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By Mark Tsirlin

Kinetics of the initial oxidation stages of diffusive silicide coatings on 8 molybdenum and niobium at 1100 - 1700 and under the pressure of 400 and 1330 Pa has been studied using methods of gravimetry and gas phase analysis of oxygen, as well as by SEK, XRD and EDMA methods. The first oxidation stage described by asymptotic equation in case of NbSi coating changed over to the stage described by parabolic equation. The asymptotic law was shown to depend on non - stationary conditions on the oxide layer boundaries. Interconnection between silicides and quartz structures, on the one hand, and peculiarities of oxidation kinetics, on the other, is [discussed. The possibility of estimation oxygen atom jump frequency in quartz and fractions of oxygen reacting with metal and with silicon proceeding from the analysis of the kinetic data was ascertained. Conditions of oxidation kine- tics transfer from asymptotic (or parabolic) stage to a non - protective "linear" stage, associated with volatile ~roduct formation, are also discussed.

Jan 1, 1995

By G. L. Hundley, D. N. Nilsen

The U.S. Department of Energy investigated the use of liquid-emulsion membranes (LEM) for the selective removal and recovery of metals such as copper and zinc from mine waste waters. This investigation included field tests of a mobile, pilot plant-scale, continuous-flow LEM system. The system was tested at copper mines with solutions containing from 100 to 1,400 ppm Cu, and at a zinc mine with a solution containing 115 ppm Zn. Typical results from the copper tests were >90% copper recovery, and zinc extraction from waste water also was typically>90%. Although all of these waste waters contained high impurity levels, pure products were produced. On several of these field tests, integrated systems were tested that resulted in recovery of metal by-products, selectiv~ precipitation of iron, and polishing to reach discharge targets for essentially all of the contained metals. In addition, some results are included from laboratory-scale tests.

Jan 1, 2000

By R. S. Celmer

The distributions of cobalt, molybdenum, copper, and selenium between nickel matte and silica-saturated iron silicate slag have been determined in the region of the metallic saturation boundary, at 1523 K. Results are given as a function of the composition of the coexisting Fe-Ni alloy and the activity of iron in the system. Under strongly reducing conditions, these minor elements display a marked preferential accumulation in the sulphide phase. It is shown that the dissolution of cobalt and molybdenum in slag follows an oxidative mechanism, and distribution equilibria are correlated with the oxygen potential. From these data, the thermodynamic properties of cobalt in nickel matte are computed. Further, comparisons of minor element partitions are made between the nickel and copper matte smelting cases under metal saturation conditions.

Jan 1, 1988

By C. E. Abbey

Cobalt, iron and manganese play various roles in copper electrowinning using lead–calcium–tin alloyed anodes. Cobalt catalyzes electrochemical water decomposition resulting in lower anode potential and reduced corrosion rates. Iron reduces cathodic current efficiency, but is used to reduce higher oxidation states of manganese that oxidize organics in solvent extraction. Manganese also produces anode scale and is generally considered a problematic impurity. The effect of the combined interaction of these three metal ions on the anode potential has not been quantified yet. The current work used a three factor, two level, three replicate central composite design of experiments to analyze the effects and potential interactions among cobalt, iron and manganese. The experiments consisted of chronopotentiometric analysis to assess anode potential after 24 h of operation. Higher [Co], lower [Mn] and either high or low [Fe] yielded lower anode potentials. Two regression models were developed to predict anode potential as a function of [Co], [Fe] and [Mn]. A method to estimate electrical energy consumption for copper electrowinning is also presented.

By J. E. Clemson

The Black Pine sediment-hosted, disseminated gold deposit is located in Cassia County, Idaho. Gold mineralization occurs in flat-lying zones 50 to 100 feet thick. Total geological ore reserves are 5.6 million tons grading 0.049 oz/t. Ore types include: non-carbonaceous, oxidized ore; carbonaceous, sulfide ore; and carbonaceous, partly oxidized ore. In the oxidized ores, native gold grains commonly occur in porous hematite pseudomorphs that have replaced disseminated framboidal and euhedral pyrite, and this gold should be readily leached by cyanide solutions. Approximately 4 % of the native gold observed in the oxidized ores is locked within gangue and may be refractory to cyanide solutions. Native gold has not been observed in the unoxidized samples, all of which are characterized by primary sulfides. It is suspected that the bulk of the gold mineralization in the sulfide ore occurs as submicroscopic particles within pyrite and will be refractory to cyanidation. It is believed that much or all of the gold observed in the oxidized samples was originally in pyrite but was released and re-precipitated during oxidation. The degree of oxidation of the pyrite and the presence/absence of preg-robbing carbonaceous material is used as a guide in delimiting zones of mineralization amenable to heap leaching.

Jan 1, 1988

By Eoghan T. M Doyle

Oxide mixtures of nickel (NiO), cobalt (COO) and chromium (Cr203) were prepared with graphite in stoichiometric amounts and the powder mixtures were compacted to produce cylindrical pellets. The composition of chromium oxide in these mixtures were varied. Pressed pellets were reduced in a flowing stream of argon-4% hydrogen gas (500 ml/min). Both slow and rapid heating methods were adopted to raise the temperature of a pellet during reduction of oxides to form superalloy powder. The reduction temperature was varied between. 1523 and 1623K. The effect of heating rate and niobium oxide addition on the microstructure of the superalloy produced was studied by using ordinary light and scanning electron microscopes. New phases formed as a result of reduction were identified by X-ray powder diffraction technique. The mechanism of reduction of oxides together with the microstructure of NiCrCo alloy are discussed. The thermodynamics of formation of ternary alloy phase is elucidated on the basis of binary phase equilibria and Gibbs free energy of mixing data for the constituent alloy compositions.

Jan 1, 1992

By R. M. Cunningham

Asarco operates one of the largest individual copper electrolytic refineries in the world at Amarillo, Texas. The feed for this refinery is a mixture of anodes produced at Asarco smelters and copper purchased t?om a number of primary and secondary sources. The variation in feed makes it imperative that the refinery practices state-of-the-art quality control to minimize the effects'of unwanted impurities in the electrolytic refining process. In late 1993, a plant designed to sigru6cantly reduce the antimony and bismuth levels in the electrolyte was commissioned. The purification plant uses ion exchange technology in conjunction with a novel strippiing system developed by Zeneca Specialties (U.K.). The strippiing system permits the recycling of the eluant and thus avoids the extremely high costs of stripping with conventional reagents. In addition, the environmental impact of treating the eluant for recovery of antimony and bismuth is minimized. This paper outlines the development of the technology and, in particular, describes the operational practices and improvements at Amarillo since the commissioning of the plant.

Jan 1, 1997

By Guillermo A. Vidal

With the introduction of monitoring technologies, process computers and Web services on Industrial Facilities the need for electrolytic processes automation has been set. Recently designed facilities have substantially improved plant layouts, automated cathode processing and copper harvesting. Despite these advancements only limited progress has been accomplished on the electric current distribution of the process. Lately a number of proposals focused on preventing short circuits and balancing cathode currents have emerged. Among these are the AZSA intercell, the Outokumpu double contact, and the Optibar InterCell Plus. Although these intercell bars are clearly superior to the conventional bar, little or conflicting data is available about their merits relative to each other. Consequently, selection of the best intercell bar for most applications is accompanied by uncertainty, which can lead to less than optimum results. A critical evaluation of the performance of the aforementioned bars on the basis of the application is provided, thereby giving the framework and guidelines for the selection of the best bar for each application.

Jan 1, 2003

By Karin Soldenhoff

Recovery of uranium in conventional ion exchange circuits, using strong base or weak base resins containing quaternary or tertiary amine functional groups, is based on an anion exchange mechanism. In saline liquors, chloride competes with uranium for the active resin sites and reduces resin loading. This results in significant negative impacts on the IX process in terms of plant throughput and operating costs. In this paper we present the results of a study on the recovery of uranium from an acidic in situ leach liquor containing approximately 9 g/L chloride. A range of resins was tested, and a high capacity strong base resin was identified with significantly enhanced loading compared to conventional resins. Other process-relevant criteria such as loading kinetics and elution efficacy are also discussed. The process developed was successfully tested during a recent ion exchange pilot plant operated in conjunction with a field-leach trial.

By Gerson de Araújo Filho

This paper shows the use of tires as fuel to be employed into blast furnaces. The tires can substitute coal or even charcoal in the blast furnaces tuyeres. The injection into tuyeres, besides the contribution for energy generation, can also produce gas for iron oxide reduction. The tires, as powder to be injected into blast furnaces, contributes for an environmental use of this waste, which helps to obtain a high value product as well. So, the advantage of using such material is that it is waste and has lower cost for preparation. The obtained results showed that the tires have good combustibility. This one was obtained in a model that simulates the same conditions occurring in the blast furnaces tuyeres; these used raw materiais include tires and mixtures of tires with coal or even with charcoal.

Jan 1, 2006

By R J. Singh, E. Z. Chacko, Devilal, S. K. Jha, Rina Sahu, Sheshank Shekhar

"Breakouts are one of the biggest problems encountered during continuous casting of steel billets. Billets get cracked locally or break completely in two parts during solidification causing the liquid part of the partially solidified billet to empty inside the cooling chamber. Proper control of important parameters is necessary to avoid break outs during continuous casting. In the present work, the nature of the break outs at a billet caster at Tata Steel was studied. Data analysis was also done for certain casting parameters and the Sulphur tracer test was conducted to understand solidification in the mould. It was found that to reduce the occurrence of break outs, it was necessary to tune the operations based on the grade being cast and the design of the mould tube being used.IntroductionA break out during the continuous casting process is a rupture of the partially solidified shell inside the secondary cooling chamber, causing the contained liquid steel to spill out. In the mid 1970s while continuous casting technology was still in early stage of development, causes of breakouts was not well understood. Today, with technological development much has been understood about breakouts but, most of the understanding has been in the slab casting process wherein due to the higher level of instrumentation, a lot of information has been gained. In billet casting however, due to the geometry of the mould housing with the tube mould, multiplied by the complexity of the multiple strands, instrumentation has not been used and obtaining data for analysis has been difficult.Breakouts at billet casters are still the main hindrances to production. A break out results in a loss in production since the strand which has had a break out is now not available to produce and thus a six strand caster would be reduced to a five strand caster, increasing the time for casting the same tonnage. Additionally extra set up time is required as more often than not a mould change is required in order to have the strand casting again."

Jan 1, 2014

By John O. Marsden

The past fifteen years have seen a number of important developments in copper hydrometallurgy, including the commercial application of biological heap leaching of secondary (chalcocite-dominant) copper ores, the commercial demonstration of chalcopyrite concentrate leaching technology using pressure leaching and biological processes, and the application of novel configurations of solution extraction circuits. Significant emphasis is now being placed on the development of effective stockpile leaching practices for primary ores (chalcopyrite and bornite-dominant mineralization). Some of these developments have been highly successful, and will pave the way for further development and commercialization. Others have been less successful. These developments are reviewed in the context of the metal price cycle and trends for the future are identified.

Jan 1, 2006

By Cristián Araya L.

A dynamic agglomeration, heap leaching, solvent extraction and electrowinning software, called NICO, has been developed in order to either design or simulate copper ore recovery plants. NICO contains a library of routines, each representing a unit operation or piece of equipment, which are assembled like a meccano to match almost any wet plant configuration. Routines include agglomeration or curing either in drums or belts, belt conveyors, heap stacking and reclaiming, heap leaching of oxide, sulfide or mixed copper ores, heap irrigation, drainage, ponds, mixer-settlers, filters, columns, coalescers, tanks, electrowinning cells, pumps, and all connections and related piping. All models are semi- phenomenological, i.e., they include all physical-chemical, mass, thermal, transport equations, which are required to represent as closely as possible the equipment or unit operation. However, operating experience has been incorporated into the model in order to make it simpler, faster and reliable. This experience has been tested in several plants in Chile since 1992. Site meteorological data is simulated also; in this way the model is responsive to weather conditions (temperature, solar radiation, ambient humidity, atmospheric pressure, wind velocity, etc). NICO has been used recently for design and optimization studies in copper plants in Chile like Radomiro Tomic, Collahuasi and Zaldivar. A user-friendly interface allows fast and comprehensive simulations. The entire plant is shown in a single graphic screen, so the user can see all the relevant information, and soft-keys are provided in order to change parameters on-line and watch their effect in final copper production in cathodes. Model also calculates and reports operating parameters, as well as estimated investments and operating costs.

Jan 1, 1999

By G. T. Lapidus, O. J. Solis-Marcial

"The oxidative dissolution of copper from refractory minerals, such as chalcopynte, represents a technological challenge that has occupied hydrometallurgists for more than half a century. Innumerable processes have been suggested, but the majority operates at high temperatures or employs corrosive media. The origin of this refractory nature is the formation of passivating phases of iron(III) or copper. One option is to add non-corrosive ligands that complex these metal ions, thereby facilitating their dissolution. In the present work, the effect of acetone in sulfuric acid solutions was studied. The initial experiments were on chalcopynte carbon paste electrodes using cyclic voltammetry, where greater reactivity was observed. Later, leaching tests with hydrogen peroxide, cupric sulfate and ozone and, as oxidants, were performed. High extractions were achieved in three hours at 50°C. The solid residues contained the iron in the form of Fe203 and FeOOH.IntroductionChalcopyrite is the most important mineral of polysulfide copper ores [1] and accounts for approximately 70% of the world's copper reserves [2]. Currently, the copper present in chalcopyrite is extracted mainly by pyrometallurgical processes, which generate environmental concerns because of the formation of SO2 gas and submicron particulates [3]. The development of a less aggressive hydrometallurgical process for the extraction of copper would constitute a possible solution to these problems. For that reason, studies of the dissolution behavior of chalcopyrite are of great technological importance [4], However, the proposed oxidative leaching routes for chalcopyrite, generally at high pressures and temperatures, have not been implemented on an industrial scale, because of the elevated costs required to equal the high copper extractions obtained in thermal processes. These extreme leaching conditions are required because of the refractory nature of chalcopyrite. Passivation has been used to explain this phenomenon, although researchers have disagreed on the composition of the layer, which is various have assumed to be sulfur, copper sulfides, and iron-bearing jarosites or hydroxides [5]. If the latter compounds are the cause, an alternative solution would be the use of polar organic solvents in the oxidative leach to decrease the formation of the passivating iron layer. In this work, the influence of acetone on the oxidative leaching of a chalcopyrite concentrate at room conditions is explored."

Jan 1, 2012

By N. Bazzanella

The hydrogen desorption kinetics of pure and Nb-doped magnesium hydride film samples was investigated by using a Sievert-type apparatus. The overall activation energy and the reaction order controlling desorption are (141±5) kJ mol-1H and n 4 for Mg hydride and (51±5) kJ mol-1H and n 1 for Nb-doped (5% at) Mg hydride indicating that, in the doped sample, hydrogen desorption is controlled by the H migration in transformed h-Mg layers. Structural analysis performed by X-Ray Diffraction (XRD) and Extended X-Ray Absorption Fine Structure spectroscopy (EXAFS) show that the catalytic effect of the Nb dopant is connected with the formation of NbH0.89 nanoclusters dispersed in the Mg hydride matrix. It is suggested that the catalysis process is also connected to the presence of Mg-Nb hydride interfaces where the transfer of H atoms preferentially occurs by connecting h-Mg grains and by the role of the MgH2-NbH0.89 interface as preferential site for the dissociation of the hydride phase.

Jan 1, 2006

By Ana E. Bohé, Georgina De Micco, Gastón G. Fouga

"In this work the reaction between several manganese oxides and chlorine is investigated in the range of temperatures between 650 and 950ºC. The reaction path for the chlorination of MnO is established, which involves recrystallization of high valence manganese oxides (Mn3O4 and Mn2O3) followed by its chlorination. For this reason, to understand the reaction of MnO, the chlorination of Mn3O4 and Mn2O3 has also been studied. The starting temperature for the reaction of these oxides is determined by non isothermal thermogravimetric measurements. The effect of temperature is analyzed, under our experimental conditions the rate of reaction is mass transfer controlled. The activation energy for the volatilization of manganese chloride is obtained which is in good agreement with volatilization enthalpy of MnCl2.IntroductionMany oxide ores which have manganese in their composition undergo chlorination processes during the extraction of refractory metals such as Ti, Hf and Nb. Although several works related with chlorination of manganese oxides were reported, there is no information about the kinetics or mechanism of the manganese oxide chlorination reactions. Okahara et al. studied the chlorination of manganese oxides and established that they react easily above 250ºC. Furthermore, they observed that chlorination of high order oxides is more difficult when there is not a reducing agent [1]. Ivashentsev studied the chlorination of manganese oxides using Cl2(g), CO(g) + Cl2(g) and COCl2(g). He established that the reaction of MnO started at 130ºC with formation of MnCl2(s), he also observed recrystallization of manganese sexquioxide [2]. Finally, the chlorination of manganese nodules from the ocean was studied by Murthy and Reddy [3] with the aim of obtaining valuable metals such as Mn, Co, Ni and Cu. They studied the influence of several parameters like temperature, carbon percentage, particle size and chlorine flow rate in the extraction process."

Jan 1, 2008

By Petr Sulovsky, Jaroslava Ledererova, Miroslav Svoboda, Michaela Suchardova

"The thinning resources of natural raw materials necessitate an increased degree of waste material recycling. The building industry offers a range of technologies enabling incorporation of industrial wastes into building materials for construction purposes in an economically acceptable way. Our research is focused on finding the appropriate technologies for specific groups of industrial waste materials (IWM). The studied IWM involve coal combustion residues (CCR), desulphurization products, sludges, metallurgical slags, and various other wastes. Many of them contain increased amounts of toxic elements that can under certain conditions get released. In order to prevent this, each specific IWM requires finding the technology that best ensures the binding of toxic elements in the building matter are fixed for the long term.Introduction The sustainable development of mankind is more than ever viewed as a matter of resources. Many aspects of the switch from a throw-away to a recycling society concern one of the largest consumers of natural resources and producer of greenhouse gases, the building industry. One of the biggest tasks lying before the researchers in the field of building materials is to find substitute or alternative raw materials that would save the thinning reserves of natural resources. The most promising and natural way is to replace the traditional raw materials with rejected and unwanted products of industrial processes, classified as wastes. These of course are not produced with the primary intention of achieving some desired properties. The usage of industrial wastes therefore involves finding the optimal way of usage their existing positive (from the point of view of utilizations) properties and minimizing the impact of their undesired properties, i.e. from the perspective of the considered application."

Jan 1, 2008

By Luciano B. Oliveira, Angela O. Costa, Sergio N. Monteiro, Luis Guilherme C. Marques

"Biofuels are gaining a relevant role in today’s world not only as a solution for the decreasing petroleum reserves but mainly as a positive contribution to the efforts in global warming mitigation. In Brazil, since 1975, the replacement of gasoline by ethanol started a so-called PROALCHOOOL program, which is now being complemented with the replacement of petroleum diesel by biodiesel. This biodiesel program was officially created in 2005 with mandatory goals, supported by legislation, of 2% addition in 2008 and 5% addition in 2013 into all commercialized regular diesel. In this work, a critical analysis of the Brazilian biodiesel program is presented. The technical aspects related to the different raw materials, including wastes, available for biodiesel conversion as well as the economical conditions associated with production costs and market logistic are discussed. The environmental benefits associated with the retention of greenhouse gases are also discussed.IntroductionToday the commonly accepted fact that the petroleum world reserves are probably passing through a maximum and start declining in terms of the total amount that can be extracted by existing technologies is motivating significant changes in our society. The continuous increase in the price of gasoline and other liquid fuels is an immediate worrisome and visible consequence. However, more than an economical problem, our civilization is already facing the effects of global warming, due to CO2 emission from burning fossil fuels, mainly from coal and petroleum. It is now realized that a large scale solution for these problems demands the prompt substitution of non-renewable fossil fuels by others that, in addition of being renewable, have a relatively lower contribution to the greenhouse gases."

Jan 1, 2008

By Shun Myung Shin, Dong Hyo Yang

Cobalt is recovered from square type of spent lithium ion batteries (LIBs) containing 5~20 % Co, 5~7 % Li, 5~10 % Ni, 15% organic chemicals, and 7% plastics together with Cu, Al, Fe, and Mn. The waste LIB was prepared by physical treatment. After screening, the crushed LIBs were separated to +8 mesh, -8/+16 mesh, and -16 mesh powder. Among these, -16 mesh powder was selected for leaching. The leaching test was investigated at 2 M H2SO4, 6 vol.% H2O2, reaction temperature 60 ?, agitation speed 300 rpm, solid/liquid ratio 50 g/ 500 ml, reaction time 1 h. The leaching efficiency of cobalt was more than 99 % and its concentration was 24.9 g/L. For removing of impurities such as copper, iron, and aluminum in the leaching solution before cobalt solvent extraction, the impurities were eliminated by pH control with alkali solution. For selective extraction of cobalt, the aqueous phase removed impurities was equilibrated with different volumes of 0.4 M Cyanex 272 saponified of 50 %. Extraction efficiency of cobalt was about 80 % at first step. Separation coefficient (ßCo/Li) of cobalt and lithium extractions was 206.5. Over 9.0 % of pure cobalt sulfate solution was obtained after stripping with H2SO4 solution.

Jan 1, 2008

By Ian M. Ritchie

Cementation or metal displacement reactions such as Cu2+ + Fe Cu + Fe2+ are among the oldest known hydrometallurgical reactions. They are still used in the recovery of some metals and in the purification of process liquors and waste water streams. However, they are often more complex than the stoichiometric reaction would suggest because they involve the simultaneous deposition of one metal onto a second which is dissolving. For example, sometimes a cementation will not take place, even though it is thermodynamically favoured. On other occasions, a cementation reaction will start but come to a halt as the depositing metal blankets the reacting surface. On yet other occasions, side reactions, catalyzed by the deposit, can be important. In this paper, the electrochemical basis of cementation reactions is described. The conditions for each of the complications encountered in these reactions are described and illustrated by examples drawn from a number of hydrometallurgical processes. The cementation reaction between activated carbon and gold thiosulfate is also briefly described, this reaction being unusual in that no dissolution of the carbon occurs.

Jan 1, 2003