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By Guo Xueyi

The reaction mechanism for the manganese dioxide reductive dissolution in acidic chloride media in the presence of ferrous/ferric ions are based on theoretical delineation and dual cell experiments. In terms of the Buttler-Volmer equation and chemical kinetic principles, a electrochemical kinetic equation was deduced, which successfully provided a theoretical basis for describing the role of Cl-, Fe2+, Fe3+ and H+ in solution, as well as their interrelationship in manganese dioxide reductive dissolution. Dual cell experimental studies indicate that the increases of Cl- and Fe2 in solution are helpful to accelerate the couple process; while, Fe3and Mn2+ hinder the coupled reaction to some degree. Higher acidity in solution is beneficial to the dissolution of MnO2. All the dual cell experimental results are consistent with the theoretical deduction. This study will be useful to understand the mechanism for the leaching of manganese nodules from the deep ocean, as well as the leaching of manganese dioxide ore from land.

Jan 1, 2003

By Xiaobing Yang, Animesh Jha, Greg Doughty

"Successful use of inert anodes should reduce the CO2 footprint in aluminum production. The search for a “holy grail” inert anode for metal electro-winning from constituent oxides using molten salt bath as an electrolytic medium is continuing. In this article we demonstrate the engineering approaches for the fabrication of intermetallic anodes, based on a quaternary Al-Ti-Cu-M (M:Ni, Fe) system for primary aluminium production. In particular, we examine the microstructural and electrochemical properties of alloys, based on the quaternary compositions. We explain the aspects of phase stability under anodic potential, which leads to the loss of anodic materials in the temperature range of 850-1050oC. The results are analysed in the context of oxidation reaction and formation of oxide layers which readily dissolve in the cryolite melt and prevent passivation. The paper also describes the conditions under which the reduction of aluminium at the graphite cathode occurs which also strongly depends on the molten salt chemistry for the nucleation of molten aluminium at the cathode.1. IntroductionOxygen-evolving inert anodes are an alternative to the conventional consumable carbon anodes for the production of primary aluminium. In this paper the materials selection criteria chosen for the engineering of anode is based on the understanding of the thermodynamic stabilities of aluminide intermetallic phases, some of which are formed and remained stable in fluoride melts. For example, the formation Al3Ti dispersed in aluminium metal via molten-fluoride flux reaction is well known in the context of aluminium casting and grain refining [1-3]. It is for this reason in our research we concentrated on the engineering of stable intermetallic phase mixture in the Al-Ti-Cu ternary system, shown in Figure 1 [4]. In this figure two compositions in the Al3-0.5zTi1-0.5zCuz family are shown with the substitution of 7 atomic % and 11 atomic % copper. However initial investigations showed that these two compositions were unsuitable due to the formation of low-temperature liquid (~540oC) and intermetallic phase, Al2Cu along the Al-Cu binary edge during solidification. The Al2Cu phase segregated along the boundaries of Al3Ti and Al5Ti2Cu, and dissolved away when electrolysis was carried out using these anodes above 800oC. The presence of consequential porosity in the anode material increased the corrosion of the alloy through local heating due to high current density at 0.8 A cm-2. The early tests were carried out with cryolite melts, shown in Figure 2, having 3 weight percent of Al2O3 in the bath at 850oC."

Jan 1, 2010

By Norihiko Fukatsu, Takashi Iwamoto, Noriaki Kurita, Koji Katahira, Kunihiro Koide, Teruo Ohashi

"The galvanic cell-type hydrogen sensor employing CaZro.9Ino.t03-a. as the solid electrolyte was designed for the measurement of hydrogen activities in molten copper under industrial .conditions. The sensor probe consists of the cap-shaped solid electrolyte with porous platinum electrode on the inside and alumina refractory tube. The gas mixture of the composition 4%H2-0.5%02-Ar was made to flow on the inside electrode. The hydrogen sensor probe was inserted directly into molten copper and the melt was used as the outer electrode. The effect of oxygen activity gradient to EMF was eliminated theoretically by measuring the oxygen activity in the melt simultaneously with an oxygen sensor. The high stability of output and excellent response to the change of hydrogen activity were obtained over the wide range of industrial copper melting conditions.IntroductionIn the metal casting process, hydrogen easily dissolves in molten metals from water vapor in the surrounding atmosphere. Owing to the large difference in hydrogen solubility between liquid and solid metal, dissolved hydrogen becomes a cause of the defects of blowholes in castings or ingots. It is necessary to control the hydrogen content in the molten metals [l]. Using proton-conducting ceramics as a solid electrolyte, high temperature-type hydrogen sensor can be constructed [2]. SrCe03- and BaCe03-based perovskite-type oxides exhibit appreciable proton conduction under hydrogen containing atmosphere at high temperature [3-5]. A hydrogen sensor for molten aluminum using CaZro.91no.103-a. has been developed and widely used in the ·process control in the aluminum melting industry [6,7]. The same type of hydrogen sensor has also been expected in the copper melting industry. .. However, CaZro.91no.103-a shows ·not only proton but also oxide ion conduction in the high temperature and at low oxygen activies like the copper melting· conditions. Then we studied the oxide ion conduction in CaZro.91no.103-a. iit · detail [8]. From the consideration on the EMF of the galvanic cell employing this material as electrolyte, it was shown that the unknown hydrogen activity may be precisely determined from cell potential which is corrected for the effect of oxygen potential gradient And the hydrogen sensor based in this principle was constructed and tested in laboratory-scale [9,10]. We repeated the similar tests in factory-scale and developed the sensor system for practical uses [11, 12]. In this report, the structure and system of the hydrogen sensor for molten copper will be introduced first. The reliability of the sensor will then be demonstrated from the results of experiments for sensor probes carried out in TYK's laboratory."

Jan 1, 2000

By Tsembel Darjaa, Toru H. Okabe, Yoshiaki Umetsu

"With the purpose of extracting molybdenum and rhenium from molybdenum sulfide concentrate; .electrolysis of slurry, solvent extraction and ·precipitation operations were carried out. The slurry of the concentrate in 10 mass% NaCl aqueous solution was continuously circulated into a vertical type 10 stack bipolar electrolytic cell consisted of carbon electrode disks, and, the concentrate was dissolved by electrochemically generated oxidizers at 313 K. The current efficiency for molybdenum dissolution was 73 % after 10 hours electrolysis, and the leach solution was found to contain 0.2 mol/l of molybdenum and 4x10-5 mol/l rhenium. This result shows the dissolution is more than 8 times faster than that obtained using a single cell. The leach solution from electro-oxidation was then subjected to a solvent extraction for rhenium which is then recovered as sulfides. After rhenium separation, molybdenum was precipitated by pH adjustment, and solid MoO3 (H2O)x crystals, free of sulfate, were obtained from the leach solution containing large amount of so42-.IntroductionIn the past, electro-oxidation using a bipolar cell was applied for leaching molybdenite concentrate and ores at U. S. Bureau of Mines [1-3] and also at Bhabha Atomic Research Center [4]. In· these previous studies, Moebious type bipolar cells, in which electrode plates were vertically inserted into the free surface of the electrolyte, were employed and its effectiveness was demonstrated.Recently, the present authors studied on leaching of Mongolian molybdenite concentrate, and the effectiveness of leaching of the concentrate by electro-oxidation in alkaline and acidic NaCl solutions was demonstrated [5]. The leaching reaction during the process can be explained by the 18 electron transfer reaction of molybdenite (MoS2) with the oxidizers produced in-situ by electrolysis of NaCl aqueous solution. Further investigation was made with respect to various process parameters for electrooxidation such as pH, pulp density and temperature of the slurry, and the dissolution behavior of minor elements such as iron, copper, and rhenium [6]. Solubilities of molybdenum in the leach solution at, various temperatures and pH .was · studied, and feasibility of molybdenum recovery by hydrolysis of molybdenum species was demonstrated. By adjusting the pH of the leach solution, molybdenum oxides or hydroxides free from sulfate were successfully obtained from the solution containing large amount of sulfate ion. Rhenium present in the concentrate at a level of several tens of mass ppm was found to dissolve into the leach solution, and co-precipitate with the molybdenum compounds. Rhenium in the leach solutions, therefore, has to be recovered before precipitation of molybdenum, otherwise it is lost in the precipitate."

Jan 1, 2000

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

By Olga K. Karakasi, Angeliki Moutsatsou, Ioanna Kavallari

"The present study focuses on the amelioration of the behaviour of high calcium fly ash (HCFA), investigating its application in a new environmental field: oil spill clean up. High calcium fly ash is a by-product of electric power plants, produced annually in large quantities, whose greater amount is landfilled. Some of its properties, such as its chemical and mineralogical composition, its fine particle size, its porosity, floating ability and hydrophobic character make it an attractive material for this purpose. Researches showed that when added to an oil spill, it forms a semi-solid phase, which allows the quite total removal of the oil, but it is not stably retained on the surface. In order to ameliorate its floating ability, the decrease in its specific gravity by mixing with a lighter material is investigated. In the present study the mixing with two materials, already used in oil spill clean up, sawdust and a polymer, has been examined. Addition of 15-25% w/w sawdust to HCFA results in a material with better performance than HCFA or sawdust alone: it has a satisfactory floating ability and allows total removal of oil. Addition of the polymer, however, has resulted in no significant amelioration of the oil sorption behaviour of HCFA, probably because no affinity between HCFA and polymer has been achieved.IntroductionCoal fly ash is a by-product of coal combustion in electric power plants, produced worldwide in huge quantities, approximately 500 million tones annually. High calcium fly ash (HCFA) is classified to class C presenting a (Al2O3 + SiO2 + Fe2O3) > 50%. The production of lignite fly ash in Greece comes up to 13 million tones annually, of which only 12% is used in construction applications, the other being landfilled [5, 6].Besides its limited application worldwide as a construction material, research is focusing on the development of new environmental applications, such as waste stabilisation and solidification, soil and water environmental improvement [9, 12]. For the application of fly ash in further environmental fields several chemical modifications have been applied, in order to improve its properties. Extensive research has been focused on the conversion of both coal and lignite fly ash to zeolite and its further application in environmental field, such as the uptake of inorganic (heavy metals and ammonium [8, 11]) or even organic compounds (methylene blue [15]) from waste water streams, or the use as molecular sieves, to adsorb water molecules, SO2 and NH3 from gas streams, due to the high cation exchange capacity and porosity of the produced zeolithic material. Furthermore, lignite fly ash has been combined with sodium silicate solution, prepared by treatment of rice husk ash, and tetrapropylammonium bromide, to synthesise hydrophobic zeolite ZSM-5 [4]."

Jan 1, 2008

By Thomas Schuman, Jaan Kers, Lucas N. W. Damoah, Xiangjun Zuo, Lifeng Zhang

"Rapid technological innovation has propelled the use of electronic equipment leading to the generation of more and more waste electrical and electronic equipments (WEEE). Printed wiring board (PWB) is a component made of one or more layers of insulating material with electrical conductors. To investigate an environmentally friendly process to recycle PWBs, PWB samples with and without additives were pyrolyzed. Liquid, gas and solid products were achieved with different conversion fraction. Analysis of the exhaust gases from the experiments using GC-MS and MS showed that without CaCO3 additives poisonous gases such as C6H6 and HBr were produced which were adequately controlled if CaCO3 was added.IntroductionPyrolysis is one of the best methods for treating complex mixtures of waste polymers and to recover the material and energy content. The process consists of thermal decomposition at moderate temperatures in total absence or small amount of oxygen in which the structures of polymers break down into smaller intermediate products "". The decomposition temperature of a substance is the temperature at which the substance breaks up into smaller substances or into its constituent atoms 2). Thermal treatment of PWBs were reported using DC Arc Plasma furnace 3), and fixed bed reactor 4). One drawback in dealing with thermal treatment of PWB scraps is the likely production of super-toxic halogenated dibenzodioxins and dibenzofurans from the bromine containing structures. Pyrolysis of organic materials contained in waste PWBs leads to the formation of gases, oils, and chars which can be used as chemical feedstock or fuels ""'. Dehalogenation of the pyrolysis product of electronic scraps is essential to make it commercially acceptable. It would be obviously the most advantageous solution as pyrolysis and dehalogenation are carried out simultaneously. Reported pyrolysis investigations are at experimental stage and have been carried out in vacuum, molten salt, fluidized bed, rotary kiln, entrained, stationary, and moving bed reactors 7). Comparing to the incineration and combustion of PWBs, the pyrolysis process has several characteristics: 8'"">) 1). Converting the organic solid substance into fuel gas, fuel oil and carbon-black as storage energy; 2) Emitting toxic substances such as sulfur, bromine and heavy metals in wastes; and 3) Keeping metals from being oxidized. Although many researches into the pyrolysis of PWB wastes have been reported, most of the works have been carried out using analytical pyrolysis techniques or very small batch reactors ""~'5). Also, most of the works for the pyrolysis of PWBs haves concentrated on the composition of the organic products, particularly the brominated organics. The current study is to investigate the pyrolysis of PWB powders in a small TG-DTA scale and a 50-gram tube furnace scale."

Jan 1, 2011

By Matthew Tunnicliffe, Akram Alfantazi, Paul Nesbitt, Farzad Mohammadi

"Lead and its alloys are proper candidates for anodes in electrowinning processes mainly because they are insoluble in the leach solutions and relatively cheap. However, the annual cost of corrosion problems associated with these anodes is millions of dollars. In this study lead-silver and lead-calcium anodes were tested under typical nickel electrowinning conditions and the effect of chloride on the corrosion performance of the anode materials was investigated. Corrosion rates of the anodes were calculated using the discharge plateau (reduction of lead dioxide to lead sulfate) after galvanostatic experiments. It was found that lead calcium anodes have the highest corrosion rate both in the presence and absence of chloride. Surface morphology of the electrodes was studied using SEM and the corrosion products were characterized using XRD.IntroductionLead (Pb) is usually the preferred material for commercial anodes since it is insoluble in the leach solution and the costs are manageable. One advantage of using an insoluble material as an anode is the higher purity of the cathodic deposits and better quality of the end product. During nickel electrowinning, metallic nickel is deposited on the cathode while oxygen evolution reaction (OER) takes place on the anode. In practice, relatively high potentials are necessary for the reaction to proceed at the desired rate because of the high overpotential of OER on lead. Lead anodes get oxidized in typical electrowinning conditions and usually have two to three years of lifetime. Although the price of each anode is insignificant, the overall cost of corrosion of these anodes is considerable, which is due to the large number of anodes used in a plant, typically two to three thousand. Therefore, corrosion is a significant problem associated with lead anodes in commercial nickel electrowinning plants and industries show interest in addressing this problem. Corrosion of lead electrodes in acidic environments has been previously the subject of many research studies [I-7]. It has been reported that, during the anodic polarization of lead, several phases may be present on the surface, depending on the potential range that is being studied [8]. Lander showed that lead is oxidized at potentials higher than 0.252 YsHE with tetragonal lead monoxide being the main reaction product [9]. At 0.666 YsHE lead can transform to lead dioxide; however, it is not stable and transforms to lead sulfate and lead oxide. At potentials higher than 1.684 YsHE, lead dioxide is eventually a stable phase and forms a protective layer on the surface [I 0, 11]. Under conditions of a typical nickel electrowinning plant, usually a 200 A/m2 current density is passed through the electrodes."

Jan 1, 2012

By Toshiyuki Hashida, Victor M. Lopez-Hirata

"Small-punch tests and determination of fracture toughness JIC were conducted at 4 and 77 K on new cryogenic JN1, JJ1 and JK2 austenitic stainless steels, after isothermal aging. Equivalent fracture strain ?qf determined by measuring the reduction of thickness in the small-punch test specimen. A linear dependence of JIC on ?qf was found in these new materials. Regression analysis of experimental data produced the following linear relation JIC = 1304.1 ?qf + 8.09 [kJm-2]. An analysis of present work relation was pursued on the basis of material properties and evaluation method of he. Results showed that the slope value has a strong dependence on material yield strength and JIC evaluation method. This linear relation is useful for the evaluation of fracture toughness JIC, measuring the equivalent fracture strain ?qf by means of small-punch test. Thus it can be useful for assessing the degradation of fracture toughness in small areas such as, the heat-affected zone in welded components.IntroductionCryogenic structural materials for superconducting magnets of fusion nuclear reactor are required to possess a good combination of strength and toughness. The mechanical properties are required beyond the capability of conventional austenitic stainless steels [1]. New cryogenic JN1, JJ1 and JK2 austenitic stainless steels were developed by the Japan Atomic Energy Research Institute (JAERI) [1]. The structure of superconducting magnets is constructed by welding of 200 = thick plates of these steels, which are solution treated at high temperatures and then water-quenched to avoid intergranular precipitation. However, the welding process involves heating and cooling [2], which cause microstructural changes in both base metal and weld. In this heterogeneous microstructure, it is important to estimate the fracture toughness of these materials at cryogenic temperatures. Therefore, it is necessary to evaluate the effect of aging process on the fracture toughness behavior of these new steels. To determine the cryogenic fracture toughness, the elastic-plastic JIC value has been co=only used [2]; however, the specimen size is much larger than heat-affected zones in welded components. Small-punch (SP) testing method, employing miniature specimens, has permitted to evaluate the fracture toughness behavior at different temperatures in different nuclear reactor materials [3,4]. Mao et al. [5,6] and Misawa et al. [7] found a linear relation between JIC value and equivalent fracture strain ?qf, determined by SP method in non-ferrous alloys and ferritic steels at room temperature and austenitic stainless steels at 4 and 77 K, respectively. So that, this kind of correlation would be very useful to assess the fracture toughness JICe values by means of SP test in small zones of welded components."

Jan 1, 2012

By F. G. Caballero, J. L. Gonzalez-Carrasco, S. Barrius, H. Carreon, M. Lieblich

"The grit blasting is a low-cost technique successfully used to enhance mechanical fixation of the implants through increasing their roughness. As a result of the severe plastic surface deformation, it produces subsurface effects such as grain refinement, hardening and compressive residual stresses which are generally evaluated with destructive techniques. In this research work, non-contacting and contacting thermoelectric power measurements are performed in blasted 316L VM and Ti-6AI-4V specimens using Ah03 and Zr02 particles which yield a coarse and a fine rough surface, respectively. This study correlates the microstructural changes induced by the grit blasting treatment and the limitations and advantages of each of the nondestructive thermoelectric techniques based on the Seebeck effect used to evaluate these biomaterials.IntroductionIt is well known that surface properties play an important role in metallic materials used in bio-medical applications. Since the biological response is correlated directly with surface properties it is comprehensible the intense activity in superficial modification by physics or chemistry methods in this field. Grit blasting, one of the most popular surface modification of metallic biomaterials, enhances the mechanical fixation of the implant through the increase in roughness [1-3]. Roughening is developed by bombarding the surface with a high-velocity jet of ceramic particles, being the final roughness a function of the processing parameters (pressure, distance, time, ... ) and blasting particles (nature, shape, size). As the plastically deformed surface layer tries to expand relatively to the intact interior of the specimen, residual compressive stress gradients develops perpendicular to the surface at shallow depths with a maximum value at a depth in the range of 5 to 60 µm. This surface treatment also may cause subtle variations in the subsurface material properties, such as increased hardness and grain size refinement, which are consequences of the significant plastic deformation through cold work. Blasted affected zones may extend to a depth of up to about 200 µm. The subsurface hardening and the near-surface compressive stress gradient playa beneficial role by retarding fatigue crack nucleation and further growth, ultimately extending the fatigue life of the metallic part [4]. In this work, two non-destructive thermoelectric techniques (NDTT), the non-contacting and contacting thermoelectric power measurements were used to analyze the subsurface induced changes on blasted Ti-6AI-4V and 316L VM specimens using Al2O3 and Zr02 particles. Detailed information on the microstructural induced effects and subsurface mechanical properties were published elsewhere [5-8]. Here the nondestructive evaluation of the involved microstructural changes is used to assess the global subsurface damage. Advantages of using nondestructive techniques during manufacturing are envisaged."

Jan 1, 2012

By Guanghua Wen, Jian Li, Mingmei Zhu, Fei Xiong, Shengjian Cao

"Small inclusions removal from molten steel in a continuous casting tundish by gas bubbles, which were generated in the turbulent flow region by introducing inert gas, was analyzed theoretically and the inclusion-bubble adhesion and flotation process was also observed by high-speed photo-graph in water model. Results showed that small inclusions in the range of 20-50µm removal from molten steel by bubbles flotation involves three stages: contact, adhesion and flotation. The inclusion-bubble adhesion processes include two ways: inclusions adhering to the upper part of the bubble and inclusions adhering to the lower part of the bubble. As the bubble floats up, the number of inclusions adhering to the bubble are increased. The proper size of bubbles, which could enhance small inclusions removal efficiency, should be controlled in the range of 1-2mm.IntroductionReducing inclusions content in molten steel is a very important way to improve quality of steel, and one of the main tasks in steel making process.A variety of methods have been used for inclusions removal in molten steel. At present, the main approaches to remove inclusions are gas stirring, slag cleaning, filtering, centrifugal separating, and by means of ultrasonic or electromagnetic field. Among these techniques, gas stirring is the most widely and effectively method for inclusions removal. Inclusions in molten steel will be aggregated and generated to form larger size inclusions, and subsequently floated to the surface of molten steel by buoyancy; meanwhile, some inclusions will be adhered to bubbles and floated together to metal-slag interface where inclusions are absorbed by the covering slag layer. Some research work showed that flow behaviors of small bubbles are different from that of big ones [1-2], and smaller bubbles are more efficiency for fine inclusions removal in molten steel.There are many methods to generate bubbles. During steelmaking process, highly turbulent flow in the ladle shroud can split introduced inert gas into small bubbles, which enhances the removal of fine inclusions from molten steel. Turbulent flow of molten steel injected into tundish from ladle shroud has a high speed and it is a strong turbulent area in continuous casting. The gas can be introduced into the shroud below the slide gate. The high turbulence flow would break up the gas into small gas bubbles. Fine inclusions will be easily adhered to small bubbles and subsequently floated to the surface of molten steel. Generation of small bubbles in ladle shroud have been studied in some literatures [3-4]. Some research have analyzed the fine inclusions removal with injecting gas from the ladle shroud by mathematical simulation, and the results show that the refining method can obviously improve the removal efficiency of fine inclusions in tundish [5-8]."

Jan 1, 2013

By Yotamu Stephen Rainford Hara

"The study focuses on the reduction mechanisms of copper, cobalt and iron during carbothermic reduction of copper-cobalt mineral sulphide concentrates in the presence of lime, in the temperature range of 1073K and 1273K. We have used three types of mineral concentrates which were derived from froth flotation from the Copperbelt region in Zambia. The reduction mechanisms were studied using thermogravimetric analysis in which selected reactions were stopped at different times for characterising the reaction mechanism using optical microscopy, XRD and SEM-EDX analyses. Using SEM-EDX analysis, we have analysed in details the stages of metallic phase formation during reduction process. Metallic cobalt and iron were embedded into copper, thereby permitting magnetic separation of the reduced metals even though copper is diamagnetic. Methods of preferential reduction of metal values were investigated by analysing the metallic phase formation.IntroductionIn conventional smelting or converting of copper sulphide minerals, metallic copper forms by giving off S02 gas on. Although in terms of overall energy balance the selective oxidation for metal production has major advantages, the process suffers from drawbacks in smelting complex concentrates containing copper, cobalt and iron sulphides minerals and these are: (i) cobalt and iron are oxidised, and consequently cobalt is lost into the slag phase. (ii) The volume of S02 gas produced is in low concentrations, which is insufficient for extracting sulphur or manufacturing sulphuric acid. The release of dilute S02 causes serious environmental pollution. The major cause for the loss of cobalt and iron into the slag, is due to that fact that the oxides of these metals are more stable than their sulphides. Since cobalt and copper are more valuable than iron, reducing conditions are required in a separate slag treatment reactor using electric arc melting for recovering the lost metal oxides from slag. This energy-intensive step makes metal making expensive.During chemical beneficiation of mineral sulphides (Cu2S, CoS, FeS) in the presence oflime (CaO), two types of equilibrium conditions may be set up either by forming CaS under reducing conditions, or by stabilizing CaS04 under oxidising conditions [l]. By comparison in the presence of carbon, CaS and metallic phases form, enabling the recovery of metals from sulphide minerals, which have been investigated by a number of authors [2-9]. During reduction of metal sulphide in the presence of lime and with carbon, it has been proven that the overall reaction le proceeds via two main steps: [5, 8, 9] (i) the anion exchange reaction between metal sulphides (MS) and CaO as shown in equation la, followed by (ii) the reduction of metal oxide (MO) via reaction lb."

Jan 1, 2013

By Marcela Morvová, Mário Janda, Morva Imrich

"The possibilities of greenhouse gas mitigation using various methods are brought out. The special case of utilization of mixture of CO2 with other greenhouse gases in a synergetic way inside non-thermal plasma based system is described in detail.Measurements on pilot system comprising pyrolysis chamber as alternative energy system (production of hydrogen and liquid tar) were made for various biomass and waste as the input material. The exhaust from this system was treated with non-thermal plasma gap suitable for up to 650Nm3/hour of exhaust gas flow. Condensable portion of exhaust is liquefied in distillation unit; produced hydrogen is stored on-line inside nano sized carbon of our own production.The CO2 removal efficiency varies depending on exhaust composition between 45 to 98%. Other oxides as CO, NOx, SOx and several hydrocarbons and VOC are also removed. The main product connected with CO2 removal is a solid powder of proteinoid nature. There exist strong probability, that precursor of the origin of life on the Earth from primary atmosphere were formed in the similar way as it is present in the electric discharge system used. Our system is equipped with on-line as well as ex-post analysis of all forms of products. We have also developed a system for recuperation of all forms of produced heat. It is stored inside as latent heat of waxes.IntroductionNatural greenhouse effect on the Earth is caused mainly by water vapour with the average absolute concentration about 4%. Other gases able to absorb long-wave radiation and thus this causing greenhouse effect are CO2, CH4, N2O, halocarbons and as precursors ozone and NOX. Some of them we produce and introduce into atmosphere in large quantities during production of energy and in transport. This factor leads to permanent increase of average temperature of air, sea and oceans, so called global warming.Nowadays large amount of data exists showing that the temperature of Earth in the last 150 years has been continually increasing. It represents about 03°C per ten years and the most of climatologist believe, that the increased concentration of greenhouse gases in the atmosphere is responsible for this effect.The most important greenhouse gas is carbon dioxide CO2. Majority of CO2 emissions comes from electric power stations working with fossil fuels, cars and industry. Burning of fossil fuels contribute up to 80% to world wide anthropogenetic emissions of CO2."

Jan 1, 2010

By Thomas F. Hagelien, Stein Tore Johansen, Svend Graadahl

"The dross appearing at the surface of an aluminium melt consists, in addition to aluminium, of mainly oxide films but also other non metallic inclusions. The inclusion particles are often poorly wetted by the metal and accumulate at the metal surface. However, in impeller stirred reactors for melt refining stirring may be exceedingly strong and inclusions accumulated at the metal surface may be entrained into the bulk metal. Concerning inclusion removal, such effects may deteriorate the effectiveness of melt refining.In this paper we investigate the surface entrainment of buoyant particles in a water model of an impeller stirred refining reactor. Under varying operating conditions the particle concentration in the bulk liquid is measured by laser light attenuation. The observed entrainment of particles is explained theoretically and metallurgical consequences of the findings are discussed.IntroductionIn the modern cast house continuos metal refining and casting is well established. One of the most distinct advances in metal refining has been the introduction of degassers which introduce bubbles into the metal. The bubbles act to remove dissolved elements together with nonmetallic inclusions. In the most efficient degassers stirring by different kind of rotors is applied to increase mass transfer and inclusion removal. However, it has been known from experience in the cast house that for violent stirring the concentration of some types of inclusions may increase from inlet to outlet of the reactor. This phenomenon has so far been attributed to production of dross in the reactor due to oxidation of metal. Due to removal of inclusions by bubbles the dross layer inside the reactor must be expected to increase in thickness by time. The removed inclusions and produced oxides due to strong stirring is removed at regular interval by the operators of the degasser. However, a fundamental understanding of the phenomena which take place in and below the dross layer is lacking. In the present work we add buoyant particles to the surface of a refining reactor and investigate how these particles may be entrained and dispersed into the liquid depending on the flow conditions. Similar investigations for gas stirred ladles have been performed by Taniguchi et al [1] who found that below a critical gas flow rate all particles are trapped at the surface. Above the critical gas flowrate the surface velocity are sufficiently high to entrain the particles. In this situation it looks like all particles are ready for the melt and a balance between terminal velocity and turbulent dispersion determine the concentration in the liquid."

Jan 1, 1999

By Sergey Komarov, Manuela Diaz, Sano. Masamichi

"Mixing time, bubble behavior and absorption rate of gas injected into a liquid bath through rotary L-shaped lances have been studied by cold models with an effort to improve refining characteristics of metallurgical processes. Two kinds of the rotary lances were tested, namely the single-hole lance and the multi-hole lance. The effects of gas flow rate, bath depth and rotation speed were examined.It is found that when gas is injected through the rotary lances, the mixing intensity and the gas absorption rate are larger than that for the gas injection through stationary lances. The effect of rotation speed decreases as the bath depth and the gas flow rate increase.The multi-hole lance produces much smaller bubbles, which lead to an increase in the volumetric mass transfer coefficient by 3-4 times as compared with the single-hole lance. However, the effect of rotation speed is smaller for the multi-hole lance. The obtained results are explained in terms of the bubble coalescence and fragmentation, the rate of which depends on the departure bubble size and the power supplied to the liquid bath.IntroductionIn recent years, there has been a growing interest in the development of gas injector for metallurgical processes. The majority of the previous work was focused on modification to the injector design to improve mixing and to increase the of chemical reaction rate. These two goals can not be necessarily achieved by the same way. Bottom nozzles and stationary immersed top lances, which have been widely applied to steelmaking processes, are effective for the bath mixing, but have a limit to decrease in the bubble size. This results from a vigorous coalescence occurring between the bubbles when they rise in the molten bath as a bubble swarm.One of the ways to ensure the small bubble size and the effective bath stirring is the gas purging through rotary injectors. A number of studies have been undertaken to improve the refining characteristics by using rotary injectors. All of them are related to aluminum refining. The SNIF equipment (The Spinning Nozzle Inert Flotation) has significantly improved the quality of aluminum products at National Luxemburg Aluminum [1]. Rotary injectors made in the form of a disc have been applied to the Alcoa 622 [2] and the GBF processes [3]. A study of the gas injection by a rotary impeller has been carried out by C. Leroy and G. Pignacelt [4]. All researchers note the significant improvement in removal of sodium, calcium, hydrogen and non-metallic inclusion."

Jan 1, 1996

By Xuewei Lv, Maojun Zhou, Xiaobo Huang, Rende Zhang

"The characterization of the surface roughness of the mineral particles is of vital importance for the studies of the mineral processing. In this study, an evaluation of the roughness of the iron ore particles, with the measurements of size distribution and the measurements of specific surface area with the liquid nitrogen absorption, was developed. The main theory of this method is the fact that the roughness of the particle influences the specific surface area apparently. The specific surface area of the particles can be measured with the laser diffraction method and the liquid nitrogen absorption method. The influence of the surface roughness of the particle can be measured with the nitrogen absorption and cannot be measured with the laser diffraction. Therefore, the roughness can be got by comparing the specific surface area with two measurement methods.IntroductionThe characterization of the surface roughness of the mineral particles is of vital importance for the studies of the mineral processing. There are three main methods for measuring the size distribution of mineral particles: sieving, laser diffraction, and sedimentationl). Many techniques involve sedimentation such as the Horiba2, 3) and the Cyclo-sizer1). In the mineral industry, size distribution is usually determined by sieving because it can be carried out accurately for all particle sizes larger than 45 . The preferred method to obtain the size distribution of finer particles is laser diffractometry. The technique has several advantages: it produces measurements in a few minutes with considerably less labor compared with the cyclo-sizer and for a range of sizes considerably wider in comparison with the sedigraph4). The equivalent-sphere size distribution reported by laser diffractometry is valid for metallurgical calculations and can be routinely used in mineral processing plants. The surface area of the particles can be measured by the BET method of nitrogen adsorption, or it can be calculated from the size distribution. However, the latter calculation requires the size distribution to be accurately known across the whole size range, and assumptions have to be made about the shapes and surface roughness of the particles and presence or absence of pores (see below). The BET method is based on the physical adsorption of gas over the whole exposed surface area and measures the surface area stemming from the roughness and open pores on the surface of the particle5). The calculation of the surface area from the size distribution is usually based on the assumption that all the particles are smooth spheres, without considering the shape and/or roughness of the particles. Determining the surface roughness of the particle with these methods, is the objective of this study."

Jan 1, 2012

By Tamas Kekesi

Anion exchange in HCl media is considered an efficient alternative to the combination of the conventional purification methods. Anion-exchange distribution functions have been determined for cobalt and the main impurity elements by the technique of batch equilibration. Results were confirmed by spectrophotometric investigations and elution tests. Based on the new and the available distribution functions, combined with the assessment of thermodynamic stability, a procedure of anion exchange separation has been devised to eliminate virtually all the impurities from the cobalt-chloride solution. Separation of copper has been enhanced by the introduction of a preliminary step under reduced conditions. The rest of the impurities are eliminated in a second anion-exchange step applying rinsing and elution stages under oxidized conditions. The optimum parameters of the procedure have been determined according to performance characteristics (purification ratios, yields and volume efficiencies) derived from the analysis of elution curves obtained with laboratory scale ion-exchange columns. Special computer programs have been developed to facilitate thermodynamic simulation, analytical correction and data processing.

Jan 1, 2003

By Lionel Ryan

In 1996, the Dominican Republic operation of Falconbridge (Falcondo) developed a 5-year Process Control Plan in conjunction with the corporate Process Control group located in Sudbury, Ontario, Canada. This plan was further refined into an analysis of the areas of the highest potential economic return for the company with the reduction shaft furnace operation being the most promising. Historically, the reduction plant, which comprises 12 shaft furnaces, has been the bottleneck of ferronickel production. Since 1996 there has been a history of control development, and the current status is that all 12 furnaces are using advanced model-based multi- variable predictive control. The combination of advanced process control (APC), improved control system performance and improved process information management has resulted in an increased throughput of 6% per shaft furnace and a reduction in operating costs of 4.5 US cent/lb of Ni. This paper reviews some of the major milestones that have been achieved in this development Keywords: Advanced Process Control; Model Based Predictive Control; Connoisseur, Reduction Shatt Furnace; Nickel Laterite Ore; Ferronickel; MonitorMV

Jan 1, 2004

By Elli Miettinen, Markku Lahtinen, Ilkka Kojo

"The recent trends of decreasing energy consumption and environmental emissions and utilization of economies of scale are strong drivers favoring continuous copper converting processes. Flash Converting benefits from low off-gas volumes and low investment and operational costs for off-gas treatment. Separate matte and blister furnaces allow the adaptation to concentrate quality changes and flexibility in layout and maintenance.The stationary blister copper bath in Flash Converting furnace is less aggressive to the furnace linings than agitated processes, resulting in low refractory consumption, long campaign life and high on-line availability.Copper Flash Converting has been successfully applied in Kennecott with a campaign life now exceeding five years. A second FCF was started at Xiangguang Copper in China in 2007. The process itself is proven, as its features are similar to those in FSF, Direct-to-Blister and Direct Outotec Nickel Flash Smelting (DON), with one significant difference: it is the easiest of all to operate.The paper presents differences between continuous Flash Converting and conventional converting based on recent experiences and studies."

Jan 1, 2009

By M. T. Ernett

Significant amounts of arsenic are often present in effluents arising from the mining of sulfide ores for the extraction of metals such as copper, gold, lead and zinc. The arsenic is usually removed from the process effluent by co-precipitation with iron because of its common occurence in the mined ore bodies and the excellent adsorptive property of the precipitated hydrous ferric oxide compound. There has been controversy, however, over the long-term stability of the arsenic-bearing ferrihydrite which is produced. This paper presents the results of laboratory studies which indicate that the cations of calcium, magnesium, zinc, cadmium and lead, increase the pH range of effective arsenic adsorption in the Fe-As precipitate from 4-7 to 4-9. The increase in the pH range is similar for all of the added cations investigated. Sulphate ions are shown to have a minimal effect on the residual dissolved arsenate concentration. Silicate ions reduce the adsorptive capacity of ferrihydrite if they are present before the arsenic is adsorbed.

Jan 1, 1994