A method for inhibiting copper powder formation during the electrolytic refining of low-arsenic copper anodes

Abstract

The present application belongs to the field of copper electrolytic refining, and relates to a method for inhibiting copper powder generation in the process of low-arsenic copper anode electrolytic refining. + The method inhibits the generation of copper powder in the process of electrolytic refining by adding a copper powder inhibitor in the process of low-arsenic copper anode electrolytic refining, so that the disproportionation reaction occurs, thereby reducing the generation of copper powder in the process of low-arsenic copper anode electrolytic refining, the content of copper powder in anode slime is reduced from 68.3% to 29.8%, the subsequent treatment steps of anode slime are simplified, the cathode current efficiency is increased from 87% to 93%, and the surface quality of cathode copper is significantly improved, and the qualified rate of A-grade copper is increased from 80% to 95%.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of copper electrolytic refining, and relates to a method for inhibiting the generation of copper powder in the electrolytic refining process of low-arsenic copper anodes. BACKGROUND

[0002] In the process of copper electrolytic refining, part of Cu + will inevitably be generated in the dissolution process of copper anodes. + Cu 2+ is extremely prone to disproportionation in the copper electrolyte to generate Cu + and metallic copper powder. Part of the generated copper powder will enter the anode sludge, causing copper loss and subsequent processing difficulties of the anode sludge; another part of the copper powder will adhere to the surface of the cathode, forming new active crystallization cores and rapidly growing into copper particles, thereby reducing the surface quality of the cathode copper.

[0003] Therefore, to reduce the impact of copper powder on the electrolysis process, it is necessary to inhibit the generation of Cu + and its disproportionation reaction as much as possible. There are two main reasons for the generation of Cu + during electrolysis: one is that part of the copper atoms in the anode are electrochemically dissolved in the form of Cu + under the action of electric current; the other is that Cu2O in the anode plate reacts with H2SO4 solution to generate Cu + . Among them, most of the Cu2O in the anode plate can be removed by early and sufficient soaking with electrolyte, while Cu + generated by electrochemical dissolution of copper atoms will inevitably occur in the copper electrolytic refining process.

[0004] The Cu + and copper powder generated in the copper electrolytic refining process of copper anode plates with impurity content in the standard state are not too harmful to the copper electrolysis process, so researchers at home and abroad have not paid too much attention to how to reduce the content of Cu + and copper powder in the electrolyte. However, with the increasing complexity of material sources, low-arsenic copper anodes are applied in the field of copper electrolytic refining. This type of copper anode shows a higher cell voltage during electrolytic refining, which is conducive to the generation of Cu + . Cu + is unstable in the electrolyte and is prone to disproportionation to generate metallic copper powder, which ultimately reduces the current efficiency of the cathode copper and the surface quality of the cathode, and makes the subsequent processing of the anode sludge more complex. SUMMARY

[0005] The present application discloses a method for inhibiting the generation of copper powder in the electrolytic refining process of low-arsenic copper anodes, to solve any of the above and other potential problems of the prior art.

[0006] To achieve the above object, the technical scheme of the present application is: a method for inhibiting copper powder generation in low-arsenic copper anode electrolytic refining process, which adds copper powder inhibitor in the low-arsenic copper anode electrolytic refining process, the copper powder inhibitor can inhibit the generation of copper powder in the electrolytic refining process + The disproportionation reaction occurs, the copper powder content in the anode slime is reduced by 29.8%, and the cathode current efficiency is increased to 93%.

[0007] Further, the method specifically comprises the following steps:

[0008] S1) loading low-arsenic copper anode plate and cathode into the electrolytic cell, then adding copper ion-containing electrolyte, and adjusting the electrolyte temperature and circulation amount;

[0009] S2) adding copper powder inhibitor into the circulation tank, uniformly and continuously adding the copper powder inhibitor in the circulation tank into the head tank, adjusting the current density, and performing electrolysis.

[0010] Further, the low-arsenic copper anode plate in S1) is loaded into the electrolytic cell, and the copper anode is fully soaked with electrolyte for 1-10h;

[0011] The cathode is 316L stainless steel.

[0012] Further, the copper ion concentration in the copper ion electrolyte in S1) is 35-55g / L, and the sulfuric acid concentration is 150-200g / L.

[0013] Further, the electrolyte temperature in S1) is 55-70℃, and the electrolyte circulation amount is 25-40L / min.

[0014] Further, the copper powder inhibitor in S2) comprises bone glue, thiourea, hydrochloric acid and an additive;

[0015] The addition amount in the electrolyte is: the bone glue concentration is 1-5mg / L, the thiourea is 1-5mg / L, the hydrochloric acid concentration is 35-75mg / L, and the concentration is 5-50mg / L.

[0016] Further, the additive is one or both of an oxidizing agent or a complexing agent.

[0017] Further, the oxidizing agent is one or more of hydrogen peroxide, persulfuric acid, sodium persulfate, hypochlorous acid, performic acid, and peracetic acid.

[0018] Further, the complexing agent is one or more of nitrosalicylic acid, ethylenediaminetetraacetic acid, bipyridine, and ethylenediamine.

[0019] Further, the method obtains a qualified rate of A-grade copper in the cathode copper of not less than 95%.

[0020] The beneficial effects of the present application are: due to the above technical scheme, the method of the present application inhibits the generation of copper powder in the low-arsenic copper anode electrolytic refining process by adding copper powder inhibitor in the low-arsenic copper anode electrolytic refining process, thereby reducing the generation of copper powder in the electrolytic refining process + The disproportionation reaction occurs, thereby reducing the generation of copper powder in the low-arsenic copper anode electrolytic refining process, reducing the copper powder content in the anode slime from 68.3% to 29.8%, simplifying the subsequent treatment steps of the anode slime, increasing the cathode current efficiency from 87% to 93%, and significantly improving the surface quality of the cathode copper, increasing the qualified rate of A-grade copper from 80% to 95%. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 The flowchart of the method for inhibiting the generation of copper powder in the low-arsenic copper anode electrolytic refining process of the present application.

[0022] Figure 2 The contrast diagram of the cathode surface before and after the treatment by the method of the present application (left: before adding, right: after adding). DETAILED DESCRIPTION

[0023] In order to further understand the present application, the technical solutions in the embodiments of the present application are described clearly and completely below in combination with the drawings and the tables. However, the described embodiments are only a part of the embodiments of the present application, and all other embodiments of a person skilled in the art without creative labor based on the embodiments in the present application are within the protection scope of the present application. These descriptions are only for further illustrating the features and advantages of the present application, and are not a limitation on the claims of the present application.

[0024] The method for inhibiting the generation of copper powder in the low-arsenic copper anode electrolytic refining process of the present application, by adding copper powder inhibitor in the low-arsenic copper anode electrolytic refining process, the copper powder inhibitor can inhibit the generation of Cu + The disproportionation reaction occurs, thereby reducing the generation of copper powder in the low-arsenic copper anode electrolytic refining process, reducing the copper powder content in the anode slime from 68.3% to 29.8%, simplifying the subsequent treatment steps of the anode slime, increasing the cathode current efficiency from 87% to 93%, and significantly improving the surface quality of the cathode copper, increasing the qualified rate of A-grade copper from 80% to 95%.

[0025] As Figure 1 shown, the method specifically comprises the following steps:

[0026] S1) loading the low-arsenic copper anode plate and the cathode into the electrolytic cell, then adding the electrolyte containing copper ions, and adjusting the temperature and circulation amount of the electrolyte;

[0027] S2) adding the copper powder inhibitor into the circulation tank, uniformly and continuously adding the copper powder inhibitor in the circulation tank into the head tank, adjusting the current density, and performing electrolysis, and the electrolysis period is 11 days.

[0028] The low-arsenic copper anode plate in S1) is loaded into the electrolytic cell, and the copper anode is first fully soaked with the electrolyte for 1-10 h;

[0029] The cathode is 316L stainless steel.

[0030] The copper ion concentration in the copper ion electrolyte in S1) is 35-55 g / L, and the sulfuric acid concentration is 150-200 g / L.

[0031] The electrolyte temperature in S1) is 55-70℃, and the electrolyte circulation amount is 25-40 L / min.

[0032] The copper powder inhibitor in S2) includes bone glue, thiourea, hydrochloric acid, and an additive;

[0033] The addition amount in the electrolyte is: the bone glue concentration is 1-5 mg / L, the thiourea is 1-5 mg / L, the hydrochloric acid concentration is 35-75 mg / L, and the concentration is 5-50 mg / L.

[0034] The additive is one or both of an oxidizing agent or a complexing agent.

[0035] The oxidizing agent is one or more of hydrogen peroxide, persulfuric acid, sodium persulfate, hypochlorous acid, performic acid, and peracetic acid.

[0036] The complexing agent is one or more of nitrosalicylic acid, ethylenediaminetetraacetic acid, bipyridine, and ethylenediamine

[0037] The method obtains a qualified rate of A-grade copper in the cathode copper of not less than 95%.

[0038] Example 1: A low-arsenic copper anode plate (its specific composition is shown in Table 1) is loaded into an electrolytic cell, and the copper anode is fully soaked in the electrolyte for 4 hours; 316L stainless steel is used as the cathode and loaded into the cell, and the electrolyte composition is controlled to be a copper ion concentration of 42 g / L and a sulfuric acid concentration of 170 g / L, the electrolyte temperature is 65℃, the electrolyte circulation amount is 30 L / min, and the current density is 300 A / m 2 The additives bone glue, thiourea, and hydrochloric acid are continuously and uniformly added to the circulating tank, and the diluted dinitrosalicylic acid solution is continuously and uniformly added to the high tank, and after 11 days of electrolysis, the copper powder content in the anode mud is detected and the cathode surface quality is observed.

[0039] During electrolysis, the bone glue concentration in the electrolyte is 2 mg / L, the thiourea is 3 mg / L, the hydrochloric acid concentration is 40 mg / L, and the dinitrosalicylic acid concentration is 20 mg / L.

[0040] Table 2 shows the main components of the anode mud before and after the addition of dinitrosalicylic acid. As can be seen from the table, the copper content in the anode mud is significantly reduced after the addition of dinitrosalicylic acid, indicating that the generation of copper powder is successfully inhibited under the action of dinitrosalicylic acid.

[0041] As Figure 2The cathode copper surface before and after adding dinitro salicylic acid is shown. It can be seen that the cathode surface is very smooth after adding the additive, and few particles are generated.

[0042] The A-grade copper qualified rate of the post-cathode copper can reach 95%, and the current efficiency can reach 93%.

[0043] Table 1: Low arsenic copper anode chemical composition table

[0044]

[0045] Table 2: Low arsenic copper anode chemical composition table before and after adding dinitro salicylic acid

[0046]

[0047] Example 2: The low arsenic copper anode plate is loaded into the electrolytic cell, and the copper anode is fully soaked in the electrolyte for 4h; 316L stainless steel is used as the cathode and loaded into the cell, and the electrolyte composition is controlled to be copper ion concentration of 42g / L, sulfuric acid concentration of 170g / L, electrolyte temperature of 55℃, electrolyte circulation amount of 30L / min, and current density of 300A / m 2 The additive bone glue, thiourea, hydrochloric acid and hydrogen peroxide are uniformly and continuously added to the circulating tank, and the diluted hydrogen peroxide is uniformly and continuously added to the high tank. After 11 days of electrolysis, the copper powder content in the anode mud is detected and the cathode surface quality is observed.

[0048] During electrolysis, the bone glue concentration in the electrolyte is 4mg / L, the thiourea is 2mg / L, the hydrochloric acid concentration is 20mg / L, and the hydrogen peroxide concentration is 30mg / L.

[0049] The A-grade copper qualified rate of the post-cathode copper can reach 95%, and the current efficiency can reach 93%.

[0050] Example 3: The low arsenic copper anode plate is loaded into the electrolytic cell, and the copper anode is fully soaked in the electrolyte for 4h; 316L stainless steel is used as the cathode and loaded into the cell, and the electrolyte composition is controlled to be copper ion concentration of 42g / L, sulfuric acid concentration of 170g / L, electrolyte temperature of 70℃, electrolyte circulation amount of 30L / min, and current density of 300A / m 2 The additive bone glue, thiourea, hydrochloric acid and hydrogen peroxide are uniformly and continuously added to the circulating tank, and the diluted hydrogen peroxide is uniformly and continuously added to the high tank. After 11 days of electrolysis, the copper powder content in the anode mud is detected and the cathode surface quality is observed.

[0051] During electrolysis, the bone glue concentration in the electrolyte is 5mg / L, the thiourea is 1mg / L, the hydrochloric acid concentration is 50mg / L, and the hydrogen peroxide concentration is 35mg / L.

[0052] The A-grade copper qualified rate of the post-cathode copper can reach 95%, and the current efficiency can reach 93%.

[0053] The above describes in detail the method for inhibiting copper powder generation in the low-arsenic copper anode electrolytic refining process provided by the embodiments of the application. The above description of the embodiments is only used to help understand the method and its core idea of the application; meanwhile, for those skilled in the art, the specific implementation and application range will be changed according to the idea of the application, and the above description should not be understood as a limitation on the application.

[0054] As some terms are used in the description and claims, those skilled in the art can understand that hardware manufacturers can use different names to refer to the same component. The description and claims of the present application do not distinguish components by name, but by the functional difference between components. As mentioned throughout the description and claims, "including" and "comprising" are open terms, which should be interpreted as "including / comprising but not limited to". "Approximately" means that within an acceptable error range, those skilled in the art can solve the technical problems within a certain error range and basically achieve the technical effects. The subsequent description of the specification is a preferred embodiment of the application, which is intended to illustrate the general principles of the application, but not to limit the scope of the application. The scope of protection of the application is defined by the appended claims.

[0055] It should also be noted that the terms "comprising", "including", or any other variant thereof are intended to cover non-exclusive inclusion, so that the products or systems including a series of elements not only include those elements, but also include other elements not explicitly listed, or include elements inherent to such products or systems. Without more limitations, the element defined by the sentence "including a" does not exclude the presence of other identical elements in the product or system including the element.

[0056] It should be understood that the term "and / or" used herein is only a description of the association relationship between the associated objects, which means that there can be three relationships, for example, A and / or B, which can represent the three cases of A alone, A and B together, and B alone. In addition, the character " / " in this paper generally represents that the front and rear associated objects have an "or" relationship.

[0057] The foregoing description illustrates and describes several preferred embodiments of the present application. However, it is to be understood that the application is not limited to the precise forms described, and that changes can be made therein without departing from the scope of the present application. Other embodiments of the application will be apparent to those skilled in the art from consideration of the specification and practice of the application disclosed herein. Therefore, the specification and examples are to be considered exemplary only, with a true scope and spirit of the application being indicated by the following claims.

Claims

1. A method for suppressing copper powder generation during the electrolytic refining of low-arsenic copper anolytes, characterized in that, This method involves adding a copper powder inhibitor during the low-arsenic copper anode electrolytic refining process. The copper powder inhibitor can suppress the Cu content during electrolytic refining. + A disproportionation reaction occurs; the method specifically includes the following steps: S1) The low-arsenic copper anode plate and cathode are loaded into the electrolytic cell, and then a copper ion-containing electrolyte is added. The electrolyte temperature and circulation rate are adjusted. The copper ion concentration in the electrolyte is 35-55 g / L, the sulfuric acid concentration is 150-200 g / L, the electrolyte temperature is 55-70℃, the electrolyte circulation rate is 25-40 L / min, and the arsenic content in the low-arsenic copper anode plate is 12 ppm. S2) Next, add the copper powder inhibitor to the circulation tank, and then continuously and evenly add the copper powder inhibitor from the circulation tank to the high-level tank, adjusting the current density to 300 A / m. 2 Electrolysis is carried out for 11 days; The copper powder inhibitor includes bone glue, thiourea, hydrochloric acid, and additives; the amount added to the electrolyte is as follows: bone glue concentration is 1-5 mg / L, thiourea concentration is 1-5 mg / L, hydrochloric acid concentration is 35-75 mg / L, and additive concentration is 5-50 mg / L. The additive is one or more of hydrogen peroxide, persulfate, sodium persulfate, hypochlorous acid, formic acid, and peracetic acid, or the additive is dinitrosalicylic acid, or the additive is a mixed solution of persulfate and bipyridine.

2. The method according to claim 1, characterized in that, The low-arsenic copper anode plate in S1) is placed in the electrolytic cell and first thoroughly rinsed with electrolyte for 1-10 hours; the cathode is made of 316L stainless steel.

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