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This symposium is dedicated to the lifetime achievements of Professor H.Y. Sohn. It covers the scientific fields, processing routes and investigation techniques in which Prof. Sohn has worked during his career and is based in the equally important three topical areas: Principles, Technologies, and Industrial practice. Professor Sohn was General Chair of the very first TMS Fall Extraction and Processing Symposium in 1983 in San Francisco which led to the Annual such symposia as this International symposium. Furthermore, the theme of that symposium was sulfide smelting, which is also included in this symposium. [ ] Professor Sohn was born in a beautiful dynastic capital Kaesung, Korea on August 21, 1941. He received his B.S. degree in 1962 from Seoul National University, M.Sc. in 1966 from the University of New Brunswick, Fredericton, N.B., Canada, and his Ph.D. degree in 1970 from theUniversity of California at Berkeley all in Chemical Engineering. After working as a Research Associate at the State University of New York at Buffalo and as a Research Engineer at Du Pont?s Engineering Technology Laboratory, Dr. Sohn joined the Department of Metallurgical Engineering at the University of Utah in 1974 and currently holds the ranks of Professor of Metallurgical Engineering and Adjunct Professor of Chemical Engineering.

Jan 1, 2006

By Payal Bakshi, Sangeeta Tiwari, Mohini Saxena, Anusha Sharma

"Recycling and reuse is perhaps the most favorable and beneficial way to solve the problem of industrial waste disposal. However, the use of industrial wastes like fly ash, tailings etc is in practice for brick manufacturing, land filling, embankments filling etc. These existing practices do not add enough value to the wastes. Moreover, some wastes may have very good potential to be incorporated in valuable products like paints. This study reveals about the value addition of industrial wastes like fly ash, copper tailing and blue dust as an extender in paints. Comparative properties and characteristics of these three wastes for application in paints are discussed. Fly ash, copper tailing and blue dust were characterized for physical, chemical and mineralogical properties and used in different paint formulation based on their potential to the particular application. Fly ash has been found very useful in enamel, primers and flat paints while copper tailing was found suitable in oil based paint formulations. The performance of fly ash and copper tailing paints were evaluated by comparing with those of conventional whiting extender. Blue dust was compared with conventional iron oxide for use in priming coats. The extender properties of these new material and paints prepared out of blue dust, fly ash, copper tailing, were found better than the existing related materials.IntroductionIndustrial development and environmental reforms should run parallel to benefit each other. This is the best policy, which must be adopted by industries for the sustainability of the current modern life. The high degree of industrialization and urbanization adds scads of waste resulting problem of pollution and challenges of their safe disposal. The nature of waste depends on the process that produces waste as its by-product. Therefore, policies/plans are prepared by keeping the view of possible potential hazards. Among the different wastes some are generated in the industries, which have great importance in the country’s economy, like fly ash waste from thermal power industry and mining waste. In India the total contribution of thermal power in the total electricity generation is more than 70% and it produces about 123 million ton of the fly ash annually [1]. On the other hand mining plus extraction of ferrous and nonferrous metals also produce waste in million tonnes of categories [2]. Since the generation of this waste is very high they cover large land area for their disposal and dumping [3]. The storage of this waste in the dumping sites for long time duration may cause problem of land, surface water, ground water and fertile soil contamination [4]. As far as Indian fly ash is concerned it does not contain toxic element over the limits of hazardous waste [5]. However, in general most of the metals deposits are found in the form of pyrite based ores. Mining wastes contain toxic elements e.g. heavy metals in varying amount, which get mobilized when pyrite get oxidized to sulphate producing sulphuric acid [6,7]. These ores contain very less amount of targeted metals in themselves thus they require extensive preprocesses for concentration of the metals [8]."

Jan 1, 2008

By T. I. Arbuzova

The present work presents the original data concerning using a high pressure torsion method and a shock wave loading technique to produce compact oxide nanomaterials and investigations of the effect of severe plastic deformation on a microstructure, crystal lattice and stability of these compounds. This allowed us to compare two ways of deformation action that can be characterized as quasi-static and dynamic effect, correspondingly. Particular attention was paid to a stoichiometry and surface composition changes upon severe plastic deformations. A procedure for studying chemistry of the oxide nanomaterials by means of nuclear microanalysis and Rutherford back scattering has been worked through. For surface studies the X-ray photoelectron spectroscopy has been used. It was shown that both distortion methods permit to produce massive nano-scale oxide materials from the coarse-grained powder during a single technological cycle. Bulk nanocrystalline materials based on LaMnO3, TiOy and ZrO2:Y2O3 were obtained by the quasi-static deformation technique. Nanoscaled ceramics of CuO, Mn3O4 and LaMnO3 were produced by the dynamic deformations. The density of the nanoceramics comes to 99%. Size effects and specific imperfection of the nanoceramics obtained lead to a set of particularities of physical properties.

Jan 1, 2006

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 Selvin Yesilay, Munevver Caki, Canbora Bayraktar, Bekir Karasu, Rahmi Imrak

"In this study, the utilization capability of the solid wastes taken from a commercial roof tile and brick factory in Eskisehir of Turkiye has been investigated in the production of stoneware bodies which can be formed by slip casting. At the first stage, X-ray fluorescent (XRF) and X-ray difractometer (XRD) analyses of the wastes were performed. Depending upon the results, a body recipe with an optimum casting concentration was adjusted. The bodies obtained from prepared slips were fired at 1160 oC as glazed and unglazed forms. Then, they were undergone certain tests in order to determine their firing shrinkage values, water absorption levels and optical parameters. To establish what kind of phase formations occurred after firing as a result of waste incorporations into bodies XRD analysis was conducted. Additionally, effects of such a compositional modification on the microstructure of the bodies were examined by a scanning electron microscope (SEM). Consequently, it was concluded that fired roof tile and brick wastes could be evaluated in both glazed and unglazed stoneware bodies. Introduction Stoneware is the general name applied to many wares fired between 1150 and 1300 °C. It has a different and denser structure than those of ceramics produced at lower temperatures. Fired stoneware possesses a lower water absorption value. When matured at a high temperature, it gives a possibility for the use of feldspar as a main ingredient [1-2]. Colors of stoneware can be brown, red, white and most of the times beige. Firing usually takes place in oxidation atmosphere but also reduction can be rarely used. This naturally has an effect on the body colors [3]. Earth, which contains clay minerals, becomes plastic mud when mixed with water, has a capability to be easily shaped and can be hardened without cracking if fired at 900-1000 °C, is referred as one of the brick and tile raw materials [4]. Natural and aesthetic appearances of buildings obtained with brick and tile products, which make them preferable especially for construction sector, are of importance. Because clays being main raw material of that type of productions generally do not exist as pure materials in nature, their usability depends on their mineralogy and impurities they contain [5]."

Jan 1, 2008

This symposium is dedicated to the lifetime achievements of Professor H.Y. Sohn. It covers the scientific fields, processing routes and investigation techniques in which Prof. Sohn has worked during his career and is based in the equally important three topical areas: Principles, Technologies, and Industrial practice. Professor Sohn was General Chair of the very first TMS Fall Extraction and Processing Symposium in 1983 in San Francisco which led to the Annual such symposia as this International symposium. Furthermore, the theme of that symposium was sulfide smelting, which is also included in this symposium. [ ] Professor Sohn was born in a beautiful dynastic capital Kaesung, Korea on August 21, 1941. He received his B.S. degree in 1962 from Seoul National University, M.Sc. in 1966 from the University of New Brunswick, Fredericton, N.B., Canada, and his Ph.D. degree in 1970 from theUniversity of California at Berkeley all in Chemical Engineering. After working as a Research Associate at the State University of New York at Buffalo and as a Research Engineer at Du Pont?s Engineering Technology Laboratory, Dr. Sohn joined the Department of Metallurgical Engineering at the University of Utah in 1974 and currently holds the ranks of Professor of Metallurgical Engineering and Adjunct Professor of Chemical Engineering.

Jan 1, 2006

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 Pinakin Chaubal

The campaign life of a modern blast furnace depends on hearth wear. Distributions of liquid iron flow and refractory temperatures have a significant influence on hearth wear. A 3-D comprehensive CFD model has been developed specifically for simulating the blast furnace hearth. It includes both the hot metal flow and conjugate heat transfer thorough the refractories. The model has been extensively validated using measurement data from actual blast furnaces. Good agreements between measured and calculated refractory temperature profiles haven been achieved. It has been used to analyze the velocity and temperature distributions and wear patterns at different furnaces and conditions. The results can be used to point out the directions for protecting the hearth.

Jan 1, 2006

By Manolete Mena

WC-Co nanocomposite powder is among the first group of materials with a promising potential for nanocrystalline-materials application. A chemical vapor synthesis (CVS) process that has previously been used for preparing the aluminides of titanium and nickel, and other metallic and intermetallic powders has been applied to the preparation of WC-Co nanocomposite powder. This CVS system was designed so that a tungsten precursor (WCl6 powder) and a cobalt precursor (CoCl2 powder) were separately fed into each evaporator in a reactor by means of specially designed powder feeders. The reduction and carburization of the vaporized chlorides by methane-hydrogen mixtures produced nanosized WC and Co composite powder. The product is a very uniform mixture of the constituent powders, which is important to ensure a high quality of the bulk cemented tungsten carbide product after consolidation. In the present work, the effects of reaction temperature, CH4 to WCl6 ratio, CH4 to H2 ratio, residence time, and Co content on the powder composition and particle size were determined. The products were characterized using XRD, carbon analyzer, and TEM.

Jan 1, 2006

By Qingcai Liu

The effect of the TiC addition on corrosion resistance of the Al2O3-C refractories in smelting reduction melts has been studied by quasi-station immersion and rotary immersion. The corrosion rate of Al2O3-C refractories is decreased with the TiC addition. The corrosion mechanism of Al2O3-C refractories is oxidization of graphite carbon by the oxides of the melts and the formation of deteriorate layer.

Jan 1, 2006

By Roland Kammel

In combination with various physical and chemical methods also electrochemical techniques are most frequently used to improve the recovery of metals from aqueous dilute process streams or effluents e.g. in electroplating, metal finishing, mining and metallurgical plants. To insure cathodic metal recoveries with favorable current efficiency and high throughputs per unit of cell volume seve¬ral types of electrolysis cells have been developed comprising extended electrode surface areas and/or intensive electrolyte. agitation. The practical experiences with these units indicate especially for the electrolytic recovery of metals whose values are high, that the treatment cost permits profitable operations with relativly short payback periods for the units. Anodic reactions can be utilized for the removal of undesired anion contents or buildups of impurities. Appropriate combinations of these recovery methods are used to improve the versatility and the overall economy. Industrial applications reveal their potentional as addidtive techniques for existing processes to reduce the metal content of effluents to values that meet the guide lines of environmental legislation whereas integrated in-operation recovery methods are nowadays increasingly introduced to approach nearly close-loop operations.

Jan 1, 1992

By Norbert Hort, Karl Ulrich Kainer, Carsten Blawert, Daniel Fechner

"With the development of new heat resistant magnesium alloys, the automotive industry has introduced several parts to the drive train. The rising number of large magnesium components will result in a higher quantity of automotive post consumer scrap and the changing legislation will force car manufacturers to take magnesium recycling into consideration. So far post consumer scrap has not been used for magnesium alloy production. Quite a reasonable amount of automotive scrap is likely to end up in a mixed light metal shredder fraction. The separation of mixed magnesium scrap according to several alloys is complex. Therefore secondary magnesium alloys made from blended post consumer scrap would be useful. For this work a matrix of potential recycling alloys was prepared by chill casting and high pressure die casting. The materials were investigated for their microstructure, mechanical properties, heat resistance and corrosion properties. The results will be presented in this paper.IntroductionWithin the last ten to fifteen years several heavy magnesium parts have been assembled in passenger cars, such as gear box housings and crank cases [1, 2]. Reasons are the lately developed new heat resistant alloys and the increasing responsibility of automotive manufacturers to reduce the vehicles weight and thereby CO2 emissions. The latter is pushed by international legislation [3, 4]. The rising quantity of magnesium in automobiles will result in an increasing amount of so called post consumer scrap at the end of the vehicles life.So far magnesium recycling was done only for clean scrap that is free from impurities, contaminations and sorted according to a chemical composition or a single alloy respectively [5- 15]. The latter is also called class 1 scrap and mainly consists of sprues and runners from magnesium die casters [15, 16]. For the upcoming automotive post consumer scrap the materials quality strongly depends on the way end of life vehicles are treated. By proper dismantling of old cars, the bigger magnesium components could be collected and possibly treated similar to class 1 scrap [15]. Up to date automotive manufacturers have no uniform recycling system for end of live vehicles. Most probably a considerable quantity of old cars will be shredded. The resulting light metal shredder fraction will contain aluminium and magnesium scrap, both from several alloys. A separation of mixed magnesium and aluminium scrap is feasible according to [17]. Other authors claimed that the grade of separation of magnesium from aluminium is still not sufficient for a proper industrial recycling process of magnesium post consumer scrap [15, 16]. If an automatic sorting is possible it will probably be very expensive [18]. Therefore, so far the main use of post consumer scrap has been the steel desulphurisation and aluminium production [15]. The use of post consumer scrap for magnesium alloy production has been considered already by [15] and [16] but some problems have to be approached."

Jan 1, 2008

By Yongxiang Yang

High temperature processing of raw materials in metals production and recycling often involves complex multi-phase fluid flow and heterogeneous chemical reactions at various scales. Good understanding of the process physics and chemistry is crucial for process operation and process development. The traditional scale-up process through laboratory scale ? pilot scale ? commercial scale route has been more and more complemented and partially replaced by full-scale process simulation. Computational fluid dynamics (CFD) has become a very useful simulation tool in process research and development. At the same time industrial applications challenge the CFD development with its complex transport phenomena, often in large-scale reactors with small-scale physics and chemistry. The current paper discusses the applications of CFD to a number of high temperature metallurgical and materials processing applications. The research was carried out by using commercial CFD codes as the framework, and the emphasis was given to the special efforts for the development and implementations of sub-models with process-dependent physical and chemical characteristics. To illustrate the application of CFD simulation to high temperature metallurgical processes and coupling of sub-models to the general-purpose CFD codes, five examples are given: (1) melting of aluminium scrap in a rotary furnace for recycling, (2) molten hot metal flow in a heterogeneous coke-bed of a blast furnace hearth, (3) gas flow heat and mass transfer in a submerge electric arc furnace for phosphorus production, (4) high temperature incineration of hazardous waste in a rotary kiln, and (5) transient heating of metals in heat treatment furnaces.

Jan 1, 2006

This symposium is dedicated to the lifetime achievements of Professor H.Y. Sohn. It covers the scientific fields, processing routes and investigation techniques in which Prof. Sohn has worked during his career and is based in the equally important three topical areas: Principles, Technologies, and Industrial practice. Professor Sohn was General Chair of the very first TMS Fall Extraction and Processing Symposium in 1983 in San Francisco which led to the Annual such symposia as this International symposium. Furthermore, the theme of that symposium was sulfide smelting, which is also included in this symposium. [ ] Professor Sohn was born in a beautiful dynastic capital Kaesung, Korea on August 21, 1941. He received his B.S. degree in 1962 from Seoul National University, M.Sc. in 1966 from the University of New Brunswick, Fredericton, N.B., Canada, and his Ph.D. degree in 1970 from the University of California at Berkeley all in Chemical Engineering. After working as a Research Associate at the State University of New York at Buffalo and as a Research Engineer at Du Pont?s Engineering Technology Laboratory, Dr. Sohn joined the Department of Metallurgical Engineering at the University of Utah in 1974 and currently holds the ranks of Professor of Metallurgical Engineering and Adjunct Professor of Chemical Engineering.

Jan 1, 2006

By S. B. Breyner, A. Ressler, D. Gregurek, A. Spanring

"The changes in process conditions that frequently decrease the service life of refractory products provided incentive for RHI AG to develop high performance bricks, especially for non-ferrous metal applications. Innovative product development was required to determine suitable refractory products for improving lining life. At the Technology Center in Leoben, Austria, practical corrosion testing methods and facilities, including an induction furnace and rotary kiln, enable detailed comparative analysis of brick wear on a pilot scale. In tests that were carried out using a fayalite type slag, the newly developed RADEX VFG magnesia-chromite grade showed very promising results compared to the standard grades. Based on the test results, optimal refractory solutions can be recommended for this challenging industrial application and field trials can be performed directly at the customer's site.IntroductionThe complexity of metallurgical processes in the non-ferrous metal industry, and especially changes to the process conditions in combination with the diversity of metal processing furnaces ''', requires a precise understanding of each individual system for appropriate refractory product selection l2'. In addition, particular importance is focused on the specific refractory consumption being as low as possible.Another important aspect results from the global shortage of resources, which forces companies to invest in recycling processes. In the base metal industry, recycling operations have resulted in significant changes; for example, operating with two slag chemistries and process temperatures will influence the performance of previously suitable linings. The raw material mix for primary smelters has also changed, including higher levels of secondary raw materials in the smelter feed."

Jan 1, 2012

By Stanko Nikolic

Ferrous calcium silicate slags are potentially important for future practice in copper converting operations and processes and can be described by the ?Cu2O?-FeO-Fe2O3-CaO-SiO2 system. Despite its industrial importance the phase equilibria in this system have not been fully investigated. Characterization of this slag system is necessary to improve the design and optimization parameters of new processes, including fluxing and operating temperatures. Experimental methods have been developed to investigate the phase equilibria of these slags at copper saturation and without copper. This technique involved equilibration of samples at a fixed oxygen partial pressure, rapid quenching, and analysis of the compositions of phases using electron probe x-ray microanalysis (EPMA). Liquidus and solidus data are reported for the primary phase fields of spinel, wollastonite and tridymite at 1250oC and an oxygen partial pressure of 10-6atm. The resulting data has been used to construct liquidus isotherms in the ?FeO?-CaO-SiO2 system both in equilibrium with and without molten copper. The experimental results were compared with the predictions of a thermodynamic computer package utilizing a self consistent thermodynamic database. The predictions of the model were in good agreement with the experimental isotherms when projected onto the FeO-CaO-SiO2 section, however the copper concentrations in the liquid phase at copper saturation were lower than predicted using the current database of the model.

Jan 1, 2006

By Esperidiana A. B. Moura, Mariana N. Sartori, Vijaya K. Rangari, Angel Visentim Ortiz, Francisco R. V. Diaz, Rene R. Oliveira

"This work presents the preparation and characterization of a nanocomposite based on Poly(butylene terephthalate) PBT and Brazilian smectitic clay (bentonite chocolate clay). Before being incorporated as clay nanoparticles in PBT resin, the clay was organically modified by the addition of a quaternary salt and sodium carbonate. PBT/Clay nanocomposite (96.3:3.70 wt %) was obtained by using a twin-screw extruder machine. After extrusion process, the nanocomposite was characterized by tensile, flexural and impact tests, SEM, Vicat, HDT, DSC, TGA and XRD tests. The results showed that the properties of the nanocomposite obtained were superior to those of neat PBT. Concerning the temperature of thermal distortion (HDT) an expressive gain of around 45 % was presented to PBT/Clay nanocomposite compared to PBT evidencing the interaction of nanofiller with the polymeric matrix.IntroductionPolymer-clay nanocomposites, also called as polymer layered silicates nanocomposites have attracted much attention from both industry and academia over the past decade because they frequently exhibit unexpected properties. In contrast to the traditional fillers, nanofillers, in particular, nanoclay, is found to be effective. The addition of a small amount (< 5 wt.%) can show significant improvement in mechanical, thermal and barrier properties, flammability resistance, and electrical/electronic properties of the final polymer nanocomposite without requiring special processing techniques. Also, as with other nano-size particles, the overall crystallization rate and the glass transition temperature are also affected. It is generally believed that the improvement of properties of nanoclay composites is directly related to the complete exfoliation of silicate layers in the polymer matrix. However, a processing technique that produces complete exfoliation is still a technical challenge [1,2]."

Jan 1, 2012

Plastics recycling has become an established national industry in Korea. However, it is still in its infant stage and experiences growing pains. In Korea, mixed plastic wastes generated from households after hand picking and/or mechanical sorting processes amount to 1,700,000 ton per year in 2005, and most of these waste are finally end up with landfill and/or incineration due to lacks of separation technologies and economical reasons. These plastic wastes can not be used as raw materials for chemical and/or thermal recycling because of their high content of PVC (upto 4.0 wt.%). In the present work, gravity separation system has been developed to remove PVC from the mixed plastic waste and recover the individual plastics. The separation system mainly consists of air classification, crushing, feeding system at fixed rate and wet-type gravity separation system. The gravity system based on centrifugal separation also consists of mixing, precleaning, separation, dewatering, recovery system, wastewater treatment system, etc. The main objective of this process to be developed is to achieve high separation efficiency of polyolefins (PE, PP, PS) with less than 0.3 wt.% PVC content and less than 10% moisture content in the final products. The system with a capacity of 0.5 ton per hour is developed and operational results are presented.

Jan 1, 2006

By M. H. Lin, S. Kou

"Czochralski pulling has been a very widely used process for growing single crystals for electronic and optical applications. Dopant segregation can significantly degrade the quality and yield of single crystals. We have used the floating-crucible technique for segregation control in Czochralski pulling, our floating crucibles being unique in that the melt passageway is very long. As such, dopant back diffusion is suppressed, even when the cross-section of the melt passageway has to be relatively large to help the melt go through or when the pulling rate is very low. Single crystals of model materials K-doped NaN03 and Pb-doped Sn have been grown with very uniform dopant concentrations. IntroductionSingle crystals of electronic and optical materials are often doped with a small amount of impurities to develop required physical properties, e.g., P and B in Si for n-type and p-type semiconductors, respectively, and Nd in YAG lasers. Dopant segregation can result in nonuniform physical properties, thus degrading the quality and yield of the resultant crystals.Figure 1 is an illustration of the conventional Czochralski process for crystal growth. Several techniques have been developed to control dopant segregation in Czochralski pulling, including the push-pull technique (1,2), the drop-pull technique (3-7) and the floating-crucible technique (8-13). The first two techniques require precise sensing devices and feedback control systems to keep the feeding rate equal to the pulling rate. The last technique is simple since the feeding rate is automatically equal to the pulling rate."

Jan 1, 1994

By E. Allaine

Carbochlorination kinetics of pure MoO3, Nb2O5, Ta2O5 and V2O5, by Cl2+CO+N2 gas mixtures was investigated between 380 and 1000 °C. Standard free energy of carhochlorination reactions and phase stability diagrams of these refractory metal compounds were calculated. The influence of total gas flow rate, temperature, reactants partial pressures on the reactivity of these oxides were investigated. The apparent activation energies were found to be about 83, 75, 110 and 100 kJ/mole below 650°C for MoO3, Nb2O5, Ta2O5 and V2O5, respectively. Above this temperature, the Arrhenius plots exhibit a rate anomaly attributed to thermal decomposition of COCl2 and/or structural changes of these refractory metal oxides. The apparent reaction order of carbochlorination of these oxides with respect to Cl2+CO was determined. For these refractory metal oxides, the reaction rate was maximum for a Cl2/CO ratio of about 1 in the chlorinating gas mixture. Results of carbochlorination of these oxides are compared and discussed.

Jan 1, 1995