WO2012133136A1 - 電解採取用陽極およびそれを用いた電解採取法 - Google Patents

電解採取用陽極およびそれを用いた電解採取法 Download PDF

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WO2012133136A1
WO2012133136A1 PCT/JP2012/057426 JP2012057426W WO2012133136A1 WO 2012133136 A1 WO2012133136 A1 WO 2012133136A1 JP 2012057426 W JP2012057426 W JP 2012057426W WO 2012133136 A1 WO2012133136 A1 WO 2012133136A1
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electrowinning
anode
oxide
catalyst layer
amorphous
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PCT/JP2012/057426
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English (en)
French (fr)
Japanese (ja)
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正嗣 盛満
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学校法人同志社
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Priority to RU2013147642/02A priority Critical patent/RU2568546C2/ru
Priority to CN201280016122.9A priority patent/CN103476970B/zh
Priority to KR1020137024065A priority patent/KR101577664B1/ko
Priority to EP12763572.0A priority patent/EP2690200B1/en
Priority to CA2831273A priority patent/CA2831273C/en
Priority to AU2012234150A priority patent/AU2012234150B2/en
Priority to ES12763572.0T priority patent/ES2557194T3/es
Priority to US14/007,488 priority patent/US20140054180A1/en
Publication of WO2012133136A1 publication Critical patent/WO2012133136A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02—Electrodes; Connections thereof
    • 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
    • C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
    • C25C1/08—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of nickel or cobalt
    • 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
    • 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

Definitions

  • the present invention relates to an electrowinning anode used for electrowinning to collect a desired metal by electrolysis, and to an electrowinning method using the same, and in particular, using a sulfuric acid-based electrolyte, the anode reaction is oxygen generation.
  • the present invention relates to an electrolytic collection anode used for certain electrolytic collection and an electrolytic collection method using the same.
  • Electrolytic extraction of metal is carried out by immersing the anode and cathode in an aqueous solution containing the ions of the metal to be collected (hereinafter referred to as electrolyte) and energizing to deposit the metal on the cathode.
  • electrolyte aqueous solution containing the ions of the metal to be collected
  • Typical electrowinning examples include copper, zinc, nickel, cobalt, lead, platinum group metals (platinum, iridium, ruthenium, palladium, etc.), noble metals (silver, gold), other transition metal elements, rare metals or critical It is prepared through the process of extracting the target metal ion after crushing ore containing any one or more of the metal elements generically named metal, dissolving the metal ion using an appropriate acid, etc.
  • the used metal or alloy is pulverized and the metal ions are dissolved, and the metal is regenerated by electrolysis using an electrolytic solution containing the target metal ions. This includes those collected.
  • the electrolytic collection includes collecting metal by electrolysis using an electrolytic solution containing a target metal ion through a process of extracting metal ions from a plating waste solution.
  • the energy consumed by electrowinning is the product of the electrolysis voltage and the amount of electricity applied, and the amount of metal obtained at the cathode is proportional to this amount of electricity. Therefore, the electric energy consumption (hereinafter referred to as a basic unit of electric energy) required for electrolytic collection per unit weight of the collected metal becomes smaller as the electrolytic voltage is lower.
  • This electrolytic voltage is the potential difference between the anode and the cathode, and the cathode reaction varies depending on the metal obtained at the cathode, and the cathode potential also varies depending on the type of reaction.
  • the anodic reaction is oxygen generation in the sulfuric acid-based electrolyte and chlorine generation in the chloride-based electrolyte, as exemplified by the type of the electrolyte described above.
  • a sulfuric acid-based electrolytic solution is used for electrolytic collection of metals such as copper, zinc, nickel, and cobalt.
  • the potential of the anode when oxygen is generated varies depending on the material used for the anode. For example, for materials with low and high catalytic activity for oxygen generation, the higher the catalytic activity, the lower the potential of the anode. Therefore, when performing electrowinning using the same electrolyte, it is important and necessary to lower the potential of the anode by using a material with high catalytic activity for the anode in order to reduce the basic unit of power consumption. It is.
  • the anode for electrowinning using a sulfuric acid-based electrolyte contains oxygen that may occur on the anode in addition to oxygen generation (hereinafter referred to as side reaction). Contrary to the generation, low catalytic activity is required.
  • side reaction oxygen generation
  • other metal ions are included in addition to zinc ions, copper ions, cobalt ions, or nickel ions, which are essential components in the electrolyte. There may be.
  • metal ions, manganese ions, lead ions, and the like are known.
  • manganese oxyhydroxide (MnOOH) and manganese dioxide (MnO 2 ) are formed on the anode.
  • Manganese compounds such as, or +2 valent lead ions are oxidized and lead dioxide (PbO 2 ) is deposited on the anode. These reactions occur on the anode at the same time as oxygen generation, which is an anodic reaction of sulfuric acid electrolyte.
  • manganese compounds and lead dioxide have low catalytic activity for oxygen generation and are not high in conductivity.
  • the anode of electrowinning using a sulfuric acid-based electrolyte is 1) high in catalytic activity for oxygen generation, and 2) a secondary oxide that precipitates metal oxide or metal oxyhydroxide on the anode.
  • the anode potential is low, in other words, the overvoltage for the anode reaction is small, and even if the electrowinning is continued, the anode potential does not increase due to the side reaction. 5) Therefore, the electrolysis voltage is low and the electrowinning is continued.
  • typical anodes for electrowinning using a sulfuric acid-based electrolyte include lead electrodes and lead alloy electrodes, as well as platinum group metals, platinum group metal oxides, and mixtures and composites on titanium substrates.
  • An electrode coated with an oxide as a catalyst layer (hereinafter referred to as a coated titanium electrode) is used.
  • a coated titanium electrode is a titanium electrode coated with a catalyst layer containing iridium oxide.
  • the catalyst layer is a mixed oxide of iridium oxide and tantalum oxide, or other mixed oxides.
  • a coated titanium electrode coated with a catalyst layer in which a metal or a metal oxide is further mixed is used.
  • the coated titanium electrode is expanded to other fields of use other than electrowinning, examples of various electrolysis processes using aqueous solutions such as electroplating, electrolytic metal foil production, salt electrolysis, electrolyzed water production, electrolysis functional water production, etc.
  • the coated titanium electrode used for the anode is disclosed in Patent Documents 1 to 7.
  • the anodes disclosed in Patent Documents 1 to 7 include not only oxygen generation but also anodes used for chlorine generation.
  • Patent Document 8 discloses a precursor solution used for producing a coated titanium electrode for electrolytic collection by a thermal decomposition method and a method for preparing the same.
  • Patent Document 9 and Patent Document 10 an electrolytic collection anode including a coated titanium electrode and an electrolytic collection method using the anode.
  • Japanese Patent Laid-Open No. 6-101083 Japanese Patent Laid-Open No. 9-87896 JP 2007-246987 A JP 2008-50675 A JP 2010-5007017 A JP 2011-17084 A JP 2011-503359 A US Patent Application Publication No. 2009/0288958 Japanese Patent No. 4516617 Japanese Patent No. 4516618
  • Patent Document 9 a zinc electrowinning anode in which a catalyst layer containing amorphous iridium oxide is formed on a conductive substrate and a zinc electrowinning method using the same.
  • a zinc electrowinning anode in which a catalyst layer containing amorphous iridium oxide is formed on a conductive substrate and a zinc electrowinning method using the same.
  • the reason why the precipitation of manganese oxyhydroxide or manganese dioxide, which is a side reaction, can be suppressed is that the catalyst layer containing amorphous iridium oxide has a higher catalytic activity for oxygen generation, and therefore oxygen generation than the side reaction occurs. This is because priority is given, so that the current during energization is consumed not by side reaction but by oxygen generation, which is the main reaction. That is, if the anode of electrowinning using sulfuric acid-based electrolyte can increase the catalytic activity for oxygen generation and cause oxygen generation preferentially over other side reactions, side reactions will be suppressed thereby. become.
  • Patent Document 10 discloses a cobalt electrowinning anode in which a catalyst layer containing amorphous ruthenium oxide is formed on a conductive substrate and a cobalt electrowinning method using the anode.
  • a catalyst layer containing amorphous ruthenium oxide is formed on a conductive substrate and a cobalt electrowinning method using the anode.
  • the catalyst layer containing amorphous iridium oxide has a selectively high catalytic activity for oxygen generation at the anode.
  • cobalt electrowinning using a chloride electrolyte it was found that the catalyst layer containing amorphous ruthenium oxide has high catalytic activity selectively for chlorine generation at the anode. .
  • the present invention responds to the above-mentioned demand, and in the electrowinning using a sulfuric acid-based electrolyte, the potential for oxygen generation is lower than that of a lead electrode, a lead alloy electrode, and a coated titanium electrode, and thereby the electrolysis voltage in electrowinning. It can be used as an anode for the electrowinning of various types of metals, and at the same time is used for electrowinning using sulfuric acid based electrolyte.
  • An object of the present invention is to provide an electrolytic extraction method that can reduce the door.
  • the present inventor has found that an anode for electrowinning in which a catalyst layer containing amorphous ruthenium oxide and amorphous tantalum oxide is formed on a conductive substrate, and this The present inventors have found that the above-mentioned problems can be solved by the electrolytic collection method using the above, and have completed the present invention.
  • the anode for electrowinning according to claim 1 of the present invention is an anode for electrowinning used for electrowinning using a sulfuric acid-based electrolyte, and is a catalyst containing amorphous ruthenium oxide and amorphous tantalum oxide.
  • the layer is formed on a conductive substrate.
  • ruthenium Since ruthenium is less than 1/3 the price of iridium, it has a catalytic activity higher than the catalytic activity for oxygen generation in the catalyst layer containing amorphous iridium oxide and amorphous tantalum oxide. It has the effect that it can be achieved with a cheaper catalyst layer containing amorphous ruthenium oxide and amorphous tantalum oxide.
  • valve metals such as titanium, tantalum, zirconium, niobium, tungsten and molybdenum, and valve metals such as titanium-tantalum, titanium-niobium, titanium-palladium and titanium-tantalum-niobium are mainly used. Alloy, an alloy of valve metal and platinum group metal and / or transition metal, or conductive diamond (for example, boron-doped diamond) is preferable, but is not limited thereto.
  • the shape may be various shapes such as a plate, a net, a rod, a sheet, a tube, a line, a porous plate, a porous, a three-dimensional porous body in which true spherical metal particles are combined. Can do.
  • a metal other than the valve metal such as iron or nickel or a conductive ceramic surface coated with the above valve metal, alloy, conductive diamond or the like may be used.
  • the catalyst layer may contain components other than amorphous ruthenium oxide and amorphous tantalum oxide as long as the electrolysis voltage during electrowinning can be reduced. Examples of such other components include, but are not limited to, platinum, iridium, ruthenium, tungsten, tantalum, iridium oxide, titanium oxide, niobium oxide, and the like.
  • An anode for electrowinning according to claim 2 of the present invention is an anode for electrowinning used for electrowinning using a sulfuric acid-based electrolyte, and is a catalyst containing amorphous ruthenium oxide and amorphous tantalum oxide.
  • the electrolysis voltage at the time of electrowinning can be reduced. It has a configuration that can be reduced by 0.05 V or more.
  • the catalytic activity for oxygen generation can be reliably increased, and the electrolysis voltage can be controlled regardless of the type of metal collected at the cathode. It has the effect of obtaining a reducing effect.
  • the anode for electrowinning according to claim 3 of the present invention is an anode for electrowinning used for electrowinning using a sulfuric acid electrolyte, and is a catalyst comprising amorphous ruthenium oxide and amorphous tantalum oxide.
  • the layer is formed on a conductive substrate.
  • Patent Document 6 discloses that, as one of comparative examples, the durability of a coating layer containing ruthenium and tantalum obtained by thermal decomposition at 480 ° C. in a sulfuric acid solution is extremely low. However, such a result is a problem that occurs when crystalline ruthenium oxide is obtained as obtained by performing thermal decomposition at a temperature of at least 350 ° C.
  • electrowinning in which a catalyst layer in a state of being made amorphous in a mixture with amorphous tantalum oxide is used as an electrowinning anode used for electrowinning using a sulfuric acid-based electrolyte. It has been found that the problem of durability against oxygen generation as in 6 does not occur.
  • the anode for electrowinning of the present invention has a current density per electrode area of 0.1 A / cm 2 or less, which is a general electrolysis condition in electrowinning using oxygen generation as an anodic reaction in a sulfuric acid electrolyte. It exhibits excellent durability under electrolytic conditions such as
  • a precursor solution containing ruthenium and tantalum is applied on the conductive substrate, and then a predetermined temperature is applied.
  • Various physical vapor deposition methods such as sputtering and CVD, chemical vapor deposition, and the like can be used in addition to the thermal decomposition method in which the heat treatment is performed. Further, among the methods for producing the anode for electrowinning according to the present invention, a production method by a thermal decomposition method will be further described.
  • ruthenium and tantalum such as inorganic compounds, organic compounds, ions, and complexes
  • a precursor solution containing various forms of ruthenium and tantalum such as inorganic compounds, organic compounds, ions, and complexes
  • the titanium substrate A catalyst layer containing amorphous ruthenium oxide and amorphous tantalum oxide is formed thereon.
  • the molar ratio of ruthenium to tantalum in the butanol solution is 30:70.
  • the thermal decomposition temperature is 280 ° C.
  • a catalyst layer made of a mixture of amorphous ruthenium oxide and amorphous tantalum oxide is formed. Further, even if the precursor solution is applied and then thermally decomposed at 260 ° C., a catalyst layer made of a mixture of amorphous ruthenium oxide and amorphous tantalum oxide is also formed.
  • the molar ratio of ruthenium and tantalum contained in the precursor solution applied to the titanium substrate If the precursor solution contains a metal component other than ruthenium and tantalum, the catalyst layer also depends on the type of the metal component and the molar ratio in all metal components contained in the precursor solution. Whether it contains amorphous ruthenium oxide and amorphous tantalum oxide varies.
  • the range of the thermal decomposition temperature at which a catalyst layer containing ruthenium and amorphous tantalum oxide is obtained tends to be widened.
  • the conditions for forming the catalyst layer containing amorphous ruthenium oxide and amorphous tantalum oxide are not only the molar ratio of such metal components, but also the preparation method and material of the precursor solution, for example, the precursor It also varies depending on the ruthenium and tantalum raw materials used in the preparation of the solution, the type of solvent, and the type and concentration of additives added to promote thermal decomposition.
  • the conditions for forming the catalyst layer containing amorphous ruthenium oxide and amorphous tantalum oxide by the thermal decomposition method are the butanol solvent in the thermal decomposition method described above. Is not limited to the ruthenium and tantalum molar ratio or the range of the thermal decomposition temperature related thereto, the above conditions are just an example, and the method for producing an electrowinning anode of the present invention is described above. In all methods other than those described above, any method can be used as long as a catalyst layer containing amorphous ruthenium oxide and amorphous tantalum oxide can be formed on the conductive substrate.
  • such a method naturally includes a method involving heat treatment in the process of preparing the precursor solution as disclosed in Patent Document 8.
  • a diffraction peak corresponding to ruthenium oxide is not observed by a commonly used X-ray diffraction method, and tantalum oxide. It can be known that a diffraction peak corresponding to is not observed.
  • the invention according to claim 4 is the anode for electrowinning according to any one of claims 1 to 3, wherein the molar ratio of ruthenium to tantalum in the catalyst layer is 30:70. is doing.
  • the molar ratio of ruthenium to tantalum in the catalyst layer is 30:70. is doing.
  • the invention according to claim 5 is the anode for electrowinning according to any one of claims 1 to 4, wherein an intermediate layer is formed between the catalyst layer and the conductive substrate.
  • an intermediate layer is formed between the catalyst layer and the conductive substrate.
  • the catalyst layer containing amorphous ruthenium oxide and amorphous tantalum oxide Compared to the catalyst layer, oxygen generation does not occur preferentially in the intermediate layer even when the electrolyte solution penetrates into the catalyst layer and reaches the intermediate layer. It has a higher durability than that, and thus has an effect of protecting the conductive substrate. At the same time, by coating such a more durable oxide or composite oxide on the conductive substrate, it is possible to suppress the corrosion of the conductive substrate due to the electrolyte as compared with the case where there is no intermediate layer. Has an effect.
  • the intermediate layer has a lower catalytic activity for oxygen generation than the catalyst layer, but sufficiently covers the conductive substrate and has an action of suppressing corrosion of the conductive substrate.
  • It can be formed of an alloy, a carbon-based material such as boron-doped diamond, a metal compound such as an oxide or sulfide, or a composite compound such as a metal composite oxide.
  • a thin film of tantalum, niobium, or the like is preferable when formed of metal
  • tantalum, niobium, tungsten, molybdenum, titanium, platinum, or the like is preferable when formed of an alloy.
  • an intermediate layer using a carbon-based material such as boron-doped diamond has a similar action.
  • the intermediate layer made of the above metal, alloy, or carbon-based material is formed by various methods such as a thermal decomposition method, a sputtering method, a CVD method, various physical vapor deposition methods, a chemical vapor deposition method, a hot dipping method, and an electroplating method. be able to.
  • a thermal decomposition method a sputtering method, a CVD method, various physical vapor deposition methods, a chemical vapor deposition method, a hot dipping method, and an electroplating method.
  • an intermediate layer made of a metal compound such as oxide or sulfide, or a metal composite oxide for example, an intermediate layer made of an oxide containing crystalline iridium oxide is suitable.
  • the catalyst layer is produced by a thermal decomposition method, it is advantageous in terms of simplifying the production process of the anode for electrolytic collection to form an intermediate layer made of an oxide or a composite oxide by the same thermal decomposition method. .
  • the invention according to claim 6 is the anode for electrowinning according to claim 5, wherein the intermediate layer is made of tantalum, niobium, tungsten, molybdenum, titanium, platinum, or an alloy of any of these metals. It has the structure which consists of one of these. With this configuration, in addition to the action obtained in claim 5, (1)
  • the intermediate layer can be formed by various methods such as a thermal decomposition method, a sputtering method, a CVD method and various physical vapor deposition methods, chemical vapor deposition methods, hot dipping methods, and electroplating methods, and is excellent in mass productivity.
  • the invention according to claim 7 is the anode for electrowinning according to claim 5, wherein the intermediate layer includes a crystalline iridium oxide and an amorphous tantalum oxide.
  • the intermediate layer includes a crystalline iridium oxide and an amorphous tantalum oxide.
  • the intermediate layer containing crystalline iridium oxide and amorphous tantalum oxide is applied by a thermal decomposition method in which a precursor solution containing iridium and tantalum is applied on a conductive substrate and then heat-treated at a predetermined temperature. It can be produced by various physical vapor deposition methods such as sputtering and CVD, and chemical vapor deposition.
  • a thermal decomposition method an intermediate layer made of crystalline iridium oxide and amorphous tantalum oxide obtained by thermally decomposing a precursor solution containing iridium and tantalum at a temperature of 400 ° C. to 550 ° C. is suitable. It is.
  • the invention according to claim 8 is the electrolytic collection anode according to any one of claims 1 to 7, wherein the metal to be electrolytically collected is copper, zinc, nickel, cobalt, platinum, gold, It has a configuration that is any one of silver, indium, lead, ruthenium, rhodium, palladium, and iridium. With this configuration, in addition to the action obtained in any one of claims 1 to 7, (1) Since the potential of oxygen generation is low, the electrolysis voltage in electrowinning can be reduced to reduce the power consumption per metal, and it can be used as an anode for electrowinning various types of metals. It has the effect of being excellent in.
  • the electrowinning method according to claim 9 of the present invention is an electrowinning method using a sulfuric acid-based electrolyte solution, and the electrowinning anode according to any one of claims 1 to 8 is used to perform a desired process. It has a configuration for collecting metal. With this configuration, (1) In an electrowinning method using a sulfuric acid-based electrolyte, the potential and electrolysis voltage of the electrowinning anode are low, and it is possible to reduce the power consumption per unit of electrowinning, and the initial cost of the electrowinning anode In addition, the maintenance cost is low, and the cost of the entire electrowinning process can be reduced.
  • the invention according to claim 10 is the electrowinning method according to claim 9, wherein the metal to be electrowinned is copper, zinc, nickel, cobalt, platinum, gold, silver, indium, lead, ruthenium, rhodium. , Palladium, or iridium.
  • the metal to be electrowinned is copper, zinc, nickel, cobalt, platinum, gold, silver, indium, lead, ruthenium, rhodium. , Palladium, or iridium.
  • the present invention has the following effects. 1) In the electrowinning of metals using sulfuric acid-based electrolytes, the potential for oxygen generation at the anode for electrowinning can be lowered compared to the conventional case. It becomes possible to reduce the voltage, and this has the effect of greatly reducing the power consumption basic unit. 2) Since the potential for oxygen generation at the electrowinning anode can be lowered compared to the conventional case, it is possible to suppress various side reactions that may occur on the electrowinning anode. It has an effect that an increase in electrolytic voltage can be suppressed in electrolytic collection during a period. 3) In addition to the above effects, it is not necessary to remove or reduce oxides, oxyhydroxides, and other compounds deposited and accumulated on the anode for electrowinning due to side reactions.
  • the cost of the catalyst layer is reduced by using ruthenium oxide and the thermal decomposition temperature is low as compared with the conventional coated titanium electrode on which the catalyst layer containing iridium oxide is formed. There is an effect that the cost in the formation process of the catalyst layer is also reduced. 9) In addition to the above effects, in the electrowinning of various metals using a sulfuric acid-based electrolytic solution, the manufacturing cost of the entire electrowinning can be greatly reduced.
  • FIG. 4 is a graph of X-ray diffraction images obtained with the electrolytic collection anodes of Example 1, Example 2, and Comparative Example 1.
  • FIG. 4 is a graph of X-ray diffraction images obtained with the electrolytic collection anodes of Example 1, Example 2, and Comparative Example 1.
  • a commercially available titanium plate (length 5 cm, width 1 cm, thickness 1 mm) was immersed in a 10% oxalic acid solution at 90 ° C. for 60 minutes for etching treatment, washed with water, and dried.
  • a butanol (n-C 4 H 9 OH) solution containing 6 vol% concentrated hydrochloric acid the molar ratio of ruthenium and tantalum is 30:70, and the total of ruthenium and tantalum is 50 g / L in terms of metal.
  • This coating solution was applied to the dried titanium plate, dried at 120 ° C. for 10 minutes, and then thermally decomposed in an electric furnace maintained at 260 ° C. for 20 minutes. This application, drying, and thermal decomposition were repeated 5 times in total to produce an electrowinning anode of Example 1 in which a catalyst layer was formed on a titanium plate as a conductive substrate.
  • the electrolytic collection anode of Example 1 was embedded in a polytetrafluoroethylene holder, and the electrode area in contact with the electrolytic solution was regulated to 1 cm 2. Opposed at a distance.
  • electrowinning between the electrowinning anode and a cathode, while electrowinning of zinc by passing one of the electrolysis current density 10 mA / cm 2 or 50 mA / cm 2 in electrode area criteria anode electrowinning, The voltage between the anode and cathode for electrowinning (electrolytic voltage) was measured.
  • the electrolytic solution was 40 ° C.
  • the anode for electrowinning in Example 2 was produced in the same manner as in Example 1 except that the thermal decomposition temperature when forming the catalyst layer was changed from 260 ° C. to 280 ° C.
  • the thermal decomposition temperature when forming the catalyst layer was changed from 260 ° C. to 280 ° C.
  • the structure of the electrowinning anode of Example 2 was analyzed by X-ray diffraction, as shown in FIG. 1, no diffraction peak corresponding to RuO 2 was observed, and a diffraction peak corresponding to Ta 2 O 5 was also observed. I could't.
  • the diffraction peak of Ti was seen, this is based on a titanium plate. That is, in the anode for electrowinning in Example 2, a catalyst layer containing amorphous ruthenium oxide and amorphous tantalum oxide was formed on a titanium plate.
  • the electrolytic collection anode of Example 2 was embedded in a polytetrafluoroethylene holder and the electrode area in contact with the electrolytic solution was regulated to 1 cm 2. Opposed at a distance.
  • electrowinning between the electrowinning anode and a cathode, while electrowinning of zinc by passing one of the electrolysis current density 10 mA / cm 2 or 50 mA / cm 2 in electrode area criteria anode electrowinning, The voltage between the anode and cathode for electrowinning (electrolytic voltage) was measured.
  • the electrolytic solution was 40 ° C.
  • Comparative Example 1 The anode for electrowinning in Comparative Example 1 was produced in the same manner as in Example 1 except that the thermal decomposition temperature when forming the catalyst layer was changed from 260 ° C to 360 ° C.
  • the structure of the electrowinning anode of Comparative Example 1 was analyzed by X-ray diffraction, as shown in FIG. 1, a diffraction peak corresponding to RuO 2 was observed, but a diffraction peak corresponding to Ta 2 O 5 was I was not able to admit.
  • the diffraction peak of Ti was seen, this is based on a titanium plate. That is, a catalyst layer containing crystalline ruthenium oxide and amorphous tantalum oxide was formed on the electrowinning anode of Comparative Example 1.
  • the electrolytic collection anode of Comparative Example 1 was embedded in a polytetrafluoroethylene holder, and the electrode area in contact with the electrolytic solution was regulated to 1 cm 2. Opposed at a distance.
  • electrowinning between the electrowinning anode and a cathode, while electrowinning of zinc by passing one of the electrolysis current density 10 mA / cm 2 or 50 mA / cm 2 in electrode area criteria anode electrowinning, The voltage between the anode and cathode for electrowinning (electrolytic voltage) was measured.
  • the electrolytic solution was 40 ° C.
  • Comparative Example 2 A commercially available titanium plate (length 5 cm, width 1 cm, thickness 1 mm) was immersed in a 10% oxalic acid solution at 90 ° C. for 60 minutes for etching treatment, washed with water, and dried. Next, in a butanol (n-C 4 H 9 OH) solution containing 6 vol% concentrated hydrochloric acid, the molar ratio of iridium and tantalum is 80:20, and the total of iridium and tantalum is 70 g / L in terms of metal.
  • a coating solution was prepared by adding chloroiridium acid hexahydrate (H 2 IrCl 6 .6H 2 O) and tantalum chloride (TaCl 5 ).
  • This coating solution was applied to the dried titanium plate, dried at 120 ° C. for 10 minutes, and then thermally decomposed in an electric furnace maintained at 360 ° C. for 20 minutes. This application, drying, and thermal decomposition were repeated a total of 5 times to produce an electrowinning anode of Comparative Example 2 in which a catalyst layer was formed on a titanium plate as a conductive substrate.
  • the electrolytic collection anode of Comparative Example 2 is embedded in a polytetrafluoroethylene holder and the electrode area in contact with the electrolytic solution is regulated to 1 cm 2. Opposed at a distance.
  • electrowinning between the electrowinning anode and a cathode, while electrowinning of zinc by passing one of the electrolysis current density 10 mA / cm 2 or 50 mA / cm 2 in electrode area criteria anode electrowinning, The voltage between the anode and cathode for electrowinning (electrolytic voltage) was measured.
  • the electrolytic solution was 40 ° C.
  • Table 1 to Table 4 show the voltages between the terminals when electrolytic collection was performed using the electrolytic collection anodes of Example 1, Example 2, Comparative Example 1, and Comparative Example 2 described above.
  • the electrowinning anode of Example 1 in which a catalyst layer containing amorphous ruthenium oxide and amorphous tantalum oxide was formed by thermal decomposition at 260 ° C.
  • the electrolysis voltage was 0 compared to the case of using the anode for electrowinning of Comparative Example 1 in which a catalyst layer containing crystalline ruthenium oxide and amorphous tantalum oxide was formed by pyrolysis at 360 ° C. .17V-0.19V was lower.
  • Example 2 when the anode for electrowinning of Example 1 was used, the electrowinning of Comparative Example 2 in which a catalyst layer containing amorphous iridium oxide and amorphous tantalum oxide was formed.
  • the electrolysis voltage was lower by 0.05V to 0.06V than when the working anode was used. That is, when an electrowinning anode (Example 1) in which a catalyst layer containing amorphous ruthenium oxide and amorphous tantalum oxide is used, crystalline ruthenium oxide and amorphous tantalum oxide are used.
  • the electrolysis voltage was significantly lower than when using the electrowinning anode (Comparative Example 1) on which the catalyst layer was formed, and a catalyst layer containing amorphous iridium oxide and amorphous tantalum oxide was formed.
  • the electrolysis voltage could be further reduced as compared with the case of using the electrowinning anode (Comparative Example 2).
  • the electrolysis voltage was lower by 0.04V to 0.06V than when the working anode was used. That is, when an electrowinning anode (Example 2) in which a catalyst layer containing amorphous ruthenium oxide and amorphous tantalum oxide is used, crystalline ruthenium oxide and amorphous tantalum oxide are used.
  • the electrolysis voltage was significantly lower than when using the electrowinning anode (Comparative Example 1) on which the catalyst layer was formed, and a catalyst layer containing amorphous iridium oxide and amorphous tantalum oxide was formed. The electrolysis voltage could be further reduced as compared with the case of using the electrowinning anode (Comparative Example 2).
  • Example 1 The electrolytic solution in Example 1 was changed to an electrolytic solution composed of 0.60 mol / L CuSO 4 and 0.90 mol / L sulfuric acid, and the other conditions were the same as in Example 1, The voltage between the anode and cathode for electrowinning (electrolytic voltage) was measured.
  • Example 2 The electrolytic solution in Example 2 was changed to an electrolytic solution composed of 0.60 mol / L CuSO 4 and 0.90 mol / L sulfuric acid, and the other conditions were the same as in Example 2, The voltage between the anode and cathode for electrowinning (electrolytic voltage) was measured.
  • Comparative Example 3 The electrolytic solution in Comparative Example 1 was changed to an electrolytic solution composed of 0.60 mol / L CuSO 4 and 0.90 mol / L sulfuric acid, and the other conditions were the same as Comparative Example 1, The voltage between the anode and cathode for electrowinning (electrolytic voltage) was measured.
  • Comparative Example 4 The electrolytic solution in Comparative Example 2 was changed to an electrolytic solution composed of 0.60 mol / L CuSO 4 and 0.90 mol / L sulfuric acid, and the other conditions were the same as Comparative Example 2, The voltage between the anode and cathode for electrowinning (electrolytic voltage) was measured.
  • Table 5 to Table 8 show the voltages between the terminals when electrolytic collection was performed using the electrolytic collection anodes of Example 3, Example 4, Comparative Example 3, and Comparative Example 4 described above.
  • the electrowinning anode of Example 3 in which the catalyst layer containing amorphous ruthenium oxide and amorphous tantalum oxide was formed by thermal decomposition at 260 ° C.
  • the electrolysis voltage was 0 compared to the case of using the anode for electrowinning of Comparative Example 3 in which a catalyst layer containing crystalline ruthenium oxide and amorphous tantalum oxide was formed by thermal decomposition at 360 ° C. .11V-0.16V was lower.
  • Example 6 when the anode for electrowinning of Example 3 was used, the electrowinning of Comparative Example 4 in which a catalyst layer containing amorphous iridium oxide and amorphous tantalum oxide was formed.
  • the electrolysis voltage was lower by 0.05V to 0.07V than when the working anode was used. That is, when an electrowinning anode (Example 3) in which a catalyst layer containing amorphous ruthenium oxide and amorphous tantalum oxide is used, crystalline ruthenium oxide and amorphous tantalum oxide are used.
  • the electrolysis voltage was significantly lower than in the case of using the electrowinning anode (Comparative Example 3) on which the catalyst layer was formed, and a catalyst layer containing amorphous iridium oxide and amorphous tantalum oxide was formed.
  • the electrolysis voltage could be further reduced as compared with the case of using the electrowinning anode (Comparative Example 4).
  • the electrolysis voltage was lower by 0.04V to 0.07V than when the working anode was used. That is, when an electrowinning anode (Example 4) in which a catalyst layer containing amorphous ruthenium oxide and amorphous tantalum oxide is used, crystalline ruthenium oxide and amorphous tantalum oxide are used.
  • the electrolysis voltage was significantly lower than in the case of using the electrowinning anode (Comparative Example 3) on which the catalyst layer was formed, and a catalyst layer containing amorphous iridium oxide and amorphous tantalum oxide was formed. The electrolysis voltage could be further reduced as compared with the case of using the electrowinning anode (Comparative Example 4).
  • Example 1 The electrolytic solution in Example 1 was changed to an electrolytic solution composed of 0.30 mol / L CoSO 4 and 2.0 ⁇ 10 ⁇ 3 mol / L sulfuric acid, and the conditions other than the current density of 10 mA / cm 2 were performed.
  • the terminal voltage (electrolysis voltage) between the anode and cathode for electrowinning was measured while electrowinning cobalt.
  • Example 2 The electrolytic solution in Example 2 was changed to an electrolytic solution composed of 0.30 mol / L CoSO 4 and 2.0 ⁇ 10 ⁇ 3 mol / L sulfuric acid, and the conditions except that the current density was 10 mA / cm 2 were carried out.
  • the terminal voltage (electrolysis voltage) between the anode and cathode for electrolytic collection was measured while performing electrolytic collection of cobalt.
  • Comparative Example 5 The electrolytic solution in Comparative Example 1 was changed to an electrolytic solution composed of 0.30 mol / L CoSO 4 and 2.0 ⁇ 10 ⁇ 3 mol / L sulfuric acid, and the conditions except that the current density was 10 mA / cm 2 were compared. As in Example 1, the terminal voltage (electrolysis voltage) between the anode and cathode for electrowinning was measured while electrowinning cobalt.
  • Comparative Example 6 The electrolytic solution in Comparative Example 2 was changed to an electrolytic solution composed of 0.30 mol / L CoSO 4 and 2.0 ⁇ 10 ⁇ 3 mol / L sulfuric acid, and the conditions except that the current density was 10 mA / cm 2 were compared. As in Example 2, the terminal voltage (electrolysis voltage) between the anode and cathode for electrolytic collection was measured while performing electrolytic collection of cobalt.
  • Table 9 to Table 12 show the voltages between the terminals when electrolytic collection was performed using the electrolytic collection anodes of Example 5, Example 6, Comparative Example 5, and Comparative Example 6 described above.
  • the electrolysis voltage was 0 compared to the case where the anode for electrowinning of Comparative Example 5 in which the catalyst layer containing crystalline ruthenium oxide and amorphous tantalum oxide was formed by pyrolysis at 360 ° C. was used. .05V was low.
  • Example 10 when the anode for electrowinning of Example 5 was used, the electrowinning of Comparative Example 6 in which a catalyst layer containing amorphous iridium oxide and amorphous tantalum oxide was formed.
  • the electrolysis voltage was 0.02 V lower than when the anode was used. That is, when the electrowinning anode (Example 5) in which a catalyst layer containing amorphous ruthenium oxide and amorphous tantalum oxide is used, crystalline ruthenium oxide and amorphous tantalum oxide are used.
  • the electrolytic voltage could be further reduced as compared with the case of using the anode for comparison (Comparative Example 6).
  • the electrolysis voltage was 0.09 V lower than when the anode was used. That is, when an electrowinning anode (Example 6) in which a catalyst layer containing amorphous ruthenium oxide and amorphous tantalum oxide is used, crystalline ruthenium oxide and amorphous tantalum oxide are used.
  • the electrolytic voltage could be further reduced as compared with the case of using the anode for comparison (Comparative Example 6).

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PCT/JP2012/057426 2011-03-25 2012-03-23 電解採取用陽極およびそれを用いた電解採取法 WO2012133136A1 (ja)

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RU2013147642/02A RU2568546C2 (ru) 2011-03-25 2012-03-23 Анод для электровыделения и способ электровыделения с его применением
CN201280016122.9A CN103476970B (zh) 2011-03-25 2012-03-23 电解提取用阳极以及使用该阳极的电解提取法
KR1020137024065A KR101577664B1 (ko) 2011-03-25 2012-03-23 전해 채취용 양극 및 그것을 이용한 전해 채취법
EP12763572.0A EP2690200B1 (en) 2011-03-25 2012-03-23 Anode for electrowinning and electrowinning method using same
CA2831273A CA2831273C (en) 2011-03-25 2012-03-23 Anode for electrowinning and method for electrowinning using same
AU2012234150A AU2012234150B2 (en) 2011-03-25 2012-03-23 Anode for electrowinning and electrowinning method using same
ES12763572.0T ES2557194T3 (es) 2011-03-25 2012-03-23 Ánodo para electroextracción y método de electroextracción que usa el mismo
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JP7273024B2 (ja) * 2018-03-07 2023-05-12 デノラ・ペルメレック株式会社 電解用電極及びその製造方法
JP7341395B2 (ja) * 2019-10-30 2023-09-11 住友金属鉱山株式会社 廃リチウムイオン電池からの銅、ニッケル、コバルトの回収方法
WO2023208026A1 (zh) * 2022-04-28 2023-11-02 中国石油化工股份有限公司 一种过渡金属掺杂的铱基复合催化剂及其制备和应用
CN115466985A (zh) * 2022-09-23 2022-12-13 中国船舶重工集团公司第七二五研究所 一种含非晶氧化铑中间层金属氧化物电极制备方法

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