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By Suzzann Nordwick

The metallurgical treatment of mercury-containing materials for precious or base metals recovery imposes many processing and environmental challenges. Mercury is usually present as elemental or cinnabar. Historically, mercury has been removed from mined ores pyrometallurgically by roasting, but hydrometallurgical methods have also been employed. For example, alkaline sodium sulfide solution acts as an universal solvent for most mercury compounds. While, most other metals are highly insoluble in this solution. This allows for a high degree of selective separation of mercury from other metals with the exception of tin, antimony and arsenic. Mercury leached with a solution of sodium hydroxide and sodium sulfide or sulfur can be re-covered by cementation or stabilized through sulfide precipitation. Hydrometallurgical technology for the pretreatment of mercury removal from gold, silver, and base metal ores using alkaline sulfide leaching will be discussed with a focus on alkaline sulfide leaching of mercury sulfide-containing materials.

Jan 1, 2003

By Petre Stelian Nita

In small steelmaking shops, in foundries and forging plants, there are not too many option to recycle the basic slags, which are not suitable for many purposes of recycling, because of their low chemical and structural stability. A solution of an adequate recycling is a direct recycling in EAF. Several quality requirements, physico-chemical properties and proportions of slags must be analysed. The progress in this fields permites to establish an adequate proportion of recycled slag, based on enough exact computation of the related property. For oxydizing slag, obtained during melting and in the first part of decarburization operation, the problem of phosphoms contents can be analysed using the phosphate capacity (C PO34-). For reducing periods, during deoxidization operation, desulphurization also occurs and the problem of the sulphur contents can be analysed using the sulphur and sulphide capacities ( Cs / Cs) Between this two complex thermodynamic indicators of the slags. a direct relation is established, using thermodynamic aspects, resulting from the equilibrium constants for dephosphorization and desulphurization process and also, using the optical basicity of slags, computable from the chemical analysis of the slags. On this basis starting from the steel quality requirements. adequate strategies can be established in order to obtain high rates of recycling (between 50-80%) of steelmaking slags. Important cost savings are obtained through this procedure, based on the correct amounts of the fresh lime, iron ore and fluidizers. Keywords: Slag, Properties, Recycling

Jan 1, 2003

By Shu Yamaguchi

The behavior of halide impurities in pyrometallurgical processes such as Wealtz kiln and MF process has been discussed based on the thermochemical data and the reported data of PbO activity in PbCl2-PbO melts. The role of PbCl(g) has been estimated to be significant in the chloridization evaporation reaction. From reported data on the PbO activity in PbC12-PbO melts, activity of PbCl2 has been calculated by the numerical integration of Gibbs-Duhem equation, and the stability domains and the composition of the liquid phase as well as the vapor pressure of PbCl2 have been estimated as functions of log P2HCI/PH2O and temperature. From the discussion of the path during cooling process on the log P2 HCI . PH2O vs. temperature diagram, the authors proposed a possible dechioridization process that utilize water vapor as a dechloridizer for the direct precipitation of PbO from gas phase.

Jan 1, 2003

By Roberto Parra

The classic criteria of the preparation of the charge for the smelting of copper concentrates in a flash furnace considers the mass and energy balance from the chemical and mineralogy composition of the concentrates. The operation parameters fixed with this method don't assure the stability of the operation and the critical problems of the slag quality and dust formation occurs very often. This paper presents the results of a laboratory test that allows the predicition of the behavior of concentrates blends in the view of the minimization of the dust formation and the magnetite control in the slag. The combustion of different copper concentrates and blends were done in a drop tube furnace. The results show that the magnetite and dust formation don't have a linear behavior with the weight proportion of the blend and some optimal blends of 2 or 3 types of concentrates can be identified. From the reasonable hypothesis that the qualitative behavior of blends in the drop tube represents the real behavior in the burner, the preparation of the charge with this approach could help to solve those operational problems.

Jan 1, 2003

By Louis W. Cope

Since its discovery, Cuba has been called the “Pearl of the Antilles.” The country remains that, albeit a little tarnished these days. In Havana, many of the buildings are being refurbished, while some new ones are under construction. Since 1991, the laws have been relaxed so that Cuba is developing a mixed economy of central control with free market. Joint venture agreements have been signed with businesses from many countries. This does not include the United States due to its embargo. But even these regulations have been relaxed some.

Jan 1, 2003

By N DavT

Pyritic tailings from the Quirke mine waste management area in Elliot Lake, Ontario were subjected to long-term column leaching experiments in two PVC columns measuring 122 cm in height and 15.2 cm in diameter. At the end of the leaching experiments, the columns were taken apart and sampled at 5 cm intervals for quantitative mineralogical and geochemical characterisation. Each column is represented by a total of ten samples. Polished sections, prepared from the samples, were studied by optical microscopy, scanning electron microscopy, electron microprobe and X-ray diffraction techniques. Mineral quantities were determined based on linear mixing models of whole rock and mineral compositions. Pyrite particle sizes were measured by image analysis interfaced to an electron microprobe. The tailings are coarse-grained (ie 96 per cent passing 75 ¦m) and composed of quartz, K-feldspar, muscovite and pyrite. Pyrite is homogenous and occurs as liberated particles displaying angular to subangular boundaries with strong dissolution features at the end of the leaching experiments. Based on up to 3518 particles measured in a sample, pyrite particle sizes range from 1.7 to 78.6 ¦m. Pyrite concentrations vary from 0.1 to 7.8 wt per cent, depending upon their location from the top of the columns. These correspond to pyrite losses of up to 99 per cent from their original level of 7.2 wt per cent in the upper half of the columns. Pyrite oxidation rates in terms of moles of pyrite oxidised per mole of pyrite per square metre per second were calculated from the effluent data and the measured pyrite particle sizes. The rates vary from 1.71+10-12 to 5.78+10-10 mole+m-2+s-1 within the 1.5 to 3.5 pH range for 10 ¦m particles. These results are comparable with the published oxidation rates at pH 2 where the dissolved oxygen is the only oxidant.

Jan 1, 2003

Pyrometallmurgical reactors constitute a key processing component in the total primary and secondary resource cycle, being involved both in primary smelting, converting and extraction, as well as the reprocessing of scrap, from aluminum cans to end-of-life automobiles. To effectively control the overall resource cycle, one needs to take a systems modeling approach of the whole cycle, seeking to also understand the dynamic process behavior of the individual components of the cycle, and then especially the part that contributes most to the chemical conversion, namely the pyrometallurgical reactor. This paper highlights the role of pyrometallurgical thermodynamics, in the whole resource cycle and specifically places equilibrium thermochemistry in the context of process dynamics where large variable inventories are recycled or maintained within the system. This paper will therefore review the semi-empirical dynamic modeling tools, which are used to model complex systems with the specific goal of developing dynamic predictive models, which also include slag-alloy chemistry, towards controlling the recycling in a feed forward manner. To illustrate the primary processing side, high carbon ferrochrome will be presented as a brief case study. It also will show how the distributed nature of the chemistry of melts in the case of primary extraction, and secondary materials such as recycled end-of-life vehicles, have a significant impact on the process outcomes and model predictions. It is therefore argued that the fundamental thermodynamics and kinetics in metallurgical reactors playa final crucial role in modeling the closed material cycle, but only when it is used in conjunction with process systems theory based on reconciled data for parameter estimation and model calibration.

Jan 1, 2003

By Edward Rosenberg

The synthesis and characterization of silica polyamine composites modified with a variety of sulfur containing ligands is described. The two most successful ligands in terms of sulfur in-corporation and mercury capture are ethylene sulfide and carbon disulfide. The ethylene sulfide forms either an amino mercaptane or a polysulfide upon reaction with amino groups on the composite. The carbon disulfide undoubtedly forms a dithiocarbamate functional group upon reaction of the amino group under basic conditions. Both materials posses excellent capture kinetics and capacities for mercury, Once captured, the mercury is extremely difficult to remove from the composite materials, even with concentrated acids, and they easily pass the TCLP test. The materials are compared with related thioether modified silica polyamine composites and appropriate potential applications are discussed.

Jan 1, 2003

By Maurizio Marezio Bertini

Ammonia - ammonium sulfate solutions were sparged in a glass reactor with a SO2/O2 gas mixture (2% SO2 and 98% O2) to leach copper from pure chalcopyrite and chalcopyrite concentrate. The SO2/O2 mixture produces higher and faster extractions than O2 by itself. The effect of temperature, particle size and free ammonia concentration was investigated. The fastest and highest recoveries were obtained at 80 oC from a chalcopyrite concentrate with a d80equal to 13 m, with about 83 gpl free ammonia, an average pH equal to 8.75 and a stirring speed of 500 rpm. The extraction process was controlled by diffusion through a product layer, according to the shrinking core model, with an activation energy of 41 kJ/mole.

Jan 1, 2003

By L Soares, W T. Hennies, F Fujimur

Barra Bonita reservoir, located in the Sao Paulo State, Brazil, has been mainly used for local navigation and electricity generation to supply a prosper region in the country. Sand mining activities in that area have an important social and economic meaning for the local community. In this reservoir there are several sand mines that produce around 45 000 m3 of sand a month. These deposits were rich in material used as concrete aggregate in the civil construction. However, nowadays a significant increase in the demand of gravel can be observed, representing a serious productive problem. This material hasnÆt been well accepted by the market and, through the years, it was disposed at open sky in piles as waste deposits. This deposits have caused environmental problems like visual impact, reduction of free spaces outside and inside the mine, source of material to erosion and sedimentation processes in lower areas, flooding as a result of the filling up process in the drainage system, among others. For a lack of an appropriate technological characterisation, this material have been mainly used to pavement internal and external areas in the mine, with lower cost associated. With the purpose of evaluate the usefulness of this material in the conventional concrete, there were conducted several tests in the disposed residue including petrographical, physical, and chemical characterisation. The petrographical analysis and the preliminary results of the study showed that the material reacts with the alkalis that are present in the conventional cement (CP-II-E-32). In order to make the application technical and economically possible a research was developed seeking forms to correct this characteristic by adding special cements with high pozzolana content. The results of the technological, physical and chemical characterisation of the products indicated the technical viability of the use of that material. The study also allowed projecting environmental improvements resulting in the elimination of the waste piles.

Jan 1, 2003

By Sharif Jahanshahi

Calcium ferrite slags are often associated with Professor Yazawa due to his pioneering work on the thermodynamics of this type of melts. Over the past years CSIRO has invested some effort in studying physico-chemical properties of such melts to fill in some gaps in our knowledge and explore opportunities for application of the understanding developed. These investigations cover thermodynamics, transport properties of calcium ferrite based slags, as well as the kinetics of reactions of such slags with refractories. The present paper provides an overview of some of these studies and highlights some of the interesting behavior of such melts, The oxidation state of copper and arsenic in calcium ferrite based slags are predominantly Cu+ and As3+, respectively, at oxygen potentials below 10-7 atm. The concentration of CU2+ in such slags becomes significant at oxygen potentials of greater than 10-7 atm at 1300 °C. The activities of CuO0.5 and AsO1.5 in calcium ferrite slags show strong deviations from the Raoultian Law, while that of CoO is very close to ideal behaviour with respect to pure solid CoO. Addition of SiO2 to calcium ferrite slags can have significant effects on the activities of FeO and Fe2O3 and hence the stability of magnetite phase. Transfer of oxygen in calcium ferrite slags is fast with diffusivity of 2x 103 cm2/s at 1350 °C and activation energy of 16 kcal/mol. Presence of solid phases, such as magnetite, has pronounced effect on the viscosity of calcium ferrite slags. The observed dependence on solid loading and shear rate indicates deviation from Newtonian behaviour. The interfacial tension between copper mattes and calcium ferrite slags is strongly dependent on the matte grade, with the determined values being much lower than the corresponding ones for interfacial tension between similar mattes and iron silicate slags. MgO, Cr2O3 and MgCr2O4 have low solubility in calcium ferrite slags and their solubility increases with increasing copper oxide content of the slag at 1300°C. The oxidation state of the slag has strong effects on phase transformation, dissolution rate and disintegration of refractories in calcium ferrite slags. Other key factors with major impact on slag-refractory interactions include viscosity and surface tension of slags as well as the contact angle between slag and refractory material,

Jan 1, 2003

By Charles W. Kenney

Mercury contamination of soil at an old chemical plant surrounded by a residential community and adjacent to a river has provided unique challenges for the current owner. Inorganic and organic mercury compounds had accumulated over the past 50 years to levels that require remediation. Hazen Research, Inc. conducted a multi-phased program to characterize contaminants and their occurrences, evaluate various treatment technologies, and demonstrate the selected technology at bench and pilot scales. A combined physical cleaning and chemical treatment was demonstrated to meet treatment goals for the site. This paper discusses the methods of process selection and results of the bench-and pilot-scale testing.

Jan 1, 2003

By Arthur E. Morris

Fifty years ago when Professor Yazawa began his career, the field of process simulation and modeling was in its infancy. Since then, tremendous progress has been made in our ability to model metal production flowsheets from mine to refined metal. This progress has come about by parallel developments in basic understanding of process chemistry and in computational techniques, This paper will review the progress made in process understanding and modeling in lead, zinc, and copper metallurgy from its inception to the present, and the role of Professor Yazawa's work in furthering this progress. Specific examples will be given for the sintering of lead concentrates, slag fuming, zinc concentrate roasting, flash smelting of copper, and pyro-extraction of zinc. Factors limiting further progress will be described.

Jan 1, 2003

By Tim O’Neil

Tire companies have historically used the mining industry as a platform to launch new technologies. And the mining industry has been receptive to that. So, while developing its Two Piece Assembly, Goodyear noted a number of trends in the mining industry: •The global market sophistication of equipment and operations requires the packaging of products and services to provide the best return on investment. •Industry consolidation and growth have resulted in fewer, more powerful mining houses, leveraging purchasing power in the marketplace. •User productivity demands continue to drive original equipment manufacturers to develop higher pay-load equipment. •Technology needs include improved ergonomics, to reduce fatigue and increase operator productivity. •Increased laws and environmental regulation prohibit on-site whole tire disposal practices.

Jan 1, 2003

By Guojun Qi

This work relates to wafer bumping technologies for flip chip packaging applications in the electronics industry. Nickel and its alloys are alternative under bump metallization (UBM) materials because of their slower reaction rates with Sn-based solder as compared to Cu-based UBMs. In this study, we compared the morphologies of the intermetallic compounds (IMC) formed between Sn-bearing solders (Sn3.5Ag and eutectie Sn-Pb) and two types of nickel- based UBMs, electro less Ni-P (EN) and sputtered nickel. Both chunky-type and needle-type of intermetallics were observed between the EN UBM and the solders. In the case 'of sputtered Ni UBM, there is only a layer of scallop-type intermetallics formed, The morphology change and growth kinetics of the IMC in thermal aging process were analysed. Kirkendall voids were noticed from samples ofSn3.5Ag solder vs Ni-P UBM that have undergone prolonged thermal aging at high temperature.

Jan 1, 2003

By Grigore Matei

The thermodynamic properties of CU2S-FeS system are important not only in the case of copper smelting but also in the case of general pyro-mctallurgy, However there are 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-Sb2SJ systems measured by the transportation method at 10S0°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

An EAF dust generated in a Swedish steel mill has been leached in hydrochloric acid at The solution obtained has been subjected to purification by cementation followed by precipitation of zinc with sodium carbonate. The thermal decomposition of the precipitate was studied using thermal analysis and X-ray diffraction. The results show that during the calcination of the precipitate three different reactions occur. The decomposition of the solid phases Zn5(CO3) (OH)6, CaZn(CO3)2 and CaCO3 occur completely at 370°C, 560°C and 940°C respectively, yielding a final product containing 61.9% ZnO and 38.1% CaO. Methods to minimize calcium and manganese in the final product are discussed.

Jan 1, 2003

By B. Zilbergleyt

Current understanding of chemical equilibrium is based exclusively on the probabilistic considerations that are correct for isolated systems with only one chemical reaction to take place. For the systems with multiple chemical interactions, current paradigm of chemical thermodynamics promotes the idea of openness, artificially flavored with coefficients of thermodynamic activity. Recently introduced thermodynamics of chemical systems and the Method of Chemical Dynamics (MCD) offer explicit accounting for the multiple chemical interactions within the system. In the new theory, thermodynamic equilibrium of the j-subsystem obeys the logistic equation derived exclusively from the currently recognized concepts of thermodynamics. Having the only one new parameter -the subsystem's reduced chaotic temperature 'tj to describe external interactions, and reaction extent Ilj as independent variable, this equation covers the whole domain of the system's possible states from true thermodynamic equilibrium through the open equilibrium to bifurcations and chaos depending on the 'tj value. The MCD brings new opportunities to thermodynamic simulation of complex metallurgical and chemical systems, allowing for the analysis of their domains of states and the area limits, and for more accurate calculation of the equilibrium compositions. Its usage is exemplified in this paper by several applications. Keywords: chemical thermodynamics, open systems. complex systems, chemical dynamics.

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 José Carlos Abreu

This work presents a kinetics study covering the effects of temperature over the reduction rates of a carbon composite briquette, aiming its use as burden in some of the new alternate ironmaking technologies, such as the Tecnored process. It is reported that increases in the temperature increases the reaction rate. Additionally, the morphology of the iron phase generated during the reduction of these briquettes is presented. It was possible to verify that three types of iron morphology occurred during the process: an external, dense and continuous iron layer, the presence of iron globules at the center of the briquettes and whiskers at the briquette's core. The measurement of the carbon content on the globules and the external iron layer is also presented

Jan 1, 2003