RECOVERING METALS FROM COMPLEX METAL SULFIDES

• US 20100199807A1
• Filed: 02/04/2010
• Published: 08/12/2010
• Est. Priority Date: 11/28/2007
• Status: Active Grant

• Current Assignee: Sherritt International Corporation
• Original Assignee: Sherritt International Corporation
• Inventors: Berezowsky, Roman, Stiksma, John
• Granted Patent: US 8,221,710 B2
• Time in Patent Office: Days
• US Class Current: 75/743
• CPC Class Codes: C01B 17/20 Methods for preparing sulfides or polysulfides, in general ammonium sulfides or polysulfides C01C; sulfides or polysulfides of metals, other than alkali metals, magnesium, calcium, strontium and barium, see the relevant groups of subclasses C01F or C01G, according to the metal
• CPC Class Codes: C01C 1/242 Preparation from ammonia and sulfuric acid or sulfur trioxide
• CPC Class Codes: C01G 31/00 Compounds of vanadium
• CPC Class Codes: C01G 31/02 Oxides
• CPC Class Codes: C01G 39/00 Compounds of molybdenum
• CPC Class Codes: C01G 39/06 Sulfides
• CPC Class Codes: C01G 53/10 Sulfates
• CPC Class Codes: C01G 53/11 Sulfides
• CPC Class Codes: C22B 23/0446 with an ammoniacal liquor or with a hydroxide of an alkali or alkaline-earth metal
• CPC Class Codes: C22B 3/12 in inorganic alkaline solutions
• CPC Class Codes: C22B 3/44 by chemical processes treatment or purification of solutions by liquid-liquid extraction C22B3/26, by ion-exchange extraction C22B3/42
• CPC Class Codes: C22B 34/225 from spent catalysts
• CPC Class Codes: C22B 34/345 from spent catalysts
• CPC Class Codes: C22B 7/006 Wet processes
• CPC Class Codes: C22B 7/009 General processes for recovering metals or metallic compounds from spent catalysts for recovering specific metals C22B11/00 - C22B61/00
• CPC Class Codes: Y02P 10/20 Recycling

Abstract

Methods for recovering base metals, including, among other metals, molybdenum and nickel, from metal sulfides containing a Group VIB metal and a Group VIII metal. Generally, the methods comprise: contacting metal sulfides with a leaching solution containing ammonia and air to dissolve the metals into the leaching solution, forming a slurry containing soluble complexes of the metals, ammonium sulphate and solid residue containing ammonium metavanadate and any carbonaceous materials. The solid residue containing ammonium metavanadate and carbonaceous materials is then separated from the slurry and metal complexes are precipitated from the slurry by adjusting the pH. A second slurry may be formed comprising a second solid residue and a primary filtrate comprising ammonium sulfate solution that is substantially free of metals. The second solid residue is separated from the primary filtrate comprising ammonium sulfate by any means suitable for separation of solids from liquids and is then dissolved, at a second pre-selected pH, to form a Group VIB metal precipitate and a Group VIII metal containing solution. Group VIB and Group VIII metals can be easily recovered from the precipitate and solution, respectively. In some embodiments Group VB metals are recovered as well.

Claims

1. A method of recovering metals from finely divided metal sulfides containing a Group VIB metal, a Group VB metal, and a Group VIII metal, the method comprising the steps of:

contacting the finely divided metal sulfides with a leaching solution containing ammonia and air to dissolve the Group VIB metal and the Group VIII metal into the leaching solution at a sufficient temperature and pressure to form a pressure leach slurry containing at least a Group VIB soluble metal complex and at least a Group VIII soluble metal complex and solid residue containing at least a Group VB metal complex;

separating and removing the solid residue containing the Group VB metal complex from the pressure leach slurry, forming a pressure leach solution;

mixing the pressure leach solution with an additive selected from the group consisting of a mineral acid, a sulfide-containing compound, and a sulphur compound under mixing conditions at a temperature in the range of 50 to 90°

C. for a sufficient amount of time to precipitate at least a portion of the Group VIB metal and at least a portion of the Group VIII metal, wherein the precipitation is carried out at a first pre-selected pH to precipitate as metal complexes at least a portion of the Group VIB metal and at least a portion of the Group VIII metal.

2. The method of claim 1, wherein the Group VB metal is vanadium, and

wherein the Group VB metal complex comprises ammonium metavanadate.

3. The method of claim 1, further comprising the step of:

recovering the precipitated metal complexes by at least a separation means selected from settling, filtration, decantation, centrifugation and combinations thereof, forming a first supernatant substantially free of at least a portion of the Group VIB metal and at least a portion of the Group VIII metal.

4. The method of claim 3, wherein the first supernatant contains 0.1 to 3% of the Group VIB metal, 1 to 20% of the Group VB metal, and 1 to 35% of the Group VIII metal.

5. The method of claim 4, further comprising the step of:

precipitating from the first supernatant at least a portion of the Group VIB metal and at least a portion of the Group VIII metal, wherein the precipitation being carried out at a second pre-selected pH to precipitate as metal complexes at least 95% of the Group VIB metal and at least 95% of the Group VIII metal initially present in the first supernatant prior to the precipitation at the second pre-selected pH.

6. The method of claim 5, further comprising the step of:

recovering the Group VIB and group VIII metal sulfides by at least a separation means selected from settling, filtration, decantation, centrifugation and combinations thereof, forming a second supernatant containing less than 100 ppm of the group VIB metal, less than 20 ppm of the Group VIII metal, and less than 100 ppm of the Group VB metal.

7. The method of claim 1, wherein at least 90% of the Group VIB metal precipitates from the pressure leach solution as a metal complex.

8. The method of claim 1, wherein the Group VIB metal is molybdenum and wherein the first pre-selected pH is in the range of 2.5 to 3.3 to precipitate greater than 90% of the molybdenum as a molybdate complex.

9. The method of claim 8, wherein the pressure leach solution (PLS) is adjusted to the first pre-selected pH by adding to the PLS at least one of a mineral acid or a sulfur compound having a sulfhydryl group or an ionized sulfhydryl group, or mixtures thereof.

10. The method of claim 9, wherein the pH of the PLS is adjusted to a pH of 3.5 or less with an acid selected from the group of sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid.

11. The method of claim 10, wherein the PLS is adjusted to a pH of 3 or less with the addition of a sulfuric acid for at least 95% of the molybdenum to precipitate out as a molybdate complex.

12. The method of claim 9, wherein the pH of the pressure leach solution is adjusted to a pH of 3 or less with at least one of a water soluble sulfide, a water soluble polysulfide, or mixtures thereof.

13. The method of claim 1, wherein the Group VIB metal is molybdenum, the Group VIII metal is nickel, the Group VB metal is vanadium, and wherein the first supernatant contains 0.1 to 3% of the molybdenum, 1 to 20% of the vanadium and 1 to 35% of the nickel.

14. The method of claim 13, wherein at least one of a water soluble sulfide, a water soluble polysulfide, or mixtures thereof is added to the first supernatant for a pH level of between 5 and 7 to obtain a precipitate of Mo, Ni, and V sulfides.

15. The method of claim 14, wherein H.sub.2S is added to the first supernatant at a pressure from atmospheric to 100 psig and at a temperature ranging from 50 to 95°

C.

16. The method of claim 6, wherein the Group VIB metal is molybdenum, the Group VIII metal is nickel, the Group VB metal is vanadium, the pressure leach solution is adjusted to a pH of 3 or less with the addition of a sulfuric acid for at least 95% of the molybdenum to precipitate out as a molybdate complex, the molybdate complex is separated from the first supernatant by filtration, H₂S is added to the first supernatant at a pressure from atmospheric to 100 psig and at a temperature ranging from 50-95°

C. to obtain a precipitate of Mo, Ni, and V sulfides, the Mo, Ni, and V sulfides are separated from the second supernatant by filtration, and wherein the second supernatant contains 100 to 1000 gpL ammonium sulfate, less than 100 ppm molybdenum, less than 20 ppm nickel, and less than 100 ppm vanadium.

71. The method of claim 57, wherein the primary filtrate comprises less than 400 ppm nickel, less than 1000 ppm of molybdenum and an ammonium sulfate content of at least 400 gpL, the pH is initially adjusted to approximately 8 with ammonia;

the primary precipitation method comprises sulfidation carried out between 90 kPa and 110 kPa overpressure with hydrogen sulfide gas at a temperature between about 90°

C. and 110°

C. for 60 to 80 minutes and the pH is adjusted at least 2 times from basic to acidic and from acidic to basic to form a primary liquid fraction and a primary solid residue;

separating the primary liquid fraction and the primary solid residue;

transferring the primary solid residue to step (a) of claim 1;

combining the primary liquid fraction with the secondary liquid fraction to form the combined solution;

subjecting the combined solution to sulfamate hydrolysis and sulfide oxidation in the presence of steam and air at a temperature ranging between 220°

C. and 240°

C. to form a purified solution comprising ammonium sulfate.

17. A method of recovering metals from finely-divided metal sulfides, the method comprising the steps of:

contacting the finely-divided metal sulfides with a leaching solution containing ammonia and air to dissolve the Group VIB metal and the Group VIII metal into the leaching solution at a sufficient temperature and pressure to form a pressure leach slurry containing at least a Group VIB soluble metal complex and at least a Group VIII soluble metal complex, ammonium sulfate and solid residue containing at least a Group VB metal complex;

separating and removing the solid residue containing the Group VB metal complex from the pressure leach slurry forming a pressure leach solution;

mixing from the pressure leach solution with an additive selected from the group consisting of a mineral acid, a sulfide-containing compound, and a sulphur compound under mixing conditions at a temperature in the range of 50 to 90°

C. for a sufficient amount of time to precipitate at least a portion of the Group VIB metal and at least a portion of the Group VIII metal, wherein the precipitation being carried out at a first pre-selected pH to precipitate as metal complexes at least a portion of the Group VIB metal and at least a portion of the Group VIII metal;

wherein the finely-divided metal sulfides contain at least a group VB metal, a Group VIII non-noble metal, a group VIB metal selected from Mo and W and combination thereof.

18. The method of claim 17, further comprising the steps of:

recovering the precipitated metal complexes by filtration, forming a first supernatant containing 0.1 to 3% of the Group VIB metal in the spent dispersed catalyst for metal recovery, 1 to 20% of the Group VB metal in the spent dispersed catalyst for metal recovery, and 1 to 35% of the Group VIII metal in the spent dispersed catalyst for metal recovery;

precipitating from the first supernatant at least a portion of the Group VIB metal and at least a portion of the Group VIII metal, wherein the precipitation is carried out at a second pre-selected pH to precipitate as metal sulfides at least 95% of the Group VIB metal and at least 95% of the Group VIII metal initially present in the first supernatant prior to the precipitation at the second pre-selected pH;

recovering the Group VIB and Group VIII metal sulfides by filtration, forming a second supernatant containing less than 100 ppm of the Group VIB metal, less than 20 ppm of the Group VIII metal, and less than 100 ppm of the Group VB metal.

19. The method of claim 18, wherein the Group VIB metal is molybdenum and wherein the pre-selected pH is in the range of 2.5 to 3.3 to precipitate greater than 90% of the molybdenum.

20. The method of claim 18, wherein the finely-divided metal sulfides have a median particle size of 0.01 to 200 microns.

21. A method of recovering metals including vanadium from finely divided metal sulfides, the method comprising the steps of:

contacting the finely divided metal sulfides with a leaching solution containing ammonia and air to dissolve the Group VIB metal and the Group VIII metal into the leaching solution at a sufficient temperature and pressure to form a pressure leach slurry containing at least a group VIB soluble metal complex and at least a group VIII soluble metal complex, ammonium sulfate and solid residue containing at least a Group VB metal complex;

separating and removing the solid residue containing ammonium metavanadate and coke from the pressure leach slurry forming a pressure leach solution;

mixing the pressure leach solution with an additive selected from the group consisting of a mineral acid, a sulfide-containing compound, and a sulphur compound under mixing conditions at a temperature in the range of 50 to 90°

C. for a sufficient amount of time to precipitate at least a portion of the Group VIB metal and at least a portion of the Group VIII metal, wherein the precipitation being carried out at a first pre-selected pH to precipitate as metal complexes at least a portion of the Group VIB metal and at least a portion of the Group VIII metal;

recovering the metal complexes by filtration, forming a first supernatant containing 0.1 to 3% of the Group VIB metal in the spent dispersed catalyst for metal recovery, 1 to 20% of the Group VB metal in the spent dispersed catalyst for metal recovery, and 1 to 35% of the Group VIII metal in the spent dispersed catalyst for metal recovery;

precipitating from the first supernatant at least a portion of the Group VIB metal and at least a portion of the Group VIII metal, wherein the precipitation being carried out at a second pre-selected pH to precipitate as metal complexes at least 95% of the Group VIB metal and at least 95% of the Group VIII metal initially present in the first supernatant prior to the precipitation at the second pre-selected pH; and

recovering the Group VIB and group VIII metal sulfides by filtration, forming a second supernatant containing less than 100 ppm of the group VIB metal, less than 20 ppm of the Group VIII metal, and less than 100 ppm of the group VB metal.

22. A method for recovering metals from metal bearing materials comprising:

(a) leaching finely divided sulfides of a Group VIB metal and a Group VIII metal with an ammonia containing leach solution at a temperature and a pressure sufficient to form a pressure leach slurry comprising at least a Group VIB soluble metal complex and at least a Group VIII soluble metal complex and a first solid residue;

(b) separating and removing the first solid residue from the pressure leach slurry to form a first pressure leach solution comprising the Group VIB soluble metal complex and the Group VIII soluble metal complex;

(c) precipitating from the first pressure leach solution, at a first pre-selected pH, a second solid residue comprising at least a portion of the Group VIB soluble metal complex to form a first slurry comprising the second solid residue and at least a portion of the Group VIII soluble metal complex;

(d) separating from the first slurry, the second solid residue and a primary filtrate substantially free of Group VIB and the Group VIII metals;

(e) dissolving the second solid residue at a second pre-selected pH to form a group VIB metal precipitate and a group VIII metal containing solution;

(f) separating the group VIB metal precipitate from the Group VIII metal containing solution; and

(g) dissolving said Group VIB metal precipitate in a dilute base at a sufficient temperature to form a Group VIB soluble metal product.

23. The method of claim 22 wherein the step (f) further comprises

(i) recovering a secondary filtrate comprising substantially the Group VIII soluble metal complex and a trace amount of the Group VIB metal;

(ii) combining the secondary filtrate with the primary filtrate from step (d) to form a combined filtrate comprising substantially the Group VIII soluble metal complex and a trace quantity of the Group VIB metal;

(iii) precipitating from the combined filtrate the Group VIB and Group VIII metals in a sulfidation process to form a third solid residue and a tertiary filtrate; and

(iv) separating the third solid residue from the tertiary filtrate and dissolving the third solid residue to form a group VIII metal product solution.

24. The method of claim 23 further comprising, subjecting the tertiary filtrate to hydrolysis to form a purified solution.

25. The method of claim 24 wherein the purified solution is ammonium sulfate.

26. The method of claim 22 wherein the precipitation step (c) is carried out at a pH in a range between 2.5 to 3.5, at a temperature between about 75°

C. and 85°

C. for at least two hours.

34. The method of claim 22, wherein at least 90% of the Group VIB metal precipitates from the pressure leach solution as a metal complex.

35. The method of claim 22, wherein the Group VIB metal is molybdenum and wherein the first pre-selected pH is in the range of 2.5 to 3.3 to precipitate greater than 90% of the molybdenum as a molybdate complex.

36. The method of claim 35, wherein the pressure leach solution (PLS) is adjusted to the first pre-selected pH by adding to the PLS at least one of a mineral acid or a sulfur compound having a sulfhydryl group or an ionized sulfhydryl group, or mixtures thereof.

37. The method of claim 36, wherein the pH of the PLS is adjusted to a pH of 3.5 or less with an acid selected from the group of sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid.

38. The method of claim 37, wherein the PLS is adjusted to a pH of 3 or less with the addition of a sulfuric acid for at least 95% of the molybdenum to precipitate out as an octamolybdate complex.

39. The method of claim 36, wherein the pH of the pressure leach solution is adjusted to a pH of 3 or less with at least one of a water soluble sulfide, a water soluble polysulfide, or mixtures thereof.

40. The method of claim 22, wherein the Group VIB metal in the used catalyst is molybdenum and the Group VIII metal.

41. The method of claim 23, wherein at least one of a water soluble sulfide, a water soluble polysulfide, or mixtures thereof is added to the combined filtrate for a pH level of between 6 and 9 to obtain a precipitate of Mo and Ni.

42. The method of claim 41, wherein H₂S is added to the combined filtrate at a pressure from atmospheric to 100 psig, a temperature ranging from 50 to 110°

C. for at least 30 minutes.

27. A method for recovering metals from metal bearing materials comprising:

(a) leaching finely divided sulfides of a Group VB metal, a Group VIB metal and a Group VIII metal with an ammonia containing leach solution at a temperature and a pressure sufficient to form a pressure leach slurry comprising at least a Group VIB soluble metal complex and at least a Group VIII soluble metal complex and a first solid residue;

(b) separating and removing the first solid residue from the pressure leach slurry to form a first pressure leach solution comprising the Group VIB soluble metal complex and the Group VIII soluble metal complex;

(c) precipitating from the first pressure leach solution, at a first pre-selected pH, a second solid residue comprising at least a portion of the Group VIB soluble metal complex to form a first slurry comprising the second solid residue and at least a portion of the Group VIII soluble metal;

(d) separating from the first slurry, the second solid residue and a primary filtrate substantially free of Group VB, Group VIB and the Group VIII metals;

(e) dissolving the second solid residue at a second pre-selected pH to form a group VIB metal precipitate and a group VIII metal containing solution;

(f) separating the group VIB metal precipitate from the Group VIII metal containing solution;

(g) dissolving said Group VIB metal precipitate in a dilute base at a sufficient temperature to form a Group VIB soluble metal product.

(h) recovering from step (f) a secondary filtrate comprising the Group VIII metal containing solution having substantially the Group VIII soluble metal complex and a trace amount of Group VB and Group VIB metals;

(i) combining the secondary filtrate with the primary filtrate from step (d) to form a combined filtrate comprising substantially the Group VIII soluble metal complex and a trace quantity of Group VB and Group VIB metals;

(j) precipitating from the combined filtrate the Group VB, Group VIB and Group VIII metals in a sulfidation process to form a third solid residue and a tertiary filtrate; and

(k) separating the third solid residue from the tertiary filtrate and dissolving the third solid residue to form a group VIII metal product solution.

28. The method of claim 27, wherein the first solid residue comprises a Group VB metal, at least a Group VB metal complex and carbonaceous material and, wherein the Group VB metal is vanadium, and wherein the Group VB metal complex comprises ammonium metavanadate.

29. The method of claim 27, wherein the separation steps (b), (d) and (f) each comprise at least a separation means selected from settling, filtration, decantation, centrifugation and combinations thereof.

30. The method of claim 27, wherein the primary filtrate comprises 0.1 to 3% of the Group VIB metal, 1 to 20% of the Group VB metal, and 1 to 35% of the Group VIII metal.

31. The method of claim 27, wherein the combined filtrate comprises at least a portion of the Group VB metal, Group VIB metal and at least a portion of the Group VIII metal, wherein the sulfidation process is carried out at a third pre-selected pH to precipitate as metal sulfides and oxy-hydroxides at least 95% of the Group VB metal, at least 95% of the Group VIB metal and at least 95% of the Group VIII metal present in the combined filtrate.

32. The method of claim 27, wherein the separation step (iv) comprises at least a separation means selected from settling, filtration, decantation, centrifugation and combinations thereof.

33. The method of claim 32 wherein the tertiary filtrate comprises less than 100 ppm of the group VIB metal, less than 20 ppm of the Group VIII metal, and less than 100 ppm of the Group VB metal.

43. The method of claim 27, wherein the Group VIB metal is molybdenum, the Group VIII metal is nickel, the Group VB metal is vanadium, the pressure leach solution is adjusted to a pH of 3 or less with the addition of sulfuric acid to precipitate and form the second solid residue comprising at least 95% of the molybdenum as an octamolybdate complex and at least 75% of the nickel as a nickel ammonium sulfate compound, at least partially dissolving the second solid residue in acidic water having a pH of 2.5 or less at a temperature of 80°

C. to form an octamolybdate precipitate and a solution of the double salt of nickel and dissolving the octamolybdate precipitate in a dilute ammonia at a temperature ranging from 50°

C. to 75°

C. to form an ammonium molybdate product.

44. The method of claim 43 further comprising:

separating the octamolybdate precipitate from the double salt of nickel solution to form the secondary filtrate;

combining the primary filtrate and the secondary filtrate to form the combined filtrate comprising at least 80% of the nickel, from 0.1 to 3% of the molybdenum, feed and from 1 to 20% of the vanadium;

adding H₂S to the combined filtrate at a pressure from atmospheric to 100 psig and at a temperature ranging from 50-110°

C. to obtain the third solid residue, which comprises a precipitate of Mo and Ni sulfides and V oxy-hydroxides;

separating the Mo, Ni, and V sulfides and oxy-hydroxides by filtration to obtain the tertiary filtrate, which comprises 100 to 1000 gpL ammonium sulfate, less than 100 ppm molybdenum, less than 20 ppm nickel, and less than 100 ppm vanadium.

45. The method of claim 44 further comprising:

dissolving the third solid residue at a pH of five or less in the presence of oxygen at a temperature between 150°

C. and 170°

C., a total pressure ranging from 150 psig to 170 psig for a time between 30 minutes and 1.5 hours to obtain a nickel sulfate product solution.

46. A method for recovering metals from metals bearing materials comprising:

(a) leaching finely divided sulfides of a Group VIB metal and a Group VIII metal with an ammonia containing leach solution at a temperature and a pressure sufficient to form a pressure leach slurry comprising at least a Group VIB soluble metal complex and at least a Group VIII soluble metal complex and a first solid residue;

(b) separating and removing the first solid residue from the pressure leach slurry to form a first pressure leach solution comprising the Group VIB soluble metal complex and the Group VIII soluble metal complex;

(c) precipitating from the first pressure leach solution, at a first pre-selected pH, a second solid residue comprising at least a portion of the Group VIB soluble metal complex to form a first slurry comprising the second solid residue and at least a portion of the Group VIII soluble metal complex;

(d) separating from the first slurry, the second solid residue and a primary filtrate substantially free of Group VIB and the Group VIII metals;

(e) dissolving the second solid residue at a second pre-selected pH to form a group VIB metal precipitate and a group VIII metal containing solution;

(f) separating the group VIB metal precipitate from the Group VIII metal containing solution;

(g) dissolving said Group VIB metal precipitate in a dilute base at a sufficient temperature to form a Group VIB soluble metal product;

(h) forming a secondary filtrate comprising substantially ammonium sulphate, the Group VIII soluble metal complex and trace amounts of the Group VIB metals;

(i) processing the primary filtrate in a primary precipitation method to form a primary solid residue and a primary liquid fraction and separately processing the secondary filtrate in a secondary precipitation method to form a secondary solid residue and a secondary liquid fraction;

(j) separating the primary solid residue from the primary liquid fraction and feeding the primary solid residue to step (a); and

(k) separating the secondary solid residue from the secondary liquid fraction and dissolving the secondary solid residue to form a Group VIII product solution.

47. The method of claim 46 further comprising combining the primary liquid fraction and the secondary liquid fraction to form a combined solution substantially free Group VIB and Group VIII metals.

48. The method of claim 47 further comprising combining the primary liquid fraction and the secondary liquid fraction to form a combined solution substantially free Group VIB and Group VIII metals.

49. The method of claim 48 further comprising subjecting the combined solution to sulfamate hydrolysis and sulfide oxidation at a temperature between 220°

C. and 240°

C., a pressure ranging from 2,000 kPa to 4,000 kPa and a retention time of between 0.5-hour and 1.5-hour to form a purified solution.

50. The method of claim 49 wherein the purified solution is ammonium sulfate.

51. The method of claim 46 wherein the precipitation step (c) is carried out at a pH not more than 3.0, at a temperature between about 75°

C. and 85°

C. for at least two hours.

54. The method of claim 46 wherein the separation steps (b), (d) and (f) each comprise at least a separation means selected from settling, filtration, decantation, centrifugation and combinations thereof.

56. The method of claim 47 wherein the primary precipitation method comprises sulfidation with a sulfur containing compound and a phosphate at a temperature and pressure and for a time sufficient to remove at least 95% of the Group VIB and Group VIII metals.

57. The method of claim 56 wherein the phosphate is a salt of di-ammonium hydrogen phosphate which is added to the primary filtrate immediately prior to sulfidation.

59. The method of claim 47 wherein the secondary precipitation method comprises sulfidation with a sulfur containing compound at a temperature and pressure and for a time sufficient to remove at least 90% of the Group VB metals and at least 95% of the Group VIB and Group VIII metals.

61. The method of claim 47, wherein the separation steps (iii) and (iv) are separation means selected from settling, filtration, decantation, centrifugation and combinations thereof.

62. The method of claim 48 wherein the combined solution comprises less than 100 ppm of the group VIB metal and less than 20 ppm of the Group VIII metal.

63. The method of claim 46, wherein at least 90% of the Group VIB metal precipitates from the pressure leach solution as a metal complex.

64. The method of claim 46, wherein the Group VIB metal is molybdenum and wherein the first pre-selected pH is in the range of 2.5 to 3.3 to precipitate greater than 90% of the molybdenum as an octamolybdate complex.

65. The method of claim 63, wherein the pressure leach solution is adjusted to the first pre-selected pH by adding to said solution at least one of a mineral acid or a sulfur compound having a sulfhydryl group or an ionized sulfhydryl group, or mixtures thereof.

66. The method of claim 64, wherein the pH of the PLS is adjusted to a pH of 3.5 or less with an acid selected from the group of sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid.

67. The method of claim 64, wherein the PLS is adjusted to a pH of 3 or less with the addition of a sulfuric acid to precipitate least 95% of the molybdenum as an octamolybdate complex.

68. The method of claim 64, wherein the pH of the pressure leach solution is adjusted to a pH of 3 or less with at least one of a water soluble sulfide, a water soluble polysulfide, or mixtures thereof.

69. The method of claim 47, wherein the Group VIB metal is molybdenum and the Group VIII metal is nickel, the pressure leach solution is adjusted to a pH of 3.5 or less with the addition of a sulfuric acid to precipitate and form the second solid residue comprising at least 95% of the molybdenum as an octamolybdate complex and at least 75% of the nickel as a nickel ammonium sulfate compound, dissolving the second solid residue in an acidic water having a pH of 2.5 or less at a temperature ranging between 75°

C. and 85°

C. to form an octamolybdate precipitate and a solution of a double salt of nickel and dissolving the octamolybdate precipitate in dilute ammonia at a temperature ranging from 50°

C. to 75°

C. to form an ammonium molybdate product.

70. The method of claim 68 further comprising:

separating the octamolybdate precipitate from the double salt of nickel solution to form the secondary filtrate comprising at least 80% of the nickel, from 0.1 to 3% of the molybdenum, and from 1 to 20% of any vanadium;

adding H₂S to the secondary filtrate at a gas overpressure ranging from 100 kPa to 500 kPa and at a temperature ranging from 50-110°

C. to precipitate the secondary solid residue comprising Mo, Ni, and V sulfides and oxy-hydroxides, obtain the secondary liquid fraction comprising 100 to 1000 gpL ammonium sulfate, less than 100 ppm molybdenum, less than 20 ppm nickel, and less than 100 ppm vanadium;

separating the secondary solid residue and the secondary liquid fraction;

dissolving the secondary solid residue at a pH of five or less in the presence of oxygen at a temperature between 150°

C. and 170°

C., a total pressure ranging from 150 psig to 170 psig for a time between 30 minutes and 1.5 hours to obtain a nickel sulfate product solution having a pH of less than 1;

combining the secondary liquid fraction with the primary liquid fraction to form a combined solution;

subjecting the combined solution to sulfamate hydrolysis and soluble sulfide species oxidation in the presence of steam and air at a temperature ranging between 220°

C. and 240°

C. to form a purified solution comprising of ammonium sulfate.

72. The method of claim 47, wherein at least one of a water soluble sulfide, a water soluble polysulfide, or mixtures thereof is added to the secondary filtrate for a pH level of between 6 and 9 to obtain Mo and Ni, precipitates from the ammonium sulfate solution.

73. The method of claim 57, wherein H₂S is added to the primary filtrate at a gas overpressure from 100 kPa to 500 kPa and at a temperature ranging from about 90°

C. to about 110°

C.

52. A method for recovering metals from metals bearing materials comprising:

(a) leaching finely divided sulfides of a Group VB metal, a Group VIB metal and a Group VIII metal with an ammonia containing leach solution at a temperature and a pressure sufficient to form a pressure leach slurry comprising at least a Group VIB soluble metal complex and at least a Group VIII soluble metal complex and a first solid residue;

(b) separating and removing the first solid residue from the pressure leach slurry to form a first pressure leach solution comprising the Group VIB soluble metal complex and the Group VIII soluble metal complex;

(c) precipitating from the first pressure leach solution, at a first pre-selected pH, a second solid residue comprising at least a portion of the Group VIB soluble metal complex to form a first slurry comprising the second solid residue and at least a portion of the Group VIII soluble metal complex;

(d) separating from the first slurry the second solid residue and a primary filtrate substantially free of Group VB, Group VIB and the Group VIII metals;

(e) dissolving the second solid residue at a second pre-selected pH to form a group VIB metal precipitate and a group VIII metal containing solution;

(f) separating the group VIB metal precipitate from the Group VIII metal containing solution;

(g) dissolving said Group VIB metal precipitate in a dilute base at a sufficient temperature to form a Group VIB soluble metal product;

(h) forming a secondary filtrate comprising substantially ammonium sulphate, the Group VIII soluble metal complex and trace amounts of Group VB and Group VIB metals;

(i) processing the primary filtrate in a primary precipitation method to form a primary solid residue and a primary liquid fraction and separately processing the secondary filtrate in a secondary precipitation method to form a secondary solid residue and a secondary liquid fraction;

(j) separating the primary solid residue from the primary liquid fraction and feeding the primary solid residue to step (a); and

(l) separating the secondary solid residue from the secondary liquid fraction and dissolving the secondary solid residue to form a Group VIII product solution.

53. The method of claim 52 wherein the first solid residue comprises a Group VB metal, the at least a Group VB metal complex and a carbonaceous material, and wherein the Group VB metal comprises vanadium and the Group VB metal complex comprises ammonium metavanadate.

55. The method of claim 52, wherein the primary filtrate comprises substantially ammonium sulfate and about 0.1 to 3% of the Group VIB metal for metal recovery, about 1 to 20% of the Group VB metal for metal recovery, and about 1 to 35% of the Group VIII metal for metal recovery.

58. The method of claim 55 wherein the primary filtrate comprises less than 500 ppm nickel and less than 1000 ppm of molybdenum and vanadium combined with an ammonium sulfate content of at least 400 gpL, the pH is initially adjusted to approximately 8 with ammonia and the primary precipitation method comprises sulfidation carried out at 100 kPa overpressure with hydrogen sulfide gas at a temperature between about 90°

C. and 110°

C. for 80 to 100 minutes and the pH is adjusted at least 2 times from basic to acidic and from acidic to basic.

60. The method of claim 58 wherein the sulfidation is carried out with hydrogen sulfide gas at an overpressure of 100 kPa, at a temperature between 90°

C. and 120°

C. at a pH between 8 and 9 and between 50 and 80 minutes.