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By Maria Salazar-Villalpando, Todd H. Gardner

"Efficient utilization of CO2 can help to decrease global warming. Methane reforming using carbon dioxide has been of interest for many years, but recently that interest has experienced a rapid increase for both environmental and commercial reasons. The use of CO2 provides a source of clean oxygen, which eliminates the need for costly oxygen separation plants. The product of dry reforming is useful syn-gas, which can be used to generate electrical power in a SOFC or in the production of synthetic fuels (hydrocarbons and alcohols). Hexaaluminate catalysts prepared at NETL may represent a product that can be utilized for the conversion of CO2 to syn-gas. In this work, transition metals dispersed in barium hexaaluminate have shown to be promising new catalysts for dry methane reforming. In this investigation, a series of BaNixAl12-yO19-d catalysts with varying Ni content were prepared by co-precipitation followed by calcination at 1400°C. CO2 reduction by dry methane reforming was carried out to determine catalyst performance as a function of temperature and carbon formation was also quantified after the reforming tests. Results of catalysts characterization, dispersion and surface area, were correlated to catalytic performance.IntroductionEfficient utilization of CO2 can help to decrease global warming. Methane reforming using carbon dioxide has been of interest for many years, but recently that interest has experienced a rapid increase for both environmental and commercial reasons. The use of CO2 provides a source of clean oxygen, which eliminates the need for costly oxygen separation plants. The product of dry reforming is useful syn-gas, which can be used to generate electrical power in a SOFC or in the production of synthetic fuels (hydrocarbons and alcohols). The dry reforming reaction has been known for a long time. Recent publications have reported studies over several catalysts. For example, the CO2 reforming of CH4 over mesoporous nanocrystalline zirconium powders (ZrO2–3%M2Ox; M: Ce, La and K) at 700ºC have shown methane conversion up to 60% (1). Similarly, the effect of Ni content (1–12 wt%) on the surface and catalytic behavior of bimetallic PtNi catalysts supported on ZSM-5 for reforming of methane with CO2 has been studied and report shows a maximum conversion of 16% and catalyst deactivation was observed during the first hour of time on stream (2). In another report, (3) Ni/a-Al2O3 catalyst was tested for syn-gas generation at 750ºC. The maximum methane conversion was 25%."

Jan 1, 2008

By Metehan Erdogan, Orhan Gökçe Göksu, Ishak Karakaya

"An experiment (mixture) design was created to optimize the process parameters of the electrochemical reduction of CaW04 to W in molten CaCl2-NaCl eutectic mixture. Temperature, applied voltage and the length of Kanthal wire winding of the CaW04 pellets were selected as the process parameters that were allowed to vary between the predetermined minimum and maximum values. The rates of the electrochemical reductions were interpreted from the variations of current and total charge vs. time graphs under different conditions. The analysis pointed out that 640°C and 2.81 V resulted in the fastest reduction. Itwas seen that the effect of Kanthal wire winding on the output current was less pronounced when compared to the other two parameters.IntroductionFFC Cambridge Process [1] has been applied to a number of metal oxides in laboratory experiments to produce metals. In nearly all of these studies, the electrolysis temperature was around 900°C, the electrolyte was pure CaCl2 or CaCl2 containing salt solutions and the anode was graphite. However, it was recently shown that the electrochemical reduction process of metal oxides in CaCl2 containing electrolytes at the mentioned high temperatures was not suitable for tungsten production [2], It was reported that as soon as WO3 contacts CaCl2, the following reaction occurs:"

Jan 1, 2012

By Hartmut Rossel

VAW aluminium AG has built a "Recycling-Technikum" (Recycling Research Centre) to add a new arm to the company's Corporate Research and Development Department. The Recycling Research Centre, a pilot plant for scientific research, has been in operation since September 1993. These state-of-the-art facilities allow the investigation and optimisation of recycling techniques in 'a global way and in detail. Research is concentrated on the unit operations - processing, melting and waste-gas purification - with the available installations making it possible to compare different alternative process combinations on a 100-kg scale. One of the main targets of VAW research is the development of recycling techniques for packaging. The paper presents an approach to recover the aluminium contained in flexible packaging materials using an integrated melting and waste-gas purification system.

Jan 1, 1995

By Laihua Wang, Peter Hayes, Hae-Geon Lee

"This paper introduces a new process for the efficient removal of dissolved gases and inclusions from liquid metals. This process involves the creation and dispersion of fine bubbles in molten metals by introducing inert or reactive gas into a region of turbulent flow. The highly turbulent metal flow splits the gas into fine bubbles and results in good mixing between the gas and molten metal phases. These conditions are ideal for contacting inclusions in the metal with the bubbles and subsequent flotation of the inclusions to the metal-slag interface where the inclusions are then absorbed by the covering slag layer. Dissolved gases, such as [H], [0], [N] in the metals are also transferred to the gas bubbles and removed from solution.The process concept has been previously demonstrated using a full-scale air/water model to simulate the ladle-to-tundish system of continuous casting of steel. The present cold modelling work has further demonstrated the ability of the process to remove gas solutes. The results indicate that the efficiency of new process is several hundred times greater than that of conventional high speed rotating injectors which are currently applied in the treatment of liquid light metals.IntroductionDuring metal smelting, refining and alloying processes, unwanted gas and second phase liquid or solid impurities are incorporated into liquid metals. In the case of steelmaking, the gas-forming impurities include [0], [H] and [N], and the solid impurities as a result of deoxidation include Ah03, Si02 inclusions. Common impurities in liquid aluminium are dissolved hydrogen and solid Ah03. To avoid subsequent problems during processing and to improve the physical properties of the metal products it is necessary to significantly reduce the level of impurities."

Jan 1, 1996

By W. Kunda

Silver nitrate solution is a very common product in hydrometallurgical processes involving the treatment of various silver bearing materials. Silver is recovered by electrolysis. The alternative method for the recovery of silver from aqueous solutions is the precipitation by hydrogen at elevated temperature and pressure. A previous study by the authors revealed the feasibility of this technique for the silver ammine sulfate system. Further study showed different behavior for silver in the silver ammine nitrate system and a systematic study was initiated to establish the optimum conditions for the process. The study showed that the process can be controlled by (1) composition of the feed solution, (2) temperature and (3) hydrogen pressure. The recovered silver product was in the form of very fine powder.

Jan 1, 1989

By Jorge Alberto Soares Tenório, Viviane Tavares de Moraes, Denise Crocce Romano Espinosa, Franco Alves Lavacchini Ramunno

"The traditional process for recovery of metals from waste electric and electronic equipment (WEEE) usually involves pyrometallurgical processing. However, the application of this technology to processing waste printed circuit boards (WPCBs) might lead to the formation of dioxins and furans, due to thermal degradation of flame-retardants and polymeric resins present in the board substrate. Therefore, this paper proposes a hydrometallurgical route for the recovery of copper. The acid leaching behavior of copper has been investigated at three different temperatures (25°C, 50°C and 75°C) with and without the addition of an oxidizing agent (hydrogen peroxide - H202). The dissolution kinetics for acid copper leaching was calculated based on chemical analysis by ICP-OES (Inductively Coupled Plasma - Optical Emission Spectroscopy). At 50°C with 1 mol/L H2S04 added 10 mL H202 (30%) each half hour under pulp density of 1 g I 10 mL, 100% of copper was extracted after 3 hours. The dissolution kinetics of copper with H2SO4-H2O 2 followed 1 - (1 - X)113 =Ket, i.e. chemically controlled reaction model.IntroductionThe information regarding the generation of waste electric and electronic equipment (WEEE) are still difficult to obtain because the estimates should take into consideration the historical production and sale of various products and the rate at which they reach the end of their life cycle, whose duration depends on the behavior of consumers [1]. Thus, the estimated overall WEEE generation varies between 25 and 50 million tons each year, which corresponds to more than 5% of all municipal waste generated [2], and this amount will increase at a rate of 3 to 5% per year, approximately three times faster than other individual types of waste [3].Printed circuit boards (PCBs) are essential parts of electric and electronic equipment (EEE), being found in virtually all electronic products, as well as in weapons systems [4]. A PCB is a basic component, which consists of a board where copper tracks are deposited. While the board behaves as an electrical insulator, the tracks connect electrically the various components attached to the board [ 5]. In addition to glass fibers, paper and resins, the PCBs contain significant amounts of metals, such as copper, iron, nickel, lead, stain, silver, gold and palladium [6]. In general, the weight fraction of metal is around 28% and the remainder of the boards is composed of plastic (19%), bromine (as flame retardant - 4%) and ceramic material (49%) [7]."

Jan 1, 2014

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 K. Krishnapisharody

A mathematical model has been developed to predict the interface dynamics and droplet generation of the buoyant phase in a two-fluid system. The model employs the well-known SIMPLE algorithm for obtaining flow fields and the Volume of Fluid (VOF) method, for interface tracking. The implementation of the model in water-oil systems, where the oil layer is placed above a recirculating water bath, is discussed. The evolution of the water-oil interface leading to the formation of oil droplets is computed realistically.

Jan 1, 2008

By Judy Che, Steven Ceccio, Gretar Tryggvason

"A detailed understanding of drop deformation and solidification is essential for quantitative predictions of geometry and properties of parts made by ballistic particle manufacturing processes. Axisymmetric results of towers built by the deposition of multiple drops are presented. In these computations, fluid flow, heat transfer, and phase change are fully coupled throughout the drop deformation and solidification process. The solution method is based on a single set of conservation equations written for all phases simultaneously. The phase boundaries are treated as imbedded interfaces by adding the appropriate source terms to the conservation equations. A parameter study demonstrates the effect of Weber number, Peclet number, and drop deposition frequency on the final shape of the structure. Numerical results show that most successful method of building uniform towers is when two conditions are met. First, each drop solidifies at the same time in the deformation cycle. Second, the cooling rate is slow enough to allow for good adhesion between drops. The ability to predict the final shape of deposited drops will greatly reduce the amount of experimentation necessary to select the desired set parameters for any artifact.IntroductionMaterial deposition techniques based on layering small molten metal drops holds the promise to build small, coherent three-dimensional structures. In this process, numerous 20-100 µm diameter drops are deposited onto a substrate with a low impact velocity (on the order of 5 mis). Both the momentum and trajectory of each drop are controlled precisely to build up complex parts. This material layering technique differs from processes such as spray forming and splat quenching which involve high impact velocities (on the order of 100 mis) and high frequency deposition with little control over individual drop placement. This process of layering small drops can produce parts with near net shape accuracy, while spray forming produces slabs of material which must then be worked to make a usable part. The ability to computationally predict final drop shape and cooling rate has the advantage of allowing the user to select parameters to produce parts with desired shape and mechanical properties. However, the development of such predictive methods requires a thorough understanding of both drop deformation and solidification"

Jan 1, 1999

By Ray Y. Lin

Chemical vapor deposition of tungsten carbide on the surface of steel has been investigated at temperatures between 400 and 550C in an atmosphere containing tungsten hexafluoride, hydrogen and benzene. The tungsten fluoride flow rate was maintained at 20 ml/min. The hydrogen flow rate was at 100 ml/min. The benzene concentration varied from 1.15 to 5.56% in the reaction gas. It was observed that the higher the temperature, the faster the deposition rate for tungsten carbide. But the dependence of the deposition rate on the benzene concentration was not systematic. From the x-ray diffraction analysis, it was observed that W, W2C and WC are all presented in the coating. The amount of each phase presented in the coating depends on the temperature and, to a less extent, on the benzene concentration. The microhardness measurement has also been done for all CVD carbide coatings obtained in this study.

Jan 1, 1992

By André Laplante

The mineralogy of the Joe Mann mine differs from that of other deposits of the Chibougamau area that are exploited by Les Mines Camchib Inc.. It is characterized by very fine first generation gold and very coarse second generation electrurn. Successful milling required adjustments of the processing flowsheet, which includes gravity, flotation, and cyanidation. A study of coarse gold liberation in the gravity/grinding circuit is described. Modifications to the flotation circuit and the reconditioning of a small capacity cyanidation circuit are presented. As a result of the circuit modifications, gold recovery increased from 65 to 81% in flotation and cyanidation. Overall gold recovery increased from 77% to 88-89%. These improvements are mostly attibutable to the recovery of -10 urn gold, whose presence in the Joe Mann ore and original circuit tails had been identified by process mineralogy.

Jan 1, 1989

By Entov Vladimir M., Gilmer R. Burgos, Andreas N. Alexandrou

"Processing of metal alloys in their mushy state represents a new trend in metal processing. As part of this process, known also as thixocasting, a specially prepared slurry at a temperature in the mushy region is injected into a die. Parts produced using this technology offer better mechanical properties than those produced by casting, and comparable to those of forged alloys.In thixocasting, semisolid slurries are highly concentrated suspensions of rounded rosette-like crystals in eutectic liquid. The mechanical behavior of the slurry is determined by the structure and properties of the skeleton formed by the alpha phase particles. The skeleton structure is almost never at equilibrium, and its evolution is, governed by a number of kinetic phenomena of different c11'aracteristic time-scales. Therefore, the skeleton structure depends on the mechanical and thermal history of the material. As a result of these kinetic processes, the rheological properties of the material, such as effective viscosity and yield stress, decrease with structure breakdown, and increase with its development. In the present investigation, the behavior of semisolid slurries during processing is modeled using the conservation equations, and a Herschel-Bulkley fluid model. The rheological parameters are assumed to be functions of the solid volume fraction, and of a structural parameter that changes with processing history. The evolution of the structural parameter is described by a first order kinetic differential equation that relates the rate of build-up and break-down of the solid"

Jan 1, 2000

By F. Qian

Direct impingement of molten metal baths by a gas jet is commonly encountered in such processes as BOF and electric arc furnace steelmaking. Shape and local fluid mechanics in the impinging region is important because it determines the interaction of the metal pool with the surroundings. Goal of the present work is to characterize and understand the interfaces at the impinging region. Using a physical model consisting of water/corn oil and water/kerosene as surrogates for metal/slag, interface shapes for slag-gas, slag-metal and metal-gas are investigated. Influence of transport properties of the two liquids on the shape and flow fields are also experimentally determined under various impinging jet conditions, namely jet momentum and jet height. The viscosity of the slag layer (corn oil or kerosene) has the most significant effect on the interface shape and the induced flow fields. The interface shapes were measured both photographically and by using a surface- tracking resistance probe. The limiting condition at which the jet breaks through the corn oil or kerosene layer and reaches the water layer was determined experimentally

Jan 1, 1994

By Vadim J. Jabotinski

This paper describes several areas of application for electron beam processing of materials. The technology and use of electron beam systems in gas phase synthesis reactions are described. Gas phase reactions may be used to generate ultra- fine metal or ceramic powder that are very pure and crystalline. Among the examples presented are: the generation of nanometer sized metal powders and the gas phase synthesis of silicon carbide for silica and methane. The experimental system is described and future theoretical and experimental objectives are identified.

Jan 1, 1998

By M. Neises, M. Roeb, C. Sattler, S. Stenger

"A two-step thermo-chemical cycle process has been developed and investigated. It is based on metal oxide redox pair systems, which can split carbon dioxide as well as water molecules by extracting oxygen atoms and reversibly incorporating them into their lattice. If concentrated solar radiation is used as the heat source, a promising method exists to produce synthesis gas from water and CO2. An easy way of operation is gained by the combination of a ceramic substrate as the absorber structure, which can be heated to high temperatures with concentrated solar radiation, and of a metal oxide coating which is capable to carry out the redox reactions. The performance and kinetics of a ferrite based redox material coated on ceramic substrates were investigated in a laboratory set-up. CO2 could be reduced with significant conversions. In addition, several side reactions were observed like the formation of carbon and like the Boudouard reaction.IntroductionThe search for alternative energy carriers and for processes able to reuse carbon dioxide stimulates the research for sustainable routes of alternative fuel production. In the scope of this search thermo-chemical processes combined with sources of concentrated solar energy have become more and more attractive. Ideally, the only raw materials for such processes are water (H2O) and carbon dioxide (CO2) enabling not only a process free of emissions, but also allow to reduce emissions of other processes by reusing CO2 to provide synthesis gas, which itself can be applied to produce chemical commodities or even better synthetic fuels like methanol or petrol.In contrast to the direct splitting of those raw materials, thermochemical cycles split water and CO2 in several steps and enable hydrogen (H2) and carbon monoxide (CO) generation at temperatures controllable by today’s technical equipment. One of the most interesting thermochemical cycles is a two-step process using metal oxide based redox systems. During the first step of this cycle (the regeneration step) the metal oxide is reduced setting some of its lattice oxygen free according to reaction (1). In the next step (the splitting) the reduced and activated material is oxidised by withdrawing oxygen from water and CO2 and at the same time hydrogen and CO is set free according to reactions (2a) and (2b) respectively."

Jan 1, 2011

By A. V. Tarasov

In order to improve technical, economic and environmental performance of hydrometallurgical processing of intermediate products containing copper and nickel, the Gintsvetmet Institute and the IMET Institute of the Russian Academy of Sciences have conducted studies into the efficiency of the use of alternating current of industrial frequency on processes applied for hydrochemical leaching of various copper- and nickel-containing materials. It has been found that: 1.Imposition of alternating current over the process of leaching of softly reduced nickel oxide with recycled copper sulfate solutions resulted in an increase by 20 to 30% of the rate of the copper cementation process and reduced by 20% its activation energy. At the same time, the recoveries of nickel, cobalt and iron to the leach solution increased up to 82.2%, 78.5% and 57.1%, respectively, and that of copper to the cement precipitate up to 74%. Optimal process conditions have been identified with respect to the current density, electrode material, copper concentration in solutions and the process temperature. 2.In the process of hydroelectrochemical sulfuric acid leaching of nickel and copper sulfides, the grain size, the phase form of sulfides, the solution composition (H2SO4, Cl?, Cu2+, Fe3+)and the current amperage had an effect on the nickel recovery to the solution, which reached 90%, while the degree of copper transfer to solution did not exceed 20%. The process of hydroelectrochemical sulfuric acid leaching of nickel and copper sulfides with an addition of Cl? made it possible to selectively recover nickel into the leach solution along with concentrating copper in the leach residue. 3.When subjecting samples of commercial-grade magnetic fractions of converter matte to sulfuric acid leaching, the imposition of electric current, the concentrations of sulfuric acid and chloride ion in the solution and the duration of the reaction process had an effect on the process. The nickel recovery was 85% and that of cobalt and iron was 95% and the recoveries reached 97.5%, 98.3% and 99.8% as a result of repeated treatment of the primary residue under similar process conditions. Up to 75% of copper, 75% of sulfur and 99.0-99.5% of palladium was concentrated in the solid reach residues. The experimental data obtained indicates that the use of AC for hydroelectrochemical sulfuric acid leaching for separation of copper- and nickel-containing intermediate products has favorable prospects.

Jan 1, 2003

By Pekka Taskinen

The converter-less nickel matte smelting technology (DON) adopted more than 20 years ago in Boliden Harjavalta smelter has been since that applied successfully to the processing of large number of nickel sulphide concentrates of various Ni-to-Cu ratios and MgO contents. The operational point of the technology is far from the conventional primary nickel smelting in the smelting-converting route. Therefore, a careful scouting of distribution equilibria of the base and trace elements in the smelting conditions of DON process has been conducted, in order to obtain quantitative information about the equilibria and thermodynamic properties of the nickel mattes at low iron concentrations, less than 10 wt% [Fe] in matte. The series of investigations has included novel experimental and analytical techniques for increasing the reliability and sensitivity of the phase equilibria as well as the element distribution observations carried out in typical high-grade nickel matte smelting conditions.

By Steven Wright

The reduction of a slag produced 6om the recycling of lead batteries was studied in a kilogram scale laboratory investigation by reacting with graphite at temperatures of 1180 and 1200°C. Simultaneous reduction of PbO, Fe203, Sb203 and As203 occurred with the Sb and As reporting to the metal while the lead content in the slag was above 2 wt%. The Sb and As distributions between metal and slag were strongly affected by temperature and slag oxidation state. The rates of reduction of PbO and Sb203 increased with increasing slag basicity and temperature and decreased as the PbO content in the slag decreased. The reduction rate of PbO from these slags was similar to other industrial lead slags at the same CaO/SiO2 ratio and temperature. The implications of the behavioural similarities of the antimonous slags during reduction with carbonaceous reductants and other lead slags are briefly discussed.

Jan 1, 1994

By W. P. lmrie

The recent years have seen many copper smelting operations become uneconomic due to a combination of low metal prices, high energy and labor costs, environmental requirements and high investment costs for modernization or replacement. Since a copper commodity requirement remains, the industry will recover, but many operations will need to determine which processes can offer the best prospect for economic operation and readiness for reliable investment and implementation. Corporate investment decisions involve the judgment of many factors in addition to topical technical aspects. Consideration of plant management and operational aspects are thus included. Taking account of such proven processes as conventional, flash and continuous smelting, plus modified conventional and new unproven processes, this paper gives a systematic approach to aid optimum choice for a modernization or grassroots investment. Actual achievements in energy form alternates, conservation and cost effectiveness are highlighted, and areas of remaining potential for energy saving are discussed.

Jan 1, 1983

By W. Kunda

A laboratory study was carried out on the treatment of sulphidic copper concentrates in aqueous chloride systems under elevated temperatures and oxygen overpressure. Exploratory tests showed that chalcopyriteoxidizes with various chloride salts to form, depending upon the pH of the system, soluble copper chloride or insoluble copper oxychloride salts; the copper can then readily be recovered from the solution or residues respectively. During the leaching, iron was oxidized to iron oxide and remained in the leach residue while the bulk of the sulphide sulphur was oxidized to the elemental form with a minor portion oxidized further to sulphate. The presence of metal chloride salts in the system increased the oxidation rates of chalcopyrite and depressed the solubilization of iron in the system. A systematic oxidation leach study carried out in (1) ammonium chloride and (2) sodium chloride systems showed that the former system required little or no HC1 addition while the latter required 2 mol of HC1 per mol of dissolved copper (plus zinc). The copper was recovered from the cuprous or cupric chloride leach solutions by cementation with iron. Extractions of 99% copper and zinc, 97% silver, and negligible iron were obtained. Sulphur was oxidized to the elemental or sulphate form; the relative proportions of the total sulphur were 60 and 30% for system (1) and 80 and 10% for system (2). A flowsheet for a conceptual process with minimal reagent requirements was proposed.

Jan 1, 1976