Bioleaching of two different types of chalcopyrite by Acidithiobacillus ferrooxidans

Two different types of chalcopyrite (pyritic chalcopyrite and porphyry chalcopyrite) were bioleached with Acidithiobacillus ferrooxidans ATF6. The bioleaching of the pyritic chalcopyrite and porphyry chalcopyrite is quite different. The copper extraction reaches 46.96% for the pyritic chalcopyrite after 48-d leaching, but it is only 14.50% for the porphyry chalcopyrite. Proper amounts of initial ferrous ions can improve the efficiency of copper extraction for the two different types of chalcopyrite. The optimum dosage of ferrous ions for the pyritic chalcopyrite and porphyry chalcopyrite is different. The adsorption of ATF6 on the pyritic chalcopyrite and porphyry chalcopyrite was also studied in this paper. It is found that ATF6 is selectively adsorbed by the two different types of chalcopyrite; the higher adsorption onto the pyritic chalcopyrite than the porphyry chalcopyrite leads to the higher copper dissolution rate of the pyritic chalcopyrite. In addition, the zeta-potential of chalcopyrite before and after bioleaching further confirms that ATF6 is more easily adsorbed onto the pyritic chalcopyrite.     

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.     

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.     

Acidithiobacillus ferrooxidans对黄铜矿和镍黄铁矿的浸出

以黄铜矿和镍黄铁矿为研究对象,初步探讨了Acidithiobacillus ferrooxidans对黄铜矿和镍黄铁矿的浸出.结果表明:有细菌参与下,黄铜矿的浸出率是无菌体系浸出率的2.41倍;镍黄铁矿的浸出率是无菌体系浸出率的1.91倍,细菌在矿物的浸出过程中起到了很好的促进作用.浸出过程中会有黄色的黄钾铁矾(K[Fe3(SO4)2(OH)6])沉淀产生,黄钾铁矾附着在矿体表面,产生"钝化现象",严重阻碍矿物的氧化.     

Mineral sulphide-lime reactions and effect of CaO/C mole ratio during carbothermic reduction of complex mineral sulphides

Mineral sulphide (MS)-lime (CaO) ion exchange reactions (MS + CaO = MO + CaS) and the effect of CaO/C mole ratio during carbothermic reduction (MS + CaO + C = M + CaS + CO(g)) were investigated for complex froth flotation mineral sulphide concentrates. Phases in the partially and fully reacted samples were characterised by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The primary phases during mineral sulphide-lime ion exchange reactions are Fe₃O₄, CaSO₄ Cu₂S, and CaS. A complex liquid phase of Ca₂CuFeO₃S forms during mineral sulphide-lime exchange reactions above 1173 K. The formation mechanisms of Ca₂CuFeO₃S liquid phase are determined by characterising the partially reacted samples. The reduction rate and extent of mineral sulphides in the presence of CaO and C increase with the increase in CaO/C ratio. The metallic phases are surrounded by the CaS rich phase at CaO/C > 1, but the metallic phases and CaS are found as separate phases at CaO/C < 1. Experimental results show that the stoichiometric ratio of carbon should be slightly higher than that of CaO. The reactions between CaO and gangue minerals (SiO₂ and Al₂O₃) are only observed at CaO/C > 1 and the reacted samples are excessively sintered.     

Kinetics of chemical leaching of chalcopyrite from low grade copper ore: behavior of different size fractions

The kinetics of the chemical leaching of copper from low grade ore in ferric sulfate media was investigated using the constrained least square optimization technique. The experiments were carried out for different particle sizes in both the reactor and column at constant oxidation-reduction potential (E_h), pH values, and temperature. The main copper mineral was chalcopyrite. About 40% of Cu recovery is obtained after 7 d of reactor leaching at 85℃ using -0.5 mm size fraction, while the same recovery is obtained at 75℃ after 24 d. Also, about 23% of Cu recovery is obtained after 60 d of column leaching for +4–-8 mm size fraction whereas the Cu recovery is as low as about 15% for +8–-12.7 and +12.7–-25 mm size fractions. A 4-stage model for chalcopyrite dissolution was used to explain the observed dissolution behaviors. The results show that thick over-layers of sulphur components cause the parabolic behavior of chalcopyrite dissolution and the precipitation of Fe3+ plays the main role in chalcopyrite passivation. In the case of coarse particles, transformation from one stage to another takes a longer time, thus only two stages including the initial reaction on fresh surfaces and S0 deposition are observed.     

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.     

通气对硫化铜矿生物浸出过程中自由细菌和吸附细菌群落动态的影响研究

生物浸出回收低品位硫化铜矿中的铜金属具有操作简单、低能耗、节约经济等优点,成为了近年来的研究热点。然而低品位硫化铜矿生物浸出效率低是其面临的主要问题之一。本文为了促进生物浸出效率,研究了强制通气条件下的低品位硫化铜矿生物浸出过程中的铜浸出率、细菌群落动态演替等特征。结果表明,适当的通气可提高细菌浓度和铜浸出率。在通气时间为4 h·d?1时,浸矿14 d后的细菌浓度和铜离子浓度最高,分别为7.61×107 个·mL?1和704.9 mg·L?1。实验可得,吸附细菌在浸矿过程的前7 d起着重要作用,而自由细菌则是在第8 d到第14 d占主导地位。这一现象主要是由于浸出过程Fe3+水解形成钝化层所致,抑制了吸附细菌与矿石的接触。同时,通过16S rDNA分析可知,Acidithiobacillus ferrooxidans和Acidithiobacillus thiooxidans对低品位硫化铜矿生物浸出过程具有重要影响。     

Structure and corrosion resistance of Al–Cu–Fe alloys

The microstructure and electrochemical properties of Al–Cu–Fe alloys with the atomic compositions of Al_(65)Cu_(20)Fe_(15),Al_(78)Cu_7Fe_(15)and Al_(80)Cu_5Fe_(14)Si_1have been studied.The alloys were produced by induction melting of pure elements with copper mold casting.The microstructure of the alloys was analyzed by X-ray diffraction and high-resolution transmission electron microscopy.The formation of quasicrystalline phases in the Al–Cu–Fe alloys was confirmed.The presence of intermetallic phases was observed in the alloys after crystallization in a form of ingots and plates.The electrochemical measurements were conducted in 3.5%NaCl solution.The electronic structure of the alloys was determined by X-ray photoelectron spectroscopy.The post corrosion surface of the samples was checked using a scanning electron microscope equipped with the energydispersive X-ray detector.It was observed that the Al_(65)Cu_(20)Fe_(15)alloy had the highest corrosion resistance.The improved corrosion resistance parameters were noted for the plate samples rather than those in the as-cast state.And the hardness of the Al_(65)Cu_(20)Fe_(15)alloy was significantly higher than the other alloy samples.     

Mechanochemical leaching of chalcopyrite concentrate by sulfuric acid

This study aimed to introduce a new cost-effective methodology for increasing the leaching efficiency of chalcopyrite concentrates at ambient temperature and pressure. Mechanical activation was employed during the leaching (mechanochemical leaching) of chalcopyrite concentrates in a sulfuric acid medium at room temperature and atmospheric pressure. High energy ball milling process was used during the leaching to provide the mechanochemical leaching condition, and atomic absorption spectroscopy and cyclic voltammetry were used to determine the leaching behavior of chalcopyrite. Moreover, X-ray diffraction and scanning electron microscopy were used to characterize the chalcopyrite powder before and after leaching. The results demonstrated that mechanochemical leaching was effective; the extraction of copper increased significantly and continuously. Although the leaching efficiency of chalcopyrite was very low at ambient temperature, the percentages of copper dissolved in the presence of hydrogen peroxide (H₂O₂) and ferric sulfate (Fe₂(SO₄)₃) after 20 h of mechanochemical leaching reached 28% and 33%, respectively. Given the efficiency of the developed method and the facts that it does not require the use of an autoclave and can be conducted at room temperature and atmospheric pressure, it represents an economical and easy-to-use method for the leaching industry.     

Occurrence mechanism of silicate and aluminosilicate minerals in Sarcheshmeh copper flotation concentrate

The Sarcheshmeh copper flotation circuit is producing 5×104 t copper concentrate per month with an averaging grade of 28% Cu in rougher, cleaner and recleaner stages. In recent years, with the increase in the open pit depth, the content of aluminosilicate minerals increased in plant feed and subsequently in flotation concentrate. It can motivate some problems, such as unwanted consumption of reagents, decreasing of the copper concentrate grade, increasing of Al₂O₃ and SiO₂ in the copper concentrate, and needing a higher temperature in the smelting process. The evaluation of the composite samples related to the most critical working period of the plant shows that quartz, illite, biotite, chlorite, orthoclase, albeit, muscovite, and kaolinite are the major Al₂O₃ and SiO₂ beating minerals that accompany chalcopyrite, chalcocite, and covellite minerals in the plant feed. The severe alteration to clay minerals was a general rule in all thin sections that were prepared from the plant feed. Sieve analysis of the flotation concentrate shows that Al₂O₃ and SiO₂ bearing minerals in the flotation concentrate can be decreased by promoting the size reduction from 53 to 38 μm. Interlocking of the Al₂O₃ and SiO₂ bearing minerals with chalcopyrite and chalcocite is the occurrence mechanism of silicate and aluminosilicate minerals in the flotation concentrate. The dispersed form of interlocking is predominant.     

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.     

外镀铜层玻璃包裹丝的巨磁阻抗效应

首先利用高频感应加热熔融拉丝法制备了Fe_(73.0)Cu_(1.0)Nb_(2.0)Si_(13.5)B_(9.0)玻璃包裹非晶丝;然后在氮气保护下480～650℃之间退火0.5 h;最后利用化学镀方法在570℃退火的玻璃包裹丝上沉积了一层铜,构成复合结构丝.利用扫描电镜测量了材料的几何尺寸,研究了玻璃包裹丝退火前后及复合结构丝的巨磁阻抗效应.结果表明,材料的软磁特性改善提高了材料的磁阻抗比,铜层与磁性层之间的电磁相互作用也影响磁阻抗比.     

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.     

A magic eggshell: Cu<Superscript>2+</Superscript> reacts with S<Superscript>2−</Superscript> to produce metal Cu,rather than CuS

In common sense, the chemical reaction between Cu²⁺ and S^2– ions produces black precipitation of CuS. However, if they are separated by an eggshell, they produce copper with trace amount of CuS on the surface of the eggshell at the side of copper chloride solution within one week. Such an unexpected phenomenon strongly indicated that Cu²⁺ is able to be reduced into metal copper when S^2– diffuses throughout the porous eggshell. The produced copper was verified by reacting with nitric acid to generate red-brown nitrogen dioxide at ambient temperature, as well as by the powder X-ray diffraction (XRD) and energy dispersive analysis of X-rays (EDS).     

Physical chemistry mechanisms of CDR system in sulphide mineral flotation

The flotation tests, zeta potential measurements, and Fourier transform infrared spectroscopy (FTIR) analysis on galena, sphalerite, and pyrite were studied in a collecting-depressing-reactivating (CDR) system. In this system, sulphide minerals were first collected and activated by the collector, and then depressed strongly by Ca(OH)₂ in a strong alkaline solution. Finally, they were reactivated by H₂SO₄. The flotation tests of pure minerals showed that in the Ca(OH)₂ depressing process sulphide minerals had similar flotation characteristics because they had already been influenced by the collector. Hence, the flotability differences between them were reduced. However, in the H₂SO₄ reactivating process considerable differences in the flotability between galena and sphalerite/pyrite were produced. That is to say, galena was relatively easy to be reactivated by H₂SO₄, but sphalerite and pyrite were not reactivated at pH > 11. The zeta potentials of sulfide minerals measured by the Zeta Plus presented irreversible characteristics on the change of pH values. The results of the FTIR spectra analysis indicated that the collectors already adsorbed on the mineral surface were removed partially by Ca(OH)₂.     

Fe6+对土壤中Cu2+浓度动态变化的影响

为了探究高铁酸钾(Fe~(6+))对于Cu~(2+)在土壤垂直方向上迁移时浓度的影响,采用土柱实验,通过加入薄层示踪剂(Cu~(2+)、Fe~(6+)),以研究Cu~(2+)溶液在下渗过程中浓度的变化,以及Fe~(6+)对其下渗过程中浓度变化的影响;同时探求高铁酸钾(Fe~(6+))对铜污染土壤进行修复时的最佳使用量和最佳作用时间。实验结果表明,Fe~(6+)十分显著地提高了土壤对于Cu~(2+)的吸附作用,有效地控制了Cu~(2+)在土壤中的向下迁移,Fe~(6+)作用于铜污染土壤的最佳使用浓度为100 mg/L,最佳作用时间为5 h。     

Preparation of Al-Cu-Fe-(Sn,Si) quasicrystalline bulks by laser multilayer cladding

(Al₆₅Cul₂₀Fe₁₅)_100-x Sn_x (x=0, 12, 20, 30) and Al₅₇Si₁₀Cu₁₈Fe₁₅ powders were cladded on a medium carbon steel (45# steel) substrate by laser multilayer cladding, respectively. The phases and properties of the produced quasicrystalline bulks were investigated. It was found that the main phases in the Al₆₅Cul₂₀Fe₁₅ sample were crystalline λ-Al₁₃Fe₄ and icosahedral quasicrystal together with a small volume fraction of θ-Al₂Cu phase. The volume fraction of icosahedral phase decreased as the Sn content in the (Al₆₅Cul₂₀Fe₁₅)_100-x Sn_x samples increased owing to the formation of β-CuSn phase. The increase of Sn content improved the brittleness of the quasicrystal samples. The morphology of the solidification microstructure in the Al₅₇Si₁₀Cu₁₈Fe₁₅ sample changed from elongated shape to spherical shape due to the addition of Si. The nanohardness of the laser multilayer cladded quasicrystal samples was equal to that of the as-cast sample prepared by vacuum quenching. In terms of hardness, the laser cladded Al₅₇Si₁₀Cu₁₈Fe₁₅ quasicrystalline alloy has the highest value among all the investigated samples.     

Antibacterial and corrosive properties of copper implanted austenitic stainless steel

Copper ions were implanted into austenitic stainless steel (SS) by metal vapor vacuum arc with a energy of 100 keV and an ions dose range of (0.5-8.0)×1017 cm-2. The Cu-implanted SS was annealed in an Ar atmosphere furnace. Glancing X-ray diffraction (GXRD), transmission electron microscopy (TEM) and Auger electron spectroscopy (AES) were used to reveal the phase compositions, microstructures, and concentration profiles of copper ions in the implanted layer. The results show that the antibacterial property of Cu-implanted SS is attributed to Cu_9.9Fe_0.1, which precipitated as needles. The depth of copper in Cu-implanted SS with annealing treatment is greater than that in Cu-implanted SS without annealing treatment, which improves the antibacterial property against S. aureus. The salt wetting-drying combined cyclic test was used to evaluate the corrosion-resistance of antibacterial SS, and the results reveal that the antibacterial SS has a level of corrosion-resistance equivalent to that of un-implanted SS.     

机械合金化Fe100-xCux体系的结构

利用XAFS和XRD方法分别研究了机械合金化80 h制备的Fe_100-xCu_x 系统的晶体结构及Fe和Cu原子的局域配位环境.结果表明,当x＞40时,样品中Fe原子的bcc结构消失,Cu原子的近邻结构基本不变,fcc晶格参数随x的增加而减小;当x＜30时, Cu原子的fcc结构消失, Fe原子的近邻结构基本不变,bcc晶格参数随Cu原子的比例减小而增大;而x=30左右时,fcc和bcc结构共存.研究结果还表明, Fe原子和Cu原子的比例不是相差很大时,Fe原子和Cu原子的近邻配位无序度会在很大的范围内变化,说明Fe-Cu二元体系不可能形成均匀的过饱和固溶体,存在Cu富集区和Fe富集区,是由多种物态组成的混合物.