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.     

Interfacial reactions of chalcopyrite in ammonia–ammonium chloride solution

The interfacial reactions of chalcopyrite in ammonia–ammonium chloride solution were investigated. The chalcopyrite surface was examined by scanning electron microscopy and X-ray photoelectron spectroscopy (XPS) techniques. It was found that interfacial passivation layers of chalcopyrite were formed from an iron oxide layer on top of a copper sulfide layer overlaying the bulk chalcopyrite, whereas CuFe_1–xS₂ or copper sulfides were formed via the preferential dissolution of Fe. The copper sulfide layer formed a new passivation layer, whereas the iron oxide layer peeled off spontaneously and partially from the chalcopyrite surface. The state of the copper sulfide layer was discussed after being deduced from the appearance of S^2–, S^2?₂, S^2?_n, S⁰ and SO^2?₄. A mechanism for the oxidation and passivation of chalcopyrite under different pH values and redox potentials was proposed. Accordingly, a model of the interfacial reaction on the chalcopyrite surface was constructed using a three-step reaction pathway, which demonstrated the formation and transformation of passivation layers under the present experimental conditions.     

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.     

Kinetics of acid-oxygen leaching of low-sulfur Ni-Cu matte at atmospheric pressure

The leaching of low-sulfur Ni-Cu matte in acid-oxygen (CuSO4-H2SO4-O2) solution at atmospheric pressure was researched. This matte was obtained from high grade Ni-Cu matte by magnetic separation, which mainly contained Ni-Cu alloy and a small quantity of sulfides. The effects of temperature, agitation speed, oxygen flow rate, particle size, acid concentration and concentration of copper ion were studied. It is found that the matte particles are leached by shrinking core mechanism and the leaching process is electrochemically controlled. In a temperature range of 30-60 ℃, the surface reaction is rate-limiting step, with an apparent activation energy of 41.9 kJ/mol. But at higher temperature (70-85℃), the rate process is controlled by diffusion through the product layer, with an apparent activation energy of 7.3 kJ/mol.     

Kinetic process of oxidative leaching of chalcopyrite under low oxygen pressure and low temperature

Kinetic process of oxidative leaching of chalcopyrite in chloride acid hydroxide medium under oxygen pressure and low temperature was investigated. The effect on leaching rate of chalcopyrite caused by these factors such as ore granularity, vitriol concentration, sodium chloride concentration, oxygen pressure and temperature was discussed. The results show that the leaching rate of chalcopyrite increases with decreasing the ore granularity. At the early stage of oxidative reaction, the copper leaching rate increases with increasing the oxygen pressure and dosage of vitriol concentration, while oxygen pressure affects leaching less at the later stage. At low temperature, the earlier oxidative leaching process of chalcopyrite is controlled by chemical reactions while the later one by diffusion. The chalcopyrite oxidative leaching rate has close relation with ion concentration in the leaching solution. The higher ion concentration is propitious for chalcopyrite leaching.     

Copper and elemental sulphur from chalcopyrite by pressure leaching

Processes employing direct oxidation under an over-pressure of air or oxygen in an aqueous sulphuric acid medium have been developed in the Sherritt Gordon Laboratories for iron, nickel, cobalt, zinc and lead sulphide concentrates. This study has recently also been extended to chalcocite, Cu₂S, concentrates. The rising interest in processes employing direct aqueous oxidation is stimulated by the fact that elemental sulphur can be produced as a by-product rather than sulphur dioxide or sulphuric acid.The present paper outlines a process which features the direct pressure oxidation of the most abundant copper sulphide mineral, chalcopyrite, CuFeS₂. The optimum conditions for a practical pressure leaching step have now been developed in the laboratory which results in the production of copper sulphate solution suitable for copper winninq by electrolysis, hydrogen reduction, solvent extraction combined with electrolysis, or other means. The leach residue yields pure elemental sulphur by-product. Copper and elemental sulphur recoveries of 98 and 85% respectively have been recorded. The fastest oxidation rate, corresponding to a leach retention time of 2.5 hr, was obtained when the copper concentrate was ground to 99.5% — 325 mesh, when a 50% stoichiometric excess of concentrate over the amount of available sulphuric acid for copper was used and when the oxygen partial pressure and temperature were maintained at 500 psi and 240°F, respectively. In an idealized form, the pressure leaching reaction can be expressed as follows:—CuFeS₂ + H₂SO₄ + 1 1/40₂ + 1/2H₂O → CuSO₄ + Fe(OH)₃ + 2S°After separation of the copper sulphate solution by filtration, elemental sulphur and excess concentrate ore recovered from the iron oxide tailing by flotation. The tailing, containing iron oxide and insolubles, is rejected. The elemental sulphur is separated from the concentrate by hot filtration, solvent extraction, distillation, or other means, and the unleached chalcopyrite is recycled to the leaching step.     

Relatedness between catalytic effect of activated carbon and passivation phenomenon during chalcopyrite bioleaching by mixed thermophilic Archaea culture at 65 °C

The relatedness between catalytic effect of activated carbon and passivation phenomenon during chalcopyrite bioleaching by mixed thermophilic Archaea culture (Acidianus brierleyi, Metallosphaera sedula, Acidianus manzaensis and Sulfolobus metallicus) at 65 °C was studied. Leaching experiments showed that the addition of activated carbon could significantly promote the dissolution of chalcopyrite for both bioleaching and chemical leaching. The results of synchrotron-based X-ray diffraction, iron L-edge and sulfur K-edge X-ray absorption near edge structure spectroscopy indicated that activated carbon could change the transition path of electrons through galvanic interactions to form more readily dissolved secondary mineral chalcocite at a low redox potential (<400 mV) and then enhanced the copper dissolution. Jarosite accumulated immediately in the initial stage of bioleaching with activated carbon but copper dissolution was not hindered. However, much jarosite precipitated on the surface of chalcopyrite in the late stage of bioleaching, which might account for the decrease of copper dissolution rate. More elemental sulfur (S⁰) was also detected with additional activated carbon but the mixed thermophilic Archaea culture had a great sulfur oxidation activity, thus S⁰ was eliminated and seemed to have no significant influence on the dissolution of chalcopyrite.     

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。     

Leaching of chalcopyrite with hydrogen peroxide in hydrochloric acid solution

The aim of this work was to investigate the leaching of chalcopyrite concentrate in hydrochloric acid with hydrogen peroxide as a strong oxidizing agent. The effects of the leaching variables on metal extraction, such as stirring speed, solid-to-liquid ratio, temperature and HCl and H₂O₂ concentrations, were studied. The maximum final copper extraction of 33% was attained with 3.0 mol/L H₂O₂ in 0.5 mol/L HCl at room temperature after 180 min of the reaction. The results showed that the copper extraction was increased in the first 60 min of reaction, after which it essentially ceased due to the fast catalytic decomposition of hydrogen peroxide. Further, solid-to-liquid ratio affected the copper extraction significantly and the highest copper extraction was obtained in the most dilute suspension (i.e., S/L ratio of 1:100). The dissolution process was described by the first order kinetics equation. The apparent activation energy of 19.6 kJ/mol suggested that the dissolution process was under diffusion control. The reaction orders for HCl and H₂O₂ were established to be 0.30 and 0.53, respectively. The results of the XRD and SEM/EDS analysis of the leaching residue indicated the generation of the elemental sulphur on mineral surfaces which tended to inhibit the leaching rate.     

铟的还原浸出动力学及分步沉淀选择性分离（英文）

开展硫化锌精矿还原浸出高铁锌浸出渣高效浸铟及浸出液中铟选择性分离的研究。结果表明：在固体物料粒度74～105μm、反应温度90℃、浸出时间300 min、硫酸浓度1.4 mol/L的条件下,铟的浸出率达95%以上。采用收缩核模型对还原浸出动力学进行分析,不同条件下的浸出实验结果表明反应受穿过固体产物层的扩散控制,活化能为17.96 k J/mol,相对于硫酸浓度的反应级数为2.41。铁粉置换沉铜过程铜和砷的沉淀率均达99%以上。98%以上的铟从含高亚铁离子浓度的硫酸锌溶液中选择性分离,获得铟含量约为2.4%的富铟渣,经酸浸-萃取-电积工艺流程进一步处理后可得到纯铟。     

Characterization and kinetic study on ammonia leaching of complex copper ore

Ammonia leaching kinetics of a complex Cu-ore assaying 8.8% Cu and 36.1% Fe was examined. Mineralogical characterization indicated that the major phase of the ore was siderite with chalcopyrite as the major sulfide mineral. The effects of parameters such as agitation, temperature, NH₃ concentration, particle size and oxygen partial pressure (p_O2) were investigated. Under the standard leaching conditions of 125–212 µm particle size, 120 °C, 1.29 mol/L NH₃ and 202 kPa of p_O2, about 83% Cu could be selectively extracted in 2.5 h. However, when using higher NH₃ concentration and lower particle size, more than 95% extraction was achieved. The leaching process was found to be surface reaction controlling. The estimated activation energy was (37.6±1.9) kJ/mol and empirical orders of reaction with respect to p_O2 and [NH₃] were about 0.2 and 1, respectively.     

AES-Untersuchungen an Passivschichten auf Eisenproben

AES investigations on passive layers on iron specimens Passive layers on iron specimens (generated in saturated calcium hydroxide solution with and without addition of calcium sulfide and sulfate) are studied with the aid of simultaneous application of Auger electron spectroscopy and ion bombardment. According to the results obtained Fe and Ca are the main constituents of the layers while the quantity of sulfur containg compunds is very low. According to the depth profiles established the concentrations of Fe, Ca and oxygen are relatively constant withing the passive layer, irrespective ot he passivation potential; variations attributed to various passivation times give rise to the assumption of structural influences. Comparisons with mixed oxides point to a passive layer composition of appr. 2 CaO·Fe₂O₃.     

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%)。     

Feasibility study on heap bioleaching of chalcopyrite

Bioleaching of chalcopyrite often encountered the formation of passivation layer, which inhibited the leaching process and resulted in a low leaching rate. This inhibitory effect can be eliminated by thermophilic biole- aching. The industrial test of BioCOP technology based on thermophiles was successfully completed, which confirmed the feasibility of chalcopyrite bioleaching. However, industrial leaching rate of chalcopyrite heap bioleaching is lower. This paper described the development status and industrial test of chalcopyrite heap bioleaching technology. The reasons for the lower efficiency of chalcopyrite heap bioleaching were analyzed. The strategies for successful chalcopyrite heap bioleaching were proposed.     

Bioleaching of chalcopyrite with Acidianus manzaensis YN25 under contact and non-contact conditions

In order to investigate the contributions of contact and non-contact cells of Acidianus manzaensis(A.manzaensis) YN25 to the bioleaching of chalcopyrite,three experiments were carried out in the modified shake flasks.The redox potential,pH,cell density,copper and iron ions in the solution were monitored,and the morphological feature and chemical composition of the leached residues were analyzed.The highest leaching efficiency of Cu and Fe was reached in the experiment where the A.manzaensis YN25 could contact the surface of the chalcopyrite.There was no precipitation of jarosite in the leached residues of three experiments,but there was elemental sulfur in the leached residues when the cells could not contact the chalcopyrite.From these results,it is apparent that the leaching of the chalcopyrite is the cooperative action of the contact and non-contact A.manzaensis YN25.     

环烷酸和硫化氢腐蚀体系的热力学分析

从热力学角度探讨了环烷酸－铁－硫化氢腐蚀体系的热力学性质,结果表明：在该体系中,腐蚀产物受硫化氢和环烷酸分压影响;钝化区为硫化氢腐蚀,硫化物在膜中的扩散为速率控制步骤;在腐蚀区为环烷酸腐蚀,环烷酸与金属表面的反应为速率控制步骤。根据相图,分析了两次出现腐蚀高峰的原因。     

Copper hydrometallurgy-current status,preliminary economics,future direction and positioning versus smelting

The heap leaching of oxide copper ores with copper cathode recovery by solvent extraction and electrowinning is now well established as a low-cost method of copper recovery. This technology has recently been applied successfully to mixed oxide and chalcocite ores, notably in Chile at Cerro Colorado, Quebrada Blanca and Zaldivar.Currently, there are significant development efforts underway to try to extend heap leaching to chalcopyrite ores.The success of heap leaching/SX/EW has also led to a revival in the development of hydrometallurgical processes to recover copper from chalcopyrite and other copper concentrates. The current status of copper hydrometallurgy is reviewed and the most commercially attractive potential applications are explored. The advantages and disadvantages of the hydrometallurgical treatment of chalcopyrite concentrates and its preliminary economics are compared with those for the current best practices in copper smelting and refining.     

Dynamics in simultaneous electro-generative leaching for sphalerite-MnO2

The principle for the electro-generative leaching was applied to simultaneous leaching of sphalerite-MnO2. A galvanic system for the bio-electro-generative leaching was set up. The effects of grain size and temperature on rate of zinc extraction fi＇om sphalerite under the conditions of presence and absence ofAcidithiobacillusferrooxidans （A.ferrooxidans） were studied, respectively. The results show that with bacteria, the maximum extraction of zinc fi＇om the ores with grain size of 16.6 μm can reach 32.01% after leaching for 12 h, while to obtain the same extraction ratio in the traditional bio-leaching route （i.e. not electro-generative one）10 d is needed to ore granules with same size. The unreacted shrinking core model was used for describing the reaction-relative and diffusion-relative phenomena presented in the process of the electro-generative leaching with and without bacteria, which is considered to be diffusion controlled. The activation energies of the anodic reaction for leaching system in the presence and absence of bacteria are 11.97 and 14.39 kj/mol, respectively, indicating that leaching rate can be decreased by A. ferrooxidans. SEM was used to study the effect ofA. ferrooxidans on the ores in the simultaneous electro-generative leaching, which indicates that the produced sulfur on the surface of the sulfides can be oxidized by A. ferrooxidans after bio-electro-generative leaching for 24 h, and the transferred charge due to the bacterial oxidation is up to 17.86%, which is an important part of the output electric quantity.     

Copper hydrometallurgy——current status, preliminary economics, future direction and positioning versus smelting

The heap leaching of oxide copper ores with copper cathode recovery by solvent extraction and electro-winning is now well established as a low-cost method of copper recovery. This technology has recently been applied successfully to mixed oxide and chalcocite ores, notably in Chile at Cerro Colorado, Quebrada Blanca and Zaldivar.Currently, there are significant development efforts underway to try to extend heap leaching to chalcopyrite ores.The success of heap leaching/SX/EW has also led to a revival in the development of hydrometallurgical processes to recover copper from chalcopyrite and other copper concentrates. The current status of copper hydrometallurgy is re-viewed and the most commercially attractive potential applications are explored. The advantages and disadvantages of the hydrometallurgical treatment of chalcopyrite concentrates and its preliminary economics are compared with those for the current best practices in copper smelting and refining.     

Recovery of gallium from zinc concentrate by pressure oxygen leaching

Zinc concentrate with high gallium content is one of the main resources of gallium.The gallium presents in the form of isomorphism in tetrahedron coordination with sulfur in sphalerite.The research was to investigate the amenability of zinc concentrate with high gallium to pressure oxygen leaching.The particle size,sulfuric acid concentration,oxygen partial pressure,additive amount,and time of reaction were studied.The extraction yields of gallium and zinc are 86%and 98%,respectively.The optimal condition is 100 g of zinc concentrate with particle size smaller than 38 lm,sulfuric acid concentration150 g L-1,leaching temperature 150℃,leaching time120 min,oxygen partial pressure 0.7 MPa,additive amount of 0.2 wt%.