EP0005007B1 - 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
EP0005007B1
EP0005007B1 EP19790300379 EP79300379A EP0005007B1 EP 0005007 B1 EP0005007 B1 EP 0005007B1 EP 19790300379 EP19790300379 EP 19790300379 EP 79300379 A EP79300379 A EP 79300379A EP 0005007 B1 EP0005007 B1 EP 0005007B1
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EP
European Patent Office
Prior art keywords
cell
concentrate
anode
cathode
grid
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.)
Expired
Application number
EP19790300379
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German (de)
English (en)
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EP0005007A1 (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
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Recyclamation Ltd
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Filing date
Publication date
Application filed by Recyclamation Ltd filed Critical Recyclamation Ltd
Publication of EP0005007A1 publication Critical patent/EP0005007A1/fr
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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 produces other solid wastes such as cobalt and nickel-containing sludges from the machining and grinding of castings and the drawing of wire.
  • An electrolytic cell for the recovery of metals from sludges and suspension is described in British Patent Specification No. 1,476,048 (Kawasaki and Ebara-Udylite Co. Ltd.).
  • This cell contains anode and cathode compartments separated by a membrane such as a sheet of felt cloth.
  • the purpose of the felt cloth is to retain all solid matter within the anode compartment, but to allow passage of metal ions from the anode compartment into the cathode compartment.
  • the concentration of such impurities in the anode compartment must steadily rise until the anode compartment becomes choked and metal recovery comes to a halt. It is then necessary to discontinue the process to enable the anode compartment to be cleaned out.
  • a process for electrolytically recovering metal values from a solid concentrate wherein 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, characterised in that the solid concentrate remains in the form of coarse particles when added to the electrolyte, in that 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, and in that further concentrate is periodically or continuously added to the cell in the vicinity of the or each anode, the solid impurities are periodically or continuously removed from the cell bottom, and the water produced in the electrolytic reaction is removed by evaporation.
  • the concentrate can be in any coarse particulate form (e.g. in the form of lumps, aggregate, or a paste or sludge formed from coarse particles), 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.
  • coarse particulate form e.g. in the form of lumps, aggregate, or a paste or sludge formed from coarse particles
  • 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 derivatives (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 or hydroxide constitutes the finely-divided insoluble particles of impurity.
  • H + ions are produced which immediately react with solid Ni(OH) 2 resulting in the formation of N1 21 cations, which migrate towards, and are deposited on, the cathode.
  • Water is released at the anode.
  • the process is preferably carried out under such conditions (e.g. electrolyte temperature; heat input; swept air velocity across the surface of the electrolyte and rate of air agitation) that water evaporates from the electrolyte at substantially the same rate as it is introduced by addition of the concentrate.
  • electrolyte does not become increasingly dilute as the recovery process proceeds.
  • the temperature and heat input may be controlled by regulating the resistance of the cell by varying the anode to cathode distance or by installing immersion heaters or heat exchangers. As the acid (H + ions) released at the anode immediately react with further concentrate the acidity of the electrolyte does not rise and the concentration of ions of the metal to be recovered is maintained at a sufficiently high level.
  • the concentrate in the vicinity of the anode(s) is preferably agitated periodically or continuously, especially by the introduction of high pressure air, to ensure that the acid released comes into contact with fresh concentrate.
  • mechanical agitation, or agitation by pumped circulation of the electrolyte is also possible.
  • a continuous stream of low pressure air may be introduced at points throughout the body of electrolyte. This air also serves to improve the rate of water evaporation.
  • the current densities which may be employed may, for example, be within the range 1 to 10A/dm z and more preferably within the range 1 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 concentrate 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, and means for withdrawing accumulated insoluble impurities from the cell bottom.
  • the grid or grids may form the anode or anodes in which case they are formed from a conducting material not significantly eroded durhig 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 row 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 of 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 are provided in the bottom connecting to a sludge transfer pump 5 which in turn delivers 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 8 mm 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 compartments 11 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 11 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 1 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 cell is first partly filled with an electrolyte containing NiS0 4 , H 3 B0 3 and the pH adjusted to a value of 4.0.
  • Compartments 11 are half filled with nickel-containing concentrate in the form of nickel hydroxide filter cake and freshly etched nickel cathode starter plates are suspended from the central bus-bar.
  • the temperature of the electrolyte is increased to 25°C by means of the immersion heaters and electrolysis is started.
  • the concentrate which takes the form of a clay-like solid containing 7 to 1396 nickel by weight, is retained in compartments 11 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 through the apertures in the grids and settles out at the bottom of the cell for periodic removal by the transfer pump 5.

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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)
  • Manufacture And Refinement Of Metals (AREA)

Claims (9)

1. Procédé de récupération électrolytique de quantités métalliques utiles, dans un concentré solide, par introduction de ce concentré dans une cellule électrolytique contenant un électrolyte aqueux, de façon que ce concentré soit retenu au voisinage d'une ou de plusieurs anodes et maintenu hors de contact avec cette anode ou ces anodes, et par excitation de la cellule de manière à produire l'électrolyse et à libérer l'acide à l'anode ou aux anodes, cet acide dissolvant les quantités métalliques à récupérer pour former des cations libérés à une ou plusieurs cathodes, procédé caractérisé en ce que le concentré solide reste sous la forme de particules grossières lorsqu'il est ajouté à l'électrolyte, en ce que les impuretés insolubles du concentré sont libérés à l'anode, ou aux anodes, sous la forme de fines particules qu'on sépare, par des écrans, du concentré n'ayant pas réagi et qui s'accumulent au fond de la cellule, et en ce qu'on ajoute, périodiquement ou en permanence, du concentré supplémentaire dans la cellule au voisinage de l'anode ou de chaque anode, les impuretés solides étant évacuées périodiquement ou en permanence du fond de la cellule et l'eau produite par la réaction électrolytique étant évacuée par évaporation.
2. Procédé selon la revendication 1, caractérisé en ce que le concentré contenu dans la cellule est agité périodiquement ou en permanence.
3. Procédé selon la revendication 2, caractérisé en ce que l'agitation se fait par introduction d'air sous pression dans la cellule.
4. Cellule électrolytique destinée à récupérer des quantités métalliques utiles dans un concentré solide, de façon que ces quantités métalliques se déposent sur une cathode au moins et que les imperetés insolubles contenues dans le concentré forment de fines particules insolubles, la cellule comportant une grille destinée à isoler le concentré de la cathode, cellule caractérisée en ce que la grille est disposée à l'intérieur de la cellule de façon que les impuretés insolubles et le concentré n'ayant pas réagi viennent en contact avec elle, cette grille comportant des ouvertures trop petites pour permettre le passage due concentré n'ayant pas réagi, mais suffisamment grandes pour permettre le passage des impuretés, de façon que ces impuretés puissent s'accumuler dans le fond de la cellule, et des moyens permettant de retirer du fond de la cellule les impuretés insolubles qui s'y sont accumulées.
5. Cellule électrolytique selon la revendication 4, caractérisée en ce que la grille ou chacune des grilles forme une anode, et en ce que cette grille ou ces grilles sont réalisées dans un matériau conducteur résistant à la corrosion dans les conditions crées par l'électrolyse.
6. Cellule électrolytique selon la revendication 4, caractérisée en ce que la grille ou les grilles sont situées entre une anode au moins et une cathode au moins.
7. Cellule électrolytique selon l'une quelconque des revendications 4 à 6, caractérisée en ce que la cellule se rétrécit vers le fond.
8. Cellule électrolytique selon l'une quelconque des revendications 4 à 7, caractérisée en ce qu'elle comporte des moyens permettant d'injecter de l'air sous pression dans la cellule au voisinage de l'anode ou des anodes, pour agiter le concentré.
9. Cellule électrolytique selon la revendication 4, caractérisée en ce qu'elle comprend un corps de cellule allongé se rétrécissant vers le bas avec une section en forme de triangle, une rangée centrale de cathodes verticales placées à l'intérieur du corps parallèlement à l'axe longitudinal de celui-ci, deux rangées d'anodes verticales placées à l'intérieur du corps parallèlement à la rangée de cathodes, et disposées de part et d'autre de cette dernière, chaque rangée de cathodes étant séparée des rangées d'anodes par une grille verticale dirigée vers le bas à partir du haut de la cellule de manière à rencontrer les parois latérales convergentes du corps de cellule au voisinage du fond de cette cellule, ces grilles divisant la cellule en un compartiment de cathode central et deux compartments d'anode latéraux, des orifices d'entrée étant prévus dans les parois latérales du corps de cellule pour introduire de l'air comprimé dans les compartiments d'anode.
EP19790300379 1978-03-15 1979-03-12 Procédé électrolytique et appareillage pour la récupération de valeurs métalliques Expired EP0005007B1 (fr)

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GB1025978 1978-03-15
GB1025978 1978-03-15

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

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Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8609340D0 (en) * 1986-04-16 1986-05-21 Imperial College Metal recovery
FI107813B (fi) * 1999-06-17 2001-10-15 Outokumpu Oy Erotuselin altaan pohjaosan erottamiseksi muusta altaasta
RU2510669C2 (ru) * 2012-08-14 2014-04-10 Арье БАРБОЙ Способ извлечения благородных металлов из упорного сырья
RU2655413C9 (ru) * 2015-02-12 2018-07-24 БЕЛОЗЕРОВА Татьяна Алексеевна Способ переработки полиметаллического сырья (варианты) и устройство для его выщелачивания

Family Cites Families (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
JPS5168405A (en) * 1974-12-10 1976-06-14 Motoo Kawasaki Suratsujinadokara kinzokuo kaishusuru hoho
US4066520A (en) * 1976-09-01 1978-01-03 Envirotech Corporation Slurry electrowinning process

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DE2960168D1 (en) 1981-04-02
EP0005007A1 (fr) 1979-10-31

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