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By H. C. E. Regidor, M. G. Mena, H. D. Mendoza

Cyanidation leaching has always been the most widely used method of extraction of gold in the world. Its low cost and high selectivity has made it the prevalent choice for mining companies, and even for the small scale miners. The use of cyanidation in small scale mining has been an issue for the longest time, mainly due to the operation’s lack of safety measures, health care or environmental protection regulations. In pursuit of more environmentally friendly methods of extraction of gold, several alternative extraction processes have been explored, one of which is chlorination. The chlorination process is advantageous when recovering refractory gold locked in sulfides, as it simultaneously oxidizes the surrounding sulfides as well as dissolve any gold exposed to the lixiviant. This research was conducted to study and develop a safer alternative way of extraction of gold from small scale mining operations, without compromising the recovery of gold. In this study, a variation of the chlorination process has been employed for a refractory flotation concentrate wherein the majority of the gold is locked in sulfides. Hypochlorite-bearing reagents were used as the leaching reagents, and the method developed was a 2-stage leaching process in differing pH conditions. The solution pH and Eh was monitored all throughout the runs, and aliquot samples were taken at time intervals for analysis. SEM-EDS imaging was used to determine the mode of oxidation of the chlorination process, and the image obtained showed that the oxidized layer followed the shape of the particle, suggesting a diffusion controlled process. XRD analysis of the sample before and halfway through leaching further confirmed the oxidation of the sulfides. The amount of gold dissolved in the aqueous solution and in the solid residue were used as the basis for the determination of the recovery of gold. An average gold recovery of up to 84.38% was obtained using the developed method in just 7 hours of leaching. This method was then employed for a pilot-plant scale test and a gold recovery of 79.2% was obtained.

Jan 1, 2018

By Shangshu Li, Xin Li, Xionggang Lu, Xingli Zou, Kai Zheng, Yinshuai Wang

Ti5Si3/TiC composite has been successfully prepared from the titanium-rich slag/SiO2/C mixtures precursors by an electrochemical process. The electrochemical production process was carried out in molten CaCl2 salt at 1000 °C and 3.8 V. A pressed cylindrical pellet of titanium-rich slag/SiO2/C mixtures served as a cathode, and a solid oxide oxygen-ion-conducting membrane (SOM) tube filled with carbon-saturated liquid tin acted as an anode. The phase transformation of the cathode pellets during electrolysis process was investigated, the microstructure of the obtained products was characterized. It is found that the reaction pathways can be divided into three main stages during the electro-reduction process. The first stage is the generation of calcium compound, the second stage is the electrochemical reduction of the compound, and the third stage is the formation of Ti5Si3/TiC composite. The prepared Ti5Si3/TiC composite exhibits homogenous and nodular particle morphology.

Mar 1, 2018

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 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 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 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 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 O. A. Olaseinde

The 2101 lean duplex stainless steel has wide potential application in storage, heat exchangers, and in the oil and gas industries. This work investigates the electrochemical behaviour of 2101 duplex stainless steel with an addition of 0.15 wt% ruthenium, using potentiodynamic techniques in 1M H2SO4 at 25º, 40º, 60º, and 80ºC. The microstructures of samples were characterized using optical metallography and scanning electron microscopy. The results showed that the ruthenium addition moved the corrosion potential of alloy 2101 to a more positive potential. All samples containing ruthenium displayed longer passive regions at 25°C and 80°C compared to those without ruthenium. Alloys without ruthenium had higher critical current density (icrit) values when compared to the alloys with ruthenium. Ruthenium additions decreased the passive current densities and inhibited anodic dissolution. At room temperature the corrosion rate of alloys with ruthenium was lower than these without ruthenium.

Jan 1, 2012

By O. A. Olaseinde

The 2101 lean duplex stainless steel has wide potential application in storage, heat exchangers, and in the oil and gas industries. This work investigates the electrochemical behaviour of 2101 duplex stainless steel with an addition of 0.15 wt% ruthenium, using potentiodynamic techniques in 1M H2SO4 at 25º, 40º, 60º, and 80ºC. The microstructures of samples were characterized using optical metallography and scanning electron microscopy. The results showed that the ruthenium addition moved the corrosion potential of alloy 2101 to a more positive potential. All samples containing ruthenium displayed longer passive regions at 25°C and 80°C compared to those without ruthenium. Alloys without ruthenium had higher critical current density (icrit) values when compared to the alloys with ruthenium. Ruthenium additions decreased the passive current densities and inhibited anodic dissolution. At room temperature the corrosion rate of alloys with ruthenium was lower than these without ruthenium.

Jan 1, 2012

By A Frydrychewicz, J. Mirza, J. Lipkowski

The objective of this work was to understand the mechanisms of action of additives, such as thiourea, that enhance gold leaching in thiosulfate solution. The leaching reaction and surface passivation were investigated using linear sweep voltammetry. Leaching currents were determined using analysis of current-potential curves and the mixed potential theory. The gold-electrolyte interface was further characterized with surface enhanced Raman spectroscopy. The results show how thiourea prevents formation of oxysulfur compounds, which passivate the gold surface. Other molecules such as 3- m ercaptopropionic acid and L-cysteine were also studied as possible additives to prevent passive layer formation.

Jan 1, 2011

By J. A. Venter, M. K. G. Vermaak

There are practical indications that flotation recovery of palladium bismuth tellurides is poor. This work tested whether this can be caused by a lack of interaction of the collector with the telluride. Impedance measurements, voltammetry and Raman spectroscopy were performed to determine the interaction of dithiocarbonate collectors (KEX) with Pd-Bi-Te. Impedance measurements showed lower capacitance values in solutions containing KEX indicating the formation of a continuous surface layer. Anodic and cathodic polarization diagrams show the mixed potential tobe higher than the reversible potential of the xanthate-dixanthogen equilibrium reaction; hence the formation of dixanthogen on the surface is possible. Electrochemically controlled in situ Raman spectroscopy did indicate the presence of bulk diethyl dixanthogen on the surface. Raman spectroscopy has confirmed the co-presence of xanthate with dixanthogen, indicating that xanthate retains its molecular integrity when it adsorbs on the surface of the Pd-Bi-Te. As a result, the mineral surface is expected to be hydrophobic and a lack of collector interaction with the mineral is not the reason for low PGM recoveries experienced. Keywords: Raman spectroscopy; Pd-Bi-Te; ethyl xanthate; platinum flotation; Great Dyke; Pd-bearing bismutho-tellurides and moncheite.

Jan 1, 2004

By M. K. G. Vermaak

There are practical indications that flotation recovery of palladium bismuth tellurides is poor. This work tested whether this can be caused by a lack of interaction of the collector with the telluride. Impedance measurements, voltammetry and Raman spectroscopy were performed to determine the interaction of dithiocarbonate collectors (KEX) with Pd-Bi-Te. Impedance measurements showed lower capacitance values in solutions containing KEX, indicating the formation of a continuous surface layer. Anodic and cathodic polarization diagrams show the mixed potential to be higher than the reversible potential of the xanthate-dixanthogen equilibrium reaction; hence the formation of dixanthogen on the surface is possible. Electrochemically controlled in situ Raman spectroscopy did indicate the presence of bulk diethyl dixanthogen on the surface. Raman spectroscopy has confirmed the co-presence of xanthate with dixanthogen, indicating that xanthate retains its molecular integrity when it adsorbs on the surface of the Pd-Bi-Te. As a result, the mineral surface is expected to be hydrophobic and alack of collector interaction with the mineral is not the reason for the low PGM recoveries experienced. Keywords: Raman spectroscopy; Pd-Bi-Te; ethyl xanthate; platinum flotation; Great Dyke; Pd-bearing bismutho-tellurides and moncheite.

Jan 1, 2004

The present work is mainly focused on developing intermetallic inert anodes for aluminum electrolysis. The anode alloy based on Al-Ti-Cu system was prepared by casting, followed by the application of a protective coating. Behaviour of corrosion and the passivation under anodic condition was characterized using the electrochemical and microscopic techniques. The results obtained clearly demonstrate that the oxide coating can provide good corrosion resistance via surface passivation of alloy anodes, rendering them inert in cryolite melt.

Jan 1, 2006

By E. Ghali, A. D. Bas

"Treatment of oxide, e.g. roasted gold ores has received relatively less attention than sulphidic ones and recently, handling of oxide gold ores is becoming essential. In this study, the influence of roasted gold ore (RGO) slurry (at 35% solid ratio) on the electrochemical dissolution of gold has been examined using pure gold and iron oxide minerals (hematite, maghemite, and magnetite) as disc electrodes by zeroresistance ammeter mode either in one or two separate containers. The presence of slurry decreased galvanic currents, i.e. corrosion rates due to the release and increase in the amount of soluble and/or insoluble species that could retard further the anodic behaviour of gold. Higher galvanic currents were observed in two separate containers than that in one container indicating the primary importance of galvanic interactions. SEM-EDS results observed iron hydro/oxide coatings on gold surface in case of magnetite test. However, in case of RGO electrode it is not a perfect passivation, although somewhat decreasing trend was observed on gold dissolution. These findings have revealed that passivation is not only a laboratory phenomenon, but also it could be responsible for the slowdown of gold dissolution in industrial practice.INTRODUCTIONThe cyanidation of gold is an electrochemical corrosion process thus; the dissolution of gold can readily be studied by electrochemical techniques. The outcome/summary of previous electrochemical studies of gold leaching can partially be summarized as follows: Filmer (1982) and Lorenzen and van Deventer (1992) reported the negative effect of pyrite and pyrrhotite on gold leaching due to the galvanic interactions; Aghamirian and Yen (2005) studied gold galvanic corrosion in presence of sulphide mineral electrodes only in one cell using zero-resistance ammeter (ZRA) mode; Dai and Jeffrey (2006) discussed, individually, the anodic and cathodic behaviours between gold and sulphide minerals, and Azizi et al. (2010, 2011) used a bed reactor to examine the influence of sulphide minerals on gold dissolution in one and two separate cells. Accordingly, a slowdown in gold leaching has generally been attributed to the passivation phenomenon, although the indication of this phenomenon is still an undergoing debate. For instance, Mrkusic and Paynter (1970) identified the passivation as the film formation of dissolved species from calcine, Crundwell (2014) explained passivation, in the case of corrosion of metals, as the formation of a layer which is composed of a new chemical species on the mineral surface and this layer inhibits or blocks further reactions. He suggested that passivation is related to the oxidation of the metal, and the formation of a passive layer that retards the rate of dissolution by several orders of magnitude. Consequently, galvanic interactions, passivation phenomena, or combinations of them are considered significant electrochemical factors affecting gold dissolution (van Deventer, Reuter, Lorenzen, & Hoff, 1990; Azizi, Petre, & Larachi, 2012). It is important to note that generalizing the influence of a mineral/metal on gold dissolution may not be correct in all cases, since contrary behaviours/results (for pyrite) have been observed (Aghamirian & Yen, 2005). Therefore, electrochemical study of gold is still a subject of research and need to be examined further in detail."

Jan 1, 2016