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By Ana E. Bohé

Chlorination process is an attractive and efficient method for the metal recovery from complex materials. The process that is performed at high temperatures, allows converting all the metals contained in the material into their respective chlorides which are further separated in a selective way. Aluminum metal matrix composites with discontinuous ceramic reinforcement of short fibers, whiskers, and particles have been gaining wide acceptance as an important engineering material in automotive, aerospace, and electronic industries. Since the ceramic reinforcements are still quite expensive and contribute significantly to the final cost of composite materials, the feasibility of their recovery from the manufacturing scrap and further recycling is a factor of increasing economic interest. In the present work, a theoretical and experimental study is given for the recovery of Al2O3 and SiC particles and short fibers from three commercially available aluminum-matrix composites produced by molten metal mixing route. The process consists of transforming the constituents of metallic alloy matrices in gaseous chlorides that are dragged by the gaseous stream, while the ceramic reinforcement remains as a solid residue in the reaction bed.

Jan 1, 2006

By A. G. Raraz

Reactive metal electrorefining presents a number of problems that pose obstacles to commercial operation. Cerium has been chosen as the surrogate for certain reactive metals because of its thermodynamic and electrochemical characteristics. A comparative review of the properties for cerium and plutonium has been presented to justify the choice of cerium as the surrogate metal for studying electrorefining. This review has addressed the electrochemical, thermodynamic, and kinetic parameters of molten salt electrorefining of cerium metal to provide an insight to this extremely important process. The cell components and configuration, current efficiency of the process, purity of the cathodically deposited metal and the power requirement of the system are evaluated for a molten CaCl2-MgCl2 salt electrolyte using a molten, stirred impure anode. Crucible designs, salt electrolyte, cell temperature and electrode materials are also evaluated. Selection of the salt electrolyte and the cell temperature have been suggested from this study.

Jan 1, 1992

By A. F. Otero

During the electrowinning (EW) of copper significant quantities of highly toxic vapors (acid mist) are produced due to the liberation of oxygen at the cathodes. Acid mist affects the health of operators, the environment and plant infrastructure. Acid mist can be decreased to acceptable levels by a combination of physical means (e.g. ventilation, plastic spheres over electrolyte) and chemical surfactants that decrease the surface tension of the electrolyte, modifying the way oxygen bubbles burst at the surface of the electrolyte. However, only few chemical surfactants are compatible with electrolytic applications, and they are not always used due to their high costs. This paper describes the application of a novel surfactant of natural origin (commercial name Mistop®) to suppress acid mist in copper EW process. Mistop® contains triterpenic saponins derived from the Chilean quillaja tree Quillaja saponaria Molina. The product is non-toxic, and poses no risks to the environment or to EW operators. Mistop® was tested at a laboratory, pilot plant and industrial scale in the world?s largest copper EW production plant at Radomiro Tomic (RT), CODELCO, Chile. At a Mistop® dosage of 8-9 ppm, acid mist decreased below the value accepted by Chilean regulations (< 0.5 mg/m3). At this dosage, Mistop® represents and economical alternative to chemical surfactants, and it is currently industrially used at RT.

Jan 1, 2003

By Daniel Kittelty

A fully instrumented laboratory electrowinning cell has been used to produce nickel cathodes from synthetic solutions containing various impurities in order to evaluate the effects of both metallic ions and organic reagents (from prior solvent extraction and other processes) on the quality of the electrodeposited nickel. The conditions used were typical of those employed in industrial electrowinning operations. The impurities were found to alter the crystal size and shape, induce the development of hydrogen pits on the deposit surface, incorporate as metal hydroxide crystals in the deposit, and alter the internal stress and current efficiency. These effects have been interpreted in terms of previously established relationships between the solution composition and the physical properties of the cathodes. The incorporation of the common metal impurity ions into the deposit have been interpreted in terms of a mass transport controlled reduction or precipitation reactions. In particular, a low concentration of aluminium ions resulted in an initial highly deleterious effect, which was replaced by a positive influence at higher concentrations. A model which involves the buffering effect of the aluminium on the pH at the cathode surface has been proposed.

Jan 1, 2003

By Florian Kongoli

The liquidus surface of multicomponent slags is an important parameter in various smelting and converting processes. It helps not only to optimize the slag, chemistry of current processes and their fluxing strategies, but also to determine the availability of new slags for more advanced technologies. In a series of our previous publications, the liquidus surface of some multicomponent iron oxide slags has been quantified at several constant oxygen potentials and the effect of the latter, ignored until that moment, was quantified along with the effect of some minor components. In this work, the liquidus surface of some iron oxide slags is quantified at constant CO2/CO ratios. This is a new convenient way for the quantitative description of the slag liquidus surface and the effect of several fluxes, especially in those processes such as slag solidification, where oxygen potential changes continuously. This type of diagram also describes more dynamically the effect of oxygen potential, clarifies the relation between CO2/CO ratio and oxygen potential in terms of the liquidus surface, which is not widely understood by metallurgist today, and reduces the gap between laboratory work and industrial experience.

Jan 1, 2002

By Florian Kongoli

Minor components and flux additions can modify the liquidus temperatures of multicomponent slags. In industrial practice, slags with various levels of minor components require various flux additions in order to achieve the lowest possible liquidus temperature The prediction and the optimization of these combinations can decrease the cost of the overall process. In this work the effect of several minor components and flux additions such as Al2O3, MgO, and CaO, on the liquidus temperatures of multicomponent iron-silicate slags has been analyzed in terms of a thermodynamic model Various simple isothermal and non-isothermal diagrams are presented. These diagrams can be used directly by the process operators to define the optimum conditions under which the fluxes can be used to achieve the desired slag liquidus temperatures.

Jan 1, 1999

By Masatsugu Morimitsu

"The novel smart anode, MSA ™, for electrowinning of non-ferrous metals such as copper, zinc, nickel, and cobalt has been developed by thermal decomposition. The smart anode consists of a titanium substrate coated with a catalytic oxide layer which comprises amorphous or less crystalline oxide coatings. The catalytic layer contains an iridium oxide-based mixture or a ruthenium oxide-based mixture. The smart anode provides a remarkable reduction in cell voltage compared to other anodes, e.g., commercially available coated titanium electrodes and lead alloy electrodes. The test data has demonstrated that a maximum voltage reduction by ca. 30% is possible compared to lead alloy anodes. The smart anode also gives some additional merits in suppressing unwanted deposits on the anode; i.e., deposition of MnOOH, Pb02, or CoOOH. The electrowinning with the smart anode is possible to be an environmentally friendly process with less energy consumption and less anode deposits.IntroductionA coated titanium electrode iridium oxide-based or ruthenium oxide-based catalytic layers is well known as an insoluble anode for oxygen or chlorine evolution in industrial electrolysis such as chloro-alkali electrolysis, electrogalvanizing or electrotinning of a steel, a thin film production by electrodeposition such as copper foil production (CFP), water electrolysis, and electrowinning of nonferrous metals. The anode is commercially produced by thermal decomposition of a precursor solution painted on a titanium substrate, and the decomposition is usually performed at 450 °C or more. The obtained catalytic oxide coating formed on the substrate contains crystalline oxide as an active component to oxygen or chlorine evolution. The author of this paper had met a problem of such a crystalline oxide coating in the application of copper foil production; the anode was unable to use for a long period because of a large amount of lead oxide (Pb02) deposited on the anode, and the cell voltage was seen to continuously increase and drastically rise by the accumulated Pb02. In this case, the voltage reduction by replacing a lead alloy anode with the dimensionally stable anode was initially observed, but was gradually lost and disappeared. Therefore, the author of this paper aimed and investigated to suppress the unwanted side reaction on the anode, and finally invented a new class of coating based on an amorphous iridium oxide mixture in 2003 [!]. The invented coating was obtained at a low temperature thermal decomposition, e.g., 360 °C, and the coating consisted of amorphous iridium oxide and amorphous tantalum oxide. This invention achieved that oxygen evolution potential shifted more negative so that the cell voltage was reduced, and no Pb02 was deposited in the electrolyte of CFP [2,3]."

Jan 1, 2012

By Issa S. AI-Kharusy

Oxidation/reduction (REDOX) alloy media, as used in wastewater treatment, is founded on the exchange of electrons. Because of this electron exchange, many contaminants are converted to harmless components which require no further treatment. Other types of contaminants are removed from the waste stream by electrochemically bonding to the alloy medium. This paper discusses the REDOX reactions, the role of the alloy medium in various treatment processes, and describes specific applications of REDOX alloy media for the removal and minimization of waste. The characteristics and handling of spent treatment media is also reviewed as a further consideration in waste minimization.

Jan 1, 1996

By D. Neuschiltz, M. Witthaut, R. Cremer

"Metastable (Ti,Al)N coatings with fee structure have been shown to exhibit superior performance as compared to TiN under conditions of wear at elevated temperatures due to their better oxidation resistance and hardness. The oxidation resistance of these coatings increases significantly with increasing Al-content. However, the deposition of (Ti,Al)N films with Ti/ Al ratios below about 30/70 leads to a hexagonal structure which is not suitable for tribological coatings. Only little is known about the location of the cubic to hexagonal phase transition and hence about the optimum composition of (Ti,Al)N hard coatings.To determine the position of this transition, Tii-xAlxN films with different Ti/Al ratios were deposited on high speed steel at substrate temperatures between 100 and 700 °C by means of reactive MSIP. The composition of the films was determined by electron probe microanalysis (EPMA) and X-ray photoelectron spectroscopy (XPS), the crystallographic structure by thin film X-ray diffraction (XRD).It could be shown that in case of deposition temperatures of 300-700 °C a two-phase region exists in the metastable TiN-AlN phase diagram, which expands with increasing temperature, wheras at 100 °C substrate temperature no two-phase region was observed. But in opposition to the phase diagram known from literature, which is based on thermodynamic estimations, the detected two-phase region is narrow for typical PVD temperatures, thus allowing the deposition of cubic single-phase Al-rich (Ti,Al)N hardcoatings for tribological applications. Based on these results, a new Ti1-xAlxN film with x = 0.62 has been developed, which showed an increase of oxidation resistance by a factor of 4."

Jan 1, 1998

By John E. Dutrizac, Tzong T. Chen

"Laboratory experiments were undertaken to ascertain the behaviour of various ""impurity"" species during the precipitation of hematite directly from ferric sulphate solutions at 225°C and in the presence of 40 or 50 g/L of hematite seed. Copper, nickel and zinc are not significantly incorporated in hematite precipitates. Although the nickel contents increase to 0.22% as the Ni concentration increases to 60 g/L, the solid solution Ni contents are low relative to the bulk Ni contents. Thus, part of the Ni may be present as tiny particles of poorly soluble NiS04.H20. Increasing germanium concentrations to 2,000 mg/L result in products containing up to 0.59% Ge. The Ge occurs either in solid solution in the hematite or is adsorbed on the nanometer-size hematite crystallites. Increasing As(V) concentrations to 10 g/L increase the AsO4 contents of the products up to 16%. However, the products consist of hematite together with As04-containing Fe(SO4)(OH) and an unknown Fe-AsO4 species. All the hematite products contain - 1% SO4 which appears to be adsorbed on the nanometer-size hematite crystallites.IntroductionDissolved iron is a common impurity in most hydrometallurgical processing circuits and, generally, the iron must be eliminated prior to the subsequent recovery of the sought after metals. Simple neutralization of iron-rich solutions yields slurries which are difficult to thicken and filter. To address these concerns, the jarosite, goethite and hematite processes have been developed, and these technologies are able to reject the dissolved iron in a readily filterable form [1]. Despite its higher cost, the hematite process offers several potential advantages. Because hematite is an iron-rich, high-density compound, its formation would reduce the mass of residue and the size of a residue storage pond. Hematite is the thermodynamically stable form of iron under ambient conditions, and this stability would facilitate the impoundment of hematite precipitates. Furthermore, hematite has some market potential for cement manufacture and even for iron making [2]. In all the commercial hematite processes, the dissolved ferric ions are first reduced to the ferrous state. Subsequently, the pH of the solution is adjusted and the solution is then oxidized. The ferric ions gradually generated during solution oxidation hydrolyze and precipitate mostly as hematite, although commercial hematite products also contain trace or minor amounts of jarosite-type compounds. However, there are potential advantages in precipitating hematite directly from ferric ion solutions, as the reduction and subsequent oxidation of the iron are not required. Although the precipitation of hematite directly from relatively concentrated ferric sulphate solutions (up to 0.5 M Fe(SO4)is) was recently demonstrated [3], the behaviour of impurity species during hematite precipitation is largely unknown. To address this issue, systematic laboratory experiments were undertaken to ascertain the behaviour of a number of ""impurity"" species during the precipitation of hematite directly from ferric sulphate solutions at 225°C, and the results are presented in this paper."

Jan 1, 2012

Iron(II), sulphur dioxide and sugars such as lactose are potential reducing agents for manganese dioxide to produce manganese(II) for subsequent hydrometallurgical treatment. The leaching of limonitic laterite and manganiferrous ores with sulphur dioxide produces iron(II) which in turn can catalyse the leaching of manganese dioxide in acid media. This paper presents a critical analysis of the kinetics of reductive dissolution of synthetic manganese dioxide and manganese ore to compare and contrast the effect of sulphur dioxide and iron(II) in acid media containing sulphate or perchlorate anions. Both one-electron and two-electron mechanisms are considered in the case of sulphur dioxide. The current knowledge on chemical speciation is used to construct an Eh-pH diagram to show the effect of complexation of Mn(II), Fe(II) and Fe(III) with sulphate. Heterogeneous and electrochemical reaction kinetic models are combined to propose reaction mechanisms which rationalize the dissolution kinetics.

Jan 1, 2003

By M. Olper, M. Maccagni, C. J. N. Buisman, C. E. Schultz

The key point of the CX-EWS process is the conversion of lead compounds, contained in the active mass of spent batteries, into lead sulphide. The obtained lead sulphide is leached with ferric fluoborate electrolyte to dissolve lead and oxidize the sulphur from sulphide to the elemental form. The lead-rich solution is fed into a diaphragm electrolytic cell depositing lead and regenerating ferric fluoborate. The introduction of sulphate reducing bacteria technology in the sulphidization step of the battery paste improves dramatically the economics of the CXEWS process, reducing the costs of chemicals, avoiding gypsum disposal and minimising the unit operations of the process. This paper describes in detail this technology change with reference to the economics of the process.

Jan 1, 2000

By M. E. Reed

Clyde Materials Handling (CMH) and WorleyParsons have developed a concept for a flash furnace feed system using the specialist pneumatic conveying equipment expertise of CMH and the flash furnace process experience of WorleyParsons. CMH has developed a proprietary volumetric feeder (called a Rotofeed) which is extremely accurate and overcomes many of the problems inherent with loss-in-weight screw feeders and drag chain conveyors, previously regarded as state-of-the-art. Initial indications are that the Clyde-WorleyParsons Feed System could deliver the following benefits to Flash Furnace operation: ? Accurate pulse-less delivery of feed material to the head of the burner leading to improved combustion performance and process stability; ? Highly accurate split to the individual quadrants of a conventional burner tube, or provision of a smooth hollow curtain to a burner without guide vanes; ? Decreased pressure pulsation in the furnace due to improved combustion control and performance; ? Decreased temperature fluctuations in the furnace due to improved combustion characteristics and hence reductions in refractory thermal stress and wear; Plant measurements have indicated a correlation between the discharge of concentrate from the drag chain conveyor and high speed pressure fluctuations in the flash furnace settler. Pilot scale test have been conducted to illustrate that the system delivers pulse-less feed to the burner with even feed distribution axially.

Jan 1, 2006

By Kongfang Feng, Fei Ruan, Zhiyu Liu, Jieyu Zhang, Xin Hong, Shaobo Zheng, Jixu Wang, Jinyin Xie

"Mixing phenomena in smelting reduction furnaces with asymmetric side blowing were studied in this paper. Mixing phenomena in a smelting reduction furnace was represented as the mixing time by electrical conductivity measurements. Experiments were performed in a water model under various operating conditions to determine the effects of horizontal angle, radial angle, inserting depth, flow rate of the upper and the lower side nozzle, the included angle between the upper side nozzle, and the lower side nozzle on mixing phenomena in smelting reduction furnace. Comparing mixing time and mixing phenomena, the optimal conditions were obtained for an asymmetric side blowing process.IntroductionIn recent years, many countries have put forward development strategies for saving resources and environment-friendly, the development of various industries had to face its influence for resources and the environment .As we all know, the steel industry is a pillar industry of the global economy, in which ironmaking is an important part of it. In the modern ironmaking process, the blast furnace is regarded as the most important equipment and tool. But with the increasing scarcity of metallurgical coke resources and considering the environmental impact of such processes, metallurgists proposed the concept of smelting reduction. Smelting reduction processes to produce hot metal from iron ore and coal were being developed as a possible alternative to the traditional blast furnace. At present, a number of smelting reduction processes had been developed all over the world, they were mainly included COREX, HISMELT, FINEX, DIOS, etc."

Jan 1, 2012

By Hector M. Henao

The FeOX-CaO-SiO2 base slag at intermediate oxygen partial pressures is very often used in non-ferrous smelting processes. This slag would also contain Al2O3 and MgO because these compounds are normal components in the ore and the refractory of a furnace. The objective of the present work is to determine the effect of Al2O3 or MgO addition on the liquidus temperatures of the plain FeOX-CaO-SiO2 slags in the atmosphere between intermediate pO2 of 10-6 and that of iron saturation at 1250 and 1300 °C. The experiments were carried out at given mass%CaO/(mass%CaO+mass%SiO2) ratios ranging from 0 to 1 and at spinel-tridimite double saturation. The experimental results show that the effect of Al2O3 or MgO addition on the plain FeOX-SiO2-CaO slag is not uniform and depends on the content of Al2O3 or MgO, the oxygen partial pressure and the mass% CaO/mass% SiO2 ratio. It is apparent that Al2O3 or MgO addition enlarges the spinel or wustite saturation area at almost all the oxygen partial pressures and temperatures of this research. The obtained phase diagrams will be useful in the metallurgical industry to assist in the selection of slag chemistry, operation condition and development of new processes.

Jan 1, 2006

By Keiji Okumura, Jiayi Shan, Jian Yang, Masamichi Sano

"A new method of deoxidation and desulfurization of molten iron with magnesium vapor has been developed. An immersion tube, which was filled with pellets of the mixture of magnesia and carbon powders, was put into the molten iron. Magnesium vapor produced by carbothermic reduction of magnesia inside the tube was injected directly into the molten iron with argon carrier gas. The effects of temperature and carrier gas flow rate on deoxidation and desulfurization were investigated. A mathematical model of the reactions was developed. The rates of deoxidation and desulfurization were controlled by mass transfers of magnesium vapor in the gas-phase and oxygen and sulfur in the liquid-phase. This method may offer high efficiency for magnesium deoxidation and desulfurization of molten iron.IntroductionMagnesium is a strong refining agent in steel-making processes1 • At steelmaking temperatures, magnesium has a very low solubility in liquid iron, and a very high vapour pressure2 • Deoxidation and desulfurization with magnesium take place essentially through the interaction of magnesium vapor with oxygen and sulfur dissolved in molten iron, and magnesium can change chemical composition of nonmetallic inclusions3 • However, addition of magnesium to the steel bath is dangerous and does not give high efficiency in the refining process4 • Furthermore, as a refining agent, the price of magnesium is higher than aluminium and CaO fluxes. In the present study, a new method of the deoxidation and desulfurization of molten iron was developed using magnesium vapour in-situ produced by carbothermic reduction of magnesium oxide. Pellets made of mixture of magnesia and carbon powders were charged into an immersion tube, which was made of alumina or graphite. The magnesium vapor was injected directly into the melt. The effects of pellet mass, experimental temperature and carrier gas flow rate were studied on the refining rate. A mathematical model of the refining reaction was proposed on the basis of the experimental results."

Jan 1, 2000

By Adam C. Powell

A new Cahn-Hilliard phase field model of transport-limited electrochemistry describes phase boundary motion due to oxidation and reduction reactions at metal-electrolyte interfaces. Benchmarks demonstrating the accuracy of the method include open circuit voltage and closed circuit current in metallothermic reduction, and linear stability theory in metal electrolysis, including a new stability criterion for reduction of liquid metal from liquid electrolyte. The model is applied here to understanding cathode interface stability in titanium electrolysis e.g. in the SOM process developed with Uday Pal, and to structure evolution in subhalide reduction of titanium dichloride by magnesium developed by Toru Okabe. Potential for application to new fuel cell and battery systems is also discussed.

Jan 1, 2006

By A. V. Tarasov

Emission of sulfur-containing gases causes most adverse impact on the natural environment in the process of nonferrous metals production. Under the conditions of Arctic regions, in particular in the region of the Norilsk Mining and Metallurgical Complex (Russia), this problem requires a special approach taking into account potential economic and socioeconomic consequences. By reducing the iron sulfide content of flotation concentrates by using new flotation reagents inhibiting pyrrhotite flotation and by applying advanced process flowsheets for flotation it is possible to increase the nonferrous metals content of flotation concentrates by 5% or more along with a corresponding reduction in SO2 formation during their subsequent pyrometallurgical processing. The ways used to resolve the environmental problems in the Norilsk region in the process of nickel and copper production, are based on the improvement of methods for elemental sulfur recovery from metallurgical off-gas by non-conventional techniques, the sulfur recovery from metallurgical gases by production of liquid sulfur dioxide and the technology for pyrometallurgical treatment of sulfide concentrates without SO2 formation. Another opportunity is the development and commercial introduction of hydrometallurgical technologies for treating copper-nickel sulfide ores.

Jan 1, 2006

By Jason Eric Sallee

Ongoing operations at the Cyprus Miami Smelter involve the use of an electric furnace for settling of copper matte from discard slag. Proper operation of the electric settling furnace is a major factor in minimizing losses of copper to the discard slag. Recent test work at the smelter has shown improvement in the operation of the electric furnace with a subsequent improvement with regard to the copper losses. This paper presents a general discussion of the Cyprus Miami Smelter operation, past results with respect to copper losses, recent operational changes and test work, and the subsequent results.

Jan 1, 1999

By Larry G. Stolarczyk

The development of geosteering technology for geothermal reservoirs is challenged by the integration of electrically small antennas in small-diameter metallic drill rods. To be useful, the antenna pattern must achieve sufficient back-lobe suppression, preferably with a forward-looking pattern. Forward-looking capability requires an antenna array with phase control. The phase-controlled antenna pattern enables imaging of geologic structures ahead of and surrounding the well bore. This paper describes the development of electric and magnetic dipole arrays for small-diameter drilling pipe.

Jan 1, 2006