WO2016151949A1 - Procédé et appareil de production de cuivre - Google Patents

Procédé et appareil de production de cuivre Download PDF

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WO2016151949A1
WO2016151949A1 PCT/JP2015/083838 JP2015083838W WO2016151949A1 WO 2016151949 A1 WO2016151949 A1 WO 2016151949A1 JP 2015083838 W JP2015083838 W JP 2015083838W WO 2016151949 A1 WO2016151949 A1 WO 2016151949A1
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Prior art keywords
copper
solution
oxidizing agent
side electrode
oxidant
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PCT/JP2015/083838
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English (en)
Japanese (ja)
Inventor
光靖 小川
知之 粟津
真嶋　正利
真博 加藤
Original Assignee
住友電気工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by 住友電気工業株式会社 filed Critical 住友電気工業株式会社
Priority to KR1020177026195A priority Critical patent/KR20170130408A/ko
Priority to US15/557,892 priority patent/US20180073156A1/en
Priority to CN201580078129.7A priority patent/CN107429413A/zh
Publication of WO2016151949A1 publication Critical patent/WO2016151949A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • 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
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/04—Diaphragms; Spacing elements
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to a method for producing copper by electrolytic refining and a copper production apparatus.
  • copper and copper alloys are metals in great demand like iron and aluminum. Therefore, it is important from the viewpoint of protecting resources to collect discarded electric wires and printed circuit boards of household electrical appliances, and to recover and reuse copper from such copper-containing copper scrap.
  • the copper wire is crushed while being covered with the resin, and then the specific gravity difference is selected.
  • fine resin still remains on the copper surface, and it is necessary to further remove the resin by burning.
  • the recovery of copper by the dry method as described above is simple, but the burden on the environment is large because carbon dioxide is generated by the combustion of the resin, and reduction processing is performed because copper is recovered as copper oxide. Is required. Furthermore, depending on the purity of the copper scrap recovered from the market as a raw material, the purity of the recovered metal copper is lowered.
  • a recovery method by a wet method is known in addition to a dry method.
  • copper is leached with sulfuric acid, hydrochloric acid or the like, and copper is recovered by electrolytic refining.
  • oxygen is generated at the anode electrode, which inevitably increases power consumption during electrolysis.
  • Patent Document 1 discloses a cathode electrode for depositing metallic copper in a solution containing monovalent copper ions, an anode electrode in an ammonia alkaline solution containing monovalent copper ions, and a gap between the cathode electrode and the anode electrode.
  • a method is described in which a diaphragm is provided, current is passed through the electrode, and electrolysis is performed while the solution is moved from the cathode electrode side to the anode electrode side to recover metallic copper.
  • metallic copper is deposited on the cathode electrode portion, and at the same time, the monovalent copper ions can be converted into divalent copper ions at the anode electrode portion, and the divalent copper ion solution is taken out.
  • the solution containing monovalent copper ions obtained by treating the copper metal waste and the complex layer in which the copper metal waste and the complex compound exist and treating the copper metal waste is used as the solution containing the electrolytic monovalent copper ions. Therefore, it is said that power consumption can be made smaller than before.
  • the treatment target solution for recovering copper contains ions of metals such as manganese, nickel, zinc, and lead, it is necessary to remove the metal ions in order to perform the electrolysis operation.
  • ammonia is used in the method described in Patent Document 1, if the copper metal waste contains a resin, the resin and ammonia may react. If the resin and ammonia react, the ammonia will be consumed excessively. Further, there is a problem that impurities in the resin are easily dissolved in the ammonia alkaline solution.
  • JP 2003-253484 A Japanese Patent Laid-Open No. 2014-040639
  • Patent Document 2 includes a solution in which an electrolytic layer is partitioned into a cathode chamber and an anode chamber by a cation exchange membrane and a metal is dissolved using an oxidizing agent, and a solution containing an oxidized oxidizing agent in a reduced state.
  • a metal production method in which electrolysis is performed to deposit metal on the surface of the cathode. According to this method, it is possible to regenerate the oxidizing agent in the anode chamber using the diamond electrode while recovering the metal in the cathode chamber. Therefore, although an initial cost is required in terms of using a diamond electrode, the main running cost is only the electricity cost required for electrolysis.
  • Patent Document 2 uses a strong oxidizing agent such as ammonium persulfate or hydrogen peroxide, and thus reacts with water and self-discharges. Has been found to occur. This phenomenon is remarkable when the solution is left standing, and the solution that has not been used for a certain period of time may be deteriorated.
  • oxidizing agents that cannot be used effectively for dissolving metals, and there is room for improvement in terms of smelting metals at a lower cost.
  • the present invention provides a method for producing copper that can obtain high-purity copper efficiently and at low cost by a wet method without increasing the burden on the environment, without producing waste liquid. Objective.
  • the method for producing copper includes: (1) a first step of dissolving copper by adding a copper-containing material to a solution containing an oxidizing agent;
  • the solution (A) containing the oxidant in a reduced state and the solution (B) in which the copper is dissolved are brought into contact with each other through a diaphragm, and an anode-side electrode is provided on the solution (A).
  • a method for producing copper that can obtain high-purity copper efficiently and at low cost by a wet method without increasing the burden on the environment, without producing waste liquid. Can do.
  • a method for producing copper according to one aspect of the present invention includes: A first step of dissolving copper by adding a copper-containing material in a solution containing an oxidizing agent; The solution (A) containing the oxidant in a reduced state and the solution (B) in which the copper is dissolved are brought into contact with each other through a diaphragm, and an anode-side electrode is provided on the solution (A).
  • the oxidizing agent is preferably one or more selected from the group consisting of iron ions, manganese ions, vanadium ions, and chromium ions. According to the invention described in (2) above, since the solution containing the oxidizing agent does not cause self-discharge, copper can be efficiently dissolved.
  • the concentration of copper in the solution (B) in which the copper is dissolved is preferably 12 g / L or more. According to the invention described in (6) above, when the copper production method is continuously performed, it can be performed while maintaining a good state in which copper can be stably electrodeposited.
  • An apparatus for producing copper according to one aspect of the present invention includes: A copper manufacturing apparatus for carrying out the copper manufacturing method according to any one of (1) to (6) above, A management tank of a solution containing an oxidizing agent, a dissolution tank, a management tank of a solution in which copper is dissolved, an electrolytic tank, and a management tank of a solution containing an oxidizing agent in a reduced state,
  • the electrolytic cell is an apparatus for producing copper, which is partitioned by an ion exchange membrane into an oxidant regeneration chamber having an anode side electrode and a plating chamber having a cathode side electrode.
  • the copper manufacturing apparatus preferably includes a plurality of the dissolution tanks. According to the invention described in (8) above, it is possible to perform copper dissolution in parallel in a plurality of dissolution tanks, which takes time compared to the second step of depositing copper. For this reason, while performing the 2nd process of depositing copper, copper can be dissolved and an oxidizing agent can be completely reacted and an efficient operation can be performed.
  • the first step of dissolving copper is a step of dissolving copper by adding a copper-containing material to the solution using a solution containing an oxidizing agent.
  • copper (Cu) is dissolved in the solution to become copper ions (Cu 2+ ), and the oxidizing agent in the solution is in a reduced state.
  • the oxidant is iron ion (Fe 3+ )
  • Fe 3+ iron ion
  • it is preferable that all the oxidizing agent in the solution is consumed in order to dissolve copper. That is, in the first step of dissolving copper, it is preferable to add an excessive amount of copper-containing material so that the oxidizing agent is completely reduced.
  • the copper-containing material may be anything as long as it contains copper. If you use products collected from the market such as waste, you can contribute to resource conservation. For example, copper wires, printed boards for personal computers and home appliances, semiconductors, electronic devices, motors, automobile shredder dust, harness connectors, and the like can be used. From the viewpoint of adding and dissolving a copper-containing material in a solution containing an oxidizing agent, it is preferable to pulverize as finely as possible to increase the surface area because the dissolution time can be shortened. Although it is preferable to use powder, other shapes may be used. Specifically, it is preferably one that has been pulverized to a state of about 3 mm or less.
  • the pulverized copper-containing material is a filter or filter cloth (bag-like material made of resin, fibers, etc.) It is preferable to use them packed in the same manner. Moreover, after dissolving copper in a solution, you may remove the insoluble matter which was not melt
  • a tray or the like may be placed on the bottom of a tank such as a dissolution tank, and the sedimented material may be taken out and collected.
  • the copper-containing material is preferably a mixed powder of copper and a material that does not substantially dissolve in a solution containing an oxidizing agent.
  • the copper-containing material is a mixed powder of copper and resin
  • the resin does not dissolve in a solution containing an oxidizing agent, and therefore can be removed from the solution by filtration or the like.
  • the copper-containing material contains a component that is soluble in a solution containing an oxidizing agent, the component accumulates in the solution as an impurity, and as an impurity in the second step of depositing copper, which will be described later. May be mixed with copper.
  • copper is a metal having a high oxidation-reduction potential, it can be recovered in a state in which almost no impurities are contained in the second step of depositing copper described later. That is, it is possible to recover only the copper by dissolving the impurities in a state where a potential at which copper is deposited is loaded.
  • the solution containing Fe 3+ dissolves most of the metals other than noble metals. Therefore, for example, in the case of using a mixed powder of copper and noble metal, the noble metal that does not dissolve in the solution containing Fe 3+ can be recovered by filtration or the like, and the copper can be recovered in the second step of depositing copper described later.
  • Specific examples of the mixture with copper include resin, gold, platinum, silver, tungsten, molybdenum, titanium, and ceramics.
  • copper-containing materials include plating sludge and polishing sludge. Resin, gold, platinum, silver, tungsten, molybdenum, titanium, and ceramics are essentially unnecessary components that are either completely insoluble in a solution containing an oxidizer or that only a very small amount slowly dissolves.
  • the oxidizing agent may be any one capable of dissolving copper and having a standard potential of 1.6 V or less.
  • the standard potential of the oxidant is 1.6 V or less, it is possible to suppress the deterioration of the solution due to self-discharge.
  • the standard potential of the oxidizing agent is preferably 1.5 V or less, and more preferably 1.4 V or less.
  • the oxidizing agent include iron ions, manganese ions, vanadium ions, and chromium ions.
  • One type of these oxidizing agents may be used alone, or a plurality of types may be mixed and used.
  • iron ions are used from the viewpoints of resource, reusability, safety, copper solubility, low electrolysis voltage, ease of valence control, distinguishability of color change, etc. It is optimal to use.
  • the solution containing the oxidizing agent may be any solution containing the oxidizing agent.
  • the oxidizing agent is iron ion, for example, a ferric sulfate solution, a ferric chloride solution, or the like can be preferably used.
  • the oxidizing agent is manganese ions, for example, manganese sulfate can be preferably used.
  • the oxidizing agent is vanadium ion, for example, vanadium sulfate can be preferably used.
  • the oxidizing agent is chromium ion, for example, chromium sulfate can be preferably used.
  • concentration of an oxidizing agent according to the kind of oxidizing agent in the solution containing the said oxidizing agent.
  • the iron ion concentration is preferably 10 g / L or more and 130 g / L or less, and 15 g / L or more and 110 g / L or less. More preferably, it is more preferably 20 g / L or more and 90 g / L or less.
  • the iron ion concentration of the ferric sulfate solution By setting the iron ion concentration of the ferric sulfate solution to 10 g / L or more, a certain amount of copper can be dissolved in the solution from the copper-containing material, and a sufficient amount of copper can be produced at one time. It becomes like this. Moreover, the risk that iron or copper salt precipitates can be reduced by setting it as 130 g / L or less.
  • the pH of the ferric sulfate solution is preferably 4 or less, more preferably 3.5 or less, and still more preferably 3 or less.
  • FIG. 1 is a schematic diagram showing how the solution changes before and after the second step of depositing copper.
  • the solution (A) 6 containing the reduced oxidizing agent and the solution (B) 5 in which copper is dissolved are brought into contact with each other through the diaphragm 4.
  • a diaphragm is provided in a normal electrolytic cell and partitioned into two chambers, one containing a reduced solution (A) 6 containing an oxidizing agent and the other containing a solution of copper (B) 5 Just put in.
  • the anode-side electrode 2 is provided in the solution (A) 6 containing the oxidant in the reduced state, and the cathode-side electrode 1 is provided in the solution (B) 5 in which the copper is dissolved. Then, both electrodes are connected to the rectifier 3, a voltage is applied, and a current is passed to perform electrolytic smelting.
  • the 2nd process which precipitates copper is demonstrated taking the case of using an iron ion as an oxidizing agent as an example, However, When other oxidizing agents are used, it can be performed on the same principle.
  • the solution (A) on the side where the anode side electrode is provided is recovered after the second step of depositing the copper, and the solution It is preferable to reuse (A) as a solution containing an oxidizing agent in the first step.
  • the solution on the side where the anode side electrode 2 is provided is the solution 8 regenerated by the oxidant, and this solution contains a large amount of Fe 3+. Exists. For this reason, when performing the manufacturing method of copper which concerns on embodiment of this invention repeatedly and continuously, it can be reused as a solution containing the said oxidizing agent.
  • the solution (B) on the side where the cathode side electrode is provided is collected, It is preferable to reuse the solution (B) as the solution (A) in the second step.
  • the solution on the side where the cathode electrode 1 is provided is the solution 7 from which the copper is deposited and removed, and this solution contains a large amount of Fe 2+. Exists. For this reason, when performing the manufacturing method of the copper which concerns on embodiment of this invention repeatedly and continuously, it can recycle as the solution (A) 6 containing the oxidizing agent of the said reduced state.
  • dissolved The concentration is preferably 12 g / L or more. This makes it possible to continuously and repeatedly produce copper while maintaining a good state in which copper can be stably deposited.
  • the copper concentration is 12 g / L or more.
  • the copper concentration is less than 12 g / L, it is preferable to stop applying the voltage.
  • the copper concentration is more preferably 15 g / L or more, and further preferably 18 g / L or more.
  • the electrolytic cell can be made movable and the anode side electrode and the cathode side electrode can be reversed. That is, after the second step of precipitating copper is completed, a copper-containing material is added to the solution regenerated by the oxidizing agent to dissolve the copper, and the anode-side electrode and the cathode-side electrode are exchanged for electrolysis. Moreover, it is possible to repeat a 1st process and a 2nd process also by replacing solutions with a pump.
  • stirring the solution may make the copper precipitation state cleaner.
  • Stirring may be performed by a general method such as circulating the solution with a pump or performing air bubbling. Or you may circulate each solution through an electrolytic cell like a redox flow battery. Further, a plurality of electrolytic cells may be connected in series or in parallel.
  • copper can also be deposited in a powder form without dare stirring the solution.
  • an additive or the like may be added to the solution (B) in which the copper is dissolved.
  • additives those commonly used in copper plating and copper electrolytic refining techniques can be used.
  • suitable additives such as substances that form a complex with the impurities may be added.
  • a substance that precipitates impurities or a substance that adsorbs impurities may be added to the solution (B) to prevent eutectoid.
  • Impurities may accumulate in the solution.
  • impurities may be removed by precipitation by adjusting pH or the like, or so-called “discard plating” may be performed in which impurities are electrodeposited by electrolysis under conditions more severe than normal conditions.
  • the copper concentration is excessively increased, it can be adjusted by the same method.
  • a solution containing no iron such as simple sulfuric acid may be used on the counter electrode side.
  • the solution (B) in which the copper is dissolved and the solution (A) containing the reduced state oxidizing agent contain a large amount of chlorine, chlorine gas may be generated during electrolysis. It is preferable that it does not contain chlorine. In addition, even if chlorine is contained in the solution, there is no problem as long as the amount is small.
  • the solution (A) and the solution (B) are preferably based on sulfuric acid because they are easy to handle.
  • the solution (A) and the solution (B) may be at room temperature, but may be at a high temperature such as 60 ° C. If the liquid temperature is too low, salt is likely to precipitate, and if the liquid temperature is too high, the electrodeposition state may become unstable or water may evaporate, making management difficult.
  • the liquid temperature of the solution (A) and the solution (B) during electrolysis is preferably 10 ° C. or more and 70 ° C. or less, more preferably 15 ° C. or more and 65 ° C. or less, and 20 More preferably, it is not lower than 60 ° C. and not higher than 60 ° C.
  • cathode side electrode Any cathode side electrode can be used as long as it can deposit copper on the electrode surface.
  • copper, platinum, gold, titanium, stainless steel, etc. can be used. From the viewpoint of depositing copper, it is preferable to use a copper foil as a seed material.
  • the electrodeposited copper may be peeled off and recovered using a stainless steel plate, a titanium plate or the like for the blank.
  • -Anode side electrode What is necessary is just to use what can maintain a stable state at the time of electrolysis as said anode side electrode.
  • carbon, lead, noble metal, titanium, tungsten, or the like can be used.
  • a titanium lath plate or the like may be coated with a noble metal.
  • the membrane is preferably a membrane that allows only hydrogen ions to pass therethrough, since it provides the best electrolysis efficiency, but it can also be used for membranes that transmit other ions.
  • an ion exchange membrane it may be a cation exchange membrane or an anion exchange membrane. It is also possible to use an unglazed plate or a filter cloth.
  • the copper manufacturing apparatus according to the embodiment of the present invention is an apparatus capable of performing the copper manufacturing method according to the embodiment of the present invention.
  • a management tank 23 of a solution in which copper is dissolved an electrolytic tank 24, and a management tank 25 of a solution containing an oxidant in a reduced state.
  • the electrolytic cell 24 is partitioned by a diaphragm 244 into a plating chamber having a cathode electrode and an oxidant regeneration chamber having an anode electrode.
  • the arrows in FIG. 2 indicate the flow through which each solution circulates. Each solution may be circulated using a pump or the like.
  • a solution containing an oxidizing agent is prepared and supplied to the dissolution tank 22.
  • Copper content 221 is added here and copper is dissolved by stirring or the like.
  • the dissolution tank 22 is preferably a circular tank in plan view. An insoluble matter is removed from the solution in which copper obtained by this is dissolved as needed, and it sends to the management tank 23 of the solution in which copper was dissolved.
  • dissolution of copper and filtration of a solution may take time.
  • the solution in which the copper is dissolved is sent to the plating chamber of the electrolytic cell 24. Further, the solution containing the reduced state oxidant prepared in the management tank of the solution containing the reduced state oxidant is supplied to the oxidant regeneration chamber of the electrolytic cell 24. Then, a voltage is applied to both solutions to conduct electricity, and electrolysis is performed. Thereby, it deposits on the surface of the cathode side electrode 241 and can obtain metallic copper with high purity.
  • the solution in the plating chamber is a solution containing the oxidant in a reduced state after copper is deposited and removed, and the solution containing the oxidant in the reduced state is taken out with a pump. To the management tank 25. Further, since the solution in the oxidant regeneration chamber is in a state of being regenerated by oxidizing the oxidant, it is sent to the management tank 21 for the solution containing the oxidant.
  • the copper manufacturing method according to the embodiment of the present invention can be repeated and continuously performed by operating the copper manufacturing apparatus according to the embodiment of the present invention.
  • each structure, such as a cathode side electrode can use the same thing as what was demonstrated in the copper manufacturing method concerning the said embodiment of this invention.
  • Example 1 (First step to dissolve copper)
  • 3000 g of electric wire pulverized waste containing about 50% by mass of copper and resin was prepared.
  • the electric wire crushed waste was a powdery material of about 1 mm.
  • 80 L of a ferric sulfate solution having an iron ion concentration of 30 g / L was prepared. Copper sulfate was added to this ferric sulfate solution to adjust the copper ion concentration to 20 g / L.
  • the ferric sulfate solution and electric wire pulverized waste were placed in a dissolution tank, stirred for 6 hours to dissolve copper, and a solution in which copper was dissolved was obtained.
  • the copper ion concentration in the solution in which copper was dissolved was 40 g / L.
  • the remaining resin was removed by filtering the liquid.
  • the electrolytic cell was partitioned using Nafion 117, which is a cation exchange membrane, as a diaphragm. And the solution in which the copper obtained above was dissolved was put on one side. On the other side, 80 L of ferrous sulfate in a state where iron ions were reduced to Fe 2+ as a solution (A) containing a reduced state oxidant was added. The iron ion concentration of ferrous sulfate was 30 g / L.
  • a copper foil was provided as a cathode side electrode in a plating chamber containing a solution in which copper was dissolved.
  • a titanium lath plate coated with platinum was provided as an anode side electrode in the oxidant regeneration chamber containing the solution (A) containing the oxidant in a reduced state.
  • a rectifier was connected to both electrodes, the voltage was applied, and it electrolyzed. The voltage at this time was 3.8V.
  • the liquid temperature was 28 ° C.
  • the above process was carried out 10 cycles, and a total of 15 kg of copper could be obtained.
  • the solution (A) on the side where the anode side electrode was provided was reused as a solution containing an oxidizing agent, and the cathode side electrode was provided.
  • the side solution (B) was reused as a solution (A) containing an oxidant in a reduced state.
  • voltage application was stopped in a state where the concentration of copper in the solution in which the copper was dissolved was 18 g / L.
  • the apparatus one having the configuration shown in FIG. 2 was used.
  • Example 2 As a solution containing an oxidizing agent, a solution having a concentration of V 4.5+ of 30 g / L and a copper ion concentration of 20 g / L was used, and as a solution (A) containing an oxidizing agent in a reduced state, V 3.5+
  • a solution (A) containing an oxidizing agent in a reduced state V 3.5+
  • copper was produced in the same manner as in Example 1 except that the voltage was 4.7 V.
  • the liquid temperature was 28 ° C.
  • electrolysis was performed for 15 hours, whereby 1300 g of copper was deposited on the cathode side electrode.
  • the purity of this copper was 99.9% or more.
  • the electrodeposition efficiency was 91%.
  • the solution containing the oxidant and the solution (A) containing the oxidant in the reduced state are prepared by dissolving vanadium oxide sulfate (VOSO 4 ) in sulfuric acid to produce a vanadium sulfate solution containing V 4+ and performing ion exchange. It was produced by electrolyzing the vanadium sulfate solution using a membrane.
  • the copper ion concentration was adjusted by adding copper sulfate.
  • the V 4.5+ means that V 5+ and V 4+ are included in half.
  • V 3.5+ means that V 4+ and V 3+ are included in half.

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Abstract

La présente invention concerne un procédé de production de cuivre qui comprend : une première étape au cours de laquelle un matériau contenant du cuivre est introduit dans une solution contenant un oxydant, de manière à dissoudre du cuivre dans celle-ci ; et une seconde étape au cours de laquelle une solution (A) qui contient un oxydant dans un état réduit et la solution (B), dans laquelle est dissous le cuivre, sont mises en contact l'une avec l'autre, un diaphragme étant interposé entre celles-ci, et une tension est appliquée entre des électrodes par attribution à la solution (A) d'une électrode de côté anode et par attribution à la solution (B) d'une électrode de côté cathode, de façon à entraîner la précipitation de cuivre sur la surface de l'électrode côté cathode, tout en régénérant l'oxydant contenu dans la solution (A). Dans cette configuration, le potentiel standard de l'oxydant est inférieur ou égal à 1,6 V.
PCT/JP2015/083838 2015-03-25 2015-12-02 Procédé et appareil de production de cuivre WO2016151949A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020177026195A KR20170130408A (ko) 2015-03-25 2015-12-02 구리의 제조 방법 및 구리의 제조 장치
US15/557,892 US20180073156A1 (en) 2015-03-25 2015-12-02 Method for producing copper and apparatus for producing copper
CN201580078129.7A CN107429413A (zh) 2015-03-25 2015-12-02 铜的制造方法以及铜的制造装置

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CN107841630B (zh) * 2017-11-08 2019-05-10 东江环保股份有限公司 线路板贵贱金属分离方法
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