Study on bioleaching of primary chalcopyrite ore with thermoacidophilic 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 l.5 to 4.0, with an optimum pH value of 2.0. The bioleaching experiments of the chalcvpyrite 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.     

Feasibility study on heap bioleaching of chalcopyrite

Bioleaching of chalcopyrite often encountered the formation of passivation layer, which inhibited the leaching process and resulted in a low leaching rate. This inhibitory effect can be eliminated by thermophilic biole- aching. The industrial test of BioCOP technology based on thermophiles was successfully completed, which confirmed the feasibility of chalcopyrite bioleaching. However, industrial leaching rate of chalcopyrite heap bioleaching is lower. This paper described the development status and industrial test of chalcopyrite heap bioleaching technology. The reasons for the lower efficiency of chalcopyrite heap bioleaching were analyzed. The strategies for successful chalcopyrite heap bioleaching were proposed.     

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。     

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

1　ＩＮＴＲＯＤＵＣＴＩＯＮＣｈａｌｃｏｐｙｒｉｔｅｉｓｏｎｅｏｆｔｈｅｍｏｓｔｉｍｐｏｒｔａｎｔｃｏｐｐｅｒｍｉｎｅｒａｌｓ.Ｂｉｏｈｙｄｒｏｍｅｔａｌｌｕｒｇｙｈａｓｇｒａｄｕａｌｌｙｂｅｃｏｍｅａｎｉｍｐｏｒｔａｎｔｔｅｃｈｎｏｌｏｇｙｉｎｔｒｅａｔｉｎｇｌｏｗ ｇｒａｄｅｃｏｐｐｅｒｏｒｅｓ,ｅｓｐｅｃｉａｌｌｙｗｈｅｎｔｈｅｍｉｎｉｎｇｉｎｄｕｓｔｒｙｈａｓｔｏｂｅｆａｃｅｄｕｐｔｏｉｎｃｒｅａｓｉｎｇｌｙｓｅｒｉｏｕｓｐｒｏｂｌｅｍｓｓｕｃｈａｓｔｈｅｐｒｏｇｒｅｓｓｉｎｇｅｘｈａｕｓｔ…     

Simulated small-scale pilot heap leaching of low-grade copper sulfide ore with selective extraction of copper

The bioleaching of low-grade copper sulfide ore and the selective extraction of copper were investigated. Lix984 dissolved in kerosene was used as extractant. The results show that it is possible to selectively leach copper from the ores by heap leaching. The copper concentration of leaching liquor after 250 d is 2.17 g/L, and the copper concentration is 0.27 g/L after solvent extraction. The leach liquor was subjected to solvent extraction, scrubbing and selective stripping for the enrichment of copper and the removal of impurities. The pregnant copper sulfate solution produced from the stripping cycle is suitable for copper electro-winning.     

生物因素对次生硫化铜矿堆浸过程动力学的影响

假定生物浸出过程细菌的作用是间接作用,以实验室柱浸模拟次生硫化铜矿生物堆浸,基于细菌生长Monod方程及收缩核模型建立细菌生长动力学因子影响硫化矿浸出速率的动力学模型,研究铜浸出速率、溶液总铁、溶液中细菌浓度与时间的关系、细菌产出率和细菌饱和系数对浸出速率影响的动力学规律。动力学研究表明,在浸出早期,氧化浸出速率、溶液中总铁浓度以及溶液中的细菌数量增长较快,而在浸出后期则增长较慢。计算与实际结果表明,细菌最大生长比速率、细菌产出率、细菌饱和常数及溶液中Fe离子的浓度均对硫化矿的氧化浸出速率有明显影响,尤其在浸出早期影响较大。应用动力学模型仿真结果与实际基本符合,可分析生物因素对浸出的影响趋势。     

Bioleaching of chalcopyrite by pure and mixed culture

The bioleaching of chalcopyrite in shake flasks was investigated by using pure Acidithiobacillusferrooxidans and mixed culture isolated from the acid mine drainage in Yushui and Dabaoshan Copper Mine in China, marked as YS and DB, respectively. The mixed culture consisted mainly of Acidithiobacillus fOrrooxidans, Acidithiobacillus thiooxidans, and Leptospirillum spp. （Leptospirillum ferriphilum and Leptospirillum ferrooxians）. The results show that the mixed culture is more efficient than the pure Acidithiobacillus ferrooxidans because of the presence of the sulfur-oxidizing cultures that positively increase the dissolution rate and the recovery of copper from chalcopyrite. The pH value decreases with the decrease of chalcopyrite leaching rate, because of the formation ofjarosite as a passivation layer on the mineral surface during bioleaching. In the bioleaching using the mixed culture, low pH is got from the sulfur oxidizing inhibiting, the formation ofjarosite. The copper extraction reaches 46.27% in mixed culture and 30.37% in pure Acidithiobacillusferrooxidans after leaching for 75 d.     

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.     

生物浸出过程中黄铜矿钝化的控制方法(英文)

在细菌浸出黄铜矿的过程中,黄铜矿表面钝化是普遍现象,成为生物浸铜技术的瓶颈问题。对比研究了普通浸出与强化浸出(加入玻璃圆珠)对铜浸出的影响。结果表明,玻璃圆珠的加入改善了浸出条件,削弱了黄铜矿的钝化效应,使黄铜矿的Cu浸出率从50%提升至 89.8%。扫描电镜(SEM)和X射线衍射(XRD)分析发现,添加玻璃圆珠的黄铜矿表面没有黄钾铁矾沉淀,钝化作用不明显;而不加玻璃圆珠的黄铜矿表面附着厚厚的结构致密的黄钾铁矾,钝化严重,从而阻碍了黄铜矿的溶解和浸出。     

混合高温菌浸出黄铜矿及浸出过程中微生物群落的演替

研究3株极端嗜热古菌(金属硫叶菌,Sulfolobus metallicus JCM 9184;瑟杜生金属球菌,Metallosphaera sedula JCM 9185和万座酸菌,Acidianus manzaensis YN25)在不同起始pH值和不同温度条件下对黄铜矿的混合浸出,并对浸矿过程中混合菌群落的动态演替进行分析.结果表明:在起始pH 1.5时的铜浸出率明显高于在起始pH 2.5时的铜浸出率,而65 ℃条件下的铜浸出率高于75 ℃时的铜浸出率.利用限制性长度多态性(RFLP)分析65 ℃、起始pH 1.5条件下的微生物群落演替,结果显示:在黄铜矿的浸出前期Sulfolobus metallicus是占据优势的菌种,而到后期Acidianus manzaensis的比例则会上升,并最后取代Sulfolobus metallicus成为优势种.     

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.     

Sustainable copper extraction from mixed chalcopyrite–chalcocite using biomass

This paper elaborated on the sustainability of the copper extraction process. In fact, an alternative copper extraction route from mixed sulphide ores, chalcopyrite and chalcocite using mesophilic biomass consortium at 33.3 °C and ferric leaching process were attempted. Bioleaching experiments were settled with a fraction size of −75+53 µm. Bacteria were used as the catalyst. A copper yield of 65.50% was obtained. On the other hand, in ferric leaching process, with a fraction size of −53+38 µm, when the temperature was increased to 70 °C, the copper leaching rate increased to 78.52%. Thus, comparatively, the mesophilic bioleaching process showed a more obvious advantage in copper extraction than leaching process with a high temperature. However, it has been resolved from the characterization performed using SEM−EDS, FTIR and XRD observations coupled with different thermodynamic approaches that, the indirect mechanism is the main leaching mechanism, with three transitory mechanisms (polysulphide, thiosulphate and elemental sulphur mechanisms) for the mixed chalcopyrite−chalcocite ore. Meanwhile, the speciation turns into Cu₂S−CuS−Cu₅FeS₄−Cu₂S before turning into CuSO₄. While ferrous oxidation and the formation of ferric sulphate occur, and there is a formation of strong acid as bacteria digest sulphide minerals into copper sulphate at low temperature, which is why this copper production scenario requires a redox potential more than 550 mV at room temperature for high copper leaching rate.     

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.     

Effect of initial pH on chalcopyrite oxidation dissolution in the presence of extreme thermophile Acidianus manzaensis

The influence of initial pH on the chalcopyrite oxidation dissolution at 65 °C was investigated by bioleaching and cyclic voltammetry experiments, and the oxidation products were investigated by XRD and Raman spectroscopy. Bioleaching results show that chalcopyrite dissolution rate increases with the decrease of the initial pH in chemical leaching, while the influence of initial pH on bioleaching is on the contrary. The presence of Acidianus manzaensis does not promote chalcopyrite dissolution under initial pH 1.0, which mainly results from serious inhibition of high acidity to the growth of Acidianus manzaensis. Electrochemical experiments results show that anodic oxidation currents of electrolyte with or without Acidianus manzaensis both increase with the increase of initial pH, and covellite and sulfur are detected on the electrode surface. The results confirm that chalcopyrite dissolution in chemical leaching is under the combined action of oxidation and non-oxidation of proton, with conversion of chalcopyrite to covellite and elemental sulfur.     

Responses of bacterial community to potential heap construction methods of fine-grained copper tailings in column bioleaching system

The column bioleaching of copper flotation tailings was comparatively investigated using layered heap construction method (LM), agglomerate heap construction method (AM), and pellets-sintering heap construction method (PM). The bacterial communities of free, attached, weakly-attached, and strongly-attached microbes in the later bioleaching stage were investigated. In AM group, the addition of lump sulphide ore resulted in the low leachate pH, high ferric iron concentration, and rapid microbial adsorption, which obtained the maximum copper extraction (60.1%) compared with LM (54.6%) and PM (43.9%) groups. The relative abundance of dominant genera and microbial communities of different microbiota underwent changes in three heap construction methods. The alpha-diversity indexes of attached, weakly-attached, and strongly-attached microbes were different, while no significant change was observed in free bacteria. The variation of whole bacterial community was significantly associated with solution pH, total iron, and ferric iron concentrations. Pearson correlation analysis and partial least square path model both indicated that attached bacteria made larger contribution to the copper extraction of tailings.     

Bioleaching of anilite by Acidithiobacillus ferrooxidans

In order to characterize the efficiency of copper bioleaching from anilite using pure cultures of Acidithiobacillus ferrooxidans in the absence and presence of ferrous sulphate,the experiments were carried out in shake flasks with or without 4 g/L ferrous sulphate(FeSO_4·7H_2O)at pH 2.0,150 r/min and 35℃.The tests show that Acidithiobacillus ferrooxidans is unable to attack anilite in iron-free 9K medium.Anilite is rapidly oxidized by bacterial leaching when ferrous sulphate is added.Chemical oxidation o...     

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.     

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.     

Copper hydrometallurgy-current status,preliminary economics,future direction and positioning versus smelting

The heap leaching of oxide copper ores with copper cathode recovery by solvent extraction and electrowinning is now well established as a low-cost method of copper recovery. This technology has recently been applied successfully to mixed oxide and chalcocite ores, notably in Chile at Cerro Colorado, Quebrada Blanca and Zaldivar.Currently, there are significant development efforts underway to try to extend heap leaching to chalcopyrite ores.The success of heap leaching/SX/EW has also led to a revival in the development of hydrometallurgical processes to recover copper from chalcopyrite and other copper concentrates. The current status of copper hydrometallurgy is reviewed and the most commercially attractive potential applications are explored. The advantages and disadvantages of the hydrometallurgical treatment of chalcopyrite concentrates and its preliminary economics are compared with those for the current best practices in copper smelting and refining.     

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.