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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 Caisa Samuelsson

Experimental studies in laboratory-scale equipment have been carried out to study the vaporisation from dust generated during the copper converting process. In the present work the vaporisation of Zn, Pb, As, Sb, and Bi from a dust collected in the electrostatic precipitator after the copper converter were studied. The results show that Pb, Bi and As were vaporised to a high degree from the dust at a temperature above 900°C in a gas containing N2, SO2 and a small amount of H2. The vaporisation was high for these elements also in a gas containing N2, SO2 and 02 at temperatures above 1120°C. In an earlier study, thermodynamic calculations showed that it is possible to selectively condense metals at high temperature' in a gas atmosphere generated during a copper converting process. The present study was carried out to verify the thermodynamic model. The results indicate that it should be possible for a selective condensation of Zn at high temperature. The temperature required for a selective condensation of Zn is dependent upon the gas atmosphere, e.g., the oxygen potential.

Jan 1, 1998

By J. R. Sarazin

Density driven convection during solidification has been recognized for some time to result in macrosegregation particularly when lower density alloying elements are rejected into the interdendritic liquid. The resulting segregates are commonly referred to as channels, freckles or A-segregates. Buoyancy driven convection leading to channel formation has been examined in three model systems possessing somewhat different materials parameters. They are the Pb-Sn eutectic system, the transparent aqueous-salt NH C1-H 0 4 2 eutectic system and the transparent organic succinonitrile-ethanol monotectic system. Convection in these systems is controlled by a balance of buoyant and viscous forces, which are strong functions of composition and temperature. Composition, temperature and flow velocity were measured and elimination of channels through heavier ternary additions is discussed.

Jan 1, 1991

By G. Van Weert

The pellet reactor was developed approximately 20 years ago in the Netherlands for softening drinking water. Since then, some 35 plants have been built, ranging in capacity up to 8500 m3/h. Applications now also include removal of phosphates and fluorides and the production of metal carbonates and sulphides from waste streams. The pellet reactor consists of a fluidized bed, wherein the process solution is thoroughly mixed with the precipitation reagent at special inlet nozzles to give over-saturation of the compound to be precipitated. In water softening applications, the compound is CaCO,. In the case of nickel or other metal waste streams, Na2CO3 solution is added in sufficient amounts to precipitate metal (hydroxy) carbonate on the fluid bed particles. These grow typically to dense spheroids, which are removed when they reach 0.8 to 1.0 mm diameter. These spheroids are easily dewatered, free flowing and low dusting. The latter property is becoming an attractive advantage in connection with new plant hygiene regulations. The operation of a 60 cm diameter pellet reactor on nickel containing plating waste is described and the properties of the produced nickel carbonate spheroids are discussed.

Jan 1, 1993

By Chuanfu Zhang, Liwei Liang, Yanxin Wu, Jinliang Wang

"According to the reaction shaft operation characteristics during the flash smelting process, 15 groups of slag samples containing high Fe3O4 were prepared by some chemical reagents, and then the slag viscosities were measured using a RTW-10 type synthetic test instrument for melt physical property by the rotating cylinder method. The effects of Fe/SiO2 ratio (mFe/mSiO2), Fe3O4 content (wFe3O4), Cu2o), MgO content (WMgO) and Cao content (wCaO) on the slag viscosity were also studied. Results show that slag viscosity is decreased with the increase of temperature, mFe/mSiO2, wCu2o, wMgO and wCao, and with the decrease of wFe3O4, under the range of slag contents: mFe/mSiO2 1.36~1.78, wFe3O4 17.83%~21.18%, wCu2o 3.51%~8.34%m wNgI 2.21%~6.57%m w/caI 6.22%~9.387% and temperature range if 1250 o/c~1450 oC. Only wFe3O4m and w/caO have great influence on the slag viscosity when temperatures as high as 1400 oC. Only wFe3O4 and wCaO have great influence on the slag viscosity when temperatures as high as 1400 oC or so. To form a freeze slag with higher viscosity inside the reaction shaft, wFe3O4 should be more than 20% and wCaO should be less then 6%.IntroductionSince its appearance in 1949, Outokumpu flash smelting technology has making continuous innovation and has become the most competitive intensified smelting technology [1], widely considered to be the standard clean smelting process [2]. At present, flash smelting technology is adopted to newly build or reconstruct most of the world's copper or nickel smelting enterprise [3]. Reaction shaft is the most important part of the flash smelting furnace. During the flash smelting process, reaction shaft must be able to withstand the following harsh conditions at the same time: 1) high temperature varying from 1400 °C to 1500 °C. 2) strong oxidative atmosphere containing 50% - 80% oxygen. 3) solid particles and melt with speed up to l00 m/s. 4) high acidic or basic slag with strong chemical corrosiveness. 5) smelting gas containing 50% - 80% SO2. 6) matte with strong dissolution."

Jan 1, 2012

By Yanhui Liu, Xuewei Lv, Chenguang Bai

A thermodynamic model for determining the surface tension of molten slag by considering the surface tension and molar volume of the pure oxide component, and their ionic radii was extended to the slag bearing high TiO2 (varying from 80 to 67%) at 1973 K. The iso-surface tension curves for the FeO-TiO2-Ti2O3 ternary system at 1973 K are almost parallel to the FeOTi2O3 line. TiO2 plays a role of surface-active solute, and its surface-active effect is attenuating with increasing the TiO2 content. The iso-surface tension curve shifts away from the TiO2 corner, indicating that the surface tension of the ternary slag decreases along with the addition of SiO2. The reasons include the addition of SiO2 with lower surface tension and the decrease of the total ion moment at the surface. Both CaO and MgO can bring about that the iso-surface tension curve shifts towards the TiO2 corner, indicating that the surface tension of the ternary slag increases along with the addition of CaO or MgO. CaO has a more pronounced effect on increasing the surface tension of the ternary slag than MgO at an equimolar amount addition. The increase of the surface tension results from both the compositional change and the variation of the slag structure.

Jan 1, 2015

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 Boyd Davis, Vladimiros Papangelakis, Joshua LaMarre, Jan de Bakker

"HCl leaching using molten salt hydrates has the potential to improve the extraction of nickel from laterite ores. However, as in other HCl leaching applications, recovery of HCl is key to process economics. Spray pyrohydrolysis, which is used in current chloride-based flowsheets, is associated with a high energy cost. The authors have developed a proposed laterite leach circuit using an alternative HCl recovery route. The leach circuit envisions a leach by concentrated (33%) HCl in an MgCl2 molten salt hydrate (MSH) or brine medium, followed by Ni/Co recovery and iron precipitation. Magnesium and chloride are precipitated from solution as magnesium hydroxychloride; this hydroxychloride is thermally decomposed to produce HCl gas. The proposed flowsheet employs a chloride leach circuit with simpler equipment and lower energy cost than in the conventional practice of pyrohydrolysis. Laboratory work investigated key aspects of the flowsheet, including precipitation of magnesium hydroxychlorides and their composition; magnesium hydroxychloride thermal decomposition; and iron control.Introduction As sulphide nickel ores become harder to mine and more complex to process, laterite ores will increase in importance. Laterite ore deposits can be divided into two main mineralogies. Limonite ores consist mostly of hydrated iron oxide, FeOOH, with 1-3% nickel substituting for the iron. Saprolite ores consist of iron-magnesium silicates, (Fe, Mg)2Si04, again with some nickel substituting for the metal ions. Limonite ores can be treated using the HP AL (High Pressure Acid Leach) process, in which the ore is reacted with sulphuric acid at high temperature in an autoclave. HP AL, however, cannot in general be used to treat saprolite ores because the magnesium enters solution and consumes sulphuric acid, which results in excessive spending on lixiviant. It is therefore desirable to find a hydrometallurgical process specifically for saprolite ores that can provide better results than the treatment options currently available."

Jan 1, 2011

By Guohui Zheng

The ever increasing quantities of solid wastes generated by various industries are at the source of the growing need for proper waste disposal methods. Thermal treatment of combustible wastes is a proven technology which permits the reduction of hazardous material having to be landfilled. However, this method is not universally applicable to waste disposal. For example, the transferal of heavy toxic metals into the thermal remediation products is a major issue of public concern. This paper focuses on the analysis of morphology changes from solid sludge to ash which is a product of the sludge combustion. The morphological parameters analyzed were particle size and external surface. They were determined using Jeol 840 Super Probe. The experiments were conducted in a computer-controlled high-temperature combustion system consisting of the thermogravimetric furnace coupled with Fourier transform infrared spectrometer (TGA-FTIR). Sludge particles were made of complex fibers trapped in the aluminosilicate matrix. At low temperatures, up to 680 K, the solid residue looked similar to the initial sludge. Between 680 K and 1180 K the sludge underwent intensive burning and steadily changed into powdered ash. At the temperature of 1050 K the ash was composed of separate, flat flakes with sizes ranging from 5 to 20 um. At 1470 K the flakes aggregated into large particles. The surface observed at 1670 K was a mixture of mullite crystals. Such structure could result from the solidification of the ash material after its melting. Morphological changes influenced the distribution of metals in the solid residue. For example, Cr was concentrated in small aggregates. Such distribution should allow for recovery of valuable metals from the solid waste residue.

Jan 1, 1996

By K. Yamada, T. Takaoka, A. Ozeki, M. Yamaga, Y. Kawai, S. Nishioka, Y. Kikuchi

"Recently, smelting reduction of chromium ore in BOF has been actively investigated as a key unit process for an innovative future stainless steelmaking. The prominent feature of this new process route is energy and process saving, and production cost saving. The development is already in the midst of application to the commercial production, however there still remain the following key technologies to be established for the full use of the process. One is a speed up of the reduction of chromium ore to match with sequential continuous casting, and the other is efficient combustion of carbonaceous materials in BOF to reduce their consumption, and hence to assure the steel quality. High degree of post combustion technology and new charging technology, i.e., ore-coal-flux-oxygen mixed injection, could be effective for those two subjects. In 2000 or beyond, the new process would have become quite popular owing to the establishment of those key technologies.Introduction Since stainless steel was invented, its production has continued to expand because of its attractive combinations of functions of excellent corrosion resistance, good formability, a pleasing appearance, and a wide range of strength levels. New types of stainless steels as well as new applications are continually being developed.Compared to the production of ordinary steels (1), stainless steel production (2,3) shows steady growth worldwide, while the former production remains on the same level, as Figure 1 shows. It can be estimated that future production would show further growth since materials consumer demands are more fashionable, or more functional, which could be satisfied by stainless steels.Thus market needs would be met, if it could be produced with reasonable production cost. The emergence of an innovative production technology is then potentially requested as VOD and AOD processes have emerged, which has saved substantial production cost. This paper describes a possibility of a future stainless steelmaking process, which uses the in-bath smelting reduction of chromium ore in BOF, and which would save production as well as energy cost."

Jan 1, 1988

By Wenxian Zhu, Patrick R. Taylor

"The small dimensions of nano-sized materials leads to novel and enhanced mechanical and physical properties. A thermal plasma reactor has been developed to study the formation of nanometer sized metal powders. A supersonic nozzle and a powder filter were designed and built. By vaporizing coarse metal powders in the plasma flame, and quenching the metal vapors through the nozzle at the rate of 107 K/sec, nanometric sized powders have been produced. The powders were collected in an airtight secondary quench-filter system. The particle size of the product power is 5 -20 nanometers, obtained through TEM analysis. The XRD analysis showed that the powder did not oxidize after the filter was handled in an inert atmosphere glove box.IntroductionNanostructured materials have been shown to exhibit improved physical and mechanical properties compared to conventional materials with larger grain sizes (1,2). There have been several methods proposed for preparing nanometer size materials. Thermally induced vapor-phase reactions have been used to produce a variety of powders. A common feature of these processes is the rapid production and cooling of condensable reaction intermediates and products, by gas-phase reactions, leading to the formation of a large number of very small particles. Thermal plasma synthesis of ultra-fine size particles has been attracting increasing interest (3,4,9-11), because it offers many advantages, especially in refractory materials processing, compared to conventional processes: (a) thermal plasma temperatures are very high(> 5000 K); (b) the rates of chemical reaction are much faster than those encountered in conventional processes; (c) high-purity materials may be obtained using fewer processing steps by collecting the product at temperatures where the by-products are in the vapor phase; ( d) the mean particle diameter can be controlled; (e) unifom sized particles may be produced with clean surfaces (these particles are particularly suitable for pressureless sintering); and, (f) high throughput per reactor volume can be achieved. In addition, the process used for generating particles determines the degree of sintering ability of the powders, since the process dictates the morphologies, the purity and its size distribution. In the future, thermal plasma synthesis nanometer size particles may play an important role in vapor phase reaction techniques and might be expected to be one of the first full scale commercial installations in the future."

Jan 1, 1998

By J. A. Bakken

Thermal plasmas are interesting for a wide range of metallurgical and chemical processing applications. The 300 kW experimental reactor PRESS, which has been in use since 1987, is operated in the transferred arc mode with three or one plasma torches . Tests include remelting of silicon fines and production of ultrafine silica. Work on a novel three stage process for production of silicon metal is under way. A 1:1 model of the plasma reactor is used to measure the wall heat flux distribution calorimetrically. The cold walls of this model are divided into several water-cooled sections. The same plasma torches as in the real hot-wall reactor are used. In parallel to the experiments and calorimetric measurements theoretical work is done on numerical modelling of one and three transferred arcs. A modified version of the flow simulation program FLUENT from Creare Ltd. is used.

Jan 1, 1991

By Ralph H. Nafziger

The Bureau of Mines, in cooperation with the Idaho National Engineering Laboratory, has electroslag melted a V-5Ti-5Cr alloy using a fused CaF2, flux. The alloy is a candidate for use in future fusion reactors. One objective of this research was to evaluate the feasibility of the electroslag melting process in separating simulated radioactive isotopes from the V alloy to demonstrate recyclability. Small amounts of Ca, Y, and Mn were added as surrogates for radioactive isotopes. Results showed that this vanadium alloy can be electroslag melted satisfactorily. The impurities added intentionally were removed or decreased successfully. Among the major alloying constituents, Cr was retained but there were some Ti losses. The latter may be controlled with process refinements. This research suggests that the electroslag melting process could be a suitable method for recycling V alloys after use in future fusion reactors, or for processing other reactive metal alloys with more immediate applications.

Jan 1, 1996

By B. Erik Ydstie, Dimitrios I. Gerogiorgis, Sridhar S. Seetharaman

"Carbothermic production of aluminium is an important alternative to electrolytic processes and has in fact been identified several decades ago as a potentially feasible and profitable process. The cornerstone principle is to take advantage of the endothermic reduction reaction between carbon and alumina instead of resorting to extreme amounts of electric energy to ionize and reduce aluminium oxide to aluminium. Electric energy is necessary only for heating purposes.The present study focuses on constructing and solving a steady-state electrothermic model for obtaining the spatial distributions for electric potential, electric field intensity and temperature. The complex issues of reaction kinetics and multiphase flow are handled by an approximation and are not addressed at the present stage, due to the lack of complete validated models. Because of its inherent complexity, the reaction slag is considered a pseudohomogeneous layer.An electrothermic simulation encompasses important research challenges, due to the limited knowledge of thermophysical properties for high-temperature multi component molten slags. Therefore, thermophysical property modeling and a systematic compilation of published data is a necessary and major first step towards enhancing understanding of the process fundamentals. Models are obtained by analyzing measurement data from numerous literature references for the density, viscosity, thermal and electrical conductivity and specific heat capacity of the slag.The electric potential, field intensity and temperature distributions obtained reveal interesting maxima which indicate localized superheating and lead to important engineering conclusions. The temperature profile calculated will serve as the foundation for the flow problem solution. This computational study will form a basis for future research towards combining the scopes of microscale CFD modeling and mesoscale process modeling into a unified modeling approach."

Jan 1, 2001

By Robert Vidal

The performance of a laboratory-scale cell for the electrolysis of an aqueous chrome alum solution was studied. Electrode potentials, pH, and Eh were recorded. An optimum catholyte pH of about 2.5, consistent with information from the literature was observed. Values exceeding this range resulted in a precipitate formation and are detected by wavering cathode potentials. The role of anodically produced dichromate ions was investigated by chemical analysis. It was found that the steady state concentration of dichromate ions varies inversely with fluid flow from catholyte to anolyte. This concentration was also reduced with the use of precious metal coated titanium anodes.

Jan 1, 1994

By Vaughan R. Voller

"Solidification systems from conduction controlled freezing of a pure material through to alloy phase change that include flow and segregation processes are described. The components in a general solidification model-variables, governing transport equations, and local scale relationship-are outlined. A central focus is the presentation of an explicit procedure for coupling between macroscopic and local scale variables.IntroductionSince the seminal work of Byres et al.[!] in the 1940's there has been a steady progress in modeling solidification systems with increasing levels of complexity. The object of this paper is to track the evolution of these solidification models and present a general modeling approach that applicable to a wide range of the solidification systems of current interest.Solidification SystemsIn a broad sense the underlying physics in a solidification process occur at two distinct length scales:1. The macroscopic scale of the process over which the governing transport equations of heat, mass and momentum hold.2. The local scale at the solid-liquid interface where the solidification phenomena are operative."

Jan 1, 1999

By Kenneth N. Ham

Hydrometallurgy covers a wide spectrum of areas and its knowledge base is enlarged and enhanced by contributions from many other fields. Dissolution of metals and alloys in aqueous media will be used to illustrate how rich the field of metal extraction can be. Comprehensive understanding of the fundamentals of metal and alloy dissolution in aqueous systems requires creative application of thermodynamic principles, solutions chemistry, ligand complexation theory, electrochemistry, transport phenomena and heterogeneous kinetics. In addition, recent developments in instrumentation in the fields of interfacial phenomena and corrosion have tremendously advanced the field of metal extraction in aqueous system. The close relationship between metal extraction in aqueous systems and various physicochemical phenomena occurring in corrosion and interfacial systems will be discussed and illustrated with examples.

Jan 1, 2002

By S. Ozbilen, B. Erdogan, M. Erdogan

To study by thermal analyses the response of precipitation hardenable alloys of Al-Cu-Mg and Al-Li-Cu-Mg system to natural and artificial ageing, a series of ternary and quaternary Al-alloys with nominal compositions of Al-l.13wt%Cu-0:65wt%Mg (alloy-I), Al-1.15wt%Cu-0.57wt%Mg-0.07wt%Li (alloy-2), Al-l.19wt%Cu-0.56wt%Mg-0.75wt%Li (alloy-3), Al-2.0lwt%Cu-0.89wt%Mg (alloy-4), Al-2.14wt%Cu"0.56wt%Mg-0.07wt%Li (alloy-5) were used in the present investigation. Samples in the form of rolled sheets are subjected to water quenching at 25EC after solution treatment at 530EC for 20 min. Alloys were aged naturally at room temperature (25EC) up to 2 months and artificially at 190EC up to 2 days. By using differential scanning calorimetry (DSC) in the temperature range of25-300EC, differential thermal analysis (DTA) in the temperature range of25-600EC together with Vicker's hardness measurements, the response to natural and artificial ageing of the alloys used in the present study were investigated. It was observed that in these alloys, GPB(Cu, Mg) zones [Guinier-Preston zones with Cu and Mg] do form during water quenching at 20EC following solutionizing heat treatment. Natural ageing of the same alloys causes formation of more GPB(Cu, Mg) zones, which results in hardening in the alloys. Artificial ageing at 190EC up to l day results in GPB zone dissolution causing preliminary decrease in hardness values while two days of artificial ageing in the alloys cause S' (Al2CuMg) precipitation confirmed by DSC/DTA analyses resulting in an increase in hardness values. Li addition up to 0.75wt% helps T1 (Al2CuLi) and T 2 (Al6CuLi3) phase formation together with S' precipitation as DSC/DTA analyses show after the same heat treatment.

Jan 1, 1998

By Jing Zhan

The fibrous precursor can be obtained by coordination precipitation process, using oxalate, cobalt chloride and ammonia. The composition and morphology of fibrous precursor were characterized by XRD, IR, DTA/TGA and SEM analysis. The results show that XRD pattern and composition of the precursor with fibrous morphology precipitated at pH=9.0 were different from that of ß-CoC2O4?2H2O precipitated at pH=1.0. The mechanism on the thermal decomposition of fibrous precursor was addressed. The influences of various conditions in pyrolysis, including the temperature, time, atmosphere, and the morphology of the precursor, on the morphology, average size and specific surface area of the Co powders were investigated in detailed. At last, the final product, fibrous cobalt powders with diameter about 0.3~0.5µm in size and 40~60 in aspect ratio, were produced by thermal decomposition at 400~500? in the weak reducing atmosphere. The structure of pores in cobalt powders was capillary tube with open ports and the majority was mesoporous.

Jan 1, 2009

By Run-sheng xu, Hai-yang WANG, Di ZHAO, Teng-fei SONG, Jian-Liang Zhang

This paper was mainly focused on the different semi-cokes and charcoal which could be new fuels for blast furnace injection. Through the comparative study with bituminous coal and anthracite coal, the properties of semi-cokes and charcoal were presented in this research. 10 indexes of different fuels were obtained by different standard experiment, including proximate analysis, ultimate analysis, igniting point, explosivity, transportation characteristic, ash properties, grindability, calorific value, combustibility and reactivity with CO2. According to the data analysis, it provided a theoretical basis for rational utilization of various blast furnace fuels, and helped to broaden the scope of the blast furnace injection fuels. This research could contribute to energy conservation, emissions reduction, and sustainable development of iron and steel enterprises.

Jan 1, 2015