally stable anodes 18 in a "roof" configuration straddling the tops of the adjacent cathode blocks 10 which also have alternately arranged inclined surfaces 26,27 -11-1 3/598GC9865.SPE, 11 j coated with an aluminium-wettable refractory coating 35 as in Figure 1. However, the blocks of the invention are not limited to this configuration of inclined surfaces 26,27 but cover other configurations such as the roof-like configuration disclosed in Figure 2.

The anodes 18 are made of or coated with any suitable non-consumable or substantially non-consumable, electronically-conductive material resistant to the electrolyte and to the anodically produced oxygen and other gases, vapours and fumes present in the cell. The anodes 18 may for example have a metal, alloy or cermet substrate which is protected in use by a cerium-oxyfluoride-based protective coating produced and/or maintained by maintaining a concentration of cerium in the electrolyte, as described in U.S. patent 4,614,569 (Duruz et al).

t. Consumable carbon anodes 15 as shown in Figures 1 and 2 may also be :o used instead of the dimensionally stable anodes 18 for the purpose of this a. I invention.

0.:..415 The cell of Figure 3 also operates as a drained cathode cell, wherein the aluminium produced on the inclined cathode surfaces 26 and 27 coated with an a.

aaluminium-wettable refractory coating 35 flows down to the bottom of these inclined surfaces where it is collected as an aluminium canal 40' in a recessed groove or channel 28' which is generally U-shaped in cross-section. This groove 28' is formed between cut-outs in the edges of the carbon blocks 10, when the blocks are fitted together. The cathode surfaces 26,27 are inclined in the longitudinal direction of the cell in order to permanently drain the product aluminium into the canal 40', and the aluminium is removed from this canal 40' at a rate to keep its aluminium level stable. In this drained configuration, the recessed grooves or channels 28' are filled with the molten aluminium forming canals Electrolysis takes place between the inclined aluminium-wetted cathode surfaces 26,27 and the facing inclined surfaces of the dimensionally-stable anodes 1 8. The inclination of the anodes 18 assists in releasing the anodically-formed gases through a central opening 19 and this can be further assisted if needed by providing ridges on the anodes 18 or making the anodes foraminate.

12 13/5/98GC9865.SPE,1 2 I LIII I In operation, the cryolite-based electrolyte 41 is usually at a temperature of about 950°C, but the invention applies also to components used in cells with electrolytes well below 900C, and as low as 700"C.

The inclined surfaces 26,27 and the recessed grooves or channels 28' of the carbon cathode blocks 10 can be made dimensionally stable by applying a coating 35 of an aluminium-wettable refractory hard metal (RHM) having little or no solubility in aluminium and having good resistance to attack by molten cryolite.

Note that the coating 35 also covers the ramming paste 14. Useful RHM include borides of titanium, zirconium, tantalum, chromium, nickel, cobalt, iron, niobium and/or vanadium. Useful cathode materials are carbonaceous materials such as anthracite or graphite.

It is preferred that the cathode top surfaces of the present invention have a coating 35 of particulate refractory hard metal boride in a colloid applied from a slurry of the particulate refractory hard metal boride in a colloid carrier, wherein '15 the colloid comprises at least one of colloidal alumina, silica, yttria, ceria, thoria, zirconia, magnesia, lithia, monoaluminium phosphate or cerium acetate. The colloidal carrier has been found to considerably improve the properties of the coating produced by non-reactive sintering.

eQ US Patent 5,651,874 (Sekhar et al) provides a method of applying refractory hard metal boride to a carbon containing component of a cell for the production of aluminium, in particular by the electrolysis of alumina dissolved in a cryolite-based molten electrolyte, this method comprising applying to the surface of the component a slurry of particulate pre-formed refractory boride in a colloidal carrier as specified above, followed by drying, and by heat treatment before or after the component is installed in the aluminium production cell.

The method of application of the slurry to the cathode block 10 of the present invention involves painting (by brush or roller), dipping, spraying, or pouring the slurry onto the block 10 and allowing to dry before another layer is added. The coating 35 does not need to be entirely dry before the application of the next layer. It is preferred to heat the coating 35 with a suitable source so as to completely dry it and improve densification of the coating. Heating and drying 13 13/5/98GC9865.SPE,13 1 11311 take place preferably in non-oxidising atmospheres at about 80-200°C, usually for half an hour to several hours and further heat treatments are possible.

The cathode block 10 may be treated by sand blasting or pickled with acids or fluxes such as cryolite or other combinations of fluorides and chlorides prior to the application of the coating. Similarly the block 10 may be cleaned with an organic solvent such as acetone to remove oily products and other debris prior to the application of the coating. These treatments will enhance the bonding of the coatings to the cathode block After coating the cathode block by dipping, painting or spraying the slurry or combinations of such techniques in single or multi-layer coatings and drying, a final coat of the colloid alone may be applied lightly prior to use.

Before or after application of the coating 35 and before use, the cathode block 10 can be painted, sprayed, dipped or infiltrated with reagents and precursors, gels and/or colloids. For instance, before applying the slurry of particulate refractory boride in the colloidal carrier the cathode block 10 can be impregnated with e.g. a compound of lithium to improve the resistance to penetration by sodium, as described in US Patent 5,378,327 (Sekhar et al).

To assist rapid wetting of the cathode block 10 by molten aluminium, the refractory coating 35 on the block 10 may be exposed to molten aluminium in the *6c* presence of a flux assisting penetration of aluminium into the refractory material, the flux for example comprising a fluoride, a chloride or a borate, of at least one S of lithium and sodium, or mixtures thereof. Such treatment favours aluminization of the refractory coating by the penetration therein of aluminium.

Figure 4 shows the aluminium flow in the cell of Figure 2 which is similar to the flow in the cell shown in Figure 3. The aluminium produced on the inclined cathode surfaces 26 and 27 coated with the aluminium-wettable refractory coating flows down these surfaces and into the channel 28 (channel 28' in the cell of Figure 3) where it is collected in the aluminium canal 40'. The direction of flow of the molten aluminium is schematically indicated in Figure 4 by arrows. As shown, the channels 28 join into two side channels 42, running along and inclined in the longitudinal direction of the cell, in order to permanently drain the product -14- 13/5/98GC9865.SPE,14 II I i I ~I _I _i 1~ aluminium. The molten aluminium is drained at a rate to keep the level of the aluminium canals 40' stable, for example by having a weir at the outflow end of the side channels 42.

As illustrated in the right hand part of Figure 4, the two longitudinally sloping surfaces 26 and 27 of each cathode block 10 can be provided with cross channels or grooves 43 which run down these sloping surfaces 26 and 27 and lead into the main channel 28 running across the cell. Any suitable number of cross grooves 43 can be provided with any suitable spacing. These cross grooves 43 guide the flow of aluminium down the sloping cathode surfaces 26,27, while restraining movement of the aluminium across the cell as it drains down these inclined cathode surfaces. Only once the drained aluminium joins the canal a.

40' can it flow freely across the cell to the side channels 28.

o. This arrangement of the cross grooves 43 down the inclined cathode surfaces 26,27, the main collecting grooves 28 across the cell, and the side 5 channels 42 provides a perfectly controlled flow of the molten aluminium over the cell bottom, avoiding turbulence due to magnetohydrodynamic forces.

tThe side channels 42 can be formed in the ends of the cathode blocks or can be made in the cell sidewalls, or can be a combination of bevels or cut-outs in the ends of the cathode blocks 10, co-operating with bevels or ledges in the cell sidewalls. Additionally or alternatively, a central channel could be provided by machining recesses in the centre parts of the inclined walls 26, 27 of the cathode blocks 10, or by making each cathode section from two cathode blocks placed end-to-end, with cut-outs in the facing ends.

It should be understood that this application is a divisional of Australian Patent Application No. 31901/95 (accepted under Serial No. 688098), and the whole contents thereof are included herein by reference.

Where the terms "comprise", "comprises", "comprised" or "comprising" are used in this specification, they are to be interpreted as specifying the presence of the stated features, integers, steps or components referred to, but not to preclude the presence or addition of one or more other feature, integer, step, component or group thereof.

15- 13/5/98GC9865.SPE,15 Finally, it is to be understood that the aforegoing description refers merely to preferred embodiments of the invention and that variations and modifications will be possible thereto without departing from the spirit and scope of the invention, the ambit of which is to be determined from the following claims.

0 0

S.

I* 0* a. a s 6 a 6 66 *6*6 S. 96 g *4* a r 16 13/5/98GC9865.SPE16 ~il~l 9( The claims defining the invention are as follows:- 1. An electrolytic cell for the electrowinning of aluminium from alumina dissolved in a fluoride-based molten electrolyte, having a cathode cell bottom having sloped, V-shaped, aluminium-wettable cathode surfaces and a series of anodes facing said sloped cathode surfaces, each sloped cathode surface forming a drained cathode surface down which a layer of produced molten aluminium is continuously drained, said cell bottom having means for collecting and evacuating the drained molten aluminium, including the means for collecting and evacuating the drained molten aluminium which includes a series of parallel recessed grooves or channels located along the bottom of said V-shaped cathode surfaces and extending below said sloped cathode surfaces for collecting and evacuating the molten aluminium drained from the bottom of said sloped cathode surfaces.

2. The electrolytic cell as claimed in claim 1, wherein said cathode cell bottom is made of carbon cathode blocks, each block having at least one sloped o top surface, side surfaces and a bottom surface, said cathode blocks being connected side-by-side transverse to said cell, the sloped top surfaces being S coated with a layer of aluminium-wettable refractory hard material, said blocks oo being further provided with steel or other conductive bars for the delivery of current, said conductive bars being generally parallel to one another and transverse to said cell.

3. The electrolytic cell as claimed in Claim 1 or Claim 2, wherein said o sloped cathode surfaces are coated with an aluminium-wettable layer including metal boride.

4. The electrolytic cell as claimed in any one of the preceding claims, wherein the molten aluminium is at a constant level within said recessed grooves or channels.

The electrolytic cell as claimed in any one of the preceding claims, wherein said recessed grooves or channels have a generally U-shaped crosssection.

6. The electrolytic cell as claimed in any one of the preceding claims, wherein said sloped cathode surfaces further include at least one cross channel or ,roove which intersects with said parallel recessed grooves or channels, said cross Schnel or groove extending longitudinally of said cell.

Clef! -1 7 5/5/99GC9865.SPE- 17 c j_ \x II I I I

Claims (13)

1. 7. The electrolytic cell as claimed in Claim 6, wherein said cell bottom includes a plurality of pairs of two longitudinally sloping parts and said cross channels or grooves run down these sloping parts, there being at the intersection of said two sloping parts a collecting recessed groove or channel, said cross channels or grooves leading to an aluminium reservoir.
2. 8. The electrolytic cell as claimed in any one of Claims 2 to 7, wherein some of said recessed grooves or channels are formed by cut-outs along the top edges of said carbon blocks.
3. 9. The electrolytic cell as claimed in any one of the preceding claims, wherein said recessed grooves or channels extend transversely of said cell and lead into at least one channel arranged longitudinally of said cell for collecting the molten aluminium. The electrolytic cell as claimed in any one of Claims 2 to 9, wherein said sloping surfaces of the carbon blocks making up said cathode cell bottom are treated to reduce sodium penetration. 9
4. 11. The electrolytic cell as claimed in any one of Claims 2 to 9, wherein said sloping surfaces of said carbon blocks making up said cathode cell bottom are coated with a layer which reduces sodium penetration. "12. The electrolytic cell as claimed in any one of Claims 2 to 9, wherein said sloping surfaces of said carbon blocks making up said cathode cell bottom are 9. coated with a layer which prior to or in use becomes harder than said carbon cathode block. %91 3. The electrolytic cell as claimed in any one of Claims 2 to 12, wherein said carbon cathode blocks remain dimensionally stable during electrolysis.
5. 14. The electrolytic cell as claimed in any one of Claims 2 to 13, wherein said carbon cathode blocks are made resistant to chemical and mechanical attack. A carbon cathode block of a drained-cathode electrolytic cell for the electrowinning of aluminium from alumina dissolved in a fluoride-based molten electrolyte, having at least one sloped top surface, side surfaces and a bottom surface, so that when several blocks are laterally placed side-by-side their top surfaces form a series of juxtaposed V-shaped surfaces, each sloped surface when coated with an aluminium-wettable refractory material forming a drained cathode tI, 'Isurface down which a layer of produced molten aluminium is continuously drained 1 8 5/5/99GC9865.$PE,-
6. 18- II C I i ~I when said cathode block is in use to electrowin aluminium, said cathode block having means for collecting and evacuating the drained molten aluminium, including means for collecting and evacuating the drained molten aluminium which include at least one recessed groove or channel, or a cut-out along at least one edge located at the bottom of said sloped surface, so that when two cathode blocks are placed side-by-side to form a V-shaped top surface a recessed groove or channel is formed between them, said recessed grooves or channels being located along the bottom of said V-shaped surfaces and extending below said V- shaped surfaces, said recessed groove or channel being such that, when in use for the electrowinning of aluminium, it collects and evacuates the molten aluminium drained from the bottom of said sloped cathode surfaces. 16. The carbon cathode block as claimed in Claim 15, wherein said bottom surface of said cathode block has a groove or like recess extending there along generally parallel to the top surface and to one side surface of said cathode :°oj block, for receiving a steel or other conductive bar for the delivery of current. 17. The carbon cathode block as claimed in Claim 15 or Claim 16, wherein said recessed grooves or channels have a generally U-shaped cross- section. *o a 18. The carbon cathode block as claimed in any one of Claims 15 to 17, further including in its top surface at least one cross channel or groove which a= intersects with, said recessed grooves or channels or cut-out.
7. 19. The carbon cathode block as claimed in any one of Claims 15 to 18, wherein its top surface is coated with a layer of aluminium-wettable refractory material.
8. 20. The carbon cathode block as claimed in any one of Claims 15 to 19, including a steel or other conductive bar secured in said groove or like recess in the bottom surface of said block by cast iron or another electrically conductive bonding material.
9. 21. A process to electrowin aluminium in a cell according to any one of Claims 1 to 14, wherein the dissolved alumina is electrolysed to produce aluminium on said sloped, V-shaped cathode surfaces, and then drained from the bottom of said sloped cathode surface into said recessed grooves or channels ,where it is collected and evacuated. 1 9- 5/5,99GC9865.SPE,- 19- I
10. 22. The process as claimed in Claim 21, wherein the product aluminium is maintained at a constant level within the recessed grooves or channels.
11. 23. An electrolytic cell for the electrowinning of aluminium from alumina dissolved as a fluoride-based molten electrolyte, substantially as described herein with reference to the accompanying drawings.
12. 24. A carbon cathode block of a drained-cathode electrolytic all for the electrowinning of aluminium from alumina dissolved in a fluoride-based molten electrolyte, substantially as described herein with reference to the accompanying drawings.
13. 25. A process to electrowin aluminium, as claimed in Claim 21, substantially as described herein with reference to the accompanying drawings. DATED this 6th day of May, 1999. MOLTECH INVENT SA By their Patent Attorneys: CALLINAN LAWRIE oo •el# ii C I 20 5/5/99GC9865.SPE,- 1 ABSTRACT An electrolytic cell for the electrowinning of aluminium from alumina dissolved in a fluoride-based molten electrolyte, having a cathode cell bottom, preferably made of made of carbon cathode blocks, comprising a series of V-shaped, sloped, aluminium-wettable cathode surfaces (26,27) and a series of anodes (15) facing the sloped cathode surfaces. Each sloped cathode surface (26,27) forms a drained cathode surface down which a layer of produced molten aluminium is continuously drained. A series of parallel recessed grooves or channels located along the bottom of the V-shaped cathode surfaces (26,27) and extending below the sloped cathode surfaces (26,27) collects and evacuated the molten aluminium drained from the bottom of the sloped cathode surfaces (26,27). 0 s 1 *00 00 00* *000 *000 -210 0 0i -G"S *i I I e I i I I 1 3