Method for preparing HPCu-6N high-purity copper through continuous and stable electrolysis

Abstract

The invention discloses a method for preparing HPCu-6N high-purity copper through continuous and stable electrolysis, and belongs to the technical field of hydrometallurgy technologies. The method comprises the following steps: (1) mounting an anion-exchange membrane in an electrolytic bath, wherein the anion-exchange membrane divides the electrolytic bath into an anode chamber and a cathode chamber; (2) injecting electrolyte into the cathode chamber and the anode chamber; and (3) electrifying the anode and the cathode, starting electrolysis, simultaneously continuously conveying the electrolyte in the anode chamber into an ion exchange column group filled with ion exchange resin, after the electrolyte is subjected to adsorption and silver removal through the ion exchange column group, conveying the adsorbed solution to a precision filter for filtering, after the filtration is completed, conveying the filtered solution into the cathode chamber, and discharging the filtered solution into the cathode chamber. And then the electrolyte in the cathode chamber is conveyed into the anode chamber to supplement the electrolyte output by the anode chamber, and circulation is formed until electrolysis is completed. Through the synergistic effect of the anion exchange membrane and the ion exchange column group, the content of impurities in copper separated out from the cathode is reduced, and continuous and stable preparation of high-purity copper is achieved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of hydrometallurgy, and relates to a method for continuously and stably preparing HPCu-6N high-purity copper through electrolysis. BACKGROUND

[0002] High-purity copper (HPCu-6N) refers to copper with a purity of 99.9999% (6N), which is widely used in the fields of electronics, semiconductors, aerospace, etc.

[0003] In the process of electrolytic refining of copper, crude copper plates are usually used as anodes, and the crude copper plates usually contain impurity elements. In the electrolysis process, impurity elements will be dissolved into ions together with copper into the electrolyte, and will be deposited at the cathode, affecting the purity of the copper deposited at the cathode. The impurity elements usually include Zn, Fe, Ag, etc., among which, Zn and Fe ions are not easy to deposit, and can be eliminated by simply adjusting the potential difference and other process coefficients, however, it is difficult to remove silver ions in depth, and when silver ions are deposited at the cathode, the purity of the copper deposited at the cathode will be affected, especially when high-purity copper is prepared, the deposition of silver ions has a more obvious effect on the purity of the high-purity copper.

[0004] Therefore, it is necessary to provide a method for continuously and stably preparing HPCu-6N high-purity copper through electrolysis, which effectively removes silver impurities in depth and realizes the stable and continuous preparation of HPCu-6N high-purity copper. SUMMARY

[0005] In order to overcome the problems in the background art, the application reduces the amount of silver ions deposited at the cathode by delivering the anode chamber electrolyte to the ion exchange column group and deeply adsorbing silver ions by chelating resin filled in the ion exchange column group to reduce the content of silver ions in the electrolyte, effectively improves the purity of the copper deposited at the cathode, and the electrolyte is output from the anode chamber, sequentially passes through the ion exchange column group and the precision filter to reach the cathode chamber, and then the electrolyte in the cathode chamber is sent back to the anode chamber to supplement the electrolyte output from the anode chamber, forming a cycle in the entire electrolysis process, which can ensure that the silver ions newly dissolved into the electrolyte from the anode pass through the ion exchange column group to remove silver each time, and then enter the cathode chamber, so that the silver content in the electrolyte in the cathode chamber can be kept at a low level at all times, realizing the stable and continuous preparation of high-purity copper.

[0006] In order to achieve the above-mentioned purpose, the application realizes the technical scheme as follows: The application provides a method for continuously and stably preparing HPCu-6N high-purity copper through electrolysis, which comprises the following steps: (1) installing a cation exchange membrane in an electrolytic cell, and separating the electrolytic cell into an anode chamber and a cathode chamber by the cation exchange membrane; (2) injecting electrolyte into the cathode chamber and the anode chamber; (3) power on the anode and the cathode, start electrolysis, and continuously deliver the electrolyte in the anode chamber to the ion exchange column group filled with ion exchange resin. After the electrolyte is adsorbed and desilverized by the ion exchange column group, the adsorbed liquid is delivered to a precision filter for filtration. After the filtration is completed, the filtered liquid is delivered to the cathode chamber. The electrolyte in the cathode chamber is delivered to the anode chamber to replenish the electrolyte output from the anode chamber, forming a cycle until the electrolysis is completed.

[0007] As a preference, the ion exchange resin includes at least one of Dowex M4195 chelate resin, iminodiacetic acid type chelate resin, and amino phosphoric acid type chelate resin. The iminodiacetic acid type chelate resin can use, for example, DIAION TM CR20 polyamine type chelate resin, IRC748, and the like; and amino phosphoric acid type chelate resin can use, for example, D418, LSC-500C, D403, and the like. When the ion exchange resin includes a plurality of chelate resins, the chelate resins are mixed in any ratio.

[0008] As a preference, the ion exchange column group is composed of a plurality of single ion exchange columns connected in series, each of which is filled with ion exchange resin. The ratio of the volume of the ion exchange column group to the total volume of the electrolyte is ion exchange column group: electrolyte = 0.4~0.6:1.

[0009] As a preference, the electrolyte is copper sulfate electrolyte or copper nitrate electrolyte.

[0010] As a preference, the copper ion content in the copper sulfate electrolyte is 20~100g / L (1L of electrolyte contains 20~100g of copper ions) based on the total volume of the electrolyte, and the sulfuric acid content is 80~140g / L (1L of electrolyte contains 80~140g of sulfuric acid) based on the total volume of the electrolyte. The amount of thiocyanate added is 10~40g / t based on the mass of the precipitated copper, and the amount of gelatin added is 20~60g / t based on the mass of the precipitated copper. Further preferably, the copper ion content is 30~60g / L.

[0011] In the process of electrolytic refining of copper, the theoretical mass of copper precipitated at the cathode can be calculated according to the formula of Faraday's first law, etc. The error between the theoretical value and the actual value is very small. Therefore, the theoretical value of high-purity copper precipitation can be calculated before electrolysis, and then the amount of thiocyanate and gelatin added to the electrolyte can be calculated according to the theoretical value, i.e. 10~40g of thiocyanate and 20~60g of gelatin are added per ton of precipitated copper.

[0012] As preferred, the copper ion content in the copper nitrate electrolyte is 20-100 g / L based on the total volume of the electrolyte, the nitric acid content is 1-50 g / L based on the total volume of the electrolyte, the thiourea addition amount is 10-40 g / t based on the mass of the deposited copper, and the gelatin addition amount is 20-60 g / t based on the mass of the deposited copper. Further preferably, the copper ion content is 30-80 g / L.

[0013] As preferred, in the step (3), the electrolysis current density is 150-300 A / m 2 , the electrolysis temperature is 15-60 ℃, the electrolysis time is 24-120 h, and the electrolyte circulation flow rate is 30-150 mL / min.

[0014] As preferred, the anode is a copper plate with a copper content greater than 99.99% and a silver content of ≤20 ppm, the cathode comprises a 316L stainless steel plate or a titanium plate with a titanium content of ≥99.5%, and the distance between the anode and the cathode is 5-9 cm.

[0015] As preferred, the precision filter has a filtering precision of 1.0 μm.

[0016] As preferred, in the step (3), the silver ion content in the electrolyte is not more than 0.1 mg / L based on the total volume of the electrolyte (not more than 0.1 mg of silver ion content in 1 L of electrolyte). Commercially available copper sulfate or copper nitrate electrolyte inevitably contains silver ions, and in order to avoid serious negative impact on the preparation of high-purity copper, an electrolyte with a low silver ion content needs to be selected.

[0017] The present application has the following advantages: 1. The present application sets up a cation exchange membrane in the electrolytic cell to separate the electrolytic cell into an anode chamber and a cathode chamber, avoids the diffusion of impurity silver ions dissolved in the electrolyte in the anode chamber to the cathode chamber during the electrolysis process, affects the purity of the cathode-deposited copper, and uses a chelating resin with high selective adsorption of silver ions (the adsorption capacity can reach more than 0.1 mg / g) to adsorb the silver ions in the electrolyte, so that the electrolyte entering the cathode chamber maintains a low silver content, thereby improving the electrolytic refining copper purity and realizing the preparation of HPCu-6N high-purity copper.

[0018] 2. The present application uses electrolyte recycling to make the electrolyte properties more stable, realize continuous and stable preparation of high-purity copper, and is conducive to improving production efficiency and reducing production cost.

[0019] 3. The present application uses a chelating resin which not only has high selective adsorption of silver ions but also has regenerability, can effectively reduce raw material consumption, and can be reused, which is conducive to reducing the amount of waste generated and reducing environmental pollution. DETAILED DESCRIPTION

[0020] The application will be further described in connection with specific examples. However, the scope of the application is not limited to the examples.

[0021] Chemical reagents not particularly specified in the examples are commercially available analytical grade.

[0022] Example 1 This example is electrolytic refining of copper according to the following method: This example uses copper plate with copper content of 99.995% and silver content of 15 ppm as anode plate, and uses 316L stainless steel plate as cathode plate.

[0023] (1) Install an anion exchange membrane in the electrolytic cell, which separates the electrolytic cell into an anode chamber and a cathode chamber, and the volume ratio of the anode chamber to the cathode chamber is 1:1.5; (2) Inject copper nitrate electrolyte into the cathode chamber and the anode chamber, the silver ion content in the electrolyte is 0.05 mg / L, the copper ion concentration is 60 g / L, the nitric acid concentration is 10 g / L, and according to the addition amount of 20 g / t, thiourea is added, and according to the addition amount of 30 g / t, gelatin is added.

[0024] (3) Put the anode plate into the anode chamber so that the anode plate is in contact with the electrolyte in the anode chamber, and put the cathode plate into the cathode chamber so that the cathode plate is in contact with the electrolyte in the cathode chamber, the distance between the anode plate and the cathode plate is 7 cm, and the power supply is turned on at the same time with the current density of 200 A / m 2 , start electrolysis, and the electrolysis process is carried out at 40℃, during the electrolysis process, the electrolyte in the anode chamber is continuously delivered to the ion exchange column group filled with ion exchange resin at a flow rate of 60 mL / min, after the electrolyte is adsorbed and desilvered by the ion exchange column group, the adsorbed liquid is delivered to the precision filter for filtration, after the filtration is completed, the filtered liquid is delivered to the cathode chamber, and then the electrolyte in the cathode chamber is delivered to the anode chamber at a flow rate of 90 mL / min to supplement the electrolyte output from the anode chamber, forming a circulation until the electrolysis is completed, the ion exchange column group is composed of 5 ion exchange columns connected in series, each ion exchange column is filled with Dowex M4195, and the volume ratio of the ion exchange column group to the total volume of the electrolyte is ion exchange column group: electrolyte = 0.5:1. After electrolysis for 48 h, the electrolysis is completed.

[0025] The silver ion content in the adsorbed liquid in the electrolysis process of this example is continuously detected, and the silver ion content in the adsorbed liquid can be stably controlled below 0.01 mg / L.

[0026] The cathode copper deposited in this example is detected, and the purity of the deposited copper reaches the requirement of HPCu-6N high purity copper.

[0027] Example 2 This example electrolytic refining of copper was carried out according to the following method: This example used copper plates with a copper content of 99.995% and a silver content of 15 ppm as anode plates, and used 316L stainless steel plates as cathode plates.

[0028] (1) The anion exchange membrane was installed in the electrolytic cell, and the anion exchange membrane separated the electrolytic cell into an anode chamber and a cathode chamber, and the volume ratio of the anode chamber to the cathode chamber was 1:1.5; (2) Copper nitrate electrolyte was injected into the cathode chamber and the anode chamber, the silver ion content in the electrolyte was 0.1 mg / L, the copper ion concentration was 20 g / L, the nitric acid concentration was 1 g / L, and thiourea was added in an amount of 10 g / t, and gelatin was added in an amount of 20 g / t.

[0029] (3) The anode plate was installed in the anode chamber so that the anode plate was in contact with the electrolyte in the anode chamber, and the cathode plate was installed in the cathode chamber so that the cathode plate was in contact with the electrolyte in the cathode chamber, and the distance between the anode plate and the cathode plate was 5 cm, and the power supply was turned on while setting the current density to 150 A / m 2 , the electrolysis was started, and the electrolysis process was carried out at 15°C, and during the electrolysis process, the electrolyte in the anode chamber was continuously delivered to the ion exchange column group filled with ion exchange resin at a flow rate of 30 mL / min, and after the electrolyte was adsorbed and desilvered by the ion exchange column group, the adsorbed liquid was delivered to a precision filter for filtration, and after the filtration was completed, the filtered liquid was delivered to the cathode chamber, and the electrolyte in the cathode chamber was delivered to the anode chamber at a flow rate of 60 mL / min to supplement the electrolyte output from the anode chamber, forming a circulation until the electrolysis was completed, the ion exchange column group was composed of 4 ion exchange columns connected in series, each ion exchange column was filled with D418, and the ratio of the volume of the ion exchange column group to the total volume of the electrolyte was ion exchange column group: electrolyte = 0.4:1. After 24 hours of electrolysis, the electrolysis was completed.

[0030] The cathode copper deposited in this example was detected, and the purity of the deposited copper reached the requirements of HPCu-6N high purity copper.

[0031] Example 3 This example electrolytic refining of copper was carried out according to the following method: This example used copper plates with a copper content of 99.995% and a silver content of 15 ppm as anode plates, and used 316L stainless steel plates as cathode plates.

[0032] (1) The anion exchange membrane was installed in the electrolytic cell, and the anion exchange membrane separated the electrolytic cell into an anode chamber and a cathode chamber, and the volume ratio of the anode chamber to the cathode chamber was 1:1.5; (2) Injecting copper nitrate electrolyte into the cathode chamber and the anode chamber, the silver ion content in the electrolyte is 0.1 mg / L, the copper ion concentration is 100 g / L, the nitric acid concentration is 50 g / L, and thiourea is added in an amount of 40 g / t, and gelatin is added in an amount of 60 g / t.

[0033] (3) Installing the anode plate into the anode chamber to make the anode plate contact with the electrolyte in the anode chamber, and installing the cathode plate into the cathode chamber to make the cathode plate contact with the electrolyte in the cathode chamber, the distance between the anode plate and the cathode plate is 9 cm, and the power supply is turned on while setting the current density to be 300 A / m 2 , starting electrolysis, and the electrolysis process is carried out at 60°C, during the electrolysis process, the electrolyte in the anode chamber is continuously delivered to the ion exchange column group filled with ion exchange resin at a flow rate of 150 mL / min, after the electrolyte is adsorbed to remove silver by the ion exchange column group, the adsorbed liquid is delivered to the precision filter for filtration, after the filtration is completed, the filtered liquid is delivered to the cathode chamber, and then the electrolyte in the cathode chamber is delivered to the anode chamber at a flow rate of 150 mL / min to supplement the electrolyte output from the anode chamber, forming a circulation until the electrolysis is completed, the ion exchange column group is composed of 6 ion exchange columns connected in series, each ion exchange column is filled with a mixture of Dowex M4195, IRC748 and LSC-500C, and the ratio of the volume of the ion exchange column group to the total volume of the electrolyte is ion exchange column group: electrolyte = 0.6:1. After electrolysis for 120 h, the electrolysis is completed.

[0034] The cathode copper precipitation in this embodiment is detected, and the purity of the precipitated copper reaches the requirement of HPCu-6N high-purity copper.

[0035] Example 4 This embodiment carries out copper electrolytic refining according to the following method: In this embodiment, a copper plate with a copper content of 99.998% and a silver content of 10 ppm is used as the anode plate, and pure titanium with a purity of ≥99.5% is used as the cathode plate.

[0036] (1) Installing the anion exchange membrane in the electrolytic cell, the anion exchange membrane separates the electrolytic cell into an anode chamber and a cathode chamber, and the volume ratio of the anode chamber to the cathode chamber is 1:2; (2) Injecting copper nitrate electrolyte into the cathode chamber and the anode chamber, the silver ion content in the electrolyte is 0.01 mg / L, the copper ion concentration is 80 g / L, the nitric acid concentration is 15 g / L, and thiourea is added in an amount of 30 g / t, and gelatin is added in an amount of 50 g / t.

[0037] (3) the anode plate is installed in the anode chamber to make the anode plate contact with the electrolyte in the anode chamber, the cathode plate is installed in the cathode chamber to make the cathode plate contact with the electrolyte in the cathode chamber, and the distance between the anode plate and the cathode plate is 8 cm, the power supply is turned on, and the current density is set to 250 A / m 2 The electrolysis process is carried out at 50°C, during which the electrolyte in the anode chamber is continuously delivered to the ion exchange column group filled with ion exchange resin at a flow rate of 90 mL / min, after the electrolyte is adsorbed and silver is removed by the ion exchange column group, the adsorbed liquid is delivered to the precision filter for filtration, after the filtration is completed, the filtered liquid is delivered to the cathode chamber, and then the electrolyte in the cathode chamber is delivered to the anode chamber at a flow rate of 120 mL / min to supplement the electrolyte output from the anode chamber, to form a cycle until the electrolysis is completed. The ion exchange column group is composed of 6 ion exchange columns connected in series, each ion exchange column is filled with DIAION TM CR20 polyamine type chelating resin, the ratio of the volume of the ion exchange column group to the total volume of the electrolyte is ion exchange column group: electrolyte = 0.6:1. After electrolysis for 72 h, the electrolysis is completed.

[0038] The silver ion content in the adsorbed liquid in the electrolysis process of this embodiment is continuously detected, and the silver ion content in the adsorbed liquid can be stably controlled below 0.005 mg / L The cathode copper deposition in this embodiment is detected, and the purity of the deposited copper reaches the requirement of HPCu-6N high-purity copper.

[0039] Example 5 This embodiment carries out electrolytic refining of copper according to the following method: This embodiment uses a copper plate with a copper content of 99.998% and a silver content of 10 ppm as the anode plate, and uses pure titanium with a purity of ≥99.5% as the cathode plate.

[0040] (1) The anion exchange membrane is installed in the electrolytic cell, and the anion exchange membrane separates the electrolytic cell into an anode chamber and a cathode chamber, and the volume ratio of the anode chamber to the cathode chamber is 1:2; (2) Copper sulfate electrolyte is injected into the cathode chamber and the anode chamber, the silver ion content in the electrolyte is 0.01 mg / L, the copper ion concentration is 45 g / L, the sulfuric acid concentration is 110 g / L, and thiocyanate is added at an addition amount of 25 g / t, and gelatin is added at an addition amount of 40 g / t.

[0041] (3) the anode plate is installed in the anode chamber to make the anode plate contact with the electrolyte in the anode chamber, the cathode plate is installed in the cathode chamber to make the cathode plate contact with the electrolyte in the cathode chamber, and the distance between the anode plate and the cathode plate is 8 cm, the power supply is turned on, and the current density is set to 250 A / m 2, electrolysis is started, and the electrolysis is carried out at 50℃. During the electrolysis, the electrolyte in the anode chamber is continuously delivered to the ion exchange column group filled with ion exchange resin at a flow rate of 90 mL / min. After the electrolyte is adsorbed to remove silver by the ion exchange column group, the adsorbed solution is delivered to a precision filter for filtration. After the filtration is completed, the filtered solution is delivered to the cathode chamber. The electrolyte in the cathode chamber is delivered to the anode chamber at a flow rate of 120 mL / min to replenish the electrolyte output from the anode chamber, forming a circulation until the electrolysis is completed. The ion exchange column group is composed of 6 ion exchange columns connected in series, and each ion exchange column is filled with D403. The ratio of the volume of the ion exchange column group to the total volume of the electrolyte is ion exchange column group: electrolyte = 0.6:1. After 72 h of electrolysis, the electrolysis is completed.

[0042] The cathode copper precipitation in this embodiment is detected, and the purity of the precipitated copper reaches the requirement of HPCu-6N high-purity copper.

[0043] Example 6 This embodiment carries out electrolytic refining of copper according to the following method: In this embodiment, a copper plate with a copper content of 99.998% and a silver content of 10 ppm is used as the anode plate, and pure titanium with a purity of ≥99.5% is used as the cathode plate.

[0044] (1) The anion exchange membrane is installed in the electrolytic cell, and the anion exchange membrane separates the electrolytic cell into an anode chamber and a cathode chamber. The volume ratio of the anode chamber to the cathode chamber is 1:2. (2) Copper sulfate electrolyte is injected into the cathode chamber and the anode chamber. The silver ion content in the electrolyte is 0.01 mg / L, the copper ion concentration is 20 g / L, the sulfuric acid concentration is 80 g / L, and thiourea is added at an addition amount of 10 g / t, and gelatin is added at an addition amount of 20 g / t.

[0045] (3) The anode plate is installed in the anode chamber to make the anode plate contact with the electrolyte in the anode chamber. The cathode plate is installed in the cathode chamber to make the cathode plate contact with the electrolyte in the cathode chamber. The distance between the anode plate and the cathode plate is 8 cm. The power supply is turned on, and the current density is set to 250 A / m 2 , electrolysis is started, and the electrolysis is carried out at 50℃. During the electrolysis, the electrolyte in the anode chamber is continuously delivered to the ion exchange column group filled with ion exchange resin at a flow rate of 90 mL / min. After the electrolyte is adsorbed to remove silver by the ion exchange column group, the adsorbed solution is delivered to a precision filter for filtration. After the filtration is completed, the filtered solution is delivered to the cathode chamber. The electrolyte in the cathode chamber is delivered to the anode chamber at a flow rate of 120 mL / min to replenish the electrolyte output from the anode chamber, forming a circulation until the electrolysis is completed. The ion exchange column group is composed of 6 ion exchange columns connected in series, and each ion exchange column is filled with DIAION TMA mixture of CR20 polyamine type chelating resin and D403, the ratio of ion exchange column set volume to electrolyte total volume is ion exchange column set: electrolyte = 0.6:1. The electrolysis is completed after 72 hours of electrolysis.

[0046] The cathode copper of this example is detected, and the purity of the precipitated copper reaches the requirement of HPCu-6N high purity copper.

[0047] Example 7 This example electrolytic refining of copper is carried out according to the following method: This example uses a copper plate with a copper content of 99.998% and a silver content of 10 ppm as the anode plate, and uses pure titanium with a purity of ≥99.5% as the cathode plate.

[0048] (1) The anion exchange membrane is installed in the electrolytic cell, and the anion exchange membrane separates the electrolytic cell into an anode chamber and a cathode chamber, and the volume ratio of the anode chamber to the cathode chamber is 1:2; (2) Copper sulfate electrolyte is injected into the cathode chamber and the anode chamber, the silver ion content in the electrolyte is 0.01 mg / L, the copper ion concentration is 100 g / L, and the sulfuric acid concentration is 140 g / L, and thiourea is added in an amount of 40 g / t, and gelatin is added in an amount of 60 g / t.

[0049] (3) The anode plate is installed in the anode chamber, so that the anode plate is in contact with the electrolyte in the anode chamber, and the cathode plate is installed in the cathode chamber, so that the cathode plate is in contact with the electrolyte in the cathode chamber, and the distance between the anode plate and the cathode plate is 8 cm, and the power supply is turned on at the same time. The current density is set to 250 A / m 2 , start electrolysis, the electrolysis process is carried out at 50℃, during the electrolysis process, the electrolyte in the anode chamber is continuously delivered to the ion exchange column set filled with ion exchange resin at a flow rate of 90 mL / min, after the electrolyte is adsorbed and desilvered by the ion exchange column set, the adsorbed liquid is delivered to the precision filter for filtration, after the filtration is completed, the filtered liquid is delivered to the cathode chamber, and the electrolyte in the cathode chamber is delivered to the anode chamber at a flow rate of 120 mL / min to supplement the electrolyte output by the anode chamber, forming a cycle until the electrolysis is completed. The ion exchange column set is composed of 6 ion exchange columns connected in series, each ion exchange column is filled with a mixture of Dowex M4195 and LSC-500C, and the ratio of ion exchange column set volume to electrolyte total volume is ion exchange column set: electrolyte = 0.6:1. The electrolysis is completed after 72 hours of electrolysis.

[0050] The cathode copper of this example is detected, and the purity of the precipitated copper reaches the requirement of HPCu-6N high purity copper.

[0051] In summary, the application guarantees that the electrolyte in the cathode chamber stably contains low silver ions through the synergistic effect of the anion exchange membrane and the ion exchange column set, thereby reducing the impurity content in the cathode copper deposition, and realizing continuous and stable preparation of high-purity copper through electrolyte recycling, which is conducive to improving production efficiency and reducing production cost.

[0052] Finally, it should be pointed out that the above preferred embodiments are only used to illustrate the technical solutions of the application and are not limiting. Although the application has been described in detail through the above preferred embodiments, those skilled in the art should understand that various changes can be made to the form and details thereof without departing from the scope defined by the claims of the application.

Claims

1. A method for the continuous and stable electrolytic preparation of HPCu-6N high-purity copper, characterized in that: The method includes the following steps: (1) An anion exchange membrane is installed in the electrolytic cell, which divides the electrolytic cell into an anode chamber and a cathode chamber; (2) Inject electrolyte into the cathode chamber and anode chamber; (3) Apply current to the anode and cathode to start electrolysis. At the same time, the electrolyte in the anode chamber is continuously transported to the ion exchange column group filled with ion exchange resin. After the electrolyte is adsorbed and desilvered by the ion exchange column group, the adsorbed liquid is transported to the precision filter for filtration. After filtration, the filtered liquid is transported to the cathode chamber, and then the electrolyte in the cathode chamber is transported to the anode chamber to replenish the electrolyte output from the anode chamber, forming a cycle until electrolysis is completed.

2. The method according to claim 1, characterized in that: The ion exchange resin includes at least one of Dow M4195 chelating resin, iminodiacetic acid type chelating resin, and aminophosphate type chelating resin.

3. The method according to claim 1, characterized in that: The ion exchange column group consists of several single ion exchange columns connected in series. Each ion exchange column is filled with ion exchange resin. The ratio of the volume of the ion exchange column group to the total volume of the electrolyte is ion exchange column group: electrolyte = 0.4~0.6:

1.

4. The method according to claim 1, characterized in that: The electrolyte is either copper sulfate electrolyte or copper nitrate electrolyte.

5. The method according to claim 4, characterized in that: The copper ion content in the copper sulfate electrolyte is 20~100g / L based on the total volume of the electrolyte, the sulfuric acid content is 80~140g / L based on the total volume of the electrolyte, the amount of thiourea added is 10~40g / t based on the mass of copper deposited, and the amount of gelatin added is 20~60g / t based on the mass of copper deposited.

6. The method according to claim 4, characterized in that: The copper ion content in the copper nitrate electrolyte is 20~100g / L based on the total volume of the electrolyte, the nitric acid content is 1~50g / L based on the total volume of the electrolyte, the amount of thiourea added is 10~40g / t based on the mass of copper deposited, and the amount of gelatin added is 20~60g / t based on the mass of copper deposited.

7. The method according to any one of claims 1-6, characterized in that: In step (3), the electrolysis current density is 150~300 A / m. 2 The electrolysis temperature is 15~60℃, the electrolysis time is 24-120h, and the electrolyte circulation flow rate is 30-150mL / min.

8. The method according to claim 1, characterized in that: The anode is a copper plate with a copper content greater than 99.99% and a silver content ≤20ppm. The cathode comprises a 316L stainless steel plate or a titanium plate with a titanium content ≥99.5%. The distance between the anode and the cathode is 5~9cm.

9. The method according to claim 1, characterized in that: The precision filter has a filtration accuracy of 1.0 μm.

10. The method according to claim 1, characterized in that: In step (3), the silver ion content in the electrolyte shall not exceed 0.1 mg / L based on the total volume of the electrolyte.