Effect of pH values on extracellular protein and polysaccharide secretions of Acidithiobacillus ferrooxidans during chalcopyrite bioleaching

The effect of pH values on the extracellular protein and polysaccharide secretions of Acidithiobacillus ferrooxidans was comparatively investigated in different phases of bacterial growth during chalcopyrite bioleaching. The results indicate that the extracellular protein is always more than the extracellular polysaccharide secreted by attached cells on the chalcopyrite, on the contrary, and is always less than the extracellular polysaccharide secreted by free cells in the solution at bacterial adaptive phase, logarithmic phase and stationary phase whenever pH value is at 1.0, 1.5, 2.0 or 2.5; free cells are mainly through the secretion of extracellular polysaccharide rather than the extracellular protein to fight against disadvantageous solution environment, such as high concentration of metal ions and unsuitable pH solution; both amounts of polysaccharide and protein secreted by attached cells are mainly positively related to the solution acidity rather than the total concentration of soluble metal ions. The experimental results imply that bacteria are mainly through secreting more extracellular polysaccharide to fight against disadvantageous environment and the extracellular protein perhaps plays an important role in oxidation？reduction reactions in the bioleaching system.

Bioleaching of low-grade copper sulfide ores by Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans

The grown conditions of Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans were investigated,and then experiments were conducted to research the bioleaching behaviors of crude ore of copper sulfide and hand-picked concentrates of chalcopyrite by Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans.The experimental results show that the bacteria grow best when the temperature is(30±1) °C and the pH value is 2.0.The bacteria concentration is 2.24×107 mL-1 in this condition.It is found that the copper extraction yield is affected by the inoculum size and the pulp density and the extraction yield increases as the inoculum size grows.The bioleaching rates reach their highest point in sulfide copper and chalcopyrite with a pulp density of 5% and 10%,respectively.Column flotation experiments of low-grade copper sulfide ores show that the bioleaching recovery reaches nearly 45% after 75 days.

Bioleaching and electrochemical properties of chalcopyrite by pure and mixed culture of Leptospirillum ferriphilum and Acidthiobacillus thiooxidans

The bioleaching of chalcopyrite was investigated using a pure and mixed culture consisting of iron-oxidizing Leptospirillum ferriphilum （L. ferriphilum） and sulfur-oxidizing Acidthiobacillus thiooxidans （.4. thiooxidans）. The electrochemical tests were conducted to investigate the bioleaching behavior of chalcopyrite by various bacteria. Bioleaching efficiency of chalcopyrite in mixed culture is higher than that in the pure culture of L.ferriphilum alone. The iron-oxidizing L.ferriphilum plays a dominant role during bioleaching of chalcopyrite in the mixed culture of L. ferriphilum and A. thiooxidans. During bioleaching, certain values of redox potential are beneficial to the decomposition of chalcopyrite. Jarosite and sulfur are observed as products of bioleaching. The addition of A. thiooxidans during leaching by L. ferriphilum can change the electrochemical control steps of leaching. The corrosion current density is substantially promoted in the culture involving bacteria, especially in the mixed culture.

Relationships among bioleaching performance, additional elemental sulfur, microbial population dynamics and its energy metabolism in bioleaching of chalcopyrite

To estimate the relationships among bioleaching performance, additional elemental sulfur （S0）, microbial population dynamics and its energy metabolism, bioleaching of chalcopyrite by three typical sulfur- and/or iron-oxidizing bacteria, Acidithiobacillus ferrooxidans, Leptospirillum ferriphilum and Acidithiobacillus thiooxidans with different levels of sulfur were studied in batch shake flask cultures incubated at 30 °C. Copper dissolution capability （71%） was increased with the addition of 3.193 g/L S0, compared to that （67%） without S0. However, lower copper extraction was obtained in bioleaching with excessive sulfur. Microbial population dynamics during chalcopyrite bioleaching process was monitored by using PCR-restriction fragment length polymorphism （PCR-RFLP）. Additional S0 accelerated the growth of sulfur-oxidizing bacteria, inhibited the iron-oxidizing metabolism and led to the decrease of iron-oxidizing microorganisms, finally affected iron concentration, redox potential and bioleaching performance. It is suggested that mixed iron and sulfur-oxidizing microorganisms with further optimized additional S0 concentration could improve copper recovery from chalcopyrite.

Mechanism of bioleaching chalcopyrite by Acidithiobacillus ferrooxidans in agar-simulated extracellular polymeric substances media

The mechanism of leaching chalcopyrite by Acidithiobacillus ferrooxidans （,4. ferrooxidans） in agar-simulated extracellular polymeric substances （EPS） media was investigated. The results indicate that bacterial EPS can release H＋ and concentrate Fe3＋; Fe2＋ is movable between agar-simulated EPS phase and bulk solution phase, but it is difficult for Fe3＋ to move due to its hydroxylation and EPS complex action; A. ferrooxidans first prefer Fe2＋ as energy to metabolize compared with chalcopyrite, and a suitable simulated EPS environment for bacterial living is at about pH 1.8; the iron precipitates and jarosites formed by a lot of biologically oxidized Fe3 cover the simulated EPS easily and form an impermeable deposit acting as a limited barrier of ion transport that attenuates the aggressiveness of the bioleaching attack. The EPS layer blocked by iron precipitates or jarosites is responsible for the chalcopyrite passivation.

Comparison of desulfurization kinetics of copper oxide sorbent

Desulfurization experiments of CuO, γ-Al2O3 and CuO/γ-Al2O3 were made in simulated flue gas by means of thermogravimetric analysis. It is found that reaction activities of CuO supported on γ-Al2O3 could be highly improved. Desulfurization kinetics of CuO/γ-Al2O3 was studied in the temperature range of 250 °C-400 °C and SO2 concentration of 0.1%-0.9%. The experimental data were tested and compared with kinetics models of volume reaction model(VRM), grain size model(GSM), random pore model(RPM) and pore-blocking model(PBM). Correlation analysis shows that VRM and RPM models do not fit experimental data well. GSM contradicts with the changes in the physical and chemical properties of Cu O/γ-Al2O3 as the desulfurization proceeds. It is found that PBM is consistent with the change of pore structure of CuO/γ-Al2O3 sorbent during desulfurization process and predicts the conversion-time curves of the sorbent well. Meanwhile, kinetics parameters are obtained and discussed.

Kinetics of the Chlorination of Copper （I） Sulphide by Calcium Chloride in the Presence of Oxygen

The chemism of the chlorination of copper （I） sulphide by calcium chloride in the presence of oxygen has been determined based on the thermodynamic analysis in the Cu2S-CaCl2-O2 system as well as characterization of used raw materials and obtained products. The influence of temperature （from 473 to 773 K）, time （from 2 to 120 min）, oxygen flow （from 20 to 100 L/h） and calcium chloride quantity （from 5 to 40%） on the chlorination degree has been investigated. Kinetic analysis and the activation energy values of 20.89 kJ/mol showed that the chlorination of copper （I） sulphide by calcium chloride in the presence of oxygen is diffusion controlled.

Iron and copper recovery from copper slags through smelting with waste cathode carbon from aluminium electrolysis

To recover metal from copper slags,a new process involving two steps of oxidative desulfurization followed by smelting reduction was proposed in which one hazardous waste(waste cathode carbon)was used to treat another(copper slags).The waste cathode carbon is used not only as a reducing agent but also as a fluxing agent to decrease slag melting point.Upon holding for 60 min in air atmosphere first and then smelting with 14.4 wt%waste cathode carbon and 25 wt%CaO for 180 min in high purity Ar atmosphere at 1450℃,the recovery rates of Cu and Fe reach 95.89%and 94.64%,respectively,and meanwhile greater than 90%of the fluoride from waste cathode carbon is transferred into the final slag as CaF_(2) and Ca_(2)Si_(2)F_(2)O_(7),which makes the content of soluble F in the slag meet the national emission standard.Besides,the sulphur content in the obtained Fe-Cu alloy is low to 0.03 wt%.

Formation of jarosite and its effect on important ions for Acidithiobacillus ferrooxidans bacteria

The precipitation of jarosite adversely affects the bio-leaching of copper sulfides in the Sarcheshmeh heap bio-leaching process. The variables of the initial concentration of ferrous iron in the growth medium, pH, and temperature were examined in the laboratory to determine how they affect the precipitation of jarosite in the presence of Acidithiobacillus ferrooxidans bacteria. It was found that the maximum ferric precipitate occurred at a ferrous sulfate concentration of 50 g/L, a temperature of 32 ℃, and an initial pH value of 2.2. The effects of the precipitation of ferric iron on the quantities of ions that are important for A. ferrooxidans bacteria in aqueous phase, i.e., ferric, sulfate, potassium, phosphate, and magnesium ions, also were assessed. The results showed relatively similar patterns for the ferric and potassium ions, and then reason might have been the co-precipitation of these ions as constituent elements of jarosite mineral. At pH values greater than 1.6, the solubility of phosphate ions decreased dramatically due to the co-precipitation of phosphate ions with the jarosite precipitate and due to the significant growth rate of A. ferrooxidans bacteria in this pH range. Due to the dissolution of a gangue constituent in the ore, the magnesium levels increased in the first few days of the bio-leaching process;thereafter, it decreased slightly.

Bioleaching of a kind of alkaline mixed copper oxide and sulphide mineral

We conducted two-stage acidification-bioleaching experiments to probe the feasibility of bioleaching for a kind of mixed alkaline copper oxide and sulphide mineral. We used the uniform design method for data analysis and experimental optimization, with initial pH value, pulp density, inoculation of bacteria and ferrous iron concentration selected as the influential factors. Polynomial regression shows that the four factors sequentially influence the copper recovery by 14.430%, 8.555%, 1.982% and 3.895%. Acid equilibrium in the bioleaching system is mainly influenced by alkaline gangue content, chemical reactions and bacterial activity. A maximal portion of refractory copper extracted reaches 71.08%. The dynamic analysis of copper recovery indicates that bioleaching goes through a lag leaching phase, prime leaching phase and leaching stationary phase corresponding to the growth phases of bacteria. Compared with the predicted value of 80.87%, the confirmatory experiment observes a 78.21% copper recovery under the optimal conditions of pH of 1.5, pulp density of 5%, bacteria inoculation of 30% and initial ferrous iron concentration of 9 g L-1. Results suggest that bioleaching is technically feasible to improving total copper recovery.

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.

Ore genesis of Badi copper deposit, northwest Yunnan Province, China： evidence from geology, fluid inclusions, and sulfur, hydrogen and oxygen isotopes

The Badi copper deposit is located in Shangjiang town, Shangri-La County, Yunnan Province. Tectonically, it belongs to the Sanjiang Block. Vapor-liquid two-phase fluid inclusions, CO2-bearing fluid inclusions, and daugh- ter-beating inclusions were identified in sulfide-rich quartz veins. Microthermometric and Raman spectroscopy studies revealed their types of ore-forming fluids： （1） low-tem- perature, low-salinity fluid; （2） medium-temperature, low salinity CO2-bearing; and （3） high-temperature, Fe-rich, high sulfur fugacity. The δ^18O values of chalcopyrite- bearing quartz ranged from 4.96‰ to 5.86%0, with an average of 5.40%0. The δD values of ore-forming fluid in equilibrium with the sulfide-bearing quartz were from - 87‰ to - 107‰, with an average of - 97.86%0. These isotopic features indicate that the ore-forming fluid is a mixing fluid between magmatic fluid and meteoric water. The δ^34S values of chalcopyrite ranged from 13.3‰ to 15.5‰, with an average of 14.3‰. Sulfur isotope values suggest that the sulfur in the deposit most likely derived from seawater. Various fluid inclusions coexisted in the samples; similar homogenization temperature to different phases suggests that the Badi fluid inclusions might have been captured under a boiling system. Fluid boiling caused by fault activity could be the main reason for the mineral precipitation in the Badi deposit.

Copper/cuprous sulfide electrode: preparation and performance

Cuprous sulfide （Cu2S） is a direct band-gap p-type semiconductor with excellent ionic/electronic hybrid conductivity. Alt- hough Cu/Cu2S/sulfide or polysulfide system is adopted as counter electrode of quantum-dots-sensitized solar cells （QDSSC）, the electrode process is seldom reported. Here, the electrochemical growth of Cu2S film on a copper （Cu） surface, the redox behaviors of sulfide and polysulfide, and the all-in-solid charge-transfer properties of Cu2S film are investigated. It is clarified that the copper electrode simultaneously undergoes an activated process, a membrane growth process, and a redox phase transformation process. The solid charge-transfer capability of CuzS is quantified with a high exchange-current density of 2.27 A/cm2, which elucidates that the Cu/CuzS electrode is a qualified material for counter electrodes of QDSSC. These results aid understanding of the physicochemical mechanism of QDSSC with a polysulfide electrolyte and Cu/Cu2S counter electrode.

Highly efficient Cu_(2)ZnSn(S,Se)_(4) bifacial solar cell via a composition gradient strategy through the molecular ink

The use of transparent conducting oxide(TCO)as a substrate in Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)thin-film solar cells allows for advanced applications,such as bifacial,semitransparent,and tandem solar cells with the capability to increase power density generation.However,the efficiency of this kind of solar cell is still below 6% based on the low-cost solution process.In this work,we develop a composition gradient strategy and demonstrate a 6.82% efficient CZTSSe solar cell on F:SnO_(2)(FTO)substrate under the ambient condition.The composition gradient is realized by simply depositing the precursor inks with different Zn/Sn ratios.To verify that the high performance of the solar cell is attributed to the composition gradient strategy rather than the sole change of the Zn/Sn ratio,devices based on absorbers with varied Zn/Sn ratios are fabricated.Furthermore,the structure and surface morphology of the CZTSSe films with/without composition gradients are examined.The presence of elemental gradient through the depth of the CZTSSe films before and after annealing is confirmed by secondary ion mass spectroscopy analysis.It is found that the composition gradient enhances the crystallinity of the absorber,reduces the surface roughness as well as device parasitic losses,contributing to a higher fill factor,open-circuit voltage,and conversion efficiency.

Electrocatalytic evolution of oxygen on NiCu particles modifying conductive alumina/nano-carbon network composite electrode

In this paper, a novel electrically conductive alumina/nano-carbon network (NCN) composite material was used as an electro- catalyst carrier. A NiCu/Al2O3 /NCN composite electrode was prepared by electrodepositing NiCu particles onto the surface of the conductive alumina/NCN composite. Morphology, composition, crystalline structure and electrochemical properties of the NiCu/Al2O3 /NCN composite electrode were investigated. The results showed that NiCu particles can be deposited onto the surface of the alumina/NCN composite by a coelectrodeposition method. NiCu particles in the form of solid solution with face-centered cubic (fcc) structure were relatively uniformly distributed over the carbon layer of the conductive ceramic between alumina grains. As-resulted NiCu/Al2O3 /NCN composite electrode had a remarkably enhanced electrochemical activity and high stabilization for oxygen evolution reaction, which indicated its potential application with enhanced performance to oxygen evolution reaction (OER). Moreover, based on the electrochemical measurement, the mechanism of the OER on the NiCu/Al2O3 /NCN composite electrode was discussed.