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By Ryosuke O. Suzuki

A new cell concept for calciothermic reduction is proposed in which the titanium dioxide instead of TiCl4 is used as the raw material for reduction, Metallic calcium is needed as the reductant of a thermochemicaily stable oxide, such as TiO2. CaCl2, is selected as the solvent of Ca and simultaneously as the solvent of CaO. The reduction system consists of a single cell where both the reduction reaction and the electrolytic reaction for recovery of reducing agent coexist in the same molten CaCl2 bath. A few mol%Ca dissolves in the melt and gives the media a strong reducing power. Sufficiently deoxidized metallic titanium deposits and forms a slightly sintered granular sponge. Both mechanisms of the halide flux deoxidation and the electrochemical deoxidation work efficiently for these fine precipitates, The reducing agent is in situ recovered by electrolysis of CaO because the molten CaCl2 he a relatively large solubility for CaO Some cell designs and modifications are proposed for industrial applications.

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 Ivan Imris

The iron production has generated many tonnes of very fine residues with high concentration of iron. In addition, during the recycling of galvanised steel scrap in the steel making processes the zinc and lead are largely concentrated in the dust. These kinds of dusts are usually dumped beside the metallurgical plants and cause environmental problems. Therefore the metal recovery from the metallurgical residues has become a major interest not only from the viewpoint of metals recycling but mainly from the viewpoint of environmental land protection. The thermodynamic analyses and laboratory experiments suggested that the metals could be recovered from metallurgical wastes by reduction roasting and by plasma smelting processes. The iron rich pellets with very high metallization may be obtained from metallurgical wastes by the reduction roasting and the inert slag and pig iron could be produced by plasma smelting processes. In both cases the iron rich products are suitable for the steel production. During the reduction roasting or plasma smelting the high volatile zinc and lead metals were removed and enriched as a secondary dust, Zn-Pb concentrate, which is suitable for processing in zinc and lead smelters. Suggested processes are commercially feasible and environmentally friendly without any solid or liquid waste.

Jan 1, 2003

By Xiao Songwen

Based on the anion coordination polyhedron growth unit theory, the polymorph transformation mechanism of antimony white (Sb2O3) in hydro-process was investigated. The new findings had been verified in the commercial-scale test and it was shown that adding a small amount of tartrate ions was economical and effective for polymorph transformation of antimony white in hydro-process.

Jan 1, 2003

By Tetsuya Uda

Our recent achievements of rare earth separation technique[1,2] and new process idea for rare earth magnet recycling[3] are reviewed, (1) Binary chloride mixtures of rare earths were separated by a new selective reduction-vacuum distillation process. According to our experimental results, apparent separation factors were 8.1 for the Pr-Nd chloride mixture and 570 for the Nd-Sm chloride mixture. These values are much higher than conventional solvent extraction methods. (2) A study of recycling process of magnet sludge was carried out. The rare earths in the neodymium magnet sludge were extracted by chlorination with FeCI2, An activated carbon was used as a de-oxidation reagent Metallic iron in the sludge was not chlorinated because the iron monochloride is not stable, The extracted rare earth chlorides were easily separated from Fe-alloy and the excess of FeCh by vacuum distillation, 96 % of neodymium and 94 % of dysprosium in the sludge were extraeted into chloride phase, By the vacuum distillation, a mixture of neodymium and dysprosium trichlorides of 99.2 % purity was recovered, On the other hand, the rare earth chlorides can be converted to the corresponding oxides by a pyrohydrolysis reaction accompanied by a formation of HCl gas, The HCI gas can chlorinate metallic iron to FeCh, Therefore, a new recycling process for rare earth magnet waste can be realized as a chlorine circulation type process. During the process, only carbon and water are consumed and there are no toxic pollutants, Moreover, the obtained rare earth oxide can be directly used as raw material in the conventional oxide electrolysis process,

Jan 1, 2003

By Ramiro Escudero G.

Since the introduction of column flotation almost forty years ago the column technology has grown into several non-mineral applications such as among others the effluent treatment, soils recovery and de-inking of recycled paper. Recent studies have demonstrated that particular characteristics of the dispersion (bubble size, gas holdup, bubble surface area flux) are needed for a given flotation column duty. In this work, two kind of spargers were tested (i.e., internal and external) using a 4 inch column lab in a two phase system. Results show that the external sparger provides a dispersion with characteristics that include those produced by the two internal spargers.

Jan 1, 2003

By Ma Ying

The continuous directional solidification technique of five kinds of special ZA alloys with eutectic, peritectic and eutectoid transfonnation under the condition of continuous casting by heated mold was studied. The mechanism of surface defects appearing in ZA alloy line was discussed and the structure of some defects were analyzed by SEM. The results show that only when the fitting of various technique factors, pressure head, outlet temperature, pulling speed and cooling condition are reasonable under a certain range, can the ZA alloy smooth line be continuously pulled out. Unreasonable techniques will result in hot tear, rough surface, mush outlet, leaking and other defects. The shape and location of solid-liquid zone have an important influence on the formation of the above defects. When the solid-liquid zone is located in the mould outlet or inner mould, the surface of solidification will protrude into the inner mould. If the remaining liquid cannot counteract the solidification contraction, a rough surface will appear. If the solidification surface further into the mould, the ingot in the mould will have a great friction force when pulling and will form a hot tear. When the solid-liquid zone is moved out of mould, the solidification surface will turn into a plane, which easily results in leaking. A vibration or unstable operation will cause an ingot winding during pulling.

Jan 1, 2003

By Varuzan Kevorkijan

A new method for faster production of functionally graded metal-ceramic laminates is based on reactive pressureless counterflow infiltration/penetration of a ceramic substrate with two different metallic infiltrants. The porous or dense ceramic preform is pressurelessly infiltrated or penetrated from one side by the first metallic infiltrant to the desired cross section of the preform, producing the top layer made up of the solidified infiltrant and the underlayer consisting of reactive infiltrated preform. The partly infiltrated preform is then completely infiltrated starting from the other side by the second metallic infiltrant, in this way fabricating the internal layer, consisting of the ceramic preform infiltrated with the second infiltrant and the bottom layer formed by the solidified second infiltrant. Systems already investigated include carbide, nitride and boride ceramic performs infiltrated with aluminum and magnesium alloys.

Jan 1, 2003

By G. C. Yao

Iron and silicon impurities can form needle and branch shape intermetallie compounds in molten aluminum when there is no manganese. It is difficult to separate them from molten aluminum by electromagnetic separation. The Fe-Si-AI and Fe-Al intermetallic compounds were transformed into Mn-Fe-Si-Al and Mn-Fe-Al compounds by the addition of manganese into molten aluminum. In molten aluminum the morphology of these intermetallic compound particles is lumpish and spherical. Migration resistance of these impurity particles is small, which is beneficial to separation. FeSiMnA4 and FeMnAI6 are paramagnetic. These impurity particles can be moved by magnetic force and can be separated from the molten aluminum.

Jan 1, 2003

By Dirk Verhulst

The Altair process employs digestion of ilmenite ore in concentrated hydrochloric acid, solvent extraction to concentrate Ti in a purified stream and spray hydrolysis to produce a TiO2 hydrate, followed by final calcining and milling. HCl gas is regenerated by pressure-swing distillation and reinjected in the leaching solution. All chloride streams are recycled. Chromium compounds generally remain in the residue. Solvent extraction provides flexibility for the removal of naturally occurring radioactive elements (NORMs) present in some ilmenites. The process was previously tested at a 5 t/day feed scale. Recent work at pilot scale (40 liter reactor) led to further improvements. Recovery of Ti in solution is now at least 90% with ilmenite ores, while crystallization at lower temperature lowers the amount of Fe in solution to about 5 g/l and improves solvent extraction, which is now conducted in columns. Higher Ti and lower Fe concentrations in the SX eluate improve the economics. A new formula for pigment production via spray hydrolysis produces a pigmentary base with a narrow particle size distribution.

Jan 1, 2003

By Maneesh Singh

During the various stages of iron & steel production a number of iron-rich by-products are generated. The traditional way to recycle them back to the blast furnace has been the balling - sintering process. These by-products can also be made into cement-bonded agglomerates for use as burden material for blast furnaces. In order to improve the quality of agglomerates the effects of various processing parameters on the properties of cement-bonded briquettes have to be controlled. This paper looks into the various aspects of producing cement-bonded agglomerates and using them as burden material for blast furnaces.

Jan 1, 2003

By Fumitaka Tsukihashi

Increasing amounts of steel scrap are being used as resources for steelmaking. Therefore, there has been a growing interest in the removal of harmful tramp elements such as antimony, zinc, tin, arsenic, bismuth, lead and copper from the molten steel. The problem that should be solved is the economic removal treatment of residual tramp elements in the steelmaking processes and the production of high quality steel by reducing the effect of the contaminated tramp elements and satisfying the environmental regulations. In this paper, the available thermodynamic data of the residual tramp elements in the molten steel arc summarized and the possibility of the removal of residual tramp elements from the molten steel is thermodynamically estimated.

Jan 1, 2003

By Bora Derin

The partial pressure ratios of sulfur and oxygen for several copper flash smelting plants were derived using the Reddy-Blander (RB) model and predicted dissolved sulfur contents available in the literature. The sulfide capacities (Cs) of six different flash smelting plants (FeO-CuOo.5- CaO-MgO-FeOu-AlO15-SiO2) slags were calculated. The log (PO2/PS2) versus matte grades of various industrial processes was determined. The PO2/PS2 ratio increased with an increase of copper grade. The calculated partial pressure ratios for the copper flash smelting are in good agreement with those of the experimental data.

Jan 1, 2003

By Jhon Cuya

Titanium dioxide is the well-known catalyst for the photodecomposition of water in UV region and its nanoparticles show better performance than its bulk materials. Furthermore, partially sulfurized TiO2 is expected to be chemically stable and have an enhanced photocatalytic activity compared with TiO2. For this purpose, the sulfurization behavior of TiO2 nanoparticles was thermogravimetically (TG) studied by a thermo-balance with a quartz spring using CS2. From the TG curve of TiO2 nanoparticles, first, the weight decrease appeared down to around 8 wt% and then sulfurization reaction started at around 500 °C at heating rate of 1O 'Cumin. The weight increase curve showed a maximum of ca 30 wt% at around 750 T and then gradually decreased to ca 12w% at 1000OC. This would be caused by the formation of TiS2 followed by the decomposition of TiS2 to lower sulfides, such as Til.08S2 and Ti3S4. From the comparison of the sulfurization of TiO2 nanpparticles with that of anatase, rutile and Ti(OH)4, it was found that TiO2 nanoparticles showed a similar behavior to that of Ti(OH)4.

Jan 1, 2003

By J. H. Huang

In this investigation, the selective precipitation of cobalt and molybdenum from Co-Mo aqueous solutions was studied in order to recover efficiently valuable elements from industrial effluents generated from a novel electrodeposition of nanocrystalline Co-based alloys process and reduce the effluent impact on environment. It was found that the behavior of cobalt in aqueous solutions was substantially affected by the presence of molybdenum. When adding 11.6 to 46.6g/L molybdenum to a 50g/L cobalt solution, the co-precipitation of molybdenum and cobalt started to occur at pH value of 3-4. However, without the presence of molybdenum, cobalt could only be precipitated out of the solution at about pH 6. Most of the molybdenum was found in the solid phase when the solution pH reached 5. After further increasing pH to greater than 7, the molybdenum dissolved back into the solution. Cobalt kept precipitating as the pH increased. When the pH was greater than 7, most of the cobalt was present in the solid phase. The chemical and physical characteristics of the precipitated materials were investigated by SEM, XRD, AAS and EDX. It was revealed that the precipitate was initially present as cobalt molybdate oxide hydrate and subsequently transformed as sodium cobalt molybdenum oxide. With further increasing the solution pH, the precipitate was transformed into cobalt hydroxide. Further investigation implied that most of molybdenum was chemically tied to the precipitate produced at the low pH, yet at the same time, physically entrapped at the high pH. The paper also presents the influence of reaction temperature and time on the precipitation process and kinetics.

Jan 1, 2003

By G. C. Yao

Iron and silicon impurities can form needle and branch shape intermetallie compounds in molten aluminum when there is no manganese. It is difficult to separate them from molten aluminum by electromagnetic separation. The Fe-Si-AI and Fe-AI intcrmetallic compounds were transformed into Mn-Fe-Si-AI and Mn-Fe-AI compounds by the addition of manganesc into molten aluminum, In molten aluminum the morphology of these intermetallic compound particles is lumpish and spherical. Migration resistance of these impurity particles is small, which is beneficial to separation. FeSiMnAl4 and FeMnAl6 arc paramagnetic. These impurity particles can be moved by magnetic force and can be separated from the molten aluminum.

Jan 1, 2003

By John Hollow

The Fort Knox Mine is an open-pit operation, located in Alaska, which started commercial production in March 1997. A conventional Mill processes 38,000 tpd of a low grade (1.0 g/t Au) free milling gold ore with a low sulphide component (below 1%). Gold production (11% from gravity and 89% from cyanidation) exceeds 400,000 ounces per year. Short retention time (20h), low temperature (7oC) and low grade make high leaching kinetics critical for the performance of the process. In April 2001, the treatment of True North ore, which represented 14.4% of the mill throughput and contained more sulphide in the form of pyrite, arsenopyrite and stibnite, resulted in a substantial drop in the average gold extraction from 87% to 72.6%. Laboratory investigations indicated that the addition of lead nitrate increased gold extraction to 91.7%. Further investigations were initiated to determine the leaching parameters and the nature of the problem. Subsequently, a lead nitrate addition scheme was implemented at the Fort Knox Mill that resulted in 2002 gold production being in excess of 31,000 ounces higher than that estimated for the non-lead nitrate reagent scheme. This paper presents the results of laboratory investigations and modifications in plant operating practices.

Jan 1, 2003

By Huaming Yang

The vanadium-doped SnO2 nanoparticle was synthesized by the co-precipitation reaction and subsequent calcination from the vanadium(III) chloride and tin(IV) chloride. The crystal size, pore size distribution, micrograph and properties of the nanocrystalline powders were examined by differential thermal analysis (DTA), thermogravimetric analysis (TGA), X-ray diffraction (XRD), desorption isotherm (Barrett-Joyner-Halenda method) and transmission electron microscopy(TEM). Thermal treatment of the precipitate powder at 600°C led to the formation of V -SnO2 nanoparticle of -10mm in crystal size. Most of the pores in the nanoparticle are about 5~15nm in diameter. Effect of doped vanadium on the crystal size of the nanopartic1e was discussed.

Jan 1, 2003

By Fumitaka Tsukihashi

Phase diagrams of the CaO-SiO2-FeOx-MgO, Al2O3 systems arc necessary for the analysis of copper smelting reactions and sintering process of iron ore. The effect of MgO and Al2O3 addition on the liquidus of the phase diagram of the CaO-SiO2-FeOx system at low oxygen partial pressure was observed. The liquid phase area changed bi the addition of MgO and Al2O3 with a changing oxygen partial pressure from 10-8 to 10-3 atm (10-3 to 10 2 Pal at 1573K. The effect of Fe3+ / Fe2+ ratio on the melting mechanism is discussed.

Jan 1, 2003

By Yoshihiko Maeda

It is said that the 21 st century will be an era of the remedy of the global environment. In order to reserve natural resources for the future and to avoid the dispersion of heavy metals after usage and to avoid pollution problems, it is extremely important to recycle heavy metals as much as possible by reasonable recovery procedures. The nonferrous metal industry is expected to play a important role in the recycling of heavy metals that are originally their products. From the depressed metal price experienced in Japan in 1980th due to the sudden change in current exchange rate between US dollar and Japanese yen, one of major nonferrous metal company, Dowa Mining, has diversified its business area not only to the so-called down stream, but also to the environmental business including metal recycling, industrial waste treatment and soil remediation by utilizing technologies and facilities once used or still used for mining and smelting of copper, zinc, lead and precious metals. In this paper some of these applications will be presented.

Jan 1, 2003