Purification of metallurgical grade silicon by electrorefining in molten salts

Electrochemical studies on silicon deposition were performed in molten salt electrolytes. Purification of metallurgical grade silicon by electrorefining was carried out in molten Si-chloride salts at temperatures from 973 K to 1223 K. It was found that the use of a liquid alloy anode of silicon and copper was beneficial in molten CaCl2 with NaCl, CaO and dissolved Si. ICP-AES analysis results showed efficient removal of metal impurities, such as titanium, aluminum and iron, which are present in significant quantities in the feedstock. The contents of boron and phosphorus in the silicon after electrorefining were reduced from 36×10-6 and 25×10-6 to 4.6×10-6 and 2.8 ×10-6, respectively. The energy consumption of electrorefining was estimated to be about 9.3 kW?h/kg.

Direct Synthesis of High Purity Silicon Wires by Electrorefining in Molten KF-NaF Eutectic

The electrochemical synthesis silicon wires by electrorefining metallurgical grade silicon in thermally dried and pre-electrolyzed molten KF-NaF eutectic were studied at temperatures 800-900 ℃ using cyclic voltammetry and ac impedance. One oxidation peak at -0.14 V could be attributed to the reaction of Si to Si4＋. A cathodic peak occurred at -0.56 V in the cyclic voltammogram and one response semicircle in the ac impedance spectrum was observed, supporting a one-step electrochemical reduction process of Si4＋-→Si. The electrochemical reaction of silicon was controlled by the diffusion process. The purity of electrorefined silicon wires was up to 99.999% by ICP-MS analysis.

Separation and recovery of copper in Cu-As-bearing copper electrorefining black slime by oxidation acid leaching and sulfide precipitation

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 ℃.

An energy saving and fluorine-free electrorefining process for ultrahigh purity lead refining

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).

Chlorine inclusion mechanism in high purity copper electrorefining from nitric acid system

A practical approach was introduced to study the inclusion mechanism of chlorine in high purity copper electrorefining from nitric acid system via cyclic voltammetry(CV) combined with electrodeposition experiments. The CV curves display an obvious reduction peak of Cu Cl intermediate, which can provide an insight into the electrochemical behavior of this inclusion. Experimental results show that the increase of HNO3 concentration is favorable to reducing the quantity of chlorine inclusion although there is a slight decline in cathodic current efficiency. The optimum conditions for copper electrorefining in nitric acid system are HNO3 concentration in solution of 1-2 mol/L, moderate temperature of ~35 ℃ with current density not exceeding 25 m A/cm2. Based on the theoretical studies, an optimized copper electrorefining experiment was designed to simulate the industrial electrolysis, by which high purity copper can be obtained with chlorine inclusion less than 10 μg/g and current efficiency higher than 90%.

Electrorefining of nickel from nickel–chromium alloy in molten LiCl–KCl

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.

Comparison of effective parameters for copper powder production via electrorefining and electrowinning cells and improvement using DOE methods

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.

Electrorefining of aluminum in urea-imidazole chloride-aluminum chloride ionic liquids

The electrochemical behavior of Al(Ⅲ)in urea-1-butyl-3-methylimidazolium chloride-aluminum chloride(urea-BMIC-AlCl_(3))ionic liquids,and the effect of potential and temperature on the characterization of cathode products,current efficiency and energy consumption of aluminum electrorefining have been investigated.Cyclic voltammetry showed that the electrochemical reduction of Al(Ⅲ)was a one-step three-electron-transfer irreversible reaction,and the electrochemical reaction was controlled by diffusion.The diffusion coefficient of Al(Ⅲ)in urea-BMIC-AlCl_(3)ionic liquids at 313 K was 1.94×10^(−7)cm^(2)/s.The 7075 aluminum alloy was used as an anode for electrorefining,and the cathode products were analyzed by XRD,SEM and EDS.The results from XRD analysis indicated that the main phase of the cathode products was aluminum.The results from SEM and EDS characterization revealed that the cathode product obtained by electrorefining−1.2 V(vs.Al)was dense and uniform,and the mass fraction of aluminum decreased from 99.61%to 99.10%as the experimental temperature increased from 313 K to 333 K.In this work,the optimum experimental conditions were−1.2 V(vs.Al)and 313 K.At this time,the cathode current efficiency was 97.80%,while the energy consumption was 3.72 kW·h/kg.

Role of trivalent antimony in the removal of As, Sb, and Bi impurities from copper electrolytes

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.

CAUSE OF FORMATION OF NODULAR COPPER PARTICLES ON ELECTROREFINED COPPER SUBSTRATE

ＣＡＵＳＥＯＦＦＯＲＭＡＴＩＯＮＯＦＮＯＤＵＬＡＲＣＯＰＰＥＲＰＡＲＴＩＣＬＥＳＯＮＥＬＥＣＴＲＯＲＥＦＩＮＥＤＣＯＰＰＥＲＳＵＢＳＴＲＡＴＥ￥Ｌｉｎ，Ｊｉａｎｘｉｎ；Ｌｉ，Ｘｕｅｌｉａｎｇ；Ｃｈｅｎ，Ｈａｎｈｅ；Ｈｅ，Ｊｉａｎｂｏ（ＨｅｆｅｉＰｏｌ...

KINETIC STUDY ON THE REMOVAL OF LEAD AND SILVERFROMCRUDEBISMUTHBYANODEREFINING

The anode refining process to remove lead and silver from crude bismuth was studied. The study was carried out with chloride melts at 400 ℃ in a crucible-in-crucible type pyrex glass electrolyzer. The kinetic regularity of the removal of lead and silver was found to be in accordance with the equation:Inc=b-kt. Values of constant k were determined for different current density.The relationship between the purity of refined bismuth and its direct yield wasalso determined. A two-stage anode refining method was established. The firststage. was to remove most part of lead (about 90%) at higher current density ;the second stage was used for removing silver and the remains of lead at lowercurrent density. Under appropriate conditions high purity (WPb < 0.001%,WAd<0.004%) of bismuth could be obtained from crude bismuth with the direct yield of bismuth up to 98%.