Physicochemical properties of arsenic sulfide sludge(ASS) from copper smelter(ASS-I) and lead-zinc smelter(ASS-II) were examined by XRD, Raman spectroscopy, SEM-EDS, TG-DTA, XPS and chemical phase analysis method. The...Physicochemical properties of arsenic sulfide sludge(ASS) from copper smelter(ASS-I) and lead-zinc smelter(ASS-II) were examined by XRD, Raman spectroscopy, SEM-EDS, TG-DTA, XPS and chemical phase analysis method. The toxicity characteristic leaching procedure(TCLP), Chinese standard leaching tests(CSLT), three-stage sequential extraction procedure(BCR) and batch leaching experiments(BLE) were used to investigate the environmental stability. The ASSs from different smelters had obviously different physicochemical and environmental properties. The phase composition and micrograph analysis indicate that ASS-I mainly consists of super refined flocculent particles including amorphous arsenic sulfide adhered with amorphous sulfur and that ASS-II mainly consists of amorphous arsenic sulfide. The valence state of arsenic in both sludges is trivalent, but the valence composition of sulfur is quite different. The ASSs have thermal instability properties. The results of TCLP and CSLT indicate that the concentrations of As and Pd in the leaching solution exceed the standard limits. More than 5% and 90% of arsenic are in the form of acid soluble and oxidizable fractions, respectively, which explains the high arsenic leaching toxicity and environmental activity of ASS. This research provides comprehensive information for the disposal of ASS from copper and lead-zinc smelter.展开更多
Physicochemical properties and leaching behaviors of two typical arsenic-bearing lime?ferrate sludges(ABLFS),waste acid residue(WAR)and calcium arsenate residue(CAR),are comprehensively described.The chemical composit...Physicochemical properties and leaching behaviors of two typical arsenic-bearing lime?ferrate sludges(ABLFS),waste acid residue(WAR)and calcium arsenate residue(CAR),are comprehensively described.The chemical composition,morphological features,phase composition and arsenic occurrence state of WAR and CAR are analyzed by ICP?AES,SEM?EDS,XRD,XPS and chemical phase analysis.The toxicity leaching test and three-stage BCR sequential extraction procedure are utilized to investigate arsenic leaching behaviors.The results show that the contents of arsenic in WAR and CAR are2.5%and21.2%and mainly present in the phases of arsenate and arsenic oxides dispersed uniformly or agglomerated in amorphous particles.The leaching concentrations of arsenic excess119and1063times of TCLP standard regulatory level with leaching rates of47.66%and50.15%for WAR and CAR,respectively.About90%of extracted arsenic is in the form of acid soluble and reducible,which is the reason of high arsenic leaching toxicity and environmental activity of ABLFS.This research provides comprehensive information on harmless disposal of ABLFS from industrial wastewater treatment of lime?ferrate process.展开更多
A new hydrometallurgical route for separation and recovery of Cu from Cu-As-bearing copper electrorefining black slime was developed. The proposed process comprised oxidation acid leaching of Cu-As-bearing slime and s...A new hydrometallurgical route for separation and recovery of Cu from Cu-As-bearing copper electrorefining black slime was developed. The proposed process comprised oxidation acid leaching of Cu-As-bearing slime and selective sulfide precipitation of Cu from the leachate. The effects of various process parameters on the leaching and precipitation of Cu and As were investigated. At the first stage, Cu extraction of 95.2% and As extraction of 97.6% were obtained at 80 ℃ after 4 h with initial H2 SO4 concentration of 1.0 mol/L and liquid-to-solid ratio of 10 mL/g. In addition, the leaching kinetics of Cu and As was successfully reproduced by the Avrami model, and the apparent activation energies were found to be 33.6 and 35.1 kJ/mol for the Cu and As leaching reaction, respectively, suggesting a combination of chemical reaction and diffusion control. During the selective sulfide precipitation, about 99.4% Cu was recovered as CuS, while only 0.1% As was precipitated under the optimal conditions using sulfide-to-copper ratio of 2.4:1, time of 1.5 h and temperature of 25 ℃.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
The heat recovery steam generator(HRSG)of copper smelting generates a large number of arsenic−coppercontaining particles,and the in-situ separation of arsenic and copper is of importance for cutting off environmental ...The heat recovery steam generator(HRSG)of copper smelting generates a large number of arsenic−coppercontaining particles,and the in-situ separation of arsenic and copper is of importance for cutting off environmental risk and realizing resource recovery.The formation of arsenic−copper-containing particles was simulated,the method of in-situ decomposition of arsenic−copper-containing particles by pyrite was proposed,and the decomposition mechanism was confirmed.It was found that particles with high arsenic content were formed in the simulated HRSG,and copper arsenate was liable for the high arsenic content.Pyrite promoted the sulfation of copper,leading to the in-situ decomposition of copper arsenate.In this process,gaseous arsenic was released,and thus the separation of arsenic and copper was realized.展开更多
An optimized hydrothermal treatment was employed to stabilize the arsenic sulfide sludge(ASS). Under the optimal conditions(160 ℃, 2 h, liquid-to-solid(L/S) ratio of 1:1, and initial pH of 2), the leaching concentrat...An optimized hydrothermal treatment was employed to stabilize the arsenic sulfide sludge(ASS). Under the optimal conditions(160 ℃, 2 h, liquid-to-solid(L/S) ratio of 1:1, and initial pH of 2), the leaching concentrations of As and Cd decreased from 504.0 and 12.0 mg/L to 1.23 and 0.03 mg/L of the treated ASS, respectively. The results indicate that the stabilization of the ASS was achieved through structure transformation from the particles into a bulk and the speciation transformation of As and Cd. Besides, sulfur in the ASS could significantly improve the stabilization property due to its melting and polymerization.展开更多
Scorodite（FeAsO4·2H2O）is the most popular phase for arsenic（As）immobilization while the reductive dissolution of Fe（Ⅲ）to Fe（Ⅱ）will promote As release.In the present study,an equilibrium between Fe（Ⅲ）...Scorodite（FeAsO4·2H2O）is the most popular phase for arsenic（As）immobilization while the reductive dissolution of Fe（Ⅲ）to Fe（Ⅱ）will promote As release.In the present study,an equilibrium between Fe（Ⅲ）and Fe（Ⅱ）was achieved in scorodite preparation system by introducing certain alcohol（methanol,ethanol,isopropanol or tert-butanol）,and thus a new mixed-valent iron arsenate black crystal formulated as Fe（Ⅱ）（5.2）Fe（Ⅲ）（8.8）（HAsO4）4（AsO4）8·H2O was prepared.In comparison with scorodite,the black crystal has higher As content（36.4%,mass fraction）and lower crystal water content（0.73%,mass fraction）.Additionally,the leaching concentration of As can be lower than the threshold value（5 mg/L）regulated by identification standards for hazardous wastes of China（GB 5080.3-2007）.Therefore,this new mixed-valent iron arsenate crystal could be classified as a non-hazardous and promising As-bearing phase in environmental applications.展开更多
The microstructure and magnetic properties of iron arsenide(FeAs) with coarse-grain and nanocrystalline structure were investigated. Coarse-grain FeAs was synthesized through high-energy ball milling and heat treatmen...The microstructure and magnetic properties of iron arsenide(FeAs) with coarse-grain and nanocrystalline structure were investigated. Coarse-grain FeAs was synthesized through high-energy ball milling and heat treatment. Nanocrystalline FeAs was obtained by ball milling of coarse-grain FeAs. The results suggest that the reduced grain size of FeAs(from >100 to 32.4 nm) is accompanied by the introduction of internal strains up to 0.568% with ball milling time from 0 to 32 h. The magnetic properties of FeAs show that the coercivity is reduced from 29.2 to 15.6 kA/m and the magnetization is increased over time of milling. The low coercivity is mainly due to the small grain size stemmed from ball milling, while the increase of magnetization is primarily caused by the change of lattice parameters of FeAs and the emergence of superparamagnetic phase at the same time.展开更多
Arsenic materials have attracted great attention due to their unique properties.However,research concerning iron-arsenic(Fe-As) alloys is very scarce due to the volatility of As at low temperature and the high melting...Arsenic materials have attracted great attention due to their unique properties.However,research concerning iron-arsenic(Fe-As) alloys is very scarce due to the volatility of As at low temperature and the high melting point of Fe.Herein,a new Fe-As alloy was obtained by mechanical alloying(MA) followed by vacuum hot-pressed sintering(VHPS).Moreover,a systematic study was carried out on the microstructural evolution,phase composition,leaching toxicity of As,and physical and mechanical properties of Fe-As alloys with varying weight fractions of As(20%,25%,30%,35%,45%,55%,65%,and 75%).The results showed that pre-alloyed metallic powders(PAMPs) have a fine grain size and specific supersaturated solid solution after MA,which could effectively improve the mechanical properties of Fe-As alloys by VHPS.A high density(> 7.350 g·cm^(-3)),low toxicity,and excellent mechanical properties could be obtained for FeAs alloys sintered via VHPS by adding an appropriate amount of As,which is more valuable than commercial Fe-As products.The Fe-25% As alloy with low toxicity and a relatively high density(7.635 g·cm^(-3)) provides an ultra-high compressive strength(1989.19 MPa),while the Fe-65% As alloy owns the maximum Vickers hardness(HVo.5 899.41).After leaching by the toxicity characteristic leaching procedure(TCLP),these alloys could still maintain good mechanical performance,and the strengthening mechanisms of Fe-As alloys before and after leaching were clarified.Changes in the grain size,micro structure,and phase distribution induced significant differences in the compressive strength and hardness.展开更多
A method to upgrade the iron grade in copper slag was proposed using lime to decompose Al_(2)O_(3)-containing fayalite melt(AFMT).Thermodynamic calculations indicated that adjusting the CaO/AFMT ratio can yield a resi...A method to upgrade the iron grade in copper slag was proposed using lime to decompose Al_(2)O_(3)-containing fayalite melt(AFMT).Thermodynamic calculations indicated that adjusting the CaO/AFMT ratio can yield a residual melt with a FeO concentration of 75−88 wt.%and produce Ca_(2)SiO_(4).In-situ observations suggested that the reaction was impeded in some way.Quenching experiments revealed that the initial reaction products consisted of calcium ferrite compounds and FeO−CaO melt.At the FeO−CaO melt/AFMT interface,Ca_(2)SiO_(4) particles precipitated,forming a dense Ca_(2)SiO_(4) film that significantly impeded mass transfer.Although trace amounts of Al_(2)O_(3) in AFMT temporarily enhanced mass transfer,they were insufficient to overcome this retardation effect.The decomposition reaction was far from achieving equilibrium,demonstrating a self-retardation effect.Measures must be implemented to eliminate this self-retardation effect and enhance the efficiency of reaction kinetics.展开更多
基金BASF New Material Pb Methanesulfonic Acid System Pb Electrolytic Refining Project,China(No.738010278)the Natural Science Foundation of Hunan Province of China for Youths(No.2020JJ5628).
基金Projects(51904354,51634010)supported by the National Natural Science Foundation of ChinaProject(51825403)supported by the National Science Fund for Distinguished Young Scholars,ChinaProjects(2018YFC1903301,2018YFC1900301)supported by the National Key R&D Program of China。
文摘Physicochemical properties of arsenic sulfide sludge(ASS) from copper smelter(ASS-I) and lead-zinc smelter(ASS-II) were examined by XRD, Raman spectroscopy, SEM-EDS, TG-DTA, XPS and chemical phase analysis method. The toxicity characteristic leaching procedure(TCLP), Chinese standard leaching tests(CSLT), three-stage sequential extraction procedure(BCR) and batch leaching experiments(BLE) were used to investigate the environmental stability. The ASSs from different smelters had obviously different physicochemical and environmental properties. The phase composition and micrograph analysis indicate that ASS-I mainly consists of super refined flocculent particles including amorphous arsenic sulfide adhered with amorphous sulfur and that ASS-II mainly consists of amorphous arsenic sulfide. The valence state of arsenic in both sludges is trivalent, but the valence composition of sulfur is quite different. The ASSs have thermal instability properties. The results of TCLP and CSLT indicate that the concentrations of As and Pd in the leaching solution exceed the standard limits. More than 5% and 90% of arsenic are in the form of acid soluble and oxidizable fractions, respectively, which explains the high arsenic leaching toxicity and environmental activity of ASS. This research provides comprehensive information for the disposal of ASS from copper and lead-zinc smelter.
基金Project(201509050)supported by Special Program on Environmental Protection for Public Welfare,ChinaProjects(51474247,51634010)supported by the National Natural Science Foundation of ChinaProject(2015CX001)supported by Grants from the Project of Innovation-driven Plan in Central South University,China
文摘Physicochemical properties and leaching behaviors of two typical arsenic-bearing lime?ferrate sludges(ABLFS),waste acid residue(WAR)and calcium arsenate residue(CAR),are comprehensively described.The chemical composition,morphological features,phase composition and arsenic occurrence state of WAR and CAR are analyzed by ICP?AES,SEM?EDS,XRD,XPS and chemical phase analysis.The toxicity leaching test and three-stage BCR sequential extraction procedure are utilized to investigate arsenic leaching behaviors.The results show that the contents of arsenic in WAR and CAR are2.5%and21.2%and mainly present in the phases of arsenate and arsenic oxides dispersed uniformly or agglomerated in amorphous particles.The leaching concentrations of arsenic excess119and1063times of TCLP standard regulatory level with leaching rates of47.66%and50.15%for WAR and CAR,respectively.About90%of extracted arsenic is in the form of acid soluble and reducible,which is the reason of high arsenic leaching toxicity and environmental activity of ABLFS.This research provides comprehensive information on harmless disposal of ABLFS from industrial wastewater treatment of lime?ferrate process.
基金financial supports from the National Natural Science Foundation of China (51634010,51904354)the National Science Fund for Distinguished Young Scholars of China (51825403)+1 种基金the National Key R&D Program of China (2018YFC1900306,2019YFC1907405)Key Research and Development Program of Hunan Province,China (2019SK2291)。
文摘A new hydrometallurgical route for separation and recovery of Cu from Cu-As-bearing copper electrorefining black slime was developed. The proposed process comprised oxidation acid leaching of Cu-As-bearing slime and selective sulfide precipitation of Cu from the leachate. The effects of various process parameters on the leaching and precipitation of Cu and As were investigated. At the first stage, Cu extraction of 95.2% and As extraction of 97.6% were obtained at 80 ℃ after 4 h with initial H2 SO4 concentration of 1.0 mol/L and liquid-to-solid ratio of 10 mL/g. In addition, the leaching kinetics of Cu and As was successfully reproduced by the Avrami model, and the apparent activation energies were found to be 33.6 and 35.1 kJ/mol for the Cu and As leaching reaction, respectively, suggesting a combination of chemical reaction and diffusion control. During the selective sulfide precipitation, about 99.4% Cu was recovered as CuS, while only 0.1% As was precipitated under the optimal conditions using sulfide-to-copper ratio of 2.4:1, time of 1.5 h and temperature of 25 ℃.
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%.
基金financially supported by the National Science Fund for Excellent Young Scholars of China(No.52022111)the National Key Research and Development Program of China(Nos.2017YFC0210401,2018YFC1900306)+1 种基金the Distinguished Young Scholars of China(No.51825403)the National Natural Science Foundation of China(Nos.51634010,51974379).
文摘The heat recovery steam generator(HRSG)of copper smelting generates a large number of arsenic−coppercontaining particles,and the in-situ separation of arsenic and copper is of importance for cutting off environmental risk and realizing resource recovery.The formation of arsenic−copper-containing particles was simulated,the method of in-situ decomposition of arsenic−copper-containing particles by pyrite was proposed,and the decomposition mechanism was confirmed.It was found that particles with high arsenic content were formed in the simulated HRSG,and copper arsenate was liable for the high arsenic content.Pyrite promoted the sulfation of copper,leading to the in-situ decomposition of copper arsenate.In this process,gaseous arsenic was released,and thus the separation of arsenic and copper was realized.
基金supported by the National Natural Science Foundation of China for Distinguished Young Scholars (No. 51825403)the National Key R&D Program of China (Nos. 2018YFC1903301, 2018YFC1900301)the National Natural Science Foundation of China (Nos. 51634010, 51904354)。
文摘An optimized hydrothermal treatment was employed to stabilize the arsenic sulfide sludge(ASS). Under the optimal conditions(160 ℃, 2 h, liquid-to-solid(L/S) ratio of 1:1, and initial pH of 2), the leaching concentrations of As and Cd decreased from 504.0 and 12.0 mg/L to 1.23 and 0.03 mg/L of the treated ASS, respectively. The results indicate that the stabilization of the ASS was achieved through structure transformation from the particles into a bulk and the speciation transformation of As and Cd. Besides, sulfur in the ASS could significantly improve the stabilization property due to its melting and polymerization.
基金Project(51634010)supported by the Key Project of National Natural Science Foundation of ChinaProject(51304251)supported by the National Natural Science Foundation of ChinaProject(201509050)supported by Special Program on Environmental Protection for Public Welfare of China
文摘Scorodite（FeAsO4·2H2O）is the most popular phase for arsenic（As）immobilization while the reductive dissolution of Fe（Ⅲ）to Fe（Ⅱ）will promote As release.In the present study,an equilibrium between Fe（Ⅲ）and Fe（Ⅱ）was achieved in scorodite preparation system by introducing certain alcohol（methanol,ethanol,isopropanol or tert-butanol）,and thus a new mixed-valent iron arsenate black crystal formulated as Fe（Ⅱ）（5.2）Fe（Ⅲ）（8.8）（HAsO4）4（AsO4）8·H2O was prepared.In comparison with scorodite,the black crystal has higher As content（36.4%,mass fraction）and lower crystal water content（0.73%,mass fraction）.Additionally,the leaching concentration of As can be lower than the threshold value（5 mg/L）regulated by identification standards for hazardous wastes of China（GB 5080.3-2007）.Therefore,this new mixed-valent iron arsenate crystal could be classified as a non-hazardous and promising As-bearing phase in environmental applications.
基金the financial support from National Key Technologies R&D Program of China (No. 2018YFC1900302)。
文摘The microstructure and magnetic properties of iron arsenide(FeAs) with coarse-grain and nanocrystalline structure were investigated. Coarse-grain FeAs was synthesized through high-energy ball milling and heat treatment. Nanocrystalline FeAs was obtained by ball milling of coarse-grain FeAs. The results suggest that the reduced grain size of FeAs(from >100 to 32.4 nm) is accompanied by the introduction of internal strains up to 0.568% with ball milling time from 0 to 32 h. The magnetic properties of FeAs show that the coercivity is reduced from 29.2 to 15.6 kA/m and the magnetization is increased over time of milling. The low coercivity is mainly due to the small grain size stemmed from ball milling, while the increase of magnetization is primarily caused by the change of lattice parameters of FeAs and the emergence of superparamagnetic phase at the same time.
基金financially supported by the National Natural Science Foundation of China (No.52104406)the Natural Science Foundation of Hunan Province (No.2022JJ20074)+1 种基金the Foundation for Innovative Research Groups of the National Natural Science Foundation of China (No.52121004)the National Natural Science Foundation of China for Distinguished Young Scholars (No.51825403)。
文摘Arsenic materials have attracted great attention due to their unique properties.However,research concerning iron-arsenic(Fe-As) alloys is very scarce due to the volatility of As at low temperature and the high melting point of Fe.Herein,a new Fe-As alloy was obtained by mechanical alloying(MA) followed by vacuum hot-pressed sintering(VHPS).Moreover,a systematic study was carried out on the microstructural evolution,phase composition,leaching toxicity of As,and physical and mechanical properties of Fe-As alloys with varying weight fractions of As(20%,25%,30%,35%,45%,55%,65%,and 75%).The results showed that pre-alloyed metallic powders(PAMPs) have a fine grain size and specific supersaturated solid solution after MA,which could effectively improve the mechanical properties of Fe-As alloys by VHPS.A high density(> 7.350 g·cm^(-3)),low toxicity,and excellent mechanical properties could be obtained for FeAs alloys sintered via VHPS by adding an appropriate amount of As,which is more valuable than commercial Fe-As products.The Fe-25% As alloy with low toxicity and a relatively high density(7.635 g·cm^(-3)) provides an ultra-high compressive strength(1989.19 MPa),while the Fe-65% As alloy owns the maximum Vickers hardness(HVo.5 899.41).After leaching by the toxicity characteristic leaching procedure(TCLP),these alloys could still maintain good mechanical performance,and the strengthening mechanisms of Fe-As alloys before and after leaching were clarified.Changes in the grain size,micro structure,and phase distribution induced significant differences in the compressive strength and hardness.
基金supported by the National Natural Science Foundation of China (No.52121004)the National Science Fund for Distinguished Young Scholars (No.51825403)+2 种基金the Science and Technology Innovation Program of Hunan Province,China (No.2021RC3013)National Key R&D Program of China (No.2022YFC3901602)the Major Science and Technology Project of Gansu Province,China (No.21ZD4GD033)。
文摘A method to upgrade the iron grade in copper slag was proposed using lime to decompose Al_(2)O_(3)-containing fayalite melt(AFMT).Thermodynamic calculations indicated that adjusting the CaO/AFMT ratio can yield a residual melt with a FeO concentration of 75−88 wt.%and produce Ca_(2)SiO_(4).In-situ observations suggested that the reaction was impeded in some way.Quenching experiments revealed that the initial reaction products consisted of calcium ferrite compounds and FeO−CaO melt.At the FeO−CaO melt/AFMT interface,Ca_(2)SiO_(4) particles precipitated,forming a dense Ca_(2)SiO_(4) film that significantly impeded mass transfer.Although trace amounts of Al_(2)O_(3) in AFMT temporarily enhanced mass transfer,they were insufficient to overcome this retardation effect.The decomposition reaction was far from achieving equilibrium,demonstrating a self-retardation effect.Measures must be implemented to eliminate this self-retardation effect and enhance the efficiency of reaction kinetics.
