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By Oscar Perales Perez, Atsuo Kasuya, Kazuyuki Tohji, Yoshiaki Umetsu

"The removal of iron and various heavy-metal ions by their incorporation into stable ferrite-type precipitates at 25°C is a promising alternative to clean up large volumes of polluted aqueous effluents. Our research work investigated the conditions to produce magnetite and various M-bearing ferrites (where M: Zn, Cu, Co, Ni, Cd, etc.) directly from aqueous solutions at 25°C by simultaneous control of the oxidizing conditions and pH. The formation of the solids was followed by monit9ring the oxidation-reduction potential (ORP) and rate of proton release during the aerial oxidation of the suspensions at constant pH (contact stage). Only mildly oxidizing conditions, represented by ORP values between -110 mV and -150 mV and a moderate oxidation rate of Fe(II) species were conducive to well-crystallized ferrites at ambient temperature.' It was also found that increasing the Fe/M mole ratio in starting· solutions enhanced the stability ·of the M-bearing ferrites at ambient temperature. When the formation of the ferrite was incomplete, aging of the sludges in their mother liquors at 25°C promoted the crystallinity of the precipitates. The mentioned conditions ·favored the suitable progress of the ferrite-forming reaction involving the oxidation of Fe(II) entities, subsequent hydrolysis of produced Fe(III) species and dehydration of the intermediate:· Furthermore,· the ferrite formation at· low temperature permits the elimination of iron and co-existing heavy metal ions to sufficiently low concentration.In tum, the characterization of the precipitates evidenced their magnetic nature (room-temperature saturation magnetization above 60 emu/g) as well as the effective incorporation of target metal ions into the ferrite structure."

Jan 1, 2000

By Ivan Imris

The iron production has generated many tonnes of very fine residues with high concentration of iron. In addition, during the recycling of galvanised steel scrap in the steel making processes the zinc and lead are largely concentrated in the dust. These kinds of dusts are usually dumped beside the metallurgical plants and cause environmental problems. Therefore the metal recovery from the metallurgical residues has become a major interest not only from the viewpoint of metals recycling but mainly from the viewpoint of environmental land protection. The thermodynamic analyses and laboratory experiments suggested that the metals could be recovered from metallurgical wastes by reduction roasting and by plasma smelting processes. The iron rich pellets with very high metallization may be obtained from metallurgical wastes by the reduction roasting and the inert slag and pig iron could be produced by plasma smelting processes. In both cases the iron rich products are suitable for the steel production. During the reduction roasting or plasma smelting the high volatile zinc and lead metals were removed and enriched as a secondary dust, Zn-Pb concentrate, which is suitable for processing in zinc and lead smelters. Suggested processes are commercially feasible and environmentally friendly without any solid or liquid waste.

Jan 1, 2003

By P. M. Swash

This paper reviews the application of some mineralogical techniques in the evaluation of the Uitkomst Ni-Cu deposit, South Africa. The low grade of the ore necessitates detailed and representative characterisation in order to establish the prospects viability. The relevant mineralogical information is generated by using optical microscopy, magnetic and heavy liquid . separations, XRD. SEM and EMPA. Methods used are briefly reviewed. The cost savings and metallurgical understanding that is provided by the mineralogical work is described especially with regard to milling, flotation and the presence of by-products (PGMs and chromite).

Jan 1, 1991

By Shivendra Sinha

Total pressure oxidation (TPOX) is widely outreached leaching practice for base metals from sulfide minerals, wherein high temperature (T ∼ 200 °C) and oxygen pressure (pO2 ∼ 25 bar) are required. These aggressive conditions intensify the oxygen mass transfer, and therefore facilitate metal dissolution. However, challenging-cum-negative aspects of such practice are energy and material intensive requirements and high oxygen demand. Thus, the present study explores the novel emulsified medium for enhancement of oxygen mass transfer, which assists faster metal dissolution at significantly lower temperature and pressure condition. It is possible to achieve quantitative dissolution (>95%) of Cu, Ni and Co from mixed sulfide minerals at T ∼ 95 °C and pO2 ∼ 2 bar using an emulsion of 2.5% (v/v) n-Hexadecane in dilute sulfuric acid. In addition, n-Hexadecane was found to be inert, stable and immiscible in a pressurized leaching system, thus can be easily separated and recycled in subsequent leaching stages. Thus, this study offers an energy efficient route for low temperature-pressure leaching of sulfides.

By Colin Dessemond

Since 1950, the traditional process has been dominating the production of lithium compounds from spodumene ores to sustain the lithium market because of its economic viability and the markets need for technical grade (99.5% purity) product. This traditional process includes thermal conversion, acid roasting and lithium leaching. However, this process has not been challenged and very few studies have tried to explain its limitation (95% lithium yield) or optimize the thermal treatment. Here, α to β spodumene conversion and lithium extraction were performed in a rotary kiln on a 2 mm to 2 cm spodumene concentrate instead of a micrometric one using a 1050 °C, 30 min conversion treatment and 250 °C, 30 min, 30% H2SO4 excess leaching treatment. X-Ray Diffraction analyses were performed on the converted material to determine the conversion rate by Rietveld analysis. It was observed after thermal treatment that the α-spodumene particles fractured and divided while the impurities remained compact. A sifting was performed after thermal treatment and it was determined that 65% of the initial mass became finer than 180 μm. X-Ray diffraction analyses and lithium content measurement were performed on both fractions and it was determined that the finer fraction had a very high lithium content of 3.24 wt%. Lithium extractions were performed on both fractions separately. While the coarser fraction’s lithium yield was only 61% the finer fraction’s lithium yield went up to 99% without any additional treatment. These observations may open more economical ways for the traditional process by potentially bypassing two third of costly steps such as grinding.

By E. Anelli

Based on experimental continuous cooling transformation (CCT) diagrams, an artificial neural network has been trained to predict the amount of microsturctural constituents and hardness resulting from and controlled cooling at rates from 150 to 0.015 K/s. It can be applied to quenching and normalizing processes of low-alloy steels with 0.05-0.30 C% and 0.4-2.0% Mn -with possible microalloying additions. Examples of the good predictive capabilities about 15 Vickers standard deviation for hardness and a few percent for volume fraction of phases) are reported' Keywords: Austenite decomposition, low. And medium-carbon steels, artificial neural networks

Jan 1, 2003

By Takashi Fujii

In the OG (Osaka Gas) process which includes a fusion process of sewage disposal sludge in coke bed knowledge of molten and fluid properties of the sludge are most important to controll the process in good condition. Thus, the softening and melting temperatures and viscosity were measured by the sessile drop technique and a rotating viscometer. Obtained results are summarized as follows: Melting character of sludge slag is varied according to their composition, but closely related to CaO/SiO2 ratio in ordinary sludge and to CaO/(Cr2O3,+Al2O3+P2O5) ratio in Cr2O3 containing sludge. Fluid property of sludge slag has a correlation with optical basicity or Riboud parameter, However, the correlation is poorer than that of metallurgical slags. Especially, chromium oxide containing sludge shows high viscosity and behaves somewhat different manner from ordinary sludge.

Jan 1, 1992

By Kazuki Morita

Dissolution mechanism and solubility of chlorine in the oxide melts, such as CaO-SiO2-Al2O3 (-Na2O), Na2O-SiO2-Al2O3 and CaO-SiO2-FeO systems, have been equilibrium technique was employed with controlled Po2 and PCl2, (Po2 = 10-6 -10 19 atm, PCl2 10-6 -10-13 atm at 1673-1748 K). The solubility of chlorine in the 40mass%CaO-40mass%SiO2- 20mass%Al2O3, slag was found to vary in proportion to Pb2/ w and pc/z/p' which proved that chlorine dissolved in the melts as C1 anion. Hence, the chloride capacity (CCI-), indicating the ability of molten oxide to absorb chlorine, has been defined as; The Ccl value was observed to increase with increasing slag basicity and temperature, and showed a reasonable relationship with that Of CS2-. Based on the result obtained in the present study, chlorine distribution during incineration with slags was predicted quantitatively.

Jan 1, 2003

By J. T. I. Poijärvi

The smelter off-gas cleaning and the weak acid treatment at Outokumpu Harjavalta Metals Oy are presented and described in this paper. The smelter consists of the copper and nickel smelters and the acid plant of three separate acid plants two of which are double contact and one single plant and of one liquid sulphur dioxide plant. The preliminary cooling and flue dust separation of the smelter off....,gases from the copper ?and nickel flash smelting furnaces and converters? in the waste heat boilers and in the hot electrostatic precipitators are described. The final cooling and cleaning of the gases in the scrubbers at the sulphuric acid plant and the treatment of the weak acid in the vacuum and in the submerged combustion evaporators for the removal of impurities are presented as well as the treatment of the condensates from the evaporators. The attention is paid to the generation of sulphur trioxide in the smelter off-gas.and to the treatment of that in the weak acid bleed-off and to the utilization of the treated acid.

Jan 1, 1992

By Zhenglong Li

A process has been developed to recover titanium from a blast-furnace slag which contains about 20-25% Ti02 and 12% Fe. In this process. "hot" slag from the blast furnace is directed to a separate furnace where it is reheated with additives to form two simple slag phases: one is titanium enriched anosovite (Ti3O5) and the other is a titanium lean non-crystal glass phase. The modified slag is then processed by conventional beneficiation techniques to produce a marketable titanium concentrate and a usable slag material. This paper focus on separating anosovite from glass by electrostatic separation and froth flotation.

Jan 1, 1996

By N. B. Gray, I. F. Taylor

"Gas injection to promote chemical reactions or mixing is a feature of many metallurgical processes. Often the aim of gas injection is to bring about a chemical reaction between the gas and liquid but most of the past physical and mathematical modelling work has ignored the influence of such reactions. In the work reported here, cold model studies have been conducted in which gas reacts with the liquid into which it was injected. The rate of liquid mixing has been measured as an indication of the mechanical energy transfer. It has been found that gas generated chemically within the liquid is significantly less effective at promoting mixing than the equivalent volume of inert gas. The relative ineffectiveness of chemically produced gas is thought to be due to smaller bubble sizes in comparison to the inert gas case. Small bubbles characteristic of chemically generated gas move with low slip velocities relative to the liquid and lead to different turbulence generation mechanisms.IntroductionIn processes such as steelmaking, copper conversion, bath smelting and ladle steel finishing gas is injected into liquid metal where it reacts chemically or simply serves as a source of agitation. An understanding of fluid flow phenomena in such situations is an essential pre-requisite to the calculation of process intensity and the optimisation of vessel productivity. Traditional physical cold modelling approaches to prediction of liquid flow in such situations are now often augmented by the techniques of computational fluid dynamics. Even with the availability of numerical modelling techniques cold physical models continue to have an important role for validation because it is generally difficult to obtain quantitative data from high temperature processes.Almost all previous cold modelling work has been based on the injection of an inert gas into water or some other non-reactive liquid. Such models do not include the significant increase in gas volume inherent in some processes. For example the oxidation of carbon in steelmaking leads to a twofold increase in molar gas flux through the reaction:"

Jan 1, 1996

By Ivan Imris

The iron production has generated many tonnes of very fine residues with high concentration of iron. In addition, during the recycling of galvanised steel scrap in the steel making processes the zinc and lead are largely concentrated in the dust. These kinds of dusts are usually dumped beside the metallurgical plants and cause environmental problems. Therefore the metal recovery from the metallurgical residues has become a major interest not only from the viewpoint of metals recycling but mainly from the viewpoint of environmental land protection. The thermodynamic analyses and laboratory experiments suggested that the metals could be recovered from metallurgical wastes by reduction roasting and by plasma smelting processes. The iron rich pellets with very high metallization may be obtained from metallurgical wastes by the reduction roasting and the inert slag and pig iron could be produced by plasma smelting processes. In both cases the iron rich products are suitable for the steel production. During the reduction roasting or plasma smelting the high volatile zinc and lead metals were removed and enriched as a secondary dust, Zn-Pb concentrate, which is suitable for processing in zinc and lead smelters. Suggested processes are commercially feasible and environmentally friendly without any solid or liquid waste.

Jan 1, 2003

By Hongfa Hu, Stavros A. Argyropoulos

"This paper describes a mathematical model which simulates numerically reaction driven fluid flow phenomena. The driving force of this reaction is an exothermic heat of mixing. In addition, the model predicts the heat and mass transfer phenomena where both heat source and heat sink co-exist in close proximity. The heat source is generated by an exothermic reaction. The heat sink is formed by a moving boundary such as the melting of a solid. This type of phenomena occur quite often in various metal processing operations in which exothermic additions are immersed in liquid metals. The model is based on the SIMPLER algorithm and uses an enthalpy method to predict the fluid flow, temperature, and concentration fields. The results indicate that the exothermic mixing reaction was responsible for an abrupt rise in temperature around the moving boundary. The intensity of this reaction was also found to be responsible for the enhanced convection of fluid and the acceleration of the moving boundary. The modelling results were also verified by experimental work which included velocity and temperature measurements in a low temperature physical model. IntroductionAlloying additions are used extensively in the treatment of liquid metals during metallurgical processes. The alloying additions introduced into liquid metals can be classified into various classes, each of which follows its own route[l]. As a major group, the exothermic additions follow two different steps during their assimilation into liquid metals. In the first step, upon immersion, a metal shell solidifies around such additions, and then melts back. At this point, the second step commences. During this second step, due to the mixing of the addition with a liquid metal, an exothermic reaction occurs, which liberates large amounts of heat, resulting in an enhanced convection in the liquid metal surrounding the addition."

Jan 1, 1994

By Dae Jin Ha

Sticking phenomenon occurring during hot rolling of two STS 430JlL ferritic stainless steels was analyzed by hot-rolling simulation tests. The sticking started from the initial nucleation stage in which the rolled materials were stuck onto the roll specimen surface, proceeded to the growth stage in which stuck fragments grew further, and reached the saturation stage. The modified 430JlL steel had a smaller number of sticking nucleation sites and slower growth rate than the conventional 430JlL steel because of higher high temperature hardness, thereby leading to less serious sticking. When the simulation test was conducted at 1070 °c, Cr oxides were formed on the surface of the rolled materials, and thus the sticking was drastically reduced because of the increased surface hardness of the rolled materials. In order to prevent the sticking, high-temperature properties of the rolled materials should be enhanced when rolled at 900°C or 1000 °C, and rolling conditions and alloying compositions, under which the oxide formation was promoted, were more important than high-temperature properties when rolled at higher temperatures than 1000 oC.

Jan 1, 2008

By Hiroyuki. Fukuyama

The pseudo-binary phase diagram of the cuspidine (3CaO2?SiO2?CaF2) - CaF2 system has been studied by electron probe microanalysis (EPMA) and X-ray diffractometry (XRD). To prevent fluorine loss in the form of a HF gas by a reaction of CaF2 with water vapor at elevated temperatures, the equilibrium experiments were conducted with the sample hermetically sealed in a platinum tube. By employing this technique, it was successfully revealed that cuspidine exists as a stable phase and congruently melts at 1684 ± 1 K, and the cuspidine - CaF2 system presents a simple eutectic type of phase diagram, of which eutectic temperature has been estimated to be around 1540 K, corresponding to the composition of 40 mass% 3CaO?2SiO2 - 60 mass% CaF2?

Jan 1, 1999

By Zhihua Wang

Through metallurgical calculation and process analysis based on metallurgical theory, it is aimed to raise the concentration of smelting oxygen and improve the update speed of reaction interface, accelerate the reaction and achieve a high-intensity smelting at the stage of converting. The PM plant has launched a theoretical research on model of high-intensity converting aiming at increasing the oxygen concentration of converting, carried out transformation of Kaldo furnace converting system, performed a series of industrial trial operations, conducted multiple rounds of tracking test and data comparison in reducing the furnace cycle, lowering the unit consumption of fuel and stabilizing the furnace lining life. The move has practically tested and verified the correctness of high-intensity smelting theory.

By Gabriel Riveros

Fire refining of copper consists of two stages copper oxidation and copper reduction. Very frequently the capacity of the anode furnace is determined by the rate of copper reduction. The analysis of factors affecting the rate of the oxygen reduction from a liquid copper with solid carbon or injected hydrocarbons pointed out the role of the mass transfer in a liquid copper in final stage of the reduction. Experimental results of copper reduction with graphite and injected natural gas in laboratory- scale crucibles showed two stages of the reduction process with a sharp change of the controlling mechanism. The estimated dynamic surface area of gas bubbles based on the measured bubble frequency and the gas flowrate allowed for the detennination of the reaction constant as a degree of the partial pre-combustion of the air/natural gas mix. The variation of the used reductant as a function of the oxygen concentration and temperature has been evaluated based on the detennined kinetic model. The intensification of copper reduction in fire refining has been discusses on the basis of obtained kinetic data and analysis of various factors detennining the time of reduction.

Jan 1, 2003

By Kenji Morinaga, Shigeru Fujino

"Preparation and vacuum ultraviolet (VUV) transmission spectra of aluminum fluoroberyllate glasses, MgF2-CaF2-SrF2-A1Fr BeF2 (MCSA-Be) and MgF2-CaF2-SrF2-AlFrYFrBeF2 (MCSAY-Be), were studied. The influence of YF3 and BeF2 on the thermal stabilization against crystallization and VUV transmittance was investigated. With increasing the BeF2 content, the crystallization tendency decreased and the absorption edge shifted to shorter wavelength in the MCSA-Be and MCSAY-Be glasses. The MCSA-20Be glass composition exhibited the shortest wavelength UV absorption edge (-147 nm) and the highest transmittance at 157 nm (60% for 2 mm sample thickness). The transmission values at 157 nm and the slope (steepness) of the absorption edge were found to be significantly influenced by the trace amount of Fe2+ derived from the BeF2 raw materials.IntroductionPure beryllium fluoride is known to be an only fluoride that forms one component glass on cooling from the molten state and is structurally similar to silica with [SiO4]4- tetrahedra. Molten BeF2 is highly viscous with a viscosity of about 106 poise near its liquidus temperature at 550""C[l]. The addition of modifying fluorides such as LiF, NaF or KF to BeF2 substantially decreases the viscosity[2]. Glass forming region of binary fluoroberyllate glasses has been mainly reported by several authors [3]. LiFBeF2 binary system is structually analogy for Mg0-Si02 system from their phase diagram and ratio of ionic radius for each cation and anion, respectively. LiF-BeF2 binary glasses seems to be promising candidates for the extreme deep vacuum ultraviolet (VUV) transmitting optical materials owing to their larger band gap. However, it is chemically unstable, and so, have no practical application for lens systems in micro lithography equipments and substrate materials for F2 (157nm) excimer laser[4]. There are also few reports on the VUV transparency of multicomponent aluminium fluoroberyllate glasses from the view point of their compositional dependencies. The purpose of this paper is to prepare deep VUV transmitting optical materials and determine the optimum glass compositions for aluminium fluoroberyllate glasses investigating their thermal stabilization against crystallization."

Jan 1, 2000

By Z. Zhang, Cuihuan Huang, Zongshu Zou, Nan Wang, Xueqian Xin

"Vitrification is considered as an attractive procedure for municipal solid waste incineration ash, which can realize the volume reduction and innocent treatment of incineration ash, as well as reuse of bottom ash. The main oxide components of molten ash slag are CaO, Al2O3, SiO2, Fe2O3, MgO, and Na2O, accounting for more than 90% of the total mass. The phase relations and thermodynamic properties of the CaO-Al2O3-SiO2-FeOx-MgO-Na2O oxide system is highly required, and is of great scientific significance for optimization of vitrification processing and sustainable resource utilization of melting slag. A study on the equilibria phase relations of CaO-SiO2-MgO-FeOx system was done by using CALPHAD method based on FactSage in this paper. The modeling parameters for the thermodynamic properties of liquid phase in CaO-SiO2-MgO-FeOx system were established and the equilibrium phase relations of MgO-SiO2-FeOx and CaO-SiO2-FeOx-MgO systems were calculated for different temperatures and oxygen partial pressures.IntroductionThe main oxide components of vitrified bottom ash slag are CaO, Al2O3, SiO2, Fe2O3, MgO, and Na2O, accounting for more than 90% of the bottom ash by weight [1]. During slag processing and modification, the knowledge of thermodynamic properties and liquidus temperature in the related slag system is highly required [2-5], which is not yet available. Through literature survey [6-9], it is clear that the systematic information on the concerned complex slag system is scarce. Most binary subsystems except FeOx-Na2O have been investigated well. Among ternary subsystems, few phase relations of the Na2O-MgO-SiO2 ternary system are available. For the phase relations of the system Na2O-MgO-Al2O3, all the studies are focused on the Al2O3-rich region. Investigation on the CaO-Al2O3-FeOx system is limited to Fe2O3-containing system with relatively higher oxygen potential. Most quaternary systems are not studied well except the CaO-MgO-Al2O3-SiO2 system, mainly due to their metallurgical importance. Figure 1 demonstrates the research status of the vitrified bottom ash slag with almost zero effort [10]. The effort here is defined based on the published literature by considering the number of publications, the investigated composition ranges, and the research details. So far the engineers in the field have to make assumptions of the thermodynamic properties of the simplified oxide system, without taking into consideration the interactions of the different oxide components, which hinders the development of the slag valorization and utilization. In order to provide thermodynamic properties for the application of the vitrified bottom ash, the six-component oxide system (CaO-MgO-Al2O3-SiO2-FeOx-Na2O) will be investigated through both experimental approach and computer modeling."

Jan 1, 2011

By J. T. I. Poijärvi

The smelter off-gas cleaning and the weak acid treatment at Outokumpu Harjavalta Metals Oy are presented and described in this paper. The smelter consists of the copper and nickel smelters and the acid plant of three separate acid plants two of which are double contact and one single plant and of one liquid sulphur dioxide plant. The preliminary cooling and flue dust separation of the smelter off-gases from the copper and nickel flash smelting furnaces and converters in the waste heat boilers and in the hot electrostatic precipitators are described. The final cooling and cleaning of the gases in the scrubbers at the sulphuric acid plant and the treatment of the weak acid in the vacuum and in the submerged combustion evaporators for the removal of impurities are pre¬sented as well as the treatment of the condensates from the evaporators. The attention is paid to the generation of sulphur trioxide in the smelter off-gas and to the treatment of that in the weak acid bleed-off and to the utilization of the treated acid.

Jan 1, 1992