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By M. A. Gimenes

The utilization of chlorination in extractive metallurgy and advanced ceramics areas has been widely investigated as a preparative route in order to obtain intermetallic compounds, which are used as precursors in the development of new materials and process. The major processes of decomposition of rare-earth ores use sulfuric acid and sodium hydroxide at high temperatures, however there is not much work concerning chlorination. In this work, a systematic study of the reaction between xenotime (REPO4), chlorine and carbon has been performed. Particular emphasis was on kinetic studies to establish optimized conditions for the reaction. The kinetics of chlorination of xenotime raw material by rare-earth elements/compounds has been studied over a temperature range from 600°C to 950°C. The influence on the rate of conversion of xenotime to RECl3 on temperature, partial pressure of chlorine, carbon content, and particle size were investigated. A global rate equation that includes these parameters has been developed. The results show that the process follows the unreacted core-shrinking model with a formation of a porous product layer. The powder X ray-diffraction technique corroborated this model showing clearly the patterns related to the formation of yttrium oxychloride (YOCl), indicating that the reaction mechanism involves the presence ofan intermediate step before the formation of lanthanide chloride.

Jan 1, 2000

By Ángel Ruiz-Sánchez

Ethylene glycol additions to aqueous acid solutions for leaching copper sulfides increase both copper and iron extractions compared to a conventional sulfuric acid leach with hydrogen peroxide (H2O2). The role of ethylene glycol is to prevent peroxide destruction, which normally occurs in solutions that contain both cupric and ferric ions. However, despite this improvement, ethylene glycol and sulfuric acid concentrations must be high (3.5 M and 0.7 M, respectively) to obtain satisfactory conversion levels at room temperature. In the present investigation, EDTA was used as an additive to complex the cupric and ferrous ions, lowering the requirements of ethylene glycol and H2SO4 to 0.11 M and 0.007 M, respectively, while minimizing oxidant decomposition. The experimental results for a mainly chalcopyrite, copper concentrate showed complete copper extraction in 24 h at room temperature, with the stoichiometric quantity of EDTA for the copper and iron dissolved. Tests using seawater were equally as successful.

By W. R. McDonald

The U.S. Bureau of Mines investigated treatment of gold and silver refractory ores and concentrates that respond poorly to conventional cyanidation techniques due to the complex mineralogy of the ore. Three types of ores were investigated: gold locked placer sands, gold locked in sulfides, and gold that is robbed from the pregnant cyanide solutions by minerals in the ore. Ore treatment included grinding, flotation, cyanidation, air oxidation, pressure oxidation, hypochlorite oxidation, roasting, and carbon in leach.

Jan 1, 1991

By V. D. Tathavadkar

Chromite ore is of immense importance for the extraction of metallic chromium and chromium chemicals. The mineralogy and crystal structure of chromite phase are therefore important part of our investigation on the extraction chemistry of chromium species. In this investigation, we have studied the effect of the processing parameters, i.e., the temperature and the oxygen potential on the microstructure and composition of mineral phases formed in the Cr2O3 ?Al2O3 -FexOy -MgO system. In particular the importance of the spinodal decomposition reaction is emphasized in the extraction of chromium as sodium chromite and sodium chromate. Experiments were carried out in order to study the differences in the crystallography of different chromite minerals. Phase equilibria in natural chromite minerals were investigated by calcining chromite mineral in air, argon, and 5% hydrogen + argon atmospheres over a temperature range from 200 to 1200 °C. The effect of the oxygen partial pressure and temperature on the phase constituents of the calcined product has been discussed. The microstructural changes were examined using scanning electron microscope (SEM) and the changes in elemental composition in different phases were analysed by electron probe micro analyser (EPMA). The results obtained from EPMA studies were used to calculate lattice parameter of the spinel lattice, and these values were compared with the values obtained from X-Ray powder diffraction data. On the basis of the experimental data, the mechanism of the spinodal decomposition of complex spinel phases is described under the influence of oxygen partial pressure and temperature.

Jan 1, 2000

By C. Burton Clark

The important role of the petrographic microscope in the petrology of refractories is discussed, based on 45 years of industrial experience by the author. Highlights of his career are used to illustrate improvements in equipment and techniques during the period. Two specific investigations are described which emphasize the interrelated use of the petrographic microscope with other instruments such as the x-ray diffractometer and scanning electron microscope. Emphasis is placed on the use of phase equilibrium diagrams for guidance in predicting and interpreting reactions that occur under non-equilibrium conditions in the manufacture and use of refractories.

Jan 1, 1982

By Miao Tian

Large quantities of copper complex resources are produced globally and urgent to be cleanly processed. This article presents a thermodynamic analysis of mixed smelting process including low-grade polymetallic copper sulfide concentrates, high copper content sulfide concentrates, metallurgical by-products (copper removal slag from lead metallurgy), and copper powder from electronic waste. A top blown smelting reactor to simulate mixed smelting process is developed using a metallurgical process simulator, METSIM. Reactor parameters, heat loss and phase distributions are estimated from actual plant data. The proper proportion between complicated primary and secondary copper resources is determined by analyzing the influence of the feed rates of various resources, oxygen, silica flux and revert on the smelting performance. Autogenous smelting process is built by optimized matching materials of copper complex resources, in terms of the reactor temperature, copper content in matte and slag, and the percentage of magnetite in slag.

By Y. Z. Zhang

Electrochemical oxidation of arsenopyrite in ferric sulphate media in the absence and presence of bacteria T jerrooxidans has been investigated for the purpose of understanding the dissolution chemistry of arsenopyrite and the bacteria attack mechanism. Mixed potential, polarization resistance measurements, polarization curve, cyclic voltammetry experiments were conducted in a ferric sulphate medium of 10g/L FeH, temp.25-35°C, pH 1.5-2.5 in the absence and presence of bacteria Tjerrooxidans, respectively. For the anodic process, a two-step reaction sequence is suggested by the electrochemical measurements. The initial step at a low potential is described by:

Jan 1, 1996

By H. Soto, J. Jara, F. Nava

A method has been developed to recover cyanide and copper from solutions containing copper complexes and thiocyanate. Copper is precipitated as copper thiocyanate or as copper cyanide depending on pH and the concentrations of thiocyanate and cyanide in the effluent. The copper precipitate assays over 50% copper and presents good dewatering characteristics. After settling it can be separated from the effluent by filtration. The solution containing the bulk of the cyanide is then oxidized with ozone to transform the remaining thiocyanate into cyanide. This results in a regenerated solution rich in free cyanide that can be recycled to the cyanidation process. Careful control of the pH of the solution is required. First, pH of the effluent is lowered to optimize the precipitation and oxidation stages, then the pH is restored to an alkaline value to regenerate the cyanide solution. Recoveries of over 96% copper and cyanide were obtained in laboratory tests using industrial solutions. With this procedure, cyanocidic gold/copper ores could be treated economically by heap leaching, since the cyanide consumed by the copper impurities could be regenerated at very low cost (most of the cost of cyanide regeneration would be compensated by the copper credits). In order to achieve this, a bleed of the barren solution could be treated by the proposed method, and then recycled to the leaching step. The volume of solution to be treated should be large enough to keep a cyanide/copper molar ratio higher than 3:1. This would assure that copper does not cause undue interferences in the leaching or the carbon adsorption stages. If the thiocyanate content is low, the oxidation stage can be avoided, and the solution can be recycled to the leaching stage directly after the solid-liquid separation stage.

Jan 1, 1997

By Stephanie Trant

Montana Tech has been engaged in fundamental research on the processing of critical materials for more than a decade. Efforts include examining novel reagents for the flotation of Rare Earth Minerals (REMs). For this paper, research results on a collector, salicyl hydroxamic acid (SHA), are presented. Various REMs were examined and include the rare earth oxides (REOs), carbonates (RECs), and phosphates (REPs) of a suite of Rare Earth Elements (REEs). Differences are attributed to solution and surface chemistry, coordination number, and ionic diameter. SHA adsorption follows an ion-exchange process that leads to chemisorbed and surface-precipitated states, depending mostly on pH. Many effects are directly attributed to lanthanide contraction. Results should also be applicable to other REM/collector systems and further suggest that REM flotation should consider dual collectors.

By John W. Ahlrichs

Microscope, electron microprobe and x-ray diffraction have been used to provide quantitative evaluation of products from the mill, smelter, refinery and other metallurgical processes. Phase compositions and their quantities are necessary for an adequate understanding of the various products obtained throughout an operation and in laboratory testing. By careful evaluation, important information can be gained in improving recoveries and increasing grades at various stages of processing. Four case histories are discussed in this paper. Quantitative microscopic counting techniques are applied to mill products to determine degrees of locking and liberation of the economic minerals. Rapid, but accurate evaluation aids the metallurgist to develop or improve the grinding and flotation circuits. In the smelter, the identification and quantification of the phases are important for predicting reaction mechanisms and kinetic trends. Mineralogic techniques have been applied to conventional smelter products, and to those obtained in laboratory tests for newly developed innovations to smelting. Small, but important, values of gold occurrences in ore are difficult to determine. Evaluation of gold usually requires special separations into various mineral concentrates, followed by assays and mineralogic determinations of the products. Numerous occurrences of solid solution constituents can be treated as by-products, but often they are deleterious to metallurgical treatment. Most solid solution problems can be unraveled by the mineralogist's tools.

Jan 1, 1981

By S. R. Reddy

Thennodynamic properties of several quaternary systems are calculated using our recently modified Margules equations. The modified Margules equations are expressed up to infinite order in the vicinity of solvent. Quaternary system of one solvent and three,solute partials are derived. First order interaction coefficients of binary, ternary and cross -interaction parameters of quaternary system are used to'evaluate the partial functions. In the original fonn of Margules equations,derived partial functions are convergent and same 'as Unified ,Interaction Parameter Fonnalism. But considering up to infinite order of the Margules coefficients, the functions are divergent, in order to overcome this restriction, Margules equations are modified to get consistent equations. Derived partial functions are thennodynamica Hy consistent with Maxwell and Gibbs Duhem relations. The derived logarithmic activity coefficient of the solvent and solutes are consistent with the ternary systems. The calculated data, ie., activity coefficient values of nitrogen and interaction coefficients are in good agreement with the data of Fe-Cr-V -N. Fe-Ni-V -N, Fe-Cr-Ta-N and Fe-Ni-Ta-N systems.

Jan 1, 1999

By Jun Enriquez

Kennecott Utah Copper aims to extend anode furnace campaigns to more than three years. As part of that goal improvements are sought on anode-furnace tuyere-area refractory performance. Kennecott and Praxair developed high pressure nitrogen refining for the Oxidation Stage which shortened anode furnace fire refining cycles by up to two hours per cycle. Future developments include optimizing the Reduction Stage’s steam-gas reforming and achieving coherent jet tuyereless refining.

By Farouk T. Awadalla

The presence of humic species in spent Bayer liquor causes many processing problems in the production of aluminum hydroxide. Ozonation of spent Bayer liquor was found to be an effective process to destroy the colored humic species. The kinetics of the decolorization in spent Bayer liquor was found to be slower than in the alkaline humic acid solution containing no alumina. However, the reaction kinetics ware enhanced by heating the solution during ozonation above room temperature. Copper ions which are used as catalyst to enhance the ozonation reaction were found to be ineffective due to the presence of large quantities of aluminum hydroxide in the liquor. Ozonation was a more favorable process than membrane separation as it achieved about 92% separation of color and produced lower amounts of organic material. The treated spent Bayer liquor can be recycled to the upstream process without causing any difficulties and the purity of aluminum hydroxide product would also be improved. A comparison of preliminary cost data indicated that ozonation compares very favorably with membrane separation in this application. Key words: ozonation, Bayer liquor, aluminum hydroxide, humic species, copper ions, membrane separation, purity and economic.

Jan 1, 1994

By Keiji Toyabe

Several purifying techniques have been developed for controlling the impurity levels in the copper electrolyte at Niihama Copper Refinery. These have been carried out as follows; i ) the study of the reaction in liberation made it possible to raise the current efficiency for arsenic removal by more than 50% and to decrease generation of arsine sharply. By applying this method, a good performance was attained at commercial operation. li) the antimony in the electrolyte can be successfully removed by contacting it with activated carbon. This procedure is applicable particularly when there is a large amount of antimony in the copper anode. lli) for the nickel sulphate recovery from the electrolyte, an electric evaporating system was developed. The characteristics of this process are, capability of continuous operation with less manpower, the high recovery ratio of nickel sulphate (more than 85% as nickel) and no black acid formation in the treated solution.

Jan 1, 1987

By J. D. Budai, D. H. Lowndes, D. P. Norton, D. K. Christen, B. C. Chakoumakos, J. R. Thompson, B. C. Sales

"Artificially-layered structures, consisting of (Sr,Ba,Ca)CuO2 layers in the tetragonal, ""infinite layer"" crystal structure, have been grown by pulsed-laser deposition. Superlattice chemical modulation is observed for structures with SrCuO2 and (Sr,Ca)CuO2 layers as thin as a single unit cell (~3.4 Å). In addition, novel thin film superconductors were formed by using the constraint of epitaxy to stabilize SrCuO2/BaCuO2 superlattices in the infinite layer structure. Using this approach, two new structural families, Ba2Srn-1CUn+l O2n+2+ d) and Ba4Srn-1CUn+3O2n+6+ d, have been synthesized which superconduct at temperatures as high as 70 K. These results represent not only the synthesis of new structural families of superconductors, but also demonstrate that pulsed-laser deposition and epitaxial stabilization can be effectively used to engineer artificially-layered thin-film materials.Advances in the understanding of epitaxial thin-film growth of the cuprates have heightened interest in creating artificially layered superconductors.(1-3) The layered structure of the copper oxide superconductors opens the possibility of forming novel materials by carefully controlling the epitaxial growth of sub-units of the crystal structures. Thin-film growth methods offer unique opportunities for the atomic engineering of new high-temperature superconducting (HTSc) materials through the ability to form artificially layered crystal structures.(4,S) Moreover, the surfaces of single-crystal substrates provide an ""atomic template"" that can be used to stabilize epitaxial films in metastable crystal structures.An important development in forming new HTSc compounds by artificially-layered epitaxy has been the epitaxial growth of (Sr,Ca)CuO2 films in the so-called infinite layer structure.(6-17) This material, which can be considered the parent compound of all of the copper oxide superconductors, has a relatively simple, layered structure consisting of CUO2 planes separated by planes of alkaline earth elements.(18) Bulk synthesis of (Sr,Ca)CuO2 with the tetragonal, infinite layer structure generally requires the use of high pressure and high temperature bulk processing techniques.(19-24) However, recent experiments show that this metastable compound can be epitaxially stabilized at less than atmospheric pressure, resulting in the growth of tetragonal (Sr,Ca)CuO2 single crystal thin films of the infinite layer defect perovskite structure by pulsed-laser deposition (PLD) over a wide range of growth conditions.(6-17)"

Jan 1, 1994

By Takao Yasugi

The majority of copper in the raw material migrates to the de-copperized dross that forms when the crude lead produced in the blast furnace is treated in the de-copperizing process. The de-copperized dross is treated in the electric furnace producing matte, speiss, and crude lead. The de-copperized dross also contains the silver. Therefore, it is important to improve the rate of silver migration to the crude lead. For this reason, the behavior of silver between the matte, speiss and crude lead phases was examined. At the same time, several tests to improve the percentage of silver migrating to crude lead were conducted.

Jan 1, 2003

By J. Daniel Bryant

Deformation processing of rapidly solidified powder alloys presents a technical challenge different in several ways from the processing of ingot based alloys. The metastable phases formed during planar flow casting of aluminum alloy 8009 (FVS0812) must be safe-guarded from high temperature excursions during processing to avoid decomposition; this restriction prohibits liquid phase sintering of particles during consolidation. The development of strong particle-particle adhesion, therefore, relies on the imposition of very large strains during forming operations to insure sufficient mechanical meshing of the aluminum particles and break-up of prior particle oxide boundaries. These strains are generally much greater than those required for metallurgical transformations in ingot based alloys. In an attempt to quantify the deformation required to improve interparticle bonding, the finite element method (FEM) was employed. Preliminary results which predict the metal flow and strain distribution in several workpiece configurations are discussed. These predictions are then correlated to measurements made on experimental subscale forgings. Lastly, experimentally measured quantities which reflect the degree of interparticle bondingg are related back to FEM model predictions.

Jan 1, 1992

By Fabiola Alvarez, Ana E. Bote, Daniel Pasquevich

"The oxidation of aluminum and its alloys was extensively studied for improving the corrosion resistance in structural materials having high specific strengths. But this reaction involves the formation of a very thin barrier layer on the metallic pieces. Furthermore, the ·recent development of the directed melt oxidation process for producing metal-ceramic; composites has renewed the interest in the study of interaction between gases and metals. Oxidation experiments in the presence of different chlorine partial pressures and at different temperatures were performed in ·a thermogravimetric balance, and microstructures were analyzed by electronic microscopy and X-ray diffraction. The oxy-chlorination kinetics was determined and the oxide formed W(IS amorphous at temperatures below 600 °C and crystalline .at higher temperatures. The appropriate experimental conditions for the fastest completed oxidation was further determined.IntroductionThe use of fine powders for the manufacture of ceramic components has significant advantages. They include excellent sinterability; low sintering temperature and better microstructure leading to improved mechanical properties. The conventional method of producing fine oxide powders involves controlled precipitation and pirolysis of suitable salts. The main limitation of the high temperature decomposition route is the evolution of environmentally unacceptable and corrosive gases. Controlled precipitation of hydroxides from solutions of salts, followed by thermal treatment involves large volumes of solutions and the calcination step that can induce grain growth (1).Direct oxidation of aluminum metal for producing alumina powder requires high temperatures for the direct oxidation of molten Al alloys by a vapor phase oxidant process (2, 3) or high technological process like thermal plasma reactor ( 4).Oxidation of high purity aluminum (5, 6) below the melting temperature· is initially characterized by a nearly linear reaction rate, followed by a rate which decreases rapidly with further weight gain. However, the oxidation rate of an aluminummagnesium alloy is much faster and it does not conform to any common oxidation law, but it is nearly parabolic at temperatures between 200 and 400 °C, an nearly linear· above 400 °C."

Jan 1, 2000

By Takahiko Okura

Most non-ferrous raw materials are associated with sulphur. To extract the metals, the sulphur is recovered typically as Sulphuric acid or liquid S02. On the other hand, natural gas may contain over 20% of hydrogen sulphide (H2S) and a huge quantity of elemental sulphur is produced through oil and gas refining processes in the world. A large fraction of the sulphur mined from natural sources is eventually returned to the earth as fertilizers, by-products of desulphurisation and neutralisation processes, or as fugitives to the atmosphere. However, the supply and demand for sulphur are in imbalance. Such situation urges to develop a new smelting process without sulphuric acid production. This paper briefly reviews the global sulphur balance and the technologies for recovering elemental sulphur. The core of this paper is a proposal to convert S02 gas to elemental sulphur by using organic materials. Some results of thermodynamic calculations and experiments are presented.

Jan 1, 2003

By R. E. Moore

The lining systems currently in use in BOF furnaces, certain steel ladles, and the slag line of electric are furnaces were developed during the late seventies through the mid-eighties using a trial and error method of combining aggregate, carbon sources, additives and binders. They are currently based on magnesia, graphite, metal additives and resin binders, the selections of each being tied to the anticipated intensity of the use conditions. The general functions of the respective constituents are well appreciated, however, there is still a great deal that is not known about how the socalled antioxidants protect the graphite nor how impurities from the graphite and the aggregate enter into the wear processes. In a simplified assessment of wear processes, it appears that if the deoxidized layer can be kept very thin, less than 810 mm in depth, and if the viscosity and quantity of the matrix glassy phases can be controlled to resist erosion of the deoxidized layer, lining life can be maximized for the various applications. This paper will discuss the characteristics of the starting materials systems currently being employed for applications requiring a deoxidation function to realize extended wear. It will not attempt to explain all the complex interrelationships between the respective constituents but will point to the potential for improvements through the use of improved constituents.

Jan 1, 1991