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By Zhongliang Tian, Yun Cheng, Yexiang Liu, Ming Jia, Yanqing Lai

"A fundamental electrochemical study of Si ions in Na3AlF6-LiF melts and electrolysis using liquid cathodes was conducted. Cyclic voltammograms (CVs) clearly showed the depolarization of silicon deposition on liquid cathode by forming chemical complexes with the liquid solvent metals. Besides, co-deposition of Al and Si is possible when Si ions are insufficient in the molten salt. Based on the electrochemical results, silicon diffusion into liquid cathode is modelled and evolution of Si activity with concentration is deduced by a mathematic approach. Electrochemical study using liquid metals as working electrodes, can be used as an alternative approach for the acquisition of basic data on alloy behavior. Galvanostatic electrolysis showed that liquid cathodes are appropriate to collect the deposited solid silicon and the highest collection efficiency is almost 85%.IntroductionRecent years have witnessed an increasing demand for solar-grade silicon (Si) by the photovoltaic industry [1-4]. The preparation of high-purity metals through electrolysis and electrorefining offer many advantages such as low cost, low-energy consumption, and environment-friendly process, and thus has been widely used worldwide. From the perspective of electrochemistry [5-7], by utilizing the electronegativity difference between the impurities and Si and controlling the relevant process parameters, it is possible in principle to electrodeposit monatomic Si from a Si4+-containing compound melt. Moreover, because the carbon content of the high-purity Si obtained through electrolysis can be effectively controlled and used as a very ideal raw material in the preparation of electronic-grade and solar-grade Si, the preparation of high-purity Si through electrolysis has received widespread attention [8,9]. Monnier et al. [9] used a graphite electrode to obtain high-purity Si (99.9 %-99.99 %) from Si02/Na3AlF6 system through electrolysis; however, because the Si was precipitated in a solid form and showed poor conductivity, the deposition rate was too slow. Olsen et al. [10] obtained high-purity Si films via electrodeposition in K2SiF6/KF-LiF system by selecting electrode materials with high surface quality (such as Ag and graphite). However, in order to ensure the film quality, the deposition current density must be relatively low (10-50 mA/cm2), resulting in a low current efficiency and low deposition rate, which are not conducive to reducing energy consumption and applying to practical use"

Jan 1, 2014

By Rodney J. Ishak

The reduction of Mn3O4 to MnO has been investigated in a thermobalance apparatus. The charge was composed of manganese ore (decomposed by heating/calcination or pre-reduction to mainly Mn304) and coke. The material was charged to a crucible, which was suspended in the balance. CO-gas was distributed through a grid in the bottom of the crucible. Two sizes of ores were used; 2.4-4.8 mm and 6.7-9.5 mm. Coke particles were in the size range 4.8-6.7 mm. Experiments were conducted in the 900-1100°C temperature range. The composition of the product gas was monitored continuously. External mass transport between bulk gas and particle surface does not seem to limit the rate of reduction. Assuming that both diffusion through product layer and chemical reaction at the interface between MnO and Mn304 are rate controlling, the data was tried both in a shrinking core model and in a grain model using regression. The grain model gives the best physical description of the process, because the reactant is in fact a porous medium. With this model the effective diffusivity was calculated to be in the 1.5-6.10-5 m2/s range. The pore size was mainly between 0.1 and 10 um.

Jan 1, 2003

By G. Archer

ASARCO, a large and diverse producer of nonferrous metals, is involved primarily in the smelting and refining of lead and copper. Lead-antimony alloys, antimony trioxide, bismuth, cadmium oxide, selenium, tellurium, silver and gold are among products which result from processing by-products of smelting and refining. The complex mixture of concentrates at some smelters and the high impurity loads at some refineries result in various drosses, sludges, dusts and slags. In this paper, the complex interplant and intraplant transfer of by-products is addressed. These by-products result in an exchange of metals between the lead circuit and the copper circuit. Examples of the transfer of by-products and the prospects for the recycle of valuable products from wastes generated by customers and unrelated processors are also discussed.

Jan 1, 1992

By Patricia A. Wells

In the remelting of scrap, the ultimate goal is to produce clean aluminum while minimizing metal losses. Recently, it has become more difficult to make significant recovery improvements in Reynolds' Reclamation Plants since metal recoveries were nearing the theoretical maximum. In an effort to gain a better understanding of the factors impacting Reynolds remelting process, a series of experiments using a Taguchi-type design was performed. Specifically, the critical variables and interactions affecting metal recovery of shredded, delacquered Used Beverage Containers (UBC) melted in a side-well reverbatory furnace were examined. This furnace was equipped with plunger-style puddlers and metal circulation. Both delacquecing and melting processes operated continuously with downtime only for necessary mechanical repairs. The experimental design consisted of an orthogonal array with eight trials, each using nominal 500;000 lb shred charge volumes. Final recovery results included molten output and metal easily recovered from dross generated during the test.

Jan 1, 1995

By P. T. Velu

Light weight aluminum alloys are the major construction materials for a number of structures in automobile and aerospace industries. Higher cost of production is the key impediment which restricts the usage of these alloys. A new electrochemical process route for the low cost production of aluminum alloys is being investigated, in which alloying elements are obtained from the dissolved compound. In the present investigation, solubility of lithium compound has been determined by measuring the EMF, when it is dissolved in the electrolyte. The solubility of Li2CO3 increased with temperature from 2.95 wt pct at 1063 K to 7.57 wt pct at 1093 K. Activities of the compound in the electrolyte were deduced using Temkin's ideal solution approach.

Jan 1, 1995

By Barry J. Welch

The production of primary aluminium can potentially lead to metal that, with minimum treatment, meets a high purity standard. Smelters that can achieve a significant proportion of their production in this manner have a competitive edge which is of growing importance as the use grows for such items as compact discs and the like. Superimposed on the desire to produce high quality metal are stringent environmental requirements that the industry must adhere to. The environmental 'legislation focuses on fluoride emissions and the approach adopted is towards a zero waste management philosophy. The fluoride recycling process does, however, result in volatile impurities being captured and recycled to the cell. Aluminium has an extremely high reduction potential and this results in a significant proportion of the recycled impurities being reduced at the electrolyte metal interface and thus contaminating the metal. This paper reviews sources of impurities and the impact of the operating procedures adopted on metal treatment.

Jan 1, 1996

By Karl A. Gschneidner

Magnetic refrigeration was first used in the mid-1920's and new developments seem to have taken place about every 20 years, and this is especially true for the mid-1990's. The active magnetic regenerator magnetic refrigerator has the promise to become the first practical machine utilizing the magnetocaloric effect for cooling (and also heating). The basic principles are briefly discussed. Since the temperature lift for the magnetocaloric effect spans about 50 K, one will need to utilize several ferromagnets with different magnetic ordering temperatures in order to reach temperatures below ~250 K. The basic properties, behaviors, limitations, and new phenomena and knowledge are discussed.

Jan 1, 1997

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 R. David Prenganan

RSR has developed a new environmentally superior process to recover lead as high purity electn:1o'i0!1 cathode from battery scrap. The process involves crushing the batteries, separating the lead bearing material from the plastic, ebonite and separators, and separating the active material (paste) from the metallic lead fraction. The paste is desulfurized using Na2C03 to convert the PbS04 to PbC03 and produce a sodium sulfate solution. The paste is further treated to decompose the PbO2 and PbC03 to Pbo. The PbO from the treated paste is easily leached, using H2SiF6 and electrown from solution using Pbo2?coated graphite anodes. The electrown lead has a purity exceeding 99.99%. RSR is in the final design stages of a plant to produce 36,000 tons per year of electrcwon cathode from battery paste in a new plant adjacent to the present Indianapolis refinery. This paper describes the work of a pilot facility operated in the early 1980's. The paper describes the patented process in detail and compares the newly designed environmentally clean electrolytic plant to present recycling plants.

Jan 1, 1990

By Gus Van Weert

Hydrometallurgical oxidation of sulphides is capital and energy intensive, with autoclave and bio-technology competing for lowest overall cost status. The use of surface aerators instead of stirred tank reactors could provide lower costs for bio-oxidation of concentrates. With this in mind, the Delft Inclined Plate reactor was designed with inclined plates above a settler shaped reactor to continuously return slurry from the lowest point in the settler to the surface of the liquid. The multiplate superstructure overcomes the scale-up restriction of the standard circular surface aeration patterns. DIP aerator energy and volume requirements for oxygen transfer from air will be presented in terms of kg O2/kWh and kg O2/m3/h transferred as a function of wt % sand in the slurry and compared to stirred tank performance. Scale up from the 4 m3 pilot unit will be discussed.

Jan 1, 1996

By K. G. Wang, M. E. Glicksman, P. Crawford

"We formulate the mathematical solution to late-stage multi particle diffusion in finite systems. The transition from finite system behavior to that for an infinite system is established. Large-scale simulations are reported regarding the dynamics of phase coarsening. Even in the case of a small volume fraction (Vv = 10-4), the particle size distribution is broader than that for the well-known Lifshitz-Slyozov limit at zero volume fraction. We also report the first simulation studies of extremely low volume fraction, for which corresponding experiments, as well as other simulations, do not exist at present for comparison. However, in the case of moderate volume fractions (Vv = 0.1), the fiucutations in the volumetric growth rate of particles are extracted from our simulations. These simulations provide additional insight into the statistical nature of diffusion interactions, including multiparticle stochastics during microstructural evolution.IntroductionPredicting microstructure evolution in alloys remains one of the cornerstones of materials science. Phase coarsening is a common process in microstrucural evolution that leads to a decrease in the excess total interfacial energy of the system. The system typically consists of separate and identifiable units, or domains, such as second-phase particles distributed in a matrix. During phase coarsening, larger particles grow at the expense of small particles. Over time, this ""competition"" results in an increase in the average size of the particle population, and in a concomitant decrease in the number of particles.Particle size and microstructure of many cast alloys depend on similar coarsening processes. Indeed, properties of these materials, such as strength, toughness, ductility, and electrical conductivity, depend on the material's average particle size and particle size distribution (PSD). Understanding and controlling microstructures in two-phase systems are clearly of widespread technological importance."

Jan 1, 2001

By LeoJ. Miller

Exploration for an ore deposit commences with an outline of the regional ore controlling environment and is followed by the application of tools to focus the target area. One of the most essential focusing is the mapping of the mineral assemblages within the area of the ore. Key elements of mineralizing fluids, either epigenetic or syngenetic, enter into mineral assemblages that extend far beyond ore deposits. Portions of these assemblages may consist of new matrix minerals or alteration of previously existing minerals. Today, ore deposits are divided into genetic classes and each class is d8fined by a specific geological environment. Ore deposits within a given class are associated with a mineralogy, that is characteristic of the ore deposit class. So faithful is the mineral assemblage surrounding, or within an ore deposit, that recognition of the assemblage may be sufficient to define the class. Porphyry copper deposits have long been noted for their halos of alter-ation minerals. The outermost ring of chlorite, epidote and calcite extend thousands of feet away from the main ore zone. The mineral associated with porphyry copper deposits have been well documented by our distinguished speaker Paul Kerr, at Santa Rita (1), and Silver Bell' (2), and by excellent papers from S. C. Creasey, 1959 (3), Sales, 1948 (4), T. S. Lovering, 1949 (5), our Co-Chairman John Guilbert, 1970 (6), and many others. Several recent porphyry copper mines have been discovered in recent years by utilizing the mineral assemblage model described by Lowell and Guilbert, 1970 (6). Dave Lowell applied his own model of mineral halos for the discovery of Kalamazoo at San Manuel (7), Arizona, and Casa Grande West, Arizona. The purpose of this paper is to outline the application of mineralogy for discoveries of deposits other than porphyry copper mines and in particular, to ore discoveries in which mineralogy has played a key roll.

Jan 1, 1981

By Zhen Zhang, Jiang Diao, Xuan Liu, Tao Zhang, Bing Xie, Hong-Yi Li

Extracting vanadium from vanadium containing hot metal by LD process has been proven an effective solution for the utilization of vanadium-titanium magnetite ore, but the systematic analyses of vanadium extraction rate and mechanism by basic slag are seldom reported. In this study, mathematical model of vanadium transfer from metal to slag was formulated and the rates of vanadium extraction of hot metal with basic slag were investigated. The results indicated that the apparent vanadium extraction rate constant, kp, were in the range of 1.33~9.07×10-4g/(cm3·s). And the rate constant was increased with the increase of final slag basicity, reaction temperature and stirring gas flow. The apparent of mass transfer parameter decreases significantly from 0.13 cm3/ s to 0 cm3/ s in 20min, and the data changed as negative due to the decrease of slag oxidation and recovery of vanadium from slag to metal.

Jan 1, 2015

By Amir Rehmat

The Institute of Gas Technology has developed a fluidized-bed process for recovering direct reduced iron from blast furnace flue dust a material currently considered to be a waste from the iron and steel industry. In the process, a portion of the carbon in the flue dust is combusted to supply energy for the endothermic reaction between carbon and steam. The reaction produces reducing gases comprised of carbon monoxide and hydrogen both of which react with iron oxides to produce reduced iron. Up to 95 percent of the iron oxides contained in the waste stream can be reduced to elemental iron. The vitiated reducing gases emanating from the process can be used as fuel in the plant. The yield of iron depends upon the quantity of iron oxide present in the flue dust and generally ranges from 20 to 30 percent of the waste stream. The investment cost estimated for a single processing train dedicated to one steel plant can be recovered in less than one year.

Jan 1, 1996

By Hideki Yamamoto

A new technology to convert fluoride gas (C2H2F4 : R-134a) contained in the exhaust gases from semiconductor manufacturing plants and refrigerators directly into a harmless substance have been established, thus, presenting a new concept for the disposal of fluoride gases such as CFCs that are associated with the global warming. Experimental results verify that chemical reactions with metal compounds can take place at substantially lower temperatures of 700- 800K as compared with combustion treatment temperatures of 1200-1500K. The reaction product is mainly metal fluoride, which chemically is a harmless material. Furthermore, this process is compact, easily controlled, safe and has low running costs. This paper deals with a new chemical reaction method for the harmless disposal of gases effecting the global warming.

Jan 1, 2003

By Junzo Hino

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

Jan 1, 2003

By Hideki Yamamoto

A new technology to convert fluoride gas (C2H2F4 ; R-134a) contained in the exhaust gases from semiconductor manufacturing plants and refrigerators directly into a harmless substance have been established, thus, presenting a new concept for the disposal of fluoride gases such as CFCs that are associated with the global warming. Experimental results verify that chemical reactions with metal compounds can take place at substantially lower temperatures of 700- 800K as compared with combustion. treatment temperatures of 1200-1500K. The reaction product is mainly metal fluoride, which chemically is a harmless material. Furthermore, this process is compact, easily controlled, safe and has low running costs. This paper deals with a new chemical reaction method for the harmless disposal of gases effecting the global warming.

Jan 1, 2003

By Tsutomu Yamamura

The electrolytic reduction mechanism of rare-earth chlorides such as LaCl3, CeCl3, NdCl3, ` SmCl3 and DyCl3 in alkali chloride baths has been investigated in NaCl, KCI and eutectic LiCI- KCI by means of electrochemical transient methods. The thermodynamic behaviors of rare-earth containing species have been discussed in the frame of Electrode potential - P02- diagram. Low current efficiency found in the case of Nd electro-winning has been attributed to the dissolution of Nd into the bath. The analyses of electrochemical measurement required the elucidation of the effects of the factors such as under-potential deposition, metal dissolution, moisture and oxygen partial pressure.

Jan 1, 2003

By Wiraseranee. Chompunoot, Kazuki Morita, Toru H. Okabe

"Aiming at the development of more effective recycling processes, dissolution behavior of rhodium into molten slag was investigated. Using a pure rhodium crucible and Na2O-SiO2 slag system, equilibration experiments were carried out for 18 h at 1423-1623 K under various oxygen partial pressures of 0.005-1 atm with varied slag basicity. Rhodium solubility increased with increasing oxygen potential, slag basicity, and temperature. Rhodium dissolved into slag as rhodate ion ([RhO2]-) by the endothermic reaction: Rh(s) + 3/4O2(g) + 1/2O2-(in slag) = [RhO2]-(in slag). In the dissolution reaction, the “rhodate capacity” of slag is newly-defined. The correlation between rhodate capacity and optical basicity is reported.IntroductionDue to its high chemical resistance and outstanding catalytic properties, rhodium (Rh), one of the platinum group metals (PGMs), is utilized in various applications such as catalysts, molten glass vessels and containers, and electronic devices. Owing to the rarity of Rh resources in nature, recycled Rh from scraps such as spent automobile catalytic converters is currently considered as an important source of Rh supply [1]. According to the recycling practices, Rh is currently mainly recovered from scraps along with other PGMs such as platinum (Pt) and palladium (Pd) by a dry process (e.g., smelting), a wet process (e.g., leaching and subsequent separation of PGMs from aqueous solution), or a combination of both processes [2]-[4]. Among these processes, smelting is commonly applied because PGMs can be effectively separated from a relatively large amount of various impurities coexisting in scraps. In the smelting process, Rh and other PGMs are collected in the collector metal (e.g., iron and copper), and impurities in scraps are removed into slag [4]-[6]. The process may be carried out at a temperature range of 1573-1973 K, in either an oxidizing or reducing atmosphere. Due to the high oxidation resistance at high temperatures, Rh is expected to be collected efficiently in the metal collector rather than being oxidized and forming RhOx in a molten slag. However, Rh loss into slag does occur in this process [7]."

Jan 1, 2011

By Hiroshi Hashimoto

For the application of sodium carbonate slag treatment to product high purity copper on an industrial scale, the counter-flow batch process that reduces the amount of utilized slag is proposed from the viewpoint of the post-treatment of slag. Based on the distribution ratios of several impurities between the slag and molten copper determined previously, the effectiveness of this process is discussed using a mathematical model and confirmed experimentally. According to the model, the slag consumption to remove Sb to a required level in case of the counter-flow batch process with 3 reactors is calculated to be around 30 % of that in the case of an ordinary batch process, where pure sodium carbonate is used as a slag at every stage.

Jan 1, 2003