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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 Ali S. Al-Watban

"In this paper, the room temperature friction and deformation properties of various polycrystalline diamonds; i.e. aggregates of diamond crystals with a ""binder"" phase of cobalt and a polycrystalline coating produced by a chemical vapour deposition processes (CVD) were studied when softer metallic and ceramic sliders were used. The experiments were conducted· at relatively low sliding speeds (10 mm/min), in a vacuum of 10-5 mbr after having cleaned the specimen surfaces by out-gassing them for about 30 min at 800 °C. As a result of increasing the number of traversals significant wear of the coated diamond by softer metallic sliders (aluminium and mild steel) was observed. With ceramic sliders, it is shown that the multiple traversals result in the formation of wear groove. With diamond silicon carbide, high friction and adhesion lead to significant metal transfer which then pre-empts cumulative deformation of the harder materials. With the diamond-cobalt composite, the friction is surprisingly low, there accumulation of wear debris on the tip of the slider but no permanent transfer of metal and the harder specimen is not damaged even after 5000 traversal.IntroductionPolycrystalline diamond is mainly produced as tool materials for the machining of hard metals and composites. Thus, the sliding friction and wear resistance are amongst the most important properties relevant to those applications.During cutting by PCD the wear mechanism is mostly influenced by the chemical affinity between the tool material and the workpiece. For example, diamond based materials are not recommended for machining ferrous materials because carbon is highly solubie in iron: This leads to the graphitisation of diamond particles and hence a high rate of diffusion wear is observed (Brookes and Lambert, 1982)."

Jan 1, 2000

By F. E. Wagner, L. J. Cabri, Y. G. Safonov, N. S. Bortnikov, A. D. Genkin, J. Friedl, G. N. Gamyanin

"A multidisciplinary investigation (including INAA, SIMS, EPMA, and Mossbauer Spectroscopy) was used to characterize gold in four of the largest Siberian mesothermal sulfide gold deposits. These are the Olympiada (""'750 metric tons gold) and Veduga (estimated at 75-100 metric tons gold) deposits in the Enisei Mountain Range and the Nezhdaninskoye (z500 metric tons gold) and Sentachan deposits in the Verchoyansk-Kolyma area. It was found that some of the mineralization is refractory in all four deposits, largely due to the occurrence of ""invisible"" gold in arsenopyrite as well as within pyrite, but with a lesser concentration. The gold concentration and its distribution varies considerably both within and between arsenopyrite grains, with implications for processing options such as heap leaching. The ore most likely to be amenable to heap leaching is the oxidized ore of the #4 orebody of the Olympiada deposit, but further quantitative mineralogical investigations are recommended for this orebody's sulfide ore and for the ores of the Nezhdaninskoye deposit. Following a full mineralogical characterization, it is possible that economic viability will depend on a combination of pre-concentration with or without pre-treatment, followed by heap leaching of some tailings products.Acknowledgements· The Russian authors performed this study under an ""Eco res"" Project which was financially supported by the Ministry of Science and New Technology of the Russian Federation. C.J. Stanley wishes to thank John Spratt and Terry Williams for help with EPMA. F.E. Wagner acknowledges the Deutsche Forschungsgemeinschaft for a grant supporting the Mossbauer studies. L.J. Cabri is grateful to the following: M. Beaulne, D. Carson and J.H.G. Laflamme for technical support, K.E. Haque for technical comments, and D.M. Hausen and W. Petruk for editorial suggestions."

Jan 1, 1997

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 Alicia E. Ares

316 L Stainless Steel samples were solidified directionally under conditions which produced the columnar to equiaxed transition. The position of the transition was located in each sample and the distance from the bottom of the ingot was measured. During solidification the distribution of temperatures were measured by means of thermocouples located strategically. From the measured temperatures the following parameters were derived; the local temperature gradient, the cooling rate and the velocities of the liquid and solidus fronts. Comparing the location of the transition and the values of these parameters it was found that the temperature gradient reaches negative values of as low as -13.44 "C/cm, and velocities of the fronts of around 0.1 cm/s. Also, a supercooling of 5.81°C were measured which was associated with the supercooling for the nucleation and growth of the equiaxed grains ahead of the columnar front. In addition the primary and secondary dendritic spacing was measured in both regions. The spacing was compared with the predictions from available models. The results are presented and discussed in the frame of the results obtained for other alloys

Jan 1, 2002

By P. Blazy

A hydrometallurgical procedure for the recovery of metal from ore, particularly of copper from sulphide materials is described. In the course of this procedure, the raw material is first of all submitted to the action of an appropriate reducing system and then treated with a ferric salt solution which brings about the selective solubilisation of the elements to be recovered with respect to those constituting the pyritic phase. This procedure is investigated using two ore samples proceeding from massive sulphide deposits, presenting different chemical and mine- ralogical characteristics. The results of this investigation are compared with those obtained by a classical process employing a ferric salt solution. It appears that one solubilisation of copper takes place under particularly advantageous conditions when our procedure is used. The principal parameters affecting leaching of zinc, lead and copper are examined. The selectivity of this treatment is evaluated by following the change during the treatment in the pyritic phase.

Jan 1, 1976

By V. V. Satya Prasad, A. Sambasiva Rao

Electroslag melting technologies have recently been developed for recycling light scrap of valuable metals and alloys such as superalloys and oxygen free high conductivity (OFHC) copper at Defence Metallurgical Research Laboratory (DMRL), Hyderabad. Conventionally, electroslag melting processes use consumable electrodes. Because of the difficulty in compaction of scrap into a consumable electrode of satisfactory quality, non-consumable electrodes such as graphite and water-cooled copper have been designed. Electroslag remelting using a water-cooled non-consumable electrode was developed to melt scrap of a nickel base superalloy. Sound ingots with smooth surface finish and properties comparable to vacuum melted superalloys could. be obtained from scrap using this process. A modified electroslag crucible melting process using graphite crucible and graphite electrode was developed for recycling OFHC copper scrap. Copper ingots with less than 10 ppm oxygen and electrical conductivity"" 100% IACS could be produced. The same process was also utilized to produce copper-based alloys such as copper-chromium and copper-titanium starting from copper scrap.

Jan 1, 2000

By Y. K. Rao

Relatively pure crystalline lead sulfate (PbSO4) can be produced by chemical vapor transport from an impure source such as the lead-acid battery paste or the roast-ore-leach-residue from a hy¬drometallurgical process-route. In a closed-reactor, transport of matter is induced by a tempera¬ture-gradient and the steady-state transfer rate can be calculated using the data on the standard free energies of formation for the species present and the pertinent binary diffusion coefficients. The present work focusses on chemical vapor transport in a tubular reactor (1.4-cm inner diameter x 10-cm long) with the source- and deposition-ends held at 850°C (T,) and 750°C (Td), respectively; PbC12(g) is the 'solvent' or 'transport agent' and NiSO4(s) placed in the source-zone -serves to maintain a sufficiently high S0,-potential such that the stability of the lead sulfate species is ensured. For the purposes of analysis, the gas-phase in the reactor is assumed to consist of eight species: H2O, PbC12, SO3, SO2. O2 HO, C12, and PbC14. The reaction between C12(g) and PbSO4(s) in the high-temperature source-zone produces PbCl2, SO2, and 02; four more reaction-equilibria in the same zone yield other species. In the low-temperature deposition-zone, reaction equilibrium involving PbC12, H2O, and SO, leads to the nucleation and growth of PbSO4 crystals; three other reaction-equilibria occur in this zone. By employing the virtual equilibrium state for the end-zones and coupling it to the Stefan-Maxwell diffusion equations for each of the gas species, the respective partial pressures for these, in the source- and deposition-zones, are computed at steady-state. From these data, the molar fluxes of PbCl2. PbCl4, and so forth, are determined. Allowing for the transport-enhancing effects of thermal convection, the net transport rate of lead (or PbSO4) is duly calculated for specified initial conditions. The predicted rates show very good agreement with measured rate data reported in the literature [ V. Plies, T. Kohlmann and R. Gruehn: Z. anorg. allg. Chem, 568, 62 (1989)

Jan 1, 1995

By G. E. Lagos

This paper analyses the scope and instruments employed by the Basel Convention for regulating the transboundary movement of hazardous wastes, the present and projected hazardous waste regulations of Chile, reviews the Chilean import/export trade of wastes of the period 1985-1995, and discusses, the influence that the Basel Convention has had on mining trade, its perceived benefits and costs, and possible effects on Chile's trade of the application of the Convention's Decision III/l. There is no quantitative estimation as to the effect of the Convention on the general volume of imported or exported materials destined for recovery, recycling, reclamation, or reuse. All recycling imports, with the possible exception of residues of petroleum oil, which occurred during the decade 1985-1995, can be classified tentatively as non hazardous. The entry into force of the Convention has had several effects on Chile's trade. It has brought home the need to have a comprehensive hazardous waste legislation, it has been a base for applying import restrictions, which in all likelihood, would .have otherwise not been applied, The benefits and costs of this import restriction, as well as those of the multilateral export ban are analyzed.

Jan 1, 1999

By D. J. Webb, D. G. Reynolds, D. W. Ashman, D. W. Goosen

Cominco Limited operates an integrated zinc-lead complex at Trail, British Columbia, Canada. Central to the successful operation of this complex is the treatment of zinc leach residues through the lead smelter. In 1997, Cominco started up a new lead smelter using KTVCET flash smelting, a state-of-the-art conventional slag fuming furnace, and a new drossing plant. The smelter has fully met the requirements for environmental performance, reduced energy consumption, and lowered labour costs. This paper provides a description of the new smelter and discusses the problems encountered during the start-up, as well as the solutions to those problems. Recent operating results are presented. Lead-Zinc

Jan 1, 2000

By A. W. Worcester

The plant is designed to produce 60,000+ tons of refined lead per year from a nominal feed consisting of 110,000 tons of SLI and industrial batteries, and 10,000 tons of lead contained in drosses and scrap. The plant will also produce as by-products polypropylene chips and detergent grade sodium sulfate, using the Engitec Impianti CX Technology. The battery separation circuit will consist of a battery breaking hammermill and a vibrating screen with water sprays to separate the battery paste from the grid metal and other battery components. The battery components, consisting of ebonite, and separator materials, will be separated' from the grid metal and classified with the use of hydrodynamic water separators. The battery paste will be treated with sodium carbonate to produce a lead carbonate paste for smelting in a reverberatory furnace. The slag from the reverberatory furnace will be campaigned through a traditional primary blast furnace to produce hard lead. The sodium sulfate liquor from the lead carbonate filtration step will be crystallized to produce anhydrous sodium sulfate. The metallic grid metal will be treated through a small rotary smelter of the Engitec design to produce a hard antimonial lead. The plant's scheduled to be commissioned 12 months after receipt of all of the Federal and state permits. The plant will be integrated into the Buick Primary Lead Smelter, located in the center of Missouri's New Lead Belt, at Boss, Missouri. This will allow The Doe Run company to fully utilize all of its existing assets.

Jan 1, 1990

By G. A. Irona

Solids injection into non-ferrous converters and furnaces is becoming increasingly important for concentrate injection, removal of impurities, and recycling of dusts and other waste materials. The fundamental design aspects of these technologies will be reviewed, including gas and particle trajectories, lance clogging, heat transfer, and mass transfer including reaction rates and mixing. The use of soda ash for removal of impurities such as antimony and selenium will be used as an example of versatility of powder injection processes.

Jan 1, 1993

By S. Yuan

Oxygen ion conducting yttria-stabilized zirconia (YSZ) tube was used to remove oxygen from molten Cu at 1373K. Outer surface of the tube was in contact with the melt and the inner surface containing a thin layer of porous Ni-ZrO2 cermet electrode was in contact with a reducing gas. The migration of oxygen species (O2-) from the Cu melt through the YSZ tube is accompanied by an equal and opposite flux of electrons maintaining electroneutrality. Without applying an external EMF, the fluxes are maximized by short circuiting the melt with the cermet electrode. For efficient oxygen removal, the YSZ tube must be thin, contact resistances should be negligible, and the electrodes must be porous and cover the entire electrolyte surface for charge transfer. This refining process is environmentally sound, can use reducing gases such as H2, CH4 and CO without running the risk of increasing H or C content of the melt.

Jan 1, 1993

By D. L. Jones

The leaching of natural chalcopyrite was studied in both ferric sulfate and ferric chloride solutions. The chemistry of the two reactions is quite different, with substantial sulfur oxidation occurring only in sulfate solutions. Ferric chloride is a more effective reagent, for the leaching rate is greatly increased with finer particles and higher (Fe+++), and unaffected by high (Fe++); none of these advantages are found with ferric sulfate. In addition, the morphology of leaching appears to be different, with ferric sulfate leaching preferentially along fissures or grain boundaries. The kinetics were found to be linear over an extended period, rather than parabolic as reported elsewhere. An explanation of the observed phenanena is proposed using the electrochemical theory of leaching, and experimental measurement of the mixed potential of the mineral during leaching.

Jan 1, 1976

By Rolando Campos

Until 1970, the Caletones Smelter of CODELCO-CHILE, División El Teniente, operated under the conventional pyrometallurgical process used by most of copper smelters. The annual copper production varied around 165.000 tons. The failure in the commissioning of the "oxygen smelting" technology in Peirce- Smith converters (1970-1972), forced further introduction of transcendental changes in the Caletones smelter operating scheme. Implemented technological innovations were based on wide studies and research works performed by División El Teniente. This paper presents a summary of technological modifications introduced, their impact on production and energetic performances, and short and medium terms improvement plans.

Jan 1, 1993

By B. L. Chulu

In the carbothermic reduction of lead sulfate to produce lead, the inclusion of soda ash (Na,CO,) in the charge provides for the control of sulfur dioxide in the effluent gas. An important mechanism in the process appears to be the carbothermic reduction of the sodium carbonate whereby sodium gas and carbon monoxide are produced. These intermediates then participate in the reduction of the lead sulfate to produce lead metal and stable sulfur species in the molten slag phase. In addition, there is some evidence that the presence of lead metal in the charge may also serve to increase the lead recovery in the process. These aspects were investigated by conducting laboratory-scale smelting tests with small charges (;3g), at 1173°K(9000C). Recovery did not exceed 74w% and the role of incipient lead metal in the charge could not be clearly assessed.

Jan 1, 1993

By Andreas Siegmund

During the decade of the nineties the conventional method of primary lead smelting (sinter machine/blast furnace) was successfully challenged by the introduction of novel direct and continuous smelting processes. In combination with a significant shift in market structure, as well as more stringent government regulations these modem technological innovations like the QSL, Kivcet, and Isa/Ausmelt processes became more than major competitors. They have proven to be economically and environmentally viable. The intensification of the metallurgical reaction by applying oxygen enriched or pure oxygen bath or flash smelting principles resulted in cost savings and a higher flexibility with respect to raw materials and additives usage. By synchronizing individual auxiliary plant sections with the smelting process a virtually waste- free production and low-emission mode of operation with nearly optimum energy exploitation is achieved. The primary lead industry will gradually substitute the sinter -blast furnace operation with novel high-energy efficient technologies in the new millennium.

Jan 1, 2003

By Y. Ono

In lightweight metal processing such as aluminum (AI) and magnesium (Mg), metal cleanliness is a crucial process parameter for refining, part manufacturing and recycling in order to obtain high quality parts and products. In this paper, techniques for cleanliness evaluation of molten AI and Mg using ultrasonic probes with clad steel buffer rods having high signal-to-noise ratio (SNR) are presented. Due to the high SNR of the ultrasonic probes used, backscattered ultrasonic signals from inclusions, which may be oxide films and/or particles, in molten Mg and those from silicon carbide particles, having an average size of 50f.Ull, added in molten AI are successfully detected with reflection configurations of pulse-echo and/or pitch-catch modes at an ultrasonic frequency of 10 MHz. In addition, relative cleanliness evaluation of molten Al and Mg is demonstrated. In order to establish the procedure and to investigate the optimum system configurations for cleanliness evaluation of molten metals, particle flow simulation system using water and polyvinyl chloride (PVC) particles has been constructed. Counting the number and measuring the size distribution of the PVC particles, having an average diameter of 128um, suspended in water with the PVC volume concentrations of 5ppm and 10ppm are performed with ultrasonic pitch-catch mode. The counted numbers of particles by the presented method and system have good agreement with the calculated results with a count error of less than 10% or two counts. Based on the results obtained with water simulation experiments, the prototype system for cleanliness evaluation of molten Mg by counting and sizing inclusions has been developed. Keywords: Ultrasound, Clad buffer rod, Molten metal, Aluminum, Magnesium, Inclusion detection, Cleanliness measurement, Counting, Sizing

Jan 1, 2003

By Yukio Ishikawa

Sumitomo Metal Mining Co,. Ltd. (SMM) has been producing 22,000 t/y of electrolytic nickel at Niihama by nickel matte electrorefining process since 1970. Although the matte electrorefining is an established process and the productivity has been greatly improved in the last 20 years, SMM has intensively developed the chloride process for the nickel production since 1970's. The nickel and cobalt refining process involving solvent extraction and electrowinning from the chloride solution has been successfully developed for the treatment of the mixed sulphide in 1975. The first application of chlorine leach to the anode slime has been succeeded since 1986. Based on those technology, the matte chlorine leach electrowinning process (MCLE) has been developed as an alternation to the relatively old technology of matte electrorefining. The new process offers significant cost down and excellent quality of the product. In 1986, the feasibility of MCLE was confirmed by the test work using the integlated pilot plant. The innovation of the chlorine leach process has been undertaken by this work. The new refining process can be divided into three stages including chlorine leach stage, purification stage and electrowinning stage. More than 99 % of nickel was extracted in atmospheric chlorine leach. Although copper ion was used for electron carrier in the chlorine leach, the excess copper from the feed matte is bled off from the leach circuit by de copperizing electrolysis. The copper ion of the pregnant solution is fixed on nickel matte by the cementation reaction. The nickel matte containing copper is processed in the chlorine leach. In the purification circuit, cobalt, iron and other impurities were removed from the nickel chloride solution. The nickel chloride solution is then fed into the electrowinning cell. Based on the process established, the new plant with a capacity of 330 t/M electrolytic nickel was commissioned in order to obtain the engineering data for design of the full scale plant in 1989. The performance of the plant was fully satisfied and the new process demonstrated the potential application of modern process control.

Jan 1, 1992

By Alan James Parker

Chalcopyrite can be converted to pure copper by the following five steps. An exothermic sulfation roast of chalcopyrite; leaching of cupric sulfate from the calcine with dilute acid; precipitation of Chevreul's salt and or other copper sulfites with ammonium sulfite or precipitation of crude copper by autoclaving ammonium sulfite and cupric sulfate at 150°C; dissolution of Chevreul's salt, or the crude copper, as cuprous sulfate, using acidic cupric sulfate in an acetonitrile-water solution as oxidant; precipitation of pure copper by thermal disproportionation of the cuprous sulfate solution. Acetonitrile and acidic cupric sulfate solution recycle. Advantages over conventional processes include lower cost, lower energy consumption as waste heat, sulfur removal as ammonium sulfate or gypsum, rather than as sulfur dioxide and rapid throughput. The net reaction is: 2 CuFeS2 + 4H20 + 15/2 02 + 8 NH3?2Cu + 4 (NR4)2 SO4 + Fe2O3

Jan 1, 1976