The present paper reports a new fluoride-free and energy-saving lead electrolytic refining process in order to solve the serious problems of the existing Betts lead electrorefining process, such as low production effi...The present paper reports a new fluoride-free and energy-saving lead electrolytic refining process in order to solve the serious problems of the existing Betts lead electrorefining process, such as low production efficiency,high energy consumption and fluorine pollution. In the process, a mixed solution of perchloric acid and lead perchlorate(HClO4-Pb(ClO4)2) with the additives of gelatin and sodium lignin sulfonate is employed as the new electrolyte. The cathodic polarization curves show that HClO4 is very stable, and there is no any reduction reaction of HClO4 during the electrolytic process. The redox reactions of lead ions in HClO4 solution are very reversible with an ultrahigh capacity efficiency, so the HClO4 acts as a stable support electrolyte with higher ionic conductivity than the traditional H2SiF6 electrolyte. The results of the scale-up experiments show that under the optimal conditions of 2.8 mol·L-1 HClO4, 0.4 mol·L-1 Pb(ClO4)2 and electrolysis temperature of 45 ℃, the energy consumption is as low as 24.5 kW·h·(t Pb)-1 , only about 20% of that by Betts method at the same current density of 20 mA·cm-2, and the purity of the refined lead is up to 99.9992%, much higher than that specified by Chinese national standard(99.994%, GB/T 469-2013) and European standard(99.99%, EN 12659–1999).展开更多
The influences of cupric ion concentration （5-35 g/L）,current density （500-2000 A/m2）,circulation rate of the electrolyte solution （15-120 mL/min）,and temperature （25-60℃） on the physical and chemical propert...The influences of cupric ion concentration （5-35 g/L）,current density （500-2000 A/m2）,circulation rate of the electrolyte solution （15-120 mL/min）,and temperature （25-60℃） on the physical and chemical properties of copper powders obtained in electrolysis cells were investigated.Two industrial processes,electrorefining （ER） cells with a synthetic electrolyte and electrowinning （EW） cells with an original solution of coppermineral leaching,were utilized to produce copper powders.Finally,the statistical full factorial method of design of experiments （DOE） was employed to investigate the interaction or the main effects of processes.The results show that increasing the copper concentration and temperature can increase the grain size,apparent density,and electrical energy consumption.On the other hand,increasing the current density and circulation rate of the electrolyte can decrease them.This production process is optimized via DOE to control the interactive and main effects to produce copper powders with favorable properties.展开更多
Electrorefining of nickel in LiCl–KCl melt was investigated using electrochemical techniques. Nickel products after electrorefining were characterized by X-ray diffraction, X-ray fluorescence, and scanning electron m...Electrorefining of nickel in LiCl–KCl melt was investigated using electrochemical techniques. Nickel products after electrorefining were characterized by X-ray diffraction, X-ray fluorescence, and scanning electron microscopy. Both cyclic voltammetry and square wave voltammetry results suggested that Ni^2+ was directly reduced to Ni metal in LiCl–KCl. Based on a preliminary study on the electrochemical behavior of nickel and chromium, electrorefining was carried out under constant potential, whereupon deposits were formed on the cathode. The purity of nickel increased from 72.62% in the original alloy to 99.83% in cathodic deposits, as determined by inductively coupled plasma atomic emission spectroscopy analysis. Almost all the nickel in the alloy could be recovered during the electrochemical process with[90% current efficiency. A lower concentration of NiCl2 in LiCl– KCl was found to be favorable for nickel electrorefining, as increased NiCl2 concentration caused severe corrosion of the nickel anode at the gas–liquid interface due to the accumulation of Cl2 gas.展开更多
The role of trivalent antimony was investigated in removing As, Sb, and Bi impurities from a copper electrolyte. Puri- fication experiments were carried out by adding a various concentrations of Sb（III） ions in a sy...The role of trivalent antimony was investigated in removing As, Sb, and Bi impurities from a copper electrolyte. Puri- fication experiments were carried out by adding a various concentrations of Sb（III） ions in a synthetic electrolyte containing 185 g/L sulfuric acid, 45 g/L Cu2＋, 10 g/L As, and 0.5 g/L Bi under stirring at 65℃ for 2 h. The electrolyte was filtered, and the structure, morphology and composition of the precipitate were analyzed by means of chemical analysis, scanning electron mi- croscopy （SEM）, X-ray diffraction （XRD）, transmission electron microscopy （TEM）, and IR spectroscopy. The precipitate is composed of irregular lumps which are agglomerated by fine dendritic and floccus particles, and it mainly consists of As, Sb, Bi, and O elements. Characteristic bands in the IR spectra of the precipitate are As-OX （X=As, Sb, Bi）, Sb-OY （Y=Sb, Bi）, O-As-O1 As-OH, Sb-OH, and O-H. The precipitate is a mixture of microcrystalline SbAsQ, （Sb,As）203, and amorphous phases. As, Sb, and Bi impurities are effectively removed from the copper electrolyte by Sb（III） ions attributing to these pre- cipitates.展开更多
基金Supported by the National Natural Science Foundation of China(21676022)the Fundamental Research Funds for the Central Universities(BHYC170A&JD701)
文摘The present paper reports a new fluoride-free and energy-saving lead electrolytic refining process in order to solve the serious problems of the existing Betts lead electrorefining process, such as low production efficiency,high energy consumption and fluorine pollution. In the process, a mixed solution of perchloric acid and lead perchlorate(HClO4-Pb(ClO4)2) with the additives of gelatin and sodium lignin sulfonate is employed as the new electrolyte. The cathodic polarization curves show that HClO4 is very stable, and there is no any reduction reaction of HClO4 during the electrolytic process. The redox reactions of lead ions in HClO4 solution are very reversible with an ultrahigh capacity efficiency, so the HClO4 acts as a stable support electrolyte with higher ionic conductivity than the traditional H2SiF6 electrolyte. The results of the scale-up experiments show that under the optimal conditions of 2.8 mol·L-1 HClO4, 0.4 mol·L-1 Pb(ClO4)2 and electrolysis temperature of 45 ℃, the energy consumption is as low as 24.5 kW·h·(t Pb)-1 , only about 20% of that by Betts method at the same current density of 20 mA·cm-2, and the purity of the refined lead is up to 99.9992%, much higher than that specified by Chinese national standard(99.994%, GB/T 469-2013) and European standard(99.99%, EN 12659–1999).
文摘The influences of cupric ion concentration （5-35 g/L）,current density （500-2000 A/m2）,circulation rate of the electrolyte solution （15-120 mL/min）,and temperature （25-60℃） on the physical and chemical properties of copper powders obtained in electrolysis cells were investigated.Two industrial processes,electrorefining （ER） cells with a synthetic electrolyte and electrowinning （EW） cells with an original solution of coppermineral leaching,were utilized to produce copper powders.Finally,the statistical full factorial method of design of experiments （DOE） was employed to investigate the interaction or the main effects of processes.The results show that increasing the copper concentration and temperature can increase the grain size,apparent density,and electrical energy consumption.On the other hand,increasing the current density and circulation rate of the electrolyte can decrease them.This production process is optimized via DOE to control the interactive and main effects to produce copper powders with favorable properties.
基金supported by the National Nature Science Foundation of China(Nos.21601200 and 21771188)Strategic Priority Research Program and Frontier Science Key Program(Nos.XD02030000 and QYZDY-SSW-JSC016)of the Chinese Academy of Sciences
文摘Electrorefining of nickel in LiCl–KCl melt was investigated using electrochemical techniques. Nickel products after electrorefining were characterized by X-ray diffraction, X-ray fluorescence, and scanning electron microscopy. Both cyclic voltammetry and square wave voltammetry results suggested that Ni^2+ was directly reduced to Ni metal in LiCl–KCl. Based on a preliminary study on the electrochemical behavior of nickel and chromium, electrorefining was carried out under constant potential, whereupon deposits were formed on the cathode. The purity of nickel increased from 72.62% in the original alloy to 99.83% in cathodic deposits, as determined by inductively coupled plasma atomic emission spectroscopy analysis. Almost all the nickel in the alloy could be recovered during the electrochemical process with[90% current efficiency. A lower concentration of NiCl2 in LiCl– KCl was found to be favorable for nickel electrorefining, as increased NiCl2 concentration caused severe corrosion of the nickel anode at the gas–liquid interface due to the accumulation of Cl2 gas.
基金support by the National Natural Scientific Foundation of China(No. 50904023)the Natural Science Research Project of the Education Department of Henan Province (No.2010B450001)+1 种基金the Innovation Scientists and Technicians Troop Construction Projects of Henan Province(No. 104100510005)the Basic and Frontier Technologies Research Projects of Henan Province, China(No. 092300410064)
文摘The role of trivalent antimony was investigated in removing As, Sb, and Bi impurities from a copper electrolyte. Puri- fication experiments were carried out by adding a various concentrations of Sb（III） ions in a synthetic electrolyte containing 185 g/L sulfuric acid, 45 g/L Cu2＋, 10 g/L As, and 0.5 g/L Bi under stirring at 65℃ for 2 h. The electrolyte was filtered, and the structure, morphology and composition of the precipitate were analyzed by means of chemical analysis, scanning electron mi- croscopy （SEM）, X-ray diffraction （XRD）, transmission electron microscopy （TEM）, and IR spectroscopy. The precipitate is composed of irregular lumps which are agglomerated by fine dendritic and floccus particles, and it mainly consists of As, Sb, Bi, and O elements. Characteristic bands in the IR spectra of the precipitate are As-OX （X=As, Sb, Bi）, Sb-OY （Y=Sb, Bi）, O-As-O1 As-OH, Sb-OH, and O-H. The precipitate is a mixture of microcrystalline SbAsQ, （Sb,As）203, and amorphous phases. As, Sb, and Bi impurities are effectively removed from the copper electrolyte by Sb（III） ions attributing to these pre- cipitates.
