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By Rzyman Michal, Nakamura Takashi, Shibata Etsuro, Grabda Mariusz, Oleszek-Kudlak Sylwia

"Tetrabromobisphenol A (TBBPA) and many systems based on the synergistic effect of brominated organic compounds with Sb2O3 are extensively used as effective brominated flame retardants (BFRs) in many materials such as plastics and textiles. Thermal degradation of BFR containing plastics leads to the formation of hydrocarbons and gaseous compounds such as HBr and SbBr3. Our thermodynamic considerations indicate that these gases can act as bromination agents for metallic oxides such as ZnO, Cu2O, CuO, PbO and FeO. Moreover, these metallic oxides have the thermodynamic tendency to brominate easier than does Sb2O3. The aim of this study was to investigate experimentally the reactivity of ZnO with 1) HBr originating from the thermal decomposition of TBBPA and 2) SbBr3, which is formed during thermal degradation of brominated flame retardant plastics. The thermal treatments of the mixture of compounds of interest were investigated by thermogravimetry coupled with mass spectrometry.IntroductionTetrabromobisphenol A (TBBPA) and many systems based on the synergistic effect of brominated organic compounds with Sb2O3 are extensively used as effective brominated flame retardants (BFRs) in materials such as plastics and textiles. For instance, 4.5 million tons of flame retardant plastics containing BFRs are produced in Japan each year. Thus, in thermal treatments such as the incineration and melting of solid wastes, BFR containing plastics are intentionally or unintentionally included in the wastes. Thermal degradation of BFR-containing plastics leads to the formation of hydrocarbons and gaseous compounds such as HBr and SbBr3 [1-5]. Our thermodynamic considerations [6] indicate that heavy metal oxides such as ZnO, Cu2O, CuO, PbO and FeO should easily react with HBr prior to Sb2O3 and also with SbBr3, the main gaseous product in the thermal decomposition of TBBPA, forming low boiling point metallic bromides suitable for the volatile separation of heavy metals. The metal oxides are also expected to qualitatively and quantitatively affect debromination and decomposition of the flame retardant."

Jan 1, 2008

By Jens Kristen Laursen

In 1999, Molymex S.A. de C.V. (Molymex), Mexico. (a company wholly owned by Molibdenos y Metales S.A. (Molymet), Chile) decided to install the Haldor Topsrae Wet gas Sulphuric Aicd (WSA) process for cleaning of the 4-5% SO2 off-gas from their molybdenum sulphide master in Cumpas, Mexico to produce sulphuric acid. The decision to install a WSA plant was based on the successful operation of a WSA plant at Molymet's molybdenum sulphide roaster in Santiago, Chile since 1993. This paper describes the process layout of the Cumpas plant, the operating experience of the Santiago plant, and the, differences in. process design between the two plants. It will furthermore summarise the applications of the WSA process for other roasting plants and smelters within the non-ferrous. metals industry producing metals such as copper, lead, and molybdenum.

Jan 1, 2002

By Eliezer Martinez-Jimenez, Gretchen T. Lapidus

"Electro-assisted reduction is an effective pretreatment to render chalcopyrite less refractory towards oxidative leaching. In this process, chalcopyrite is selectively converted to chalcocite or copper metal in an electrolytic cell under ambient conditions, while ferrous ion is leached into solution. However, the reaction velocity is hampered by the formation of a ferrous sulfide passivating layer on the solid surface, especially at elevated solid to liquid ratios. In the present work, several strategies for overcoming this problem were evaluated. On one hand, specific ligands for ferrous ion were added in order to increase its solubility and, on the other, an anode material which promotes the oxidation of the sulfide ion was chosen. Leaching tests showed citric acid to be an effective ligand for both ferrous and ferric ions and, in combination with a lead-silver anode, significantly increased the kinetics of chalcopyrite reduction and subsequent copper leaching.IntroductionAttempts to oxidize chalcopyrite at a rapid rate in aqueous solutions, below their normal boiling point, have met with difficulties because of passivation by some of its own components. An alternative line of research explores reductive pretreatment, transforming the chalcopyrite into less refractory copper phases, which can later be oxidized. A recompilation of these efforts up until 2000 was published by Dreisinger and Abed [1]. However, this practice usually requires large excesses of reducing agents, such as copper, lead, aluminum or iron, and in this last case at near-boiling temperatures, in highly"

Jan 1, 2012

By Pranav Deshpande

The wear behavior of metal matrix composites differs from that of the monolithic metallic counterparts because composite materials have multiple constituents in their structures and these constituents wear at different rates. It was observed that under low wear stresses, abrasive wear prevailed. As the wear stress increases, pullout of reinforcement occurs and both abrasive wear and wear due to pullout contribute to the overall composite wear. A model of wear taking into account both types of wear has been developed. A critical pullout wear stress was suggested for each composite. Below the critical wear stress, no pullout of reinforcement occurs. It turns out that the critical wear stress simply equals to the ratio of the interfacial strength between the matrix and the reinforcement to the friction coefficient between the reinforcement and the wear counter surface. The critical wear stress is independent of the particle size of the reinforcement. From data on wear of 53% WC composites, the equation of wear for 32% WC composites was obtained. Experimental results agreed well with the predicted wear rate of this composites. This provides an excellent verification of the wear model developed by Lin and Deshpande. Wear data from Modi et al. in the literature were also perfectly fitted with the model.

Jan 1, 2006

By David B. George

In spite of the many well-known problems inherent in Pierce-Smith converting, it remains the dominant copper converting process. Continuous copper converting and direct concentrate to blister smelting have been commercially available for over 25 years and now produce approximately 15% of copper smelter production. The two fully commercialized continuous converting processes, Mitsubishi MI Process and Kennecott-Outokumpu Flash Converting, and several emerging converting processes are reviewed with view of their potential, limitations, and environmental performance. Some myths regarding these technologies and Peirce-Smith converting are also challenged.

Jan 1, 2002

By Kouji Mimura, Masahito Uchikoshi, Minoru Isshiki

"HfO2 is expected to be a gate dielectric used in ULSI alternatives to S1O2. Although the materials used in ULSI are required to be significantly pure, commercial Hf contains > 2 mass% Zr. It is important to establish a process for removing Zr from Hf. In the present study, anion-exchange separation using a multi-column method was employed. The separation tests were carried out at variety of temperatures and flow rates. The decrease in the flow rate of the mobile phase made the elution curves of both Hf(IV) and Zr(IV) broaden contrary to the case of Co(II), Cu(II), or Fe(III). This is caused by the difference in adsorption rate on the anion exchange resin. In addition, more than one column was connected in series in order to enhance the separation. As a result, the content of Zr(IV) was successfully reduced to 1/100 of that relative to the raw material.IntroductionHafnium is one of the most important materials in modem society. The main applications of Hf metal are as a control rod in a nuclear reactors because of its large neutron-capture cross-section and as an additive to various alloys because of its corrosion resistance [1]. In addition to those applications, attention has been recently paid to HfCh as a high-x"" dielectric used in ultra large scale integration, ULSI, as well as ZrCh, AI2O3 and La2C>3, which are expected to be alternatives to conventional S1O2 thin films [2].The materials used in ULSI are required to have a high purity in order to avoid unexpected errors due to impurities. Furthermore, high purity Hf is indispensable for investigating the intrinsic properties of Hf metal. Thus, it is significant to establish the purification process for Hf from both the industrial and academic perspectives."

Jan 1, 2012

By Hiroshi Maeta, Takao Kino, Hirota Osono, Kikuo Matsusaka, Azusa Shida

"Prior to refine an ultra-high purity material, it is necessary to estimate the surface cleanness of a base material. In this report, the cleaning method of a surface for refining of an ultra-high purity aluminum has been studied. Aluminum sample of 99.999% purity was p9lished mechanically and electrically and washed with various solvents. Surface composition and a depth profile near the surface were examined. Based on the experimental results, surface structure of an ultra-high purity aluminum was discussed.IntroductionRecently, studies on high purity metals have become of interest, and we have reported .various properties of an ultra- high purity aluminum1- 2)In order to purify a metal, it is necessary to clean a work area and to make vacuous as possible. So, we are studying the purification of aluminum by an ultra-high vacuum refining system and a zone refining system set up in a clean room with cleanliness class of 1000.Now, in order to avoid a mixing of impurities into the refining metal, a surface cleanness of a base metal is very important factor. The purity of the base aluminum used our work is 99.999%, but the surface state of the base aluminum is not clear. Aims in this work .are to investigate the surface state and to obtain the cleaning method of the base aluminum.Experimental procedureSamples used in this work were 99.9% (3N), 99.99%(4N) and 99.999% (SN) aluminum produced industrially and 99.9999% (6N) aluminum purified by us."

Jan 1, 2000

By K. Th. Mavrommatis

Cleanness of steel is justified, measured and estimated in steelmaking process through different concepts which are mainly based on operational, empirical or semiempirical parameters and describe ?cleanness as a state?. In this work a theoretical concept is developed, considering ?cleanness as a process? and introducing a dynamic aspect into the quantification of cleanness of a steel melt, linking operational parameters with physicochemical variables, which are based on first principles. This concept and the here derived and developed variables and parameters are based on the earlier defined agglomeration index (AI) of a steel melt, the ratio of the mean inclusions diameter (MID) to the mean inter-particle distance (MIPD), which is shown to be a measure of the agglomeration tendency of the melt after deoxidation, and can serve both, to monitoring cleanness during steelmaking operation and to be useful as a basis for mathematical modelling of cleanness and of the metallurgical measures in plant, associated with production of clean steels.

Jan 1, 2006

Today’s world relies upon advanced green technologies that are made of critical elements with unique properties. Examples include rare earth elements (REEs) that are critical in the manufacturing of wind turbines and electric/hybrid vehicle batteries, key components of a greener future that face supply uncertainty and near zero recycling. To tackle their supply challenges, activities have begun for urban mining from waste electrical and electronic equipment (WEEE) that contain considerable amount of REEs, but their current level of recycling is less than 1%. Current recycling practices use either pyrometallurgy, which is energy intensive, or hydrometallurgy that utilizes large volumes of acids and solvents and generates large volumes of hazardous waste. In this study, we developed a novel and sustainable process to recycle REEs from WEEE, NiMH batteries in particular. The developed process relies on supercritical fluid extraction (SCFE) utilizing CO2 as the solvent, which is abundant, safe, cost effective, and inert. The effect of seven operating parameters, namely temperature, pressure, residence time, sample to chelating agent ratio, agitation rate, complex formulation, and methanol addition on REE extraction efficiency was investigated, and optimum operating conditions were determined. This work is the first to utilize a very efficient and safe process that runs at low temperature to extract metals from postconsumer products with minimum hazardous waste generation, while offering about 90% leaching efficiency for REEs. We expect our process to find widespread applicability in urban mining of REEs using green chemistry.

By Heikki Jalkanen

Oxygen converting of hot metal (LD/BOF) is contemplated as an object of simulation. Oxygen converting is a highly complex thermo-chemical process comprising a series of matter and energy transformation and transportation steps that makes the simulation very challenging. The basic principles of CONSIM 5 oxygen converter simulator are presented. Simulator is a comprehensive combination of a physical model with several empirical submodels describing all properties and processes that affect the final result of a converter blow, final mass and composition of steel, slag, dust and converter gas as well as the end temperature of steel. CONSIM simulator is used for simulation of series of high and low carbon steel blows. Simulated steel temperatures, oxygen consumption, blow time and iron oxide content of slag are compared with measured values. Problems of simulation and requirements for quantitative simulation of oxygen converter process are discussed.

Jan 1, 2006

By Luiz R. P. De Andrade Lima

This paper presents a mathematical model for the oxide copper ore heap leaching process. The data used in the model include physical-chemical, .geometrical and operational data, as: leachable metals ore contents, .flow rate and acid concentration, parameters of passivity, ore size distribution, the average residence time of the solution in the heap, height, irrigated area and weight of ore in the heap. In this model the heap is divided into horizontal and plane layers of constant area. The flow of the liquid in the heap is considered unidirectional and the solid-fluid reaction model is considered under diffusive control. The average residence time of the solution into the heap and the apparent effective diffusivity of the acid through the ore particles have .a significant influence on the rate of the copper extraction and its concentration in the pregnant solution; therefore these parameters are used in the model calibration. When this algorithm was applied to a laboratory test, the results showed that the model is adequate to predict the process performance.

Jan 1, 1999

By Laurentiu Nastac

"The importance of investigating solute redistribution during the unidirectional solidification of multi-component alloys is broadly discussed in the literature. A previously developed analytical model that was experimentally validated for Al-Cu, Sn- Bi and Fe-Si dilute binary alloy systems is used in this article to study in detail the solute redistribution, the liquid/solid interface stability based on an extended transient constitutional undercooling criterion and the size of the initial transient region during the unidirectional solidification of Ti-6-4 and Ti-17 alloys. A comparison between Ti-6-4 and Ti-17 alloy systems with respect to interface stability and the size of the initial transient region is also provided. The effective partition coefficients of the alloying elements in these alloys were determined based on specially designed experimental measurements.IntroductionThe importance of investigating solute redistribution during alloy solidification is broadly discussed in the literature [1-5]. One of the relevant applications of this study would be the mathematical modeling of equiaxed and columnar solidification of multicomponent alloys. This includes the instability of the solid/liquid interface. There are several mass and heat transfer processes that involve the calculation of solute redistribution during directional solidification such as industrial directional solidification processes, continuous casting, remelting processes, Czochralski crystal growth technique, floating zone techniques, etc."

Jan 1, 2012

By J. E. Murphy

Neodymium was electrowon into a Mg-Cd molten cathode at 650 °C from NdC1,-KC1 electrolyte. With the chloride system, neodymium was deposited into the molten alloy cathode until the neodymium concentration reached 20 wt pct. The alloy was then vacuum melted to remove the Mg and Cd. The current efficiency exceeded 80 pct under optimum conditions and the purity of the metal was 99.9 pct after vacuum melting. As an alternative approach, neodymium was electrowon at 1,030 °C from Nd,O, dissolved in a molten fluoride eleotrolyte. With the oxide-fluoride electrolyte, the metal was electrowon in a molten state with current efficiencies up to 60 pct. The purity of the metal was 99.8 pct with oxygen and carbon as major impurities. A number of problems were encountered including anode effect, low oxide solubility in the electrolyte, high neodymium metal solubility in the electrolyte, and reactivity of the metal with the cell materials. Approaches to improved cell, operation and prospects for commercial adoption of the electrolytic production of neodymium metal are discussed.

Jan 1, 1995

By Christopher Solnordal

A mathematical model was developed to simulate the performance of the reaction shaft at BHP-Billiton?s Olympic Dam copper flash smelter. In order to have confidence in the predictions of the mathematical model, validation was performed by comparing and reconciling the predictions from the model with the results from a campaign of sampling and plant measurements. The model was based on the computational code CFX4.4 utilizing a combustion sub-model purpose-built by CSIRO. The combustion sub-model employed the concept of a composite particle which contained the three components of the solid charge: concentrate, flux and returned dust. Plant measurements were made and samples taken immediately below the burner and through a port halfway down the reaction shaft. Parameters measured included temperature, solid loading and SO2 concentration in the gas. Comparison of the measured and predicted values then showed that: predicted far field gas temperatures were within ±50C of measured values; predicted temperatures in the central plume were lower than measured, and, the predicted plume width was slightly smaller than measured. An optimum composite particle size of 19 m was identified for use in future modeling work at Olympic Dam.

Jan 1, 2006

By Peng Peng, Ouo Cheng, Guodong Lai, Lijuan Chu, Zebiao Zhang

"The pressure acid leaching residue of zinc concentrate contains a large quantity of sulfur. The present study attempts to leach sulfur using a mixture of ammonium sulfide and water solution at 25°C. Effects of three leaching variables: ammonium sulfide concentration, leaching time, liquid/solid ratio on the sulfur leaching rate were investigated. The process conditions were optimized using response surface methodology based on the central composite design. From the analysis of variance (ANOVA), the significant factors on response were identified. The optimum conditions for leaching elemental sulfur from pressure acid leaching residue of zinc concentrate were obtained using an ammonium sulfide concentration of 2.5 mol/L, leaching liquid-solid ratio of 6.5:1 and leaching time of 7 min. Under the optimum experimental conditions, a maximum of 98.50% of total sulfur was extracted. The experimental results obtained agreed satisfactorily with the model predictions, with a correlation coefficient (R2) of 0.99.IntroductionSulfur is widely used in agriculture, medicine, rubber, building materials, gunpowder, wine and sugar, and other fields [1]. Currently the world sulfur production is 40Mt, out of which more than 90% is recovered from industrial processes, and 10% is natural [2], This highlights the importance of sulfur recovery. As the pressure leaching technologies [3] continue to mature and are increasingly applied to refining, a large quantity of high-sulfur residue is produced [4-5]. It is desirable to recover sulfur from this residue, so that it is economically advantageous, and reduces environmental pollution [6]."

Jan 1, 2012

By F. Begazo

The most common approach to increase production in copper refineries is to increase current densities. However, if these increases are not well thought out beforehand and are not properly and effectively controlled, the end results could be reduced plant performance and a deterioration in cathode quality. Both of these factors result in lower efficiencies and increased costs. At the Ilo Refinery of Southern Peru Copper Corporation, a modernization and expansion program was implemented shortly after the Refinery was purchased from Minero Peru, in 1994. This program was intended to increase production from 195,200 mtpy of cathode to 227,000 mtpy over a 3-year period. Part of this production increase would come from increasing current density. During the period from 1994 to 1997, current density at the Ilo Refinery was increased from 218 A/m2 to 230 A/m2, while plant efficiencies were maintained at consistently high levels. The current efficiencies were maintained at >97.5% and time efficiencies were maintained at >98%. During 1998, additional increases in current density were implemented while the high plant performance was maintained at the same levels. By the end of 1998, the current density was 241 A/m2, while current efficiency and time efficiency of 98% were maintained. This paper describes the control processes used at the Ilo Refinery to maintain high plant performance levels while increasing the current density. Additionally, expected plant performances from extended test programs at current densities up to 280 A/m2, for future production increases, are reviewed and discussed.

Jan 1, 1999

By I. Van de Voorde

In this paper, results are presented concerning the search to implement Supported Liquid Membranes (SLM) Technology for the recovery of copper, nickel and zinc from electroplating and other effluents to prevent metal waste. A study of the influence of the individual parameters and of their combined effect on mass transfer in small-scale laboratory equipment has been performed, enabling to set forward the appropiate operating conditions for a pilot plant installation. The SLM pilot plant has been tested extensively, including short and long term runs, with real process solutions. It was demonstrated that the SLM technolgy is applicable for solutions containing 800 mg/L of metal ions, but also to the treatment of solutions with low metal content of origin other than plating shops. It was demonstrated by system analysis that the recycled salts are usable to produce metal electrolytes (for example Watt's nickel bath).

Jan 1, 2003

By Norbert L. Piret

During smelting of copper, arsenic in the feed reports to a large extent to the gas phase and some enters the anode copper. From the gas phase it is transferred during wet gas cleaning directly, or indirectly after dust processing, to aqueous solution. During the electrorefining and anode slimes processing, the anode arsenic content is also transferred to aqueous solution. Technology for the efficient removal of arsenic from process streams and cleaning of aqueous effluents is well established. However, the arsenic-bearing products, which thereby are generated, can vary widely in consistency, quality and quantity, from large amounts of gypsum contaminated with water-soluble arsenic compounds to residues with high arsenic content ' or arsenic products. Arsenic management in a copper smelter not only is involved with the duty of compliance to the gaseous and aqueous emissions standards but also should have as objective the minimization of the generation of arsenic-bearing and, in general, heavy metal-bearing solid waste. The present paper outlines options and the associated economic aspects for minimization of arsenic-bearing solid waste generation, for improvement of the environmental compatibility of the residues to be deposited and for the .production of commerciable arsenic compounds under appropriate market conditions.

Jan 1, 1999

By Patrick R. Atkins

Energy issues will have increasing impacts on decision making in all facets of society over the next few decades. Industrial users of energy and producers of products that affect energy use must be fully aware of the implications of their processes and products on the energy situation. This paper describes a model that has been developed for the aluminum industry that allows scenarios to be evaluated to gain improved understanding of possible implications for our businesses. A brief overview of the model is provided.

Jan 1, 2006

By Toshihide Takenaka

Improvement of corrosion resistance of Mg metal by addition of rare earth metal (RE) was studied, and the effect of surface oxide layer with RE was investigated. The corrosion resistance of Mg was remarkably improved by adding a small amount of RE, and the suitable RE content was clarified. The corrosion resistance of Mg was particularly bettered by conversion coating using a solution including both RE(NO3)3 and Mg(NO3)2. This result indicates that the surface oxide layer consisting of both Mg and RE gives good corrosion resistance to Mg metal. In this study, direct electrodeposition of Mg metal containing RE was also tried in molten chloride with RE chloride, and it was shown that electrolysis could be performed stably. The RE content in the deposited Mg metal was depended on the concentration of RE chloride in the bath and the cathode potential, and Mg metal containing the suitable RE content for its corrosion protection was obtained easily by direct electrolysis.

Jan 1, 2006