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双语推荐：黄铜矿

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采用XRD、XPS和MLA等检测研究海相火山岩型黄铜矿及斑岩型黄铜矿化学浸出的差异性。结果表明:在化学浸出过程中,海相火山岩型黄铜矿与斑岩型黄铜矿浸出特性有很大的差异,这是由于两种黄铜矿表面形成中间产物的性质不同。两种黄铜矿化学浸出的产物除单质硫S8之外,还有非化学计量的中间产物Cu3.5Fe4S2.5、Cu5Fe4S及Cu3.5Fe1.5S5生成。海相火山岩型黄铜矿的中间产物以Cu3.5Fe4S2.5为主,斑岩型黄铜矿的中间产物以Cu3.5Fe1.5S5为主。海相火山岩型黄铜矿与斑岩型黄铜矿具有不同的溶解途径:海相火山岩型黄铜矿受到H+的腐蚀后矿物中的Cu—S断裂,Cu2+与Fe2+同时溶解,而斑岩型黄铜矿受到H+腐蚀后Fe2+优先溶解。
The chemical leaching different characteristics of chalcopyrite with different genetic types (marine volcanic and porphyry) were investigated by XRD, XPS and MLA analysis. The results show that the difference between marine volcanic chalcopyrite and porphyry chalcopyrite during chemical leaching is generated by intermediate formed on the surface of chalcopyrite with different chemical and structural properties. Nonstoichiometric intermediate products, such as Cu3.5Fe4S2.5, Cu5Fe4S and Cu3.5Fe1.5S5, also form during two kinds of chalcopyrite leaching, besides sulphur S8. The main intermediate product of marine volcanic chalcopyrite is Cu 3.5 Fe 4 S 2.5 , while Cu 3.5 Fe 1.5 S 5 is mainly in porphyry chalcopyrite. The leaching mechanism of marine volcanic chalcopyrite and porphyry chalcopyrite is different. During the leaching process of marine volcanic chalcopyrite, Cu2+and Fe2+are dissolved simultaneously after the broken of Cu—S bond attacked by proton. However, Fe2+dissolv

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采用生物浸出和循环伏安试验研究初始pH对黄铜矿在65℃条件下氧化溶解的影响,分别采用XRD和拉曼光谱分析黄铜矿生物浸出过程中和电极表面形成的氧化产物。化学浸出结果表明：黄铜矿溶解速率随着初始pH的减小而增大,然而初始pH对黄铜矿生物浸出的影响却正好相反。当初始pH为1.0时,万座嗜酸两面菌的加入几乎没有促进黄铜矿的溶解,这主要是由于高酸度严重抑制了万座嗜酸两面菌的生长。电解液中存在或不存在万座嗜酸两面菌时黄铜矿的阳极氧化电流都随着初始pH的增大而增大,同时在黄铜矿电极表面检测到了单质硫和铜蓝。结果表明,在化学浸出过程中黄铜矿是在质子作用和氧化作用下溶解的,黄铜矿氧化生成了铜蓝和单质硫。
The influence of initial pH on the chalcopyrite oxidation dissolution at 65℃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

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通过吸附、动电位、接触角和摇瓶浸出试验研究Leptospirillum ferriphilum菌作用前后黄铜矿表面性质的变化。采用不同能源物质（亚铁和黄铜矿粉）培养L.ferriphilum菌。结果表明,细菌可以很快吸附在黄铜矿表面,并且固体能源物质培养的细菌比液体能源物质培养的细菌可以更多、更快地吸附在矿物表面。与细菌作用后,黄铜矿的等电点朝着细菌等电点的方向移动。在添加与不添加能源物质时,黄铜矿的接触角表现出不同的变化趋势。XRD、SEM/EDS检测表明浸出过程中在黄铜矿表面生成了硫和黄钾铁矾。通过EDS检测可知在黄铜矿的分解过程中,铁优先从黄铜矿表面释放出来。在浸出过程中黄铜矿表面生成了钝化层,从而导致其浸出率很低。通过研究推测钝化层的主要成分是硫,而不是黄钾铁矾。
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. Furt

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采用电化学测试和X射线光电子能谱(XPS)测试分析黄铜矿与斑铜矿在酸性细菌培养基中的电化学溶解过程。斑铜矿直接氧化反应比还原反应更容易发生，但黄铜矿既难被氧化，又难被还原。斑铜矿具有更高的氧化速率，从而比黄铜矿更容易被溶解。铜蓝(CuS)是黄铜矿与斑铜矿溶解过程的中间产物。因此，斑铜矿的溶解途径主要为直接氧化过程，中间产物铜蓝(CuS)可能限制其进一步溶解。黄铜矿的溶解途径包含了还原?氧化过程，其中，黄铜矿首先被还原为与斑铜矿类似的中间产物，再进一步被氧化，并产生铜蓝(CuS)，而黄铜矿的最初还原过程是其溶解过程的主要限制步骤。
The electrochemical dissolution process of chalcopyrite and bornite in acid bacteria culture medium was investigated by electrochemical measurements and X-ray photoelectron spectroscopy (XPS) analysis. Bornite was much easier to be oxidized rather than to be reduced, and chalcopyrite was difficult to be both oxidized and reduced. The relatively higher copper extraction of bornite dissolution can be attributed to its higher oxidation rate. Covellite (CuS) was detected as the intermediate species during the dissolution processes of both bornite and chalcopyrite. Bornite dissolution was preferred to be a direct oxidation pathway, in which bornite was directly oxidized to covellite (CuS) and cupric ions, and the formed covellite (CuS) may inhibit the further dissolution. Chalcopyrite dissolution was preferred to be a continuous reduction?oxidation pathway, in which chalcopyrite was initially reduced to bornite, then oxidized to covellite (CuS), and the initial reduction reaction

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酸性矿山废水(AMD)的形成对环境造成严重危害,而从源头上控制其产生是一项重要的处理措施。本研究利用课题组前期研制的钝化剂三乙烯四胺二硫代氨基甲酸钠(DTC-TETA)对常见硫化矿物黄铜矿进行处理后,通过不同体系的摇瓶实验比较,研究该钝化剂对黄铜矿的化学氧化和生物氧化过程的影响,并利用SEM、XRD和XPS对黄铜矿进行分析,探讨钝化剂的作用机制。结果表明,钝化剂处理过的黄铜矿经过20 d的化学、生物氧化后,产生的铜离子浓度分别是其相应对照的17%和48%,说明钝化剂能有效抑制黄铜矿的氧化速率。SEM结果表明,黄铜矿表面在钝化剂处理后,经过氧化受到的侵蚀明显减少,这是由于钝化剂在黄铜矿表面形成包膜有效隔绝氧化剂和细菌对黄铜矿的接触。样品的XRD和XPS分析结果说明了经钝化剂处理过的黄铜矿在氧化过程中可形成一些产物,但这没有改变黄铜矿的氧化进程。因此,黄铜矿经钝化剂DTC-TETA处理后其氧化速率受到抑制,表明表面钝化法是一项处理硫化物矿物避免产生AMD造成危害的可行技术,这对于从源头上控制AMD具有重要意义。
Acid mine drainage(AMD)has been recognized as one of the most serious long- term environmental problems associated with mining. The oxidation of sulfide-rich tailing is the source of AMD. Therefore source control of AMD is regarded as a most effective way to pre-vent its environmental impact. In this study, a coating agent, sodium triethylenetetramine bisdithiocarbamate(DTC-TETA), was explored to minimize the oxidation of chalcopyrite. Scanning electron microscope(SEM), X-ray diffraction(XRD)and X-ray photoelectron spectroscopy (XPS)were used to examine the mechanisms of chalcopyrite oxidation inhibition by the agent. The coating effectively decreased the oxida-tion rate of chalcopyrite during 20 day of experiment. The concentrations of copper ion in chemical and biological oxidation systems treated with the coating agent were only 17%and 48%of the corresponding controls. Compared to uncoated one, the surface corrosion of the chal-copyrite coated with DTC-TETA was significantly reduced

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通过Zeta电位分析、X射线光电子能谱分析、铜离子吸附试验、第一性原理计算及Hallimond浮选试验综合揭示了铜离子在黄铜矿表面同样存在着吸附行为，铜离子对黄铜矿同样具有活化作用，主要诱因是铜离子与表面活化位的硫作用，从而增加疏水性。这种吸附作用在一定条件下有利于黄铜矿自身的浮选。浮选矿浆中的铜离子主要来源于黄铜矿的表面氧化溶解和矿物内流体包裹体的释放，这些离子的存在及吸附使黄铜矿具有自活化特性。
The adsorption behaviors of copper ions on chalcopyrite surfaces were investigated based on zeta potential measurements, X-ray photoelectron spectroscopy, copper ion adsorption experiments, first-principles calculations, and Hallimond tube cell flotation experiments. The results show that copper ions activate the chalcopyrite as a result of the interactions between copper ions and sulfur on the chalcopyrite surface. This adsorption increases the flotation rate under certain conditions, and this is beneficial for the flotation of chalcopyrite. The copper ions in the flotation pulp are mainly derived from surface oxidation dissolution and the release of fluid inclusions, and these effects enable chalcopyrite to be activated.

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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。
The chalcopyrite was bioleached using ferrous and ferric solution. The variations of main experimental parameters including the pH value, ferrous and ferric concentration, bacterial adsorption rate and copper leaching efficiency in the leaching solution were investigated. The results show that the ferric concentration can affect the morphologies of jarosite. As the flocculent jarosite gradually forms in the ferric bioleaching solution, the floccule jarosite forms and cover on the chalcopyrite surface, which prevents the leaching process. In the ferrous bioleaching solution, the crustose and nodulated jarosite is generated and dispersed in the solution, which cannot prevent the sequential dissolution of the chalcopyrite.

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为了探明磷灰石在微生物浸出黄铜矿体系中的溶出特性及其对黄铜矿浸出的影响,选择粒径小于43μm的磷灰石与粒径小于74μm的黄铜矿以及At.f菌组成矿浆浸出体系,考察不同At.f菌接种量对于磷灰石溶出速率的影响及对黄铜矿浸出效果的影响。结果表明:浸出体系中含低浓度PO3-4可以提高铜的浸出效率;当At.f菌接种量为5%时,微生物浸出体系中磷灰石溶出的PO3-4浓度最小,为0.62 mg/L,此时黄铜矿的最终浸出率最高,达到57.4%,比PO3-4溶液浓度最高时体系的铜浸出率提高近30%。通过对微生物浸出前、后的浸渣进行扫描电镜、能谱分析和XRD分析发现,浸出后磷灰石表面浸蚀不明显,而黄铜矿表面浸蚀明显,同时浸渣中有新物质铵黄铁矾生成;磷灰石对于新生成的沉淀有一定的吸附作用,而且溶出较低浓度的PO3-4体系能提高黄铜矿的浸出。
To make sure the dissolution characteristics of apatite in the chalcopyrite bioleaching system and the influence on the chalcopyrite leaching efficiency, the apatite with particle size of less than 43 μm, chalcopyrite with 74 μm and Acidithiobacillus ferrooxidans (At.f) were used to prepare a bioleaching system. And the influence of different At.f inoculation amount on the apatite dissolution rate and chalcopyrite leaching effect were studied. The results show that chalcopyrite leaching efficiency can be improved when there exists PO 4 3? with low concentration in the bioleaching system. And PO43? reaches the lowest concentration of 0.62 mg/L in the bioleaching system when the At.f inoculation amount is 5%, and the final chalcopyrite leaching rate reaches the highest of 57.4%, which is 30%higher than that in the bioleaching system with the highest concentration of PO43?. Scanning electron microscope (SEM), energy dispersive spectroscope and X-ray diffraction (XRD) analyses

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本文通过显微观察和电子探针分析,发现大平山铜矿矿石中砷元素主要以硫化物方式,呈毒砂和少量砷黝铜矿独立矿物赋存于矿石中.毒砂主要呈自形-半自形粒状、他形粒状,赋存方式主要有:(1)以独立矿物呈稀疏浸染状分布于矿石中,局部呈条带状和中等稠密浸染状分布于矿石中;(2)呈交代方式与黄铁矿和黄铜矿伴生于矿石中,毒砂形成一般晚于黄铁矿和黄铜矿;(3)有少数毒砂被晚期黄铜矿、黄铁矿晶体包裹.砷黝铜矿呈他形粒状与黄铁矿、黄铜矿和毒砂共生,往往交代黄铁矿和黄铜矿.硫同位素分析结果表明砷主要来自晚期岩浆热液,或可能来自晚期火山热液;铅同位素分析结果表明砷可能主要来自上地壳.
The detection of Arsenic,under the microscope,appeared chiefly in the form of sulphide from the Dapingshan Copper deposit using electron microprobe analysis,with the appearance of arsenopyrite and a small amount of tennatite independently distributed in the ore.Arsenopyrites are mainly found in the form of automorphic-hypidiomorphic granular texture and xenomorphic granular texture.Its mode of occurrence are as follows:firstly,it acts as an independent sparsity disseminated mineral with partial strip and medium dense dissemination distributed in ore;secondly,it replaces the paragenic chalcopyrite and pyrite in ore after their formation;finally,small amounts of arsenopyrites are often wrapped with late crystal form of chalcopyrite and pyrite.The content of tennantite in ore is modest,and the paragenesis of xenomorphic granular texture with chalcopyrite,pyrite and arsenopyrite often leads to the replacement of chalcopyrite and pyrite.The current Sulfur isotope analysis revealed the deriv

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在丁铵黑药浮选体系中，研究含有-OH和-CSS-的2,3-二羟基丙基二硫代碳酸钠(SGX)对黄铜矿和方铅矿的抑制效果，并通过动电位和吸附量的测试，探讨抑制剂 SGX 与矿物的相互作用机理。浮选试验研究结果表明：在整个pH范围内，抑制剂SGX对黄铜矿有活化作用，而对方铅矿有很强的抑制作用。随着抑制剂SGX用量的增加，方铅矿的回收率迅速下降，而黄铜矿的回收率有小幅度的升高。在矿浆pH为6的条件下，人工混合矿浮选得出的精矿中铜的品位和回收率分别为29.52%和82.15%。通过动电位和吸附量的测试结果可知，抑制剂SGX在方铅矿表面有较强的吸附，而在黄铜矿表面吸附很弱。
Sodium 2,3-dihydroxypropyl dithiocarbonate (SGX), which contains-OH and-CSS- in the molecule, was used to explore selective depression of galena from chalcopyrite in the flotation tests with ammonium dibutyl dithiophosphate (DDTP), and zeta potential and adsorption measurements were performed to study the interaction between SGX and minerals. The flotation tests of single minerals show that SGX has slight activation on chalcopyrite and strong depression on galena in the whole pH range. With SGX dosage increasing, the recovery of galena decreases rapidly, while that of chalcopyrite increases slightly. At pH=6, the copper grade and recovery of concentrate are 29.52% and 82.15% respectively when mixture of two minerals is tested. Zeta potential and adsorption measurements indicate that SGX has strong adsorption on galena and slight adsorption on chalcopyrite.

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