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By Nickolas J. Themelis

Nearly thirty two million tons of municipal solid wastes (MSW) are combusted annually in over one hundred U.S. Waste-to-Energy (WTE) power plants, thus reducing the use of fuel oil by about 1.6 billion gallons of fuel oil. One of the advanced WTE processes is the 0.9-million ton/y SEMASS facility at Rochester. Mass. Most of the combustion in the three giant combustion chambers occurs while the injected shredded wastes are in suspension, i.e .? in flash combustion mode. The velocity. temperature, and concentration profiles in the SEMASS combustion chamber were simulated by representing the combustible fraction of MSW by the simplified formula C6HIO04 and using the CFD program Fluent to solve the turbulent energy and mass transport equations. After validation against plant data. this model will be used to examine options for increasing the productivity of WTE combustion chambers, such as optimum distribution of primary and secondary air and oxygen enrichment.

Jan 1, 2003

By S. G. Galbraith

We have used the principles of supramolecular chemistry to develop reagents to transport metal salts. These reagents have separated charged "compartments" which recognize a metal cation and its attendant anion(s). They are easy to manufacture as they are structurally related to the commercial hydroxy-oxime extractants for copper. Efficient protocols for loading and stripping of these extractants depend on the novel feature that they bind the metal salt in a zwitterionic form of the ligand. Transfer of the phenolic protons to the pendant amines generates the charged "compartments" to accommodate the metal cation and its attendant anion(s). This paper focuses on how these types of reagent can be used to recover base metals from sulfate and chloride media in flowsheets in which solvent extraction effects separation and concentration operations, interfacing between conventional leach and electrowin/reduction processes. Work on the development of reagents that have high selectivity for metal chloride/sulfate transport, convenient stripping protocols and appropriate hydrolytic stability will be described.

Jan 1, 2003

By Lenny Winkel

With the aim to develop a solar-driven process for the extraction of copper from sulfide concentrates research on the decomposition of copper sulfides under inert atmospheres has been initiated. Thermogravimetric measurements on chalcocite (CuzS) revealed that copper is formed already at 1823 K. Chalcopyrite (CuFeS2) also disintegrates at this temperature, although at a lower rate. Copper and iron have been identified in the solid residue. The results confirm the feasibility of copper extraction by direct decomposition of sulfides under atmospheric pressure. The decomposition under inert atmosphere prevents generation of SO2, it also alters the behavior of volatile impurities during decomposition of copper sulfide concentrates. Chemical eqUilibrium calculations for chalcopyrite contaminated with enargite (Cu3AsS4) have shown that the absence of an oxidic slag allows for a complete evaporation of arsenic and subsequent separation from intermediate sulfides. The need to better assess the potential of direct sulfide decomposition has prompted the development of an experimental setup for studying the decomposition reactions. The experiment has been devised such that data on the decomposition kinetics and on impurity removal can be obtained at temperatures up to 2500 K.

Jan 1, 2003

By Pengfu Tan

In order to understand and control the formation of dioxins and furans in iron ore sinter plants and to possibly avoid expensive end-of-pipe removal stages, thermodynamic calculations on the stability of PCDD/Fs have been combined with sinter process modeling by means of kinetic simulations and computational fluid dynamics. Three thermodynamic databases of PCDD/Fs, derived using the Group Additivity approach and two computational molecular modeling methods, MNDO and PM3, respectively, combined with the SGTE database have been used to model the PCDDIF formation and the PCDD/F isomer distributions in iron ore sintering. The results show very similar conditions for the PCDD/F formation using the different databases. Concerning the isomer distributions of toxic PCDD/Fs, the calculated data derived from the MNDO method showed optimum agreement with measured values from industrial furnaces. The thermodynamic calculations also proved that the isomer distributions found in combustion processes are equilibrium values, while the concentration ratio of PCDDs and PCDFs in the wind boxes does not represent an equilibrium state. A CFD model of iron ore sintering was developed including the kinetics of 15 relevant chemical reactions with the aim of describing the temperature fields and the gas flow patterns in the sintering bed. On the basis of these information and experimental observations reported in the literature possible pathways for the PCDD/F formation in sinter plants have been identified: PCDD/Fs are formed in the critical temperature region of 250 to 450°C below the combustion zone, are then carried downwards with the gas and condensed close to the bottom of the sinter bed. Transported to the discharge end with the solid mixture, they are again released into the gas phase when the flame front approaches the bottom. PCDD/Fs are also formed in the last wind boxes when the hot off-gases cool down and reach the critical temperature range. Consequently, methods to reduce the dioxin formation reactions are proposed including inhibitor addition to the sinter feed and off-gas quenching.

Jan 1, 2003

By Philip Arthur

The ISASMELT process is making a significant contribution to the global metals industry. ISASMELT furnaces are now operating successfully in eight different countries and treating approximately 3 million tonnes of concentrates and secondary materials per year. The process is currently used in both lead and copper smelting. The most recently commissioned plants were in Germany and China, one for treating scrap copper and the other treating low-grade copper concentrates. The Copper ISASMEL T furnace ("CIF") at Mount Isa Mines Limited ("MIM") has continued to set new operational records, with throughput of more than I million tonnes of concentrate per year and very low operating costs. This paper summarises the latest operational data from the Mount Isa Copper ISASMELT plant and outlines the successful approach to industrial R&D taken by MIM in the development of the ISASMEL T process.

Jan 1, 2003

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