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By Katsutoshi Inoue

The sulfuric acid leaching of spent hydrodesulfurization catalysts yields an acidic solution rich in rare metals such as molybdenum, vanadium, cobalt, and nickel in addition to aluminum. For the purpose of separating and recovering the rare metals from the solution, basic solvent extraction characteristics of the metals involved with commercially available acidic organophosphorus reagents like TR-83, PC-88A, PIA-8 and CYANEX 272 as well as aliphatic alpha-hydroxyoxime LIX 63 from sulfuric acid media were investigated in the present work. It was demonstrated that CYANEX 272, PIA-8 and LIX 63 possessed excellent selectivity for molybdenum and vanadium over the other metals at comparatively low pH. Further, recovery of molybdenum and vanadium from the total leach liquor by the selected extractants was discussed. Additionally, in order to achieve preferential separation and recovery of cobalt and nickel over an appreciable amount of aluminum from the raffinate obtained after recovering molybdenum and vanadium, a systematic investigation was conducted on synergistic extraction behaviors of the mixed solvents of LIX 63 in combination with a series of acidic extractants such as CYANEX 272, PIA-8, PC-88A, D2EHPA, TR-83 and OPEHPA for cobalt, nickel and aluminum. It was elucidated that all of these mixtures could exhibit a good synergistic effect for extraction of cobalt and nickel, and that the lower the pKa of the acidic extractants, the greater the synergism. Contrarily, the extraction of aluminum, was considerably suppressed by LIX 63. Effective extraction of cobalt and nickel away from aluminum was accomplished from the sulfate solution at low pH (1.0 - 2.5) with the mixtures. In particular, the mixtures consisting of LIX 63 and CYANEX 272 or PIA-8 appeared to be the most feasible and economic from an industrial point of view, yielding acceptable separation efficiency for cobalt and nickel over aluminum and .a low acidity requirement for stripping cobalt and nickel as well as negligible degradation of LIX 63. Aluminum can be readily recovered as sulfate salt from the raffinate obtained after recovering molybdenum, vanadium, cobalt and nickel as outlined above by conventional crystallization method.

Jan 1, 1995

By Peng Jianping, Feng Naixiang, Di Yuezhong, Wang Yaowu, Pan Xijuan

A vacuum silicon thermal reduction lithium process is developed in present work which used lithium hydroxide, alumina and calcium oxide as raw materials. The process contains two steps, which are that Li5AlO4 clinker is prepared in ambient environment, and that metal lithium is extracted from Li5AlO4 clinker with ferro-silicon alloy as reductant in vacuum. On the basis of thermodynamic analysis and investigative experiments, feasibility of this process is proved. The results show that Li5AlO4 can be generated by calcination lithium hydroxide and alumina, the burning loss is above 31% under the conditions of calicination temperature above 750℃ and time more than 90min. The main phases of calcination product are Li5AlO4 and CaO. When the calcination product is reduced by ferro-silicon alloy in vacuum, the lithium reduction ratio can be over 80% under the conditions of reduction temperature 1200℃ and reduction time 60min.

Jan 1, 2014

By Y. K. Rao

In the carbonyl process for the refining of crude nickel CO(g) reacts with nickel in the 310-370K range producing nickel tetracarbonyl, Ni(C0)4(g). Iron and cobalt impurities also form gaseous carbonyls but their partial pressures are low. The carbonyl is led to a decomposer plant wherein the gas disproportionates in the 500-600K range depositing pure metal on nickel pellets that move countercurrent to the gas-flow. This system serves to illustrate the fundamental principles involved in the vapor phase mass transport of elements, against temperature-gradient, under the influence of chemical potential gradient. Unlike in the crystal growth, the source is at a lower temperature (say 350K) whereas the seed is in the hot-zone (say 550K) of the closed ampoule-type reactor. By assuming virtual gas-solid equilibria in the end zones, with diffusion of gaseous species between them acting as a slight perturbation, the quasi-steady- state mass-transport rates are computed for a range of CO-pressures and temperatures.

Jan 1, 1993

By F. Elgersma

A high purity electrolysis solution is essential for hydrometallurgical zinc winning processes. For this reason ferric iron containing compounds such as jarosite are precipitated as iron and impurity collector during the calcine leaching. Jarosite thus forms a chemical waste and creates environmental problems. This research contributes to the development of a wet jarosite treatment process, where less contaminated jarosite is produced which can act as an iron source. The present work studies jarosite precipitation kinetics and the uptake of zinc cations in batch and continuous experiments. The distribution coefficient for zinc in continuous experiments is constant for a wide ratio of zinc over ferric ions in the solution. Addition of NH, + ions in batch experiments accelerates the conversion rate equivalent to the driving force increment. Addition of 50,2-ions above the stoichiometric ratio increases the conversion rate less then could be expected from the increase in the estimated driving force. Zinc ions tend to retard the conversion rate. An increasing reaction temperature increases the conversion rate. Below 75 ?C the conversion rate approximates zero.

Jan 1, 1990

By Robert E. Moore

Synthetic spinel is proving to be a highly effective refractory for specific applications, but its cost limits applications. Formation of spinel from a raw material such as diaspore or bauxite could provide a simple and less costly starting material. In the study reported here, finely ground (-325 mesh) diaspore from Missouri and bauxite from Guyana and China are combined with hard burned MgO (-325 mesh) in appropriate proportions to yield spinel and spinel with secondary phases. A classical sintering and dilatometer study was completed, followed by a microstructure study to determine completeness of the reactions and morphologies of the reaction products.

Jan 1, 1993

By F. H. (Sam) Froes, C. Suryanarayana, K. C. Russell, C. M. Ward-Close

"Far from equilibrium synthesis allows development of novel crystal structures and microstructures, leading to achievement of enhanced physical and mechanical properties. A number of ""far from equilibrium"" techniques are reviewed with emphasis on the amount of departure from equilibrium. The ability of two such techniques, mechanical alloying (MAl, and physical vapor deposition (PVD) to develop novel structures are discussed in detail. For the MA process emphasis is placed on intermetallic compound compositions. Solubility extension, beyond rapid solidification (RS) levels, is found in terminal compositions but not for the intermetallics. Nanostructure-sized grains (< 100nm) form which can be retained after ""low temperature"" compaction. On continued milling in many cases the nanometer-sized grains transform to an amorphous structure. Ordering is destroyed by MA, except in those intermetallics with large negative enthalpies of formation. For the PVD process, a review of application to terminal light alloy compositions is presented. This includes a new high-temperature aluminum alloy, layered materials with nanometer spacing, corrosion-resistant magnesium alloys and low-density titanium compositions. IntroductionTo enhance the mechanical property combinations of advanced structural materials innovations in process/synthesis are required [1-6]. In this paper the capability of various ""far from equilibrium"" synthesis techniques [7,8] to produce novel constitutional and microstructural effects, and hence potentially enhanced physical and mechanical properties, in advanced materials is presented. The application of two such methods, mechanical alloying (MA) and physical vapor deposition (PVD) is discussed in detail. For the MA process emphasis is on intermetallic compositions with consideration given to solid solubility extension, microstructural refinement, amorphization, and formation of intermetallic compounds. For the PVD process application to terminal light alloy compositions is discussed."

Jan 1, 1994

By QIE Jun-mao, DONG Fang, DENG Hao-hua

The DIL402C thermal dilatometer and STA449C thermal analyzer were employed to test the linear expansion and contraction coefficient，CP and DSC curve of 304 stainless steel. The result showed that the linear expansion coefficient range was 20.9700×10-6～21.5712×10-6 and the linear contraction coefficient range was 21.2528×10-6～21.9471×10-6.The linear expansion and contraction coefficient were higher than other steel grade，so the 304 stainless steel belonged to the crack sensitive steel. Because of the crystal phase transformation occurred during the 1000~1400 ℃,the curve of CP fluctuated obviously and the defects of casting blank occurred easily. Chosen 1414℃ as the liquidus temperature of 304 stainless steel based on the analysis results of DSC. The curve of DSC was unsmooth during 1450～1100℃，the crystal phase transformation occurs and thermal stability of slab was inferior.When the initial solidified shell formed in this temperature range,the thickness of the shell would be nonuniform and the surface defects occurred more easily.

Jan 1, 2015

By Takeshi Nagano

"Prior to discussing future trends of non-ferrous metals smelting and refining, the past developments are looked back. Social and economic environments in Japan over the past two decades are reviewed. Technological developments to comply with these environments are explained, taking for examples the cases of the Mitsubishi continuous smelting and converting process and Onahama's jumbo tank system for copper tankhouse. After considering the factors which will influence the improvements in non-ferrous processing, future trends are forecasted generally for copper, zinc, lead, aluminum and rare earth metals. Recent development works in Japan for the future are also introduced. In the discussed area, it appears that the emergence of new innovative processes would be difficult. The progress will be made rather toward the sophistication of the existing technologies, utilizing the advancement of the related technologies such as computers, electronics, etc. IntroductionThis paper discusses the future trends of non-ferrous metals smelting and refining on the occasion of the international symposium, ""The Metallurgical Processes for the Year 2000 and Beyond"".It is considered that the improvement of technology is greatly influenced by the social and economic environments which surround it. From this standpoint, review was made of Japanese case over the past two decades. Various new technologies were developed also in the non-ferrous metal world to comply with the requirements under the above environments. The examples are described in the cases of the Mitsubishi continuous smelting and converting process and Onahama's jumbo tank system for copper electro-refining.After foreseeing the major factors which will affect the technological developments in the future, the trends are forecasted for copper, zinc, lead, aluminum and rare earth metals generally. Some development works in Japan, which will give suggestions for future trends, are also introduced in some detail."

Jan 1, 1988

By C. J. Newman

The Kidd Creek Copper Smelter has been expanded from its original design of 59,000 tonnes of copper per year to over 120,000 tonnes per year. Modifications to the process gas handling system and acid plant have been made to accommodate this higher production rate and to generally optimize the operation. The gas handling system associated with the continuous smelting process is discussed in terms of boiler accretions and modifications to minimize their impact on operations; design changes to effect reductions in high pressure drop duct configurations; material changes to overcome corrosion and plant additions to improve gas cleaning capability. The acid plant is reviewed with references to changes? made to accommodate the increased SO2 gas strength resulting from the higher smelting rates.

Jan 1, 1992

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 Run-sheng xu, Hai-yang WANG, Di ZHAO, Teng-fei SONG, Jian-Liang Zhang

This paper was mainly focused on the different semi-cokes and charcoal which could be new fuels for blast furnace injection. Through the comparative study with bituminous coal and anthracite coal, the properties of semi-cokes and charcoal were presented in this research. 10 indexes of different fuels were obtained by different standard experiment, including proximate analysis, ultimate analysis, igniting point, explosivity, transportation characteristic, ash properties, grindability, calorific value, combustibility and reactivity with CO2. According to the data analysis, it provided a theoretical basis for rational utilization of various blast furnace fuels, and helped to broaden the scope of the blast furnace injection fuels. This research could contribute to energy conservation, emissions reduction, and sustainable development of iron and steel enterprises.

Jan 1, 2015

By Lamar S. Todd

The direct production of metal from a sphalerite concentrate is an attractive route for primary zinc. A series of operations and conditions have been selected to efficiently cause the following overall exothermic reaction. The process uses a continuous circulation of molten copper for material and energy transfer between the unit operations. Sulfide concentrate is reduced with an excess of superheated copper to make a copper alloy and white metal. The alloy is stripped of volatile metals under vacuum and some metals can be separately condensed. The residual copper and the white metal are fed into a copper converter to be blown with oxygen for desulfurizing and the superheated copper is recycled. The paper will include a detailed material flow sheet for the process, discussion of the operating conditions of the individual units, behavior of minor elements, and zinc quality.

Jan 1, 1999

By John M. Gaines

Lead concentrates from the Viburnum Trend in the Southeast Missouri Lead district are sintered prior to smelting to bind the particles together homogenize the feed, and reduce the sulfur content. Good sinter forms competent masses about 4 to 6 inches across, that hal!e about 15% porosity and good mechanical strength to withstand transport and the weight of the overlying load in the smelter. Bad sinter has poor mechanical strength and forms fine fragments that retard the circulation of reducing gases in the furnace and lengthen the time required for reduction. The productivity of the lead smelter depends on good sinter feed. Because some lead sinter plants produce bad sinter about 20% of the time, this applied mineralogy study has been undertaken to determine the mineralogical and microtextural differences between good and bad sinter. A reflected light microscopic study of 130 polished sections has shown that good and bad sinters differ distinctly in their mineralogy, tex1ure. and character of, porosity. Good sinter consists of hardystonite, franklinite. lead-zinc-bearing magnesium-calcium silicate, lead silicate matrix, and large crystals of calcium-magnesium-iron silicate, together with minor amounts of lead oxides, lead-zinc silicate, metallic lead, specular hematite, magnetite, lead-iron-bearing zincite and zinc-Iead-magnesium-bearing wustite in a tightly intergrown mesh of crystals and with an evenly distributed porosity of 15% to 20%. Electron microprobe analyses show that the principal phases contain lead (or zinc): hardystonite (4-20% Pb) franklinite (2-14% Pb) and lead silicate matrix (65-74% Pb). Bad sinter differs from good sinter in the greater abundance of lead silicate matrix, galena metallic lead, and lead oxides and the lesser abundance of hardystonite, franklinite and calcium-magnesium-iron silicate. Bad Sinter is characterized by a lack of an intimate intergrowth of the constituent phases. Its porosity is much lower commonly 0 to 5% and those pores are concentrated in local areas rather than distributed evenly throughout the sinter.

Jan 1, 1991

By David Cocke

Study of surface and subsurface interfacial chemistry of metallic and similar systems has its enormous technological importance. Copper, for example, is a common component of many alloys and bulk amorphous systems. It is being increasingly studied today because of its use for electronic interconnect systems where processing is done below 200 ºC. Since several types of copper oxides exist, and the degree of their formation is dependent on temperature, perhaps characterization by EDS-SEM depth profiling and EIS might delineate one type of oxide from another. In this paper, we described our work on transformation of copper oxides with temperature ranging from 70 to 350 °C and their characterization by SEM, EDS, and XRD. We also showed the use of the phase angle portion of the impedance as a means to identify the predominant structure and the transition through Cu3O2 between the predominant stable CuO and Cu2O.

Jan 1, 2009

By Cong Wang, Kexin Jiao, Yongan Zhao, Haibin Zuo, Jianliang Zhang

Traditional refractory materials for blast furnace hearth lining are mainly composed of carbon bricks and the ceramic cup. However, these materials can’t meet the demands for long service life design of blast furnaces. In this paper, a new refractory called carbon composite brick (CCB) was introduced, which combined the advantages of carbon bricks and the ceramic cup. In this case, the resistance of the CCB against corrosion was equal to the ceramic cup and the thermal conductivity of the CCB was equal to carbon bricks. From the results of more than 20 blast furnaces, the CCB could be well used in small blast furnaces and large blast furnaces. In the bad condition of low grade burden and high smelting intensity, the CCB gave full play to the role of cooling system, and effectively resisted the erosion of hot metal to improve the service life of blast furnaces.

Jan 1, 2015

By Min Chen, Lei Xu, Weijun Huang, Shuai Zhang

For the purpose of extending the service life of MgO-C bricks used as linings of vanadium-extraction converters, the effect of Fe addition on properties of MgO-C bricks was investigated. The results showed the addition of Fe could effectively improve the sinterability of the oxidized layer of the MgO-C refractory at 1400°C due to the effect of FeO (formed by oxidation of Fe) on formation of MgO-FeOss and modification of the microstructure, and excellent corrosion resistance against vanadium containing slag was also obtained due to the increase of compactness of the oxidized layer and concentration of FeO in the oxidized layer. Consequently, it is considered that MgO-C brick by introducing the new phase of Fe is a favorable substitute of MgO-C refractory to be used as linings of vanadium-extraction converters.

Jan 1, 2015

By A. A. Bustos

A model was developed to simulate the blow-by-blow operation of the converting process. From the weights, compositions and temperatures of all converter feeds the model calculates the composition and tonnage of both converter matte and slag as well as bath temperature at the end of each blow. The development of the model and its application to the converter aisle operation are described. There is good agreement between model predictions and observed results. At the present time the model is being used to investigate different converting schemes and their effect on pay metal recoveries, slag chemistry and temperature of the bath. Future work involves the use of the simulation model as a process control tool for the converting operation.

Jan 1, 1988

By Kimio Itagaki

The distribution behaviours of the VA elements between the gas, slag and matte phases in copper smelting were evaluated on the basis of the thermodynamic data, most of which were determined by the authors. The distribution is basically dependent on the process factors such as temperature, the content of the element in charge, the amount of the waste gas and degree of vapour saturation with the elements. The thermodynamic quantities such as the activity coefficients of the VA elements in matte, the activities of iron and copper, SO2 or 02 potential and the distribution ratio of the elements between the slag and matte phases seriously affect the distribution, and the behaviours in various smelters could be explained systematically and reasonably by considering the changes in these quantities, In oxidation smelting at PSO2= 0.1 to 1 atm, the proportion of arsenic and bismuth in gas is predomi22t for the arsenic and bismuth distributions in both smelting and converting stages. The degree of vapour saturation has serious effect on the distribution, and sufficient contact between gas and matte phases is desirable for transferring arsenic and bismuth into gas phase.The elimination of antimony by means of vaporization is not significant. In reduction smelting at po2 = 10-11 atm, the proportions of arsenic and antimony in the gas phase are quite small, but the proportion of bismuth does not change significantly.

Jan 1, 1983

By Carlos A. Nogueira

Spent Ni-Cd batteries contain in the electrode materials heavy metals like Ni, Cd and Co, which must be recycled due to environmental problems. Pyrometallurgy is normally used for recycling these end-of-life products, but alternative processes by hydrometallurgy, integrating also physical operations, can be used. Hydrometallurgy seems to be useful, because metals can be efficiently recuperated in chemical forms with commercial value. The economical viability of this recycling process can be improved increasing the treatment capacity, through the application to different types of residues with similar characteristics like Ni-MH and domestic batteries, or other residues containing Ni/Co, like sludges, dusts or spent catalysts. Spent Ni-Cd batteries were first physically processed using shredding and wet sieving operations. Best results were achieved using an output of 6 mm in the shredder and 1.4-2 mm in the physical separation by wet sieving, resulting a fine fraction containing 70% of the initial electrode material and only 6% of the initial scrap. The acid leaching of the obtained material in the previous operation was studied, being the parameters like: temperature, H2SO4 concentration and the liquid/solid ratio (L/S) optimized. The values attributed to the factors which concerned the best results obtained on the leaching process were mainly influenced by Ni recovery. In opposition, Co and Cd were easily leached in a wide range of conditions. To attain an overall recovery, with minimum costs, of the three metals, the values of T~100ºC, [H2SO4]=2.3-2.7 M and L/S=8-10 L/kg were considered the most appropriate.

Jan 1, 2006

By Nieves Iglesias

The removal of the refractoriness of a gold bearing pyrite- arsenopyrite ore is studied. Flotation concentrates were prepared and leached with a dilute acidic ferric sulfate solution. The elemental sulfur film which forms on arsenopyrite in the oxidation process is not responsible for the low rate of the arsenic dissolution observed. A positive effect on the leaching rate is observed when Ag&apos; is added. This pretreatment eliminates the refractory nature of concentrates.

Jan 1, 1993