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By Sasa Djokic

In developed countries, the difference between demanded and produced quantities of non-ferrous and rare metals are compensated by secondary raw materials recycling and reprocessing of by-products from both ferrous and non-ferrous extractive metallurgy. Utilization of non-ferrous and rare metals from the metallic secondary raw materials is very significant, both for recovery of the metal value and contribution to the environment protection. Similar to all non-developed countries, the extractive metallurgy in Serbia was based on available natural resources and not so strict environment protection regulations, which was either insufficient or completely absent. Today, Serbia is at the beginning of development of efficient and economical technical and technological solutions in order to ?ecologize? technogenic systems by waste materials, secondary raw materials and degraded soils regeneration (by recycling and revitalization). Several metallurgical technogenic systems in Serbia, together with secondary raw materials classification according to their potentiality for metal extraction by using the existing technologies and expected economical and ecological effects of recycling, are discussed in this paper.

Jan 1, 2005

By Bora Derin, Sertac Yazici, M. Seref Sonmez

"In this study, the recycling conditions of waste liquor obtained after the production of tungsten boride powder from calcium tungstate by self-propagating high temperature synthesis (SHS) and the following hydrochloric acid leaching were investigated in detail. Environmentally unfriendly and extremely acidic (pH~ -0.3) liquor consisting of calcium, magnesium, and boron ions was treated with 1 M sodium carbonate solution to precipitate magnesium carbonate and calcium carbonate phases. The obtained amorphous precipitates were heated up to the temperature of 400°C for re-crystallization. As a result, MgO, CaC03 and CaMg(C03)z phases were obtained, while sodium, boron, chlorine ions were remain in the solution. The present study is still in progress.IntroductionSelf-propagating high temperature synthesis (SHS) is one of the techniques used in the production of a variety of advanced ceramics, inter-metallic, organic and inorganic compounds, oxygen free single crystals, and polymers [ 1, 2]. The reaction becomes selfsustaining and propagates in the reactant mixture, after initiation in SHS process. SHS products may contain the mixture of several unwanted compounds and elements. Therefore following acidic leaching process may be needed to purify the target product. In the previous study, calcium tungstate (Ca W04), magnesium (Mg) and boric acid (B20 3) mixture were reacted to produce tungsten boride powder by SHS process according to the Reaction 1. Then, magnesium and calcium containing byproducts (i.e. MgO, Mg3B206 and Ca3B206) found in the SHS product were leached out by using concentrated hydrochloric acid (HCl) solution to obtain pure tungsten boride powder [3].Ca W04 + 0.5B203 + 4.5Mg = WB + 4.5Mg0 + Cao (1)After the leaching, filtrate solution consisting of different amounts of magnesium, calcium, and boron requires additional treatment for the environmentally acceptable disposal.Several works were carried out about magnesium precipitation conditions and kinetics from brines. Rabadzhieva et al. investigated the precipitation of Mg(OH)z from brines by using NaOH as well as caustic soda [ 4]. Turek ve Gnot investigated the precipitation efficiency of Mg(OH)z for the temperature range between 10-40°C, while the reaction was kinetically experimented by Alamdiri et al [5, 6]. Homogeneous precipitation of nesquehonite (MgC03.3H20) by the reaction of MgCli with (NH4)2C03 in supersaturated solutions and factors that influence the precipitation of MgC03.3H20, such as reaction temperature, initial concentration, stirring speed, titration speed, equilibration time, have been studied by Wang et al [7]. The precipitation of Mg(OH)z by calcium hydroxide from aqueous solutions was studied by Baird et al. [8]. Stratful et al. focused on conditions influencing the precipitation of magnesium ammonium phosphate from wastewaters [9]. 1031"

Jan 1, 2011

Sm-Co alloy is a kind of magnetic material with high power and has been applied in modern industry widely. In this study, the wet chemical co-precipitation was developed for synthesis of the Sm-Co alloy oxide precursor. The thermodynamic analysis of the studied system was done to clarify the solution behavior theoretically based on the thermodynamic equilibrium and simultaneous equilibrium. Then, the experiments were done to address the various effects on the wet chemical process, including solution pH, reactant concentration, dispersant, reaction temperature and time, etc. It is found that by precise control of the process, the Sm-Co alloy oxide precursor was synthesized with fine crystallization and special size & size distribution.

Jan 1, 2005

By Zenjiro Asaki

The copper concentrate particles dissolve quickly into the molten matte in the smelting furnace of Mitsubishi Process, which indicates that the sulfide smelting is essentially a gas/liquid reaction. In this paper, theoretical calculation has been made on the rate of oxidation of FeS component in the matte to form FeO by rising gas bubbles using the penetration theory. The results showed that all the oxygen in the bubble of 1.2 cm in diameter, which is the maximum stable diameter, is consumed in 3 ms. This time required is sufficiently short, and it results in the actual operation of smelting furnace of 1100% oxygen-efficiency. These calculations indicate that most smelting reactions are completed just under the lance, except slag formation.

Jan 1, 2002

By M. Nilmani, H. Pham

"A mathematical model was developed for the dissolution of particles in gas-stirred liquid baths, linking the hydrodynamic flow field of the bath, the average particle trajectory and liquid-side mass transfer controlled dissolution kinetics. The model was validated by comparison with experimental data for the dissolution rates of urea particles in gas-stirred aqueous CaCl2 solutions measured during this study. The dissolution rates of urea. particles were measured using an image analysis system.The effects of operating conditions on the dissolution rates of urea particles were investigated. It was found that the key operating parameters influencing the utilisation efficiency of particles were the gas flowrate, particle diameter and lance submergence. An optimisation of the operating conditions for the model urea-aqueous CaCl2 system indicated that the utilisation efficiency increased with decreasing gas flowrate and decreasing particle size for a given lance submergence.IntroductionThe utilisation solid reagents in molten baths varies from one process to another, depending upon the rates and mechanisms of the reactions between the particles and melts, as well as the trajectory and residence time of the particles in the melts. Previous studies have not attempted to predict the utilisation efficiency of injected solids by coupling the motion of the particle with its dissolution rate. Instead, the particles have usually been assumed to remain suspended in the bath until completely dissolved, and the mass transfer coefficients were based on the average specific mechanical energy dissipation rates in the bath. Investigations of this nature relevant to the present study have been undertaken by Apelian et al. [1], Brucato et al. [2] and Langberg and Nilmani[3]. The objective of the present study was to develop a mathematical model, incorporating both the reaction kinetics between the particles and liquid and the particle motion simultaneously, to predict the dissolution rates and times of the particles. The mathematical model was validated by comparison with experimental dissolution rates of a cold model analogue system measured using an image analysis technique, and then applied to optimise the operating conditions in the model system."

Jan 1, 1996

By Zhongming Ren

"A new process of near net shape continuous casting of metal pipe has been put out. The specialty of the process is that no inner core is used. The principle of the process has been presented, and the effect of several factors on the thickness of the pipe has been investigated experimentally and numerically. It is shown that the temperature and the level of the molten metal, cooling intensity of the mold, and the velocity of casting influenced the thickness of the pipe apparently. In order to improve evenness of the thickness of the pipe, the mold was dedicatedly designed, and special methods were taken. By this process, a metallic material like ""bamboo"" was fabricated.IntroductionMetal pipe is a widely used material. Up to now, many processes have been put out to produce the pipe. However, the processes are usually expensive and inefficient. For instance, the welding pipe, which is most widely used, is produced through continuous casting of slab, rolling of the slab into sheet, and welding, with several times of heating and processing. Continuous casting of pipe can not produce small diameter of pipe, which is mostly needed, due to the inner core. Even though. OCC process is novel in fabricating the pipe with small diameter, it is inefficient. In this paper, the no-inner core continuous casting of pipe was proposed. With this process, pipe with small diameter can be produced efficiently. The influence of several parameters on the thickness and evenness of piper wall. With this process, a ""bamboolike"" pipe was fabricated.ExperimentThe experimental apparatus is shown in Fig. I. It is composed of mold, furnace, melt level adjuster, and dummy pipe. In the process, the level of the melt was adjusted at a proper position, then the mold along with the dummy pipe was inserted into the melt in a certain depth. The melt in the mold began solidifying, forming a solid shell. After that, the dummy pipe was pulled upward in a certain speed, drawing the solid shell out of the mold. Thus, a pipe was continuously cast."

Jan 1, 2000

By A. V. Tarasov, V. M. Paretsky

"A mathematical model of the low-temperature (soft) nickel oxide reduction (SNOR) in a tubular kiln has been developed including an equation describing changes in the nickel oxide content of the solid material along the length of the kiln; an equation describing the changes in the content of reagents ensuring nickel reduction (i.e., hydrogen and carbon monoxide) in the gas phase along the kiln length; as well as the temperature along the kiln length. The kinetic relationships used for the development of the model had been determined based on experiments conducted specially for this purpose. Model investigations were conducted to determine the distribution of such parameters along the length of the kiln as the contents of metals oxides in the solids, partial pressure of hydrogen and carbon monoxide, variations of the temperature depending on the SNOR process conditions, including the kiln rotation speed. Based on the data obtained, a simplified regression model of the reducing roasting process was developed.IntroductionAt the SeveroNickel complex (Russia) a technology has been developed and is being introduced on a commercial scale for low-temperature (soft) nickel oxide reduction (SNOR) in tubular kilns.The SNOR process has a number of advantages, the main of which are the higher degree of metallization and higher chemical activity of reduced nickel oxide attributable to the lower fusion of the surface of the grains of reduced material due to lower process temperature (800-1000°C) and improved reducing ability of the gaseous phase. However, the fact that the process is conducted in a gaseous phase sets higher requirements to the consistency of its composition necessitating careful continuous monitoring and control of the main process parameters."

Jan 1, 2001

By F. Leclerc, V. Rebeyrolle, M. Revil-Baudard, A. Jardy, M. Založnik, H. Combeau

"Since the quality of Vacuum Arc Remelted ingots is linked to their chemical homogeneity and metallurgical structure, a modeling study of the solidification during VAR has been undertaken. It is based on the solution of the coupled transient heat, momentum and solute transport equations during the remelting of a cylindrical ingot. Solidification mechanisms implemented in the model include a full coupling between energy and solute transport in the mushy zone, and accounting for nucleation and finite diffusion of solutes at the microscopic scale, in both solid and liquid phases. This modeling can be applied to actual multi-component alloys. In this paper, the macrosegregation in Zircaloy 4 ingots is investigated. To validate the model, one single melt of a homogeneous electrode has been specifically performed. The comparison between the predicted macrosegregation and the experimental results shows the importance of accounting for solutal convection to forecast properly the macrosegregation in remelted ingots.IntroductionVacuum Arc Remelting of zirconium alloy ingots is a key step in the manufacturing process of fuel assembly components in nuclear reactors. The control of the chemical homogeneity is indeed fundamental to ensure the quality and the in-reactor performance of the final products. Despite the use of electromagnetic stirring to homogenize the liquid melt composition, chemical heterogeneities develop in the mushy zone during the solidification stage. One of the main challenges for zirconium producers, as well as titanium producers, is to master the VAR process in order to control the macrosegregation in remelted ingots. Macrosegregation results from the association of microsegregation and transport phenomena. The latter are primarily due to the flow in the liquid and mushy parts. It is now well established [1-4] that the hydrodynamics of the melt pool in a VAR ingot depends on the combined action of the followings: thermal and solutal buoyancy, self-induced electromagnetic force and the periodic centrifugal force caused by the angular movement generated by the stirring. However, for zirconium alloy ingots, the effects of thermal and solutal buoyancy forces on macrosegregation through their influence on the flow in the mushy zone have not been clearly identified."

Jan 1, 2012

By Tsisana Gagnidze

A processing of technogenous wastes, which involve a gold-containing sulphide minerals, is a potential source to supplement the gold reserves. Hence, searching of ecologically safe and economically reasonable methods for processing of gold-containing technogenous wastes is a topical problem. To increase a parameters of gold extraction and to simplify a technology of the processing of above-mentioned wastes of sulphide minerals, an investigations have been carried out in the direction of the use of the method of electrochemical leaching without any preliminary processing of the mineral. It was established experimentally that an introduction of nitrogen containing organic additive into chloride solution favours to reduce a Red/Ox potential of the solution from 0,8÷1,2 V to 0,35÷0,5V, which permits to conduct the process of direct electrochemical leaching at ?soft? oxidation regimes at temperatures 20-300C C without an environmental contamination by molecular chlorine and with a high degree of a gold extraction up to 80-90%.

Jan 1, 2008

By Jenq-Gong Duh, Jyh-Wei Lee

"Hard chromizing process is a method for developing a surface modified coating providing wear, corrosion resistance and high temperature surface protection. Two carbon steels with 0.45 wt% and 0.95 wt% carbon contents, respectively, were chromized with pack cementation process at 950'C for 4 and 9 hours, respectively. The phase transformation and microstructure phenomena of chromized coating layer and matrix of two steels were studied with X-ray diffractometer and electron probe microanalyzer. (Cr,Fe)23C6 and (Cr,Fe)7C3 carbides and (Cr,Fe)2N1-x nitride phases were observed on the chromized surfaces. The thickness of chromized layers obeyed the parabolic rate law. The mechanism and diffusional kinetics of the chromizing process were proposed. The diffusivity of chromium in the (Cr,Fe)7C3 carbide phase was calculated using the moving boundary method.IntroductionChromizing process is one of the surface treatment technologies that can produce a chromium contained surface layer with sufficient corrosion and wear resistance on the steel matrix [1-7]. The relatively low cost and no ""line-of-sight"" restrictions are main advantages of chromizing. Adequate bonding strength of these coatings to the substrate was reported [7]. Chromizing process can be classified into soft chromizing and hard chromizing [2]. Soft chromizing is applied to steels containing less than 0.1wt% carbon through which chromium will be diffused. High temperature oxidation resistance improvement is the main purpose of soft chromizing process. On the contrary, the hard chromizing can be applied to steel containing more than 0.3wt% carbon, and very hard chromium nitride and carbide layers will be formed on the surface, which are very resistant to wear, corrosion and temperature [5-7]. In the previous studies on the Fe-Mn-Al-Cr alloy [5,7] and carbon steels [6], the thickness (X) of chromizing layers was analyzed and found the parabolic rate Jaw prevailed:"

Jan 1, 2004

By N. Kanari

Reactivity of MgO towards C12+air, C12+N2 and C12+CO gas mixtures was studied up to 1000 °C. Carbochlorination of MgO occurs at temperatures lower than that of its oxychlorination. Effects of gas flow rate, temperature and partial pressure of the carbochlorinating gas mixture on the reaction rate were investigated. The apparent activation energy of MgO carbochlorination is 49 kJ1 mol between 425°C and 600°C. At 550 °C, the apparent reaction orders with respect to C12+CO, C12 and CO, are 2.37, 1.47 and 0.89, respectively. At this temperature, the maximum reaction rate was obtained using a C12+CO gas mixture having a Cl2lCO molar ratio equal to about 0.6.

Jan 1, 1998

By V. M. Lsoitko

Statistical methods of technological mineralogy are used to model processing flowsheets in order to improve ore dressing efficiencies. The procedure involves determining geological and mineralogical characteristics of ores, classifying ore types and metallurgical procedures, and developing computer programs to interpret essential mineralogical parameters from on-stream analysis data. The on-stream analysis data include magnetism, radioactivity, luminescence and assays. The data are interpreted by computer and appropriate adjustments are made automatically in the plant.

Jan 1, 1989

By Akira Yazawa

In the field of pyrometallurgy, the equilibrium evaluation has recently become easy by use of thermodynamic software, but it is strongly desired to estimate the amounts of non-equilibrium minor components to simulate practical processes. However, simple physico-chemical technique can not be applied to evaluate practical non-equilibrium components for many reasons. As an engineering solution for postulated equilibrium system, the activity coefficient is modified and introduced as the simulation parameter referred to as the "adjustment coefficient." This modified thermodynamic calculations were adopted to various sulfide roasting processes where many solid phases are participating and the system is not necessarily in equilibrium. Successful simulation was realized by assigning suitable adjustment coefficients for minor components which form a pseudo solid solution in the calcine. Some examples from sulfation roasting and dearsenizing roasting were discussed. In the smelting system, the loss of copper in slag is caused by equilibrium and non- equilibrium reasons, that is, chemical dissolution and entrainment of copper in slag. The total copper content of slag was simulated by use of the adjustment coefficient for entrained copper.

Jan 1, 1998

By F. A. Myzenkov

The technology developed by the authors uses new methods for raw material smelting in electric furnaces, a new autogenous method and apparatus for subliming smelting for antimony trioxide production and separation of antimony and gold. Concentrate produced from the ore deposits in Yakutia has the following average contents of main constituents, % by weight: 29.4 Sb, 1.2 Fe, 13.1 S, 40.0 SiO2, 0.2 As, 2.6 CaO and 45 g/t of Au. Unlike the technology used abroad a new autogenous method makes it possible to increase considerably specific capacity and reduce gold losses with antimony trioxide by several times. At the same time mineralogical composition of trioxide has improved considerably ? it has mainly a cubic base with prevalence of senarmontite. The content of a main component (Sb2O3) in the final product has increased from 99.0% up to 99.6% which means better quality and makes it suitable for use in special technologies. Despite a lower antimony content of the concentrate (29.4% as compared with over 33% as common in the world practice), an antimony recovery of 85.3% into a commercial-grade product has been achieved, as well as a gold recovery of 96.65% into a gold-antimony alloy. The technology for processing gold-antimony materials developed and introduced at the Ryaztsvetmet plant is unique in the world with respect to gold recoveries.

Jan 1, 2006

By Han-Tao Hu

Keywords: RH refining process, flow of molten steel, two-phase flow, gas holdup, circulation rate, mathematical modeling A three-dimensional mathematical model for the flow of the molten steel in the whole degasser during the RH refining process has been proposed and developed with considering the physical characteristics of the process, particularly the behaviors of gas-liquid two-phase flow in the up-snorkel and the momentum exchange between the two phases. The fluid flow fields and the gas holdups of liquid phases and others respectively in a 90 t RH degasser and its water model unit with a 1/5 linear scale have been computed using this model. The results showed that the flow pattern of molten steel in the whole RH degasser could be well modeled by the model. The liquid can be fully mixed during the refining process except the area close to the free surface of liquid and zone between the two snorkels in the ladle, but there is a boundary layer between the descending liquid stream from the down-snorkel and its surrounding liquid, which is a typical liquid-liquid two phase flow, and the molten steel in the ladle is not in a perfect mixing state. The lifting gas blown is rising mostly near the up-snorkel wall, which is more obvious under the conditions of a practical RH degasser, and the flow pattern of the bubbles and liquid in the up-snorkel is closer to an annular flow. The calculated circulation rates for the model unit at different lifting gas rates are in good agreement with the determined values.

Jan 1, 2005

By Jesse White, Arlin Olson

"An Engineering Scale Technology Demonstration (ESTD) unit utilizing the THOR fluidized bed steam reforming technology was built and operated by Hazen Research, Inc. for the purpose of denitrating and solidifying various Department of Energy (DOE) radioactive tank waste surrogates into granular products. The ESTD offered the opportunity to investigate the operational characteristics of two fluidized beds in series to test process system designs such as those for fluidization, feeding, and product collection. Operational characteristics that were evaluated included bed attrition rate, particle growth, and elutriation; and the effects that variations in process parameters (e.g., fluidizing gas flow rate, feed composition, feed injection method, and gas distributor design) had upon these characteristics were observed. Testing of the process systems on this scale allowed for design changes to be made where the cost in time and money were significantly less by comparison to those same modifications being made on the commercial scale.IntroductionFluidized bed steam reforming (FBSR) offers a moderate temperature (620-750°C) continuous method by which various liquid wastes can be processed irrespective of whether they contain organics, nitrates, sulfates/sulfides, chlorides, fluorides, volatile radionuclides or other aqueous components. The FBSR technology has exhibited the potential to process these wastes into either a carbonate or crystalline ceramic (mineral) granular product.Pilot scale testing was performed using the THOR Treatment Technologies, LLC (ITT) FBSR process, as it offered the opportunity to evaluate multiple aspects in an environment more conducive to experimentation. Process changes and system modifications could be made faster and with less cost impact as compared with changes to an assembled commercial plant. These aspects include verification of process chemistry and kinetics, evaluation of materials of construction, equipment sizing and design, and the interactions of the systems. Evaluation of process chemistry allowed for the verification of thermodynamic and kinetic models, and was used in conjunction with these models to improve the database and modeling assumptions. It also allowed for the reevaluation of data from earlier bench scale testing with the opportunity for long-term operations. These long-term effects may include the buildup of one or more elements that results in the formation of eutectics leading to the destabilization of a fluidized bed, or the shift in particle size as a result of attrition or agglomeration. The pilot plant also provided an environment to evaluate materials of construction."

Jan 1, 2014

By Valery Kaplan

Sulfur emission in the form of SO2 in flue gases is one of the most serious atmospheric pollutants associated with coal combustion and non-ferrous metals production. The carbonate eutectic method for removing SO2 from flue gases at 723–923 K was initially proposed in the 1970s but despite its great efficiency (SO2 concentration in the flue gas after purification reached 0.003 volume %), it could not be implemented by industry due to the complexity of the carbonate melt regeneration stage. Earlier we proposed a method suited to coal-firing power stations where the melt was regenerated using CO as a reducing agent. However, most metallurgical plants do not use coal and therefore lack a large source of CO. Here we propose a method for removing sulfur from the carbonate eutectic melt by purging it with natural gas or a natural gas/air mixture, which are available in the vast majority of metallurgical plants. This reaction leads to the reduction of sulfate to H2S gas that leaves the melt. The experiments we conducted show that nearly complete sulfur removal from the melt is possible at 823 K and that the reaction rate is sufficiently high for a large scale process. One can foresee that this carbonate melt-based SO2 removal technique may become a practical and economically attractive method for limiting sulfur emission to the atmosphere from non-ferrous metallurgical processing plants.

The oxidation of zinc vapour plays a very important part in the operation of the Imperial Smelting Process. The kinetics of the reoxidation of zinc vapour by carbon dioxide and water vapour onto quartz and zinc oxide substrates is qualitatively understood and this pertains to the conditions found as the gases are being transferred from the furnace to the splash condenser. However, re-oxidation also occurs in the shaft of the furnace where the solid substrates are sinter and metallurgical coke. It was found that there was a threefold increase in the rate of oxidation on sinter, compared to quartz and a 30 to 300 increase in rate on the coke. This was attributed to the high surface area offered by these materials.

Jan 1, 2003

The oxidation of zinc vapour plays a very important part in the operation of the Imperial Smelting Process. The kinetics of the reoxidation of zinc vapour by carbon dioxide and water vapour onto quartz and zinc oxide substrates is qualitatively understood and this pertains to the conditions found as the gases are being transferred from the furnace to the splash condenser. However, re-oxidation also occurs in the shaft of the furnace where the solid substrates are sinter and metallurgical coke. It was found that there was a threefold increase in the rate of oxidation on sinter, compared to quartz and a 30 to 300 increase in rate on the coke. This was attributed to the high surface area offered by these materials.

Jan 1, 2003

By S. R. Reddy, R. G. Reddy

"The Margules equation is used for interpreting excess Gibbs energy of several ternary systems. In the present study activity coefficient of a dilute solute, 2, in a binary solvent 1-3 was derived. The derived expression is used to interpret logarithmic activity coefficient of oxygen and sulfur in several metallic systems. Self interaction parameter of the solute is derived from the partial function of solute using constant compositional path. An expression for logarithmic activity coefficient and self - interaction parameter of solute is also derived using Maclaurin infinite series. The derived equation is based on Maclaurin infinite series used successfully to deduce thermodynamics of self interaction of oxygen as a interstitial atom in two metallic systems. The predicted thermodynamic parameters values using Maclaurin infinite series and Margules equations, are in excellent agreement with the experimental data and also our predictions are far more accurate than the predictions made by other models.1 IntroductionIn most of the pyrometallurgical high temperatures processes, interactions of solutes such as oxygen, nitrogen and sulfur, with the solvent atoms are most important during refining processes. There are numerous theories are developed [1-25] to interpret the thermodynamics of solutes in multicomponent alloy systems. Which are mainly developed using statistical or Quasichemical equations.Wagner [4] developed one energy parameter ideal solvent model based on activity coefficient of solutes compositional dependency. He used one energy interaction term which is not able to account for interaction energy parameters for the same solute concentration at different solvent compositions and also it is ineffective model to predict for strong interacting systems."

Jan 1, 1996