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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 James E. Simpson, Suresh V. Garimella, III de Groh

"An experimental and numerical study of the horizontal Bridgman growth of pure succinonitrile (SCN) and of a succinonitrile-1.0 mol. % acetone alloy (SCN-1.0 mol. % ACE) has been performed. Experiments at growth rates of 0, 2 and 40 µmis were investigated. The solid/liquid interface was stable (non-dendritic and non-cellular); however, it was not flat. Rather, it was significantly distorted by the influence of convection in the melt and, for the growth cases, by the moving temperature boundary conditions along the ampoule. For the alloy, the interface was determined to be unstable at growth rates greater than 2.8 µmis, but stable for the no-growth and 2 µmis growth cases. When compared to the pure SCN interface, the alloy interface forms closer to the cold zone,· indicating that the melting temperature has been suppressed by the addition of the alloying element. Two-dimensional computer simulations were performed for the no-growth case for both the pure and alloy materials. These simulations indicate that a primary longitudinal convective cell is formed in the melt. The maximum magnitude of velocity was calculated to be 1.515 mmls for pure SCN and 1. 724 mm/s for the alloy. The interface shape predicted by the computer simulation agrees well with the experimentally determined shape for the pure SCN case. In ongoing work, numerical simulations of the process during growth conditions are being performed.IntroductionIncreasingly, advanced materials used in the aerospace, automotive, optics and electronics fields require low levels of defects and high levels of solute uniformity. Directional solidification by the Bridgman process is widely used for synthesis of these high-quality materials. During Bridgman crystal growth, heat and mass transfer by both thermal and solutal gradient-driven convection and diffusion influence the shape of the solid/liquid interface and dopant segregation levels, and hence, directly determine the final crystal quality. Key process parameters include the applied furnace temperature distribution and rate of translation, ampoule properties and furnace orientation."

Jan 1, 1999

By D. J. Senor

Closed chamber incineration (CCI) is a novel technique by which irradiated nuclear graphite may be destroyed without the risk of radioactive cation release into the environment. The process utilizes an enclosed combustion chamber coupled with molten carbonate fuel cells (MCFCs). The transport of cations is intrinsically suppressed by the MCFCs, such that only the combustion gases are conducted through for release to the environment. An example CCI design was developed which had as its goal the destruction of graphite fuel elements from the Fort St. Vrain reactor (FSVR). By employing CCI, the volume of high level waste from the FSVR will be reduced by approximately 87 percent. Additionally, the incineration process will convert the Sic coating on the FSVR fuel particles to SiO2, thus creating a form potentially suitable for direct incorporation in a vitrification process stream. The design is compact, efficient, and makes use of currently available technology.

Jan 1, 1994

By P. Umadevi

In the light of the discovery of the new super-conducting YBa2Cu3O7-x (YBCO), reactions in the Y2O3¬CuO-BaO system at 1300°C was investigated. The search was for any new phase that may be formed in the system at 1300°C (only 950°C reactions are known so far). 35 mixtures of different compositions were prepared and heated at 1300°C. No new phase was obtained. It was found that YBCO is decomposed at this temperature and Y2O3 and BaCO3 are the major components in the solid obtained after firing in air. However, on cooling the melt slowly and annealing at 950°C YBCO reforms. Such reactions on cooling might have implications on processing of the superconductor YBCO for practical applications as well as on its crystal growth by flux method.

Jan 1, 1989

By N. A. Barcza

DC plasma-arc technology using a hollow graphite electrode (cathode) has been successfully implemented in the primary metallurgical industry in South Africa up to the 30 MW scale. Mintek has applied its expertise base, established over the past fifteen years, to testing the treatment of metallurgical wastes such as carbon- and stainless-steel plant dusts, lead- and zinc-containing slags, and residues from the base-metal industry. Favourable results have been achieved, and disposable products were produced. The evaluation of numerous wastes indicates that recovery of zinc as metal gives the best economic return from these sources. Direct recovery via a splash condenser or electrolytic zinc extraction from fume are the two preferred alternatives under review. In both instances dehalogenation is an important issue, but can be achieved by suitable treatment processes. The Enviroplas technology provides a flexible, commercially viable approach to the treatment of a wide variety of wastes. Mintek, together with its associate Pyromet CC, are installing a plasma- arc pilot-plant facility with both an ISP lead-splash condenser of about 5 t/d condensed zinc capacity and a combustion chamber to burn zinc vapour to zinc oxide. This will demonstrate the suitability of the Enviroplas technology for treating specific metallurgical wastes, so that customized industrial plants can be engineered based on large-scale testwork.

Jan 1, 1994

"Depletion of known ore reserves and increased demand for precious metals have caused a revolution in biohydrometallurgical processing technology for gold recovery. Known ore deposits and future discoveries are most likely to be lower grade sulfide ores that can be difficult to recover with current leaching technology. Future metal recovery operations will increasingly use bio-oxidation techniques.Bacteria are an integral part of mineral cycling and mineral transformation in nature. Although biological processes are recognized as part of the mineralization and oxidation reactions in some ore deposits, they have only recently been applied to enhancing metal recovery in hydrometallurgical procedures. This paper explores the traditional metallurgical application of biological leaching and oxidation reactions and reviews the complete range of bacteria available for metal recovery systems. Pre-treatment of ores with bacteria improves metal recoveries in tank leaching systems and shows promise for heap leaching methods.IntroductionThere is no longer any question that bacteria playa natural role in the on-going transformation of some ore deposits (1,2). As applied to sulfide ores, a few strains have been specifically identified that exhibit a natural leaching potential (3). These bacteria can be isolated from waters and soils in old mining districts where they contribute to continuing leaching and pollution problems in acid drainage and heavy metal solubilization. Sulfur and iron bacteria as well as many heterotrophic strains have also been found in ore deposits and sedimentary rocks at depths up to 2000 meters (4). Their presence in both ore deposits and processed ores shows the microbial association with natural leaching and the potential role that bacteria can play in the development of new leaching technology."

Jan 1, 1988

By L. R. Verney

About 75% of the market economy countries's supply of cobalt is produced in Central Africa by Zafre and Zambia. Zafre alone accounts for more than 55% and has the resources and capacity to increase output significantly at any time so its dominant position is unlikely to be challenged in the foreseeable future. Other producers from domestic resources are Canada, Australia and South Africa; and Cuba, probably the most important producer outside of the Market Economy countries. Belgium, Norway, France, Japan and Finland produce cobalt from imported materials. While there are "cobalt ores", inMorocco, USA, Canada and the USSR, the mineralisation is complex and cobalt extraction is costly. In ZaPre and Zambia cobalt is a by-product of copper; in Canada, Australia, France, and Cuba it is a by-product of nickel; and in South Africa it is a by-product from the production of Platinum Group Metals. Thus the levels of cobalt production are inevitably related to the production of other primary metals. While some cobalt is produced by predominantly pyrometallurgical methods most of the world's cobalt is produced hydrometallurgically. The existence of large hydro-electric power plants and the mineralogy of the copper and cobalt concentrates encouraged research and development in Zafre of the recovery of copper and cobalt by electrowinning from sulfate solutions; much pioneering work was carried out, which lead to construction of the two largest copperlcobalt hydrometallurgical plants in the world, at Shituru and Luilu. Similar systems were adopted in Zambia. In Canada high pressure hydrometallurgical processes based on the sulfate system were developed and adopted in Australia, the Philippines, Finland and South Africa. Meanwhile developments in chloride hydrometallurgical extraction of nickel and cobalt lead to its use in the extraction of cobalt in Norway, France and Japan.

Jan 1, 1988

By Renato G. Bautista

The chemistry of the separation of metals from each other and from the other undesirable components involve multiple simultaneous chemical reactions. In the case of leaching, the heterogeneous chemical reactions between the solid and the liquid phase may be limited to a few reactions. In the homogeneous liquid phase, the number of simultaneous chemical reactions could be double or triple that of the number of heterogeneous reactions:. The rate of dissolution becomes very dependent on the changing concentrations of the significant chemical species taking part in the multiple reactions in both the heterogenous and homogeneous phase. The rate expression developed for the process must take into account the mechanism of chemical reactions in order to best represent the actual process. This paper also examine the role of mass transfer with chemical reaction in the develpoment of the rate equations for dissolution, liquid-liquid extraction, membrane separation, precipitation, and electrodeposition.

Jan 1, 1996

By Ken-ichi Machida

"Surface modification of R-Fe-N intermetallic compounds was made to improve their magnetic property and nitrogenabsorbing ability, arid high-performance resin-bonded magnets and nitrogen storage materials were developed: Surface coating for Sm2Fe11Nx by the zinc metal produced via photodecomposition of Zn(C2Hs)2 was effective to avoid the further oxidation in the molding process of the fine powders for bonded magnets and the resulting (BH)max values were improved to -186 kJm-3. Meanwhile, R2Fe17 as the mother compounds for RzFe11Nx was highly active for decomposition of NH3 molecule and subsequent nitrogen absorption as metal nitrides. Furthermore, even inert Nz molecule was dissociated on them by impregnating Ru metal and the resulting nitrogen atoms were absorbed in the crystal lattice of R2Fe17. These results demonstrated that the nitrogen storage system was established by cycling the nitrogenation and hydrogenation of RzFe11/R2Fe11Nx materials.IntroductionProcessing for rare earth metals and intermetallic compounds requires well-controlled conditions in order to avoid the oxygen contamination involved in it due to their high reactivity, as causes the serious damage for materials such as magnets, metal hydride for hydrogen storage, and so on. Rare earth-iron intermetallic compounds, R2Fe17, provide the corresponding metal nitrides (R2Fe11Nx) by heating in N2 or a mixed gas stream ofNH3-H2 [l] and, among them, Sm2Fe11N3 has been particularly noted as one of the promising materials for high-performance permanent magnets such as bonded ones [2- 6]. Usually, the nitrogenation for Sm2Fe17 is made in Nz, but it needs the much more hard conditions of reaction pressure (-10 MPa), temperature (-550°C) and time (-72 h) than the nitrogenation in the NH3-H2 mixture [l]. In the latter case, a significant amount of nitrogen can be interstitial introduced in· the R2Fe17 crystal lattice (x=-7) under the more moderate conditions than in N2 (at 0.1 MPa and -450°C for -3 h) [3-6] and then, in a similar manner as metal hydride systems [7], the excess nitrogen in RzFe1 7Nx (x>3) is reversibly desorbed by heating at a temperature around 500°C in Ar to form the RzFe11N3 compounds. This behavior of nitrogen absorption and desorption has a close relation to the sites for nitrogen in the crystal lattices."

Jan 1, 2000

By Thomas R. Wildeman

Experimental methods for studying vapors over solid minerals are reviewed and an especially developed method using atomic absorption is described. The method is used to study vapor pressures over Te. Ag, Au, Ag2Te, and AuTe2 from 250°C through 10S0oe. Vapor pressures observed and, concurrently. sintering properties are significantly altered by the form of the solid. The vapor pressures of the tellurium compounds reveal complex processes occurring on the surfaces of the solids. The data given also point out a method of recovering precious metals from their telluride minerals w

Jan 1, 1987

By David M. Davidson

Seven intrusive phases have been mapped to date in the 1 b.y. Red Bluff Granite Complex (RBGC) near El Paso, Texas. This batholith is 20 km2 in area and intrudes older supracrustal units as well as a trachyte ignimbrite cap. Two early microgranite sills are spatially separated 6 km from a porphyritic, three-phase "ring complex" by a tin-bearing, biotite granite which cores the RBGC. These units are intruded, in turn, by a riebeckite granite which locally exhibits lineated and pegmatitic textures as well as exceptionally high light REE and Zr values (800 ppm La; 3,000 ppm Zr). The riebeckite granite is exposed in three separate occurrences within the Franklin Mountains. REE values in the RBGC are depleted in HREE and show distinct negative Eu anomalies. Typical La/Yb ratios are 5:1-2:1 with Eu values ranging from 10-80 ppm. The mineral source of the high REE values in the riebeckite granite has not yet been specifically identified, but is believed to be zircon.

Jan 1, 1988

By Scott A. Howard

MgO is routinely used as the basis for refractory materials, however, its susceptibility to hydration may result in dimensional instability and subsequent failure. The addition of boron has been shown to reduce th,e hydration susceptibility of MgO yet its dissolution into certain grades of steel may degrade their performance. In order to predict the efficacy of reducing hydration susceptibility by the incorporation of mono-, di-and tri-and quadravalent cations, the lattices of various cation-substituted systems were modeled. To more accurately simulate the substituted lattices, either cation or anion vacancies were incorporated to maintain electrical neutrality and all possible arrangements of defects in a 2x2x2 MgO supercell were investigated. Correlations were then made between the lattice energies of these systems and their susceptibility to hydration as reported in the literature. The results indicate the presence of higher charged cations tended to increase lattice stability while the cations with lower valency tended to have lower lattice energies. The relatively small body of experimental results available in the literature are consistent' with this study's results.

Jan 1, 1989

By Onuralp Yucel, Ahmet Turan, Murat Alkan, Hasan Ozer

SHS (Self-propagating High-temperature Synthesis) is one of the important methods to synthesize B4C powders. The process contains the reaction of boron oxide powders (B2O3) with magnesium reducing agent and carbon black carburizer. SHS products are leached in HCl media to purify synthesized B4C powders in the following step. In the present study, effects of various functional additives (KClO3, KHSO4, MgSO4.7H2O, NaCl, MgO and Na2SO4) in the SHS stage were carried out. Various proportions of the additives were mixed with the initial SHS charge mixtures. Two different molar ratios were employed in the initial SHS mixtures as 1:3:0.8 B2O3:Mg:C and 1:2.5:0.8 B2O3:Mg:C. After the SHS step, HCl leaching process was applied to the SHS products. Filter cakes were dried and characterized by using X-Ray Diffraction Spectroscopy, BET and chemical analysis techniques.

Jan 1, 2015

By R. Burkhard

Recovery of metals from complex mixed wastes is a challenging task of modem material and waste management strategies. Thermal methods are an important tool in this respect. Plasma turned out to be particularly useful for treatment of complex or toxic wastes and residuals. In order to study plasma processes at reasonable costs, a pilot plasma plant has been used and wastes like ~pent Raney-Nickel catalysts, copper and ah.:lminum drosses, and. other metal containing wastes were investigated. The paper summarizes the most significant findings

Jan 1, 1995

By S. Seetharaman

In the processing of molten metals, it is extremely important to monitor continuously the concentration levels of various minor elements, In the production of common metals like copper, iron and aluminium electrochemical sensors involving solid, as well as liquid electrolytes are being increasingly used to measure the concentrations of minor elements The present paper deals with the electrochemical principles underlying these measurements and the possible errors involved. One of the major difficulties in the case of the solid electrolytes is to correct for the consequences oldie electronic contribution to the conduction of the electrolyte. The application of the electrochemical sensors for molten metals processing involves designing of these probes to withstand the industrial operating conditions. In this respect, significant achievements have been made with respect to the design of oxygen probes for liquid metals in general and liquid copper in particular. Some of the salient design features are discussed in the paper, The application of auxiliary electrodes for impurities in molten metals like phosphorus in copper and silicon in iron are taken up. The development of oxygen sensors for slags is given special attention. Recent developments' in the field of sensor technology, as applied to metals processing are highlighted.

Jan 1, 1996

By Dajian Wang

To obtain the thermodynamic properties of a multicomponent liquid alloy system over the whole range of concentration at an arbitrary temperature, the free volume cell theory has been applied to derive the formula of activity coefficients of liquid solutions based on the infinitely dilute solutions at some temperature. The linear logarithmic relationship between activity coefficients of binary dilute solutions and reciprocal of absolute temperature have been verified, and are in good agreement with the experimental values from the literature. The Monte-Carlo algorithm was used to calculate the nonlinear end value equations of binary systems, then the free volume parameters obtained were correlated with the activity coefficients of liquid binary, ternary, and quaternary systems at an arbitrary temperature. Three dimensional a-X-T diagrams of some binary systems representing the temperature and concentration dependence of activities were plotted. The calculated results regarding non-ferrous alloy systems have been statistically examined with the experimental values from the literature. Hence, this simple approach could be useful for analyzing thermodynamic properties of liquid alloy systems.

Jan 1, 2000

By Nicholas E. Vanderborgh

Projections show that domestic coal will serve for the majority of energy supplies during the next decades. Thorough chemical cleaning of this coal can be accomplished in long-residence time, slurry-transport systems to produce high-quality fuel product. Concurrently, mineral recovery from coals will supplement existing ores. This paper describes this concept and gives preliminary engineering considerations for mineral recovery during transport operations.

Jan 1, 1982

By J. E. Dutrizac

The behaviour of the lanthanide elements during the precipitation of sodium and potassium jarosites at 98oC from sulphate media was systematically investigated. The lower atomic weight lanthanide elements (La to Gd) are characterized by the limited solubility of their alkali-lanthanide sulphates, such as NaNd(SO4)2?H2O, which commonly contaminate the jarosite precipitates. Hence, single phase jarosite-type compounds were precipitated only from solutions containing <0.4 g/L of the La to Sm lanthanides. The sulphates of the heavier atomic weight lanthanide elements (Tb to Lu) have significantly higher solubilities such that solutions containing up to 10 g/L of the individual lanthanides could be investigated without the precipitation of alkali-lanthanide sulphate species. Even at the highest lanthanide concentrations, however, none of the jarosite precipitates incorporated more than 0.3 wt% of any of the lanthanide elements. Comparable levels of lanthanide incorporation were noted in both Na-jarosite and K-jarosite. Although the mass of the jarosite precipitate increased with increasing ferric sulphate concentration or with increasing pH, the extent of lanthanide incorporation was not significantly affected. Clearly, the trivalent lanthanide elements do not substitute extensively for trivalent iron in the jarosite structure. This behaviour likely reflects the significantly lower hydrolyzability and larger size of the trivalent lanthanide ions relative to ferric ions.

Jan 1, 2003

By Masafumi Maeda

Our aim in this project was to develop a new copper refining technology utilizing pyrometallurgical treatment and a raw materials preparation technique. In the recycling process; raw material is not an idealized concentrate of copper sulfide but is composed of various types of scrap, industrial wastes such as sludge, ash and slag, and municipal wastes. Since we cannot expect oxidation heat in this process as in sulfide smelting, organic materials are viewed as an alternative energy source. Quality of the copper produced is targeted as 99.99% and an intermediate grade will also be marketable. To benefit the plant, rare metals and other nonferrous metals will also be recovered The overall system is described in this paper, specific topics outlined and preliminary research presented. Current Japanese technology for recycling copper based materials is briefly reviewed.

Jan 1, 1995

By Edwin de Jesús Deveaux

After 32 years of operations beneficiating lateritic nickel ore in a fully integrated pyrometallurgical complex, Falconbridge Dominicana (FALCONDO), situated at Bonao and La Vega Provinces, Dominican Republic, has become profitable with one of the lowest nickel grade content processing plants in the world, and literally without any by-product (granulated slag, will be utilized in the future as a post-processing subproduct). To December 2002, mineral reserves were 64.1 million tonnes containing laterite grading as low as 1.15 % Ni when full dilution is applied. At a cut-off grade of 1.20% Ni, the reserves will provide 15-20 years of production. The mineralized thickness over the seven active deposits averages 6 m. Development of very selective and unique mining practices, together with improvements in the process plant, are key to achieving the production goal (30 kt Ni/yr) and to meet the quality standards for the ferronickel produced. Keywords: Laterites, grade control, mining methods, environment

Jan 1, 2004