US20020012620A1 - Bacterial leaching of copper and zinc without iron leaching - Google Patents
Bacterial leaching of copper and zinc without iron leaching Download PDFInfo
- Publication number
- US20020012620A1 US20020012620A1 US09/334,653 US33465399A US2002012620A1 US 20020012620 A1 US20020012620 A1 US 20020012620A1 US 33465399 A US33465399 A US 33465399A US 2002012620 A1 US2002012620 A1 US 2002012620A1
- Authority
- US
- United States
- Prior art keywords
- iron
- solubilization
- leaching
- ore
- phosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/18—Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the present invention relates generally to the field of bacterial leaching of minerals.
- sulfide ores contain the iron mineral, pyrite (FeS 2 ), as well as valuable sulfide minerals, for example zinc sulfide (sphalerite, ZnS).
- FeS 2 iron mineral
- sulfide minerals for example zinc sulfide
- ZnS zinc sulfide
- pyrite solubilization involves both the oxidation of sulfide or sulfur and that of ferrous iron while sphalerite solubilization involves only the oxidation of sulfide or sulfur.
- a method of leaching zinc from ore comprising:
- the inhibitor may be an anion, for example: phosphate; nitrate; chloride; and mixtures thereof.
- the inhibitor may be a respiratory inhibitor, for example: azide; cyanide; and mixtures thereof.
- the inhibitor may be selected from the group consisting of phosphate, nitrate, chloride, azide, cyanide and combinations thereof.
- the ore may be composed of tailings or mixtures of minerals.
- the iron or sulfur-oxidizing bacteria are selected from the group consisting of: Thiobacillus ferrooxidans; Thiobacillus thiooxidans; and a mixture thereof.
- the inhibitor is phosphate or chloride and the potassium salt is in the medium at a concentration of 10-100 mM.
- the bacterial growth medium comprises:
- a growth media for iron-oxidizing or sulfur-oxidizing bacteria for bacterial leaching of a mineral from ore comprising:
- a method of leaching a mineral from ore comprising:
- the ore may be selected from the group consisting of pyrite, sphalerite, chalcopyrite and mixtures thereof.
- the metal may be zinc, copper or mixtures thereof.
- the inhibitor may be an anion.
- the anion may be selected from the group consisting of phosphate, nitrate, chloride and mixtures thereof.
- the inhibitor may stimulate solubilization of the sulfide mineral.
- Table 1 is a summary of the inhibition of Fe 2+ oxidation and S 0 oxidation by the various compounds.
- Table 2 is a summary of the growth inhibition by the various compounds.
- Table 3 is a summary of the effects of various anions on bioleaching of pyrite and sphalerite mixtures.
- Table 4 is a summary of the effects of various anions and concentrations thereof in bioleaching of chalcopyrite and sphalerite mixture.
- Table 5 is a summary of the effects of anions on bioleaching of a complex sulfide ore.
- FIG. 1 is a graph of the effect of phosphate and chloride on the Fe 2+ and S 0 oxidation during the growth of T. ferrooxidans and T. thiooxidans respectively in Micro-oxymax experiments.
- FIG. 2 is a bar graph representation of the inhibition of Fe solubilization by potassium phosphate in T. ferrooxidans bacterial leaching of tailings.
- FIG. 3 is a bar graph of representation of the inhibition of Fe solubilization by potassium phosphate in T. thiooxidans bacterial leaching of tailings.
- FIG. 4 is a bar graph representation of the inhibition of Fe solubilization by potassium phosphate in bacterial leaching of tailings with both T. ferrooxidans and T. thiooxidans.
- FIG. 5 is a time course of extraction of copper and zinc from ore.
- bacterial strains Thiobacillus ferrooxidans SM-4 and Thiobacillus thiooxidans SM-6 (FIGS. 1, 3 and 4 and Table 2) or SM-7 (Table 5) were used. Specifically, T. ferrooxidans was grown on Fe 2+ or S 0 while T. thiooxidans was grown only on sulfur.
- HP medium described in Suzuki et al, 1990, Appl Environ Microbiol 56:1620-1626, consisting of: 0.4 g (NH 4 ) 2 SO 4 , 0.1 g K 2 HPO 4 , 0.4 g MgSO4.7H 2 O per liter, adjusted to pH 2.3 with H 2 SO 4 was used for growth of bacteria on Fe 2+ , for growth in a Micro-oxymaxTM respirometer (both Fe 2+ and S 0 growth), and for mineral leaching experiments, as described below. For growth on Fe 2+ , 33.3 g FeSO 4 .7H 2 O per liter (pH 2.3, filter-sterilized) was added to the above-described HP medium.
- the medium used for growth on S 0 was Starkey No. 1 medium: 0.3 g (NH 4 ) 2 SO 4 , 3.5 g KH 2 PO 4 , 0.5 g MgSO 4 .7H 2 O, 0.25 g CaCl 2 , 18 mg FeSO 4 .7H 2 O per liter, adjusted to pH 2.3 with H 2 SO 4 .
- Elemental sulfur powder sulfur precipitated, BDH Chemicals, Toronto
- 2.5 g was spread on the surface of 100 ml medium in 250 ml ErlenmeyerTM flasks after the addition of 5% (v/v) inoculum. Flasks were then covered with tissue paper and incubated at 25° C. for 4 days without shaking or stirring.
- 1.0 liter medium in 2.8 liter FernbachTM flasks supplemented with 25 g sulfur were used and the cultures were incubated at 28° C.
- the rate of ferrous iron and sulfur oxidation by the resting cells was determined by the oxygen consumption rate (nmol O 2 /min) in a GilsonTM Oxygraph with a ClarkTM oxygen electrode at 25° C.
- the reaction mixture in a total volume of 1.2 ml contained 10-100 ⁇ l cell suspension, 0.5 ⁇ mol FeSO 4 or 0.1 ml elemental sulfur suspension (32 mg in 500 ppm Tween-80TM) and 0.1 M ⁇ -alanine-H 2 SO 4 at pH 3.0 (standard condition) or varying inhibitory concentrations of salts at pH 3.0, as described below.
- standard biological oxidation inhibitors, sodium azide and sodium cyanide in 0.1 M ⁇ -alanine-H 2 SO 4 at pH 3.0 was studied.
- the oxidation of Fe 2+ or S 0 was differentially affected by various inhibitors as shown in Table 1. Specifically, 0.1 M potassium sulfate did not inhibit either Fe 2+ or S 0 oxidation while 0.3 M potassium sulfate inhibited Fe 2+ oxidation (10%) to a lesser extent than S 0 oxidation (30%). However, 0.1 M potassium phosphate inhibited Fe 2+ oxidation (60%) but not S 0 oxidation, while increasing the potassium phosphate concentration to 0.3 M inhibited Fe 2+ oxidation to a similar extent as seen with 0.1 M potassium phosphate, (60%) although S 0 oxidation was now inhibited somewhat (30%), as a result of the increased potassium phosphate concentration.
- Potassium chloride inhibited Fe 2+ oxidation at a concentration of 0.1 M (30%) and at 0.3 M (40%) but inhibited S 0 only at the 0.3 M concentration and to a lesser extent (10%).
- Potassium nitrate inhibited Fe 2+ oxidation very strongly at both 0.1 M and 0.3 M (90% and 100% respectively) but inhibited S 0 oxidation only at 0.3 M (85%) and not at 0.1 M (10%).
- Sodium azide inhibited Fe 2+ oxidation strongly at either 10 ⁇ M (90%) or 50 ⁇ M (95%) while the difference in inhibition of S 0 oxidation was much more pronounced at 50 ⁇ M than 10 ⁇ M (90% versus 35%).
- FIGS. 2 to 4 show the concentration of Zn and Fe solubilized after 14 days of bacterial leaching of flotation tailings.
- addition of potassium phosphate at concentrations of 25-100 mM drastically reduced the Fe solubilization with only 50% reduction in Zn leaching.
- potassium chloride had little effect on Zn selectivity, but potassium nitrate reduced the Fe leaching similar to phosphate, although, in this instance, Zn leaching was also considerably inhibited. Furthermore, neither sodium azide nor sodium cyanide had a significant effect after 14 days although there was a slight inhibitory effect on both Fe and Zn leaching after two days. As can be seen in FIG. 3, potassium phosphate strongly inhibited Fe leaching with T thiooxidans at 10-100 mM. Furthermore, KNO 3 and KCl also reduced Fe leaching at high concentrations, albeit to a much smaller degree. As can be seen in FIG. 4, when both T. ferrooxidans and T. thiooxidans were present, potassium phosphate was again the most effective inhibitor of Fe leaching without inhibiting Zn leaching extensively. Thus, at 10 mM potassium phosphate, 70% Zn was solubilized with no Fe leaching.
- iron or sulfur-oxidizing bacteria may be used.
- leaching of other minerals may be done in the absence of iron leaching, provided of course that the other minerals are present in a sulfur-containing ore.
- sulfide minerals may include for example sphalerite, chalcopyrite, covellite (CuS), chalcocite (Cu 2 S) molybdenite (MOS 2 ), galena (PbS), stibnite (Sb 2 S 3 ) argentite (Ag 2 S), millerite (NiS), pentiandite ((Ni or Co)Fe) 9 S 8 , and mixtures thereof.
- CuS covellite
- MOS 2 molybdenite
- PbS galena
- Sb 2 S 3 stibnite
- argentite Ag 2 S
- millerite NaS
- pentiandite ((Ni or Co)Fe) 9 S 8 , and mixtures thereof.
- this list is for illustrative purposes and is by no means intended to be exhaustive.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biotechnology (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Microbiology (AREA)
- Biochemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Thiobacillus ferrooxidans and Thiobacillus thiooxidans play major roles in bacterial leaching of metals from ores and tailings through their oxidative action on ferrous iron (Fe2+) and sulfide or sulfur (S0). We have studied the effects of various inhibitors such as cyanide, azide and anions (phosphate, nitrate, chloride) on Fe2+ or S0 oxidation by resting cells, on Fe2+ or S0 as an energy source for growth and finally on leaching of Fe or Zn from a sample containing pyrite (FeS2) and sphalerite (ZnS). All of these inhibitors inhibited Fe2+ oxidation more strongly than S0 oxidation and generally stopped the growth on Fe2+ at lower concentrations than on S0. All three anions inhibited the leaching of Fe more strongly than Zn leaching, but potassium phosphate was the most selective. In the leaching experiments with T. ferrooxidans and T. thiooxidans either singly or combined, phosphate at 10-100 mM reduced the Fe leaching almost completely (by 90-over 95%) without affecting the Zn leaching (0-40%). Furthermore, the method can be used for recovery of other minerals from other sulfide ores.
Description
- The present invention relates generally to the field of bacterial leaching of minerals.
-
- Most sulfide ores contain the iron mineral, pyrite (FeS2), as well as valuable sulfide minerals, for example zinc sulfide (sphalerite, ZnS). As a consequence, bacterial leaching of metals is hampered by concurrent leaching of iron from pyrite, as the separation and removal of solubilized iron from the leached metal, for example, zinc, are difficult and expensive. However, it is important to note that pyrite solubilization involves both the oxidation of sulfide or sulfur and that of ferrous iron while sphalerite solubilization involves only the oxidation of sulfide or sulfur.
- Clearly, it would be advantageous to be able to inhibit iron oxidation without inhibiting sulfur oxidation, to inhibit growth on iron without inhibiting growth on sulfur and to inhibit bacterial solubilization of iron without inhibiting bacterial solubilization of another mineral, for example, zinc and/or copper. As a result, it would be possible to solubilize sphalerite in the absence of pyrite solubilization, meaning that the added and expensive step of removal of the solubilized iron would not be necessary.
- It is therefore an object of the invention to provide methods of inhibiting iron oxidation without inhibiting sulfur oxidation, inhibiting growth on iron without inhibiting growth on sulfur and inhibiting bacterial solubilization of iron without inhibiting bacterial solubilization of another mineral, for example, zinc and/or copper.
- According to one aspect of the invention there is provided a method of leaching zinc from ore comprising:
- providing a quantity of ore including pyrite (FeS2) and sphalerite (ZnS);
- providing iron-oxidizing or sulfur-oxidizing bacteria, said bacteria being capable of bacterial solubilization of pyrite and sphalerite to iron and zinc respectively;
- providing a bacterial growth medium capable of supporting growth of the iron-oxidizing or sulfur-oxidizing bacteria;
- supplementing the growth medium with an inhibitor that inhibits pyrite solubilization but does not inhibit sphalerite solubilization or inhibits sphalerite solubilization to a lesser extent than pyrite solubilization;
- placing the ore and the iron-oxidizing or sulfur-oxidizing bacteria in the growth medium; and
- incubating the bacteria and the ore under conditions permitting solubilization of the sphalerite to zinc. Thus, the bacteria act to solubilize the sphalerite to zinc without solubilization of the iron, thereby allowing recovery of the zinc from the ore without the added step of having to remove the iron.
- The inhibitor may be an anion, for example: phosphate; nitrate; chloride; and mixtures thereof.
- The inhibitor may be a respiratory inhibitor, for example: azide; cyanide; and mixtures thereof.
- The inhibitor may be selected from the group consisting of phosphate, nitrate, chloride, azide, cyanide and combinations thereof.
- The ore may be composed of tailings or mixtures of minerals.
- Preferably, the iron or sulfur-oxidizing bacteria are selected from the group consisting of:Thiobacillus ferrooxidans; Thiobacillus thiooxidans; and a mixture thereof.
- Preferably, the inhibitor is phosphate or chloride and the potassium salt is in the medium at a concentration of 10-100 mM.
- Preferably, the bacterial growth medium comprises:
- 0.4 g/L (NH4)2SO4;
- 0.1 g/L K2HPO4;
- 0.4 g/L MgSO4.7H2O; and
- 10-100 mM phosphate or chloride,
- adjusted to pH 2.3 with H2SO4.
- According to a second aspect of the invention, there is provided a growth media for iron-oxidizing or sulfur-oxidizing bacteria for bacterial leaching of a mineral from ore comprising:
- 0.4 g/L (NH4)2SO4;
- 0.1 g/L K2HPO4;
- 0.4 g/L MgSO4.7H2O; and
- 10-100 mM phosphate or chloride,
- adjusted to pH2.3 with H2SO4.
- According to a third aspect of the invention, there is provided a method of leaching a mineral from ore comprising:
- providing a quantity of ore including chalcopyrite (CuFeS2) or pyrite (FeS2) or similar iron-containing minerals and sulfide mineral of a metal;
- providing iron-oxidizing or sulfur-oxidizing bacteria, said bacteria being capable of bacterial solubilization of pyrite and the sulfide mineral to iron and the metal respectively;
- providing a bacterial growth medium capable of supporting growth of the iron-oxidizing or sulfur-oxidizing bacteria;
- supplementing the growth medium with an inhibitor that inhibits iron solubilization but does not inhibit solubilization of the sulfide mineral or inhibits solubilization of the sulfide mineral to a lesser extent than iron solubilization;
- placing the ore and the iron-oxidizing or sulfur-oxidizing bacteria in the growth medium; and
- incubating the ore and the bacteria under conditions permitting solubilization of the sulfide mineral to the metal. Thus, the above-described method can be used for bacterial solubilization of other sulfide minerals from pyrite-containing ores.
- The ore may be selected from the group consisting of pyrite, sphalerite, chalcopyrite and mixtures thereof.
- The metal may be zinc, copper or mixtures thereof.
- The inhibitor may be an anion. The anion may be selected from the group consisting of phosphate, nitrate, chloride and mixtures thereof.
- The inhibitor may stimulate solubilization of the sulfide mineral.
- The solubilization of metals may occur at different times, permitting the separate recovery of each metal.
- One embodiment of the invention will now be described in conjunction with the accompanying drawings in which:
- Table 1 is a summary of the inhibition of Fe2+ oxidation and S0 oxidation by the various compounds.
- Table 2 is a summary of the growth inhibition by the various compounds.
- Table 3 is a summary of the effects of various anions on bioleaching of pyrite and sphalerite mixtures.
- Table 4 is a summary of the effects of various anions and concentrations thereof in bioleaching of chalcopyrite and sphalerite mixture.
- Table 5 is a summary of the effects of anions on bioleaching of a complex sulfide ore.
- FIG. 1 is a graph of the effect of phosphate and chloride on the Fe2+ and S0 oxidation during the growth of T. ferrooxidans and T. thiooxidans respectively in Micro-oxymax experiments.
- FIG. 2 is a bar graph representation of the inhibition of Fe solubilization by potassium phosphate inT. ferrooxidans bacterial leaching of tailings.
- FIG. 3 is a bar graph of representation of the inhibition of Fe solubilization by potassium phosphate inT. thiooxidans bacterial leaching of tailings.
- FIG. 4 is a bar graph representation of the inhibition of Fe solubilization by potassium phosphate in bacterial leaching of tailings with bothT. ferrooxidans and T. thiooxidans.
- FIG. 5 is a time course of extraction of copper and zinc from ore.
- Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the preferred methods and materials are now described. All publications mentioned hereunder are incorporated herein by reference.
- Herein, a study of iron and sulfur oxidation byThiobacillus thiooxidans and Thiobacillus ferrooxidans in the presence of varying concentrations of various anions and respiratory inhibitors is described. Specifically, the anions used were phosphate, nitrate and chloride while the respiratory inhibitors used were cyanide and azide. That is, it is shown that: iron oxidation can be inhibited without inhibition of sulfur oxidation; bacterial growth on iron can be inhibited without inhibition of bacterial growth on sulfur; and bacterial solubilization of iron can be inhibited without inhibition of bacterial solubilization of sulfur. Thus, the method described herein can be utilized to recover a variety of minerals in iron-containing ores without the added step of separating the mineral of interest from iron solubilized from pyrite.
- The invention will now be described by way of examples, although it is to be understood that the invention is not limited to these examples.
- Materials and Methods
- In this embodiment of the invention, bacterial strainsThiobacillus ferrooxidans SM-4 and Thiobacillus thiooxidans SM-6 (FIGS. 1, 3 and 4 and Table 2) or SM-7 (Table 5) were used. Specifically, T. ferrooxidans was grown on Fe2+ or S0 while T. thiooxidans was grown only on sulfur. HP medium, described in Suzuki et al, 1990, Appl Environ Microbiol 56:1620-1626, consisting of: 0.4 g (NH4)2SO4, 0.1 g K2HPO4, 0.4 g MgSO4.7H2O per liter, adjusted to pH 2.3 with H2SO4 was used for growth of bacteria on Fe2+, for growth in a Micro-oxymax™ respirometer (both Fe2+ and S0 growth), and for mineral leaching experiments, as described below. For growth on Fe2+, 33.3 g FeSO4.7H2O per liter (pH 2.3, filter-sterilized) was added to the above-described HP medium. Cultures were grown in shake flasks (100 ml) with 10% inoculum (v/v) in 250 ml Erlenmeyer™ flasks at 25° C. at 120 rpm for 24 hours. It is of note that for large scale growth, medium volume and flask size were increased.
- The medium used for growth on S0, unless otherwise indicated, was Starkey No. 1 medium: 0.3 g (NH4)2SO4, 3.5 g KH2PO4, 0.5 g MgSO4.7H2O, 0.25 g CaCl2, 18 mg FeSO4.7H2O per liter, adjusted to pH 2.3 with H2SO4. Elemental sulfur powder (sulfur precipitated, BDH Chemicals, Toronto), 2.5 g, was spread on the surface of 100 ml medium in 250 ml Erlenmeyer™ flasks after the addition of 5% (v/v) inoculum. Flasks were then covered with tissue paper and incubated at 25° C. for 4 days without shaking or stirring. For large scale growth, 1.0 liter medium in 2.8 liter Fernbach™ flasks supplemented with 25 g sulfur were used and the cultures were incubated at 28° C.
- For the resting cell experiments, cells from large scale growth were filtered through Whatman™ No. 1 filter paper under suction before centrifugation at 8000× g. The cells were washed in 0.1 M β-alanine-H2SO4 (pH 2.3) and suspended in the same buffer to a concentration of 50 mg wet cells per ml.
- The rate of ferrous iron and sulfur oxidation by the resting cells was determined by the oxygen consumption rate (nmol O2/min) in a Gilson™ Oxygraph with a Clark™ oxygen electrode at 25° C. The reaction mixture in a total volume of 1.2 ml contained 10-100 μl cell suspension, 0.5 μmol FeSO4 or 0.1 ml elemental sulfur suspension (32 mg in 500 ppm Tween-80™) and 0.1 M β-alanine-H2SO4 at pH 3.0 (standard condition) or varying inhibitory concentrations of salts at pH 3.0, as described below. Specifically, the effect of standard biological oxidation inhibitors, sodium azide and sodium cyanide in 0.1 M β-alanine-H2SO4 at pH 3.0 was studied.
- Growth inhibition studies were carried out in a Micro-oxymax™ respirometer at Cominco Research in Trail, British Columbia, wherein the O2 and CO2 consumption (at 52 minute intervals) of cultures at 26° C. were monitored over time (45-50 hours). Each flask contained a total volume of 100 ml, comprised of 5 ml inoculum culture plus 95 ml HP medium with varying concentrations of inhibitors plus Fe2+ or S0 as growth substrate (33.3 g FeSO4.7H2O or 25 g sulfur per liter). In the S0 medium, HP medium was supplemented with 18 mg FeSO4.7H2O per liter. A growth curve was generated from the monitored O2 and CO2 consumption rates over time, as described below.
- Bacterial leaching was performed in shake flask experiments with 250 ml Erlenmeyer™ flasks containing 95 ml of HP medium with and without inhibitors unless otherwise specified, 4 ml of inoculum (Fe2+-grown T. ferrooxidans, S0-grown T. thiooxidans or both) and 5 g of floatation tailings supplied by Cominco Research were used, as described below. The flasks were grown at 26° C. on a rotary shaker at 150 rpm for 14 days. At various time intervals, 5 ml samples were taken to determine the concentrations of dissolved zinc and iron in the leachate as well as the percentage of zinc and iron remaining in the precipitate (after filtration of the leachate).
- Inhibition of Oxidation
- The oxidation of Fe2+ or S0 was differentially affected by various inhibitors as shown in Table 1. Specifically, 0.1 M potassium sulfate did not inhibit either Fe2+ or S0 oxidation while 0.3 M potassium sulfate inhibited Fe2+ oxidation (10%) to a lesser extent than S0 oxidation (30%). However, 0.1 M potassium phosphate inhibited Fe2+ oxidation (60%) but not S0 oxidation, while increasing the potassium phosphate concentration to 0.3 M inhibited Fe2+ oxidation to a similar extent as seen with 0.1 M potassium phosphate, (60%) although S0 oxidation was now inhibited somewhat (30%), as a result of the increased potassium phosphate concentration. Potassium chloride inhibited Fe2+ oxidation at a concentration of 0.1 M (30%) and at 0.3 M (40%) but inhibited S0 only at the 0.3 M concentration and to a lesser extent (10%). Potassium nitrate inhibited Fe2+ oxidation very strongly at both 0.1 M and 0.3 M (90% and 100% respectively) but inhibited S0 oxidation only at 0.3 M (85%) and not at 0.1 M (10%). Sodium azide inhibited Fe2+ oxidation strongly at either 10 μM (90%) or 50 μM (95%) while the difference in inhibition of S0 oxidation was much more pronounced at 50 μM than 10 μM (90% versus 35%). Furthermore, sodium cyanide inhibited Fe2+ oxidation strongly at 10 μM (90%) and 50 μM (95%) but inhibited S0 oxidation only moderately at 50 μM (25%). Thus, to summarize, potassium phosphate, potassium chloride and potassium nitrate all inhibited the oxidation of Fe2+ more strongly than the oxidation of S0. It is of note that phosphate and nitrate were more effective than chloride in this inhibition. Potassium sulfate, on the other hand, did not inhibit the Fe2+ oxidation even as much as S0 oxidation. Furthermore, the respiration inhibitors, sodium azide and sodium cyanide, also showed a stronger inhibition of Fe2+ oxidation.
- Inhibition of Growth
- Growth inhibition results shown in Table 2 indicate the same differential inhibition as seen in Table 1, with the exception of potassium nitrate which inhibited both Fe2+ and S0 growth strongly. It is of note that the S0 oxidation in Table 1 was studied at
pH 3, as we have previously shown that S0 oxidation by T. ferrooxidans is lower at pH 2.3. FIG. 1 shows that S0 oxidation was actually stimulated by 50 mM phosphate or chloride, while Fe2+ oxidation was inhibited. - Selective Leaching of Zinc
- FIGS.2 to 4 show the concentration of Zn and Fe solubilized after 14 days of bacterial leaching of flotation tailings. As can be seen, T. ferrooxidans (FIG. 2) solubilized more zinc than T. thiooxidans (FIG. 3), leaching nearly 100% (1.65 g/l) of the zinc, but also solubilized around 50% of total iron (2.75 g/l from the tailings plus 334 mg/l from 5% culture inoculum=3.08 g/l). However, as shown in FIG. 2, addition of potassium phosphate at concentrations of 25-100 mM drastically reduced the Fe solubilization with only 50% reduction in Zn leaching. It is of note that potassium chloride had little effect on Zn selectivity, but potassium nitrate reduced the Fe leaching similar to phosphate, although, in this instance, Zn leaching was also considerably inhibited. Furthermore, neither sodium azide nor sodium cyanide had a significant effect after 14 days although there was a slight inhibitory effect on both Fe and Zn leaching after two days. As can be seen in FIG. 3, potassium phosphate strongly inhibited Fe leaching with T thiooxidans at 10-100 mM. Furthermore, KNO3 and KCl also reduced Fe leaching at high concentrations, albeit to a much smaller degree. As can be seen in FIG. 4, when both T. ferrooxidans and T. thiooxidans were present, potassium phosphate was again the most effective inhibitor of Fe leaching without inhibiting Zn leaching extensively. Thus, at 10 mM potassium phosphate, 70% Zn was solubilized with no Fe leaching.
- Stimulation of Copper Solubilization by Anions, Phosphate and Chloride
- In this example, the effect of anions on metal solubilization from different mineral combinations was examined. Specifically, as shown in Table 3, bioleaching of a mixture of pyrite (FeS2) and sphalerite (ZnS) by Thiobacillus ferrooxidans was affected by potassium phosphate exactly as expected based on the results obtained with flotation tailings, shown in FIG. 2. That is, potassium phosphate caused a strong inhibition of iron solubilization and moderate to no reduction of Zn solubilization. Potassium chloride showed a moderate inhibition of iron leaching, but stimulated zinc leaching.
- When the study was extended to a mixture of chalcopyrite (CuFeS2) and sphalerite, however, an additional effect of phosphate was observed as shown in Table 4. Specifically, potassium phosphate not only reduced iron oxidation but also increased the solubilization of Cu (from 9% to 20%). Extraction of Zn was slightly reduced by phosphate, but chloride stimulated Zn extraction. The bacterial leaching of a complex sulfide ore from the Flin Flon mine containing 4.9% Cu, 12.5% Zn, 30% Fe and 37.5% S, which is a mixture of pyrite, chalcopyrite and sphalerite, with small amounts of carbonates and pyrrhotite, showed stimulation of both Cu and Zn leaching by chloride as well as phosphate. In fact, the highest level of Cu leaching using this ore is nearly five times greater than previously reported values in the absence of additional anions (Lizama and Suzuki, 1988, Biotechnol Bioeng 32: 110-116). The stimulation was likely caused by the increased sulfur oxidation under these conditions (FIG. 1) to sulfuric acid, since whenever high concentrations of copper and zinc were leached, the pH of the leachate was very low (pH 1.5 to 2.0) while the pH of chemical control without bacteria remained at 3 to 4. Additionally, as shown in FIG. 5, the time course leaching of Cu and Zn is not identical. As can be seen in FIG. 5, copper solubilization may be largely finished prior to zinc leaching, suggesting that copper may be recovered first, prior to proceeding to zinc leaching and recovery. That is, copper and zinc can be recovered from a complex ore without the need for separation simply by replacing the media following completion of copper leaching because of this lag time.
- Discussion
- The effect of inorganic anions onT. ferrooxidans is known to be highly complex (Ingledew, 1982, Biochim Biophys Acta 683:89-117). Sulfate was considered essential for iron oxidation (Lazaroff, 1963, J Bacteriol 85:78-83) and replacement of sulfate with chloride or nitrate resulted in inhibition of iron oxidation (Lazaroff, 1963; Razzell and Trussell, 1963, J Bacteriol 85:595-603). However, it was shown that this sulfate requirement could be satisfied with selenate, that is, SeO4 2− rather than SO4 2− (Lazaroff, 1977, J Gen Microbiol 101:85-91). Sulfate is believed to affect an electron transfer component involved in the Fe2+ oxidation (Fry et al, 1986, Arch Biochem Biophys 246:650-654). It is of note that these studies centered on the sulfate requirement rather than inhibition by anions. However, it is hypothesized in Ingledew, 1982, that sulfate may have a role in lowering the redox potential of Fe2+/Fe3+ couple, making it more reducing and the oxidation of sulfur by T. ferrooxidans is also sensitive to ions (Razzell et al, 1963).
- It is remarkable that the inhibition by various anions of Fe2+ oxidation, of growth on Fe2+ and of Fe-leaching follows the same pattern. The effect of phosphate on the selective leaching of Zn with nearly total inhibition of Fe leaching was particularly impressive. Since phosphate can react with both ferrous and ferric iron, the inhibition by phosphate may be different from simple anion inhibition. It could have a specific effect on Fe leaching from pyrite by T. ferrooxidans possibly by binding Fe on the surface of pyrite or cells.
- It is of note that the concentration of potassium phosphate even at 10 mM is much higher than those required for growth of bacteria (McCready et al, 1986,Hydrometallurgy 17:61-71; Lizama and Suzuki, 1988, Biotecnol Bioeng 32:110-116)., which is 0.1 mM-0.57 mM, and might have some effect on the chemical (galvanic) interaction between pyrite and sphalerite, but since bacteria always stimulate the Zn solubilization beyond the chemical rate (Lizama and Suzuki, 1991, Can J Microbiol 37:304-311) and potassium nitrate can also reduce Fe solubilization, as discussed above, the effect of phosphate on these bacterial activities is the most likely explanation. That is, as discussed above and as shown in FIGS. 2 to 4, the addition of potassium phosphate strongly inhibited iron leaching by T. thiooxidans and T. ferrooxidans without inhibiting zinc leaching extensively.
- Furthermore, as discussed above, the bacterial leaching of copper from chalcopyrite in the presence of sphalerite is stimulated by the addition of phosphate. Chloride stimulates zinc solubilization from sphalerite. Phosphate and chloride however both stimulate copper solubilization in a complex sulfide ore consisting of chalcopyrite, sphalerite and pyrite.
- These stimulatory effects are in agreement with the observed stimulation of sulfur oxidation (FIG. 1) by 50 mM phosphate and chloride. When the sulfide portion of metal sulfides is oxidized to sulfate, the resulting metal sulfates are often soluble.
- To summarize, it has been shown that iron oxidation can be inhibited without inhibition of sulfur oxidation, that growth on iron can be inhibited without inhibition of growth on sulfur and that bacterial solubilization of iron can be inhibited without inhibition of bacterial solubilization of sulfur or sometimes even with the activation of sulfur solubilization. As a result, the above-described method can be used to solubilize sulfide minerals within pyrite-containing ores in the absence of bacterial solubilization of iron. This in turn eliminates the expensive step of removing solubilized iron from the leachate, thereby making the process of bacterial solubilization of minerals from pyrite much more cost effective.
- In other embodiments of the invention, other iron or sulfur-oxidizing bacteria may be used.
- In yet other embodiments of the invention, leaching of other minerals may be done in the absence of iron leaching, provided of course that the other minerals are present in a sulfur-containing ore. These sulfide minerals may include for example sphalerite, chalcopyrite, covellite (CuS), chalcocite (Cu2S) molybdenite (MOS2), galena (PbS), stibnite (Sb2S3) argentite (Ag2S), millerite (NiS), pentiandite ((Ni or Co)Fe)9S8, and mixtures thereof. As will be appreciated by one skilled in the art, this list is for illustrative purposes and is by no means intended to be exhaustive.
- Since various modifications can be made in our invention as herein above described, and many apparently widely different embodiments of same made within the spirit and scope of the claims without department from such spirit and scope, it is intended that all matter contained in the accompanying specification shall be interpreted as illustrative only and not in a limiting sense.
Claims (20)
1. A method of leaching zinc from ore comprising:
providing a quantity of ore including pyrite (FeS2) and sphalerite (ZnS);
providing iron-oxidizing or sulfur-oxidizing bacteria, said bacteria being capable of bacterial solubilization of pyrite and sphalerite to iron and zinc respectively;
providing a bacterial growth medium capable of supporting growth of the iron-oxidizing or sulfur-oxidizing bacteria;
supplementing the growth medium with an inhibitor that inhibits pyrite solubilization but does not inhibit sphalerite solubilization or inhibits sphalerite solubilization to a lesser extent than pyrite solubilization;
placing the ore and the iron-oxidizing or sulfur-oxidizing bacteria in the growth medium; and
incubating the bacteria and the ore under conditions permitting solubilization of the sphalerite to zinc.
2. The method according to claim 1 wherein the inhibitor is an anion.
3. The method according to claim 2 wherein the anion is selected from the group consisting of: phosphate; nitrate; chloride; and mixtures thereof.
4. The method according to claim 1 wherein the inhibitor is a respiratory inhibitor.
5. The method according to claim 4 wherein the respiratory inhibitor is selected from the group consisting of: azide; cyanide; and mixtures thereof.
6. The method according to claim 1 wherein the inhibitor is selected from the group consisting of phosphate, nitrate, chloride, azide, cyanide and combinations thereof.
7. The method according to claim 1 wherein the ore is composed of tailings.
8. The method according to claim 1 wherein the iron or sulfur-oxidizing bacteria are selected from the group consisting of: Thiobacillus ferrooxidans; Thiobacillus thiooxidans; and a mixture thereof.
9. The method according to claim 1 wherein the inhibitor is phosphate or chloride.
10. The method according to claim 9 wherein the phosphate or chloride is in the bacterial growth medium at a concentration of 10-100 mM.
11. The method according to claim 9 wherein the phosphate or chloride is a potassium salt.
12. The method according to claim 11 wherein the potassium salt is in the bacterial growth medium at a concentration of 10-100 mM.
13. The method according to claim 1 wherein the bacterial growth medium comprises:
0.4 g/L (NH4)2SO4;
0.1 g/L K2HPO4;
0.4 g/L MgSO4.7H2O; and
10-100 mM phosphate or chloride,
adjusted to pH 2.3 with H2SO4.
14. A growth media for iron-oxidizing or sulfur-oxidizing bacteria for bacterial leaching of a mineral from ore without iron leaching comprising:
0.4 g/L (NH4)2SO4;
0.1 g/L K2HPO4;
0.4 g/L MgSO4.7H2O; and
10-100 mM phosphate or chloride,
adjusted to pH 2.3 with H2SO4.
15. A method of leaching a mineral from ore comprising:
providing a quantity of ore including an iron ore and a sulfide mineral of a metal;
providing iron-oxidizing or sulfur-oxidizing bacteria, said bacteria being capable of bacterial solubilization of the iron ore and the sulfide mineral to iron and the metal respectively;
providing a bacterial growth medium capable of supporting growth of the iron or sulfur-oxidizing bacteria;
supplementing the growth medium with an inhibitor that inhibits iron solubilization but does not inhibit solubilization of the sulfide mineral or inhibits solubilization of the sulfide mineral to a lesser extent than iron solubilization;
placing the ore and the iron or sulfur-oxidizing bacteria in the growth medium; and
incubating the ore and the bacteria under conditions permitting solubilization of the sulfide mineral to the metal.
16. The method according to claim 15 wherein the ore comprises pyrite, sphalerite, chalcopyrite, covellite (CuS), chalcocite (Cu2S), millerite (NiS), pentlandite ((Ni or Co)Fe)9S8 or mixtures thereof.
17. The method according to claim 15 wherein the metal is selected from the group consisting of zinc, copper and mixtures thereof.
18. The method according to claim 15 wherein the inhibitor is selected from the group consisting of phosphate, nitrate, chloride and mixtures thereof.
19. The method according to claim 15 wherein the inhibitor stimulates solubilization of the sulfide mineral.
20. The method according to claim 15 wherein the solubilization of metals occurs at different times, permitting the separate recovery of each metal.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002241064A CA2241064A1 (en) | 1998-06-19 | 1998-06-19 | Bacterial medium for zinc leaching without iron leaching |
CA2,241,064 | 1998-06-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
US20020012620A1 true US20020012620A1 (en) | 2002-01-31 |
Family
ID=4162566
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/334,653 Abandoned US20020012620A1 (en) | 1998-06-19 | 1999-06-17 | Bacterial leaching of copper and zinc without iron leaching |
Country Status (2)
Country | Link |
---|---|
US (1) | US20020012620A1 (en) |
CA (1) | CA2241064A1 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030034301A1 (en) * | 2001-07-27 | 2003-02-20 | Perriello Felix Anthony | Method and apparatus for recovery of metals with hydrocarbon-utilizing bacteria |
US20050112740A1 (en) * | 2003-10-20 | 2005-05-26 | Haase Richard A. | Waste metals recycling-methods, processed and systems for the recycle of metals into coagulants |
US20170293689A1 (en) * | 2012-02-01 | 2017-10-12 | Futurewei Technologies, Inc. | System and Method for Organizing Multimedia Content |
CN108004400A (en) * | 2016-10-28 | 2018-05-08 | 中国科学院过程工程研究所 | Suppress the method for oxidation of pyrite in a kind of biological metallurgy process |
CN108249721A (en) * | 2018-03-20 | 2018-07-06 | 河北工业大学 | The minimizing technology of zinc in a kind of phosphatization solid hazardous waste |
CN113355519A (en) * | 2021-06-03 | 2021-09-07 | 上海第二工业大学 | Method for leaching copper in waste circuit board by using microwave-enhanced thiobacillus ferrooxidans |
CN115704059A (en) * | 2021-08-11 | 2023-02-17 | 有研工程技术研究院有限公司 | Method for recovering zinc, lead and silver in zinc-oxygen press slag through combination of microbial leaching and chloride salt leaching |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7455715B2 (en) | 2001-07-13 | 2008-11-25 | Teck Cominco Metals Ltd. | Heap bioleaching process for the extraction of zinc |
CA2353002C (en) | 2001-07-13 | 2009-12-01 | Teck Cominco Metals Ltd. | Heap bioleaching process for the extraction of zinc |
CN114532356B (en) * | 2022-03-01 | 2023-10-31 | 广东工业大学 | Composition for killing bacterial spores, preparation method and method for killing bacterial spores |
CN115232981B (en) * | 2022-08-24 | 2024-05-14 | 深圳市中金岭南有色金属股份有限公司 | Biological leaching method of copper-zinc flotation tailings based on aeration oxidation and waste acid curing |
-
1998
- 1998-06-19 CA CA002241064A patent/CA2241064A1/en not_active Abandoned
-
1999
- 1999-06-17 US US09/334,653 patent/US20020012620A1/en not_active Abandoned
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030034301A1 (en) * | 2001-07-27 | 2003-02-20 | Perriello Felix Anthony | Method and apparatus for recovery of metals with hydrocarbon-utilizing bacteria |
US6875356B2 (en) | 2001-07-27 | 2005-04-05 | Global Biosciences, Inc. | Method and apparatus for recovery of metals with hydrocarbon-utilizing bacteria |
US20050112740A1 (en) * | 2003-10-20 | 2005-05-26 | Haase Richard A. | Waste metals recycling-methods, processed and systems for the recycle of metals into coagulants |
US20170293689A1 (en) * | 2012-02-01 | 2017-10-12 | Futurewei Technologies, Inc. | System and Method for Organizing Multimedia Content |
CN108004400A (en) * | 2016-10-28 | 2018-05-08 | 中国科学院过程工程研究所 | Suppress the method for oxidation of pyrite in a kind of biological metallurgy process |
CN108249721A (en) * | 2018-03-20 | 2018-07-06 | 河北工业大学 | The minimizing technology of zinc in a kind of phosphatization solid hazardous waste |
CN113355519A (en) * | 2021-06-03 | 2021-09-07 | 上海第二工业大学 | Method for leaching copper in waste circuit board by using microwave-enhanced thiobacillus ferrooxidans |
CN115704059A (en) * | 2021-08-11 | 2023-02-17 | 有研工程技术研究院有限公司 | Method for recovering zinc, lead and silver in zinc-oxygen press slag through combination of microbial leaching and chloride salt leaching |
Also Published As
Publication number | Publication date |
---|---|
CA2241064A1 (en) | 1999-12-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Brandl | Microbial leaching of metals | |
Ahonen et al. | Catalytic effects of silver in the microbiological leaching of finely ground chalcopyrite-containing ore materials in shake flasks | |
US4752332A (en) | Treating manganese-containing ores with a metal sulfide | |
CA2132440C (en) | Oxidation of metal sulfides using thermotolerant bacteria | |
Hiskey | Thiourea leaching of gold and silver—technology update and additional applications | |
Muñoz et al. | Silver-catalyzed bioleaching of low-grade copper ores.: Part I: Shake flasks tests | |
US20020012620A1 (en) | Bacterial leaching of copper and zinc without iron leaching | |
Manafi et al. | Shake flask and column bioleaching of a pyritic porphyry copper sulphide ore | |
Elzeky et al. | Effect of bacterial adaptation on kinetics and mechanisms of bioleaching ferrous sulfides | |
Sato et al. | Effect of silver chloride on the bioleaching of chalcopyrite concentrate | |
Sicupira et al. | Assessing metal recovery from low-grade copper ores containing fluoride | |
Işıldar et al. | Biorecovery of metals from electronic waste | |
JP2011047030A (en) | Method of leaching copper sulfide ore | |
Gupta et al. | Selective and non-selective bioleaching of manganese from a manganese-containing silver ore | |
Bang et al. | The oxidation of galena using Thiobacillus ferrooxidans | |
CA2275098A1 (en) | Bacterial leaching of copper and zinc without iron leaching | |
CA2518047C (en) | Method for controlling oxygen when separating minerals from a slurry | |
Sugio et al. | Isolation and characterization of Acidithiobacillus ferrooxidans strain D3-2 active in copper bioleaching from a copper mine in Chile | |
US5992640A (en) | Precious metals recovery from ores | |
JP4395561B2 (en) | Copper leaching method | |
Harahuc et al. | Effect of anions on selective solubilization of zinc and copper in bacterial leaching of sulfide ores | |
Donati | Enhancement of copper dissolution from a sulfide ore by using Thiobacillus thiooxidans | |
JP2012188697A (en) | Method for leaching copper | |
US6379919B1 (en) | Method for isolating thiocyanate resistant bacteria | |
Kim et al. | Bioleaching of Pyrrhotite with Bacterial Adaptation and Biological Oxidation for Iron Recovery. Metals 2021, 11, 295 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: MANITOBA, UNIVERSITY OF, THE, CANADA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SUZUKI, ISAMU;HARAHUC, LESIA;REEL/FRAME:010071/0774 Effective date: 19971022 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |