Silver-catalyzed bioleaching of low-grade copper ores. Part II: Stirred tank tests

A study of the effect of different variables (inoculation, aeration, silver complexants, [Ag], [Fe³⁺], temperature and chemical activation stage) on the silver-catalyzed bioleaching of two different low-grade copper ores has been carried out in stirred tanks. The catalyzed bioleaching process was greatly affected by bacterial activity. Aeration and the use of different complexing agents (thiosulfate and thiosulfate plus cupric ions) did not enhance but also did not inhibit the copper kinetics in the silver-catalyzed process. On the contrary, the presence of 5 g/L Cl⁻ inhibited the catalytic effect of silver. The effect of silver concentration was tested on two different low-grade copper ores in the range between 10 and 500 mg Ag/kg for the lower K-ore and between 1.4 and 35.7 g Ag/kg Cu for the PVD ore, the former with a higher content of copper. Silver catalysis was effective for both ores but the PVD ore was basically unaffected by silver concentration in the range studied. Maximum copper extractions and copper dissolution rates were obtained with a very small amount of silver (3.6 g Ag/kg Cu). In all cases, the copper recovery was at least twice that in the absence of silver (∼ 30%). High ferric concentrations have been tested in the absence and in the presence of silver. The presence of silver was essential to improve the copper extraction from chalcopyrite in acidic ferric sulfate solutions. However, bioleaching experiments conducted with silver and 1 g/L Fe³⁺ produced lower copper extractions (20%) compared to experiments where ferric iron was absent (55%). The copper dissolution in the silver-catalyzed lower K-ore bioleaching is temperature dependent, with an optimum temperature around 35 °C. The activation energies of the copper dissolution process were 109.7 and 20 kJ/mol in the ranges of temperature between 15 and 28 °C and 28 and 45 °C respectively. The chemical activation stage establishes optimum conditions that promote higher copper extractions in the presence of silver.     

Silver catalyzed bioleaching of low-grade copper ores. Part III: Column reactors

A study of the effect of different variables (inoculation, [Ag], silver addition mode, reactivation of the ore (i.e. delayed silver addition), composition of the pregnant liquid solution, ore particle size, pH and aeration) on the silver-catalyzed bioleaching of two different low-grade copper (> 600 μm) has been investigated in column reactors.The two low-grade copper ores tested, lower K-ore and Pinto Valley Dump ore, behaved similarly during the silver catalyzed process. After more than 300 days of leaching, the addition of both silver and bacteria improved the copper extraction from both low-grade chalcopyritic ores. Copper extraction in the presence of silver displays paralinear kinetics with two stages very well defined, with the first stage being much faster than the second one.Copper extraction from the K-ore surpassed 70% after 350 days of bioleaching using low concentrations of silver (1.4 g Ag/kg Cu). The addition of silver was effective even after the bioleaching process was started. Conversely, silver addition mode and aeration were not significant variables in the bioleaching process. The effect of a pregnant liquid solution collected from a first bioleaching experiment demonstrated that the build up of the solution can negatively affect the copper extraction during the silver-catalyzed chalcopyrite process.Copper extraction from PVD ore surpassed 60% after 300 days of bioleaching using 1.24 g Ag/kg Cu. Copper extraction was substantially affected by both [Ag] and ore particle size. For the ranges between 0.25 and 1.00 g Ag/kg Cu and between < 5.08 × 10⁴ and < 1.27 × 10⁴ μm, the dissolution of copper was favoured with the highest amount of silver and the smallest particle size. On the other hand, silver concentration, pH and silver addition mode were not influential variables in the process.Chemical analyses, XRD and SEM/EDX studies were carried out on different residues after 100, 200 and 325 days of experimentation. Chemical analysis showed that copper is selectively bioleached in the presence of silver and bacteria, while silver remains in the solid phase. The SEM study showed that pyrite remains mainly unattacked during the bioleaching of chalcopyrite from the low-grade copper ore. Jarosite, gypsum and elemental sulphur precipitates have been identified on the residues.     

Influence of microwave pretreatment on the bioleaching behaviour of low-grade complex sulphide ores

Mineralogical information on the mechanisms by which microwave pretreatment improves the bioleaching behaviour of low-grade complex sulphide ore, and an interpretation of the interrelationship between mineralogy, microwave processing, and bioleaching process are provided in this study. The influence of microwave irradiation on the bioleaching behaviour and mechanisms of a low-grade complex sulphide ore subjected to microwave heating in a kitchen type microwave oven at a power output 1100 W for 5 min was investigated in a mixed mesophilic bacterial culture through bioleaching experiments and electrochemical techniques. Results revealed that microwave treatment improved the bioleaching of behaviour of the ore, with more effect on copper and iron dissolutions than on zinc and lead. Both microwave treated and untreated samples showed similar electrochemical behaviour. However, microwaved samples displayed higher reactivity, dissolution rates, dissolution currents, current densities and a decreased polarization resistance. Increase in dissolution of the microwaved treated samples resulted from phase changes in the ore which promoted galvanic interaction within the system, decrease in the amounts of sulphur contents, and an increase in electrochemical sites resulting from an increase in the number of cracks induced by microwave heating.     

Leaching of chalcopyrite with ferric ion. Part III: Effect of redox potential on the silver-catalyzed process

This study examines the effect of redox potential on silver-catalyzed chalcopyrite leaching. Leaching tests were carried out in stirred Erlenmeyer flasks with 0.5 g chalcopyrite mineral, 1 g Ag/kg Cu and 100 mL of a sulphate solution of Fe³⁺/Fe²⁺ (with redox potential ranging between 300 and 600 mV Ag/AgCl) at pH 1.8, 180 rpm and 35°C or 68 °C. Unlike uncatalyzed leaching, an increase of the redox potential increased copper dissolution in the presence of silver ions, as the regeneration of Ag⁺ requires a high concentration of oxidizing agent, Fe³⁺. Additionally, the high reactivity of the mineral surface when silver was present could have been responsible for inhibiting the nucleation of hydrolysis products of Fe³⁺ on it. Excessive addition of silver transformed the chalcopyrite surface into copper-rich sulphides such as covellite, CuS, and geerite, Cu₈S₅, preventing the formation of CuFeS₂/Ag₂S galvanic couple and the recycling of silver ions.     

Bacterial leaching of low-grade ZnS concentrate using indigenous mesophilic and thermophilic strains

In this study low-grade sphalerite has been treated by the bioleaching process using native cultures of Acidithiobacillus ferrooxidans and Sulfobacillus thermosulfido-oxidans in order to determine the ability of these bacteria to the leaching of zinc. The effects of bacterial strain, pH, temperature, pulp density, iron precipitation, and initial concentration of ferric iron on the zinc leaching were evaluated. The bioleaching experiments were carried out in shake flasks at pH 1.5, 180 rpm, 33 °C and 60 °C for mesophilic and thermophilic bacteria, respectively. Compared with the use of laboratory reference strains or control conditions, zinc recovery from the respective concentrate was greater when native isolates were employed. The experimental data show that the selection of the suitable pH and temperature during the bioleaching processes would be important. The results indicate that the increase in pulp density generates a decrease in the dissolved zinc concentration. The maximum zinc extraction reached was 87% using native thermophile S. thermosulfido-oxidans culture after 30 days.     

Column Bioleaching of a Low-Grade Silicate Ore of Uranium

The bioleaching of a low-grade Indian uraninite ore (triuranium octoxide, U₃O₈: 0.024%), containing ferro-silicate and magnetite as the major phases, and hematite and pyrite in minor amounts, has been reported. Experiments were carried out in laboratory scale column reactors inoculated with enriched culture of Acidithiobacillus ferrooxidans isolated from the source mine water. The pH effect on uranium recovery was examined with the same amounts of ores in different columns. With the presence of 10.64% Fe in the ore as ferro-silicate, the higher uranium biorecovery of 58.9% was observed with increase in cell count from 6.4 × 10⁷ to 9.7 × 10⁸ cells/mL at pH 1.7 in 40 days as compared to the uranium recovery of 56.8% at pH 1.9 with a corresponding value of 9.4 × 10⁸ cells/mL for 2.5-kg ore in the column. The dissolution of uranium under chemical leaching conditions, however, recorded a lower value of 47.9% in 40 days at room temperature. Recoveries were similar with 6-kg ore when column leaching was carried out at pH 1.7. The bioleaching of uranium from the low-grade ore of Turamdih may be correlated with the iron(II) and iron(III) concentrations, and redox potential values.     

Possibility of using chemical fertilizers instead of 9K medium in bioleaching process of low-grade sulfide copper ores

The possibility of applying chemical fertilizers as a source of nutrients for bacterial growth in bioleaching process was investigated. In the first part of the experiment the nutrient content of four sulfide copper ore samples was determined. The results confirmed that the amount of calcium, magnesium and sulfur were sufficient to support bacterial growth, whereas nitrogen, phosphorous and potassium were not sufficient. Therefore, N, P, and K from a chemical fertilizer source were applied to the sulfide copper ores to make a cost-effective bioleaching process. According to shake flask experiments by using mesophilic, iron-sulfur oxidizing bacteria, bacterial activity and copper recovery in some proposed media was satisfactory compared to 9K medium. Additionally, potassium had positive effect on the copper ore bioleaching while NO₃⁻ and Cl⁻ had inhibitory effect on the bacterial activity.     

Silicate mineral dissolution in the presence of acidophilic microorganisms: Implications for heap bioleaching

Silicate minerals are found with sulfide minerals and therefore, can be present during heap bioleaching for metal extraction. The weathering of silicate minerals by chemical and biological means is variable depending on the conditions and microorganisms tested. In low pH metal rich environments their dissolution can influence the solution chemistry by increasing pH, releasing toxic trace elements, and thickening of the leach liquor. The amenity of five silicate minerals to chemical and biological dissolution was tested in the presence of either ‘Ferroplasma acidarmanus’ Fer1 or Acidithiobacillus ferrooxidans with olivine and hornblende being the most and least amenable, respectively. A number of the silicates caused the pH of the leach liquor to increase including augite, biotite, hornblende, and olivine. For the silicate mineral olivine, the factors affecting magnesium dissolution included addition of microorganisms and Fe²⁺. XRD analysis identified secondary minerals in several of the experiments including jarosite from augite and hornblende when the medium contained Fe²⁺. Despite acidophiles preferentially attaching to sulfide minerals, the increase in iron coupled with very low Fe²⁺ concentrations present at the end of leaching during dissolution of biotite, olivine, hornblende, and microcline suggested that these minerals supported growth. Weathering of the tested silicates would affect heap bioleaching by increasing the pH with olivine, fluoride release from biotite, and production of jarosite during augite and hornblende dissolution that may have caused passivation. These data have increased knowledge of silicate weathering under bioleaching conditions and provided insights into the effects on solution chemistry during heap bioleaching.     

Column bioleaching of a low grade nickel-bearing sulfide ore containing high magnesium as olivine,chlorite and antigorite

This work investigates the bioleaching of Jinchuan low grade nickel-bearing sulfide ore containing rather high levels of olivine, chlorite and antigorite (MgO 30–35%) present in the main gangue minerals using a mixed mesophiles which are composed of Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans. It aims to test the technical feasibility to recover valuable metals from Jinchuan low-grade nickel-bearing sulfide ore by bioleaching process. The tolerance of the mixed bacteria to Mg²⁺ could be improved markedly from 10 g/L to 25 g/L after nearly 2 years adaptation. A nickel recovery of 91% and a cobalt recovery of 81% were achieved in 312 days column leaching process including 60 days acid pre-leaching stage and 252 days bioleaching stage.     

Visualisation of pyrite leaching by selected thermophilic archaea: Nature of microorganism–ore interactions during bioleaching

In this study, pyrite (FeS₂) was leached by Acidianus brierleyi, Metallosphaera sedula and Sulfolobus metallicus during a 60 day experimental period. Leaching occurred over a redox potential range of 800 to 860 mV (S.H.E.) and in the presence of increasing Fe³⁺ levels. A modified ferrozine assay was developed to detect the increase of iron in solution as bioleaching of the ore progressed. For the first time, the interactions of these extreme thermophiles with the metal sulfide ore particles were extensively documented using SEM and TEM. As the pyrite degraded, there appeared to be a progression of deposited structures forming, ranging from sub-micron precipitates and disc-shaped structures on the ore's surface, which ultimately were similar for all leaching cultures. Furthermore, the residues resulting from the leaching of pyrite by M. sedula, the most active thermophile, were characterised using SEM/EDX, and appeared to be dominated by iron sulfate precipitates. The nature of the deposits formed, together with our other results, indicate that A. brierleyi, M. sedula and S. metallicus acted through the ‘contact’ and ‘non-contact’ sub-mechanisms of the indirect bioleaching mechanism for the dissolution of pyrite. The role of the bioleaching microorganisms is thus to maintain sufficient levels of Fe³⁺ and acid during pyrite leaching, for maximal mineral dissolution.     

低品位硫化镍铜矿生物浸出工艺研究

研究了某低品位硫化镍铜矿的生物浸出工艺矿物学,考察了接种量、初始pH、矿石粒度、浸出周期对该矿摇瓶浸出过程的影响。在矿石粒度-0.074 mm占90%、矿浆浓度2%、细菌接种量30%、初始pH 1.5、浸出周期30天、摇床转速150 r/min的条件下,可获得最大的镍铜浸出率,分别为89.79%和41.80%。     

Leaching of chalcopyrite with ferric ion. Part IV: The role of redox potential in the presence of mesophilic and thermophilic bacteria

This paper reports a study on the effect of redox potential in chalcopyrite bioleaching in the presence of iron- and sulphur-oxidizing bacteria. Bioleaching tests were carried out in stirred Erlenmeyer flasks at 180 rpm, with 0.5 g of chalcopyrite mineral, 99 ml of a sulphate solution of Fe³⁺/Fe²⁺ (with the redox potential ranging between 300 and 600 mV Ag/AgCl) at pH 1.8 and 1 ml of a mesophilic (35 °C) or thermophilic (68 °C) culture. The overoxidation of the leaching solution, due to the activity of iron-oxidizing microorganisms (Acidithiobacillus ferrooxidans, Leptospirillum ferrooxidans and Sulfolobus BC), favoured the precipitation of jarosite on chalcopyrite surfaces followed by passivation. Iron- and sulphur-oxidizing microorganisms, such as A. ferrooxidans and Sulfolobus BC adapted for 4 months to elemental sulphur as the sole energy source, recovered their iron-oxidizing ability after being in contact with Fe²⁺.     

Copper recovery from chalcopyrite concentrates by the BRISA process

The technical viability of the BRISA process (Biolixiviación Rápida Indirecta con Separación de Acciones: Fast Indirect Bioleaching with Actions Separation) for the copper recovery from chalcopyrite concentrates has been proved. Two copper concentrates (with a copper content of 8.9 and 9.9 wt.%) with chalcopyrite as the dominant copper mineral have been leached with ferric sulphate at 12 g/L of ferric iron and pH 1.25 in agitated reactors using silver as a catalyst. Effects of temperature, amount of catalyst and catalyst addition time have been investigated. Small amounts of catalyst (from 0.5 to 2 mg Ag/g concentrate) were required to achieve high copper extractions (>95%) from concentrates at 70 °C and 8–10 h leaching. Liquors generated in the chemical leaching were biooxidized for ferrous iron oxidation and ferric regeneration with a mixed culture of ferrooxidant bacteria. No inhibition effect inherent in the liquor composition was detected. The silver added as a catalyst remained in the solid residue, and it was never detected in solution. The recovery of silver may be achieved by leaching the leach residue in an acid-brine medium with 200 g/L of NaCl and either hydrochloric or sulphuric acid, provided that elemental sulphur has been previously removed by steam hot filtration. The effect of variables such as temperature, NaCl concentration, type of acid and acidity–pulp density relationship on the silver extraction from an elemental sulphur-free residue has been examined. It is possible to obtain total recovery of the silver added as a catalyst plus 75% of the silver originally present in concentrate B (44 mg/kg) by leaching a leach residue with a 200 g/L NaCl–0.5 M H₂SO₄ medium at 90 °C and 10 wt.% of pulp density in two stages of 2 h each. The incorporation of silver catalysis to the BRISA process allows a technology based on bioleaching capable of processing chalcopyrite concentrates with rapid kinetics.     

Microbial extraction of nickel from Sukinda chromite overburden by Acidithiobacillus ferrooxidans and Aspergillus strains

In this study, the recovery of nickel from a low-grade chromite overburden was attempted by employing two fungal strains, Aspergillus niger and Aspergillus fumigatus, and a mixed culture of mesophilic acidophiles (predominantly Acidithiobacillus ferrooxidans). Various factors were studied for bioleaching of chromite overburden such as, temperature, pH and pulp density. It was found that the At. ferrooxidans culture solubilized nickel effectively at temperatures ranging from 30 °C to 37 °C, whereas the organism was not able to solubilize nickel at higher temperatures, such as 45 °C. The use of higher pulp density resulted in a decrease of the percent nickel recovery whereas lower pulp density resulted in higher recovery values. Besides, increased supplemental ferrous iron increased the leaching efficiency of the At. ferrooxidans culture. The maximum nickel solubilization was 40%, at 2% pulp density, and 24%, at 10% pulp density, at 30 °C after 28 days leaching at 150 rpm.In the case of fungal strains, a comparison of leach ability of chromite overburden and roasted overburden was made. The factors studied were pulp density and reaction time. The adapted fungal strain showed better leaching results as compared to the unadapted strains. The in situ nickel leaching efficiency of a laboratory stock culture of A. niger showed maximum recovery of 34% nickel with roasted chromite overburden, at 2% pulp density, while 32% nickel was solubilized by A. fumigatus, under the same conditions at 30 °C and 150 rpm, after 28 days incubation.     

Dissolution of uranium from silicate-apatite ore by Acidithiobacillus ferrooxidans

Bioleaching of a low-grade Indian silicate-apatite uranium ore containing 0.024% U₃O₈ and 10.6% iron with minor amounts of base metals has been reported. The studies involved extraction of uranium using enriched culture containing Acidithiobacillus ferrooxidans (A. ferrooxidans) derived from the source mine water employing bio-chemically generated ferric ion as an oxidant. Parameters such as particle size of the ore, pulp density, and pH of lixiviant media were optimised. Maximum uranium bio-dissolution of 98% was achieved using ore of mixed particles of < 76 μm size. Uranium bio-recovery was found to be 96% at the pulp density (PD) of 10% (w/v) and 20% (w/v) with the particles of < 76 μm size in 40 days at 2.0 pH and 35 °C temperature. At 1.7 pH and 20% (w/v) PD, 98% uranium bio-recovery was achieved with a rise in redox potential from 595 mV to 715 mV in 40 days. Uranium bio-dissolution may be correlated with the generation of ferric ions through the bio-chemical action on the ore. The work illustrated the efficacy of leaching of uranium by the involvement of bacteria by indirect mechanism.     

Use of mesophilic and thermophilic bacteria for the improvement of copper extraction from a low-grade ore

Bioleaching was examined for copper extraction from a low grade ore using mesophilic and moderate thermophilic bacteria. Five equal size columns were used for the leaching of the ore. Sulfuric acid solution with a flow rate of 3.12 L.m-2.h-1 and pH 1.5 passed through each column continuously for 90 d. In the first and the second column, bioleaching was performed without agglomeration of the ore and on the agglomerated ore, respectively. 28wt% of the copper was extracted in the first column after 40 d, while this figure was 38wt% in the second column. After 90 d, however, the overall extractions were almost the same for both of them. Bioleaching with mesophilic bacteria was performed in the third column without agglomeration of the ore and in the fourth column on the agglomerated ore. After 40 d, copper extractions in the third and the fourth columns were 62wt% and 70wt%, respectively. Copper extractions were 75wt% for both the columns after 90 d. For the last column, bioleaching was performed with moderate thermophilic bacteria and agglomerated ore. Copper extractions were 80wt% and 85wt% after 40 and 90 d, respectively. It was concluded that crushing and agglomeration of the ore using bacteria could enhance the copper extraction considerably.     

Dissolution kinetics of spent petroleum catalyst using two different acidophiles

Leaching studies using spent petroleum catalyst containing Ni, V and Mo were carried out using two different acidophiles, iron oxidizing (IOB) and sulfur oxidizing (SOB) bacteria. XRD analysis proved the existence of V in oxide form, Ni in sulfide form, Mo both in oxide and sulfide forms, and sulfur in elemental state. Both bacteria showed similar leaching kinetics at the same leaching parameters, such as pH, nutrient concentration, pulp density, particle size and temperature. The dissolution kinetics for Ni and V was much higher than Mo. Bioleaching kinetics was observed to follow dual rates, initially faster followed by a slower rate. So, dissolution mechanism was based on surface- and pore-diffusion rate. The dissolution process was found to follow 1st order kinetics. Unified dissolution rate kinetics equations were developed using 1st order rate kinetics. Various thermodynamic parameters were also calculated. Rate determining step for both the bacteria were evaluated and the average D₁ (surface) and D₂ (pore) values were found to be around 7 × 10^− 9 and 1 × 10^− 10 cm² respectively. The lower value of D₂ suggested that the pore diffusion is the rate determining step during bioleaching process.     

Bioleaching of an organic-rich polymetallic concentrate using stirred-tank technology

The bioleaching of a concentrate produced from a black shale ore in an industrial operation in Poland was assessed. Following preliminary batch culture tests, processing in continuous conditions was tested to determine the main specifications for the application of the stirred-tank technology to this organic-rich polymetallic concentrate.The experimental work was carried out in a laboratory-scale unit consisting of three stirred tanks (50 L or 20 L) using an acidophilic and moderate thermophilic (42 °C) bacterial population. Different configurations of the unit and key operating parameters were tested (nutrient medium composition, solids concentration, agitation and aeration rates). The analysis of both bacterial community structure and mineralogical characteristics of the concentrate and the bioleach residues were implemented in order to better understand the chemical and biochemical reactions occurring in the system. Using the data produced during the continuous operation, downstream processing assessment for both copper and silver recovery was also carried out.The best copper recovery obtained in the continuous operation was 92% and hot brine leaching of the bioleaching residue (PLINT Process) permitted the recovery of 92% of the silver. Copper and silver recoveries seemed to be limited by incomplete chalcopyrite dissolution. A preliminary techno-economical evaluation of the concentrate bioleach processing, including bioleaching and copper and silver recoveries, demonstrated the potential economical feasibility. Silver recovery plays an important role in the process's finances. This study presents promising results that encourage further investigation of bioleach processing.     

Electrochemical bioleaching of high grade chalcopyrite flotation concentrates in a stirred bioreactor

The main objective of this study is to improve the basic understanding of electrochemical bioleaching as an advanced hydrometallurgical process suitable for the treatment of high grade complex sulfide ores and to use this understanding for analyzing the potential of this process for copper recovery from high grade chalcopyrite ores and flotation concentrates. Using a typical flotation concentrate from the Sarcheshmeh copper processing complex (located in the south-east of Iran) and mixed mesophilic as well as moderately thermophilic microorganisms, leaching experiments were performed in a stirred bioreactor. The emphasis was given on the comparison between the results of bioleaching and that of electrochemical bioleaching tests. From the results of this study, it can be pointed out that compared to the conventional bioleaching; the electrochemical bioleaching of chalcopyrite flotation concentrate leads to about 35% more copper recovery. It seems that the main reason for increasing copper recovery by electrochemical bioleaching is the control of redox potential between 400 and 425 mV. Under this condition, the precipitation of iron oxy-hydroxides on the surface of chalcopyrite, which can act as a diffusion barrier and prevents chalcopyrite dissolution, is significantly reduced. This leads to a higher electrochemical reduction of chalcopyrite and its improved dissolution.     

微裂纹对硫化铜矿生物浸出的影响研究

利用紫金山低品位硫化铜矿,研究了微裂纹对铜生物浸出效果的影响。分别利用颚式破碎机、对辊破碎机和高压辊磨机对硫化铜矿进行破碎,采用体式显微镜、扫描电镜、核磁共振岩心成像系统和比表面积分析仪对矿石微裂纹及孔隙度进行观察统计与表征。结果表明,高压辊磨较颚式破碎和对辊破碎可以产生更多的微裂纹,同时高压辊磨破碎铜矿样品的孔隙度均高于颚式破碎和对辊破碎。-1.7mm粒级铜矿样品摇瓶浸出试验表明,由于高压辊磨破碎样品的比表面积和孔隙度更大,铜矿物与浸出液接触更加充分,浸出效果比颚式破碎和对辊破碎好。另外,-6.7+3.35mm粒级铜矿样品生物柱浸试验结果表明,含有更多微裂纹的高压辊磨破碎样品铜浸出率比颚式破碎提高9.10~15.43个百分点,比对辊破碎提高3.12~9.45个百分点。