Selenium distillation slag(SDS)is a high-value-added secondary resource with a high recovery value.This paper aims to investigate the leaching behavior and kinetics of selenium,tellurium,and copper in the SDS acid oxi...Selenium distillation slag(SDS)is a high-value-added secondary resource with a high recovery value.This paper aims to investigate the leaching behavior and kinetics of selenium,tellurium,and copper in the SDS acid oxidation leaching process with H_(2)SO_(4) and H_(2)O_(2).The experimental results showed that under the optimum conditions,the contents of selenium,tellurium,and copper in the SDS were reduced from 22.13 wt%,3.58 wt%,and 6.42 wt%to 3.06 wt%,0.27 wt%,and 0.33 wt%,respectively.Correspondingly,the recovery rates are 87.08%,97.15%and 99.7%.The leaching processes of selenium and tellurium were controlled by diffusion and chemical reactions,and the leaching behavior of copper was controlled by chemical reactions.Below 45℃,the activation energies for selenium,tellurium,and copper were found to be 26.47,62.18 and 19.67 kJ/mol,respectively.In addition,the contents of lead,silver and gold in the leaching residue are increased to 46.8 wt%,8.35 wt%and 0.27 wt%,respectively.These substances can be utilized as raw materials for the recovery of these valuable metals.Importantly,the entire process does not generate toxic or harmful waste,making it a green and environmentally friendly method for resource recovery.展开更多
The phase transformation of galena in H_(2)SO_(4)-Fe_(2)(SO_(4))_(3) system under oxygen pressure was investigated.Results indicated that the critical conditions for the phase transformation of galena into lead jarosi...The phase transformation of galena in H_(2)SO_(4)-Fe_(2)(SO_(4))_(3) system under oxygen pressure was investigated.Results indicated that the critical conditions for the phase transformation of galena into lead jarosite(Pb-J)were 130℃,30 g/L H_(2)SO_(4),15 g/L Fe^(3+),and an oxygen partial pressure of 0.4 MPa.Furthermore,increased Fe^(3+)concentration and oxygen partial pressure did not enhance jarosite formation.Conversely,lowering the temperature and increasing the H_(2)SO_(4) concentration facilitated PbSO_(4) formation and inhibited its further conversion to Pb-J.Additionally,the effects of potassium sulfate,sodium sulfate,and high concentrations of zinc sulfate on the phase transformation of galena were examined through leaching tests,XRD,SEM-EDS,and FT-IR analyses.All three sulfates inhibited the conversion of galena to Pb-J.Among these,potassium sulfate prevented Pb-J formation and converted it more thoroughly into potassium jarosite.However,high concentrations of zinc sulfate facilitated the crystallization of both PbSO_(4) and Pb-J,which altered the morphology of the product.Zinc ions coprecipitated with Pb-J,thereby integrating into the product.展开更多
In this study,a synergistic sulfidation-acid leaching process was proposed to recover valuable metals from gypsum residue and zinc-containing fume.The equilibrium phase composition of the sulfidation reaction and calc...In this study,a synergistic sulfidation-acid leaching process was proposed to recover valuable metals from gypsum residue and zinc-containing fume.The equilibrium phase composition of the sulfidation reaction and calculations of the thermodynamic stability region show that 89.36%Zn,>99%Pb and>99%Cu of gypsum residue and zinc-containing fume can be sulfured to ZnS,PbS and Cu 2 S,under sufficient sulfur partial pressure,low oxygen partial pressure and 400-1000℃.Sulfidation roasting experiments show that the sulfidation rate of Cu,Pb and Zn reach 81.43%,88.25% and 92.31%,respectively,under the roasting conditions of material mass ratio of 30 g:10 g,carbon dosage of 3.75 g,roasting temperature of 800℃ for 3 h.E−pH plots show that ZnS,PbS and Cu_(2)S can be enriched in the leaching residue,under leaching conditions at 25℃,pH<4 and-0.4 V<φ(E)<0.04 V.The leaching experiments showed that the sulfide is retained in the leaching residue,while the leaching rates of Cu,Pb and Zn are 1.94%,2.05% and 1.51%,respectively,under the conditions of 25℃,C_(HCl) of 0.5 mol/L,L/S of 5 mL/g,stirring rate of 300 r/min,and stirring time of 30 min.This study provides a new approach for the synergistic disposal of gypsum residue and zinc containing fume.展开更多
Full-component pyrolysis can process organic components and reduce cathode materials, making it a key focus in green recycling of lithium-ion batteries (LIBs). However, the leaching mechanism and kinetics of pyrolyzed...Full-component pyrolysis can process organic components and reduce cathode materials, making it a key focus in green recycling of lithium-ion batteries (LIBs). However, the leaching mechanism and kinetics of pyrolyzed black powder in organic acid systems remain unclear, with most research still at the laboratory stage. This study pioneers the exploration of the leaching behavior and reaction mechanism of valuable metal extraction from industrial-scale pyrolyzed black powder using citric acid. The effects of various leaching conditions on the extraction of metals were investigated by single factor experiments and response surface method. Under optimal conditions, the leaching efficiencies of Li, Ni, Co, and Mn all exceeded 97%. Kinetic analysis revealed that the leaching process was controlled by internal diffusion, with the apparent activation energies for Li, Ni, Co, and Mn being 17.89, 23.14, 20.27, and 15.21 kJ/mol, respectively. Additionally, residue characterization identified FePO4 formation as the primary inhibitor of iron dissolution.展开更多
In view of the difference in coordination capacity of the glycine ion(Gly−),a selective leaching process for treating with spent lithium-ion batteries(LIBs)in the alkaline glycinate system was proposed.The effects of ...In view of the difference in coordination capacity of the glycine ion(Gly−),a selective leaching process for treating with spent lithium-ion batteries(LIBs)in the alkaline glycinate system was proposed.The effects of retention time,leaching temperature,concentration of glycine ligand,liquid-solid ratio(L/S),pH,stirring speed,and H_(2)O_(2) dosage on the leaching efficiency of valuable metals and the dissolution of impurities were investigated.When the spent LIBs were leached in 3 mol/L glycine aqueous solution with pH of 8,L/S of 5 mL:1 g and H_(2)O_(2) dosage of 5 vol.%at 90℃and stirring speed of 400 r/min for 3 h,lithium,cobalt,nickel,and manganese recoveries were 96.31%,83.18%,91.56%,and 31.16%,respectively,but Ca,Al,Fe,and Cu were almost insoluble.Meanwhile,the kinetic study showed that the activation energies for the leaching of Li,Co,Ni,and Mn were all in the range of 45−61 kJ/mol.The results indicate that the leaching process is all controlled by chemical reactions.展开更多
The fluorine-based chemical method shows great potential in leaching lithium(Li) from lepidolite. Leaching kinetics of Li in a mixture of sulfuric acid and hydrofluoric acid, which is a typical lixivant for the fluori...The fluorine-based chemical method shows great potential in leaching lithium(Li) from lepidolite. Leaching kinetics of Li in a mixture of sulfuric acid and hydrofluoric acid, which is a typical lixivant for the fluorine-based chemical method, was carried out under crucial factors such as different HF/ore ratios(1:1-3:1 g/mL) and leaching temperatures(50-85℃). The kinetics data fit well with the developed shrinking-core model, indicating that the leaching rate of Li was controlled by the chemical reaction and inner diffusion at the beginning of leaching(0-30 min) as a calculated apparent activation energy(Ea) of 20.62 kJ/mol. The inner diffusion became the rate-limiting step as the leaching continues(60-180 min). Moreover, effects of HF/ore ratio and leaching temperature on selective leaching behavior of Li, Al and Si were discussed. 90% of fluorine mainly existed as HF/F-in leaching solution, which can provide theoretical guidance for further removal or recovery of F.展开更多
Based on the momentum and mass conservation equations, a comprehensive model of heap bioleaching process is developed to investigate the interaction between chemical reactions, solution flow, gas flow, and solute tran...Based on the momentum and mass conservation equations, a comprehensive model of heap bioleaching process is developed to investigate the interaction between chemical reactions, solution flow, gas flow, and solute transport within the leaching system. The governing equations are solved numerically using the COMSOL Multiphysics software for the coupled reactive flow and solute transport at micro-scale, meso-scale and macro-scale levels. At or near the surface of ore particle, the acid concentration is relatively higher than that in the central area, while the concentration gradient decreases after 72 d of leaching. The flow simulation between ore particles by combining X-ray CT technology shows that the highest velocity in narrow pore reaches 0.375 m/s. The air velocity within the dump shows that the velocity near the top and side surface is relatively high, which leads to the high oxygen concentration in that area. The coupled heat transfer and liquid flow process shows that the solution can act as an effective remover from the heap, dropping the highest temperature from 60 to 38 ℃. The reagent transfer coupled with solution flow is also analyzed. The results obtained allow us to obtain a better understanding of the fundamental physical phenomenon of the bioleaching process.展开更多
Zinc extraction from crude zinc oxide(CZO)is beneficial to the full utilization of secondary resources and environmental protection.In this paper,a systematic investigation was carried out to study the leaching behavi...Zinc extraction from crude zinc oxide(CZO)is beneficial to the full utilization of secondary resources and environmental protection.In this paper,a systematic investigation was carried out to study the leaching behavior of CZO by using ammonia-ammonium carbonate solution.It was found that the maximum leaching rate of zinc from CZO dust was 95.7%under the conditions of[Zn]T:[NH 3]T:[CO_(3)^(2−)]=1:7.00:1.75,liquid to solid ratio 5:1,leaching temperature 30℃ and leaching time 60 min.Compared with pure zinc oxide(PZO)leaching,the CZO leaching required longer time and more leaching agents,which is caused by the Cd^(2+),Pb^(2+) and other metal cationic impurities in CZO.The metal cationic impurities dissolved in the leaching solution and combined with ammonium to form complexes,consuming leaching agents and affecting zinc leaching.展开更多
The mechanism of oxygen pressure acid leaching of sphalerite catalyzed by Fe^3+/Fe^2+self-precipitation was investigated in this study.Artificial sphalerite was fabricated with varying amounts of iron content via the ...The mechanism of oxygen pressure acid leaching of sphalerite catalyzed by Fe^3+/Fe^2+self-precipitation was investigated in this study.Artificial sphalerite was fabricated with varying amounts of iron content via the sintering of ZnS and FeS and used for the pressure acid leaching experiment.The variations in the potential of the pressure leaching system were investigated by using a self-designed potential autoclave.The results showed that compared to the non-iron sphalerite,there was a violent redox reaction between the 25.70%Fe-artificial sphalerite and dissolved oxygen during the process of pressure leaching;and the catalytic mechanism was attributed to the redox couple Fe^3+/Fe^2+,where Fe3+oxidizes the H2S gas film and the reduced Fe2+state is subsequently oxidized by the dissolved oxygen.Furthermore,the effect of temperature,H2SO4 concentration,and oxygen partial pressure on the artificial sphalerite with different iron contents was studied.The sphalerite samples with iron content were observed to dissolve more easily in sulfuric acid compared to the non-iron samples.Moreover,the activation energy of artificial sphalerite was observed to be lower in the sample with 25.70%iron content(22.26 kJ/mol)compared to that with no iron(32.31 kJ/mol);and the apparent reaction orders were obtained with respect to H2SO4 concentration(1.10 and 1.36)and oxygen partial pressure(1.29 and 1.41),respectively.A comprehensive kinetic model was developed on the basis of the experimental data and the fitted leaching ratio plot;and the kinetic equations for the leaching of sphalerite catalyzed by Fe^3+/Fe^2+self-precipitation were determined.展开更多
To recover zinc from electric arc furnace(EAF)dust,a process of primary normal pressure leaching and secondary alkaline pressure leaching is proposed.First,under the alkaline pressure leaching system,the experiment of...To recover zinc from electric arc furnace(EAF)dust,a process of primary normal pressure leaching and secondary alkaline pressure leaching is proposed.First,under the alkaline pressure leaching system,the experiment of pure zinc ferrite being reduced by iron powder was carried out.Under the optimal reduction conditions(i.e.,temperature of 260℃,NaOH concentration of 6 mol/L,liquid-to-solid ratio of 50 mL/g,and a 5-fold excess of iron powder),89%of zinc was extracted.The iron in the reduced residue exists as a magnetite phase.Subsequently,the normal pressure leaching experiment was carried out with EAF dust as raw material,and 66%zinc was leached.The main phase of zinc in normal leaching residue was determined to be zinc ferrite.Then,the normal leaching residue was reduced by iron powder under the alkaline pressure leaching system,and 66.5%of zinc was extracted.After the two-stage leaching process,the leaching rate of zinc in EAF dust can achieve 88.7%.The alkaline pressure leaching solution can be returned as the normal pressure leaching solution,and the magnetite in the alkaline pressure leaching residue can be recovered by magnetic separation.展开更多
Inner Mongolian serpentine ore was subjected to sulfuric acid leaching tests,and the effects of the leaching process parameters on the leaching efficiency of different metals were investigated.The leaching efficiency ...Inner Mongolian serpentine ore was subjected to sulfuric acid leaching tests,and the effects of the leaching process parameters on the leaching efficiency of different metals were investigated.The leaching efficiency of Mg,Fe,Al,Ni,and Co reaches 93.98%,60.09%,82.08%,90.58%,and 94.06%,respectively,under the leaching conditions of 5 mol/L H_(2)SO_(4),liquid/solid ratio of 4 mL/g,and leaching temperature 100℃.Hence,the valuable metals in serpentine were effectively recovered by sulfuric acid leaching.The leaching behaviors of Mg,Fe,and a small amount of Al were analyzed using X-ray diffraction.The results show that the unreacted Mg and Fe remained as MgFe_(2)O_(4),and Al formed Al_(2)Si_(2)O_(5)(OH)_(4) in the leaching residue.The kinetics of Mg and Ni in the leaching process was studied respectively.The leaching kinetics of Mg conformed to the shrinking core model with an activation energy of 16.95 kJ/mol,which was controlled by the combination of the diffusion and chemical reaction.The leaching kinetics of Ni accorded with the Avrami equation with an activation energy of 11.57 kJ/mol,which was controlled by diffusion.In the study,the valuable metal elements were extracted from serpentine minerals with high efficiency and low cost,which possessed important practical values.展开更多
Physical and chemical properties of electric arc furnace （EAF） dust from Tianjin seamless Pipe Company were measured and analyzed. The zinc leaching tests in alkaline medium were carried out under variation of leach...Physical and chemical properties of electric arc furnace （EAF） dust from Tianjin seamless Pipe Company were measured and analyzed. The zinc leaching tests in alkaline medium were carried out under variation of leaching agent concentration, leaching temperature, leaching cumulative time and solid-to-liquid ratio. The thermodynamics and kinetics of the zinc leaching process were also analyzed. The results show that the EAF dust contains 10% （mass fraction） zinc and the median particle size is 0.69 μm. The zinc recovery of 73.4% is obtained tinder the condition of 90 ℃, 6 mol/L NaOH, and 60 min leaching time. With the increase of concentration of NaOH and the cumulative time, zinc leaching will be significantly increased. The kinetics study demonstrates that the leaching reaction is chemically controlled and the reaction activation energy is 15.73 kJ/mol.展开更多
A batch of column experiments was carried out to investigate the change of Cr（Ⅵ） concentration leached out from chromium-containing slag with HCI as leaching agent, and to study influences of pH, ratio of solid mas...A batch of column experiments was carried out to investigate the change of Cr（Ⅵ） concentration leached out from chromium-containing slag with HCI as leaching agent, and to study influences of pH, ratio of solid mass to solution volume, flow velocity and temperature on Cr（Ⅵ） leaching. The optimal parameters were obtained for Cr（Ⅵ） leaching and a fitting model was established to describe the procedure of Cr（Ⅵ） leaching. The results show that Cr（Ⅵ） concentration in leachate increases with decreasing pH and increasing flow velocity and temperature. Moreover, Cr（Ⅵ） leaching percentage increases with increasing ratio of solid mass to solution volume. The optimal parameters for Cr（Ⅵ） selective leaching are as follows： pH=3.0, 1：5 of ratio of solid mass to solution volume, 180 mL/min of flow velocity and 40 ℃ of temperature. The procedure of Cr（Ⅵ） leaching fits well with the model： v= 1.87t^-0.54, indicating that the leaching rate of Cr（Ⅵ） declines in an exponential order of-0.54.展开更多
Based on the law of temperature changes in the leaching dump and the forming process of heat flux, the basic balance equation of heat flow in dump was established, the dissipated heat flow from dump to the atmosphere ...Based on the law of temperature changes in the leaching dump and the forming process of heat flux, the basic balance equation of heat flow in dump was established, the dissipated heat flow from dump to the atmosphere was analyzed to estimate the surface temperature of the ore particle in dump and discover the law of forced heat convection of heat flow transfer in dump. And the lixiviate flow formula taking a certain heat flow out of dump was deduced by using the inversion method. Through theoretic analysis, combining Dexing copper mine heap leaching production practice, the results show that the heat flow of chalcopyrite leaching emitted is not so great, but the heat flow of pyrite leaching and sulphur oxidation produced take up a higher proportion of total heat flow; the dissipated heat flow takes up a lower proportion, and most of heat flow is absorbed by itself, thus the inside temperature rises gradually; and the saturation flow form for leaching is adopted, which makes the lixiviate seepage in the transitional flow or even in the turbulent flow, so as to accelerate the heat flow diffusing and keep the leaching dump temperature suitable for bacteria living.展开更多
According to the chemical equations, the flux and concentration of oxygen required during bacterial lea- ching sulfuric mineral were investigated; the rule of air bubble transmitted in granular was researched in the D...According to the chemical equations, the flux and concentration of oxygen required during bacterial lea- ching sulfuric mineral were investigated; the rule of air bubble transmitted in granular was researched in the Dump Leaching Plant of Dexing Copper Mine. The results show that lack of oxygen in dump leaching is the critical factor of restricting leaching reaction. Pyrite is the primary oxygen-consuming mineral in bioleaching. When its content is too high, it needs a great deal of oxygen for reaction and competes for the finite oxygen with objective minerals, and thus the leaching velocity decreases greatly. The average size of ore particles and diameter of bubbles are the key parameters affecting the mass transfer coefficient. Reverse analysis was adopted, and it shows that 44.8 m^3 air per unit ore can meet the requirement of production if the molar ratio of pyrite to chalcopyrite is 10.展开更多
A laboratory leaching experiment with samples of different grades was carried out, and an analytical method of concentration of leaching solution was put forward. For each sample, respectively, by applying phase space...A laboratory leaching experiment with samples of different grades was carried out, and an analytical method of concentration of leaching solution was put forward. For each sample, respectively, by applying phase space reconstruction for time series of monitoring data, the saturated embedding dimension and the correlation dimension were obtained, and the evolution laws between neighboring points in the reconstructed phase space were revealed. With BP neural network, a prediction model of concentration of leaching solution was set up and the maximum error of which was less than 2%. The results show that there exist chaotic characteristics in leaching system, and samples of different grades have different nonlinear dynamic features; the higher the grade of sample, the smaller the correlation dimension; furthermore, the maximum Lyapunov index, energy dissipation and chaotic extent of the leaching system increase with grade of the sample; by phase space reconstruction, the subtle change features of concentration of leaching solution can be magnified and the inherent laws can be fully demonstrated. According to the laws, a prediction model of leaching cycle period has been established to provide a theoretical foundation for solution mining.展开更多
For the low-grade copper sulfide ores with 0.99% of copper, of which 41.5% was primary copper sulfide, and 54.5% was secondary copper sulfide, well-controlled column bioleaching on a novel equipment was carried out to...For the low-grade copper sulfide ores with 0.99% of copper, of which 41.5% was primary copper sulfide, and 54.5% was secondary copper sulfide, well-controlled column bioleaching on a novel equipment was carried out to investigate the optimal conditions of pre-leaching, particle sizes of ores, temperature, spray intensity and strain consortium. Results show that copper extraction of 91.11% can be obtained after 90 d with the optimal p H value of pre-leaching of 0.8; the p H values of pre-leaching significantly affect the final copper extractions. Copper extractions of 93.11%, 91.04% and 80.45% can be obtained for the bioleaching of ores with particles size of 5-8 mm, 5-15 mm and 5-20 mm, respectively. Copper extractions are 83.77% and 91.02% for bioleaching under the conditions of room temperature and 35 oC. Copper extractions are 77.25%, 85.45% and 91.12% for the bioleaching when flow rate of spray was 5 L/（h·m2）, 10 L/（h·m2） and 15 L/（h·m2）, respectively. Additionally, the strain consortium C3 is the best among the four strain consortia in bioleaching. By considering the energy consumption, the optimal conditions of bioleaching in this work are determined as p H of pre-leaching of 0.8, particles size of 5-15 mm, temperature of 35 ℃, spray intensity of 15 L/（h·m2）, and strain consortium C3.展开更多
A feasible approach to selectively recover iron and rare earth elements(REEs)from red mud through acid leaching-coordination-solvent extraction was proposed.The leaching efficiencies of Fe,Al,Ti,Sc,La,Ce,Nd and Y can ...A feasible approach to selectively recover iron and rare earth elements(REEs)from red mud through acid leaching-coordination-solvent extraction was proposed.The leaching efficiencies of Fe,Al,Ti,Sc,La,Ce,Nd and Y can reach up to 95.9%,82.1%,68.3%,93.3%,82.3%,96.9%,98.3%and 95.6%,respectively,under the optimal condition in the leaching process.Aliquat 336 showed excellent extraction performance of iron in chloride-rich solution,and the maximum extraction efficiency can reach over 96%in one time extraction while the loss of other metals was less than 10%,under the condition of Aliquat 336 concentration(v/v)of 30%,aqueous-organic ratio of 1.0 and extraction time of 20 min.Furthermore,P204 can effectively extract the scandium while Al and most other REEs remain in the aqueous phase.This approach may provide a new insight for the recovery of valuable resources from red mud.展开更多
Applying spent lithium iron phosphate battery as raw material,valuable metals in spent lithium ion battery were effectively recovered through separation of active material,selective leaching,and stepwise chemical prec...Applying spent lithium iron phosphate battery as raw material,valuable metals in spent lithium ion battery were effectively recovered through separation of active material,selective leaching,and stepwise chemical precipitation.Using stoichiometric Na2S2O8 as an oxidant and adding low-concentration H2SO4 as a leaching agent was proposed.This route was totally different from the conventional methods of dissolving all of the elements into solution by using excess mineral acid.When experiments were done under optimal conditions(Na2S2O8-to-Li molar ratio 0.45,0.30 mol/L H2SO4,60℃,1.5 h),leaching efficiencies of 97.53% for Li^+,1.39%for Fe^3+,and 2.58% for PO4^3−were recorded.FePO4 was then recovered by a precipitation method from the leachate while maintaining the pH at 2.0.The mother liquor was concentrated and maintained at a temperature of approximately 100℃,and then a saturated sodium carbonate solution was added to precipitate Li2CO3.The lithium recovery yield was close to 80%.展开更多
Zinc leaching residue(ZLR) contains high content of valuable metals such as zinc and iron. However, zinc and iron mainly exist in the form of zinc ferrite, which are difficult to separate and recover. This study propo...Zinc leaching residue(ZLR) contains high content of valuable metals such as zinc and iron. However, zinc and iron mainly exist in the form of zinc ferrite, which are difficult to separate and recover. This study proposed a new process involving sulfidation roasting, magnetic separation and flotation to recover zinc and iron in ZLR. Through sulfidation roasting of ZLR with pyrite, zinc and iron were converted into ZnS and Fe3 O4. The effects of pyrite dosage, roasting temperature and roasting time on the sulfidation of zinc in ZLR were investigated. The results showed that the sulfidation percentage of zinc reached 91.8% under the optimum condition. Besides, it was found that ball-milling was favorable for the separation and recovery of zinc and iron in sulfidation products. After ball-milling pretreatment, iron and zinc were enriched from sulfidation products by magnetic separation and flotation. The grade of iron in magnetic concentrates was 52.3% and the grade of zinc in flotation concentrates was 31.7%, which realized the recovery of resources.展开更多
基金Project(2022YFC2904900) supported by the National Key Research and Development Program of ChinaProject(U1902221) supported by the National Natural Science Foundation of China。
文摘Selenium distillation slag(SDS)is a high-value-added secondary resource with a high recovery value.This paper aims to investigate the leaching behavior and kinetics of selenium,tellurium,and copper in the SDS acid oxidation leaching process with H_(2)SO_(4) and H_(2)O_(2).The experimental results showed that under the optimum conditions,the contents of selenium,tellurium,and copper in the SDS were reduced from 22.13 wt%,3.58 wt%,and 6.42 wt%to 3.06 wt%,0.27 wt%,and 0.33 wt%,respectively.Correspondingly,the recovery rates are 87.08%,97.15%and 99.7%.The leaching processes of selenium and tellurium were controlled by diffusion and chemical reactions,and the leaching behavior of copper was controlled by chemical reactions.Below 45℃,the activation energies for selenium,tellurium,and copper were found to be 26.47,62.18 and 19.67 kJ/mol,respectively.In addition,the contents of lead,silver and gold in the leaching residue are increased to 46.8 wt%,8.35 wt%and 0.27 wt%,respectively.These substances can be utilized as raw materials for the recovery of these valuable metals.Importantly,the entire process does not generate toxic or harmful waste,making it a green and environmentally friendly method for resource recovery.
基金Projects(2023AG05008,202302AB080012)supported by the Yunnan Major Scientific and Technological Program,ChinaProject(202405AC350015)supported by the Science and Technology Talent Programme of Yunnan Province,China。
文摘The phase transformation of galena in H_(2)SO_(4)-Fe_(2)(SO_(4))_(3) system under oxygen pressure was investigated.Results indicated that the critical conditions for the phase transformation of galena into lead jarosite(Pb-J)were 130℃,30 g/L H_(2)SO_(4),15 g/L Fe^(3+),and an oxygen partial pressure of 0.4 MPa.Furthermore,increased Fe^(3+)concentration and oxygen partial pressure did not enhance jarosite formation.Conversely,lowering the temperature and increasing the H_(2)SO_(4) concentration facilitated PbSO_(4) formation and inhibited its further conversion to Pb-J.Additionally,the effects of potassium sulfate,sodium sulfate,and high concentrations of zinc sulfate on the phase transformation of galena were examined through leaching tests,XRD,SEM-EDS,and FT-IR analyses.All three sulfates inhibited the conversion of galena to Pb-J.Among these,potassium sulfate prevented Pb-J formation and converted it more thoroughly into potassium jarosite.However,high concentrations of zinc sulfate facilitated the crystallization of both PbSO_(4) and Pb-J,which altered the morphology of the product.Zinc ions coprecipitated with Pb-J,thereby integrating into the product.
基金Projects(52174269,52374293)supported by the National Natural Science Foundation of ChinaProject(2022RC1123)supported by the Science and Technology Innovation Program of Hunan Province,China。
文摘In this study,a synergistic sulfidation-acid leaching process was proposed to recover valuable metals from gypsum residue and zinc-containing fume.The equilibrium phase composition of the sulfidation reaction and calculations of the thermodynamic stability region show that 89.36%Zn,>99%Pb and>99%Cu of gypsum residue and zinc-containing fume can be sulfured to ZnS,PbS and Cu 2 S,under sufficient sulfur partial pressure,low oxygen partial pressure and 400-1000℃.Sulfidation roasting experiments show that the sulfidation rate of Cu,Pb and Zn reach 81.43%,88.25% and 92.31%,respectively,under the roasting conditions of material mass ratio of 30 g:10 g,carbon dosage of 3.75 g,roasting temperature of 800℃ for 3 h.E−pH plots show that ZnS,PbS and Cu_(2)S can be enriched in the leaching residue,under leaching conditions at 25℃,pH<4 and-0.4 V<φ(E)<0.04 V.The leaching experiments showed that the sulfide is retained in the leaching residue,while the leaching rates of Cu,Pb and Zn are 1.94%,2.05% and 1.51%,respectively,under the conditions of 25℃,C_(HCl) of 0.5 mol/L,L/S of 5 mL/g,stirring rate of 300 r/min,and stirring time of 30 min.This study provides a new approach for the synergistic disposal of gypsum residue and zinc containing fume.
基金Projects(52174269, 52374293) supported by the National Natural Science Foundation of ChinaProjects(2024CK1009, 2022RC1123) supported by the Science and Technology Innovation Program of Hunan Province,China。
文摘Full-component pyrolysis can process organic components and reduce cathode materials, making it a key focus in green recycling of lithium-ion batteries (LIBs). However, the leaching mechanism and kinetics of pyrolyzed black powder in organic acid systems remain unclear, with most research still at the laboratory stage. This study pioneers the exploration of the leaching behavior and reaction mechanism of valuable metal extraction from industrial-scale pyrolyzed black powder using citric acid. The effects of various leaching conditions on the extraction of metals were investigated by single factor experiments and response surface method. Under optimal conditions, the leaching efficiencies of Li, Ni, Co, and Mn all exceeded 97%. Kinetic analysis revealed that the leaching process was controlled by internal diffusion, with the apparent activation energies for Li, Ni, Co, and Mn being 17.89, 23.14, 20.27, and 15.21 kJ/mol, respectively. Additionally, residue characterization identified FePO4 formation as the primary inhibitor of iron dissolution.
基金Projects(51974137,52274299)supported by the National Natural Science Foundation of ChinaProject(2023M733190)supported by the China Postdoctoral Science Foundation。
文摘In view of the difference in coordination capacity of the glycine ion(Gly−),a selective leaching process for treating with spent lithium-ion batteries(LIBs)in the alkaline glycinate system was proposed.The effects of retention time,leaching temperature,concentration of glycine ligand,liquid-solid ratio(L/S),pH,stirring speed,and H_(2)O_(2) dosage on the leaching efficiency of valuable metals and the dissolution of impurities were investigated.When the spent LIBs were leached in 3 mol/L glycine aqueous solution with pH of 8,L/S of 5 mL:1 g and H_(2)O_(2) dosage of 5 vol.%at 90℃and stirring speed of 400 r/min for 3 h,lithium,cobalt,nickel,and manganese recoveries were 96.31%,83.18%,91.56%,and 31.16%,respectively,but Ca,Al,Fe,and Cu were almost insoluble.Meanwhile,the kinetic study showed that the activation energies for the leaching of Li,Co,Ni,and Mn were all in the range of 45−61 kJ/mol.The results indicate that the leaching process is all controlled by chemical reactions.
基金Project(51474237)supported by the National Natural Science Foundation of China
文摘The fluorine-based chemical method shows great potential in leaching lithium(Li) from lepidolite. Leaching kinetics of Li in a mixture of sulfuric acid and hydrofluoric acid, which is a typical lixivant for the fluorine-based chemical method, was carried out under crucial factors such as different HF/ore ratios(1:1-3:1 g/mL) and leaching temperatures(50-85℃). The kinetics data fit well with the developed shrinking-core model, indicating that the leaching rate of Li was controlled by the chemical reaction and inner diffusion at the beginning of leaching(0-30 min) as a calculated apparent activation energy(Ea) of 20.62 kJ/mol. The inner diffusion became the rate-limiting step as the leaching continues(60-180 min). Moreover, effects of HF/ore ratio and leaching temperature on selective leaching behavior of Li, Al and Si were discussed. 90% of fluorine mainly existed as HF/F-in leaching solution, which can provide theoretical guidance for further removal or recovery of F.
基金Projects(50934002,51104011) supported by the National Natural Science Foundation of ChinaProject(IRT0950) supported by Program for Changjiang Scholars and Innovative Research Team in Chinese UniversityProject(20100480200) supported by China Postdoctoral Science Foundation
文摘Based on the momentum and mass conservation equations, a comprehensive model of heap bioleaching process is developed to investigate the interaction between chemical reactions, solution flow, gas flow, and solute transport within the leaching system. The governing equations are solved numerically using the COMSOL Multiphysics software for the coupled reactive flow and solute transport at micro-scale, meso-scale and macro-scale levels. At or near the surface of ore particle, the acid concentration is relatively higher than that in the central area, while the concentration gradient decreases after 72 d of leaching. The flow simulation between ore particles by combining X-ray CT technology shows that the highest velocity in narrow pore reaches 0.375 m/s. The air velocity within the dump shows that the velocity near the top and side surface is relatively high, which leads to the high oxygen concentration in that area. The coupled heat transfer and liquid flow process shows that the solution can act as an effective remover from the heap, dropping the highest temperature from 60 to 38 ℃. The reagent transfer coupled with solution flow is also analyzed. The results obtained allow us to obtain a better understanding of the fundamental physical phenomenon of the bioleaching process.
基金Project(2020YFC1909805)supported by the National Key Research and Development Program of ChinaProjects(51504293,51574284)supported by the National Natural Science Foundation of China+2 种基金Project(2018-GX-A7)supported by Qinghai Provincial Major Scientific and Technological Special Project of ChinaProject(2020SK2125)supported by the Key Research and Development Program of Hunan Province,ChinaProject(CSUZC202129)supported by Open Sharing Fund for the Large-scale Instruments and Equipments of Central South University,China。
文摘Zinc extraction from crude zinc oxide(CZO)is beneficial to the full utilization of secondary resources and environmental protection.In this paper,a systematic investigation was carried out to study the leaching behavior of CZO by using ammonia-ammonium carbonate solution.It was found that the maximum leaching rate of zinc from CZO dust was 95.7%under the conditions of[Zn]T:[NH 3]T:[CO_(3)^(2−)]=1:7.00:1.75,liquid to solid ratio 5:1,leaching temperature 30℃ and leaching time 60 min.Compared with pure zinc oxide(PZO)leaching,the CZO leaching required longer time and more leaching agents,which is caused by the Cd^(2+),Pb^(2+) and other metal cationic impurities in CZO.The metal cationic impurities dissolved in the leaching solution and combined with ammonium to form complexes,consuming leaching agents and affecting zinc leaching.
基金Projects(51804136,51764016)supported by the National Natural Science Foundation of ChinaProject(U1402271)supported by the Joint Funds of the National Natural Science Foundation of China+2 种基金Project(20181BAB216017)supported by the Jiangxi Provincial Natural Science Foundation,ChinaProject(GK-201803)supported by the Research Fund Program of State Key Laboratory of Rare Metals Separation and Comprehensive Utilization,ChinaProjects(yy2016001,yy2016012)supported by the Research Fund Program of the State Key Laboratory of Pressure Hydrometallurgical Technology of Associated Nonferrous Metal Resources,China。
文摘The mechanism of oxygen pressure acid leaching of sphalerite catalyzed by Fe^3+/Fe^2+self-precipitation was investigated in this study.Artificial sphalerite was fabricated with varying amounts of iron content via the sintering of ZnS and FeS and used for the pressure acid leaching experiment.The variations in the potential of the pressure leaching system were investigated by using a self-designed potential autoclave.The results showed that compared to the non-iron sphalerite,there was a violent redox reaction between the 25.70%Fe-artificial sphalerite and dissolved oxygen during the process of pressure leaching;and the catalytic mechanism was attributed to the redox couple Fe^3+/Fe^2+,where Fe3+oxidizes the H2S gas film and the reduced Fe2+state is subsequently oxidized by the dissolved oxygen.Furthermore,the effect of temperature,H2SO4 concentration,and oxygen partial pressure on the artificial sphalerite with different iron contents was studied.The sphalerite samples with iron content were observed to dissolve more easily in sulfuric acid compared to the non-iron samples.Moreover,the activation energy of artificial sphalerite was observed to be lower in the sample with 25.70%iron content(22.26 kJ/mol)compared to that with no iron(32.31 kJ/mol);and the apparent reaction orders were obtained with respect to H2SO4 concentration(1.10 and 1.36)and oxygen partial pressure(1.29 and 1.41),respectively.A comprehensive kinetic model was developed on the basis of the experimental data and the fitted leaching ratio plot;and the kinetic equations for the leaching of sphalerite catalyzed by Fe^3+/Fe^2+self-precipitation were determined.
基金Project(51504292)supported by National Natural Science Foundation of ChinaProject(2018JJ3678)supported by the Natural Science Foundation of Hunan Province,China。
文摘To recover zinc from electric arc furnace(EAF)dust,a process of primary normal pressure leaching and secondary alkaline pressure leaching is proposed.First,under the alkaline pressure leaching system,the experiment of pure zinc ferrite being reduced by iron powder was carried out.Under the optimal reduction conditions(i.e.,temperature of 260℃,NaOH concentration of 6 mol/L,liquid-to-solid ratio of 50 mL/g,and a 5-fold excess of iron powder),89%of zinc was extracted.The iron in the reduced residue exists as a magnetite phase.Subsequently,the normal pressure leaching experiment was carried out with EAF dust as raw material,and 66%zinc was leached.The main phase of zinc in normal leaching residue was determined to be zinc ferrite.Then,the normal leaching residue was reduced by iron powder under the alkaline pressure leaching system,and 66.5%of zinc was extracted.After the two-stage leaching process,the leaching rate of zinc in EAF dust can achieve 88.7%.The alkaline pressure leaching solution can be returned as the normal pressure leaching solution,and the magnetite in the alkaline pressure leaching residue can be recovered by magnetic separation.
基金Project(51574286)supported by the National Natural Science Foundation of China。
文摘Inner Mongolian serpentine ore was subjected to sulfuric acid leaching tests,and the effects of the leaching process parameters on the leaching efficiency of different metals were investigated.The leaching efficiency of Mg,Fe,Al,Ni,and Co reaches 93.98%,60.09%,82.08%,90.58%,and 94.06%,respectively,under the leaching conditions of 5 mol/L H_(2)SO_(4),liquid/solid ratio of 4 mL/g,and leaching temperature 100℃.Hence,the valuable metals in serpentine were effectively recovered by sulfuric acid leaching.The leaching behaviors of Mg,Fe,and a small amount of Al were analyzed using X-ray diffraction.The results show that the unreacted Mg and Fe remained as MgFe_(2)O_(4),and Al formed Al_(2)Si_(2)O_(5)(OH)_(4) in the leaching residue.The kinetics of Mg and Ni in the leaching process was studied respectively.The leaching kinetics of Mg conformed to the shrinking core model with an activation energy of 16.95 kJ/mol,which was controlled by the combination of the diffusion and chemical reaction.The leaching kinetics of Ni accorded with the Avrami equation with an activation energy of 11.57 kJ/mol,which was controlled by diffusion.In the study,the valuable metal elements were extracted from serpentine minerals with high efficiency and low cost,which possessed important practical values.
基金Project(20876014) supported by the National Natural Science Foundation of China
文摘Physical and chemical properties of electric arc furnace （EAF） dust from Tianjin seamless Pipe Company were measured and analyzed. The zinc leaching tests in alkaline medium were carried out under variation of leaching agent concentration, leaching temperature, leaching cumulative time and solid-to-liquid ratio. The thermodynamics and kinetics of the zinc leaching process were also analyzed. The results show that the EAF dust contains 10% （mass fraction） zinc and the median particle size is 0.69 μm. The zinc recovery of 73.4% is obtained tinder the condition of 90 ℃, 6 mol/L NaOH, and 60 min leaching time. With the increase of concentration of NaOH and the cumulative time, zinc leaching will be significantly increased. The kinetics study demonstrates that the leaching reaction is chemically controlled and the reaction activation energy is 15.73 kJ/mol.
基金Projects(2006AA06Z374 2007AA021304) supported by the National High-Tech Research and Development Program of China
文摘A batch of column experiments was carried out to investigate the change of Cr（Ⅵ） concentration leached out from chromium-containing slag with HCI as leaching agent, and to study influences of pH, ratio of solid mass to solution volume, flow velocity and temperature on Cr（Ⅵ） leaching. The optimal parameters were obtained for Cr（Ⅵ） leaching and a fitting model was established to describe the procedure of Cr（Ⅵ） leaching. The results show that Cr（Ⅵ） concentration in leachate increases with decreasing pH and increasing flow velocity and temperature. Moreover, Cr（Ⅵ） leaching percentage increases with increasing ratio of solid mass to solution volume. The optimal parameters for Cr（Ⅵ） selective leaching are as follows： pH=3.0, 1：5 of ratio of solid mass to solution volume, 180 mL/min of flow velocity and 40 ℃ of temperature. The procedure of Cr（Ⅵ） leaching fits well with the model： v= 1.87t^-0.54, indicating that the leaching rate of Cr（Ⅵ） declines in an exponential order of-0.54.
文摘Based on the law of temperature changes in the leaching dump and the forming process of heat flux, the basic balance equation of heat flow in dump was established, the dissipated heat flow from dump to the atmosphere was analyzed to estimate the surface temperature of the ore particle in dump and discover the law of forced heat convection of heat flow transfer in dump. And the lixiviate flow formula taking a certain heat flow out of dump was deduced by using the inversion method. Through theoretic analysis, combining Dexing copper mine heap leaching production practice, the results show that the heat flow of chalcopyrite leaching emitted is not so great, but the heat flow of pyrite leaching and sulphur oxidation produced take up a higher proportion of total heat flow; the dissipated heat flow takes up a lower proportion, and most of heat flow is absorbed by itself, thus the inside temperature rises gradually; and the saturation flow form for leaching is adopted, which makes the lixiviate seepage in the transitional flow or even in the turbulent flow, so as to accelerate the heat flow diffusing and keep the leaching dump temperature suitable for bacteria living.
基金Project(2004CB19206) supported by State Key Fundamental Research and Development Program of China project(50321402) supported by the National Science Fundfor Distinguished Young Scholars of China project(50321402) supported by NationalFund for Creative Research Groups of China
文摘According to the chemical equations, the flux and concentration of oxygen required during bacterial lea- ching sulfuric mineral were investigated; the rule of air bubble transmitted in granular was researched in the Dump Leaching Plant of Dexing Copper Mine. The results show that lack of oxygen in dump leaching is the critical factor of restricting leaching reaction. Pyrite is the primary oxygen-consuming mineral in bioleaching. When its content is too high, it needs a great deal of oxygen for reaction and competes for the finite oxygen with objective minerals, and thus the leaching velocity decreases greatly. The average size of ore particles and diameter of bubbles are the key parameters affecting the mass transfer coefficient. Reverse analysis was adopted, and it shows that 44.8 m^3 air per unit ore can meet the requirement of production if the molar ratio of pyrite to chalcopyrite is 10.
基金Project(51374035)supported by the National Natural Science Foundation of ChinaProject(2012BAB08B02)supported by the National“Twelfth Five”Science and Technology,ChinaProject(NCET-13-0669)supported by New Century Excellent Talents in University of Ministry of Education of China
文摘A laboratory leaching experiment with samples of different grades was carried out, and an analytical method of concentration of leaching solution was put forward. For each sample, respectively, by applying phase space reconstruction for time series of monitoring data, the saturated embedding dimension and the correlation dimension were obtained, and the evolution laws between neighboring points in the reconstructed phase space were revealed. With BP neural network, a prediction model of concentration of leaching solution was set up and the maximum error of which was less than 2%. The results show that there exist chaotic characteristics in leaching system, and samples of different grades have different nonlinear dynamic features; the higher the grade of sample, the smaller the correlation dimension; furthermore, the maximum Lyapunov index, energy dissipation and chaotic extent of the leaching system increase with grade of the sample; by phase space reconstruction, the subtle change features of concentration of leaching solution can be magnified and the inherent laws can be fully demonstrated. According to the laws, a prediction model of leaching cycle period has been established to provide a theoretical foundation for solution mining.
基金Projects(51374248,51320105006) supported by National Natural Science Foundation of ChinaProject(NCET-13-0595) supported by the Program for New Century Excellent Talents in University,ChinaProject(2014T70692) supported by the China Postdoctoral Science Foundation
文摘For the low-grade copper sulfide ores with 0.99% of copper, of which 41.5% was primary copper sulfide, and 54.5% was secondary copper sulfide, well-controlled column bioleaching on a novel equipment was carried out to investigate the optimal conditions of pre-leaching, particle sizes of ores, temperature, spray intensity and strain consortium. Results show that copper extraction of 91.11% can be obtained after 90 d with the optimal p H value of pre-leaching of 0.8; the p H values of pre-leaching significantly affect the final copper extractions. Copper extractions of 93.11%, 91.04% and 80.45% can be obtained for the bioleaching of ores with particles size of 5-8 mm, 5-15 mm and 5-20 mm, respectively. Copper extractions are 83.77% and 91.02% for bioleaching under the conditions of room temperature and 35 oC. Copper extractions are 77.25%, 85.45% and 91.12% for the bioleaching when flow rate of spray was 5 L/（h·m2）, 10 L/（h·m2） and 15 L/（h·m2）, respectively. Additionally, the strain consortium C3 is the best among the four strain consortia in bioleaching. By considering the energy consumption, the optimal conditions of bioleaching in this work are determined as p H of pre-leaching of 0.8, particles size of 5-15 mm, temperature of 35 ℃, spray intensity of 15 L/（h·m2）, and strain consortium C3.
基金Project(21707167)supported by the Natural Science Foundation of China
文摘A feasible approach to selectively recover iron and rare earth elements(REEs)from red mud through acid leaching-coordination-solvent extraction was proposed.The leaching efficiencies of Fe,Al,Ti,Sc,La,Ce,Nd and Y can reach up to 95.9%,82.1%,68.3%,93.3%,82.3%,96.9%,98.3%and 95.6%,respectively,under the optimal condition in the leaching process.Aliquat 336 showed excellent extraction performance of iron in chloride-rich solution,and the maximum extraction efficiency can reach over 96%in one time extraction while the loss of other metals was less than 10%,under the condition of Aliquat 336 concentration(v/v)of 30%,aqueous-organic ratio of 1.0 and extraction time of 20 min.Furthermore,P204 can effectively extract the scandium while Al and most other REEs remain in the aqueous phase.This approach may provide a new insight for the recovery of valuable resources from red mud.
基金Project(Z20160605230001)supported by Hunan Province Non-ferrous Fund Project,China。
文摘Applying spent lithium iron phosphate battery as raw material,valuable metals in spent lithium ion battery were effectively recovered through separation of active material,selective leaching,and stepwise chemical precipitation.Using stoichiometric Na2S2O8 as an oxidant and adding low-concentration H2SO4 as a leaching agent was proposed.This route was totally different from the conventional methods of dissolving all of the elements into solution by using excess mineral acid.When experiments were done under optimal conditions(Na2S2O8-to-Li molar ratio 0.45,0.30 mol/L H2SO4,60℃,1.5 h),leaching efficiencies of 97.53% for Li^+,1.39%for Fe^3+,and 2.58% for PO4^3−were recorded.FePO4 was then recovered by a precipitation method from the leachate while maintaining the pH at 2.0.The mother liquor was concentrated and maintained at a temperature of approximately 100℃,and then a saturated sodium carbonate solution was added to precipitate Li2CO3.The lithium recovery yield was close to 80%.
基金Project(2018YFC1900305)supported by the National Key R&D Program of ChinaProject(51825403)supported by the National Science Foundation for Distinguished Young Scholars,China+1 种基金Projects(51634010,51474247,51904354)supported by the National Natural Science Foundation of ChinaProject(2019SK2291)supported by the Key Research and Development Program of Hunan Province,China。
文摘Zinc leaching residue(ZLR) contains high content of valuable metals such as zinc and iron. However, zinc and iron mainly exist in the form of zinc ferrite, which are difficult to separate and recover. This study proposed a new process involving sulfidation roasting, magnetic separation and flotation to recover zinc and iron in ZLR. Through sulfidation roasting of ZLR with pyrite, zinc and iron were converted into ZnS and Fe3 O4. The effects of pyrite dosage, roasting temperature and roasting time on the sulfidation of zinc in ZLR were investigated. The results showed that the sulfidation percentage of zinc reached 91.8% under the optimum condition. Besides, it was found that ball-milling was favorable for the separation and recovery of zinc and iron in sulfidation products. After ball-milling pretreatment, iron and zinc were enriched from sulfidation products by magnetic separation and flotation. The grade of iron in magnetic concentrates was 52.3% and the grade of zinc in flotation concentrates was 31.7%, which realized the recovery of resources.
