EP0005007B1 - Elektrolytisches Verfahren und Vorrichtung zur Rückgewinnung von Metallwerten - Google Patents

Elektrolytisches Verfahren und Vorrichtung zur Rückgewinnung von Metallwerten 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
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Prior art keywords
cell
concentrate
anode
cathode
grid
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Expired
Application number
EP19790300379
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English (en)
French (fr)
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EP0005007A1 (de
Inventor
John Frederick Cannell
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Recyclamation Ltd
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Recyclamation Ltd
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Publication date
Application filed by Recyclamation Ltd filed Critical Recyclamation Ltd
Publication of EP0005007A1 publication Critical patent/EP0005007A1/de
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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)
  • Manufacture And Refinement Of Metals (AREA)
  • Electrolytic Production Of Metals (AREA)

Claims (9)

1. Verfahren zur elektrolytischen Gewinnung von Metallanteilen aus einem festen Konzentrat, wobei das Konzentrat in eine Elektrolysezelle, die einen wässrigen Elektrolyten enthält, eingebracht wird, so daß das Konzentrat in der Nähe einer oder jeder Anode gehalten und dessen Berührung mit einer oder jeder Kathode vermieden wird, und wobei die Zelle derart aktiviert wird, daß Elektrolyse stattfindet und an der oder jeder Anode Säure freigesetzt wird, die die Metallanteile unter Bildung von Kationen, die an der oder jeder Kathode entladen werden, löst, dadurch gekennzeichnet, daß das feste Konzentrat in Form grober Partikel bei Zugabe zu dem Elektrolyten bleibt, daß die unlöslichen Verunreinigungen im Konzentrat an der oder jeder Anode als feine Partikel freigesetzt werden, die durch Sieben von dem nicht umgesetzten Konzentrat getrennt werden und sich am Zellenboden ansammeln, und daß weiteres Konzentrat periodisch oder kontinuierlich der Zelle in Nachbarschaft der oder jeder Anode zugeführt wird, daß die festen Verunreinigungen periodisch oder kontinuierlich vom Zellenboden entfernt werden, und daß das bei der elektrolytischen Reaktion gebildete Wasser durch Verdampfen entfernt wird.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Konzentrat in der Zelle periodisch oder kontinuierlich aufgerührt wird.
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß das Aufrühren durch Einleitung von Druckluft in die Zelle erfolgt.
4. Elektrolysezelle zur Gewinnung von Metallanteilen aus einem festen Konzentrat, wobei die Metallanteile auf mind. einer Kathode abgeschieden werden, und die unlöslichen Verunreinigungen in dem Konzentrat unlösliche feine Partikel bilden, und die ein Netz oder Gitter zum Fernhalten des Konzentrats von der Kathode aufweist, dadurch gekennzeichnet, daß das Netz oder Gitter innerhalb der Zelle derart angeordnet ist, daß die unlöslichen Verunreinigungen und das nicht umgesetzte Konzentrat mit diesem in Kontakt stehen, wobei das Netz oder Gitter Öffnungen aufweist, die zu klein sind, um den Durchtritt von nicht umgesetzten Konzentrat zu gestatten, die jedoch so groß sind, daß die Verunreingungen durchtreten und sich am Zellenboden ansammeln können, und daß Mittel vorgesehen sind, die angesammelten unlöslichen Verunreinigungen vom Zellenboden abzuziehen.
5. Elektrolysezelle nach Anspruch 4, dadurch gekennzeichnet, daß das oder jedes Netz oder Gitter eine Anode bildet und aus einem leitenden Material besteht, das unter den Elektrolysebedingungen korrosionsbeständig ist.
6. Elektrolysezelle nach Anspruch 4, dadurch gekennzeichnet, daß das oder jedes Gitter oder Netz zwischen zumindest einer Anode and mindestens einer Kathode angeordnet ist.
7. Elektrolysezelle nach mindestens einem der Ansprüche 4 bis 6, dadurch gekennzeichnet, daß sie auf den Zellenboden hin sich verjüngt.
8. Elektrolysezelle nach mindestens einem der Ansprüche 4 bis 7, dadurch gekennzeichnet, daß sie im Bereich der Anode oder Anoden zum Aufrühren des Konzentrats Vorrichtungen zur Einleitung von Druckluft in die Zelle aufweist.
9. Elektrolysezelle nach Anspruch 4, dadurch gekennzeichnet, daß sie einen länglichen Zellenkörper aufweist, der sich in Richtung auf den Zellenboden hin verjüngt und desser Querschnitt dreieckig ist; daß sie eine Reihe zentral und vertikal angeordneter Kathoden innerhalb des Zellenkörpers und parallel zu dessen Längsachse, 2 Reihen vertikal angeordneter Anoden innerhalb des Zellenkörpers parallel zu und seitlich von den Kathoden aufweist, wobei jede Kathodenreihe von den Anodenreihen durch ein verticales Netz oder Gitter, das sich von dem oberen Bereich der Zelle abwärts bis zu den sich verjüngenden Seitenwänden des Zellenkörpers in der Nähe des Zellenbodens erstreckt, getrennt ist, wobei die Netze oder Gitter die Zelle in eine zentral angeordnete Kathodenkammer und zwei seitliche Anodenkammern aufteilen; und wobei Einlässe in den Seitenwänden des Zellenkörpers zur Zuführung von Druckluft in die Anodenkammern vorgesehen sind.
EP19790300379 1978-03-15 1979-03-12 Elektrolytisches Verfahren und Vorrichtung zur Rückgewinnung von Metallwerten Expired EP0005007B1 (de)

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

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EP0005007B1 true EP0005007B1 (de) 1981-02-25

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* 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

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* 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

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