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By Günter Petzow, Hans Leo Lukas, Hans Jürgen Seifert

"The CALPHAD method (CALculation of PHAse Diagrams) has been extensively developed in the last 25 years and became a useful tool in materials science. Thermodynamic descriptions for the functions of state of unary, binary and ternary phases are derived by the optimization of phase diagrams. These functions are stored in computerized thermochemical databases and can be combined to extrapolate to multi component systems. Depending on special demand, the actually most advantagous presentations of the calculated results can be chosen: tables or in a clear graphical form as phase diagrams, phase amount diagrams or volatility diagrams. The method will be desribed by the system Ti-Si-C-N-O including the ceramic subsystem Si3N4-SiC-TiCi,N1_1,-C-N-O which is very important for the development of ceramic composites. The calculations give the thermodynamic stabilities of the condensed phases as function of temperature, concentration and partial pressure of different gas species. Adjusting the sintering conditions to these results the formation of unfavourable compounds or liquid phases can be suppressed.IntroductionThe CALculation of PHAse Diagrams (CALPHAD-method) of multicomponent systems provides the possibility to plan experiments very efficiently and avoid the experimental trial and error approach for the development of materials. The main problem for best use of calculated results is their interpretation with regard to the specific applications under consideration. Tables give the exact quantitative data for the treated phenomena. However, most important to make best use of these thermodynamic data is their graphical representation especially designed for the solution of specific problems, scientific as well as application oriented. Only well chosen graphical representations support a comprehensive understanding of the thermodynamic interrelationships and the transfer to the problem."

Jan 1, 1996

By Jafar Safarian

Bauxite is the main raw material used for the production of alumina (Al2O3) through the well-known commercial Bayer process. This process has significant challenges such as limitation in using low-grade bauxites as they contain significant amounts of impurities such as Fe, Si, Ti. The Bayer process residue, which is known as red mud, is also a global environmental challenge due to huge amount of this low value residue production. An alternative sustainable process with high potential to solve these problems and produce valuable and consumable by-products is a pyrometallurgical-hydrometallurgical process in which the low-grade bauxite ore is treated through a smelting-reduction process, yielding iron alloys and a calcium-aluminate slag. Alumina is then produced from the slag by hydrometallurgical treatment. In the present work, the reduction of pellets produced from different bauxite ores by hydrogen is studied and it is shown that complete iron oxides reduction is possible. Further smelting and smelting-aluminothermic reduction of the reduced pellets show that iron and silicon ferroalloys can be produced, in addition to a proper slag for alumina extraction.

By Kenneth N. Han

Ammonia has been found to be an effective leaching reagent for gold, silver and platinum group metals in the presence of appropriate oxidants. Electrochemical and kinetic aspects of the dissolution of elemental gold in ammoniacal solutions have been investigated. The cathodic reaction of aurous di-ammine on the gold cathode has been investigated first. From this investigation, the standard electro-potential of the cathodic reaction .and hence. the Gibbs free energy of formation of the aurous di-ammine were established. The solubility of gold in ammoniacal solutions was also examined in relation to ammonia concentration, temperature and concentration of various oxidants. The anodic reaction of the gold disk in ammonia? in the presence? of various oxidants including oxygen, ozon, hypochlorite, hydrogen peroxide, cupric and cobaltic ammine, and iodine was also examined and the results have been discussed. Excellent dissolution yielding of gold and many other metals, typically better than 95% recovery in 1'-2 'hours of leaching at a temperature ranging 80°C to 190°C has been observed. Test results of the dissolution of gold from elemental state as well as other sources including sulfidic ores and scrap are presented.

Jan 1, 1998

By John J. Mortvedt

Application of some by-products of the metals industry which contain plant nutrients to agricultural lands could constitute resource recovery instead of costly disposal. Some industrial by-products contain appreciable concentrations of heavy metal contaminants, such as Cd, Cr, Ni, and Pb. After land application, these metals may be absorbed by plants and enter the human food chain or be leached to groundwaters. Plant uptake of these heavy metals varies with plant species:, soil pH, soil texture, and the particular metal. Certain leafy vegetables can absorb significant amounts of heavy metals, while absorbed metals are usually poorly translocated to cereal grains. Allowable heavy metal concentrations in fertilizers now are not regulated, but EPA is considering such regulations. Heavy metal impurities in animal feed supplements are regulated by the states; so some by-products may not be permitted for this use.

Jan 1, 1992

By L. J. Friedman

Smelter operating and environmental requirements demand high on-stream time (high reliability) from the primary smelter sulfur retention device - the sulfuric ?acid plant. The key to reliable smelter sulfuric acid plant operation is the gas cooling and cleaning system. Problems in the gas cleaning system cause corrosion, plugging, equipment failure, etc - plant down time, in the contact section of the plant. The last fifteen years have seen major changes in gas cleaning system design _to the current standard of brick lined venturi scrubber, packed gas cooling tower with plate type liquor coolers and lead or plastic tube precipitators, The current? design offers improved' impurity scrubbing along with increased reliability. in addition, a number of alternate gas cleaning systems have been offered Chemetica LAB System; Monsanto DuPont D:Jna-Wave Syatem1 Lurgi venturi scrubber with lead star gas cooler. This paper will review the design and operating advantages, disadvantages, and risk of the standard gas cleaning system and compare it to the alternate systems. _

Jan 1, 1992

By Terence Makanyire, Animesh Jha

The dissolution and chemical properties of vanadium, zirconium, and niobium in rutile lattice are analyzed by comparing the octahedral site preference energies, with respect to Ti4+ ion in the solvent phase. The oxides are often present in rutile lattice and interfere in achieving the quality of pigment grade TiO2 due to favourable Gibbs energy for dissolution in the solvent rutile matrix. Binary mixtures of V2O5 { TiO2; Nb2O5 { TiO2 and ZrO2 { TiO2 with compositions of 80, 85, 90, 95 and 97 wt% TiO2 were made, pelletized and sintered at 1100 °C for 24 hours. The solidsolution mixtures were then cooled and leached in 2M NaOH for 3 hours at 60 °C. Phase and lattice parameter characterizations, and microstructural and compositional analyses were then carried out using X-ray diraction and SEM/EDX, respectively. The leachates were analysed by Atomic Absorption Spectroscopy (AAS), using which the solute dissolution model for oxides were investigated.

Jan 1, 2014

By Takeshi Nagano

Copper pyrometallurgy in Japan has experienced quite fundamental changes in last fifteen years. The severe environmental restriction coupled with increase of energy costs accelerated the development work of the new continuous process in Mitsubishi Metal Corporation. After several years of pilot plant test work the commercial plant was put into operation at Naoshima Smelter in 1974, the design capacity of which was 4,000 tonnes of copper per month. Many modifications and improvements have been incorporated into the process and 7,200 tonnes per month of copper production was achieved in 1983, proving that continuous process was much more economical than conventional process. It is now possible to design and operate the continuous process in wide range of capacity. This paper will review the process and describe the progress of the process in these 10 years. 311

Jan 1, 1985

By Kafui Nyavor

The indirect, and the direct contact mechanisms of bacteria oxidation of sulfides were studied using Thiobacillus ferrooxidans and pyrite. The aim was to determine which of the two generally aeeepted mechanisms played a dominant role, if any, during acid mine drainage (AMD) formation from the oxidation of sulfide minerals. The results show that at a pH of 4.5 where T. ferrooxidans are quite active, but where initial chemical oxidation of pyrite to Fe2+ is limited, the bacteria were unable to directly oxidize pyrite to any significant extent. Whereas, in the presence of Fe2+, T. ferrooxidallS assisted oxidation of pyrite by the indirect mechanism was observed and sustained over the pH and Eb range where the bacteria is active. The results lead to the conclusion that the direct contactmechanism of pyrite oxidition by T. ferrooxidans is insignificant. The predominant, and possibly the only, pathway involves the indirect bacteria oxidation of available Fe2+ to Fe3+, which in turn oxidizes FeS2 to generate additional Fe2+ and acidity in a cyclic process.

Jan 1, 1996

By Nagahiro Saito, Takahiro Ishizaki, Mituhito Hirota, Akio Fuwa

"Owing to their extremely high toxicity in the environment, the dioxins have been attracting social, technical and scientific attention in recent years. The authors theoretically had predicted the thermodynamic properties of all the dioxins via quantum chemistry and statistical thermodynamics and elucidated the generation-decomposition behavior of dioxins in the equilibrium calculation· of C-H-0-Cl system. In actual combustion processes, it is said that metallic compounds have much influences on the dioxins behavior. The aim of this study is to reveal the roles of metallic compounds the generation-decomposition behavior of dioxins is revealed from the viewpoints of quantum chemistry. Especially, the catalytic effect of copper has been investigated for the reaction, 2HCl(g)--H2(g}+Cl2(g) and for the etherification reaction from precursors, which is Phenol(g) here, to dioxins. The catalytic role of Cu is shown to have much influence on the generation -decomposition of dioxins.1. IntroductionIt is well known that dioxins are very harmful not only for our health but also for that of our children and grandchildren because they are very stable substance and their reaction rates of decomposition are considerably low. On the other hands, it is not well know how dioxins are generated and decomposed; the generation-decomposition conditions and paths as well as the catalysts to decompose them'1l. The authors believe that the thermodynamic and kinetic study of dioxins is useful to find a solution to these issuers. The authors have been investigating the following problems to reveal the generation-decomposition behavior of dioxins; (a) the prediction of the thermodynamic parameters of dioxins (2), (3), (b) the generation -decomposition behavior of non-chlorinated dioxins by the thermodynamic equilibrium calculations in C-H-O system(4) and (c) the generation-decomposition behavior of dioxins by the thermodynamic equilibrium calculations in C-H-O-CI system(5). Summaries of these thermodynamic researches are as follows.(I) The thermodynamic parameters for dioxins, which had been unknown and/or inaccurate'6 l, could be predicted and are available within the scientific accuracy."

Jan 1, 2000

By Kelly J. Driscoll

Impure zinc (98.5%) was electrorefined to high purity zinc (99.995%) using a fused salt electrolyte of molar composition 1: 1 : 1 :2 ZnCI2:KCl:NaCl:LiCl with a current efficiency of about 90% at 723 K. A recessed channel electrorefining cell was developed which achieved excellent mixing of both the metal and the electrolyte and by ensuring a very small anode to cathode spacing the voltage drop across the cell was 0.16 V and at a current density of 7kA m-2. The physical characteristics of the cell were observed using a low temperature model which showed the formation of droplets and rivulets which provided mixing. The application of this approach to the refining of other non-ferrous metals is discussed.

Jan 1, 1992

By Michael A. Krstich

A soil washing pilot plant to treat soils at the U.S. Department of Energy (DOE) owned Fernald Environmental Management Project (FEMP), was designed based on extensive bench-scale testing. The system's design incorporated a combination of physical separation and' chemical extraction processes and was tested on two soils. The textural composition of the two soils was approximately 20 percent sand, 60 percent silt, and 20 percent clay. Since this grain size distribution was not considered optimum for physical separation techniques, thesoil washing pilot plant had to be designed with selected equipment to provide specific soil size fractions during processing operations. A trommel, vibrating screen deck, centrifuge, and attrition scrubber were used in the system to selectively separate specific soil size fractions at 4.75, 2, 0.3, and 0.02 millimeters (mm). The trammel used high pressure water [1000 pounds per square inch (psi)] during the initial step of the process to reduce soil aggregates to single grain composition, separate out greater than 4.75 mm gravel, and dislodge chemical contaminants from the individual soil particles. The vibrating double-screen deck provided 2 - 4.75 and 0.3 - 2 mm soil fractions that, when combined, averaged greater than 75 percent solids for both soils. The centrifuge was designed to take the less than 0.3 mm soil slurry from the screen deck and produce a particle size of 0.02 mm. The centrifuge produced a high solids stream that averaged greater than 70 percent solids for both soils. These 0.02 to 0.3 mm soil solids from the centrifuge were combined with the 0.3 to 4.75 mm soil solids from the screen deck and processed through the attrition scrubber. The data collected from the pilot-plant operation was used to aid in the design of a full-scale system and was instrumental in formulating full-scale process operations and the selection of equipment.

Jan 1, 1995

By C. E. Abbey

Cobalt, iron and manganese play various roles in copper electrowinning using lead–calcium–tin alloyed anodes. Cobalt catalyzes electrochemical water decomposition resulting in lower anode potential and reduced corrosion rates. Iron reduces cathodic current efficiency, but is used to reduce higher oxidation states of manganese that oxidize organics in solvent extraction. Manganese also produces anode scale and is generally considered a problematic impurity. The effect of the combined interaction of these three metal ions on the anode potential has not been quantified yet. The current work used a three factor, two level, three replicate central composite design of experiments to analyze the effects and potential interactions among cobalt, iron and manganese. The experiments consisted of chronopotentiometric analysis to assess anode potential after 24 h of operation. Higher [Co], lower [Mn] and either high or low [Fe] yielded lower anode potentials. Two regression models were developed to predict anode potential as a function of [Co], [Fe] and [Mn]. A method to estimate electrical energy consumption for copper electrowinning is also presented.

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 James R. Craig

The slags generated during gasification of petroleum coke are heterogeneous and con-sist of many different phases. These phases are important because their physical properties affect the operability of gasifiers and because they concentrate many elements that are present in the petroleum coke feed in only minor to trace quantities. An understanding of the chemistry and physical nature of these slag phases is necessary to predict behavior in the gasifier and in considering the ultimate use or disposal of the materials. Slags typically consist of silicate glasses, calcium-silicates, free iron-nickel metallic phases, iron sulfides, and aluminum oxide spinels enriched in iron, chromium, and vanadium. The partitioning of elements among these phases has been analyzed and will be discussed.

Jan 1, 1989

Arsenic occurs naturally in rocks and soils, water, air, plants and animals. It can be further released into the environment through natural activities such as volcanic action, erosion of rocks and through human actions. Higher levels of arsenic tend to be found more in ground water sources than in surface water sources of drinking water. Compared to the rest of USA, western states have more systems with arsenic levels greater than 10 parts per billion (ppb). The US Environmental Protection Agency (EPA) has historically regulated arsenic in drinking water at 50 ppb, but the agency has lowered the maximum contaminant level (MCL) for arsenic to 10 ppb-to be in compliance by January 2006.This paper reviews briefly a) aqueous arsenic chemistry and removal mechanisms and b) the available treatment processes to attain the drinking water standard of 10 ppb by 2006. The combining of an appropriate removal method with an existing system depends on several factors such as nature of arsenic, the water source, existing plant equipment and processes site conditions etc. The paper also includes one or two case studies from the State of Arizona. Key words: Arsenic, Drinking water, Treatment Technologies

Jan 1, 2005

By Rodney T. Jones

DC arc furnaces were first used industrially for the reductive smelting of chromite fines to produce ferrochromium thirty years ago. Since then, they have been used for a variety of applications, including the smelting of ilmenite to produce titania slag and pig iron, the recovery of cobalt from non-ferrous smelter slags, and the smelting of nickel laterite ores to produce ferronickel. The power of these furnaces has increased from 12 MW to 72 MW for ferrochromium, and to 80 MW for ferronickel. The largest of these furnaces requires two electrodes to carry sufficient current to generate this much power. A review is presented of various DC arc furnaces in use, along with a discussion of the likely ways in which furnace power might be increased further in the future.

Jan 1, 2014

By C. J. Newman

Prior to 1995, the smelting process at the Kennecott Utah Copper Corporation (KUCC) smelter consisted of Noranda reactors and Pierce-Smith converters. In the consideration of expansion opportunities, the existing process did not lend itself to a program geared towards processing the total output of KUCC mining and milling operations. During 1989 and 1990, a number of smelting options were evaluated. The final selection was the Outokumpu flash smelting process, coupled with the new Kennecott-Outokumpu flash converting technology. Facilities were designed and installed to process 1:0 million tonnes per year of copper concentrate, with the ability to expand to 1.2 million tonnes per year. Following the shutdown of the smelter facility utilizing the Noranda technology in May 1995, the flash smelting, furnace commenced operation in June with the flash converting furnace startup following a few weeks later. The smelter has achieved design production targets and environmental goals. Current operating rates are at or above design rates for concentrate and matte processing. Emissions are lower than the permit levels and equate to less than 3.5 kg of SO2 per tonne of copper. This paper outlines the design, construction, startup and the first two years of operation of the modernized KUCC smelter.

Jan 1, 1998

By Dalene Joalet Steenkamp

Excavation of industrial-scale furnaces allows for the systematic study of reaction sequences by identifying the different reaction zones within the furnace. In 2013, Transalloys excavated a 48 MVA submerged arc furnace that was used for silicomanganese production using the ore-based route. The excavation method was reported elsewhere as was observations made in terms of refractory wear and modes of electrical energy dissipation prior to excavation. The paper presented here, reports on the process reaction zones observed during the excavation and subsequent phase chemical analyses of a number of process samples obtained during the excavation. The zones identified were a loose burden zone, a dry coke-bed zone, a wet coke-bed zone, a hard build-up zone, and an alloy zone. The results are compared to observations made in the excavation of an industrial-scale SAF and a pilot-scale SAF in Norway. The presence of the hard build-up zone below one of the electrodes and absence of a slag zone below all three electrodes are unique features of the SAF excavated at Transalloys.

By Carlos Antonio da Silva

Steel refining reactors based on chemical heating are being used as an alternative to ladle furnaces. They show a high degree of flexibility in respect to heating rate in addition to carrying out refining reactions such as de-S, inclusion removal, alloying etc. IR-UT and CAS-DB are examples of such reactors. Their performance is dependent upon geometrical characteristics as well as operational conditions which determine the flow field inside the vessel. A physical model of the IR-UT process of the Companhia Siderurgica de Tubarao, steel plant located in Serra, Espirito Santo, Brazil, was developed to assess the features of the flow field and its influence on the metallurgical behavior. Results of the physical model were used to optimize the process parameters in the industrial unit.

Jan 1, 2003

By R. Schuhmann

The thermodynamic data and calculations which underlie the design of the Q-S process for coppermaking are summarized. The efficient production of crude copper and slag of low copper content in a single con¬tinuous converter requires the establishment and control of gradients in oxygen activity and other physico-chemical variables throughout the reactor. These gradients are established by stagewise introduction of oxygen and solid feed materials to provide: (a) flash oxidation of sulfides above the bath, utilizing the great bulk of the oxygen, (b) conversion of high grade matte or white metal to crude copper by bottom blowing with restricted bath turbulence, (c) close approach to equilibrium staging of converting and deconverting reactions along the length of the slag layer, from a maximum oxygen activity near the metal discharge end to a minimum at the slag discharge end, and (d) completion of slag cleansing by deconverting. In terms of the Phase Rule, the Q-S process involves a system with a minimum of 5 components (Cu, Fe, S, O, and SiO2) and several liquid, solid, and gaseous phases. Accordingly, basic data from previously reported studies on simpler systems are utilized to prepare an equilibrium diagram for the 5-component system and to generate a quantitative thermodynamic model for the Q-S process. This model shows in particular the ranges of oxygen activities (measured by equivalent CO2/CO ratios) involved in the Q-S process and the relations of oxygen activity to temperature and other important physico-chemical variables of coppermaking.

Jan 1, 1976