Process for making copper foil

• US 5,366,612 A
• Filed: 04/19/1993
• Issued: 11/22/1994
• 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: Jordan, Thomas L., Kohut, Stephen I., Clouser, Sidney J., Eamon, Michael A.
• Primary Examiner(s): Gorgos, Kathryn
• Assistant Examiner(s): Wong, Edna
• Application Number:
  US08/049,176
• Time in Patent Office: 582 Days
• Field of Search: 205/104, 205/73, 205/77, 205/138, 204/108
• US Class Current: 205/73
• 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 3/04 by leaching C22B3/18 takes precedence
• CPC Class Codes: C22B 3/26 by liquid-liquid extraction using organic compounds
• CPC Class Codes: C25D 1/04 Wires; Strips; Foils
• CPC Class Codes: Y02P 10/20 Recycling

Abstract

The present invention relates to a process for making copper foil 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 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 rotating cathode, and applying an effective amount of voltage across said anode and said cathode to deposit copper on said cathode; and

(G) continuously removing copper foil from said cathode.

Claims

1. A process for making copper foil 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 rotating cathode, and applying an effective amount of voltage across said anode and said cathode to deposit copper on said cathode; and

(G) continuously removing copper foil from said 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 copper-bearing material is copper ore, smelter flue dust, copper cement, copper sulfate or copper-containing waste.

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

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

6. The process of claim 1 wherein said extractant in step (B) is dissolved in kerosene.

7. 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.

8. 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.

9. 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.

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

11. The process of claim 1 wherein prior to or during step (F) said 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.

12. The process of claim 1 further comprising the step of adding to said stripping solution prior to or during step (F) at least on active-sulfur containing material and/or at least one gelatin.

13. The process of claim 1 wherein I/I_l during step (F) is about 0.4 or less.

14. A process for making copper foil 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, said extractant comprising 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;

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

(G) continuously removing copper foil from said cathode.

15. The process of claim 14 wherein said ion exchange resin is characterized by the presence of at least one functional group selected from --SO₃^-, --COO^-, ##STR9##

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

17. A process for making copper foil from a copper-bearing material comprising:

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

(B) contacting said copper-rich leaching solution with an effective amount of a water-insoluble extractant to transfer copper ions from said copper-rich leaching solution to said extractant to form a copper-rich extractant and a copper-depleted leaching solution, said extractant comprising at least one water-insoluble organic compound characterized by a hydrocarbon linkage with at least one --0H group and at least one ═

NOH group attached to different carbon atoms on said hydrocarbon linkage;

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

(D) contacting said copper-rich extractant with an effective amount of at least one sulfuric acid stripping solution to transfer copper ions from said copper-rich 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 rotating cathode, and applying an effective amount of voltage across said anode and said cathode to deposit copper on said cathode; and

(G) continuously removing copper foil from said cathode.

18. A process for making copper foil from a copper-bearing material, said process 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-1) contacting said copper-rich aqueous leaching solution with an effective amount of at least one copper-beating water-insoluble extractant from step (C-2) to transfer copper ions from said copper-rich aqueous leaching solution to said copper-beating 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 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 copper-rich stripping solution and a copper-depleted extractant;

(E) separating said copper-rich stripping solution from said copper-depleted extractant, recirculating said copper-depleted extractant to step (B-2);

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

(G) continuously removing copper foil from said cathode.

19. A process for making copper foil 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) adding at least one additive to said copper-rich stripping solution and flowing said copper-rich stripping solution between an anode and a rotating cathode;

said additive being 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; and

applying an effective amount of voltage across said anode and said cathode to deposit copper on said cathode; and

(G) continuously removing copper foil from said cathode.

20. A process for making copper foil 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 rotating cathode, and applying an effective amount of voltage across said anode and said cathode to deposit copper on said cathode; and

(G) continuously removing copper foil from said cathode, and applying to at least one side of said foil at least one roughened layer of copper or copper oxide.

21. A process for making copper foil 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 rotating cathode, and applying an effective amount of voltage across said anode and said cathode to deposit copper on said cathode; and

(G) continuously removing copper foil from said cathode, and applying to at least one side of said foil 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.

22. A process for making copper foil 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 rotating cathode, and applying an effective amount of voltage across said anode and said cathode to deposit copper on said cathode; and

(G) continuously removing copper foil from said cathode, and applying to at least one side of said foil at least one metallic layer, the metal in said metallic layer being selected from the group consisting of tin, chromium, and chromium-zinc alloy.

23. A process for making copper foil 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 rotating cathode, and applying an effective amount of voltage across said anode and said cathode to deposit copper on said cathode; and

(G) continuously removing copper foil from said cathode, and applying to at least one side of said foil 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.