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By Yun Li

An innovative lead recycling process from scrap lead-acid battery paste is presented. The novelty in the process is avoiding SO2 generation and emission by using reductive sulfur-fixing technique. Iron-bearing secondary wastes produced from metallurgical industry were utilized as sulfur-fixing agent to capture sulfur in the form of FeS (s) instead of generation of SO2 (g). Na2CO3 molten salt was added to the smelting system to speed the reactions and improve valuable metals’ recovery and sulfur-fixation efficiency. Furthermore, this process can simultaneously co-treat various lead and iron-bearing wastes. At the same time, some precious metals, such as Au and Ag, contained in iron-bearing wastes can be recovered. The feasibility and reliability of this process was investigated thermodynamically and experimentally with the help of HSC 9.0 database and XRD and SEM-EDS analysis. A possible reaction mechanism and path in PbSO4–Fe2O3–Na2CO3–C smelting system was also clarified.

By S. Seetharaman, Du Siehen

"In the processing of molten metals, it is extremely important to monitor continuously the concentration levels of various minor elements. In the production of common metals like copper, iron and aluminium electrochemical sensors involving solid as well as liquid electrolytes are being increasingly used to measure the concentrations of minor elements. The present paper deals with the electrochemical principles underlying these measurements and the possible errors involved. One of the major difficulties in the case of the solid electrolytes is to correct for the consequences of the electronic contribution to the conduction of the electrolyte.The application of the electrochemical sensors for molten metals processing involves designing of these probes to withstand the industrial operating conditions. In this respect, significant achievements have been made with respect to the design of oxygen probes for liquid metals in general and liquid copper in particular. Some of the salient design features are discussed in the paper. The application of auxiliary electrodes for impurities in molten metals like phosphorus in copper and silicon in iron are taken up. The development of oxygen sensors for slags is given special attention. Recent developments in the field of sensor technology, as applied to metals processing are highlighted.1. IntroductionThe rapid technological advancement today require precise control of the process parameters and the impurity levels. Most of the molten metals processing in industrialized countries are often steered by suitable computer models, either phenomenological or simulations based on theoretical principles. These models often require that the process parameters are continuously monitored so that the progress is followed and modified suitably as and when required. It is common practice to measure temperatures by incorporating temperature sensors at the various strategic points of the reactor. In the case of monitoring the composition changes in the various phases, the method of sampling followed by routine chemical analysis involves a time lag as well as uncertainties in sampling and analysis. In this respect, electrochemical sensors have the advantage of generating accurate data when properly applied and increasing attention is being paid in the development of electrochemical sensors for various common species in molten metals processing. In the present paper, the developments in this area over the years are outlined and typical process applications are discussed. A greater emphasis will be laid on sensors based on oxygen conducting electrolytes and their application to the production of common metals like iron and copper."

Jan 1, 1996

By Jussi Vaamol

A commercial CFD-code was used to solve isothermal flow fields of gas and liquid in a Peirce-Smith converter. The model was validated with a 1/4 scale water model, and parametric study. Limits of the modeling technique used were recognized, but calculated results indicate that the present model predicts the general flow field with reasonable accuracy. The model was used to examine general flow conditions in an industrial scale PS-converter. Typical scaling factors of physical models were also evaluated with the aid of predicted bubble distribution, patterns of the flow fields and magnitude of flow velocities. The numerical simulations were found to open new viewpoints to the fluid dynamic related phenomena in the PS-process.

Jan 1, 1998

By R. Boom, Y. V. Meteleva-Fischer, B. Kraaijveld, H. Kuntzel

"Segregation of impurities during refining of metallurgical grade silicon (MG-Si) is an option to produce solar grade silicon (SG-Si). Directional solidification is a last step in production of SG-Si effective for removal of metallic impurities. The possibility is investigated to use metallic impurities originally present in MG-Si for removing boron and phosphorus. MG-Si has been treated using two methods: 1) alloying with calcium and 2) refining with Na2O-CaO-SiO2 slag, both by controlled cooling. The microstructure of silicon and the impurities distribution have been studied before and after the treatments. Using EPMA phosphorus and boron have been detected in 1-2 wt% concentration range in several intermetallic compounds in grain boundaries after both treatments. This observation points to a different possible mechanism of silicon refining from boron and phosphorus. Controlled cooling improves migration of phosphorus and boron to the silicide phases in grain boundaries, which can be removed by acid leaching treatment.2. IntroductionStandards for silicon solar cells and growing demand on “green” energy require economical and efficient route to the production of solar grade silicon. Refining of cheap metallurgical grade silicon is one of the promising options, where application of existing metallurgical approaches can result in cost-efficient production on industrial scale. Focus in refining is on impurities, which are most difficult to remove: B, P, Al, Ti, due to their large segregation coefficient in silicon and low vapour pressure [1]. Moreover, more environmentally friendly technology in comparison to the traditional Siemens process [2] will be in accordance with societal needs. Based on properties of common impurities in metallurgical grade silicon, alloying refining and slag refining are suggested as competitive techniques having potential effect on removal of impurities harmful for conversion of solar energy [3, 4]. Alloying with Ca followed by acid leaching was found to be effective for removal of Fe and Ti from silicon [5] and to enhance also removal of boron [6] and phosphorus [7, 8]. In the work of Inoue et al. [8] drastically increasing removal of phosphorus from silicon has been observed with an increase of Ca content and a thermodynamics-based explanation was provided. Since phosphorus has been found to condense in the secondary precipitate mainly composed of CaSi2, it can be removed together with iron and titanium by consecutive acid leaching treatment. Slag refining is one of the metallurgical methods proposed to be effective for refining of metallurgical grade silicon from boron [9, 10]. Slags with additions of the following oxides to silica have shown positive effect on removal of boron: CaO [11-13], Na2O [11,14]. Mechanism of slag refining from boron is based on oxidation of boron followed by its incorporation in the slag network [9,11]; the same mechanism is suggested for refining from phosphorus taking into account that oxides of boron and phosphorus are known as network-formers [15]."

Jan 1, 2012

By G. Kyle Green

Zirconium chlorinator residues contain an array of rare earths, scandium, unreacted coke, and radioactive thorium and radium. Because of the radioactivity, the residues must be disposed in special waste containment facilities. As these sites become more congested, and with stricter environmental regulations, disposal of large volumes of wastes may become more difficult. To reduce the mass of disposed material, the U.S. Bureau of Mines (USBM) developed technology to recover rare earths, thorium and radium, and unreacted coke from these residues. This technology employs an HCl leach to solubilize over 99% of the scandium and thorium, and over 90% of the rare earths. The leach liquor is processed through several solvent extraction stages to selectively recover scandium, thorium, and rare earths. The leach residue is further leached with an organic acid to solubilize radium, thus allowing unreacted coke to be recycled to the chlorinator. The thorium and radium waste products, which comprise only 2.1% of the original residue mass, can then be sent to the radioactive waste facility.

Jan 1, 1995

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 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 Kazuhiro Nisizono, Takashi Kuroki, Nobuyuki Mori, Keisaku Ogi

"The improvement of critical current density and mechanical property is essential to the practical application of the superconductive oxides. A solidification technique is developed in this study for the growth of columnar or single Y123 crystal with finely dispersed Y211 and Ag particles through a monotecto-peritectic reaction of Li.(Ba-Cu-Ag-0 rich liquid)+ Y211-+ Y123+Lz(Ag rich liquid). The large solidification rate and temperature gradient can refine the Ag and Y211 particles. But Ag-free region is widely formed along the crystal growth direction in the central part of the Y123 cell. Since this phenomenon occurs because of the cellular growth, it is necessary to narrow Y123 cell width or to grow Y123 crystal with flat freezing interface. By controlling crystal growth direction using a seed crystal, Y123 columnar or single crystal with uniformly dispersed fine Ag particles are obtained. The· behavior of Ag and Y211 particles during the solidification of Y123 crystal is simulated by the peritectic growth model of faceted Y123 crystals.IntroductionY-Ba-Cu-0 superconducting oxide (YBCO) with high critical temperature also has excellent superconducting characteristic under the high magnetic field. The critical current density (Jc) has been enhanced by ·using unidirectional-solidification technique, which can overcome the weak-link problem at grain boundaries and control the crystal orientation and the distribution of Y211 particles which give effective magnetic flux pinning centers in the Yl23 matrix [1-4].In addition to improving superconducting properties, it is necessary to improve mechanical property for the practical application. The silver addition to the melt-textured YBCO superconducting oxide has been reported as the effective method to improve mechanical properties without degrading superconducting properties. Since the material properties are considered to be largely affected by silver particle size, form, dispersion state etc. in the Y123 phase, it is important to control Ag distribution in YBCO/Ag composites. Besides, it is also reported that the silver addition improve the corrosion resistance to the water and CO2 [5,6]. Nishizono et al. [7-9] have reported that the silver distribution in the YBCO/Ag composites is largely affected by the solidification condition, but yet some unclear points are also remained. YBCO has been also fabricated by the zone melting method [10-12], and Furuya et al. [5] and Hirano et al. [13] have reported the fabrication of silver added YBCO composites, but the distribution and behavior of Ag are not investigated in detail"

Jan 1, 2000

By Y. Z. Zhang

Cyanide has generated environmental concerns because of its toxicity, and it may not respond to the treatment of complex and refractory gold ores. Gold leaching by thiourea is one of the most promising substitutes of cyanide. However, the high reagent consumption has hindered thiourea from its commercial application in gold extraction. The process chemistry and mechanism of thiourea degradation has been discussed on the basis of chemical bonding theory, thermodynamics and electrochemistry in this paper. Progresses on the decreasing of thiourea consumption have been summarised. The potential application of thiourea in gold extraction has been evaluated.

Jan 1, 1996

By Nural Kuyucak

Acid mine drainage (AMD) occurs at operating and abandoned mine sites as a result of oxidation of sulphide minerals, and is characterized by low pH and heavy metal contamination (e.g. Fe, Zn, Cu, Cd, Al, Mn). It usually requires treatment before release in order to meet regulatory requirements. Chemical methods, such as lime neutralization and sulphide precipitation, are commonly used to treat AMD. However, the conventional processes require high capital and operating costs, and constant attention for many years into the future. In addition, the amount of sludge produced by conventional lime treatment processes poses an increasingly significant disposal problems at decommissioned mining operations. There is, therefore, an urgent need to develop passive, cost-effective processes for mitigating AMD and seepages originating from tailings and waste rock areas. Noranda Technology Centre (NTC) has been evaluating various methods being developed by other institutions, and exploring new ideas, to achieve passive in situ processes for treating AMD. These methods include anoxic limestone (ALS), lime-organic mixture (LOM), biosorbents (BIOS) and biotrench (BT). Current investigations at NTC involve preliminary bench-scale testing. Based on the outcome of the bench tests, a field test will be performed at a selected site. Details of the bench tests are discussed in the paper. Key Words: Acid mine drainage, treatment, metals removal, passive treatment, anoxic lime, limestone, biological treatment, sulphate reducing bacteria, biosorption, biosorbent

Jan 1, 1993

By S. Shrivastava

A structure based model has been developed for the prediction of viscosities of K20-B20, melts. These melts exhibit an anomalous behavior of viscosity with continuous variation in B203 content. A maximum and a minimum are observed at low temperatures, which disappear on raising the temperature above the softening range. The addition of K20 to the borate melts causes two opposing phenomena: (1) depolymerization effects and the related breakdown of network structure resulting in the formation of singly bonded oxygens, which weakens the structure and hence causes a decreases in viscosity, and (2) the formation of four coordinated borons (BO4 tetrahedra) which strengthen the structure leading to an increase in the viscosity. The structural changes taking place in these melts on varying the temperature and the alkali content have been reviewed and are incorporated in developing this model. The predicted values are in excellent agreement with the experimental values over the whole temperature and composition range.

Jan 1, 1992

By Nourreddine Menad

Plastic materials have been associated with electric and electronic applications since the early days of the electrical industry. Plastics can amount to 30 percents of the scrap mass. Generally, they are treated with flame retardants such as halogenated ones and they can result in different toxic chemical compounds. These plastics can be used as combustibles in the recovery of copper and precious metals. However, during their combustion, halogenated flame retardants can produce dibenzo-p-dioxins and dibenzo-furans. The estimated thermodynamic data of several organic compounds resulting from combustion of electric and electronic scrap, have been used in conjunction with the program HSC to calculate the conditions for dioxin and furan formation. The results show that the formation of the dioxins is dependent on the quantities of carbon, hydrogen, chlorine and oxygen reacting in a given system, as well as on parameters such as temperature and pressure.

Jan 1, 1998

By P. M. Prasad

The last two decades have witnessed the emergence of numerous hydrometallurgical and direct processing techniques for the extraction of some metals from pocketed/lean/complex sulfide ore deposits. A new approach with some inherent technological merits, investigated in recent years, is the lime-enhanced reduction of metal sulfides. Thermodynamic aspects relevant to the lime-enhanced reduction of metal sulfides by H2,C0 and C are discussed. A survey of the researches on the basic features of and factors influencing the lime-scavenged reduction of selected sulfides and sulfide concentrates reveals that lime tremendously enhances the sulfide reduction rates (up to 100 times) and drastically reduces the sulfur emission into off-gas to negligible levels. Further successful practice of lime-enhanced reduction requires only a moderate temperature of reduction (characteristic of each sul¬fide) and, in the case of gaseous reduction, relatively low gas flow rates. Relevant kinetic aspects of the concerned reactions that have a bearing on process development and its understanding are also briefly discussed. A conceptual scheme of general applicability for the processing of sulfide concentrates by the lime-enhanced reduction technique consists of three main steps: (0 lime-enhanced reduction by a suitable reagent (e,g., H,2, CO, gasified coal, water gas), (ii) separation of the product metal from the dry slag (CaS + unused CO) by mechanical separation, magnetic/gravity concentration or flotation and (iii) melting and refining by standard procedures. This novel approach, which is patently less complex, is expected to employ basically simpler flow sheets at comparatively lower operational temperatures and aid in pollution abatement. Potential for developing such a route for the small scale extraction of metals like copper, molybdenum and antimony is indicated. Possibility of utilizing this technique for the production of fibers/ filaments of some metals is also outlined.

Jan 1, 1983

By N. Kanari

Reactivity of MgO towards C12+air, C12+N2 and C12+CO gas mixtures was studied up to 1000 °C. Carbochlorination of MgO occurs at temperatures lower than that of its oxychlorination. Effects of gas flow rate, temperature and partial pressure of the carbochlorinating gas mixture on the reaction rate were investigated. The apparent activation energy of MgO carbochlorination is 49 kJ1 mol between 425°C and 600°C. At 550 °C, the apparent reaction orders with respect to C12+CO, C12 and CO, are 2.37, 1.47 and 0.89, respectively. At this temperature, the maximum reaction rate was obtained using a C12+CO gas mixture having a Cl2lCO molar ratio equal to about 0.6.

Jan 1, 1998

By Wilhelm Wendt

About five years ago we showed that it is possible to use the spectral in- formation in the light emitted by the off-gas flame of a PS converter for on-line production control. Very recently measurements have been performed using improved optical equipment and data evaluation software, resulting in both improved accuracy and the establishment of new optical process parameters. Using the optical signals the slag heats could be stopped at a predetermined Cu content of the white metal with an accuracy of +0.2% Cu m the range 74-78% Cu. A good correlation was found between the slag composition and optical data, providing a possibility for on-line monitoring of the SiO2 content of the slag. The measurements indicate the possibility of predicting the optimum end-point of the copper-making stage and having real time information on the impurity removal. Factors influencing the optical parameters, such as blowrate, Pb content, temperature etc. will be discussed.

Jan 1, 1993

By D. A. Robbins

The Resource Conservation and Recovery Act. of 1976 (RCRA) requires testing of waste materials as part of the determination of whether these materials are classified and managed as hazardous wastes. The adoption of one standard testing procedure and its application to all types of waste materials has stirred much controversy. In the center of this controversy is the appropriateness of this testing procedure in characterizing non-ferrous metal intermediates and slags. The authors have evaluated the relative availability of metals in several types of copper and lead slags as defined by various testing protocols. Also discussed is the relationship between the chemical character of the slag and the availability of metals to leaching and certain metallurgical practices that can influence metals availability.

Jan 1, 1983

By P. N. Anyalebechi

The effects of a cross-hatched grooved mold surface topography, casting speed, and superheat on the morphology of solidifying shells of aluminum alloy 3003 have been characterized by a series of immersion tests. The cross-hatched grooves were 0.232 mm deep with wavelength or spacing between 1 mm and 15 mm. The shells solidified at casting speed of less than 10 mm/s on the 1 mm spaced cross-hatched grooved mold surface were fairly uniform with little or no localized variations in thickness. However, the propensity for non-uniform shell growth morphology was exacerbated by an increase in casting speed, melt superheat, and the wavelength of the cross-hatched grooves. This is provisionally attributed to their effects on interfacial heat transfer and wetting of the mold surface by the molten metal.

Jan 1, 2008

By Yurniko Nakamura

Hydriding properties and crystal structure of a Ti-V- Mn solid solution alloy have been studied by P-C isotherm measurements and neutron and X-ray powder diffraction. The absorption P-C isotherm at 298K shows two plateau regions at 0.01MPa and 1MPa. The X-ray diffraction data have demonstrated that three phases with a BCC, a pseudo-cubic FCC and an FCC structure form subsequently with increase of the hydrogen content. Crystal structure of the latter two phases has been determined by Rietveld refinement of the neutron diffraction data. The FCC phase is the di-hydride of CaF2 type with hydrogen occupation in the T sites. The pseudo-cubic FCC phase is the mono-hydride of NaCl-type with hydrogen occupation in the 0 sites, which has not been reported so far. The lattice constants of the mono-hydride (Ti1.0V1.1Mn0.9)H_2.7 are a'=0.407 nm for two axes and c'=0.390 nm for the third axis. The a'axis is shorter by 4% than the c'axis. This pseudo-cubic FCC lattice is formed by contraction of 5% of the a axis and expansion of about 30% of the c axis from the original BCC lattice.

Jan 1, 2002

By Byung-Su Kim

The recovery of elemental sulfur from sulfur dioxide has important implications for coal- burning power plants and nonferrous metal smelters. The thermodynamic analyses showed calcium sulfide to be suitable for recovering elemental sulfur from sulfur dioxide. At the temperatures of 1023 to 1153 K under the sulfur dioxide partial pressures of 5.0 - 60.1 kPa, elemental sulfur from sulfur dioxide was recovered by its reaction with calcium sulfide. The kinetics of this reaction were measured at the same conditions using a thermogravimetric analysis technique. This reaction scheme would be attractive if the coproduct calcium sulfate can be reduced to regenerate calcium sulfide. This is the topic of another paper. At 1073 K under the sulfur dioxide partial pressure of 25.8 kPa, 48 % of the original calcium sulfide was converted to calcium sulfate in an hour. Under the same conditions, 55 % of the regenerated calcium sulfide were converted to calcium sulfate in an hour even after third regeneration.

Jan 1, 1999

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