WO2021234978A1 - Procédé de démarrage pour système de fabrication de solution électrolytique d'acide sulfurique - Google Patents

Procédé de démarrage pour système de fabrication de solution électrolytique d'acide sulfurique Download PDF

Info

Publication number
WO2021234978A1
WO2021234978A1 PCT/JP2020/034959 JP2020034959W WO2021234978A1 WO 2021234978 A1 WO2021234978 A1 WO 2021234978A1 JP 2020034959 W JP2020034959 W JP 2020034959W WO 2021234978 A1 WO2021234978 A1 WO 2021234978A1
Authority
WO
WIPO (PCT)
Prior art keywords
sulfuric acid
solution
electrolytic
acid solution
concentration
Prior art date
Application number
PCT/JP2020/034959
Other languages
English (en)
Japanese (ja)
Inventor
一 井芹
晴義 山川
裕都喜 山本
Original Assignee
栗田工業株式会社
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.)
Filing date
Publication date
Application filed by 栗田工業株式会社 filed Critical 栗田工業株式会社
Priority to CN202080098615.6A priority Critical patent/CN115298360A/zh
Priority to US17/912,910 priority patent/US20230079765A1/en
Priority to EP20936154.2A priority patent/EP4155434A1/fr
Publication of WO2021234978A1 publication Critical patent/WO2021234978A1/fr

Links

Images

Classifications

    • 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
    • C25B1/22—Inorganic acids
    • 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
    • C25B1/29—Persulfates
    • 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
    • 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
    • C25B15/02—Process control or regulation
    • C25B15/021—Process control or regulation of heating or cooling
    • 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
    • C25B15/02—Process control or regulation
    • C25B15/023—Measuring, analysing or testing during electrolytic production
    • C25B15/025—Measuring, analysing or testing during electrolytic production of electrolyte parameters
    • C25B15/027—Temperature
    • 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
    • C25B15/087—Recycling of electrolyte to electrochemical cell
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/13—Single electrolytic cells with circulation of an electrolyte

Definitions

  • the present invention relates to a method for setting up a system for producing an electrolytic sulfuric acid solution suitable for cleaning and modifying the surface of various materials, particularly an etching treatment performed prior to a plating treatment on the surface of a plastic material.
  • a sulfuric acid solution containing a persulfuric acid component such as peroxomonosulfuric acid or peroxodisulfuric acid has extremely strong oxidizing properties. Utilizing this strong oxidizing property, a sulfuric acid solution containing a persulfuric acid component is used for cleaning and surface modification of various materials such as metals, silicon, glass, and plastics.
  • a sulfuric acid solution containing a persulfuric acid component can be produced by electrolyzing a solution mainly containing a sulfuric acid component.
  • a system for producing an oxidizing solution containing a persulfate component (hereinafter, may be referred to as an electrolytic sulfuric acid solution) produced by electrolyzing this solution mainly composed of a sulfuric acid component stores, for example, an electrolytic sulfuric acid solution.
  • Patent Document 1 describes a technique for producing electrolytic sulfuric acid for application to an etching treatment of a resin surface performed for plating the surface of a plastic material. ..
  • an electrolytic sulfuric acid solution obtained by electrolyzing sulfuric acid so that the sulfuric acid concentration is 60 to 87 wt%, the solution temperature is 50 to 80 ° C., and the persulfuric acid concentration is 3 g / L or more.
  • Patent Document 1 is filled with sulfuric acid having a predetermined concentration in an initial state, and peroxo is obtained by electrolyzing sulfuric acid by applying a predetermined current from a DC power supply unit to the anode and cathode of this solution. It is described to produce a persulfuric acid solution such as disulfuric acid. Further, Patent Document 1 describes as a comparative example an example in which the surface of an ABS resin is etched using a mixed solution of sulfuric acid and hydrogen peroxide instead of an electrolytic sulfuric acid solution. In this comparative example, a plating film is provided. It is stated that although it is formed, there is a problem with the long-term stability of the treatment due to the consumption of hydrogen peroxide.
  • the system for producing the electrolytic sulfuric acid solution is an active component in the electrolytic sulfuric acid solution at the time of starting up the system for the first time after completion, at the time of starting up the system after exchanging the electrolytic sulfuric acid solution, or by stopping the operation of the system.
  • the system is restarted when the persulfuric acid concentration drops, the surface of various materials cannot be immediately cleaned or reformed.
  • the sulfuric acid solution itself or the electrolytic sulfuric acid solution having a low persulfuric acid concentration is used until the persulfuric acid concentration reaches a predetermined value according to the purpose. It is necessary to operate the electrolytic cell to continue electrolysis. Therefore, there is a problem that energy is required to obtain an electrolytic sulfuric acid solution having a persulfuric acid concentration required for cleaning and reforming the surface of various materials, and the system cannot be started up in a short time.
  • the present invention has been made in view of the above problems, and can complete the start-up of a system for producing an electrolytic sulfuric acid solution containing a persulfuric acid component produced by electrolyzing sulfuric acid in a short time and reduce energy consumption. It is an object of the present invention to provide a method for setting up an electrolytic sulfuric acid solution production system capable of capable.
  • the present invention is a method for setting up a system for producing an oxidizing solution containing a persulfate component, which is produced by electrolyzing a solution mainly containing a sulfuric acid component, in the system.
  • a hydrogen peroxide solution is added to all or part of the existing sulfuric acid component-based solution to adjust the oxidizing power of the sulfuric acid component-based solution to an enhanced state, and the solution is supplied to the electrolytic cell.
  • a method for setting up an electrolytic sulfuric acid solution manufacturing system that performs electrolysis (Invention 1).
  • the system is started up in the system at the first operation after the completion of the system, after the exchange of the oxidizing solution containing the persulfuric component in the system, and then the operation of the system is stopped. It is preferable that the system is operated after the concentration of the persulfuric component in the oxidizing solution stored in the system has decreased (Invention 2).
  • the system at the time of starting up the production system of the oxidizing solution containing the persulfuric acid component produced by electrolyzing the solution mainly containing the sulfuric acid component, that is, the first time after the completion of the system.
  • the system may be operated.
  • the oxidant concentration (persulfuric acid concentration) of the solution mainly composed of the sulfuric acid component held therein is lower than the oxidant concentration of the target oxidative solution.
  • a hydrogen peroxide solution is added to a solution mainly composed of a sulfuric acid component in the system to adjust the oxidative power to an enhanced state, and then electrolysis is performed by an electrolytic cell to obtain the target oxidant concentration.
  • An acidic solution can be produced in a short time. This makes it possible to significantly reduce the time and energy consumption required to set up the electrolytic sulfuric acid solution manufacturing system.
  • the solution mainly containing a sulfuric acid component contained in the system is not only a solution containing no persulfuric acid component at all, but also has an oxidizing agent concentration (persulfuric acid concentration) as a target value. It shall also include a reduced oxidizing solution.
  • invention 3 it is possible to set the concentration suitable for the treatment for both the oxidizing agent concentration and the sulfuric acid concentration of the solution mainly containing the sulfuric acid component existing in the system.
  • the hydrogen peroxide solution, sulfuric acid and / or water are used according to the measured values of the sulfuric acid concentration and / or the persulfuric acid concentration in the solution mainly containing the sulfuric acid component existing in the system.
  • a concentration adjustment step to add an electrolytic treatment step of electrolyzing the solution according to the measured value of each concentration so that the persulfuric concentration becomes the target value, and a temperature so that the temperature of the oxidizing solution becomes the target value. It is preferable to have a temperature adjusting step of heating or cooling the solution according to the measured value of (Invention 4).
  • an oxidizing solution containing a persulfuric acid concentration, a sulfuric acid concentration, and a persulfuric acid component having a temperature suitable for the target treatment can be efficiently supplied in a short time after the start-up of the system. Is possible.
  • the system creates a solution between a storage tank for storing the oxidizing solution, an electrolytic cell for treating the oxidizing solution, and the storage tank and the electrolytic cell.
  • a circulation pipe provided with a liquid feeding mechanism for circulation, a control mechanism for controlling the temperature of the oxidizing solution in the storage tank and / or the temperature of the solution supplied to the electrolytic cell, a hydrogen peroxide addition mechanism, and the like. It is preferable to have a mechanism for adding sulfuric acid and / or water (Invention 5).
  • a solution mainly containing a sulfuric acid component is electrolyzed in an electrolytic cell to generate an oxidizing solution containing a persulfate component, and this oxidizing property is obtained.
  • the solution is stored in the storage tank, and the oxidizing solution is circulated between the storage tank and the electrolytic cell, and the temperature is controlled when the desired oxidant concentration and sulfuric acid concentration are reached. This makes it possible to produce an oxidizing solution containing a persulfuric acid component having a desired sulfuric acid concentration, persulfuric acid concentration and temperature.
  • the hydrogen peroxide solution is added to the solution mainly composed of the sulfuric acid component existing in the system from the addition mechanism of the hydrogen peroxide solution to adjust the persulfuric acid concentration of the oxidizing solution.
  • the sulfuric acid concentration is adjusted by adding sulfuric acid and / or water from the addition mechanism of sulfuric acid and / or water to adjust the liquid to be electrolyzed, and this is supplied to the electrolytic cell.
  • the hydrogen peroxide solution is added to all or part of the solution mainly composed of the sulfuric acid component existing in the system at the time of starting up the electrolytic sulfuric acid solution manufacturing system. Then, after adjusting the solution mainly composed of the sulfuric acid component to a state in which the oxidizing power is enhanced, the time and energy consumption required for starting up the electrolytic sulfuric acid solution production system are significantly reduced by performing electrolysis with an electrolytic cell. Can be reduced to.
  • the electrolytic sulfuric acid solution to be produced is an oxidizing solution containing a persulfuric acid component produced by electrolyzing a solution mainly composed of a sulfuric acid component.
  • peroxodisulfuric acid is produced according to the following reaction formula (1). 2HSO 4 - ⁇ H 2 S 2 O 8 + 2e - ⁇ (1)
  • peroxodisulfuric acid is produced from peroxodisulfuric acid by the equilibrium reaction represented by the formula (2), and further, hydrogen peroxide is produced by the equilibrium reaction represented by the formula (3). Therefore, oxidizing substances such as peroxodisulfuric acid, peroxodisulfuric acid (here, peroxodisulfuric acid and peroxomonosulfuric acid are collectively referred to as persulfuric acid), and hydrogen peroxide are mixed in the electrolytic solution of sulfuric acid. All of these have strong oxidizing power.
  • FIG. 1 shows an electrolytic sulfuric acid solution manufacturing system according to a first embodiment to which the method for setting up the electrolytic sulfuric acid solution manufacturing system of the present invention can be applied.
  • the electrolytic sulfuric acid solution manufacturing system 1 includes a storage tank 2 that receives the electrolytic sulfuric acid solution 3 and a heater 4 as a temperature control mechanism arranged in the storage tank 2.
  • the storage tank 2 is provided with a circulation pipe 5 that exits the bottom of the storage tank 2 and returns to the storage tank 2 again.
  • a circulation pump 6 as a liquid feeding mechanism
  • a heat exchanger 7 for cooling as a temperature control mechanism
  • an electrolytic cell 8 connected to a DC power supply 9 are provided. It is provided.
  • An anode electrode 8A, a bipolar electrode 8B, and a cathode electrode 8C are provided in the electrolytic cell 8, respectively.
  • the electrolytic sulfuric acid solution 3 is refluxed to the storage tank 2 via the circulation pipe 5, and this is repeatedly circulated.
  • the amount of current in the electrolytic cell 8 is controlled so that the concentration of persulfuric acid such as peroxodisulfuric acid produced by the electrolytic sulfuric acid solution 3 becomes a desired concentration according to the treatment using the electrolytic sulfuric acid solution 3. good.
  • a target treatment for example, a treatment such as etching of a resin molded body may be performed.
  • concentration adjustment step adjustments are made so as to reach the desired persulfuric acid concentration and sulfuric acid concentration in a short time when the electrolytic sulfuric acid solution manufacturing system 1 is started up (concentration adjustment step). For this adjustment, for example, hydrogen peroxide solution is added, and sulfuric acid and / or water is added as necessary to produce an electrolyzed liquid to which the respective ratios (concentrations) are adjusted.
  • the persulfuric acid concentration can be adjusted by producing a persulfuric acid (peroxomonosulfuric acid) component having strong oxidizing properties by the reaction of the following formula (4). Because. H 2 SO 4 + H 2 O 2 ⁇ H 2 SO 5 + H 2 O ... (4)
  • the hydrogen peroxide solution to be added a hydrogen peroxide solution having an arbitrary concentration such as 35 wt% hydrogen peroxide solution used as a general industrial chemical can be used, but the hydrogen peroxide solution in the electrolytic sulfuric acid solution 3 can be used. Since the amount added to set the oxidant concentration to the desired value is small, it is preferable to use a high-concentration hydrogen peroxide solution, and general industrial chemicals and EL grade chemicals for the electronic industry can be used properly.
  • the sulfuric acid in the reaction of the above formula (4) the sulfuric acid having a concentration of 70 to 98 weight is preferable, but general industrial chemicals and EL grade chemicals for the electronic industry can be used properly.
  • the sulfuric acid concentration of the electrolyzed liquid is too high, it is necessary to dilute it, or if a hydrogen peroxide solution is used for this dilution, the oxidizing property of the electrolyzed liquid may become too high.
  • water for dilution City water such as tap water can be used as the water used for diluting sulfuric acid, but it is desirable to use pure water to avoid contamination with various cations and anions, and cleaning and modification of the surface of various materials. Ultrapure water can also be used depending on the treatment target applied to the quality.
  • the amount of the hydrogen peroxide solution, sulfuric acid and water (pure water) added may be determined based on the result of measuring the properties of the electrolytic sulfuric acid solution 3 at the time of startup.
  • an oxidant concentration meter or a sulfuric acid concentration meter may be installed in the storage tank 2 or the circulation pipe 5, and the amount of hydrogen peroxide solution, sulfuric acid or pure water added may be determined based on the measurement results.
  • hydrogen peroxide solution and, if necessary, sulfuric acid or water are additionally added to make the persulfuric acid concentration (oxidizing agent concentration). You just have to do the operation to increase.
  • the method for measuring the persulfuric acid concentration is not particularly limited as long as it can measure the correct value, and absorptiometry, redox titration, Raman spectroscopy, polarograph method, potentiometric method, etc. may be used. can.
  • the sulfuric acid concentration measured by the sulfuric acid concentration meter is lower than the target value, add sulfuric acid to adjust the concentration.
  • the sulfuric acid concentration is higher than the target value, water and / or hydrogen peroxide solution is added to adjust the concentration.
  • the method for measuring the sulfuric acid concentration is not particularly limited as long as it can measure a correct value, and a density measurement method, a neutralization titration method, an ultrasonic propagation velocity measurement method, a pack test method, or the like can be used. ..
  • a sulfuric acid solution (electrolyzed liquid) having an improved persulfuric acid (oxidizing agent concentration) is supplied to the electrolytic cell 8 for electrolysis, and it is necessary until the persulfuric acid concentration and the sulfuric acid concentration reach the desired values. It circulates accordingly and continues electrolysis (electrolysis treatment step). Further, the temperature of the electrolytic sulfuric acid solution 3 in the storage tank 2 may be adjusted to a target temperature by heating with the heater 4 so that the temperature becomes a desired temperature (temperature adjustment step).
  • FIG. 2 shows an electrolytic sulfuric acid solution manufacturing system according to a second embodiment to which the method for setting up the electrolytic sulfuric acid solution manufacturing system of the present invention can be applied.
  • the electrolytic sulfuric acid solution manufacturing system 1 has a storage tank 2 that receives the electrolytic sulfuric acid solution 3, a pipe 5A that exits the bottom of the storage tank 2 and communicates with the intermediate tank 10, and an intermediate tank 10 to the storage tank 2.
  • a recirculating pipe 5B is provided, and the pipe 5A is provided with a liquid feed pump 6A as a liquid feed mechanism, while the pipe 5B is provided with a liquid feed pump 6B as a liquid feed mechanism and a temperature control mechanism.
  • a heat exchanger 7A for heating is provided.
  • the bottom of the intermediate tank 10 is provided with a circulation pipe 5C that exits the bottom of the intermediate tank 10 and returns to the intermediate tank 10 again.
  • the circulation pipe 5C includes a circulation pump 6C as a liquid feeding mechanism, a heat exchanger 7B for cooling as a temperature control mechanism, and an electrolytic cell 8 connected to a DC power supply 9 in order from the outlet side (base end side). It is provided.
  • the electrolytic cell 8 is provided with an anode electrode 8A, a bipolar electrode 8B, and a cathode electrode 8C.
  • This oxidizing solution (electrolytic sulfuric acid solution 3) is preferably cooled by the cooling heat exchanger 7B in order to improve the electrolytic efficiency by the electrolytic cell 8.
  • the electrolytic sulfuric acid solution 3 is returned to the dragon interlude 10 via the circulation pipe 5C, and this is supplied from the pipe 5B to the storage tank 2 by the liquid feed pump 6B. At this time, it is preferable to heat the electrolytic sulfuric acid solution 3 with the heating heat exchanger 7A so that the temperature becomes a desired temperature according to the treatment using the electrolytic sulfuric acid solution 3.
  • the amount of current in the electrolytic cell 8 may be controlled so that the concentration of persulfuric acid such as peroxodisulfuric acid produced by the electrolytic sulfuric acid solution 3 becomes a desired concentration according to the treatment using the electrolytic sulfuric acid solution 3. Then, the electrolytic sulfuric acid solution 3 may be used to perform a desired treatment such as etching of a resin molded product.
  • a hydrogen peroxide solution is added to the sulfuric acid solution to adjust the electrolyzed liquid to be electrolyzed, and the electrolyzed liquid is made liquid necessary for various treatments and reforming treatments.
  • the intermediate tank 10 and the electrolytic cell 8 can be circulated to obtain the electrolytic sulfuric acid solution 3 until they have a similar oxidizing power, and then the electrolytic sulfuric acid solution 3 can be adjusted to a predetermined temperature and supplied to the storage tank 2, the storage tank 2 can be supplied. Can be used as it is as a processing tank. Further, the electrolytic sulfuric acid solution 3 can be produced in parallel with the desired treatment in the storage tank 2. For example, in a plating component manufacturing line that uses an electrolytic sulfuric acid solution for etching a resin surface performed for plating the surface of a plastic material, the storage tank 2 can be used as an etching tank.
  • a hydrogen peroxide solution if necessary, sulfuric acid and / or
  • water By adding water to prepare a solution to be electrolyzed with enhanced oxidative properties and energizing the electrolyzed cell 8 to perform electrolysis, the desired persulfate concentration and sulfuric acid concentration can be obtained in a short time.
  • the electrolytic sulfuric acid solution 3 can be produced, and the start-up of the electrolytic sulfuric acid solution production system can be completed in a short time.
  • salts such as persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate are not added, electrolysis of cation components other than hydrogen ions caused by the persulfates is performed. There is no contamination with the sulfuric acid solution. Furthermore, since only the liquid is added, it has the effect of being easy to handle.
  • the present invention is not limited to the above embodiment, and various modifications can be carried out.
  • the means for adding sulfuric acid, hydrogen hydrogen solution, and water are controlled to the optimum values by calculation / control means such as a personal computer based on the measurement results of the sulfuric acid concentration meter and the oxidant concentration meter. Therefore, the addition of sulfuric acid, hydrogen peroxide solution and water, and the automation of the electrolysis time (circulation time) by the electrolysis cell 8 may be performed.
  • the sulfuric acid concentration, the persulfuric acid concentration and the temperature of the electrolytic sulfuric acid solution 3 can be variously changed according to the treatment target.
  • the electrolytic cell 8 a current of 20 A was passed between the anode electrode 8A and the cathode electrode 8C from the DC power source 9, and the circulating sulfuric acid solution was electrolyzed.
  • an electrode (diamond electrode) in which diamond was formed on the surface of a silicon wafer was used as the anode electrode 8A, the cathode electrode 8C, and the bipolar electrode 8B. Further, the electrode areas of the anode electrode 8A and the cathode electrode 8C were both set to 5.2 dm 2 . Then, the circulating liquid (sulfuric acid solution) that passed through the electrolytic cell 8 was returned to the storage tank 2.
  • the persulfuric acid concentration in the circulating fluid is appropriately measured, circulated until the properties of the circulating fluid reach the liquid properties used for etching set above, and electrolysis by the electrolytic cell 8 is continued.
  • Sulfuric acid solution 3 was produced.
  • the electrolytic sulfuric acid solution 3 in the storage tank 2 was heated to a set temperature (60 ° C.) by using an electric heater (heater 4) installed in the storage tank 2.
  • the persulfuric acid concentration was determined from the difference between the oxidant concentration measured by the iodine titration method and the oxidant concentration measured by the permanganate titration method.
  • the iodine titration method to release the I 2 by adding KI to analyte solution was collected a small amount component, determine the amount of I 2 and the I 2 was titrated with Na 2 S 2 O 3 standard solution, The total oxidant component concentration is measured by a method of obtaining the oxidant concentration from the amount of I 2.
  • permanganate titration is a measurement method in which potassium permanganate is titrated into a small amount of the solution to be measured, and only the concentration of hydrogen peroxide in the solution to be measured can be determined.
  • the persulfuric acid concentration is calculated by subtracting the oxidant concentration corresponding to the hydrogen peroxide concentration from the total oxidant concentration obtained by the iodine titration method.
  • ABS resin test piece (BULKSAM TM-25, manufactured by Techno-UMG Co., Ltd .: 40 mm ⁇ 130 mm ⁇ t3 mm) was immersed in the electrolytic sulfuric acid solution 3 produced as described above for 10 minutes for etching. Specifically, the test piece attached to the jig was immersed in the storage tank 2. Then, the etched test piece was immersed in warm water at 50 ° C. for 10 minutes, washed with water, and further immersed in a neutralizing solution (concentrated hydrochloric acid 50 mL / L, 35 ° C.) for 1 minute.
  • a neutralizing solution concentrated hydrochloric acid 50 mL / L, 35 ° C.
  • the test piece was immersed in a palladium-tin colloidal catalyst solution (palladium concentration 0.11 g / L, tin concentration 10.7 g / L, concentrated hydrochloric acid 180 mL / L, 40 ° C.) for 2 minutes, washed with water, and then activated (activated solution). It was immersed in concentrated hydrochloric acid (100 mL / L, 40 ° C.) for 10 minutes for activation treatment. After washing this test piece with water, it was immersed in an electroless nickel plating solution (nickel concentration 8.0 g / L, pH 9.0, 40 ° C.) for 15 minutes to perform a plating treatment. It was confirmed that silver nickel plating was deposited on the entire surface of the test piece that had undergone this plating process.
  • a palladium-tin colloidal catalyst solution palladium concentration 0.11 g / L, tin concentration 10.7 g / L, concentrated hydrochloric acid 180 mL / L, 40 ° C
  • ABS resin test piece used in Comparative Example 1 was not subjected to an etching treatment, but was subjected to a plating pretreatment under the same conditions as in Comparative Example 1, and further subjected to a plating treatment. On the test piece that had undergone this plating treatment step, plating was sparsely deposited on a surface area of about 10% or less, and it was found that the test piece was unsuitable as a plating product without the etching treatment.
  • Example 1 Using the same electrolytic sulfuric acid solution manufacturing system 1 as in Comparative Example 1, the liquid property of the electrolytic sulfuric acid solution 3 containing the persulfuric acid component used for resin etching for pretreatment to plate the ABS resin molded body is as follows: sulfuric acid concentration 78 wt%, persulfuric acid. A concentration of 7 g / Las S 2 O 8 and a temperature of 60 ° C. were set, and the electrolytic sulfuric acid solution 3 was produced by the following steps.
  • the electrolytic cell 8 was energized under the same conditions as in Comparative Example 1 described above, and the circulating fluid that had passed through the electrolytic cell 8 was returned to the storage tank 2. At this time, the concentration of persulfuric acid in the circulating fluid was appropriately measured, and electrolysis was continued until the properties of the circulating fluid reached the liquid properties used for etching set above to produce the electrolytic sulfuric acid solution 3. At this time, the electrolytic sulfuric acid solution 3 in the storage tank 2 was heated to a set temperature (60 ° C.) by using an electric heater (heater 4) installed in the storage tank 2.
  • the ABS resin test piece was subjected to etching treatment and plating pretreatment under the same conditions as in Comparative Example 1, and further plating treatment was performed. It was confirmed that silver nickel plating was deposited on the entire surface of the test piece that had undergone this plating treatment step, as in Comparative Example 1.
  • Electrolyzed sulfuric acid solution manufacturing system 2 Storage tank 3 Electrolyzed sulfuric acid solution 4 Heater (temperature control mechanism) 5,5C Circulation piping 5A Piping 5B Piping 6,6C Circulation pump 6A, 6B Liquid transfer pump 7 Heat exchanger (temperature control mechanism) 7A Heat exchanger for heating (temperature control mechanism) 7B Cooling heat exchanger (temperature control mechanism) 8 Electrolytic cell 8A Anode electrode 8B Bipolar electrode 8C Cathode electrode 9 DC power supply 10 Intermediate tank

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Automation & Control Theory (AREA)
  • Analytical Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

Du peroxyde d'hydrogène est ajouté, conjointement avec de l'acide sulfurique et/ou de l'eau selon les besoins, à une solution d'acide sulfurique qui se trouve dans un réservoir de stockage (2) ou similaire d'un système de fabrication de solution électrolytique d'acide sulfurique (1), ce qui permet d'ajuster la puissance d'oxydation de la solution d'acide sulfurique à un état augmenté, et la solution d'acide sulfurique est acheminée dans une cellule électrolytique (8) et électrolysée. Le système de fabrication de solution électrolytique d'acide sulfurique (1) est démarré, par exemple, lorsque le système de fabrication de solution électrolytique d'acide sulfurique (1) fonctionne pour la première fois après avoir été achevé, ou lorsque celui-ci fonctionne après qu'une solution contenant de l'acide sulfurique dans le système a été échangée ou après que la concentration de composants d'acide persulfurique dans la solution électrolytique d'acide sulfurique stockée dans le système a diminué en raison de l'arrêt du fonctionnement du système. En démarrant le système de fabrication de solution électrolytique d'acide sulfurique de cette manière, le démarrage de ce système, qui fabrique une solution électrolytique d'acide sulfurique comprenant des composants d'acide persulfurique qui sont générés par électrolyse de l'acide sulfurique, peut être achevé en un court laps de temps, et la consommation d'énergie peut être réduite.
PCT/JP2020/034959 2020-05-18 2020-09-15 Procédé de démarrage pour système de fabrication de solution électrolytique d'acide sulfurique WO2021234978A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN202080098615.6A CN115298360A (zh) 2020-05-18 2020-09-15 电解硫酸溶液制备系统的启动方法
US17/912,910 US20230079765A1 (en) 2020-05-18 2020-09-15 Startup method for electrolytic sulfuric acid solution manufacturing system
EP20936154.2A EP4155434A1 (fr) 2020-05-18 2020-09-15 Procédé de démarrage pour système de fabrication de solution électrolytique d'acide sulfurique

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020-086988 2020-05-18
JP2020086988A JP7484407B2 (ja) 2020-05-18 2020-05-18 電解硫酸溶液製造システムの立上げ方法

Publications (1)

Publication Number Publication Date
WO2021234978A1 true WO2021234978A1 (fr) 2021-11-25

Family

ID=78606144

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/034959 WO2021234978A1 (fr) 2020-05-18 2020-09-15 Procédé de démarrage pour système de fabrication de solution électrolytique d'acide sulfurique

Country Status (5)

Country Link
US (1) US20230079765A1 (fr)
EP (1) EP4155434A1 (fr)
JP (1) JP7484407B2 (fr)
CN (1) CN115298360A (fr)
WO (1) WO2021234978A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006114880A (ja) * 2004-09-17 2006-04-27 Kurita Water Ind Ltd 硫酸リサイクル型洗浄システムおよび硫酸リサイクル型過硫酸供給装置
JP2006278915A (ja) * 2005-03-30 2006-10-12 Kurita Water Ind Ltd 硫酸リサイクル型洗浄システム
JP2012215462A (ja) * 2011-03-31 2012-11-08 Chlorine Engineers Corp Ltd 酸化性物質の総濃度測定方法、酸化性物質の総濃度測定用濃度計およびそれを用いた硫酸電解装置
JP2016167560A (ja) * 2015-03-10 2016-09-15 栗田工業株式会社 電解硫酸溶液の製造方法および電解硫酸溶液製造装置
JP2017171830A (ja) * 2016-03-25 2017-09-28 独立行政法人国立高等専門学校機構 複合材の処理方法
JP2019044229A (ja) 2017-09-01 2019-03-22 栗田工業株式会社 Ａｂｓ系樹脂表面のめっき前処理方法、ａｂｓ系樹脂表面のめっき処理方法、及びａｂｓ系樹脂めっき製品

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006114880A (ja) * 2004-09-17 2006-04-27 Kurita Water Ind Ltd 硫酸リサイクル型洗浄システムおよび硫酸リサイクル型過硫酸供給装置
JP2006278915A (ja) * 2005-03-30 2006-10-12 Kurita Water Ind Ltd 硫酸リサイクル型洗浄システム
JP2012215462A (ja) * 2011-03-31 2012-11-08 Chlorine Engineers Corp Ltd 酸化性物質の総濃度測定方法、酸化性物質の総濃度測定用濃度計およびそれを用いた硫酸電解装置
JP2016167560A (ja) * 2015-03-10 2016-09-15 栗田工業株式会社 電解硫酸溶液の製造方法および電解硫酸溶液製造装置
JP2017171830A (ja) * 2016-03-25 2017-09-28 独立行政法人国立高等専門学校機構 複合材の処理方法
JP2019044229A (ja) 2017-09-01 2019-03-22 栗田工業株式会社 Ａｂｓ系樹脂表面のめっき前処理方法、ａｂｓ系樹脂表面のめっき処理方法、及びａｂｓ系樹脂めっき製品

Also Published As

Publication number Publication date
JP7484407B2 (ja) 2024-05-16
CN115298360A (zh) 2022-11-04
US20230079765A1 (en) 2023-03-16
JP2021181594A (ja) 2021-11-25
EP4155434A1 (fr) 2023-03-29

Similar Documents

Publication Publication Date Title
EP1801265B1 (fr) Systeme nettoyant de type recyclant d'acide sulfurique et dispositif d'alimentation en acide persulfurique de type recyclant d'acide sulfurique
JP4407529B2 (ja) 硫酸リサイクル型洗浄システム
KR20150043304A (ko) 반도체 기판의 세정 방법 및 세정 시스템
JP2007059603A (ja) 硫酸リサイクル型洗浄システム
TWI419999B (zh) 電解方法
WO2021234978A1 (fr) Procédé de démarrage pour système de fabrication de solution électrolytique d'acide sulfurique
JP2012204546A (ja) 電子材料洗浄方法および洗浄装置
JP4600667B2 (ja) 硫酸リサイクル型洗浄システムおよび硫酸リサイクル型洗浄方法
JP2006278687A (ja) 硫酸リサイクル型枚葉式洗浄システム
JP4407557B2 (ja) 硫酸リサイクル型洗浄方法および硫酸リサイクル型洗浄システム
JP6988977B1 (ja) 樹脂成形体のエッチング方法及び樹脂成形体のエッチング処理システム
JP2016167560A (ja) 電解硫酸溶液の製造方法および電解硫酸溶液製造装置
JP2006150320A (ja) 排水加熱分解システム
WO2021220527A1 (fr) Procédé de gravure pour article moulé en résine et système de traitement par gravure pour article moulé en résine
JP4561993B2 (ja) 硫酸リサイクル型過硫酸供給装置
JP2008294020A (ja) 洗浄液供給システムおよび洗浄システム
JP2008038213A (ja) 特に高純度な硫酸銅水溶液又は硫酸鉄を含む硫酸銅水溶液の製造方法及び製造装置、並びに特に高純度な硫酸銅水溶液又は硫酸鉄を含む硫酸銅水溶液
JP4038253B2 (ja) 酸性水及びアルカリ水製造用電解槽
WO2009098756A1 (fr) Procédé et appareil de production d'une solution aqueuse de sulfate de cuivre de grande pureté ou d'une solution aqueuse de sulfate de cuivre contenant du sulfate de fer, et solution aqueuse de sulfate de cuivre de grande pureté ou solution aqueuse de sulfate de cuivre contenant du sulfate de fer
US20220145478A1 (en) Electrodialysis salt splitting regenerant generation for wac and wba resin combined with sodium hypochlorite on-site generation process
JP5995242B2 (ja) 窒素除去方法及びその装置
JP3786863B2 (ja) 洗浄水の製造装置
JP4816888B2 (ja) 硫酸リサイクル型洗浄システム
WO2022038817A1 (fr) 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
TW202225103A (zh) 電滲析裝置、水處理系統及方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20936154

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2020936154

Country of ref document: EP

Effective date: 20221219