EP0127492B1 - Verfahren zur Behandlung einer Ablauflösung besonders bestimmt für die elektrolytische Gewinnung von Zink - Google Patents

Verfahren zur Behandlung einer Ablauflösung besonders bestimmt für die elektrolytische Gewinnung von Zink Download PDF

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Publication number
EP0127492B1
EP0127492B1 EP84400765A EP84400765A EP0127492B1 EP 0127492 B1 EP0127492 B1 EP 0127492B1 EP 84400765 A EP84400765 A EP 84400765A EP 84400765 A EP84400765 A EP 84400765A EP 0127492 B1 EP0127492 B1 EP 0127492B1
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EP
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Prior art keywords
zinc
solution
catholyte
fact
process according
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English (en)
French (fr)
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EP0127492A1 (de
Inventor
Michel Laveyne
Claude Palvadeau
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Preussag Weser Zink GmbH
Minemet Recherche SA
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Preussag Weser Zink GmbH
Minemet Recherche SA
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    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
    • D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
    • 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
    • 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
    • C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
    • 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

Definitions

  • the present invention relates to a process for treating a purge solution using an electro-extraction process of a recoverable metal such as zinc associated with a membrane electrolysis process.
  • This electrolytic treatment process the objective of which is to produce a solution, with a view to its rejection in order to form a purge, poor in zinc and sulfuric acid, will be called thereafter exhaustion by electro-electrodialysis.
  • the production of zinc by hydrometallurgical and electrolytic means involves a terminal operation of treatment by electrolysis of solutions obtained by sulfuric leaching of roasted sulphide ores.
  • Some of the mineral impurities go into solution during leaching and more or less completely escape the purification process which precedes electrolysis.
  • impurities that do not deposit on the electrodes tend to concentrate in the electrolyte.
  • concentration becomes too high the solubility of zinc sulphate decreases and they tend to disturb the course of the electrolytic process. It is therefore necessary to carry out a “purge of a fraction of the electrolyte. These purges cause significant losses of zinc and sulfuric acid and they also have the disadvantage of being very polluting.
  • the invention relates to a particular treatment of a solution taken at a particular stage of the extraction process with a view to its rejection.
  • FIG 1 is a block diagram illustrating an example among the conventional methods of zinc extraction by electrolytic means.
  • Reference 10 designates the roasted sulphide ores constituting the essential raw material. These ores undergo leaching 12 intended to dissolve the zinc as much as possible and to slow down, as far as possible, the dissolution of impurities.
  • leaching comprises three operations, an operation 12a of "neutral” leaching and an operation 12b of "acid” leaching and an operation 12c of precipitation of iron.
  • the solution obtained after acidic leaching and precipitation of iron is subjected to neutral leaching.
  • the solution 18 formed is a purified solution rich in zinc sulfate.
  • This is then subjected to electrolysis 20.
  • the solution undergoes several cascade electrolysis as indicated by the references 20a and 20b.
  • Zinc is deposited on the cathodes and the depleted solution 22 which has undergone electrolysis contains a large amount of sulfuric acid and it is reused for the leaching of ores 10. It is therefore noted that the treatment is carried out in a closed loop if although the impurities which do not disappear during the purification 16, during the electrolysis 20, or during the precipitation of the residues (12b, 12c) accumulate and can reach very high values.
  • iron can be insolubilized in the form of goethite, hematite or jarosite.
  • iron alkaline elements Na + , K + and NH 4 +
  • SO 42. sulphate ions
  • This mode of elimination can be more advantageous for the implementation of exhaustion by electro-electrodialysis.
  • the main impurity that which fixes the purging rate of the installation is generally magnesium, the zinc ores in their great majority containing magnesium.
  • the implementation of the electrolytic extraction of zinc begins to pose problems when the concentration of magnesium exceeds 15 to 20 grams per liter. The problem posed by magnesium is accentuated when the concentrates used as raw materials are of the dolomitic type.
  • manganese Another impurity whose accumulation is likely to cause some problems is manganese.
  • the presence of this element is necessary, but it must not also exceed a determined concentration.
  • Halogens, especially fluorine and chlorine can also accumulate in the electrolyte and become troublesome for the electrolysis of zinc sulfate.
  • magnesium which most often fixes the purge rate of a zinc extraction installation by electrolytic means, the invention is described with reference to the separation of magnesium. However, those skilled in the art will readily appreciate that it also applies to other impurities which may accumulate.
  • the purge can relate to part of the leach solution purified and rich in zinc sulfate.
  • the purge can also be carried out during electrolysis, between several treatment stages as indicated by the reference 28.
  • the purge relates to the solution of zinc sulphate depleted by electrolysis. It can be considered that this purging of the depleted solution is the most judicious since it is the solution which contains the least zinc, which constitutes the product of interest. However, this solution is very acid and requires the use of a large amount of neutralizing agents.
  • Neutralization-precipitation can sometimes be preceded by an electrolytic exhaustion of the solution.
  • the solution constituting the purge can be directly marketed.
  • the purified neutral solution of zinc sulphate can sometimes be used directly for the production of zinc salts or lithopone.
  • products obtained by simple evaporation of the solutions can sometimes be sold. However, these are relatively rare cases, given the small market for these products.
  • One of the aims of the present invention is to provide a purge treatment method integrated into the main scheme.
  • EED electro-electrodialysis
  • An American patent, US-A-4,030,989 proposes to carry out electrolysis in the presence of ion-exchange membranes in order to avoid the need for a neutralization step in the main circuit, in particular the electro-recovery circuit.
  • any purges are always carried out on the anolyte, that is to say on the most acidic part of the circuit.
  • the object of the invention is a method of extracting a recoverable metal, such as zinc, by electrolytic means applied, in the case of the electrolytic recovery of zinc, to part of the flow of the purified solution rich in zinc sulphate whose pH is advantageously between 2 and 5 and the zinc content advantageously between 100 and 150 grams per liter, part of the stream which constitutes the purge.
  • a recoverable metal such as zinc
  • Said aqueous solution rich in recoverable metal salt supplying the cathode compartment is depleted in recoverable metal, which deposits at the cathode and the acidity of the catholyte after electro-electrodialysis being less than 1 N, said catholyte depleted in recoverable metal salt being subjected to a neutralization treatment for rejection;
  • the anode compartment being supplied with a second solution whose concentration is less than 0.5 N, the acidity of the anolyte is regulated by the flow rate and the physico-chemical composition of said second solution to a value less than 1 N, said anolyte being recycled in said primary circuit.
  • Electro-electrodialysis is an electrolysis carried out in an electrolyser with several compartments separated by an anionic membrane, that is to say an anion exchange. This depletion can be done in a series of electrolysers or in several series connected in cascade.
  • the neutralization of the exhausted purge solution can be carried out by standard reagents such as lime, soda or sodium carbonate.
  • manganese can be subjected to a specific oxidation treatment in the form of manganese dioxide to selectively separate it from zinc and magnesium, the main metals contained in the purge solution.
  • the precipitation by neutralization is preferably staggered so as to be able to recover the elements of value included in the purge.
  • the purge solution can be taken from one or more different locations in the implementation of the method.
  • purge 24 may correspond to a sample of the raw leach solution which is rich in zinc sulfate.
  • the metal to be recovered is deposited.
  • reactions which one can qualify as parasites which can be, for example, the reduction of protons to form hydrogen which is released.
  • the anions in particular the sulfates, migrate from the catholyte to the anolyte, through the exchange membrane, however in principle, the cations do not cross the latter.
  • anion exchange membranes in particular have a lack of selectivity, in particular with respect to protons.
  • the selectivity of anion exchange membranes with respect to sulphate ions can be characterized by an apparent transport number of this ion in the membrane defined as follows: in which t so4 - is the intensity of the electric current transported by the sulphate ions in the membrane of I T the total electric current passing through the membrane.
  • One of the characteristics of the invention resides in making up for, at least partially, the deviation from the ideality of the membrane by regulating the acidity of the anolyte.
  • This regulation is in particular carried out by determining a suitable flow rate of the solution becoming the anolyte.
  • This flow rate should be such that the acidity at the outlet of the anode compartment is between 0.1 N and 1 N.
  • all the solutions substantially neutral can meet the constraints specified above. Mention may for example be made of the so-called purified neutral electrolyte solutions, the solutions resulting from the filtrations, the various washing waters before and after use. Mention may also be made of ferrous sulphate solutions which use a different anodic reaction, namely the oxidation of ferrous iron to ferric iron in place of the oxidation of water.
  • the acidity of the solution feeding the cathode compartment is less than 0.5 N.
  • the acidity in the cathode compartment should be maintained at a value greater than about 0.1 N.
  • the purge at the outlet of the cathode compartment be as low as acidic as possible. It is therefore necessary to achieve a compromise between the acidity constraints relating to the quality of the cathodic deposit and those relating to the acidity of the purge; a good compromise consists in choosing an acidity of the catholyte of between 0.1 N and 1 N, preferably around 0.6 N.
  • the zinc concentration of the purge is 10 to 40 grams per liter, in any case, in a first stage of electrolysis.
  • the feed rate of the cathode compartment is determined by the quantity of impurities to be purged. Given the constraints relating to the acidity of the catholyte, set out above, the flow rate of the anolyte feed can be determined. Experimentally, it has been verified that the flow ratio between the anolyte and the catholyte can vary from approximately 5 to 20. It has been observed that, on the one hand, there is a tendency to form concentration and concentration gradients. on the other hand a rise in temperature.
  • the recirculation of electrolytes - anolyte or catholyte - on atmospheric cooling towers, commonly used in zinc electrolysis plants is suitable for regulating the temperature of these solutions to values less than or equal to 40 ° C.
  • Temperature regulation can also be done exclusively on the catholyte. Under these conditions, the exhaustion by electro-electrodialysis of the zinc sulphate solutions takes place with a positive temperature gradient between the anolyte and the catholyte. This temperature difference, made possible by the use of a membrane, can reach 20 to 30 ° C, with a maximum temperature of the anolyte of 60 to 70 ° C and the catholyte of 40 ° C.
  • the treatment of catholyte depleted in zinc sulfate must, to comply with certain legislation in force and for economic reasons, include a stage of elimination and / or recovery of zinc.
  • This elimination and / or recovery can be carried out, for example, by selective precipitation using a base.
  • This base can be chosen, for example, from the group consisting of alkali hydroxides and carbonates.
  • the low acidity of the depleted catholyte allows a basic economy and makes it possible to envisage the use of ion-exchange compounds in the form of resin or in liquid form.
  • the zinciferous precipitate is separated from the stock solutions and can be recycled to the zinc extraction process, more precisely to the leaching operation. It is also advantageous for the overflow of the settling to undergo neutralization, by means of appropriate bases, so as to remove the impurities whose discharge is regulated. This precipitation can be done in two stages so as to separate, when the effluent contains it, the magnesium from the manganese. To do this, a person skilled in the art can use all the techniques already known, in particular that consisting in making precipitation which is both basic and oxidizing for manganese.
  • the depleted catholyte is subjected to the oxidation of a strong oxide such as ozone, persulfate, chlorine dioxide and a base which may be weak, to precipitate the manganese dioxide.
  • a strong oxide such as ozone, persulfate, chlorine dioxide and a base which may be weak
  • This manganese dioxide can be usefully recycled in the main circuit since the latter is a user of manganese dioxide.
  • the zinc can be precipitated at a controlled pH (around 11) according to techniques well known to those skilled in the art, giving a zinc hydroxide and / or a basic zinc sulphate. The precipitate can be used and recycled in the main circuit. It can also be used for the precipitation of manganese dioxide.
  • the solution thus freed from manganese and zinc is then neutralized to precipitate the magnesium.
  • lime When lime is used, the magnesia can be completely precipitated in two stages, the second stage being carried out by a stronger base than lime, for example sodium hydroxide.
  • the purge is carried out by separation of a part of the purified rich solution, and the method further comprises the treatment of this purge solution by the treatment method indicated above, the anolyte formed during this treatment. being directed to the zinc recovery process.
  • an advantageous embodiment of the invention provides a particular method for fixing a heterogeneous membrane with selective permeability, comprising a substrate and a coating. This process includes moistening the membrane, applying it against a seal forming a closed loop, drying the portion of membrane which is outside the seal defining the closed loop while the part placed inside remains moistened, the stripping of the membrane substrate in the dry part thereof, and the bonding of this dry part on a support.
  • Both homogeneous and heterogeneous membranes can also be fixed to a frame according to the technique known to those skilled in the art of the filter press or by wedging the membrane between a frame provided with a groove and a closed elastic seal. forcefully entered the groove so as to wedge the membrane between the groove and the elastic seal.
  • the groove is preferably in the form of a dovetail.
  • the treatment according to the invention has many advantages. First, the losses of sulfuric acid are very low because the solution actually purged comes from the catholyte of the electrodialysis, and this catholyte is very depleted in sulfate ions since the membrane is of the anionic type.
  • the low acidity of the catholyte facilitates the recovery of residual zinc.
  • Zinc is recovered at the cathode in an extremely pure form.
  • the depleted catholyte 40 is then subjected to neutralization 44 with lime, at a pH of the order of 5.5.
  • Zinc precipitates as basic sulfate.
  • a decantation 48 allows the separation of the heavy products 50 containing the basic salt and a liquid effluent 52 which contains the manganese and the magnesium.
  • the liquid effluent 52 is then subjected to a new neutralization 54 with lime 56, at a pH of the order of 9 to 12.
  • the treatment of the materials formed 58 allows the separation of solid materials 60 containing manganese hydroxides and magnesium and calcium sulphate, and a liquid effluent 62, which can be recycled upstream of the leaching of roasted sulphide ores, or simply rejected after a readjustment of the pH to 8.
  • the heavy zinciferous products 50 are recycled to the leaching operation 12, while the anolyte 42 is returned to the electrolysis operation, the only products extracted are on the one hand zinc 38 and on the other hand the solids 60 and in some cases liquid effluent 62.
  • the electrolysis cell of FIG. 3 has compartments 32 and 34 of catholyte and anolyte respectively, separated by the anionic membrane 36.
  • the cell comprises a cell 62 which contains a cathode 64 and an anode 66.
  • the cathode 64 is advantageously formed of aluminum, and anode 66 of lead or lead-silver alloy.
  • the excess catholyte corresponding to the quantity of purified solution 26 introduced into the circulation loop, passes through a weir 68 into a receptacle 70 before being discharged as indicated by the reference 72, in the form of the depleted catholyte.
  • the catholyte circulates in the cell. It is taken at 74, at the bottom of the cell, and a pump 76 circulates it in a heat exchanger 78 which maintains it for example at 40 ° C., taking account of any indirect losses, and in an apparatus 80 for measuring the pH.
  • the excess overflows through a weir 82 and reaches a decanter 84 in which Mn0 2 which may have precipitated can be separated as indicated by the reference 86.
  • the liquid effluent constitutes the enriched solution 42 transmitted to electrolysis.
  • the anolyte also circulates advantageously and it is removed by an outlet 88 formed at the bottom of the tank, by a pump 90 which circulates it in a heat exchanger 92 which maintains it between 40 ° C and 70 ° C then in an apparatus 94 for pH measurement.
  • the distance separating the cathode from the membrane is 40 millimeters, and the distance separating the anode from the membrane is 20 millimeters.
  • the anolyte is preferably introduced transversely to the electrodes while the catholyte is transmitted from above.
  • the permeability of the membranes is almost zero so that the catholyte can have a level higher than that of the anolyte; in this way, the catholyte whose density is lower than that of the anolyte, can overflow while the differential hydrostatic pressures applied to the membrane balance.
  • the purified solution that is used for purging generally has a high concentration of zinc, which is often around 150 grams per liter. Magnesium is present at the rate of approximately 15 grams per liter and manganese at the rate of approximately 7.5 grams per liter. Its pH is greater than 1.5, of the order of 5.
  • the acidified anolyte if it comes from the purified neutral solution, also contains about 150 grams per liter of zinc, but the catholyte contains only 5 to 40 grams per liter. In fact, this low concentration is due to the deposit of zinc on the cathode.
  • the quantity of solution introduced is adjusted so that the zinc concentration remains within this range during the treatment.
  • the acid is present in the electrolyte at a rate of 0.1 to 0.6 N.
  • the current density is of the order of 200 to 800 amperes per square meter, preferably 400 amperes per square meter.
  • this acidity of the catholyte is at least 0.6 N because, when it is less than 0.3 N, the zinc deposits which form can be brittle and dendritic. Likewise, it is desirable that the current density and the temperature of the catholyte do not exceed the values of 800 amperes per square meter and approximately 50 ° C. respectively when the zinc deposits formed must be smooth and not very brittle.
  • the faradic yield of the reaction is most often between 0.75 and 0.98, and it is preferable that the concentration of zinc is at the top of the indicated range, that is to say near 40 grams per liter, because the faradaic yield is then in the upper part of the indicated range, at 0.95 and even more.
  • the anion exchange membranes sold on the market are suitable for implementing the process, but the use of the heterogeneous membrane sold under the registered trademark IONAC A3475 from IONAC CHEMICAL COMPANY is preferable. Indeed, this membrane lends itself very well to fixing by gluing on a frame, advantageously formed of plastic.
  • This mounting method according to the invention firstly includes humidification of the entire membrane, then, while it is still wet, its application between a seal forming a closed loop. The part of the membrane outside the joint delimiting the closed loop is then dried, the part placed inside the joint being kept wet. As soon as the external part is dry, it is stripped at the periphery of its active coating to reveal the support, woven, generally made of polypropylene or polyvinyl chloride, which is glued to the plastic frame.
  • the treatment according to the invention then comprises the neutralization of the depleted catholyte formed by electro-electrodialysis.
  • This reaction carried out at a pH of the order of 5.5, causes the precipitation of zinc according to the reactions:
  • Decantation allows the separation of basic zinc sulphate and gypsum which are returned to the leaching operation. The gypsum is then removed with the leach residue.
  • This effluent lends itself well to recycling at the iron precipitation stage in processes using the jarosite route as an iron outlet.
  • the composition of the electrolytes is mainly fixed by that of the purified neutral solution, by its feed rate (Da) in the anode compartment of the electrolyser and by the ratio between the latter and the rate neutral solution introduced into the cathode compartment (Dc).
  • FIG. 4 The block diagram of this particular arrangement is shown in FIG. 4.
  • the anode compartments 34 of the different electrolysers are supplied as well as the cathode compartments of cells of the first series with purified neutral solution 26.
  • the depleted catholyte 95 leaving the cells of this series supplies the cathode circuit 32 of the second series of electrolysers.
  • the advantage of such an organization of the electrolysis cells lies in the possibility of exhausting the purge solutions in zinc sulfate as well as possible while minimizing the consumption of electrical energy necessary for the treatment.
  • the anolytes 98 and 97 extracted from each series of cells are sent to the electrolysis of the main process.
  • the test workshop was composed of three cells with for each cell a cathode of 0.275 m 2 of active surface, a cathode diaphragm box and two Pb / Ag anodes.
  • the production of zinc cathode per cell was 3.1 kilograms per day.
  • the intensity was 110 amps per hour.
  • the temperature was 38 ° C. in the cathode and anode compartments.
  • the output rate of the catholyte was 0.98 liters per hour.
  • the faradaic efficiency was 98%, the voltage across the cell 6.25 volts.
  • the zinc deposits were compact and easy to detach from the support cathode.
  • the lead content in the zinc was less than 10 grams per tonne.
  • Example 3 The same workshop as cited in Example 3 was used to work with higher temperatures in the anode compartment of the cell.
  • the temperature in the cathode compartment was 42 ° C.
  • the temperature in the anode compartment was 62 ° C.
  • the output rate of the catholyte was 0.94 liters per hour.
  • the faradaic efficiency was 98%, the voltage across the cell 5.2 volts.
  • the zinc deposits were compact and easy to detach from the support cathode.
  • the lead content in the zinc was less than 10 grams per tonne.
  • Example 4 The same workshop as cited in Example 4 was used to work with feeding the anode compartment with water instead of purified zinc sulphate solution.
  • the temperature in the cathode compartment was 42 ° C.
  • the temperature in the anode compartment was 62 ° C.
  • the output rate of the catholyte was 0.9 liters per hour.
  • the faradaic efficiency was 95%, the voltage across the cell 3.8 volts.
  • the zinc deposits were compact and easy to detach from the support method.
  • the lead content in the zinc was less than 10 grams per tonne.

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Claims (15)

1. Verfahren zur Behandlung durch Elektro-Elektrodialyse einer wäßrigen, an verwertbarem Metallsalz reichen Lösung, die eine Ablaßlösung eines ersten Extraktionskreislaufes des verwertbaren Metalls darstellt, in dem die Anoden- und Kathodenräume der Elektro-Elektrodialysezelle getrennt versorgt werden, die wäßrige, an verwertbarem Metallsalz reiche, den Kathodenraum versorgende Lösung an verwertbarem Metall erschöpft wird, wobei sich das Metall an der Kathode niederschlägt, der Säuregrad des Katholyten nach Elektro-Elektrodialyse unter 1 n beträgt und der an verwertbarem Metallsalz verarmte Katholyt zur Entsorgung neutralisiert wird, der Anodenraum mit eineir zweiten Lösung mit einer Konzentration unter 0,5 n versorgt wird, der Saüregrad des Anolyten durch den Durchsatz und die physico-chemische Zusammensetzung dieser zweiten Lösung auf einen Wert unter 1 n eingestellt und der Anolyt in den ersten Kreislauf zurückgeführt wird.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß außerdem die Temperatur des Katholyten eingestellt wird.
3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß außerdem die Temperatur des Anolyten eingestellt wird.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß außerdem der Anolyt in das Extraktionsverfahren des verwertbaren Metalls zurückgeführt wird.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das verwertbare Metall Zink ist und die wäßrige Lösung des verwertbaren Metallsalzes eine gereinigte neutrale Zinksulfatlösung mit einem pH-Wert über 1,5 ist.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die gereinigte neutrale Lösung in einer Kaskade von Elektrolysern erschöpft wird.
7. Verfahren nach Anspruch 5 oder 6, dadurch gekennzeichnet, daß die Behandlung des an Zinksulfat verarmten Katholyten durch
- Neutralisation mit einer Base und Abtrennung eines basischen Zinksalzes und eines Abflusses und
- Zurückführung eines Zinkhydroxids oder eines basischen Zinksulfats in das Extraktionsverfahren durchgeführt wird.
8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß außerdem der Abfluß aus der vorhergehenden Neutralisation auf einen pH-Wert im Bereich von 11 neutralisiert wird und die Magnesium und Mangan enthaltenden Niederschläge abgetrennt werden.
9. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß außerdem
- Mangan nach Oxidation in Mangandioxid selektiv ausgefällt wird,
- das Mangandioxid abgetrennt wird,
- der Abfluß nach der Abtrennung des Mangandioxids auf einen pH-Wert von 11 neutralisiert wird, um daraus mit Soda Magnesium zu entfernen,
- der Natriumsulfat enthaltende Abfluß nach Abtrennung des Magnesiumhydroxids in die Ausfällungsstufe des Eisens zurückgeführt wird bei Verfahren, in denen das Eisen in Form von Jarosit entfernt wird.
10. Verfahren nach einem der Ansprüche 5 bis 9, dadurch gekennzeichnet, daß der Katholyt mit einer Zinksulfatkonzentration unter 40 g/I Zink verwendet wird.
11. Verfahren nach einem der Ansprüche 5 bis 10, dadurch gekennzeichnet, daß der Anolyt und der Katholyt getrennt in geschlossenen Kreisläufen zirkuliert werden.
12. Verfahren nach einem der Ansprüche 5 bis 11, dadurch gekennzeichnet, daß außerdem in den Anolyten ein Teil des Elektrolyten eingeführt wird, der im Verlauf der Elektrolyse des Zinkextraktionsverfahrens entnommen wurde.
13. Verfahren zur Extraktion von Zink durch
- Auslaugen von gerösteten sulfidischen Erzen unter Bildung einer an Zinksulfat reichen Rohauslauglösung,
- Reinigung der Rohauslauglösung unter Bildung einer gereinigten angereicherten Lösung,
- Elektrolyse der gereinigten angereicherten Lösung unter Bildung von Zink, das sich an der Kathode niederschlägt, und einer an Zinksulfat verarmten Lösung,
- Zurückführen der an Zinksulfat verarmten Lösung in die Auslaugstufe und
- Ablassen eines Teils mindestens einer der Lösungen, damit die Konzentration der Verunreinigungen, wie Magnesium, die während der Reinigungs-, Elektrolyse- und Fällungsstufen praktisch nicht abgetrennt werden, einen vorbestimmten Wert nicht übersteigt, dadurch gekennzeichnet, daß das Ablassen das Abtrennen eines Teils der gereinigten angereicherten Lösung umfaßt und diese Ablaßlösung in einem Kathodenraum einer Elektro-Elektrodialyse-Zelle nach einem der Ansprüche 1 bis 8 behandelt wird und der während dieser Behandlung erhaltene Anolyt in das Zinkwiedergewinnungsverfahren zurückgeführt wird.
14. Verfahren nach Anspruch 13, dadurch gekennzeichnet, daß der Teil der gereinigten angereicherten Lösung zum Teil in den Anodenraum und zum Teil in den Kathodenraum eingeführt wird, wo er mit dem durch die Elektro-Elektrodialyse-Behandlung verarmten Katholyten vermischt wird.
15. Verfahren zur Behandlung einer wäßrigen, ein verwertbares Metallzalz enthaltenden Lösung nach einem der Ansprüche 1 bis 14, dadurch gekennzeichnet, daß eine Membran der Elektrolysezelle durch folgende aufeinanderfolgende Stufen befestigt wird :
- Aufeuchten der Membran,
- Anbringen der Membran an eine eine geschlossene Schleife bildende Dichtung,
Trocknen des Membranbereichs, der sich außerhalb der die geschlossene Schleife begrenzenden Dichtung befindet, während der sich im Inneren befindende Bereich angefeuchtet bleibt,
- Blankmachen des Substrats im trockenen Bereich der Membran und
- Ankleben des trockenen Bereichs auf einen Träger.
EP84400765A 1983-04-25 1984-04-18 Verfahren zur Behandlung einer Ablauflösung besonders bestimmt für die elektrolytische Gewinnung von Zink Expired EP0127492B1 (de)

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AT84400765T ATE36012T1 (de) 1983-04-25 1984-04-18 Verfahren zur behandlung einer ablaufloesung besonders bestimmt fuer die elektrolytische gewinnung von zink.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8306805A FR2544750B1 (fr) 1983-04-25 1983-04-25 Procede de traitement d'une solution de purge notamment destinee a un procede d'extraction de zinc par voie electrolytique
FR8306805 1983-04-25

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EP0127492B1 true EP0127492B1 (de) 1988-07-27

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SE451333B (sv) * 1985-12-20 1987-09-28 Norzink As Forfarande for hydrometallurgisk framstellning av zink
US6048458A (en) * 1995-12-01 2000-04-11 Eastern Power Limited Apparatus and method for waste recycling and conversion
US6485696B1 (en) * 1998-10-30 2002-11-26 The United States Of America As Represented By The Secretary Of The Interior Recovery/removal of metallic elements from waste water using ozone
ES2159263B1 (es) * 1999-12-17 2002-04-16 Tecn Reunidas S A Proceso para la produccion electrolitica de zinc o de compuestos de zinc de alta pureza a partir de materias primas primarias y secundarias de zinc.
US7820135B2 (en) * 2008-06-30 2010-10-26 Uop Llc Catalyst composition with nanometer crystallites for slurry hydrocracking
DOP2011000007A (es) * 2010-01-07 2017-10-15 Barrick Gold Corp Produccion de concetrados de sulfato de cinc de una solucion diluida de sulfato de cinc.
CN113113689A (zh) * 2021-03-05 2021-07-13 蚌埠睿德新能源科技有限公司 一种废旧铅酸蓄电池的酸液回收方法

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US3357823A (en) * 1964-05-08 1967-12-12 Treadwell Corp Recovery of gold, silver, copper and zinc by alkaline cyaniding with electrodialysis
GB1481663A (en) * 1975-01-09 1977-08-03 Parel S Electrowinning of metals
US4171250A (en) * 1975-10-29 1979-10-16 David B. Dean Method for zinc ore extraction
FR2346457A1 (fr) * 1976-04-02 1977-10-28 Elf Aquitaine Recuperation du zinc des solutions residuelles de l'electrodeposition
US4030989A (en) * 1976-05-11 1977-06-21 Anglonor S. A. Electrowinning process

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FI841551A0 (fi) 1984-04-18
ATE36012T1 (de) 1988-08-15
ES531886A0 (es) 1984-12-16
KR910005837B1 (ko) 1991-08-05
CA1236792A (fr) 1988-05-17
BR8401891A (pt) 1984-12-04
ES8502170A1 (es) 1984-12-16
FR2544750A1 (fr) 1984-10-26
NO841618L (no) 1984-10-26
FI76839C (fi) 1988-12-12
US4557908A (en) 1985-12-10
AU2667884A (en) 1985-10-31
AU576755B2 (en) 1988-09-08
ZA842847B (en) 1985-03-27
FR2544750B1 (fr) 1988-09-16
FI841551A (fi) 1984-10-26
EP0127492A1 (de) 1984-12-05
KR850000048A (ko) 1985-02-25
DE3472982D1 (en) 1988-09-01
FI76839B (fi) 1988-08-31

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