Fe(Ⅲ)has been proved to be a more eff ective oxidant than dissolved oxygen at ambient temperature,however,the role of Fe(Ⅲ)in pyrite acidic pressure oxidation was rarely discussed so far.In this paper,in-situ electr...Fe(Ⅲ)has been proved to be a more eff ective oxidant than dissolved oxygen at ambient temperature,however,the role of Fe(Ⅲ)in pyrite acidic pressure oxidation was rarely discussed so far.In this paper,in-situ electrochemical investigation was performed using a flow-through autoclave system in acidic pressure oxidation environment.The results illustrated that increasing Fe(Ⅲ)concentrations led to raising in redox potential of the solution,and decreased passivation of pyrite caused by deposition of elemental sulfur.Reduction of Fe(Ⅲ)at pyrite surface was a fast reaction with low activation energy,it was only slightly promoted by rising temperatures.While,the oxidation rate of pyrite at all investigated Fe(Ⅲ)concentrations increased obviously with rising temperatures,the anodic reaction was the rate-limiting step in the overall reaction.Activation energy of pyrite oxidation decreased from 47.74 to 28.79 kJ/mol when Fe(Ⅲ)concentration was increased from 0.05 to 0.50 g/L,showing that the reaction kinetics were limited by the rate of electrochemical reaction at low Fe(Ⅲ)concentrations,while,it gradually turned to be diffusion control with increasing Fe(Ⅲ)concentrations.展开更多
Gold bearing pyrite leaching was conducted in H2SO4-Fe2(SO4)3 system at different reaction temperatures,with different ferric ion concentrations,sulfuric acid concentrations and stirring speeds.The leaching kinetics...Gold bearing pyrite leaching was conducted in H2SO4-Fe2(SO4)3 system at different reaction temperatures,with different ferric ion concentrations,sulfuric acid concentrations and stirring speeds.The leaching kinetics and mechanism were studied.When the temperature ranged between 30-75 °C,the pyrite leaching was mainly controlled by chemical reaction with positive correlation to the ferric ion concentration.The activation energy obtained from Arrhenius empirical formula is 51.39 k J/mol.The EDS and XPS analyses suggest that the oxidation of sulfur within pyrite is through a series of intermediate stages,and eventually is oxidized to sulphate accompanied with the formation of element sulfur.This indicates a thiosulfate oxidation pathway of the gold bearing pyrite oxidation in H2SO4-Fe2(SO4)3 system.展开更多
This study investigated the effects of H2O2 treatment on xanthate interaction and flotation separation of chalcopyrite and pyrite by making use of a series of laboratory flotation experiments and surface analysis tech...This study investigated the effects of H2O2 treatment on xanthate interaction and flotation separation of chalcopyrite and pyrite by making use of a series of laboratory flotation experiments and surface analysis techniques.Flotation test results showed that H2O2 treatment influenced the flotation behaviors of the two minerals;however,flotation of pyrite was depressed more significantly than that of the chalcopyrite.Under well-controlled H2O2 concentration,the selective separation of chalcopyrite from pyrite was realized at pH 9.0,at which the recovery of chalcopyrite was over 84%and that of pyrite was less than 24%.Zeta potential,UV-visible and IR spectrum measurements revealed that the collector interacted differently with the two minerals after H2O2 treatment,and the surface of chalcopyrite adsorbed much greater amount of xanthate than that of the pyrite.IR and XPS analyses showed that the H2O2 treatment significantly changed the surface properties of pyrite to very hydrophilic species that inhibited the adsorption of collector and thus depressed the floatability of pyrite.While,the surface of chalcopyrite remained mildly inert to H2O2,as a result,the adsorption of xanthate and its oxidation to dixanthogen were very effective,which enhanced the flotation of chalcopyrite.展开更多
Simulated heap bioleaching of low-grade high pyrite-bearing chalcocite ore was conducted at 40 °C with aeration of CO_2 and N_2.Ore samples were collected at day 43,64,85,106 and subjected to microbial community ...Simulated heap bioleaching of low-grade high pyrite-bearing chalcocite ore was conducted at 40 °C with aeration of CO_2 and N_2.Ore samples were collected at day 43,64,85,106 and subjected to microbial community analysis by 16S rRNA gene clone library.Phylogenetic analyses of 16S rDNA fragments revealed that the retrieved sequences are mainly related to genus Acidithiobacillus,Leptospirillum and Sulfobacillus.Aeration of CO_2 and N_2 significantly impacted the microbial community composition.When CO_2 was aerated,the proportion of genus Acidithiobacillus considerably increased,whereas the proportion of genus Leptospirillum and genus Sulfobacillus declined.However,with the aeration of N_2,the proportion of genus Acidithiobacillus and Leptospirillum increased,but genus Sulfobacillus decreased.When there was no aeration,the microbial community was similar to the inocula with the proportion of genus Leptospirillum mounted.These results indicated that the limitation of oxygen could change the bioleaching microbial community and the aeration of CO_2 and N_2 was favourable for the growth of sulfur-oxidizer(At.caldus) and iron-oxidizer(L.ferriphilum) respectively,which could be used for the regulation of microorganisms' role in mineral bioleaching.展开更多
Formation of pyrite (FeS 2) films through electrodeposition from aqueous solutions which contain different source materials has been investigated. Na 2S 2O 3·5H 2O is used as sulfur source material, FeSO 4·7...Formation of pyrite (FeS 2) films through electrodeposition from aqueous solutions which contain different source materials has been investigated. Na 2S 2O 3·5H 2O is used as sulfur source material, FeSO 4·7H 2O, FeCl 2·4H 2O and FeCl 3·6H 2O are used as iron source materials respectively. The samples are annealed in N 2 atmosphere at 400 ℃ and 500 ℃ respectively. From XRD (X-ray diffraction) patterns of the films, it is found that there are peaks of FeS 2, FeS and Fe 7S 8 in all films, but there are sharp and more peaks characterizing FeS 2 in the film from Na 2S 2O 3 +FeSO 4 than other films, and 400 ℃ is the more suitable temperature than 500 ℃ for annealing the samples in N 2 atmosphere. In addition, one solution can be used repeatedly.展开更多
The role of CaCl2 during the high temperature chloridizing-reduction roasting process was investigated, aiming at acquiring high strength blast furnace burden with high iron grade and low nonferrous metals content. Th...The role of CaCl2 during the high temperature chloridizing-reduction roasting process was investigated, aiming at acquiring high strength blast furnace burden with high iron grade and low nonferrous metals content. The effects of CaCl2 dosage on pelletizing, preheating and reduction were investigated. The results show that CaCl2 can improve the wet drop strength but reduces the thermostability of pyrite cinder green balls. When the dosage of CaCl2 exceeds 1%, the compressive strength of preheated pellets decreases while the growth of iron oxide particles is improved. Furthermore, the compressive strength of pre-reduced pellets increases but the metallization degree of pre-reduced pellets decreases with CaCl2 additive. The removal tests indicate that Zn can be removed completely without CaCl2 additive, Cu is removed only under the condition with CaCl2 additive and part of Pb must be removed by CaCl2 additive.展开更多
Sulfate rocks and organic sulfur from sedimentary organic matter are conventionally assumed as the original sulfur sources for hydrogen sulfide (H2S) in oil and gas reservoirs. However, a few recent experiments prel...Sulfate rocks and organic sulfur from sedimentary organic matter are conventionally assumed as the original sulfur sources for hydrogen sulfide (H2S) in oil and gas reservoirs. However, a few recent experiments preliminarily indicate that the association of pyrite and hydrocarbons may also have implications for H2S generation, in which water effects and natural controls on the evolution of pyrite sulfur into OSCs and H2S have not been evaluated. In this study, laboratory experiments were conducted from 200 to 450°C to investigate chemical interactions between pyrite and hydrocarbons under hydrothermal conditions. Based on the experimental results, preliminary mechanism and geochemical implications were tentatively discussed. Results of the experiments showed that decomposition of pyrite produced H2S and thiophenes at as low as 330°C in the presence of water and n-pentane. High concentrations of H2S were generated above 450°C under closed pyrolysis conditions no matter whether there is water in the designed experiments. However, much more organic sulfur compounds (OSCs) were formed in the hydrous pyrolysis than in anhydrous pyrolysis. Generally, most of sulfur liberated from pyrite at elevated temperatures was converted to H2S. Water was beneficial to breakdown of pyrite and to decomposition of alkanes into olefins but not essential to formation of large amounts of H2S, given the main hydrogen source derived from hydrocarbons. In addition, cracking of pyrite in the presence of 1-octene under hydrous conditions was found to proceed at 200°C, producing thiols and alkyl sulfides. Unsaturated hydrocarbons would be more reactive intermediates involved in the breakdown of pyrite than alkanes. The geochemistry of OSCs is actually controlled by various geochemical factors such as thermal maturity and the carbon chain length of the alkanes. This study indicates that the scale of H2S gas generated in deep buried carbonate reservoirs via interactions between pyrite and natural gas should be much smaller than that of thermochemical sulfate reduction (TSR) due to the scarcity of pyrite in carbonate reservoirs and the limited amount of long-chained hydrocarbons in natural gas. Nevertheless, in some cases, OSCs and/or low contents of H2S found in deep buried reservoirs may be associated with the deposited pyrite-bearing rock and organic matters (hydrocarbons), which still needs further investigation.展开更多
Well-crystallized hexagonal hematite (α-Fe2O3) platelets were synthesized by hydrothermal process, using a highly concentrated ferric hydroxide as precursor. The precursor was prepared by adding ammonia to the ferr...Well-crystallized hexagonal hematite (α-Fe2O3) platelets were synthesized by hydrothermal process, using a highly concentrated ferric hydroxide as precursor. The precursor was prepared by adding ammonia to the ferric sulfate solution which was obtained by leaching pyrite cinders with sulfuric acid. Structure and morphology of the synthesized products were investigated by X-ray diffraction, scanning electron microscope, transmission electron microscope and selected area electron diffraction. The results reveal that the reaction temperature has significant effects on the structure, size and shape of the synthesized hematite particles. Typical hexagonal hematite platelets, about 0.4-0.6 μm in diameter and 0.1 μm in thickness, were prepared at 230 ℃ for 0.5 h. Al^3+, contained in the sulfuric acid leaching solution as an impurity, plays an extremely important role in the formation of hexagonal hematite. In addition, a possible mechanism about the formation of hexagonal hematite platelets was proposed.展开更多
FeS2/Fe composites were mechanochemically prepared with iron powder and pyrite for the stabilization of ferrite arsenate sludge(FAS).The effects of preparation parameters on stabilization performance were investigated...FeS2/Fe composites were mechanochemically prepared with iron powder and pyrite for the stabilization of ferrite arsenate sludge(FAS).The effects of preparation parameters on stabilization performance were investigated.The results show that the optimum conditions are FeS2/Fe molar ratio of 5:5,milling time of 2 h,ball-to-material mass ratio of 15:1 and milling with stainless steel ball.Then,the composites were characterized by XRD,SEM,FTIR,etc.The physicochemical properties of FeS2/Fe mixture change dramatically,which is responsible for its excellent performance.Finally,the stabilization process of FAS was optimized.When the FAS is mixed with composites at mass ratio of 4:1 and milled for 30 min,the As leaching concentration of FAS can be reduced from 639.15 to 4.74 mg/L with the stabilization ratio of 99.2%.展开更多
基金supported by the Science and Technology Foundation of Guizhou Province,China(No.[2020]1Y163)the National Natural Science Foundation of China(No.41827802).
文摘Fe(Ⅲ)has been proved to be a more eff ective oxidant than dissolved oxygen at ambient temperature,however,the role of Fe(Ⅲ)in pyrite acidic pressure oxidation was rarely discussed so far.In this paper,in-situ electrochemical investigation was performed using a flow-through autoclave system in acidic pressure oxidation environment.The results illustrated that increasing Fe(Ⅲ)concentrations led to raising in redox potential of the solution,and decreased passivation of pyrite caused by deposition of elemental sulfur.Reduction of Fe(Ⅲ)at pyrite surface was a fast reaction with low activation energy,it was only slightly promoted by rising temperatures.While,the oxidation rate of pyrite at all investigated Fe(Ⅲ)concentrations increased obviously with rising temperatures,the anodic reaction was the rate-limiting step in the overall reaction.Activation energy of pyrite oxidation decreased from 47.74 to 28.79 kJ/mol when Fe(Ⅲ)concentration was increased from 0.05 to 0.50 g/L,showing that the reaction kinetics were limited by the rate of electrochemical reaction at low Fe(Ⅲ)concentrations,while,it gradually turned to be diffusion control with increasing Fe(Ⅲ)concentrations.
基金Project(51474075)supported by the National Natural Science Foundation of China
文摘Gold bearing pyrite leaching was conducted in H2SO4-Fe2(SO4)3 system at different reaction temperatures,with different ferric ion concentrations,sulfuric acid concentrations and stirring speeds.The leaching kinetics and mechanism were studied.When the temperature ranged between 30-75 °C,the pyrite leaching was mainly controlled by chemical reaction with positive correlation to the ferric ion concentration.The activation energy obtained from Arrhenius empirical formula is 51.39 k J/mol.The EDS and XPS analyses suggest that the oxidation of sulfur within pyrite is through a series of intermediate stages,and eventually is oxidized to sulphate accompanied with the formation of element sulfur.This indicates a thiosulfate oxidation pathway of the gold bearing pyrite oxidation in H2SO4-Fe2(SO4)3 system.
基金Projects(51704329,51705540) supported by the National Natural Science Foundation of ChinaProject(2015CX005) supported by the Innovation Driven Plan of Central South University,China+1 种基金Project(B14034) supported by the National “111” Project,ChinaProject(2018TP1002) supported by the Collaborative Innovation Center for Clean and Efficient Utilization of Strategic Metal Mineral Resources,China
文摘This study investigated the effects of H2O2 treatment on xanthate interaction and flotation separation of chalcopyrite and pyrite by making use of a series of laboratory flotation experiments and surface analysis techniques.Flotation test results showed that H2O2 treatment influenced the flotation behaviors of the two minerals;however,flotation of pyrite was depressed more significantly than that of the chalcopyrite.Under well-controlled H2O2 concentration,the selective separation of chalcopyrite from pyrite was realized at pH 9.0,at which the recovery of chalcopyrite was over 84%and that of pyrite was less than 24%.Zeta potential,UV-visible and IR spectrum measurements revealed that the collector interacted differently with the two minerals after H2O2 treatment,and the surface of chalcopyrite adsorbed much greater amount of xanthate than that of the pyrite.IR and XPS analyses showed that the H2O2 treatment significantly changed the surface properties of pyrite to very hydrophilic species that inhibited the adsorption of collector and thus depressed the floatability of pyrite.While,the surface of chalcopyrite remained mildly inert to H2O2,as a result,the adsorption of xanthate and its oxidation to dixanthogen were very effective,which enhanced the flotation of chalcopyrite.
基金Project(51404033)supported by the National Natural Science Foundation of ChinaProject(2010CB630905)supported by the National Basic Research Program of China
文摘Simulated heap bioleaching of low-grade high pyrite-bearing chalcocite ore was conducted at 40 °C with aeration of CO_2 and N_2.Ore samples were collected at day 43,64,85,106 and subjected to microbial community analysis by 16S rRNA gene clone library.Phylogenetic analyses of 16S rDNA fragments revealed that the retrieved sequences are mainly related to genus Acidithiobacillus,Leptospirillum and Sulfobacillus.Aeration of CO_2 and N_2 significantly impacted the microbial community composition.When CO_2 was aerated,the proportion of genus Acidithiobacillus considerably increased,whereas the proportion of genus Leptospirillum and genus Sulfobacillus declined.However,with the aeration of N_2,the proportion of genus Acidithiobacillus and Leptospirillum increased,but genus Sulfobacillus decreased.When there was no aeration,the microbial community was similar to the inocula with the proportion of genus Leptospirillum mounted.These results indicated that the limitation of oxygen could change the bioleaching microbial community and the aeration of CO_2 and N_2 was favourable for the growth of sulfur-oxidizer(At.caldus) and iron-oxidizer(L.ferriphilum) respectively,which could be used for the regulation of microorganisms' role in mineral bioleaching.
文摘Formation of pyrite (FeS 2) films through electrodeposition from aqueous solutions which contain different source materials has been investigated. Na 2S 2O 3·5H 2O is used as sulfur source material, FeSO 4·7H 2O, FeCl 2·4H 2O and FeCl 3·6H 2O are used as iron source materials respectively. The samples are annealed in N 2 atmosphere at 400 ℃ and 500 ℃ respectively. From XRD (X-ray diffraction) patterns of the films, it is found that there are peaks of FeS 2, FeS and Fe 7S 8 in all films, but there are sharp and more peaks characterizing FeS 2 in the film from Na 2S 2O 3 +FeSO 4 than other films, and 400 ℃ is the more suitable temperature than 500 ℃ for annealing the samples in N 2 atmosphere. In addition, one solution can be used repeatedly.
基金Project(51504155)supported by the National Natural Science Foundation of ChinaProject(BK20140337)supported by the Basic Research Program of Jiangsu Province+2 种基金ChinaProject(SDY2013A13)supported by the Young Teacher Natural Science Fund of Soochow UniversityChina
文摘The role of CaCl2 during the high temperature chloridizing-reduction roasting process was investigated, aiming at acquiring high strength blast furnace burden with high iron grade and low nonferrous metals content. The effects of CaCl2 dosage on pelletizing, preheating and reduction were investigated. The results show that CaCl2 can improve the wet drop strength but reduces the thermostability of pyrite cinder green balls. When the dosage of CaCl2 exceeds 1%, the compressive strength of preheated pellets decreases while the growth of iron oxide particles is improved. Furthermore, the compressive strength of pre-reduced pellets increases but the metallization degree of pre-reduced pellets decreases with CaCl2 additive. The removal tests indicate that Zn can be removed completely without CaCl2 additive, Cu is removed only under the condition with CaCl2 additive and part of Pb must be removed by CaCl2 additive.
基金the National Natural Science Foundations of China(No.41472095 and No.40902034)the Foundation of State Key Laboratory of Petroleum Resources and Prospecting,China University of Petroleum,Beijing(No.PRP/open-1508)PetroChina Innovation Foundation(No.2012D-5006-0104)
文摘Sulfate rocks and organic sulfur from sedimentary organic matter are conventionally assumed as the original sulfur sources for hydrogen sulfide (H2S) in oil and gas reservoirs. However, a few recent experiments preliminarily indicate that the association of pyrite and hydrocarbons may also have implications for H2S generation, in which water effects and natural controls on the evolution of pyrite sulfur into OSCs and H2S have not been evaluated. In this study, laboratory experiments were conducted from 200 to 450°C to investigate chemical interactions between pyrite and hydrocarbons under hydrothermal conditions. Based on the experimental results, preliminary mechanism and geochemical implications were tentatively discussed. Results of the experiments showed that decomposition of pyrite produced H2S and thiophenes at as low as 330°C in the presence of water and n-pentane. High concentrations of H2S were generated above 450°C under closed pyrolysis conditions no matter whether there is water in the designed experiments. However, much more organic sulfur compounds (OSCs) were formed in the hydrous pyrolysis than in anhydrous pyrolysis. Generally, most of sulfur liberated from pyrite at elevated temperatures was converted to H2S. Water was beneficial to breakdown of pyrite and to decomposition of alkanes into olefins but not essential to formation of large amounts of H2S, given the main hydrogen source derived from hydrocarbons. In addition, cracking of pyrite in the presence of 1-octene under hydrous conditions was found to proceed at 200°C, producing thiols and alkyl sulfides. Unsaturated hydrocarbons would be more reactive intermediates involved in the breakdown of pyrite than alkanes. The geochemistry of OSCs is actually controlled by various geochemical factors such as thermal maturity and the carbon chain length of the alkanes. This study indicates that the scale of H2S gas generated in deep buried carbonate reservoirs via interactions between pyrite and natural gas should be much smaller than that of thermochemical sulfate reduction (TSR) due to the scarcity of pyrite in carbonate reservoirs and the limited amount of long-chained hydrocarbons in natural gas. Nevertheless, in some cases, OSCs and/or low contents of H2S found in deep buried reservoirs may be associated with the deposited pyrite-bearing rock and organic matters (hydrocarbons), which still needs further investigation.
基金Project(2008A090300016) supported by the Key Science and Technology Item of Guangdong Province,ChinaProject(ZKJ2010022) supported by the Precious Apparatus Opening Center Foundation of Central South University,China
文摘Well-crystallized hexagonal hematite (α-Fe2O3) platelets were synthesized by hydrothermal process, using a highly concentrated ferric hydroxide as precursor. The precursor was prepared by adding ammonia to the ferric sulfate solution which was obtained by leaching pyrite cinders with sulfuric acid. Structure and morphology of the synthesized products were investigated by X-ray diffraction, scanning electron microscope, transmission electron microscope and selected area electron diffraction. The results reveal that the reaction temperature has significant effects on the structure, size and shape of the synthesized hematite particles. Typical hexagonal hematite platelets, about 0.4-0.6 μm in diameter and 0.1 μm in thickness, were prepared at 230 ℃ for 0.5 h. Al^3+, contained in the sulfuric acid leaching solution as an impurity, plays an extremely important role in the formation of hexagonal hematite. In addition, a possible mechanism about the formation of hexagonal hematite platelets was proposed.
基金Projects(2018YFC1900305,2018YFC1903301)supported by the National Key R&D Program of ChinaProject(51825403)supported by the National Natural Science Foundation for Distinguished Young Scholars of China+1 种基金Project(51634010)supported by the National Natural Science Foundation of ChinaProject(2017RS3010)supported by the Science and Technology Program of Hunan Province,China
文摘FeS2/Fe composites were mechanochemically prepared with iron powder and pyrite for the stabilization of ferrite arsenate sludge(FAS).The effects of preparation parameters on stabilization performance were investigated.The results show that the optimum conditions are FeS2/Fe molar ratio of 5:5,milling time of 2 h,ball-to-material mass ratio of 15:1 and milling with stainless steel ball.Then,the composites were characterized by XRD,SEM,FTIR,etc.The physicochemical properties of FeS2/Fe mixture change dramatically,which is responsible for its excellent performance.Finally,the stabilization process of FAS was optimized.When the FAS is mixed with composites at mass ratio of 4:1 and milled for 30 min,the As leaching concentration of FAS can be reduced from 639.15 to 4.74 mg/L with the stabilization ratio of 99.2%.