Method for removing impurities in high-purity copper electrodeposition process

Abstract

The application relates to a method for removing impurities in a high-purity copper electrodeposition process, which comprises the following steps: mixing a sodium sulfide precipitant with high-purity copper electrodeposition circulating liquid, stirring and reacting, then performing solid-liquid separation to obtain pretreated electrodeposition circulating liquid; and sequentially passing the pretreated electrodeposition circulating liquid through a mercapto type selective silver-removing resin and a strong alkaline anion exchange resin to obtain a decontaminated liquid. The method combines sodium sulfide chemical precipitation pretreatment with mercapto type silver-removing resin and strong alkaline anion exchange resin series connection deep purification, realizes efficient and synchronous removal of silver and chlorine impurities, reduces the silver content in the decontaminated liquid to below 0.005 mg / L, meets the requirements of 6N and above high-purity copper, and the removal method does not cause secondary pollution, and the resin can be regenerated and recycled.

Description

Technical Field

[0001] This invention belongs to the field of metallurgical technology and relates to a method for purifying the electrodepositer solution during the high-purity copper electrodeposition process, and more particularly to a method for removing impurities during the high-purity copper electrodeposition process. Background Technology

[0002] High-purity copper (purity ≥ 6N) possesses excellent electrical and thermal conductivity and ductility, and is commonly used in high-end electronic information fields such as semiconductor chip lead frames, vacuum electronic devices, and superconducting wires. Electrodeposition is the mainstream process for producing ultra-high-purity copper, and the purity of the product directly depends on the cleanliness of the electrodeposition cycle solution. Silver and chloride are the most common impurities in high-purity copper electrodeposition systems. Silver ions preferentially precipitate at the cathode, leading to excessive silver content in the copper product and affecting its electrical properties. Chloride ions not only corrode electrodes and production equipment but also form stable complexes with copper ions, reducing current efficiency. Furthermore, chloride ions easily form pinholes and pits on the cathode surface, deteriorating the surface quality of the copper product.

[0003] In existing technologies, the methods for removing impurities from copper electrodepositers are mainly divided into two categories: chemical precipitation and resin adsorption. Chemical precipitation alone can usually only remove a single impurity. For example, using organic sulfides such as thiourea and carbon disulfide to precipitate silver ions not only has limited impurity removal accuracy and cannot meet the production requirements of 6N and above ultra-high purity copper, but also easily introduces toxic and harmful organic impurities, causing secondary pollution. Although resin adsorption alone can achieve deep impurity removal, the adsorption load is too high when facing high concentrations of impurities, the resin is prone to rapid saturation and deactivation, the service life is greatly shortened, and it is difficult to simultaneously and efficiently remove silver ions and chloride ions, two impurities with different properties.

[0004] Furthermore, existing technologies have not conducted systematic research on the synergistic removal of silver and chlorine impurities in high-purity copper electrodeposition systems, and cannot simultaneously solve problems such as incomplete impurity removal, easy introduction of additional impurities, and high operating costs. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide a method for removing impurities during the high-purity copper electrowinning process. This method achieves efficient and simultaneous removal of silver and chlorine impurities through deep purification by combining sodium sulfide chemical precipitation pretreatment with a series of thiol-type silver removal resin and a strong basic anion exchange resin. The silver content in the impurity removal solution is reduced to below 0.005 mg / L, meeting the requirements for 6N and above high-purity copper. Moreover, the removal method does not cause secondary pollution, and the resin can be regenerated and recycled.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] This invention provides a method for removing impurities during the high-purity copper electrowinning process, the method comprising:

[0008] (1) Mix sodium sulfide precipitant with high-purity copper electrowinning circulating solution, stir and react, and then perform solid-liquid separation to obtain pretreated electrowinning circulating solution;

[0009] (2) The pretreatment electrodeposition circulating solution is passed sequentially through a mercapto-type selective silver removal resin and a strong base anion exchange resin to obtain a purification solution.

[0010] This invention provides a method for removing impurities during the high-purity copper electrowinning process. First, sodium sulfide precipitant is added to the electrowinning circulating solution. After stirring, precipitation, and solid-liquid separation, pretreatment is completed. Then, the pretreated solution is sequentially passed through a mercapto-type selective silver removal resin and a strongly basic anion exchange resin for deep impurity removal. The pretreatment relies on the low solubility product of silver sulfide and silver chloride to simultaneously remove most silver and chloride impurities, reducing the resin adsorption load. After fractional adsorption by the resin, the silver concentration in the liquid phase is below 0.005 mg / L, meeting the production standard for 6N high-purity copper. The process includes resin desorption, regeneration, and recycling. There is no addition of harmful reagents or secondary pollution, overcoming the shortcomings of existing processes such as incomplete impurity removal and excessive resin load.

[0011] In some embodiments, the amount of sodium sulfide precipitant used in step (1) is 0.1wt% to 0.3wt% of the mass of the high-purity copper electrowinning circulating solution.

[0012] In some embodiments, the high-purity copper electrowinning circulating solution includes: 20 g / L to 50 g / L of copper ions, 80 g / L to 160 g / L of sulfuric acid, ≤10 mg / L of silver ions, and ≤200 mg / L of chloride ions.

[0013] In some embodiments, the stirring reaction time in step (1) is 15 min to 20 min.

[0014] In some embodiments, the liquid-to-solid ratio of the pretreatment electrodeposition circulating solution in step (2) to the mercapto-type selective silver removal resin is 100:1 to 300:1, wherein the unit of liquid-to-solid ratio is mL / g.

[0015] In some embodiments, the liquid-to-solid ratio of the pretreatment electrodeposition circulating liquid in step (2) to the strongly basic anion exchange resin is 20:1 to 30:1, wherein the unit of liquid-to-solid ratio is mL / g.

[0016] In some embodiments, the removal method further includes desorption and regeneration treatments of the adsorbed saturated mercapto-type selective silver removal resin and strong base anion exchange resin, respectively, and the regenerated mercapto-type selective silver removal resin and strong base anion exchange resin are reused in step (2).

[0017] In some embodiments, the desorption treatment of the adsorbed saturated mercapto-based selective silver removal resin satisfies at least one of the following conditions:

[0018] (a1) Desorption treatment was carried out using hydrochloric acid solution with a concentration of 150 g / L to 190 g / L;

[0019] (a2) The solid-liquid ratio for desorption treatment is 1:0.5 to 1:0.8, and the unit of solid-liquid ratio is g / mL;

[0020] (a3) The desorption treatment temperature is 60℃~70℃;

[0021] (a4) The desorption treatment time is 4h~6h.

[0022] In some embodiments, the desorption treatment of the adsorbed saturated strong basic anion exchange resin satisfies at least one of the following conditions:

[0023] (b1) The desorption treatment was carried out using a nitric acid solution of 80 g / L to 100 g / L;

[0024] (b2) The solid-liquid ratio for desorption treatment is 1:0.6 to 1:0.9, and the unit of solid-liquid ratio is g / mL;

[0025] (b3) The desorption treatment temperature is 50℃~60℃;

[0026] (b4) The desorption treatment time is 3h~5h.

[0027] In some embodiments, the regeneration treatment of the mercapto-based selective silver removal resin satisfies at least one of the following conditions:

[0028] (c1) Regeneration treatment is carried out using a hydrochloric acid solution with a concentration of 50 g / L to 60 g / L;

[0029] (c2) The solid-liquid ratio of the regeneration treatment is 1:0.5~1:0.75, where the unit of solid-liquid ratio is g / mL;

[0030] (c3) The regeneration temperature is 30℃~40℃;

[0031] (c4) The regeneration process takes 1 to 2 hours.

[0032] In some embodiments, the regeneration treatment of the strongly basic anion exchange resin satisfies at least one of the following conditions:

[0033] (d1) Regeneration treatment was carried out using a sodium hydroxide solution with a concentration of 80 g / L to 100 g / L;

[0034] (d2) The solid-liquid ratio of the regeneration treatment is 1:0.5~1:0.75, where the unit of solid-liquid ratio is g / mL;

[0035] (d3) The regeneration treatment temperature is 35℃~45℃;

[0036] (d4) The regeneration treatment time is 1.5h~2.5h.

[0037] The numerical range described in this invention includes not only the point values ​​listed above, but also any point values ​​between the above numerical ranges that are not listed. Due to space limitations and for the sake of brevity, this invention will not exhaustively list the specific point values ​​included in the range.

[0038] Compared with the prior art, the present invention has the following beneficial effects:

[0039] This invention achieves efficient and simultaneous removal of silver and chloride impurities from high-purity copper electrowinning circulating solutions by constructing a synergistic process of simultaneous pre-removal through chemical precipitation and deep purification through a series of bifunctional resins. On one hand, utilizing the solubility product characteristics of silver sulfide and silver chloride, most silver and chloride impurities are removed simultaneously during the pretreatment stage, effectively reducing the adsorption load on subsequent resins and preventing rapid saturation and deactivation of a single resin due to high load operation, thus extending resin lifespan. On the other hand, through the tandem specific adsorption of a mercapto-type selective silver removal resin and a strongly basic anion exchange resin, the silver content in the electrowinning circulating solution is reduced to below 0.005 mg / L, while ensuring that the chloride content meets the standards, fully satisfying the requirements for 6N and above high-purity copper electrowinning. Furthermore, the entire process does not use toxic or harmful organic reagents, avoiding secondary pollution, and the resin can be reused through desorption and regeneration, significantly reducing operating costs. Detailed Implementation

[0040] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention.

[0041] The "range" disclosed in this invention can be defined in the form of a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of the specific range. This type of range definition can include or exclude endpoints; any endpoint can be independently included or excluded, and they can be arbitrarily combined, meaning any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60~120 and 80~110 are listed for specific parameters, it is understood that ranges of 60~110 and 80~120 are also expected. Furthermore, if minimum range values ​​1 and 2 are listed, and maximum range values ​​3, 4, and 5 are also listed, then the following ranges are all expected: 1~3, 1~4, 1~5, 2~3, 2~4, and 2~5. In this invention, unless otherwise stated, the numerical range "a~b" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0~5" indicates that all real numbers between "0" and "5" have been listed in this article; "0~5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is described as an integer ≥2, it is equivalent to listing integers such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc. For instance, when a parameter is described as an integer selected from "2~10", it is equivalent to listing the integers 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0042] In this invention, "a combination of at least two" refers to a quantity greater than or equal to two, unless otherwise specified. For example, "any combination of one or at least two" means one or more or more items. It can be understood that when referring to "a combination of at least two," it refers to any suitable combination of multiple items, that is, a combination of "at least two" items carried out in a manner that does not conflict with and enables the implementation of this invention.

[0043] Unless otherwise specified, all embodiments and optional embodiments of the present invention can be combined with each other to form new technical solutions.

[0044] The term "embodiment" as used in this invention means that a specific feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment or implementation of the invention. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a mutually exclusive, independent, or alternative embodiment. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described in this invention can be combined with other embodiments.

[0045] Those skilled in the art will understand that the order in which the steps are written in the methods of the various embodiments does not imply a strict execution order. The detailed execution order of each step should be determined by its function and possible internal logic. Unless otherwise specified, all steps of the present invention may be performed sequentially or randomly, but are preferably performed sequentially. For example, if the method includes steps (a) and (b), it means that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the method may also include step (c), meaning that step (c) can be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0046] In this invention, open-ended technical features or solutions described using terms such as "comprising" do not exclude additional members beyond those listed unless otherwise specified. They can be considered as providing both closed-ended features or solutions comprised of the listed members and open-ended features or solutions that include additional members beyond the listed members. For example, A includes a1, a2, and a3. Unless otherwise specified, it may also include other members or exclude additional members. This can be considered as providing both technical features or solutions where "A is composed of a1, a2, and a3" or "A is selected from a1, a2, and a3," and technical features or solutions where "A includes not only a1, a2, and a3, but also other members."

[0047] In this invention, unless otherwise specified, the features or solutions corresponding to "and / or" include any one of two or more of the related listed items, as well as any and all combinations of the related listed items. These arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. For example, "A and / or B" represents a group consisting of A, B, and "a combination of A and B". "Containing A and / or B" can mean "containing A, containing B, and containing A and B", or "containing A, containing B, or containing A and B", and can be appropriately understood according to the context.

[0048] In this invention, the terms "first aspect," "second aspect," "third aspect," "fourth aspect," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first," "second," "third," "fourth," etc., serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on the quantity.

[0049] In this invention, "optional" means that something is optional, that is, it refers to either "with" or "without". If there are multiple "optional" options in a technical solution, unless otherwise specified, and there are no contradictions or mutual constraints, then each "optional" option is independent.

[0050] In this invention, "room temperature" generally refers to 4℃~35℃, and can refer to 20℃±5℃. In some embodiments of this invention, room temperature refers to 20℃~30℃.

[0051] This invention addresses the shortcomings of existing technologies, such as the difficulty in simultaneously and efficiently removing silver and chlorine impurities from high-purity copper electrowinning circulating solutions, the easy introduction of additional impurities, and the excessively high load and short lifespan of single-resin purification. By analyzing the chemical behavior of silver and chlorine impurities in the copper sulfate system and the mechanism of existing purification processes, this invention proposes a synergistic treatment process combining simultaneous pre-purification via chemical precipitation with deep purification via a dual-functional resin series connection. This invention utilizes silver sulfide (Ksp≈6.3×10⁻⁶). -50 ) and silver chloride (Ksp≈1.8×10 -10 By utilizing the solubility product characteristics of silver ions, and adding an appropriate amount of sodium sulfide as a precipitant, most silver ions are precipitated as silver sulfide. Simultaneously, the chloride ions present in the solution react with the remaining silver ions to form silver chloride precipitate, removing most silver and chloride impurities during the pretreatment stage and significantly reducing the adsorption load on subsequent resins. Based on this, a mercapto-type selective silver removal resin and a strongly basic anion exchange resin are connected in series to deeply adsorb the remaining trace amounts of silver and chloride ions, ensuring that the impurity content in the effluent meets the electrodeposition requirements for 6N and above high-purity copper. Furthermore, the resin desorption and regeneration process parameters are optimized to achieve resin recycling and reuse. The entire process does not use toxic or harmful organic reagents, avoiding secondary pollution.

[0052] This invention provides a method for removing impurities during the high-purity copper electrowinning process, the method comprising:

[0053] (1) Mix sodium sulfide precipitant with high-purity copper electrowinning circulating solution, stir and react, and then perform solid-liquid separation to obtain pretreated electrowinning circulating solution;

[0054] (2) The pretreatment electrodeposition circulating solution is passed sequentially through a mercapto-type selective silver removal resin and a strong base anion exchange resin to obtain a purification solution.

[0055] This invention provides a method for removing impurities during the high-purity copper electrowinning process. First, sodium sulfide precipitant is added to the electrowinning circulating solution. After stirring, precipitation, and solid-liquid separation, pretreatment is completed. Then, the pretreated solution is sequentially passed through a mercapto-type selective silver removal resin and a strongly basic anion exchange resin for deep impurity removal. The pretreatment relies on the low solubility product of silver sulfide and silver chloride to simultaneously remove most silver and chloride impurities, reducing the resin adsorption load. After fractional adsorption by the resin, the silver concentration in the liquid phase is below 0.005 mg / L, meeting the production standard for 6N high-purity copper. The process includes resin desorption, regeneration, and recycling. There is no addition of harmful reagents or secondary pollution, overcoming the shortcomings of existing processes such as incomplete impurity removal and excessive resin load.

[0056] When the amount of sodium sulfide precipitant is too small, it cannot fully react with silver ions in the electrowinning circulating solution to form silver sulfide precipitate, resulting in insufficient removal rate of silver impurities in the pretreatment. Furthermore, the excessive residual silver ions increase the adsorption load on the subsequent mercapto-type silver removal resin, accelerating resin saturation and deactivation and shortening its service life. Simultaneously, the adsorption and co-precipitation effect of silver sulfide precipitate cannot assist in the removal of chloride ions, reducing the simultaneous removal effect of chloride impurities. When the amount is too large, excess sulfide ions react with copper ions in the solution to form copper sulfide precipitate, causing unnecessary loss of copper resources. It also introduces excessive sulfide ion impurities, competing for adsorption sites on mercapto resins and increasing the exchange load on strongly basic anion exchange resins, affecting the subsequent deep impurity removal effect. Moreover, residual sulfide ions will generate corrosive hydrogen sulfide gas during electrowinning, and may even cause sulfide inclusions in the cathode copper product, reducing product purity.

[0057] In some embodiments, the amount of sodium sulfide precipitant used in step (1) is 0.1wt% to 0.3wt% of the mass of the high-purity copper electrowinning circulating solution, for example, it can be 0.1wt%, 0.2wt% or 0.3wt%, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0058] In some embodiments, the high-purity copper electrowinning circulating solution includes: 20 g / L to 50 g / L of copper ions, 80 g / L to 160 g / L of sulfuric acid, ≤10 mg / L of silver ions, and ≤200 mg / L of chloride ions.

[0059] The concentration of copper ions is 20 g / L to 50 g / L, for example, it can be 20 g / L, 25 g / L, 30 g / L, 35 g / L, 40 g / L, 45 g / L or 50 g / L, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0060] The concentration of sulfuric acid is 80 g / L to 160 g / L, for example, it can be 80 g / L, 90 g / L, 100 g / L, 120 g / L, 140 g / L, 150 g / L or 160 g / L, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0061] In some embodiments, the stirring reaction time in step (1) is 15 min to 20 min, for example, it can be 15 min, 16 min, 17 min, 18 min, 19 min or 20 min, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0062] In some embodiments, the liquid-to-solid ratio of the pretreatment electrodeposition circulating solution in step (2) to the mercapto-type selective silver removal resin is 100:1 to 300:1, wherein the unit of the liquid-to-solid ratio is mL / g, and it can be, for example, 100:1, 150:1, 200:1, 250:1 or 300:1, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0063] In some embodiments, the liquid-to-solid ratio of the pretreatment electrodeposition circulating liquid to the strongly basic anion exchange resin in step (2) is 20:1 to 30:1, wherein the unit of the liquid-to-solid ratio is mL / g, and it can be, for example, 20:1, 21:1, 24:1, 25:1, 27:1, 28:1 or 30:1, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0064] In some embodiments, the removal method further includes desorption and regeneration treatments of the adsorbed saturated mercapto-type selective silver removal resin and strong base anion exchange resin, respectively, and the regenerated mercapto-type selective silver removal resin and strong base anion exchange resin are reused in step (2).

[0065] In some embodiments, the desorption treatment of the adsorbed saturated mercapto-based selective silver removal resin satisfies at least one of the following conditions:

[0066] (a1) The desorption treatment is carried out with a hydrochloric acid solution of 150 g / L to 190 g / L, for example, it can be 150 g / L, 155 g / L, 160 g / L, 165 g / L, 170 g / L, 175 g / L, 180 g / L, 185 g / L or 190 g / L, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0067] (a2) The solid-liquid ratio for desorption treatment is 1:0.5 to 1:0.8, and the unit of solid-liquid ratio is g / mL. For example, it can be 1:0.5, 1:0.6, 1:0.7 or 1:0.8, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0068] (a3) The desorption treatment temperature is 60℃~70℃, for example, it can be 60℃, 62℃, 65℃, 66℃, 68℃ or 70℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0069] (a4) The desorption treatment time is 4h to 6h, for example, it can be 4h, 4.5h, 5h, 5.5h or 6h, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0070] In some embodiments, the desorption treatment of the adsorbed saturated strong basic anion exchange resin satisfies at least one of the following conditions:

[0071] (b1) The desorption treatment is carried out with a nitric acid solution of 80 g / L to 100 g / L, for example, 80 g / L, 85 g / L, 90 g / L, 95 g / L or 100 g / L, but not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0072] (b2) The solid-liquid ratio for desorption treatment is 1:0.6 to 1:0.9, and the unit of solid-liquid ratio is g / mL. For example, it can be 1:0.6, 1:0.7, 1:0.8 or 1:0.9, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0073] (b3) The desorption treatment temperature is 50℃~60℃, for example, it can be 50℃, 52℃, 54℃, 55℃, 56℃, 58℃ or 60℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0074] (b4) The desorption treatment time is 3h to 5h, for example, it can be 3h, 3.5h, 4h, 4.5h or 5h, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0075] In some embodiments, the regeneration treatment of the mercapto-based selective silver removal resin satisfies at least one of the following conditions:

[0076] (c1) Regeneration treatment is carried out with a hydrochloric acid solution of 50 g / L to 60 g / L, for example, 50 g / L, 52 g / L, 54 g / L, 55 g / L, 56 g / L, 58 g / L or 60 g / L, but not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0077] (c2) The solid-liquid ratio of the regeneration treatment is 1:0.5 to 1:0.75, where the unit of the solid-liquid ratio is g / mL. For example, it can be 1:0.5, 1:0.55, 1:0.6, 1:0.65, 1:0.7 or 1:0.75, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0078] (c3) The temperature for regeneration is 30℃~40℃, for example, it can be 30℃, 32℃, 35℃, 36℃, 38℃ or 40℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0079] (c4) The regeneration time is 1h to 2h, for example, it can be 1h, 1.2h, 1.5h, 1.6h, 1.8h or 2h, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0080] In some embodiments, the regeneration treatment of the strongly basic anion exchange resin satisfies at least one of the following conditions:

[0081] (d1) Regeneration treatment is carried out using a sodium hydroxide solution of 80 g / L to 100 g / L, for example, it can be 80 g / L, 85 g / L, 90 g / L, 95 g / L or 100 g / L, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0082] (d2) The solid-liquid ratio of the regeneration treatment is 1:0.5 to 1:0.75, where the unit of the solid-liquid ratio is g / mL. For example, it can be 1:0.5, 1:0.55, 1:0.6, 1:0.65, 1:0.7 or 1:0.75, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0083] (d3) The temperature for regeneration is 35℃~45℃, for example, it can be 35℃, 36℃, 38℃, 40℃, 42℃, 44℃ or 45℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0084] (d4) The regeneration time is 1.5h to 2.5h, for example, it can be 1.5h, 1.6h, 1.8h, 2h, 2.1h, 2.4h or 2.5h, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0085] As a preferred embodiment of the removal method provided by the present invention, the removal method includes:

[0086] (1) Mix sodium sulfide precipitant with high-purity copper electrowinning circulating solution, stir and react for 15 min to 20 min, and then perform solid-liquid separation to obtain pretreated electrowinning circulating solution;

[0087] The high-purity copper electrowinning circulating solution includes: 20 g / L to 50 g / L of copper ions, 80 g / L to 160 g / L of sulfuric acid, ≤10 mg / L of silver ions, and ≤200 mg / L of chloride ions.

[0088] The amount of sodium sulfide precipitant used is 0.1wt%~0.3wt% of the mass of the high-purity copper electrowinning circulating fluid;

[0089] (2) The pretreatment electrodeposition circulating solution is passed sequentially through a mercapto-type selective silver removal resin and a strong base anion exchange resin to obtain a cleaned solution;

[0090] The liquid-to-solid ratio of the pretreatment electrodeposition circulating solution to the mercapto-type selective silver removal resin is 100:1 to 300:1, wherein the unit of the liquid-to-solid ratio is mL / g.

[0091] The liquid-to-solid ratio of the pretreatment electrodeposition circulating solution to the strongly basic anion exchange resin is 20:1 to 30:1, wherein the unit of the liquid-to-solid ratio is mL / g.

[0092] (3) The saturated mercapto-type selective silver removal resin and strong base anion exchange resin are subjected to desorption and regeneration treatment. The mercapto-type selective silver removal resin and strong base anion exchange resin after regeneration treatment are reused in step (2).

[0093] The desorption treatment of saturated mercapto-type selective silver removal resin meets the following conditions: the desorption treatment is carried out with hydrochloric acid solution of 150 g / L to 190 g / L, the solid-liquid ratio is 1:0.5 to 1:0.8, the unit of solid-liquid ratio is g / mL, the temperature is 60℃ to 70℃, and the time is 4h to 6h.

[0094] The desorption treatment of saturated strong basic anion exchange resin meets the following conditions: the desorption treatment is carried out with 80 g / L to 100 g / L nitric acid solution, the solid-liquid ratio is 1:0.6 to 1:0.9 (unit: g / mL), the temperature is 50℃ to 60℃, and the time is 3h to 5h.

[0095] The regeneration treatment of the mercapto-type selective silver removal resin meets the following conditions: the regeneration treatment is carried out with a hydrochloric acid solution of 50 g / L to 60 g / L, the solid-liquid ratio is 1:0.5 to 1:0.75, where the unit of solid-liquid ratio is g / mL, the temperature is 30℃ to 40℃, and the time is 1h to 2h.

[0096] The regeneration treatment of strongly basic anion exchange resin shall meet the following conditions: the regeneration treatment shall be carried out with 80 g / L to 100 g / L sodium hydroxide solution, the solid-liquid ratio shall be 1:0.5 to 1:0.75, where the unit of solid-liquid ratio is g / mL, the temperature shall be 35℃ to 45℃, and the time shall be 1.5 h to 2.5 h.

[0097] To clearly illustrate the technical solution of the present invention, in the following embodiments and comparative examples, the composition of the high-purity copper electrowinning circulating solution is: 40 g / L copper ions, 130 g / L sulfuric acid, 10 mg / L silver ions, 200 mg / L chloride ions, and the remainder is deionized water.

[0098] Example 1

[0099] This embodiment provides a method for removing impurities during the high-purity copper electrowinning process, including:

[0100] (1) Mix sodium sulfide precipitant with high-purity copper electrodeposition circulating solution, stir and react for 18 min, and then perform solid-liquid separation to obtain pretreated electrodeposition circulating solution;

[0101] The amount of sodium sulfide precipitant used is 0.2 wt% of the mass of the high-purity copper electrowinning circulating solution;

[0102] (2) The pretreatment electrodeposition circulating solution is passed sequentially through a mercapto-type selective silver removal resin (Tulsimer CH-97S) and a strong base anion exchange resin (Tulsimer A-62) to obtain a cleaned solution;

[0103] The liquid-to-solid ratio of the pretreatment electrodeposition circulating solution to the mercapto-type selective silver removal resin is 200:1, wherein the unit of the liquid-to-solid ratio is mL / g.

[0104] The liquid-to-solid ratio of the pretreatment electrodeposition circulating solution to the strongly basic anion exchange resin is 25:1, wherein the unit of the liquid-to-solid ratio is mL / g.

[0105] (3) The saturated mercapto-type selective silver removal resin and strong base anion exchange resin are subjected to desorption and regeneration treatment. The mercapto-type selective silver removal resin and strong base anion exchange resin after regeneration treatment are reused in step (2).

[0106] The desorption treatment of the adsorption-saturated mercapto-type selective silver removal resin met the following conditions: the desorption treatment was carried out with 160 g / L hydrochloric acid solution, the solid-liquid ratio was 1:0.6, the unit of solid-liquid ratio was g / mL, the temperature was 65℃, and the time was 5 h.

[0107] The desorption treatment of the adsorption-saturated strong basic anion exchange resin meets the following conditions: the desorption treatment is carried out with 90 g / L nitric acid solution, the solid-liquid ratio is 1:0.8, the unit of solid-liquid ratio is g / mL, the temperature is 55℃, and the time is 4 h.

[0108] The regeneration treatment of the mercapto-type selective silver removal resin meets the following conditions: the regeneration treatment is carried out with 55 g / L hydrochloric acid solution, the solid-liquid ratio is 1:0.65, where the unit of solid-liquid ratio is g / mL, the temperature is 35℃, and the time is 1.5 h.

[0109] The regeneration treatment of the strongly basic anion exchange resin meets the following conditions: the regeneration treatment is carried out using a 90 g / L sodium hydroxide solution, the solid-liquid ratio is 1:0.65, where the unit of solid-liquid ratio is g / mL, the temperature is 40℃, and the time is 2 h.

[0110] Example 2

[0111] This embodiment provides a method for removing impurities during the high-purity copper electrowinning process, including:

[0112] (1) Mix sodium sulfide precipitant with high-purity copper electrowinning circulating solution, stir and react for 15 min, then perform solid-liquid separation to obtain pretreated electrowinning circulating solution;

[0113] The amount of sodium sulfide precipitant used is 0.1 wt% of the mass of the high-purity copper electrowinning circulating solution;

[0114] (2) The pretreatment electrodeposition circulating solution is passed sequentially through a mercapto-type selective silver removal resin (Tulsimer CH-97S) and a strong base anion exchange resin (Tulsimer A-62) to obtain a cleaned solution;

[0115] The liquid-to-solid ratio of the pretreatment electrodeposition cycle solution to the mercapto-type selective silver removal resin is 100:1, wherein the unit of the liquid-to-solid ratio is mL / g.

[0116] The liquid-to-solid ratio of the pretreatment electrodeposition circulating solution to the strongly basic anion exchange resin is 20:1, wherein the unit of the liquid-to-solid ratio is mL / g.

[0117] (3) The saturated mercapto-type selective silver removal resin and strong base anion exchange resin are subjected to desorption and regeneration treatment. The mercapto-type selective silver removal resin and strong base anion exchange resin after regeneration treatment are reused in step (2).

[0118] The desorption treatment of the adsorption-saturated mercapto-type selective silver removal resin meets the following conditions: the desorption treatment is carried out with 150 g / L hydrochloric acid solution, the solid-liquid ratio is 1:0.5, the unit of solid-liquid ratio is g / mL, the temperature is 60℃, and the time is 4 h.

[0119] The desorption treatment of the adsorption-saturated strong basic anion exchange resin meets the following conditions: the desorption treatment is carried out with 80 g / L nitric acid solution, the solid-liquid ratio is 1:0.6, the unit of solid-liquid ratio is g / mL, the temperature is 50℃, and the time is 3h.

[0120] The regeneration treatment of the mercapto-type selective silver removal resin meets the following conditions: the regeneration treatment is carried out with 50 g / L hydrochloric acid solution, the solid-liquid ratio is 1:0.5, where the unit of solid-liquid ratio is g / mL, the temperature is 30℃, and the time is 1 h.

[0121] The regeneration treatment of strongly basic anion exchange resin meets the following conditions: the regeneration treatment is carried out using an 80 g / L sodium hydroxide solution, the solid-liquid ratio is 1:0.5, where the unit of solid-liquid ratio is g / mL, the temperature is 35℃, and the time is 1.5 h.

[0122] Example 3

[0123] This embodiment provides a method for removing impurities during the high-purity copper electrowinning process, including:

[0124] (1) Mix sodium sulfide precipitant with high-purity copper electrodeposition circulating solution, stir and react for 20 min, and then perform solid-liquid separation to obtain pretreated electrodeposition circulating solution;

[0125] The amount of sodium sulfide precipitant used is 0.3 wt% of the mass of the high-purity copper electrowinning circulating solution;

[0126] (2) The pretreatment electrodeposition circulating solution is passed sequentially through a mercapto-type selective silver removal resin (Tulsimer CH-97S) and a strong base anion exchange resin (Tulsimer A-62) to obtain a cleaned solution;

[0127] The liquid-to-solid ratio of the pretreatment electrodeposition cycle solution to the mercapto-type selective silver removal resin is 300:1, wherein the unit of the liquid-to-solid ratio is mL / g.

[0128] The liquid-to-solid ratio of the pretreatment electrodeposition circulating solution to the strongly basic anion exchange resin is 30:1, wherein the unit of the liquid-to-solid ratio is mL / g.

[0129] (3) The saturated mercapto-type selective silver removal resin and strong base anion exchange resin are subjected to desorption and regeneration treatment. The mercapto-type selective silver removal resin and strong base anion exchange resin after regeneration treatment are reused in step (2).

[0130] The desorption treatment of the adsorption-saturated mercapto-type selective silver removal resin met the following conditions: the desorption treatment was carried out with 190 g / L hydrochloric acid solution, the solid-liquid ratio was 1:0.8, the unit of solid-liquid ratio was g / mL, the temperature was 70℃, and the time was 6 h.

[0131] The desorption treatment of the adsorption-saturated strong basic anion exchange resin meets the following conditions: the desorption treatment is carried out with 100 g / L nitric acid solution, the solid-liquid ratio is 1:0.9, the unit of solid-liquid ratio is g / mL, the temperature is 60℃, and the time is 5 h.

[0132] The regeneration treatment of the mercapto-type selective silver removal resin meets the following conditions: the regeneration treatment is carried out with 60 g / L hydrochloric acid solution, the solid-liquid ratio is 1:0.75, where the unit of solid-liquid ratio is g / mL, the temperature is 40℃, and the time is 2h.

[0133] The regeneration treatment of the strongly basic anion exchange resin meets the following conditions: the regeneration treatment is carried out with a 100 g / L sodium hydroxide solution, the solid-liquid ratio is 1:0.75, where the unit of solid-liquid ratio is g / mL, the temperature is 45℃, and the time is 2.5 h.

[0134] Example 4

[0135] This embodiment provides a method for removing impurities during the high-purity copper electrowinning process. Except that the amount of sodium sulfide precipitant used is 0.05 wt% of the mass of the high-purity copper electrowinning circulating solution, the rest is the same as in Example 1.

[0136] Example 5

[0137] This embodiment provides a method for removing impurities during the high-purity copper electrowinning process. Except that the amount of sodium sulfide precipitant used is 0.35 wt% of the mass of the high-purity copper electrowinning circulating solution, the rest is the same as in Example 1.

[0138] Example 6

[0139] This embodiment provides a method for removing impurities during the high-purity copper electrowinning process. Except for the liquid-to-solid ratio of the pretreatment electrowinning circulating solution to the mercapto-type selective silver removal resin being 80:1, the rest is the same as in Example 1.

[0140] Example 7

[0141] This embodiment provides a method for removing impurities during the high-purity copper electrowinning process. Except for the liquid-to-solid ratio of the pretreatment electrowinning circulating solution to the mercapto-type selective silver removal resin being 320:1, all other aspects are the same as in Example 1.

[0142] Example 8

[0143] This embodiment provides a method for removing impurities during the high-purity copper electrowinning process. Except for the liquid-to-solid ratio of the pretreatment electrowinning circulating solution to the strongly basic anion exchange resin being 10:1, the rest is the same as in Embodiment 1.

[0144] Example 9

[0145] This embodiment provides a method for removing impurities during the high-purity copper electrowinning process. Except for the liquid-to-solid ratio of the pretreatment electrowinning circulating solution to the strongly basic anion exchange resin being 40:1, the rest is the same as in Embodiment 1.

[0146] Comparative Example 1

[0147] This comparative example provides a method for removing impurities during the high-purity copper electrowinning process. Except for the absence of sodium sulfide precipitant, it is identical to Example 1, including:

[0148] (1) The high-purity copper electrodeposition circulating solution is passed sequentially through a mercapto-type selective silver removal resin (Tulsimer CH-97S) and a strong basic anion exchange resin (Tulsimer A-62) to obtain a cleaned solution;

[0149] The liquid-to-solid ratio of the high-purity copper electrowinning circulating solution to the mercapto-type selective silver removal resin is 200:1, wherein the unit of the liquid-to-solid ratio is mL / g.

[0150] The liquid-to-solid ratio of the high-purity copper electrodeposition circulating solution to the strongly basic anion exchange resin is 25:1, wherein the unit of the liquid-to-solid ratio is mL / g.

[0151] (2) The saturated mercapto-type selective silver removal resin and strong base anion exchange resin are subjected to desorption and regeneration treatment. The mercapto-type selective silver removal resin and strong base anion exchange resin after regeneration treatment are reused in step (1).

[0152] The desorption treatment of the adsorption-saturated mercapto-type selective silver removal resin met the following conditions: the desorption treatment was carried out with 160 g / L hydrochloric acid solution, the solid-liquid ratio was 1:0.6, the unit of solid-liquid ratio was g / mL, the temperature was 65℃, and the time was 5 h.

[0153] The desorption treatment of the adsorption-saturated strong basic anion exchange resin meets the following conditions: the desorption treatment is carried out with 90 g / L nitric acid solution, the solid-liquid ratio is 1:0.8, the unit of solid-liquid ratio is g / mL, the temperature is 55℃, and the time is 4 h.

[0154] The regeneration treatment of the mercapto-type selective silver removal resin meets the following conditions: the regeneration treatment is carried out with 55 g / L hydrochloric acid solution, the solid-liquid ratio is 1:0.65, where the unit of solid-liquid ratio is g / mL, the temperature is 35℃, and the time is 1.5 h.

[0155] The regeneration treatment of the strongly basic anion exchange resin meets the following conditions: the regeneration treatment is carried out using a 90 g / L sodium hydroxide solution, the solid-liquid ratio is 1:0.65, where the unit of solid-liquid ratio is g / mL, the temperature is 40℃, and the time is 2 h.

[0156] Comparative Example 2

[0157] This comparative example provides a method for removing impurities during the high-purity copper electrodeposition process. Except for the absence of mercapto-type selective silver removal resin and strongly basic anion exchange resin, it is identical to Example 1, including:

[0158] (1) Mix sodium sulfide precipitant with high-purity copper electrodeposition circulating solution, stir and react for 18 min, and then perform solid-liquid separation to obtain pretreated electrodeposition circulating solution;

[0159] The amount of sodium sulfide precipitant used is 0.2 wt% of the mass of the high-purity copper electrowinning circulating fluid.

[0160] In this comparative example, the pretreatment electrodeposition circulating solution was used as the impurity removal solution.

[0161] Comparative Example 3

[0162] This comparative example provides a method for removing impurities during the high-purity copper electrodeposition process. Except for the substitution of the positions of the mercapto-type selective silver removal resin and the strongly basic anion exchange resin, the method is identical to that in Example 1, including:

[0163] (1) Mix sodium sulfide precipitant with high-purity copper electrodeposition circulating solution, stir and react for 18 min, and then perform solid-liquid separation to obtain pretreated electrodeposition circulating solution;

[0164] The amount of sodium sulfide precipitant used is 0.2 wt% of the mass of the high-purity copper electrowinning circulating solution;

[0165] (2) The pretreatment electrodeposition circulating solution is passed sequentially through a strong basic anion exchange resin (Tulsimer A-62) and a mercapto-type selective silver removal resin (Tulsimer CH-97S) to obtain a cleaned solution;

[0166] The liquid-to-solid ratio of the pretreatment electrodeposition circulating solution to the mercapto-type selective silver removal resin is 200:1, wherein the unit of the liquid-to-solid ratio is mL / g.

[0167] The liquid-to-solid ratio of the pretreatment electrodeposition circulating solution to the strongly basic anion exchange resin is 25:1, wherein the unit of the liquid-to-solid ratio is mL / g.

[0168] (3) The saturated mercapto-type selective silver removal resin and strong base anion exchange resin are subjected to desorption and regeneration treatment. The mercapto-type selective silver removal resin and strong base anion exchange resin after regeneration treatment are reused in step (2).

[0169] The desorption treatment of the adsorption-saturated mercapto-type selective silver removal resin met the following conditions: the desorption treatment was carried out with 160 g / L hydrochloric acid solution, the solid-liquid ratio was 1:0.6, the unit of solid-liquid ratio was g / mL, the temperature was 65℃, and the time was 5 h.

[0170] The desorption treatment of the adsorption-saturated strong basic anion exchange resin meets the following conditions: the desorption treatment is carried out with 90 g / L nitric acid solution, the solid-liquid ratio is 1:0.8, the unit of solid-liquid ratio is g / mL, the temperature is 55℃, and the time is 4 h.

[0171] The regeneration treatment of the mercapto-type selective silver removal resin meets the following conditions: the regeneration treatment is carried out with 55 g / L hydrochloric acid solution, the solid-liquid ratio is 1:0.65, where the unit of solid-liquid ratio is g / mL, the temperature is 35℃, and the time is 1.5 h.

[0172] The regeneration treatment of the strongly basic anion exchange resin meets the following conditions: the regeneration treatment is carried out using a 90 g / L sodium hydroxide solution, the solid-liquid ratio is 1:0.65, where the unit of solid-liquid ratio is g / mL, the temperature is 40℃, and the time is 2 h.

[0173] Performance Characterization

[0174] The contents of silver ions, chloride ions, and copper ions in the impurity removal solutions obtained in the above examples and comparative examples were determined. The contents of silver ions and copper ions were determined using inductively coupled plasma atomic emission spectrometry (ICP-AES); the contents of chloride ions were determined using ion chromatography. The results are shown in Table 1.

[0175] The copper loss rate is calculated using the following formula:

[0176] Copper loss rate = (copper ion concentration in high-purity copper electrowinning circulating solution - copper ion concentration in impurity removal solution) / copper ion concentration in high-purity copper electrowinning circulating solution × 100%.

[0177] Table 1

[0178]

[0179] As can be seen from Examples 1 to 3 in Table 1, the high-purity copper electrowinning impurity removal method provided by the present invention can achieve efficient and simultaneous deep removal of silver and chloride impurities. After treatment, the silver ion concentration is ≤0.005mg / L, the chloride ion concentration is ≤9mg / L, and the copper loss rate is ≤0.4%, which fully meets the production requirements of 6N and above ultra-high purity copper electrowinning.

[0180] Comparison of Comparative Examples 1 and 2 with Example 1 shows that when only dual resins are used for purification, high concentrations of silver and chlorine impurities will cause the resins to quickly become saturated and deactivated, failing to achieve a deep impurity removal effect; when only chemical precipitation pretreatment is used, only most impurities can be removed, but the concentration of silver and chlorine cannot be reduced to the level required for ultra-high purity copper electrowinning.

[0181] A comparison between Comparative Example 3 and Example 1 shows that when the resin series sequence is reversed, the residual silver ions in the solution will react with chloride ions to form [AgCl2]. - When anionic complexes are adsorbed by strongly basic anion exchange resins, they not only contaminate the anion exchange resins and reduce their chlorine removal capacity, but also prevent thiol-based silver removal resins from effectively removing the complexed silver, ultimately reducing the removal efficiency of both silver and chlorine.

[0182] A comparison of Examples 4 and 5 with Example 1 shows that the dosage of sodium sulfide precipitant needs to be controlled within the range of 0.1wt% to 0.3wt%. When the dosage of sodium sulfide is too low, it cannot fully react with silver ions to form silver sulfide precipitate, resulting in insufficient removal rate of silver and chlorine impurities during pretreatment, leading to excessive concentrations of silver and chlorine in the final effluent. When the dosage of sodium sulfide is too high, excessive sulfide ions will react with copper ions to form copper sulfide precipitate, causing unnecessary loss of copper resources and increasing the copper loss rate.

[0183] A comparison of Examples 6 and 7 with Example 1 shows that when the liquid-to-solid ratio of the pretreatment electrowinning circulating solution to the mercapto-type selective silver removal resin is too low, the amount of resin used will be too large, which will increase the process cost; when the liquid-to-solid ratio is too high, the amount of resin used will be insufficient, and the silver ion concentration cannot be reduced to below 0.005 mg / L, which will not meet the requirements for high-purity copper electrowinning.

[0184] A comparison of Examples 8 and 9 with Example 1 shows that when the liquid-to-solid ratio of the pretreatment electrowinning circulating solution to the strongly basic anion exchange resin is too low, the amount of resin used is too large. Although this can further reduce the chloride ion concentration in the effluent, it will increase the process cost. When the liquid-to-solid ratio is too high, the amount of resin used is insufficient, and the chloride ion concentration cannot be reduced to below 10 mg / L, which cannot meet the requirements of the electrowinning process.

[0185] The resin was regenerated and desorbed five times, then reused in the pretreatment electrowinning circulating solution. The contents of silver, chloride, and copper ions in the purified solution were then measured. Silver and copper ion contents were determined using inductively coupled plasma atomic emission spectrometry (ICP-AES); chloride ion content was determined using ion chromatography. The results are shown in Table 2. Since Comparative Example 2 did not use mercapto-type selective silver removal resin or strongly basic anion exchange resin, no measurements were performed in Comparative Example 2.

[0186] Table 2

[0187]

[0188] As shown in Examples 1-3 of Table 2, the desorption-regeneration method provided by the present invention can effectively restore the adsorption performance of the resin. After five adsorption-desorption-regeneration cycles, the copper loss rate showed no significant change and was basically consistent with the results of the first run.

[0189] A comparison of Examples 4-9 with Example 1 shows that under conditions deviating from the optimal process parameters, the impurity removal effect after resin regeneration decreases to varying degrees, but the trend remains consistent with the initial run. Among these, the groups with insufficient sodium sulfide and excessively high resin liquid-to-solid ratios exhibited more significant increases in silver and chlorine concentrations after regeneration.

[0190] A comparison of Comparative Examples 1 and 3 with Example 1 shows that under unreasonable process conditions, the impurity removal effect of the regenerated resin will be further reduced. This is because when the resin is used directly without pretreatment, it will quickly adsorb a large number of impurities, resulting in incomplete desorption and a faster decline in performance after regeneration. When the resin series sequence is reversed, the anion exchange resin will be contaminated by silver complexes, which are difficult to completely remove through conventional desorption and regeneration, leading to a continuous decrease in dechlorination capacity after regeneration.

[0191] In summary, this invention achieves efficient and simultaneous removal of silver and chloride impurities from high-purity copper electrowinning circulating solutions by constructing a synergistic process of simultaneous pre-removal through chemical precipitation and deep purification through a series of bifunctional resins. On one hand, utilizing the solubility product characteristics of silver sulfide and silver chloride, most silver and chloride impurities are removed simultaneously during the pretreatment stage, effectively reducing the adsorption load on subsequent resins and preventing rapid saturation and deactivation of a single resin due to high load operation, thus extending resin lifespan. On the other hand, through the tandem specific adsorption of a mercapto-type selective silver removal resin and a strongly basic anion exchange resin, the silver content in the electrowinning circulating solution is reduced to below 0.005 mg / L, while ensuring that the chloride content meets the standards, fully satisfying the requirements for 6N and above high-purity copper electrowinning. Furthermore, the entire process does not use toxic or harmful organic reagents, avoiding secondary pollution, and the resin can be reused through desorption and regeneration, significantly reducing operating costs.

[0192] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A method for removing impurities during the high-purity copper electrowinning process, characterized in that, The removal method includes: (1) Mix sodium sulfide precipitant with high-purity copper electrodeposition circulating solution, stir and react, and then perform solid-liquid separation to obtain pretreated electrodeposition circulating solution; (2) The pretreatment electrodeposition circulating solution is passed sequentially through a mercapto-type selective silver removal resin and a strong base anion exchange resin to obtain a cleaned solution.

2. The removal method according to claim 1, characterized in that, The amount of sodium sulfide precipitant used in step (1) is 0.1wt%~0.3wt% of the mass of the high-purity copper electrowinning circulating solution.

3. The removal method according to claim 1 or 2, characterized in that, The high-purity copper electrowinning circulating solution includes: 20 g / L to 50 g / L of copper ions, 80 g / L to 160 g / L of sulfuric acid, ≤10 mg / L of silver ions, and ≤200 mg / L of chloride ions.

4. The removal method according to any one of claims 1 to 3, characterized in that, The stirring reaction time in step (1) is 15 min to 20 min.

5. The removal method according to any one of claims 1 to 4, characterized in that, In step (2), the liquid-to-solid ratio of the pretreatment electrodeposition circulating solution to the mercapto-type selective silver removal resin is 100:1 to 300:1, wherein the unit of the liquid-to-solid ratio is mL / g; And / or, the liquid-to-solid ratio of the pretreatment electrodeposition circulating solution in step (2) to the strongly basic anion exchange resin is 20:1 to 30:1, wherein the unit of liquid-to-solid ratio is mL / g.

6. The removal method according to any one of claims 1 to 5, characterized in that, The removal method further includes desorption and regeneration treatments of the adsorption-saturated thiol-type selective silver removal resin and strong base anion exchange resin, respectively, and the thiol-type selective silver removal resin and strong base anion exchange resin after regeneration treatment are reused in step (2).

7. The removal method according to claim 6, characterized in that, The desorption treatment of saturated mercapto-based selective silver removal resin satisfies at least one of the following conditions: (a1) Desorption treatment was carried out using hydrochloric acid solution with a concentration of 150 g / L to 190 g / L; (a2) The solid-liquid ratio for desorption treatment is 1:0.5 to 1:0.8, and the unit of solid-liquid ratio is g / mL; (a3) The desorption treatment temperature is 60℃~70℃; (a4) The desorption treatment time is 4h~6h.

8. The removal method according to claim 6, characterized in that, The desorption treatment of saturated strong basic anion exchange resins satisfies at least one of the following conditions: (b1) The desorption treatment was carried out using a nitric acid solution of 80 g / L to 100 g / L; (b2) The solid-liquid ratio for desorption treatment is 1:0.6 to 1:0.9, and the unit of solid-liquid ratio is g / mL; (b3) The desorption treatment temperature is 50℃~60℃; (b4) The desorption treatment time is 3h~5h.

9. The removal method according to claim 6, characterized in that, The regeneration treatment of the mercapto-type selective silver removal resin meets at least one of the following conditions: (c1) Regeneration treatment is carried out using a hydrochloric acid solution with a concentration of 50 g / L to 60 g / L; (c2) The solid-liquid ratio of the regeneration treatment is 1:0.5~1:0.75, where the unit of solid-liquid ratio is g / mL; (c3) The regeneration temperature is 30℃~40℃; (c4) The regeneration process takes 1 to 2 hours.

10. The removal method according to claim 6, characterized in that, The regeneration treatment of strongly basic anion exchange resin meets at least one of the following conditions: (d1) Regeneration treatment was carried out using a sodium hydroxide solution with a concentration of 80 g / L to 100 g / L; (d2) The solid-liquid ratio of the regeneration treatment is 1:0.5~1:0.75, where the unit of solid-liquid ratio is g / mL; (d3) The regeneration treatment temperature is 35℃~45℃; (d4) The regeneration treatment time is 1.5h~2.5h.

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