The present invention relates to a method of adaptation of a bacterial culture and leaching process. More particularly, the method of the present invention is particularly intended to facilitate the production of a bacterial culture for use in leaching under select conditions, including pH. Further, the leach of the present invention, utilising the adapted bacterial culture, is intended to provide reduced acid consumption and lower iron concentrations in the resulting pregnant leach solution when compared with biological leach processes of the prior art.
The following discussion of the background art is intended to facilitate an understanding of the present invention only. The discussion is not an acknowledgement or admission that any of the material referred to is or was part of the common general knowledge as at the priority date of the application.
Biomining, biological leaching or bio-leaching is the utilisation of microorganisms to assist in the dissolution of valuable metals from ores. In general, the dissolution of mineral sulfides in bacterial systems is the result of ferric ion and proton attack via the polysulfide pathway (Rohwerder et al., 2008). The conditions for such a reaction are generally dictated by the ability of the microorganism to efficiently catalyze the leaching process.
Previous studies have demonstrated that bioleaching of mineral sulfides occurs favorably at pH<3 (Halinen et al., 2009), with the majority of heap bioleaching processes of low grade ore being treated with a solution pH between 1.5 to 2.5 (Plumb et al., 2008). At such pH conditions, the bio-oxidation acidophilic microorganisms convert ferrous ion to ferric ion which is needed for the leaching of sulfide minerals.
Bioleaching of materials at a high pH range has been studied previously (Cameron, et al., 2009a; Cameron, et al., 2009b; Cameron, et al., 2010; Halinen et al., 2009; Plumb et al., 2008). Importantly, the majority of results published suggest that above a pH of 2 the rate of leaching is significantly decreased and the percentage of metals recovered is reduced (Plumb et al., 2008). Halinen et al., 2009 reported the rate of bioleaching of nickel and zinc at pH 1.5 is 3 to 4 times faster than the rate of leaching observed at pH 3. It is suggested that the lack of dissolved ferric ion and diffusion barriers created by iron oxide precipitates minimised the rate of leaching at pH 2.5 to 3.
Interestingly, Cameron et al. (2009a; 2009b; 2010), has successfully demonstrated bioleaching of low-grade ultramafic nickel suphide ore at temperatures of 5° C. to 30° C., and 45° C., at pH 3 by mixed microbial culture previously adapted to the ore, using freshwater. The apparent success of Cameron's studies may be largely contributed to the adapting the microbes to specific conditions and feed materials prior to the bioleaching procedure.
The use of adapted microorganisms prior to leaching can enhance the leaching efficiency by 2 to 4 times when compared to unadapted culture (Li and Ke, 2001a; Li and Ke, 2001b).
Biomining is generally applied commercially as a heap leaching operation. A typical heap leach involves crushing and agglomeration of an ore or concentrate, followed by the stacking (for example 6-10 meters high) on an impermeable membrane. Sulfuric acid is percolated through the heap and additional aeration provided from at or near the bottom of the heap enhancing the microorganisms' growth. The native or inoculated microbial flora's growth causes the mineral dissolution, releasing the metal of interest in a leachate solution, or pregnant leach solution (PLS). The PLS is further processed for metal recovery by solvent extraction/electrowinning (SX/EW). The heterogeneous nature of the heap bio-leaching process results in large variation in temperature, particle size and reaction chemistry within the heap. Consequently, the rate of bio-leaching throughout the heap may vary, usually requiring extensive leaching periods of 300-450 days to ensure that as much of the heap is leaching effectively as possible.
One of the major costs associated with heap leaching operations is acid consumption. Acid consumption rates vary depending on the ore composition. This is further influenced by the operating pH and to a lesser extent the temperature.
Bioleaching of metal sulphides at extreme pH (<2) can result in the dissolution of gangue materials. Undesirably cations, such as aluminium, manganese, amorphous silica and specifically excessive ferric, can further result in releasing toxic trace elements, thickening of leach liquor thus potentially interfering with liquid flow in heap leaching, formation of passivation of sulphide minerals by jarosite formation or can be problematic during recovery of base metals during refinery (Dopso et al., 2009, Halinen et al., 2009).
Another important consideration for heap leaching is the downstream processing of the PLS. Final effluents from bioleaching operations generally have to be neutralised to remove iron and sulphate as stable end products by the addition of limestone or lime to increase of the pH of effluent to approximately 3. Therefore, it is understood by the Applicants that bioleaching of metals at high pH may potentially improve the downstream metals recovery processes, as well as reducing the operating costs.
The mineralogy of the specific ore can have a significant impact on the acid consumption properties and solution composition of the bacterial leaching system. Depending on the composition of the feed sample, the dissolution of mineral sulfides can be classified as either acid-producing or acid consuming. The majority of the gangue present in most ore samples, include magnesium silicates, and are acid consuming (Rawlings et al., 2003; Strömberg and Banwart, 1999). Therefore, maintaining of solution pH within a desirable range with the addition of sulfuric acid can be a major cost during a bioleaching operation (Watling, 2006). The application of pre-leaching of ore containing high levels of magnesium gangue prior to the bioleaching phase have shown to reduce time required to stabilize the pH level between 1.7-2.2 (Zhen et al., 2009; Qin et al., 2009). However, such a method has resulted in higher overall acid consumption at greater than 600 g kg-1 ore (Zhen et al., 2009; Qin et al., 2009). Halinen et. al. (2009) has demonstrated that an increase of pH from 1.5 to 2.0 during the column leaching of a particular black schist ore can reduce the acid consumption from 160 g kg-1 ore to 38 g kg-1 ore.
Ideally, in a heap leaching operation, target metals such as nickel and copper are solubilised with minimal acid consumption and iron dissolution. It is generally understood that microbial growth is favored at a lower pH. Accordingly, low pH, below about pH 2.5, has to date been utilised to increase leaching efficiency in heaps.
The present invention has as one object thereof to overcome substantially the abovementioned problems of the prior art, or to at least provide a useful alternative thereto.
Throughout this specification, unless the context requires otherwise, the word “comprise” or variations such as “comprises” or “comprising”, will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group of integers.
Other definitions for selected terms used herein may be found within the detailed description of the invention and apply throughout. Unless otherwise defined, all other scientific and technical terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which the invention belongs.
The invention described herein may include one or more range of values (eg. size, displacement and field strength etc). A range of values will be understood to include all values within the range, including the values defining the range, and values adjacent to the range which lead to the same or substantially the same outcome as the values immediately adjacent to that value which defines the boundary to the range.
In accordance with the present invention there is provided a method of adaptation of a bacterial culture for use in the treatment of ores and concentrates, the method comprising the method steps of:
Exposing the bacterial culture to increasing levels of pH over a period of time, whereby the bacterial culture is operative at a pH of above 2.5.
Preferably, the bacterial culture is operative at a pH of above 3.5.
Still preferably, the bacterial culture is operative at a pH of between about 3.5 to 5.
Preferably, the bacterial culture is a salt tolerant culture.
Still preferably, the salt tolerant culture is capable of operation at chloride concentrations of greater than about 100 g/L.
Still further preferably, the salt tolerant culture is capable of operation at total dissolved solids (TDS) levels of greater than about 115 g/L.
The temperature of step (i) is preferably about 45 to 55° C.
Still preferably, the temperature of step (i) is between about 50 to 55° C.
In one form of the present invention the bacterial culture is a bacterial culture capable of oxidising sulphide ores and concentrates.
In accordance with the present invention there is further provided a leaching process comprising the process steps of:
Preferably, the adaptation of the bacterial culture of step (i) adapts that bacterial culture to operate at a pH above 3.5.
Still preferably, the adaptation of the bacterial culture of step (i) adapts that bacterial culture to operate at a pH between about 3.5 to 5.
Still further preferably, the adaptation of the bacterial culture of step (i) adapts that bacterial culture to operate at a pH of about 5.
The leaching of step (ii) is preferably conducted at the same or similar pH to that to which the bacterial culture has been adapted in step (i).
In one form of the present invention the bacterial culture may be adapted in step (i) to additional conditions, including conditions of salinity.
The leaching of step (ii) is preferably conducted at the same or similar additional conditions to that to which the bacterial culture has been adapted in step (i).
In one form of the present invention the leach is conducted in the form of a heap leach utilising one or more heaps. In another form of the present invention the leach is conducted in one or more tanks.
In a still further form of the present invention the leach provides a target metal recovery of greater than about 70% at a pH of between about 3.0 to 3.5. Preferably, the leach provides a target metal recovery of greater than 70% at a pH of greater than about 3.5. Still preferably, the target metal is nickel.
The leaching process of the present invention preferably consumes relatively low amounts of acid. Further, the leaching process of the present invention preferably produces a pregnant leach solution containing relatively low levels of iron.
The present invention will now be described, by way of example only, with reference to several embodiments thereof and the following drawings, in which:—
The method of adaptation of a bacterial culture of the present invention begins, in one form, with the selection of a salt tolerant bacterial culture. The selection of a salt tolerant bacterial culture is predicated on the observation that iron tends to precipitate from solution with high salt levels. Accordingly, salt tolerant bacterial cultures are adapted to leaching with low levels of iron in solution. The pH of the bacterial culture is increased in pH increments of 0.5 to a pH of at least 2.5, for example 3.5, at which point the majority of iron is precipitated. The bacterial culture of the present invention is adapted to operate effectively at 50 to 55° C. However, a range of about 45 to 55° C. is anticipated by the Applicants. The Applicant has deposited a sample of such an adapted bacterial culture, specifically prepared for use in the leaching of base metals, with the Australian Government's National Measurement Institute as Accession No. V08/027581. Additional samples specifically prepared for use in the leaching of copper and nickel have also been deposited with Accession Nos. V08/027580 and V08/027582, respectively.
The outcome of the adaptation process is assessed and if considered successful the pH is increased further in smaller increments. Kinetic and recovery data of the culture is noted as a measure of performance.
The tests of the bacterial culture are conducted in agitated vessels as opposed to shakers so as to mimic as closely as possible industrial conditions. The culture undergoing adaptation is split and further adapted, or re-adapted, to conditions of other starter cultures. Such conditions may include fresh water. The starter cultures are then mixed with the adapted culture and the process repeated. This is intended to produce pH resistance, or adaptation of high pH, in each of a range of cultures, being for example copper fresh, copper salt, base metal fresh, base metal salt, high arsenic, ferric oxidisers and so on.
It is envisaged that a final pH target of 10 may be achievable to facilitate gold leaching.
The adapted bacterial culture of the present invention may be utilised in a leach process comprising the process steps of:
Adapting a bacterial culture to operate at a pH of above 2.5; and
Leaching an ore or concentrate to which the adapted bacterial culture of step (i) has been added or is added in one or more heaps at a pH above 2.5.
The adaptation of the bacterial culture of step (i) adapts that bacterial culture to operate at a pH above 3.5, for example between about 3.5 to 5, further at about 5.
The leaching of step (ii) is conducted at the same or similar pH to that to which the bacterial culture has been adapted in step (i). The bacterial culture may be adapted in step (i) to additional conditions, including conditions of salinity.
The leaching of step (ii) is conducted at the same or similar additional conditions to that to which the bacterial culture has been adapted in step (i).
The leaching process of the present invention is envisaged to consume relatively low amounts of acid. Further, the leaching process of the present invention produces a pregnant leach solution containing relatively low levels of iron.
Iron is precipitated in one or more of the or each heap, or the or each leach tank, dependent upon the form of leach utilised. It is envisaged that the leaching process of the present invention will either not require a precipitation circuit or the precipitation circuit required will be significantly smaller than that required by prior art operations of a similar size and nature.
The present invention will now be described with reference to several non-limiting examples, as follows.
The objective of this initial test work was to develop a proprietary bacterial culture of the Applicant, being termed culture Ni—S-J065, so that the culture is capable of operating at a higher pH of 2.5, 3.0 or 3.5. The culture Ni—S-J065 is the culture referred to above and deposited under Accession No. V08/027581. The development of the culture to operate at higher pH was be carried out in a stepwise procedure, under saline conditions of 100 g/L or (115 g/L TDS) and at 50-55° C.
Each stage of the development ran for 3 months, while targeting >70% Ni oxidation before each scale up. Bacterial counts will also be monitored for growth and development.
Culture Development—Batch stirred tank reactor tests to develop culture Ni—S-J065 to leaching metal from a first ore sample at high pH.
Amenability Study—The best performing culture will be selected to be used in an amenability and compare the performance of the high pH leaching culture to the original Ni—S-J065 culture.
1.1. OK Nutrient Media (pH 1.6-1.8)
Dissolve all solids in 500 mL of distilled or tap water, pH adjust to 1.6-1.8 with H2S04 (98% AR grade), before makeup up to 1 L with distilled or tap water.
Solution Sample Preparation for Assay
1.1.1. Sampling
1.2.2. Solution Preparation
Calibration of Diluent (use for preparation for solution assay)
1.1.2. Determining SG of HCl.
1.1.3. Calibration of Bottle Top Dispenser.
1.1.4. Calibration of Pipette.
Check calculation sheet to ensure averaged dilution factor is between 1.49 and 1.51.
Ferrous Iron Titration
1.1.5. Titration procedures
1.1.6. Titration Calculation
Cr2O72−+14H++6Fe2+→2Cr3++7H2O+6Fe3+
Fe2+ ppm=mL of titration×557.6
1.1.7. Titration Solution
1.1.7.1. Buffer Solution
1.1.7.2. Iron Indicator
1.1.7.3. Standard Potassium Dichromate Stock Solution
Sample Preparation
Saline Adaptation
Summary of Salt information
Bacterial Development
Adaptation and Amenability
Termination of Amenability Study
As described in Example 1 above, for the development of cultures capable of operating at high pH's, it was considered advantageous to select a starting culture that was not dependent on high ferric levels for leaching to progress. The Applicant has chalcopyrite and saline tolerant cultures that naturally operate in low ferric environments at conventional pH's (below 2), and the saline culture (Deposited as Accession No. V08/027581) was chosen as the starting point, as it also operates in low total iron environments due to tendency of the iron to precipitate in the highly saline environment.
As ferric iron begins to precipitate beyond pH 3 due to exceeding the solubility product, in a similar manner that precipitation is noted in the Applicant's saline culture, this culture was thought to be the best match to the proposed leaching conditions. Using the Applicant's procedures set out at Example 1 above, this culture was then adapted to operate at higher pH's.
A culture designated Ni—S-J065B was used in these studies, being derived directly from the culture prepared by the method of Example 1 above. The cultures were grown in 3 L stirred tank reactors and were maintained on nickel concentrate suspended in water. The desirable pH of the solution was achieved by addition of concentrated sulphuric acid. A customised water bath was used to regulate the temperature in the bioreactor at approximately 55° C. and aeration was provided to the culture by compressed air introduced into the mixing zone of the reactor.
Prior to its use, Ni—S-J065B was adapted to saline condition of 100 g/L Cl− (115 g/L TDS), and a subculture of Ni—S-J065B was gradually adapted to a solution pH of 3.5. To distinguish the newly developed culture from the original inoculum, it was renamed to Ni—S-J069B.
A high magnesia ore sample, designated J062A, was split using rotary splitter to provide samples as feed for bacterial development work and metallurgical analysis. A Head sample of the ore was assayed for Ni, Co, Zn, Cu, Fe, Al, Ca, Mg, Mn, S (Total), S (Elemental), S2− (Sulphide), SO42−, C (Total), CO32−, and an ICP Scan.
Acid consumption studies were carried out on sample crushed to P100=9.5 mm using a bottle roll technique. Concentrated sulphric acid was used to maintain the solution pH 1.8 to simulate conventional bioleaching conditions. Acid addition was recorded and used to calculate the total quantity of acid consumed by the ore.
Head grade assay revealed the ore, J062A, to contain 0.68% nickel, 11.30% iron and 20.10% magnesium.
Mineralogical analysis indicates the main nickel bearing sulphide to be pentlandite at 2.18% of the total sample. Chalcopyrite is the other economic sulphide with a concentration of 0.14%. The main sulphide gangue occurs as pyrrhotite (2.18%). Magnesium is found in the form of forsterite (56.1%), edenite (18.8%), clinochlore (7.9%) and dolomite (2.9%). There appears to be a low level of liberation of nickel sulphides, however at the 3 mm crush size the majority of the grains have some exposure to the surface of the particle, indicating potential for leaching.
In order to understand the acid consumption characteristic of the ore under bioleaching solution acid consumption tests using a bottle roll technique at pH 1.8 was carried on ore crushed to 100% passing 9.5 mm.
The bioleaching of J062A ore was carried out at a temperature of 55° C. at various solution pH value. Preliminary results indicated that nickel recoveries between all cultures were similar, see
Redox potential measurements throughout the study revealed that the readings fluctuated during the first 20 days in all cultures before increasing and stablising at a constant value, as seen in
As is shown in
Sulphuric acid used to maintain the solution pH for each of the cultures was recorded during the study and used as a method of comparing acid consumptions between the tests. Preliminary analysis revealed that the cumulative quantity of acid needed to maintain the solution pH at low pH, is greater than for those tests at higher pH, as can be seen with reference to
It should be noted that acid consumptions are comparatively higher compared to the bottle roll test above due mainly to the much finer particle size of the leach test, compared with the bottle roll test.
As can be seen with reference to the above description, a microbial culture capable of leaching at high pH, and in saline solution of 100 g/L Cl− was developed using the Applicant's procedures. The results have shown the culture is capable of leaching ore containing high levels of magnesium with solution pH values of 3 to 3.5 resulting in nickel recovery greater than 70%. Under these conditions, initial test work has indicated low levels of iron in solution and the acid consumption was reduced significantly, from approximately 736 kg/t of ore at pH 1.8 to 33 kg/t of ore at pH 3.5.
Further testing was undertaken, in the manner described for Example 2 above, to investigate the performance of the Applicant's bacterial culture. A summary of the controls and variables utilised in this testing is provided in the Table in
The table immediately below shows the summary of head assay results on the ore and concentrate used in this study:
The table immediately below provides a summary of metal recoveries based on residue assay and acid consumed for the completed test:
The total acid consumption value noted in the table above is when nickel or copper reach a maximum percentage of recovery.
For each culture, initial pH and adjusted pH values were measured. The pH was adjusted by the addition of 98% H2SO4. Cumulative sulphuric acid is calculated in kilograms of 98% H2SO4 consumed per ton of ore. When acid is not added cumulative value reach steady state.
In
A sample of the Applicant's high pH leaching culture was submitted for microbial characterisation studies. Terminal restriction fragment length polymorphism (T-RFLP) technique was used to identify the microbes present in the culture. The majority of the microbes identified in the culture are Acidithiobacillus caldus, Alicyclobacillus sp, Acidithiobacillus sp and Acidimicrobium sp (see
Modifications and variations such as would be apparent to the skilled addressee are considered to fall within the scope of the present invention.
Number | Date | Country | Kind |
---|---|---|---|
2012901968 | May 2012 | AU | national |
2013204372 | Apr 2013 | AU | national |
Filing Document | Filing Date | Country | Kind |
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PCT/AU2013/000496 | 5/14/2013 | WO | 00 |