EP0429748A1 - Electrode for the recovery of metals from a solution containing metal-ions - Google Patents

Electrode for the recovery of metals from a solution containing metal-ions Download PDF

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Publication number
EP0429748A1
EP0429748A1 EP90110925A EP90110925A EP0429748A1 EP 0429748 A1 EP0429748 A1 EP 0429748A1 EP 90110925 A EP90110925 A EP 90110925A EP 90110925 A EP90110925 A EP 90110925A EP 0429748 A1 EP0429748 A1 EP 0429748A1
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EP
European Patent Office
Prior art keywords
solution
belt
cathode
metal
deposited
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EP90110925A
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German (de)
French (fr)
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EP0429748B1 (en
Inventor
Harri Heinke
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De Nora Deutschland GmbH
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Heraeus Elektroden GmbH
Heraeus Elektrochemie GmbH
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/007Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells comprising at least a movable electrode
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C5/00Electrolytic production, recovery or refining of metal powders or porous metal masses
    • C25C5/02Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06Operating or servicing
    • C25C7/08Separating of deposited metals from the cathode

Definitions

  • the invention relates to a device for the continuous electrolytic removal of metals from a solution containing metal ions by means of a cathode surface which is partially immersed in the solution and which runs through the solution and is in the form of an endless flexible strip, the deposited metal being removed from the solution from the cathode surface and with an anode within the solution.
  • an electrolysis cell for the electrolytic deposition of metals from liquid containing metal ions, in particular process wastewater which contains a large number of planar electrodes spaced parallel to one another in a trough, the cathodes having openings and each are connected to the current source by means of connection resistors of different sizes, so that the cathodes are each subjected to the same current density.
  • EP-OS 248 118 discloses an electrolytic device for the continuous production of metal foils from a solution containing metal ions in a tank, the cathode partially immersed in the solution being designed as a drum or continuous endless belt; it is surrounded in its immersed area by a spaced anode which is provided with channels or openings for the electrolyte access. The metal deposited on the cathode is separated from the cathode after leaving the solution.
  • the cathode has a surface made of metal, for example titanium or tantalum, while the anode is made of titanium, for example.
  • An acidic metal ion solution for example of copper sulfate and sulfuric acid, is used as the solution.
  • the object of the invention is to apply metals which deposit inhomogeneous form from a solution containing metal ions; a largely automatic device is to be created, so that labor-intensive operations for removing the deposited material can be omitted.
  • the strip is fed to a drying device which has a filament for emitting heat radiation.
  • a collecting device for the deposited electrolyte-containing metal is arranged below the stripping device, which is followed by a separating device.
  • a major advantage can be seen in the simple optimization by setting the belt circulation speed and current density, so that these parameters can be optimally adapted to the concentration and temperature of the solution.
  • Another advantage is the fact that continuous application can be automated to a large extent.
  • the device according to the invention has a trough 1 containing the solution and made of electrolyte-resistant material, such as, for example, stainless steel or plastic.
  • a cathode roller 2 which is electrically connected to the negative pole of a voltage source 4 and is rotatably mounted about a horizontal axis 3.
  • the cathode roller On its side assigned to the bottom of the trough 1, the cathode roller is surrounded by a semicircular or U-shaped anode 5 made of expanded metal or perforated metal with an activation layer which is connected to the positive pole of the voltage source 4.
  • the electrolyte level is designated by reference number 6.
  • the metallic surface of the flexible belt 7 running around the cathode roller is at the potential of the cathode roller 2, ie it is also electrically connected to the negative pole of the voltage source 4.
  • the flexible belt 7 comprises the cathode roller 2 to approximately 0.6 times its circumference, the belt 7 outside the electrolyte solution 8 via deflection rollers 9, 10, 11 through the various work stations, such as drying device 12, stripping device 13 and rinsing device 14 to be led.
  • the deflection roller 10 is driven by a schematically illustrated electric motor 15.
  • the axis of the deflection roller 11 is supported by a suspension, so that the flexible band 7 is always tensioned and transported.
  • the deflection roller 11 which is electrically connected to the negative pole of the voltage source 4 and is pressed against the deposition surface of the band 7, is additionally provided.
  • the cathode roller 2 with its own drive, with the electric motor 15 possibly being omitted.
  • the flexible band 7 is made of titanium or a titanium-based alloy, the cathode roller 2 also consisting of titanium or titanium-based alloy.
  • an electrically conductive plastic band or another metal band instead of a titanium band, which has a coating of titanium or another valve metal, such as tantalum.
  • the anode is also made of valve metal, such as Titanium or tantalum. It is also possible to use a solid metal anode.
  • the drying device 12 consists of an electric heat radiation device with incandescent filaments 16, which dries, for example by infrared radiation, the metal deposited on the strip surface, which may contain liquid electrolyte particles, to the extent that it can be fed to the mechanically operating stripping device 13.
  • the stripping device 13 has brushes 17 rotating about horizontal axes, below which there is a collecting device 18. The axes of the rotating brushes 17 are arranged at an angle between 30 and 60 ° to the tape running direction in order to remove the stripped material from the tape.
  • the material is fed to the funnel-shaped collecting device 18 located below the stripping device 13 by free fall.
  • a separating device 19 is arranged below the collecting device.
  • the rinsing device 14 adjoins the scraper device 13 and is additionally provided with rotating scratching brushes 20.
  • the rinsing is optionally reinforced by a gaseous or liquid medium which is supplied via nozzles.
  • the solution containing metal ions is supplied through an inlet opening 21 located at the bottom of the trough 1, while an outlet opening 22 is provided in the side wall of the trough 1 to discharge the depleted electrolyte.
  • a separating device 23 designed as a diaphragm or ion exchange membrane can be inserted between anode 5 and cathode roller 2. She shares the electrolyte space of the trough into a catholyte space 24 facing the cathode roller 2 and an anolyte space 25 located on the other side of the separating device 23.
  • the belt circulation speed is approx. 0.84 m / min with a current density of 6500 A / m2. It is possible to provide a belt circulation speed in the range from 0.3 m / min to 1.44 m / min, a higher circulation speed having to be compensated for by a larger current density; the maximum current density is 10,000 A / m 2 .
  • At least 50% of the circumference of the cathode roller is immersed in the electrolyte or catholyte, i.e. at least 50% of the circumference of the roller is below the electrolyte level designated with number 6.
  • the temperature of the electrolyte solution is in the range from 20 to 100 ° C.
  • the temperature in the drying device 12 is below the limit temperature of the strip in order to avoid diffusion between the deposited metal and the strip.
  • the flexible band 7 is fed to the cathode roller 2 via deflection roller 11 after leaving the rinsing device 14 and is immersed in the solution 8.
  • the flexible strip 7 is contacted via cathode roller 2 and / or deflection roller 11 and, if appropriate, deflection rollers 9 and 10.
  • metal is deposited from the solution, which after passing through the solution bath on the other side the cathode roller 2 again leaves the electrolyte bath; the material 27 consisting of the deposited metal and liquid electrolyte particles is symbolically indicated by dots.
  • the flexible belt 7 is then first fed to the drying device 12, in which the Constant material is dried by heat radiation using incandescent filament 16 to the extent that it can be fed to the subsequent stripping device 13 for the purpose of mechanical separation by means of rotating brushes and scrapers.
  • the electrolyte-containing metal stripped from the brushes and scrapers leaves the belt and is fed by free fall to the funnel-shaped collecting device 18, the metal essentially being a conglomerate of powder and coherent lumps of deposit; to improve the material flow, the collecting device can be provided with a vibrator; the electrolyte-containing metal is then separated from the remaining electrolyte particles in a separating device 19 by pressing and filtering, so that a redissolution of the deposited metal is prevented.
  • the belt then passes through the rinsing device 14, in which the belt 7 is cleaned of all separation products by means of revolving scratching brushes 20, so that it can again be fed to the cathode roller 2 in the trough 1.
  • a zinc sulfate solution for example, is fed to the trough 1 as the electrolyte solution, while the deposited metal essentially consists of zinc. It is of course also possible to use the device according to the invention for the electrolytic discharge of other metals - for example heavy or noble metals - from other alkaline or acidic solutions containing metal ions.

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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)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

For the continuous electrolytic recovery of metals in nonhomogeneous form from a solution containing metal ions, use is made of an endless flexible titanium belt (7) as cathode area. The belt (7) is partially immersed in the solution and passes through it, being guided in the solution around a cathode roller (2) which is partially surrounded by a titanium anode (5) with an activation coating. After leaving the solution the metal deposited as a nonhomogeneous material is removed from the flexible belt by a stripper device (13). <IMAGE>

Description

Die Erfindung betrifft eine Vorrichtung zum kontinuierlichen elektrolytischen Austragen von Metallen aus einer Metallionen enthaltenden Lösung mittels einer teilweise in die Lösung eintauchenden, durch die Lösung laufenden, als endloses flexibles Band ausgebildeten Kathodenfläche, wobei das abgeschiedene Metall außerhalb der Lösung von der Kathodenfläche entfernt wird und mit einer innerhalb der Lösung befindlichen Anode.The invention relates to a device for the continuous electrolytic removal of metals from a solution containing metal ions by means of a cathode surface which is partially immersed in the solution and which runs through the solution and is in the form of an endless flexible strip, the deposited metal being removed from the solution from the cathode surface and with an anode within the solution.

Aus der DE-PS 36 40 020 ist eine Elektrolysezelle zur elektrolytischen Abscheidung von Metallen aus Metallionen enthaltender Flüssigkeit, insbesondere Prozeßabwasser, bekannt, welche eine Vielzahl von flächenhaften, zueinander im Abstand parallel angeordneten Elektroden in einem Trog enthält, wobei die Kathoden Öffnungen aufweisen und je nach Abstand zur Anode über verschieden große Anschlußwiderstände mit der Stromquelle verbunden sind, so daß die Kathoden jeweils mit der gleichen Stromdichte beaufschlagt werden.From DE-PS 36 40 020 an electrolysis cell for the electrolytic deposition of metals from liquid containing metal ions, in particular process wastewater, is known, which contains a large number of planar electrodes spaced parallel to one another in a trough, the cathodes having openings and each are connected to the current source by means of connection resistors of different sizes, so that the cathodes are each subjected to the same current density.

Als problematisch erweist sich bei einer solchen Anlage die verhältnismäßig lohnintensive Einzelentnahme der mit dem abgeschiedenen Metall versehenen Kathodenfläche sowie das verhältnismäßig arbeitsaufwendige Entfernen des abgeschiedenen Materials.In such a system, the relatively wage-intensive individual removal of the cathode surface provided with the deposited metal and the relatively labor-intensive removal of the deposited material prove to be problematic.

Aus der EP-OS 248 118 ist eine elektrolytische Vorrichtung zur kontinuierlichen Herstellung von Metallfolien aus einer in einem Tank befindlichen Metallionen enthaltenden Lösung bekannt, wobei die teilweise in die Lösung eingetauchte Kathode als Trommel oder umlaufendes Endlosband ausgeführt ist; sie wird in ihrem eingetauchten Bereich von einer im Abstand angeordneten Anode umgeben, die mit Kanälen bzw. Öffnungen für den Elektrolytzutritt versehen ist. Das auf der Kathode abgeschiedene Metall wird nach Verlassen der Lösung von der Kathode abgetrennt.EP-OS 248 118 discloses an electrolytic device for the continuous production of metal foils from a solution containing metal ions in a tank, the cathode partially immersed in the solution being designed as a drum or continuous endless belt; it is surrounded in its immersed area by a spaced anode which is provided with channels or openings for the electrolyte access. The metal deposited on the cathode is separated from the cathode after leaving the solution.

Die Kathode weist dabei eine aus Metall bestehende Oberfläche, beispielsweise aus Titan oder Tantal, auf, während die Anode beispielsweise aus Titan besteht. Als Lösung wird eine saure Metallionen-Lösung, beispielsweise aus Kupfersulfat und Schwefelsäure, eingesetzt.The cathode has a surface made of metal, for example titanium or tantalum, while the anode is made of titanium, for example. An acidic metal ion solution, for example of copper sulfate and sulfuric acid, is used as the solution.

Als problematisch erweist sich hier die kontinuierliche Ausbringung von Metallen mittels bewegter Kathode, sofern es nicht möglich ist, homogene, kompakte sich selbst tragende Metallschichten auf der Kathode abzuscheiden; schwierig wird es insbesondere bei schlammähnlichen Metallstrukturen bzw. Dendriten oder andersartigen undefinierbaren Metallstrukturen, wie z.B. Kugelstrukturen, die untereinander keine homogene Schichten bei der Abscheidung bilden.The continuous application of metals by means of a moving cathode proves to be problematic here, provided it is not possible to deposit homogeneous, compact, self-supporting metal layers on the cathode; it becomes particularly difficult with sludge-like metal structures or dendrites or other types of undefinable metal structures, such as Spherical structures that do not form homogeneous layers with each other during the deposition.

Die Erfindung stellt sich die Aufgabe, in inhomogener Form sich abscheidende Metalle aus einer Metallionen enthaltenden Lösung auszubringen; dabei soll eine weitgehend selbsttätig arbeitende Vorrichtung geschaffen werden, so daß lohnintensive Arbeitsgänge zur Entfernung des abgeschiedenen Materials entfallen können.The object of the invention is to apply metals which deposit inhomogeneous form from a solution containing metal ions; a largely automatic device is to be created, so that labor-intensive operations for removing the deposited material can be omitted.

Die Aufgabe wird erfindungsgemäß durch die kennzeichnenden Merkmale des Anspruchs 1 gelöst.The object is achieved by the characterizing features of claim 1.

In einer bevorzugten Ausführungsform wird das Band nach Verlassen der Lösung vor dem Erreichen der Abstreifvorrichtung einer Trockenvorrichtung zugeführt, welche Glühwendel zur Abgabe von Wärmestrahlung aufweist. Unterhalb der Abstreifvorrichtung ist eine Sammelvorrichtung für das abgeschiedene elektrolythaltige Metall angeordnet, an die sich eine Abtrennvorrichtung anschließt. Weitere vorteilhafte Ausgestaltungen des Gegenstandes der Erfindung sind in den Unteransprüchen angegeben.In a preferred embodiment, after leaving the solution and before reaching the stripping device, the strip is fed to a drying device which has a filament for emitting heat radiation. A collecting device for the deposited electrolyte-containing metal is arranged below the stripping device, which is followed by a separating device. Further advantageous refinements of the subject matter of the invention are specified in the subclaims.

Ein wesentlicher Vorteil ist in der einfachen Optimierung durch Einstellung von Bandumlaufgeschwindigkeit und Stromdichte zu sehen, so daß diese Parameter jeweils der Konzentration und Temperatur der Lösung optimal angepaßt werden können. Ein weiterer Vorteil ist in der weitgehenden Automatisierbarkeit der kontinuierlichen Aufbringung zu sehen.A major advantage can be seen in the simple optimization by setting the belt circulation speed and current density, so that these parameters can be optimally adapted to the concentration and temperature of the solution. Another advantage is the fact that continuous application can be automated to a large extent.

Im folgenden ist der Gegenstand der Erfindung anhand der in der Figur dargestellten Querschnittsdarstellung näher erläutert.The subject matter of the invention is explained in more detail below with reference to the cross-sectional illustration shown in the figure.

Gemäß der Figur weist die erfindungsgemäße Vorrichtung einen die Lösung enthaltenden Trog 1 aus elektrolytbeständigem Werkstoff, wie beispielsweise Edelstahl oder Kunststoff, auf. In dem Trog befindet sich eine mit dem negativen Pol einer Spannungsquelle 4 elektrisch verbundene Kathodenwalze 2, die um eine horizontale Achse 3 drehbar gelagert ist. Die Kathodenwalze ist auf ihrer dem Boden des Troges 1 zugeordneten Seite von einer halbkreisförmigen bzw. U-förmigen Anode 5 aus Streckmetall bzw. perforiertem Metall mit einer Aktivierungsschicht umgeben, die mit dem positiven Pol der Spannungsquelle 4 verbunden ist. Das Elektrolyt-Niveau ist mit Bezugsziffer 6 bezeichnet. Das um die Kathodenwalze laufende flexible Band 7 befindet sich mit seiner metallischen Oberfläche auf dem Potential der Kathodenwalze 2, d.h. es ist ebenfalls mit dem negativen Pol der Spannungsquelle 4 elektrisch verbunden. Das flexible Band 7 umfaßt die Kathodenwalze 2 zu etwa dem 0,6-fachen ihres Umfanges, wobei das Band 7 außerhalb der Elektrolyt-Lösung 8 über Umlenkrollen 9, 10, 11 durch die verschiedenen Arbeitsstationen, wie Trockenvorrichtung 12, Abstreifvorrichtung 13 und Abspülvorrichtung 14 geführt wird. Die Umlenkrolle 10 wird dabei von einem schematisch dargestellten Elektromotor 15 angetrieben. Die Achse der Umlenkrolle 11 ist durch eine Federung abgestützt, so daß das flexible Band 7 stets gespannt ist und transportiert wird. Zur Kontaktierung des flexiblen Bandes 7 ist zusätzlich die mit dem negativen Pol der Spannungsquelle 4 elektrisch verbundene Umlenkrolle 11 vorgesehen, welche gegen die Abscheidungsfläche des Bandes 7 gepreßt wird. Darüber hinaus ist es auch möglich, die Kathodenwalze 2 mit einem eigenen Antrieb zu versehen, wobei gegebenenfalls Elektromotor 15 wegfallen kann. Weiterhin ist es möglich, die Kathodenwalze 2 mit einer Kühlung zu versehen, um eine hohe Stromdichte auf dem die Kathode umlaufenden flexiblen Band 7 zu erzielen.According to the figure, the device according to the invention has a trough 1 containing the solution and made of electrolyte-resistant material, such as, for example, stainless steel or plastic. In the trough there is a cathode roller 2, which is electrically connected to the negative pole of a voltage source 4 and is rotatably mounted about a horizontal axis 3. On its side assigned to the bottom of the trough 1, the cathode roller is surrounded by a semicircular or U-shaped anode 5 made of expanded metal or perforated metal with an activation layer which is connected to the positive pole of the voltage source 4. The electrolyte level is designated by reference number 6. The metallic surface of the flexible belt 7 running around the cathode roller is at the potential of the cathode roller 2, ie it is also electrically connected to the negative pole of the voltage source 4. The flexible belt 7 comprises the cathode roller 2 to approximately 0.6 times its circumference, the belt 7 outside the electrolyte solution 8 via deflection rollers 9, 10, 11 through the various work stations, such as drying device 12, stripping device 13 and rinsing device 14 to be led. The deflection roller 10 is driven by a schematically illustrated electric motor 15. The axis of the deflection roller 11 is supported by a suspension, so that the flexible band 7 is always tensioned and transported. For contacting the flexible band 7, the deflection roller 11, which is electrically connected to the negative pole of the voltage source 4 and is pressed against the deposition surface of the band 7, is additionally provided. In addition, it is also possible to provide the cathode roller 2 with its own drive, with the electric motor 15 possibly being omitted. Furthermore, it is possible to provide the cathode roller 2 with cooling in order to achieve a high current density on the flexible belt 7 running around the cathode.

Das flexible Band 7 besteht aus Titan bzw. einer Titan-Basis-Legierung, wobei die Kathodenwalze 2 ebenfalls aus Titan bzw. Titan-Basis-Legierung besteht. Es ist jedoch auch möglich, anstelle eines Titanbandes ein elektrisch leitendes Kunststoffband bzw. ein anderes Metallband einzusetzen, welches eine Beschichtung aus Titan oder einem anderen Ventilmetall, wie beispielsweise Tantal, aufweist. Die Anode besteht ebenfalls aus Ventilmetall, wie z.B. Titan oder Tantal. Weiterhin ist es auch möglich, eine Anode aus massivem Metall einzusetzen.The flexible band 7 is made of titanium or a titanium-based alloy, the cathode roller 2 also consisting of titanium or titanium-based alloy. However, it is also possible to use an electrically conductive plastic band or another metal band instead of a titanium band, which has a coating of titanium or another valve metal, such as tantalum. The anode is also made of valve metal, such as Titanium or tantalum. It is also possible to use a solid metal anode.

Die Trockenvorrichtung 12 besteht aus einer Elektrowärmebestrahlungsvorrichtung mit Glühwendeln 16, welche beispielsweise durch Infrarotbestrahlung das auf der Bandoberfläche abgeschiedene Metall, welches gegebenenfalls flüssige Elektrolytpartikel enthält, soweit trocknet, daß es der mechanisch arbeitenden Abstreifvorrichtung 13 zugeführt werden kann. Die Abstreifvorrichtung 13 weist um horizontale Achsen rotierende Bürsten 17 auf, unterhalb derer sich eine Sammelvorrichtung 18 befindet. Die Achsen der rotierenden Bürsten 17 sind dabei in einem Winkel zwischen 30 und 60° zur Bandlaufrichtung angeordnet, um das abgestreifte Material vom Band zu entfernen. Das Material wird der unterhalb der Abstreifvorrichtung 13 befindlichen trichterförmigen Sammelvorrichtung 18 durch freien Fall zugeführt. Unterhalb der Sammelvorrichtung ist eine Abtrennvorrichtung 19 angeordnet. An die Abstreifvorrichtung 13 schließt sich die Abspülvorrichtung 14 an, welche zusätzlich mit rotierenden Kratzbürsten 20 versehen ist. Die Abspülung wird gegebenenfalls durch ein gasförmiges oder flüssiges Medium verstärkt, welches über Düsen zugeführt wird.The drying device 12 consists of an electric heat radiation device with incandescent filaments 16, which dries, for example by infrared radiation, the metal deposited on the strip surface, which may contain liquid electrolyte particles, to the extent that it can be fed to the mechanically operating stripping device 13. The stripping device 13 has brushes 17 rotating about horizontal axes, below which there is a collecting device 18. The axes of the rotating brushes 17 are arranged at an angle between 30 and 60 ° to the tape running direction in order to remove the stripped material from the tape. The material is fed to the funnel-shaped collecting device 18 located below the stripping device 13 by free fall. A separating device 19 is arranged below the collecting device. The rinsing device 14 adjoins the scraper device 13 and is additionally provided with rotating scratching brushes 20. The rinsing is optionally reinforced by a gaseous or liquid medium which is supplied via nozzles.

Die Zuführung der Metallionen enthaltenden Lösung erfolgt durch eine am Boden des Troges 1 befindliche Eingangsöffnung 21, während zur Abführung des abgereicherten Elektrolyten eine Ausgangsöffnung 22 in der Seitenwand des Troges 1 vorgesehen ist.The solution containing metal ions is supplied through an inlet opening 21 located at the bottom of the trough 1, while an outlet opening 22 is provided in the side wall of the trough 1 to discharge the depleted electrolyte.

Zwischen Anode 5 und Kathodenwalze 2 kann eine als Diaphragma oder Ionenaustauschermembran ausgebildete Trennvorrichtung 23 eingesetzt sein. Sie teilt den Elektrolytraum des Troges in einen der Kathodenwalze 2 zugekehrten Katholytraum 24 und einen auf der anderen Seite der Trennvorrichtung 23 befindlichen Anolytraum 25.A separating device 23 designed as a diaphragm or ion exchange membrane can be inserted between anode 5 and cathode roller 2. She shares the electrolyte space of the trough into a catholyte space 24 facing the cathode roller 2 and an anolyte space 25 located on the other side of the separating device 23.

Die Bandumlaufgeschwindigkeit beträgt ca. 0,84 m/min bei einer Stromdichte von 6500 A/m². Es ist möglich, eine Bandumlaufgeschwindigkeit im Bereich von 0,3 m/min bis 1,44 m/min vorzusehen, wobei eine größere Umlaufgeschwindigkeit durch eine größere Stromdichte kompensiert werden muß; als maximale Stromdichte sind 10.000 A/m2 vorgesehen.The belt circulation speed is approx. 0.84 m / min with a current density of 6500 A / m². It is possible to provide a belt circulation speed in the range from 0.3 m / min to 1.44 m / min, a higher circulation speed having to be compensated for by a larger current density; the maximum current density is 10,000 A / m 2 .

Vom Umfang der Kathodenwalze sind mindestens 50 % im Elektrolyten bzw. Katholyten eingetaucht, d.h. mindestens 50 % des Walzenumfanges befinden sich unterhalb des mit Ziffer 6 bezeichneten Elektrolytniveaus. Die Temperatur der Elektrolytlösung liegt dabei im Bereich von 20 bis 100°C.At least 50% of the circumference of the cathode roller is immersed in the electrolyte or catholyte, i.e. at least 50% of the circumference of the roller is below the electrolyte level designated with number 6. The temperature of the electrolyte solution is in the range from 20 to 100 ° C.

Die Temperatur in der Trockenvorrichtung 12 liegt dabei unterhalb der Grenztemperatur des Bandes, um eine Diffusion zwischen dem abgeschiedenen Metall und dem Band zu vermeiden.The temperature in the drying device 12 is below the limit temperature of the strip in order to avoid diffusion between the deposited metal and the strip.

Im oberen Bereich des Troges 1 befinden sich zusätzliche Öffnungen 26 zur Gasausbringung bzw. Gasabsaugung der im Verfahren sich entwickelnden Gase.In the upper area of the trough 1 there are additional openings 26 for the gas discharge or gas extraction of the gases developing in the process.

Im Betrieb wird das flexible Band 7 nach Verlassen der Abspülvorrichtung 14 über Umlenkrolle 11 der Kathodenwalze 2 zugeführt und in die Lösung 8 eingetaucht. Die Kontaktierung des flexiblen Bandes 7 erfolgt dabei über Kathodenwalze 2 und/oder Umlenkrolle 11 sowie gegebenenfalls Umlenkrollen 9 und 10. Während des Band-Umlaufes auf der Unterseite der Kathodenwalze 2 wird aus der Lösung Metall abgeschieden, welches nach Durchlaufen des Lösungsbades auf der anderen Seite der Kathodenwalze 2 das Elektrolyt-Bad wiederum verläßt; das aus dem abgeschiedenen Metall und flüssigen Elektrolytpartikeln bestehende Material 27 ist symbolisch durch Punkte angedeutet. Das flexible Band 7 wird anschließend zunächst der Trockenvorrichtung 12 zugeführt, in der das abge schiedene Material durch Wärmestrahlung mittels Glühwendel 16 soweit getrocknet wird, daß es der anschließenden Abstreifvorrichtung 13 zwecks mechanischer Abtrennung mittels umlaufender Bürsten und Schaber zugeführt werden kann. Das von den Bürsten und Schabern abgestreifte elektrolythaltige Metall verläßt das Band und wird durch freien Fall der trichterförmigen Sammelvorrichtung 18 zugeführt, wobei das Metall im wesentlichen ein Konglomerat aus Pulver und zusammenhängenden Abscheidungsbrocken darstellt; zur Verbesserung des Materialflusses kann die Sammelvorrichtung mit einem Vibrator versehen sein; das elektrolythaltige Metall wird anschließend in einer Abtrennvorrichtung 19 durch Pressen und Filtern von restlichen Elektrolytpartikeln getrennt, so daß eine Wiederauflösung des abgeschiedenen Metalls verhindert wird. Anschließend durchläuft das Band die Abspülvorrichtung 14, in welcher mittels umlaufender Kratzbürsten 20 das Band 7 von sämtlichen Abscheidungsprodukten gereinigt wird, so daß es erneut der Kathodenwalze 2 im Trog 1 zugeführt werden kann.In operation, the flexible band 7 is fed to the cathode roller 2 via deflection roller 11 after leaving the rinsing device 14 and is immersed in the solution 8. The flexible strip 7 is contacted via cathode roller 2 and / or deflection roller 11 and, if appropriate, deflection rollers 9 and 10. During the strip circulation on the underside of the cathode roller 2, metal is deposited from the solution, which after passing through the solution bath on the other side the cathode roller 2 again leaves the electrolyte bath; the material 27 consisting of the deposited metal and liquid electrolyte particles is symbolically indicated by dots. The flexible belt 7 is then first fed to the drying device 12, in which the abge Different material is dried by heat radiation using incandescent filament 16 to the extent that it can be fed to the subsequent stripping device 13 for the purpose of mechanical separation by means of rotating brushes and scrapers. The electrolyte-containing metal stripped from the brushes and scrapers leaves the belt and is fed by free fall to the funnel-shaped collecting device 18, the metal essentially being a conglomerate of powder and coherent lumps of deposit; to improve the material flow, the collecting device can be provided with a vibrator; the electrolyte-containing metal is then separated from the remaining electrolyte particles in a separating device 19 by pressing and filtering, so that a redissolution of the deposited metal is prevented. The belt then passes through the rinsing device 14, in which the belt 7 is cleaned of all separation products by means of revolving scratching brushes 20, so that it can again be fed to the cathode roller 2 in the trough 1.

Als Elektrolyt-Lösung wird beispielsweise eine Zinksulfat-Lösung dem Trog 1 zugeführt, während das abgeschiedene Metall im wesentlichen aus Zink besteht. Es ist selbstverständlich auch möglich, die erfindungsgemäße Vorrichtung zum elektrolytischen Austragen von anderen Metallen - beispielsweise Schwer-oder Edelmetallen - aus anderen Metallionen enthaltenden alkalischen oder sauren Lösungen einzusetzen.A zinc sulfate solution, for example, is fed to the trough 1 as the electrolyte solution, while the deposited metal essentially consists of zinc. It is of course also possible to use the device according to the invention for the electrolytic discharge of other metals - for example heavy or noble metals - from other alkaline or acidic solutions containing metal ions.

Claims (8)

Vorrichtung zum kontinuierlichen elektrolytischen Austragen von Metallen aus einer Metallionen enthaltenden Lösung mittels einer teilweise in die Lösung eintauchenden, durch die Lösung laufenden, als endloses flexibles Band ausgebildeten Kathodenfläche, wobei das abgeschiedene Metall außerhalb der Lösung von der Kathodenfläche entfernt wird, und mit einer innerhalb der Lösung befindlichen Anode, dadurch gekennzeichnet, daß das flexible Band wenigstens auf dem Teil seiner Oberfläche, auf dem sich Metall abscheidet, metallisch ausgebildet ist, daß außerhalb der Lösung (8), in Bandumlaufrichtung gesehen, nacheinander eine Abstreifvorrichtung (13) sowie eine Abspülvorrichtung (14) für das abgeschiedene Metall angeordnet sind und daß das Band mittels Umlenk- und/oder Antriebsrollen geführt ist.Apparatus for the continuous electrolytic removal of metals from a solution containing metal ions by means of a cathode surface which is partially immersed in the solution and which runs through the solution and is in the form of an endless flexible strip, the deposited metal being removed from the cathode surface outside the solution and with one inside the Anode located in solution, characterized in that the flexible strip is metallic at least on the part of its surface on which metal is deposited, and that outside the solution (8), viewed in the strip circulation direction, a stripping device (13) and a rinsing device ( 14) are arranged for the deposited metal and that the band is guided by means of deflection and / or drive rollers. Vorrichtung nach Anspruch 1, dadurch gekennzeichnet, daß zum Antrieb des Bandes (7) die Kathodenwalze (2) vorgesehen ist.Apparatus according to claim 1, characterized in that the cathode roller (2) is provided for driving the belt (7). Vorrichtung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß zum Antrieb des Bandes eine außerhalb der Lösung befindlichen Umlenkrolle vorgesehen ist.Apparatus according to claim 1 or 2, characterized in that a deflection roller located outside the solution is provided for driving the belt. Vorrichtung nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß in Bandumlaufrichtung gesehen, vor der Abstreifvorrichtung (13) eine Trockenvorrichtung (12) vorgesehen ist.Device according to one or more of claims 1 to 3, characterized in that a drying device (12) is provided in front of the stripping device (13) when viewed in the direction of the strip travel. Vorrichtung nach Anspruch 4, dadurch gekennzeichnet, daß die Trockenvorrichtung (12) Glühwendel (16) zur Abgabe von Wärmestrahlung aufweist.Apparatus according to claim 4, characterized in that the drying device (12) has an incandescent filament (16) for emitting thermal radiation. Vorrichtung nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Abstreifvorrichtung (13) rotierende Bürsten (17) enthält, deren Rotationsachsen parallel zur Ebene des die Abstreifvorrichtung durchlaufenden flexiblen Bandes (7) angeordnet sind.Device according to one or more of claims 1 to 5, characterized in that the stripping device (13) contains rotating brushes (17) whose axes of rotation are arranged parallel to the plane of the flexible belt (7) passing through the stripping device. Vorrichtung nach Anspruch 6, dadurch gekennzeichnet, daß unterhalb der Abstreifvorrichtung (13) eine Sammelvorrichtung (18) für das abgeschiedene elektrolythaltige Metall angeordnet ist, an die sich eine Abtrennvorrichtung (19) anschließt.Apparatus according to claim 6, characterized in that a collecting device (18) for the deposited electrolyte-containing metal is arranged below the stripping device (13), which is followed by a separating device (19). Vorrichtung nach einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß zur kathodischen Kontaktierung des Bandes (7) die Kathodenwalze (2) und/oder eine Umlenkrolle (11) vorgesehen sind.Device according to one or more of claims 1 to 7, characterized in that the cathode roller (2) and / or a deflection roller (11) are provided for the cathodic contacting of the strip (7).
EP90110925A 1989-11-29 1990-06-09 Electrode for the recovery of metals from a solution containing metal-ions Expired - Lifetime EP0429748B1 (en)

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EP0429748B1 (en) 1994-09-21
DE59007241D1 (en) 1994-10-27
ATE111974T1 (en) 1994-10-15
DE4035328A1 (en) 1991-06-06

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