A calcified roasting-acid leaching process was developed as a highly effective method for the extraction of valuable metals from low nickel matte in the presence of CaO additive. The influences of process parameters o...A calcified roasting-acid leaching process was developed as a highly effective method for the extraction of valuable metals from low nickel matte in the presence of CaO additive. The influences of process parameters on the metal extraction were studied, including the roasting temperature, roasting time, addition of CaO, H2SO4 concentration and liquid-solid ratio. Under the optimum condition, 94.2% of Ni, 98.1% of Cu, 92.2% of Co and 89.3% of Fe were recovered. Additionally, 99.6% of Fe was removed from the leachate as goethite by a subsequent goethite iron precipitation process. The behavior and mechanism of CaO additive in the roasting process was clarified. The role of CaO is to prevent the formation of nonferrous metal ferrite phases by a preferential reaction with Fe2O3 during the roasting process. The metal oxides(Cu O and NixCu1-xO) remained stable during high-temperature roasting and were subsequently efficiently leached using a sulfuric acid solution.展开更多
A clean and efficient route for the utilization of ilmenite concentrates was proposed by direct carbothermic reduction in microwave field.High dosage of Na_(2)CO_(3),which can be recycled,was added to accelerate the r...A clean and efficient route for the utilization of ilmenite concentrates was proposed by direct carbothermic reduction in microwave field.High dosage of Na_(2)CO_(3),which can be recycled,was added to accelerate the reduction reaction of ilmenite concentrates.After microwave heating in the temperature range of 1073−1123 K for 20 min,the main products were Na_(2)TiO_(3) and metallic Fe with the metallization ratios being as high as 92.67%−93.21%.The reduction products were processed by water leaching,ball-milling in CO2 atmosphere and magnetic separation in turn.The final products after magnetic separation were Fe-rich materials and Ti-rich materials(90.04 wt.%TiO2),which can be used to produce iron and TiCl4 or TiO2.The optimized heating temperature was 1123 K in terms of metallization ratios,magnetic separation and caking property of the reduction products.Besides,the reduction mechanism of ilmenite concentrates with the addition of Na_(2)CO_(3) in microwave field was also proposed.展开更多
The interfacial reactions of chalcopyrite in ammonia–ammonium chloride solution were investigated.The chalcopyrite surface was examined by scanning electron microscopy and X-ray photoelectron spectroscopy(XPS)techniq...The interfacial reactions of chalcopyrite in ammonia–ammonium chloride solution were investigated.The chalcopyrite surface was examined by scanning electron microscopy and X-ray photoelectron spectroscopy(XPS)techniques.It was found that interfacial passivation layers of chalcopyrite were formed from an iron oxide layer on top of a copper sulfide layer overlaying the bulk chalcopyrite,whereas CuFe1-xS2 or copper sulfides were formed via the preferential dissolution of Fe.The copper sulfide layer formed a new passivation layer,whereas the iron oxide layer peeled off spontaneously and partially from the chalcopyrite surface.The state of the copper sulfide layer was discussed after being deduced from the appearance of S2-,S22-,Sn2-,S0 and SO42-.A mechanism for the oxidation and passivation of chalcopyrite under different pH values and redox potentials was proposed.Accordingly,a model of the interfacial reaction on the chalcopyrite surface was constructed using a three-step reaction pathway,which demonstrated the formation and transformation of passivation layers under the present experimental conditions.展开更多
The hydrogen reduction of Panzhihua ilmenite concentrate in the temperature range of 900?1050 °C was systematicallyinvestigated by thermogravimetric analysis (TG), X-ray diffraction (XRD) and scanning electron mi...The hydrogen reduction of Panzhihua ilmenite concentrate in the temperature range of 900?1050 °C was systematicallyinvestigated by thermogravimetric analysis (TG), X-ray diffraction (XRD) and scanning electron microscopy (SEM) methods. It wasshown that the products of the Panzhihua ilmenite reduced at 900 °C were metallic iron and rutile. Above 1000 °C, ferrouspseudobrookite solid solution was generated. During the reduction process, element Mg gradually concentrated to form Mg-rich zonewhich can influence the metallization process. The reduction reaction proceeded topochemically and its related reduction kineticswere also discussed. The kinetics of the reduction indicated that the rate-controlling step was the diffusion process. The apparentactivation energy of the hydrogen reduction of Panzhihua ilmenite was calculated to be 117.56 kJ/mol, which was larger than that ofsynthetic ilmenite under the same reduction condition.展开更多
Titanium germanium intermetallics (TixGey)were directly prepared from titanium oxide (TiO2) and germanium oxide(GeO2) powders mixture by using an electrodeoxidation process. The electrochemical experiment was ca...Titanium germanium intermetallics (TixGey)were directly prepared from titanium oxide (TiO2) and germanium oxide(GeO2) powders mixture by using an electrodeoxidation process. The electrochemical experiment was carried out in a molten fluxCaCl2-NaCl at 800℃ with a potential of 3.0 V. The results show that monolithic germanide Ti5Ge3 intermetallic can be directlyproduced from TiO2-GeO2 or CaTiO3-GeO2 precursors (both molar ratios are 5:3), and the obtained Ti5Ge3 powders exhibithomogenous particle structure. In addition, the phase composition of the final product can be dramatically affected by the initialmolar ratio of TiO2 to GeO2. The reaction mechanism of the electrodeoxidation process was discussed based on the experimentalresults. It is suggested that the electrodeoxidation process is an environmentally friendly method for the preparation of Ti-Geintermetallics.展开更多
NbC-Sn composite powder was successfully prepared from SnO2,Nb2O5and carbon by electrochemical reduction andcarbonization in CaCl2-NaCl molten salt at900°C.The reaction pathway was investigated by terminating ele...NbC-Sn composite powder was successfully prepared from SnO2,Nb2O5and carbon by electrochemical reduction andcarbonization in CaCl2-NaCl molten salt at900°C.The reaction pathway was investigated by terminating electrochemicalexperiments for various durations.The influence of carbon on the final products was considered.NbC particles were obtained byleaching the composite with acid.The results showed that the aggregated NbC-Sn composite powdev contained NbC particles about50-100nm and Sn particles about200nm.SnO2was reduced to Sn in the sintering process.Nb2O5was electrochemically reduced toNb in molten salt,experiencing some intermediate products of calcium niobates and niobium suboxides.Nb metal obtained wasconverted to NbC with assistance of carbon.The reduction of Nb oxides may be incomplete and Nb3Sn would be formed if carbon isinsufficient in the cathodic pellet.NbC with good dispersity is produced by leaching NbC-Sn with HCl.展开更多
An electrochemical study on the redox behavior of indium in the eutectic LiCl-KCl system at 450 ℃ was carried out with the transient techniques of cyclic voltammetry and chronopotentiometry on an inert molybdenum ele...An electrochemical study on the redox behavior of indium in the eutectic LiCl-KCl system at 450 ℃ was carried out with the transient techniques of cyclic voltammetry and chronopotentiometry on an inert molybdenum electrode. The reduction of In(Ⅲ) was found to be a two-step process involving In(Ⅲ)/In(Ⅰ) and In(Ⅰ)/In couples at the potentials of about-0.4 and-0.8 V versus Ag/AgCl, respectively. The redox mechanism was further confirmed by the theoretical evaluation of the number of transferred electrons based on cyclic voltammetry and characterizations of the precipitates generated by the potentiostatic electrolysis. The diffusion coefficients of indium ions in the eutectic LiCl-KCl melt at 450 ℃ were estimated by cyclic voltammetry and chronopotentiometry. The results obtained through the two methods are in fair agreement, delivering an average diffusion coefficient of approximately 1.8×10^(-5)cm^(2)/s for In(Ⅲ), and 1.4×10^(-4)cm^(2)/s for In(Ⅰ).展开更多
The crystal structure,physical,chemical and phase transition properties of trititanium pentoxide(Ti_(3)O_5)have aroused a broad range of research effort since the 1950s.Different crystalline forms(α,β,γ,δandλ)of ...The crystal structure,physical,chemical and phase transition properties of trititanium pentoxide(Ti_(3)O_5)have aroused a broad range of research effort since the 1950s.Different crystalline forms(α,β,γ,δandλ)of Ti_(3)O_5 exhibit various properties.Particularly,reversible phase transitions betweenλ-andβ-Ti_(3)O_5 have been attracting increasing research interest,which brings new potential applications of Ti_(3)O_5 materials in the field of energy and data storage.More recently,Ti_(3)O_5 materials have shown excellent performance in trace detection,microwave absorption and virus adsorption,which has expanded its application fields.Here,the essential properties of different crystal forms of Ti_(3)O_5 are described in detail.An intensive overview of Ti_(3)O_5 preparation methods and applications is comprehensively summarized.展开更多
The phase diagram of ZrO_(2)−CaO−TiO_(2)system was essential for the development of photocatalytic materials and refractory materials.In this work,the ZrO_(2)−CaO−TiO_(2)system was accessed by using the CALPHAD method...The phase diagram of ZrO_(2)−CaO−TiO_(2)system was essential for the development of photocatalytic materials and refractory materials.In this work,the ZrO_(2)−CaO−TiO_(2)system was accessed by using the CALPHAD method.The substitutional solution models were used to describe liquid and solid solution phases,the sub-lattice models were used to describe ternary compounds,and then the thermodynamic parameters were obtained by the least square method combined with literature experiment results.The acquired thermodynamic parameters were used to calculate the isothermal sections of the ZrO_(2)−CaO−TiO_(2)system at 1473 and 1673 K.There existed a good agreement between experimental and predicted phase relationships,the experimental points which were inconsistent with calculated results may be attributed to experimental errors and the sluggish kinetics of cations for ZrO_(2)-based materials.In order to further verify the validity of the database,the thermodynamic parameters were also used to simulate the thermodynamic properties(specific heat capacity,enthalpy,and entropy)of CaZrTi_(2)O_(7) within 5%errors.Good consistency demonstrated that the present thermodynamic database was self-consistent and credible.展开更多
Titanium aluminum(TiAl)scraps with a high oxygen content were treated with yttrium(Y)in a liquid chemical deoxidization process for recycling.The Gibbs free energy and the equilibrium constant of the deoxidization rea...Titanium aluminum(TiAl)scraps with a high oxygen content were treated with yttrium(Y)in a liquid chemical deoxidization process for recycling.The Gibbs free energy and the equilibrium constant of the deoxidization reaction were calculated,and the effects of the yttrium content and the system pressure on the oxygen content in the product were determined.The results showed that the oxygen in TiAl scraps could be removed by yttrium,and the oxygen content of the deoxidized TiAl scraps had only 10%of the original content after deoxidization.Furthermore,the oxygen content of the deoxidized TiAl scraps was decreased with the increase of yttrium addition.The higher the chamber pressure,the greater the oxygen content in the final TiAl alloys.These results were consistent with calculated values.The microstructure of the deoxidized alloys was akin to that of the original material;however,Y_(2)O_(3) particles were observed in the deoxidized alloys.展开更多
基金Projects(U1860203,U1860108,51574164) supported by the National Natural Science Foundation of China
文摘A calcified roasting-acid leaching process was developed as a highly effective method for the extraction of valuable metals from low nickel matte in the presence of CaO additive. The influences of process parameters on the metal extraction were studied, including the roasting temperature, roasting time, addition of CaO, H2SO4 concentration and liquid-solid ratio. Under the optimum condition, 94.2% of Ni, 98.1% of Cu, 92.2% of Co and 89.3% of Fe were recovered. Additionally, 99.6% of Fe was removed from the leachate as goethite by a subsequent goethite iron precipitation process. The behavior and mechanism of CaO additive in the roasting process was clarified. The role of CaO is to prevent the formation of nonferrous metal ferrite phases by a preferential reaction with Fe2O3 during the roasting process. The metal oxides(Cu O and NixCu1-xO) remained stable during high-temperature roasting and were subsequently efficiently leached using a sulfuric acid solution.
基金financially supported by the National Natural Science Foundation of China(Nos.51734002,51474141)China Postdoctoral Science Foundation(No.2020M671071)Independent Research and Development Project of State Key Laboratory of Advanced Special Steel,Shanghai Key Laboratory of Advanced Ferrometallurgy,Shanghai University,China(No.SKLASS 2019-Z014)。
文摘A clean and efficient route for the utilization of ilmenite concentrates was proposed by direct carbothermic reduction in microwave field.High dosage of Na_(2)CO_(3),which can be recycled,was added to accelerate the reduction reaction of ilmenite concentrates.After microwave heating in the temperature range of 1073−1123 K for 20 min,the main products were Na_(2)TiO_(3) and metallic Fe with the metallization ratios being as high as 92.67%−93.21%.The reduction products were processed by water leaching,ball-milling in CO2 atmosphere and magnetic separation in turn.The final products after magnetic separation were Fe-rich materials and Ti-rich materials(90.04 wt.%TiO2),which can be used to produce iron and TiCl4 or TiO2.The optimized heating temperature was 1123 K in terms of metallization ratios,magnetic separation and caking property of the reduction products.Besides,the reduction mechanism of ilmenite concentrates with the addition of Na_(2)CO_(3) in microwave field was also proposed.
基金Project(2014CB643405)supported by the National Basic Research Program of China
文摘The interfacial reactions of chalcopyrite in ammonia–ammonium chloride solution were investigated.The chalcopyrite surface was examined by scanning electron microscopy and X-ray photoelectron spectroscopy(XPS)techniques.It was found that interfacial passivation layers of chalcopyrite were formed from an iron oxide layer on top of a copper sulfide layer overlaying the bulk chalcopyrite,whereas CuFe1-xS2 or copper sulfides were formed via the preferential dissolution of Fe.The copper sulfide layer formed a new passivation layer,whereas the iron oxide layer peeled off spontaneously and partially from the chalcopyrite surface.The state of the copper sulfide layer was discussed after being deduced from the appearance of S2-,S22-,Sn2-,S0 and SO42-.A mechanism for the oxidation and passivation of chalcopyrite under different pH values and redox potentials was proposed.Accordingly,a model of the interfacial reaction on the chalcopyrite surface was constructed using a three-step reaction pathway,which demonstrated the formation and transformation of passivation layers under the present experimental conditions.
基金Project(2014CB643403)supported by the National Basic Research Program of ChinaProjects(51225401,51304132,51574164)supported by the National Natural Science Foundation of China+1 种基金Project(14JC1491400)supported by the Science and Technology Commissions of Shanghai Municipality,ChinaProject(2013GZ0146)supported by the Sichuan Province,China
文摘The hydrogen reduction of Panzhihua ilmenite concentrate in the temperature range of 900?1050 °C was systematicallyinvestigated by thermogravimetric analysis (TG), X-ray diffraction (XRD) and scanning electron microscopy (SEM) methods. It wasshown that the products of the Panzhihua ilmenite reduced at 900 °C were metallic iron and rutile. Above 1000 °C, ferrouspseudobrookite solid solution was generated. During the reduction process, element Mg gradually concentrated to form Mg-rich zonewhich can influence the metallization process. The reduction reaction proceeded topochemically and its related reduction kineticswere also discussed. The kinetics of the reduction indicated that the rate-controlling step was the diffusion process. The apparentactivation energy of the hydrogen reduction of Panzhihua ilmenite was calculated to be 117.56 kJ/mol, which was larger than that ofsynthetic ilmenite under the same reduction condition.
基金Project(51574164)supported by the National Natural Science Foundation of ChinaProject(2014CB643403)supported by the National Basic Research Program of China
文摘Titanium germanium intermetallics (TixGey)were directly prepared from titanium oxide (TiO2) and germanium oxide(GeO2) powders mixture by using an electrodeoxidation process. The electrochemical experiment was carried out in a molten fluxCaCl2-NaCl at 800℃ with a potential of 3.0 V. The results show that monolithic germanide Ti5Ge3 intermetallic can be directlyproduced from TiO2-GeO2 or CaTiO3-GeO2 precursors (both molar ratios are 5:3), and the obtained Ti5Ge3 powders exhibithomogenous particle structure. In addition, the phase composition of the final product can be dramatically affected by the initialmolar ratio of TiO2 to GeO2. The reaction mechanism of the electrodeoxidation process was discussed based on the experimentalresults. It is suggested that the electrodeoxidation process is an environmentally friendly method for the preparation of Ti-Geintermetallics.
基金Projects(51404057,50874026)supported by the National Natural Science Foundation of ChinaProject(N150204014)supported by Fundamental Research Funds for the Central Universities,China
文摘NbC-Sn composite powder was successfully prepared from SnO2,Nb2O5and carbon by electrochemical reduction andcarbonization in CaCl2-NaCl molten salt at900°C.The reaction pathway was investigated by terminating electrochemicalexperiments for various durations.The influence of carbon on the final products was considered.NbC particles were obtained byleaching the composite with acid.The results showed that the aggregated NbC-Sn composite powdev contained NbC particles about50-100nm and Sn particles about200nm.SnO2was reduced to Sn in the sintering process.Nb2O5was electrochemically reduced toNb in molten salt,experiencing some intermediate products of calcium niobates and niobium suboxides.Nb metal obtained wasconverted to NbC with assistance of carbon.The reduction of Nb oxides may be incomplete and Nb3Sn would be formed if carbon isinsufficient in the cathodic pellet.NbC with good dispersity is produced by leaching NbC-Sn with HCl.
基金the National Natural Science Foundation of China(Nos.51904003,U1703130,51704011)the China Postdoctoral Science Foundation(No.2019M651466)the Foundation of Anhui Province Key Laboratory of Metallurgical Engineering&Resources Recycling of China(Nos.SKF18-01,SKF19-05).
文摘An electrochemical study on the redox behavior of indium in the eutectic LiCl-KCl system at 450 ℃ was carried out with the transient techniques of cyclic voltammetry and chronopotentiometry on an inert molybdenum electrode. The reduction of In(Ⅲ) was found to be a two-step process involving In(Ⅲ)/In(Ⅰ) and In(Ⅰ)/In couples at the potentials of about-0.4 and-0.8 V versus Ag/AgCl, respectively. The redox mechanism was further confirmed by the theoretical evaluation of the number of transferred electrons based on cyclic voltammetry and characterizations of the precipitates generated by the potentiostatic electrolysis. The diffusion coefficients of indium ions in the eutectic LiCl-KCl melt at 450 ℃ were estimated by cyclic voltammetry and chronopotentiometry. The results obtained through the two methods are in fair agreement, delivering an average diffusion coefficient of approximately 1.8×10^(-5)cm^(2)/s for In(Ⅲ), and 1.4×10^(-4)cm^(2)/s for In(Ⅰ).
基金financial supports from the National Natural Science Foundation of China(Nos.52004157,U1860203,52022054,51974181)the Shanghai Sailing Program,China(No.21YF1412900)+5 种基金the Shanghai Rising-Star Program,China(No.19QA1403600)the Shanghai Engineering Research Center of Green Remanufacture of Metal Parts,China(No.19DZ2252900)the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning,China(No.TP2019041)the“Shuguang Program”supported by the Shanghai Education Development Foundation and the Shanghai Municipal Education Commission,China(No.21SG42)the Independent Research and Development Project of State Key Laboratory of Advanced Special Steel,Shanghai Key Laboratory of Advanced Ferrometallurgy,Shanghai University,China(No.SKLASS 2020-Z10)the Science and Technology Commission of Shanghai Municipality,China(No.19DZ2270200).
文摘The crystal structure,physical,chemical and phase transition properties of trititanium pentoxide(Ti_(3)O_5)have aroused a broad range of research effort since the 1950s.Different crystalline forms(α,β,γ,δandλ)of Ti_(3)O_5 exhibit various properties.Particularly,reversible phase transitions betweenλ-andβ-Ti_(3)O_5 have been attracting increasing research interest,which brings new potential applications of Ti_(3)O_5 materials in the field of energy and data storage.More recently,Ti_(3)O_5 materials have shown excellent performance in trace detection,microwave absorption and virus adsorption,which has expanded its application fields.Here,the essential properties of different crystal forms of Ti_(3)O_5 are described in detail.An intensive overview of Ti_(3)O_5 preparation methods and applications is comprehensively summarized.
基金the Open Project of State Key Laboratory of Advanced Special Steel and Shanghai Key Laboratory of Advanced Ferrometallurgy,China(No.SKLASS2019-11)the National Natural Science Foundation of China(No.52104305).
文摘The phase diagram of ZrO_(2)−CaO−TiO_(2)system was essential for the development of photocatalytic materials and refractory materials.In this work,the ZrO_(2)−CaO−TiO_(2)system was accessed by using the CALPHAD method.The substitutional solution models were used to describe liquid and solid solution phases,the sub-lattice models were used to describe ternary compounds,and then the thermodynamic parameters were obtained by the least square method combined with literature experiment results.The acquired thermodynamic parameters were used to calculate the isothermal sections of the ZrO_(2)−CaO−TiO_(2)system at 1473 and 1673 K.There existed a good agreement between experimental and predicted phase relationships,the experimental points which were inconsistent with calculated results may be attributed to experimental errors and the sluggish kinetics of cations for ZrO_(2)-based materials.In order to further verify the validity of the database,the thermodynamic parameters were also used to simulate the thermodynamic properties(specific heat capacity,enthalpy,and entropy)of CaZrTi_(2)O_(7) within 5%errors.Good consistency demonstrated that the present thermodynamic database was self-consistent and credible.
基金supported by Key Laboratory for Ecological Metallurgy of Multimetallic Mineral (Ministry of Education) Open Subjectthe National Natural Science Foundation of China-China Baowu Steel Group Joint Research Fund for Iron and Steel (No.U1860203)the National Natural Science Foundation of China (No.U1760109)。
文摘Titanium aluminum(TiAl)scraps with a high oxygen content were treated with yttrium(Y)in a liquid chemical deoxidization process for recycling.The Gibbs free energy and the equilibrium constant of the deoxidization reaction were calculated,and the effects of the yttrium content and the system pressure on the oxygen content in the product were determined.The results showed that the oxygen in TiAl scraps could be removed by yttrium,and the oxygen content of the deoxidized TiAl scraps had only 10%of the original content after deoxidization.Furthermore,the oxygen content of the deoxidized TiAl scraps was decreased with the increase of yttrium addition.The higher the chamber pressure,the greater the oxygen content in the final TiAl alloys.These results were consistent with calculated values.The microstructure of the deoxidized alloys was akin to that of the original material;however,Y_(2)O_(3) particles were observed in the deoxidized alloys.