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
Battery grade γ-MnO2 powder was investigated as an oxidant and an adsorbent in combination with Fe/Al coagulants for removal of arsenic from contaminated water. Simultaneous oxidation of As(III) and removal by coprec...Battery grade γ-MnO2 powder was investigated as an oxidant and an adsorbent in combination with Fe/Al coagulants for removal of arsenic from contaminated water. Simultaneous oxidation of As(III) and removal by coprecipitation/adsorption (one step process) was compared with pre-oxidation and subsequent removal by coprecipitation/adsorption (two step process). The rate of As(III) oxidation with MnO2 is completed in two stages: rapid initially followed by a first order reaction. As(III) is oxidised to As(V) by the MnO2 with a release of approximately 1:1 molar Mn(II) into the solution. No significant pH effect on oxidation of As(III) was observed in the pH range 4 - 6. The rate showed a decreasing trend above pH 6. The removal of As(V) by adsorption on the MnO2 decreased significantly with increasing pH from 4 to 8. The adsorption capacity of the γ-MnO2 with particle size 90% passing 10 μm was determined to be 1.5 mg/g at pH 7. MnO2 was found to be more effective as an oxidant for As(III) in the two step process than in the one step process.展开更多
Fenton and Fenton-like processes,which could produce highly reactive species to degrade organic contaminants,have been widely used in the field of wastewater treatment.Therein,the chemistry of Fenton process including...Fenton and Fenton-like processes,which could produce highly reactive species to degrade organic contaminants,have been widely used in the field of wastewater treatment.Therein,the chemistry of Fenton process including the nature of active oxidants,the complicated reactions involved,and the behind reason for its strongly pH-dependent performance,is the basis for the application of Fenton and Fenton-like processes in wastewater treatment.Nevertheless,the conflicting views still exist about the mechanism of the Fenton process.For instance,reaching a unanimous consensus on the nature of active oxidants(hydroxyl radical or tetravalent iron)in this process remains challenging.This review comprehensively examined the mechanism of the Fenton process including the debate on the nature of active oxidants,reactions involved in the Fenton process,and the behind reason for the pH-dependent degradation of contaminants in the Fenton process.Then,we summarized several strategies that promote the Fe(Ⅱ)/Fe(Ⅲ)cycle,reduce the competitive consumption of active oxidants by side reactions,and replace the Fenton reagent,thus improving the performance of the Fenton process.Furthermore,advances for the future were proposed including the demand for the high-accuracy identification of active oxidants and taking advantages of the characteristic of target contaminants during the degradation of contaminants by the Fenton process.展开更多
Iron and oxalic acids are widely distributed in the atmosphere and easily form ferric oxalate complex(Fe(III)-Ox).The tropospheric aqueous-phase could provide a medium to enable the photo-Fenton reaction with Fe(III)-...Iron and oxalic acids are widely distributed in the atmosphere and easily form ferric oxalate complex(Fe(III)-Ox).The tropospheric aqueous-phase could provide a medium to enable the photo-Fenton reaction with Fe(III)-Ox under solar irradiation.Although the photolysis mechanisms of Fe(III)-Ox have been investigated extensively,information about the oxidation of volatile organic compounds(VOC),specifically the potential for Secondary Organic Aerosol(SOA)formation in the Fe(III)-Ox system,is lacking.In this study,a ubiquitous VOC methacrolein(MACR)is chosen as a model VOC,and the oxidation of MACR with Fe(III)-Ox is investigated under typical atmospheric water conditions.The effects of oxalate concentration,Fe(III)concentration,MACR concentration,and pH on the oxidation of MACR are studied in detail.Results show that the oxidation rate of MACR greatly accelerates in the presence of oxalate when compared with only Fe(III).The oxidation rate of MACR also accelerates with increasing concentration of oxalate.The effect of Fe(III)is found to be more complicated.The oxidation rate of MACR first increases and then decreases with increasing Fe(III)concentration.The oxidation rate of MACR increases monotonically with decreasing pH in the common atmospheric water pH range or with decreasing MACR concentration.The production of ferrous and hydrogen peroxide,pH,and aqueous absorbance are monitored throughout the reaction process.The quenching experiments verify that·OH and O_(2)^(+)are both responsible for the oxidation of MACR.MACR is found to rapidly oxidize into small organic acids with higher boiling points and oligomers with higher molecular weight,which contributes to the yield of SOA.These results suggest that Fe(III)-Ox plays an important role in atmospheric oxidation.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.
文摘Battery grade γ-MnO2 powder was investigated as an oxidant and an adsorbent in combination with Fe/Al coagulants for removal of arsenic from contaminated water. Simultaneous oxidation of As(III) and removal by coprecipitation/adsorption (one step process) was compared with pre-oxidation and subsequent removal by coprecipitation/adsorption (two step process). The rate of As(III) oxidation with MnO2 is completed in two stages: rapid initially followed by a first order reaction. As(III) is oxidised to As(V) by the MnO2 with a release of approximately 1:1 molar Mn(II) into the solution. No significant pH effect on oxidation of As(III) was observed in the pH range 4 - 6. The rate showed a decreasing trend above pH 6. The removal of As(V) by adsorption on the MnO2 decreased significantly with increasing pH from 4 to 8. The adsorption capacity of the γ-MnO2 with particle size 90% passing 10 μm was determined to be 1.5 mg/g at pH 7. MnO2 was found to be more effective as an oxidant for As(III) in the two step process than in the one step process.
基金supported by the National Natural Science Foundation of China(Nos.22206050 and 52270047).
文摘Fenton and Fenton-like processes,which could produce highly reactive species to degrade organic contaminants,have been widely used in the field of wastewater treatment.Therein,the chemistry of Fenton process including the nature of active oxidants,the complicated reactions involved,and the behind reason for its strongly pH-dependent performance,is the basis for the application of Fenton and Fenton-like processes in wastewater treatment.Nevertheless,the conflicting views still exist about the mechanism of the Fenton process.For instance,reaching a unanimous consensus on the nature of active oxidants(hydroxyl radical or tetravalent iron)in this process remains challenging.This review comprehensively examined the mechanism of the Fenton process including the debate on the nature of active oxidants,reactions involved in the Fenton process,and the behind reason for the pH-dependent degradation of contaminants in the Fenton process.Then,we summarized several strategies that promote the Fe(Ⅱ)/Fe(Ⅲ)cycle,reduce the competitive consumption of active oxidants by side reactions,and replace the Fenton reagent,thus improving the performance of the Fenton process.Furthermore,advances for the future were proposed including the demand for the high-accuracy identification of active oxidants and taking advantages of the characteristic of target contaminants during the degradation of contaminants by the Fenton process.
基金The authors gratefully acknowledge financial support from the Ministry of Science and Technology of the People’s Republic of China(Grant Nos.2017YFC0210005 and 2016YFE0112200).
文摘Iron and oxalic acids are widely distributed in the atmosphere and easily form ferric oxalate complex(Fe(III)-Ox).The tropospheric aqueous-phase could provide a medium to enable the photo-Fenton reaction with Fe(III)-Ox under solar irradiation.Although the photolysis mechanisms of Fe(III)-Ox have been investigated extensively,information about the oxidation of volatile organic compounds(VOC),specifically the potential for Secondary Organic Aerosol(SOA)formation in the Fe(III)-Ox system,is lacking.In this study,a ubiquitous VOC methacrolein(MACR)is chosen as a model VOC,and the oxidation of MACR with Fe(III)-Ox is investigated under typical atmospheric water conditions.The effects of oxalate concentration,Fe(III)concentration,MACR concentration,and pH on the oxidation of MACR are studied in detail.Results show that the oxidation rate of MACR greatly accelerates in the presence of oxalate when compared with only Fe(III).The oxidation rate of MACR also accelerates with increasing concentration of oxalate.The effect of Fe(III)is found to be more complicated.The oxidation rate of MACR first increases and then decreases with increasing Fe(III)concentration.The oxidation rate of MACR increases monotonically with decreasing pH in the common atmospheric water pH range or with decreasing MACR concentration.The production of ferrous and hydrogen peroxide,pH,and aqueous absorbance are monitored throughout the reaction process.The quenching experiments verify that·OH and O_(2)^(+)are both responsible for the oxidation of MACR.MACR is found to rapidly oxidize into small organic acids with higher boiling points and oligomers with higher molecular weight,which contributes to the yield of SOA.These results suggest that Fe(III)-Ox plays an important role in atmospheric oxidation.
