A method for preparing a copper electrolyte electrowinning copper removal anode plate

Abstract

This invention discloses a method for preparing a copper electrolyte electrowinning copper-removing anode plate, comprising the following steps: melting and removing slag to obtain a Pb solution; adding other alloying elements to the Pb solution, controlling the temperature, stirring and mixing thoroughly, and then holding at the temperature; the other alloying elements include Ca, Sn, and Cs; removing slag again, and casting to obtain a blank plate; rolling, cutting, punching, and forming to form a perforated plate, thus obtaining the copper electrolyte electrowinning copper-removing anode plate. This invention, by adding a certain amount of Cs, can make the alloy grains small, the structure uniform and dense, and the corrosion resistance good, thus enhancing the alloy strength and improving corrosion resistance. Simultaneously, the addition of Cs reduces the resistivity of the PbO2 surface film, effectively reducing the oxygen evolution overpotential and reducing power consumption. Furthermore, the repeated rolling of the blank plate in this invention helps to enhance the density of the structure and improve corrosion resistance; the perforated anode plate increases the surface area, thereby reducing the oxygen evolution overpotential of the anode.

Description

Technical Field

[0001] This invention relates to the field of copper electrolysis technology, and specifically to a method for preparing a copper electrolyte electrowinning anode plate. Background Technology

[0002] During copper electrolysis, the electrochemical dissolution reaction at the anode causes the concentration of copper ions in the electrolyte to increase continuously. The increase in copper ions in the electrolyte is about 1.2%-2.0% of the amount dissolved at the anode. At the same time, some impurities (As, Sb, Bi, etc.) in the anode plate will dissolve in the electrolyte and continuously accumulate to form flocculent matter, which affects the quality of the cathode copper. Therefore, it is necessary to regularly remove copper and impurities from the copper electrolyte.

[0003] Currently, most domestic enterprises use electrowinning to purify copper electrolyte. Lead alloy plates are used as anodes, and starting or residual electrodes are used as cathodes. Under direct current, electrowinning forms black copper plates and copper-removing sludge containing impurities such as As, Sb, and Bi, thus purifying the copper electrolyte. Traditional electrowinning lead alloy plates are mainly Pb-Sn-Ca plates, with the addition of certain amounts of Sn and Ca to improve the hardness and conductivity of the anode plate. The lead in the anode plate reacts with sulfate ions in the electrolyte to form lead sulfate, which, after oxidation, forms a dense lead dioxide film for discharge reaction. Because copper ore resources often contain small amounts of Ag, HCl is often added in actual production to generate AgCl precipitate, reducing Ag loss. Cl... - The presence of ions can disrupt the density and stability of the lead oxide film, leading to flaking of flaky material on the lead plate surface, deformation of the lead plate itself, and affecting the distance between the anode and cathode during electrodeposition. This results in a high oxygen evolution overpotential and increased energy consumption. Therefore, there is an urgent need to develop a highly efficient, energy-saving, and corrosion-resistant copper electrolyte electrodeposition anode plate for copper removal. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention aims to provide a method for preparing a copper electrolyte electrowinning copper removal anode plate.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] A method for preparing a copper electrolyte electrowinning copper removal anode plate includes the following steps:

[0007] S1. Melt pure Pb by rapid heating, then add NH4Cl to remove slag;

[0008] S2. Add other alloying elements to the melted and slag-removed Pb liquid obtained in step S1, control the temperature, stir and mix thoroughly, and then keep warm; the other alloying elements include Ca, Sn and Cs, and based on the total mass of Ca, Sn, Cs and Pb, the amount of Ca added is 0.08%-0.09%, the amount of Sn added is 1.5%-2.0%, and the amount of Cs added is 0.03-0.05%;

[0009] S3. After adding NH4Cl again to remove slag, the slag-removed Pb-Sn-Ca-Cs alloy liquid is cast to obtain a blank plate.

[0010] S4. Roll, cut, punch, and form the blank plate obtained in step S3 to form a perforated plate, thereby obtaining the Pb-Sn-Ca-Cs alloy anode plate, namely the copper electrolyte electrowinning copper removal anode plate.

[0011] Furthermore, in step S1, the melting temperature of pure Pb is 400°C.

[0012] Furthermore, in step S2, the temperature for stirring and mixing after adding other alloying elements is 500℃-600℃, and the stirring time is 60-90min.

[0013] Furthermore, in step S2, the heat preservation time is 5-10 minutes.

[0014] Furthermore, in step S4, the rolling process employs hot and cold cross-rolling, with cold rolling performed after hot rolling is completed and the material has naturally cooled.

[0015] The beneficial effects of this invention are as follows: By adding a certain amount of Cs, the alloy grains become smaller, the structure becomes more uniform and dense, and the corrosion resistance is better, thus enhancing the alloy strength and improving corrosion resistance. Simultaneously, the addition of Cs reduces the resistivity of the PbO2 surface film, effectively reducing the oxygen evolution overpotential and lowering power consumption. Furthermore, the repeated rolling of the blank plate in this invention helps to enhance the density of the structure and improve corrosion resistance; the punching method used in the anode plate increases the surface area, thereby reducing the oxygen evolution overpotential of the anode. Attached Figure Description

[0016] Figure 1 This is a flowchart illustrating the methods of various embodiments of the present invention. Detailed Implementation

[0017] The present invention will be further described below with reference to the accompanying drawings. It should be noted that this embodiment is based on the present technical solution and provides detailed implementation methods and specific operation processes, but the protection scope of the present invention is not limited to this embodiment.

[0018] Example 1

[0019] This embodiment provides a method for preparing a copper electrolyte electrowinning copper removal anode plate, such as... Figure 1 As shown, it includes the following steps:

[0020] S1. Melt pure Pb rapidly at 400℃, then add NH4Cl to remove slag;

[0021] S2. Add other alloying elements to the melted and slag-removed Pb liquid obtained in step S1, control the temperature at 500℃, stir thoroughly for 60 minutes, and then keep warm for 5 minutes; the other alloying elements include Ca, Sn and Cs, and based on the total mass of Ca, Sn, Cs and Pb, the amount of Ca added is 0.09%, the amount of Sn added is 1.5%, and the amount of Cs added is 0.03%;

[0022] S3. After adding NH4Cl again to remove slag, the slag-removed Pb-Sn-Ca-Cs alloy liquid is cast to obtain a blank plate.

[0023] S4. After hot and cold cross-rolling the blank plate obtained in step S3 five times, it is cut and punched to form a copper electrolyte electrowinning copper removal anode plate.

[0024] The copper electrolyte electrowinning anode plate alloy obtained in this embodiment has a hardness of 30.9 HV.

[0025] The copper electrolyte electrowinning anode plate obtained in this embodiment was subjected to cell voltage detection at a low current density of 100 A / m. 2 With an H2SO4 concentration of 180 g / L and a temperature of 50 °C, the cell voltage was 2.02 V. The results show that the copper electrolyte electrowinning anode plate obtained in this embodiment is relatively energy-efficient.

[0026] In addition, ultra-high current density (5000A / m 2 An accelerated corrosion test was conducted on the copper electrolyte electrowinning copper removal anode plate obtained in this embodiment. The anode failed after 8.4 hours, which is equivalent to a conventional lifespan of 875 days. The results show that the copper electrolyte electrowinning copper removal anode plate obtained in this embodiment has a long lifespan and is corrosion resistant.

[0027] Example 2

[0028] This embodiment provides a method for preparing a copper electrolyte electrowinning copper removal anode plate, such as... Figure 1 As shown, it includes the following steps:

[0029] S1. Melt pure Pb rapidly at 400℃, then add NH4Cl to remove slag;

[0030] S2. Add other alloying elements to the melted and slag-removed Pb liquid obtained in step S1, control the temperature at 500℃, stir thoroughly for 60 minutes, and then keep warm for 5 minutes; the other alloying elements include Ca, Sn and Cs, and based on the total mass of Ca, Sn, Cs and Pb, the amount of Ca added is 0.09%, the amount of Sn added is 2.0%, and the amount of Cs added is 0.05%;

[0031] S3. After adding NH4Cl again to remove slag, the slag-removed Pb-Sn-Ca-Cs alloy liquid is cast to obtain a blank plate.

[0032] S4. After hot and cold cross-rolling the blank plate obtained in step S3 five times, it is cut and punched to form a copper electrolyte electrowinning copper removal anode plate.

[0033] The alloy hardness of the copper electrolyte electrowinning copper removal anode plate obtained in this embodiment is 31.7HV.

[0034] The copper electrolyte electrowinning anode plate obtained in this embodiment was subjected to cell voltage detection at a low current density of 100 A / m. 2 Under the conditions of H2SO4 concentration of 180 g / L and temperature of 50℃, the cell voltage was 1.98 V. The results show that the copper electrolyte obtained in this embodiment is relatively energy-efficient for copper removal anode plates.

[0035] In addition, at ultra-high current density (5000 A / m 2 Under the conditions described above, the copper electrolyte electrowinning copper removal anode plate obtained in this embodiment was subjected to an accelerated corrosion test. The anode failed after 8.8 hours, which is equivalent to a conventional lifespan of 917 days. The results show that the copper electrolyte electrowinning copper removal anode plate obtained in this embodiment has a long lifespan and is corrosion resistant.

[0036] Example 3

[0037] This embodiment provides a method for preparing a copper electrolyte electrowinning copper removal anode plate, such as... Figure 1 As shown, it includes the following steps:

[0038] S1. Melt pure Pb rapidly at 400℃, then add NH4Cl to remove slag;

[0039] S2. Add other alloying elements to the melted and slag-removed Pb liquid obtained in step S1, control the temperature at 600℃, stir thoroughly for 90 minutes, and then keep warm for 10 minutes; the other alloying elements include Ca, Sn and Cs, and based on the total mass of Ca, Sn, Cs and Pb, the amount of Ca added is 0.08%, the amount of Sn added is 1.65%, and the amount of Cs added is 0.05%;

[0040] S3. After adding NH4Cl again to remove slag, the slag-removed Pb-Sn-Ca-Cs alloy liquid is cast to obtain a blank plate.

[0041] S4. After hot and cold cross-rolling the blank plate obtained in step S3 five times, it is cut and punched to form a copper electrolyte electrowinning copper removal anode plate.

[0042] The alloy hardness of the copper electrolyte electrowinning copper removal anode plate obtained in this embodiment is 31.4 HV.

[0043] The copper electrolyte electrowinning anode plate obtained in this embodiment was subjected to cell voltage detection at a low current density of 100 A / m. 2 With an H2SO4 concentration of 180 g / L and a temperature of 50 °C, the cell voltage was 1.96 V. The results show that the copper electrolyte electrowinning copper removal anode plate obtained in this embodiment is relatively energy-efficient.

[0044] In addition, at ultra-high current density (5000 A / m 2 Under these conditions, the copper electrolyte electrowinning copper removal anode plate obtained in this embodiment was subjected to an accelerated corrosion test. The anode failed after 8.5 hours, which is equivalent to a conventional lifespan of 885 days. The results show that the copper electrolyte electrowinning copper removal anode plate obtained in this embodiment has a long lifespan and is corrosion resistant.

[0045] When using conventional lead alloy anode plates for electrolysis, the cell voltage is 2.2V and the conventional lifespan is 730 days under the same conditions. Therefore, the copper electrolyte electrowinning and copper removal anode plates prepared in the above embodiments have significantly better performance than conventional lead alloy anode plates.

[0046] For those skilled in the art, various corresponding changes and modifications can be made based on the above technical solutions and concepts, and all such changes and modifications should be included within the protection scope of the claims of this invention.

Claims

1. A method for preparing a copper electrolyte electrowinning copper removal anode plate, characterized in that, Includes the following steps: S1. Melt pure Pb by rapid heating, then add NH4Cl to remove slag; S2. Add other alloying elements to the Pb liquid obtained after melting and slag removal in step S1, control the temperature, stir and mix thoroughly, and then keep it at the temperature. The other alloying elements are Ca, Sn, and Cs. Based on the total mass of Ca, Sn, Cs, and Pb, the amount of Ca added is 0.08%-0.09%, the amount of Sn added is 1.5%-2.0%, and the amount of Cs added is 0.03%-0.05%. S3. After adding NH4Cl again to remove slag, the slag-removed Pb-Sn-Ca-Cs alloy liquid is cast to obtain a blank plate. S4. Roll, cut, punch, and form the blank plate obtained in step S3 to form a perforated plate, thereby obtaining the Pb-Sn-Ca-Cs alloy anode plate, namely the copper electrolyte electrowinning copper removal anode plate.

2. The preparation method according to claim 1, characterized in that, In step S1, the melting temperature of pure Pb is 400℃.

3. The preparation method according to claim 1, characterized in that, In step S2, the temperature for stirring and mixing after adding other alloying elements is 500℃-600℃, and the stirring time is 60-90min.

4. The preparation method according to claim 1, characterized in that, In step S2, the heat preservation time is 5-10 minutes.

5. The preparation method according to claim 1, characterized in that, In step S4, the rolling process employs hot and cold cross-rolling, with cold rolling performed after hot rolling is completed and the material has naturally cooled.

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