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By T. Wang, R. G. Reddy, D. Mantha

"A new eutectic LiN03-NaN03-KN03-KN02 quaternary molten salt system was calculated using thermodynamic modeling. The eutectic temperature was predicted to be 100°C. The melting point and heat capacity of the salt eutectic composition were determined using DSC. The experimentally determined melting point is in excellent agreement with the predicted value. The melting point is more than 124°C lower than that of the KN03-NaN03 solar salt. The density of the molten salt was experimentally determined as function of temperature. Using the density, heat capacity and the melting point, thermal energy storage density and gravimetric storage density of the quaternary molten salt were calculated and compared with that of solar salt. The larger storage density value of this molten salt indicates that this salt has a better energy storage capacity for solar power generation systems.IntroductionMolten salts have been used as thermal energy storage media for solar energy applications. Nitrates are being used in the solar energy applications for their low melting point, low unit cost, high heat capacity, high thermal stability, negligible vapor pressure and high energy storage density [l]. Solar salt (NaN03/KN03: 60/40) is the most popular thermal energy storage medium which is currently being used with the freezing point of 221 ·c [2]; another ternary system HITEC® which contains NaN03, KN03 and NaN02 has freezing point of 141°C [3]. Newer nitrate salt mixtures are being studied and projected as potential candidates for thermal energy storage (TES) and heat transfer (HT) applications. Based on these favorable features, molten salt can work directly as the energy storage medium below 500°C [l]. Development and synthesis of newer molten salt mixtures with freezing point lower than those currently used for thermal energy storage applications is necessary for sustained utilization of solar energy. The approach to develop lower freezing point molten salt mixtures is by the prediction of new eutectic mixtures and also by the development of new nitrate compounds."

Jan 1, 2012

By Daniel K. Kim

The charge for the copper refinery is a mixture of anodes produced at San Manuel from BHP source concentrate and copper purchased from external sources. Control of unwanted impurities in the tankhouse - is very important and beneficial. Currently available removal/recovery technologies were reviewed for the control of bismuth and antimony levels in the electrolyte. Recent studies have focused on solvent extraction (SX) technology and generated successful results for the removal and subsequent recovery of bismuth and antimony. The SX system employs the reagent, ACORGA SBX-50, in conjunction with a patented high chloride stripping system. The latter enables recycle of the eluant, avoiding the high costs associated with conventional systems, such as regeneration of resin. Concerns over potential transfer of organics and chloride ion to the electrolyte were readily addressed, solved and demonstrated using conventional, established technology. This paper describes the benefits of electrolyte purification, the flexibility afforded by the SX system, the operational practices necessary for maintaining adequate control of bismuth and antimony impurities in the electrorefining environment and possibilities for future development /exploitation of the Zeneca SX system at the San Manuel refinery.

Jan 1, 1998

By Yoichi Takeda

Copper solubility in Si02-CaO-FeOx slag equilibrated with copper matte in 10% S02 atmosphere at 1573K was estimated. Essential parameters are activity coefficients of copper oxide and sulfide, oxygen and sulfur potentials and activity of copper in the slag-matte system. A large number of experiments provide proper parameters to calculate copper solubility in slag. A classical thermodynamic model postulating CUOO.5 and CuSo.; molecules assists in estimating copper solubility in slag. Additions of Si02 and CaO reduce copper solubility almost in any condition. Copper loss, that is function copper solubility and slag volume, in the silica saturated Si02-FeOx binary slag is minimally equilibrated with less than 66% copper matte while copper loss in the 50% FeOx-SiOrCaO ternary slag saturated with 2CaOSi02 is minimally equilibrated with over 66% copper matte. This slag composition has potential for continuous copper converting, direct copper production or high-grade matte production.

Jan 1, 2003

By Jr. Napolitano, Jr. Sanders

"Morphological evolution of a dendritic growth front in a binary alloy is simulated using a cellular automaton approach to establish the feasibility of modeling such growth with a local rule-based scheme. The motivation for this work is derived from the need to predict the development of solidification structures within real components of complex geometry, where significant constraint of the thermal and solutal fields may exist. Such cases present complex boundaries and large domain sizes, which may preclude the effective use of more conventional methods. In this work, a model is presented which couples a two-dimensional alternate-direction-implicit finite-difference diffusion solution with a cellular automaton growth algorithm to simulate morphological evolution in alloys solidifying under directional growth conditions. Temperature, composition, and interface curvature are incorporated into a local growth potential which is used by the automaton, allowing the interface to evolve. Alloy solidification is simulated over a range of experimental conditions, producing various structures. Issues addressed include morphological instability, primary spacing selection, interface curvature, microsegregation, and tip conditions.IntroductionThe development of dendritic structure plays an essential role in alloy solidification. Virtually every microstructural feature, within a cast alloy component, is related to the interface morphology present during solidification. Conventional solidification theory, describing dendrite tip kinetics and mushy zone phenomena, provides a means for estimating overall microstructural parameters for an alloy solidified under steady-state conditions. Microstructural prediction for actual components, which are finite in size and complex in geometry, requires a description of the evolution of the interface morphology under transient conditions and geometrical constraint and an understanding of how the structure propagates through the mold. Any useful simulation tool must be equipped to handle these circumstances within the limits of computational feasibility."

Jan 1, 1998

By M. Elbert Nigri

Radioactive wastewaters from nuclear source of electrical energy production need to be treated and disposed of properly. Sr, Ca, Mg and Ba are common elements in this effluent, which can cause incrustation in process equipments and being unsafe to human health (90Sr). Fixation of CO2 can be applied to remove the ions mentioned before and to provide a solution where CO2 is sequestered and the deleterious elements precipitated, becoming one of the possible steps to reuse the water into the process. Moreover, removal of several metals from distinct wastewater has been evaluated using bone char through adsorption. The chemical similarity between calcium and strontium makes the exchange of these two metals favorable in the hydroxyapatite structure contained in bone char. This paper evaluated the combined action of precipitation and adsorption process with injection of CO2 and bone char addition in simulated nuclear wastewater. Removal levels of 89.0% (Sr) and 83.3% (Ca) were obtained in the combined process. The presence of bone char as seed increased the precipitation kinetics, allowing a Sr removal of 85.2% in five minutes, higher than 75.3% obtained in absence of seeds. However, removal of 91.6% (Sr) and 89.8% (Ca) were obtained in absence of seeds at 24 h. Analysis of solids have evidenced that CO2 was consumed to precipitate the metals as carbonates, since the hydroxides are formed at higher pH’s.

By Kenneth McGowan

"The aluminum industry is the 5th largest consumer of energy and the largest consumer of energy on a per-weight basis. Process heating accounts for 25% of the energy consumed to manufacture aluminum. Consequently, the generation of this energy results in the production of a significant amount of CO2 (over 3.75 million metric tons in 2003)1. As a result, the Aluminum Industry Technology Roadmap of 2003 listed the development of improved refractory materials as a goal to reduce energy use and decrease greenhouse gas creation. The result of a R&D effort addressing this desire is the development of patented microporous refractory materials for metal contact applications in all furnace areas including the belly band. It has been demonstrated that this material can reduce energy consumption up to 38% in furnaces and significantly reduce heat loss in launder and trough systems. Furthermore the material developed is non-wetting and remains un-penetrated by metal throughout its lifetime. The material does not contribute to the formation of corundum. As a result, the energy efficiency of an older lining remains intact compared to standard refractory materials which may have an initial high insulating value (such as lightweights and board) or standard dense refractory (even with penetration inhibitors) both of which show a rapid increase in thermal conductivity as the refractory is penetrated with aluminum and formed corundumIntroductionThe aluminum industry is the second largest producer of metal in the United States, behind the iron and steel industry. It is the 5th largest consumer of energy and the largest consumer of energy on a per-weight basis. Process heating is required to melt, hold, purify, alloy, and heat treat the metal and accounts for 25% of the energy consumed to manufacture aluminum. As such, process heating is the second largest energy consuming operation. Smelting, which utilizes an electrolytic reduction process is the largest energy consuming operation1.Most process heating is accomplished through the use of fossil fuels, either directly or indirectly. The choice of fuel is dependent on a plant’s location and fossil fuel availability. Table I shows the processes impacted by refractories and the calculated BTU’s generated by usage of the respective fuels as well as the Metric Tons (MT) of metal passed through each process in 20001."

Jan 1, 2009

By Wade L. Karlsen

"Revision surgery to replace joints in the human body requires materials that are strong, long-lasting, and biocompatible. Metallic implants made of cobalt-chromium-molybdenum alloys are already popular because of their proven corrosion and wear resistance properties, but there is an on-going effort to economically improve their performance. Alloying with inert nitrogen can enhance the mechanical properties of the alloy, enhance its corrosion resistance, and elevate the temperature at which the metallic implants can be thermally treated, without increasing the threat to the human body. The current work has produced a high-nitrogen Co-Cr-Mo alloy through HIP consolidation of metal powders that have undergone nitriding in a mechanically fluidized bed. The already fine microstructure of the powders combined with the increased nitrogen content resulted in significant property gains in the consolidated materials.IntroductionMetallic implants made of cobalt-chromium-molybdenum alloys are already popular because of their proven corrosion and wear resistance properties, but there is an ongoing effort to improve their performance. Research on a Stellite 21 cobalt-chromiummolybdenum alloy has shown that nitrogen alloying can be desirable from several standpoints [l]. Firstly, it has indicated that nitrogen can enhance the mechanical properties of the alloy, which could allow more demanding implant designs. The same work also demonstrated that nitrogen can elevate the temperature at which the metallic implants can be thermally treated, which is desirable in situations in which surface textures are to be sintered to the implant to enhance its fixation properties. Finally, that research work discovered that, not only does nitrogen not harm the corrosion resistance of the cobalt-chromium-molybdenum alloys, but it may in fact enhance it. Combining this with the fact that small amounts of nitrogen are not considered a threat to the human body, makes nitrogen alloying an attractive alternative for enhancing the properties of Co-Cr-Mo."

Jan 1, 2000

By Batric Pesic

Solvent extraction of nickel and cobalt from the real leach solutions was studied by using a novel extraction system. The extraction system was a mixture of 2,6-bis-[5-n-nonylpyrazol-3¬y]] pyridine (BNPP) and dinonylnaphthalene sulfonic acid (DNSSA). The BNPP represents a novel molecule, which was designed and synthesized in our laboratory. Real solutions for the study were prepared by leaching of two different cobalt-nickel bearing concentrates, cobaltite [CoAsS] concentrate from Blackbird Mine, Idaho, and siegenite [(Ni,Co)3S4] concentrate from Missouri Lead-Belt. The major strength of the system was the selectivity of extraction toward nickel and cobalt from iron containing solutions. Other metals such as Mn, Mg, Ca, Al and As were not extracted. Due to the irreversibility of copper extraction, its removal from solution was required prior to the extraction of nickel and cobalt. Zinc was not as strongly extracted (i.e. its stripping was readily achieved) as was copper . Flowsheets for the recovery of nickel and cobalt were also developed.

Jan 1, 1997

By K. D. Peaslee, V. L. Richards, C. H. Rawlins, S. N. Lekakh

"Steel-making processes generate carbon dioxide air emissions and a slag co-product. The aim of this project was to develop a functional sequestration system using steelmaking slag to permanently capture carbon dioxide emitted in steelmaking offgas. A possible parallel benefit of this process would be rapid chemical stabilization of the slag minerals with reducing swelling or leaching.This paper summarizes the original results of the project, including mineralogical and structural features of carbon sequestration with steel making slag, mathematical modeling of reaction phenomena using a modified shrinking core model, METSIM modeling of several possible industrial applications, a thermo-gravimetrical study of the reaction between slags and different gases, and design and testing for a lab scale apparatus consisted of two reactors.1. IntroductionThe U.S. produces 9-14 Mt of steelmaking slag annually, which represents approximately 10-15 wt. % of crude steel output.1,2 Primary uses for steelmaking slag include high quality mineral aggregate, Portland cement, unconfined fill, soil conditioning, and pH neutralization of abandoned mine drainage.3,4 The key factor prescribing slag use is the alkaline-earth metal (e.g. Ca and Mg) oxides content, which contribute to overall basicity and cementitious strength. However, as-produced steelmaking slag is chemically unstable. Calcium and magnesium oxides readily form hydroxides and carbonates through reaction with atmospheric gases. Both hydroxide and carbonate formation produce substantial mechanical swelling leading to heave failure in confined construction applications, thus many states dictate stockpile aging for 3-6 months prior to commercial use.5,6 Sequestration of carbon dioxide is a natural corollary to forced carbonation. The conversion of CaO/MgO to carbonates serves both to stabilize the slag, and permanently capture and store the CO2."

Jan 1, 2008

By Patrick R. Taylor

Ilmenite concentrate and methane are fed to a non-transferred arc thermal plasma reactor to produce a powder that is primarily TiC and Fe. This material has promising characteristics for powder metallurgy applications. Free energy minimization plots were used to predict the feasibility of the reaction. An estimate of the optimum molar ratio between the ilmenite concentrate and methane was made based on the mineral composition. Argon-helium mixtures were used as plasma gases. The effects of power input level, carrier gas flow rate, powder feeding rate, and methane-ilmenite molar ratio were studied and the behavior of the system characterized. Two different powder injection angles were tried. A mathematical model to describe the temperature profiles in the reactor was formulated and solved. The product has been characterized by x-ray diffraction and atomic absorption. A conversion of 97 % of Ti to TiC was achieved. It was found that minor amounts of titanium oxides, iron carbide and free carbon are also present. TEM and SEM were used to study the morphology.

Jan 1, 1996

By S. J. Buckler

Many chemical and metallurgical processes use submerged gas injection to increase contact area between gas and liquid phases in order to promote faster overall reaction or refining rates. The total interfacial area produced by gas injection through lances, nozzles or tuyeres is both an important design parameter for new vessels and a measurement for estimating the maximum processing capacity of existing equipment. Estimating total interfacial area from submerged injection into industrial pyrometallurgical vessels from existing knowledge is a problem with two aspects. The first difficulty is the difference in behaviour of cold (aqueous) and hot (molten metal) systems, implying that existing models and correlations of gas-liquid behaviour developed in low temperature systems are not necessarily appropriate for estimation of high temperature behaviour. The second difficulty is the issue of scale-up of correlations from laboratory to industrial sized vessels. The work presented in this paper is part of an ongoing experimental investigation, at the GK Williams CRC for Extractive Metallurgy, to quantify the total gas-liquid interfacial area available in pyrometallurgical vessels using chemical measurement methods. The effects of three operating variables, injected gas flow rate, nozzle diameter and nozzle submergence, on total interfacial area are quantified in a IOOL aqueous system - the first stage of a three stage process in examining the implications for scale-up of high temperature, medium-scale results are discussed. The results of work at high, injected gas flow rates (up to 500/min) show that the submerged Froude number is not sufficient for use as the sole variable in a predictive model of total interfacial area. Further work is being undertaken to identify other dimensionless variables that will better represent the gas-liquid characteristics in submerged injection that influence the formation of total interfacial area. The second and third stages of the experimental investigation involve measuring the total interfacial area in a large-scale (1000L) aqueous sodium sulphite and small-medium scale molten metal baths.

Jan 1, 2002

By Ragnhild E. Aune, Mark William Kennedy, Shahid Akhtar, Jon Arne Bakken

"In the present study classical induction design tools are applied to the problem of heating nonmagnetic metal billets, using 50 Hz AC. As an example of great practical industrial interest, the induction heating of aluminum billets is addressed specifically. The predicted work piece power is compared with the measured work piece power for a long and a short coil, using well established methods, such as those of Burch and Davis, introduced in 1926/28, Dwight and Bagai in 1935, Baker in 1944/57, Vaughan and Williamson in 1945, and by Tudbury in 1960. A calculation methodology based on a combination of the available tools is also introduced and discussed. The method has proven to give an error of <10% of the actual work piece power. An equation for Tudbury's work piece shortness correction factor is disclosed for the first time.IntroductionInduction heating of metal billets is a practical problem, with a geometry suitable for solution using analytical methods. This paper will examine solutions related specifically to round work pieces in round coils, although the methods presented can be extended to other regular shapes of work pieces and coils[l]. The methods can also be extended to ferromagnetic materials with slight changes[2-3]. It is assumed that the coil and work piece have a consistent diameter over their entire length and that the work piece is at least as long as the coil. Correction factors can be derived for the cases where the work piece is shorter than the coil.The study of induction heating by coils began in the late 19th century with theoreticians like Heaviside[ 4]. The work of Burch and Davis[ 5-7] in the 1920' s greatly improved the theoretical understanding of induction applied to metallurgy. Many investigators in the 1930's-1950's: Dwight and Bagai[8], Baker[l-2, 9], Vaughan and Williamson[3, 10] and others[l 1-12] added to our understanding with clearer mathematics, solutions for specific applications, semi-empirical modifications and practical design tools. Much of the accumulated knowledge is available in books, such as Tudbury's practical text or Simpson's engineering guide from 1960[13-14]. Perhaps the best description and derivation of the theoretical and semi-empirical solutions can be found in Davies[15]."

Jan 1, 2011

By J. W. Evans

Mathematical modeling has now become a standard technique in the development of new technology and the improvement of existing technology in the processing industries. Physical modeling has a longer history but a smaller following at present. The paper reviews some examples of the application of both types of modeling in non-ferrous metal extraction, particularly within the copper and aluminum industries. The objective is to show that well founded models can lead to results that have practical consequence in scaleup, design and operation.

Jan 1, 1993

By O. Durand

The Cerro Verde Hydrometallurgical Plant, located at Arequipa in the southern part of Peru, started its operation in 1977 with a design capacity of 33,000 MT/year of copper cathodes. The plant has treated 61,055,000 MT of ore mainly oxides with a content of 1.01% total copper and 0.67% of soluble copper. The leaching plant has three pads that produce 4.0 gpl copper solution. The solvent extraction plant has four trains with three extraction stages, two stripping stages with a single mixer in all stages. The mixer-settlers are 316 stainless steel and the pumps are vertical turbines. The flowrates of 1,300 gal/mil of aqueous and 1,300 gal/min of organic at a 1/1 ratio. The electrowinning plant contains 208 commercial cells and 18 starting sheet cells. Each cell has 47 anodes and 46 cathodes. In addition to describing the hydrometallurgical plant, this paper also mentions efforts directed at reducing costs and improving operations. The initial results from leaching secondary sulfides, which started October 1985, are also discussed.

Jan 1, 1987

By M. Giralico

Optimized mixer settler designs will now handle flows of over 25,000 GPM. The size and expense of the equipment hamper experimental settler optimization efforts. Computational Fluid Dynamics (CFD) is a timely and predictable tool for settler design development. In the past, CFD has been used to evaluate only the flow field in pumped and auxiliary tanks. A similar numerical analysis is used to evaluate settler flow and phase separation. Phase separation is analyzed using multiple species for the aqueous and organic phase. Experimental validation shows good agreement between the computational and experimental solutions in both flow field and phase separation. The computational model is used to show performance differences between various choices of settler geometry, liquid depth, with variable flow rates. Understanding the differences allows the development of optimized settler designs. System improvements are predicted to lower entrainment levels further and/or allow new smaller footprint designs. This paper focuses on the major design components of the settler and how future technological advances will lead to further improvements in their design. LIGHTNIN?s new designs will handle tomorrow?s production requirements, while maximizing profits.

Jan 1, 2003

By K. Narayana Swamy

Experimental results of 3-phase mixing in a physical model of a CCRL for metals refining, at high levels of bottom gas injection (up to a superfIcial gas velocity (Us) of 12.5 cm/min), are presented. A thermal tracer technique was used to elucidate both longitudinal mixing and interphase heat transfer. The results indicate that even under conditions of significant bottom gas injection, it should be possible to maintain acceptably low longitudinal mixing (D. < 20 cm2/s and D/uL < 0.1) in the CCRL. Interphase mass-transfer coefficients of the order of 0.02 cm/s and higher, are predicted from the measured interphase heat transfer coefficients using the mass and heat transfer analogy. Adequate performance is likely to be possible for an industrial CCRL, based on extrapolation of these results to full-scale conditions.

Jan 1, 1996

By D. W. Lawler

Prior to the manufacture of sulphuric acid in metallurgical plants, the SO2 rich gas from the smelter, roaster, or furnace must be cleaned to removed particulates, volatile contaminants, SO3, and water. Cleaning is accomplished by contacting the. gas with cooled weak acid. The system is designed so that all the contaminants, originally in the gas are captured in the weak acid, which then becomes an effluent from the plant. Historically, the entire weak acid effluent stream has been treated for disposal, with no attempt to recycle or recover any part if it. This is becoming increasingly environmentally unacceptable, and operators must consider better methods of treatment and recovery. In this paper, Kvaerner Chemetics discuss a number of options that allow the contaminants to &apos;be separated from the acid&apos; value. This will result in an acid byproduct that can be sold or used elsewhere, and will minimize the volume of hazardous byproducts that must be discharged.

Jan 1, 1998

By Yotamu Stephen Rainford Hara, Animesh Jha

The investigation focuses on a low temperature recovery of Cu and Co from a 40 wt% SiO2-(30 wt%Fe,6 wt%Al)2O3-10wt% CaO-7wt%CuO-7wt%CoO slag over a temperature range of 1173K to 1323K. The alloy phases containing Cu-Co and Fe-Co alloy formed via the carbothermic reduction of oxides: MO + C = M + CO(g), where M represents metallic copper, cobalt or iron. In the direct reduction of oxides, the recovery of metallic phase was well below 90% at 1323K, due to the kinetic barrier which was analysed and attributed to oxygen and metal-ion transport in the slag. This barrier was overcome by adding CaSO4 and carbon, which yields a matte (MS) phase via MO + CaSO4 + 4C = MS + CaO + 4CO reaction. Lime thus produced in situ participates in metal oxide/metal sulphide reduction reactions, which are analysed with the help of X-ray powder diffraction, scanning electron microscopy, and thermogravimetric analysis.

Jan 1, 2014

By Z. Jing, L. Qihou, C. Jun, L. Hui, Z. Yumeng

Three phases of Bi2O3 were first synthesized by extraction-stripping precipitation and post decomposition from BiCl3 leaching solution. The as-prepared Bi2O3 were characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectra (FT-IR), scanning and transmission electron microscopy (SEM, TEM), UV-vis diffuse reflectance spectroscopy (UV-vis DRS), Brunauer-Emmett-Teller (BET) and X-ray photoelectron spectroscopy (XPS). The photocatalytic performances of the oxides were investigated by decomposing rhodamine B (RB) under visible irradiation. It shows that the Bi2O3 with different crystal structures and morphology were obtained under different decomposition temperature. The band gaps of as-prepared samples were 2.36, 2.41, and 2.78 eV for b-Bi2O3, a-Bi2O3, and d-Bi2O3, respectively, and the photocatalytic activities followed the order: b-Bi2O3 > a-Bi2O3 > d-Bi2O3, which was in good accordance with the photoluminescence spectra measurement results. The b-Bi2O3 exhibited the best photocatalytic performance which can effectively degrade 99.23% RB within 240 min.

Mar 1, 2018

By Ramana G. Reddy, M. R. Bogala

Transition metal silicides have good potential for converting waste heat into electrical energy at higher temperatures. Transition metal silicides are used as thermoelectric alloys at higher temperatures because of their low toxicity, high natural abundance, good transport properties, and better thermal stabilities. In this article, thermodynamic, and thermoelectric properties of promising metal silicides are reviewed, calculated, and compared for waste heat recovery application. Higher manganese silicide (Mn4Si7) was produced from easy one-step self-propagating high-temperature synthesis (SHS) procedure of arc-melting technique. Characterization of the alloy phases were done using X-ray diffraction (XRD). In this study, lattice constants, Vickers microindentation hardness, and thermoelectric (TE) properties (Seebeck coefficient, electrical conductivity, thermal conductivity, and figure of merit) of Mn4Si7 alloy were experimentally determined, and compared with the reported literature values.

Mar 1, 2017