Method for processing anode sludge
View Patent ↗The invention relates to a hydrometallurgical method for separating the precious metals and impurities of anode sludge obtained from copper electrolysis. According to the method, anode sludge copper is separated in atmospheric leaching; calcinated in two steps for separating selenium and for sulfatizing silver; the sulfatized silver is separated by leaching into a neutral aqueous solution, from which it can be separated by reduction or by extraction.
1. A hydrometallurgical method for separating valuable metals and impurities from anode sludge obtained from copper electrolysis and containing at least 30% copper, wherein the method comprises:
(a) leaching the anode sludge at atmospheric pressure in a sulfuric acid solution in the presence of oxygen, at a temperature of 80-100° C. for dissolving some copper from the sludge while leaving silver, gold, platinum metals and residual copper in the sludge,
(b) removing the copper solution from the sludge such that the copper content of the sludge is at least 3%,
(c) calcinating the sludge in a first step for removing selenium as selenium dioxide and in a second step for sulfatizing silver and copper in the sludge,
(d) leaching the sludge into a neutral aqueous solution for dissolving sulfatized silver and copper while leaving gold and platinum metals in the residue,
(e) separating silver from the aqueous solution,
(f) separating gold from the residue obtained from silver and copper leaching, and
(g) separating platinum metals from the residue obtained from gold separation.
2. A method according to claim 1 , wherein step (a) comprises leaching the anode sludge at a temperature of 95- 100° C.
3. A method according to claim 1 , wherein step (a) comprises leaching the anode sludge in the presence of air or oxygen gas.
4. A method according to claim 1 , wherein the first calcination step comprises calcinating the sludge at a temperature of 450-600° C. for oxidizing selenium and for creating SeO 2 gas.
5. A method according to claim 4 , wherein the first calcination step oxidizes the selenium using oxygen bearing gas.
6. A method according to claim 1 , wherein the first calcination step oxidizes the selenium using oxygen bearing gas and sulfur dioxide.
7. A method according to claim 1 , wherein the first calcination step oxidizes the selenium using oxygen and sulfur trioxide.
8. A method according to claim 1 , wherein the second calcination step comprises calcinating with concentrated sulfuric acid.
9. A method according to claim 1 , wherein the second calcination step is carried out in a calcination furnace after the first calcination step, at a lower temperature than the first calcination step.
10. A method according to claim 9 , wherein the second calcination step is carried out at a temperature of 300-420° C.
11. A method according to claim 1 , wherein step (d) comprises leaching at a temperature of 80-100° C.
12. A method according to claim 1 , wherein step (e) comprises separating silver from aqueous solution by cementing with copper.
13. A method according to claim 12 , comprising cementing silver with a copper bar or a copper plate, so that the solution flow on the copper surface is maintained high.
14. A method according to claim 1 , wherein step (e) comprises separating silver from the aqueous solution by extraction.
15. A method according to claim 1 , wherein step (e) comprises separating silver from the aqueous solution by electrolysis.
16. A method according to claim 1 , comprising leaching the leaching residue of step (a) into sulfuric acid for leaching and separating impurities.
17. A method according to claim 16 , wherein the sulfuric acid content is at least 400 g/l.
18. A method according to claim 1 , comprising separating valuable metals of the sludge from the leaching residue after neutral leaching by leaching into hydrochloric acid by means of an oxidizing agent and separating gold from the solution by reducing the gold and the platinum metals.
19. A method according to claim 18 , comprising treating the leaching residue from chloride leaching with concentrated sulfuric acid.
20. A method according to claim 19 , comprising using the acid solution from leaching with concentrated sulfuric acid as a silver sulfatizing agent in the second calcination step.
21. A method according to claim 18 , comprising separating gold by reducing with SO 2 gas.
22. A method according to claim 18 , comprising separating gold by extracting with dibutyl carbitol.
23. A method according to claim 18 , comprising separating platinum group metals from the hydrochloric acid solution by cementing with iron.
24. A method according to claim 1 , wherein after step (b) the copper content of the sludge is at least 10%.