EP0005007A1 - Procédé électrolytique et appareillage pour la récupération de valeurs métalliques - Google Patents

Procédé électrolytique et appareillage pour la récupération de valeurs métalliques Download PDF

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Publication number
EP0005007A1
EP0005007A1 EP79300379A EP79300379A EP0005007A1 EP 0005007 A1 EP0005007 A1 EP 0005007A1 EP 79300379 A EP79300379 A EP 79300379A EP 79300379 A EP79300379 A EP 79300379A EP 0005007 A1 EP0005007 A1 EP 0005007A1
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EP
European Patent Office
Prior art keywords
cell
concentrate
anode
cathode
metal values
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
EP79300379A
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German (de)
English (en)
Other versions
EP0005007B1 (fr
Inventor
John Frederick Cannell
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.)
Recyclamation Ltd
Original Assignee
Recyclamation Ltd
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 Recyclamation Ltd filed Critical Recyclamation Ltd
Publication of EP0005007A1 publication Critical patent/EP0005007A1/fr
Application granted granted Critical
Publication of EP0005007B1 publication Critical patent/EP0005007B1/fr
Expired legal-status Critical Current

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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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions

Definitions

  • the present invention relates to a process and also to an electrolytic cell for electrolytically recovering metal values from a solid concentrate.
  • the metal finishing industry produces liquid effluents containing nickel, cobalt, zinc, copper and iron cations which are conventionally precipitated as hydroxides or carbonates which are converted to low value filter cake which up to now has been discarded.
  • This filter cake typically contains, in the case of nickel effluent, 7 to 12% of nickel by weight, the remainder consisting mainly of ferric hydroxide, water and foreign bodies.
  • the metal treatment industry also produce other sol id wastes such as cobalt and nickel-containing sludges from the machining and grinding of castings and the drawing of wire.
  • a process for electrolytically recovering metal values from a solid concentrate characterised in that the concentrate is introduced into an electrolytic cell containing an aqueous electrolyte so that the concentrate is retained in proximity to the or each anode and kept out of contact with the or each cathode, and energising the cell so that electrolysis takes place and acid is released at the or each anode, which acid dissolves the said metal values to form cations which are discharged at the or each cathode, and insoluble impurities in the concentrate are released at the or each anode as fine particles which are separated by screening from the unreacted concentrate and accumulate in the bottom of the cell.
  • the concentrate can be in any form (e.g. course particulate, lump, aggregate, paste or sludge), provided that it can be separated from the insoluble impurities by screening. If the concentrate is not already in a suitable form it can be converted to pellets or briquettes before being subjected to the process.
  • any form e.g. course particulate, lump, aggregate, paste or sludge
  • the metal to be recovered must be a metal which will electroplate from solution and must be such that plating conditions in the cell can be maintained by dissolving metal from a solid concentrate maintained in the vicinity of the anode(s) below solution level, e.g. by gravity or by an indexing pusher mechanism.
  • suitable metals are Ni, Cu, Co, Sn and Zn.
  • electrolytes examples include sulphuric, hydrochloric and sulphamic acids; solutions of ammonia and its salts and derivitives (e.g. ammines and amines).
  • the electrolysis is preferably started by utilising an electrolyte containing cations of the metal to be recovered. It is not normally necessary to add further electrolyte solution.
  • the insoluble impurities released at the anode(s) are separated from the concentrate by screening through a grid, mesh or woven fabric, dependant on particle size, and suspended between the anode(s) and cathode(s).
  • a grid, mesh or woven fabric dependant on particle size, and suspended between the anode(s) and cathode(s).
  • the or each anode itself may be in the form of a grid, mesh or woven fabric.
  • the size of the apertures in the grid is so chosen that the concentrate is retained until it has been almost totally reacted but so that the resulting fine particles of insoluble impurity can pass through without clogging.
  • the concentrate is the above mentioned-nickel hydroxide from the nickel plating industry, in the form of a filter cake.
  • the nickel values are recovered by the process of the invention and ferric oxide constitutes the finely-divided insoluble particles of impurity.
  • the current densities which may be.employed may, for example, be within the range I to IOA/dm 2 and more preferably within the range I to 5A/dm 2 in order to build up a massive cathode deposit with minimal internal stress.
  • 3A/dm 2 of cathode has been found to be suitable for plating nickel from a sulphate solution.
  • an electrolytic cell for recovering metal values from a solid concentrate so that the metal values are deposited on the or each cathode and insoluble impurities in the concentrate form fine particles, characterised in that the cell incorporates at least one grid having apertures too small to allow passage of the cmcentrate for isolating the concentrate from the or each cathode, but large enough to permit passage of the impurities so that they may accumulate in the bottom of the cell.
  • the grid or grids may form the anode or anodes in which case they are formed from a conducting material not significantly eroded during the electrolytic process, e.g. platinum-plated titanium, lead or graphite.
  • a separate grid is used.
  • This may be of any suitable insoluble material such as perforated polypropylene sheet, woven polypropylene filter cloth, "Terylene” or other polyester net or plastics coated metal mesh.
  • the anodes are preferably conventional "insoluble anodes", e.g. of platinum-coated titanium, lead or graphite depending upon the nature of the electrolyte.
  • the grid or grids divide the interior of the cell into one or more anode and cathode compartments.
  • Provision for periodically or continuously agitating the concentrate mass by means of injection of pressurised air is preferably provided, and also means for ensuring continuous electrolyte circulation within the anode and cathode compartments, e.g. inlets for low pressure air or mechanical stirrers.
  • a pH probe located in an external circulating loop, may be arranged to actuate a high pressure air blower for agitating the concentrate when the pH falls below a pre-set value. Alternatively, such a blower may be actuated on a time basis by a cam controller.
  • the pH of the electrolyte is preferably regulated to maintain an optimum value in the anode compartments, e.g. within the range of 0 to 10, and 1.0 to 10 in the cathode.compartment , depending on the metal to be recovered and the electrolyte used.
  • the cell is preferably tapering, e.g. triangular in cross-section, and may for example be constructed from ebonite-lined mild steel plate. It may have two lateral rows of anodes with a central low of cathodes, each row of anodes being separated from the cathodes by a substantially vertical grid. Thus, it has a central cathode compartment and two lateral anode compartments.
  • the cell In use the cell is initially filled with electrolyte and a quantity pf concentrate placed in each of the two anode compartments so that it contacts the anodes and is retained by the grids. Electrolysis is started and hydrogen ions are released which cause the metal values to dissolve and the resulting cations then migrate to the cathodes.
  • the starting electrolyte contains cations of the metal to be deposited. If not, no deposition of the metal to be recovered takes place until the concentration of those metal cations in the electrolyte has reached the minimum level for plating.
  • the fine impurities released in the anode compartments pass through the grid or grids and sink to the bottom of the cell for removal, e. g. by a sludge pump which may deliver to a settlement cone, from which the supernatant . electrolyte is returned by gravity to the cell in the vicinity of the anode or anodes.
  • This cell comprises an elongated hollow tapering cell body 1 which serves as a container for the electrolyte having two lateral sides 2 which converge towards the bottom 3.
  • Two outlets 4 are provided in the bottom connecting to a sludge transfer pump 5 which in turn del ivers to a settlement cone 6 of known type.
  • the container Above the container are supported three spaced and parallel bus bars which are connected to a rectified source of electrical energy 7 in such a way that the central bar is negatively charged and the lateral bus bars are each positively charged.
  • a vertical grid 10 constructed from 10 mm thick injection moulded perforated polypropylene panels.
  • the perforations are square in section and taper from 4 mm diagonal on the anode side to 8mm diagonal on the cathode side.
  • the grids extend vertically to meet the sides of the container near the bottom and the grids divide the container into two lateral anode comparments II and one central cathode compartment 12.
  • a high pressure air agitation manifold 13 supplied periodically by compressed air from a blower actuated by a cam controller (not shown).
  • Compartments II and 12 are also provided with low pressure air agitation pipes 16 for continuous electrolyte circulation. Provision is made for periodically dosing the central compartment with a flocculating agent by metering pump 17.
  • An extraction fan 18 causes air to be drawn across the surface of the electrolyte in container I to remove the water vapour generated by the hot electrolyte which is maintained at a temperature of 40 - 60°C by means of immersion heaters 19 and the heating effect of the current passing between anodes and cathodes. Before venting to atmosphere the extracted air passes through a fume scrubber 20.
  • the concentrate which takes the form of a clay-like solid containing 7 to 13% nickel by weight, is retained in compartments I by the vertical grids 10. Due to the converging configuration of the side walls 2 it is held, by gravity, in contact with anodes 8 thus becoming anodic itself and dissolving continually in the electrolyte, the nickel being deposited on the cathodes for subsequent recovery.
  • Fe(OH) 3 which is present as an impurity in the nickel concentrate, passes 3 through the apertures in the grids and settles out at the bottom of the cell for periodic removal by the transfer pump 5.

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)
  • Manufacture And Refinement Of Metals (AREA)
EP19790300379 1978-03-15 1979-03-12 Procédé électrolytique et appareillage pour la récupération de valeurs métalliques Expired EP0005007B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB1025978 1978-03-15
GB1025978 1978-03-15

Publications (2)

Publication Number Publication Date
EP0005007A1 true EP0005007A1 (fr) 1979-10-31
EP0005007B1 EP0005007B1 (fr) 1981-02-25

Family

ID=9964581

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19790300379 Expired EP0005007B1 (fr) 1978-03-15 1979-03-12 Procédé électrolytique et appareillage pour la récupération de valeurs métalliques

Country Status (2)

Country Link
EP (1) EP0005007B1 (fr)
DE (1) DE2960168D1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1987006274A1 (fr) * 1986-04-16 1987-10-22 Imperial College Of Science & Technology Recuperation de metal
WO2000079024A1 (fr) * 1999-06-17 2000-12-28 Outokumpu Oyj Element pour la separation d'un reservoir electrolytique
RU2510669C2 (ru) * 2012-08-14 2014-04-10 Арье БАРБОЙ Способ извлечения благородных металлов из упорного сырья
RU2655413C2 (ru) * 2015-02-12 2018-05-28 БЕЛОЗЕРОВА Татьяна Алексеевна Способ переработки полиметаллического сырья (варианты) и устройство для его выщелачивания

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3788965A (en) * 1972-04-07 1974-01-29 2C 2B Corp Hydrometallurgical solubilizer with selective electroplating mechanism
US3836443A (en) * 1970-06-04 1974-09-17 Gregor D Mac Electrowinning of ores
GB1476048A (en) * 1974-12-10 1977-06-10 Ebara Udylite Kk Electrolytic method of recovering metals
US4066520A (en) * 1976-09-01 1978-01-03 Envirotech Corporation Slurry electrowinning process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3836443A (en) * 1970-06-04 1974-09-17 Gregor D Mac Electrowinning of ores
US3788965A (en) * 1972-04-07 1974-01-29 2C 2B Corp Hydrometallurgical solubilizer with selective electroplating mechanism
GB1476048A (en) * 1974-12-10 1977-06-10 Ebara Udylite Kk Electrolytic method of recovering metals
US4066520A (en) * 1976-09-01 1978-01-03 Envirotech Corporation Slurry electrowinning process

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1987006274A1 (fr) * 1986-04-16 1987-10-22 Imperial College Of Science & Technology Recuperation de metal
WO2000079024A1 (fr) * 1999-06-17 2000-12-28 Outokumpu Oyj Element pour la separation d'un reservoir electrolytique
RU2510669C2 (ru) * 2012-08-14 2014-04-10 Арье БАРБОЙ Способ извлечения благородных металлов из упорного сырья
RU2655413C2 (ru) * 2015-02-12 2018-05-28 БЕЛОЗЕРОВА Татьяна Алексеевна Способ переработки полиметаллического сырья (варианты) и устройство для его выщелачивания
RU2655413C9 (ru) * 2015-02-12 2018-07-24 БЕЛОЗЕРОВА Татьяна Алексеевна Способ переработки полиметаллического сырья (варианты) и устройство для его выщелачивания

Also Published As

Publication number Publication date
DE2960168D1 (en) 1981-04-02
EP0005007B1 (fr) 1981-02-25

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