WO2022038817A1 - Procédé de suppression de réduction de concentration pour composant d'acide peroxysulfurique dans une solution d'acide sulfurique contenant un composant d'acide peroxysulfurique, et dispositif de suppression de réduction de concentration pour composant d'acide peroxysulfurique - Google Patents

Procédé de suppression de réduction de concentration pour composant d'acide peroxysulfurique dans une solution d'acide sulfurique contenant un composant d'acide peroxysulfurique, et dispositif de suppression de réduction de concentration pour composant d'acide peroxysulfurique Download PDF

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WO2022038817A1
WO2022038817A1 PCT/JP2021/010453 JP2021010453W WO2022038817A1 WO 2022038817 A1 WO2022038817 A1 WO 2022038817A1 JP 2021010453 W JP2021010453 W JP 2021010453W WO 2022038817 A1 WO2022038817 A1 WO 2022038817A1
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component
sulfuric acid
acid component
persulfuric acid
persulfuric
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PCT/JP2021/010453
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English (en)
Japanese (ja)
Inventor
一 井芹
晴義 山川
裕都喜 山本
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栗田工業株式会社
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/22—Roughening, e.g. by etching
    • C23C18/24—Roughening, e.g. by etching using acid aqueous 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
    • C25B1/01—Products
    • 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
    • C25B1/01—Products
    • C25B1/28—Per-compounds
    • C25B1/30—Peroxides
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes

Definitions

  • the present invention is a pre-plating treatment performed prior to a plating treatment on a sulfuric acid solution containing an oxidizing substance, particularly a plastic material surface, which is used for surface cleaning and surface modification treatment of various materials such as metal, silicon, glass and plastic.
  • the present invention relates to a method for maintaining the properties of a sulfuric acid solution containing an oxidizing substance used for (resin etching) in a stable state.
  • the present invention also relates to an apparatus for carrying out a method for maintaining the properties of a sulfuric acid solution containing an oxidizing substance in a stable state.
  • a sulfuric acid solution containing a persulfuric acid component such as peroxomonosulfuric acid, peroxomonosulfate, peroxodisulfate, and peroxodisulfate has extremely strong oxidizing power. Therefore, it is used for cleaning and surface modification of various materials such as metal, silicon, glass, and plastic by utilizing this strong oxidizing power.
  • Patent Document 1 a sulfuric acid-containing treatment liquid is circulated and circulated in an electrolytic cell for a metal material to generate a persulfuric component, and aluminum is used in the treatment liquid having an oxidation-reduction potential of +1.5 to +3.5 V.
  • a method for producing a porous film having a step of forming pores in the aluminum film by anodizing the film is described.
  • Patent Document 2 when a contaminant or the like adhering to a silicon wafer or the like is washed and peeled off with a persulfuric acid component solution having a high peeling effect, the persulfuric acid component is regenerated and used for washing while repeatedly using the sulfuric acid solution.
  • a sulfuric acid recycling cleaning system is described.
  • Patent Document 3 describes a method for pre-plating the surface of the ABS-based resin, which treats the ABS-based resin in a solution obtained by electrolyzing sulfuric acid, and describes a treatment tank provided with a constant temperature heater and a circulation pump.
  • a persulfate component solution is generated by electrolyzing the sulfuric acid supplied to the electrolytic cell, which is composed of a circulation system having a continuous electrolytic cell from the piping provided with the electrolytic cell and a piping supplied from the electrolytic cell to the treatment tank.
  • An apparatus for supplying this persulfate component solution to a treatment tank via a pipe is exemplified.
  • a sulfuric acid solution containing a persulfuric acid component can be produced by various methods such as electrolysis of sulfuric acid, mixing of sulfuric acid and hydrogen peroxide, and dissolution of a persulfuric acid component salt in sulfuric acid. Further, in order to maintain the concentration of the persulfuric component as a strong oxidizing agent which is an active ingredient in the solution, the persulfuric component is generated and supplied by the method as described above.
  • the sulfuric acid solution containing the persulfuric acid component can be widely used for surface cleaning and surface modification of various materials, but when impurities are mixed in the solution, the concentration of the active ingredient decreases in a short time. However, the oxidative activity may be lost.
  • impurities include dissolved metal components typified by copper ions, chromium ions, and iron ions.
  • a plating pretreatment resin etching
  • the metal component fixed to the jig for attaching the part to be plated may be brought into the solution by dissolving in the plating pretreatment solution (sulfate solution containing the persulfate component).
  • the persulfuric acid component In a situation where such impurities are present and the concentration of the active ingredient is significantly reduced, in order to maintain the concentration of the active ingredient in the sulfuric acid solution containing the persulfuric acid component, that is, the concentration of the persulfuric acid component, the persulfuric acid component must be used. It is effective to increase the supply speed, but for this purpose, it is necessary to increase the size of the electrolytic device. In addition, in order to increase the supply rate of the persulfuric acid component by the method of adding the persulfuric acid component salt to the sulfuric acid or the method of adding hydrogen peroxide to the sulfuric acid, sulfuric acid, the persulfuric acid component salt, hydrogen peroxide, etc. are used. It is necessary to increase the amount of necessary ingredients used.
  • Patent Document 5 describes a method for treating an etching waste liquid containing ammonium persulfate, sulfuric acid and copper as main components, wherein the waste liquid is a metal selected from the group consisting of platinum group metals.
  • An electrolytic treatment step in which a plated titanium material is used as a pair of parallel anodes, and copper is deposited on the cathode in a current density range of 1.5 to 5.0 A / dm 2 and at a liquid temperature of 34 ° C or lower.
  • a method for treating an etching waste liquid which comprises arranging the cathode plate at a predetermined angle with respect to the pair of parallel anodes. This method relates to a waste liquid treatment method for precipitating and removing copper contained in a solution on a cathode (cathode electrode) by electrolysis of the solution.
  • Japanese Unexamined Patent Publication No. 2016-145381 Japanese Unexamined Patent Publication No. 2006-278689 Japanese Unexamined Patent Publication No. 2019-44229 Japanese Patent No. 6288213 Japanese Patent No. 3254580
  • Patent Document 5 is a technique relating to a method for treating an etching wastewater, and is an object of the present invention to generate and maintain a persulfuric component which is an active ingredient for surface cleaning and surface modification treatment of various materials. There was a problem that it could not be done.
  • the present invention first circulates or stores a sulfuric acid solution having a concentration of 50% by weight or more containing a persulfuric acid component as an oxidizing agent component in a sulfuric acid solution containing the persulfuric acid component. It is a method of suppressing a decrease in the concentration of the persulfuric acid component in the sulfuric acid solution containing the persulfuric acid component by discharging and removing the mixed dissolved metal component from the sulfuric acid solution and generating the persulfuric acid component.
  • Electrolysis in which the electrode and the sulfuric acid solution containing the persulfuric acid component are brought into contact with each other in the electrolytic part including the pole, and the sulfuric acid solution containing the persulfuric acid component is electrolyzed by applying a current to the anode electrode and the cathode electrode.
  • a sulfuric acid solution containing a persulfuric acid component generated at the anode electrode during the step and the electrolytic step is supplied to the circulation or storage system, and a metal component dissolved in the sulfuric acid solution containing the persulfuric acid component at the cathode electrode.
  • Concentration of the persulfuric acid component in a sulfuric acid solution containing a persulfuric acid component which comprises a step of suppressing a decrease in the concentration of the above-mentioned step of suppressing the decrease in the concentration and a step of removing the metal component deposited on the cathode electrode to the outside of the system.
  • a method for suppressing a decrease is provided (Invention 1).
  • the present inventor has a sulfuric acid concentration containing one or more persulfuric acid components selected from peroxomonosulfuric acid, peroxomonosulfuric acid, peroxodisulfuric acid, and peroxodisulfuric acid salt as the oxidizing agent component.
  • a sulfuric acid solution peroxymonosulfuric solution containing a persulfuric component
  • the persulfuric component can be generated at the anode electrode, while at the cathode electrode.
  • the anode electrode and the cathode electrode used in the electrolytic part are electrodes whose contact surface is coated with conductive diamond, and the liquid temperature of the sulfuric acid solution containing a persulfuric acid component in the contact step is set.
  • the temperature is preferably 30 ° C. or higher (Invention 2).
  • the anode electrode and the cathode electrode are used as electrodes whose contact surface is covered with conductive diamond, and the temperature of the sulfuric acid solution containing the persulfate component is 30 ° C. or higher. It is possible to suppress the wear of the anode electrode and the cathode electrode while generating the persulfate component at the electrode and the precipitation of the dissolved metal component at the cathode electrode.
  • the current densities at the anode electrode and the cathode electrode in the electrolysis step are 1 to 50 A / dm 2 (Invention 3).
  • invention 3 by setting the current densities at the anode electrode and the cathode electrode to 1 to 50 A / dm 2 , the persulfate component is generated at the anode electrode and the dissolved metal component is deposited at the cathode electrode. While doing so, it is possible to suppress wear of the anode electrode and the cathode electrode.
  • an index of the concentration of the persulfuric acid component or the concentration of the persulfuric acid component in the sulfuric acid solution containing the persulfuric acid component is preferable to control the amount of current energized to the anode electrode and the cathode electrode of the electrolytic part according to the measurement result of the oxidizing power and / or the measurement result of the metal ion concentration in the sulfuric acid solution containing the persulfuric acid component.
  • the amount of current energized to the anode electrode and the cathode electrode is controlled according to the measurement results of each factor such as the concentration of the persulfuric acid component and the concentration of the dissolved metal component.
  • the concentration of the persulfuric acid component can be maintained at a suitable level, and the precipitation of metal can be set as a suitable condition.
  • the dissolved metal component discharged from the sulfuric acid solution containing the persulfuric acid component in the metal component removing step is used.
  • a metal having a standard electrode potential noble than hydrogen is used.
  • a metal having a standard electrode potential nobler than hydrogen is efficiently reduced by a reaction at the cathode electrode during electrolysis, and is therefore suitable for precipitation and removal at the cathode electrode. Is.
  • the present invention secondly comprises a system in which a sulfuric acid solution having a concentration of 50% by weight or more containing a persulfuric acid component as an oxidizing agent component is circulated or stored, and the dissolved metal component mixed in the sulfuric acid solution is contained in the sulfuric acid solution. It is a device that suppresses a decrease in the concentration of the persulfuric acid component in the sulfuric acid solution containing the persulfuric acid component by discharging and removing it from the persulfuric acid component, and circulates or circulates the sulfuric acid solution containing the persulfuric acid component.
  • An electrolytic unit provided with an anode electrode and a cathode electrode for electrolyzing a sulfuric acid solution containing the persulfuric acid component of the storage system, a power supply device for supplying a current required for electrolysis to the anode electrode and the cathode electrode, and a power supply device.
  • a supply mechanism that supplies the sulfuric acid solution containing the persulfuric acid component generated at the anode electrode to the system that circulates or stores the sulfuric acid solution containing the persulfate component, and discharges / removes the metal component precipitated at the cathode electrode to the outside of the system.
  • a device for suppressing a decrease in the concentration of a persulfuric acid component in a sulfuric acid solution containing a persulfuric acid component which is provided with a removal mechanism for removing the persulfuric acid component (Invention 6).
  • the concentration of sulfuric acid in the electrode portion containing one or more persulfuric acid components selected from peroxomonosulfuric acid, peroxomonosulfuric acid, peroxodisulfuric acid, and peroxodisulfuric acid salt as the oxidizing agent component is performed by performing electrolytic treatment of 50% by weight or more of a sulfuric acid solution (a sulfuric acid solution containing a persulfuric acid component) in the electrolytic part under appropriate conditions, the persulfuric acid component can be generated at the anode electrode, while the persulfuric acid component can be produced at the cathode electrode.
  • a dissolved metal component that promotes a decrease in the concentration of the persulfuric component in the sulfuric acid solution is deposited. Therefore, the sulfuric acid solution containing the persulfuric acid component generated at the anode electrode by the supply mechanism is supplied to the system that circulates or stores the sulfuric acid solution containing the persulfuric acid component, and the metal component precipitated at the cathode electrode is outside the system by the removal mechanism. By discharging and removing the persulfuric acid component, it is possible to suppress a decrease in the concentration of the dissolved metal component in the sulfuric acid solution containing the persulfuric acid component.
  • the electrolytic unit comprises an open type electrolytic reaction tank or a closed type electrolytic cell provided with an anode electrode and a cathode electrode, and the supply mechanism circulates a sulfuric acid solution containing the persulfate component.
  • the supply mechanism circulates a sulfuric acid solution containing the persulfate component.
  • it has a liquid feeding pipe and a liquid feeding mechanism for supplying a sulfuric acid solution containing a persulfate component from the stored system to the electrolytic part, and the removing mechanism removes the metal component deposited at the cathode electrode of the electrolytic part outside the system. It is preferable to provide a discharge flow path for discharging to (Invention 7).
  • the sulfuric acid solution containing the persulfuric acid component generated at the anode electrode is circulated or stored in the liquid feed pipe and the liquid feed mechanism of the supply mechanism to circulate or store the sulfuric acid solution containing the persulfuric acid component.
  • the metal component deposited at the cathode electrode can be discharged to the outside of the system from the discharge flow path of the removal mechanism.
  • the metal component as a solid deposited at the cathode electrode can be separated and removed in the discharge flow path.
  • invention 9 it is preferable to provide a temperature controlling means for controlling the temperature of the sulfuric acid solution containing the persulfuric acid component in the electrolytic section (invention 9).
  • the electrode is worn due to the temperature of the sulfuric acid solution containing the persulfuric acid component in contact with the anode electrode and the cathode electrode, the persulfuric acid component is generated, and the dissolved metal component is precipitated at the cathode electrode. Since they are different, these can be optimized by controlling the temperature of the sulfuric acid solution containing the persulfuric acid component by the temperature adjusting means.
  • a means for measuring the concentration of the persulfuric acid component in the sulfuric acid solution containing the sulfuric acid component or an index of the concentration of the persulfuric acid component in the system for circulating or storing the sulfuric acid solution containing the persulfuric acid component It is preferable to have a means for measuring the oxidizing power and / or a means for measuring the metal ion concentration in the sulfuric acid solution containing the persulfuric acid component (Invention 10).
  • the concentration of the persulfuric acid component and the metal ion concentration in the sulfuric acid solution containing the persulfuric acid component are measured according to the measurement results.
  • the concentration of the persulfuric acid component is maintained at an appropriate level and the precipitation of metal is a suitable condition. can do.
  • the anode electrode and the cathode electrode used in the electrolytic part are electrodes whose wetted surface is coated with conductive diamond (invention 11).
  • the electrode whose wetted surface is coated with conductive diamond is excellent in production efficiency and durability of the electrode, and is suitable for electrolysis of a sulfuric acid solution containing a persulfuric acid component.
  • a sulfuric acid solution containing a persulfuric component as an oxidizing agent component in a system for circulating or storing a sulfuric acid solution containing a persulfuric component Is electrolyzed to generate a persulfuric component generated at the anode electrode, which is supplied to a system for circulating or storing a sulfuric acid solution containing the persulfuric component, and the dissolved metal precipitated at the cathode electrode is persulfurized.
  • Cu 2+ copper ion
  • the sulfuric acid solution containing the persulfuric acid component to be treated contains one or more persulfuric acid components selected from peroxomonosulfuric acid, peroxomonosulfuric acid, peroxodisulfate, and peroxodisulfate as the oxidizing agent component. It is a sulfuric acid solution containing. These persulfuric acid components may be contained alone or may contain two or more kinds.
  • the sulfuric acid solution containing the persulfuric acid component is, for example, a sulfuric acid solution (electrolytic sulfuric acid solution) obtained by electrolyzing a sulfuric acid-containing solution to generate a persulfuric acid component, or a persulfuric acid component by adding hydrogen peroxide to the sulfuric acid.
  • the generated solution or the like can be used, and in particular, it can be suitably applied to an electrolytic sulfuric acid solution.
  • the sulfuric acid solution containing the persulfuric acid component preferably has a sulfuric acid concentration of 50% by weight or more, and in the case of electrolytic sulfuric acid, it is preferably 60 to 87% by weight, particularly 70 to 83% by weight.
  • the persulfuric acid concentration in the initial state is 2 g / L or more, particularly 3 to 20 g / L, although it depends on the intended use.
  • the impurities that promote the decrease in the concentration of the oxidant mixed in the sulfuric acid solution containing the persulfuric acid component as described above are not limited as long as they are deposited on the cathode electrode by the electrolytic operation, but they are higher than the standard electrode potential of hydrogen.
  • Noble metal components are suitable. Specifically, since copper ions tend to cause a decrease in the oxidizing agent component, it is desirable to remove it.
  • the concentration in the sulfuric acid solution containing the persulfuric acid component of the impurity that promotes the decrease in the concentration of the oxidizing agent as described above is about 5000 mg / L or less, particularly about 3000 to 1 mg / L. If the impurity concentration exceeds 5000 mg / L, there are too many impurities and it is difficult to remove them.
  • FIG. 1 shows a device for suppressing a decrease in the concentration of a persulfuric acid component in a sulfuric acid solution containing a persulfuric acid component according to the first embodiment of the present invention.
  • the device 1 for suppressing a decrease in the concentration of the persulfuric acid component is a storage tank 2 as a system for storing and circulating a sulfuric acid solution 3 containing a persulfuric acid component, and a temperature control mechanism arranged in the storage tank 2.
  • a heater 4 is provided.
  • the storage tank 2 is provided with a feed pipe 5 for a treatment liquid (sulfuric acid solution 3) that exits the bottom of the storage tank 2 and communicates with the electrolytic cell 8 as an electrolytic cell, and is connected to the electrolytic cell 8.
  • a circulation flow path is formed by communicating the liquid return pipe 11 with the storage tank 2.
  • the feed pipe 5 is provided with a circulation pump 6 as a liquid feed mechanism and a heat exchanger 7 for cooling as a temperature control means in order from the base end side of the storage tank 2. Further, a DC power supply 9 is connected to the electrolytic cell 8 via a current-carrying conductor wire 10. In the electrolytic cell 8, an anode pole 8A and a cathode pole 8B whose wetted surface is covered with conductive diamond are provided, respectively. Further, the return pipe 11 is provided with a filter 12.
  • the processing liquid feed pipe 5 and the return pipe 11 are provided with an inlet valve 13 and an outlet valve 14 of the electrolytic cell 8 immediately before and after the electrolytic cell 8, respectively.
  • a metal component discharge pipe 15 as a discharge flow path provided with a valve 16 is connected to the electrolytic cell 8 side of the inlet valve 13 of the feed pipe 5, while the outlet valve 14 of the return pipe 11 of the processing liquid is connected.
  • An air suction pipe 17 having a valve 18 and open to the atmosphere is connected to the electrolytic cell 8 side, and the metal component discharge pipe 15 and the air suction pipe 17 constitute a mechanism for removing metal components. ..
  • the storage tank 2 is provided with a means for measuring the oxidizing power and a means for measuring the metal ion concentration, which are indicators of the concentration of the persulfuric acid component in the sulfuric acid solution containing the persulfuric acid component (not shown) or the concentration of the persulfuric acid component.
  • the means for measuring the concentration of the persulfuric component and the like and the means for measuring the metal ion concentration are not particularly limited as long as they can measure correct values and do not interfere with the implementation of the method of the present invention.
  • the method of measuring online and the method of measuring offline are both applicable.
  • an absorptiometric method As a method for measuring the concentration of the persulfuric component or the oxidizing power as an index thereof, an absorptiometric method, a redox titration method, a Raman spectroscopy, a polarograph method, a potential measurement method and the like are exemplified. Further, examples of the method for measuring the concentration of the dissolved metal component include an absorptiometry method, a fluorescence hardness method, a titration method, an ICP emission analysis method, an atomic absorption method, and a method using a concentration analysis test paper.
  • a pre-plating treatment is performed when a system for storing and circulating a sulfuric acid solution 3 containing a persulfuric acid component by electrolytic treatment is plated on an ABS resin molded body as a plastic member.
  • the sulfuric acid solution 3 containing the persulfuric acid component filled in the storage tank 2 is heated to about 50 to 80 ° C. by the heater 4.
  • the temperature of the sulfuric acid solution 3 containing the persulfuric acid component may be adjusted by controlling the heater 4 with a temperature sensor (not shown) provided in the storage tank 2.
  • the etching process can be performed by immersing the resin molded body in the storage tank 2 and taking out the resin molded body after a predetermined time has elapsed. This etching process will be repeated.
  • the metal component when the metal component is dissolved in the sulfuric acid solution 3 containing the persulfuric acid component by heating this etching solution and repeating the etching process, it is an oxidizing agent. It was found that the concentration of sulfuric acid decreased, but at the same time, the dissolved metal component was precipitated at the cathode electrode.
  • electrolysis is performed when the electrode is reversed by the repolarization operation during electrolysis or when the device is stopped.
  • the metal component previously deposited on the cathode electrode is redissolved in the sulfuric acid solution 3 containing the persulfuric acid component as an ionic state.
  • the dissolved metal component in the sulfuric acid solution 3 containing the persulfuric acid component continues to remain in the circulation system of the sulfuric acid solution 3 containing the persulfuric acid component, although the concentration varies, and the concentration of the active component decreases. Will continue to promote.
  • the inlet valve 13 and the outlet valve 14 are opened, and the circulation pump 6 is driven in a state where the valve 16 of the metal component discharge pipe 15 and the valve 18 of the air suction pipe 17 are closed.
  • the sulfuric acid solution 3 containing the persulfate component is supplied to the electrolytic cell 8 from the bottom of the storage tank 2 via the feed pipe 5 to perform the electrolytic treatment.
  • the sulfuric acid solution 3 containing the persulfuric acid component is temperature-controlled by the heat exchanger 7 to a predetermined temperature.
  • peroxodisulfuric acid is produced at the anode electrode 8A of the electrolytic cell 8
  • peroxodisulfuric acid is produced from the peroxodisulfuric acid by an equilibrium reaction. It also produces hydrogen peroxide. Therefore, by electrolyzing sulfuric acid, a persulfuric acid component such as peroxodisulfuric acid and peroxomonosulfuric acid and an oxidizing agent component such as hydrogen peroxide are generated in the electrolytic solution of sulfuric acid, and the sulfuric acid solution 3 containing the persulfuric acid component is produced. Persulfuric acid component increases.
  • the sulfuric acid solution 3 containing the persulfuric acid component with the increased persulfuric acid component is returned from the return pipe 11 to the storage tank 2.
  • the solid impurities contained in the sulfuric acid solution 3 containing the persulfuric acid component are removed by the filter 12. In this way, the decrease in the concentration of the sulfuric acid solution 3 containing the persulfuric acid component in the storage tank 2 can be compensated.
  • the liquid temperature of the sulfuric acid solution 3 containing the persulfate component in contact with the anode electrode 8A and the cathode electrode 8B causes the persulfate component to be generated at the anode electrode 8A, and the precipitation of the dissolved metal component at the cathode electrode 8B is hindered.
  • the temperature is not high, but when the electrolytic treatment is performed at a low temperature, the anode electrode 8A and the cathode electrode 8B whose wetted surface is covered with conductive diamond are severely worn, so that the life of the electrode is extended. From the viewpoint of the above, it is preferable to control the temperature to 30 ° C. or higher.
  • the current density in the electrolytic cell 8 at the time of electrolysis of the sulfuric acid solution 3 containing the persulfuric acid component is such that the persulfuric acid component is generated at the anode electrode 8A and the precipitation of the dissolved metal component at the cathode electrode 8B is not hindered.
  • the range is set to 1 to 50 A / dm 2 from the viewpoint of efficiently suppressing a decrease in the concentration of persulfuric acid, which is an active ingredient, and preventing wear of the anode pole 8A and the cathode pole 8B. Is preferable.
  • the operating conditions of the electrolytic cell 8 as described above are the measurement result of the persulfate component concentration by the persulfate component concentration measuring means provided in the storage tank 2, and the measurement result of the metal ion concentration by the metal ion concentration measuring means. It is preferable to control the amount of current energized in the anode pole 8A and the cathode pole 8B according to the above.
  • the metal component discharge pipe 15 When opened, the metal component discharge pipe 15 is arranged under the electrolytic cell 8, so that the sulfuric acid solution 3 containing the persulfate component remaining in the electrolytic cell 8 is discharged from the metal component discharge pipe 15 to the outside of the system by its own weight. It can be discharged as a liquid. As a result, the concentration of the dissolved metal component in the sulfuric acid solution 3 containing the persulfuric acid component can be reduced, and the effect of suppressing the decrease in the concentration of the persulfuric acid component can be obtained.
  • the electrolytic cell 8 is turned and energized for a short time so as to reverse the anode pole 8A and the cathode pole 8B, and the metal component deposited on the cathode pole 8B (anode pole after turning) is quickly discharged. It may be redissolved in the solution in the electrolytic cell 8 and discharged / removed in the same manner.
  • the persulfate component remaining in the electrolytic cell 8 is contained by opening the valve 16 of the metal component discharge pipe 15 and the valve 18 of the air suction pipe 17 with the sulfuric acid solution 3 containing the persulfate component in the electrolytic cell 8.
  • a cleaning liquid having excellent metal solubility is supplied into the electrolytic cell 8 by a pump or the like separately provided in the electrolytic cell 8, and the cathode electrode of the electrolytic cell 8 is supplied.
  • the metal component deposited on 8B may be promptly made into a solution in the electrolytic cell 8 and discharged / removed in the same manner.
  • the electrolytic cell 8 may be redirected and energized for a short time so as to reverse the anode pole 8A and the cathode pole 8B.
  • FIG. 2 shows a device for suppressing a decrease in the concentration of a persulfuric acid component in a sulfuric acid solution containing a persulfuric acid component according to the second embodiment of the present invention.
  • the device 21 for suppressing a decrease in the concentration of the persulfuric acid component is a storage tank 22 as a system for storing and circulating a sulfuric acid solution 23 containing a persulfuric acid component, and a temperature control mechanism arranged under the storage tank 22.
  • the heater 24 is provided.
  • a treatment liquid stirring mechanism 22A is arranged on the bottom surface of the storage tank 22, and an electrolytic electrode 25 as an electrolytic part having an anode electrode 25A and a cathode electrode 25B whose wetted surface is covered with conductive diamond. Is suspended and is directly immersed in a sulfuric acid solution 23 containing a persulfuric acid component.
  • a DC power supply device 26 is connected to the electrolytic electrode 25 via a current conducting wire 27.
  • the cleaning tank 28 of the electrolytic electrode 25 filled with the electrode cleaning liquid 29 having excellent metal solubility is provided outside the storage tank 22, and the electrolytic electrode 25 may be manual or automatic. It is possible to transfer between the storage tank 22 and the cleaning tank 28 by an arbitrary moving mechanism 30.
  • the sulfuric acid solution 23 containing the persulfuric acid component filled in the storage tank 22 is heated to about 50 to 80 ° C. by the heater 24. Then, the etching process can be performed by immersing the resin molded body in the storage tank 22 and taking out the resin molded body after a predetermined time has elapsed. At this time, if the metal component is dissolved in the sulfuric acid solution 3 containing the persulfuric acid component, the concentration of the persulfuric acid, which is an oxidizing agent, decreases. It can be replenished by producing a sulfuric acid component.
  • the conditions and control of the electrolysis treatment by the electrolysis electrode 25 in the storage tank 22 may be the same as those in the first embodiment described above.
  • the electrolysis treatment is stopped and the electrolysis electrode 30 is used by the moving mechanism 30.
  • the electrolysis electrode 30 is used by the moving mechanism 30.
  • the electrode 25 for electrolysis was turned and energized for a short time so as to reverse the anode pole 25A and the cathode pole 25B, and the metal component deposited on the cathode pole 25B (anode pole after turning).
  • the electrode cleaning liquid 29 of the cleaning tank 28 may be discharged to the outside of the system.
  • the precipitated metal component may be physically peeled off from the electrode and removed as long as the cathode electrode 25B is not damaged.
  • a filter for separating and removing the deposited metal component may be provided in the metal component discharging pipe 15, and the metal component may be separated and removed in the metal component discharging pipe 15 as a solid deposited at the cathode electrode. ..
  • the electrolysis treatment and the regeneration may be sequentially performed by using a plurality of electrolysis electrodes 25, whereby the treatment in the storage tank 22 may be continuously possible.
  • the sulfuric acid solution 3 containing the initial persulfuric acid component is not limited to the one obtained by electrolyzing sulfuric acid, but may be a solution obtained by adding hydrogen peroxide to sulfuric acid, or may be a combination of both.
  • Examples 1 to 8 and Comparative Examples 1 to 3 Using the device 21 for suppressing the decrease in the concentration of the persulfuric acid component having the configuration shown in FIG. 2, a sulfuric acid solution 23 (capacity 200 mL: hereinafter referred to as a test solution) containing copper ions and the persulfuric acid component is held in the storage tank 22 for electrolysis. Electrolysis was continued for 1 hour while producing a persulfuric acid component at the anode electrode 25A of the electrode 25. As the test solution, copper sulfate / pentahydrate was dissolved in sulfuric acid solutions of various concentrations as shown in Table 1 so as to have various dissolved copper concentrations shown in Table 1, and the test solution was heated to the temperature shown in Table 1.
  • the anode electrode 25A and the cathode electrode 25B each having an electrode area of 20 cm 2 and whose wetted surface is covered with conductive diamond, are immersed in the test solution, and the DC power supply device 26 is used to obtain a current density of 5 A / dm. A current was applied to each electrode so as to be 2 .
  • the test liquid was stirred using a stirring mechanism and controlled to a predetermined liquid temperature by the heater 24.
  • Example 9 and Comparative Example 4 A test solution having the same composition as that of Example 1 was prepared, and the electrolysis operation was carried out for 1 hour under the same temperature and electrolysis conditions as in Example 1. After the completion of electrolysis, the electrode 25 for electrolysis was pulled up from the test solution and washed to remove the copper component precipitated at the cathode electrode 25B. The electrode 25 for electrolysis was immersed in the test solution again, and the electrolysis operation was performed for 1 hour under the same electrolysis conditions. This operation was repeated until the total electrolysis time was 24 hours. Then, the test solution was collected in a closed container and stored at rest for 20 days under the condition of 40 ° C. to completely decompose the persulfuric acid component in the test solution.
  • test solution 200 mL
  • test solution 200 mL
  • test solution 200 mL
  • a small amount of 35% hydrogen peroxide was added and mixed with the test solution so that the concentration of the persulfuric component was equivalent to 0.5 g / L, and the concentration (initial concentration) of the persulfuric component was immediately measured.
  • concentration of the persulfuric acid component in the test solution was measured. The measurement results were applied to Eq. (2) to calculate the rate of decrease in the concentration of the persulfuric acid component.
  • Persulfuric acid component concentration reduction rate (%) (1-PF / PI) x 100 ... (2) (In the formula, PI is the concentration of the persulfuric acid component at the start of the test, and PF is the concentration of the persulfuric acid component at the end of the test.)
  • Comparative Example 4 a test solution was prepared in the same manner except that electrolysis was not performed in Example 9. Using this test solution, the rate of decrease in the concentration of the persulfuric acid component was calculated in the same manner.
  • the concentration decrease rate of the persulfuric acid component was 92% in Comparative Example 4, whereas the concentration decrease rate of the persulfuric acid component was 18% in Example 9. rice field.
  • the concentration of the dissolved copper component in the test solution can be reduced, and the persulfuric acid component can be reduced. It was confirmed that the decrease in the concentration of the persulfuric acid component (oxidizing agent), which is the active component in the sulfuric acid solution containing the above, was reduced.

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Abstract

Un dispositif de suppression de réduction de concentration (1) selon la présente invention comprend un réservoir de stockage (2) pour une solution d'acide sulfurique (3) qui contient un composant d'acide peroxysulfurique, et un dispositif de chauffage (4) qui est disposé dans le réservoir de stockage (2). Un tuyau d'alimentation (5) qui sort du fond du réservoir de stockage (2) et qui est en communication avec une cellule électrolytique (8) est prévu, et un tuyau de retour (11) qui est relié à la cellule électrolytique (8) est en communication avec le réservoir de stockage (2), formant ainsi un trajet d'écoulement circulatoire. De plus, une anode (8A) et une cathode (8B) qui ont chacune une surface de contact liquide revêtue de diamant conducteur sont respectivement situées dans la cellule électrolytique (8). Un tuyau d'évacuation de composant métallique (15) comprenant une soupape (16) est relié au tuyau d'alimentation (5) plus près de la cellule électrolytique (8) par rapport à une soupape côté entrée (13) du tuyau d'alimentation (5) en liquide traité, et un tuyau d'admission d'air (17) ayant une soupape (18) est relié au tuyau de retour (11) plus près de la cellule électrolytique (8) par rapport à une soupape côté sortie (14) du tuyau de retour (11). À l'aide d'un tel dispositif de suppression de réduction de concentration (1), il est possible de supprimer la réduction de la concentration d'un composant d'acide peroxysulfurique qui est le composant actif d'une solution d'acide sulfurique contenant le composant d'acide peroxysulfurique.
PCT/JP2021/010453 2020-08-19 2021-03-15 Procédé de suppression de réduction de concentration pour composant d'acide peroxysulfurique dans une solution d'acide sulfurique contenant un composant d'acide peroxysulfurique, et dispositif de suppression de réduction de concentration pour composant d'acide peroxysulfurique WO2022038817A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004351363A (ja) * 2003-05-30 2004-12-16 Kurita Water Ind Ltd 金属イオンを含む有機化合物含有水の処理方法及び処理装置
JP2011127166A (ja) * 2009-12-16 2011-06-30 Toshiba Corp エッチング処理方法、微細構造体の製造方法、およびエッチング処理装置
JP2012169562A (ja) * 2011-02-16 2012-09-06 Kurita Water Ind Ltd 窒化物半導体材料の表面処理方法および表面処理システム
JP2018184626A (ja) * 2017-04-25 2018-11-22 栗田工業株式会社 洗浄システム

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004351363A (ja) * 2003-05-30 2004-12-16 Kurita Water Ind Ltd 金属イオンを含む有機化合物含有水の処理方法及び処理装置
JP2011127166A (ja) * 2009-12-16 2011-06-30 Toshiba Corp エッチング処理方法、微細構造体の製造方法、およびエッチング処理装置
JP2012169562A (ja) * 2011-02-16 2012-09-06 Kurita Water Ind Ltd 窒化物半導体材料の表面処理方法および表面処理システム
JP2018184626A (ja) * 2017-04-25 2018-11-22 栗田工業株式会社 洗浄システム

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