Method for producing basic copper carbonate and method for producing copper oxide

Abstract

To provide a method for producing basic copper carbonate, capable of producing basic copper carbonate with a reduced amount of copper salt-derived impurities such as chlorine.SOLUTION: The method for producing basic copper carbonate includes: a step A of simultaneously supplying a copper salt aqueous solution and an alkaline aqueous solution A containing an alkali metal carbonate into a reaction tank; and a step B of simultaneously supplying a copper salt aqueous solution and an alkaline aqueous solution B containing an alkali metal carbonate and an alkali metal hydroxide into the reaction tank. The pH of the alkaline aqueous solution B is greater than the pH of the alkaline aqueous solution A.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a method for producing basic copper carbonate and a method for producing copper oxide. [Background technology]

[0002] Copper plating technology is used in the manufacture of many electronic materials, including printed circuit board wiring, printing rolls, electrolytic foils, and wires. As a result, there is a demand for technologies related to copper oxide used in copper plating. One example is the technology to manufacture basic copper carbonate, which is a raw material in the manufacture of copper oxide.

[0003] Patent Document 1 discloses a method for producing basic copper carbonate, which comprises mixing an aqueous solution containing copper ions with an aqueous solution containing carbonate ions, maintaining the pH in the range of 7 to 10 while heating the aqueous solution to react reactants, and filtering and washing the precipitated reaction product to obtain basic copper carbonate. Patent Document 1 also describes that it focuses on basic copper carbonate, which can be used in place of copper oxide as a plating material in copper plating treatment and generates copper oxide by thermal decomposition, and aims to provide a method for producing a copper plating material in which the by-products produced during the production are easily filtered and separated and the filtration rate is high. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 02-289423 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention provides a method for producing basic copper carbonate that can produce basic copper carbonate with reduced amounts of impurities derived from copper salts, such as chlorine. [Means for solving the problem]

[0006] According to the present invention, there are provided a method for producing basic copper carbonate and a method for producing copper oxide, which are shown below.

[0007] 1. A step A of simultaneously supplying an aqueous copper salt solution and an aqueous alkaline solution A containing an alkali metal carbonate into a reaction vessel; A step B of simultaneously supplying an aqueous copper salt solution and an aqueous alkaline solution B containing an alkali metal carbonate and an alkali metal hydroxide into a reaction vessel; Including, The method for producing basic copper carbonate, wherein the pH of the alkaline aqueous solution B is higher than the pH of the alkaline aqueous solution A. 2. A step A of simultaneously supplying an aqueous copper salt solution and an aqueous alkaline solution A containing an alkali metal carbonate into a reaction vessel; A step B of simultaneously supplying an aqueous copper salt solution, an aqueous alkali solution b1 containing an alkali metal carbonate, and an aqueous alkali solution b2 containing an alkali metal hydroxide into a reaction tank; Including, A method for producing basic copper carbonate, in which the pH of the obtained alkaline aqueous solution B is higher than the pH of the alkaline aqueous solution A by the following <procedure>. <Procedure> The supply amount of the alkaline aqueous solution b1 per unit time is X b1 mL / min, the supply amount of the alkaline aqueous solution b2 per unit time is X b2 When expressed as mL / min, X b1 mL of the alkaline aqueous solution b1 and X b2 1 mL of the alkaline aqueous solution b2. 3. In the method for producing basic copper carbonate according to 1. or 2., A method for producing basic copper carbonate, comprising carrying out the step B after the step A. 4. In the method for producing basic copper carbonate according to any one of 1. to 3., The method for producing basic copper carbonate, wherein the copper salt comprises copper chloride. 5. In the method for producing basic copper carbonate according to any one of 1. to 4., The method for producing basic copper carbonate, wherein the alkali metal carbonate comprises sodium carbonate. 6. In the method for producing basic copper carbonate according to any one of 1. to 5., The method for producing basic copper carbonate, wherein the alkali metal hydroxide comprises sodium hydroxide. 7. In the method for producing basic copper carbonate according to any one of 1. to 6., The method for producing basic copper carbonate, wherein the pH of the alkaline aqueous solution A is 7.0 or more and 13.0 or less. 8. In the method for producing basic copper carbonate according to any one of 1. to 7., The content of the alkali metal carbonate in the alkaline aqueous solution A is from 0.1 mol / L to 10 mol / L. 9. In the method for producing basic copper carbonate according to any one of 1. to 8., A method for producing basic copper carbonate, wherein in the step A, the pH in the reaction tank is adjusted to 6.0 or more and 10.0 or less by adjusting the amount of the aqueous alkaline solution A supplied per hour. 10. In the method for producing basic copper carbonate according to any one of 1. to 9., A method for producing basic copper carbonate, wherein the temperature in the reaction tank in step A is 25°C or higher and 95°C or lower. 11. The method for producing basic copper carbonate according to any one of 1. to 10., The method for producing basic copper carbonate, wherein the pH of the alkaline aqueous solution B is 9.0 or more and 14.0 or less. 12. The method for producing basic copper carbonate according to any one of 1. to 11. The content of the alkali metal carbonate in the alkaline aqueous solution B is from 0.1 mol / L to 10 mol / L. 13. In the method for producing basic copper carbonate according to any one of 1. to 12., The content of the alkali metal hydroxide in the alkaline aqueous solution B is from 0.1 mol / L to 10 mol / L. 14. In the method for producing basic copper carbonate according to any one of 1. to 13., A method for producing basic copper carbonate, wherein the ratio of the number of moles of the alkali metal hydroxide to the number of moles of the alkali metal carbonate in the alkaline aqueous solution B is 1.10 or more. 15. In the method for producing basic copper carbonate according to any one of 1. to 14, A method for producing basic copper carbonate, wherein in the step B, the pH in the reaction tank is adjusted to 6.0 or more and 10.0 or less by adjusting the amount of the aqueous alkaline solution B supplied per hour. 16. In the method for producing basic copper carbonate according to any one of 2. to 14, In the step B, the pH in the reaction tank is adjusted to 6.0 or more and 10.0 or less by adjusting the amount of the aqueous alkaline solution b1 supplied per hour and / or the amount of the aqueous alkaline solution b2 supplied per hour. 17. In the method for producing basic copper carbonate according to any one of 1. to 16, The method for producing basic copper carbonate, wherein the temperature in the reaction tank in step B is 25°C or higher and 95°C or lower. 18. In the method for producing basic copper carbonate according to any one of 1. to 17, A method for producing basic copper carbonate, wherein a ratio of the number of moles of the alkali metal hydroxide used in the step A and the step B to the total number of moles of the alkali metal carbonate used in the step A and the step B is 1.10 or more. 19. A step of obtaining basic copper carbonate by the method for producing basic copper carbonate according to any one of 1. to 18. and step C of obtaining copper oxide using the obtained basic copper carbonate as a raw material. 20. The method for producing copper oxide according to 19., The method for producing copper oxide, wherein the pH in the reaction tank in step C is 9.0 or higher. 21. The method for producing copper oxide according to 19. or 20., The method for producing copper oxide, wherein the temperature in the reaction tank in step C is 45°C or higher and 95°C or lower. Effect of the Invention

[0008] According to the present invention, it is possible to provide a method for producing basic copper carbonate that can produce basic copper carbonate with reduced amounts of impurities derived from copper salts, such as chlorine. [Brief description of the drawings]

[0009] [Figure 1] 1 is a flowchart showing an example of a method for producing basic copper carbonate according to the first embodiment. [Diagram 2] FIG. 1 is a schematic diagram showing an example of a method for producing basic copper carbonate according to a first embodiment. [Diagram 3] 1 is a flowchart showing an example of a method for producing basic copper carbonate according to a second embodiment. [Figure 4] FIG. 2 is a schematic diagram showing an example of a method for producing basic copper carbonate according to a second embodiment. [Diagram 5] 1 is a flowchart showing an example of a method for producing copper oxide according to an embodiment of the present invention; [Figure 6] FIG. 1 is a schematic diagram showing an example of a method for producing copper oxide according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] 1. Method for producing basic copper carbonate The method for producing basic copper carbonate according to the present invention will now be described.

[0011] The method for producing basic copper carbonate according to the first embodiment includes step A of simultaneously supplying an aqueous copper salt solution and an alkaline aqueous solution A containing an alkali metal carbonate into a reaction vessel, and step B of simultaneously supplying an aqueous copper salt solution and an alkaline aqueous solution B containing an alkali metal carbonate and an alkali metal hydroxide into the reaction vessel, wherein the pH of the alkaline aqueous solution B is higher than the pH of the alkaline aqueous solution A. The method for producing basic copper carbonate according to the second embodiment includes step A of simultaneously supplying an aqueous copper salt solution and an aqueous alkali solution A containing an alkali metal carbonate into a reaction tank, and step B of simultaneously supplying an aqueous copper salt solution, an aqueous alkali solution b1 containing an alkali metal carbonate, and an aqueous alkali solution b2 containing an alkali metal hydroxide into the reaction tank, wherein the pH of the aqueous alkali solution B obtained by the following <procedure> is higher than the pH of the aqueous alkali solution A. <Procedure> The supply amount of the alkaline aqueous solution b1 per unit time is X b1 mL / min, the supply amount of the alkaline aqueous solution b2 per unit time is X b2 When expressed as mL / min, X b1 mL of the alkaline aqueous solution b1 and X b2 1 mL of the alkaline aqueous solution b2. In this specification, the "first embodiment" and the "second embodiment" are collectively referred to as "the present embodiment."

[0012] Basic copper carbonate is a divalent copper ion, Cu 2+ and carbonate ion CO 3 2- and hydroxide ion OH - The composition of the basic copper carbonate according to the present embodiment is not particularly limited, but for example, dicopper (II) carbonate dihydroxide Cu 2 (OH) 2 (CO 3 ) and tricopper(II) bis(carbonate) dihydroxide Cu 3 (OH) 2 (CO 3 ) 2 Preferably, copper(II) carbonate dihydroxide Cu 2 (OH) 2 CO 3 Includes.

[0013] Basic copper carbonate is, for example, a copper ion, Cu 2+ In a solution containing carbonate ions, 3 2- The resulting solution is obtained by adding an aqueous alkaline solution containing

[0014] For example, when copper chloride is used as the copper ion source and sodium carbonate is used as the alkali, the reaction to produce basic copper carbonate proceeds as shown in the following reaction formula (1). 2Na 2 CO 3 +2CuCl 2 +H 2 O→CuCO 3 Cu(OH) 2 +4NaCl+CO 2 ↑···(1)

[0015] In addition, when copper chloride is used as the copper ion source and sodium carbonate and sodium hydroxide are used as the alkali, the carbon dioxide produced by the reaction between copper chloride and sodium carbonate reacts with sodium hydroxide to produce sodium carbonate again. Therefore, the amount of sodium carbonate used can be reduced, and the emission of carbon dioxide outside the reaction system can also be reduced. In this case, the reaction theoretically proceeds as shown in the following reaction formula (2). Na 2 CO 3 +2NaOH+2CuCl 2 →CuCO 3 Cu(OH) 2 +4NaCl···(2)

[0016] Although the reaction according to reaction formula (2) has the above-mentioned advantages, it has the problem of increasing the amount of impurities derived from copper salts, such as chlorine.

[0017] Therefore, the inventors have conducted extensive research and found that the amount of impurities derived from copper salts can be reduced by combining a treatment step with an alkaline aqueous solution having a relatively low pH with a treatment step with an alkaline aqueous solution having a relatively high pH. In other words, according to the method for producing basic copper carbonate according to this embodiment, it is possible to produce basic copper carbonate with a reduced amount of impurities derived from copper salts. Reducing the amount of impurities is preferable because it makes it possible to improve the quality of products such as copper oxide produced from basic copper carbonate and further plating solutions produced from copper oxide.

[0018] Furthermore, according to the method for producing basic copper carbonate according to the present embodiment, it is possible to suppress the particle size of the basic copper carbonate from becoming finer. If the particle size becomes too fine, handling becomes difficult, so it is desirable to suppress the particle size from becoming finer to a certain extent.

[0019] In the method for producing basic copper carbonate according to this embodiment, the order of step A and step B is not particularly limited. From the viewpoint of further reducing the amount of impurities derived from the copper salt and further suppressing the refinement of the particle size, however, it is preferable to carry out step B after step A.

[0020] (1) First embodiment The method for producing basic copper carbonate according to the first embodiment includes step A of simultaneously supplying an aqueous copper salt solution and an alkaline aqueous solution A containing an alkali metal carbonate into a reaction vessel, and step B of simultaneously supplying an aqueous copper salt solution and an alkaline aqueous solution B containing an alkali metal carbonate and an alkali metal hydroxide into the reaction vessel, wherein the pH of the alkaline aqueous solution B is higher than the pH of the alkaline aqueous solution A.

[0021] Fig. 1 is a flow chart showing an example of a method for producing basic copper carbonate according to embodiment 1. Hereinafter, the method for producing basic copper carbonate according to embodiment 1 will be described with reference to the flow chart in Fig. 1. First, ion-exchanged water, which serves as a diluent, is placed in a reaction tank. Next, an aqueous copper salt solution and an aqueous alkaline solution A containing an alkali metal carbonate are simultaneously fed into the reaction vessel (step A). Next, the copper salt aqueous solution and an alkaline aqueous solution B containing an alkali metal carbonate and an alkali metal hydroxide are simultaneously fed into the reaction vessel (step B). The resulting basic copper carbonate slurry is then washed, dehydrated and dried to obtain basic copper carbonate powder.

[0022] FIG. 2 is a schematic diagram showing an example of a method for producing basic copper carbonate according to the first embodiment. According to the manufacturing method shown in the schematic diagram of FIG. 2, first, ion-exchanged water serving as a diluent (not shown) is placed in a reaction vessel 101 . Next, the copper salt aqueous solution from the copper salt aqueous solution storage tank 102 and the alkaline aqueous solution A from the alkaline aqueous solution A storage tank 103 are simultaneously supplied into the reaction tank 101 (step A). ​​The supply amount of the copper salt aqueous solution can be controlled by a supply amount control device 112. The supply amount of the alkaline aqueous solution A can be controlled by a supply amount control device 113. Next, the copper salt aqueous solution from the copper salt aqueous solution storage tank 102 and the alkaline aqueous solution B from the alkaline aqueous solution B storage tank 104 are simultaneously supplied into the reaction tank 101 (step B). The supply amount of the alkaline aqueous solution B can be controlled by the supply amount control device 114. The resulting basic copper carbonate slurry is then fed to a washing tank 105 for washing, fed to a centrifuge 106 for dehydration, and fed to a dryer 107 for drying, to obtain basic copper carbonate powder.

[0023] (2) Second embodiment The method for producing basic copper carbonate according to the second embodiment includes step A of simultaneously supplying an aqueous copper salt solution and an aqueous alkali solution A containing an alkali metal carbonate into a reaction tank, and step B of simultaneously supplying an aqueous copper salt solution, an aqueous alkali solution b1 containing an alkali metal carbonate, and an aqueous alkali solution b2 containing an alkali metal hydroxide into the reaction tank, wherein the pH of the aqueous alkali solution B obtained by the following <procedure> is higher than the pH of the aqueous alkali solution A. <Procedure> The supply amount of the alkaline aqueous solution b1 per unit time is X b1 mL / min, the supply amount of the alkaline aqueous solution b2 per unit time is X b2 When expressed as mL / min, X b1 mL of the alkaline aqueous solution b1 and X b2 1 mL of the alkaline aqueous solution b2.

[0024] Fig. 3 is a flow chart showing an example of a method for producing basic copper carbonate according to the second embodiment. Hereinafter, the method for producing basic copper carbonate according to the second embodiment will be described with reference to the flow chart of Fig. 3. First, ion-exchanged water, which serves as a diluent, is placed in a reaction tank. Next, an aqueous copper salt solution and an aqueous alkaline solution A containing an alkali metal carbonate are simultaneously fed into the reaction vessel (step A). Next, an aqueous copper salt solution, an aqueous alkaline solution b1 containing an alkali metal carbonate, and an aqueous alkaline solution b2 containing an alkali metal hydroxide are simultaneously supplied into the reaction tank (step B). The resulting basic copper carbonate slurry is then washed, dehydrated and dried to obtain basic copper carbonate powder.

[0025] FIG. 4 is a schematic diagram showing an example of a method for producing basic copper carbonate according to the second embodiment. According to the manufacturing method shown in the schematic diagram of FIG. 4, first, ion-exchanged water serving as a diluent (not shown) is placed in a reaction vessel 101 . Next, the copper salt aqueous solution from the copper salt aqueous solution storage tank 102 and the alkaline aqueous solution A from the alkaline aqueous solution A storage tank 103 are simultaneously supplied into the reaction tank 101 (step A). ​​The supply amount of the copper salt aqueous solution can be controlled by a supply amount control device 112. The supply amount of the alkaline aqueous solution A can be controlled by a supply amount control device 113. Next, the copper salt aqueous solution from the copper salt aqueous solution storage tank 102, the alkaline aqueous solution b1 from the alkaline aqueous solution b1 storage tank 141, and the alkaline aqueous solution b2 from the alkaline aqueous solution b2 storage tank 142 are simultaneously supplied into the reaction tank 101 (step B). The supply amount of the alkaline aqueous solution b1 can be controlled by the supply amount control device 151. The supply amount of the alkaline aqueous solution b2 can be controlled by the supply amount control device 152. The resulting basic copper carbonate slurry is then fed to a washing tank 105 for washing, fed to a centrifuge 106 for dehydration, and fed to a dryer 107 for drying, to obtain basic copper carbonate powder.

[0026] Hereinafter, each step of the method for producing basic copper carbonate according to this embodiment will be described.

[0027] <Process A> The method for producing basic copper carbonate according to this embodiment includes a step A of simultaneously supplying an aqueous copper salt solution and an aqueous alkaline solution A containing an alkali metal carbonate into a reaction vessel 101.

[0028] In the step A, it is preferable to supply the copper salt aqueous solution and the alkaline aqueous solution A to a reaction vessel 101 containing a diluent (not shown), and to stir the inside of the reaction vessel 101 with a stirring blade 108 .

[0029] The diluent serves as a buffer to suppress abrupt changes in pH and temperature due to the reaction by diluting the reaction solution in the reaction tank 101. As the diluent, for example, water such as ion-exchanged water can be used.

[0030] The diluent may contain a water-soluble solvent, for example, one or two selected from the group consisting of alcohols such as methanol, ethanol, and isopropanol, acetone, alkylamines such as ethylamine and trimethylamine, glycerin, and polyethylene glycol.

[0031] The copper salt aqueous solution and the alkaline aqueous solution A may be mixed in advance and fed into the reaction tank through one feed path, or each may be fed into the reaction tank through a separate feed path. Figures 2 and 4 show an example in which the copper salt aqueous solution and the alkaline aqueous solution A are fed through separate feed paths. From the viewpoint of easily controlling the supply amounts of the copper salt aqueous solution and the alkaline aqueous solution A individually, it is preferable to supply the copper salt aqueous solution and the alkaline aqueous solution A through separate supply routes.

[0032] The copper salt aqueous solution according to this embodiment contains a copper salt and water.

[0033] The copper salt according to the present embodiment is not particularly limited, and may be any salt containing copper ions.The copper salt according to the present embodiment includes, for example, one or more selected from the group consisting of copper chloride, copper bromide, copper sulfate, copper nitrate, copper acetate, copper cyanide and copper hydroxide, preferably one or two selected from the group consisting of copper chloride and copper sulfate, more preferably copper chloride.

[0034] The copper salt aqueous solution according to the present embodiment may be an aqueous solution prepared by dissolving the above-mentioned copper salt in water, or may be a copper chloride waste liquid, a copper sulfate waste liquid, a copper nitrate waste liquid, or the like, which is an etching waste liquid from electronic circuit boards such as printed circuit boards.

[0035] The aqueous copper salt solution according to this embodiment may contain a water-soluble solvent, for example, those listed as water-soluble solvents that may be contained in the diluent.

[0036] The copper salt aqueous solution according to this embodiment may contain an acid, for example, hydrochloric acid, in order to suppress precipitation of the copper salt.

[0037] From the viewpoint of improving the reaction efficiency, the content of copper ions in the aqueous copper salt solution according to this embodiment is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 5% by mass or more, even more preferably 7% by mass or more, even more preferably 9% by mass or more, and is, for example, 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less.

[0038] The alkaline aqueous solution A according to this embodiment contains an alkali metal carbonate and water.

[0039] The alkali metal carbonate according to the present embodiment is not particularly limited, but includes, for example, one or two selected from the group consisting of sodium carbonate, lithium carbonate, potassium carbonate, magnesium carbonate, and calcium carbonate, and preferably includes sodium carbonate.

[0040] The aqueous alkaline solution A according to this embodiment may contain a water-soluble solvent, and as the water-soluble solvent, those listed as the water-soluble solvents that may be contained in the aqueous copper salt solution can be used.

[0041] From the viewpoint of adjusting the pH inside the reaction tank 101 to the desired pH, the pH of the alkaline aqueous solution A in this embodiment is preferably 7.0 or more, more preferably 7.5 or more, even more preferably 8.0 or more, even more preferably 8.5 or more, even more preferably 9.0 or more, even more preferably 9.5 or more, even more preferably 10.0 or more, even more preferably 10.5 or more, even more preferably 11.0 or more, even more preferably 11.5 or more, even more preferably 12.0 or more, and is preferably 13.0 or less, more preferably 12.5 or less.

[0042] From the viewpoint of adjusting the pH inside the reaction tank 101 to a desired level, the content of alkali metal carbonate in the alkaline aqueous solution A in this embodiment is preferably 1 mass% or more, more preferably 3 mass% or more, even more preferably 5 mass% or more, even more preferably 7 mass% or more, even more preferably 9 mass% or more, even more preferably 11 mass% or more, and is preferably 20 mass% or less, more preferably 15 mass% or less, and even more preferably 13 mass% or less.

[0043] The content of alkali metal carbonate in the alkaline aqueous solution A in this embodiment, from the viewpoint of adjusting the pH inside the reaction tank 101 to the desired pH, is preferably 0.1 mol / L or more, more preferably 0.2 mol / L or more, even more preferably 0.4 mol / L or more, even more preferably 0.6 mol / L or more, even more preferably 0.8 mol / L or more, and even more preferably 1.0 mol / L or more, and is, for example, 10 mol / L or less, preferably 8 mol / L or less, more preferably 6 mol / L or less, even more preferably 4 mol / L or less, even more preferably 2 mol / L or less, and even more preferably 1.5 mol / L or less.

[0044] In step A, it is preferable to adjust the pH in the reaction tank 101 to a certain range by adjusting the amount of alkaline aqueous solution A supplied per hour. Specifically, when the pH in the reaction tank 101 approaches the upper limit of the following range, the supply amount of alkaline aqueous solution A supplied per hour from the alkaline aqueous solution A storage tank 103 is reduced by the supply amount control device 113, and when the pH in the reaction tank 101 approaches the lower limit of the following range, the supply amount of alkaline aqueous solution A supplied per hour from the alkaline aqueous solution A storage tank 103 is increased by the supply amount control device 113.

[0045] From the viewpoint of improving the reaction efficiency, the pH in the reaction tank 101 in step A is preferably 6.0 or more, more preferably 6.5 or more, even more preferably 7.0 or more, even more preferably 7.2 or more, and is preferably 10.0 or less, more preferably 9.5 or less, even more preferably 9.0 or less, even more preferably 8.5 or less, even more preferably 8.0 or less, even more preferably 7.8 or less.

[0046] In step A, the pH in the reaction tank 101 is adjusted by adjusting the amount of alkaline aqueous solution A supplied per hour to preferably 6.0 or more, more preferably 6.5 or more, even more preferably 7.0 or more, even more preferably 7.2 or more, and preferably 10.0 or less, more preferably 9.5 or less, even more preferably 9.0 or less, even more preferably 8.5 or less, even more preferably 8.0 or less, even more preferably 7.8 or less.

[0047] The temperature in reaction tank 101 in step A is preferably 25°C or higher, more preferably 35°C or higher, even more preferably 45°C or higher, even more preferably 55°C or higher, and even more preferably 60°C or higher, from the viewpoint of improving the reaction efficiency, and is preferably 95°C or lower, more preferably 85°C or lower, even more preferably 75°C or lower, and even more preferably 70°C or lower, from the viewpoint of suppressing side reactions.

[0048] <Process B> The method for producing basic copper carbonate according to the first embodiment includes a step B of simultaneously supplying an aqueous copper salt solution and an aqueous alkaline solution B containing an alkali metal carbonate and an alkali metal hydroxide into a reaction vessel 101. The method for producing basic copper carbonate according to the second embodiment also includes a step B in which an aqueous copper salt solution, an aqueous alkaline solution b1 containing an alkali metal carbonate, and an aqueous alkaline solution b2 containing an alkali metal hydroxide are simultaneously supplied into a reaction tank 101.

[0049] When step B is carried out after step A, it is preferable to supply an aqueous copper salt solution and an aqueous alkaline solution B to the reaction tank 101 containing the reaction solution after completion of step A, and to stir the inside of the reaction tank 101 with a stirring blade 108.

[0050] The copper salt aqueous solution and the alkaline aqueous solution B may be mixed in advance and fed into the reaction tank through one feed path, or each may be fed into the reaction tank through a separate feed path. Figure 2 shows an example in which the copper salt aqueous solution and the alkaline aqueous solution B are fed through separate feed paths. From the viewpoint of easily controlling the supply amounts of the copper salt aqueous solution and the alkaline aqueous solution B individually, it is preferable to supply the copper salt aqueous solution and the alkaline aqueous solution B through separate supply routes.

[0051] As the copper salt and alkali metal carbonate used in step B, the copper salt and alkali metal carbonate listed as being used in step A can be used.

[0052] The alkaline aqueous solution B according to this embodiment contains an alkali metal hydroxide and water.

[0053] The alkali metal hydroxide according to the present embodiment is not particularly limited, but includes, for example, one or more selected from the group consisting of sodium hydroxide, lithium hydroxide, potassium hydroxide, magnesium hydroxide, and calcium hydroxide, and preferably includes sodium hydroxide.

[0054] The aqueous alkaline solution B according to this embodiment may contain a water-soluble solvent, and as the water-soluble solvent, those listed as the water-soluble solvents that may be contained in the aqueous copper salt solution can be used.

[0055] The pH of the alkaline aqueous solution B according to this embodiment is higher than the pH of the alkaline aqueous solution A according to this embodiment.

[0056] From the viewpoint of adjusting the pH in the reaction tank 101 to the desired range, the pH of the alkaline aqueous solution B in this embodiment is preferably 9.0 or more, more preferably 9.5 or more, even more preferably 10.0 or more, even more preferably 10.5 or more, even more preferably 11.0 or more, even more preferably 11.5 or more, even more preferably 12.0 or more, even more preferably 12.5 or more, even more preferably 13.0 or more, even more preferably 13.3 or more, and is, for example, 14.0 or less, preferably 13.8 or less.

[0057] The content of alkali metal carbonate in the alkaline aqueous solution B in this embodiment, from the viewpoint of adjusting the pH in the reaction tank 101 to the desired range, is preferably 1 mass% or more, more preferably 3 mass% or more, even more preferably 5 mass% or more, even more preferably 7 mass% or more, even more preferably 8 mass% or more, and is preferably 20 mass% or less, more preferably 15 mass% or less, even more preferably 13 mass% or less, even more preferably 11 mass% or less, and even more preferably 9 mass% or less.

[0058] The content of alkali metal carbonate in the alkaline aqueous solution B in this embodiment, from the viewpoint of adjusting the pH in the reaction tank 101 to the desired range, is preferably 0.1 mol / L or more, more preferably 0.2 mol / L or more, even more preferably 0.4 mol / L or more, even more preferably 0.6 mol / L or more, even more preferably 0.8 mol / L or more, and even more preferably 0.9 mol / L or more, and is, for example, 10 mol / L or less, preferably 8 mol / L or less, more preferably 6 mol / L or less, even more preferably 4 mol / L or less, even more preferably 2 mol / L or less, even more preferably 1.5 mol / L or less, even more preferably 1.2 mol / L or less, and even more preferably 1.0 mol / L or less.

[0059] The content of alkali metal hydroxide in the alkaline aqueous solution B in this embodiment, from the viewpoint of adjusting the pH in the reaction tank 101 to the desired range, is preferably 1 mass% or more, more preferably 3 mass% or more, even more preferably 5 mass% or more, and even more preferably 6 mass% or more, and is preferably 20 mass% or less, more preferably 15 mass% or less, even more preferably 13 mass% or less, even more preferably 11 mass% or less, even more preferably 9 mass% or less, and even more preferably 7 mass% or less.

[0060] From the viewpoint of adjusting the pH in the reaction tank 101 to the desired range, the content of the alkali metal hydroxide in the alkaline aqueous solution B in this embodiment is preferably 0.1 mol / L or more, more preferably 0.2 mol / L or more, even more preferably 0.4 mol / L or more, even more preferably 0.6 mol / L or more, even more preferably 0.8 mol / L or more, even more preferably 1.0 mol / L or more, even more preferably 1.2 mol / L or more, even more preferably 1.4 mol / L or more, even more preferably 1.6 mol / L or more, even more preferably 1.7 mol / L or more, and is, for example, 10 mol / L or less, preferably 8 mol / L or less, more preferably 6 mol / L or less, even more preferably 4 mol / L or less, even more preferably 2 mol / L or less, and even more preferably 1.8 mol / L or less.

[0061] The ratio of the number of moles of alkali metal hydroxide to the number of moles of alkali metal carbonate in the alkaline aqueous solution B according to this embodiment is preferably 1.10 or more, more preferably 1.20 or more, even more preferably exceeding 1.20, even more preferably exceeding 1.30, even more preferably exceeding 1.40, even more preferably exceeding 1.50, even more preferably exceeding 1.60, even more preferably exceeding 1.70, even more preferably exceeding 1.80, and even more preferably exceeding 1.90. This allows the amount of alkali metal carbonate used to be reduced. If the amount of alkali metal carbonate used can be reduced, the amount of carbon dioxide gas and / or carbonate ions generated by the reaction of the alkali metal carbonate can be reduced, which is preferable from the viewpoint of protecting the global environment. In addition, since an alkali metal carbonate is generally dissolved in water or the like before use in a reaction, if the amount of alkali metal carbonate used can be reduced, the frequency of dissolving operations can be reduced, which is preferable from the viewpoint of improving production efficiency. Furthermore, if the amount of alkali metal carbonate used can be reduced, the total amount of alkali used can be reduced while still allowing the reaction for obtaining basic copper carbonate to proceed appropriately. In this specification, the total amount of alkali used is the sum of the number of moles of alkali metal ions in the alkali metal carbonate and the number of moles of alkali metal ions in the alkali metal hydroxide used in the production method for basic copper carbonate according to this embodiment. In other words, the total amount of alkali used in the present invention is the total amount of alkali used converted into the amount of alkali metal ions. The ratio of the number of moles of alkali metal hydroxide to the number of moles of alkali metal carbonate in the alkaline aqueous solution B according to this embodiment is preferably 3.00 or less, more preferably 2.50 or less, even more preferably 2.30 or less, even more preferably 2.10 or less, even more preferably 2.00 or less, even more preferably 1.95 or less, even more preferably 1.70 or less, even more preferably 1.60 or less, even more preferably 1.50 or less, even more preferably 1.40 or less, and even more preferably 1.35 or less. This makes it possible to further reduce the amount of impurities derived from copper salts.

[0062] In the step B of the first embodiment, it is preferable to adjust the pH in the reaction tank 101 to a certain range by adjusting the supply amount of the alkaline aqueous solution B per hour. Specifically, when the pH in the reaction tank 101 approaches the upper limit of the following range, the supply amount of the alkaline aqueous solution B from the alkaline aqueous solution B storage tank 104 per hour is reduced by the supply amount control device 114, and when the pH in the reaction tank 101 approaches the lower limit of the following range, the supply amount of the alkaline aqueous solution B from the alkaline aqueous solution B storage tank 104 per hour is increased by the supply amount control device 114.

[0063] From the viewpoint of improving the reaction efficiency, the pH in the reaction tank 101 in step B of the first embodiment is preferably 6.0 or more, more preferably 6.5 or more, even more preferably 7.0 or more, even more preferably 7.2 or more, and is preferably 10.0 or less, more preferably 9.5 or less, even more preferably 9.0 or less, even more preferably 8.5 or less, even more preferably 8.0 or less, even more preferably 7.8 or less.

[0064] In step B of the first embodiment, the supply amount of the aqueous alkaline solution B per hour is adjusted to adjust the pH in the reaction tank to preferably 6.0 or more, more preferably 6.5 or more, even more preferably 7.0 or more, even more preferably 7.2 or more, and preferably 10.0 or less, more preferably 9.5 or less, even more preferably 9.0 or less, even more preferably 8.5 or less, even more preferably 8.0 or less, even more preferably 7.8 or less.

[0065] In the step B of the second embodiment, it is preferable to adjust the pH in the reaction tank 101 to a certain range by adjusting the supply amount of the alkaline aqueous solution b1 per hour and / or the supply amount of the alkaline aqueous solution b2 per hour. Specifically, when the pH in the reaction tank 101 approaches the upper limit of the following range, the supply amount of the alkaline aqueous solution b1 and / or b2 per hour from the alkaline aqueous solution b1 storage tank 141 and / or the alkaline aqueous solution b2 storage tank 142 is reduced by the supply amount control device 151 and / or 152, and when the pH in the reaction tank 101 approaches the lower limit of the following range, the supply amount of the alkaline aqueous solution b1 and / or b2 per hour from the alkaline aqueous solution b1 storage tank 141 and / or the alkaline aqueous solution b2 storage tank 142 is increased by the supply amount control device 151 and / or 152.

[0066] From the viewpoint of improving the reaction efficiency, the pH in the reaction tank 101 in step B of the second embodiment is preferably 6.0 or more, more preferably 6.5 or more, even more preferably 7.0 or more, even more preferably 7.2 or more, and is preferably 10.0 or less, more preferably 9.5 or less, even more preferably 9.0 or less, even more preferably 8.5 or less, even more preferably 8.0 or less, even more preferably 7.8 or less.

[0067] In step B of the second embodiment, the pH in the reaction tank is adjusted to preferably 6.0 or more, more preferably 6.5 or more, even more preferably 7.0 or more, even more preferably 7.2 or more, and preferably 10.0 or less, more preferably 9.5 or less, even more preferably 9.0 or less, even more preferably 8.5 or less, even more preferably 8.0 or less, even more preferably 7.8 or less, by adjusting the supply amount of the aqueous alkaline solution b1 per hour and / or the supply amount of the aqueous alkaline solution b2 per hour.

[0068] The temperature in the reaction tank 101 in step B is preferably 25°C or higher, more preferably 35°C or higher, even more preferably 45°C or higher, even more preferably 55°C or higher, and even more preferably 60°C or higher, from the viewpoint of improving the reaction efficiency, and is preferably 95°C or lower, more preferably 85°C or lower, even more preferably 75°C or lower, and even more preferably 70°C or lower, from the viewpoint of suppressing side reactions.

[0069] The ratio of the number of moles of the alkali metal hydroxide used in step A and step B to the total number of moles of the alkali metal carbonate used in step A and step B is preferably 1.10 or more, more preferably 1.20 or more, even more preferably more than 1.20, even more preferably more than 1.3, and even more preferably more than 1.35. This allows the amount of alkali metal carbonate used to be reduced. If the amount of alkali metal carbonate used can be reduced, the amount of carbon dioxide gas and / or carbonate ions generated by the reaction of the alkali metal carbonate can be reduced, which is preferable from the viewpoint of protecting the global environment. In addition, since an alkali metal carbonate is generally dissolved in water or the like before use in a reaction, if the amount of alkali metal carbonate used can be reduced, the frequency of dissolving operations can be reduced, which is preferable from the viewpoint of improving production efficiency. Furthermore, if the amount of alkali metal carbonate used can be reduced, the total amount of alkali used can be reduced while still allowing the reaction for obtaining basic copper carbonate to proceed appropriately. The ratio of the number of moles of alkali metal hydroxide to the number of moles of alkali metal carbonate in the alkaline aqueous solution B according to this embodiment is preferably 2.00 or less, more preferably 1.80 or less, even more preferably 1.60 or less, even more preferably 1.50 or less, even more preferably 1.45 or less, and even more preferably 1.40 or less. This makes it possible to further reduce the amount of impurities derived from copper salts.

[0070] The basic copper carbonate slurry obtained through steps A and B may be used as a raw material for the synthesis of copper oxide etc. in the form of a slurry, or may be washed, dehydrated and further dried to form a powder. These unit operations can be carried out using commonly used methods and equipment.

[0071] In the washing step, for example, a basic copper carbonate slurry is supplied to a washing tank 105, the basic copper carbonate is precipitated, the supernatant liquid is removed, ion-exchanged water is supplied, and washing can be performed by stirring with a stirring blade 108.

[0072] Alternatively, after centrifuging the basic copper carbonate slurry, the solid content may be supplied to a washing tank 105, ion-exchanged water may be supplied, and the solid content may be stirred with a stirring blade 108 to perform washing.

[0073] The temperature in the cleaning tank is preferably 20° C. or higher and 90° C. or lower, more preferably 40° C. or higher and 70° C. or lower, so that impurities can be removed more easily.

[0074] The number of washing steps is not particularly limited, and may be repeated until the basic copper carbonate has a desired purity.

[0075] The dehydration means in the dehydration step is not particularly limited. For example, the washed basic copper carbonate slurry may be dehydrated using a centrifugal separator 106 or by suction filtration.

[0076] In the drying step, for example, the basic copper carbonate cake obtained in the dehydration step is dried in a dryer 107 such as a box dryer or a continuous dryer. The drying temperature is not particularly limited, but from the viewpoint of removing moisture while suppressing deterioration of the basic copper carbonate, it is preferably 60° C. or higher, more preferably 70° C. or higher and even more preferably 80° C. or higher, and from the viewpoint of preventing denaturation of the basic copper carbonate, it is preferably 150° C. or lower, more preferably 120° C. or lower, and even more preferably 100° C. or lower.

[0077] The use of the basic copper carbonate according to the present embodiment is not particularly limited, but it can be used, for example, as a raw material for copper oxide. The basic copper carbonate according to the present embodiment may also be used as a raw material for paints, ceramic materials, agricultural chemicals, plating solutions, etc.

[0078] 2. How to make copper oxide Hereinafter, the method for producing copper oxide according to this embodiment will be described.

[0079] The method for producing copper oxide according to this embodiment includes a step of obtaining basic copper carbonate by the above-mentioned method for producing basic copper carbonate, and a step C of obtaining copper oxide using the obtained basic copper carbonate as a raw material.

[0080] 5 is a flowchart showing an example of the copper oxide production method according to the present embodiment. Hereinafter, the copper oxide production method according to the present embodiment will be described with reference to the flowchart in FIG.

[0081] First, the basic copper carbonate slurry obtained by the above-mentioned method for producing basic copper carbonate is washed. Next, the washed basic copper carbonate slurry and an aqueous alkaline solution C containing an alkali metal hydroxide are fed into a reaction vessel, and then aged for a certain period of time to obtain a copper oxide slurry (step C). The resulting copper oxide slurry is then washed, dehydrated and dried to obtain copper oxide powder. Although the method for producing copper oxide using a basic copper carbonate slurry as a raw material has been described above, the properties of the basic copper carbonate used as a raw material in the method for producing copper oxide according to this embodiment are not particularly limited, and either a basic copper carbonate slurry or a basic copper carbonate powder may be used.

[0082] FIG. 6 is a schematic diagram showing an example of a method for producing copper oxide according to this embodiment.

[0083] First, the basic copper carbonate slurry is supplied from the reaction tank 101 to the cleaning tank 105, and the basic copper carbonate slurry is cleaned in the cleaning tank 105. Next, the basic copper carbonate slurry from the cleaning tank 105 and the alkaline aqueous solution C containing an alkali metal hydroxide from the alkaline aqueous solution C storage tank 122 are supplied to the reaction tank 121, and then aged for a certain period of time to obtain a copper oxide slurry (step C). The supply amount of the alkaline aqueous solution C can be controlled by the supply amount control device 132. The resulting copper oxide slurry is then fed to a washing tank 105 for washing, fed to a centrifuge 106 for dehydration, and fed to a dryer 107 for drying, to obtain copper oxide powder.

[0084] <Process C> From the viewpoint of improving the reaction efficiency, the pH in the reaction tank 121 in step C is preferably 9.0 or more, more preferably 9.5 or more, even more preferably 10.0 or more, even more preferably 10.5 or more, even more preferably 11.0 or more, and is, for example, 14.0 or less, preferably 13.5 or less.

[0085] From the viewpoint of improving the reaction efficiency, the temperature in the reaction tank 121 in step C is preferably 45°C or higher, more preferably 50°C or higher, even more preferably 55°C or higher, even more preferably 60°C or higher, even more preferably 65°C or higher, even more preferably 70°C or higher, even more preferably 75°C or higher, and is, for example, 95°C or lower, preferably 90°C or lower, more preferably 85°C or lower.

[0086] The maturation time in the reaction tank 121 in step C is preferably 30 minutes or more, more preferably 60 minutes or more, and even more preferably 90 minutes or more, from the viewpoint of improving the reaction efficiency.

[0087] The copper oxide slurry obtained through step C may be washed, dehydrated, and dried to obtain a powder state. These unit operations can be carried out using commonly used methods and equipment. Specifically, the contents described as the washing step, dehydration step, and drying step of basic copper carbonate can be adopted.

[0088] The use of the copper oxide according to this embodiment is not particularly limited, but it can be used, for example, as a raw material for agricultural chemicals, plating solutions, and the like.

[0089] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements within the scope of the present invention are included in the present invention. EXAMPLES

[0090] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, the examples were tested at 23° C. and a relative humidity of 50%.

[0091] [Example 1] (1) Synthesis of basic copper carbonate <Process A> First, 2.1 L of ion-exchanged water was placed in a reaction vessel, stirred, and heated to 65°C.

[0092] Next, while stirring the inside of the reaction tank, the copper salt aqueous solution 1 and the alkaline aqueous solution A were simultaneously supplied under the conditions shown in Table 1, and step A was started.

[0093] In step A, the pH and temperature in the reaction tank were maintained at 7.5 and 65° C., respectively, by adjusting the amount of the aqueous alkaline solution A supplied.

[0094] The copper salt aqueous solution 1 was prepared by dissolving copper(II) chloride dihydrate (manufactured by Ikoma Pharmaceutical Co., Ltd.) in ion-exchanged water, and further adding hydrochloric acid so that the content of chloride ions derived from hydrochloric acid was 1.0 mass %. The alkaline aqueous solution A was prepared by dissolving sodium carbonate (light ash (for industrial use), manufactured by Tokuyama Corporation) in ion-exchanged water.

[0095] [Table 1]

[0096] <Process B> After 135 minutes had elapsed from the start of the supply of step A, the supply of the alkaline aqueous solution A was stopped, the supply amount per unit time of the copper salt aqueous solution 1 was changed according to the conditions shown in Table 2, and the supply of the alkaline aqueous solution B was started according to the conditions shown in Table 2, thereby completing step A and starting step B.

[0097] In step B, the pH and temperature in the reaction tank were maintained at 7.5 and 65°C, respectively, by adjusting the amount of aqueous alkaline solution B supplied.

[0098] The alkaline aqueous solution B was prepared by dissolving sodium carbonate (light ash (industrial use) manufactured by Tokuyama Corporation) and liquid caustic soda (manufactured by Kaneka Corporation) in ion-exchanged water.

[0099] After 345 minutes had elapsed from the start of step B, the supply of the aqueous copper salt solution 1 and the aqueous alkaline solution B was stopped, and step B was terminated.

[0100] [Table 2]

[0101] The amounts of the alkaline components used in the synthesis of basic copper carbonate in Example 1 are as shown in Table 3.

[0102] [Table 3]

[0103] After completion of step B, the basic copper carbonate slurry produced in the reaction tank was washed with ion-exchanged water, dehydrated by suction filtration, and further dried in a dryer at 80° C. to obtain powdered basic copper carbonate.

[0104] (2) Synthesis of copper oxide The basic copper carbonate slurry obtained by the above method was fed into a reaction vessel, the temperature inside the reaction vessel was adjusted to 80°C, an aqueous sodium hydroxide solution was further fed into the reaction vessel to adjust the pH inside the reaction vessel to 11.0, and the mixture was aged for 2 hours to obtain a copper oxide slurry. Next, the copper oxide slurry produced in the reaction tank was washed with ion-exchanged water, dehydrated by suction filtration, and further dried in a dryer to obtain powdered copper oxide.

[0105] [Comparative Example 1] (1) Synthesis of basic copper carbonate Unlike Example 1, which used two types of alkaline aqueous solutions, alkaline aqueous solution A and alkaline aqueous solution B, in Comparative Example 1, basic copper carbonate was synthesized using one type of alkaline aqueous solution, alkaline aqueous solution x. In Comparative Example 1, the supply amount of the aqueous alkaline solution x was changed midway through the process. The process before the change is called process x, and the process after the change is called process y.

[0106] <Process x> First, 2.1 L of ion-exchanged water was placed in a reaction vessel, stirred, and heated to 65°C.

[0107] Next, while stirring the inside of the reaction tank, the copper salt aqueous solution 1 and the alkaline aqueous solution x were simultaneously supplied under the conditions shown in Table 4 to start step x.

[0108] In the step x, the pH and temperature in the reaction tank were maintained at 7.5 and 65° C., respectively, by adjusting the supply amount of the aqueous alkaline solution x.

[0109] The alkaline aqueous solution x was prepared by dissolving sodium carbonate (light ash (industrial use) manufactured by Tokuyama Corporation) and liquid caustic soda (manufactured by Kaneka Corporation) in ion-exchanged water.

[0110] [Table 4]

[0111] <Process y> After 135 minutes had elapsed from the start of step x, the supply amounts per unit time of the aqueous copper salt solution 1 and the aqueous alkali solution x were changed to the conditions shown in Table 5, and step y was started.

[0112] In the step y, the pH and temperature in the reaction tank were maintained at 7.5 and 65° C., respectively, by adjusting the supply amount of the aqueous alkaline solution x.

[0113] After 345 minutes had elapsed from the start of step y, the supply of the aqueous copper salt solution 1 and the aqueous alkali solution x was stopped, and step y was terminated.

[0114] [Table 5]

[0115] The amount of the alkaline component used in the synthesis of basic copper carbonate in Comparative Example 1 is as shown in Table 6.

[0116] [Table 6]

[0117] After the step y was completed, the basic copper carbonate slurry produced in the reaction tank was washed with ion-exchanged water, dehydrated by suction filtration, and further dried in a dryer at 80° C. to obtain powdered basic copper carbonate.

[0118] (2) Synthesis of copper oxide Powdered copper oxide was obtained by the same production method as in Example 1 using the basic copper carbonate slurry obtained by the above method as a raw material.

[0119] The amounts of alkaline components used in the synthesis of basic copper carbonate in Example 1 and Comparative Example 1 are summarized in Table 7.

[0120] The basic copper carbonate and copper oxide obtained by the above method were analyzed by spectrophotometry. The chlorine content in the basic copper carbonate and the chlorine content in the copper oxide obtained by the analysis are shown in Table 7.

[0121] The volume-average median diameter D of the basic copper carbonate and copper oxide obtained by the above method is 50 was measured using a particle size distribution analyzer (Microtrack Bell MT3300EXII). The results are shown in Table 7.

[0122] [Table 7]

[0123] The basic copper carbonate obtained in Example 1 had a reduced chlorine content compared to the basic copper carbonate obtained in Comparative Example 1. This shows that the method for producing basic copper carbonate according to this embodiment can reduce the amount of impurities derived from copper salts, such as chlorine.

[0124] Furthermore, the basic copper carbonate obtained in Example 1 had less refined particle size than the basic copper carbonate obtained in Comparative Example 1. This shows that the method for producing basic copper carbonate according to this embodiment can suppress refinement of the particle size of basic copper carbonate.

[0125] The copper oxide obtained in Example 1 had a reduced chlorine content compared to the copper oxide obtained in Comparative Example 1. This shows that the method for producing copper oxide according to this embodiment can reduce the amount of impurities derived from copper salts, such as chlorine.

[0126] Furthermore, the copper oxide obtained by the production method of Example 1 had less refinement of the particle size than the copper oxide obtained by Comparative Example 1. This shows that the copper oxide production method according to this embodiment can suppress refinement of the particle size of the copper oxide. [Explanation of symbols]

[0127] 101 Reactor 102 Copper salt aqueous solution storage tank 103 Alkaline aqueous solution A storage tank 104 Alkaline aqueous solution B storage tank 105 Cleaning tank 106 Centrifuge 107 Dryer 108 Stirring blade 112 Supply volume control device 113 Supply volume control device 114 Supply volume control device 141 Alkaline aqueous solution b1 storage tank 142 Alkaline aqueous solution b2 storage tank 151 Supply volume control device 152 Supply volume control device 121 Reactor 122 Alkaline aqueous solution C storage tank 132 Supply volume control device

Claims

1. A step A of simultaneously supplying an aqueous copper salt solution and an aqueous alkaline solution A containing an alkali metal carbonate into a reaction vessel; A step B of simultaneously supplying an aqueous copper salt solution and an aqueous alkali solution B containing an alkali metal carbonate and an alkali metal hydroxide into a reaction vessel; Including, The method for producing basic copper carbonate, wherein the pH of the alkaline aqueous solution B is higher than the pH of the alkaline aqueous solution A.

2. A step A of simultaneously supplying an aqueous copper salt solution and an aqueous alkaline solution A containing an alkali metal carbonate into a reaction vessel; A step B of simultaneously supplying an aqueous copper salt solution, an aqueous alkali solution b1 containing an alkali metal carbonate, and an aqueous alkali solution b2 containing an alkali metal hydroxide into a reaction tank; Including, A method for producing basic copper carbonate, in which the pH of the obtained alkaline aqueous solution B is higher than the pH of the alkaline aqueous solution A by the following <procedure>. <Procedure> The supply amount of the alkaline aqueous solution b1 per unit time is X ｂ１ mL / min, the supply amount of the alkaline aqueous solution b2 per unit time is X ｂ２ When expressed as mL / min, X ｂ１ mL of the alkaline aqueous solution b1 and X ｂ２ 1 mL of the alkaline aqueous solution b2 is mixed with the above solution.

3. In the method for producing basic copper carbonate according to claim 1 or 2, A method for producing basic copper carbonate, comprising carrying out the step B after the step A.

4. In the method for producing basic copper carbonate according to claim 1 or 2, The method for producing basic copper carbonate, wherein the copper salt comprises copper chloride.

5. In the method for producing basic copper carbonate according to claim 1 or 2, The method for producing basic copper carbonate, wherein the alkali metal carbonate comprises sodium carbonate.

6. In the method for producing basic copper carbonate according to claim 1 or 2, The method for producing basic copper carbonate, wherein the alkali metal hydroxide comprises sodium hydroxide.

7. In the method for producing basic copper carbonate according to claim 1 or 2, The method for producing basic copper carbonate, wherein the pH of the alkaline aqueous solution A is 7.0 or more and 13.0 or less.

8. In the method for producing basic copper carbonate according to claim 1 or 2, The content of the alkali metal carbonate in the alkaline aqueous solution A is from 0.1 mol / L to 10 mol / L.

9. In the method for producing basic copper carbonate according to claim 1 or 2, A method for producing basic copper carbonate, wherein in the step A, the pH in the reaction tank is adjusted to 6.0 or more and 10.0 or less by adjusting the amount of the aqueous alkaline solution A supplied per hour.

10. In the method for producing basic copper carbonate according to claim 1 or 2, The method for producing basic copper carbonate, wherein the temperature in the reaction tank in step A is 25° C. or higher and 95° C. or lower.

11. In the method for producing basic copper carbonate according to claim 1 or 2, The method for producing basic copper carbonate, wherein the pH of the alkaline aqueous solution B is 9.0 or more and 14.0 or less.

12. In the method for producing basic copper carbonate according to claim 1 or 2, The content of the alkali metal carbonate in the alkaline aqueous solution B is 0.1 mol / L or more and 10 mol / L or less.

13. In the method for producing basic copper carbonate according to claim 1 or 2, The content of the alkali metal hydroxide in the alkaline aqueous solution B is 0.1 mol / L or more and 10 mol / L or less.

14. In the method for producing basic copper carbonate according to claim 1 or 2, a ratio of the number of moles of the alkali metal hydroxide to the number of moles of the alkali metal carbonate in the alkaline aqueous solution B is 1.10 or more.

15. The method for producing basic copper carbonate according to claim 1, In the step B, the pH in the reaction tank is adjusted to 6.0 or more and 10.0 or less by adjusting the amount of the aqueous alkaline solution B supplied per hour.

16. The method for producing basic copper carbonate according to claim 2, In the step B, the pH in the reaction tank is adjusted to 6.0 or more and 10.0 or less by adjusting the amount of the aqueous alkaline solution b1 supplied per hour and / or the amount of the aqueous alkaline solution b2 supplied per hour.

17. In the method for producing basic copper carbonate according to claim 1 or 2, The method for producing basic copper carbonate, wherein the temperature in the reaction tank in step B is 25° C. or higher and 95° C. or lower.

18. In the method for producing basic copper carbonate according to claim 1 or 2, a ratio of a molar number of the alkali metal hydroxide used in the step A and the step B to a total molar number of the alkali metal carbonate used in the step A and the step B is 1.10 or more.

19. A step of obtaining basic copper carbonate by the method for producing basic copper carbonate according to claim 1 or 2; and step C of obtaining copper oxide using the obtained basic copper carbonate as a raw material.

20. 20. The method for producing copper oxide according to claim 19, The method for producing copper oxide, wherein the pH in the reaction tank in the step C is 9.0 or higher.

21. 21. The method for producing copper oxide according to claim 19 or 20, The method for producing copper oxide, wherein the temperature in the reaction tank in the step C is 45° C. or higher and 95° C. or lower.

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