WO2016052725A1 - Additive for high-purity copper electrolytic refining and method for producing high-purity copper - Google Patents

Abstract

This additive for high-purity copper electrolytic refining is an additive that is added into a copper electrolyte solution in electrolytic refining for high-purity copper, and is composed of a nonionic surfactant which has a hydrophobic group containing an aromatic ring and a hydrophilic group containing a polyoxyalkylene group. This additive for high-purity copper electrolytic refining has a dispersion term dD of the Hansen solubility parameters satisfying 10 ≤ dD ≤ 20, a polarity term dP of the Hansen solubility parameters satisfying 6 ≤ dP ≤ 9, and a hydrogen bonding term dH of the Hansen solubility parameters satisfying 9 ≤ dH ≤ 11.

Description

High purity copper electrolytic refining additive and method for producing high purity copper

The present invention relates to an additive for high-purity copper electrolytic refining for producing high-purity copper with greatly reduced impurities such as sulfur and silver concentration, and a production method using the additive.
This application claims priority based on Japanese Patent Application No. 2014-205310 filed in Japan on October 4, 2014 and Japanese Patent Application No. 2015-169882 filed in Japan on August 29, 2015. The contents are incorporated herein.

As described in Patent Document 1, as a method for producing high-purity copper, a copper sulfate aqueous solution is electrolyzed, copper deposited on the cathode is used as an anode, and further, a low current density of 100 A / m ² or less in the copper nitrate aqueous solution. There is known a method of performing two-stage electrolysis with re-electrolysis.

In addition, as described in Patent Document 2, by using a polyoxyethylene-based surfactant such as PEG (polyethylene glycol) in combination with a copper sulfate electrolyte containing chlorine ions, glue and the like, and an active sulfur component, A method for producing an electrolytic copper foil with improved mechanical properties and cathode adhesion is known. Furthermore, as described in Patent Document 3, by using a smoothing agent such as PVA (polyvinyl alcohol) and a slime accelerator such as PEG, the copper surface is smooth and the amount of impurities of silver and sulfur is small. A method for producing high purity electrolytic copper is known.

Japanese Patent Publication No. 08-990 JP 2001-123289 A JP 2005-307343 A

As in the manufacturing method disclosed in Patent Document 1, the two-stage manufacturing method in which the copper sulfate bath is electrolyzed and the copper nitrate bath is electrolyzed has a problem that the electrolysis is troublesome. In addition, the use of nitric acid has a problem that the environmental load is high and the wastewater treatment becomes complicated.

When conventional additives (PVA, PEG, etc.) are used, it is difficult to increase the current density, and when liquid agitation is performed to increase the current density, slime rises, which adheres to the cathode and lowers the purity of electrolytic copper. In addition, since the additive strongly suppresses dissolution of the anode, the anode dissolution overvoltage is increased, so that a large amount of slime is generated during anode dissolution, the yield of the cathode is reduced, and the amount of slime attached to the cathode is increased. Further, since the conventional additive suppresses the deposition reaction of the cathode, there is a problem that the purity of the electrodeposited copper is increased and the purity is lowered when the electrolytic solution contains a sulfate group.

Also, water-soluble polymer additives such as PEG and PVA are extremely hydrophilic, have poor UV absorption, are difficult to perform quantitative analysis by high performance liquid chromatography (HPLC), and have a high decomposition rate. Accurate concentration management is difficult. Furthermore, when PEG is used, there is a problem that dendrites on the surface of the electrolytic copper are likely to occur. When PVA is used to solve the problem, the surface of the electrolytic copper becomes smooth, but the impurity silver is not sufficiently reduced. . Moreover, the manufacturing method using surfactants, such as PEG, described in Patent Document 2 has a high content of sulfur and the like in electrolytic copper, and it is difficult to obtain high-purity electrolytic copper.

The present invention eliminates the above-mentioned problems in conventional production methods for the production of high-purity copper. By using an additive comprising a surfactant having a specific hydrophobic group and hydrophilic group, generation of slime is achieved. The above-mentioned additive and a production method using the additive are provided, in which high-purity copper in which the concentration of impurities such as sulfur is significantly reduced can be suppressed.

The present invention relates to an additive for high-purity copper electrolytic refining having the following configuration and a method for producing high-purity copper.
[1] An additive added to a copper electrolyte in electrolytic refining of high-purity copper, comprising a nonionic surfactant having a hydrophobic group containing an aromatic ring and a hydrophilic group containing a polyoxyalkylene group High purity, wherein the dispersive component dD of the Hansen solubility parameter is 10 ≦ dD ≦ 20, the polar component dP is 6 ≦ dP ≦ 9, and the hydrogen bonding component dH is 9 ≦ dH ≦ 11 Additive for copper electrolytic refining.
[2] The disperse component dD of the Hansen solubility parameter of the additive is 12 ≦ dD ≦ 17, the polar component dP is 7 ≦ dP ≦ 9, and the hydrogen bond component dH is 9 ≦ dH ≦ 11 The additive for high purity copper electrolytic refining according to [1].
[3] A nonionic surfactant having a hydrophobic group containing an aromatic ring and a hydrophilic group containing a polyoxyalkylene group, the dispersion component dD of the Hansen solubility parameter is 10 ≦ dD ≦ 20, and the polar component A method for producing high-purity copper, in which dP is 6 ≦ dP ≦ 9 and an additive having a hydrogen bonding component dH of 9 ≦ dH ≦ 11 is added to a copper electrolyte to perform electrolysis.
[4] The method for producing high-purity copper as described in [3] above, wherein the concentration of the additive in the copper electrolyte is 2 to 500 mg / L.
[5] The method for producing high-purity copper as described in [3] or [4] above, wherein the copper electrolyte is a copper sulfate solution, a copper nitrate solution, or a copper chloride solution.
[6] A copper sulfate solution having a copper concentration of 5 to 90 g / L, a sulfuric acid concentration of 10 to 300 g / L, a nitric acid concentration of 0.1 to 100 g / L, or a hydrochloric acid concentration of 10 to 300 g / L The method for producing high-purity copper as described in [5] above, wherein a copper chloride solution is used as the copper electrolyte.
[7] The method for producing high-purity copper as described in any one of [3] to [6] above, wherein high-purity copper having a sulfur and silver concentration of 1 ppm or less is produced.

Since the additive of the present invention has a hydrophobic group of an aromatic ring and a hydrophilic group of a polyoxyalkylene group, it suppresses silver ions and sulfur ions in the electrolytic solution from being deposited on the cathode, Significantly reduce sulfur concentration.
Further, the additive of the present invention has a Hansen solubility parameter dispersion component dD of 10 ≦ dD ≦ 20, a polar component dP of 6 ≦ dP ≦ 9, and a hydrogen bonding component dH of 9 ≦ dH ≦ 11. As a result, anode slime is remarkably suppressed. Specifically, for example, according to a preferred embodiment of the present invention, the generation rate of anode slime is suppressed to 20% or less.

Incidentally, a conventional surfactant, for example, PEG having a Hansen solubility parameter dispersion component dD of 3.6, a polar component dP of 14.3 and a hydrogen bonding component dH of 16.9 is added to the copper sulfate electrolyte. When the copper electrolysis is performed, the slime generation rate is about 30% or more, which is remarkably high. If there is much slime, this will be taken in to the surface of electrolytic copper and will cause a sulfur content to increase.

The additive of the present invention has a hydrophobic group containing an aromatic ring and a hydrophilic group of a polyoxyalkylene group, thereby suppressing the deposition of silver ions and sulfate ions in the electrolyte on the cathode. In addition to greatly reducing the silver concentration and sulfur concentration, the hydrophobic group and the hydrophilic group maintain an appropriate balance, and thus have the effect of suppressing the generation of anode slime. It becomes difficult for copper to be taken in, and these synergistic effects can greatly reduce the amount of sulfur and silver contained in electrolytic copper. Furthermore, the carbon concentration of electrolytic copper is low. Further, since the additive of the present invention does not contain sulfur in the molecular skeleton, the sulfur content of the cathode is extremely low.

Specifically, according to the additive according to a preferred embodiment of the present invention, high-purity electrolytic copper having a sulfur concentration and a silver concentration of 1 mass ppm or less can be obtained.

In the additive of the present invention, the anode is moderately dissolved and anode slime is hardly generated. Therefore, according to a preferred embodiment of the present invention, the cathode yield can be 80% or more.

[Specific description]
Hereinafter, an embodiment of the present invention (hereinafter referred to as the present embodiment) will be specifically described.
The additive of the present embodiment is an additive added to the copper electrolyte in the electrolytic refining of high-purity copper, and has a nonionic property having a hydrophobic group containing an aromatic ring and a hydrophilic group containing a polyoxyalkylene group The dispersion component dD of the Hansen solubility parameter is 10 ≦ dD ≦ 20, the polar component dP is 6 ≦ dP ≦ 9, and the hydrogen bond component dH is 9 ≦ dH ≦ 11. It is a featured additive for high purity copper electrolytic refining.

The additive of the present embodiment is composed of a nonionic surfactant having a hydrophobic group containing an aromatic ring and a hydrophilic group containing a polyoxyalkylene group. The hydrophobic group containing an aromatic ring of the additive is, for example, a phenyl group or a naphthyl group, and examples thereof include monophenyl, naphthyl, cumyl, alkylphenyl, styrenated phenyl, distyrenated phenyl, and tristyrenated phenyl. . The hydrophilic group containing a polyoxyalkylene group of the additive is, for example, a polyoxyethylene group or a polyoxypropylene group, and may contain both a polyoxyethylene group and a polyoxypropylene group.

Specific compounds of the additive of the present embodiment include, for example, polyoxyethylene monophenyl ether, polyoxyethylene naphthyl ether, polyoxyethylene styrenated phenyl ether, polyoxyethylene distyrenated phenyl ether, polyoxyethylene tristyrene Phenyl ether, polyoxyethylene cumyl phenyl ether, polyoxypropylene monophenyl ether, polyoxypropylene naphthyl ether, polyoxypropylene styrenated phenyl ether, polyoxypropylene distyrenated phenyl ether, polyoxypropylene tristyrenated phenyl ether And polyoxypropylene cumyl phenyl ether.

Thus, the additive of this embodiment has the hydrophobic group and the hydrophilic group, and silver ions and sulfate ions in the electrolytic solution are deposited on the cathode by having the hydrophobic group and the hydrophilic group. And the silver concentration and sulfur concentration of electrolytic copper are greatly reduced.

Furthermore, the additive of the present embodiment maintains an appropriate balance between the hydrophobic group and the hydrophilic group as indicated by the Hansen solubility parameter. Specifically, the additive has a Hansen solubility parameter dispersion component dD of 10 ≦ dD ≦ 20, a polar component dP of 6 ≦ dP ≦ 9, and a hydrogen bonding component dH of 9 ≦ dH ≦ 11. is there.

In general, the liquid Hansen solubility parameter (HSP) is used as an index of the balance between hydrophobic groups and hydrophilic groups. The HSP is an index indicating the degree to which a certain substance is dissolved in another substance. The solubility parameter δ is indicated by the position of a coordinate point in a three-dimensional space with the dispersion component dD, polar component dP, and hydrogen bond component dH as coordinate axes, and δ = (dD ² + dP ² + dH ² ) ^0.5. It can be expressed by the following formula.

HSP can show the solubility of a substance in various solvent compositions, and its phase solubility can be expressed by the HSPdistance (Ra) formula shown in the following formula (1). The smaller the HSPdistance (Ra), the higher the compatibility. The HSPdistance (Ra) of the two substances A and B can be expressed by the following formula (1). In the formula (1), dD _A , dP _A , and dH _A are a dispersion component dD, a polar component dP, and a hydrogen bonding component dH of the substance A, respectively. DD _B , dP _B , and dH _B are a dispersion component dD, a polar component dP, and a hydrogen bond component dH of the substance B, respectively.
HSPdistance (Ra) = {4 × (dD _A −dD _B ) ² + (dP _A −dP _B ) ² + (dH _A −dH _B ) ² } ^0.5 (1)

The Hansen solubility parameters of common solvents are described in known literature (Hansen Solubility Parameters: A User's Handbook, Charles Hansen, 2007, 2nd edition, etc.), and the Hansen solubility parameters of specific solvents are Can be determined by measuring the solubility by dissolving it in another solvent in which the Hansen solubility parameter has been determined. It can also be calculated using HSPiP (Hansen SolubilityluParameters in Practice) software. Specifically, the dispersion component dD, the polar component dP, and the hydrogen bond component dH can be calculated by automatically dividing the molecule from the structural formula of the substance using the Y-MB tool in HSPiP. In this specification, the dispersion component dD, the polar component dP, and the hydrogen bonding component dH of each additive were calculated from the structural formula of the additive using a Y-MB tool of HSPiP software.

It should be noted that the Hansen solubility parameters (dD, dP, dH) of the additive used in this embodiment do not indicate compatibility between the additive and an electrolytic solution composed of a mineral acid, a copper compound, and water. The inherent solubility parameter of the additive indicates the relationship between the additive and the electrodeposition effect from the newly found knowledge that it has a correlation with the electrodeposition suppressing effect.

Further, HLB (Hydrophile-Lipophile Balance) is known as a parameter representing the hydrophilic / lipophilic balance of the surfactant. HLB represents only the action on water and oil, but HSP shows the solubility of substances in various solvent compositions, and HLB and HSP have no correlation and are different indexes.

The additive of this embodiment is a nonionic ion whose Hansen solubility parameter dispersion component dD is 10 ≦ dD ≦ 20, polar component dP is 6 ≦ dP ≦ 9, and hydrogen bond component dH is 9 ≦ dH ≦ 11. Surfactant. Preferably, the additive dispersion component dD is 12 ≦ dD ≦ 17, the polar component dP is 7 ≦ dP ≦ 9, and the hydrogen bonding component dH is 9 ≦ dH ≦ 11.

In the additive of the present embodiment, the values of the dispersion component dD, the polar component dP, and the hydrogen bonding component dH reflect the balance between the hydrophilic group and the hydrophobic group and the molecular weight of these functional groups. The above ranges of the values of the component dP and the hydrogen bonding component dH are the optimum ranges in which the generation of anode slime is suppressed, the electrolytic copper surface is smooth, and high-purity copper with a very small amount of impurities such as sulfur is electrolytically deposited. Show.

Specifically, the dispersion component dD of the Hansen solubility parameter of the additive is 10 ≦ dD ≦ 20, the polar component dP is 6 ≦ dP ≦ 9, and the hydrogen bonding component dH is 9 ≦ dH ≦ 11. As a result, generation of anode slime is greatly suppressed. For example, the generation rate of anode slime is suppressed to 20% or less.

On the other hand, if the hydrophilic group of the additive is too large, the effect of suppressing the cathode deposition by the hydrophilic group becomes too strong, and the deposited surface becomes rough. On the other hand, if the hydrophobic group is too large, the oiliness becomes stronger and the adsorptivity increases, the above-mentioned suppression effect by the hydrophobic group becomes too strong, the precipitation state deteriorates similarly, and the surfactant itself is difficult to dissolve in the electrolyte. .

Specifically, when the dispersion component dD of the additive exceeds 20, the polar component dP is less than 6, and the hydrogen bonding component dH is less than 9, the solubility of the additive in the copper electrolyte is remarkably reduced. To do. Further, when the dispersion component dD of the additive is less than 10, the polar component dP exceeds 9, and the hydrogen bonding component dH exceeds 11, the additive has an excessively high anodic dissolution inhibiting effect, and the precipitation surface becomes rough. As the anode slime increases.

The additive of the present embodiment is used by being added to a copper electrolyte in electrolytic refining of high purity copper. The concentration of the additive is preferably in the range of 2 to 500 mg / L, and more preferably in the range of 10 to 300 mg / L. When the concentration of the additive is less than 2 mg / L, the effect of addition is poor, so the smoothness of the surface of the electrolytic copper is lowered, and the sulfur in the electrolytic solution adheres to the surface of the electrolytic copper and is easily taken in. Increases sulfur concentration. On the other hand, when the concentration of the additive exceeds 500 mg / L, the adhesion of the additive to the anode surface is too strong and the amount of slime generated increases, and this is taken into the cathode copper with an excessive amount of additive. The sulfur concentration and silver concentration in copper increase.

The copper electrolyte in which the additive of this embodiment is used is a copper compound solution of a mineral acid such as a copper sulfate solution, a copper nitrate solution, or a copper chloride solution.
When a copper sulfate solution is used as the copper electrolyte, the sulfuric acid concentration is preferably 10 to 300 g / L. If the sulfuric acid concentration is less than 10 g / L, copper hydroxide is generated in the electrolytic copper and the precipitation state deteriorates. On the other hand, when the sulfuric acid concentration exceeds 300 g / L, the sulfuric acid uptake amount in the electrolytic copper increases, and the sulfur concentration increases. The sulfuric acid concentration is more preferably 20 to 100 g / L. When the copper electrolyte is a copper nitrate solution, the nitric acid concentration is preferably 0.1 to 100 g / L, more preferably 1 to 50 g / L. When the copper electrolyte is a copper chloride solution, the hydrochloric acid concentration is preferably 10 to 300 g / L, more preferably 15 to 75 g / L.

In any of the copper electrolytes of the copper sulfate solution, the copper nitrate solution, and the copper chloride solution, the copper concentration of the electrolyte solution is preferably 5 to 90 g / L (the copper sulfate pentahydrate concentration is 20 to 350 g / L, nitric acid (The copper trihydrate concentration is 19 to 342 g / L, and the copper chloride dihydrate concentration is 13 to 241 g / L). When the copper concentration is less than 5 g / L, electrolytic copper is precipitated in a powder form, so that the purity is lowered. On the other hand, when the copper concentration exceeds 90 g / L, the electrolytic solution is easily taken into the electrolytic copper, so that the purity is lowered. The copper concentration in the copper electrolyte is more preferably 40 to 80 g / L.

When the electrolytic solution is a copper sulfate solution or a copper nitrate solution, the chloride ion concentration of the electrolytic solution is preferably 200 mg / L or less. When the chloride ion concentration exceeds 200 mg / L, chloride is easily taken into electrolytic copper, and the purity of electrolytic copper is lowered. The lower limit of the chloride ion concentration is preferably 1 mg / L, and the chloride ion concentration is more preferably 10 to 100 mg / L.

The additive of the present embodiment is composed of a nonionic surfactant having a hydrophilic group such as a polyoxyethylene group and a hydrophobic group such as a phenyl group or a naphthyl group, and has strong ultraviolet absorption and hydrophobicity. Therefore, quantitative analysis by high performance liquid chromatography (HPLC) is possible. Therefore, the concentration of the additive is measured by HPLC, and the reduced amount of the additive is supplemented so that the concentration of the additive is maintained in the range of 2 to 500 mg / L, more preferably in the range of 10 to 300 mg / L. Then, it is good to perform copper electrolytic refining.

Examples of the present invention are shown below together with comparative examples. The sulfur concentration and silver concentration of electrolytic copper were measured for the central portion of electrolytic copper that was electrolytically purified by GD-MS (glow discharge mass spectrometry).
The slime generation rate was obtained by the following equation.
Slime generation rate (%) = 100− (weight of deposited copper) / (dissolution amount of anode (weight)) × 100
The Hansen solubility parameters dD, dP and dH of the additives (A to C) were calculated by inputting the structural formula of the additive in the SMILES format using the formula of HSPiP (Hansen Solubility Parameters in Practice) software. In each example, dD, dP, and dH were changed by changing the number of added moles of polyoxyethylene groups that are hydrophilic groups. For example, in polyoxyethylene dodecyl ether CH ₃ (CH ₂ ) ₁₁ O (C ₂ H ₄ O) nH (n is the number of added moles), when n = 9, dD = 13.9, dP = 6.3 , DH: 9.4, and when n = 20, dD = 10.0, dP: 9.0, dH = 12.5.
The smoothness was indicated by ○ mark when there was no dendride (dendritic protrusion) or powdery precipitation, Δ mark when it was slight, and x mark when there was a lot. Specifically, the samples where 2-5 dendriides were observed per 10 cm ² were marked with Δ. Moreover, x was attached | subjected to the sample by which 6 or more dendride was seen per 10 cm < ² >, or the sample by which powdery precipitation was seen. The other samples were judged as having no dendride generation or powdery precipitation and marked with ○.

[Example 1]
A copper sulfate solution having a sulfuric acid concentration of 100 g / L, a copper sulfate pentahydrate concentration of 200 g / L, and a chloride ion concentration of 100 mg / L is used as an electrolyte, and additives A, B, and C are used. A, B, and C were added at 30 mg / L. For the anode, electrolytic copper having a sulfur concentration of 5 ppm by mass and a silver concentration of 8 ppm by mass was used. Electrolysis was performed at a current density of 200 A / m ² and a bath temperature of 30 ° C., and the additive concentration was measured by HPLC using an ODS column every 12 hours, and decreased so that the additive concentration was maintained at 30 mg / L. The copper content was replenished and electrolytic copper was refined. The results are shown in Table 1.
The additives A, B, and C used are as follows.
Additive A: Polyoxyethylene monophenyl ether additive B: Polyoxyethylene naphthyl ether additive C: Polyoxyethylene distyrenated phenyl ether

As shown in Table 1, when the dispersion component dD is 12 ≦ dD ≦ 17, the polar component dP is 7 ≦ dP ≦ 9, and the hydrogen bonding component dH is 9 ≦ d ≦ 11, the slime generation rate No. 1 to No. 6 were obtained with a smooth surface of 20% or less, a sulfur concentration of about 0.5 mass ppm or less, and a silver concentration of 1.0 mass ppm or less. Therefore, it is preferable that the additive has a dispersion component dD of 12 ≦ dD ≦ 17, a polar component dP of 7 ≦ dP ≦ 9, and a hydrogen bonding component dH of 9 ≦ d ≦ 11.

 

[Example 2]
Under the same conditions as in Example 1, electrolytic copper was electrolytically refined using the additives A, B, and C of the Hansen solubility parameters dD, dP, and dH shown in Table 2. The results are shown in Table 2. As shown in Table 2, the dD value, dP value, and dH value of the additives A, B, and C are the same as the sample No. of Example 1. 1 to No. Compared to 6, No. 10 has a high dD value. No. 11 has a high dD value and a low dP value. No. 12 had a low dD value, but the silver and sulfur concentrations were about 1 ppm by mass or less. Thus, when the dispersion component dD of the Hansen solubility parameter is 12 ≦ dD ≦ 17, the polar component dP is 7 ≦ dP ≦ 9, and the hydrogen bond component dH is 9 ≦ d ≦ 11, the sulfur concentration It was confirmed that low-purity, high-purity electrolytic copper was obtained.

 

Example 3
Additives shown in Table 3 under the same conditions as in Example 1 except that a copper nitrate solution having a nitric acid concentration of 5 g / L, a copper nitrate trihydrate of 200 g / L, and a chloride ion concentration of 100 mg / L was used as the electrolyte. Electrolytic copper was electrolytically refined using A, B, and C. The results are shown in Table 3.
As shown in Table 3, even when a copper nitrate solution is used as the electrolyte, the values of the polarization component dD, the polar component dP, and the hydrogen bonding component dH of the Hansen solubility parameter are 12 ≦ dD ≦ 17 and 7 ≦ dP ≦ 9, respectively. 9 ≦ d ≦ 11, the slime generation rate was low, and the sulfur and silver contents of electrolytic copper were both as low as 1 mass ppm or less, and the smoothness of the electrolytic copper surface was excellent.

 

Example 4
The electrolytic copper was subjected to electrolytic refining in the same manner as in Example 1 except that the amount of the additive A in the concentration shown in Table 4 was used (Sample Nos. 30 to 35). The results are shown in Table 4. Further, electrolytic copper was electrolytically refined in the same manner as in Example 3 except that the additive B was used in an amount corresponding to the concentration shown in Table 4 (Sample Nos. 36 to 41). The results are shown in Table 4.
As shown in Table 4, sample Nos. With additive concentrations of 2 to 500 mg / L. Nos. 31 to 34 and 37 to 40 are sample Nos. With additive concentrations of 0.1 mg / L and 800 mg / L. There were fewer impurities than 30, 35, 36, and 41, and the smoothness of the surface of the electrolytic copper was good. Accordingly, the concentration of the additives A and B is preferably 2 to 500 mg / L.

 

Example 5
A copper sulfate solution was used as an electrolytic solution, the sulfuric acid concentration and the copper concentration were adjusted as shown in Table 5, and additive A was added to this electrolytic solution to a concentration of 30 mg / L, as in Example 1. Then, electrolytic copper was electrolytically refined (Sample Nos. 50 to 54). The results are shown in Table 5.
Example 3 except that a copper nitrate solution was used as the electrolytic solution, the nitric acid concentration and the copper concentration were adjusted as shown in Table 5, and additive B was added to this electrolytic solution to a concentration of 30 mg / L. In the same manner as above, electrolytic copper was electrolytically refined (Sample Nos. 55 to 59). The results are shown in Table 5.
As shown in Table 5, sample Nos. With sulfuric acid concentration of 10 to 300 g / L and copper concentration of 5 to 90 g / L. Nos. 51 to 53 had few electrolytic copper impurities, and the smoothness of the electrolytic copper surface was good. Sample Nos. With nitric acid concentrations of 0.1 to 100 g / L and copper concentrations of 5 to 90 g / L. Nos. 56 to 58 had few electrolytic copper impurities, and the smoothness of the electrolytic copper surface was good. On the other hand, sample Nos. With sulfuric acid concentration, nitric acid concentration and copper concentration deviating from the above ranges. In Nos. 50, 54, 55, and 59, the surface of the electrodeposited copper was rough and / or the amount of slime generated was large. Therefore, the sulfuric acid solution used as the electrolyte preferably has a sulfuric acid concentration of 10 to 300 g / L and a copper concentration of 5 to 90 g / L, and the copper nitrate solution has a nitric acid concentration of 0.1 to 100 g / L and a copper concentration of 5 to 90 g / L. The range of is preferable.

 

According to the additive for high-purity copper electrolytic refining and the method for producing high-purity copper using the same according to the present invention, high-purity copper that significantly reduces impurities such as sulfur and silver concentration while suppressing generation of slime Can be manufactured.

Claims (7)

1. An additive added to copper electrolyte in electrolytic refining of high-purity copper, comprising a nonionic surfactant having a hydrophobic group containing an aromatic ring and a hydrophilic group containing a polyoxyalkylene group. High-purity copper electrolytic refining characterized in that the parameter dispersion component dD is 10 ≦ dD ≦ 20, the polar component dP is 6 ≦ dP ≦ 9, and the hydrogen bond component dH is 9 ≦ dH ≦ 11 Additives.
2. The dispersion component dD of the Hansen solubility parameter of the additive is 12 ≦ dD ≦ 17, the polar component dP is 7 ≦ dP ≦ 9, and the hydrogen bonding component dH is 9 ≦ dH ≦ 11. High purity copper electrolytic refining additive.
3. It is made of a nonionic surfactant having a hydrophobic group containing an aromatic ring and a hydrophilic group containing a polyoxyalkylene group, the dispersion component dD of the Hansen solubility parameter is 10 ≦ dD ≦ 20, and the polar component dP is 6 ≦ dP ≦ 9, a method for producing high-purity copper in which electrolysis is performed by adding an additive having a hydrogen bond component dH of 9 ≦ dH ≦ 11 to a copper electrolyte.
4. The method for producing high-purity copper according to claim 3, wherein the concentration of the additive in the copper electrolyte is 2 to 500 mg / L.
5. The method for producing high-purity copper according to claim 3 or 4, wherein the copper electrolyte is a copper sulfate solution, a copper nitrate solution, or a copper chloride solution.
6. A copper sulfate solution having a copper concentration of 5 to 90 g / L, a sulfuric acid concentration of 10 to 300 g / L, a nitric acid concentration of 0.1 to 100 g / L, or a hydrochloric acid concentration of 10 to 300 g / L. The method for producing high-purity copper according to claim 5, wherein:
7. The method for producing high-purity copper according to any one of claims 3 to 6, wherein high-purity copper having a sulfur and silver concentration of 1 ppm or less is produced.