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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 Geir Wedde, Anders Sorhuus

"Vast quantities of energy are released as heat to the environment from industrial operations. Many countries target waste heat recovery to mitigate CO2 emission. Exhaust gases from industries such as primary aluminium smelting, carry a substantial portion of the waste heat generated. For a cost efficient capture of more valuable heat (higher exergy), heat exchangers should operate on the exhaust gases upstream of the gas treatment plants. Heat exchange surface would be exposed to dust laden gases with risk of fouling. Heat exchangers of innovated design and operation have overcome the potential of excessive fouling rates. Heat exchangers of the ""shell and tube"" design have been demonstrated for exhaust gases from ferroalloy as well as primary aluminium smelters. In addition to the heat recovery, gas cooling results in smaller gas treatment plants with lower costs and reduced emission. The aluminium experience is exampled in the paper.IntroductionIndustrial usage of energy continues to grow as a result of increasing volumes of production, a trend that is likely to continue in the coming decades as living standards keep rising globally. World energy consumption (Figure la) is to grow 49 % by 2035 (ref. 2010) as reported by EIA [1]. The industrial sector consumes somewhat more than 50% of the total world energy consumption predominantly the energy increased demand comes from non-OECD countries in Asia. The industrial consumption by production of metals iron and steel accounts for 14 % and for non-ferrous metals 3 % mostly for aluminium production (Figure lb). Aluminium production will be discussed in this paper as an example of an industry with large quantities of waste heat to recover"

Jan 1, 2012

By Baicheng Liu, Houfa Shen, Wensheng Li

"In order to understand the formation of macrosegregation in steel ingots, a mixture model has been developed which accounts for coupled mass, momentum, species, and energy transport to describe the sedimentation of free equiaxed grains during solidification. In this model, the mushy zone is divided into the slurry and porous regimes according to a solid packing fraction. Settling velocity of equiaxed grains in the slurry regime is given by an explicit expression. The solidification of a binary steel ingot (Fe-0.36wt.%C) with a two-dimensional geometry is numerically simulated. It is demonstrated that the predicted macrosegregation patterns agree to some extent with classical experimental results. Further refinement of this model is still necessary for realistically simulating steel ingot solidification.IntroductionModeling macrosegregation in steel ingots is still a challenging study, mainly due to the length scale of the products and the complexity of global multiphase transport phenomena coupled with microscopic solidification kinetics [l]. The thermal-solutal convection and the motion of equiaxed grains are the two main mechanisms responsible for macrosegregation. But there are few models that deal with the motion of equiaxed grains, which is confirmed as the main phenomenon that explains the negative macrosegregation along the centerline of large steel ingots [2]. A model which takes into account melt convection and grain sedimentation was first proposed by Beckermann and co-workers ([3], and references therein). More recently, similar multiphase solidification models with advanced nature have been presented by Wu and Ludwig [1,4] and Combeau and co-workers [5,6]. It is known that the application of these sophisticated models to steel ingot casting is at its beginning.In this paper, a solidification model based on continuum mixture approach, using much less sophisticated relations to obtain the settling velocity of free equiaxed grains, has been proposed in order to predict the macrosegregation in steel ingots. The model is applied to simulate the solidification of a binary steel ingot with a two-dimensional geometry, and preliminary modeling results are presented."

Jan 1, 2011

By Richard D. Hagni

Polished sections of pyrometallurgical intermediate products from a simulated commercial flash furnace were examined by reflected light microscopy, scanning electron microscopy-energy dispersive spectrometry and electron backscatter analysis, and microprobe analysis for phase and textural relationships. The smelter feed is a copper concentrate from a porphyry copper deposit. The concentrate consists primarily of chalcopyrite, bornite and pyrite with smaller amounts of covellite, chalcocite, molybdenite, magnetite, galena, and sphalerite. The flash furnace reactions for pyrite and chalcopyrite can be observed by reflected light microscopy. Reacted angular particles of pyrite exhibit successive rims of fibrous pyrrhotite and hematite or magnetite. Reacted angular chalcopyrite particles show successive rims of bornite, digenite, and chalcocite. Spherical particles, formed by the complete melting of former pyrite particles, consist of variable amounts of granular pyrrhotite with magnetite rims and minor hematite. Spherical particles, formed by the complete melting of former chalcopyrite particles, exhibit exsolution intergrowths with varying proportions of intermediate solid solution, bornite, digenite, and chalcocite and have rims of hematite, magnetite, and copper-iron spinel. Sphalerite and molybdenite do not show evident mineralogical reactions.

Jan 1, 1987

By Chikabumi Yamauchi, Masami Tashiro, Toshiharu Fujisawa, Hiroyuki Snano

"Rare earth metals usually contain large amount of oxygen because of their reactiveness, and therefore oxygen removal is one of the major problems on the purification of rare earth metals. In the present research work, halide flux treatment at high temperature under inert gas atmosphere was applied to the oxygen removal from neodymium. NdF3 was used as a halide flux. Deoxidation reaction and its mechanism were discussed based on the experimental results. Halide flux treatment is very effective for oxygen removal from rare earth metals.IntroductionSolid Sate Electrotransport (SSE) process has been successfully applied for the elimination of interstitial gaseous impurities from chemically active metals[l]-[5]. However, to achieve a higher effectiveness of the SSE process, it is required a very low initial impurity content in the metal. In case of rare earth metals, it is known that they usually contain large amount of oxygen that should be lowered as much as possible before applying the SSE process. In addition, if effective oxygen removal is achieved by simple process, it is significant also from the industrial viewpoint. In the present work, the application of a halide flux treatment is investigated to remove oxygen from neodymium by using NdF3 as a flux. At first, deoxidation reaction and its mechanism were discussed based on the phase diagram of the Nd-NdF3-Ndp3 quasi-ternary system. Based on the results, oxygen content in deoxidized neodymium was calculated theoretically and it was verified by deoxidation experiments."

Jan 1, 1998

By Felipe Daroch, Maria C. Ruiz, Rafael Padilla

Copper concentrates with high arsenic contents must be pretreated before conventional smelting to prevent environmental pollution with arsenic compounds. In this work, experimental results concerning the selective removal of arsenic and antimony from copper concentrates are presented. The process consists of an alkaline digestion using concentrated NaHS-NaOH solutions to transform the arsenic and antimony sulfides into soluble compounds. A water leaching follows the digestion to dissolve the arsenic and antimony, leaving clean copper sulfide solid residues. The laboratory scale tests were carried out using a copper–arsenic concentrate with 15.05% As and 1.42% Sb. The results showed that the most important digestion variables were temperature and concentrations of NaHS and NaOH. Over 97% of arsenic and 92% of antimony could be removed in 10 min of digestion using 8.9 M NaOH and 100% excess of NaHS at 80 °C. The subsequent water leaching was performed at 80°C for 20 min.

Jan 1, 2015

By Liu Wei-feng

Base on the thermodynamic calculation of vapor pressure of lead, antimony and arsenic at high temperature, the possibility of separating lead, antimony and arsenic in different temperature was analyzed ,and the practice of producing qualified antimony white from lead-antimony alloy by direct blowing was introduced in detail in this paper. The blast furnace reduction smelting was brief introduced firstly, and then alkaline refining was applied to removing arsenic from lead-antimony alloy that contains As1%,Sb39%,Pb58%,the arsenic in the treated lead-antimony alloy could decrease to 0.009% by that method. The antimony white containing Sb2O3 99.5% could be produced by air blowing in the special furnace at 650? from the treated lead-antimony alloy. And the electrolytic lead could be achieved by electrolysis from the lead-rich alloy which contained 83% lead.With high-grade product being obtained the process was shortened. The technology has been applied successfully many years in Guangxi, China.

Jan 1, 2009

By Jinrong Zhang

Major components of soil were tested for their ability to attenuate cyanide. Feldspar, kaolinite, plagioclase and bauxite are found to degrade cyanide at an appreciable amount mainly through adsorption. A soil near a mining site in northern Nevada was studied in detail using a tall column. Many species of cyanide were anlyzed to determine the mechanisms of the reactions of cyanide with soil. Volatilization, adsorption, oxidation, precipitation and complexing were quantitatively identified, being 5 to 10, 11.7, 4.2, 7.3 and 4 per cent of the total cyanide added, respectively. It is found that the oxidation of cyanide to cyanate is due to the catalytic effect of nickel and copper leached from the soil. Precipitation of metal-cyanide complexes occurred at low pH values.

Jan 1, 1991

An EAF dust generated in a Swedish steel mill has been leached in hydrochloric acid at The solution obtained has been subjected to purification by cementation followed by precipitation of zinc with sodium carbonate. The thermal decomposition of the precipitate was studied using thermal analysis and X-ray diffraction. The results show that during the calcination of the precipitate three different reactions occur. The decomposition of the solid phases Zn5(CO3) (OH)6, CaZn(CO3)2 and CaCO3 occur completely at 370°C, 560°C and 940°C respectively, yielding a final product containing 61.9% ZnO and 38.1% CaO. Methods to minimize calcium and manganese in the final product are discussed.

Jan 1, 2003

By F. Tailoka

Microporous membranes have been used to create a very fine dispersion of bubbles which greatly enhances the mass transfer of electroactive species to the electrode. Using this system, it has been shown that it is possible to electrowin copper as a coherent planar deposit, at high current densities, from copper chloride solutions.

Jan 1, 1990

By W. B. Carter, A. T. Hunt, G. W. Book

"Combustion Chemical Vapor Deposition (CCVDSM ), an open air, flame assisted CVD process, is under development. The CCVD process produces non-line-of-sight, epitaxial deposition. Materials deposited include YBa2Cu3Ox' Y2BaCuOx, BaTiO3, Y2FesOI2, ZrO2, yttria stabilized ZrO2 (YSZ), partially (yttria) stabilized ZrO2 (PSZ), and amorphous silica. Two modifications of the CCVD process are being studied. Liquid fuel CCVD deposition, involves the combustion of an organic solvent that contains dissolved reagents carrying the desired coating cations. Gaseous fuel CCVD deposition uses a flammable gas as fuel. A non-flammable solution containing dissolved reagents is either aspirated into the flame or mixed with the fuel gas as an aerosol prior to its combustion. Substrates to be coated are held near the flames' ends.IntroductionThin films and coatings can be deposited using a wide variety of techniques including chemical vapor deposition (CVD). CVD is ""a materials synthesis process whereby constituents of the vapor phase react chemically near or on a substrate surface to form a solid product.""lIn conventional CVD processing, gases carrying coating constituents flow into a reaction vessel where deposition occurs onto a heated substrate. The deposition process is often conducted at reduced pressure. Both cold and hot wall reaction chambers are used. Heat can be provided by a resistance furnace, rf induction, or high-intensity radiation lamps. Plasma, microwave, photo, laser, RF, and electron-enhanced CVD processes have been developed. The necessity of using a reaction vessel limits the substrate size and affects coating economics. Although most CVD depositions are performed as batch processes, continuous deposition can be accomplished with the use of appropriate hardware.The chemical vapor deposition of thin, dense oxide films has been accomplished in the open atmosphere with a flame assisted process. The process is called combustion chemical vapor deposition (CCVDSM).2 Two modifications of the CCVD process have been developed. The liquid fuel CCVD process involves the combustion of an organic solvent in which reagents (containing the coating cations) are dissolved. The gaseous fuel CCVD process uses a flammable gas as fuel. In this modification, a non-flammable solution containing dissolved reagents is either aspirated into the flame or mixed with the fuel gas as an aerosol of small droplets prior to its combustion. Substrates to be coated are held near the flames' ends."

Jan 1, 1994

By Annette Revet

Aluminum fluxes have been used for the remelting of secondary aluminum since the beginning of the recycling industry. During the last sixty years, a number of fluxes have been designed, researched and tested at the laboratory and plant scale. Fluxes are primarily a mixture of potassium chloride and sodium chloride with the addition of some other chloride and fluoride containing salts. The conventional Mining methods of potassium chloride and sodium chloride yield products that are not high in purity without costly reprocessing or additional refining. In 1993, Kalium Chemicals, Ltd. began supplying flux mixtures to the aluminum industry. Kalium produces potassium chloride and sodium chloride which are mined and refined by a patented solution-mining process. The salts produced by this process are high in purity with lower concentrations of iron oxide, sulfates, and other impurities. This paper will present the different mining methods used in the production of sodium chloride and potassium chloride. The paper Will address how these mining methods affect the purity of the final product as well as the effect of purity on the performance of the fluxing salt.

Jan 1, 1995

By Luis M. González, Guzmánm Guillermo D., Davis Juan C.

"The Teniente converter (CT) of the Ventanas Smelter and Refinery of Codelco-Chile has two tuyeres for dry concentrate injection directly into the melt.The diluted phase injection system can feed 15 to 20 kg of concentrate for 1 kg of air, which creates a very abrasive solid/gas phase. The tuyeres commonly used lasted for about 3.5 days due to the accelerated decay of the shell, and 1.5 hours were necessary for the replacement of new ones in the reactor.Tests were carried out with common shell tuyeres with a tungsten based welding cover, and a life span of 28 days was reached, increasing the Teniente converter operational continuity between 1.5 to 2 %."

Jan 1, 2009

By Tam Tran

Over the last decade, halide (chloride, bromide and iodide) systems have been evaluated as alternative lixiviants for the processing of gold to replace cyanidation which has been widely used in commercial practice. This paper first reviews the development of processes promoted by Kaljas Ltd / Lachlan Resources (Australia) and Great Lakes Corp (USA) using different bromide/bromine systems in the early 1990's. Several research groups subsequently evaluated the use of iodide/iodine and chloride/chlorine for gold extraction, showing similar characteristics of gold/silver dissolution and recovery. A critique is :given on the advantages and the ,shortfalls of halide systems as alternative lixiviants. The stability of gold? halide complexes is discussed, based on practical experience and thermodynamic modelling of their speciation, The iodide system provides the most stable gold / silver complex for easier handling. However, the cost of iodide inhibits its application for are processing. In this critique, emphasis is given on the cheapest system, which involves the use of chloride for leaching (in conjunction with an appropriate oxidant). However the chloride-base leachant has a major drawback which is related to the unstable nature of gold chloride in a reducing environment.

Jan 1, 1998

By Fathi Habashi

Solid gas reactions of metallurgical importance can be classified into three groups: Physical processes, e.g., drying and sublimation Chemical processes which may be an addition or a thermal decomposition reaction Electrochemical processes which may be addition, oxidation-reduction, or displacement reactions. Examples are given and the role of the boundary layer is emphasized.

Jan 1, 1996

By Fathi Habashi

In the past five years Cuba has been attempting to more than double its nickel production by constructing two new ammonia leaching plants. No metals are yet produced on commercial scale but a variety of oxides and sulfides. This report updates the Cuban nickel industry as a result of two visits : one at the invitation of the Cuban Ministry of Basic Industries in 1987 and the other as a consultant to the United Nations for the Cuban Laterite Project in 1989.

Jan 1, 1993

By S. Z. El-Tawil, K. A. El-Barawy, M. B. Morsi, M. M. Nasr, Z. I. Zaki

"Tue sulphatization of zinc concentrate produced from heated zinc concentrate of Um Ghieg area, eastern desert by ammonium sulphate as sulphatizing agent is carried out at different conditions to achieve the appreciable formation of soluble sulphates. The maximum zinc recovery as soluble sulphate equfils to 95% upon using 1.5 stoichiometry ammonium sulphate at 600 °C for one hour. Tue obtained leached zinc sulphate solution is subjected· to purification process to prepare high pure zinc metal and zmc compounds such as pure zinc sulphate, zinc caibonate and zinc oxide. The products obtained are analyzed chemically and identified by X-ray analysisTue mechanism and kinetics of the sulphatization process of zinc concentrate are considered where the activation energy is calculated and equals to 33.3 K.J.mol""1 A process flowsheet for the overall sulphatization process of zinc concentrate by ammonium sulphate is proposed.IntroductionConsiderable reserves of zinc ores are present in Um Ghieg area eastern desert, Egypt. The possibility of extraction zinc from these ores and preparing its valuable compounds by choosing a more feasible technology become of vital importance. An attention is focused on the sulphatizing roasting processes (1-9) to achieve the appreciable formation of soluble sulphates. Previous publications are reported in our division by El. Tawil and others (10-16) using ammonium sulphate as sulphatizing agent for the successful treatment of nonferrous bearing materials.Therefore, the present work aims to study the different factors affecting the sulphatizing roasting process of local zinc coocentrate by anunonium sulphate to extract completely zinc and preparing its main compounds. Tue mechanism and kinetics of the different chemical reactloos that 1ake place in the process are considered."

Jan 1, 2000

By Patrick R. Taylor

Iron phosphate glasses are promising host matrices for vitrifying actinide rich nuclear wastes materials because of their high solubility of actinide oxides, high chemical durability, and relatively low melting temperatures. An iron phosphate waste form was developed at the University of Missouri-Rolla. The structure and property of the waste form were well characterized by materials techniques. However, to scale the process and advance it to commercial viability, it is necessary to understand the processing parameters, such as the partitioning of waste elements and the viscosity as a function of temperature. Viscosity of 40 Fe203 - 60 P205 mole % iron phosphate melts (prepared with phosphorous pentoxide and ferric oxide) at 1000-1200 C was measured by the rotating-spindle method. It was discovered that this fluid has non-Newtonian behavior. Experiments were performed to study flow properties following the Standard Test methods for Rheological Properties of Non-Newtonian Materials by Rotational (Brookfield) Viscometer (ASTM D 2196-86). Samples prepared using ammonium phosphate and ferric oxide showed Newtonian behavior and the temperature dependence of the viscosity was studied over the range of 1000 to 1200 degrees C. The difference in flow behavior between the two fluids was analyzed in terms of preparation conditions and variation in the final composition and phases. The partitioning behavior of waste elements in the iron phosphate glass was studied by melting in a high temperature furnace and JCP analysis. The experimental results show that the solubility of Ce and Sr in phosphate glasses is significantly higher than the solubility associated with borosilicate glasses. This strengthens the conclusion that iron phosphate may be a viable alternative to borosilicate glass for immobilization of high heavy-metal-content wastes and actinide rich wastes.

Jan 1, 2002

By P. Mazumder

Numerical analysis is carried out to examine the effects of thermosolutal convection on the formation of complex patterns in directionally solidified binary alloys. A finite-difference analysis is used for dynamic modeling of a two-dimensional prototype of Vertical Bridgman system that takes into account heat transfer in the melt, crystal, and the ampoule; melt flow and solute transport. Actual temperature data from experimental measurements are used for accurately describing the thermal boundary conditions. A range of complex dynamical behavior is predicted in the melt flow due to flow transitions and this is found to be directly related to the spatial patterns observed experimentally in the solidified alloys. The model is applied to single phase solidification in the Al-Cu and Pb-Sn systems to characterize the effect of convection on the macroscopic shape of the interface. The application of the model to hyper-peritectic alloys in the Sn-Cd system shows that the presence of oscillating flow can give rise to a novel convection induced microstructure in which a tree-like primary phase in the center of the sample is embedded in the surrounding peritectic matrix.

Jan 1, 1999

By Min Chen, Nan Wang, Zhen Tian, Yingying Shen

"The enrichment behavior of phosphorus in CaO-SiO2-FeOx-P2O5 slag was studied by making an investigation on the distribution of phosphorous content in slag and 2CaO·SiO2 phase. The research results showed that the existing 2CaO·SiO2 solid particles in slag were the sites for the phosphorous enrichment. The enrichment process of phosphorus in CaO-SiO2-FeOx-P2O5 slag can be recognized as: mass transfer of phosphorus from bulk slag toward the surface of 2CaO·SiO2 particle, superficial dissolution reaction of phosphorus to 2CaO·SiO2 and diffusion of phosphorus through the product layer of 2CaO·SiO2-3CaO·P2O5 solid solution to the inner of 2CaO·SiO2 particle. Compared to the 2CaO·SiO2 particles with larger size (500µm to 1000µm), the completion time of enrichment was shorter for the particles with smaller size (less than 50µm).IntroductionDuring ironmaking and steelmaking, significant amounts of slag are produced. Contrast to the high utilization of ironmaking slag, the treatment of steelmaking slag is more difficult and challengeable, and therefore, an alternative approach is to recycle the steelmaking slag inside the ironmaking and steelmaking process itself. The main limitation to the reuse of steelmaking slag inside the process is that the refining process may be aggravated caused by the phosphorous accumulation if it is used in the blast furnace burden [1]. At the same time, the phosphorous content of steelmaking slag (approximately 1%~5% P2O5) is too low for it to be used as raw material for fertilizer [2, 3]. Moreover, owing to the diminishing supply of global iron ores with low phosphorous content, the control of phosphorus in iron and steelmaking processes has become an increasing problem, and as a result, more amounts of high phosphorus containing steelmaking slag are produced. Therefore, a valuable approach is quite appreciated in which the steelmaking slag is recycled within the ironmaking and steelmaking process and at the same time, the high phosphorus-containing phases in the steelmaking slag, suitable for use as fertilizer can be separated and recycled effectively [4]."

Jan 1, 2011