EP2528704A1 - Procédé et dispositif pour produire une poudre métallique - Google Patents

Procédé et dispositif pour produire une poudre métallique

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Publication number
EP2528704A1
EP2528704A1 EP11736667A EP11736667A EP2528704A1 EP 2528704 A1 EP2528704 A1 EP 2528704A1 EP 11736667 A EP11736667 A EP 11736667A EP 11736667 A EP11736667 A EP 11736667A EP 2528704 A1 EP2528704 A1 EP 2528704A1
Authority
EP
European Patent Office
Prior art keywords
solution
metal
anolyte
electrolytic cell
yield
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
EP11736667A
Other languages
German (de)
English (en)
Other versions
EP2528704B1 (fr
EP2528704A4 (fr
Inventor
Ville Nieminen
Henri Virtanen
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.)
Outotec Finland Oy
Original Assignee
Outotec Oyj
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Filing date
Publication date
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Publication of EP2528704A1 publication Critical patent/EP2528704A1/fr
Publication of EP2528704A4 publication Critical patent/EP2528704A4/fr
Application granted granted Critical
Publication of EP2528704B1 publication Critical patent/EP2528704B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • 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
    • C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
    • C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals

Definitions

  • the invention relates to the production of finely divided metal powder.
  • the invention relates to a dissolution-precipitation method and arrangement for producing metal powder.
  • the end product in many metal manufacturing processes is a plate-like object in cathode form.
  • This kind of end product is obtained for example by means of pyrometallurgical production routes utilizing electrolysis.
  • a metal anode that is pyrometallurgically made of a concentrate is electrolytically refined to cathode copper, which can for example be cast into products with various different forms.
  • These types of methods can be used for producing copper, nickel or cobalt products, among others.
  • the metal received as the end product of the manufacturing process would be obtained in some other form than as a uniform solid object, such as a cathode plate.
  • a uniform solid object such as a cathode plate.
  • Particularly methods where the end product is obtained as pure metal powder would be extremely useful.
  • the patent publication US2005/0023151 introduces a method where copper powder is made by electrolytically precipitating copper from copper sulfate on a cathode.
  • the method makes use of a ferrous/ferric anode reaction, by which the energy consumption of the method is reduced.
  • Said publication also describes a through-flow arrangement where the precipitated copper powder is recovered from the electrodes by means of an electrolyte flowing through the electrodes.
  • a drawback with the method and arrangement illustrated in the publication US2005/0023151 is, among others, an unreliable recovery of copper from the cathodes, owing for example to the precipitation of copper in various different locations in the chamber containing electrodes, and to the attachment of copper on the cathode.
  • the object of the invention is to eliminate above mentioned drawbacks of the prior art and to set forth a new method and arrangement for manufacturing metal powder in a solution-precipitation method making use of electrolysis.
  • dissolved yield metal is mixed with a solution containing at least one intermediary metal for precipitating the dissolved yield metal into a yield metal powder.
  • a first part of an acid-containing starting solution is brought to the anode side of the electrolytic cell as an anolyte, to be in contact with the anode and the supply material containing yield metal, and a second part of the acid-containing starting solution, which also contains intermediary metal in addition to acid, is brought to the cathode side of the electrolytic cell, as a catholyte to be in contact with the cathode;
  • the yield metal is oxidized and dissolved in the anolyte by conducting electric current to the anode;
  • the intermediary metal contained in the second part of the starting solution is reduced on the cathode side; and anolyte solution and catholyte solution are brought into a precipitation chamber for mixing the oxidized yield metal dissolved in the first part of the starting solution and the second part of the starting solution
  • the arrangement according to the invention is an arrangement for producing metal powder by precipitating yield metal powder by mixing dissolved yield metal powder with a solution containing at least one intermediary metal.
  • the arrangement according to the invention comprises an electrolytic cell for dissolving the yield metal located on the anode side of the electrolytic cell and for oxidizing it in the anolyte, and for reducing, on the cathode side, the dissolved intermediary metal located on the cathode side of the electrolytic cell; a precipitation chamber arranged essentially separately from the electrolytic cell; as well as means for feeding anolyte solution and cathode solution respectively from the anode side and the cathode side of the electrolytic cell to the precipitation chamber for mixing the oxidized yield metal that is dissolved in the anolyte, and the cathode solution containing reduced intermediary metal, outside the electrolytic cell.
  • a correct mixing ratio With a correct mixing ratio and an effective precipitate recovery, the creation of yield metal agglomerates can be prevented in the precipitation step, and consequently the homogeneity of the yield metal particles contained in the powder is enabled with respect to their size.
  • a correct mixing ratio also facilitates a process with a better efficiency, which can be utilized for reducing the amount of energy needed in the process for producing a certain quantity of yield metal mass.
  • anode side and cathode side refer to those parts of the electrolytic cell that contain anolyte or catholyte in the vicinity of the anode or cathode, respectively.
  • the “anode side” or the “cathode side” need not be a uniform part of the electrolytic cell, but the “anode side” or the “cathode side” may consist of several mutually separate elements comprising an anode or a cathode and anolyte or catholyte, respectively.
  • the expression “diaphragm” refers to any suitable film or thin mechanical obstacle, such as a membrane, an industrial textile or the like.
  • the expression “oxidation state”, “oxidation level” or a corresponding expression refers to a charge level where an atom appears alone or apparently in a molecule. Thus the expressions “oxidation state”, “oxidation level” or a corresponding expression can also refer to the apparent charge of an atom.
  • the first part of the starting solution contains intermediary metal for boosting the dissolution of yield metal on the anode side.
  • the first part of the circulating solution created as a result of mixing the anolyte solution and the catholyte solution is returned to anolyte.
  • the first part of the starting solution is composed of the first part of the circulating solution.
  • the second part of the circulating solution created as a result of mixing the anolyte solution and the catholyte solution is returned to catholyte.
  • the second part of the starting solution is composed of the second part of the circulating solution.
  • the circulating solution is returned essentially completely back to electrolyte, in which case the circulating solution is essentially composed of the first part of the circulating solution and of the second part of the circulating solution.
  • the circulating solution is essentially composed of the first part of the circulating solution and of the second part of the circulating solution.
  • the obtained circulating solution is recirculated in an arrangement to be used in the process in one of the embodiments of the invention, so that the circulating solution is partly or completely, after the mixing step and after the yield metal precipitate is separated from the solution, returned back to anolyte and/or catholyte. Now the intermediary metal is again reduced in the catholyte.
  • an electrolytic regeneration of the intermediary metal in the catholyte which means that in some embodiments of the invention, it is essentially not necessary to feed in the process new solution containing intermediary metal.
  • the anolyte in some embodiments of the invention contains intermediary metal
  • said intermediary metal intensifies the dissolution of the yield metal in such process conditions, for example with relatively low acid contents, where dissolution with the combined effect of electric current and acid solution would not be efficient.
  • the anolyte and the catholyte are mechanically separated by an electroconductive diaphragm.
  • the electrolytic cell comprises an electroconductive diaphragm provided in between the anode side and the cathode side of the electrolytic cell for mechanically separating the anode side and the cathode side.
  • an electroconductive separator solution is conducted in between the two diaphragms separating the anolyte and the catholyte in order to prevent a premature mixing of the anolyte and the catholyte.
  • the electrolytic cell comprises two electroconductive diaphragms provided in between the anode side and the cathode side of the electrolytic cell for mechanically separating the anode side and the cathode side by means of an electroconductive separator solution placed in the space between the two diaphragms.
  • the anolyte and the catholyte can in an embodiment of the invention be separated by means of an electroconductive diaphragm.
  • electroconductive diaphragm refers to a diaphragm that is electroconductive to such extent that the diaphragm facilitates an effective operation of the electrolytic cell.
  • the electroconductivity of the diaphragm may be lower than the electroconductivity of those solutions that are mechanically separated by the diaphragm.
  • the purpose of the diaphragm is to mechanically separate the solutions located on different sides of the diaphragm, i.e. to serve as a mechanical obstacle, while at the same time being electroconductive to that extent that the electrolytic cell is capable of functioning effectively.
  • This diaphragm divides the electrolytic cell to an anode part (or anode side) , where the anolyte is located, and to a cathode part (or cathode side) , where the catholyte is located.
  • the anolyte and the catholyte cannot be mixed together without disturbing the anode and cathode reactions, and metal powder cannot be formed in the vicinity of those electrodes in the electrolytic cell.
  • the yield metal is copper.
  • the yield metal is selected among the following group: nickel, cobalt, zinc, silver, gold, ruthenium, rhodium, palladium, osmium, iridium, platinum, manganese, zirconium, tin, cadmium and indium.
  • the intermediary metal is vanadium. Further, in an embodiment of the invention, the intermediary metal is selected among the following group: titanium, chromium and iron. Further, in an embodiment of the invention, the intermediary metal is selected among the following group: manganese, zirconium, molybdenum, technetium, tungsten, quicksilver, germanium, arsenic, selenium, tin, antimony, tellurium and copper. In the various embodiments of the invention, the yield metals and intermediary metals can be selected among a group that depends on various different process parameters, particularly on the pH value of the electrolyte (i.e. on the oxygen content) .
  • the supply material containing yield metal is placed in the anode.
  • the yield metal located on the anode side of the electrolytic cell is placed in the anode of the electrolytic cell.
  • the kinetics in the dissolution step are rapid, as the quantity of yield metal dissolved in the anolyte is directly proportional to the charge that has flown through the anode.
  • the quantity of yield metal that is dissolved in the anolyte can be efficiently and accurately controlled, which facilitates a more precise control of the process dynamics, and an improvement in reliability.
  • the yield metal is selected so that the selected yield metal is dissolved in the anolyte as a soluble salt of the acid that is contained in the first part of the starting solution .
  • the electrolytes are placed in an oxygen-free environment, in order to prevent the oxidation of the yield metal and/or intermediary metal that is contained in the electrolytes.
  • This makes it easier to control the acid content of the electrolytes, which means that the balance of chemical reactions taking place in the different solutions of the process and containing for example yield metal and/or intermediary metal can be adjusted more accurately, which in turn improves the reliability and efficiency of the process, among others .
  • the starting solution contains sulfuric acid. Further, in an embodiment of the invention the sulfuric acid content in the starting solution is at least 50 g/1 and preferably within the range 50 g/1 - 1,500 g/1. In an embodiment of the invention, the starting solution contains hydrochloric acid or nitric acid. Further, in an embodiment of the invention the hydrochloric acid content in the starting solution is within the range 15 g/1 - 500 g/1. Yet in an embodiment of the invention the starting solution contains, in addition to hydrochloric acid, also alkaline chloride, the content of which in the starting solution is within the range 15 g/1 - 500 g/1.
  • the suitability of an acid in the starting solution depends, among others, on the supply material, the yield metal and the intermediary metal in question.
  • the solutions may also contain more than one acid.
  • a man skilled in the art is capable, by routine testing, of finding a suitable acid for a certain supply material, yield metal and intermediary metal, and a suitable content for said acid.
  • a sulfuric acid content of the starting solution that is at least 50 g/1 provides for an efficient oxidation of a copper anode and its dissolution in the anode, when the intermediary metal is vanadium.
  • a suitable acid, and content for said acid must be chosen so that the yield metal is dissolved from the supply material to the anolyte, instead of the oxidation of the intermediary metal. Therefore the anolyte pH (i.e. oxygen content) must be suitable.
  • the oxygen content must be as high as possible .
  • the electrolytic cell comprises at least one bag defined by a diaphragm in order to restrict the anolyte and/or catholyte inside the bag. Further, in an embodiment of the invention the electrolytic cell comprises means for conducting the separator solution from a space left in between two diaphragms to the anode side and/or the cathode side.
  • Figure 1 is a flowchart illustrating an embodiment of a method according to the invention
  • Figure 2 is a schematical illustration of an embodiment of an arrangement according to the invention.
  • Figure 3 is a schematical block diagram illustrating an embodiment of a method according to the invention.
  • FIG. 4 is a schematical illustration of an embodiment of the electrolytic cell in an arrangement according to the invention.
  • Figure 5 shows scanning electron microscope images (SEM images) of copper powder produced by an embodiment of the invention.
  • the first part of the starting solution i.e. the part that is fed as the anolyte
  • the starting solution may contain two or even several different intermediary metals.
  • the first and second part of the starting solution are identical in composition.
  • the type of intermediary metal suited in the method essentially depends on the selected yield metal, which should be dissolved in the anolyte in step S2, and which is later precipitated into powder in the mixing step S3.
  • the intermediary metal and the selected yield metal together define the other features of the starting solution suited in the method, particularly the acid contained in the solution, and content of said acid in the solution.
  • the pH value of the solution must be such that in the prevailing process conditions, on the anode side there is more advantageously carried out the oxidation of yield metal and its dissolution in the anolyte than the oxidation of the intermediary metal in the anolyte.
  • This kind of process conditions i.e. functional windows, can be found for many different pairs of yield metal and intermediary metal. In the light of the description of the present invention as well as in the light of the Pourbaix diagrams of various different intermediary metals and yield metals, the finding of these functional windows represents routine testing for a man skilled in the art .
  • the starting solution can be produced in many different ways, which depend, among others, on the suitable intermediary metal.
  • One way is for example to dissolve, in an aqueous solution of a suitable acid, oxide containing the desired intermediary metal.
  • the acid content of the starting solution and the oxidation number of the dissolved intermediary metal can thereafter be adjusted to be suitable with respect to the starting solution.
  • the adjusting of the oxidation number of the intermediary metal can be carried out for example electrolytically.
  • step SI When the starting solution is formed in step SI, it is fed as electrolyte in an electrolytic cell, where supply material containing yield metal is located on the anode side.
  • step 2 yield metal is dissolved on the anode side of the electrolytic cell from the supply material to the anolyte, as the yield metal is at the same time oxidized, and on the cathode side the intermediary metal of the starting solution is reduced from a high potential value to a low potential value.
  • the intermediary metal content and the content of the dissolved yield metal in the solutions is as high as possible.
  • a certain solution volume gives more precipitated yield metal powder in the mixing step S3 than in a situation where the contents of the intermediary metal and/or dissolved yield metal in the solutions are low.
  • the method according to Figure 1 can be realized by means of an arrangement illustrated schematically in Figure 2, where the employed supply material is present as an anode 2, which provides for rapid kinetics in the dissolution of yield metal, while the dissolution of the supply material is directly proportional to the charge flowing through the anode 2.
  • the dissolution reactions can be controlled particularly accurately by using electricity; in a given period of time, the mass quantity of yield metal dissolved and oxidized on the anode is accurately proportional to the employed quantity of electricity, according to Faraday's laws.
  • an . equimolar quantity of the intermediary metal is regenerated (reduced) on the cathode.
  • the arrangement of Figure 2 also comprises a cathode 4, an anode side 6 of the electrolytic cell, a cathode side 8, anolyte filtering equipment 10, a precipitation chamber 12, separator equipment 16, and cleaning equipment 18 for the circulating solution.
  • the anolyte 1 and the catholyte 3 are mechanically separated by means of an electroconductive separator solution 5 placed in the intermediate space 11 and by means of two electroconductive diaphragms 7 that define the intermediate space.
  • the purpose is to ensure that the yield metal cations created on the anode side and the intermediary metal that is reduced to a low-potential value on the cathode side do not get into mutual contact in the electrolytic cell.
  • the separator solution 5 provided in the intermediate space 11 can also be maintained at a higher hydrostatic pressure than the anolyte 1 and the catholyte 3.
  • step S3 anolyte solution is conducted from the anode side of the electrolytic cell and catholyte solution is conducted from the cathode side thereof, for example by means of suitable pipes or in some other way, to the precipitation chamber 12, in a suitable ratio away from the vicinity of the electrodes 2, 4.
  • the mixing ratio of the solutions can be controlled easily and accurately, and it can be optimized according to the process conditions. With a correct mixing ratio and an effective precipitate recovery, the creation of yield metal agglomerates can be prevented in the precipitation step, and consequently the homogeneity, with respect to their size, of the yield metal particles contained in the yield metal powder 14 is ensured.
  • a correct mixing ratio also facilitates a process with a better efficiency, which results in reducing the amount of energy needed in the process for producing a certain quantity of yield metal mass.
  • the precipitation chamber 12 there is mixed, or there can be continuously mixed the anolyte solution and the catholyte solution conducted in the chamber 12.
  • the anolyte solution Prior to conducting the anolyte solution into the precipitation chamber 12, it can in some embodiments of the invention be also purified of metallic impurities and/or other possible impurities disturbing the yield metal precipitation process in an anolyte filtering equipment 10 that is suited for this purpose.
  • the oxidized yield metal of the anolyte solution is reduced and precipitated into solid yield metal powder 14, at the same time as the intermediary metal reduced in the catholyte solution is oxidized back to its high-potential value.
  • step S4 yield metal for example by centrifuging the circulating solution in separator equipment 16 suited for the purpose.
  • the created circulating solution is recirculated back to the electrolytic cell in step S5, part of it into anolyte 1 and part into catholyte 3.
  • any dissolved yield metal that is possibly left in the circulating solution is removed therefrom, as well as yield metal particles, in cleaning equipment 18 suited for this purpose.
  • the cleaning operation can be carried out for example electrolytically by reduction and filtering. A thorough removal of yield metal, both dissolved and precipitated, from the circulating solution prior to recirculating the circulating solution back to the electrolytic cell is useful for the reliability of the process, for improving process efficiency and the controllability of the particle size of the yield metal powder.
  • the composition of the circulating solution is essentially identical with the composition of the starting solution, because in precipitation, the intermediary metal is oxidized back into its starting solution value, and the yield metal dissolved in the anolyte 1 on the anode side is precipitated and separated from the solution.
  • the circulating solution created in the method can be reused as a starting solution.
  • an essentially closed electrolyte circulation can be used in the process, without a need to separately add/remove solution to or from the anode side 6 of the electrolytic cell, or to or from the cathode side 8.
  • the method of Figure 1 is generally realized as a continuous electrolyte circulation, as a result of which in the precipitation chamber 12 there is continuously accumulated yield metal powder 14 to be separated from the circulating solution and to be recovered, until the recirculation of the electrolyte solution (circulating electrolyte) in the arrangement is stopped, or when the yield metal contained in the supply material (anode 2) is completely dissolved in the electrolytic cell.
  • the recovered yield metal powder 14 is treated in a finishing treatment in step S6, and the process is stopped.
  • the finishing treatment for the recovered yield metal powder 14 can be carried out simultaneously with the other steps of the process, in the course of the process of separating yield metal powder 14 and feeding it to the finishing treatment equipment (not illustrated) .
  • the employed intermediary metal is vanadium, which in its high- potential value is V 3+ in cations.
  • the employed yield metal is copper, which is located in the supply material serving as the anode 2.
  • the starting solution containing the vanadium intermediary metal in V 3+ cations can be produced for instance by dissolving vanadium oxide V2O3 for instance to an aqueous solution of sulfuric acid.
  • the sulfuric acid content of said solution being for example within the range 50 g/1 - 1500 g/1
  • its first part is fed to the anode side 6 of the electrolytic cell as the anolyte 1
  • the second part is fed to the cathode side 8 as the catholyte 3.
  • the V 3+ cations are reduced on the cathode side 8 to V 2+ cations in the catholyte 3
  • copper is dissolved from the anode 2 to the anolyte 1 as oxidized Cu 2+ cations. Consequently, the anode reaction is Cu° -> Cu 2+ 2e ⁇ , and the cathode reaction is V 3+ + e " -> V 2+ .
  • the intermediary metal may in some embodiments of the invention participate in corresponding reactions, thus improving both dissolution and oxidation, in such process conditions, for example with fairly low acid contents, where dissolution and oxidation with the combined effect of a mere electric current and an acid solution would not be efficient.
  • the precise mechanism how the intermediary metal participates in the dissolution and oxidation of the yield metal depends on the selected yield metal and intermediary metal.
  • vanadium when the yield metal is copper and the intermediary metal is vanadium, vanadium may be oxidized on the anode side 6 into an intermediary oxidation state V 5+ , which is even higher than the V 3+ state, whereafter the V 5+ reacts with copper, thus oxidizing and dissolving copper. Now the "over- oxidized” vanadium V 5+ is reduced back to its original high-potential value V 3+ . On the anode side 6, a corresponding "overoxidation" to an intermediate oxidation state is also possible with other intermediary metals than vanadium.
  • anolyte solution and catholyte solution are conducted and mixed in a suitable ratio, for example in the ratio 1:3, in the precipitation chamber 12, where copper is precipitated through the reaction 2V 2+ + Cu 2+ -> 2V 3+ + Cu° .
  • anolyte and catholyte are in theory needed in the mixing ratio 1:2, in order to make all V 2+ and Cu 2+ cations present in the solutions participate in the precipitation of copper.
  • An optimal mixing ratio depends on the reaction state of the anode reactions and on the current efficiency, as well as on the reaction state and current efficiency of the cathode reactions.
  • the efficiency and reliability of the process it is useful to ensure that any remarkable amounts of V 2+ and/or Cu 2+ cations are not left in the circulating solution.
  • the real mixing ratio of anolyte and catholyte can be 1:N, where N > 2.
  • the value of the parameter N also depends on how the circulating solution is cleaned before feeding it back to the electrolytic cell.
  • the finding of a suitable mixing ratio is obvious routine testing for a man skilled in the art.
  • the remaining circulating solution is cleaned in the cleaning equipment 18 of any copper that is possibly left in the solution in the separation process, both of solid copper and dissolved, unprecipitated Cu 2+ cations.
  • the cleaning can be carried out for example electrolytically by precipitating and filtering.
  • the remaining circulating solution is essentially the same in composition as the starting solution, containing as a result from the precipitation reaction vanadium cations V 3+ and sulfuric acid in aqueous solution.
  • This circulating solution is again divided in a suitable ratio into anolyte 1 on the anode side 6 and into catholyte 3 on the cathode side 8.
  • the same circulation electrolyte can again be conducted through the arrangement and the method for precipitating more/new copper powder 14 to the precipitation chamber 12.
  • the solid yield metal powder 14 separated from the solution is finished ( Figure 1, step S6) in a finish treatment arrangement.
  • the separation and finish treatment processes can include many different steps, depending on the desired properties of the end product.
  • the yield metal powder 14 separated from the circulation electrolyte is washed in water for minimizing impurities carried along from the solution, whereafter the yield metal powder 14 is dried and coated with a passivation layer for preventing an oxidation of the powder, among others.
  • the yield metal powder 14 is subjected to various separate washing operations. In between the washing operations, the yield metal powder 14 is separated from the washing liquid.
  • the yield metal powder 14 that is obtained from the separator equipment 16, which is separated from the circulating electrolyte by centrifuging but is still wet is mixed in water in the mass mixing ratio 1:20 (one part of wet yield metal powder 14 and 20 parts of water) three times. In between the mixing operations, the yield metal powder 14 is separated from the washing liquid.
  • the washing equipment for realizing several successive washing operations can be for example a conveyor-belt type arrangement, where the wet yield metal powder 14 is poured on a conveyor belt, which conveys the yield metal powder 14 to the washing liquid, from which the yield metal powder is poured on the next conveyor belt, etc. Now the settling of the yield metal powder 14 takes place when it is separated from the washing liquid, i.e. when the washing liquid containing yield metal powder is poured on the conveyor belt.
  • the separated yield metal powder can naturally also be washed by many known methods, for example by means of a syphon.
  • electrolytic cell structures can be designed for dissolving and oxidizing yield metal on the anode side of an electrolytic cell, and for reducing intermediary metal on the cathode side of an electrolytic cell.
  • the electrolytic cell structure illustrated schematically in Figure 4 can be used in the arrangement for producing yield metal powder 14 in a reliable and efficient way, with a good efficiency.
  • both the anode side 6 and the cathode side 8 comprise several sections, i.e. diaphragm bags, defined by a diaphragm 7.
  • Each diaphragm bag respectively includes an anode 2 or a cathode and anolyte 1 or catholyte 3.
  • the anodes 2 and the cathodes 4 are connected to a power source (not illustrated) .
  • electroconductive separator solution 5 which in one embodiment of the invention contains intermediary metal in a suitable high-potential value, i.e. in an oxidized state; in the case of the above described example, the separator solution 5 may contain for example V 3+ ions.
  • the electrolytic cell of Figure 4 comprises a feed pipe 9 for feeding separator solution to the intermediate space 11 left between the diaphragm bags, an overflow channel 13 for the separator solution 4, drain channels 15 for the anolyte solution and the catholyte solution, as well as a protective film 17.
  • the electrolytic cell of Figure 4 can be connected to another arrangement, for example to a precipitation chamber 12 (not illustrated in Figure 4), by intermediation of the drain channels 15 and the feed pipe 9.
  • the separator solution 5 serves as the starting solution, in which case the composition of the separator solution 5 is identical to that of the starting solution.
  • the starting solution can be- fed to the intermediate space 11 of the electrolytic cell illustrated in Figure 4 through the apertures provided in the feed pipe 9.
  • the separator solution 5 flows to the diaphragm bags as anolyte 1 and catholyte. 3 through perforations provided in the diaphragms 7.
  • the diaphragm can be semi-permeable, so that the separator solution 5 (starting solution) has access to flow in a controlled fashion through the diaphragm 7 as anolyte 1 and/or catholyte 3.
  • the obtained catholyte solution, containing reduced intermediary metal, as well as the anolyte solution containing dissolved or oxidized yield metal, can be conducted to the precipitation chamber 12 for example through outlets 15.
  • the outlets 15 can serve as overflow channels for removing excess electrolyte from the arrangement, in which case anolyte solution and/or catholyte solution can be brought in the precipitation chamber 12 via another route, for example through suction inlets provided for this purpose.
  • the circulating solution created in the precipitation chamber 12 can in turn be recirculated, after possible cleaning steps, for example via a feed pipe 9 back to the intermediate space 11 and further to anolyte 1 and/or catholyte 3.
  • a feed pipe 9 back to the intermediate space 11 and further to anolyte 1 and/or catholyte 3.
  • the permeability of the diaphragms 7 can be selected separately for the diaphragms 7 on the anode side 6 and/or for the diaphragms 7 on the cathode side 8.
  • the hydrostatic pressure of the separator solution 5 placed in the intermediate space 11 can be adjusted to be higher than the hydrostatic pressure of the electrolytes contained in the diaphragm bags located in the separator solution 5.
  • the diaphragms 7 are selected to be such that they are completely impermeable to solution, circulating solution and/or starting solution can be fed to the anode side 6 and/or to the cathode side 8, for example to the diaphragm bags, directly and not through the intermediate space 11.
  • ion-selective membranes instead of the diaphragms 7, there can be used for example ion-selective membranes that only permeate ions of a certain type.
  • the electrolytic cell structure is covered by a protective film 17, by means of which the intermediate space 11 can be pressurized for example with nitrogen gas or with some other inert gas in order to prevent a possible oxidation caused by air or the surrounding environment. Also the diaphragm bags can be closed and pressurized with nitrogen in order to prevent oxidation .
  • the cell structure of Figure 4 enables a reliable separation of the anolyte and the catholyte in the electrolytic cell, which reduces premature oxidation and/or reduction reactions. Consequently, by using the electrolytic cell structure according to Figure 4, there is achieved a good efficiency in the method. In addition, the risk of a premature precipitation of the yield metal powder in the electrolytic cell is reduced, which improves the reliability of the method and makes the maintenance of the equipment easier.
  • the starting solution was fed to the electrolytic cell, where copper anode was oxidized and dissolved in the anolyte.
  • the measured content of the dissolved copper was roughly 4 g/1.
  • anolyte solution was conducted from the anode side, and catholyte solution was conducted from the cathode side to the precipitation chamber, which in this example was a glass bottle.
  • the mixing ratio of the anolyte solution and the catholyte solution was 1:3.
  • copper powder was formed in the precipitation chamber, according to the description above.

Abstract

L'invention porte sur un procédé et un dispositif pour produire une poudre métallique. Dans le procédé, un métal utile dissous est mélangé dans une solution contenant au moins un métal intermédiaire pour précipiter le métal utile dissous en une poudre de métal utile (14). Dans le procédé, la première partie d'une solution de départ contenant un acide est introduite sur le côté anode (6) d'une cellule électrolytique en qualité d'anolyte (1) pour entrer en contact avec l'anode et la matière d'alimentation contenant un métal voulu, et la seconde partie de la solution de départ contenant un acide, qui contient aussi le métal intermédiaire, est introduite sur le côté cathode (8) de la cellule électrolytique pour entrer en contact avec la cathode (4) en qualité de catholyte (3). Le métal à produire est oxydé et dissous dans l'anolyte (1) sous l'effet de l'amenée d'un courant électrique dans l'anode (2) ; le métal produit contenu dans la seconde partie de la solution de départ est réduit sur le côté cathode (8) ; et la solution d'anolyte et la solution de catholyte sont introduites dans une chambre de précipitation (12) pour mélanger le métal produit dissous, oxydé, et la seconde partie de la solution de départ contenant le métal intermédiaire réduit.
EP11736667.4A 2010-01-29 2011-01-25 Procédé et dispositif pour produire une poudre métallique Not-in-force EP2528704B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI20105083A FI124812B (fi) 2010-01-29 2010-01-29 Menetelmä ja laitteisto metallipulverin valmistamiseksi
PCT/FI2011/050056 WO2011092375A1 (fr) 2010-01-29 2011-01-25 Procédé et dispositif pour produire une poudre métallique

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EP2528704A1 true EP2528704A1 (fr) 2012-12-05
EP2528704A4 EP2528704A4 (fr) 2016-11-23
EP2528704B1 EP2528704B1 (fr) 2018-10-03

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KR (1) KR101529373B1 (fr)
CN (1) CN102725086B (fr)
EA (1) EA021918B1 (fr)
ES (1) ES2703254T3 (fr)
FI (1) FI124812B (fr)
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Cited By (2)

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EP3795717A4 (fr) * 2018-05-16 2022-03-23 Sumitomo Metal Mining Co., Ltd. Procédé de production d'une solution d'acide sulfurique et cuve d'électrolyse pouvant être utilisée au cours dudit procédé de production
US11781228B2 (en) 2018-05-16 2023-10-10 Sumitomo Metal Mining Co., Ltd. Method for manufacturing sulfuric acid solution and electrolyzer used thereof

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RU2600305C1 (ru) * 2015-05-08 2016-10-20 Федеральное государственное бюджетное учреждение науки Институт высокотемпературной электрохимии Уральского отделения Российской Академии наук СПОСОБ ЭЛЕКТРОХИМИЧЕСКОГО ПОЛУЧЕНИЯ ПОРОШКА ИРИДИЯ С УДЕЛЬНОЙ ПОВЕРХНОСТЬЮ БОЛЕЕ 5 м2/г
CN110565115B (zh) * 2016-03-09 2022-04-05 Ｊｘ金属株式会社 高纯度锡
CN107030290B (zh) * 2017-04-27 2019-02-01 上海交通大学 一种纳米锡粉的制备工艺
CN107513730B (zh) * 2017-08-31 2019-06-14 北京工业大学 连续制备钨粉和钴粉的装置以及方法
CN107955952A (zh) * 2017-11-02 2018-04-24 马鞍山市宝奕金属制品工贸有限公司 一种利用铁渣生产高纯铁粉的方法
KR102602595B1 (ko) 2021-11-22 2023-11-16 (주)선영시스텍 금속 분말 세척장치
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US11781228B2 (en) 2018-05-16 2023-10-10 Sumitomo Metal Mining Co., Ltd. Method for manufacturing sulfuric acid solution and electrolyzer used thereof

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EA201290714A1 (ru) 2013-02-28
FI124812B (fi) 2015-01-30
CN102725086A (zh) 2012-10-10
JP5676649B2 (ja) 2015-02-25
JP2013518189A (ja) 2013-05-20
ES2703254T3 (es) 2019-03-07
KR20120115999A (ko) 2012-10-19
KR101529373B1 (ko) 2015-06-16
CN102725086B (zh) 2015-04-22
WO2011092375A1 (fr) 2011-08-04
EA021918B1 (ru) 2015-09-30
US20120298523A1 (en) 2012-11-29
FI20105083A0 (fi) 2010-01-29
FI20105083A (fi) 2011-07-30
EP2528704B1 (fr) 2018-10-03
EP2528704A4 (fr) 2016-11-23

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