Electronic structures of monoclinic and hexagonal pyrrhotite were studied using density functional theory method,together with their flotation behavior. The main contribution of monoclinic pyrrhotite is mainly from Fe...Electronic structures of monoclinic and hexagonal pyrrhotite were studied using density functional theory method,together with their flotation behavior. The main contribution of monoclinic pyrrhotite is mainly from Fe 3d, while that of hexagonal pyrrhotite is from Fe 3d, Fe 3p and S 3s. The hexagonal pyrrhotite is more reactive than monoclinic pyrrhotite because of large density of states near the Fermi level. The hexagonal pyrrhotite shows antiferromagnetism. S—Fe bonds mainly exist in monoclinic pyrrhotite as the covalent bonds, while hexagonal pyrrhotite has no covalency. The main contributions of higest occupied molecular orbital(HOMO) and lowest unoccupied molecular obital(LUMO) for monoclinic pyrrhotite come from S and Fe. The main contribution of HOMO for hexagonal pyrrhotite comes from Fe, while that of LUMO comes from S. The coefficient of Fe atom is much larger than that of S atom of HOMO for hexagonal pyrrhotite, which contributes to the adsorption of Ca OH+ on the surface of hexagonal pyrrhotite when there is lime. As a result, lime has the inhibitory effect on the floatation of hexagonal pyrrhotite and the coefficient of Fe is very close to that of S for monoclinic pyrrhotite. Therefore, the existence of S prevents the adsorption of Ca OH+on the surface of monoclinic pyrrhotite, which leads to less inhibitory effect on the flotation of monoclinic pyrrhotite.展开更多
The floatability of different crystalline structures of pyrrhotite(monoclinic and hexagonal) was studied.It is shown that the floatability of monoclinic and hexagonal has obvious difference,and that the flotation reco...The floatability of different crystalline structures of pyrrhotite(monoclinic and hexagonal) was studied.It is shown that the floatability of monoclinic and hexagonal has obvious difference,and that the flotation recovery of monoclinic pyrrhotite is larger than that of hexagonal pyrrhotite using different collectors.When butyl dithiophosphate is used as the collector,the recovery is larger than that by sodium butyl xanthate and sodium diethyl dithiocarbamate.At the pH values ranging from 6 to 9,monoclinic pyrrhotite can be floated well,and the flotation recovery is higher than 90%.Monoclinic and hexagonal pyrrhotites are more easily activated by Cu2+ in acidic conditions than in alkaline conditions.But Cu2+ cannot activate hexagonal pyrrhotite using sodium diethyldithiocarbamate as the collector.By the measurement of contact angle,it is indicated that monoclinic and hexagonal pyrrhotites float well and are easily activated by Cu2+ when dithiophosphate is used as the collector.Using sodium diethyl dithiocarbamate as a collector,the relationship between potential and pH range for pyrrhotite flotation is established.At pH 5,the optimal potential range for flotation of monoclinic pyrrhotite is about 125-580 mV(vs SHE),with the maximum flotation occurring at about 350 mV(vs SHE);the optimal potential range for flotation of hexagonal pyrrhotite is 200?580 mV(vs SHE),with the maximum flotation occurring at about 300 mV(vs SHE).展开更多
Elective culture of Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans in 9K medium modified with pyrrhotite was studied.Bioleaching of flotation concentrate of sphalerite by the selected bacteria was ca...Elective culture of Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans in 9K medium modified with pyrrhotite was studied.Bioleaching of flotation concentrate of sphalerite by the selected bacteria was carried out.The results show that the microorganisms cultured by pyrrhotite are a mixture of Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans,of which the capability to oxidize ferrous to ferric irons is enhanced by the high mass ratio of Fe to S in pyrrhotite.Three pyrrhotite samples were separated into various parts with corresponding S/Fe ratios by magnetic separation and were used to culture the elective bacteria as the substrate.The association of the cultures could provide a more rapid and complete oxidation of sphalerite than that of bacteria cultivated by conventional methods.展开更多
The bioleaching of pyrrhotite was investigated using Sulfobacillus thermosulfidooxidans.The effects of pH,pulp concentration,inoculation amount,external addition of ferrous and ferric ions were examined.The pH is foun...The bioleaching of pyrrhotite was investigated using Sulfobacillus thermosulfidooxidans.The effects of pH,pulp concentration,inoculation amount,external addition of ferrous and ferric ions were examined.The pH is found to exert a profound effect on the leaching process for controlling the bacterial activity and precipitation of ferric ions mainly as jarosite.The results show that low pulp content increases the leaching rate of iron.The inoculation amount from 1×107 cell/mL to 1×108 cell/mL has positive effects on the leaching rate.The results also imply that addition of ferrous sulfate(1 g/L) is required for the bacteria to efficiently drive the extraction of iron,however,the leaching efficiency has no obvious enhancement when 2 g/L ferrous sulfate was added.Comparatively,addition of ferric sulfate(2 g/L) significantly inhibits the bioleaching process.At the end of bioleaching,jarosite and sulfur are observed on the surface of pyrrhotite residues by using XRD and SEM.With the passivation film formed by jarosite and sulfur,the continuous iron extraction is effectively blocked.展开更多
The electrode process of diethyldithiocarbamate on the surface of pyrrhotite was studied using systematic electrochemical analysis, including cyclic voltammetry, chronopotentiometry and galvanostatic. Experimental res...The electrode process of diethyldithiocarbamate on the surface of pyrrhotite was studied using systematic electrochemical analysis, including cyclic voltammetry, chronopotentiometry and galvanostatic. Experimental results show that tetraethylthioram disulphide（TETD） is electrodeposited on pyrrhotite electrode surface in the presence of 1.0×10^-4 mol/L diethyldithiocarbamate when the electrode potential is higher than 0.25 V. The electrochemical kinetics parameters of the electrode process of diethyldithiocarbamate on surface of pyrrhotite are calculated as follows： the exchange current density is 2.48μA/cm^2 , and the transmission coefficient is 0.46. The electrodeposition includes two steps electrochemical reaction. The first reaction is electrochemical adsorption of diethyldithiocarbamatc ion, then the adsorbed ion associates with a diethyldithiocarbamate ion from the solution and forms tetraethylthioram disulphide on the surface of pyrrhotite.展开更多
Bioleaching and electrochemical experiments were conducted to evaluate pyrrhotite dissolution in the presence of pure L.ferriphilum and mixed culture of L. ferriphilum and A. caldus. The results indicate that the pyrr...Bioleaching and electrochemical experiments were conducted to evaluate pyrrhotite dissolution in the presence of pure L.ferriphilum and mixed culture of L. ferriphilum and A. caldus. The results indicate that the pyrrhotite oxidation behavior is the preferential dissolution of iron accompanied with the massive formation of sulfur in the presence of L. ferriphilum, which significantly hinders the leaching efficiency. Comparatively, the leaching rate of pyrrhotite distinctly increases by 68% in the mixed culture of L. ferriphilum and A. caldus at the 3rd day. But, the accumulated ferric ions and high p H value produced by bioleaching process can give rise to the rapid formation of jarosite, which is the primary passivation film blocking continuous iron extraction during bioleaching by the mixed culture. The addition of A. caldus during leaching by L. ferriphilum can accelerate the oxidation rate of pyrrhotite, but not change the electrochemical oxidation mechanisms of pyrrhotite. XRD and SEM/EDS analyses as well as electrochemical study confirm the above conclusions.展开更多
Using sodium diethyldithiocarbamate as a collector the flotation behavior of pyrrhotite was investigated. The relationship between potential and pH range for pyrrhotite flotation was established. The results show that...Using sodium diethyldithiocarbamate as a collector the flotation behavior of pyrrhotite was investigated. The relationship between potential and pH range for pyrrhotite flotation was established. The results show that the flotation of pyrrhotite is dependent on pulp potential at certain pH values. Pyrrhotite has good floatability from pH 2 to pH 12, and poor flotability at pH>12. Cyclic voltammetry and Fourier transform infrared spectrum analysis show that the major adsorption product of DDTC on pyrrhotite is tetraethylthiuram disulfide. The intensity of Fourier transform infrared signals of tetraethylthiuram disulfide adsorbed on pyrrhotite and the anode current of a pyrrhotite electrode and flotation response of pyrrhotite are correlated with pulp potentials.展开更多
Bacterial leaching of single sulfide minerals and polymetallic sulfide ores was operated in shake flasks and small-scaled columns.The results show that bioleaching of jamesonite is not accessible,the iron extraction r...Bacterial leaching of single sulfide minerals and polymetallic sulfide ores was operated in shake flasks and small-scaled columns.The results show that bioleaching of jamesonite is not accessible,the iron extraction rate of pyrrhotite bioleaching reaches 98.2% after 26 d,and the zinc extraction rate of marmatite bioleaching reaches 92.3%,while the corresponding iron extraction reaches only 13.6% after 29 d.Pulp density has a significant effect on metal extraction of pyrrhotite and marmatite bioleaching.The corresponding metal extraction rate decreases with the increase of pulp density.For the polymetallic sulfide ores,zinc extraction of 97.1% is achieved after bioleaching in shake flasks for 10 d,while only 7.8% is obtained after bioleaching in small-scaled column.Analytical results of scanning electron microscopy(SEM) and energy dispersive X-ray analysis(EDX) reveal that large amount of calcium sulfate is formed on the mineral surface.展开更多
基金Project supported by the Open Foundation of Guangxi Key Laboratory for Advanced Materials and Manufacturing Technology,China
文摘Electronic structures of monoclinic and hexagonal pyrrhotite were studied using density functional theory method,together with their flotation behavior. The main contribution of monoclinic pyrrhotite is mainly from Fe 3d, while that of hexagonal pyrrhotite is from Fe 3d, Fe 3p and S 3s. The hexagonal pyrrhotite is more reactive than monoclinic pyrrhotite because of large density of states near the Fermi level. The hexagonal pyrrhotite shows antiferromagnetism. S—Fe bonds mainly exist in monoclinic pyrrhotite as the covalent bonds, while hexagonal pyrrhotite has no covalency. The main contributions of higest occupied molecular orbital(HOMO) and lowest unoccupied molecular obital(LUMO) for monoclinic pyrrhotite come from S and Fe. The main contribution of HOMO for hexagonal pyrrhotite comes from Fe, while that of LUMO comes from S. The coefficient of Fe atom is much larger than that of S atom of HOMO for hexagonal pyrrhotite, which contributes to the adsorption of Ca OH+ on the surface of hexagonal pyrrhotite when there is lime. As a result, lime has the inhibitory effect on the floatation of hexagonal pyrrhotite and the coefficient of Fe is very close to that of S for monoclinic pyrrhotite. Therefore, the existence of S prevents the adsorption of Ca OH+on the surface of monoclinic pyrrhotite, which leads to less inhibitory effect on the flotation of monoclinic pyrrhotite.
基金Project(50774094) supported by the National Natural Science Foundation of China
文摘The floatability of different crystalline structures of pyrrhotite(monoclinic and hexagonal) was studied.It is shown that the floatability of monoclinic and hexagonal has obvious difference,and that the flotation recovery of monoclinic pyrrhotite is larger than that of hexagonal pyrrhotite using different collectors.When butyl dithiophosphate is used as the collector,the recovery is larger than that by sodium butyl xanthate and sodium diethyl dithiocarbamate.At the pH values ranging from 6 to 9,monoclinic pyrrhotite can be floated well,and the flotation recovery is higher than 90%.Monoclinic and hexagonal pyrrhotites are more easily activated by Cu2+ in acidic conditions than in alkaline conditions.But Cu2+ cannot activate hexagonal pyrrhotite using sodium diethyldithiocarbamate as the collector.By the measurement of contact angle,it is indicated that monoclinic and hexagonal pyrrhotites float well and are easily activated by Cu2+ when dithiophosphate is used as the collector.Using sodium diethyl dithiocarbamate as a collector,the relationship between potential and pH range for pyrrhotite flotation is established.At pH 5,the optimal potential range for flotation of monoclinic pyrrhotite is about 125-580 mV(vs SHE),with the maximum flotation occurring at about 350 mV(vs SHE);the optimal potential range for flotation of hexagonal pyrrhotite is 200?580 mV(vs SHE),with the maximum flotation occurring at about 300 mV(vs SHE).
基金Project(50621063)supported by the National Natural Science Foundation of ChinaProject(2004CD619205)supported by the Major StateBasic Research Development Program of China
文摘Elective culture of Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans in 9K medium modified with pyrrhotite was studied.Bioleaching of flotation concentrate of sphalerite by the selected bacteria was carried out.The results show that the microorganisms cultured by pyrrhotite are a mixture of Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans,of which the capability to oxidize ferrous to ferric irons is enhanced by the high mass ratio of Fe to S in pyrrhotite.Three pyrrhotite samples were separated into various parts with corresponding S/Fe ratios by magnetic separation and were used to culture the elective bacteria as the substrate.The association of the cultures could provide a more rapid and complete oxidation of sphalerite than that of bacteria cultivated by conventional methods.
基金Project(2010CB630903) supported by the National Basic Research Program of China
文摘The bioleaching of pyrrhotite was investigated using Sulfobacillus thermosulfidooxidans.The effects of pH,pulp concentration,inoculation amount,external addition of ferrous and ferric ions were examined.The pH is found to exert a profound effect on the leaching process for controlling the bacterial activity and precipitation of ferric ions mainly as jarosite.The results show that low pulp content increases the leaching rate of iron.The inoculation amount from 1×107 cell/mL to 1×108 cell/mL has positive effects on the leaching rate.The results also imply that addition of ferrous sulfate(1 g/L) is required for the bacteria to efficiently drive the extraction of iron,however,the leaching efficiency has no obvious enhancement when 2 g/L ferrous sulfate was added.Comparatively,addition of ferric sulfate(2 g/L) significantly inhibits the bioleaching process.At the end of bioleaching,jarosite and sulfur are observed on the surface of pyrrhotite residues by using XRD and SEM.With the passivation film formed by jarosite and sulfur,the continuous iron extraction is effectively blocked.
文摘The electrode process of diethyldithiocarbamate on the surface of pyrrhotite was studied using systematic electrochemical analysis, including cyclic voltammetry, chronopotentiometry and galvanostatic. Experimental results show that tetraethylthioram disulphide（TETD） is electrodeposited on pyrrhotite electrode surface in the presence of 1.0×10^-4 mol/L diethyldithiocarbamate when the electrode potential is higher than 0.25 V. The electrochemical kinetics parameters of the electrode process of diethyldithiocarbamate on surface of pyrrhotite are calculated as follows： the exchange current density is 2.48μA/cm^2 , and the transmission coefficient is 0.46. The electrodeposition includes two steps electrochemical reaction. The first reaction is electrochemical adsorption of diethyldithiocarbamatc ion, then the adsorbed ion associates with a diethyldithiocarbamate ion from the solution and forms tetraethylthioram disulphide on the surface of pyrrhotite.
基金Project(2010CB630903) supported by the National Basic Research Program of ChinaProject(51374249) supported by the National Natural Science Foundation of China
文摘Bioleaching and electrochemical experiments were conducted to evaluate pyrrhotite dissolution in the presence of pure L.ferriphilum and mixed culture of L. ferriphilum and A. caldus. The results indicate that the pyrrhotite oxidation behavior is the preferential dissolution of iron accompanied with the massive formation of sulfur in the presence of L. ferriphilum, which significantly hinders the leaching efficiency. Comparatively, the leaching rate of pyrrhotite distinctly increases by 68% in the mixed culture of L. ferriphilum and A. caldus at the 3rd day. But, the accumulated ferric ions and high p H value produced by bioleaching process can give rise to the rapid formation of jarosite, which is the primary passivation film blocking continuous iron extraction during bioleaching by the mixed culture. The addition of A. caldus during leaching by L. ferriphilum can accelerate the oxidation rate of pyrrhotite, but not change the electrochemical oxidation mechanisms of pyrrhotite. XRD and SEM/EDS analyses as well as electrochemical study confirm the above conclusions.
文摘Using sodium diethyldithiocarbamate as a collector the flotation behavior of pyrrhotite was investigated. The relationship between potential and pH range for pyrrhotite flotation was established. The results show that the flotation of pyrrhotite is dependent on pulp potential at certain pH values. Pyrrhotite has good floatability from pH 2 to pH 12, and poor flotability at pH>12. Cyclic voltammetry and Fourier transform infrared spectrum analysis show that the major adsorption product of DDTC on pyrrhotite is tetraethylthiuram disulfide. The intensity of Fourier transform infrared signals of tetraethylthiuram disulfide adsorbed on pyrrhotite and the anode current of a pyrrhotite electrode and flotation response of pyrrhotite are correlated with pulp potentials.
基金Project(51374248) supported by the National Natural Science Foundation of ChinaProject(NCET-13-0595) supported by Program for New Century Excellent Talents in University,China+1 种基金Project(2012AA061501) supported by the National High Technology Research and Development Program of ChinaProject(20120162120010) supported by the Research Fund for the Doctoral Program of Higher Education of China
文摘Bacterial leaching of single sulfide minerals and polymetallic sulfide ores was operated in shake flasks and small-scaled columns.The results show that bioleaching of jamesonite is not accessible,the iron extraction rate of pyrrhotite bioleaching reaches 98.2% after 26 d,and the zinc extraction rate of marmatite bioleaching reaches 92.3%,while the corresponding iron extraction reaches only 13.6% after 29 d.Pulp density has a significant effect on metal extraction of pyrrhotite and marmatite bioleaching.The corresponding metal extraction rate decreases with the increase of pulp density.For the polymetallic sulfide ores,zinc extraction of 97.1% is achieved after bioleaching in shake flasks for 10 d,while only 7.8% is obtained after bioleaching in small-scaled column.Analytical results of scanning electron microscopy(SEM) and energy dispersive X-ray analysis(EDX) reveal that large amount of calcium sulfate is formed on the mineral surface.
