WO2021234978A1 - Startup method for electrolytic sulfuric acid solution manufacturing system - Google Patents

Startup method for electrolytic sulfuric acid solution manufacturing system Download PDF

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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
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Prior art keywords
sulfuric acid
solution
electrolytic
acid solution
concentration
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PCT/JP2020/034959
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French (fr)
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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Priority to EP20936154.2A priority Critical patent/EP4155434A1/en
Priority to CN202080098615.6A priority patent/CN115298360A/en
Priority to US17/912,910 priority patent/US20230079765A1/en
Publication of WO2021234978A1 publication Critical patent/WO2021234978A1/en

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    • 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

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Abstract

Hydrogen peroxide is added, along with sulfuric acid and/or water as necessary, to a sulfuric acid solution that is in a storage tank 2 or similar of an electrolytic sulfuric acid solution manufacturing system 1, thereby adjusting the oxidizing power of the sulfuric acid solution to a heightened state, and the sulfuric acid solution is supplied to an electrolytic cell 8 and electrolyzed. The electrolytic sulfuric acid solution manufacturing system 1 is started up, for example, when the electrolytic sulfuric acid solution manufacturing system 1 operates for the first time after being completed, or when the same operates after a sulfuric acid-including solution in the system has been exchanged or after the concentration of persulfuric acid components in the electrolytic sulfuric acid solution stored in the system has decreased due to stopping the operation of the system. By starting up the electrolytic sulfuric acid solution manufacturing system in this manner, the startup of this system which manufactures an electrolytic sulfuric acid solution including persulfuric acid components that are generated by electrolyzing sulfuric acid can be completed in a short time, and energy consumption can be reduced.

Description

電解硫酸溶液製造システムの立上げ方法How to set up an electrolytic sulfuric acid solution manufacturing system
　本発明は、各種材料の表面の洗浄や改質、特にプラスチック材料表面へのめっき処理に先立って行われるエッチング処理に好適な電解硫酸溶液を製造するシステムの立上げ方法に関する。 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.
　ペルオキソ一硫酸、ペルオキソ二硫酸といった過硫酸成分を含む硫酸溶液は、きわめて強い酸化性を有する。この強い酸化性を利用して、過硫酸成分を含む硫酸溶液は、金属、シリコン、ガラス、プラスチックなどの各種材料の洗浄や表面改質に利用されている。 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.
　過硫酸成分を含む硫酸溶液は、硫酸成分を主体とする溶液を電気分解して生成することができる。この硫酸成分を主体とする溶液を電気分解することで生成される過硫酸成分を含む酸化性溶液（以下、電解硫酸溶液という場合がある）を製造するシステムは、例えば、電解硫酸溶液を貯留する貯留槽と、電解セル及び直流電源と、貯留槽と電解セルの間で溶液を循環させるための循環ポンプを備えた配管と、循環液を加温・冷却するためのヒーターや熱交換器などとから構成される。そして、硫酸成分を主体とする溶液を循環させながら電解セル内の電極に通電して電気分解を行うことで電解硫酸溶液を生成する。このようなシステムを用いて電解硫酸を製造する方法として、プラスチック材料表面をめっきするために行われる樹脂表面のエッチング処理に適用するために電解硫酸を製造する技術が特許文献１に記載されている。 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. A storage tank, an electrolytic cell and a DC power supply, a pipe equipped with a circulation pump for circulating a solution between the storage tank and the electrolytic cell, and a heater and a heat exchanger for heating and cooling the circulating liquid. Consists of. Then, while circulating a solution mainly composed of a sulfuric acid component, an electrode in the electrolytic cell is energized to perform electrolysis to generate an electrolytic sulfuric acid solution. As a method for producing electrolytic sulfuric acid using such a system, 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. ..
　この特許文献１に記載の電解硫酸の製造方法では、硫酸濃度が６０～８７ｗｔ％、溶液の温度が５０～８０℃及び過硫酸濃度が３ｇ／Ｌ以上になるよう硫酸を電気分解した電解硫酸溶液によりＡＢＳ樹脂表面をエッチングすることで、ＡＢＳ系樹脂表面のブタジエン成分が溶解するとともに親水性の官能基が露出し粗面化する。これによりこのエッチング処理を施したＡＢＳ系樹脂にめっきを施すと十分に密着しためっきを析出させることができる。この電解硫酸溶液によるエッチング処理は、従来クロム酸を用いて行われてきた樹脂エッチングに比べ環境負荷の少ない有効な処理方法として提案されている。さらに、特許文献１には、初期状態において所定の濃度の硫酸が充填されていて、この溶液を陽極および陰極に直流電源ユニットから所定の電流を通電して、硫酸を電気分解することにより、ペルオキソ二硫酸等の過硫酸溶液を生成することが記載されている。また、特許文献１には、電解硫酸溶液の代わりに、硫酸と過酸化水素との混合溶液を用いてＡＢＳ樹脂表面をエッチングした例が比較例として記載されており、この比較例では、めっき皮膜は形成されるものの、過酸化水素の消費により処理の長期安定性に問題があることが記載されている。 In the method for producing electrolytic sulfuric acid described in Patent Document 1, 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. By etching the surface of the ABS resin, the butadiene component on the surface of the ABS resin is dissolved and the hydrophilic functional groups are exposed and the surface is roughened. As a result, when the ABS-based resin subjected to this etching treatment is plated, a plating that is sufficiently adhered can be deposited. This etching treatment with an electrolytic sulfuric acid solution has been proposed as an effective treatment method having a smaller environmental load than the resin etching conventionally performed using chromic acid. Further, 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.
特開２０１９－０４４２２９号公報Japanese Unexamined Patent Publication No. 2019-044229
　このように、電解硫酸溶液を用いた各種材料表面の洗浄や改質処理は、環境への影響の点で非常に有効な方法である。しかしながら、電解硫酸溶液を製造するシステムは、竣工後の初回のシステムの立上げ時、電解硫酸溶液の交換後のシステムの立上げ時、あるいはシステムの稼働停止により電解硫酸溶液中の有効成分である過硫酸濃度が低下した場合のシステムの再立上げ時などには、すぐに各種材料表面の洗浄や改質処理を行うことができる状態にない。すなわち、前述したような電解硫酸溶液製造システムを立上げる場合には、準備段階として、硫酸溶液自体あるいは過硫酸濃度が低くなった電解硫酸溶液を、目的に応じた所定の過硫酸濃度になるまで電解セルを稼働して電気分解を継続する必要がある。このため、各種材料表面の洗浄や改質処理に必要な過硫酸濃度の電解硫酸溶液を得るまでにエネルギーを要し、短時間にシステムを立上げられない、という課題がある。 As described above, cleaning and reforming the surface of various materials using an electrolytic sulfuric acid solution is a very effective method in terms of environmental impact. However, 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. When the system is restarted when the persulfuric acid concentration drops, the surface of various materials cannot be immediately cleaned or reformed. That is, when setting up the electrolytic sulfuric acid solution manufacturing system as described above, as a preparatory step, 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.
　具体的には、プラスチック材料表面をめっきするために行われる樹脂表面のエッチング処理に電解硫酸溶液を用いるめっき部品の製造ラインにおいて、エッチング槽の定期点検等によりエッチング液を入れ換えた際の再立上げ後や電解硫酸溶液製造システムの再立上げ後には、所定の濃度に調整した硫酸溶液を電解セルに循環通液しながら、有効なエッチング効果が得られる液性まで電解を継続しなければならず、めっき部品の製造を開始できるまでに長時間を要し、さらに、めっき製品の製造を開始するまでの間に多くのエネルギーを消費する、という課題がある。これらの課題は、例えばめっき前処理用のエッチング槽の容量が大きい場合など、電解硫酸溶液製造システムの保有溶液量が多い場合に特に顕著である。 Specifically, in a manufacturing line for plated parts that uses an electrolytic sulfuric acid solution for the etching process of the resin surface that is performed to plate the surface of plastic materials, restarting when the etching solution is replaced by periodic inspection of the etching tank, etc. After that, or after restarting the electrolytic sulfuric acid solution manufacturing system, the electrolytic solution must be circulated through the electrolytic cell while the sulfuric acid solution adjusted to a predetermined concentration is circulated to the electrolytic cell, and the electrolysis must be continued until the liquid property provides an effective etching effect. There is a problem that it takes a long time to start manufacturing plated parts, and a lot of energy is consumed before starting manufacturing of plated products. These problems are particularly remarkable when the amount of the solution possessed by the electrolytic sulfuric acid solution production system is large, for example, when the capacity of the etching tank for plating pretreatment is large.
　本発明は上記課題に鑑みてなされたものであり、硫酸を電気分解して生成した過硫酸成分を含む電解硫酸溶液を製造するシステムの立上げを短時間に完了できるとともにエネルギー消費量を低減することが可能な電解硫酸溶液製造システムの立上げ方法を提供することを目的とする。 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.
　上記目的を達成するために、本発明は、硫酸成分を主体とする溶液を電気分解して生成する過硫酸成分を含む酸化性溶液を製造するシステムの立ち上げ方法であって、前記システム内に存在する硫酸成分を主体とする溶液の全部あるいは一部に過酸化水素水を添加して前記硫酸成分を主体とする溶液の酸化力を高めた状態に調整し、その溶液を電解セルに供給して電気分解を行う、電解硫酸溶液製造システムの立上げ方法を提供する（発明１）。上記発明（発明１）においては、前記システムの立ち上げが、該システムの竣工後の初回稼働時、該システム内の過硫酸成分を含む酸化性溶液の交換後、該システムの稼働停止によりシステム内に貯留している酸化性溶液中の過硫酸成分の濃度が低下した後の稼働時のいずれかであることが好ましい（発明２）。 In order to achieve the above object, 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. Provided is a method for setting up an electrolytic sulfuric acid solution manufacturing system that performs electrolysis (Invention 1). In the above invention (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).
　かかる発明（発明１，２）によれば、硫酸成分を主体とする溶液を電気分解して生成する過硫酸成分を含む酸化性溶液の製造システムの稼立ち上げ時、すなわちシステムの竣工後の初回稼働時、該システム内の硫酸含有溶液交換後、は該システムの稼働停止によりシステム内に貯留している電解硫酸溶液中の過硫酸成分の濃度が低下した後の稼働時などには、前記システム内に保有されている硫酸成分を主体とする溶液の酸化剤濃度（過硫酸濃度）は目的とする酸化性溶液の酸化剤濃度よりも低下している。そこで、過酸化水素水を該システム内の硫酸成分を主体とする溶液に添加して酸化力を高めた状態に調整した後、電解セルにより電気分解を行うことで、目的とする酸化剤濃度の酸性溶液を短時間で製造することができる。これにより電解硫酸溶液製造システムの立上げに必要な時間とエネルギー消費量を大幅に低減することが可能となる。なお、本発明において、前記システム内に保有されている硫酸成分を主体とする溶液とは、過硫酸成分を全く含まないもののみならず、酸化剤濃度（過硫酸濃度）が目的とする値より低下した状態の酸化性溶液も含むものとする。 According to the inventions (Inventions 1 and 2), 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. During operation, after exchanging the sulfuric acid-containing solution in the system, or after the concentration of the persulfuric acid component in the electrolytic sulfuric acid solution stored in the system decreases due to the shutdown 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. Therefore, 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. In the present invention, 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.
　上記発明（発明１，２）においては、前記システム内に存在する硫酸成分を主体とする溶液の全部あるいは一部にさらに硫酸及び／又は水を添加することが好ましい（発明３）。 In the above inventions (Inventions 1 and 2), it is preferable to further add sulfuric acid and / or water to all or part of the solution mainly composed of sulfuric acid component existing in the system (Invention 3).
　かかる発明（発明３）によれば、前記システム内に存在する硫酸成分を主体とする溶液の酸化剤濃度と硫酸濃度の両方を目的とする処理に好適な濃度とすることができる。 According to the invention (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.
　上記発明（発明３）においては、前記システム内に存在する硫酸成分を主体とする溶液中の硫酸濃度及び／又は過硫酸濃度の測定値に応じて前記過酸化水素水、硫酸及び／又は水を添加する濃度調整工程と、前記過硫酸濃度が目的値となるように各濃度の測定値に応じて溶液を電気分解する電解処理工程と、前記酸化性溶液の温度が目的値となるように温度の測定値に応じて該溶液の加温又は冷却を行う温度調整工程とを有することが好ましい（発明４）。 In the above invention (Invention 3), 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).
　かかる発明（発明４）によれば、目的とする処理に好適な過硫酸濃度、硫酸濃度及び温度の過硫酸成分を含む酸化性溶液を、前記システムの立ち上げ後短時間で効率良く供給することが可能となる。 According to the present invention (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.
　上記発明（発明３又は４）においては、前記システムが、前記酸化性溶液を貯留する貯留槽と、前記酸化性溶液を処理する電解セルと、前記貯留槽と前記電解セルとの間に溶液を循環させるための送液機構を備えた循環配管と、前記貯留槽内の酸化性溶液の温度及び／又は前記電解セルに供給する溶液の温度を制御する制御機構と、過酸化水素添加機構と、硫酸及び／又は水の添加機構とを備えることが好ましい（発明５）。 In the above invention (Invention 3 or 4), 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).
　かかる発明（発明５）によれば、電解硫酸溶液製造システムの通常の稼働時には硫酸成分を主体とする溶液を電解セルにおいて電気分解して過硫酸成分を含む酸化性溶液を生成し、この酸化性溶液を貯留槽に貯留するとともに、酸化性溶液を貯留槽と電解セルとの間を循環させ、所望とする酸化剤濃度及び硫酸濃度となったら温度制御を行う。これにより所望の硫酸濃度、過硫酸濃度及び温度の過硫酸成分を含む酸化性溶液を製造することができる。そして、電解硫酸溶液製造システムの立ち上げ時には、過酸化水素水の添加機構から該システム内に存在する硫酸成分を主体とする溶液に過酸化水素水を添加して酸化性溶液の過硫酸濃度を目的とする値に近づけるとともに、硫酸及び／又は水の添加機構から硫酸及び／又は水を添加することで硫酸濃度を調節して、被電解処理液を調整し、これを電解セルに供給して電解処理することで、電解硫酸溶液製造システムの立上げに必要な時間とエネルギー消費量を大幅に低減することができる。 According to the present invention (Invention 5), during normal operation of the electrolytic sulfuric acid solution production system, 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. Then, at the time of starting up the electrolytic sulfuric acid solution production system, 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. While approaching the target value, 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. By the electrolytic treatment, the time and energy consumption required to start up the electrolytic sulfuric acid solution production system can be significantly reduced.
　本発明の電解硫酸溶液製造システムの立上げ方法によれば、電解硫酸溶液製造システムの立上げ時に前記システム内に存在する硫酸成分を主体とする溶液の全部あるいは一部に過酸化水素水を添加して前記硫酸成分を主体とする溶液の酸化力を高めた状態に調整した後、電解セルにより電気分解を行うことで、電解硫酸溶液製造システムの立上げに必要な時間とエネルギー消費量を大幅に低減することができる。 According to the method for setting up the electrolytic sulfuric acid solution manufacturing system of the present invention, 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.
本発明の電解硫酸溶液製造システムの立上げ方法を適用可能な第一の実施形態による電解硫酸溶液製造システムを示す概略図である。It is a schematic diagram which shows the electrolytic sulfuric acid solution manufacturing system by the 1st Embodiment to which the start-up method of the electrolytic sulfuric acid solution manufacturing system of this invention can be applied. 本発明の電解硫酸溶液製造システムの立上げ方法を適用可能な第二の実施形態による電解硫酸溶液製造システムを示す概略図である。It is a schematic diagram which shows the electrolytic sulfuric acid solution manufacturing system by the 2nd Embodiment to which the start-up method of the electrolytic sulfuric acid solution manufacturing system of this invention can be applied.
　以下、本発明の電解硫酸溶液製造システムの立上げ方法について添付図面を参照して詳細に説明する。 Hereinafter, the method for setting up the electrolytic sulfuric acid solution manufacturing system of the present invention will be described in detail with reference to the attached drawings.
＜第一の実施形態＞
［電解硫酸溶液］
　本実施形態において、製造対象となる電解硫酸溶液は、硫酸成分を主体とする溶液を電気分解することで生成される過硫酸成分を含む酸化性溶液である。ここで、硫酸を電気分解すると、以下の反応式（１）に従ってペルオキソ二硫酸が生成する。
　２ＨＳＯ４ －　　→　　Ｈ２Ｓ２Ｏ８　　＋　　２ｅ－　・・・（１） <First embodiment>
[Electrolytic sulfuric acid solution]
In the present embodiment, 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. Here, when sulfuric acid is electrolyzed, peroxodisulfuric acid is produced according to the following reaction formula (1).
2HSO 4 - → H 2 S 2 O 8 + 2e - ··· (1)
　また、ペルオキソ二硫酸から式（２）に示す平衡反応でペルオキソ一硫酸が生成し、さらには式（３）に示す平衡反応で過酸化水素が生成する。したがって、硫酸の電解液中にはペルオキソ二硫酸、ペルオキソ一硫酸（ここではペルオキソ二硫酸とペルオキソ一硫酸を総称して過硫酸とする）、過酸化水素といった酸化性物質が混在する。これらはいずれも強い酸化力を有する。
　Ｈ２Ｓ２Ｏ８　　＋　　Ｈ２Ｏ　　⇔　　Ｈ２ＳＯ５　　＋　　Ｈ２ＳＯ４　・・・（２）
　Ｈ２ＳＯ５　　＋　　Ｈ２Ｏ　　⇔　　Ｈ２Ｏ２　　＋　　Ｈ２ＳＯ４　・・・（３） Further, 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.
H 2 S 2 O 8 + H 2 O ⇔ H 2 SO 5 + H 2 SO 4 ... (2)
H 2 SO 5 + H 2 O ⇔ H 2 O 2 + H 2 SO 4 ... (3)
［電解硫酸溶液製造システム］
　次に上述したような電解硫酸溶液を製造する電解硫酸溶液製造システムについて説明する。図１は本発明の電解硫酸溶液製造システムの立上げ方法を適用可能な第一の実施形態による電解硫酸溶液製造システムを示している。 [Electrolytic sulfuric acid solution manufacturing system]
Next, an electrolytic sulfuric acid solution manufacturing system for manufacturing the electrolytic sulfuric acid solution as described above will be described. 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.
　図１において、電解硫酸溶液製造システム１は、電解硫酸溶液３を受ける貯留槽２と、この貯留槽２内に配置された温度制御機構としての加熱器４とを備える。この貯留槽２には、該貯留槽２の底部を出て再度貯留槽２に還流する循環配管５が設けられている。この循環配管５には、出口側（基端側）から順に送液機構としての循環ポンプ６と温度制御機構としての冷却用の熱交換器７と直流電源９に接続された電解セル８とが設けられている。この電解セル８内には、アノード電極８Ａとバイポーラ電極８Ｂとカソード電極８Ｃとがそれぞれ設けられている。 In FIG. 1, 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. In the circulation pipe 5, in order from the outlet side (base end side), a circulation pump 6 as a liquid feeding mechanism, a heat exchanger 7 for cooling as a temperature control mechanism, and 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.
［電解硫酸溶液の製造方法］
　次に上述したような電解硫酸溶液製造システム１を用いた電解硫酸溶液３の製造方法について説明する。まず、貯留槽２に硫酸成分を主体とする溶液を入れたら循環ポンプ６により循環配管５を経由して電解セル８に供給する。そして、直流電源９から所定の電流を通電して、硫酸成分を主体とする溶液を電気分解することで生成されるペルオキソ二硫酸等の過硫酸成分を含む酸化性溶液（電解硫酸溶液３）を製造する。この際、電解セル８による電解効率を向上させるため、熱交換器７により電解硫酸溶液３を冷却することが好ましい。この電解硫酸溶液３を、循環配管５を経由して貯留槽２に還流し、これを繰り返して循環させる。このとき電解硫酸溶液３により生成するペルオキソ二硫酸等の過硫酸の濃度を、該電解硫酸溶液３を用いた処理に応じた所望とする濃度となるように電解セル８における電流量を制御すればよい。そして、貯留槽２内に貯留された電解硫酸溶液３の温度が、該電解硫酸溶液３を用いた処理に応じた所望の温度となるように加熱器４により加熱することが好ましい。このようにして貯留槽２に張り込んだ電解硫酸溶液３を用いて、目的とする処理、例えば樹脂成形体のエッチングなどの処理を行えばよい。 [Manufacturing method of electrolytic sulfuric acid solution]
Next, a method for producing the electrolytic sulfuric acid solution 3 using the electrolytic sulfuric acid solution production system 1 as described above will be described. First, a solution containing a sulfuric acid component as a main component is placed in the storage tank 2 and then supplied to the electrolytic cell 8 by the circulation pump 6 via the circulation pipe 5. Then, an oxidizing solution (electrolytic sulfuric acid solution 3) containing a persulfuric acid component such as peroxodisulfuric acid, which is produced by electrolyzing a solution mainly composed of sulfuric acid by applying a predetermined current from the DC power source 9, is applied. To manufacture. At this time, in order to improve the electrolysis efficiency of the electrolytic cell 8, it is preferable to cool the electrolytic sulfuric acid solution 3 with the heat exchanger 7. The electrolytic sulfuric acid solution 3 is refluxed to the storage tank 2 via the circulation pipe 5, and this is repeatedly circulated. At this time, if 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. Then, it is preferable to heat the electrolytic sulfuric acid solution 3 stored in the storage tank 2 by the heater 4 so that the temperature becomes a desired temperature according to the treatment using the electrolytic sulfuric acid solution 3. Using the electrolytic sulfuric acid solution 3 packed in the storage tank 2 in this way, a target treatment, for example, a treatment such as etching of a resin molded body may be performed.
［電解硫酸溶液製造システムの立上げ方法］
　上述したような電解硫酸溶液の製造工程において、電解硫酸溶液製造システム１の立ち上げ時、具体的には、電解硫酸溶液製造システム１の竣工後の初回稼働時、該システム１の過硫酸溶液３の交換後、又は該システム１の稼働停止によりシステム内に貯留している過硫酸溶液３中の過硫酸成分の濃度が低下した後の稼働時などには、貯留槽２に貯留されている電解硫酸溶液３は、過硫酸成分の濃度が所望とする処理のための目的とする濃度より低いのでそのままでは使用できない。そこで従来は、所望とする過硫酸濃度となるまで、貯留槽２と循環配管５と電解セル８との間で電解硫酸溶液３の循環を継続する必要があった。このため、所望とする過硫酸濃度の電解硫酸溶液３を得るまでに長い時間と大きなエネルギーを要し、短時間で電解硫酸溶液製造システム１を立上げられない、という問題点があった。 [How to set up an electrolytic sulfuric acid solution manufacturing system]
In the electrolytic sulfuric acid solution manufacturing process as described above, when the electrolytic sulfuric acid solution manufacturing system 1 is started up, specifically, at the first operation after the completion of the electrolytic sulfuric acid solution manufacturing system 1, the persulfuric acid solution 3 of the system 1 is operated. Electrolysis stored in the storage tank 2 during operation after the replacement of the system 1 or after the concentration of the persulfuric acid component in the persulfuric acid solution 3 stored in the system has decreased due to the shutdown of the system 1. The sulfuric acid solution 3 cannot be used as it is because the concentration of the persulfuric acid component is lower than the desired concentration for the desired treatment. Therefore, conventionally, it has been necessary to continue the circulation of the electrolytic sulfuric acid solution 3 between the storage tank 2, the circulation pipe 5, and the electrolytic cell 8 until the desired persulfuric acid concentration is reached. Therefore, it takes a long time and a large amount of energy to obtain the electrolytic sulfuric acid solution 3 having a desired persulfuric acid concentration, and there is a problem that the electrolytic sulfuric acid solution manufacturing system 1 cannot be started up in a short time.
　そこで、本実施形態においては、電解硫酸溶液製造システム１の立ち上げ時に所望とする過硫酸濃度及び硫酸濃度に短時間で到達するように調整を行う（濃度調整工程）。この調整は、例えば、過酸化水素水を添加し、さらに必要に応じて硫酸及び／又は水を添加することにより、それぞれの比率（濃度）を調整した被電解処理液を製造する。 Therefore, in the present embodiment, 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.
　これは、硫酸と過酸化水素と混合することにより、下記式（４）の反応により強い酸化性を有する過硫酸（ペルオキソ一硫酸）成分を生成することで、過硫酸濃度を調整することができるからである。
　Ｈ２ＳＯ４＋Ｈ２Ｏ２　⇔　Ｈ２ＳＯ５＋Ｈ２Ｏ　・・・（４） By mixing sulfuric acid and hydrogen peroxide, 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)
　ここで、添加する過酸化水素水は、一般的な工業薬品として使用される３５ｗｔ％の過酸化水素水などの任意の濃度の過酸化水素水を用いることができるが、電解硫酸溶液３中の酸化剤濃度を目的とする値とするための添加量が少なくて済むことから、高濃度の過酸化水素水を用いることが好ましく、一般工業薬品や電子工業用ＥＬグレード薬品を使い分けることができる。 Here, as 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.
　また、上記式（４）の反応における硫酸としては、濃度７０～９８重量のものが好ましいが、一般工業薬品や電子工業用ＥＬグレード薬品を使い分けることができる。 Further, as 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.
　さらに、被電解処理液の硫酸濃度が高すぎる場合には、希釈する必要があるか、この希釈に過酸化水素水を用いると、被電解処理液の酸化性が高くなりすぎる場合があるので、このような場合には、希釈用に水を添加することが好ましい。硫酸の希釈に用いる水は、水道水などの市水を使用することが可能であるが、各種カチオンやアニオンの混入を避けるために純水を使用するのが望ましく、各種材料表面の洗浄や改質に適用する処理対象によっては超純水を使用することもできる。 Furthermore, if 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. In such cases, it is preferable to add 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.
　これら各成分の添加方法に特に制限はないが、最終的な硫酸濃度に応じてあらかじめ水に濃硫酸を溶解した硫酸溶液を電解硫酸溶液製造システム１の貯留槽２に張り込み、急激な反応に注意しながら過酸化水素を緩やかに混合し、被電解処理液を調整する方法が好ましい。また、濃度調整された硫酸溶液と過酸化水素水を別途混合した被電解処理液を貯留槽２に張り込む方法でもよい。この操作の過程で、循環ポンプ６を稼働させるとともに電解セル８に通電し、循環液（被電解処理液）の電気分解を開始すればよい。 There is no particular limitation on the method of adding each of these components, but be careful of rapid reactions by filling the storage tank 2 of the electrolytic sulfuric acid solution production system 1 with a sulfuric acid solution in which concentrated sulfuric acid is dissolved in water in advance according to the final sulfuric acid concentration. A method of adjusting the electrolyzed liquid to be electrolyzed is preferable by gently mixing hydrogen with respect to the electrolyzed solution. Alternatively, a method of filling the storage tank 2 with a solution to be electrolyzed, which is a mixture of a sulfuric acid solution whose concentration has been adjusted and a hydrogen peroxide solution, may be used. In the process of this operation, the circulation pump 6 may be operated and the electrolytic cell 8 may be energized to start electrolysis of the circulating liquid (electrolyzed liquid).
　この過酸化水素水、硫酸及び水（純水）の添加量は、立ち上げ時の電解硫酸溶液３の性状を測定した結果に基づき決定すればよい。例えば、貯留槽２や循環配管５などに酸化剤濃度計や硫酸濃度計を設置しておき、この測定結果により過酸化水素水、硫酸又は純水の添加量を決定すればよい。具体的には、電解硫酸溶液３の過硫酸濃度が目的とする値よりも低い場合には、過酸化水素水及び必要に応じて硫酸や水を追加添加して過硫酸濃度（酸化剤濃度）を高める操作を行えばよい。ここで、過硫酸濃度の測定法としては、正しい値が測定できる方法であれば特に制限はなく、吸光光度法、酸化還元滴定法、ラマン分光法、ポーラログラフ法、電位測定法などを用いることができる。 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. For example, 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. Specifically, when the persulfuric acid concentration of the electrolytic sulfuric acid solution 3 is lower than the target value, 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. Here, 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.
　また、硫酸濃度計で測定された硫酸濃度が目的とする値よりも低い場合には硫酸を添加して濃度調整を行う。一方、硫酸濃度が目的とする値よりも高い場合には水および／または過酸化水素水を添加して濃度調整を行う。ここで、硫酸濃度の測定法としては、正しい値が測定できる方法であれば特に制限はなく、密度測定法、中和滴定法、超音波伝搬速度測定法、パックテスト法などを用いることができる。 If the sulfuric acid concentration measured by the sulfuric acid concentration meter is lower than the target value, add sulfuric acid to adjust the concentration. On the other hand, when the sulfuric acid concentration is higher than the target value, water and / or hydrogen peroxide solution is added to adjust the concentration. Here, 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. ..
　そして、この過硫酸（酸化剤濃度）を向上させた硫酸溶液（被電解処理液）を電解セル８に供給して電気分解し、過硫酸濃度及び硫酸濃度が目的とする値なるまるまで必要に応じて循環して電解を継続する（電解処理工程）。さらに、貯留槽２内の電解硫酸溶液３の温度が所望とする温度となるように加熱器４で加温することで、目的とする温度に調整すればよい（温度調整工程）。 Then, 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).
＜第二の実施形態＞
　次に本発明の第二の実施形態について説明する。第二の実施形態は、電解硫酸溶液製造システム１が異なる以外、前述した第一の実施形態と同じ作用効果を発揮する。 <Second embodiment>
Next, a second embodiment of the present invention will be described. The second embodiment exhibits the same effects as those of the first embodiment described above, except that the electrolytic sulfuric acid solution manufacturing system 1 is different.
［電解硫酸溶液製造システム］
　図２は本発明の電解硫酸溶液製造システムの立上げ方法を適用可能な第二の実施形態による電解硫酸溶液製造システムを示している。図２において、電解硫酸溶液製造システム１は、電解硫酸溶液３を受ける貯留槽２と、この貯留槽２の底部を出て中間槽１０に連通する配管５Ａと、中間槽１０から貯留槽２に還流する配管５Ｂとが設けられており、配管５Ａには送液機構としての送液ポンプ６Ａが設けられている一方、配管５Ｂには送液機構としての送液ポンプ６Ｂと、温度制御機構としての加熱用の熱交換器７Ａが設けられている。また、中間槽１０の底部には、この中間槽１０の底部を出て、再度中間槽１０に還流する循環配管５Ｃが設けられている。この循環配管５Ｃには、出口側（基端側）から順に送液機構としての循環ポンプ６Ｃと温度制御機構としての冷却用の熱交換器７Ｂと直流電源９に接続された電解セル８とが設けられている。この電解セル８は、アノード電極８Ａとバイポーラ電極８Ｂとカソード電極８Ｃとが設けられている。 [Electrolytic sulfuric acid solution manufacturing system]
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. In FIG. 2, 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. Further, 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.
［電解硫酸溶液の製造方法］
　次に上述したような電解硫酸溶液製造システム１を用いた電解硫酸溶液３の製造方法について説明する。まず、中間槽１０に硫酸成分を主体とする溶液を入れたら、中間槽１０から循環ポンプ６Ｃにより循環流路５Ｃを経由して電解セル８に供給し、直流電源９から所定の電流を通電して、硫酸成分を主体とする溶液を電気分解してペルオキソ二硫酸等の過硫酸成分を含む酸化性溶液（電解硫酸溶液３）を製造する。この酸化性溶液（電解硫酸溶液３）は、電解セル８による電解効率を向上させるため、冷却用熱交換器７Ｂにより冷却することが好ましい。この電解硫酸溶液３を循環配管５Ｃを経由して龍間奏１０に返送し、これを送液ポンプ６Ｂにより配管５Ｂから貯留槽２に供給する。このとき電解硫酸溶液３の温度が、該電解硫酸溶液３を用いた処理に応じた所望の温度となるように加熱用熱交換器７Ａにより加熱することが好ましい。このとき電解硫酸溶液３により生成するペルオキソ二硫酸等の過硫酸の濃度が該電解硫酸溶液３を用いる処理に応じた所望とする濃度となるように電解セル８における電流量を制御すればよい。そして、この電解硫酸溶液３を用いて、例えば樹脂成形体のエッチングなど目的とする処理を行えばよい。 [Manufacturing method of electrolytic sulfuric acid solution]
Next, a method for producing the electrolytic sulfuric acid solution 3 using the electrolytic sulfuric acid solution production system 1 as described above will be described. First, a solution mainly composed of a sulfuric acid component is put into the intermediate tank 10, then the solution is supplied from the intermediate tank 10 to the electrolytic cell 8 via the circulation flow path 5C by the circulation pump 6C, and a predetermined current is applied from the DC power supply 9. Then, a solution mainly composed of a sulfuric acid component is electrolyzed to produce an oxidizing solution (electrolytic sulfuric acid solution 3) containing a persulfate component such as peroxodisulfuric acid. 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. At this time, 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.
［電解硫酸溶液製造システムの立上げ方法］
　上述したような第二の実施形態において、電解硫酸溶液製造システム１の立ち上げ時には、前述した第一の実施形態と同様に過酸化水素水、必要に応じて硫酸及び／又は水を添加してやればよい。この場合、過酸化水素水、硫酸及び／又は水の添加する位置に特に制限はなく、貯留槽２、中間槽１０、配管５Ａ、５Ｂ、循環配管５Ｃなどに添加することができるが、特に中間槽１０に添加することが一般的である。また添加方法にも特に制限はなく、ポンプを用いて添加するなど汎用的な方法を適用することができる。 [How to set up an electrolytic sulfuric acid solution manufacturing system]
In the second embodiment as described above, when the electrolytic sulfuric acid solution manufacturing system 1 is started up, hydrogen peroxide solution, and if necessary, sulfuric acid and / or water may be added in the same manner as in the first embodiment described above. good. In this case, there is no particular limitation on the position where the hydrogen peroxide solution, sulfuric acid and / or water is added, and the hydrogen peroxide solution, sulfuric acid and / or water can be added to the storage tank 2, the intermediate tank 10, the pipes 5A and 5B, the circulation pipe 5C and the like, but particularly in the middle. It is common to add it to the tank 10. Further, the addition method is not particularly limited, and a general-purpose method such as addition using a pump can be applied.
　このような第二の実施形態によれば、硫酸溶液に過酸化水素水を添加して被電解処理液を調整し、この被電解処理液を各種処理や改質処理に必要となる液性に近い酸化力を有するまで中間槽１０と電解セル８を循環させて電解硫酸溶液３とし、その後貯留槽２に電解硫酸溶液３を所定の温度に調整して供給することができるので、貯留槽２をそのまま処理槽として用いることができる。さらに貯留槽２での所望とする処理と並行して、電解硫酸溶液３の製造を行うことができる。例えば、プラスチック材料表面をめっきするために行われる樹脂表面のエッチング処理に電解硫酸溶液を用いるめっき部品製造ラインにおいては、貯留槽２をエッチング槽として利用することができる。 According to such a second embodiment, 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. Since 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.
　上述した第一の実施形態及び第二の実施形態の電解硫酸溶液製造システムの立上げ方法によれば、電解硫酸溶液製造システム１の立上げ時に、過酸化水素水、必要に応じ硫酸及び／又は水を添加して酸化性を高めた被電解処理液を調整し、この被電解処理液を電解セル８に通電して電気分解を行うことで、短時間で所望とする過硫酸濃度及び硫酸濃度の電解硫酸溶液３を製造することができ、短時間で電解硫酸溶液製造システムの立上げを完了することができる。これにより、各種材料表面の洗浄処理や改質処理に必要となる液性に近い酸化力を有する溶液を、短時間の電解処理により得ることができ、洗浄や改質処理を開始するまでに要するエネルギー使用量を大幅に削減することが可能となる。 According to the method for setting up the electrolytic sulfuric acid solution manufacturing system of the first embodiment and the second embodiment described above, when the electrolytic sulfuric acid solution manufacturing system 1 is set up, a hydrogen peroxide solution, if necessary, sulfuric acid and / or 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. As a result, a solution having an oxidizing power close to liquid required for cleaning and reforming the surface of various materials can be obtained by short-time electrolytic treatment, and it is necessary to start the cleaning and reforming treatment. It is possible to significantly reduce the amount of energy used.
　また、本実施形態によれば、例えば過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩などの塩を添加することがないので、過硫酸塩に起因する水素イオン以外のカチオン成分の電解硫酸液への混入が生じることもない。さらに、液体のみを添加しているので取り扱いが容易である、という効果も奏する。 Further, according to the present embodiment, since 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.
　以上、本発明の電解硫酸溶液製造システムの立上げ方法について添付図面を参照して説明してきたが、本発明は上記の実施形態に限定されず種々の変形実施が可能である。例えば、硫酸、過酸化水素水及び水の添加手段を、硫酸濃度計及び酸化剤濃度計の測定結果に基づいて、それぞれの添加量をパーソナルコンピュータなどの演算・制御手段により最適値に制御することで、硫酸、過酸化水素水及び水の添加や電解セル８による電解時間（循環時間）を自動化するなどしてもよい。また、電解硫酸溶液３の硫酸濃度、過硫酸濃度及び温度は処理対象に応じて種々変更可能である。 Although the method for setting up the electrolytic sulfuric acid solution manufacturing system of the present invention has been described above with reference to the attached drawings, the present invention is not limited to the above embodiment, and various modifications can be carried out. For example, 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. Further, 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.
　以下に実施例及び比較例を示し、本発明をより具体的に説明する。ただし、本発明はこれらの記載により何ら限定されるものではない。 Examples and comparative examples are shown below, and the present invention will be described more specifically. However, the present invention is not limited to these descriptions.
［比較例１］
　ＡＢＳ樹脂成形体にめっきする前処理のための樹脂エッチング用いる過硫酸成分を含む電解硫酸溶液３の液性として、硫酸濃度７８ｗｔ％、過硫酸濃度７ｇ／Ｌ　ａｓ　Ｓ２Ｏ８及び温度６０℃を設定し、図１に示す電解硫酸溶液製造システム１で電解硫酸溶液３を以下の工程により製造した。 [Comparative Example 1]
As the liquid of the electrolytic sulfuric acid solution 3 containing a persulfate component used resin etching for pretreatment of plating the ABS resin molding, a sulfuric acid concentration of 78 wt%, persulfate concentration 7g / L as S 2 O 8 and the temperature 60 ° C. After setting, the electrolytic sulfuric acid solution 3 was produced by the electrolytic sulfuric acid solution production system 1 shown in FIG. 1 by the following steps.
　はじめに、貯留槽２に純水と９６ｗｔ％硫酸とを合計液容量１５Ｌとなるよう添加・混合し、硫酸濃度が７８ｗｔ％となるよう硫酸溶液を調整した。この硫酸溶液を循環ポンプ６を稼働させて流量２Ｌ／分で循環配管５から電解セル８に供給した。この際、電解セル８を循環する硫酸溶液の液温が５０℃以下となるよう、熱交換器７を用いて温度調整した。 First, pure water and 96 wt% sulfuric acid were added and mixed in the storage tank 2 so as to have a total liquid capacity of 15 L, and the sulfuric acid solution was adjusted so that the sulfuric acid concentration was 78 wt%. This sulfuric acid solution was supplied from the circulation pipe 5 to the electrolytic cell 8 at a flow rate of 2 L / min by operating the circulation pump 6. At this time, the temperature was adjusted by using the heat exchanger 7 so that the temperature of the sulfuric acid solution circulating in the electrolytic cell 8 was 50 ° C. or lower.
　電解セル８では、直流電源９からアノード電極８Ａとカソード電極８Ｃとの間に２０Ａの電流を通電し、循環している硫酸溶液の電気分解を行った。このアノード電極８Ａ、カソード電極８Ｃ、バイポーラ電極８Ｂとしては、シリコンウエハ表面にダイヤモンドを成膜した電極（ダイヤモンド電極）を使用した。また、アノード電極８Ａとカソード電極８Ｃの電極面積はいずれも５．２ｄｍ２とした。そして、電解セル８を通過した循環液（硫酸溶液）は貯留槽２に戻した。この際、循環液（硫酸溶液）中の過硫酸濃度を適宜測定し、循環液の性状が上記で設定したエッチングに用いる液性に達するまで循環し、電解セル８による電気分解を継続して電解硫酸溶液３を製造した。このとき貯留槽２内の電解硫酸溶液３は貯留槽２に設置した電気ヒーター（加熱器４）を用いて設定温度（６０℃）となるよう加温した。 In 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. As the anode electrode 8A, the cathode electrode 8C, and the bipolar electrode 8B, an electrode (diamond electrode) in which diamond was formed on the surface of a silicon wafer was used. 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. At this time, the persulfuric acid concentration in the circulating fluid (sulfuric acid solution) 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. 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.
　ここで、過硫酸濃度は、ヨウ素滴定法により測定した酸化剤濃度と過マンガン酸滴定法により測定した酸化剤濃度の差より求めた。ここで、ヨウ素滴定法とは、少量分取した測定対象液にＫＩを加えてＩ２を遊離させ、そのＩ２をＮａ２Ｓ２Ｏ３標準溶液で滴定してＩ２の量を求め、そのＩ２の量から酸化剤濃度を求める方法で、全酸化剤成分濃度が測定される。一方、過マンガン酸滴定は、少量分取した測定対象液に過マンガン酸カリウムを滴定する測定法で、測定対象液中の過酸化水素濃度のみを求めることができる。過硫酸濃度は、ヨウ素滴定法で求めた全酸化剤濃度から過酸化水素濃度に相当する酸化剤濃度を差し引くことにより算出する。 Here, 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. Here, 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. On the other hand, 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.
　これらの工程により、設定した液性の電解硫酸溶液３を製造するまでに２．５時間を要した。また、この間の電解に要した消費電力量は１ｋＷｈであった。 By these steps, it took 2.5 hours to produce the set liquid electrolytic sulfuric acid solution 3. The power consumption required for electrolysis during this period was 1 kWh.
　上述したようにして製造した電解硫酸液３にＡＢＳ樹脂試験片（ＢＵＬＫＳＡＭ　ＴＭ－２５、テクノＵＭＧ（株）製：４０ｍｍ×１３０ｍｍ×ｔ３ｍｍ）を１０分間浸漬してエッチングを行った。具体的には治具に取り付けた試験片を貯留槽２に浸漬した。そして、このエッチング後の試験片を５０℃の温水に１０分間浸漬した後、水洗し、さらに中和液（濃塩酸５０ｍＬ／Ｌ，３５℃）に１分間浸漬した。次に、試験片をパラジウム－スズコロイド触媒液（パラジウム濃度０．１１ｇ／Ｌ，スズ濃度１０．７ｇ／Ｌ，濃塩酸１８０ｍＬ／Ｌ，４０℃）に２分間浸漬し、水洗した後に活性化液（濃塩酸１００ｍＬ／Ｌ，４０℃）に１０分間浸漬して活性化処理を行った。この試験片を水洗した後、無電解ニッケルめっき液（ニッケル濃度８．０ｇ／Ｌ，ｐＨ９．０，４０℃）に１５分浸漬することでめっき処理を行った。このめっき処理工程を経た試験片には、全面に銀色のニッケルめっきが析出することが確認できた。 An 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. Next, 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.
［参考例］
　比較例１で使用したＡＢＳ樹脂試験片にエッチング処理を施すことなく、比較例１と同じ条件でめっき前処理を施し、さらにめっき処理を行った。このめっき処理工程を経た試験片には、表面積の約１０％以下程度でまばらにしかめっきが析出しておらず、エッチング処理がなければ、めっき製品としては不適当であることがわかった。 [Reference example]
The 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.
［実施例１］
　比較例１と同じ電解硫酸溶液製造システム１を用い、ＡＢＳ樹脂成形体にめっきする前処理のための樹脂エッチング用いる過硫酸成分を含む電解硫酸溶液３の液性として、硫酸濃度７８ｗｔ％、過硫酸濃度７ｇ／Ｌ　ａｓ　Ｓ２Ｏ８、温度６０℃を設定し、電解硫酸溶液３を以下の工程により製造した。 [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.
　はじめに、貯留槽２に純水と９６ｗｔ％硫酸とを合計液容量１５Ｌとなるよう添加・混合し、硫酸濃度が７８ｗｔ％となるよう硫酸溶液を調整した。この硫酸溶液を循環ポンプ６を稼働させて流量２Ｌ／分で循環配管５から電解セル８に供給した。この際、電解セル８を稼働させない状態、すなわち溶液の電気分解を行わない状態で、循環ポンプ６を稼働し循環配管５と貯留槽２との間で硫酸溶液を循環させた。 First, pure water and 96 wt% sulfuric acid were added and mixed in the storage tank 2 so as to have a total liquid capacity of 15 L, and the sulfuric acid solution was adjusted so that the sulfuric acid concentration was 78 wt%. This sulfuric acid solution was supplied from the circulation pipe 5 to the electrolytic cell 8 at a flow rate of 2 L / min by operating the circulation pump 6. At this time, the circulation pump 6 was operated and the sulfuric acid solution was circulated between the circulation pipe 5 and the storage tank 2 in a state where the electrolytic cell 8 was not operated, that is, the solution was not electrolyzed.
　次に貯留槽２へ３５ｗｔ％過酸化水素水を０．０５Ｌ添加した。この過酸化水素水の添加により液温が上昇するので、熱交換器７を用いて５０℃以下に冷却した。その後、硫酸溶液中の硫酸濃度を測定し、測定結果に応じて９６ｗｔ％硫酸を少量添加し、硫酸濃度７８ｗｔ％に調整して被電解処理液とした。その後、電解セル８を稼働して、この被電解処理液を循環ポンプ６を稼働させて循環配管５から流量２Ｌ／分で電解セル８に供給した。この際、電解セル８に供給される被電解処理液の液温が５０℃以下となるよう、熱交換器７を用いて温度を調整した。 Next, 0.05 L of 35 wt% hydrogen peroxide solution was added to the storage tank 2. Since the liquid temperature rises due to the addition of this hydrogen peroxide solution, it was cooled to 50 ° C. or lower using a heat exchanger 7. Then, the sulfuric acid concentration in the sulfuric acid solution was measured, and a small amount of 96 wt% sulfuric acid was added according to the measurement result to adjust the sulfuric acid concentration to 78 wt% to prepare a liquid to be electrolyzed. After that, the electrolytic cell 8 was operated, and the electrolyzed liquid was supplied to the electrolytic cell 8 from the circulation pipe 5 at a flow rate of 2 L / min by operating the circulation pump 6. At this time, the temperature was adjusted by using the heat exchanger 7 so that the temperature of the electrolyzed liquid supplied to the electrolytic cell 8 was 50 ° C. or lower.
　電解セル８では、前述した比較例１と同じ条件で通電し、電解セル８を通過した循環液は貯留槽２に戻した。この際、循環液中の過硫酸濃度を適宜測定し、循環液の性状が上記で設定したエッチングに用いる液性に達するまで電気分解を継続し、電解硫酸溶液３を製造した。このとき貯留槽２内の電解硫酸溶液３は貯留槽２に設置した電気ヒーター（加熱器４）を用いて設定温度（６０℃）となるよう加温した。 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.
　これらの工程により、設定した液性の電解硫酸溶液３を調整するまでに１０分を要した。また、この間に電解に要した消費電力量は０．０７ｋＷｈであった。これらのことから、所要時間及び消費電力量のいずれも比較例１と比較して約１／１５となっており、システムの立上げを短時間で完了できるとともにエネルギー消費量を大幅に低減することできることがわかる。 It took 10 minutes to prepare the set liquid electrolytic sulfuric acid solution 3 by these steps. In addition, the power consumption required for electrolysis during this period was 0.07 kWh. From these facts, both the required time and the power consumption are about 1/15 of those in Comparative Example 1, and the system start-up can be completed in a short time and the energy consumption can be significantly reduced. I know I can do it.
　上述したようにして製造した電解硫酸液３を用いて、比較例１と同じ条件でＡＢＳ樹脂試験片にエッチング処理及びめっき前処理を施し、さらにめっき処理を行った。このめっき処理工程を経た試験片には、比較例１と同様に全面に銀色のニッケルめっきが析出することが確認できた。 Using the electrolytic sulfuric acid solution 3 produced as described above, 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.
１　電解硫酸溶液製造システム
２　貯留槽
３　電解硫酸溶液
４　加熱器（温度制御機構）
５，５Ｃ　循環配管
５Ａ　配管
５Ｂ　配管
６，６Ｃ　循環ポンプ
６Ａ，６Ｂ　送液ポンプ
７　熱交換器（温度制御機構）
７Ａ　加熱用熱交換器（温度制御機構）
７Ｂ　冷却用熱交換器（温度制御機構）
８　電解セル
８Ａ　アノード電極
８Ｂ　バイポーラ電極
８Ｃ　カソード電極
９　直流電源
１０　中間槽 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

Claims (5)

  1. 　硫酸成分を主体とする溶液を電気分解して生成する過硫酸成分を含む酸化性溶液を製造するシステムの立ち上げ方法であって、
    　前記システム内に存在する硫酸成分を主体とする溶液の全部あるいは一部に過酸化水素水を添加して前記硫酸成分を主体とする溶液の酸化力を高めた状態に調整し、その溶液を電解セルに供給して電気分解を行う、電解硫酸溶液製造システムの立上げ方法。     It is a method of starting up a system for producing an oxidizing solution containing a persulfuric acid component, which is produced by electrolyzing a solution mainly composed of a sulfuric acid component.
    A hydrogen peroxide solution is added to all or part of the sulfuric acid-based solution existing in the system to adjust the oxidizing power of the sulfuric acid-based solution to an enhanced state, and the solution is electrolyzed. A method for setting up an electrolytic sulfuric acid solution manufacturing system that supplies cells to the cell for electrolysis.
  2. 　前記システムの立ち上げが、該システムの竣工後の初回稼働時、該システム内の過硫酸成分を含む酸化性溶液の交換後、該システムの稼働停止によりシステム内に貯留している酸化性溶液中の過硫酸成分の濃度が低下した後の稼働時のいずれかである、請求項１に記載の電解硫酸溶液製造システムの立上げ方法。 The system is started up in the oxidizing solution stored in the system due to the shutdown of the system after the replacement of the oxidizing solution containing the persulfuric component in the system at the first operation after the completion of the system. The method for setting up an electrolytic sulfuric acid solution manufacturing system according to claim 1, which is one of the operations after the concentration of the persulfuric component in the above is reduced.
  3. 　前記システム内に存在する硫酸成分を主体とする溶液の全部あるいは一部にさらに硫酸及び／又は水を添加する、請求項１又は２に記載の電解硫酸溶液製造システムの立上げ方法。 The method for setting up an electrolytic sulfuric acid solution manufacturing system according to claim 1 or 2, wherein sulfuric acid and / or water is further added to all or part of the solution mainly composed of sulfuric acid component existing in the system.
  4. 　前記システム内に存在する硫酸成分を主体とする溶液中の硫酸濃度及び／又は過硫酸濃度の測定値に応じて前記過酸化水素水、硫酸及び／又は水を添加する濃度調整工程と、前記過硫酸濃度が目的値となるように各濃度の測定値に応じて溶液を電気分解する電解処理工程と、前記酸化性溶液の温度が目的値となるように温度の測定値に応じて該溶液の加温又は冷却を行う温度調整工程とを有する、請求項３に記載の電解硫酸溶液製造システムの立上げ方法。 The concentration adjustment step of adding the hydrogen peroxide solution, sulfuric acid and / or water according to the measured value of the sulfuric acid concentration and / or the persulfate concentration in the solution mainly containing the sulfuric acid component existing in the system, and the excess. An electrolytic treatment step of electrolyzing the solution according to the measured value of each concentration so that the sulfuric acid concentration becomes the target value, and the solution of the solution according to the measured value of the temperature so that the temperature of the oxidizing solution becomes the target value. The method for setting up an electrolytic sulfuric acid solution manufacturing system according to claim 3, further comprising a temperature adjusting step of heating or cooling.
  5. 　前記システムが、前記酸化性溶液を貯留する貯留槽と、前記酸化性溶液を処理する電解セルと、前記貯留槽と前記電解セルとの間に溶液を循環させるための送液機構を備えた循環配管と、前記貯留槽内の酸化性溶液の温度及び／又は前記電解セルに供給する溶液の温度を制御する制御機構と、過酸化水素添加機構と、硫酸及び／又は水の添加機構とを備える、請求項３又は４に記載の電解硫酸溶液製造システムの立上げ方法。 The system includes a storage tank for storing the oxidizing solution, an electrolytic cell for processing the oxidizing solution, and a circulation mechanism for circulating the solution between the storage tank and the electrolytic cell. It is provided with a pipe, 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 a sulfuric acid and / or water addition mechanism. , The method for setting up the electrolytic sulfuric acid solution manufacturing system according to claim 3 or 4.
PCT/JP2020/034959 2020-05-18 2020-09-15 Startup method for electrolytic sulfuric acid solution manufacturing system WO2021234978A1 (en)

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JP2017171830A (en) * 2016-03-25 2017-09-28 独立行政法人国立高等専門学校機構 Processing method of composite material
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Publication number Priority date Publication date Assignee Title
JP2006114880A (en) * 2004-09-17 2006-04-27 Kurita Water Ind Ltd Sulfuric acid recycling cleaning system and sulfuric acid recycling persulfuric acid feeder
JP2006278915A (en) * 2005-03-30 2006-10-12 Kurita Water Ind Ltd Sulfuric acid recycling type cleaning system
JP2012215462A (en) * 2011-03-31 2012-11-08 Chlorine Engineers Corp Ltd Total concentration measurement method for oxidizing substance, concentration meter for measuring total concentration of oxidizing substance, and sulfuric acid electrolytic apparatus using the same
JP2016167560A (en) * 2015-03-10 2016-09-15 栗田工業株式会社 Production method of electrolytic sulfuric acid solution and production apparatus of electrolytic sulfuric acid solution
JP2017171830A (en) * 2016-03-25 2017-09-28 独立行政法人国立高等専門学校機構 Processing method of composite material
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