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By G. L. Peralta

Geothermal energy is an important source of power in more than 12 countries and is a potential source in 50 countries. However, the exploration and use of geothermal resources generate residues such as scale and sludge. The scale is from the steam distribution pipes while the sludge is from cooling ponds. These solids contain significant levels of elements which are of environmental importance notably, arsenic, sulfur, copper, zinc and lead that require safe treatment and disposal. The compositions, phases, textures, morphologies and size of scale and sludge particles have been studied by laser particle size analysis, light microscopy, scanning electron microscopy, X-ray microanalysis, and X-ray diffraction. In addition, their leachability was tested with protocol leaching procedures and sequential extractions. The detailed spatial relationships and speciation of the environmentally significant constituents have received particular emphasis. The information obtained is useful in understanding how the scale and sludge are formed, their leaching behavior if disposed of in a landfill and in developing appropriate treatment strategies.

Jan 1, 1994

By Lamar S. Todd

The direct production of metal from a sphalerite concentrate is an attractive route for primary zinc. A series of operations and conditions have been selected to efficiently cause the following overall exothermic reaction. The process uses a continuous circulation of molten copper for material and energy transfer between the unit operations. Sulfide concentrate is reduced with an excess of superheated copper to make a copper alloy and white metal. The alloy is stripped of volatile metals under vacuum and some metals can be separately condensed. The residual copper and the white metal are fed into a copper converter to be blown with oxygen for desulfurizing and the superheated copper is recycled. The paper will include a detailed material flow sheet for the process, discussion of the operating conditions of the individual units, behavior of minor elements, and zinc quality.

Jan 1, 1999

By D. E. Woolley

The rate of reduction of iron oxide from calcia-silica-alumina slag by carbon in liquid iron has been measured over the temperature range 1400-1600°C by monitoring the rate of carbon monoxide (CO) evolution. Slags containing ferric iron have been used in order to study the reduction of both ferric and ferrous cations. Results show that ferric iron is reduced before ferrous iron, so that the ferrous iron concentration increases initially. It is also shown that the rate constant, k, decreases at low reaction rates, or, equivalently, at low concentrations. The authors conclude that the reaction occurs in two periods. During the first period, ferric iron is reduced to ferrous iron. During the second period, ferrous iron is reduced to metallic iron, and the rate-limiting step during the second period is the mass transfer of ferrous cations in the slag phase to the slag-metal interface.

Jan 1, 1998

By F. J. J. van Loo, A. A. Kodentsov, J. A. van Beek, M. R. Rijnders

"A periodic layered morphology of the reaction zone has been observed in several annealed solid/solid diffusion couples, including metal/metal and metal/ceramic couples. This morphology is characterized by a regular array of alternating layers, which are either single-phase layers or bands of particles embedded in an intermetallic matrix phase. A description of several systems showing periodic layer formation is given. It is shown that the periodic layered structure with the single phase layers and the one with the bands of particles have a different mechanism of formation.IntroductionSolid state reactions in ternary systems can produce a variety of reaction zone morphologies if there are two or more reaction products. Three types of morphology have been described in detail: 1) simple layered; 2) isolated precipitates in a singlephase layer; 3) interpenetrating columnar (lamellar) or interwoven structure. Understanding the factors that govern the formation of different morphologies is of importance in many fields of engineering. For solid state displacement reactions the conditions governing the formation of these morphologies are well understood [1-4]. For example, the development of a layered or aggregate reaction zone depends on the relative diffusivities of the components through the reaction products.This paper is concerned with the periodic layered morphology which has been observed in various solid state systems. We consider this to be a fourth type of reaction layer morphology. Two manifestations of periodic layered morphology may be distinguished. One form consists of regularly spaced layers of particles of one reaction product embedded in a matrix phase (another reaction product). The other form consists of single-phase layers embedded in a matrix phase. It will be shown that each manifestation has its own mechanism of formation. In section A we consider a system (Ag/Ti-foil/Si) in which periodic layer formation will be explained as a special case of the Liesegang phenomenon. In section B we consider systems where the periodic layered structure has a different origin."

Jan 1, 1996

By Jean P. Murray

The extractive metallurgical industry is a major consumer of high-temperature process heat. It is, consequently, a major contributor of C02 emissions and other greenhouse gases derived from the combustion of fossil fuels for heat and electricity generation, or from the process itself. These emissions can be substantially reduced by replacing fossil fuels with solar energy as the source of process heat. Concentrated solar radiation can supply a large amount of thermal energy to endothermic reactions at temperatures exceeding 2000 K. Another potential for C02 emission reduction exists as well. Thermodynamically, the total amount of energy required for metal production at any given temperature is the enthalpy change of the reaction, AH. Of this total, an amount equal to the Gibbs free energy AG must be supplied as high quality energy in the form of electrical work or by using a reducing agent. Many conventional metallurgical electrolytic processes and reducing furnaces are unable to add only the thermodynamically required electricaVchemical energy due to process inefficiencies. Electrical work in excess of AG for the reaction may be used to supply process heat, or excess chemical reducing agent burned to supply process heat. Besides the thermodynamic and economic drawback, this inefficiency results in excess C02 emissions derived from the combustion of fossil fuels. With these practices, energy becomes an important cost element of the metal produced. Highly-concentrated solar energy has the demonstrated potential to separate these two forms of process energies, allowing the addition of only the thermodynamically required high-quality energy while high-temperature solar process heat is provided to the reactor. Examples of metal oxide reduction processes that have been studied experimentally in solar furnaces include the production of Fe, Al, AI/Si alloy, Mg, Zn, Tic, Sic, CaC2, TIN, Si3N4, and AIN by carbothermic reduction of their oxides, and the high-temperature solar- electrothermal reduction of ZnO.

Jan 1, 1999

By P. M. Prasad

The last two decades have witnessed the emergence of numerous hydrometallurgical and direct processing techniques for the extraction of some metals from pocketed/lean/complex sulfide ore deposits. A new approach with some inherent technological merits, investigated in recent years, is the lime-enhanced reduction of metal sulfides. Thermodynamic aspects relevant to the lime-enhanced reduction of metal sulfides by H2,C0 and C are discussed. A survey of the researches on the basic features of and factors influencing the lime-scavenged reduction of selected sulfides and sulfide concentrates reveals that lime tremendously enhances the sulfide reduction rates (up to 100 times) and drastically reduces the sulfur emission into off-gas to negligible levels. Further successful practice of lime-enhanced reduction requires only a moderate temperature of reduction (characteristic of each sul¬fide) and, in the case of gaseous reduction, relatively low gas flow rates. Relevant kinetic aspects of the concerned reactions that have a bearing on process development and its understanding are also briefly discussed. A conceptual scheme of general applicability for the processing of sulfide concentrates by the lime-enhanced reduction technique consists of three main steps: (0 lime-enhanced reduction by a suitable reagent (e,g., H,2, CO, gasified coal, water gas), (ii) separation of the product metal from the dry slag (CaS + unused CO) by mechanical separation, magnetic/gravity concentration or flotation and (iii) melting and refining by standard procedures. This novel approach, which is patently less complex, is expected to employ basically simpler flow sheets at comparatively lower operational temperatures and aid in pollution abatement. Potential for developing such a route for the small scale extraction of metals like copper, molybdenum and antimony is indicated. Possibility of utilizing this technique for the production of fibers/ filaments of some metals is also outlined.

Jan 1, 1983

By R. J. St. Eloi

The Kidd Creek Copper Smelter has been expanded from its original design of 59,000 tonnes of copper per year to over 120,000 tonnes per year .. Modifications to the process gas handling system and acid plant have been made to accommodate this higher production rate and to .generally optimize the operation. The gas handling system associated with the continuous smelting process is discussed in terms of boiler accretions and modifications to minimize their impact on operations; design changes to effect reductions in high pressure drop duct configurations; material changes to overcome corrosion and plant additions to 'improve gas cleaning capability. The acid plant is reviewed with references to changes made to accommodate the increased S02 gas strength resulting from the higher smelting rates;

Jan 1, 1992

By C. J. Newman

The Kidd Creek Copper Smelter has been expanded from its original design of 59,000 tonnes of copper per year to over 120,000 tonnes per year. Modifications to the process gas handling system and acid plant have been made to accommodate this higher production rate and to generally optimize the operation. The gas handling system associated with the continuous smelting process is discussed in terms of boiler accretions and modifications to minimize their impact on operations; design changes to effect reductions in high pressure drop duct configurations; material changes to overcome corrosion and plant additions to improve gas cleaning capability. The acid plant is reviewed with references to changes? made to accommodate the increased SO2 gas strength resulting from the higher smelting rates.

Jan 1, 1992

By Florian Kongoli

Non-ferrous smelting slags .can contain magnesia, which substantially increases the liquidus temperature. One option to counter this increase is to flux with calcia. In this work, experimental liquidus measurements including new measurements on industrial slags have been compared with a FACT-based thermodynamic model, which predicts the liquidus surface of multi-component iron silicate smelting slags containing both magnesia and calcia. The predictions, which agree well with experimental results, are summarized in both isothermal and non-isothermal diagrams to give a quantitative description of the liquidus surface.

Jan 1, 1998

By F. Elgersma

A high purity electrolysis solution is essential for hydrometallurgical zinc winning processes. For this reason ferric iron containing compounds such as jarosite are precipitated as iron and impurity collector during the calcine leaching. Jarosite thus forms a chemical waste and creates environmental problems. This research contributes to the development of a wet jarosite treatment process, where less contaminated jarosite is produced which can act as an iron source. The present work studies jarosite precipitation kinetics and the uptake of zinc cations in batch and continuous experiments. The distribution coefficient for zinc in continuous experiments is constant for a wide ratio of zinc over ferric ions in the solution. Addition of NH, + ions in batch experiments accelerates the conversion rate equivalent to the driving force increment. Addition of 50,2-ions above the stoichiometric ratio increases the conversion rate less then could be expected from the increase in the estimated driving force. Zinc ions tend to retard the conversion rate. An increasing reaction temperature increases the conversion rate. Below 75 ?C the conversion rate approximates zero.

Jan 1, 1990

By F. H. (Sam) Froes, C. Suryanarayana, K. C. Russell, C. M. Ward-Close

"Far from equilibrium synthesis allows development of novel crystal structures and microstructures, leading to achievement of enhanced physical and mechanical properties. A number of ""far from equilibrium"" techniques are reviewed with emphasis on the amount of departure from equilibrium. The ability of two such techniques, mechanical alloying (MAl, and physical vapor deposition (PVD) to develop novel structures are discussed in detail. For the MA process emphasis is placed on intermetallic compound compositions. Solubility extension, beyond rapid solidification (RS) levels, is found in terminal compositions but not for the intermetallics. Nanostructure-sized grains (< 100nm) form which can be retained after ""low temperature"" compaction. On continued milling in many cases the nanometer-sized grains transform to an amorphous structure. Ordering is destroyed by MA, except in those intermetallics with large negative enthalpies of formation. For the PVD process, a review of application to terminal light alloy compositions is presented. This includes a new high-temperature aluminum alloy, layered materials with nanometer spacing, corrosion-resistant magnesium alloys and low-density titanium compositions. IntroductionTo enhance the mechanical property combinations of advanced structural materials innovations in process/synthesis are required [1-6]. In this paper the capability of various ""far from equilibrium"" synthesis techniques [7,8] to produce novel constitutional and microstructural effects, and hence potentially enhanced physical and mechanical properties, in advanced materials is presented. The application of two such methods, mechanical alloying (MA) and physical vapor deposition (PVD) is discussed in detail. For the MA process emphasis is on intermetallic compositions with consideration given to solid solubility extension, microstructural refinement, amorphization, and formation of intermetallic compounds. For the PVD process application to terminal light alloy compositions is discussed."

Jan 1, 1994

By Mingchun Lu, Yunjin Yan

"This paper describes a new type of bell-less top installed on two relined blast furnaces at Tianjin Iron Works and another new-built at Echeng Steel Works in China. A compact installation was presented for existing furnace top innovation with the least reformation of existing top structure. A water cooling and sealing gearbox used for driving the chute discards completely the traditional idea about necessity of continuous supply of cooling gas for the gearbox. A multiring spreader and its dozens of selectable charging patterns enables an operator to achieve optimal burden distribution easily under the condition of a minimum investment of control equipment. Some useful conclusions have been made through a small-size model and a full-scale model tests. The excellent characteristics and the superiority of the new top have been fully proved at both works.IntroductionIt is known that there are some advantages with the bell-less top of a blast furnace: suitable for furnace to operate at high top pressure, capable of realizing optimal burden distribution, less investment and maintenance costs, etc. But why do most of blast furnaces in the world still remain using conventional bell top. One of the concerns is that current bell-less tops still have some shortcomings:1) The height of a current bell-less top might be lower than three or four-bell top or two-bell plus valve seal top, but still much higher than an ordinary two-bell top.2) The gearbox for driving the rotating chute is positioned onto the lip of the furnace. It is subject to attack by crude hot bf gas. Continuously pumping cooling gas (pressurized nitrogen or clean bf gas) into the gearbox is indispensable to withstand such a harsh working environment. Therefore, a plant furnished with blower8 and its ancillaries has to be built, It involves a large sum of investment and much expense in its annual running costs.3) Although the current bell-less charging device as a means of controlling burden distribution possesses a wide range of freedom, it is difficult to realize optimal burden distribution. There are some large blast furnaces realized better burden distribution, but sophisticated control means is indispensable so that the investment of control means is much higher."

Jan 1, 2000

By A. S. Rao

In the original roast-leach-electrowin (RLE) circuit at the Chambishi Cobalt Plant, commissioned in 1978, the separation of nickel and zinc from cobalt in aqueous streams was achieved by successive stages of precipitation using lime. However, this technique was not able to meet the increasingly stringent metal quality requirements of customers whilst maintaining acceptable process recoveries. Intensive process development work was carried out and, in July 1988, an ion exchange circuit for nickel removal was commissioned using DOW XFS 4195 resin and for the first time Z.C.C.M. produced high purity cobalt metal containing less than 0.10% nickel. Following further work, a solvent extraction circuit for zinc removal, using DZEHPA, was commissioned in February 1991 in order to enhance cobalt recovery by reducing co-precipitated cobalt losses. This paper outlines the process development, design, commissioning and subsequent operation of these nickel ion exchange and zinc solvent extraction circuits.

Jan 1, 1993

By Muammer Kaya, Sait Kursunoglu

"The aim of this study was to investigate the effectiveness of ascorbic (C6H8O6) / oxalic (C2H2O4) acid as a reductant for the simultaneous recovery of zinc and manganese from a spent and mixed zinc-carbon and alkaline battery powder in sulphuric acid leaching. The effects of sulfuric acid concentration, ascorbic/oxalic acid dosages, reaction temperature and leaching time on the zinc and manganese dissolutions were investigated according to 2k full factorial experimental design; then, a simple optimization study was carried out for the best reductant. The optimum reductive acid leaching conditions were determined at 3 hours leaching time, 70°C leaching temperature, 0.5M sulfuric acid concentration, 13 g/L ascorbic acid dosage, 1/20 g/mL solid/liquid ratio and 200 rpm stirring speed. Under these conditions, the dissolution efficiencies were 99.9% for Zn and 99.3% for Mn. When our results were compared with the previous results, our findings were better than previous studies.In addition, the manganese dissolution kinetics was undertaken, and the activation energy was found to be 7.04 kJ/mol. Selective precipitations of Zn and Mn from acid solutions were carried out using NaOH and KOH. Using 3M NaOH as precipitating agent at room temperature and at pH 8; 95.4% of Zn and at pH 10; 93.7% of Mn were precipitated from the leaching solution. Under the same conditions, using 3 M KOH at pH 8; 91.6% of Zn and at pH 10, 96.4% of Mn were precipitated. Based on the experimental results obtained, an appropriate flow sheet was proposed to recover zinc and manganese."

Jan 1, 2012

By Kimio Itagaki

The distribution behaviours of the VA elements between the gas, slag and matte phases in copper smelting were evaluated on the basis of the thermodynamic data, most of which were determined by the authors. The distribution is basically dependent on the process factors such as temperature, the content of the element in charge, the amount of the waste gas and degree of vapour saturation with the elements. The thermodynamic quantities such as the activity coefficients of the VA elements in matte, the activities of iron and copper, SO2 or 02 potential and the distribution ratio of the elements between the slag and matte phases seriously affect the distribution, and the behaviours in various smelters could be explained systematically and reasonably by considering the changes in these quantities, In oxidation smelting at PSO2= 0.1 to 1 atm, the proportion of arsenic and bismuth in gas is predomi22t for the arsenic and bismuth distributions in both smelting and converting stages. The degree of vapour saturation has serious effect on the distribution, and sufficient contact between gas and matte phases is desirable for transferring arsenic and bismuth into gas phase.The elimination of antimony by means of vaporization is not significant. In reduction smelting at po2 = 10-11 atm, the proportions of arsenic and antimony in the gas phase are quite small, but the proportion of bismuth does not change significantly.

Jan 1, 1983

By M. Moinpour, E. Liao, C. Y. Aw, D. J. Brown, P. W. Cheung

"Currently, silicon-based insulated-gate field-effect devices are being widely developed as the basic structural elements in a new generation of chemical microsensors. In this paper, we discuss some of the process considerations related to the fabrication of the Chemically Sensitive Field-Effect Transistor (CHEMFET). This ion-sensitive CHEMFET (or ISFET as it is often called) can be used for pH measurements (i.e., as a pH sensor) when the gate insulator of the electrolyte/insulator interface is made of Si3N4 obtained by the LPCVD method. Effects of processing parameters such as the Si3N4 deposition rate, gas composition, total flow rate, annealing treatment, etc. on Si/Si02, Si/Si3N4 and Si/Si02/Si3N4 structures are discussed in relation to the CHEMFET fabrication. Their effects on the electrical characteristics and chemical response of the sensor are also examined. Capacitance-Voltage (C-V) measurements and ESCA analysis have been used to interpret the results. The Si3N4/Si02 double dialectric layer provides improved ion blocking for the gate insulator in electrolyte solutions with enhanced pH sensitivity over time. The stability and performance of the fabricated CHEMFET sensors were tested by measuring the pH sensitivity in various storage conditions. The SEM analysis was used to evaluate the hydration effect at the ISFET's gate insulator with respect to different storage conditions.IntroductionThere has been a continuous interest in the development and fabrication of various chemical microsensors for chemical and biomedical applications over the last fifteen years. The application of semiconductor (particularly silicon) technology to the area of sensor fabrication has led to an emergence of a new generation of miniaturized, microelectronic, solid-state chemical sensors. There are numerous clinical situations where continuous monitoring of body electrolytes concentrations such as Na+, K+, Ca+2 , etc. and blood gases (pH, Po2 , and PC02) would be essential for the effective diagnosis and management of patients under critical conditions. Solid- state microsensors can be used for direct and continuous in vivo measurement of the above parameters in most instances."

Jan 1, 1988

By Paul E. Queneau

The QS (Queneau-Schuhmann) copper converter is a gently sloped, stepped, horizontal kiln-type tilting reactor in which desired bath oxygen activity, compositional and temperature gradients are created by countercurrent flow of matte and slag phases through a series of controlled bubble plume, mixer-settler configurations. Flow of gas and slag is normally concurrent. Copper sulfide concentrates are top-fed, employing oxygen flash burners. Oxygen and oxygen-carbonaceous fuel mixtures are bottom-blown into the smelting bath through judiciously located, independently regulated submerged injectors. Composition and mass flow rates of injector inputs are controlled to produce bubble plumes of desired character, without jetting through and out of the bath. The mixer-settler pattern can be reinforced if desired by employment of suspended shallow baffles. State-of-the-art instrumentation provides timely information required to govern key process variables. The outstanding capabilities of the QS converter for coppermaking have now been indicated by the current success of industrial QSL (Queneau-Schuhmann-Lurgi) leadmaking reactors. Modified converter designs are employed for leadmaking, nickelmaking and steelmaking.

Jan 1, 1993

By Batric Pesic

Calcium silicate slag (Di-Cal) and magnesium oxide condensate (MgO) are the by-products of magnesium smelting operations, As these oxides have acid neutralizing and metal precipitating properties, it was decided to examine their reactions with (a) individual heavy metals and (b) with a mixture of metals in solution, The resulting solid reaction products were further tested with respect to the stability of the contained metals, The stability of the solid precipitates were examined as a function of the method of precipitation and as function of the solution pH With respect to the method of precipitation, the performance of Di-Cal and MgO was compared to the performance of lime, an industry standard for heavy metal precipitation, Four different pH solutions (4,0, 5,0, 7,0 and 1 LO) were used to study the effect of pH on the stability of the precipitates. It was found that Di-Cal, in most cases, produced the most stable precipitates and thus, outperformed lime, Metal precipitates prepared by the addition of MgO were the most soluble for each metal studied, except for Se,

Jan 1, 2001

By R. S. Celmer

The distributions of cobalt, molybdenum, copper, and selenium between nickel matte and silica-saturated iron silicate slag have been determined in the region of the metallic saturation boundary, at 1523 K. Results are given as a function of the composition of the coexisting Fe-Ni alloy and the activity of iron in the system. Under strongly reducing conditions, these minor elements display a marked preferential accumulation in the sulphide phase. It is shown that the dissolution of cobalt and molybdenum in slag follows an oxidative mechanism, and distribution equilibria are correlated with the oxygen potential. From these data, the thermodynamic properties of cobalt in nickel matte are computed. Further, comparisons of minor element partitions are made between the nickel and copper matte smelting cases under metal saturation conditions.

Jan 1, 1988

By L. J. Lutz

The U.S. Bureau of Mines has developed an electrorefining process to recover Ni, Co, Cr, and other metals from mixed and contaminated superalloy scrap. The superalloy scrap is cleaned then directly electrodeposited as a Ni -Co deposit. The process recovers approximately 90 pct of the Ni-Co available from the scrap as a 99t pct pure Ni-Co alloy. During electrorefining the electrolyte undergoes a purification process which results in Cr and other refractory metals reporting to the purification residue. Operating data is given for a 3-L compartmented electrolytic cell. Techniques for the removal of Fe, Cr, and trace impurities from the recycled electrolyte are outlined. The economics of a facility producing 15 mt/d of a Ni-Co alloy are also discussed.

Jan 1, 1993