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By J. C. Agarwal

Most metals are produced from minerals containing one or more of the desired metals, some contaminating metals, silicate, oxides, carbonates, and sulfides. Therefore, in the production of metals, there is generally a gaseous effluent in pyrometallurgical processes and a liquid effluent in hydrometallurgical processes. There are also solid residues such as waste ore, tailings, dust, and slag, created by the metal recovery processes. There are two important distinctions between the effluents and the residues: I. Effluents ? gases and liquids ? affect the neighboring environment for miles from the point of emission, while residues affect only the soil on which they are stored or dumped. 2. The environmental and economic effects of effluents are known and felt essentially immediately. By contrast, the environmental effects of the residues may not be known for a long time. For these reasons, the economic impact and the potential corrective actions required are very different for effluents and residues.

Jan 1, 1992

By William Petruk

A mineralogical and image analysis study was conducted on samples of U tailings from pilot-plant runs on Midwest ore in Northern Saskatchewan. The tailings had been subjected to simulated weathering for the equivalent of 10 years in a tailings facility (lysimeter). The pH varied from 7.0 at the beginning of the test to 5.9 at the end. The results show that during the simulated weathering sane of the gersdorffite, uraninite, galena and pyrite had oxidized, with gersdorffite being the most reactive and pyrite the least. Reaction was evident at the top of the lysilleter , but was most intense at the seepage discharge. sane of the released ions precipitated as Ni, Pb, and U arsenates, sulfarsenates, sulfates and oxides on particles of all minerals. Green crystals of Ni sulfate and white crystals of ca sulfate had precipitated at the surface of the lysilleter. Clay minerals and chlorite had washed from the top of the lysirneter towards the seepage discharge.

Jan 1, 1989

By Li Cheng

The SKS copper smelting process was jointly developed by Shuikoushan Mining Corp. and ENFI (Beijing Central Engineering and Research Institute for Non-ferrous Metallurgical Industries) in China. It is a new bath copper concentrate smelting process with oxygen enriched air. The pilot plant testwork was completed successfully in 1993. SKS has demonstrated to be an advanced bottom blown smelting process. This technology got the First Class Prize of Scientific and Technological Progress awarded by CNNC (China National Non-ferrous Metal Industry Corp.) in 1994. The SKS process has significant capital and operating cost advantages. Its environmental and industrial safety and hygiene performance represents a substantial improvement when compared to conventional technologies. The technology has generated great interest in the Chinese metallurgical industry. Feasibility studies and basic designs have been carried out to incorporate in retrofit and green field smelter projects in China and abroad. This paper describes the history of the pilot plant operating data (50 tonnes dry feed/day), and discusses the features of the SKS technology, its application and possible future trends.

Jan 1, 1999

By Robert H. Hsu

Palladium finely dispersed in a substrate of kieselguhr, Pd/k for short, has been successfully used for hydrogen storage, separation and pumping for a number of years at the Savannah River Site (SRS). Recently SRS has developed a new pd/k flow through bed (FTB) prototype for separating hydrogen from other gases and simultaneously storing the hydrogen on palladium. The FTB uses single-pass liquid nitrogen cooling during hydrogen absorption/separation/storage and electrical heating for desorption/unloading of hydrogen. Fourteen absorption-desorption or loading/unloading cycles using hydrogen have been conducted with the new FTB prototype. Test results show that all design performance objectives have been successfully achieved: recover 295% of hydrogen gas from feed gas, produce 99.9% hydrogen product gas and < 5% hydrogen in discharge gas. This paper will discuss characteristics of the palladium-coated kieselguhr or diatomaceous earth, design and operation of the FTB, and results of performance tests such as separation efficiency, hydrogen storage capacity and system heat transfer characteristics.

Jan 1, 2002

By Batric Pesic

A hydrometallurgical process for recovery of Zn and Mn from Bunker Hill Water Treatment Plant sludge was developed. The process is unique because it treats an unusual combination of metals, Zn and Mn. Another non-standard feature of the process is that leaching takes place with ~S04 in the presence of a reductant (SO2). Zn and Mn are recovered simultaneously by electrowinning, Zn on a cathode and Mn on an anode, as MnO2 The major purpose of the process is to detoxify the sludge by removing toxic heavy metals. The recovered metal values could be marketed to offset the overall costs of water and sludge processing. This work is presented in two separate parts, 1. Leaching and Solution Purification, and II. Electrowinning. This paper covers only the first part of the hydrometallurgical process: Leaching and Solution Purification. Initially, the paper briefly discusses the history of the pollution problem at the Bunker Hill Superfund Site, the origin of heavy metals in the mine waters, and the development and use of the water treatment plant. The leaching of sludge was examined as a function of the following parameters: constant vs. initial pH, initial vs. delayed addition of SO2, temperature, and pulp density. It was found that leaching with H2SO4 at pH 2.0 for 15 minutes (at 60°C), followed by S02 addition for another 15 minutes, could completely dissolve Zn and Mn. Solution purifIcation was done in three stages. In the first stage iron was removed by adjustment of pH (to pH 5.0) and oxidation offerrous to ferric iron (with H2O2). In the second stage, Cu and Cd were removed by Zn dust cementation. Finally, Co and Ni were precipitated with the organic reagents 1-2 nitroso-naphthol and nitroso, respectively. Electrowinning of Zn and Mn is discussed separately in Part II of this paper.

Jan 1, 1996

By M. Kawakami

In relation to the designing of a new-type blast furnace, the reaction of carbonaceous materials with C02 is expected to occur at as low temperature as possible. In order to get a highly reactive carbonaceous material at low temperature, the reaction kinetics was investigated by measuring such quantities as the reaction rate from weight loss, the amount of CO adsorption and specific surface area by BET method. The reaction rates were large in the order of the Bintyo char, metallurgical coke, graphite and glassy carbon. If the rate was converted to the rate per unit area, however, those of the Bintyo char was smaller than that of graphite. Thus, it is suggested that the rate of the Bintyo char is influenced by the pore diffusion of C02. The rate had a positive relation with the amount of CO adsorption, showing that the rate determining step would be the desorption of CO from the active side on the surface. The rate independent of surface area was derived, combining al\ the obtained data.

Jan 1, 2003

By Tiffany Brown

In the thiosulfate gold leaching process, thiosulfate is used to complex gold following electrocatalytic oxidation of the native metal by Cu(II)-ammines. Unfortunately, Cu(II) complexes also catalyse the undesirable conversion of thiosulfate to polythionates. We have been seeking alternatives to ammonia, which fulfil the role of ammonia but minimize thiosulfate decomposition. One aspect of these studies has involved the determination of the rate of thiosulfate oxidation by the Cu(II) complexes from UV-Visible spectral changes. Various ligand classes, including pyridyls, polyamines, aminocarboxylates and picolinates, have been tested and the majority found to inhibit thiosulfate decomposition. Interesting variations in reactivity with the nature and denticity of the ligand and L/M ratio have been observed. In the case of open chain polyamine ligands with 2 to 5 nitrogen donors, the rate of thiosulfate oxidation was generally found to decrease with the denticity and the concentration of each ligand. Saturation of the Cu(II) coordination sphere appears to inhibit the oxidation of thiosulfate when excess thiosulfate is present. The Cu(II) complex of the branched polyamine ligand, tris(2-aminoethyl)amine (tren) exhibits this behaviour in excess thiosulfate. Interestingly, when the [Cu(tren)(OH2)]2+ complex is in excess oxidation of thiosulfate was observed. This unexpected finding prompted a spectrophotometric study of this reaction which has revealed that the oxidation of thiosulfate involves several processes, two of which involve the formation and decay of a tetrathionate radical.

Jan 1, 2003

By Ali Akbar Mottahedi

Chromate conversion coating is a process for making a complex layer at the surface of zinc galvanized steel which makes the metal more resistant to corrosion, especially at marine atmosphere, and increases the adhesiveness of color. In this work the influences of various compositions on commercial zinc galvanized steel sheet to the color of chromate conversion coating has been investigated at normal temperature and the factors that affect the control and optimization of the process have been determined. A bath composition of 20 g/liter Cr203 and 10 g/liter NaOH and a dipping time of 50 seconds at room temperature (25-30°C) make a desirable color of chromate coating. A slow agitation at a constant pH of I (with additions of NaOH or H2SO4) assures a constant bath condition and develops the color. This kind of coating has more corrosion resistance and this bath condition and composition are also more economical.

Jan 1, 2003

By L. Y. Zhang

The current status of metal hydride alloys for NiMH batteries was systematically reviewed. Extensive application-oriented research and development has successfully made the NiMH battery an important part, with growing potential, among rechargeable batteries. The rare earth based metal hydrides (AB5) have been considered the best alloy material for use in the negative electrode in NiMH batteries. However, being in demand for high performance electronic markets, the still young NiMH industry is facing serious technical challenges in developing better products. Among all the efforts to respond to the challenges, advanced AF3, alloys are in great demand: the capacity enhancement race requires new or improved alloys possessing higher volumetric capacity; price competition mandates MH materials with low cost; high performance under severe service environments calls for alloys with high corrosion resistance when subjected to electrochemical cycling; and finally, high power service requires the negative electrode to deliver current at high rates.

Jan 1, 1997

By Michael S. Moats, Alexander Derrick

"The Winand Diagram was developed and has been used for decades to illustrate the interaction between polarization, mass transport and inhibition on the resulting structure of a metal electrodeposit. Recently, Adcock et al. criticized the Winand Diagram and developed their own structural diagram based on nucleation and plating overpotentials. Their work was based on zinc electrodeposition using a galvanostatic staircase method. This work explores the nucleation and plating overpotentials for copper electrodeposition using conditions typical for primary electrowinning and the galvanostatic staircase experimental technique. Additionally, the effects of organic additives and plating substrate on these overpotentials are reported.IntroductionThe control of electrodeposited structures is critically important to modem electrometallurgy operations to insure proper quality and efficient energy use. Electrodeposition of base metals for primary recovery (e.g. electrowinning or electrorefining), while similar to plating for decorative or device manufacturing, differs in the need to produce deposits that cover large areas and grow to significant thickness. Thus, controlling nucleation and particularly growth of electrodeposits is critically important for base metal electrometallurgical operations.The control of nucleation and growth on an industrial scale is most influenced by five parameters - current density, temperature, metal concentration, electrolyte agitation and additives. The effects of these parameters on electrodeposition are interrelated. To describe their effects on the type ofelectrodeposits generated and provide practitioners with a useful tool, Winand developed what is known as the Winand Diagram [1-2]. An adapted version of the Winand Diagram is shown in Figure 1.Winand characterized electrodeposits using Fischer's classification [3] and plotted the various deposit types versus inhibition on a vertical axis and the ratio of current density to bulk metal concentration on the horizontal axis. Inhibition intensity is a complex parameter and is still not well understood even though Fischer introduced the term in 1960 [4]. Often, inhibition intensity is simplified to equal the concentration of organic additive at the deposit surface and is related to the inverse of the exchange current density of the metal being deposited. The ratio of current density to bulk metal concentration is used to represent the ratio of crystallization overvoltage to mass transport of the depositing ion. As such i/iL could also be along the horizontal axis, where iL is the limiting current density of the electrodeposition reaction."

Jan 1, 2012

By L. L. Tavlarides, N. V. Deorkar

"Recovery/Recycling of metal ions from industrial process waste streams is a preferred alternative to disposal by conventional techniques. This paper presents methods for preparation of inorganic chemically active adsorbents to be used in fixed bed adsorbers. Methods for immobilization of chelating agents on the inorganic supports are discussed. The prepared adsorbents are characterized to determine coverage density of functional groups, effect of pH on metal ion removal efficiency, regeneration efficiency and uptake capacity. Results from the laboratory scale and bench scale experiments are presented here.IntroductionRemoval of heavy metal ions from processing wastes in various industries is an important problem. Waste streams in electroplating, electronic, catalyst preparation and hydrometallurgical industries contain metal ions such as copper, nickel, chromium, lead, tin, cadmium, silver, gold and platinum. One major concern for the non-ferrous metal industry is secondary recovery of precious metals and cyanide from cyanide leachate from smelter residue and hydrometallurgical waste streams.Recovery methods recently considered include evaporation, electrolyte metal recovery, reverse osmosis (1), adsorption, ion exchange (2,3), membrane separation (4,5) and Solvent extraction. These processes have met with various levels of limited success. The use of liquid ion exchange molecules to selectively extract metal ions for on-site treatment of these waste streams is currently receiving substantial interest (6,7). This interest seems from an awareness of the advances made in the development of commercial extractants for metal ion separation in hydrometallurgical industries (8). However, separation by solvent extraction processes is generally considered to be economical in the range of aqueous metal ion concentrations from 0.01 to 1.0 mol/lit (9). In order to exploit the selectivity of chelating agents, the idea of immobilizing chelating agent into a solid matrix has attracted growing attention in recent years. Many supports such as inorganic oxides, organic polymers, cellulose powder and polyurethane foam can be used for immobilization of chelating agents. Over the last decade, considerable efforts have been directed toward attachment/introduction of chelating agents into a polymer matrix (10,11). Inorganic supports as compared to polymer supports provide high mechanical strength, chemical and thermal stability, and high reaction rates due to open pore structure. On the contrary, organic resins shrink and swell, thus affecting mass transfer (12). Many of the disadvantages of polymer supports can be excluded by the use of inorganic supports. Innovative use of immobilization techniques can produce inorganic chemically active adsorbents with comparable capacity, stability and reaction rates. Consequently, the objective of our program is the development of inorganic chemically active adsorbents to be used in a fixed-bed unit operation as an alternative heavy metal ion recovery process. Methods of preparation of inorganic chemically active adsorbents, (ICAAs) characterization and applications are discussed in this paper. A brief summary of the results from laboratory scale studies and bench scale studies is presented."

Jan 1, 1996

By Sergei A. Degterov

A thermodynamic database for the slag, matte and liquid copper phases in the Cu-Ca-Fe-Pb-Zn-Si-O-S system has been developed for the ranges of compositions of importance to the production of copper. When used with the Gibbs energy minimization software and other databases of the F*A*C*T thermodynamic computing system, this database will permit the calculation of matte-slag-copper-gas phase equilibria that take place during copper smelting and converting. The calculations reproduce within experimental error limits all available experimental data on phase diagrams, activities of components, enthalpies of mixing, matte - alloy miscibility gap and tie-lines. The calculated solubilities of Cu in both S-free slag and slag equilibrated with matte are also in good agreement with experiment under all studied conditions, such as at SiO2 saturation, in equilibrium with Fe, Cu or Cu-Au alloys, at fixed oxygen or SO2 partial pressures and at different contents of Pb, Zn and CaO in the slag. Sulfide contents (sulfide capacities) of the slags are predicted within experimental error limits. The distribution of Pb and Zn among matte, slag, copper and gas has been calculated. The calculations are in good agreement with experimental data and predict the distributions under conditions which are difficult to study experimentally, such as at magnetite saturation or under various oxygen partial pressures and iron to silica ratios in the slag.

Jan 1, 1999

By V. Bredykhin

The efficiency of scrap processing depends firstly on reliability of information about its chemical composition. The paper presents the results of the investigation and development regarding solid copper alloy scrap in the range of lump size 40÷300 mm. Nowadays the sorting of lump scrap is done by two methods: 1. Sorting according to metals and alloys is done at places of scrap generation, and further till metallurgical processing each lot has its "certificate"; 2. Hand sorting of scrap is done according to the marks on solid items in special shops using proximate analyzers or manually by experienced workers. This sorting process is labor - consuming low efficient and involves mistakes. The informational method is a promising trend in the copper scrap sorting. The method is direct, i.e. as a result of sorting the chemical composition of each scrap lump or main elements is determined, and assured data of qualitative and quantitative composition are received.

Jan 1, 2006

By Zdzistaw MiGzkowski

At KGHM Polska Miedi S.A. a direct flash smelting process is used for smelting of chalcocite concentrate for the production of blister copper. The paper presents a model of complex oxidation process of single concentrate grains smelted at KGHM. The description covers main chemical reactions, phenomena of heat and mass ex-change inside the grains and between a grain and the surrounding space. In the model, two zones describing the course of process inside the grain were distinguished: ? The first one, which moves faster towards the centre of a grain, both organic and carbonate carbon are freed. The process takes place without the presence of oxygen and results in an increase of the temperature in the core of the particle. ? The second zone moves slower into the grain and the rate of the movement is deter-mined by the presence of oxygen. In that zone the sulphur is eliminated and the oxidation of the organic compounds vapours moving from deeper layers of a grain takes place. Based on the results of laboratory tests, the coefficients that describe the oxygen transportation into the grain and decide the progress in the chemical reaction were determined. The paper contains the results of model calculations for single grains reacting in environment of various content of oxygen as well as the results of model calculations for the laboratory reactor system.

Jan 1, 2003

By Ian M. Ritchie

Cementation or metal displacement reactions such as Cu2+ + Fe Cu + Fe2+ are among the oldest known hydrometallurgical reactions. They are still used in the recovery of some metals and in the purification of process liquors and waste water streams. However, they are often more complex than the stoichiometric reaction would suggest because they involve the simultaneous deposition of one metal onto a second which is dissolving. For example, sometimes a cementation will not take place, even though it is thermodynamically favoured. On other occasions, a cementation reaction will start but come to a halt as the depositing metal blankets the reacting surface. On yet other occasions, side reactions, catalyzed by the deposit, can be important. In this paper, the electrochemical basis of cementation reactions is described. The conditions for each of the complications encountered in these reactions are described and illustrated by examples drawn from a number of hydrometallurgical processes. The cementation reaction between activated carbon and gold thiosulfate is also briefly described, this reaction being unusual in that no dissolution of the carbon occurs.

Jan 1, 2003

By S. -H. Jeon, Y. -S. Choi

"The three dimensional current distribution on the rectangular cathode is predicted using a boundary element method with a linear element of trigonal type. The effect of cell geometry and anode shape on current distribution is simulated. Calculated results compare well with experimental results. The proper combination of anode size and distance between electrodes increase the current uniformity.The importance of electrodeposition as a fabrication technology in the electronics industry is large and growing. The main advantages of this wet processing method, in comparison to other dry processing methods, lie in its high yield, rapid processing and low cost. In nearly every application of electrodeposition the pursuit of deposit uniformity, especially thickness uniformity, has been technically imperative. The thickness uniformity of the deposit depends largely on the current distribution over the cathode. The current distribution is primarily determined by the geometrical characteristics of the electrodes and the cell. Also the polarization at the electrode surface and the mass transfer affect the current distribution.The current distribution is an important consideration for those involved in designing electrochemical systems and electroplating systems in particular. Although it is important, the common practice in industry is to use trial and error method to design the cell that optimize the uniformity of current distributions in electroplating. The purpose of this paper is to illustrate the useof boundary element method to predict three-dimensional current distribution in rectangular cell.The calculation of the current distribution is possible by various numerical techniques, which include the finite difference method (FDM)1, the finite element method (FEM)2, and the boundary element method (BEM)3,4. These methods of the numerical calculation have various problems, respectively, but the BEM is considered to be the most efficient. This is due to the fact that the BEM has the advantage of solving field equations only on the surface of a calculation domain. A good comparison between the BEM and the FEM for the secondary current distribution in a Hull cell was made by Matlosz et al.5The fundamentals on the theory of current distribution in electroplating are well-established in the literature by a number of authors.6, 7, 8 However, a small fraction of these works have been specially addressed to three-dimensional analysis, and, mostly thel·10 have focused on the problem qualitatively rather than quantitatively.Extending the previous work to three-dimension, we developed the program for the quantitative calculation of 3-dimensional current distribution using a boundary element method with a linear element of trigonal type. Integrals with singularity from the fundamental solution have been analytically computed and it is shown in detail in the Iiterature11. This paper deals with the three dimensional current distribution for the electrode position of copper in a cubic type cell and the effect of anode shape, size and the distance between electrodes on current distribution is studied."

Jan 1, 1997

By Yang Tian-zu

The separation of precious metals from base metals containing in gold-antimony alloys by selective chlorination leaching under controlling potential was studied in this work. The effects of the consumption of hydrogen peroxide, the concentration of hydrochloric acid, the concentration of sulfuric acid, leaching temperature, leaching time and the liquid-solid ratio in hydrochloric acid system on the leaching efficiencies of the base metals have been investigated. The optimal leaching conditions of the gold-antimony alloys are as follows: hydrochloric acid concentration 4.0mol?L-1, sulfuric acid concentration 1.2mol?L-1, liquid-solid ratio L:S=7.5:1, the leaching temperature 80 0C, leaching time 2h, and the oxidation potential of the leaching system 400±20mV( vs SCE).The leaching efficiencies of copper, nickel and antimony are more than 99% and the gold leaching efficiency is about 0.042% under the above leaching conditions. The base metals containing in the gold-antimony alloy are separated from the precious metals thoroughly.

Jan 1, 2006

By Ryokichi Shimpo, Akio Fuwa

"In order to elucidate the present status of process-control technology, survey study has been made on the present process control schemes of representative copper smelting and converting processes in Japan. Conceptual control flow diagrams have been deduced and shown on respective functional reactors, i.e. drying, smelting, converting and fire-refining units, where the objective OUTPUT items are correlated to the INPUT variables through respective CAUSE-AND-EFFECT RELATIONSHIPSFuture view has been also discussed on several feasible and desirable improvement and refinement ~n measurements and control system for better copper smelting and converting operations.INTRODUCTIONIn other to seek for the better and efficient operation in copper smelting and converting process, survey study has been first conducted on the present process-control schemes of respective functional unit processes, i.e. drying, smelting, converting and refining unit processes, of representative copper production processes in Japan. Conceptual process flow chart of control scheme has been then deduced where output items are correlated to input items through the respective cause-and-effect relationships.After this survey study, future view has been discussed on the feasible and desirable improvement and refinement in the measurement and control system in these processes. Emphasis has been placed on the better and precise measurements of temperature, oxygen partial pressures in respective furnaces and end-point in converting and refining unit operations."

Jan 1, 1989

By N. S. Narayanan

Monazite, one of the major sources of rare earths, is normally opened by digestion with hot concentrated caustic soda solution. Caustic digestion dissolves phosphate and leaves a hydrated mixed metal oxides cake containing thorium, uranium and rare earths. By leaching this cake with hydrochloric acid at pH 3.0 to 3.2 bulk of the rare earths are preferentially removed and separated. The slurry left after removal of major portion of rare earths contains all the thorium and uranium present In the feed monazite. In addition this slurry also contains substantial quantities of rare earths. Solvent extraction tests were carried out to develop a process to separate rare earths, thorium and uranium present in the mixed chloride solution obtained by dissolving the above slurry in hydrochloric acid. Based on these tests a solvent extraction flow sheet was developed with di-2-ethyl hexyl phosphonic acid mono 2-ethyl hexyl ester as the extractant. The details of experimental work and results obtained are discussed and a flow sheet for processing monazite Incorporating the new process is suggested.

Jan 1, 1997

By Blas Melissari, Stavros A. Argyropoulos

"In this paper a computational approach was employed to estimate the melting of solid spheres immersed in different liquid metals and under different convective conditions. The spheres are made from the same material as the liquid metal. The SIMPLER algorithm was implemented using a three-dimensional system in Cartesian co-ordinates. Experimental validation of the dimensionless correlation was carried out in two fluids with vastly different Prandtl numbers. The dimensionless heat transfer coefficient (Nusselt number) is obtained as a function. of the Reynolds and Prandtl number.IntroductionThere is a paucity of dimensionless convective heat transfer correlations applicable to fluids like liquid metals. The existing correlations cover single Prandtl number metals [l] or at most two different Prandtl number metals [2]. A knowledge of heat transfer rates from particles at high flux levels has become increasingly important to the design of energy transfer systems. Melting of solid particles has been studied extensively as it relates to many engineering and environmental applications, such as materials processing, space applications, water resource and energy conversion. When objects are immersed in a fluid with a temperature higher than their melting point, they melt and produce molten material that then mixes with the surrounding fluid. These objects experience not only size variation but also changes in their shape. This observation is more pronounced when the melting occurs in a forced convective flow.Yuge performed pioneering experimental work on the heat transfer from a sphere to air under mixed convection [3]. He suggested procedures for predicting the Nusselt number. Hieber et al [4] studied the spherical system analytically, but their study was limited to flow with small Reynolds numbers. Many researchers studied the melting dynamics of ice spheres in water at different convective regimes. Aziz et al [5] and Hao et al [6] performed measurements of the heat transfer coefficient in the water system by measuring the melting time of ice spheres in forced convection. Hao et al [7] performed visualization studies of ice spheres melting in water under mixed convection regime. All of this groundbreaking work, however, did not involve the use of liquid metals"

Jan 1, 2004