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Thallium is a very minor element found in lead ores. It's behaviour during lead smelting has recently become of much greater interest due to the effects it had on the health of waste heat boiler maintenance contractors at a Canadian smelter. In this paper the behaviour of thallium in both traditional and direct lead smelting processes will be examined using computational thermodynamics techniques. Yazawa and his coworkers have made extensive use of computational thermodynamics to examine and illustrate pyrometallurgical processes. It has been shown that thallium behaviour during smelting is strongly influenced by the extent of oxidation of the lead concentrate and by the presence or absence of chlorine in the charge. The condensation behaviour of thallium species in the waste gas handling system was also modelled and it has been confirmed thallium-rich deposits can form at the high temperatures prevailing in waste heat boilers.

Jan 1, 2003

By Sang-Su Lee

This paper shows the application of the porous plug system in the Mitsubishi continuous copper smelting and converting process. This system has already been adopted and utilized in the steel industry to enhance productivity. Recently, some copper smelters have adopted this system but the results have not been satisfactory. The porous plug system was installed at the anode furnace in December 2001 to reduce the oxidation time and decrease the oil consumption. A good effect was that the nitrogen stirring of the melt through porous plugs improved the melt heat transfer. As the result of the enhancing heat transfer the oil consumption and the build-up inside the furnace were actually decreased. But until now the oxidation time has not been sufficiently reduced. In the future, further research and tests are needed in order to increase the productivity and save costs.

Jan 1, 2003

Hazardous waste has often very complicated chemical compositions in a variety of physical forms and is normally processed in rotary kiln incinerators. Due to large variations in waste types and difficulties in feed characterization, the complex transport processes within the incinerator are not well understood, and the incineration process meets challenges in a smooth operation, and expects various uncertainties in the process chemistry and emission control. For better understanding of the incineration process, simulation was carried out by using Computational Fluid-dynamics (CFD) to characterize temperature and species distribution in the incinerator. In order to catch certain aspects of thermal and chemical behavior, a novel approach is proposed to represent approximately the waste streams and the subsequent combustion process. Hazardous waste in various forms from an industrial-rotary-kiln waste incinerator is firstly converted to a hydrocarbon-based virtual fuel mixture with approximately the same HIC molar ratio and calorific value. The simulation of the combustion process of the simplified hazardous waste was proceeded with a combustion model. The distribution of temperature and chemical species especially the remaining CO in the system is preliminarily investigated. Distribution of CO concentration, as a good indicator of emission level for the incineration process, could be used to evaluate the emission control. The predicted temperature distribution has been compared with available measurement data from an operating rotary kiln waste incinerator at A VR-Chieme, in the Netherlands. Reasonable agreement has been reached between the measured and predicted temperature data. [n the next step, measurement of species distribution in the system is planned to further validate the combustion model.

Jan 1, 2003

By Hector Henao

To provide thermodynamic data for converting the nickel matte to liquid nickel, an experimental study was conducted in the phase equilibrium between the Ni-S alloy and the CaO-Al2O3 based slag melted in a MgO crucible at 1873 K under controlled Pso2 of 10.1 kPa and Po2 in a range between 2.5x 10-and 10.1 Pa by using CO-CO2-SO2 gas mixtures. The content of nickel in the slag at Po, of 10.1 Pa, above which solid NiO is expected to precipitate in the equilibrium state, was found to be 4, I mass% and the contents of sulfur and oxygen in the nickel melt were 0.4 and 02 mass%, respectively. ft was clarified that increase in the temperature reduces the solubility of nickel in the slag and the contents of sulfur and oxygen in the alloy, The distribution of minor elements such as gold, silver, copper, cobalt, iron, arsenic and antimony between the Ni-S alloy and the CaO-Al2O3 based slag was also studied. The distribution ratios of iron and cobalt, defined by (%X in slag)/[%X in alloy] where X is the minor element, are larger values than that of nickel, while those of copper, silver and antimony are similar to that of nickel. The distribution ratios of arsenic and gold are lower than that of nickel in the higher range of oxygen partial pressure.

Jan 1, 2003

By F. Kongoli

Viscosity is an important parameter of copper smelting and converting processes. It affects the settling of matte or metal droplets in the slag, distribution of elements etc. Despite this importance, confusion exists on the viscosity of copper smelting slags as a result of disagreements found among the measured viscosity data of several authors especially in the slags of high ferric iron content and close to magnetite precipitation. In this work a critical review of the existing data on the viscosity of copper smelting slags has been first carried out and the effect of oxygen potential on the viscosity of copper smelting slags has been clarified through a coupled quantification of viscosity and liquidus temperature. The confusion in the literature has been clarified and the importance of the relation between the viscosity and the liquidus temperature is discussed.

Jan 1, 2003

By Akira Nishikawa

During the twentieth century the copper smelting industry achieved dramatic expansion corresponding to the vast growth of global economy. This was largely due to innovations in pyro-metallurgical processes, such as autogenous smelting and continuous smelting and converting technologies. However, as copper production capacity increased, its impact on the environment also could not be ignored, and thus with increasing global environmental awareness, many smelting operations either had to renew or rebuild their facilities. In addition to these changes, in places like Japan and Europe, with scarce primary resources, the treatment and recovery of metals from a variety of items such as car shredder dust, used electrical appliances and electronic devices, on top of scraps traditionally treated, is having a profound effect on the reduction of waste and the preservation of primary resources. Thus compared to the days when copper smelting focused on the environmental control in order to break with "Smoke Stack Industry", copper smelting today is making an important contribution to the sustainable development of human society.

Jan 1, 2003

By Takahiro Miki

Soldering material widely used is Sn-Pb alloy, which have low melting point and excellent electrical, strength properties and wettability. However, Pb is one of the toxic elements, which is undesirable due to environmental and safety reasons, thus Pb-free alternative alloy is preferred for new soldering material. Sn-Ag and Sn-Zn based alloys have been viewed as very promising candidates, among many potential substitutes. Addition of third element to these alloys will decrease melting point of the alloys. Hence, Sn-Ag-In and Sn-Zn-Mg alloys are expected to be suitable for replacing Sn-Pb solder alloy. In order to design new Pb-free soldering materials, it is crucial to understand precise thermodynamic properties and phase diagrams of alloy systems. In the present work, ion current ratios of Ag to In and Mg to Zn were measured for Sn-Ag-In and Sn-Zn-Mg alloys by mass spectrometry, respectively. Also, the authors reviewed the thermodynamic properties of terminal binary alloys determined by other researchers and evaluated a thermodynamic functions to express the excess Gibbs free energy of each binary alloy. Thermodynamic functions to express the excess Gibbs free energy of liquid Sn-Ag-In and Sn-Zn-Mg ternary alloys were determined, utilizing the assessed Gibbs free energy of terminal binary alloys with the measured ion current ratios using mass spectrometer.

Jan 1, 2003

By Zhitong Sui

Based on several case studies on the precipitating behavior of valuable nonferrous metal compounds (VNMC) in molten slags a green technology for the recovery of VNMC from molten slags was proposed. This technology involves three steps: (I) The selective enrichment of the dispersed VNMC into the designed mineral phase in the molten slag; (2) The selective coarsening of the designed mineral phase to a critical grain size in the molten slag; (3) The selective separation from tailing of the grown mineral phase in the solidified slag by dressing or hydrometallurgy processes. This is a clean and low cost technique and has a great capacity to deal with a large quantity of slags. The utilization of the recovered VNMC such as Titanium, Boron, Vanadium compounds was summarized as examples of application. It was confirmed by experiments that the precipitating behavior of the designed mineral phases like Perovskite(CaTiO3), Suanite(2MgO*B2O3) and Sincosite(CaOoV2O5*P2O5) in molten slags is obviously affected by operation factors such as temperature, chemical composition, heat-treatment, additives and so on. The precipitating kinetics and mechanism of the VNMC from molten slags during solidification processes were also investigated.

Jan 1, 2003

By Bora Derin

This work deals with the recovery of valuable metals from the ancient copper smelting slags located in Küre-Turkey. In this process, copper and cobalt were recovered in metallic form and/or as their compounds, whereas iron was recovered as magnetic oxide or pigment. Abrasive grit material was produced using reduced final slag. The process stages involved carbothermal reduction in a DC arc furnace, granulation, leaching, chemical precipitation, selective sulfidizing roasting and product preparations. In this paper, the process stages were described as theoretically and experimentally whereas slag and products were characterized in detail.

Jan 1, 2003

By D. Papazoglou

This work was undertaken to investigate the thermodynamic and kinetic feasibility of using hot sulfur dioxide bearing gases from smelting processes to selectively sulfate the nickel in nickel laterite ores for subsequent extraction in water. The environmental benefits of this approach, as opposed to releasing the gas to the atmosphere, and the economic benefit of directly utilizing the SO2 rather than converting it to sulfuric acid are strong drivers for such a process. A thermodynamic analysis indicated that selective sulfation of the nickel could be feasible under appropriate conditions and these were explored through a series of laboratory scale experiments. Laterite samples were reacted at temperatures between 500 and 800°C with an equilibrated mixture of sulfur dioxide, oxygen and nitrogen in a fixed bed reactor. Tests were conducted on saprolitic ore from Bulong, Western Australia:, limonitic ore from New Caledonia and gamieritic ore from Indonesia. Nickel extractions were highest from the limonite and relatively low from the other ores. The maximum selective extraction of nickel from the limonite in a single stage sulfation was 73%. Sulfation of other elements present in the laterites was also examined. A two-stage process was also identified which involved sulfation using a strong sulfation potenrial followed by weaker sulfation potential to attempt to convert ferric sulfate formed in the first stage to ferric oxide. This increased the extraction for the limonite ore to around 84% Ni, 95% Co and 2% Fe. Direct sulfation of laterite could be feasible in locations where sulfide smelting or roasting operations are relatively close to laterite deposits.

Jan 1, 2003

By E. V. Verhoej

The proposed EU directive on the restriction of the use of certain hazardous substances in electrical and electronic equipment promotes the substitution of lead in consumer electronics to reduce emissions from lead in the end of life phase. In this paper, the consequences of substituting lead in solders is assessed using the Eco-Indicator-99 method for the examples. The base metal production system is considered as an interconnected network modeled dynamically in Simulink 4 and Matlab 6 (Mathworks Inc 2000), where the recovery and production of metal components of the assessed product partially overlap. This approach requires global modeling of metal production processes and mass balances and resulting allocation choices. It also reveals the susceptibility of LCA scores to different choices in the modeling and data availability and uncertainty. Besides the comparison between lead-free and lead-containing solders, other side effects are revealed. Lead is carrier material for the recycling and production of many co-elements in the interconnected production and recovery system. Substitution may have adverse effects such as temporary shortages of other connected metals that are often not considered in normal LCA assessments, thus leading to erroneous results. The suggested approach provides directions for including these extemal effects and for further assessment of the environmental effects of substituting lead. This paper shows that in order to assess the environmental aspects of metallurgy, dynamic modeling of the total system is required based on the fundamental thermodynamics in each metallurgical reactor, the basis of this dynamic model. With this the true environmental impact of metallurgy can be explained. In the case of lead free solder, it is shown that the mining of substitutes has a very much larger impact.

Jan 1, 2003

By Supachai Surapunl

The distribution behavior of VA minor elements (As, Sb and Bi) in the smelting stage of the Mitsubishi process were evaluated thermodynamically based on thermodynamic data and operating data. The fractional distributions between the gas, slag and matte phases considered as the degree of vapor saturation of l.0 are as follows: 53.8, 27.2 and 19% for As, 23.6, 56.6 and 19.8% for Sb, and 91.3, l.1 and 7.6% for Bi, respectively. Arsenic is mostly distributed to the gas and slag phases. It is effectively eliminated by volatilizing and slagging. Antimony is mainly in the slag phase, which is suitably removed by slagging. Bismuth is easily vaporized to gas phase. The degree of vapor saturation has a large effect on the distribution behaviors of the three elements between the three phases. The amount of a minor element in the charge has an effect on the distribution of As but no effect on the distributions of Sb and Bi. Increasing matte grade and temperature results in the change of distributions for As and Sb, significantly. The change in the distribution ratio between slag and matte phases also considerably affects the distributions of As and Sb. The distribution behavior of Bi is not significantly changed by the change in matte grade, temperature and distribution ratio.

Jan 1, 2003

By Hiroshi Hashimoto

For the application of sodium carbonate slag treatment to product high purity copper on an industrial scale, the counter-flow batch process that reduces the amount of utilized slag is proposed from the viewpoint of the post-treatment of slag. Based on the distribution ratios of several impurities between the slag and molten copper determined previously, the effectiveness of this process is discussed using a mathematical model and confirmed experimentally. According to the model, the slag consumption to remove Sb to a required level in case of the counter-flow batch process with 3 reactors is calculated to be around 30 % of that in the case of an ordinary batch process, where pure sodium carbonate is used as a slag at every stage.

Jan 1, 2003

By Grigore Matei

The thermodynamic properties of CuzS-FeS system are important not only in the ease of copper smelting but also in the case of general pyro-metallurgy. However there arc not many reported activity data In this study, activities of FeS and CU2S in the Cu2S-FeS system were calculated using the Darken's method from the activity data of the Cu2S-FeS-Sb2S3 systems measured by the transportation method at 1050°C. The activities of Cu2S and FeS in the Cu2S-FeS system showed negative deviation from the ideal behaviour and satisfied the relation of the Gibbs-Duhem equation.

Jan 1, 2003

By Etsuro Shibata

The saturated solubility of chromium oxide and the valence of chromium in the slag are important matters when considering how to effectively utilize chromium-containing slags. The experimental data of various types of slags cited in the literature were arranged according to the optical basicity in order to evaluate the effects of the oxygen potential and the slag composition. The saturated solubility of chromium oxide and the Cr2+/ Cr3+ ratio tend to decrease with the increase of the optical basicity of the slag at an oxygen potential below 10.5 atm. However, at an oxygen potential of 0.21 atm, the saturated solubility and the Cr6+/Cr3+ ratio tend to increase with an increase of the optical basicity. A practical approach was suggested to reduce chromium in the stainless steel slag and simultaneously recover it as a ferroalloy by the direct smelting reduction of chromium oxide in the molten slag using some reductant in a small furnace.

Jan 1, 2003

By Yuzuru Sato

Viscosity has been measured for various molten binary alloys of nickel with iron, cobalt and chromium in order to clarify the behavior of viscous flow of molten nickel alloys. The entire concentration range for iron and cobalt and 0-67at% of chromium content were studied. The measurement method was an oscillating cup viscometry using an alumina crucible that was precisely machined. The temperature was up to about 1880K for all the measurements. The results represented good Arrhenian relationship although some measurements included overcooled temperatures. The isothermal viscosities increased monotonously with an addition of iron and chromium into nickel. The addition of cobalt increased after stationariness. The isothermal viscosities showed concave curves. Activation energies increased monotonously by adding all the elements into nickel. These phenomena were considered to be related to the thermodynamic properties such as the heat of mixing and the structures of mixture melts.

Jan 1, 2003

By Junzo Hino

Most of the waste that contains a small portion of copper is landfilled. The recycling process of copper from the waste, such as shredder residue, should be developed in order to save mineral resources and prevent environmental pollution. Shredder residue, generated from disposed automobiles and electric appliances, consists of many types of plastics, glasses and metals. The combustion heat of plastics is efficiently used for smelting in the recycling process that consists of melting and reduction. Because the waste contains numerous components the knowledge of the distribution behaviors of the main components is necessary to develop the recycling process. The distribution behaviors in the recycling process are evaluated by using the thermodynamic calculation program, HSC Chemistry. The calculation results are compared with the practical operation data of the recycling process and discussed.

Jan 1, 2003

By Brajendra Mishra

Molten Salt electrolytic processes offer unique opportunities to extract and refine metals where gaseous or metallothermic reduction, hydro metallurgical extraction and aqueous electrolytic methods are thermodynamically constrained. Production of aluminum and magnesium by molten salt electrolysis are well known commercial processes. Several other reactive metals, such as lanthanides and actinides, as well as beryllium and calcium, make use of molten salt processing for extraction and refining. This presentation describes the science of molten salt chemistry and electrochemistry for winning and refining of several metals. In addition, recovery of metals from waste process salts by molten salt reduction as well as oxidation have been discussed. Material issues in design of molten salt reactors have been included. Various applications have been presented through case studies. Experimental data have been included to justify the suitability as well as limitations of these specific processes.

Jan 1, 2003

By E. Munnik

The Chambishi Metals Cobalt Plant in Zambia has recently installed a novel oxidation/precipitation pressure leach process as part of the COSAC (Cobalt from Slag and Copper as by-product) Project. An iron-cobalt-copper alloy, produced by the carbothermic reduction of slag, is atomized and pumped to the COSAC Leach Plant, where cobalt and copper are recovered as dissolved sulphate salts, and iron is rejected primarily as hematite. Cobalt and copper are subsequently recovered as cathode metal in the existing Chambishi operation by conventional electrowinning. This paper examines the challenges faced during the design and subsequent successful commissioning of the COSAC Leach Plant.

Jan 1, 2003

By V. Montenegro

Smelting of copper concentrates in Teniente Converter produces highly oxidized slag, containing from 4 to 10 % Cu and from 15 to 25 % of Fe304. Copper recovery requires magnetite reduction at a level of 5%, determining the degree of cuprous oxide co-reduction and the liberation of copper matte inclusions. The rate of slag reduction is controlled by the mass transfer to the reaction interface. Slag stirring affects the rate of reduction and enhances coalescence of mechanically entrained copper matte inclusions. Slag reduction and sedimentation in the AC electric furnace is a commonly used method of slag cleaning. Utilization of DC electric furnace creates beneficial conditions introducing slag electrolysis additionally to chemical reductions with carbon of coke and electrodes. Application of external magnetic field, interacting with a direct current in an electric furnace, induces magnetohydrodynamic phenomena, such as intensive stirring and electromagnetic buoyancy force acting on inclusions. Laboratory scale research in simulated DC electric furnace with a superimposed magnetic field showed a significant acceleration of the rate of slag reduction and copper removal. Continuous measurement of gas flow and composition allowed for determination of the reduction rate along the time. Application of external magnetic field in the reduction of the industrial slag in a crucible simulated DC electric furnace results such as the increase of the reduction rate from 2 to 3 times, compared with the identical conditions in the AC electric furnace. Interaction of non-homogeneous electric field with crossed permanent magnetic field induces vigorous slag stirring, enhance mass transfer and accelerate the rate of the slag reduction. Additional participations of the slag electrolysis in the magnetite and cuprous oxide reduction as well as the acceleration of the settling of the inclusions by the electromagnetic buoyancy force affect the slag cleaning intensification.

Jan 1, 2003