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By James O'Brien, Lyman Frost, Grant Hawkes, S. Elangovan, Manohar Sohal, J. S. Herring, Joseph Hartvigsen, Carl Stoots

"Pressing environmental and energy security concerns have brought much needed attention to economic production of hydrogen as the secondary energy carrier for non-electrical markets as well as to meet increasing demand for crude upgrading and desulfurization. While steam reforming of natural gas is currently the dominant method of hydrogen production, it is depleting a valuable fossil fuel while emitting green house gases. Thus, in the long run, efficient, environmentally friendly, and economic means of hydrogen production using nuclear and renewable energy needs to be developed. High temperature electrolysis using solid oxide electrolyte cells is an exceptionally efficient means of generation of high purity hydrogen. It is also capable of directly converting steam and CO2 into synthesis gas. This co-electrolysis process enables conversion of CO2 recovered from concentrated industrial sources into a feedstock for synthetic fuels production. Use of CO2 provides a means of storing hydrogen in a concentrated and convenient form – a hydrocarbon. This is also an effective storage medium for intermittent renewable energy sources such as wind and solar.Ceramatec, Inc and the Idaho National Laboratory are applying solid oxide fuel cell technology to the production of synthesis gas by high temperature co-electrolysis of steam and carbon dioxide. This technology utilizes solid oxide fuel cell stacks to electrochemically remove oxygen from steam and CO2, leaving a clean stream of hydrogen and carbon monoxide suitable for fuel synthesis. By varying the relative concentrations of carbon dioxide and steam, the hydrogen to carbon monoxide product ratio can be controlled as required by the desired type of synthetic fuel being produced from the syngas. The resultant synthesis gas has been used as the feedstock to produce synthetic methane and Fischer Tropsch liquid fuels.Alkaline and proton exchange membrane electrolysis cells typically operate below 100°C, while solid oxide electrolysis cells operates in the 750-850°C range. This higher temperature improves the efficiency significantly. Practically, it translates into a lower cell operating voltage, 1.1-1.4V for high temperature electrolysis vs. ~1.8V for water electrolysis. Hydrogen production is stoichiometric with current in all types of electrolyzers.Carbon dioxide is a valuable resource as a feedstock for energy storage as a hydrocarbon. There is a vast amount of renewable energy that cannot be effectively utilized as grid electricity, but which could be used to convert CO2 to hydrocarbons, offering a solution to the even more difficult (than supplying grid power) challenge of production of sustainable, domestic transportation fuels. Conventional electrolysis and chemical processes could be deployed to accomplish this conversion. However, high temperature co-electrolysis of CO2 and steam to produce synthesis gas using solid oxide fuel cell technology has the potential of improving the efficiency by nearly 50%. A domestic synfuel industry will enable a much larger reliance on intermittent renewable energy than can be accommodated by conventional electric demand profiles while increasing our energy security."

Jan 1, 2010

By V. I. Lakshmanan

Crown ethers are gaining importance in separation technology specifically for rare earth elements (REE, La to Lu plus Y) and precious metals (Au, Ag, Pt, Pd, Rh and Ir) due to their specific binding ability, metal complex stability and high extraction efficiency. The selectivity of crown ethers in extraction of these metals depends on different factors, including the cavity diameter and nature of a donor atom of the crown ether, size and charge of the metal ion, diluents and counter ion. Demand for strategic REE and precious metals are consistently increasing in the world while the separation of these metals is most challenging tasks. In this paper, the use of crown ethers in separation of REE and precious metals, reaction mechanisms and simplified process flowsheets will be elucidated. New reagents with high selectivity for the separation of these metals are further expected to produce high purity metals.

By Arthur E. Morris

Process modeling software is used extensively in process engineering, but there is a notable lack of affordable software for educational uses. This paper describes two educationally oriented software programs for thermochemical modeling of processes involving metals, minerals, and ceramic materials. Both programs run as Excel@ spreadsheet files. The first is FREED, a thermodynamic database program containing datafiles for 2500 species. It contains the entire U. S. Bureau of Mines and most of the U. S. Geological Survey database, plus data for scores of other species drawn from various sources. Several modules are available for manipulating and viewing the data. The second program is THERBAL, for making thermodynamic calculations using FREED data. Equilibrium calculations can be made for systems with non-ideal solutions, for a specified set of pressure, temperature, and input amounts of reactants. An optional heat balance is also calculated. The results are displayed as tables or charts in Excel worksheets. Examples of the use of THERBAL will be given for the reforming of natural gas for DRI production, DRI production, and EAF steelmaking. Some observations will be made on its use in the classroom. The development of FREED and THERBAL was initially carried out at the Department of Metallurgical Engineering, University of Missouri - Rolla as part of a project to preserve and enhance the Bureau of Mines database. The current versions were developed privately by the authors.

Jan 1, 2002

By Ray Y. Lin, Randall A. Blue

"Joining of silicon carbide with infrared using a mixture of Si-30wt.%C as the brazing material has been investigated. Joining was performed at a temperature of 1500 °C in a flowing argon atmosphere for processing times ranging from 5 to 60 seconds. The joining filler materials include thin film silicon obtained by thinning down silicon wafers to about 70 /!m and graphite powder of a 15 /!m average particle size. Joint strengths were determined with a specially designed shear-in-compression jig for testing shear strengths of brittle materials. Cross section examinations of the joined specimens with optical microscopy, scanning electron microscopy and transmission electron microscopy have shown that all joints are essentially void free with excellent wetting between the base SiC and the brazing material. Silicon carbide in the B form has been identified as the reaction product in the joining zone with a transmission electron microscope (TEM) and selected area diffiaction (SAD) analysis. At 1500 °C with a joining time of 60 seconds, the joint has consisted of primarily SiC. With such a high SiC content in the joint, the joint strength is comparable to those by other joining techniques, such as diffusion bonding, as reported in the literature. A kinetic model for the formation of SiC from liquid silicon and carbon is proposed to explain the observed joint microstructural evolution.IntroductionSilicon carbide is of great interest for high temperature structural applications because of its excellent high temperature strength, wear resistance and anticorrosive characteristics [1]. Even though the interest in SiC is high, the use of the material has been limited by the high cost and difficulties involved in forming components of complicated shapes [2]. It is these limitations that necessitate the development of effective joining techniques that are cost effective and able to provide strong joints."

Jan 1, 1996

By Marco Olper

After two years of extensive research a new and innovative modification to the CX-EW process has been exploited. This process, called CX-EWS, avoids completely all the critical aspects of the previous process which affected the cost of the energy, of the chemicals and of The maintenance of the insoluble anodes. All these benefits reflect a saving of about 30% of The operating costs compared to the present traditional production and allow for a total operating costs of less than 6.5 cts/lb. lead (net of raw material cost). With this new technology it is allowed for the first time the treatment in the same plant facilities of both primary lead sulphide concentrate and spent batteries. The paper describes the technical and economical aspect of the new process with a feasibility study for 150,000 t/y spent battery facility throughput.

Jan 1, 1995

By Jaroslav Horskoý, Miroslav Raudenský, Bogdan Filipic, Božidar Sader

This paper describes main elements and practical use of the computational system for automated setting of optimized casting conditions in the continuous casting of steel. The system consists of the heat transfer model of the process, empirical metallurgical criteria, and optimization algorithm. The physical model of the, strand temperature distribution relies on the classical Bennon-Incropera mixture continuum formulation for the convective-diffusive heat transport. Fluid flow effects are considered through enhanced thermal conductivity of the liquid phase. The model is solved by the operator-splitting Crank-Nicolson finite volume version of the Voller-Swaminathan scheme. The solution procedure is coupled with the IDS solidification analysis package. Boundary conditions for the strand cooling rely on combination of the generic and plant-specific mold, spray, and roll heat transfer coefficients ' by coping the effects of the casting speed, casting temperature, casting powder, mold oscillation mode, steel grade, water or air-mist spray type, running water, trapped water on the rolls, and radiation. The caster safety and productivity and the quality of the strand are related to nine empirical metallurgical criteria. The criteria ensure the caster safety and economy as well limit the internal, longitudinal, and transversal surface cracking possibility. The problem of finding optimum casting parameter values is stated as a minimization problem based on the analytical form of the cooling criteria evaluated from the steady-state temperature distribution of the strand. To solve the optimization problem, a genetic algorithm is employed. The algorithm explores process parameters settings heuristically by applying the principles of biological evolution. It starts with a random set of solutions and iteratively improves them through selection and variation. Solutions are evaluated by running the heat transfer model of the process and extracting the values of the empirical metallurgical criteria.

Jan 1, 2000

By M. Tokumasu, T. Mutoh, Y. Sugawara

"In October 1986, a process computer was introduced in order to achieve an optimum combustion of pulverized coal at the reverberatory furnaces. The secondary combustion air volume is controlled based on the nitrogen oxide concentration of the off-gas from the reverberatory furnaces. The carbon monoxide concentration has strong relation with the concentration of nitrogen oxide under the situation of using alternative fuels, such as chipped tires and p,ulverized coal. Using this computer aided combustion control system, both nitrogen oxide and carbon monoxide concentrations were stabilized and conventional monitoring and controlling apparatuses were absorbed into this computer system. Due to this easily operated system, labor cost was reduced and the operation of the reverberatory furnaces and the off-gas treatment plant became stable.IntroductionOnahama Smelter and Refinery started its operation in April 1965 as a large scale copper smelter and refinery in Japan. The green charged reverberatory furnaces were introduced and bunker C oil was chosen as the fuel for the reverberatory furnaces. After the oil crises, Onahama was forced to use cheaper fuels such as coal and waste tires, i.e., alternative fuels instead of the expensive oil. As the amount of the alternative fuels fed to the reverberatory furnaces increased, the concentrations of nitrogen oxide and carbon monoxide in the off-gas became unstable. Consequently, the fluctuation of the combustion condition became not to be negligible in view point of a combustion efficiency and pollution regulations. A process computer has been introduced to overcome these off-gas troubles and to reduce the operating cost of the smelter.Outline of Operation HistoryInitially, the operation started by one reverberatory furnace and then the capacity was expanded almost twice by additional furnace in December 1972. As shown in Figure I, the smelting throughput was depressed after oil crises in 1973 and 1978. From 1983 to 1985, some copper mines stopped their operations because of low price of copper metal. During this period, Onahama suffered from the shortage of concentrate production levels were depressed."

Jan 1, 1989

By T. T. Nguyen, D. R. Gunasegaram, D. Celentano

"Heat transfer rates at the casting-mold interface are believed to be substantially reduced by the formation of an interfacial gap during the course of solidification of aluminum alloys in permanent molds. In the current work, the effect of force-cooling a permanent composite mold on (i) the initiation and growth characteristics of the gap and (ii) interfacial heat transfer rates are studied. Interesting comparisons are made with the case where no cooling is employed. Casting and mold displacements are measured using L VDTs, and the mold is force-cooled by air jets.IntroductionIn a gravity casting situation where an aluminum alloy solidifies in a permanent mold, a gap initiates and grows between the shrinking casting and the expanding mold (1). It is widely believed that the formation of this gap, customarily referred to as an 'air gap', results in a substantial reduction in the heat transfer coefficient at the casting-mold interface (2), and hence is an important factor in solidification studies.The nature of the air gap formation process is thermo-mechanical. The rate of heat loss from the casting first determines the rate of solidification, which, in turn, decides when the gap initiates. The reason for this is the requirement for the solidified casting surface 'skin' to gain sufficient thickness, and hence strength, to be self-supporting. Once the gap initiates, the gap width controls the rate of heat loss from the casting, which, again, determines the rate at which the gap expands."

Jan 1, 1997

By Ross W. Smith

Microorganisms are increasingly finding use in mineral processing and hydrometallurgy both for the enhancement of mineral engineering operations and for the remediation of mineral industry wastes. Some of the applications, such as biologically assisted leaching of sulfide ores and biooxidation of refractory sulfide gold ores, are established commercial processes. Others, such as the use of organisms for the removal of heavy metal ions from dilute aqueous streams, are nearing commercial application. Other uses of microorganisms are potentially possible. These include use of microorganisms in leaching non-sulfide ores, the flocculation or flotation of minerals and remediation of toxic chemicals discharged from mineral engineering operations.

Jan 1, 1993

By J. S. Becker

Technology developed and first implemented in the United Kingdom enables very low grade aluminum scraps containing oils, organics, plastics and ferrous metals to be directly charged, without pretreatment, into a unique melting furnace. The system has been in full scale production for over three years. The oxy-fuel-based furnace design incorporates internal afterburning in the furnace's hot zone, producing excellent thermal efficiency and very low emissions. The furnace is inherently low in NOx. This paper will provide both theoretical background and extensive operating results for this new melting concept. Applications describing both purpose built new furnaces and retrofits of existing reverberatory furnaces will be presented. Extensive operating emissions data will be presented.

Jan 1, 1996

By E. F. Vegman, Ndabezinhle Dube

"In the practice of conventional sintering, production is always afflicted with the problem of being unable to get a uniform quality of produced sinter in the bed. Invariably the top layer of the sinter cake is composed of weak but highly sinter, while the bottom layer is over-fused, forming a sinter that is very strong but less reducible. These symptoms point to a variable distribution of the heat balance in the process of sintering which results in a deficit of heat in the top layers of the sinter bed and an excess of heat in the bottom layers, due to an increasing input of regenerated heat in the heat balance down the bed. This causes losses in the productivities of the sinter machine and the blast furnace.The current work was designed to improve on the solution to the above problem through the establishment of a more accurate combustion zone heat balance of the sintering process. This development is mostly on the method of determining the regenerated heat input in the overall heat balance. Previous methods were based on the assumption that the width and the velocity of the combustion zone remain constant through out its whole life, which is not the case since tests have shown that both its width and velocity increase as the combustion zone moves down the bed. In this work, these factors have been taken into account. Tests and calculations using the model were carried out for haematite and limonitic ores. The high sensitivity of the model to changes in the sinter mix composition and sintering conditions was demonstrated.The results present the following prospects:• The minimum theoretically possible coke breeze consumption during the sintering of any type of iron ore fines, under any sintering conditions, can be established.• The model can be used to control the metallurgical quality of the sinter in any point in the sinter bed since calculation data includes desired basicity, combustion zone temperature and FeO content in the sinter produced."

Jan 1, 2001

By Junzo Hino

Most of the waste that contains a small portion of copper is landfilled. The recycling process of copper from the waste, such as shredder residue, should be developed in order to save mineral resources and prevent environmental pollution. Shredder residue, generated from disposed automobiles and electric appliances, consists of many types of plastics, glasses and metals. The combustion heat of plastics is efficiently used for smelting in the recycling process that consists of melting and reduction. Because the waste contains numerous components the knowledge of the distribution behaviors of the main components is necessary to develop the recycling process. The distribution behaviors in the recycling process are evaluated by using the thermodynamic calculation program, HSC Chemistry. The calculation results are compared with the practical operation data of the recycling process and discussed.

Jan 1, 2003

By Mansoor Barati, Shaghayegh Esfahani

"The slag from extraction of ferrous and non-ferrous metals is a potential heat source which if treated properly can contribute to recovery of a significant amount of energy. The waste heat of slag may be used to generate steam, synthetic fuel gas, or electricity. Although several technologies have been investigated for this purpose, very little has been achieved in terms implementing the technology in industry. In this article, the development and application of various granulation techniques are reviewed and the methods to recover energy from granulated slag are discussed.IntroductionEvery year, more than 422 million tons of slag is being produced around the world as a by-product of the metal manufacturing at temperatures of up to 1300-1600°C [1, 2]. Currently slags are either disposed of or treated by processes such as granulation. Through the granulation process, most slags can be converted into a material which may be fully used as a cement feedstock. Conventional cement production is an energy intensive process with large emissions of CO2; therefore, the replacement can both be energy saving and environmentally friendly. However, for this purpose, the slag should have what is known as a “glassy” content (i.e. it should be amorphous) which requires rapid cooling rates that are not easily achieved due to the very low thermal conductivity. The main challenge in all these processes is to granulate the slag at a high cooling rate while the heat is also being recovered."

Jan 1, 2012

By Maija-Leena Metsiirinta

The behaviour of copper and lead in zinc roasting has been studied in laboratory scale roasting experiments as well as in large scale trials in an industrial fluidized bed, with the background of Outokumpu Kokkola Zinc smelter. Commercial zinc concentrates with a low and high ( up to 3 wt % ) copper content and with a low and high ( up to 3.5 wt % ) lead content were oxidized to various desulphurisation degrees in the fluidized bed to establish the reaction mechanisms and the paths for copper and lead oxidation in the roasting. Influences of the agglomerate size on the roasting kinetics and micro- scale phenomena were also determined. Optical microscopy was used on the calcine and the findings are presented as numerous photographs of the polished cross sections. SEM/EDS techniques were used for analyzing chemically the phases and particle morphologies present in the samples. Computational thermodynamics was applied to the complex phase equilibria occurring during roasting in the agglomerating calcine. A complete oxidation of zinc concentrate with a high copper and lead content requires a careful control of oxygen coefficient in the roasting in order to maintain a stable operation of the fluidized bed. Oxygen coefficient thus seems to have a significant impact on the hydrodynamic stability of the fluidized bed with fine raw materials.

Jan 1, 2003

By Maija-Leena Metsärinta

The behaviour of copper and lead in zinc roasting has been studied in laboratory scale roasting experiments as well as in large scale trials in an industrial fluidized bed, with the background of Outokumpu Kokkola Zinc smelter. Commercial zinc concentrates with a low and high ( up to 3 wt % ) copper content and with a low and high (up to 3.5 wt % ) lead content were oxidized to various desulphurisation degrees in the fluidized bed to establish the reaction mechanisms and the paths for copper and lead oxidation in the roasting. Influences of the agglomerate size on the roasting kinetics and micro-scale phenomena were also determined. Optical microscopy was used on the calcine and the findings are presented as numerous photographs of the polished cross sections. SEMIEDS techniques were used for analyzing chemically the phases and particle morphologies present in the samples. Computational thermodynamics was applied to the complex phase equilibria occurring during roasting in the agglomerating calcine. A complete oxidation of zinc concentrate with a high copper and lead content requires a careful control of oxygen coefficient in the roasting in order to maintain a stable operation of the fluidized bed. Oxygen coefficient thus seems to have a significant impact on the hydrodynamic stability of the fluidized bed with fine raw materials.

Jan 1, 2003

By H. D. Freeman

The occurrence of gold in refractory gold ores varies widely and affects the recovery process. The determination of gold and the composition of the associated minerals are important in selecting an appropriate processing scheme. However, locating the gold in an ore sample is a difficult task which requires perseverance, luck, and experience. Our experience has led to the development of a relatively fast and reliable means of deter-mining the mineralogy of ore samples through analysis combining an energy-dispersive x-ray analyser coupled to a scanning electron microscope (SEM). In some cases, a wave length dispersive spectrometer or microprobe is used to further quantify the various mineral compositions. The SEM/microprobe analysis identifies the source of problems that may arise during the recovery of gold from refractory gold ores.

Jan 1, 1981

By Patrick R. Taylor

Glass is used for immobilization of radioactive and hazardous wastes due to its durability and ability to accept a variety of waste constituents into its network structure. Alternative high temperature vitrification techniques have the advantage of increased throughput, increased waste loading and being applicable to variable and heterogeneous waste streams. However, the increased processing temperature places further concerns on the increased volatilization of contaminants, and increased corrosion and erosion of me Iter components. A database of melt properties at higher temperatures, such as partitioning, viscosity, density and electrical conductivity, in the temperature range of 1400-20000 K are being developed.

Jan 1, 2000

By A. Jakobsson

Studies of the rate of interdissolution in oxide systems in the solid state are of importance in materials processing through the powder-metallurgical route. As there is a need for following the rate of the such reactions continuously, a new method based on high temperature X-ray diffraction was developed. Mechanical mixtures of the oxides were placed in a high-temperature X-ray diffraction unit and the changes in the intensity and position of the peaks with highest intensity for both the components were followed as functions of time. A suitable theoretical model has been developed in order to interpret the experimental data and evaluate the diffusion coefficients. The method was applied in the case of the system MgO-NiO. The results obtained are compared with those obtained by another new method, based on solid-state galvanic cell technique with calcia stabilized zirconia electrolyte, developed in the Department of Theoretical Metallurgy. The advantage of the present techniques to monitor the progress of the reaction continuously make them suitable for computer control of such processes.

Jan 1, 1995

A simulation of a capper concentrate smelter was built with a capacity of 450,000 tons per year. The system's components to simulate were three : a Reverbetory furnace, a Wiente ' s modified converter ( TMC ) and two cranes. The system was classified as dynamic, stochastic and discrete. In the simulation language choice it was concluded that the most advantageous one was GPSS/H. The model verification was done through the interactive Debugger that the language has and the statistical validation was done through the result variables of sane activities, that as a whole characterize the system (charged matte and charged concentrate to the TMC, skimming white metal and skimning slag). The validation was done comparing the simulation results of these variables with the ones obtained for those variables in a specific month in the smelter. The comparison consisted in a difference of means test and in all cases the equality was accepted with a 95% of confidence. The animation tool was PROOF, a general purpose animator, that is used after processing the simulation.

Jan 1, 1994

By Ernie M. Crist, Laurentiu Nastac, Frank Spadafora

"This paper describes the modeling techniques and the experimental and computer results for two casting processes that are under development and optimization. These processes are described as follows:1) Electromagnetic stirring (EMS) during casting of Ti-6Al-4V round ingots using the plasma arc cold hearth melting (PAM) process: The purpose of EMS is to establish a singlemelt PAM process capable of consistently producing as-cast ingots without helium porosity and also having no need for surface conditioning prior to secondary processing.. The modeling approach is based on the numerical solution of Maxwell's equations, fluid flow, and heat transfer equations, and mesoscopic modeling of the grain structure.2) Casting of Ti-6Al-4V slabs using the single-melt PAM process: The purpose of slab casting is to improve yield by eliminating an intermediate blooming step for converting round ingots to slabs. The modeling approach is based on the numerical solution of fluid flow and heat transfer equations. The effects of pouring and mold temperatures on the pool and temperature profiles were studied. Also, the torch effects (such as the torch standoff and its traversing path) on the pool and temperature profiles were investigated and the best-case scenario was used in the experiments. Evaluation results at RMI Titanium Company showed that the plates made from the slabs met the mechanical properties and microstructure requirements.Acknowledgment. This work was conducted by the National Center for Excellence in Metalworking Technology (NCEMT) operated by Concurrent Technologies Corporation (CTC) under contract No. N00014-00-C-0544 to the US. Navy as part of the US. Navy Manufacturing Technology Program. Dr. K. b. Yu from RMI and my colleagues from CTC are acknowledged for their comments on this work."

Jan 1, 2004