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By Takeshi Nagano

Copper pyrometallurgy in Japan has experienced quite fundamental changes in last fifteen years. The severe environmental restriction coupled with increase of energy costs accelerated the development work of the new continuous process in Mitsubishi Metal Corporation. After several years of pilot plant test work the commercial plant was put into operation at Naoshima Smelter in 1974, the design capacity of which was 4,000 tonnes of copper per month. Many modifications and improvements have been incorporated into the process and 7,200 tonnes per month of copper production was achieved in 1983, proving that continuous process was much more economical than conventional process. It is now possible to design and operate the continuous process in wide range of capacity. This paper will review the process and describe the progress of the process in these 10 years. 311

Jan 1, 1985

By N. M. Komkov

The main operation of obtaining zinc from sulfide raw materials by hydrometallurgical technologies is the oxidation roasting of zinc concentrates in fluidized bed furnaces. The technical-economic parameters are determined by the parameters of the roasting process, which depend on the composition of the initial raw materials, the temperature of the bed and on other factors. The predetermined roasting temperature is maintained due to the change of specific efficiency as well as to the quantity of the heat removed from the bed. The efficiency of caissons depends at a high degree on the composition and the thickness of the accretion formed on the surface of the caissons. Forecasting the roasting results is impossible unless we know the mechanism of the accretion formation. The aim of the present paper is the thermodynamic analyses of the behavior of the charge compositions under roasting and the determination of the potential mechanism of the accretion formation. The thermodynamic analyses show that under conditions of the oxidation roasting the thermodynamic probability of the formation of zinc sulfate is higher than the probability of the oxide formation until a temperature of873 OK is reached. The thermodynamic probability of the formation of the lead sulfate is higher than the probability of oxide formation in the entire temperature range of roasting. The probability of formation of ferrites and silicates of zinc decreases only insignificantly the sulfate stability. The results of the investigation of the accretions composItion formed under roasting of concentrates with particle sizes less than 0.02 J..lm (60%), containing 65% of sphalerite (ZnS), 12% of pyrite and chalcopyrite (FeS2 and CufeSz) each, 3% of galenite (PbS), 7% of silica and other non-ore minerals, have shown that the composition of accretion varies depending on the depth of the accretion layer. The accretions on the caissons and the thermo-siphons consist mostly of zinc sulfate (more than 50%). The accretions of forehamber consist mostly of zinc oxide. They also contain ferrites and silicates. The formation of the sulfate zinc accretion in the cold parts of the fluidized bed furnace (the caissons and thermo-siphons) may be explained by a lower temperature on the surface and probably by a catalytic influence of the present oxides in the formation of S02 and sulfates. The nature of the structure of the accretion in the hotter parts of the furnace may supposedly be explained by the formation of elemental vaporous zinc during roasting.

Jan 1, 2003

By C. S. Ek

Tests have been performed to recover silver and lead from residues produced after a super-hot leaching in a zinc hydrometallurgical plant operating with jarosite precipitation. When this residue is leached in ammoniaammonium sulfate or in diethylenetriamine solutions, lead dissolution is not complete and its recovery from the aqueous solutions is either difficult, due to the operating conditions, either expensive due to the amount of added reagents. In both cases, silver is partly dissolved, partly left in a new residue still containing lead and baryum sulfates. The best treatment seems to include a selective flotation producing first a silver concentrate assaying about I % Ag, then a 50 % lead concentrate collecting the baryum salts, and a final quartz-gypsum tailing. Metal recoveries can reach 50 % and 80 %, respectively.

Jan 1, 1989

By N. Kanari

The kinetics of oxychlorination of MgO by Cl2+O2 was studied in the temperature range of 850 °C - 1025 °C, using thermogravimetric analysis. The effects of C12/02 ratio, gas velocity, temperature and partial pressure of reactive gases on the reaction rate were investigated. The oxychlorination process was characterized by an apparent activation energy of about 214 kJ/mol. The reaction orders with respect to C12+O2. C12 and O2 at 950 °C were about 0.65.0.98, and -0.37, respectively. Some data about oxychlorination kinetics of MgO, Cr2O3, and MgCr2O4 contained in chromite were compared. Efficiency of using oxychlorination for the removal of iron oxides contained in magnesia was demonstrated.

Jan 1, 1999

By N. L. Piret

Reprocessing of low zinc-bearing residuals with a zinc content of less than 10%, originating from the iron and steel industry, has been given more and more attention in the last few years, due to the potential landfill liability and the increasing cost of disposal by dumping. Whereas, recycling of hazardous electric arc furnace dust is already being performed commercially on a large scale in the U.S., Japan and Western Europe, almost no reprocessing takes place in the case of these low grade zinc-bearing materials. In blast furnaces and basic oxygen furnaces dusts and / or sludges are generated at a rate of 1 to 2 % of the respective production. The technologies for the retreatment of these types of materials, either commercially available or still being developed are briefly described hereafter. They involve internal recycling, upgrading by physical separation methods, separate hydrometallurgical processing and pyrometallurgical treatment. Their scope and limitations are critically assessed in terms of technological applicability, economic feasibility and environmental compatibility. Since, the possibtlity of achieving economic profitability is unlikely with this type of material, the main criteria for acceptability of the treatment process are: generation of a iron-rich material, suitable for treatment by the iron/steel industry, acceptance of the non--ferrous metal-bearing sub-product by zinc smelters, generation of non-hazardous waste materials.

Jan 1, 1992

By Wenzhou Yu, Cong Zhang, Wenhui Ma, Gang Wang, Kuixian Wei

"A novel technique was successfully developed for nickel further purification by vacuum directional solidification. The removal effect of impurities in nickel was studied based on theoretical analysis and experiments. High removal efficiency of impurities in nickel can be realized according to theoretical analysis. The experimental results show that the vacuum directional solidification treatment could increase the nickel purity from 99.96% to 99.996%. Since vacuum directional solidification could effectively remove the impurities from nickel with low contamination and low cost, it is a potential route to obtain high-purity nickel for commercial application.IntroductionNickel is widely used in metallurgy, machinery, petroleum industry, chemical industry, construction industry, light industry, and other industries for its ductility, medium hardness, ferromagnetism and high chemical activity. Nickel-based alloy is an important material for the key parts of aircraft, tanks, submarines, radars, nuclear reactors and aerospace fields [1-5]. Generally, nickel contains Si, P, S, Fe, Cu, Zn, As, Cd, Sn, Sb, Pb, Bi, Al, Mn, Mg and other impurity elements, which may hinder the commercial application of nickel. Therefore, it is necessary to refine the crude nickel for the high purity nickel."

Jan 1, 2014

By John Hanna

The University of Alabama Mineral Resources Institute (MRI) has developed a unique process for selective fatty acid flotation of carbonate gangue from sedimentary apatites (francolite) in the pH range of 4-6, without collector conditioning of the pulp. The process, which does not require an apatite depressant, was modified to beneficiate a high MgO siliceous phosphate matrix from South Florida. The modified process includes two flotation stages, one for carbonate removal, as mentioned above, and the other for phosphate recovery from the siliceous gangue. The selective flotation separation of the carbonate and phosphate from siliceous constituents of the matrix at various pH levels and collector dosages are discussed. In the carbonate flotation stage, about 70% of the MgO was rejected in the froth, and the phosphate flotation stage produced concentrates analyzing about 31% P20S' 0.7% MgO and 4% acid insolubles. The overall P20S recovery in the two stages is about 85%.

Jan 1, 1989

By J. W. Lyman

The U.S. Department of the Interior, Bureau of Mines, investigated methods to recover valuable rare-earth materials from NdFeB magnet scrap. Although several processing techniques were evaluated" the best separation of rare earths from the NdFeB magnet ,scrap was obtained by sulfuric acid dissolution followed by precipitation of recyclable rare-earth salts. Both sodium and ammonium intermediate double-salt precipitates' that can be converted to a variety of useful neodymium products were investigated. The sodium system showed a neodymium recovery of 98 pct, while the ammonium system yielded 70 pct during double-salt precipitation. The iron-rich effluent following the rare-earth recovery was treated to produce sodium and ammonium iron jarosites that can be disposed of or converted to hematite. By following this new procedure, many materials handling and economic disadvantages found with fluoride or oxalate direct precipitation were avoided.

Jan 1, 1992

By Ramana G. Reddy

Thermodynamic modeling and experimental study on impurity capacities and their distribution between mattes or metal and slags in smelting, converting and refining of non-ferrous metals was discussed. A brief review on the recent developments in copper smelting and converting is presented. The analysis showed that, copper smelting capacity increased by a factor of 10 since 60's, smelting rate increased by a factor of more than 5 and process fuel equivalent decreased by a factor of 2. A thermodynamic model for prediction of impurities capacities in slags and their distribution in mattes and slags was developed. The impurities capacities (i.e. sulfur and arsenic) of slags were calculated a priori with no adjustable parameters using the Reddy-Blander model. The capacities predictions were made in a wide range of matte and slag compositions, Pso, and temperatures in conditions pertaining to copper and lead industrial slags. The calculated results for sulfide and arsenate capacities are in good agreement with the available experimental and industrial copper and lead industrial slags data. The sulfide and arsenate capacities in copper slags (fayalite, ferrite and olivine) and lead slags are reviewed. The application of RB model predicted ratios of 02 and S2 partial pressures in industrial copper smelting processes are discussed. Application of this model for the prediction of Sb, Bi and other impurity capacities and their distribution ratios in mattes or metal and slags, in industrial smelting and refining processes is discussed.

Jan 1, 2003

By E. J. Peuraniemi

Primary copper production using suspension smelting techniques like Outokumpu Flash Smelting always causes some dust formation. Flue dust particles are formed when sulphide feed material reacts violently with oxygen inducing particle disintegration and total desulphurisation of fragments. In the process, flue dust follows the off-gases to the heat recovery boiler (HRB) where its sulphation takes place because of prevailing conditions. Sulphation releases heat and causes also a drop in particle melting temperature and, further, particle sticking to the walls and heat exchange tube banks. Sulphation of synthetic CU20 particles were examined using a laboratory scale fluid-bed reactor. This study aims to a better understanding of flue dust behaviour in a HRB and, thus, to a better operational practise and design of a HRB. The effect of PSO/PO2 -ratio and temperature on the sulphation kinetics were tested. Standard chemical analysis, light optical and scanning electron microscopy with energy dispersive spectroscopy were used to examine the samples.

Jan 1, 2001

By Qinmeng Wang

The oxygen bottom blown copper smelting process is a new technology which has been widely applied to the copper production in China. In this work, a computational thermodynamics model for this technology has been established, based on smelting mechanism and theory of Gibbs free energy minimization. The calculated results from the model agree well with the actual industrial data, indicating that the model can be used for the predictions under different operating conditions. The tendencies of the key parameters (such as Cu losses and Fe3O4 content in slag) and the distribution ratios of the minor elements (such as Pb, Zn, As, Sb and Bi) can be predicted by adjusting the oxygen/ore ratio charged into the bottom blown copper smelting furnace. The model can be used to monitor and optimize the industrial operations of the oxygen bottom blown copper smelting process.

By Larry M. Southwick

Considerable process and equipment development and analysis were conducted during design of Freeport Sulfur's laterite nickel facilities in the late 1950's. These covered ore concentration at Moa Bay, Cuba, and concentrate refining at Port Nickel, Louisiana. Both facilities utilized acid pressure leaching and product refining steps that were similar to those later used elsewhere in the laterite processing industry. Unfortunately, developments in Cuba removed the Moa Bay facilities from Freeport control. This deprived the project of a start-up that would have allowed thorough resolution of difficulties and a quicker attainment of production capacity. This meant lost opportunity to positively prove and complete the technology when optimum resources and staff were available. This paper reviews the original rationale of how design was developed via laboratory, bench scale and pilot studies by Freeport Sulfur. Some later operating problems will also be discussed. This case is unusual, but the lessons learned may be instructive in the application of difficult and complicated technologies, as well as the need to understand and retain access to the original development and design activities Keywords: Moa Bay, Freeport Sulfur, Port Nickel, acid pressure leaching, pilot plant, pachuca, Chemical Construction, pressure letdown, cobalt, titanium

Jan 1, 2004

By S. Seetharaman

The present paper presents. the concept of micro-models and illustrates the application of the same in the simulations metallurgical processes. Development of micromodels requires access to accurate thermodynamic, thermophysicaland kinetic information for the relevant systems with suitable models to extrapolate the data as functions of temperature and composition. Experimental measurements and modelling of the thermodynamic properties, sulphide capacities and viscosities of oxide melts carried out in the department are presented. The incorporation of these models in process models, with special reference to ladle refining of steel is illustrated. Typical example of micro-modelling of solid-gas reactions is also presented.

Jan 1, 1999

By Djona M. Gaballah I.

Selective chlorination of unroasted and roasted spent hydrorefming catalysts was studied between 300 and 600°C using the following gas mixtures : C12+CO, C12+N2 and CI2+air. Such materials contain Co, Ni and Mo compounds supported by alumina and/ or silica. They also contain variable amounts of V compounds, C, S, etc., accumulated during the life time of the catalyst. Direct oxychlorination of the C+S rich sample allows higher extraction rates than those obtained by the carbochlorination of the same roasted one. It seems that the roasting step doesn't favor the economic metals' recovery. Results of the chlorination of C+S poor spent catalysts, in the presence of CO, in the chlorinating gas mixture, or of carbon added to the sample, were comparable. Cobalt and nickel chlorides were .extracted from the chlorination residues by their dissolution with acidified water, whereas molybdenum and vanadium chlorinated compounds were recovered by selective condensation from the vapor phase. The recovery rates of valuable metals as well as the selectivity were higher for the chlorination of spent catalysts than results obtained by the hydrometallurgical processing of the same sample. Results of the scale-up of the oxychlorination of the unroasted sample confirmed those of the laboratory scale. The global recovery rates were about 88 pct of cobalt, 93 pct of molybdenum and 76 pct of vanadium. The carbochlorination was applied to the recovery of W and Ti from Denox catalyst that is a carbon and sulfur free one. Recovery rates higher than 99 pct at temperatures lower than 500 °C could be obtained. This may indicate that the chlorination process can be applied to the treatment of various industrial wastes or by-product containing transition and/or refractory metal compounds A flow - sheet for the pretreatment of these materials is proposed.

Jan 1, 1995

By Xie Hao

According to its raw materials orthogonal test scheme is designed and a large number of systemic experiments were carried out in order to study the sintering characteristics of three types of fine ores in Kunming Iron&Steel Co.Ltd(KISC). The effects of carbon mixture ratio and basicity on sintering time, agglomeration ratio, physical properties and utilize coefficient were researched via single factor analysis and range analysis. The experimental results show the best mixture ratio of each fine ore. Analysis found that the influence of the carbon mixture ratio is more significant than which of the basicity on the sintering process except agglomeration ratio of foreign ore.

Jan 1, 2009

By B. Nowak

For sources with an iron-to-vanadium ratio of far above 1, it is proposed to leach in acid and to oxidize under autoclave conditions. During this oxidation process, it is experimentally shown that divalent iron contained in this solution will be oxidized to trivalent iron, whereas free acid contained will be consumed by this reaction. In case no acid is present or already fully consumed, a solid consisting of ferric compounds and an iron-vanadium-co-precipitate will form that can be filtered from the solution. If choosing the right reaction conditions, this filter cake has an iron-to-vanadium ratio of close to 1, whereas the liquid remainder is almost vanadium free. This precipitate, identified as FeVO4, 1.1 H2O, can be processed by conventional technologies such as caustic leaching, or probably salt roasting or reduction with aluminum, yielding common marketable products.

By Kuniaki Murase, Tetsuji Hirato, Koji Nitta, Yasuhiro Awakura

"The redox behavior of copper species in an ""ammonium imide"" room temperature molten salt was examined in order to clarify the applicability of the salt to the electroplating media of various metals. Trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)- amide (TMHA-Tf2N), having an electrochemical window of 5.6 V (50 °C), and corresponding copper(II) salt were synthesized. In TMHA-Tf2N media monovalent copper ion, Cu(I), was stable and Cu metal was oxidized, or corroded, in the presence of Cu(II) species. Cathodic electrodeposition of copper metal and anodic dissolution of it were, thus, one-electron reaction and their current efficiencies were almost 100%.IntroductionElectrodeposition of metals from aqueous solutions is an important soft process for manufacturing thin-film materials, surface finishing, and extractive metallurgy. However, the electrodeposition of base metals, such as zinc, chromium, and nickel, from aqueous media inevitably accompanies hydrogen evolution, which lowers the cathodic current efficiency of metal deposition. Since the electrodeposition of aluminium, titanium, and rare earths from aqueous media is actually impossible due to their largely negative redox potentials, nonaqueous media such as aprotic organic solvent and high-temperature molten salts have been employed for the electrodeposition of these metals. Room temperature molten salts (RTMS),1, 2) or room temperature ionic liquids, have also been developed as a promising electrolytes for the electrodeposition of base metals. In this field, chloroaluminates of alkylpyridinium or alkylimidazolium cation have been well investigated for aluminium3) or alluminium-alloy4-5) electroplating media. On the other hand, in order to avoid high hygroscopicity arising from the use of aluminium chloride, attempts have been made to combine the alkylimidazolium cations with fluorine-containing hydrophobic anions, e.g. BF4-,6) CF3SO3- (TfO-),7) (CF3SO2)2N- (Tf2N-),8) and H(HF)n-ions,9) and investigated for electrodeposition media.'°) Recently, a new series of RTMS consisting of tetraalkylammonium cations and Tf2N- anion, sometimes abbreviated as TFSI- anion, was found independently by MacFarlane et al.11, 12) and Matsumoto et al. 13) This type of RTMS, which is commonly named ""ammoniumimide"" salt, has a wide electrochemical window of ca. 5 V and, thus, the RTMS seems to be suited for practical application as a solvent for the electrodeposition process. In this paper, we report the electrochemical behavior of copper species in an ammoniumimide RTMS, trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)amide (TMHA-Tf2N)."

Jan 1, 2000

By K. S. Barros, D. C. R. Espinosa, J. A. S. Tenório

Over the past several decades, electrodialysis membranes have been employed for the removal of metals from galvanizing industry effluents. However, for its technical viability, it is useful to know some properties of the system to avoid, for example, precipitation of inorganic salts, destruction of the membrane and an increase in the energy consumption. The scope of the present study is to use chronopotentiometry to determine limiting current densities, transition times and resistances of the cationic membrane HDX 100 using a synthesized solution of the galvanizing industry effluent prepared with copper sulfate and sulfuric acid in different concentrations: 0.1, 0.5 and 1.0 g/L of Cu +2. The current-voltage and chronopotentiometric curves obtained have clearly defined regions and it was verified that the Cu+2 concentration causes a significant increase in the limiting current densities and in transition times. However, a high decrease in resistance occurred because at the highest concentrations, it is more difficult to reach the zero concentration value at the membrane surface. Besides, the pH increase causes a significant decrease in the limiting current density and in the transport number, but a slight increase in the resistance due to the presence of hydrogen. The results obtained confirm that the chronopotentiometry method is a valuable tool to determine membrane properties.

Mar 1, 2017

By N. M. Komkov

The main operation of obtaining zinc from sulfide raw materials by hydrometallurgical technologies is the oxidation roasting of zinc concentrates in fluidized bed furnaces. The technical-economic parameters are determined by the parameters of the roasting process, which depend on the composition of the initial raw materials, the temperature of the bed and on other factors. The predetermined roasting temperature is maintained due to the change of specific efficiency as well as to the quantity of the heat removed from the bed. The efficiency of caissons depends at a high degree on the composition and the thickness of the accretion formed on the surface of the caissons. Forecasting the roasting results is impossible unless we know the mechanism of the accretion formation. The aim of the present paper is the thermodynamic analyses of the behavior of the charge compositions under roasting and the determination of the potential mechanism of the accretion formation. The thermodynamic analyses show that under conditions of the oxidation roasting the thermodynamic probability of the formation of zinc sulfate is higher than the probability of the oxide formation until a temperature of 873°K is reached. The thermodynamic probability of the formation of the lead sulfate is higher than the probability of oxide formation in the entire temperature range of roasting. The probability of formation of ferrites and silicates of zinc decreases only insignificantly the sulfate stability. The results of the investigation of the accretions composition formed under roasting of concentrates with particle sizes less than 0.02 um (60%), containing 65% of sphalerite (ZnS), 12% of pyrite and chalcopyrite (FeS2 and CuFeSz2 each, 3% of galenite (PbS), 7% of silica and other non-ore minerals, have shown that the composition of accretion varies depending on the depth of the accretion layer. The accretions on the caissons and the thermo-siphons consist mostly of zinc sulfate (more than 50%). The accretions of forchamber consist mostly of zinc oxide. They also contain ferrites and silicates. The formation of the sulfate zinc accretion in the cold parts of the fluidized bed furnace (the caissons and thermo-siphons) may be explained by a lower temperature on the surface and probably by a catalytic influence of the present oxides in the formation of S02 and sulfates. The nature of the structure of the accretion in the hotter parts of the furnace may supposedly be explained by the formation of elemental vaporous zinc during roasting.

Jan 1, 2003

Several processes are now available for the recovery of free and WAD cyanide from gold plant solutions and pulps. In the past, the incentive for evaluating cyanide recovery in gold plant flowsheets has been economic. In many cases, it has been possible to demonstrate (at least in the laboratory and on paper), an improvement in process economics by; (i) reducing the costs of tailings detoxification, (ii) recycling cyanide at lower cost than the purchase/delivery price of new cyanide, and (iii) generating additional revenue via by¬product sales. Despite these convincing arguments, few cyanide recovery plants have been built at operating gold mines. Also, there is arguably an even more compelling reason for mining companies to consider cyanide recycling. With the growing storm of negative public opinion that the use of cyanide in the mining industry is attracting - following several highly publicized spills over the last couple of years - the time has come for the gold industry to demonstrate environmental diligence and stewardship in the use of this commodity that is so vital for their industry. There is no doubt that the widespread implementation of cyanide recycling will reduce the impact of the cyanidation process on the environment, both by reducing the risk of spills (with less cyanide being transported from manufacturing plants to gold mines), and by reducing the loading of toxic and non-toxic metals and ions in the tailings. In this paper, the various processes that are available for cyanide recovery are discussed, along with the process chemistry. Results of several laboratory and pilot plant trials that have been conducted over the last few years are also presented.

Jan 1, 1998