Growth of covellite crystal onto azurite surface during sulfurization and its response to flotation behavior

In this work,the growth of copper sulfide crystal onto azurite surfaces during sulfurization and its response to flotation are investigated.Filed emission scanning electron microscopy-energy dispersive X-ray spectroscopy(FESEM) and X-ray diffraction(XRD) studies confirmed that the sulfurization of azurite is not limited to the mineral surface,but rather penetrates into the bulk to form covellite crystal(synCuS),creating favorable conditions for the stable adsorption of xanthate and greatly promoting the azurite flotation.Additionally,as demonstrated by X-ray photoelectron spectroscopy(XPS) and time of flight secondary ion mass spectrometry(TOF-SIMS) analyses,a redox reaction occurred during this process,and Cu(Ⅱ) onto the mineral surface was reduced to Cu(Ⅰ).Correspondingly,reduced S^(2-) was oxidized to(S_(2))^(2-),(S_n)^(-2),and even to deeper oxidation state S~0,(S_(x)O_(y))^(n-) and SO_(4)^(2-).Excess sodium sulfide strengthens copper sulfide to form onto the azurite surface,and provides enough raw material for crystal copper sulfide to grow,resulting in the formation of "flake-like" covellite with a better crystallinity.However,the floatability of azurite decreased dramatically under this condition,because the generated massive colloidal copper sulfide in flotation pulp deteriorates the flotation environment,resulting in a decreased effective adsorption of collector onto azurite surfaces.

Electrochemical Characteristics of Natural Mineral Covellite

Electrochemical characteristics of covellite (CuS) are of importance from flotation and metallurgical point of view, as well as due to its potential application in solid state solar cells and in photocatalytic reactions. Also, the compound CuS appears as an intermediary product or a final product in electrochemical oxidation reactions of chalcocite (Cu2S) which exhibits supercapacitor characteristics. Natural copper mineral covellite has been investigated in inorganic sulfate acid electrolytes, as well as in strong alkaline electrolyte. Physical properties of covellite were characterized by X-ray diffraction (XRD) and the active surface was examined by optical and electron microscopy (EM) before and after oxidation in galvanostatic regime. Different electrochemical methods (galvanostatic, potentiostatic, cyclic voltammetry and electrochemical impedance spectroscopy - EIS) have been used. The capacitance of around 21 Fcm-2 (geometric area), serial resistance of about 90 Ωcm2 and leakage resistance of about 1200 Ωcm2 have been measured in 1 M H2SO4. The addition of cupric ions in sulfate electrolyte leads to the significant increasing of the capacitance, but having the increase of self-discharge as a negative side phenomenon. The capacitance of around 6.7 Fcm-2 (geometric area), serial resistance of about 80 Ωcm2 and leakage resistance of about 380 Ωcm2 have been measured in 6 M KOH.

Effects of bacterially produced precipitates on the metabolism of sulfate reducing bacteria during the bio-treatment process of copper-containing wastewater

A large volume of bacterially produced precipitates are generated during the bio-treatment of heavy metal wastewater.The composition of the bacterially produced precipitates and its effects on sulfate reducing bacteria (SRB) in copper-containing waste stream were evaluated in this study.The elemental composition of the microbial precipitate was studied using electrodispersive X-ray spectroscopy (EDX),and it was found that the ratio of S:Cu was 1.12.Combining with the results of copper distribution in the SRB metabolism culture,which was analyzed by the sequential extraction procedure,copper in the precipitates was determined as covellite (CuS).The bacterially produced precipitates caused a decrease of the sulfate reduction rate,and the more precipitates were generated,the lower the sulfate reduction rate was.The particle sizes of bacterially generated covellite were ranging from 0.03 to 2 m by particles size distribution (PSD) analysis,which was smaller than that of the SRB cells.Transmission electron microscopy (TEM) analysis showed that the microbial covellite was deposited on the surface of the cell.The effects of the microbial precipitate on SRB metabolism were found to be weakened by increasing the precipitation time and adding microbial polymeric substances in later experiments.These results provided direct evidence that the SRB activity was inhibited by the bacterially produced covellite,which enveloped the bacterium and thus affected the metabolism of SRB on mass transfer.