Reduction of lime consumption when treating refractor gold ores or concentrates

• US 7,604,783 B2
• Filed: 10/11/2005
• Issued: 10/20/2009
• Est. Priority Date: 12/22/2004
• Status: Active Grant

• Current Assignee: Placer Dome Technical Services Limited
• Original Assignee: Placer Dome Technical Services Limited
• Inventors: Ferron, Cesare Giosue, King, James A., Ji, Jinxing, Fleming, Christopher Andrew
• Primary Examiner(s): Mayes; Melvin C
• Assistant Examiner(s): DAVIS, SHENG HAN
• Application Number:
  US11/249,120
• Publication Number:
  US 20060133974A1
• Time in Patent Office: 1,470 Days
• Field of Search: None
• US Class Current: 423/36
• CPC Class Codes: C22B 11/04 by wet processes extraction of metal compounds by leaching in organic solutions C22B3/16; treatment or purification of solutions by liquid-liquid extraction C22B3/26
• CPC Class Codes: C22B 3/08 Sulfuric acid , other sulfurated acids or salts thereof
• 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: Y02P 10/20 Recycling

Abstract

The present invention is directed to a precious metal recovery process in which basic ferric sulphates and/or jarosites are controlled by a number of mechanisms, including control of the oxidation reaction conditions in the first autoclave compartment, hot curing of the autoclave discharge slurry, and/or contacting of the autoclave feed slurry with the hot cured discharge liquid.

Claims

1. A precious metal recovery process, comprising:

(a) oxidizing an aqueous feed slurry in an autoclave, the feed slurry comprising a precious metal-containing material and sulphide sulphur, wherein at least most of the sulphide sulphur is oxidized to sulphate sulphur and wherein at least a portion of the sulphate sulphur is in the form of a reactive iron-containing precipitate;

(b) removing, from the autoclave, an aqueous discharge slurry comprising discharge solids and aqueous discharge liquid, the discharge solids comprising at least a portion of the precious metal and at least most of the reactive iron-containing precipitate, and wherein the aqueous discharge slurry comprises an acid;

(c) prior to contact of an acid consumer other than the reactive iron-containing precipitate with at least most of the discharge solids, allowing at least most of the reactive iron-containing precipitate in the discharge solids to react with the acid in the aqueous discharge liquid to form a hot cured slurry, the hot cured slurry comprising the discharge solids and a dissolved iron-containing species derived from the reaction of the acid and reactive iron-containing species;

(d) after step (c), contacting the discharge solids with the acid consumer;

(e) leaching at least most of the precious metal from the discharge solids to form a dissolved precious metal; and

(f) recovering the dissolved precious metal.

2. The process of claim 1, wherein the reactive iron-containing precipitate comprises basic ferric sulphate, the dissolved iron-containing species comprises dissolved ferric sulphate, and the acid comprises sulphuric acid, wherein the precious metal is gold, wherein in step (c), the temperature of the aqueous discharge slurry is maintained at or above 60°

Celsius, and wherein, in step (c), the aqueous discharge slurry is held in a stirred vessel and wherein, in the step (c)

at least about 50% of the basic ferric sulphates in the aqueous discharge slurry is converted into dissolved ferric sulphate according to the following equation;

2Fe(SO₄)(OH)_(s)+H₂SO₄=Fe₂(SO₄)_3(aq)+2H₂O.

3. The process of claim 2, wherein the hot cured slurry comprises a liquid phase comprising dissolved ferric sulfate and a solid phase comprising the discharge solids and wherein the hot cured slurry comprises one or more of:

i) from about 10 to about 140 g/l dissolved ferric sulphate in the liquid phase of the hot cured slurry;

ii) no more than about 3 wt % basic ferric sulfate in the solid phase of the hot cured slurry;

iii) no more than about 1 wt % jarosites in the solid phase of the hot cured slurry; and

iv) from about 10 to about 40 g/l sulphuric acid in the liquid phase of the hot cured slurry, wherein, in step (d), the pH of any liquid in contact with the discharge solids is increased from a first pH in the range of from about pH 2.0 to about pH 5.0 to a second pH in the range of from about pH 9.0 to about pH 11.0.

4. The process of claim 2, wherein, after step (c), the hot cured slurry comprises:

i) from about 10 to about 140 g/l dissolved ferric sulphate, and

ii) from about 10 to about 40 g/l sulphuric acid, wherein the discharge solids, after step (c) comprise;

iii) no more than about 5 wt % basic ferric sulphates, and

iv) no more than about 5 wt % jarosites, wherein a liquid phase of the hot cured slurry after step (c) comprises at least about 70% of the ferric iron in the aqueous discharge slurry before step (c), further comprising;

after step (c) and before step (d), separating at least a portion of the liquid phase from a solid phase comprising the discharge solids, wherein the separated liquid phase comprises no more than about 1 wt % solids, and wherein the separated solid phase comprises no more than about 70 vol. % liquid.

5. The process of claim 2, wherein the hot cured slurry temperature is from about 70°

to about 120°

C.

6. The process of claim 2, wherein the hot cured slurry has a total iron content, wherein at least about 80% of the total iron content is from the dissolved ferric sulphate and wherein no more than about 20% of the total iron content is from the basic ferric sulphate.

7. The process of claim 3, further comprising:

(g) separating a solid phase of the hot cured slurry from the liquid phase, wherein the solid phase comprises at least most of the precious metal, and the liquid phase comprises at least most of the dissolved ferric sulphate and sulphuric acid.

8. The process of claim 7, wherein prior to step (g), but after step (c), the hot cured slurry temperature ranges from about 30°

to about 50°

C.

9. The process of claim 7, wherein the liquid phase comprises at least about 90% of the dissolved ferric sulphate and sulphuric acid and wherein any liquid reporting to the solid phase comprises no more than about 10% of the dissolved ferric sulphate.

10. The process of claim 7, further comprising after step (g):

(h) contacting the separated liquid phase with the acid consumer.

15. The process of claim 1, wherein the allowing step is performed in one or more hot cure vessels and wherein a residence time of the at least most of the reactive iron-containing precipitate in the one or more hot cure vessels ranges from about 1 hour to about 24 hours.

17. The process of claim 10, wherein the acid consumer is selected from the group consisting of limestone, lime, and combinations thereof.

18. The process of claim 10, wherein the liquid phase pH is increased from a first pH ranging from about pH 0.5 to about pH 1.3 to a second pH ranging from about pH 4.5 to about pH 10.0.

19. The process of claim 10, wherein the acid consumer comprises first and second acid consumers and wherein step (h) comprises the sub-steps:

(h1) performing a first neutralization step, wherein the first acid consumer is contacted with the dissolved ferric sulphate and sulphuric acid to form a first neutralization slurry; and

(h2) performing a second neutralization step, wherein the second acid consumer differs from the first acid consumer and wherein the second acid consumer is contacted with the first neutralization slurry to form a second neutralization slurry.

20. The process of claim 19, wherein the first acid consumer is limestone and wherein the first neutralization slurry comprises ferric hydroxide and gypsum.

21. The process of claim 20, wherein the second acid consumer is lime, wherein the acid consumer is added during step h2 to form a second neutralization slurry, and wherein the acid consumer is added in a sufficient amount to achieve a second neutralization slurry pH of about pH 7.0 or greater.

22. The process of claim 10, wherein the added acid consumer causes the separated a liquid phase to have a pH of pH 7.0 or greater, and further comprising:

(i) thereafter subjecting the separated liquid phase to a liquid/solid separation step to form a tailings solid residue and a recycle liquid.

23. The process of claim 22, wherein the recycle liquid is contacted with the hot cured slurry prior to step (h).

24. The process of claim 7, wherein the separated liquid phase is contacted with the precious-metal containing material prior to step (a).

25. The process of claim 7, wherein the separated solid phase comprises no more than about 10 wt% basic ferric sulphates and/or jarosites.

26. The process of claim 7, wherein the separated solid phase is contacted with the acid consumer, wherein the pH of the any liquid reporting to the separated solid phase is increased by the acid consumer from a first pH ranging from about pH 2 to about pH 5 to a second pH ranging from about pH 9 to about pH 11.

27. The process of claim 26, wherein the acid consumer is lime.

57. The process of claim 1, wherein the aqueous discharge slurry has a dissolved iron concentration of more than 1 gram/liter.

11. A precious metal recovery process, comprising:

(a) oxidizing sulphide sulphur in an aqueous feed slurry in an autoclave, the feed slurry comprising a precious metal-containing material, wherein at least most of the sulphide sulphur is oxidized to sulphate sulphur and wherein at least a portion of the sulphate sulphur is in the form of basic iron sulphate in a solid phase;

(b) removing, from the autoclave, an aqueous discharge slurry comprising discharge solids and aqueous discharge liquid, the discharge solids comprising at least a portion of the precious metal and at least most of the solid-phase basic iron-sulphate, and wherein the aqueous discharge slurry comprises sulphuric acid;

(c) allowing at least most of the solid-phase basic iron sulphate in the aqueous discharge solids to react with the sulphuric acid in the aqueous discharge liquid to form a hot cured slurry comprising ferric sulphate dissolved in the aqueous discharge liquid, wherein the allowing step (c) is performed in one or more hot cure vessels and wherein a residence time of the at least most of the solid-phase basic iron sulfate in the one or more hot cure vessels ranges from about 1 hour to about 24 hours;

(d) thereafter separating the aqueous discharge liquid from the aqueous discharge solids, wherein at least most of the dissolved ferric sulphate is in the separated aqueous discharge liquid and wherein the separated aqueous discharge solids comprise sulphuric acid;

(e) contacting an acid consumer with at least one of the separated aqueous discharge liquid and the separated discharge solids to form at least one of neutralized aqueous discharge liquid and neutralized aqueous discharge solids, respectively;

(f) contacting a lixiviant, at a pH above about pH 7.0, with the neutralized discharge solids to dissolve at least most of the precious metal; and

(g) recovering the dissolved precious metal.

12. The process of claim 11, wherein the precious metal is gold, wherein in step (c), the aqueous discharge slurry has a discharge slurry temperature, wherein the discharge slurry temperature is maintained at or above 60 degrees Celsius, and wherein, in step (c), the aqueous discharge slurry is held in a stirred vessel.

13. The process of claim 11, wherein the acid consumer is selected from the group consisting essentially of lime, limestone, and combinations thereof and wherein, in step (e), any liquid in the discharge solids has a discharge solids pH and wherein the discharge solids pH is increased from a first pH in the range of from about pH 2.0 to about pH 5.0 to a second pH in the range of from about pH 9.0 to about pH 11.0, and further comprising:

(h) contacting dissolved ferric sulphate in the separated aqueous discharge liquid with the acid consumer to convert at least most of the dissolved ferric sulphate to ferric hydroxide.

16. The process of claim 11, wherein step (c) is conducted prior to contact of at least most of the solid-phase basic iron sulphate with an acid consumer other than basic ferric sulphate.

28. The process of claim 11, wherein the solid-phase basic iron sulphate comprises basic ferric sulphate and wherein the precious metal is gold.

29. The process of claim 11, wherein step (c) is conducted at a temperature of at least 60°

C. and within a stirred hot cure vessel.

30. The process of claim 29, wherein step (c) is conducted at a temperature ranging from about 70°

to about 120°

C.

31. The process of claim 11, wherein the solid-phase basic iron sulphate comprises Fe(OH)(SO₄)_(s) and the dissolved ferric sulphate comprises Fe₂(SO₄)_3(aq) in a dissolved state, and wherein step (c) further comprises converting at least about 50% of the solid-phase Fe(OH)(SO₄)_(S) to the Fe₂(SO₄)_3(aq) in the dissolved state.

32. The process of claim 11, wherein the hot cured slurry comprises:

the dissolved ferric sulphate at a concentration ranging from about 10 g/l to about 140 g/l; and

the sulphuric acid at a concentration ranging from about 10 g/l to about 40 g/l; and

wherein at least one of the following true;

i) the hot cured slurry comprises no more than about 3 wt % of the solid-phase basic iron sulphate; and

ii) the hot cured slurry comprises no more than about 1 wt % of jarosites in the solid phase.

33. The process of claim 11, wherein the hot cured slurry has a total iron content, wherein at least about 80% of the total iron content is from the dissolved ferric sulphate and no more than about 20% of the total iron content is from the solid-phase basic iron sulphate.

34. The process of claim 11, wherein after step (c) but prior to and/or during step (d), the hot cured slurry temperature is reduced to a temperature ranging from about 30°

to about 50°

C.

35. The process of claim 11, wherein the aqueous discharge liquid comprises at least about 90% of the dissolved metal sulphates and sulphuric acid and wherein the discharged solid comprises no more than about 10% of the dissolved metal sulphates.

36. The process of claim 11, wherein the aqueous discharge liquid is contacted with the acid consumer.

37. The process of claim 36, wherein the acid consumer comprises at least one of limestone, lime, and a mixture thereof.

38. The process of claim 11, wherein step (e) comprises the substeps:

(e1) providing a first neutralization step, wherein a first acid consumer is contacted with the dissolved ferric sulphate and sulphuric acid to form the neutralized separated aqueous liquid; and

(e2) providing a second neutralization step, wherein a second acid consumer, the second acid consumer being different than the first acid consumer, is contacted with the separated aqueous discharge solids to form the neutralized discharge solids.

41. The process of claim 36, wherein through contact with the acid consumer the aqueous discharge liquid pH is increased from a first pH ranging from about pH 0.5 to about pH 1.3 to a second pH ranging from about 4.5 to about pH 10.0.

42. The process of claim 36, wherein the aqueous discharge liquid pH is about pH 7 or greater and wherein the aqueous discharge liquid pH 7 or greater is achieved by adding a sufficient amount of the acid consumer, and further comprising:

subjecting the aqueous discharge liquid to a liquid/solid separation step to form a tailings solid residue and a recycle liquid.

43. The process of claim 42, wherein the recycle liquid is contacted with the hot cured slurry prior to step (d).

44. The process of claim 11, wherein a portion of the aqueous discharge liquid is contacted with the precious-metal containing material prior to step (a).

45. The process of claim 11, wherein the discharge solids comprises no more than about 10 wt % solid phase jarosites and/or the basic metal sulphates.

46. The process of claim 11, wherein the discharge solids are contacted with the acid consumer, wherein the discharge solids have a discharge solids pH and wherein the discharge solids pH is increased from a first pH ranging from about pH 2 to about pH 5 to a second pH ranging from about pH 9 to about pH 11.

47. The process of claim 46, wherein the acid consumer is lime.

58. The process of claim 11, wherein the aqueous discharge slurry has a dissolved iron concentration of more than 1 gram/liter.

14. A precious metal recovery process, comprising:

(a) oxidizing an aqueous feed slurry in an autoclave, the feed slurry comprising a precious metal-containing material and sulphide sulphur, wherein at least most of the sulphide sulphur is oxidized to sulphate sulphur and wherein at least a portion of the sulphate sulpur is in the form of a reactive iron-containing precipitate;

(b) removing, from the autoclave, an aqueous discharge slurry comprising discharge solids and aqueous discharge liquid, the discharge solids comprising at least a portion of the precious metal and at least most of the reactive iron-containing precipitate, wherein the reactive iron-containing precipitate comprises basic iron sulphate, and wherein the aqueous discharge slurry comprises an acid;

(c) allowing at least most of the reactive iron-containing precipitate in the aqueous discharge solids to react with the acid to form a dissolved iron-containing species, wherein the dissolved iron-containing species comprises dissolved ferric sulphate, and wherein the acid comprises sulphuric acid;

(d) after step (c), contacting the discharge solids with an acid consumer, wherein the acid consumer is predominantly lime, wherein liquid in contact with the discharge solids has a discharge solids pH, wherein the discharge solids pH is increased from a first pH in the range of from about pH 2.0 to about pH 5.0 to a second pH in the range of from about pH 9.0 to about pH 11.0;

(e) contacting the dissolved ferric sulphate in the aqueous discharge liquid with lime and/or limestone to convert at least most of the dissolved ferric sulphate to ferric hydroxide;

(f) leaching at least most of the precious metal from the discharge solids to form a dissolved precious metal; and

(g) recovering the dissolved precious metal.

53. The process of claim 14, wherein the acid consumer is other than the reactive iron-containing precipitate, wherein the allowing step (c) is conducted prior to contacting the acid consumer with at least most of the discharge solids of step (d), wherein the at least most of the reactive iron-containing precipitate in the discharge solids reacts with the acid in the aqueous discharge liquid to form the dissolved iron-containing species, wherein the aqueous discharge liquid forms a hot cured slurry comprising the discharge solids and the dissolved iron-containing species and wherein the dissolved iron-containing species is derived from the reaction of the acid with the reactive iron-containing species.

54. The process of claim 53, wherein, after step (c), the hot cured slurry comprises:

i) from about 10 to about 140 g/l dissolved ferric sulphate, and

ii) from about 10 to about 40 g/l sulphuric acid, wherein the discharge solids, after step (c), comprise;

iii) no more than about 5 wt % basic ferric sulphates, and

iv) no more than about 5 wt % jarosites, wherein a liquid phase of the hot cured slurry after step (c) comprises at least about 70% of the ferric iron in the aqueous discharge slurry before step (c), and further comprising;

after step (c) and before step (d), separating at least a portion of the liquid phase from a solid phase comprising the discharge solids, wherein the separated liquid phase comprises no more than about 1 wt % solids, and wherein the separated solid phase comprises no more than about 70 vol. % liquid.

55. The process of claim 53, further comprising:

(h) after step (c), separating a solid phase of the hot cured slurry from a liquid phase, wherein prior to the separating step (h) the hot cured slurry temperature ranges from about 30°

to about 50°

C., wherein the solid phase comprises at least most of the precious metal, and the liquid phase comprises at least most of the dissolved ferric sulphate and sulphuric acid, wherein the liquid phase comprises at least about 90% of the dissolved ferric sulphate and sulphuric acid and wherein any liquid reporting to the solid phase comprises no more than about 10% of the dissolved ferric sulphate.

56. The process of claim 53, wherein the acid consumer comprises first and second acid consumers and wherein step (e) comprises the sub-steps:

(e1) performing a first neutralization step, wherein the first acid consumer is limestone, wherein the limestone is contacted with the dissolved ferric sulphate and sulphuric acid to form a first neutralization slurry comprising ferric hydroxide and gypsum; and

(e2) performing a second neutralization step, wherein the second acid consumer is lime, wherein the lime is contacted with the first neutralization slurry to form a second neutralization slurry, wherein the second acid consumer is lime, wherein the lime is added is added in a sufficient amount to achieve a second neutralization slurry pH of about pH 7.0 or greater, and further comprising;

(i) thereafter subjecting the second neutralization slurry to a liquid/solid separation step to form a tailings solid residue and a recycle liquid, wherein the recycle liquid is contacted with the hot cured slurry prior to step (d).

59. The process of claim 14, wherein the aqueous discharge slurry has a dissolved iron concentration of more than 1 gram/liter.

39. The process of 38, wherein the first acid consumer is limestone and wherein the neutralized separated aqueous liquid comprises ferric hydroxide and gypsum solids.

40. The process of claim 39, wherein the second acid consumer is lime and wherein the second acid consumer is added in an effective amount during step e2 to achieve a neutralized discharge solids pH of about pH 7 or greater.

48. A precious metal recovery process, comprising:

(a) oxidizing sulphide sulphur in an aqueous feed slurry in an autoclave, the feed slurry comprising a precious metal-containing material, wherein at least most of sulphide sulphur is oxidized to sulphate sulphur and wherein at least a portion of the sulphate is in the form of basic iron sulphate in a solid phase;

(b) removing, from the autoclave, an aqueous discharge slurry comprising discharge solids and aqueous discharge liquid, the discharge solids comprising at least a portion of the precious metal and at least most of the solid-phase basic iron sulphate, and wherein the aqueous discharge slurry comprises sulphuric acid;

(c) allowing at least most of the solid-phase basic iron sulphate in the aqueous discharge solids to react with the sulphuric acid to form ferric sulphate dissolved in the aqueous discharge liquid;

(d) thereafter separating the aqueous discharge liquid from the discharge solids, wherein at least most of the dissolved ferric sulphate is in the separated aqueous discharge liquid and wherein the separated aqueous discharge solids comprise sulphuric acid;

(e) contacting the separated discharge solids with an acid consumer to consume at least most of the sulphuric acid and dissolved metal sulphates to form a neutralized discharge solids, wherein the acid consumer is predominantly lime and/or limestone, wherein the separated discharge solids have a discharge solids pH, wherein the discharge solids pH is increased from a first pH in the range of from about pH 2.0 to about pH 5.0 to a second pH in the range of from about pH 9.0 to about pH 11.0;

(f) contacting the dissolved ferric sulphate in the aqueous discharge liquid with lime and/or limestone to convert at least most of the dissolved ferric sulphate to ferric hydroxide;

(g) contacting a lixiviant, at a pH above about pH 7.0, with the neutralized discharge solids to dissolve at least most of the precious metal; and

(h) recovering the dissolved precious metal.

49. The process of claim 48, wherein the acid consumer is other than the basic iron sulphate, wherein the allowing step (c) is conducted prior to contacting the acid consumer with at least most of the discharge solids of step (e), wherein the at least most of the basic iron sulphate in the discharge solids reacts with the sulphuric acid in the aqueous discharge liquid to form the dissolved ferric sulphate, wherein the aqueous discharge liquid forms a hot cured slurry comprising the discharge solids and the dissolved ferric sulphate and wherein the dissolved ferric sulphate is derived from the reaction of the sulphuric acid with the basic iron sulphate.

50. The process of claim 49, wherein, after step (c), the hot cured slurry comprises:

i) from about 10 to about 140 g/l dissolved ferric sulphate, and

ii) from about 10 to about 40 g/l sulphuric acid, wherein the discharge solids, after step (c), comprise;

iii) no more than about 5 wt % basic iron sulphates, and

iv) no more than about 5 wt % jarosites, wherein a liquid phase of the hot cured slurry after step (c) comprises at least about 70% of the ferric iron in the aqueous discharge slurry before step (c), and further comprising;

after step (c) and before step (d), separating at least a portion of the liquid phase from a solid phase comprising the discharge solids, wherein the separated liquid phase comprises no more than about 1 wt % solids, and wherein the separated solid phase comprises no more than about 70 vol. % liquid.

51. The process of claim 49, further comprising:

(i) after step (c), separating a solid phase of the hot cured slurry from a liquid phase, wherein prior to the separating step (i) the hot cured slurry temperature ranges from about 30 °

to about 50°

C., wherein the solid phase comprises at least most of the precious metal, and the liquid phase comprises at least most of the dissolved ferric sulphate and sulphuric acid, wherein the liquid phase comprises at least about 90% of the dissolved ferric sulphate and sulphuric acid and wherein any liquid reporting to the solid phase comprises no more than about 10% of the dissolved ferric sulphate.

52. The process of claim 49, wherein the acid consumer comprises first and second acid consumers and wherein step (e) comprises the sub-steps:

(e1) performing a first neutralization step, wherein the first acid consumer is limestone, wherein the limestone is contacted with the dissolved ferric sulphate and sulphuric acid to form a first neutralization slurry comprising ferric hydroxide and gypsum; and

(e2) performing a second neutralization step, wherein the second acid consumer is lime, wherein the lime is contacted with the first neutralization slurry to form a second neutralization slurry, wherein the second acid consumer is lime, wherein the lime is added is added in a sufficient amount to achieve a second neutralization slurry pH of about pH 7.0 or greater, and further comprising;

(i) thereafter subjecting the second neutralization slurry to a liquid/solid separation step to form a tailings solid residue and a recycle liquid, wherein the recycle liquid is contacted with the hot cured slurry prior to step (d).

60. The process of claim 48, wherein the aqueous discharge slurry has a dissolved iron concentration of more than 1 gram/liter.