EP0429748A1 - Electrode pour la récupération de métaux à partir d'une solution contenant des ions métalliques - Google Patents

Electrode pour la récupération de métaux à partir d'une solution contenant des ions métalliques 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
Authority
EP
European Patent Office
Prior art keywords
solution
belt
cathode
metal
deposited
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP90110925A
Other languages
German (de)
English (en)
Other versions
EP0429748B1 (fr
Inventor
Harri Heinke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
De Nora Deutschland GmbH
Original Assignee
Heraeus Elektroden GmbH
Heraeus Elektrochemie GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Heraeus Elektroden GmbH, Heraeus Elektrochemie GmbH filed Critical Heraeus Elektroden GmbH
Publication of EP0429748A1 publication Critical patent/EP0429748A1/fr
Application granted granted Critical
Publication of EP0429748B1 publication Critical patent/EP0429748B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • C25C7/007—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells comprising at least a movable electrode
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
    • C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
    • 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
    • C25C7/06—Operating or servicing
    • C25C7/08—Separating 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.

Landscapes

  • 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)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
EP90110925A 1989-11-29 1990-06-09 Electrode pour la récupération de métaux à partir d'une solution contenant des ions métalliques Expired - Lifetime EP0429748B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3939433 1989-11-29
DE3939433 1989-11-29

Publications (2)

Publication Number Publication Date
EP0429748A1 true EP0429748A1 (fr) 1991-06-05
EP0429748B1 EP0429748B1 (fr) 1994-09-21

Family

ID=6394404

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90110925A Expired - Lifetime EP0429748B1 (fr) 1989-11-29 1990-06-09 Electrode pour la récupération de métaux à partir d'une solution contenant des ions métalliques

Country Status (3)

Country Link
EP (1) EP0429748B1 (fr)
AT (1) ATE111974T1 (fr)
DE (2) DE59007241D1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021093343A1 (fr) * 2019-11-15 2021-05-20 清华大学 Procédé de préparation de particules métalliques par dépôt électrochimique continu
US20220090281A1 (en) * 2019-01-14 2022-03-24 Zhejiang Haihong Holding Group Co., Ltd. Device and method for preparing high-purity titanium powder by continuous electrolysis

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4123196A1 (de) * 1991-07-12 1993-01-14 Heraeus Elektrochemie Elektrode fuer das austragen von metallen aus metallionen enthaltender loesung
DE4320566A1 (de) * 1993-06-22 1995-01-05 Daimler Benz Ag Vorrichtung und Verfahren zur elektrolytischen Abscheidung von im Auswaschwasser von Lackierkabinen vorhandenem Lack

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE513509A (fr) *
US2099873A (en) * 1934-06-14 1937-11-23 Martin M Sternfels Machine and process for producing flake metal by electrodeposition
CA1073851A (fr) * 1975-09-13 1980-03-18 Sachio Kamata Appareil a polir les plaques cathodiques
WO1990003456A1 (fr) * 1988-09-27 1990-04-05 Eastman Kodak Company Dispositif de recuperation de metal

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4647345A (en) * 1986-06-05 1987-03-03 Olin Corporation Metallurgical structure control of electrodeposits using ultrasonic agitation
DE3640020C1 (de) * 1986-11-24 1988-02-18 Heraeus Elektroden Elektrolysezelle zur elektrolytischen Abscheidung von Metallen

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE513509A (fr) *
US2099873A (en) * 1934-06-14 1937-11-23 Martin M Sternfels Machine and process for producing flake metal by electrodeposition
CA1073851A (fr) * 1975-09-13 1980-03-18 Sachio Kamata Appareil a polir les plaques cathodiques
WO1990003456A1 (fr) * 1988-09-27 1990-04-05 Eastman Kodak Company Dispositif de recuperation de metal

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Band 90, Nr. 14, 2. April 1979, Seite 543, Zusammenfassung Nr. 112125j, Columbus, Ohio, US; & PL-A-87 839 (AKADEMIA GORNICZO-HUTNICZA) 15-04-1977 *
CHEMICAL ABSTRACTS, Band 92, Nr. 13, Juni 1980, Seite 522, Zusammenfassung Nr. 223332k, Columbus, Ohio, US; & CA-A-1 073 851 (DOWA MINING CO., LTD etc.) 18-03-1980 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220090281A1 (en) * 2019-01-14 2022-03-24 Zhejiang Haihong Holding Group Co., Ltd. Device and method for preparing high-purity titanium powder by continuous electrolysis
US11821096B2 (en) * 2019-01-14 2023-11-21 Zhejiang Haihong Holding Group Co., Ltd. Device and method for preparing high-purity titanium powder by continuous electrolysis
WO2021093343A1 (fr) * 2019-11-15 2021-05-20 清华大学 Procédé de préparation de particules métalliques par dépôt électrochimique continu

Also Published As

Publication number Publication date
EP0429748B1 (fr) 1994-09-21
DE59007241D1 (de) 1994-10-27
ATE111974T1 (de) 1994-10-15
DE4035328A1 (de) 1991-06-06

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