AU2004239345A1

AU2004239345A1 - Treatment of base metal concentrate by a two-step bioleaching process

Info

Publication number: AU2004239345A1
Application number: AU2004239345A
Authority: AU
Inventors: Clint Bowker; Paul Harvey
Original assignee: BHP Billiton SA Ltd
Current assignee: BHP Billiton SA Ltd
Priority date: 2003-05-19
Filing date: 2004-05-15
Publication date: 2004-11-25
Anticipated expiration: 2024-05-15
Also published as: AR044408A1; ZA200509214B; WO2004101834A2; AU2004239345B2; CN1697887A; PE20050453A1; WO2004101834A3; AP2005003447A0; US20070028721A1; CA2526104A1; AP1973A; CN100339493C

Description

WO 2004/101834 PCT/ZA2004/000052 TREATMENT OF BASE METAL CONCENTRATE BACKGROUND OF THE INVENTION [0001] This invention relates to the treatment of a base metal containing concentrate. 5 [0002] The recovery of a base metal such as copper from a concentrate, which contains arsenic, using a bioleaching process, can be problematic for it is necessary to avoid producing a bioleach residue which is contaminated with arsenic. [0003] US patent No. 6,461,577 addresses the problem of arsenic toxicity of extremely thermophilic bacterial cultures by means of a two-stage leaching process. 10 In a first mesophilic stage a major part of the arsenic contained in the material being treated is leached from the material and then oxidised from As(Ill) to As(V). The remaining leachable metal content of the material being treated is leached out in a second thermophilic stage. The concentration of pentavalent arsenic falls quickly and the toxic effect thereof on the thermophilic bacteria thus falls at the same rate. 15 [0004] It is desirable though to remove the soluble arsenic as ferric arsenate which passes EPA limits and is safe for land disposal and which, to the extent possible, is not in a bioleach residue. SUMMARY OF INVENTION [0005] The invention provides a method of treating a concentrate containing at least 20 one base metal which includes the steps of subjecting the concentrate to a primary WO 2004/101834 PCT/ZA2004/000052 mesophilic and moderate thermophilic bioleaching process to leach sulphides in the concentrate, processing a residue of the primary bioleach process to recover at least one metal from the primary bioleach residue, subjecting a residue from the metal recovery process to a thermophilic secondary bioleaching process to release the at 5 least one base metal from the metal recovery residue into solution, and recovering the at least one base metal at least from the solution produced by the thermophilic secondary bioleaching process. [0006] The primary bioleaching process may be carried out at a temperature of from 35 0 C to 500C. 10 [0007] Preferably the at least one base metal is also recovered from a solution produced by the primary bioleach bioleaching process. [0008] The method preferably includes the step of preleaching the concentrate, before the primary bioleach bioleaching process, using leach solution from at least one of the bioleaching processes. Preferably the leach solution is derived from the 15 primary bioleaching process and the thermophilic secondary bioleaching process. [0009] The preleaching step is used to remove easily leachable base metal from the concentrate before the primary bioleaching process. Elemental sulphur which may accumulate during the preleach step due to rapid leaching of easily leachable sulphides, may be removed during the bioleaching stages, especially during the 20 thermophilic secondary bioleaching process at elevated temperatures. [0010] The primary bioleaching process may be carried out in a series of continuously stirred tank reactors which are operated at a temperature of from 35°C 2 WO 2004/101834 PCT/ZA2004/000052 to 50 0 C in the presence of an active mixed culture of mesophilic and moderate thermophilic microorganisms. [0011] A mixed culture of mesophile (200C to 400C) and moderate thermophile (400C to 550C) microorganisms is preferably used to maximise sulphide bioleaching 5 and sulphur biooxidation during the treatment process. The mixed culture may contain microorganisms like Leptospirillum ferrooxidans and Acidithiobacillus caldus, a good iron oxidiser and a good sulphur oxidiser respectively. [0012] The primary bioleach process may also contain thermophilic microorganisms, which are not effectively active at the temperature range of 35 0 C to 500C. Such 10 microorganisms will, however, still be living but will be dormant or slowly metabolising. When the temperature increases during the thermophilic secondary bioleaching process these microorganisms will reactivate their activity. This may be very useful for base metal concentrates, as the thermophilic secondary bioleaching stage would be continuously re-inoculated. 15 [0013] The pH of the concentrate or pulp in reactors in which the primary bioleaching is carried out may be controlled at a value of from 1,2 to 1,7. This may be achieved by the addition of limestone or raffinate produced in the base metal recovery step, to the reactors. [0014] Oxygen may be supplied to the concentrate in the reactors in the form of 20 enriched air which may contain from 95% to 98% oxygen, during at least part of the bioleaching processes. 3 WO 2004/101834 PCT/ZA2004/000052 [0015] An objective of operating the primary bioleaching process under the aforementioned conditions is to maximise the leaching of the sulphides in the concentrate and to maximise mass loss, and to minimise the precipitation in pentavalent form of arsenic which may be present in solution. The product from the 5 primary bioleach residue may contain high concentrations of elemental sulphur due to the maximised bioleaching conditions. [0016] In the metal recovery process toxic silver may be removed from the primary bioleaching residue. The silver may be removed using a brine leaching process. [0017] The thermophilic secondary bioleaching process may be carried out in a 10 series of continuously stirred tank reactors at a temperature of from 65°C to 800C in the presence of active quantities of extreme thermophilic microorganisms. [0018] The method may include the step of controlling the pH of the pulp in the thermophilic reactors at a value of from 1,,0 to 1,7. This may be achieved by the addition of limestone or raffinate produced in the metal recovery step. Oxygen & 15 carbon dioxide may be supplied to the reactors in the form of enriched gas containing from 95% to 98% oxygen and 1% to 5% carbon dioxide. [0019] An objective of operating the thermophilic secondary bioleaching process under the aforementioned parameters is to maximise the oxidation of sulphides minerals and mass loss, and to minimise the precipitation in pentavalent form of 20 arsenic which may be present in solution. [0020] Furthermore sulphur oxidation at thermophilic temperature conditions is maximised and thus any elemental sulphur produced during the proceeding pre 4 WO 2004/101834 PCT/ZA2004/000052 leach and primary bioleach may be fully oxidised. This is very important if further treatment of the thermophilic secondary bioleach residue is required for precious group metals (PGM's) recovery like gold. Elemental sulphur increases cyanide consumption during cyanidation to recover gold and thus contributes significantly to 5 the increase in cyanidation costs. Additionally, elemental sulphur not oxidised decreases the acid produced in the bioleach solution and thus may decrease the effectiveness of any preleach step using recycled bioleach solution. [0021] As indicated the at least one base metal is recovered from the leach solutions produced by the bioleaching processes. Preferably the pH of the solution 10 produced in the preleaching step is adjusted to maximise recovery of the at least one base metal using solvent extraction techniques. [0022] Arsenic present in the solution may be caused to precipitate as ferric arsenate by increasing the pH of the solution to at least 2. [0023] The pH of the solution may be increased by the addition of limestone slurry to 15 the solution. [0024] The pH adjustment may be carried out in a series of continuously stirred tank reactors which are operated at a temperature of from 60 0 C to 80 0 C. [0025] The at least one base metal, eg. copper, may be recovered by concentrating the copper and stripping, followed by cathode production by electrowinning. 20 5 WO 2004/101834 PCT/ZA2004/000052 BRIEF DESCRIPTION OF THE DRAWING [0026] The invention is further described by way of example with reference to the accompanying drawing which is a flow sheet illustrating various steps in a method of treating a concentrate obtaining at least one base metal in accordance with the 5 principles of the invention. DESCRIPTION OF PREFERRED EMBODIMENT [0027] In the method of the invention a concentrate 10 which contains a base metal such as copper and which may have a high arsenic content is subjected to a preleaching step 12. In this step the fresh concentrate is contacted with bioleach 10 overflow solutions 14 and 16 respectively produced in subsequent primary and thermophilic secondary bioleaching stages 18 and 20. [0028] The solutions 14 and 16 are rich in ferric and remove easily leachable copper from the feed 10. This ensures a lower residual copper tenor in the bioleaching tanks in the stages 18 and 20. 15 [0029] The product 22 of the preleaching stage is subjected to solid/liquid separation 24. An overflow solution 26 from the separation step 24 is directed to a pH adjustment stage 28 while the underflow 30, diluted with water 32 and raffinate 34 from a solvent extraction section 36, is fed to the primary bioleaching stage 18. [0030] The purpose of the primary bioleaching stage 18 is to oxidise sulphide 20 minerals in the feed and release base metals of interest into solution. The bioleaching is carried out in a series of continuously stirred tank reactors which are 6 WO 2004/101834 PCT/ZA2004/000052 operated at a temperature of 35 0 C to 500C in the presence of active quantities of mesophilic and moderate thermophilic microorganisms. [0031] The pH of the pulp of the reactors in the primary bioleaching stage is controlled at a value of from 1,2 to 1,7 by the addition of limestone 40 or raffinate 34. 5 Oxygen 42, required for the oxidative reaction, is supplied in the form of enriched air with an oxygen content of from 95% to 98%. [0032] By operating the primary bioleaching stage 18 under the aforementioned conditions the oxidation of the sulphide minerals and the mass loss are maximised while, if arsenic is present in the feed, the precipitation thereof in pentavalent form is 10 minimised. [0033] The product 44 of the primary bioleaching section 18 reports to bioleach thickening and washing 46. As has been indicated the overflow solution 14 is fed to the preleaching step 12 while the underflow 48 is the feed to a metal recovery section 50. 15 [0034] The purpose of the step 46 is to separate the liquids and the solids so that the base metals of interest and arsenic, if present, report to the pH adjustment section 28 via the preleaching step 12. In the metal recovery step 50 toxic silver 52 is removed from the primary bioleaching residue 48 using a brine leaching or other suitable method. 20 [0035] The residue 54 from the metal recovery step is repulped with water 56 and raffinate 34 and the resulting slurry is fed to the thermophilic secondary bioleaching stage 20. 7 WO 2004/101834 PCT/ZA2004/000052 [0036]The purpose of the stage 20 is to oxidise, to the extent possible, the sulphide minerals and the elemental sulphur which were not leached in the primary bioleaching stage 18. The base metals of interest are thereby released into solution. The thermophilic secondary bioleaching process is carried out in a series of 5 continuously stirred tank reactors which are operated at a temperature of from 650C to 800C in the presence of active quantities of extreme thermophilic microorganisms. [0037] The pH of the pulp in the thermophilic reactors is controlled at a value of from 1,0 to 1,7 by the addition of limestone 40 or raffinate 34. Oxygen 42 required for the oxidative reactions is supplied in the form of enriched gas with an oxygen content of 10 from 95% to 98%. Carbon dioxide 57 may be required for improved thermophilic cell growth is supplied in the form of enriched gas with a carbon dioxide content of 1% to 5% by volume. By operating the thermophilic secondary bioleaching sections under these conditions the oxidation of the sulphide minerals and the mass loss are maximised while the precipitation of arsenic which may be present in the slurry 54, in 15 the form of pentavalent arsenic, is minimised. [0038] The product 60 of the thermophilic bioleaching section 20 reports to a bioleach thickening and washing step 62. The overflow solution 16 is fed to the preleaching section 12 while the underflow 64 is directed to a tailings pond 66 for disposal. If the underflow 64 contains PGM's then the underflow is directed to a 20 metal recovery step 67 where the metal is removed from the underflow using cyanide as a leaching process for gold or other suitable method. 8 WO 2004/101834 PCT/ZA2004/000052 [0039] The purpose of the step 62 is to separate liquid and solids so that base metals of interest and arsenic, if present, are reported in solution to the pH adjustment section 28 via the preleaching stage 12. [0040] The pH adjustment section 28 includes a series of continuously stirred tank 5 reactors which are operated at a temperature of from 600C to 800C. The pH of the solution 26 is increased to a required level using limestone 40 or any other suitable neutralising agent. The product 70 of the pH adjustment section is then thickened in a step 72. The thickener underflow 74, which contains precipitated ferric arsenate, is directed to a tailings pond 76 for disposal. The overflow from the thickener step 10 reports as pregnant leach solution (PLS) 80 to the solvent extraction section 36. [0041] The purpose of the pH adjustment section 28 is to increase the pH of the pregnant leach solution, which is fed to the solvent extraction section 36, to above 2,0 so that the solvent extraction efficiency is maximised. Arsenic which-is present in the solution 26 is caused, by the increase in the pH, to precipitate primarily as ferric 15 arsenate which is not readily dissolved. The ferric arsenate passes EPA limits and is safe for land disposal. [0042] In the solvent extraction section 36 dissolved copper is recovered from the pregnant leached solution. The copper is stripped followed by cathode production (84) by electrowinning. 20 [0043] In the process of the invention the base metal containing concentrate is subjected to primary mesophilic and or moderate thermophilic leaching, metal recovery and thermophilic secondary leaching in combination so that secondary sulphides are successfully and economically leached in the primary section, toxic 9 WO 2004/101834 PCT/ZA2004/000052 silver is removed in the metal recovery section, and a residue containing unleached primary sulphides and elemental sulphur is leached to completion successfully and economically in the thermophile secondary section. If arsenic is present in the concentrate the primary and thermophilic secondary sections are operated so that 5 the redox potential of the solutions produced result in the natural oxidation of As(III) to As(V). Arsenic precipitation in the bioleaching sections is intentionally minimised so that the arsenic is precipitated externally in the pH adjustment section 28. This avoids the production of a bioleach residue contaminated with arsenic. [0044] It is cost effective to reduce the arsenic reporting to the thermophilic stage 20 10 by causing the arsenic to precipitate in a separate dedicated process step ie. the pH adjustment section 28. By minimising precipitation in the mesophilic stage 18 the mass loss throughout the process is maximised. This reduces the capital and operating cost of the downstream processes including the thermophilic section 20. [0045] Furthermore sulphur oxidation at thermophilic temperature conditions is 15 maximised and thus any elemental sulphur produced during the proceeding pre leach and primary bioleach may be fully oxidised. This is important if further treatment of the thermophilic secondary bioleach residue is required for precious group metals (PGM's) recovery like gold. Elemental sulphur increases cyanide consumption during cyanidation to recover gold and thus contributes significantly to 20 the increase in cyanidation costs. Additionally, elemental sulphur not oxidised decreases the acid produced in the bioleach solution and thus may decrease the effectiveness of any preleach step using recycled bioleach solution. 10

Claims

1. A method of treating a concentrate containing at least one base metal which includes the steps of subjecting the concentrate to a primary mesophilic and moderate thermophilic bioleaching process to leach sulphides in the 5 concentrate, processing a residue of the primary bioleach process to recover at least one metal from the primary bioleach residue, subjecting a residue from the metal recovery process to a thermophilic secondary bioleaching process to release the at least one base metal from the metal recovery residue into solution, and recovering the at least one base metal at least from the solution 10 produced by the thermophilic secondary bioleaching process.

2. A method according to claim 1 wherein the primary bioleaching process is carried out at a temperature of from 350C to 500C.

3. A method according to claim 1 or 2 wherein the at least one base metal is also recovered from a solution produced by the primary bioleach bioleaching 15 process.

4. A method according to any one of claims 1 to 3 which includes the step of preleaching the concentrate, before the primary bioleach bioleaching process, using leach solution from at least one of the bioleaching processes.

5. A method according to claim 4 wherein the leach solution is derived from the 20 primary bioleaching process and the thermophilic secondary bioleaching process. 11 WO 2004/101834 PCT/ZA2004/000052

6. A method according to claim 4 or 5 wherein the preleaching step is used to remove easily leachable base metal from the concentrate before the primary bioleaching process.

7. A method according to claim 4, 5 or 6 wherein elemental sulphur which 5 accumulates during the preleach step due to rapid leaching ofeasily leachable sulphides is removed during the bioleaching stages.

8. A method according to any one of claims 4 to 7 which includes the step of adjusting the pH of a solution produced in the preleaching step to maximise recovery of the at least one base metal using solvent extraction techniques. 10

9. A method according to claim 8 which includes the step of causing arsenic in the solution to precipitate as ferric arsenate by increasing the pH of the solution to at least 2.

10. A method according to claim 8 or 9 wherein the pH adjustment is carried out at a temperature of from 600C to 800C. 15

11. A method according to any one of claims 1 to 10 wherein the primary bioleaching process is carried out in a series of continuously stirred tank reactors which are operated at a temperature of from 35°C to 50OC in the presence of an active mixed culture of mesophilic and moderate thermophilic microorganisms. 20

12. A method according to any one of claims 1 to 11 wherein a mixed culture of mesophile and moderate thermophile microorganisms are used to maximise 12 WO 2004/101834 PCT/ZA2004/000052 sulphide bioleaching and sulphur biooxidation during the primary bioleaching process.

13. A method according to claim 12 wherein the mixed culture contains. Leptospirillum ferrooxidans and Acidithiobacillus caldus. 5

14. A method according to claim 12 or 13 wherein the mixed culture of microorganims also contains thermophilic microorganims, which are not effectively active at the temperature range of 35 0 C to 50 0 C.

15. A method according to any one of claims 1 to 14 wherein the pH of the concentrate during the primary bioleaching processes is controlled at a value of 10 from 1,2 to 1,7.

16. A method according to any one of claims 1 to 15 which includes the step of supplying air with an oxygen content of from 95% to 98% to the concentrate during at least part of the bioleaching processes.

17. A method according to any one of claims 1 to 16 which includes the step of 15 removing toxic silver from the primary bioleaching residue.

18. A method according to any one of claims 1 to 17 wherein the thermophilic secondary bioleaching process is carried out at a temperature of from 650C to 80'C in the presence of active quantities of extreme thermophilic microorganims. 13 WO 2004/101834 PCT/ZA2004/000052

19. A method according to any one of claims 1 to 18 which includes the step of controlling the pH of the concentrate during the secondary bioleaching process at a value of from 1,0 to 1,7.

20. A method according to any one of claims 1 to 19 which includes the step of 5 supplying air with a carbon dioxide content of from 1% to 5% to the concentrate during at least part of the bioleaching processes.

21. A method according to any one of claims 1 to 20 wherein the at least one base metal is copper which is recovered by concentrating the copper and stripping, followed by cathode production by electrowinning. 14