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By Y. C. Avniel, T. E. Warner

"It is important to be able to measure sulphur and nitrogen in molten iron and steel on-line. Unfortunately, there are no solid electrolytes which are stable under oxidising conditions and in which the ions of these species are mobile. In this paper, novel applications of beta alumina electrolytes are described and the results compared with data in the literature. Excellent agreement was obtained confirming this approach as a viable method of detecting elements whose ions are not mobile in solid electrolytes.IntroductionIn the past two decades, the rate of many processes in steelmaking have increased substantially. The sophistication of chemical analysis has also increased but analytical equipment is frequently positioned a significant distance from the operating plant which dictates that time is spent taking a sample, sending it to the analytical facility, preparation of the analytical sample prior to insertion into the equipment. In many cases, the time taken for analysis can exceed the time taken for the actual process and is now the rate defining step. Furthermore, most analytical methods are unable to distinguish between the amount of element which is dissolved in the steel and that contained in precipitates. Even if the analytical equipment could separate these two, the distribution would have changed between the molten steel and the cast sample. It would be an advantage to analyse on-line for impurities in molten metals."

Jan 1, 1997

By Takashi Yoshida

"This paper will discuss the recent situation and future of the zinc industry from the technical point of view. It includes recent problems faced by the zinc industry and technological developments. One of the biggest problems of the zinc industry is raw materials. Traditional zinc concentrate becomes much complicated with respect to its chemical and physical properties. Thus, each process faced various problems. Also, secondary resources, generating so called recycling processes, become much more important. Recycling is, of course, a very important aspect for sustainable development of society. Secondary raw material also includes a great variety of impurities not included or very low levels in traditional zinc concentrate. Some problems are caused by these impurities. To overcome these problems some technological challenges have been taking place. Details will be discussed in the symposium.IntroductionZinc is a very useful metal based on its elechtro-chemical, chemical and physical properties. The most important usage is galvernizing of steel which is used for automobile, construction and a very wide range of other indutries. Also, zinc is used for dicasting and other alloys such as brass. Smelting of zinc is different from other metal because of its electro-chemical properties. Many parameters should be controled compared with other metals such as iron and copper. Typical zinc smelting processes are the Imperial Smelting Process (ISP) and the electlolytic process. The ISP process is a pyro-metallurgical process using a blast furnace. The electrolytic process is a hydrometallurgical process. Both processes are energy intensive, and the smelting process cost is increasing because of higher energy costs. The situation of the ISP is very severe because of higher coke prices. Recently, many ISP plants have been shut down because of economic reasons"

Jan 1, 2012

By Akira Yazawa

The similarities and differences in copper, nickel and lead smelting processes are discussed based on the sulfur-oxygen chemical potential diagrams and the free energy minimization assessments using a thermodynamic software. The prominent features of copper smelting are ascribable to the fact that copper has a strong affinity for sulfur but weak for oxygen and the liquid phase immiscibility between Cu and Cu2S. During the oxidation of sulfides, nickel metal is not stable except at temperatures higher than 1500°C, well miscible with its sulfide, and is oxidized more easily than copper. Metallic lead looks as stable as copper during the oxidation of the concentrate but Pb and PbS. are much more miscible with each other and the vaporization loss is considerable. In the reductive smelting of oxides, the effects of oxygen potential and temperature on the copper contents in slag are not significant due to the monovalent character of copper and the reduction of copper content in slag is not easy in practice. The effect of the slag compositions on the oxidic metal contents of slag is much more significant for lead than either copper or nickel. Due to the immiscible nature between Pb and Fe, high grade lead bullion is easily obtained and lead is more tolerant to impurities.

Jan 1, 1998

By Dirk Verhulst

The Altair Hydrochloride Pigment Process is a new ?third route?, besides the established high-temperature chloride process and the older sulfate process, to manufacture TiO2 pigment from ilmenite ore. It has been tested at a scale of 5 t/day feed. The ore concentrate is digested in high-acid, high total chloride solution (+/- 39% Cl). Titanium and iron both go into solution. Iron is separated as FeCl2 crystals after reduction and cooling. Titanium is transferred by solvent extraction into a purified, high-Ti stream. It is spray-hydrolyzed to produce a TiO2 hydrate and further calcined with additives into high-quality pigment. HCl solutions generated by pyrohydrolysis and spray hydrolysis are treated by pressure-swing distillation to regenerate HCl gas for re-injection into the digestion reactor. All chloride streams are recycled. Recent work has concentrated on optimization, particularly in 3 areas: - Solvent extraction: a new organic mixture, including a new diluent, makes it possible to work at room temperature, to avoid TiO2 hydrolysis problems and to improve phase disengagement and impurity separation. - Pigment finishing: a systematic study of the parameters involved, followed by long runs in the best conditions confirm pigment quality. - Flow sheet optimization: innovative modifications of the conditions of spray hydrolysis and pyrohydrolysis, combined with re-routing of streams achieve significant energy savings. A 100 t/year pilot plant including these features as well as other process improvements is under construction.

Jan 1, 2006

By G. R. Waters

NMR360 is developing a suite of chloride-based metals extraction processes, with the first commercial operation scheduled for commissioning late in 2018. It is critical, therefore, that with the introduction of any new technology, that the circuits do not suffer from mechanical failures which will compromise the operation. Although chloride leaching is at atmospheric pressure and relatively low temperature, the main challenge is preventing corrosion, since the high proton activity makes even a small amount of acid behaves as though it were concentrated. An additional challenge in concentrated chloride circuits is the potential for solids precipitation. In this context, therefore, correct valve selection is crucial, and NMR360 has partnered with CGIS to ensure that the Severe Service Valves (SSVs) needed will perform over and above the definitions of the Manufacturers Standardization Society (MSS) of the Valve and Fittings Industry. This paper outlines what the minimum requirements are for SSVs in chloride leaching applications, drawing on five decades of industry experience from one of Canada’s leading valve experts.

By S. W. White

Plasma arc technology is increasingly being used to process a number of waste materials. In present research, plasma technology is being investigated to treat waste magnesium baghouse dust, which is a waste material from the Magnetherm process. This dust contains mostly MgO, but also contains NazO, CaO, and KzO. Plasma energy is to be used along with a reducing agent to produce pure gaseous magnesium while keeping the other materials in a slag. The magnesium will then be collected by rapid quenching. A non-transferred arc plasma torch is ideal for this reaction because of its high enthalpy and improved energy efficiency over conventional methods. Another advantage of plasma is that it allows for the pre-heating or pre-reacting of fine particles before contact with the melt. Thermodynamic calculations using the Gibb energy minimization method were used to determine the most stable compositions of the materials at various temperatures. Energy balances have also been calculated. These results conclude that we can recover approximately 98% of the magnesium with a proper quenching technique. The calculated results are compared with the experimental data, and good agreement between them was observed.

Jan 1, 1999

By Chen Zhang

Polycrystalline Ti-rich NiTi thin films have been deposited from a single NiTi target using a DC magnetron sputtering system. Free standing film was obtained by using a single crystal silicon substrate. Thickness ofthe thin films is controlled at around 12 pm. In this investigation, the effect of deposition temperature on the microstructure and transformation temperatures of the thin films is studied. Influence of post heat treatment temperatures on the properties of the thin films is also investigated. Transformation temperatures of the thin films are determined by differential scanning calorimetry (DSC). The surface microstructure of the thin films is studied using a scanning electron microscope (SEM), and the crystallinity is determined using x-ray diffractometry. It is found that the thin film deposited on a hot substrate is crystalline even when the substrate temperature is as low as 300°C, while the normal crystallization temperature for an amorphous thin film is around 500°C. The microstructure of the film deposited on a hot substrate shows a very fine grain size. The grain size increases with increasing substrate temperature during deposition. The effect of post deposition heat treatment on grain size is minimal.

Jan 1, 1999

By Zhijing Zhang, Ramana G. Reddy

"The viscosity of molten oxides is one of the important physical properties since viscosity has a decisive influence on fluid flow. The knowledge of the viscosity of molten oxides is essential for modeling and controlling of metallurgical process. In the present study, viscosities of high basic Na2O-B2O3 and Na2O-SiO2 binary melts and viscosities of Na2O-SiO2-B2O3 ternary melts were measured as a function of temperature and composition. Experiments were carried out using rotary viscometer and graphite components. Our experimental results were compared with those in literature. Based on the current experimental data, the previously developed viscosity model was modified. The characteristic features of viscosities of these melts have been discussed. The predicted viscosity results are in excellent agreement with the present experimental data in the temperature range with molten state samples. IntroductionThe viscosity of molten oxides is one of the important physical properties since this property has a decisive influence on fluid flow, and is one of key factors to be taken into consideration in process modeling. The manufacturing operations require the viscosity of molten oxides to be within certain ranges. Although, some viscosity measurements on borosilicate systems have been carried out [1-4], the viscosity data in literature are available only for a few temperatures and cover small composition ranges. The agreement between the results of these works is not satisfactory [I-4]. Even the viscosities of binary systems Na2O-B2O 3 and Na2O-SiO2 generally are well studied, the available viscosity data in literature are only found in the composition range of O to 0.333 mole fraction ofNa2O. The aim of the present study is to provide a base with accurate experimental data for reliable model extrapolation."

Jan 1, 1999

By Chikabumi Yamauchi, Mitsuru Tanahashi, Toshiharu Fujisawa

"Thermodynamic properties of impurities in molten silicon are of prime importance in developing economical production methods of solar grade silicon. In the present research work, thermodynamic properties of boron, the most difficult element to remove from molten silicon, were measured by chemical equilibration techniques at 1723 and 1773 K. Activity coefficients and self-interaction parameters of boron in molten silicon were determined by equilibrating the melt with solid BN under controlled nitrogen partial pressures. Interaction parameters between boron and nitrogen in molten silicon were also determined by equilibrating the molten Si-B alloys with solid Si3N4• Based on the data obtained, the stability diagram of the Si-B-N system was established.IntroductionPhotovoltaic power generation using a silicon solar cell is expected to be the most promising energy source, because it is inexhaustible, cleaner and more safety than conventional energy sources, such as thermal or atomic power generation. At present, expensive off-grade silicon for semiconductor (SEG-Si) is used for a solar cell production. However, if a large-scale photovoltaic energy conversion using silicon solar cell comes into wide use in the near future, silicon will be sure to be in short supply for the cell. Therefore, a development of a new large scale process for solar grade silicon (SOG-Si) production is definitely necessary, which can remove contained impurities from silicon.Among the impurities contained in silicon, boron is one of the most difficult ones to remove by a zone melting or an unidirectional solidification, because its segregation coefficient in silicon is close to unity (0.8). In addition, boron behaves as a p-type silicon semiconductor dopant and, therefore, its content in SOG-Si must be severely controlled. Although some attempts to remove boron by various metallurgical methods have been carried out [I -4], quantitative analysis has not been made due to lack in the information on the thermodynamic properties of boron in molten silicon. From this view point, the activity of boron in molten silicon was determined in the present study by chemical equilibration techniques at 1723 and 1773 K."

Jan 1, 1998

By Linfeng Zhou, Rong Sun, Guanghui Li, Zhiwei Peng, Tao Jiang

Dust, or airborne particulate matter, from metal smelting can be either mechanically or thermally generated and it negatively affects the indoor air quality as well as the fugitive emissions from the plant. The thermally generated dust is often referred to as fume and it is typically generated whenever liquid metal comes into contact with air. For practical reasons, such as vehicle access, etc. it is often difficult to collect 100% of the fume. It is therefore highly desirable to develop processes and optimize operational procedures so that fuming can be kept to a minimum. In this series of experiments, the mechanism of active oxidation and fume formation from liquid silicomanganese under an impinging air jet in the temperature range 1400-1600°C has been explored. Characteristic properties of the fume have been established; particle diameter, shape, size distribution, and elemental composition are reported. The oxidation process is described in terms of vaporization, oxidation and agglomeration. In the boundary layer, two competing mechanisms seem to be operative in parallel: a direct oxidation of Mn vapor, and a two-step oxidation of silicon. The thermodynamic and kinetic conditions governing the two mechanisms are discussed.

Jan 1, 2016

By P. J. Uggowitzer, H. Kaufmann

"New Rheocasting is a novel route of semi-solid casting, in which the globular semi-solid precursor material is produced by controlled cooling of only slightly superheated melts in conventional steel crucibles. The resulting semi-solid slugs are placed into the sleeve of a vertical Squeeze Casting Machine and then filled into steel dies. Solidification occurs under hydraulic pressures up to 100 MPa Due to the reduced cost of precursor material, reduced investment cost and easier recycling, the New Rheocasting process offers cost reductions of up to 25% over conventional semi-solid casting · routes. The New Rheocast products are pore free, pressure tight, weldable and heat treatable castings.In the present work the New Rheocasting Process is introduced and the influence of heat treatment on mechanical properties of the New Rheocast alloy A356 is discussed.The alloy A356 is cast under ideal New Rheocasting conditions into a step die on an UBE HVSC 350 Squeeze Casting machine. As-east, TS and T6 heat treatment conditions with variations in solutionizing and aging time/temperature parameters are applied and the samples are tested by tensile testing. Alternatively, the same heat treatment conditions are applied to conventional Squeeze Casting parts and compared with New Rheocasting.Questions of potential cost savings due to modified heat treatment conditions are also addressed in this paper."

Jan 1, 2000

By J. Etay, S. Daugan, Y. Fautrelle

"New type of electromagnetic parametric instabilities arising at the free surface of liquid metal in the presence of a low frequency magnetic field are presented. First, the mechanism of the instability is analysed in an idealised case. Then, the experimental device working with mercury is described. Various shapes, both regular and irregular, of free surface are found. A experimental stability diagram is obtained. Measurements of the deformation performed on photographs are compared with physical orders of magnitude.IntroductionWhen a liquid metal pool of electroconductivity a is submitted to an A.C. magnetic field B = B0 cos mt, electrical currents j are induced in the liquid metal and interact with the applied magnetic field to create electromagnetic body forces F = j x B. Those Lorentz forces comprise both a mean value (time average) and an oscillating part. Those forces are widely used in many metallurgical processes to stirr a liquid metal or to control its free surface, e. g., in aluminium continuous casting or electromagnetic levitation problems (1-3). When liquid metal free surfaces are submitted to AC. magnetic fields, the shape of those interfaces may interact with the applied field and leads to a various instabilities. A review of these instabilities may be found in Fautrelle (4). That instabilities may be a problem for the control of processing as electromagnetic levitation or quasi-levitation."

Jan 1, 1999

By Chao Li, Qian Li, Yong-bin Yang, Kai Li, Qiang Xie, Yuan-yuan Zhu, Dong-ye Li, Qi-bing Tan

"The permeability of sintering mix is a vital technological property in sintering process. However, it can only be measured by off-line method on samples picked from the production. In order to acquire the properties of sintering mix accurately, on-line measuring of permeability is urgently required. Based on the reflection characteristics of bed permeability on pipe flowing parameters, a new method is presented in this paper for on-line measuring of sintering mix permeability. The measurement can be performed by blowing gas flow in the bed with the measuring pipe. Measuring results are obtained by picking the data on flowing rate and pressure in the pipe. The function of flowing rate to pressure may be certain for samples with the same permeability. Thus, the permeability was determined by contrasting this function to the result of off-line measuring, and the relative coefficient or R2 value was more than 99%.IntroductionThe permeability of sintering mix is a vital technological property in sintering process, which directly determines production and quality of sinter, or even determines whether the sinter production is carried out smoothly [1,3].The permeability have more obvious influence on vertical sintering speed, which is mainly related to air quantity passing through material bed. Under certain inducing capacity and negative pressure, the vertical sintering speed mainly depends on the permeability of sintering mix. Low permeability may make burning through point of sintering move back, and the sinter mix cannot be burnt through. High permeability may make burning through point of sintering move forward, improving production efficiency by increasing the speed of sintering machine [4] Good permeability means a small resistance of fan ,reduction of negative pressure of sintering machine, and full contact between air and sulfide, which can strengthen physical-chemical reaction during sintering process and increase desulphurization rate. In gas well through material layer process, gas-solid desulfurization reaction and gas-solid-liquid heat exchange are completed and hot gas through the combustion zone supplies the sintering process with heat. Finally uniform sintering of the material layer in height and width direction is achieved [5] While high permeability index leads to weak sinter strength, fast sintering speed, short residence time of high temperature region and little liquid phase. Moreover, liquid phase in the fast cooling process is too late to fully crystallize but forming glass phase which is harmful to sinter strength as well. Bad permeability means a big fan resistance and increase of negative pressure of sintering machine, which make the air pass through material layer difficultly. When air and mix contact difficultly, removal of sulfide reduces so that desulfurization is incomplete. Meanwhile, low caking efficiency, slow sintering speed and easily burnt sinter , reduce sinter output. Therefore appropriate permeability of sintering mix is the premise of stable burning through point and satisfactory sinter output and quality."

Jan 1, 2013

By Dieter Offenthaler

Catalysts used in petroleum industry often contain valuable amounts of PGMs. The typical recycling route for those materials is the pyrometallurgical one, but this treatment way offers limited flexibility with respect to small charge weights. A new process, combining a pyrometallurgical pre-treatment step of the ceramic carriers with a hydrometallurgical leaching procedure overcomes this disadvantage. It not only allows the economical treatment of even very small charge weights, but also gives the possibility to maximize the PGM yield by individually adapting the process to the different charge materials. Due to an ingenious process design, where all leaching agents and effluents are recycled in a closed loop and therefore no waste waters leave the process, process operation becomes very economical. However, the temperature-time-regime in the pyrometallurgical pre-treatment step is of major importance for the success of the whole process. Therefore various investigations have been done to identify how the different process variables in the pyrometallurgical pre-treatment influence the subsequent leaching procedure. It turned out, that the adjustment of the correct phase-modification in the ceramic carrier materials during the pyrometallurgical treatment is the key factor of this process step. Although it is a troublesome issue to exactly adjust the correct phase modifications, it is the prerequisite to take advantage of the benefits of this new process concept.

Jan 1, 2006

By Rejane Tubino Geyer

The volume of electric arc furnace (EAF) plus oxygen (BOF) slag produced yearly in the world is about 84 million ton. Because of this, the study of recycling processes as a way to solve the storage problem of these slags rise in importance. There are, however, some inconvenients on using this byproduct: lime, which takes part of the process of steel production, remains as a non-reactive raw product in the slag. Since lime reacts in presence of humidity, forming expansive compounds, slag use is strongly limited. There are some utilizations for the electric arc furnace and oxygen slag in the Civil Construction Industry, mainly as base, subbase and asphalt covering in highways. However, independently of the type of recycling, a period of "cure" of about six months is necessary. Because of this slow cure process this byproduct may turn non-competitive in some regions if compared, for example, with the natural aggregate. The objective of this work is to present the flowsheet of the slags production as a residue both at the electric and oxygen steel plants and, through a bibliographic review, to analize the possibilities and limiting factors for the use of steelmaking slags in the Civil Construction Industry.

Jan 1, 1996

The paper concerns an unconventional, yet promising, use of waste magnesite dust and fines. In India a significant amount of this dust is generated from some of the integrated iron and steel industries, refractory and cement plants, during calcination of raw magnesite. However. it is possible to utilize this dust, which is normally a waste, conveniently and economically for the production of magnesium. chemicals. A bench scale study was carried out to determine the rate of formation of sulfated com¬pounds of Mg.Ca,and Fe, inter alla, present in the dust system containing MeO constituents (in which Me=Mg.Ca,Fe,Si,Al etc.) Effects of various process parameters, which affect the reaction rate as also the purity of the product ,were also studied. Some work carried out to develop the process flow charts involving the salient steps to produce magnesium chemicals commercially is reported in the paper .

Jan 1, 1992

By M. Neises, M. Roeb, C. Sattler, S. Stenger

"A two-step thermo-chemical cycle process has been developed and investigated. It is based on metal oxide redox pair systems, which can split carbon dioxide as well as water molecules by extracting oxygen atoms and reversibly incorporating them into their lattice. If concentrated solar radiation is used as the heat source, a promising method exists to produce synthesis gas from water and CO2. An easy way of operation is gained by the combination of a ceramic substrate as the absorber structure, which can be heated to high temperatures with concentrated solar radiation, and of a metal oxide coating which is capable to carry out the redox reactions. The performance and kinetics of a ferrite based redox material coated on ceramic substrates were investigated in a laboratory set-up. CO2 could be reduced with significant conversions. In addition, several side reactions were observed like the formation of carbon and like the Boudouard reaction.IntroductionThe search for alternative energy carriers and for processes able to reuse carbon dioxide stimulates the research for sustainable routes of alternative fuel production. In the scope of this search thermo-chemical processes combined with sources of concentrated solar energy have become more and more attractive. Ideally, the only raw materials for such processes are water (H2O) and carbon dioxide (CO2) enabling not only a process free of emissions, but also allow to reduce emissions of other processes by reusing CO2 to provide synthesis gas, which itself can be applied to produce chemical commodities or even better synthetic fuels like methanol or petrol.In contrast to the direct splitting of those raw materials, thermochemical cycles split water and CO2 in several steps and enable hydrogen (H2) and carbon monoxide (CO) generation at temperatures controllable by today’s technical equipment. One of the most interesting thermochemical cycles is a two-step process using metal oxide based redox systems. During the first step of this cycle (the regeneration step) the metal oxide is reduced setting some of its lattice oxygen free according to reaction (1). In the next step (the splitting) the reduced and activated material is oxidised by withdrawing oxygen from water and CO2 and at the same time hydrogen and CO is set free according to reactions (2a) and (2b) respectively."

Jan 1, 2011

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 Omid Marzoughi

Chromium has a wide range of applications, including as an alloy addition in various steels and also as a corrosion resistance coating. Carbothermal reduction of chromite ore (FeCr2O4) in a submerged arc furnace is an important industrial process for extracting chromium, but the energy consumption is excessive. It is suggested that one area for future research is the low temperature carbothermic solid state reduction of chromite to produce an intermediate product, which can subsequently be upgraded to ferrochromium. In this regard, a thermodynamic model has been developed to investigate this process and the effects of temperature, carbon additions and ore composition on the recovery of chromium and the grade of the ferrochromium, have been studied. Further development of the model may allow it to be applied to the simulation of other processes for the recovery of chromium from chromite ores.

By Patrik Fredriksson

Thermodynamic data concerning FeO-containing slags is of importance in ladle refining of steel. With a view to generate a set of reliable and self-consistent thermodynamic data for these slags, experimental determination of the activities of FeO in binary and ternary slags was carried out using the gas equilibration method involving CO-C02-Ar gas mixtures at steelmaking temperatures. The slag samples in Pt crucibles were quenched after the equilibration and subjected to chemical analysis. The thermodynamic activities of "FeO" in the slags were calculated from the experimental data. The results are incorporated into a thermodynamic description of silicate melts in the present laboratory. The model is based on a Temkin-Lumsden approach and is able to compute the thermodynamics of higher order systems from the lower order ones.

Jan 1, 2003