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By Isabella Lancellotti, Fabrizio Passarini, Luisa Barbieri, Fernanda Andreola, Ivano Vassura, Luciano Morselli

"The techniques able to incorporate wastes by means of a heat treatment present the advantage to fix the residue with chemical bonds. Among these techniques there are vitrification and sintering which are characterised by different operating temperatures in the range of 950-1500°C and the involved raw materials develop silicatic crystalline phases and glassy matrices capable to immobilize heavy metal contents in the waste matrix. In this work incinerator bottom ash, polishing and glazing ceramic sludges have undergone to thermal treatments in order to valorise the waste as secondary raw material for the obtainment of re-products. The chemical efficiency of the process adopted has been evaluated by comparing the results of release tests applied to the as-received wastes and to the thermally treated materials in order to verify the effectiveness of the different matrices to fix the waste components.IntroductionVitrification is one of the most promising technological options for the treatment of some kinds of waste. The high temperature involved in the process (1200-1500°C) leads to the complete destruction of organic pollutants, such as dioxins, and glassy network formed can incorporate heavy metals. Some vitrification processes naturally occur: glasses produced by volcanic eruptions, such as obsidians (Na2O-K2O-Al2O3-SiO2) and basaltic (CaO-MgO-Al2O3-SiO2) rocks, are basically inert materials even when they contain toxic elements, because these are embedded in an extremely stable glassy matrix. The disadvantage of vitrification is that it is an energy-intensive process involving relatively high costs, therefore its use is better justified if a high-quality product with optimised properties can be fabricated. The most effective way to improve the properties of the vitrified material is the transformation into glass ceramic. This is a fine-grained polycrystalline material (typically from 50% to 98% of the volume may be crystalline) formed when a glass of suitable composition is heat treated and hence undergone to controlled crystallisation (phenomenon named devitrification). The three key variables in the design of a glass-ceramic are: glass composition which controls glass viscosity related to the effectiveness of nucleation and rapidity of crystallisation; glass-ceramic phase assemblage (that is, the types of crystals and the proportion of crystals to glass) which is responsible for many of the physical and chemical properties; nature of the crystalline microstructure (crystal size and morphology and the textural relationship among the crystals and glass) which is the key to many mechanical and optical properties. In particular, a partly crystalline material can be obtained by powder sintering."

Jan 1, 2008

By Dhanesh Chandra

Long term stability studies were conducted on four variants of LaNi5; 10,000 hydriding/dehydriding cycles were used to evaluate their suitability for a metal hydride cooling system. Thermodynamic and structural studies were conducted to determine changes in these materials during cycling test period. The hydrogen sorption properties of LaNi5.2, and Lao 9Gd0.1Ni5 and LaNi4.75In0.27 were seriously degraded during the tests but the LaNi4.8Sn0.22 hydride was virtually unaffected. Hydride isotherms were measured at the beginning and at intervals through out the test period to observe the nature and extent of damage degradation in the sorption properties. X-ray diffraction studies of the alloys (LaNi5.2, LaO.9Gd0.1Ni5 LaNi4 8Sn0.22) and their respective hydride, before and after test, provided insight with regards to the observed changes in the hydride properties. Electron microscopic studies were also conducted to evaluate the changes in particle sizes.

Jan 1, 1989

By Henrik Gudbrandsen, Geir Martin Haarberg, Ana Maria Martinez, Karen S. Osen, Sverre Rolseth

"The Several approaches were tried for developing an electrochemical route for producing high purity silicon from molten salts. K2SiF6 and metallurgical grade silicon were used as the source of silicon. Molten LiF-KF and pure KF with additions of K2SiF6 were used as electrolytes at temperatures from 550 - 900 oC. Silicon was cathodically deposited and anodically dissolved in the fluoride electrolytes. High electrorefining efficiency was obtained for many elements after electrolysis experiments at constant potential or constant current. The main challenge was to reduce the contents of boron and phosphorus. Another difficulty was to remove inclusions of solidified electrolyte. The lowest energy consumption was estimated to be ~ 3 kWh/kg Si, while the best current efficiency for Si deposition was found to be ~ 95 %.IntroductionSilicon is the most important material for photovoltaic power generation devices because of high feasible efficiency, low ecological impact and slow degradation. Development of a new and less expensive route for producing silicon of the desired quality is necessary in order to make solar cells competitive. Electrochemical routes may be an alternative possibility, and many laboratory studies have been reported over the past few decades. Most of the studies have been performed in molten salts, chloride or fluoride, at moderate temperatures so that solid silicon was deposited at the cathode. The production of high purity silicon has shown an annual increase of about 25 %, due to the increasing demand of solar grade silicon (SoG-Si). For future increased use of solar energy it is important to develop alternative, more energy efficient and cheaper processes for SoG-Si production compared to the Siemens process.Common silicon sources have been SiO2 and K2SiF6 for electrowinning and MG-Si in the case of electrorefining. A serious challenge is to find an oxygen evolving anode for electrolytes containing dissolved oxides. Especially at moderate to high temperatures and in molten fluoride electrolytes this is a difficult task.Many experimental results have been reported in molten chloride electrolytes. Nohira et al. [1-3] and Chen et al. [4] cathodically deposited silicon by electrodeoxidation of solid SiO2 in molten CaCl2 by potentiostatic electrolysis. An alternatice approach is to use electrorefining of low-cost metallurgical grade silicon (MGSi) to produce SOG-Si. In previous studies [5], an MG-Si anode was used, and silicon was successfully electrodeposited on a molybdenum wire in a CaCl2 based melt. It was found that the anode was strongly passivated due to the precipitation of silicon. Also, some deposits detached from the molybdenum wire because of the poor adherence to the cathode.Considering the Cu-Si alloy which has a good segregation effect for some impurities, and should not passivate, could be a good candidate anode for electrorefining. [6]."

Jan 1, 2014

By Youliang He

Twin-roll casting is an integrated casting and rolling process that involves the continuous solidification of a melt and the plastic deformation of the solidified metal between two rotating rolls. Computer modeling is a valuable tool to help engineers understand the metallurgical process during twin-roll casting. However, commercially available software can only model either the fluid flow/heat transfer of the melt or the plastic deformation of the solid, but not both. In this study, an object-oriented finite element program was developed to simulate the steady-state fluid flow, solidification and plastic deformation of an A7,31 magnesium alloy in a horizontal twin-roll caster. The melt, the mush zone and the solid were treated as a generalized Newtonian flow in an Eulerian reference frame and different constitutive equations were employed to describe the material behaviours. The effect of operational parameters on the solidification process was discussed based on the simulation results.

Jan 1, 2010

By Xueming Lv

The rotary kiln-electric furnace (RKEF) process is the main method for producing ferronickel from nickel laterite ore. However, this process is energy intensive as it involves several high temperature steps. Therefore, a novel process is proposed to directly produce ferronickel from nickel laterite ore by semi-molten reduction, which is expected to be realized in a rotary hearth furnace (RHF). The RHF process is able to shorten the flow sheet, decrease the reaction temperature as well as reduce energy consumption. In this study, the influence of basicity on reduction of nickel laterite ore was investigated. The results showed that it is possible to produce the ferronickel nugget directly at 1400 °C when the quaternary basicity [(mCaO + mMgO)/(mSiO2 + mAl2O3)] was fixed at 0.60. Under this experimental condition, the grade and the recovery ratio of nickel reached 11.53% and 98.59%, and the grade and recovery ratio of Fe were 84.16% and 68.72%, respectively.

By Feng Liu

A thermal upgrading process by which nickel value can be concentrated in a ferronickel alloy is a possible alternative to treat Sudbury pyrrhotite (Po) tailings with nickel content of 0.5–1.5 wt%. The basis of this process is precipitation of Ni from Po at high temperature once Fe/S ratio in the iron-deficient Po is shifted towards stoichiometric or near stoichiometric FeS (troilite) either by the addition of iron and/or the removal of sulfur. For the iron addition route, the reaction between elemental iron and nickeliferous pyrrhotite to produce ferronickel alloy and Ni-depleted iron sulfide phase plays a critical rule. In this paper, the formation mechanism of ferronickel alloy was investigated using the diffusion couple technique to better understand the nickel diffusion behavior in the iron and sulfide phases.

By Yafei Xiong, Yue Wang, Guotao Xu, Shuzhong Li, Huaiyuan Li

"The composition, properties and structure of taphole clay with high strength and friendly surrounding used in a new blast furnace with 3800 M3 volume was studied. The developed taphole clay had been applied in the blast furnace for four months, pouring times were 11-13 every day, flowing rate of hot iron was 7.5 t/min and the consumption of taphole clay was 0.49Kg per ton iron, which can make the new blast furnace attach the designed production quickly and decrease the cost of hot iron. The taphole clay is easy to be opened in the channel of hot iron which can be remained in stable shape under the corrosion of slag or hot iron, and it dose not produce poisonous smoke in yellow or dark color in the use process. The development of new taphole clay is useful to improve the work surrounding of the blast furnace.IntroductionIn the iron-making process, the taphole clay's function is filling up the taphole and protecting the formation as well as the growth of the clay in the blast furnace, maintaining the enough taphole depth; simultaneously it is easily to open a hole and knock out the clay. The taphole clay has a good performance of molten slag and hot iron resistance. The traditional taphole clay uses coal tar or carbolineum as a binder, and the performance of taphole clay is good, but it has the black and yellow poisonous smoke, which is harmful for work condition. Through the investigation on the binder's composition and poisonous performance of taphole clay, the environmental taphole clay is developed by some foreign companies, which is named the third generation product with benzene is less than 300ppm, and it has been used in European steel companies. This application of the taphole clay with high strength and environment-friendly using in 3800m3 blast furnace is introduced and the performance is discussed and analyzed in this paper."

Jan 1, 2012

By Gui-fang ZHANG, Zhe SHI, Lei GAO

Secondary V-recycling slag, an industrial waste containing high gallium is being dumped continuously, which causes the loss of gallium. Thus, the alkali fusion process was employed to recover gallium from this slag. The effects factors on extraction of gallium such as roasting temperature, roasting time, alkali fusion agent concentration and CaO concentration were investigated in the paper. The experimental results indicated that excessive roasting temperature and roasting time is unfavorable to the recovery rate of gallium. The appropriate roasting temperature and duration are 1000 and 2 hours, respectively; The appropriate proportioning of Na2CO3: NaOH is 2:1 when the concentration of alkali fusion agent weighs 0.4 times the mass of the slag; In order to remove SiO2 from the leaching liquor, CaO should be used as an additive in the roasting process. The appropriate concentration of CaO should weigh 0.2 times the mass of the slag. Employing these optimal alkali fusion conditions in the roasting process, gallium recovery is above 90%

Jan 1, 2015

By Tadafumi Adschiri

"Supercritical water can provide an unique reaction atmosphere for synthesizing metal oxide nanoparticles. Due to the drastic change of properties of water around the critical point, including density, dielectric constant and ionic product, the reaction phase with O 2 or H2 gas and the reaction rate and equilibrium can be varied to synthesize new materials or define particle morphologies. In this work, hydrothermal crystallization experiments are performed with several types of flow apparatus that allow convenient manipulation of variables such as temperature, pressure, and residence time. Key features in the flow modes and material preparation are discussed. The proposed supercritical hydrothermal synthesis method has the following desirable features: i) nanoparticles can be produced, ii) morphology of the produced particles can be controlled with small changes in pressure or temperature, and iii) a reducing or oxidizing atmosphere can be applied by introducing oxygen or hydrogen or other gases. An overview of this method is given for functional material synthesis of significant industrial interest including barium hexaferrite magnetic particles, YAO/Tb phosphor fine particles and lithium cobalt fine crystals.IntroductionHydrothermal crystallization, a method of metal oxide formation from metal salt solutions, is typically used at temperatures ranging from 373 K to 473 K. We are developing a new process for hydrothermal crystallizations that uses temperatures in the range of 673 K to 723 K, which is just above the critical temperature of water1 • 8 • In this work, we refer to this process as supercritical hydrothermal synthesis. The supercritical state of water allows one to vary reaction rate and reaction equilibrium by shifting the dielectric constant and solvent density with pressure and temperature. From of our research on material production in supercritical water, we have identified the following specific features of the supercritical hydrothermal synthesis method: (i) ultrafine particles can be produced, (ii) morphology of the produced particles can be controlled to some extent with pressure and/or temperature, and (iii) a homogeneous reducing or oxidizing atmospheres can be provided by introducing gases, such as O 2, H2, H2O 2• and so on.1"

Jan 1, 2000

By P. N. Anyalebechi

The effects of solidification rate (0.4-26.1 K/s) and alloying elements on the cast microstructures of aluminum alloy 5182 have been investigated with directionally cooled laboratory-size ingots. The alloying elements examined included Mg (3.6-4.7 wt.%), Mn (0.35-0.75 wt.%), Fe (0.11- 0.42 wt.%), Cu (0.03-0.25 wt.%), and Si (0.11-0.28 wt.%). These reflect the chemical compositions of AA 5182 end stocks with high recycled used beverage container (UBC) content. For a given chemical composition, the average dendrite cell and constituent phase particle size decreased with increase in average solidification rate. In general, within the level investigated, Mg did not have a significant effect on the types, volume fractions, and average sizes of the constituent phase particles. However, increase in Mn, Si, Fe, and Cu increased average sizes and volume fractions of the constituent phase particles.

Jan 1, 2010

By José Brant, Douglas Torres, Rogério Navarro, Rodrigo Souza, Eduardo Brocchi

The steelmaking process requires the input of ferro-alloys to implement the adjustment of some elements composition in the final product. In the particular case of stainless steel production, the high carbon FeCr alloy stands out as one important precursor. However in the production of this material a certain quantity of fine powder with remarkable chromium and carbon content is also generated, which, in turn, could be processed through alkaline roasting in order to selectively recovery this element in a subsequent aqueous route. In the present work, this process is investigated, using excess of NaOH as oxidizing agent, and H2O2 for precipitating chromium as Cr(OH)3, which is next calcinated to Cr2O3. According to the results, the global achieved recovery has shown to be around 98%, suggesting that the proposed route can be seen as a potential process for chromium oxide production from the mentioned fine powder.

Jan 1, 2015

By R. Togashi, S. Kuramochi, T. Yamada

In 1972, the Akita Zinc Co., Ltd. commenced operations with an annual capacity of 86,000 tonnes of electrolytic zinc, and it has operated with an annual capacity of 156,000 t-Zn since 1974. The business surroundings for non-ferrous metals production have become more severe with the high Yen rate for the dollar and low domestic demand in the last few years. Consequently, the company tried to survive with some improvements and succeeded to reduce operating costs and to improve profitability as follows: 1) expansion of its production capacity to. 196,000 t-Zn annually, 2) saving man-power by the introduction of fully-automated machines for cathode handling in the cellhouse, 3) improvement of the hematite process by means of the recovery of rare-metals. These improvements made Akita Zinc a competitive refinery in the modern world. We have been trying to improve the operations more and more. One of the challenges is to purify the iron oxide made in the hematite process by applying an As removal process, which is coming into operation in the near future.

Jan 1, 2000

By Seref Sonmez, Onuralp Yücel, Kagan Benzeşik

The aim of this study is processing of domestic molybdenum concentrate to produce technical grade molybdenum trioxide may be the starting material for the production of various molybdenum products. In order to determine the optimum parameters for the total oxidizing roasting process of molybdenite concentrate to produce MoO3 and purify the MoO3 product by removing the copper content; first, MoS2 was roasted by controlling reaction temperature and duration in a chamber type furnace. The highest Mo concentration rate was obtained as 56.6 wt% of Mo at 650 °C for the roasting duration of 45 min. Secondly, roasted product was leached with H2SO4 to remove copper. Leaching conditions were optimized by investigating the effects of different H2SO4 concentrations and S/L ratios. The minimum copper content was obtained as 0.13 wt% at leach residue. The raw materials and the products were characterized by using AAS (atomic absorption spectrometry) and XRD (X-Ray Diffraction) techniques.

Mar 1, 2017

By Nicolas Reynier

The separation of radionuclide during rare earth element (REE) production is an important requirement for developing the Canadian REE mining industry. Separation of actinides from REE is often a large concern in the rare earth industry because of the need to manage the radioactive nuclides. A patented process developed for actinides extraction from radioactive wastes was applied to REE ore. Objectives were to optimize the process for REE leaching from ore, and separate radioactive impurities from sulphuric and nitric liquor by ion exchange (IX). Ore leaching was optimized using a surface response plan to ensure statistical significance. In optimized conditions, solubilization yields ranged from 90–95% for Th, 60–75% for U, 48–55% for LREE, and 59–75% for HREE in sulphuric and nitric media. Both media were compared for radionuclide removal from rich REE-bearing mineral liquor by IX. Actinides separation ranged from 92–97% for Th and 69–96% for U in sulphuric and nitric media.

By Hector Henao

To provide thermodynamic data for converting the nickel matte to liquid nickel, an experimental study was conducted in the phase equilibrium between the Ni-S alloy and the CaO-Ah03 based slag melted in a MgO crucible at 1873 K under controlled Pso2 of 10.1 kPa and pO;, in a range between 2.5x,IO,2 and 10.1 Pa by using CO-C02-S0Z gas mixtures. The content of nickel in the slag at POz of 10.1 Pa, above which solid NiO is expected to precipitate in the equilibrium state, was found to be 4.1 mass% and the contents of sulfur and oxygen in the nickel melt were 0.4 and 0.2 mass%, respectively. It was clarified that increase in the temperature reduces the solubility of nickel in the slag and the contents of sulfur and oxygen in the alloy. The distribution of minor elements such as gold, silver, copper, cobalt, iron, arsenic and antimony between the Ni-S alloy and the CaO-AI20) based slag was also studied. The distribution ratios of iron and cobalt, defined by (%X in slag)/[%X in alloy] where X is the minor element, are larger values than that of nickel, while those of copper, silver and antimony are similar to that of nickel. The distribution ratios of arsenic and gold are lower than that of nickel in the higher range of oxygen partial' pressure.

Jan 1, 2003

By Jitka Jandová

In this study, hydrometallurgical processing of waste ZnO flue dust arising during zinc removal from galvanized low-alloy steel sheets was investigated on a laboratory-scale to obtain electrolytic zinc. The flue dust was separated from flue gases, generated during heating waste galvanized steel sheets in an electric furnace under air atmosphere at temperatures of about 1000oC. The dust, comprising tetragonal ZnO and insignificant amounts of SiO2, was contaminated by Fe, Mn, Pb, Al, Mg, Pb, Cu and Ca. The dust was leached in 0.5 and 1.0M H2SO4 and/or in 20 and 30% NaOH at different temperatures and different liquid-to-solid ratios to determine the optimum conditions leading to the highest possible selectivity of leaching and efficiency of Zn extraction in minimum time. The subsequent electrowinning process was performed with refined zinc sulphate leach liquors and/or with untreated zinc caustic solutions. Zinc sulphate leach liquors were purified using a combination of a hydrolytic pH-controlled precipitation, cementation and carbon refining. Effects of operational variables on Zn electrowinning have been studied for both sulphate and caustic electrolytes. The conventional plate-plate electrowinning cell has been explored in this study. Comparison of results obtained for both zinc electrowinning from acid sulphate and alkaline solutions is presented contribution.

Jan 1, 2003

By Eun Duck Park

The gold catalyst supported on iron oxide was prepared from gold dissolved in aqua regia by a deposition-precipitation method and applied to CO oxidation in the absence and presence of hydrogen. Some characterization methods such as X-ray diffraction (XRD), nitrogen adsorption, transmission electron microscopy (TEM), temperature programmed reduction (TPR), temperature programmed oxidation (TPO), and the pulsed CO chemisorption with temperature programmed desorption (TPD) were conducted to explain different catalytic activities of Au/Fe2O3 catalyst pretreated at different conditions. The particle size of gold was about 10 nm for Au/Fe2O3 calcined in air at 373 and 573 K. For complete CO oxidation, the decreasing CO conversion with a reaction time was observed at low temperatures but its initial catalytic activity can be restored by a heat treatment at high temperatures. This catalyst was quite active for the selective CO oxidation in the presence of hydrogen especially at low temperatures. In the presence of hydrogen, the deactivation was significantly diminished.

Jan 1, 2006

By R. K. F. Lam

Unacceptable levels of impurity were noted in high purity chromium melting. Analysis of recent melting data determined that oxygen content in chromium is the critical parameter. Thermodynamics studies identify zirconia to be the most stable oxide in the presence of liquid chromium, followed by alumina and silica. Iron oxide reacts readily with liquid Cr. A certain degree of chemical reaction between liquid chromium and oxides does occur, contamination by the crucible is therefore unavoidable. Equilibrium constants indicate that a chromium oxide addition decreases 'ceramic dissolution and reduces impurity contamination. Safe operating conditions with oxygen content between 1190 ppm and 2500 ppm were identified. Additions of chromium oxide (Cr2O3) of 161 grams and 264 grams to liquid chromium yielded acceptable levels of impurity, and oxygen content was respectively increased to 1624 ppm and 2 179 ppm. A new process of melting high purity chromium with chromium oxide addition for controlling the activity of Cr2O3 is recommended.

Jan 1, 1997

By Nexhmedin Lohja

The production of high-carbon ferrochromium in a submerged electric furnace based on double-level technology has some advantages compared to close-type furnaces with one tap hole. These advantages include the reduction of the specific energy consumption for the overall process, good separation of ferrochromium from slag, an effective treatment of raw materials including lean chrome ores (low percentage of Cr2O3) etc. An outline of the operation of this furnace along with the production line of briquettes from fines of chrome ore by using organic and inorganic binders, will be followed by a description of the recent work carried out to improve the energy consumption in this furnace through a pre reduction process of Cr2O3 ores by the off-gas energy recuperated from the furnace and the use of SiC in the feed. A short theoretical analysis of the new work will also be given.

Jan 1, 2006

By A. D. Neuman, C. C. Davis, M. R. Lopez, A. C. Martinez, T. A. Nothwang, F. G. Hampel, S. L. Voit

"One of the thrust areas for the Global Nuclear Energy Partnership (GNEP) program is the development of actinide bearing fuels for transmutation in a fast reactor. Mixed Oxide (MOX) fuel has an extensive fast reactor irradiation history and thus is being considered for use as a baseline composition from which minor actinides can be incorporated for use as a transmutation fuel. The current study involves characterization of precursor powders and pellets destined for the Advanced Test Reactor in Idaho. These pellets will have three compositions: one standard MOX composition, (U0.80Pu0.20)O1.98, and two compositions of minor actinide mixed oxide (MAMOX) with oxygen to metal ratios (O/M) of (U0.75Pu0.20Am0.03Np0.02)O1.98 and (U0.75Pu0.20Am0.03Np0.02)O1.95. The precursor powders were characterized using a field emission gun scanning electron microscope (FEG-SEM) to determine particle morphology, size, and size distribution. An electron probe microanalyzer (EPMA) was used to characterize element distributions in the pellets.IntroductionThe fundamental purpose of GNEP is to enable a fuel recycling partnership between member nations. The customer nations utilize the fuel for electricity generation provided by and subsequently recycled by the supplier nation. The supplier nation recycles the actinide constituents, mainly uranium and plutonium, in advanced nuclear power reactors, and thus reducing waste volumes [1, 2]. Nuclear materials are strictly controlled through the International Atomic Energy Agency. One of the thrust areas supported by the GNEP program is the development of actinide bearing fuels for transmutation in a fast reactor under the U.S. Advanced Fuel Cycle Initiative (AFCI) in order to transmute long-lived transuranic actinide isotopes into shorter-lived fission products [3].MOX fuel has an extensive fast reactor irradiation history and thus is being considered for use as a baseline composition into which minor actinides can be incorporated for use as a transmutation fuel [4]. Irradiation performance data on oxide fuels with high concentrations of minor actinides is limited, which has prompted this study. This paper discusses the characterization results of precursor powders and pellets prepared for the Advanced Test Reactor in Idaho to determine the effects of including minor actinides in the fuel, and addresses two fuel test matrices proposed by Hilton et al. [3]. The pellets will have three compositions: one standard MOX composition, (U0.80Pu0.20)O1.98, and two compositions of MA-MOX with O/M of (U0.75Pu0.20Am0.03Np0.02)O1.98 and (U0.75Pu0.20Am0.03Np0.02)O1.95. The precursor powders, uranium oxide (depleted, DUO2 and highly enriched, HEUO2), neptunium oxide, NpO2, americium oxide, AmO2, and plutonium oxide, PuO2, were characterized using a FEG-SEM for particle morphology, size, and size distribution. The morphology of the actinide powders was studied in the areas of flowability and porosity in order to predict manufacturability. The MOX pellets were characterized using an EPMA in order to determine impurity levels and locations."

Jan 1, 2008