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By J. A. Gonzalez-Dominguez

During the electrorefining of lead by the Betts process, ionic concentration gradients become established within the slimes layer. These gradients contribute to precipitation of secondary products and to gradients in electrode potential applied to slimes filaments, and thereby affect the dissolution of noble impurities. This paper describes the experimental results obtained when a typical lead anode was dissolved under galvanostatic conditions with concurrent interruption of current at preset slimes thicknesses. Reference electrodes were incorporated within the lead anode to follow the potential gradients across the slimes electrolyte. Samples of the slimes electrolyte were withdrawn in-situ and their compositional changes were related to transport processes across the slimes layer. Upon current interruption the anodic overpotential decays, first abruptly (as the uncompensated ohmic drop disappears), and then slowly (due to the presence of a back E.M.F. created by ionic concentration gradients that decay slowly). Current interruption measurements showed that: (A) concentration gradients exist across the slimes layer, (B) inner solution potentials within the slimes layer can be larger than those measured from reference electrodes located in the bulk electrolyte, (C) secondary products can shift the inner solution potential to negative values that reverse upon re-dissolution and (D) ionic diffusion is seen upon current interruption but it is complex and difficult to model due to the presence of processes that can support the passage of internal currents. SEM and X-ray diffraction analysis of the slimes filaments indicated that secondary reactions leading to the formation of Si02 and PbF2 take place (mainly at the anodelslimes interface). The onset of these reactions and their relationship to the Pb-F-Si-H20 Eh-pH diagram are linked to the industrial operation of the Betts process.

Jan 1, 1994

By A. A. EI-Geassy

High-grade iron ore fines rejected from the DRI plants (>96%Fe2O3) were isothermally reduced in 30-60%CO/H2 gas mixtures at 973-1273K. The freshly reduced reaction products were then subsequently carburised in either Hz/CO or H2/CO/S mixtures at 823-1 073K for 30-120 min. The thermogarvimetric technique was used to follow up both of reduction and carburisation reactions as a function of time. The carburised samples were characterized by X-ray and Mossbauer techniques. Chemical and carbon analyses were also applied. The influence of temperature and gas composition on the reduction behavior was investigated. The calculated values of apparent activation energy, application of gas-solid mathematical formulations were correlated with the microstructures to predict the reduetion mechanism. The influenee of carburization time, temperature, CO contents in H2/CO or H2/CO/S were investigated. A conversion extent of Fe to Fe3C was taken as a measurable index for the efficiency of carburization rcaction under the different experimental conditions.

Jan 1, 2003

By A. A. el-Geassy

High-grade iron ore fines rejected from the DRl plants (>96%Fe20) were isothermally reduced in 30-60%COIH2 gas mixtures at 973-1273K. The freshly reduced reaction products were then subsequently carburised in either H2/CO or H2/CO/S mixtures at 823-1073K for 30-120 min. The thermogarvimetric technique was used to follow up both of reduction and carburisation reactions as a function of time. The carburised samples were characterized by X-ray and Mossbauer techniques. Chemical and carbon analyses were also applied. The influence of temperature and gas composition on the reduction behavior was investigated. The calculated values of apparent activation energy, application of gas-solid mathematical formulations were correlated with the microstructures to predict the reduction mechanism, The influence of carburization time, temperature, CO contents in H2/CO or H2/CO/S were investigated. A conversion extent of Fe to Fe3C was taken as a measurable index for the efficiency of carburization reaction under the different experimental conditions.

Jan 1, 2003

By N. M. Komkov

The main operation of obtaining zinc from sulfide raw materials by hydrometallurgical technologies is the oxidation roasting of zinc concentrates in fluidized bed furnaces. The technical-economic parameters are determined by the parameters of the roasting process, which depend on the composition of the initial raw materials, the temperature of the bed and on other factors. The predetermined roasting temperature is maintained due to the change of specific efficiency as well as to the quantity of the heat removed from the bed. The efficiency of caissons depends at a high degree on the composition and the thickness of the accretion formed on the surface of the caissons. Forecasting the roasting results is impossible unless we know the mechanism of the accretion formation. The aim of the present paper is the thermodynamic analyses of the behavior of the charge compositions under roasting and the determination of the potential mechanism of the accretion formation. The thermodynamic analyses show that under conditions of the oxidation roasting the thermodynamic probability of the formation of zinc sulfate is higher than the probability of the oxide formation until a temperature of873 OK is reached. The thermodynamic probability of the formation of the lead sulfate is higher than the probability of oxide formation in the entire temperature range of roasting. The probability of formation of ferrites and silicates of zinc decreases only insignificantly the sulfate stability. The results of the investigation of the accretions composItion formed under roasting of concentrates with particle sizes less than 0.02 J..lm (60%), containing 65% of sphalerite (ZnS), 12% of pyrite and chalcopyrite (FeS2 and CufeSz) each, 3% of galenite (PbS), 7% of silica and other non-ore minerals, have shown that the composition of accretion varies depending on the depth of the accretion layer. The accretions on the caissons and the thermo-siphons consist mostly of zinc sulfate (more than 50%). The accretions of forehamber consist mostly of zinc oxide. They also contain ferrites and silicates. The formation of the sulfate zinc accretion in the cold parts of the fluidized bed furnace (the caissons and thermo-siphons) may be explained by a lower temperature on the surface and probably by a catalytic influence of the present oxides in the formation of S02 and sulfates. The nature of the structure of the accretion in the hotter parts of the furnace may supposedly be explained by the formation of elemental vaporous zinc during roasting.

Jan 1, 2003

By Kimio Itagaki

The distribution ratios of Ag, Pb, As, Sb and Bi for the Cu2S-FeS or Ni3S2-FeS matte / FeOx SiO2, FeOx-SiO2-CaO or FeOx-CaO slag equilibration in a MgO crucible were determined experimentally at 1523~1573K under controlled partial pressures of S2 and O2 at given PSO2 of 10.1, 50.7 and 101.3 kPa (0.1, 0.5 and 1 atm) and be observed dependency of distribution ratio on the matte grade, SO2 pressure and slag basicity were analyzed on the basis of thermodynamics,

Jan 1, 2003

By Z. M. Zheng

Cyclic voltammetry, potential step, and ac impedance techniques were applied to study the electrochemical reaction of arsenopyrite in chloride solutions. The relationship between anodic current density and time in potential step measurements indicates that the oxidation of arsenopyrite is irreversible. The results of the constant potential coulometry show that the stoichiometric factor of the total electron involved in the overall reaction is 14. It is proposed that the dissolution of arsenopyrite is retarded by coverage of sulfur produced in the reaction as an intermediate product. The measured results of ac impedance strongly support the proposition. The proposed reaction mechanism also explains satisfactorily the charging current density and Tafel slopes measured in potential step measurements.

Jan 1, 1995

By Julian Johnson

The effect of changing redox potential (Eh) on the high temperature sulfuric acid leaching of Western Australian dry-land nickel laterite ores has been investigated. In particular, the effect of added reductant (sulfur, sodium sulfite) or oxidant (potassium chromate) on Eh, leaching kinetics, metal extractions, acid utilisation and leach residues has been determined. Three separate ores - nonhonitic ores from Murrin Mumn and Bulong, and limonitic ore from Cawse - were used in the study. Sulfur addition varied from 0 to 7.8 kg/t ore. The total acid loading was kept constant at 430 kg/t (Murrin Murrin ore) and 330 kglt (Cawse ore), whilst acid loading for Bulong ore was varied according to the presence of either reductant or oxidant. The extraction of both nickel and cobalt from limonite ore remained unaffected when small amounts of sulfkr were added, but addition of even small amounts of reductant to nontronitic ore decreased both nickel and cobalt extraction. Increased manganese and iron dissolution were observed as the levels of reductant increased, accompanied by a decrease in chromium dissolution. As the iron dissolution increased, free acidity decreased, with a subsequent decrease in nickel extraction. In contrast, addition of oxidant lead to reduced iron and manganese dissolution and slower extraction of nickel and cobalt. Keywords: Limonite, Nonhonite, Eh, Nickel Extraction

Jan 1, 2004

By Eduard Ouerra, Nuo Jin

"The use of polytetrafluoroethylene, PTFE, as a solid sorbent for elemental sulfur during pressure oxidation of chalcopyrite was investigated. The effects of agitation, PTFE particle size and lingin sulfonate addition were evaluated using leaching conditions that were otherwise similar to those employed in the CESL process. The effects of these factors and their interactions on chalcopyrite oxidation are explained in terms of interfacial forces and solid-solid interactions. Using relatively fine PTFE powder with vigorous agitation resulted in about 100% copper extraction in less than 90 minutes without the need for grinding of the flotation concentrate.IntroductionThe extraction of copper from sulfide ores has always been dominated by the conventional pyrometallurgical smelting process. Though much effort has been made to develop various hydrometallurgical processing routes, smelting remains as the dominant process, treating approximately 80% of the chalcopyrite concentrates worldwide [1]. However, some of recently emerged techniques for treating chalcopyrite through hydrometallurgical routes are showing results that are competitive with smelting in terms of economical feasibility. Representative methods include: Activox Process, CESL Process, Anglo/UBC Process, High Temperature Pressure Oxidation, and Bio-Oxidation. Among these, the CESL processes operate at a medium temperature range (typically 140-150GC) and oxygen pressure of 100 psi, with chloride as a catalyst, and reportedly achieve copper extractions of about 95% with a light regrinding of flotation concentrate to a p95 of 45 ìðé [2]. In spite of this satisfactory extraction result, the leach residues contain significant amounts of conglomerates which contain a small amount of unreacted concentrate [2], The conglomerations are formed because the elemental sulfur generated is liquid and sticky (melting point of sulfur being 119°C), and has a tendency to wet the sulfide mineral surface, a fact which inhibits the oxidation of the minerals. The overall process chemistry of the CESL process may be summarized as follows [3]:"

Jan 1, 2012

By D. W. Collins

Several organic and inorganic substances are widely used to control deposit structure and morphology during the electroprocessing of copper. Methods for monitoring the levels of thiourea, glue and guar gum during electrorefining and electrowinning have been successfully developed under the trade names of Reatrol and CollaMat. Other instrumental methods have been developed for additives and decomposition products associated with the electroplating of copper and other metals. Generally, these methods have been found to be either insufficiently sensitive or lacking in the desired selectivity for some or all of the additives. These procedures have mostly employed DC techniques; i.e., cyclic voltammetry, Tafel analysis, etc. In this work, chronopotentiometry (CP) and AC voltammetry were used to examine the interaction of glue, guar gum, thiourea and chloride during the electroplating of copper onto a platinum electrode. In addition, the interactions between the additives have been explored. It was found that glue in pure electrolyte (H2S04 and CuS04 only) had no effect on the chronopotentiogram. Glue was only active if chloride ions were present. The addition of thiourea resulted in several different chronopotentiograms depending on the presence of either chloride or chloride and glue. Thiourea used in conjunction with glue and chloride showed a significant increase in the polarization during copper deposition when compared to the electrolyte containing only glue and chloride. The use of a modified channel electrode further increased the sensitivity of CP. The use of AC voltammetry was explored as a technique to monitor some of the additives. AC voltammograms have more spectral detail then their DC counterparts and it is possible to monitor some of the additives at very low concentrations with AC techniques.

Jan 1, 1999

By Jian Li, S. Penttila, W. Zheng

"Materials selection for Gen IV supercritical water reactor in-core components faces major challenges due to severe operating condition. Beside high-temperature mechanical properties, SCC and general corrosion resistance of commercially available materials are also major focuses in recent research. Recent reports suggest that certain types of surface modifications are beneficial to SCW corrosion resistance. In this study, the effects of surface modifications are investigated, and possible mechanisms for improved corrosion performance are discussed.IntroductionThe current Canadian pressure-tube supercritical water reactor (SCW) design specifies a core outlet temperature of 625°C under 25 MPa of pressure, with peak cladding temperature as high as 850°C. Challenges in materials selection include high-temperature mechanical properties, corrosion resistance, SCC resistance and radiation damage. Most of the SCW corrosion test results available are below 730°C. Early work by Allen [1] summarized the corrosion resistance of alloy groups including Ni-based super alloys, stainless and ferritic/matensitic (F/M) steels that can potentially be used for SCW reactors. F/M steels can only be used at low temperature sites (e.g. down stream piping). At 500°C and 25 MPa, F/M steels develop a thick but mechanically stable oxide layer. However, the long term stability of the surface oxide layer is largely unknown. Ni-based alloys appear to form very thin surface oxide, however pitting was observed in the vicinity of some intermetallic precipitates [2-5], and dissolution of major alloying components could pose significant problems for down stream piping [6]. In addition, concerns of Helium formation due to Ni transmutation prevented this alloy group to be used as fuel cladding. The corrosion resistant austenitic stainless steels (e.g. 316L) are found to be susceptible to localized corrosion such as pitting, intergranular attack and stress corrosion cracking (SCC) [7]."

Jan 1, 2012

By Bora Derin, Onuralp Yucel, M. Seref Sonmez, Murat Alkan

"Latest stage in the production of boron carbide by metallothermic methods using magnesium was the leaching process. Boron carbide particles obtained by self-propagating high temperature synthesis contained several impurities such as magnesium oxide and magnesium borates after the metallothermic reactions. Removal of such contaminates by hydrometallurgical methods required to produce high purity boron carbide. Leaching by concentrated hydrochloric acid solutions resulted in the production of pure boron carbide together with high magnesium and boron containing solutions. Removal of such ions from the spent liquor was the necessity to have dischargeable solution. In this study, precipitation of magnesium and boron compounds from relevant chloride containing spent liquors and the production of saleable products was aimed. The effects of chemical reagents, pH of the solution on the precipitation efficiency of magnesium and boron compounds were investigated in the study. Chemical analysis and the characterisationof solid phases by using x-ray diffraction analysis were the latest stage.Introduction A variety of advanced ceramics, inter-metallic, organic and inorganic compounds, oxygen free single crystals, and polymers can be synthesized by using different SHS techniques [1, 2, 3]. In the SHS process, after initiation, reaction becomes self-sustaining and propagates in the reactant mixture. A high amount of heat which is generated during the process accelerates the reaction rate and thus it makes the process highly productive and economically feasible for different production scales. After the SHS process obtained powder mixture needs to reacted with acidic solutions to purify the product. In this case B2O3 was reacted together with C and Mg to synthesis fine B4C powder resulted in the production of MgO as well according to the Eq. 1 and then MgO was removed from the mixture by leaching with the concentrated HCl solution as shown in Eq. 2, respectively [4, 5]."

Jan 1, 2008

By L. E. Murr

Preliminary studies of bacterial attachment to MoSp (molybdenite) have indicated a low correlation between dislocation density in the (0001) basal plane and the density of attached microbes. In the present investigation, poly- crystalline thin sections of CuFeSp (chalcopyrite) have been ion-etched or carefully comminuted to electron transparency and observed in the transmission electron microscope. The thinned test sections were then immersed in a culture solution in which bacterial attachment occurred. The attached bacteria were biologically stained in a uranyl acetate solution and the entire thin CuFeSp sections or tiny particles containing thin, electron transparent edges with bacteria attached were observed in the transmission electron microscope, allowing the coincidence of bacteria and their density to be directly observed in relation to lattice dislocations and crystallographic orientations of the exposed surfaces. This technique has the advantage of exposing crystallographic orientations where dislocation lines intersect the free mineral surface, and the emergence sites of dislocations could in principle be directly investigated as a possible preferential attachment site for bacteria. Bacteria morphologies were also extensively observed in the scanning electron microscope. The implications of the results are that although a strong correlation between dislocation density and distribution and bacterial attachment, density, and distribution has not been established, systematic multiplication of dislocation densities in crystalline mineral particles to be leached could enhance leaching rates by increasing the reaction rates as well as the density of attached bacteria at crystalline, metal-rich phases. Techniques for dislocation production in mineral and ore bodies and the particular implications in chalcopyrite leaching are discussed in relation to in-situ leaching where comminution is attained by explosives and the generation of strong shock waves in an ore body. The present study demonstrates the use of microanalytical and microscopic techniques in the investigation of fundamental microstructural phenomena in hydrometallurgical processes.

Jan 1, 1976

By K. J. Cathro

A hydrometallurgical process is described for the recovery of copper from chalcopyrite concentrates. The process is based on a cupric chloride leach, the concentrate having first been "activated" by heating it with sulphur at a temperature near 400°C. This activation process converts most of the iron of the chalcopyrite to pyrite, which is insoluble in the cupric chloride leachant. The copper is converted to the mineral idaite, which dissolves readily in hot cupric chloride: at 106°C, 98% of the copper is extracted in a three-stage countercurrent leach, the leaching tirqe being 1 hour per stage. The sulphur of the chalcopyrite appears as elemental sulphur, which is recycled for the activation of further concentrate, the final leach residue consisting of pyrite, plus the gangue present in the original concentrate. The copper extracted can be recovered by electrowinning, using a diaphragm cell. Current efficiency (one-electron basis) is about 70% but the cell voltage is only about 1 V, so that power consumption is three times lower than for the conventional sulphate electrowinning process. The leachant is simultaneously regenerated in the anode compartment. The behaviour of minor elements in the concentrate has also been studied.

Jan 1, 1976

By John Nauman

Liquid ferrous silicates that are related to cop- per slags have been studied as media for the transfer of heat in pyrometallurgical processes. The effective thermal diffusivities have been measured from 1025Oto 1400°C, and values in the range of 0.004 to 0.007 cm2/ sec have been obtained. The heat-transfer characteristics of these slags have been determined by measuring the rise of temperature of a cold nickel sphere immersed in the liquid slag. The sphere is spun about its vertical axis to obtain a well characterized flow of liquid about the sphere. The principal barrier to the transfer of heat from the bulk slag to the metal sphere is a solid shell of slag that forms around the sphere and subsequently melts. It appears that the detailed nature of this shell is important to theheat- transfer process. A mathematical model is used to predict the rate of heating of the sphere, and to evaluate various aspects of the system that can influence the transfer of heat.

Jan 1, 1976

By Suchun Zhang

The alkaline oxidation of refractory gold concentrates containing arsenopyrite and pyrite at ambient temperatures and pressures has been found to be accompanied by the simultaneous dissolution of gold without the addition of cyanide. A detailed study has been made of the kinetics of the oxidation of the pure minerals and of several concentrates. The reaction products of the oxidation of arsenic and sulphur have been monitored using chromatographic techniques. In the case of arsenopyrite, thiosulfate, monothioarsenate, arsenate and sulfite are the principal products while thiosulfate has been confirmed to be the dominant product of pyrite oxidation. Gold, either as added powder or as a constituent of the concentrates has been found to dissolve simultaneously during the alkaline oxidation of both arsenopyrite and pyrite, and this appears to be associated with the in-situ formation of thiosulfate as a lixiviant. The effects of temperature, stirring speed, oxygen partial pressure, alkalinity and pulp density on the oxidation of arsenopyrite and the dissolution of gold have also been investigated. Keywords: Gold, dissolution, arsenopyrite, pyrite, alkaline, oxidation, thiosulfate, thioarsenate

Jan 1, 2005

By Józef Czemecki

Polish copper concentrates are characterized by high levels of impurities, particularly Pb and As. Two technologies are being used for copper concentrate smelting at KGHM Polska Meidz S.A., namely the shaft furnace process (Legnica Copper Smelter, Glogów I Copper Smelter) and a single-stage process for direct to blister concentrate smelting in a flash furnace (Glogów II Copper Smelter). Both technologies are used at different physical and chemical conditions which results, in different impurities behavior. The paper presents flow sheets for copper production in a plant using the shaft furnace process and in another in which a single stage flash process is used. The metals distribution in particular semi-products is given as well as a method for elimination of impurities from the copper production cycle. Methods are also discussed for alloy and matte converting and copper refining to obtain low Pb and As concentrations in anode copper (0.3% Pb and 1500 ppm As maximum) that are being used in the KGHM Polska Meidz plants. Useful co-operation between the plants using different technologies, aimed at the limiting the effect of undesired impurities on the quality of blister copper produced, is also described.

Jan 1, 1998

By Batric Pesic

Calcium silicate slag (Di-Cal) and magnesium oxide condensate (MgO) are the by-products of magnesium smelting operations, As these oxides have acid neutralizing and metal precipitating properties, it was decided to examine their reactions with (a) individual heavy metals and (b) with a mixture of metals in solution, The resulting solid reaction products were further tested with respect to the stability of the contained metals, The stability of the solid precipitates were examined as a function of the method of precipitation and as function of the solution pH With respect to the method of precipitation, the performance of Di-Cal and MgO was compared to the performance of lime, an industry standard for heavy metal precipitation, Four different pH solutions (4,0, 5,0, 7,0 and 1 LO) were used to study the effect of pH on the stability of the precipitates. It was found that Di-Cal, in most cases, produced the most stable precipitates and thus, outperformed lime, Metal precipitates prepared by the addition of MgO were the most soluble for each metal studied, except for Se,

Jan 1, 2001

By Grant E. Casley

Since 1970 Mount Isa fines Limited has made a significant increase in blister copper production from approximately 100,000 to 155,000 mt per annum and in fact 161,040 mt were produced in the calendar year 1974. Flowsheet developments including fluidised bed roasting and converter slag flotation are discussed, particularly their contributions to minimising major equipment changes in smelting and converting. The use of model- ling and simulation techniques for such an exercise is mentioned. The paper reports the alterations made to both equipment and operating techniques in the reverberatory furnace and converter sections to achieve the regular production of 250 mt of blister per converter day from a 41% Cu matte grade. The effects of flux composition on converting performance are highlighted. The air quality control programme is discussed in relation to its restriction of blister copper production.

Jan 1, 1976

By Osamu Yamamoto

In antibacterial evaluation of carbon-ceramic composites, we prepared two type composites with emphasis on carbon-ZnO system; one was porous carbon materials containing ZnO nano-particles and another was porous ZnO coated with carbon thin film. Porous carbon samples containing ZnO at highly dispersed state were prepared by carbonizing the resin exchanged by Zn2+ ion. Porous ZnO coated with carbon thin film was obtained by the pyrolysis of poly (vinyl alcohol). Antibacterial activity of these composites obtained was evaluated by measuring the changes in electrical conductivity with bacteria growth. The antibacterial activity on the composites increased with the increase of t he amount of ZnO in composite and decreased with the increase of carbonization temperature. The antibacterial activity for Staphylococcus aureuswas found to be stronger than that for Escherichia coli. No activity of the carbon samples without ZnO was observed. The occurrence of antibacterial activity was supposed to be due to the generation of hydrogen peroxide from ZnO in composite. In the present work, antibacterial activity of carbon-ZnO composites was studied in the details.

Jan 1, 2006

By R. W. Lawrence

A method by which it is possible at an oxidation potential below 680 mV SHE to achieve quantitative conversion of sulphide sulphur to elemental sulphur instead of sulphate in a biological leach of chalcopyrite and bornite has been investigated. The process chemistry, biological phenomena and process flowsheet options are discussed. Several copper concentrates have been evaluated and have been found to be amenable to th process. Results to study the progression of chalcopyrite decomposition during the leach are presented and mineralogical factors affecting the requirement for silver addition are discussed. A chloride addition method for improving silver recovery is described. The results of a small scale continuous leach test have demonstrated that continuous operation can be carried out with high copper extraction and stoichiometric conversion of sulphide sulphur to elemental sulphur.

Jan 1, 1985