EP0753604B1 - Anode for the electrowinning of metals - Google Patents

Anode for the electrowinning of metals Download PDF

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Publication number
EP0753604B1
EP0753604B1 EP96111010A EP96111010A EP0753604B1 EP 0753604 B1 EP0753604 B1 EP 0753604B1 EP 96111010 A EP96111010 A EP 96111010A EP 96111010 A EP96111010 A EP 96111010A EP 0753604 B1 EP0753604 B1 EP 0753604B1
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EP
European Patent Office
Prior art keywords
anode
electrolyte
copper
metal
titanium
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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.)
Expired - Lifetime
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EP96111010A
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German (de)
French (fr)
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EP0753604A1 (en
Inventor
Nikola Dr. Anastasijevic
Gerhard Adolf Jedlicka
Karl Lohrberg
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MG Technologies AG
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Metallgesellschaft AG
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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

Definitions

  • the invention relates to an anode for electrolysis Extraction of a metal from a ionogenic metal containing electrolytes, with the application of a DC electrical voltage between the anode and one or two at a distance of 10 to 100 mm from the anode in the electrolyte arranged flat cathode or cathodes the metal on the Cathode is deposited and the anode is an in essential horizontal power supply Carrier rail located outside the electrolyte and with the mounting rail two grid-like, at least half in Electrolytes are essentially parallel Metal surfaces (anode grid) are electrically connected.
  • the anode is particularly intended for the extraction of copper.
  • An anode of this type is known from DE-C-37 31 510. Current densities in the range of 600 to 1200 A / m 2 are used for copper extraction. Perforated or lattice-like anodes are also known from U.S. Patents 3,915,834 and 4,113,586. The breakthroughs in the anode surface are said to reduce disturbances due to gas development and to even out the current distribution in the electrolyte.
  • FR-A-2560223 describes anodes with grid-shaped anode surfaces and current conductor rods with a Cu core and a Ti jacket. Parallel anode grids, which are spaced apart by spring elements, are described in GB-A-2001102.
  • the invention has for its object an anode for high and to create the highest current densities so that with it equipped electrolysis high metal separation performance can provide. At the same time, malfunctions are said to occur in the anode avoided as much as possible by gas evolution. According to the invention this succeeds with the anode with the Claim 1 combination of features.
  • Power is supplied to the anode from the outside via the Copper conductors and from there via one or more copper rods as well as their titanium jacket on the anode grid. Thereby can carry high currents of several 1000 A to the anode grid be directed.
  • the partitions For a mechanically stable anode structure provide the partitions that fill the space between the anode grids divide, the partitions also ensure the guidance of the rising gas bubbles.
  • the area of the two anode grids, which is intended for immersion in the electrolyte have a height of at least 1 m.
  • the area of the associated cathodes can be made correspondingly large, which improves the separation performance.
  • the titanium sheath surrounding the bars protects against the corrosion attack of the electrolyte.
  • the copper rod pressed into the titanium sheath during manufacture of the sheathing To do this, it is recommended to use elevated temperatures in the range of 400 to 700 ° C apply.
  • the simultaneous production of the Copper rods with the associated titanium sheath can in itself known way e.g. by composite extrusion or other Way.
  • the electrolysis container (1) of FIG. 1 has an inlet (2) for the electrolyte and a drain (3). Partially immersed in the electrolyte bath (4) are in the container (1) successively arranged cathodes (K) and anodes (A). Each Cathode and each anode is with a horizontal one Carrier rail (6) equipped, cf. also Fig. 2, by the an external DC voltage source (not shown) Current is conducted to the electrode.
  • the mounting rail (6) of the Anode according to the invention has a copper conductor (6a) inside on, which is shown in Fig. 4. To protect against corrosion the mounting rail (6) is surrounded by a cover made of titanium sheet, which is not shown in detail.
  • each anode (A) two parallel metal grids, here as anode grids (7) and (8). It can be Act expanded metal mesh, but it is also possible to Lattice structure through a dense arrangement of holes in one Manufacture metal surface.
  • the anode grid (7) and (8) consist of titanium, which is used for activation in itself known manner with mixed oxides based on Ru and / or Ir is coated. With the inside of the anode grid (7) and (8) are titanium sheets (10), (11), (12) and (13) through Spot welding connected. These are titanium sheets (10) to (13) again with the titanium jacket (15) (see FIGS. 3 and 5) welded, which surrounds the copper rods (16).
  • the distance between the two anode grids (7) and (8) is usually 20 to 80 mm.
  • the edge area (7a) and (8a) of the Anode grid is angled, cf. Fig. 3, and the two Anode grids are connected there, what the arrangement gives additional stability.
  • the titanium sheets (10) to (13) are, as Fig. 3 shows, somewhat curved and act like elastic Springs holding the anode grid (7) and (8) with light pressure tell apart.
  • Partitions (25) and (26) are e.g. also made of titanium sheet.
  • the walls (25) and (26) are with the Titanium jacket of the copper rod (16) welded and also with the bent edge regions (7a) and (8a) of the anode grid (7) and (8) electrically connected. This makes them work Partitions (25) and (26) mechanically stabilizing, conduct Strcm from the copper rod (16) to the edge areas (7a) and (8a) the anode grid and also act as a guide for the rising gas bubbles.
  • 1 is the better one Clarity because of the partition (25) only with an anode (A) shown.
  • each anode leaves no gas bubbles significant disability rise and that Leave the electrolysis bath (4). This is especially true at high Current densities are of great importance because of the increased gas formation disturbs the movement of the ions in the electrolyte and the Can locally reduce ion concentration.
  • FIG. 4 shows an enlarged view of how the copper conductor (6a) the mounting rail (6) with a copper rod (16) Screwing is connected.
  • the screw (20) with its thread in a threaded blind hole (21) at the upper end of the copper rod (16).
  • the surfaces pressed against each other (22) on the copper conductor (6a) and on the front end of the copper rod (16) are serrated or otherwise roughened to the ohmic To keep the resistance at the current transition low.
  • the titanium sheath (15) surrounding the copper rod (16) omitted for clarity.
  • the cross-sectional area of the Copper rods don't necessarily have to be circular, it is e.g. a rectangular or oval shape possible.
  • For the titanium sheath (15) usually have wall thicknesses in the range of 0.2 up to 1 mm in question.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)

Description

Die Erfindung betrifft eine Anode für die Elektrolyse zur Gewinnung eines Metalls aus einem das Metall ionogen enthaltenden Elektrolyten, wobei unter Anlegen einer elektrischen Gleichspannung zwischen der Anode und einer oder zwei im Abstand von 10 bis 100 mm von der Anode im Elektrolyten angeordneten flächigen Kathode oder Kathoden das Metall an der Kathode abgeschieden wird und wobei die Anode eine im wesentlichen horizontale, der Stromzuführung dienende, außerhalb des Elektrolyten befindliche Tragschiene aufweist und mit der Tragschiene zwei gitterartige, mindestens zur Hälfte im Elektrolyten befindliche, im wesentlichen parallele Metallflächen (Anodengitter) elektrisch leitend verbunden sind. Die Anode ist insbesondere zum Gewinnen von Kupfer vorgesehen.The invention relates to an anode for electrolysis Extraction of a metal from a ionogenic metal containing electrolytes, with the application of a DC electrical voltage between the anode and one or two at a distance of 10 to 100 mm from the anode in the electrolyte arranged flat cathode or cathodes the metal on the Cathode is deposited and the anode is an in essential horizontal power supply Carrier rail located outside the electrolyte and with the mounting rail two grid-like, at least half in Electrolytes are essentially parallel Metal surfaces (anode grid) are electrically connected. The anode is particularly intended for the extraction of copper.

Eine Anode dieser Art ist aus DE-C-37 31 510 bekannt. Hierbei werden bei der Kupfergewinnung Stromdichten im Bereich von 600 bis 1200 A/m2 angewandt. Gelochte oder gitterartige Anoden sind ferner aus den US-Patenten 3 915 834 und 4 113 586 bekannt. Die Durchbrechungen in der Anodenfläche sollen Störungen durch Gasentwicklung vermindern und die Stromverteilung im Elektrolyten vergleichmäßigen. FR-A-2560223 beschreibt Anoden mit gitterförmigen Anodenflächen und Stromleiterstangen mit Cu-Kern und Ti-Mantel. Parallele Anodengitter, die durch Federelemente im Abstand gehalten werden, sind in GB-A-2001102 beschrieben.An anode of this type is known from DE-C-37 31 510. Current densities in the range of 600 to 1200 A / m 2 are used for copper extraction. Perforated or lattice-like anodes are also known from U.S. Patents 3,915,834 and 4,113,586. The breakthroughs in the anode surface are said to reduce disturbances due to gas development and to even out the current distribution in the electrolyte. FR-A-2560223 describes anodes with grid-shaped anode surfaces and current conductor rods with a Cu core and a Ti jacket. Parallel anode grids, which are spaced apart by spring elements, are described in GB-A-2001102.

Der Erfindung liegt die Aufgabe zugrunde, eine Anode für hohe und höchste Stromdichten zu schaffen, so daß die damit ausgerüstete Elektrolyse hohe Metallabscheideleistungen erbringen kann. Gleichzeitig sollen in der Anode Störungen durch Gasentwicklung möglichst vermieden werden. Erfindungsgemäß gelingt dies mit der Anode mit der im Patentanspruch 1 genannten Merkmalskombination.The invention has for its object an anode for high and to create the highest current densities so that with it equipped electrolysis high metal separation performance can provide. At the same time, malfunctions are said to occur in the anode avoided as much as possible by gas evolution. According to the invention this succeeds with the anode with the Claim 1 combination of features.

Die Stromzuführung zur Anode erfolgt von außen über den Kupferleiter und von dort über einen oder mehrere Kupferstäbe sowie durch deren Titan-Mantel auf die Anodengitter. Dadurch können hohe Ströme von mehreren 1000 A zu den Anodengittern geleitet werden. Für einen mechanisch stabilen Anodenaufbau sorgen die Trennwände, die den Raum zwischen den Anodengittern teilen, auch sorgen die Trennwände für die Führung der aufsteigenden Gasblasen. Die Fläche der beiden Anodengitter, die für das Eintauchen in den Elektrolyten vorgesehen ist, kann eine Höhe von mindestens 1 m aufweisen. Die Fläche der zugehörigen Kathoden kann entsprechend groß ausgebildet werden, was die Abscheideleistung verbessert.Power is supplied to the anode from the outside via the Copper conductors and from there via one or more copper rods as well as their titanium jacket on the anode grid. Thereby can carry high currents of several 1000 A to the anode grid be directed. For a mechanically stable anode structure provide the partitions that fill the space between the anode grids divide, the partitions also ensure the guidance of the rising gas bubbles. The area of the two anode grids, which is intended for immersion in the electrolyte have a height of at least 1 m. The area of the associated cathodes can be made correspondingly large, which improves the separation performance.

Während des Betriebs der Elektrolyse befinden sich die Kupferstäbe der Anoden im Elektrolyten, bei dem es sich z.B. um Kupfersulfat handelt. Der die Stäbe umgebende Titan-Mantel schützt gegen den Korrosionsangriff des Elektrolyten. Um den notwendigen guten Stromübergang zwischen dem Kupferstab und dem ihn umgebenden Titan-Mantel zu erreichen, wird der Kupferstab beim Herstellen der Ummantelung in den Titan-Mantel eingepreßt. Hierzu empfiehlt es sich, erhöhte Temperaturen im Bereich von 400 bis 700°C anzuwenden. Die gleichzeitige Herstellung des Kupferstabs mit zugehöriger Titan-Ummantelung kann in an sich bekannter Weise z.B. durch Verbundstrangpressen oder auf andere Weise erfolgen.The are in operation during the electrolysis Copper rods of the anodes in the electrolyte, which are e.g. around Copper sulfate. The titanium sheath surrounding the bars protects against the corrosion attack of the electrolyte. To the necessary good current transfer between the copper rod and the to reach the surrounding titanium coat, the copper rod pressed into the titanium sheath during manufacture of the sheathing. To do this, it is recommended to use elevated temperatures in the range of 400 to 700 ° C apply. The simultaneous production of the Copper rods with the associated titanium sheath can in itself known way e.g. by composite extrusion or other Way.

Ausgestaltungsmöglichkeiten der Anode werden mit Hilfe der Zeichnung erläutert. Es zeigt:

Fig. 1
eine Metallgewinnungs-Elektrolyse im Längsschnitt in schematischer Darstellung,
Fig. 2
eine Anode im Längsschnitt, geschnitten nach der Linie II-II in Fig. 3,
Fig. 3
einen Querschnitt durch die Anode der Fig. 2, geschnitten nach der Linie III-III,
Fig. 4
die Verbindung zwischen der Tragschiene und einem Kupferstab im Längsschnitt und
Fig. 5
einen Querschnitt durch einen Kupferstab mit Titan-Mantel.
Design options of the anode are explained with the help of the drawing. It shows:
Fig. 1
a metal extraction electrolysis in longitudinal section in a schematic representation,
Fig. 2
an anode in longitudinal section, cut along the line II-II in Fig. 3,
Fig. 3
3 shows a cross section through the anode of FIG. 2, cut along the line III-III,
Fig. 4
the connection between the mounting rail and a copper rod in longitudinal section and
Fig. 5
a cross section through a copper rod with a titanium jacket.

Der Elektrolysebehälter (1) der Fig. 1 weist einen Zulauf (2) für den Elektrolyten und einen Ablauf (3) auf. Teilweise eingetaucht in das Elektrolytbad (4) sind im Behälter (1) aufeinanderfolgend Kathoden (K) und Anoden (A) angeordnet. Jede Kathode und jede Anode ist mit einer horizontal verlaufenden Tragschiene (6) ausgestattet, vgl. auch Fig. 2, durch die von einer äußeren Gleichspannungsquelle (nicht dargestellt) der Strom zur Elektrode geleitet wird. Die Tragschiene (6) der erfindungsgemäßen Anode weist im Innern einen Kupferleiter (6a) auf, der in Fig. 4 dargestellt ist. Zum Schutz vor Korrosion ist die Tragschiene (6) von einer Hülle aus Titanblech umgeben, die nicht im einzelnen dargestellt ist.The electrolysis container (1) of FIG. 1 has an inlet (2) for the electrolyte and a drain (3). Partially immersed in the electrolyte bath (4) are in the container (1) successively arranged cathodes (K) and anodes (A). Each Cathode and each anode is with a horizontal one Carrier rail (6) equipped, cf. also Fig. 2, by the an external DC voltage source (not shown) Current is conducted to the electrode. The mounting rail (6) of the Anode according to the invention has a copper conductor (6a) inside on, which is shown in Fig. 4. To protect against corrosion the mounting rail (6) is surrounded by a cover made of titanium sheet, which is not shown in detail.

Wie aus Fig. 1 bis 3 hervorgeht, gehören zu jeder Anode (A) zwei parallele Metallgitter, die hier als Anodengitter (7) und (8) bezeichnet werden. Es kann sich hierbei um Streckmetallgitter handeln, doch ist es auch möglich, die Gitterstruktur durch eine dichte Anordnung von Löchern in einer Metallfläche herzustellen. Die Anodengitter (7) und (8) bestehen aus Titan, welches zur Aktivierung in an sich bekannter Weise mit Mischoxiden auf Ru- und/oder Ir-Basis beschichtet ist. Mit der Innenseite der Anodengitter (7) und (8) sind Titanbleche (10), (11), (12) und (13) durch Punktschweißen verbunden. Diese Titanbleche (10) bis (13) sind wiederum mit dem Titan-Mantel (15) (vgl. Fig. 3 und 5) verschweißt, der die Kupferstäbe (16) umgibt.As can be seen from FIGS. 1 to 3, each anode (A) two parallel metal grids, here as anode grids (7) and (8). It can be Act expanded metal mesh, but it is also possible to Lattice structure through a dense arrangement of holes in one Manufacture metal surface. The anode grid (7) and (8) consist of titanium, which is used for activation in itself known manner with mixed oxides based on Ru and / or Ir is coated. With the inside of the anode grid (7) and (8) are titanium sheets (10), (11), (12) and (13) through Spot welding connected. These are titanium sheets (10) to (13) again with the titanium jacket (15) (see FIGS. 3 and 5) welded, which surrounds the copper rods (16).

Der Abstand der beiden Anodengitter (7) und (8) beträgt üblicherweise 20 bis 80 mm. Der Randbereich (7a) und (8a) der Anodengitter ist abgewinkelt, vgl. Fig. 3, und die beiden Anodengitter sind dort miteinander verbunden, was der Anordnung zusätzliche Stabilität verleiht. Die Titanbleche (10) bis (13) sind, wie Fig. 3 zeigt, etwas gebogen und wirken wie elastische Federn, welche die Anodengitter (7) und (8) mit leichtem Druck auseinanderhalten.The distance between the two anode grids (7) and (8) is usually 20 to 80 mm. The edge area (7a) and (8a) of the Anode grid is angled, cf. Fig. 3, and the two Anode grids are connected there, what the arrangement gives additional stability. The titanium sheets (10) to (13) are, as Fig. 3 shows, somewhat curved and act like elastic Springs holding the anode grid (7) and (8) with light pressure tell apart.

Wie aus Fig. 3 ersichtlich, sind zwischen den Anodengittern (7) und (8) zwei vertikale, parallel zu den Gittern verlaufende Trennwände (25) und (26) angeordnet, welche den Raum zwischen den Anodengittern teilen. Diese Trennwände bestehen z.B. ebenfalls aus Titanblech. Die Wände (25) und (26) sind mit dem Titan-Mantel des Kupferstabs (16) verschweißt und auch mit den umgebogenen Randbereichen (7a) und (8a) der Anodengitter (7) und (8) elektrisch leitend verbunden. Dadurch wirken die Trennwände (25) und (26) mechanisch stabilisierend, leiten Strcm vom Kupferstab (16) bis in die Randbereiche (7a) und (8a) der Anodengitter und wirken ferner als Führung für die aufsteigenden Gasblasen. In Fig. 1 ist der besseren Übersichtlichkeit wegen die Trennwand (25) nur bei einer Anode (A) eingezeichnet.As can be seen from Fig. 3, between the anode grids (7) and (8) two vertical ones parallel to the grids Partitions (25) and (26) arranged, which the space between share the anode grid. These partitions are e.g. also made of titanium sheet. The walls (25) and (26) are with the Titanium jacket of the copper rod (16) welded and also with the bent edge regions (7a) and (8a) of the anode grid (7) and (8) electrically connected. This makes them work Partitions (25) and (26) mechanically stabilizing, conduct Strcm from the copper rod (16) to the edge areas (7a) and (8a) the anode grid and also act as a guide for the rising gas bubbles. 1 is the better one Clarity because of the partition (25) only with an anode (A) shown.

Die Gitterstruktur jeder Anode läßt entstehende Gasblasen ohne nennenswerte Behinderung aufwärts steigen und das Elektrolysebad (4) verlassen. Dies ist besonders bei hohen Stromdichten von großer Bedeutung, da die verstärkte Gasbildung die Bewegung der Ionen im Elektrolyten stört und die Ionenkonzentration örtlich verringern kann.The lattice structure of each anode leaves no gas bubbles significant disability rise and that Leave the electrolysis bath (4). This is especially true at high Current densities are of great importance because of the increased gas formation disturbs the movement of the ions in the electrolyte and the Can locally reduce ion concentration.

In Fig. 4 ist vergrößert dargestellt, wie der Kupferleiter (6a) der Tragschiene (6) mit einem Kupferstab (16) durch Verschrauben verbunden ist. Hierbei greift die Schraube (20) mit ihrem Gewinde in ein Gewinde-Sackloch (21) am oberen Ende des Kupferstabs (16) ein. Die gegeneinander gepreßten Flächen (22) am Kupferleiter (6a) und am Stirnende des Kupferstabs (16) sind gezähnt oder in anderer Weise angerauht, um den ohmschen Widerstand beim Stromübergang niedrig zu halten. In Fig. 4 wurde der Titan-Mantel (15), der den Kupferstab (16) umgibt, der besseren Übersichtlichkeit wegen weggelassen. Der Durchmesser der Kupferstäbe (16), vgl. auch Fig. 5, liegt zumeist im Bereich von 10 bis 40 mm. Die Querschnittfläche der Kupferstäbe muß nicht unbedingt kreisförmig sein, es ist auch z.B. eine rechteckige oder ovale Form möglich. Für den Titan-Mantel (15) kommen üblicherweise Wandstärken im Bereich von 0,2 bis 1 mm in Frage.4 shows an enlarged view of how the copper conductor (6a) the mounting rail (6) with a copper rod (16) Screwing is connected. The screw (20) with its thread in a threaded blind hole (21) at the upper end of the copper rod (16). The surfaces pressed against each other (22) on the copper conductor (6a) and on the front end of the copper rod (16) are serrated or otherwise roughened to the ohmic To keep the resistance at the current transition low. 4 the titanium sheath (15) surrounding the copper rod (16) omitted for clarity. The Diameter of the copper rods (16), cf. 5, too mostly in the range of 10 to 40 mm. The cross-sectional area of the Copper rods don't necessarily have to be circular, it is e.g. a rectangular or oval shape possible. For the titanium sheath (15) usually have wall thicknesses in the range of 0.2 up to 1 mm in question.

Claims (3)

  1. Anode for electrolysis for recovering a metal from an electrolyte containing the metal in ionogenic form, where by applying an electric d.c. voltage between the anode and one or two plate cathodes, which are arranged in the electrolyte at a distance of 10 to 100 mm from the anode, the metal is precipitated at the cathode, where the anode has a substantially horizontal mounting rail which serves as power lead and is disposed outside the electrolyte, and two grid-like, substantially parallel metal surfaces (anode grids), at least half of which is immersed in the electrolyte, are connected with the mounting rail in an electrically conductive way, where the mounting rail has a copper conductor and with the copper conductor at least one vertical copper rod is connected, where between the copper conductor and the copper rod a direct transfer of current exists, the copper rod is enclosed by a shell (15) of titanium and the copper rod is press-fitted into the shell, where the two anode grids (7, 8) are conductively connected with the titanium shell of the copper rod through spring members (10, 11, 12, 13) of a titanium sheet, and the space between the two anode grids is divided by at least two vertical metal sheets (25, 26), where each metal sheet is connected with the titanium shell and one edge portion (7a, 8a) each of the anode grids.
  2. The anode as claimed in claim 1, characterized in that the surface of the two anode grids, which is provided for immersion into the electrolyte, has a height of at least 1 m.
  3. The anode as claimed in claim 1 or 2, characterized in that the copper conductor of the mounting rail is screw-connected with the vertical copper rod.
EP96111010A 1995-07-12 1996-07-09 Anode for the electrowinning of metals Expired - Lifetime EP0753604B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19525360A DE19525360A1 (en) 1995-07-12 1995-07-12 Anode for the electrolytic extraction of metals
DE19525360 1995-07-12

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EP0753604A1 EP0753604A1 (en) 1997-01-15
EP0753604B1 true EP0753604B1 (en) 2000-06-14

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EP (1) EP0753604B1 (en)
AU (1) AU704628B2 (en)
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PE (1) PE11797A1 (en)

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KR100296374B1 (en) * 1998-12-17 2001-10-26 장인순 Method and apparatus for decontaminating contaminated soil in radioactive waste drum by electro-electric method
KR20010073752A (en) * 2000-01-20 2001-08-03 마대열 Electroplating boosbar manufacturing process
DE102004008813B3 (en) * 2004-02-20 2005-12-01 Outokumpu Oyj Process and installation for the electrochemical deposition of copper
US8038855B2 (en) * 2009-04-29 2011-10-18 Freeport-Mcmoran Corporation Anode structure for copper electrowinning
US9150974B2 (en) 2011-02-16 2015-10-06 Freeport Minerals Corporation Anode assembly, system including the assembly, and method of using same
US20120231574A1 (en) * 2011-03-12 2012-09-13 Jiaxiong Wang Continuous Electroplating Apparatus with Assembled Modular Sections for Fabrications of Thin Film Solar Cells
ITUB20152450A1 (en) * 2015-07-24 2017-01-24 Industrie De Nora Spa ELECTRODIC SYSTEM FOR ELECTRODUCTION OF NON-FERROUS METALS
ES2580552B1 (en) * 2016-04-29 2017-05-31 Industrie De Nora S.P.A. SAFE ANODE FOR ELECTROCHEMICAL CELL

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US4134806A (en) * 1973-01-29 1979-01-16 Diamond Shamrock Technologies, S.A. Metal anodes with reduced anodic surface and high current density and their use in electrowinning processes with low cathodic current density
IT1114623B (en) * 1977-07-01 1986-01-27 Oronzio De Nora Impianti DIAPHRAGM MONOPOLAR ELECTROLYTIC CELL
US4391695A (en) * 1981-02-03 1983-07-05 Conradty Gmbh Metallelektroden Kg Coated metal anode or the electrolytic recovery of metals
DE3209138A1 (en) * 1982-03-12 1983-09-15 Conradty GmbH & Co Metallelektroden KG, 8505 Röthenbach COATED VALVE METAL ANODE FOR THE ELECTROLYTIC EXTRACTION OF METALS OR METAL OXIDES
DE3406797C2 (en) * 1984-02-24 1985-12-19 Conradty GmbH & Co Metallelektroden KG, 8505 Röthenbach Coated valve metal anode for the electrolytic extraction of metals or metal oxides
DE3421480A1 (en) * 1984-06-08 1985-12-12 Conradty GmbH & Co Metallelektroden KG, 8505 Röthenbach COATED VALVE METAL ELECTRODE FOR ELECTROLYTIC GALVANIZATION

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US5679240A (en) 1997-10-21
MX9602725A (en) 1997-09-30
PE11797A1 (en) 1997-04-19
AU5944896A (en) 1997-01-23
AU704628B2 (en) 1999-04-29
DE19525360A1 (en) 1997-01-16
DE59605429D1 (en) 2000-07-20
EP0753604A1 (en) 1997-01-15

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