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By K. A. Natarajan, Abha Kumari

In this paper, electroleaching and electrobioleaching of ocean manganese nodules are discussed along with the role of galvanic interactions in bioleaching. Polarization studies using a manganese nodule slurry electrode system indicated that the maximum dissolution of iron and manganese due to electrochemical reduction occurred at negative DC potentials of -600 and -1,400 mV(SCE). Electroleaching and electrobioleaching of ocean manganese nodules in the presence of Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans at the above negative applied DC potentials resulted insignificant dissolution of copper, nickel and cobalt in IMH2S04 and in sulfuric acid solution at pH 0.5 and 2.0. Mechanisms involved in electrobioleaching of ocean manganese nodules are discussed. Galvanic leaching of ocean manganese nodules in the presence of externally added pyrite and pyrolusite for enhancement of dissolution was also studied. Various electrochemical and biochemical parameters were optimized, and the electroleaching and galvanic processes thus developed are shown to yield almost complete dissolution of all metal values. This electrobioleaching process developed in the laboratory may be cost effective, energy efficient and environmentally friendly. Keywords: Ocean manganese nodules, Electroleaching, Electrobioleaching, Galvanic interactions

Jan 1, 2003

By Henrik Gudbrandsen, Anne Støre, Ana Maria Martinez, Karen Sende Osen, Ole Kjos

The light rare earth metals Nd, Pr, La, Ce as well as some alloys with Fe, are today produced in China by electrolysis in molten fluorides using oxide raw materials. A major challenge is to obtain a good cell operation without de-composing the electrolyte leading to emissions of per fluorinated carbon (PFC) green-house gases to the atmosphere. This work is focused on understanding the fundamental requirements to run the electrolysis cells for DyFe alloy production in an ef ficient and environmental friendly way. Electrolysis experiments was carried out in DyF 3-LiF melts at 1050 °C. A Fe rod was used as consumable cathode and the (consumable) anode was made of graphite. To establish at which anode potential PFC occurred and thus enabling optimisation of the oxide batch feed rate, analysis of the anode gases was performed with Fourier Transform Infrared Spectrometer (FTIR). The produced DyFe alloy was characterised by X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDS).

Mar 1, 2017

By V. A. Luganov

During the treatment of raw materials containing arsenic and antimony, problems in the distribution of these elements in the process products occur. In a number of cases in processing of copper-bearing materials, it is possible (or necessary) to obtain speiss. The purpose of the present research is to study the theoretical aspects and analyze the technological possibilities of producing copper-bearing speiss and the subsequent electrometallurgical processing with copper extraction as well as arsenic and antimony utilization. Copper arsenide (Cu3As) and copper antimonide (Cu3Sb) are the main components of the speiss. A thermodynamic analysis of the electrochemical oxidation of Cu3As and Cu3Sb, carried out using Pourbaix diagrams, showed that in a pH range from 0 to 2, oxidation potential 0.45-0.55V, ions of copper and arsenic and antimony trioxide are in the equilibrium. The kinetic study has shown, that with an increase in the polarization potential, the dissolution process changes from chemical to diffbsion control. An increase in temperature stabilizes the electrolysis process due to dissolution of arsenic trioxide forming on the anode. Electrolysis of speiss using a cathode diaphragm with the solution pH = 1-2, current density 150-200 A/m2 and temperature 60-70°C makes it possible to obtain cathode copper with a current efficiency of 95-96% and to remove the arsenic from the process during the electrolyte cleaning process. The arsenic content in the cathode copper did not surpass 0.002%. As the result of the research, a technological flowsheet for copper-lead speiss processing was developed. At the present time this technology is undergoing pilot testing.

Jan 1, 1999

By Derek Fray

Molten salts have been used for the extraction of metals since the 19th century but, recently, many interesting processes have been investigated using mixtures of molten salts and different cathodic materials. In several existing processes, the cation is simply discharged from melt but, in some cases, complications arise when the electrode potentials of the cations are relatively close. For example, the co-deposition of sodium with aluminium in the Hall-Heroult process is discussed in terms of electrode potentials of the components in the molten electrolyte. Similar considerations will also be given to the anodic reactions with respect to chlorine, oxygen, carbon dioxide or monoxide evolution from chloride-oxide melts. In some cases, the cathodic product interacts with the cathode to produce new and exciting products such as nanotubes from carbon or titanates and reduced titanium oxides from titanium dioxide. Depending on the electrode potentials, it is also possible to completely change the cathodic reaction from discharge of the cation in the salt to ionisation of the anions in the cathode. Examples are given of the reduction of metal oxides to produce metals, high technology alloys and nanomaterials and the cathodic refining of liquid metals.

Jan 1, 2006

By Alicia Esther Ares, Carlos Enrique Schvezov, Alejandra Silvina Roman, Claudia Marcela Méndez

In this paper the structure of aluminum based alloys and their corrosion behavior by using different electrochemical techniques as characterization methods are considered. Currently, it becomes imperative to know the role of the Al2Cu against the susceptibility to corrosion of these alloys. The present work aims to studying the electrochemical behavior of aluminum base alloys with the following compositions: Al-1wt.%Cu, Al-4.5wt.%Cu and Al-15wt.%Cu (with different grain structures), in 1M NaCl solutions, at room temperature. Cyclic potentiodynamic polarization tests were performed and were found that the alloys with more than 1wt.%Cu in the matrix have an unstable behavior and without tendency to reach passivity. The equivalent circuits derived from electrochemical impedance spectroscopy technique (EIS) generally showed two capacitive contributions. The susceptibility to corrosion becomes a complex function, not only of copper concentration and structure, but also with interdendritic spacings and distribution of phases in the alloys.

Jan 1, 2015

By L. Sun

Recently, micro-tubular solid oxide fuel cells (SOFCs) have attracted the attention of many researchers because of their numerous advantages over larger tubular and planar SOFCs. These include excellent thermal shock properties giving rapid startup/shutdown capability, a high volumetric power density compared to larger tubular SOFCs, and reduced sealing problem compared to planar SOFCs. In order to screen cathode materials for micro-tubular SOFCs, the perovskite cathodes were deposited, using a variety of methods, on 10.5 mol % yttria-stabilized zirconia (YSZ) tubes. Their electrochemical properties were then evaluated by using electrochemical impedance spectroscopy and steady-state polarization methods, based on a three electrode configuration, and with the reference electrode position carefully optimized. The oxygen reduction reaction kinetics at the cathode/electrolyte half cell were then investigated in detail.

Jan 1, 2005

By H. Moslemi

Metal sulphides are usually semiconductor and their electrical conductivity is low; therefore they are sources of electrons and promote electrochemical reactions. This phenomenon is of significant importance in sulphide flotation. The formation of a hydrophobic surface on the sulphide minerals is the result of various electrochemical reactions. Potential difference in the mineral-liquid interface plays an important role in the kinetics of the reactions, and consequently, on the flotation behaviour of sulphides. The value of the potential difference is influenced by different oxidation-reduction reactions at the interface area, and is measured by a two-electrode system in which an electrode is applied as reference electrode. In this study, we attempted to measure open-circuit potentials of pyrite, pyrrhotite, and steel electrodes with respect to the reference electrode. To verify the results, two reference electrodes, saturated calomel and gold, were used. Time-potential relations with respect to both reference electrodes show that the potential of both pyrite and pyrrhotite increases with time; however, this trend decreases for steel except when at pH 12. The results show a potential drop by an increase in pH value, except for steel, for which the opposite holds. This paper discusses galvanic interactions between minerals and grinding media in the grinding circuits, as well as among other minerals in the flotation processes.

Jan 1, 2012

By A. Dell’Era, M. Pasquali, C. Lupi

"An electrochemical cell has been designed to treat very diluted cobalt solutions, i.e. those deriving from recycling processes of lithium-ion batteries. A reticulated vitreous carbon sponge was used as cathode and a Pt-coated Ti net as anode. A controlled potential electrolysis has been carried out in a solution flowing in the cell and maintained at a constant pH of 6.5. Considering the cathode dimensions (10.0 cm * 10.0 cm * 1.25 cm), rather high volumes of solution (>1 litre) can be treated with flow rates up to 1.6 l/min. The process yield is obviously related to the solution concentration; it has been observed that, starting with a solution containing 200 ppm of Co2+, the yield is initially ~35-40%, but it decreases to ~20% when 80% of the initial cobalt content has been electrowon. The yield increases up to ~50% if the carbon electrode is coated by cobalt. The conditions allowing a fast and complete removal of cobalt are outlined. Introduction Industrial liquid effluents containing heavy metal ions arise not only during hydrometallurgical processing, but also in many sector of chemical industries utilizing metal catalysts and process reagents. These waste solutions containing low quantities of metallic ions can be treated by chemical precipitation, solvent extraction, ion exchange, etc. before final discharge. All these techniques could be efficient for complying the aqueous effluents with the severe rules related to the environmental impact, but they can not directly produce metals. Particularly the chemical precipitation presents two main drawbacks, huge amount of sludge prodction and reagent costs to produce this useless and sometime dangerous sludge that have to be considered. Electrochemical technologies can be used for the treatment of effluents polluted by metal ions, showing the following advantages in comparison with other processes: 1. recovering of the polluting substances in metallic forms, with subsequent reusing; 2. absence of process slag, which should be subsequently disposed of. In this work an electrochemical reactor with a reticulated vitreous carbon cathode and a platinated titanium net anode has been designed and utilized for removal Co from waste aqueous solutions. Porous materials have been used as electrodes for this cell, as their high specific surface area favours the treatment of these low metal content solutions (1-7). This kind of electrodic material presents very interesting chemical-physical characteristics such as: low density, low thermal expansion and high electrical and thermal conductivities; particularly the reticulated vitreous carbon (RVC) presents a very elevated void volume, rigid structure, good resistance to temperatures in non-oxidizing environments and very low resistance to fluid flow."

Jan 1, 2008

By Melvin H. Miles

"Considerable research has been conducted on the anodic oxidation of methanol in fuel cells. The electrochemical reduction of carbon dioxide in aqueous solutions to form methanol is the same reaction in reverse, i.e. CO2 + 6 H+ + 6 e- ? CH3OH + H2O. The same catalysts and conditions may operate for both reaction directions. This carbon dioxide reduction reaction, however, must be able to compete with the electrochemical reduction of water to form hydrogen gas. Thermodynamically, the reduction of CO2 to form CH3OH is slightly more favorable than the reduction of water. The use of nearly neutral electrolytes rather than acidic electrolytes makes the reduction of CO2 kinetically more favorable. The thermodynamics of various reaction steps are presented. Similarities exist with the electrochemical reduction of CO2 and the green-plant photosynthesis process that converts CO2 to carbohydrates.IntroductionVirtually all of the oxygen in the earth’s atmosphere is of biological origin having been generated by green-plant photosynthesis from water and carbon dioxide [1]. The net reaction can be represented byCO2 + H2O ? O2 + [CH2O] (carbohydrates, etc.) (1)Chlorophyll and enzymes promote this reaction, and the energy required comes from sunlight. The actual photosynthesis process is a complex multistage reaction and requires 469 kJ mol-1 of energy supplied by the sun. Isotope tracer experiments using 18O have shown that both the oxygen atoms in the O2 molecule originate from H2O, whereas oxygen atoms in the carbohydrates come from CO2 [1]. The total amount of water on the earth is split by photosynthesis and reconstituted by respiration and combustion once every 2 million years or so. The photosynthetically generated oxygen gas temporarily enters the atmosphere and is recycled about once every 2000 years [1]. The carbon dioxide is partly recycled in the atmosphere and oceans after an average residence time of 300 years and is partly fixed by precipitation of CaCO3 and other carbonate minerals [1]."

Jan 1, 2008

By Zhongning Shi, Ramana G. Reddy, Min Li, Zhaowen Wang

Electrodeposition of cobalt from cobalt tetrafluoroborate (Co(BF4)2) was investigated using 1- butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4) ionic liquid. The experiments were conducted at 353 K. Chronoamperometry experiments confirm that the electrodeposition of cobalt on tungsten electrode proceeds via three-dimensional instantaneous nucleation with diffusion-controlled growth process. The average diffusion coefficient of Co(II) was found to be 7.5 × 10-8 cm2s-1 at 353 K, which is in good agreement with the estimated value from cyclic voltammetry. The electrochemical deposit was characterized using SEM-EDS and XRD methods. The SEM image shows formation of a dense and compact deposit at - 0.75 V. The EDS and XRD analysis confirm that the obtained deposit is pure cobalt metal.

Jan 1, 2015

By H. J. Sohn, S. G. Doo

A systematic study was carried out to investigate the reduction reaction mechanism of oxygen on pyrite surface using electrochemical techniques. The polarization curves showed two distinct regions, the Tafel region for superoxide formation and limiting current region for diffusion of dissolved oxygen to form hydrogen peroxide. These results were confirmed with a-c impedance measurements.

Jan 1, 1990

By J. Howarth

Two electrochemical processing methodologies have been used to electrogenerate bromine-laden solutions for gold-leaching purposes. In the first process, a laboratory-scale cell in which the anode and cathode compartments were separated by a cation-exchange membrane was employed. The bromine produced by electrolysis of a 4% bromide solution was used to leach gold from a low-grade ore. The pregnant leach solution was then returned to the cell to recommence the cycle. High current efficiencies (90-93%) were maintained over six cycles. In the second process, an undivided hypochlorite generating cell (Chloropac"') was used to generate bromine from a simulated leach solution. Electrolyses were performed on a pilot-scale (100-150 gallons) with solutions containing different levels of bromide ion. The current efficiencies were also high (80-90%) and unaffected by the bromide concentration (over the range 2.5-5%) provided the electrolysis was run to low conversion « 15%). The Chloropac module was capable of delivering 0.6 kg bromine per hour at a power cost of $0.09 per kg. Using these figures, a detailed economic assessment for a 1000 metric tonnes (MT) per day gold ore processing plant was made. Electrolytic regeneration of bromine in a gold leach/recovery circuit dramatically improves the process economics over cyanidation.

Jan 1, 1991

By K. Enns, J. J. Byerley

"While thiocyanate (SCN-) is used in a number of industrial processes (production of polyacrylonitrile filaments, synthesis of agricultural chemicals and certain metallurgical solvent extraction and flotation circuits) it is recognized more as an undesirable by-product associated with ' the metallurgical industry. Thiocyanate is present at low concentrations in some waste streams from the iron and steel industry. Of particular significance is the formation of thiocyanate during cyanidation of gold and silver ores, concentrates, tailing s and residues. The thiocyanate levels present in the resulting effluents may range from a few mg/I to several thousand mg/I.At present, thiocyanate does not appear to be as hazardous in the environment as cyanide (CN-) at the same concentration although its interaction with other species and resulting decomposition of products may be unacceptable. Of course the presence of thiocyanate in the leaching circuit and ultimately in the effluent streams may add considerably to the oxidative requirments of any non-selective treatment process for cyanidation wastes.With respect to the thiocyanate as it relates to the cyanidation process, two aspects are evident. Thiocyanate forms and persists in the cyanidation circuit resulting in a ""fouling"" condition with subsequent loss of leaching activity. In order to reduce or control this problem, it is common practice for some mills to discharge daily as much as 20% of the barren leach liquor. Besides contributing to fouling of the leach liquor the formation of thiocyanate represents an irreversible loss of reagent cyanide. It is noteworthy that in some present or proposed mill practice reagent cyanide loss through thiocyanate formation may reach 50%(1). The purpose of this paper is to discus s the application of controlled electrooxidation of thiocyanate with the view of suggesting a process for regenerating cyanide from waste thiocyanate(2). The paper describes the important theoretical aspects and presents experimental data obtained for thiocyanate electrooxidation using both small and large scale electrochemical reactors. Some economic conclusions are presented."

Jan 1, 1984

By Bing Li, Miao Shen, Qiang Wang, Yuqi Chen

Electrochemical methods including cyclic voltammograms, square wave voltammograms, chronopotentiometry are applied to characterize the reduction potentials of Na+ and Li+ ions in LiCl-KCl melts. According to theoretical calculation, the reduction potential for Na+ is slightly more negative than Li+ in NaCl-LiCl-KCl melts at 450℃. However, by electrochemical measurements, the reduction potential of Na+ is slightly more positive than Li+ in the above melt and the potential difference between Na+ and Li+ reaches 0.16-0.2V on an inert W electrode in 1.0-2.0 wt% NaCl-LiCl-KCl melts. An active Pb electrode is used to improve the removal rate of Na+ from LiCl-KCl melts. The reduction potentials for both Na+ ions and Li+ ions on a Pb electrode shift to more positive values and the reduction currents become larger. After 6h electrolysis on a Pb electrode at -3.0V, the practical removal efficiency of Na+ ions reaches 90.12% and the reduced products contain metallic Na and Li with a Na/Li mass ratio of 4.25/1.

Jan 1, 2015

By Jingwei Lou, Bing Li, Suzhen Li, Miao Shen, Jianguo Yu

"As a main impurity in primary lithium metal, magnesium is difficult to remove because of the very close relative volatility of the two metals. Electrochemical refining provides a possibility to completely remove Mg in the LiCl-KCl melt prior to Li reduction. MgCl2 reduction processes in LiCl-KCl- MgCl2 melt were investigated by cyclic voltammetry (CV), square wave voltammetry (SWV), chronoamperometry and chronopotentiometry. Then potentiostatic electrolysis was carried out and Mg (II) ion was reduced onto a liquid lead cathode from the LiCl-KCl-MgCl2 melt at the Mg deposition potential. The results show that Mg ( II ) is reduced in one step with two-electron transfer. The reduction potential of Mg ( II ) was well defined. The reduction of Mg( II) results in Li ( I ) underpotential deposition at 0.2V more negative potential than that of Mg( II) reduction. Therefore, in order to prevent Li ( I ) from codeposition with Mg, accurately controlling Mg ( II) reduction potential during the potentiostatic electrolysis was necessary. Ninety three to 99 % removal rate of MgCl2 was achieved after 8-12 h electrolysis when liquid lead was used as cathode.IntroductionMetallic Li has been widely used in batteries, light weight alloys and in fusion reactors because of its excellent properties. Currently, the only way in industry to produce metallic Li is by electrowinning from molten LiCl-KCl at about 450 °C [l-5]. LiCl-KCl is the only electrolyte used, because they presents a lower eutectic temperature and KCl shows a slightly higher theoretical decomposition voltage than LiCl, as shown in Table l .The produced metallic Li generally contains 1-2 wt% impurities including Na, K, Al, Ca, Mg, Si, etc. [6l, which are derived from the corresponding metal chloride compounds or metal oxide compounds existing in the LiCl and/or KCl raw materials. These impurities have to be removed by subsequent vacuum distillation at high temperatures to meet the requirements for metal Li purity in the final products. Separation of Mg from Li by vacuum distillation is difficult because their relative volatilities are very close, as shown in Table 2."

Jan 1, 2011

By F. Tailoka, G. Zhao

Pb is an unwanted impurity in Al for which there is no established method of removal. As it interacts strongly with alkali metals, separation was achieved by adding Na or K to molten Al at 953-1 003 K. Direct Na addition led to considerable evaporative loss but in-situ addition by electrochemical titration from a eutectic NaCl-KCl or KCl-BaCl2 mixture was found far more effective, in some cases reducing Pb content below detection levels within 2 h of titration. K appeared more effective than Na at low Pb concentrations but the use of Na was preferred as it is less toxic and explosive. Na removal from Al-Na and Na-Pb alloys was also carried out electrochemically, the use of these two alloys rather than the eutectic salt as a source of Na avoiding liberation of Cl2 at the anode

Apr 1, 1995

By Kazuya Koyama

We are studying the hydrometallurgical recycling process of indium from an Indium-Tin-Oxide(ITO) target. For this process, it is necessary to remove Sn(IV) ions from the aqueous hydrochloric acid solutions containing In(III). In this study, the removal of Sn(IV) ions by a potentiostatic electrolysis method was examined. The polarization measurements and potentiostatic electrolyses were carried out under a nitrogen atmosphere. In the Sn(IV) solution, current begins to rise at the cathode potential of -0.26 V vs. SHE, and increases with a reduction in the cathode potential. In the In(III) solution, current begins to rise at a cathode potential of -0.43 V vs. SHE. Metallic tin was electrodeposited without indium electrodeposition at the cathode potentials of -0.30 and -0.40V vs. SHE. More than 98% of the Sn(IV) was removed at the cathode potential of -0.40 V after the electrolysis for 3hrs. Both tin and indium were electrodeposited at the cathode potential of -0.50V vs. SHE.

Jan 1, 2006

By G. R. Doughty

It is shown that sodium can be removed very readily from molten aluminium by the use of a beta"-alumina, the more highly conducting form of beta-alumina, provided that the surface of the tube is wetted by a layer of salt. From current/time plots the theoretical amount of sodium removed has been calculated and excellent agreement obtained. The beta"-alumina tubes can be immersed directly in the Al without fracturing if they are pre-heated for a few minutes prior to immersion. According to its stability beta"-alumina should be attacked by molten Al at low Na contents, but in these experiments the salt acted as a protective layer. Magnesium chloride is a relatively cheap salt, whose Mg product can be used within a foundry. The only other product is NaCl, which can be used in-house as a flux or sent for disposal. No polluting gases are used or produced and no drosses created. The time for removal of sodium was quite short, comparable to that for chlorination

Jun 21, 1905

By Q. G. Liu

New solid-state electrochemical sensors 1;.1sing Li2SO4-Ag2SO4 electrolytes have been developed to measure SO2 and/or SO3 in gas mixtures. Silver embedded in part of the electrolyte is used as the reference electrode. Although single-phase electrolyte sensors yield accurate results for one to two days, a two-phase electrolyte cell exhibits excellent long-term chemical stability. For example, stable and accurate potent iometric responses have been obtained over a six mo.nth period. The. advantages of the two-phase electrolyte ( 23 mol% Ay 2SO4 ) cell include excellent mechanical strength on temperature cycling and an insensitivity to compositional variations in the electrolyte and to temperature fluctuations. Experimental tests have shown excell.ent results in SO2-air. mixtures with the SO2 concentration ranging from 3 to 10,000 ppm (vol). However, the SO2 concentration range was limited by a lack of standard gas mixtures, and our sensor cells can be used to measure S02 concentrations significantly less than or larger than our experimental range. Results also indicate that the presence of significant concentrations of CO2 and H2O in the gas mixture has no effect on the sensor response. Thus the two-phase electrolyte ( 23 mol% Ag2S04) sensor has exceptional selectivity, reliability and long-term chemical and mechanical stability.

Jan 1, 1985

By Toshiyuki Nohira, Eiichi Takeuchi, Tetsuo Oishi, Hideki Ono, Hirokazu Konishi

The Dy-Nd-Pr-Ni alloy sample was prepared by cathodic potentiostatic electrolysis at 0.65 V (vs. Li+/Li) for 1 h using a Ni plate in a molten LiCl-KCl-DyCl3-NdCl3-PrCl3 system at 723 K. The highest mass ratio (Dy/Nd+Pr) in the alloy sample was observed to be 50 at 0.65 V. Anodic potentiostatic electrolysis at 2.20 V for 12 h was conducted using the Nd-Fe-B magnet electrode in a molten LiCl-KCl system. All elements were almost dissolved from the magnet, and the original form of the magnet disintegrated. After anodic potentiostatic electrolysis at 2.20 V, cathodic potentiostatic electrolysis was conducted at 1.00 V for 5 h using a Mo plate in order to remove the dissolved Fe from the bath. Finally, cathodic potentiostatic electrolysis was conducted at 0.65 V for 12 h using a Ni plate. The mass ratio of Dy/Nd in the alloy sample was determined to be about 18.

Jan 1, 2015