WO2007027732A2 - Methods for in-situ formation of slots in a soderberg anode - Google Patents

Methods for in-situ formation of slots in a soderberg anode Download PDF

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Publication number
WO2007027732A2
WO2007027732A2 PCT/US2006/033797 US2006033797W WO2007027732A2 WO 2007027732 A2 WO2007027732 A2 WO 2007027732A2 US 2006033797 W US2006033797 W US 2006033797W WO 2007027732 A2 WO2007027732 A2 WO 2007027732A2
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WO
WIPO (PCT)
Prior art keywords
anode
soderberg
aluminum
plate inserts
carbon
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PCT/US2006/033797
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French (fr)
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WO2007027732A3 (en
Inventor
Xiangwen Wang
Alton T. Tabereaux
Jerry L. Roddy
Alain J. Belda
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Alcoa Inc.
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Application filed by Alcoa Inc. filed Critical Alcoa Inc.
Priority to BRPI0615403-4A priority Critical patent/BRPI0615403A2/en
Priority to EP06813942A priority patent/EP1920086A2/en
Priority to CA002619085A priority patent/CA2619085A1/en
Priority to AU2006284903A priority patent/AU2006284903A1/en
Priority to EA200800720A priority patent/EA012225B1/en
Publication of WO2007027732A2 publication Critical patent/WO2007027732A2/en
Publication of WO2007027732A3 publication Critical patent/WO2007027732A3/en

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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/06Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
    • C25C3/08Cell construction, e.g. bottoms, walls, cathodes
    • C25C3/12Anodes
    • C25C3/125Anodes based on carbon
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/06Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
    • C25C3/16Electric current supply devices, e.g. bus bars
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/06Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
    • C25C3/22Collecting emitted gases

Abstract

A self-baking, Soderberg type carbon anode (40) for use in an aluminum electrolyses cell (1) to form product aluminum (11), where the anode (40) is consumable in molten electrolyte (12) in the cell, the anode having top, bottom and side surfaces and multiple layers of vertically disposed plate inserts (48) meltable in the molten electrolyte, the plate inserts (48) preferably made of aluminum and are capable of melting to create hollow slots (52) at the bottom of the anode facilitating any gas bubbles (60) generated to channel to the side of the anode into the electrolyte (12).

Description

METHODS FOR IN-SITU FORMATION OF SLOTS IN A SODERBERG ANODE
Cross-Reference to Related Application
This application claims priority to U.S. Application No. 11/215,586 filed August 30, 2005, which is incorporated herein by reference.
Field of the Invention
The present invention relates to the use of slots in self baking carbon anodes for use in aluminum electrolysis cells, where the slots channel anode gas away from anode surfaces.
Background of the Invention
Aluminum is produced conventionally by the electrolysis of alumina dissolved in cryolite-based (usually as NaF plus AlF3) molten electrolytes at temperatures between about 900° C and 1000° C; the process is known as the Hall-Heroult process. A HaIl- Heroult reduction cell/"pot" typically comprises a steel shell having an insulating lining of refractory material, which in turn has a lining of carbon that contacts the molten constituents. Conductor bars connected to the negative pole of a direct current source are embedded in the carbon cathode substrate that forms the cell bottom floor. In general carbon anodes are consumed with evolution of carbon oxide gas (CO2 and CO), as gas bubbles and the like.
As used to produce aluminum by the Hall-Heroult electrolytic process, there are two anode technologies. One is a pre-baked anode characterized by U.S. Patent No. 2,480,474, mentioned previously, and U.S. Patent Application Publication No. 20050199488, filed on March 11, 2004 (Barclay et al.) The other is a "Soderberg" self- baking anode cell technology characterized by U.S. Patent No. 3,996,117 (Graham et al.). In a pre-baked cell, there are usually between 10 and 40 anodes, depending on cell size (amperage). Soderberg cells have only one large self-baking anode having an approximate size of 2-3 meters wide and 5-6 meters in length. This self-baking is taught by Soderberg in U.S. Patent No. 1 ,440,724.
As described by Edwards et al. in Aluminum and Its Production, MCGraw-Hill, New York, 1930, pp. 300-307, carbon anodes can be made of a mixture of carbon, pitch and tar, which is pressed into molds and subsequently baked in a baking oven, or they can be made by the Soderberg technique. In the Soderberg technique, a steel casing is used to hold a carbonaceous electrode paste of carbon and tar-pitch. The electrode mix is gradually baked to provide a dense, baked carbon electrode of good conductivity which is gradually moved toward the electrolytes, where it is eventually consumed.
The consumption of carbon anodes in molten electrolyte is shown in U.S. Patent Specification Nos. 2,480,474 and 3,756,929 (Johnson Fig. 6a and Schmidt-Hatting et al. Fig. 1, respectively). Anodes are at least partially submerged in the bath and those anodes as well as their support structures are replaced regularly once the carbon is consumed. Alumina is fed into the bath during cell operation and it is important to have good alumina dissolution. The anode gas bubbles will help to create/cause bath flow and turbulence. It is important to create a good turbulence by anode gas bubbles to the extent favorable to increase alumina dissolution.
Traditional technology relied on natural flow of gases from under the carbon anodes during the aluminum reduction process, but this delayed gas bubble removal and decreases efficiencies and aluminum production. This presence and build up of gas generated during electrolysis has been a continuing problem in the industry and a cause of high energy requirements, and to efficiently operate the electrolysis cells, the electrodes must be properly designed. With their large bottom surface area, Soderberg anodes can present serious problems in gas evolution. In a self-baking Soderberg-type electrolysis cell, during electrolysis, a large quantity of anode gas (40 to 50 kg CC^/hour) is produced on the single anode bottom surface, and the anode gas has to travel a considerable distance before it can be released from the bottom surface of the anode. The gas bubbles coalesce and grow even larger before they escape from large anode bottom surface. This process of the anode gas bubble formation, coalescence, and release/escape from anode surface creates significant cell instability, and therefore, Soderberg cells usually have a lower current efficiency than pre-baked cells. At the same time, the anode gas bubbles cover a large percentage of the bottom anode surface, which results in a significant increase in electrical resistance and cell voltage, resulting in a higher energy consumption than pre-baked cell technologies. For example, U.S. Patent No. 3,996,117 (Graham et al.), discloses a carbon block anode disposed between a steel jacket in which an anode gas, primarily CO2, is substantially trapped below an alumna-containing crust. In U.S. Patent No. 5,030,335 (Olsen), the trapped CO2 gas was recognized as a problem during the passing of the CO2 gas to a disposal burner, since the gas would also contain pitch volatiles and the combustion product would have to be wet or dry cleaned. Also, breaks in the crust would allow gas escape in the furnace building. In Olsen, a plurality of liftable cover plates was used as seals. In Olsen, the side steel jacket/manifold for the Soderberg anode is more clearly shown. None of these previous two Soderberg cell designs solves problems of CO2 gas formation of the bottom of the anode.
What is needed is a Soderberg carbon anode design that will quickly channel anode gas out of the bottom horizontal surface to improve cell current efficiency, increase cell stability and reduce electrical resistance.
Summary of the Invention It is a main object of this invention to provide a cell/Soderberg anode design that reduces the amount of gas bubbles at the bottom surface of self-baking Soderberg anodes.
The above needs are met and object accomplished by providing a series of meltable plate inserts and corresponding slots in a Soderberg anode. In one aspect,an aluminum electrolysis cell having such an Soderberg anode is provided, the Soderberg-type carbon anode consumable in molten electrolyte, having top, bottom and side surfaces, with electrically conducting vertical metal pins disposed within the anode body, the anode operating in molten electrolyte in an aluminum electrolysis cell, where gas bubbles are generated at the anode bottom surface, wherein the anode is moveable in a vertical downward direction into the molten electrolyte as the anode is consumed, and wherein the anode has a plurality of outward slots at the bottom of the anode surface along a horizontal axis of the anode. The slots are exposed to the molten electrolyte and are configured to allow anode gas bubbles to pass out of the electrolyte and away from the anode without plugging the slots. The anode includes a plurality of layers or rows of plate inserts, the plate inserts comprising at least one of aluminum, aluminum oxide, cryolite and mixtures thereof, where a bottom layer of inserts will melt/dissolve with downward movement of the anode into the molten electrolyte to form slots at the bottom of the anode upon contact with the electrolyte. The slots of the anode may be of any orientation (e.g., a vertical orientation) and are generally non-continuous. The non-continuous slots are formed in the Soderberg carbon anode such that bubbles and coalesced bubbles generated on the electrolyte surfaces flow into the slots, and the slots promote movement of the bubbles away from the center of the anode bottom surface and towards the side of the anode. In this regard, the plate inserts may be the appropriate dimension to achieve the desired slot dimension with respect to width, length and height. The width of plate inserts (therefore the slot width) may be selected such that they allow continuous channeling of a significant quantity of anode gas and a proper gas flow velocity. Preferably, the slots will not collapse or become plugged with anode gases. The plate insert height decides the slot depth, which dictates the life span of each slot. For example, the width of slots (thickness of plate inserts) may be from about 0.75 cm to 1.5 cm, preferably 1.0 cm to 1.3 cm for conventional Soderberg- style anodes. In conventional Soderberg anodes, the plate insert height may be between 6 cm to 50 cm, preferably 9 cm to 20 cm, which may produce slots lasting between 6 days to 14 days in conventional carbon anodes. The length of the plate inserts depends on the Soderberg anode width. The strength and integrity of the anode carbon are also taken into account.
The top-most slot forming plates may be positioned between the rows of steel anode stubs/pins/spikes. Slots may thus be formed/located in the canter locations between the rows of anode stubs/spikes (not touching the stubs). To insure there is sufficient number of slots during operation, the insert plates may be inserted between every other row of pins (alternated in inserting plates between adjacent rows of steel anode stubs).
In another aspect, a self-baking Soderberg-type carbon anode consumable in molten electrolyte is provided, the anode having top, bottom and side surfaces and containing a plurality of layers of vertically disposed plate inserts, the plate inserts comprising at least one of aluminum, aluminum oxide, cryolite and mixtures thereof, the plate inserts being capable of melting to create the slots at the bottom of the anode thereby, allowing any gas generated upon operation of the anode to pass through the slots to the side of the anode. In one embodiment, the plate inserts are aluminum or a low impurity aluminum alloy. Thus, the anode may include a plurality of plate inserts surrounded by carbon-based anode material. The plate inserts may be disposed at various vertical levels within the anode. For example, the plate inserts may be disposed at four distinct layers within the anode. The layers of plate inserts may be distinct or the layers may overlap, such as along a horizontal axis of the anode, (e.g., a first set of plate inserts may be disposed about a first horizontal axis and a second set of plate inserts may be disposed about a second horizontal axis, the distance between the two horizontal axis being less than the length of a set of plate inserts). The plate inserts may be aligned in a vertical direction, wherein a plurality of the plate inserts are aligned with a vertical axis of the anode, (e.g., a first set of plate inserts may be aligned with a first vertical axis and a second set of plate inserts may be aligned with a second vertical axis). In a particular embodiment, the anode includes at least four distinct layers of plate inserts, each layer including a plurality of the plate inserts. The anode may also include a plurality of slots located proximal the bottom portion of the anode. The slots are formed by melting of the plate inserts, as described.
In another aspect, methods of forming a Soderberg anode are provided, the methods including the steps of adding carbon paste to an upper portion of a casing containing a Soderberg anode, inserting plate inserts into the carbon paste, and lowering the carbon paste toward a molten electrolyte. The methods may include the step(s) of adding additional carbon paste to the upper portion of the casing and/or inserting additional plate inserts into the carbon paste. Any of the above steps may be concomitant to the step of producing aluminum with an aluminum electrolysis cell interconnected to the Soderberg anode. The number of plate inserts/slots and configurations of plate inserts/slots may be selected to effectively and efficiently restrict large gas bubble formation and channel the anode gas away from the anode surface during operation of an electrolytic cell, thus improving cell current efficiency and cell stability. Also, reducing the amount of gas bubbles at the bottom surface of Soderberg anodes will significantly reduce the electrical resistance, lower the total cell voltage, and thereby reduce the cell electrical energy consumption. Methods of producing aluminum using the above- described Soderberg anodes are also provided.
As may be appreciated, various ones of the above-noted aspects, approaches and/or embodiments may be combined to yield various inventive carbothermic production systems and methods. These and other aspects, advantages, and novel features of the invention are set forth in part in the description that follows and will become apparent to those skilled in the art upon examination of the following description and figures, or may be learned by practicing the invention.
Brief Description of the Drawings A full understanding of the invention can be appreciated from the following
Detailed Description of the Invention when read with reference to the accompanying drawings wherein:
Figure 1 is a cross-sectional broken away view of one type prior art, traditional, self-baking Soderberg anode type cell similar to that illustrated in U.S. Patent Specification 3,996,117;
Figure 2 is a schematic broken away view partly in section, front view, of part of a self-baking Soderberg anode type cell of this invention, showing a plurality of slots and embedded aluminum plate inserts within the anode;
Figure 3 is a schematic broken away view partly in section, side view, of the cell shown in Figure 2;
Figure 4 is an enlarged partial view of the operating portion of Figure 3 showing the anode in transition, in an aluminum electrolysis cell, where a slot is formed after an aluminum plate insert is melted, and where the surrounding carbon anode, shown as a dotted line, is producing bubbles and these bubbles flow into the slot, for ease of bubble removal.
Figure 5 is a schematic cross-sectional view top view of a self-baking Soderberg anode showing one positioning of the aluminum plate inserts at two vertical levels of the anode.
Figure 6 is a comparative graph of anode pot voltage noise (V) of Soderberg cells, with traditional Soderberg anodes vs. slotted Soderberg anodes;
Figure 7 (a) and 7 (b) are comparative graphs of typical anode potential vs. time showing results of gas bubble size formation and release on anode surfaces of traditional Soderberg anodes and slotted Soderberg anodes;
Figure 8 (a) and 8 (b) are comparative graphs of pot cell voltage (v) vs. time showing voltage fluctuation of a traditional Soderberg anode cell and a slotted Soderberg anode cell; and Figure 9 is comparative graph of anode gas bubble voltage drop as measured on Soderberg anodes with and without slots.
Detailed Description of the Invention Figure 1 illustrates one type of traditional self-baking Soderberg type carbon based anode 13 operating in molten electrolyte 12 in an aluminum electrolysis cell 1. This cell 1 includes a steel shell 10, a product molten aluminum metal pool 11 and an electrolyte bath 12. Anode gas (primarily CO2) bubbles appear as large trapped bubbles 2, at the bottom 3 of anode 13, coalescing into larger bubbles 4 near the side 5 of anode 13 and finally releasing as big bubbles 6, traveling upward as shown by the arrow 7. Suspended in bath 12 is a positive (+) Soderberg anode 13. Associated with the Soderberg anode are metal, usually steel spikes/conductors/pins 14a, 14b and 14c, which are connected to the positive side of a source of electrical current. A metal, usually steel jacket 15 is provided on the upper sides of the anode, where the anode constituents have not yet hardened sufficiently (unbaked) to render themselves self-supporting. As the anode is consumed, as shown by the irregular bottom 3, it is moved downward into the electrolyte as shown by dark top arrow 17.
Surrounding the anode a manifold 16 can be used to provide an upper side for the porous crust 28 and to promote fume collection usually through a conventional exhaust burner (not shown). The pool (or pad) 11 of molten aluminum is supported on carbonaceous block lining 19 and carbonaceous tamped lining 20. The carbonaceous linings can be supported on an alumina fill 21. Optionally, there can be interposed between the tamped lining and the fill some quarry tile 22. A layer of red brick 23 can be situated next to the quarry tile 22. A mica mat 18 can be used for the purpose of providing an extra degree of safety against current flow through shell 10.
The cathode current is supplied through steel bars, 24, to the block lining 19. The current supply is indicated by plus and minus signs on the anode 13 and on connector bar 24 respectively.
A plate 25, provided on the upper edge of steel shell 10 can serve the purpose of protecting carbonaceous lining when the crust 28 is being broken for the purpose of feeding additional alumina to the bath 12. The crust 28 is formed of loose particles 29a of alumina. On its lower side, the crust becomes, in part, a sintered alumina-rich material 29b. Operating parameters are selected such that a frozen layer 30 of alumina and bath bounds the sides of the aluminum metal pad 11 and bath 12. It is preferred that layer 30 extend at least down to the bottom of the slope of tamped lining 20.
As shown in this prior art Soderberg anode 13, both bottom 3 and side 5 are flat, and bubbles 2 and 4 are essentially trapped below the anode side between positive and negative poles in a semi-continuous bubble layer. In order to facilitate the release of these bubbles, the Soderberg anode shown in Figures 2-5 was developed.
As shown in Figures 2-5, this new and improved self-baking Soderberg type carbon based anode 40 has top 42, bottom 44 and side 46 surfaces, the bottom surface 44 contacting and being immersed in molten electrolyte 12, usually a molten cryolite electrolyte based on Na3AlF6 (NaF + AlF3), which will operate at a temperature from about 800° C to about 1100° C, usually from 900° C to 1000° C. A produced aluminum pool (or pad) 11 is formed beneath the molten electrolyte 12, the aluminum also acting as cathode. The cathode connector bar is shown as 24 and metal anode conductors as 14. The Soderberg anode 40 can be made from either dry or wet paste which typically comprises 20 wt. % to 30 wt. % coal tar/petroleum pitch and 70 wt. % to 80 wt. % calcined petroleum coke. Also shown in Figures 2-5 are metal anode conductors, such as steel, spikes/stubs/pins 14 (hereinafter "pins"); metal, such as steel, anode casing/jacket 15. Also shown is lining 20, the bottom portion of which may have a connector bar 24. Anode beam 57 for raising or lowering the anodes is also shown in Figures 2-3. Slot bottom edge is shown as 63 and the slot's surrounding anode is shown as 40'.
As shown in Figures 2-4, meltable aluminum-containing sheets, plates, or inserts, hereinafter "plate inserts" 48 are disposed within the anode 40 as layers or rows along horizontal axis, such as axis 66, and at a plurality of vertical levels 50. These plate inserts are capable of melting as the bottom 44 of the anode 40 bakes in the molten cryolite 12, to create outward vertical, hollow slots 52, shown here in idealized form as completely melted, best shown in the side view of Figures 3 and 4, at the bottom of the anode. Thus, anode gases (e.g., CO2) generated during operation of the electrolysis cell may easily channel through the open slots 52 to the side of the anode, as shown in Figure 4. The plate inserts (e.g., solidified/fused/molded plates) may comprise aluminum and any other tolerable levels of other materials that, upon melting, do not result in unacceptable level of impurities in the aluminum being produced. Such other materials may comprise various aluminum oxides (e.g., one or more of Al2O3; A12O3»H2O; A12O3 »2H2O and A12O3 »3H2O) such as molded or fused aluminum oxides, and/or cryolite (also molded or fused). As used herein, cryolite includes Na3AlF6, AlF3 and like additives. The aluminum may be in alloy form, such as an aluminum alloy comprising one or more of Fe, Ni, Cu, Zn, Co, or other metal materials. For example, the plate inserts may be aluminum, such as consisting essentially of aluminum, or the plate inserts may be a low impurity aluminum alloy, e.g., an aluminum alloy having less than about 0.1 wt% Fe, less than about 0.02 wt% Ni; less than about 0.05 wt% Cu; less than about 0.02 wt% Zn and/or less than about 0.02 wt% Co, so that when the aluminum alloy melts, the amount of non- aluminum components in the product melt will be commercially acceptable. The use of aluminum plates as a plate material is also desirable in that aluminum will remain a solid during the carbon paste baking step, which occurs at a temperature of between 300° C to 600° C.
The height 54, length 56 and width of the inserts 48 may be tailored in accordance with the size of the anode 40. For conventional Soderberg anodes, the slots 52 and plate inserts 48 generally have a height 54 of from about 6 cm to 50 cm, preferably 13 cm to 20 cm. For conventional anodes, if the plate inserts are under 6 cm, increased labor cost due to the number of plates that would have to be inserted during operation of the cell may be realized, and for plate inserts over 50 cm, there could be possible bleed through of paste if cryolite is used; also, anode integrity would be at risk. For conventional anodes, the length 56 of the plate inserts and slots generally ranges from about 50 cm to about 120 cm, depending on the length of the anode side. For conventional anodes, if the plate insert length is under 50 cm, the majority of the anode surface cannot be covered by the slots, and therefore, is not as effective. For conventional anodes, the width (thickness) is generally between 0.75 cm and 1.5 cm.
Referring to Figure 4, for a clearer picture of cell operation, an enlarged partial view of the side view of Figure 3 is shown. In Figure 4, the anode 40 has moved downward and completely melts the bottom layer plate insert providing slot 52 by heat from the molten electrolyte, which has a temperature higher than the melting point of the plate insert. The melted plate insert falls to the metal pad, and left behind is a rectangular slot, such as slot 52 in Figure 4. This slot 52 channels gas bubbles 60 out of the local anode surface, shown by dotted lines 13'. The plate inserts 48 are surrounded by the anode, except when plate inserts 48 interface with molten electrolyte 12 so the anode continues to react with the molten electrolyte, generating bubbles 60 and being consumed. The bubbles 60 will flow into slots 52 left after the plate inserts melt. Generally, there is coalescing into large agglomerations of bubbles. Larger bubbles will further coalesce into giant blanket type of bubbles 61. The arrows 7 show the upward path of the bubbles. In both Figures 1 and 4, when the bubbles exit the electrolyte 12, they become part of the gaseous atmosphere above the electrolyte. Also shown are optional manifold 16 and the crust of loose particles 29a of alumina and sintered alumina-rich material 29b. The carbonaceous block lining 19 contains connector bars 24. The metal pins are not shown in Figure 4 for sake of simplicity. The aluminum plate inserts 48 are interdispersed throughout the anode body 40 in no necessarily particular arrangement, but preferably, at multiple layers (e.g., one, two, three, four layers or more) in vertical columns 64, one beneath the other, and aligned in between pins 14, as best shown in Figure 2. The aluminum plate inserts 48 are disposed between the metal pins 14 as shown in Figure 2. As shown in Figure 5, the metal pins can be offset at an angle as shown, where, in that situation, the plate inserts will also be offset and generally parallel to the metal pins. In Figure 5, the set of plate inserts 48a, correspond to top plate insert 48a in Figure 2, whereas the plate insert shown in dotted form 48b corresponds to the plate insert 48b in the next column and layer, one layer down in Figure 2. End to end plate insert 48c can also be used and can be attached to or separate from the other inserts.
The slots 52 can be formed and maintained in Soderberg anodes by periodically inserting plate inserts 48 into the unbaked carbon anode paste or briquettes at the top of anodes. The slot forming plates are generally inserted in a substantially vertical position into the carbon anode paste at the top of the anodes between the steel anode pins 14.
As the anode is consumed, the plate inserts 48 will move down along with the whole anode mass. They will melt (leaving empty space and formation of slots 52 upon contact with electrolyte) and the metal will be recovered in the metal pad once the anode section (with plates) travels down into the bath. The plate inserts should not contaminate aluminum metal quality.
Figures 2-4 show where aluminum plates are inserted from the top of the anode along with charging anode paste and vertical slots are created once aluminum metal leaks out into metal pool below after the anode section travels down and in contact with molten bath.
In addition to the top to bottom plate insert arrangement for making vertical slots in the Soderberg anodes, the specifics of the plate inserts (or slots dimension) including the number of plate inserts used, the spacing of and sizes of the plate inserts are considered part of the invention. The number of slots/inserts in the Soderberg anode can be tailored to reduce the pot noise (e.g., increasing pot stability) and reduce anode gas bubble voltage drop.
Examples Anode gas bubble voltage drop with and without slots in Soderberg anodes is demonstrated in Figure 9, which is a comparison of anode gas bubble voltage drop as measured at different locations on Soderberg anodes with and without slots. The Soderberg anodes without slots are shown as voltages 120 and the Soderberg anodes with slots are shown as voltages 125. The gas bubble voltage drop on regular Soderberg anodes can be higher than 0.4 V. When slots are present in the surface, the gas bubble voltage drop can be reduced to as low as 0.15V, a difference as high as 0.25V. This is important because this is the potential of pot voltage saving by introducing slots in the Soderberg anode.
The presence of the slots reduces anode gas bubble size prior to the anode gas release/escape from the Soderberg anode surface. Shown in Figure 7(a) is an anode potential (in reference to an Al metal electrode) responding to repetitive processes of Soderberg anode gas bubble formation → coalesce → release from the anode surface where there are no slots. Each peak and valley in the spectrum represents a cycle of gas bubbles from formation to release. The magnitude of the voltage potential fluctuation, as well as the time taken to accomplish the cycle, determine the size of the anode gas formation prior to its release. When slots are present in the Soderberg anode surface, the anode gas bubble size, as well as the gas bubble formation and release processes can be modified. As seen in Figure 7(b), the magnitude of the anode potential is substantially reduced. The greatly reduced anode gas bubble size (formation and release under a Soderberg anode) under the presence of numerous slots in the Soderberg anode surface translates into reduced bubble voltage drop and a more stable pot with reduced noise. Pot voltage fluctuations on Soderberg anodes with and without slots are shown in Figures 8(b) and 8(a) respectively. The magnitude of anode gas bubble size also translates the pot stability (noise). Shown in Figure 8 (a), the typical pot voltage fluctuations are recorded on a traditional Soderberg pot. The pot voltage fluctuates from a low of 4.2V to a high of 4.5V, as influenced primarily by anode gas bubble formation and release processes. The magnitude of the cell voltage fluctuation can be significantly reduced with the formation of slots in the Soderberg surface by disrupting the large gas bubble formation on the anode surface. Figure 8(b) shows a cell voltage variation vs. time with a substantially reduced magnitude of fluctuation when slots are present. The cell voltage varies from a low of 4.3V to a high of 4.4V. Figure 8(b) shows a cell voltage time recording having a much smaller voltage fluctuation as influenced by the slots to disrupt big gas bubble formation and release on the Soderberg anode surface.
Experimental Soderberg anodes containing vertically disposed aluminum plate inserts which melted in a hot cryolite bath at about 1000° C were tested vs. traditionally unslotted Soderberg anodes for differences in bubble noise, defined as "short term" pot voltage peak to peak difference. The results indicated that "slotted" Soderberg cells have a greater potential for reducing gas bubble noise due to the higher noise associated with the large size of the single Soderberg anode.
As shown in Figure 6, the pot noise was generally higher in the Soderberg pots with traditional anodes than a pot with anodes containing slots. Traditional Soderberg anodes with high noise are shown as 100, and traditional Soderberg anodes with low noise are shown as 105, while slotted Soderberg anodes are shown as 110. The pot noise was lowest in the Soderberg anode with slots 110, (0.04-0.05 volt). There was an 80% reduction in the pot noise when comparing with high noise traditional pots 100, (-0.200 volt.). There was a 40% reduction in pot noise when comparing with traditional low noise pots 105. This means on an average the slots can reduce the pot noise as high as 0.100 volts. Less pot noise also means better pot operation and high current efficiency.
While various embodiments of the present invention have been described in detail, it is apparent that modifications and adaptations of those embodiments will occur to those skilled in the art. However, it is to be expressly understood that such modifications and adaptations are within the spirit and scope of the present invention.

Claims

What is claimed is:
1. A self-baking Soderberg type carbon anode consumable in molten electrolyte, having top, bottom and side surfaces, wherein the carbon anode has a plurality of vertically disposed plate inserts selected from the group consisting of aluminum, aluminum oxide, cryolite and mixtures thereof, meltable in molten cryolite electrolyte, said plate inserts capable of melting to create hollow slots at the bottom of the anode, allowing any gas bubbles generated upon operation of the anode to pass through the slots to the side of the anode.
2. The carbon anode of claim 1 , wherein the plate inserts are aluminum.
3 The carbon anode of any of the preceding claims, wherein the plate inserts are a low impurity aluminum, the alloy having less than about 0.1 wt% Fe; less than about 0.02 wt% Ni; less than about 0.05 wt% Cu; less than about 0.02 wt% Zn and less than about 0.02 wt% Co.
4. The carbon anode of any of the preceding claims, wherein the plate inserts have a height of from about 6 cm to about 50 cm and a width of from about 0.75 cm to about 1.5 cm.
5. The carbon anode of any of the preceding claims, wherein the top-most plate inserts are disposed between the conducting metal pins.
6. The carbon anode of any of the preceding claims, where the anode comprises coal tar and petroleum pitch.
7. An aluminum electrolysis cell comprising:
(1) at least one, consumable, self-baking Soderberg-type carbon anode, having top, bottom and side surfaces with electrically conducting vertical metal pins disposed within the anode body; (2) a molten electrolyte in which the at least one carbon anode is placed so the bottom surfaces of the anode contact the electrolyte to self- bake the bottom of the anode, and where gas bubbles are generated at the anode bottom surface; (3) means to vertically move the at least one carbon anode in a downward direction into the molten electrolyte as the at least one carbon anode is consumed by the electrolyte; and (4) a plurality of layers of plate inserts selected from the group consisting of aluminum, aluminum oxide, cryolite and mixtures thereof within the at least one carbon anode, which inserts will melt with downward movement of the anode into the molten electrolyte to provide hollow slots communicating with the electrolyte, which slots can channel gas bubbles from the bottom of the at least one carbon anode into the electrolyte.
8. The electrolysis cell of claim 7, wherein the at least one carbon anode comprises coal tar and petroleum pitch.
9. The electrolysis cell of any of claims 7 and 8, wherein the molten electrolyte is a molten cryolite bath and the plate inserts are aluminum.
10. The electrolysis cell of any of claims 7-9, wherein the molten electrolyte is a molten cryolite bath and the plate inserts are a low impurity aluminum alloy, the alloy having less than about 0.1 wt% Fe; less than about 0.02 wt% Ni; less than about 0.05 wt%Cu; less than about 0.02 wt% Zn and less than about 0.02 wt% Co.
11. The electrolysis cell of any of claims 7-10, wherein the molten electrolyte has a temperature of from about 800° C to about 1100° C.
12. The electrolysis cell of any of claims 7-10, wherein the molten electrolyte has a temperature of from about 900°C to about 1000°C.
13. The electrolysis cell of any of claims 7-12, wherein the plate inserts have a height of from about 6 cm to about 50 cm and a width of from about 0.75 cm to about 1.5 cm.
14. The electrolysis cell of any of claims 7-13, wherein the top-most plate inserts are disposed between the conducting metal pins.
15. The electrolysis cell of any of claims 7-14, wherein the gas bubbles generated do not coalesce into large agglomerations of bubbles at the bottom of the anode.
16. A method of producing a Soderberg anode comprising: adding carbon paste to an upper portion of a casing interconnected to a Soderberg anode; inserting a plurality of meltable plates into the carbon paste; and lowering the carbon paste toward a molten electrolyte.
17. A method for producing aluminum, the method comprising: contacting a molten electrolyte with a Soderberg anode; heating the molten electrolyte to a temperature of from about 900°C to about 1000°C; dissolving a plate contained in the anode to form a slot, wherein gases generated during the heating of the molten electrolyte may pass through the slot and away from the Soderberg anode.
18. A method as recited in claim 17, wherein the generated gases pass through the slot without plugging the slot.
PCT/US2006/033797 2005-08-30 2006-08-29 Methods for in-situ formation of slots in a soderberg anode WO2007027732A2 (en)

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BRPI0615403-4A BRPI0615403A2 (en) 2005-08-30 2006-08-29 methods for in-situ slot formation in a soderberg anode
EP06813942A EP1920086A2 (en) 2005-08-30 2006-08-29 Methods for in-situ formation of slots in a soderberg anode
CA002619085A CA2619085A1 (en) 2005-08-30 2006-08-29 Methods for in-situ formation of slots in a soderberg anode
AU2006284903A AU2006284903A1 (en) 2005-08-30 2006-08-29 Methods for in-situ formation of slots in a soderberg anode
EA200800720A EA012225B1 (en) 2005-08-30 2006-08-29 Methods for in-situ formation of slots in a soderberg anode

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US11/215,586 US7384521B2 (en) 2005-08-30 2005-08-30 Method for reducing cell voltage and increasing cell stability by in-situ formation of slots in a Soderberg anode
US11/215,586 2005-08-30

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Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NO20053072D0 (en) * 2005-06-22 2005-06-22 Norsk Hydro As Method and apparatus for aluminum production.
US8771497B2 (en) * 2007-04-20 2014-07-08 Mitsui Chemicals, Inc. Electrolyzer, electrodes used therefor, and electrolysis method
FR2948689B1 (en) * 2009-07-29 2011-07-29 Alcan Int Ltd GROOVED ANODE OF ELECTROLYTIC TANK
FR2970979A1 (en) * 2011-01-28 2012-08-03 Rio Tinto Alcan Int Ltd ANODE MANUFACTURING METHOD
FR3028265A1 (en) * 2014-11-12 2016-05-13 Rio Tinto Alcan Int Ltd PROCESS FOR HANDLING A PLURALITY OF ANODES INTENDED FOR THE PRODUCTION OF ALUMINUM BY IGNEOUS ELECTROLYSIS
CN105256332A (en) * 2015-11-13 2016-01-20 湖南创元铝业有限公司 Pre-baking anode for aluminum electrolysis and aluminum electrolysis cell
WO2018058204A1 (en) * 2016-09-29 2018-04-05 Caete Engenharia Ltda Carbonaceous anode for aluminium electrolysis with aluminium insert and process for construction thereof
CN106894055B (en) 2016-12-30 2018-07-17 山西精之铝科技有限公司 The continuous aluminium frame anode aluminium cell of built-in conductor
AU2018247009B2 (en) 2017-03-31 2023-07-06 Alcoa Usa Corp. Systems and methods of electrolytic production of aluminum
BR112021011476A2 (en) 2018-12-19 2021-08-31 R + D Carbon Ltd ANODE FOR ALUMINUM ELECTROLYSIS AND ITS MANUFACTURING METHOD
CN113336550A (en) * 2021-05-28 2021-09-03 河南中孚铝业有限公司 Production method of porous anode carbon block for electrolytic aluminum
CN113737224B (en) * 2021-10-09 2023-01-20 中国铝业股份有限公司 Novel anode for continuous anode aluminum electrolytic cell and paste thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2917441A (en) * 1955-12-28 1959-12-15 Reading Anthracite Company Self baking electrode construction
US2958641A (en) * 1958-05-20 1960-11-01 Reynolds Metals Co Anode for alumina reduction cells
US4342637A (en) * 1979-07-30 1982-08-03 Metallurgical, Inc. Composite anode for the electrolytic deposition of aluminum

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1440724A (en) 1919-09-08 1923-01-02 Norske Elektrokemisk Ind As Electrode for electric furnaces and process for manufacturing the same
US2480474A (en) 1945-12-14 1949-08-30 Reynolds Metals Co Method of producing aluminum
CH536360A (en) 1970-12-01 1973-04-30 Alusuisse Process for the production of aluminum by electrolysis of aluminum oxide in a fluoride melt flow
US3996117A (en) 1974-03-27 1976-12-07 Aluminum Company Of America Process for producing aluminum
US4602990A (en) 1983-02-17 1986-07-29 Commonwealth Aluminum Corporation Low energy aluminum reduction cell with induced bath flow
NO168542C (en) 1989-05-24 1992-03-04 Elkem Aluminium DEVICE FOR GAS COLLECTION IN OVENS FOR MELT ELECTROLYTIC ALUMINUM PREPARATION.
US5380416A (en) * 1993-12-02 1995-01-10 Reynolds Metals Company Aluminum reduction cell carbon anode power connector
US5746906A (en) * 1995-08-10 1998-05-05 Koppers Industries, Inc. Coal tar pitch blend having low polycyclic aromatic hydrocarbon content and method of making thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2917441A (en) * 1955-12-28 1959-12-15 Reading Anthracite Company Self baking electrode construction
US2958641A (en) * 1958-05-20 1960-11-01 Reynolds Metals Co Anode for alumina reduction cells
US4342637A (en) * 1979-07-30 1982-08-03 Metallurgical, Inc. Composite anode for the electrolytic deposition of aluminum

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US7384521B2 (en) 2008-06-10
US20070045104A1 (en) 2007-03-01
EA200800720A1 (en) 2008-08-29
CA2619085A1 (en) 2007-03-08
EP1920086A2 (en) 2008-05-14
WO2007027732A3 (en) 2007-08-23
EA012225B1 (en) 2009-08-28
AU2006284903A1 (en) 2007-03-08
CN101379223A (en) 2009-03-04

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