Catalytic effect of visible light and Cd2+ on chalcopyrite bioleaching

The effects of visible light and Cd²⁺ ion on chalcopyrite bioleaching in the presence of Acidithiobacillus ferrooxidans (A. ferrooxidans) were studied by scanning electron microscopy (SEM), synchrotron radiation X-ray diffraction (SR-XRD), and X-ray photoelectron spectroscopy (XPS). The results of bioleaching after 28 days showed that the copper dissolution increased by 4.96% with only visible light, the presence of Cd²⁺ alone exerted slight inhibition effect on chalcopyrite dissolution and the concentration of dissolved copper increased by 14.70% with visible light and 50 mg/L Cd²⁺. The results of chemical leaching showed that visible light can promote the circulation of iron. SEM results showed that Cd²⁺ promoted the attachment of A. ferrooxidans on chalcopyrite surface under visible light. SR-XRD and XPS results indicated that visible light and Cd²⁺ promoted chalcopyrite dissolution, but did not inhibit the formation of passivation. Finally, a model of synergistic catalysis mechanism of visible light and Cd²⁺ on chalcopyrite bioleaching was proposed.     

嗜酸氧化亚铁硫杆菌（ATCC 23270）浸出黄铜矿过程中的EPS、Cu2+和Fe3+的相互作用机制（英文）

采用超声-离心方法提取嗜酸氧化亚铁硫杆菌(ATCC 23270)胞外多聚物(EPS)、EPS中的Cu2+、Fe3+离子,研究生物浸出黄铜矿过程中Cu2+、Fe3+和EPS的相互作用机制。结果表明:与Fe3+离子相比,Cu2+离子可刺激细菌产生更多的EPS;当Cu2+离子浓度从0.01mol/L增加到0.04mol/L时,EPS中Fe3+/Cu2+质量比从4:1降低到2:1;从1%黄铜矿的无铁9K介质中提取的EPS中铜铁含量是从含0.04mol/LCu2+离子的9K介质中提取的量的2倍。在生物浸出黄铜矿过程中,黄铜矿表面结合黄铁钾钒的EPS层减弱了Cu2+、Fe3+离子的迁移,逐渐成为离子扩散壁垒。     

Bioleaching of chalcopyrite by UV-induced mutagenized Acidiphilium cryptum and Acidithiobacillus ferrooxidans

The original strains Acidithiobacillus ferrooxidans GF and Acidiphilium cryptum DX1-1 were isolated from the drainage of some caves riched in chalcopyrite in Dexing Mine in Jiangxi Province of China.The optimum temperature and pH for growth were 30℃and 3.5 for Ac.cryptum DX1-1,and 30℃and 2.0 for At.ferrooxidans GF,respectively.For Ac.cryptum DX1-1,the optimum UV radiating time was 60 s and the positive mutation rate was 22.5%.The growth curves show that Ac.cryptum after mutagenesis reached stationary phase ...     

EPS-contact-leaching mechanism of chalcopyrite concentrates by A. ferrooxidans

The effect of extracelluar polymeric substances（EPS） on the bioleaching chalcopyrite concentrates in the presence of ironand sulphur-oxidizing bacteria （A. ferrooxidans） was studied. The bacterial number, pH, redox potential, and the concentrations of Fe^2＋ and Cu^2＋ ions were investigated. The leached residues were analyzed by the X-ray diffraction and FT-IR. The results indicate that the EPS makes the bacteria adhere to the chalcopyrite surface easily and it is helpful for bacteria in disadvantageous environment At the same time, EPS film layer with Fe^3＋ deposits on the surface of chalcopyrite and becomes a barrier of oxygen transfer to chalcopyrite to passivate chalcopyrite, and creates the high redox potential space through concentrating Fe^3＋ ions to accelerate bioleaching pyrite in chalcopyrite concentrates. The results suggest that EPS formation promotes bioleaching pyrite and inhibits bioleaching chalcopyrite, especially under high potential condition.     

Surface characterization of chalcopyrite interacting with Leptospirillum ferriphilum

The alteration of surface properties of chalcopyrite after biological conditioning with Leptospirillum ferriphilum was studied by adsorption, zeta-potential, contact angle and bioleaching tests. The strains of L. ferriphilum cultured using different energy sources (either soluble ferrous ion or chalcopyrite) were used. The adhesion of bacteria to the chalcopyrite surface was a fast process. Additionally, the adsorption of substrate-grown bacteria was greater and faster than that of liquid-grown ones. The isoelectric point (IEP) of chalcopyrite moved toward that of pure L. ferriphilum after conditioning with bacteria. The chalcopyrite contact angle curves motioned diversely in the culture with or without energy source. The results of X-ray diffraction patterns (XRD), scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) analysis indicate that the surface of chalcopyrite is covered with sulfur and jarosite during the bioleaching process by L. ferriphilum. Furthermore, EDS results imply that iron phase dissolves preferentially from chalcopyrite surface during bioleaching. The copper extraction is low, resulting from the formation of a passivation layer on the surface of chalcopyrite. The major component of the passivation layer that blocked continuous copper extraction is sulfur instead of jarosite.     

铁闪锌矿的Leptospirillum ferrooxidans菌浸出及电化学性能(英文)

采用纯种L.ferrooxidans菌研究矿浆浓度、pH及外加Fe3+离子对铁闪锌矿生物浸出的影响。结果表明,锌的浸出率随着矿浆浓度的降低而增加。在生物浸出过程中调节pH值到1.6对铁闪锌矿的溶解有促进作用。外加Fe3+离子加速了铁闪锌矿的生物浸出,但当外加Fe3+离子浓度超过2.5g/L时,促进作用变弱。这是因为高浓度的Fe3+离子会对细菌生长产生抑制作用且促进黄钾铁矾的生成。在L.ferrooxidans菌存在条件下,利用电化学测试方法进一步了解有、无外加Fe3+离子时铁闪锌矿的溶解过程。实验数据表明,外加Fe3+离子可以增加腐蚀电流密度,有利于锌的提取。交流阻抗谱表明,添加Fe3+离子后没有改变反应过程的控制步骤。     

元素硫对黄铜矿生物浸出行为及群落结构的影响(英文)

研究3种典型铁/硫代谢菌—Acidithiobacillus ferrooxidans,Leptospirillum ferriphilum及Acidithiobacillus thiooxidans混合浸出黄铜矿过程中铁/硫氧化活性、群落结构(PCR-RFLP)的变化,以及不同浓度的元素硫对其影响。结果发现,加入3.193g/L元素硫能促进细菌的表观硫氧化活性,改变浸矿体系的群落结构,并进一步影响钝化层的形成、金属离子的溶出,其浸出率(71%)较未添加硫的(67%)有一定程度的提高。而过量的元素硫会抑制铜的浸出(浸出率44%)。     

Preservation of moderately thermophilic culture by freeze drying and frozen preservation way and effect on subsequent bioleaching of chalcopyrite

Freeze drying and frozen preservation way was used to preserve a moderately thermophilic culture for bioleaching of chalcopyrite concentrate.After preservation of 15 months,the cell viability rate decreases to 22% with a cell density of 7×107 mL-1.When the growth time was extended from 8 days to 14 days,cell density would increase in a large scale to about 3×108 mL-1.In the bioleaching experiments,unpreserved and preserved cultures were compared for dissolving chalcopyrite concentrate.Before 44 days,the unpreserved culture can reach a high copper extraction of about 17.4 g/L.While the preserved culture shows a rather low copper extraction,which is only 9.7 g/L.When the bioleaching time was extended to 80 days,copper extraction by preserved culture increases remarkably,and the concentration of copper finally achieves up to 18.3 g/L.On the other hand,copper extraction by the unpreserved culture does not show remarkable increase from 44th to the 80th day,and finally the total copper extraction is 19.8 g/L.As a result,total copper extraction in 80 days by preserved culture approaches that by unpreserved culture and freeze drying and frozen preservation even after 15 months does not bring much decrease of bioleaching ability.     

Relatedness between catalytic effect of activated carbon and passivation phenomenon during chalcopyrite bioleaching by mixed thermophilic Archaea culture at 65 °C

The relatedness between catalytic effect of activated carbon and passivation phenomenon during chalcopyrite bioleaching by mixed thermophilic Archaea culture (Acidianus brierleyi, Metallosphaera sedula, Acidianus manzaensis and Sulfolobus metallicus) at 65 °C was studied. Leaching experiments showed that the addition of activated carbon could significantly promote the dissolution of chalcopyrite for both bioleaching and chemical leaching. The results of synchrotron-based X-ray diffraction, iron L-edge and sulfur K-edge X-ray absorption near edge structure spectroscopy indicated that activated carbon could change the transition path of electrons through galvanic interactions to form more readily dissolved secondary mineral chalcocite at a low redox potential (<400 mV) and then enhanced the copper dissolution. Jarosite accumulated immediately in the initial stage of bioleaching with activated carbon but copper dissolution was not hindered. However, much jarosite precipitated on the surface of chalcopyrite in the late stage of bioleaching, which might account for the decrease of copper dissolution rate. More elemental sulfur (S⁰) was also detected with additional activated carbon but the mixed thermophilic Archaea culture had a great sulfur oxidation activity, thus S⁰ was eliminated and seemed to have no significant influence on the dissolution of chalcopyrite.     

Bacterial leaching of chalcopyrite and bornite with native bioleaching microorganism

A native mesophilic iron-oxidizing bacterium, Acidithiobacillus ferrooxidans, has been isolated （30 ℃） from a typical, lead-zinc concentrate of Dachang Mine in the region of Liuzhou located in the southwest of China. Two typical copper sulfide minerals, chalcopyrite and bornite, were from Meizhou Copper Mine in the region of Guangdong Province, China. Variation of pH and cell growth on time and effects of some factors such as temperature, inoculation cell number, and pulp density on the bioleaching of chalcopyrite and bornite were investigated. The results obtained from the bioleaching experiments indicate that the efficiency of copper extraction depends on all of the mentioned variables, especially the pulp density has more effect than the other factors on the microorganism. In addition, the results show that the maximum copper recovery was achieved using a mesophilic culture. The copper dissolution reached 51.34% for the chalcopyrite while it was 72.35% for the bornite at pH 2.0, initial Fe（ Ⅱ ） concentration 9 g/L and pulp density 5%, after 30 d.     

Enhancing recovery of uranium column bioleaching by process optimization and kinetic modeling

This research aimed to enhance the column bioleaching recovery of uranium ore by Acidithiobacillus ferrooxidans. Seven factors were examined for their significance on bioleaching using a Plackett–Burman factorial design. Four significant variables ([Fe²⁺]_initial, pH, aeration rate and inoculation percent) were selected for the optimization studies. The effect of these variables on uranium bioleaching was studied using a central composite design (CCD). The optimal values of the variables for the maximum uranium bioleaching recovery (90.27±0.98)% were as follows: [Fe²⁺]_initial=2.89 g/L, aeration rate 420 mL/min, pH 1.45 and inoculation 6% (v/v). [Fe²⁺]_initial was found to be the most effective parameter. The maximum uranium recovery from the predicted models was 92.01%. This value was in agreement with the actual experimental value. The analysis of bioleaching residue of uranium ore under optimum conditions confirmed the formation of K-jarosite on the surface of minerals. By using optimal conditions, uranium bioleaching recovery is increased at column and jarosite precipitation is minimized. The kinetic model showed that uranium recovery has a direct relation with ferric ion concentration.     

绢云母对黄铜矿微生物浸出的影响

采用以Acidithiobacillus ferrooxidans为主的混合菌,研究绢云母对微生物浸出黄铜矿的影响。结果表明,铜的浸出率随着绢云母粒度的减小而增加,随着绢云母质量分数的增加而呈先升高后降低的趋势。在添加粒度为-33μm、质量分数为5.0%的绢云母时,铜的最高浸出率为54.88%,比不添加绢云母时的铜浸出率提高了约12%,表明绢云母能促进黄铜矿的微生物浸出。绢云母的加入可使浸出体系pH值降低,最终pH值低于1.22。在浸出过程中,新生成的物质主要是铵黄铁矾,它覆盖于黄铜矿的表面,对微生物浸出铜有一定的阻碍作用。     

Comparative study on bioleaching of two different types of low-grade copper tailings by mixed moderate thermophiles

The bioleaching of two different types of low-grade copper tailings, acid-leaching tailings (ALT) and copper flotation tailings (CFT) by mixed moderate thermophiles, and the variation of mineralogical and microbiological characteristics during their dissolution processes were comparatively investigated. Results showed that bioleaching behaviors of the two types of tailings were significantly different. In ALT bioleaching, lower redox potential, higher [Fe³⁺]/[Fe²⁺] ratio and higher cell density in solution were obtained. These resulted in higher total copper, primary copper sulfide and secondary copper sulfide extractions, compared with CFT bioleaching. X-ray diffraction analysis suggested that gypsum and some metal organic complexes were detected in CFT bioleaching, which could cause the sluggish oxidation of sulphide minerals. The shifts of microbial community in the leachates and leaching residues varied greatly between ALT and CFT bioleaching. The percentage of iron-oxidizing bacteria in ALT bioleaching was higher than that of CFT, but the sulfur-oxidizing bacteria percentage was the opposite. The archaeon F. thermophilum L1 was detected in ALT but not in CFT.     

Effect of Cu ions on bioleaching of marmatite

The effect of Cu^2＋ ions on bioleaching of marmatite was investigated through shake leaching experiments. The bacteria inoculated are a mixed culture ofAcidithiobacillusferrooxidans, Acidithiobacillus thiooxidans and Lepthospirillumferrooxidans. The results show that zinc is selectively leached, and the addition of appropriate content of Cu^2＋ ions has positive effect on the bioleaching of marmatite. SEM and EDX analyses of the leaching residue reveal that a product layer composed of iron sulfide, elemental sulfur and jarosite forms on the mineral surface. The biooxidation of elemental sulfur is catalyzed by the Cu^2＋ ions, which eliminate the barrier to bioleaching of marmatite and keep low pH value. With the addition of 0.5 g/L Cu^2＋ ions, the maximum zinc extraction rate reaches 73% after 23 d at the temperature of 30 ℃ with the pulp density of 10%, while that of iron is only about 10%.     

Effect of pH values on extracellular protein and polysaccharide secretions of Acidithiobacillus ferrooxidans during chalcopyrite bioleaching

The effect of pH values on the extracellular protein and polysaccharide secretions of Acidithiobacillus ferrooxidans was comparatively investigated in different phases of bacterial growth during chalcopyrite bioleaching. The results indicate that the extracellular protein is always more than the extracellular polysaccharide secreted by attached cells on the chalcopyrite, on the contrary, and is always less than the extracellular polysaccharide secreted by free cells in the solution at bacterial adaptive phase, logarithmic phase and stationary phase whenever pH value is at 1.0, 1.5, 2.0 or 2.5; free cells are mainly through the secretion of extracellular polysaccharide rather than the extracellular protein to fight against disadvantageous solution environment, such as high concentration of metal ions and unsuitable pH solution; both amounts of polysaccharide and protein secreted by attached cells are mainly positively related to the solution acidity rather than the total concentration of soluble metal ions. The experimental results imply that bacteria are mainly through secreting more extracellular polysaccharide to fight against disadvantageous environment and the extracellular protein perhaps plays an important role in oxidation–reduction reactions in the bioleaching system.     

Isolation and identification of moderately thermophilic acidophilic iron-oxidizing bacterium and its bioleaching characterization

A moderately thermophilic acidophilic iron-oxidizing bacterium ZW-1 was isolated from Dexing mine, Jiangxi Province, China. The morphological, biochemical and physiological characteristics, 16S rRNA sequence and bioleaching characterization of strain ZW-1 were studied. The optimum growth temperature is 48 ℃, and the optimum initial pH is 1.9. The strain can grow autotrophically by using ferrous iron or elemental sulfur as sole energy sources. The strain is also able to grow heterotrophically by using peptone and yeast extract powder, but not glucose. The cell density of strain ZW-1 can reach up to 1.02×108 /mL with addition of 0.4 g/L peptone. A phylogenetic tree was constructed by comparing with the published 16S rRNA sequences of the relative bacteria species. In the phylogenetic tree, strain ZW-1 is closely relative to Sulfobacilus acidophilus with more than 99% sequence similarity. The results of bioleaching experiments indicate that the strain could oxidize Fe2+ efficiently, and the maximum oxidizing rate is 0.295 g/(L·h). It could tolerate high concentration of Fe3+ and Cu2+ (35 g/L and 25 g/L, respectively). After 20 d, 44.6% of copper is extracted from chalcopyrite by using strain ZW-1 as inocula.     

Effects of microorganisms on surface properties of chalcopyrite and bioleaching

The alteration of surface properties of chalcopyrite after biological conditioning with Acidithiobacillusferrooxidans and Acidithiobacillus caldus was evaluated by Zeta-potential, adsorption studies, FT-IR spectra and contact angle measurement. The Zeta-potential studies show that the iso-electric point（IEP） of chalcopyrite after bacterial treatment moves towards the IEP of pure cells, indicating the adsorption of cells on chalcopyrite surface. The FT-IR spectra of chalcopyrite treated with bacterial cells show the presence of the cell functional groups signifying cells adsorption. Due to the formation of elemental sulfur and intermediate copper sulphides on chalcopyrite surface, the contact angle and surface hydrophohicity of chalcopyrite increase at the initial bioleaching stage. Chalcopyrite bioleaching by Acidithiobacillus ferrooxidans has higher copper extraction, which agrees with the fact that Acidithiobacillus ferrooxidans adsorbed on chalcopyrite surface is much more than Acidithiobacillus caldus. The results support the direct mechanism of sulfide oxidations in bioleaching chalcopyrite.     

STUDY ON BIOLEACHING OF PRIMARY CHALCOPYRITE ORE WITH THERMOACIDOPHLIC ARCHAE

A high temperature-tolerating thermoacidophilic archae (TA) was isolated from water samples collected from a hot sulfur-containing spring in the Yunnan Province, China, and was used in bioleaching experiments of a low-grade chalcopyrite ore. The TA grow at temperatures ranging from 40 to 80℃, with 65℃ being the optimum temperature, and at pH values of 1.5 to 4.0, with an optimum pH value of 2.0. The bioleaching experiments of the chalcopyrite ore were conducted in both laboratory batch bioreactors and leaching columns. The results obtained from the bioreactor experiments showed that the TA bioleaching rate of copper reached 97% for a 12-day leaching period, while the bioleaching rate was 32.43% for thiobacillus ferrooxidans (Tf) leaching for the same leaching time. In the case of column leaching, tests of a two-phase leaching (196 days), that is,a two-month (56 days) Tf leaching in the first phase, followed by a 140-day TA leaching in the second phase were performed. The average leaching rate of copper achieved for the 140-day TA leaching was 195mg/(L· d), while for the control experiments, it was as low as 78mg/(L· d) for the Tf leaching, indicating that the TA possesses a more powerful oxidizing ability to the chalcopyrite than Tf. Therefore, it is suggested that the two-phase leaching process be applied to for the heap leaching operations, whereas, the TA can be used in the second phase when the temperature inside the heap has increased, and the primary copper sulfide minerals have already been partially oxidized with Tf beforehand in the first phase.     

Mechanism of silver-influenced bacterial leaching of chalcopyrite, pyrite and a copper ore

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EPS-contact-leaching mechanism of chalcopyrite concentrates by A. ferrooxidans

The effect of extracelluar polymeric substances(EPS) on the bioleaching chalcopyrite concentrates in the presence of iron- and sulphur-oxidizing bacteria (A.ferrooxidans) was studied.The bacterial number,pH,redox potential,and the concentrations of Fe2+and Cu2+ ions were investigated.The leached residues were analyzed by the X-ray diffraction and FT-IR.The results indicate that the EPS makes the bacteria adhere to the chalcopyrite surface easily and it is helpful for bacteria in disadvantageous environment.At the same time,EPS film layer with Fe3+ deposits on the surface of chalcopyrite and becomes a barrier of oxygen transfer to chalcopyrite to passivate chalcopyrite,and creates the high redox potential space through concentrating Fe3+ ions to accelerate bioleaching pyrite in chalcopyrite concentrates.The results suggest that EPS formation promotes bioleaching pyrite and inhibits bioleaching chalcopyrite,especially under high potential condition.