Process for making copper metal powder, copper oxides and copper foil

• US 5,458,746 A
• Filed: 08/09/1994
• Issued: 10/17/1995
• Est. Priority Date: 04/19/1993
• Status: Expired due to Term

• Current Assignee: Nikko Materials USA, Inc. (Eternal Materials Co., Ltd.)
• Original Assignee: Magma Power Co. (Berkshire Hathaway Incorporated), Gould Electronics Incorporated (Eternal Materials Co., Ltd.)
• Inventors: Peckham, Peter, Burgess, David P., Kohut, Stephen J., Haines, Ronald K., Gort, Wendy M., Jenkins, Jackson G.
• Primary Examiner(s): Niebling, John
• Assistant Examiner(s): Mee, Brendan
• Application Number:
  US08/287,703
• Time in Patent Office: 434 Days
• Field of Search: 204/106, 205/74, 75/753
• US Class Current: 205/77
• CPC Class Codes: C22B 15/0067 with acids or salts thereof
• 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 is directed to a process for making copper metal powder from 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) 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, said extractant comprising (i) at least one oxime characterized by a hydrocarbon linkage with at least one --OH group and at least one ═NOH group attached to different carbon atoms on said hydrocarbon linkage, (ii) at least one betadiketone, or (iii) at least one ion-exchange resin; (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 to form a first electrolyte solution; (F) advancing said first electrolyte solution to an electrolytic cell equipped with at least one first anode and at least one first cathode, and applying an effective amount of voltage across said first anode and said first cathode to deposit copper metal powder on said first cathode; and (G) removing copper metal powder from said first cathode. In one embodiment the copper metal powder is converted to copper foil. In one embodiment the copper metal powder is converted to cuprous oxide, cupric oxide or a mixture thereof; these copper oxides can be readily dissolved in sulfuric acid and used to make copper foil.

Claims

1. A process for making copper foil from a copper-bearing material selected from the group consisting of copper ore, smelter flue dust, copper cement and copper-containing waste, said process 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) 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;

said extractant comprising (i) at least one oxime characterized by a hydrocarbon linkage with at least one --OH group and at least one ═

NOH group attached to different carbon atoms on said hydrocarbon linkage, (ii) at least one betadiketone, or (iii) at least one ion-exchange resin;

(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 to form a first electrolyte solution;

(F) advancing said first electrolyte solution into an electrolytic cell equipped with at least one first insoluble anode and at least one first cathode, and applying an effective amount of voltage across said first anode and said first cathode to deposit copper metal powder on said first cathode, said first electrolyte solution containing impurities carried over from one or more of said contacting steps;

(G) removing copper metal powder from said first cathode;

(H) dissolving said copper powder from step (G) in an aqueous sulfuric acid solution to form a second electrolyte solution;

(I) flowing said second electrolyte solution in an electroforming cell between a second anode and a second cathode, said second cathode being a rotating cathode, and applying an effective amount of voltage across said second anode and said second cathode to deposit copper foil on said second cathode, said second electrolyte solution being characterized by the addition of one or more of an active-sulfur containing material, a gelatin, molasses, guar gum, a polyalkylene glycol, dithiothreitol, an amino acid, acrylamide, sulfopropyl disulfide, tetraethylthiuram disulfide, benzyl chloride, epichlorohydrin, chlorohydroxylpropyl sulfonate, an alkylene oxide, a sulfonium alkane sulfonate, thiocarbamoyldisulfide, selenic acid, or a mixture of two or more thereof; and

(J) removing said copper foil from said second cathode.

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

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

4. The process of claim 1 wherein said extractant in step (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.

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

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

7. The process of claim 1 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^-, ##STR9##

8. The process of claim 1 wherein said first electrolyte solution formed in step (E) has a copper ion concentration in the range of about 2 to about 60 grams per liter and a free sulfuric acid concentration in the range of about 70 to about 290 grams per liter.

9. The process of claim 1 wherein said second electrolyte 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.

10. The process of claim 1 with the step of applying to at least one side of said foil from step (J) at least one roughened layer of copper or copper oxide.

11. The process of claim 1 with the step of applying to at least one side of said foil from step (J) at least one metallic layer, the metal in said metallic layer being selected from the group consisting of indium, zinc, tin, nickel, cobalt, copper-zinc alloy and copper-tin alloy.

12. The process of claim 1 with the step of applying to at least one side of said foil from step (J) at least one metallic layer, the metal in said metallic layer being selected from the group consisting of tin, chromium, and chromium-zinc alloy.

13. The process of claim 1 with the steps of applying to at least one side of said foil from step (J) at least one roughened layer of copper or copper oxide, then applying to said roughened layer at least one first metallic layer, the metal in said first metallic layer being selected from the group consisting of indium, zinc, tin, nickel, cobalt, copper-zinc alloy and copper-tin alloy, then applying to said first metallic layer at least one second metallic layer, the metal in said second metallic layer being selected from the group consisting of tin, chromium, and chromium-zinc alloy.

14. A process for making copper foil directly from a copper-bearing material selected from the group consisting of copper ore, smelter flue dust, copper cement and copper-containing waste, said process 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) 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;

said extractant comprising (i) at least one oxime characterized by a hydrocarbon linkage with at least one --OH group and at least one ═

NOH group attached to different carbon atoms on said hydrocarbon linkage, (ii) at least one betadiketone, or (iii) at least one ion-exchange resin;

(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 to form a first electrolyte solution;

(F) advancing said first electrolyte solution into an electrolytic cell equipped with at least one first insoluble anode and at least one first cathode, and applying an effective amount of voltage across said first anode and said first cathode to deposit copper metal powder on said first cathode, said first electrolyte solution containing impurities carried over from one or more of said contacting steps;

(G) removing copper metal powder from said first cathode;

(H'"'"') calcining said copper metal powder from step (G) to form cupric oxide, cuprous oxide, or a mixture thereof;

(H) dissolving said cupric oxide, cuprous oxide or mixture thereof in an aqueous sulfuric acid solution to form a second electrolyte solution;

(I) flowing said second electrolyte solution in an electroforming cell between a second anode and a second cathode, said second cathode being a rotating cathode, and applying an effective amount of voltage across said second anode and said second cathode to deposit copper foil on said second cathode, said second electrolyte solution being characterized by the addition of one or more of an active-sulfur containing material, a gelatin, molasses, guar gum, a polyalkylene glycol, dithiothreitol, an amino acid, acrylamide, sulfopropyl disulfide, tetraethylthiuram disulfide, benzyl chloride, epichlorohydrin, chlorohydroxylpropyl sulfonate, an alkylene oxide, a sulfonium alkane sulfonate, thiocarbamoyldisulfide, selenic acid, or a mixture of two or more thereof; and

(J) removing copper foil from said second cathode.

15. The process of claim 14 wherein said second electrolyte 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.

16. The process of claim 14 with the step of applying to at least one side of said foil from step (J) at least one roughened layer of copper or copper oxide.

17. The process of claim 14 with the step of applying to at least one side of said foil from step (J) at least one metallic layer, the metal in said metallic layer being selected from the group consisting of indium, zinc, tin, nickel, cobalt, copper-zinc alloy and copper-tin alloy.

18. The process of claim 14 with the step of applying to at least one side of said foil from step (J) at least one metallic layer, the metal in said metallic layer being selected from the group consisting of tin, chromium, and chromium-zinc alloy.

19. The process of claim 14 with the steps of applying to at least one side of said foil from step (J) at least one roughened layer of copper or copper oxide, then applying to said toughened layer at least one first metallic layer, the metal in said first metallic layer being selected from the group consisting of indium, zinc, tin, nickel, cobalt, copper-zinc alloy and copper-tin alloy, then applying to said first metallic layer at least one second metallic layer, the metal in said second metallic layer being selected from the group consisting of tin, chromium, and chromium-zinc alloy.

20. The process of claim 14 with the step of separating said copper-rich aqueous solution formed in step (A) from said copper-bearing material.

21. The process of claim 14 wherein said aqueous leaching solution comprises sulfuric acid or ammonia.

22. The process of claim 14 wherein said extractant in step (B) 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.

23. The process of claim 14 wherein said extractant in step (B) comprises at least one compound represented by the formula ##STR11## wherein R¹ and R² are independently hydrogen or hydrocarbyl groups.

24. The process of claim 14 wherein said extractant in step (B) comprises at least one compound represented by the formula ##STR12## wherein R¹ and R² are independently alkyl groups or aryl groups.

25. The process of claim 14 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##

26. The process of claim 14 wherein said first electrolyte solution formed in step (E) has a copper ion concentration in the range of about 2 to about 60 grams per liter and a free sulfuric acid concentration in the range of about 70 to about 290 grams per liter.

28. The process of claim 24 with the step of separating said copper-rich aqueous solution formed in step (A) from said copper-bearing material.

29. The process of claim 24 wherein said aqueous leaching solution comprises sulfuric acid or ammonia.

30. The process of claim 24 wherein said extractant in step (B) comprises at least one compound represented by the formula ##STR14## wherein R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are independently hydrogen or hydrocarbyl groups.

31. The process of claim 24 wherein said extractant in step (B) comprises at least one compound represented by the formula ##STR15## wherein R¹ and R² are independently hydrogen or hydrocarbyl groups.

32. The process of claim 24 wherein said extractant in step (B) comprises at least one compound represented by the formula ##STR16## wherein R¹ and R² are independently alkyl groups or aryl groups.

33. The process of claim 24 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^-, ##STR17##

34. The process of claim 24 wherein said first electrolyte solution formed in step (E) has a copper ion concentration in the range of about 2 to about 60 grams per liter and a free sulfuric acid concentration in the range of about 70 to about 290 grams per liter.

27. A process for making cupric oxide, cuprous oxide or a mixture thereof directly from a copper-bearing material selected from the group consisting of copper ore, smelter flue dust, copper cement and copper-containing waste, said process 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) 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;

said extractant comprising (i) at least one oxime characterized by a hydrocarbon linkage with at least one --OH group and at least one ═

NOH group attached to different carbon atoms on said hydrocarbon linkage, (ii) at least one betadiketone, or (iii) at least one ion-exchange resin;

(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 to form a first electrolyte solution;

(F) advancing said first electrolyte solution into an electrolytic cell equipped with at least one first insoluble anode and at least one first cathode, and applying an effective amount of voltage across said first anode and said first cathode to deposit copper metal powder on said first cathode, said first electrolyte solution containing impurities carried over from one or more of said contacting steps;

(G) removing copper metal powder from said first cathode; and

(H'"'"') calcining said copper metal powder from step (G) to form cupric oxide, cuprous oxide, or a mixture thereof.

35. A process for making copper foil directly from a copper-bearing material selected from the group consisting of copper ore, smelter flue dust, copper cement and copper-containing waste, said process including sequential steps (A), (B-1), (C-1), (B-2), (C-2), (D), (E), (F), (G), (H), (I) and (J), said process 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 step (A) with an effective amount of at least one copper-bearing water-insoluble extractant from step (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;

said extractant comprising (i) at least one oxime characterized by a hydrocarbon linkage with at least one --OH group and at least one ═

NOH group attached to different carbon atoms on said hydrocarbon linkage, (ii) at least one betadiketone, or (iii) at least one ion-exchange resin;

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

(B-2) contacting said first copper-depleted aqueous leaching solution from step (C-1) with an effective amount of at least one copper-depleted extractant from step (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 step (B-1);

(D) contacting said copper-rich extractant from step (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 step (B-2);

(F) advancing said first electrolyte solution from step (E) to an electrolytic cell equipped with at least one first insoluble anode and at least one first cathode, and applying an effective amount of voltage across said first anode and said first cathode to deposit copper powder on said first cathode, said first electrolyte solution containing impurities carried over from one or more of said contacting steps;

(G) removing copper powder from said first cathode;

(H) dissolving said copper powder from step (G) in a sulfuric acid solution to form a second electrolyte solution and placing said second electrolyte solution in an electroforming cell equipped with a second anode and a second cathode, said second cathode being a rotating cathode, said second electrolyte solution being characterized by the addition of one or more of an active-sulfur containing material, a gelatin, molasses, guar gum, a polyalkylene glycol, dithiothreitol, an amino acid, acrylamide, sulfopropyl disulfide, tetraethylthiuram disulfide, benzyl chloride, epichlorohydrin, chlorohydroxylpropyl sulfonate, an alkylene oxide, a sulfonium alkane sulfonate, thiocarbamoyldisulfide, selenic acid, or a mixture of two or more thereof;

(I) flowing said second electrolyte solution between said second anode and second cathode, and applying an effective amount of voltage across said second anode and second cathode to deposit copper foil on said second cathode; and

(J) removing said copper foil from said second cathode.

36. (Amended) A process for making cuprous oxide, cupric oxide or a mixture thereof directly from a copper-bearing material selected from the group consisting of copper ore, smelter flue dust, copper cement and copper-containing waste, said process including sequential steps (A), (B-1), (C-1), (B-2), (C-2), (D), (E), (F), (G) and (H'"'"'), said process 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 step (A) with an effective amount of at least one copper-bearing water-insoluble extractant from step (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;

said extractant comprising (i) at least one oxime characterized by a hydrocarbon linkage with at least one --OH group and at least one ═

NOH group attached to different carbon atoms on said hydrocarbon linkage, (ii) at least one betadiketone, or (iii) at least one ion-exchange resin;

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

(B-2) contacting said first copper-depleted aqueous leaching solution from step (C-1) with an effective amount of at least one copper-depleted extractant from step (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 step (B-1);

(D) contacting said copper-rich extractant from step (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 step (B-2);

(F) advancing said first electrolyte solution from step (E) into an electrolytic cell equipped with at least one first insoluble anode and at least one first cathode, and applying an effective amount of voltage across said first anode and said first cathode to deposit copper metal powder on said first cathode, said first electrolyte solution containing impurities carried over from one or more of said contacting steps;

(G) removing copper metal powder from said first cathode; and

(H'"'"') calcining said copper metal powder at a sufficient temperature and for an effective period of time to form cuprous oxide, cupric oxide or a mixture thereof.

37. A process for making copper foil directly from a copper-bearing material selected from the group consisting of copper ore, smelter flue dust, copper cement and copper-containing waste, said process including sequential steps (A), (B-1), (C-1), (B-2), (C-2), (D), (E), (F), (G), (H'"'"'), (H), (I) and (J), said process 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 step (A) with an effective amount of at least one copper-bearing water-insoluble extractant from step (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;

said extractant comprising (i) at least one oxime characterized by a hydrocarbon linkage with at least one --OH group and at least one ═

NOH group attached to different carbon atoms on said hydrocarbon linkage, (ii) at least one betadiketone, or (iii) at least one ion-exchange resin;

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

(B-2) contacting said first copper-depleted aqueous leaching solution from step (C-1) with an effective amount of at least one copper-depleted extractant from step (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 step (B-1);

(D) contacting said copper-rich extractant from step (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 step (B-2);

(F) advancing said first electrolyte solution from step (E) into an electrolytic cell equipped with at least one first insoluble anode and at least one first cathode, and applying an effective amount of voltage across said first anode and said first cathode to deposit copper metal powder on said first cathode, said first electrolyte solution containing impurities carded over from one or more of said contacting steps;

(G) removing copper metal powder from said first cathode;

(H'"'"') calcining said copper metal powder to form cuprous oxide, cupric oxide or a mixture thereof; and

(H) dissolving said cuprous oxide, cupric oxide or mixture thereof from step (H'"'"') in a sulfuric acid solution to form a second electrolyte solution and placing said second electrolyte solution in an electroforming cell equipped with a second anode and a second cathode, said second cathode being a rotating cathode, said second electrolyte solution being characterized by the addition of one or more of an active-sulfur containing material, a gelatin, molasses, guar gum, a polyalkylene glycol, dithiothreitol, an amino acid, acrylamide, sulfopropyl disulfide, tetraethylthiuram disulfide, benzyl chloride, epichlorohydrin, chlorohydroxylpropyl sulfonate, an alkylene oxide, a sulfonium alkane sulfonate, thiocarbamoyldisulfide, selenic acid, or a mixture of two or more thereof;

(I) flowing said second electrolyte solution between said second anode and second cathode, and applying an effective amount of voltage across said second anode and second cathode to deposit copper foil on said second cathode; and

(J) removing said copper foil from said second cathode.