TW200934894A - Aqueous solution of highly-pure copper sulfate or copper sulfate including iron sulfate, process and apparatus for producing the same - Google Patents

Abstract

An aqueous solution of highly-pure copper sulfate or copper sulfate including iron sulfate, and a process and apparatus for producing the same, in which a copper ion can be eluted effectively and an aqueous solution of highly-pure copper sulfate or copper sulfate including iron sulfate can be obtained at a high level of production efficiency, is provided. An ion generating cell is divided into an anode part and a cathode part by a hydrogen ion-exchange membrane. In the cathode part, hydrogen gas is evolved from the surface of a cathode. In the anode part where an aqueous solution of dilute sulfuric acid or dilute iron sulfate is provided, a copper ion is eluted from an anode which comprises pure copperplate or a highly-pure copperplate of 6N or more to the anode part, and then, an aqueous solution of copper sulfate or copper sulfate including iron sulfate is produced in the anode part.

Description

200934894 IX. Description of the Invention [Technical Field] The present invention relates to a method and a device for producing a high-purity copper sulfate aqueous solution or a copper sulfate-containing copper sulfate aqueous solution, and a high-purity copper sulfate aqueous solution or an iron sulfate-containing copper sulfate aqueous solution. . [Prior Art] Conventionally, in the case of performing copper plating, an aqueous solution of copper sulfate hydrate is used as a plating solution in order to obtain necessary copper ions. However, when impurities other than copper are contained, the film properties of the plating layer are lowered. In addition, in recent years, a high-purity product using a copper material having a purity of 6 N (99.99 99%) or more as an anode (Anode) material has been produced, and high purity has been required for copper sulfate which is a raw material for a base bath of a shovel gold bath. As described above, the plating solution is supplied to the soluble anode method. In this case, copper ions are supplied to the plating solution, and a copper-phosphorus alloy (a copper plate, a copper plate, a copper ball or the like) is used as an anode to dissolve copper ions. When a copper copper sulfate bath-soluble anode method is used, a film called a black film is generated on the surface of the anode for the purpose of delaying the inactivation of the anode or suppressing the occurrence of copper powder by a disproportion reaction. In view of the fact that such a black film is a composite of phosphorus, an oxide, a hydroxide, a chloride, or the like in the alloy copper, it is possible to maintain a sound film system while maintaining a functional film under appropriate and appropriate conditions. difficult. Therefore, the black film is in actual industrial operation, repeating a number of slips and producing a formed film, but at this time, the film that has fallen off becomes a paste or a powder of a powder, such as a powder, which contaminates the plating solution, and has The occurrence of nodule is equal to the problem of adverse effects of the film formation surface. In the field of printed circuit boards, the soluble anode method using copper is prevalent. In the field of module substrates in the emerging field, the demand for micronization is more stringent, so the problem of sliding particles is a problem that cannot be ignored. Therefore, in such fields, it is required to change from an insoluble anode method to an insoluble anode method which cannot form a black film. || However, in the general insoluble anode method, even if the copper in the plating solution is consumed, the copper ion monomer cannot be replenished, and the additive is decomposed or deteriorated due to the strong oxidation reaction generated by the anode, so that there is a long-term stabilization operation. It is impossible. In order to solve such a problem, for example, it is proposed to provide a storage device for accommodating a storage material of a copper material in a dissolution tank containing a trivalent iron ion solution (for example, Patent Document 1). According to the manufacturing apparatus described in Patent Document 1, the oxidation of the anode Q copper material is suppressed, and copper ions can be supplied to the solution, and the insoluble anode method can be used for a long period of time. Therefore, in industrial operations, not only a dilute sulfuric acid aqueous solution having high-purity copper ions but also a high-purity sulfuric acid 'copper aqueous solution or an iron sulfate-containing copper sulfate aqueous solution is required. In addition, in the field of semiconductor devices, the circuit material of the multilayer circuit of the high-end product is converted from A1 to Cu, and the circuit formation step is also performed by the conventional RIE method (Reactive Ion Etching). Gradually converted to the dual damascene method, but in the copper double damascene step used now, 'the copper silicate bath is still dominated by the copper silicate bath step-5-200934894. . However, in the copper sulphate bath-soluble anode method, the purity or soundness of the membrane quality is not sufficient, and the application of the copper sulfate bath insoluble anode method in the production apparatus described in Patent Document 1 or the gold plating bath and copper ion generation are required. High purity of materials, etc.

In addition, due to the diversification of packaging technology, copper posts (post) are used in the bump structure*. In addition, the review is applicable to the structure of copper in the field of MEMS 0 (Micro-Electro-Mechanical Systems), in the field of fine mineral gold. The use of copper is gradually increasing, and therefore, the demand for gold plating bath, supply, and high purity of a material that generates copper ions is increased. In view of the above requirements, in order to efficiently generate copper ions, copper sulfate having a small amount of impurities is obtained, and a hydrogen ion exchange membrane partitions ions to form a tank into an anode chamber and a cathode chamber, and in the cathode chamber, hydrogen gas is released from the vicinity of the cathode. Further, in the anode chamber, a cathode formed of a conductor cage and a raw material copper, and a method for producing a composition in which copper ions are eluted in the anode chamber (for example, Patent Document 2). [Problem to be Solved by the Invention] The manufacturing method and manufacturing apparatus described in Patent Document 2 are based on the problem of the invention to be solved by the above-mentioned Japanese Patent Laid-Open Publication No. JP-A-2003- No. According to the above configuration, copper ions can be easily generated, and copper sulfate can be obtained stably. -6-200934894 However, in the manufacturing method and manufacturing apparatus described in Patent Document 2, the raw material copper contained in the conductor cage formed of titanium or the like is dissolved in the composition of the dilute sulfuric acid aqueous solution, and the copper ion is changed due to an increase in electric resistance. It is not easy to dissolve in an aqueous solution efficiently, and impurities are eluted from the conductor cage material. Even in a small amount, the purity of the aqueous copper sulfate solution is lowered. When the raw material copper is dissolved in a conductor cage formed of titanium or the like, the resistance of the conductor itself cannot be prevented due to the low electrical conductivity of the material, and leakage current is generated from the cage itself. In addition, the electric current of the raw material copper itself is also energized in contact with the cage material, and the contact resistance also occurs here. As compared with the device directly energized to the plate, the electric resistance is increased, Joule heat is generated, and energy is consumed and becomes no. The disadvantages of efficiency, high power consumption, etc. In addition, since the copper material sheet received in the cage does not have a uniform surface as an electrode on a macroscopic scale, it is uneven current distribution and is unstable. This result is that the electrolysis efficiency is lowered and the production efficiency is lowered. Further, in Patent Document 2, in order to form a copper sulfate aqueous solution containing a specific range of copper as an electric scoop bath base liquid product, the generated copper sulfate aqueous solution is heated and dried to make the copper concentration into a physically limited range of pentahydrate'. After the salt is calculated, it is necessary to calculate the required amount, and it is necessary to dissolve the 'salt in a dilute sulfuric acid aqueous solution to form a plating bath base liquid. Therefore, in each step after the solution is generated, the chance of contamination is increased, and the purity of the product is made. Reduced, and the problem of rising manufacturing costs. The present invention provides a high-purity copper sulfate aqueous solution or a high-purity copper sulfate aqueous solution containing a high-purity copper sulfate aqueous solution or an iron sulfate-containing copper sulfate aqueous solution or a sulfuric acid containing iron sulfate 200934894, which can efficiently obtain copper ions efficiently in view of the above circumstances. A method for producing a copper aqueous solution, a production apparatus, and a high-purity copper sulfate aqueous solution or an iron sulfate-containing copper sulfate aqueous solution are used. The method for producing the high-purity copper sulfate aqueous solution or the iron sulfate-containing copper sulfate aqueous solution of the present invention is characterized in that the hydrogen ion exchange membrane partitions the ion generating tank into an anode* chamber and a cathode chamber, and the cathode chamber is released from the cathode surface. And extracting copper ions into the anode chamber in the anode chamber, and extracting copper ions from the anode formed by the pure copper copper plate or the high-purity copper plate of 6N or more. An aqueous solution of copper sulfate or an aqueous solution of copper sulfate containing iron sulfate is produced. According to the manufacturing method of the above composition, since the copper ion is directly eluted from the pure copper copper plate or the high-purity copper plate of 6N (99.9999%) or more in the dilute sulfuric acid aqueous solution or the dilute aqueous iron sulfate solution, the elution efficiency is increased. The so-called pure copper copper plate refers to a copper plate having a composition of 4N (99.99%) or more. Q In addition, when the stirring flow of the electrolyte (dilute sulfuric acid aqueous solution or dilute aqueous iron sulfate solution) is applied to the surface of the anode, the oxidation and diffusion of the interface are activated, so that the copper surface can be flatly corroded when the copper ions are eluted (Erosion ). In addition, by using a pure copper copper plate or a high-purity copper plate of 6N or more at the anode, the passivation resistance of the anode surface is increased, and the applied current can be formed by using a copper plate of a general 4N (99.99%) degree. The electrode has a higher current, so the dissolution efficiency of the copper ion to the dilute sulfuric acid aqueous solution or the dilute iron sulfate aqueous solution is further improved. Thereby, an aqueous solution of copper sulfate having high quality and particularly high purity or an aqueous solution of copper sulfate containing iron sulfate can be produced. 200934894 The method for producing a high-purity copper sulfate aqueous solution or an iron sulfate-containing copper sulfate aqueous solution according to the present invention is the ion generating tank, wherein the volume division ratio and the inter-electrode ratio of the anode chamber and the cathode chamber are in a range of 4:3 to 5: The composition of 1. Further, the method for producing a high-purity copper sulfate aqueous solution or an iron sulfate-containing copper sulfate aqueous solution according to the present invention is the ion generating tank, and the volume division ratio and the interelectrode ratio of the anode chamber and the cathode chamber are 2:1. According to the manufacturing method of the above composition, by making the volume ratio of the cathode chamber smaller than the volume of the anode chamber, the amount of the electrolyte on the cathode chamber side can be reduced and the electric resistance can be shortened due to the shortening of the energization distance. Thereby, even if the voltage is applied to the electrode, the copper ions can be efficiently eluted, and when the voltage is applied to the counter electrode, the copper ions can be more efficiently eluted. Further, the capacity of the anode chamber in which copper ions are eluted is larger than that in the cathode chamber, so that the production amount of the aqueous copper sulfate solution or the aqueous solution of copper sulfate containing iron sulfate is larger than that of the cathode chamber. G. The method for producing a high-purity copper sulfate aqueous solution or an iron sulfate-containing copper sulfate aqueous solution according to the present invention includes a water extraction step of taking out an aqueous solution in the anode chamber, and a water extraction step according to the aqueous solution, and measuring the aqueous solution taken out from the anode chamber The concentration measurement step of the copper ion concentration and the aqueous solution having the copper concentration measured in the concentration measurement step are returned to the aqueous solution reflux step in the anode chamber, and the measurement is based on the measurement of the copper ion concentration in the concentration measurement step. A voltage, and/or an applied current is applied to the anode and cathode. According to the manufacturing method of the above composition, since the copper ion concentration of the aqueous solution in the anode chamber is directly measured by Real_Time 200934894, it is not necessary to heat and dry the produced aqueous solution to prepare a bath salt for the base bath of the product. . Further, since the aqueous solution used for the concentration measurement is directly returned to the anode chamber, the amount of the aqueous solution is not depleted. In addition, based on the measurement of the copper ion concentration, it is possible to control the application of a voltage or a current to each electrode to dissolve the copper ions to the most suitable state. Therefore, in the most suitable state for maintaining high efficiency, an aqueous solution of copper sulfate or sulfuric acid can be produced. Aqueous copper sulfate solution of iron. The apparatus for producing a high-purity copper sulfate aqueous solution or an iron sulfate-containing copper sulfate aqueous solution according to the present invention includes an ion generating tank, a hydrogen ion exchange membrane that partitions the inside of the ion generating tank into an anode chamber and a cathode chamber, and the cathode chamber. a pure copper copper plate or a high-purity copper plate of 6N or more which is provided in the anode chamber by electrification to discharge copper ions from the cathode which is supplied with hydrogen gas from the surface and supplied with a dilute sulfuric acid aqueous solution or a dilute aqueous solution of iron sulfate. The formed anode is formed.

❹ According to the manufacturing apparatus of the above composition, since copper ions are directly dissolved in a dilute sulfuric acid aqueous solution or a dilute aqueous solution of ferric sulfate from a pure copper copper plate or a high-purity copper plate of 6 N or more, the elution efficiency is increased. Further, when the agitating flow of the electrolyte is applied to the surface of the anode, the oxidation and diffusion of the interface are activated, so that when the copper ions are eluted, the surface of the anode can be flatly corroded (Erosion). Further, when a high-purity copper plate of 6 N or more is used for the anode, since the surface of the anode is difficult to passivate, the applied current can be made to be a high current, so that the elution efficiency of the copper ion to the dilute sulfuric acid aqueous solution or the dilute aqueous iron sulfate solution is further enhanced. Thereby, an aqueous solution of copper sulfate having a high quality of the cartridge and a high-purity aqueous solution of copper sulfate containing -10-200934894 can be produced. The apparatus for producing a high-purity copper sulfate aqueous solution or an iron sulfate-containing copper sulfate aqueous solution according to the present invention has an aqueous solution water extraction means for taking out an aqueous solution in the anode chamber, and a copper ion for measuring an aqueous solution taken out from the anode chamber according to the aqueous solution water extraction means. The concentration concentration measuring means and the aqueous solution reflux means for returning the aqueous solution having the copper concentration measured in the concentration measuring means back to the anode chamber are provided, and the measurement of the copper separation & concentration in the concentration measuring means is performed, and the control is performed. A concentration control means for applying a voltage and/or an applied current to the anode and the cathode. According to the manufacturing apparatus of the above composition, since the copper ion concentration of the aqueous solution in the anode chamber is directly measured by Real-Time, it is not necessary to heat and dry the aqueous solution after the production, and the salt for building the base bath of the product is prepared. step. Further, since the aqueous solution used for the concentration measurement is directly returned to the anode chamber, the amount of the aqueous solution is not depleted. In addition, based on the measurement of the copper ion concentration, it is possible to control the voltage or current applied to the Q of each electrode to make the copper ion elution optimal, so that an aqueous solution of copper sulfate or sulfuric acid can be produced in an optimum state for maintaining high efficiency. Aqueous copper sulfate solution of iron. * The apparatus for producing a high-purity copper sulfate aqueous solution or an iron sulfate-containing copper sulfate aqueous solution according to the present invention may be characterized in that the volume division ratio and the inter-electrode ratio of the anode chamber and the cathode chamber in the ion generation tank are 4: 3~ 5: The composition of 1 . Further, the apparatus for producing a high-purity copper sulfate aqueous solution or an iron sulfate-containing copper sulfate aqueous solution according to the present invention may be used in the ion generating tank to form a volume division ratio of the anode chamber and the cathode chamber of the above -11 - 200934894 and a composition between the electrodes. . According to the apparatus having the above configuration, by reducing the volume division ratio of the volume of the cathode chamber, the cathode chamber side can be reduced, and the electric resistance can be reduced by shortening the energization distance, and the copper ions can be efficiently eluted even if the voltage is applied. And when the voltage is applied, the copper ions can be eluted more efficiently. In addition, the capacity of the anode chamber in which copper ions are eluted is larger than that in the cathode chamber of the aqueous solution of copper sulfate or copper sulfate containing copper sulfate. The high-purity copper sulfate aqueous solution or the iron sulfate-containing solution of the present invention is produced by the above production method. Further, a high-purity copper sulfate aqueous solution or a ferric sulfate-containing liquid is produced by the above-described production apparatus. The high-purity copper sulfate aqueous solution or the iron sulfate-containing φ solution of the present invention is a gold-plated bath base liquid product of the above-described production method or high-purity quality produced by the production apparatus. The method for producing high-purity copper sulfate aqueous solution or the iron sulfate-containing solution of the present invention and the manufacturing apparatus thereof are plate-shaped anodes formed of a pure copper copper plate and a high-purity copper plate, which have low electric resistance, can be pressed, and do not perform special operations, and have an improved anode. The tendency of dissolution in the chamber is such that oxygen and free hydrogen are re-bonded, and water is also produced in a concentrated manner, and the concentration of the electrolyte is small. In addition, since the effective electrolytic area of the anode is substantially constant: the enthalpy ratio is 2:1 and the volume is smaller than the amount of cation electrolyte. The electrode chamber of the high counter electrode outside the electrode is large, and the amount produced is higher than that of copper sulfate water-soluble copper sulfate water, which can form high copper sulfate water or 6N or more to reduce the electrolytic oxygen amount to the limit, which is effective. 'Dilute sulfuric acid water-12- 200934894 The change in the amount of water reduction in the solution or the aqueous solution of dilute iron sulfate is small, and the sulfate ion in the aqueous solution is effectively managed. In addition, the oxidizing property in the anode interface is high, and the diffusion is also rapid. Therefore, the generation or liberation of Cu2 + ions can reduce the occurrence of a passivation layer on the surface of the anode, and can reduce the generation of copper powder due to the deuteration reaction. EFFECTS OF THE INVENTION According to the method and apparatus for producing a high-purity copper sulfate aqueous solution or an iron sulfate-containing copper sulfate aqueous solution according to the present invention, high-quality and high-purity copper sulfate can be produced with high productivity by the above-described composition and action. An aqueous solution or an aqueous solution of copper sulfate containing iron sulfate can reduce the chance of mixing impurities by reducing the number of steps, thereby achieving simultaneous improvement in quality, shortening of production time, and cost. The best mode for carrying out the invention φ The following describes an embodiment of a method for producing a high-purity copper sulfate aqueous solution or a copper sulfate-containing copper sulfate aqueous solution and a manufacturing apparatus thereof, which will be described with reference to the drawings. The method for producing a high-purity copper sulfate aqueous solution or a copper sulfate-containing copper sulfate aqueous solution according to the present embodiment can produce a copper sulfate aqueous solution or an aqueous solution containing copper sulfate or the like using the manufacturing apparatus shown in any one of Figs. . [First Embodiment] The following is a first embodiment of a method for producing a high-purity copper sulfate aqueous solution or a sulfuric acid-containing copper sulfate aqueous solution containing sulfur-13-200934894 in accordance with the present invention, and will be described with reference to Fig. 1 . . "Manufacturing Apparatus of Copper Sulfate Aqueous Solution or Ferric Sulfate-Containing Copper Sulfate Aqueous Solution" The apparatus for producing copper sulfate aqueous solution or iron sulfate-containing copper sulfate aqueous solution of the present embodiment (hereinafter simply referred to as a manufacturing apparatus) 1 is provided with an ion generating tank 2. The hydrogen ion exchange membrane 23 of the anode chamber 21 and the cathode chamber 22 is partitioned inside the ion generating tank 2, the cathode 24 provided in the cathode chamber 22, which is energized to release hydrogen gas from the surface, and the dilute sulfuric acid aqueous solution or dilute sulfuric acid is supplied. The anode chamber 21 of the iron aqueous solution is composed of a pure copper copper plate or an anode 25 formed of a high-purity copper plate of 6N (99.9999%) or more, which is eluted with copper ions in the anode chamber 21. The composition of the manufacturing apparatus 1 of the present embodiment will be described in detail below. The ion generating tank 2 has an open box shape above the inside, and stores a predetermined dilute sulfuric acid aqueous solution or a dilute iron sulfate aqueous solution therein. Further, the ion generating tank 2 is placed at a position of an anode chamber 21 to be described later, and a pipe omitted in the drawing is connected to a side wall near the bottom portion, and a dilute sulfuric acid aqueous solution containing copper ions or an aqueous solution of dilute ferric sulfate produced by the anode 21 can be sent outside. In the present embodiment, as the dilute sulfuric acid aqueous solution stored in the ion generating tank 2, for example, a dilute sulfuric acid aqueous solution H2S04 of a degree of 30 to 220 g/l (degree of ionization of 1 to 9 to 2.2 N) may be used or contained therein. Bivalent iron ion Fe2+, or trivalent iron ion Fe3 +. The hydrogen ion exchange membrane 23 is closely connected to the opposite side walls and the bottom of the ion generating-14-200934894 tank 2, and the ion generating tank 2 is separated into the anode chamber 21 and the cathode chamber 22, and the example shown in FIG. It is provided near the center of the ion generating tank 2. The hydrogen ion exchange membrane 23 selectively permeates the cesium ion H+. As a semi-permeable membrane, the water ion and the hydrogen ion H+ pass through the iron ion, but do not transmit the iron ion Fe2+, Fe3+ or the copper ion Cu2+ described later. Negative ions of metal ions and sulfate ions S042_. Further, the hydrogen ion exchange membrane 23 may selectively pass through the hydrogen ion H + , and a commercially available cationic resin or a hydrogen ion selective permeable membrane may be used. An anode 25 is provided in the anode chamber 21. The anode 25 is connected to a plate electrode on the positive electrode side of a direct current current supply device (refer to reference numeral 40 in Fig. 3). In the example of the drawing, in the anode chamber 21, a side wall opposite to the hydrogen ion exchange membrane 23 is disposed ( The left side of Figure 1). The anode 25 of the present invention is formed of a pure copper copper plate or a high purity bismuth copper plate of 6 N or more, and elutes a dilute sulfuric acid aqueous solution or a dilute iron sulfate aqueous solution stored in the anode chamber 21 with copper ions Cu2 + . As the anode 25, for example, a 6N8 (99.999998%) high-purity copper plate or the like can be suitably used. " The anode 25 is as shown in the figure, and it is preferable to form a plate shape. The plate-shaped electrode formed of a pure copper copper plate or a high-purity copper plate of 6N or more is used as the anode 25, and the copper ion Cu2+ is efficiently eluted into the aqueous solution of the dilute sulfuric acid. In particular, by using a high-purity copper plate of 6 N or more as an anode, since the surface of the anode is difficult to passivate, the applied current can be made to a high current, so that the dissolution efficiency of the copper ion to the iron sulfate solution is further enhanced. In addition, when the agitating flow of the electrolyte (dilute sulfuric acid aqueous solution or dilute iron sulfate aqueous solution) is applied to the surface of the anode-15-200934894 25, the oxidation and diffusion of the interface are activated, so that when the copper ions are eluted, the anode surface can be flatly corroded. (Erosion) prevents the anode 25 from being preferentially dissolved in the vicinity of the liquid surface of the dilute sulfuric acid aqueous solution or the dilute aqueous iron sulfate solution. Further, when a copper plate having a purity of less than 6 N is used as the anode 25, even if the external electrolytic current is a low current, the surface of the anode is rapidly blunt due to impurities in the copper, and it is difficult to efficiently dissolve the copper ion Cu2+. The solution of dilute aqueous solution of ferric sulfate. In order to improve the elution efficiency of copper ions, the shape and size of the anode 25 are preferably as large as possible in the shape and size of the surface area. Further, the shape and size of the anode 25 are appropriately determined in consideration of the volume or shape of the ion generating tank 2 and the anode chamber 21, the manufacturing efficiency, and the like. By using the anode 25 of the present invention, a high-quality and high-purity copper sulfate aqueous solution or a ferric sulfate-containing copper sulfate aqueous solution can be produced in the anode chamber 21. A cathode 24 is provided in the cathode chamber 22. The cathode 24 is connected to a negative electrode* electrode of a DC current supply device (not shown). The electrode is formed in a plate shape in the example of the drawing, and is disposed in the cathode chamber 22 in the vicinity of the side wall facing the hydrogen ion exchange membrane 23 ( The right side of Figure 1). The shape and size of the cathode 24 are preferably such that the shape and size of the surface area are as large as possible in order to increase the reactivity in the ion generating tank 2. In addition, as the material of the cathode 24, the reactivity with the dilute sulfuric acid aqueous solution or the dilute ferric sulfate aqueous solution is low, and the conductivity is excellent, and the embrittlement reactivity to hydrogen-16-200934894 may be low. For example, pure copper may be used. Copper alloy, Pt, Au, Ag, etc. Further, it may be applied to a surface of a Cu, Ti, C, or Pb material or the like, and may be coated with an electrode of a platinum group oxide structure such as Ir or Ru. [Manufacturing Method of Copper Sulfate Aqueous Solution or Ferric Sulfate-Containing Copper Sulfate Aqueous Solution] The method for producing a copper sulfate aqueous solution containing copper ions or a copper sulfate aqueous solution containing iron sulfate in the present embodiment is distinguished from the hydrogen ion exchange membrane 23 by $ The sub-groove 2 is formed into an anode chamber 21 and a cathode chamber 22, in which hydrogen gas is released from the surface of the cathode 24, and in an anode chamber 21 supplied with a dilute sulfuric acid aqueous solution or a dilute aqueous solution of ferric sulfate, from a pure copper copper plate, or 6N The anode 25 formed of the high-purity copper plate dissolves copper ions in the anode chamber 21, and in the anode chamber 21, a method of producing a copper sulfate aqueous solution or a copper sulfate aqueous solution containing iron sulfate is used. The production method of the copper sulfate aqueous solution or the iron sulfate-containing copper sulfate aqueous solution using the production apparatus 1 of the present embodiment will be described in detail below. Q When a copper sulfate aqueous solution or a copper sulfate aqueous solution containing iron sulfate is produced, the inside of the ion generating tank 2 is first filled with a dilute sulfuric acid aqueous solution or a dilute aqueous iron sulfate solution. In this state, water molecules, sulfuric acid ion S042·, hydroxide ion OH—, {iron ion Fe 2 + (Fe 3 + )}, undissociated sulfuric acid molecules, and hydrogen ions H+ are present in the cathode chamber 22, In the anode chamber 21, there are water molecules, sulfuric acid ions S042_, hydrogen ions H+, hydroxide ions, "iron ions Fe2 + (Fe3 + )}, undissociated sulfuric acid molecules, and trace copper ions Cu2+. Further, the above-mentioned iron ion Fe2 + (Fe3 + ) is present only when a dilute aqueous solution of ferric sulfate is used. -17- 200934894 Next, an electrolysis current of 2 to 15 A/dm2 is applied to the anode 25 and the cathode 24 by a direct current current supply means (refer to reference numeral 40 in Fig. 3). When an electrolysis current is applied to each electrode, near the surface of the cathode 24, the hydrogen ions H + in the cathode chamber 22 are released as hydrogen gas H2. At this time, in order to maintain the electrical neutrality of the cathode chamber 22, the positive ions must move from the anode chamber 21 to the cathode chamber 22, but since the hydrogen ion exchange membrane 23 is zoned between the two chambers 21, 22, only the anode chamber 21 is internally The hydrogen ions H + move to the cathode chamber 22. In this case, the copper ion Cu2 + and the iron ion Fe2 + (Fe3 + ) are not allowed to permeate through the hydrogen ion exchange membrane 23, and remain in the state in the anode chamber 21. Here, the upper limit of the electrolysis voltage applied to each electrode is changed depending on the stirring condition of the aqueous solution in the anode chamber 21, the temperature, the concentration, and the like, but may be set to a range in which the degree of oxygen bubbles does not occur on the surface of the anode 25. Next, by the above action, the hydrogen ion concentration of the anode chamber 21 is lowered. That is, the cations in the anode chamber 21 are reduced. At the anode 25, an electrolytic current is applied to a pure copper copper Q plate constituting the anode 25, or a 6N high purity copper plate. In a state where the cation (hydrogen ion H+) in the anode chamber 21 is lowered, the copper ion Cu2+ is dissolved from the anode 25' from the anode 25' to the dilute sulfuric acid aqueous solution or the dilute iron sulfate aqueous solution stored in the anode chamber 21 by being energized at the anode 25 of the anode chamber 21. The cation concentration in the initial state before the energization maintains the electrical neutrality in the anode chamber 21. At this time, the magnitude of the electrolysis current applied to the anode 25 is proportional to the amount of copper ion Cu2+ eluted from the anode 25. In this state, by continuously energizing the anode 25 and the cathode 24, "hydrogen gas H2 is continuously generated from the cathode, and the concentration of hydrogen ions -18 - 200934894 in the cathode chamber 22 is continuously reduced. Therefore, by the hydrogen ion exchange membrane 23, only the hydrogen ions H + inside the anode chamber 21 are continuously moved to the cathode chamber 22' to reduce the hydrogen ion H+ inside the anode chamber 21, that is, the cation concentration. As a result, a plate-shaped anode 25' formed of a pure copper copper plate or a high-purity copper plate of 6 N or more continuously dissolves a high-concentration copper ion Cu2 + aqueous solution of dilute sulfuric acid or an aqueous solution of dilute ferric sulfate stored in the anode chamber 21. By this, it is possible to efficiently produce a high-quality and high-purity aqueous solution of dilute sulfuric acid containing copper & ionic Cu2+ or an aqueous solution of dilute ferric sulfate. The produced dilute sulfuric acid aqueous solution containing copper ion Cu2+ or the aqueous solution of dilute ferric sulfate may be taken out through a pipe which is omitted from the pattern provided in the anode chamber 21, or may be a batch from the opening of the anode chamber 21. The method of taking out. Further, after the produced aqueous solution is taken out from the anode chamber 21, the dilute sulfuric acid aqueous solution containing the copper ion Cu2 + or the dilute sulfuric acid aqueous solution Q liquid can be continuously produced by supplying the dilute sulfuric acid aqueous solution or the dilute aqueous sulfuric acid solution to the ion generating tank 2. . As described above, according to the copper sulphate aqueous solution or the ferric sulphate-containing copper sulphate aqueous solution manufacturing method and manufacturing apparatus of the present embodiment, the pure copper copper plate provided in the anode chamber 21' or the anode formed by the 6N high-purity copper plate is used. In order to directly dissolve copper ions in a dilute sulfuric acid aqueous solution or a dilute aqueous solution of ferric sulfate, high-concentration copper ions can be efficiently eluted. Further, when a stirring flow of the electrolytic solution is applied to the surface of the anode 25, oxidation and diffusion of the interface are activated, so that when the copper ions are eluted, the surface of the anode 25 can be flatly corroded. In addition, by using a high-purity copper plate of 6N or more at the anode, due to the anode -19-

200934894 25 The surface is difficult to passivate, and the applied current can be the dissolution efficiency of high-electrode copper ion to the aqueous solution of iron sulfate. Thereby, a high-quality and oblique solution or an aqueous solution of copper sulfate containing iron sulfate can be produced with high manufacturing efficiency, and the opportunity for mixing impurities can be reduced, and the present invention can be simultaneously obtained. In addition, the impotence solution reaching the target copper ion concentration can be borrowed. The electrolyte solution is quickly supplied from the piping omitted from the drawing, and the aqueous copper acid solution of the copper sulfate aqueous solution can be continuously produced. In addition, a pipe connected to the anode chamber 21 is connected to a plating tank or the like, and a predetermined position such as a copper ion plating tank to be produced is quickly supplied. [Second embodiment] The following is a description of a method for producing a copper sulfate aqueous solution of high-purity iron sulfate according to the present invention and a manufacturing apparatus thereof, which will be described with reference to Fig. 2 . In the following description, the same configurations are given to the same configurations, and the detailed description is omitted. "Manufacturing device" The copper sulfate aqueous solution or the sulfur-containing liquid production device 10 of the present embodiment includes the ion generating tanks 2A and 2, so that the copper sulfate water having a higher degree of lift is reduced in quality by the number of steps and the chamber 21 is lowered. The water-soluble outside is supplemented with Cu2+, which is omitted from the new or sulfuric acid-containing sulphur, and the second embodiment of the above-mentioned electro-copper aqueous solution or sulfur-containing solution is used to dissolve the ion in the water-soluble zone of the first embodiment of the copper sulphate. -20- 200934894 The hydrogen ion exchange membrane 23 in the anode chamber 21A and the cathode chamber 22A in the tank 2A, the cathode 24 in the cathode chamber 22A which is energized to release hydrogen gas from the surface, and the anode chamber 21A in which the ferric sulfate aqueous solution is supplied An anode 25 formed of a 6N high-purity copper plate which is supplied with copper ions in the anode chamber 21A by electric current, is provided in the ion generating tank 2, and the cathode chamber 22A is made by the ratio of the hydrogen ion exchange membrane 23 The volume ratio is smaller than the volume of the anode chamber 21A, and the ratio between the electrodes on the cathode chamber 22A side is shorter than the ratio between the electrodes on the anode chamber 21A side, as shown in Fig. 2, the anode chamber. 21A and Division ratio and the electrode chamber volume between the electrodes 22A of the ratio is 2: 1. The manufacturing apparatus 10 of the present embodiment is incorporated in the ion generating tank 2A so that the ratio of the volume of the cathode chamber 22A is smaller than the volume of the anode chamber 21A by the ratio of the hydrogen ion exchange membrane 23, and the cathode chamber 22 can be reduced. The amount of electrolyte on the A side, and the ratio of the electrodes between the poles on the cathode chamber 22A side to the poles on the anode side 2 1 A side is shorter than the usual 1:1 groove setting, and the distance between the electrodes is shortened, which can be reduced. resistance. Thereby, even if the voltage is applied to each of the electrodes 24 and 25, the copper ions can be efficiently eluted. Further, by applying a voltage to each of the electrodes 24 and 25, copper ions can be efficiently eluted. Further, since the capacity of the anode chamber 21A in which copper ions are eluted is larger than that in the cathode chamber 22A, the amount of production of the aqueous copper sulfate solution or the aqueous solution of copper sulfate containing copper sulfate can be increased as compared with the amount of the cathode chamber. The manufacturing apparatus 10 of the present embodiment is incorporated in the ion generating tank 2A, and the volume division ratio and the inter-electrode ratio of the anode chamber 21 and the cathode chamber 22 are generated in the range of 1:3 -21 - 200934894 to 5:1, and the work efficiency is obtained. The upper range is preferably 4:3~5:1. When the volume division ratio and the inter-electrode ratio of the anode chamber 21A and the cathode chamber 22A are smaller than the ratio of the anode chamber 21A side of 4:3, the effect of improving the production efficiency and the like cannot be obtained because the distance between the electrodes is shortened. When the volume division ratio of the anode chamber 21A and the cathode chamber 22A and the ratio between the electrodes are larger than the ratio of the anode chamber 2 1A side of 5:1, the amount of hydrogen ions in the cathode chamber || 22A is significantly increased, and the cathode chamber 22A The polar chamber space on the side is too narrow, and there is a possibility that the electrolyte overflows or the conduction surface abnormally decreases and the abnormal discharge occurs due to reaction bubbles or the like from the cathode 24. Further, in the ion generating tank 2A, the volume division ratio of the anode chamber 21 and the cathode chamber 22 and the ratio between the electrodes are preferably 2:1 in terms of the above-mentioned manufacturing efficiency and the like. "Manufacturing Method" In the manufacturing method of the present embodiment, as described above, by using the manufacturing apparatus 10, the amount of the electrolytic solution of the cathode chamber 22A can be reduced by producing an aqueous solution of copper sulfate or an aqueous solution of copper sulfate containing iron sulfate. Reduce the resistance between the electrodes. Thus, even if the voltage is applied to the anode 25 and the cathode 24, the copper ions can be efficiently eluted. Further, by applying a voltage to the anode 25 and the cathode 24, copper ions can be more efficiently eluted. Further, since the capacity of the anode chamber 21A in which copper ions are eluted is larger than that in the cathode chamber 22A, the amount of production of the aqueous copper sulfate solution or the aqueous solution of copper sulfate containing copper sulfate can be increased as compared with the amount of the cathode chamber. -22-200934894 [Third embodiment] The third embodiment of the method and apparatus for producing a high-purity copper sulfate aqueous solution or an iron sulfate-containing copper sulfate aqueous solution according to the present invention will be described below with reference to Fig. 3 . In the following description, the same reference numerals are given to the same components as in the first embodiment, and the detailed description is omitted. "Manufacturing device" The apparatus for producing 11 of a copper sulfate aqueous solution or a copper sulfate aqueous solution containing iron sulfate according to the present embodiment includes an ion generating tank 2, and hydrogen ion exchange for arranging the anode chamber 21 and the cathode chamber 22 inside the ion generating tank 2 The membrane 23, the cathode 24 provided in the cathode chamber 22, and the cathode 24 which discharges hydrogen gas from the surface, and the anode chamber 21 supplied with the aqueous solution of ferric sulfate are energized to dissolve copper ions in the anode chamber 21. A manufacturing apparatus for an anode 25 formed of a purity copper plate or a high-purity copper-plated copper plate of 6 N or more, having an aqueous solution taking water 31 of an aqueous solution taken out in the anode chamber 21, and measuring from the anode chamber 2 1 according to the aqueous solution taking unit 31 The concentration measuring means 3 2 of the extracted copper ion concentration of the aqueous solution and the aqueous solution having the measured copper ion concentration in the concentration measuring means 32 are returned to the aqueous solution reflux means 33 in the anode chamber 21, and the concentration is measured based on the concentration. The measurement of the copper ion concentration in the means 32 controls the direct current supplied from the direct current supply device 40 to the anode 25 and the cathode 24 to apply a voltage, and/or Means for controlling the concentration of the applied current slightly Coming to 34 components. -23- 200934894 The aqueous solution water taking means 31 is in the ion generating tank 2, and the water inlet port provided on the anode chamber 21 side is taken from the dilute sulfuric acid aqueous solution or the dilute ferric sulfate which is stored, produced, or produced in the anode chamber 21. The aqueous solution is supplied to the concentration measuring means 32 to be described later via the water taking pipe. The aqueous solution water taking means 31 is exemplified in Fig. 3, and is formed into a tubular shape so as to be disposed from the opening portion of the anode chamber 21 into the anode chamber 21, but is not limited thereto, and may be connected to the side wall of the anode chamber 21, for example. The piping composition can be suitably used. The concentration measuring means 3 2 measures the copper ion concentration or the iron ion concentration of the aqueous solution fed from the anode chamber 2 1 by the aqueous solution taking means 31, and is formed, for example, by an absorbance meter or the like. The concentration measuring means 32 of the present embodiment is provided with a connection portion for omitting the measurement data of the copper ion concentration to the concentration control means 34 which will be described later. Further, the concentration measuring means 32 may be composed of a measurement data display portion formed of, for example, a display or the like. The aqueous solution reflux means 3 3 is obtained by taking the water from the anode ' chamber 2 1 by the aqueous solution taking means 31, and feeding it to the anode chamber 21 by the aqueous solution having the concentration measured by the concentration measuring means 3 2 through the water taking pipe, as shown in FIG. In the illustrated example, a return port is provided slightly above the open portion of the anode chamber 21. Here, the dilute sulfuric acid aqueous solution or the dilute ferric sulfate aqueous solution stored in the anode chamber 21 may be disposed in any one of the above-mentioned dilute sulfuric acid aqueous solution or dilute ferric sulfate aqueous solution passage. 24- 200934894 Location. In addition, the cartridge means may be built into the concentration measuring means. Further, the concentration control means 34 is based on the measurement of the concentration measurement of the copper ion concentration of the hand, and the control of the pressure applied to the anode 25 and the cathode 24, and/or the application of the current, is omitted from the pattern input from the concentration measuring means 32. The input portion and the direct current current supply means 40, which will be described later, are omitted in the drawings. Further, the concentration control means 34 may be provided with, for example, a display portion of the copper ion concentration measurement data displayed. The DC current supply means 40 is a power supply for supplying an electrolysis current to the anode 24, and includes a control adjustment means for controlling the voltage 供给 supplied to each electrode. Further, the DC current supply means 40 supplies not only the electrolytic electrode 25 and the cathode 24 but also the current for the concentration measuring means control means 34 and the squeezing means omitted. The basic operation system for producing a copper sulfate-containing copper sulfate-containing copper sulfate aqueous solution using the manufacturing apparatus 11 of the present embodiment is the same as the method described in the first aspect, and further, for example, the ion concentration measurement and the respective electrodes 24 are described below. 25 electrolytic systems supplied. In the manufacturing apparatus 11 of the present embodiment, the copper ion which is energized outside the group 32 of the copper sulfate aqueous solution 32 is outputted by the control unit, and the cathode current and the electric current are in the anode 3 2 . The concentration is given to the aqueous solution or the implementation mode, and the copper current is controlled or the sulfuric acid 25-200934894 iron-containing copper sulfate aqueous solution is produced, and the dilute sulfuric acid aqueous solution stored in the anode chamber 21 of the ion generating tank 2 is diluted or diluted. The aqueous solution of iron sulfate is taken up by the aqueous solution taking unit 31, and sent to the concentration measuring means 32 via the water taking pipe. The concentration measuring means 3 2 measures the copper ion concentration of the dilute sulfuric acid aqueous solution or the dilute iron sulfate aqueous solution, and sends the measurement data to the concentration control means 34, and the copper ion concentration in the concentration measuring means 32 is measured to end the diluted sulfuric acid. The aqueous solution or the dilute aqueous solution of ferric sulfate is returned to the anode chamber 21 again via the aqueous solution reflux means 0 33. Next, the concentration control means 34 is based on the copper ion concentration data sent from the concentration measuring means 32, and when the copper ion concentration of the dilute sulfuric acid aqueous solution or the dilute ferric sulfate aqueous solution exceeds the threshold ,, the DC current supply means 40 sends an instruction pair. When the anode 25 and the cathode 24 are applied with a voltage, and/or a control signal for stopping the current, when the copper ion concentration is lower than the valve, the DC current supply means 40 sends an indication to the anode 25 and the cathode 24 to apply a voltage, and/or The current continues to control the signal. The Q DC current supply means 40 controls the application of a voltage and/or an applied current to the anode 25 and the cathode 24 based on the control signal sent from the concentration control means 34. That is, when the concentration of copper ions in the dilute sulfuric acid aqueous solution or the dilute iron sulfate aqueous solution in the anode chamber 21 is high, the electrolyte is replenished in the anode chamber 21A and the cathode chamber 21B to lower the concentration or stop the application of current to the electrodes 24, 25. Further, when the concentration of copper ions in the dilute sulfuric acid aqueous solution or the dilute iron sulfate aqueous solution from which the water is taken in the anode chamber 21 is low, the current is continuously applied to the respective electrodes 24 and 25. By controlling the applied voltage and/or the applied current in this manner, the manufacturing apparatus 11 of the present embodiment -26-200934894 stops when the concentration of copper ions in the aqueous solution of dilute sulfuric acid or the aqueous solution of dilute ferric sulfate is as high as the target enthalpy Copper ions are dissolved. When the copper ion concentration reaches the target enthalpy, the diluted aqueous solution of dilute sulfuric acid or the aqueous solution of dilute ferric sulphate is taken out from the anode chamber 21 or taken out from the opening portion of the anode chamber 21 via a piping omitted from the drawing. At this time, as described above, the concentration measuring means 32 or the concentration control means 34 is provided with the measurement data indicating portion and the sensing portion which are omitted from the drawing, and the operator can visually confirm or mechanically induce copper sulfate. An aqueous solution or an aqueous solution of copper sulfate containing iron sulfate is produced. Therefore, the diluted aqueous solution of dilute sulfuric acid or the aqueous solution of dilute ferric sulfate can be quickly taken out from the anode chamber 21 manually or automatically, and the fresh dilute sulfuric acid aqueous solution or the aqueous solution of dilute ferric sulfate for the next generation can be immediately stored in the anode chamber 21. Improve manufacturing efficiency. Further, when the concentration of copper ions in the dilute sulfuric acid aqueous solution or the dilute iron sulfate aqueous solution which is produced is not increased, the copper ions can be further eluted so that the copper ion concentration reaches the target enthalpy. As described above, according to the manufacturing apparatus 11 of the present embodiment, since the copper ion concentration or the iron ion concentration of the aqueous solution in the anode chamber 21 is directly measured by Real-Time, it is not required to be heated as in the conventional heat drying. The aqueous solution, the steps of making the bath salt, etc., can reduce the steps and maintain the quality. In addition, the aqueous solution used for the concentration measurement is not directly deteriorated by analysis, and is directly returned to the anode chamber 2, and the aqueous solution is not contaminated or lost due to analysis. In addition, since the voltage or current is applied to each of the electrodes 24 and 25 based on the measurement of the copper ion concentration, the copper ion is most suitable for elution. Therefore, copper sulfate can be produced in an optimum state for maintaining high efficiency. 27- 200934894 Aqueous solution or aqueous solution of copper sulphate containing ferric sulphate' can also be automated in operation. Further, in the manufacturing apparatus 11 of the present embodiment, the copper ion concentration in the dilute sulfuric acid aqueous solution or the dilute iron sulfate aqueous solution is set to reach the target by the connection of the piping omitted from the pattern provided in the anode chamber 21. After the application of the electrolysis current to the anode 25 and the cathode electrode 24 from the DC current supply means 40, the solenoid valve is opened, and the produced dilute φ sulfuric acid aqueous solution or dilute iron sulfate aqueous solution is supplied outside the anode chamber 21. Thereby, the production effect of the dilute sulfuric acid aqueous solution containing copper ions or the aqueous solution of the dilute sulfuric acid can be further enhanced. [Embodiment] [Examples] Hereinafter, examples of the copper sulfate aqueous solution or the iron sulfate-containing copper sulfate aqueous solution of the present invention and a production apparatus thereof will be described in more detail, but the present invention is not limited to the embodiment. . In the present embodiment, the manufacturing apparatus 1 (test example 1), 1 〇 (test example 2), and 1 1 (test example 3) shown in Figs. 1 to 3 were produced, and a molten iron sulfate aqueous solution containing copper ions was produced. experimenting. [Manufacturing Apparatus] First, an ion generating tank 2 formed of an anode chamber 21 and a cathode chamber 22 having a volume of 2 L as shown in Figs. 1 and 3 was produced using an acrylic plate (Test Examples 1 and 3). -28- 200934894

Further, similarly, using an acrylic plate, an anode chamber 21A having a volume of 2 L (electrolyte volume of 1 mm×100 mm×200 mm) and a volume of 1 L (electrolyte volume of 100 mm×100 mm×100 mm) were produced as shown in FIG. 2 . Ion generating tank 2A formed in the cathode chamber 22A (Test Example 2) ° Further, a commercially available cation exchange membrane was used for the hydrogen ion exchange membrane which partitioned the anode chamber and the cathode chamber. Next, as the anode 25, a copper plate having a size of 100 mm x 200 mm x 20 mm (contact water area: 100 mm x 100 mm) is formed using high purity copper of 6 N or more (corresponding to 6N8: copper purity of 99.99998%), as shown in Fig. 1 As shown in FIG. 3, in the anode chambers 21 and 2 1 A of the ion generating tanks 2 and 2A, they are disposed on the side wall side (the left side in FIGS. 1 to 3) facing the hydrogen ion exchange membrane 23. In addition, as the cathode 24, a plate of a size of 100 mm x 200 mm x 20 mm (contact water area: 100 mm x 100 mm) is formed of pure copper equivalent to 4N8 (copper purity: 99.998%), as shown in Figs. The cathode chambers 22 and 22A of the tanks 2 and 2A are disposed on the side wall side (the right side in FIGS. 1 to 3) facing the hydrogen ion exchange membrane 23, and the manufacturing apparatus 1 shown in FIG. 1 (test example) 1: The ion generating tank 2) and the manufacturing apparatus 1A shown in Fig. 2 were used (Test Example 2: using the ion generating tank 2A). Further, in the manufacturing apparatus using the ion generating tank 2, as shown in Fig. 3, an aqueous solution water taking means 31 formed by a Teflon (registered trademark) tube is disposed, and the tip end portion is inserted into the anode chambers 21, 21A. Teflon -29- 200934894 (registered trademark) The water intake pipe formed by the tube is connected to the water inlet side of the measuring means 32 (made by Atotech Japan Co., Ltd.: copper, sub-instant analysis device). On the side of the concentration measuring means 32, an aqueous solution return section 33 formed of a Teflon (registered trademark) tube is connected, and the tip end portion is disposed slightly above the opening portion of the anode chamber 2 to be returned to the copper ion concentration after measurement. The composition of the dilute aqueous solution of ferric sulfate in the cation 2 1 , 2 1 A. Then, the measurement data output (Measure Port) of the concentration measuring means 32 is connected to a concentration control means 34 of a personal computer (ThinkPad manufactured by IBM Corporation), and the external communication interface of the personal computer (concentration control 34) is connected to the DC current supply means 40. The external interface of the Yamato plating machine: the precision gold-plated YPP-15100 for wafers was formed into a manufacturing apparatus 1 1 as shown in Fig. 3 (Test Example 3: sub-groove 2). φ [Test Example 1] In the manufacturing apparatus 1 shown in Fig. 1, the composition of the copper ion concentration can be measured in real time by connecting the liquid water taking means 31, the concentration measuring means 32, and the aqueous solution reflux means as shown in Fig. 3. Next, as a solution, a super-pure water containing 18.2 Μ Ω of a special-grade reagent sulfuric acid was added, and a dilute sulfuric acid solution of 180 g/L was measured by S04. The commercially available high-purity electrolytic iron became 13 g/L. To a dilute aqueous solution of ferric sulfate. Next, a dilute sulfuric acid aqueous solution was supplied to each of the anode 21 and the cathode chamber 22, and each was stored at 2 L. The concentration of iron is separated from the water flow hand, the shape of the chamber is out of the shape of the means of gold test communication with water soluble 33 > blocking water soluble, the pole chamber -30- 200934894 In addition, the electrolytic current of the anode 25 and cathode 24 plus the cathode 24 The current density on the side is 8.5 A/dm2 and the energization time is 5 hours. [Test Example 2] The manufacturing apparatus 10 shown in Fig. 2 was connected to the aqueous solution taking unit 31, the concentration measuring means 3, and the aqueous solution reflux means 3 3 as shown in Fig. 3, and the composition of the copper ion concentration was measured immediately. Next, as the electrolytic solution, ultra-pure water containing a special-grade reagent sulfuric acid of 18.2 ΜΩ was added to make the amount of S〇4 180 g/L, and the commercially available high-purity electrolytic iron was measured and dissolved to become 13 g/L. The resulting dilute aqueous solution of ferric sulfate was supplied to a dilute sulfuric acid aqueous solution, the anode chamber 21A was stored 2 L, and the cathode chamber 22A was stored at 1 L. Further, the current density of the electrolysis current to the anode 25 and the cathode 24 was 8.5 A/dm 2 on the side of the cathode 24, and the energization time was 5 hours. The evaluation results of Test Example 1 and Test Example 2 above are shown in Fig. 4 and Table 1. [Table 1] Voltage [mV] Test Example 1 (6N 1:1 tank) Test Example 2 (6N 2:1 tank) Maximum difference (MAX.) 7,290 mV 5,500 mV 1,790 Minimum (MIN·) 6,610 mV 5,110 mV 1,500 ( Maximum-minimum difference) 680 390 290 Average (AVE·) 6,838 mV 5,220 mV 1,619 As shown in the diagram of Figure 4 and Table 1, the electrolysis current is applied so that the current density on the side of the cathode 24-31 - 200934894 is 8.5 A/dm2. Test Example 2 of 2:1 tank (anode 21: cathode 11) Comparison with Test Example 1 of 1:1 tank (anode 21: cathode 21) showed that the applied voltage was low. The integrated average 値 is compared with the case where the voltage is applied, which is 6.8 V with respect to Test Example 1, and the test Example 2 is applied with a voltage lower than 5.2 V, and the resistance between the electrodes is low. Further, as shown in the graph of FIG. 4, the electrolysis voltage rises, and generally, the higher the applied voltage is, the passivation of the anode interface is likely to continue, and the rising curve becomes steep, but when a high-purity copper plate of 6 N or more is used at the anode, In Test Example 1 and Test Example 2, the curves of the same curvature were drawn because the current density resistance became high. However, when observing the difference between the maximum enthalpy and the minimum enthalpy of the applied voltage, the variation range of 680 mV in Test Example 1 was 390 mV in Test Example 2, and the test example 2 and 1:1 groove of 2:1 groove were tested. 1 comparison shows that the voltage fluctuation range becomes smaller and stable. It is considered that the lower the applied voltage is, the more stable it is, and the longer the electrolysis time can be extended to the passivation. When the average voltage A(Ave.) - the minimum 〇 voltage 値 (Min.) is expressed, the test example 1 is 68 3 8 - 66 1 0 = 228, Test Example 2 is 522 0 - 5110 = 110. At this time, the test of 2:1 groove is also shown. Example 2 is low and stable. From the above results, it can be judged that the method for producing copper sulfate aqueous solution or the aqueous solution of copper sulfate containing copper sulfate according to the present invention and the manufacturing apparatus thereof are as in the viewpoint of industrial production, as in Test Example 2, 2: 1 tank, for example, Test Example 1: 1 slot is suitable for operation. In addition, regarding the electrolysis efficiency (the ratio of the theoretical electrolysis enthalpy and the actual electrolysis amount obtained by the electric equivalent X electrode area X current 値X time), both sides are -100-200934894 to 100% (Test Example 1: 102%, Test Example 2: 99.8%) 'The ideal 値, no big difference was observed. [Test Example 3] Using the production apparatus 11 shown in Fig. 3, a continuous production test of an aqueous copper sulfate solution or an aqueous solution of copper sulfate containing iron sulfate was carried out. As an electrolyte, a super-purified water containing a special grade of sulfuric acid and a resistive yttrium of g 18.2 Μ Ω is used, and the amount of S04 is 180 g/L, and the commercially available high-purity electrolytic iron is measured and dissolved to become 13 g/L. An aqueous solution of dilute sulfuric acid was supplied to each of the anode chamber 21 and the cathode chamber 22 to store 2 L each. Then, by the concentration control means 34 and the DC current supply means 4, the current is changed from the stage of 500 mA to 10A, and the electrolysis current is supplied to the anode 25 and the cathode 24, and the observation is made that the surface of the anode is not passive. High current density. In addition, the target concentration of copper ions is 35 g/L. In the above Test Example 3, the measurement results of the component compositions are shown in Table 2. [Table 2] Composition of Ag Cu Fe Na Pb S04 Concentration <l(mR/l) 34·2_ 0.05 (mg/l) <l(mg/l) 190 (g/l) At intervals of about 30 minutes After the observation, the applied current was 9a or less. 'Although copper powder was generated from the anode due to the deuteration reaction, but no blunt-33-200934894 was observed. However, if the applied current exceeds 9 A, the deuteration is generated from the anode. Copper powder is more obvious, and it is considered to be passivated at 10 A, 2 hours. Therefore, it can be concluded that the method and apparatus for producing copper sulfate aqueous solution or copper sulfate-containing aqueous solution of the present invention have an appropriate correct current density of 8.5 A/dm2 during operation. In addition, the energization time to the copper ion concentration of 35 g/L (working time per batch) was calculated by the interval between copper ion concentration and electro-chemical calculation, and was calculated to be about 7 hours. Compared with the conventional manufacturing method and manufacturing apparatus, the manufacturing method and the manufacturing apparatus of the present invention can produce the ferric sulphate having the same degree of copper ion concentration in about 1/45 of the time in the range of about 3 weeks (320 hours) per batch. The aqueous solution showed excellent manufacturing efficiency. In addition, as shown in Table 2, the concentration of Ag and Pb in the dilute aqueous solution of iron sulfate at a copper ion concentration of 3 4.2 g/L is less than 1 mg/L, and the concentration of Na is 0.05 mg/L, which is very rare. The measurement results. [Test Example 4] In this test example, a copper plate formed of 6N (corresponding to 6N8) of high-purity copper and a commercially available 4N (corresponding to 4N8) of pure copper was used as the anode 25. Next, in the manufacturing apparatus 10 shown in FIG. 2, an aqueous solution water taking means 31, a concentration measuring means 3, an aqueous solution reflux means 3 3 as shown in FIG. 3 are connected, and the composition of the copper ion concentration can be measured immediately, and the test is carried out. A comparative evaluation was made when a copper plate having a different purity was used as the anode 25. Next, as the electrolytic solution, ultra-pure water of 18.2 ΜΩ was added to the resistor 硫酸-34-200934894, and the amount of S04 was 180 g/L. The commercially available high-purity electrolytic iron was metered and dissolved to 13.5 g/ The dilute aqueous solution of ferric sulfate produced by L was separately supplied to the dilute sulfuric acid aqueous solution 'anode chamber 2 1 A for storage 2 L, and the cathode chamber 22A for 1 L. Further, the current density of the electrolysis current to the anode 25 and the cathode 24 was 9 A/dm 2 on the side of the cathode 24, and the energization time was 6.5 hours. e In addition, when pure copper of 4N is used as the anode 25, the electrolyte temperature exceeds 5 (TC, and the ion generation tank 2 and the hydrogen ion exchange membrane 23 are destroyed by Joule heat. In this test example, the cooler and the special are used. In the glass cooling pipe, the cooling pipe was placed in the ion generating tank 2, and a solution for cooling the aqueous solution of the dilute ferric sulfate was placed. The test was carried out under the condition that the liquid temperature of the dilute aqueous solution of the molten iron sulfate was raised to 40 ° C. The evaluation results using 6N (equivalent to 6N8) of high-purity copper and 4N (equivalent to 4N8) of pure copper are shown in Figure 5 and Table 3. ❹ [Table 3] Euphemism in copper solution (mg) /1) Ag As Pb Zn 6N <0.01 0.02 0.007 0.08 4N 0.05 0.04 0.04 0.1

As shown in the graph of Fig. 5, when 6N (corresponding to 6N8) of high-purity copper is used as the anode 25, the voltage changes extremely smoothly, and there is no significant discoloration on the surface of the anode 25, and it is considered that no copper powder is produced at all. . The anode 25 of high-purity copper using 6N - 35 - 200934894 (corresponding to 6N8) is used at a flow density of 9 A/dm 2 on the cathode 24 side, and can be used without any problem under an operating condition of 6.5 hours. On the other hand, when 4N (corresponding to 4N8) pure copper is used as the anode, as shown in FIG. 5, about 20 minutes after the start of energization, the electrode interface is invented to exhibit incomplete resistance and passivation, even after the passivation is eliminated. The voltage 'movement amplitude is still intense, the surface of the anode 25 is discolored or rough, and a large amount of copper powder is produced. The concentration of copper ions in the aqueous solution is about 35 g/L when any of 6N high-purity copper and 4N copper is used as the anode 25, although it is not inferior, since the applied voltage is increased by using 4N pure copper as the anode 25, Therefore, the dissolution efficiency of copper ions becomes low. Further, in the aqueous solution in the anode chamber 21 in which the anode 25 of the 4N copper was used, the amount of the copper powder residue which was simply filtered was about 1.73 g, which was very large. Further, when 6N-purity copper was used as the anode 25, the amount of copper powder residue could not be detected, and the result was about ❹ zero. From this result, it is shown that when a high-purity copper 'anode 25 of 6N (corresponding to 6N8) is used, a high-purity copper sulfate aqueous solution can be obtained, and even when an electrolyte containing iron ions (iron sulfate) is used, it can be made high. The solution to efficiency. Further, as described above, when 4N pure copper is used as the anode 25, countermeasures against cooling of the electrolytic solution are required because of low electric efficiency or generation of copper powder residue 'and high Joule heat generation amount'. In addition, in the impurity analysis results shown in Table 3, the use of 6N high-voltage 25-generation pure pure but purely purely for the electrolysis of pure-36-200934894 copper as the anode 25, compared with the use of 4N pure copper, The mass of each of Ag and Zn becomes very small. In this test example, the use of high-purity electrolytic iron, the addition of the iron electrolyte, the addition of the impurities contained in the pure iron, so that the background number is increased, but when the high-purity copper of 6N is used as the anode 25, and when copper is used, The difference shown in the mass produced is large. From the above results, the method for producing and producing a copper sulfate aqueous solution of the high-purity copper sulfate aqueous solution of the present invention has a high rate, and the water solute produced by the production method and the production apparatus is small, and has high copper ion. The concentration is excellent in the characteristics of the aqueous solution. INDUSTRIAL APPLICABILITY According to the method for producing and producing a high-purity copper sulfate aqueous solution or an aqueous solution containing copper iron sulfate according to the present invention, it is possible to efficiently produce a copper sulfate aqueous solution or a sulfuric acid-containing sulfuric acid Q liquid with high purity and purity. By reducing the number of steps, it is possible to reduce the amount of impurities mixed into the machine to achieve improved quality, shortened production time and reduced cost. It is extremely effective in the industry. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] A schematic diagram showing an example of a device for producing a copper sulfate aqueous solution of a high-purity copper sulfate aqueous solution of the present invention. Fig. 2 is a schematic view showing another example of the apparatus for producing a copper sulfate aqueous solution of high-purity copper sulfate aqueous solution of the present invention;

Pb, and ions on a slightly 4N pure or sulfur-containing effect liquid, mixed sulfuric acid to produce high copper water soluble, can therefore, or sulfur or sulfur -37-200934894 [Figure 3] to explain the high purity sulfuric acid of the present invention A schematic diagram of another example of a copper aqueous solution or a device for producing a copper sulfate aqueous solution containing iron sulfate. Fig. 4 is an explanatory view showing an embodiment of a method for producing a high-purity copper sulfate aqueous solution or an aqueous solution containing copper sulfate having a ferric sulfate according to the present invention. Fig. 5 is an explanatory view showing an embodiment of a method for producing a high-purity copper sulfate aqueous solution or an aqueous solution containing copper sulfate having a ferric sulfate according to the present invention. 0 [Description of main component symbols] 1, 10, 11: manufacturing equipment (manufacturing device) of high-purity copper sulfate aqueous solution or iron sulfate-containing copper sulfate aqueous solution, 2: ion generating tank, 21: anode chamber, 22: cathode chamber, 23: hydrogen ion exchange membrane, 24: cathode, 25: anode, 3 1 : aqueous solution, 3 2: concentration measurement means, 33: aqueous solution reflux means, 34: concentration control means, 4: DC current supply means -38-

Claims (1)

200934894 X. Patent Application No. 1 · A method for producing a high-purity copper sulfate aqueous solution or a ferric sulfate-containing copper sulfate aqueous solution, characterized in that a hydrogen ion exchange membrane partitions an ion generating tank into an anode chamber and a cathode chamber, and the cathode chamber Hydrogen is released from the surface of the cathode, and in the anode chamber of the dilute sulfuric acid aqueous solution or the aqueous solution of dilute ferric sulfate, the anode is formed from a pure copper copper plate or a high-purity copper plate of 6 N or more, and copper ions are eluted in the anode chamber. In the anode chamber, an aqueous solution of copper sulfate or an aqueous solution of copper sulfate containing iron sulfate is produced. 2. The method for producing a high-purity copper sulfate aqueous solution or an iron sulfate-containing copper sulfate aqueous solution according to the first aspect of the patent application, wherein a volume division ratio and an inter-electrode ratio range of the anode chamber and the cathode chamber are used in the ion generation tank For 4: 3 to 5: 1. 3. The method for producing a high-purity copper sulfate aqueous solution or a copper sulfate-containing copper sulfate aqueous solution according to the first aspect of the patent application, wherein the ion generation tank, the volume division ratio of the anode chamber and the cathode chamber, and the ratio between electrodes 2:1° " 4. A method for producing a high-purity copper sulfate aqueous solution or a ferric sulfate-containing copper sulfate aqueous solution, which is a method for producing a copper sulfate aqueous solution or an iron sulfate-containing copper sulfate aqueous solution according to claim 1 The present invention is characterized in that it comprises a water extraction step of taking out an aqueous solution in the anode chamber, a water extraction step according to the aqueous solution, a concentration measuring step of measuring a copper ion concentration of the aqueous solution taken out from the anode chamber, and -39-200934894, the concentration measuring step The aqueous solution having a measured copper concentration is returned to the aqueous solution refluxing step in the anode chamber, and based on the measurement of the copper ion concentration in the concentration measuring step, a voltage is applied to the anode and the cathode, and/or an applied current is applied. An apparatus for producing a high-purity copper sulfate aqueous solution or a ferric sulfate-containing copper sulfate aqueous solution, comprising: an ion generating tank; and a hydrogen ion exchange membrane φ partitioning the inside of the ion generating tank into an anode chamber and a cathode chamber, the cathode a cathode provided in the chamber, which is supplied with hydrogen from the surface, a dilute sulfuric acid aqueous solution or a dilute aqueous solution of ferric sulfate, and is supplied with a copper copper plate or 6N by electrification to dissolve copper ions in the anode chamber. The anode formed by the above high-purity copper plate is formed. 6. A device for producing a high-purity copper sulfate aqueous solution or a copper sulfate-containing copper sulfate aqueous solution Q solution, which is a manufacturing device of a high-purity copper sulfate aqueous solution or an iron sulfate-containing copper sulfate aqueous solution according to claim 5 of the patent application scope, An aqueous solution water taking means for taking out an aqueous solution in the anode chamber, a concentration measuring means for measuring a copper ion concentration of the aqueous solution taken out from the anode chamber according to the aqueous water collecting means, and a copper concentration in the concentration measuring means are measured The aqueous solution, the aqueous solution reflux means returned to the anode chamber, and the measurement of the copper ion concentration in the concentration measuring means, controlling the voltage applied to the anode and the cathode, and the concentration control means of -40-200934894 / or the applied current to make. 7_ Manufactured as a high-purity copper sulfate aqueous solution or an iron sulfate-containing copper sulfate aqueous solution according to claim 5, wherein a volume division ratio and an inter-electrode ratio range of the anode chamber and the cathode chamber in the ion generation tank For 4: 3 to 5: 1. 8. The method for producing a high-purity copper sulfate aqueous solution or a copper sulfate-containing copper sulfate aqueous solution according to claim 5, wherein the ion generating 6-slot, the anode chamber and the cathode chamber have a volume division ratio and an electrode The ratio of the ratio is 2:1°. 9. A high-purity copper sulfate aqueous solution or an iron sulfate-containing copper sulfate aqueous solution, which is produced by the production method according to any one of claims 1 to 4. A high-purity aqueous copper sulfate solution or a copper sulfate aqueous solution containing iron sulfate, which is produced by the production apparatus according to any one of claims 5 to 8. 〇 -41 -