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By Jan Vrestal, Josef Tomiska, Pavel Broz

"Thermodynamic investigations on fcc solid ternary Fe-Ni-Cr alloys have been performed by means of the computer-aided Knudsen cell mass spectrometry. Ternary T.AP.-series (Thermodynamically adapted power series) are used for the algebraic representation of the thermodynamic excess properties. At 1650 K the molar excess Gibbs energy GE is negative over the whole field of stable fcc phase. The molar heat of mixing HE is exothermic in the predominant part of the fcc phase field. Only between the section with a constant ratio of mole fraction Xcr/XNi = 0.64 and the fcc phase field boundary the HE values are slightly endothermic. The results of this work can be used successfully for phase diagram calculations.IntroductionThermodynamic investigations on multicomponent alloy systems such as the Fe-Ni-Cr ternary system including the three binary boundary systems are very time-wasting and usually beset with considerable experimental difficulties. Additionally, the required experimental equipment is very expansive and the obtained results are not always satistying. Therefore it is understandable that many phase diagram calculations are based only on few experimental values of the molar excess free Gibbs energy GE. Consequently, Kundrat and Elliott [1] as well as Hillert and Qiu [2] used in their reassessments of the phase diagram of the Fe-Ni-Cr system thermodynamic data mainly assumed and/or optimized by means of various reasoning.Lee [3] reported recently, a revision of the used thermodynamic description of the Fe-Ni liquid phase is necessary to obtain a better agreement with the experimental data on the bcc/liquid or fcc/liquid tie lines and liquidus temperatures in the Fe-rich region of the Fe-Ni-Cr ternary system than in the previous assessments. This is 'in full agreement with mass spectrometric investigations of Fe-Ni alloys in the liquid and in the fcc solid phase, published earlier [4,5]. Indeed, phase diagram calculations based upon the molar excess free Gibbs energies GE obtained in these studies yield liquidus and solidus lines in excellent agreement with experimental phase diagram data [5]. Nevertheless, these experimental data have not been considered later on any more, not even in the revision by Lee [3]."

Jan 1, 1996

By W. G. Davenport

The flash furnace is used for smelting concentrate to (i) high-Cu matte and (ii) molten metallic copper. It is also used for converting solidified/crushed matte to molten metallic copper. This is flash converting. It consists (Table 20.1, Fig. 20.1) of: (a)tapping molten 65 to 72% Cu matte from a flash smelting furnace (b) granulating the molten matte to ?1/2 mm particles in a 103 m3/hour water torrent (c) crushing the granulated matte to 50 µm in a vertical roller mill (d)drying the crushed matte (e) feeding the dry particulate matte to a second flash furnace for oxidation converting to molten copper. In 2000, flash converting is being used by Kennecott Utah Copper (George, et al; 1995; Newman et al, 1998, 1999a,b). A second installation is being designed for the Chuquicamata smelter (www.outokumpu.com [October 12, 2000]), The potential uses of flash converting are: (a) as the second half of a flash smelting/flash converting coppermaking sequence (b) as a continuous converting alternative to batch submerged tuyere converting. This chapter uses our flash furnace matrix to determine the %O2-in-blast, industrial oxygen and oil requirements for converting solidified 65% and 72% Cu matte to molten copper. It then discusses choice of feed matte grade and other aspects of the process.

Jan 1, 2001

By Chuanfu Zhang, Jinliang Wang

"Brickless reaction shaft is the latest progress for flash smelting furnace. However, there are many factors influence the melting point of the freeze slag inside brickless reaction shaft, and their variational regularities are not obvious, thus, it is difficult for conventional methods to analyze accurately the complex data. In this research, the experiment data of slag melting point were processed based on optimal discrimination plane. For this method, two orthogonal vectors were firstly built up based on the Fisher's criterion, and then the experiment data were projected onto the two vectors, thus, two-dimensional feature vectors were extracted as criteria to determine the factors effect degree on the slag melting point. Results show that the CaO content is the greatest factor to the melting point of the freeze slag inside brickless reaction shaft, the content of Fe3O4, SiO2, Cu2 O and MgO is the second, and the FeO content is the last.IntroductionBrickless reaction shaft is the latest progress of flash smelting furnace reaction shaft. To research the influence factors on the slag melting point inside the brickless reaction shaft is significant to form freeze slag with compact structure, good heat insulation, certain intensity, appropriate thickness and reasonable distribution, to extend furnace life, to reduce energy consumption, and to promote safe production.However, due to the complex components, there are many factors influence the melting points of the freeze slag inside brickless reaction shaft, and their variational regularities are not obvious. Therefore, it is difficult for conventional methods, such as variance analysis, data fitting, etc., to analyze accurately the complex experiment data.Pattern recognition can easily classify information, even if there are many influencing factors. For pattern recognition, there are some sub-disciplines such as discriminant analysis, feature extraction, error estimation, cluster analysis (together sometimes called statistical pattern recognition), grammatical inference, parsing and matching (sometimes called syntactical and structural pattern recognition) [1, 2]."

Jan 1, 2012

By Xuling Chen, Zhiyun Ji, Min Gan, Wenqi Li, Xiaohui Fan, Zhiyuan Yu

"Specularite and vanadium-titanomagnetite are difficult to granulate, and with the increase of their proportions, the permeability of sintering bed is deteriorated together with the combustion velocity of fuel for the shortage of air through the sintering bed, which can lower sintering speed and specific production capacity significantly. The biomass fuel has a higher combustion velocity than coke breeze, therefore the productivity of specularite and vanadium-titanomagnetite ore can be improved remarkably by replacing coke breeze partly with biomass fuel .The results showed that, when the proportion of biomass fuel replacing coke is 40%,the sintering speed and specific production capacity of 35% specularite were improved from 19.06mm/min, 1.33 t/(m2·h)to 21.45mm/min, 1.47 t/(m2·h),and that of 55% vanadium-titanomagnetite were improved from 17.23mm/min, 1.11 t/(m2·h)to 22.80mm/min, 1.44 t/(m2·h). As a conclusion, biomass fuel is effective to strengthen sintering of refractory iron ore.IntroductionThe iron and steel industry of our country has achieved significant development in the recent years. In 2010, the output of steel has reached to 0.627 billion tons. The increasing scale of iron and steel has led to rigorous domestic iron ore environment, and the reserves of hematite and magnetite that have superior sintering characteristics are on the decline with continually exploiting and utilizing [1]. Therefore, the RIO (refractory iron ores) SP (specularite) and VT (vanadium-titanomagnetite) have to be applied vastly. However, the quality of sinters can be deteriorated when utilizing RIO in high proportion due to their poor granulation and metallogenic performances [2, 3]. Generally, the ratio of SP is 3~5%,which should not exceed 10% in our country currently [4]. Though high rate of VT is adopted in PZH steel for a long time, the productivity is obviously low compared with normal sintering [5]."

Jan 1, 2012

By Ruiqing Li

It is possible to purify some liquid metals by exploiting the difference between the vapour pressure of the bulk metal and the minor constituents or impurities. The rates of purification can be improved by carrying out the process under reduced pressure, that is, so called, vacuum. Some commercial examples of vacuum refining are the purification of molten tin to eliminate trace amounts of lead and the refining of cobalt, also to remove lead. The objective of this paper is to review the basic theory behind vacuum refining technology in order to show how the feasibility of vacuum refining can be determined simply for a particular system by evaluating Olette's Volatility Refining Criteriont.

Jan 1, 1991

By George P. Demopoulos

In this paper the production and stability of crystalline scorodite (FeAsO4·2H2O) is discussed both on the basis of previously published work as well as recent work performed in our laboratory. The production of scorodite, especially from arsenic-rich and iron-deficient sulphate solutions offers a number of operational advantages such as high arsenic content, stoichiometriciron demand, and excellent dewatering characteristics. In addition to hydrothermal production of scorodite the work done over the last 10 years in our laboratory has determined that it is feasible to produce scorodite by step-wise lime neutralization at 90°C. The atmospheric scorodite possesses the same structural and solubility characteristics with the hydrothermally produced scorodite. Long term equilibration tests (up to 66 weeks) in the pH range 5 to 9 and temperatures from 22 °C to 75 °C revealed scorodite to undergo slow incongruent dissolutionyielding a highly metastable nano-sized 2-line ferrihydrite phase. The equilibrium arsenic concentration with this phase was 0.35, 0.96 and 5.87 mg/L at pH 5, 6, and 7 respectively at 22°C. In the presence of gypsum slightly lower concentrations were measured, this being more pronounced at pH>7. It was tentatively deduced that a Fe-Ca-AsO4 association (in the form of a phase resembling the mineral yukonite) contributes to the lowering of As concentration. Finally thermodynamic calculations determined that scorodite is stable in the presence of ferrihydriteunder oxic conditions up to pH 6.75 at 22 °C or higher pH at lower temperature and gypsum-saturated solutions. Keywords: Scorodite, Crystallization, Arsenic, Solubility, Stability, Precipitation, Disposal, Extraction, Processing, Metals, and Environment.

Jan 1, 2005

By P. J. Mackey

New and emerging, as well as proven technologies for the smelting of copper, nickel, lead and zinc are briefly reviewed. The number of new technologies available today is greater than at any time in the past, and interest and development activities remain high despite the economic dif-ficulties faced by the non-ferrous metallurgical industry. Part of the impetus is provided by the realization that only the most cost effective producers will remain competitive, and that new technology is one key to cost effectiveness. The commercially proven "new" copper smelting processes can now be considered to be conventional- technology, and are expected to dominate copper smelting for acme time. There is a growing. interest in continuous copper converting, although direct smelting and converting to copper in one vessel remains the- ideal. There is little activity in nickel smelting. After many years. of development, it appears that several new direct lead smelting processes will soon be a commercial reality. The electrolytic zinc process is expected to continue its dominance, although there is a renewed interest in pyrometallurgical approaches. One of the new zinc processes, and a molybdenum smelting process, illustrate the possibilities of using plasma technology in non-ferrous metallurgy. In the area of complex sulphides, there is perhaps less interest in the treatment of bulk con¬centrate, and more in the treatment of so-called dirty copper concentrates. Much of the technology ancillary to smelting has remained relatively unchanged, and more effort must be made to advance the technology in areas such as materials handling, gas cleaning and sulphur fixation, and energy recovery. More attention to engineering design is also needed. Escalating capital costs may make mini-smelters attractive, but imaginative technology and innovative engineering will be required to make them cost effective. Finally, a glimpse is offered of the smelter of the future.

Jan 1, 1983

By Zbigniew Zurecki

The selection of atmosphere composition is critical for controlling surface quality of reactive aluminum alloys during solution treatments. An improper selection of annealing atmosphere can result in surface blistering in AI-Mg and sub-surface depletion of lithium in AI-U ingots. To determine optimum atmosphere compositions for homogenizing A1-Mg and Al-Li alloys, Ii number of exploratory experiments were carried out in air, nitrogen, and carbon dioxide based atmospheres including reactive impurities or additive such as moisture and sulfur hexafluoride. This paper describes the influence of these atmospheres on high-temperature oxidation and sub-surface defects. The results are discussed in terms of the change in Pilling-Bedworth ratio.

Jan 1, 1996

By Atul Kurnar

In the present research a two-cell polymer electrolyte membrane fuel cell stack (PEMFCS) with SS-316 bipolar plates has been tested. Different flow field designs were studied and a modified multi-parallel channel design is proposed. The stack is stable within ±3 mV even after 1000 hours of continuous operation, indicating efficient water management and effective removal of any metal ions from the stack. Also no iron is detected in membrane electrode assembly (MEA) by EDAX analysis after 1000 hours of cell operation. Results indicate that high operating pressures beyond 138 kPa didn't significantly increase the performance of cell, however added much to the pressurization cost of the system. Tests at different temperatures showed that at temperatures below 80°C, external humidification could be completely removed. The prototype stack is also tested under variable load conditions simulating highway-driving schedule. The experimental efficiency of PEMFCS is 48%, which is in good agreement with the model predicted efficiency of 53.8 %. Results show that 59% of the total losses are due to ohmic polarization in the cell. Further analysis on applications of the stack in automotive transportation system is in progress.

Jan 1, 2002

By Ivan Imris

The common problem of new and conventional technology of copper production is the copper losses in the slags, which may be divided into mechanical and physico-chemical losses. In the first group can be included particles of mechanically entrained or floated unsedimented matte particles which coexist with slag. On the other hand, the physico-chemical losses are caused by solubility of copper in the slag in the form of sulphide and oxide. The copper losses in the slags from different processes has been predicted by calculation from thermodynamic data and compared with those determined by microscopic examination and quantitative electron microprobe analysis. Depending on the forms of copper losses in the slag the reduction of copper losses in the slag or the slag cleaning process could be suggested.

Jan 1, 2003

By J. Y. Hwang

The relationship between coal characterization and physical cleaning has not been well understood due to the complex nature of coal. Therefore, it is difficult to apply the results of coal characterization to predict and evaluate the performance of a physical separation (e.g. flotation). Eight U.S. bituminous coals were analyzed and studied petrographically in conjunction with washability and flotation tests. The results show that grindability correlates to ash and fixed carbon contents; liberation determined directly by petrographic techniques is close to liberation determined indirectly by washability; and an ideal separation efficiency can be determined by measuring the inertinite content and the washability separation efficiency using a heavy liquid with a density of 1.4. The ideal separation efficiency was attained for most coals by packed column flotation. The ideal separation efficiency can be used for comparing process technologies and process parameters.

Jan 1, 1988

By Pengfu Tan

In order to understand and control the formation of dioxins and furans in iron ore sinter plants and to possibly avoid expensive end-of-pipe removal stages, thermodynamic calculations on the stability of PCDD/Fs have been combined with sinter process modeling by means of kinetic simulations and computational fluid dynamics. Three thermodynamic databases of PCDD/Fs, derived using the Group Additivity approach and two computational molecular modeling methods, MNDO and PM3, respectively, combined with the SGTE database have been used to model the PCDDIF formation and the PCDD/F isomer distributions in iron ore sintering. The results show very similar conditions for the PCDD/F formation using the different databases. Concerning the isomer distributions of toxic PCDD/Fs, the calculated data derived from the MNDO method showed optimum agreement with measured values from industrial furnaces. The thermodynamic calculations also proved that the isomer distributions found in combustion processes are equilibrium values, while the concentration ratio of PCDDs and PCDFs in the wind boxes does not represent an equilibrium state. A CFD model of iron ore sintering was developed including the kinetics of 15 relevant chemical reactions with the aim of describing the temperature fields and the gas flow patterns in the sintering bed. On the basis of these information and experimental observations reported in the literature possible pathways for the PCDD/F formation in sinter plants have been identified: PCDD/Fs are formed in the critical temperature region of 250 to 450 °C below the combustion zone, are then carried downwards with the gas and condensed close to the bottom of the sinter bed. Transported to the discharge end with the solid mixture, they are again released into the gas phase when the flame front approaches the bottom. PCDD/Fs are also formed in the last wind boxes when the hot off-gases cool down and reach the critical temperature range. Consequently, methods to reduce the dioxin formation reactions are proposed including inhibitor addition to the sinter feed and off-gas quenching.

Jan 1, 2003

"Mechanical alloying (MA) synthesizing technology and thennohydrogen processing (THP) were utilized to produce nanocrystalline Ti-MMC's reinforced by TiB intermetallic compound by using TiH2-B powder mixtures. Powders MA'ed up to 8 hours were examined by X-ray diffraction and SEM study. All MA'ed powders afterwards were HIP'ed at 700, 800 and 950EC for 1 hour. Detailed XRD, SEM and TEM study of the samples were carried out to determine the structure and micrography of the Ti-TiB MMC material processed by MA+THP approach followed by HIP'ing at high temperatures.IntroductionThe fiber reinforced titanium base composites [1,2] which possess a great resistance to high temperature have been investigated. In these studies fibers of C and SiC were used as reinforcing materials. However, these fibers react with Ti-matrix at elevated temperature resulting in product formation at the interface between the matrix and the fiber. Because of the chemical reactions, strength of the product MMC material diminishes.In conventional techniques of whisker reinforced composite material production, the mixtures of matrix metal powders and dispersed fibers are consolidated by hot pressing, HIP and/or hot extrusion. These techniques, however, have some shortcomings. Hard and brittle fibers could be broken during mixing cycle of the processing. Consolidation techniques could also be the cause for fiber breakdown. Attaining of the uniform dispersion of fibers into the metal matrix is not an easy process. The chemical reactions at elevated temperature exposures in the interface between the matrix material and fiber reinforcement cause product formations leading to poor mechanical properties."

Jan 1, 1998

By M. Fujikawa, S. Goto, M. Nishikawa

"The semi-pilot scale plant for injection smelting of zinc calcine was operated under the committee of Joint Research Organization of Injection Metallurgy. The capacity of the plant is 10 ton metallic zinc per day. The plant was designed by the resul ts of basic and bench scale tests of the capacity of 1 ton metallic zinc per day which was published at ""Zinc '85"". The equipments of the plants, operational conditions, results of the operation such as recovery of zinc in injection furnace and condenser, combustion rate of powdered coke and consumption of energy in this process are presented in this paper. The results of the study of the feasibility of the commercial plant of 100,000 ton zinc per year by the injection smelting are also discussed in the paper. IntroductionThe research committee of new smelting process of zinc by injection was established in 1981 under the finantial support of Mining Promoting Foundation of Japan. Six zinc producing companies joined in this organization. The price of zinc was very low at that time and the energy cost, especially, cost of electric power in Japan was extremely high. Invention of a new economical process for zinc extraction had been stronglydesired. The author proposed a injection smelting of zinc as a economical process in energy saving after a calculation of thermodynamical equilibrium and heat balance(1 )(2).The research committee has been studying the injection process since 1981. The small basic experiment by using a crucible furnace was carried out from October 1981 to March 1983 and the reaction of reduction of calcine by injection smelting was ascertained (2). Vaporizatipon of zinc and behaviours of impurities were examined. After the basic experiment, the bench scale test with the production capacity of zinc of 1 ton per day was carried on from November 1983 to October 1984.The bench scale tests were carried out to obtain the proper design of feeding devices of calcines and coke into a furnace and also to obtain fundamental data for enlargement of this smelting process(3,4). The recovery of metallic zinc in this small equipments was about 50% and main loss of zinc was formation of dross in the condenser."

Jan 1, 1988

By R. Hurman Eric

Within the Ag-Pb-S ternary system, the boundaries of the immiscibility region together with the tie-line distributions were re-established at 925°C by the equilibrium-quenching technique where samples were kept in evacuated and sealed silica capsules. Activities of Pb were measured by the dew-point method along the Ag-Pb binary at 925°C, 1100° and l200°C, positive deviations were observed and the results were modeled by the Krupkowski formalism. Activities of Ag, Pb, and S, along the ternary miscibility gap were calculated at 925°C by utilizing the boundaries binary thermodynamics, phase equilibria and tie-lines. Activities of PbS within the pseudobinary Ag2S-PbS mattes were also measured by the dew-point technique and the results were again modeled by the Krupkowski formation where negative deviations were observed.

Jan 1, 2003

By R. Hurman Eric

Within the Ag-Pb-S ternary system, the boundaries of the immiscibility region together with the tie-line distributions were re-established at 925°C by the equilibrium-quenching technique where samples were kept in evacuated and sealed silica capsules. Activities of Pb were measured by the dew-point method along the Ag-Pb binary at 925°C, 1100° and 1200°C. positive deviations were observed and the results were modeled by the Krupkowski formalism. Activities of Ag, Pb, and S, along the ternary miscibility gap were calculated at 925°C by utilizing the boundaries binary thermodynamics, phase equilibria and tie-lines. Activities of PbS within the pseudobinary Ag2S-PbS mattes were also measured by the dew-point technique and the results were again modeled by the Krupkowski formation Where negative deviations were observed.

Jan 1, 2003

By Lenny Winkel

With the aim to develop a solar-driven process for the extraction of copper from sulfide concentrates research on the decomposition of copper sulfides under inert atmospheres has been initiated. Thermogravimetric measurements on chalcocite,(Cu2S) revealed that copper is formed already at 1823 K. Chalcopyrite (CuFeS2) also disintegrates at this temperature, although at a lower rate. Copper and iron have been identified in the solid residue. The results confirm the feasibility of copper extraction by direct decomposition of sulfides under atmospheric pressure. The decomposition under inert atmosphere prevents generation of SO2, it also alters the behavior of volatile impurities during decomposition of copper sulfide concentrates. Chemical equilibrium calculations for chalcopyrite contaminated with enargite (Cu3AsS4) have shown that the absence of an oxidic slag allows for a complete evaporation of arsenic and subsequent separation from intermediate sulfides. The need to better assess the potential of direct sulfide decomposition has prompted the development of an experimental setup for studying the decomposition reactions. The experiment has been devised such that data on the decomposition kinetics and on impurity removal can be obtained at temperatures up to 2500 K.

Jan 1, 2003

By Emil B. Milosavljevic

Problems associated with distillation and other classical methods for analyzing operationally defined cyanide (CATC, WAD, Total and Free Cyanide) will be discussed. These methods often achieve incomplete, species dependent cyanide recoveries and suffer from serious interferences. Depending on the relative concentrations of interferents and other matrix constituents, underestimation (ultimately Type II errors probability of not detecting a constituent when it is actually present) or overestimation (ultimately Type I errors -probability of deciding a constituent is present when it is actually absent) of the cyanide levels present in a ,given sample may occur, causing in the first case false security and in the second case, excessive cyanide treatment costs. Mahy, if not all, enumerated problems can be solved by using novel flow injection (FI) gas-diffusion amperometric methods. A modification of the recently approved FI ligand exchange (FIILE) method for determination of available cyanide (USEPA Method OIA-'l677) that obviates sulfide interference will be discussed. Eight laboratory round-robin data obtained for the FI UV -digestion (FIIUV) method that determines total cyanide (Proposed Method OIA-1678) will also be presented. In addition, some methods for cyanide speciation will be presented. Finally, research needed for developing reliable methods for determination of operationally defined cyanide in solid samples will be summarized.

Jan 1, 1998

By Varadarajan Seshadri

A physical model based on similarity principles was constructed for simulating the RH degasser of CST (Companhia Siderurgica Tubarao, Vitoria, ES, Brazil) to evaluate the circulation rate of the metal which essentially defines the degree of exposure of the metal to vacuum in the chamber and thus of the refining rate, The circulation rate on the other hand will influence the decarburization rate and removal of dissolved gases like nitrogen and hence it is essential to optimise this parameter to get maximum refining efficiency with minimum refining times, thus improving the productivity of the secondary refining process. Mixing characteristics in the ladle is evaluated by pulse tracer addition using conductivity-meters located at the down leg as well as at several locations in the ladle. The influence of gas injection through nozzles in the upleg with simultaneous bottom injection of gas as well as nozzle blockage on the circulation rates were investigated. Also simulation experiments of kinetics of decarburization were carried out using CO2 adsorption-desorption process in sodium hydroxide solution as circulating fluid and the effect of, bottom gas flow rate in this case was also evaluated. The results were carried over to prototype and to optimize the process.

Jan 1, 2003

By Mitsutaka Hino

The contents of gangue minerals, such as Al2O3. P2O5, crystalline water and so forth in the iron ore imported to Japan tend to increase year by year. Though the increments of such gangue contents arc approximately 0.1-0.2 mass%, some problems for the blast furnace operation in ironmaking process have already been reported, In order to clarify the mechanism of harmful effect caused by the small increment of gangue minerals, mainly Al2O3. on the blast furnace operation, the dripping behavior of Fe,O-CaO-SiO2-Al2O3-MgO slag from the iron funnel, which simulated the micro-porosity in sinter ore, has been observed with the wide range of basicity, Al2O3, Fe2O and MgO contents. The effect of MgO on the dripping behavior of slag has been summarized in this paper. It was found that the addition of 2mass% MgO resulted in large increase of hold-up on the most of the conditions. When Fe2O content was less than 20mass% and the basicity was lower than 0.8, MgO lowered the hold-up even if the slag contained 10mass% Ah03. Every slag hold-up showed the minimum at the basicity of less than unity on the conditions of constant Fe2O and Al2O3 contents, This trend became remarkable when the slag contained 2 mass% MgO.

Jan 1, 2003