High-efficiency self-cleaning inducer for copper electrolyte and synthesis method thereof

Abstract

The application discloses a kind of copper electrolyte high-efficiency self-cleaning inducing agent and synthesis method thereof, comprising the following steps: S1, titanium sulfate is mixed with sulfuric acid solution and is calcined at 150-300 degrees Celsius;S2, the material obtained by calcining in step S1 is finely ground to more than 80% of-300 mesh;S3, using the mass concentration 20%-30% sulfuric acid solution, the material after fine grinding in step S2 is soaked, then filtered, and the obtained solid material is the final copper electrolyte high-efficiency self-cleaning inducing agent.The self-cleaning inducing agent synthesized by the application can be regenerated and reused.Using the self-cleaning inducing agent prepared by the synthesis method of the application for electrolyte purification can avoid the problems of high energy consumption and easy production of toxic and harmful gases that harm the environment in traditional processes, achieving carbon reduction and clean production.The self-cleaning inducing agent prepared by the synthesis method of the application has the advantages of high purification efficiency, simple synthesis method, low cost, environmental friendliness, recyclability and the like.

Description

Technical Field

[0001] This invention relates to the field of copper electrolysis technology, specifically to a highly efficient self-purification inducer for copper electrolyte and its synthesis method. Background Technology

[0002] During copper electrolytic refining, impurities such as arsenic, antimony, bismuth, and nickel in the anode continuously dissolve and accumulate in the electrolyte. When these impurities reach a certain concentration, they affect the quality of the cathode copper. To maintain the copper, acid, and impurity concentrations in the electrolyte within permissible ranges, the electrolyte must be purified and adjusted to ensure the normal operation of the electrolysis process. The current mainstream purification process involves discharging a portion of the electrolyte in an open circuit, then concentrating the electrolyte to be purified through vacuum evaporation → water-cooled crystallization to produce crude copper sulfate → continuous removal of copper and impurities such as arsenic, antimony, and bismuth using an induced process → and finally, cryogenic crystallization to produce crude nickel sulfate. Although this process has been used for many years and has become relatively mature through continuous optimization and improvement, achieving good results, it still suffers from problems such as complex processes, high costs for equipment, reagents, and energy, environmental pollution, and the potential generation of toxic arsine gas during production, endangering the safety of workers. Summary of the Invention

[0003] To address the shortcomings of existing technologies, this invention aims to provide a highly efficient self-purification inducer for copper electrolytes.

[0004] To achieve the above objectives, the present invention adopts the following technical solution:

[0005] A method for synthesizing a highly efficient self-purification inducer for copper electrolyte includes the following steps:

[0006] S1. Mix titanium sulfate with sulfuric acid solution and calcine at 150-300 degrees Celsius;

[0007] S2. Grind the material obtained from roasting in step S1 to a fineness of -300 mesh or higher (80%).

[0008] S3. Soak the finely ground material from step S2 in a sulfuric acid solution with a mass concentration of 20%-30%, then filter it. The resulting solid substance is the final high-efficiency self-purification inducer for copper electrolyte.

[0009] Furthermore, in step S1, the sulfuric acid solution has a mass concentration of 98% and is used in an amount that is 1-1.5 times the mass of titanium sulfate.

[0010] Furthermore, in step S1, the roasting time is 2-3 hours.

[0011] The present invention also provides a highly efficient self-purification inducer for copper electrolyte prepared by the above method.

[0012] The present invention also provides a method for using the highly efficient self-purification inducer for copper electrolyte prepared by the above method, specifically including the following steps:

[0013] A1. Heat the electrolyte to be purified and add Sb2O5 to remove bismuth;

[0014] A2. Add a highly efficient self-purification inducer to the copper electrolyte to achieve adsorption and co-precipitation of arsenic, antimony, and bismuth;

[0015] A3. The high-efficiency self-purification inducer of the copper electrolyte after adsorption and co-precipitation is regenerated and reused.

[0016] Further, in step A1, the electrolyte to be purified is heated to 60°C, and Sb2O5 is added at a dosage of 5 g / L while stirring, and the reaction time is 1 h.

[0017] Further, in step A2, a copper electrolyte high-efficiency self-purification inducer is added to the electrolyte that has been heated and bismuth removed in step A1 at a dosage of 10 g / L, and stirring is started at the same time. The adsorption and co-precipitation time is 2 hours, and then filtration is performed.

[0018] Further, the specific process of step A3 is as follows: the copper electrolyte high-efficiency self-purification inducer after adsorption and co-precipitation is mixed with water, NaOH solution is added to adjust the pH to 8-13, and desorption is carried out by stirring at 50-100℃ for 1-4 hours. The regenerated copper electrolyte high-efficiency self-purification inducer and the desorbed liquid are obtained by filtration. The regenerated copper electrolyte high-efficiency self-purification inducer is reused after acid washing.

[0019] The beneficial effects of this invention are as follows:

[0020] (1) This invention provides a method for synthesizing a copper electrolyte self-purification inducer. The synthesized self-purification inducer can be regenerated and reused, thereby achieving self-sufficiency and infinite recycling of the self-purification inducer. The self-purification inducer can be used to achieve rapid and autonomous adjustment of the electrolyte composition of the electrolysis system.

[0021] (2) The self-purifying inducer prepared by the synthesis method of this invention is used to purify the electrolyte. The basic principle of purification is the complexation precipitation method, that is, firstly, Sb2O5 is used to complex Bi(III) in the electrolyte, and then TiOSO4, Ti4O5(SO4)3, and Ti7O are added as the main components. 13 The self-purifying inducer of SO4 involves various titanium oxides that complex with As(III), As(V), Sb(III), and Sb(V) in the electrolyte, ultimately achieving the co-precipitation of arsenic, antimony, and bismuth elements in the electrolyte, thus purifying the electrolyte. Purifying the electrolyte through this process avoids the high energy consumption and environmental hazards associated with traditional processes, achieving carbon reduction and cleaner production.

[0022] (3) The self-purification inducer prepared by the synthesis method of the present invention has the advantages of high purification efficiency, simple synthesis method, low cost, environmental friendliness and recyclability. Attached Figure Description

[0023] Figure 1 This is a flowchart of the synthesis method of the high-efficiency self-purification inducer for copper electrolyte of the present invention;

[0024] Figure 2 This is a flowchart illustrating the method of using the high-efficiency self-purification inducer for copper electrolyte of the present invention. Detailed Implementation

[0025] The present invention will be further described below with reference to the accompanying drawings. It should be noted that this embodiment is based on the present technical solution and provides detailed implementation methods and specific operation processes, but the protection scope of the present invention is not limited to this embodiment.

[0026] Example 1

[0027] like Figure 1 As shown, 50g of titanium sulfate was mixed with 60g of 98% concentrated sulfuric acid, stirred evenly, and then placed in a muffle furnace for calcination at 200℃ for 3 hours. After calcination, the calcined residue was ground to at least 80% of -300 mesh, and then soaked in 20% sulfuric acid for 1 hour. The residue was then filtered to obtain the final high-efficiency self-purification inducer for copper electrolyte. The main components of the product obtained by calcining titanium sulfate with H2SO4 were TiOSO4, Ti4O5(SO4)3, and Ti7O4. 13 (SO4).

[0028] like Figure 2 As shown, the high-efficiency self-purifying inducer for copper electrolyte prepared according to the method is used to purify the electrolyte. The specific process is as follows:

[0029] Add 1 L of electrolyte to a beaker and heat to 60 °C in a constant temperature water bath with stirring. First, add 5 g of Sb₂O₅ and react for 1 hour. Then, add 10 g of copper electrolyte high-efficiency self-purification inducer and continue stirring for 2 hours. After adsorption, cool to 28–32 °C without stirring the liquid. After cooling, perform vacuum filtration. The filtrate is the purified electrolyte. Wash the filter residue with water. After washing, desorb the filter residue: add 20 ml of pure water to the filter residue, stir, and adjust the pH to 8 with 20% sodium hydroxide solution. Stir at 50 °C for 4 hours to desorb (As, Sb, and Bi desorption rates all reach over 85%). The purified electrolyte after desorption is washed with sulfuric acid at pH 1.5 and then filtered before reuse. The comparison of electrolyte composition before and after self-purification is shown in Table 1.

[0030] Table 1

[0031] Cu As Sb Bi <![CDATA[H2SO4]]> g / L before adsorption 43.2 14.28 0.56 0.63 183.7 After adsorption g / L 43.4 0.98 0.031 0.045 181.4

[0032] Example 2

[0033] like Figure 1 As shown, 50g of titanium sulfate was mixed with 75g of 98% concentrated sulfuric acid, stirred evenly, and then placed in a muffle furnace for calcination at 150℃ for 2 hours. After calcination, the calcined residue was ground to at least 80% of -300 mesh, and then soaked in 30% sulfuric acid for 1 hour. The final electrolyte self-purifying agent was obtained by filtration. The main components of the product obtained by calcining titanium sulfate with H2SO4 were TiOSO4, Ti4O5(SO4)3, and Ti7O4. 13 (SO4).

[0034] like Figure 2 As shown, the high-efficiency self-purifying inducer for copper electrolyte prepared according to the method is used to purify the electrolyte. The specific process is as follows:

[0035] Add 1 L of electrolyte to a beaker and heat to 60 °C in a constant temperature water bath with stirring. First, add 5 g of Sb₂O₅ and react for 1 hour. Then, add 10 g of copper electrolyte high-efficiency self-purification inducer and continue stirring for 2 hours. After adsorption, cool to 28–32 °C without stirring the liquid. After cooling, perform vacuum filtration. The filtrate is the purified electrolyte. Wash the filter residue with water. After washing, desorb the filter residue: add 20 ml of pure water to the filter residue, stir, and adjust the pH to 12 with 20% sodium hydroxide solution. Stir at 80 °C for 1.5 hours to desorb (As, Sb, and Bi desorption rates all reach over 85%). The purified electrolyte after desorption is washed with sulfuric acid at pH 1.5 and then filtered before reuse. The comparison of electrolyte composition before and after self-purification is shown in Table 2.

[0036] Table 2

[0037] Cu As Sb Bi <![CDATA[H2SO4]]> g / L before adsorption 45.8 14.27 0.51 0.58 187.2 After adsorption g / L 44.9 1.21 0.028 0.034 184.6

[0038] Example 3

[0039] like Figure 1 As shown, 50g of titanium sulfate was added to 50g of 98% concentrated sulfuric acid, stirred evenly, and then placed in a muffle furnace for calcination at 300℃ for 3 hours. After calcination, the calcined residue was ground to at least 80% of -300 mesh. The ground material was then soaked in 20% sulfuric acid for 1 hour, and filtered to obtain the final electrolyte self-purifying agent. The main components of the product obtained by calcining titanium sulfate with H2SO4 were TiOSO4, Ti4O5(SO4)3, and Ti7O4. 13 (SO4).

[0040] like Figure 2 As shown, the high-efficiency self-purifying inducer for copper electrolyte prepared according to the method is used to purify the electrolyte. The specific process is as follows:

[0041] Add 1L of electrolyte to a beaker and heat to 60℃ in a constant temperature water bath with stirring. First, add 5g of Sb₂O₅ and react for 1 hour. Then, add 10g of copper electrolyte high-efficiency self-purification inducer and continue stirring for 2 hours. After adsorption, cool to 28-32℃ without stirring the liquid. After cooling, perform vacuum filtration. The filtrate is the purified electrolyte. Wash the filter residue with water. After washing, desorb the filter residue: add 20ml of pure water to the filter residue, stir, and adjust the pH to 10 with 20% sodium hydroxide solution. Stir at 50℃ for 3 hours to desorb (As, Sb, and Bi desorption rates all reach over 85%). The purified electrolyte after desorption is washed with sulfuric acid at pH 1.5 and then filtered before reuse. The comparison of electrolyte composition before and after self-purification is shown in Table 3.

[0042] Table 3

[0043] Cu As Sb Bi <![CDATA[H2SO4]]> g / L before adsorption 46.2 14.35 0.49 0.61 189.0 After adsorption g / L 45.7 1.26 0.031 0.039 187.2

[0044] Example 4

[0045] like Figure 1 As shown, 50g of titanium sulfate was mixed with 70g of 98% concentrated sulfuric acid, stirred evenly, and then placed in a muffle furnace for calcination at 180℃ for 2 hours. After calcination, the calcined residue was ground to at least 80% of -300 mesh. The ground material was then soaked in 30% sulfuric acid for 1 hour and filtered to obtain the final electrolyte self-purifying agent. The main components of the product obtained by calcining titanium sulfate with H2SO4 were TiOSO4, Ti4O5(SO4)3, and Ti7O4. 13 (SO4).

[0046] like Figure 2 As shown, the high-efficiency self-purifying inducer for copper electrolyte prepared according to the method is used to purify the electrolyte. The specific process is as follows:

[0047] Add 1L of electrolyte to a beaker and heat to 60℃ in a constant temperature water bath with stirring. First, add 5g of Sb₂O₅ and react for 1 hour. Then, add 10g of copper electrolyte high-efficiency self-purification inducer and continue stirring for 2 hours. After adsorption, cool to 28-32℃ without stirring the liquid. After cooling, perform vacuum filtration. The filtrate is the purified electrolyte. Wash the filter residue with water. After washing, desorb the filter residue: add 20ml of pure water to the filter residue, stir, and adjust the pH to 13 with 20% sodium hydroxide solution. Stir at 100℃ for 1 hour to desorb (As, Sb, and Bi desorption rates all reach over 85%). The purified electrolyte after desorption is washed with sulfuric acid at pH=1.5 and then filtered before reuse. The comparison of electrolyte composition before and after self-purification is shown in Table 4.

[0048] Table 4

[0049]

[0050]

[0051] For those skilled in the art, various corresponding changes and modifications can be made based on the above technical solutions and concepts, and all such changes and modifications should be included within the protection scope of the claims of this invention.

Claims

1. A method for synthesizing a highly efficient self-purification inducer for copper electrolyte, characterized in that, Includes the following steps: S1. Mix titanium sulfate with sulfuric acid solution and calcine at 150-300 degrees Celsius; the sulfuric acid solution has a mass concentration of 98% and is used in an amount of 1-1.5 times the mass of titanium sulfate, and the calcine time is 2-3 hours. S2. Grind the material obtained from roasting in step S1 to a fineness of -300 mesh or higher (80%). S3. Soak the finely ground material from step S2 in a sulfuric acid solution with a mass concentration of 20%-30%, then filter it. The resulting solid substance is the final high-efficiency self-purification inducer for copper electrolyte.

2. A highly efficient self-purifying inducer for copper electrolyte prepared by the method of claim 1.

3. A method for using a highly efficient self-purifying inducer for copper electrolyte prepared by the method of claim 1, characterized in that, Specifically, the steps include the following: A1. Heat the electrolyte to be purified and add Sb2O5 to remove bismuth; A2. Add a highly efficient self-purification inducer to the copper electrolyte to achieve adsorption and co-precipitation of arsenic, antimony, and bismuth; A3. The high-efficiency self-purification inducer of the copper electrolyte after adsorption and co-precipitation is regenerated and reused.

4. The method of use according to claim 3, characterized in that, In step A1, the electrolyte to be purified is heated to 60°C, and Sb2O5 is added at a dosage of 5 g / L while stirring. The reaction time is 1 hour.

5. The method of use according to claim 3, characterized in that, In step A2, add the copper electrolyte high-efficiency self-purification inducer at a dosage of 10 g / L to the electrolyte that has been heated and bismuth removed in step A1, and start stirring at the same time. The adsorption and co-precipitation time is 2 hours, and then filter after the adsorption and co-precipitation are completed.

6. The method of use according to claim 3, characterized in that, The specific process of step A3 is as follows: the high-efficiency self-purification inducer of copper electrolyte after adsorption and co-precipitation is mixed with water, NaOH solution is added to adjust the pH to 8-13, and desorption is carried out by stirring at 50-100℃ for 1-4 hours. The regenerated high-efficiency self-purification inducer of copper electrolyte and the desorbed liquid are obtained by filtration. The regenerated high-efficiency self-purification inducer of copper electrolyte is reused after acid washing.

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