Methods for graded treatment of copper electrolyte

Abstract

This application provides a method for the cascaded treatment of copper electrolyte, relating to the field of copper electrolyte purification and impurity removal. The method includes: performing a first-stage electrowinning copper removal process on a high-arsenic copper-containing electrolyte, controlling the copper content of the electrolyte after the first-stage copper removal to be no less than 25 g / L, and recovering Grade A copper; performing a second-stage electrowinning copper removal process on the electrolyte after the first-stage copper removal, controlling the copper content of the electrolyte after the second-stage copper removal to be no less than 9 g / L, and recovering No. 1 standard cathode copper; and performing a third-stage electrowinning copper removal process on the electrolyte after the second-stage copper removal, controlling the copper content of the electrolyte after the third-stage copper removal to be no more than 0.5 g / L, and recovering black copper slag. The cascaded treatment method for copper electrolyte provided in this application employs a cascaded purification and impurity removal process, achieving good impurity removal efficiency, with removal rates of As, Sb, and Bi of no less than 95%, 80%, and 75%, respectively, and a direct recovery rate of Cu of no less than 80%. The system energy consumption is no higher than 200 kWh / t. Cu .

Description

Technical Field

[0001] This application relates to the field of copper electrolyte purification and impurity removal, and in particular to a method for graded treatment of copper electrolyte. Background Technology

[0002] The grade of copper anodes refined by pyrometallurgical processes is generally 99.2%–99.7%, and standard cathode copper is often produced by electrolytic refining. During electrolysis, some impurities in the crude copper dissolve into the electrolyte along with the anode. When these impurities accumulate to a certain concentration, they affect copper crystal nucleation and reduce the quality of the cathode copper. Therefore, extensive research has been conducted both domestically and internationally on impurity removal from copper electrolytes. The main methods include electrowinning, solvent extraction, ion exchange, chemical precipitation, and adsorption. Among these, electrowinning is the most widely used in industry, while the other methods remain largely in the laboratory research stage.

[0003] Electrowinning for copper removal and impurity removal in industrial applications mainly includes conventional electrowinning (conventional method), induced electrowinning (induced method), and cyclone electrowinning (cyclone method). The conventional method involves concentrating a high-impurity electrolyte in a copper removal electrolytic cell, causing copper and impurities to co-deposit on the cathode to form sponge copper. This method can electrowinet copper and arsenic to Cu < 0.5 g / L and As 1–3 g / L in a single pass. However, it suffers from a low direct copper recovery rate of approximately 33%, and the problem of impurities forming a vicious closed-loop cycle in the copper smelting system, severely impacting production efficiency, increasing energy consumption, and generating highly toxic AsH3 gas in the later stages of electrowinning. The induced method maximizes the arsenic deposition rate by controlling the copper concentration in the electrolyte while ensuring no AsH3 gas is released. However, it requires high control over the main and auxiliary electrolytes; has a low direct copper recovery rate; produces large quantities of black copper; and consumes more energy. Electrolytic electrowinning separates metal ions based on their deposition potential differences, using high-speed solution flow to eliminate the effects of concentration polarization. It is suitable for processing solutions with complex compositions and low concentrations, achieving a direct copper recovery rate of over 65%. However, this method is energy-intensive, consuming up to 3300 kW·h per ton of copper. Furthermore, the process is carried out in a closed electrolytic cell, resulting in low automation and high labor intensity. Additionally, the H2 and O2 generated during the later stages of electrowinning can easily accumulate, posing an explosion risk.

[0004] In summary, in view of the problems existing in the prior art, this application proposes a new process for copper electrolyte step-by-step copper removal and purification, which has the characteristics of low energy consumption, low cost, high direct copper recovery rate (over 80%), good impurity removal effect, and environmental friendliness, and has practical significance and good application prospects. Summary of the Invention

[0005] The purpose of this application is to provide a method for the graded treatment of copper electrolyte to solve the above-mentioned problems.

[0006] To achieve the above objectives, this application adopts the following technical solution:

[0007] A method for graded treatment of copper electrolyte includes:

[0008] The high-arsenic copper-containing electrolyte was subjected to a first-stage electrowinning process to remove copper, and the copper content of the electrolyte after the first-stage copper removal was controlled to be no less than 25 g / L, so as to recover Grade A copper.

[0009] The copper content of the first-stage copper removal solution is controlled to be no less than 9 g / L, and the No. 1 standard cathode copper is recovered.

[0010] The copper content of the liquid after secondary copper removal is controlled to be no more than 0.5 g / L, and black copper slag is recovered.

[0011] Preferably, the high-arsenic copper-containing electrolyte is pumped into a primary electrolytic cell via a frequency converter pump, and the primary electrolytic cell is an electrolytic cell employing a parallel flow solution circulation method.

[0012] Preferably, the circulation rate of the high-arsenic copper-containing electrolyte is 90 L / min-140 L / min, and the current density is 280 A / m. 2 -380A / m 2 The temperature of the high-arsenic copper-containing electrolyte is 50℃-60℃.

[0013] Preferably, the copper stripping solution is pumped into a secondary electrolytic cell via a frequency converter pump. The secondary electrolytic cell is an electrolytic cell that uses a parallel flow solution circulation method.

[0014] Preferably, the circulation rate of the copper removal solution after the first stage is 90 L / min-140 L / min, and the current density is 280 A / m. 2 -380A / m 2 The temperature of the liquid after the first-stage copper removal is 50℃-60℃.

[0015] Preferably, the secondary copper removal solution is pumped into a tertiary electrolytic cell via a frequency converter pump. The tertiary electrolytic cell is a closed electrolytic cell that uses a parallel flow solution circulation method.

[0016] Preferably, the circulation rate of the secondary copper removal solution is 90 L / min-140 L / min, and the current density is 500 A / m. 2 -600A / m 2 The temperature of the liquid after the secondary copper removal is 50℃-60℃.

[0017] Preferably, the three-stage electrolytic cell is a closed electrolytic cell.

[0018] Preferably, in the high-arsenic copper electrolyte, the removal rates of As, Sb, and Bi are not less than 95%, 80%, and 75%, respectively, and the direct recovery rate of Cu is not less than 80%.

[0019] Preferably, the high-arsenic copper electrolyte has the following composition: Cu 45-50 g / L, H2SO4 150-190 g / L, Ni 11-13 g / L, As 10-13 g / L, Sb 0.2-0.5 g / L, Bi 0.05-0.2 g / L, Pb 0.015-0.030 g / L, Zn 0.15-0.30 g / L, and Fe 1.0-1.5 g / L.

[0020] Compared with the prior art, the beneficial effects of this application include:

[0021] The copper electrolyte cascade treatment method provided in this application involves a cascade purification and impurity removal process, which uses a first-stage electrowinning process to remove copper from a high-arsenic copper-containing electrolyte, followed by a second-stage electrowinning process and a third-stage electrowinning process to remove impurities. This process achieves excellent impurity removal efficiency, with removal rates of As, Sb, and Bi not less than 95%, 80%, and 75%, respectively, and a direct recovery rate of Cu not less than 80%. The system energy consumption is no higher than 200 kWh / t. Cu Compared with existing technologies, it features low energy consumption, low cost, high direct copper recovery rate, good impurity removal effect, and environmental friendliness, and has broad application prospects in the field of copper electrolyte purification. Attached Figure Description

[0022] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the embodiments will be briefly described below. It should be understood that the following drawings only show some embodiments of this application and should not be regarded as a limitation on the scope of this application.

[0023] Figure 1 This is a schematic diagram of the process flow for the copper electrolyte cascade treatment method provided in the embodiment. Detailed Implementation

[0024] As used in this article:

[0025] "Prepared from" is synonymous with "comprising". The terms "comprising", "including", "having", "containing", or any other variations thereof as used herein are intended to cover non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that includes the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or elements inherent to such composition, step, method, article, or apparatus.

[0026] The conjunction "composed of..." excludes any unspecified elements, steps, or components. If used in a claim, this phrase makes the claim closed, excluding materials other than those described, except for associated conventional impurities. When the phrase "composed of..." appears in a clause of the body of a claim rather than immediately following it, it limits only the elements described in that clause; other elements are not excluded from the claim as a whole.

[0027] When a quantity, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value with any lower or preferred value, regardless of whether the range is disclosed individually. For example, when the range “1–5” is disclosed, the described range should be interpreted as including ranges “1–4”, “1–3”, “1–2”, “1–2 and 4–5”, “1–3 and 5”, etc. When numerical ranges are described herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within that range.

[0028] In these embodiments, unless otherwise specified, the portions and percentages are all by weight.

[0029] "Parts by mass" refers to the basic unit of measurement that expresses the mass ratio of multiple components. One part can represent any unit mass, such as 1g or 2.689g. If we say that component A has "a" parts by mass and component B has "b" parts by mass, it means the ratio of the mass of component A to the mass of component B is a:b. Alternatively, it can mean that the mass of component A is aK and the mass of component B is bK (K is any number representing a multiplier). It is important to understand that, unlike the number of parts by mass, the sum of the mass parts of all components is not limited to 100 parts.

[0030] "And / or" is used to indicate that one or both of the described situations may occur, for example, A and / or B includes (A and B) and (A or B).

[0031] A method for graded treatment of copper electrolyte includes:

[0032] The high-arsenic copper-containing electrolyte was subjected to a first-stage electrowinning process to remove copper, and the copper content of the electrolyte after the first-stage copper removal was controlled to be no less than 25 g / L, so as to recover Grade A copper.

[0033] The copper content of the first-stage copper removal solution is controlled to be no less than 9 g / L, and the No. 1 standard cathode copper is recovered.

[0034] The liquid after secondary copper removal is subjected to tertiary electrowinning for copper removal and impurity removal. The copper content of the liquid after tertiary copper removal is controlled to be no more than 0.5 g / L, and black copper slag is recovered.

[0035] In one optional embodiment, the high-arsenic copper-containing electrolyte is pumped into a primary electrolytic cell via a frequency converter pump. The primary electrolytic cell is an electrolytic cell employing a parallel flow solution circulation method.

[0036] In an optional embodiment, the circulation rate of the high-arsenic copper-containing electrolyte is 90 L / min-140 L / min, and the current density is 280 A / m. 2 -380A / m 2 The temperature of the high-arsenic copper-containing electrolyte is 50℃-60℃.

[0037] Optionally, the circulation rate of the high-arsenic copper-containing electrolyte can be any value between 90 L / min and 140 L / min, and the current density can be 280 A / m. 2 290A / m 2 300A / m 2 310A / m 2 320A / m 2 330A / m 2 340A / m 2 350A / m 2 360A / m 2 370A / m 2 380A / m 2 Or 280A / m 2 -380A / m 2 The temperature of the high-arsenic copper electrolyte can be any value between 50°C, 55°C, 60°C, or any value between 50°C and 60°C.

[0038] In an optional embodiment, the primary copper stripping solution is pumped into a secondary electrolytic cell via a variable frequency pump. The secondary electrolytic cell is an electrolytic cell employing a parallel flow solution circulation method.

[0039] In an optional embodiment, the circulation rate of the primary copper stripping solution is 90 L / min-140 L / min, and the current density is 280 A / m. 2 -380A / m 2 The temperature of the liquid after the first-stage copper removal is 50℃-60℃.

[0040] Optionally, the circulation rate of the primary copper removal solution can be any value between 90 L / min and 140 L / min, and the current density can be 280 A / m. 2 290A / m 2 300A / m2 310A / m 2 320A / m 2 330A / m 2 340A / m 2 350A / m 2 360A / m 2 370A / m 2 380A / m 2 Or 280A / m 2 -380A / m 2 The temperature of the liquid after primary copper removal can be any value between 50°C, 55°C, 60°C, or any value between 50°C and 60°C.

[0041] In an optional embodiment, the secondary copper stripping solution is pumped into a tertiary electrolytic cell via a frequency converter pump, wherein the tertiary electrolytic cell is a closed electrolytic cell.

[0042] In one optional embodiment, the circulation rate of the secondary copper removal solution is 90 L / min-140 L / min, and the current density is 500 A / m. 2 -600A / m 2 The temperature of the liquid after the secondary copper removal is 50℃-60℃.

[0043] Optionally, the circulation rate of the secondary copper removal solution can be any value between 90 L / min, 100 L / min, 110 L / min, 120 L / min, 130 L / min, 140 L / min, or 90 L / min - 140 L / min, and the current density can be 500 A / m. 2 550A / m 2 600A / m 2 Or 500A / m 2 -600A / m 2 The temperature of the secondary copper removal solution can be any value between 50°C, 55°C, 60°C, or any value between 50°C and 60°C.

[0044] By controlling the circulation flow rate and current density, the output of black copper slag and the amount of system return material are reduced, effectively improving the direct recovery rate of standard copper and reducing system energy consumption and production costs. The use of parallel flow technology can avoid problems such as concentration polarization and anode passivation, and can make the electrolyte flow parallel across the cathode surface at a suitable speed, greatly improving electrode efficiency and the quality of electrolytic copper.

[0045] In one optional implementation, the three-stage electrolytic cell is a closed electrolytic cell.

[0046] The use of a closed electrolytic cell in the three-stage electrowinning copper stripping stage prevents the escape of acid mist and AsH3 gas, effectively reducing environmental pollution and harm to the health of operators.

[0047] In an optional embodiment, the removal rates of As, Sb, and Bi in the high-arsenic copper electrolyte are not less than 95%, 80%, and 75%, respectively, and the direct recovery rate of Cu is not less than 80%.

[0048] In an optional embodiment, the high-arsenic copper-containing electrolyte has the following composition: Cu 45-50 g / L, H2SO4 150-190 g / L, Ni 11-13 g / L, As 10-13 g / L, Sb 0.2-0.5 g / L, Bi 0.05-0.2 g / L, Pb 0.015-0.030 g / L, Zn 0.15-0.30 g / L, and Fe 1.0-1.5 g / L.

[0049] The implementation schemes of this application will be described in detail below with reference to specific embodiments. However, those skilled in the art will understand that the following embodiments are only for illustrating this application and should not be regarded as limiting the scope of this application. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Where the manufacturers of reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0050] Example 1

[0051] like Figure 1 As shown, this embodiment provides a method for the graded treatment of copper electrolyte, specifically including the following steps:

[0052] The composition of the copper electrolyte used in this embodiment is as follows: Cu 45-50 g / L, H2SO4 150-190 g / L, Ni 11-13 g / L, As 10-13 g / L, Sb 0.2-0.5 g / L, Bi 0.05-0.2 g / L, Pb 0.015-0.030 g / L, Zn 0.15-0.30 g / L, and Fe 1.0-1.5 g / L.

[0053] (1) First-stage copper removal: The copper electrolyte is pumped to the first-stage copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 140 L / min and the current density is 300 A / m. 2The solution temperature was 54℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the first copper removal was not less than 25 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the first copper removal electrowinning products were tested, and the chemical composition content met the Grade A copper (Cu-CATH-1) standard.

[0054] (2) Secondary copper removal: The copper removal solution after the primary copper removal is pumped to the secondary copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 140 L / min, and the current density is 350 A / m³. 2 The solution temperature was 50℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the second copper removal was not less than 9 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the electrowinning products after the second copper removal were tested, and the chemical composition content met the No. 1 standard copper (Cu-CATH-2) standard.

[0055] (3) Tertiary impurity removal: The copper removal solution after the secondary copper removal is pumped to the tertiary copper removal and impurity removal electrolytic cell via a frequency converter. This electrolytic cell is a closed electrolytic cell; the solution circulation flow rate is 100 L / min, and the current density is 600 A / m³. 2 The solution temperature was 60℃; during the electrowinning process, the concentration of copper ions in the solution was sampled and analyzed to control the concentration of copper ions in the solution after the three-stage copper removal and impurity removal to be no more than 0.5 g / L; the removal rates of the main impurities As, Sb and Bi were 95.4%, 82.3% and 75.1% respectively, the direct recovery rate of Cu was 83%, and the generated black copper slag was stored in a centralized manner.

[0056] Example 2

[0057] This embodiment provides a method for the graded treatment of copper electrolyte, specifically including the following steps:

[0058] The composition of the copper electrolyte used in this embodiment is as follows: Cu 45-50 g / L, H2SO4 150-190 g / L, Ni 11-13 g / L, As 10-13 g / L, Sb 0.2-0.5 g / L, Bi 0.05-0.2 g / L, Pb 0.015-0.030 g / L, Zn 0.15-0.30 g / L, and Fe 1.0-1.5 g / L.

[0059] (1) First-stage copper removal: The copper electrolyte is pumped to the first-stage copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 140 L / min and the current density is 280 A / m. 2The solution temperature was 60℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the first copper removal was not less than 25 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the first copper removal electrowinning products were tested, and the chemical composition content met the Grade A copper (Cu-CATH-1) standard.

[0060] (2) Secondary copper removal: The copper removal solution after the primary copper removal is pumped to the secondary copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 140 L / min, and the current density is 320 A / m³. 2 The solution temperature was 50℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the second copper removal was not less than 9 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the electrowinning products after the second copper removal were tested, and the chemical composition content met the No. 1 standard copper (Cu-CATH-2) standard.

[0061] (3) Tertiary impurity removal: The copper removal solution after the secondary copper removal is pumped to the tertiary copper removal and impurity removal electrolytic cell via a frequency converter. This electrolytic cell is a closed electrolytic cell; the solution circulation flow rate is 120 L / min, and the current density is 600 A / m³. 2 The solution temperature was 50℃; during the electrowinning process, the concentration of copper ions in the solution was sampled and analyzed to control the concentration of copper ions in the solution after the three-stage copper removal and impurity removal to be no more than 0.5 g / L; the removal rates of the main impurities As, Sb and Bi were 95.6%, 82.1% and 81.5% respectively, the direct recovery rate of Cu was 87%, and the generated black copper slag was stored in a centralized manner.

[0062] Example 3

[0063] This embodiment provides a method for the graded treatment of copper electrolyte, specifically including the following steps:

[0064] The composition of the copper electrolyte used in this embodiment is as follows: Cu 45-50 g / L, H2SO4 150-190 g / L, Ni 11-13 g / L, As 10-13 g / L, Sb 0.2-0.5 g / L, Bi 0.05-0.2 g / L, Pb 0.015-0.030 g / L, Zn 0.15-0.30 g / L, and Fe 1.0-1.5 g / L.

[0065] (1) First-stage copper removal: The copper electrolyte is pumped to the first-stage copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 140 L / min, and the current density is 350 A / m. 2The solution temperature was 60℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the first copper removal was not less than 25 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the first copper removal electrowinning products were tested, and the chemical composition content met the Grade A copper (Cu-CATH-1) standard.

[0066] (2) Secondary copper removal: The copper removal solution from the primary stage is pumped to the secondary copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 140 L / min, and the current density is 360 A / m³. 2 The solution temperature was 50℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the second copper removal was not less than 9 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the electrowinning products after the second copper removal were tested, and the chemical composition content met the No. 1 standard copper (Cu-CATH-2) standard.

[0067] (3) Tertiary impurity removal: The copper removal solution after the secondary copper removal is pumped to the tertiary copper removal and impurity removal electrolytic cell via a frequency converter. This electrolytic cell is a closed electrolytic cell; the solution circulation flow rate is 130 L / min, and the current density is 550 A / m³. 2 The solution temperature was 55℃. During the electrowinning process, the concentration of copper ions in the solution was sampled and analyzed to ensure that the concentration of copper ions in the solution after the three-stage copper removal and impurity removal was not greater than 0.5 g / L. The removal rates of the main impurities As, Sb and Bi were 97.2%, 83.9% and 78.7% respectively, and the direct recovery rate of Cu was 84%. The black copper slag produced was collected and stored.

[0068] Comparative Example 1

[0069] The composition of the copper electrolyte used in this comparative example is as follows: Cu 45-50 g / L, H2SO4 150-190 g / L, Ni 11-13 g / L, As 10-13 g / L, Sb 0.2-0.5 g / L, Bi 0.05-0.2 g / L, Pb 0.015-0.030 g / L, Zn 0.15-0.30 g / L, and Fe 1.0-1.5 g / L.

[0070] (1) First-stage copper removal: The copper electrolyte is pumped to the first-stage copper removal electrolytic cell via a frequency converter. This electrolytic cell is a plate and frame electrolytic cell with bottom-in and top-out flow. The solution circulation rate is 140 L / min and the current density is 300 A / m³. 2The solution temperature was 54℃. During the electrowinning process, the concentration of copper ions in the solution was sampled and analyzed to ensure that the concentration of copper ions in the solution after the first copper removal was not less than 25 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the first copper removal electrowinning products were tested, and the chemical composition content did not meet the standard of Grade A copper (Cu-CATH-1).

[0071] (2) Secondary copper removal: The copper removal solution after the primary copper removal is pumped to the secondary copper removal electrolytic cell via a frequency converter. This electrolytic cell is a plate and frame electrolytic cell with bottom inlet and top outlet flow. The solution circulation rate is 140 L / min, and the current density is 350 A / m³. 2 The solution temperature was 50℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the second copper removal was not less than 9 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the electrowinning products after the second copper removal were tested. The chemical composition content did not meet the No. 1 standard copper (Cu-CATH-2) standard.

[0072] (3) Tertiary impurity removal: The copper removal solution after the secondary copper removal is pumped to the tertiary copper removal and impurity removal electrolytic cell via a frequency converter. This electrolytic cell is a closed electrolytic cell; the solution circulation flow rate is 100 L / min, and the current density is 600 A / m³. 2 The solution temperature was 60℃; during the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to control the copper ion concentration in the solution after the three-stage copper removal and impurity removal to be no more than 0.5 g / L; the removal rates of the main impurities As, Sb and Bi were 63.9%, 60.8% and 57.4% respectively, the direct recovery rate of Cu was 53.2%, and the generated black copper slag was collected and stored.

[0073] As can be seen from the comparison between Comparative Example 1 and the Examples, different circulation methods have a significant impact on the processing results, and the primary and secondary products do not meet the relevant standards. The circulation method provided in this application can achieve better impurity removal rate and direct copper recovery rate.

[0074] Comparative Example 2

[0075]

Stage 1

[0076]

Step 2

[0077] (1) First-stage copper removal: The copper electrolyte is pumped to the first-stage copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 140 L / min and the current density is 280 A / m. 2 The solution temperature was 60℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the first copper removal was not less than 25 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the first copper removal electrowinning products were tested, and the chemical composition content met the Grade A copper (Cu-CATH-1) standard.

[0078] (2) Secondary copper removal: The copper removal solution after the primary copper removal is pumped to the secondary copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 140 L / min, and the current density is 320 A / m³. 2The solution temperature was 50℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the second copper removal was not less than 9 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the electrowinning products after the second copper removal were tested. The chemical composition content met the No. 1 standard copper (Cu-CATH-2) standard, and the direct recovery rate of Cu was 65.6%. The black copper slag produced was collected and stored.

[0079] By comparing the single-stage and two-stage processing in Comparative Example 2 with the three-stage processing in the embodiment, it can be seen that the three-stage processing technology provided by this application can achieve a better direct copper recovery rate.

[0080] Comparative Example 3

[0081] Different copper stripping cycle volumes

[0082] The composition of the copper electrolyte used in this comparative example is as follows: Cu 45-50 g / L, H2SO4 150-190 g / L, Ni 11-13 g / L, As 10-13 g / L, Sb 0.2-0.5 g / L, Bi 0.05-0.2 g / L, Pb 0.015-0.030 g / L, Zn 0.15-0.30 g / L, and Fe 1.0-1.5 g / L.

[0083] (1) First-stage copper removal: The copper electrolyte is pumped to the first-stage copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 70 L / min, and the current density is 280 A / m. 2 The solution temperature was 60℃. During the electrowinning process, the concentration of copper ions in the solution was sampled and analyzed to ensure that the concentration of copper ions in the solution after the first copper removal was not less than 25 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the first copper removal electrowinning products were tested, and the chemical composition content did not meet the standard of Grade A copper (Cu-CATH-1).

[0084] (2) Secondary copper removal: The copper removal solution after the primary copper removal is pumped to the secondary copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 140 L / min, and the current density is 320 A / m³. 2The solution temperature was 50℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the second copper removal was not less than 9 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the electrowinning products after the second copper removal were tested, and the chemical composition content met the No. 1 standard copper (Cu-CATH-2) standard.

[0085] (3) Tertiary impurity removal: The copper removal solution after the secondary copper removal is pumped to the tertiary copper removal and impurity removal electrolytic cell via a frequency converter. This electrolytic cell is a closed electrolytic cell; the solution circulation flow rate is 120 L / min, and the current density is 600 A / m³. 2 The solution temperature was 50℃. During the electrowinning process, the concentration of copper ions in the solution was sampled and analyzed to ensure that the concentration of copper ions in the solution after the three-stage copper removal and impurity removal was not greater than 0.5 g / L. The removal rates of the main impurities As, Sb and Bi were 91.8%, 77.3% and 70.1% respectively, and the direct recovery rate of Cu was 90.3%. The black copper slag produced was collected and stored.

[0086] As can be seen from the above, when the primary copper removal cycle volume is relatively small, the chemical composition content of the primary copper removal electrowinning product does not meet the Class A copper (Cu-CATH-1) standard; ultimately, the removal rates of As, Sb, and Bi all decrease significantly.

[0087] Different secondary copper stripping cycle volumes

[0088] The composition of the copper electrolyte used in this comparative example is as follows: Cu 45-50 g / L, H2SO4 150-190 g / L, Ni 11-13 g / L, As 10-13 g / L, Sb 0.2-0.5 g / L, Bi 0.05-0.2 g / L, Pb 0.015-0.030 g / L, Zn 0.15-0.30 g / L, and Fe 1.0-1.5 g / L.

[0089] (1) First-stage copper removal: The copper electrolyte is pumped to the first-stage copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 140 L / min and the current density is 280 A / m. 2 The solution temperature was 60℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the first copper removal was not less than 25 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the first copper removal electrowinning products were tested, and the chemical composition content met the Grade A copper (Cu-CATH-1) standard.

[0090] (2) Secondary copper removal: The copper removal solution after the primary copper removal is pumped to the secondary copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 70 L / min, and the current density is 320 A / m³. 2 The solution temperature was 50℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the second copper removal was not less than 9 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the electrowinning products after the second copper removal were tested. The chemical composition content did not meet the No. 1 standard copper (Cu-CATH-2) standard.

[0091] (3) Tertiary impurity removal: The copper removal solution after the secondary copper removal is pumped to the tertiary copper removal and impurity removal electrolytic cell via a frequency converter. This electrolytic cell is a closed electrolytic cell; the solution circulation flow rate is 120 L / min, and the current density is 600 A / m³. 2 The solution temperature was 50℃; during the electrowinning process, the concentration of copper ions in the solution was sampled and analyzed to ensure that the concentration of copper ions in the solution after the three-stage copper removal and impurity removal was not greater than 0.5 g / L; the removal rates of the main impurities As, Sb and Bi were 91.1%, 77.2% and 68.2% respectively, the direct recovery rate of Cu was 72.5%, and the generated black copper slag was collected and stored.

[0092] As can be seen from the above, when the secondary copper removal cycle volume is relatively small, the chemical composition content of the secondary copper removal electrowinning product does not meet the No. 1 standard copper (Cu-CATH-2) standard; ultimately, the removal rates of As, Sb, and Bi, as well as the direct recovery rate of copper, all show a significant decrease.

[0093] Different three-stage impurity removal cycle volumes

[0094] The composition of the copper electrolyte used in this comparative example is as follows: Cu 45-50 g / L, H2SO4 150-190 g / L, Ni 11-13 g / L, As 10-13 g / L, Sb 0.2-0.5 g / L, Bi 0.05-0.2 g / L, Pb 0.015-0.030 g / L, Zn 0.15-0.30 g / L, and Fe 1.0-1.5 g / L.

[0095] (1) First-stage copper removal: The copper electrolyte is pumped to the first-stage copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 140 L / min and the current density is 280 A / m. 2The solution temperature was 60℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the first copper removal was not less than 25 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the first copper removal electrowinning products were tested, and the chemical composition content met the Grade A copper (Cu-CATH-1) standard.

[0096] (2) Secondary copper removal: The copper removal solution after the primary copper removal is pumped to the secondary copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 140 L / min, and the current density is 320 A / m³. 2 The solution temperature was 50℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the second copper removal was not less than 9 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the electrowinning products after the second copper removal were tested, and the chemical composition content met the No. 1 standard copper (Cu-CATH-2) standard.

[0097] (3) Tertiary impurity removal: The copper removal solution after the secondary copper removal is pumped to the tertiary copper removal and impurity removal electrolytic cell via a frequency converter. This electrolytic cell is a closed electrolytic cell; the solution circulation flow rate is 50 L / min, and the current density is 600 A / m³. 2 The solution temperature was 50℃; during the electrowinning process, the concentration of copper ions in the solution was sampled and analyzed to ensure that the concentration of copper ions in the solution after the three-stage copper removal and impurity removal was not greater than 0.5 g / L; the removal rates of the main impurities As, Sb and Bi were 82.2%, 76.1% and 70.2% respectively, the direct recovery rate of Cu was 87.2%, and the generated black copper slag was collected and stored.

[0098] As can be seen from the above, when the amount of copper removed in the three-stage process is relatively small, the removal rates of As, Sb, and Bi decrease significantly.

[0099] Different current densities at different levels

[0100] The composition of the copper electrolyte used in this comparative example is as follows: Cu 45-50 g / L, H2SO4 150-190 g / L, Ni 11-13 g / L, As 10-13 g / L, Sb 0.2-0.5 g / L, Bi 0.05-0.2 g / L, Pb 0.015-0.030 g / L, Zn 0.15-0.30 g / L, and Fe 1.0-1.5 g / L.

[0101] (1) First-stage copper removal: The copper electrolyte is pumped to the first-stage copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 140 L / min and the current density is 500 A / m.2 The solution temperature was 60℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the first copper removal was not less than 25 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the first copper removal electrowinning products were tested, and the chemical composition content met the Grade A copper (Cu-CATH-1) standard.

[0102] (2) Secondary copper removal: The copper removal solution after the primary copper removal is pumped to the secondary copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 140 L / min, and the current density is 320 A / m³. 2 The solution temperature was 50℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the second copper removal was not less than 9 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the electrowinning products after the second copper removal were tested, and the chemical composition content met the No. 1 standard copper (Cu-CATH-2) standard.

[0103] (3) Tertiary impurity removal: The copper removal solution after the secondary copper removal is pumped to the tertiary copper removal and impurity removal electrolytic cell via a frequency converter. This electrolytic cell is a closed electrolytic cell; the solution circulation flow rate is 120 L / min, and the current density is 550 A / m³. 2 The solution temperature was 55℃. During the electrowinning process, the concentration of copper ions in the solution was sampled and analyzed to ensure that the concentration of copper ions in the solution after the three-stage copper removal and impurity removal was not greater than 0.5 g / L. The removal rates of the main impurities As, Sb and Bi were 91.3%, 77.4% and 71.3% respectively, and the direct recovery rate of Cu was 70.6%. The black copper slag produced was collected and stored.

[0104] As can be seen from the above, when the primary current density is relatively high, the removal rates of As, Sb, and Bi, as well as the direct recovery rate of copper, all decrease significantly.

[0105] [Different Secondary Current Densities] The composition of the copper electrolyte used in this comparative example is as follows: Cu 45-50 g / L, H2SO4 150-190 g / L, Ni 11-13 g / L, As 10-13 g / L, Sb 0.2-0.5 g / L, Bi 0.05-0.2 g / L, Pb 0.015-0.030 g / L, Zn 0.15-0.30 g / L, Fe 1.0-1.5 g / L.

[0106] (1) First-stage copper removal: The copper electrolyte is pumped to the first-stage copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 140 L / min, and the current density is 350 A / m.2 The solution temperature was 60℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the first copper removal was not less than 25 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the first copper removal electrowinning products were tested, and the chemical composition content met the Grade A copper (Cu-CATH-1) standard.

[0107] (2) Secondary copper removal: The copper removal solution after the primary copper removal is pumped to the secondary copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 140 L / min, and the current density is 100 A / m³. 2 The solution temperature was 50℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the second copper removal was not less than 9 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the electrowinning products after the second copper removal were tested, and the chemical composition content met the No. 1 standard copper (Cu-CATH-2) standard.

[0108] (3) Tertiary impurity removal: The copper removal solution after the secondary copper removal is pumped to the tertiary copper removal and impurity removal electrolytic cell via a frequency converter. This electrolytic cell is a closed electrolytic cell; the solution circulation flow rate is 130 L / min, and the current density is 550 A / m³. 2 The solution temperature was 55℃. During the electrowinning process, the concentration of copper ions in the solution was sampled and analyzed to ensure that the concentration of copper ions in the solution after the three-stage copper removal and impurity removal was not greater than 0.5 g / L. The removal rates of the main impurities As, Sb and Bi were 92.1%, 76.6% and 71.3% respectively, and the direct recovery rate of Cu was 72.8%. The black copper slag produced was collected and stored.

[0109] As can be seen from the above, when the secondary current density is relatively low, the removal rates of As, Sb, and Bi, as well as the direct recovery rate of copper, all decrease significantly.

[0110] [Different Three-Stage Current Densities] The composition of the copper electrolyte used in this comparative example is as follows: Cu 45-50 g / L, H2SO4 150-190 g / L, Ni 11-13 g / L, As 10-13 g / L, Sb 0.2-0.5 g / L, Bi 0.05-0.2 g / L, Pb 0.015-0.030 g / L, Zn 0.15-0.30 g / L, Fe 1.0-1.5 g / L.

[0111] (1) First-stage copper removal: The copper electrolyte is pumped to the first-stage copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 140 L / min, and the current density is 350 A / m.2 The solution temperature was 60℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the first copper removal was not less than 25 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the first copper removal electrowinning products were tested, and the chemical composition content met the Grade A copper (Cu-CATH-1) standard.

[0112] (2) Secondary copper removal: The copper removal solution after the primary copper removal is pumped to the secondary copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 140 L / min, and the current density is 320 A / m³. 2 The solution temperature was 50℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the second copper removal was not less than 9 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the electrowinning products after the second copper removal were tested, and the chemical composition content met the No. 1 standard copper (Cu-CATH-2) standard.

[0113] (3) Tertiary impurity removal: The copper removal solution after the secondary copper removal is pumped to the tertiary copper removal and impurity removal electrolytic cell via a frequency converter. This electrolytic cell is a closed electrolytic cell; the solution circulation flow rate is 130 L / min, and the current density is 200 A / m³. 2 The solution temperature was 55℃; during the electrowinning process, the concentration of copper ions in the solution was sampled and analyzed to ensure that the concentration of copper ions in the solution after the three-stage copper removal and impurity removal was not greater than 0.5 g / L; the removal rates of the main impurities As, Sb and Bi were 54.8%, 46.2% and 42.7% respectively, the direct recovery rate of Cu was 80.3%, and the generated black copper slag was collected and stored.

[0114] As can be seen from the above, when the current density of the three stages is relatively low, the removal rates of As, Sb and Bi all decrease significantly, and the direct recovery rate of copper also decreases by 3.7%.

[0115] [Different Temperature Levels] The composition of the copper electrolyte used in this comparative example is as follows: Cu 45-50 g / L, H2SO4 150-190 g / L, Ni 11-13 g / L, As 10-13 g / L, Sb 0.2-0.5 g / L, Bi 0.05-0.2 g / L, Pb 0.015-0.030 g / L, Zn 0.15-0.30 g / L, Fe 1.0-1.5 g / L.

[0116] (1) First-stage copper removal: The copper electrolyte is pumped to the first-stage copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 140 L / min, and the current density is 350 A / m.2 The solution temperature was 85℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the first copper removal was not less than 25 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the first copper removal electrowinning products were tested, and the chemical composition content did not meet the Grade A copper (Cu-CATH-1) standard.

[0117] (2) Secondary copper removal: The copper removal solution from the primary stage is pumped to the secondary copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 140 L / min, and the current density is 360 A / m³. 2 The solution temperature was 50℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the second copper removal was not less than 9 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the electrowinning products after the second copper removal were tested, and the chemical composition content met the No. 1 standard copper (Cu-CATH-2) standard.

[0118] (3) Tertiary impurity removal: The copper removal solution after the secondary copper removal is pumped to the tertiary copper removal and impurity removal electrolytic cell via a frequency converter. This electrolytic cell is a closed electrolytic cell; the solution circulation flow rate is 130 L / min, and the current density is 550 A / m³. 2 The solution temperature was 55℃. During the electrowinning process, the concentration of copper ions in the solution was sampled and analyzed to ensure that the concentration of copper ions in the solution after the three-stage copper removal and impurity removal was not greater than 0.5 g / L. The removal rates of the main impurities As, Sb and Bi were 94.4%, 77.1% and 73.2% respectively, and the direct recovery rate of Cu was 84.1%. The black copper slag produced was collected and stored.

[0119] As can be seen from the above, when the primary copper removal temperature is relatively high, the chemical composition of the primary copper removal electrowinning product does not meet the Class A copper (Cu-CATH-1) standard. As a result, the removal rate of As decreases to a certain extent, and the removal rates of Sb and Bi decrease significantly.

[0120] [Different Secondary Temperatures] The composition of the copper electrolyte used in this comparative example is as follows: Cu 45-50 g / L, H2SO4 150-190 g / L, Ni 11-13 g / L, As 10-13 g / L, Sb 0.2-0.5 g / L, Bi 0.05-0.2 g / L, Pb 0.015-0.030 g / L, Zn 0.15-0.30 g / L, Fe 1.0-1.5 g / L.

[0121] (1) First-stage copper removal: The copper electrolyte is pumped to the first-stage copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 140 L / min, and the current density is 350 A / m. 2 The solution temperature was 60℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the first copper removal was not less than 25 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the first copper removal electrowinning products were tested, and the chemical composition content met the Grade A copper (Cu-CATH-1) standard.

[0122] (2) Secondary copper removal: The copper removal solution from the primary stage is pumped to the secondary copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 140 L / min, and the current density is 360 A / m³. 2 The solution temperature was 20℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the second copper removal was not less than 9 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the second copper removal electrowinning products were tested, and the chemical composition content met the No. 1 standard copper (Cu-CATH-2) standard.

[0123] (3) Tertiary impurity removal: The copper removal solution after the secondary copper removal is pumped to the tertiary copper removal and impurity removal electrolytic cell via a frequency converter. This electrolytic cell is a closed electrolytic cell; the solution circulation flow rate is 130 L / min, and the current density is 550 A / m³. 2 The solution temperature was 55℃. During the electrowinning process, the concentration of copper ions in the solution was sampled and analyzed to ensure that the concentration of copper ions in the solution after the three-stage copper removal and impurity removal was not greater than 0.5 g / L. The removal rates of the main impurities As, Sb and Bi were 91.1%, 76.9% and 68.2% respectively, and the direct recovery rate of Cu was 76.5%. The black copper slag produced was collected and stored.

[0124] As can be seen from the above, when the secondary copper removal temperature is low, the removal rates of As, Sb, and Bi, as well as the direct copper recovery rate, all decrease significantly.

[0125] [Different Three Temperature Levels] The composition of the copper electrolyte used in this comparative example is as follows: Cu 45~50g / L, H2SO4 150~190g / L, Ni 11~13g / L, As 10~13g / L, Sb 0.2~0.5g / L, Bi 0.05~0.2g / L, Pb 0.015~0.030g / L, Zn 0.15~0.30g / L, Fe 1.0~1.5g / L.

[0126] (1) First-stage copper removal: The copper electrolyte is pumped to the first-stage copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 140 L / min, and the current density is 350 A / m. 2 The solution temperature was 60℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the first copper removal was not less than 25 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the first copper removal electrowinning products were tested, and the chemical composition content met the Grade A copper (Cu-CATH-1) standard.

[0127] (2) Secondary copper removal: The copper removal solution from the primary stage is pumped to the secondary copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 140 L / min, and the current density is 360 A / m³. 2 The solution temperature was 50℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the second copper removal was not less than 9 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the electrowinning products after the second copper removal were tested, and the chemical composition content met the No. 1 standard copper (Cu-CATH-2) standard.

[0128] (3) Tertiary impurity removal: The copper removal solution after the secondary copper removal is pumped to the tertiary copper removal and impurity removal electrolytic cell via a frequency converter. This electrolytic cell is a closed electrolytic cell; the solution circulation flow rate is 130 L / min, and the current density is 550 A / m³. 2 The solution temperature was 25℃. During the electrowinning process, the concentration of copper ions in the solution was sampled and analyzed to ensure that the concentration of copper ions in the solution after the three-stage copper removal and impurity removal was not greater than 0.5 g / L. The removal rates of the main impurities As, Sb and Bi were 78.2%, 71.9% and 63.4% respectively, and the direct recovery rate of Cu was 84.2%. The black copper slag produced was collected and stored.

[0129] As can be seen from the above, when the copper removal temperature is relatively low in the third stage, the removal rates of As, Sb and Bi all decrease significantly.

[0130] Comparative Example 4

[0131] [Concentration of the electrolyte after copper removal] The composition of the copper electrolyte used in this comparative example is as follows: Cu 45-50 g / L, H2SO4 150-190 g / L, Ni 11-13 g / L, As 10-13 g / L, Sb 0.2-0.5 g / L, Bi 0.05-0.2 g / L, Pb 0.015-0.030 g / L, Zn 0.15-0.30 g / L, Fe 1.0-1.5 g / L.

[0132] (1) First-stage copper removal: The copper electrolyte is pumped to the first-stage copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 140 L / min and the current density is 280 A / m. 2 The solution temperature was 60℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the first copper removal was not less than 10 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the first copper removal electrowinning products were tested, and the chemical composition content did not meet the Grade A copper (Cu-CATH-1) standard.

[0133] (2) Secondary copper removal: The copper removal solution after the primary copper removal is pumped to the secondary copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 140 L / min, and the current density is 320 A / m³. 2 The solution temperature was 50℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the second copper removal was not less than 9 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the electrowinning products after the second copper removal were tested, and the chemical composition content met the No. 1 standard copper (Cu-CATH-2) standard.

[0134] (3) Tertiary impurity removal: The copper removal solution after the secondary copper removal is pumped to the tertiary copper removal and impurity removal electrolytic cell via a frequency converter. This electrolytic cell is a closed electrolytic cell; the solution circulation flow rate is 120 L / min, and the current density is 600 A / m³. 2 The solution temperature was 50℃; during the electrowinning process, the concentration of copper ions in the solution was sampled and analyzed to ensure that the concentration of copper ions in the solution after the three-stage copper removal and impurity removal was not greater than 0.5 g / L; the removal rates of the main impurities As, Sb and Bi were 93.4%, 78.1% and 69.2% respectively, the direct recovery rate of Cu was 84.4%, and the generated black copper slag was collected and stored.

[0135] As can be seen from the above, when the copper ion concentration in the liquid after primary copper removal is too low, the chemical composition of the primary copper removal electrowinning product does not meet the Class A copper (Cu-CATH-1) standard; the removal rates of As, Sb, and Bi all decrease to a certain extent.

[0136] [Concentration of the electrolyte after the second stage of copper removal] The composition of the copper electrolyte used in this comparative example is as follows: Cu 45-50 g / L, H2SO4 150-190 g / L, Ni 11-13 g / L, As 10-13 g / L, Sb 0.2-0.5 g / L, Bi 0.05-0.2 g / L, Pb 0.015-0.030 g / L, Zn 0.15-0.30 g / L, Fe 1.0-1.5 g / L.

[0137] (1) First-stage copper removal: The copper electrolyte is pumped to the first-stage copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 140 L / min and the current density is 280 A / m. 2 The solution temperature was 60℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the first copper removal was not less than 10 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the first copper removal electrowinning products were tested, and the chemical composition content met the Grade A copper (Cu-CATH-1) standard.

[0138] (2) Secondary copper removal: The copper removal solution after the primary copper removal is pumped to the secondary copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 140 L / min, and the current density is 320 A / m³. 2 The solution temperature was 50℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the second copper removal was not less than 3g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 minutes. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the electrowinning products after the second copper removal were tested. The chemical composition content did not meet the No. 1 standard copper (Cu-CATH-2) standard.

[0139] (3) Tertiary impurity removal: The copper removal solution after the secondary copper removal is pumped to the tertiary copper removal and impurity removal electrolytic cell via a frequency converter. This electrolytic cell is a closed electrolytic cell; the solution circulation flow rate is 120 L / min, and the current density is 600 A / m³. 2 The solution temperature was 50℃; during the electrowinning process, the concentration of copper ions in the solution was sampled and analyzed to ensure that the concentration of copper ions in the solution after the three-stage copper removal and impurity removal was not greater than 0.5 g / L; the removal rates of the main impurities As, Sb and Bi were 93.2%, 78.2% and 69.1% respectively, the direct recovery rate of Cu was 83.7%, and the generated black copper slag was collected and stored.

[0140] As can be seen from the above, when the copper ion concentration in the secondary copper removal solution is too low, the chemical composition of the secondary copper removal electrowinning product does not meet the Class A copper (Cu-CATH-2) standard; the removal rates of As, Sb, and Bi all decrease to a certain extent.

[0141] [Concentration of the electrolyte after three-stage copper removal] The composition of the copper electrolyte used in this comparative example is as follows: Cu 45-50 g / L, H2SO4 150-190 g / L, Ni 11-13 g / L, As 10-13 g / L, Sb 0.2-0.5 g / L, Bi 0.05-0.2 g / L, Pb 0.015-0.030 g / L, Zn 0.15-0.30 g / L, Fe 1.0-1.5 g / L.

[0142] (1) First-stage copper removal: The copper electrolyte is pumped to the first-stage copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 140 L / min and the current density is 280 A / m. 2 The solution temperature was 60℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the first copper removal was not less than 10 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the first copper removal electrowinning products were tested, and the chemical composition content met the Grade A copper (Cu-CATH-1) standard.

[0143] (2) Secondary copper removal: The copper removal solution after the primary copper removal is pumped to the secondary copper removal electrolytic cell via a variable frequency pump. This electrolytic cell is a plate and frame electrolytic cell with parallel flow solution circulation; the solution circulation rate is 140 L / min, and the current density is 320 A / m³. 2 The solution temperature was 50℃. During the electrowinning process, the copper ion concentration in the solution was sampled and analyzed to ensure that the copper ion concentration in the solution after the second copper removal was not less than 9 g / L. Small pieces of electrowinning copper plates were randomly selected and soaked in 10% hydrochloric acid solution for 15 min. They were then thoroughly washed with deionized water to remove foreign contaminants from the copper plates. After drying, the electrowinning products after the second copper removal were tested, and the chemical composition content met the No. 1 standard copper (Cu-CATH-2) standard.

[0144] (3) Tertiary impurity removal: The copper removal solution after the secondary copper removal is pumped to the tertiary copper removal and impurity removal electrolytic cell via a frequency converter. This electrolytic cell is a closed electrolytic cell; the solution circulation flow rate is 120 L / min, and the current density is 600 A / m³. 2 The solution temperature was 50℃; during the electrowinning process, the concentration of copper ions in the solution was sampled and analyzed to ensure that the concentration of copper ions in the solution after the three-stage copper removal and impurity removal was not greater than 1.0 g / L; the removal rates of the main impurities As, Sb and Bi were 83.4%, 78.1% and 72.3% respectively, the direct recovery rate of Cu was 83.7%, and the generated black copper slag was collected and stored.

[0145] As can be seen from the above, when the copper ion concentration in the liquid after the tertiary copper removal is too high, the removal rates of As, Sb, and Bi all decrease to some extent.

[0146] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.

[0147] Furthermore, those skilled in the art will understand that although some embodiments herein include certain features included in other embodiments but not others, combinations of features from different embodiments are intended to be within the scope of this application and form different embodiments. For example, in the foregoing claims, any of the claimed embodiments can be used in any combination. The information disclosed in this background section is intended only to enhance the understanding of the general background of this application and should not be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

Claims

1. A method for the cascade treatment of copper electrolytes, characterized in that, The application relates to a method for recovering copper from high-arsenic copper-containing electrolyte. The high-arsenic copper-containing electrolyte is subjected to primary copper removal by electro-deposition, the copper content of the solution after the primary copper removal is controlled to be not less than 25 g / L, and A-grade copper is recovered; The solution after the primary copper removal is subjected to secondary copper removal by electro-deposition, the copper content of the solution after the secondary copper removal is controlled to be not less than 9 g / L, and No.1 standard cathode copper is recovered; The solution after the secondary copper removal is subjected to tertiary copper removal by electro-deposition, the copper content of the solution after the tertiary copper removal is controlled to be not more than 0.5 g / L, and black copper residue is recovered; The high-arsenic copper-containing electrolyte is pumped into a primary electrolytic tank by a frequency conversion pump, and the primary electrolytic tank is an electrolytic tank adopting a parallel flow solution circulation flow mode; The circulating amount of the high-arsenic copper-containing electrolyte is 90 L / min-140 L / min, the current density is , and the temperature of the high-arsenic copper-containing electrolyte is 50℃-60℃. The solution after the primary copper removal is pumped into a secondary electrolytic tank by a frequency conversion pump, and the secondary electrolytic tank is an electrolytic tank adopting a parallel flow solution circulation flow mode; The circulating amount of the primary copper removal solution is 90 L / min-140 L / min, the current density is , and the temperature of the primary copper removal solution is 50℃-60℃. The solution after the secondary copper removal is pumped into a tertiary electrolytic tank by a frequency conversion pump, and the tertiary electrolytic tank is a closed electrolytic tank adopting a parallel flow solution circulation flow mode; The circulating amount of the secondary copper removal liquid is 90 L / min-140 L / min, the current density is , and the temperature of the secondary copper removal liquid is 50℃-60℃.

2. The method of copper electrolyte cascade treatment according to claim 1, characterized in that, The tertiary electrolytic tank is a closed electrolytic tank.

3. The method of copper electrolyte cascade processing according to claim 1, characterized in that, In the high-arsenic copper-containing electrolyte, the removal rates of As, Sb and Bi are not less than 95%, 80% and 75% respectively, and the direct recovery rate of Cu is not less than 80%.

4. The method for the cascade treatment of copper electrolyte according to any one of claims 1-3, characterized in that, said high-arsenic copper electrolyte has a composition of Cu 45-50 g / L, 150-190 g / L, Ni 11-13 g / L, As 10-13 g / L, Sb 0.2-0.5 g / L, Bi 0.05-0.2 g / L, Pb 0.015-0.030 g / L, Zn 0.15-0.30 g / L, Fe 1.0-1.5 g / L.

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