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By H. Y. Sohn

The purpose of this article is to analyze critically and quantitatively the effect of chemical equilibrium on the overall rates of fluid-solid reactions. It is shown through a mathematical analysis that a reaction with a small equilibrium constant (a positive standard free energy of reaction) is more likely to be rate-controlled by pore diffusion or mass transfer than a reaction with a large equilibrium constant. The overall reaction rate of the former also tends to be slow. Furthermore, the apparent activation energy of such a reaction approaches the standard enthalpy of reaction (M-f'), rather than the true activation energy of the chemical reaction. The Law of Additive Reaction Times developed by the author is shown to apply to equilibrium-limited fluid-solid reactions and to be useful in quantitatively analyzing the behavior of such reactions.

Jan 1, 2003

By James A. Voigt

The efficient separation of metal species from aqueous streams by precipitation techniques requires 'a fundamental understanding of the various processes that occur during precipitation. These processes include particle nucleation, particle growth by solute deposition, agglomerate formation, and agglomerate break-up. The application of the population balance approach has been used to develop a kinetic model that accounts for these competing kinetic processes. The usefulness of the model is illustrated through its application to the precipitation of yttrium hydroxynitrate, YHN. The kinetic parameters calculated from the model equations and system-specific solution chemistry are used to describe several aspects of the effect of pH on the precipitation of the YHN. Implications with respect to the simultaneous precipitation of more than one cation type are also discussed through use of example systems: The effects of solution chemistry, precipitator design, and solvent choice are considered.

Jan 1, 1996

By Songsong Wang

Recently, replacing Pierce-Smith converting process with the oxygen bottom-blowing continuous converting technology has become a new research focus. Based on the principle of Gibbs free energy minimization, the thermodynamic model of oxygen bottom-blowing continuous converting multiphase equilibrium system has been established. The elements distribution behavior is calculated at the same burden composition and operation parameters as the industrial production. The results show that the absolute errors of the mass fraction (wt%) of Cu, Fe, S, Pb, Zn, As, Sb, Bi in crude copper are 0.06, 0.0030, 0.070, 0.38, 0.39, 0.020, 0.017, 0.034, 0.010, respectively, and the absolute errors of the mass fraction (wt%) of Cu, Fe, S, Pb, Zn, As, Sb, Bi in slag are 0.53, 0.81, 0.020, 0.23, 2.5, 0.0048, 0.0010, 0.0030, 1.49, respectively. The calculated results agree well with the actual industrial production data, indicating that the model can be well applied in the oxygen bottom-blowing continuous converting practice.

By Lin Li, Xiang Li, Yifang Zheng, Jilai Xue, Jun Zhu

"Al drops and gas bubbles in the anode-cathode space of aluminum electrolysis cell are of great importance for cell operation improvement in metal loss, current efficiency and energy consumption. A direct observation on the Al drop, gas bubble and ultrasound was carried out through a see-through cell. The Al drop immersed into the cryolitic melt was found moving up and down irregularly in the anode-cathode space without electrolysis, which was then completely dissolved into the melt. During electrolysis, the Al drop came to the anode area and reacted with the gas bubbles generated on the anode. Under ultrasound, the gas bubbles were removed from the anode surface while the Al drop was kept on the side of anode. The observed phenomena were useful for technology improvement in reducing the anode-cathode distance or lowering the energy consumption in aluminum electrolysis.IntroductionDuring aluminum electrolysis, aluminum metal drop and anodic gas bubble are in close contact each other within the anode-cathode space, and the interaction between them can produce significant impact on metal loss, current efficiency and energy consumption. The motions of the Al drop and the gas bubble are also related to the dissolution of aluminum metal into cryolitic melt and the cell voltage drop due to the bubble layer covering the anode surface.A number of studies have been carried out using different types of see-through cells, where the dissolving process of metal Al into cryolitic melts (metal fog) in the anode-cathode space was directly observed and photographed [1, 2]. With the similar method, some direct observations on the anodic bubble behaviors with and without ultrasound were performed during aluminum electrolysis [3-6]. However, to our best knowledge, there is no published work on direct observation on the behavior of Al drops and anodic gas bubbles staying together within the same anode-cathode space, as well as the motion and interaction of them in cryolite-alumina melts."

Jan 1, 2011

By T. J. White

Each year, thousands of tons of toxic concentrates are produced as the unwanted byproducts of industrial operations and smelting activities. The fate of these materials remains open, as in general their consumption is limited and potential markets contracting. Xtaltite (pronounced crystal-tight) is a Synthetic Mineral Immobilization Technology (SMITE) optimized for the concentration, detoxification and consolidation of toxic metal wastes. In this approach, we seek to mimic nature to produce durable synthetic minerals that survive for aeons in well characterized geological settings. This approach has high public acceptability because the concept is easily understood by the layperson and the long term stability of the waste form may be predicted with confidence. In addition, where Xtaltite is used for mine backfill, a system of ecologically sustainable mining development is established. This paper details the design and fabrication of Xtaltite under oxidizing and reducing conditions. To illustrate and contrast these stabilization regimes, specific reference will be made to the treatment of thallium, chrom~um and arsenic wastes. Waste form performance under TCLP, dynamic boiling water tests and in other leaching media will be compared and discussed with respect to their relevance to different disposal options.

Jan 1, 1995

By P. J. Uggowitzer, H. Kaufmann

"New Rheocasting is a novel route of semi-solid casting, in which the globular semi-solid precursor material is produced by controlled cooling of only slightly superheated melts in conventional steel crucibles. The resulting semi-solid slugs are placed into the sleeve of a vertical Squeeze Casting Machine and then filled into steel dies. Solidification occurs under hydraulic pressures up to 100 MPa Due to the reduced cost of precursor material, reduced investment cost and easier recycling, the New Rheocasting process offers cost reductions of up to 25% over conventional semi-solid casting · routes. The New Rheocast products are pore free, pressure tight, weldable and heat treatable castings.In the present work the New Rheocasting Process is introduced and the influence of heat treatment on mechanical properties of the New Rheocast alloy A356 is discussed.The alloy A356 is cast under ideal New Rheocasting conditions into a step die on an UBE HVSC 350 Squeeze Casting machine. As-east, TS and T6 heat treatment conditions with variations in solutionizing and aging time/temperature parameters are applied and the samples are tested by tensile testing. Alternatively, the same heat treatment conditions are applied to conventional Squeeze Casting parts and compared with New Rheocasting.Questions of potential cost savings due to modified heat treatment conditions are also addressed in this paper."

Jan 1, 2000

By John R. Goode

The fist part of this paper comprises a general discussion on refractory gold ores and their mineralogy. Processing methods now in use are reviewed and test procedures for the important methods are discussed. Factors determining the selection of a process are outlined. The paper includes a survey of production plants using pressure oxidation, roasting and biological oxidation to process refractory ore. The status of processes under development is briefly reviewed.

Jan 1, 1993

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 Cajsa Samuelsson, Theo Lehner

Converting and refining play a central role in the extraction of metals. Sweden has a long tradition as an experimental play ground for metallurgists, chemists and alchemists, developing new methods and technologies. Presenters of papers are usually happy in recording successful developments. But reporting failures can be as great a value as the former. In the paper experiments and experience in process development are illustrated, differences between ferrous and non-ferrous developments are highlighted and industrial learning curves are discussed. 53

Jan 1, 2009

By C. -S. Jiang

In most copper refineries, addition agents are added at predetermined rates with no further monitoring of their activity or concentration in the electrolyte. Increasingly stringent cathode quality requirements, and a desire for better process control in tankhouse operations, have recently directed a number of refineries to search for a better addition agent control strategy. Extensive development work has been carried out at the Noranda Technology Centre for the monitor in of glue and thiourea in copper refinery electrolyte using cyclic voltammetry (cv~. Data from both synthetrc and commercial electrolytes are presented, showing the ability of CV to produce reliable and easily identifiable fingerprints of addition agent concentrations in copper refinery electrolyte.

Jan 1, 1991

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 Yu Hu, Gabriella Tranell, Song Zhang, Eivind Johannes Øvrelid

"In the present research, recycling feedstock of silicon for Photovoltic (PV) application is investigated. Whether these recycling feedstocks are reliable in the future use is discussed in this work to assess the properties of the crystal silicon ingot, which is commercially pulled from top-cuts of casted multicrystalline ingot via one kind of Czochralski method - FerroTech. Dopant is the acceptor type Boron (B) and growth direction was <100>. Crystal diameter and the length were 190mm and about 1700mm, which were controlled by the temperature and the pulling speed, then cut to 156mm * 156mm wafers with 2000um and 200um thickness. Resistivity measurements of these wafers by Four Point Probe (FPP) are in good agreement to the calibrated profile after Rapid Thermal Process (RTP). In this work, the Minority Carrier Lifetime MCI, shown by Carrier Density Image (CDI) and Quasi Steady State Photo Conductance (QSSPC), gives the mapping results on the cross section and the relationship to the injection level, increases in an arrange from 40us to 90us along the ingot height, which is abnormal distribution compared to the standard ingot. Then Oxygen and other metal impurities distributions, measured by Flourier Transform Infra - Red (FTIR) respectively, account for the novel phenomenon of the continuously increased MCI. Various types of heat treatments were performed on these wafers (different ingot and different positions) in N 2 and 0 2 mixture atmosphere. Before and after heat treatment, micro-defects were revealed by copper decoration and etching work. Solar cells are fabricated by Energy Research Center of the Netherlands from the experimental ingot, and processed under an industrial standard line. Compared to results of the reference mono-crystalline and multi-crystalline silicon solar cells, the performances of experimental ones show excellent efficiency values up to 18.5%, and Jsc values up to 37mA/cm2.IntroductionThe PV industry has gone through rapid development, with a high growth rate resulting in an increasing demand for silicon feedstock. In addition, costs in production need to be reduced such that solar energy can compete other conventional and renewable energy. Searching low cost, reliable and efficient feedstock is one promoting way to improve and enhance the competitiveness of the PVindustry.More and more researchers start searching new raw materials for PV application [1]-[4]. The key to make full use of low cost raw materials is to control the distribution and effect of impurities, such as Carbon, Nitrogen, and other metal contamination [5]."

Jan 1, 2013

By H. Fukuyama

The wetting behavior of single crystalline MgO by fayalite-type slag melts has been studied by the sessile drop technique incorporated with high temperature X-ray radiography. The experiments were performed under oxygen partial pressures of 10-6 and 10-4 Pa at 1473 K. Mass ratios of iron to silica, Fe/Si~, in the slag employed were 1.4 and 2.0. To investigate the interfacial reaction, experiments using high density MgO crucibles were also conducted. The reactions at the interfaces were examined by Electron Probe Microanalysis. The contact angles between the slag melts and the MgO substrates were found to be relatively low, ranging from 30 to 10 degrees. The surface tension of the slag was 0.4 N/m for a slag of Fe/Si02 = 2.0. Two phases, magnesiowiistite and olivine, were observed at the interface. Interdiffusivity in magnesiowiistite solid solution was determined as a function of iron oxide content. Phase relations between magnesiowilstite and olivine, and the growth rates of both phases, are also discussed

Jan 1, 1996

Equilibrium calculational software programs can be effectively utilized to illustrate the importance of activity or concentration, solubility, temperature, solution pH, solution potential, and ligand complexation to students studying hydrometallurgy. The calculational program STABCAL will be demonstrated. illustrative examples for the creation of diagrams such as EH-pH, activity or concentration-pH and activity or concentration-EH will be presented to demonstrate the fundamentals of real hydrometallurgical systems. Speciation, titration and mixing will be used to simulate or predict operational processes. Applications will include treatment of Acid Mine Drainage (Berkeley Pitlake water and sediments), mass balance potential/pH diagrams, leaching and selective separation of metals from electroplating sludge, metal adsorption at femhydrite surfaces, and flowsheet development for treating mercury sulfide K106 sludge.

Jan 1, 2002

By K. Fagerlund

Methods for simulation of settler reactions, matte-slag separation and matte settling in copper flash smelting have been examined. The reaction, separation and settling phenomena of slightly oxidized chalcopyrite samples and cuprous sulfide-magnetite mixtures in fayalite type slags were examined at about 1300°C under inert atmosphere. Two methods based on introduction of molten samples of oxidized chalcopyrite concentrates or synthetic matte-magnetite mixtures onto the surface of molten iron silicate slag were tested. In the first method the samples were water quenched and polished specimens were studied and analysed using light optical microscope, scanning electron microscope, energy dispersive spectrometer. In the second method processes taking place after the introduction of samples onto the slag are followed "in situ" using X-ray transmission image monitoring. Great differences were observed in separation and settling behaviour of low and high grade copper mattes produced as a results of interaction of initial samples and slag.

Jan 1, 1997

By R. Stefaniuk, T. Le, J-Y Huôt, H. Henein

"One of the most important process variables in gas atomization is the gas to metal (G/M) mass ratio as it has a direct effect on the mean particle size of the atomized powder. If this ratio can be controlled during the atomization process, the powder produced would be more uniform and the d50 more predictable. Thus, atomization using a tundish or gravity feed from a crucible would be more stable. In gas atomization, the gas flow rate can be easily monitored; while it is very difficult to determine the molten metal flow rate. This research paper presents a new method of recording the molten metal height with time using a conducting metal height detector. The metal height recorded in real time during atomization was used to characterize using a model the friction losses in the metal delivery system. It is found that the integrity of the metal delivery tube and the cleanliness of the melt play a key role in the maintaining a stable metal feed.IntroductionIn the gas atomization process, molten metal is normally fed to the system either continuously using a tundish or in most cases a certain amount of metal is melted in a crucible and flows into the atomizing chamber under gravity. In the first case, the metal flow rate is believed to be constant during the atomization process despite the presence of slag or dross on the molten metal surface. In the second case, the amount of molten metal is depleted with time and the rate at which the metal flow decreases with time varies from test to test in a seemingly unpredictable fashion.' Furthermore, most atomization systems are confined units and the metal level in the crucible cannot be detected by a visualization method. In industry as well as in laboratories, the metal flow rate is normally calculated on either the mass of input material or the mass of total production divided by the duration of the test. This figure is not accurate enough and obviously cannot be used as a control parameter for the gas to metal ratio as it is only determined after the completion of an atomization run. The need exists for a metal flow rate measurement and control methodology; thereby the d50 of the powder produced may be estimated and controlled in real time. Clearly, the smaller the variation of the G/M ratio during the atomization process the more uniform the powder produced and hence the size of the particles can be predicted."

Jan 1, 1994

By Benoit DeBecker

Laboratory-scale experiments have shown that chromium metal could be recovered from chromate wastes by modifying slightly the chromium electrowinning flow-sheet. After reduction by sulhr dioxide and precipitation of chromic hydroxide, the solid residue is dissolved in the chrome alum solution and the metallic impurities are removed by cementation on manganese. The presence of dissolved manganese in the electrolyte does not affect the cathodic deposition of chromium and it eliminates the anodic production of Cr(V1).

Jan 1, 1994

By C. A. Nogueira, F. Margarido

"A research work has being carried out annmg at evaluating the possibility of treating simultaneously several electrochemical systems of spent batteries using the same process, in order to overcome the high costs and difficulties of selective collection and sorting. Zn-Mn02 systems, representing more than 75% of portable battery market, shall be treated in dedicated processes. The treatment assessment using a single hydrometallurgical process of the other major systems (NiCd, NiMH and Li-ion), having Ni and Co as main metals, was the aim of the research work here reported. Sulfuric acid leaching was demonstrated to be adequate for dissolving more than 90% of the metals of interest contained in batteries. The subsequent separation of metals by solvent extraction, using organophosphorous extractants like DEHPA and Cyanex 272, allowed the production of pure solutions of rare earths, cadmium/manganese, cobalt, nickel and lithium, enabling their further recovering.IntroductionRecycling is the best approach for end-of-life management of spent batteries mainly by environmental reasons but also motivated by resources conservation and, in some cases, by economic profits. Most relevant electrochemical systems of portable cells are Zn-Mn02 (ZMB, alkaline and saline), nickel-cadmium (NiCd), nickel-metal hydride (NiMH) and lithium-ion (LIB). These batteries are collected, sorted and usually treated separately, applying for pyrometallurgical or hydrometallurgical technologies, the former being the most common.Several processes have been developed and some of them industrially applied, as described in some available review papers [l, 2]. In Europe for ZMB systems the oldest processes are Batrec [3] and Citron [4]. Although having differences in details, both are based on pyrometallurgical recovery of zinc by distillation, in metallic or oxide forms, being manganese retained in the slag together with iron. Hydrometallurgical alternatives are also available, like Zincex [5] and Recupyl [ 6] processes, both using sulfuric acid solutions as leachant. The application of the existing technologies to battery recycling, instead of using dedicated processes, is other alternative already tested, being the Waeltz furnace or the Imperial Smelting some examples."

Jan 1, 2012

By Kafui Nyavor

The indirect, and the direct contact mechanisms of bacteria oxidation of sulfides were studied using Thiobacillus ferrooxidans and pyrite. The aim was to determine which of the two generally aeeepted mechanisms played a dominant role, if any, during acid mine drainage (AMD) formation from the oxidation of sulfide minerals. The results show that at a pH of 4.5 where T. ferrooxidans are quite active, but where initial chemical oxidation of pyrite to Fe2+ is limited, the bacteria were unable to directly oxidize pyrite to any significant extent. Whereas, in the presence of Fe2+, T. ferrooxidallS assisted oxidation of pyrite by the indirect mechanism was observed and sustained over the pH and Eb range where the bacteria is active. The results lead to the conclusion that the direct contactmechanism of pyrite oxidition by T. ferrooxidans is insignificant. The predominant, and possibly the only, pathway involves the indirect bacteria oxidation of available Fe2+ to Fe3+, which in turn oxidizes FeS2 to generate additional Fe2+ and acidity in a cyclic process.

Jan 1, 1996

By Pragna N. H. Bhakta

The minerals industry is under political and economic pressure to reduce its processing wastes and minimize their impact on the environment: Recycling is one of the means by which the minerals Industry can reduce the quantities of effluents and residues that are discharged to the environment. The wise use of available resources is not only an environmental necessity but also an economic benefit as natural mineral resources are depleted and/or become more complex. The purpose of this paper is to review the technical and regulatory issues that will help shape the future of minerals recycling over the next ten years. Research and development to address technical issues will be discussed with emphasis on the Bureau of Mines recycling research program.

Jan 1, 1992