阅读说明：本技术 一种并流沉淀法降低铜电解过程漂浮阳极泥的方法 (Method for reducing floating anode mud in copper electrolysis process by parallel flow precipitation method ) 是由 吴克富 姚夏妍 李学国 关甫江 李银丽 牛永胜 鲁兴武 李俞良 程亮 于 2020-05-22 设计创作，主要内容包括：本发明一种并流沉淀法降低铜电解过程漂浮阳极泥的方法,以解决由于漂浮阳极泥引起的阴极铜长粒子的问题,本发明通过Na<Sub>2</Sub>SO<Sub>3</Sub>在电解过程调节Sb、Bi的价电子数,通过H<Sub>2</Sub>O<Sub>2</Sub>在电解过程调节As的价电子数,将漂浮阳极泥转变为沉淀阳极泥,防止阴极铜表面生成阳极泥粒子,提高阴极铜的表观质量。(The invention discloses a method for reducing floating anode mud in a copper electrolysis process by a parallel-flow precipitation method, which aims to solve the problem of long cathode copper particles caused by the floating anode mud 2 SO 3 Adjusting the valence electron numbers of Sb and Bi in the electrolytic process through H 2 O 2 The valence electron number of As is adjusted in the electrolytic process, the floating anode mud is converted into the precipitated anode mud, anode mud particles are prevented from being generated on the surface of cathode copper, and the apparent quality of the cathode copper is improved.)

1. A method for reducing floating anode mud in a copper electrolysis process by a cocurrent precipitation method is characterized by comprising the following steps:

step 1: measurement of Cu in electrolyte²⁺、H₂SO₄And the concentration of other impurity ions, when the concentration of copper ions is 40-50g/L and the concentration of sulfuric acid is 160-180g/L, the concentration of Na is 400-500mg/L₂SO₃Adding the mixture in a dripping mode, wherein the dripping flow rate is 10-15 drops/min; adding 30% hydrogen peroxide in a dropwise manner at a dropping flow rate of 20-30 drops/min after 10 times dilution, then measuring electrolyte, slowly feeding the electrolyte from a high-level tank, starting a steam heating device, feeding the electrolyte into an electrolytic tank, a low-level tank and a pipeline, starting a circulating pump to control the temperature of the electrolyte to be 50-65 ℃, and then reading the flow according to the flow displayed by a flowmeter to enable the temperature of the electrolyte to reach 30-35L/min;

step 2: after the magnetization is finished, the copper anode and the starting sheet are placed in an electrolytic bath, and the area S of the starting sheet entering the electrolyte is calculated₃The formula J according to the current density is current/S₃Determining the magnitude of the current, wherein the current density: 220 to 280A/m²After the current is determined, the direct current power supply is turned on to start electrolysis, and the weight ratio of gelatin: 20-150 g/t, thiourea: 20-150 g/t, hydrochloric acid: dripping hydrochloric acid, thiourea and gelatin in an amount of 100-250 g/t;

and step 3: after the electrolysis test is finished, the residual anode and the cathode copper are taken out, boiled and washed by dilute sulfuric acid, dried in vacuum and weighed.

2. The method for reducing floating anode slime in copper electrolysis by using cocurrent precipitation according to claim 1, wherein the method comprises the following steps: in said step 1 Na₂SO₃The dropping flow rate of (2) was 10 drops/min.

3. The method for reducing floating anode slime in copper electrolysis by using cocurrent precipitation according to claim 1, wherein the method comprises the following steps: the dropping flow rate of the hydrogen peroxide in the step 1 is 20 drops/min.

4. The method for reducing floating anode slime in copper electrolysis by using cocurrent precipitation according to claim 1, wherein the method comprises the following steps: the temperature of the electrolyte in the step 1 is controlled at 60 ℃.

5. The method for reducing floating anode slime in copper electrolysis by using cocurrent precipitation according to claim 1, wherein the method comprises the following steps: in the step 2, the dripping amount of the gelatin is 80g/t, the dripping amount of the thiourea is 80g/t, and the dripping amount of the hydrochloric acid is 150 g/t.

Technical Field

The invention relates to the technical field of copper electrolysis smelting, in particular to a method for reducing floating anode mud in a copper electrolysis process by a parallel flow precipitation method.

Background

Electrolytic refining is the main method for producing high-purity copper. The high-purity copper is obtained from crude copper through electrolysis, the electrolyte of the high-purity copper inevitably contains impurities such As arsenic, antimony, bismuth and the like, when the valence electron number and the content of the arsenic, the antimony and the bismuth are changed, the precipitated anode mud is converted into floating anode mud, the As ion concentration is 10-30g/L, the Sb and Bi ion concentration is more easily formed in the copper electrolysis process within the range of 0.1-1g/L, and the floating anode mud is SbAsO formed by As, Sb and Bi in different valence states₄、BiAsO₄The floating anode mud is light in specific gravity, easy to suspend in electrolyte, low in solubility and high in surface activity, is easy to attach to cathode copper, is particularly easy to generate anode mud particles, influences the apparent quality of the cathode copper, and accelerates the formation of the floating anode mud when the concentration of As, Sb and Bi ions in the electrolyte exceeds a standard, so that the amount of the floating anode mud in the copper electrolyte can be reduced by adjusting and maintaining proper concentration and valence electron number of the As, Sb and Bi ions. Therefore, the main task of reducing the floating anode slime of the copper electrolyte is to promote the valence electron number of As in the electrolyte to be increased, reduce the valence electron number of antimony bismuth and promote As, Sb and Bi to form the precipitated anode slime in the electrolytic process. Based on this, the invention passes Na₂SO₃The valence electron number of Sb and Bi is reduced in the electrolytic process through H₂O₂The valence electron number of As is increased in the electrolytic process, the quantity of floating anode mud formed by As, Sb and Bi in the electrolytic process is reduced, and the influence on the quality of cathode copper is reduced.

Disclosure of Invention

The invention aims to provide a method for reducing floating anode mud in a copper electrolysis process by a cocurrent flow precipitation method, which can reduce the number of counter-cathode copper particles, improve the apparent quality of cathode copper and improve the economic benefit of enterprises.

In order to achieve the purpose, the invention discloses a method for reducing floating anode mud in a copper electrolysis process by a cocurrent flow precipitation method, which is characterized by comprising the following steps:

step 1: measurement of Cu in electrolyte²⁺、H₂SO₄And the concentration of other impurity ions, when the concentration of copper ions is 40-50g/L and the concentration of sulfuric acid is 160-180g/L, the concentration of Na is 400-500mg/L₂SO₃Adding the mixture in a dripping mode, wherein the dripping flow rate is 10-15 drops/min; adding 30% hydrogen peroxide in a dropwise manner at a dropping flow rate of 20-30 drops/min after 10 times dilution, then measuring electrolyte, slowly feeding the electrolyte from a high-level tank, starting a steam heating device, feeding the electrolyte into an electrolytic tank, a low-level tank and a pipeline, starting a circulating pump to control the temperature of the electrolyte to be 50-65 ℃, and then reading the flow according to the flow displayed by a flowmeter to enable the temperature of the electrolyte to reach 30-35L/min;

step 2: after the magnetization is finished, the copper anode and the starting sheet are placed in an electrolytic bath, and the area S of the starting sheet entering the electrolyte is calculated₃The formula J according to the current density is current/S₃Determining the magnitude of the current, wherein the current density: 220 to 280A/m²After the current is determined, the direct current power supply is turned on to start electrolysis, and the weight ratio of gelatin: 20-150 g/t, thiourea: 20-150 g/t, hydrochloric acid: dripping hydrochloric acid, thiourea and gelatin in an amount of 100-250 g/t;

and step 3: after the electrolysis test is finished, the residual anode and the cathode copper are taken out, boiled and washed by dilute sulfuric acid, dried in vacuum and weighed.

In the technical scheme of the method for reducing floating anode mud in the copper electrolysis process by using the parallel-flow precipitation method, the further preferable technical scheme is characterized in that:

1. in said step 1 Na₂SO₃The dropping flow rate of (2) is 10 drops/min;

2. the dropping flow rate of the hydrogen peroxide in the step 1 is 20 drops/min;

3. the temperature of the electrolyte in the step 1 is controlled at 60 ℃;

4. in the step 2, the dripping amount of the gelatin is 80g/t, the dripping amount of the thiourea is 80g/t, and the dripping amount of the hydrochloric acid is 150 g/t.

Compared with the prior art, the invention has the beneficial effects that: anode mud passing through Na₂SO₃The valence electron number of Sb and Bi is reduced in the electrolytic process through H₂O₂The valence electron number of As is increased in the electrolytic process, the quantity of floating anode mud formed by As, Sb and Bi in the electrolytic process is reduced, the number of counter-cathode copper particles is reduced, the apparent quality of cathode copper and the economic benefit of enterprises are improved, and no arsine detector is arranged in the whole operation process.

Detailed Description

The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.