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%)。     

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.     

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。     

Comparison on the leaching kinetics of chalcocite and pyrite with or without bacteria

The acid leaching, ferric leaching, and bioleaching of chalcocite and pyrite minerals were conducted in two sets of 3L stirred reactors. The dissolution rates of copper and iron were correlated with leaching conditions. In the acid leaching process, the dissolution rate of chalcocite was around 40wt.% while that of pyrite was less than 4%. In the ferric leaching process with high ferric concentration, only 10 wt.% of iron in pyrite was leached out at the same retention time though the copper recovery over 60 wt.% in chalcocite. For the bioleaching process, the chalcocite leaching rate was highly increased, nearly 90 wt.% of copper was leached out, and the iron dissolution of pyrite exceeded 70 wt.%. For the two minerals, the bioleaching shows the highest leaching rate compared with the acid leaching or ferric leaching. In uncontrolled bioleaching process, pyrite could be dissolved effectively. The experimental data were fitted to the shrinking core and particle model. The results show that in all the leaching tests, the chalcocite leaching was mainly controlled by diffusion, while for the pyrite leaching, chemical reaction is the main rate-determining step.     

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.     

云南某含银铜矿伴生银矿物强化回收实验研究

云南某含银铜矿石银品位为21.77 g/t,主要赋存于黄铜矿、游离银和磁黄铁矿中,在选别过程中铜硫分离时兼顾银的回收具有一定的难度。采用抑硫浮铜流程,研究筛选出石灰及Z200作为合适的调整剂和高效捕收剂,在抑制黄铁矿、磁黄铁矿的同时强化银的回收。最终闭路试验获得了品位23.92%、回收率97.10%的铜精矿,且含银136.38 g/t,银的回收率达到77.05%,实现了铜硫分离的同时强化银的回收。     

云南某铜尾矿中铜和金的选矿回收试验

云南某铜尾矿主要金属矿物有黄铜矿、黄铁矿、磁黄铁矿等,黄铜矿以原生硫化铜为主,金以裸露金和黄铜矿包裹金为主。为综合回收其中有价铜、金,进行了选矿试验。试样在磨矿细度为-200目占85%的情况下采用两次粗选、第二次粗选后扫选、两次精选、第二次精选后扫选、混精矿再磨至-325目占85%、粗选后扫选精矿再磨至-325目占85%、中矿循序返回流程处理。最终获得铜品位15.51%、回收率68.34%、产率1.41%的铜金精矿,其中的金品位19.93 g/t、回收率54.04%,银品位231.72 g/t、回收率41.89%。     

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.     

The biological leaching of an auriferous pyrite ore

The oxidation of an auriferous pyrite ore sample was evaluated in biological leaching experiments for subsequent gold recovery via cyanidation. In batch cultures, organisms derived from the mine site oxidized pyrite and ferrous iron at pH values as low as pH 0.6. The recovery of gold was variable in shake flask experiments. In stirred tank bioreactor leaching, gold recovery was proportional to the extent of iron dissolution by bioleaching. The leaching of arsenic from the sample was also directly proportional to iron dissolution.     

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.     

Impact of silver sulphides on gold cyanidation with polymetal sulphides

Gold leaching was influenced in association with silver and polymetal sulphide minerals. A packed bed was adopted to single out the galvanic and passivation effects with four sets of minerals: pyrite–silica, chalcopyrite–silica, sphalerite–silica and stibnite–silica. Pyrargyrite enhanced Au recovery to 77.3% and 51.2% under galvanic and passivation effects from pyrite (vs 74.6% and 15.8%). Pyrargyrite in association with sphalerite also enhanced Au recovery to 6.6% and 51.9% (vs 1.6% and 15.6%) under galvanic and passivation effects from sphalerite. Pyrargyrite associated with chalcopyrite retarded gold recovery to 38.0% and 12.1% (vs 57% and 14.1%) under galvanic and passivation effects. Accumulative silver minerals enhanced Au recovery to 90.6% and 81.1% (vs 74.6% and 15.8%) under galvanic and passivation impacts from pyrite. Silver minerals with sphalerite under galvanic and passivation effects enhanced Au recovery to 71.1% and 80.5% (vs 1.6% and 15.6%). Silver minerals associated with chalcopyrite retarded Au recovery to 10.2% and 4.5% under galvanic and passivation impacts (vs 57% and 14.1%). Stibnite retarded Au dissolution with pyrargyrite and accumulative silver minerals. Pyrargyrite and accumulative silver enhanced gold dissolution for free gold and gold associated with pyrite and sphalerite. Gold dissolution was retarded for gold and silver minerals associated with chalcopyrite and stibnite.     

纳米比亚某含银硫化铜矿选矿试验研究

纳米比亚Karas矿区罗雷铜矿区的原生矿铜主要以黄铜矿、斑铜矿等硫化铜矿物形式存在,银分别以银黝铜矿为主的独立银矿物和以黄铜矿为载体的载体银矿物形式存在,铜、银品位分别为0.60%和3.03 g/t。浮选试验结果表明,矿样适当细磨至-0.074 mm占80%,以石灰做调整剂,Z200做捕收剂,在矿浆p H值为8的条件下,可获得铜品位22.3%,银品位61.8 g/t的含银铜精矿,铜、银回收率分别为90.6%和51.8%。     

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.     

Acid equilibrium during bioleaching of alkaline low-grade sulfide copper ore

This article reports the study on acid equilibrium during bioleaching of alkaline low-grade copper sulfide ore. Adding auxiliary agents 1# （sulfur） and 2# （pyrite） makes bacterial leaching of copper and acid production carried out simultaneously because the auxiliary agents can be oxidized by bacteria and the oxidation products involve acid. The acid required for dissolving alkaline gangue during bacterial leaching is produced, and acid equilibrium is reached during the ore bio-leaching. The recovery of copper reaches more than 95%.     

紫金山铜金矿中金铜银的赋存状态研究

采用矿物自动分析仪(MLA)、扫描电镜(SEM)、X射线衍射(XRD)研究了紫金山金铜矿入选矿石中有价元素铜、金、银的赋存状态以及分选过程中的金属走向。结果表明,铜矿物主要有蓝辉铜矿、铜蓝、硫砷铜矿,金银以游离矿物和硫化物包裹体为主。铜矿物常见沿明矾石溶蚀孔洞或碎裂缝隙充填,与黄铁矿密切连生,从原矿中分选铜矿物,理论品位为Cu 69.70%,理论回收率93.55%。中粒金嵌布于铜矿物和黄铁矿矿物粒间或裂隙,可随着铜和硫的回收进入铜、硫精矿,金的理论回收率分别为57.19%和27.27%;微细金粒包裹于明矾石和石英中,随脉石损失于尾矿中。银以显微银为主,多见呈微细粒包裹于硫化矿物中,铜精矿和硫精矿中银的理论回收率分别为56.96%和26.71%。     

嗜酸氧化亚铁硫杆菌浸出黄铜矿中氧化还原电位、黄铁钾钒和胞外聚合物的关系和影响(英文)

在合成的胞外聚合物(EPS)溶液中,研究不同起始总铁量、不同Fe(III)与Fe(II)摩尔比条件下嗜酸氧化亚铁硫杆菌浸出黄铜矿过程中pH、电位、可溶性铁离子和Cu2+浓度随浸出时间的变化。结果表明:当溶液电位低于650mV(vsSHE)时,因细菌产生的EPS可通过絮凝黄铁钾钒延缓污染,即使铁离子浓度达到20g/L,黄铁钾钒对细菌浸出黄铜矿的阻碍作用也不是致命的,但随着铁离子浓度的增加而增加;细菌氧化的铁离子容易吸附在黄铜矿表面的EPS表层,有黄铁钾钒的EPS层是弱离子扩散壁垒,细菌通过把EPS空间内外的Fe2+氧化成Fe3+,进一步创造高于650mV的电位,导致EPS层离子扩散性能的快速恶化,严重地和不可逆地阻碍生物浸出黄铜矿。     

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.     

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.     

微生物浸出Pb-Zn-Sn黄铜矿及其生物群落的演替分析

研究了Pb-Zn-Sn黄铜矿精矿在混合中度嗜热微生物槽浸过程中的细菌群落结构变化,并监测浸出体系中金属离子浓度、溶液电位、溶液pH值变化,通过聚合酶链式反应-限制性片段长度多态性（PCR-RFLP）技术分析微生物群落的结构变化。结果表明,最终铜浸出率高达85.6%,在浸出前期,Acidithiobacillus caldus为优势群落,从第18天开始到浸出结束,Sulfobacillus thermosulfidooxidans为优势群落,但Leptospirillum ferriphilum丰度变化较小。试验结果表明,适当较高的溶液电位和合适的铁离子浓度对黄铜矿精矿的生物浸出作用很关键。     

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.