嗜热布氏酸菌对梅州黄铜矿的生物浸出过程特性

研究了嗜热布氏酸菌对梅州黄铜矿的浸出机理和浸出过程特性. 嗜热布氏酸菌(简称A.B菌)在梅州黄铜矿表面的吸附过程符合朗格缪尔等温线,最大吸附量XAm 5.00×108 cell/g,吸附平衡常数KA 5.88×10-7 mL/cell. 梅州黄铜矿的浸出主要是通过A.B菌的直接氧化起作用. 单独A.B菌处理时,铜浸出速率为0.0137 g/(L·h),是Fe3+化学氧化速率的6倍. A.B菌(65℃)对梅州黄铜矿的浸出速率是常温氧化亚铁硫杆菌(简称T.F)的16倍(31℃). A.B菌生长和浸矿的最适温度均为65℃,微生物生长最佳pH为2.0,而浸矿最适pH为1.5. A.B菌处理10 d可使铜浸出率达91.3%,具有潜在的工业应用价值.     

Catalytic mechanism of manganese ions and visible light on chalcopyrite bioleaching in the presence of Acidithiobacillus ferrooxidans

The bioleaching of chalcopyrite is low cost and environmentally friendly,but the leaching rate is low.To explore the mechanism of chalcopyrite bioleaching and improve its leaching rate,the effect and mechanism of manganese ions(Mn²⁺) and visible light on chalcopyrite mediated by Acidithiobacillus ferrooxidans(A.ferrooxidans) were discussed.Bioleaching experiments showed that when both Mn²⁺ and visible light were present,the copper extraction was 14.38% higher than that of t...     

低品位黄铜矿在嗜热布氏酸菌下的循环伏安分析

电解液中含与不含布氏酸菌时,采用循环伏安法研究了黄铜矿-碳糊电极与电解液之间的电化学行为,并探讨了温度、阴极电位、Fe2+和Cu2+对循环伏安曲线的影响. 结果表明,低品位黄铜矿在0.45 V出现生成多硫化合物的氧化峰,在-0.25和-0.43 V出现生成Cu5FeS4和Cu2S的还原峰. 温度升高促进黄铜矿氧化分解,65℃时的峰电流为35℃时的2倍. 添加适量Fe2+和Cu2+能促进黄铜矿的氧化分解.     

A dynamic analysis of chalcopyrite bioleaching in continuous flow reactor systems

A dynamic analysis of chalcopyrite bioleaching was performed in continuous flow systems. In contrast to a previous batch analysis¹ in which the influence of particle surface area on reaction rate was not accounted for, the unsteady‐state change in particle surface area was integrated into the dynamic analysis by application of the modified PBM.² The current study extends the analysis to include the influence of convective flow on the system. It is demonstrated that the analysis can be used to determine feasible control strategies for operating near the steady‐state maximum rate that is stable. Two strategies were evaluated for the purpose of increasing the leaching rates, showing that an increased rate of 56% is feasible. Analysis on experimental data showed that increased rates can be achieved by controlling the biomass concentration and ferric:ferrous ion ratio at an optimum by increasing the solids loading [m/v] in the reactor. © 2011 American Institute of Chemical Engineers AIChE J, 58: 2428–2440, 2012     

细菌浸出黄铜矿的工艺影响因素研究

以黄铜矿为研究对象,研究了细菌接种量、矿石粒度、温度、pH等浸出因素对该矿样细菌浸出的影响,得到了黄铜矿最佳浸出工艺条件,为该技术的应用提供了一定的理论基础.     

Fe2(SO4)3溶液细菌辅助浸出高砷金精矿

利用摇瓶实验对纯Fe2(SO4)3溶液浸出高砷金精矿进行了研究,考察了温度及Fe3+浓度的影响,并与细菌直接浸矿进行了对比. 同时,在Fe2(SO4)3溶液中加入高密度嗜中温氧化亚铁硫杆菌、嗜中温氧化硫硫杆菌、中度嗜热西伯利亚硫杆菌,考察其对Fe2(SO4)3溶液的辅助浸出作用. 结果表明,Fe3+溶液化学浸出可迅速溶解高砷金精矿,随温度升高,浸出率先升后降,80℃时达最大;浸出前期Fe3+浓度的积累对浸出速率影响不大,初始Fe3+浓度越高As的浸出率越高,但当Fe3+浓度高于40 g/L,由于沉淀严重,浸出率降低;连续浸出情况下,Fe3+浓度可维持恒定,10 g/L的Fe3+可保持较快的矿物浸出速率. 对照实验表明,较高的矿浆浓度对浸矿菌生长繁殖有显著影响. 高密度浸矿菌可维持Fe2(SO4)3溶液中较高的Fe3+浓度并及时消除反应产生的S层的阻碍,有利于Fe2(SO4)3溶液对矿物的浸出.     

Ag+对含砷金精矿生物浸出的影响

研究了Ag+对含砷金精矿生物浸出的影响,测量了浸出液中铁、银、砷浓度及氧化还原电位(Eh)的变化,考察了Ag+对细菌密度的影响,并对浸渣进行了光谱表征. 结果表明,Ag+对含砷金精矿的生物浸出有一定的促进作用且在高浓度Fe3+条件下催化作用明显;低Ag+浓度下含砷金精矿的生物浸出率提高约10%,但Ag+浓度过高将影响细菌生长,导致浸出速率下降. Ag+催化含砷金精矿生物浸出是Ag+取代矿物表面的砷并生成Ag2S,之后被Fe3+氧化分解,重新产生Ag+,从而加速矿物的氧化分解.     

Chloride‐promoted leaching of chalcopyrite concentrate by biologically‐produced ferric sulfate

The effects of chloride ions on chalcopyrite leaching by biologically‐produced ferric sulfate solution and on the iron‐oxidizing culture were determined. Chloride ions significantly increased chalcopyrite leaching by ferric sulfate at 67 °C and 87 °C, but slowed down the leaching at 50 °C. At 90 °C, chloride at 5 g dm^?3 (0.25 g Cl^? g^?1 concentrate) increased the copper yield from 60 to 100% in approximately 2 weeks. Further increase in Cl^? concentration did not affect the leaching. Addition of chloride increased both leaching yields and iron precipitation, which shows that the passivation was not due to iron precipitation. A decreased Ag‐potential of 60 mV against an Ag/AgCl reference electrode in the presence of Cl^? indicates the accumulation of partially oxidized forms of dissolved sulfur compounds such as thiosulfate and polythionate instead of elemental sulfur and, thus, a decrease in sulfur passivation. A chloride concentration of 5 g dm^?3 did not affect the iron oxidation rate of the iron‐oxidizing culture dominated by Leptospirillum ferriphilum. Copyright © 2004 Society of Chemical Industry     

Study on the kinetics of hazardous pollutants adsorption and desorption by biomass: Mechanistic considerations

The kinetics of biosorption and desorption of lindane, diazinon and 2-chlorobiphenyl by inactive activated sludge and Rhizopus arrhizus biomass was studied. The effects of solution initial concentration, temperature and type of biomass on the observed biosorption and desorption rates were also examined. The results of the present work show that the biosorption rates are reasonably rapid, with equilibrium attained within 4 h by activated sludge and 1 h by R. arrhizus. The observed biosorption kinetics consist of a rapid initial stage followed by a slower second stage. The observed rate of organic pollutants biosorption by activated sludge during the first stage can be described by second order kinetics. The biosorption of lindane by both biomass types is reversible and the desorption process is rapid and could be described by zero order kinetics when activated sludge is used as adsorbent. The type of biomass can have a significant effect on the observed biosorption and desorption rates.     

Electrochemical behaviour of chalcopyrite in the presence of silver and Sulfolobus bacteria

The electrochemical behaviour of massive chalcopyrite electrodes has been studied in an acid medium (pH1.5) containing silver ions (0.02gdm–3Ag+) and thermophilic bacteria (68°C). Preliminary tests on particulate electrodes made from graphite, elemental sulfur and Ag2S were included to determine the electrochemical response of reactants (Ag+) and products (S° and Ag2S) associated with the dissolution of chalcopyrite in the presence of silver. Massive chalcopyrite electrodes under potential scan showed a dependence on the dissolution of the Ag2S film with both the time of contact with the silver solution and [Ag+]. As well as Ag2S, metallic silver was detected on the chalcopyrite surface. It has been demonstrated that Fe3+ and bacteria play an important role in the regeneration of the Ag2S film. The breakdown of this film is a requirement for the further dissolution of chalcopyrite. The bioleaching of chalcopyrite with thermophilic microorganisms in the presence of silver decreased the decomposition potential of the electrode and favoured its electrodissolution. Bioleaching treatment in the presence of silver ions for periods of time longer than two weeks did not improve the surface reactivity. However, in the initial stages of the process, the lower reactivity of the bioleached electrodes was probably related to a toxic effect of silver on the microorganisms.     

Cu2+, Fe2+ and Fe3+ analysis of bioleaching solutions using chronoamperometry and BDD electrode

In this work, a boron-doped diamond (BDD) electrode was evaluated for the electroanalytical determination of millimolar concentrations of Cu²⁺, Fe²⁺ and Fe³⁺ using chronoamperometry. The interfering role that each ion plays on the quantitative determination of other metal ion concentrations was also assessed. No interference from other metal ions was observed when Fe³⁺ and Fe²⁺ were analysed. By contrast, reduction of Fe³⁺ took place at the same potential where [Cu²⁺] was measured causing a minor interference to the Cu²⁺ signal. A multiple linear regression (MLR) calibration model was made for each analyte using real bioleaching samples, which demonstrated high coefficients of determination and adequate standard errors. The methods developed were used to monitor bioleaching of chalcopyrite for 4 months. The electroanalytical methods are particularly well-suited for analysing Cu²⁺, Fe³⁺ and Fe²⁺ concentration in acidic mine drainage (AMD) and bioleaching environments.     

Passivation of titanium in molybdate-containing sulphuric acid solution

The effect of molybdate ions on the passivation reaction of commercial pure (CP) Ti in sulphuric acid solution was studied by conducting an immersion test, measuring dc polarization curves and electrochemical impedance spectroscopy (EIS). It is found that the addition of molybdate in boiling sulphuric acid with concentrations higher than 10⁻³ M could greatly reduce the corrosion rate to a negligible value. dc Polarization curves showed that the passivation behaviour was strongly affected by the solution temperature as well as the concentration of molybdate ion present in the sulphuric acid. The passive film resistance (R_pf) determined by EIS was found to increase with the externally applied anodic potential and/or with the molybdate ion concentration. The increase of R_pf is mainly attributed to the thickening process of oxide film at more noble potentials.     

Electrochemical behaviour of chalcopyrite in the presence of silver and Sulfolobus bacteria

The electrochemical behaviour of massive chalcopyrite electrodes has been studied in an acid medium (pH1.5) containing silver ions (0.02gdm?3Ag+) and thermophilic bacteria (68°C). Preliminary tests on particulate electrodes made from graphite, elemental sulfur and Ag2S were included to determine the electrochemical response of reactants (Ag+) and products (S° and Ag2S) associated with the dissolution of chalcopyrite in the presence of silver. Massive chalcopyrite electrodes under potential scan showed a dependence on the dissolution of the Ag2S film with both the time of contact with the silver solution and [Ag+]. As well as Ag2S, metallic silver was detected on the chalcopyrite surface. It has been demonstrated that Fe3+ and bacteria play an important role in the regeneration of the Ag2S film. The breakdown of this film is a requirement for the further dissolution of chalcopyrite. The bioleaching of chalcopyrite with thermophilic microorganisms in the presence of silver decreased the decomposition potential of the electrode and favoured its electrodissolution. Bioleaching treatment in the presence of silver ions for periods of time longer than two weeks did not improve the surface reactivity. However, in the initial stages of the process, the lower reactivity of the bioleached electrodes was probably related to a toxic effect of silver on the microorganisms.     

Effect of supplementary cementitious materials (binder type) on the pore solution chemistry and the corrosion of steel in alkaline environments

The pore solution compositions of paste samples produced with Ordinary Portland Cement (PC), slag 25%, 50% and 75%, fly ash 30%, condensed silica fume (SF) 7%, and a ternary blend of 50% PC, 43% slag and 7% SF were determined. Not only are there significant variations in the concentration of the major cations and anions but also, and equally important from the perspective of development of the passivity of steel in solution, in the level of dissolved oxygen and redox potential.Further, the impact of changes in the pore solution chemistry of cement pastes with SCMs on the passivation and corrosion of steel was investigated with mild steel in simulated pore solutions (SPS). Sulphides and thiosulphates, typically found in slag bearing pastes, appeared to reduce the chloride threshold concentration and increase the rate of corrosion in SPS, which has potential implication for the long term performance of reinforced concrete structures.     

Electrode passivation by reaction products of the electrochemical and enzymatic oxidation of p-phenylenediamine

The electrochemical and enzymatic oxidation of p-phenylenediamine (PPD) was studied under various conditions to evaluate its reversibility and stability when used as a laccase redox mediator. In accordance with published results, PPD oxidation during cyclic voltammetry showed that a passivation occurred with cycling in static systems without laccase. Such passivation was observed both in McIlvaine and acetate buffers on glassy carbon and platinum electrodes. Our results suggest that the oxidised form of PPD reacts with other PPD molecules in their reduced state to form a polymer on the surface of the electrode. When laccase is present in solution, PPD is only found in its oxidised state and another behaviour is observed at the electrode, with the appearance of a redox couple with an E’ centered at about −25 mV vs. Ag/AgCl in 0.1 M acetate buffer. These redox waves are attributed to the formation of soluble PPD oligomers. RRDE experiments showed no passivation, meaning that in order to form a film, the reaction products from the first oxidation of PPD must be further oxidised in a slow, homogeneous reaction. Results from these experiments have a significant importance in the design of efficient enzyme-modified electrodes since PPD diffusion in the thick polymer layers used to immobilise enzymes is a much slower process than in free solution, which allows enough time for the oxidation products to further react at the electrode and to polymerise on its surface. Passivation can therefore be observed with modified electrodes, even under hydrodynamic conditions, while similar conditions will provide a reversible system on bare electrodes. An example of this consequence of the reactivity of PPD oxidation products on the mediator's reversibility is given through experiments with a modified glassy carbon RDE functionalised with a thick layer of poly(ethyleneimine) microcapsules. In such case, the cyclic voltammograms showed that the oxidation and reduction processes are broader than at a bare electrode and that higher scan rates or rotation rates must be used to avoid passivation.     

镀铬层在Na2S溶液中的耐蚀性研究

通过称量法测试了镀铬层在不同温度、不同质量分数Na2S溶液中的腐蚀速率,并采用恒电位极化法研究了镀铬层在Na2S溶液中的电化学行为,分析了各因素对镀铬层腐蚀行为的影响。研究结果表明：镀铬层在Na2S溶液中的腐蚀过程有钝化产生;同一温度条件下,提高浓度可加速镀铬层的钝化。     

碳钢在含硫水溶液中的电化学行为

采用稳态极化曲线法研究了20#碳钢在硫化钠水溶液中的电化学行为。结果表明：随着硫化钠含量的增大，腐蚀速率先增大后降低，硫化钠质量分数为2％时腐蚀速率最大；当硫化钠质量分数大于1％时，碳钢电极表面经阳极极化可以生成钝化膜；随着添加的氨水浓度的增加，加剧了碳钢的腐蚀；SO42-的添加，碳钢在硫化钠水溶液中的腐蚀速率基本没影响；随着C1-浓度的增加，碳钢在硫化钠水溶液中的腐蚀速率增大；同时，C1-可以阻止碳钢电极表面钝化性能。     

The anodic properties of FeCr alloys in organic solvents

The influence of the water concentration on the passivation of FeCr alloys in sulfuric acid—organic solvents solutions has been investigated with the aid of potentiodynamic curves of the anodic polarisation. The dependence of the passivation potential or the break potential from the chromium concentration in the alloys and the water concentration in the solution has been determined. At low water concentrations the passivation potential decreases with increasing water content. This fact can be accounted for by the strengthening of the electrolyte structure and the resulting decrease of the solvolytic capabilities of solvents. In this range of water concentrations the salt—hydroxid type of the film is formed on the surface of the alloy. The increasing concentration of chromium in the alloy facilitates the formation of the films. At high water concentrations, when water molecules are used for the solvation of cations, only the alloys containing more than 18 per cent of Cr can form a stable anodic film below the passivation potential of iron. The passivation potential for the alloys which contain lower amounts of chromium has been found to increase as the water concentration increases. This is due to the fact that Fe⁺² compounds from the anodic layer are exhibiting higher solubility in the solutions.     

Electrochemical Recognition of Metalloproteins by Bromide-modified Silver Electrode - A New Method

A bromide–modified silver electrode is reported, in the present study, to catalyze the redox reactions of metalloproteins. This study describes that the bromide ions show very good redox behavior with silver electrode. The cathodic and anodic peak potentials were related to the concentration of bromide ions involved in making bromide-modified silver electrode. The electrode reaction in the bromine solution was a diffusion-controlled process. Positive potential shift of the bromide ions was seen when different proteins were added to the solution using a silver electrode. New cathodic and anodic peaks were observed at different potential ranges for myoglobin, cytochrome c and catalase. A linearly increasing cathodic peak current of bromide ions was seen when the concentration of superoxide dismutase was increased in the test solution. However, no change for albumin was observed when its concentration was increased in the test solution. Present data proves our methodology as an easy-to-use analysis for comparing the redox potentials of different metalloproteins and differentiating the metallo-from non-metalloproteins. In this study, we introduced an interesting method for bio-electrochemical analyses.     

Inhibition of hematite on acid mine drainage caused by chalcopyrite biodissolution

Even though biodissolution of chalcopyrite is considered to be one of the key contributors in the formation of acid mine drainage (AMD), there are few studies to control AMD by inhibiting chalcopyrite biodissolution. Therefore, a novel method of using hematite to inhibit chalcopyrite biodissolution was proposed and verified. The results indicated that chalcopyrite biodissolution could be significantly inhibited by hematite, which consequently decreased the formation of AMD. In the presence of hematite, the final biodissolution rate of chalcopyrite decreased from 57.9% to 44.4% at 20 day. This in turn suggested that the formation of AMD was effectively suppressed under such condition. According to the biodissolution results, mineral composition and morphology analyses, and electrochemical analysis, it was shown that hematite promoted the formation and accumulation of passivation substances (jarosite and Cu_2-xS) on chalcopyrite surface, thus inhibiting the biodissolution of chalcopyrite and limiting the formation of AMD.