Investigation on microwave heating for direct leaching of chalcopyrite ores and concentrates

The use of microwave energy in materials processing is a relatively new development presenting numerous advantages because of the rapid heating feature. Microwave technology has great potential to improve the extraction efficiency of metals in terms of both a reduction in required leaching time and an increase in the recovery of valuable metals. This method is especially pertinent in view of the increased demand for environment-friendly processes. In the present study, the influence of microwave heating on the direct leaching of chalcopyrite ores and concentrates were investigated. The results of microwave leaching experiments were compared with those obtained under conventional conditions. During these processes, parameters such as leaching media, temperature, and time have been worked to determine the optimum conditions for proper copper dissolution. Experimental results show that microwave leaching is more efficient than conventional leaching. The optimum leaching conditions for microwave leaching are the solid-to-liquid ratio of 1:100 g/mL, the temperature of 140℃, the solution of 0.5 M H₂SO₄ + 0.05 M Fe₂(SO₄)₃, and the time of 1 h.     

Use of ionic liquid in leaching process of brass wastes for copper and zinc recovery

Brass ash from the industrial brass manufacturer in Turkey was leached using the solutions of ionic liquid (IL) 1-butyl-3-methyl-imidazolium hydrogen sulfate ([bmim]HSO₄) at ambient pressure in the presence of hydrogen peroxide (H₂O₂) and potassium peroxymonosulfate (oxone) as the oxidants. Parameters affecting leaching efficiency, such as dissolution time, IL concentration, and oxidizing agent addition, were investigated. The results show that [bmim]HSO₄ is an efficient IL for the brass ash leaching, providing the dissolution efficiencies of 99% for Zn and 24.82% for Cu at a concentration of 50vol% [bmim]HSO₄ in the aqueous solution without any oxidant. However, more than 99% of zinc and 82% of copper are leached by the addition of 50vol% H₂O₂ to the [bmim]HSO₄ solution. Nevertheless, the oxone does not show the promising oxidant behavior in leaching using [bmim]HSO₄.     

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.     

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.     

Effects of substrate temperature and ambient oxygen pressure on growth of Ba(Fe1/2Nb1/2)O3 thin films by pulsed laser deposition

Ba(Fe1/2Nb1/2)O3 thin films were grown on Pt/TiO2/SiO2/Si substrates with pulsed laser deposition (PLD) at temperatures ranging from 823 to 923 K with the varied ambient oxygen pressure. X-ray diffraction (XRD) data confirmed the single phase of polycrystalline Ba(Fe1/2Nb1/2)O3 thin films. The effects of substrate temperature and ambient oxygen pressure on the surface morphologies of the thin films were investigated by atomic force microscopy (AFM) and the growth dynamics of thin films was discussed. Larger grains and denser surface morphologies were observed with increasing substrate temperature. While finer grains were produced with increasing ambient oxygen pressure due to more frequent collisions between the ejected species and ambient oxygen molecules. The influence of the substrate temperature and ambient oxygen pressure on the dielectric properties was also discussed. Improved dielectric constant and decreased dielectric loss was observed for the thin film deposited at evaluated temperature.     

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.     

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.     

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.     

Preparation of Cu-SiO<Subscript>2</Subscript> composite aerogel by ambient drying and the influence of synthesizing conditions on the structure of the aerogel

A copper-doped silica composite aerogel with high specific surface area was prepared using a sol-gel method at ambient pressure. A drying control chemical additive (DCCA) N,N-dimethylformamide (DMF) was introduced to the composite sol of tetraethyl orthosilicate (TEOS) and copper nitrate (Cu(NO3)2·3H2O) during the synthesizing process. The influence of the preparation conditions including Cu loading, catalyst concentration and heat treatment on the structure of copper-doped silica was investigated. The results showed that the obtained aerogel particles were uniformly distributed. The pore diameter was in a range of 2 to 15 nm. Heavier Cu loading benefited the formation of CuO crystalline, and reduced the specific surface area and pore diameter. When the catalyst concentration was high, the aggregation of Si-O network was reduced with the increase of it. The composite aerogel exhibited a good thermal stability after the heat treatment at high temperature.     

Ultrasonic measurements of single-crystal gold under hydrostatic pressures up to 8 GPa in a Kawai-type multi-anvil apparatus

Ultrasonic measurements were conducted on single-crystal gold at ambient condition and hydrostatic pressures up to 8 GPa at room temperature in a Kawai-type multi-anvil apparatus. The P-wave velocities measured at high pressures were in good agreement with Daniels and Smith’s ultrasonic study. The three independent elastic constants of gold at ambient condition were determined to be C11=192.7 GPa, C12=162.9 GPa, and C44=42.4 GPa. On the basis of an analysis of previous elastic data and the present ultrasonic data, the pressure derivatives of three elastic constants were estimated to be C1 ′1= 7.12,C 1′2 = 6.24,and C4′4 = 1.82. The calculated values of isothermal bulk modulus (KT0) and its pressure derivatives ( KT ′0) are KT0 = 166.44 GPa and KT ′0= 6.56. This indicates that Anderson et al.’s model of equation of state of gold might underestimates pressure about 1 GPa at pressure around 23 GPa and ambient temperature. Our results explained the discrepancies among the models of equation of state of gold proposed previously.     

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.     

Electromigration in eutectic SnAg solder reaction couples with various ambient temperatures and current densities

The electromigration behavior of eutectic SnAg solder reaction couples was studied at various temperature (25 and 120℃ when the current density was held constant at 104 A/cm2 or 5×103 A/cm2. Under the current density of 104 A/cm2, scallop type Cu₆Sn₅ spalls and migrates towards the direction of electron flow at room ambient temperature (25℃), but transforms to layer type Cu₃Sn and leaves Kirkendall voids in it at high ambient temperature (120℃). Under the current density of 5×103 A/cm2 plus room ambient temperature, no obvious directional migration of metal atoms/ions is found. Instead, the thermal stress induced by mismatch of dissimilar materials causes the formation of superficial valley at both interfaces. However, when the ambient temperature increases to 120℃, the mobility of metal atoms/ions is enhanced, and then the grains rotate due to the anisotropic property of β-Sn.     

Efficient and selective recovery of Ni,Cu, and Co from low-nickel matte via a hydrometallurgical process

Low-nickel matte was intensively characterized, and Ni, Cu, and Co were determined to exist mainly as (Fe,Ni)₉S₈ and FeNi₃, Cu₅FeS₄, and (Fe,Ni)₉S₈ and Fe₃O₄ (in isomorphic form), respectively. The efficient and selective extraction of Ni, Cu, and Co from the low-nickel matte in an (NH₄)₂S₂O₈/NH₃·H₂O solution system was studied. The effects of (NH₄)₂S₂O₈ and NH₃·H₂O concentrations, leaching time, and leaching temperature on the metal extraction efficiency were systematically investigated. During the oxidative ammonia leaching process, the metal extraction efficiencies of Ni 81.07%, Cu 93.81%, and Co 71.74% were obtained under the optimal conditions. The relatively low leaching efficiency of Ni was mainly ascribed to NiFe alloy deactivation in ammonia solution. By introducing an acid pre-leaching process into the oxidative ammonia leaching process, we achieved the high extraction efficiencies of 98.03%, 99.13%, and 85.60% for the valuable metals Ni, Cu, and Co, respectively, from the low-nickel matte.     

Reductive leaching of manganese from low-grade pyrolusite ore in sulfuric acid using pyrolysis-pretreated sawdust as a reductant

Manganese (Mn) leaching and recovery from low-grade pyrolusite ore were studied using sulfuric acid (H₂SO₄) as a leachant and pyrolysis-pretreated sawdust as a reductant. The effects of the dosage of pyrolysis-pretreated sawdust to pyrolusite ore, the concentration of sulfuric acid, the liquid/solid ratio, the leaching temperature, and the leaching time on manganese and iron leaching efficiencies were investigated. Analysis of manganese and iron leaching efficiencies revealed that a high manganese leaching efficiency was achieved with low iron extraction. The optimal leaching efficiency was determined to be 20wt% pyrolysis-pretreated sawdust and 3.0 mol/L H₂SO₄ using a liquid/ solid ratio of 6.0 mL/g for 90 min at 90℃. Other low-grade pyrolusite ores were tested, and the results showed that they responded well with manganese leaching efficiencies greater than 98%.     

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.     

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.     

界面反应法制备Ag@AgCl纳米棒及其光催化性能研究

采用界面反应法合成了一种表面负载Ag纳米颗粒的Ag@AgCl纳米棒复合物。通过IR、XRD、SEM、TEM、XPS等手段对所制备材料进行表征。结果表明,采用界面法可以在常温、常压下将纳米颗粒负载在Ag纳米棒上。对所制备材料的光催化性能进行研究,由测试结果可知,该纳米复合材料在可见光下催化亚甲基蓝（MB）的活性要明显优于二氧化钛（P-25）,且光照15 min后MB的降解可达96%。研究结果将为银/卤化银体系材料的开发及在可见光光催化领域的应用提供新的思路。     

Decompression-induced disorder to order phase transition in low-melting ionic liquid [OMIM][PF6]

In situ pressure-induced Raman spectral changes of 1-octyl-3-methyl imidazolium hexafluorophosphate （[OMIM][PF6]） have been investigated under the pressure up to 5.86 GPa at room temperature. The results indicated that [OMIM][PF6] experienced a phase transition at about 4.12 GPa during compression, and it was thought as a phase transition of liquid to a superpressurized glass. Upon decompression, from the obvious change of Raman spectra of [OMIM][PF6] at about 0.48 GPa, it could be inferred that a decompression-induced disorder to order phase transition in [OMIM][PF6] occurred. The phase behavior of [OMIM] [PF6] at low temperature under atmospheric pressure was also investigated in detail. The result showed that Raman spectra of [OMIM][PF6] varied slightly and no crystallization occurred upon cooling. These facts suggested that a disorder to order phase transition was induced by decompression in [OMIM][PF6], and [OMIM][PF6] served as a superpressurized glass under the pressure above 4.12 GPa, which was similar to the glassy state at low temperature.     

Kinetic study on the direct nitridation of silicon powders diluted with α-Si3N4 at normal pressure

Silicon nitride (Si₃N₄) powders were prepared by the direct nitridation of silicon powders diluted with α-Si₃N₄ at normal pressure. Silicon powders of 2.2 μm in average diameter were used as the raw materials. The nitriding temperature was from 1623 to 1823 K, and the reaction time ranged from 0 to 20 min. The phase compositions and morphologies of the products were analyzed by X-ray diffraction and scanning electron microscopy, respectively. The effects of nitriding temperature and reaction time on the conversion rate of silicon were determined. Based on the shrinking core model as well as the relationship between the conversion rate of silicon and the reaction time at different temperatures, a simple model was derived to describe the reaction between silicon and nitrogen. The model revealed an asymptotic exponential trend of the silicon conversion rate with time. Three kinetic parameters of silicon nitridation at atmospheric pressure were calculated, including the pre-exponential factor (2.27 cm·s^?1) in the Arrhenius equation, activation energy (114 kJ·mol^?1), and effective diffusion coefficient (6.2×10^?8 cm²·s^?1). A formula was also derived to calculate the reaction rate constant.     

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.