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By Mototsugu Matsuno

A new process has been developed to treat fly ash generated from municipal incinerators, which contains not only toxic metals such as lead and cadmium, but also dioxins. The process includes the following steps; fly ash is formed into green pellets with some additives and the pellets are then roasted to eliminate or stabilize the toxic metals and to decompose dioxins. A pilot plant with a capacity of approximately 100 kg/hr was used to test the process. The tests verified that heavy metals were either volatilized or stabilized and dioxins were decomposed by high-temperature roasting. The pelletized ash was found to be non-toxic, so that it can be recycled as artificial lightweight aggregate. It was also found that volatilized metals collected as secondary ash can be recycled as smelting resources.

Jan 1, 2003

By Elizabeth M. Ho

Oxidants are added in uranium leaching in acid media to convert iron(II) in solution to iron(III). Iron(III) has an important role in the leaching of uranium by acting as an electron transfer agent for the oxidation of uranium(IV) to uranium(VI). The oxidation of iron(II) to iron(III) in sulfate solutions using sulfur dioxide/oxygen (SO2/O2) was carried out under typical uranium leaching conditions (pH 1-2, 20-50°C) to confirm literature trends and this work was then extended to the use of SO2/O2 in the leaching of uranium ore. The oxidation rate was found to be dependent on the initial SO2/O2 volumetric ratio and the oxygen mass transfer rate, but was independent of the initial iron(III) concentration above about 200 ppm at pH 2. The presence of 55 ppm organic extractant (Alamine 336) decreased the reaction rate. The oxygen mass transfer coefficient (kLa) for the mixing tank system was measured and was found to decrease with increasing solids density in a 1 g L-1 MgSO4.7H2O solution.

Jan 1, 2003

By George S. Dulikravich

An advanced semi-stochastic algorithm for constrained multi-objective optimization has been adapted and combined with experimental testing and verification to determine optimum concentrations of aJ10ying elements in heat-resistant and corrosion-resistant H-Series austenitic stainless steel alloys. The objective was to simultaneously maximize a number of alloy's mechanical properties. This research will result in a rigorous tool for the design of high-strength H-Series steels and other types of alloys unattainable by any means existing at the present time. Such a material-by-design tool will also be able to reduce or minimize the need for the addition of expensive elements such as Cr, Ni, Co, Nb, Ti, V, etc. and still obtain the optimum properties of an aJ1oy.

Jan 1, 2003

By J. E. Dutrizac

The behaviour of the lanthanide elements during the precipitation of sodium and potassium jarosites at 98oC from sulphate media was systematically investigated. The lower atomic weight lanthanide elements (La to Gd) are characterized by the limited solubility of their alkali-lanthanide sulphates, such as NaNd(SO4)2?H2O, which commonly contaminate the jarosite precipitates. Hence, single phase jarosite-type compounds were precipitated only from solutions containing <0.4 g/L of the La to Sm lanthanides. The sulphates of the heavier atomic weight lanthanide elements (Tb to Lu) have significantly higher solubilities such that solutions containing up to 10 g/L of the individual lanthanides could be investigated without the precipitation of alkali-lanthanide sulphate species. Even at the highest lanthanide concentrations, however, none of the jarosite precipitates incorporated more than 0.3 wt% of any of the lanthanide elements. Comparable levels of lanthanide incorporation were noted in both Na-jarosite and K-jarosite. Although the mass of the jarosite precipitate increased with increasing ferric sulphate concentration or with increasing pH, the extent of lanthanide incorporation was not significantly affected. Clearly, the trivalent lanthanide elements do not substitute extensively for trivalent iron in the jarosite structure. This behaviour likely reflects the significantly lower hydrolyzability and larger size of the trivalent lanthanide ions relative to ferric ions.

Jan 1, 2003

By Guy Xueyi

The environmental impact assessment of the Imperial Smelting Process for metallic zinc and lead production in Shaoguan Smelter, China, was carried out by the life cycle assessment method. The detailed inventory analysis of the Input/Output in the process during 1998-2000 was conducted and the allocation was done among the main products of zinc, lead and sulfuric acid, according to the system expansion and substitution principle, The environmental impacts were assessed by using the following five Eco-indicators: Gross Energy Requirement (GER), Global Warming Potential (GWP), Acidification Potential (AP), Heavy Metal Toxicity&apos; (HMT) and Solid Waste Burden (SWB). The results from this study are useful to address the environmental situation of the technology practice in this smelter, and provide a scientific basis for the further improvement.

Jan 1, 2003

By Andreas Siegmund

Cast or rolled lead anodes employed in zinc electrowinning typically contain between 0.5?1.0% silver to decrease the overall corrosion rate. The production of cast lead-silver or lead-silver-calcium anodes often results in the formation of numerous holes, voids or laps in the anode surface that can initiate internal corrosion in localized areas. In rolled anodes the presence of internal porosity is significantly reduced, thus resulting in extended service life. The obtained grain structure of cast or rolled Pb-Ag anodes, however, requires a relatively long period of time to form a stable protective PbO2/MnO2 layer that can evolve oxygen without excessive lead contamination of the cathode. Therefore, these anodes are often mechanically, chemically or electrochemically conditioned prior to being placed in the electrowinning process. RSR Technologies has developed an improved anode for zinc electrowinning. The anode consists of a rolled Pb-Ag-Ca-alloy with controlled surface grain structure. The preferred calcium and silver content of the alloy is 0.05?0.08 % and 0.3?0.4%, respectively. Since May 2001, industrial-scale tests have been carried out at two zinc refineries in North America in industrial electrowinning cells. The controlled grain structure of these anodes allows forming an adherent protective oxide coating within a short period of several days when placed in an electrowinning cell without the necessity of being preconditioned. Anode sludge growth is evenly distributed. The anodes stay dimensionally stable and no short-circuits have been observed. Consequently, low corrosion rates and improved current efficiencies have been achieved.

Jan 1, 2003

By Fumito Tanaka

The Mitsubishi process is the sole pyrometallurgical process for the continuous production of blister copper from copper concentrates and has been successfully operated around the world. The development of calcium ferrite slag (CaO-FeOx-Cu20), the so-called "C-slag", has enabled continuous converting from matte to blister copper in the commercial scale operations. Commercial interests in the slag led to many papers over the CaO-FeOx slag. However, CU2O- bearing slag has not been studied well due to experimental difficulties. The authors have quantified the thermodynamic properties ofthe CaO-FeOx-Cu2O system. The results have been utilized to analyze various issues related to the converting furnace, such as the magnetite precipitation from the slag or from blister copper and to develop better controlling criteria for the continuous converting operation.

Jan 1, 2003

By Jan Dabrovska

Solidification and cooling of a continuously cast slab and simultaneous heating of a mould is a very complicated problem of transient heat and mass transfer. Nowadays, the solving of such a problem is impossible without numerical models of the temperature field not only of the slab itself, while it is being processed through the whole concasting machine (Caster), but of the mould as well. Two original numerical models have been developed and used in the investigation of a continuously cast steel slab. The first (one of two) 3D model of the temperature field of a concasting is capable of simulating the temperature field of a caster. Experimental research and data acquisition have to be conducted simultaneously with the numerical computation-not only to confront it with the actual numerical model, but also to make it more accurate throughout the process. After computation, it is possible to obtain the temperatures at each node of the network, and at each time of the process. The utilization of the numerical model of solidification and cooling of a concasting plays an indispensable role in practice. The potential change of technology-on the basis of computation-is constantly guided by the effort to optimize, i.e. to maximize the quality of the process. The user can therefore choose any appropriate longitudinal or cross-section of a slab and display or print the temperature field in a 3D or 2D graph whenever necessary. The second numerical model of dendritic segregation of elements assesses critical points of slabs from the viewpoint of their increased susceptibility to crack and fissure. In order to apply this model, it is necessary to analyze the heterogeneity of samples of the constituent elements (Mu, Si and others) and impurities (P, S and others) in characteristic places of the solidifying slab. The numerical model, based on measurement results obtained by an electron micro-probe, generates distribution curves showing the dendritic segregation of the analyzed element, together with the distribution coefficients of the elements between the liquid and solid states. The combination of both models enables the prediction of cracks and fissures in critical points of the continuously cast carbon-steel slab. Both models had been applied in the industrial investigation of a cast low-carbon-steel slab.

Jan 1, 2003

By Jose Bengoa

Low metal prices and environmental restrictions are always a challenge for copper smelters operation and its productivity. Thus, in order to reduce production costs and control gas emissions, improvements of the Teniente Converter (CT) operation were made at 110 Smelter Plant of Southern Peru Copper Co" 110, Peru, and the main objective was to increase its capacity for smelting copper concentrates without affecting normal operation, The present work eorresponds to a recent study conducted during the normal industrial operation of the Teniente Converter in this plant and, it shows the effect of increasing air oxygen enrichment from 28 to 34% on its productivity. The results show an increasing of concentrate smelting rate from 800 to 1370 tpd and hence a notorious improving in copper production, and practically no effect on the refractory consumption. The increment of the concentrate throughput, increases also the SO2 concentration and the sulfuric acid production, showing the effort done by this operation in order to accomplish the environmental Peruvian regulation,

Jan 1, 2003

By Ragnhild Aune

In fire refining of copper, the affinities of various impurity elements on dissolved oxygen is of great significance. Further, in the design of oxygen probes in liquid copper, the influence of solute interactions on the activity of oxygen need to be considered in order to evaluate the oxygen concentration in molten copper. The present paper presents a series of measurements of the activities of oxygen in liquid Cu-M-o alloys (where M stands for Mn, Zn, As, Se or Te) carried out by the present group employing the solid electrolyte galvanic cell technique. Extreme care was taken to control the oxygen potentials in the inert gas atmosphere, and to keep the oxygen levels very low in the molten metal. The oxygen content was determined by analysis of the samples taken out from the melt. The results obtained showed that Mn has a strong negative influence on the activity coefficient of oxygen in liquid copper. A similar, but less prominent effect was observed in the case of Zn. Arsenic had no influence on the activity of oxygen in Cu (liq.). Se and Te had slight negative effect on oxygen activities in copper at XO > 10-5, while at lower oxygen levels the interaction coefficients were found to be positive. The results obtained were compared with empirical models for the calculation of interaction coefficients available in literature.

Jan 1, 2003

By K. H. Ho

This paper describes a simplified numerical model which is used to study the skull formation of liquid metal on a rapidly rotating disc in centrifugal atomisation. The skull formation is one of the problems limiting the wide use of centrifugal atomisation. The enlarging skull on the atomising disc reduces the yield of metal powder produced and produces a resistance to the centrifugal force which worsens the quality of the powder. It is costly and often difficult to study the flow behaviour by experiments due to the complex heat transfer and phase transformation during the processing. Computer modelling is therefore a powerful tool for mechanistic understanding of centrifugal atomisation. This paper investigates the flow pattern of the melt on the rotating disc as a function of initial temperature, melt flow rate and disc rotation speed as well as the physical properties of the melt, such as density, surface tension and viscosity using the commercial package Flow-3D. Keywords: Solidification, Rotating disk, Centrifugal Atomization

Jan 1, 2003

By A. V. Tarasov

In order to improve technical, economic and environmental performance of hydrometallurgical processing of intermediate products containing copper and nickel, the Gintsvetmet Institute and the IMET Institute of the Russian Academy of Sciences have conducted studies into the efficiency of the use of alternating current of industrial frequency on processes applied for hydrochemical leaching of various copper- and nickel-containing materials. It has been found that: 1.Imposition of alternating current over the process of leaching of softly reduced nickel oxide with recycled copper sulfate solutions resulted in an increase by 20 to 30% of the rate of the copper cementation process and reduced by 20% its activation energy. At the same time, the recoveries of nickel, cobalt and iron to the leach solution increased up to 82.2%, 78.5% and 57.1%, respectively, and that of copper to the cement precipitate up to 74%. Optimal process conditions have been identified with respect to the current density, electrode material, copper concentration in solutions and the process temperature. 2.In the process of hydroelectrochemical sulfuric acid leaching of nickel and copper sulfides, the grain size, the phase form of sulfides, the solution composition (H2SO4, Cl?, Cu2+, Fe3+)and the current amperage had an effect on the nickel recovery to the solution, which reached 90%, while the degree of copper transfer to solution did not exceed 20%. The process of hydroelectrochemical sulfuric acid leaching of nickel and copper sulfides with an addition of Cl? made it possible to selectively recover nickel into the leach solution along with concentrating copper in the leach residue. 3.When subjecting samples of commercial-grade magnetic fractions of converter matte to sulfuric acid leaching, the imposition of electric current, the concentrations of sulfuric acid and chloride ion in the solution and the duration of the reaction process had an effect on the process. The nickel recovery was 85% and that of cobalt and iron was 95% and the recoveries reached 97.5%, 98.3% and 99.8% as a result of repeated treatment of the primary residue under similar process conditions. Up to 75% of copper, 75% of sulfur and 99.0-99.5% of palladium was concentrated in the solid reach residues. The experimental data obtained indicates that the use of AC for hydroelectrochemical sulfuric acid leaching for separation of copper- and nickel-containing intermediate products has favorable prospects.

Jan 1, 2003

The reported values of the standard reduction potentials of the Au(NH3)2+/Au(0) and Au(S2O3)23-/Au(0) couples are reviewed to emphasise the experimental difficulties associated with the measurement of reliable values for these quantities. The standard reduction potential for Ag(I)/Ag(0) in ammonia and thiosulphate solutions measured at ionic strength 0.1 and 25oCis used to predict the following relevant stability constants () for gold complexes based on the linear free energy correlations: Au(NH3)2+2 = 1013, Au(S2O3)23-2 = 1024 and Au(NH3)43+4 = 1033. The equilibrium constant ( 10-11) for the reaction Au(S2O3)23- + 2NH3 = Au(NH3)2+ + 2S2O32- based on these stability constants is in reasonable agreement with the measured value (10-9) based on potentiometric and spectroscopic data when excess ammonia was added to a solution of Na3Au(S2O3)2. This also indicates that the stability constant of Au(NH3)2+ is 9 to11 orders of magnitude less than that of Au(S2O3)23-. Relevant species distribution and Eh-pH diagrams based on the revised data are presented.

Jan 1, 2003

By H. Masuda

The lijima Zinc Refinery started operation in 1972, and has today an annual capacity of 200,000t-Zn. The hematite process was employed for the first time and the ideal of waste-free refinery has been pursued for 30 years. In recent years, however, only half of the hematite produced would be sold to the cement industry and hence a reduction of arsenic level has been necessary in order to sell the entire amount produced. The arsenic cementation process with zinc powder, developed through a long time laboratory research was found among some options as the best for the hematite process. The construction work started in 2000 and the facility was put into operation in 2001, As a result in the same year all hematite were sold to the cement industry. The outline of this project, present operations and technical issue are reported in this paper.

Jan 1, 2003

By Hiroyuki Matsuura

The effects of P20S or Na20 addition on the reaction rate of CO2 dissociation on the surface of FexO-base molten oxides was investigated at 1773K by isotope exchange methodl-6_ The rate constant decreased with increasing P20S content of molten oxides and the residual rate constant was observed at high P20S content On the other hand, the rate constant increased with increasing Na2O content for FexO-SiO2 melts. The rate constant was evaluated by the composition of oxides and the rate controlling step of CO2 dissociation was discussed.

Jan 1, 2003

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