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By Jingwei Lou, Bing Li, Suzhen Li, Miao Shen, Jianguo Yu

"As a main impurity in primary lithium metal, magnesium is difficult to remove because of the very close relative volatility of the two metals. Electrochemical refining provides a possibility to completely remove Mg in the LiCl-KCl melt prior to Li reduction. MgCl2 reduction processes in LiCl-KCl- MgCl2 melt were investigated by cyclic voltammetry (CV), square wave voltammetry (SWV), chronoamperometry and chronopotentiometry. Then potentiostatic electrolysis was carried out and Mg (II) ion was reduced onto a liquid lead cathode from the LiCl-KCl-MgCl2 melt at the Mg deposition potential. The results show that Mg ( II ) is reduced in one step with two-electron transfer. The reduction potential of Mg ( II ) was well defined. The reduction of Mg( II) results in Li ( I ) underpotential deposition at 0.2V more negative potential than that of Mg( II) reduction. Therefore, in order to prevent Li ( I ) from codeposition with Mg, accurately controlling Mg ( II) reduction potential during the potentiostatic electrolysis was necessary. Ninety three to 99 % removal rate of MgCl2 was achieved after 8-12 h electrolysis when liquid lead was used as cathode.IntroductionMetallic Li has been widely used in batteries, light weight alloys and in fusion reactors because of its excellent properties. Currently, the only way in industry to produce metallic Li is by electrowinning from molten LiCl-KCl at about 450 °C [l-5]. LiCl-KCl is the only electrolyte used, because they presents a lower eutectic temperature and KCl shows a slightly higher theoretical decomposition voltage than LiCl, as shown in Table l .The produced metallic Li generally contains 1-2 wt% impurities including Na, K, Al, Ca, Mg, Si, etc. [6l, which are derived from the corresponding metal chloride compounds or metal oxide compounds existing in the LiCl and/or KCl raw materials. These impurities have to be removed by subsequent vacuum distillation at high temperatures to meet the requirements for metal Li purity in the final products. Separation of Mg from Li by vacuum distillation is difficult because their relative volatilities are very close, as shown in Table 2."

Jan 1, 2011

By David R. Sadedin

The highly negative Gibbs free energies of hydrogen atom reactions suggest that refractory oxides such as titanium dioxide should be easily reduced by hydrogen atoms. These reactions appear to be most favourable at low temperatures; oxides should be reducible even at room temperature. Since hydrogen atoms are produced in plasmas containing hydrogen a number of investigators have used hydrogen plasmas of various sorts to test these possibilities for reducing refractory oxides, in particular TiO2. None of these attempts has succeeded, a small degree of reduction being achieved in only a thin layer near the surface. A deeper consideration shows that several factors complicate the reactions expected on the basis of the negative Gibbs free energy. One factor is that the back reaction by water molecules produces molecular hydrogen, not hydrogen atoms, and the metal atoms that have been reduced may be immediately re-oxidised. In plasmas there are complications due to diffusion, thermal and charge boundary layers and charged particle reactions. Interpreting the results of hydrogen atom reactions is difficult. Hydrogen is not detectable by electron dispersive spectroscopy and amorphous products are not determinable by x-ray diffraction. Another consideration is economics. The cost of producing hydrogen atoms has a large bearing on the metals for which hydrogen atom reduction may be competitive. In this paper these factors are discussed, some necessary basic studies are highlighted and the general principles of a laboratory reactor are given, together with the results of tests using ZnFe2O4, ZnO and TiO2 as test oxides.

Jan 1, 2006

By Takashi Ikeda, Masafumi Maeda

"Demand for solar cells is increasing linearly throughout the world. Last year production totaled 3000 tons worldwide. The market size of solar silicon is expected to increase further because of international ""political"" demand to reduce carbonaceous emission from energy consumed. Most elemental silicon is produced by the carbon reduction of Silica in an electric arc furnace. Purity of silicon at this stage is 90-99%. Major impurities are Fe, Ti, Ca· and Al, and minor ones are P, B and carbon. The oxidizing metallurgical process is no longer effective to remove transitfon metals because those are less noble to silicon. Nonmetallic impurities such as phosphorus and boron must be reduced to 0.001ppm for semiconductor use. The most common process for high purity silicon is the Siemens C process, which is basically distillation of hydro-chlorinated silicon followed by CVD of SiHCl3. The cost of such silicon is expensive to allow its popular use in solar cells. Currently scrap silicon -of semiconductors is used for this; however, the supply-of that scrap is limited to just a portion of semiconductor production.In this paper world demand for silicon will be reviewed and some of the processes proposed summarized.IntroductionSilicon is element 14 in atomic number and has an atomic weight of 28.0855. Little elemental silicon is found in the earth, and it is mostly found as oxides or silicate. The Clark number of silicon is very large and the second in its number. If we were discussing the volatility of silicon element on the globe, we would never worry about it. However, it is very difficult to obtain pure elemental silicon because a high purity silicon compound is very rare. In most cases these are silica (silicon oxide SiO2). As shown in Table 1, there are many grades of silica ore classified mainly by their content of iron and alumina."

Jan 1, 2000

By F. W. Warnaars

Chanarcillo is a historically well-known silver deposit which produced over 100 million ounces. High grade vein-type mineralization is confined to a prominent set of nearly vertical, NNW to NE fractures that intersected limestones, andesites and tuffs of Early Cretaceous age. A significant amount of disseminated silver mineralization extends laterally outward from the fractures for considerable distances in pyritic carbonaceous limestones, whereas more competent volcanic beds rarely contain lateral mineralization. Local exposures of skarns are mostly barren. Silver and minor base metal mineralization was probably formed peripheral to a granodioritic intrusion inferred to exist at shallow depth. Part of this intrusion is exposed nearby where it contains significant hydrothermal mineralization and alteration. This intrusion was dated at 83.8 m.y.

Jan 1, 1987

By Fumito Tanaka

The Mitsubishi process is the sole pyrometallurgical process for the continuous production of blister copper from copper concentrates and has been successfully operated around the world. The development of calcium ferrite slag (CaO-FeOx-Cu20), the so-called "C-slag", has enabled continuous converting from matte to blister copper in the commercial scale operations. Commercial interests in the slag led to many papers over the CaO-FeOx slag. However, CU2O- bearing slag has not been studied well due to experimental difficulties. The authors have quantified the thermodynamic properties ofthe CaO-FeOx-Cu2O system. The results have been utilized to analyze various issues related to the converting furnace, such as the magnetite precipitation from the slag or from blister copper and to develop better controlling criteria for the continuous converting operation.

Jan 1, 2003

By R. Singh, C. Gong, J. Chaudhry

"Metalorganic chemical vapor deposition (MOCVD) is an ideal technique for the deposition of conducting and non-conducting oxide based thin film materials. In this paper we have presented a study of photo assisted MOCVD for the low temperature deposition of a number of oxide based advanced materials. We have used incoherent light sources as the source of optical and thermal energy in our MOCVD system. The vacuum ultraviolet (VUV) and ultraviolet (UV) photons can enhance the surface reaction of the absorbed molecules through the perturbation of the electronic state of binding between the absorbed molecules and the solid surface. Unlike plasma process, no surface damage is expected and high quality materials have been deposited. At a given substrate temperature, the performance of deposited film depends on the lamp configuration.INTRODUCTIONMetalorganic chemical vapor deposition (MOCVD) has become the standard manufacturing technique for the deposition of large area thin films of compound semiconductors. l.(.w-cost, high crystalline quality, atomically clean and sharp interfaces, atomic layer epitaxy, high throughput rates and potential for direct writing are some attractive features of MOCVD. Due to a number of potential advantages mentioned above, MOCVD is considered as an ideal technique for the deposition of various electronic and optical materials for a wide variety of applications. Rapid isothermal processing based on incoherent radiation as the source of optical and thermal energy is emerging as the key low thermal budget (integral of processing time and temperature) processing technique for the fabrication of current and next generation of microelectronic and optoelectronic devices and circuits [1]. In this paper we have demonstrated that the design of the lamp assembly plays an important role in determining the properties of the materials deposited by RIP assisted MOCVD. We have studied the growth rates, structural properties and electrical properties of Y2O3/Si structure. At a given substrate temperature, best results are obtained for the lamp assembly that provides maximum number of VUV and UV photons."

Jan 1, 1994

By Cameron Hams

Noranda's Process Reactor and Codelco's Teniente Converter are physically similar vessels, which leads to the commonly held misconception that the two processes are the .same. However, notable differences in chemistry, operating philosophy, and construction make them quite dissimilar. This paper compares and contrasts the Noranda Reactor and the Teniente Converter, and attempts to explain some of the apparent differences in behaviour and performance. The results of a worldwide survey of most operating Noranda Reactors and Teniente Converters, along with those processes that have ceased operation or are planning to be started-up in the future, are presented.

Jan 1, 1999

By Goran Vukovic

The use of gas purging plugs in the copper industry is a widely used practice. They provide substantial improvements especially in anode refining furnaces, where savings in process time and energy are obtained as well as refractory wear and buildups inside the furnace are minimized. The newly developed system, enables purging plugs to be implemented in both stationary and tilting furnaces, is in operation in vessels on three continents. An additional advantage in these furnaces above all other benefits is the significantly improved melting rate. This innovative and patented gas purging system consists of a purging plug cooling device and a slidable, cooled piping system. It provides compensation for any thermal expansion in the furnace lining and minimizes the risk of undesirable copper infiltration. User experiences and results of this widely used system are reported in this paper.

Jan 1, 2014

By Xiang Sun

Microwave processing has been under continuous development as an advanced heating method in modern industries. However, problems with uneven heating still remain. Although heating uniformity is highly dependant on the properties of the materials being heated, proper furnace design to prevent uneven field distribution is another important factor. As an alternative to experimental measurements and adjustments to find appropriate furnace parameters, computer simulation is a convenient method for modeling, understanding, and improving the uniformity of microwave heating. This paper discusses current modeling technologies as well as applicable techniques for improving microwave heating uniformity. The purpose is to give a basic understanding on how to find, analyze, and minimize the problems associated with uneven heating in microwave processing.

Jan 1, 2006

By Shijie Wang

In pressure oxidation leaching of copper anode slimes, than 65% of the tellurium is m' cxtraoted during decopperizing. About l0- 15% of the selenium is also dissolved simultane¬ously by severe leach conditions. Current operation for the treatment of the leachate is to constantly recirculate the leach solution through a bed of copper turnings. The tellurium and sele¬nium are precipitated from the leach liquor as copper telluride and copper selenide and sepa¬rated from the solution by filtration. In order to improve the reaction efficiency and reduce the process cost, viz, minimize the copper addition, cut retention time, and reduce the energy consumption; a chemical reducing agent is studied and the cementation process tested in the laboratory. In this paper, the test results are presented and the process chemistry is discussed.

Jan 1, 2003

By R. G. Reddy

Nickel solubilities in spent pickling solutions (i.e. HF-HNO3-H2O solutions ) were measured as a function of HF and HNO3 acid concentrations. The chemical analysis of the industrial pickling solutions and sludges were made. The stable phases observed in the sludges are FeF3?3H2O, and ( FeCr ) F3?3H2O. Pure Ni, and stainless steel type 316 were used in this study. The results showed that the solubility of Ni increased with increase in concentrations of HF in pickling solution at a fixed concentration of HNO3: An excellent agreement between the experimental solubility data and the theoretical data was obtained. X-ray diffraction analysis showed that the solid solubility product formed is mainly NiF2?4H2O compound.

Jan 1, 1992

By I. J. Moon

The reduction behavior of hematite by H2 and H2-CO gas mixtures was investigated to elucidate the reduction mechanism at 800-950 °C. The hematite compacts were made by Cold Isostatic Pressing to produce compacts of uniform shape and size. The compacts were sintered at 1000° C for 30min, and showed a contraction of 29%. Mercury pressure porosimeter was used for measuring the total porosity, pore size distribution and pore surface area of the compacts. Reduction was measured by means of weight-loss technique using Cahn Balance (Model : TG-171, capacity log, accuracy f 10pg). Microscopic examination and X-ray analysis were used to correlate the structure of reduced compacts with the mechanisms of reduction. Neither chemical reaction control nor diffusion control is adequate in describing the complete course of reduction of the hematite compact. The reduction of hematite compacts was initially controlled by the chemical reaction at oxidelmetal interface. The reaction goes through a transition phase .where it is undergoing a mixed control, followed by the diffusion control towards the end of the reduction. The values of apparent activation energies for chemical reaction control were 3.48-8.43 kcal/mol depending on the gas compositions.

Jan 1, 1997

By Motohiro Horiguchi, Kazuo Ichii, Toshio Oishi

"As a fundamental study to prepare copper-based alloys with rare earths (RE: La, Gd, Nd, Ce and Y) without any inclusions, the solubility of rare earth in liquid copper was experimentally determined. Liquid copper alloys were equilibrated with carbon and rare earth carbide in a graphite crucible in an argon atmosphere at 1523-1873 K.Solubilities of rare earth in liquid copper were determined by approaching the equilibrium values from both the lower and the ·higher concentrations than those expected· in the preliminary experiments. They were expressed as a function of temperature. Carbon in Cu-RE alloy was also analyzed and thermodynamically discussed.IntroductionOver the past several years, the demand for highly conductive and high strength copper-based alloys, such as Cu-Cr, Cu-Zr and Cu-Cr-Zr for use in electronic materials has increased.1 -7 These alloying elements are very reactive and easily oxidized to form oxide inclusions during melting. To avoid the oxide inclusions, it may be effective to utilize the strong reducing power of carbon in conditions under which no carbides form.In this study, to provide fundamental data for producing Cu-RE( rare earth) alloys without any inclusions, the solubility of rare earth in liquid copper in equilibrium with .carbon .was determined and discussed on the basis of the experimental results and the thermodynamic data.ExperimentalSample preparation for equilibrium experimentsOxygen-free copper (99.99%), lanthanum (99.9%), gadolinium (99.9%), neodymium (99.9%), cerium (99.9%) and yttrium (99.9%), and their oxides were used as starting materials.Each rare earth carbide was prepared by mixing rare earth oxide with carbon, which is a little more than the stoichiometric composition, pressing it into a tablet form and sintering at about 2000.K for 20 ks in a vacuum furnace using a graphite crucible. Powder X-ray analysis showed that only the carbon and rare earth carbide (REC2) was present in each sample.Cu-RE mother alloys (5-20 mass % RE) were prepared beforehand by mixing metallic rare earth with oxygen-free copper, and melting in an electric arc furnace."

Jan 1, 2000

Four slag types covering the range of Fe-Ca-Si-O compositions and two iron blast furnace slags were melted at 1300 °C and doped with 1% of arsenic, antimony, cadmium, zinc and chromium. The melts were either slow cooled or quenched and the solidified slags were leached according to TCLP procedures. The morphology of the solidified slags was characterised using XRD, optical and electron microprobe techniques. Theoretical considerations showed that the capacity of the molten slag to hold the above toxic elements depended upon slag basicity and this was confirmed in practice. The experiments showed that the leaching of the toxic elements was a function of surface area and the phases present, both of which were affected by the mode of cooling. Iron silicate slags produced in nonferrous smelting operations and blast furnace slag from ferrous smelting operations both show promise of being suitable media for immobilising low levels of toxic elements and complying with current regulatory requirements.

Jan 1, 1994

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 Chen Song

In the experiments of purifying the solution of chlorine leaching from nickel concentrate with N235, the effects of organic phase composition on purifying efficiency have been studied. From the results obtained, the optimal organic phase composition is found to be 25%N235+12%isomerous alcohol +63%sulfonic kerosene (VIV) and the saturated content of cobalt in organic phase is7.95 g*dm3. And then the serial experiment is carried out. The results show that at the given organic phase composition, the purified solution contains p(Ni) >200 gm dm3, p(Ni)l p(Co) >50000 and the contents of Cu, Fe, Mn, Zn meet the technical criterion of standard nickel electrolyte. The cobalt chloride solution contains p(Co) >I10 g L-1, p(Co) lp(Ni)>50000 and the enrichment of cobalt has been achieved.

Jan 1, 2006

By Alessandro Blasi, Massimo Morgana, Corradino Sposato, Pietro Garzone, Giuseppe Devincenzis

A comparison among (2-ethylhexyl)-mono (2-ethylhexyl) ester Phosphonic acid (P507), Secondary-octyl phenoxy acetic acid (CA-12) and Bis(2,4,4-trimethylpentyl) phosphinic acid (Cyanex272), in heavy rare earths separation via hydrometallurgical processes has been investigated. The separation coefficients, , were obtained and the extraction selectivity has been evaluated using a mixture of heavy rare earths from Samarium to Ytterbium. The experimental results indicated that P507 and Cyanex 272 display a greater affinity for heavier rare earths while CA12 proved to be more effective for the lighter rare earth metals.

Jan 1, 2014

By J. van Driel

NOx is a growing concern for acid plant operators due to recent legislation reducing the allowable stack limits, as well as continually more stringent requirements for product acid quality. NOx also causes a major problem during maintenance as NOx rich acid residues fume following exposure to moisture in the air. Until recently, the solution for NOx related issues was to treat the symptom, rather than the cause. NOx in product acid was treated using chemicals and the NOx in the plant stack was generally left untreated. As part of an environmentally driven change in concentrates, Budel Zink installed the first gas phase NOx destruction process to be incorporated into a commercial scale acid plant. Nitrogen oxides contained in the process gas are reduced selectively with ammonia over a catalyst to form nitrogen and water. As a result, the NOx reduction is in agreement with the permit requirements.

Jan 1, 2002

By Takuya Shinagawa

After vitrification of the residues from a municipal solid waste incinerator, the vitrified products can be used as a construction material, and the dust can be used as raw materials for the non- ferrous industry. The NKK electric-resistance furnace is operated under a reducing atmosphere, and heavy metals such as zinc and lead in the ash vaporize to form dust. Also, dust from the NKK electric-resistance ash melting furnace is composed of water insoluble zinc and lead components and water soluble NaCl and KCI. This is why, The concentration of zinc and lead in the dust after washing is sufficiently high for the dust to be used as a raw material for the zinc and lead industry. NKK developed a heavy metal recovery process in which zinc and lead in the dust are reclaimed as a raw material for smelting by making the best use of the characteristics of the dust.

Jan 1, 2002

By Takaaki Ishikawa

The distribution equilibria of lead, zinc and copper between CaO-Si02-Ah03 melts and liquid copper were measured at 1623K under a controlled H2-C02 atmosphere. The distribution ratios were plotted against the oxygen partial pressure, and reasonable oxide forms dissolved in the melts were estimated from the slopes of the plots. The activity coefficients of zinc oxide (ZnO), lead oxide (PbO) and cuprous oxide (CuO0.5) increased with increasing slag basicity, defined by XCao/Xsio2 The temperature dependence of the activity coefficients was also measured.

Jan 1, 2003