EP0992615A1 - Startkathoden aus Kupferband für die Kupferelektrolyse und Verfahren zu deren Herstellung - Google Patents
Startkathoden aus Kupferband für die Kupferelektrolyse und Verfahren zu deren Herstellung Download PDFInfo
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- EP0992615A1 EP0992615A1 EP98118542A EP98118542A EP0992615A1 EP 0992615 A1 EP0992615 A1 EP 0992615A1 EP 98118542 A EP98118542 A EP 98118542A EP 98118542 A EP98118542 A EP 98118542A EP 0992615 A1 EP0992615 A1 EP 0992615A1
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- Prior art keywords
- copper
- copper strip
- soft
- thickness
- rolled
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/4998—Combined manufacture including applying or shaping of fluent material
- Y10T29/49988—Metal casting
- Y10T29/49991—Combined with rolling
Definitions
- the invention relates to starting cathodes made of copper tape for copper electrolysis as well a process for the production of the starting cathodes.
- the invention had for its object to provide starting cathodes made of copper strip for copper electrolysis, which exclude a "memory effect" during copper electrolysis, with which a high production output of electrolytic copper can be achieved and which can also be produced from directly deformed copper strip material present as a coil are. Furthermore, a suitable method for the production of the starting cathodes is to be created, which is also particularly suitable for processing conventionally produced copper strip
- the frequency of short circuits could be reduced considerably and current yields of 98 to 99% were achieved.
- the thickness of the copper band for the ear strips could also be reduced to preferably 0.3 to 0.5 mm.
- the specified strength of the copper strip of 210 to 240 N / mm 2 is achieved, for example, by post-treatment on a skin pass mill.
- the hard-rolled copper strip is soft-annealed at furnace temperatures of 700 to 750 ° C, preferably at 720 to 750 ° C, the furnace temperature being reduced from 750 ° C to 720 ° C in the direction of flow.
- the throughput speed of the copper strip essentially depends on the strip width and the strip thickness. For starter sheets for starting cathodes with a width of 930 mm and a thickness of 0.3 to 0.8 mm, this is 20 to 55 m / min.
- the copper strip can be produced in a conventional casting and rolling plant and wound up as a coil. The hard-rolled copper strip is then unwound in a separate system, soft annealed in an annealing furnace, treated in a subsequent degreasing and pickling unit (scale and oxide removal) and straightened in a straightening and dividing system and cut to the required length of 840 to 1250 mm.
- the starting cathodes are separated, sorted and hung in the prepared receptacle for the crane for hanging in the electrolysis bath. It is of significant advantage that no separate special system for producing the starter plates is required, but that a hard-rolled copper strip is produced which is known per se and which can also be obtained from a third party. This also applies to a further variant, according to which the hard-rolled copper strip is soft-annealed within the casting and rolling plant and is available as further-processed cathode as soft-annealed copper strip in the form of a coiled coil.
- the annealing of the rolled copper strip can be carried out in a vertical or horizontal type annealing furnace. Before the soft annealing, the copper strip should be degreased, brushed, rinsed with water and dried. After the annealing, it is advisable to pickle and neutralize the cooled copper strip.
- SF-Cu was rolled on a conventional casting and rolling machine to a copper strip with a width of 930 mm and a thickness of 0.5 mm.
- the hard-rolled copper strip has a tensile strength of 263 N / mm 2 and is available as a coiled coil.
- Starting cathodes are produced under the following conditions in a separate system, consisting of a decoiler, annealing furnace, degreasing and pickling unit, straightening and compartment system as well as the assembly system for the ears and contact bars.
- the unreeled, hard-rolled copper strip passes through a horizontal suspension belt furnace, the heating zones of which are set to temperatures in the range from 750 to 720 ° C.
- the belt speed is 35 m / min.
- Soft annealing takes place in a protective gas atmosphere.
- the soft annealed, cooled copper strip has a tensile strength of 217 N / mm 2 .
- the degreasing and pickling unit also removes scale and oxide.
- the copper strip is cut into lengths of 970 mm and the starter plates 970 x 930 mm thus obtained are straightened.
- starter plates which are further assembled are completely flat and smooth, have no external damage, such as scratches, and are free of grease, emulsions and oil.
- the dry, clean starter sheets are transported to a riveting machine to attach the necessary ear strips, which are made from 0.4 mm thick copper tape, which is made from the same type of material as the starter sheets. After attaching the "ears" to the starter plates, the contact rods are attached.
- hard-rolled copper strip is produced from SF-Cu and coiled as a coil.
- the 930 mm wide, hard-rolled copper strip has a thickness of 0.635 mm after the rolling process.
- the copper strip is degreased, brushed, rinsed with clear water and dried.
- the hard-rolled copper strip then runs through a floating belt furnace at a speed of 27.5 m / min, the furnace temperatures are in the range from 750 to 720 ° C.
- the cooled copper strip has a tensile strength of 217 N / mm 2 . It is then pickled, neutralized, reeled up as a coil and stored temporarily.
- the soft-annealed copper strip which is in the form of a coil, is unwound in a separate system and further processed into starting cathodes in a straightening and compartment system, as well as in the assembly system for the ears and contact rods, as in Example 1.
- the sheet thickness of the ears attached to the starter cathodes is 0.5 mm.
- Starting cathodes are produced analogously to Example 1, with the only difference that the casting and rolling system, the annealing furnace, the degreasing and pickling unit, the straightening and compartment system and the packaging system are arranged in one line. This eliminates the need to rewind and unwind the hard-rolled or soft-annealed copper strip according to Example 1 or Example 2.
- the copper strip material consists of SF-Cu and is reduced to a thickness of 0.8 mm by the rolling process.
- the temperatures in the suspension belt furnace are also 750 to 720 ° C, the throughput speed is 23 m / min.
- the soft-annealed, cooled copper strip has a tensile strength of 232 N / mm 2 .
- the dimensions of the starter plates are also 970 x 930 mm.
- the ears riveted to the starter plates have a thickness of 0.6 mm.
- the starting cathodes produced according to the above examples were used for electrolysis experiments and have the following parameters: Starting cathodes 970 x 930 mm made of SF-Cu S1 S2 S3 S4 Sheet thickness mm 0.5 0.635 0.8 0.5 Tensile strength N / mm 2 217 217 232 263 Ear thickness mm 0.4 0.5 0.6 0.4 annealed Yes Yes Yes No
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- Metallurgy (AREA)
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- Organic Chemistry (AREA)
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- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mechanical Engineering (AREA)
- Electrolytic Production Of Metals (AREA)
- Metal Rolling (AREA)
Abstract
Description
Die Erfindung betrifft Startkathoden aus Kupferband für die Kupferelektrolyse sowie ein Verfahren zur Herstellung der Startkathoden.The invention relates to starting cathodes made of copper tape for copper electrolysis as well a process for the production of the starting cathodes.
In der Kupferelektrolyse wird das schmelzmetallurgisch hergestellte Kupfer-Rohmetall,
das eine Reinheit von 99,0 bis 99,8 aufweist, anodisch vorwiegend als Cu 2+ gelöst und
kathodisch hoch selektiv als Reinkupfer (High-Grade) abgeschieden. Für die
kathodische Abscheidung werden entweder elektrolytisch erzeugte, dünne Unterlagen
(Starterbleche) oder Permanentkathoden aus Edelstahl verwendet. Das im Rahmen der
Kupferelektrolyse gewonnene Elektrolytkupfer besitzt einen Reinheitsgrad von 99,95
bis 99,99 % und wird zur Herstellung von Halbzeugen aus diesem Metall und seinen
Legierungen eingesetzt.
Die zur Erzeugung von Starterblechen dienenden Unterlagen bestehen entweder aus
kaltgewalztem poliertem Kupfer, Edelstahl oder Titan. Die Starterbleche werden in
sogenannten Mutterblechbädern erzeugt Nach einer elektrolytischen Abscheidung im
wiederkehrenden Rhythmus von jeweils 24 Stunden aufden Mutterblechen erfolgt die
Abtrennung der Niederschläge entweder mittels automatischer Strippingmaschine
oder manuell. Diese als Unterlagen bezeichneten Bleche, welche in Länge und Breite
annähernd den Anoden- bzw. Kathodenabmessungen entsprechen, sind 0,5 bis 1 mm
dick und wiegen ca. 4 bis 7 kg. Die Präparation zu Starterblechen beinhaltet im
Wesentlichen das ggf. erforderliche Beschneiden von ungeraden, rissigen Kanten, das
Richten und das Anbringen von zwei Befestigungsstreifen ("Ohren" aus geschnittenen
o.g. Unterlagen oder gewalztem Kupferband) an den Kathodenstab mittels
automatischer Nietmaschine. Diese Technologie der Herstellung von "Starterblechen"
ist veraltet und nicht mehr wirtschaftlich. Das istein seit langem bestehendes Problem
für die Kupferindustrie, weil der Bedarf an Edelstahlblechen und der erforderliche
hohe Qualitätsstandard für Starterbleche zu hohen Kosten sowohl hinsichtlich des
Beschaffungs- als auch Arbeits-, Energie- und Zeitaufwandes sowie zu einer hohen
Abfallrate bei der Starterblechproduktion führt. Zum Beispiel hat das Starterblech
gewöhnlich ein Festmaß, das durch die Größe des Elektrolysebades begrenzt ist.
Industriell ist es jedoch von Bedeutung, daß die Mutterblechanode wegen der hohen
Energie- und Arbeitskosten bei der Anodenproduktion und der Wiederaufarbeitung der
Anodenreste nach der elektrolytischen Metallabscheidung eine optimale Größe besitzt.
Die Anode muß jedoch eine nahezu vollständige und gleichmäßige Abdeckung des
Mutterbleches aufweisen, so daß deshalb in der Praxis die Anodengröße der Größe
der Mutterbleche und anderen Prozeß variablen angepaßt wird, um die Herstellungskosten
für Starterbleche zu senken. Das führt in der Regel zur Herstellung von zwei
Anodensorten, welche sich in der Geometrie unterscheiden:
- Mutterblechanoden und
- Produktionsanoden.
Die bekannten Folgen sind Kurzschlüsse, die zu niedrigen Stromausbeuten und einer Senkung der Produktionsmenge führen, einhergehend mit einer Verschlechterung der Kathodenqualität.
Bei dem zwischenzeitlich in der Praxis zur Anwendung gelangten Kupferraffinierprozeß unterder Bezeichnung "ISA-Prozeß" werden aus Edelstahl bestehende Permanentkathoden eingesetzt. Auf diesen scheidet sich das Kupfer über einen Zeitraum von gewöhnlich 7 Tagen ab und wird mechanisch mittels automatischer Stripppingmaschine in Form von Blechen abgetrennt.
Der "ISA-Prozeß" ist sehr kostenaufwendig und führt zu hohen Gestehungskosten für das raffinierte Kupfer. Außerdem sind für den "ISA-Prozeß" große Bestände an Edelstahlblechen erforderlich, die zu zusätzlichen Lagerhaltungskosten führen.
Ein weiterer Nachteil des "ISA-Prozeßes" besteht darin, daß die zur Elektrolytregenerierung benötigten Starterbleche für die Entkupferungselektrolyse in der Regel von Fremdbetrieben zugekauft werden müssen.
Die Wirtschaftlichkeit einer Kupferelektrolyse ist im wesentlichen von der Qualität der als Startkathoden eingesetzten Kupferbleche sowie deren Herstellungskosten abhängig.
In der WO 97/42360 ist ein Verfahren zur Herstellung von Kupferkathodenstarterblechen beschrieben, bei dem raffiniertes Kupfer geschmolzen und anschließend durch kontinuierliche Gieß- und Walzverfahren zu Bändern mit einer Dicke von 0,635 bis 1,778 mm (0,025 bis 0,070 inch), was einer Reduzierung der Ausgangsmaterialdicke von 25 bis 98 % entspricht, verarbeitet werden. Dabei ist es erforderlich, daß das Gießen in horizontaler Lage erfolgt und auch in horizontaler Lage zu der Reduzieranlage, einem Walzwerk, transportiert wird. Das in der ersten Verfahrensstufe erhaltene Gießband sollte eine Dicke von 5,08 mm bis 38,1 mm (0,2 bis 1,5 inch) aufweisen. Weiterhin ist wesentlich, daß das gewalzte Band während oder nach dem Walzen wedergerollt noch anderweitig deformiert werden darf, um den sogenannten "Memory-Effekt" (eine horizontale Wölbung von einigen mm) beim Einsatz als Starterbleche auszuschließen. Der "Memory-Effekt" ist die Hauptursache für auftretende Kurzschlüsse während der Kupferelektrolyse.
Aus dem gewalzten Band werden die Starterbleche ausgeschnitten und in an sich bekannter Weise für den Elektrolyseprozeß konfektioniert.
Diese vorgeschlagene Verfahrensweise zur Herstellung von Kupferkathodenstarterblechen ist bedingt durch die hohen Anlagekosten sehr aufwendig. Die Anlage ist auf die üblichen Breitenabmessungen der Startkathoden ausgelegt und ausschließlich für die Herstellung von Startkathoden bestimmt. Bezogen auf die mögliche Kapazität einer solchen Anlage von ca. 200.000 t/Jahr und dem Jahresbedarf einer Elektrolyse von ca. 35 t/Jahr an Startkathoden ergeben sich Probleme hinsichtlich einerwirtschaftlichen Auslastung. Dadurch werden die Startkathoden in ihrem Gestehungspreis sehr teuer. Außerdem ist dieses Verfahren aufdie Verarbeitung von Raffinatkupfer beschränkt. Von Nachteil ist außerdem, daß das gewalzte Kuperband zur Herstellung der Startkathoden weder gerollt noch anderweitig deformiert werden darf. Das hat zur Folge, daß das gewalzte Kupferband nicht als Coil aufgewickelt werden kann, sondern nur in Form von vorgefertigten Blechzuschnitten transportiert und zwischengelagert werden kann bzw. die gewalzten Bleche direkt innerhalb der Linie zu Startkathoden verarbeitet werden müssen. Ferner ist zu befürchten, daß infolge derdurch die Walzvorgänge entstehenden Verformungen ein "Memory-Effekt" der Startkathoden während der Kupferelektrolyse nicht vollständig ausgeschlossen werden kann. In der vorgenannten Druckschrift sind auch keine Ergebnisse angegeben, die belegen, daß ein "Memory-Effekt" beim Einsatz derhergestellten Startkathoden nicht eintritt.In copper electrolysis, the crude metal, which is produced by melting metallurgy and has a purity of 99.0 to 99.8, is anodically predominantly dissolved as Cu 2+ and is deposited cathodically in a highly selective manner as pure copper (high-grade). Either electrolytically produced, thin substrates (starter plates) or permanent cathodes made of stainless steel are used for the cathodic deposition. The electrolytic copper obtained in the course of copper electrolysis has a degree of purity of 99.95 to 99.99% and is used to manufacture semi-finished products from this metal and its alloys.
The documents used to produce starter plates consist of either cold-rolled polished copper, stainless steel or titanium. The starter sheets are produced in so-called mother sheet baths. After electrolytic deposition on the mother sheets in a recurring rhythm of 24 hours, the precipitation is separated either by means of an automatic stripping machine or manually. These sheets, referred to as documents, which approximately correspond in length and width to the anode or cathode dimensions, are 0.5 to 1 mm thick and weigh approximately 4 to 7 kg. The preparation for starter sheets essentially includes the necessary cutting of odd, cracked edges, the straightening and the attachment of two fastening strips ("ears" from the above-mentioned documents or rolled copper tape) to the cathode rod using an automatic riveting machine. This technology of producing "starter plates" is outdated and no longer economical. This has been a long-standing problem for the copper industry because the need for stainless steel sheets and the high quality standard required for starter sheets lead to high costs in terms of procurement, labor, energy and time as well as a high waste rate in starter sheet production. For example, the starter sheet usually has a fixed size that is limited by the size of the electrolysis bath. From an industrial point of view, however, it is important that the mother plate anode has an optimal size because of the high energy and labor costs involved in anode production and the reprocessing of the anode residues after electrolytic metal deposition. However, the anode must have an almost complete and uniform covering of the mother plate, so that in practice the anode size is variably adapted to the size of the mother plates and other processes in order to reduce the production costs for starter plates. This usually leads to the production of two types of anodes, which differ in their geometry:
- Mother sheet metal anodes and
- Production anodes.
The known consequences are short circuits, which lead to low current yields and a reduction in the production quantity, along with a deterioration in the cathode quality.
In the meantime used in copper refining process under the name "ISA process", stainless steel permanent cathodes are used. The copper deposits on these over a period of usually 7 days and is mechanically separated in the form of sheets using an automatic stripping machine.
The "ISA process" is very expensive and leads to high production costs for the refined copper. In addition, large stocks of stainless steel sheets are required for the "ISA process", which lead to additional storage costs.
Another disadvantage of the "ISA process" is that the starter plates required for electrolyte regeneration for decoupling electrolysis generally have to be purchased from external companies.
The economic viability of copper electrolysis essentially depends on the quality of the copper sheets used as starting cathodes and their manufacturing costs.
WO 97/42360 describes a process for producing copper cathode starter sheets in which refined copper is melted and then by continuous casting and rolling processes into strips with a thickness of 0.635 to 1.778 mm (0.025 to 0.070 inch), which reduces the starting material thickness corresponds to 25 to 98%. It is necessary that the casting takes place in a horizontal position and is also transported in a horizontal position to the reducing system, a rolling mill. The casting tape obtained in the first stage of the process should have a thickness of 5.08 mm to 38.1 mm (0.2 to 1.5 inches). It is also essential that the rolled strip may not be rolled or otherwise deformed during or after rolling in order to exclude the so-called "memory effect" (a horizontal curvature of a few mm) when used as starter plates. The "memory effect" is the main cause of short circuits that occur during copper electrolysis.
The starter sheets are cut out of the rolled strip and assembled in a manner known per se for the electrolysis process.
This proposed procedure for the production of copper cathode starter sheets is very complex due to the high investment costs. The system is designed for the usual width dimensions of the starting cathodes and is intended exclusively for the production of starting cathodes. With regard to the possible capacity of such a plant of approx. 200,000 t / year and the annual requirement for electrolysis of approx. 35 t / year for starting cathodes, problems arise with regard to economic utilization. This makes the starting cathodes very expensive in their cost price. In addition, this process is limited to processing raffinate copper. Another disadvantage is that the rolled copper strip for the production of the starting cathodes must neither be rolled nor deformed in any other way. The consequence of this is that the rolled copper strip cannot be wound up as a coil, but can only be transported and temporarily stored in the form of prefabricated sheet metal blanks, or the rolled sheets have to be processed directly within the line to form starting cathodes. It is also to be feared that, due to the deformations caused by the rolling processes, a "memory effect" of the starting cathodes during copper electrolysis cannot be completely ruled out. In the aforementioned publication there are also no results which prove that a "memory effect" does not occur when the manufactured starting cathodes are used.
Der Erfindung lag die Aufgabe zugrunde, Startkathoden aus Kupferband für die
Kupferelektrolyse zu schaffen, die während der Kupferelektrolyse einen "Memory-Effekt"
ausschließen, mit denen eine hohe Produktionsleistung an Elektrolytkupfer
erreicht werden kann und die auch aus direkt verformten, als Coil vorliegendem
Kupferbandmaterial herstellbar sind.
Ferner soll ein geeignetes Verfahren zur Herstellung der Startkathoden geschaffen
werden, das insbesondere auch zur Verarbeitung von konventionell hergestelltem
Kupferband geeignet istThe invention had for its object to provide starting cathodes made of copper strip for copper electrolysis, which exclude a "memory effect" during copper electrolysis, with which a high production output of electrolytic copper can be achieved and which can also be produced from directly deformed copper strip material present as a coil are.
Furthermore, a suitable method for the production of the starting cathodes is to be created, which is also particularly suitable for processing conventionally produced copper strip
Erfindungsgemäß wird die Aufgabe durch die in den Ansprüchen 1 und 4
angegebenen Merkmale gelöst Geeignete Ausgestaltungsvarianten für die neuen
in den Ansprüche 2 und 3 und für deren Herstellung in den Ansprüche 5 bis 14
angegeben.
Durch den erfindungswesentlichen Verfahrensschritt, das gewalzte Kupferband einem
zusätzlichen Weichglühvorgang zu unterziehen, ist es gelungen, den ansonsten beim
Einsatz von Startkathoden in der Elektrolyse auftretenden "Memory-Effekt" zu
beseitigen. Dadurch bedingt kommt es während der Kupferelektrolyse zu wesentlich
weniger Kurzschlüssen und zu einerhöheren Stromausbeute. Die Kupferelektrolyse
kann somit effizienter und mit einer höheren Kathodenleistung durchgeführt werden.
Vorteilhaft wirkt sich auch der Einsatz von Kupfersorten gemäß den DIN-Vorschriften
1708, 1787 und 17670 aus, die im Vergleich zu Elektrolyt- bzw. Raffinatkupfer höhere
Gehalte an metallischen Verunreinigungen enthalten. Überraschenderweise zeigte
sich, daß beim Einsatz von Startkathoden aus diesen Kupfersorten der Mengenanteil
des reineren elektrolytisch abgeschiedenen Kupfers größerwird. Im Vergleich zu den
gemäß der WO 97/42360 eingesetzten Starterblechen, die eine Mindestdicke von
mindestens 0,635 mm aufweisen müssen, haben Versuche ergeben, daß beim Einsatz
von gewalzten und weichgeglühten Starterblechen die Blechdicke auf einen Wert von
unter 0,5 mm verringert werden kann, wobei 0,3 mm die untere Grenze bilden. Im
Vergleich zu dickeren Starterblechen verringern sich dadurch die Materialeinsatzkosten
und außerdem besteht die Möglichkeit, im Elektrolysebad eine höhere Anzahl
an Startkathoden einzusetzen. Dies ist vor allem auch nur dadurch möglich, weil die
gewalzten und weichgeglühten Starterbleche zu keinem "Memory-Effekt" führen. Beim
Einsatz der erfindungsgemäßen Startkathoden in der Kupferelektrolyse konnte die
Kurzschlußhäufigkeit erheblich reduziert werden und es wurden Stromausbeuten von
98 bis 99 % erreicht.
Infolge der geringeren Dicke der Starterbleche und deren geringeres Gewicht konnte
auch die Dicke des Kupferbandes für die Ohrenstreifen auf vorzugsweise 0,3 bis 0,5
mm reduziert werden.
Die angegebene Festigkeit des Kupferbandes von 210 bis 240 N/mm2 wird z.B. durch
eine Nachbehandlung auf einem Dressiergerüst erreicht.
Das Weichglühen des walzharten Kupferbandes erfolgt bei Ofentemperaturen von 700
bis 750 °C, vorzugsweise bei 720 bis 750 °C, wobei die Ofentemperatur in Durchlaufrichtung
von 750 °C auf 720 °C reduziert wird. Die Durchlaufgeschwindigkeit des
Kupferbandes ist im wesentlichen von der Bandbreite und der Banddicke abhängig.
Für Starterbleche für Startkathoden mit einer Breite von 930 mm und einer Dicke von
0,3 bis 0,8 mm beträgt diese 20 bis 55 m/min. Zur Durchführung des Weichglühvorganges
bieten sich verfahrenstechnisch verschiedene Möglichkeiten an. Das
Kupferband kann innerhalb einer herkömmlichen Gieß- und Walzanlage hergestellt
und als Coil aufgehaspelt werden. In einergesonderten Anlage wird dann das
walzharte Kupferband abgehaspelt, in einem Glühofen weichgeglüht, in einer
anschließenden Entfettungs- und Beizeinheit (Zunder und Oxydentfernung) behandelt
und in einer Richt- und Abteilanlage gerichtet und auf die erforderliche Länge von 840
bis 1250 mm zugeschnitten. Bei dieser Ausführungsvariante kann ein Dressieren des
Kupferbandes entfallen. Danach werden die Ohren mittels einer Niet-und Richtmaschine
angenietet und die Kontaktstäbe angebracht. In einer abschließenden
Adjustageeinheit erfolgt das Vereinzeln, Sortieren und Einhängen der Startkathoden in
die vorbereitete Aufnahme für den Kran zum Einhängen in das Elektrolysebad. Von
wesentlichem Vorteil ist, daß keine gesonderte spezielle Anlage zur Herstellung der
Starterbleche benötigtwird, sondern von einem in an sich bekannter Verfahrensweise
hergestellten walzharten Kupferband ausgegangen wird, das auch von einem Dritten
bezogen werden kann.
Dies trifft auch aufeine weitere Variante zu, gemäß der das walzharte Kupferband
noch innerhalb der Gieß- und Walzanlage weichgeglüht wird und zurweiteren
Verarbeitung zu Startkathoden als weichgeglühtes Kupferband in Form eines
aufgehaspelten Coils vorliegt. Dies wird dann zur Herstellung der Startkathoden
abgehaspelt und der Richt- und Abteilanlage zugeführt. Die weitere Verarbeitung
erfolgt dann wie vorstehend beschrieben.
Fernerbesteht die Möglichkeit, die Startkathoden innerhalb einer Fertigungslinie
herzustellen, wobei dann die Verfahrensschritte des Aufhaspelns und Abhaspelns des
Coils aus gewalztem bzw. weichgeglühtem Kupferband entfallen. Das Weichglühen
des gewalzten Kupferbandes kann in einem Glühofen vertikaler oder horizontaler
Bauart durchgeführtwerden. Vordem Weichglühen sollte das Kupferband entfettet,
gebürstet, mit Wasser gespült und getrocknet werden. Nach dem Glühen ist es
zweckmäßig, das abgekühlte Kupferband zu beizen und zu neutralisieren.According to the invention the object is achieved by the features specified in claims 1 and 4. Suitable design variants for the new ones are given in claims 2 and 3 and for their manufacture in claims 5 to 14.
The process step essential to the invention of subjecting the rolled copper strip to an additional soft annealing process has succeeded in eliminating the "memory effect" which otherwise occurs when starting cathodes are used in electrolysis. As a result, there are significantly fewer short circuits and a higher current efficiency during copper electrolysis. The copper electrolysis can thus be carried out more efficiently and with a higher cathode output. The use of copper types in accordance with DIN regulations 1708, 1787 and 17670, which contain higher levels of metallic impurities than electrolyte or raffinate copper, also has an advantageous effect. Surprisingly, it was found that when starting cathodes made from these types of copper are used, the proportion of purer electrodeposited copper increases. In comparison to the starter plates used according to WO 97/42360, which must have a minimum thickness of at least 0.635 mm, tests have shown that when using rolled and soft-annealed starter plates, the plate thickness can be reduced to a value of less than 0.5 mm, with 0.3 mm forming the lower limit. Compared to thicker starter plates, this reduces the material costs and there is also the possibility of using a higher number of starting cathodes in the electrolysis bath. Above all, this is only possible because the rolled and soft-annealed starter plates do not lead to a "memory effect". When using the starting cathodes according to the invention in copper electrolysis, the frequency of short circuits could be reduced considerably and current yields of 98 to 99% were achieved.
As a result of the smaller thickness of the starter plates and their lower weight, the thickness of the copper band for the ear strips could also be reduced to preferably 0.3 to 0.5 mm.
The specified strength of the copper strip of 210 to 240 N / mm 2 is achieved, for example, by post-treatment on a skin pass mill.
The hard-rolled copper strip is soft-annealed at furnace temperatures of 700 to 750 ° C, preferably at 720 to 750 ° C, the furnace temperature being reduced from 750 ° C to 720 ° C in the direction of flow. The throughput speed of the copper strip essentially depends on the strip width and the strip thickness. For starter sheets for starting cathodes with a width of 930 mm and a thickness of 0.3 to 0.8 mm, this is 20 to 55 m / min. There are various procedural options for performing the soft annealing process. The copper strip can be produced in a conventional casting and rolling plant and wound up as a coil. The hard-rolled copper strip is then unwound in a separate system, soft annealed in an annealing furnace, treated in a subsequent degreasing and pickling unit (scale and oxide removal) and straightened in a straightening and dividing system and cut to the required length of 840 to 1250 mm. In this embodiment variant, there is no need to skin the copper strip. The ears are then riveted using a riveting and straightening machine and the contact rods are attached. In a final adjustment unit, the starting cathodes are separated, sorted and hung in the prepared receptacle for the crane for hanging in the electrolysis bath. It is of significant advantage that no separate special system for producing the starter plates is required, but that a hard-rolled copper strip is produced which is known per se and which can also be obtained from a third party.
This also applies to a further variant, according to which the hard-rolled copper strip is soft-annealed within the casting and rolling plant and is available as further-processed cathode as soft-annealed copper strip in the form of a coiled coil. This is then unwound to produce the starting cathodes and fed to the straightening and compartment system. Further processing then takes place as described above.
There is also the possibility of producing the starting cathodes within a production line, in which case the process steps of reeling and uncoiling the coil from rolled or soft-annealed copper strip are omitted. The annealing of the rolled copper strip can be carried out in a vertical or horizontal type annealing furnace. Before the soft annealing, the copper strip should be degreased, brushed, rinsed with water and dried. After the annealing, it is advisable to pickle and neutralize the cooled copper strip.
Die Erfindung soll nachstehend an einigen Beispielen erläutert werden.The invention will be explained below using a few examples.
SF-Cu wurde aufeiner herkömmlichen Gieß- und Walzanlage zu einem Kupferband mit einer Breite von 930 mm und einer Dicke von 0,5 mm gewalzt. Das walzharte Kupferband besitzt eine Zugfestigkeit von 263 N/mm2 und liegt als aufgehaspeltes Coil vor. In einer separaten Anlage, bestehend aus Abhaspelvorrichtung, Glühofen, Entfettungs- und Beizeinheit, Richt- und Abteilanlage sowie der Konfektionsierungsanlage für die Ohren und Kontaktstäbe werden Startkathoden unter folgenden Bedingungen hergestellt. SF-Cu was rolled on a conventional casting and rolling machine to a copper strip with a width of 930 mm and a thickness of 0.5 mm. The hard-rolled copper strip has a tensile strength of 263 N / mm 2 and is available as a coiled coil. Starting cathodes are produced under the following conditions in a separate system, consisting of a decoiler, annealing furnace, degreasing and pickling unit, straightening and compartment system as well as the assembly system for the ears and contact bars.
Das abgehaspelte walzharte Kupferband durchläuft einen horizontalen Schwebebandofen, dessen Heizzonen auf Temperaturen im Bereich von 750 bis 720 °C eingestellt sind. Die Banddurchlaufgeschwindigkeit beträgt 35 m/min. Das Weichglühen erfolgt unter Schutzgasatmosphäre. Das weichgeglühte, abgekühlte Kupferband besitzt eine Zugfestigkeit von 217 N/mm2. Nach dem Weichglühen erfolgt in der Entfettungs- und Beizeinheit noch eine Entfernung von Zunder und gebildetem Oxyd. In der nachfolgenden Richt- und Abteilanlage wird das Kupferband in Längen von 970 mm geschnitten und die so erhaltenen Starterbleche 970 x 930 mm werden gerichtet. Wesentlich ist, daß die zurweiteren Konfektionierung gelangenden Starterbleche vollkommen plan und glatt sind, keinerlei äußerliche Beschädigungen, wie z.B. Kratzer, aufweisen und fett-, sowie emulsions- bzw. ölfrei sind. Die trockenen, sauberen Starterbleche werden zu einer Nietmaschine transportiert, um die erforderlichen Ohrenstreifen zu befestigen, die aus 0,4 mm dickem Kupferband gefertigt sind, das aus der gleichen Materialsorte wie die Starterbleche besteht. Nach dem Befestigen der "Ohren" an den Starterblechen werden noch die Kontaktstäbe angebracht.The unreeled, hard-rolled copper strip passes through a horizontal suspension belt furnace, the heating zones of which are set to temperatures in the range from 750 to 720 ° C. The belt speed is 35 m / min. Soft annealing takes place in a protective gas atmosphere. The soft annealed, cooled copper strip has a tensile strength of 217 N / mm 2 . After the soft annealing, the degreasing and pickling unit also removes scale and oxide. In the subsequent straightening and compartment system, the copper strip is cut into lengths of 970 mm and the starter plates 970 x 930 mm thus obtained are straightened. It is essential that the starter plates which are further assembled are completely flat and smooth, have no external damage, such as scratches, and are free of grease, emulsions and oil. The dry, clean starter sheets are transported to a riveting machine to attach the necessary ear strips, which are made from 0.4 mm thick copper tape, which is made from the same type of material as the starter sheets. After attaching the "ears" to the starter plates, the contact rods are attached.
Innerhalb einer herkömmlichen Gieß- und Walzanlage mit integriertem Schwebebandofen als letzte Verfahrensstufe wird walzhartes Kupferband aus SF-Cu hergestellt und als Coil aufgehaspelt. Das 930 mm breite, walzharte Kupferband hat nach dem Walzvorgang eine Dicke von 0,635 mm. Nach dem Walzvorgang wird das Kupferband entfettet, gebürstet, mit klarem Wasser gespült und getrocknet. Das walzharte Kupferband durchläuft anschließend einen Schwebebandofen mit einer Geschwindigkeit von 27,5 m/min, die Ofentemperaturen liegen im Bereich von 750 bis 720 °C. Das abgekühlte Kupferband besitzt eine Zugfestigkeit von 217 N/mm2. Es wird danach noch gebeizt, neutralisiert, als Coil aufgehaspelt und zwischengelagert. In einer gesonderten Anlage wird das als Coil vorliegende, weichgeglühte Kupferband abgehaspelt und analog wie im Beispiel 1 in einer Richt- und Abteilanlage sowie der Konfektionierungsanlage für die Ohren und Kontaktstäbe zu Startkathoden weiterverarbeitet. Die Blechdicke der an den Starterkathoden befestigten Ohren beträgt 0,5 mm. In a conventional casting and rolling plant with an integrated floating belt furnace as the last stage of the process, hard-rolled copper strip is produced from SF-Cu and coiled as a coil. The 930 mm wide, hard-rolled copper strip has a thickness of 0.635 mm after the rolling process. After the rolling process, the copper strip is degreased, brushed, rinsed with clear water and dried. The hard-rolled copper strip then runs through a floating belt furnace at a speed of 27.5 m / min, the furnace temperatures are in the range from 750 to 720 ° C. The cooled copper strip has a tensile strength of 217 N / mm 2 . It is then pickled, neutralized, reeled up as a coil and stored temporarily. The soft-annealed copper strip, which is in the form of a coil, is unwound in a separate system and further processed into starting cathodes in a straightening and compartment system, as well as in the assembly system for the ears and contact rods, as in Example 1. The sheet thickness of the ears attached to the starter cathodes is 0.5 mm.
Analoge wie im Beispiel 1 werden Startkathoden hergestellt, lediglich mit dem Unterschied, daß die Gieß- und Walzanlage, der Glühofen, die Entfettungs- und Beizeinheit, die Richt- und Abteilanlage sowie die Konfektionierungsanlage in einer Linie angeordnet sind. Dadurch entfällt das gemäß Beispiel 1 oder Beispiel 2 notwendige Auf- und Abhaspeln des walzharten bzw. weichgeglühten Kupferbandes. Das Kupferbandmaterial besteht aus SF-Cu und wird durch den Walzvorgang auf eine Dicke von 0,8 mm reduziert. Die Temperaturen im Schwebebandofen betragen ebenfalls 750 bis 720 °C, die Durchlaufgeschwindigkeit liegt bei 23 m/min. Das weichgeglühte, abgekühlte Kupferband weist eine Zugfestigkeit von 232 N/mm2 auf. Die Abmessungen der Starterbleche betragen ebenfalls 970 x 930 mm. Die an den Starterblechen angenieteten Ohren haben eine Dicke von 0,6 mm.Starting cathodes are produced analogously to Example 1, with the only difference that the casting and rolling system, the annealing furnace, the degreasing and pickling unit, the straightening and compartment system and the packaging system are arranged in one line. This eliminates the need to rewind and unwind the hard-rolled or soft-annealed copper strip according to Example 1 or Example 2. The copper strip material consists of SF-Cu and is reduced to a thickness of 0.8 mm by the rolling process. The temperatures in the suspension belt furnace are also 750 to 720 ° C, the throughput speed is 23 m / min. The soft-annealed, cooled copper strip has a tensile strength of 232 N / mm 2 . The dimensions of the starter plates are also 970 x 930 mm. The ears riveted to the starter plates have a thickness of 0.6 mm.
Analog wie im Beispiel 1 wurden unter gleichen Bedingungen Startkathoden hergestellt, jedoch ohne Weichglühen.Analogous to example 1, starting cathodes became the same under the same conditions manufactured, but without soft annealing.
Die gemäß den vorgenannten Beispielen hergestellten Startkathoden wurden für
Elektrolyseversuche eingesetzt und haben folgende Parameter:
Jedes Elektrolysebad wurde mit 30 Anoden und 31 Kathoden besetzt. Der Anodenabstand beträgt 105 mm. Die Laufzeit einer Anodenreise wurde mit 21 Tagen festgelegt. Je Bad wird über den Elektrolyteinlauf ein Volumenstrom von 18 bis 20 l/min zugeführt. Die Qualität dereingesetzten Startkathoden wurde wie folgt bewertet.
- -A:
- Prüfung der Geradheit der verwendeten Starterbleche und produzierten Kathoden durch Ausmessen nach jeweils 2 Tagen nach Inbetriebnahme.
- -B:
- Stromausbeute des jeweiligen Bades nach 9 Tagen.
- - C:
- Anzahl der aufgetretenen Kurzschlüsse
- -A:
- Check the straightness of the starter plates used and the cathodes produced by measuring after 2 days after commissioning.
- -B:
- Current yield of the respective bath after 9 days.
- - C:
- Number of short circuits that occurred
Folgende Ergebnisse wurden erzielt:
Die Ergebnisse belegen, daß die erfindungsgemäßen Startkathoden S1 bis S3 beim Einsatz in der Kupferelektrolyse zu keinem "Memory-Effekt" führen. Im Gegensatz dazu kommt es beim Einsatz der nicht weichgeglühten Startkathoden S4 in der Kupferelektrolyse zu einem "Memory-Effekt" in erheblichem Ausmaß. Die besten Ergebnisse wurden mit den Startkathoden S1 erzielt, die vorallem hinsichtlich der erzielten Stromausbeute überlegen sind.The results show that the starting cathodes S1 to S3 according to the invention at Use in copper electrolysis does not lead to a "memory effect". In contrast this occurs when the non-annealed S4 start cathodes are used in the Copper electrolysis to a "memory effect" to a considerable extent. The best Results were achieved with the starting cathodes S1, especially with regard to the achieved electricity yield are superior.
Claims (18)
Priority Applications (17)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ES98118542T ES2156425T3 (en) | 1998-10-01 | 1998-10-01 | INITIATING CATODES CONSTITUTED OF COPPER TAPE FOR THE ELECTROLYSIS OF COPPER AND PROCESS FOR ITS MANUFACTURE. |
EP98118542A EP0992615B1 (en) | 1998-10-01 | 1998-10-01 | Startkathoden aus Kupferband für die Kupferelektrolyse und Verfahren zu deren Herstellung |
DE59800478T DE59800478D1 (en) | 1998-10-01 | 1998-10-01 | Copper cathode starting sheets for copper electrolysis and manufacture thereof |
AT98118542T ATE199172T1 (en) | 1998-10-01 | 1998-10-01 | COPPER CATHODE STARTING SHEETS FOR COPPER ELECTROLYSIS AND MANUFACTURE THEREOF |
AU60866/99A AU762788B2 (en) | 1998-10-01 | 1999-09-23 | Starting cathodes made of copper band for copper electrolysis and a method for the production thereof |
RU2000117461/02A RU2221088C2 (en) | 1998-10-01 | 1999-09-23 | Starting cathode of copper band for electrolysis of copper and method for making it |
PCT/EP1999/007070 WO2000020661A1 (en) | 1998-10-01 | 1999-09-23 | Starting cathodes made of copper band for copper electrolysis and a method for the production thereof |
JP2000574752A JP2002526662A (en) | 1998-10-01 | 1999-09-23 | Starting cathode comprising copper strip for copper electrolysis and method for producing the same |
US09/555,539 US6350355B1 (en) | 1998-10-01 | 1999-09-23 | Starting cathodes made of copper band for copper electrolysis and a method for the production thereof |
BRPI9907135-5A BR9907135B1 (en) | 1998-10-01 | 1999-09-23 | Copper strap activation cathodes for cupric electrolysis and process for manufacturing activation cathodes. |
CNB998017329A CN1283844C (en) | 1998-10-01 | 1999-09-23 | Starting cathodes made of copper band for copper electrolysis and a method for the production thereof |
MXPA00004551A MXPA00004551A (en) | 1998-10-01 | 1999-09-23 | Starting cathodes made of copper band for copper electrolysis and a method for the production thereof. |
CA002312375A CA2312375C (en) | 1998-10-01 | 1999-09-23 | Starting cathodes of copper strip for copper electrolysis and method of producing same |
IDW20001008A ID24867A (en) | 1998-10-01 | 1999-09-23 | COOKING CATEGODES OF COPPER FOR ELECTROLYSIS AND COPYING METHODS |
DE19982000T DE19982000D2 (en) | 1998-10-01 | 1999-09-23 | Starting cathodes made of copper tape for copper electrolysis and processes for their production |
ARP990104924A AR021841A1 (en) | 1998-10-01 | 1999-09-29 | INITIATING CATTURES CONSTITUTED OF COPPER RIBBON FOR COPPER ELECTRICILISIS, AND PROCEDURE FOR THE MANUFACTURE OF SUCH CATHODS. |
PE1999000991A PE20001209A1 (en) | 1998-10-01 | 1999-09-30 | INITIATING CATHODES CONSTITUTED OF COPPER TAPE FOR COPPER ELECTROLYSIS AND PROCEDURE FOR ITS MANUFACTURING |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP98118542A EP0992615B1 (en) | 1998-10-01 | 1998-10-01 | Startkathoden aus Kupferband für die Kupferelektrolyse und Verfahren zu deren Herstellung |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0992615A1 true EP0992615A1 (en) | 2000-04-12 |
EP0992615B1 EP0992615B1 (en) | 2001-02-14 |
Family
ID=8232728
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98118542A Expired - Lifetime EP0992615B1 (en) | 1998-10-01 | 1998-10-01 | Startkathoden aus Kupferband für die Kupferelektrolyse und Verfahren zu deren Herstellung |
Country Status (16)
Country | Link |
---|---|
US (1) | US6350355B1 (en) |
EP (1) | EP0992615B1 (en) |
JP (1) | JP2002526662A (en) |
CN (1) | CN1283844C (en) |
AR (1) | AR021841A1 (en) |
AT (1) | ATE199172T1 (en) |
AU (1) | AU762788B2 (en) |
BR (1) | BR9907135B1 (en) |
CA (1) | CA2312375C (en) |
DE (2) | DE59800478D1 (en) |
ES (1) | ES2156425T3 (en) |
ID (1) | ID24867A (en) |
MX (1) | MXPA00004551A (en) |
PE (1) | PE20001209A1 (en) |
RU (1) | RU2221088C2 (en) |
WO (1) | WO2000020661A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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EP2383840B1 (en) * | 2005-02-03 | 2016-04-13 | Auto-Kabel Management GmbH | Electrical flat ribbon conductor for motor vehicles |
DE102006050705B4 (en) * | 2006-10-24 | 2009-01-02 | Auto-Kabel Management Gmbh | battery lead |
CN113369824B (en) * | 2021-06-30 | 2022-04-29 | 福建紫金铜业有限公司 | Production process of novel copper alloy plate strip material for welding |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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GB1294694A (en) * | 1969-11-04 | 1972-11-01 | British Insulated Callenders | Improvements in or relating to the electrolytic refining of copper |
EP0417318A1 (en) * | 1989-03-30 | 1991-03-20 | Nippon Steel Corporation | Method of producing rollable metal sheet based on quench-solidified thin cast sheet |
WO1997042360A1 (en) * | 1996-05-03 | 1997-11-13 | Asarco Incorporated | Copper cathode starting sheets |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5942166Y2 (en) * | 1978-08-22 | 1984-12-08 | 三井金属鉱業株式会社 | Beading press for seed plate |
US5286315A (en) * | 1989-03-30 | 1994-02-15 | Nippon Steel Corporation | Process for preparing rollable metal sheet from quenched solidified thin cast sheet as starting material |
DE4041854A1 (en) * | 1990-12-24 | 1992-06-25 | Kabelmetal Ag | METHOD FOR PRODUCING A GREEN PATINA ON A SEMI-PRODUCT CONSTRUCTED FROM COPPER |
JPH06136586A (en) * | 1992-10-28 | 1994-05-17 | Sumitomo Metal Mining Co Ltd | Cathode plate for electrolysis |
JPH10212562A (en) * | 1997-01-27 | 1998-08-11 | Nippon Foil Mfg Co Ltd | Final annealing method for copper foil coiled stock |
-
1998
- 1998-10-01 EP EP98118542A patent/EP0992615B1/en not_active Expired - Lifetime
- 1998-10-01 ES ES98118542T patent/ES2156425T3/en not_active Expired - Lifetime
- 1998-10-01 AT AT98118542T patent/ATE199172T1/en not_active IP Right Cessation
- 1998-10-01 DE DE59800478T patent/DE59800478D1/en not_active Expired - Fee Related
-
1999
- 1999-09-23 CN CNB998017329A patent/CN1283844C/en not_active Expired - Fee Related
- 1999-09-23 RU RU2000117461/02A patent/RU2221088C2/en not_active IP Right Cessation
- 1999-09-23 JP JP2000574752A patent/JP2002526662A/en active Pending
- 1999-09-23 US US09/555,539 patent/US6350355B1/en not_active Expired - Fee Related
- 1999-09-23 MX MXPA00004551A patent/MXPA00004551A/en unknown
- 1999-09-23 BR BRPI9907135-5A patent/BR9907135B1/en not_active IP Right Cessation
- 1999-09-23 DE DE19982000T patent/DE19982000D2/en not_active Expired - Fee Related
- 1999-09-23 WO PCT/EP1999/007070 patent/WO2000020661A1/en active IP Right Grant
- 1999-09-23 AU AU60866/99A patent/AU762788B2/en not_active Ceased
- 1999-09-23 ID IDW20001008A patent/ID24867A/en unknown
- 1999-09-23 CA CA002312375A patent/CA2312375C/en not_active Expired - Fee Related
- 1999-09-29 AR ARP990104924A patent/AR021841A1/en active IP Right Grant
- 1999-09-30 PE PE1999000991A patent/PE20001209A1/en not_active Application Discontinuation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1294694A (en) * | 1969-11-04 | 1972-11-01 | British Insulated Callenders | Improvements in or relating to the electrolytic refining of copper |
EP0417318A1 (en) * | 1989-03-30 | 1991-03-20 | Nippon Steel Corporation | Method of producing rollable metal sheet based on quench-solidified thin cast sheet |
WO1997042360A1 (en) * | 1996-05-03 | 1997-11-13 | Asarco Incorporated | Copper cathode starting sheets |
Also Published As
Publication number | Publication date |
---|---|
PE20001209A1 (en) | 2000-12-28 |
BR9907135A (en) | 2000-10-03 |
AR021841A1 (en) | 2002-08-07 |
AU762788B2 (en) | 2003-07-03 |
DE19982000D2 (en) | 2002-07-25 |
CA2312375A1 (en) | 2000-04-13 |
ID24867A (en) | 2000-08-31 |
US6350355B1 (en) | 2002-02-26 |
EP0992615B1 (en) | 2001-02-14 |
ES2156425T3 (en) | 2001-06-16 |
JP2002526662A (en) | 2002-08-20 |
DE59800478D1 (en) | 2001-03-22 |
BR9907135B1 (en) | 2009-08-11 |
ATE199172T1 (en) | 2001-02-15 |
CN1287580A (en) | 2001-03-14 |
AU6086699A (en) | 2000-04-26 |
RU2221088C2 (en) | 2004-01-10 |
WO2000020661A1 (en) | 2000-04-13 |
MXPA00004551A (en) | 2002-04-24 |
CN1283844C (en) | 2006-11-08 |
CA2312375C (en) | 2008-05-13 |
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