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EP0979596A1 - Electrode type söderberg for making silicon alloys and silicon metal - Google Patents

Electrode type söderberg for making silicon alloys and silicon metal

Info

Publication number
EP0979596A1
EP0979596A1 EP98916756A EP98916756A EP0979596A1 EP 0979596 A1 EP0979596 A1 EP 0979596A1 EP 98916756 A EP98916756 A EP 98916756A EP 98916756 A EP98916756 A EP 98916756A EP 0979596 A1 EP0979596 A1 EP 0979596A1
Authority
EP
European Patent Office
Prior art keywords
casing
central core
electrode
die
furnace
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP98916756A
Other languages
German (de)
French (fr)
Other versions
EP0979596B1 (en
EP0979596B9 (en
Inventor
René BOISVERT
Jacques Dostaler
Jacques Dubois
Dieter W. Ksinsik
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Becancour Silicon Inc
Original Assignee
Becancour Silicon Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from CA002204425A external-priority patent/CA2204425A1/en
Application filed by Becancour Silicon Inc filed Critical Becancour Silicon Inc
Priority to SI9830264T priority Critical patent/SI0979596T1/en
Publication of EP0979596A1 publication Critical patent/EP0979596A1/en
Publication of EP0979596B1 publication Critical patent/EP0979596B1/en
Application granted granted Critical
Publication of EP0979596B9 publication Critical patent/EP0979596B9/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B7/00Heating by electric discharge
    • H05B7/02Details
    • H05B7/10Mountings, supports, terminals or arrangements for feeding or guiding electrodes
    • H05B7/107Mountings, supports, terminals or arrangements for feeding or guiding electrodes specially adapted for self-baking electrodes
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B7/00Heating by electric discharge
    • H05B7/02Details
    • H05B7/06Electrodes
    • H05B7/08Electrodes non-consumable
    • H05B7/085Electrodes non-consumable mainly consisting of carbon
    • H05B7/09Self-baking electrodes, e.g. Söderberg type electrodes

Definitions

  • This invention relates to a self-baking electrode for the production of silicon alloys and silicon metal.
  • Self-baking electrodes also called “Soderberg electrodes”
  • Self-baking electrodes basically consist of a carbon- containing material such as anthracite, pet coke, tar and pitch, which is filled into a steel casing held in position within an electric arc furnace by means of contact shoes and a suspension/slipping device.
  • the application of high electric currents plus the heat of the arc struck by the electrode during the furnace operation develops sufficient heat to melt the material filled into the casing and form a paste, then cokify the so-formed paste, and finally bake the electrode.
  • the steel casings of the Soderberg electrodes presently in use are in majority round in shape and provided with a series of inwardly projecting fins extending radially towards the center of the electrode in order to provide mechanical strength to the electrode, heat penetration within the electrode through the conductivity of the fins and act as current conductor.
  • the fins and the casing are typically made of regular steel, and their amount, length and physical shape depend on what is considered optimum for thorough baking as per each geometric design.
  • both the paste and casing have to be replaced. This is done high on top of the electrode column so that there is sufficient static pressure for compaction, and for running through the various stages of the temperature pattern from softening of the paste up to the heat generated by current flow. Consumption of tlie electrode is compensated by regular slipping of the electrode llirough the contact shoes. The iron casing and tlie fins passing down the contact shoes at each slipping burn and oxidize or melt, and thereby fall into die mix.
  • tlie iron pick-up is of such a magnitude that the Soderberg technology cannot be applied to produce commercial grade silicon metal where, depending on the quality grade for Si, the Fe content has to be below 1 %, below 0.5%, below 0.35% or even below 0.2% .
  • silicon metal has been produced exclusively by using a so-called “pie-baked” electrode, which is an amorphous carbon or semi-graphitized electrode produced in specific manufacturing units and then supplied in sections of typically 2 to 2.5 m length.
  • These pre-baked electrodes which are usually 4 to 6 times more expensive than Soderberg electrodes, are to be connected to each other by specific devices, which can be nipples and sockets or a system of male/female design cuts at the ends of each section of the electrode. In operation in a silicon metal furnace, these connections between pieces of electrodes are limiting factors for energy transfer from one electrode to the other underneath the contact shoe.
  • Soderberg technology The periodic slippings of the casing do slightly contaminate the Si not only with the iron of the casing, but also with die alloying elements used in the casing material to provide the maximum possible heat oxidation protection. These contaminants tend to make silicon metal produced this way unsuitable for its application in the chemical industry to produce methylchlorosilanes out of silicon metal. Casings made of regular steel also have their disadvantages as vital properties for functioning are decreased by heat, the furnace atmosphere and die time they are exposed to those.
  • Another object of die present invention is to provide a new electrode system which allows the production of silicon metal in a Soderberg-type furnace without any modification to the existing slipping system or addition of another slipping system. Thanks to the electrode according to the invention, the same furnace can produce both FeSi of any grade and Si metal wi iout any downtime between die gradual change from one product to the other and each time at the lowest electrode cost.
  • the electrode according to the invention overcomes ie problems associated with prior art: silicon metal contamination, core breakages as a result of extrusion forces, casing deformation, loss of production and capital expense for installation of new slipping systems. It also provides a way to convert bigger and more efficient ferro-silicon Soderberg-type furnaces instead of existing silicon metal furnaces with pre-baked electrode technology.
  • die present invention relates to an in situ self-baking electrode suitable for use in an electric arc furnace, the electrode comprising: an elongated open ended electrically conductive casing that extends generally vertically within the furnace in use; a central core disposed within and spaced from the casing, the central core being made of a heat conductive material; at least one framework widiin the casing, die framework securing the central core to an inner surface of the casing for holding centrally the central core widiin the casing and for preventing an extrusion of the central core downward; and a carbonaceous electrode paste surrounding die central core, the paste being devised to cure into a solid electrode upon heating and to bond to die central core.
  • the present invention also relates to an electric arc furnace embodying a self- baking electrode as described hereinbefore. More particularly, the electric arc furnace comprises an electric arc furnace comprising: a furnace body containing a charge to be heated; an in situ self-baking electrode comprising: an elongated open ended electrically conductive casing having an upper end and a bottom end, said casing extending generally vertically widiin die furnace body and being free to slip vertically through a slipping mechanism; a central core disposed within and spaced from the casing the central core being made of heat conductive material; at least one framework within the casing, the framework securing the central core to an inner surface of the casing for holding centrally the central core within the casing and for preventing an extrusion of the central core downward through the bottom end of the casing; a carbonaceous electrode paste surrounding the central core the paste being devised to cure into a solid electrode upon heating and to bond to the central core; means for retaining the casing in a generally vertical position within the furnace body;
  • a further object of die present invention is to propose a process for forming in situ a self-baking electrode in an electric arc furnace, the process comprising the steps of: a) providing an elongated open ended electrically conductive casing; b) disposing an elongated central core of conductive heat material widiin and spaced from die casing; c) securing the central core to an inner surface of the casing and holding it centrally within the casing; d) sliding die elongated electrically conductive casing within die furnace for extending generally vertically dierein; e) introducing a quantity of carbonaceous electrode paste in die casing and surrounding die central core, the paste being devised to cure into a solid electrode upon heating and to bond to the central core; and
  • the central core of the electrode preferably consists of carbon or carbidic bars or rods connected to each odier so that the heat transfer is essentially uninterrupted in their connection.
  • Use can also be made of metal rods or bars.
  • a core in the form of bars or rods can be hollowed to allow inside cooling through injection of di-atomic or inert gases. Such is particularly useful to control and influence the arc at die tip of die electrode and the baking of the electrode.
  • die material forming the casing is selected so as to be electrically conductive to transfer electric power from the contact shoes into the Soderberg paste while preferably preventing undesired metallic contamination by either Ti, V, Ta, Cr, Zr or Ni.
  • the casing can be made of Cu or brass, or of an aluminum alloy or aluminum of sufficient strengtii to support the pressure of the filling of Soderberg paste without deformation or dents.
  • the electrode according to the invention allows a user to switch from the production of ferrosilicon using regular Soderberg electrodes to the production of silicon metal using the technology described hereinabove, without any downtime, and since no additional devices to guide the graphite core are required, switch-back to Soderberg technology is possible and only with this technology.
  • an important improvement in die electrode according to the invention lies in that the central core of the electrode which is secured to die casing is "released" from its function of transferring compression forces for the extrusion as for die electrode described in prior art as indicated above.
  • Figure 1 is a side elevational view, partly in section, schematically illustrating an electric arc furnace in which an electrode according to the present invention is used;
  • Figure 2 is a side elevational cross-section view of an electrode according to a preferred embodiment of the invention, shown above a conventional Soderberg electrode;
  • Figure 3 is a cross section view of the electrode of Figure 2, taken along line 1I-II in Figure 2.
  • an electric arc furnace (2) in which an electrode (4) according to die present invention may be employed is illustrated.
  • the furnace (2) is of a conventional design and may be used for smelting for example, ferrosilicon and silicon metal.
  • the furnace (2) comprises a furnace body (6) formed of an outer steel shell and a suitable refractory material.
  • a curtain (8) is extending upwardly from the furnace body (6) and it has an upper end engaged by the hood (10) or cover of die furnace body (6).
  • the electrode (4) extends vertically within the furnace body (6) through an opening (12) in die hood (10).
  • the furnace (2) comprises electric means for providing an electric arc in the furnace (2) for smelting a charge (14) in the furnace body (6).
  • the electric means comprises a contact, such as a contact shoe (16), connected to die electrode (4).
  • the contact shoe (16) is mounted on the electrode (4) with a conventional half-ring (18).
  • the furnace (2) may also be provided " with a water-cooled jacket (20) for cooling the electrode (4) above the contact shoe (16).
  • Retaining means are provided for retaining die electrode (4) vertically within the furnace (2).
  • the retaining means preferably comprises regulation cylinders (22) and two slipping bands (24) mounted on an upper floor (26) of die furnace building and supporting the electrode (4).
  • the self- baking electrode (4) comprises an elongated open ended electrically conductive casing (30) for extending generally vertically within the furnace (2) in use.
  • This casing (30) has an upper end (31) and a bottom end (33).
  • a central core (32) made of a heat conductive material, preferably made of a carbonaceous material, is disposed within and spaced from the casing (30).
  • the casing (30) and the central core (32) define an annular channel (34) in which a carbonaceous electrode paste (36), preferably Soderberg paste, can be fed, molten and baked.
  • a carbonaceous electrode paste (36) is surrounding the central core (32), the paste
  • the central core (32) can be shaped as a bar or otiier defined shapes and is held centrally within the casing (30) by at least one framework (37) which prevents relative movement of the central core (32) with respect to the casing (30) due to the paste movement between die core (32) and the casing (30).
  • the casing (30) is made of a thin-walled ordinary steel or a tiiicker- walled Dural ® so that the rigidity of the walls can stand the radial pressure of die filled-in Soderberg paste (36).
  • the filling of the Soderberg paste (36) into die electrode casing (30) is done in a quasi continuous manner so as to minimize the
  • the casing (30) is preferably made of a material unalloyed with a metal selected from me group consisting of titanium, vanadium, tantalum, chrome, zirconium and nickel, for preventing contamination of the silicon metal to be produced in the furnace (2) with one of said metal upon an ongoing consumption of die casing in the furnace (2). More preferably in this case, the casing (30) is made of a metal selected from the group consisting of copper, brass and aluminum.
  • the framework (37) securing the central core (32) to an inner surface of the casing (30) preferably comprises a pair of opposite rods (38), each rod (38) extending generally horizontally and having a first end (40) driven into the central core (32) and a second end (42) secured to an inner surface of the casing (30).
  • a bar (44) is extending through the central core (32) below the pair of rods (38), the bar (44) having its opposite outer ends (46) projecting out from the central core (32).
  • the framework (37) further comprises two lateral frame members (48), each connecting together the second end (42) of each rod (38) to a corresponding outer end (46) of the bar (44).
  • two further rods (60) may preferably be provided for preventing the central core (32) from twisting or rotating within die casing (30).
  • Each of said rods (60) comprises a first end (62) secured to the central core (32) and a second end (64) secured to the inner wall of the casing (30), the two rods (60) being tangent with the central core (32).
  • spread-out sheets (47) may be fixed to die inner surface of the casing (30) to better prevent an extrusion of the baked paste (36) downward.
  • the framework (37) alone prevents very well any extrusion of the baked electrode (36) downward, die baked electrode (36) bonding against the framework (37).
  • a conventional Soderberg electrode (49) is illustrated below the electrode (4) according to the present invention.
  • This conventional Soderberg electrode (49) comprises a casing (50) and fins (52) mounted on die inner wall of the casing (50).
  • a self-baked electrode (54) is formed within the casing (50) and both die electrode (54) and casing (50) moved down in unison. This type of electrode is well known in the art and does not need further description.
  • tiiis conventional Soderberg electrode (48) may have the same diameter as the diameter of the electrode (4) according to the invention, showing that it is possible to easily switch from the production of ferrosilicon using a regular Soderberg electrode (49) to die production of a silicon metal using an electrode according to the invention without any downtime or shutdown of die whole furnace.
  • the particular structure of the electrode according to the invention allows for a great reduction in the volume of metal, such as steel, that is normally used for preventing the extrusion of the self-baked electrode downwards.
  • the electrode according to the invention it is possible to obtain a silicon metal containing less tiian 0.5% Fe, with a casing still made of steel.
  • the present invention uses, in a well balanced system, the heat conductivity of the central core (32) to bake die surrounding Soderberg paste (36). It does not necessitate a relative movement of the baked electrode (36) with respect to its surrounding casing (30) as is the case with the compound electrodes known in prior art and for use in die silicon metal production.
  • the process for forming in situ a self-baking electrode (4) in an electric arc furnace (2) comprises me following sequence of steps. a) An elongated open ended electrically conductive casing is provided. b) An elongated central core (32) of conductive heat material is disposed widiin and spaced from die casing (30). c) The central core (30) is secured to an inner surface of die casing (30) and held centrally within the casing (30). d) The elongated electrically conductive casing (30) is slid within the furnace
  • a quantity of carbonaceous electrode paste (36) is introduced in the casing (30) surrounding the central core (32).
  • the paste (36) is devised to cure into a solid electrode upon heating and to bond to the central core (32).
  • An electric arc is present in the furnace (2) in a well know manner which do not need furtiier description.
  • the central core (32) is secured to die casing (30) by driving respectively into two opposite sides of the central core (30), a first end (40) of a corresponding rod (38) of a pair of opposite rods (38) and then securing a second end (42) of each of said opposite rods (38) to an inner surface of die casing (30) such that each rod (38) is extending generally horizontally within the casing
  • a bar (44) is inserted through the central core (32) below the two rods (38) such that the opposite outer ends (46) of the bar (44) are projecting out from the central core (32).
  • the second end (42) of each rod (38) is respectively connected to a corresponding outer end (46) of the bar (44) with a lateral frame member (48).
  • the casing (30), in step d) may preferably be slid on top of a previous Soderberg-type self-baking electrode (49) used for die production of ferrosilicon, as shown in figure 2.
  • the casing (30) used for the production of silicon may have substantially the same diameter as die outer casing (50) of die Soderberg electrode (48).

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Furnace Details (AREA)
  • Silicon Compounds (AREA)
  • Discharge Heating (AREA)
  • Ceramic Products (AREA)

Abstract

The self-baking electrode suitable for use in an electric arc furnace comprises an elongated open ended electrically conductive casing for extending generally vertically within the furnace. A central core made of a heat conductive material is disposed within and spaced from the casing. A framework within is securing the central core to an inner surface of the casing for holding centrally the central core within the casing and for preventing an extrusion of the central core downward. The central core is surrounded by a carbonaceous electrode paste devised to cure into a solid electrode upon heating and to bond to the central core. This self-baking electrode allows the production of silicon metal in a Söderberg-type furnace without any modification to the usual slipping system or addition of another slipping system. An electrode according to the invention allows the same furnace to produce both FeSi of any grade and Si metal without any downtime between the gradual change from one product to the other and each time at the lowest electrode cost.

Description

ELECTRODE TYPE SODERBERG FOR MAKING SILICON ALLOYS AND SILICON METAL
FIELD OF THE INVENTION
This invention relates to a self-baking electrode for the production of silicon alloys and silicon metal.
BRIEF DESCRIPTION OF THE PRIOR ART
The use of self-baking electrodes (also called "Soderberg electrodes") for the production of ferro-alloys has been known for about 75 years (see US Patent no. 1 ,440,724 of September 1919 and US Patent no. 1 ,441 ,037 of January 1923 both in the name of Soderberg). Self-baking electrodes basically consist of a carbon- containing material such as anthracite, pet coke, tar and pitch, which is filled into a steel casing held in position within an electric arc furnace by means of contact shoes and a suspension/slipping device. The application of high electric currents plus the heat of the arc struck by the electrode during the furnace operation develops sufficient heat to melt the material filled into the casing and form a paste, then cokify the so-formed paste, and finally bake the electrode. The steel casings of the Soderberg electrodes presently in use are in majority round in shape and provided with a series of inwardly projecting fins extending radially towards the center of the electrode in order to provide mechanical strength to the electrode, heat penetration within the electrode through the conductivity of the fins and act as current conductor. The fins and the casing are typically made of regular steel, and their amount, length and physical shape depend on what is considered optimum for thorough baking as per each geometric design.
As the electrode is consumed during the production of silicon or ferro-alloy, both the paste and casing have to be replaced. This is done high on top of the electrode column so that there is sufficient static pressure for compaction, and for running through the various stages of the temperature pattern from softening of the paste up to the heat generated by current flow. Consumption of tlie electrode is compensated by regular slipping of the electrode llirough the contact shoes. The iron casing and tlie fins passing down the contact shoes at each slipping burn and oxidize or melt, and thereby fall into die mix. Because of this consumption/oxidation, tlie iron pick-up is of such a magnitude that the Soderberg technology cannot be applied to produce commercial grade silicon metal where, depending on the quality grade for Si, the Fe content has to be below 1 %, below 0.5%, below 0.35% or even below 0.2% .
Therefore, so far, silicon metal has been produced exclusively by using a so- called "pie-baked" electrode, which is an amorphous carbon or semi-graphitized electrode produced in specific manufacturing units and then supplied in sections of typically 2 to 2.5 m length. These pre-baked electrodes, which are usually 4 to 6 times more expensive than Soderberg electrodes, are to be connected to each other by specific devices, which can be nipples and sockets or a system of male/female design cuts at the ends of each section of the electrode. In operation in a silicon metal furnace, these connections between pieces of electrodes are limiting factors for energy transfer from one electrode to the other underneath the contact shoe.
Because of the heat and current transfer pattern, nipples and sockets are prone to breaking with abrupt changes of power in the furnace - as caused by any type of power shutdown - so that electrode breakages are part of undesired negative influences on operation.
Furthermore, their strength is relatively low as compared to the Soderberg electrodes, which do not contain the weak spots due to connectors or nipples, making it more solid and accepting higher specific power per square section.
Therefore, reduction of electrode costs using the self-baking principle is one of the main challenges of every silicon metal producer.
Many attempts have been undertaken to develop a type of Soderberg electrode which would allow a cheaper production of silicon metal while meeting all the criteria for reducing the amount of iron in the produced metal.
In the 70' , Nippon Denko of Japan developed a system in which tlie casings and fins usually made of steel were replaced by casings and fins made of aluminum
(see Japanese Patents nos. 951,888 and 835,596). This attempt to use aluminum for both the casing and fins has never been used industrially, because of the lack of mechanical stability and the substantially different conductivity of aluminum compared to steel.
Another approach was undertaken by M. Cavigli (see Italian Patent no. 606,568 of July 1960). In this patent, it was suggested to remove the fins from the outer casing and to adjust the relative movement of tlie paste wiUi respect to die outside casing by sliding or extruding U e inner contents of the casing as a central consumable member. Iron crosses were provided within the casing to support tlie electrode while it baked. These iron crosses held the electrode while allowing a relative movement between die casing and the electrode by either pressing or reducing the suspension weight. This system has been in operation in one plant in Italy. It permits to reduce the iron contamination, as the slipping of die casing represents only 1/10 of the slipping of the electrode itself. However, it does not permit to reach die same low level in iron impurities as obtained widi conventional pre-baked electrodes.
Another approach has been undertaken by Bruff (see US Patent no. 4,527,329 of July 1985). This patent suggests to separate the baking of the paste from the one that takes place by tlie application of heat through Ohm's resistance and conductivity in and below die contact shoes. Thus, a separate baking installation is located way above die contact shoes. Moreover, a device is provided to cut and remove Uie iron casing underneath the baking system, well above die contact shoes, so that basically a shaped pre-baked-like electrode enters the contact shoes. This system operates in a small furnace of about 10MW at Elkem Kristiansand. However, there are severe restrictions in the use for higher powered furnaces widi larger diameter electrodes, which are die manufacturing standard for cost efficiency in the developed world.
A similar solution has also been disclosed in German Patent Application no. 4,036,133 of May 1991 in the name of E. Svana.
A further system based on a relative movement of a self-baking electrode widi respect to an external casing has been disclosed by Persson in US Patent no.
4,575,856 of March 1986. In this patent, die iron crosses used by Cavigli in his system are replaced by smaller graphite electrodes put concentrically into die casing. The small electrodes are supported and moved by a separate slipping/holding device, which allows tfieir relative movement within the casing.
An improved system based on a "transfer" from a conventional pre-baked electrode to one of the extruded type as described by Cavigli and Persson is described in Canadian patent no. 2,081 ,295.
The disadvantages of this system mainly result from the physical strength limitations of the graphite electrode core and its limited potential to absorb compression, tension and bending forces as the electrode core is essentially unguided over lengths of up to 14 m and can deviate from its vertical position for various reasons. Furthermore, the casing which, in diis system, is essentially an extrusion dye, needs to be slipped down occasionally to compensate for heat damages between and underneath the contact shoes. Without such periodic slipping, damages would reach high up in die contact shoes, and liquid paste would start to drip and thereby provoke disturbances known as "green" breakages in the
Soderberg technology. The periodic slippings of the casing do slightly contaminate the Si not only with the iron of the casing, but also with die alloying elements used in the casing material to provide the maximum possible heat oxidation protection. These contaminants tend to make silicon metal produced this way unsuitable for its application in the chemical industry to produce methylchlorosilanes out of silicon metal. Casings made of regular steel also have their disadvantages as vital properties for functioning are decreased by heat, the furnace atmosphere and die time they are exposed to those.
OBJECTS OF THE PRESENT INVENTION
It is an object of die present invention to provide a new and improved self- baking electrode.
Another object of die present invention is to provide a new electrode system which allows the production of silicon metal in a Soderberg-type furnace without any modification to the existing slipping system or addition of another slipping system. Thanks to the electrode according to the invention, the same furnace can produce both FeSi of any grade and Si metal wi iout any downtime between die gradual change from one product to the other and each time at the lowest electrode cost.
The electrode according to the invention overcomes ie problems associated with prior art: silicon metal contamination, core breakages as a result of extrusion forces, casing deformation, loss of production and capital expense for installation of new slipping systems. It also provides a way to convert bigger and more efficient ferro-silicon Soderberg-type furnaces instead of existing silicon metal furnaces with pre-baked electrode technology.
SUMMARY OF THE INVENTION
Accordingly, die present invention relates to an in situ self-baking electrode suitable for use in an electric arc furnace, the electrode comprising: an elongated open ended electrically conductive casing that extends generally vertically within the furnace in use; a central core disposed within and spaced from the casing, the central core being made of a heat conductive material; at least one framework widiin the casing, die framework securing the central core to an inner surface of the casing for holding centrally the central core widiin the casing and for preventing an extrusion of the central core downward; and a carbonaceous electrode paste surrounding die central core, the paste being devised to cure into a solid electrode upon heating and to bond to die central core. The present invention also relates to an electric arc furnace embodying a self- baking electrode as described hereinbefore. More particularly, the electric arc furnace comprises an electric arc furnace comprising: a furnace body containing a charge to be heated; an in situ self-baking electrode comprising: an elongated open ended electrically conductive casing having an upper end and a bottom end, said casing extending generally vertically widiin die furnace body and being free to slip vertically through a slipping mechanism; a central core disposed within and spaced from the casing the central core being made of heat conductive material; at least one framework within the casing, the framework securing the central core to an inner surface of the casing for holding centrally the central core within the casing and for preventing an extrusion of the central core downward through the bottom end of the casing; a carbonaceous electrode paste surrounding the central core the paste being devised to cure into a solid electrode upon heating and to bond to the central core; means for retaining the casing in a generally vertical position within the furnace body; and electric means for generating an electric arc in the furnace, the electric means comprising a contact on die casing.
A further object of die present invention is to propose a process for forming in situ a self-baking electrode in an electric arc furnace, the process comprising the steps of: a) providing an elongated open ended electrically conductive casing; b) disposing an elongated central core of conductive heat material widiin and spaced from die casing; c) securing the central core to an inner surface of the casing and holding it centrally within the casing; d) sliding die elongated electrically conductive casing within die furnace for extending generally vertically dierein; e) introducing a quantity of carbonaceous electrode paste in die casing and surrounding die central core, the paste being devised to cure into a solid electrode upon heating and to bond to the central core; and
0 contacting die casing to an electric power source; and g) generating with the electric power source an electric arc into the furnace.
The central core of the electrode preferably consists of carbon or carbidic bars or rods connected to each odier so that the heat transfer is essentially uninterrupted in their connection. Use can also be made of metal rods or bars. Whatever be the material used for the manufacture of the central core, such a core in the form of bars or rods can be hollowed to allow inside cooling through injection of di-atomic or inert gases. Such is particularly useful to control and influence the arc at die tip of die electrode and the baking of the electrode. In accordance with the invention, die material forming the casing is selected so as to be electrically conductive to transfer electric power from the contact shoes into the Soderberg paste while preferably preventing undesired metallic contamination by either Ti, V, Ta, Cr, Zr or Ni. Advantageously, the casing can be made of Cu or brass, or of an aluminum alloy or aluminum of sufficient strengtii to support the pressure of the filling of Soderberg paste without deformation or dents.
Such a possible selection makes the invention particularly useful to produce silicon metal of suitable quality for application in the Rochow-direct syndiesis.
Indeed, one has only to select the material forming die conductive core and supporting casing so that the resulting metallic additions to die melting contains suitable amounts of Al and/or Cu and/or zinc and/or tin as are required in d e silicon thus produced.
Advantageously, the electrode according to the invention allows a user to switch from the production of ferrosilicon using regular Soderberg electrodes to the production of silicon metal using the technology described hereinabove, without any downtime, and since no additional devices to guide the graphite core are required, switch-back to Soderberg technology is possible and only with this technology.
As can be appreciated, an important improvement in die electrode according to the invention lies in that the central core of the electrode which is secured to die casing is "released" from its function of transferring compression forces for the extrusion as for die electrode described in prior art as indicated above.
Consequently, it does not expose die core material to the risk of buckling when compressed, and tiiereby of breaking. It furthermore eliminates the need for a separate slipping device to perform the functions of the central core, and thereby die substantial costs for irreversible retro-fitting of existing furnaces from die pre-baked carbon-electrode design to the extruded concept as described hereinabove.
Furthermore, it allows a much safer application of a hollow core electrode, where in the case of the extruded principle, the presence of such a central hole in the central core further weakens mechanically the core in cross section, in particular at the level of the nipples or connectors, with an even more pronounced susceptibility to breakages or damages in the column while performing the extrusion increments. A non restrictive description of a preferred embodiment will now be given widi reference to the appended drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a side elevational view, partly in section, schematically illustrating an electric arc furnace in which an electrode according to the present invention is used;
Figure 2 is a side elevational cross-section view of an electrode according to a preferred embodiment of the invention, shown above a conventional Soderberg electrode; and
Figure 3 is a cross section view of the electrode of Figure 2, taken along line 1I-II in Figure 2.
DESCRIPTION OF A PREFERRED EMBODIMENT
Referring to figure 1 , an electric arc furnace (2) in which an electrode (4) according to die present invention may be employed is illustrated. The furnace (2) is of a conventional design and may be used for smelting for example, ferrosilicon and silicon metal. As well known in the art, the furnace (2) comprises a furnace body (6) formed of an outer steel shell and a suitable refractory material. A curtain (8) is extending upwardly from the furnace body (6) and it has an upper end engaged by the hood (10) or cover of die furnace body (6). The electrode (4) extends vertically within the furnace body (6) through an opening (12) in die hood (10). The furnace (2) comprises electric means for providing an electric arc in the furnace (2) for smelting a charge (14) in the furnace body (6). The electric means comprises a contact, such as a contact shoe (16), connected to die electrode (4). The contact shoe (16) is mounted on the electrode (4) with a conventional half-ring (18). The furnace (2) may also be provided" with a water-cooled jacket (20) for cooling the electrode (4) above the contact shoe (16). Retaining means are provided for retaining die electrode (4) vertically within the furnace (2). The retaining means preferably comprises regulation cylinders (22) and two slipping bands (24) mounted on an upper floor (26) of die furnace building and supporting the electrode (4).
Referring more particularly to figures 2 and 3, the self- baking electrode (4) according to the present invention comprises an elongated open ended electrically conductive casing (30) for extending generally vertically within the furnace (2) in use. This casing (30) has an upper end (31) and a bottom end (33). A central core (32) made of a heat conductive material, preferably made of a carbonaceous material, is disposed within and spaced from the casing (30). The casing (30) and the central core (32) define an annular channel (34) in which a carbonaceous electrode paste (36), preferably Soderberg paste, can be fed, molten and baked. In otiier words, a carbonaceous electrode paste (36) is surrounding the central core (32), the paste
(36) being devised to cure into a solid electrode upon heating and to bond to die central core (32).
The central core (32) can be shaped as a bar or otiier defined shapes and is held centrally within the casing (30) by at least one framework (37) which prevents relative movement of the central core (32) with respect to the casing (30) due to the paste movement between die core (32) and the casing (30).
Preferably, the casing (30) is made of a thin-walled ordinary steel or a tiiicker- walled Dural® so that the rigidity of the walls can stand the radial pressure of die filled-in Soderberg paste (36). The filling of the Soderberg paste (36) into die electrode casing (30) is done in a quasi continuous manner so as to minimize the
"falling" height and also the total length above the contact shoes.
In case where silicon metal is to be produced in the furnace (2), the casing (30) is preferably made of a material unalloyed with a metal selected from me group consisting of titanium, vanadium, tantalum, chrome, zirconium and nickel, for preventing contamination of the silicon metal to be produced in the furnace (2) with one of said metal upon an ongoing consumption of die casing in the furnace (2). More preferably in this case, the casing (30) is made of a metal selected from the group consisting of copper, brass and aluminum.
As shown in Figures 2 and 3, the framework (37) securing the central core (32) to an inner surface of the casing (30) preferably comprises a pair of opposite rods (38), each rod (38) extending generally horizontally and having a first end (40) driven into the central core (32) and a second end (42) secured to an inner surface of the casing (30). A bar (44) is extending through the central core (32) below the pair of rods (38), the bar (44) having its opposite outer ends (46) projecting out from the central core (32). The framework (37) further comprises two lateral frame members (48), each connecting together the second end (42) of each rod (38) to a corresponding outer end (46) of the bar (44). Referring to figure 3, two further rods (60) may preferably be provided for preventing the central core (32) from twisting or rotating within die casing (30). Each of said rods (60) comprises a first end (62) secured to the central core (32) and a second end (64) secured to the inner wall of the casing (30), the two rods (60) being tangent with the central core (32).
Although not essential, spread-out sheets (47) may be fixed to die inner surface of the casing (30) to better prevent an extrusion of the baked paste (36) downward. However, experiments have shown that the framework (37) alone prevents very well any extrusion of the baked electrode (36) downward, die baked electrode (36) bonding against the framework (37).
Referring to figure 2, a conventional Soderberg electrode (49) is illustrated below the electrode (4) according to the present invention. This conventional Soderberg electrode (49) comprises a casing (50) and fins (52) mounted on die inner wall of the casing (50). A self-baked electrode (54) is formed within the casing (50) and both die electrode (54) and casing (50) moved down in unison. This type of electrode is well known in the art and does not need further description. As can be appreciated, tiiis conventional Soderberg electrode (48) may have the same diameter as the diameter of the electrode (4) according to the invention, showing that it is possible to easily switch from the production of ferrosilicon using a regular Soderberg electrode (49) to die production of a silicon metal using an electrode according to the invention without any downtime or shutdown of die whole furnace. The particular structure of the electrode according to the invention allows for a great reduction in the volume of metal, such as steel, that is normally used for preventing the extrusion of the self-baked electrode downwards. As a matter of fact, with the electrode according to the invention, it is possible to obtain a silicon metal containing less tiian 0.5% Fe, with a casing still made of steel.
Extensive studies of the baking pattern of both a conventional Soderberg electrode and a compound electrode where the center of the electrode is of a solid material having a substantially different thermal and electiical conductivity have shown that when die electrode comprises a central core with a high conductivity, die heating and baking pattern is higher in the contact shoe area as compared to the conventional Soderbetg technology. More specifically, baking of the paste occurs from the centre of the high heat conducting solid core against the surrounding Soderberg paste towards the casing. In contrast, with a conventional Soderberg electrode, baking of the paste occurs from the casing and die fins, that is from die outside of the electrode, toward die inside of the same, as mis is not a different conductivity between the core and the Soderberg material.
The present invention uses, in a well balanced system, the heat conductivity of the central core (32) to bake die surrounding Soderberg paste (36). It does not necessitate a relative movement of the baked electrode (36) with respect to its surrounding casing (30) as is the case with the compound electrodes known in prior art and for use in die silicon metal production.
The process for forming in situ a self-baking electrode (4) in an electric arc furnace (2), according to die present invention, comprises me following sequence of steps. a) An elongated open ended electrically conductive casing is provided. b) An elongated central core (32) of conductive heat material is disposed widiin and spaced from die casing (30). c) The central core (30) is secured to an inner surface of die casing (30) and held centrally within the casing (30). d) The elongated electrically conductive casing (30) is slid within the furnace
(2) for extending generally vertically therein. e) A quantity of carbonaceous electrode paste (36) is introduced in the casing (30) surrounding the central core (32). The paste (36) is devised to cure into a solid electrode upon heating and to bond to the central core (32). f) An electric arc is present in the furnace (2) in a well know manner which do not need furtiier description.
Preferably in step c), the central core (32) is secured to die casing (30) by driving respectively into two opposite sides of the central core (30), a first end (40) of a corresponding rod (38) of a pair of opposite rods (38) and then securing a second end (42) of each of said opposite rods (38) to an inner surface of die casing (30) such that each rod (38) is extending generally horizontally within the casing
(30). A bar (44) is inserted through the central core (32) below the two rods (38) such that the opposite outer ends (46) of the bar (44) are projecting out from the central core (32). The second end (42) of each rod (38) is respectively connected to a corresponding outer end (46) of the bar (44) with a lateral frame member (48). In the case where die electrode (4) formed is used for the production of silicon metal, the casing (30), in step d), may preferably be slid on top of a previous Soderberg-type self-baking electrode (49) used for die production of ferrosilicon, as shown in figure 2. In this case, the casing (30) used for the production of silicon may have substantially the same diameter as die outer casing (50) of die Soderberg electrode (48). As mentioned before, one can see tiiat it is possible to easily switch from the production of ferrosilicon using a regular Soderberg electrode (48) to die production of a silicon metal using an electrode according to the invention witiiout any downtime or shutdown of the whole furnace.

Claims

WHAT IS CLAIMED IS:
1. An in situ self-baking electrode (4) suitable for use in an electric arc furnace (2), the electrode (4) being characterized in that it comprises: an elongated open ended electrically conductive casing (30) that extends generally vertically within die furnace (2) in use; a central core (32) disposed widiin and spaced from die casing (30), the central core (32) being made of a heat conductive material; at least one framework (37) widiin the casing (30), the framework (37) securing the central core (32) to an inner surface of the casing (30) for holding centrally the central core (32) within the casing (30) and for preventing an extrusion of the central core (32) downward; and a carbonaceous electrode paste (36) surrounding die central core (32), the paste (36) being devised to cure into a solid electrode upon heating and to bond to the central core (32).
2. An in situ self-baking electrode (4) as defined in claim 1, characterized in mat the casing (30) is made of a material unalloyed with a metal selected from the group consisting of titanium, vanadium, tantalum, chrome, zirconium and nickel for preventing contamination of a product to be produced in the furnace with any of said metal upon an ongoing consumption of die casing (30) in die furnace (2).
3. An in situ self-baking electrode (4) as defined in anyone of claims 1 and 2, characterized in that the central core (32) is made of a carbonaceous material.
4. An in situ self-baking electrode (4) as defined in anyone of claims 1 to 3, characterized in that the casing (30) is made of a metal selected from the group consisting of copper, brass and aluminum.
5. An in situ self-baking electrode (4) as defined in anyone of claims 1 to 4, characterized in that the at least one framework (37) comprises: a pair of opposite rods (38), each rod (38) extending generally horizontally and having a first end (40) driven into the central core (32) and a second end (42) secured to an inner surface of the casing (30); a bar (44) extending through the central core (32) below die pair of rods (38) and having opposite outer ends (46) projecting out from the central core (32); and two lateral frame members (48), each connecting together the second end (42) of each rod (38) to a corresponding outer end (46) of the bar (44).
6. An in situ self-baking electrode (4) as defined in anyone of claims 1 to 5, characterized in that the central core (32) is hollowed for allowing inside cooling through injection cooling gases.
7. An electric arc furnace (2) comprising: a furnace body (6) containing a charge (14) to be heated; an in situ self-baking electrode (4) comprising: an elongated open ended electrically conductive casing (30) having an upper end (31) and a bottom end (33), said casing (30) extending generally vertically within the furnace body (6) and being free to slip vertically dirough a slipping mechanism (24); a central core (32) disposed within and spaced from the casing (30), the central core (32) being made of heat conductive material; at least one framework (37) widiin the casing (30), the framework (37) securing the central core (32) to an inner surface of the casing (30) for holding centrally die central core (32) within the casing (30) and for preventing an extrusion of the central core (32) downward through the bottom end (33) of die casing (32); a carbonaceous electrode paste (36) surrounding the central core (32), the paste (36) being devised to cure into a solid electrode upon heating and to bond to die central core (32); means for retaining (22,24) the casing (30) in a generally vertical position within the furnace body (6); and » 15 electric means for generating an electric arc in the furnace, the electric means comprising a contact (1 ) on the casing (30).
8. An electric arc furnace (2) as defined in claim 7, characterized in tiiat die casing (30) is made of a material unalloyed with a metal selected from die group consisting of titanium, vanadium, tantalum, chrome, zirconium and nickel for preventing contamination of a product to be produced in the furnace (2) widi any of said metal upon an ongoing consumption of the casing (30) in the furnace (2).
9. An electric arc furnace (2) as defined in claim 7 or 8, characterized in that the central core (32) is made of a carbonaceous material.
10. An electric arc furnace (2) as defined in anyone of claims 7 to 9, characterized in tiiat the casing (30) is made of a metal selected from die group consisting of copper, brass and aluminum.
11. An electric arc furnace (2) as defined in anyone of claims 7 to 10, characterized in that the at least one framework (37) comprises: a pair of opposite rods (38), each rod (38) extending generally horizontally and having a first end (40) driven into the central core (32) and a second end (42) secured to an inner surface of the casing (30); a bar (44) extending through die central core (32) below the pair of rods (38) and having opposite outer ends (46) projecting out from the central core (32); and two lateral frame members (48), each connecting together the second end (42) of each rod (38) to a corresponding outer end (46) of the bar (44).
12. An electric arc furnace (2) as defined in anyone of claims 7 to 11, characterized in that the central core (32) is hollowed for allowing inside cooling through injection cooling gases.
13. A process for forming in situ a self-baking electrode (4) in an electric arc furnace (2), die process comprising me steps of: a) providing an elongated open ended electrically conductive casing (30); b) disposing a central core (32) of conductive heat material within and spaced from die casing (30); c) securing the central core (32) to an inner surface of die casing (30) and holding it centrally within the casing (30); d) sliding generally vertically the elongated electrically conductive casing (30) widiin the furnace (2); e) introducing a quantity of carbonaceous electrode paste (36) in the casing
(30) so diat said paste (36) surrounds the central core (32), die paste (36) being devised to cure into a solid electrode upon heating and to bond to die central core (32); and f) contacting the casing (30) to an electric power source; and g) generating with said electric power source an electric arc into the furnace
(2).
14. A process as defined in claim 13, wherein step c) comprises die steps of:
- driving respectively into two opposite sides of die central core (32) a first end (40) of a corresponding rod (38) of a pair of opposite rods (38) and securing a second end (42) of each of said opposite rods (38) to an inner surface of die casing (30) such that each rod (38) is extending generally horizontally within die casing (30);
- inserting a bar (44) through the central core (32) below said two rods (38) and such that opposite outer ends (46) of said bar (44) are projecting out from the central core (32); and
- connecting togetiier widi a respective lateral member (48), die second end (42) of each rod (38) to a corresponding outer end (46) of the bar (44).
15. A process as defined in claim 13, wherein: - the electrode (4) tiiat is formed is used for the production of silicon metal; me process being characterized in that:
- in step d), the casing (30) is connected on top of a previous Soderberg-type self-baking electiode (49) used for die production of ferrosilicon, said Soderberg electrode (49) comprising an outer casing (50); and in tiiat
- the casing (30) of the electrode (4) tiiat is formed has substantially the same diameter as said outer casing (50) of die Soderberg electrode (49).
AMENDED CLAIMS
[received by the International Bureau on 27 August 1998 (27.08.98); original claims 1, 7 and 13 amended; remaining claims unchanged (5 pages)]
1. An in situ self-baking electrode (4) suitable for use in an electric arc furnace (2), the electrode (4) being characterized in that it comprises: an elongated open ended electrically conductive casing (30) that extends generally vertically within the furnace (2) in use; a central core (32) disposed within and spaced from the casing (30), the central core (32) being made of a heat conductive material free of iron; at least one framework (37) within the casing (30), the framework (37) securing the central core (32) to an inner surface of the casing (30) for holding centrally the central core (32) within the casing (30) and for preventing an extrusion of the central core (32) downward; and a carbonaceous electrode paste (36) surrounding the central core (32), the paste (36) being devised to cure into a solid electrode upon heating and to bond to the central core (32).
2. An in situ self-baking electrode (4) as defined in claim 1 , characterized in that the casing (30) is made of a material unalloyed with a metal selected from the group consisting of titanium, vanadium, tantalum, chrome, zirconium and nickel for preventing contamination of a product to be produced in the furnace with any of said metal upon an ongoing consumption of the casing (30) in the furnace (2).
3. An in situ self-baking electrode (4) as defined in anyone of claims 1 and 2, characterized in that the central core (32) is made of a carbonaceous material.
4. An in situ self-baking electrode (4) as defined in anyone of claims 1 to 3, characterized in that the casing (30) is made of a metal selected from the group consisting of copper, brass and aluminum.
5. An in situ self-baking electrode (4) as defined in anyone of claims 1 to 4, characterized in that the at least one framework (37) comprises: a pair of opposite rods (38), each rod (38) extending generally horizontally and having a first end (40) driven into the central core (32) and a second end (42) secured to an inner surface of the casing (30); a bar (44) extending through the central core (32) below the pair of rods (38) and having opposite outer ends (46) projecting out from the central core (32); and two lateral frame members (48), each connecting together the second end (42) of each rod (38) to a corresponding outer end (46) of the bar (44).
6. An in situ self-baking electrode (4) as defined in anyone of claims 1 to 5, characterized in that the central core (32) is hollowed for allowing inside cooling through injection cooling gases.
7. An electric arc furnace (2) comprising: a furnace body (6) containing a charge (14) to be heated; an in situ self-baking electrode (4) comprising: an elongated open ended electrically conductive casing (30) having an upper end (31 ) and a bottom end (33), said casing (30) extending generally vertically within the furnace body (6) and being free to slip vertically through a slipping mechanism (24); a central core (32) disposed within and spaced from the casing (30), the central core (32) being made of heat conductive material free of iron; at least one framework (37) within the casing (30), the framework (37) securing the central core (32) to an inner surface of the casing (30) for holding centrally the central core (32) within the casing (30) and for preventing an extrusion of the central core (32) downward through the bottom end (33) of the casing (32); a carbonaceous electrode paste (36) surrounding the central core (32), the paste (36) being devised to cure into a solid electrode upon heating and to bond to the central core (32); means for retaining (22,24) the casing (30) in a generally vertical position within the furnace body (6); and electric means for generating an electric arc in the furnace, the electric means comprising a contact (16) on the casing (30).
8. An electric arc furnace (2) as defined in claim 7, characterized in that the casing (30) is made of a material unalloyed with a metal selected from the group consisting of titanium, vanadium, tantalum, chrome, zirconium and nickel for preventing contamination of a product to be produced in the furnace (2) with any of said metal upon an ongoing consumption of the casing (30) in the furnace (2).
9. An electric arc furnace (2) as defined in claim 7 or 8, characterized in that the central core (32) is made of a carbonaceous material.
10. An electric arc furnace (2) as defined in anyone of claims 7 to 9, characterized in that the casing (30) is made of a metal selected from the group consisting of copper, brass and aluminum.
11. An electric arc furnace (2) as defined in anyone of claims 7 to 10, characterized in that the at least one framework (37) comprises: a pair of opposite rods (38), each rod (38) extending generally horizontally and having a first end (40) driven into the central core (32) and a second end (42) secured to an inner surface of the casing (30); a bar (44) extending through the central core (32) below the pair of rods (38) and having opposite outer ends (46) projecting out from the central core (32); and two lateral frame members (48), each connecting together the second end (42) of each rod (38) to a corresponding outer end (46) of the bar (44).
12. An electric arc furnace (2) as defined in anyone of claims 7 to 11 , characterized in that the central core (32) is hollowed for allowing inside cooling through injection cooling gases.
13. A process for forming in situ a self-baking electrode (4) in an electric arc furnace (2), the process comprising the steps of: a) providing an elongated open ended electrically conductive casing (30); b) disposing a central core (32) of conductive heat material free of iron within and spaced from the casing (30); c) securing the central core (32) to an inner surface of the casing (30) and holding it centrally within the casing (30); d) sliding generally vertically the elongated electrically conductive casing (30) within the furnace (2); e) introducing a quantity of carbonaceous electrode paste (36) in the casing
(30) so that said paste (36) surrounds the central core (32), the paste (36) being devised to cure into a solid electrode upon heating and to bond to the central core (32); and f) contacting the casing (30) to an electric power source; and g) generating with said electric power source an electric arc into the furnace
(2).
14. A process as defined in claim 13, wherein step c) comprises the steps of:
- driving respectively into two opposite sides of the central core (32) a first end (40) of a corresponding rod (38) of a pair of opposite rods (38) and securing a second end (42) of each of said opposite rods (38) to an inner surface of the casing (30) such that each rod (38) is extending generally horizontally within the casing (30);
- inserting a bar (44) through the central core (32) below said two rods (38) and such that opposite outer ends (46) of said bar (44) are projecting out from the central core (32); and
- connecting together with a respective lateral member (48), the second end (42) of each rod (38) to a corresponding outer end (46) of the bar (44).
15. A process as defined in claim 13, wherein: - the electrode (4) that is formed is used for the production of silicon metal; the process being characterized in that:
- in step d), the casing (30) is connected on top of a previous Sδderberg-type self-baking electrode (49) used for the production of ferrosilicon, said Soderberg electrode (49) comprising an outer casing (50); and in that
- the casing (30) of the electrode (4) that is formed has substantially the same diameter as said outer casing (50) of the Soderberg electrode (49).
EP98916756A 1997-05-02 1998-04-27 Söderberg electrode for making silicon alloys and silicon metal Expired - Lifetime EP0979596B9 (en)

Priority Applications (1)

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SI9830264T SI0979596T1 (en) 1997-05-02 1998-04-27 Söderberg electrode for making silicon alloys and silicon metal

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
CA002204425A CA2204425A1 (en) 1997-05-02 1997-05-02 Electrode for silicon alloys and silicon metal
CA2204425 1997-05-02
US08/958,323 US5854807A (en) 1997-05-02 1997-10-27 Electrode for silicon alloys and silicon metal
US958323 1997-10-27
PCT/CA1998/000409 WO1998051129A1 (en) 1997-05-02 1998-04-27 Electrode type söderberg for making silicon alloys and silicon metal

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EP0979596A1 true EP0979596A1 (en) 2000-02-16
EP0979596B1 EP0979596B1 (en) 2002-07-17
EP0979596B9 EP0979596B9 (en) 2003-01-02

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AU (1) AU7024998A (en)
BR (1) BR9809347B1 (en)
ES (1) ES2177000T3 (en)
IS (1) IS1955B (en)
NO (1) NO315630B1 (en)
PL (1) PL189321B1 (en)
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WO2000011226A1 (en) * 1998-08-25 2000-03-02 Pyromet (Proprietary) Limited Söderberg-type composite electrode for arc smelting furnace

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GB227822A (en) * 1924-01-17 1925-08-13 Norske Elektrokemisk Ind As Improvements in or relating to electrodes for electric furnaces
US4133968A (en) * 1977-05-26 1979-01-09 Frolov Jury F Apparatus for forming self-sintering electrodes
DE3840827A1 (en) * 1988-12-03 1990-06-07 Hoechst Ag ELECTROTHERMIC REDUCTION STOVES
DE4010353A1 (en) * 1990-03-28 1991-10-02 Mannesmann Ag Operating metallurgical furnace with self-baking electrode - lockable traction rod within electrode
FR2724219B1 (en) * 1994-09-05 1996-10-25 Pechiney Electrometallurgie DEVICE FOR MOUNTING A SELF-COOKING COMPOSITE ELECTRODE FOR ELECTRIC ARC OVEN

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BR9809347A (en) 2000-07-04
PL336590A1 (en) 2000-07-03
WO1998051129A1 (en) 1998-11-12
NO315630B1 (en) 2003-09-29
PL189321B1 (en) 2005-07-29
EP0979596B1 (en) 2002-07-17
AU7024998A (en) 1998-11-27
ES2177000T3 (en) 2002-12-01
IS1955B (en) 2004-11-15
IS5219A (en) 1999-10-15
EP0979596B9 (en) 2003-01-02
BR9809347B1 (en) 2011-11-16
SK149399A3 (en) 2000-08-14
NO995254L (en) 1999-12-29
NO995254D0 (en) 1999-10-27
SK286447B6 (en) 2008-10-07

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