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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 Jun Li, Lin Chen, Tian-zu Yang, Wei-feng Liu, Wan-da Bin

"The Chinese bismuth production accounts for more than 80% all over the world in 2011. The main raw materials of bismuth smelting are bismuth concentrate and by-products of Cu or Pb smelting process. Many traditional methods of bismuth smelting in china was reviewed in this paper, such as reverberating furnace smelting, blast furnace smelting, fire-refining, ferric chloride leaching-hydrolysis, slurry electrolysis, and so on. But all the traditional pyrometallurgy or hydrometallurgy process have such shortages of low recovery, poor environment, and high cost. Therefore new technologies are introduced into the smelting process of bismuth concentrate, such as low-temperature alkaline smelting and side-blown bath smelting with oxygen-enrichment. These technologies have got great progress on energy saving, emission reduction, and friendly environment. Finally the development direction of new technology on bismuth smelting was prospected.IntroductionAs a green metal, bismuth has a wider applications, just extending from the traditional medicine, metallurgical-chemical engineering, low-melting alloys, solders, catalyst, and electronics to cosmetics, flame retardant, storage battery, semiconductor, supper conductor and nuclear energy etc[1,2,3,4,5,6,7]. This will increase the production of bismuth and promote the development and progress of bismuth smelting technology. At present, The major bismuth-product countries are China, Mexico, Peru, KZ, Bolivia and Canada etc, and China are dominating. A survey from the USGS[8] showed that Chinese bismuth production were 12,500 tonnes and got 80% of the world's in 2011. Thus the technology of Chinese bismuth smelting have a great representativeness."

Jan 1, 2013

By Dong Joon Min, Joo Hyun Park, Mi Sun Choi, Jae Hong Shin

Sublimation of ZrCl4 is important for the production of nuclear grade metallic Zr in Kroll’s process. The sublimation kinetics of ZrCl4 was investigated by TGA under both isothermal and non-isothermal conditions. The sublimation rate of ZrCl4 increased with increasing temperature under isothermal conditions. ZrCl4 sublimation was confirmed to be a zero-order process under isothermal conditions, whereas it was first-order kinetics under non-isothermal conditions. The activation energy of ZrCl4 sublimation under isothermal conditions was 21.7 kJ/mol. The activation energy for non-isothermal sublimation was 101.4 kJ/mol and 108.1 kJ/mol with the Kissinger method and Flynn- Wall-Ozawa method, respectively. These non-isothermal activation energies were very close to the heat of sublimation (103.3 kJ/mol). Sublimation occurs by two elementary steps: surface reaction and desorption. Therefore, the overall activation energy of ZrCl4 sublimation is 104.8(±3.4) kJ/mol. The activation energy of the surface reaction and desorption steps are proposed to be 83.1 kJ/mol and 21.7 kJ/mol, respectively.

Jan 1, 2014

By Francis Vanbellen

Umicore Precious Metals Refining operates an integrated precious metals smelting and refining plant in Hoboken, Belgium. Once a smelter and refiner of complex concentrates, the plant today?s feed consists exclusively of industrial and consumer recycled products, making it the world?s largest recycling facility for precious metals. Unlike the fairy tale of the Frog Prince, it took much more than a princess? kiss to successfully realize this makeover. A completely renewed plant has been built over the past decade. The most visible technological innovation was the commissioning of the Pb-Cu smelter. Its flexibility towards very different types of feed makes it perfectly suited as main entry to the Hoboken flow sheet. A new Cu-leaching & electro winning plant and precious metals refinery make up the Precious Metals Operations (PMO) whose targets are fast throughput and maximized yields for gold, silver and the platinum group metals. The Base Metals Operations (BMO), flexibly process the by-products from the PMO, valorizing ?impurities? like indium, tellurium, selenium and others. Off gas and waste water treatments ensure compliance with strict environmental standards. Precious metals recycling is an art that goes beyond mastering a unique flow sheet. Umicore Precious Metals Refining offers a complete recycling service, taking care of sampling and assaying, metals management and logistics. The quality of this integral service is recognized through the attribution of ISO certifications for our operational activities, sampling and the environmental care. And it?s an art that follows Michelangelo?s experience: ?Art is 5% of inspiration and 95% of transpiration.?

Jan 1, 2006

By A. Perillo

The process, realized in. the Kivcet furnace, can convert continuously lead concentrates, residues and secondary lead bearing materials into a lead bullion free of sulphur and a discardable slag. The lead recovery can be up to 99%. The long experience of about three years at Portovesme demonstrates the capability of the furnace to smelt a very. high range of lead raws without interruption of the operation. The operating costs are very competitive in comparison to the traditional technology. The work place and environment are clean and new tight regulations for the? hygiene control are met. The Kivcet furnace can be considered as consisting of three parts (reaction shaft, waste gas shaft and electro-furnace) connected with a common hearth. The technical basis of the furnace construction is the application of a number of design elements .which have mostly been used before in designs of industrial furnaces, such as open hearth furnace, refining furnace and other furnaces dealing with liquid meta1s. Refractory wear in the reaction shaft with typical pattern from watercooling soon has been stabilized and since maintained. No deformation of the furnace shell and no leakage of metal or s:l:ag through the bottom is? appeared after three years' operations.

Jan 1, 1990

By Duclerc Fernandes Parra, Luis Filipe Carvalho Pedroso de Lima, Washington Luiz Oliani, Danilo Marin Fermino, Ademar Benevolo Lugao

The modified polypropylene was obtained from isotactic polypropylene (iPP) in spheres by irradiation with gamma rays in the presence of acetylene. A new morphology with distinct rheology is obtained by this process in which occurs: degradation, branching and/or crosslinking. The objective of this study was to investigate the effects of thermal aging on the crystallinity and morphology of the modified polypropylene, High Melt Strength Polypropylene (HMS-PP). The thermal stability was evaluated after aging of samples using a stove at temperature of 90 °C, in presence of air at different periods of time. Aging effects were characterized by: Thermogravimetry analysis (TG), Differential scanning calorimetry (DSC), Infrared spectroscopy (FTIR) and Scanning electron microscopy (SEM). In thermooxidative conditions, the formation of oxidation products essentially involves a hydrogen abstraction by the peroxyl radical, leading to hydroperoxides as primary products and chemical degradation in the immediate crack tips. The effect of thermal degradation (chain scission and oxygen diffusion) on iPP was a more intense crack formation. Surface cracks increased with the aging time. In comparison of iPP, the modified PP samples had a morphological barrier inhibiting the penetration of oxygen into the sample and in consequence limit the propagation of degradation

Jan 1, 2015

By D. H. Rubisov

The neural networks modelling approach is one of the most elegant black-box type methods to model industrial processes. In this paper, this approach is applied to model the performance of the CEZ zinc electrowinning plant. The model that was built was found to exhibit an excellent predictive ability for voltage and current density. The model was also used to investigate the sensitivity of the process to various key variables such as temperature, current density, zinc and sulphuric acid concentration, etc. Optimal regimes for zinc production were identified from the power consumption standpoint.

Jan 1, 1996

By Afshin Sadri

Acousto Ultrasonic-Echo (AU-E) is a technique developed to provide accurate measurements of the refractory lining wear in operating smelters based on the principles of stress wave propagation. The objective of the system is to provide feedback for the continuous optimization of the overall smelter operation. In some cases, the AU-E refractory lining measurements have allowed clients to extend their smelter campaigns and operate safely for several years beyond their planned reline schedule. In other cases, AU-E results inform clients of serious issues within their furnace allowing them to shut down their smelters ahead of predicted failures and possible disasters. This paper presents the results of several smelter AU-E inspections of the hearth and sidewall. These case studies demonstrate how the AU-E results were used to positively affect the smelter operation.

By B. Q. Li, Y. Shu, K Lynn

"This paper discusses the effects of magnetic field and internal radiation on the melt flow and solidification morphology during solidification processing of oxide crystals for optoelectronic and remote sensing applications. The numerical solution of the integral differential equation characterizing the internal radiation and the magnetohydrodynamic equations describing the magnetic and transport phenomena is obtained by applying the combined discontinuous and continuous finite element method. The results show that both internal radiation and an externally applied magnetic field can have important effects on the melt flow and solidification behavior during the melt processing of oxide materials.IntroductionOptical single crystals are widely used in optical and electronic devices. These crystals are often grown from high temperature oxide melts under strictly controlled conditions. As in the well-known single crystal growth processes for semiconductor wafers, thermal gradient in the melt is a major contributing fuctor to the oxide melt pool. Unlike the semiconductor single crystal growth processes, however, the oxide melt is semitransparent and internal thermal radiation plays an important role in redistributing the thermal energy in the melt pool. Our recent experience with pilot-scale plant measurements also shows that the oxide melt is electrically conducting, although its electrical conductivity is considered much lower than the liquid metal or semiconductor melt.The fact that the oxide melt is absorbing and emitting in the thermal radiation frequency range makes it difficult to study the thermal energy transport in the melt pool. This is because thermal radiation is governed by a hyperbolic differential equation, which is different from those describing the transport processes in liquids. Also, our understanding of how thermal radiation interacts with other transport mechanisms such as convection and conduction is rather limited at point in time, in particular in high temperature oxide melts for optical single crystal processing."

Jan 1, 2004

By Peter C. Hayes

"The high temperature reduction of solids through the use of reactive gas atmospheres has application in a wide range of industrially important processes. Whilst significant advances have been made in understanding and describing these processes, some key aspects of the chemical reactions and reaction mechanisms operating in these systems, for example, the transformation from metal oxide to metal, remain poorly understood. A number of different product morphologies have been identified in these reaction systems and the reaction rates have been shown to be critically dependent on the product structure.Theoretical examination of the elementary process steps taking place in the region of the gas/metal/metal oxide interface, combined with electron microscope studies of the resultant product microstructures, have enabled the key process and material variables responsible for the development of the various product morphologies to be identified. By considering i) established criteria for the stability of moving interfaces in a thermodynamic potential gradient, ii) the relative rates of chemical reactions on the oxide and metal surfaces, and iii) key process phenomena and physico-chemical properties of the solid phases, the mechanisms and conditions for the formation of various product morphologies are identified. Interestingly the analysis points to direct analogies between these phase transformations and, the phenomena and microstructures observed in metal solidification, and the potential to develop generic models of these fluid/solid reaction systems."

Jan 1, 2013

Physical and chemical methods were investigated to tower thorium levels in Eneabba Ilmenite from the natural levels of 180-500 ppm to give Becher Process synthetic rutile with less than 100 ppm thorium. Chemlcal treatments, but not physical separations were successful. A pilot plant trial of a sodium hydroxide leach (25M NaOH at 75°C and 40 wt% solids for Ih) followed by a sulphuric acid leach (3M H2S04 at 90°C and 60 wt% solids for 211) confirmed that thorium could be removed to below 100 ppm. However, the activity of the ilmenite was not lowered to the same extent

Jan 1, 1996

By D. E. Woolley

The rate of reduction of iron oxide from calcia-silica-alumina slag by carbon in liquid iron has been measured over the temperature range 1400-1600°C by monitoring the rate of carbon monoxide (CO) evolution. Slags containing ferric iron have been used in order to study the reduction of both ferric and ferrous cations. Results show that ferric iron is reduced before ferrous iron, so that the ferrous iron concentration increases initially. It is also shown that the rate constant, k, decreases at low reaction rates, or, equivalently, at low concentrations. The authors conclude that the reaction occurs in two periods. During the first period, ferric iron is reduced to ferrous iron. During the second period, ferrous iron is reduced to metallic iron, and the rate-limiting step during the second period is the mass transfer of ferrous cations in the slag phase to the slag-metal interface.

Jan 1, 1998

By Jiann-Yang Hwang, Ying Qin, Shu-Jing Zhu

Metallurgical Oil Sludge (MOS) is a byproduct created in the process of steelmaking. More than a million tons of MOS are generated each year throughout the world. The material contains hazardous components such as heavy metals and pathogenic organics, which can cause serious environmental problems and health issues. Landfill, combustion, and pyrolysis have been investigated for the disposal of MOS. However, these methods are unsatisfactory since they are unable to reach the clean environment goal. In this study, we investigate the possibility of using MOS as a reductant in a high temperature metallurgical process. The results are reported and discussed.

Jan 1, 2015

By Sheng Dai, Yuan Lee, Haiming Xiao, J. P. Young

"There are numerous analytical applications of scatter-emission and/or absorption spectroscopy applied to liquids and solids in the temperature range of 0 to 350°C. In this paper an all-silica fiberoptic probe is described which is useful for spectral analyses from 0 to 1600 K and can be used in harsh chemical environments. The probe has been used for Raman spectral analyses of many molten salt and solid material systems to 1000°C. It has applications for such studies at higher temperature ranges. The instrumentation required along with the demonstrated and proposed applications of the all-silica probe are presented and discussed.IntroductionThere are many kinds of scatter-emission spectroscopies that are of value for analytical measurements. Fluorescence, reflectance, arc or spark emission are descriptors for some of these. Raman scatter spectroscopy is also quite a useful technique for analytical measurements.In Figure 1, we give a simplified explanation of the Raman effect. If one shines monochromatic light into a sample, light may be absorbed, exciting the sample to some virtual state. We know from experience that almost all of the light is re-emitted in the same wavelength range. This is called Rayleigh or Mei scattering and is designated in the figure by the arrows in both examples that point up and down from the same lower energy state. A very small percentage (the order of 10-4%) of the monochromatic light is re-emitted leaving the sample at a vibrationally-excited state. Thus, this light is at a distinctly lower energy compared to the exciting radiation. This is called a Stokes shift and is represented in the left-hand example by an arrow descending to a more energetic vibrational state. If the sample is not at a temperature of absolute zero, some of this vibrationally excited state will be thermally populated. That portion of the sample still absorbs and re-emits exciting radiation as Rayleigh scattered light, but a small percentage of the exciting light is re-emitted as the sample relaxes to the lower vibrational state. The energy of this light is of higher energy and is called an anti-Stokes shift, depicted in the example to the right. Notice that the energy separation of the Stokes or anti-Stokes shifted emission from that of the exciting radiation is the same, and expressed in ~cm-I. The intensity of either shifted emission is a function of the population of the vibrational energy states; therefore, the ratio of the intensity of Stokes to anti-Stokes signal varies with absolute temperature. We will come back to this point later."

Jan 1, 1997

By Richard A. Leiby

The recycling of lead-acid batteries in the United States has become a challenge as to how to balance ever increasing environmental regulation and cost with efficient operations. East Penn's captive secondary lead smelter has developed into a recycling facility producing lead, polypropylene, sulfuric acid, ammonium bisulfite, and non-hazardous discard slag. The emphasis has been to design a facility to comply with environmental regulations, to eliminate wastes, and to produce products, while at the same time, continuing to supply the company's battery manufacturing raw material needs.

Jan 1, 1993

By N. Kanari

Reactivity of MgO towards C12+air, C12+N2 and C12+CO gas mixtures was studied up to 1000 °C. Carbochlorination of MgO occurs at temperatures lower than that of its oxychlorination. Effects of gas flow rate, temperature and partial pressure of the carbochlorinating gas mixture on the reaction rate were investigated. The apparent activation energy of MgO carbochlorination is 49 kJ1 mol between 425°C and 600°C. At 550 °C, the apparent reaction orders with respect to C12+CO, C12 and CO, are 2.37, 1.47 and 0.89, respectively. At this temperature, the maximum reaction rate was obtained using a C12+CO gas mixture having a Cl2lCO molar ratio equal to about 0.6.

Jan 1, 1998

By H. Y. Sohn, M. Pérez-Tello, P. J. Smith, K. M. Riihilahti

A three-dimensional computer model for the Kennecott-Outokumpu flash converting process for copper matte is presented. The model incorporates the transport of momentum, heat and mass, and reaction kinetics between the gas and particles in a particle-laden turbulent gas jet. The k-E model is used to describe gas-phase turbulence in an Eulerian framework. The particlephase is treated from a Lagrangian viewpoint which is coupled to the gas phase through the source terms in the Eulerian gas-phase governing equations. Matte particles were represented as Cu2S·yFeSx. Based on experimental observation, the oxidation products were assumed to be Cu2O, CuO, Fe3O4, and SO2. A reaction mechanism involving the external mass transfer of oxygen to the particle surface and diffusion of the oxygen through the oxide layers of CuzO/Fe304 and CuO/Fe3O4 is proposed. Predictions of the mathematical model were compared with the experimental data collected in a large laboratory furnace. A reasonable agreement between the model predictions and the measurements was obtained in terms of fractional conversion of the oxidation reactions and of sulfur remaining in the reacted particles. The simulation of an industrial flash converting furnace was also performed. Higher oxidation rates, more even distribution of particles, and thus a more efficient use of the reactor volume are predicted with a burner having a distributor cone, than with a single-entry burner.

Jan 1, 1999

By M Philip Schwarz

"This paper reviews the status of computational modelling of a variety of common metals reduction processes, namely the blast furnace, rotary kiln and fluidised bed, and one new process not yet commercialised, namely smelting-reduction as in the HIsmelt Process. In each case, the last decade has seen the emergence of the capability to simulate the processes using multi-phase reacting computational fluid dynamics techniques. In some cases this capability is still in the process of being developed, and the next few years will see the maturing of the modelling techniques. As they become established, it will be possible to apply them to further refine the older technologies such as blast furnaces and rotary kilns, and assist in the optimisation, commercialisation and acceptance of the newer technologies such as fluidised bed and molten bath reduction. The development of a computational fluid dynamic model of bath smelting-reduction is described in some detail to illustrate how a large number of complex and interacting phenomena can be successfully simulated within a CFD framework. IntroductionPyrometallurgical reduction processes, such as the iron blast furnace, have become increasing more sophisticated through the centuries, so that today they are often highly efficient. There are continuing pressures, however, to refine existing processes and develop new ones. The imperatives are often economic, given that the long-term trend in the price of metals is always downward. In recent times, there has been the additional need to improve the environmental impact of metal production. Given that they almost inevitably require the use of carbon, metal reduction processes are large sources of greenhouse gases, and even a relatively small improvement in efficiency can be valuable in reducing CO2 production. Local environmental issues, such as the need to control of particulate emissions, are also driving incremental improvements in equipment.In addition to the economic and environmental drivers mentioned above, new process development is also being driven by the need to process new ores, and the need to produce unrefined metal in a form more compatible with alternative routes for downstream processing. An example of the latter is the production of DR! (Direct Reduced Iron) as a feed for EAF Electric Arc Furnace) in mini-mills.Further improvement of processes that have already been honed by continual plant experimentation over many years is not an easy task. To deliver further gains in efficiency, throughput, or product quality requires a highly sophisticated tool: one such tool· is computational modelling."

Jan 1, 2001

By Wen-Ming Chien, Vamsi Krishna Kamisetty, Amrita Mishra, Ivan Gantan, Prathyusha Mekala, Dhanesh Chandra

"The phase equilibrium and characterization studies by using high temperature X-ray diffraction (XRD) and differential scanning calorimetric (DSC) methods have been performed for binary organic thermal energy storage materials. The organic thermal energy storage materials undergo a solid-solid state phase transition before melting which stores large amounts of thermal energy. Two materials [tris(hydroxymethyl)aminomethane(TRIS) and 2-Amino-2-methyl-l, 3- propanediol(AMPL)] were used for this study. Binary samples of AMPL-TRIS were prepared to perform high temperature XRD characterization and DSC studies and the binary AMPL-TRIS phase diagram was developed. The high temperature solid-state phases of AMPL and TRIS were characterized as a disordered BCC structure. It was found there is virtually no solubility of TRIS in AMPL or vice versa below -75 °C. The maximum solubility of TRIS in AMPL is 11% TRIS at 75 °C. The eutectoid transformation was shown at 19%TRIS-81%AMPL composition and at a temperature of 75°C. Lattice expansion calculations on single phase of TRIS and AMPL have been performed.IntroductionThermal energy storage materials can store a large amount of heat due to the presence of thermal transitions from the orientationally ordered to disordered phases occurring before melting. These molecules (such as amine and alcohol derivatives of neopentane) can reorient as a whole about the central carbon atom to form orientationally disordered crystals (ODIC) and their spherical shape makes them reorient relatively easier. Thermal energy storage materials are becoming increasingly important as a renewable energy resource. These molecules undergo large changes in enthalpies at solid-solid transitions. The presence of these compounds with large enthalpy changes are identified as potential thermal energy materials and some of die applications are solar cell systems [1-3]. Binary mixtures have been found as a way to adjust the transition properties in addition to pure compounds [4]. Tris(hydroxyrnethyl)aminomethane (TRIS, C(CH2OH)3NH2) and AMPL, CH3C(CH2OH)2NH2) are two important thermal energy storage materials."

Jan 1, 2012

By H. Saint-Raymond, F. Gruy, P. Gardin, M. Cournil

"The control of inclusion elimination is getting more and more important to obtain clean steel. This paper presents a methodology under development for predicting cluster growth and elimination in ladle - RH system. The first key point is to express the collision efficiency, which is very specific for alumina cluster due to the non-wetting fluid. Second, a description of the two-phase flow in the system is necessary. In our calculations with Fluent CFD package and Lagrangian approach for bubbles, bubble growth is implemented, which improves the predictions. Using global reactor decomposition makes possible the prediction of the time evolution of cluster distribution. Important effect of fractal dimension is demonstrated.IntroductionElaboration of new steel grades requires not only to have a high purity in terms of C, O and N content but also to eliminate particles such as alumina or slag droplets. Flow optimisation making easier inclusion elimination is then a key figure to satisfy cleanliness requirements. Mathematical models of flow and inclusion behaviour are widely used for this purpose (1, 2). But having a predictive tool is still a challenge, because the number of phases is important in steelmaking industry: liquid steel, slag layer, bubbles and inclusions (with a large range of composition and rheology). The paper presents the methodology which is developed at IRSID to predict oxygen content evolution during RH degassing.The main mechanisms which have to be considered are :-inclusion growth by turbulent aggregation of elementary inclusions (keeping in mind that liquid steel is a non-wetting medium for inclusions); the difficulty is to express collision efficiency for alumina particles,-inclusion removal by flotation; the difficulty for alumina clusters stems from the complex morphology of particle; fortunately, the use of fractal concept makes it possible to cope with this problem.The paper describes the general modelling of inclusion removal taking into account the previous mechanisms. Hydrodynamic parameters are obtained by means of Fluent CFD package and a specific coding is developed for cluster growth."

Jan 1, 2001