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CN-121992202-A - Recovery method of copper anode electrolytic precipitation slag

CN121992202ACN 121992202 ACN121992202 ACN 121992202ACN-121992202-A

Abstract

The invention discloses a method for recycling copper anode electrolytic precipitation slag, and relates to the technical field of resource recycling. The invention firstly mixes and bakes copper anode electrolytic precipitation slag and auxiliary agent, and then carries out water leaching on the obtained roasting slag. In the roasting stage, the molar ratio of arsenic to tin in the copper anode electrolytic precipitation slag is less than 1.6, so that the volatilization rate of arsenic can be improved, and meanwhile, copper and nickel can be completely converted into water-soluble compounds in the low-temperature roasting process, so that the arsenic, copper and nickel and tin and lead can be separated and recovered respectively.

Inventors

  • LI JUN
  • MAO ANZHANG
  • LIU XIAOWEN
  • ZHOU ZHAOAN

Assignees

  • 广东飞南资源利用股份有限公司

Dates

Publication Date
20260508
Application Date
20260226

Claims (10)

  1. 1. A method for recovering copper anode electrolytic precipitation slag, comprising: Mixing and roasting copper anode electrolytic precipitation slag and an auxiliary agent to obtain roasting slag and arsenic-containing flue gas, wherein the molar ratio of arsenic to tin in the copper anode electrolytic precipitation slag is less than 1.6, and the auxiliary agent comprises sulfuric acid and sulfate; And leaching the roasting slag by water to obtain water leaching slag and copper-nickel solution.
  2. 2. The recycling method according to claim 1, wherein the roasting temperature is controlled to be 350 ℃ to 500 ℃ and the roasting time is controlled to be 1h to 5h; Preferably, the roasting temperature is controlled to be 350-400 ℃ and the roasting time is controlled to be 2-4 h.
  3. 3. The method according to claim 1, wherein the auxiliary agent is obtained by mixing concentrated sulfuric acid and sulfate, the mass ratio of the added amount of the concentrated sulfuric acid to the copper anode electrolytic precipitation slag is (60-120): 100, and the mass ratio of the added amount of the sulfate to the copper anode electrolytic precipitation slag is (10-40): 100, wherein the concentrated sulfuric acid is a sulfuric acid aqueous solution with a mass fraction of 98.3%; preferably, the auxiliary agent is obtained by mixing concentrated sulfuric acid and sulfate, wherein the mass ratio of the added amount of the concentrated sulfuric acid to the copper anode electrolytic precipitation slag is (70-90): 100, and the mass ratio of the added amount of the sulfate to the copper anode electrolytic precipitation slag is (20-30): 100.
  4. 4. A recovery method according to any one of claims 1 to 3, wherein the sulphate is selected from at least one of sodium sulphate, potassium sulphate and ammonium sulphate.
  5. 5. The recovery method according to claim 1, wherein the temperature of the water immersion is controlled to be 15 ℃ to 35 ℃ and the time of the water immersion is controlled to be 0.5h to 2.0h during the water immersion.
  6. 6. The method according to claim 1 or 5, wherein the mass of water corresponding to 1kg of the roasting slag is controlled to be 6L-12L during the water leaching process.
  7. 7. The recovery method according to claim 1, wherein the copper-nickel solution is returned to the water leaching stage and is sent to an electrolysis or extraction process for recovery of copper-nickel after copper ions are greater than 45 g/L.
  8. 8. The recovery method according to claim 1, wherein the dry basis in the copper anode electrolytic precipitation slag contains arsenic 10% -20%, tin 8% -17%, copper 9% -20%, nickel 1% -3%, lead 3% -8%, antimony 5% -10% and iron 0.1% -1.2% by mass.
  9. 9. The recovery method of claim 1, wherein the copper anode electrolytic precipitation slag is ground and then calcined.
  10. 10. The recovery method of claim 9, wherein the mass ratio of particles smaller than 325 mesh is greater than 80% after grinding.

Description

Recovery method of copper anode electrolytic precipitation slag Technical Field The invention relates to the technical field of resource recovery, in particular to a method for recovering copper anode electrolytic precipitation slag. Background The precipitate slag produced in the anodic electrolytic refining process of nickel-copper containing high arsenic Gao Xigao is rich in copper, nickel, tin, arsenic, antimony and lead, and a small amount of noble metals, and is mainly used for leaching copper-nickel by wet oxygen pressure or strong oxidation, and the rest slag is subjected to strong reduction, vulcanization and smelting treatment to recover valuable metals such as tin, antimony and the like. Because the oxygen pressure needs expensive oxygen autoclave equipment, the direct strong reduction sulfidation smelting can dilute the enrichment ratio of noble metals because of the excessive copper content of the materials and the burden, and the integral strong reduction sulfidation smelting needs to add a large amount of vulcanizing agent, the grade of the obtained copper product (the copper matte produced by the strong reduction sulfidation smelting) is too low, and the cost of the strong reduction sulfidation smelting treatment and the subsequent deep processing is greatly increased. Therefore, development of a recovery process for the precipitate slag produced in the electrolytic refining process of the high-arsenic Gao Xigao nickel-copper anode is needed at present, so that low-cost recovery and utilization of resources are realized. In view of this, the present invention has been made. Disclosure of Invention The invention aims to provide a recovery method of copper anode electrolytic precipitation slag, which aims to provide a low-cost recovery process for high-impurity copper anode electrolytic precipitation slag and improve the recovery rate of each element. The invention is realized in the following way: in a first aspect, the invention provides a method for recovering copper anode electrolytic precipitation slag, comprising: Mixing and roasting copper anode electrolytic precipitation slag and an auxiliary agent to obtain roasting slag and arsenic-containing flue gas, wherein the molar ratio of arsenic to tin in the copper anode electrolytic precipitation slag is less than 1.6; and leaching the roasting slag by water to obtain water leaching slag and copper-nickel solution. In an alternative embodiment, the roasting temperature is controlled to be 350-500 ℃ and the roasting time is controlled to be 1-5 h; Preferably, the roasting temperature is controlled to be 350-400 ℃ and the roasting time is controlled to be 2-4 h. In an alternative embodiment, the auxiliary agent is obtained by mixing concentrated sulfuric acid and sulfate, wherein the mass ratio of the added amount of the concentrated sulfuric acid to the copper anode electrolytic precipitation slag is (60-120): 100, and the mass ratio of the added amount of the sulfate to the copper anode electrolytic precipitation slag is (10-40): 100, and the concentrated sulfuric acid is a sulfuric acid aqueous solution with the mass fraction of 98.3%; Preferably, the auxiliary agent is obtained by mixing concentrated sulfuric acid and sulfate, wherein the mass ratio of the added amount of the concentrated sulfuric acid to the copper anode electrolytic precipitation slag is (70-90) 100, and the mass ratio of the added amount of the sulfate to the copper anode electrolytic precipitation slag is (20-30) 100. In an alternative embodiment, the sulfate is selected from at least one of sodium sulfate, potassium sulfate, and ammonium sulfate. In an alternative embodiment, the temperature of the water immersion is controlled to be 15-35 ℃ and the time of the water immersion is 0.5-2.0 h. In an alternative embodiment, during the water immersion process, the mass of 1kg of roasting slag corresponding to water is controlled to be 6L-12L. In an alternative embodiment, the copper nickel solution is returned to the water leaching stage and after copper ions are greater than 45g/L, is sent to an electrolysis or extraction process for recovery of copper nickel. In an alternative embodiment, the dry basis in the copper anode electrolytic precipitation slag contains, by mass, 10% -20% arsenic, 8% -17% tin, 9% -20% copper, 1% -3% nickel, 3% -8% lead, 5% -10% antimony, and 0.1% -1.2% iron. In an alternative embodiment, the copper anode electrolytic precipitation slag is first ground and then calcined. In an alternative embodiment, the mass ratio of particles smaller than 325 meshes is more than 80 percent after grinding. The invention has the following beneficial effects that the copper anode electrolytic precipitation slag and the auxiliary agent are mixed and roasted, and then the obtained roasting slag is immersed in water. In the roasting stage, the molar ratio of arsenic to tin in the copper anode electrolytic precipitation slag is less than 1.6, so that the arsenic vola