Control method of chalcopyrite passivation in bioleaching

Passivation is a common phenomenon on the surface of chalcopyrite in the process of bioleaching. The ordinary leaching and strengthening leaching by adding glass beads were carried out. The results show that the passivation of chalcopyrite was greatly weakened in strengthening leaching due to the change of leaching conditions. The copper leaching efficiency was increased from 50% to 89.8% through adding beads. The SEM and X-ray diffraction （XRD） analyses illustrate that there are few jarosite precipitates and weak passivation on the surface of chalcopyrite in strengthening leaching. In contrast, there are thick and compact jarosite precipitate and obvious passivation in ordinary leaching, which hinders further dissolution of chalcopyrite.

Relationship and effect of redox potential,jarosites and extracellular polymeric substances in bioleaching chalcopyrite by acidithiobacillus ferrooxidans

The changes of pH,redox potential,concentrations of soluble iron ions and Cu^2＋ with the time of bioleaching chalcopyrite concentrates by acidithiobacillus ferrooxidans were investigated under the different conditions of initial total-iron amount as well as mole ratio of Fe（III） to Fe（II） in the solutions containing synthetic extracellular polymeric substances （EPS）.When the solution potential is lower than 650 mV （vs SHE）,the inhibition of jarosites to bioleaching chalcopyrite is not vital as EPS produced by bacteria can retard the contamination through flocculating jarosites even if concentration of Fe（III） ions is up to 20 g/L but increases with increasing the concentration of Fe（III） ions;jarosites formed by bio-oxidized Fe3＋ ions are more easy to adhere to outside surface of EPS space on chalcopyrite;the EPS layer with jarosites acts as a weak diffusion barrier to further rapidly create a high redox potential of more than 650 mV by bio-oxidizing Fe^2＋ ions inside and outside EPS space into Fe^3＋ ions,resulting in a rapid deterioration of ion diffusion performance of the EPS layer to inhibit bioleaching chalcopyrite severely and irreversibly.

Adsorption and activation of copper ions on chalcopyrite surfaces:A new viewpoint of self-activation

The adsorption behaviors of copper ions on chalcopyrite surfaces were investigated based on zeta potential measurements, X-ray photoelectron spectroscopy, copper ion adsorption experiments, first-principles calculations, and Hallimond tube cell flotation experiments. The results show that copper ions activate the chalcopyrite as a result of the interactions between copper ions and sulfur on the chalcopyrite surface. This adsorption increases the flotation rate under certain conditions, and this is beneficial for the flotation of chalcopyrite. The copper ions in the flotation pulp are mainly derived from surface oxidation dissolution and the release of fluid inclusions, and these effects enable chalcopyrite to be activated.

Comparison of electrochemical dissolution of chalcopyrite and bornite in acid culture medium

The electrochemical dissolution process of chalcopyrite and bornite in acid bacteria culture medium was investigated by electrochemical measurements and X-ray photoelectron spectroscopy（XPS） analysis. Bornite was much easier to be oxidized rather than to be reduced, and chalcopyrite was difficult to be both oxidized and reduced. The relatively higher copper extraction of bornite dissolution can be attributed to its higher oxidation rate. Covellite（CuS） was detected as the intermediate species during the dissolution processes of both bornite and chalcopyrite. Bornite dissolution was preferred to be a direct oxidation pathway, in which bornite was directly oxidized to covellite（CuS） and cupric ions, and the formed covellite（CuS） may inhibit the further dissolution. Chalcopyrite dissolution was preferred to be a continuous reduction-oxidation pathway, in which chalcopyrite was initially reduced to bornite, then oxidized to covellite（CuS）, and the initial reduction reaction was the rate-limiting step.

Surface species of chalcopyrite during bioleaching by moderately thermophilic bacteria

X-ray diffraction （XRD） and X-ray photoelectron spectroscopy （XPS） analyses were carried out to investigate the surface species and interfacial reactions during bioleaching of chalcopyrite by different strains of moderately thermophilic bacteria （45 °C）. Results show that monosulfide （CuS）, disulfide （S22？）, polysulfide （Sn2？）, elemental sulfur （S0） and sulfate （SO42？） are the main intermediate species on the surface of chalcopyrite during bioleaching byA. caldus,S. thermosulfidooxidans andL. ferriphilum. The low kinetics of dissolution of chalcopyrite inA. caldus can be mainly attributed to the incomplete dissolution of chalcopyrite and the passivation layer of polysulfide. Polysulfide and jarosite should be mainly responsible for the passivation of chalcopyrite in bioleaching byL. ferriphilumorS. thermosulfidooxidans. However, elemental sulfur should not be the main composition of passivation layer of chalcopyrite during bioleaching.

Sulfur composition on surface of chalcopyrite during its bioleaching at 50°C

The composition of passive layer of chalcopyrite was investigated by X-ray photoelectron spectroscopy（XPS）, accompanied with cyclic voltammetry（CV）. The leaching experiment shows that the extraction rates of Cu with leaching for 30 d by sterile control and microorganisms are 4.0% and 21.5%, respectively. In comparison, 3.8% and 10.5% Fe are leached by sterile control and microorganisms, respectively. The results of XPS studies suggest that Fe atoms dissolve preferentially from the chalcopyrite lattice, and disulfide（S22-）, polysulfide（Sn2-） and elemental sulfur（S0） are identified on the chalcopyrite surfaces leached by sterile control and microorganisms. Additionally, sulfate（SO42-） is detected on the chalcopyrite surfaces leached by microorganisms, and most of it probably originates from jarosite. The analysis of CV results reveals that metal-deficient sulfide（Cu1-xFe1-yS2-z, yx） and elemental sulfur（S0） passivate the surface of chalcopyrite electrode. The elemental sulfur and/or jarosite coating on the chalcopyrite surface may have impact on the leaching process; however, the disulfide, polysulfide or metal-deficient sulfide plays a more key role in the chalcopyrite leaching.

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.

Agglomeration−aggregation and leaching properties of mechanically activated chalcopyrite

The effect of mechanical activation on the granulometric parameters,microstructure,and leaching efficiency of chalcopyrite was evaluated,and the occurrence/transition of agglomeration and aggregation was discussed.The results showed that in 8 h of milling treatment,the agglomeration and the microstructure did not affect each other.However,with prolonging milling time,the crystallite size tended to reach a saturation value,and the stagnating microstructural changes led to the replacement of agglomeration by aggregation.The leaching results indicated that the mechanical activation can strongly enhance the reactivity of chalcopyrite and the hindering effect of aggregation on leaching was considerably greater than that of agglomeration.Consequently,after 8 h of milling,the maximum Cu leaching rate of 80.13%was achieved after 4 h of acid leaching.

Improving of copper extraction from chalcopyrite by using NaCl

The addition of NaCl in the ammonium persulfate-APS(as an oxidant)leaching was investigated.APS has some advantages compared with conventional oxidants and its standard redox potential(E°)is2.0V.Effect of six parameters such as NaCl concentration,APS concentration,temperature,time,liquid–solid ration(L/S),and stirring speed on the leaching behavior was studied.Results showed that metals extraction increased with increasing of NaCl concentration,APS concentration,leaching temperature(up to333K),and L/S ratio.During oxidative leaching of sulfide minerals,the occurrence of elemental sulfur layer on particle surface is known as primary problem that causes low metal extraction.According to the results,the passivation effect of sulfur layer and low dissolution problems can be eliminated in the presence of chloride ions.Copper and iron extraction yields were obtained as75%and80%,respectively under leaching conditions as follows:APS concentration250g/L;NaCl concentration150g/L;time180min;temperature333K;stirring speed400r/min;and L/S250mL/g.

Effect of sodium pyrophosphate on the flotation separation of chalcopyrite from galena

The effect of sodium pyrophosphate （SPH） on the separation of chalcopyrite from galena was examined through flotation, adsorption, electrokinetic studies and infrared spectral analysis. Differential flotation tests indicate that satisfactory separation can be achieved within the pH range from 2.5 to 6 using SPH to depress the galena, but not the chalcopyrite when O-isopropyl-N-ethyl thionocarbamate （IPETC） is used as the collector. The electrophoretic mohilities of both the minerals dramatically become negatively charged following SPH adsorption in the pH range from 2.5 to 12, The infrared spectral analysis suggests that chemical adsorption occurs on galena surface treated by SPH, indicating that a chelate complex has formed. At weakly acidic pH values, the adsorption density of IPETC onto galena is significantly reduced in the presence of SPH. However, the amount of IPETC adsorbed onto chalcopyrite almost remains at the same level. Since the observed adsorption density of IEPTC onto chalcopyrite is quite high compared to galena, the observed flotation results are explained. A possible mechanism for the interaction between the two sulphide minerals and SPH is discussed.

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.

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.

Electrochemical mechanism and flotation of chalcopyrite and galena in the presence of sodium silicate and sodium sulfite

The electrochemical mechanism involved in the selective separation of chalcopyrite from galena was investigated by flotation and electrochemical methods in the presence of sodium sulfite and sodium silicate,respectively,as a single depressant and their mixture as a combined depressant.Flotation tests revealed that the floatability of chalcopyrite was unaffected by depressants and its recovery remained constant(>80%)within the studied dosage range.Galena flotation was severely depressed with descending depressing order as follows:combined depressant﹥sodium silicate﹥sodium sulfite.Electrochemical analysis confirmed the high affinity of depressants on the galena surface,resulting in the formation of hydrophilic species,such as lead sulfite,lead sulfate,and lead orthosilicate.The oxidation of chalcopyrite surface and depressants did not exhibit any signals;conversely,the self-oxidation of chalcopyrite was depressed.The results of cyclic voltammograms well agreed with flotation results,demonstrating that chalcopyrite primarily reacted with the collector O-isopropyl-N-ethyl thionocarbamate and that galena mostly reacted with depressants.

Cu-state evolution during leaching of bornite at 50 ℃

The bioleaching of bornite with mixed moderately thermophilic culture at 50 °C was investigated. The intermediary species formed during the leaching of bornite were characterized by XRD and XPS. In addition, the evolution of Cu-state during leaching of bornite was further studied by applying φh–p H diagram and cyclic voltammetry. The results showed that the bornite was more likely to be leached at high redox potential. Furthermore, the intermediary sulfides, such as isocubanite, covellite, chalcopyrite, disulfide, and polysulfide, were formed in the course of bornite dissolution. The Cu 2 p photoelectron spectrum revealed that the valence of copper in bornite and intermediary sulfide formed in the dissolution of bornite is ＋1. The bornite and chalcopyrite can be converted into each other, and both can be further converted to covellite and/or chalcocite.

Catalytic effect of visible light and Cd^2+on chalcopyrite bioleaching

The effects of visible light and Cd^2+ion on chalcopyrite bioleaching in the presence of Acidithiobacillus ferrooxidans(A.ferrooxidans)were studied by scanning electron microscopy(SEM),synchrotron radiation X-ray diffraction(SR-XRD),and X-ray photoelectron spectroscopy(XPS).The results of bioleaching after 28 days showed that the copper dissolution increased by 4.96%with only visible light,the presence of Cd2+alone exerted slight inhibition effect on chalcopyrite dissolution and the concentration of dissolved copper increased by 14.70%with visible light and 50 mg/L Cd^2+.The results of chemical leaching showed that visible light can promote the circulation of iron.SEM results showed that Cd^2+promoted the attachment of A.ferrooxidans on chalcopyrite surface under visible light.SR-XRD and XPS results indicated that visible light and Cd^2+promoted chalcopyrite dissolution,but did not inhibit the formation of passivation.Finally,a model of synergistic catalysis mechanism of visible light and Cd2+on chalcopyrite bioleaching was proposed.

Flotation behaviors and mechanisms of chalcopyrite and galena after cyanide treatment

Adsorbing tests between CN? and chalcopyrite or galena were conducted firstly, and then flotation tests of the twocyaniding minerals were investigated in butyl xanthate (BX) system. Results showed that the interaction between CN? and the twomineral surfaces were both chemical adsorption and can be described by the Langmuir adsorption isotherm model. In the optimumcondition of pH 6.5 and 4.0 mg/L BX, the recovery of cyaniding chalcopyrite and galena reached 82.1% and 63.9%, respectively. BXimproved the hydrophobicity of the surfaces of the two minerals, although CN? reduced the contact angle on the surface of minerals.The inhibitory effect of CN? on chalcopyrite far outweighed galena. Electrostatic adsorption exists in the interaction between BX andthe surface of galena after cyanide treatment in the pH range of 4.2?8.4, while the interactions between BX and the surface ofchalcopyrite after cyanide treatment is chemical adsorption.

Preservation of moderately thermophilic culture by freeze drying and frozen preservation way and effect on subsequent bioleaching of chalcopyrite

Freeze drying and frozen preservation way was used to preserve a moderately thermophilic culture for bioleaching of chalcopyrite concentrate.After preservation of 15 months,the cell viability rate decreases to 22% with a cell density of 7×107 mL-1.When the growth time was extended from 8 days to 14 days,cell density would increase in a large scale to about 3×108 mL-1.In the bioleaching experiments,unpreserved and preserved cultures were compared for dissolving chalcopyrite concentrate.Before 44 days,the unpreserved culture can reach a high copper extraction of about 17.4 g/L.While the preserved culture shows a rather low copper extraction,which is only 9.7 g/L.When the bioleaching time was extended to 80 days,copper extraction by preserved culture increases remarkably,and the concentration of copper finally achieves up to 18.3 g/L.On the other hand,copper extraction by the unpreserved culture does not show remarkable increase from 44th to the 80th day,and finally the total copper extraction is 19.8 g/L.As a result,total copper extraction in 80 days by preserved culture approaches that by unpreserved culture and freeze drying and frozen preservation even after 15 months does not bring much decrease of bioleaching ability.

Effect of temperature,oxygen partial pressure and calcium lignosulphonate on chalcopyrite dissolution in sulfuric acid solution

The pressure leaching mechanism of chalcopyrite was studied by both leaching tests and in-situ electrochemical measurements. The effects of leaching temperature, oxygen partial pressure, and calcium lignosulphonate, on copper extraction and iron extraction of chalcopyrite pressure leaching were investigated. The leaching rate is accelerated by increasing the leaching temperature from 120 to 150 ℃ and increasing oxygen partial pressure to 0.7 MPa. The release of iron is faster than that of copper due to the formation of iron-depleted sulfides. Under the optimal leaching conditions without calcium lignosulphonate, the copper and iron extraction rates are 79% and 81%, respectively. The leaching process is mixedly controlled by surface reaction and product layer diffusion with an activation energy of 36.61 k J/mol. Calcium lignosulphonate can effectively remove the sulfur passive layer, and the activation energy is 45.59 k J/mol, suggesting that the leaching process with calcium lignosulphonate is controlled by surface chemical reactions. Elemental sulfur is the main leaching product, which is mixed with iron-depleted sulfides and leads to the passivation of chalcopyrite. Electrochemical studies suggest that increasing the oxygen partial pressure leads to increasing the cathodic reaction rate and weakening the passivation of chalcopyrite.

Simultaneous electrogenerative leaching of chalcopyrite concentrate and MnO_2

In order to enhance the electrogenerative leaching rate of chalcopyrite concentrate reasonably, the principle of generative process was applied to simultaneous leaching of chalcopyrite concentrate and MnO2. The results show that Cu^2＋ and Mn^2＋ in addition to electrical energy could be acquired in the simultaneous electrogenerative leaching process. The leaching cell has the open circuit potential of about 1.0 V and gains quantity of electricity of about 700 C. The optimum leaching rates of Cu^2＋ and Mn^2＋ are 23.10% and 22.1%, respectively after electrogenera- tive leaching for about 10 h under the present conditions.