Process for making copper wire

• US 5,516,408 A
• Filed: 10/26/1994
• Issued: 05/14/1996
• Est. Priority Date: 04/19/1993
• Status: Expired due to Fees

• Current Assignee: Gould Electronics Incorporated (Eternal Materials Co., Ltd.)
• Original Assignee: Magma Power Co. (Berkshire Hathaway Incorporated), Gould Electronics Incorporated (Eternal Materials Co., Ltd.)
• Inventors: Mills, Bradford A., Peckham, Peter, Young, Sharon K., Kohut, Stephen J., Bay, Adam G., Wright, Roger N., Eamon, Michael A.
• Primary Examiner(s): Niebling, John
• Assistant Examiner(s): Wong, Edna
• Application Number:
  US08/329,235
• Time in Patent Office: 566 Days
• Field of Search: 204/106, 204/108, 205/76, 205/77, 205/101, 205/138
• US Class Current: 205/580
• CPC Class Codes: C22B 15/00 Obtaining copper
• CPC Class Codes: C22B 15/0065 Leaching or slurrying with organic compounds C22B3/16
• CPC Class Codes: C22B 15/0067 with acids or salts thereof
• CPC Class Codes: C22B 3/04 by leaching C22B3/18 takes precedence
• CPC Class Codes: C22B 3/26 by liquid-liquid extraction using organic compounds
• CPC Class Codes: C25C 1/12 of copper
• CPC Class Codes: C25C 5/02 from solutions
• CPC Class Codes: C25D 1/04 Wires; Strips; Foils
• CPC Class Codes: Y02P 10/20 Recycling

Abstract

This invention relates to a process for making copper wire directly from a copper-bearing material, comprising: (A) contacting said copper-beating material with an effective amount of at least one aqueous leaching solution to dissolve copper ions into said leaching solution and form a copper-rich aqueous leaching solution; (B) contacting said copper-rich aqueous leaching solution with an effective amount of at least one water-insoluble extractant to transfer copper ions from said copper-rich aqueous leaching solution to said extractant to form a copper-rich extractant and a copper-depleted aqueous leaching solution; (C) separating said copper-rich extractant from said copper-depleted aqueous leaching solution; (D) contacting said copper-rich extractant with an effective amount of at least one aqueous stripping solution to transfer copper ions from said extractant to said stripping solution to form a copper-rich stripping solution and a copper-depleted extractant; (E) separating said copper-rich stripping solution from said copper-depleted extractant; (F) flowing said copper-rich stripping solution between an anode and a cathode, and applying an effective amount of voltage across said anode and said cathode to deposit copper on said cathode; (G) removing said copper from said cathode; and (H) converting said removed copper from (G) to copper wire at a temperature below the melting point of said copper.

Claims

1. A process for making copper wire directly from a copper-bearing material, comprising:

(A) contacting said copper-bearing material with an effective amount of at least one aqueous leaching solution to dissolve copper ions into said leaching solution and form a copper-rich aqueous leaching solution;

(B) contacting said copper-rich aqueous leaching solution with an effective amount of at least one water-insoluble extractant to transfer copper ions from said copper-rich aqueous leaching solution to said extractant to form a copper-rich extractant and a copper-depleted aqueous leaching solution;

(C) separating said copper-rich extractant from said copper-depleted aqueous leaching solution;

(D) contacting said copper-rich extractant with an effective amount of at least one aqueous stripping solution to transfer copper ions from said extractant to said stripping solution to form a copper-rich stripping solution and a copper-depleted extractant;

(E) separating said copper-rich stripping solution from said copper-depleted extractant;

(F) flowing said copper-rich stripping solution between an anode and a cathode, and applying an effective amount of voltage across said anode and said cathode to deposit copper on said cathode;

(G) removing said copper from said cathode; and

(H) converting said removed copper from (G) to copper wire at a temperature below the melting point of said copper.

2. The process of claim 1 wherein said copper that is removed from said cathode during (G) is in the form of copper foil, and (H) comprises:

(H-1) slitting said copper foil into a plurality of strands of copper wire; and

(H-2) shaping said strands of copper wire from (H-1) to provide said strands with desired cross-sections.

3. The process of claim 1 wherein said copper that is removed from said cathode during (G) is in the form of copper powder, and (H) comprises:

(H-1) extruding said copper powder to form copper rod or wire; and

(H-2) drawing said copper rod or wire from (H-1) to form copper wire of desired cross-section.

4. The process of claim 1 wherein during step (G) said copper while on said cathode is score cut to form a thin strand of copper which is removed from said cathode, and during step (H) said thin strand of copper is shaped to form copper wire of desired cross-section.

5. The process of claim 1 wherein said copper-beating material is copper ore, copper concentrate, copper smelter products, smelter flue dust, copper cement, copper sulfate or copper-containing waste.

6. The process of claim 1 further comprising the step of separating said copper-rich aqueous solution formed in (A) from said copper-bearing material.

7. The process of claim 1 wherein said aqueous leaching solution comprises sulfuric acid, halide acid or ammonia.

8. The process of claim 1 wherein said extractant in (B) is dissolved in an organic solvent selected from the group consisting of kerosene, benzene, naphthalene, fuel oil and diesel fuel.

9. The process of claim 1 wherein said extractant in (B) comprises at least one compound represented by the formula ##STR6## wherein R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are independently hydrogen or hydrocarbyl groups.

10. The process of claim 1 wherein said extractant in (B) comprises at least one compound represented by the formula ##STR7## wherein R¹ and R² are independently hydrogen or hydrocarbyl groups.

11. The process of claim 1 wherein said extractant in (B) comprises at least one compound represented by the formula ##STR8## wherein R¹ and R² are independently alkyl groups or aryl groups.

12. The process of claim 1 wherein said extractant in (B) comprises at least one ion exchange resin.

13. The process of claim 12 wherein said ion exchange resin is a copolymer of styrene and divinylbenzene characterized by the presence of at least one functional group selected from --SO₃¹³, --COO^--, ##STR9##

14. The process of claim 12 wherein said ion exchange resin is a copolymer of styrene and divinylbenzene.

15. The process of claim 1 wherein said stripping solution comprises sulfuric acid.

16. The process of claim 1 wherein said copper that is removed during (G) is in the form of copper foil or copper wire, and during (F) said copper-rich stripping solution has a copper ion concentration in the range of about 40 to about 150 grams per liter and a free sulfuric acid concentration in the range of about 70 to about 170 grams per liter.

17. The process of claim 1 wherein said copper that is removed during (G) is in the form of copper foil or copper wire, and prior to or during (F) at least one active-sulfur containing material or at least one gelatin is added to said copper-rich stripping solution.

18. The process of claim 1 wherein said copper that is removed during (G) is in the form of copper foil or copper wire, and prior to or during (F) at least one additive selected from the group consisting of molasses, guar gum, polyethylene glycol, polypropylene glycol, polyisopropylene glycol, dithiothreitol, proline, hydroxyproline, cysteine, acrylamide, sulfopropyl disulfide, tetraethylthiuram disulfide, benzyl chloride, epichlorohydrin, chlorohydroxylpropylsulfonate, ethylene oxide, propylene oxide, sulfonium alkane sulfonate, thiocarbamoyldisulfide and selenic acid is added to said copper-rich stripping solution.

19. The process of claim 1 wherein said copper that is removed during (G) is in the form of copper foil or copper wire, and I/_L during (F) is about 0.4 or less.

20. The process of claim 1 wherein said copper that is removed during (G) is in the form of copper powder, and during (F) said copper-rich stripping solution has a copper ion concentration in the range of about 1 to about 60 grams per liter and a free sulfuric acid concentration in the range of about 70 to about 300 grams per liter.

21. The process of claim 1 wherein said copper that is removed during (G) is in the form of copper powder, and prior to or during (F) at least one additive selected from the group consisting of gelatin, benzotriazole, thiourea, chloride ions, sodium sulfate, and one or more sulfonates is added to said copper-rich stripping solution.

22. The process of claim 1 wherein said copper that is removed during (G) is in the form of copper powder, and I/I_L during (F) is about 0.8 or greater.

23. A process for making copper wire directly from a copper-beating material, comprising:

(A) contacting said copper-bearing material with an effective amount of at least one aqueous leaching solution to dissolve copper ions in said leaching solution and form a copper-rich aqueous leaching solution;

(B-1) contacting said copper-rich aqueous leaching solution from (A) with an effective amount of at least one copper-beating water-insoluble extractant from (C-2) to transfer copper ions from said copper-rich aqueous leaching solution to said copper-bearing extractant to form a copper-rich extractant and a first copper-depleted aqueous leaching solution;

(C-1) separating said copper-rich extractant from said first copper-depleted aqueous leaching solution, advancing said copper-rich extractant to (D);

(B-2) contacting said first copper-depleted aqueous leaching solution from (C-1) with an effective amount of at least one copper-depleted extractant from (E) to transfer copper ions from said first copper-depleted aqueous leaching solution to said copper-depleted extractant to form a copper-bearing extractant and a second copper-depleted aqueous leaching solution;

(C-2) separating said copper-bearing extractant from said second copper-depleted aqueous leaching solution, recirculating said copper-bearing extractant to (B-1);

(D) contacting said copper-rich extractant from (C-1) with an effective amount of at least one aqueous stripping solution to transfer copper ions from said copper-rich extractant to said stripping solution to form a first electrolyte solution and a copper-depleted extractant;

(E) separating said first electrolyte solution from said copper-depleted extractant, recirculating said copper-depleted extractant to (B-2);

(F) advancing said first electrolyte solution to an electrolytic cell equipped with at least one anode and at least one rotating cathode, and applying an effective amount of voltage across said anode and said cathode to deposit copper on said cathode in the form of copper foil;

(G) removing said copper foil from said cathode;

(H-1) slitting said copper foil into a plurality of strands of copper wire; and

(H-2) shaping said strands of copper wire from (H-1) to provide said strands with desired cross-sections.

24. A process for making copper wire directly from a copper-bearing material, comprising:

(A) contacting said copper-bearing material with an effective amount of at least one aqueous leaching solution to dissolve copper ions in said leaching solution and form a copper-rich aqueous leaching solution;

(B-1) contacting said copper-rich aqueous leaching solution from (A) with an effective amount of at least one copper-bearing water-insoluble extractant from (C-2) to transfer copper ions from said copper-rich aqueous leaching solution to said copper-bearing extractant to form a copper-rich extractant and a first copper-depleted aqueous leaching solution;

(C-1) separating said copper-rich extractant from said first copper-depleted aqueous leaching solution, advancing said copper-rich extractant to (D);

(B-2) contacting said first copper-depleted aqueous leaching solution from (C-1) with an effective amount of at least one copper-depleted extractant from (E) to transfer copper ions from said first copper-depleted aqueous leaching solution to said copper-depleted extractant to form a copper-bearing extractant and a second copper-depleted aqueous leaching solution;

(C-2) separating said copper-bearing extractant from said second copper-depleted aqueous leaching solution, recirculating said copper-beating extractant to (B-1);

(D) contacting said copper-rich extractant from (C-1) with an effective amount of at least one aqueous stripping solution to transfer copper ions from said copper-rich extractant to said stripping solution to form a first electrolyte solution and a copper-depleted extractant;

(E) separating said first electrolyte solution from said copper-depleted extractant, recirculating said copper-depleted extractant to (B-2);

(F) advancing said first electrolyte solution from (E) to an electrolytic cell equipped with at least one first anode and at least one cathode, and applying an effective amount of voltage across said anode and said cathode to deposit copper on said first cathode;

(G) removing copper powder from said cathode;

(H-1) extruding said copper powder to form copper rod or wire; and

(H-2) drawing said copper rod or wire from (H-1) to form copper wire with a desired cross-section.

25. A process for making copper wire directly from a copper-bearing material, comprising:

(A) contacting said copper-bearing material with an effective amount of at least one aqueous leaching solution to dissolve copper ions in said leaching solution and form a copper-rich aqueous leaching solution;

(B-1) contacting said copper-rich aqueous leaching solution from (A) with an effective amount of at least one copper-bearing water-insoluble extractant from (C-2) to transfer copper ions from said copper-rich aqueous leaching solution to said copper-bearing extractant to form a copper-rich extractant and a first copper-depleted aqueous leaching solution;

(C-1) separating said copper-rich extractant from said first copper-depleted aqueous leaching solution, advancing said copper-rich extractant to (D);

(B-2) contacting said first copper-depleted aqueous leaching solution from (C-1) with an effective amount of at least one copper-depleted extractant from (E) to transfer copper ions from said first copper-depleted aqueous leaching solution to said copper-depleted extractant to form a copper-bearing extractant and a second copper-depleted aqueous leaching solution;

(C-2) separating said copper-bearing extractant from said second copper-depleted aqueous leaching solution, recirculating said copper-bearing extractant to (B-1);

(D) contacting said copper-rich extractant from (C-1) with an effective amount of at least one aqueous stripping solution to transfer copper ions from said copper-rich extractant to said stripping solution to form a first electrolyte solution and a copper-depleted extractant;

(E) separating said first electrolyte solution from said copper-depleted extractant, recirculating said copper-depleted extractant to (B-2);

(F) advancing said first electrolyte solution from (E) into an electrolytic cell equipped with at least one anode and at least one rotating cathode, and applying an effective amount of voltage across said anode and said cathode to deposit copper on said cathode;

(G) score-cutting said copper to form a thin strand of copper and removing said strand of copper from said cathode; and

(H-1) shaping said strand of copper from (G) to provide copper wire with a desired cross-section.

26. A process for making copper wire directly from a copper-bearing material, comprising:

(A) contacting said copper-bearing material with an effective amount of at least one aqueous leaching solution to dissolve copper ions in said leaching solution and form a copper-rich aqueous leaching solution;

(B-1) contacting said copper-rich aqueous leaching solution from (A) with an effective amount of at least one copper-bearing water-insoluble extractant from (C-2) to transfer copper ions from said copper-rich aqueous leaching solution to said copper-bearing extractant to form a copper-rich extractant and a first copper-depleted aqueous leaching solution;

(C-1) separating said copper-rich extractant from said first copper-depleted aqueous leaching solution, advancing said copper-rich extractant to (D);

(B-2) contacting said first copper-depleted aqueous leaching solution from (C-1) with an effective amount of at least one copper-depleted extractant from (E) to transfer copper ions from said first copper-depleted aqueous leaching solution to said copper-depleted extractant to form a copper-bearing extractant and a second copper-depleted aqueous leaching solution;

(C-2) separating said copper-bearing extractant from said second copper-depleted aqueous leaching solution, recirculating said copper-bearing extractant to (B-1);

(D) contacting said copper-rich extractant from (C-1) with an effective amount of at least one aqueous stripping solution to transfer copper ions from said copper-rich extractant to said stripping solution to form a first electrolyte solution and a copper-depleted extractant;

(E) separating said first electrolyte solution from said copper-depleted extractant, recirculating said copper-depleted extractant to (B-2);

(F) advancing said first electrolyte solution to an electrolytic cell equipped with at least one anode and at least one rotating cathode, and applying an effective amount of voltage across said anode and said cathode to deposit copper on said cathode;

(G) removing said copper from said cathode; and

(H) converting said removed copper from (G) to copper wire at a temperature below the melting point of said copper.

27. The process of claim 26 wherein said copper-bearing material is copper ore, copper concentrate, copper smelter products, smelter flue dust, copper cement, copper sulfate or copper-containing waste.

28. The process of claim 26 with the step of separating said copper-rich aqueous solution formed in (A) from said copper-bearing material.

29. The process of claim 26 wherein said aqueous leaching solution comprises sulfuric acid, halide acid or ammonia.

30. The process of claim 26 wherein said extractant is dissolved in an organic solvent selected from the group consisting of kerosene, benzene, naphthalene, fuel oil and diesel fuel.

31. The process of claim 26 wherein said extractant comprises at least one compound represented by the formula ##STR10## wherein R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are independently hydrogen or hydrocarbyl groups.

32. The process of claim 26 wherein said extractant comprises at least one compound represented by the formula ##STR11## wherein R¹ and R² are independently hydrogen or hydrocarbyl groups.

33. The process of claim 26 wherein said extractant comprises at least one compound represented by the formula ##STR12## wherein R¹ and R² are independently alkyl groups or aryl groups.

34. The process of claim 26 wherein said extractant comprises at least one ion exchange resin.

35. The process of claim 34 wherein said ion exchange resin is a copolymer of styrene and divinylbenzene characterized by the presence of at least one functional group selected from --SO₃^--, --COO^--, ##STR13##

36. The process of claim 34 wherein said ion exchange resin is a copolymer of styrene and divinylbenzene.

37. The process of claim 26 wherein said stripping solution comprises sulfuric acid.

38. The process of claim 26 wherein said copper that is removed during (G) is in the form of copper foil or copper wire, and during (F) said copper-rich stripping solution has a copper ion concentration in the range of about 40 to about 150 grams per liter and a free sulfuric acid concentration in the range of about 70 to about 170 grams per liter.

39. The process of claim 26 wherein said copper that is removed during (G) is in the form of copper foil or copper wire, and prior to or during (F) at least one active-sulfur containing material and/or at least one gelatin is added to said copper-rich stripping solution.

40. The process of claim 26 wherein said copper that is removed during (G) is in the form of copper foil or copper wire, and prior to or during (F) at least one additive selected from the group consisting of molasses, guar gum, polyethylene glycol, polypropylene glycol, polyisopropylene glycol, dithiothreitol, proline, hydroxyproline, cysteine, acrylamide, sulfopropyl disulfide, tetraethylthiuram disulfide, benzyl chloride, epichlorohydrin, chlorohydroxylpropylsulfonate, ethylene oxide, propylene oxide, sulfonium alkane sulfonate, thiocarbamoyldisulfide and selenic acid is added to said copper-rich stripping solution.

41. The process of claim 26 wherein said copper that is removed during (G) is in the form of copper foil or copper wire, and I/I_L, during (F) is about 0.4 or less.

42. The process of claim 26 wherein said copper that is removed during (G) is in the form of copper powder, and during (F) said copper-rich stripping solution has a copper ion concentration in the range of about 1 to about 60 grams per liter and a free sulfuric acid concentration in the range of about 70 to about 300 grams per liter.

43. The process of claim 26 wherein said copper that is removed during (G) is in the form of copper powder, and prior to or during (F) at least one additive selected from the group consisting of gelatin, benzotriazole, thiourea, chloride ions, sodium sulfate, and one or more sulfonates is added to said copper-rich stripping solution.

44. The process of claim 26 wherein said copper that is removed during (G) is in the form of copper powder, and I/_L, during (F) is about 0.8 or greater.