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By Nobuhiro Kuriyama

Electrochemical activation behavior of an AB2-Laves-phase type hydrogen storage alloy, Zr0,9Ti0.lNi1.lCo0.1Mn0.6V0.2 was studied to make clear activation process of pellet-type metal hydride electrodes. An alkaline treatment of the electrodes with heated alkaline solution gave alloy surface enriched with nickel, and the treated electrode was more easily activated. The treated electrode desorbed more hydrogen during the first charge-discharge cycle, and was activated without induction period. A cross sectional view of the activated electrode showed finer pulverization of alloy particles than the annealed alloy, and impedance spectroscopy indicated larger surface area of the electrode using the as-cast alloy. Since the as-cast alloy contains inhomogeneities, multi-phase microstructure and stress in the particle, the finer pulverization of alloy particles with hydrogenation are considered to increase surface area in an earlier cycle in the case of the as-cast alloy, which leads larger reaction area and faster activation of the as-cast alloy electrode.

Jan 1, 2002

By Sharif Jahanshahi

Calcium ferrite slags are often associated with Professor Yazawa due to his pioneering work on the thermodynamics of this type of melts. Over the past years CSIRO has invested some effort in studying physico-chemical properties of such melts to fill in some gaps in our knowledge and explore opportunities for application of the understanding developed. These investigations cover thermodynamics, transport properties of calcium ferrite based slags, as well as the kinetics of reactions of such slags with refractories. The present paper provides an overview of some of these studies and highlights some of the interesting behavior of such melts. The oxidation state of copper and arsenic in calcium ferrite based slags are predominantly Cu+ and As3+, respectively, at oxygen potentials below 10.1 atm. The concentration ofCu2+ in such slags becomes significant at oxygen potentials of greater than 10'1 atm at 1300 ?C. The activities of CuOo.s and AsOl.S in calcium ferrite slags show strong deviations from the Raoultian Law, while that of CoO is very close to ideal behaviour with respect to pure solid CoO. Addition of Si02 to calcium ferrite slags can have significant effects on the activities of FeO and Fe2O3 and hence the stability of magnetite phase. Transfer of oxygen in calcium ferrite slags is fast with diffusivity of 2xlO?3 cm2/s at 1350 °C and activation energy of 16 kcal/mol Presence of solid phases, such as magnetite, has pronounced effect on the viscosity of calcium ferrite slags. The observed dependence on solid loading and shear rate indicates deviation from Newtonian behaviour. The interfacial tension between copper mattes and calcium ferrite slags is strongly dependent on the matte grade, with the determined values being much lower than the corresponding ones for interfacial tension between similar mattes and iron silicate slags. MgO, Cr2O3 and MgCr2O4 have low solubility in calcium ferrite slags and their solubility increases with increasing copper oxide content of the slag at 1300 °c. The oxidation state of the slag has strong effects on phase transformation, dissolution rate and disintegration of refractories in calcium ferrite slags. Other key factors with major impact on slag-refractory interactions include viscosity and surface tension of slags as well as the contact angle between slag and refractory material.

Jan 1, 2003

By Chai Li-yuan

Anodizing behaviors of magnesium alloys AZ31 at constant applied current, based on the electrolyte solution free of chromate or fluoride, were investigated. The anodizing process was influenced by constituents of electrolyte greatly. Therein, the oxylate salts, which led to the occurrence of the two totally different processes, played a determinant role in anodizing. They were stable and sparking process respectively. The morphology of anodizing film was observed by SEM and the structure of film was analyzed by XRD. During the stable process, a brown thin film was formed, however the sparking process led to the formation of white hard thick film. The functions of some kinds of additives, such as ammonia, glyceryl alcohol and PVP etc were also studied. Some of them had great effect on surface morphology of anodic film and some of them affected stability of anodizing process significantly.

Jan 1, 2006

By Katsutoshi Inoue

The sulfuric acid leaching of spent hydrodesulfurization catalysts yields an acidic solution rich in rare metals such as molybdenum, vanadium, cobalt, and nickel in addition to aluminum. For the purpose of separating and recovering the rare metals from the solution, basic solvent extraction characteristics of the metals involved with commercially available acidic organophosphorus reagents like TR-83, PC-88A, PIA-8 and CYANEX 272 as well as aliphatic alpha-hydroxyoxime LIX 63 from sulfuric acid media were investigated in the present work. It was demonstrated that CYANEX 272, PIA-8 and LIX 63 possessed excellent selectivity for molybdenum and vanadium over the other metals at comparatively low pH. Further, recovery of molybdenum and vanadium from the total leach liquor by the selected extractants was discussed. Additionally, in order to achieve preferential separation and recovery of cobalt and nickel over an appreciable amount of aluminum from the raffinate obtained after recovering molybdenum and vanadium, a systematic investigation was conducted on synergistic extraction behaviors of the mixed solvents of LIX 63 in combination with a series of acidic extractants such as CYANEX 272, PIA-8, PC-88A, D2EHPA, TR-83 and OPEHPA for cobalt, nickel and aluminum. It was elucidated that all of these mixtures could exhibit a good synergistic effect for extraction of cobalt and nickel, and that the lower the pKa of the acidic extractants, the greater the synergism. Contrarily, the extraction of aluminum, was considerably suppressed by LIX 63. Effective extraction of cobalt and nickel away from aluminum was accomplished from the sulfate solution at low pH (1.0 - 2.5) with the mixtures. In particular, the mixtures consisting of LIX 63 and CYANEX 272 or PIA-8 appeared to be the most feasible and economic from an industrial point of view, yielding acceptable separation efficiency for cobalt and nickel over aluminum and .a low acidity requirement for stripping cobalt and nickel as well as negligible degradation of LIX 63. Aluminum can be readily recovered as sulfate salt from the raffinate obtained after recovering molybdenum, vanadium, cobalt and nickel as outlined above by conventional crystallization method.

Jan 1, 1995

By Young-Geun Park

A new decarburization model for the RH system was constructed for calculating the decarburization reaction using a three-dimensional fluid dynamics program. The entire fluid flow in the RH process was calculated by evaluating the shape and volume of the plume zone, formed by Ar gas blown through multiple nozzles on the wall of the snorkel. On the basis of this fluid flow, the decarburizaiton reaction was calculated through establishing the decarburization reaction model, which considers the thermodynamics, reaction kinetics, and the decarburization sites (Ar bubble surface, bath surface, and the CO bubble fomtation at inner sites). The results from this model were compared with a real RH operation results with good agreement. Because it is possible to predict the carbon concentration at various conditions using this model, it may be useful in increasing the decarburizaiton rate. Key words : RH process, plume zone, decarburization, Ar bubble surface, bath surface, inner site, circulation flow rate.

Jan 1, 2001

By Agnes Y. Lee

he U.S. Bureau of Mines developed a method to treat lead-contaminated soil and ebonite battery casing wastes to produce a nonhazardous material. The cleanup procedure involves wet screening to separate a minus 18-mesh soil fraction; removal of metal1ic lead, rocks, wood, etc. ; carbonation to change lead sulfate to acid-soluble lead carbonate; size reduction; acid leaching; and rinsing. The casing wastes undergo size reduction and washing to remove the lead sulfate sludge before carbonation. Similarly, the minus 18-mesh soil is carbonated, then acid leached and rinsed. In leaching, fluosilicic acid (H SiF,) and hydrogen peroxide (H20,) are used to dissolve lead compounds. An electrowinning method is employed to strip lead from the lead-rich leachate. The acid content in the leachate is replenished with fresh H,SiF, acid prior to recycling. Treated casing wastes and soils pass the Toxicity Characteristic Leaching Procedure (TCLP) test and can be reclassified as nonhazardous materia1s. Based on this process, a conceptual pilot plant has been designed which will be demonstrated on wastes from two Superfund sites.

Jan 1, 1993

By J. B. W. Bailey

The Noranda Horne smelter in Quebec, Canada has change considerably during the last two decades to accommodate varying custom concentrate receipts, closure of the Horne mine, better working conditions, environmental programmes, new technology and increased energy and labour costs. This paper highlights the reasons for changing the smelter from two calcine charged and one wet charge reverberatory furnaces fired by coal to a smelter using. tonnage oxygen oil, natural gas and coal in a single wet charged reverberatory furnace and a Noranda Process continuous Reactor. The current operation 1 described, including three major topics; the use of oxygen/fuel burners on the charge banks of the reverberatory furnace which has increase the smelting rate from 680 to 1100 tonnes of concentrate per day; the oxygen enrichment of the Noranda Process converting air to achieve smelting rates of over 1800 tonnes of concentrate per day; the converting of the mixture of 73 percent copper matte produced from the Noranda Process and the 33 percent copper matte produced from the reverberatory furnace.

Jan 1, 1983

By Hai-Peng Guo, Lu Jiang, Xiao-Man Yan, Bing Xie, Hong-Yi Li

Traditional, calcium compounds cannot be used in vanadium extraction processing due to the limitation of sodium roasting technology, which results in unsatisfied dephosphorization for vanadium-containing hot metal in converter and thus increasing the dephosphorization burden for subsequent steelmaking. The calcium roasting technology is an alternative for vanadium extraction and allows adding lime into vanadium slag in converter. In the present study, vanadium was leached by soda from roasted vanadium slag with high calcium content. Effects of roasting temperature and time, leaching temperature, Na2CO3 concentration andliquid to solid ratio on vanadium leaching rate were studied. The results show that 94% of vanadium was extracted by roasting the vanadium slag at 950℃ for 2.5h and then leaching in 160g/L Na2CO3 liquid at 95℃ for 1h with liquid to solid ratio of 10:1 ml/g. Impurities of Si and P reacted with calcium and formed insoluble Ca2SiO4 and Ca3(PO4)2 respectively.

Jan 1, 2015

By Jagdish C. Agarwal

Although copper ranks very low in the order of abundance of elements in the crust of the earth, it has been one of the first metals utilized by mar, at his emergence from the Stone Age, about 10,000 years ago. Use of copper for weapons, tools, utensils and ornaments dates back to the twilight of history, 6,000-5,000 B.C. Native copper outcrops and the malleability of the metal explain its very early use by the cave-dwellers. The working, melting and extraction of copper from its minerals are among the oldest metallurgical achievements of the human race. The oldest complete smelting installations for the extraction of copper from its minerals, dated about the fourth millenium B.C., were recently discovered in the Timna Valley, Wadi Arabah, Israel. (1) The history of the developments of the extractive metallurgy of copper has been adequately reviewed recently. (2,3) The center of copper production migrated from the Eastern Mediterranean to Northern Europe (Mansfeld, Germany, Swansea, Wales) towards the end of the Middle Ages (1500 A.D.). The production of the metal was boosted tremendously in North America since the end of the nineteenth century (Fig. 1).

Jan 1, 1976

By Patrick R. Taylor

A kinetic study of the fluosilicic acid leaching of galena was performed under the presence of different oxidants. Fluosilicic acid concentration, agitation speed, concentration of solids and particle size, type and concentration of oxidant, and temperature were the variables studied. Hydrogen peroxide was found to be the most effective oxidant, its effectiveness being proportional to its concentration. As expected, an increase of leaching temperature increased the overall extraction and extraction rate. The same was found by decreasing the galena particle size. It is thought that leaching using hydrogen peroxide is controlled by fluid film mass transfer due to the calculated apparent activation energy. Reaction by-products such as sulfur and sulfur compounds retard the leaching rate. A mathematical model is proposed and compared to experimental results.

Jan 1, 2003

By SIMON TIMBILLAH

The chalcopyrite-molybdenite (Cu-Mo) flotation industry is increasingly turning to organic depressants as suitable replacements for inorganic reagents, such as NaHS, due to environmental and safety concerns as well as high consumption rates of the inorganic reagents. This presents an opportunity for improvements or design and synthesis of alternative reagents. Disodium carboxymethyl trithiocarbonate (Orfom® D8) depressant is an organic depressant with a carboxylate group on one end and a trithiocarbonate group at the other end. Fundamental results are shown regarding the interaction of the Orfom® D8 depressant in the bulk flotation of a Cu-Mo concentrate from an operating North American mine. Cyclic Voltammetry on pure copper and Fourier Transform Infrared Spectroscopy (FT-IR) and X-ray Photoelectron Spectroscopy (XPS) measurements on pure chalcopyrite with Orfom® D8 depressant treatment are also reported. Through such characterization techniques a potential adsorption mechanism of Orfom® D8 on the mineral surface was identified and its depressant characteristics in the Cu-Mo flotation systems explained.

By B. Wasmund, K. Adham, K. O'Keefe, C. Lee

"Metal chlorides (e.g. iron and nickel) can be pyrohydrolysed at elevated temperatures to yield an HCl rich off-gas and a metal oxide product. Typically, the high energy requirement for pyrohydrolysis is provided by the combustion of a hydrocarbon fuel with air. Here, it is demonstrated that the use of oxygen-enriched combustion can result in lower fuel requirements and higher HCl concentrations. In addition, the oxygen enrichment can result in a smaller volume of off-gas and thus, smaller and less expensive process equipment. This new concept can be applied to both the spray roaster (SR) and the fluidized bed reactor (FBR). Similar to the aircombustion case, the oxygen-enriched process can use a direct contact venturi scrubber, to recover energy from the roaster off gas, but at a higher efficiency. The new process also uses an absorption tower for capturing HCl from the roaster off-gas, but generates a stronger HCl solution than is possible with pyrohydrolysis in air.BackgroundIn recent years, the metallurgical industry has become increasingly involved with developing methods for extracting metals, upgrading products or cleaning metallic products by using hydrochloric acid. These applications of chloride metallurgy often result in metal chloride solutions, which should be processed to regenerate HCl for reuse, and to recover the metal value as a product or by-product oxide [2, 3, 4].The pyrohydrolysis of metal chloride solutions has been done in two types of air roasters: spray and fluidized bed. The existing roasters burn a hydrocarbon fuel in air, to provide the required energy for evaporating the feed solution and to provide an elevated temperature for the chloride pyrohydrolysis to occur, according to the following reactions:"

Jan 1, 2011

By R. J. Kuczynski

The U.S. Bureau of Mines operated a 2,000-9 (4.4-lb) batch process development unit for recovering platinum-group metals (PGM) from automobile catalysts. Virgin monolith, used pellet and used monolith catalyst samples were tested. Leaching twice with 1-pct sodium cyanide (NaCN) solution at 160' C for 1 h in a pressure vessel dissolved over 95 pct of the PGM from virgin catalysts and over 90 pct from used pellet catalysts. Over 85 pct of the PGM was dissolved from used monolith catalysts when a third leaching step was added. PGM concentrates as metallic powder containing over 99.8 pct of the dissolved PGM and analyzing greater than 70 pct PGM were recovered by heating the pregnant leach solutions from virgin catalysts to 250' C and used catalyst to 275" C for 1 h. The solution after heating contained primarily sodium carbonate from cyanide decomposition and less than 0.2 ppm total cyanide.

Jan 1, 1993

By A. Andreas Hejja

Flow of slag and settling of matte in slag resistance electric furnaces are discussed in conjunction with furnace geometries, stirring action of the electrodes, buoyancy and electromagnetic effects. The rectangular electric furnace was regarded as a channel reactor and the mode of slag flow as a channel flow. The flow is affected both by buoyancy and electromagnetic forces, however the effect of electromagnetic forces is minimal. The flow velocity is made up of two components; (i) that developed by the action of the electrodes, and (ii) the bulk flow velocity determined by the smelting rate and the volume of the reactor. Slag samples were taken from various depths of the molten bath and were analyzed microscopically to determine the size and distribution of matte particles, The action of the electrodes was described by a simple mathematical formula indicating a balanced settling rate in the area of electrode action.

Jan 1, 1996

By C. Pereira

Spent nuclear fuel (SNF) can be treated in a molten salt electro refiner for conversion into metal and mineral waste fonns for geologic disposal. The fuel is dissolved in molten chloride salt. Non-transuranic fission products in the molten salt are ion-exchanged into zeolite A, which is subsequently mixed with glass and consolidated. Zeolite was found to be effective in removing fission product cations from the molten salt. Breakthrough of cesium and the alkaline earths occurred more rapidly than was observed for the rare earths. The effluent composition as a function of time is presented, as well as results for the distribution of fission products along the length of the column. Effects of temperature and salt flow rate are also discussed.

Jan 1, 1996

By Shuqiang Guo, Dingsheng Tan, Weizhong Ding, Zunyu Hu

"The mixture of hydrochloric acid and magnesium chloride is a good lixiviant for leaching of laterite. The solution can enhance the leaching ability because of the proton activity deviated positively from ideal. Otherwise, the existence of magnesium chloride in the lixiviant affects the dissolution behavior of magnesia, which may be an advantage of the process with less hydrochloric acid consumption. An investigation of magnesia particle dissolved in strong hydrochloric acid solution has been conducted. Influences of concentration of the magnesium chloride and hydrochloric acid and temperature on magnesia dissolution were studied. The dissolution mechanism was also discussed in this paper.IntroductionThere has recently been much interest in the use of hydrochloric acid leaching processes for recovering metal from ores or secondary resources [l-41_ Compared with sulfuric acid, the use of hydrochloric acid as lixiviant offers significant advantages including faster leaching kinetics even at atmospheric conditions, higher leaching rate and greater solubility for most metal chlorides [5-61 .With the gradual decline of the nickel sulfide supply, the extraction of nickel from laterites has become increasingly attractive [7-s1. Nickel may be co=ercially recovered from laterites both by pyrometallurgical and hydrometallurgical processes. The drawbacks of pyrometallurgical processes include the requirement of high grade ores, substantial energy input and loss of cobalt bound within ores. The extraction of Ni from lower grade nickel laterites ores is suited by hydrometallurgical routes, which play an increasingly important role with depletion of higher grade deposits."

Jan 1, 2014

By Alan P. Prosser

The heap leaching of gold ores by cyanide solution was simulated by computer program. The program uses only basic m1neralogical and chemical data; no process testwork data, such as column leach results, are required. The simulation can be used to forecast the consequences of various changes before and during the testwork, design and operation stages of a particular ore-process system. Also, data about the state of different parts of the heap at various times help create an understanding of what is happening. The effects of mineralogical and process variables on the overall performance of the ?heap leaching process are illustrated. Comparisons are made to column leach tests and production data. The potential of the simulation strategy is discussed for making better use of operating experience and for suggesting specific research objectives. It has become clear that more attention should be paid to other metals that dissolve in the solution.

Jan 1, 1989

By J. K. Brimacombe, I. V. Samarasekera, B. G. Thomas

"Mathematical models have been developed for the processing of static cast steel ingots and are app1ied to investigate the mechanisms for the formation of panel cracks. Panel cracking is an intermittent but persistent defect that causes affected steel ingots to be scrapped. A two-dimensional, finite-element, heat-transfer model was formulated and employed to calculate the temperature distribution in both large and small steel ingots during the various processing stages from initial casting to the start of rolling, including solidification, cooling in the mold and in air, reheating in the soaking pit, and subsequent air cooling. The stress state in the ingot arising from the calculated temperature variations was then determined. This involved the development of a transient, elasto-visco-plastic, finite element, thermal stress model, including the effects of phase transformation volume changes and kinetics creep, and temperature-dependent, mechanical properties. The results of the mathematical model predictions of temperature and stress were then used to determine the mechanisms and to suggest solutions for two different types of panel crack formation. Mid-face panel cracks apparently form during air cooling when the mid-face surface temperature is between the Arl and 500~C. Off-corner panel cracks appear to initiate internally during the early stages of reheating but do not propagate to the surface until much later. IntroductionPanel crack formation in static-cast steel ingots is a defect that has been plaguing the steel industry for several decades. Although the problem is intermittent, it is also serious since affected ingots must be scrapped. Panel cracks are manifested as two distinct types of cracking problems. ""Mid-face"" panel cracks are found exclusively in small, 2 to 6 ton, medium carbon steel (0.3 to 0.7% C) ingots and usually exhibit a single, continuous, longitudinal crack down the center of one of the ingot faces as shown in Fig. l (l). ""Off-corner"" panel cracks often form roughly oval, discontinuous crack patterns on the wide faces of large, 20 to 30 ton ingots as seen in Fig. 2 (2). They affect only low carbon steels (0. l to 0.2% C) with high manganese content. Both defects affect only aluminum-treated steels and are caused by a combination of intermediate temperature ductility loss involving aluminum-nitride precipitation and thermal stress generation. The ductility problem has received a good deal of attention which was the subject of a recent review (3). The present study was undertaken to investigate the thermal stress aspects of the problem through the development of mathematical models of heat transfer and stress generation in static-cast steel ingots. The ultimate objective was to elucidate the mechanisms of formation for both types of panel crack and to evaluate possible solutions to the problem."

Jan 1, 1986

By S Ivanaj

Oxidation of chalcopyrite from a copper concentrate in an electrochemical cell having separate-anodic and cathodic compartments was studied by potentiodynamic, potentiostatic and galvanostatic experiments. Oxidation of chalcopyrite particles was mainly realized by in-situ electrogenerated FeIII and Cull ions. The use of an ion exchange membrane, in this experimental set, avoids the reduction of the ferric and cupric ions. The effects of particle size, current feeder potential, current intensity and pulp density were studied to optimize the oxidation parameters. Selective complete oxidation of chalcopyrite was achieved. Oxidation of pyrite was negligible. Mom than 85 % of sulfur was obtained in its elemental form. This may allow selective extraction- of copper from the chalcopyrite concentrate without sulfur dioxide emissions.

Jan 1, 1995

By Fathi Habashi

The recovery of uranium from wet process phosphoric acid was applied on industrial scale in the 1940's by using octylpyrophosphoric acid as an extractant. Later, more efficient reagents were used, e.g., di(2-ethylhexyl) phosphoric acid and actylphenyl phosphoric acid. In the 1970's the rare earths in Kola phosphate were recovered in Finland and recently (1997) in Norway using HNO, as a leaching agent and di(2-ethylhexyl) phosphoric acid as solvent. It was demonstrated later on laboratory scale that both uranium and rare earths could be extracted from the rock by tributyl phosphate but at different pH values provided that the rock is leached with nitric or hydrochloric acids instead of the commonly used sulfuric. This new concept opens the way to the possibility of treating phosphate rock by in-situ, dump, or vat leaching for the recovery of phosphate values as well as uranium and the rare earths. Another solvent extraction process is used industrially for the purification of phosphoric acid using butyl and amyl alcohols.

Jan 1, 1998