Process for recycling junk lead-acid batteries

• US 4,118,219 A
• Filed: 07/01/1977
• Issued: 10/03/1978
• Est. Priority Date: 02/19/1976
• Status: Expired due to Term

• Current Assignee: GNB Batteries, Inc. (Transdigm Group Incorporated)
• Original Assignee: Gould, Inc. (Transdigm Group Incorporated)
• Inventors: Klang, James Kenneth, Elmore, Marion Edward
• Primary Examiner(s): Ozaki, G.
• Application Number:
  US05/812,437
• Time in Patent Office: 459 Days
• Field of Search: 75/77, 75/120, 75/103, 423/92, 423/98, 423/433, 423/539, 423/619
• US Class Current: 75/432
• CPC Class Codes: H01M 10/54 Reclaiming serviceable parts of waste accumulators
• CPC Class Codes: Y02W 30/84 Recycling of batteries or fuel cells

Abstract

A hydrometallurgical process for recycling the paste and electrolyte of junk lead-acid batteries begins by separating the paste and electrolyte from the junk batteries. The paste and electrolyte are then reacted to increase the lead sulfate content of the paste and reduce the acid content of the electrolyte. Excess liquid is then removed from the mixture of paste and electrolyte, after which the paste is mixed with an aqueous ammoniacal ammonium sulfate solution to dissolve a substantial portion of the lead sulfate from the paste. The remaining solid materials are then separated from the resulting pregnant lead solution, after which lead carbonate is precipitated from the pregnant lead solution by the addition of ammonium carbonate, ammonium bicarbonate or carbon dioxide. The precipitated lead carbonate is removed from the spent liquid and either converted to lead oxide by calcining, or mixed with sulfuric acid and then calcined or reacted with a chemical reducing agent to convert lead dioxide therein to lead oxide, and the lead oxide-containing material is then mixed with sulfuric acid in a second sulfating reaction to increase the lead sulfate content thereof. The resulting product is mixed with an aqueous ammoniacal ammonium sulfate solution to dissolve further lead sulfate therefrom. The resulting pregnant lead solution is separated from any solid materials remaining therein, after which lead carbonate is precipitated from the solution.

Claims

1. A process for recycling the paste and electrolyte of junk lead-acid batteries, said process comprising the steps of

(a) separating the paste and electrolyte from the junk batteries,

(b) reacting the paste and electrolyte to increase the lead sulfate content of the paste and reduce the acid content of the electrolyte,

(c) mixing the resulting paste with an aqueous ammoniacal ammonium sulfae solution to dissolve a substantial portion of the lead sulfate from the paste,

(d) separating the resulting pregnant lead solution from any solid materials therein,

(e) and precipitating lead carbonate from the pregnant lead solution.

2. The process of claim 1 wherein said electrolyte contains an insufficient amount of sulfuric acid to react with all the lead oxide in said paste, and additional sulfuric acid is added to the mixture of paste and electrolyte to react with the excess lead oxide and thereby further increase the lead sulfate content of the paste.

3. The process of claim 1 wherein excess liquid is removed from the mixture of paste and electrolyte prior to mixing the paste with the aqueous ammoniacal ammonium sulfate solution.

4. The process of claim 1 wherein lead dioxide in the paste is converted to lead oxide prior to mixing with the electrolyte.

5. The process of claim 4 wherein said paste is calcined to convert the lead dioxide to lead oxide.

6. The process of claim 4 wherein a chemical reducing agent is added to the paste to convert the lead dioxide to lead oxide.

7. The process of claim 6 wherein said paste is ground before the addition of said chemical reducing agent thereto.

8. The process of claim 1 wherein the precipitated lead carbonate is removed from the mother liquor and converted to lead oxide.

9. The process of claim 1 wherein the precipitated lead carbonate is mixed with sulfuric acid and then calcined to produce basic lead sulfates.

10. The process of claim 1 wherein the precipitated lead carbonate is fed to a reduction furnace where it is converted to substantially pure lead.

11. The process of claim 1 which includes the steps of converting lead dioxide to lead oxide in the solid materials separated from the pregnant lead solution, mixing the resulting materials with sulfuric acid to increase the lead sulfate content thereof, and mixing the resulting product with an aqueous ammoniacal ammonium sulfate solution to dissolve a substantial portion of the lead sulfate therefrom.

12. The process of claim 11 wherein said solid materials separated from the pregnant lead solution are calcined to convert the lead dioxide to lead oxide.

13. The process of claim 11 wherein a chemical reducing agent is added to said solid materials separated from the pregnant lead solution to convert the lead dioxide to lead oxide.

14. The process of claim 13 wherein said solid materials are ground before the addition of said chemical reducing agent thereto.

15. The process of claim 11 which includes the steps of separating the resulting pregnant lead solution from any solid materials remaining therein, and precipitating lead carbonate from the pregnant lead solution.

16. The process of claim 1 wherein ammonium sulfate is removed from the solution from which the lead carbonate has been precipitated.

17. The process of claim 1 wherein at least a portion of the solution from which the lead carbonate has been precipitated is recycled to the aqueous ammoniacal ammonium sulfate solution.

18. The process of claim 17 wherein ammonia and ammonium sulfate are added to the recycled solution.

19. A process for recycling the paste of junk lead-acid batteries, said process comprising the steps of

(a) reacting the paste from the junk batteries with sulfuric acid to convert lead oxide therein to lead sulfate and thereby increase the lead sulfate content of the paste,

(b) mixing the resulting paste with an aqueous ammoniacal ammonium sulfate solution to dissolve a substantial portion of the lead sulfate from the paste,

(c) separating the resulting pregnant lead solution from any solid materials remaining therein,

(d) and precipitating lead carbonate from the pregnant lead solution.

20. A process for recovering lead from junk lead-acid batteries comprising the steps of

(a) removing all the internal components of the batteries, including the acid, from the battery cases and mixing said internal components together to convert lead oxide therein to lead sulfate,

(b) adding ammoniacal ammonium sulfate to said mixture to leach the lead from said mixture,

(c) precipitating lead carbonate from the resulting solution and removing the precipitate from the solution,

(d) and converting the lead carbonate to lead oxide by the removal of carbon dioxide from the carbonate.

21. A process for recovering lead from junk lead-acid batteries comprising the steps of

(a) removing all the internal components of the batteries, including the acid, from the battery cases and mixing said internal components together to convert lead oxide therein to lead sulfate,

(b) adding ammoniacal ammonium sulfate to said mixture to leach the lead from said mixture,

(c) precipitating lead carbonate from the resulting solution and removing the precipitate from the solution,

(d) and mixing the lead carbonate with sulfuric acid and then calcining the resulting mixture to produce basic lead sulfates.

22. A process for recovering lead from junk lead-acid batteries comprising the steps of

(a) removing all the internal components of the batteries, including the acid, from the battery cases and mixing said internal components together to convert lead oxide therein to lead sulfate,

(b) adding ammoniacal ammonium sulfate to said mixture to leach the lead from said mixture,

(c) precipitating lead carbonate from the resulting solution and removing the precipitate from the solution,

(d) and converting the lead carbonate to substantially pure lead in a reduction furnace.

23. A process for recycling the paste from junk lead-acid batteries, said process comprising the steps of

(a) separating a paste containing lead dioxide from the junk batteries,

(b) converting the lead dioxide in the paste to a form of lead that is soluble in an aqueous ammoniacal ammonium sulfate solution.

(c) mixing the resulting soluble lead product with an aqueous ammoniacal ammonium sulfate solution to dissolve a substantial portion of the lead from said soluble lead product,

(d) and removing the lead from the resulting pregnant lead solution.

24. The process of claim 23 wherein said lead dioxide is converted to lead oxide by calcining the paste, and said lead oxide is then converted to lead sulfate.

25. The process of claim 23 wherein said lead dioxide is converted to lead oxide by adding a chemical reducing agent to the paste, and said lead oxide is then converted to lead sulfate.

26. The process of claim 25 wherein the paste is ground before the addition of the chemical reducing agent.

27. The process of claim 23 wherein said lead dioxide is converted to lead oxide, and said lead oxide is then converted to lead sulfate by reacting the paste with electrolyte separated from the junk batteries.

28. The process of claim 23 wherein the lead is removed from said pregnant lead solution by separating said solution from any solid materials therein, and then precipitating lead carbonate from the pregnant lead solution.

29. A process for recycling the paste from junk lead-acid batteries, said process comprising the steps of

(a) separating a paste containing lead sulfate, lead oxide and lead dioxide from the junk batteries,

(b) converting the lead dioxide in the paste to lead oxide,

(c) reacting the paste with sulfuric acid to convert the lead oxide therein to lead sulfate,

(d) mixing the resulting paste with an aqueous ammoniacal ammonium sulfate solution to dissolve a substantial portion of the lead sulfate from the paste,

(e) and removing the lead from the resulting pregnant lead solution.

30. Lead oxide produced by reacting the paste from junk batteries with sulfuric acid to convert lead oxide therein to lead sulfate, mixing the resulting paste wiith an aqueous ammoniacal ammonium sulfate solution to dissolve a substantial portion of the land sulfate from the paste, separating the resulting pregnant lead solution from any solid materials remaining therein, precipitating lead carbonate from the pregnant lead solution and removing the precipitate from the solution, and converting the lead carbonate to lead oxide by the removal of carbon dioxide from the carbonate.