Comparative study on the passivation layers of copper sulphide minerals during bioleaching

The bioleaching of copper sulphide minerals was investigated by using A. ferrooxidans ATF6. The result shows the preferential order of the minerals bioleaching as djurleite>bornite>pyritic chalcopyrite>covellite>porphyry chalcopyrite. The residues were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). It is indicated that jarosite may not be responsible for hindered dissolution. The elemental sulfur layer on the surface of pyritic chalcopyrite residues is cracked. The compact surface layer of porphyry chalcopyrite may strongly hinder copper extraction. X-ray photoelectron spectroscopy (XPS) further confirms that the passivation layers of covellite, pyritic chalcopyrite, and porphyry chalcopyrite are copper-depleted sulphide Cu₄S₁₁, S8, and copper-rich iron-deficient polysulphide Cu₄Fe₂S₉, respectively. The ability of these passivation layers was found as Cu₄Fe₂S₉>Cu₄S₁₁>S₈>jarosite.     

不同类型黄铜矿的生物浸出研究

研究了两种不同类型(黄铁矿型,斑岩型)黄铜矿生物浸出的差异.实验结果表明:两类黄铜矿生物浸出差别很大,48 d后黄铁矿型黄铜矿浸出率为46.96%,斑岩型黄铜矿浸出率为14.5%.对Fe2+、矿物表面Cu2p谱图和矿床特征的分析发现:适量的Fe2+能促进黄铜矿的浸出,但最佳用量不一样;浸渣表面产物不同,斑岩型黄铜矿表面出现富铜层,阻碍了浸出继续进行;与原矿相比,铜结合能都降低,符合Hiroyoshi等提出黄铜矿浸出的两步溶解模型;两类黄铜矿生物浸出的差异是由成矿岩体、围岩、伴生矿物和元素、成矿温度和压力等因素综合决定的.     

Triton X-100对氧化亚铁硫杆菌氧化活性及浸出黄铜矿的影响

为提高黄铜矿的微生物浸出效果,研究了非离子表面活性剂Triton X-100对氧化亚铁硫杆菌(Acidithiobacillus ferrooxidans)氧化Fe2+和S0的活性以及浸出黄铜矿的影响,并采用XRD对浸出后的产物进行了表征.结果表明,Triton X-100对氧化亚铁硫杆菌氧化Fe2+有一定的抑制作用,而对氧化S0则显现出促进作用;Triton X-100可显著改善黄铜矿的微生物浸出效果,当其质量浓度为30 mg·L-1时,黄铜矿中铜的浸出率提高了52.15%.Triton X-100的加入提高了氧化亚铁硫杆菌对黄铜矿浸出过程中间产物硫的生物利用性和消解作用,从而提高了浸出体系中细菌浓度和Fe3+浓度,进而促进了黄铜矿的溶解.     

不同成因类型黄铜矿细菌浸出钝化

利用嗜酸氧化亚铁硫杆菌为浸矿菌种,采用SEM,XRD和XPS等手段研究2种不同成因类型黄铜矿(黄铁矿型和斑岩型)表面钝化机理.研究结果表明:2种类型黄铜矿表面形成的钝化层性质不同.黄铁矿型黄铜矿浸渣中产生S8和硫砷铜矿,其表面结构疏松;而斑岩型黄铜矿浸渣中出现Cu18.32Fe15.9S32和Cu2S,表面结构致密.黄铁矿型黄铜矿浸渣表面阻碍层为硫及其多聚物,斑岩型黄铜矿浸渣表面为富铜贫铁层.它们阻碍黄铜矿的继续浸出,且富铜贫铁层对黄铜矿的钝化能力强于硫层对黄铜矿的钝化能力.     

Dissolution characteristics of sericite in chalcopyrite bioleaching and its effect on copper extraction

The effects of sericite particle size, rotation speed, and leaching temperature on sericite dissolution and copper extraction in a chalcopyrite bioleaching system were examined. Finer particles, appropriate temperature and rotation speed for Acidithiobacillus ferrooxidans resulted in a higher Al3+ dissolution concentration. The Al3+ dissolution concentration reached its highest concentration of 38.66 mg/L after 48-d leaching when the sericite particle size, temperature, and rotation speed were -43 μm, 30℃, and 160 r/min, respectively. Meanwhile, the sericite particle size, rotation speed, and temperature can affect copper extraction. The copper extraction rate is higher when the sericite particle size is finer. An appropriately high temperature is favorable for copper leaching. The dissolution of sericite fitted the shrinking core model, 1-(2/3)α-(1-α)2/3=k₁t, which indicates that internal diffusion is the decision step controlling the overall reaction rate in the leaching process. Scanning electron microscopy analysis showed small precipitates covered on the surface of sericite after leaching, which increased the diffusion resistance of the leaching solution and dissolved ions.     

Bioleaching of chalcopyrite and bornite by moderately thermophilic bacteria：an emphasis on their interactions

Interactions between chalcopyrite and bornite during bioleaching by moderately thermophilic bacteria were investigated mainly by X-ray diffraction, scanning electron microscopy, and electrochemical measurements performed in conjunction with bioleaching experiments. The results showed that a synergistic effect existed between chalcopyrite and bornite during bioleaching by bothAcidithiobacillus caldus and Leptospirillum ferriphilum and that extremely high copper extraction could be achieved when chalcopyrite and bornite coexisted in a bioleaching system. Bornite dissolved preferentially because of its lower corrosion potential, and its dissolution was accelerated by the gal-vanic current during the initial stage of bioleaching. The galvanic current and optimum redox potential of 390?480 mV vs. Ag/AgCl pro-moted the reduction of chalcopyrite to chalcocite (Cu2S), thus accelerating its dissolution.     

Bioleaching of chalcopyrite and bornite by moderately thermophilic bacteria: an emphasis on their interactions

Interactions between chalcopyrite and bornite during bioleaching by moderately thermophilic bacteria were investigated mainly by X-ray diffraction, scanning electron microscopy, and electrochemical measurements performed in conjunction with bioleaching experiments. The results showed that a synergistic effect existed between chalcopyrite and bornite during bioleaching by both Acidithiobacillus caldus and Leptospirillum ferriphilum and that extremely high copper extraction could be achieved when chalcopyrite and bornite coexisted in a bioleaching system. Bornite dissolved preferentially because of its lower corrosion potential, and its dissolution was accelerated by the galvanic current during the initial stage of bioleaching. The galvanic current and optimum redox potential of 390-480 m V vs. Ag/Ag Cl promoted the reduction of chalcopyrite to chalcocite(Cu2S), thus accelerating its dissolution.     

Effect of pH values on the extracellular polysaccharide secreted by Acidithiobacillus ferrooxidans during chalcopyrite bioleaching

The pH value plays an important role in the bioleaching of sulphide minerals. The effect of pH values on the extracellular poly-saccharide secreted by Acidithiobacillus ferrooxidans was investigated in different phases of bacterial growth during chalcopyrite bioleach-ing. It is found that extracellular polysaccharide secretion from the cells attached to chalcopyrite is more efficiently than that of the free cells in the bioleaching solution. Three factors, pH values, the concentration of soluble metal ions, and the bacterial growth and metabolism, affect extracellular polysaccharide secretion in the free cells, and are related to the bacterial growth phase. Extracellular polysaccharide secretion from the attached cells is mainly dependent on the pH value of the bacterial culture.     

氧化亚铁硫杆菌对黄铜矿表面性质及其浸出的影响

通过测定吸附量、Zeta电位和接触角,并通过对原子力显微镜表面进行表征及摇瓶浸出试验考察不同能源(Fe2+、单质硫和黄铜矿)培养的氧化亚铁硫杆菌A.ferrooxidans对黄铜矿表面性质的影响及其与黄铜矿浸出的关系。研究结果表明:不同能源培养的A.ferrooxidans菌对黄铜矿表面性质的影响规律相似;A.ferrooxidans菌均能快速吸附在黄铜矿表面,而矿驯化的A.ferrooxidans菌在矿表面的附着能力更强;细菌的吸附使黄铜矿的等电点朝细菌的等电点方向偏移,且由于在黄铜矿表面生成了硫膜和不稳定铜硫化物使得黄铜矿表面接触角增大,疏水性增强;在浸矿初期,细菌与黄铜矿作用以直接作用机理为主。     

黄铁矿促进黄铜矿微生物浸出影响因素

采用摇瓶实验,以氧化亚铁硫杆菌(Acidithiobacillus ferrooxidans,At.f)浸出黄铁矿--黄铜矿,重点研究了基础培养基、矿物配比和粒度组成等因素的影响.黄铁矿能促进黄铜矿的微生物浸出,以采用无Fe 9K培养基效果较好,它对应铜浸出率是9K培养基的1.68倍;采用宽粒级矿物时铜浸出效果较好,且铜浸出率与黄铁矿和黄铜矿的质量比有关,当质量比为2∶2时铜浸出率最高可达45.58%;黄铁矿含量大小是影响铜浸出率高低的实质,当质量比小于等于5∶2时以At.f菌的氧化作用为主,当质量比为10∶2时以硫化矿间的原电池效应为主.浸渣的X射线衍射分析表明,采用无Fe 9K培养基时浸渣中生成的钝化物黄钾铁矾较少,故黄铁矿可以很好地替代9K培养基中的FeSO4,并能与黄铜矿形成原电池效应,从而促进铜的浸出.     

Bioleaching of copper oxide ore by Pseudomonas aeruginosa

Bioleaching is an environmentally friendly method for extraction of metal from ores. In this study, bioleaching of copper oxide ore by Pseudomonas aeruginosa was investigated. Pseudomonas aeruginosa is a heterotrophic bactermm that can produce various organic acids in an appropriate culture medium, and these acids can operate as leaching agents. The parameters, such as particle size, glucose percentage in the culture medium, bioleaching time, and solid/liquid ratio were optimized. Optimum bioleaching conditions were found as follows： particle size of 150-177 μm, glucose percentage of 6%, bioleaching time of 8 d, and solid/liquid ratio of 1：80. Under these conditions, 53% of copper was extracted.     

金属离子对细菌浸出复杂金属硫化矿的影响

研究了金属催化离子 Ag+ ,Hg2 + ,Bi3+对细菌浸出复杂金属硫化矿的影响。发现 Ag+能极大的提高金属浸出率 ,将 Cu的浸出率从 30 .2 7%提高到 99.99% ,钴的浸出率从 19.10 %提高到 31.79%。三种金属对 Cu浸出的影响大小顺序为 Ag+ >Hg2 + >Bi3+ ,对 Co浸出的影响大小顺序为 Ag+ >Bi3+ >Hg2 +。催化离子浸出效果的差异主要是由于催化离子毒性对细菌生长影响造成的。     

氧化亚铁硫杆菌在废弃线路板粉末上的吸附及对Cu的浸出

利用氧化亚铁硫杆菌(Thiobacillus ferrooxidans,T.f菌)浸出废弃线路板粉末中Cu,研究T.f菌在线路板粉末上的吸附,并通过对照试验比较浸出过程中吸附在线路板粉末上和游离于溶液中的T.f菌在浸出中的作用.结果显示,在6 h内,T.f菌在线路板粉末上的吸附达到平衡,吸附的T.f菌生物量占系统总生物量的72%￣82%,吸附T.f菌的作用在浸出中更为重要.     

Effect of synergistic adsorption of anion surfactants and heavy metal ions onto kaolinite surfaces

The experiments were performed in solution for the synergistic adsorption of dodecylbenzene sulfonate and copper ions onto kaolinite surfaces. The results showed that the former enhances the binding constant of copper ions onto kaolinite surfaces, but copper ions deduce the binding constant of dodecylbenzene sulfonate onto kaolinite surfaces. At the same time, they depress the proton release or absorb each other during their adsorption on kaolinite surfaces.     

Thin-layer heap bioleaching of copper flotation tailings containing high levels of fine grains and microbial community succession analysis

Thin-layer heap bioleaching of copper flotation tailings containing high levels of fine grains was carried out by mixed cultures on a small scale over a period of 210 d. Lump ores as a framework were loaded at the bottom of the ore heap. The overall copper leaching rates of tailings and lump ores were 57.10wt% and 65.52wt%, respectively. The dynamic shifts of microbial community structures about attached microorganisms were determined using the Illumina MiSeq sequencing platform based on 16S rRNA amplification strategy. The results indicated that chemolithotrophic genera Acidithiobacillus and Leptospirillum were always detected and dominated the microbial community in the initial and middle stages of the heap bioleaching process; both genera might be responsible for improving the copper extraction. However, Thermogymnomonas and Ferroplasma increased gradually in the final stage. Moreover, the effects of various physicochemical parameters and microbial community shifts on the leaching efficiency were further investigated and these associations provided some important clues for facilitating the effective application of bioleaching.     

含钴矿石摇瓶生物浸出比较试验的研究

对含钴矿石进行了工艺矿物学研究,明确了该含钴矿石的主要化学成分、粒度分布、矿物组成与嵌布特征.研究表明,硫化矿物主要为硫铜钴矿、黄铜矿、斑铜矿、辉铜矿、铜蓝、黄铁矿等.硫铜钴矿大多数以单体形式赋存,还有一部分为连生体.该含钴矿石含钴163%,铜105%,铁124%,硫1500%.用实验室驯化培养的具有良好抗钴性能的ZY101菌种对此含钴矿石进行摇瓶浸出实验研究,浸出结果表明:利用优良菌种浸出,钴浸出率达8571%.对比生物法与非生物的高铁溶液浸出,生物法钴浸出率提高6326%,耐钴ZY101浸矿菌浸钴效果显著.     

新型二烷基黄原酸酯捕收剂DIDTC浮选机理

合成了一种活性二烷基黄原酸酯捕收剂——S-十二烷基,O-异丙基-黄原酸酯(DIDTC)并将其用于浮选分离黄铜矿和黄铁矿.浮选实验结果表明DIDTC具有比丁基黄药更好的选择性,紫外可见光谱证明DIDTC对铜离子比铁离子具有更强的吸附性.采用红外光谱和吸附实验研究了DIDTC对黄铜矿表面的吸附机理,实验结果表明在碱性环境中DIDTC可能通过其分子中的S原子和O原子同时与黄铜矿表面的铜原子发生了键合,并在浓度较高时形成多层吸附.另外,还采用普遍微扰理论和基于GGA/PW91作为交换相关函的密度泛函计算对上述结果进行了捕收剂的构效关系分析.     

柠檬酸强化黄铜尾矿的生物浸矿

通过摇瓶试验研究混合硫杆菌浸出黄铜矿尾矿砂,并初步探讨不同矿浆质量浓度和柠檬酸质量浓度对浸提实验的影响。研究结果表明,添加柠檬酸在一定质量浓度范围内对黄铜矿尾矿砂的硫杆菌浸提有促进作用。在整个浸提实验中,浸矿效率最高达到44.8%,溶液中柠檬酸质量浓度和矿浆质量浓度都会直接影响细菌的氧化活性和浸矿效果。     

Enhancement of Au-Ag-Te contents in tellurium-bearing ore minerals via bioleaching

The purpose of this study was to enhance the content of valuable metals, such as Au, Ag, and Te, in tellurium-bearing minerals via bioleaching. The ore samples composed of invisible Au and Au paragenesis minerals (such as pyrite, chalcopyrite, sphalerite and galena) in combination with tellurium-bearing minerals (hessite, sylvanite and Tellurobismuthite) were studied. Indigenous microbes from mine drainage were isolated and identified as Acidithiobacillus ferrooxidans, which were used in bioleaching after adaption to copper. The effect of the microbial adaption on the bioleaching performance was then compared with the results produced by the non-adaptive process. The microbial adaption enhanced the Au-Ag-Te contents in biological leaching of tellurium-bearing ore minerals. This suggests that bioleaching with adapted microbes can be used both as a pretreatment and in the main recovery processes of valuable metals.     

Cu（II）、Ni（II）离子在蛇纹石表面的吸附及对其浮选的影响

通过吸附量测试、纯矿物浮选和红外光谱分析,研究Cu2+和Ni2+离子在蛇纹石表面的吸附过程及对蛇纹石浮选的活化机理。 Cu2+和Ni2+离子在蛇纹石表面的吸附符合二级动力学模型,等温吸附过程符合Langmuir等温吸附模型,吸附能够自发进行,为物理吸附和化学吸附的共同作用,Cu2+和Ni2+离子在蛇纹石表面的吸附量随pН值升高而增大。 Cu2+和Ni2+离子在弱碱性条件下对蛇纹石具有活化作用,活化机理为铜镍的氢氧化物沉淀和羟基络合物作用于蛇纹石表面,形成活性位点,黄药在活性位点上吸附生成黄原酸铜或黄原酸镍,从而使蛇纹石表面疏水性增大,浮选受到活化。