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。     

黄铜矿生物浸出过程的硫形态转化研究进展

黄铜矿生物浸出过程中会生成元素硫及其他含硫中间产物和衍生物,它们对黄铜矿溶解产生钝化或促进作用。研究黄铜矿生物浸出过程的硫形态转化,可以有效了解阻碍或促进黄铜矿生物浸出的关键物质形态以及影响这些形态形成的机制,从而为进一步了解黄铜矿的钝化机制、揭示黄铜矿的溶解机制奠定理论基础。介绍了黄铜矿生物浸出过程产生的含硫中间产物和衍生物及其硫形态转化研究的进展。     

黄铜矿生物浸出过程中Fe(Ⅱ)和Fe(Ⅲ)的行为

采用Fe(Ⅱ)和Fe(Ⅲ)对黄铜矿进行生物浸出,主要研究浸出过程中体系的pH值、铁离子浓度、细菌吸附率及铜浸出率变化规律。结果表明:介质中Fe(Ⅲ)含量不同,生成黄钾铁矾的形态不同。在Fe(Ⅲ)生物浸出体系中,絮状的黄钾铁矾逐渐生成并全部覆盖在黄铜矿表面,阻碍黄铜矿的浸出过程。在Fe(Ⅱ)生物浸出体系中,生成皮壳状、结核状的黄钾铁矾分散于浸出液中,不覆盖在黄铜矿表面,对黄铜矿的浸出没有阻碍作用。     

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.     

可见光和Cd2+对黄铜矿生物浸出的催化作用(英文)

利用扫描电镜(SEM)、同步辐射X射线衍射(SR-XRD)和X射线光电子能谱(XPS)研究在酸性氧化亚铁硫杆菌存在下,可见光和镉离子(Cd²⁺)对黄铜矿生物浸出的影响。生物浸出28天后的结果表明,光照下铜的溶解提高4.96%;Cd²⁺单独存在对黄铜矿的浸出有轻微的抑制作用;可见光和50mg/LCd²⁺同时存在时,溶解铜的浓度提高14.70%。化学浸出结果表明,可见光能促进体系中铁元素的循环。SEM结果显示,Cd²⁺在可见光下促进酸性氧化亚铁杆菌在黄铜矿表面的附着。综合SR-XRD和XPS结果可知,可见光和Cd²⁺促进黄铜矿的浸出,但不会抑制钝化物的形成。提出可见光和Cd²⁺对黄铜矿生物浸出协同催化作用机制的模型。     

古菌生物浸出黄铜矿过程中的表观硫氧化活性表征

对4株纯的极端嗜热古菌及它们的混合菌在生物浸出黄铜矿过程中的硫氧化活性进行对比研究。结果表明,混合菌比纯菌拥有更高的硫氧化活性,它大幅度促进黄铜矿浸出率的提高。表征嗜热古菌硫氧化活性的参数值通常受很多因素的影响,以致在不同的硫氧化菌和不同的条件下生物浸出黄铜矿时,这些参数很难准确地反映出相应的硫氧化活性。因此,期待找到一种能有效表征浸矿菌硫氧化活性的方法。     

3种典型能量代谢菌浸出黄铜矿及其硫形态的转化

比较了3种典型嗜中温铁/硫代谢菌——Acidithiobacillus ferrooxidans、Leptospirillum ferriphilum及Acidithiobacillus thiooxidans单独及混合浸出黄铜矿过程中细菌硫氧化、铁氧化情况。同时利用XRD、硫的K边X射线吸收近边结构光谱(XANES)等分析手段研究3种细菌单独/混合浸出黄铜矿过程中矿物组成成分和矿物表面硫的形态变化。结果表明:在浸出初期电位低于400 mV(vs SCE)时,黄铜矿的浸出速率较快,此后电位迅速升高至540 mV,黄铜矿浸出速率明显变慢。混合菌浸出时体系的硫/铁氧化活性较单一菌高,根据XANES拟合分析发现,混合菌浸出时矿物表面元素硫及黄钾铁矾积累量明显减少,浸出初期辉铜矿产量明显高于单一细菌浸出的。     

聚乙二醇对氧化亚铁硫杆菌浸出黄铜矿的影响

为提高黄铜矿生物浸出率,研究聚乙二醇(PEG)对Acidithiobacillus ferrooxidans strain XZ11 Fe2+氧化活性和黄铜矿生物浸出过程的影响,并采用SEM和EDS对浸出后矿物表面形貌和相组成进行表征。结果表明:相对分子质量大于200的PEG对Acidithiobacillus ferrooxidans Fe2+氧化活性具有一定的促进作用,添加30 mg/L PEG 2000时,浸出20 d后,铜浸出量高达451.70 mg/L,较不添加FEG时提高了1.11倍;添加PEG时,黄铜矿表面的侵蚀面呈沟壑状,出现溶蚀坑,并生成Fe3+的羟基化多聚物Fe(Ⅲ)—O—OH。PEG的添加提高了浸出体系中细菌浓度和Fe3+浓度,加速了黄铜矿的溶解。     

利用光生空穴清除剂强化光催化黄铜矿生物浸出（英文）

通过嗜酸氧化亚铁硫杆菌(Acidithiobacillus ferrooxidans)研究光生空穴清除剂(抗坏血酸、草酸、腐质酸和柠檬酸)对光催化黄铜矿生物浸出的影响。设置4组生物浸出实验:(1)可见光+0 g/L光生空穴清除剂;(2)可见光+0.1 g/L不同光生空穴清除剂(抗坏血酸、草酸、腐植酸和柠檬酸);(3)黑暗+0.1 g/L不同光生空穴清除剂(抗坏血酸、草酸、腐植酸和柠檬酸);(4)黑暗+0 g/L光生空穴清除剂(对照组)。结果表明,光照条件下,抗坏血酸和草酸作为光生空穴清除剂时,能够显著促进黄铜矿生物浸出。可见光+0 g/L光生空穴清除剂组的铜离子溶出率比对照组高18.7%;可见光+0.1 g/L草酸组和可见光+0.1 g/L抗坏血酸组的黄铜矿溶出率分别比对照组高30.1%和32.5%。SEM,XRD和FT-IR分析表明,抗坏血酸和草酸作为光生空穴清除剂能够捕获光生空穴和抑制黄钾铁矾在黄铜矿表面形成,从而促进光催化黄铜矿的生物浸出。     

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。     

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。     

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.     

嗜酸热异养菌TC-2的分离鉴定及其对微生物浸矿的影响

从云南腾冲酸性热泉分离出一株嗜酸热异养菌TC-2。该菌呈长杆状,细胞大小为(2.0～5.0)μm×(0.3～0.5)μm,革兰氏染色反应为阴性,能形成芽孢。该菌生长温度范围为45～70℃,最适生长温度为55℃,适宜生长的pH值为1.5～4.0,最适宜生长的pH值为2.5,该菌能利用多种有机物生长。16SrDNA序列分析显示其与Alicyclobacillus sendaiensis的16SrDNA相似性大于99%。该菌自身没有浸矿作用,但对Acidianus manzaensis、Sulfolobus metallicus和Metallosphaera sedula等高温浸矿菌的浸矿有一定促进作用。     

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.     

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.