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By D. G. C. Robertson

The thermodynamics and kinetics of the reactions involved in fuming zinc from oxide slags using coal or coke were first studied in 1955 and have been the subject of many investigations since that time. The key reaction is ZnO(in slag) + CO = Zn(g) + CO2 This paper will review the some of the recent work, and will add new insights obtained in experiments carried out by the authors. In the first series of experiments it was shown that the reaction does not occur at an appreciable rate, as is expected from thennodynamic considerations. In the second series of experiments it was shown that zinc does not fume from the slag at a significant rate unless a reductant has been added. This again is in accord with thermodynamic considerations, but is in contradiction to some of the experimental results reported in the literature. A third series of experiments was carried out with excess coke being present, so that the rate of supply of reductant was not in any way controlling the rate. The kinetics of zinc oxide reaction were then found to be independent of the zinc oxide concentration, but increased with increasing basicity, and temperature. The presence of high concentrations of FeO in the slag also improves the kinetics. At low zinc oxide coneentrations iron oxide reduction occurred in parallel with zinc oxide reduction. We propose that (under the conditions of this work) the kinetics were controlled by a chemical step, namely the rate of desorption of an adsorbed CO2 species. This is the same mechanism as reported by Belton and co-workers for the kinetics of the reduction of FeO. This explains why the reduction of metal oxides in slags by hydrogen is often faster than by CO.

Jan 1, 2003

By Maija-Leena Metsärinta

The behaviour of copper and lead in zinc roasting has been studied in laboratory scale roasting experiments as well as in large scale trials in an industrial fluidized bed, with the background of Outokumpu Kokkola Zinc smelter. Commercial zinc concentrates with a low and high ( up to 3 wt % ) copper content and with a low and high (up to 3.5 wt % ) lead content were oxidized to various desulphurisation degrees in the fluidized bed to establish the reaction mechanisms and the paths for copper and lead oxidation in the roasting. Influences of the agglomerate size on the roasting kinetics and micro-scale phenomena were also determined. Optical microscopy was used on the calcine and the findings are presented as numerous photographs of the polished cross sections. SEMIEDS techniques were used for analyzing chemically the phases and particle morphologies present in the samples. Computational thermodynamics was applied to the complex phase equilibria occurring during roasting in the agglomerating calcine. A complete oxidation of zinc concentrate with a high copper and lead content requires a careful control of oxygen coefficient in the roasting in order to maintain a stable operation of the fluidized bed. Oxygen coefficient thus seems to have a significant impact on the hydrodynamic stability of the fluidized bed with fine raw materials.

Jan 1, 2003

By Kazuki Morita

A new route to produce solar grade silicon (SOG-Si 6N) from metallurgical grade (MG-Si 98%) has been developed in Japan, which may satisfy the increasing demand for solar cells in the near future. Since some elements such as P and B have very large segregation coefficients, solidification refining is not effective for their removal and costly processes, such as electron beam vacuum melting and oxidation plasma refining, are required. According to our previous results which showed the effectiveness of leaching procedure with Ca addition for Fe and Ti removal, possibility of P and B removal by acid leaching was focused expecting that their affinities for Ca in molten silicon might be considerable. Hence, the effects of Ca addition on the thennodynamic properties of P and B in molten silicon alloys have been investigated for overall control and optimization of the SOG-Si production process in the present study. The interaction parameters between Ca and P, and Ca and B were determined by chemical equilibration techniques at 1723 K. Although the interaction parameter between Ca and B was slightly negative, that between Ca and P showed a large negative value. Also, the results for the leaching test with various amount of Ca addition revealed that the removal fractions of both elements, especially P, drastically increased with increase in the Ca content, which showed very good agreement with the prediction from the interaction parameters derived in the present work. The present results suggest that the preliminary leaching procedure can reduce the processing time and energy for SOG-Si refining. Keywords: Silicon, Solar Cell, Refining, Acid Leaching, Thennodynamics. Interaction, Phosphorus, Boron, Calcium

Jan 1, 2003

By Tang Chaoho

Laboratory research on the reducing and matte smelting of Jamesonite concentrate has been carried out. The influence of the process conditions such as the smelting temperature, the amount of pyrite cinder (the agent of fixed sulfur) and the amount of additives on the smelting process have been studied. Under the optimum condition the direct recovery ratios of antimony and lead are 83.26% and 68.50% respectively. The ratio of fixed sulfur is 98.97% but more than 15% lead and 30% silver remained in the ferrous matte. The key problem to be solved of this new process is how economical and effective is the recovery of silver and lead in ferrous matte.

Jan 1, 2003

By Jesús Contreras

Since the commencement of its activities in Huelva in 1970, Atlantic Copper has maintained a course of action that has been more demanding than the successive environmental legislations current at different times. As its primary objective it has sought compatibility between the protection of the environment and both its industrial activity and the social and economic development of the area in which its Metallurgical Complex is located. For this reason, since the seventies it has maintained a continuous programme of investments which have allowed it to attain its present environmental situation. As a consequence of the Environmental Policy of Atlantic Copper, in April 1998 it obtained certification for its Integrated System of Environmental Management (SIGMA) according to international standard IS0-14001, and under European Community Regulation 1836/93 (replaced by the 76112001) for the Eco-Management and Eco-Audit System (EMAS). The SIGMA formalises the environmental management practices of Atlantic Copper and engages it to have available a system that can be fully audited. Atlantic Copper was the first European Company in the non-ferrous metallurgical sector to obtain both the UNE-EN-ISO 14001 certification and the EMAS registration. The present paper reviews the actions by Atlantic Copper in environmental matters that have allowed it to achieve its present position. It also describes the coming stages of improvement planned and the modifications to be carried out in the near future, in particular the criteria for the selection of technologies on the basis of the concept of BAT (Best Available Techniques) introduced by the European Union, and always guided by the final objective of converting Atlantic Copper into a reference within the sector, comparable to the best designed and operated installations in the world.

Jan 1, 2003

By Peter G. Smith

Tri-calcium aluminate (TCA) is a dominant alkaline component of the red mud residue from the Bayer process. A method being considered for industrial implementation partially neutralizes the residue by contacting it with gaseous CO2. This paper outlines the chemistry of CO2neutralisation of TCA under conditions relevant to the treatment of Bayer residue. CO2 neutralisation of the liquor is fast. It results in the formation of amorphous aluminium hydroxide and dawsonite that agglomerate together. Neutralisation of solid TCA is slower and leads to the formation of calcite, dawsonite and amorphous aluminium hydroxide. The dissolution of TCA in partially neutralised slurries causes pH reversion. However the carbonated solutions contain a store of bicarbonate that can supply aqueous carbon dioxide to complete the transformation. The pH at which the carbonation is carried out will affect the degree of TCA transformation during the carbonation process. In particular, if the pH of the carbonation is too low (near 7.0), calcite precipitation is inhibited and the degree of transformation is low. Controlling the carbonation pH helps to optimise the neutralisation process.

Jan 1, 2003

By Takahiko Okura

Most non-ferrous raw materials are associated with sulphur. To extract the metals, the sulphur is recovered typically as sulphuric acid or liquid SOz, On the other hand, natural gas may contain over 20% of hydrogen sulphide (HzS) and a huge quantity of elemental sulphur is produced through oil and gas refining processes in the world. A large fraction of the sulphur mined from natural sources is eventually returned to the earth as fertilizers, by-products of desulphurisation and neutralisation processes, or as fugitives to the atmosphere. However, the supply and demand for sulphur are in imbalance. Such situation urges to develop a new smelting process without sulphuric acid production. This paper briefly reviews the global sulphur balance and the technologies for recovering elemental sulphur. The core of this paper is a proposal to convert SO2 gas to elemental sulphur by using organic materials. Some results of thermodynamic calculations and experiments are presented.

Jan 1, 2003

By Brad Wahlquist

An ex-situ biological treatment system was implemented at a gold mine site in South Dakota. The system removes selenium and nitrate from a mixture of groundwater and surface water runoff at ambient water temperatures. The Applied Biosciences? system replaced a denitrification system that did not perform consistently, did not treat for selenium and required heating of the influent water. Installation was completed in phases starting with the selenium circuit being brought into operation in February, 2002 and the nitrate circuit in March, 2002. System design can accommodate average flows of 380 L/min (100 gallons/minute) and a maximum flow of 1,136 L/min (300 gallons/min). Four cells were designed to remove nitrate from approximately 30 mg/L to below 10 mg/L and two cells were designed to remove selenium from 0.01 mg/L and higher, to below 0.005 mg/L. No pretreatment is required to operate the system at ambient temperatures, which can fall as low as -12C in the winter, and treat water at temperatures ranging between 8C to 16C. Nutrient requirements are met using a sugar based nutrient mixture that includes a balanced C:N:P:S ratio, trace elements and vitamins. Since start up, the system has consistently been in compliance for nitrate and selenium, treating water to below detection limits for both contaminants. This paper discusses laboratory biotreatability testing of a system designed to remove selenium, arsenic, and nitrate and full-scale implementation and optimization of a system to remove nitrate and selenium.

Jan 1, 2003

By Zhang Duomo

A novel homogenous precipitation method, including microwave heating, solution conductivity controlling and freeze drying, was developed for the preparation of US nanoparticles. The effects of the precipitation conditions on the structure and morphology of CdS particles were discussed individually. It was found that under the experimental conditions the particle sizes were controllable in the range of 14nm to 100nm. Blend-type CdS was obtained from nitrate or sulphate solution and the more stable wurtzite-type US was obtained from chloride solution, which was ascribed to the coordination of C1 and Cd2+ altering the supersaturation of the solution as well as the different growth units and their connecting patterns, In the precipitation process the surface of US nanoparticles were surface modified with CH3CHSCOOH. The results demonstrate that the bifunctional thiols of thioglycolic acid modified the surface through Cd-S coordination bonding and the induced counter ion AOT-SO3 as the balance charge further increased the stability and dispersity of US nanoparticles. This surface-modified US nanoparticles had been used to prepare nonlinear optics and self-assemble catalysts.

Jan 1, 2003

By Hiroyuki Sano

A closed recycling process for the low-grade scrap of Al-based composite materials was developed. In this process flux treatment with water-soluble halide is a key technique. In the present work, flux treatment conditions were discussed from the viewpoint of the separation and the recovery of the base material, reinforcement and flux. Optimum separation condition was obtained for the NaCl-KCI-KF flux treatment. The recovered aluminum alloy can be recycled for various usages. The recovered SiC particles cannot be reused as reinforcement because of the coexistence of the contamination, therefore it is necessary to eliminate these contaminates or to find another use. The recovered flux is reusable with supplemental addition of fluoride.

Jan 1, 2003

By Maurizio Marezio Bertini

Successful treatment of contaminated sediments was achieved by sparging either 0.5 M NaOH solutions or distilled water with an SO2/O2 gas mixture. Metals such as Cu, Pb, Cr and Cd were successfully removed in a relatively short time. The effect of temperature and pH was investigated. Higher temperatures produced faster and higher recoveries with Pb and Cr more affected to temperature increase than Cu and Cd. The removal of copper, up to 50% percent, was achieved in alkaline solutions through the formation of copper sulfite complexes. The complete removal of metals such as Cu, Pb, Cr and Cd required that part of the treatment be carried out in acidic solutions. A preliminary cost analysis was carried out.

Jan 1, 2003

By Noel A. Warner

Modern steelmaking is based on direct use of oxygen in high intensity batch reactors. A totally new approach is proposed in this paper, based on the view that pursuit of high intensity is unlikely to lead to successful coal-based continuous steelmaking. By substituting carbon dioxide and water vapor as the oxidants rather than using oxygen directly, the intensity is greatly reduced. Accordingly. subsurface formation of carbon monoxide bubbles can be avoided by careful manipulation of the three participating rate processes, gaseous diffusion, interfacial chemical kinetics and liquid phase mass transfer. Steelmaking can then be carried out without explosive ejection of molten droplets and the generation of micro-spray but rather in a controlled and fumeless fashion. The vital component is the introduction of generic melt circulation technology. Three melt circulation loops in series are envisaged. Starting with a composite feed of iron ore fines, pulverized coal and lime flux, a metallized solid raft floating on molten iron is propelled out of the ironmaking loop onto the first of two downstream steelmaking loops. In the first, a liquid slag is formed, primary decarburization is undertaken not with oxygen but rather with CO2 and H2O and the melt is desulfurized. The semi-product stream enters the third melt circulation loop, where open-channel decarburization is effected along with dephosphorization to yield a low carbon steel product. Alternatively, the melt leaves the last loop to irrigate a packed tower countercurrent to argon at around 100 mbar to continuously produce ultra-low carbon (ULC) steel.

Jan 1, 2003

By Rafael Padilla

In the production of copper from chalcopyrite (CuFeS2) concentrates by the smelting and converting technology, the ambient pollution with gaseous S02 and toxic metals such as arsenic compounds is still a serious problem, especial1y in the converting step due to the batch nature of the conventional Peirce Smith process. Non-SO2 emitting alternatives are leaching processes. However, few of them have had a limited industrial application and they are not very effective in discarding safely the toxic impurities. A combination of pyro-hydrometal1urgical methods: the sulfidation of chalcopyrite and subsequent leaching of the sulfidized material is a non-polluting alternative to treat not only clean chalcopyrite concentrates but also complex chalcopyrite-enargite concentrates. In this article, this alternative is discussed concerning the thermodynamics and kinetics of the sulfidation of chalcopyrite with gaseous sulfur. The kinetics of the leaching of the sulfidized concentrate in an H2SO4-NaCI-O2 system is also discussed.

Jan 1, 2003

By Maija-Leena Metsiirinta

The behaviour of copper and lead in zinc roasting has been studied in laboratory scale roasting experiments as well as in large scale trials in an industrial fluidized bed, with the background of Outokumpu Kokkola Zinc smelter. Commercial zinc concentrates with a low and high ( up to 3 wt % ) copper content and with a low and high ( up to 3.5 wt % ) lead content were oxidized to various desulphurisation degrees in the fluidized bed to establish the reaction mechanisms and the paths for copper and lead oxidation in the roasting. Influences of the agglomerate size on the roasting kinetics and micro- scale phenomena were also determined. Optical microscopy was used on the calcine and the findings are presented as numerous photographs of the polished cross sections. SEM/EDS techniques were used for analyzing chemically the phases and particle morphologies present in the samples. Computational thermodynamics was applied to the complex phase equilibria occurring during roasting in the agglomerating calcine. A complete oxidation of zinc concentrate with a high copper and lead content requires a careful control of oxygen coefficient in the roasting in order to maintain a stable operation of the fluidized bed. Oxygen coefficient thus seems to have a significant impact on the hydrodynamic stability of the fluidized bed with fine raw materials.

Jan 1, 2003

By Moto Goto

Today, Pierce-Smith converters, coupled together with various types of smelting units, are used in most of the world's smelters, However, due to the "batch" processing nature, and problems associated with fugitive emissions during the transfer of melt and blowing stages, this arrangement will unlikely be adopted in future smelters. Modern day alternative processes include the Mitsubishi Process, Outokumpu Flash Smelting and Flash Converting Process, the Noranda Process, and the Ausmelt Process, but only the Mitsubishi Process is a "truly continuous" smelting and converting operation, producing a constant flow of blister without tapping, and is economically proven by long term commercial operations. This paper reviews recent advances in modern continuous converting technologies, with a special section devoted to operation of the "first standalone Mitsubishi C-furnace" coupled together with a Noranda Reactor, at Port Kembla Copper Pty, Ltd. in Australia.

Jan 1, 2003

By Andreas Dietrich

Laser off-gas measurement of CO, O2 and temperature has been carried online in EAFs. A visualization screen shows the values of CO and Oxygen and temperature for the entire heat, and includes the status of furnace equipment. The historical data of the heats are stored such that the furnace performance can be evaluated and optimized. A short comparison between laser based and conventional systems has been carried out related to speed, influence of dust, water, pressure, protection for bag house explosions. A high water and/or dust content in the sample does not represent a problem for this type of system. The measurement method works without interruption even under worst conditions such as dirty scrap, carbon injection etc. The installation was developed in conjunction with Marienhuette, Graz. They are 100% scrap based with a tap to tap time of ca. 46 min. Keywords: Laser Measurement, Off Gas, CO, O2, Temperature

Jan 1, 2003

By Jinxing Ji

The thiosulfate lixiviant system for leaching of gold has been under extensive investigation for nearly two decades and consists of ammonium thiosulfate, copper and ammonia. There are several challenges with this system. The occurrence of ammonia must be taken into account from a health and hygiene aspect in the workplace, and also from an environmental perspective with significant levels of ammonia and copper in the tailings. Copper accelerates the leaching rate but causes excessive thiosulfate degradation. A new lixiviant system that has been investigated consists only of sodium thiosulfate without copper and ammonia. Gold leaching is carried out in an enclosed reactor with slightly elevated oxygen overpressure and temperature. Extensive leaching experiments were carried out to minimize thiosulfate degradation and polythionate formation while maximizing the gold extraction. For the preg-robbing carbonaceous ore sample tested, gold leaching was essentially complete within six hours and the thiosulfate consumption was lower than in the typical ammoniacal thiosulfate system. The gold thiosulfate complex in the pregnant leach solution was found to be quite stable under ambient conditions. This new leaching system has the advantages of being more environmentally friendly, has a shorter residence time, lower thiosulfate consumption, lower oxygen consumption, and is easier to control.

Jan 1, 2003

By Md. Maniruzzaman

The quenching performance of a liquid quenchant can be controlled by controlling the agitation in the quench tank. Without agitation, a vapor layer or bubbles form at the hot part surface and the natural convention of the quenchant limit the heat extraction rate at the quenched part surface. Resistance to the heat extraction rate can be reduced by breaking the vapor layer or by inducing a turbulent convection at the part surface through agitation (Le. forced circulation of the quenchant). To determine the effects of agitation on the quench performance of a mineral oil based quenchant, the CHTE quench probe system was used with AISI4140 steel probe tip. Quenching performance of the oil is evaluated by computing the effective heat transfer coefficients of the steel probe as a function of surface temperature using Lumped Parameter Analysis. In addition, computational fluid dynamics (CFO) simulation of the quench tank with an impeller type agitator has been done to understand and predict the fluid flow pattern in the tank. CFO simulation also provides insights for determination of optimal location of the impeller and the quench probe tip. Keywords: CHTE Quench Probe, agitation, CFD simulation, liquid quenchant, 4140 steel

Jan 1, 2003

By Paul B. Queneau

U.S. plants solely devoted to recovering values from metal-rich wastes have established market niches based on one or more competitive advantages: superior process technology, access to key feedstocks, unique equipment, special knowledge of markets, and an appropriate exit for outfall water. Plant methodology, competitiveness, environmental factors, and economics are examined, with particular attention to feedstocks, technologies, products, and outputs.

Jan 1, 2003

By Rak-Jun Choi

Plasma-induced damage of InGaN/GaN multiple quantum well (MQW) light-emitting diodes (LEDs) has been studied in terms of forward turn-on and reverse breakdown voltages, together with etch rate and surface morphology. The physical degradation of sidewall along with rough surface morphology of n-GaN caused by increased ion scattering induced the deterioration of the forward and reverse voltages. It was found that the turn-on voltage is sensitive to the surface roughness of the etched n-GaN and the breakdown voltage is strongly affected by the sidewall contamination. Annealing under nitrogen after the mesa etching improved the electrical properties of the InGaN/GaN MQW LEOs. Efficient blue light-emitting diodes (LEOs) were fabricated using InGaN/GaN triangular MQWs. The LEOs with triangular QWs showed a lower operation voltage and 2.4 times higher light output power than those with the rectangular MQW LEOs at 20 rnA and 20 "C. The intensity of electroluminescence (EL) at 20 mA was almost independent of ambient temperature in the triangular QW LEO, but decreased substantially in the rectangular one.

Jan 1, 2003