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By Jerome P. Downey

Technologies developed within the field of extractive metallurgy to recover, concentrate, and purify metals and industrial minerals from ores, have served as the foundation for all of the subsequent environmental remediation, materials recycling, and waste management technologies. This paper discusses the application of classical extractive engineering principles to the development of a thermal process for the recovery of mercury from solid wastes. Process development is presented as a series of logical stages, which begin with a thorough characterization of the site-specific waste, move on to bench and pilot scale testing of the process options, and end with a functional process flowsheet. This paper also presents thermodynamic data on many mercury species of interest to the minerals, power, and chemical industries. These data can be used to model the speciation and recovery of the mercury as a function of various process parameters.

Jan 1, 2003

By Catherine Williams-Beam

Thallium is more toxic to humans than mercury, cadmium, lead, copper or zinc. Its chemical behavior resembles the alkali metals (K, Rb, Cs). It occurs almost exclusively in natural waters the monovalent thallous cation. The solubilities of thallous compounds are relatively high so that monovalent thallium is readily transported through aqueous routes into the environment. The major sources of thallium are the base metal sulfides and precious metal bearing sulfides. Therefore, it is often present as a contaminant constituent in waters emanating from heavy metal sulfide bearing deposits. Thallium can be effectively removed from wastewater to <2 µg/L by reductive precipitation of thallium sulfide. Effective thallium sulfide precipitation requires a controlled solution potential/pH combination. The required potential can be effectively achieved by utilizing a particulate iron slurry or packed column environment. Experimental results will be presented and discussed.

Jan 1, 2003

By C. A. Morais

The present work describes the development of an efficient and relatively simple process to obtain high grade CeO2 from a mixed rare earth chloride solution. The process involves cerium oxidation and precipitation by addition of a KMnO4-NaCO3 solution. The experiments were carried out at room temperature (25 1° C). The results indicated that the major parameters affecting cerium recovery are the molar ratio of KMnO4/Ce, the initial acidity of the chloride feed solution and final pH of Ce(OH)4 precipitation. In strong acid solutions (pH < 1), the oxidation of Cl to Clo took place in addition to the oxidation of Ce(III) to Ce(IV), so increasing the permanganate consumption. Conversely, low acidity (pH >3) led to coprecipitation of the other rare earth elements. Under the selected conditions, cerium was selectively precipitated as ceric hydroxide, together with some manganese dioxide. Further purification was carried out by the dissolution of Ce(OH)4 in HCl, followed by precipitation as cerium carbonate. The filtrate was neutralised with a Na2CO3 solution in order to recover the associated rare earth elements for further separation. The final product, assaying 99.7 % CeO2, was obtained with a recovery of nearly 100%.

Jan 1, 2003

By Patrick R. Taylor

The synthesis of high-purity ultra-fine barium strontium titanate powders (BST: BaO6Sro.4TiO3) has been performed in a non-transferred are D.C. thermal plasma reactor. Slurries of aqueous solutions of dissolved barium and strontium nitrates and solid titanium dioxide powders were used as precursors. Oxygen and argon were used as carrier gases, and pure argon and combinations of argon and nitrogen were used as plasma gases. The plasma torch power was varied, as well as the oxygen flow rate and the total molar concentration of the precursors. A graphite plate was designed to protect the torch electrode and lower the level of impurities in the product. A thermochemical analysis of the Ba(NO3)2-Sr(NO3)2-TiO2-H2O-O2 system was performed to predict the conditions for the formation of BST and the feasibility of the reaction, The powders collected from the different sections of the reactor were characterized using Transmission and Scanning Electron Microscopy, X-Ray Diffraction, and ICP chemical analysis. The powders produced showed high conversion to BST, ultra-fine particle size (< 30 rim) and high purity, which makes this a potential process to produce ceramic materials for electronic devices.

Jan 1, 2003

By Sang Han Son

The vapor pressures of FeCI2 and ZnC12 in the FeCl2-ZnCl2 system were measured by the transpiration method at 873K and 917K. The vapor pressure data were interpreted to indicate the formation of complex ions in the FeCl2-ZnCl2 melts. It is presumed that the complex molecule FeZnCl4 as well as FeCI2 and ZnCI2 exists in the vapors in equilibrium with molten FeCl2-ZnCl2 mixtures. The activities in the FeCl2-ZnCI2 system are shown a negative deviation from Raoult&apos;s law. These results suggest the formation of complex ions such as ZnCl42- in molten FeCI2-ZnCI2 mixtures.

Jan 1, 2003

By N. J. Tannyan

Laboratory bath smelting tests were conducted to determine the feasibility of smelting nickel- copper concentrate directly to a low iron matte in one step. Concentrate, air/oxygen and a silica flux were fed to a matte-slag bath kept in MgO crucibles at I 300°C. Various oxygen enrichments and smelting rates were used to maintain 0.5 to 2 wt% iron in the product matte. The slag losses are comparable to those obtained under similar industrial conditions. Due to the highly oxidizing conditions required to produce mattes with low iron contents, it is not recommended to target iron contents below about 2% in the matte. The specific bath smelting rates were equal to or higher than those in various industrial bath smelting processes.

Jan 1, 2003

By W. H. Jay

Sulphide-containing minerals, particularly iron, lead to acid formation. In turn, the acid generates effluents such as copper acid drainage (AMD). The Berkeley Pit in Butte, Montana, USA and Mt Lyell in Tasmania, Australia, represent just two of many sites throughout the world for which acceptable treatment methods are required. In the gold cyanidation process, the presence of copper creates both a significant cost impediment and a potential environmental hazard. The tailings dam failure at Baia Mare in Romania which led to the release of copper and zinc cyanides created a major environmental disaster. The application of non-toxic water soluble polymers and ion exchange resins to selectively recover copper from AMD solutions, and the in-plant treatment of copper cyanide solutions and slurries to recover copper and recycle cyanide to prevent cyanide entering the tailings impoundment will be discussed. The economics of the various processes will be highlighted.

Jan 1, 2003

By Qiang Yu

This paper reports on a research project supported by NSF, which aims at developing a multi-scale methodology for systematic microstructure prediction in thermo-mechanical processing of metals. This methodology is based on combining mesoscopic microstructure models with macroscopic process formulations and involves the following three main steps: (I) based on the given global processing conditions, the gross deformation patternof the entire workpiece is modeled using a continuum-based algorithm, (2) the resulting parameters are then extracted from the continuum-based simulation, post-processed and passed on to the mesoscopic numerical module, and (3) the microstructural changes are finally modeled at the mesoscopic scale. This approach is expected to overcome the disadvantages of current microstructure prediction practice employing empirical relationships between microstructural features and processing parameters. Keywords: Thermo-mechanical processing, Microstructure, Grain growth; Recrystallization; Mesoscopic models; Finite Element Method

Jan 1, 2003

By L. Sh. Tsemekhman

A new technology for the treatment of copper nickel-containing concentrate after high-grade matte flotation to blister copper with the production of liquid silicate slags in a vertical autogenous unit with upper oxygen blow has been considered. The copper and nickel behavior in the process of sulphide copper concentrate interaction with silicate melt containing oxide copper has been studied. The general mechanisms of such interaction are found.

Jan 1, 2003

By Toshihide Takenaka

The management of radioactivated stainless steel from a terminated nuclear reactor will become an important subject in the near future. The separation of the elements in stainless steel should be effective to reduce the management labor. In this study, the separation of the elements in stainless steel by an electrorefining tcchnique was investigated in an aqueous solution. The electrochemical reactions of the elements in stainless steel werc studied by voltammetry and potentio-static electrolysis was carried out. A stainless steel anode was dissolved electro-chcmically with good anodic current etliciency in a chloride solution. The residue, where Ni was concentrated, was found on the anode after electrolysis. The electrodeposit in a stainless steel cathode consisted mainly of Fe and Cr and the Ni content in it was less than 0.5wt% under suitable condition. It is concluded that an electrorefining technique is effective for the separation of the elements in stainless steel.

Jan 1, 2003

By Ramana G. Reddy

Thermodynamic modeling and experimental study on impurity capacities and their distribution between mattes or metal and slags in smelting, converting and refining of non-ferrous metals was discussed. A brief review on the recent developments in copper smelting and converting is presented. The analysis showed that, copper smelting capacity increased by a factor of 10 since 60&apos;s, smelting rate increased by a factor of more than 5 and process fuel equivalent decreased by a factor of 2. A thermodynamic model for prediction of impurities capacities in slags and their distribution in mattes and slags was developed. The impurities capacities (i.e. sulfur and arsenic) of slags were calculated a priori with no adjustable parameters using the Reddy-Blander model. The capacities predictions were made in a wide range of matte and slag compositions, PSo, and temperatures in conditions pertaining to copper and lead industrial slags. The calculated results for sulfide and arsenate capacities are in good agreement with the available experimental and industrial copper and lead industrial slags data. The sulfide and arsenate capacities in copper slags (fayalite, ferrite and olivine) and lead slags are reviewed. The application of RB model predicted ratios of O2 and S2 partial pressures in industrial copper smelting processes are discussed. Application of this model for the prediction of Sb, Bi and other impurity capacities and their distribution ratios in mattes or metal and slags, in industrial smelting and refining processes is discussed.

Jan 1, 2003

By A. V. Tarasov

Investigations of thermodynamic properties of Cu-Ni and Cu-Ni-S systems and mattes have been conducted with the aid of a MC-130 I mass-spectrometer designed for studies of processes of vapor formation of hardly volatile substances. The instrument comprised a combination of an evaporator of Knudsen chamber type with a mass-spectrometer for analysis of the vapor phase. In the process of studies of molten Cu-Ni-S systems and commercial-grade mattes within a temperature interval of 1400-1800 K the partial pressure of sulfur was measured by means of complete isothermal evaporation and the partial pressure of copper and nickel by comparison of ionic currents. The partial pressure values of the components above the molten Cu-Ni-S were used for calculation of activities of the respective components in the melt. The copper and nickel activity data obtained was used for assessing the amount of dissolved losses of these metals in autogenous smelting slags.

Jan 1, 2003

By Yasuo Ojima

The mainstream of copper smelting processes in the world today is a combination of Outokumpu type Flash smelting and PS (Pierse Smith) converting process. Presently it can be estimated that about 50% of the worldwide copper production is produced by the Flash smelting process and 80% by the PS converting process. PS converting process due to its operational flexibility and despite its batch character of operation has been widely used in many smelters for more than 100 years. However, an environmental issue has been pointed out related to this process because of the difficulty of handling the fugitive gases. Recently several copper smelters in the world have been newly construeted and others have executed major modification and modernization. The continuous converting process has been applied in many of them instead of PS converting process. This paper compares PS to the emerging continuous converting process and makes a prospect of the future of the copper converting process.

Jan 1, 2003

By Yong .. Jun Wu

Laminated ceramics have received widely scientific and commercial attention because their properties, such as mechanical properties and electrical properties, can be tailored by adjusting the structure, thickness and composition of the different layers. For example, ferroelectric Bi4Ti3O12 (BIT) which has a positive temperature coefficient of dielectric constant (,E) can be used to modify the negative tE of typical microwave dielectric ceramic BaNd2Ti4O12(BNT), However, BaNd2Ti4O12/Bi4TiO12/Bi4Ti3O12/BaNd2Ti4O12 (BNT/BIT/BNT) laminated ceramics could not be prepared by the general method because the optimal sintering temperature of BaNd2Ti4O12 ceramic (around 1350°C) was much higher than that of Bi4Ti3O12 ceramic (around 1100°C). In this research, a new method of spark plasma sintering (SPS) combined with post-sintering was successfully proposed to prepare BNT/BIT/BNT laminated ceramics. It was divided into three steps. In first step, the BaNd2Ti4O12 ceramics were prepared by conventional sintering method. In second step, the calcined and pre-pressed Bi4Ti3O12 powders were sandwiched between BaNd2Ti4O12 ceramic pellets and spark plasma sintered at 900°C for 10min to synthesize BNT/BIT/BNT composite ceramics. In the last step, a post-sintering was employed to reoxidize the partially reduced BNT/BIT/BNT composite ceramics. The results of scanning electron microscopy (SEM) and electron probe microanalysis (EPMA) showed that BNT layer and BIT layer were well bonded and no significant interfacial infiltration between them was observed. The sandwiched BNT/BIT/BNT ceramic with 10.7% BIT in volume has a dielectric constant of 92.85, a low dielectric loss of 01068 and a small temperature coefficient of dielectric constant of 35 ppm/°C at MHz.

Jan 1, 2003

By Takashi Araki

In this work, we have elucidated the two-step oxidative reaction mechanism of 2,4,5-trichlorophenol by adsorbing oxygen atom for oxidative decomposition reaction of 2,4,5-trichlorophenol on oxide catalyst surface using ab initio molecular orbital calculation. In the first oxidation, total energies of reaction products have been shown extremely stabilized at all oxidation positions. This reaction occurs due to charge transfer from benzene ring to adsorbing oxygen atom. As a result, 1£ bonding of benzene ring are weakened. However, the benzene ring of 2,4,5-trichlorophenol does not perform cleavage reaction. In the second oxidation, the benzene ring of2,4,5-trichlorophenol can perform cleavage reaction, since the second oxidation obtains larger stabilized energies than the first oxidation.

Jan 1, 2003

By Varuzan Kevorkijan

A new method for faster production of functionally graded metal-ceramic laminates is based on reactive pressureless counterflow infiltration/penetration of a ceramic substrate with two different metallic infiltrants. The porous or dense ceramic preform is pressurelessly infiltrated or penetrated from one side by the first metallic infiltrant to the desired cross section of the preform, producing the top layer made up of the solidified infiltrant and the underlayer consisting of reactive infiltrated preform. The partly infiltrated perform is then completely infiltrated starting from the other side by the second metallic infiltrant, in this way fabricating the internal layer, consisting of the ceramic perform infiltrated with the second infiltrant and the bottom layer formed by the solidified second infiltrant. Systems already investigated include carbide, nitride and boride ceramic performs infiltrated with aluminum and magnesium alloys.

Jan 1, 2003

By Takao Yasugi

The majority of copper in the raw material migrates to the de-copperized dross that forms when the crude lead produced in the blast furnace is treated in the de-copperizing process. The de-copperized dross is treated in the electric furnace producing matte, speiss, and crude lead. The de-copperized dross also contains the silver. Therefore, it is important to improve the rate of silver migration to the crude lead. For this reason, the behavior of silver between the matte, speiss and crude lead phases was examined. At the same time, several tests to improve the percentage of silver migrating to crude lead were conducted.

Jan 1, 2003

By Niloy K. Nath

Two layer sintering by charging green sinter mix with normal coke rate in the upper layer and reduced coke rate in the lower layer, can substantially reduce the coke rate and also improve the sinter quality by producing more uniform thermal profile through out the bed height. The two-layer sintering process have been analyzed by numerical simulation of the process by a detailed CFD based model, considering all the important phenomena like gas-solid reaction, melting and solidification, flow through porous bed, heat and mass transfer etc. Optimization techniques like genetic algorithm, differential evolution is then applied to evaluate the optimum coke rate in the two layers of the bed to produce the ideal thermal profile and melting fraction in the sinter bed for optimum sinter quality. Through this optimization method both high quality sinter with minimum return fines can be achieved along with reduced coke rate. Application of a genetic algorithm for this type of process optimization has several advantages over the traditional optimization techniques since it can identify global optimum condition and perform multi-objective optimization much easily for complex industrial process like iron ore sintering. Keywords: Two-layer Sintering, Iron Ore Sinter Quality, Ergun&apos;s Equation, Gas-solid reaction, Melting Fraction, Multi Objective Optimization, Pareto Set, Genetic Algorithm

Jan 1, 2003

By Guo Xueyi

The morphological characteristics of the nickel particles electrodeposited from chloride dominant aqueous solution was investigated. The effects of the electrolyte constituents, the parameters for the electro-deposition on the morphology of the nickel particles were addressed. It is evidenced that not only the particle size but also the morphology of the deposited nickel particles strongly depend on the electrolyte constituents and technical operation conditions. The electro-crystallization mechanism of the metallic nickel particles deposited at high current density was elucidated. The ultra-fine nickel particles with flake, nodular or dendrite shape may be produced by controlling the duration for electro-deposition.

Jan 1, 2003

By Rodney L. Williamson

Vacuum arc remelting (V AR) is an industrial metallurgical process widely used throughout the specialty metals industry to cast large alloy ingots. Part of the V AR control problem consists of adjusting arc current to control electrode melt rate which also depends on the electrode temperature distribution. Because the temperature distribution responds very slowly (1-4 hours depending on size and material) to changes in melt power, the melt rate response is history dependent and highly nonlinear. The situation is complicated further because measurement of the electrode temperature distribution is not practical. To solve the problem of accurate, responsive melt rate control. a low order electrode melting model has been developed and incorporated into a V AR process controller. Data from laboratory and industrial tests show that the goal of responsive, accurate melt rate control has been achieved, even when melting under highly dynamic process conditions. Keywords: Vacuum Arc Remelting. Model-Based Control

Jan 1, 2003