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By Dong Joon Min, Joo Hyun Park, Mi Sun Choi, Jae Hong Shin

Sublimation of ZrCl4 is important for the production of nuclear grade metallic Zr in Kroll’s process. The sublimation kinetics of ZrCl4 was investigated by TGA under both isothermal and non-isothermal conditions. The sublimation rate of ZrCl4 increased with increasing temperature under isothermal conditions. ZrCl4 sublimation was confirmed to be a zero-order process under isothermal conditions, whereas it was first-order kinetics under non-isothermal conditions. The activation energy of ZrCl4 sublimation under isothermal conditions was 21.7 kJ/mol. The activation energy for non-isothermal sublimation was 101.4 kJ/mol and 108.1 kJ/mol with the Kissinger method and Flynn- Wall-Ozawa method, respectively. These non-isothermal activation energies were very close to the heat of sublimation (103.3 kJ/mol). Sublimation occurs by two elementary steps: surface reaction and desorption. Therefore, the overall activation energy of ZrCl4 sublimation is 104.8(±3.4) kJ/mol. The activation energy of the surface reaction and desorption steps are proposed to be 83.1 kJ/mol and 21.7 kJ/mol, respectively.

Jan 1, 2014

By John R. Howell

"SUMMARYThe process of producing a new cast component requires significant design and development by both the design engineer and the foundry engineer. This effort strives to produce a high quality component at minimum cost. To assist in this development, an analysis system, consisting of several computer programs, has been developed to simulate the metal casting process. This system incorporates analytical geometric solid modeling, finite element analysis, results display, and an innovative technique to model the casting mold with surface boundary conditions.The simulation has produced excellent thermal results and work is in progress to develop techniques to enable use of this data in additional analyses to predict porosity and residual stress. Research is required to produce working parametric formulations of material properties. Software development is required to develop good fluid flow analyses for large. 3D models to simulate filling of and convection in molds.Integrating this system of programs is difficult due to proprietary database structures used by software developers. However, an acceptable means has been accomplished' to move data from one program to another. Further software development is required to facilitate this task. INTRODUCTIONThe process of producing a new cast component requires significant design and development by both the design and foundry engineer. This effort strives to produce a high quality, reliable component at minimum cost in a timely manner. The design engineer needs to know the physical and mechanical properites which can be expected in the actual part at critical areas. This will enable him to design a part with minimum material while fulfilling the performance required. The foundry engineer needs to produce a sound, quality casting with a minimal amount of material In risers, the feeding system and machining stock. This must be done with a minimum· investment in tooling and development time and maximum productivity of labor and capital employed. This task Is continually being made more difficult because of increased competition in the marketplace and the use of castings in more severe service. This has strongly influenced the need for high quality castings.The task of developing a new casting is difficult for both the design and foundry engineer. To assist in this development, Deere & Company has been engaged in the development of an analysis system to simulate material processes. A major portion of this program involves simulation of the metal casting process. This analysis system has evolved into a package of computer programs which simulates casting solidification and subsequent cooling through the finite element method"

Jan 1, 1986

By Takahiko Okura

Most non-ferrous raw materials are associated with sulphur. To extract the metals, the sulphur is recovered typically as Sulphuric acid or liquid S02. On the other hand, natural gas may contain over 20% of hydrogen sulphide (H2S) and a huge quantity of elemental sulphur is produced through oil and gas refining processes in the world. A large fraction of the sulphur mined from natural sources is eventually returned to the earth as fertilizers, by-products of desulphurisation and neutralisation processes, or as fugitives to the atmosphere. However, the supply and demand for sulphur are in imbalance. Such situation urges to develop a new smelting process without sulphuric acid production. This paper briefly reviews the global sulphur balance and the technologies for recovering elemental sulphur. The core of this paper is a proposal to convert S02 gas to elemental sulphur by using organic materials. Some results of thermodynamic calculations and experiments are presented.

Jan 1, 2003

By Young-Geun Park

A new decarburization model for the RH system was constructed for calculating the decarburization reaction using a three-dimensional fluid dynamics program. The entire fluid flow in the RH process was calculated by evaluating the shape and volume of the plume zone, formed by Ar gas blown through multiple nozzles on the wall of the snorkel. On the basis of this fluid flow, the decarburizaiton reaction was calculated through establishing the decarburization reaction model, which considers the thermodynamics, reaction kinetics, and the decarburization sites (Ar bubble surface, bath surface, and the CO bubble fomtation at inner sites). The results from this model were compared with a real RH operation results with good agreement. Because it is possible to predict the carbon concentration at various conditions using this model, it may be useful in increasing the decarburizaiton rate. Key words : RH process, plume zone, decarburization, Ar bubble surface, bath surface, inner site, circulation flow rate.

Jan 1, 2001

By Adriana de Aquino Soeiro da Silva, Joao Alves Sampaioa, Luiz Carlos Bertolino, Francisco Manoel Garrido, Marta Eloisa Medeiros

"Brazil has a large agricultural potential and its production success is related to the chemicaland physical soil characteristics. Therefore, the demand in the use of a great quantity offertilizers to compensate the low amount of nutrients in the soil includes about 40% of foodproduction costs. In order to develop economical alternatives to traditional fertilizers, rockswith potential use in agriculture will be studied. In this work the potassium rock, a greensandslate, will be chemically and structurally characterized for the development of a potassiumthermophosphate. This alternative fertilizer will be obtained based on a fusion of a ponderedmixture of potassium, magnesium and phosphate rocks to be applied in the Brazilianagriculture. Preliminary characterization results indicate that the greensand slate presents ahigh percentage of glauconite, quartz and micas.Keywords: Potassium thermophosphate, alternative fertilizers, greensand slate.IntroductionBrazil has a great agricultural potential and its production success is closely related to thesoil's chemical and physical characteristics. However, the country's soils present lownutrients content and high acidity due to weather conditions. Thus, the use of a high amountof fertilizers makes up for the soils' lack of nutrients and accounts for 40% of food productioncosts. Therefore, research on obtaining new alternative fertilizers is a constant worry due tothe increase on food demand [ 1].The lack of raw material for the preparation of NPK fertilizers in Brazil is a concern and theissue of potassium fertilizers a priority. Such a fact is because in 2008 only 608.000 tons ofKCl were produced, corresponding to just 10% of the Brazilian necessity. Thus, the use ofrocks as agricultural nutrients can contribute to reduce the need for industrial fertilizers.This way, the development of a new agricultural raw material originated from a rock thatalready exists in the country's soil is of great importance for the mineral and agriculturalsectors."

Jan 1, 2011

By T. Ueno

Naoshima Smelter & Refinery of Mitsubishi Materials Crop. commissioned a new Mitsubishi continuous copper smelter in May 1991. Process offgas volume of the conventional reverberatory furnace line, one of the previous smelters having been shut down, was very large and thus two acid plants had been operated. It was expected that the offgas volume would be reduced at the new smelter to about a half of the sum of those from previous two 1 smelters and the sulfur dioxide strength would be increased. So various alternatives were studied to minimize the operation cost. And it was decided to utilize both of the plants with minor modifications by diluting the gas either with air or with dilute gases. The acid plants now receive offgases from the new copper smelter, a sintering machine of a lead smelter and a decomposer of waste acid. The paper discusses plant design, operation, improvements and modifications realized in relation with the retrofitting of the copper smelter.

Jan 1, 1992

By Jan Dabrovska

Solidification and cooling of a continuously cast slab and simultaneous heating of a mould is a very complicated problem of transient heat and mass transfer. Nowadays, the solving of such a problem is impossible without numerical models of the temperature field not only of the slab itself, while it is being processed through the whole concasting machine (Caster), but of the mould as well. Two original numerical models have been developed and used in the investigation of a continuously cast steel slab. The first (one of two) 3D model of the temperature field of a concasting is capable of simulating the temperature field of a caster. Experimental research and data acquisition have to be conducted simultaneously with the numerical computation-not only to confront it with the actual numerical model, but also to make it more accurate throughout the process. After computation, it is possible to obtain the temperatures at each node of the network, and at each time of the process. The utilization of the numerical model of solidification and cooling of a concasting plays an indispensable role in practice. The potential change of technology-on the basis of computation-is constantly guided by the effort to optimize, i.e. to maximize the quality of the process. The user can therefore choose any appropriate longitudinal or cross-section of a slab and display or print the temperature field in a 3D or 2D graph whenever necessary. The second numerical model of dendritic segregation of elements assesses critical points of slabs from the viewpoint of their increased susceptibility to crack and fissure. In order to apply this model, it is necessary to analyze the heterogeneity of samples of the constituent elements (Mu, Si and others) and impurities (P, S and others) in characteristic places of the solidifying slab. The numerical model, based on measurement results obtained by an electron micro-probe, generates distribution curves showing the dendritic segregation of the analyzed element, together with the distribution coefficients of the elements between the liquid and solid states. The combination of both models enables the prediction of cracks and fissures in critical points of the continuously cast carbon-steel slab. Both models had been applied in the industrial investigation of a cast low-carbon-steel slab.

Jan 1, 2003

By Junmo Ahn

This study investigated leaching kinetics by alternative lixiviants for copper leaching from chalcopyrite (CuFeS2), the most abundant copper resource in the world. As a refractory sulfide mineral, chalcopyrite shows low copper extraction due to passivation on chalcopyrite surface. Also, decrease of copper grade with high portion chalcopyrite requires the alternative leaching procedure to increase copper recovery. Therefore, alternative lixiviants such as sulfurous acid and methanesulfonic acid (MSA) were tested for both concentrate and low grade ore to enhance copper extraction. Also, an oxidant, hydrogen peroxide, was compared to ferric to find out the improvement of leaching kinetic. In concentrate leaching tests, 30 g/L MSA showed the highest copper extraction (47%), compared to other lixiviants at 75 °C. Periodical H2O2 addition enhanced copper extraction, and above 90% of copper extraction was observed within 96 h by periodical addition of 0.6% H2O2 at 75 °C. The activation energy of chalcopyrite leaching by MSA and H2O2 achieved 40 kJ/mol, which is chemical reaction control. The results of low grade ore leaching tests indicates that no significant difference among lixiviants (H2SO4, H2SO3 and MSA) with ferric was observed, all of which achieved around 37% within 24 h at room temperature. However, significant increase of copper extraction (>80%) was observed at both 20 g/L MSA and 10 g/L H2SO4 conditions by the addition of 10% H2O2.

By T. R. A. Davey

A simple model for metal solution behaviour may be derived, on the basis of dilute solution solubilities (where? log concentration of solute varies linearly with reciprocal temperature) and not-so-dilute region solubilities (where the log of the alpha-function at saturation frequently varies linearly with reciprocal temperature) and assuming activity to vary according to the quadratic formalism in between. Matte binary systems usually exhibit regular .solution behaviour when the constituent species are chosen appropriately. In many recent papers, metal solubilities in .slags are expressed as the sum of several different and supposedly independant molecular species (e.g. oxides, sulfides, chlorides), Such a view is untenable because of the now proven ionic nature of slags. Some possible reasons for the great effect of sulfur on copper solubilities in slags are discussed.

Jan 1, 1985

By D. J. Murdock

Cominco Ltd. has developed a number of innovative technologies for electrowinning. The paper discusses the application of these technologies to the copper industry. Tankhouse and cell design will be discussed in addition to anode cleaning and cathode handling. Specific examples of the application of this technology to the copper industry are cited.

Jan 1, 1987

By R. A. Roberti

Most copper refineries use conventional wheel systems to cast anodes. over a period of time the copper moulds that are used become warped and cracks develop. To control mould warpage, the mould's are either rejected after a certain warpage is reached, or the shape is restored by mechanical means. The cracks, unless they are very severe, are repaired by a peening process. Even with regular maintenance to control warpage and cracks, the moulds have a limited useful life. If warpage and cracks are not controlled, anode quality deteriorates and tankhouse operations are seriously affected. -An intensive study was initiated to develop means of controlling mould warpage which culminated in the d?evelopment of technology to control mould warpage to within ±1. 5 mm, and at the same time effectively contr0l: cracking and significantly increase the mould life-. The warpage control has been achieved by using a unique mould design. Mould cavities are present on both sides of the mould and periodic inverting controls the wa-rpage in the cavities. The mould casting procedure has been developed and all production wheels have been converted to the new mould design. The performance characteristics of these moulds will be detailed. 21

Jan 1, 1987

By F. Ajersch, P: Tsantrizos, K: Shanker

"TiN films have been deposited on various substrates by a novel reactive plasma technology. In this process, a nitrogen source (NH3 or N2) and TiCl4 are reacted in the jet of a plasma torch, and are deposited onto a substrate forming TiN films at a high growth rate ( > 2µm/min). It was found that the process parameters strongly affect the microstructure, thickness, density, and growth rate of the TiN films. These parameters include source of nitrogen (NH3 or N2, N/Ti ratio, temperature of substrate, and spray distance. In general, it was found that thick and dense coatings were deposited when the N:Ti ratio was kept low, and the substrate temperature was high. Also, for the series of conditions investigated, NH3 was found to give much better results than N2•. The limitations and advantages of this technique are also discussed in this paper.IntroductionTiN is an extremely hard material and is used in many wear applications, particularly as a protective coating on cutting tools to extend their Iife(1.2). Owing to its excellent chemical stability, TiN is also frequently used as a diffusion barrier in the electronics industry for sub-micron Al/TiN/Si ohmic contact systems (3) or as a coating on high-temperature resistant alloys in gas turbine applications (4), based on its good resistance to oxidation. Other applications include decorative coatings in the jewelry industry, and specialized applications such as solar energy absorbers and transparent heat mirrors(5).TiN films can be deposited/formed using various techniques. The main techniques of deposition are CVD (Chemical Vapour Deposition) and PVD (Physical Vapour Deposition). Each of these techniques can have many variations in equipment characteristics, reactants as well as a range of process parameters (pressure and temperature). In the CVD process, TiN is generally deposited onto a heated substrate where a chemical reaction takes place. The reaction can be one of reduction(6) (e.g.: TiCI4 + 0.5N2 + 2H2 --> TiN + 4HCI), of thermal decomposition(7) (e.g. decomposition of titanium dialkylamide), or of displacement (e.g. TiCI4 + NH3 --> TiN + 3HCI + 0.5CI2)' The displacement and reduction reactions are the most common."

Jan 1, 1994

By Fathi Habashi

The recovery of uranium from wet process phosphoric acid was applied on industrial scale in the 1940's by using octylpyrophosphoric acid as an extractant. Later, more efficient reagents were used, e.g., di(2-ethylhexyl) phosphoric acid and actylphenyl phosphoric acid. In the 1970's the rare earths in Kola phosphate were recovered in Finland and recently (1997) in Norway using HNO, as a leaching agent and di(2-ethylhexyl) phosphoric acid as solvent. It was demonstrated later on laboratory scale that both uranium and rare earths could be extracted from the rock by tributyl phosphate but at different pH values provided that the rock is leached with nitric or hydrochloric acids instead of the commonly used sulfuric. This new concept opens the way to the possibility of treating phosphate rock by in-situ, dump, or vat leaching for the recovery of phosphate values as well as uranium and the rare earths. Another solvent extraction process is used industrially for the purification of phosphoric acid using butyl and amyl alcohols.

Jan 1, 1998

By Wenzhou Yu, Cong Zhang, Wenhui Ma, Gang Wang, Kuixian Wei

"A novel technique was successfully developed for nickel further purification by vacuum directional solidification. The removal effect of impurities in nickel was studied based on theoretical analysis and experiments. High removal efficiency of impurities in nickel can be realized according to theoretical analysis. The experimental results show that the vacuum directional solidification treatment could increase the nickel purity from 99.96% to 99.996%. Since vacuum directional solidification could effectively remove the impurities from nickel with low contamination and low cost, it is a potential route to obtain high-purity nickel for commercial application.IntroductionNickel is widely used in metallurgy, machinery, petroleum industry, chemical industry, construction industry, light industry, and other industries for its ductility, medium hardness, ferromagnetism and high chemical activity. Nickel-based alloy is an important material for the key parts of aircraft, tanks, submarines, radars, nuclear reactors and aerospace fields [1-5]. Generally, nickel contains Si, P, S, Fe, Cu, Zn, As, Cd, Sn, Sb, Pb, Bi, Al, Mn, Mg and other impurity elements, which may hinder the commercial application of nickel. Therefore, it is necessary to refine the crude nickel for the high purity nickel."

Jan 1, 2014

By Richard D. Hangi

Process mineralogy techniques are uniquely applicable to industrial problems related to the extractive metallurgy of nickel, cobalt, and associated metals. Reflected 1ight microscopy, together with selected determinations by scanning electron microscopy-energy dispersive spectrographic analysis and electron probe microanalysis, provides the means to identify the ore minerals cobalt and nickel ores, determine the abundance of each ore mineral, assess the extent of intergrowth between the cobalt and nickel minerals and other ore and gangue minerals in the ores and concentrates, and predict the potential success of cobalt and nickel extraction by grinding, flotation, pyrometallurgical, and hydrometallurgical treatments. In addition, the extent of locking of the cobalt and nickel minerals with each other and with the gangue minerals can be directly observed by reflected light microscopy. Where ores have been treated by hydrometallurgical procedures, reflected light microscopy can serve to determine the causes of excessive leach consumption. Finally, the partitioning of cobalt and nickel between high-temperature synthetic phases produced by pyrometallurgical treatment can be precisely determined by process mineralogy techniques. Case histories from cobalt and nickel deposits illustrate the value of applied mineralogical techniques in the study of cobalt and nickel ores, beneficiation, hydrometallurgial, and pyrometallurgical products.

Jan 1, 1993

By Dmitri Nassyrov, In-ho Jung

"All relevant thermodynamic and phase diagram data in the CaO-Fe10-CaF2 system were critically reviewed. One set of model parameters describing the Gibbs energy of all phases has been obtained as a result of critical evaluation of the available data and optimization of the model parameters. The Modified Quasichemical Model was used to describe the interactions in the liquid phase. All calculations were performed using the FactSage thermochemical software.IntroductionSlags contaimng CaF2 are of significant interest to the steelmaking community. Notable examples of slags containing significant amounts of CaF2 include Electro-slag Remelting (ESR) slags [1] and mould flux for continuous casting [2]. The role of these slags is, among other things, to refine steel by absorbing inclusions and dissolved impurities. During slag-steel interaction, some iron from the steel will inevitably get oxidized and form iron oxides which will dissolve into the slag. With this in mind, it is important to understand the interaction between CaF2 and Fe,0 for accurate prediction of slag composition and process optimization. A thermodynamic optimization of the CaO-FetO-CaF2 was thus undertaken."

Jan 1, 2013

By I. S. Blair

The Mufulira smelter (1, 2,' 3, 4,) is one of three smelters situated on the Zambian Copperbelt to treat concentrates and other intermediate products produced in the area. Two mining companies, Roan Consolidated Mines Limited (RCM) and Nchanga Consolidated Copper Mines Limited (NCCM) each have 51% Zambia Government participation. RCM operates two smelters, one at its Mufulira Division and the other at its Luanshya Dl vision. NCCM operates one smelter at its Rokana Division (5). The Mufulira smelter was commissioned in 1937 with two reverberatory furnaces and four converters. The final product, blister copper, was cast from a holding furnace. In 1952 two anode furnaces and a common casting wheel were installed to feed a new and adjacent electrolytic refinery. In 1956 the smelter was extended to accommodate increasing production from the new Chibuluma mine and expansion at Mufulira mine. A third reverberatory furnace, a fifth converter and duplicate anode processing and casting facility were added. The Copperbelt smelters suffered a loss of production potential when higher ash content coals were used in reverberatory smelting furnaces from 1966 onwards. This, and the planned production increases from Mufulira and other RCM mines, indicated a smelting shortfall of 55,000 tonnes of copper a year in the combined capacity of the RCM smelters.

Jan 1, 1976

By D. Papazoglou

This work was undertaken to investigate the thermodynamic and kinetic feasibility of using hot sulfur dioxide bearing gases from smelting processes to selectively sulfate the nickel in nickel laterite ores for subsequent extraction in water. The environmental benefits ofthis approach, as opposed to releasing the gas to the atmosphere, and the economic benefit of directly utilizing the S02 rather than converting it to sulfuric acid are strong drivers for such a process. A thermodynamic analysis indicated that selective sulfation of the nickel could be feasible under appropriate conditions and these were explored through a series of laboratory scale experiments. Laterite samples were reacted at temperatures between 500 and 800°C with an equilibrated mixture of sulfur dioxide, oxygen and nitrogen in a fixed bed reactor. Tests were conducted on saprolitic ore from Bulong, Western Australia, limonitic ore from New Caledonia and garnieritic ore from Indonesia. Nickel extractions were highest from the limonite and relatively low from the other ores. The maximum selective extraction of nickel from the limonite in a single stage sulfation was 73%. Sulfation of other elements present in the laterites was also examined. A two-stage process was also identified which involved sulfation using a strong sulfation potential followed by weaker sulfation potential to attempt to convert ferric sulfate formed in the first stage to ferric oxide. This increased the extraction for the limonite ore to around 84% Ni, 95% Co and 2% Fe. Direct sulfation of laterite could be feasible in locations where sulfide smelting or roasting operations are relatively close to laterite deposits.

Jan 1, 2003

By Patricio Ruz, Gabriel Riveros, Carolina Ramirez, Andrzej Warczok, Rober Treimer

"Continuous converting of copper matte produces slag with high cuprous oxide content. The corrosion of chrome-magnesite refractories with slag of high cuprous oxide content is a major problem. Properties of olivine type of slag make the slag very attractive for matte smelting and converting.Analysis of phenomena determining the slag infiltration into the porosity of a refractory and dissolution of refractory components in the slag allowed for better understanding of the mechanisms of refractory destruction.The results of laboratory scale tests of the olivine slag infiltration into open porosity and corrosion showed dominating effects of slag temperature and cuprous oxide content. The optical and X-ray examination of slag samples permitted the definition of the mechanism of formation of new phases and refractory deterioration. 71"

Jan 1, 2009

By Nils Eivind Kamfjord, Mari K. Næss, Halvard Tveit, Edin H. Myrhaug

"As a part of the FUME research programme being done by the Norwegian Ferroalloy Research Association (FFF), the SINTEF Group and NTNU, several measurements towards quantifying the gaseous and solid emissions from the draining of the silicon furnaces for metal have been carried out.Based on the measured size distribution of the formed fume particles and known particle growth theory, an estimate of the growth time for the given particles has been calculated. The formation time for the measured NO amount has also been calculated based on the fume measurements and a thermodynamic model of the furnace gases combusting with air. The two “formation” times are in the same order of magnitude and they are therefore used as parameters in a CFD model, modelling that the formed fume particles are heating up the surrounding air and thereby forming NO according to the Zeldovich mechanism. The measurements show an approximately equal constant NO formation per fume particle. The CFD model shows results in the same order of magnitude, supporting that the particle growth and NO formation happen under near stoichiometric conditions and are controlled by the formation of SiO2 fume.IntroductionNOx is the common notion for the two gases nitric oxide (NO) and nitrogen dioxide (NO2) formed during combustion of fuels. The main sources for human made NOx emissions is on-/offshore transportation industry, power generations based on fossil fuels, agriculture and other industries [1]."

Jan 1, 2012