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By N. Kanari

Reactivity of MgO towards C12+air, C12+N2 and C12+CO gas mixtures was studied up to 1000 °C. Carbochlorination of MgO occurs at temperatures lower than that of its oxychlorination. Effects of gas flow rate, temperature and partial pressure of the carbochlorinating gas mixture on the reaction rate were investigated. The apparent activation energy of MgO carbochlorination is 49 kJ1 mol between 425°C and 600°C. At 550 °C, the apparent reaction orders with respect to C12+CO, C12 and CO, are 2.37, 1.47 and 0.89, respectively. At this temperature, the maximum reaction rate was obtained using a C12+CO gas mixture having a Cl2lCO molar ratio equal to about 0.6.

Jan 1, 1998

By Jerome P. Downey

In the thermal treatment of electric arc furnace (EAF) dusts, zinc is reduced, volatilized, and ultimately recovered either as liquid metal in a splash condenser or as solid zinc oxide in bag filters. During the process, the duet's chlorine and fluorine content also enters the gas phase and condenses as dross in the splash condenser or as salts which contaminate the zinc oxide product. Pretreatment of EAF dust by pyrohydrolysis appeared to offer a means of minimizing the duet's halogen content. The primary research objectives were to experimentally verify the technical viability of pyrohydrolysis and delineate the process parameters requisite for efficient halogen removal. To this end, representative EAF duet samples were secured and characterized by x-ray diffraction, scanning electron microscopy, and Mössbauer analyses. Specific- experimentation focused on the response of halogen extraction to variations in temperature, retention time, water vapor partial pressure, and various additives. The experimental results proved that 97 to 99 percent chlorine extraction and 80 to 85 percent fluorine extraction are consistently achieved when EAF dusts are blended with silica and roasted at temperatures of 850°C or greater in a furnace atmosphere of 75% steam (diluted by air). A statistical analysis further established that more than- a single optimal point exists, thus affording flexibility in parameter selection (e.g., by increasing temperature, the necessary retention time and additive concentrations are decreased). The findings substantiate the feasibility of pyrohydrolysis roasting in reducing the chlorine and fluorine in the EAF dust to a level that will obviate industrial concerns about halogen contamination. The end-product of the pyrohydrolysis procedure is a de-halogenated, self-fluxing calcine which can be directly charged to a plasma or flame reactor. The paper includes design parameters and flow diagrams illustrating the pyrohydrolysis process integrated with the plasma and flame reactor technologies.

Jan 1, 1992

By I. Gaballah

About forty percent of the SOx emissions are generated during the processing of metal sulfides of Cu, Pb, Zn, Ni, etc. Although new technologies for metal sulfide's smelting allow the production of H2S04 with a reasonable cost and decrease the emissions of sulfur oxides, the generated quantity of SOx is considered as a serious threat to environment. This paper suggests alternatives for low temperature processing of complex sulfide ores or concentrates 'CSO or CSC' under neutral, reducing and chlorinating atmospheres or their combination. At T > 400 "C, The neutral and reducing treatments allow the decomposition of pyrite and the partial recovery of sulfur as So and H2S. At 300 "C, the chlorinating treatment of CSC is fast, exothermic and allows the separation of FeC13 from the valuable elements' chlorides. It also generates SyCIx that can be either reduced by H2 or hydrolyzed in presence of sodium sulfide. The recovery rate of elemental sulfur with respect to the sulfur input exceeds 90 %.

Jan 1, 1999

By E. vanHuyssteen

A method of establishing the relationship between the mineralogy of a sinter and its subsequent processing behaviour in a lead blast furnace is demonstrated. It involves: 1) analyzing the Zn-spinels, hardystonite, larsenite, Pb-silicates, Pb-arsenates, Pb-(Ca)-sulphates and other femtes with an electron microprobe; 2) determining the extent of elemental substitutions in various mineral structures; 3) establishing a sequence in which the various phases formed during sintering. In this manner the relationship between the bulk chemistry of a sinter formulation and the speciation of elements into various phases in the sinter can be established. Specifically, the-substitution of Mg for Zn in hardystonite significantly influences sinter production. Mg substitution releases Zn into the surrounding matrix. This Zn reacts with the Pb-silicate to form larsenite thereby reducing the amount of Pb-silicate available for anhydrite digestion. Excessive amounts of residual anhydrite thus result if the sinter formulation is based solely on the CaO/Si& ratio.

Jan 1, 1993

By Eltefat Ahmadi

Iron-free titanium oxycarbonitride (TiOxCyNz) is a promising feedstock for production of titanium tetrachloride (TiCl4) at low temperatures. In this study, the effects of leaching variables such as temperature, time, particle size of staring material and concentration of the leaching solutions were evaluated on iron removal from nitrided Malaysian ilmenite by Becher process. The nitrided ilmenite was prepared by isothermal reduction with graphite at 1200 °C for 3 h in H2-N2 atmosphere. The aerated leaching experiments were conducted at 50–90 °C with addition of 0.3–2.0 wt% of NH4Cl catalyst. The highest extent of iron removal (XFe) was obtained at about 96.2% for the sample leached at 90 °C for 7 h with 2.0 wt% NH4Cl. The iron concentrate and titanium oxycarbonitride product were characterized by ICP-OES, XRD, XRF and SEM-EDX analyses. The results indicated that the aeration leaching process was a successful route to prepare low-iron titanium oxycarbonitride.

By lchiro Aoi, Hideo Nakae, Makoto Yoshida, Makoto Ishino

"The influence 6f gravity on the microstructure of unidirectionally solidified Cu-Pb monotectic, Ag-Si and Fe-C eutectic alloys is studied. In order to examine the influence of gravity in a lg environment, both the upward (opposite to direction of gravity) and downward (direction of gravity) unidirectional solidifications are carried out. The results are as follows: (1) For the upward solidified Ag-Si eutectic alloy, the eutectic Si continuously grows. On the other hand, in the downward solidified Ag-Si alloy, the Si grows discontinuously and disperses into the ex-Ag matrix. (2) No morphological difference in the eutectic growth is observed between the upward and downward solidified Fe-C eutectic alloys. (3) In the case of the upward solidified Cu-Pb monotectic alloy, a banded structure, which consists of Pb-rich layers and Cu-rich layers, is observed. However, such a banded structure -is not observed in the downward specimen. (4) The banded structure is not found in the upward solidified Cu-Pb-0.05 mass % Al and Cu-Pb-0.1 mass % Al alloys. In the Cu-Pb-0.05 mass% Al alloy, a fibrous -L 2 phase grows continuously parallel to the growth direction at low growth rate. Only 500 mass ppm addition of aluminum induces the morphological change of the monotectic L2 phase.IntroductionThe influence of gravity on the solidification of eutectic and monotectic alloys has been investigated in microgravity environments [l-9]. The purpose of these studies was to obtain a homogeneous microstructure of eutectic or monotectic alloys, most of which alloys tend to solidify with macro-segregation under gravity. However, in most of the previous experiments, e.g., in free fall systems, in aircraft or in space laboratories, the growth rate was too high to realize a planar solid/liquid interface. This would be due to the limited time for solidification. Thus, it was difficult to examine the influence of gravity on the planar coupled growth of the eutectic or monotectic alloy. In this study, both the downward U.D.S. (unidirectional solidification by gravity) and upward U.D.S. (opposite direction to gravity) are carried out in order to examine the influence of gravity on the coupled growth in a lg environment [l0, 11]. In the case of the downward U.D.S. using the current Bridgman method, the molten alloy must be confined between the crucible and the solid."

Jan 1, 2000

By Onuralp Yucel, Ahmet Turan, Murat Alkan, Hasan Ozer

SHS (Self-propagating High-temperature Synthesis) is one of the important methods to synthesize B4C powders. The process contains the reaction of boron oxide powders (B2O3) with magnesium reducing agent and carbon black carburizer. SHS products are leached in HCl media to purify synthesized B4C powders in the following step. In the present study, effects of various functional additives (KClO3, KHSO4, MgSO4.7H2O, NaCl, MgO and Na2SO4) in the SHS stage were carried out. Various proportions of the additives were mixed with the initial SHS charge mixtures. Two different molar ratios were employed in the initial SHS mixtures as 1:3:0.8 B2O3:Mg:C and 1:2.5:0.8 B2O3:Mg:C. After the SHS step, HCl leaching process was applied to the SHS products. Filter cakes were dried and characterized by using X-Ray Diffraction Spectroscopy, BET and chemical analysis techniques.

Jan 1, 2015

By Boyd Davis, Vladimiros Papangelakis, Joshua LaMarre, Jan de Bakker

"HCl leaching using molten salt hydrates has the potential to improve the extraction of nickel from laterite ores. However, as in other HCl leaching applications, recovery of HCl is key to process economics. Spray pyrohydrolysis, which is used in current chloride-based flowsheets, is associated with a high energy cost. The authors have developed a proposed laterite leach circuit using an alternative HCl recovery route. The leach circuit envisions a leach by concentrated (33%) HCl in an MgCl2 molten salt hydrate (MSH) or brine medium, followed by Ni/Co recovery and iron precipitation. Magnesium and chloride are precipitated from solution as magnesium hydroxychloride; this hydroxychloride is thermally decomposed to produce HCl gas. The proposed flowsheet employs a chloride leach circuit with simpler equipment and lower energy cost than in the conventional practice of pyrohydrolysis. Laboratory work investigated key aspects of the flowsheet, including precipitation of magnesium hydroxychlorides and their composition; magnesium hydroxychloride thermal decomposition; and iron control.Introduction As sulphide nickel ores become harder to mine and more complex to process, laterite ores will increase in importance. Laterite ore deposits can be divided into two main mineralogies. Limonite ores consist mostly of hydrated iron oxide, FeOOH, with 1-3% nickel substituting for the iron. Saprolite ores consist of iron-magnesium silicates, (Fe, Mg)2Si04, again with some nickel substituting for the metal ions. Limonite ores can be treated using the HP AL (High Pressure Acid Leach) process, in which the ore is reacted with sulphuric acid at high temperature in an autoclave. HP AL, however, cannot in general be used to treat saprolite ores because the magnesium enters solution and consumes sulphuric acid, which results in excessive spending on lixiviant. It is therefore desirable to find a hydrometallurgical process specifically for saprolite ores that can provide better results than the treatment options currently available."

Jan 1, 2011

By A. Mukhopadhyay

Gas stirring, simultaneous arcing, chemical additions are some basic steps in the secondary steel making. From tap to team however, there are enough uncertainties and several in-situ decision making required to match the fmal composition and temperature in the given amount of processing time. Currently available control algorithms rely on overall material and heat balance coupled with a self-learning regression based tuning of model constants. In this paper we demonstrate the capabilities of Computational Fluid Dynamics (CFD) in modeling and analyzing the thermo-chemical aspects of secondary Steelmaking. These models take advantage of scientific and engineering advances in computational tools and provide almost real time speed of analysis. This can be a very effective tool for operator training, process debugging and improvement as well as new innovations. Keywords: Argon purging, Secondary steelmaking, Arcing, Ladle Furnace, Process Control.

Jan 1, 2003

By V. Jiricny

There is a growing need to process galvanized steel scrap from automobiles, etc., in order to remove the zinc coating that otherwise causes problems in remelting of the scrap in electric arc furnaces. One approach that has moved to the pilot plant stage is that of Metal Recovery Technologies, Inc., of East Chicago (MRI). That company leaches the zinc fiom the scrap with a sodium hydroxide solution. The leached and washed scrap can then be returned to the steel industry. What is left is a sodium hydroxidelzincate solution which must be processed to recover the zinc and the NaOH. Presently, this is done by MRI using electrodeposition on planar electrodes at moderate current density and the resulting zinc is in the form of fine powder which is hard to process into, say, zinc for galvanizing. MRI has supported an investigation of a novel electrode, the spouted bed electrode (SBE), for zinc electrodeposition. In laboratory cells, zinc particles with low porosity have been grown up to 3mm in size. Microanalysis of the deposited zinc showed low level of impurities. DC energy consumption values were usually in the range of 2-2.5 kWg which is well below the energy consumption of the existing cells (and of present-day cells for electrowinning from acid sulfate electrolytes). These results were achieved at current densities (few thousand A/m2) that are much higher than possible with conventional electrodes. Discussion is provided of the scale-up of the cell to a commercial scale.

Jan 1, 1998

By Toshio Suzuki, Machiko Ode, Won Tae Kim, Seong Gyoon Kim

"The Ostwald ripening and growth and coarsening of the secondary dendrite arm are studied using a phase-field model. The phase-field parameters are obtained at a thin interface limit proposed by Kim et al. In Ostwald ripening analysis, the difference of the concentration due ·to· the curvature effect is shown. The third power of the average particle radius Rav is proportional to time and the ripening constant shows a good agreement with the value by Deppers et al. The particle radii distribution shows the transition behavior to attain a self-similar stationary shape. The growth and coarsening behavior of the secondary dendrite arm is also analyzed using a phase-field model. The estimated arm spacing and its dependence on time are in good agreements with experimental data.IntroductionThe ripening or coarsening process controls the microstructure during the late stage of solidification. The ripening phenomena are recognized firstly by the Ostwald [1]. The first quantitative analysis for the Ostwald ripening in the limit of vanishing solid fraction was provided by Lifshitz, Slyozov and Wagner (LSW) [2,3]. In their study, that the mean radius grows proportional to the cubic root of time and the size distribution of precipitations shows a ""self-similar"" shape are shown. Most of the studies for the Ostwald ripening confirm or predict these two general rules above. In case of finite solid fraction, the general rules are observed but the ripening constant is larger and the self-similar shape is wider than the LSW prediction respectively [4-6]. To analyze· the high solid fraction system, the theories that consider the solute field correlation are proposed [4,7-8]. In the theory, however, since the particle is treated as the point, the effect of the concentration field deviation from the monopole field should be taken into account. Recently the numerical simulation, in which not only diffusive transportation of solute but also convection effect is considered, has been done using a phase-field model [9]."

Jan 1, 2000

By A. S. Rao

In the original roast-leach-electrowin (RLE) circuit at the Chambishi Cobalt Plant, commissioned in 1978, the separation of nickel and zinc from cobalt in aqueous streams was achieved by successive stages of precipitation using lime. However, this technique was not able to meet the increasingly stringent metal quality requirements of customers whilst maintaining acceptable process recoveries. Intensive process development work was carried out and, in July 1988, an ion exchange circuit for nickel removal was commissioned using DOW XFS 4195 resin and for the first time Z.C.C.M. produced high purity cobalt metal containing less than 0.10% nickel. Following further work, a solvent extraction circuit for zinc removal, using DZEHPA, was commissioned in February 1991 in order to enhance cobalt recovery by reducing co-precipitated cobalt losses. This paper outlines the process development, design, commissioning and subsequent operation of these nickel ion exchange and zinc solvent extraction circuits.

Jan 1, 1993

By Florian Kongoli

Non-ferrous smelting slags .can contain magnesia, which substantially increases the liquidus temperature. One option to counter this increase is to flux with calcia. In this work, experimental liquidus measurements including new measurements on industrial slags have been compared with a FACT-based thermodynamic model, which predicts the liquidus surface of multi-component iron silicate smelting slags containing both magnesia and calcia. The predictions, which agree well with experimental results, are summarized in both isothermal and non-isothermal diagrams to give a quantitative description of the liquidus surface.

Jan 1, 1998

By Tobias Dubberstein, Hans-Peter Heller

The viscosity of Fe-Cr-Mn-Ni TRIP/TWIP (Transformation Induced Plasticity, Twinning Induced Plasticity) steel with varied nickel content is investigated using a vibrating finger viscometer. The viscosity of the melt is calculated from the change in power input in the field coil by an immersed finger into the liquid steel to maintain a constant peak-to-peak amplitude of the sine wave of oscillator compared to the idle state. Nickel content in steel is varied from 3 wt% to 9 wt%. The dynamic viscosity (η) at 1600 °C for 3 wt% Ni is 3.73±0.14 mPas, for 6 wt% Ni 3.50±0.03 mPas, and for 9 wt% Ni 3.93±0.09 mPas. There is a kink from low to high nickel content in viscosity values of Fe-Cr-Mn-Ni alloys. This phenomenon can be explained by a change in coordination number in the melt, as reported for Fe-Ni binary system in literature. The availability of viscosity data delivers relevant input to model free fall atomization processes of FeCrMnNi alloys.

Jan 1, 2015

By N. Menad

Thermal treatments of five different types of non-ferrous metallurgical wastes, under controlled atmosphere, were carried out at temperatures lower than 800 °C. The aim of these treatments was to reduce the toxic elements content and to increase that of valuable metals in the residue. <Best results were obtained by their treatments in air or hydrogen or successively both of them. Simple treatments using air or hydrogen of three samples allowed the elimination of more than? 95 % of their toxic elements and&apos; almost doubled their valuable metals&apos; concentration. For the rest two samples, combined treatment was necessary for their efficient decontamination and the concentration of valuable metals, in the treatments residue, to a reasonable value. Most of the solids issued from these treatments can be recycled in .the current non-ferrous metallurgical processes.

Jan 1, 1995

By Akira Yazawa

The similarities and differences in copper, nickel and lead smelting processes are discussed based on the sulfur-oxygen chemical potential diagrams and the free energy minimization assessments using a thermodynamic software. The prominent features of copper smelting are ascribable to the fact that copper has a strong affinity for sulfur but weak for oxygen and the liquid phase immiscibility between Cu and Cu2S. During the oxidation of sulfides, nickel metal is not stable except at temperatures higher than 1500°C, well miscible with its sulfide, and is oxidized more easily than copper. Metallic lead looks as stable as copper during the oxidation of the concentrate but Pb and PbS. are much more miscible with each other and the vaporization loss is considerable. In the reductive smelting of oxides, the effects of oxygen potential and temperature on the copper contents in slag are not significant due to the monovalent character of copper and the reduction of copper content in slag is not easy in practice. The effect of the slag compositions on the oxidic metal contents of slag is much more significant for lead than either copper or nickel. Due to the immiscible nature between Pb and Fe, high grade lead bullion is easily obtained and lead is more tolerant to impurities.

Jan 1, 1998

By B. Mishra, W. A. Averill

"The application of various hydrometallurgical, pyrometallurgical and electrochemical processes in the extraction, purification and production of radioactive metals as well as the use of various materials, ego metals and alloys, ceramics, polymers, etc. in the process, construction and handling equipment in the nuclear industry has generated a large stockpile of radioactively contaminated waste material and scrap metal which can not be directly discarded, recycled or considered for long-term storage due to its volume and potential hazards, without the separation of radionuclides. This paper reviews the emerging methods that have been investigated and suggested for dealing with some of these wastes and scrap material.The separation technologies studied for the recovery of radioactive components from the pyrometallurgical and electrochemical processing wastes have been discussed in details with results from some of the recent theoretical and physical modeling work as well as the data obtained from the actual waste treatment. Specific processes shall be described in terms of its advantages and limitations. These emerging separation technologies are being considered by the US Department of Energy as alternatives for dealing with the issues of environmental management [EM] and decontamination and decommissioning [D&D].IntroductionThe high temperature carbothermic or metallothermic smelting reduction methods for metal production are associated with the generation of significant quantity of waste as slags, flue dusts, sludges, residues, effluent salts etc. Certain hydrometallurgical processes also generate lots of aqueous waste due to the inherent nature of the technique. Also, the gas-based reduction processes are not applicable to many stable metal compounds, such as alumina, titania, beryllia, lanthanide and actinide oxides, etc. due to thermodynamic considerations. All these methods cause substantial environmental hazard. There is a need to develop alternative processes which have low waste or ideally a ""zero-waste"" generation.Pyrochemical processes using molten salts provide a unique opportunity for the extraction and refining of many reactive and valuable metals either directly from the beneficiated ore (aluminum, beryllium, neodymium, plutonium, uranium, etc.) or from other process effluent that contain reactive metal compounds. The processes reduce metal compounds electrolytically (A12O 3 and BeCI2) on a carbon anode or by calciothermic reduction (Po, Nd). The by-product, in the latter case, is a calcium oxide saturated halide salt. The waste-treatment to recycle the halide has to be done as a separate step or stored as a contaminated waste. A successful separation technology can provide a new insight to the waste minimization strategy for the nuclear industry."

Jan 1, 1996

By J. V. Atwood

The U.S. Bureau of Mines has developed a novel Double Membrane Electrolytic Cell (DMEC) that exhibits unique features for recycling contaminated metals and metal alloys. The DMEC incorporates two anionic ion exchange membranes, separating anodic and cathodic regions of the cell. The ion exchange membranes prevent significant transport of unwanted cationic impurities to the catholyte from the impure anolyte while the anion/cation balance in cell compartments is maintained through the free movement of anions between compartments. The membrane barrier makes it possible to electro refine highly contaminated materials or to electrowin from solution while utilizing alternate anode reactions. Sinceanolyte and catholyte cross contamination has been eliminated, premium cathode products are produced. The DMEC has been tested at bench, pilot, and commercial scales. Configuration of the DMEC, cell operation, scale, up efforts, and significant design factors are discussed. Two separate recycling investigations utilizing DMEC technology are presented. The first investigation examines recovery of high purity cobalt and nickel from severely contaminated super aIloy scrap. The second involves? upgrading contaminated cobalt in the U.S. Government&apos;s National Defense Stockpile. Capital and operating costs for both potential applications are presented.

Jan 1, 1995

By Qingchun Yu, Baoqiang Xu, Yongnian Dai, Bin Yang, Fulong Zhu

"In this paper, the mechanism of the carbothermic reduction-chlorination process to extract aluminum from alumina in vacuum was investigated. The carbon monoxide (CO) content of the gas, phases of the reduction slag, surface morphology of the reduction slag and the product aluminum were measured by means of gas chromatography (GC), XRD, and SEM. The experimental results indicated that the content of CO in the gas decreased, but Al4C3 increased with time at 1773K during the carbothermic reduction process of alumina. AlCl(g) and graphite (C) were produced by the reaction between Al4C3 and AlCh(g) at 1773K, and then aluminum beads generated after the decomposition of AlCl(g). It implied the mechanism of alumina carbothermic reduction-chlorination process in vacuum involves three steps as follows: the carbothermic reduction of A}z03 to produce Al4C3, the chlorination of Al4C3 by AlCh(g) to produce AlCl(g), and the decomposition of AlCl(g) to produce Al(l).IntroductionAluminum is the basic raw material for many industries [1], and it is used extensively because of various excellent properties such as light weight, good malleability, high strength, excellent thermal conduction, high corrosion resistance and so on [2]. Industrial production of aluminum currently includes refining alumina and electrolytic aluminum processes. However, its development has been effected by some factors such as high energy consumption and heavy environmental burdens [3]. In the past several decades, there had been numerous attempts to produce aluminum by new methods. Extracting aluminum from alumina or bauxite directly by carbothermic reduction-chlorination process had been studied [ 4-6]. Although the alumina carbothermic reduction process [7~9] had been studied, the mechanism of the carbothermic reduction-chlorination process had not been systematically elucidated.In order to investigate the mechanism of the carbothermic reduction-chlorination process in vacuum, GC, XRD and SEM techniques will be used to determine the CO content and to characterize the surface morphology and composition of the slags at various temperatures."

Jan 1, 2011

By Sang Han Son

The vapor pressures of FeCL2 and ZnCL2 in the FeCL2?ZnCL2 system were measured by the transpiration method at 873K and 9I7K, The vapor pressure data were interpreted to indicate the formation of complex ions in the FeCL2?ZnCL2 melts, It is presumed that the complex molecule FeZnCl4 as well as FeCL2 and ZnCL2 exists in the vapors in equilibrium with molten FeCL2-ZnCL2 mixtures, The activities in the FeCL2-ZnCL2 system are shown a negative deviation from Raoult&apos;s law. These results suggest the formation of complex ions such as ZnCL14 in molten FeCI2?ZnCL2 mixtures.

Jan 1, 2003