In order to illustrate the thermodynamic characteristics of arsenic during alkaline pressure oxidation leaching process oflead anode slime(NaNO3as oxidant;NaOH as alkaline reagent),theφ-pH diagrams of As-Na-H2O,N-H2O...In order to illustrate the thermodynamic characteristics of arsenic during alkaline pressure oxidation leaching process oflead anode slime(NaNO3as oxidant;NaOH as alkaline reagent),theφ-pH diagrams of As-Na-H2O,N-H2O,As-N-Na-H2Osystems at ionic mass concentration of0.1mol/kg and temperatures of298,373,423and473K were established according tothermodynamic calculation.The results show that the existence forms of arsenic are associated with pH value,which mainly exists inthe forms of H3AsO4,24H AsO-,24HAsO-,H2AsO2-and As2O3in lower pH region,while it mainly exists in the form of3AsO4-when pH>11.14.High alkali concentration and high temperature are advantageous to the arsenic leaching.The alkaline pressureoxidation leaching experiments display that the tendency of arsenic leaching rate confirms the thermodynamic analysis resultsobtained from theφ-pH diagrams of As-N-Na-H2O system,and the highest leaching rate of arsenic reaches95.85%at453K.展开更多
Solution-phase hydrogen reduction(Sp HR)was introduced into V_(2)O_(3)preparation to overcome disadvantages of traditional reduction roasting,which include a long process,high energy consumption,and generation of poll...Solution-phase hydrogen reduction(Sp HR)was introduced into V_(2)O_(3)preparation to overcome disadvantages of traditional reduction roasting,which include a long process,high energy consumption,and generation of pollution.The research mainly focuses onφ-pH diagrams and kinetics of SpHR.Thermodynamic analysis ofφ-pH diagrams for the V-H_(2)O system demonstrates that V_(2)O_(3)preparation via Sp HR requires a high temperature,a high vanadium concentration,and sufficient hydrogen in acidic solution.Kinetic analyses show that the activation energy of V_(2)O_(3)preparation via SpHR is 38.0679 k J/mol,indicating that the reduction is controlled by a combination of interfacial chemical reaction and internal diffusion.Effects of H;partial pressure(slope K=0.05246)on the reaction rate is not as significant as the vanadium concentration(K=1.58872).V_(2)O_(3)crystals with a purity of 99.59%and a vanadium precipitation rate of 99.83%were obtained under the following conditions:pH=5-6,c(V_(2)O_(3))=0.5 mol/L,p(H;)=4 MPa,m(PdCl;)=10 mg,T=250℃,and t=2.5 h.展开更多
基金Project(51564031) supported by the National Natural Science Foundation of ChinaProject(0201352042) supported by the Cooperation between School and Enterprise of China
文摘In order to illustrate the thermodynamic characteristics of arsenic during alkaline pressure oxidation leaching process oflead anode slime(NaNO3as oxidant;NaOH as alkaline reagent),theφ-pH diagrams of As-Na-H2O,N-H2O,As-N-Na-H2Osystems at ionic mass concentration of0.1mol/kg and temperatures of298,373,423and473K were established according tothermodynamic calculation.The results show that the existence forms of arsenic are associated with pH value,which mainly exists inthe forms of H3AsO4,24H AsO-,24HAsO-,H2AsO2-and As2O3in lower pH region,while it mainly exists in the form of3AsO4-when pH>11.14.High alkali concentration and high temperature are advantageous to the arsenic leaching.The alkaline pressureoxidation leaching experiments display that the tendency of arsenic leaching rate confirms the thermodynamic analysis resultsobtained from theφ-pH diagrams of As-N-Na-H2O system,and the highest leaching rate of arsenic reaches95.85%at453K.
基金financially supported by the National Key R&D Program of China(No.2020YFC1909700)Outstanding Young and Middle-aged Science and Technology Innovation Team Project of Hubei Province,China(No.T201802)the National Natural Science Foundation of China(No.52004187)。
文摘Solution-phase hydrogen reduction(Sp HR)was introduced into V_(2)O_(3)preparation to overcome disadvantages of traditional reduction roasting,which include a long process,high energy consumption,and generation of pollution.The research mainly focuses onφ-pH diagrams and kinetics of SpHR.Thermodynamic analysis ofφ-pH diagrams for the V-H_(2)O system demonstrates that V_(2)O_(3)preparation via Sp HR requires a high temperature,a high vanadium concentration,and sufficient hydrogen in acidic solution.Kinetic analyses show that the activation energy of V_(2)O_(3)preparation via SpHR is 38.0679 k J/mol,indicating that the reduction is controlled by a combination of interfacial chemical reaction and internal diffusion.Effects of H;partial pressure(slope K=0.05246)on the reaction rate is not as significant as the vanadium concentration(K=1.58872).V_(2)O_(3)crystals with a purity of 99.59%and a vanadium precipitation rate of 99.83%were obtained under the following conditions:pH=5-6,c(V_(2)O_(3))=0.5 mol/L,p(H;)=4 MPa,m(PdCl;)=10 mg,T=250℃,and t=2.5 h.
